Chemistry (Annual Reports - Vol.59-1962)

Annual Reports
On The Progress Of Chemistry
G. 0. ASPINALL,D.Sc., F.R.S.E., F.R.I.C. WILSON BAKER, M.A., D.Sc., F.R.S. C. H. BsMFoRD,&I.A., Sc.D., F.R.I.C. J. W. BARXETT, Ph.D., A.R.C.S., F.R.I.C. R. P. BELL, N.A., F.R.S. D. M. BROWN,Ph.D. G. M. BURNETT, Ph.D., D.Sc. I. G. M. CAYPBELL,B.Sc., Ph.D. G. E. COATES,>LA., D.Sc., F.R.I.C. T. COTTRELL, D.Sc., B.Sc., F.R.I.C. D. P. CRAIQ, Ph.D., D.Sc., F.R.I.C. D. F. ELLIOTT, Ph.D., A.R.C.S., A.R.I.C. V. GOLD, D.Sc., Ph.D. R. H. HALL, Ph.D., A.R.C.S., F.R.I.C. C. H. HASSALL, M.Sc., Ph.D., F.R.I.C. A. W. JOHNSON, Ph.D., A.R.C.S. Sc.D., C. KEYBALL,N.A., Ph.D., F.R.I.C.
J. G. J. J.
A. KITCHENER,D.Sc., Ph.D. KOHNSTAM, Ph.D. W. LINNETT,M.A., D.Phil., F.R.S. F. W. MCONIE, M.A., D.Phil., D.Sc. R. S. NYHOLY, D.Sc., F.R.I.C., F.R.S. L. E. ORQEL,M.A., D.Phil., F.R.S. L. N. OWEN,Ph.D., DSc., F.R.I.C. R. A. RAPHAEL, D.Sc., F.R.I.C., F.R.s.
J.M.RoBERTsoN,C.B.E.,M.A.,D.SC.,F.R.S.
A. G. SHARPE, M.A., Ph.D., F.R.I.C. K. W. SYKES, M.A., D.Phil. J. C. TATLOW,B.Sc., Ph.D., F.R.I.C. H. J. V. TYRRELL,B.Sc., M.A. B. C. L. WEEDON,D.Sc., A.R.C.S., F.R.I.C. D. H. WHIFREN, M.A., D.Phil. M. C. WHITINQ, M.A., Ph.D., A.R.C.S. W. WILD, Ph.D.
Eio dtr
R. S. CAHN, M.A., D.Phil.Nat., F.R.I.C.
Deputy Editor L. C CROSS, Ph.D., A.R.C.S., F.R.I.C. .
Assistant Editors
I. J. CANTLON, Ph.D.
N. KEEN, Ph.D.
Contributors
R. C. R. K.
M. ACHESON, M.A., D.Phi1. C. BARKER, B.Sc., Ph.D. F. BARROW,B.Sc., M.A., D.Phi1. W. BENTLEY, A . , B.Sc., D.Phil. K
J. H. KNOX, B.Sc., Ph.D.
M. L. MCGLASHAN, Ph.D., D.Sc., F.R.I.C.

S. MARES, M.Sc., D.Phil. J. NEREB, B.A. J. MILLEN, B.Sc., Ph.D. NICHOLLS,B.Sc., Ph.D., A.R.I.C. K. H. OVERTON,Ph.D., 13.S~. C. W. REES, B.Sc., Ph.D. D. H. REID, B.Sc., Ph.D. R. E. RICHARDS,M.A., D.Phil., F.R.S. D. J. SUTOR,M.Sc., Ph.D. (N.Z.), M.A., Ph.D. (Cantab.) M. C. R. SYJIONS, D.Sc., F.R.I.C. T. L. V. ULBRICHT,B.Sc., Ph.D. J. V. WESTWOOD, M.Sc., F.R.I.C. A. M, WHITE, B.Sc., Ph.D. R. F. M. WHITE, B.Sc., Ph.D., A.R.I.C. D. W. WILSON, XSc., F.R.I.C. G. A. D. D.
B. CAPON,B.Sc., Ph.D. P. F. S. CARTWIUQHT, M.Sc., Ph.D.,
F.B.I.C. W. COCHRAN, Ph.D., F.R.S. B. A. CRAIG, M.Sc., D.Phi1. L. CROMBIE,Ph.D., D.Sc., F.R.I.C. G. EQLINTON,B.Sc., Ph.D. D. F. ELLIOTT, Ph.D., B.Sc. C. P. FAWCETT, B.Sc., P1i.u. R . P. H. GASSER,M.A., D.Phi1. V. GOLD, Ph.D., D.Sc. G. W. GRAY,B.Yc., Ph.D. A. K. HOLLIDAY, Ph.D., D.Sc., F.R.I.C. J. HONEYXAN, X.A., B.SC., Ph.D., D.Sc. V. T. JAXES B.Sc.. PI1.D.. A.R.I.C. I .
THE CHEMICAL SOCIETY
Annual Reports
On The Progress Of Chemistry
FOR 1962
Volume LIX
LONDON 1963
THE CHEMICAL SOCIETY

PATRON
HER MAJESTY THE QUEEN
President
J. M. ROBERTSON, C.B.E., M.A., D.Sc., F.R.S.
H. J. EMEL~US, C.B.E., M.A., D.Sc., F.R.S. SIR CYRIL HINSHELWOOD, O.N., M.A., Sc.D., F.R.S. E.L. HIRST,C.B.E., D.Sc., LL.D., F.R.S.
SIR CHRISTOPEER INQOLD, F.R.I.C., D.Sc., F.R.S. SIRERICRIDEAL,M.B.E.,M.A., D.Sc.,F.R.S. LORDTODD, X.A., D.Sc., F.R.S.
D. H. R. BARTON,D.Sc., Ph.D., F.R.S. E. J. BOWEN, M.A., D.Sc., F.R.S. J . CHATT, M.A., Sc.D., F.R.S.
E. R. H. JOKES, D.Sc., F.R.I.C., F.R.S. B. LYTHQOE, M.A., Ph.D., F.R.S. M. S ~ C E Y , Ph.D., D.Sc., F.R.S.
Honorary Secretaries
A. W.
JOHNSON, Sc.D., Ph.D., A.R.C.S.
E. W. SYRES, M.A., D.Phil. J, W. LINNETT, M.A., D.Phil., F.R.S.
D.Sc., Ph.D., F.R.I.C. G. 0. ASPINALL, J. BADDILEY, D.Sc., Ph.D., F.R.S. L. J. BELLAMY, B.Sc., Ph.D. W. COCKER,M.A., D.Sc., F.R.I.C., M.R.I.A. D. P. CMG, M.Sc., D.Sc. L. CROXBIE, D.Sc., F.R.I.C. F. S. DAINTOP;,M.A., Sc.D., F.R.S. D. H. EVERETT, M.B.E., M.A., D.Phil. B.Sc., Ph.D. G. W. A. FOWLES, W. GERRARD, D.Sc., Ph.D., F.R.I.C. R. N. HASZELDINE, M.A., Sc.D., F.R.I.C.
I. HOLLIDAY, ( Ph.D., D.Sc., F.R.I.C. HONEYMAN, Ph.D., D.Sc. R. KATRITZKY, M.A., D.Phil., Ph.D. J. KING, B.Sc., M.A., D.Phi1. E. A. MOELWYN-HUQHES, D.Phil., D.Sc. Sc.D. W. J. ORVILLE-THOMAS, Ph.D., D.Sc. H. M. POWELL, B.Sc., M.A., F.R.S. R. A. RAPHAEL, D.Sc., F.R.I.C., F.R.S. J. C. ROBB,DSc., Ph.D. A. I. VOGEL, XSc., D.Sc., F.R.I.C.
A. J. A. T.
Ex OWcio
SIR JAMES COOK, DSc., F.R.I.C., F.R.S. (Chairman of the Chemical Council) D. H. HEY, D.Sc., F.R.I.C., F.R.S. (Chairman of the Publication Committee) E. D. HUGHES, D.Sc., F.R.I.C., F.R.S. (Chairman of the Joint Library Committee)
General Secretary
J. I . RUCKKEENE, M.B.E., T.D., M.A. t
Librarian
R. G. GRIFFIN, F.L.A.
CONTENTS
PAQE
GENERAL AND PHYSICAL CHEMISTRY 1. INTRODUCTION. Richards By R. E. . 2. ULTRA-HIGH VACUA. By R. P. H. Gasser . 3. GAS-PHASE OXIDATION. By J. H. Knox . 4. ELECTRON SPIN RESONANCE. M. C. R. Syrnons By . 5. NUCLEAR MAGNETICRESONANCE ELECTROLYTE IN SOLUTIONS. By R. A. Craig . 6. EQUILIBRIUM PROPERTIESLIQUIDMIXTURES. By OF M. L. McGlashan . By 7. SPECTROSCOPY OF DIATOMIC MOLECULES. R. F. Barrow and A. J. Merer . INORGANIC CHEMISTRY 1. INTRODUCTION. Holliday and D. Nicholls By A. K. 2. TYPICAL ELEMENTS.By A. K. Holliday . 3. THE TRANSITION ELEMENTS. By D. Nicholls .
7 7 18 45 63 73 99
129 130 152
ORGANIC CHEMISTRY 1. INTRODUCTION. By L. Crombie and V. Gold . 2. PHYSICAL PROPERTIES ORGANICSTRUCTURE. AND By D. J. Millen and R. F. M. White . 3. REACTION MECHANISMS. By C. W. Rees and B. Capon 4. GENERAL METHODS. By C. C. Barker and G. W. Gray 5. ALIPHATIC COMPOUNDS, By G. Eglinton . 6. ALICYCLIC COMPOUNDS. By K. H. Overton . 7. AROMATIC COMPOUNDS. By D. H. Reid . 8. HETEROCYCLIC COMPOUNDS. By R. M. Acheson . 9. ALKALOIDS. By K. W. Bentley . 10. CARBOHYDRATES.By J. Honeyman . 11. NUCLEIC ACIDS. By T. L. V. Ulbricht .
187 189 207 254 268 281 307 319 342 359 37 1
BIOLOGICAL CHEMISTRY 1. INTRODUCTION. D. F. Elliott . By 384 2. THE BIOSYNTHESIS PORPHYRINS. G. S. Marks . 385 OF By 3. VITAMIN B12. By A. M. White . 400 4 THE NICOTINAMIDE . COENZYMES AND THEIR APOENZYMES. By C. P. Fawcett 413 5 . METABOLISM STEROID OF HORMONES. V. H. T. James 426 By
ANALYTICAL CHEMISTRY. By D. W. Wilson, J. V. Westwood, and P. F. s. Cartwright 1. INTRODUCTION 436 2. GENERAL 437 3. BASICOPERATIONSAND APPARATUS . 438 4 QUALITATIVE ANALYSIS . 440 5. METHODSOF SEPARATION. 443
vi
CONTENTS
6. GRAVINETRIC AKD TITRIMETRIC ANALYSIS . 7. INSTRUMENTAL END-POINT DETERMINATIONS 8. DETERMINATIONELEMENTS ORGANIC OF IN COMPOUNDS
9. SPECTROSCOPIC ANALYSIS 10. ELECTRICAL METHODS 11. THERMAL METHODS
. .
. . .
. .
PAQE
449 457 473

476
. 480
499
501 506
515
CRYSTALLOGRAPHY 1. GENERAL.By W. Cochran . 2. ORGANICSTRUCTURES. D. J. Sutor By INDEX OF AUTHORS INDEX O F SUBJECTS
.
.
.
.
.
. .
556 566
NOTE ON PRINCIPAL REFERENCES USED
ANNUAL REPORTS
ON THE
PROGRESS OF CHEMISTRY
GENERAL AND PHYSICAL CHEMISTRY
1. INTRODUCTION
THE reports this year cover a small number of selected topics, and refer to developments over a'period of more than one year. The extensive and detailed studies of the thermodynamic properties of liquid mixtures have not been reported for some time, so this work is summarised in considerable detail. We also include reports on the kinetics of oxidation reactions and on the uses of ultra-high vacuum techniques. The availability of such low pressures now has a very important bearing on the study of gas-solid surface phenomena. I n recent years impressive progress has been made in the study of energy levels of simple molecules. The accurate and extraordinarily detailed information available from the spectra of these molecules is a challenge to the theoretical chemist, and we report the present state of this field of work. The study of electron-spin resonance spectra has grown in a most remarkable way in recent years; it therefore seemed desirable to include a further report on this subject. A report on nuclear magnetic resonance spectroscopy of organic compounds appeared last year, and this is now supplemented by an account of work which has been done on solutions of electrolytes.
R.E. R.
2. ULTRA-HIGH V A C U A As this subject has not been reported on previously, the intention is to give a rather general account of results of interest to chemists. Sufficient references have been included to make it possible for those who wish t o pursue the subject further t o do so. By ultra-high vacuum, a pressure below mm. Hg will be implied. A simple calculation based on the kinetic theory of gases demonstrates the advantage t o be gained by reducing the pressure from the conventional mm.) t o the ultra-high vacuum region. The high-vacuum region (ca. rate of collision of gas molecules with a surface, p, is given by p = P(SnmkT)-4 collisions cm.-2 sec.-l where rn = the mass of a molecule. For oxygen a t loF6mm. and 23" c , is 5 x 1014 collisions cm.-2 sec.-l. A typical metal surface has ca. 10l5 u so that, unless the colliding gas has a very small probability of atoms
G E N E R A L A N D PHYSICAL CHEMISTRY
sticking, a surface which was clean originally will become covered by a monolayer of gas within a few seconds. However, a thousand-fold decrease in pressure increases the time for monolayer formation by the same factor and the surface stays clean long enough to be studied. It is also possible t o investigate the interaction of the surface with an experimental gas a t pressures in the loe7 mm. region without significant interference from the residual vapour. It is in the field of gas/metal-surface interactions that the most considerable progress has been made and with which this report will mainly deal. Experimental Methods.-There is evidence that pressures approaching the ultra-high vacuum region were being obtained a t times when conventional ionization gauges were recording pressures in the ordinary highvacuum region. This is now known to be due to the X-ray limit of an ionization gauge, which arises as follows. The impact of the electrons, comprising the grid current, causes the grid metal to emit soft X-rays. These X-rays eject electrons from the positive-ion collector and thus give rise to a current at the collector in the same sense as that which records the pressure. The usefulness of the conventional ionization gauge is limited by this process to the recording of pressures down to the mm. region. A pioneering paper in the ultra-high vacuum field is that of Alpert,l who, recognizing the limitations of the ionization gauge, designed a new gauge with a much lower X-ray limit. He also demonstrated the conditions under which ultra-high vacuum could be obtained repeatedly and without sealing off the apparatus from the pumps. The ionization gauge designed by Bayard and Alpert 2 is widely used in ultra-high vacuum studies. It reduces the X-ray limit to below 10-10 mm. by inverting the arrangement of the electrodes. The cathode is outside the cylindrical wire grid and the positive-ion collector is a fine wire running axially down the grid. This wire collects positive ions produced by electron bombardment in the volume defined by the grid. The positive ion current thus produced is directly proportional to the gas density, and therefore to the pressure. This fine wire collector presents a much smaller area for X-ray bombardment than the usual collector so that the X-ray limit is correspondingly lower. Current modifications to the original gauge include : (i) The use of lanthanum boride-coated filaments. These give off thermionic electrons a t much lower temperatures than tungsten, which is normally used. This is an improvement because one of the problems associated with the use of thermionic gauges is that of the interaction of the hot filament with the gases in the system; the lower the filament temperature, the less important are these undesirable side reactions. (ii) The use of still finer wires to reduce the X-ray limit even further. An important condition for obtaining ultra-high vacua is to avoid completely the use of greased taps. Alpert has designed an all-metal closure valve which is turned off by forcing a metal cone very hard into a metal seating. Movement is allowed by use of a flexible metal diaphragm, attached t o the cone. Although such a valve does not switch off completely, con,
D. Alpert, J. Appl. Phys., 1953, 24, 860. R. T. Bayard and D. Alpert, Rev. Sci. Instr., 1950, 21, 571.
G A S S E R : U L T R A - H I G H VACUA
ductances as low as 10-14 1. sec.-l can be obtained. It has the very important properties that it is robust, and can be heated t o temperatures as high as 500" c without harm. It thus becomes possible to outgas an entire vacuum assembly by heating it as a whole in a bake-out oven. It is common to use temperatures approaching the softening point of glass. Further outgassing of the metal electrode assembly of the gauge is usually necessary, and electron bombardment or radio-frequency heating t o red-heat will accomplish this. Conventional diffusion pumps can be used for ultra-high vacuum work, provided that a very efficient trap is incorporated between the pump and the apparatus, to collect back-streaming vapour. A common and reliable trap is a vessel, cooled with liquid air, so designed that back-streaming molecules have to make many collisions with the cold walls before they reach the apparatus. Non-refrigerated traps have also been used with success; trapping materials include rolled up copper foil and artificial mm. can be obtained zeolite.4 By these means a pressure of ca. 3 x as a matter of routine. On isolation of the system from the pumps, the pressure can be reduced still further by operating the gauge a t a high emission (Le. cathode to grid) current, when it will act as an " ion pump " of maximum pumping speed about 2 1. sec.-l. When operating the gauge as a measuring device, this pumping is reduced as far as possible by using small (10-100 FA) emission currents. As an alternative to diffusion pumps, " getter-ion " pumps can be used. The details of the mode of operation of these pumps are still not clear, but in principle they are considered to transfer gas from the gaseous phase to the walls of the pump by a combination of gettering and ionic pumping. The backing pressure required for them to start up can be obtained by cooling an adsorbent material in liquid air. It is thus possible to have a completely oil-free system. I n spite of this, however, hydrocarbons are produced in the system from impurities in the getter. The Theoretical Approach to Ultra-high Vacua.-The experimental methods described above represent a well-tried but largely empirical technique, and it is useful to consider the factors which limit the attainment of ultra-high vacua. The strength of binding of molecules of the atmospheric gases to the walls of the apparatus plays an important part in determining the rate a t which the apparatus can be pumped out. I f the molecules,are strongly held they cannot be removed, but neither do they evaporate, and thus they make no contribution t o the vapour pressure. Weakly-held molecules evaporate rapidly and are removed by the pump. It is thus the molecules with intermediate binding energies which give rise to the continuous evolution of gas experienced in unbaked apparatus. A quantitative treatment has shown that, a t room temperature, gases with heats of adsorption in the range 15-25 kcal. mole-1 are the most troublesome. However, on raising the temperature to 300" c these gases are rapidly evolved. This
D. Alpert, Westinghouse Research Lab. Scientific Paper 1744 (East Pittsburgh, U.S.A. 1953). L. L. Levenson and N. Milleron, Trans. Vacuum Syrnp., 1961, 91. J. P. Hobson, Trans. Vacuum Syrnp., 1961, 26.
10
result implies that rather less extreme conditions of outgassing than those previously described may be adequate t o achieve ultra-high vacua, a conclusion which can be confirmed by the Reporter who has obtained pressures below mm. after bake-out in the 250-3OO"c range. Besides outgassing from the walls, another factor which may limit the attainment of ultra-high vacua is the diffusion of gas from the atmosphere through the walls of the apparatus.l Glass is a very convenient constructional material and is widely used in vacuum apparatus, so that it is important t o know in what circumstances the inflow of gas becomes significant. There is much information about the permeation of helium, and data are now also available for other gases.6 The relative importance of the permeation of various gases can best be appreciated by considering their build-up in a sealed-off system. Consider a vitreous silica bulb of capacity 330 C.C. with walls 1 mm. thick and surface area 100 sq. em. a t 25" c. Then, starting with a negligible pressure, at the end of one year the pressures would be: loW4 mm. of He, mm. of Ne, and mm. of H,. No other gases would be present. Even after 100 years only a few molecules of oxygen would have penetrated. There is a marked difference in permeability between various types of glass. I n a bulb as specified the time taken for the pressure of helium t o build up t o mm. would be as follows: Silica, 3 days; Pyrex, a month; soda-lime, about 100 years. All gases permeate glass a t a rate directly proportional to their partial pressure, the flow being molecular. Steel walls are impermeable to all gases a t room temperature except hydrogen, which flows as atoms. The lowest pressure which could possibly be obtained would occur, of course, when there were no gaseous molecules present a t all. This situation has been approached through a combination of ultra-high vacuum and cryo-, genic techniques.7 The apparatus was first pumped down to ca. mm. and isolated from the pumps. Then part of it was immersed in a liquid helium bath, when physical adsorption of the residual gas occurred on the cold walls. Extrapolation from measurements a t high coverage indicates that, a t equilibrium, the pressure in the cold part should be in the region of 10-35 mm., i.e. there is no gas molecule within its volume for most of the time. Results.-Any property of a surface which is modified by the adsorption of gas can, in principle, be used to study the gas-surface interaction. I n this section three widely used techniques utilizing ultra-high vacua will be described. FieEd-emission microscopy. This is probably the most important and informative method of studying gas-metal interactions. * The principle of operatioh of the field-emissionmicroscope lies in the modification, by a very large potential gradient, of the potential-energy barrier preventing the escape of electrons from the surface of the metal. Under the influence of a gradient of ca. lo7 v cm.-l, electrons can tunnel through the distorted
F. J. Norton, Trans. Vacuum Syrnp., 1961, 8. J. P. Hobson, Trans. Vacuum Symp., 1961, 146. R. Gomer, " Field Emission and Field Ionisation," Oxford University Press,
1961.
GASSER: ULTRA-HIGH V A C U A
11
barrier at a rate which is approximately independent of temperature, in the A range 0-300" K . Currents of the order of loA7 can be drawn a t temperatures hundreds of degrees below that at which thermionic emission is appreciable. The actual current obtained depends on the work function, #, of the surface in a complex manner. However, the appearance of a term of the form exp(4312)shows that i will vary very markedly with changes in 4. The large voltage gradients required for a field-emission microscope are obtained by making the field-emission source in the form of a very fine point (ca. 1000 A diameter), and mounting it at the centre of a bulb of about 5 em. radius. The inner surface of the bulb is coated with conducting and fluorescent layers and the application of 1-20 kv. to this screen produces the necessary voltage gradient at the tip. The fluorescent screen provides a visual demonstration of differences in work function of the surface, magnified some 105-106 times. The observed regions of light and dark, from a clean tip, are due to the differences in work function of the various crystal planes present at the surface. Adsorption of a gas alters the work function, and therefore the field-emission pattern, of a tip. This has been used to study the physical adsorption of inert gases on tungsten.9 with the perhaps surprising results (i) that the adsorbed gas retains liquid-like properties below the bulk melting point of the adsorbate, and (ii)that adsorption gives rise to a substantial dipole moment (0.1-0.8 D) in the adsorbate. The heats of adsorption, however, are in the expected range, 2-10 kcal. molew1. From the large number of papers dealing with chemisorption on fieldemission tips, it has been possible to build up a fairly detailed picture of the surface processes involving diatomic molecules and refractory metals, particularly tungsten. Hydrogen, oxygen, nitrogen, and carbon monoxide are all adsorbed rapidly, and without activation, even at low temperatures ((70" K). The homonuclear molecules are dissociated into atoms, but carbon monoxide is adsorbed without decomposition. The migration of adsorbed species over the surface has been studied at low temperatures (ca. 20-70' K). To do this, part of the tip is given a multimolecular-layer deposit of gas at liquid helium temperature, where the adsorbed layers are immobile. On warming the tip, migration of the physically adsorbed layers occurs (at 27 O K for oxygen) on to the clean regions of the surface, where they become chemisorbed and immobile. More physically adsorbed gas can now migrate over the new deposit and extend the region of chemisorption. This process produces changes in the fieldemission pattern, and it continues until either all the tip is covered or all the original deposit of gas is used up. If the latter happens, no further change in the field-emissionpattern occurs until the migration of chemisorbed atoms sets in at much higher temperatures (about 500" K for oxygen). The activation energies for the two types of migration are about 1 kcal. mole-1 and 25 lwal. mole-l. At still higher temperatures the gas desorbs and eventually the pattern of the clean tip is regained. From these measurements the heats of desorption are obtained. For many systems, the activation energy for migration is about one-fifth of the binding energy of the atom to the surface.
OG. Ehrlich and F. G. Hudda, J . Chem. Phys., 1959, 30, 493.
12
G E N E R A L AND P H Y S I C A L CHEMISTRY
The field-emission microscope has recently been used to study the interaction of simple hydrocarbons with an iridium tip10 It was suggested that, for ethylene, adsorption is dissociative and that heating progressively dehydrogenates the adsorbed species, hydrogen being evolved, until a carbonaceous deposit is left. Related t o the field-emissionmicroscope is the field ion microscope. This is essentially a field-emission microscope operated in reverse with the tip as anode, instead of the screen. For its operation it requires a reasonable pressure of gas (ca. mm.), and either hydrogen or helium is commonly used. When a gas molecule comes into the region of high potential gradient, near the tip, it may be ionized by the tunnelling of one of its electrons on to the tip. The positive ion thus produced is accelerated to the screen. The pattern produced on the screen by many such ions is characteristic of the surface of the tip. The resolution of the field ion microscope is greater than that of the field-emissionmicroscope and, indeed, is so great that it has been possible t o see the effect of a single nitrogen molecule upon the pattern from a tungsten tip.11 This very refined technique is unfortunately limited t o the observation of very strongly-bound species. This is because the potential gradients required are some ten times greater than for the fieldemission microscope, and subject the tips to such great mechanical stress, ca. 1011 dyne cm.-2, that any weakly bound species, including atoms of the tip itself, may be field desorbed. Flash-$lament experiments. This technique was introduced in 1953 and, since then, has been widely used as a method of studying the interaction of simple gases with the very high-melting metals. The principle of the method is as follows. The metal is rapidly heated electrically to about 2000K, i.e. flashed, in an ultra-high vacuum to remove the adsorbed layers of atmospheric gases. The experimental gas is then admitted to the mm. range is established. On cooling apparatus and a pressure in the the filament, gas is adsorbed. After a chosen time the filament is flashed thus desorbing all the gas and causing a rapid rise in the pressure. Provided that the time constant of the pressure-measuring equipment is short compared with the flashing time (usually ca. 1 sec.), the evolution of gas can be recorded accurately on an oscilloscope or fast writing recorder. The kinetic theory of gases gives the number of molecules which have collided with a filament of known dimensions and the desorption curve gives the number which have stuck. The results of these experiments are expressed in terms of the probability that, on striking the surface, a molecule is adsorbed. For nitrogen on tungsten there is general agreement that there is a strong probability of a fruitful collision,12,13, l4 which is independent of coverage over a l6 wide range. Similar results have been obtained for carbon monoxide,15~
l o J. l1 G. l 2 J.
l3
l4
l5 l6
G. J. G. J.
R. Arthur and R . S . Hansen, J. Chem. Phys., 1962, 36, 2063. Ehrlich and F. G. Hudda, J. Chem. Phys., 1962, 36, 3233. A. Becker and C. D. Hartman, J . Phys. Chem., 1953, 57, 153. Ehrlich, J . Chem. Phys., 1961, 34, 29. Eisinger, J . Chem. Phys., 1958, 28, 165. Ehrlich, J. Chem. Phys., 1961, 34, 39. Eisinger, J. Chem. Phys., 1957, 27, 1206.
13
oxygen,17 and hydrogen.18 I n all these cases the probability lay in the range 20-60y0. In marked contrast to these results was the behaviour of oxygen on silicon,lS where the sticking probability started at only lyo,for a clean surface, and declined exponentially with coverage. A detailed study of the shapes of the desorption curves gives further information about surface processes. A striking feature observed for many systems is the evolution of gas in discrete stages.13, 15, 20, 2 1 For example, after adsorption a t 115 K nitrogen is evolved from tungsten in three steps. The lowest arises from a physically-adsorbed molecular species while the other two are due t o chemisorbed atomic states, of which the predominant one has atoms bound with an energy of about 155 kcal. molev1. I n the desorption of carbon monoxide from tungsten 21 one physically adsorbed and three chemically adsorbed species have been identified. Kinetic analysis of the desorption curves is also possible and gives the order, and therefore the mechanism, of the desorption processes. Evaporated metalJilms. The use of evaporated metal films for the study of gas-metal interactions was introduced in 1940 and has given much information. The particular property measured in early experiments was the calorimetric heat of adsorption, and its variation with coverage.22 However, more recent work in this field has cast some doubt on the interpretation of the results.23 It was suggested that two effects may have occurred during the evaporation of these films which led t o the accumulation of gas of unknown composition in the system and therefore to an uncharacterized film. These effects are: (i) replacement by the evaporated metal of gas molecules adsorbed on the substrate surface, and (ii) heating of the inner wall of the vessel, which then desorbs gas. It is, however, possible to prepare an evaporated metal film under ultra-high vacuum conditions 24, 2 5 , 26 by evaporating the metal in short bursts. Measurements on such films include those of sticking probabilities and catalytic activity. I n the latter case, a substantial difference in behaviour between films prepared in the mm. and mm. regions has been found. The ultra-high vacuum films are more reactive, but are much reduced in catalytic activity by small quantities of oxygen. The Nature of Adsorptive Processes.-The first important distinction to be drawn in the discussion of surface processes is that between physical and chemical adsorption. At a low enough temperature any gas will be physically adsorbed by any surface. This completely non-specific character of physical adsorption is the result of the operation of van der Waals forces between gas and surface, these forces being themselves non-specific. On the other hand chemisorption is a very specific process, which is characterized
J . Chem. Phys., 1959, 30, 412. J. Eisinger, J . Chem. Phys., 1958, 29, 1154. l9 J. Eisinger and J. T. Law, J . Chem. Phys., 1959, 30, 410. 2 o R. A. Pasternak and H. U. D. Wiesendanger, J . Chenz. Plays., 1961, 34, 2062. 2 1 P. A. Redhead, Trans. Paraday SOC., 1961, 57, 641. 2 2 B. M. W. Trapnell, Chemisorption, Butterworths, 1955. 23 T. W. Hickmott and G. Ehrlich, J . Phys. and Chem. Solids, 1958, 5, 47. 2 4 P. Della Porta and S. Origlio, Vucuum, 1961, 1 , 26. 1 2 5 S. Wagener, J . Phys. Chem., 1957, 61, 267. 2 6 R. W. Roberts, Trans. Faraday SOC., 1962, 58, 1159.
1 7 J . Eisinger, l8
14
G E N E R A L A N D P H Y S I C A L CHEMISTRY
by the rearrangement of electrons t o give rise to a primary chemical bond. The experimental criterion which is widely used to distinguish between these two possibilities is the change in heat content of the process. An adsorption process occurs spontaneously, and therefore has a negative change in free-energy. Therefore in the equation
AF = AH - TAX AH will be negative, since normally the entropy of gas localized on a surface will be smaller than in the gas phase, making A negative. Thus adsorption X
is exothermic. Physical adsorption is akin to the condensation of a vapour and is expected t o have AH comparable with a latent heat of evaporation, i.e. I AH I < ca. 10 kcal. mole-I. Chemisorption should have the full value of AH associated with the formation of a chemical bond, i.e. I AH > ca. 20 kcal. moleA1. The precise nature of the bond involved in chemisorption has been widely discussed.2' It has been concluded that, although allrali-metal atoms are adsorbed on tungsten as the &positive ions, this is an uncommon mechanism and most simple species are held by predominantly covalent bonds. Evidence in support of the covalent-bond postulate come's from infrared spectroscopic studies of carbon monoxide adsorbed on iron; a peak at about 5 p has been attributed t o the metal-carbon monoxide linear structure.28 Attempts t o give a quantitative theoretical account of the bond involved in chemisorption have met with comparatively little success. This is scarcely surprising in view of the electronic complexity of the system and the failure of theoretical chemistry to give a detailed account of any systems other than very simple ones. Physical adsorption. Comparatively little work on physical adsorption seems to make use of specifically ultra-high vacuum techniques. There is, however, a series of papers dealing with the interaction of helium, nitrogen, and argon with a Pyrex-glass surface a t temperatures in the range 4-90' K.' The results can all be expressed in terms of the Dubinin-Radushkevich equation log10 0 = log10 0 - D[log,o P/Pol2 , where 0 is the number of molecules adsorbed per sq. cm., omis the number in a monolayer, D = A T 2 where A is a constant, P is the pressure above the adsorbed layer, and Po is the vapour pressure of the adsorbate a t the temperature of the experiment. It is the extrapolation of these results to low coverage of the surface which yields the equilibrium pressure in an ultra-high vacuum system a t very low temperatures, referred to earlier. Chemisorption. A new approach to the atomic and molecular processes occurring on metal surfaces, instead of the not very successful electronic treatment, has been suggested by E h r l i ~ h . 30 ~ ,I n this approach the aim ~ is to start with experimentally-determined energy parameters and interpret them in terms of the well-established concepts of chemical thermodynamics and kinetics.
27
28 28
so
P. G. G. G.
M. Gundry and F. C. Tompkins, Quart. Rev., 1960, 14, 257. Blyholder and L. D. Neff, J . Phys. Chem., 1962, 66, 1464. Ehrlich, J . Chem. Phys., 1959, 31, 1111. Ehrlich, Trans. Vacuum Bymp., 1961, 126.
15
One of the most remarkable Qbservationswas the sharp cut-off of chemisorption from the gaseous phase of nitrogen, hydrogen, and carbon monoxide at the end of the three transition series. Among the transition metals themselves there is a considerable and apparently arbitrary variation in activity towards these gases. Thus, for example, nitrogen is not adsorbed by nickel and platinum, which do however adsorb hydrogen. This behaviour can be rationalized as follows. The energy parameters involved in the formation of a dilute layer of a diatomic gas, which is adsorbed as atoms, are (i) the dissociation energy of the molecule, D , and (ii) the binding energy of the atom to the metal, Only if is somewhat greater than D/2 will appreciable adsorption occur, e.g. for hydrogen, a dilute layer corresponding to about 1% coverage will only be stable at 10-3 mm. and 200" K if is greater than 54 kcal. mole-1 (D= 103 kcal. mole-l). Thus a metal may form reasonably strong bonds to the atoms, but if < D/2 an atomic layer, once produced on the surface, is only stable as long as migration of the ad32 atoms is prevented. Such a situation can be realized e ~ p e r i m e n t a l l y . ~ ~ ~ Both copper and mercury are inactive towards gaseous hydrogen but, at liquid air temperatures, chemisorb atomic hydrogen (readily produced from molecular hydrogen by the action of a hot filament). As long as the temperature is kept low enough to prevent migration, the layers are stable, but on warming, collisions of ad-atoms occur and the metal can no longer compete successfully, so that molecular hydrogen is evolved. Nitrogen has a very large dissociation energy so that it is only expected to be chemisorbed on those elements with which it forms a very strong bond; among the transition metals these are particularly titanium, zirconium, niobium, tantalum, molybdenum, and tungsten, which are also elements with which it forms very stable interstitial-type nitrides. Thus, whether or not chemisorption occurs depends on the balance between two large energy parameters. Moreover the dependence is an exponential one so that, just as in the case of the solubility of an ionic compound in water, extreme specificity is expected. Migration of adsorbed species. While moving over the surface of a metal an adsorbed atom experiences changes in potential energy which are characteristic of the surface,'and it can therefore serve as a probe for the investigation of that surface.29t 30 Two extreme types of potential-energy variation over the surface can be imagined. (i) The potential energy is uniform over the whole surface-in this case a migrating atom encounters no barrier and migration requires no activation energy. (ii) The potential energy is a minimum at an adsorption site and rises very rapidly on moving away from this site. If the potential energy curve does not overlap with that of a neighbouring site, an atom can only migrate by f i s t desorbing, and the activation energy for migration is the same as for atomic desorption. I n this context an adsorption site is identified with a surface metal atom. The results of field-emission microscope studies indicate that the situation is intermediate between (i) and (ii). Overlap between the potential energy curves of adjacent sites leads to a periodically-varying potential energy over the surface. The energy difference between the peaks and
x.
3 1 K . B. Blodgett, J . Chern. Phys., 1958, 29, 39. 32 J. Pritchard and F. C. Tompkins, Trans. Faraday SOC., 1960, 56, 540.
16
valleys is the activation energy for migration; this is usually about one-fifth of the binding energy of the atom to the surface. One very important conclusion can be drawn from the picture of a surface outlined above, namely that although it is meaningful to talk of adsorption " sites " these do not vary very greatly in energy from the rest of the surface. Even at the least favourable positions, i.e. on the potential energy peaks, the binding energy of the atom is still about 431/5. This emphasizes the difficulty which an attempt a t an electronic description of adsorption necessarily encounters, in that it has t o account for a strong surface-ad-atom interaction over the whole surface. Rates of adsorption and desorption. The above model of a surface can 30 The distance be used t o predict the activation energy for between adjacent potential energy minima is the lattice spacing of the metal which will not, in general, be the same as the internuclear distance in the diatomic molecule t o be adsorbed. The formation of the transition state in the reaction can be described as follows. One atom of the incoming molecule binds on t o a site of minimum potential. This makes it impossible for the other atom also to be a t a minimum since the distances do not match. It will be a t a site of energy higher by about the activation energy for migration. This situation is the transition state. The energy quantities involved in its formation are (i) the dissociation energy of the molecule, (ii) the strength of the gas-metal bond, and (iii)the activation energy for migration, Em,, x / 5 ) . Then for the more strongly-bound atom the heat of adsorp(m. tion, -AH,, is given by -AH, = x - o/2, and for the less strongly-bound atom
-AH,
=x
- D/2
- Emig..
The total energy taken in is the activation energy E and E = AH, A H , = D - 231 Emig. = AH Emig. where - A H is the change in heat content observed calorimetrically. As long as this has a reasonable value, the gas molecule has a lower energy even in its transition state than in the gaseous phase and no activation energy is required. To take a particular case, consider-hydrogen being adsorbed on tungsten. Here D = 103 kcal. mole-l, x = 74 kcal. mole-l, and Emig. 16 lwal. mole-1. = Thus E is negative and no activation energy is required. So far it has not been possible to give a convincing account of the dependence of the rate of adsorption on c o n ~ e n t r a t i o n . ~ ~ the limited number For of systems investigated, the rate of adsorption on metals is constant with coverage up to a critical adsorbed-atom/surface-atom ratio, and then diminishes rapidly. The critical ratio depends on the gas, temperature, and surface preparation. This constancy of rate is a surprising result, contradicting as it does the prediction of the Langmuir hypothesis of chemisorption. According to this, one would expect the rate of adsorption to depend on the rate a t which gas molecules encounter vacant sites on the substrate, and therefore to decrease with increasing coverage. The desorption of gases may follow either first- or second-order kinetics.
G A S S E R : ULTRA-HIGH VACUA
17
First-order kinetics are associated with the desorption of atoms or of a molecular gas which is adsorbed without decomposition. Thus for carbon monoxide the rate equation is -dn/dt = 3.1013.n.exp (-751O3/RT). Oxygen is alone among the diatomic gases in desorbing as atoms. The activation energy for desorption, 147 kcal. mole-I) is close t o the estimated value of the binding energy, as expected. Nitrogen and hydrogen are evolved from tungsten according to the second-order equation -dn/dt = A.n2.exp ( - E I R T ) . For nitrogen E is 81 kcal. mole-1 and for hydrogen, a t low coverage, it is 31 kcal. mole-1. This activation energy is also the heat of adsorption (2% D ). The frequency factor in both cases closely approximates to the collision number of a two-dimensional gas. This behaviour can be rationalized as follows. Both gases are adsorbed with a substantial evolution of heat and with zero activation energy. On desorption therefore) the activation energy required will be close to the heat of adsorption. If the heat of an adsorption is small there will be no adsorption of the diatomic gas, though atomic adsorption may occur. The activation energy for desorption of such an atomic layer is also the activation energy for migration. The origin of the difference in the desorption kinetics of oxygen and other diatomic gases lies in the very strong bonds that oxygen forms to metals. For all systems there will be competition between the atomic and molecular desorption processes, though normally one or other will dominate. The ratio of atoms to molecules, for the systems quoted above, is given approximately by
For hydrogen and nitrogen on tungsten < D, and the exponential factor ensures that the molecular process dominates. For oxygen the reverse is true. One of the classical concepts of physical chemistry is the dynamic nature of chemical equilibrium, and it is instructive to examine the conditions for dynamic equilibrium between adsorbed and free gas-molecules. Adsorption will occur until the chemical potential of a molecule in the gas phase is the same as that of an adsorbed molecule, at which time the rates of adsorption and desorption will be equal. The theory of rate processes 33 gives the adsorption isotherm, on equating the two rates, as
1- 8
e _ _ _ _ -- _ _ .exp ( & / k T ) fads.

kTf,,,
where 6 is the fractional coverage, faas. andfgasare the partition functions of the adsorbed gas and free gas respectively, and E is the heat of adsorption evolved per molecule. If now P is reduced, then 8 must decrease. The
S. Glasstone, K. J. Laidler, and H. Eyring, McGraw-Hill, 1941.
The Theory of Rate Processes,
18
rate-determining step in the re-establishment of equilibrium will be the desorption process, since the adsorption process is non-activated. Separating out the desorption rate (dLv/dt)des. = B exp (-Q/RT) where Q is the heat of adsorption and the pre-exponential factor, B, can be expressed by K x f(O), where f (0) is the fraction of the surface from which desorption can occ&, and K is a constant. Now if the average time spent by a molecule on the surface is z then (cW/dt)des.= Nads./r = Nmono. -f(e>/z -*. K = (Nmono./z) -exp ( Q / R T ) .*. z exp (-Q/RT) = zo (a constant) . z = zoexp (Q/RT). : Thus as the heat of adsorption (Q) increases, so does the average time a molecule spends on the surface. I n the limiting case, where there is no binding energy, z = z and ro is estimated to be of the order of the period , of a vibration of the surface atoms, i.e. ca. 10-13 see. From this, the average lifetime of an adsorbed species for various values of Q can be calculated, e.g. a t room temperature for Q = 15 kcal. moleb1, z sec., while for Q = 30 kcal. mole-l, z 100 years. Thus, if the position of equilibrium is altered by reducing the pressure, the rate of attainment of equilibrium may be very small. From the foregoing survey it can be seen that, by studying the behaviour of very simple systems, some insight into the fundamental behaviour of gas-metal systems has been obtained. It remains, of course, to study the adsorption behaviour of more complex gases and of systems in which chemical reactions are occurring a t a surface.
R. P. H. G.
3. GAS-PHASE OXIDATION
GAS-PHASE oxidation has been covered from time to time in Annual Reports 1 but the most recent reviews have been brief. The subject has now been comprehensively treated by Minkoff and Tipper in their book Chemistry of Combustion Reactions which covers the literature t o the end of 1961. However, a number of projects which were then at intermediate stages have since been materially advanced and merit more detailed treatment. The highlights of recent developments, in the Reporters opinion, are (1) the shock-tube experiments of Kistiakowsky and his co-workers on the oxidation of methane and acetylene, (2) the detailed work of Baldwin and his co-workers on the hydrogen-oxygen reaction, (3) the establishment, in considerable detail, of the mechanism of oxidation of methane and (4)the full confirmation of the thermochemistry of the HO, radical by Foner and Hudson. The oxidation of alkanes, olefins, and oxygenated compounds is
Annual Reports, 1950, 47, 39; 1954, 51, 83; 1955, 52, 13; 1957, 54, 41. G. J. Minkoff and C. F. H. Tipper, Chemistry of Combustion Reactions, Butterworths Scientifh Publns., London 1962.
a
KNOX: GAS-PHASE OXIDATION
19
now, at last, yielding to sustained pressure and there is an increasing amount of more fundamental work being carried out/on the rates of elementary reactions of simple radicals such as 0, OH, H, CH,, etc. Experiments on the oxidation of alkyl radicals, produced other than by oxidising alkanes, are still in the early stages. Shock Tubes and Flames.-Somewhat unexpectedly the chemical reactions occurring in shock waves and flames are often simpler than those occurring at lower temperatures although the techniques for studying them are more m c u l t . This is because the reactions are very fast; only bimolecular reactions are important and slow degenerate branching reactions do not occur. Schott and Kinsey,3 and Skinner and Ruherwein 4 carried out the first successful oxidations in shock tubes with hydrogen and methane, respectively. The former authors observed the ultraviolet emission of OH from the shocked gas. and determined the temperature-dependence of the induction period ti. log [O,]ti (mole ~ m . sec.) = -13.65 - ~ 17,100/4.576T. Since ti is inversely proportional to the rate constant of the branching 0, = OH 0. This reaction they deduced that this could only be H result has been confirmed by Suzuki and Fujimoto although, for some unexplained reason, their induction periods are some five times greater. Kistiakowsky and his co-workers 6 have extended the technique by using several different methods for following the oxidation of methane and acetylene in a shock tube. Gardiner has determined the induction period for the oxidation of acetylene between 1600" and 2020"E by measurement of the change in absorption of soft X-rays. His induction periods, for ignition of mixtures of 1.35% of acetylene and 2.04% of oxygen in xenon, are in precise agreement with those of Schott and Kinsey 3 for the hydrogen-oxygen reaction. Bradley and Kistiakowsky 8 have determined the mechanism of the reaction between 950" and 1090"K by use of a time-of-flight mass spectrometer attached to the shock tube. The induction periods observed agree with other determinations and these results, combined with those of Gardiner,' suggest very strongly that the branching reaction is again H 0, = OH 0. The observation of diacetylene in the products suggests that the other important reactions are 0 + C,H, = OH + C,H
C,H OH
+ C,H2 = C,H, + H + C2H2= H,O + C,H.
Kistiakowsky and Richards
have measured the vacuum ultraviolet
G . L. Schott and J. L. Kinsey, J. Chem. Phys., 1958, 29, 1177. G . B. Skinner and R. A. Ruherwein, J. Phys. Chem., 1959, 63, 1736. M. Suzuki and S. Fujimoto, 9th Internat. Symposium on Combustion, 1962, preprints. G. B. Kistiakowsky, Proc. Chern. SOC.,1962, 289. [Centenary Lecture.] W. C. Gardiner, J. Chem. Phys., 1961, 35, 2252. J. N. Bradley and G. B. Kistiakowsky, J. Chem. Phys., 1961, 35, 264. G. B. Kistiakowsky and L. W. Richards, J. Chem. Phys., 1962, 36, 1707.
20
emission from shocked acetylene-oxygen-argon mixtures, containing 8599% of argon, between 1400" and 2500" K. The induction periods again agree with those of Schott and K i n ~ e y . ~ time constant for the acceleraThe tion of the reaction, z, was also determined. For the branching reaction H 0, = OH 0, the rate constant and time constant are related by [O,] x z = l/k. The calculated value of Jc agrees precisely with that deter0, = OH 0, from hydrogenmined by Fenimore and Jones lo for H flame studies. From the ratio of ti/z it is deduced that the reaction increases in rate by a factor of lo4 during the induction period. Hand and Kistiakowsky l1 have studied the ionisation accompanying the combustion, which closely parallels the light emission. They conclude, in the light of Hand's earlier experiments l2 on the light emission from acetylene-oxygen flames, that both light emission and ionisation arise from similar sources, namely reactions of CH with 0: CH + 0 = CHO+ + e-
CH
+ 0 = CO" + H = CO + H + hv.
Although CH is not included in Bradley and Kistiakowsky's mechanism 8 it probably arises from C,H 0, = CH CO, or C2H 0 = CH + CO. I t s presence in the detonation of acetylene-oxygen mixtures a t 2080"1 ~ ~ 1 3 and in flash-initiated explosions,14 is well established. The ionisation reaction is supported by Green and Sugden,15 who find that CHOf is by far the most important primary ion in hydrocarbon flames. The shock-tube oxidation of methane has been studied by Bradley and Kistiakowsky,8 Hand and Kistiakowsky l1 and by Asaba et aL16 While the different results are in good agreement, they are not as simply explained as are those from acetylene. The time constant of the acceleration is the same as that for acetylene-oxygen ignitions, but the induction periods are much longer and have a higher activation energy. Kistiakowsky et a .8* l1 E obtained 33 kcal., and Asaba et al. 53 kcal. for rich mixtures, and 20 kcal. for weak mixtures.16 Kistiakowsky et l1 conclude that the reaction in the induction period must be a straight-chain, forming a C, hydrocarbon. When this has accumulated the oxidation is effectively that of acetylene. The first part of this conclusion is confirmed by flame studies but the formation of a C, hydrocarbon does not seem necessary to account for 0, = OH 0. branching by the reaction H Fristom and his co-workers 1 7 have studied the methane-oxygen flame a t l/lOth and 1/20th atmosphere pressure, using mass-spectrometer probing
P. Fenimore and G. W. Jones, J . Phys. Chem., 1958, 62, 693. W. Hand and G. B. Kistiakowsky, J . Chem. Phys., 1962, 37, 1239. W. Hand, J . Chem. Phys., 1962, 36, 2521. 13 R. K. Lyon and P. H. Kydd, J . Chem. Phys., 1961, 34, 1069. 1 4 R. G. W. Norrish, G. Porter, and B. A. Thrush, Proc. Roy. SOC., 1953, A , 216,
10 C. 11C. 1 2 C.
1 5 J. A. Green and T. M. Sugden, 9th Internat. Symposium on Combustion, 1962, preprints. 16 T. Asaba, Y. Yoneda, N. Kakihara, and T . Hikita, 9th Internat. Symposium on Combustion, 1962, preprints. 1 7 R. M. Fristom, C. Gruenfelder, and S. Favin, J . Phys. Chem., 1960, 64, 1386; 1961, 65, 587; A. A. Westenberg and R. M. Fristom, J . Phys. Chem., 1960, 64, 1393; 1961, 65, 591.
165.
21
for analysis. They show that all important reactions are bimolecular. The reaction is at first a straight-chain, but later branches through formation of H atoms. These appear to arise from the reaction CO OH = CO, H, whose rate constant is well known.l8 Once H atoms are formed the reaction H 0, = OH 0 can occur. The basic correctness of this mechanism is confirmed by comparison of the calculated value of the rate constant of CO OH = CO, H a t 1950"K with the accepted value. Fristom has also carried out a study with a spherical flame l9 at reduced pressure and confirmed earlier findings. The more recent study indicates, in more detail, the reactions involving H, 0, CH,, and OH. The methane-oxygen-argon flame (5.5% methane) has been studied by Levy et aZ.20 The results agree with those of Fristom.lg I n the presence of 0-36y0of hydrogen bromide the time scale of the reaction up to the complete consumption of methane is doubled, and thereafter hydrogen bromide has no effect. The authors suggest that chain branching occurs by the 0, = CHO OH H and that hydrogen bromide reacts reaction CH, mainly with OH.20 It seems more likely, however, that branching is due to H 0, = OH 0 and that the hydrogen bromide intercepts H atoms HBr = H, Br. The bromine atoms regenerate hydrogen bromby H ide by reacting with methane, but as soon as the methane is exhausted the hydrogen bromide is quickly converted into Br,, and the rate of consumption of the residual carbon monoxide is then the same as in the absence of hydrogen bromide. Fenimore and Jones 21 have shown that the ethane and ethylene flames are similar t o that of methane. Both flames commence with a zone of stra,ight-chain reaction. The main reaction, removing ethylene, is 0 + C,H, = (C,H,O)* = CH, + CHO. This decomposition of the activated ethylene oxide molecule is confirmed by the high yield of methane (up to 20% of ethylene consumed) obtained in the presence of a large excess of hydrogen. The rate constant derived for addition of oxygen atoms to ethylene agrees well with values derived from low-temperature work.,, With ethane, the main attacking species are H and OH but the fate of the ethyl radical is uncertain. The main conclusion from the flame and shock-tube studies is that hydrocarbon flames (apart from acetylene) are essentially hydrogen-carbon monoxide-oxygen flames fed by the decomposition products of a straightchain, oxygen-catalysed, pyrolysis of the hydrocarbons. This conclusion casts doubt on the interpretation advanced by Falconer and van Tiggeln 2 3
+ +
+ +
+ +
L. I. Avramenko and R. V. Lorentso, Zhur. $2. Khirn., 1950, 24, 207; C. P. Fenimore and G. W. Jones, J . Pizys. Chem., 1958, 62, 1578. l9 R. M. Fristom, 9th Internat. Symposium on Combustion, 1962, preprints. 2o A. Levy, J. W. Droege, J. J. Tighe, and J. F. Foster, 8th Internat. Symposium on Combustion, Williams and Wilkens, Baltimore, Md., 1962, 524. 21 C. P. Fenimore and G., W. Jones, 9th Internat. Symposium on Combustion, 1962, preprints. 2 2 ( a ) R. J. Cvetanovic, J . Chern. Phys., 1960, 33, 1063; ( b ) L. Elias and H. I. Schiff, Canad. J . Chem., 1960, 38, 1657. 2 3 W. E. Falconer and A. van Tiggeln, 9th Internat. Symposium on Combustion, 1962, preprints.
22
for their flame-speed measurements on higher hydrocarbons. They have calculated overall activation energies of 3 0 4 0 kcal. and mean molecular weights of chain carriers of 23-28, for the flames of the butanes and neopentane. The results are interpreted in terms of mechanisms similar to those proposed for low-temperature slow oxidations. The validity of the extrapolation is certainly doubtful when it is remembered that even at 500" c pyrolysis reactions are becoming dominant in hydrocarbon combustion.24 Hydrogen-Oxygen &action.-Our present understanding of this reaction owes much to the work of Baldwin and his co-w~rkers.~~,It is now well 26 established that in an aged reactor coated with boric acid, which preserves HO, and H202, the main elementary reactions occurring just above the second limit are
OH
+ H, = H,O + H H + 0, = OH + 0 0 + H, = O H + H
(1)
(2)
(3)
(4)
H 3-0, + M = H 0 2 + M
HO,
+ HO,
+ M'
= =
H20, 20H
+ 0,
+ M'
H,O,
(the numbering of equations in this section is that of Baldwin). The sequence (l), (4), (lo), (7) constitutes a straight-chain, and reactions (2) and (3) are responsible for chain branching. Chain termination probably occurs by
+ H,O, = H,O + OH O H + H20, = H,O + HO,

H
(14)
(15)
since H,02, by virtue of reaction (7), can be regarded as equivalent to two free radicals. This mechanism, with minor modifications, predicts with high precision the kinetics of the slow reaction outside the second limit. The rate of oxidation is only slightly greater than the rate of decomposition of the hydrogen peroxide present. Various rate-constant ratios can be obtained by comparison of predicted and experimental rates. For example, the ratio k15/k1 is found to be 7.1 a t 500" c . A value of 6 has been obtained by Baldwin and Bratten 27 from a study of the decomposition of hydrogen peroxide, in the presence of hydrogen, in a flow system. This study has firmly established that the reaction is unimolecular in its second-order region. The rate constant, with nitrogen as activating gas, is k, = 1.7 x lo1, exp (-46,000/1.9872') mole-1
~ 1 1 1 sec.-l .~
2 4 V. Ya. Shtern and N. Ya. Chernyak, Doklady Akd. Nauk S.S.S.R., 1951, 78, 91; J. W. Falconer and J. H. Knox, Proc. R o y . SOC., 1959, A, 250, 493. 26 R . R. Baldwin and L. Mayor, Trans. P a r a d a y SOC., 1960, 56, 80, 103; R. R. Baldwin, P. Doran, and L. Mayor, ibid., p. 93. 26 R. R. Baldwin, P. Doran, and L. Mayor, 8th Internat. Symposium on Combustion, Williams and Wilkins, Baltimore, Md., 1962, p. 103. 2 7 R. R. Baldwin and D. Bratten, 8th Internat. Symposium on Combustion, Williams and Wilkins, Baltimore, Md., 1962, p. 110.
K N O X : GAS-PHASE OXIDATION
23
in full accord with all reliable previous work.2* The study 27 also estnbmust be (14) not (14a), lished that the reaction between H and H202
H + H,O, = H, + HO2 (14a) since hydrogen accelerates the decomposition. If reaction (14a) occurs, hydrogen should have no effect on the rate since the sequence
is simply replaced by
which is kinetically equivalent.
If reaction (14) occurs we have
This is now a chain reaction. The work also establishes that reaction (6) is inadmissible since it would require
HO,
+ H 2 0 2= H 2 0 +
0 2
+ OH,
(6)
the decomposition of H202 inert gases, to be a chain reaction. in The earlier work of Baldwin et aZ.25showed that as the second limit is approached the quadratic branching reaction (8) HO, + H = 20H (8) becomes important. The overall reaction should still be entirely homogeneous and the nature of the surface should have no effect on the explosion limit. This is not strictly true and, in newly coated vessels, the limit was somewhat raised, indicating some surface initiation a t the limit. 2 9 I n the slow oxidation the hydrogen peroxide concentration builds up to a maximum a t the maximum rate of reaction. Since the position of the second limit is generally found by the withdrawal method, there is some doubt as to whether the peroxide reaches a stationary concentration before the mixture explodes. Baldwin and Doran 29 have investigated the effect of withdrawal rate, and of arrest of the withdrawal, and find that both have a considerable effect on the limit. They conclude that a t 500"c the stationary concentration of hydrogen peroxide is reached before ignition, but a t lower temperatures the build-up is slow since the limit a t first increases as the withdrawal rate is reduced, although further reduction lowers the limit again. The latter effect is attributed to the effect of accumulated water which, because of its high third-body efficiency, increases the rate of reaction (4) t o the detriment of (2). A more extensive study a t 500" c has confirmed this,30 and predicted that water should be about five times as efficient as hydrogen in reaction (4). This explanation has been substantiated by the direct experiments of
28 P. A. Giguere and I. D. Liu, Canad. J . Chem., 1957, 35, 283; D. E. Hoare, J. B. Protheroe, and A. D. Walsh, Trans. Paraday SOC., 1959, 55, 548; C. K. McLane, J . C h m . Phys., 1949, 17, 379; C. N. Sattedeld and T. W. Stein, J . Phys. Chem., 1957, 61, 537. R. R. Baldwin and P. Doran, Trans. Paraday Soc., 1961, 57, 1578. 30 R. R. Baldwin, P. Doran, and L. Mayor, Trans. Paraday SOC., 1962, 58, 2410.
24
Baldwin and Brooks 31 on the inhibiting effect of water a t the second limit in vessels coated with potassium chloride and boric acid. The efficiency relative t o hydrogen is 6.4 and is unaffected by temperature or surface between 460" and 540" C . This value compares well with previous values 5.5 (Nalbandyan 32a), 5.0 (Voevodskii and Talrose 32b), 6-5 (Ashmore and Tyler 3Zc). The first limit has been reinvestigated by Ivanov and Nalbandyan 33 with a potassium tetraborate surface. The results confirm Baldwin's earlier conclusion 34 that the predominant termination reaction is removal of hydrogen atoms a t the walls. They obtain a termination efficiency of 0.5 x which compares with Baldwin's value, in a vessel freshly coated with potassium chloride, of 6.6 x a t 520" c. Inhibition of the hydrogen-oxygen reaction. Baldwin and Simmons 35 carried out a careful investigation of the inhibition of the hydrogen-oxygen reaction by ethane, a t the first and the second limit, in a potassium chloridecoated vessel and showed that the effect was due to removal of H atoms by the reaction
H
+ CzH6
Hz
+ C2H5.
(16)
The alternative inhibition reaction with OH was unimportant, except a t high oxygen mole-fractions. The work showed that the same proportion of ethyl radicals resulted in chain-termination, whatever the pressure, and they therefore concluded that the final removal of ethyl was by the reactions (17) and (5). C2H.5 0,= C2H4 HO2 (17)
H 0 2 = Wall destruction
(5)
The main features of the inhibition by ethane were the linear fall in the second limit with ethane mole-fraction, i, and the inverse quadratic-relation at the first limit i = / - u / P 2 (where P = explosion limit pressure). The I results with added methane were strikingly The second limit was only slightly depressed until a critical concentration of methane was reached, when explosion was suppressed completely. Baldwin, Corney, and Walker 36 had to assume that some product of the reaction was responsible for the suppression of explosion. They also concluded that, a t concentrations of methane just insufficient to suppress explosion, the limit was thermal, not isothermal as is usual a t the second limit. A significant observation was the high rate of slow reaction when the inhibitor concentration was just sufficient t o suppress ignition. It seemed most likely that the inhibition arose from formaldehyde. The course of the reaction was visualised as follows. Initially there is virtually no inhibition since the only likely reaction of CH, with oxygen is CH, O2 = CH20 OH, which yields
R. R. Baldwin and C. T. Brooks, Trans. Furaday SOC.,1962, 58, 1782. 32 (a) A. B. Nalbandyan, Zhur. $2. Khim., 1945, 19, 210; (b) V. V. Voevodski and V. L. Talrose, ibid., 1948, 22, 1192; (c) P.G . Ashmore and B. J. Tyler, J. Catalyszs,
31
1962, 1, 39. 33 0 A. Ivanov and A. B. Nalbandyan, Kinetikai Kutaliz, 1960,1,337 (transl. 311). . 3 4 R. R. Baldwin, Trans. Faraday Soc., 1956, 52, 1344. 3 5 R. R. Baldwin and R. F. Simmons, Trans. Furaday XOC., 1955, 51, 680; 1957, 53, 955, 964. 36 R. R. Baldwin, N. S. Corney, and R . W. Walker, Trans. Furaday Xoc., 1960, 56, 802.
25
The concentration of H therefore increases exponentially. At the same time the concentration of CH,O increases and begins to inhibit the reaction by virtue of reactions (18) and (19).
OH rather than HO,.
CH,O CHO
+ H = CHO + H2 + 0, = CO + HO,.
(18) (19)
The final stationary concentration of CH,O may, or may not, be sufficient to suppress ignition completely. The experimental results suggest that the establishment of a critical concentration of formaldehyde, at which the branching coefficient is zero, is not a sufficient condition for suppression of ignition, but rather that the rate of the initial burst of reaction must be below a critical value. The final condition is thus thermal. This is supported by the strong effect of diameter on the critical inhibitor concentration and the slight effect of surface. The more recent work of Baldwin, Booth, and Walker 37 has confirmed this view. With methane concentrations just sufficient to suppress the limit, they observe a whitish glow when the expected explosion limit is crossed during withdrawal of the mixture. The glow is often accompanied by a small pressure pulse due to self-heating. The thermal nature of the limit is finally established by the effect of inert gases. Confirmation of the rBle of formaldehyde has been obtained by Baldwin and Cowe 38 who have studied the inhibition of the first and the second limit. The inhibition picture is similar to that of ethane. It requires the removal of CHO radicals by CHO 0, = CO HO, rather than by CHO = CO H or CHO 0, = CO, OH. The rate constant for reaction (18) is El, = 6 x 10l1T4 exp (-3000/1.987T) mole-1 ~ m sec.-l. . ~ The data also enable k, to be determined. The value when taken with those obtained by Fenimore and Jones l o from flame studies gives E, = 3.3 x 1014 exp (-17,600/1-987T) mole-1 ~ 1 1 1 .sec.-l. ~ Voevodskii has used the inhibition of the hydrogen-oxygen reaction by hydrocarbons to evaluate other rate constants of hydrogen-atom reactions. The values have recently been listed.39 Azatyan, Voevodskii, and Nalbandyan40 have obtained a value of E, by an ingenious and independent method. The first explosion limits of mixtures of carbon monoxide and oxygen, containing 0.7-8y0 of hydrogen, were determined. When a suitable surface such as magnesium oxide is chosen all termination reactions are diffusion-controlled and the mechanism is rather simple, comprising O H + CO = CO, + H (20) H + 0, = O H + 0 (2)
0 H
37
+ H, = O H + H + Wall = Destruction + Wall = Destruction
(3) (21) (22)
R. R. Baldwin, D. Booth, and R. W. Walker, Trans. Faraday SOC., 1962, 58, 60. 3 8 R . R. Baldwin and D. W. Cowe, Trans. Faraday SOC.,1962, 58, 1768. 39 V. V. Voevodskii and V. N. Kondratiev, Progress in Reaction Kinetics, ed. G . Porter, Pergamon Press, London and New York, 1961, Vol. I, p. 41. 40 V. V. Azatyan, V. V. Voevodskii, and A. B. Nalbandyan, Kinetika i Kataliz, 1961, 2, 340 (transl. 315).
26
GENERAL AND PHYSICAL C H E M I S T R Y
and the explosion limit is given by

[O,him. =
(b1/2k2)(1 ~22/h[Hzl)* Since E,, and k,, can be calculated from diffusion theory, E, and k, can be determined by measurement of the explosion pressure a t different small concentrations of hydrogen. The results give k, = 1.0 x 1014 exp (-15,900/1.9862') mole-1 ~ r n sec.-l .~
k, = 6.7 x 1013 exp (-1lY700/1-986T) ), Y, YY The absolute value of E, calculated a t 1400" K is half the value obtained by Fenimore and Jones lo and the value a t 800" K is identical with that of Baldwin and C ~ w e . ~ The enthalpy change in reaction (2) is +16 kcal. * and therefore the back reaction probably has zero activation energy. Oxidation of Carbon Monoxide.-Little advance has been made in this field in the last year or two. Cusin and James have studied the inhibition of the oxidation by cyanogen (C,N,) 41 and by ethane.42 The two systems show similar features. At about 900" c, the ignition of either cyanogen alone or cyanogen-carbon monoxide mixtures takes place only when all the cyanogen has been converted into carbon monoxide. The mechanism of inhibition is probably 0 + C,N2 = CNO + CN i competition with the branching reactions n 0 + co = CO,*
CO,*
+ 0 , = co, + 2 0 .
The kinetics of the inhibition suggest that the initiation of the oxidation is a first-order activation process - rather than the bimolecular reaction CO 0, = CO, 0. At lower temperatures (600-700" c) and low concentrations the inhibitor seems to act by adsorption on sites which can normally initiate the oxidation. At higher pressures it also acted homogeneously, as a t high temperatures. Kondratiev and Ptichkin 43 have studied the oxidation of carbon monoxide by ozone between 25" and 160" c. The reaction is chemiluminescent and the authors propose that the initiation is by decomposition of ozone t o give oxygen atoms. They 'deduce from their results, and assumed mechanism, that E ( 0 CO) - E ( 0 0,) = 3-8 kcal. The Slow Oxidation of Formaldehyde and Methane.-The slow oxidation of formaldehyde and methane has received renewed attention from Russian workers. FormaZdehyde. Markevich and Filippova 4 4 have used Kovalski's differential calorimetric method 4 5 to show the profound effect of surface on the
41F. Cusin and H. James, J. Chirn. phys., 1961, 58, 162, 730.
42
43
F. Cusin and H. James, J . Chim. phys., 1962, 59, 454. V. N. Kondratisv and I. I. Ptichkin, Kinetika i Kataliz, 1961, 2, 492 (transl.
449).
44
A. M. Markevich and L. F. Filippova, Zhur. $2. Khim., 1959, 33, 2214 (transl.
4 5 A. A. Kovalski and M. L. Bogoyavlenskaya, Zhur. $2. Khim., 1946, 20, 1325; see Semenov " Some Problems in Chemical Kinetics " (Transl. Bradley), Pergamon Press, London and New York, 1959, Vol. I, 187.
358).
27
oxidation and have thereby confirmed previous work carried out in static 46 and flow systems,*7 and partly explained the irreproducibility of much of the earlier work.48 With Pyrex reaction vessels coated with potassium tetraborate about 70% of the heat of the reaction is liberated close to the walls of the reaction vessel, yet throughout the reaction the temperature rise a t the centre gives an accurate measure of the rate of reaction so that there was no change in the percentage heterogeneity. (See also V a n ~ e e . ~ *I)n this reaction vessel, the only detectable products are carbon monoxide, dioxide, and water, and the rate of reaction is given accurately by Rate = Ic[CH20]2[0,]0. These results combined with those obtained in a flow system 47 give log,, k = 19.1 - 50,000/4*5817 in mole-1 ~ m sec.-l) between 380" and (k . ~ 550" c. With a clean surface the reaction is faster, and in clean silica peroxidic products can be isolated. They appear to arise from hydrogen peroxide initially formed by the reactions CH20 + HO2 = CHO + H 2 0 2 CHO + 0 , = CO + H02. I n the borate surface any hydrogen peroxide would be rapidly d e ~ t r o y e d . ~ ~ Markevich and Filippova 4 4 f h d marked activation-energy differences between the borate-coated surface (50 kcal.) and the clean silica surface (26 kcal.). This observation may have some bearing on the activation energy changes observed by Harding and Norrish 50 in the oxidations of formaldehyde and of ethylene (where formaldehyde is probably the branching intermediate) from 21 (26) kcal. at 350" c t o 39 (42) kcal. at 460" c and (53) kcal. a t 550" c (values in parentheses are for ethylene). The isolation of considerable amounts of hydrogen peroxide from the oxidations of both formaldehyde and methane raises the question of its role as a possible branching agent in these oxidations. The definitive work of Baldwin and Bratten 27 gives the following lifetimes for hydrogen peroxide (k in an inert-gas concentration (assumed nitrogen) of 10-5 mole ~ m . - ~ , about 0-5 atm. at 340" c).
Temp. ("c) Lifetime (sec.) 360 5600 380 400 420 1850 650 230 440 90 460 37 480 500 16 7.2 620 3.4
Markevich and Pecherskaya 51 have found that, in a molybdenum-glass

4 6 M. D. Scheer, 5th Internat. Symposium on Combustion, Williams and Willrins, Baltimore, Md., 1955, 435. 4 7 A. A. Anisonyan, S. Ya. Beider, A. M. Markevich, and A. B. Nalbandyan, Zhur. Jiz. Klzim., 1959, 33, 1695 (transl. 115). 4 8 R. Fort and C. N. Hinshelwood, Proc. Roy. Soc., 1930, A, 129, 284; R. Spence, J., 1936, 649; F. F. Snowdon and D. W. G. Style, Trans. Paraday SOC., 1039, 35, 426; D. W. E. Axford and It. G. W. Norrish, Proc. Roy. SOC., 1948, A , 192, 518; M. Vanpee, Bull. SOC. chim. belges, 1953, 62, 285; A. M, Markevich and L. F. Filippova, Zhur. $2. Khim., 1957, 31, 2649. 4 9 D. E. Cheaney, D. A. Davies, A. Davis, D. E. Hoar0, J. Protheroe, and A. D. Walsh, 7th Internat. Symposium on Combustion, Buttemorths Scientific Publns., London 1959, 183. A. J. Harding and R. G. W. Norrish, Nature, 1949, 163, 797. 61 A. M. Markevich and Yu. I. Pecherskaya, Zhur. $2. Xhint., 1961, 35, 1418 (transl. 697).
28
GENERAL A N D PHYSICAL CHEMISTRY
reaction vessel, the oxidation a t 330", 390", and 420" c commences with no pressure change although formaldehyde is consumed, probably by the overall reaction CH,O 0, = CO H,O,, and that the reaction is slightly au tocatalytic, as previously observed by Vanpee.48 The addition of up to 10 mm. of hydrogen peroxide to 15 mm. of formaldehyde 300 mm. of air a t 420" c has no lasting catalytic effect, although it removes the slight initial autocatalysis. The results of Baldwin and Bratten 27 show that the pyrolysis of 10 mm. of hydrogen peroxide a t 420" c should generate hydroxyl radicals at a rate of 5 mm. min.-l. The observed initial rate, in the absence of added peroxide, is 4 mm. min.-l and with 10 mm. of peroxide 12 mm. min.-l. Either the chains are exceedingly short or the decompo. sition of the peroxide is somehow short-circuited and does not give hydroxyl radicals. This problem is general throughout hydrocarbon oxidation where substantial yields of hydrogen peroxide are obtained, but where it has very little catalytic effect. A possible explanation is that activation of the peroxide is short-circuited by the collision of a partially activated molecule with formaldehyde, and the occurrence of the reaction
HO*OH*
+ CH,O
2H20
+ CO.
In other words, we are dealing with a non-Maxwellian distribution of energy among the peroxide molecules, particularly in the region of 40 kcal. and above. The above reaction is sterically plausible and highly exothermic, and there is some evidence for it in the oxidation of methane. Methane. An important series of papers on the oxidation of methane has appeared under the names of Karmilova, Enikolopyan, Nalbandyan and Semenov. The reaction was studied in a static system in a 200 ml. silica reaction vessel washed with hydrofluoric acid, and aged for 12 months. The surface was believed to be one of silicic acid and therefore of type (i) in Walsh's nomenclature.49 The reaction was studied a t 423,52a472", 491", and 513" c.52b The reaction is initially autocatalytic and a t a small percentage conversion reaches a maximum rate which is maintained, in spite of consumption of the reactants, until nearly the end of the reaction. The major products are carbon monoxide, dioxide, and water, with traces of hydrogen and methanol. Formaldehyde and hydrogen peroxide are intermediate products formed in small yield. The stoicheiometry of the reaction up to the maximum rate is accurately represented by
CH,
+ $0, = CO + 2H20.
Later, carbon monoxide is oxidised t o dioxide and the yield of the former sometimes passes through a maximum. The overall activation energy of the reaction is 41.5 kcal. for the stoicheiometric mixture. This agrees with Egerton, Minkoff, and Salooja's value 53 for the same mixture but the latter also obtained lower values ( 2 3 4 1 kcal.) for richer mixtures. Karmilova, Enikolopyan, and Nalbandyan 5 2 tacitly assume that the activation
5 2 L. V. Karmilova, N. S. Enikolopyan, and A. B. Nalbandyan, ( a ) Zhur. $2. Khim., 1957, 31, 851; ( b ) ibid., 1960, 34, 550 (transl. 261). 5 3 Sir A. C. Egerton, G. J. Minkoff, and K. C. Salooja, PTOC. Roy. SOC.,1956, A , 235, 158.
29
energy is independent of the methane : oxygen ratio. The overall order of the reaction is 2.7 and the partial orders 1.62 for methane, 0.96 for oxygen, and 0.10 for total pressure. The low exponent of total pressure contrasts with the value of unity obtained by Norrish and F0ord.5~ However, they used a soda-glassreaction vessel [type (ii)or (iii) surface] and their rates were about 20 times smaller. Diffusion-controlled termination might therefore have occurred in their experiments. Karmilova et ~ 1 . ~ 5 5 investigating the r61e of formaldehyde, have shown that it appears somewhat before hydrogen peroxide although both reach ma-ximumpressures at the maximum rate of reaction. From Markevichs results 44 on formaldehyde they conclude that the peroxide arises from the oxidation of formaldehyde and is not the degenerate branching intermediate, as had been suggested by Egerton, Minkoff, and Salooja.53 The maximum formaldehyde concentration rises, with an activation energy of 7.8 kcal., while that of hydrogen peroxide falls; it increases linearly with methane pressure and is independent of oxygen pressure, above 50 mm. The induction period of the reaction falls, with an activation energy of 36 kcal. These observations are quantitatively explained by the mechanism advanced by Karmilova, Enikolopyan, Nalbandyan, and Semenov : 5 6
Denoting the rate of the ith reaction by ri it was not difficult to show that, at maximum rate when the chains are long, r2 = T , ~ ; r2 = r,; and r l = r2 r2, = r5 r,. Hence the maximum formaldehyde concentration is given by FmaXa( k J ~ 4 / k 2 < k 5 ? ) / ~ = [CH,]. The observed activation energy is then EF = 5(E2 E, - E2#- E,). Since both the reactions for F,,. of OH are exothermic, and that of HO, with methane is endothermic, E , and E2>are likely to be small while E , - E5#should be somewhat less than the difference in bond strength between methane and formaldehyde (about 25 kcal.). The experimental value of E , = 7 . 8 kcal. is obviously reasonable. The mechanism also predicts that the reaction should be of second order in methane and first order in oxygen, in reasonable agreement with experiment. The acceleration constant is (k,rC,/k,)[CH,][O,]. If the reaction accelerates exponentially during the induction period, ti, the temperature dependence of l/ti should be the same as that of 4.
R. G. W. Norrish and S. G . Foord, Proc. Roy. SOC.,1936, A, 157, 503. L. V. Karmilova, N. S . Enikolopyan, and A. B. Nalbandyan, Zhur. $2. Khim., 1960, 34, 990 (transl. 470). 5 6 L. V. Karmilova, N. S. Enikolopyan, A. B. Nalbandyan, and N. N. Semenov, Zhur. $2. Khim., 1960, 34, 1176 (transl. 562).
54
55
30
The experimental activation energy of the induction period was 36 kcal. and this agrees well with that predicted from the mechanism, since Ed = Em,,. rate - E, = 33 kcal. Furthermore, Ed should be somewhat greater than E,, which is expected to be about 30 kcal. The mechanism gives a very good account of the kinetics of the reaction up to the point of maximum rate and vindicates Norrish's original postulate 57 that formaldehyde is the branching intermediate. Features of the reaction which are not considered are (1) the role of hydrogen peroxide as a possible branching agent, (2) the maintenance of the maximum rate of reaction in spite of consumption of reactants, and (3) the formation of carbon dioxide. I n a fourth paper 58 the effect of added hydrogen peroxide is examined. Even in amounts several times in excess of those normally present a t maximum rate, the induction period is only slightly reduced and the maximum rate unaltered. This has been confirmed by Mari et aL59 It is, however, interesting that a t 472" c, when 1.5 mm. of peroxide is added t o 235 mm. of a stoicheiometric mixture, the yield of formaldehyde initially rises rapidly. Thereafter it rises more slowly to the same maximum as is obtained in the absence of peroxide. Meanwhile, the peroxide concentration falls gradually but is always greater than that normally present a t maximum rate. It appears then, that hydrogen peroxide can act as an initiator in the earliest stages but not once any quantity of formaldehyde has appeared. The constancy of the rate of oxidation, in spite of considerable consumption of the reactants, has been noted both by Karmilova et ~ 1 . and by ~ 2 ~ Mari et aZ.,6o but their explanations are radically different. The former 6 1 suggest that a new chain-branching system appears in the later stages of the reaction which just compensates for the expected decline in rate as methane and oxygen are consumed. The system involves the formation of hydrogen atoms which can cause branching by reaction (9). CO + O H = C 0 2 + H
H2 + O H = H 2 0 + H H + 0, = O H + 0 H + RH = H2 + R
This scheme also accounts for the formation of carbon dioxide. Application of the kinetic tracer method 6 2 has confirmed the general correctness of this idea by showing that all the carbon dioxide produced in the later stages arises from carbon monoxide. Additional confirmation comes from the calculation of the relative rates of removal of carbon monoxide and methane by using the known rate constant data for the reactions of OH.lS
57
R. G. W. Norrish, Proc. Roy. SOC.,1935, A, 150, 36.
L. V. Karmilova, N. S. Enikolopyan, and A. B. Nalbandyan, Zhur. $2. Khim., 1961, 35, 1043 (transl. 512). 59 R . Mari, M. Letort, M. Dzierzynski, and M. Niclause, J. Chim. phys., 1962, 59, 596. 6 o R. Mari, M. Letort, and M. Niclause, J. Chim. phys., 1962, 59, 324. 61 L. V. Karmilova, N. S. Enikolopyan, A. B. Nalbandyan, and V. T. Il'in, Zhur. $2. Khim., 1961, 35, 1435 (transl. 706). 8 2 L. V. Karmilova, N. S. Enikolopyan, and A. B. Nalbandyan, Zhur. $2. Khim., 1961, 35, 1458 (transl. 717).
58
31
Mari, Letort, and Niclause,60 on the other hand, consider that the high rate of reaction is maintained because of modification of the surface of the reaction vessel. Mari et uZ.63 have shown that it is necessary to add some eight times the quantity of formaldehyde normally present a t maximum rate, in order to make the reaction start a t this rate. But the pressure-time curves are then of an unexpected shape, starting at a high rate which then declines and finally increases again. This is thought to be due t o acclimatisation of the reaction-vessel surface during the reaction, and pretreatment of the Pyrex reaction vessel with water vapour for several hours certainly accelerates the subsequent reaction. Although the theory of Karmilova et al. is the more attractive, some account should certainly be taken of surface modification during the course of a reaction. The theory of Karmilova et al. supposes that all methyl peroxy radicals decompose to formaldehyde and hydroxyl. Fisher and Tipper 6 4 have shown that this may not be so. In an aged silica reaction vessel a t 400" c measura.ble yields of methyl hydroperoxide are formed in the acetonephotosensitised oxidation of methane and, subsequently, in the oxidation of methane alone. Pyrolysis of methyl hydroperoxide a t 345" c gives formaldehyde and methanol as the major products, probably mainly by heterogeneous decomposition. The methanol which Karmilova et al. report may have come from this source. The lifetime of the peroxide is about 30 sec. and its stability, as regards homogeneous decomposition, must be considerably greater than that of the higher alkyl hydro peroxide^.^^ It is probable that CH,O, abstracts hydrogen from formaldehyde rather than from methane. The oxidation of methane by traces of oxygen has been studied a t 950-1050" c by Germain and Sueur,66 in a flow system. The reaction is autocatalytic and the maximum rate is held until all the oxygen (initially 0--5%) is consumed. The main products are H,, H,O, CO, CO,, C2H4, and C,H,. The carbon dioxide probably arises by reaction (7), molecular hydrogen from H atoms, ethane from unoxidised methyl, and ethylene from ethane. The mechanism is thus similar to that a t lower temperatures. The high-temperature oxidation of methane has also been investigated by Cabannes and his co-workers 6 T who passed a mixture of methane and oxygen over a platinum plate heated to between 600" and 1300"c. From the profile of gas velocity, temperature, and composition, determined by suitable probes, the degree of heterogeneity can be calculated. On clean platinum the reaction is 20% heterogeneous and on platinum coated with alumina it is entirely homogeneous. Enikolopyan and Bel'gorskii 6 8 have compared the oxidation of methane and methanol in glass reactors, coated with potassium tetraborate and
6 3 R. Mari, M. Letort, M. Dzierzynsbi, and M. Niclause, J. Chim.phys., 1962, 59, 589; Compt. rend., 1961, 252, 3241. 6 4 I. P. Fisher and C. F. 3. Tipper, Nature, 1962, 195, 489. 65A. Kirk and J. H. Knox, Trans. Faraday SOC.,1960, 56, 1296. D. 6 6 J. E. Germain and R. Sueur, Bull. SOC. chim. France, 1961, 1008. 67 F. Cabannes and Y . Fukuchi-Thibaut, Bull. SOC. chim. France, 1961, 947; F. Cabannes and P. Valentin, ibid., 1962, 166. 6 8 N. S. Enikolopyan and I. M. Bel'gorskii, Zhur. $2. Khim, 1960, 34, 1571 (transl.
749).
32
silver, using differential calorimetry. On the former surface both reactions are homogeneous and autocatalytic, and depend upon formaldehyde as the branching agent. On silver both are heterogeneous and, while the oxidation of methane produces no formaldehyde, that of methanol produces more formaldehyde than the homogeneous oxidation. Thus the effect of silver must be to destroy free radicals, rather than formaldehyde. Barber and Cuthbert 69 have reported some preliminary work on the oxidation of methane in an electric discharge (200 w, 13,560 kc. sec.-1), analysing the products by mass spectrometry. With the discharge through the methane the products are the same as without oxygen (ethane, hydrogen, traces of acetylene). With the discharge through the oxygen the major product is ethane, with smaller amounts of methane and carbon dioxide. Enikolopyan and Konereva 70 have studied the oxidation of methane, catalysed by nitromethane, with the object of establishing whether nitromethane or nitrogen dioxide is the true catalyst. The results are inconclusive. The fall in the nitromethane concentration is slower in oxidisingmethane than in the absence of oxygen, and kinetic-tracer experiments by Miller et aZ.71 show tihat the nitromethane is not only destroyed in the reaction, but formed from CH, and NO,. A striking feature is the sudden fall in the concentration of nitromethane a t a certain stage in the reaction, coinciding with a peak in the heat evolution. This sudden burst of activity seems to be due, to a partial ignition of the accumulated carbon monoxide. The ignition apparently produces a flood of radicals but is quickly inhibited and cannot be detected by any change in the CO concentration. Alkanes.-The present state of knowledge of the oxidation of alkanes has been reviewed in a non-specialist article by C ~ l l i s . ~ ~ The Zower uZEanes. The most significant recent work is that of Zeelenberg et aZ. who have followed the oxidation of isobutane 7 3 and neopentane 7 4 in a static system, from the early stages of the induction period, by gas chromatography. Gas chromatography is now regarded as the most satisfactory tool for studying complex oxidations. 7 5 Sandler and Beech,76 for example, determined some 30 products from the oxidation of n-pentane, and Wright 7 7 some 38 products from the oxidation of o-xylene. Zeelenberg's work on isobutane shows that all the initial products of the reaction increase exponentially with time. Isobutene is the major initial product (about 85% of isobutane oxidised) a t about 300" C. Other initial products are
M. Barber and J. Cuthbert, Nature, 1961, 190, 1001. N. S. Enikolopyan and G. P. Konereva, Izvest. Alcad. Nauk S.X.S.R., Otdel. Ichim. Nauk, 1959, 1100; 1960, 419; 1961, 230 (transl. 210). 71 V. B. Miller, P. L. Levin, G . P. Konereva, M. B. Neiman, and N. S. Enikolopyan, Zhur. $2. Khim., 1960, 34, 1980 (transl. 940). 7 2 C. F. Cullis, Chem. and Ind., 1962, 23. 7 3 A . P. Zeelenberg and A. F. Bickel, J., 1961, 4014. 7 4 A. 9 . Zeelenberg, Rec. Trav. chim., 1962, 81, 720. 7 5 J. W. Falconer and J. H. Knox, Proc. Roy. Xoc., 1959, A , 250,493; R. E. Ferguson and C. R. Yokeley, 7th Internat. Symposium on Combustion, Butterworths Scientific Publns., London 1959, p. 113; G . Kyryacos, H. R. Menapace, and C. E. Boord, Analyt. Chem., 1959, 31, 222; C. F. Cullis, A. Fish, F. R. F. Hardy, and E. A. Warwicker, Chem. and Ind., 1961, 1158. 7 6 S. Sandler and J. A. Beech, Canad. J. Chem., 1960, 38, 1455. 7 7 F. J. Wright, J. Phys. Chem., 1962, 66, 2023.
70
33
isobutene oxide (10%) and propionaldehyde (6%), with traces of acetone and propene. All can be derived from the decomposition of the two possible peroxy-radicals. The isobutene is probably formed by an HO, radical chain, which has been suggested for other hydrocarbon^.'^ With neopentane the HO, radical chain cannot operate, since there is no olefin with the neopentane carbon skeleton. The initial products at 260-290" c are isobutyraldehyde (85%), acetone (lo%), and traces of pivalaldehyde, dimethyloxetan, epoxyisobutane, and neopentyl alcohol. Isobutene is the major hydrocarbon produced and becomes the major product when the isobutyraldehyde is being consumed during the later stages of the reaction. The main path of oxidation appears to be
(CH,),C*CH, X 0, (CH,),C.CH,
+ +
= =
(CH,),C*CH, XH (CH3),C*CH2.O, (CH,),CH*CHO CH,O.
Seakins 79 has reinvestigated the oxidation of propane, paying particular attention to the yields of peroxides and aldehydes. He has confirmed the existence of the negative temperature coefficient between 320" and 390" c and showed that coating the Pyrex reaction vessel with potassium chloride, while reducing the overall rate of reaction, does not affect the ratio of reaction rate to peroxide concentration. He deduces that the surface destroys the branching agent but does not affect the primary chain length, the peroxide being identified as the branching agent. Unfortunately the peroxide was not characterised. Since it is likely to be mainly hydrogen peroxide, which is inactive as a catalyst, the interpretation is doubtful. A major problem in hydrocarbon oxidation is the source of methanol, which is often an important product. It is generally supposed to arise from the reaction
CH,O
+ RH = CH,.OH + R
but Hanst and Calvert have shown that methoxy-radicals, derived from the pyrolysis of dimethyl peroxide at 110-150" c, can be readily oxidised to formaldehyde, presumably by the reaction
CH,O
+ 0,
CH,O
+ HO,
which is 20 kcal. exothermic. Neiman, Efremov, and Serdyuk have gone some way to solving the problem by application of the kinetic-tracer method. By adding 14CH,*CH0 and l4CH3*N=NCH,to a propene-oxygen mixture at 315" c they have shown that -75% of the methanol recovered arises from acetaldehyde, a primary product of the oxidation of propene, and that 75% of the acetaldehyde gives methanol. The experiments with azomethane establish that at least some of the methanol can come fro= methyl radicals, which also give formaldehyde and methane.
( a ) J. H. Knox, Trans. Paraday SOC., 1960, 56, 1225; ( b ) see rsf. 24. M. Seakins, Proc. Roy. SOC.,1961, A , 261, 281. 8 o P. L. Hanst and J. G. Calvert, J. Phys. Chem., 1959, 63, 104. M. B. Neiman, V. Y . Efremov, and N. K. Serdyuk, Kinetika i Kataliz, 1960.
70
'*
1, 345 (transl. 319).

B
34
Neiman et ~
2 postulate ~the following scheme . ~

- co f C H 3
-+
0,
CH,.OH
+ other products
X CH,*CHO+ CH,*CO
/
LCH,CO,
--+ + CO,. CH,O
If all the methoxy-radicals form methanol the yield of methanol derived from acetylperoxy-radicals should equal the yield of carbon dioxide derived from the acetaldehyde. Tracer experiments with CH3*14CH0show, on this assumption, that 50% of the methyl groups in the acetaldehyde form methanol, via the acetylperoxy-radical, and the other 25% via methyl. Neiman et al. suggest that the methyl radicals give rise to methanol by way of CH, 0, = CH302 and CH30, RH = CH3*OH RO. The second reaction is implausible and the suggestion that methanol arises from the heterogeneous decomposition of methyl hydroperoxide e4 seems more reasonable. Neiman et al. also demonstrate the increasing ease of hydrogen abstraction, relative t o oxidation, as the reaction proceeds. This is a, general feature of oxidation, due to the formation of substances with weaker C-H bonds as oxidations proceed. The results establish the molecular precursor of methanol in any system where acetaldehyde is formed, but they do not necessarily establish the free-radical precursor as methoxyl. Nor do they explain the formation of methanol in the oxidation of ethane and ethylene, where acetaldehyde was a minor product of the reaction.82 The importance of the surface in hydrocarbon oxidation has been reemphasised by Satterfield and Reid,83 who have correlated the effectiveness of surfaces in destroying hydrogen peroxide with the yields of other products. Thus aldehyde yields are low on surfaces which destroy peroxides, while ethylene yields are high under the same conditions. It has also been shown 84 that pretreatment of a reaction vessel with hydrogen fluoride accelerates the oxygen-induced pyrolysis of propane a t 600"c , as does conditioning the reaction vessel by carrying out several runs with added nitric oxide. H g e hydrocarbons. The oxidation of heptane has been studied by ihr Ohlman et a t 200-250" c. The reaction is autocatalytic, starting with a pressure decrease, presumably due t o the formation of a peroxide. The initial rate of pressure decrease is proportional to the hydrocarbon pressure. No pressure decrease is observed by Kende and Gal 8 6 in their work on the oxidation of n-hexane, inhibited by styrene, a t about 230" C. This is probably because they used a reaction vessel coated with potassium chloride. The acceleration constant of the oxidation falls in proportion to the amount of styrene added. Tracer experiments show that a high proportion of the
82 J. H. Knox and C. H. J. Wells, see p. 158 of ref. 2. a3 C. N. Satterfield and R. C. Reid, J. Chem. and Eng. Data, 1961, 6, 302. * 4 ( a )V. A. Poltorak and V. V. Voevodskii, 2hur.Ji.z. Khim., 1961, 35, 284 (transl. 176); (b) R. Martin, 3 . Niclause, and M. Dzierzynski, Compt. rend., 1962, 254, 1786. 1 s 5 G . Ohlman, H. Steinert, G . Lischke, and E. Leibnitz, 2. phys. Chem. ( L e i p i g ) , 1962, 218, 42. s 6 I. Kende and D. Gal, Combustion and Flame, 1962, 6, 109.
35
carbon dioxide in the products comes from the styrene, and the inhibition is therefore due to the competitive oxidation of the styrene, rather than its action as a radical trap. The nature of the peroxides formed in low-temperature oxidations has been clarified by Cartledge and Tipper 8 7 who have demonstrated the formation of mono-, di-, and tri-peroxides in the oxidation of heptane at 240310" c. These are thought to arise from internal abstraction by peroxyradicals.
CH,-CHCH,*CH ,.CH ,-CH2.CH,
0.0-
+CH,*CHCH ,*CH,*CH*CH 2*CH3+ I

0-OH
RH
0,
CH,*CH*CH,.CH,CH*CH2CH2*CH3 +CH,*CH*CH2*CH,.CH*CH ,CH I I I I

O*OH 0.00-OH O*OH
Competitive oxidations. The wide differences in reactivity of different hydrocarbons towards oxygen are well known. They may arise from different rates of attack of the free radicals on the hydrocarbons, different rates of branching, and different efficiencies of production of the branching intermediates.88 Competitive oxidation studies by Falconer, Knox, and Trotman-Dickenson 89 have shown that only small differences can be attributed to the chain-propagating steps. Between 320" and 495" c the radical or radical mixture attacking ethane, propane, cyclopropane, isobutane, and neopentane has a selectivity rather greater than C and less than CF,, 1 CH,O, or CH,. Individual oxidation studies strongly suggest that HO, is the chain-propagating radical, but the thermochemistry of the HO, radical reactions makes this questionable. Foner and Hudson have redetermined the heat of formation of HO, by the electron-impact method. The new values for the bond strengths in H,O, are D[H-OOH] = 89.6 & 2 kcal.; D[H-001 = 45-7 & 2 kcal. Nearly all hydrogen-abstraction reactions by HO, are therefore endothermic, and its reactivity and selectivity should be comparable with that of a bromine atom for which D[H-Br] = 87 kcal. The competitive experiments taken alone would be better interpreted if OH were the radical removing the hydrocarbons. Experiments at lower temperatures with ketone photosensitisation 91 have shown that the radicals removing the hydrocarbons have very similar reactivities to those at higher temperatures. The radicals were thought to be CH,O,, C,H,O,, and C3H702 but there is some doubt about this. 0lefins.-In the last few years there has been renewed interest in the oxidation of ole fin^.^^ Skirrow and Williams 93 have investigated the oxidation of isobutene between 250" and 320" c, analysing the products by gas
8 7 J. Cartledgeand C. F. H. Tipper, Proc. Roy. Xoc., 1961, A, 261, 388; Combustion and Flame, 1961, 5, 87. 8 8 J. H. Knox, Trans. Faraday SOC., 1959, 55, 1362. 8 9 W. E. Falconer, J. H. Knox, and A. F. Trotman-Dickenson, J., 1961, 782. S. N. Foner and R. L. Hudson, J. Chem. Phys., 1962, 36, 2681. 91 W. E. Falconer, J. H. Knox, and A. F. Trotman-Dickenson, J., 1961, 4285. 9 2 G. Skirrow, Proc. Roy. SOC., 1958, A, 244, 345; A. Blundell and G . Skirrow, e'bid., p. 331; J. D. Mullen and G. Skirrow, ibid., p. 312. 93 G. Skirrow and A. Williams, Proc. Roy. SOC., 1962, A, 268, 537.
36
chromatography. The initial products are acetone and formaldehyde, in equimolar amounts. Isobutyraldehyde and ~~methylacraldehyde also may be initial products. Later, carbon monoxide and dioxide, water, and propene appear. Hydrogen peroxide is the main peroxidic product, but some methallyl peroxide appears later in the reaction. Kinetic analysis of the reaction is difficult as it starts with a pressure decrease, a common although unexplained feature of many olefin oxidations. Cullis, Fish, and Turner 94 have studied the oxidation of 2-methylbut-2ene (isopentene) a t 265" c and find that acetaldehyde and acetone in equimolar amounts are the major initial products. Later products are carbon monoxide, dioxide, water, and methanol with smaller amounts of propaldehyde, isopropyl and t-butyl alcohol, and butan-2-one. Using isopentenes labelled with 14C, a t atoms 2 and 4, they have established that all products except t-butyl alcohol are formed without rearrangement of the carbon skeleton. The methanol appears t o come from the CH, group of the acetaldehyde, as shown independently by Neiman et aZ.81 The first stage of the oxidation of an olefin now seems clear, and with ethylene,s2 propene,S1 i s ~ b u t e n e and isopentene ,~~ 95 i t can be represented by the stoicheiometric equation
949
\C=d
It is difficult to avoid the conclusion that a four-membered ring transitionstate must be formed somewhere in this process. Cullis, Fish, and Turner believe that the oxygen molecule adds directly to the double bond, t o give a ring peroxide which subsequently decomposes into two carbonyl compounds. This has the advantage of explaining the pressure decrease usually observed, but work on the oxidation of alkanes 7 g b 9 8* rules this out. I n the oxidation of propane,'* for example, the yield of propene passes through a maximum due to its own oxidation. The maximum concentration and the dependence of propene yield on extent of reaction are independent of the rate of oxidation as a whole. I t s consumption must therefore be controlled by the prevailing oxidation of the alkane, and can only be by a free-radical process. Skirrow and Williams 93 proposed a mechanism based upon OH as the chain carrier:
(CH,),C:CH, OH (CH3),CCH20H 0 ,
+ 0,- \c-0 + o=<. -/-
+ +
=
=
(CH,),C*CH,*OH (CH,),C*CH,.OH= (CH,),CO
0.0
+ CH2O + OH.
However, an equally plausible scheme, involving H02, can be written

(CH,),C:CH2
+ H 0 2 = (CX3),C*CH2 (CH3),C0 + CH2*OH =

+
0-OH 0, = CH20 HO,.
CH,*OH
Thus the detailed mechanism for the formation of the carbonyl compounds is not finally established. The oxidation of isobutene, catalysed by hydrogen bromide, has been
94
95
C. F. Cullis, A. Fish, and D. W. Turner, Proc. Roy. SOC., 1961, A , 262, 318. C. F. Cullis, A. Fish, and D. W. Turner, Proc. Boy. SOC., 1962, A , 267, 433.
K N O X : G A S - P H A S E OXIDATION
37
studied by Hurst, Skirrow, and Tipper 9 0 and follows a similar study of the catalysed oxidation of isobutane.97 The reaction between 145" and 195" c is autocatalytic, giving Br*CH;C(CH,),*O*OH as the major product. The kinetics are not fully explained, but the branching reaction seems to be bimolecular between ROOOH and HBr. The chain reaction must involve abstraction of H from HBr by RO, since the reaction stops when all the hydrogen bromide is exhausted. Aromatics.-Drillat and his co-workers 98 have reinvestigated the oxidation of benzene a t about 600" c and have confirmed that the reaction is of the degenerately branching type. The slow oxidations of the three isomeric xylenes have been compared by Wright.99 The ortho-isomer is the most reactive and the overall orders for ortho-, metct-, and para-isomers are 1.9, 2.8, and 1.5, respectively. The activation energies are all about 40 kcal. The rates of oxidation increase with xylene pressure, but are independent of oxygen pressure above a certain limit. Competitive-oxidation experiments show that the differences in reactivity do not lie in the chain-propagating steps ; the dependence of the acceleration constants on xylene pressure suggests that the differences lie in the rates of branching. I n an analytical study of the oxidation of o-xylene 7 7 in a flow system, 38 products were identified by gas chromatography. The main products formed, without destruction of the benzene ring when 72% of the xylene had reacted, are 2-methylstyrene (14% molar of xylene reacted), toluene (lo%), benzene (6y'), o-tolualdehyde (5%), benzofuran (5y0), o-ethyland toluene (4%). Those formed by degradation of the ring are CO (200~0), (60yO),H?,o (l5O%), CH, (25%)> HZ (20y0)7 C,H, (lo%), and CzH, (5%). Wright concludes that the initial step probably preserves the ring but, once it is ruptured, extensive degradation takes place rapidly. o-Tolualdehyde seemed the most likely branching agent. Barnard and Hawtin l o o have examined the oxidation of p-xylene, in a static system, between 460" and 510" c. The main products are carbon monoxide and dioxide, with small amounts of toluene, hydrogen, and methane. The order of the reaction is 3, contrasting with Wright's value of 1-5.77 Formaldehyde in 2% yield is also reported and, since its addition removes the induction period, it is considered to be the most likely branching agent. The mechanism suggested is similar to that of Enikolopyan et al. for methane. 56 Jones et aZ.lol have studied the oxidation of several aromatic hydrocarbons in a flow system, with a fine rain of metallic particles as heat exchangers. They agree with other workers that benzene, toluene, and the xylenes are relatively unreactive and tend to give extensively degraded
P. Hurst, G. Skirrow, and C. F. H. Tipper, Proc. Roy. SOC., 1962, A , 268, 405. E. R. Allen and C. F. H. Tipper, Proc. Roy. SOC.,1960, A , 258, 251. 9 8 J. Drillat and P. Laffitte, Compt. rend., 1960, 251, 2359; J. Drillat, ibid., 1961, 252, 1155; R . Ben Aim and J. Drillat, Bull. SOC.chiin. France, 1962, 519. 99 F. J. Wright, J. Phys. Chem., 1960, 64, 1944. loo J. A. Barnard and P. Hawtin, Combustion and Flame, 1961, 5, 249. lol J. H. Jones, M. R . Fenske, D. G . Hutton, and H. D. Allendorf, J. Chem. and Eng. Data, 1961, 6, 623.
96
97
38
products, whereas ethyl- and isopropyl-benzenesgave large yields of styrene and methylstyrene, with smaller yields of benzaldehyde and acetophenone. This is codrmed by Kroger and Bigorajski lo2who have oxidised ethylbenzene, styrene, benzene, and toluene, in a static system, at 3 8 0 4 1 0 " , 310-340", 415", and 450" C, respectively. Styrene is the principal product of the oxidation of ethylbenzene, and formaldehyde and benzaldehyde are the principal products from styrene, accounting initially for about 70 yoof the hydrocarbons disappearing. With benzene and toluene the main products are oxides of carbon and water, although traces of benzaldehyde are obtained from toluene. There seems little doubt that benzenes substituted only with methyl groups undergo extensive degradation. Whether the initial reaction preserves the ring or not is questionable, although Wright's results 7 7 certainly indicate that some of the initial reaction preserves the ring intact. With benzene substituted with higher alkyl groups, or olefinic groups, the situation is different. They are oxidised initially in the same way as the alkanes or olefins, obtained by replacing the phenyl group by hydrogen. Oxygenated Compounds.-Acetaldehyde. Chamboux and Lucquin lo3 have mapped the various oxidation regions of acetaldehyde-oxygen mixtures at temperatures between 200" and 500" c. Their results are similar to those of Ben Aim and Lucquin for n-pentane.lo4 Six types of oxidation can be distinguished: (i) a slow straight-chain reaction at low temperatures and pressures ; (ii)a slow branched-chain reaction; (iii) a slow branched-chain reaction showing a " pic d'arr6t " just before reaction ceases; and (iv) ignitions at low temperatures in an ignition peninsula, and at higher temperatures and pressures. Regions (iii) and (iv) enclose two further regions: (v) single and double cool flames and (vi) third-stage ignitions which occur within a narrow peninsula, extending over a moderate pressure range but with narrow temperature limits from the ignition boundary into the cool-flame region. Sokoleva, Markevich, and Nalbandyan l o 5 have measured the rate of initiation of the oxidation of acetaldehyde between 320" and 380" c, by oxidising mixtures of about 1% of acetaldehyde in air in a flow reactor of molybdenum-glass, which preserves HO, and hydrogen peroxide. Yields of formaldehyde and hydrogen peroxide were determined for the first 20% consumption of the acetaldehyde. The peroxide yield rises linearly with time, and is unaffected by the addition of formaldehyde. Thus it does not arise from the secondary oxidation of formaldehyde. The initial rate of formation follows the equation [ d[H202]/dt = k [ 0 2 ] CH3*CK0l2. The Authors deduce that the mechanism is
C H 3 * C H 0 0 , = CH,*CO HO, CH,*CHO H O , = C H 3 * C 0 H202 HO, = Wall termination
+ +
(1)
(2) (3)
C. Kroger and G. Bigorajski, Erdol u. Kohle, 1962, 15, 109. J. Chamboux and M. Lucquin, J. Chim. phys., 1962, 59, 797. 1 0 4 R . Ben Aim and M. Lucquin, J. Chim. phys., 1959, 56, 475, 649. lo5 N. A. Sokoleva, A. M. Markevich, and A. B. Nalbandyan, Zhur. $ . Khim., 2 1961, 35, 850 (transl. 415).
102
los
39
This scheme gives the observed rate expression only if reaction (2) is the controlling step in a long chain. Then k = k,k,/k3. However, the other main reaction product is formaldehyde and this is almost certainly formed via the reactions CH,*CO = CH, CO; CH, 0, = CH,O OH Reactions (2) and (3) must therefore involve OH, not HO,, if the overall process is a chain reaction as assumed. Denoting these reactionsoby (2') and (3'), k = k1k2,/lc3,. The observed activation energy of 30 kcal. is then E, E' - E i . Thus 30 kcal. is the maximum value for El, giving , D[CH,*CO-HI < 76 kcal., a rather low value. AZcohoZs. The work of Cullis and Newitt 106 on ethanol has been extended to the propyl alcohols lo7and the four butyl alcohols,lo8in the temperature range 3 5 0 4 5 0 " c. The initial products, where possible, are an aldehyde, or ketone, and hydrogen peroxide in equimolar yields. The oxidations are similar to those of the alkanes, and are most simply explained by an HO, radical chain. For example, with propan-2-01
(CH,),CH*OH X(H0,) = (CH,),C(OH) XH(33-20,) (CH,),C(OH) 0 , = (CH,)&O Hop
With t-butyl alcohol this chain cannot occur; the alcohol is analogous 60 neopentane. It differs from the others in exhibiting only a high-temperature oxidation region. The others show low-temperature oxidation zones, negative temperature coefficients, and sometimes cool flames. Other initial products may be formed in smaller quantities : isobutyl alcohol gives acetone and formaldehyde, in addition to isobutyraldehyde and hydrogen peroxide, and s-butyl alcohol gives acetaldehyde, in addition to ethyl methyl ketone and hydrogen peroxide. These further products can arise from the decomposition of the relevant peroxy-radicals. t-Butyl alcohol gives as initial products only acetone and an unidentified C, compound. These findings have been confirmed by experiments by Blumberg et d 1 0 9 in which the liquid-phase and the gas-phase oxidation of ethanol, under pressure, are compared. Esters. Fish and Waris I1O have started a programme of investigation of the oxidation of esters, -withethyl acetate in a flow system at 2 5 0 4 5 0 ' C. There is a negative temperature coefficient between 350" and 380" c. Acetic acid and formaldehyde are the major low-temperature products (in the ratio of about 5 : 1 ) ; acetaldehyde begins to appear at 350" c. A peroxide mechanism is invoked to account for the products. Oxidation of Alkyl Radicals.-The study of the direct oxidation of alkyl radicals formed by photolysis or pyrolysis has proved difficult, and much of lo6 C. F. Cullis and E. J. Newitt, Proc. Roy. SOC., 1956, A , 237, 530; 1957, A, 242,
516.
lo' C. F. Cullis and E. J. Newitt, Proc. Roy. SOC., 1960, A, 257, 402; A. R. Burgess, C. F. Cullis, and E. J. Newitt, J., 1961, 1884; A. R. Burgess and C. F. Cullis, ibid., p. 3014; A. R. Burgess, J. Appl. Chern., 1961, 1 , 235. 1 lo8 C. F. Cullis and E. A. Warwicker, Proc. Roy. SOC.,1961, A, 264, 392. l o D E. A. Blumberg, G. E. Zaikov, Z . K. Maizus, and N. M. Emanuel, Kinetika i Kutaliz, 1960, 1 510 (transl. 477). , l l o A . Fish and A. Waris, J., 1962, 4513.
40
the earlier work is conflicting and difficult to interpret. However, recent work on methyl gives a more consistent picture. Methyl. There is no question that methyl radicals readily associate with oxygen to give methylperoxy-radicals which, in the first instance, must be excited. It is gradually becoming evident that most of the chemical reactions which follow are those of thermalised peroxy-radicals, although this still requires confirmation. Subbaratham and Calvert, ll1 and Drever and Calvert,ll2 in complementary investigations have established the main features of the oxidation of methyl a t room temperature. They have made direct infrared absorption measurements of photo-oxidising azomethane, in a 70-1. reaction vessel with an optical system of 40 m. path-length. Reaction mixtures contained about 1 mm. of azomethane and 1-740 mm. of oxygen. The total pressure was made up to 740 mm. with inert gas. Irrespective of oxygen pressure, roughly equimolar amounts of formaldehyde and methanol are obtained with smaller amounts of formic acid and methyl hydroperoxide. Since different inert gases have no effect, CH,*O*OHdoes not arise from abstraction by activated CH,*O*O, which would otherwise decompose. Experiments with hexadeuteroazomethane, CD,*N:N*CD,, in the presence of acetaldehyde, gave only CD,*O*OD and thus CD,*O*Odoes not abstract hydrogen from acetaldehyde or azomethane. The products must therefore be explained by radical-radical reactions of thermalised peroxy-radicals. The likely reactions are 2CH,-O*O = 2CH30 + 0, (1)
CH30 2CH30 = CH,O + CH,-OH + CH,*O*O = CH,-O.OH + CH,O or C H 3 . 0 H + H.CO,H. (2)
(3)
I n the presence of added formaldehyde the peroxide yield falls and that of methanol rises. This means that the CH,O radical can abstract from CH,O, while CH,*O*Ocannot :
CH,O
+ CH,O
CH,*OH
+ CHO.
(4)
Shanin and Kutschke 113 have studied the same reaction between 20" and 160" c , using mass-spectrometric analysis. They have established that CH,*O*OHis a reaction product a t all temperatures, but considerable precautions have t o be taken to prevent its destruction on the metal parts of the apparatus. The addition of tetradeuteromethane gives no CH,O*O*D and so CH,*O*Odoes not abstract deuterium from tetradeuteromethane a t 100"c , confirming Calvert's results.lll~ 112 At this temperature the quantum yield of peroxide was about 0.5 and much greater than the value obtained by Calvert. Blake and Kutschke 11* have oxidised di-t-butyl peroxide a t 160"C. The overall rate of decomposition is unaffected by added oxygen and so the reaction is non-chain. The main initial product is formaldehyde, in
N. D. 113 M. 1961, 39,
l11
112
R. Subbaratham and J. G . Calvert, J . Amer. Chem. Soc., 1962, 84, 1113. F. Drever and J. G. Calvert, J . Amer. Chem. Soc., 1962, 84, 1362. Shanin and K. 0. Kutschke, J . Phys. Chem., 1961, 65, 189; Canad. J . Chem.,
73. R. Blake and K. 0. Kutschke, Canad. J . Chern., 1961, 39, 278.
1l4A.
41
similar yield t o acetone. Small quantities of methanol are also formed. Later in the oxidation the formaldehyde pressure reaches a stationary value, carbon monoxide appears, and the pressure of methanol increases more rapidly. Kinetic tracer experiments show that all the carbon monoxide arises from formaldehyde, indicating that some species abstract from CH,O giving CHO which is oxidised t o HO, and CO. The absence of methanol as a major initial product indicates that most of the CH,*O*O radicals decompose by CH,.O.O = CH,O + OH (5) The formation of methanol later in the reaction, when the formaldehyde has accumulated, together with the previous observation of methyl hydroperoxide,l13 indicates that reaction (6) occurs : CH,.O.O + CH,O = CH,*O.OH + CHO. (6) That methyl hydroperoxide would decompose to give methanol was found by independent experiments, when the peroxide was admitted to the reaction vessel. Reaction (6) does not occur a t room temperature, according t o the results of Calvert. The results of Kutschke are in general agreement with those of Fisher and Tipper,64 who introduced reaction (6) t o explain the formation of methanol and methyl hydroperoxide in the photo-oxidation of methane at 400" c. Hoare and Wellington 115 have also studied the oxidation of methyl radicals, formed by the photolysis and pyrolysis of di-t-butyl peroxide, at 50", loo", and 135" c, and by the photolysis of acetone a t 200"c . Oxygen pressures were 0-5 mm. There is no evidence for any change of mechanism over this range as would have been expected by comparison of the results of Calvert and Kutschke. The initial products are formaldehyde and methanol, carbon monoxide appearing later. As the reaction proceeds the quantum yield of formaldehyde falls and that of methanol rises to a maximum ; the quantum yield of carbon monoxide rises continuously. Adding formaldehyde increases the initial quantum yield of methanol towards unity and also that of carbon monoxide. Hoare and Wellington claim that the initial quantum yields of formaldehyde and methanol are both 0.5. This conflicts with Blake and Kutschke's result 11*and, indeed, their own experimental data 115 suggest that the true initial quantum yield of formaldehyde is considerably greater than that of methanol. There is therefore some doubt as t o the interpretation of their results. The authors assume that the methanol which they observe is initially formed as methanol, not methyl hydroperoxide, but there is no real evidence that this is the case. In order t o explain the methanol formed, in the presence of added formaldehyde, they propose reaction (a), but this conflicts with the evidence of Hanst and Calvert *O that methoxyl radicals oxidise to formaldehyde and HO, at about 200" c. There is obviously more work still to be done in this field. The main pitfall seems to be failure to distinguish between methanol and methyl hydro115 D. E. Hoare and C. A. Wellington, 8th Internat. Symposium on Combustion, Williams and Wilkins, Baltimore, Md., 1962, p. 472.
42
GENERAL A N D P H Y S I C A L CHEMISTRY
peroxide in the products. Further work is required on the oxidation of can methoxyl, to establish whether reaction (4) occur a t high temperatures. This is relevant in connexion with the source of methanol in hydrocarbon oxidation. The effect of inert gases requires further investigation, to establish finally whether activated peroxy-radicals are chemically important or not. The general picture which emerges is that CH,*O*Oradicals, a t about room temperature, undergo only disproportionation. At higher temperatures they mostly decompose t o formaldehyde but some abstract to give methyl hydroperoxide, which will generally be analysed as methanol. Johnson and Salmon 116 have shown that the only important product from the y-ray-initiated oxidation of methane a t room temperature is methyl hydroperoxide. This conflicts with the results of photochemical experiments, but can probably be explained by the presence of HO, radicals which react by
CH,*O*O
+ KOz = CH,-O*OH + 0,.
(7)
The results are similar to those of photosensitised oxidations.117 The predominant decomposition of methylperoxy to formaldehyde and OH, which is assumed in all mechanisms for the oxidation of methane, has been confirmed by the flash photolysis work of McKellar and Norrish,llS who have observed the spectra of both OH and CH20 in the flash photolytic oxidation of methyl iodide, some 30 psec. after the initiating flash. The results of the fast-flow experiments of Avramenko and Postnikov 119 conflict with those of the photochemical work. When methyl radicals, produced by the pyrolysis of acetone, are oxidised at a total pressure of 0.63 mm. Hg, methyl hydroperoxide is the only product detected in the products condensed on a cold finger. No formaldehyde is found even with the reactor a t 450" c, although some carbon dioxide is obtained (about 30% of the peroxide). The system was checked by measuring the rate constant for recombination of methyl radicals by determining the saturation yield of methyl hydroperoxide, when the oxygen was added a t different distances downstream from the methyl radical source. The rate constant was in good agreement with the accepted value. The rate constant for CH, O2 = CH,*O*O was determined from the variation of the yield of peroxide with oxygen concentration, and the value is almost the same as that found by Hoare and Walsh,120 although obtained a t a much lower total pressure. The authors 119 propose that two reactions are involved, a bimolecular reaction which gives activated CH,*O*O radicals, which then abstract from acetone, and a thermolecular reaction which gives thermalised CH,.O-O radicals which also abstract hydrogen from acetone :
CH,
116 1' 1
CH, + 0 , = CH,*O*O* 4 CH,*O.OH + 0, + M = CH,*O*O + M +CH,*O.OH.
Their rate constant is then k8 while that of other workers is k,
+ k,[M].
(8) (9)
G. R. A. Johnson and G. A. Salmon, J . Phys. Chern., 1961, 65, 177. J. S. Watson and B. de B. Darwent, J . Phys. Chem., 1957, 61, 577; A. B. Nalbandyan, Dokludy A k ud. Nuuk S.S.S.R., 1952, 86, 589; J. Gray, J., 1952, 3150. 118 J. F. McKellar and R. G. W. Norrish, Proc. Roy. SOC., 1961, A , 254, 147. 110 L. I. Avramenko and L. M. Postnikov, Izvest. Akad. Nuuk S.S.S.R., 1960, 1921 (transl. 1796). 1957, 53, 1102. lZo D. E. Hoare and A. D. Walsh, Trans. Faraduy SOC.,
43
The complete absence of formaldehyde in the products is difficult to explain and makes it questionable whether the peroxide could have arisen from a gas-phase abstraction from acetone. It could have been formed in the cold trap used to collect the products. The formation of unexpected products seems to be a feature of the fast-flow experiments of Avramenko and his co-workers. A complementary study has been made by Avramenko and Kolesnikova 1 2 1 on the oxidation of the radical derived by reaction of hydrogen atoms with methanol. This may be either CH,OH or CH,O. The authors favour the former. The oxidation products are formaldehyde and hydrogen peroxide in yields consistent with the reactions
CH,OH
+ 0, ZHO,
= =
CH,O H,02
.+ HO, + 0,.
(10)
The rate constant is k,, = 2.4 x 10l2exp [ -2500/1.987T] mole-1 ~ ~ 1 sec.-l. 1 . ~ Bell and Macdowell 122 have studied the merOther alkyl radicals. cury-photosensitised oxidation of isobutane between 30" and 100" c. The main product is t-butyl hydroperoxide, with about half the amount of acetone t-butyl alcohol. The dependence of the quantum yield, which is low, on light intensity and reactant concentration shows that the reaction is non-chain and that the peroxide is probably formed by
C,H,-O*O
+ HO, = C,H,*O.OH + 0,.
The results are thus' in agreement with those from other mercury-photosensitised oxidations.l17 The oxidation at 25" c of t-butyl radicals, generated by photolysis of azoisobutane, has been studied by Thomas and C a l ~ e r t , l * ~ using the long-path infrared technique.111, 112 Azoisobutane pressures were about 0.1 mm. and oxygen pressures 20 and 740 mm. The main initial products are acetone, formaldehyde, and t-butyl alcohol and hydroperoxide, in comparable yields, with smaller quantities of methanol. As with methyl radicals there is no chain reaction and all the products can be explained on the basis of radical-radical reactions with the addition of C,H,*O = CH,*CO*CH, CH,, which accounts for the acetone and provides a source of CH,, CH,-O*O and CH,O. The Reactions of Oxygen Atoms.-The literature on the reactions of oxygen atoms, up to the end of 1959, has been authoritatively reviewed by Kaufman.lZ4 We mention here the more recent work on the reactions of oxygen atoms with organic compounds. For the purpose of deriving kinetic data oxygen atoms can be generated in several ways : (1) by the mercury-photosensitiseddecomposition of nitrous oxide 125(r which gives N2 0 ; (2) by photolysis of nitrogen
L. I. Avramenko and R. V. Kolesnikova, Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Nauk, 1961, 591 (transl. 545). l Z 2 K .M. Bell and C. A. Macdowell, Canad. J. Chem., 1961, 39, 1419, 1424. lZ3 S. S. Thomas and J. G. Calvert, J. Amer. Chem. SOC., 1962, 84, 4207. lZ4 F. Kaufman, " Progress in Reaction Kinetics," ed. G. Porter, Pergamon Press, London and New York, 1961, Vol. I, p. 1. lZ5 ( a ) R. J . Cvetanovic, J . Chem. Phys., 1955, 23, 1203; ( b ) S. Seto and R. J. Cvetanovic, Canad. J. Chem., 1958, 36, 970.
121
44
giving NO 0; (3) by passing a silent discharge through oxygen,las giving 0 0,; and (4) by titrating nitrogen atoms with nitric oxide, giving 0 N2.2zu The reactions of oxygen atoms are hydrogen-abstraction, addition to double bonds and possibly insertion into C-H and C-C bonds. The existence of the insertion reactions proposed by Avramenko and his co-workers has been doubted by K a ~ f m a n ,who does not accept their mechanisms. l~~ The recent work concerns carbon tetrachloride, 127 benzene, 128 toluene, 129 methanol, 30 acetaldehyde, 131 and 1,2-dichloroet hane .13 2 Ung and Schiff,l2' using methods (3)and (4)for generating oxygen atoms, find that with carbon tetrachloride the products are chlorine, carbonyl chloride, and carbon monoxide and dioxide. They propose that oxygen atoms add t o carbon tetrachloride and that the complex decomposes
+ +
+ CCl,
[OCCI,]
7coc12 + c1, kco + 2c1,.

~111.~ sec.-l.
Carbon dioxide is then formed by a rapid reaction of carbonyl chloride with oxygen atoms. The rate constant for the addition reaction is
k = 2.0 x 1O1O exp [ -4500/1.987T] mole-1
The low A factor is noteworthy. Boocock and Cvetanovic,128and Jones and Cvetanovic l 2 9 [method (l)] have found that the reactions with benzene and toluene are some 100 times slower than with olehs. The products are mainly polymeric and no mechanism could be derived. Avramenko, Kolesnikova, and Kuznetsova 130 [method (3)] have found that with methanol the only products are formaldehyde and a small yield of hydrogen peroxide. Since the radical derived by hydrogen-abstraction from methanol 121 gives a substantial yield of hydrogen peroxide on oxidation they conclude that the oxygen atom must react directly with methanol, t o give formaldehyde and water :
0
+ CH,*OH = C H 2 0 + H20.
The rate constant of the reaction is
=5
x l o l l exp [ -3100/1.987T] r n o l e - l ~ m .sec.-l. ~
With acetaldehyde, the products are methyl hydroperoxide, keten, and glycollaldehyde, and completely different from those obtained by Cvetanovic l 3 3 (only biacetyl). The products suggest that insertion into C-H
1 2 6 L. I. Avramenko and R. V. Kolesnikova, Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Nauk, 1955, 386; 1958, 277. 12' A. Y. M. Ung and H. I. Schiff, Canad. J. Chem., 1962, 40, 486. 1 2 8 G. Boocock and R. J. Cvetanovic, Canad. J. Chem., 1961, 39, 2436. 1 2 9 G. R. H.Jones and R . J. Cvetanovic, Canad. J. Chem., 1961, 39, 2444. 1 3 0 L.I. Avramenko, R. V. Kolesnikova, and N. L. Kuznetsova, Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Nauk, 1961, 599 (transl. 522). 131 L. I. Avramenko, R. V. Kolesnikova, and M. F. Sorokin, Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Nauk, 1961, 1005 (transl. 930); 1231 (transl. 1141). 1 3 2 L. I. Avramenko, R. V. Kolesnikova, and N. L. Kuznetsova, Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Naulc, 1961, 1565 (transl. 1462). 133 R. J. Cvetanovic, Canad. J. Chem., 1956, 3 , 775. 4
SYMONS: ELECTRON S P I N RESONANCE
45
bonds occurs. The rate constant, based upon the rate of formation of acetic acid, is
= 3.6
x l o l l exp [ -2750/1.987T] mole-1
~ 1 1 1sec.-l. .~
The value calculated for 300" K is about 30 times lower than Cvetanovic's value. With 1,e-dichloroethane the main products are hydrochloric acid and carbon monoxide. It is suggested that 0 attacks the C-C bond, with rupture of the molecule and formation of CH, as one product. As this reaction is endothermic, it is most improbable. The rate constant for the reaction, whatever its nature, is
= 1.2
x 1013exp [ -5500/1.987T] mole-1
sec.-l.
Elias and Schiff 2o [method (4)]have obtained the rate constant for reaction with n-butane as
Ic
= 3.1
x 1013exp [ -4200/1.987T] mole-1 ~ msee.-'. . ~
The picture of activation energies is reasonably consistent, but that of the A factors is unsatisfactory. Further work is required to resolve the disagreement between the results of Avramenlco and those of Schiff, Cveianovic, and Kaufman.
J. H. K.
4. ELECTRON SPIN RESONANCE
DURING past two years the output of research papers in this field has the
increased t o such a level that it is no longer possible t o give adequate attention to more than a small percentage of them. This report follows its predecessor in stressing what seem to the Reporter t o be the more chemical aspects, t o the neglect of advances in instrumental methods, theoretical implications, ferro and antiferromagnetism, and biological applications. Recent general reviews include those of Weissman 2 and Shulman which, taken together with articles on this subject in earlier issues of the Annual Reviews of Physical Chemistry, constitute a most useful and authoritative account. Other reviews contain discussions of recent advances in the fields of transition-metal chemistry, * organic free radicals, and inorganic free radicals.6 Transition-metal Complexes.-Two more important books on ligand field theory and related topics have appeared.', 8 Host crystals for transition metal and other I' impurity " ions, other than the alkali and alkaline-earth
Ann. Reports, 1960, 57, 68. S. I. Weissman, Ann. Rev. Phys. Chem., 1961, 12, 151. R. G. Shulman, Ann. Rev. Phys. Chem., 1962, 13, 325. D. E. O'Reilly, Advances in Catalysis, 1960, 12, 31. M. C. R. Symons, " Advances in Physical Organic Chemistry," ed. V. Gold, Academic Press, London, 1963, Vol. I. " Free Radicals in':norganic Chemistry," 36, Adv. in Chem., A.C.S., 1962. 7 C. J. Ballhausen, Ligand Field Theory, McGraw-Hill, New York, 1962. 8 C. K. Jorgensen, " Absorption Spectra and Chemical Bonding in Complexes," Pergamon Press, Oxford, 1962.
F.
46
halides, include aluminium oxide containing V3+,9Cr3+,10 and Gd3+,11and titanium dioxide containing Mn4+ 1 2 9 1 3 Considerable attention has been given to near neighbourinteractions,l0-16 especially bivalent manganese pairs in zinc fl~oride.1~ These studies are important to the study of ferro- and antiferro-magnetisrn.l6 Hayes l7has reviewed results for transition-metal ions in unusual valence states, which are formed on exposure to high energy radiation. Several studies of complexes having aromatic ligands have been reported.18 Dorain 1 9 has analysed the spin-resonance spectrum of quadrivalent rhenium in potassium hexachloroplatinate(IV), and Rubins 20 the spectrum of ferrous ions in zinc fluorosilicate. Covalent bonding. Shulman 3 has concluded that the interesting suggestion by Marshall and Stuart,21 that it is not necessary to invoke covalent bonding in order to understand hyperhe interactions with ligand nuclei, cannot be maintained since the theory neglected the effect of mbonding, which is known from electron spin resonance 22 and nuclear magnetic resonance 23 studies to be of great importance. Calculations support this view.24 Covalent bonding in cuc164- ions has been discussed by Thornley et ~ 1 . 2 ~ d l Transition-metal complexes. Electron spin resonance spectra having relatively narrow lines have been recorded for a variety of d l complexes at room temperature. This means that the efficient relaxation processes which usually operate both for octahedrally and tetrahedrally co-ordinated complexes of this class are unimportant, and this can generally be understood in terms of the very low symmetry of the ligand environment. Golding 26 has studied single crystals containing vanadyl oxalate, but the level-scheme used to discuss the resulting hyperfine and g-tensors differs from that proposed for similar complexes, by Ballhausen and Gray.Z7 These authors have discussed bonding in " oxycations " such as V02+,in the light of specG. M. Zverev and A. M. Prokhorov, J. Exp. Theor. Phys. (U.S.S.R.),1960, 38,
449.
l o H. Statz, L. Rimai, M. 5. Weber, G. A. de Mars, and G. F. Koster, J. Appl. Phys., 1961, 32, 218s. l1 S. Gekchwmd and J. P. Remeika, Phys. Rev., 1961, 122, 757. l2 H. G. Andresen, J . Chem. Phys., 1961, 35, 1090. l3 H. G. Andresen, Phys. Rev., 1960, 120, 1606. l4 J. Owen, M. R. Brown, B. A. Coles, and R. W. H. Stevenson, J. Phys. SOC. Japan, 1962, 17, Suppl. B-I, 428. l5 J. Owen, J . Appl. Phys., 1962, 35, 335. l6 M. R. Brown, B. A. Coles, and J. Owen, Phys. Rev. Letters, 1961, 7, 246. IT W. Hayes, J. Phys. Soc. Japan, 1962, 17, Suppl. B-I, 456. I s H. H. Dearman, W. W. Porterfield, and H. M. McConnell, J . Chem. Phys., 1961, 34, 696; J. C. W. Chien and C. R. Boss, J. Amer. Chem. SOC., 1961, 83, 3767; R. D. Feltham, J . Inorg. Nuclear Chem., 1961, 16, 197. l9 P. B. Dorain and R. Rahn, J . Chem. Phys., 1962, 36, 561. 2 o R. S. Rubins, Proc. Phys. Xoc., 1962, 80, 244. 21 W. Marshall and R. Stuart, Phys. Rev., 1961, 123, 2048. 2 2 L. Helmholz, A. V. GUZZO, and R. N. Sanders, J . Chem. Phys., 1961, 35, 1349. 23 R. G . Shulman and K. Knox, Phys. Rev. Letters, 1960, 4, 603. 2 4 R. G. Shdman and S. Sugano, Phys. Rev. Letters, 1961, 7, 157. 2 5 J. H. M. Thornley, B. W. Mangum, J. H. E. Grfiths, and J. Owen, Proc. Phys. SOC.,1962, 78, 1263. 2 6 R. M. Golding, MoZ. Phys., 1962, 5, 369. 2 7 C. J. Ballhausen and H. B. Gray, Inorg. Chem., 1962, 1, 111.
SYMONS: ELECTRON SPIN RESONANCE
47
tral and magnetic data, and consider that a form of double x-bonding is important and is largely responsible for the unusual properties of such complexes. A quinquevalent chromium complex, formed when chromate was added t o oleum,2*had magnetic and optical properties very similar t o those of the aquated vanadyl ion and the ion CrOC1,2-.29 Addition of fluoride ion to aqueous solutions containing the ion Ti(H20),3+ resulted in a complex, containing two fluoride ligands, which gave a wellresolved spectrum at room temperature,30 in marked contrast with the aquated ion, which had to be cooled t o extremely low temperatures before any absorption could be detected. Again, various interesting compounds containing tervalent titanium, linked by chloride bridges t o aluminium alkyl complexes, have narrow spectra a t room temperature, which sometimes contain hyperfine structure from 27Al,31 and possibly also from h ~ d r i d e .33 ~ , ~ Two groups of workers have studied the interesting peroxy-ion of quinquevalent chromium, Cr(0,)43-.34,35 This ion, in marked contrast with the hypochromate ion, CrOp3-,36 gave rise to a narrow spin resonance absorption at room temperature, and the axially symmetric g-tensor was very similar to that found, for example, for vanadyl salts.26 It seems 34 that one oxygen of each peroxide ligand is slightly closer to chromium than the other, and it is suggested that the unpaired electron is largely confined t o that d-level which is not directed towards any of the oxygen atoms. Exposure of calcium tungstate single crystals t o y-radiation resulted in the formation of two distinct paramagnetic centres, one of which has been tentatively identified as the hypotungstate ion, Spin-resonance absorption from this centre, as might be expected by comparison with other tetrahedral d l o x y i o n ~ , was only detectable at very low temperatures, and ~* the g-values and hyperfine coupling constants were also in accord with expectation for this ion. The nature of the other centre, which was shown t o contain two equivalent tungsten atoms,37 is still uncertain. Other transition-metal complexes. Amongst other unusual complexes studied by spin resonance methods were tricyclopentadienyl trinickel dicarbonyl,39 various nitroso-derivatives,40~41 and peroxy-bridged dicobalt am mine^.*^ The nickel complex is unusual in that most stable complexes of this type are diamagnetic. The theory of g-values has been extended
Mishra and M. C. R. Symons, Proc. Chem. SOC.,1962, 23. Hare, I. Bernal, and H. B. Gray, Inorg. Chem., 1962, 1 831. , 30 Waters and A. H. Maki, Phys. Rev., 1962, 125, 233-4. 31 Maki and E. W. Randall, J . Amer. Chem. SOC.,1960, 82, 4109. 32A. Zefirova, N. N. Tikhomirova, and A. E. Shilov, Doklady Akad. Nauk K. S.S.S.R., 1960, 132, 1082. 3 3 H. J. M. Bartelink, H. Bos, J. Smidt, C. H. Vriassen, and E. H. Adema, Rec. Trav. chim., 1962, 81, 225. 34 J D. Swalen and J. A. Ibers, J. Chem. Phys., 1962, 37, 17. . 3 5 B. R. McGarvey, J . Chem. Phys., 1962, 37, 2001. 36 N. Bailey and M. C. R. Symons, J., 1957, 203. 37 H. Zeldes and R . Livingston, J. Chem. Phys., 1961, 34, 247. 38 A. Carrington, D. J. E. Ingram, K. Lott, and M. C. R. Symons, Proc. Roy. SOC.,1960, A, 254, 101. 39 H. C. Longuet-Higgins and A. J. Stone, Mol. Phys., 1962, 5, 417. 4 0 I. Bernal and E. F. Hockings, Proc. Chem. SOC., 1962, 361. 41 I. Bernal and S. E. Harrison, J. Chem. Phys., 1961, 34, 102. 4 2 G. L. Goodman, H. G. Hecht, and J. A. Weil, Free Radicals in Inorganic Chemistry, No. 36, Adv. in Chem., A.C.S., 1962, p. 90.
28
29
H. C. C. R. E. L. A. H.
48
t o cover this case and it was concluded that the unpaired electron is in an A2" orbital on all three nickel atoms.39 The nitroso-compounds are interesting in that the unpaired electron is clearly delocalised on to nitrogen,40, 41 although only the isotropic part of the 14N hyperfine coupling tensor has been measured. It was concluded that the complex ion Cr(CN),NO3- is best described as a derivative of Cr+,41 but that Fe(CN),N03- is better described in terms of molecular orbitals delocalised to a considerable extent onto the ligands.40 Organic and Inorganic Free Radicals.-These have been studied extensively in fluid and rigid solutions and oriented in single crystals. Much of the work has been consolidation of advances reported earlier.1 I n this report attention is focused primarily on new developments. Preparative methods. Electrolytic methods have been used extensively, especially as an alternative t o the use of alkali metals, for the preparation of r a d i ~ a l - a n i o n s . ~ ~ example, an important new class of radicals, the For nitroalkane anions, RN02-, has recently been prepared by this method,44 and identified by electron spin resonance. Flow techniques have been used for the study of unstable radicals.45 Very recently a range of very unstable organic radicals, including several which had been detected previously in rigid glasses, have been prepared utilising hydroxyl radicals generated in a flow system by reactions such as 4 6
Ti3+
+ H 2 0 2+TiOH3+ + *OH.
These results, which will most likely have been published in full before this report appears, are very important since the method is far simpler than that of electron bombardment in ~itu,47and a t the same time, should enable investigators to characterise transient radical intermediates in a variety of reactions. For example, attack by hydroxyl radicals. on alcohols occurs largely on cc-hydrogen,as previously deduced from spectra of trapped radicals at 77" K . ~ * The great improvement in resolution thaf, results, is well illustrated by comparing spectra assigned t o the radical CH,C*Me,*OH. Each component of the triplet of overlapping lines detected originally 48 has been split into septets. This minor splitting can arise only by interaction with the six y-protons for which a hyperfine coupling constant of 1.3 gauss was found.46 Addition to ally1 alcohol occurred a t room t e m p e r a t ~ r ewhereas ,~~ attack on allylic hydrogen was diagnosed for the reaction a t 77" K.48 Hydrogen atoms, formed by photolysis of various simple inorganic molecules such as hydrogen iodide, often add t o substrates in rigid matrixe? at 4.2"K. This pethod has been used to prepare the radicals HC0,49H2CN,50 and probably CH,=CH,51by addition to carbon monoxide, hydrogen cyanide
L. H. Piette, P. Ludwig, and R. N. Adams, Analyt. Chem., 1962, 34, 916. L. H. Piette, P. Ludwig, and R. N. Adams, J . Arner. Chem. SOC., 1962, 84, 4212. 4 6 T. J. Stone and W. A. Waters, Proc. Chem. SOC., 1962, 253. 4 6 R. 0. C. Norman, Nature, 1962, 196, 891; R. 0 C. Norman, November Meeting . of The Chemical Society, London, 1962. 4 7 R. W. Fessenden and R. H. Schuler, J . Chem. Phys., 1960, 33, 935. 4 8 J. F. Gibson, M. C . R. Symons, and M. G. Townsend, J., 1959, 269. 4 9 F. J. Adrian, E. L. Cochran, and V. A. Bowers, J . Chem. Phys., 1962, 36, 1661. s o E. L. Cochran, F. J. Adrian, and V. A. Bowers, J . Chem. Phys., 1962, 36, 1938. s1 F. J. Adrian, E. L. Cochran, and V. A. Bowers, " Free Radicals in Inorganic Chemistry," No. 36, Adv. in Chem., A.C.S., 1962, p. 50.
43
44
49
and acetylene respectively. I n contrast, photolysis of hydrogen bromide in various unsaturated organic solids gave radicals which are thought to be the product of bromine-atom addition,52 and which have been tentatively identified as having a bromine atom which acts as a bridge between the olefinic carbon atoms. This result, if correct, is of considerable significance as regards the study of addition mechanisms, In the Reporters opinion, however, it is surprising that radicals formed by reaction with hydrogen atoms are not detected. Since radicals of the type postulated are likely to have considerable bromine atom character, one might expect to find g-values well removed from 2-0023 and with considerable anisotropy . Unfortunately, g-values were not reported, but in most instances little or no anisotropy is apparent in the published spectra. The spectra were poorly resolved, and in the light of these considerations, the conclusions drawn must be treated as tentative. It was claimed 52 that, since photolysis of deuterium bromide resulted in the formation of identical radicals, bromine atom addition must have occurred. This conclusion is not compelling, and an examination of the spectra recorded, and especially of the apparent hyperfine splittings, suggests to the Reporter that the trapped radicals are allylic in type, probably resulting from attack by hydrogen or deuterium atoms on appropriate allylic protons. Bamford and Ward 5 3 have prepared radicals close to the surface of various solids by application of a high-frequency discharge and bonded tritium atoms have been used as an internal source of high-energy radiation.54 Russell and his co-workers 55 found that various nitro-aromatic compounds, in strongly alkaline media, reacted to give high yields of the corresponding radical-anions. It was suggested that these may be formed by a bimolecular electron-transfer between the parent molecules and their conjugate bases.55 This corresponds to the mechanism proposed for the formation of aromatic radical-cations in sulphuric acid. 56 It has similarly been found that radical-anions were formed by the interaction between certain aromatic compounds and the corresponding dihydro-derivatives, in strongly alkaline media. 5 7 Aromatic radical-cations appear to be formed on the surface of silicaalumina catalysts, containing ferric oxide, by loss of an electron from the parent hydrocarbon^,^* although the spectra were so poorly resolved that identification is not certain. Similar radicals were formed by interaction with aluminium chloride,59and Adams and Nicksic 6 0 have found that a variety of unidentified radicals were formed by the interaction of aluminium chloride with a range of alkyl chlorides, with or without addition of benzene.
P. L. Abell and L. H . Piette, J . Amer. Chem. SOC.,1962, 84, 916. C. H. Bamford and J. C. Ward, Trans. Faraday SOC.,1962, 58, 971. 5 4 J. Kroh and J. W. Spinks, J . Chem. Phys., 1962, 35, 760; J. Kroh and J. W. Spinks, ibid., 1961, 34, 1853. 5 5 G. A. Russell, E. G. Janzen, and E. T . Strom, J . Amer. Chem. SOC., 1962, 84, 4153. 56A. Carrington, F. Dravnieks, and M. C. R. Symons, J., 1959, 947. 5 7 G. A. Russell, E. G. Janzen, and E. T. Strom, J . Amer. Chem. SOC., 1962, 84, 4155. 5 8 J. J. Rooney and R. C. Pink, Trans. Faraday SOC., 1962, 58, 1632. 5 9 J. J. Rooney and R. C. P n , Proc. Chem. SOC.,1961, 142. ik 6 o J. Q. Adams and S. W. Nicksic, J . Amer. Chem. SOC., 1962, 84, 4355.
52
53
50
Aromatic radicals i n solution. Equal population of the symmetric and antisymmetric levels of the benzene anion results in an even distribution of the unpaired electron. Substituents which do not directly participate in the n-electron framework will nevertheless lift the degeneracy of these levels, an electron-releasing substituent favouring the antisymmetric and an electron-attracting substituent the symmetric level. To some extent this description can also be expected to be useful for weakly conjugated anions. Tuttle and Weissman demonstrated this effect for alkyl substitution,61and Bolton and Carrington 6 2 have found that this description is valid in many instances. Furthermore, they were able to resolve the small coupling to alkyl protons for alkyl groups formally a t nodes in the unpaired electron's orbital, and to explain 6 3 nicely the resulting trends in terms of slight admixture of the symmetric level. Mechanisms for the required admixture were discussed,63 and T ~ t t l ewho~studied the spectra of the toluene and ,~ o-xylene anions, as a function of temperature and deuterium substitution, adduces evidence for vibronic mixing of states for the latter ion. Replacement of the t-butyl group in the t-butyl benzene anion by Me,Si and Me3Ge resulted in dramatic changes in the ring-proton coupling constants which suggest strongly that whilst Me3C- favours the antisymmetric form, the other groups favour the symmetric form. This was rationalised in terms of weak d - n bonding with silicon and germani~m.6~ Many other substituted benzene radicals have been studied which are better described in terms of molecular orbitals which embrace the p-n levels of the substituent. These include various p-substituted nitrobenzene anions,66 for which the relationship A, A , = -2.3 gauss is closely obeyed, provided A,, the isotropic hyperfine coupling constant to the meta-protons, is taken as positive. This result suggests, surprisingly, that the total spin-density in the ring is constant. Various phenoxy-radicals, including PhO*,have been identified as intermediates in the oxidation of the corresponding phenols, 4 5 and certain semiquinone cations have been prepared in sulphuric acid by reduction of the corresponding q ~ i n o n e s . ~ ' Several studies of 13C hyperfine coupling in semiquinone anions have been reported,68 and Karplus ,and Fraenkel 6 9 have accounted for the results in terms of positive contributions from direct 0'-n interactions and negative contributions from indirect 0-n interactions from spin-density on adjacent carbon atoms. Several new radicals derived from aromatic hydrocarbons or related compounds have been described. Three groups have independently re-
61
62
63
T. R. Tuttle and S. I. Weissman, J . Amer. Clzem. SOC.,1958, 80, 5342. J. R. Eolton and A. Carrington, MoZ. Phys., 1961, 4, 497. J. R. Bolton, A. Carrington, A. Forman, and L. E. Orgel, MoZ. Phys., 1962,
5, 43.
64 66
T. R. Tuttle, J . Amer. Chem. SOC.,1962, 84, 1492; 2839. J. R. Bolton and A. Carrington, Trans. Faraday SOC., press. in a s A . H. Maki and D. H. Geske, J . Amer. Chem. SOC.,1961, 83, 1852. 67 J. R. Bolton, A. Carrington, and J. dos Santos-Veiga, MoZ. Phys., 1962, 5, 465. 6 8 H. L. Strauss and G. K. Fraenkel, J. Chem. Phys., 1961, 35, 1738; D. C. Reitz, F. Dravnieks, and J. E. Wertz, ibid., 1960, 33, 1880. 6 s X I . Karplus and G. K. Fraenkel, J . Chem. Phys., 1961, 35, 1312.
S P M O N S : ELECTRON S P I N R E S O N A N C E
51
ported the resonance spectrum of the tropylium radical, C7H7,in solution,70 in an amorphous solid,7l or in single crystal^.'^ Bernal, Rieger, and Fraenkel73 have prepared the negative ion of azulene and various derivatives, and by judicious substitution with deuterium have been able to assign hyperfine coupling constants to all protons. They have discussed the results in terms of c-n interactions which, for theoretical reasons, are considered to depend strongly upon the ring bond angles. An earlier report 74 of the spin resonance spectrum of this ion is now known to be incorrect.75 The spectra for the positive and negative ions of biphenylene have been compared and can be understood satisfactorily in terms of molecular-orbital theory.76 The pyracene cation has a very interesting resonance spectrum 7 7 which shows that the methylene protons interact very strongly with the unpaired electron, suggesting that hyperconjugation is particularly important in this radical. The spectrum is also of interest in that satellite lines arising from second-order effects, which can normally be ignored, are well resolved. Extra lines have also been detected in the spectrum of ethyl radicals in liquid ethane.78 Spectra for corresponding aromatic cations and anions, which are generally very similar, have been discussed in detail by M ~ L a c h l a n . ~ ~ However, the spectra for 9,lO-dimethylanthracene cations 80, 81 and anions are markedly different, the hyperfine coupling to the methyl protons of the anion being about half that to the methyl protons of the cation. This result is best understood in terms of the theory of hyperconjugation. Indeed, as has been stressed,s2 electron spin resonance is probably one of the most direct methods of studying this phenomenon, which has been so extensively studied by methods which appear to be fraught with pitfalls. Furthermore, it probably provides the most compelling evidence yet found for carboncarbon and carbon-nitrogen hyperconjugation.82 Coupling constants to 14N in N-heterocyclic compounds have been measured for a variety of radical anions.g3-87 Carrington and dos SantosVeiga 83 have deduced that QN is about 25 gauss, and that contributions from spin-density on adjacent carbons, through a-n interactions, are small. That they should be relatively small compared with the situation for 13C,
J. dos Santos-Veiga, Mol. Phys., 1962, 5, 639. S. Arai, J. Shida, K. Yamaguchi, and Z. Kuri, J . Chem. Phys., 1962, 36, 1885. 72D. Wood and H. M. McConnell, J. Chem. Phys., 1962, 3 9 1150. ', 73 I Bernal, P. H. Rieger, and G . K. Fraenkel, J. Chem: Phys., 1962, 37, 1489. . 74H. Brown and R. C. Jones, J. Chem. Phys., 1962, 36, 2809. W. 7 5 H.W. Brown and R . C. Jones, J. Chem. Phys., 1962, 3 4 1571. ', 7 8 A . Carrington and J. dos Santos-Veiga, Mol. Phys., 1962, 5, 285. 7 7 E. de Boer and E. L. Mackor, Mol. Phys., 1962, 5, 537. '* R. W. Fessenden, J. Chem. Phys., 1962, 37, 747. 7 9 A. D. McLachlan, Mol. Phys., 1961, 4, 49. J. A. Brivati, R. Hulme, and M. C. R. Symons, Proc. Chem. Soc., 1961, 384. J. R. Bolton, A. Carrington, and A. D. McLachlan, MoZ. Phys., 1962, 5, 31. 8 2 M. C. R. Symons, Tetrahedron, 1962, 18, 333. 8 a A . Carrington and J. dos Santos-Veiga, Mol. Phys., 1962, 5, 21. 8 4 N. M. Atherton, F. Gerson, and J. N. Murrell, Mol. Phys., 1962, 5, 509. 8 5 F. Bruin, F . W. Meineker, M. Bruin, and A. Zahlan, J. Chem. Phys., 1962, 36, 2783. 8 6 R. L. Ward, J. Amer. Chem. SOC., 1961, 83, 3623. 8 7 C. A. McDowell, K. F. Paulus, and J. R. Rowlands, Proc. Chem. SOC., 1962, 60.
70
71
52
discussed above,69is reasonable since the direct interaction on nitrogen will involve the non-bonding o-lone-pair electrons.83 However, Ward 86 has concluded that contributions from adjacent carbon atoms may be important. Atherton et aLS4 have pointed out that these conclusions are based upon the use of Huckel theory and they have found, by direct measurement of the spectrum of the anion of 3,5-lutidine7 that the theory of Karplus and Fraenkel 69 adequately accounts for their results, and that, indeed, contributions from spin on adjacent carbon atoms are small, though not negligible. Melchior and Maki 88 have estimated an isotropic coupling of 5.29 gauss for 14Nfrom the spin resonance spectrum of the p-phenylenediamine cation. This result is in marked contrast with the value of 0.28 gauss recently estimated for the structurally similar Wursters blue cat,ion.*g Bolton et aZ.90 have remeasured and reinterpreted the spectrum of Wursters blue, and concluded that earlier interpretations were incorrect. Their value for the 1 N 4 coupling constant was 7-0 gauss. It seems probable that the spectrum for the NNNN-tetramethylbenzidine cation 91 has been similarly misinterpreted and thefact that such errors can arise in the interpretation of these very well-resolved spectra underlines one of the major problems in this field. A hyperfine coupling of about 50 gauss has been assigned to the methylene protons of the cyclohexadienyl radical,92formed by addition of a hydrogen atom to benzene. If this interpretation is correct, the coupling is extremely large, and would not be predicted from known values for other radicals, even when the favourable orientation of these protons is taken into consideration. It seems possible that the bond angles a t the saturated carbon atom deviate somewhat from the tetrahedral angle, in a sense that makes hyperconjugation more favourable (cf. ref. 77). I n contrast, the results reported by Norman and his co-workers 4 6 for the radical formed by addition of hydroxyl to benzene include a value of 36 gauss for the aliphatic proton. This value is in good accord with expectation. The spectrum assigned t o the phenyl radical 9 3 may also be considered in this context. Finally the Reporter is loth to leave this section without making a passing reference t o the extremely interesting, and most relevant , nuclear magnetic resonance studies of various paramagnetic nickel chelates. 94 The workers involved have extensively exploited a freak situation which arises for many of these complexes, which gives rise t o narrow lines. One of the advantages of this over the methods described here is that relative signs of proton coupling constants could be obtained directly. Carbon n-radicals. This term is intended to describe radicals in which the unpaired electron is largely localised in a 2p-orbitdl on trigonallyT. Melchior and A. H. Maki, J. Chem. Phys., 1961, 34, 471. K, H. Hausser, 2. Naturforsch., 1959, A , 14, 425; Naturwiss., 1960, 47, 251. J. R. Bolton, A. Carrington, and J. dos Santos-Veiga, Mol. Phys., 1962, 5, 615. 91 Z. Galus and R. N. Adams, J. Chem. Phys., 1962, 36, 2814. 9 2 H. Fischer, J. Chem. Phys., 1962, 37, 1093; S. Ohnishi, T. Tanei, and I. Nitta, J . Chem. Phys., 1962, 37, 2402. 93 I. I. Chkheidze, Yu. N. Molin, N. Ya. Bouben, and V. V. Voevodsky, Doklady Akad. Nauk S.S.S.R., 1960, 130, 1291. 9 4 D. R. Eaton, A. D. Sosey, R. E. Benson, W. D. Phillips, and T. L. Cains, J. Amer. Chem. Xoc., 1962, 84, 4100.
88M.
89
53
hybridised carbon. Following the pioneer work of Whiffen and others, outlined in the previous Report,l a spate of studies describing radicals of this type, formed by high-energy irradiation and oriented in single crystals of the parent compound, has appeared. I n most instances radicals could be identified by the number of oc- and B-protons interacting with the unpaired electron, since these protons give rise to highly characteristic hyperhecoupling tensors. For example, carbon n-radicals have been recognised in irradiated single crystals of sucrose,95 acetyl-L-glutamic acid,96 DL-tartaric DL-aspartic acid,98 and various other mono- and di-carboxylic acids.99 Radiolysis of solid alkyl halides at low temperature gave, generally, alkyl radicals.100 The spectra obtained were relatively well resolved for randomly-oriented radicals and hence interpretation was less ambiguous than in many instances. Nevertheless, several spectra could not be interpreted satisfactorily. Hyperfine coupling to fluorine in the radicals F,6*CQ*NH2 and lol 102 F6H*CO*NH2 has been observed, and it was concluded that the major interaction observed is the result of some 11 yo charge transfer from fluorine through n-bonding,l o 2 giving positive spin density directly on fluorine. Nevertheless, despite this delocalisation, and that which must surely occur onto the carbonyl oxygen, the isotropic or-proton coupling was as large as that for methyl radicals. This apparent insensitivity of the oc-proton coupling to substituents, which is commonly found for this class of radical, has not been satisfactorily explained as yet. Ward 1 0 3 prepared the unusual radical (I),by reduction of tetramethyl- 1,3-~yclobutanedione. The spectrum displayed well-resolvedsatellite lines from radicals Me Me containing 13C, but the coupling constants ascribed )c-c.*to the carbonyl carbon atoms differ remarkably from those observed for carbonyl carbon atoms in other o=c Me Me (I) alkyl ketyls.lo4 This may be a result of the markedly different bond angles associated with the cyclic radical. Other n-radicals. The majority of other radicals studied can also be classed as n-radicals, as distinct from a-radicals discussed in the next section. Of the former class, many have the unpaired electron considerably localised on nitrogen. These include nitroalkane anions, studied in aqueous solution,44 for which an unusually large isotropic hyp:rfine coupling of 25 gauss was found, and mono- and dialkyl-nitroxides, R,NQ, which are isoelectronic with the better known ketyls, and appear to be fairly stable.15
g5
96 97
H. Shields and P. Hamriek, J . Chem. Phys., 1962, 37, 202.
M. Katayama, J . Chem. Phys., 1962, 37, 2143.
D. V. G. L. N. RaO and W. Gordy, J . Chem. Phye., 1962, 36, 1143. T. S. Jaseja and R. S. Anderson, J . Chem. Phys., 1962, 36, 2727. 9 9 A. Horsfield, J. R. Morton, and D. H. Whiffen, Mol. Phys., 1961, 4, 327; Nature, 1961, 189, 481; Mol. Phys., 1961, 4, 169; Trans. Faraday SOC., 1961, 57, 1657. loo P. B. Ayscough and C. Thomson, Trans. Faraday SOC.,1962, 58, 1477. lol R. J. Lontz and W. Gordy, J . Chem. Phys., 1962, 37, 1357. lo2 R. J. Cook, J. R. Rowlands, and D. H. Whiffen, Proc. Chem. SOC., 1962, 252. Io3 R. L. Ward, J . Chem. Phys., 1962, 36, 2230. Io4 N. Hirota and S. I. Weissman, J . Amer. Chenz. SOC., 1960, 82, 4424. lo5 J. C . Baird and J. R. Thomas, J . Chem. Phys., 1961, 35, 1507.
98
54
The isotropic 14N hyperfine coupling is normal for n-radicals of this type, but the proton hyperfine coupling constants are very interesting. No coupling was detected from protons directly attached to nitrogen, and, since the other parameters were quite comparable with those observed for dialkyl radicals, it seems likely that this absence of hyperfine interaction is due to a rapid proton-transfer equilibrium with the solvent. One of these radicals, di-s-butyl nitroxide, stands out in that it is the first species for which hyperhe structure from 170 has been detected in an electron spin resonance spectrum.lO6 Several radicals having the SO,- group attached to nitrogen are now known. I n addition to the very stable ion ON(S0,),2- the ions N(S0,)22-,107 +H2N(S03)-,108 and HN(SO,)- lo9 have been identified and studied in various single crystals exposed to y-radiation. Rowlands 109 has compared the hyperfine parameters for I4Nobtained at room temperature and at 77" K, in the last three radicals. He concluded that the marked increase in the anisotropic part of the hyperfine coupling tensor for the radicals HN(S0,)and +H,N(SO,)-, which occurred on cooling, can be understood in terms of hindered rotation which is quenched at 77" K. The radical-ion NH,+, which is isoelectronic with methyl, has been pre111 The 14Nand 1H hyperpared by irradiating ammonium perchlorate.110~ fine coupling constants, measured at room temperature, show that this radical is planar and rotating rapidly. Rotation was at least partially quenched on cooling.lll A radical containing two equivalent nitrogen atoms, formed when potassium azide 112is irradiated, may be N, but is more likely to be N,- with the n-levels split by the crystal field.l13 The radical NF,, formed by the reversible dissociation of N2F,, gave a broad structureless absorption with a g-valueof 2.010 in the gas phase.l14 This radical, which is isoelectronic with N0,2-, is of interest since all the atoms should give hyperfine contributions to the spectrum and hence a detailed picture of the orbibal of the unpaired electron might be constructed. Unfortunately, the published spectrum of this radical, in a rigid matrix, is so complicated that these parameters have not yet been estimated. 51 A wide variety of oxy-radicals of the non-metals have been prepared, and the results have been summarised and discussed.115 These include radicals identified as N022- and N03,116 which are formed in irradiated
J. C. Baird, J . Chern. Phys., 1962, 37, 1879. A . Horsfield, J. R . Morton, J. R. Rowlands, and D. H. Whiffen, Mol. Phys., 1962, 5, 241 lo* J. R. Mowlands and D. H. Whiffen, Nature, 1962, 193, 61. lo9 J. R. Rowlands, Mol. Phys., 1962, 5, 565. 110 T Cole, J . Chern. Phys., 1961, 35, 1169. . 111 J. S. Hyde and E. S. Freeman, J . Phys. Chern., 1961, 65, 1636. 112 R. B. Horst, J. H. Anderson, and D. F. Milligan, J . Phys. and Chem. Solids, 1962, 23, 157. 113 M. C. R. Symons, J., 1963, 570. 114 L. H. Piette, F. A. Johnson, K. A. Booman, and C. F. Colburn, J . Chem. Phys., 1961, 35, 1481. 115 M. C. R. Symons, " Free Radicals in Inorganic Chemistry," No. 36, Adv. i n Chem., A.C.S., 1962, p. 76. 1 1 6 P . W.Atkins and M. C. R. Symons, J . , 1962, 4794.
lo6
lo'
55
nitrates 117 or doped and irradiated alkali-halide crystals. 118 The radical NO, is not strictly a n-radical since the unpaired electron is in a non-bonding orbital, comprising the in-plane 2 p oxygen atomic orbitals. Chantry et aZ.119 also claim to have detected NO, and the isoelectronic radical GO,-, and they adduce evidence for an in-plane distortion in these radicals. This does not seemko have occurred for the radical formed in irradiated potassium nitrate. l 1 7 s 120 Parameters for chlorine dioxide in rigid sulphuric acid have been estimated with fair accuracy,i21and the results confirm the identification made earlier of a radical trapped in irradiated potassium perchlorate.122 Photolysis of the rigid solution of chlorine dioxide in sulphuric acid gaye a new radical, 1 2 1 which is probably chlorine monoxide. Dissolution of sodium dithionite in water gave a radical which has been conclusively identified as SO2-, from its isotropic 33S hyperfine structure.f23 The hydroxyl radical remains elusive. A radical formed in irradiated Li2S0,,2H,0 1 2 4 has been tentatively identified as hydroxyl,12S but the parameters are quite different from those derived from a radical in irradiated ice.126 However, the results given for this radical 126 are difficult to understand in terms of the hydroxyl r a d i ~ a 1 . l ~ ~ a-Radicals. If the orbital of the unpaired electron has appreciable s-character on any atom with a magnetic nucleus, this will greatly increase the magnitude of the isotropic hyperfine coupling above the small values resulting from configuration interaction, found for n-radicals. In these circumstances, it is possible to calculate approximately the s- and p character for the orbital on the atom concerned and hence obtain an indication of the hybridisation. This has been done for the radical GO,-; the bond angle, estimated from the hybridisation, was found to be 134".lZ7 Similar calculations for the radical NO, 128 have shown that the calculated hybridisation and bond angle are very similar to those for C02-.129 This is in accord with Walah's conclusion that isoelectronic molecules of this type should have very similar shapes.130 The unpaired electron is found to be considerably more delocalised on to oxygen on going from C 0 , - to NO,, in accord with trends in electronegativity.l 2 9 This is reflected in the relative tendencies of these radicals to dimerise.
117 J. Cunningham, J. A. McMillan, B. 0. Smaller, and E. Yasaitis, J . Phys. and Chem. Solids, 1962, 23, 167. 118 C. Jaccard, Phys. Rev., 1961, 124, 60. 119 G. W. Chantry, A. Horsfield, J. R. Morton, and D. H. Whiffen, MoZ. Phys., 1962, 5, 589. l z o D . Shoemaker and E. Boesman, Compt. rend., 1961, 252, 2099; 2866. * la1 P. W. Atkins, J. A. Brivati, N. Keen, M. C. R. Symons, and P. A. Trevalion, J., 1962, 4785. 122 T. Cole, Proc. Nat. Ac a d . Sci., 1960, 46, 506. I z 3 A. Horsfield, quoted in Reference 115. lz4 P. E. Wigen and J. A. Cowen, J . Phys. and Chem. Solids, 1960, 17, 26. l Z 5 D. W. Ovenall, J . Phys. and Chem. Solids, 1961, 21, 309. lZ6 J. A. McMillan, M. S. Matheson, and B. 0. Smaller, J . Chem. Phys., 1960, 33, 609. I27 D. W. Ovenall and D. H. Whiffen, MoZ. Phys., 1961, 4 135. , 12* H.Zeldes and R. Livingston, J . Chem. Phys., 1961, 35, 563. lZg P. W. Atkins, N. Keen, and M. C. R. Symons, J., 1962, 2873. 130 A. D. Walsh, J., 1953, 2266.
56
G E N E R A L AND PHYSICAL CHEMISTRY
The radicals Po32-,131 and ClO, 121, form an interesting sequence ; when possible d-orbital contributions are neglected, the p : s ratio, estimated from the hyperfine coupling tensors, is close to that expected for sp3 hybridisation. In contrast, the radical NO,,- deviates only slightly from planarity, the p : s ratio being about 9.117 Isotropic proton hyperfine coupling constants for o-radicals having a hydrogen atom attached to the atom on which the unpaired electron is largely localised are extremely large, as judged by results for the formyl radical,4g,134 and the radical HP0,-.135 If this generalisation is correct it means that such an unpaired electron is strongly delocalised on to the proton. It would be interesting t o see if this effect can be transmitted I through several bonds in a o-framework. The essential difference between the proton-coupling mechanisms for planar and bent radicals appears t o be that, for the former, interactions involve excitation of electrons from filled to empty orbitals, whilst for the latter, excitation into the half-filled level is important. Adrian et aL51have reported results for the vinyl radical, formed by additiov of a hydrogen atom to acetylene. This radical is isoelectronic with H,CN, which has an unpaired electron largely localised in a 2p-level on nitrogen in the radical plane.50 This electron is strongly, and equally, delocalised on to the two protons, hyperconjugation being unusually effective presumably because of tbe short carbon-nitrogen bond. This was not found for the radical H,C=CH however, and it seems probable that the unpaired electron is in a hybridised orbital similar to that for HCO. Interactions with the Medium and Restricted Motions.-NuZtipZe trapping sites. Following their studies of hydrogen atoms in rare-gas matrices, Bowers et aZ.,136 have made an extensive study of the hyperfine coupling and g-values of alkali-metal atoms in several rare gases. The results were more difficult t o interpret, but the presence of closely-spaced groups of lines a t field values near those required by theory seems to be good evidence for a variety of trapping sites. It has been proposed that " extra " features in the spectra of nitrogen dioxide, in certain rare gases, is also evidence for multiple trapping but an alternative explanation has been offered (see section on Restricted rotation). Solvation and ion-pairing. I n addition t o the highly characteristic hyperfine contributions from alkali-metal ions in contact ion-pairs, discussed previously, 1 relatively minor changes in proton hyperfine coupling constants, on varying the solvent,138-140 may be the result of changing ion-solvent
A. Horsfield, J. R. Morton, and D. H. Whiffen, MoZ. Phys., 1961, 4, 473. G. W. Chantry, A. Horsfield, J. R. Morton, and D. H. Whiffen, MoZ. Phys., 1962, 5, 233. 133 T. Cole, J . Chem. Phys., 1961, 35, 1169. lS4 J. A. Brivati, N. Keen, and M. C. R. Symons, J., 1962, 237. 135 J. R. Morton, MoZ. Phys., 1962, 5, 217; P. W. Atkins, N. Keen, and M. C. R. Symons, J., 1963, 250. 136 V. A. Bowers, E. L. Cochran, S . N. Foner, and C. K. Jen, Fifth Internat. Symp. on Free Radicals, Uppsala, 1961, A, 3, 1. 137 J. B. Farmer, D. A. Hutchinson, and C. A. McDowell, Fifth Internat. Symp. on Free Radicals, Uppsala, 1961, A, 3, 44. 138 S. H. Glarum and L. C . Snyder, J . Chem. Phys., 1962, 36, 2989. 139 E. W. Stone and H. Maki, J . Chem. Phys., 1962, 37, 1326.
131
132
S Y M O N S : ELECTRON SPIN R E S O N A N C E
57
interactions or the formation of specific ion-pairs. It is interesting that the isotropic 14N hyperfine coupling constants for various aryl nitro-anions increased markedly on going from methyl cyanide' to as solvent, but those for nitroalkane anions remained constant at the high value of about 25 gauss. It was suggested 44 that this may be connected with rotation of the nitro-group out of the plane of the benzene ring. An alternative explanation, which also accommodates the large coupling constant for the alkyl derivatives, is that the nitro-group deviates to a slight extent from planarity, thus adding nitrogen 2s-character directly to the orbital of the unpaired electron. The Reporter recalls that the structurally similar ion is almost certainly ~ y r a m i d a 1 . l ~ ~ The interesting difference between the spectra attributed t o the anion of m-dinitrobenzene, prepared electrolytically in methyl cyanide 141and by reaction with alkali metals in dimethoxyethane, 142 has been interpreted in terms of specific ion-pairing in the latter solvent, whereby the cation is associated with only one nitro-group at a given time.2 The extremely large changes which were observed can then be understood if two nearly degenerate states are involved. Ward 1 4 3 has recently established that the ion formed in dimethosyethane still contains two nitrogen atoms, but his claim that this is conclusive proof of the ion-pair theory is not strictly true, since chemical reduction of one of the nitro-groups might have occurred, giving an anion cont,aining two non-equivalent nitrogen atoms. Restricted rotation. The asymmetric pattern of shoulders and peaks in the spectra of nitrogen dioxide in various rare-gas mixtures 1 3 7 , 144 has been explained quantitatively, by using the parameters derived by Zeldes and Livingston,128in terms of molecules free to move about the long (oxygenoxygen) axis 0nly.l29,145, 1 4 6 It is probable that specific movements such as this, which may give rise to gross modifications, are important in many studies of trapped radicals.109~1 7 Small fluctuations are also significant, 1 as is shown by the highly asymmetric octet of hyperfine lines obtained for specific orientations of vanadyl oxalate in a single crystal.26 Intramolecular rotation of methyl groups has been studied by several workers as a function of !emperature.l47, l 4 * For example, Horsfield et aZ.14' studied the radical MeCHC0,H and found that above about 200" K the methyl group has no preferred orientation and is reorienting rapidly since two sets of quartets were detected. Below 100"K the spectra were more complex, but could be interpreted in terms of non-equivalent p-protons. Thus under these conditions one orientation is preferred for a relatively long
140 K. Hirota, J. Chem. Phys., 1962, 37, 1884; Y Deguchi, Bull. Chem. SOC. a p a n , . J 1962, 83, 1260. 1 4 1 D. 1. Geske and A. H. Maki, J. Amer. Chem. SOC., 1960, 82, 2671. l a z R . L. Ward, J. Chem. Phys., 1960, 32, 410. 143 R. L. Ward, J . Chem. Phys., 1962, 36, 1405. 144 C. K. Jen, 5. N. Foner, E. L. Cochran, and V. A. Bowers, Phys. Rev., 1958,112, 1169. 145 M. C. R. Symons, Chem. SOC. Symp., Queen Mary College, London, Nov. 1961. 146 F. J. Adrian, J. Chem. Phys., 1962, 36, 1692. 14' A. Horsfield, J. R. Morton, and D. H. Whiffen, MoZ. Phys., 1962, 5, 115. 1 4 8 C. Heller, J. Chem. Phys., 1962, 36, 175; I. Miyagawa and K. Itoh, ibid., p. 2157.
58
time interval. Between 100"and 200 O K four hyperfine components remained sharp, but the remainder broadened greatly. Maki 149 has detected two different ortho-proton coupling const,ants for aromatic anions containing the
-dH which he interpreted in terms group FO
of hindered rotation about the carbon-carbon bond. Similar arguments have been presented by others 150 to explain curious line-width alternations in the spectra of p-dinitro- and p-dihydroxy-aromatic ions. Equilibration between alternative orientations was relatively rapid in these instances so that individual species were not detected, and on warming, the broadened components narrowed until the " normal " spectrum was obtained. The very ?mall hyperfine coupling to the p-proton in the ketyl (Me,C)(Me,CH)CO- 161 has been explained in terms of a preferred conformation in which the proton is constrained close to the plane of the radical.82 A similar explanation has been given 152 for the small coupling constant for the p-proton in R2CH*N02radicals,44and it was suggested that the coupling constant obtained is not a residual value for the extreme in-plane conformation, but rather an " average " for radicals undergoing restricted oscillations between preferred conformations. 1 5 2 A very intereeting line-width alternation has been discovered for primary alkyl radicals, RCH,, in rare gases a t 4.2"K.153 If the two a-protons are equivalent, each triplet associated with them will consist of a narrow central component flanked by broad asymmetric lines. The required equivalence can be achieved by suitable rotation about the carbon-carbon bond. This situation is well illustrated by the spectrum of trapped n-propyl radicals which was dominated by three narrow components. I n previous work only these narrow lines were detected, and no explanation could be found for the apparent absence of coupling to the a-protons. Finally, it seems probable that .another long-standing problem, the interpretation of the nine-component spectrum attributed to polymethylmethacrylate radicals, can be understood in terms of an alternation of line-widths resulting from the superposition of spectra for two rotational i ~ o m e r s . 1 ~ ~ Other Factors Contributing to Line-widths.-HyperJine coupling and g-value anisotropy. Spin-resonance spectra of radicals in solution, like those of transition-metal complexes, often appear slightly asymmetric as a result of variations in line-width, which generally reflect the gross changes which occur on cooling to low temperatures. These major changes can in favourable cases give the magnitudes of the principal values of the hyperfine and g-tensors, and it is often helpful to study spectra in both fluid solution and rigid 155 This technique is of little use for aromatic radical ions
14*
150
J. R. Bolton and A. Carrington, Mol. Phys., 1962, 5, 161; A. Carrington, ibid., p. 425; J. H. Freed and G . K. Fraenkel, J . Chem. Phys., 1962, 37, 1156. l 5 I N . Hirota and S. I. Weissman, J. Amer. Chem. SOC.,1960, 82, 4424. 1 5 2 E. W. Stone and H. Maki, J. Chem. Phys., 1962, 37, 1326. 153 E. L. Cochran, F. J. Adrian, and V. A. Bowers, J . Chem. Phys., 1961, 34, 1161. I54 M. C. R. Symons, J., 1963, 1186. 1 5 5 R. Neiman and D. Kivelson, J . Chem. Phys., 1961, 35, 156; H. R. Gersmann and J. D. Swalen, ibid., 1962, 36, 3221; J. A. McMillan and B. 0. Smaller, ibid., 1961, 35,
763.
A. H.Maki, J. Chem. Phys., 1961, 35, 761.
S Y M O N S : ELECTRON SPIN RESONANCE
59
since the spectra are so full of detail that, when rigid glasses are studied, single broad structureless spectra are obtained. It is, therefore, surprising that relatively narrow lines have been detected for certain aromatic cations adsorbed on solids.58 In the Reporters opinion this could arise if these planar ions are free to move rapidly in their own plane, whilst not being free to tumble haphazardly. The form of the anisotropic hyperfine coupling to a-protons is fortuitously such that this rotation will reduce it to a very small value, so that the dominant remaining interaction is the isotropic coupling, as was found experimentally. The theory developed by McConnell, to explain the variations in linewidths for paramagnetic molecules in fluid solution, has been extended to cover radicals containing nuclei having hyperfine tensors with different principal directions,l56 and has led to the prediction, based entirely on linewidth analysis, that the sign of the isotropic coupling to 14N,in certain Nheterocyclic anions, is positive. The possibility of distinguishingthe relative signs of proton coupling constants from trends in line-widths has been disc~ssed.1~6~ 77 Nolle and Morgan 157 found that the very broad hyperfine components in the spectrum of aquated manganous ions in dilute solutions narrowed markedly either on raising the temperature or increasing the microwave frequency. They concluded from a careful analysis of their data and a comparison with earlier studies of the proton resonance spectra of similar solutions, that the line-widths were determined largely by spin-lattice relaxation. Electron-transfer reactions. Weissman has reviewed the application of electron spin resonance to the measurement of rates of very rapid electrontransfer reactions.15* He and his co-workers have considerably extended his pioneer work in this field. The rate of the intermolecular electron transfer between naphthalene and its anion could be estimated from the line broadening of any of the twenty-five hyperfine components, provided a suitable correction was made.159 I n solvents of poor ion-solvating ability ion-pairs and free ions could be detected separately, each giving rise to narrow lines.lsO Hence the rate of interconversion was slow, much slower incidentally than the rate of electron transfer between either the free ion and naphthalene, or the ion-pair and naphthalene, the former being, for most solvents, the faster.lsO The latter observation is somewhat surprising and of considerable interest in the field of reaction mechanism. Studies of intramolecular electron-transfer have been extended to the mono-anion of diphenyl ether for which, as far as could be judged by linewidth measurements, the unpaired electron is evenly distributed throughout the m01ecule.l~~ This is in accord with the finding 1 6 1 that the dianion has no low-lying triplet state.
156 J. W. H. Schreurs and D. Kivelson, J. Chem. Phys., 1962, 36,117; A. Carrington and H. C. Longuet-Higgins, Mol. Phys., 1962, 5, 447. 15 A. W. Nolle and L. 0. Morgan, J. Chem. Phys., 1962, 36, 378. 158 S. I. Weissman, 2. Electrochem., 1960, 64, 47. 159 P. J. Zandstra and S. I. Weissman, J. Chem. Phys., 1961, 35, 767. 160 N. M. Atherton and S. I. Weissman, J. Arner. Chem. Soc., 1961, 83, 1330; P. J. Zandstra and S. I. Weissman, ibid., 1962, 84, 4408. 161 D. H. Eargle and S. I. Weissman, J . Chem. Phys., 1961, 34, 1840.
60
Others have found the spin-resonance method convenient for studying rates of intermolecular electron-transfer reactions.162 Orbital degeneracy. The markedly broader hyperfine components found for benzene anions compared with less symmetrical anions in similar environments is associated with the fact, discussed above, that the electron is in an orbitally degenerate state. Similar broadening, coupled with a short relaxation time, has been found for the coronene cation in sulphuric acid.163 However, the anion of cyclo-octatetracene has a spectrum with very narrow hyperfine components despite the orbital degeneracy expected for the planar symmetrical ion. This difference has been discussed 164 in terms of two equivalent distorted structures, having alternate short and long bonds. Triplet States and Charge-transfer Complexes.-Excited states of organic molecules. I n addition to relatively intense transitions, with Am = 2, for the triplet states of optically-excited organic molecules in rigid glasses, transitions, with Am = 1, can sometimes be detected, in which case the zero-field parameters can be estimated with some accuracy. l G 5 This means that the far more elaborate task of studying dilute '' solutions " of these organic molecules, in diamagnetic transparent host-crystals, may often be unnecessary, except that no proton hyperfine coupling can be detected from the glasses. McDowell and his co-workers 1 6 6 have demonstrated by electron spin resonance that excitation of benzophenone to its triplet state can result in energy transfer to neighbouring naphthalene molecules. The naphthalene triplet was clearly identified, but the triplet of benzophenone could not be det,ected. However, excited triplet states of several substituted benzophenones have been studied in rigid glasses by this technique.167 Ground-state organic triplet molecules. A very interesting recent development in this field is the discovery 1 6 8 , 169 that diphenylcarbene, Ph,C, has a triplet ground state that can be studied by spin-resonance methods. Brandon et a1.168 studied single crystals of benzophenone containing diphenyldiazomethane, at 77" K, after exposure to light to decompose the diazocompound. Very large zero-field splitting of the 0 and &1 levels was detected, in accord with the expected structure of this carbene which localises both electrons considerably on the central carbon atom, thus giving rise t o a large spin-spin interaction. The 2s character on carbon was small, so that the molecule is linear. The triplet molecule PhN has also been prepared, by photolysis of the azide.170 An interesting example of dimerisation to give triplet species was dis1 6 2 M. T. Jones and S. I. Weissman, J. Amer. Chem. Soc., 1962, 84, 4269; P. Ludwig and R. W. Adams, J. Chem. Phys., 1962, 37, 828. 1 6 3 J. R. Bolton and A. Carrington, MoZ. Phys., 1961, 4, 271. 164 A. D. McLachlan and L. C. Snyder, J. Chenz. Phys., 1962, 36, 1159. 1 6 5 W. A. Yager, E. Wasserman, and R. M. R. Cramer, J. Chem. Phys., 1962,37,1148. 1 6 6 J . B. Farmer, C. L. Gardner, and C. A. McDowell,J. Chem. Phys., 1961,34, 1058. 1 6 7 L. H. Piette, J. H. Sharp, T. Kuwama, and J. N. Pitts, J. Chem. Phys., 1962, 36, 3094. 1 6 8 R. W. Brandon, G. L. Closs, and C. A. Hutchison, J. Chem. Phys., 1962,37,1878. 1 6 9 R. W. Murray, A. M. Trozzolo, E. Wasserman, and W. A. Yager, J . Amer. Chern. SOC.,1962, 84, 3213. 1 7 0 G. Smolinsky, E. Wasserman, and W. A. Yager, J. Amer. Chenz. Xoc., 1962, 84, 3220.
61
covered by Hirota and Weissman.l71 For example, when a solution of an alkali-metal ketyl of fluorenone in 2-methyltetrahydrofuran was cooled rapidly to 77" K, the spin-resonancespectrum showed, in addition to a single line due to the monomeric ketyl, two broad asymmetric lines with shoulders, characteristic of the transition with Am = 1 of a triplet molecule, together with a sharp line at half field characteristic of the triplet transition with Am = 2. The extent of dimerisation depended both upon the nature of the solvent and the cation, and the separation between the two " perpendicular '' components of the fine-structure doublet decreased from 119 to 73 gauss on going from the lithium to the potassium salt. Thus the dimer seems to be one in which the cation is shared by two anions. However, under other conditions, similar ion " trimers ", in which two radicals are thought to be joined by a single alkaline-earth cation, gave the spin-resonance spectrum characteristic of the ketyl radical, with no observable coupling between the unpaired electrons.172 Thus the formation of a triplet molecule under these conditions appears to be a very subtle phenomenon, which may possibly provide a method for distinguishing between " contact " and '' solvent shared " ion-pairs.l 7 3 This phenomenon is comparable in a sense to that studied by Chesnut and Phillips 174 who made the somewhat surprising discovery that, in certain circumstances, the spin-resonance spectra of single crystals of salts having doublet-state radical anions were characteristic of triplet-state species. A typical salt showing this phenomenon of preferential pairing in the solid state was the methyltriphenylphosphonium salt of the anion of tetracyanoquinodimethane, TCNQ. The results showed that the ground state of the interacting pairs is a singlet, with a thermally accessible triplet state. These salts are often semi-conductors and therefore of considerable interest. The theory underlying this pairwise interaction has been discussed extensively by McConnell and his co-workers 175in terms of a mobile " exciton " triplet state. Results for the salt (CS+),(TCNQ)~~further illustrate this phenomenon and are interpreted in terms of the triplet exciton theory.176 The mobility of these excitons has been illustrated by an interesting experiment in which a crystal of Ph,PMe+(TCNQ),- was X-irradiated, to give a low concentration of doublet radicals, before measurement. On warming, the triplet absorption lines broadened in the usual characteristic manner, but so also did that due to the trapped radical. The only reasonable explanation for this was that spin-exchange with mobile excitons was occurring.175 The general theory underlying spin densities and spin correlations in triplet states has been discussed by M~Lach1an.l~~ Charge-transfer complexes. New light has been shed on the interesting
Hirota and S. I. Weissman, Mol. Phys., 1962, 5, 537. N. Hirota and S. I. Weissman, J. Amer. Chem. SOC.,1961, 83, 3533. 173 T. R. GriEiths and M. C. R. Symons, Mol. Phys., 1960, 3 90. , 174 D. B. Chesnut and W. D. Phillips, J. Chem. Phys., 1961, 35, 1002. 175 R. M. Lynden-Bell and H. M. McConnell, J. Chem. Phys., 1962, 37, 794; H M. . McConnell and H. Sterlicht, ibid., 36, 2393. H. M. McConnell, H. 0. GriEith, and D. Pooley, J. Chem. Phys., 1962, 36, 2518. 177 A. D. McLachlan, Mol. Phys., 1962, 5, 51.
171 N.
172
62
Q E N E R A L A N D P H Y S I C A L CHEMISTRY
question as t o the stage a t which a charge-transfer complex can be thought of as a pair of radical-ions rather than neutral molecules. Certain complexes of powerful donors and acceptors show characteristic charge-transfer absorption in the 12,000 cm.-l region, when dissolved in very poor ionising solvents. However, in better ionising solvents this absorption gives way, in favourable instances, to one characteristic of equivalent quantities of the corresponding radical cations and anions, although frequently one or other of these reacts to give further products fairly rapidly. Concordant results have been obtained by electron spin resonance methods,178using chloranil and NN,-dimethylaniline or NNNN-tetramethyl-p-phenylenediamine. n chloroI form or ethylene dichloride as solvent, no spin-resonance spectrum was detected, but in methyl cyanide or ethanol, spectra characteristic of the corresponding cation and anion were initially observed, although that of the latter decreased rapidly. Thus it seems that electron transfer, leading to separate solvated ions, will occur when the net solvation energy exceeds the energy required for the charge-transfer process, which is given approximately by the energy of the charge-transfer band for the complex, in non-ionising solvents. The rate of such reactions will presumably be governed by the time taken for the solvent t o become fortuitously organised in a satisfactory manner in the vicinity of the complex. I n solid complexes the Reporter expects a similar demarcation. Thus, if one pair of interacting molecules reacted to give the radical ions, then these require a stabilising solvent if the reverse reaction is to be avoided, or alternatively must be able to become trapped a t defects or react with impurities or on surfaces. The former situation can be achieved provided reaction goes completely to give an ionic crystal. The latter probably always occurs to some slight extent to give, in effect, a low concentration of trapped radicals which are not directly related to the complex itself. Trapped Electrons.--P- Centres. Doyle and Williams have studied Fcentres in sodium h~dride,17~ Kasai and Otomo give results for electron and excess centres which may be of this class in doped zinc sulphide crystals.lsO A variety of other interesting centres associated with impurities are also described in this work.ls0 A further study of F-centres in sodium chloride 181 has revealed that on bleaching with F-centre light a narrower spinresonance absorption remains. This is thought to be due to a new centre, described as a B-centre, which appears to be very similar to an F-centre, having the same g-values and similar optical absorption, but a different relaxation time. It has been established that P centres are diamagnetic,ls2 in accord with the usual model of two electrons paired in the ground level of an anion vacancy. Indeed, all other electron-excess centres such as R, M and N centres appear to be diamagnetic.ls3
1 7 8 J. W. Eastman, G. Engelsma, and M. Calvin, J . Amer. Chem. Soc., 1962, 84, 1339; I. Isenberg and S. .L. Baird, ibid., p. 3803. 179 W. T. Doyle and W. L. Williams, Phys. Rev. Letters, 1961, 6, 537. 1 8 O P . H. Kasai and Y. Otomo, J. Chem. Phys., 1962, 37, 1263. 181 G. A. Noble and J. J . Markham, J. Chem. Phys., 1962, 36, 1340. 182A. R. Reinberg and L. I. Crossweiner, Phys. Rev., 1961, 122, 1734. 183 P. R. Moran, S. H. Christenson, and R. H. Silsbee, Phys. Rev., 1961, 124, 442.
C R A I G : R E S O N A N C E I N ELECTROLYTE S O L U T I O N S
63
An interesting centre somewhat related to these, consisting of a hydrogen atom in a calcium-ionvacancy, has been detected in single crystals of calcium fluoride treated with hydrogen a t high temperatures. Extensive hyperfine structure from surrounding fluoride ions has enabled a rather precise description of this centre to be given.la4 Metal solutions. Solutions of metals in ammonia and related solvents still remain largely an enigma. Electron spin-lattice relaxation times have been st~died,18~ it was concluded that the main relaxation mechanism and is via hyperfine coupling to the 14N nucleus. When alkali halide salts were added to metal-ammonia solutions the originally very narrow spin-resonance absorption broadened markedly and shifted monotonically to high field.186 Variations in g-values with the nature of the cations and anions resembled, qualitatively, those found for g-values of F-centres in alkali halide crystals. EZectrons in non-ionic solids. It is often postulated that, after irradiation, paramagnetic centres detected by electron spin resonance or optical spectroscopy are the cations formed b y electron ejection. Although there is some evidence for trapped electrons from optical ~ t u d i e s , ~ 8 ~ evidence from electron spin resonance studies is meagre. However, Dolan 188 has recently detected a line with a half-width of about 9 gauss and a g-value close to 2.0023 from ultraviolet-irradiated organic glasses containing NNNNtetramethyl-p-phenylenediamine which may possibly be due to trapped electrons. There is no doubt that the corresponding cation, Wursters blue, is formed under these conditions, but the result, unfortunately, does not greatly advance our knowledge of the electron trap. It is conceivable that the parent amine acts as a trap, to give the corresponding radical anion. However, for the vast majority of studies of irradiated non-ionic solids, or solid solutions, the evidence from spin-resonance studies is that the final result is homolytic bond-fission rather than electron ejection and trapping.
M. C. R. S.
5 . NUCLEAR MAGNETIC RESONANCE IN ELECTROLYTE SOLUTIONS

A. Introduction.-The chemical shifts of nuclear resonances in solution depend on the electron distribution in the molecule or ion containing the nucleus, and on any fields which may be set up in the molecule by interactions with other molecules or ions. Magnetically distinct nuclei may show separate resonances, but a sufficiently rapid chemical exchange between them can result in a single resonance of some intermediate value of chemical
J. L. Hall and R. T. Schumacher, Phys. Rev., 1962, 127, 1892. V. L. Pollak, J . Chem. Yhys., 1961, 34, 864; C. A. Hutchison, Jr., and D. E. OReilly, ibid., p. 1279; D. E. OReilly, ibid., 35, 1856. lS6 R. Catterall, J. Corset, and M. C. R. Symons, J. Chem. Phys., 1963, 38, i the n press. M. R. Ronayne, J. P. Guarino, and W. H. Hamill, J. Amer. Chem. SOC.,1962, 84, 4230; J. Jortner and B. Sharf, J . Chem. Phys., 1962, 37, 2506. l s 8 E . Dolan, J . Chem. Phys., 1962, 37, 2508.
lS4 lS5
64
shift. The rate of nuclear relaxation depends on the intensities and correlation times of fluctuating interactions between a nucleus and the magnetic and electric fields it experiences. These fields arise from neighbouring molecules or ions and fluctuate randomly on account of continual thermal motion. There will be an interaction between a nuclear magnetic moment and the magnetic field and, for a nucleus with non-zero quadrupole moment, an interaction with the gradient of the electric field. The intensities of both these interactions are affected by distances of molecular separation, and that of the latter by the symmetry of molecular arrangement. The correlation times can be determined by a molecular-tumbling rate or by the rate of a chemical exchange. It follows that measurements of both chemical shifts and nuclear relaxation rates should yield useful information on the structure of electrolyte solutions and the molecular processes going on within them. Much of the early work in this field has been mentioned in earlier Reports 1, and there has been a more recent, but rather uncritical, review by Shcherbakov. Nuclei whose resonances in electrolyte solutions have been studied include those in solute ions, such as 23Na (in sodium ion) and 35Cl (in chloride and perchlorate ion), as well as those in solvent molecules, such as IH and 170in water. B. Magnetic Resonance of Solvent Nuclei.-( a) Proton chemical ~ h & . On dissolving a substance in water there is nearly always a change in the chemical shift of the proton resonance of the solvent. The changes in many cases are relatively small however (a few p.p.m.) and since the necessary susceptibility corrections, which may therefore be significant, have usually been omitted, most of the measurements made so far are only of moderate accuracy. The development 4 of suitable internal reference standards should improve the situation. Studies of aqueous acids in which the chemical shift of the exchangeaverage proton resonance has yielded dissociation data,ls have been extended by Gillespie and White5 using acid as solvent. Solutes included water, sulphur trioxide, various hydrogen sulphates, acetone and fluoro- and chlorosulphuric acids. The relation between chemical shift and composition which applies, depends upon the molecular nature of the entities present, so that measurements sometimes enable it decision to be made between several possible species. Often however the situation is not so simple and the observed changes in chemical shift on dissolving even simple salts in water are not easily accounted for. The single resonance exhibited will still be an exchange average, for there will be continual rapid exchange of protons between a variety of different situations, but the exact nature of these situations and
J. A. Pople, Ann. Reports, 1959, 56, 78; J. E. Prue, ibid., 1960, 57, 79; E. 0. Bishop, ibid., 1961, 58, 55. J. A. Pople, W. G. Schneider, and H. J. Bernstein, High-resolution Nuclear Magnetic Resonance, McGraw-Hill, New York, 1959. V. A. Shcherbakov, Zhur. strukt. Khim., 1961, 2, 452. * R. A. Y. Jones, A. R. Katritzky, J. N. Murrell, and N. Sheppard, J., 1962,
La I
nrno
v.
R. J. Gillespie and R. F. M. White, Canad. J. Chem., 1960, 38, 1371.
CRAIG : RESONANCE I N E L E C T R O L Y T E S O L U T I O N S
65
the relative number of protons in each is unknown. I n a strong electrolyte solution we may distinguish broadly between three types of water molecules : those near cations (with various degrees of " binding "), those near anions (similarly), and those which are free from the influence of ions; in each the shielding of the protons will be different. A rapid interchange of water molecules from one environment t o another, or of simple proton exchange between water molecules, or both, serves t o render all protons magnetically equivalent as far as nuclear magnetic resonance measurements a t room temperature are concerned. The pioneering study of the proton resonances of aqueous electrolytes by Shoolery and Alder served t o introduce two concepts in terms of which all subsequent measurements have been interpreted. Hydration of ions resulted in an increase in disorder in the arrangement of water molecules with the breaking of hydrogen-bonds and a consequent change to high field in proton chemical shift. Polarization of the water molecules by ions, on the other hand, gave a decrease in chemical shift. Only for 1 : 1 electrolytes was the structure-breaking effect dominant, the chemical shift increasing linearly with rise in concentration. Departures from linearity a t high concentrations were taken to mean that all the water molecules had been affected and Fabricand and Goldberg,' in a more precise extension of the investigation, attributed definite breaks a t 3-4M in the chemical shiftconcentration plots to this cause. They found that the sum of ionic radii was directly proportional to the cube root of the concentration a t which the relation changed and deduced that the ion separation at this stage was 2 . 6 B , corresponding t o a single water molecule. Additional and very comprehensive measurements of proton chemical shifts in electrolyte solutions have been made by Hertz and Spalthoff * and by hind ma^^.^ The last worker has attempted t o subdivide the effect of various ions into several contributions which can be estimated theoretically. Measurements on solutions of certain potassium salts in aqueous butane1,3401 by Mavel et al.1 have indicated a specific diol-salt interaction. ( b ) Proton relaxation in aqueous solutions. The presence of solutes in water is found to increase the rate of proton relaxation, sometimes drastically ; paramagnetic materials have an enormous effect, diamagnetic solutes a much smaller one. Vdovenko and Shcherbakov found that the proton relaxation rate in water mas increased by the addition of alkali-metal 11 and alkaline-earth l2 nitrates and halides. Larger effects were found for smaller ions, i.e. for those which are more effective in altering the proton chemical shift. This was attributed to immobilization of those water molecules involved in ion hydration; the correlation time for them was longer and their relaxation faster. The relaxation time observed, which was an average value owing
J. N. Shoolery and B. Alder, J. Chem. Phys., 1955, 23, 805. P. Fabricand and S. Goldberg, J. C'hem. Phys., 1961, 34, 1624. H. G. Hertz and W. Spalthoff, 2. Elektrochem., 1959, 63, 1096. J. C. Hindman, J. Chem. Phys., 1962, 36, 1000. l o H. Buc, 0. Martin, G. Mavel, and J. Nhel, J. Chim. phys., 1962, 59, 284. l1 V. M. Vdovenko and IT. Shcherbakov, Zhur. s t r u k t . Khim., 1960, 1 122. A. , l 2 T-. 31. Vdovenko and V. A. Shcherbakov, Zhur. strukt. Khim., 1960, 1 28. ,
' B.
66
to rapid exchange, was hence smaller than the value for pure water by an amount which depended on the quantity of salt added. The relaxation of protons in solutions of paramagnetic ions has attracted attention for a number of years. Recent studies by Gutowsky and his coworkers 13, l4 on the temperature dependence of the longitudinal and transverse relaxation-times, T, and T,, have shown that proton relaxation in these solutions should be regarded as the result of an interplay of several mechanisms operating simultaneously. Spin-lattice relaxation is determined mainly by dipolar interactions for which the correlation time is that of molecular motion of the hydrated ion, essentially its rotation. I n cases where the transverse relaxation is faster, the scalar spin-exchange interaction between the electron spin of the ion and the nuclear spin of the proton is important. Its correlation time is determined by the relative values of the relaxation time for the electron spin and of the chemical-exchangelimited life-time of protons in the hydration sphere. The authors have shown that, for solutions of a number of transition-metal ions, it is possible to account for the experimental T,and T,values, including their changes with temperature, by assuming suitable temperature dependence of the several correlation times. The situation in solutions containing complexes of copper(I1) and ethylenediamine has been investigated by Morgan, Murphy, and Cox l5 and Cox and Morgan l6 along the same lines. A detailed consideration of how the electron-spin relaxation time is determined mainly by distortion of the hydrated complex, resulting from collision with other molecules, and the effects on T,and T,has been given by Bloembergen and Morgan.17 Pearson et aZ.18 have shown how, in certain cases, it is possible to prove that the rate of chemical exchange is the main factor determining the rate of transverse relaxation, so that measurements of line width can enable the kinetics of the exchange reactions to be studied. The method has been applied to the exchange of protons and ligands of several transition-metal complexes. The pH-dependence of T,in water has been studied further by Meiboom l9 and has been shown to be due to a spin-spin splitting of the proton resonance by 170, which is incompletely averaged out by proton-exchange reactions. By studying relaxation rates under different conditions the kinetics of the various proton-exchange reactions have been determined. Proton-relaxation measurements on solutions of nickel(=) cyanide, in aqueous ammonia, have enabled Blackie and Gold 2o t o identify the complexes present in these systems and t o determine certain equilibrium
l 3 R. A. Bernheim, T. H. Brown, H. S. Gutowsky, and D. E. Woessner, J. Chem. Phys., 1959, 30, 950. l 4 T. H. Brown, R. A. Bernheim, and H. S. Gutowsky, J . Chern. Phys., 1960, 33, 1593. l 5 L. 0. Morgan, J. Murphy, and P. F. Cox, J . Amer. Chem. SOC., 1959, 81, 5043. l 6 P. F. Cox and L. 0. Morgan, J. Amer. Chem. Xoc., 1959, 81, 6409. l 7 N. Bloembergen and L. 0. Morgan, J . Chem. Phys., 1961, 34, 842. R. G. Pearson, J. W. Palmer, M. M. Anderson, and A. L.Allred, 2. E'lektrochem., 1960, 64, 110. l 9 S. Meiboom, J. Chem. Phys., 1961, 34, 375. 2O M. S. Blackie and V. Gold, J., 1959, 4033.
CRAIG : RESONANCE I N ELECTROLYTE SOLUTIONS
67
constants.21 Addition of paramagnetic salts has been shown by Freymann and Freymann 22 to cause line broadening and a chemical-shift change in the proton resonances of ethanol and of pyridine. For each solvent the resonances of different protons were affected differently, and the results indicated the molecular site of complex formation. ( c ) Oxygen-I7 resommes. Studies of the resonance of the small amount of the nucleus 170(abundance 0-0037%, spin 5 / 2 ) in water have provided information on ion hydration. Jackson, Lemons, and Taube 23 found that a solution of aquopenta-amminecobalt(111) chloride gave separate 7O resonances, some 130 p.p.rn. apart, for solvent water and for ligand water in This is to be expected since the H,Othe cation [(NH3)5Co(H20)]3+. exchange in this ion is known to be very slow (half-life 28 hr.).24 Addition of cobalt(I1) perchlorate caused a 300 p.p.m. low-field shift of the solvent peak which then appeared a t the exchange-average position, between the resonance of water in hydrated Go2+ (very far t o low field) and that of free water. As expected the resonance of the water molecule bound t o Go3+ was not shifted. Solutions of perchlorates and nitrates of various diamagnetic cations (Li+, Be2+,Mg2+, Ba2+, Sn2+, Hg2+, Al3+, Ga3+, Ri3+) showed 2 3 separate 170 resonances for the oxyanion and for water. Addition of cobalt(I1) salts to these solutions gave the expected low-field shift of the solvent peak, but in some cases (A13+,Be2+, and Ga3+)a small residual peak was left a t the original position. This was attributed t o an aquo-cation with slow rate of see.). I n the other cases, no water exchange (half-life greater than separate resonance was observed and the hydrated ions must be relatively unstable. The actual 170shift observed in the former cases will depend on the number of water molecules involved in the new aquo-cation, and the authors suggested a method which should enable the hydration number of the cation to be determined. Further measurements of 1 7 0 chemical shifts by Lewis et aLZ5were for aqueous solutions of the various rare-earth cations. The results have been satisfactorily accounted for in terms of the electronnucleus spin-exchange interaction and a suitable model of the bonding in the hydrated ions. The nuclear relaxation of 170 enriched water, containing various parain magnetic ions, has been studied by Connick and his co-workers. If it is assumed that an ion can promote relaxation only in its hydration sphere, measurements of T,enable a lower bound to be estimated 26 for the rate of exchange of water molecules aktached to the ion. The values obtained agree reasonably well with chemically determined rates of other ligandexchange reactions and, for Mn2+ solutions, with results deduced by Bernheim et aZ.13 from proton-relaxation rates. It has been pointed out l8 that this means that proton exchange in this case occurs by transfer of whole water
M. S. Blackie and V. Gold, J., 1959, 4037. 2 2 M . Freymann and R. Freymann, Compt. rend., 1960, 250, 3638. 23 J. A. Jackson, J. F. Lemons, and H. Taube, J . Chem. Phys., 1960, 32, 553. 2 4 A. C. Rutenburg and H. Taube, J . Chem. Phys., 1952, 20, 825. 2 5 W. B. Lewis, J. A. Jackson, J. F. Lemons, and H. Taube, J . Chem. Plzys., 1962, 36, 694. 2 6 R. E. Connick and E. D. Stover, J . Phys. Chem., 1961, 65, 2075.
21
68
molecules. Swift and Connick 2 7 have recently extended this work by making a detailed study of the temperature dependence of T 2 for 1 7 0 in solutions of Mn2+, Cu2+, Ni2+, Co2+, and Fe2+. They attempted t o infer which of several possible relaxation mechanisms was operative in each case and deduced activation energies for the chemical exchange processes involved. Analogous interpretation of the line broadening of 14N resonances in aqueous ammonia solutions, containing copper and nickel salts, has yielded estimates of the rate of ligand exchange in ammine complexes.28 C. Magnetic Resonance of Solute Nuclei.-Resonance measurements of nuclei present in electrolyte ions have not been very plentiful so far. Many of the nuclei concerned, having spins of more than +,possess non-zero electric quadrupole moments, and nuclear relaxation, brought about by interactions with fluctuating electric-field gradients, may be so rapid that the resonances are too broad t o be detected. Thus resonances of 35Cl and 37Cl (both of spin 3/2) are observed in chloride solutions where the nuclear environment is spherically symmetrical or nearly so, but generally not observed in compounds containing covalently-bound chlorine. Wertz 29 found that the 35Cl line obtained from a 3~-solution sodium chloride, made 0-02Mwith respect of t o a cadmium salt, increased in width by 70y0, and proportionally for smaller amounts. Most of the nuclei were still present as C1- ions, but these were evidently exchanging with the ligands of chlorocadmate complexes, and the signal observed was an exchange average of intermediate chemical shift and width. The 35Clresonance of the symmetrical perchlorate ion has also been readily 0bserved.~0 Other nuclei (with spins greater than Q) for which resonances have been studied in electrolyte solutions include : 79Br(spin 3/2), slBr (3/2), 12'1 (5/2), 23Na (3/2), s5Rb (5/2), 133Cs(7/2), 27Al(5/2), 69Ga (3/2), 71Ga (3/2), and 14N (1) (including nitrate, nitrite, cyanide, and ammonium and its alkyl derivatives). ( a ) Pluorine-I9 resonances. I n contrast t o those nuclei just discussed the 19F nucleus (spin 8) usually gives quite a sharp resonance and as the simple fluoride ion or in fluoro-complex ions its chemical shift has been the subject of several investigations. The molar proton chemical-shift found by Shoolery and Alder for fluoride ion indicated the existence of a strong polarizing effect on the water molecules, probably involving hydrogen-bonding. This should produce low shielding of the fluorine nucleus; the change in 19F chemical shift to high field found by the authors as more potassium fluoride was added t o concentrated solutions was as expected, since hydration must diminish if there is insufficient water available. Carrington et aZ.31, 32 found that the addition of methanol, ethanol, and acetone t o 0-4i\l-potassiumfluoride solutions gave an increase in 19Fchemical
T. J. Swift and R. E. Connick, J . Chem. Phys., 1962, 37, 307. J. P. Hunt and H. W. Dodgen, J . Chem. Phys., 1961, 35, 2261. 2 9 J. E. Wertz, J . Phys. Chem., 1957, 61, 51. 30 Y . Masuda and T. Kanda, J . Phys. SOC. Japan, 1954, 9, 82. 31 A. Carrington and T. Hines, J . Chem. Phys., 1955, 28, 727. 32 A. Carrington, P. Dravnicks, and 3 . C. R. Symons, ,WoZ. Phys., 1960, 3, 174. 1
27 28
CRAIG : R E S O N A N C E I N E L E C T R O L Y T E S O L U T I O N S
69
shift, as might be expected if these substances tend t o form weaker hydrogenbonds with fluoride ion. A linear relation between the chemical shift and the amount of additive was taken t o imply that there was no preferential solvation, except possibly with glycol. That addition of formamide caused the chemical shift t o move in the opposite direction supports the hydrogenbond model, as does the shift t o low field which accompanied a lowering of temperature. The addition of several alkali-metal halides was found to cause shifts which were proportional t o the amount of halide added, and an attempt was made t o assign (as done for proton shifts by Shoolery and Alder) molar l9F shift-parameters t o various ions. Such an assignment assumes that the molar shifts are additive but, as inspection of their results reveals that this does not appear t o be the case, the parameters obtained should be viewed with caution. Furthermore the interpretation of the results that was offered is not entirely satisfactory. The r81e of the cations can be regarded as that of polarizing the fluoride-ions and lowering the shielding, but the largest cations might be expected to be least effective, whereas the reverse trend was found. I n addition, the trend in the parallel effect of anions is in the same direction, with respect to ion size, and an attempt t o consider the interaction here in terms of polarization of an intermediate solvent molecule between the two ions was equally inadequate. One possible way of accounting for the order of the effects of different cations is to regard the smallest cations as being more strongly hydrated and thereby rendered less effective in polarizing fluoride ions. The cation of highest atomic weight is then the strongest polarizer and has the lowest molar chemical shift. Further evidence on this matter from chlorine resonances and alkali-metal resonances is given below. Connick and Poulson 33 found that increase in concentration produced opposite effects in the I9F chemical shift in dilute potassium and sodium fluoride solutions. The change in chemical shift with concentration in potassium fluoride solutions was reversed a t higher concentrations and the chemical shift was thought t o pass through a minimum a t about 4 M . No really satisfactory explanation of this has been advanced as yet. Solutions of KHF, and of mixtures of KHF, and KF have been studied by Wang and Skripov.34 The observed changes in 19P chemical shift with concentration fitted in with a rapid exchange between the three species P-, HF,-, and HF, if due allowance was made for the changes in degree of dissociation of the last two species. The measurements, however, were only accurate to 2 p.p.m. and could not elucidate the problem of potassium fluoride solutions where the change to the minimum chemical shift is only about 0.6 p.p.m. A similar investigation by Borodin and Skripov 3 5 of aqueous hydrofluoric acid over the entire composition range yielded results which could not be accounted for in terms of simple exchange between the three fluorine-containing species, and the authors inferred the presence of another species in very concentrated solutions.
33 34
I-C.Wang and F. I. Skripov, Soviet Phys. Doklady, 1961, 6, 27.
R. E. Connick and R. E. Poulson, J , Phys., Chem. 1958, 62, 1002.
35
P. M. Borodin and F. I. Skripov, Izvest. Vysshikh. Ucheb. Zavedenii, Radiofiz.,
1958, 1 37. ,
70
Two separate fluorine resonances were found by Connick and Poulson 36 in solutions containing comparable amounts of aluminium nitrate and sodium fluoride. These lines were ascribed to A1F2+ and All?,+, and there was good agreement between the relative peak intensities and the concentration ratios calculated from known stability constants. Exchange of fluoride between the two complexes must be slow-the peak separation indicated an exchange time of a t least 8 msec. Addition of sodium salts was found 33 t o cause proportional increases in the 19F chemical shift of both species t o an extent which seemed to be independent of the anions. The authors also observed 37 separate resonances in solutions of certain other metal-fluoride complexes, indicating the existence of different fluorine-containing species (in many cases unidentified) between which any fluoride exchange must be slow. The 19F spectrum of ammonium hexafluorosilicate was found by Muetterties and Phillips 38 t o show a strong line from 2sSiF,2-and two weak satellites from 29SiF,2-; addition of ammonium fluoride gave an extra line. Evidently any fluoride exchange between these species must be quite slow. Acidification, however, caused line broadening, suggesting the occurrence of an acid-catalysed exchange reaction for which a mechanism was proposed. There was no such evidence in the case of the analogous hexafluorophosphate or arsenate. ( b ) Resomnces of other nuclei. A very large low-field shift (over 400 p.p.m. mole-l) of the 35Cl resonance, with change in concentration, has been found for cobalt(I1) chloride solutions by C h e ~ n u t . The line observed ~~ was the exchange-average resonance of free chloride ion and a small amount of CoClf-the latter having a very large paramagnetic chemical shift,. A reduction in chemical shift on addition of various nitrates, more pronounced for those with cations of higher charge, was probably due t o increased removal of water by hydration of the added cations, with subsequent displacement of the equilibrium: CO(H,O)~+ C1- + CoC1+ + H,O + in favour of CoClf. The well-known colour change from pink t o blue on heating such solutions, which is associated with this dehydration reaction, is accompanied by a similar alteration in chemical shift. Different alkali-metal and alkaline-earth chlorides show various 35Cl chemical shifts, but similar line widths.29 Evidently the various cations surrounding the chloride ion, in these cases, affect the screening of the nucleus without altering the essential symmetry of its environment. Hindman 9 has found the 35Cl chemical shift of various alkali-metal chloride solutions to decrease linearly with increase in concentration. As with the 1 F chemical shifts of fluoride solutions, the larger cations seemed more 9 effective in displacing the halogen resonance, suggesting greater ion-ion interaction. A parallel is found in the behaviour of the resonances of cationic nuclei. Only rubidium and czesium chloride solutions show any change in alkali313
37 38
39
R. E. Connick and R. E. Poulson, J. Amer. Chem. SOC.,1957, 79, 5193. R. E. Connick and R. E. Poulson, J. Phys. Chem., 1959, 63, 568. E. L. Muetterties and W. D. Phillips, J. Amer. Chem. SOC.,1959, 81, 1084. D. B. Chesnut, J. Chem. Phys., 1960, 33, 1234.
CRAIG : RESONANCE I N ELECTROLYTE SOLUTIONS
71
metal chemical shift with concentration.9 Wertz and Jardetzky 40, 41 have observed no differences a t all in chemical shift for 23Na resonances in many different salt solutions. One simple explanation is that ion association, which becomes possible a t high concentrations, is significant only for the larger cations. Smaller cations, because of their greater polarizing power, fend to be hydrated more and thus their closer contact with anions is prevented. The lower molar proton chemical-shifts of the smaller cations and anions fib in with this idea. The changes in chemical shift, with increase in concentration,for rubidium and czesium resonances in chloride solutions are towards low field-in the same direction as the resonances observed 4 2 for the solid salts-so that simple reduction in ionic separation might be expected to lower the screening. Wang 43 found a similar trend for the 1 F chemical shifts in concentrated 9 solutions of the potassium and ammonium fluorides, towards the values observed in the solid. The relative insensitivity of the position of the 133Cs resonance, in caesium chloride solutions, to the addition of organic solvents 32 reflects the weak solvent-interactions of the large cation. The chemical shifb decreased linearly with addition of salts, the effect evidently being largely due to the anions, and was again greatest for the largest halide ions. A steady shift t o low field of the 1 2 7 1 resonance with increase in concentration for sodium and potassium iodide solutions, found by Ito and Yamagata,44 was of the same general type. Different behaviour has been observed by Richards et 46 for Zo5Tl resonances, with change in concentration, in thallium(1) salt solutions. There was a considerable departure from linearity which has been quantitatively accounted for in terms of the increased formation of specific ion-pairs at quite moderate concentrations. As with acid dissociation studies, simple exchange principles enabled quite satisfactory estimates to be made of the assooiation constants for Tl+OAc-, Tl+OH-, and TlfFe(CN)63-. Carbon-13 resonances have been investigated in aqueous solutions of 13C-enrichedcarbon dioxide by Patterson and Ettinger.47 The results are in agreement with current views on the entities present in carbonate solutions. The 35C1, 79Br,and 1271 resonances of solutions of the halides show an increase in line width with increase in con~entration.~~, As they are 48 quadrupolar, the main relaxation mechanism for these nuclei is through their interaction with fluctuating electric-field gradients, and line broadening can be accounted for by a departure from spherical symmetry of the ion's environments or an increase in the correlation time of the molecular movements responsible for the fluctuations (see below). Wertz and Jardetzky 41,
a . 5 Z4 9
443
J. E. Wertz and 0. Jardetzky, J . Chem. Phys., 1956, 25, 357. 0. Jardetzky and J. E. Wertz, J . Amer. Chem. Soc., 1960, 82, 318. 4 2 H. S. Gutowsky and B. R. McGarvey, J . Chem. Phys., 1953, 21, 1423. 4 3 I-C. Wang, Zhur. strukt. Khim., 1961, 2, 367. 4 4 J. Ito and Y. Yamagata, J . Phys. SOC. Japan, 1958, 13, 1182. 4 5 R. Freeman, R. P. H. Gasser, R. E. Richards, and D. H. Wheeler, MoZ. Phys., 1959, 2, 75. 4 6 R. P. H. Gasser and R. E. Richards, Mol. Phys., 1959, 2, 357. 4 7 A. Patterson and R. Ettinger, Z . EZektrochem., 1960, 64, 98. 4 8 H. G. Hertz, Z. EZektrochem., 1961, 65, 20. 49 J. E. Wertz, J. Chem. Phys., 1956, 24, 484.
40
41
72
G E N E R A L AND PHYSICAL CHEMISTRY
have found similar effects in the 2sNa resonances of many sodium salts. I n concentrated solutions (5M and above) of sodium iodide, thiocyanate, perchlorate, phosphates, and hydroxide and of some organic salts, there was an increasing broadening of the resonance. At such concentrations there is probably insufficient water for symmetrical hydration of the sodium ion and its immediake neighbourhood will start t o include other ions. Ion-pairing was suggested and, in the case of salts of some hydroxy- and keto-acids, even weak complexing of the sodium ion. The addition of an alcohol to aqueous solutions caused considerable broadening of the 23Na resonance, suggesting that alcohol molecules tend to displace water molecules from the hydrated ion; extreme broadening was suggested as the reason why no sodium resonance could be detected for many solutions of sodium salts in organic solvents. The fact that no significant broadening was observed in some cases (sodium bromide, chloride, fluoride, and azide) may reflect a lower ion-pairing tendency associated with anions of smaller polarizability, but may be due only to low relative solubility, so that penetration of the cation hydration-sphere does not occur. Some recent attempts have been made to calculate theoretically the magnitude of quadrupolar contributions to the nuclear relaxation of ions in solution. Valiev 5 0 has considered the case of a diamagnetic ion present in aqueous solution as a stable hydrated complex; internal vibrations of the polar ligands in the complex cause the fluctuating electric-field gradients a t the nucleus, which bring about relaxation. The calculated values of T, accounted for the experimental line widths for the hydrated ions 27A13+, 69Ga3+,and 71Ga3f but not for those of 23Na+, 79Br-, or 1271where the presumed lability of the complex rendered the model inapplicable. Valiev and Khabibullin 51 have suggested a second model for such cases, in which fluctuations in electric-field gradients a t the nucleus are brought about by both rotational and translational random-movements of neighbouring water dipoles, and have been able to account qualitatively for the experimental line widths 44 of 1 2 7 1 resonances in sodium and potassium iodide solutions. It has been claimed 5 2 that an essential difference in the temperature dependence of T,for the two models should provide an unambiguous method of detecting stable complex formation. Somewhat similar calculations have been made by Hertz 48 for the case of a halide ion sirmounded by freely-rotating water dipoles. I n addition he was able to account for the observed line broadening, which occurs with increase in concentration, by considering interionic effects. Not only will the correlation time for rotation of the water molecules around an ion increase under the influence or other ions, but the electric fields from these ions will make an increasingly important contribution to the field gradients experienced by the nucleus. Comparison with experimental values enabled inininial values of the distance of closest a'pproach of ions t o be estimated, for several alkali-metal and alkaline-earth bromides and iodides, a t various conccritmtions. In many cases the values obtained showed quite good
5O
51
K. A. Valiev, Soviet Phys. J.E.T.P., 1960, 10, 77. I<. A. Va!iev :mil R. 3 . Khabibullin, Russ. J . Phys. Chem., 1961, 35, 1118. 1 5 2 I<. A. Valiev, Soviet Phys. J.E.T.P., 1960, 11, 883.
McGLASHAN : EQUILIBRIUM PROPERTIES O F MIXTURES
73
agreement with those found from activity-coefficient considerations and in some ca,ses suggested the occurrence of ion association. However, such calculations must be only approximate for they neglect changes in the viscosity of the solutions which occur as the concentration changes. These must affect the correlation times for both water-molecule movement and for ion diffusion. Indeed, measurements by Richards and Yorke 53 on the line width of slBr resonances in bromide solutions suggest that, if allowances are made for viscosity changes, there is no evidence for ion association except possibly in the case of the czesium salt. From line-width measurements of halogen resonances in solutions containing cadmium, zinc, and mercury salts Hertz 54 has deduced the rates of bromide and iodide exchange for the various halogeno-complex ions. R. A. C.
6 . EQUILIBRIUM PROPERTIE8 OF LIQUID MIXTURES
INthe last decade the only Reports on liquid mixtures have been one by Cruickshank and Everett 1 on statistical mechanical theories of liquids and liquid mixtures, and brief and rather specialized sections on liquid mixtures in two Reports by Rowlinson on the physical properties of fluids. I n view of the fact that this Reporter reviewed the subject in another place a year ago, he will for the most part concentrate here on work published in 1962. The papers read a t a symposium held a t Berkeley in September 1961, as a tribute to Professor J. H. Hildebrand on the occasion of his eightieth birthday, have been p ~ b l i s h e d . ~ splendid new monograph, written in His collaboration with Professor R. L. S ~ o t t sums up the present status of ,~ the theory of regular solutions, the study of which he has for half a century made peculiarly his own. A large part of this Report will now be devoted to what is in effect an extended review of Hildebrand and Scotts Regular Solutions.
Regular Solutions.-In the development of the concept of a regular solution three more or less equivalent ideas have been used: (1) maximum randomness, (2) ideal entropy of mixing a t constant volume, and (3) absence of selective chemical attractions. 6 With regard to the first of these ideas the case is strongly made that for liquid mixtures of reasonably spherically-symmetrical molecules except in the neighbourhood of the critical point, . . . thermal agitation causes practically random mixing. This Reporter is, however, puzzled by statements (for example < Completely random mixing, and therefore regular
R . E. Richards and B. A. Yorke, MoZ. Phys., in the press. H. G. Hertz, 2. Elektrochem., 1961, 65, 36. A. J. B. Cruickshank and D. H. Everett, A m . Reports, 1953, 50, 80. J. S. Rowlinson, Ann. Reports, 1955, 52, 56; 1959, 56, 22. M. L. McGlashan, Ann. Xev. Phys. Chem., 1962, 13, 409. J. Phys. Chenz., 1962, 66, 577-654. J. 13. Hildebrand and R. L. Scott, Regular Solutions, Prentice-Hall, Englewood Cliffs, N.J., 1962. Ref. 5, p. 39. Ref. 5, p. 29.
53
54
74
entropy of mixing, . . s, that the first idea implies the second. For mixing with no change in volume or in temperature the final (mixed) state will usually have a different energy from the initial (unmixed) state, the difference being of course the energy of mixing. The interpretation of a difference between the entropies of two states of a system as a measure of the logarithm of the ratio of the probabilities of the two states is valid only when the two states have the same energy and volume. Whether it follows from the first idea or not, the second idea deserves thorough investigation. We shall therefore look a t such experimental facts as are available t o see whether the excess entropy XV* of mixing a t constant volume, calculated from the directly-measured excess entropy XpE of mixing a t constant pressure, is after all close t o zero for mixtures of substances which might be expected t o form regular solutions. Hildebrand lo has shown that when the partial molar entropy of solution (derived from the temperature coefficient of the solubility) of iodine a t 25 C, in a wide variety of solvents in which it dissolves to give regular
TABLE Excess entTopies of mixing at constant volume, and excess 1. entropies and free energies of mixing at constant pressure, for equimolar mixtures
T TSvE TSpE GPE Pair (OK) (cal. mole-l) (cal. mole-l) (cal. moleA1) Ref. Cc1, f CyClO-C,&1, 298 6*2* 18.7 16.7 a -1 273 26 CC14 C(CH314 76 9(4 6.6 298 5.8 c 1 c 4 CeH, 19.5 9(4, b 8.3 298 -13.9 C6H6 f C,H4C1, 6.2 9(4, b 39.7 n-C6H14 n-Cl,H3, f 303 79.9 - 17.0 9(e) 193 323 9 ( 4 , 12, c n-C&14 n-C,F14 298 -23; -48* i-C&18 -!- n-C,F,, 303 -60 182 326 9 y 176 89 C6H6 f 1-C8H18 313 142 C6H6 CJClO-C6H1, 298 73 125 77 e C,3H, CyClO-C,H10 308 41 64 65 f In the calculation of TSvE the volume held constant was that of the unmixed liquids at 1 atm. except for two cases marked * where it was that of the mixture at 1 atm. M. Diaz-Peiia and M. L. McGleshan, Trans. Faraday SOC.,1961, 57, 1511. b L. A. K. Staveley, W. I. Tupman, and K. R. Hart, Trans. Faraday SOC., 1955, 51, 323. C R. D. Dunlap, R. G. Bedford, J. G. Woodbury, and S. D. Furrow, J . Amer. Chem. SOC., 1959, 81, 2927; A. G. Williamson and R. L. Scott, J . Phys. Chem., 1961, 65, 275; R. D. Dunlap and R. L. Scott, ibid., 1962, 66, 631. S. Weissman and S. E. Wood, J. Chewa. Phys., 1960, 32, 1153. S. E. Wood, J. Amer. Chem. SOC., 1957, 79, 1777. f R. W. Hermsen and J. M. Prausnitz, Chem. Eng. Sci., 1963, in press.
+ +
+ +
(violet) solutions, is plotted against the ideal value, --R In x , of the partial molar entropy of mixing, the points fall on a curve (a remarkable enough observation in itself; see below for further examples) which is not very different from a straight line of unit slope. When the results are corrected from constant pressure t o constant volume the points fall on a straight line of unit slope as they should if SvE = 0. Smith and Walkley l1 have shown
Ref. 8, p. 26. (a) G . Scatchard, Trans. Faraday SOC., 1937, 33, 160; R. L. Scott; (b) Discuss. Faraday Soc., 1953, 15, 44; (c) J . Chem. Phys., 1956, 25, 193; ( d ) J . Phys. Chem., 1960, 64, 1241; (e) M. L. McGlashan, K. W. Morcom, and A. G . Williamson, Trans. Paraday Soc., 1961, 57, 601; (f)Ref. 5, p. 105. l o J. H. Hddebrand, J . Phys. Chem., 1960, 64, 370; Ref. 5, p. 36. l 1 E. B. Smith and J. Walkley, Trans. Paraday Xoc., 1960, 56, 1276; Ref. 5, p. 38.
McGLASHAN
: E Q U I L I B R I U M P R O P E R T I E S OF M I X T U R E S
75
that solutions of stannic iodide behave in the same way. When we turn t o ordinary liquid mixtures, however, the evidence is not so convincing. Table 1 shows values of T S P , together with values of TSpEand of the excess Gibbs function GpE for comparison, for most of the pairs of substances which might reasonably be expected t o form regular mixtures and for which sufficient data are available. For seven of the ten pairs of substances TSvE is closer to zero than TSpE. Of the other three pairs one, n-C6HI4 n-CI6Hs4, may be dismissed on the grounds that the molecules are far from spherically symmetrical, and another, C6H6 C2H4CI2,if we accept Hildebrand and Scotts ruling 12 that systems for which all the excess functions are small (less than about 50 calories) are to the zeroth approximation ideal and are not suited for testing the validity of a rough concept like that of the regular (CH,),, however, cannot easily solution. The third discrepant case, CCl, be dismissed. I n fact it is difficult to think of any pair of substances more suitable for testing the theory of regular solutions. Moreover, if we accept the ruling quoted above we are left with only five (the last five in the table) of the seven pairs for which TXvE is closer to zero than TSpE. I n none of these can the discrepancy between TXvE and zero reasonably be overlooked. We now turn t o the last, and perhaps the most fruitful, of the three more or less equivalent ideas. Regular solutions are defined as those in which there are no specific interactions such as may arise from the effects of molecular shape, dipole moment, charge transfer, or hydrogen bonding. For regular solutions, defined in this way, many fascinating regularities are observed. Attention has already been drawn to one such example. Here are some others: the partial molar volume of iodine (or of stannic iodide, or of bromine), in very dilute solution, is a smooth function of the solubilit,y parameter (4.v.) the solvent for a variety of solvents; of the solubility of any one of the three substances iodine, stannic iodide, or sulphur, is a smooth function of the corresponding solubility of either of the other substances for a variety of solvents l 3 (the solubilities spread over the range to lo-, mole per cent); for a given gas the solubility of the gas is a smooth function of the solubility parameter of the solvent for a variety of solvents, and for a given solvent the solubility of a gas is a smooth function of the pair-interaction energy parameter of the gas for a variety of gases. (Yen and McKetta l4 have recently shown that the solubilities of N,O in a variety of solvents agree well with Hildebrands maps.) Quite apart from their intrinsic interest and their usefulness for prediction, these regularities provide a criterion for regular behaviour so that deviations enable us t o recognize some kind of specific interaction or complexing. Examples of specific interactions which have been revealed in this way are discussed by Hildebrand and Scott.15 Of one such case, C6H, CCl,, they say l6 It is surprising that no evidence for such strong compound formation is found in the thermodynamic functions for mixing the two liquids.
Ref. 5, p. 106. E. B. Smith and J. Walkley, Trans. Paraday SOC., 1960, 56, 219. L. C. Yen and J. J. McKetttt, J. Chem. and Eng. Data, 1962, 7, 288. I5 Ref. 5, especially pp. 40, 47, 85, 119, 127, and 135. l6 Ref. 5, p. 136.
l2 l3
76
It is true that the heat of mixing is positive (compare C6H6 + CHCl, for
which it is negative), but we must expect that the observed heat of mixing will be the result of a positive regular contribution and a negative complexing contribution. The latter might be expected t o become increasingly dominant as the temperature is lowered, so that the heat of mixing should decrease with decreasing temperature. That is just what happens for C,H6 CC1,; the heat of mixing decreases rapidly with decreasing temperature (but probably not rapidly enough to become negative before the mixture freezes) in striking contrast to the behaviour of mixtures with no specific interactions for which the heat of mixing apparently always increases with decreasing temperature. Solubility parameter equations. For regular solutions the solubility parameter equations of Hildebrand and Scatchard have been used for the calculation of free energies and energies of mixing, of solubilities, of critical mixing temperatures and liquid-liquid coexistence curves, and of volume changes on mixing. The solubility parameter 6 of a substance is defined by the relation
6 = A,U/V,
where A,U is the energy of vaporization and V is the volume of the substance. Excess free energies. The excess Helmholtz function AvE for mixing a t constant volume (a) differs trivially from the excess Gibbs function GpE, for mixing a t constant pressure, and (b) for a regular solution, is equal t o the excess energy U v E , since by t,he definition of a regular solution, SvE = 0. Any of the quantities AvE, GpE, or UvE is then given for a regular solution by the relation l9
[GPE 21 AVE = UvE] = ((1 - x)V, XV,}+(l - #(6, - 6,)2, (2) where V , and V, are the molar volumes of the pure substances, x is the mole fraction of the second substance, is the corresponding volume fraction defined by the relation
4 = xV,/{(1 - 4v1 3%) (3) and 6, and 6, are the solubility paramekers of the pure substances. Scott has said 2o Solubility-parameter theory does in fact fit the free energy data on most binary systems of non-polar non-electrolytes to within 10 t o 20 per cent of thermal energies (60 to 120 calories per mole a t 25 c) or t o within the experimental uncertainty of the solubility parameters (which is sometimes large). I n Fig. 1 most of the available values of GpE, a t temperatures near room temperature, for pairs of substances which might reasonably be expected to form regular mixtures (but excluding fluorocarbons: see below) have been plotted against the right-hand side of equation (2). If the solutions were
l7 J. M. Prausnitz, J . Phys. Chenz., 1962, 66, 640; J. M. Prausnitz and R. Anderson, Amer. Inst. Chem. Engi?aeers J., 1961, 7, 96; R. Anderson, R. Cambio, and J. M. Prausnitz, ibid., 1962, 8, 66. l8 M. L. McGlashan, Experimental Thermochemistry, Vol. 2, ed. H. A. Skinner, Interscience, New York, 1962, Ch. 15: Heats of Mixing? l9 Ref. 5, pp. 91 et seq. 2 o R. L. Scott, Ann. Rev. Phys. Chem., 1956, 7, 43; Ref. 5 , p. 103.
3icGLASHAN
: EQUILIBRIUN PROPERTIES O F MIXTURES
77
accurately regular all the points shown in Fig. 1 would lie on the diagonal drawn through the origin. The broken diagonals shorn Scott's bounds taken as k90 cal. mole-l. It is clear that Scott's statement is true, as far as it goes, since all but one of the values of GpE lie within his bounds, but it is also clear, since the excess free energies of all these mixtures are so small
013
-20 0
FIG. 1. Excess free energies
40
--$ ;
/ 1I I 80 120 (a, - $)2/cal.molo'
I60
G p E for " regular solutions " plotted against t h e righthand side of equation (2) for x = 0.5. The straight line was drawn w i t h unit slope according t o equation (2). The broken lines were drawn 90 cal. mole-l (2: 0.15RT) above and below the theoretical line. 1 = cyclo-C6H,2 CCI,." 2 = CyClO-C6H1, C6H,.a 3 = cyclo-C6H,2 f n-C6HI4." 4 = C,H,, +acyclo-C6H5*CH,." 5 = cyclo-C6H,, C(CH,),." 6 = CyCl0-C6Hl2 n-C,H,,. 7 = C,H, CCl,.al b 8 = C,H, C2H4C12.a 9 = CCl, CHCl,." 10 = CCl, C(CH,),.a 11 = CCl, CH,La 12 = CH,I CH,Cl,.a 13 = CH,I CHCl,.a 14 = C6H6 n-C,H,,." 15 = C,H6 n-C,H14.u* 16 = C,H,.CH, n-C6HI4." 17 = C,H,-CH, n-C,H16.a 18 = C6H5*CH, C6H,l*CH3.C 19 = eel, CH,Cl,.d 20 = n-C6Hl4 f CC14.b 21 = C,H, i-C,H,,.e 22 = sic1, Ccl,.f 23 = TiC1, ccl,.g 24 = cyclo-C,H, + C5Hlo.h ' Most of the points relate t o 25" c and all t o temperatures between 0 c (10) and 65" c (18); according t o Hildebrand and Scott (Ref. 5 , p. 169) the right-hand side of equation (2) should be roughly independent of temperature. a Data taken from J. S. Rowlinson, " Liquids and Liquid Mixtures," Butterworths, London, 1959, Chap. 4. b S. D. Christian, E. Neparko, and H. E. Affsprung, J . Phys. Chem., 1960, 64, 442. C G. Schneider, 2. phys. Chem. (Frankfurt), 1961, 27, 171. C. S. Mueller and A. J. Ignatowski, J . Chem. Phys., 1960, 32, 1430. S. Weissmstn and S. E. Wood, J . Chem. Phys., 1960, 32, 1153. f W. R. King and L. N. Canjar, J . Chem. und E n g . Data, 1962, 7, 351. g G . A. Ryder, M. R. Kamal, and L. N. Canjar, J . Chem. and Eng. Data, 1961, 6, 594. R. W. Hermsen and J. M. Prausnitz, Chem. Eng. Sci., 1963, in press.
+ +
+
+ +
+ +
+ +
(less than about 90 cal. mole-l), that the predictive power of equation (2) is not great. Only if we can find suitable mixtures with values of GpE much larger than 90 cal. mole-1 shall we be able t o make a searching test of equation (2). The only such solutions known are those wntsining fluorocarbons. 21 For mixtures of fluorocarbons with each other the observed values 21 of z1 R. L. Scott, J . Phys. Chem., 1958, 62, 136.
78
GpE are very small (less than about 10 cal. moleF1) in agreement with equation (2). For the few mixtures which have been studied z1 of fluorocarbons with substances such as carbon tetrachloride or aromatic hydrocarbons the observed values of GpE, inferred from liquid-liquid coexistence curves, are large (250-350 cal. moleF1) and equation (2) predicts their values within Scott's 90 cal. mole-l or so. The agreement of these few large values of GpE with equation (2) is one of the most impressive achievements of solubility-parameter theory. When we turn to values of GpE for mixtures of fluorocarbons with aliphatic hydrocarbons,21 however, equation (2) fails, by three or four times the allowed 90 cal. mole-l, to account for the unusually high observed values. For example, for n-C6Hl, n-C6Fl, a t 25" c GpE (obs.) = 330 cal. mole-1 while GpE (calc. from eqn. 2) = 80 cal. mole-1. Fluorocarbons have been called 21 " anomalous " but it is tempting, in view of the apparently " regular " behaviour of fluorocarbons with carbon tetrachloride and with benzene, to ascribe the anomaly to the aliphatic hydrocarbons. Against this view, however, is the striking similarity of the large deviations from regularity for CP, Kr, and for CF, CH4.21pz2 SoZubiZities. The mole-fraction solubility, xs,of a solid solute is given for a regular solution by the relation 23
--In xs = J
rTo
(ApH20/RT2) dT
+ (1
- +)2(6,
- d2)2V2/RT,
(4)
where ArH20 is the molar heat of fusion and T ois the melting point of the pure solute. The first term in equation (4)is, of course, independent of the solvent. By contrast with equation (2))for the excess free energies, equation (4) for solubilities is quite remarkably successful. Its success is no doubt due to the much greater disparities in the solubility parameters with which we are now dealing. For example, the greatest value of (d1 for the pairs of substances in Fig. 1 is 5.76 cal. em.+ while for those in Fig. 2 it is 67-24 cal. A comparison of theory and experiment is shown in Fig. 2 for the solubility of iodine in a variety of solvents. For " regular " (violet) solutions the fit is for the most part excellent. The only notable discrepancies occur for the aliphatic hydrocarbons (the points labelled 13, 14, and 15 in Fig. 2) for which the observed solubilities are considerably greater than those predicted by equation (4). The solubility in the compact hydrocarbon cyclohexane ( 5 ) is, however, " regular." The complexing solvents, benzene (a), p-xylene (b), and mesitylene (c), deviate 24 in order of increasing donor strength from the theoretical line, 'and the still stronger donor, ether (j), deviates even more. Plots of the solubilities 2 5 of stannic iodide, naphthalene, rhombic sulphur, white phosphorus, and aluminium bromide would all give agreement with equation (4)similar to that shown in Fig. 2. For these solutes too the observed solubilities in aliphatic hydrocarbons are considerably greater than those predicted by equation (4). For
Z 2 X .
23
24
25
Thorp and R. L. Scott, J . Phys. Chern., 1956, 60, 670. Ref. 5 , p. 122. H. Hiraoka and J. H. Hildnbrand, J. Phys. Chem., 1963, 67, in press. Ref. 5, pp. 116 et seq.
McGLASHAN
: EQUILIBRIUM PROPERTIES
O F MIXTURES
79
none of the solutes iodine, bromine, or stannic iodide is the solubility in fluorocarbons abnormal.26, 21 The solubilities of naphthalene and of phenanthrene in fluorocarbons, however, are a good deal smaller than those calculated from equation (4).263 2 1 This is an effect of the same sign as that mentioned above, for the free energies of mixtures of aliphatic hydrocarbons
I
4
2.
where z@ the mole-fraction solubility of iodine a t 25' c, is FIG.2. Values of --In z@, plotted against the second term on the right-hand side of equation (4) for a variety of solvents. The circles and squares relate to solutions classified by Hildebrand and Scott (Ref. 5 , p. 164) as violet (" regular ") and as non-violet respectively. The straight line has unit slope and the intercept on the ordinate has the value given by Hildebrand and Scott (Ref. 5, p. 122) for the first term on the right-hand side of equation ( 4 ) . The solubilities, molar volumes, and solubility parameters were taken from Ref. 5, pp. 164 and 171, and for CC1,-CF3 from Ref. 24. 1 = CS,. 2 = CHC1,. 3 = TiC1,. 4 = CCl,. 5 = cyclo-C,H,,. 6 = SiC1,. 7 = CC13.CF3. 8 = CClZF.CClF2. 9 = CyClO-c,c1,Fp,. 10 = CyClO-C,F1,CF3. 11 = n-C,F,,. 12 = (C,F,),N. 13 = n-C7Hl,. 14 = i-CsHls. 15 = (CH3),C*C,H,. a = C,H,. b = p-C,H,(CH,),. c = 1,3,5-C,H3(CH,),. d = CHBr,. , e = l,2-C,H,Br2. f = 1,2-C2H,C1,. g = l,l-CzH4C12. h = cis-C,H,Cl,. i = t~um-C,H,Cl,. j = (C,H,),O.
and fluorocarbons, in which (6, - 6,)2 is not big enough to account for the observed result, but is in contrast to the apparently normal behaviour of the free energies of fluorocarbons with aromatic hydrocarbons. Omar and Dokoupil 27 have shown that the solubility of solid nitrogen in liquid hydrogen, at temperatures between 27" and 33" K, agrees remarkably well with that calculated according to equation ( 4 ) . For solid oxygen
26 Ref. 5 , pp. 116 et seq.; L. W. Reeves and J. H. Hildebrand, J . Phys. Chern., 1956, 60, 949.
27
M. H. Omar and Z. Dokoupil, Physicu, 1962, 28, 461.
80
they found, again in agreement with the theory, that the solubility was effectively zero. Separation into two liquid phases. The critical solution temperature TC is given for a regular solution by the relation 28 RTC = 2xc(1 - xC)V12V22(61 6,)2//((1 - xc)Vl xcV2}3, (5) where the critical composition xc is given by
(6) With sufficient accuracy for most purposes the critical solution temperature is given,21 after substitution of (6) in ( 5 ) and approximation, by the simple relation RTC -N (61 - 62),( V1 V,)/4. (7) The compositions, x and x, of the coexisting phases of a regular solu tion, a t any temperature less than TC, given by the relations 29 are R T In (x/x)= ((1 - #), - (1 - #),)(a, - 6,)2Vl, (8) R T l n ((1 - x)/(l - x)) = ( # 2 - #2)(S, - 6,)2V2. (9) The upper critical-solution temperatures of liquid phosphorus, and of stannic iodide, in a variety of solvents, generally fall in the order of increasing solubility parameter of the solvent, as they should according to equations ( 5 ) and (6), or (7). The predicted temperatures are not very close to those observed, but probably agree within the accuracy with which the solubility parameters are known, especially when room-temperature solubility-parameters are used a t temperatures far above room temperature ; for example SnI,+ SiC1, unmixes a t 140 C. Taking (6, - 6,) = 4.1 ca1.3 cm.-3/2, from Hildebrand and Scotts list,30 we calculate TC= 290 c. Reversing the calculation, we use the experimental value TC= 140 c and calculate (6, - 8,) = 3.5 ca1.6 cm.p3I2. Hildebrand and Scott 29 press for more determinations 31 of the compositions of coexisting phases a t room temperature, where comparison with the theory is more straightforward. Mixtures containing a fluorocarbon characteristically give upper criticalsolution temperatures. The excellent agreement between observed and calculated critical-solution temperatures for mixtures of a fluorocarbon with a liquid like carbon tetrachloride or benzene, other than an aliphatic hydrocarbon, was implied above in connexion with the excess free energies. For mixtures of a fluorocarbon with an aliphatic hydrocarbon, however, the calculated TCis always far lower than the observed value; according to solubility-parameter theory these solutions should not unmix until far below room temperature. The critical composition is always displaced to a mole fraction of the non-fluorocarbon less, and sometimes considerably less,32 than 0-5in agreement with equation (6);the coexisting phases curve is much more nearly symmetrical in the volume fraction than in the mole fraction. Fujishiro and Hildebrand 31 found, however, in agreement with previous
xc = ( V , - (V22 - VJ,
+ V12)4)/(V2
+
Vl).
Ref. 5, p. 143. Ref. 5, p. 142. 30 Ref. 5, p. 171. 31 R. Fujishiro and J. H. Hildebrand, J. Phys. Chem., 1963, 66, 573. 3 2 I<. Shinods and J. H. Hildebrand, J. Phys. Clbem., 1958, 62, 481; 1961, 65, 1885.
28
29
McGLASHAN
: EQUILIBRIUM PROPERTIES
O F MIXTURES
81
conclusions about mixtures of an aliphatic hydrocarbon and a fluorocarbon, that cyclohexane and perfluorotributylamine were mutually less soluble than they would have been if equations (8) and (9) had been obeyed. Volume changes on mixing. According t o solubility-parameter theory the volume change, VpE, on mixing a t constant pressure, is given by the relation 33 VpE = nBGpE = ( c c T / S ~ ) G ~ ~ , (10) where ci, @, and 6 are mean values of the expansivity, compressibility, and solubility parameter, respectively, and n !x 1 for many normal liquids. An equation of essentially the same form as (10) follows from first-order conforinal solution theory. 34 The most serious short-coming of equation (10) is its failure to allow VP and GpE to have opposite signs as is the case, for example, for CCl, C(CH,),. The introduction of that possibility, and the qualitatively successful prediction of the conditions under which it should occur, are by contrast the outstanding achievement of the so-called molecular theory which will be discussed below. For mixtures of an aliphatic hydrocarbon and a fluorocarbon equation (10) predicts values of VpE considerably smaller than those found.3 At high dilution the excess partial molar volume, VZE, of the solute is given according to solubility-parameter theory by the relation 36 V 2 E / V 2 0= ( Vz - V,O)/V,O = a,OT( 6, - 62)2/d12, (11) where O refers to the pure substance. The (strikingly large: 41 and 21 ~ 1 2 1 . ~ mo1e-I respectively !) excess partial molar volumes of iodine and of bromine a t high dilution in perfluoroheptane agree fairly well with the values calcuHildebrand and his colleagues 3 7 have recently lated from equation (ll).36 against a for a series of solutes a t high , plotted values of ((V 2 - V2O)/Vzo}t dilution in the same solvent (CCl, or CS,). I n each case the points lie astonishingly close to a straight line, in agreement with the form of equation (11). The fact that the slope of the line is considerably greater than that calculated is surely of minor importance. Aliphatic hydrocarbons again show significant deviations, as also do C6HC CS, for which there is other evidence 38 of donor-acceptor interaction. Smith and Walkley 39 have reviewed the available experimental values of the partial molar volumes of gases in solution in non-polar solvents. They concluded that equation (11) gives a much better account of these results than Prigogines molecular theory which grossly overestimates the effect of a disparity in the sizes of the two kinds of molecule. An even better account, however, is given by a simple free volume theory.40 Donor-Acceptor Complexes.-It seems natural t o continue this Report
Ref. 5, p. 108. H. C. Longuet-Higgins, Proc. Roy. SOC.,1951, A, 205, 247. 3 5 Ref. 5, p. 109; I. &I. Croll and R. L. Scott, J. Plzys. Chenz., 1958, 62, 954; D. E. L. Dyke, J. S. Rodinson, and R. Thaclier, Trans. Faraday Soc., 1959, 55, 903. 3 6 Ref. 5 , p. 110. 3 7 Ref. 5 , p. 110; R. Fujishiro, K. Xininoda, and J. H. Hildebrand, J. Phys. Chem., 1961, 65, 2268. 3 8 Ref. 5, p. 136. 3 9 E. 13. Smith and J. Walkleg., J. P h p . Chem., 1962, 66, 597. 4 0 J. IlalBley, to be published.
s3
34
82
CC
with a discussion of some of the complexes which cause deviations from regularity. Following the discovery by Benesi and Hildeb~-and,~l in 1948, of the intense ultraviolet absorption, characteristic of a complex, in solutions of iodine in aromatic hydrocarbons, Mulliken 4 2 developed an extension of the Lewis acid-base theory, in a quantum-mechanical form, as a basis for the interpretation of spectroscopic results on complexes. Since then a tremendous number of papers have been published on donor-acceptor complexes. Happily, the field has recently been thoroughly covered in a book by Briegleb,43and even more recently, but more briefly, in a review by Mulliken and Person.44 Other recent reviews include those of Murrell45 and of Mason 4 6 on charge-transfer spectra, of Andrews and Keefer 4 7 on molecular complexes of the halogens, and of Hassel and Ramming 48 on the determination of the structures of solid complexes. Mulliken and Person 44 emphasize that there is no sharp distinction between charge-transfer complexes and (hydrogen-bonded complexes. In particular, charge-transfer and hydrogen-bonded complexes show close parallelisms in their infrared spectra. Hydrogen bonds have been thoroughly dealt with in a recent book by Pimentel and M ~ L e l l a nand~ proceedings , ~ the of a symposium on hydrogpn bonding have been published.50 A great deal of attention has been paid t o the dependence of the frequency vCT of the charge-transfer band of iodine complexes on the ionization potential, ID,of the donor. It now seems clear 44 ( a ) that for a given group of donors, such as the aromatic hydrocarbons (n-donors) or the amines (n-donors), vCTis a function only of ID,b ) that the function is different for ( 44 different groups of donors,51and ( c ) that the function is of the predicted form and not (quite) linear as used to be supposed. Many new donors, especially lone-pair- or n-donors, and many new acceptors, including notably the iodine atom produced by flash photolysis, 52 have been studied.43,4 4 Methods for the extraction of equilibrium constants for complex formation, from spectroscopic results, have been extensively discussed.5
((
439
439
41 H. A. Benesi and J. H. Hildebrand, J . Amer. Chem. SOC., 1948, 70, 2832; 1949, 71, 2703. 1950, 72, 600; 1952, 74, 811; J. Phys. 4 2 R. S. Mulliken, J . Amer. Chem. SOC., Chem., 1952, 56, 801; Rec. Trav. chim., 1956, 75, 845. 4 3 G. Briegleb, Elektronen-Donator-Acceptor-Komplexe, Springer, Berlin, 1961. 4 4 R. S. Mulliken and W. B. Person, Ann. Rev. Phys. Chem., 1962, 13, 107. 4 5 J. N. Murrell, Quart. Rev., 1961, 15, 191. 4 6 S. F. Mason, Quart. Rev., 1961, 15, 353. 4L. J. Andrews and R. M. Keefer, Adv. Inorg. Chem. Radiochem., 1961, 3, 91. 4 8 0. Hassel and Chr. Romming, Quart. Rev., 1962, 16, 1. 4 9 G. L. Pimentel and A. L. McLellan, The Hydrogen Bond, Freeman, San Francisco, 1960. 5 0 Hydrogen Bonding, ed. D. Hadii, Pergamon, London, 1959. 51 See also Ref. 5, p. 85; J. Walkley, D. N. Glew, and J. H. Hildebrand, J . Chem. Phys., 1960, 33, 621. 5 2 R. L. Strong and J. PBrano, J . Amer. Chem. Soc., 1961, 83, 2843; T. A. Gover and G. Porter, Proc. Roy. SOC., 1961, A, 262, 476; G. Porter, Z. G. Szabo, and M. G. Townsend, ibid., 1962, A , 270, 493. 5 3 W. Liptay, 2. Elektrochem., 1961, 65, 375; M. Tamres, J . Phys. Chem., 1961, 65, 654; H. Fritzsche, 2. Chem., 1961, 1, 263; A. Tockstein, ibid., 1961, 1 180, 298; , P. K. Karmalkar, 2. phys. Chem. ( L e i p i g ) , 1961, 218, 189; H. J. G. Hayman, J. Chenz. Phys., 1962, 37, 2290.
M C G L A S H A N : EQUILIBRIUM
PROPERTIES
OF M I X T U R E S
83
Person 54 has discussed the linear relations found between the entropy and enthalpy of complex formation for a series of different donors with a given iodine] acceptor. A theoretical treatment 5 5 of [aromatic hydrocarbon complexes leads t o the conclusion that the iodine molecule lies on the sixfold axis of benzene, whereas Mulliken and Person 44 say " the question as t o the actual geometry of the 1 : 1 complexes between halogens and aromatic hydrocarbons in solution [as distinct from the situation in the crystal where each halogen molecule interacts with two or more benzene molecules] must probably be considered as an open one." Dewar and his colleagues have continued 56 to expound the " whole-complex molecular-orbital method " of theoretical treatment of charge-transfer complexes. The numerous recent papers on spectrometric measurements on chargetransfer or hydrogen-bonded complexes will not be reviewed here. Freezing-point measurements have been used by Rastogi and Girdhar 57 to establish the existence of a 1 : 1 and a 1 : 2 compound, in the solid, for dioxan chloroform, in agreement with the assumption used 5 8 to interpret free energy and enthalpy measurements. Goates and his colleagues 5 9 have recently found a solid 1 : 2 compound, which they had missed in earlier work,60 as well as a 1 : 1 compound for benzene carbon tetrachloride, and have thus confirmed the work of Rastogi and Nigam.61 Goates and his colleagues have also found solid compounds formed from other aromatic hydrocarbons carbon t e t r a ~ h l o r i d eand 1 : 2 compounds from aromatic ,~~ acetonitrile.62 Anderson and Prausnitz 63 have confirmed hydrocarbons the existence of a 1 : 1 complex of benzene carbon tetrachloride, in solution, by spectrophotometric measurements in the ultraviolet region. The presence of three methyl groups on the benzene ring (in mesitylene) increases the formation constant of the complex, in support of the view 43, 6 o that the aromatic ring acts as a donor to the empty 3d level of a chlorine atom. Stevenson and Coppinger 64 have investigated the n +o* transition in the ultraviolet region for triethylamine chloroform, fluorotrichloromethane, carbon tetrachloride, and bromotrichloromethane. I n line with previous studies 65 on hydrogen bonding they expected triethylchloroform to give a blue shift relative to triethylamine inert amine solvent. Instead they found a large red shift. The interaction was independent.of any hydrogen bond formed (the tetrahalides gave even larger red shifts) and must be due t o charge transfer.
+ +
W. B. Person, J. Amer. Chem. SOC., 1962, 84, 536. K. Fukui, A. Imamura, T. Yonezawa, and C. Nagata, Bull. Chem. SOC. Japan, 1961, 34, 1076; 1962, 35, 33. 5 6 M. J. S. Dewar and H. Rodgers, J . Amer. Chem. SOC., 1962, 84, 395. 5 7 R. P. Rastogi and H. L. Girdhar, J . Chem. and Eng. Data, 1962, 7, 176. 5 8 M. L. McGlashan and R. P. Rastogi, Trans. Faraday SOC., 1958, 54, 496. 5 9 J. B. Ott, J. R. Goates, and A. H. Budge, J . Phys. Chem., 1962, 66, 1387. J. R. Goates, R. J. Sullivan, and J. B. Ott, J . Phys. Chem., 1959, 63, 589. 61R. Rastogi and R. K. Nigam, Trans. Faraday Xoc., 1959, 55, 2005. P. 6 2 J. R. Goates, J. B. O t t , and A. H. Budge, J . Phys. Chem., 1961, 65, 2162. 1 3 R. Anderson and J. M. Prausnitz, J . Chem. Phys., 1963, in the press. ~ 6 4 D. P. Stevenson and G. M. Coppinger, J . Amer. Chem. Soc., 1962, 84, 149. 6 5 D. P. Stevenson, G. M. Coppinger, and J. W. Forbes, J . Anter. Chem. SOC., 1961, 83, 4350.
54
55
84
G E N E R A L AND P H Y S I C A L CHEbIISTRY
Prausnitz and Anderson 6 6 measured H E for acetone
45" c and found that it is about ten times larger than for acetone
zene. They argued that the small value for acetone benzene is due not to near ideality but to near cancellation of a positive '' physical " contribution (present alone in acetone cyclohexane) and a negative '' chemical " (complexing) contribution. If this interpretation is correct then raising the temperature should decrease the fraction of complexes formed and dHE/dT should be positive, as is in fact observed. Prausnitz and his colleagues 6 7 have also used similar arguments to account for the results of their instructive new measurements of HE for nitromethane hexane, hexene, 1,5-hexadiene7 hexyne, and benzene; H E was always positive but decreased with the ionization potential of the hydrocarbon, as would be expected if the observed positive value of H E contained a negative contribution arising from the formation of a charge-transfer complex. They have similarly interpreted their measurements of V" for some of those pairs, and for benzene each of a series of acceptors, in terms of trends in the extent of complexing. Scott and his colleagues 68 have measured GE a t 0" c, VE a t 20" c, and H E a t 0" and 35" c, for 1H-pentadecafluoroheptane acetone. When the {negative) enthalpy of complex formation, deduced from nuclear magnetic resonance measurements which they have also made, was subtracted from the observed S-shaped enthalpy of mixing, a (positive) enthalpy of " physical " mixing was left which agreed well with the observed enthalpy of mixing of perfluoroheptane acetone. This paper should be read by all those (including the Reporter 58) who have succumbed to the temptation to treat solutions as " ideal associated " 69a by ascribing the whole of the excess functions to complex formation. The Molecular Theory of Solutions.-For want of a better name we group together under " the molecular theory of solutions " the more or less equivalent theoretical treatments, all based on the principle of corresponding states, of P r i g ~ g i n eScott,gcKirkwood and his colleague^,^^ Brown77land others. ,~~~ The various versions of the theory have been neatly summarized by Rowlinson.7 2 The essential assumptions common to all versions are : ( a )in calculations of the thermodynamic excess functions only the " configurational " or " residual " parts of the functions need be considered; these are determined entirely by the sum of all the pair-wise interaction energies uij of the mole-
+ cyclohexane a t + ben-
J. M. Prausnitz and R. Anderson, Amer. Inst. Chem. Engineers J., 1961, 7, 96. R. Anderson, R. Cambio, and J. M. Prausnitz, Amer. Inst. Chem. Engineers J., 1962, 8, 66; J. M. Prausnitz, J. Phys. Chem., 1962, 66, 640. 6 8 D. L. Anderson, R. A. Smith, D. B. Myers, S. K. Alley, A. G. Williamson, and R. L. Scott, J . Phys. Chem., 1962, 66, 621. 6 9 I. Prigogine, " The Molecular Theory of Solutions," North-Holland, Amsterdam,
66 67
1957: (a) Cli. 10; (b) Ch. 8-12; (c) Ch. 10, equation 10.7.8; ( d ) Ch. 10, equations 10.7.4-8; ( e ) Ch. 19; ( f ) Ch. 14. 7 0 Z. W. Salsburg, P. J. Wojtowicz, and J. G. Kirkwood, J . Chena. Phys., 1957, 26, 1533; P. J. Wojtowicz, Z. W. Salsburg, and J. G. Kirkwood, ibid., 1957, 27, 505. 71 W. B. Brown, Phil. Trans., 1957, A, 250, 175, 231; Proc. Roy. SOC., 1957, A , 240, 561. 7 2 J. S. Rowlinson, " Liquids and Liquid Mixtures," Butterworths, London, 1959: (a) Ch. 9; (b) Ch. 4; ( c ) p. 326; ( d ) p. 338; ( e ) p. 127; ( f )p. 132; ( g ) Ch. 6.
M C G L A S H A N : EQUILIBRIUM
PROPERTIES OF MIXTURES
85
cules; (b) the energy of interaction uij(r) of any two molecules i and j is given by a universal function
( 12) Zcij(r) = Eijf (r/oij) of the distance r between the centres of the molecules, where E~~ and oij are, respectively, an energy and a distance characteristic of the pair and conveniently chosen as the co-ordinates of the minimum in the function f [equation (12) is of course the basis of the principle of corresponding states] ; arid ( c ) the universal function f is taken to be the Lennard-Jones (12 - 6) function (for further discussion of which see below) so that
The random mixing approximation t o the one liquid version of the theory follows from the additional assumption that a liquid mixture of mole fraction x has the configurational properties of a hypothetical pure liquid for which the pair interaction energy #(r) is given by the formula
#(r) = (1 - x ) 2 u 1 1 ( r ) 2x(1 - x ) u 1 2 ( T ) 4- x 2 u 2 2 ( r ) . (14) If, and only if,71 the uijs are given by an (n - in) function such as the Lennard-Jones (12 - 6) function (13), then # ( r ) for the hypothetical liquid is also given by the same function. The two liquid versions of the theory follow from the alternative assumption that a mole of liquid mixture has configurational properties which are the sum of those of (1 - x) mole of one hypothetical pure liquid and of x mole of another hypothetical pure liquid.gc* 2 7 It is usual, but not necessary, to expand the appropriate expression for the excess free energy, or other excess function, as a Taylor series about the values eO0and oooof the characteristic energy and distance, respectively, of some reference liquid. The series are usually truncated after the square terms. Finally, in order t o calculate the properties of the mixture from in those of the pure substances it is necessary to express c12 and c12 terms of E ~ E ~ ~ oil, ,and 022. The assumptions usually made are the geometric-mean , ~ rule El2 = ( w 2 2 ) 8 (15) for the ES, and the arithmetic-mean rule
0 1 2 = 3011 022) (16) for the 0s. Equation (15) will be further discussed below. The most important achievement of this theory is undoubtedly the successful prediction that when the 0s (or the critical volumes) are approximately equal, but the ES (or the critical temperatures) differ considerably, for a pair of liquids, then GE will be positive and VE will be negative, a result which could never have been predicted by earlier theories, I n particular, B: for mixtures of A
when TAC : TBC 2 but VAc $ VBc then HE > GE > 0 and VE > 0 (17) but; when TAc $ TBC but VAc 2: VBc then GE > H E > 0 and VE < 0. (18)
86
The successful application of rules (17) and (18) to two pairs of mixtures is shown in Table 2.
TABLE Comparison of the equimolar excess functions for 2. pairs of mixtures with rules (17) and (18)
91 0.79 0.76 80 103 0.18 91 0.70 0.94 117 102 -0.34 The data were taken from Ref, 72b for the first two mixtures, and from Ref. 76, for the second two mixtures.
+ C,H'* Ar + CH, CO + CH,

cc1,
CCI,
+B
T
(OK)
CE
T A ~ / T B '~ A ~ / V B (C mole-l) J 1.00 0.90 70 1.28 0.91 320
HE
+ C(CH,),
298 273
(J mole-') 148 310
VE (cm.8 mole-') 0.16 -0.5
The main difficulties in the further evaluation of Che theory are those of disentangling the separate deficienciesof the various built-in approximations and assumptions: failure of the pure liquids to obey the principle of corresponding states, leading to different predictions according to the choice of reference liquid; uncertainties in the values of some of the derivatives of the configurational free energy of the reference liquid ; the premature truncation of slowly convergent series; deficiencies in the (12 - 6) function for the pair interaction energies; failure of the geometric-mean rule (15). The molecular theory should apply best t o mixtures of such simple molecules as argon, krypton, xenon, and methane, for which the assumption of central interactions [equation (la)] is accurate, slightly less well to mixtures containing oxygen, nitrogen, carbon monoxide, and carbon tetrafluoride, and so on. Whatever else is said for or against the molecular theory it has certainly brought about a host of splendid new measurements of the excess functions of liquid mixtures of simple molecules a t temperatures far below room temperature, near the boiling points of the mixtures. The results of such experiments, and comparisons with the theory, have recently been reviewed in several places.,$ 3, 7 3 New measurements in this field include those of Pool et ~ 1 . (aE~ VE ~ 4 and for CO N,, 0, $- N,, and Ar N,, a t 83.82"K ; QE for Ar $- 0, at 83.82' and 89-57"K and VE a t 83-82"and 90" K ; H E for Ar 0, and Ar N, a t 84" K ) ; of Wilhelm and Schneider 7 5 (GE for Ar Kr a t 87-50"K for 0 < xK; < 0.14 only); of Lambert and Simon 7 6 (HEand VE for Ar CH4 and CO CH, a t 91.2" K ) ; of Knaap et aL7' (HEfor H, D,, H, HD, 0, at and H D D,, at 20.4" K ) ; and of Burn and Din 78 (GE for Ar 90-100" K ; in fair agreement with Pool et al.74"). The difficulties described above can be well illustrated by a synthesis of
+ +
+ +
+ + + +
N. G. Parsonage and L. A. K. Staveley, Quart. Rev., 1959, 13, 306. ( a ) R. A. H. Pool, G. Saville, T. M. Herrington, B. D. C. Shields, and L. A. K. Staveley, Trans. Faruday Soc., 1962, 58, 1692; ( b ) G. Saville and L. A. K. Staveley, Trans. Faruday Soc., to be published; G. Saville, D.Phil. Thesis, University of Oxford, 1961. 7 5 G. Wilhelm and G. Schneider, 2. phys. Chem. (Frankfurt), 1962, 32, 62. 7 6 M . Lambert and M. Simon, Physica, 1962, 28, 1191. " H. F. P. Knaap, R. J. J. van Heijningen, J. Korving, and J. J. M. Beenakker, Physicu, 1962, 28, 343. 7 8 I. Burn and F . Din, Trans. Furaduy Xoc., 1962, 58, 1341.
73
74
MCGLASHAN : EQUILIBRIUM PROPERTIES OF M I X T U R E S
87
the remarks of Beenakker and his colleagues 79 and of Staveley and his colleagues 74 on the three pairs Ar O,, Ar N,, and 0, N,, t o which a good deal of attention has recently been paid. Experimental values of the configurational enthalpy for the reference substance, and of its first and second temperature derivatives, are required showed that for Ar, for calculations of GE, HE, and TSE. Knobler et nZ.79b O,, and N,, the configurational enthalpies apparently do not conform with the principle of corresponding states, so that the reduced values of the configurational enthalpy, and a fortiori of its first temperature derivative, depend on the choice of the reference substance. They further showed, in view of those facts, and the fact that a plot of reduced configurational enthalpy was almost linear over the relevant temperature range, that no meaningful value of the second temperature derivative could be found. Experimental values of the orthobaric volume for the reference substance, and of its first and second temperature coefficients, a,re required for calculashowed that, although the orthobaric volumes tions of VE. Knobler et for Ar, 0,,and N,, conformed well with the principle of corresponding states, a plot of reduced orthobaric volume was so nearly linear over the relevant range that no meaningful value of the curvature could be found. Pool et aE.74a showed that the neglect of terms in derivatives higher than a 2 V / a T 2 for the reference substance is unjustifiable in Prigogine's equation 69c for VE. Values of the parameters E and CT for the pure substances are usually obtained by fitting experimental values of the second virial coefficient B t o values calculated according to the (12 - 6) function. Saville and Staveley 7 4 b have shown that the (12 - 6) function does not fit B, over the experimental temperature range, for Ar, O,, or N,, so that different values of E and 0 can be chosen according to the range of temperatures considered. Both the Leiden and the Oxford groups found that the values, and sometimes even the signs, of excess functions calculated according t o the theory, depended strongly on the set of parameters E and cr chosen for the pure substances, and even more strongly on the choice of a reference substance. Thus according to Knaap et uZ.79a predicted value of VE for 0, N, a t the x = 0.5 and T = 80" K ranges from +0.9 t o -0.15 mole-1 depending the on the choice of parameters, while according to Pool et aZ.74a predicted .~ value for one choice of parameters is -0.71 or -2.36 ~ 1 1 1mole-1 depending on whether 0, or N, is chosen as the reference substance. The observed . ~ value is -0-2 ~ mmole-1 according t o the Leiden and -0.31 mole-1 according to the Oxford (In view of the experimental difficulties it is not surprising to find unresolved discrepancies among the results of these and other workers.) Knobler et aZ.79b concluded that no comparison is worth while with values " calculated " from the theory. Pool et aZ.74a have given a comparison with Prigogine's equations 69d but have concluded that " The indifferent agreement with experiment is not surprising in the light of what has been said, and in fact it is doubtful if one is justified in expecting the present theories
7 9 ( a ) H. F. P. Knaap M. Knoester, and J. J. M. Beenakker, Physica, 1961, 27, 309; (b) C. M. Knobler, R . J. J. van Heijningen, and J. J. M. Beenakker, ibid., p. 296; (c) C. M. Knobler, H. F. P. Knaap, and J. J. M. Beenaklrer, ibid., 1960, 26, 142.
88
t o be quantitatively s~ccessfuI.~ Pool et al. 74a showed, moreover, that no Of &ArAr, EO,O,/&ArAr, and EN,N,/EArAr and OArAr, c 0 2 0 , / ~ A r A r and oN,N,/GArAr could be chosen so as to give a SimUltaneOUS fit of the excess functions for the three pairs. It is possible that some of the discrepancies are due either to orientation dependence of the pair interaction energy for 0, and N,, or t o failure of the geometric-mean rule (15). More measurements 7 5 are urgently needed on mixtures of Ar, Kr, and Xe, for which any discrepancies cannot be ascribed to the first possibility. The second possibility is best studied (see below) by second virial coefficient measurements on the gas mixtures. Lambert and Simons 7 6 results agree qualitatively with Prigogines equations as was shown in Table 2. For CO CH, there is, moreover, fair CM,, however, the calculated result,s quantitative agreement. For Ar are far too large; the theory overestimates the effect of a difference in molecular sizes as noted above,39 and as has been pointed out before.69a,72c According t o Lambert and Simon 713 the excess entropy for CO CH, is everywhere negative, rather than positive a t low concentrations of CO and negative at high concentrations, as had previously been found by Staveley and his colleagues.30 Knaap et aZ.77 have shown that their results, for the heats of mixing of the hydrogen isotopes, agree well with those calculated from Prigogines equations 69e for mixtures of isotopic molecules. Salsburg 81 has continued earlier 7O theoretical work on the oneliquid theory of liquid mixtures. A new approximation: +(r) = -kT In [(l - x)2 exp(ull(r)/kT) 2 4 1 - 4 exp(u,,(r)/kT) x 2 exp(u,,(r)/kT)I, (19) which Salsburg calls the pseudo-pair potential approximation [compare the random mixing approximation of equation (14)], was shown to provide a lower bound to the correct pair interaction energy of the hypothetical pure liquid, whereas the random mixing approximation provides an upper bound. Form of the Pair Interaction Energy.-Unfortunately the Lennard-Jones (12 - 6 ) , or other (n - m) form, is firmly built-in 71 to the molecular theory of solutions. A number of recent papers 8 2 cast doubts, to put it mildly, on the validity of the (12 - 6) function, especially 82c a t the very distances, close to the minimum, which are of crucial importance in liquids or solids. It is well known 83 that the second virial coefficient of a gas is insensitive t o the detailed shape of the pair interaction energy. Not much can then be
8O V. Mathot, L. A. K. Staveley, J. A. Young, and N. G. Parsonage, Trans. Paraday Xoc., 1956, 52, 1488; R. A. H. Pool and L. A. K. Staveley, ibid., 1957, 53, 1186. 81 Z. W. Salsburg, *J. Chem. Phys., 1962, 36, 1974. 8 2 ( a ) I. Amdur and T. F. Schatzki, J . Chem. Phys., 1957, 27, 1949; ( b ) A. Michels, J. I .Levelt, and W7. Graaf, Physica, 1958, 24, 659; J. M. Levelt, ibid., 1960, 26, N de 361; (c) E. A. Guggenheim and M. L. McGlashan, Proc. Roy. SOC., 1960, A , 255, 456; MoZ. Phys., 1960, 3, 563; ( d ) W. B. Brown and J. S. Rowlinson, ibid., p. 35; J. S. Rowlinson, ibid., p. 265; ( e ) B. E. F. Fender and G. D. Halsey, J . Chem. Phys., 1962, 36, 1881; (f) e f . 74; ( 9 )M. R . Jones and L. A. K. Staveley, provisional results personR ally communicated; al. R. Jones, D.Phi1. Thesis, University of Oxford, 1963. 83 J. 0. Hirschfelder, C. F. Curtiss, and R. B. Bird, Molecular Theory of Gases and Liquids, Wilej-, Xew York, 1954, p. 207.
McCLASHAN : E Q U I L I B R I U M P R O P E R T I E S OF M I X T U R E S
89
said in favour of a function which fails, as the (12 - 6) function is now known 8Zb, e s f , to fail, even to fit the second virial coefficients of the inert gases. Fender and Halsey *2e go as far as to say The inadequacies of the Lennard-Jones (12 - 6) potential function in providing a complete interpretation of the rare gases are now well known. Both Fender andHalsey82e and Jones and Staveley 8Zg have made new measurements which extend our knowledge of the second virial coefficients of Ar and Kr to much lower temperatures. The two sets of measurements are in good agreement. Both groups concluded that the second virial coefficients of Ar and Kr could not be fitted by the (12 - 6) function [or 82e by the so-called (exp - 6) function], but that at least for Ar they could be fitted, within experimental error, by the function deduced by Guggenheim and McGlashan 82c from their study of the crystal and other data for Ar. This latter function, which has received further support from the quantum-mechanical study of Dalgarno and Kingst0n,~4 strikingly diEerent from the (12 - 6) function. is In spite of the growing weight of the evidence against it the (12 - 6) function still has its defenders. Thus Barker 855 says . , . the 12 - 6 potential provides a reasonably accurate description of the interaction between argon atoms and again 85b < < Thus the results [for the critical constants calculated from the virial equation with the 12 - 6 virial coefficients up to the fourth] may be taken as an indication that the potential function for the interaction between Ar atoms is probably not very different from the 12 - 6 function. This Reporter believes that we now know that the (12 - 6) function is seriously wrong, that a detailed knowledge of the actual pair interaction energy is urgently needed, and that such knowledge can be gained only by piecing together information 82c about different small segments of the curve. Thus quantum theory gives information about the interaction at great distances,84, the equilibrium properties of crystals about the interaction 86 in the immediate neighbourhood of the minimum,82cscattering experiments about the interactions in the steep repulsive region,s7 and so on. I n this connexion the scattering experiments of Amdur and his colleagues are of outstanding importance, and it is good to read in their latest paper 8 7 that new results for the Ar-Ar interaction will soon be published. A good deal of attention has lately been given 8 8 to the Kihara 89 potential which for spherical molecules has the form u ( r ) = c{(----)12 2a CT r - 2a
84
2(--)3)6} 0 - 2a r-2a
A. Dalgarno and A. E. Kingston, Proc. Phys. SOC.,1961, 78, 607. (a) J. A. Barker, J . Chern. Phys., 1962, 37, 1061; (b) J. A. Barker and J. J. Monaghan, ibid., 1962, 36, 2571. 8 6 K. S. Pitzer, Adv. Chem. Phys., 1959, 2, 59. 8 7 I. Amdur and R. R. Bertrand, J . Chem. Phys., 1962, 36, 1078; see also previous papers by Amdur and his colleagues. 8 8 ( a ) J. M. Prausnitz and R. N. Keeler, Amer. I n s t . Chenz. Engineers J., 1961, 7 399; (b) J. M. Prausnitz and A. L. Myers, Amer. Inst. Chem. Engineers J., 1963, 9, 5; , J. M. Prausnitz and A. L. Myers, Anzer. Inst. Chem. Engineers J . , 1963, 9, in press; ( c ) F. Danon and K. S. Pitzer, J . Chem. Phys., 1962, 38, 425; ( d ) Ref. 5, p. 74. 89 T. Kihara, Rev. M o d . Pliys., 1953, 2 5 , 831.
85
90
where a is the radius of the molecule. The second virial coefficientsof argon calculated from this three-parameter function agree 8 g b with the experimental results, certainly much better than those calculated from the (12 - 6) function, and perhaps within experimental error, The Relation between e,, and ell, e,,.-Measurements of the second virial coefficients of gas mixtures lead directly,g0,82e, provided only that equation (12) is obeyed, to information about the relation between E,, and E , ~ , E,,, and in particular enable a test to be made of the geometric-mean rule
El2 = ( E l l E 2 2 ) 4 (21) Until this year there were no second virial coefficient measurements whatever on any mixtures of the simplest gases Ar, Kr, Xe, and CH,. Happily, there are now three sets of measurements on such mixtures. Two independent groups have made measurements on Ar Kr, Fender and Halsey 82e at temperatures between 108" and 124"K, and Jones and Staveley 82g between 110"and 176" K and at 298" K. The two sets of results for BIZ, the "mixed" second virial coefficient, agree well at 1 2 4 " but ~ unfortunately diverge at lower temperatures until at 110"K Fender and Halsey's B,, is about 25 ~ 1 1 1mole-l, or 10% less negative than that of .~ Jones and Staveley. Consequently the two groups have come to different conclusions about the applicability of the geometric-mean rule (21). By using Guggenheim and McGlashan's method Jones and Staveley have shown that the geometric-meanrule is obeyed well within their experimental error. Fender and Halsey, however, have shown that their results are fitted much better by a harmonic-mean rule. It remains to be seen which group is right. This Reporter backs Staveley's group and the geometric-mean rule, but clearly much work remains urgently to be done. Thomaes et aZ.91 have measured the second virial coefficientsof Ar CH, a t temperatures between 108" and 295" K (and also Ne Kr between 120" and 294" K ; since neon does not obey the principle of corresponding states for quanta1 reasons, connected with its low mass, we shall not discuss the CH, Thomaes et al. gave, as a test of results for Ne + Kr here). E'or Ar Guggenheim and McGlashan's method and of the geometric-mean rule, a plot which showed clearly (they actually said " One can see that all the points lie on the same curve except those for neon-krypton") that the geometric-mean rule was obeyed within their experimental error, though in another place in the paper they said unaccountably '' For the two mixtures we study the ' Guggenheim-McGlashan test ' fails. The observed discrepancy is due at least partly to the approximations made to obtain rule 3 [the geometric-mean rule]." The quantum theory of dispersion forces s6 can tell us about the relation of u12(r) ull(r), and uZ2(r) at values of T many times greater than 0, only where u cc r-6. Nevertheless a number of workers have boldly used London's together with formula,S2or more recently the Kirkwood-Muller formula,82e
E. A. Guggenheim and M. L. McGlashan, Proc. Roy. SOC.,1951, A , 206, 335. G. Thomaes, R. van Steenwinkel, and W. Stone, MoZ. Phys., 1962, 5 , 301. 92 ( a ) T. M. Reed, J.'Phys. Chem., 1955, 59, 425, 428; ( b ) F. Kohler, Monatsh., 1957, 88, 857; (c) J. M. Prausnitz, Amer. Inst. Chem. Engineers J . , 1959, 5, 3; ( d ) G. H. Hudson and J. C. McCoubrey, Trans. Paraday SOC.,1960, 56, 761; ( e ) R . J. Mw, Trans. Paraday SOC.,1961, 57, 187; (f) Ref. 91; (9) Ref. 5, pp. 66, 97.
go
91
McGLASHAN
: EQUILIBRIUM PROPERTIES O F MIXTURES
91
equation (13), to derive relations between E,, and E,,. The usual '' justifhation " for the geometric-mean rule (21) is the fact that London's formula reduces to that form when the two substances have equal ionization potentials and equal values of CT. gender and Halsey justify their use of the harmonic mean by the observation that the Kirkwood-Miiller formula reduces t o that form when the two substances have equal magnetic SUSceptibilities and equal values of 0. Several authors 9 Z a , a, have used values of E~, calculated from London's formula, rather than from the geometric mean, to '' explain " the anomalous properties of hydrocarbon fluorocarbon mixtures. Unfortunately that which offers a reasonably satisfactory explanation for the unusually large excess-functions of those mixtures predicts for other mixtures, such as carbon tetrachloride, benzene, or iodine, fluorocarbons, anomalies which 21 are not found.93~ Munn g2e has also shown that the use of London's formula, rather than the geometric mean, accounts for the conclusion by Rowlinson and his colleagues,94 from the results of their measurements of the critical temperatures of mixtures of aliphatic hydrocarbon aromatic hydrocarbon, that for these mixtures q2is unusually small. Rowlinson's conclusion is supported by a comparison of the excess functions 7 Z d for such mixtures with those predicted by the molecular theory, and by the results of measurements 95 of the solubility of the vapours of volatile hydrocarbons in solvents of high molecular weight. His conclusion was not supported by earlier measurements 94, 96 of the second virial coefficients of mixtures of benzene cyclohexane, but is su~ported,~' spite of their assertion 98 to the in contrary, by Bottomley and Coopes's new and probably more accurate measurements. Rowlinson 97 reminds us that none of these results can show whether the relative weakness of E,~is caused by a real weakness of the 1-2 forces or by an unusual strength of the 1-1 forces. i-butane 99 Other new measurements of B,, include those on n-butane (70" to 170" C ; B,, follows Lewis and Randall's rule B,, = +Bll 4B2,; also the liquid mixtures are shown to be ideal at 70" to 134"c ) ; on ether acetone, ether methyl iodide, and acetone chloroform loo(50" to 90" C ; for the first and second pairs B,, is much greater, and for the third much less, due to hydrogen bonding, than the arithmetic mean of B,, and B z 2 ) ; propane n-heptane and propane n-octane 101 (65" to 140"c; on Guggenheim and McGlashan's method gives a useful fit when it is slightly extended to take account of deviations from the principle of corresponding states, caused by disparities in the lengths of the molecules); on n-butane
Ref. 5, p. 98. E. J. Partington, J. S. Rowlinson, and J. F. Weston, Trans. Farday SOC., 1960, 56, 479 (and appendix by J. D. Cox and D. Stubley). O K A. J. Ashworth and D. H. Everett, Trans. Paraday SOC., 1960, 56, 1609. O 6 F. Waelbroeck, J. Chem. Phys., 1955, 23, 749; J . Chim. phys., 1957, 54, 710. @ J S. Rowlinson, Nature, 1962, 194, 470. '. O 6 G. A. Bottomley and I. H. Coopes, Nature, 1962, 193, 268. J. F. Connolly, J. Phys. Chem., 1962, 66, 1082. looSh. D. Zaalishvili and L. E. Kolysko, Zhur. $2. Khim., 1960, 34, 2596; 1961, 35, 2613; 1962, 36, 846. M. L. McGlashan and D. J. B. Potter, Proc. Roy. Soc., 1962, A , 267, 478.
O3
O4
92
perfluoro-n-butane, and dimethyl ether 1H-heptafluoropropane 102 (10" to 50" c ; the values of B,, for the first mixture indicate weaker attractive forces than usual, between pairs of like molecules; the values of B,, for the second mixture indicate hydrogen bonding) ; on hydrogen methane 1 0 3 (-93" to 10"c ; values of B were derived from isotherms a t pressures up to about 50 atm.); and on propane methyl chloride l o 4 (193" t o 293" K). Interesting accounts have been given of the application of the principle of corresponding states to mixtures of light non-polar gases by Leland et aZ.,105 of the application of the Stockmayer potential to mixtures of gases in which one or both components are polar by Blanks and Prausnitz,lOG and of the application of Kihara's potential t o mixtures of light gases by Prausnitz and Myers.107 The determination of values of B,, from measurements of the solubility of solids (or mercury in compressed gases has been discussed by Rowlinson and his colleagues.lo8 New measurements have been reported by Omar and Dokoupil logon solid oxygen hydrogen, and by King and Robertson on solid naphthalene each of six simple gases. Kielich ll1 has calculated the effect of anisotropic dispersion forces, and of quadrupole and octopole moments, on the values of B,, for some nonpolar molecules. For N, CO, and for 0, CO, his calculations agree well with experiment. Parsonage and Scott 112 have shown that the effect of octopole-octopole interactions cannot account for more than a small CH,. part of the anomalous free energies of mixtures such as CF, Lattice Theory of Mixtures.--In the lattice theory 113it is supposed that each molecule consists of a number of " elements " of one or more kinds, that each element has a number of, "contact points," that each element occupies one site on a lattice, and that the configurational energy of a mixture may be expressed as the sum of contributions, one from each of the nearest-neighbour " contacts " of the contact points of one molecule with the contact points of other molecules. A searching test of the lattice theory lies in the extent to which the energy of interchange, calculated according t o the t'heory from the energy of mixing U V E a t constant volume,g", d , remains the same throughout a series of mixtures of molecules in which there are altogether only two kinds, a and b, of contact point, three kinds a-a, b-b, and a-b of contact, and one , energy of interchange u = 2uab - u , - ubb. For example, any. pair of n-alkanes can be regarded as having only two kinds of contact points : those
102T. B. Tripp and R. D. Dunlap, J. Phys. Chem., 1962, 66, 635. 1 0 3 W. H. Mueller, T. W. Leland, and R. Kobayashi, Amer. Inst. Chem. Engineers J., 1961, 7, 267. 1 0 4 W. Kapallo and K. Schafer, 2. Elektrochem., 1962, 66, 508. 1 0 5 T. W. Leland, R.Kobayashi, and W. H. Mueller, Amer. Inst. Chem. Engineers J., 1961, 7, 535. 1 0 6 R. F. Blanks and J. M. Prausnitz, Amer. Inst. Chem. Engineers J., 1962, 8, 86. lo' J.M. Prausnitzand A. L. Myers, Amer. Inst. Chem. Engineers J . , 1963,9, 5. 108 ( a ) J. S. Rowlinson and J. M. Richardson, Ad v. Chem. Phys., 1959, 2, 85; ( b ) D. Stubley and J. S. Rowlinson, Trans. Paraday SOC., 1961, 57, 1275. 1oDM. H. Omar and Z. Dokoupil, Physica, 1962, 28, 472. 110 A. D. King and W. W. Robertson, J . Chem. Phys., 1962, 37, 1453. 111 S. Kielich, Physica, 1962, 28, 511, 1123. 112 N. G. Parsonage an: R. L. Scott, J . Chem. Phys., 1962, 37, 304. 11s E. A. Guggenheim, Mixtures," Oxford University Press, London, 1952.
McGLASHAN
93
of " end " -CH3 and " middle " -CH2- or -CH2-CH2- elements. McGlashan and his colleagues have continued their studies 114, of mixtures of n-alkanes and have now shown 1 1 4 b ~ for a wide variety of pairs of n-alkanes at 115 20" c that UvE can indeed be calculated, probably within the experimental error, from a single value of the energy of interchange u. Another test of the lattice theory lies in the extent t o which u (and hence UvE for a given pair of substances) is independent of temperature. McGlashan and his colleagues lud found, in further agreement with the theory, that UvE is independent of temperature for n-hexane n-hexadecane between 10"and 60" c. By extrapolation of their measurements of the enthalpy of mixing HpE (which is positive between 10" and 50" C, but decreases rapidly with increasing temperature), and as a corollary of the hypothesis that UvE should remain independent of temperature a t higher temperatures, they predicted that HpE should change sign at about 65" c and become negative a t higher temperatures. This prediction was challenged by Holleman and Hijmans 116who claimed as one of the consequences of their new theory (based on an extended form of the principle of corresponding states together with Brmsted's principle of congruence) that the excess functions for mixtures of n-alkanes cannot change sign. Their view of the heats of mixing was therefore that, since they are known t o be positive a t room temperatures, they must remain positive at higher Cemperatures in agreement with the earlier experiments of van der Waals and Hermans. 117 Scott,ll8 on the other hand, claims that it is a consequence of Holleman and Hijmans's own theory that HpE must be negative a t all temperatures ! New measurements 119 of HpE for n-hexane n-hexadecane a t 40", 7 5 O , and 100"C, however, confirm that HpE does change sign a t about 65" c and does become increasingly negative a t high temperatures as McGlashan et al. had predicted. Holleman and Hijmans 1 2 0 have now also made new measurements on several mixtures of n-alkanes at high temperatures. They also find t h a t HpE does change sign and become negative a t higher temperatures? and they have now invited this Reporter to eat the '' jolly good dinner '? 120 which had been a t stake for over two years (the experiments are not easy) in a friendly wager on this question. The simplest application of the lattice theory is that t o " strictly regular mixtures " 113in which the two kinds of molecule are more or less spherical and of similar size so that a molecule of each kind can be regarded a's consisting of just one element with a number, equal to the co-ordination number of the lattice, of identical contact points. As in the case of mixtures of chain molecules the lattice theory implies that UvE should be independent
11* M. L. McGlashan and K. W. Morcom, Trans. Faruday SOC., (a) 1961, 57, 581; (b) 1961, 57, 901; ( c ) M. L. McGlashan and A. G. Williamson, ibid., p. 588; ( d ) 3%. L. McGlLtshan, K. W. Morcom, and A. G. Williamson, ibid., p. 601. 115 W. Brzostowski, J. A. Larkin, and M. L. McGlashan, to be published. 116 Th. Holleman and J. Hijmans, Physica, 1962, 28, 604. 117 J. H. van der Waals and J. J. Hermans, Rec. Traw. clzim., 1949, 68, 181; 1950, 69, 949, 971; J. H. van der Waals, ibid., 1951, 70, 101. 118 R . L. Scott, personal communication, December 1962. 119 J. A. Friend, J. A. Larkin, A. Maroudas, and M. L. McGlashan, Nature, 1963, in the press. lZo J. Hijmans, personal communication, January 1963.
94
of temperature. Diaz-Peiia and McGlashan 121 found that this was so within experimental error for carbon tetrachloride cyclohexane, between 10" and 55" C , when the volume held constant during mixing a t a given temperature was made the same a t all temperatures.122 Goates and his colleagues have continued 123 previous work 124 on the application of the lattice theory to (alcohol hydrocarbon) mixtures. Here more than two kinds of contact point must be allowed; they actually allowed five kinds. They wrongly d , e , 3 identified heats of mixing a t constant pressure with the energy of mixing calculated from the theory, and unjustifiably ignored the temperature dependence of the free energy of interchange w. Their fit of the heats of mixing 125 of the fifteen mixtures, made from each of the first five normal aliphatic alcohols with each of the hydrocarbons benzene, toluene, and ethylbenzene, is less surprising in view first of the similarity both in shape and in magnitude of the heats of mixing of all these mixtures, and secondly of the variations allowed in the values of the several energies of interchange. Recent contributions to the lattice statistics (" the Ising problem ',) of strictly regular mixtures have been made by Brush,l26 by Guttman,12' by Hartmann and Schrnidtke,l2* by Knxseman A r e t ~ and by~Guggenheim , ~ ~ and McGlashan,l30 and to the statistics of the arrangements of monomers and dimers on a lattice by Temperley and Fisher 131 and by Kasteleyn.lSa Fluendy and Smith 133 have reviewed the application of Monte Carlo methods to these and other physicochemical problems. Measurements of Excess Functions.-Equilibrium stills for the measurement of the composition x of the liquid and y of the vapour phases a t given T or at given P have been reviewed,134and at least two useful new equilibrium stills have been described.*35 When P, x, y, are measured a t given T the results can be used to calculate values of GpE, provided that the second virial coefficients are known so that the often important and as often neglected correction can be made for the imperfection of the vapour. 72e The use of the Gibbs-Duhem relation to check the thermodynamic consistency of such results 72f has been further discussed in recent papers.lS6
121
122 123 124
M. Diaz-Pefia and M. L. McGlashan, Trans. Faraday SOC., 1961, 57, 1511. See also S. E. Wood and J. A. Gray, J . Amer. Chem. Sw., 1952, 74, 3733.
J. R. Goates, R. L. Snow, and J. B. Ott, J. Phys. Chem., 1962, 66, 1301. J. R. Goates, R. L. Snow, and M. R. James, J . Phys. Chem., 1961, 65, 335. 126 R. V. Mrazek and H. C. van NBSS, Amer. Inst. Chem. Engineers J., 1961, 7, 190. lZ6 S. G. Brush, J . Chem. Phys., 1961, 34, 1852. 1 2 7 L. Guttman, J. Chem. Phys., 1961, 34, 1024. 1 2 8 H. Hartmann and H.-H. Schmidtke, 2. phys. Chem. (Frankfurt), 1961, 28, 151. 1 2 9 F. E. J. Kruseman Aretz, Physica, 1962, 28, 736, 781 ; see also F. E. J. Kruseman Aretz and E. G. D. Cohen, ibid., 1960, 26, 967, 981. 130 E. A. Guggenheim and M. L. McGlashan, MoZ. Phys., 1962, 5, 433. 131H. N. V. Temperley and M. E. Fisher, Phil. Mag., 1961, 6, 1061; M. E. Fisher, Phys. Rev., 1961, 124, 1664. 132 P. W. Kasteleyn, Physica, 1961, 27, 1209. lS3 M. A. -D. Fluendy and E. B. Smith, Quart. Rev., 1962, 16, 241. 134 E. HAla J. Pick, V. Fried, and 0. Vilim, " Vapour-Liquid Equilibrium," Pergamon, London, 1958. 136 H. Schuberth, 2. Chem., 1961. 1, 312; K. Wiesener and K. Schwabe, 2. Elektrochem., 1962, 66, 36. 136B. C . - Y . Lu, I. H. Spinner, and J. C. K. Ho, Canad. J . Chem. Eng., 1962, 4 , 0 16; L. C. Tao, I n d . Eng. Chem. (Pundamentals), 1962, 1 119. ,
M c G L A S H A N : EQUILIBRIUM PROPERTIES O F MIXTURES
95
Far too much effort is still being put into the much less useful measurements of T,x, y, a t given P (usually 1 atm.). Increasing use is being made of methods 1 3 8 for the integration of the Gibbs-Duhem relation, so as t o obtain values of GE from measurements of P , x only,ls7or of P , y only.138 Calorimeters suitable for the measurement of heats of mixing have been reviewed 18 with emphasis on the need for careful elimination of any vapour phase in contact with the liquids, and on the need for careful attention to the completeness of mixing. Several useful new calorimeters have recently been described.139 Direct measurement of the excess volume of mixing is becoming more common;140this method is both more accurate and more convenient than the old method of calculation from measured densities. References to measurements of excess functions, published before about Eovember 1961, are available.72, New measurements on mixtures of " condensed gases have already been discussed in this Report. Here we shall catalogue new measurements, not previously discussed in this Report or elsewhere. Brown and his colleagues have continued their outstanding measure ments of G", H E , and VE for series of related compounds. Their latest measurements 141were of V" on each of ten alcohols benzene, on each of the three pairs from acetone, nitromethane, and acetonitrile, and on each of those three substances benzene, and carbon tetrachloride, all a t 25", 35") and 45" c. Sackmann and his colleagues have continued their study of the excess functions for the six pairs from CCl,, SiCl,, SnCl,, and TiC14, and the comparison of their results with Prigogine's molecular theory, by measurements of HEa t 4.7" and 20.2" c,142 of the dielectric constants a t 20" c.143 and Vapour pressures and activity coefficients (but without correction for gas imperfection) have also been measured for CCl, SiC1, and for CCl, TiC1, Nfvlt and Erdo.; a t 30") 40,and 50" c by Canjar and his c01leagues.l~~ have continued their study of the PVIT relations of the three pairs from CCl,, C,H,, and C,H,Cl by measurement 145 of VE (and of molar refractivities) a t 25" c, and have agcain found poor agreement with Prigogine's equations. Palit and his colleagues have continued their study of weak dipolar
))
1 3 7 J. A. Barker, Austral. J . Chem., 1953, 6, 207; S. D. Christian, J . Phys. Chem., 1060, 64, 764; H. W. Prengle and 35. A. Pike, J . Chem. and Eng. Data, 1961, 6, 400; L. C. "no, Ijtd. E n y . Chem., 1061, 53, 307; A. G. Williamson and R. L. Scott, J . Phys. Chem., 1961, 65, 375; Sh. D. Zaalishvili and L. E. Kolysko, Zhur. Jiz. Khim., 1962, 36, 887: J. J. Ljunglin and H. C . van Ness, Chem. Eng. Sci., 1962, 17, 531. 1 3 8 S. D. Christian, E. Separko, and H. E. Affsprung, J . Phys. Chem., 1960, 64, 443: F. Gibbard, ibid., 1961, 65, 1048; A. Bellemans, C. Lefebvre, and J.-L. Guisset, Bull. Soc. chin&.belges, 1060, 69, 441. 1 3 9 J. A. Lnrkin and M. L. McGlashan, J . , 1961, 3425; I. Brown and W. Fock, Austral. J . Chem., 1961, 14, 387; K. Amaya, Bull. Chem. SOC. Japan, 1961, 34, 1271; H. J. Dittricli, 31. Kulanek. and G. During, 2. Phys. Chem. ( L e i p i g ) ,1962, 219, 387; A. Kolhe and H. Snckman, 2. yhys. Chenb. (Frankfurt), 1962, 31, 19; U. Onken, ibid., 1963. 33, 162; H. Arm, Helc. Chim. d c t a , 1962, 45, 1551. 140 Ref. 131; Ref. 7%; Ref. 141. 141'1. Brown and F. Smith, Austral. J . Chem., 1962, 15, 1, 9. 1 4 2A. Kolbo and H. Snckmann, 2. phys. Chenz. (Frankfurt), 1962, 31, 19. 1 4 3 H. Sackmann and H. Kehlon, 2. Elektrochem., 1962, 66, 446. 124 G. A. Ryder, 31. R. Kamal, and L. N. Canjar, J . Chem. and Eng. Data, 1961, 6, 594; W. R. King and L. N. Canjar, ibid., 1962, 7, 351. 1 4 j J. Nj.vlt and E. Erdos, Coll. Czech. Chem. Comm., 1962, 27, 1229.
96
interactions by measurement 146 of H E and VE for C6H6 C6H,C1 and C,H,.CH, C6H,C1. They have again found that Prigogine's equations 69f for solutions with small orientational effects could be made to fit when E~~ was treated as an adjustable parameter not equal t o (.511~22)f. Findlay has continued previous (GE) work (with Copp) on triethylamine alcohols by measurements of H E a t 25" and 40" or 45" c, and has also measured HE for pyridine toluene a t 25" and 45" c and for pyridine p-xylene a t 25", 45". and 65" c. Holder and Whalley 148 have measured aVE/aP for C',H, CCl, and C,H6 C6H12 a t 25" to 75" c and have discussed their results in terms of the molecular theory (cf. Ref. 121 for similar measurements 011 the third pair CCI, C6H12 of Scatchard's famous " triangle "). Missen : \ i d his colleagues 149 have measured GE (but without any gas correcmethanol (35" c, 0-50" c), tions) mid H" for carbon tetrachloride ethanol (-, 35" c), propan-1-01 (35" c, 0-50" c), butan-1-01 (35" c , 35" c ) ,and octan-l-ol(60"C, 0-50" c ) ,and have given an interesting discussion .of their results. Low and Moelwyn-Hughes l 5 0 have measured heat capacities and adiabatic compressibilities for acetone + methyl iodide at -20" t o 35" c and have derived and discussed quantities from which CpE, T'", aVI':/dT, and aVE/aP can easily be calculated. Kapallo and Schafer 151have measured GE and H E at -80" to -40" c for the three pairs from propane, methyl chloride, znd methyl bromide, and have found that the G"s agree quite well with those calculated from the solubility-parameter equations. Amaycz 1 5 2 has published a paper, reminiscent of Hirobe's classic paper, containing the results of measurements of H E on no less than twentytwo different mixtures of a polar a non-aromatic non-polar compound or I an aromatic non-polar compound. of ; polar Other measurements of excess functions include the following. Cyclon-hexane, and n-dodecane: VE a t 15", 25", and 35" c ( VE > 0; hesane qf. mixtures of n - a l l ~ a n e s ) .Diethylamine ~~~ triethylamine: GE a t 50" by 3" to 70" c, H E a t 14", 18", and 25" c.15, Methyl formate dimethylformamicie: G" atl 60" c.lj5 Methyl acetate methanol, acetone chloroaniline: H x a t 20" and 35" c.l56 Tri-isobutyl phosform, cyclohexane phatc n-hesane, carbon tetrachloride, and di-isobutyl ether: G" a t 23" to 45" c and H E at 25' c.15' Benzene cyclohexsne ethyl acetate, and toluene ethanol: H E a t 35" c.158 Benzene n-octane: vapour pres-
+ +
+ +
+ +
146
S. N. Uhattnchuryya, A. V. Anantaraman, and S. R. Palit, Physica, 1962, 28,
633.
la7
14* 148
T. J. V. Findlay, Austral. J. Chem., 1961, 14, 520, 6.46.
G. A. Holder arid E. Whalley, T r a m . Faraday SOC.,1962, 58, 2085, 2108. G. C. Partzskevopoulos and R. W. Missen, Trans. Paradup Soc., 1962, 58, 869; J..E. A. Otterstedt axid R. W. Missen, ibid., 1962. 58, 879. 1 5 0 D. I. R. Low and E. A. Moelwyn-Hughes, Proc. Roy. Soc., 1962, A, 267, 381. l j l W. Kapallo and I<. Xchiifer, Z. Elektroclhem., 1962, 66, 508. lS2 I<. Amaya, Bull. Cheti~.SOC. ,Japaii, 1961, 34, 1278. 153 J. G6mez-IbiiGcz and Chia-Tsun Liu, J. Phys. Chem., 1961, 65, 2145. l j 4 13. J. Eittricli and E. linuer, 2. phys. Cl~ein.( L e i p i g ) , 1962, 219, 224; H. J. Bittrich, 31. Kulmek, and G. DLiring. ibid., p. 387. 1 5 j 31. Rother, M. Steinbroclicr, a i d H. J. Bittrich, 2. phys. Chem. (Leipzig), 196.3, 220, 89. lK6 U. Onlen, 2. phys. Chem. (Fraizkfurt), 1962, 33, 162. I<. Schwabe and K. Wiesener, 2. Elektrochem., 1962, 65, 39. 158 A. 1'. Ratnnm, C. I-. Rao, and P. S. Blurti, Chem. Eng. Sci., 1962, 17, 393.
JlcGL-4SHAN
97
sure, volume of liquid and vapour, compressibility of liquid. 159 Benzene
cyclopentane: GE a t 25", 35", and 45" c (see Table 1).160 Perfluoro-nhesane n-hexane: (aP/aT)va t 25" to 45" c, and review of excess functions (see Table 1).161 Dinzethylformamide water: 'VE, HE, and boiling points.162 Dimethyl sulphoxide water: density and viscosity a t 25" c , ~ and a t 25", 45", and 65" c,lG4 refractive index a t 25" c,lG3, and HE a t 164 25" c.164 Dimethyl sulphoxide each of five alcohols, and acetic acid: HE a t 25" c.lG5 Water pyridine: HE and partial pressures a t 40" c.166 Water methanol: CpE a t 10" to 60" c, and water propan-2-01: CpE at 20" to 70" c.16' Water methanol, propan-1-01, and propan-8-01: densities a t 25" c and refractive indices a t 20" and 25" c.l68 Water methanol: lH,O CH,*OIHand 2H,0 CH3*02H: a t 25" c.lG9Water proHE panol: H E a t 25", 50", and 75" c.170a Water propyl acetate, propanol propyl acetate: HE a t 25", 50", and 75" c ; methanol cyclohexane: HE a t 25", 35", 47" and, in the two-phase region, a t 64-7" c.170b Water prot-butanol: panol propyl acetate: HEa t 27", 50, and 75" c . l 7 O C Water partial pressures a t 25" c, and an interesting discussion of water t alcohol methanol mixtures in genera1.171 (An analysis of existing data for water and ethanol has been given by G O l l e ~ . ~Water ~~) hydrogen peroxide: C, a t 25" to 60" c and an interesting discussion of the excess functions for that pair.173 Water heavy water: HE = 7.6 cal. mole-1 for x = 0.5 a t 95" c.174 Phase Diagrams.-After looking a t a large number of Russian papers, particularly those on boiling-point diagrams and azeotropy, or on ternary liquid-liquid diagrams, this Reporter can do no better than another 175 in a similar predicament and remark that they represent " a particularly strong effort." The same remark can be made of the work of Swietoslawski's school in Warsaw; this work can, however, easily be found by those intere ~ t e d . l Boiling-point diagrams and azeotropy have been reviewed in a ~~
+ +
+ + +
+ -+
159
J. F. Connolly and G. A. Kandalic, J . Chem. and Eng. Data, 1968. 7,
137.
R. W. Hermsen and J. 31. Prausnitz, ChenE. Eng. Sci., 1963, in the press. R. D. Dunlap and R. L. Scott, J . Phys. C'henz., 1962, 00, 631. 1 6 2 IB. E. Geller, Zhur. $2. Khim., 1961, 35, 1105; T. M.Ivanova and B. E. Geller, ibid., p. 1221. 163 R. G. LoBel and D. A. I. Goring, J . Chem. and Eng. Data, 1962, 7, 100. 164 J. M. G. Cowie and P. M. Toporowski, Canad. J . Chem., 1961, 39, 2240. 165 J. J. Lindberp and I. Pietilii, Suomen Kem., 1962, 35, B, 30. 166 K. L. Yarym-Agaev, V. Ya. Rudin, V. A. Titova, and E. A. Kogan, Zlr~cr. $2. Kllim., 1961, 35, 2285. 1 6 7 T. Katayamn, Client. Eng. (Japan), 1962, 20, 361. 1 6 * K.-Y. Chu and A. R. Thompson, J . Chem. and Eitg. Data, 1962, 7, 355. 169L. Benjamin and G. C. Benson, Canad. J . Chem., 1963, in the press. l i 0 ( a )V. P. Belousov, Vestjiik Leitingrad Uniw., 1961, No. 4,144; ( b )Ti. P. Belousov, I. S. Zhigunov, and A. G. Morwhevsky, ibid., 1961, No. 22, 111; V. P. Belousov, A. G. Morachovsky, and A. V. Storonkin, ibid., 1962, No. 4 96. , 171A. C. Brown and D. J. G. Ives, J . , 1962, 1608. F. Golles, Monatsh., 1961, 92, 981; 1962, 93, 191, 201. 1 ' 3 P. A. Giguere and J. L. Carmichael, J . Chem. coid Ettg. Data, 1062. 7,
160
161
526.
li4 li5
176
V. P. Skripov and L. V. Povyshev, Zhur. f i z . Khivt., 1962, 36, 325. B. J. Alder, -4nn. R e v . Phys. Chertb., 1961, 12, 193. In Bull. 3 c ( i d . polotL. Sci., S e r . Sci. chim.
I)
98
b00k.l~~ Leland and his colleagues 178 and Thodos and his colleagues 1 7 9 have discussed the prediction of liquid-vapour equilibria from the principle of corresponding states, and Schuberth I8O the prediction of liquid-vapour equilibrium for hetero-azeotropic systems with low mutual solubility. Haselden and Snowden 181have published a full account of the (S-LV) equilibria for carbon dioxide propene and cyclopropane at temperatures from 100" to 260" K and at pressures up to about 2 atm. Russian groups have studied L-V equilibrium, in the critical region, for nitrogen carbon dioxide,lga acetylene ammonia,183 and ethylene ethanol.184 Omar and Dokoupil lS5have made further measurements on the ( L V ) equilibrium a t high pressures for hydrogen nitrogen. Redlich and his colleagues have continued their notable series on the thermodynamics of solutions with a of study lS6 the use of equations of state, and in particular the equation of Redlich and Kwong, to predict liquid-vapour critical behaviour in binary mixtures. A good deal of attention has been paid recently to the critical vaporization of mixtures of n-alkanes. Reamer and Sage 187 have studied ethane n-decane; Thodos and his colleagues ethane propane 188 and methane ethane n-butane;1s9 and McKetta and his colleagues lgO methane n-butane. I n all these mixtures of n-allcanes no more than two fluid phases (L V) ever coexist. Much the most interesting event in this field, however, is the n-heptane at pressures near observation by Kohn 1 9 1 that for methane 40 atm. three fluid phases (L, about 64 moles yo methane; L, and V both nearly pure methane) can coexist between the melting point of heptane and the boiling point of methane. A quadruple point [(S-L,-L,-V) where S is pure heptane] exists at -103.5" c and 23.0 atm. At the Wattens Symposium in August 1959 Rowlinson and Freeman lg 2had reported the n-octadecylcyclohexane existence of such quadruple points for ethane (C,,H,,) and for ethane 18-ethylpentatriacontane (C3,H76), and also the any of five existence of a lower critical-solution temperature for ethane other (C24to C3,) long-chain paraffin hydrocarbons. Even earlier they had
+ +
177 Ref. 134; see also E. H&la,Coll. Czech. Chem. Cornrn., 1962, 27, 1071, and previous papers. 178 T. W. Leland, P. S. Chappelear, and B. W. Gamson, Amer. Inst. Chem. Engineers J . , 1962, 8, 482. 179 V. S. Mehra, G. M. Brown, and G. Thodos, Chem. Eng. Sci., 1962, 17, 33. 1 8 0 H. Scliuberth, 2. phys. Chem. (Leipzig), 1961, 217, 236; 1962, 219, 143. lS1 G. G. Haselden and P. Snowden, Trans. Paraday Soc., 1962, 58, 1515. lS2 I. R. Krichevskii, N. E. Khazanova, L. S. Lesnevskaya, and L. Yu. Sandalova, Khim. Prom., 1962, 169. ls3 E. S. Lebedeva, and S. M. Khodeeva, Zhur. $2. Khim., 1961, 35, 629, 2602. l84 D. S. Tsiklis and A. N. Kofman, Zhur. $2. Khim., 1961, 35, 1120. l S 5 M. H. Omar and Z . Dokoupil, Physica, 1962, 28, 33. 1 8 6 0. Redlich and A. T. Kister, J . Chem. Phys., 1962, 36, 2002. l S 7 R. H. Reamer and B. H. Sage, J . Chem. and Eng. Data, 1962, 7, 161. l s 8 D . E. Matschki and G. Thodos, J . Chem. and Eng. Data, 1962, 7 232. , lS0 J. C. Forman and G. Thodos, Amer. Inst. Chem. Engineers J., 1962, 8 209. l V 0 L. R. Roberts, R. H. Wang, A. Azarnooth, and J. J. McKetta, J . Chem. an Eng. Data, 1962, 7, 484. l s 1 J. P. Kohn, Amer. Imt. Chern. Engineers J., 1961, 7, 514. l S 2 J. S. Rowlinson and P. I. Freeman, Pure Appl. Chem., 1961, 2, 329.
BARROW AND MERER: SPECTROSCOPY O F D I A T O M I C MOLECULES
99
reported 1 g 3 the existence of such lower critical-solution temperatures for a wide variety of mixtures of a hydrocarbon polymer in a hydrocarbon solvent. (The pair polyisobutene benzene is remarkable for having a n upper critical-solution temperature a t 23' c and a lower critical-solution temperature a t about 160" c!) Rowlinson and his colleagues have now confirmed l g 4 Kohn's results for methane n-heptane, and have published 195 a study of the liquid-liquid miscibility of a wide range of C4 t o C, hyirocarbons with nethane, a t temperatures between the melting point of the less volatile component and the critical temperature of methane. They find that there is a region of incomplete miscibility within this temperature range for some hydrocarbons ccntaining five carbon atoms and for almost all (including n-hexane, q.v.) hydrocarbons containing six or more carbon atoms. Many of the systems give lower critical-solution temperatures. I n others a solid phase intervenes and there is a (S-L,-L,-V) quadruple point. Shim and Kohn 196 have recently published a study of the phase equilibria for niethane n-hexane between -110" and 150" c. They have reported, i n disagreement with Davenport and Rowlinson who found a lower critical-solution temperature a t -90-6" c, t h a t there is no region where three fluid phases coexist, that is t o say that the liquids are completely miscible. Liquid-liquid immiscibility a t temperatures approaching the critical tcnipcrature of the more volatile component had of course been observed inany times before, i 2 g but only for systems containing a polar component. 'l'he implications of the discovery t h a t such behaviour can occur with pairs of non-polar compoiinds have been discussed by Rowlinson and his col728 and by Delmas, Patterson, et al.Ig7
31. L. McG.
7. SPECTROSCOPY OF DIATOMIC MOLECULES
THElast comprehensive discussion of the spectroscopy of diatomic molecules A collection of spectroscopic constants, containing some later information, appeared in 1951. I n the decade 1950-60, more than 1000 papers on this subject have appeared. Thc present Report clearly cannot attempt t o be comprehensive; rather the aim is to select for discussion topics which point t o what seem to be significant trends in the development of the subject. It will mainly be concerned with the electronic spectra of diatomic molecules in the gas phase.
\ i n s given in Herzberg's bool;,l published in 1950.
3, 215.
lg3
1'15
l S 3P. I. Frcoman and J. S. Rowlinson, PoZymer, 1960, 1, 20; see also C. H. Baker, It'. 13. Brown, G. Gee, J. S. Rowlinson, D. Stubley, and R. E. Yeadon, Polymer, 1962,
A. J. Davenport and J. S. Rowlinson, Trans. Faraday SOC.,1963, 59, 78. J. Shim and J. P. Kohn, J . Chern. and Eng. Data, 1962, 7, 3. l g 7 G. Delmas, D. Patterson, and T. Somcynsky, J . Polymer Sci., 1962, 57, 59; G. Delnms, D. Patterson, and D. Bohme, Trans. P a f a d a y SOC.,1962, 58, 2116. G. Herzberg, " Molocular Spectra and Molecular Structure. I. Diatomic molecules," van Yostrand, New York, 1950. 2 " Donnbes Spectroscopiques Concernant les Mol6cules Diatomiques," ed. B. Rosen, Hermann, Paris,1951;" Atlas des Longueurs d'Onde Caracthristique des Bandes d'hmist-ion e t d'Ahsorption des hIol6cules Diatomiques," ed. B. Rosen, Hermann, Paris, 1952.
lS6
Ettgineers J., 1963, 7, 428.
A. J. Davenport, P. I. Freeman, and J. S. Rowlinson, Amer. Inst. Clbem.
100
Several reviews, often under more general titles, have been published, particularly in the Annual Reports 3 and in the Annual Review of Physical Chemi~t7-y.~ The spectroscopy of diatomic molecules in the Schumann region 5 ( A < 2000 A) and the spectroscopy of flames 6 have been reviewed. 3luch information of spectroscopic interest is contained in reports of hight emperatwe chemistry. Bibliographies 13 covering the period 1950-60, and a neu.~letter,~ giving both information in advance of formal publication and references t o published work, have been circulated privately. Techniques.-The main emphasis in diatomic spectroscopy is still directed towards the determination of the positions of energy levels rather than t o the measurement of the intensities of transitions between them, and technical progress is largely restricted to refinements of established methods. In most cases, high resolution is obtained by large grating spectrographs in conventional mountings, but effective use has also been made of the very high resolving power available from oil-immersion spectrographs.10 The analysis of the rotational structure of a not too complicated band-system may involve the measurement of some thousands of lines, so that some degree of automation of measurement, and of reduction to wave-numbers, is now conimon in many laboratories. The increasing use of spectrographs of higher resolving power has led to the demand for sharper wavelength standards than are provided by the iron arc, and thorium lines, excited in electrodeless discharges by microwave power, are often used : tables of wavelengths have been pub1ished.l' Wavelength standards are reviewed in the report of the International Commission.l 2 The techniques of excitation of spectra in emission remain, because of their complexity, largely empirical, and are often handed down in verbal laboratory traditions. While electric discharges of various kinds remain the most important sources of emission spectra, other methods may be helpful. Interest in high-temperature chemistry has stimulated work on the thermal emission spectra obtained in King (carbon-tube) furnaces and in shock-tube
'
J. IT. Linnott, A n ) ) .Reports, 1953, 50, 9 ; J. H. Callomon, ibid., 1955, 52, 72; I. 31. Rlills, ibid., 1'360, 57, 42. A . B. F. Duncan, A ~ L . Phys. Chenz., 1954, 5, 185: H. Sponer, ibid., 1955, Rev. 6, 193: T. Fijrster, ibid., 1037, 8, 331; G. Herzberg, ibid., 1958, 9, 315; W. C. Price, ibid., 1960, 11, 133; D. A. Ramsay, ibid., 1961, 12, 255. 1. C. Price, Adis. Spectroscopy, 195'3, 1,56; P. G. Wilkinson, J . Mol. Spectroscopy, % ' 3961. 6, 1; G. Herzberg, A. Monfils, and B. Rosen, Miin. SOC.R o y . S c i . Libge, 1961, S k . I-, 146. 4, A . G. Gnydon, Adz.. Spectroscopy, 1961, 2, 23; T. M. Sugden, -4)in. Rcz.. Phys. Clwti., 1963, 13, 369. L. Firewer and A. W.Searcy, Ann. Rev. P I L ?Chem., 1956,7, 259; J. L. Margrave, ~. ibitl., 1959, 10, 457; P. W. Gilles, ibid., 1961, 12, 355; J. Drowart and P. Goldfinger, ibitl.. 1962, 13, 459. (;. Herzberg and L. L. Howe, " Bibliography of Spectra of Diatomic Molecules 1930- 1960," Ottawa; R. S. Mulliken, " Bibliography on Diatomic Molecules, 19501960.'' Chicago. J . G. Phillips and S. P. Davis, Newsletter, " Analysis of Molecular Spectra,''
prl<cloy. E. Hulthhn, N. Johansson, and U. Pilsiiter, Arkiv F p . , 1958,14, 31 ; E. HulthBn, 3.Jolicznsson, and L. Koffman, ibid., 1960, 16, 499. l 1 R. Zalubas, " Sew Description of Thorium Spectra," A-at. Bur. Stand. Res. Ilonograph, X o . 17, 1960. 1 2 Commission des fitalons dc Longueur d'Onde et des Tables de Spectres, Trans. I)iteniational Astroiiovtical Union, 1962, XI-4, 97.
B A R R O W A N D M E R E R : S P E C T R O S C O P Y O F D I A T O M I C MOLECULES
101
excitation. The spectroscopic study of flames is of especial importance because in favourable circumstances quantitative measurements of concentrations can be made. Some earlier work with conventional sources needs repeating with the fast high-resolution spectrographs now available, and some detailed analyses of this kind on molecules of particular physico-chemical or astrophysical interest such as H,, N,, OH, CN, and C, have either been published13-15 or are in progress. Another example is provided by the elegant study of the ultraviolet resonance fluorescence spectrum l6 of I,. Observations on the excitation of molecular spectra by proton beams l 7 are of astrophysical importance. Analyses of the spectra of some molecules are rendered diflicult, and indeed sometimes impossible, by the complex pattern from isotopic species present in their natural abundances. The use of electrodeless discharges is particularly important here, for some band-systems can be excited with less than milligram quantities of separated isotopes. This method was used some years ago in a determination of the nuclear spin of 77Se through observations l8 on a band system of (77Se),, and more recently in studies of SnS,lg Pb0,20 and CuCl.,l The study of electronic spectra in absorption is often of particular importance, especially for species whose electronic states are more or less predissociated. The first useful extensions of the study of absorption spectra to species of limited stability were provided by the technique of flash photolysis. Although comparatively few diatomic molecules have yet been studied in this way, the results for such species as HS,22CS,23 SO,24C10,25Br0,25 and I0 25, 26 are of sufficient interest to suggest that this approach is a fruitful one. High-intensity flashes of short duration are required as sources of continua for the study of transient absorption spectra. A review has been given,27aand the characteristics of some of these sources have been measured.27 b
l 3 ( a ) G. H. Dieke, J . M o l . Spectroscopy, 1958, 2, 494; (b) G. Herzberg and L. L Howe, Canad. J . Phys., 1959, 37, 636. l4 G. H. Dieke and D. C. Heath, Johns Hopkins Univ. SpectroscopicReport No. 17, 1959; P. K. Carroll, Proc. Roy. SOC.,1963, A, 272, 270. l5 G. H. Dieke and H. M. Crosswhite, J . Quantitative Spectroscopy and Radiative Transfer, 1962, 2, 97. l6 R. D. Verma, J . C'hem. Phys., 1960, 32, 738. l7 E. M. Reeves, R. W. Nicholls, and D. A. Bromley, Proc. Phys. Soc., 1960, 76, 217; E. M. Reeves and R. W. Nicholls, ibid., 1961,78, 588; R. H. Hughes, J. L. Philpot, and C. Y. Fan, Phys. Rev., 1961, 123, 2084; L. Herman, H. I. S. Ferguson, and R. W. Nicholls, Canad. J . Phys., 1961, 39, 476. l 8 S. P. Davis and F. A. Jenkins, Phys. Rev., 1951, 83, 1269; S. P. Davis, ibid., 1954, 93, 159. l9 A. E. Douglas, L. L. Howe, and J. R. Morton, J . MoZ. Spectroscopy, 1961, 7, 161. 2 o R. F. Barrow, J. L. Deutsch, and D. N. Travis, Natzlre, 1961, 191, 374. K. Rao and J. K. Brody, J . Chem. Phys., 1961, 35, 776. 2 2 J. W. C. Johns and D. A. Ramsay, Canad. J. Phys., 1961, 39, 210. 23 R. F. Barrow, R. N. Dixon, A. Lagerqvist, and C. V. Wright, Arlciv Fys., 1961, 18, 543. 2 4 R .G. W. Norrish and G. A. Oldershaw, Proc. Roy. SOC.,1958, A, 249, 498; W. D. McGrath and J. J. McGarvey, J . Chem. Phys., 1962, 37, 1574. 2 5 R. A. Durie and D. A. Ramsay, Canad. J . Phys., 1958, 36, 35. 2 6 R. A. Durie, F. Legay, and D. A. Ramsay, Canad. J . Phys., 1960, 38, 444. 2 7 (a) J. S. Courtney-Pratt (ed.), Proceedings of the Fifth International Congress on High-speed Photography, Society of Motion Picture and Television Engineers,
102
G E N E R A L AND PHYSICAL C H E M I S T R Y
Primary excitation by a pulsed electrical discharge may also be u~ed.27~ Little work has yet been done in this way, but some novel results have been obtained. I n particular, it has been shown that the ground state of Be0 28 is the lowest known lC+ state, which cannot arise from normal atoms, Be lS, 0 3P, and that the ground state of the BN 29 molecule is 3Il. Gaseous species which at low temperatures disproportionate to give solids of high lattice energy, as in the equilibrium 30, 31 AlF,(c) 2Al(Z) = 3AlF(g), may yet be stable in the gas phase a t high temperatures, through the increase in entropy. The use of high-temperature, carbon-tube furnaces has greatly increased our knowledge of the absorption spectra of these molecules. Their identification may often be made more readily by mass-spectroscopic studies, which lead in turn t o determinations of their heats of dissociation, but the most reliable treatments of the equilibria involve Third Law methods, for which knowledge of the vibration frequencies and of the moments of inertia is required, so that the two techniques are complementary. Transient high temperatures may be produced in other ways, for example or Several absorption in shock tube e~periments,~2 by fla~h-heating.~3 spectra have been observed in this way, and shock heating has been applied to the determination of absolute intensities of electronic transitions. These techniques detect absorption from the molecular ground states. A sensitive double-beam absorption spectrometer 34 has been described for the determination of very small concentrations of molecules, particularly in an excited metastable level, and has been applied to the measurement of the intensity of absorption from the f i s t excited state of N,, A3X:,+. Concentrations of unstable species, adequate for the study of their absorption spectra, may be obtained by condensation in low-temperature matrices.35 Sharp lines are observed in the electronic absorption spectra of OH and of NH trapped in argon matrices 36 a t 4'K, the origins being shifted by 150300 cm.-l to longer wavelengths from their positions in the gas phase. C, and C, absorption spectra 37 have been reported, and rough estimates of the
New York, 1962; ( 6 ) W. H. Parkinson and E. M. Reeves, Proc. Roy. SOC.,1961, A , 262,409; E. M. Reeves, Proc. Phys. Soc., 1963,81,47; ( c )L. 5. Nelson and D. A. Ramsay, J. Chem. Phys., 1956, 25, 272; W. R. S. Garton and A. Rajaratnam, Proc. Phys. Soc., 1957, A , 70, 815. z 8 B. A. Thrush, Proc. Chem. Soc., 1960, 339. 2 9 B. A. Thrush, Nature, 1960, 186, 1044. 3 O W. P. Witt and R. F. Barrow, Trans. Faraday Soc., 1959, 55, 730. 31 K. Wieland, XVIIIth International Congress of Pure and Applied Chemistry, p. 259. 3 2 R .W. Nicholls and W. H. Parkinson, J . Chem. Phys., 1957, 26, 423; W. H. Parkinson, Proc. Phys. Soc., 1961, '78, 705; H. Guenebaut, G. Pannetier, and P. Goudmand, Bull. SOC. chim. France, 1962, 80. 3 3 L. S. Nelson and N. A. Kuebler, J. Chem. Phys., 1962, 37, 47; J. G. Kay, N. A. Kuebler, and L. S. Nelson, Nature, 1962, 194, 671. 3 4 0. Oldenberg, D. G . Bills, and N. P. Carleton, J . Opt. SOC. Amer., 1961, 51, 526. 3 5 J. L. Franklin and H. P. Broida, Ann. Rev. Phys. Chem., 1959, 10, 145; A. M. Bass and H. P. Broida, " Stabilization of Free Radicals at Low Temperatures," Nat. Bur. Stand. Monograph, No. 12, 1960; A. M. Bass and H. P. Broida, " Formation and Trapping of Free Radicals," Academic Press, New York, 1960. 3 6 G. W. Robinson and M. McCarty, J . Chem. Phys., 1958, 28, 350. 37 R . L. Barger and H. P. Broida, J . Chem. Phys., 1962, 37, 1152; W. Weltner and P. N. Wdsh, ibid., 1962, 37, 1153.
BARROW AND MERER: SPECTROSCOPY O F DIATOMIC MOLECULES
103
oscillator strengths of the transitions have been made. Many of these spectra have also been studied in the near-infrared region. Interaction with the matrix leads, in the case of polar molecules such as HC1 38 and LiF,39o t spectra which differ notably from those a t low pressures in the gas phase. S has also been studied:4ouat 2 0 " its ~ , ~ fundamental band lies at 668 cm.-1 (for S2S2), independently of matrix material, and the identity of the absorbing species is confirmed by the isotope effect. This frequency is very much less than that for the ground state, in the gas phase, which is 721 cm.-l. Emission spectra may also be observed from trapped species: many of these are similar to the spectra obtained by subjecting solidified gases to electron and ion bombardment.40b The analysis of low-energy inelastic collisions, between electrons and oxygen molecules, not only reveals the vibrational structure in the ground state, but also gives indications of the thresholds of several excited electronic states.41 Magnetic rotation spectra. There has been some revival of interest in magnetic rotation spectra,42, 43 and the theory 4 4 of the effect has been extended.45 I n the presence of a magnetic field, optical activity may be displayed by a sample which, in the absence of the field, is inactive. This is the Faraday effect.4s If a continuous source is used and the sample is observed between crossed Nicol prisms, light will then pass through the system only a t frequencies corresponding to an absorption frequency of the sample, and an emission spectrum corresponding to the lines of the absorption spectrum will be observed. The magneto-optical rotatory power changes rapidly with frequency within the width of an absorption line 45 so that it is meaningless, in this situation, to describe or to attempt to measure optical or magneto-optical rotatory powers. The significant quantity is the total line intensity, and detailed formuh have been given for the intensities, both for magnetic rotation spectra and for the, so far unobserved, optical rotation spectra. The conditions 4 2 for strong magnetic rotation spectra are : (i) the transition must be sensitive to the magnetic field, either through a conventional Zeeman effectY47 associated with a magnetic moment coupled to the total angular momentum J,or through a perturbation by a state with a magnetic moment. I n the latter case, the lines strong in the magnetic rotation spectrum are not necessarily the intense lines in the absorption spectrum; (ii) the lines must be sharp, i.e. of natural width comparable to the . Zeeman splitting. New results for IC1 and IBr are of interest, and may be correlated with
3sH. Vu, J . Rech. Cent. N a t . Rech. Sci. (France), 1960, 53, 313; L. J. Schoen, D. E. Mann, C. Knobler, and D. White, J . Chem. Phys., 1962, 37, 1146. 3 B M. J. Linevsky, J . Chem. Phys., 1961, 34, 587. 4 0 ( a ) B. Meyer, J . Chem. Phys., 1962, 37, 1577; ( b ) ref. 65. 41 G. J. Schulz and J. T. Dowell, Phys. Rev., 1962, 128, 174. 4 2 W. H. Eberhardt, Cheng Wu-Chieh, and H. Renner, 3. Mol. Spectroscopy, 1959, 3, 664. 4 3 W. H. Eberhardt and H. Renner, J . Mol. Spectroscopy, 1961, 6, 483. 4 4 T. Carroll, Phys. Rev., 1937, 52, 822. 4 5 R. Serber, Phys. Rev.,1932, 41, 489. 4 8 H. F. Hameka, J . Chem. Phys., 1962, 36, 2540; H. F. Hameka, ibid., 1962, 37, 2209. 4 7 F. H. Crawford, Reports Progr. Phys., 1940, 6, 155.
104
GE N E R AL A N D P H YSICAL CHEMISTRY
recent high-resolution studies of the absorption spectra.48,49 I n ICl, the + transition 3111 lX+ appears strongly in the visible region, and as far as v f = 28 provides a text-book example of a magnetic rotation spectrum. Suddenly a t about 96% of the dissociation energy, the intensity drops and the structure becomes highly complex. The interpretation of this effect follows from the study of the absorption spectrum, which shows that it arises by a violent perturbation of the levels v = 28 and upwards in 3 1. The inter1, action reaches its climax a t v = 35, at which point it becomes impossible to assign vibrational quantum numbers t o the bands. The level v = 0 in 3r10+must be responsible for the perturbations, since the first level so fa,r identified in this state is v = 1. The case of IBr is somewhat more complicated. Two regions of magneticrotationspectrum appear. One consists of the transition 3111-1C+, which seems t o be perturbed a t v = 32 and becomes weaker and more complex '
0 0 2 y
0
f ~ " " f f r f ' r r ' ~ '
1 0
20
30
FIG. 1.
The rotational constant B plotted against v for the 31To+ and O+ states of IBr.49
until w f = 38 when the simple structure returns, but with low intensit,y. I n a second region between 17550 and 18100 cm.-l, three pairs of diffuse bands, separated by a ground state interval, are seen, corresponding to the transition 3110+ lC+which would not be expected to appear in the mag+ netic rotation spectrum. The isotope shifts in this region are anomalous, and it seems therefore that this region of the magnetic rotation spectrum arises by perturbation of 3110+ with an unknown magnetic state. This state is not seen in the absorption spectrum which, however, reveals perturbations in v = 30, 31, and 32 of 3111,which lie too low to be caused by 3110+, must and therefore arise from an unseen non-magnetic state. Although the study of the 3H0+f- 1C+system 4 9 fails t o elucidate the magnetic rotation spectrum state proves to be particularly interesting in that, by in this region, the 3110+ interaction with a repulsive O + state, two stable O + states are formed (see Figs. 1, 2). The approximate quantization of the 31T0+ state is carried over
4 8 E. Hulthhn, N. Johansson, and U. Pilsiiter, Arkiv Fys., 1958,14, 31; E. Hulthh, N. Jarlsater, and L. Koffman, ibid., 1960, 18, 479. 4 9 L.-E. Selin, Arkiw Fys., 1962, 21, 479, 529; L.-E. Selin and B. Soderberg, ibid., 1962, 21, 515.
BARROW AND M E R E R : S P E C T R O S C O P Y O F D I A T O M I C M O L E C U L E S
1%
into the upper Of state, but discrete energy levels seem t o appear only where levels with the same J numbering in the 3110+ upper O + states coincide. and Thus the absorption spectrum consists of selected regions of discrete bands at irregular values of v', separated by regions without discrete absorption. I n the absorption process the transition 3rZ0+ +- lC+ is thought to be the first step, and this is followed either by predissociation or by radiationless transition t o the O + state, which has a normal set of vibrational and rotational levels. ForbiddenTransitions.-EZectric dipole transitions. Under certain circumstances transitions appear which contradict the four usual selection rules for electric dipole transitions, A s = 0 ; AN = 0, & 1 ; X + ++ X-; and g f--, u. /
25 .
O+ states. The black regions indicate the positions of the vibrational levels to which transitions are observed (i.e., each region contains several rotational levels). To avoid confusion the regions are drawn to the left of the O+ curve though they belong to the O+ state.49 (Figs. 1 and 2 are reproduced, with permission, from L.-E. Selin, A r k i v FysiE, 1962, 21, 529.)
FIG. 2 . Potential curves of the
3rIIo+ and
rA
3.5
It would be wrong t o suppose that these transitions are of interest only in

technical spectroscopy. I n 1950, Herzberg wrote " in order t o arrive a t a better theoretical understanding of the electronic structure of diatomic molecules, particularly of their excited states, much more experimental material is needed. At present, in most cases only a few electronic states are known for a given molecule. A great deal of further detailed work is necessary before the knowledge of the electronic structure of molecules reaches the stage already attained by our knowledge of the electronic structure of atoms." It will normally be the case, and particularly for honionuclear molecules, where theg .f--,u rule imposes an added restriction, that complet'e information can come only through the study of forbidden transitions, or sometimes, of forbidden perturbations.
106
The rule most frequently broken is Ah' = 0. However, as atomic numbers increase, Hund's case c is often approached, and transitions forbidden by the rules for case-a and case-b states become allowed according to the case-c rules, AQ = 0, -+1. These are not true forbidden transitions, and their intensities can be used as a criterion of the extent to which case-c coupling is approached. Thus in the halides of Group IIIA, the ground 2 states are 1 +, and the first excited state is 3 I I , followed by 1II. The transitions III t-lZ + are known for all these molecules (except BI),but 311+- lZ + is known only for AlCl 50 and for heavier molecules.51 I n the limit of case-c, the transition 311-1C gives two distinct systems, l(3111)-1Z+and O+(3110+)-1Z+, former with P,Q, and R branches, and the latter with the P and R branches only. I n the Cameron bands of COYhowever, which arise from a3II-lZ +, and in a new system of SiO,52 1Z--3II,three sub-bands, each with P, Q, and R branches of roughly comparable intensity, are found. GaH seems to present a case near the limit:53 1(3111),O+(3110+)-1E+ have the appearance of separate systems, but weak structure has been assigned to 2(311,)-1E+. I n N,, the transition C311u-X1Zg+,54 and a Rydberg series,55 311u-lZg+, have been observed; the series shows interesting variations of intensity, which may depend on a change of coupling case along the series. 3E+-1Z + transitions are known for several molecules, for example, N2,57and CS.58 I n this transition, made allowed by spin-orbit interaction, the selection rules are A J = 0, & l ; AN = &l, so that four branches are found, forming two close pairs whose separations depend on the triplet splitting of the 3Z state. I n N, this system gives rise to the Vegard-Kaplan bands, which are only with difKculty observed in absorption:57there seems to be a considerable increase in intensity in the sense N, < CO < CS. The same structure is shown by the system lEu--X3Zg- in 02,59 except that here the antisymmetric levels are missing. This system is again weak; for the rotational analysis, plates were taken with a path of 350 m., at a pressure of 2.7 atmospheres. Several doublet-quartet systems have now been analysed from observations in emission. I n SiF,60 the spin-splitting in the upper state of the transition 4 2 - - 2 I l is well resolved and the spin-splitting constants have been evaluated. A similar transition is known in GeH,61 while ScO 62 and La0 6 3 have 4 ground states which combine with excited states ,II and ,E. In C a 211(a)-4X transition twelve branches are expected in each sub-band, obeyD. Sharma, Astrophys. J., 1951, 113, 210. For references, see R. F. Barrow, Trans. Paraday Soc., 1960, 56, 952; Proc. Phys. SOC.,1960, 75, 933. 62R. D. Verma and R. S. Mulliken, Canad. J. Phys., 1961, 39, 908. 63 M. L. Ginter and K. K. Innes, J . Mol. Spectroscopy, 1961, 7, 64. 5 4 Y. Tanaka, J. Opt. SOC. Amer., 1955, 45, 663. 55M. Ogawa and Y. Tanaka, Canad. J. Phys., 1962, 4 , 1593. 0 66G. Herzberg and T. J. Hugo, Canad. J. Phys., 1955, 33, 757. 6 7 P. G . Wilkinson, J . Chem. Phys., 1959, 30, 773. 5 8 A. Lagerqvist, B. Westerlund, C. V. Wright, and R . F. Barrow, Arkiv Fys., 1958, 14, 387. 5 9 G . Herzberg, Canad. J. Phys., 1953, 31, 657. s o R . D. Verma, Canad. J . Phys., 1962, 40, 586. 6 * B .Kleman and E. Werhagen, Arkiv Pys., 1953, 6, 399. c 2 L. Akerlind, Arkiv Fys., 1962, 22, 41. 9 3 L. Akerlind, Arkiv Fys., 1962, 22, 65.
61
B A R R O W A N D M E R E R : S P E C T R O S C O P Y O F DIATOMIC M O L E C U L E S
107
ing the selection rules AJ = 0, &l; AN = 0, &l, &2, &3: their intensities vary widely, and branches with AN = &3 have not been observed. For 2C-4X, ten branches are expected, according to the rules AJ = 0, rfrl; AN = rfrl. Nitric oxide, dissolved in various organic solvents,64 shows absorption bands which have been ascribed to the predicted transition 411-X211. Bands assigned to the same transition are observed in emission in low temperature matrices 65 ( M bands). However, in solution, y o = 25900 cm.-l, while the origin of the M bands is calculated, from the isotope effect, to lie at 37965 cm.-l, so that the two systems are Werent. This transition has not yet been observed in the gas phase. The rule AA = 0, &1 can be broken, and the system 3Au-X3C,- has been observed in 0, in absorption:59however, the bands are very weak, and it appears that the AA rule is very strictly obeyed when there is no change of multiplicity. The Hopfield-Birge system d-XIC+ in CO is now known to arise from the transition 3A-lC+, following the analysis 6 6 of the triplet bands, d3A-a311. The corresponding transition in N,, 3Au-X1X,,+, has not yet been observed. Intensity formulE for C-A transitions have been given.67 Holding to about the same degree of approximation as AR = 0, &l is the rule C + t/L,C-,though again the strictness is somewhat relaxed for intermultiplicity transitions. I n 0, the transition 68 32,+-3&(Herzberg bands) is the most intense of the three forbidden systems in the ultraviolet region which contribute to the spectrum of the light of the night sky (nightglow), while lC--lC+ transitions are known for CO 69 and N2,70and electric dipole transitions between lC+ and 3C- states are known for C 0 , 5 6 N2,71 CS,23 and NBr.72 The transition lC+--llZ- consists of a single & branch, while 3C+-3C- bands have seven strong &-form branches, with six weak satellites obeying AN = &2. 3CT-1C2 transitions have five branches, obeying AJ = 0, & l ; AN = 0, &Z. No 2X--2C+ systems are known. I n CO, the state PE-, known from its interactions with A111,73 has recently been observed in absorption, PC--XIX +.69 The analogous transition, dlCu---XIZg+,in N,, has also been observed in absorption. 7 0 I n N,, the appearance of these highly forbidden bands is explained by perturbations with a group of lIIu states lying some 30000 cm.-l above. The Herzberg bands of O,, which are about 10-6 times as intense 7 4 as the
6 4 T. S. Piper and R. S. Drago, J. Chem. Phys., 1962, 36, 241; S. R. La Paglia, ibid., 1962, 37, 457. 6 5 H. P. Broida and M. Peyron, J . Chem. Phys., 1960, 32, 1068. P. K. Ca,rroll, J . Chem. Phys., 1962, 36, 2861. 6 7 I. KOVBCS, Canad. J . Phys., 1960, 38, 955. 6 8 G. Herzberg, Canad. J. Phys., 1952, 30, 185. 6 9 G. Herzberg, personal communication. 'O P. G. Wilkinson and R . S. Mulliken, J. Chem. Phys., 1959, 31, 674. ' l M . Ogawa and Y. Tanaka, J . Chem. Phys., 1960, 32, 754; P. G. Wilkinson, ibid., 1960, 32, 1061; G . H. Dieke and D. F. Heath, ibid., 1960, 33, 432. 7 2 E. R. B. Milton, H. B. Dunford, and A. E. Douglas, J . Chem. Phys., 1961, 35,
1202.
7 3 R. F. Schmid and L. Gero, 2. Physik, 1937, 106, 206; J. L. Deutsch and R. F. Barrow, Proc. Phys. Soc., 1962, 80, 561. '* R. W. Ditchburn and P. A. Young, J. Atmos. Terrest. Phys., 1962, 24, 127.
108
B3Xu--X3C,-, Schumann-Runge bands, have the structure expected, but the branch intensities do not agree with those predicted on the assumption that spin-orbit coupling is solely responsible for the appearance of the system. Good examples of the transition 3C--11:+ provided by CO,S6 N2,71 are and CS.23 I n N,, the transition is B3X,--X1C,+, where the upper state. B, is the upper state of the infrared Y bands of the active nitrogen afterglow. The transition 23-X receives intensity from perturbations of B with higher l Z U + and lIIu states. The rotational structure consists of an unresolved Q branch (QQ,QP,and QB) with two satellites ( S B and OP). The predicted five branches are resolved in CS, although their course is unusual following strong perturbations with AfrI and with other states. A transition lC + -+ 3Cc, but with unusual structure, is found 7 2 in NBr. Only two branches appear, and it is suggested that the lower state consists of the Fl levels of a ,X- state, and that the branches are Q P and SR. This explanation is plausible if the 3 2 - state lies between Hunds cases-b and -c, since in case-c a 3 X - state goes over to a O f state (Pl levels) and a 1 state ( P , and F , levels). However a transition (,X--, case-c, Fl)+3Z(case-b) would also give the observed structure. Although the selection rule g u holds very strictly for homonuclear diatomic molecules, it applies less strictly, and can be broken, in the case of a heteronuclear molecule made up of two isotopes of the same element, such as HD.75, 76 Although they are extremely weak, the fundamental and fist three overtones of the vibration-rotation spectrum of HD have been observed, and very precise values of molecular constants determined. The intensity of this lCg+-lXg+ transition depends on the small dipole moment which arises when the molecule vibrates: the electrons lag slightly behind the centre of positive charge in the vibrating molecule. The overtone bands observed are very little less intense than the fundamental, presumably through an increase of the dipole moment with increasing amplitude of vibration. A contribution to the transition moment associated with pure rotation and rotation-vibration spectra depends on the net charge residing on the molecule as well as the difference in masses of the nuclei.77 The intensities of these spectra for molecule-ions such as HD + and (C135C137) + should be appreciable. Quadrupole and magnetic-dipole transitions. For electric-dipole radiation the rule g f--,u holds strictly, but for quadrupole and magnetic-dipole radiation the rule is g g ; u -++ u. This results from the selection rule for the symmetries of the rotational levels ; for electric-dipole radiation the rule is f--, -,while for quadrupole and magnetic-dipole radiation it is +-+ ; - +-+ -. Quadrupole and magnetic-dipole transitions are distinguished by different selection rules for J . I n magnetic-dipole transitions the rule is exactly the same as for electric-dipole radiation, A J = 0, & l ; J = 0 t/L,J = 0, but for quadrupole transitions, A J = 0,&l,&2 J J = 0 t/+J = 0, J = 1 ; J = +/4J = Q.
T5
76
77
R. - . 4 Durie and G. Herzberg, Canad. J. Phys., 1960, 38, 806. G. Herzberg, T r a m . Roy. SOC. Canada, 1962, 46, 1. F. 0.Ellison, J. Chem. Phys., 1962, 36, 478.
B A R R O W AND M E R E R : S P E C T R O S C O P Y O F D I A T O M I C M O L E C U L E S
109
The best known examples of magnetic-dipole transitions come from the spectra, of 0, and N,. I n O,, the infrared and the atmospheric bands are assigned to the magnetic-dipole transitions a1A,-X3&- and blXg +-X3Cg(rather than to the electric-dipole transitions u-g) on the basis o f their exceedingly low intensity and from consideration of the low-lying molecular orbitals. The lowest singlet transition in N,, which gives the Lyman-BirgeHopfield bands, is similarly ascribed to the magnetic-dipole transition alIIg-X1&+. This assignment has now been proved 78 by the observation of weak 0 and X branches, which in a 1II-lZ system can arise only from a quadrupole transition. 79 Thus, in these bands, both magnetic-dipole and electric-quadrupole transitions contribute to the intensity, to the extent of about 85% and 15% re~pectively.~~ was the first example known of This an electric-quadrupole electronic band system : the corresponding system lIIg-l&,+ has been observed g o in P,, but the quadrupole branches have not been seen. The unresolved Q branch of the 0-0 band of the transition blZ,+-alAgin 0, is observed in emission 81 in a discharge through oxygen in helium at 19080 A. This is forbidden, both as an electric-dipoletransition and as a magnetic-dipoletransition, since AA = 2, and it must therefore arise from an electric-quadrupole transition. An electric-quadrupole vibration-rotation spectrum 76, 8,~ 8 3 has been observed for H,. Here the fundamental and first two overtone bands have been studied for very long paths (40 km. atm. for the 3-0 band). The strongest lines in each band are X l),Q(l), and X(0). The spectrum is some( what complicated by the presence of the induced-dipole absorption spectrum, which appears as broad diffuse lines whose intensities vary as the square of the pressure. In the 1-0 band, the effect of pressure is to split the lines into two broad components, which, for the Q(1) line, are called Q p and Q R . The intensities of the three quadrupole bands have been calculated to lie in the order 1-0 : 2-0 : 3-0 = 1 : 0.20 : 0.028. The spin re-orientation spectrum of 0, consists of transitions F,-F,, F,-F, in the triplet levels of X3Eg-, and may be classed as a magnetictransition. The lines lie in the microwave region near dipole 3Cg--3C,2 cm.-l and have been measured with great accuracy to give the triplet ~ p l i t t i n g . A~ ~ similar spectrum should be given by SO, and, a t shorter wavelengths, by s, and other similar molecules : however, these have not yet been observed. No example appears to be known of a magnetic-dipole transition in a heteronuclear &at oniic molecule.8 5 Intensities.-Absolute values. Until comparatively recently, few values
P. G. Wilkinson, Astrophys. J., 1957, 126, 1. P. G. Wilkinson and R . S. Mulliken, Astrophys. J., 1957, 126, 10. A. E. Douglas and K. S. Rao, Canad. J . Phys., 1958, 36, 565. s1 J. F. Noxon, Canad. J . Phys., 1961, 39, 1110. 8 2 G. Herzberg, Canad. J . Res., 1950, A , 28, 144. 83 D. H. Rank, B. S. Rao, P. Sitaram, A. F. Slomba, and T. A. Wiggins, J . Opt. SOC.Amer., 1962, 52, 1004. 13* J. H. Burkhalter, R. S. Anderson, W. V. Smith, and W. Gordy, Phys. Rev., 1950, 79, 651; R. S. Anderson, C. M. Johnson, and W. Gordy, ibid., 1951, 83, 1060. s 5 G. H. Dieke and H. M. Crosswhite, Bumblebee Report No. 87, Johns Hopkins University, 1948.
79
110
of the absolute intensities of electronic transitions in unstable radicals in the gas phase had been measured. The methods available depended upon the determination of the optical extinction coefficient and required a knowledge of the radical concentration : they also depended on the relation between the experimental line widths and the resolving power of the spectrometer. With reactive species (as opposed to stable molecules such as the halogens and hydrogen halides) 86 these difficulties were such that different determinations of the oscillator strength,f,for a particular transition often differed by a factor of two or more.87 Direct determinations, of much greater precision, have now been made of the radiative life-times of excited states.88 I n this method, the upper state of the transition to be studied is populated by electron bombardment. The electron beam is then cut off, and the decay of light output with time is measpred. The average life, z, is determined from the first-order decay constant. This is related to the osciElator strength, f, by
f = (mch2/8n2e2) (d/d) (1/z),

where d, d are the degeneracies of upper and lower states, and A is the wavelength of the transition. The case of the first excited state of nitrogen, A3C,+, the upper state of the Vegard-Kaplan bands, A 3&+-X1&,+, is of unusual interest, These bands are very weak in absorption and a path of about 4 meter-atmospheres is required for observation. The state B3E,+ is therefore highly metastable, and this has permitted the use of an ingenious method 8Sa for the determination of its life-time. A steady concentration of molecules in is maintained by a discharge. Now the life-time in A3C,+ is the reciprocal of the Einstein coefficient, A , of the Vegard-Kaplan system, defined by n = A N where n is the number of photons emitted per ~ min. ~
TABLE1
Molecule CH CN
N 2
co+
3 2 OH
86
Transition B 2Z-X 211 A2A-X21T BZZ+-X%+ A2II-X2Z+ A3C,t+-X1Cg+ B 3rII,-A 3Xu+ C311u-B311g B2Zu+-X%,+ A311-X3ZA2Z+-X211
Radiative life-time of excited state (sec.) (10.0 f 4-01 x 10-7 (5.6 f 0.6) x (8.5 f 1.0) x 10-8 (2.6 f 0.6) x loF6 2 f 0.9 (1.2 & 0.4) x (4.45 & 0-6) x (6.58 f 0.35) x (4.25 f 0.6) x 5.5 x 10-7 7.2 x 10-7
Ref. 87 87 90 91 89 89, 98 88 88 87 92 93
R. S. Mulliken and C. A. Rieke, Reports Progr. Phys., 1941, 8, 231. R. G . Bennett and F. W. Dalby, J . Chem. Phys., 1960, 32, 1716. 8 8 R. G. Bennett and F. W. Dalby, J . Chem. Phys., 1959, 31, 434. 89 (a) N. P. Carleton and 0. Oldenberg, J. Chem. Phys., 1962, 36, 3460; ( b ) ref. 98. 9oR. G. Bennett end F. W. Dalby, J . Chem. Phys., 1962, 36, 399. O1 R. G . Bennett and F. W. Dalby, J. Chem. Phys., 1960, 32, 1111. n 2 T .Carrington, J . Chem. Phys., 1959, 31, 1243; see also ref. 127b. O 3 M. Lapp, J. Quantitative Spectroscopy and Radiative Transfer, 1961, 1, 30.
B7
B A R R O W A N D M E R E R : SPECTROSCOPY O F D I A T O M I C MOLECULES
111
the Vegard-Kaplan system, and N is the concentration of metastable molecules in state A%:,+ per ~111.~.n was determined by measuring the absolute intensity of emission by spectrophotographic comparison against a standard lamp. N was found from the intensity of absorption in the system B311,-A3X:,+ (the first positive system) with a double-beam absorption spectrometer,34 by using a second nitrogen discharge as background source. The measurements give directly the ratio of the transition probabilities of the B-A and A-X systems, which is found to be (1.6 & 0.4) x lo6. By combining this figure with the transition probability of the first positive system,gg the radiative life-time of A3&+ is found to be 2(&0.9) sec. Values of some recently determined radiative life-times are given in Table 1. Measurements of absolute intensities have also been reported for 3Zc,+-X3Zc,-94 and blZ,+-alAg 81 in O,, and for the y 95 and 6 96 bands of NO. f-values at the long-wavelength end of the Schumann-Runge system in 0, have been measured 9 7 by studying the absorption in the shock-heated gas: the transition probability is found t o decrease with increasing internuclear separation. Thef-value at the 0-0 band of the first positive system of N, is found to be (2.8 & 0.7) x lod3from measurements of the radiation from shock-heated nitrogen.98 Theoretical calculations of absolute intensities, again for the most part in systems of kinetic or astrophysical interest, have been made, for example, for the transition 99 2Cu+-2&+ in H,-, and for various systems 100 of C2. Experimental measurements of relative intensities for several forbidden systems in N, have also been made.70 Relative intensities of bands within a system. If rotational and vibrational terms are separable, the relative vibrational transition probability, or band strength, may be written as the product of the square of a transition moment multiplied by a vibrational overlap integral :
where R,(r) is the electronic transition moment, Tv,, is the r-centroid of the band, and qv.,vxis the Franck-Condon factor, given by
The r-centroid lo1 is defined by
R. W. Ditchburn and P. A. Young, J . Atmos. Terrest. Phys., 1962, 24, 127. J. W. Daiber and M. J. Williams, J. Quantitative Spectroscopy and Radiative Transfer, 1961, 1 135. , 9 6 S. P. Erkovich and Yu. P. Pisarevskii, Optics and Spectroscopy, 1960, 9, 141. 9 7 C. T. Treanor and W. H. Wurster, J . Chem. Phys., 1960, 32, 758. D * W. H. Wurster, J. Chem. Phys., 1962, 36, 2111. sg B. K. Gupta, Physica, 1960, 26, 335. loo E. Clementi, Astrophys. J., 1960, 132, 898. lol R. W. Nicholls and W. R. Jamain, Proc. Phys. SOC., 1956, 69, 253.
g4 95
112
and represents an average internuclear separation associated with the d-d transition. I n a first approximation, if the variation of transition moment with internuclear separation is neglected, the band strength is directly proportional to the Franck-Condon factor. The transition moment will, in fact, generally vary with internuclear separation, particularly for valencyshell transitions where it will often be the case that as r goes to infinity the transition goes over into one forbidden in the separated atoms.86 The variation of transition moment with distance may be determined if experimental measurements of relative intensities are combined with calculated values of q and of r . This is a subject of obvious importance, particularly in astrophysics lo2 and, for example, in the study of flamesi;103 The techniques of measurement of intensities, particularly for overlapped bands, have been discussed.lo4 Franclc-Condon factors have been calculated for systems of N,, N2+,105,106 02, 1 0 7 , 108 C0,109 CO+,110 N0,lll Be0,112 MgO,111-113 SrO,lll Ba0,112 a O y l l l ,1 1 4 Si0,111, 115 TiO,lle VO,lll, 1 1 7 RbH,118 MgH,112 and CaH.112 r-centroids have been calculated for systems of N2+,lo6C0,19 C0+,l1O Mg0,113 A10,114 Si0,ll5 TiO,ll6 and RbH.ll* The variation of transition moment with internuclear separation has been studied experimentally for the following systems : O,, Schumann-Runge system;lfg N,, Vegard-Kaplan bands;12O CN, B-X system;l21 BeO, C-X system;122and TiO, a - ~ y s t e m . l The basis for the Condon parabolae of intensity distribu~~ tion has been dis~ussed.12~ Intensity distributions may be used to estimate rough values of r:-re in a system.125 Quite recently it has been suggested that there may, in some cases, be
lo2 R. W. Nicholls, The Airglow and the Aurorae, p. 302, Pergamon Press, London, 1956. lo3D. Robinson and R. W. Nicholls, J . Quantitative Spectroscopy and Radiative Transfer, 1961, 1 76. , l o 4 A . G. Gaydon, T h e Spectroscopy of Flames, Chapman and Hall, London, 1957. lo5 R. W. Nicholls, J . Res. Nat. Bur. Stand., 1961, A , 65, 451. lo6 R. W. Nicholls, Canad. J . Phys., 1962, 40, 523. lo I. T. Yakubov, Optics and Spectroscopy, 1960, 9, 212. l o 8R. W.Nicholls, Canad. J . Phys., 1960, 38, 1705. lo9 N. L. Singh and D. C. Jain, Proc. Phys. SOC.,1961, 78, 399. 1 1 0 R. W. Nicholls, Canad. J . Phys., 1962, 40, 1772. l l 1 R . W. Nicholls, J . Res. Nat. Bur. Stand., 1962, A , 66, 227. 112 F. S. Ortenberg, Optics and Spectroscopy, 1960, 9, 82. 113 S. S. Prasad and K. Prasad, Proc. Phys. SOC.,1962, 80, 311. 114 N. R. Tawde and V. M. Korwar, Proc. Phys. SOC., 1962, 80, 794. 115 A. T. McGregor, R. W. Nicholls, and W. R. Jarmain, Canad. J . Phys., 1961, 39, 1215. 116 S. S Prasad, Proc. Phys. Soc., 1962, 79, 1078. . 11 F. S. Ortenberg, Optics and Spectroscopy, 1961, 11, 417. 118 D. C. Jain, Proc. Phys. SOC., 1963, 81, 171. l l 9 G. R. HBbert and R. W. Nicholls, Proc. Phys. SOC., 1961, 78, 1024. l20 N. P. Carleton and C. Papaliolios, J . Quantitative Spectroscopy and Radiutive Transfer, 1962, 2, 241. 121 S. S. Prasad, Indian J . Phys., 1960, 34, 584. 122 N. R. Tawde and N. S. Murthy, Proc. Indian Acad. Sci., 1960, 51, A , 919. F. S. Ortenberg, Optics and Spectroscopy, 1960, 9, 80. 124 R. W. Nicholls, Nature, 1962, 193, 966. 1 2 5 N. R. Tawde and A. P. Walvekar, Indian J . Phys., 1960, 34, 397; M. BBcart, Cornpt. rend., 1962, 254, 831.
B A R R O W ,4ND M E R E R : S P E C T R O S C O P Y O F D I a T O M I C M O L E C U L E S
113
serious limitations t o the validity of some of this work. I n the f i s t place, it has often been assumed t,hat the intensity ratio of two bands of a system with a common upper state, say 0-0 and 0-3, would be constant, irrespective of discharge conditions. It has now been found 126 that, at least in the system C3rII,-B3rI, in N,, the intensity ratio of, for example, the 0-1 t o 0-3 band varies markedly with the current density, and possibly with the gas pressure. I n the second place, work on the B2C+-X211 system of OH indicates 127 that it may be by no means adequate to consider as separable the vibrational and rotational terms in the intensity, so that it may be a poor approximation to consider the transition probability as constant over all the lines of a band unless both states are very similar, and there is little cancellation in the formation of the overlap integral. This effect is likely to be most serious for light molecules and for systems with a large variation of transition moment with distance. 128 The correction for vibration-rotation interaction t o rotational temperatures measured from the 0-0 band of OH is as much as 200" a t about 3 0 0 0 " ~ . Molecular Energy Levels.-Potential energy curves. Potential energy curves of high accuracy are needed for many problems, but a t present there is no completely satisfactory method of constructing them. For light molecules such as H,, of course, remarkably accurate results can be achieved lZ9 by calculation ; for heavier molecules, necessarily rather crude approximations must be made, but results sufficiently reliable t o guide experimental work are beginning t o be obtained,l30 both for ground and for excited states. Most potential energy curves are therefore calculated from spectroscopic data and will be reliable only over the range of energies observed. Commonly Rydberg's 131 method, as modified by Klein l 3 2 and improved by Rees 133 (the RKR method), is used: this is equivalent to the Dunham treatment for low vibrational l 3 5 Amongst others, curves are now available for certain states of H2,136--13*BeH+,139CH+,139OH,140HF,141
lZ6 lZ7
'
Roy. SOC.,1962, A, 269, 311. lzsT. C. James, J . Chem. Phys., 1961, 35, 767. 129 W. Kolos and C. C. J. Roothaan, Rev. Mod. Phys., 1960, 32, 219. 1 3 0 S. Fraga and B. J. Ransil, J. Chem. Phys., 1961, 35, 669; H. Lefebvre-Brion, C. Moser, and R. K. Nesbet, ibid., 1961, 35, 1702; E. Theal Stewart, Ann. Reports, 1961, 58, 7. 131 R. Rydberg, 2. PhysiE, 1931, 73, 376; ibid., 1933, 80, 514. 132 0. Klein, 2. Physik, 1932, 76, 221. 1 3 3 A. L. G. Rees, Proc. Phys. SOC., 1947, 59, 998. 13*W. R. Jarmain, Canad. J . Phys., 1960, 38, 217. 135 A. C. Hurley, J . Chem. Phys., 1962, 36, 1117. 136 J. T. Vanderslice, E. A. Mason, W. G. Maish, and E. R. Lippincott, J . Chem. Phys., 1960, 33, 614; J. Mol. Spectroscopy, 1959, 3, 17; 1960, 5, 83. 137 D. Steele and E. R. Lippincott, J . Chem. Phys., 1961, 35, 2065. 138 I. Tobias and J. T. Vanderslice, J. Chem. Phys., 1961, 35, 1852. 139 S. H. Read, J. T. Vanderslice, and F. Jenc, J. Chem. Phys., 1962, 37, 205. 140 R. J. Fallon, I. Tobias, and J. T. Vanderslice, J . Chem. Phys., 1961, 34, 167. 141 R. J. Fallon, J. T. Vanderslice, and E. A. Mason, J . Chem. Phys., 1960, 32, 98; 1960, 33, 944.
3 . W. Pillow and S. E. F. Smallwood, Proc. Phys. Soc., 1962, 80, 560. 1 (a) T. C. James, J . Chem. Phys., 1960, 32, 1770; (b) R. C. M. Learner, Proc.
114
I2.l69
LiH,142, 143 RbH,142 C2,143, 144 CN 145 N29 1 3 7 , 146 CO,147 N0,148 02, 143, 1 4 9 Br2,150and 137 Examination of some of these results has suggested a new form of potential function which provides an inverse-power dependence a t large distances, and explicit relations between the potential constants and the spectroscopically observed quantities have been given.l 5 l The third approach is empirical, and many such functions have been proposed, the assumption being made that the potential curve fits a function whose parameters can be calculated from a limited number of observed spectroscopic constants. The simplest functions use only three constants, but it has been pointed out that a universal function of this kind cannot e ~ i s t . l 5 ~ The applicability and simplicity of some of these functions 154-159 have been compared by using the RKR method as a yardstick 152, 153 (see also refs. 160-167). The smoothness assumed.for most calculated potential curves has no theoretical justification, but most experimental curves will be fairly smooth.lB8 AG-v curves. I n several cases it has become clear that a large number of terms in the expression for the vibrational energy,
1379
1529
may be required t o fit the experimental results, so that extrapolations t o give we (and, similarly, B, and other constants) may be difficult t o perform.
142N. Singh and D. C. Jain, Proc. Phys. SOC.,1962, 79, 753. L. 143 N. L. Singh and D. C. Jain, Canad. J. Phys., 1962, 40, 420. 144 S. H. Read and J. T. Vanderslice, J. Chem. Phys., 1962, 36, 2366. 145 R. J. Fallon, J. T. Vanderslice, and R. D. Cloney, J. Chem. Phys., 1962, 37,
1097.
146
14
J. T. T7anderslice, E. A. Mason, and E. R. Lippincott, J. Chem. Phys., 1959,
I. Tobias, R. J. Fallon, and J. T. Vanderslice, J. Chem. Phys., 1960, 33, 1638. J. T. Vanderslice, E. A. Mason, and W. G. Maish, J. Chem. Phys., 1960, 31, 738; J. T. Vanderslice, ibid., 1962, 37, 384. 140 J. T. Vanderslice, E. A. Mason, and W. G. Maish, J. Chem. Phys., 1960, 32, 515. 1 5 0 N. L. Singh and D. C. Jain, Proc. Phys. SOC.,1962, 79, 274. 151 H. W. Woolley, J. Chem. Phys., 1962, 37, 1307. 152 Y. P. Varshni, Rev. Mod. Phys., 1957, 29, 664; 1959, 31, 839. 153 D. St,eele, E. R. Lippincott, and J. T. Vanderslice, Rev. Mod. Ph,ys., 1962, 34, 239. 154 P. M. Morse, Phys. Rev., 1929, 34, 57. 155 H M. Hulburt and J. 0. Hirschfelder, J. Chem. Phys., 1941, 9, 61; 1961, 35, . 1901. 156 N. Rosen and P. M. Morse, Phys. Rev., 1932, 42, 210. 15 G. Poschl and E. Teller, 2. Physik, 1933, 83, 143. 158 J. W. Linnett, Trans. Puraduy SOC., 1940, 36, 1123; 1942, 3 , 1. 8 159 A. A. Frost and B. Musulin, J . Chem. Phys., 1954, 22, 1017; J . Amer. Chem. SOC., 1954, 76, 2045. 160 Y. P. Varshni and R. C. Shukla, Proc. Plzys. Soc., 1960, 76, 794; Trans. Faraday SOC.,1961, 57, 537; J . Phys. Chem., 1961, 65, 2224; J . Chem. Phys.,1961,35,582. l e l C. L. Beckel, J. Chem. Phys., 1960, 33, 1885; E. J. Finn and C. L. Beckel, ibid., p. 1887. 162 W. L. Clinton, J. Chem. Phys., 1962, 36, 555, 556. 163 L. C. Cusachs, Cahiers de Phys., 1962, 16, 85. 164 R. Grandrnontagne, J. Phys. Radium, 1961, 22, 842. 165 M. R . Katti, Indian J. Phys., 1962, 36, 180. 166 T. Tietz, Acta Phys. Hung., 1961, 13, 359. 16 W. A. Bingel, 2. Nuturforsch., 1961, 16a, 668. 168 E. R . Davidson, J. Chem. Phys., 1962, 36, 2527.
148
30, 129.
115
The ground state of H, provides an example of this b e h a v i ~ u r .1690 ~ A ~~ , theoretical enumeration of the infLuence of various molecular-orbital configurations on the spacing of the vibrational levels in this state has now been given.169* It is concluded that there is a correlation between the shape of the AG-v curve and the variable ionic character of the H, molecule. It seems that it is necessary and sufficient to include (o,lso,ls') in the wave function in order to reproduce the shape observed for the AG-v curve, which has a slight positive curvature at small v and increasing negative curvature at large v. The observed curve may be fitted very exactly, especially with the addition of ( ~ ~ogZp)and (n,2p 2,2p), and it is possible that dissocia2 s tion energies in more complicated molecules can be estimated quite well using extremely simple wave-functions and the observed values of the fwst few AG's. For the ground state of I,, a pronounced tail is observed in the AG-v curve a t high v (see page 127). Crossing of potential energy curves. The Landau-Zener formula giving the probability of an electronic jump near the crossing-point of two potential surfaces has been re-examined,170and it has been found that the limits within which this formula applies are not often attained in practice. The interaction energy of the states that cross can be written E ~ ~ (and , the B ) if true Hamiltonian is written as the sum of a simple Hamiltonian H , and a perturbation operator V , i.e.,
=Ho
+ V,
then the approximation made in the Landau-Zener-Stuekelberg treatment is that
is constant, and that the potential energy curves are straight lines in the region of the crossing-point. The more exact treatment has considered the problem as a time-dependent perturbation, and formule for the interaction have been derived which hold for attractive and repulsive potential-energy curves. A generally applicable formula for the probability that the molecule has not crossed over into the second state by time t is
E12(B)dB. The fact that 'v is not zero for an interaction between two potentialenergy curves means that the separation of nuclear and electronic motion 171 Of (Born-Oppenheimer approximation) is invalid for such a course, when two potential energy curves do cross, the result is a perturbation of the energy levels of the two states as discussed below.
l a D (a;) M. Shafi and C. L. Beckel, J . Chem. Phys., 1962, 37, 2732; ( b ) G, M. Leks, id., p. 1418. l70 C. A. Coulson and K . Zalewski, Proc. Roy. SOC., 1962, A , 268, 437. 171 A. Witkowski, Bu1.l. Acad. polon. Sci., Ser. Sci. math. astron., 1961, 9, 697.
but its use is limited by the diEculty of computing
116
Perturbations. Examples of the intersection of potential-energy curves and the resulting perturbations have recently been analysed in the spectra of H2,172 CN,173, 1 7 4 CO,73 CS,23, 1 7 5 N0,176--178 AgD,179, 180 and IBr.49 Perturbations in the state B 3 n gof C, have been explained lS1by repulsion between the curves for A 3 n g and B3Hgwhich do not actually cross. For H2, CS, and N O both the states involved in the perturbations appear in the absorption spectra, so that the courses of the energy levels can be followed and the values of the perturbing matrix element, H , determined. In H2,172 the BICu+-CIHuperturbations are heterogeneous, AA = & l , and H 9 cm.-l: state B has a vibration frequency approximately twice that of state C, so the appearance of the absorption spectrum is roughly that of alternately unperturbed vibrational levels of C and perturbed B C levels. For NO, the interacting states are B211 and C211 in one case,176, 1 5 7 a n d H2C and H2nin a ~ e c 0 n d . l The first interaction has been studied ~~ in great detail. The variation of H as a function of excitation reveals a maximum near the 3-0 band of the C-X system and thus pin-points the exact region of crossing of the potential energy curves. Another interesting homogeneous perturbation (AA = 0) occurs in the spectrum of silver hydride, where the value of H is so large that only one state appears in the spectrum. Here the interactions are between the lZ+ states formed by the addition of a hydrogen atom to the 2 and 2 0 states of P the silver atom (see Fig. 3). I n AgH, the analysis shows that the state A lC + makes as if t o dissociate at a point only about 8000 cm.-l above its minimum, but then suddenly recovers itself and extrapolates to Ag(,P3/2). It is assumed 180 that the unseen l X + state from Ag(2D3,2)has a potential and energy curve with a minimum lying on the curve for 1C+(2P3/2), that 180 in the avoided crossing causes the perturbations. For AgD the levels AlX+ have been seen only to the point of the first kink in the curve: the levels are also violently perturbed. The homogeneous perturbation 0 +-3110+ in IBr has been discussed above. Interaction between the states B2Z+ and A211 in C N provides a good example of heterogeneous perturbations. I n particular, u = 10 in A2I-I perturbs u = 0 in B2Z +, and studies of the intensities of perturbed and extra lines provide information about the kinetics of formation of excited C X in active nitrogen flames. 1 7 3 Derived interaction parameters 174 explain both the positions of the observed lines and the observed Zeeman splittings. The possibility is envisaged of detecting microwave resonance between the energy levels in the neighbourhood of a perturbation. The study of perturbations is frequently important in that it may provide
1799
172 173
A. Monfils, Bull. class. sci., Acad. roy. Belg., 1961, 47, 585. N. H. Kiess and H. P. Broida, J. Mol. Spectroscopy, 1961, 7, 194. 17*H.E. Radford and H. P. Broida, Phys. Rev., 1962, 128, 231.
175
176
See ref. 58.
177
G . Herzberg, A. Lagerqvist, and E. Miescher, Canad. J. Phys., 1956, 34, 622. A. Lagerqvist and E. Miescher, Helv. Phys. Acta, 1958, 31, 221. 1 7 8 E. Miescher and K. P. Huber, Technical note, University of Basle, September,
179
lSo
1962.
lS1
U. Ringstrom, Arkiv Fys., 1962, 21, 145. R. C. M. Learner, Proc. Roy. Soc., 1962, A , 269, 327. D. C. Jain and P. Sah, Canad. J. Phys., 1962, 40, 1269.
B A R R O W A N D M E R E R : SPECTROSCOPY O F DIATOMIC MOLECULES
117
information (about molecular states) which is otherwise inaccessible. I n CO, the state n302n, Z - was first recognized 73 by its interactions with P A lll (although the forbidden transition IIZ--XIZ + has now been observed 69). CS provides good examples of perturbations made possible by spin-orbit interaction. l S 2 , 183 Here some of the very large perturbations of AlII arise by interaction with 3 X + and 3Z- states; constants for the from the analysis of the perturbations agree well triplet states derived
8,
FIU. 3. Suggested potential curves for AgH before and after interaction. 1 C ( 2 P )and 1 (2D) X curves before interaction. A l X and BIX after interaction.l*O (Reproduced, with permission, from Learner, Proc. Roy. SOC.,1963, A , 269, 327.)
wit,h those determined later by direct observation of the transitions 3C+ 3X---X1C+ in a b s ~ r p t i o n . ~ ~ Predissociation. Predissociations are classified as b, a, or c depending on whether the dissociation limit of the stable state lies above, approximately at, or below the crossing point with the predissociating state. It has now been shown lS4 that there are notable differences of behaviour when the crossing point is on the left-hand side of the potential-energy curve for the stable stmate, near the minimum, or on the right-hand side (i.e., if rc is the internuclear distance at the crossing point and re the internuclear distance in the stable state, according as r c < , w , or > r e ) . This classification is denoted by superscripts -, i, or respectively. The superscript zero is used for those cases where the curves lie close but do not cross.
KOVBCS, Canad. J . Phys., 1958, 36, 309. I. KOV&CS, Canad. J . Phys., 1958, 36, 329. lS4 R. S. Mulliken, J . Chsne. Phys., 1960, 33, 247.
lS2 I.
lS3
118
G E N E R A L A N D P H Y S I O A L CHEMISTRY
A case which is of some practical importance, but which has hitherto been neglected, is the c- case. I n the familiar case, cf, consideration of the effective potential-energy curves for the rotating molecule shows that there is a critical J value above which classical predissociation takes place, and that this J decreases with increasing v: tunnelling through the potential barrier is possible for smaller J values. I n contrast with this case, in c- the critical J value for a given vibrational level increases with v, and the tunnelling region lies above the classical region. Predissociation should now be strong near and below the critical J value (and, by tunnelling, above). It is suggested that an example of weak case c- predissociation occurs in the IT+state of CN+,185for which the levels up to J = 7 are missing in v = 2 and those up to J = 13 in v = 3. A stronger c- predissociation may be that in the state L3II, of Si,.1*6 Pine-structure esfects. The energy levels of the 4X- state in SiF 6o do not follow theoretical prediction,ls7 and the treatment hag been revised,l88 without making the approximation that the two p-type doubling constants, y I and yz, are equal. The fit with experiment is improved, but not perfect. Anomalous structure in A311i of NH,lS9in the corresponding state of PH,lgO and in 411u of O,+ 1919 1 9 2 is explained in terms of spin-spin interaction.l93, 1 9 4 It is also found 1 9 5 that the interaction between spin and rotation, which in a case-b state contributes the term H , = +Y[J(J 1) - X(S 1) - N ( N I)] to the rotational energy, must be included for multiplet rI and A states, as well as multiplet X states. Explicit formulae have been given for the energy, WRS,of the spin-rotation interaction for any degree of coupling between cases-a and -b. The full treatment of the rotational terms of a state such as A3Hi of NH must include perturbations by I I I states, spin-spin interaction, and, for levels below J = 3, where Hund's case-b does not apply exactly, spin-rotation interaction. Fine structure in the level N = 2 the C3n, state of hydrogen has been resolved,l96 and calculations have now been made of the fine structures of the lowest eight rotational levels of this state:lg7 these have explained anomalous spin-splitting.198 It is assumed that the observed splitting is caused entirely by spin-orbit and spin-other orbit interactions, together with spin-spin perturbations, rather than by mixing with other states or by spin-rotation- interaction.
KOV~CS, Optics and Spectroscopy, 1963, 13, i the press. n Lichten, Phys. Rev., 1960, 120, 848. 1 9 7 P. R. Fontana, Phys. Rev.. 1962, 125, 220. 198 E.W. Foster and 0. W. Richardson, Proc. Roy. SOC., 1947, A, 189, 175; 1953, A , 217, 433.
1961.
E. Douglas and P. M. Routly, Astrophys. J., 1954, 119, 303. A. E. Douglas, Canad. J. Phys., 1955, 33, 801. A. Bud6 and I. K O V ~ C2., Physilc, 1940, 116, 693. S 188 J. T. Hougen, Canad. J. Phys., 1962, 40, 598. 189 R. N. Dixon, Caiaad. J. Phys., 1959, 37, 1171. lgoF. Legay, Canad. J. Phys., 1960, 38, 797. 1 9 1 I. KOVACS, Acta Phys. Hung., 1959, 10, 255. l9Z I. KovBcs and S. Weniger, J . Phys. Radium, 1962, 23, 377. l g 3 I. KOVBCS, Acta Phys. Hung., 1960, 12, 67. 1 9 4 I. KOVBCS, Acta Phys. Hung., 1961, 13, 303.
186 A.
186
lg6 W.
BARROW A N D M E R E R : SPECTROSCOPY O F DIATOMIC MOLECULES
119
Isotope effects. In addition to the usual vibrational and rotational mass effects, small effects have been observed for HgH l 9 9 and for H,.200 I n a comparison of lg8HgHand 2ooHgH, the difference in nuclear volume leads to a small isotope splitting. I n studies of H,, HD, and D,, a very small difference is found between D,(H,) and D,(D,). This arises from the effect of nuclear motion on the electronic energy of two separated atoms and the corresponding effect in the molecule. The application of calculated corrections to the observed values leads t o estimates of De(COH2), D, value the for infinite mass, which agree most satisfactorily one with another, and with the calculated value.129 D,(H,) is given as 36113.0 0.3 cm.-l. New Species.-One of the classical applications of spectroscopy is that of the identification of transient or reactive species, and we now discuss some recent observations in this field. IntermetaZZic compounds. Interest in high temperature chemistry and the development of mass-spectroscopictechniques has led to the discovery of a number of new species, often of surprising stability. Some years ago a band system, attributed at the time to AlC, but which perhaps arises from Al,, was observed in absorption and in thermal emission when aluminium was heated under reducing conditions in a King hrnace.201 Since then, diatomic spectra of the Group IB elements have been obtained, CU,,~O* Ag2,202b 2, 2039 ,O* and CuAgY2O5 Au CuAu,206 and AgAu.,07 The molecules containing gold are particularly stable, and several compounds with elements of other groups have been detected. AuBe,208,AuMg,204A u C ~AuBaY2lo , ~ ~ ~ and AuAl ,O* all give band-systems in the visible region of the spectrum, while AuSn,,ll AuCr,212 and AuPd have been detected mass-spectrometrically. Rotational analyses have been carried out for Cu, 213 and for I n both cases the ground states are 1Z+ (or O+), and the values of re are 2.219 and 2.338 A, respectively, somewhat shorter than would have been expected from single-bond covalent radii. The dissociation energies of many of these molecules have been determined by mass-spectrometric studies of the high-temperature equilibria. The values of Do for Cu,, Ag,, and Au, are interesting: they are 45.5, 37.6,
-+
lg9 T. L. Porter, J. Opt. SOC. Amer., 1962, 52, 1201; T. L. Porter and S. P. Davis, <bid., p. 1206. 2 o o G. Herzberg and A. M o d s , J. Mol. Spectroscopy, 1960, 5, 482. 201 P. B. Zeeman, Canad. J. Phys., 1954, 32, 9. 2 0 2 (a) B. Kleman and S. Lindqvist, Arkiv Fys., 1954, 8, 333; (b) B. Kleman and S. Lindqvist, Arleiv Fys., 1955, 9, 385. 203 B. Kleman, S. Lindqvist, and L.E. Selin, Arkiv Fys., 1954, 8, 505. 204 J. Ruamps, Ann. Phys., 1959, [13], 4, 1111. 2 0 5 K. C. Joshi and K. Majumdar, Proc. Phys. SOC., 1961, 78, 197. 2 0 6 J. Ruamps, C m p t . rend., 1954, 239, 1200. 2 0 7 J. Ruamps, Proc. Colloq. Spectroscop. Internationale VI, Amsterdam, 1956, Pergamon Press, 1957. z o 8 R. F. Barrow, W. J. M. Gissane, and D. N. Travis, unpublished work. 2 0 g J. Schiltz, Compt. rend., 1961, 252, 1750. 210 J. Schiltz, Compt. rend., 1961, 253, 1777. 211 M. Ackerman, J. Drowart, F. E. Stafford, and G . Verhaegen, J. Chem. Phys., 1962, 36, 1557. 212 M. Ackermrtn, F. E. Stafford, and G. Verhaegen, J. Chem. Phys., 1962, 36, 1560. 213 D. N. Travis and R. F. Barrow, Proc. Chem. Soc., 1962, 64. 214R. Barrow and D. N. Travis, Proc. Roy. SOC.,1963, A, in the press. F.
120
and 51.5 kcal./mole, respectively (with an estimated uncertainty of 2.2 kcal.). This sequence is followed in other diatomic compounds of these elements. The strongest bonds are formed by gold and the weakest by silver, while copper is intermediate. There is mass-spectrometric evidence for molecules of this type formed from elements of other groups, such as GaP and GaAs.,16 No doubt many more species of this kind await discovery. Dissociation energies of the homonuclear molecules have been correlated with bond energies in the solid.217 Mercury and the rare gases. Band systems arising from very weaklybound molecules, such as Hg,, have been known for a long time. New observations on the absorption bands observed in pure mercury vapour, in the region 2700 t o 2970 8, have been reported and detailed calculations of the spectra of HgAr and of HgKr have been made.219 Structure provisionally assigned t o a transition [W2P,) K + l + [&(lS,) K+l has been observed,220and bands arising from mixed rare gas molecules or, more probably, their positive ions, have been reported, for example, for HeNe?+,221 ArXe?+,222 KrXe?+.223 These bands show little structure, and so that the information that can be derived from them is limited. However, the molecule XeO gives rise to a system near 5577 8, the wavelength of lXo-lDz in O(I), which shows both vibrational and rotational s t r ~ c t u r e . ~ , ~ The heads can be represented by the equation
Y = 20097
+ [142v - 9 . 9 ~ +~0 - l d 3 ]
[360v - 1 2 * 0 ~ ~ ]
and extrapolations give Do = 1.5; Do = 7.7 kcal./mole. Branches in the rotational structure have been picked out, but there is a good deal of overlapping, and a, rotational analysis has not yet been given. A band which appears t o arise from XeN has also been observed.225 DoubZy charged positive ions. Until recently the spectroscopy of diatomic species has been confined t o the study of neutral molecules or of singly charged positive ions. In 1958, a band was observed in the vacuum ultraviolet region a t 1590 8, emission from a hollow-cathode discharge in in nitrogen a t low pressure.226 The band consists of single R and P branches, with B rv B, and the lines show alternating intensity. Since only the one band is observed, it is evidently a 0-0 band. The transition could therefore conceivably be lZ-lZ, in N,, or 2C-2Z in ??,+. However the rotaM. Ackerman, F. E. Stafford, and J. Drowart, J . Chem. Phys., 1960, 33, 1784. A. J. Ahearn and C . J. Thurmond, J . Phys. Chem., 1962, 66, 575. 217 G. Verhaegen, F. E. Stafford, P. Goldfinger, and M. Ackerman, Trans. Faraday Soc., 1962, 58, 1926. 21* I. Agirbiceanu and A. Ichimescu, B u l . Inst. Politek. Bucaresti, 1959, 21, 41. 219 A. Michels, H. deKluiver, and C . A. Tenseldam, Physica, 1959, 25, 1321. 2 z O L . Herman and R. Herman, Nature, 1962, 195, 1086. 2 2 1 H J. Oskam and H. M. Jongerius, Physica, 1958, 24, 1092. . 2 2 2 H. M. Jongerius, J. L. vanKoeveringe, and H. J. Oskam, Physica, 1959, 25, 406. 2 2 3 W. Friedl, 2. Naturforsch., 1959, 14a, 848. 2 2 4 C. D. Cooper, G. C . Cobb, and E. L. Tolnas, J . NoZ. Spectroscopy, 1961, , 223. 7 2 2 5 L. Herman and R. Herman, Nature, 1962, 193, 156. 2 2 6 P. K. Carroll, Canad. J . Phys., 1958, 36, 1585.
215
216
B A R R O W A N D M E R E R : S P E C T R O S C O P Y OF D I A T O M I C M O L E C U L E S
121
tional constants for the two states do not agree with those for any known state of these species. It is now believed 227 that the band arises from a analogous to the Mulliken bands of C2. This transition lCu+-lCg+in N2++, identification is supported by the results of a theoretical treatment in which the potential energy curve for a doubly charged positive ion is derived from the corresponding curve for the isoelectronic neutral 229 It is predicted that band-systems of other doubly charged ions such as 022+ and NO2 + should be observable. + should also possess a potential minimum in the ground state : 2 3 0 calculated constants are re = 0.71 A; cue = 3295 cm.-l; D,= 28 kcal./mole. Other Molecules.-Finally, there follows a brief summary of recent work on some molecules, of particular interest, not discussed above. AZkaZi-metal molecules. Rotational analyses of some of the ultraviolet bands in the absorption spectra of Li2,231,2 3 2 Na2,231 and K2 233 have shown that they arise by transitions from the ground states XI&+ to excited lrIu states. These lI1, states appear to be Rydberg states, and it is therefore possible to determine, by extrapolation, the molecular ionization potentials. The difference in molecular and atomic ionization potentials is equal to the difference between the dissociation energies of the molecule-ions and of the neutral molecules, thus ip(M) - ip(M2) = D(MZ+) - D(M2). Results, in cm.-l, are as follows:
Li Na K
iP(M) 43490 41450 35010
iP(M2) 40000 39300 33000 4iP) 3490 2150 2010
Thus the ions, M2+, are appreciably more stable than the neutral molecules, a conclusion which is supported by calculation.234 Hydrogen halides. The predicted transition between the ionic state VIE+ and the ground state X I C + of the hydrogen halides was first observed 235 in emission for H F and DF. Similar bands of HC1 have been analysed,236 and part of the system of HBr has been observed but not analy~ed.23~ The transitions observed in these systems are between states of low v f to high v. Extensive information 238 on states of lower d f has been provided by the study of the vibration-rotation bands of HF excited in a hydrogen-fluorine diffusion flame, where bands up to 9 4 and 9-5 have
P. K. Carroll and A. C. Hurley, J. Chem. Phys., 1961, 35, 2247. 2 2 8 A .C. Hurley and V. W. Maslem, J. Chem. Phys., 1961, 34, 1919. 2 2 9 A. C. Hurley, J. Mol. Xpectroscopy, 1962, 9, 18. 2 3 0 S. Fraga and B. J. Ransil, J. Chem. Phys., 1962, 37, 1112. 231 R. F. Barrow, D. N. TravG, and C. V. Wright, Nature, 1960, 187, 141. 232 R. Velasco, Anales real. SOC. espaii. Pis. Quim, 1960, 56, A , 175. 233 E. W. Robertson and R. F. Barrow, Proc. Chem. SOC., 1961, 329. 2 3 4 J. E. Faulkner, J. Chem. Phys., 1957, 27, 369. 235 J. W. C. Johns and R. F. Barrow, Proc. Roy. SOC., 1958, A , 251, 504. 236 J. K . Jacques and R. F. Barrow, Proc. Phys. SOC., 1959, 73, 538. 2 3 7 J. G. Stamper and R. F. Barrow, J. Phys. Chem., 1961, 65, 250. 238 D. E. Mann, B. A. Thrush, D. R. Lide, J. J. Ball, and A. Acquista, J. Chem. Phys., 1961, 34, 420.
227
122
been observed. Information is thus available for the rotational and vibrational levels of the ground state of HF over most of the range from d = 0 ' to the dissociation limit. As in the case of H,, it is found that a large number of terms is required to express the variation with v f f of B,, of D,, and of the vibrational energy, G,. Predissociation by rotation is observed in the ground state, and leads to a rather precise value for the dissociation energy of HF. Constants for the excited states, V(on4o*, lZ+), are as follows:
To, (cm.-l)
HF HCl HBr 83275 76245 (74900)
we (cm.-l)
re
(A)
1158.5 877.2 (790)
2.092 2.530 (2.7)
The values for HBr have been e s t i m ~ t e d . , ~ ~ The absorption spectra of HBr 239 and of DBr 240 in the Schumann region have been studied with high resolution, and some thirty electronic states have been found between 8.2 and 10.4 ev. The states divide roughly into two groups, those with B B", and those with B 0.5 B". Neither vibrational structure nor Rydberg series are obvious features of the spectra, and the isotope relations are not always clear. Many of the bands have unusual structures, suggesting that the normal coupling cases are not always followed in these highly excited states. Rotational analyses of the vacuum ultraviolet bands, B and C , of DC1 have been given.241 Although systems of HCl+ and of HBr+ are well known, no spectra 235 of HF+ or of HI+ have yet been observed. Electron-impact measurements have provided data on these ~pecies.2~~ Nitrogen. The large number of states known for the N, molecule have been classified 243 and a detailed review of the spectroscopic information about this molecule has been given.244 The lower-lying states 245 arise from the configurations . nu40g2, . . zu40gzg, . . . nu3ag2ng: . and constants for these states are given in Table 2.70, 71, 243, 246 It will be seen that only one state remains to be observed, 3Au,and that, apart from b'lZ,+, the states of a given configuration have closely similar vibrational and rotational constants. A theoretical treatment z45 shows that the lXu+ state is highly ionic, and predicts that the transition t o the ground state should be strong. The state b' is in fact the lowest I&+ state of N, to which an intense transition to the ground state occurs. Two other states 'Zu+ and 5Zg+arise from the ground state atoms. The former is repulsive, but the latter, which is important in that it causes predissociations in and in B3Hg and is also involved in the Lewis-
. .
R. F. Barrow and J. G. Stamper, Proc. Roy. SOC., 1961, A , 263, 259, 277. J. G. Stamper, Canad. J . Phys., 1962, 40, 1279. 241 J. G. Stamper, Canad. J . Phys., 1962, 4 , 1274. 0 242D. Frost and C. A. McDowell, Canad.,+ Chem., 1958, 36, 39. C. 243 R. S. Mulliken in " The Threshold of Space (ed. M. Zelikoff), Pergamon Press, London, 1957, p. 169. 2 4 4 A. Lofthus, " The Molecular Spectrum of Nitrogen," Oslo University, 1960. 2 4 6 R. S. Mulliken, Canad. J . Chem., 1958, 36, 10. 24sP. G. Wilkinson and N. B. H o d , J . Chem. Phys., 1956, 24, 528.
23s
240
B A R R O W A N D M E R E R : S P E C T R O S C O P Y O F D I A T O M I C MO LEC U LES
123
TABLE Low-lying states of N2 2.

Configuration
nu3ug2ng
n4ugq7
7ru4ug2
State Too 103672 b&+ 7 1697.7 wlAu 67738.2 alCUBYCCzL- 65850.6 [60500] 49757 A3&+ 68951.2 dIIg 59314 B311g 0 X1C,+
me
Be
1.154 1.498 1-480 1.472 [ 1-46] 1-439 1.616 1-638 1.998
751.6 1548 1530.0 1517-7 [1490] 1460.4 1694.1 1734.1 2358.1
The constants for 3Au are estimated values.243
Rayleigh afterglow, has a shallow minimum. Calculated constants 247 are To, 77925; 12, = 1100; cr), = 650 cm.-l; re = 1.558. It may be = assigned the molecular-orbital configuration
but the properties of the observed state must be partly determined by interaction with more highly excited 5Eg+ s t a t e ~ . ~ ~ * There now seems to be no evidence for the existence of a long-lived following metastable state of N, at about 8 ev, which had been suggested,249 the observation of ions and of resonance radiation of Ba(I1) from a xenonnitrogen discharge to which Ba vapour had been added. Chemi-ionization by nitrogen-atom recombination provides an explanation of the phenomena.250 Other work on nitrogen includes studies of afterglows,251 of excitation in high tension discharges,252 and of the absorption spectrum 253 at the short-wavelength end of the Schumann region. I n N2+,new observations 254 in the B2Xu+-X2&,+ system have been reported, bands of the 211g-A211u system have been a n a l y ~ e dand~ the ,~ ~ Z existence of an excited 4 state discussed.256 A collection of band-head measurements of N2 and of N2+,has been Carbon monoxide-lead telluride. The lowest states of CO are rather similar to those of N,, and of the states arising from the first two excited configurations (n40n* and nWn*) only the 1C+ and 1A states remain unobserved. The state n302n*3A has been identified by rotational analysis of the triplet bands.66 Transitions from the ground state to only two of the
P. K. Carroll, J . Chem. Phys., 1962, 37, 805. 2 4 8 R . Mulliken, J . Chem. Phys., 1962, 37, 809. S. 2 4 9 C. Kenty, J . Chem. Phys., 1961, 35, 2267. 260 C. Gatz, F. T. Smith, and H. Wise, J . Chem. Phys., 1961, 35, 1500; A. B. King and C. Gatz, ibid., 1962, 37, 1566; C. Kenty, ibid., p. 1567. 2 5 1 0. Oldenberg, Planet Space Science, 1959, 1, 40; Y. Tanaka and A. S. J m a , J . Opt. SOC. Amer., 1961, 51, 1239; L. Herman and R. Herman, Nature, 1961, 191, 346; W.B. Kunkel and A. L. Gardner, J . Chem. Phys., 1962, 37, 1785; R. A. Young, ibid., 1962, 36, 2854. 252 G. Pannetier and L. Marsigny, J . Chem. Phys., 1962, 59, 856. 253 Y. Tanaka, Mkm. SOC. Roy. Sci. Lidge, 1961, 4, 198; N. Damany-Astoin, L. Sanson, J. Romand, and B. Vodar, ibid., p. 202. 2 5 4 D. C. Tyte, Proc. Phys. Soc., 1963, 81, 163. 2 5 5 Y. Tanaka, T. Namioka, and A. S. Jursa., Canad. J . Phys., 1961, 39, 1377. 2 5 6 V. (4ermak and Z . Herman, Coll. Czech. Chem. Comm., 1962, 27, 1493. 2 5 7 L. Wdlace, Astrophys. J., 1962, 135, 977.
247
124
excited states from these configurations are allowed. With increasing atomic number, the pattern changes. I n SiO and SiS, and in later members, the (partly) ionic excited state 2z3cr2n*lZ+ falls a t much lower energies than in N,: its character as lC+ has been established by rotational analysis in the cases of SiS,258 SnS,lS and PbOa20 It is also this state which is presumably the upper state of the strong system of P,, A lC:,+-XIC, +. The large decrease in excitation energy of this state on going from N, to P,, or from CO to SiO, may be associated with the fall in ionization potential on going from the first-row to the second-row elements. The absorption spectra of heavy molecules such as PbO 2o and PbS 25s are qualitatively different from that of CO; in place of the single low-lying allowed transition in CO, AIII-XIC+, a t least six systems are observed for PbO and seven for PbS. SnS l9 presents an intermediate case. Either new, low-lying, molecular orbitals are available for the heavy molecules or the coupling changes towards Hunds case-c. Evidence from the character and number of the observed states suggests that the latter is the more likely conclusion. Dissociation energies of some of these molecules have been determined mass-spectrometrically as follows :
Do(SnS) 260
D,(PbS) Do(PbSe) 261 D,(PbTe)
261
= 110.1 5 3.0 kcal./mole = 79.1

= =
& 2.8 ,, 61.5 2.5 51.4 & 2.0 ,,

yy
,, ,,
,,
Nitric oxide. The absorption spectrum of nitric oxide 262, 2 6 3 is peculiarly complicated through the overlap of transitions to weakly bound nonRydberg states (with extensive vibrational structure) with Rydberg transitions t o states converging on NO+ (which is more tightly bound than NO). These states lie unusually low in odd-electron molecules and except for the which has not yet been certainly identified, the lowest excited predicted 4n[iy state is a Rydberg state, A2X +, which may be written [NO +, XIZ +I 380. The properties of the non-Rydberg states are summarized in Table 3.262-264 They arise from the configurations ( ~ c r ) ~ ( w n ) ~ (andt ) ~ vn ( x c ~ ) ( w n ) ~ ( zwhich lead t o states notably less stable than the ground m)~, state. X12+, The ground state of the NO+ ion is ( x ~ r ) ~ ( w n ) ~ and a transition crn4nA 1 n + X has been analysed:266 perturbations in this system give evidence for a 3 2 - state from cr2n3n. The value of AG,, 2344-4crn.-l,
2 5 8 R . F. Barrow, J. L. Deutsch, A. Lagerqvist, and B. Westerlund, PTOC. Phys. SOC., 1961, 78, 1307. 259R. Barrow, P. W. Fry, and R. C. Le Bargy, Proc. Phys. Xoc., 1963, in the F. press. 260 R. Colin and J. Drowart, J. Chem. Phys., 1962, 37, 1120. 261 R. F. Porter, J. Chern. Phys., 1961, 34, 583. 2 6 2 A. Lagerqvist and E. Miescher, Helv. Phys. Acta, 1958, 31, 221. 263 A. Lagerqvist and E. Miescher, Canad. J. Phys., 1962, 40, 352. 2 6 4 E. Miescher, Helv. Phys. Acta, 1956, 29, 401 ;E. Miescher, J. Quantit. Spectroscopy and Radioactive Transfer, 1962, 2, 421.
B A R R O W A N D M E R E R : S P E C T R O S C O P Y O F DIATOMIC MOLECULES
125
TABLE Non-Rydberg states of NO 3.

Configuration
07r4d
State G2ZB'2A
TOO
We
2Cf
62503 59415 ?unstable 45486 (25900) ( y 9
1087.6 1216.6
-
Be 1.245 1.330
-
(*C-)
027r37r2
B2Ii1,
1037.7 1903.8
1.126 1.705
(4J&)
027r47r
x n 2 r
Notes :Bands ascribed to the transition 4Z---4II have been observed but no detailed analysis has yet been given.26j For the 411-X211 transition, see p. 106. The configuration 0 2 ~ 3 also gives 211, 2IIi, and 2 0 states. The 2 4 , state has not ~ 2 been observed, but there is evidence for two non-Rydberg aII stab, 211 and 211s a t 64287 and 65931 cm. - l respectively.263
agrees well with the Raman shifts of 2330 and 2340 crn.-l observed for NO+ in solids and in solution, respectively.267 Three Rydberg series have been analysed in the absorption spectrum of nitric oxide a t the short-wavelength end of the Schumann 269 Of these, one, the y-series, converges on AlII of NO+, and may be written [0z4n, A1II]npa,2 I I : n = 4 , s . . .lo. The bands follow the formula Y = 147830 - R / ( n - 1 ~ 7 8 ) ~ . Thus the first ionization potential of NO is given by 147830 - To0(A1II) 74746 cm.-l, or 9.267 & 0.005 ev, in good agree= ment with values 9.25 & 0.03 270 and 9-25 & 0.02 2 7 1 ev obtained by photoionization. Two other series, a and p, follow the formuke a : Y = 114680 - R / ( n - 1.10)2; n = 3 , 4 . . . 10 ~; 16: Y = 133550 - R/(n - 1 ~ 6 7 )n = 4, 5 , . . . 14. These series are thought t o be a : [a2n3n, +]nscr,2C + a3E p : [02z3;2, ? 3np0, ? . Thus present information about NO+ may be summarized as follows:
State AlIT
* 58804 39934 X1C+ 0 2377-1 2.002 * Two very different values have been given for the vibrational interval in the /3 series, 1341 2 6 8 and 1980 2 6 9 cm.l-.
I
3c-
Too 73084
?
we
1608.9 [1150]
Be 1.587 1.25
a3if
2 6 5 M. Ogawa, Science o Light, 1954, 3 39, 87; M. Brook and J. Kaplan, Phys. f , Rev., 1954, 96, 1540. 2 6 6 E. Miescher, Helv. Phys. Acta, 1956, 29, 135. 267 W. R. Angus and A. H. Leckie, Proc. R o y . SOC.,1935, A , 149, 327; 1935, A 150, 615; Trans. Paraday Xoc., 1935, 31, 958. 2 6 B Y . Tanaka, Sci. Papers Inst. Phys. Chem. Res., T o k y o , 1942, 39, 456. 2 6 s K. P. Huber, Helv. Phys. Acta, 1961, 34, 929. H. Hurzeler, M. G. Inghram, and J. D. Morrison, J . Chem. Phys., 1958, 28, 76. K. Watanabe, J . Chem. Phys., 1957, 26, 542.
126
As is to be expected, there are close parallels with the lower excited states of N,. I n addition, there is a large number of states of NO whose identification as Rydberg states, converging on the ground state of NO+, follows from their values of cr), and of Be (Table 4). Comparison with the states of O,, N,, CO, and their ions, has assisted in the identification of some of these ~tates,~~9 but this is rendered diflicult by overlapping and by perturbations, so that series are not obvious features of the spectrum in this region, and more work remains to be done. It is remarkable how closely the constants for A2X+, the first Rydberg state, agree with those for XIS+ in NO+. This suggests that it may be possible to predict, rather accurately, the constants of the isoelectronic monohalide ions such as CF+, whose spectra have nqt yet been observed, from observations on the lowest Rydberg states of
TABLE4.
Rydberg states of NO converging on NO+ (X1c+).263, 269

1'00
State
s
M
we
2z:+
2Zf
5so 5do
H' 2 I I an: H 211 P 2A E 2Z+ D 2Z+

2 n
" "
?
3d6
4sa
2Z+
4do 3pn 3so
67135 64659 64290 62717 62706 62039 60863 53291 52373 44199
AGi 2377 2348

-
2379 AG, 2339 AG, 2315 2373.6 2323.9 2395 2374.8
Be 1.979 2.037 B, 1.85 2.017 2.014 Bo = 1.967 1.986 2.003 2.002 1.997
the neutral molecules. The atomic dissociation products for several of these states have been 272n and potential energy curves d r a ~ n . ~ ~ , Transitions between excited states give rise to several systems observed in emission in the visible and infrared regions.263, z 7 Z c 8,. I n comparison with O,, rather little is known about the electronic states of S,. The structure of the well-known system B3Zu--X3C,- is interesting but is not yet fully understood.273, 7 4 The upper state is exten2 sively perturbed, perhaps by a state 31-Iu, and the observation of branches TR31,RP31, PR13, and NP,3 enables the spin-splitting constants in the ground state to be determined.275 y is small, ca. -0.007 cm.-l, but h is quite large, and increases with v thus:
A,
= 11.6,
+ 0*077,(V + *) + 0.0013,(~+
&)2.
Several other systems have been observed in emission, both a t long waveThe lower state of some of the lengths 2 7 4 and in the ultraviolet regi0n.2~~ latter systems is probably the lZg+ state from the lowest configuration . . . nU4og2ng2, its position relative to X 3 X g - is not yet known. but
2 7 2 (a) D. D. Konowalow and J. 0. Hirshfelder, Phys. Fluids, 1961, 4, 637; (b) R. A. Young and R. L. Sharpless, Disczlss. Faraday Soc., 1962, 33, 228; (c) W. H. Wurster, C. E. Tremor, and H. M. Thompson, J. Chem. Phys., 1962, 37, 2560. 273 K. Ikenoue, Science of Light, 1960, 9, 79. 2 7 4 J. E. Meakin and R . F. Barrow, Canad. J . Phys., 1962, 40, 377. 2 7 6 R. F. Barrow and J. M. Ketteringham, Canad. J. Phys., 1963, 41, 419. 2 7 6 Y . Tanaka and M. Ogawa, J. Chem. Phys., 1962, 36, 726.
127
The value of the dissociation energy has not yet been established beyond doubt: however it seems probable that
Do
4 4 ev, or .
0298
= 102
& 3 k~al./mole.~~~
PF. The spectrum of the molecule PF, isoelectronic with SO, has recently been observed.28 Both singlet and triplet systems were observed and it appears that the ground state is 3Z-. However in place of the expected 3C--3Z- system, there appeared a system 3H-3X-. The two singlet states from the lowest configuration, 1A and l1: +, were both observed, but their positions relative to X3C- are not known. A 2Z-2rZtransition in PF+ has also been a n a l y ~ e d . ~ ~ ~ system of C1, CE,, I,. A new analysis 2 7 9 of bands of the 3110,+-1Cg+ has led to improved constants for both states. A resonance fluorescence system has been observed 280 in the Schumann region, and gives information about the ground state constants at large values of v. A study of the resonance fluorescence system of I, has provided accurate information about the course of the ground-state vibrational levels to a point very close to the dissociation limit.16 The dissociation energy, Do, is 124526 & 1.5 cm.-l. Between 4.6 and 6 . 4 & the form of the potential energy curve for the ground state suggests that in this region dispersion forces are more important than valency forces.281 Rotational structure has also been studied for the following molecules : Hydrides. CH 2 8 2 (atlas, 3000-5000 A), OH (vibrati~n-rotation;~~~ A22+-X2H ;284 C2z +, B2C+-A2C+ 285), MgH, MgD,286 CaH,287, 288 SrH,288 BaH,288 ZnH, ZnD,289AlD,290 YbH.Zg1 Oxides. Mg0,293As0,1g4AsO +,295 Se0,296TiOY2g7 YO.298
2 7 7 L. Brewer, J . Chem. Phys., 1959, 31, 1143; R. Colin, P. Goldfinger, and M. Jeunehomme, Nature, 1960, 187, 408. 2 7 8 A. E. Douglas and M. Frackowiak, Canad. J . Phys., 1962, 40, 832. 2 7 9 W. G. Richards and R. F. Barrow, Proc. Chem. SOC., 1962, 297. 2 8 0 Y. V. Rao and P. Venkateswarlu, J . Mol. Spectroscopy, 1962, 9, 173. 281 G. L. Caldow and C. A. Coulson, Trans. Faraday SOC., 1962, 58, 633. 2 8 2 A. M. Bass and H. P. Broida, Nat. Bur. Stand., Monograph, No. 24, 1961. 283 L. Wallace, Astrophys. J., 1960, 132, 894; A. M. Bass and D. Garvin, J . Mol. Spectroscopy, 1962, 9, 114. 2 8 4 G. H. Dieke and H. M. Crosswhite, J . Quantitative Spectroscopy and Radiative Transfer, 1962, 2, 97. 285 L. Herman, P. Felenbok, and R. Herman, J . Phys. Radium, 1961, 22, 83. 2 8 6 M. A. Khan, Proc. Phys. SOC., 1961, 77, 1133; 1962, 80, 209, 523. 2 8 7 M. A. Khan, Proc. Phys. SOC.,1962, 80, 593. 2 E 8 G. Edvinsson, I. Kopp, and B. Lindgren, Nuturwiss., 1968, 49, 418. M. A. Khan, Proc. Phys. SOC., 1962, 80, 599. 2 9 0 M. A. Khan, Proc. Phys. SOC., 1962, 79, 745. 291 I. Kopp, Naturwiss., 1962, 49, 202. 2 9 2 Yu. Ya. Kuzyakov, V. M. Tatievskii, and L. N. Tunitskii, Optics and Spectroscopy, 1960, 9, 84. 293 L. Brewer and S. Trajmar, J . Chem. Phys., 1962,36, 1585; L. Brewer, S. Trajmar, and R. A. Berg, Astrophys. J., 1962, 135, 955. 2 9 4 L. Klynning, Naturwiss., 1962, 49, 252. 295 C. V. V. S. N. K. Santaram and P. T. Rao, Proc. Phys. SOC., 1962, 79, 1093. 2 9 6 R. F. Barrow and E. W. Deutsch, Proc. Phys. SOC.,1962, 80, 993. 2 9 7 A. V. Petterson and B. Lindgren, Arkiv Fys., 1962, 22, 491. 2 9 8 U. Uhler and L. Akerlind, Arkiv Fys., 1961, 19, 1.
128
HaEides. LiF (vibration-rotation),299 MgCl,300 CaC1,301 GaCl,302 CC1,303 SnF,304 BiF,305 BiCl,306 CuC1,307 CN 308 and C,.309 Values of the dissociation energies of B,, C,, and of CN are reported as folIows : D0"(B2) 310 = 65.5 - 5.5 ; Do"(C,; I&+) 311 = 144; & D0"(CN)312 = 174 -= kcal./rnole. j3 Vibrational structure in the ground state of H,+ has been detected by electron-impact experirnents.313
R. F. B. A. J. &I. R. F. BARROW. R. A. CRAIG. R. P. H. GASSER. J. H. KNOX.
29g
M.L. MCGLASHAN. A. J. MERER. R. E. RICHARDS. M. C. R. SYMONS.
K. P. Vasilevskii and V. I. Baikov, Optics and Spectroscopy, 1961, 11, 21. E. Morgan and R. F. Barrow, Nature, 1961, 192, 1182. 301 E. Morgan and R. F. Barrow, Nature, 1960, 185, 754. 302 I. R. Bartky, J . Mol. Spectroscopy, 1960, 5, 206. 303 R.D. Gordon and G. W. King, Canad. J . Phys., 1961,39,252; R. D. Verma and R. S. Mulliken, J . Mol. Spectroscopy, 1961, 6, 419. 3 0 4 R. F. Barrow, I. Kopp, and A. J. Merer, Proc. Phys. Soc., 1962, 79, 749. 3 0 5 T. A. P. Rao and P. T. Rao, Canad. J . Phys., 1962, 40, 1077. 306 B. N. Khanna, J . Mol. Spectroscopy, 1961, 6, 319. 3 0 7 P. M. Rao, R. K. Asundi, and J. K. Brody, Canad. J . Phys., 1962, 4 , 412, 0 423, 1443; A. Lagerqvist and V. Lazarova-Girsamof, Arkiv Fys., 1962, 20, 543. 308 G. Pannetier, L. Marsigny, and M. Bremond, J . Chim. phys., 1962, 59, 730; G. Pannetier and L. Marsigny, Bull. SOC. chim. France, 1962, 1537. 309E.A. Ballik and D. A. Ramsay, unpublished work. 310 G. Verhaegen and J. Drowart, J . Chem. Phys., 1962, 37, 1367. 311 L. Brewer, W. T. Hicks, and 0. H. Krikorian, J . Chem. Phys., 1962, 36, 182. 312H. T. Knight and J. P. Rink, J . Chem. Phys., 1961, 35, 199. 313 L. Kerwin, P. Marmet, and E. Clarke, Canad. J . Phgs., 1961, 39, 1240.
300
INORGANIC CHEMISTRY
1. INTRODUCTION
THEnumber of papers dealing with organometallic compounds continues t o increase, and the dividing line between organic and inorganic compounds is becoming increasingly difficult t o define. In this Report, we direct attention to those papers where the emphasis is on the properties of elements other than carbon, although organic groups may be used extensively in some cases to elucidate or illustrate these properties. As in the last few years, complex compounds, and compounds of boron, silicon, and phosphorus, continue t o occupy a large proportion of the Report; it is perhaps not too fanciful to hope that sooner rather than later the intensive studies on these particular non-metals may produce groups of inorganic atoms which are as versatile and as tractable in their behaviour as the familiar organic groups such as methyl, ethyl, and phenyl. The appearance of a new journal 1 devoted exclusively to inorganic chemistry is to be welcomed. The second volume of the revised Brauers Handbook has followed the first with commendable rapidity; two new textbook^,^ and new editions of two established have also appeared. Tables of atomic weights on the new 12C = 12 standard have been published. General reviews cover inorganic heterocycles, 6 dissolution of metals in fused halides, reactions in liquid ammonia,s properties of metal-amine solutions, high-temperature inorganic chemistry, vinyl compounds of metals, and primary solid hydrides.1 A. K. H. D. N.
Inorganic Chenzistry, American Chemical Society, 1962, 1 . Handbuch der Praparativen anorganischen Chemie, ed. G. Brauer, Ferdinand Enke Verlag, Stuttgart, Part 1 , 1962. 1 P. J. Durrant and B. Durrant, Introduction to Advanced Inorganic Chemistry, Longmans, London, 1962; F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Interscience, New York, 1962. R. B. Heslop and P. L. Robinson, Inorganic Chemistry, 2nd edn., Elsevier, Amsterdam, 1963; A. F. Wells, Structural Inorganic Chemistry, 3rd edn., Oxford University Press, London, 1962. Report of the Commission on Atomic Weights, P u r e Appl. Chem., 1962, 5, 255. H. Garcia-Fernandez, Bull. Soc. chirn. France, 1961, 245. E. A. Ukshe and N. G. Bukun, Uspekhi Khim., 1961, 30, 243 (90). * G. W. A. Fowles and D. Nicholls, Quart. Rev., 1962, 16, 19. E. C. Evers, J . Chem. Educ., 1961, 38, 590. l o A. W. Searcy, Prog. Inorg. Chem., 1962, 3, 49; D. Seyferth, ibid., 129; T. R . P. Gibb, ibid., 315.
* Throughout this section, numbers in parentheses a t the end of referencesto Russian periodicals indicate the corresponding page number in the English or U.S. translation.
130
INORGANIC CHEMISTRY
2. TYPICAL ELEMENTS
(Iroup 0.-The first definite, stable compounds of an inert gas have been reported ; tensiometric titration of xenon with platinum hexafluoride yields --, the compound xenon hexafluoroplatinate(v), XeS(PtF6) a stable orangeyellow solid which sublimes when heated and is analogous t o the previouslydiscovered dioxygenyl hexafluoroplatinate, 0,+(PtF6) Both compounds -. have similar lattice energies, and the high electron-affinity of the PtF, group is the important factor in stabilising these compounds.1 Reaction of xenon with fluorine under pressure a t 400" gives xenon tetrafluoride as a colourless solid, stable a t ordinary temperatures, and probably possessing a tetrahedral or square-planar structure. Inductive heating of xenon with fluorine yields the unstable solid xenon difluoride which probably disproportionates t o give xenon and the tetrafluoride.s Group 1.-A re-examination of the structure of ethyl-lithium in hydrocarbon solvents suggests the presence of a single, probably hexameric species ;* t-butyl-lithium is, however, tetrameric, with lithium and a-carbon atoms occupying the vertices of interpenetrating tetrahedra.5 Lithium perchlorate reacts with N-methylpropionamide in the absence of solvent to give complexes in which carbonyl oxygen atoms are linked to the lithium ion.6 Two new crystalline forms of sodium peroxide are reported,' one stable above 512". Group II.-Diethylberyllium forms complex salts MX,nBeEt, ( n = I , 2, 4), e.g. KF,BeEt,, by direct addition.* The suggestion that the colour of complexes of 2,2'-bipyridyl and beryllium allryls is due to electrontransfer from the beryllium t o the bipyridyl is now supported by the preparation of the deep-green paramagnetic compound bipy,Be from bipyridyllithium and beryllium chloride. Reaction of sodium hydride with diethylberyllium Et\BS..H... / Et yields sodium hydroberyllate, stable t o 200' N a 2 Et/ *... H...:Be\Et] (I) and containing no solvent ether, for which the structure (1) is suggested.10 Complexes of beryllium chloride with dialkyl sulphides have been reported. l1 Pure magnesium hydride is prepared by reaction of the elements at 400" under pressure in presence of a trace of iodine.12 Further investiga-
[
a
N. Bartlett, Proc. Chem. Soc., 1962, 218; N. Bartlett and D. H. Lohmann,
ibid., p. 115.
H. H. Claassen, H. Selig, and J. G. Malm, J . Amer. Chem. Soc., 1962, 84, 3593. R. Hoppe, W. DBhne, H. Mattauch, and K. M. Rodder, Angew. Chem., 1962, 74, 903. T. L. Brown, D. W. Dickerhorf, and D. A. Bafus, J. Amer. Chem. SOC., 1962, 84, 1371. M. Weiner, G . Vogel, and R. West, Inorg. Chem., 1962, 1, 654. 6 A. F. Diorio, E. Lippincott, and L. Mandelkern, Nature, 1962, 195, 1296. R. L. Tallmann and J. L. Margrave, J. Inorg. Nuclear Chem., 1961, 21, 40. * W. Strohmeier and F. Gernert, Chem. Ber.,.1962, 95, 1420. G. E. Coates and S. I. E. Green, J., 1962, 3340; cf. Ann. Reports, 1961, 58, 80. l o G . E. Coates and G . F. Cox, Chem. and Ind., 1962, 269. I1N. S. Sitdykova, N. Ya. Turova, K. N. Semenenko, and A. V. Novoselova, Z h w . neorg. Kizim., 1961, 6, 2512 (1271). l a T. N. Dymova, Z. K. Sterlyadkina, and V. Safronov, Zhur. neorg. Khim., 1961, 6, 763 ( 389); T. N. Dymova, Z. K. Sterlyadkina,and N. G . Eliseeva, ibid., p. 765 (392).
HOLLIDAY : TYPICAL ELEMENTS
131
tion of the reaction of diborane with dialkylmagnesium suggests that the initial product is of the type RMg[HBR(BH,),]; when heated to 100" this yields magnesium borohydride.l3 Group III.-The stereochemistry of some Group 1 1elements has been 1 1 reviewed.l4 The relative acceptor strengths of some Group I 1 and Group I halides, with respect to ethyl acetate as reference Lewis base, have been V determined by measurement of the infrared shift in the carbonyl stretching frequency.l5 Boron. Boron has been prepared by the reduction of boron trifluoride with sodium.16 An extensive study of the borides of magnesium and aluminium indicates the existence of MgB,, MgB,, MgB,, and AlB,; hydrolysis of MgB, may yield the ion [BH2(OH),]-.17 Diborane prepared by the reaction of boron trifluoride and lithium aluminium hydride in ether contains ethyl fluoride as impurity, but can be purified by fractionation.18 A new boron hydride of probable formula B&&, is formed when an alcoholic solution of the salt (Et3NH)2(B,oHl,) is passed through an acidic ionexchange column and the eluant hydr01ysed.l~ Reaction of the same salt with a base yields the ion (BloH,0H)2- which is obtained as the thermally stable potassium salt; the ion (B20H18)2-is obtained in good yield by oxidation of the decahydrodecaborate ion (BloHlo)2- with an aqueous ferric salt.2G However, oxidation of the same ion with an acidic ceric solution yields another isomer of the ion, which is converted into the original isomer by hydrochloric acid.2I The formation and reactions of the ions (B10Hlo)2and (B1,H1,)2- have been further investigated; they react readily with donor molecules containing oxygen or sulphur, are stable to strong acids and bases and to oxidising agents, are the anions of strong acids in aqueous solution, and readily undergo partial or complete substitution with halogens to give stable ions such as (BloH61,)2-and (BlOCll,)2-.22 Possible sequential substitution reactions of this kind have been predicted the ore tic all^.^^ Sodium decaboronate, NaBloHl,, apparently exists in two forms, one prepared by the reaction of sodium hydride, and the other by reaction of alkali, with d e ~ a b o r a n e . ~ ~ Substituted decaboranes can be prepared from this salt, and addition reactions with amines or phosphines (X) give salts M+(BloH,,X)-; with X = NEt,H, hydrolysis by acid occurs thus:
[ B I ~ H ~ ~ ( H N E ~H30+ ~)Il 3 R.
+ 2H20 +2% + B(OH), + B,HI3(HNEt2)
Bauer, 2. Naturforsch., 1962, 17b, 277. l4 D. C. Bradley, Progr. Stereochem., 1962, 3, 1. l5 M. F. Lappert, J., 1962, 542. l 6 V. I. Khachishvili, T. G. Mozdokeli, R. Ya. Smolyar, and Ya. V. Asatiani, Zhur. neorg. Khim., 1961, 6, 1493 (767). l7 P. Duhart, Ann. Chim. (France), 1962, 7, 339. lS C. J. Danby, E. Gobbett, and J. W. Linnett, J., 1962, 2076. A. R. Pitochelli and M. F. Hawthorne, J . Amer. Chem. Soc., 1962, 84, 3218. 2o A. Kacmarczyk, R. D. Dobrott, and W. N. Lipscomb, Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 729. 21 A. R . Pitochelli, W. N. Lipscomb, and M. F. Hawthorne, J. Amer. Chem. SOC., 1962, 84, 3026. * 2 W. H. Knoth, H. C. Miller, D. C. EngIand, G . W. Parshall, and E. L. Muetterties, J. Amer. Chem. SOC., 1962, 84, 1056; A. R. Pitochelli, R. Ettinger, J. A. Dupont, and M. F. Hawthorne, {bid., p. 1058. 23 R. Hoffman and W. N. Lipscomb, J. Chem. Phys., 1962, 37, 520. 2 4 N. J. Blay, R. J. Pace, and R. L. Williams, J., 1962, 3416.
132
I N 0 R Gt A N I C C H E MI S T R Y
and from the enneaborane derivative so formed ions of type (BgHI2X)are produced by proton abstraction, and ions (BgH12)- by the same process and ligand expulsion.25 The anion (BIoH15)- is precipitated as the quaternary phosphonium salt by addition of a phosphonium halide to an acid solution of the salt Na2BloH,,.26 Some reactions of the new hydride B,oH16 are reported; heating in presence of iodine a t 150"yields decaborane, and reaction with hydrogen iodide breaks the central B-B bond with formation of pentaborane-9 and B5H81.27 The decomposition of tetraborane-10 and the pyrolysis of decaborane have been studied kinetically 28 and the rates of reaction of decaborane with some nitriles and sulphides have been determined.29 Treatment of pentaborane with deuterium chloride in presence of aluminium chloride gives rapid exchange of hydrogen and deuterium in the 1-position.30 Synthesis of some long-chain quaternary borohydrides has resulted in hydrocarbon-soluble salts with reducing pr0perties.~1 There is evidence for a complex between sodium borohydride and diborane, possibly NaBH4,BH3, in ethereal solvents. 3 2 Mechanisms of hydrolysis and methanolysis of sodium borohydride have been investigated ; finely divided metals such as platinum are reported t o be very effective catalysts for hydrolysis. 33 The reaction of butadiene and diborane gives two compounds of empirical formula B2C4H12,formulated as 1,2-tetrarnethylenediborane (2) and 1y2-( '-methy1trimethylene)diborane (3).34 Reaction of pentaborane-9 with 1
alkynes in presence of 2,6-dimethylpyridine gives compounds of type B,H6C,RR', but reaction with acetylene in a silent discharge yields " carborane-3," B,C2H5, which appears to be a member of a series B,C,H,+, formed by acetylene-borane reactions, and probably has a trigonal-bipyramidal structure with the three boron atoms coplanar and the two carbon atoms a t the apices.35 A new synthesis of amine-borines, by reduction of phenyl borate with aluminium and hydrogen in presence of the appropriate
z 5 H. C. Beachell and D. E. Hoffman, J . Amer. Chem. SOC., 1962, 84, 180; B. M. Graybill, A. R. Pitochelli, and M. F. Hawthorne, Inorg. Chem., 1962, 1, 622. 2 6 J. A. Dupont and M. F. Hawthorne, Chem. and Ind., 1962, 405. 2 7 R. N. Grimes and W. N. Lipscomb, Proc. Nat. Acad. Sci. U.S.A., 1962, 48, 496. 2 8 A. J. Owen, J., 1961, 5438; G. L. Brennan and R. Schaeffer, J . Inorg. Nuclear Chem., 1961, 20, 205. 2 9 I. Dunstan and J. V. GrifEths, J., 1962, 1344. 3 O T. P. Onak and R. E. Williams, Inorg. Chem., 1962, 1, 106. 31 E. A. Sullivan and A. A. Hinckley, J . Org. Chem., 1962, 27, 3731. 3 2 E. B. Baker, R. B. Ellis, and W. S. Wilcox, J . Inorg. Nuclear Chem., 1961, 23, 41. 33 R. E. Davis, E. Bromels, and C. K. Kibly, J . Amer. Chem. SOC., 1962, 84, 885; R. E. Davis, ibid., p. 892; R. E. Davis and J. A. Gottbrath, ibid., p. 895; H. C. Brown and C. A. Brown, ibid., p. 1494. 3 4 H. G. Weiss, W. J. Lehmann, and I. Shapiro, J . Amer. Chem. SOC., 1962, 84, 3840. 35 T. P. Onak, R. E. Williams, and H. G . Weiss, J . Amer. Chem. SOC., 1962, 84, 2830; I. Shapiro, C. D. Good, and Rt. E. Williams, ibid., p. 3837.
HOLLIDAY
: TYPICAL ELEMENTS
133
amine, is reported ;36 dimethylamino-derivatives of boron can be prepared by reaction of the compound Al(NMe,), with alkyl- or a l k o x y - b o r i n e ~ . ~ ~ Some hitherto unknown bis(alkylamino)borines have been prepared by treatment of dimethylamino-n-propylthioborinewith a primary amine at 70, e.g.,
Me,N.BH*SC,H,
+ ZRNH, + ( R N H ) , B H + C3H,SH + Me,NH.
On heating the product above 150, an N-trialkylborazole is produced.38 The stability of aminoborines in relation t o the substituents on the nitrogen Dichlorodimethylaminoborine, and boron atoms has been i n ~ e s t i g a t e d . ~ ~ Me,N*BCl2, dimerises, whereas dimethyldimethylaminoborine, Me&*BMe,, does not ; when these are heated together the intermediate compound Me,N*BClMe is formed, and this is stable t o disproportionation but slowly forms a solid dimer.40 The reaction of hydrogen chloride with trisdimethylaminoborine in ether yields the compound [Cl,B(HNMe,),]Cl, and this is also obtained by reaction of hydrogen chloride with chlorobisdimethylamin~borine.~~ Trimethylamine-triborane, Me,N*B,H,, is cleaved by triphenylphosphine t o give the triphenylphosphine adduct of a new boron hydride, (Ph,P*BH,),, with H,- /H the possible structure (a), i . e . a 2 : 1 adduct of the HYB--H I (4) parent hydride of the diboron compounds.42 New ph3p+ + pph,3 diboron compounds B,(NMe,),- ,$lZ have been prepared by reaction of tetrakisdimethylaminodiboron with hydrogen chloride in ether.43 The existence of trisdifluoroborinylamine, N(BF,),, stabilised by B-N n-bonding, is predicted on theoretical grounds.44 Boron-nitrogen ring compounds continue t o receive attention ; mixtures of isomeric fluoroborazoles, B,N,H,F, and difluoroborazoles, B,N,H,F,, have been synthesised by reaction of P diborane with tetrafluorohydrazine a t 140-160,45 N\ C B/ I C I BBB-trisdialkylaminoborazoles, (R,NB*NH), (R = Me, I E t , Prr, Pri),by reaction of secondary amines with BBBRAN, /N,R B trichloroborazole, 46 and NNN-t r i a 1k y 1b o r a z o 1e s , I ( s i (BH-NR),, by heating the borine adduct RNH,*BH, H with a thiol RSH,whereupon the intermediate compound RNH*BH*SR splits out RSH to give the b o r a ~ o l e . ~ ~ Thermal dehydrochlorination of the addition compound of boron trichloride and 2,6-dimethylE. C. Ashby and W. E. Foster, J . Arner. Chem. SOC.,1962, 84, 3408. J. K. Ruff, J . Org. Chem., 1962, 27, 1020. 38 B. M. Mikhailov and V. A. Dorokhov, Izvest. Akad. N a u k S.S.S.R., Otdel. khim. N a u k , 1961, 1163 (1082). 39 G. M. Wyman, K. Niedenzu, and J. W. Dawson, J., 1962, 4068; D. W. Aubrey, M. F. Lappert, and M. K. Majumdar, ibid., p. 4088. 4 0 F. C. Gunderloy and C. E. Erickson, Inorg. Chem., 1962, 1, 349. 4 1 H. Noth and S. Lukas, Chena. Ber., 1962, 95, 1505. 4 2 B. M. Graybill and J. K. Ruff, J . Amer. Chem. SOC., 1962, 84, 1062. 4 3 H. Noth and W. Meister, 2. Naturforsch., 1962, 17b, 714. 4 4 A . D. Buckingham, Proc. Chem. SOC., 1962, 351. 4 5 R. K. Pearson and J. W. Frazer, J . Inorg. Nuclear Chem., 1961, 21, 188. 413 W. Gerrard, H. R. Hudson, and E. F. Mooney, J., 1962, 113. 4 7 B. M. Mikhailov and V. A. Dorokhov, Izvest. Akad. Nauk S.S.X.R., Otdel. khim. N a u k , 1961, 1346 (1251).
36 37
134
INORGANIC CHEMISTRY
aniline yields the dichloroborazole (5) (R = 2,6-Me2C,H,) in which the single B-H l n is stable to nu~leophiles.~8 ik The preparation of N-lithioborazoles, and reaction of these with B-chloroborazoles has given new polymers consisting of borazole rings linked through B-N bonds, e.g., compound (6) (n < 23); similar units linked through B-O-B bonds are obtained
Me B - N N MeB,
L
Me
_-
,BMe
I\:
B I MeN,
l N \
BI ,NMe
Me
B Me
-1
(6)
by controlled hydrolysis of B-chloroborazoles.4~ Reaction of boron trichloride or boron tribromide with ortho-substituted anilines gives fused-ring borazoles in which each B-N unit of a borazole ring is bridged as shown in (7) ;50 but reaction with fully a-substituted amines (e.g., ButNH,) yields tetrameric borazynes, (RN-BX),, and not trimeric borazoles; these are solids
X R
RN<B-N\ BX
and are generally much more stable than the borazoles. Structural studies suggest a boat form of the ring structure (8; X = Cl); the relatively inaccessible boron atoms account for the low reactivity. 51 Monomeric phosphinoborines have been prepared by reaction of alkylchloroborines with lithium albylphosphines:
Et,N.BCl,
+ BLiPEt, -+
Et,N*B(PEt,),
+ 2LiC1.
These compounds are reactive liquids ; reaction with hydrogen chloride gives, e.g., Et,N*BCl*PEt,, and this on reduction with sodium-potassium alloy yields the diboron compound (9).52
I
Et2N.
PEt2
MeC=N, MeC=N
Et2P
B ,-
B(
NEt2
,N=CMe N, N=CMe
(9)
4 8 R. K. Bartlett, H. S. Turner, R. J. Warne, M. A. Young, and (in part) W. 5. McDonald, Proc. Chem. SOC., 1962, 153. 4 9 R. I. Wagner and J. L. Bradford, I n o r g . Chem., 1962, 1, 93, 99. 6 o J. J. Harris and B. Rudner, J . Org. Chem., 1962, 27, 3848. s1 H.S. Turner and R. J. Warne, Proc. Chem. SOC., 1962, 69. 5*H. Noth and W. Schragle, Angew. Chem., 1962, 74, 587.
HOLLIDAY
TYPICAL ELEMENTS
135
Several examples of phosphinodecaboranes, BloH1,(PX,),, have been investigated ; in bis(chlorodiphenylphosphino)decaborane, phosphorus is the attached at the 6- and 9-positions; reaction with a primary amine gives BloH12(Ph,P-NHR),, and with sodium azide BloHl,(Ph2PN,), is obtained; exchange of the attached phosphino-groups with acetonitrile has been noted.53 Reaction of dimethylaminodifluorophosphine with the unstable carbon monoxide adduct of tetraborane yields the stable compound B,H,*F,P*NH,, where co-ordination is probably through the phosphorus atom. 54 The reaction of boron with air or oxygen at temperatures above 1600" gives the solid oxide B60.55 A reactive form of boron monoxide, (BO),, which is soluble in alcohols and reacts with boron trichloride to form diboron tetrachloride, is obtained by dehydration of hypoboric acid, which is reformed on addition of water t o the oxide; a boroxole ring structure is suggested for the latter.56 The cyclic structure of the trimeric boron oxyfluoride, B303F3, has been confirmed by mass-spectroscopic observations; the boron-oxygen bonds appear to be intermediate in character between B-0 and -B=O+, and conditions (high temperature and low pressure) for dissociation to the monomer have been defined. Addition of hydrogen to the high-temperature reaction system, BF, B,O,, yields gaseous products such as B,03F2H.57 Cyclic boronates have been prepared from phenylboronic anhydride and appropriate diols, and the stability of their amine complexes discussed with respect to ring size and s ~ l s t i t u e n t s . ~ ~ The introduction of boron into a metal-chelate ring system is reported;59 bis(dimethylg1yoximato)nickel reacts with BX, (X = alkyl or halogen) compounds to effect ring closure through 0-B-0 bonding to give structure (10). A new class of non-stoicheiometric crystalline inclusion compounds, of general formula (MeO),B*(amine),,(solvent),(n < 1 and x < 3), is reported; the compounds can be sublimed without change of composition.60 Numerous cationic species of boron sulphides, up to BIOS,+,have been identified by mass spectrometry in the vapour of B,S,.61 Several studies of reactions of thiols with boron compounds are reported; trialkylborons, R,B, and alkanethiols, R'SH, yield esters of diallcylthioboric acid, R,B-SR' , from which the SR' group is displaced by ammonia to give R , B o N H , ; ~ ~ with
53 H. Schroeder, J. E. Reiner, and T. L. Heying, Inorg. Chem., 1962, 1, 618; R . J. Pol& and T L. Heying, J . Org. Chem., 1962,27, 1482;.L. I. Zakharkin and V. I. Stanko, . Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Naulc, 1961, 2078 (1936). 64 G. Ter Haar, M. A. Fleming, and R. W. Parry, J . Amer. Chem. Soc., 1962, 84,
1767.
66
H. F. Rizzo, W. C. Simmons, and H. 0. Bielstein, J . Electrochem. SOC., 1962,

A. L. McCloskey, R. J. Brotherton, and 5. L. Boone, J . Amer. Chem. SOC., 1961,
109, 1079.
66
83, 4750; cf. Ann. Reports, 1961, 58, 85.
5 7 M. Farber, J . Chem. Phys., 1962, 36, 661,.1101; R. F. Porter and W. P. Sholette, ibid., 37, 198; W. J. Lehmann, C. 0. Wilson, JW., and I. Shapiro, J . Inorg. Nuclear Chem., 1961, 21, 25; cf. Ann Reports, 1961, 58, 85. 6 8 A . Finch and J. C. Lockhart, J., 1962, 3723. 6 9 F. Umland and D. Thierig, Angew. Chem., 1962, '74, 388; G. N. Schrauzer, Chem. Ber., 1962, 95, 1438. 6 0 D . M. Young and C . D. Anderson, Canad. J . Chem., 1962, 40, 1805. 61 F. T. Greene and P. W. Gilles, J . Amer. Chem. SOC., 1962, 84, 3598. 6 2 B. M. Mikhailov and Yu. N. Bubnov, Zhuv. obshchei Khim., 1961, 31, 160 (150).
136
I N O R G A N I C CHEMISTRY
diethylaminoborine the thiol affords an alkylthiodiethylaminoborine, e.g. , E ~ , N * B H o S R 'and with the thiol and boric oxide in boiling benzene, ;~~ cu-mercaptoalkylborates (HS*[CH,];O),B are formed.64 Metal thioborates, e.g., CUBS and AgBS, which are unreactive, are formed by direct union of the elements a t 800".65 The reaction of metal sulphates M1,S04 and M'ISO, with boric acid and sulphur trioxide gives bis-sulphatoborates, e.g., MI[ B(SO,),], MI1[ B(SO4),],, and tris-sulphatodiborates, e.g., MII[B,O( SO,),] ; these are sensitive to hydrolysis.66 The chemistry of the boron sub-halides and related compounds with B-B bonds has been reviewed.67 Treatment of boric esters with sulphur tetrafluoride gives successive replacement of alkoxy-groups by fluorine, finally yielding boron trifluoride.68 Some addition compounds of boron trifluoride with primary aromatic diamines have been prepared and characterised.69 Diboron tetrafluoride reacts with oxygen to give boron trifluoride and a stable solid, (B,O,F),; with nitric oxide, the products are mainly nitrous oxide and nitrogen. 70 Labelled boron trichloride is conveniently prepared by heating together silver chloride and boron above 600" in vacz~o; 70% yield is 0btained.~1 An examination of the infrared a spectra of phosphoryl chloride-boron trichloride and similar addition compounds suggests that these are oxygen-co-ordinated and not ionic.7 2 Steric e&cts which control the replacement of chlorine atoms in boron trichloride by dialkyl- and diaryl-amino-groups have been studied ; complete replacement does not occur if, e.g., the alkyl groups are branched in the ct-position, although mixed tris(dialliy1amino)-compounds, e.g., R,N*B(NPr',), (R = Me, Et), are thermally stabh73 The thermal decomposition of diboron tetrachloride yields boron-chlorine compounds which are coloured solids ; one of these is the red dodecaboron undecachloride, B,,Cl,,, which gives a single broad paramagnetic resonance band in cyclopentane solution. The solid is only slightly decomposed below its m.p. (115"), but is hydrolysed in basic solution : 2B12Cl11 + 140H- + 3H2 + 4B0,- + 2[B1,Cl,(OH)2]2- + 2 H 2 0 + 6C1-. With an excess of trimethylamine, the addition compound (B,,C1,,,2Me3N), is formed.74 The existence of the tetraiodoborate ion, B14-, has been confirmed, and the tropenium salt prepared.75 The reaction of boron trichloride with sodium or potassium thiocyanate in liquid sulphur dioxide
6 3 B. 31. Mikhailov and V. A. Dorskhov, Zhur. obshchei Khirn., 1961, 31, 3750 (3504). 6 4 R. C. Cass and H. B. Silver, Chem. and Ind., 1962, 265. 6 5 J. Flahaut, L. Domange, and J. K. Korn, Compt. rend., 1962, 254, 299. 6 6 G. Schott and H. U. Kibbel, 8.unorg. Chew,., 1962, 314, 104. 6 7 A. K. Holliday and A. G. Massey, Chem. Rev., 1962, 62, 303. 6 8 A. Dornow and M. Siebrecht, Chem. Ber., 1962, 95, 763. 6 9 A. Kreutzberger and F. C. Ferris, J . Org. Chem., 1962, 27, 3496. 7 0 A. K. Holliday and F. B. Taylor, J., 1962, 2767. 71 K. H. Lieser, H. W. Kohlschutter, D. Maulbecker, and H. Elias, 2. anorg. Chem., 1961, 313, 191. 7 2 M. E. Peach and T. C. Waddington, J., 1962, 3450. 73 D. W. Aubrey, W. Gerrard, and E. F. Mooney, J., 1962, 1786. 7 4 G. Urry, E. P. Schram, and S. I. Weissman, J . Amer. Chem. SOC., 1962, 84, 2654. 7 5 K. H. Harman and F. E. Cummings, J . Amer. Chem. Xoc., 1962, 84, 1751.
HOLLIDAY : TYPICAL E L E M E N T S
137
yields boron tri-isothiocyanate, B(NCS),, which has acceptor properties ; complex isothiocyanatoborates, e.g., Na[BH(NCS),] and Li[B(NCS),], are prepared (as etherates) by the reaction of the appropriate borohydride with ethereal thiocyanogen. 76 Aluminium. Bisdimethylaminoaluminium hydride adds on two molecules of bis(dimethy1aminoborine) t o give the adduct HA1(NMe2),,2(BH,*NMe2), but the structure of this is uncertain.77 Alkali-metal aluminium hydrides can be prepared directly and in good yield by reaction of the metal or its hydride with aluminium and hydrogen in ether solvents a t 140" under pressure.78 A variety of compounds containing A1-N bonds have been produced by using tetramethyltetrazen as a source of dimethylaminoradicals, e.g., MeAl(NMe,), and (Et,Al*NMe,),.7 9 Polymers containing A1-N bonds have been prepared by formation and then condensation of addition compounds of triphenylaluminium with aliphatic amines in toluene, and some of these have been characterised, e.g., (Me,N*AlPh,), and (MeN*A1Ph),.S0 The use of an aromatic amine with non-ortho ring substituents (e.g., p-toluidine) in this reaction yields crystalline tetramers (C,H,Al-NAr),, analogous to the tetrameric borazynes ; a cubic structure, with aluminium and nitrogen atoms a t the corners, is suggested.81 The reaction of trimethylammonium chloride and ethylaluminium chloride in toluene a t room temperature probably yields the salt (MeNH,)(EtA1Cl,).s2 The white crystalline trimer (Et2P*A1C1,),is formed by the reaction of aluminium chloride with 1 mol. of lithium diethylphosphide in ether; with 4 mol. of the latter, the solid Li[Al(PEt,),] is obtained.83 A new lowtemperature form of the aluminate, LiA1O2, prepared by heating lithium carbonate with alumina a t 600 is reported.84 Polymeric phthalocyaninealuminium compounds have been prepared with organo- and organosiloxygroups bonded to the aluminium, e.g., pcAl-O*SiPh, (pc = C3,Hl6Ns); others contain A1-O-A1 bonds and some are resistant to h y d r o l y s i ~ . ~ ~ Solvated complex halogeno-acids, HAlX,,dioxan (X = C1, Rr), have been obtained by reaction of aluminium metal and hydrogen halide in dioxan.86 Gallium, indium, and thallium. Trimethylaminegallane and the corresponding trideuterogallane have been prepared, and the vibrational frequencies assigned; there is evidence that the Ga-H bond is stronger than the A1-H bond in the corresponding aluminium adducts. 8 7 Trialkylgallanes,
O,
7 6 D. B. Sowerby, J . Amer. Chem. SOC.,1962, 84, 1831; F. Klanberg, 2. anorg. Chem., 1962, 316, 197. 7 7 J. K. Ruff, Inorg. Chem., 1962, 1 612. , 7 8 E . C. Ashby, Chem. and Ind., 1962, 108. 7 9 N. Fetter and B. Bartocha, Cunad. J . Chem., 1962, 40, 342. A. W. Laubengayer, K. Wade, and G. Lengnick, Inorg. Chem., 1962, 1 632. , J. Idris Jones and W. S. McDonald, Proc. Chem. SOC., 1962, 366. 8 2 J. D. Smith, J., 1962, 4734. 83 G. Fritz and G. Trenczek, 2. unorg. Chem., 1961, 313, 236; Angew. Chem., 1962, 74, 942. 8 4 H.-A. Lehmann and H. Hesselbarth, 2. anorg. Chem., 1961, 313, 117. 8 5 J. E. Owen and M. E. Kenney, Inorg. Chem., 1962, 1 331, 334. , 8 6 J. A. Miliotis and A. G. Galinos, Compt. rend., 1962, 254, 3368. 8 7 D. F. Shriver, R. L. Amster, and R. C. Taylor, J . Amer. Chem. Soc., 1962, 84, 1322; N. X. Greenwood, A. Storr, and M. G. H. Wallbridge, Proc. Chem. SOC.,1962, 249.
138
R,Ga, have been prepared by the reaction of gallium trihalides with aluminium alkyls in the presence of potassium chloride, and dialkylgallanes, R,GaH, by the reaction of dialkylgallium halides with dialkylaluminium hydrides under similar conditions; R,GaH is converted into R,GaR' by reaction with olefins or acetylenes.88 Gallium nitride has been prepared by the reaction :
G a 2 0 3+ 2NH3 -+ 2GaN
+ 3H20
at 480"; it decomposes above 600O.89 Co-ordination compounds of types (GaL,)+X- and (GaL,)+(GaX,)- (L = monodentate ligand; X = C1, Br) have been prepared from GaX and Ga(GaX,), respectively, with a variety of ligand~.~OSome complexes of gallium(r1r) halides with o-phenanthroline have been described.91 The compounds InSF and InSeF have been prepared by heating a mixture of indium(n1) fluoride and the sulphide or selenide at 400".92 Complexes of thallium(m) iodide and nitrate with ammonia, 2,2'-bipyridyl, and 1,lO-phenanthroline are reported.93 Thallium(1)methoxide has been shown to be tetrameric, with the structure (1 ) . 9 4 1
T I -OMe
I /
I/.'
Group IV.--Carbon. New methods for the preparation of cyanides, cyanates, and thiocyanates, using reactions in fused alkali or alkaline-earth chlorides, are described, e.g.g5
Me2SiC1 KCN +Me,SiCN SiCl, 4KSCN+ Si(SCN),
+ KCI + 4KC1.
The products obtained by the fluorination of cyanogen depend upon the mode of fluorination; reaction with silver difluoride a t 105-115" does not give the same product (F,N*CF,*CF,*NF,)as direct fluorination but gives instead the compound (12); this does not react with water but decomposes above 150" to give nitrogen, tetrafluoroethylene, and other products.gs Silicon. The occurrence of multiple bonding with particular reference to silicon has been reviewed,97and the r6le of the 3d-orbitals in forming n-bonds from silicon and other elements to oxygen has been discussed.98
J. J. Eisch, J . Arner. Chem. SOC.,1962, 84, 3605, 3830. M. R. Lorenz and B. B. Binkowski, J . Electrochem. SOC.,1962, 109, 24. Q 0 F. M. Brewer. J. R. Chadwick. and G. Garton, J . Inorg. Nuclear Chem., 1961,
88
23, 45.
Q l B .N. Ivanov-Emin, L. A. Niselhon. Ya. I. Rabovik, and L. E. Larionova, . Zhur. neorg. Khim., 1961, .6, 1142 (583). Q 2 H. Hahn and W. Nickels, Z. anorg. Chem., 1962, 314, 303. Q 3 F. Ya. Kul'ba, Yu. A. Makashev, and V. E. Mironov, Zhur. neorg. Khirn., 1961, 8, 1481 (758). Q 4 L. F. Dahl, G. L. Davis, D. L. Wsmpler, and R. West, J . Inorg. Nuclear Chem., 1962, 24, 357. 9 s W. Sundsrmeyer, Z. afaorg. Chem., 1962, 313, 290. Q 6 H. J. Emelbus and G. L. Hurst, J., 1962, 3276. 9 7 I. R. Beattie and T. Gibson, Nature, 1962, 193, 1041. Q 8 D W. J. Cruickshank, J., 1961, 5486. .
HOLLIDAY : TYPICAL E L E M E N T S
139
The preparation of high-purity silicon from silane by heating it above 777" is described.99 Conversion of silane into higher silanes can be achieved with 68% conversion in an ozoniser, and mixed hydrides, e.g., SiH3,PH2 and GeH,,PH, can be prepared similarly.l o o I n the preparation of silane derivatives from silicon, it is usually necessary to activate the latter, but reaction of unactivated silicon with cuprous chloride-activated hydrogen chloride a t 300-400 O gives a 99% yield of trichlorosilane.101 Methylation of phenylsilane has been effected with diazomethane.102 Bisaminomethyl(dimethy1)silane, Me2Si(CH,*NH2),, has been prepared by the reaction of bischloromethyl(dimethy1)silanewith bisphthalimidomethyl(dimethyl)silane, and its propertie$ are described.103 Considerable progress has been made in the chemistry of disilane and its derivatives. Disilane has been obtained in good yield by reaction of iodosilane vapour with sodium amalgam at ordinary temperatures, and 1,2-dimethyldisilane by analogous methods. Reaction of the previously reported iododisilane, H,Si*SiH,I, with mercuric sulphide yields the sulphide (H3Si*SiH2),S,with ammonia the trisdisilanylamine (H,Si*SiH,),N (both spontaneously inflammable in air), and with silver bromide disilanyl bromide, H,Si*SiH,Br. Other disilane derivatives synthesised include the chloride and the cyanide, and the oxide (Me3Si*SiMe2),0.lo4 From chloropentamethyldisilane, octamethyltrisilane, Me,Si,, has been prepared by reaction with chlorotrimethylsilane and sodium-potassium a.lloy; use of the chloropentamethyldisilane alone gave decamethyltetrasilane, MeIoSil.lo5 Some interesting new compounds containing Si-B bonds have been prepared by the reaction:106
R,SiLi
+ ClB(NMe,), +R,Si*B(NMe,), + LiCl
j,, ,,
R,Si*BCl(NMe,)
+ Me,NH,HCl.
New silazides have been prepared by several methods; thus, lithium azide and chlorotriphenylsilane in tetrahydrofuran give triphenylsilazide, Ph,SiN,, and this on reaction with triphenylphosphine gives nitrogen and the compound Ph,Si*N:PPh,; sodium azide in pyridine can be used to form the same triphenylsilazide and also the diazide Ph,Si(N,),. 107 Methyl silazides, e.g., Me,SiN,, have also been prepared, by reaction of chlorotrimethylsilane with sodium azide at 250" in an anhydrous melt of zinc and potassium chlorides as solvent, or with sodium azide in tetrahydrofuran in
9 9 C. H. Lewis, H. C. Kelly, M. B. Giasto, and S. Johnson, J . Electrochem. Soc., 1961, 108, 1114. 100 J. E. Drake and W. L. Jolly, Chem. and Ind., 1962, 1470; E. J. Spanier and A. G. MacDiarmid, Inorg. Chem., 1962, 1, 432. l o l P. G. Dudani and H. G. Plust, Nature, 1962, 194, 85. l o 2 K. Kramer and A. Wright, Angew. Chem., 1962, 74, 468. lo3J. Goubeau and H. D. Fromm, 2. anorg. Chem., 1962, 317, 41. l o 4L. G. L. Ward and A. G. MacDiarmid, J . Inorg. Nuclear Chem., 1961, 20, 345; 1961, 21, 287; A. D. Craig and A. G. MacDiarmid, ibid., 1962, 24, 161; A . D. Craig, J. V. Urenovitch, and A. G. MacDiarmid, J . , 1962, 548. lo5 U. G. zu Stolberg, Angew. Chem., 1962, 74, 696. lo6 H. Noth and G. Hollerer, Angew. Chem., 1962, 74, 718. lo' N. Wiberg, F. Raschig, and R. Sustmann, Angew. Chem., 1962, 74, 388, 716.
140
INORGANIC CHEMISTRY
presence of aluminium azide as catalyst ; the compounds Me,Si(N,), and MeSi(N,), have been obtained similarly.108 The structure of tetramethylNN-bis(trimethylsilyl)cyclodisilazane, reported last year, has been confirmed,lo9and some other, unstable N-silyl-tri- and -tetra-silazanes have been prepared.l1 It now seems probable that the compound prepared by reaction of silver cyanamide with iodosilane, formulated as disilylcyanamide, (siH,),N.CN, may be a di-imide, since the analogous reaction with chloroMe,Si*N:C :N*SiMe,; the trimethylsilane gives bistrimethylsilylcarbodi-imide, corresponding sulphur compound has the structure (Me,Si)~*S*N(SiMe,),.lll Further work on silylphosphines has been carried out; synthesis by the general reaction, LiPR, R,SiCl,-,, has given, e.g., (Et,P),SiCl and Et,SiH*PEt,, and st phosphonium salt has been obtained by the reaction:112
Me,Si*PEt, + EtI -+ (Me,Si*PEt,)I.
Silicon halides Six, (X = F, Cl, Br) react with tertiary phosphines and their oxides to give co-ordination compounds, SiX,,(PR,),, SiX4,(OPR2),,and SiX4,(OPR3)4.113 The preparation of black and yellow forms of silicon monoxide, condensed from the gaseous product of a silicon-silica reaction at 1200, is reported.114 Condensation of chloromethyl(dimethyl)silanolwith dichlorodimethylsilane in the presence of triethylamine yields the compound (13);
Me
CIH,C-Si Me
I
Me
-0-Si
Me
I
y
-CHICl RZSi
I
Sib2
YH SiR,
1
Me
-0-Si
Me
HN
0 (14)
(13)
si/R2
the central silicon atom is replaced by germanium by using dichlorodimethylgermane in the synthesis.115 Mixed siloxane-silazane ring compounds, e.g., (14; R = Me), have been obtained by reaction of dihalogenopolysiloxanes, C1(SiR20);SiR,C1 ( n = 1, 2, 3), with ammonia in ether.116 Several compounds in which silicon and aluminium are linked through oxygen or nitrogen have been prepared; thus, reaction of the compound Me,Si*O*AlCl, with methyl-lithium yields Me,Si*O*AlMe,,which is dimeric in benzene and has the structure (15);it is thermally stable and is not cleaved by trimethylamine at 3Oo.ll7 Similar compounds, in which the aluminiumlo8 W. Sundermeyer, Angew. Chem., 1962, 74,717, 875; idem, 2. anorg. Chem., 1962, 313, 290; R . West and J. S. Thayer, J. Amer. Chem. SOC., 1962, 84, 1763; J. W. Connolly and G. Urry, Inorg. Chem., 1962, 1, 718. log P. J. Wheatley, J., 1962, 1721; cf. A n n . Reports, 1961, 58, 90. 110 W. Fink, Helv. Chim. Acta, 1962, 45, 1081. J. Pump and U. Wannagat, Annalen, 1962, 652, 21; idem, Angew. Chem., 1962, 74,117 ; E. A. V. Ebsworth and M. J. Mays, ibid., p. 117 ;U. Wannagat and H. Kuckertz, ibid., p. 117; cf. Ann. Reports, 1961, 58, 90. 112 G. Fritz, G. Poppenburg, and M. G. Rocholl, Nuturwiss., 1962, 49, 255; G. Fritz and G. Poppenburg, ibid., p. 449. 113 K. Issleib and H. Reinhold, 2. anorg. Chem., 1962, 314, 113. l14H.-H. Emons and H. Boenicke, 2. Chew., 1961, 1, 370. 115 M. Wicber and M. Schmidt, Angew. Chern., 1962, 74, 903. 116 C. R. Kriiger and E. G. Rochow, Angew. Chem., 1962, 74, 491. 11 H. Schmidbaur and M. Schmidt, J. Anzer. Chem. SOC., 1962, 84, 1069.
HOLLIDAY
TYPICAL ELEMENTS
141
attached methyl groups are replaced by -OSiR, groups, have also been prepared; further reaction gives anionic species, thus (with R = Me) :118
R,SiONa
+ AlC1, + [(R,SiO),Al],
MI[ (R,SiO) ,Al(OSiR,)
+N1(R,SiO)
2].
The reaction of aluminium chloride with tetrameric dialkylcyclosiloxanes also leads to the formation of Si-0-A1 bonds, e.g., in structure (16),119and
SiMe,
(16)
(17)
SiMe3
the silazalane (17) has been prepared by reaction of hexainethyldisilazaae with aluminium chloride .I20 Reaction of sodium triphenylsilyl oxide and mercuric chloride gives (Ph,SiO),Hg as an unstable intermediate, which spontaneously rearranges, with migration of a phenyl group from silicon t o mercury, and yields Ph,Si*O*HgPh; the latter, when heated, gives diphenylmercury and polymeric phenyl-silicones.121 The new compound, methyl silyl sulphide, H,Si*SMe, has been prepared from methanethiol and the trimethylamine adduct of iodosilane; as a donor molecule to borine it is weaker than dimethyl sulphide but comparable to disilyl sulphide, (H3Si),S.122 The reaction of chlorodimethylsilylmethanethiol and sulphuryl chloride is 2C1SiMe2.CH,*SH + SO,Cl2 -+ ClSiMe,-CH,.S*S*CH,SiMe,Cl SO, + 2HC1. + The reactions of some nitrogen donor molecules (e.g., pyridine, trimethylamine, and 2,2'-bipyridyl) with the tetrahalides of silicon, germanium, and tita,nium, and with chloromethylsilanes, have been investigated. 124 Germanium, tin, and lead. Germane has been prepared by reduction of aqueous germanate solutions with alkali borohydrides, and higher germanes by decomposition of germane in an ozoniser.125 The formation of hexaaryldigermanes from germanium tetrachloride and arylmagnesium halide has been shown to proceed via the germyl Grignard reagent, Ar,Ge*MgX; hydrolysis of the latter (Ar = o-, m-, or p-C,H,Me) yields the hydride Tri-iodatrifluoromethylgermane, CF,*GeI,, has been prepared Ar,GeH. by the reaction of trifluoroiodomethane with germanium(rr) iodide ; treatment with the appropriate silver halide, AgX, replaces the iodine by the halide, and with X = F, aqueous potassium fluoride dissolves the compound 11* H. Schmidbaur and M. Schmidt, Angew. Chem., 1962, 7 , 328, 589. 4
llS A. A. Zhadanov, K. A. Andrianov, and A. A. Bogdanova, Izvest. AEad. Nauk S.S.S.R., Otdel. k h i m . N a u k , 1961, 1261 (1172). 1 2 * H . Schmidbaur and M. Schmidt, Angew. Chem., 1962, 74, 327. 121 A. K. Ghosh, C. E. Hansing, A. I. Stutz, and A. G. MacDiarmid, J., 1962, 403. lZ2 B. Sternbach and A. G. MacDiarmid, J . Inorg. Nuclear Chem., 1961, 23, 225. 123M. Wieber and M. Schmidt, Angew. Chem., 1962, 74, 002. 124 I. R. Reattie and G. J. Leigh, J . Inorg. Nuclear Chem., 1961, 23, 55. 125 J. E. Drake and W. L. Jolly, J., 1962, 2807. 126 F. Glockling and K. A. Hooton, J., 1962, 3509.
142
INORGANIC CHEMISTRY
to give the salt K,(CF,*GeP,). 12' Some germyl pseudohalides, e.g., GeH,*NCO, have been prepared by reaction of germyl bromide with the silver pseudohalide ; however, silver thiocyanate yields the isothiocyanate GeH,*NCS.128 The difluorides of germanium and tin are readily prepared by reaction of the metal (M) with hydrofluoric acid; in presence of an excess of fluoride ion, complex anions MF3- are formed, GeF3- being more stable to hydrolysis than SnF3-.129 Germanium tetrafluoride has been shown to be a powerful acceptor molecule, forming both 1 : 1 and 1 : 2 addition compounds with methyl cyanide, and 1 : 1 compounds with, e.g., ammonia, piperidine, phosphine, and trimethylphosphine. l 3 0 An examination of the microwave spectrum of germyl fluoride (first reported last year) suggests some degree of a-bonding in the Ge-F bonds.131 The occurrence of tin(@ has been detected in the oxidation of tin(I1) Alkylcompounc@ by trioxalatocobaltate(rn) ions in aqueous s01ution.l~~ stannanes have been prepared by reaction of the appropriate tin(rv) halide with alkylaluminium compounds; good yields are obtained by " binding " the aluminium chloride also produced, e.g., by addition of an amine or lithium chloride.l33 Tetrakisiodomethylstannane, Sn(CH,I),, has been prepared from the corresponding br0mide.13~ Interest in the various forms of diphenyltin continues; a six-membered ring of tin atoms is suggested as the nucleus of the hexamer (SnPh,),, prepared by decomposition of diphenylstannane in ~yridine.1~5 Many new compounds containing Sn-N bonds are now reported; methods of preparation of these compounds, of general formula R,Sn(*N<),-, (z= 1, 2, 3, or 4), from the corresponding alkylchlorostannanes, R,SnCl,, include treatment with a Grignard reagent (e.g., Et,N*MgBr), reaction with a lithium alkylamide, LiNR,, or reaction with the corresponding organosilicon compound; in the latter case, 1 : 1 addition of a secondary silylamine, R,Si*NHR, to the tin compound (e.g., Me,SnBr) is followed by elimination of bromotrimethylsilane, on heating, to give Me,Sn*NHR.136 With a tertiary silylamine, the 1 : 1 addition compound is stable to heat and in these compounds (18) the tin is five-co-ordinated; a structural investigation of the 1 : 1 addition compound of pyridine and trimethylchlorostannane, Me,Sn(py)Cl, indicates that here also tin is five co-ordinate.137 I n ultraviolet light, tetrafluoroethylene has been shown to
lZ7 lZ8
H.C. Clark and C. J. Willis, J . Amer. Chem. SOC.,1962, '84, 898. E. L. Muetterties, Inorg. Chem., 1962, 1, 342. R. C. Aggarwal and M. Onyszchuk, Proc. Chem. SOC., 1962, 20.
T. N. Srivastava, J. E. Griffiths, and M. Onyszchuk, Canad. J . Chem., 1962, 40,
739.
129 lS0
J. E. GrifEths and K. B. McAf'ee, jun., Proc. Chem. SOC., 1961, 456; cf. Ann. Reports, 1961, 58, 91. 132 W. C. E. Higginson, R. T. Leigh, and R. Nightingale, J., 1962, 435. 133 W. P. Neumann and H. Niermann, Annalen, 1962, 653, 164; W. P. Neumann, ibid., p. 157; J. C. vaa Egmond, M. J. Jamsen, J. G. A. Luijten, G. J. M. van der Kerk, and G. M. van der Want, J . Appl. Chem., 1962, 12, 17. 134 K. Hoppner and D. Walkiewitz, 2. Chem., 1962, 2, 23. 135 W. P Neumann and K. Konig, Angew. Chem., 1962, 74, 215. . 136 G. J. M. van der Kerk, J. G. A. Luijten, and M. J. Janssen, Chimia (Switz.), 1962, 16, 10; E. W. Abel, D. Brady, and B. R. Lerwill, Chem. and Ind., 1962, 1333; K. Sisido and S. Kozima, J . Org. Chem., 1962, 27, 4051; K. Jones and M. F. Lappert, Proc. Chem. SOC., 1962, 358. 137 I. R. Beattie, G. P. McQuillan, and R . Hulme, Chem. and Ind., 1962, 1429.
HOLLIDAY
: TYPICAL ELEMENTS
143
add across the Sn-Sn bond of substituted distannanes to give R,Sn*C,F,*SnR (R = Ph, Me).l3* I n the hydrolysis of dialkyl-tin(1v) compounds, dimeric intermediates, R4Sn,X,02 (X = halogen, CO,-), are formed; suggested alternative structures for these are (19) and (20).139
R,SnX
Me ,S
R2SnX2
0
i-NEt
RzSnX /
SnR,X ~
(19)
Rn , S
SnR2
Br Sn
Me3
\?
(18)
R2SnX
/ o*
R2SnX2
(20)
There is evidence that in trimethylplumbane, Me,PbH, the lead-attached hydrogen is acidic, and the equilibrium 2Me,PbH + Me,PbMe,PbH,+ is postulated. 140 Group V.--Nitrogen. Active nitrogen reacts with boron trichloride and with germane to form diboron tetrachloride and germanium(n) nitride, respectively; in the reaction with ammonia a t -196, active nitrogen yields hydrazine as an unstable intermediate.141 The formation of NH radicals as intermediates in the Raschig synthesis of hydrazine has been suggested.lg2 Substantial amounts of hydrazine are obtained by glow-dischargeelectrolysis of ammonia-water mixtures (<50% of water) ; the mechanism of formation of hydrazine from ammonia by this method appears to involve formation of NH, radicals.lg3 Hydrazinolysis of trialkylchlorosilanes in the gas phase yields bistrialkylsilyldiazanes, R,Si*NH*NH*SiR,,which on oxidation give nitrogen and hexa-alkyldisilanes; di-alkyldichlorosilanes give chains, ( *SiR,*NH*NH*),, but, if 1,2-dirnethylhydrazine is used, the compound R,ClSi*NMe*NMe*SiClR,(R = Me) is obtained. The existence of the hydrazinium cation N2HG2+ is confirmed by preparation of the salts N,H6(SbC16)2,N,H6(BP4),. reaction of alkali amides with some 144 The imides of elements in Group-111, -IV, and -V, in liquid ammonia as solvent, have been studied conductometrically; imido- rather than amido-anions, e.g., [B(NH),]- and [P(NH)3]3--,P formed.145 The reactions of nitric are oxide with some organometallic compounds have been investigated ; with the alkyls of Group-I1 or - 1 eleme5ts (M), addition to the metal is followed 11 by rearrangement to give M-0-( R)N*and addition of another NO molecule to yield M-O-N(R)-NO, but with the alkyls of Group V, addition of the second NO molecule is followed immediately by splitting-out of nitrous oxide and formation of R-MzO ; with dimethylphosphine, the reaction is :146
4NO
+ Me,PH--+
2N,O
+ Me,PO,H.
1 3 8 M . A. A. Beg and H. C. Clark, Chem. and Ind., 1962, 140. 139 D. L. Alleston, A. G. Davies, and B. N. Figgis, Proc. Chem. SOC., 1061, 457. 140 C. Duffy, J. Feeney, and A. K. Holliday, J . , 1962, 1144. 141 E. R. Zabolotny and H. Gesser, J . Phys. Chem., 1962, 66, 408; R. Storr, A. N. Wright, and C. A. Winkler, Canad. J . Chem., 1962, 40, 1296. 142 J. Fischer and J. Jander, 2. anorg. Chem., 1961, 313, 14, 36. la3A. Hickling apd G. R. Newns, J . , 1961, 5177, 5186. 144 H. Bock, 2. Naturforsch., 1962, lYb, 423, 426. 145P. W. Schenk and J. B. P. Tripathi, Angew. Chem., 1962, 94, 116. 146 M. H. Abraham, J. H. N. Garland, J. A. Hill, and L. F. Larkworthy, Chem. and Ind., 1962, 1615; M . Halmmm and L. Kugel, J., 1962, 3272.
144
INORGANIC CHEMISTRY
No addition of nitric oxide to metallic sodium (to form NaNO) occurs between 190" and 230"; instead, sodium oxide is first formed, and this then adds on nitric oxide to give mixtures of Na,NO, and Na,N,O,; the infrared spectrum of the hyponitrite ion N,0,2- has been further ~tudied.l4~ Vapour-phase oxidation of hydrogen cyanide by nitrogen dioxide a t 200-350 O over a suitable catalyst yields cyanogen :
2HCN
+ NO,+
(CN),
+ NO + H,O.
The nitric oxide is oxidised and then re-cycled and the reaction is a useful means of synthesising cyan0gen.1~~ Azide dimethylamine, Me,N*N3, has been prepared by reabtion of sodium azide and dimethylchloroamine in an inert solvent a t ordinary temperature. 149 Further spectroscopic studies of the isomers of dinitrogen tetrafluoride suggest that these are the cis- and trans-l,2-forms; the nature of the more reactive cis-isomer was previously uncertain. 50 Nitrogen fluorides and their organic derivatives have been reviewed.151 The reactions of the nitrosyl fluoride-hydrogen fluorides, NOF,3HF and NOF,5HF, with many elements and compounds have been studied ; the usual products are the metal fluoride and nitrosyl fluoride. Nitryl fluoride-penta( hydrogen fluoride), N02F,5HF,has been obtained from nitryl fluoride and hydrogen f l ~ 0 r i d e . I The reaction of dinitrogen tetra~~ fluoride and nitric oxide a t 300" yields the intensely-coloured nitroso-difluoramine F,N*NO-it is suggested that the pink colour of N,F, is due to this as jmpurity.153 Phosphorus. A survey of structure and reactions in phosphorus chemistry has a p ~ e a r e d . 1 A ~ ~ new method of preparing metallic phosphides, by reduction of the oxides with phosphine, is suggested.155 The structures of the pentaphenyls of phosphorus, arsenic, and bismuth have been studied ; a square-pyramidal configuration of the phenyl groups, with the Group-V atom within the pyramid, is postulated.156 The " hybrid '' diphosphine, Me,P*P(CF,),, has been prepared; it is less stable than either Me,P-PMe, or (CF,),P*P(CF,),, and can act both as an acceptor (e.g., t o trimethylamine) or as a donor (e.g., to borine).157 The reaction of bistrifluoromethylphosphorus(III) iodide with silver carbonate yields the diphosphoxane, (CF,),P*O*P(CF,),; the corresponding Me,P*O*PMe, undergoes immediate rearrangement and disproportionation.158 Trisilylphosphine, P(SiH,),, has been prepared as a colourless, inflammable liquid by the reaction of monoE. Eachbaur, Monatsh., 1962, 93, 129. W. L. Fierce and W. J. Sandner, I n d . Eng. Chem., 1961, 53, 985. l a s H . Bock and K. L. Kompa, Angew. Chem., 1962, 74, 327. I5O J. H. Noggle, J. B. Baldeschwieler, and C. B. Colburn, J . Chem. Phys., 1962, 37, 182. 151 C. J. Hoffmann and R. G. Neville, Chem. Rev., 1962, 62, 1. 152 F. Seel and H. Semmler, Chimia (Switz.), 1962, 16, 290; F. Seel, W. Birnkraut, and D. Werner, Angew. Chem., 1961, 73, 806. 153 C. B. Colburn and F. A. Johnson, Inorg. Chem., 1962, 1, 715. 154 N. L. Paddock, Roy. Inst. Chem. Lectures, 1962, No. 2. 155 G. V. Samsonov, L. L. Vereikina, and Yu. V. Titkov, Zhur. neorg. Khim., 1961, 6, 749 (382). 156 P. J. Wheatley and G. Wittig, Proc. Chem. Xoc., 1962, 251. 1 ' L. R. Grant, JU"., 5 and A. B. Burg, J . Arner. Chem. SOC., 1962, 84, 1834. 158 J. E. GriEiths and A. B. Burg, J . Amer. Chem. SOC., 1962, 84, 3442.
14'
148
HOLLIDAY: TYPICAL ELEMENTS
145
bromosilane with potassium dihydrogen phosphide in dimethyl ether at low temperature. Several new aminophospliines of the types ArP(NR,), and ArP(NR',)*NR, have been prepared; they form 1 : 1 addition compounds with methyl iodide, and complexes with mercuric iodide.160 Compounds of similar type, e.g., P(NMe2)3and MeP(NMe,),, form 1 : 1 addition compounds with substituted borines; from these, aminoborines, Me,N*BX, (e.g., X =Me, F, Cl), are obtained by heating.161 Reaction of phosphoryl chloride and an excess of methylamine gives PO(NHMe),, phosphoric tri-N-methylamide, and this, when heated to 300, eliminates amine to give first the diphosphoryl compound, P,O,(NMe),, and finally a substance of composition PN0.16, If chlorodiphenylphosphineis allowed to react with ammonia or chloramine in tetrachloroethane as solvent, a solvated compound, (Ph2PN),, is formed and this, when heated, loses solvent and gives a mixture of (Ph,PN), and (Ph,PN), ; the same compounds are obtained if hydrazine hydrochloride is used instead of amrn0nia.16~ Triphenylphosphine imine, Ph,PNH, reacts with substituted borines to give 1 : 1 addition compounds.164 Interest continues in the phosphonitrilic compounds (phosphazens) and the subject has been reviewed;l65routes from phosphorus pentachloride to phosphazens have also been discussed.166 A novel P-N 'ring compound (21) has been
Et
synthesised by reaction of an N-alkylbistrimethylsilylaminewith phosphorus trichloride.167 Phosphonitrilic bromides have been prepared by methods analogous to those used for chlorides,16s and reaction of phosphonitrilic chlorides with thiols has yielded mercaptophosphazens, e.g. compound (22); the structures of several of these have been e 1 ~ c i d a t e d . l ~ ~ reaction of The benzoyl chloride effects conversion of alkoxycyclophosphazens into 1,3,5triazines. 1 7 0 The basicity of some aminophosphazens has been measured; several of these, e.g., N,P,(NH,),, are comparable in base strength with free amines.171 Reaction of phosphorus trichloride with tetrasulphur tetranitride yields the compound (P2NC17), the structures of this and ;
E. Amberger and H. Boeters, Angew. Chem., 1962, 74, 32. G. Ewart, D. S. Payne, A. L. Porte, and (in part) A. P. Lane, J., 1962, 3984. 161 R. R. Holmes and R. P. Wagner, J. Amer. Chem. SOC.,1962, 84, 357. 162 R. R. Holmes and J. A. Forstner, Inorg. Chem., 1962, 1, 89. 163 H. H . Sisler, H . S. Ahuja, and N. L. Smith, Inorg. Chem., 1962, 1, 84. 164R. Appel and F. Vogt, Chem. Ber., 1962, 95, 2225. 165 R. A. Shaw, B. W. Fitzsimmons, and B. C. Smith, Chern. Rev., 1962, 62, 247. l a 6 M . Becke-Goehring and E. Fluck, Angew. Chem., 1962, 74, 382. 16' E. W. Abel and G. Willey, Proc. Chem. Xoc., 1962, 308. 168 K. John and T. Moeller, J. Inorg. Nuclear Chem., 1961, 22, 199. 169 A. P. Carroll and R. A. Shaw, Chem. and I n d . , 1962, 1908; N. Boden, J. W. Emsley, J. Feeney, and L. H. Sutcliffe, ibid., p. 1909. 1 7 0 B. W. Fitzsimmons, C. Hewlett, and R. A. Shaw, Proc. Chem. SOC., 1962, 340. l 7 I D . Feakins, W. A. Lust, and R. A. Shaw, Chem. and I n d . , 1962, 510.
159
l60
146
of the related P3NCI12 have been investigated and are shown to be (Cl,P:N*PCl,:N*PCl,)(PCl,) (Cl,P:N*PCl,)(PCl,) respectively; these and appear to be members of a general class, [Cl,P:N~(PCl,N),*PCl,](PCI,), obtainable from reactions of phosphonitrilic chlorides with phosphorus pentachloride. Treatment of (P2NC1,), with sulphur dioxide gives POCl,,SOCl, and P3N,0C1,.172 A similar compound, P,NOCl,, is obtained by reaction of phosphorus trichloride with dinitrogen tetroxide, and has the structure Cl,P:N*P(O)Cl,. Several oxy- and thio-chlorobromides of phosphorus (e.g., POClBr, and PSC1,Br) have been prepared by reaction of phosphorus pentoxide or pentasulphide with phosphorus(v) chlorobr~mides.~~~ subject of condensed The phosphates and arsenates has been reviewed.17, Although the reaction of tri-n-butylphosphine with sulphur has long been known, isolation of the product, Bun3PS,has only recently been achieved; reaction of Bun,PBr, with hydrogen sulphide gives the related Bun,PS,HBr.l76 Substituted diphosS)RR', can be used to synthesise substituted phine disulphides, RR'P( S)*P( diphosphines by reaction with alkylphosphines, R",P ; with R" = Bu, equimolar amounts of two isomericl diphosphines are obtained. With R = R', reaction of the disulphide with a halogen (X) gives R,P(S)X and then R,PCI,, formulated as (R,PC1,)(R,PCl4) for X = C1; for X = Br, further addition gives R,PBr,, i.e. (R,PBr,)Br,. l77 Reaction of bis(trifluor0methy1thio)- or bis(trifluoromethylse1eno)-mercury with iodobis(trifluoromethyl)-phosphine or -arsine gives the compounds (CF,),X*YCF, (X = P, As; Y = S, Se).178 Diphosphoryl tetrafluoride, P&F4, has now been prepared by dehydration of difluorophosphoric acid with phosphorus(v) oxide; a comparison of the Raman spectrum with that of the corresponding tetrachloride suggests the structure 0:PF2*0*PF,:0.179 Fluorophosphoranes, RPF,, are now conveniently prepared by fluorination of alkyldichlorophosphines with either arsenic or antimony trifluoride.lSo Triferrocenylphosphine, P[Fe(C,H,),],, has been prepared by a Friedel-Crafts reaction of ferrocene and phosphorus trichloride. Arsenic, antimony, and bismuth. Diarsine may be prepared by distilling arsenic trichloride into ethereal lithium aluminium hydride at -190" and warming slowly.lS2 Trisilylarsine has been prepared by the reaction,
3SiH,Br
+ 3KAsH, +As( SiH,), + 3KBr + 2AsH,
172 E. Fluck, 2. anorg. Chem., 1962, 315, 181, 191; M. Becke-Goehring, E. Fluck, and W. Lehr, 2. Naturforsch., 1962, 17b, 126. 1 7 3 M. Becke-Goehring, A. Debo, E. Fluck, and W. Goetzee, Chem. Ber., 1961, 94, 1383; E. Fluck, ibid., p. 1388. 17* W. Kuchen, H. Ecke, and H. G. Beckers, 2. anorg. Chem., 1962, 313, 138. 175 E. Thilo, Adv. Inorg. Chem. Radiochem., 1962, 4, 1. 176 R. A. Zingaro and R. E. McGlothlin, J. Org. Chem., 1961, 26, 5205. 177 L. Maier, J. Inorg. Nuclear Chem., 1962,24, 275; W. Kuchen and K. Strolenberg, Angew. Chem., 1962, 74, 27; W. Kuchen, H. Buchwald, K. Strolenberg, and J. Matten, Annalen, 1962, 652, 28. 17* H. J. EmeMus, K. J. Packer, and N. Welcman, J., 1962, 2529. 179E. A. Robinson, Canad. J. Chem., 1962, 40, 1725. lSo R. Schmutzler, Chem. and Ind., 1962, 1868. lS1 G. P. Sollott and E. Howard, jun., J. Org. Chem., 1962, 27, 4034. lS2 P. J. Fensham, J. Inorg. Nuclear Chem., 1961, 23, 139.
HOLLIDAY
: TYPICAL ELEMENTS
147
in dimethyl ether a t low temperature; the product is colourless and burns in air.ls3 The reaction of some amines with trisdimethylaminoarsine yields compounds of type (23; X = Bu, Ph, NMe,).ls4 Ring structures are suggested for condensed polyfluoroarsenatesobtained by heating K(AsF,OH), 185 and decomposition of triphenylarsenic(m) azide yields the tetrameric cyclic diphenylarsenonitride (24 ; R = Ph).I86 Isopropenyl and vinyl derivatives
Me,N -As -N-X
I
(23)
XN - A s
- NMez
of antimony, R,SbX, (R = CH,:CH, CH,:CMe; X = C1, Br, I),have been isolated.187 A soluble polymeric form of antimonic acid has been obtained by ion-exchange methods, and complexes of the acid with polyhydroxycompounds have been investigated.188 Evidence that fluorination by antimony trifluoride is initiated by a free electron-pair on the antimony has been presented. 189 I n liquid sulphur dioxide as solvent, the compound SbCl,F, exists also in the form (SbC1,)(SbF6), and hence addition of sodium fluoride yields the salt Na(SbCl,F,), whereas reaction with arsenic trifluoride gives (AsCl,)(SbF,) and SbF3.1g0 The structure of " bismuth monochloride " is notable, being made up of large Big5+cations and (Bi,C1,)2- and (BiC1J2- as anions.lgl Perfluoroalkylbismuth compounds, e.g. Me,(CF,)Bi and Me(CF,),Bi, have been prepared by treating trimethylbismuth with a perfluoroalkyl iodide.192 Group V1.-Oxygen. Reviews on compounds of the oxide-water sysand on oxide melts have appeared.194 The new compound ammontem lg3 ium ozonide has been prepared by the low-temperature ozonisation of ammonia ; it displays the characteristic absorption spectrum of an ozonide, but decomposes above -126" to give ammonium nitrate, oxygen, and water.lg5 If ammonia is absorbed on the surface of anhydrous lithium hydroxide, reaction with ozonised oxygen produces Li(NH,),O,, which is very soluble in liquid ammonia but decomposes when the ammonia is removed.196
Amberger and H. Boeters, Angew. Chem., 1962, '94, 293. H. J. Vetter and H. Noth, Angew. Chem., 1962, 74, 943. 185 L. Kolditz and B. Nussbucker, 2. anorg. Chem., 1961, 312, 299; L. Kolditz and D. Renno, ibid., 1962, 315, 46. lE6 W. T. Reichle, Tetrahedron Letters, 1962, 51. A. N. Nesmeyanov, A. E. Borisov, and N. V. Novikova, Izvest. Aka&. Nauk S.S.S.R., Otdel. khim. Nauk, 1961, 1578 (1473). S. H. Gate and E. Richardson, J . Inorg. Nuclear Chem., 1961, 23, 257, 265. R. Muller and C . Dathe, 2. anorg. Chem., 1961, 313, 207. l Q o L. Kolditz, D. Weisz, and U. Calov, 2. anorg. Chem., 1962, 316, 261. l g l A. Hershaft and J. D. Corbett, J . Chem. Phys., 1962, 36, 90. l D 2 T N. Bell, B. J. Pullman, and B. 0. West, Proc. Chem. SOC., . 1962, 224. lD3 0. Glemser, Angew. Chem., 1961, 73, 785. lD4 J. D. Mackenzie, A d v . Inorg. Chem. Radiochem., 1962, 4, 293. lD5 I. J. Solomon, K. Hattori, A. J. Kacmarek, G. M. Platz, and M. J. Klein, J . Amer. Chem. Soc., 1962, 84, 34. A. J. Kacmarek, J. M. McDonough, and I. J. Solomon, Inorg. Chem., 196?, 1 , 659.
lE3 E.
lS4
148
INORGANIC CHEMISTRY
Sulphur. The reaction of elementary sulphur with a diaryldiazomethane gives a tetra-arylethylene sulphide in good yield : I 9 7
2Ar,CN,
+ S-+Ar,C-CAr,
S '/
+ 2N,.
When tetraphenyltin and sulphur are heated together a t 190", the principal product is the trimer, (Ph,SnS),, which has a cyclic structure of alternate tin and sulphur atoms analogous to that of the (R,SnS), compounds.198 Tetrasulphur tetranitride has been prepared by heating ammonium chloride with sulphur monochloride vapour, and trisulphur dinitrogen tetroxide, S3N204, reaction of thionyl chloride vapour with a heated mixture of by sulphur and ammonium chloride.l g 9 An electron-spin resonance spectral study of sulphur nitride anions, e.g., S4N4-, indicates delocalisation of the n-electrons over the ring.200 The existence of sulphur nitride cations, e.g., S4N,f, is suggested by cryoscopic and conductivity measurements on S4N3C1in solution. ,01 Reaction of trithiazyl chloride with dimethyl sulphoxide yields an alkylated disulphur nitride; this forms a conducting solution and is probably dissociated, in the excess of dimethyl sulphoxide used as solvent :202
(NSCl),
+ 6Me,SO -+ 3(Me2S*N:SMe,)C1 + 3S0,.
Addition of chloramine t o dialkyl sulphides gives sulphiminium salts, e.g., (R,S*NH,)Cl (R = Me, Et) ; de-protonation of the corresponding sulphate (R2NH,),SO4 gives a sulphimine, R,S:NH, stable below 30.203 Imidobisulphuryl chloride, ClSO,*NH*SO,Cl, is prepared by reaction of phosphorus pentachloride with sulphamic acid, and subsequent treatment of the initial product, Cl,P:N*SO,Cl, with chlorosulphonic acid ; the same compound is formed directly by reaction of this acid with urea; fluorosulphonic acid with urea gives the fluoride, HN(SO,F),. 204 A thiohydroxylamine-S-sulphonate, H,N*S*SO,-, is obtained by reaction of a thiosulphate with a hydroxylamine0sulphonate ; it gives unstable thiohydroxylamine on acid hydrolysis. 205 Reaction of ammonia with SOF, in presence of sodium fluoride in ether yields the etherate of iminosulphuroxydifluoride, HN :SOF,, as a colourless liquid ; removal of ether, and dehydrofluorination, gives a rubbery poly(oxyfluorosulphur nitride), ( *N:SOF*),, apparently analogous to rubbery phosphonitrilic chloride polymer.206 The ring structure of a-sulphanuric chloride, (=N:SOCl*),,is now found to be a non-planar chair form with approximately tetrahedral bonding around the sulphur, and the S-N-S angle -120.207 An extensive study of reactions of sulphides in liquid
A. Schonberg and E. Frese, Chem. Ber., 1962, 95, 2810. M. Schmidt, H.-J. Dersin, and H. Schumann, Chem. Ber., 1962, 95, 1428. W. L. Jolly and M. Becke-Goehring, Inorg. Chem., 1962, 1, 76. 2oo D. Chapman and A. G. Massey, Trans. Faraday Soc., 1962, 58, 1291. 2 0 1 M. Becke-Goehring and H. P. Latscha, 2. Naturforsch., 1962, 17b, 125. 2 0 2 M. Recke-Goehring and H. P. Latscha, Angew. Chenz., 1962, 74, 695. 203 R. Appel and W. Buchner, Chem. Ber., 1962, 95, 849. 204 R. Appel and G. Eisenhauer, Chem. Ber., 1962, 95, 246; R. Appel, M. BeckeGoehring, G. Eisenhauer, and J. Hartenstein, ibicl., p. 625. 2 0 5 R. Gosl and A. Meuwsen, 2. anorg. Chem., 1962, 314, 334. 2 0 6 G. W. Parshall, R. Cramer, and R. E. Foster, Inorg. Chem., 1962, 1 677. , 107 A. J. Banister and A. C. Hazell, Proc. Chem. SOC., 1962, 382.
197 198 lS9
H O L L I D A Y : T Y P I C A L ELEMENTS
149
ammonia has been continued; silicon disulphide yields compounds such as SiS(NH,), and SiS:NH, whereas germanium disulphide gives ammonium salts such as NH4( GeS,*NH,) which gives (NH,),(Ge,S,) when heated ; stannic sulphide behaves similarly.208 Some isothiocyanates, e.g., P(NCS), and As(NCS),, have been prepared in acetonitrile or liquid .sulphur dioxide as solvent by reaction of a metal thiocyanate with the appropriate chloride.209 The reaction of phenylphosphine with sulphur monochloride yields the compound (C,H,PS,), for which a cyclic structure is suggested.210 A method for the preparation of disulphur monoxide, S,O, by heating a heavy-metal oxide with sulphur in vacuo, has been reported.211 Further studies of the sulphuric acid solvent system have been made; Raman spectral studies of sulphuric acid-sulphur trioxide and deuterium sulphate-sulphur trioxide mixtures give evidence for the existence of species such as H,S4013 at high sulphur trioxide concentrations, and for the non-ionic dissociation of oleum to give H2S3010 and sulphuric acid. Similar studies of solutions of sulphur trioxide in fluoro- and chloro-sulphuric acids give evidence for, e.g., H,S20,F and HS,O,Cl. I n concentrated solutions of tetra(hydrogen sulphato)boric acid, HB(HSO,),, in sulphuric acid, elimination of disulphuric acid gives polymers containing B-O-B bonds; attempts to produce salts of the acid by metathesis of potassium hydrogen sulphate and H(BHSO,), gave instead polysulphatoborates containing six-memberedrings of alternate sulphur and oxygen atoms.212 The chemistry of sulphur tetrafluoride has been reviewed,213 and bond lengths and angles, and the dipole moment have been determined.214 Alkyl-, fluoroalkyl-, and aryl-sulphur trifluorides have been synthesised by fluorination of the appropriate disulphides with silver difl~oride.21~ The preparation of disulphru. decafluoride by photochemical reduction of sulphur chloride pentafluoride by hydrogen is reported, and some reactions of the decafluoride in sealed glass tubes a t 150-200 O have been investigated ; halogens (X) yield SF,X, but SF,CN is not formed with cyanogen; ammonia gives NSF, and S,,N, when in excess.216 It is suggested that Lewis acids may attack sulphur hexafluoride by co-ordination to a fluorine atom; in support of this, a slow reaction with anhydrous aluminium chloride occurs a t 180-200" to give some aluminium fluoride, chlorides of sulphur, and chlorine; sulphur trioxide at 250" gives some SO,F,.217 New methods of preparing sulphur chloride pentafluoride have been described, e.g., by reaction of chlorine trifluoride with sulphur, or chlorine monofluoride with sulphur tetrafluoride. 218 Reactions of SClF, with some metal carbonyls are
H. Behrens and J. Ostermeier, Clzem. Ber., 1962, 95, 487. D. B. Sowerby, J. Inorg. Nuclear Chern., 1961, 22, 205. 210E. Fluck and R. M. Reinisch, Chem. Ber., 1962, 95, 1388. 211 A. R. Vasadeva Murthy, Nature, 1962, 193, 773. 212 R. J. Gillespie and E. A. Robinson, Cunad. J . Chem., 1962, 40, 658, 675, 784,
208
209
1009.
213
W. C. Smith, Angew. Chem., 1962, 74, 742.
214W.Tolles and W. D. Gwina, J . Chem. Phys., 1962, 36, 1119. M. 215 W. A. Sheppard, J . Arner. Chem. Xoc., 1962, 84, 3058.
216 B. Cohen and A. G. MacDiarmid, Chem. and I n d . , 1962, 1866; H. L. Roberts, J., 1962, 3183. 217 J. R. Case and F. Nyman, Nature, 1962, 193, 473. 218F. Nyman and H. L. Roberts, J., 1962, 3180.
150
reported, e.g., with nickel carbonyl, nickel chloride difiuoride is obtained.210 Pentafluorosulphuroxyaryl compounds, ArO-SF, have been prepared by reaction of, e.g., toluene or chlorobenzene with bispentafluorosulphur peroxide, F,S*0*0*SF,;220 the latter compound, SF,Cl, and S2F1, all react photochemically with sulphur dioxide to give pentafluorosulphur fluorosulphate, F,S*0*S02F.221 Some reactions of pentafluorosulphurhypofluorite are also reported; it decomposes a t 210" to give oxygen and sulphur hexafluoride, and reacts with sulphur tetrafluoride to give a mixture of SF6,SOP,, F,S*O*O*SF,,and F,S*O*SF,, .and with carbon monF oxide to give F,CO and Peroxydisulphuryl 8 fluoride,F02S*O*O*S02F, behave as an oxygenat. \ ...... o-:-F 4 can ing agent (e.g., to carbon monoxide and trifluoro, s ; F':.......... : o o O-i-F (25) phosphine), or as a fluorosulphonating agent (e.g., to HgO, C5H8),or as both (e.g., to SOClF). ReF action at ordinary temperature with tetrafluoroethylene gives tetrafluorobis(fluorosulphonato)ethane, C2F4(S03F),,and with sulphur tetra fluoride, tetra fluorobis(fluorosulphonat 0) sulphur(VI), SF4(S0,F),, is obtained; this has the structure (25).223 Xelenium and tellurium. Perfluoroalkyl silyl selenides, SiH3*SeRF (RF = CF,, C3F,), have been prepared by reaction of iodosilane with bis(perfluoroalkyl)selenomercury, Hg(SeRF),; they decompose slowly at ordinary temperatures to give fluorosilanes and other pr0ducts.22~ Salts of imidoselenic acids, M,(O,Se*N*SeO,)(M = K, Ag), have been prepared by reaction of SeO,F, with ammonia and then treatment with alkali.3Z5 Fluoroselenic acid, HSeO,F, may be prepared by reaction of anhydrous hydrofluoric acid with selenium trioxide.226 Raman spectral studies of selenious acid indicate the presence of the species SeO,2- and HSe0,- only when alkali is added; in water alone, dissociation of H2Se03 is negligible.227 An extensive study of complexes of both tellurium-(n) and -(Iv)?with various urea derivatives as ligands, has been continued ; with ethylenethiourea (etu) many complexes, Te(etu),X,, have been prepared; and with X = Br, two forms, probably cis and trans, have been isolated.228 Group VII.-Reviews have been published on halogen cations,22g organoand the silicon compounds of fluorine,930 new fluoroalkyl c0mpounds,23~
!..I
'
219
220
A. G. Massey and K. J. Packer, J., 1961, 5554. J. R. Case, R. Price, N. H. Ray, H. L. Roberts, and J. Wright, J., 1962,
2107.
H. J. Emelbus and K. J. Packer, J., 1962, 771. S. M. Williamson and G . H. Cady, Inorg. Chem., 11962, 1, 673. J. M. Shreeve and G . H. Cady, J. Amer. Chem. SOC.,1961, 83, 4521. 2 2 4 E. A. V. Ebsworth, H. J. Emelkus, and N. Welcman, J., 1962, 2290. 2 2 5 A. Engelbrecht, Monatsh., 1961, 92, 1269. 2 2 6 H. Bartels and E. Class, Helv. Chim. Acta, 1962, 45, 179. 2 2 7 G. E. Walrafen, J. Chem. Phys., 1962, 36, 90. 2 2 8 0. Foss and W. Johannesen, Acta Chem. Scand., 1961, 15, 1939, 1940, 1941; 0. Foss and 1.-J. Johannesen, ibid., p. 1943; 0. Foss and S. Hauge, ibid., pp. 1615, 1616, 1623; 0. Foss and S. Fossen, ibid., pp. 1618, 1620; 0. Foss and K. Marpy, ibid., pp. 1945, 1947. S2Q J. Arotsky and M. C. R. Symons, Quart. Rev., 1962, 16, 282. aso 0.V. Odabashyan, V. A. Ponomarenko, and A. D. Petrov, Uspekhi Khim., 1961, 30, 941 (407). 231 H. J. Emelbus, Angew. Chem., 1962, 74, 189.
221
222
223
H O L L I D A Y : TYPICAL ELEMENTS
151
fluorides of the actinides.232 The reaction of many chloro-compounds, e.g., CCl,, COCl,, S02C1,, RSiC1, and PCl,, with molten alkali or alkaline-earth fluorides affects quantitative exchange of halogens to give the corresponding fluoro-compounds.233 The reabtion of fluorine with halides of rubidium gives fluorohalogenates, e.g., RbBrF4.2s4 A large number of stable molecular complexes of interhalogen compounds with pyridine and its derivatives have been prepared.235 The structure of the compound KF,2A1Et3 has now been cofimed as KEt3A1*F*A1Et,; A1-C bond lengths are normal the for sp3-hybrid bonds, and the Al-F distance is the same as in cryolite; bonding sp-hybridisation of the fluorine atom is suggested, with some A1-F nby overlap of fluorine 2 p with vacant aluminium 3d-orbitals.236 The reaction of trifluoromethyl iodide with nitric oxide and dinitrogen tetrafluoride is activated thermally and by ultraviolet radiation, and the product is 2-fluoro-l-trifluoromethyldiazen 1-oxide, F,C*NO :NF.237 Further studies have been made in liquid hydrogen chloride as a solvent; solubilities and reactions of compounds containing doubly-bonded oxygen have been studied, and also compounds containing multiple bonds, e.g., acetylenes, olefins, and nitriles ; all these act as solvo-bases.238 The effect of strong acids on periodic acid has been studied spectrophotometrically; in strong aqueous acids, there is evidence for the cation [I(OH),]+, but in 65% oleum an orange solid, probably 120,, is The colour of solutions of iodine in sulphuric acid and oleum has been confirmed as due to I+, and there is evidence for the existence here of Is+,13f,and H2103+also; from 65% oleum, white crystals of the iodyl compound, (IO)HS,O,, can be obtained."O The reaction of iodine with an excess of silver perchlorate in ether at low temperatures yields the complex, AgC10,,I(C104) and some I(C10J3; in ethyl alcohol, the monoperchlorate, I(C104), is the only prod ~ An infrared ~ & ~ study of the structure of iodine dioxide has confirmed ~ the structure (10)+( 10,) 242 I n methylene dichloride as solvent, iodine -. and hydrogen sulphide form a 1 : 1 addition compound; there is evidence for the equilibrium z43
H,S,I,
+ (H,SI)+ + I-.
A. K. H.
N. Hodge, Adv. Fluorine Chem., 1961, 2, 138. W. Sundermeyer, 2. anorg. Chern., 1962, 314, 100. 2 3 4 H. Bode and E. Klesper, 2. unorg. Chem., 1961, 313, 161. 2 3 5 M. T. Rogers and W. K. Meyer, J . Phys. Chem., 1962, 66, 1397. 2 3 6 G. Natta, G . Allegra, G. Perego, and A. Zambelli, J. Amer. Chem. SOC., 1961, 83, 5033. 237 J. W. Frazer, B. E. Holder, and E. F. Worden, J. Inorg. Nuclear Chem., 1962, 24, 45. 2 3 * M. E. Peach and T. C. Waddington, J., 1962, 600, 2680. 238 H. C. Mishra and M. C. R.. Symons, J., 1962, 1194. a 4 0 J. Arotsky and M. C. R. Symons, Nature, 1962, 193, 678; J. Arotsky, H. C. Mishra, and M. C. R. Symons, J., 1962, 2582. Za1N. W. Alcock and T. C. Waddington, J., 1962, 2570. 2 4 2 J. H. Wise and H. H. Hannan, J . Inorg. Nuclear Chem., 1961, 23, 31. 2 4 3 J. Jander and G. Tiirk, Chem. Ber., 1962, 95, 881.
232
233
152
INORGANIC CHEMISTRY
3. T H E TRANSITION ELEMENTS
ONCE again a large number of publications have been concerned with complexes of the transition elements, As in .previous years, organometallic compounds and complexes not conveniently discussed under the particular groups will be treated separately. Great advances have been made in the halogen chemistry of the transition metals, and the preparations of previously non-existent halides will be mentioned in the particular groups. The chemistry in the groups will be described, wherever possible, in order of ascending oxidation numbers of the elements, and within each oxidation state the order will be that of ascending atomic weights. General reviews published during the year have been concerned with the cyanide complexes of the transition metals and with the use of nuclear magnetic resonance spectroscopy in inorganic chemistry.2 Scandium, Yttrium, and the Rare Earths.-Zerovalent tris(bipyridyls), Sc(bipy),, and Y(bipy),,STHF are obtained upon reduction of the corresponding trichlorides with lithium in tetrahydrofuran (THF) in the presence of 2 , 2 ' - b i p ~ i d y l . ~ n the absence of the reducing agent, the complexes I ScCl,(bipy), and ScCl,(phen), (phen = 1,lo-phenanthroline) can be isolated.* Thermal-stability studies a t 340-440 " on the light rare-earth oxalates give the following relative order of stabilities : Gd > Sm > Nd > La > Pr > Ce. Erbium and lutetium oxalates are stabilised by traces of water, and decomposition a t 350" begins only after a long induction period.5 I n the scandium(111) chloride-caesium chloride phase diagram there is a congruentlymeking phase of composition cs3scc16, and a 3 : 2 compound, cs,sc,c1,, with a peritectic point a t 619".6 The composition and solubility of cerium(111) chloride alcoholates have been investigated; one to four molecules of aliphatic alcohols co-ordinate, and solubilities have been determined for CeCl,(EtOH),, CeCl,(PrOH),, and CeCl,( BuOH),. The solid acid chelates formed by tripositive rare-earth ions from cerium to samarium with the protonated EDTA ligand are monohydrated, while the rest are anhydrous. Infrared studies indicate that the change in hydration number is accompanied by a change in co-ordination of the EDTA ligand from penta- to hexa-dentate. * Numerous papers have appeared on the thermodynamics of formation of rare-earth chelates with amino-acid ligands.9 Colourless, diamagnetic, complex fluorides, M,CeF, and M2CeF6 (M = Na, Rb, Cs), have been obtained from the fluorination of mixtures of cerium(rv) oxide
1
2
W. P. Griffith, Quart. Rev., 1962, 16, 188. E. L. Muetterties and W. D. Phillips, A d v . Inorg. Chem. Radiochem., 1962, 4,
231.
3 S. Herzog, G. Byham, and P. Wulfert, 2. Chem., 1961, 1, 370; S. Herzog and K. Gustav, 2. Nuturforsch., 1962, 17b, 62. 4 E. N. Ivanov-Emin, L. A. Nisel'son, and L. A. Larionova, Zhur. neorg. Khim., 1961, 6, 170 (334). 5 A. Glasner and M. Steinberg, J . Inorg. Nuclear Chem., 1961, 22, 39, 156. 6 R . Gut and D. M. Gruen, J . Inorg. Nuclear Chem., 1961, 21, 259. 7 F. R . Hartley and A. W. Wylie, J., 1962, 679. 8 R. S, Kolat and J. E. Powell, Inorg. Chem., 1962, 1, 485. 9 T. Moeller and R. Ferrus, J . Inorg. Nuclear Chem., 1961, 20, 261; idem, Inorg. Chem., 1962, 1, 49; T. Moeller and L. C. Thompson, J . Inorg. Nuclear Chem., 1962, 24, 499; L. C. Thompson, Inorg. Chem., 1962, 1 490; J. L. Mackey, M. A. Hiller, and , J. E. Powell, J . Phys. Chem., 1962, 66, 311.
NICHOLLS
: THE TRANSITION ELEMENTS
153
and alkali-metal chlorides ; Na,CeF, is tetragonal while Cs,CeF7 and Rb,CeF, have cubic structures. Przeseodymium fluorides are prepared similarly.10 The separation of the rare earths by volatilisation of their oxides at 2500" in a solar furnace has been investigated; cerium(1v) oxide can be separated pure from its mixtures with lanthanum(II1) oxide in this way.l1 The Actinides.-The actinide oxides have been the subject of a review.12 Hydrolysis of uranium monocarbide gives gelatinous hydrous uranium(~ v ) oxide together with gaseous products consisting of methane (86 vol. o/o), hydrogen (11 vol. yo)and other c - 6 hydrocarbons.l 3 Salts containing 2c the pentacarbonatothorate(Iv) ion have been prepared. They can be precipitated quantitatively with hexa-amminecobalt(II1) chloride as [CO(NH,)~],[T~(CO,),],~H~~. l4 Thorium(m) chloride reacts with carboxylic acids to form tetracarboxylates with monobasic acids and bisdicarboxylates with dibasic acids.15 While uranium(1v)perchlorate is unstable and cannot be isolated, a dimethylacetamide complex, U(ClO,),,GAcNMe,, is formed when the chloride analogue is treated with silver perchlorate in acetone and the ligand added.l6 Uranium(1v) oxide cannot be used as a refractory in view of its reaction, and consequent swelling, with oxygen, forming U,O,. The fluorite structure can, however, be stabilised by forming solid solutions with tervalent oxides of lanthanum or yttrium.17 The oxidation of the U4+aq. ion has been studied by l80tracer techniques. With oxygen or ozone only one of the oxygens in the U0,2+ product is derived from the oxidising agent, but with lead and manganese dioxides both oxygens are derived from the oxidiser.ls I n view of the short U=O distance in uranyl compounds it has been suggested that there is interaction between the lone pairs on the oxygens and the vacant orbitals on uranium.19 Ammonium diuranate is very variable in composition but, from a comparison of the infrared spectra of various uranium oxide hydrates, its structure appears to be UO,( OH),,xNH,,yH,0.20 Plutonium(1v) complex halides can be prepared by the chlorination of melts containing plutonium(II1) chloride and an allCali-metalchloride at 0.8 atm. at 50" above the melting point.2l Some evidence has been found for plutonium(vI) fluoride in the high-temperature oxidation of plutonium(m) fluoride with dry oxygen.22 Quadrivalent
l o R. Hoppe and K.-M. Rodder, 2. anorg. Chem., 1961, 313, 154; R. Hoppe and W. Liebe, ibid., p. 221. l1 I. Trombe and M. Foex, Compt. rend., 1962, 255, 1447, 1516. l 2 L. E. J. Roberts, Quart. Rev., 1961, 15, 442. l3 M. J. Bradley and L. M. Ferris, Inorg. Chem., 1962, 1, 683. l4 I. I. Chernyaev, V. A. Golovnya, and A. K. Molodkin, Zhur. neorg. Khim., 1961, 6, 394 (200); 809 (413). l5 S. Prasad and S . Kumar, J . Indian Chem. SOC., 1962, 39, 444. l6 K. W. Bagnall, D. Brown, and A. M. Deane, J., 1962, 1655. l7 W. B. Wilson, C. A. Alexander, and A. F. Gerds, J . Inorg. Nuclear Chern., 1961,
G. Gordon and H. Taube, Inorg. Chem., 1962, 1, 69. M. E. Dyatkina, V. P. Markov, I. V. Tsapkina, and Yu. N. Mikhailov, Zhur. neorg. Kfim., 1961, 6, 575 (293). 2 o A. M. Deane, J . Inorg. Nuclear. Chem., 1961, 21, 238. 21 R. Benz and R. M. Douglass, J . Inorg. Nuclear Chem., 1961, 23, 135. 2 2 C. J. Mandleberg, D. Davies, and K. E. Francis, J . Inorg. Nuclear C h e w , 1961,
l9
20, 242.
21, 92.
154
INORGANIC CHEMISTRY
americium has been stabilised by co-ordination with fluoride ions. On dissolution of americium(1v) hydroxide in ammonium fluoride solutions, no disproportionation occurs ; by using rubidium fluoride, Rb,AmF, can be precipitated. 23 The compound UCl,,PCl,, prepared a t room temperature from phosphorus pentachloride and uranium(v1) oxide, dissociates in phosphorus oxychloride to form PCI,+ and UcI6-q Electrolysis of the solution gives uranium(n) chloride a t the anode and phosphorus tri- and penta-chloride a t the cathode.24 The chemistry of uranium fluorides has been re~iewed.~5 The oxide U308 is converted into uranium(@ fluoride by fluorine a t 1000 lb./in.2.26 Hydrogen chloride reacts with mono- and poly-uranates of potassium t o give the uranyl chlorides, K,UO,Cl,, K,(UO,),Cl,, K,(U0,),C18, and K,(U0,),C110.27 Contrary to earlier reports, the reduction of neptunium(vI) in chloride media is very slow a t room temperature, and a satisfactory absorption spectrum of this ion can thus be obtained. The accelerated reduction in the presence of platinum is not due to a catalytic effect but t o reduction by the platinum itself.38 The chemistry and structure of peroxouranates has been reviewed.29 Titanium, Zirconium, and Hafnium.-Absorption spectra studies of the hydrates formed by Ti3+ in low or moderate concentrations show that these have tetragonal bipyramidal and not octahedral ~yrnrnetry.~O The first hydrolysis constant for the aquotitanium(1 1 ion has been measured potentio1) metrically.31 Tervalent and bivalent chlorides of titanium are antiferro= magnetic with ,ueff. 1.31 B.M. for titanium(1n) chloride and 1.08 B.M. for titanium(I1) chloride. Magnetically-dilute complexes, e.g., Ti(Urea),(ClO,),, show the expected moment, ,u = 1.72 B.M. Antiferromagnetic interaction probably occurs also in the lower-Talent chlorides of zir~onium.3~ Reduction of zirconium(1v) iodide with aluminium yields zirconium(II1) iodide ;33 zirconium(11 bromide has been prepared by reduction of zirconium(Iv) 1) bromide with finely powdered zirconium.34 Electromigration studies of titanium(1v) ions in hydrochloric acid show that anionic complexes are ~ predominantly formed only a t concentrations greater than 1 0;35 the solid phases H,[Ti(OH),Cl,] and H,[Ti(OH),Cl,] have been detected in the TiC14-HC1-H,0 system.36 Hexafluorotitanates(1v) have been prepared from titanium(1v) fluoride and amines in acetone solution saturated with hydrogen
23 L. B. Asprey and R. A. Penneman, Inorg. Chem., 1962, 1, 135; F. H. &use and L. B. Asprey, ibid., p. 137. 24 R . E. Panzer and J. F. Suttle, J. Inorg. Nuclear Chem., 1961, 20, 229. 2 6 I. V. Tananaev, N. S. Nikolaev, Yu. A. Luk'yanychev, and A. A. Opalovskii, Uspekhi Khim., 1961, 1490 (654). 26 R. E. Greene and G. S. Petit, J. Inorg. Nuclear Chem., 1962, 24, 393. 27 J. Lucas, Compt. rend., 1962, 255, 313. 2s D. Cohen and B. Taylor, J. Inorg. Nuclear Chenz,., 1961, 22, 151. 29 I. I. Chernyaev, V. A. Golovnya, and G. V. Ellert, Zhur. neorg. Khim., 1961, 6, 790 (403). 80 I. I. Antipova-Karataeva, E. E. Vainshtein, and Yu. I. Kutsenko, Zhur. neorg. Khim, 1961, 6, 2329 (1181). 31 R. L Pecsok and A. N. Fletcher, Inorg. Chem., 1962, 1, 155. . 32 J. Lewis, D. J. Machin, I. E. Newnham, and R. 8. Nyholm, J., 1962, 2036. 33 G. W. Watt and W. A. Baker, J. Inorg. Nuclear Chem., 1961, 22, 49. 34 H. L. Schlafer and H. Skoludek, 2. anorg. Chem., 1962, 316, 15. 3 5 B. I. Nabivanets, Zhur. neorg. Khim., 1962, 7, 412 (210). 36 G. M. Toptygina and I. S. Morozov, Zhur. neorg. Khim., 1961, 6, 1685 (861).
NICHOLLS
: THE T R A N S I T I O N E L E M E N T S
155
fluoride; their X-ray d spacings and infrared spectra are reported.37 While trimethylamine rapidly reduces titanium(1v) chloride, pyridine forms TiC14,2pywhich is stable in the absence of excess of ~ y r i d i n e . ~ * The first aminolyses of titanium(IT)fluoridehave been reported ;with di-n-propylamine the products are R2NTiF, and (R2NH,+),TiF62 -.39 Several new addition compounds of titanium(1v) chloride with esters have been reported; they Titanium(1v) are of the types TiCl,,PhCO,Me and TiC14,2Me*C6H,*C0,Me.40 alkoxides yield mono-, di-, tri-, and tetra-substituted derivatives with 2-hydroxyethylamine ; Ti(OR),(0 *C,H,*NH,) and Ti(OR),( O*C,H,-NH,), are dimeric in benzene.41 Biscyclopentadienyltitanium dichloride is ammonolysed in liquid ammonia, (n-C,H,),TiCl(NH,) and (n-C,H,),Ti(NH,), being probable products. 4 2 Reaction of cyclopentadienylsodium with dichlorodiethoxytitanium(1v) yields (n-C,H,)Ti(OEt), which is monomeric in benzene and yields (n-C,H,)TiCl, upon treatment with acetyl chloride.43 The yellow, solid oxychloride, TiOCl,, is formed in reactions between titanium(1v) chloride and arsenic, antimony, and bismuth trioxides.44 Only one peroxide phase, Ti(O*OH)(OH),,is formed when hydrated titanium dioxide is treated at 0" or -20" with hydrogen peroxide of a wide variety of concentration^.^^ Complex peroxy-compounds with oxalic acid, Ti02(C20,),3H,0, can be isolated in the solid state.46 Titanyl bisacetylacetonate, prepared by reaction of acetylacetone with titanyl di-n-propoxide, has been shown to be monomeric and hence five-co-ordinate in benzene.47 Other five-co-ordinate titanium complexes prepared include the products of the reactions of titanium(1v) alkoxide with the chelating agents salicylaldehyde and methyl salicylate;48 these contain three alkoxide groups and one chelate. A crystallographic study of the titanium-sulphur system has been reported. 4 9 Tetranitratozirconium(1v) has been prepared as colourless, sublimable crystals by means of the reaction:50
ZrC1,
+ 4N,O, +Zr(NO,), + 4N0,Cl.
It is very hygroscopic and rapidly reacts with toluene at room temperature to give nitro-compounds. Treatment of zirconium tetra-acetylacetonate
8 7 J. A. Chandler, R. S. Drago, and R. Latham, jun., J . Inorg. Nuclear Chem., 1961, 21, 283. s8 I. R. Beattie and G. J. Leigh, J . Inorg. Nuclear Chem., 1961, 23, 55. 3 g J. A. Chandler, J. E. Wuller, and R. S. Drago, Inorg. Chem., 1962, 1 65; J. A. , Chandler and R. S. Drago, ibid., p. 356. 4 0 B. Mori, J. Gohring, D. Cassimatis, and B. P. Susz, Helw. Chim. Acta, 1962, 45, 77. 41 D. M. Puri and R. C. Mehrotra, J . Indian Chem. SOC., 1962, 39, 447. 4 2 R. S. Dickson and B. 0. West, Austral. J . Chem., 1962, 14, 555. 4 3 A . N. Nesmeyanov, 0. V. Nogina, and A. M. Berlin, Izvest., Akad. Nauk S.S.S.R., Otdel. chim. N a u k , 1961, 804 (743). 4 4 P. Ehrlich and W. Engel, 2. anorg. Ch.em., 1962, 317, 21. 4 5 S. 2. Makarov and L. V. Ladeinova, Izvest., Akad. Nauk S.S.S.R., Otdel. chim. N a u k , 1961, 958 (889). 4 6 G . V. Jere and C. C. Patel, J . Inorg. Nuclear Chem., 1961, 20, 343. 4 7 A. N. Nesmeyanov, 0. V. Nogina, and IT. Dubovitskii, Izvest., Akad. Nauk A. S.X.X.R., Otdel. chim. N a u k , 1961, 437 (403). 4 8 A . Yamamoto and S. Kambara, J . Inorg. Nuclear Chem., 2961, 21, 58. 4 g Y. Jeannin, Ann. Chim. (France), 1962, 7, 57. 6 o B. 0. Field and C. J. Hardy, Proc. Chem. SOC., 1962, 76.
156
INORGANIC CHEMISTRY
with carboxylic acids yields tetra-acyloxyzirconiums, [X(CH,),CO,],Zr (X = H, Cl).51 The infrared spectrum of ZrC1,,2EtOAc shows it to have the cis-octahedral structure while TiBr4,2EtOAc and Ti14,2EtOAc are probably trccns-o~tahedral.~~ Hydrolysis of zirconium alkoxides, Zr(OR),, with secondary or tertiary alkoxide groups leads t o polymeric zirconium oxide alkoxides having low number-average degrees of polymerisation. 53 With hydrazine, alkoxides form the complexes Ti(OPri),,N,H,, Zr(OPrI),,N,H,, and Ti(OEt),,iN,H, of unknown s t r ~ c t u r e . ~ ,In weakly acid media, electrically neutral sulphate complexes are formed by the addition of sulphate ions t o polymeric zirconium cations; when an excess of sulphate is present the poly-ion chain is ruptured with the formation of anionic complexes.55 Vanadium, Niobium, and Tantalum.-The solid portion of the V-VC phase diagram shows that the VC phase does not extend to VC1.oo,terminating a t v O8 a t 1000o.56 The phase VSl.02-VS1.22exhibits antiferromagc .8 netism owing t o vanadium(I1)-vanadium(rn) intera~tion.~'Tris-B,B'-bipyridylniobium(0) is obtained as violet crystals upon reduction of niobium(v) chloride in tetrahydrofuran with lithium and 2,2'-bipyridyl; it has the expected magnetic moment of 1.75 B.M.58 Vanadium(I1) chloride does not dissociate or disproportionate a t 900-1 100* ; disproportionation of vanadium(m) chloride becomes appreciable at 425" in an atmosphere of argon.59 Hydrates of vanadium(@ halides, e.g., VF2,4H,0 and V12,6H,0, can be isolated when solutions of vanadium(v) oxide in the respective acids are reduced cathodically.60 Some new five-co-ordinate vanadium(II1) compounds, VC13,2SMe2, VC13,2SEt2, and VBr3,2NMe,, have been isolated. Dipole-moment measurements strongly suggest that these have the transtrigonal bipyramidal structure.61 Lower aliphatic alcohols co-ordinate with vanadium(rr1) chloride to give green solid alcoholates, e.g., VC13,4MeOH, and vanadium(II1) alkoxides can be prepared by using lithium methoxide and ethoxide on the trichloride.62 The reaction of an excess of formic acid with vanadium(=) and vanadium(1n) chlorides yields vanadium(1v) formate ; this compound decomposes, when heated in an inert atmosphere, to give vanadium(1v) oxide.63 Disproportionation of vanadium( m) bromide has provided the first route t o the hitherto unknown tetrabr~mide.~,The phases NbC13.1-3.2 and TaC13.1--3.2 appear upon disproportionation of the tetra5 1 E. M. Brainina, R. Kh. Freidlina, and A. N. Nesmeyanov, Izvest., Akad. Nauk X.S.X.R., Otdel. chim. Naulc, 608 (560). 5 2 M. F. Lappert, J., 1962, 542. 63 D. C. Bradley and D. G. Carter, Canad. J . Chem., 1962, 40, 15. 5 4 M. S. Bains and D. C. Bradley, Canad. J . Chem., 1962, 40, 1350. 5 5 B. I. Nabivanets, Zhur. neorg. Klzim., 1961, 6, 1319 (677). 5 6 E. K. Storms and R. J. McNeal, J . Phys. Chem., 1962, 66, 1401. 5 7 G. M. Loginov, Zhur. neorg. Khim., 1961, 6, 261 (133). 5 8 S. Herzog and R. Schuster, 2. Naturforsch., 1962, 17b, 62. 59M. A. Oranskaya and I. L. Perfilova, Zhur. neorg. Khim., 1961, 6, 257 (131); M. A. Oranskaya, Yu. S. Lebedev, and I. L. Perfilova, ibid., p. 259 (132). 6 0 H.-J. Seifert and B. Gerstenberg, 2. anorg. Chem., 1962, 315, 56. 61 M. W. Duckworth, G. W. A. Fowles, and R. G. Williams, Chem. and Ind., 1962, 1285. 6 a D .C. Bradley and M. L. Mehta, Canad. J . Chem., 1962, 40, 1710. 6 3 P. H. Crayton and R. N. Vance, jun., J . Inorg. Nuclear Chem., 1961, 23, 154. 6 4 S. A. Shchukarev, T. A. Tolmacheva, and V. M. Tsinsius, Zhzcr. neorg. Khwn., 1962, 7, 679 (345).
NICHOLLS
157
halides at 290" ; at higher temperatures the niobium phase forms a hexagonal NbC12.66 with NbCl,, but TaC1,.1-3.2 forms only TaC1, and TaC1,.65 Primary and secondary amines solvolyse vanadium(1v)chloride at room temperature, two V-C1 bonds being broken;66 with vanadium(1v) fluoride, the adducts VF,,NH,, VP,,pyridine, and VP4,SeF4have been isolated.67 Reaction of potassamide with K,VO( SCN), in liquid ammonia yields VO(NH,), which undergoes deammoniation at room temperature to give the imide VO(NH).68 The bonding in VO(H,O),2+ has been described in terms of molecular orbitals. The most significant feature of the electronic structure of V02+ seems to be the existence of considerable oxygen-to-vanadium n-bonding.69 The reduction of vanadium(v) by an excess of stannous ions in dilute hydrochloric acid yields a mixture of vanadium(II1) and vanadium(1v) uia an initial step involving a two-equivalent change in oxidation states. 70 The fluorometallates, M,VOF,, M,NbOF,, and M3TaOF6 (M = K, NH,), have been prepared by bromination of the transition metal in methanol and addition of the resultant solution to the alkali-metal fluoride solution in methanol. The charge-transfer spectra of vanadium(v) oxychloride in hydrocarbon solvents have been reported and complexes isolated with benzophenone [VOCl,,PhCOPh], camphor [VOC!,,(C10H160),], quinoline [VOCl,,C,H,N], and acridine [VOCl,,C1,HgN].72 The oxyiodides of niobium, NbOI, and NbOI,, have been isolated from mixtures of niobium, niobium(n1) oxide, and iodine in a temperature gradient.73 The phosphorus oxychloride complexes, NbCl,,POCl, and TaCl,,POCl,, are unimolecular in benzene and partly dissociated in nitrobenzene.74 The amine derivatives of niobium(v) and tantalum(v) chlorides and bromides have received extensive study. When secondary aliphatic amines react with these halides, monomeric aminolysis products, e.g., NbCl,(NEt,),,NHEt,, TaBr,(NMe,),,NHMe,, are obtained. Complete replacement of the halogen atoms in these halides has been achieved by reaction with lithium dialkylamides, giving, e.g., Ta(NR,),. The reaction with niobium(v) chloride, however, results in some reduction of the niobium especially as the lengths of the alkyl chains on the nitrogen increase ;distillation of an NbC1,-LiNEt, mixture gives Nb(NEt,)4. With the sulphur donors dimethyl and diethyl sulphide, niobium(v) and tantalum(v) halides give 1 : 1 adducts but with tetrahydrothiophen 1 : 2 complexes are formed.,, It is not yet known whether these are seven-coordinate or possess the ionic structure [MX,,S(CH,),S] fX-. Anion-exchange studies, and potential measurements with a, quinhydrone-calomel cell on perchloric acid solutions of tantalum(v) in hydrofluoric acid, have been
65
66
P. FrGre, Ann. Chim. (France), 1962, 7 85. , M. W. Duckworth and G. W. A. Fowles, J . Less-Common Metals, 1962, 4, 338. 6 7 R. G. Cave11 and H. C. Clark, J., 1962, 2692. 6 8 0. Schmitz-Dumont and R. Eickermann, 2 anorg. Chein., 1962, 313, 241. . 6 9 C. J. Ballhausen and H. B. Gray, Inorg. Chem., 1962, 1, 111. 'OD. 5 Drye, W. C. E. Higginson, and P. Knowles, J., 1962, 1137. . 71 A. E. Baker and H. M. Haendler, Inorg. Chem., 1962, 1, 127. 7 2 H . - L .Krauss and G. Gnatz, Chem. Ber., 1962, 95, 1023. 73 H. Schafer and R . Gerken, 2. anorg. Chem., 1962, 317, 105. 7 4 B. A. Voitovich and A. S. Barabanova, Zhur. neorg. Khim., 1961, 6, 2098 (1073). 7 5 P. J. H. Carnell and G. W. A. Fowles, J. Less-Common Metals, 1962, 4, 40. 7 6 D. C. Bradley and I. M. Thomas, Canad. J. Chem., 1962, 40, 449, 1355. 7 7 F. Fairbrother and J. F. Nixon, J., 1962, 180.
158
INORGANIC CHEMISTRY
interpreted in terms of the species TaF,-, TaF,2-, TaFS3-, and TaFg4-; evidence for the co-ordination number nine in TaF9*- is discussed.78 Chromium, Molybdenum, and Tungsten.-The diamagnetic complex, K,Cr( CN),, containing zerovalent chromium is obtained as a green precipitate upon reduction of potassium hexacyanochromate(II1) with potassium in liquid ammonia. 79 Reduction of [Mo(bipy),]Cl, with the lithium salt of 2,2-bipyridyl in tetrahydrofuran results in the formation of tris-2,2bipyridylmolybdenum(0).80 Several new routes t o chromium(n) fluoride have been investigated ; in the chromium difluoride-chromium trifluoride system, the existence of a single fluoride covering the solid-solution range, CrF2.40-2.45, been established. has The oxidation of chromium(n) perchlorate by sodium azide gives the complex hexa-aquochromiumIm) and penta-aquomonoarnminechromium(m) ions, and a binuclear chromium(1 1 1) ammine which is probably (H,0),Cr*NH*Cr(H20),.82 Molybdenum@) bromide and iodide can be obtained from molybdenum(@ chloride by reaction with the appropriate fused lithium halide. They yield derivatives of the types [(&t~,Br,)x,]~-and [(Mo618)X4] = c1, Br, I, or OH), in&(x cating that bromo- and iodo-molybdenum(n) compounds are likely t o contain the polynuclear groups Mo,Br8 and Mo,18 which are structurally similar to Mo,C~,.*~The o-phenylenebisdimethylarsine complexes, Mo(diars),X, (X = C1, Br, I), are isomorphous with the corresponding rhenium compounds and have magnetic moments in the range 2.8-2.9 B.M. ; they appear t o be the first known examples of octahedral bivalent molybdenum having the de4configuration.84 The spectroscopic and magnetic properties of some molybdenum complexes in oxidation states of +3, +4, and +5 have been studied. The visible spectra of the chloride and cyanide complexes arise from d-d-transitions, while the spectra of thiocyanate complexes and of complexes of molybdenum(v) with organic ligands arise from charge-transfer transitions. The low magnetic moments of molybdenum(v) complexes are attributed t o d i m e r i s a t i ~ n . ~ ~ new bromides of tungsten have been Two prepared; tungsten(n1) bromide from the dibromide and liquid bromine in a sealed tube at 50, and tungsten(rv) bromide from the pentabromide and n tungsten metal i a temperature gradient.86 I n the fluorides, K2NaCrF, and K2NaFeF,, the potassium and fluorine ions are in cubic close-packed array with the smaller chromium or iron and sodium ions in octahedral holes.87 New tervalent cationic complexes includ6 those with picolylamine [Cr(pic),]3+ and [Mo(pic),13+, diethylenetriamine [Cr(dien),13+, and triethylenetetramine [Cr(trien)Cl,]+.88 I n the violet [CrA,C13] (A = N substituted amide) there is considerable evidence to support the view that
P. Varga and H. Freund, J . P h p . Chem., 1962, 66, 21, 187. A. Heintz, J . Inorg. Nuclear Chem., 1961, 21, 262. 8 0 S. Herzog and I. Schneider, 2. Chem., 1962, 2, 24. 81 B. J. Sturm, I n o r g . Chem., 1962, 1, 665. 8 2 M . Ardon and B. E. Mayer, J., 1962, 2816. a3 J. C. Sheldon, J., 1962, 410. 8 4 J. Lewis, R. S. Nyholm, and I?. W. Smith, J., 1962, 2592. 8 s P. C. H. Mitchell and R. J. P. Williams, J., 1962, 4570. R. E. McCarley and T. M. Brown, J . Amer. Chem. rSoc., 1962, 84, 3216. a 7 K. Knox and D. W. Mitchell, J . Inorg. NucEeur Chem., 1961, 21, 253. 0. Kling and H.-L. Schlafer, 2. anorg. Chem., 1961, 313, 186; G. J. Sutton, Austral. J . Chem., 1962, 15, 232.
78L. 79E .
NICHOLLS
: T H E T R A N S I T I O N ELEMENTS
159
the amides are co-ordinated through oxygen.89 Whereas molybdenum(v) chloride is reduced by alkali-metal halides in iodine monochloride, molybdenum(&) chloride is oxidised ; in both cases tetra-halogenomolybdates(1v) are formed, M,MoX, (M = K, Rb, Cs, Te; X = C1, Br).90 The quinquevalent oxychlorides, CrOC1, and MoOCl,, have been isolated. The chromium compound is stable at low temperatures in the absence of light, but above 0" it gradually disproportionates into chromium(VI) oxychloride and a chromium(m) comp~und.~l The structural unit of molybdenum pentafluoride is a tetramer with molybdenum atoms at the corners of a square; the metal atoms are linearly linked by bridging fluorine atoms.92 The first complex halides of molybdenum(v) have been precipitated from liquid sulphur dioxide solutions of molybdenum(v) chloride with rubidium and caesium chlorides. The dark green RbMoC1, and CsMoC1, have magnetic moments of 2.1-2.2 B.M.93 The hydrolysis of the MoOC~,~- i 5-6~1-hydroion n chloric acid involves dimerisation, with the production of hydrogen and chloride ions :94
MoOC1,2-
+ H,O + [MoOCl,],04- + 2H+ + 2C1-.
The reflectance spectra of (NH,),CrOCl, and (NH,),MoOCl, have been measured. The charge-transfer transitions involve the excitation of an electron from the metal-oxygen n-bonding orbital into orbitals located mainly on the metal atom.95 Molybdenum(v)chloride is capable of abstracting the oxygen from triphenylphosphine oxide to form molybdenum(v) oxychloride which then complexes with excess of the ligand to give MoOC1,,2Ph3PO; with a large excess of ligand, oxidation to MoO,Cl, occurs.96 Tungsten(vI) chloride gives aminobasic halides, T;lrCl,(NHR),, upon reaction with primary aliphatic amines ; secondary and tertiary amines initially co-ordinate but in the presence of an excess of the amine the tungsten is reduced to the quadrivalent state. The products identified are (NH,R,),WCl, and WC1,(NR2),2NHR, with secondary amines, and WCI,*NR, and (NHR,),WCl, with tertiary arnh~es.~'The chemical properties of molybdenum(vr) fluoride have been investigated. The reaction with phosphorus trifluoride is 2MoF, + PF, ---+ 2MoF, + PF, and nitric oxide causes reduction to NO+MoF,- (probably via NOF and MOP,). 9 8 Tungsten(vI) oxychloride forms addition compounds with ethers, ketones, methyl cyanide, and pyridine ; solvolysis occurs with alcohols, &ketones, and carboxylic acids, typical products being WOCl,( OMe),
C. L. Rollinson and R. C. White, Inorg. Chem., 1962, 1, 281. A. J. Edwards, R. D. Peacock, and A Said, J., 1962, 4643. 91 H.-L. Krauss and G. Munster, 2 Naturforsch., 1962, 17b, 344; I. A. Glukhov . and S. S . Eliseev, Zhur. neorg. Khim., 1962, 7, 81 (40). g 2 A. J. Edwards, R. D. Peacock, and R. W. H. Small, J., 1962, 4486. 9 3 E. Allen, D. A. Edwards, and G. W. A. Fowles, Chem. and Ind., 1962, 1026. 9 4 G. P. Haight, jun., J. Inorg. Nuclear Chem., 1962, 24, 663. g 5 H. B. Gray and 0. R. Haze, Inwg: Chem., 1962, 1, 363. 9 6 S. M. Horner and S. Y . Tyree, jun., Inorg. Chem., 1962, 1, 122. 9 7 B. J. Brisdon, G. W. A. Fowles, and B. P. Osborne, J., 1962, 1330. 9 8 J. R . Geichman, E. A. Smith, S. S. Trond, and P. R. Ogle, Inorg. Chem., 1962, 1, 661; T. A. O'Donnell and D. F. Stewart, J. Inorg. Nuclear Chem., 1962, 24, 309.
89
90
160
INORGANIC CHEMISTRY
WOCl,( *O*CMe:CH*CO*Ph), WOC1(*O*C,H,*CO,)(*O*C6H4*C02H).99 and The basic formula of the perchromate ion has been established as [CrO(OJ,OH]-; several salts have been isolated, and all are violently explosive.100 Adducts of chromium oxide diperoxide, CrO,, with pyridine, 2,2-bipyridyl, and 1,lO-phenanthrolinehave low magnetic moments ( p = 0-4-0-9 B.M.) showing that they contain chromium(vI). The magnetic moments of chromium diperoxide (CrO,) adducts are in the range 2-7-24 B.M. indicating chromium to be in the oxidation state +4.11 Two main products, Mo40,,2- and H~MO~OO,,, obtained upon acidification of molybdate Mo0,2- ions.102 are The preparation and properties of 12-tungstochromic, 12-tungstoarsenic, and 12-tungstomanganicacids have been described, and the thermal deconiposition of 12-heteropolytungstates studied.103 Manganese, Technetium, and Rhenium.-The visible and ultraviolet spectra of the green tetrahedral [MnX,12- anions (X = C1, Br, I) have been systematically studied ;qualitative interpretations of the spectra are in agreement with the predictions of the ligand-field theory. lo4 The colourless 1 Mn manganese( 1)complexeswith the chelating ligand 2-picolylamine7 pic, X, (X = C1, Br, I),(Mn pic3)Iz,and ( M i pic,)(ClO,),, have six-co-ordinatestructures; for one other complex, Mn pic Cl,, the structure is unknown.lo5 Rhenium(=) is stabilised by co-ordination with cyanide ion in Na31.Re(CN),,H20] ; it is prepared by the sodium amalgam reduction of perrhenate in the presence of excess of sodium cyanide.lo6 Five-co-ordination of rhenium(1r)occurs in ReX,(TAS) [X = C1, Br, I ; TAS = bis-(o-diphenylarsinopheny1)phenylarsine] ; the quadridentate tris-(o-diphenylarsinopheny1)arsine(&AS) forms ReX2(QAS).lo7 The spin-free manganese(@ complexes, [Mn(bipy O,),] (C104)3 and [Mn(bipy02)3](s208)1.5, are obtained from aqueous manganese(rI1)sulphate in the presence of 2,2-bipyridyl 1,l-dioxide upon oxidation with perchlorate or persulphate.lo8 The existence of at least three classes of complex of tertiary monophosphines with rhenium halides has been established. I n the solid state [ReX3,PR,], are probably halogen-bridged polymers containing octahedral rhenium(=) ; [ReX,(PR,)] only exists where X = C1, and the compounds [ReX,(PR,),] are polymers containing rheniumrhenium bonds in the solids.109 The previously reported bis(triphenylphosphine)rhenium(m) chloride has been shown, by infrared measurements, to contain oxygen.1l0 Manganese(rv) fluoride can be prepared by heating the trifluoride in fluorine at 400,and, by heating an equimolar mixture of lithium and manganese(=) fluorides in a stream of fluorine at 350, LiMnF,
9 9 H. Funk and G. Mohaupt, 2. anorg. Chem., 1962, l o o W. P. GrifZth, J., 1962, 3948.
315, 204.
lox
l o z M. K. Cooper and J. E. Salmon, J., 1962, 2009. lo8D. H. Brown and A. J. Hyde, J., 1962, 3186; D. H. Brown, ibid., pp. 3189,
J. E. Fergusson, C. J. Wilkins, and J. F. Young, J., 1962, 2136.
3322, 4408. 1 0 4 F. A. Cotton, D. M. L. Goodgame, and M. Goodgame, J. Amer. Chem. SOC., 1962, 84, 167. l o 5 G. J. Sutton, Austral. J. Chem., 1962, 14, 550. lo6 S. Sen, 2. anorg. Chem., 1962, 315, 315. R. J. Mawby and L. M. Venanzi, J., 1962, 4447. l o * R . S. Nyholm and A. Turco, J., 1962, 1121. looJ. Chatt and G . A. Rowe, J., 1962, 4019. I 1 O C. J. L. Lock and G . Wilkinson, Chem. and Ind., 1962, 40.
N I C H O L L S : T H E T R A N S I T I O N ELEMENTS
161
is obtained.l'l Crystalline hydrates of the acids H2ReX, (X = F, C1, Br) and of salts of these acids and the iodo-acid, H2Rd6, with the cations [Co(NH3),ISSand [Cr(NH,),],+, have been described.112 Potassium tetracyanodioxorhenate(Iv) is reduced in solution by borohydride ion to the dark blue K,Re(OH),(CN),.l13 Several new halides of rhenium have been isolated.114 Rhenium(vI) chloride is a dark solid which hydrolyses to rhenium(1v) oxide and perrhenate :SRe(vr)+ Re(Iv) 2Re(v11). Bromine reacts with rhenium at 650" to give the pentabromide; the tribromide is obtained on heating the pentabromide in vacuo or in an inert atmosphere. Rhenium heptasulphide is reduced by hydrogen to rhenium(vI) sulphide.115 I n 65% oleum, permanganates and chromates evolve oxygen ; the resulting solutions (blue with manganese and green with chromium) contain manganese(1v) and chromium(v) respectively. Iron, Ruthenium, and Osmium.-A new class of iron isocyanide complexes have the structure [(RCH,*NC),FeCN]Br,and studies of their reactions with nucleophiles and alkyl halides have been made.117 Tris-(o-diphenylarsinopheny1)arsinereacts with nitrosylruthenium compounds to give RuX2( &AS) ; in these compounds six-co-ordination appears to be preserved despite stringent steric requirements of the chelating agent.118 The quadrivalent ferrocyanide ion, Fe(CN),4-, is virtually absent in acid solution, where protonation occurs to HFe(cN)63- and H2Fe(CN),2-.119 The previously reported hydrazine complex, [Ru2C12(N2H,),]C14, has been proved to be [RuCl(NH,),]Cl,, and its crystal structure has been determined.120 Several new osmium halides have been prepared;l21 these are the three iodides, OsI, OsI,, and OSI,, and two bromides, OsBr, and OsBr,. Heptavalent osmium has been reported from two sources. The emerald green, paramagnetic OsOF, has been prepared by fluorination of osmium(1v) oxide; it hydrolyses to osmium(vIn) oxide, and gases smelling of ozone are evolved.122 Characterisation of the compounds A2BB10, (A = Ca, Sr, Ba, B = a variety of uni-, bi-, and ter-valent cations and B1 = 0 s or Re) shows that many of thein have the ordered perovskite structure; in Ba,LiOsO, there is some evidence for osmium(vn).I23 Cobalt, Rhodium, and Iridium.-Finely divided cobalt, nickel, and palladiethylphosphine), forming the dium react at 200 with o-phenylenebis( zerovalent M[C,H,(PEt,),] ; the neighbouring Group V I I I metals do not
Hoppe, 'W. Dahne, and W. Klemm, A n n a l e n , 1962, 658, 1. Brauer and H. D. Allardt, 2. anorg. Chem., 1962, 316, 134. H. L. Walter, J. Kleinberg, and E. Griswold, Inorg. Chem., 1962, 1, 10. l14R. Colton, Nature, 1962, 194, 374; idem, J., 1962, 2078. 115 K. Traore, G. Coeffier, and J. Brenet, Compt. rend., 1962, 491; idem, Bull. SOC. china. France, 1962, 361. 116 H. C. Mishra and M. C. R. Symons, Proc. Chem. SOC., 1962, 23. 1 1 7 W. Z. Heldt, J . Inorg. Nuclear Chem., 1961, 22, 305; ibid., 1962, 24, 73, 265. l l * J. G. Hartley and L. M. Venanzi, J., 1962, 182. 119 J. Jordan and G. J. Ewing, Inorg. Chem., 1962, 1, 587. 1 2 0 C. K. Prout and H. M. Powell, J., 1962, 137. 1 2 1 J. E. Fergusson, B. H. Robinson, and W. R. Roper, J., 1962, 2113; S. A. Shchukarev, N. I. Kolbin and I. N. Semenov, Zhur. neorg. Khim., 1961, 6, 1246 (638); I. N. Semenov and N. I. Kolbin, ibid., 1962, 7, 219 (111). 1z2 N. Bartlett, N. K. Jha, and J. Trotter, Proc. Chem. Soc., 1962, 277. 1 2 3 A. W. Sleight, J. Longo, and R. Ward, Inorg. Chem., 1962, 1, 245.
I l l R. 112 G . 113 P.
F
I62
INORGANIC CHEMISTRY
react except in the presence of hydrogen, in which case iron gives the dihydride ~~~~S-{F~H,[C~H,(PE~,),],~.~~~ Two rhodium(1) complexes with 2,2'bipyridyl have been described. It is suggested that the diamagnetic Rh(bipy),C104,3H20 is the perchlorate of the tetragonal trans-[Rh(bipy), (H,O),] + cation, but the structure of the paramagnetic Rh(bipy),N0,,3H20 is less certain.125 Detailed studies have been made of the effect of adding chloride, bromide, and thiocyanate ions t o solutions of cobalt(I1) in acetic acid and ethanol. From ion-migration and spectrophotometric measurements the ionic species present are postulated to be (Cox)+,(Cox,), (COX,)-, and COX^)^-.^^^ I n other solvents, e.g., nitromethane, acetone, and dimethylformamide, there is considerable interaction between the solute cobalt (II) chloride and the solvent. 1 2 7 Complexes containing the tetrahedral [CoX,I2- ion (X = C1, Br, I) can be isolated from ethanolic solution; their Racah parameters ( B ' ) and spin-orbit coupling constants (A') show that appreciable overlap of metal and ligand orbitals occurs.128 Magnetic and spectrophotometric measurements indicate that cobalt(I1) complexes with N-substituted salicylaldimines are tetrahedral in the solid state and in benzene solution; in pyridine they take up two molecules of solvent and become 0ctahedral.1~~ The ultraviolet spectra of these complexes, however, show that the N-methyl derivative has a configuration different from the others ; it is probably planar.130 Tetramethylene sulphone forms the unstable compounds Co(C,H8S0,)C1, and CO(C,H~SO,)~(C~O~),, in which the sulphone presumably is bidentate through the two oxygen atoms. 131 With pyrazine and some methylpyrazines cobalt(I1) halides form several halogenbridged dimers, [LCoX,],, in which the cobalt atom is tetrahedral, and polymeric complexes, [LCoX,], or [L2CoX2],, in which the cobalt is usually 0ctahedral.1~2 There has been little evidence that oxyacids can form fourmembered rings with elements of tetrahedral symmetry; methyl- and ethylphosphinic acids, however, form blue cobalt@) salts with the strain-free polymeric structure ( l).133 Reactions of cobalt(@ halides with amines,
J. Chatt, F. A. Hart, and D. T. Rosevear, J., 1961, 5504. B. Martin, W. R. McWhinnie, and G . M. Waind, J . Inorg. Nuclear Chem., 1961, 23, 207. l e aP. J. Pro11 and L. H. Sutcliffe, J . Phys. Chem., 1961, 65, 1993; S. A. Shchukarev and 0. A. Lobaneva, Zhur. neorg. Khim., 1961, 6, 804 (410). 12'S. Buffagni and T. M. Dunn, J . , 1961, 5105; D. A. Fine, J . Amer. Chem. SOC., 1962, 84, 1139. 128 F. A. Cotton, D. M. L. Goodgame, and M. Goodgame, J . Amer. Chem. SOC., 1961, 83, 4690. Iz9 B. 0. West, J., 1962, 1374; L. Sacconi, M. Ciampolini, F. Maggio, and F. P. Carasino, J . Amer. Chem. Soc., 1962, 84, 3246. I3O H. Nishikawa, S. Yamada, and R. Tsuchida, 2. anorg. Chem., 1962, 316, 278. I3l C. H. Langford and P. 0. Langford, Inorg. Chem., 1962, 1, 184. 132A. P. Lever, J. Lewis, and R. S. Nyholm, J., 1962, 1235. B. 133 G . E. Coates and D. S. Golightly, J . , 1962, 2523.
124
125
NICHOLLS
163
phosphines, and arsines have been extensively investigated. 134 Tetrahedral compounds, CoX2,2EtNH2, CoX2,2Et2NH, CoX2,3EtPH2,and CoX2,2Et2PH, are formed with primary and secondary aliphatic amines and phosphines ; aromatic phosphines can form the octahedral (PhPH,),,CoI,. With triethylamine the complex formed, CoCl,,Et,N, may contain doubly halogenbridged dimers, while, with triethyl-phosphine and -arsine, tetrahedral CoX,,2PEt3 and CoX2,2AsEt3are formed. The bright blue CoC1,,2A1C13, formed when the chlorides are melted together and cooled, is, structurally, cobalt(I1) chloroaluminate, Co(AlCl,),. The crystal structure of this compound shows, surprisingly, that the cobalt is octahedrally co-ordinated.135 Infrared spectra of the binuclear M6[Co,(CN),,],4H,0 (M = NayK) indicate similar metal-metal bonding in the [Co2(CN),,]6- ion as in the isoelectronic molecule Mn2(CO),,. l 3 6 The f i s t well-characterised rigorously square-planar and spin-free complex of cobalt(I1) has been formed with the ligand maleonitriledithiolate (MNT) (2) ; [Bun4NfI2Co(MNT),has a magnetic moment of 3.92 B.M.13' Other cobalt(=) 2complexes studied during the year include those with Nc = ; > methyl isocyanide,138 benzimidazole,l 3 9 the enolate anion of dipivaloylmethane,l40 and o-phenylenebisdimethylarsine. 141 The X-ray structure deter(2) mination of carbonatotetra-amminecobalt(m) bromide shows that the carbonate group acts as a chelate to form a four-membered ring. The cobalt atom is thus surrounded by two oxygen and four nitrogen atoms at the corners of a somewhat distorted 0ctahedron.1~2 The thermal decomposition of hexa-amminecobalt(m) azide yields a diammine of cobalt(=) azide :143
[CO(NH3)61(N3)3
[ ::.]
* Co(NH3)2(N3),+ 4NH3 + 1'5N2.
The synthesis and properties of the new nitritopenta-ammines, [(NH3),M*ONO]"+ [M = Rh(nI), Ir(Irr), Pt(w)], have been described.144 The reaction of trisethylenediamineiridium( III) iodide with potassamide in liquid ammonia leads t o a sequence of products corresponding to the successive removal of protons from the ligand nitrogen atoms. Of these products, [Ir(en-H),(en)]I and K,[Ir(en-2H),(en H)] have been isolated and characterised; the former also results from the reduction of Ir(en),I, with potassium in ammonia.145
134 W. E. Hatfield amd J. T. Yoke, tert., Inorg. Chern., 1962,1,463, 470,475; D. M. L. Goodgame, M. Goodgame, and F. A. Cotton, ibid., p. 239; K. Issleib and G. Wilde, 2. anorg. Chem., 1962, 312, 287. 1 3 5 J. A. Ibers, Ada Cryst., 1962, 15, 967. 136 R. Nast, H. Ruppert-Mesche, and M. Helbig-Neubauer, 2. anorg. Chem., 1961, 312, 314. 13' H. B. Gray, R. Williams, I. Bernal, and E. Billig, J . Amer. Chern. SOC., 1962, 84, 3596. 138 A. Sacco and F. A. Cotton, J . Amer. Chern. SOC., 1962, 84, 2043. 139 M. Goodgame and F. A. Cotton, J . Amer. Chem. Soc., 1962, 84, 1543. l40F. A. Cotton and R. H. Soderberg, J . Amer. Chem. SOC., 1962, 84, 872. l a l T . M. Dunn, R. S . Nyholm, and S . Yamada, J., 1962, 1564. 142 G. A. Barclay and B. F. Hoskins, J . , 1962, 586. 143 T. B. Joyner and F. H. Verhoek, Inorg. Chern., 1962, 1, 557. 144 F. Basolo and G. S . Hammaker, Inorg. Chern., 1962, 1, 1. 145 G. W. Watt, L. E. Sharif, and E. P. Helvenston, Inorg. Chem., 1962, 1, 6.
164
Nickel, Palladium, and Platinum.-Zerovalent nickel and palladium complexes, [ML,], [MLL], and [ML], [M = Ni, Pd; L = chelate ditertiary phosphine, e.g., Me,P*CH,*CH,*PMe,; L = ditertiary arsine, e.g., oC,H,(AsMe,),, or tritertiary phosphine], have been isolated by reduction of the corresponding nickel(@ and palladium(I1) complexes with a variety of reducing agents. 146 Nuclear magnetic resonance and infrared spectroscopy show no evidence of hydrogen bound to platinum in tris(tri-p-fluorophenylphosphine)platinum, so that this can be considered to be a true platinum(0) compound.14 Nickel dissolves anodically in acetonitrile and dimethylformamide containing tetramethylammonium chloride, as a mixture of nickel(1) and nickel@). Nickel(1) is stable enough to be titrated against iodine.148 Two reviews have appeared concerning the stereochemistry of complexes of nickel(=), palladium(n), and platinum(II).149 The phase diagram of the system nickel chloride-cesium chloride shows two congruently-melting compounds, CsNiC1, and Cs,NiCl,. In the latter, the nickel is surrounded by four chloride ions tetrahedrally, the fifth chlorine being considerably more distant. l50 Complex nickel(I1) fluorides can be classified according to their magnetic behaviour. Normal paramagnetic compounds include Li,NiF, and (NH,),NiF,,2H20, while KNiF, and M,NiF, (M = K, Rb, NH,, T1) are antiferromagnetic; MNiF, (M = Na, NH,, Rb) are weakly ferromagnetic.151 In bis(thiosemicarbazidato)nickel(n) the nickel atom co-ordinates two sulphur and two nitrogen atoms in a transplanar configuration.152 The paramagnetic [NiN02en,]C104contains octahedrally-co-ordinated n i ~ k e 1 . 1 ~ ~ reflection spectra of nickel(=) comThe -aminoethylcyclohexane (am) show that plexes of the bidentate 1-amino-1 there is slight distortion from octahedral in the violet Ni am,Br, while the pale blue Ni am,(CCl,*CO,), is strongly di~torted.1~4 There are two new types of tetrahedral nickel(I1) complexes. Dark green di-iodabis(pyridine) nickel(=) and light green di-iodobis-(p-picoline)nickel(r) contain nitrogen bonded tetrahedrally to nicke1,155 and isopropyl- and s-butyl-salicylaldiminonickel(rc) are the first tetrahedral nickel@) chelates.156 The relationship between solution paramagnetism and solute association in certain nickel(rr) complexes is now well established. I n solvents of low co-ordinating power, monomers interact to form an associated species, thereby producing effective five- or six-co-ordination of some or all of the nickel atoms in the aggregate. Solutions of nickel@) acetylacetonate in benzene contain trimeric units of Ni(acac),, and the solution paramagnetism of the bisT. C. Franklin and C. R. Parsons, J . Electrochem. SOC., 1962, 109, 641. C. M. Harris and S. E. Livingstone, Rev. Pure Appl. Chem., 1962, 12, 16; J. R. Miller, Adv. Inorg. Chem. Radiochem., 1962, 4, 133. 1 5 0 E. Iberson, R. Gut, and D. M. Gruen, J. Phys. Chem., 1962, 66, 65. 151 W. Rudorff, J. Kandler, and D. Babel, 2. anorg. Chem., 1962, 317, 261. 152 L. Cavalca, M. Xardelli, and G. Fava, Acta Cryst., 1962, 15, 1139. lS3 F. J. Llewellyn and J. M. Waters, J., 1962, 3845. 154 C. K. Jorgensen, 2. anorg. Chem., 1962, 316, 12. lS5 M. D. Glonek, C. Curran, and J. V. Quagliano, J. Amer. Chem. Soc., 1962, 84, 14. 156 L. Sacconi, P. L. Orioli, P. Paoletti, and M. Ciampolini, Proc. Chem. SOC., 1962, 255.
146 147 148 149
J. Chatt, F. A. Hart, and H. R. Watson, J., 1962, 2537. A. D. Allen and C. D. Cook, Proc. Chem. SOC.,1962, 218.
NICHOLLS
THE T R A N S I T I O N ELEMENTS
165
(R ON-salicylaldimine)nickel(1) complexes is dependent upon the nature of 1 the substituent R Complexes of palladium(I1)halides with secondary and tertiary phosphines have been investigated. Those complexes, of formula PdXPR,L, (X = C1, Br, I, SCN; R = Et, Ph; L = secondary or tertiary phosphine), have the novel phosphorus-bridgedstructure (3).15* I n yellow crystalline trans-(Et,N,O),PdCl,, co-ordination is from the oxygen a t 0 m s . 1 ~ Five-co-ordin- p ~ d L , PhZ p
(3) ate complexesof palladium(I1)with tris-o-diphenyl- x ' "pApdKL arsinophenylarsine, of the type [PdX(QAS)] +, Ph2 are probably trigonal bipyramidal. 160 Some substitution reactions of palladium(I1) complexes have been studied. Ethyleneag-bis(dipheny1arsine) (EDA) reacts with the compounds [Pd en X,] (X = Cl, Br), to give [Pd(EDA)X,] and [Pd(en),]X,, while [Pd en 12] gives only [Pd(EDA)I2].1G1 Interaction of unidentate ligands (L), e.g., ammonia and pyridine , with halogen-bridged anionic complexes, (NEt4)2(Pt,X,)(X = Br, I),has led to isolation of [NEt4][PtLX,].162 From pure quadrupole resonance of the halogens in K,PdX, (X = C1, Br) and K,MBr, (M = Pd, Pt), aiid use of Townes and Dailey's relationship, it is concluded that the former compounds have 60% covalent character and the latter 40y0.163 A large amount of work on the preparation and isomerism of platinum complexes has been published, particularly in the Russian journals, e.g., ref. 164. Isomerisation of solutions of cis- and trans-bis(triethylphosphine)dichloroplatinum( is rapid in sunlight ; the very different II) dipole moments of the isomers are reflected in the solvent dependence of the steady state.165 Two remarkable oxidations with platinum hexafluoride have been discovered. With oxygen, a compound of composition F,o,Pt can be obtained either on mixing oxygen and platinum(v1) fluoride or by fluorination of platinum in a glass or silica apparatus. Upon hydrolysis this compound gives the PtF,,- ion (which cannot be otherwise synthesised in aqueous media), and, in view of its magnetic properties ( p = 2-84 B.M.) and X-ray powder photograph (whichis very similar to that of NOOsF,), it is formulated as dioxygenyl hexafluoroplatinate(v). This formulation stimulated the discovery of XePtF,, an orange solid, stable at room temperature and sublimable in vacuo.166
1' J. P. Fackler, J . Amer. Chem. SOC., 5 1962, 84, 24; H. C. Clark, K. MacVicar, and R. J. O'Brien, Canud. J . Chem., 1962, 40, 822; R. H. Holm, J . Amer. Chem.SOC., 1961, 83, 4683; R. H. Holm and K. Swaminathan, Inorg. Chem., 1962, 1, 599. 1 5 8 R. G. Hayter, Nature, 1962, 193, 872; idem, J . Amer. Chem. SOC., 1962, 84,
/x
3046.
159
160 161
162
R. D. Brown and G. E. Coates, J., 1962, 4723. C. A. Savage and L. M. Venanzi, J., 1962, 1549. G. W. Watt and R. Layton, Inorg. Chem., 1962, 1, 496.
S. E. Livingstone and A. Whitley, Awtral. J. Chem., 1962, 15, 175. K. Ito, D. Nakamura, Y. Kurita, K. Ito, and M. Kubo, J . Amer. Chem. SOC., 1961, 83, 4526. 164 V. I. Belova, Ya. K. Syrkin, and L. I. Baranova, Zhur. neorg, Khim., 1961, 6, 625 (319); A. V. Babaeva and N. I. Ushakova, ibid., p. 151 (297); L. N. Essen and D. P. Alekseeva, ibid., p. 857 (436); B. Ud-Din and J. C. Bailar, j u . , J . Inorg. Nuclear Chem., 1961, 22, 241. 165P. Haake and T. A. Hylton, J . Amer. Chem. SOC.,1962, 84, 3774. 166 N. Bartlett and D. H. Lohmann, Proc. Chem. SOC.,1962, 115; N. Bartlett, ibid., p. 218.
166
INORGANIC CHEMISTRY
Copper, Silver, and Gold.-A mass-spectrometric examination of the absolute isotopic abundance ratio in natural silver has led to the value for the atomic weight of silver, on the unified scale (12C = 12), of 107.8694 & 0-0026.167 Compounds containing triphenylgermyl groups bonded to copper, silver, and gold have been prepared by reaction of the complexes R,PMX [M = CU(I), Ag(I), Au(I)] with triphenylgermyl-lithium. The gold compound, Ph,GeAuPPh,, is stable to air and water but the stability falls off in the series Au > Ag > C U . ~ ~ ~ of silver perchlorate Adducts and borofluoride with triphenyl derivatives of some Group V elements have been synthesised; they are of the types Ph,N,AgClO,, (Ph3Sb),,AgC10,, and Ph,Bi,AgClO,. Azobenzene forms 3PhN2Ph,2AgC10,,PhN2Ph,CuC10,, and 3PhN2Ph,2AgBF,.169 I n (AgCl),en, the ethyleiiediamine acts as a bridging group between the two silver ions, while Ag en C is probably dimeric, having 1 linearly co-ordinated silver.170 Stability constants of copper(1) and copper(@ complexes with several nitrogen donors have been measured, and electrode potentials for the Cu2f-Cu+ complexes calculated; in every case there is preferential stabilisation of the cuprous state. 171 Copper(=) bromide is reduced upon reaction with potassium diphenylphosphide, forming redviolet CuPPh, and tetraphenyldiphosphine. Treatment of copper(I) bromide with an excess of KPPh, results in the formation of K ( c ~ P P h , ) . l 7 ~ Unlike silver@)complexes with oxine, 2-hydroxyquinoline forms a 1 : 1 complex, Ag(C,H,*NO).1 7 3 Pyridine and quinoline N-oxides co-ordinate with copper(@ salts to give a variety of products. The mono-complexes, Cu(C,H,*NO)X, (X = C1, Br), have the unusually low magnetic moments of 0.4-0.8 B.M. This has led to their being formulated as binuclear oxygenbridged structures in which electron-exchange demagnetisation can occur between pairs of adjacent copper atoms Wia the oxygens.17, Two types of chelate are formed with copper(n) and pyrazinylmethyl 2-pyridyl ketone. One type consists of a six-membered chelate ring in which the pyrazine
(4)
HcyN]
N
nitrogen is bonded to copper (4), and in the other type, ( 5 ) , the pyridine nitrogen is bonded to copper forming a five-membered chelate ring.175
E. A. C. Crouch and A. K. Turnbull, J., 1962, 161. F. Glockling and K. A. Hooton, J., 1962, 2658. 169 R. H. Nuttall, E. R. Roberts, and D. W. A. Sharp, J., 1962, 2854. 170 0. Newmann and D. B. Powell, J., 1962, 3447. 171 C. J. Hawkins and D. D. Perrin, J., 1962, 1351. 173 K. Issleib and H.-0. Frohlich, Chem. Ber., 1962, 95, 375. 173 W. W. Wendlandt and J. Haschke, Nature, 1962, 379. 174 C. M. Harris, E. Kokot, S. L. Lenzer, and T. N. Lockyer, Chem. and Ind., 1962, 651; K. Issleib and A. Kreibach, 2. anorg. Chem., 1962, 313, 338. 176 N. Naqui, E. L. Amma, and Q. Fernando, J. Inorg. Nuclear Chem., 1962, 24, 609.
167
168
NICHOLLS : THE TRANSITION ELEMENTS
167
Studies on copper(n)-a-amino-acid chelates indicate that three different environments of copper atoms can be found depending upon the amino-acid. I n copper(n) a-amino-a-methyl-propionate and l-aminocyclopentane-lcarboxylate, the copper atoms appear to be truly four-planar co-ordinate.170 Copper(@ N-arylglycinates have two structures ;the usual chelate amino-acid structure ( 6 ) is more stable than the type (7) in which nitrogen no longer acts as a donor. The addition compounh (Me*CO*CH*CO,Et),Cu(C,H,N),
OC-0,
HC-HN'
Ar I ,NH-CH,
cu
'o-co
and (MeCO*CH 2Et) C5H5N) are probably five- co-ordinate, the 430 2Cu( additional molecule of heterocyclic base being free in the crystal 1atti~e.l'~ The addition of nitrate ions to copper(=) salts in acetonitrile andethylacetate results in the formation of nitrato-complexes according t o a concentrationdependent equilibrium :I78
Cu2+
+ 2N03- + &(NO3)+ + NO,- + Cu(NO,),.
The polarographic behaviour of copper ions in a number of non-aqueous solvents has been studied. The copper(1) ion is stable with respect to disproportionation in propan-1-01, propan-2-01, acetone, and nitromethane ; its stability appears to be due to a lower solvation energy of the copper(=) ion in these solvents.17B A review has appeared dealing with the higher oxidation states of silver.l*o Zinc, Cadmium, and Mercury.-The cadmium(1) ion, Cd22+,has been identified by Raman spectroscopy on molten 0-67Cd2( AlC1,),-0-33 Cd(AlC1,) 2. l8 Four - co-ordinate non-electrolytes, [M(diars)X,] (X = C1, Br, I, ClO,), are formed by all three metals in this group with o-phenylenebisdimethylarsine. I n solution, some formation of a salt [M1l(diars),](M1lX,) occurs; this is most evident for the complexes [Hg(diars)12].182 Ceramic techniques being used, three compounds can be prepared in the CdO-B,03 system; they are 3CdO,B,O,, 2Cd0,B20,, and 2Cd0,3B203.183 The degree of complex halide formation of cadmium salts in molten sodium nitratepotassium nitrate increases in the series C1- < Br- < I-.184 The action of
17% D. P. Graddon and L. Munday, J. Inorg. Nuclear Chem., 1961, 23, 231; D. P. Graddon, ibid., 1961, 22, 85. 177D. Graddon and E. C. Watton, J. Inorg. Nuclear Chem., 1961, 21, 49. P. 1 8 . J. Hathaway and A. E. Underhill, J., 1962, 2256. 'B L 7 B I. V. Nelson, R. C. Carson, and R. T. Iwamoto, J. I n o r g . iluclear Chem., 1961, 22, 279. lSo J. A. McMillan, Chem. Rev., 1962, 82, 65. J. D. Corbett, Inorg. Chem., 1962, 1, 700. ls2 J. Lewis, R. S. Nyholm, and D. J. Phillips, J., 1962, 2177; G. J. Sutton, Austral. J . Chem., 1962, 14, 545. lS3 P. B. Hart and E. G. Steward, J. Irwrg. Nuclear Chem., 1962, 24, 633. 184 D. Inman and J. O'M. Bockria, Trans. Faraday Soc., 1961, 57, 2308.
168
INORGANIC CHEMISTRY
anhydrous hydrogen chloride on bispyridinecadmium chloride produces (pyH),CdCI, ; in aqueous hydrochloric acid (pyH)CdCl, is formed.185 Cadmium(=) forms 1 : 1, 1 : 2 and 1 : 3 complexes with amino-acids; the most stable are those involving ligands capable of forming five-membered chelate rings, e.g., glycinate, a-alaninate.la6 Some new complexes of mercury@) with oxygen donors are unusual in being six-co-ordinate; white crystals, (HgL6)(C1o4),,have been isolated (with L = pyridine N-oxide, dimethyl sulphoxide, tetrahydrothiophen oxide, and thioxan oxide).ls7 A cryst a1- stru cture examination of bismethyIthiomercury shows it to contain simple molecules of (MeS),Hg in which the S-Hg-S group is linear.188 Triphenylphosphine reacts with quaternary iodomercurates in acetone or ethanol, giving iodo(triphenylphosphine)mercury(n:) together with either a quaternary iodomercurate (with a higher I : Hg ratio than the reactant) or a quaternary iodide. (Ph,P)2HgX, and (Ph3PHgX,), (X = C1, Br) are converted by methyl iodide into the corresponding trimethylphosphonium iodomercurates. The reaction involves halogen exchange as well as quaternisation :
(Ph3P).HgX2
+ (n + 2)MeI -+ (Ph,PMe).HgI(,+,) + 2MeX.
Complexes.-( a) General. General reviews appearing during the year

have been concerned with polymeric co-ordination compounds,1 the present state and future development of co-ordination chemistry,2 and with the coupling of vibrational and electronic motions in degenerate electronic states of inorganic complexe~.~ There has been a rapid exploitation of Mossbauer spectra (resonant y-ray absorption in solids) in physicochemical investigations; most of the spectra so far recorded are for iron compounds. Of particular interest from the chemical point of view is the attempt to correlate the isomer shift observed in various compounds with a detailed formulation of the electronic environment of the iron nucleus, I n potassium ferrate, the isomer shift is smaller than predicted for a 3&2electron configuration, presumably because the 3d electron density is augmented by d3s hybridisation in the tetrahedral FeOa2- ion. The data on the cyclo-octatetraeneironcarbonyls, C,H,Fe,(CO), and c8H8Fe( Go),, suggest essentially completely covalent bonding between the iron atom and the n-electron distribution in the cyclo-octatetraene ring. The charge density of the delocalised n-electrons is essentially the same in the C4 residue of C,H,Fe(CO), as in the two C, residues in C,H,Fe,(CO), t o which the iron atoms are bonded. This is consistent with earlier X-ray data showing iron to have a quasi-octahedral configuration comprising three
lE5
H. Buss, H. W. Kohlschutter, and D. Maulbecker, 2. Naturforsch., 1962, 17b,
485.
lE6 J. H. Smith, A. M. Cruickshmk, J. T. Donoghue, and J. F. Pysz, jun., Inorg. Chem., 1962, 1, 148. R. L. Carlin, J. Roitman, M. Dankleff, and J. 0. Edwards, Inorg. Chem., 1962, 1, 182. l s s D . C. Bradley and N. R. Kunchur, Chern. and Ind., 1962, 1240. l a gG. B. Deacon and B. 0. West, J., 1961, 5127; idem, J . I n o r g . Nuclear Chem., 1962, 24, 169. I. Haiduc, Uspekhi Khim., 1961, 1124 (498). A. A. Grinberg, Uspekhi Khim., 1961, 755 (334). A. D. Liehr, Progr. Inorg. Chem., 1962, 3, 281.
NICHOLLS
169
CO groups and three of the eight carbon-carbon bonds.* The lattice energies
and crystal-field stabilisation energies have been presented for some oxides and halides of metals in the first and second transition series. It is shown that some further stabilisation ( metal lattice stabilisation ) is present in the metal lattice which masks the effect of the crystal field upon the experimental enthalpies of formation of these compounds. From a comparison of the variation of lattice energy with atomic number in the actinide oxides and halides it appears likely that the 5f shell rather than the 6d is progressively filled in these compounds. Simple relationships have been derived for lattice energies and heats of hydration of bivalent cations in the calcium to zinc series. The lattice energies ( U ) of octahedrally co-ordinated compounds in this series are represented by: - U = C I - n,A, where C is a constant, I is the ionisation potential of the atom, n, the number of 3d electrons in e, antibonding orbitals, and A is a constant numerically comparable with the spectroscopic ligand-field splitting factor.6 There has been a revival of interest in the study of rotatory dispersion curves, i.e. molecular rotation plotted against wavelength, as a tool for structural and stereochemical investigations of complexes. A dissymmetric d 3 or d6 complex with C, symmetry may give two or three circular dichroism bands in the wavelength region of the higher energy ligand-field absorption band, whereas the corresponding D,complex can give no more than one such absorption in that region. The observation that the (-)-trisoxalatocobalt(m) ion gives two circular dichroism bands in the 4000-5000 A region indicates that some of the ions have approximate C, symmetry.7 While cis- and trans-isomers of the inert chromium(III), cobalt(m), and rhodium(m) benzoylacetonates can be separated, only the more stable trans-isomerscan be isolated from the labile complexes of tervalent aluminium, manganese, and iron : the configurations of these cis- and trans-isomers have been established by use of proton magnetic resonance.* I n the tervalent transition-metal acetylacetonates from titanium to cobalt, the n +n* transition energy increases with increasing number of de electrons and this is attributed to metal-ligand n-interaction. I n order to explain the normal value of the ligand-field splitting parameter, A, it is suggested that the metal-ligand n-interaction occurs between the d, orbitals of the metal and both higher, empty 7c* orbitals and lower filled n orbitals of the l i g a n d ~ . ~ unusual spectral An effect observed in the proton magnetic resonance spectra of diamagnetic substituted cobalt(m) and rhodium(II1) acetylacetonates suggests that the chelate rings give rise to long-range magnetic anisotropic shielding normally associated with aromatic systems. This could represent the first physical
G. K. Wertheim and R. H. Herber, J. Chem. Phys., 1962, 36, 2497; idem, J . Amer. Chem. SOC., 1962, 84, 2274; G. K. Wertheim, W. R. Kingston, and R. H. Herber, J. Chem. Phys., 1962, 37, 687; cf. Ann. Reports, 1961, 58, 464. M. F. C. Ladd and W. H. Lee, J . Inorg. Nuclear Chem., 1961, 23, 199; idem, J., 1962, 2837. G. C. A. Schuit, Rec. Trav. chim., 1962, 81, 21, 481. J. G. Brushmiller, E. L. Amma, and B. E. Douglas, J. Amer. Chem. SOC., 1962, 84, 3227; R. E. Ballard, A. J. McCaffery, and S. F. Mason, Proc. Chem. SOC., 1962, 331; A. J. McCaffery and S. F. Mason, ibid., p. 388. * R. C. Fay and T. S. Piper, J. Amer. Chem. Soc., 1962, 84, 2303. D. W. Barnum, J. Inorg. Nuclear Chem., 1961, 22, 183, 221; T. S. Piper and R . L. Carlin, J. Chem. Phys., 1962, 36, 3330.
170
I N O R G A N I C CHEMISTBY
evidence for aromaticity in such chelate rings.l0 The contributions of n-bonding in the silver-nitrogen bond to the stabilities of silver complexes with substituted pyridines have been discussed by means of a relationship - log Kmn, where L, is a between the stabilisation factor Sf (log K,., n-bonding ligand), and Hammetts o factor for the substituents.1l The nuclear spin coupling constants between platinum and phosphorus in squareplanar platinum(I1) complexes appear to be largely determined by the strength of the bond between these two elements. I n the compounds P),PtCI,], the triethyl phosphite ligand has [(EtO),P],,PtCl,, and [(Bun3 smaller o-bond donor power than tri-n-butylphosphine, and consequently the acceptor properties of the phosphorus d orbitals in this complex are stronger and the coupling constant larger.12 A thermodynamic study of the solubilities of dimethylglyoximenickel and ethylmethylglyoximenickel shows that the crystal energy of the former is about 10 kcal. more than that of the latter. A large part of this difference is attributed to nickel-nickel bonding in the dimethylglyoximenickel.l3 The stabilities of bivalent-metal alkanedicarboxylates are in the Irving-Williams stability order for chelate complexes, and it seems likely therefore that chelation forces predominate in aqueous solutions of these salts.14 A general theory has been formulated to account for the number-average degree of polymerisation of metal oxide alkoxides; it provides a rational interpretation of some oxide alkoxides of tin, cerium, and ursnium.15 A general paper has dealt with the classification of inorganic co-ordination polymers. Measurements of melt viscosity and conductivity as a function of temperature indicate that monoamminedichlorozinc() is polymeric; 1 1 depolymerisation occurs in co-ordinating solvents. A co-ordinationpolymer having an inorganic backbone has been prepared by reaction of chromium(rn) acetylacetonate with diphenylphosphinic acid. The structure of the product, (AcCHAc),Cr(OPPh,O) ,Cr(AcCHAc),, probably involves double diphenylphosphinate bridges.l6 The polyfunctional ligand naphthazarin forms 1 : 1 polymers (containing two molecules of water) with bivalent cobalt, nickel, and zinc, in which the metals are octahedrally co-ordinated; with copper, Cu, naph, contains four-co-ordinate copper.l7 Studies on metal-amine complexes in ion-exchange show that complexes of 2-aminoethanol with silver(I),nickel(II), and copper@), and of ethylenediamine with nickel(n), copper(n), and zinc(=) are much more stable in the resin than in solution. Cross-linking by the diamine binding the metal ions together occurs much more readily on the resin where the metal ions are closer together than in dilute solutions.l8 A new chromatographic technique,
P. Collman, R . L. Marshall, and W. L. Young, Chem. and Ind., 1962, 1381. H. Irving and J. J. R. F. da Silva, Proc. Chem. Soc., 1962, 250. l2 A. Pidcock, R. E. Richards, and L. M. Venanzi, Proc. C h e m SOC., 1962, 184. C . V. Banks and S. Anderson, J . Amer. Chem. Soc., 1962, 84, 1486. l4 R. H. Jones and D. I. Stock, J., 1962, 306. 16D. C. Bradley and H. Holloway, Canud. J. Chem., 1962, 40, 1176. l6 B. P. Block and G. Barth-Wehrenalp, J . Inorg. Nuclear Chem., 1962, 24, 365, 1962, 84, 1749. 371; B. P. Block, J. Simkin, and L. R. Ocone, J . Amer. Chem. SOC., l7 R. S. Bottei and P. L. Gerace, J . Inorg. Nuclear Chem., 1961, 23, 245. L. Cockerel1 and H. F. Walton, J . P h p . Chem., 1962, 66, 75; M. G. Sunjaraman and H. F. Walton, ibid., p. 78.
l o J.
l1
NICHOLLS
171
ligand exchange, has been used to separate compounds that form complexes with metal ions. The ion-exchanger containing the complexing metal ion effects the separation of ligands having different co-ordinative valencies.19 I n an interesting low-temperature application of zone melting, the separation of solutes differing in solubility (especially diastereoisomers) is achieved by freezing the solution and causing a molten zone to traverse the charge.20 Further studies have been made on the photoracemisation of + octahedral chelates. The complexes [Co en,13+ and [Co en2(C20,)] are stable to both photoracemisation and photodecompositionbut [Co en(C,O,),]photoracemises and [CO(C,O,),]~- photodecomposes with some photoracemisation.21 The energy spectrum resulting from the 5d8 configuration in a square-planar ligand-field has been calculated; the ordering of the d orbitals is d, = d, < dz2 < d,, < d z 8 - y 2 . 2 2 The spectra of transitionmetal oxyanions, in particular permanganate and chromate, have been studied and the effect of the solvent and of complex-forming ions (e.g. Ag+) disc~ssed.~3 The l7O magnetic resonance of a number of oxyanions shows a high degree of paramagnetic shielding of the oxygen nuclei; the relation between the 170chemical shifts and the ultraviolet and visible spectra of these anions is accounted for theoreti~ally.2~ Thermally stable, zerovalent, complexes with the diphosphine, Me2P*CH2*CH2*PMe2, been isolated have with all members of the first transition series except titanium and manganese. Octahedral M(diphosphine), (M = V, Cr, Mo, or W) and tetrahedral M(diphosphine), (M = Fe or Co) are obtained by the reduction of higher-valent complexes with sodium naphthalide in tetrahydrofuran. 25 The metals from manganese to zinc react with suspensions of nitrosyl tetrafluoroborate in methyl cyanide or ethyl acetate to give solutions of bivalent-metal tetrafluoroborates. From these solutions complexes can be prepared, e.g., Cu(BF4),,4MeCN and Fe(BF4),,6MeCN.26 Dimethyl sulphoxide forms solvates with many transition-metal halides, e.g., CrC13,5DMS0 and FeC1,,4DMSO ; in some cases autocomplexing occurs :27
2CoC1,
+ 6DMSO + Co(DMSO),++ + CoC1,- -.
Views concerning the structure of EDTA complexes of bivalent cations have been summarised and it is concluded that these complexes are quinquedentate in aqueous solution.28 For chelates of EDTA, diethylenetriamineacid a correlation has penta-acetic acid and triethylenetetraminehexa-acetic been established between the charge : size ratio of the metal ion and the degree of covalency in the metal-oxygen bond.29 Several new ligands
F. Helfferich, J . Arner. Chem. SOC.,1962, 84, 3237, 3242. V. F. Doron and S. Kirschner, Inorg. Chem., 1962, 1, 539. a1 S. T. Spees and A. W . Adamson, Inorg. Chem., 1962, 1, 531. 2 2 R. F. Fenske, D. S. Martin, jun., and K. Ruedenberg, Inorg. Chem., 1962, 1, 441. 23 M. C. R. Symons and P. A. Trevalion, J., 1962, 3503. 2 4 B. N. Figgis, R. G. Kidd, and R. S. Nyholm, Proc. Roy. SOC., 1962, A , 269, 469. 2 5 J. Chatt and H. R. Watson, J., 1962, 2545. B. J. Hathaway, D. G. Holah, and A. E. Underhill, J., 1962, 2444. H. L. Schlafer and H. P. Opitz, 2. anorg. Chem., 1961, 313, 178; V. Gutmann and L. Hubner, Monatsh., 1961, 92, 1261; V. Gutmann and G. Schober, ibid., 1962, 93, 212. 2 8 W. C. E. Rigginson, J . , 1962, 2761. 2 9 R. E. Sievers and J. C. Bailar, jun., Inorg. Chem., 1962, 1, 174.
l9
2o
172
INORGANIC CHEMISTRY
have been described during the year. The chelate dimethyl-3-methylthio). propylarsine (8) forms crystalline complexes, M(As-S)X, (X = C1, Br, I , with copper(I), palladium(n), and p l a t i n u m ( ~ ~ The ~ ) . ~ ligand 2-2-hydroxyethylpyridine is for the most part bidentate; cobalt(@ and nickel(=) chlorides, however, yield co-ordination compounds in which only the nitrogen atom of the pyridine ring acts as a d0nor.~1 Very stable complexes (9) are formed by almost all transition metals with 1-2-pyridyl-2-2-pyridylmethylenehydrazine; their stability constants are sufficiently high to enable transition aetals to be extracted from their EDTA complexes.32 The
H
1 CHICH2
SMe
@yyJ
\
CHI- **Me2
(8)
N+M+N
(9)
,O*CH2, qO.CH2;;CMe O.CH2
(0)
effect of reducing steric hindrance to co-ordination, with respect to the additional effect of low ligand-ligand repulsion, has been demonstrated for the constrained phosphite ester 4-methyl-2,6,7-trioxa-l-phosphabicyclo[2,2,2]octane (10). The bicyclic base forms tetrahedral complexes, (CuL,), ClO,, and (AgL,)NO,, in which the maximum co-ordination number is achieved with only ligand molecules.33 The reaction of metal ions [Co(n), CO(III), Ni(n), Cu(n), and Z~(II)] with the zwitterion betaine have been studied and the infrared spectra of the complexes produced have been a~signed.~4 The first complexes in which a transition metal is co-ordinatively saturated with nitrate ligands have been ~repared.~5 Tetramethylammonium tetranitratocobaltate(n) is obtained from nitromethane solutions of tetramethylammonium and cobalt(=) nitrates. Magnetic studies indicate that the [Co(ONO,),]2- ion is tetrahedral. Oxidation of potassium tetranitropalladate(n) with concentrated nitric acid yields K,Pd(NO,), as an orange-red solid stable in air but immediately hydrolysed in aqueous solution. There has been considerable interest shown in reactions of co-ordin1 ated ligands. Ethylenediamine- and propylenediamine-nickel(1 )complexes react with acetone to form Schiff-base complexes, e.g. ( l l ) ,with two, three, and four N-isopropylidene groups. With triethylenetetraminecopper(TI) or -nickel( 11) complexes and acetone, co-ordination compounds are obtained having three secondary amine and one azomethine donor groups.36 Sometimes metal ions can facilitate the formation of an organic molecule that otherwise cannot be isolated because of competing reactions. Thus attempts to prepare Schiff bases between or-diketones and 2-mercaptoethylamine result in the production of thiazolines; in the presence of nickel(=) ions,
B. Chiswell and S. E. Livingstone, J . Inorg. Nuclear Chem., 1961, 23, 37. E. Uhlig and H. Schon, 2. anorg. Chem., 1962, 316, 25. 32 J. F. Geldard and F. Lions, J . Amer. Chem. SOC., 1962, 84, 2262. 33 J. G. Verkade and T. S. Piper, Inorg. Chem., 1962, 1, 453. 3 4 J. V. Quagliano, S. Kida, and J. Fujita, J . Amer. Chem. SOC., 1962, 84, 724. 3 5 F. A. Cotton and T. G. Dunne, J . Amer. Chem. Soc., 1962,84,2014; R. Eskanazi, J. Raskovan, and R. Levitus, Chem. a d Id., 1962, 1327. 3 6 M . M. Blight and N. F. Curtis, J., 1962, 1204, 3016; D. A. House and N. F. Curtis, J . Amer. Chem. SOC., 1962, 84, 3248.
30
31
NICHOLLS : T H E TRANSITION ELEMENTS
173
however, Schif-basecomplexes (12) are formed which contain a novel tetradentate ligand.37 The chelate trisacetylacetonates of chromium(m), cobalt(In), and rhodium(m) can be nitrated by treatment with copper(rr) nitrate and acetic anhydride, and formylated with dimethylformamide in the presence of phosphorus oxychloride.38 The ligand-field splitting of d orbitals in eight-co-ordinate complexes of dodecahedral structure has been deduced from the known order of these
Me 2C
II
CMe2
II
orbitals in a cube, by considering the effect on individual d orbitals of the distortion of the cube into the dodecahedron. The most stable orbital is d,, and this orbital is not used in dodecahedral d4sp3hybridi~ation.,~ Infrared spectra in the C-N stretching region provide a means of distinguishing between terminal and bridging cyanide groups in complex cyanides; the bridging cyanides exhibit the higher absorption frequency.40 Infrared spectra also clearly distinguish between a unidentate and a bidentate carb~nato-group.~~ Trends found in the infrared spectra of trans[MX(COR)(PEt,),] (M = Pt, Pd; X = NO,, NCS, NO,, halogen; R = Me, Ph) have been explained with the help of resonance structures, and the spectra of trans-[PtCl(CX,)(PMe,),] and cis-[Pt(CX,),(PMe,),] (X = H, D) have been used to confirm the previous assignment of the Pt-C stretching modes.42 Changes in the electronic structures of chelate acetylacetonate rings through substitution in the ligand have been observed in their infrared spectra, and more quantitative information deduced from force-constant calculations using the perturbation method.43 Investigations of metal-ligand n-bonding in octahedral complexes of bivalent cobalt, nickel, and iron with 2,3-bismethyliminobutane (BMI), 1,2-dihydro-2-methyliminopyridine, 1,2,3,6and tetrahydro-2,6-bismethyliminopyridine(TBMI) show that conjugative dn-pn bonding is greatest in complexes of BMI particularly with iron(@. The stereochemical relationships associated with the planar tridentate ligand TBMI favour spin pairing in the d7 cobalt(=) ion.44 (b) Mechanisms of reactions of inorganic complexes. Only the briefest review can be made of the large number of publications in this field. The oxidation of vanadium(m) by iron(n1) in aqueous perchloric acid paoceeds by two distinct routes.45 First a single-stage reaction,
M. C. Thompson and D. H. Busch, J . Amer. Chem. SOC., 1962, 84, 1762. J. P. Collman, R. L. Marshall, W. L. Young, and J. D. Goldby, Inorg. Chem., 1962, 1, 704. 39 M. Randic, J . Chem. Phys., 1962, 36, 2094. 4 0 D. A. DOWS, A. Haim, and W. K. Wilmarth, J . Inorg. Nuclear Chem., 1961, 21, 33. 41 J. Fujita, A. E. Martell, and K. Nakamoto, J . Chem. Phys., 1962, 36, 324. 4 a D .M. Adams and G. Booth, J., 1962, 1112; D. M. Adams, J., 1962, 1220. 4 3 K. Nakamoto, Y. Morimoto, and A. E. Martell, J . Phys. Chem., 1962, 66, 346. 4 4 P. E. Figgins and D. H. Busch, J . Phys. Chem., 1961, 65, 2236. 4 5 W. C. E. Higginson and A. G. Sykes, J., 1962, 2841.
37
38
174
FeIII VII1--+ FeII VIV, occurs and this is followed by the secondary reactions, FeIII VIV FeII Vv and Vv V"I -+ 2VIV. The replaceby a ment of an ammonia molecule in [GO(NH,)~(OAC)]~+ second carboxylate group results in a hundred-fold increase in the uncatalysed rate of reduction by Cr2+aq. It seems likely that this replacement by a ligand producing a weaker field increases the probability of electron transfer by lowering the energy of the acceptor antibonding d orbital of cobalt.46 Studies on freeradical reactions of co-ordination compounds show that, in the pentane-2,4dione chelates, co-ordination changes the site of radical attack. The increase in the rate of attack with increasing number of d electrons of the metal ion suggests that the back-donation of electrons from the metal to the organic ligand is very important in determining the relative r e a ~ t i v i t i e s . ~ ~ A method for the kinetic study of moderately fast reactions uses a noncomplexing salt to depress the freezing point of water to a temperature low enough to increase the reaction ha1f;time to a t least twenty seconds.48 The stopped-flowmethod has been used to study the rates of dissociation in acid solution of nickel@) and copper(n) complexes with a series of nitrogencontaining ligands; the importance of the dissociative process in determining the stability of nickel(rr) complexes has been further e~tablished.~s I n the acid-catalysed aquation of [Co(CN),N,I3-, and in the substitution of water in [CO(CN),OH,]~-by azide ions, there is strong evidence for S,1 mechanisms involving the pentaco-ordinate intermediate, [Co(CN),]2-.50 The equilibrium between cis- and trans-[Co en2C12]C104 dimethylformamide in and dimethylacetamide has been studied spectrophotometrically. The amount of cis-isomer at equilibrium increases with chloride concentration in a way that is consistent with the formation of a strong ion-pair between chloride and the cis-isomer and a weak one with the trans-isomer.51 The isomerisation of hydroxoamminecobalt(1n) complexes, e.g., trans[Co en2(NH,)( 0H)l2+, probably occurs via an intramolecular mechanism involving a unimolecular dissociation of one end of an ethylenediarnine chelate ring under the labilising influence of the hydroxyl gr0up.52 The kinetics of the reactions of ethylenediamine with Co(EDTA)- and Co(PDTA)- (PDTA = propylenediaminetetra-acetate) have been investigated. The determination of the absolute configurations of Co(EDTA)-, [Co(EDTA)XI2-, Co(PDTA)-, and [Co(PDTA)X]2- (X = C1, Br) constitute the first examples of unequivocal deduction of configuration from the kinetics and stereochemistry of a reaction of an octahedral ion.53 The racemisation of d-[Co(EDTA)]- proceeds very slowly in acid media by a pH-independent path with a high activation energy and a positive entropy
J . Amer. 4 7 R. 4 8 C. 4 9 R.
K. D. Kopple and R. R. Miller, Proc. Chem. SOC., 1962, 306; R. T. M. Fraser, Chem. SOC., 1961, 83, 4920. J. Gritter and E. L. Patmore, Proc. Chem. SOC., 1962, 328. S. Garner and J. Bjerrum, Acta Chem. Scand., 1961, 15, 2055. G . Wilkins, J., 1962, 4475; G. A. Melson and R. G . Wilkins, ibid., p. 4208. 60A. Haim and W. K. Wilmarth, Inorg. Chem., 1962, 1, 573, 583. 61M. L. Tobe and D. W. Watts, J., 1962, 4614. 6sD. F. Martin and M. L. Tobe, J., 1962, 1388. 63 D. H. Busch, K. Swaminathan, and D. W. Cooke, Inorg. Chem., 1962, 1, 260; D. H. Busch and K. Swaminatham, J. Inorg. Nuclear Chern., 1961,23, 150; D. H. Busch and D. W. Cooke, ibid., p. 145.
46
NICHOLLS
: THE T R A N S I T I O N ELEMENTS
175
change; this rules out a dissociative (XN1) mechanism. A strong base catalysis of racemisation is observed ;its path probably involves nucleophilic attack by a hydroxyl ion with the formation of a symmetrical sevenco-ordinate intermediate. 5 4 A seven-co-ordinate intermediate in which five ligands form a symmetrical square pyramid with the remaining two situated above the base in the (z y)x-planehas been discussed theoretically. The two models considered are those in which the angle between the two ligands above the base is the tetrahedral angle and An attempt has been made to measure the extent to which the co-ordination of a ligand to a metal affects the ionisation of acid side-groups on the ligand.56 When Fe2+ forms a complex with pyridine-2-aldoxime7the acid strength of the oxime groups increases from pK" = 10.22 (free ligand) to pK" = 7.13 in the tris-complex at 25". From reaction rates of diethylenetriamineaquoplatinum(@ with various ligands it is concluded that an aquo-complex formed by an Lj"2 reaction with water is the principal intermediate in the totally first-order reactions of platinum(@ There is good kinetic and spectral evidence that association between nitrite ion and cis-[Pt(NH,) , NO,)Cl] gives a transient intermediate, [Pt(NH,)2( NO,),Cl]-, ( which probably has a tetragonal pyramidal structure ; elimination of chloride ion then occurs to give ~is-[Pt(NH,),{N0,),].5~ I n the base hydrolysis of chloroamineplatinum(1v) complexes, the predominant species formed are amido-complexes, e.g., [Pt(NH,),(NH2)C1]2, but considerable reduc+ tion to platinum(I1) occurs in those complexes containing trans-chlorogroups.59 (c) Carbonyls. A molecular-orbital energy-level scheme has been presented for the large class of metal carbonyls and nitrosyls in which one particularly strong M-CO or M-NO bond dominates the overall ligandfield.60 The Raman spectra of several carbonyls have been measured. I n nickel tetracarbonyl there is direct evidence for partial multiple metalcarbon bonding and conjugation between M-C and C-0 bonds. The carbonyls, CdCo(CO), and Hg[Co(CO),],, do not contain bridging carbonyl groups but have a three-fold principal molecular axis containing the atoms O-C-Co-Cd( Hg)-Co-C-0 with the staggered D,,configuration for the entire molecule.61 The photoproduction of group V I metal hexacarbonyl derivatives, e.g., M(CO),,CH,CN and Mo(C0),,2pC,H4*(NH,),, has been thought to proceed by a mechanism involving the M(CO), radical as initiating species ;62 now tungsten pentacarbonyl has been identified with a half-life
54D. W. Cooke, Y. Ae Im, and D. H. Busch, Inorg. Chem., 1962, 1, 13. 55N. Hush, Austral. J . Chem., 1962, 15, 378. S. 5 6 G. I. H. Hanania and D. H. Irvine, J., 1962, 2745, 2750. 5 7 H. B. Gray and R. J. OIcott, Inorg. Chem., 1962, 1, 481. 5 8 P. Haake, Proc. Chem. Soc., 1962, 278. 5 9 R. C. Johnson, F. Basolo, and R. G. Pearson, J . Inorg. Nuclear Chern., 1962, 24, 59; A. A. Grinberg and Yu. N. Kukushkin, Zhur. neorg. Khim., 1961, 6, 1084 (554). 6 0 H. B. Gray, I. Bernal, and E. Billig, J. Amer. Chem. SOC., 1962, 84, 3404. 6 1H. Stamrnreich, K. Kawai, 0. Sda, and P. Krumholz, J. Chem. Phys., 1961, 35, 2168, 2175. 6 2 W. Strohmeier and G. Schonauer, Chem. Ber., 1962, 95, 1767; W. Strohmeier, D. Von Hobc, G. Schonauer, and H. Laporte, 2. Naturforsch., 1962, 17b, 502; G. R. Dobson, M. F. A. El Sayed, I. W. Stolz, and R. K. Sheline, Inorg. Chem., 1962, 1, 526.
176
INORGANIC CHEMISTRY
of about two minutes at room temperature, during the ultraviolet irradiation of W(CO), solution.63 That this irradiation is not essential in the production of these carbonyl derivatives has been demonstrated by the production of the tris-nitrile compounds, (CH,CN),M(CO), (M = Mo, W, Cr), which are conveniently prepared by refluxing the carbonyl in an excess of acetoOne or two carbonyl groups in Ni(CO), andMo(CO), are directly replaceable by monodentate arsenic ligands. Bidentate nitrogen and s d phur donors replace two carbonyl groups forming M(CO),L (M = Cr, Mo, W; L = 2,2'-bipyridyl, 2,5-dithiahexane), and tridentate sulphur donors can form LM(CO), (L = 3,6,9-trithiaundecane). The reaction of the bipyridyl derivatives of molybdenum and tungsten carbonyls with bromine results in the formation of compounds, M(CO),( bipy)Br,, which appear to be sevencovalent derivatives of molybdenum(I1) and t u n g s t e n ( ~ ~ ) . ~ ~assignThe ment of carbonyl stretching frequencies in the substituted carbonyls, L,M(CO),_,, where M is a d6 atom or ion, has been attempted.66 I n the compounds, MoL,(CO), (L = unidentate sulphur donor), prepared by the action of the ligands on cycloheptatrienemolybdenum tricarbonyl, the C-0 stretching frequencies show that dialkyl sulphides have a substantial tendency to function as macceptors.6 7 The carbonylation reaction, MeMn(CO), CO --+ MeCOMn(CO),, is first-order in both reactants.68 Thermally-unstable acylcobalt tetracarbonyls (and their perfluoro-analogues) can be isolated as triphenylphosphine derivatives by reaction of sodium cobalt tetracarbonyl with acyl halides or acyl anhydrides, or with alkyl halides and carbon monoxide.69 A number of transition-metal carbonyls are protonated in strong-acid solutions giving species such as [HFe(CO),(PPh,),] +, [H (Mo(CO),(n-C,H,) >,I +, and [HCr(CO),C6H5Me] I n most cases the presence of a metal-hydrogen +. bond can be demonstrated only from the nuclear magnetic resonance spectra, but a few salts can be isolated, e.g., [ (n-C,H, l?e(C0)2)2H]PF6, which the in infrared spectra confirm the presence of the M-H bond. The binuclear carbonyl-n-cyclopentadienyl-molybdenum and -tungsten compounds are unusual among protonated species in that the hydrogen is associated with two metal at0ms.7~ The addition of manganese pentacarbonyl hydride to some fluoro-olehs gives a-bonded organomanganese compounds, e.g., HCF,*CF,*Mn(CO), which contains octahedrally co-ordinatedmanganese. It' is possible to replace two carbonyl groups of perfluoropropyliron tetracarbony1 iodide with pyridine or 2,2'-bipyridyl, but only one with triphenylphosphine.71 Reduction of nickel carbonyl with sodium borohydride in
63
I. W. Stolz, G. R. Dobson, and R. K. Sheline, J . Amer. Chem. Soc., 1962, 84,
D. P . Tate, W. R . Knippls, and J. M. Augl, Inorg. Chem., 1962, 1, 433. 65G. Bouquet and M. Brigorghe, Bull. SOC. chim. France, 1962, 433; H. C. E. Mannerskantz and G. Wilkinson, J., 1962, 4454; M. H. B. Stiddard, J., 1962, 4712. 6 6 L. E. Orgel, Inorg. Chem., 1962, 1, 25. 6 7 F. A. Cotton and F. Zingales, Inorg. Chem., 1962, 1, 145. 6 8 F. Calderazzo and F. A. Cotton, Inorg. Chem., 1962, 1, 30. 6 9 R . F. Heck and D. S. Breslow, J. Amer. Chem. Soc., 1962, 84, 2499; W. Hieber and E. Lindner, Chem. Ber., 1962, 95, 2042. 70A. Davison, W. McFarlane, L. Pratt, and G . Wilkinson, J., 1962, 3653. 71 P. M. Treichel, E. Pitcher, and F. G. A. Stone, Inorg. Chem., 1962, 1, 511; R. A. Plowman and F. G. A. Stone, {bid., p. 518.
64
3589.
NICHOLLS
THE TRANSITION ELEMENTS
177
liquid ammonia proceeds according to :72

2Ni(CO),NH, + 2e-
+H2Ni,(CO), + 2NH2-.
Several mixed metal carbonyls have been synthesised. A fairly general method seems to involve the reaction of the sodium salt of a metal carbonyl, or a cyclopentadienylmetal carbonyl, with an organometallic or carbonyl halide of the other metal; typical products are (CO),CoMn(CO), and R3SnMn( CO), (R = alkyl or aryl).7 3 Dicobalt octacarbonyl reacts with tetravinylsilicon to give purple nonacarbonyl(vinylsilicon)tricobalt, Co3(CO),SiCH,:CH2; its structure is unknown but is expected to be similar These latter complexes to that of the known complexes CO,(CO)&R.~~ are obtained as violet crystals from the [Co(CO),]- ion by reaction with carbon tetrachloride (giving R = Cl), bromoform (giving R = H), and benzotrichloride (giving R = Ph). 7 5 By reaction of tetracarbonylferrate, [Fe(C0),l2-, with nitrite or hydroxylamine an orange-yellow carbonylimine, [Fe(CO),NH],, has been obtained. Withnitric oxide this yields [Fe(NO),NH], which contains bridging NH groups. Ammonia co-ordination compounds, Fe(CO),NH3andMn,(CO),NH3, obtained are upon reaction of hydroxylamine-2-sulphonic R, ,R 0 II acid with alkaline solutionsof tetracarbonyl- , /N / C \ A, - N ferrate and pentacarbonylmanganate ions, , \ C Ni Ni + respectively.76 Dialkylcyanamides react N o 'R 'R (13) with nickel carbonyl forming orange, airsensitive, diamagnetic carbonyl-bridged complexes (13). 7 A convenient synthesis of dicarbonyldinitrosyl-iron(0) uses the reaction of iron pentacarbonyl with nitrosyl chloride; the new derivatives, (Ph,P)Fe(CO)(NO), and (Ph,As),Pe(NO),, have been described.78 Manganese carbonyl halides react with a variety of unidentate ligands giving monosubstituted compounds, Mn(CO),LX (X = C1, Br, I). Disubstituted derivatives are obtained with some unidentate ligands and bidentate ligands; Mn(CO),LX (L = bidentate As, P, S ligand) are mono79 meric, octahedral non-electrolytes containing manganese(1). Reduction of Mn(CO),PR, and [Mn(CO),PR,], with alkali-metal amalgam gives phosphine-substituted carbonylmanganates(-1) ; these give hydrides, e.g., HMn(CO),(PR,), upon treatment with acids.80 The infrared spectrum of Mn,(CO),P(CF,),I excludes the possibility of carbonyl bridging so that the binuclear complex probably contains phosphorus and iodine bridges.81 Phosphine-substituted cobalt(1)carbonyl halides, Co(CO),PPh,X (X = I, Br),
, ,
5
H. Behrens and H. Zizlsberger, J . pralct. Chem., 1961, 14, 249. R. D. Gorsich, J. Arner. Chem. Soc., 1962, 84, 2486; K. K. Joshi and P. L. Pauson, 2. Naturforsch., 1962, 17b, 565; W. Hieber and T. Kruck, Chem. Ber., 1962, 95, 2027. 7 4 S. F . A. Kettle and I. A. Khan, Proc. Chem. Soc., 1962, 82. 7 5 G . Bor, L. Mark6, and B. Marld, Chem. Ber., 1962, 95, 333. 76W. Hieber and H. Beutner, 2. anorg. Chem., 1962, 317, 63. 7 7 H. Bock, Angew. Chem., 1962, 74, 695. 7 8 D. W. McBride, S. L. Stafford, and F. G. A. Stone, Inorg. Chem., 1962, 1, 386. 7 9 A. G. Osborne and M. H. B. Stiddard, J., 1962,4715; R. J. Angelici and F. Basolo, J . Arner. Chem. SOC., 1962, 64, 2495. 8 0 W. Hieber, G. Faulhaber, and F. Theubert, 2. anorg. Chem., 1962, 314, 125. 8lH. J. Emelkus and J. Grobe, Angew. Chern., 1962, 74, 467.
73
73
178
INORGANIC CHEMISTRY
are obtained upon mild halogenation of [Co(CO),PPh,]- anions with trifluoroiodomethane and N-bromosuccinimide.8 2 The bisphosphineiridium(I) carbony1 halide, [IrCl(CO)(Ph,P),], shows a striking reactivity towards a large number of molecules. Hydrogen reacts with it as a Lewis acid, oxidising ; the iridium to the diamagnetic non-electrolyte, [Ir111H2Cl(CO)(PPh,),I this compound, when treated with hydrogen chloride in ether, reacts to give [IrDIHCI,(CO)(PPh,),] and hydrogen. 83 Well-defined adducts, of formula [FeCl,(CO),( PEt,Ph,- ,),I, are formed when carbon monoxide reacts under mild conditions with [FeCl,(PEf,Ph,,,),] (n = 1-3). With cobalt(1) only those complexes where n = 3 can be isolated, and the corresponding nickel(n) complexes do not form a d d u ~ t s . ~ 4 (d) Nitrosyb. The gas-phase reaction between nitrosyl chloride and nickel carbonyl yields the grey-green, paramagnetic nitrosyl dihalides of nickel, Ni(NO)Cl,. The infrared spectrum of this compound indicates that in the solid there are co-ordinated NO groups present in two different environments. Nitric oxide is not evolved below 150" but triphenylphosphine reacts at 100" in a sealed tube forming (Ph,P),Ni(NO)C1.85 Dimeric dinitrosylcobalt halides react with organo-phosphines, -arsines, and -stibines in solution forming diamagnetic monomers, Co(NO),LX. I n the molten state, disproportionation occurs :
[CO(NO)~C~]~ 6PPh3 +Co(NO)(PPh,)s Co(OPPh3)2C12
+ OPPh3 + 14N2-
Dinitrosylrhodium chloride undergoes a similar disproportionation upon reaction with these ligands a t room temperature.86 The manganese nitrosyl carbonyl derivatives, Mn(NO),L, Mn(NO)(CO),L, Mn(NO)(CO),L,, and Mn(NO),L,X (L = PR,, AsR,, SbR,; X = halogen), are considerably more stable than the unsubstituted compounds. Reduction of Mn(NO),(PPh,),Br with sodium borohydride gives MnH(NO)2(PPh,)2.87 I n nitroso(dimethy1dithiocarbamato)cobalt, [Co(NO) (S,CN(CH,), I,], the co-ordination round the cobalt atom is that of a rectangular-based pyramid with the NO molecule a t the apex and the four sulphur atoms a t the corners of the base. The dithiocarbamate ligands me planar; the N-0 bond is inclined a t 139" to the pyramidal axis, and the NO group appears to form an unsymmetrical n-complex with the cobalt atom.88 An electron-spin resonance study of the [Fe(CN),N0]3- ion shows that the unpaired electron is delocalised between the iron and the nitric oxide ligand. Experimental data suggest that these metal-nitrosyl complexes should be considered as molecular species with electrons delocalised to different extents rather than as containing charged ligands.89 Oxidation of chromium(IT) by nitric oxide produces three chromium(m) complexes which can be separated by ion-exchange; one of these has been identified as [Cr(H,O),N0I2+ and has been isolated as the sulphate.90 Studies on the nitrato-complexes of nitrosylruthenium have
82
84
85
8SL.
W. Hieber and E. Lindner, Chem. Ber., 1962, 95, 273. Vaska and J. W. Diluzio, J. Amer. Chem. SOC., 1962, 84, 679.
G. Booth and J. Chatt, J., 1962, 2099. C. C. Addison and B. F. G. Johnson, Proc. Chem. Xoc., 1962, 305. W. Hieber and K. Heinecke, 2. anorg. Chem., 1962, 316, 305, 321. W. Hieber and H. Tengler, 2. anorg. Chem., 1962, 318, 136. P. R. H. Alderman, P. G. Owston, and J. M. Rowe, J . , 1962, 668. I. Bernal and E. F. Hockings, Proc. Chem. SOC.,1962, 361. M. Ardon and J. I. Herman, J., 1962, 507.
a6
89
NICHOLLS
179
shown that the complex most readily extracted in tri-n-butyl phosphate is [Ru(NO)(NO,),( H,O),] ; cationic species isolated by ion-exchange have been assigned the formuls [Ru(NO)(NO,),(H20),]f, [Ru(NO)(N0,)(H,0)4]2 , + and [RU(NO)(H,O)~]~+.~~ (e) OZeJin complexes. A review has appeared concerning olefin, acetylene, and n-allylic complexes of transition metal~.~aYellow, crystalline bis(tripheny1phosphine)ethylenenickel is formed in the reaction of nickel acetylacetonate with diethylaluminium ethoxide in benzene containing triphenylphosphine. Displacement of ethylene -is achieved with other o l e h and acetylene donors forming (PPh,),NiD (D = CH,:CHPh, PhC:CPh, e t ~ . ) . ~ ~ Silver-olefin complexes, AgN0,,C4H6 and 2AgNO3,C4H6, are precipitated when butadiene is passed through 8M-silvernitrate solution at 15.94 Silver fluoroborate absorbs gaseous olefins, e.g. , ethylene, propene, and butenes, at room temperature forming solid complexes of high stability.95 Copper(1) halides form 1 : 1 complexes with aryl-substituted 1,l-dicyanoethylenes and also with the chelating o l e h s norbornadiene, dicyclopentadiene, and cyclo0ctadiene.9~ A complete crystal-structure study of rhodium(1) chloride-l,5cyclo-octadiene has confirmed that the rhodium atom is in an approximately square-planar configuration, being bonded to two bridging chlorine atoms and the double bond centres of a cyclo-octadiene The ethylene complex, (C,H4),RhC12(C,H,),, which is probably similar in structure, has been prepared from rhodium(1rr) chloride hydrate and ethylene in aqueous rnethan01.9~ The planar platinum complexes, Pt(olefin)(PPh,), (olefin = trans-stilbene, truns-4,4-dinitrostilbeneY and acenaphthylene), are formed from cis-[Cl,Pt(PPh,),] in ethanol containing hydrazine hydrate and the olefin at 60.99 Mesityl oxide derivatives of platinum and palladium halides have dissimilar structures. The palladium compound, C6H,,C10Pd, has
been reformulated as a n-allylic derivative (14) on the basis of its infrared and proton magnetic resonance spectra. I n contrast to this palladium compound, reagents like dimethyl sulphoxide and triphenylphosphine displace the mesityl oxide ligand in the platinum derivative, forming L,PtCl,. High-resolution proton magnetic resonance studies exclude a n-allylic
R. M. Wallace, J . Inorg. Nuclear Chem., 1961, 20, 283. R. G. Guy and B. L. Shaw, Adv. Inorg. Chem. Radiochem., 1962, 4, 78. O 3 G. Wilke and G. Herrman, Angew. Chem., 1962, 74, 693. O 4 J. W. ICraus and E. W. Stern, J . Arner. Chem. Soc., 1962, 84, 2893. O 5 H. W. Quinn and D. N. Glew, Canad. J . Chem., 1962, 40, 1103. *13 G. N. Schrauzer and S. Eichler, Chem. Ber., 1962, 95, 260. 9 7 J. A. Ibers and R. G. Snyder, Acta Cryst., 1962, 15, 923; idem, J . Amer. Chem. SOC., 1962, 84, 495. O 8 R . Cramer, Inorg. Chem., 1962, 1, 722. J. Chatt, B. L. Shaw, and A. A. Williams, J., 1962, 3269.
O1
Oa
180
INORGANIC CHEMISTRY
structure, and the polymer structure (15)is proposed.loO A further example of n-allylic bonding in palladium compounds is that presented by the revised structure for " butadiene palladous chloride " ( 16).lo1 The crystalstructure determination on the n-allyl, [PdCl(C3H5),], has confirmed the st'ructure suggested on spectroscopic evidence; the plane of the ally1 group is approximately perpendicular to the plane of the (PdCl), bridge.12 The first perfluoro-n-allylic complex has been isolated from the reaction of tricarbonyloctafluorocyclohexa-1,3-dieneironwith caesiurn fluoride in tetrahydrofuran;13 n-C,F,Fe(cO), F- --+ I.n-C,F,Fe(CO),]-. Bis(cyc1opentadieny1)nickelreacts with tetrafluoroethylene when heated in tetrahydrofuran at SO", giving a new n-allylic derivative logof unusual structure (17).
CHlC I
Ni
('7)
The diamagnetic, octahedral molybdenum complex ( 18), prepared from Mo(CO), and ethyl sorbate at 130, undergoes reaction lo5 with methanol to form the binuclear complex (19). The stable cation, [Re(CO),(C,H,),] +,
Me
MeOH
Me
Me
Et0,C
coc o '
Me
'
('9)
has been isolated as its hexafluorophosphate; it is colourless and diamagnetic and probably contains n-bonded C,H, ligands in &-octahedral positions.lo6 Cations containing penta- and hexa-dienylcarbonium ions as ligands are obtained by hydride abstraction from the corresponding alcohols, e.g.,lo7
H
HClOa
Fe
oc '.I -'co co
loo
0C':e~CO
co
G. W. Parshall and G . Wilkinson, Chem. and Ind., 1962, 261. l o l B . L. Shaw, Chern. and I d . , 1962, 1190. I o 2 J. M. Rowe, Proc. Chern. Soc., 1962, 66. l o 3 G . W. Parshall and G. Wilkinson, J . , 1962, 1132. l o 4D. W. McBride, R. L. Pruett, E. Pitcher, and F. G. A. Stone, J . Amer. Chem. SOC., 1962, 84, 497. lo6 R. P. M. Werner and S . Manastyrskyj, J . Inorg. Nuclear Chem., 1961, 21, 278. lo6 E. 0. Fischer and K. Ofele, Angew. Chem., 1962, 74, 76. J. E. Mahler and R. Pettit, J . Amer. Chern. SOC.,1962, 84, 1511.
NICHOLLS : T H E T E A N S I T I O N ELEMENTS
181
Two butadieneiron carbonyls have been prepared from Fe,(CO) in n-hexane. I n C,H,Fe(CO),, an unstable orange liquid, the olefin is readily replaced by triphenylphosphine ; crystalline C,H,Fe,(CO), is stable in air.10s The coordination around the iron atom in tetracarbonyl(acry1onitrile)ironis essentially trigonal bipyramidal, the equatorial plane containing two Fe-CO bonds and one from iron to the C=C double bond in acry10nitrile.l~~ tricarbonyl, Intramolecular distances (X-rays) in 2,4,6-triphenyltroponeiron [C,H30(C,H,),]Fe(CO),, clearly indicate bonding of the Fe{CO), fragment with only two of the three double bonds in the ring.ll0 Irradiation of solutions of cyclo-octatetraeneiron tricarbonyl in benzene, in the presence of excess of cyclo-octatetraene, gives rise to yellow complexes which are Fe(CO), adducts of hitherto unknown C,Hs dimers.lll The molecular structure of C,H,Fe(CO), shows that it contains a new form of cyclo-octatetraene ring-a distorted tub form in which six of the eight atoms of the ring are very nearly coplanar.112 The synthesis of n-bonded metal compounds containing the cyclopropene ring has been attempted.l13 Triphenylcyclopropenyl bromide reacts with the [Co(CO),]- and [Fe(CO),N0I3anions giving compounds in which the cyclopropene ring may be intact, e.g. (20); an alternative structure for the cobalt compound is that containing the four-memberedring system (21). Very stable and unreactive compounds
$k!
j-+co(co)3
0
ICO)3
(20)
(21)
result from the interaction of hexafluorobut-2-yne with iron and cobalt and carbonyls and with carbonyl-n-cyclopentadienyl-cobalt -nickel; typical products are C9Fl,0Fe(CO), [probable structure (22)], C,F,Co,(CO),, C,F,Ni,( n-C5H5),,and (n-C5H,)CoC,Fl,.
I n the last compound, nuclear magnetic resonance spectroscopy clearly shows two types of CF, groups to be present, and hence its structure is as shown in (23). These are the f i s t examples of a cyclic carbon system bound to a single metal atom by both G bonds and donor olefinic bonds.ll4
lo8
110 lo9
D. L. Smith and L. F. Dahl, J . Amer. Chern. Xoc., 1962, 84, 1743. N. Schrauzer and S. Eichler, Angew. Chem., 1962, 74, 585. 1 1 2 B. Dickens and W. N. Lipscomb, J. Amer. Chem. Soc., 1961, 83, 4862. 113 C. E. Coffey, J. Amer. Chem. Xoc., 1962, 84, 118. 1 1 4 J. L. Boston, D. W. A. Sharp, and G . Wilkinson, J., 1962, 3488.
l l 1 G.
H.D. Murdoch and E. Weiss, Helv. Chim. Actu, 1962, 45, 1156. A. R . Luxmoore and M. R. Truter, Actu Cryst., 1962, 15, 1117.
182
INORGANIC CHEMISTRY
(f) Acetylene complexes. The photochemical displacement of a carbonyl group from a metal complex by diphenylacetylene has been used in the preparation of n-C,H,Mn( CO),PhCiCPh. 116 Complex acetylides of palladium(I1) and palladium(0) have been prepared in liquid ammonia by the reactions :
K,Pd(CN), 2KC:CR -+ K,[Pd(CN),(CiCR),] 2KCN K,[Pd(CN),(CiCR),] 2K -+ K,Pd(CiCR), 2KCN.
The platinum compounds are obtained similarly. Ammonia-insoluble K2Pt(CiCR),is diamagnetic and pyrophoric, and can be oxidised with dry oxygen in ammonia to the tetra-alkynylplatinate(n).116Ethynyl(tertiary phosphine)copper(I)complexes, RCiCCu(PR,),, are dimeric in nitrobenzene and rather more associated in benzene when n = 1 ; they are monomers when n = 2. A crystallographic investigation of PhCiCCuPMe, shows that the complex contains tetrameric units, each with a zig-zag chain of four copper atoms. Gold alkynyls, e.g., (PhCiCAu),, (ButCiCAu),, and their complexes with donor molecules, have been described ; towards PhCiCAu, the order of donor strength is PR, > P(OR), > RNC > AsR, > SbR, > Amines. The alkynyls are probably n-bonded between the alkynyl groups and the gold atorns.l17 Diphenylzinc reacts with two moles of phenylacetylene in ether t o give Zn(PhCiC),. If a 1 : 1 ratio of reactants is used, the intermediate formed, PhZnCiCPh, disproportionates in ether and ammonia to ZnPh, and Zn(PhCiC),. Passage of gaseous acetylene through a suspension of zinc amide in ammonia produces the soluble non-electrolyte, Zn(CiCH),,2NH,.118 (g) Complexes with aromatic systems. Weak complexes are formed between titanium(rv) chloride and benzene, 1 , l -diphenylethane, 1,1,3,3-tetraThere is strong phenylbut-l-ene, and I-methyl-l,3,3-triphenylindane. evidence that the titanium(1v) chloride is interacting with the phenyl groups in the olefins 1,l-diphenylethylene and 1 ,1,3,3-tetraphenylbut-l-ene.11s The reflectance and infrared spectra of [CoHg,(sCN),,C,H,] show that the cobalt is octahedrally co-ordinated and that all six SCN groups serve to bridge the two metal atoms. Since [CoHg,(SCN),] is non-existent, and unlikely therefore to act as a host lattice for benzene, it is suggested that the
Ph
I=[
_-.-
.-:::: 4P,I APd::.xl Pd
Ph
CI Ph
Ph
CI . Ph
)=( --.
Ph
(24)
Ph
Ph
benzene molecule forms nbonds simultaneously with two mercury atoms being the fourth ligand of each.120 Tetraphenylcyclobutadienepalladium(n) chloride (24) is obtained upon treatment of the bisbenzonitrilepalladium(n)
115 116
W. Strohmeier, H.Laporte, and D. Von Hobe, Chem. Ber., 1962, 95,
455.
R. Nast and W. Horl, Chem. Ber., 1962, 95, 1470; R. Nast and W.-D. Heinz,
ibid., p. 1478. 117 G. E. Coates and C. Parkin, J . Inorg. Nuclear Chem., 1961, 22, 59; idem, J., 1962, 3220. 118 R. Nast, 0.Kunzel, and R. Muller, Chem. Ber., 1962, 95, 2155. 119 B. Elliott, A. G. Evans, and E. D. Owen, J., 1962, 689. 120 R. Bauer, M. Schellenberg, and G . Schwatzenbach, Helw. Chim. Acta, 1962, 45, 775.
NICHOLLS
I83
chloride and diphenylacetylene reaction product with hydrochloric acid.121 Some n-complexesof transition metals with heterocycleshave been described. With Mn, (CO) o, pyrrole forms t ricarbonyl-n- olylmanganese, pyrr (n-C,H,N)Mn(CO), ; with nickel carbonyl, duroquinone and an olefin (cyclo-octadiene, bicycloheptadiene, or dicyclopentadiene) forms diamag122 netic n-complexes, (olefh)Ni(C6H1202). New carbonylcyclopentadienyl cations synthesised during the year include [(n-C,H,)Fe(CO), olefin]+, [(n-C,H,)Cr(NO),CO]f, [(n-C,H,)Mo(CO),]f, apd [(n-C,H,)W(CO),]+ ; these are isolated as the tetrachl~roaluminates.~~~ Stable cations (26) are produced by hydride abstraction from (n-C,H,)Fe(CO),R (R = Et, Pr", Pri) in a reaction which is reversible; the o-bonded alkyl complexes (25) are
-' H
regenerated upon treatment of the ethylenic complexes with sodium borohydride. 1 2 4 The yellow-brown paramagnetic cation, [Cr(C,H,),] +, can be isolated as its'tetraphenylboron salt from the solution obtained by oxidation of biscyclopentadienylchromium with ally1 iodide.l25 Thorium(IV) and uranium(rv) chlorides react with potassium cyclopentadienide to give the n-cyclopentadienyls, Th(n-C,H,), and U(n-C,H,),. Molybdenum(v) chloride, however, gives diamagnetic Mo(C,H,), in which three of the cyclopentadiene rings are o-bonded.126 New cyclopentadiene-metalcarbonyls include the dimers [(n-C,H, M(CO),], (M = Os, Ru) and n-C,H, Tc(CO),, all of which are obtained by treating the appropriate carbonyl halide with sodium cyclopentadienide in an ether solvent.12' Nucleophilic addition of C,H,to the cation [Co(C,H,),]+ gives a red-brown diamagnetic complex of formula Co,C,,H,,. There is considerable spectroscopic evidence for formulating this complex as bis-[~-cyclopentadienylcobalt(~)-n-cyclopentadienyl1-endo]cyclopentadiene (27).128 Complexes containing cyclopentadienyl and isonitrile groups have now been described. Hexakis(pheny1isocyanide)man121 A. T. Blomquist and P. M. Maitlis, J. Amer. Chem. Xoc., 1962, 84, 2329. 122 K. K. Joshi and P. L. Pauson, Proc. Chem. SOC., 1962, 326; G. N. Schrauzer and H. Thyret, 2. Naturforsch., 1961, 17b, 73. 1 2 3 E. 0. Fischer and P. Kuzel, 2. anorg. Chem., 1962, 317, 226; E. 0. Fischer, K. Fichtel, and K. Ofele, Chem. Ber., 1962, 95, 249; E. 0. Fischer and K. Fichtel, ibid., 2063. lZ4 M. L. H. Green and P. L. I. Nagy, Proc. Chem. Xoc., 1962, 74; idem, J . Amer. Chem. SOC., 1962, 84, 1310. lz6 E. 0. Fischer and K. Ulm, Chem. Ber., 1962, 95, 692. 126 E. 0. Fischer and Y. Hristidu, 2. Naturforsch., 1962, lyb, 275; E. 0. Fischer and A. Treiber, ibid., p. 276; E. 0. Fischer and Y. Hristidu, Chem. Ber., 1962, 95, 253. 1 ' E. 0. Fischer and K. Bittler, 2. Naturforsch., 1962, 17b, 274; E. 0. Fischer 2 and A. Vogler, ibid., p. 421; C. Palm, E. 0. Fischer, and F. Baumgarter, Naturwiss., 1962, 49, 279. 12* E. 0. Fischer, W. Fellman, ar!d G . E. Herberich, Chem. Ber., 1962, 95, 2254; H. P. Fritz and H. J. Keller, ibid., p. 2259.
metal bond ; cyclohexyl isonitrile reacts with (C,H,)Pd(C6Hg)to give the novel
NICHOLLS : THE TRANSITION ELEMENTS
185
accepting capacity of the perfluoro and hydrocarbon derivatives. Thus bis(pentafluoropheny1)mercury (which is thermally stable at 250 ") forms stable neutral co-ordination compounds with 2,2'-bipyridyl and 1,2-bis(diphenylphosphine)ethane.137 The l9F nuclear magnetic resonance spectra of a variety of fluorocarbon derivatives of metals have been reported. The large shift to low field found for the absorption by a CF, group bonded directly to manganese, rhenium, iron, or cobalt is not observed if a carbonyl group is interposed between the metal and the CF2 group. This magnetic screening effect is probably related to the presence of low-lying excited states in the metal-carbon bonds so that the paramagnetic contribution to the screening constants of the fluorine nuclei is substantially increased.13* Metal-carbon 0bonds are split by molecular hydrogen ; diphenylmanganese reacts in tetrahydrofuran at room temperature to give manganese and benzene. Hydrogenation of (n-C,H,),TiMe, produces methane and leaves (n-C,H,),Ti. 139 Electronic effects due to substituents in complexes of t,he type n-X*C,H,Cr(CO), have been discussed in terms of simple molecular-orbital theory and it has been shown that the degree of charge-transfer to the central metal atom is related to the electron-donating power of X.140 The bisbiphenylchromium(1)cation disproportionates slowly when irradiated or heated in aqueous or methanolic solution into bisbiphenyl-chromium(0) . and -chromium(n) I 4 1 The benzoic acid-containingcation, [PhCO,H][Ph,]Cr +, has been isolated as its tetraphenylboron salt. 142 The disproportionation of organomercury halides by tertiary phosphines has been applied to perchlorovinylmercury chloride :
2CC1,:CCIHgCl
+ 2Ph 3P+ (Ph3P),HgCl ,+ (CCl,:CCl) ,Hg.
The reaction is by no means general, however ; addition of triethylphosphine to an ethereal solution of methylmercury bromide results in salt formation and gives [MeHgPEt,]Br. 143 The vapour pressures of dimethyl-zin and -mercury have been measured ; these compounds have Trouton's constants which are normal for non-associated liquids.1 4 4 Molecular Hydrides of the Transition Elements,-Many of these have been mentioned in previous sections. A Tilden lecture of the Chemical Society has dealt with their chemistry.145 A single-crystal X-ray determination of the structure of (n-C,H,),MoH, shows that the molecule is wedge-like, the angle between the eclipsed cyclopentadiene rings being 25 & 3". The Mo-H bond length is approximately 1-1 A and the H-Mo-H bond angle approximately 90".146 I n octahedral OsHBr(CO)(PPh,),, the Os-P bond
1 ' R. D. Chambers, G. E. Coates, J. G. Livingstone, and W. K. R. Musgrave, 3 J., 1962, 4367. 138 E. Pitcher,A. D. Buckingham, and F. G. A. Stone,J. Chem. Phys., 1962,36,121. 139 K. Clams and H. Bestian, Annalen, 1962, 654, 8. 140 D. A. Brown and H. Sloan, J., 1962, 3849. 141 F. R. Hein and H. Scheel, 2. anorg. Chem., 1961, 312, 264. 142 T. F. Burger and H. Zeiss, Chem. and Ind., 1962, 183. 143 D. Seyferth and R . H. Towe, Inorg. Chem., 1962, 1, 185; R . J. Corss, A. Lander, and G. E. Coates, Chem. and Ind., 1962, 2013. 144 L. H. Long and J. Cattanach, J. Inorg. Nuclear Chem., 1961, 20, 340. J. Chatt, Proc. Chern. Soc., 1962, 318. 146 M. J. Bennett, M. Gerloch, J. A. McCleverty, and R. Mason, Proc. Chem. Soc., 1962, 357.
186
INORGANIC CHEMISTRY
trans to the assumed position of hydrogen is longer than expected from the sum of the covalent radii. The other Os-P bonds are shorter and bent
towards Os-H, showing analogy with the structure of [PtHBr(Et,P),].147 Lithium aluminium hydride reduction of [FeCl,(diphosphine),](FeCl,) and [FeCl,(diphosphine),] [diphosphine = C,H,(PMe,),, C,H4(PEt,),, and also o-C,H,(PEf,),] gives mono- and di-hydrides, [FeHCl(diphosphine),], and [FeH,(diphosphine),]. 14s The reduction of perrhenate in aqueous ethylenediamine with potassium gives a compound, K,ReH,, which is identical with those described earlier as KRe,4H20 and KReH4,2H,O, and in view of its diamagnetism it may contain a dimeric anion with a rheniurn-rhenium bond.149
D. N. A. K. HOLLIDAY. D. NICHOLLS.
P. L. Orioli and L. Vaska, Proc. Chem. SOC.,1962, 333. J. Chatt and R. G . Hayter, J., 1961, 5507. 1 4 8 A. P. Ginsberg, J. M. Miller, and E. Koubeck,J. Amer. Chem. SOC., 1961, 83,
14' 148
4909.
ORGANIC CHEMISTRY
1. INTRODUCTION
A SLIGHT alteration has been made in the arrangement of this year's Report by the introduction of sections on " Physical Properties and Organic Structure " and " Reaction Mechanisms " in place of the customary " Theoretical " section. The change reflects the increasing use and greater power of physical methods in structure determination. As a result, this Report contains no collected account of the quantitative study of organic equilibria or of theoretical investigations of molecular structure and properties. It is hoped t o rectify these omissions on a future occasion. I n recent years the study of stereochemistry has become more and more integrated with other aspects of structural investigation and all sections of this Report contain material of stereochemical interest. A separate section under this heading has therefore been discontinued, a policy which will be subject t o review in future years. It was intended to include a separate section on steroids this year. Owing to illness of a Reporter, this has not been possible. At short notice, Dr. Overton, with the help of Dr. C. J. W. Brookes, Dr. J. Elks, and Professor w. Klyne, has included in the " Alicyclic '' section a brief summary of some of the more important steroid papers published during 1962. The section on " Reaction Mechanisms '' is planned as a representative account of current work and illustrates the extent to which mechanistic studies of organic reactions are being pursued. Lack of space has prevented the inclusion, this year, of detailed reports on several important topics, of which the stereochemistry of substitution a t phosphorus and silicon atoms are especially noteworthy and regrettable omissions. Important studies on simple heterolytic reactions have concerned olefin-forming eliminatioru and the clear demonstration of the formation of a tetrahedral intermediate in an electrophilic aromatic substitution. There has been extensive work on intramolecular catalysis of hydrolytic reactions as models for enzyme catalysis. The almost simultaneous appearance of several textbooks on enzyme mechanisms within the general context of organic reaction mechanisms underlines the importance of this approach. Theoretical problems of general interest have been provided by a challenging attack on the basis for " non-classical " carbonium ions and by a proposed re-definition of the concept of aromaticity. Ideas on the latter subject and consequently on the status of the Hiickel rule have been stimulated by experimental work on large conjugated rings (annulenes), in particular on their nuclear magnetic resonance spectra. Important developments in several fields are t o be expected from studies of the chemistry of diazirine, the cyclic isomer of diazomethane.
L. Ingraham, " Biochemical Mechanisms," {ohn Wiley & Sons, Inc., New York, 1962; E. M. Kosower, " Molecular Biochemistry, McGraw-Hill Publ. Co., New York, 1962; S. G. Waley, " Mechanisms of Organic and Enzymic Reactions," Oxford Univ. Press, 1962.
188
ORGANIC CHEMISTRY
There has again been intensive work on certain general methods such as the Wittig synthesis, hydroboration, and modified uses of lithium aluminium hydride, sodium borohydride, and related systems. Aluminium hydride shows a valuable selectivity and there has been interest in catalytic hydrogenation with catalysts prepared by treating noble metal salts with sodium borohydride. The methylene-transfer reagents, dimethylsulphoniummethylide and dimethylsulphoxonium methylide, have a useful r81e to play in synthesis. Characterisation of natural acetylenes from the Compositz continues apace and the remarkable structural relations of these to other compounds which occur with them in Nature are becoming clearer. Interest in the nature of the insect-attractant substances, many of which are simple compounds, is widening. The structures of various prostoglandins have been cleared up. Photochemical transformations, especially of terpenoids and steroids, have been extensively investigated and many interesting products are reported. Optically active trans-cyclo-octene has been reported and the nonadrides, as represented by glauconic and byssochlamic acid, are an unusual new class of natural product. The past year has seen considerable advances in the tetracycline antibiotic field : a fully biologically active prototype of the tetracycline series has been made and there has been progress in biosynthetic studies. A particularly elegant synthesis of griseofulvin has been effected. Progress with the betanidine problem has been reported and a new structure is proposed for xylindein. 4H-Pyran has been obtained. The years work on alkaloids offers much to the chemical connoisseur and biogenetic schemes, hypothetical or experimentally supported, are again of interest. Study of the nucleic acids has made considerable advance, particularly from a biochemical aspect, since the last Report. The value of nuclear magnetic resonance spectroscopy in carbohydrate chemistry is being increasingly recognised. A useful index of review articles in organic chemistry which were published during 1940-1960 has appeared. Its value and continuity is enhanced by the annual appearance of the Bibliography of Chemical Reviews which commenced with coverage of the year 1958 and has now reached 1961.
L. c. V. G .
N. Kharasch, W. Wolf, and E. C. P. Harrison, Index to Reviews, Symposia Volumes and Monographs in Organic Chemistry for the Period 1940-1960, Pergamon, Oxford, 1962.
MILLEN A N D W H I T E : P RO P E RT IE S ASD
STRUCTURE
189
2. PHYSICAL PROPERTIES A N D ORGANIC STRUCTURE
THISsection of the Report surveys the application of physical methods to the determination of structures of organic compounds. Attention is devoted mainly to spectroscopic methods including resonance techniques ; diffraction methods are referred to only occasionally and incidentally, since these are covered elsewhere ; but optical rotatory dispersion, molecular polarisability, mass spectrometry, and dipole moments are included. No attempt has been made to survey work prior to 1962, except that where recent developments have arisen directly from work in the last few years reference is made to such papers. New booksl-3 include discussions of the information which the various techniques may yield. Reviews have appeared on the use of microwave spectro~copy,~ electron magnetic resonance, nuclear magnetic resonance,6-8 and optical rotatory dispersion 9, lo for structural determinations. A collection of structures recently determined by microwave spectroscopy has also been made.ll Volume I11 of Progress in Xtereochemistry l 2 and Volume I11 of Methods of Experimental Physics l3 (which is devoted entirely to the determination of molecular structure) have appeared. Varian Associates have published a collection of nuclear magnetic resonance spectra of organic compounds.l4 Bond Distances and Angles-The significance of the variously defined bond lengths re, r,, and rS, in spectroscopy, and rm and rg in electron diffraction, has been discussed.15 Carbon-carbon bond lengths have continued to be the subject of much discussion,16 and a summary of such distances for open-chain molecules has been drawn up.17 Bartell has put forward the view that interactions between non-bonded atoms in quite simple molecules are important in determining bond angles and distances. Wilson,lg on the other hand, in a critical examination of various theories concerning
Elucidation of Structures by Physical and Chemical Methods, Part I, ed. K. W. Bentley, J. F. Macfarlan and Co. Ltd., Edinburgh, and John Wiley, London, 1962. Determination of Organic Structures by Physical Methods, ed. F. C. Nachod and W. D. Phillips, Vol. 1 , Academic Press, New York, 1962. 1 J. D. Roberts, An Introduction to Spin-Spin Splitting in High-Resolution Nuclear Magnetic Resonance Spectra, Benjamin, New York, 1961. 4 E. B. Wilson, Pure Appl. Chem., 1962, 4, 1. J. F. Gibson, Roy. Inst. Chem. Lectures, Monographs, Reports, 1962, 86, 37. J. Delmau, Bull. Soc. chim. France, 1962, 1. R. A. Y. Jones and A. R. Katritzky, Chem. and Ind., 1962, 522. * R. A. Y. Jones and A. R. Katritzky, Angew. Chem., 1962, 74, 60. K. Mislow, Ann. New York Acad. Xci., 1962, 93, 457. l o M. K. Hargreaves, Nature, 1962, 195, 560. l1 W. Maier, Pure Appl. Chem., 1962, 4 157. , l 2 Progress in Stereochemistry, Vol. 111, ed. P. B. D. de la Mare and W. Klyne, Butterworths Scientific Publns., London, 1962. l3 Methods of Experimental Physics. Vol. 1 1 Molecular Physics, ed. D. 1. Williams, Academic Press, New York, and London, 1962. l4 N.M.R. Spectra Catalogue, compiled by N. S. Bhacca, L. F. Johnson, and J. N. Shoolery, Varian Associates, Palo Alto, Calif. l5 D. R. Lide, Tetrahedron, 1962, 17, 125. l6 Epistologue on Carbon-Carbon Bonds, ed. M. J. S. Dewar, Tetrahedron, 1962, 17, 123. l7 B. P. Stoicheff, Tetrahedron, 1962, 17, 135. L. S Bartell, Tetrahedron, 1962, 17, 177. . l9 E. B. Wilson, Tetrahedron, 1962, 17, 191.
190
ORGANIC CHEMISTRY
variations in bond lengths and angles has concluded that steric repulsion is not an important factor in simple molecules. He further concludes that the hybridisation theory does not have predictive status and that, although there i8 good evidence of conjugation (in certain molecules) from barrier heights resisting rotation, evidence of the effect from bond lengths is much less certain. Lide l5 has argued that the C-C bond distances in the considerable number of molecules for which accurate information is now available can be understood on the basis that change of hybridisation is the major cause of variation. The effect of delocalisation on C-C bonds is regarded as negligible, though where lone pairs may be involved in conjugation (as in CN, CO, CF, CC1, etc.) it leads to significant bond-shortening. Mulliken 2o has likewise emphasised that isovalent conjugation is expected t o have a larger effect on bond lengths than sacrificial conjugation has. Covalent radii for carbon in different states of hybridisation have been put forward. l 5 Aliphatic Compounds.-Hydrocarbons. The high-resolution Raman spectrum of ethane,21 when combined with previous infrared work, leads t o the following parameters: C-C 1.538; C-H 1.106 A, andLH-C-H 108.8". Parameters have also been obtained for hexadeuteroethane. For butadiene a trans-structure has been confirmed;22no evidence of a cis-form was found in a search for the microwave spectrum.23 The structure of butatriene has also been confirmed, and bond distances have been evaluated.24 The structural parameters which have been obtained for t-butylacetylene (3,3dimethylbut-l-yne)reveal a C-C bond adjacent to the triple bond which is 0-02-0.04 A longer than in methylacetylene ( p r ~ p y n e ) .A ~ ~ second isomer of 1,3,5-hexatriene has been identified and shown from its infrared spectrum t o have the cis-configuration.26 Oxygen groups. Anomalous rotatory dispersion curves associated with xanthates and acylthioureas can be used for stereochemical studies of alcohols and cc-substituted carboxylic acids. 27, 28 A single conformation has been suggested for diethyl ether, and rotational isomerism of higher ethers has been considered t o account for their molecular polarisabilities. 29 Three rotational isomers have been suggested to explain the infrared spectrum of butyl vinyl ether, and energy differences between the isomers have been evaluated.30 Rotational isomers have also been reported for trans2-chlorovinyl methyl ether, but no rotational isomerism is found for the
R. S. Mulliken, Tetrahedron, 1962, 17, 247. B. P. Stoicheff, Canad. J . Phys., 1962,40, 358; D. W. Lepard, D. M. C . Sweeney, and H. L. Welsh, Canad. J . Phys., 1962, 11, 1567. 2 2 D. J. Marais, N. Sheppard, and B. Stoicheff, Tetrahedron, 1962, 17, 163. 23 D. R. Lide, J. Chem. Phys., 1962, 37, 2074. 2 4 A. Almenningen, 0. Bastiansen, and M. Traetteberg, Acta Chem. Scand., 1961, 15, 1557. a5 L. J. Nugent, D. E. Mann, and D. R. Lide, jun., J . Chem. Phys., 1962, 36, 965. E. R. Lippincott and T. E. Kenney, J . Amer. Chem. SOC.,1962, 19, 3641. 2' B. Sjoberg, D. J. Cram, L. Wolf, and C. Djerassi, Acta Chem. Scand., 1962, 16, 1079. 2B C . Djerassi, K. Undheim, and A. M. Weidler, Acta Chem. Scand., 1962, 16, 1147. 2 9 M. J. Aroney, R. J. W. Le FGvre, and J. Saxby, J., 1962, 2886. 30 E. M. Popov, N. S . Andrew, and G. I. Kagan, Optics and Spectroscopy, 1962, 12, 17.
2O
2l
MILLEN AND W H I T E : PROPERTIES A N D STRUCTURE
191
cis-isomer in any phase.31 Infrared and Raman spectra of dialkoxy- 32 and dialkylthio-methanes 33 have been discussed in terms of rotational isomerism. Temperature-dependences of infrared, Raman and nuclear magnetic resonance spectra of diethyl ketone 3 4 indicate an equilibrium between a t least two conformational isomers. A similar study has been made for unsaturated ketones ;35 trans-pent-3-en-2-oneexists exclusively in the s-cis-form in the solid and in equilibrium with the s-trans-form in the liquid state. Molecular polarisabilities of some simple carboxylic esters 36 indicate that the C0,R group is non-planar, assumption of 30" rotation of the C-O-R triangle about the ( C 0 ) - 0 bond usually reconciling calculation with observation. On the other hand, a completely planar skeleton has been deduced for methyl formate 3 7 in the gas phase from its microwave spectrum. Diethyl oxalate 38 is probably a mixture of cis- and trans-isomers, neither of which is planar, and esters of other dibasic acids probably consist of several forms. Similar studies of cyclic dibasic acid anhydrides 39 indicate that maleic, succinic, citraconic, itaconic, phthalic, and naphthalic anhydride have flat structures, while glutaric, diphenic, camphoric, and cineolic anhydride have non-planar structures. The measured molar Kerr constants enable the more appropriate of alternative conformations t o be chosen. The nuclear magnetic resonance spectra 4 0 of two of the isomers of 3-methyl-5-phenylpenta-2,4-dienoic acid and the corresponding esters have been observed. These establish the isomers as 2-cis,4-cis-and 2-trans,4-cis ; the 4-cis-isomers have preferred 3-s-trans-conformation. Mass-spectroscopic studies 41 of normal long-chain methyl esters and hydrocarbons have been reported. Proton magnetic resonance spectra 4 2 of phosphorus esters indicate that these molecules spend an important fraction of time in a single preferred general conformation. Rotation is considered to be rapid around P-C and P-0-C linkages. Dipole moments 4 3 of some peroxy-compounds have been reported and interpreted for esters of aliphatic peracids on the basis of a skew conformation about the peroxy-group with the acyl group twisted out of the C-0-0 plane. Halogen compounds. A re-examination 44 of the microwave spectrum of chloroform has led to a revised C-H bond length of 1.100 A, not significantly different from that for methyl chloride (1.096 A) ; a C-C1 distance of 1.758 A is to be compared with 1.781 A for methyl chloride. Structural
31
Y. Mikawa, S. Morita, and S. Tsunakawa, Bull. Chem. SOC. Japan, 1962, 35,
1109.
32 K. Nukada, Bull. Chem. SOC. Japan, 1961,34,1615,1624; 1962,35,3; Spectrochim. Acta, 1962, 18, 745. 3 3 D. Welti and D. Whittaker, J., 1962, 4372. 3 4 R. N. Jones and K. Noack, Canad. J . Chem., 1961, 39, 2214. 3 5 K . Noack and R. N. Jones, Canad. J . Chem., 1961, 39, 2225. 36 R. J. W. Le F'6vre and A, Sundaram, J., 1962, 3904. 37 R. F. Curl, J. Chem. Phys., 1959, 30, 1529. 38 M. J. Aroney, D. Izsak, and R. J. W. Le FBvre, J., 1962, 3997. 39 R. J. W. Le F'6vre and A. Sundaram, J., 1962, 4009. 4 0 R. H. Willey, T. H. Cramford, and C. E. Staples, J . Org. Chem., 1962, 27, 1535. 41 D. Nguyh, R. Ryhage, S. Stkillberg-Stenhagen, and E. Stenhagen, Arkiw Kemi, 1962, 18, 393. 4 4 T. H. Stiddall, tert., and C. A. Prohaska, J . Amer. Chem. SOC., 1962, 84, 3467. 4 3 F. Verderame and J. G. Miller, J . Phys. Chem., 1962, 66, 2185. 4 4 M. Jen and D. R. Lide, J . Chem. Phys., 1962, 36, 2525.
192
ORGANIC CHEMISTRY
parameters for methylene chloride,45ethyl chloride,46chloromethylsilane,47 and 1 ,l-dichlorocyclopropane48 include C-C1 bond distances of 1-77, 1.788, H 1.788, and 1.73 A, respectively. Structural informaI tion has also been reported for propargyl fluorideY4Q c H C H z trichlorofluoromethane~50and for t-butyl cyanide,25 H2C * chlorideY5l bromide.52 The microwave spectrum of and F (I) fiuoroprene 2 3 indicates a trans-planar configuration (11. Hydrogen and fluorine nuclear magnetic resonance spectra 53 of polysubstituted ethanes over the temperature range 2 5 0 4 5 0 "K have been interpreted to provide values of differencesbetween potential-energy minima of rotamers. The first detailed microwave spectroscopic study of rotational isomerism has appeared;54 the spectra of the trans- and gauche-forms of propyl fluoride have been analysed. The energy minimum for the gaucheform occurs at a dihedral angle of 63" and lies below that of the transform by 0.47 5 0.31 kcal./mole. An approximate estimate has been given of the barrier at the cis-configuration and also of the lower barrier separating the gauche- and the trans-configuration. Barriers resisting rotation of the methyl groups are included in the Table on p. 195. As a result of a detailed analysis 5 5 of infrared spectra of alkyl halides, criteria have been proposed to distinguish, not only between primary, secondary, and tertiary halides, but also between conformations about the adjacent C-C bond. Rotational isomerism of alkyl halides has also been discussed in relation to molecular polarisabilities,5* dipole and dielectric relaxation. 58 The presence of five rotational isomers in estimated proportions has been reported for n-butyl chloride, and hindered rotation in s-butyl chloride has also been studied.59 The nuclear magnetic resonance coupling constants 6 o between methine protons of 2,3-disubstituted n-butanes have been used to obtain qualitative estimates of rotamer populations. For meso-2,3-dibromo-, -2,3-dichloro-, and -2,3-diphenylbutane, form (2) is favoured, whilst for meso-2,3ciiacetoxybutane, conformations with gauche-acetoxy- M e x & : (2) substituents possess a lower energy than those with a H trans-arrangement, possibly indicating an electrostatic attraction between acetoxy-groups.
45W. H.Flygare and W. D. Gwinn, J. Chem. Phys., 1962, 36, 787. 4 6 R. H. Schwendeman and G. D. Jacobs, J . Chem. Phys., 1962, 36, 1245. 4 7 R. H.Schwendeman and G. D. Jacobs, J. Chem. Phys., 1962, 36, 1251. 4 8 W. H. Flygare, A. Narath, and W. D. Gwinn, J . Chem. Phys., 1962, 36, 200. 4 9 B. E. Job and J. Sheridan, Nature, 1962, 193, 677. 5 0 J. H. N. Loubser, J . Chem. Phys., 1962, 36, 2808. 5 1 W. Zeil, M. Winnewisser, and K. Muller, 2. Nuturforsch., 1961, 16a, 1250. 5 2 W . Zeil, M. Winnewisser, and W. Huttner, 2. Nuturforsch., 1961, 16a, 1248. 5 3 H. S. Gutowsky, G. G. Bedford, and P. E. McMahon, J . Chem. Phys., 1962, 36, 3353. 54E. Hirota, J. Chem. Phys., 1962, 37, 283. 55 J. J. Shipman, V. L. Folt, and 8. Krimm, Spectrochim. Actu, 1962, 18, 1603. 56 M. Aroney, D. Izsak, and R . J. W. Le FBvre, J., 1962, 1407. 6 7 H. Lumbroso, C m p t . rend., 1962, 254, 2750. 6 8 J. Meinnel and G . Martin, Arch. Sci., 1961, 14 (10th Ampere Colloquium), 56. 5 9 T. Ukafi and R. A. Bonham, J . Amer. Chern. SOC., 1962, 84, 3631. 60F. A. L. Anet, J . Amer. Chem. SOC., 1962, 84, 747; A. A. Bothner-By and C. Naar-Colin, ibid., 84, 743, 1962.
MILLEN A N D W H I T E : PROPERTIES A N D S T R U C T U R E
193
Nitrogen groups. It has been shown that formamide 61 has a non-planar equilibrium structure with a low barrier to inversion, the N-H bonds making angles of about 10" with the N-CHO plane. A similar non-planar equilibrium structure with easy inversion is indicated for cyanamide.62 A detailed vibrational assignment has been made for N-methylformamide 6 3 on the basis of a trans-structure though the possibility of the presence of a small proportion of the cis-isomer is not excluded, but it has been suggested that neither a trans- nor a cis-structure will, if rigid, account for the complexity of the band contours;64 possibly inversion is important here also. The extent of the deviation from a planar configuration about the nitrogen atom has been discussed for various amines and amides in terms of infrared spectra 6 5 and for cyclic imines in terms of ultraviolet spectra.66 Dipole moments of imides and amides, including acetamide derivatives, and their structural interpretations have also been reported.67 Infrared spectra of partially deuterated amides 6 8 show two N-H stretching frequencies, which are attributed to bonds cis and trans to the carbonyl group. 15N-Substituted amides69 have been used to provide further evidence on the problem of the assignments for the amide group; the view is put forward that, for the solid phase at least, the usual assignments of C-0 stretch and NH, deformation should be interchanged. N-Methylthioformamide exists in cis- and trans-forms in solution, but N-methylthioacetamide is found only in the trans-configuration.7 0 The dipole moments of acetanilide 71 derivatives indicate that the phenyl ring is inclined a t 46" & 5" to the plane of the acetyl group. The temperature-dependence of the nuclear magnetic resonance spectra 7 2 of substituted amides has given values of the energy barrier and frequency factor for internal rotation about the central C-N bond, the probable error in the determined energy barriers being less than &O-8 kcal./mole. The energy barrier depends on the solvent and also on the concentration of the amide ; in carbon tetrachloride the barrier decreases monotonically with dilution, while in dibromomethane the barrier initially increases to a maximum and then decreases with increasing dilution. Acyclic imides . normally have trans-trans-configurations about the CO-NHCO group in the solid, but in solution in non-polar solvents transcis-configurations are found in associated molecules, which are probably hydrogen-bonded dirners.T3 The infrared spectra of a number of diamines
61
62
C. C. Costain and J. M. Dowling, J . Chem. Phys., 1960, 32, 158. D. J. Millen, G. Topping, and D. R. Lide, J . MoZ. Spectroscopy, 1962, 8,
153.
I. Suzuki, Bull. Chem. SOC. Japan, 1962, 35, 540. R. L. Jones, J . Mol. Spectroscopy, 1961, 7, 460. 6 5 P. J. Krueger, Nature, 1962, 194, 1077. 6 6 A. T. Bottini and C. P. Nash, J . Amer. Chem. SOC.,1962, 84, 734. 6 7 C. M. Lee and W. D. Kumler, J . Amer. Chem. SOC., 1962, 84, 565. 6 8 A. G. Moritz, Nature, 1962, 195, 800. 6 9 R. N. Kniseley, Spectrochim. Acta, 1962, 18, 1217. 7 0 I. Suzuki, Bull. Chem. SOC. Japan, 1962, 35, 1456. 7 1 M. Gomel, H. Lumbroso, and D. Peltier, Compt. rend., 1962, 254, 3857. 7 2 M. T. Rogers and J. C. Woodbrey, J . Phys. Chem., 1962,66, 540; J . C. Woodbrey and M. T. Rogers, J . Amer. Chem. SOC., 1962, 84, 13. 73 T. Uno and K. Machida, Bull. Chem. SOC. Japan, 1962, 35, 1226.
63
64
194
ORGANIC CHEMISTRY
and salts have been reported and the trans-trans-trans-configuration is suggested for NN - dimethylet hylenediamine hydrochloride. 74 Wide-line proton magnetic resonance and infrared spectra 7 5 of polycrystalline samples of salts of urea, thiourea, and formamidine disulphide (CC-dithiobisformamidine) have been obtained. If it is assumed that proton transfer has occurred, the nuclear magnetic resonance spectra are consistent with protonation of the urea and thiourea salts a t oxygen or sulphur; in formamidine disulphide dihydrochloride the protons are all located in the NH, groups. Further evidence has been provided for the view that salts of both acetamide and NN-substituted acetamides have oxonium-type structures. 76 The wide-line nuclear magnetic resonance spectra of glycine obtained for various orientations of a single crystal in N ,NH2 the magnetic field show that the NH3+ group H2N C H2 * C)! C02H (3) is a regular tetrahedron whose axis lies along N, the C-N bond; the N-H bond distance was determined to be 1.077 & 0.01 8. The high-resolution nuclear magnetic resonance spectrum of the new amino-acid lathyrine shows that it is ,I !(2-aminopyrimidin-4-y1)alanine (3). N-Thiobenzoyl and N-phenylthioacetyl derivatives of a-arnino-acids have desirable spectroscopic properties for spectropolarimetric studies. 7 9 The N-phenylthioacetyl derivatives have strong Cotton effects which are suitable for establishing absolute configurations. Mass spectra of amino-acids have been reported.80 The dipole moment g1 and structure 82 of formaldoxime in the vapour phase have been determined; the configuration is found to be (4), whereas the infrared intensities of hydroxyl bands in some amidoximes 83 suggest structure (5) rather than (6).
r J
cis-trans-Isomerism of 1,l-methylenedi-(4-hydroxyiminopyridinium) halides has been reported from an infrared The structure of the zwitterion 85 which results from proton transfer in certain oximes containing a dimethylamine group has been discussed. The proton magnetic resonance spectra 86 of several ketone 2,4-dinitrophenylhydrazonesand semicarbM. E. Baldwin, Spectrochim. Acta, 1962, 18, 1455. C. R. Redpath and J. A. S. Smith, Trans. Paraday SOC.,1962, 58, 462. 7 6 W. Kutzelnigg and R. Mecke, Spectrochim. Acta, 1962, 18, 549; W. D.Kumler, J . Amer. Chem. SOC.,1961, 83, 4983; D. Cook, Canad. J . Chem., 1962, 4 , 2362. 0 7 7 W. E. Webb and W. G. Moulton, J . Chem. Phys., 1962, 36, 1911. 8 E. A. Bell and R. 0. Forster, Nature, 1962, 194, 91. 7 9 B. Sjoberg, B. Karl&, and R. Dahlbom, Acta Chem. Scand., 1962, 16, 1071. 8 0 K . Biemann and J. A. McCloskey, J . Amer. Chem. SOC.,1962, 84, 3192. 8 1 M. G. K. Pillai, J . Phys. Chem., 1962, 66, 179. 8 2 I. N. Levine, J . Mol. Spectroscopy, 1962, 8 276. , 83 J. Barrans, T. Marty, and R. Mathis, Compt. rend., 1962, 254, 2736. 8 4 J. Tregellas-Williams, Austral. J . Chem., 1962, 15, 150. s 5 J. J. Noman, Canad. J . Chem., 1962, 40, 2023. 8 6 G. J. Karabatsos, J. D. Graham, and F. M. Vane, J . Amer. Chem. SOC., 1962, 84, 753.
74
75
MILLEN
A N D WHITE:
PROPERTIES AND STRUCTURE
195
azones in different solvents provide information of the stereoisomerism about the C=N group; measurement of peak areas leads t o an evaluation of the syn-anti-composition. Nuclear magnetic resonance and infrared measurements 87 indicate that sulphaniloylguanidine has structure (7) rather than (8).
(7) p-NH2.C,H**SO2*N:C(NH,) 2
p-NH,*C,H,*SO ,*NH*C(NH,):NH (8)
Comparison of spectra of free succinonitrile and that bound in metal complexes where the gauche-configuration is established supports the conclusion that the gauche-form of free succinonitrile is the more stable;s8 adiponitrile and glutaronitrile have been examined in a similar way.89 Other groups. The infrared spectrum of ethane- 1,2-dithiol closely parallels that of 1,2-dichloroethane, showing the presence of a single form (trans) in the solid, and trans- and gauche-forms in equilibrium in the liquid. It seems likely that in di(alky1thio)ethanes the trans-form becomes predominant in the liquid as the size of the alkyl group increases.g0 The following three-fold barriers (kcal./mole) to internal rotation in free molecules (gas-phase) bring up to date a recent survey.98
CH,*PH, CH,.SnH, CH,Cl.SiH, C H ,Cl*CH,
(CH3)2NH
CH,*CH=C=O
1-96 0.65 2.55 3.685' 3-28 1-20
Ref. 91 92
47
46 93 94
truns-CH,CH,*CH,F guuche-CH, CH ,*CH2F CH,*AsF, cis-CH,*CH=CHF

(CH3)2S
2.69 2.8 7 1.32 1-06 2*17*
Ref. 54 54 95 96 97
* Revised values. Homocyclic Compounds.-3- , 4-, and 5-Membered rings. Carbon-carbon

distances have been obtained for cyclobutane 99 from its rotational Raman spectrum, but a definite decision between a planar and a non-planar ring has not been made though the latter is favoured. For bromocyclobutane the microwave spectrum 100 establishes a non-planar equilibrium structure with a low-frequency bending vibration; a detailed structure has been obtained for the " equatorially "-substituted isomer ; the " axial " isomer was not detected. Correlations of substituent effects on the C-H stretching vibration of various cyclopropyl lol and cyclobutyl 102 derivatives have been
G. Schwenker, Arch. Pharm., 1962, 295, 753. 8 s I .Matsubara, Bull. Chem. SOC. Japan, 1961, 34, 1710, 1719. I. Matsubara, Bull. Chem. SOC. Japan, 1962, 35, 27.3 D. Welti and D. Whittaker, J., 1962, 4372. 91 T. Kojima, E. L. Breig, and Chun C. Lin, J. Chem. Phys., 1961, 35, 2139. 9 2 P. Cahill and S. Butcher, J . Chem. Phys., 1961, 35, 2255. 9 3 W. G. Fateley and F. A. Miller, Spectrochim. Acta, 1962, 18, 977. 9 4 B. Bak, D. Christensen, J. Christiansen, L. Hansen-Nygaard, and J. RastrupAndersen, Spectrochim. Acta, 1962, 18, 1421. 9 6 L. J. Nugent and C. D. Cornwell, J . Chem. Phys., 1962, 37, 523. 9 6 R. H. Beaudet and E. B. Wilson, J . Chem. Phys., 1962, 37, 1133. 9 7 H. D. Rudolph and H. D. Dreizler, 2. Naturforsch., 1962, Ira, 712. 9 8 D. J. Millen, " Progress in Stereochemistry," ed.W. Klyne and P. B. D. de la Mare, Butterworths Scientific Publns., London, Vol. 1 1 1962, p. 138. 1, 9 9 R. C. Lord and B. P. Stoicheff, Canad. J . Phys., 1962, 40, 725. l o o W. G. Rothschild and B. P. Dailey, J . Chem. Phys., 1962, 36, 2931. l o l H. Weitkamp, U. Hasserodt, and F. Korte, Chem. Ber., 1962, 95, 2280; P. G. Gassman, Chem. and Ind., 1962, 740. lo2 G. Chiurdoglu, T. Doehaerd, and M. Duts, Bull. SOC. chirn. belges, 1961, 70, 642.
196
ORGANIC CHEMISTRY
made and some information obtained on nortricyclene 103 derivatives. Infrared and nuclear magnetic resonance spectra lo4have been used to establish structures of cyclobutane derivatives obtained from the reaction of chlorotrifluoroethylene with olefins. The nuclear magnetic resonance spectra of cyclopentane and cyclopentene systems have been reported. 105 The microwave spectrum of cyclopentene lo6shows it to have a non-planar equilibrium carbon skeleton with a dihedral angle between the two skeletal plapes of 22". Cyclopentanol exists at least partly in a non-planar conformation since two C-0 stretching bands have been observed.107 The broad aromatic peak in the nuclear magnetic resonance spectrum of cis1,2-diphenylcyclopentenehas been found to narrow when the sample is heated, which has been interpreted as evidence of restricted rotation of the phenyl groups; there is no evidence of restricted rotation in the stilbenes, diphenylcyclopropanes, or trans-1,2- diphenylcyclopentane. 108 6-Membered rings. The main features of the barrier governing the chair-chair conversion of cyclohexane are becoming clear. The activation energy for the conversion is found to be 11.5 & 2 kcal./mole.log From previous work the energy of the boat form has been estimated as 5.5 kcal./mole above that of the chair form.l10 Free-energy changes for the equatorial-axial conversion have been obtained for methyl, ethyl, isopropy1,lll and thioalkyl groups.112 From ultrasonic absorption measurements on methylcyclohexane an activation energy of 6.36 kcal./mole has been estimated.113 The diequatorial isomer of trans-4-chlorocyclohexanol is found to be more stable than the diaxial form in carbon disulphide solution by 0.76 kcal./mole. 114 Chemical-shift differences for isomeric nitrocyclohexanes provide information about the axial or equatorial conformation of the nitro-group.l15 Conformational free-energy differences 116 for substituted cyclohexanes have been studied by nuclear magnetic resonance spectroscopy. The mass spectra of cycloalkane derivatives have been discussed.117 The structures of cyclohexane-1,3-diols have been established from the nuclear magnetic
0. E. Pollard, Spectrochim. Acta, 1962, 18, 837. Tarrant, R. W. Johnson, jun., and W. S. Brey, jun., J . Org. Cheno., 1962, 27, 602. lo5 J. D. Park, R. L. Settine, B. A. Parkin, jun., and G, W. Hedrich, J . Org. Chem., 1962, 27, 898. lo6 G. W. Rathjens, jun., J . Chem. Phys., 1962, 36, 2401. l ' G. Chiurdoglu and W. Masschelein, Bull. SOC. o chim. belges, 1962, 71, 59. lo* D. Y. Curtin, H. Grun, Y. G. Hendrickson, and H. E. Knipmeyer, J . Amer. Chem. Xoc., 1961, 83, 4838. log F. R. Jensen, D. S. Noyce, C. H. Sederholm, and A. J. Berlin, J . Amer. Chem. SOC.,1962, 84, 386. 110 N. L. Allinger and L. A. Freiberg, J . Amer. Chem. SOC., 1960, 82, 2392; W. S. Johnson, V. J. Bauer, J. L. Margave, M. A. Frisch, L. H. Dreger, and W. N. Hubbard, ibid., 1961, 83, 606. ll1 N.L.Allinger and Shih-en Hu, J . Amer. Chem. Xoc., 1962,84, 370; W. L. Allinger, L. A. Freiberg, and Shih-en Hu, ibid., p. 2836. 112 E. E. Eliel and L. A. Pilato, Tetrahedron Letters, 1962, 103. 113 M. E. Pedinoff, J . Chem. Phys., 1962, 36, 777. 114 Y. Takeoka, Bull. Chem. SOC. Japan, 1962, 35, 1371. 115 A. C. Huitric and W. F. Trager, J . Org. Chem., 1962, 27, 1926. 116 E. E. Eliel and M. H. Gianni, Tetrahedron Letters, 1962, 97. 117 J. Laune, Ind. chim. belge, 1962, 27, 245.
lo3 lo4 P.
MILLEN A N D W H IT E : PROPERTIES
AND STRUCTURE
197
resonance spectra of the pure compounds; cyclohexane-1,3-diol, m.p. 116", has the trans-conformation, as has 5,5-dimethylcyclohexane-1 ,3-dio17m.p. 108 '. 118 Nuclear magnetic resonance spectra of 4-alkylcyclohexanols have also been obtained.llg The stereochemistry of isomeric cis- and truns-2(chloropheny1)cyclohexanols(with o-, m-, and p-chlorine) and the corresponding acetoxy-derivatives has been investigated similarly. The results are consistent with a chair form having the aromatic ring in the equatorial orientation.120 The proton magnetic resonance spectra 121 of cis-, muco-, and allo-inositol hexa-acetate as a function of temperature have given enthalpies of activation and Arrhenius factors for some of the skeletal oscillations of the six-membered ring. Optical rotatory dispersion curves for a few cyclohexanone-typeketones 122 are of unusually large amplitude; it has been suggested that a twist conformation provides a possible explanation of abnormal amplitudes in decalone derivatives. A small amount of a twist form is probably present in 2-methylTo cyclohexanone at equi1ibri~rn.l~~ assist the understanding of the optical properties of &-unsaturated ketones, it is helpful to treat the composite carbonyl-carbon n-system as an inherently dissymmetric chromophore ; this often enables one t o determine absolute configuration or conformation. 124 Optical rotatory dispersion of @?-unsaturated ketones has also been discussed.125 Combining the observed Cotton effect of (+)-3-methylcyclohexanone with the observed effect of a 3-keto-5%-steroid or its bicyclic analogue leads t o a calculated Cotton effect for 1- and 4-methyl-3-ketosteroids. The observed amplitudes differ from the calculated values, the difference being ascribed to a conformational distortion of the cyclohexanone ring owing t o steric interaction between an equatorial methyl group and a suitably located hydrogen atom in another ring.lZ6 It has been shown that in a series of phenylcholestanones those with an axial phenyl group on the carbon next t o the carbonyl group are distinguished by an abnormally intense n --+* transition; this is attributed to mixing in of an allowed n charge-transfer transition, which also provides a n explanation of the large Cotton effect.12' The n -+ n* component of the mixed transition has a magnetic dipole transition moment along the carbonyl axis, and the charge transfer aspect leads to a component of electric dipole transition moment along the same axis, thus satisfying the condition for the development of optical rotatory power. The attribution of both the optical rotatory strength of the transition and its intensity enhancement to the mixing-in of the
H. Finegold and H. Kwart, J. Org. Chem., 1962, 27, 2361. A. H. Lewin and S. Winstein, J . Amer. Chem. SOC.,1962, 84. 2464. 1 2 0 A. C. Huitric, W. G. Clarke, jun., K. Leigh, and D. C. Staiff; J . Org. C12em., 1962, 27, 715. 1 2 1 S. Brownstein, Canad. J. Chem., 1962, 40. 870. 1 2 2 C. Djerassi and W. Klyne, Proc. Nut. Acid. Sci. U.S.A., 1962, 48, 1093. 1 2 3 C. Beard, C. Djerassi, T. Elliott, and R. C. C. Tao, J . Amer. Chem. SOC., 1962, 84, 874. 124 A. Moscowitz, K . Mislow, M. A. W. Glass, and C . Djerassi, J . Amer. Chern. SOC., 1962, 84, 1945; K. Mislow and J. G. Berger, ibid., p. 1956. 125 C. Djerassi, R . Records, E. Bunnenberg, K. Mislow, and A. Moscowitz, J . Amer. Chenz. SOC., 1962, 84, 870. 126 C. Djerassi, E. Lund, and A. A. Akhrem, J . Amer. Chem. SOC., 1962, 84, 1249. 12' R. C. Cookson and J. Hudec, J., 1962, 429.
118
119
198
ORGANIC CHEMISTRY
charge-transfer component requires that the rotatory strength be proportional to the square root of the intensity enhancement.l2* Rotatory powers of several asymmetric ketones have been found to approximate t o this relationship. 128 Optical activity of alicyclic ketones is considered in calculations based on the one-electron model of optical activity.129 The dipole moment of 2-fluorocyclohexanone l 3 O suggests that this compound is a mixture of equatorial and axial conformers, the former predominating, the amount depending on the solvent ; similar measurements 131 indicate that 2-chloro- and 2-bromo-cyclohexanone are also mixtures of the conformers. An extension of these arguments 132 leads to the view that the equatorial conformation is found a t position 4 in 4-fluoro-5#?-cholestan-3-one. It has been suggested from an infrared and Raman study 133 that cyclohexane-l,4-dione oscillates between the two boat forms through an intermediate skew-form. The infrared spectra of cyclohexane-l,3-dione and its 5,5-dimethyl derivative 13*show that even in the solid state both molecules exist in the enolic form and internal hydrogen bonding is suggested. 4-Benzoylcyclohexane-1,3-dione found t o enolise completely in chlorois form ;I35 nuclear magnetic resonance and infrared work indicate that dehydroacetic acid enolises completely, only one enol, the a-pyrone, being formed. 136 Characteristic carbon-halogen frequencies have been assigned for cyclohexene derivatives ; deviation from planarity about the double bond is indicated for 1,2-dibromocyclohexene.137 Larger rings. Nuclear magnetic resonance spectra provide evidence for the structures of substituted cycloheptadienes obtained by 1 &addition to troponoid systems.138 A study of the dipole moments of 5,6,8,9-tetrahydrobenzocyclohepten-7-one, bicyclo[5,4,0]undecan-4-one, and 6,7,8,9-tetrahydro-5H-benzocyclohepteneshows that the cyclohept-4-en-1-one system consists of a mixture of boat and chair forms, the latter ~ r e d 0 r n i n a t i n g . l ~ ~ The nuclear magnetic resonance spectra of annulenes and dehydroannulenes have been obtained and have been interpreted in relation t o the aromaticity of the compounds. [14]Annulene, [24]annulene, and tetradehydro[ 24lannulene are non-aromatic, while monodehydro[ 14]annulene, [ 18lannulene and tridehydro[18]annulene are aromatic 140 (see also section 7 of this Report). Aromatic rings. The presence of two strong O-H stretching vibrations
12* lZD 130 131 P.
S. F. Mason, J., 1962, 3285; Mol. Phys., 1962, 5, 343. M. Vc.Volkenshtein and I. 0. Levitan, Zhur. strukt. Khim., 1962, 3, 80. N. L. Allinger and H. M. Blatter, J . Org. Chem., 1962, 27, 1523.
$2.
Mauret and J. Petrissans, Compt. rend., 1962, 254, 3662; T. N. Pliev, Zhur. Khim., 1961, 35, 2144. 132 N. L. Allinger, M. A. Darooge, and C. L. Neumann, J . Org. Chem., 1962, 27, 1082. 133 N. L. Allinger and L. A. Freiberg, J . Amer. Chem. SOC., 1961, 83, 5028. 134 C. Duval and J. Lecomte, Compt. rend., 1962, 254, 36. 135 K. Kotera, J . Pharm. SOC. Japan, 1961, 81, 1525. 136 S. Forsen and M. Nilsson, Arkiv Kemi, 1961, 17, 523. 13 G. Chiurdoglu, R. Ottinger, J. Reisse, and A. Toussaint, Spectrochim. Acta, 1962, 18, 215. lSs 0. L. Chapman, D. J. Paslo, and A. A. Griswold, J . Amer. Chem. SOC., 1962, 84, 1213. 139 N. L. Allinger and W. Szkrybalo, J. Org. Chem., 1962, 27, 722. 140 L. M. Jackman, F. Sondheimer, Y. Amiel, D. A. Ben-Efraim, Y. Gaoni, R. Wolovsky, and A. A. Bothner-By, J . Amer. Chem. SOC., 1962, 84, 4307.
MILLEN A N D W H I T E : PROPERTIES AND STRUCTURE
199
in the infrared spectrum of o-t-alkylphenols has been ascribed to the existence of cis- and trans-isomers in which the hydroxyl group is co-planar with the ring.141 cis-trans-Isomerism is also indicated for monodeuterated primary aromatic amines by the observation of two N-D stretching frequencies.142 The observation of only one N-D frequency for picramide is held to indicate bilateral hydrogen bonding. 143 Studies of molecular polarisability show that measured molar Kerr constants can be reconciled with an s-truns-conformation for cinnamaldehyde, an s-cis-conformation for benzylideneacetophenone, mainly s-truns-s-cis for cinnamylideneacetophenone, s-cis-s-cis for dibenzylideneacetone, and struns-s-cis,s-cis-s-transfor dicinnamylideneacetone,provided that in certain cases the phenyl groups are twisted 20-30" out of the plane, around the 1,4-axis. A twist of 41" is indicated for each phenyl group of benzophen0ne.1~4 Similar measurements with diphenyl ether suggest a conformation with a twist of 37" between the phenyl g r 0 ~ p s . l Two bands in the ~~ infrared spectrum of dihydroxybenzaldehyde which were formerly taken to indicate the presence of a monomer and a dimer are now attributed to Fermi resonance.146 The correlation between structure and mass-spectral features of benzoate-type esters has been discussed.147 The significant difference between the ultraviolet spectra of benzylideneaniline and styrene has been attributed to non-planarity of the former; protonation gives a spectrum resembling that of styrene. 14* A detailed microwave-spectroscopic study of nine isotopic species of benzonitrile has given a complete rs structure of a benzene derivative and has revealed angular distortions of about 270,149 the ring angles, starting from the substituent, being 122.5" & 0.6", 118.4" & 0.6", and 120.3" -= 0.4". J Carbon-halogen bond distances have been obtained for m-chlorofluorobenzene,150 and the possibility of structural determination by microwave spectroscopy of a molecule as laxge as 2-fluoronaphthalene has . been examined.1 5 1 Polycyclic compounds. The ultraviolet spectra and optical rotatory dispersion of optically active biaryls have been investigated. This work 152 provides the first instance of conformational and configurational correlations of atropisomers by means of optical rotatory dispersion. The magnetically anisotropic double bond in bicyclic Diels-Alder adducts deshields protons in an exo-configuration and shields protons in an endo-configuraK. U. Ingold, Canad. J . Chem., 1962, 40, 111. A. G. Moritz, Spectrochim. Acta, 1962, 18, 671. A. N. Hambly and B. V. O'Grady, Chem. and Ind., 1962, 459. 144 R. Bramley and R. J. W. Le Fevre, J., 1962, 56. 145 R. J. W. Le Fevre, A. Sundaram, and K. M. S. Sundaram, Bull. Chem. SOC. Japan, 1962, 35, 690. 146 S. Pinchas, J., 1962, 2835. 1 ' T. Aczel and H. E. Lumpkin, Analyt. Chem., 1962, 34, 33. 4 14* P. Brocklehurst, Tetrahedron, 1962, 18, 299. 149 B. Bak, D. Christensen, W. B. Dixon, L. Hansen-Nygaard, and J. RastrupAndersen, J . Chem. Phys., 1962, 37, 2027. 150.A. Rachman, P. Kokeritz, and H. Selen, J . Mol. Spectroscopy, 1962, 8, 338. 51 B. Bak, D. Christensen, L. Hansen-Nygaard, and J. Rastrup-Anderson, Spectrochim. Acta, 1962, 18, 229. 1 5 2 K. Mislow, M. A. W. Glass, R. E. O'Brien, P. Rutkin, D. H. Steinberg, J. Weiss, and C. Djerassi, J. Amer. Chem. Soc., 1962, 84, 1455.
141 142 143
200
ORGANIC CHEMISTRY
t i ~ n . l This enables the configuration of a proton or proton-bearing ~~ substituent t o be ascertained by the change in chemical shift when the double bond is removed by hydrogenation, but if the double bond carries a magnetically anisotropic substituent interpretation of the results is more difficult. I n 5-nitrobornene the nitro-group is in the endo-configuration. The nuclear magnetic resonance spectra of substituted azulenes and the corresponding conjugated acids show that monoprotonation occurs in the five-membered ring. 154 Infrared, ultraviolet, and nuclear magnetic resonance spectra have been used to characterise the tetramethyl[2,2 Jparacyclophane obtained from a saturated aliphatic precursor. 155 A theoretical treatment of conformations of the decalins has been presented.156 Terpenes and steroids. Terpene systems investigated by nuclear magnetic resonance include unsaturated systems of the type CH2*CMe:CH*CH,X,157 triterpenes of the lupane series,158and rotenone and related compounds (in which asymmetric shielding of the l-proton by the 12-carbonyl group can be used t o decide on the cis- or trans-fusion of the B/C rings 159). Optical rotatory dispersion and infrared and nuclear magnetic resonance spectra have been used in determining the structure of ivalin, a new sesquiterpene lactone.160 Mass spectra 161of unsaturated pentacyclic triterpenoids have been reported. Mass spectra combined with other spectroscopic methods 162 have been used to determine the structures of two minor products of the pyrolysis of thujone which, previously thought t o be Cg ketones, are in fact C,, ketones. Calculations relating t o optical activity and conformation of some alicyclic terpenes have been based on the one-electron model of optical activity. l 6 3 Optical circular dichroism has been applied t o the study of the stereochemistry of ~ t e r 0 i d s . l ~ ~is frequently convenient t o use the readily It prepared nitrite esters rather than xanthates for differentiating between epimeric pairs of steroidal alcoh01s.l~~ The nitrites show a multiple Cotton effect in a convenient spectral region and the rotatory dispersion curves can be used t o differentiate epimeric alcohols even in the presence of the A*-3-keto-portion. Introduction of halogen atoms or y to a keto-group leads t o unexpected rotatory dispersion results; 166 these have been interpreted as due to conformational distortion from the chair form towards a boat-like conformation as a result of electrostatic repulsion.
153
S. S. Danyluk and W. G. Schneider, Canad. J . Chem., 1962, 40, 1777. D. T. Longone and C. L. Warren, J. Amer. Chem. SOC.,1962, 84, 1507. 1 5 6 J. Levisalles and J. C. N. Ma, Bull. SOC. chim. France, 1962, 1597. 1 5 7 R. B. Bates, R. H. Carnighan, R. 0. Rakutis, and J. H. Schauble, Chern. and Ind., 1962, 1020. 1 5 8 J.-M. Lehn and G . Ourisson, Bull. SOC. chim. France, 1962, 1137. 1 5 9 L. Crombie and J. W. Lown, J., 1962, 775. l 6 0 W. Herz and G. Hogenaner, J. Org. Chem., 1962, 27, 905. 1 6 1 C. Djerassi, H. Budzikiewicz, and J. M. Wilson, Tetrahedron Letters, 1962, 263. 1 6 2 W. von E. Doering, M. R. Willcott, 111, and M. Jones, jun., J. Amer. Chem. SOC., 1962, 84, 1224. 1 6 3 M. V. Volkenshtein and I. 0. Levitan, Zhur. strulct. Khim., 1962, 3, 87. 1 6 4 M. Legrand and R. Viennet, Compt. rend., 1962, 254, 322; L. Velluz, ibid., p. 969. 1 6 5 C. Djerassi, I T. Harrison, 0. Zagneetko, and A. L. Nussbaum, J . Org. Chem., . 1962, 27, 1173. 1 6 6 C. S. Barnes and C. Djerassi, J . Amer. Chem. SOC., 1962, 84, 1962.
154
R. R. Fraser, Canad. J. Chem., 1962, 40, 78.
MILLEN AND W H I T E : PROPERTIES A N D STRUCTURE
201
Molecular-polarisability studies of cholesterol, cholest-5-ene, cholest-5en-3-one, cholesteryl chloride, bromide, iodide, and epicholesteryl chloride 16' indicate that the halogen atoms are attached equatorially in the cholesteryl halide and axially in epicholesteryl chloride. Mass spectrometry has been used for both analytical 168 and structural 169 studies of steroids. Mass spectra of steroids with lreto-groups in all possible nuclear positions have been reported. Characteristic features in the spectra are mainly due t o cleavage of the C-C bond in the ring adjacent to the carbonyl group and also t o retention of the charge on the oxygen-containing fragment. It is suggested that this technique can locate, or at least reduce, the possible positions of attachment of a carbonyl g r 0 ~ p . l ~ ~ Nuclear magnetic resonance studies of steroids show that spatial vicinity of hydroxyl and methyl groups can cause a chemical shift to low field for the methyl signal, a feature which may be of use in the study of the stereochemistry of ster0ids.1~0 Spectra of steroids with hydrocarbon side chains have been obtained and the methyl regions have been assigned.171 Physical methods have been used in studies of the structure of diginin and diginigenin,l72 otobain, 1 7 3 rearrangement products of 2a-hydroxytestosterone and its diacetate,l74 and the products of Claisen rearrangement of cestrone ally1 ether.175 Heterocyclic Compounds.--SmaEZ rings. The microwave spectrum of the parent compound of the recently discovered diazirines proves conclusively that diazirine has the cyclic structure (9): dipole moment and bond distances have been e ~ a l u a t e d . 1 ~ ~ Four-membered cyclic sulphones have been investigated by means of infrared and nuclear magnetic resonance spectroscopy. Conformations of furanose derivatives in solution have been H,C 1 IY N (9) , studied by proton magnetic resonance. l 7 * Isomers of fluoroN oxetanes have been investigated by fluorine nuclear magnetic resonance.179 Proton magnetic resonance spectra of pyrrolines and pyrroline oxides accord with the *N=CH*formulation of the bases.lS0 Nuclear magnetic resonance studies of pyrrole include an investligation of the thiocyanation products of pyrrole lS1 and an examination of the coupling constants of
J. M. Eckert and R. J. W. Le F&vre,J., 1962, 1081. L. E. Peterson, Chem. and I n d . , 1962, 264. 169 H. Budzikiewicz and C. Djerassi, J. Amer. Chem. SOC., 1962, 84, 1430. 170 Y. Kawazoe, Y. Xato, M. Natsume, H. Hasegawa, T. Okamoto, and K. Tsuda, Chem. and Pharm. Bull. (Japan), 1962, 10, 338. 171 G. Slomp and F. A. MacKellar, J. Amer. Chem. SOC., 1962, 84, 204. 172 C. W. Shoppee, R. Lack, and. A. V. Robertson, Proc. Chenz. SOC., 1962, 65. l i 3 T. Gilchrist, R. Hodges, and A. L. Portc, J., 1962, 1780. 174 R. L. Clarke, J . Amer. Chenz. SOC., 1962, 84, 467. 175 P. G. Holton, J. Org. Chem., 1962, 27, 357. 176 L. Pierce and V. Dobyns, J . Amer. Chem. SOC., 1962, 84, 2651. 17' G. Stork and I. J. Borowitz, J . Amer. Chem. SOC., 1962, 84, 313. l i 8 R. J. Abraham, K. A. McLauchlan, L. D. Hall, and L. Hough, Chem. and Ind., 1962, 213. 179 J. F. Harris and D. D. Coffman, J. Amer. Chem. SOC.,1962, 84, 1553. 180 R. Bennett and D. E. McGreer, Cunad. J. Chem., 1962, 40, 177. lS1 S. Gronowitz, A.-B. Hornfeldt, B. Gestblom, and R. A. Hoffman, Arlciv Kern;, 1962, 18, 151.
167
168
202
ORGANIC CHEMISTRY
pyrroles. l B 2 The proton resonance spectra of cis- and trans-hydroxy-I;proline show that the ring in each compound is buckled in solution.ls3 Both molecules exist in C, or envelope conformations. I n the trans-compound C-4 projects out of the plane of the other ring atoms, the angle of buckle being approximately 53", while in the cis-compound C-5 is out of plane, the angle of buckle being approximately 70". Nuclear magnetic resonance spectra have been used in proving the structures of 3,4-dehydro-proline and -prolinamide. 84 A complete rs structure has been obtained for f ~ r a n . 1 8 ~ Infrared, ultraviolet, and nuclear magnetic resonance spectra show that the compound described in the literature as thiolan-3,4-dithione is probably &methyl-172-dithiole-3thione . Thiophen-3,4-dithiol exists in the dithiol form. l 8 6 l7O Nuclear magnetic resonance spectra of benzofurazan oxide show two resonance lines, adding support to the N-oxide structure.187 The spectra are temperature-dependent owing to an equilibrium (10). The average lifetime of the tautomers is about sec. a t 45", the activation energy is 17.2 & 1.5 kcal./mole, and the frequency factor lies between 3 x 1014 and 3 x 10l6 sec.-1.
r
1
Rotational constants and dipole moment have been reDorted for thiazole. 88 Isomeric arninoisoxazolones have been identified & $amino5- and 5-amino-3-isoxazolone. 189 Arylazopyrazolones have infrared spectra consistent with an azo-keto-structure.190 The nuclear magnetic resonance spectra of pyridine derivatives show that the coupling constants are little affected by substituents, except by strong electron-donors in the 3-position. The chemical shifts reflect the donor or acceptor properties of substituents, but anisotropy effects have to be borne in mind; 2- and 6-hydroxypyridine derivatives occupy a special position owing t o their pyridone structure. lS1 Dipole moments of phenyl derivatives of some N-heterocycles have been reported: for phenyl-substituted 2-phenylpyridines internal rotation is
lS2 S. Gronowitz, A.-B. Hornfeldt, B. Gestblom, and R. A. Hoffman, Arkiv K e m i , 1962, 18, 133. lS3 R. J . Abraham and K. A. McLauch1an;MoZ. Phys., 1962,5, 195; R. J. Abraham and K. A. McLauchlan, ibid., p. 513. lE4 A. V. Robertson and B. Witkop, J . Amer. Chem. SOC., 1962, 84, 1697. lS5 B. Bak, D. Christensen, W. B. Dixon, L. Hansen-Nygaard, J. R. Andersen, and M. Schottlander, J. Mol. Spectroscopy, 1962, 9, 124. lS6 S. Gronowitz and P. Moses, Acta Chem. Scand., 1962, 16, 105. P. Diehl, H. A. Christ, and F. B. Mallory, HeZv. Chim. Acta, 1962, 45, 504. B. Bak, D. Christensen, L. Hansen-Nygaard, and J. Rastrup-Andersen, J . MoZ. Spectroscopy, 1962, 9, 222. lS9 C. L. Bell, C. N. V. Nambury, and L. Bauer, J. Org. Chem., 1961, 26, 4923. l g oF.. A. Snavelly, W. S. Trahanovsky, and F. H. Suydam, J . Org. Chesn., 1962, 27, 994. l g l W. Briigel, 2. Elektrochem., 1962, 66, 159.
MILLEN A N D WHITE:
PROPERTIES A N D STRUCTURE
203
restricted.192 The infrared and Raman spectra of piperazine lg3 have been assigned on the basis of the chair form. The possibility of a boat-chair transformation in the solid piperidinium halides 1 9 * has been considered but is regarded as unlikely. Molecular-polarisability studies of tropinone and 3-halogenotropanes in benzene solution show that piperidine rings in a chair conformation with equatorially disposed N-methyl groups are contained in the preferred conformations.195 The infrared and nuclear magnetic resonance spectra l g 6 of quinolizidine and monomethylquinolizidines indicate that in all except one of these compounds the ring system exists predominantly in the trans-fused conformation. The exception is 4-methylquinolizidine in which the 10- and the 4-hydrogen atoms are trans to one another; this compound appears to adopt a conformation in which the rings are cis-fused and the methyl group is equatorial. The stereochemistry of the proton salts is similar to that of the free bases. Two possible methiodides of quinolizidine have been prepared and their structures determined. The spectra of methoxypyridine cations have features expected for pyridinium ions,19' whereas with 4-mercaptopyridine and 4-mercaptoquinoline protonation occurs at the sulphur atoms.198 For hydrochlorides of aminopyridines the cations are represented well by amidinium str~ctures.1~9 The proton resonance spectra of indolizinium perchlorate and its methyl derivatives in trifluoroacetic acid show that protonation occurs preferentially at the 3-position.200 The proton magnetic resonance spectra of coumarins 201 confirm the ethylenic nature of the 3,4-double bond, and provides a convenient means of distinguishing between 3- and 4-substituted coumarins. The proton spectrum of pisatin 202 shows that the molecule contains a chromanocoumaran ring and is 3-hydroxypterocarpin. The proton spectrum of desosamine 203 (map. 86-87') shows that the 1-, 2-, 3-, and &hydrogen atoms are in the axial configuration. The configurations at positions 1, 2, and 3 of methyl chalcoside and chalcose have been established by mutually consistent chemical, nuclear magnetic resonance, and rotational data ; the configuration at position 5 has been deduced from nuclear magnetic resonance data. 204 Proton resonance spectra of six-membered heterocycles containing oxygen and sulphur have been used in studies of intramolecular
l g 2 C. W. N. Cumper, D. G . Redford, and A. I. VogeI, J., 1962, 1176, 1182; C. W. N. Cumper, R. F. A. Ginman, and A. I. Vogel, ibid., pp. 1188, 4518, 4525. lS3 P. J. Hendra and D. B. Powell, Spectrochim. Ada, 1962, 18, 299. lS4 A. Cabana, and C. Sandorfy, Canad. J. Chem., 1962, 40, 615. I g 5 J. M. Eckert and R. J. W. Le F$vre, J., 1962, 3991. lS6 T. M. Moynehan, K. Schofield, R. A. Y . Jones, and A. R. Katritzky, J., 1962, 2637. lS7 E. Spinner and J. C . B. White, J., 1962, 3115. lS8 E. Spinner, J., 1962, 3127. l g S E. Spinner, J., 1962, 3119. M. Fraser, A. Melera, B. B. Molloy, and D. H. Reid, J., 1962, 3288. 201 S. S. Dharmatti, G. Govil, C . R . Kanekar, C. L. Khetrapal, and Y. P. Virmani, Proc. Indian Acad. Sci., 1962, 54, A, 71. 2 0 2 D. D. Perrin and D. R. Perrin, J . Amer. Chem. SOC., 1962, 84, 1922. 203 P. W. K. Woo, J. W. Wion, L. Durham, and H. S. Mosher, Tetrahedron Letters, 1962, 735. 2 0 4 P. W. K. Woo, H. W. Dion, and L. F. Johnson, J . Amer. Chem. Soc., 1962, 84, 1066.
204
ORGANIC CHEMISTRY
mobility and conformation.* 0 5 Proton resonance spectra of pyranose derivatives in solution have been reported.206 The nuclear magnetic resonance spectra of 1,4-dioxans71 ,3-dioxolans7 and 174-dioxano[2,3-b][ 1,4]dioxan have been interpreted by two methods ; characteristic shifts have been observed for the groups studied.207 The proton magnetic resonance spectrum of 173,5-trithian208 indicates a rapidly oscillating chair structure in which axial and equatorial hydrogen are indistinguishable. An ax : eq ratio of 2 : 1 in the spectrum of a-trithioacet,3,5-frithian7and the aldehyde shows that this is cis-truns-2,4,6-trimethyl-l earlier assignment of y-trithioacetaldehyde as a eutectic mixture of the aand the p-isomer has been confirmed. Similar nuclear magnetic resonance measurements show that a-trithiobenzaldehyde is cis-truns-2,4,6-triphenyl1,3,5-trithian7while the #?-compoundis the all-cis-isomer. Characteristic frequencies are reported for sulphoxides 209, 210 and 88dioxides, and cis-trans-isomers of 2,2-diphenyl-l,3-dithian 1,3-dioxidehave been identified.210 Structures of cyclic sulphites have been discussed in relation to their dipole moments; by using steric arguments to eliminate certain configurations it is concluded that cyclic tetramethylene sulphite has a chair configuration with an equatorial S=O bond.211 Alkuloids and nucleosides. The outstanding feature of recent work on alkaloids has been the application of mass spectrometry to structural and stereochemical problems. Work reported deals with polyneuridine and indole alkal0ids,21~ tabersonine,213 refractine and aspidofractine,214vindolinine,215 aspidoalbine,216 echitamidine,217 nucleosides,21* eburnamenine,219 purine derivatives,220ananferine,221 pyrifoline and refractidine,222 mos205 H.Friebolin, s. Kabuss, W. Maier, and A. Luttringhaus, Tetrahedron Letters, 1962, 683. 2 0 6 L. D. Hall, L. Hough, K. A. McLauchlan, and K. Pachler, Chem. and Ind., 1962, 1465. 207 E. Caspi, T. A. Wittstruck, and D. M. Piatak, J . Org. Chem., 1962, 27, 3183. 208 E. Campaigne, N. F. Chamberlain, and B. E. Edwards, J . Org. Chem., 1962, 27, 135. 2 0 9 S. Pinchas, D. Samuel, and M. Weiss-Broday, J., 1962, 3968. W. Otting and F. A. Neugebauer, Chem. Ber., 1962, 95, 540. 2 1 1 R. Riemschneider and V. Wuscherpfennig, 2. Naturforsch., 1962, 17b, 516. 2 1 2 L. D. Antonaccio, N. A. Pereira, B. Gilbert, H. Vorbrueggen, H. Budzikiewicz, J. M. Wilson, L. J. Durham, and C. Djerassi, J . Amer. Chem. SOC., 1962, 84, 2161. 213 M. Plat, J. Le Men, M.-M. Janot, J. M. Wilson, H. Budzikiewicz, L. J. Durham, Y. Nakagawa, and C. Djerassi, Tetrahedron Letters, 1962, 271. 2 1 4 C. Djerassi, T.George, N. Finch, H. F. Lodish, H. Budzikiewicz, and B. Gilbert, J . Arner. Chem. SOC.,1962, 84, 1499. 215 C. Djerassi, S. E. Flores, H.. Budzikiewicz, J. M. Wilson, J. L. Durham, J. Le Men, M.-M. Janot, M. Plat, M. Gorman, and N. Neuss, Proc. Nat. Acad. Sci. U.S.A., 1962, 48, 113. 216 C. Djerassi, L. D. Antonaccio, H. Budzikiewicz, J. M. Wilson, and B. Gilbert, Tetrahedron Letters, 1962, 1001. 217 C. Djerassi, Y. Nakagawa, H. Budzikiewicz, J. M. Wilson, J. Le Men, H. Poisson, and M.-M. Janot, Tetrahedron Letters, 1962, 653. 218 K. Biemann and J. A. McCloskey, J . Amer. Chem. SOC., 1962, 84, 2005. 219 H. K. Schnoes, A. L. Burlingame, and K. Biemann, Tetrahedron Letters, 1962, 993. 2 2 0 G. Spiteller and M. Spiteller-Friedmann, Monatsh., 1962, 93, 632. 221A. Rother, J. M. Bobbitt, and A. E. Schwarting, Chem. and Ind., 1962, 654. 2 2 2 B. Gilbert, J. M. Ferreira, R. J. Owellen, C. E. Swanholm, H. Budzikiewicz, L. J. Durham, and C. Djerassi, Tetrahedron Letters, 1962, 59.
M I L L E N AND W H I T E : P R O P E R T I E S A N D S T R U C T U R E
205
sambine (diphlorrhyncine),223 and the periwinkle alkaloids vincamine and 1l-methoxy~incamine.~~~ Chemical shifts of the 19-methyl group and infrared analysis can be used to classify heteroyohimbine alkaloids into six stereochemical groups.2 2 5 The stereochemistry of rauniticine, raunitidine, isoraunitidine, mayumbine, and raunitorine has been completely described.225 Optical rotatory dispersion studies have been reported for aporphine alkaloids.226 The proton magnetic resonance spectra of nucleotides 2 2 7 lead to assignment of specific conformations for the sugar ring, but the analysis is valid only if the theory relating coupling constants and dihedral angles in these compounds is quantitatively correct. Free Radicals.-In this section results obtained from electron-spin resonance studies are summarised. A study of the spectra of ultraviolet-irradiated isotopically substituted methanol 2 2 8 as a function of isotopic substitution, time of irradiation, and temperature permitted the identification with considerable certainty of the radicals: *CH,*OH,*CH2*OD, *CH3,CD,, *CHO,and *CDO,and evidence CD,*O*. The was obtained for the radicals *CD,*OH,GOD, *COH,CH3*O*, spectra of formyl 2 2 9 and deuteroformyl radicals support the conclusion that the radical is not a n-electron radical. X-Irradiation of a single crystal of methylmalonic acid shows that the two main species produced by the radiation are the *CMe(CO,H), and the *CHMe*CO,Hradicals ;230 analysis of the spectra of the radical *CMe(CO,H), at room temperature, 7 7 " ~ ~ and 4.2" K, shows that the three methyl protons are equivalent, the methyl group executing nearly free rotation about the C-C bond at 4.2"K. The electron-spin resonance of an irradiated single crystal of racemic tartaric acid grown from water wa.s found to be complex, whereas a deuterated single crystal gave a spectrum which could be analysed.231 The radical formed probably has struct,ure (11).
H,C -C ('2)
7 - C -CH3
I I
COZH
y-Irradiation of ( )-isovaline probably causes abstraction of NH, and formation of the radical ( 12).232 Similar irradiation of a single crystal of acetyl-L-glutamic acid results in the initial production of the unstable radical (13), which is transformed into a more stable radical, and possible
2 2 3 X. Monseur, R. Goutarel, J. Le Men, J. M. Wilson, H. Budzikiewicz, and C. Djerassi, Bull. SOC. chim. France, 1962, 1088. 2 2 4 M. Plat, Due Dohkac Manh, J. Le Men, M.-M. Janot, H. Budzikiewicz, J. M. Wilson, L. J. Durham, and C. Djerassi, Bull SOC.c72irn. France, 1962, 1082. 2 2 5 M. Shamma and J. B. Moss, J . Amer. Chem. SOC.,1962, 84, 1739. 2 2 6 C. Djerassi, K. Mislow, and M. Shamma, Experientia, 1962, 18, 5 3 ; M. Shamma, ibid., p. 64. 2 2 7 C. D. Jardetzky, J . Amer. Chena. SOC., 1962, 84, 62. 2 2 8 P. J. Sullivan and W. S. Koski, J . Amer. Chem. SOC., 1962, 84, 1. 2 2 9 F. J. Adrian, E. L. Cochran, and V. A. Bowers, J. Chem. Phys., 1962, 36, 1661. 230 C. Heller, J. Chern. Phys., 1962, 36, 175. 231 D. V. G. L. N. Rao, and W. Gordy, J . Chem. Phys., 1962, 36, 1143. 230 T. S. Jaseja and R. S . Anderson, J. Chem. Phys., 1962, 36, 1098.
('$1)
206
ORGANIC CHEMISTRY
structures of the latter have been h ~ f e r r e d . ~ ~ s free radical produced The by y-irradiation of N-carbamoylglycine has the structure ( 14).234
H02C. CH
A study of the spectra 235 of irradiated single crystals of alanine shows that the reorientation of the methyl group of the radical R*CHMe* quenched is a t low temperatures, and the lifetime of reorientation was estimated. For alanine the potential barrier and frequency factor were found to be 3.6 & 0.2 kcal./mole and (10 & 4) x 10l2sec.-l. Free radicals produced by y-irradiation of single crystals of N-acetylmethionone probably have the chemical forms (15) and (16).236
C0,H
(15) CH,*CO-NH.CH
I
CO,H CH,*CO*NH*C* I CH,WH ,*CH ,
(16)
*SCH,*CH,
I n strong acid solution semiquinones exist as doubly protonated species, h y p e r h e splitting in the electron-spin resonance spectra being due t o both the added protons and t o the aromatic ring protons.237 The line-width alteration in the spectrum of the durosemiquinone cation is ascribed t o cis-trans-isomerism, the lifetime of each isomer being comparable with the inverse frequency separation between proton hyperfine cornponent~.~38 Organometallic and Organometalloid Compounds.-Infrared and nuclear magnetic resonance studies indicate that ethyl-lithium exists as a single species in hydrocarbon solvents, probably a h e ~ a r n e r . Molecular con~~~ figurations of boric Z4O and boronic esters 240, 241 have been discussed and the effect of bridging on the B-C1 stretching frequency 2 4 2 has been examined. The infrared spectra of di(alky1amino)phenylborons 241 indicate the presence of two rotational isomers arising from restricted rotation about the B-N bond. Vibrational spectra for a number of organotin 243 and organogermanium 244 compounds have been obtained. The infrared spectrum of
Mikio Katayama, J. Chtm. Phys., 1962, 37, 2143. D. V. G. L. N. Rao and M. Katayama, J. Chem. Phys., 1962, 37, 382. 2 3 5 I. Miyagawa and K. Itoh, J. Chem. Phys., 1962, 36, 2157. 2 3 6 E. Cipollini and W. Gordy, J. Chem. Phys., 1962, 37, 13. 2 3 7 J. R. Bolton, A. Carrington, and J. Dos Santos-Veiga,Mol. Phys., 1962, 5, 465. 238 J. R. Bolton and A. Carrington, MoZ. Phys., 1962, 5, 161. 2 3 9 T. L. Brown, D. W. Dickerhoof, and D. A. Bafus, J. Amer. Chem. Soc., 1962, 84, 1371. 2 4 0 H. Lumbroso and A. Grau, Bull. SOC. chim. France, 1961, 1866. 241 E. Burch, W. Gerrard, M. Goldstein, E. F. Mooney, and H. A. Willis, SpectroJ. chim. Acta, 1962, 18, 1403. 2 4 2 A. Finch, P. J. Hendra, and E. J. Pearn, Spectrochim. Acta, 1962, 18, 51. 243 V. S. Griffiths and G. A. W. Derwish, J. Mol. Spectroscopy, 1962, 9, 83; W. F. Edge11 and C. H. Ward, ibid., 1962, 8, 343; T. V. Yakovleva, A. A. Petrou, and V. S. Zavgorodnii, Optics and Spectroscopy, 1962, 12, 106. 2 4 4 N. A. Chumaerskii, Optics and Spectroscopy, 1962, 13, 37.
233
234
CAPON A N D R E E S : REACTION MECHANISMS
207
germyl cyanide has been analysed: there was no evidence of an isocyanide form.2 4 5 A detailed structural determination of silyl isothiocyanate has been made.246 Temperature-dependence of the infrared spectrum indicates a possible structural change when hexaethyldisiloxane is heated.247 The stereochemistry of optically active organosilicon compounds has been discussed.24 *
D. J. M. R. F. M. W.
3. REACTION MECHANISMS
SEVERAL books and the reports of two symposia 2 dealing wholly or largely with organic reaction mechanisms were published in 1962. Nucleophilic Substitution at Saturated Carbon. Transient Carbonium Ions. Aliphatic Reaxrangements.-Classiml and non-classical curbonium ions. There is considerable interest as to whether non-classical ions are reaction intermediates or merely transition states for the interconversion of classical ions. H. C. Brown has pointed out 3 that suggestions for nonclassical ions have multiplied fantastically in recent years 4 often without reasonable scientific basis and has examined the evidence for a number of the suggestions. The high rates of solvolyses of compounds (1) (2), and (3) have been attributed to the stabilisation of the transition states through formation of incipient non-classical ions (4), ( 5 ) ,and (6), but Brown suggests that they may be explained in other ways. He suggests that the high reactivity of compound (1) may result from a release of non-bonding compression on going to the transition state (Le., is due to a raised initial-state free-energy rather than to a reduced transition-state free-energy). However, in the Reporters view the arguments already presented by Ingold and by Winstein and his co-workers 6 that-alarge part of the high reactivity results from
245
246
T. D. Goldfarb, J . Chern. Phys., 1962, 37, 642. D. R. Jenkins, R. Kewley, and T. M. Sugden, Trans. Faraday SOC., 1962, 58,
1284.
G. G. Kirei and M. P. Lisitsa, Optics and Spectroscopy, 1962, 12, 206. L. H. Sommer, Angew. Chern., 1962, 74, 176. ( a ) J. Hine, Physical Organic Chemistry, McGraw-Hill, New York, 2nd edn., 1962 ; ( b ) A. Streitwieser, Solvolytic Displacement Reactions, McGraw-Hill, New The York, 1962; ( c ) M. J. S. Dewar, Hyper~onjugation,~~ Ronald Press Co., New York, 1962; (d) L. Ingraham, Biochemical Mechanisms, Wiley, New York, 1962; ( e ) E. L. Eliel, Stereochemistry of Carbon Compounds, McGraw-Hill, New York, 1962; (f)W. A. Pryor, Mechanisms of Sulphur Reactions, McGraw-Hill,New York, 1962; ( 9 ) S. G. Waley, Mechanisms of Organic and Enzymic Reactions, Oxford, 1962; ( h ) Comprehensive Biochemistry, ed. M. Florkin and E. H. Stotz, Elsevier, New York, 1962; (i) Progress in Stereochemistry, ed. P. B. D. de la Mare and W. Klyne, Butterworths Scientific Publns., London. Vol. 111, 1962. ( a ) The Transition State, Chern. SOC. Special Publ., No. 16, 1962; ( b ) Peroxide Reaction Mechanisms, ed. J. 0. Edwards, Interscience, New York, 1962. H. C. Brown in ref. 2 ( a ) , p. 140. See Y. Pocker, Ann. Reports, 1959, 56, 172; 1960, 57, 166; M. D. Johnson, <bid., 1961, 58, 173. C. K. Ingold, Structure and Mechanism in Organic Chemistry, Cornell Univ. Press, Ithaca, New York, 1953, p. 514. S. Winstein, B. K. Morse, E. Grunwald, K. C. Schreiber, and J. Corse, J . Amer. 1952, 74, 1113. Chem. SOC.,
247
248
t.
208
ORGANIC CHEMISTRY
synartetic acceleration or anchimeric assistance are convincing. Brown's alleged linear relation between the logarithm of the rates of solvolysis of certain toluene-p-sulphonates and the rates of the reactions of the corresponding ketones with sodium borohydride is unconvincing since too few other points are presented to define the normal line to test the divergence of the triphenylethyl system. Nevertheless, as Brown points out, the evidence
D-
CH2
(2)
for the stabilisation of transition states through incipient phenonium-ion formation in several other reactions is very slight. The high reactivity of cyclopropylmethyl and cyclobutyl derivatives is still not fully understood. The small effect of a phenyl substituent in the 3- and the 4-position on the reactivity of cyclopropylmethyl naphthalene2-sulphonate indicates that there is.little positive charge dispersed t o the methylene-carbon atoms whilst the moderately large effect of a methyl substituent a t position 2 has been taken t o indicate that some positive charge is dispersed t o this atom. These results support the view that the transition state involves incipient formation of an ion which is stabilised by resonance between structures (7) and (8) [ L e . , a non-classical ion, though different from
(7)
9 +
4-
r-7
(8)
(S)]. However, a phenyl substituent a t position 2 has only a small effect on the rate of acetolysis of cyclopropylmethyl arenesulphonates. 10 Furthermore, the rate-accelerating effect of the cyclopropyl group is not always associated with rearrangement. Each successive replacement of an isopropyl group by a cyclopropyl group in the series (9)-(12) results in a large
>?< L +
X
Y
I
v
X
(10)
246 X
v P;-a
X ('1)
(9)
Relative r a t e
23,500
(12) 23,500 x 1080
[X = p - n i t r o b e n z b a t e ] See ref. 2(a), p. 153, Fig. 4. R. A. Sneen, K. M. Lewandowski, I. A. I. Taha, and B. R. Smith, J . Anter. Chena. SOC., 1961, 83, 4843. E. F. Cox, M. C. Caserio, M. S . Silver, and J. D. Roberts, J . Amer. Chem. SOC., 1961, 83, 2719. 10 J. W. Wilt and D. D. Roberts, J . Org. Chem., 1962, 27, 3430.
CA4PON A N D R E E S : X E A C T I O N M E C H A N I S M S
209
increase in the rate of solvolysis in aqueous dioxan and the products are the unrearranged alcohols.11 Hence with these compounds there is either some factor which strongly favours formation of only the cyclopropylmethanols from the non-classical ion or a non-classical ion is not involved. An investigation of the corresponding cyclobutyl derivatives would be of considerable interest. The rate of solvolysis of 1-cyclobutyl-1 -methylethyl p-nitrobenzoate in aqueous acetone is only 5-10 times faster than that of t-butyl p-nitrobenzoate and the product is a complex mixture.12 The stabilising effect of the cyclopropyl group on carbonium ions is so great that the tricyclopropylmethyl cation is stable in concentrated sulphuric acid. l3 The nuclear magnetic resonance spectrum of this ion somewhat surprisingly consists of only a single sharp band a t 6-85 z. The reported absence l4 of a deuterium isotope effect in the solvolyses of compounds (13) and (14),
which has been quoted as evidence against the formation of the cation (5) in the rate-determining step, is i n ~ o r r e c t . 1 ~ There is in fact a small effect but this, unfortunately, provides no clear evidence on the structure of the transition state. Similarly the isotope effect in the acetolysis of 2,2-dideutero-5,5-diphenylcyclopentyl toluene-p-sulphonate l 6 provides no conclusive evidence on the occurrence of phenyl participation. Brown has also pointed out 3 that the exo-norbornyl acetate obtained with retention of configuration l7 on acetolysis of exo-norbornyl toluene-psulphonate (3) may not have been formed from the non-classical ion (6) but could have come equally from a classical ion since attack on such an ion from the exo-side would be strongly favoured sterically. He attributes the large rate-difference between the exo- and the endo-norbornyl toluene-psulphonate t o the inertness of the latter, caused by steric hindrance t o ionisation, though this is not very convincing. It is interesting that Kleinfelter and Schleyer l8 have shown that the temperature-dependence of the nuclear magnetic resonance spectrum of the carbonium ion obtained when 1,2-di-pmethoxyphenyl-2-norborneol is dissolved in sulphuric acid indicates the presence of a rapidly equilibrating pair of ions (15) and (16) rather than of a non-classical ion (17). Brown did not challenge the view that the acetol1 H. Hart and J. M. Sandri, J. Amer. Chem. SOC., 1959, 81, 320; H. Hart and P. A. Law, ibid., 1962, 84, 2462. l2 C. F. Wilcox and M. E. Mesirov, J. Amer. Chem. SOC., 1962, 84, 2757. l3 N. C. Deno, H. G. Richey, J. X. Lui, J. D. Hodge, J. J. Houser, and M. J. Wisotsky, J. Amer. Chem. SOC., 1962, 84, 2016; see Chem. Eng. News, Nov. 26th, 1962,
p. 48.
l4
l5
S. BorEi6, M. Nikoleti6, and D. E. Sunko, Chern. and Ind., 1960, 527. S. BorEi6, M. Nikoletid, and D. E. Sunko, J . Amer. Chem. SOC., 1962, 84, 1615. R. A. Sneen, R. W. Jenkins, and F. C. Riddle, J. Amer. Chem. SOC., 1962, 84,
1598.
S. M'instein and D. S. Trifan, J. Amer. Chem. SOC., 1952, '74, 1147. D. C. Kleinfelter and P. von R. Schleyer, Abs. Papers, Amer. Chem. Soc., 141st Meeting, March 1962, 28-0; 142nd Meeting, September 1962, 56-Q; quoted by H. C. Brown in ref. 2(a), p. 158.
l7
210
ORGANIC CHEMISTRY
lysis of 2-p-methoxyphenyl-l-methylpropyl p-bromobenzenesulphonate involves a p-methoxyphenonium nor that the solvolyses of cholesteryl and norbornenyl derivatives l g b involve non-classical ions formed by participation of the double bonds. A particularly striking example of such homo-
allylic participation has been found by Rogan 2O in the acetolysis of 4methylpent-3-enyl toluene-p-sulphonate (18), a compound with a less rigid structure than the cholesteryl and norbornenyl derivatives. The rate of solvolysis is 1200 times greater than that of ethyl toluene-p-sulphonate, and the products are 2-cyclopropylpropene (21) and 4-methylpent-3-enyl acetate (20) (see also p. 221). The difference in the rates of ethanolysis of 2,3 -diphenylcyclopropenylmethyl and
Me- C-CH
$H2
\ /
-CH2
(21)
CH2
toluene-p-sulphonates is very slight,Z1 indicating the absence of participation by the double bond as shown in formula (22). There is similar nonparticipation by the double bond in the solvolyses of cyclohex-3-enylmethyl derivatives 2 2 and of 3-methylenecyclobuty1 bromides.23 Homoallylicparticipation has also been investigated in the steroid field 24 and in the solvolysis of cyclo(22) oct -3-enyl p -bromobenzenesulphonate. . ph .___ __ - CH2----OTs A potentially very powerful method for the investigation of carbonium ions has been discovered by Brown and Bell 26 who showed that the carbonium ion formed when diphenylmethyl chloride is dissolved in aqueous diethylene glycol dimethyl ether may be trapped by sodium borohydride to yield diphenylmethane: Deamination of endo-2-aminomethylnorbornane(23) by nitrous acid
j $
l9 ( a ) S. Winstein, M. Brown, K. C. Schreiber, and A. H. Schlesinger, J . Amer. Chem. SOC.,1952, 74, 1140; (b) see ref. l(b), pp. 153, 152, for summary. 2 0 J. B. Rogan, J . Org. Chem., 1962, 27, 3910. 21 R. Breslow, J. Lockhart, and A. Small, J . Amer. Chem. SOC., 1962, 84, 2793. 2 2 C. F. Wilcox and S. S. Chibber, J . Org. Chem., 1962, 27, 2332. 23 E. F. Kiefer and J. D. Roberts, J . Amer. Chem. SOC., 1962, 84, 784. 2 4 W. J. A. Vandenheuvel, R. M. Moriarty, and E. S. Wallis, J . Org. Chem., 1962, 27, 725; W. J. A. Vandenheuvel and E. S. Wallis, ibid., p. 1233; C. W. Ghoppee and G. A. R. Johnston, J., 1962, 2684; G. H. Whitham, Proc. Chem. SOC.,1962, 330. 2 5 A. C. Cope, Sung Moon, and P. E. Peterson, J . Amer. Chem. Soc., 1962, 84,
1935.
26
H. C. Brown and H. M. Bell, J . Org. Chem., 1962, 27, 1928.
CAPON A N D REES: REACTION MECHANISMS
21 1
gives mainly bicyclo[3,2,l]octan-2(endo)-ol(28) and a little of the isomer (27).27 The alcohols obtained from the optically active amine are both partially racemised but the extent of racemisation differs, the endo (28) being more highly racemised than the exo isomer (27). These results are not compatible with a mechanism involving only the non-classical ion (25) since then racemic products would be expected, nor is it; compatible with one involving only the enantiomeric cations (24) and (26) as sole intermediates since then the extent of racemisation of the two alcohols should be the same. There must be at least; two product-forming intermediates and Berson and Reynolds-Warnhoff 27 suggest.the annexed scheme (23) --+ (28). Classical ion (24) is apparently diverted to mesomeric cation and to products
bfaster than it is transformed into its conformational isomer [the enantiomer of (29)] which is known to yield bicyclo[2,2,2]octan-2-01 (34).28 The bicyclo[2,2,2]octan-2-01(34) obtained from optically active exo-2aminomethylnorbornane (28) is partially racemised and so cannot be derived
(-> (28)
meso (32)
(+I (33)
(+I (34)
HO
(3(34)
exclusively from the non-classical ion (30), but racemisation would result from the classical ion (31). Other products from this reaction are exobicyclo[3,2,l]octan-2(exo)-ol (33) of yet undetermined optical purity and meso-bicyclo[3,2,l loctan-3- 01 (32).28 There is less aryl migration in the deamination of lJ2,2-tri-(methoxyphenyl)[l-14C]ethylamine (35) than in that of the corresponding phenyl
27
28
J. A. Berson and P. Reynolds-Warnhoff, J. Amer. Chern. SOC., 1962, 84, 682. J. A. Berson and D. WiUner, J. Amer. Chern. SOC.,1962, 84, 675.
212
ORGANIC CHEMISTRY
compound (36).29a If this reaction involves formation of the classical ion (37)then the extent of migration wl depend on the ease with which the il aryl group undergoes electrophilic attack and the electrophilicity of the carbonium ion-centre. A p-methoxy-group will enhance the ease of electrophilic attack but will decrease the electrophilicity of the carbonium-ion centre because of resonance between structures (38)and (39), and this second effect must more than counterbalance the first.
Ar2CH - CHAr
I
14
Ar2CH J4CHAr
NH2 (35) Ar=p-Me0.CsH4
(37)+
- E H e- M e O (38)
t - ) - C H o & l e
(36) Ar =
Ph
(39)
Deamination of optically active erythro- (40) and threo- 1 -amino-2-pmethoxyphenyl-1-phenylpropan-2-01 gave ketonic products [(42)and (43) from the erythro-isomer] where ratios of enantiomers 29b were nearly identical
:M @ e :H
H: R @
OH
(40)
JI
Me
(41)
OH
(41)
.AMe
'Ph
H (43)
Retention
JI
O &
Me
(42)
Ph
(43)
Inversion
Retention
R = p-Me-C,H, or p-MeO-C,H,
SimilarIy for the threo-series
SCHEME 1.
with those obtained from erythro- and threo-1-amino-1-phenyl-Z-p-tolylpropan-2-01. Both reactions proceed with predominant retention of configuration a t the reaction centre. The results have been taken to indicate 29b that, the high-energy carbonium ion [ (41) for the erythro-isomer] generated a t C-1 reacts at once with the migrating p-aryl group before there is any
2 9 ( a ) W. A. Bonner and T. A. Putkey, J. Org. Chew., 1962, 27, 2348; ( b ) C. J. Collins, M. M. Staum, and B. M. Benjamin, ibid., p. 3525.
213
rotation about the 1,2-bond so that the products reflect the conformation of the initial state (see Scheme 1 for the erythro-series). When the migrating group is o-tolyl which has different steric requirements, the product ratio is 2,l different. The nitrous acid deaminations of 5,5-dimethylbicyclo[ ,l]hex2p-ylamine 30 and 2-1- and 2-2-naphthyl[1-W]ethylamine 31 have also been investigated. Ion-pair return and related phenomena. Ion-pair return has been investigated by measuring the lSO equilibration 32 of diphenylmethyl p-nitro[~nrbonyZ-~sO]benzoate the isomerisation of the corresponding thionbenand zoate t o the thiobenzoate.33 Solrolysisof thep-nitrobenzoate in 90:L aqueous acetone is accompanied by equilibration of the carbonyl-oxygen atoms in The the unsolvolysed e ~ t e r . 3 ~ rates of solvolysis (E,) and oxygen equilibration (Eeq) are both of the first order, and Ee,/lc, = 3. The kinetic behaviour
I8O
II
k2 +
PhzCH-O-C-Ar
Products
(44)
(46)
and the slow exchange between ester and p-nitrobenzoic acid indicate that the p-nitrobenzoate portion remains associated with the original diphenylmethyl group. A mechanism is proposed, (44) -+ (46), involving ion-pair return from an ion-pair intermediate (45) in which the carboxylat e- oxygen atoms are equivalent. Diphenylmethyl thionbenzoate undergoes a similar isomerisation to the thiobenzoate concurrently with its ethanolysis,33 there being 17% of ethanolysis and 837; of isomerisation. Substituent effects
PhzCH S Products
- 5- Ph.
0
indicate that the ethanolysis involves ionisation since p = -3.6. No diphenylmethyl p-methoxythiobenzoate was formed when the thionbenzoate was allowed to rearrange in the presence of potassium p-methoxythiobenzoate, indicating that return from free ions is unimportant. The oxygen-equilibration of triphenylmethyl [carbonyl- lSO]benzoate in dry acetone is suppressed by addition of lithium azide, the product then being triphenylmethyl azide.34 A t low azide concentrations the rate constant for the disappearance of azide is only slightly larger than the rate constant for equilibration. These results suggest that azide captures an intermediate which in its absence yields rearranged ester. This intermediate is probably a solvent-separated ion pair. It is suggested 34 for this and for other reactions that the dual (intimate and solvent-separated) ion-pair hypothesis is
30
J. Meinwald, P. G. Gassman, and J. J. Hurst, J. Amer. Cliem. SOC., 1962, 84,
3722.
A. G. Forman and C. C. Lee, Canad. J. Chem., 1962, 40, 1130. H. L. Goering and J. F. Levy, Tetrahedron Letters, 1961, 644; J . Amer. Chem. Soc., 1962, 84, 3853. 3 3 S. G. Smith, Tetrahedron Letters, 1962, 979. 34 C. G. Swain and Gen-Ichi Tsuchihashi, J. Amer. Chem. SOC., 1962, 84, 2021.
31
32
214
ORGANIC CHEMISTRY
unnecessary. I n the presence of lithium and tetrabutylammonium bromide the reactions of 2-p-methoxyphenyl-l-methylethyl toluene-p-sulphonate and 2pmethoxyphenyl-1-methylpropyl p -bromobuzenesulphonate in acetic acid are largely diverted from solvolysis to bromide formation.35 This is also thought to involve trapping of solvent-separated ion pairs. Optically active 1-methylheptyl p-bromobenzenesulphonate yields inverted alcohol of 77y0 optical purity on solvolysis in 75 vol. yo aqueous dioxan.36 I n the presence of sodium azide, however, 100% optically pure inverted alcohol is obtained. This suggests that the solvolysis proceeds either by SN2displacement by water to yield inverted alcohol or by a pathway involving an intermediate which leads to either racemisation or retention. Azide ion must then capture this intermediate, which may be a carbonium ion or an oxonium ion formed in an SN2displacement by dioxan. Isobutyl p-bromobenzenesulphonate and 1-methylheptyl toluene-p-sulphonate undergo ethanolysis with 100% inversion of configuration.3' The rates of reaction of 4-phenoxybenzyl and 4-methoxybenzyl chlorides with a series of anions have been measured.3* With the weak nucleophiles, Ph*SO,- and NO,-, the rate ratios, ICp-MeO/kp-PhO, the two substrates are similar to the for ratio for the XNl solvolyses but with strong nucleophiles, e.g., N3-, the ratio is considerably less. The results suggest that the transition state for ionisation has already been reached before bond formation with benzenesulphonate and nitrate ions begins or that these weak nucleophiles react with fully developed carbonium ions. In aqueous acetone cis- (47) and trans-5-methylcyclohex-2-enol (48) undergo racemisation and isomerisation.39 With each isomer the rate of racemisation is several times faster than that of isomerisation. Experiments with 180-labelledalcohols show that the racemisation of the cis-isomer is
(+) (47)
Mea 2
OH
Me
(+) (48)
(4 9)
M e @
.If
Rac.
OH
(50)
almost exclusively intramolecular but that of the truns-isomer is intermolecular. These results are interpreted to mean that the carbonium ion (49) from the trans-alcoholis solvated by two water molecules, but that from the cis-alcohol (50) by only one (derived from the original hydroxyl group) because of steric hindrance by the 5-methyl group.
35
S. Winstein, P. E. Klinedist, aqd E. Clippinger, J . Amer. Chem. SOC., 1961, 83,
4986.
H. Weiner and R. A. Sneen, J.' Amer. Chem. SOC., 1962, 84, 3599. A. Streitwieser and A. C. Waiss, J . Org. Chem., 1962, 27, 290. 38G. Kohnstam, A. Queen, and T. Ribar, Chem. and I n d . , 1962, 1287. 39 H. L. Goering and R. R. Josephson, J . Amer. Chem. SOC., 1962, 84, 2779.
36 37
C A P O N A N D REES: R E A C T I O N M E C H A N I S M S
215
Elimination-uddition mechanism. cc-Chlorodibenzyl ketone, but not or-chloroacetone,underwent ready methanolysis in the presence of 2,6-lutidine. The reaction was of the first order in chloro-ketone and also in 2,6lutidine but independent of lutidiniurn ion concentration. An elimination-
Ph*fH*CO.CHzPh
Slow
o y I
Ph.CH*C=CHPh CI
,
C7H9N
C7H9NH'
c 1
(51) Ph CH.CO. CHzP h I (54)

OMe
(52)
0 \ PhKH- C = CHPh
/
(5.3)
addition mechanism [either two steps as shown (51) + (54) or concerted] is pr~posed.~O The intermediate (53) may be stabilised by resonance between structures (55), (56), and (57). A similar intermediate (59) is thought to occur in the Favorski rearrangement of 6-toluene-p-sulphonyloxyisophorone
(55)
(56)
(57)
(58) which with an excess of methanolic sodium methoxide yields the rearrangement products, the methylcyclopentanecarboxylates (62) and (63) as well as 2- and 6-methoxyisophorone (60) and (61).41 It is possible that
COzMe
aCO 2Me
*O
41
A. W. Fort, J . Arner. Chern. SOC.,1962, 84, 2620. A. W. Fort, J. Arner. Chem. SOC., 1962, 84, 2625.
216
ORGANIC CHEMISTRY
all four products come from the same intermediate (59), the niethanecyclopentanecarboxylates by reaction with methoxide ions and the methoxyphorones by reaction with methanol, a view which is supported by the virtual absence of the former when the reaction is carried out in the presence of a trace of sodium methoxide. The much greater ease of replacement of the dialkylsulphonyl groups by (64) than in alkyl aryl ethoxide ions in cow-dialkylsulphonyl-p-xylenes sulphones has led t o the suggestion of an elimination-addition mechanism (64) -+(66).42 This is supported by the observation that in the presence of
EtOq
piperidine, a base without activity by itself, partial replacement of an alkylsulphonyl group by piperidine occurred. This could result from trapping of the intermediate (65). The absence of deuterated starting material in a partially completed reaction in O-deuterated ethanol suggests that the elimination is concerted. Base-promoted replacement reaction with 3-bromo-3-methylbut-1 -yne in 80% ethanol probably proceeds by the elimination-addition mechanism (68) --+ (72),43which is supported by the observation of deuterium exchange by unchanged bromide when the reaction is carried out in 80% ethan[ 2H]ol-deuterium oxide and of a cornmon-ion mass-law effect (see also the section on carbenes, p. 242).
Me Me-C-CZCH
I
y , e I
Br
Me I Me-C-CnC-
Me Me-C-C=CI
Br (68)
(70)
Me Me-C=C =C:
Me Me- C- C 3 CH
(72)
OEt
1,3-Hydride shifts. Deoxideation of propan-1-01with bromoform and aqueous potassium hydroxide t o give cyclopropane does not involve an intermediate carbene (74) since 1,1-dideuteropropan-1-01yields deuterated cyclopropane with loss of only a few per cent of deuterium.44 It is thought that P the small deuterium loss results from a 173-hydrideshift (75) + (76). A similar hydride shift occurs in the deamination of n-[ 1-14C]propylaminewith
CH,-CH,*CH: (74) CH,*CH,*CD , +
(75)
+ +CH,CH,*CHD,
(76)
4 z A . T. Kader and C. J. M. Stirling, J., 1962, 3425. 43 V. J. Shiner and J. W. Wilson, J. Amer. Chern. SOC., 1962, 84, 2402; V. J. Shiner, J. W. Wdson, G. Heinemann, and N. Solliday, ibid., p. 2408. 4 4 P. S. Skell and I. Starer, J. Amer. Chem. SOC., 1962, 84, 3962.
(71)
217
nitrous acid.45,46 It was shown by Roberts and Halman 4 7 that the propan-1-01obtained from this reaction was partially rearranged. They attributed this t o methyl migration as (77), but Reutov and Shatkina 4 5 have now shown that 14C is found only at positions 1 and 3 of the propan-1-01and hence only hydrogen shifts have ,5.!3 (77) occurred. That this was mainly a 1,3-shift (78) + (79), c < 2 c c ~ 2 and not two 1,2-shifts, (80) -+ (82), was shown by Karabatsos and Orzech 46 since [ 1,l,2,2-2H,]propylamine yields propanol with most of the protons at positions 1 and 3.
( 7 8) CH3-CD 2-CD 2+ + +CH2-CD Z-CHD 2 ( 7 9) CH,-CD,-CDz+ +CH,-CD+-CD, -+ +CH2-CHD-CD,
(80)
(81)
(82)
Neighbouring-groupparticipation by oxygen groups. Solvolysis of o-phenoxycarbonyldiphenylmethyl bromide (83) in aqueous acetone is 60-80
fPhOH
times faster than that of the para-isomer, and the product is 3-phenylphthalide (85),48 i.e., the reaction involves neighbouring-group participation by the ester group. Attempts to prepare the analogous o-methoxy-carbonyl compound yielded only Me\C = 0 3-phenylphthalide. Participation, however, does not occur in the solvolysis of the fluorene ester (86),presumably" because of the unfavourable geometry of this molec~le.~9 The solvolyses of 10-acetyl-la-halogeno-transdecalin occur with participation of the ketone group as shown in cypher (87).50 General reactions. There have been further measurements of rate constants with sufKcient accuracy to show the variation of activation energy with ternperat~re.~l-~S Although there does not appear to be universal
324
45 46
47 48 49
50
0. A. Reutov and T. N. Shatkina, Tetrahedron, 1962, 18, 237. G. J. Karabatsos and C. F. Orzech, J. Amer. Chem. SOC., 1962, 84, 2838. J. D. Roberts and M. Halmann, J. Amer. Chem. SOC.,1953, 75, 5759. A. Singh, L. J. Andrews, and R. M. Keefer, J. Amer. Chem. SOC., 1962, 84,
1179.
84, 3959.
R . E. Lovins, L. J. Andrews, and R. M. Keefer, J. Amer. Chem. SOC., 1962,

G. Baddeley, E. K. Baylis, B. G. Heaton, and J. W. Rasburn, Proc. Chem.
Soc., 1961, 451.
51G. Kohnstam and D. Tidy, Chem. and Ind., 1962, 1193.

5 2 J. Biordi and E. A. Moelwyn-Hughes,J., 1962, 4291; E. A. Moelwyn-Hughes, ibid., p. 4301. 53 J. B. Hyne, R. Wills, and R. E. Wonkka, J. Amer. Chem. SOC., 1962, 84, 2914
218
ORGANIC CHEMISTRY
agreement as to whether the quantity d(ANi)/dT should be identified with ACt,52, 5 4 there is no doubt that the quantity ACt/A8Z provides a t least a useful empirical criterion of mechanism for solvolyses in aqueous organic solvents. 5 5 This criterion indicates that solvolysis in 70% aqueous acetone of PriOTs and p-X*C,H,*CH,*OTs where X = H, Me, or NO,, and Ts = p-C,H&e*SO,, does not occur by an 8,l m e ~ h a n i s m . ~ n few investiI~ gations of this kind is the product composition determined to the same degree of accuracy as the rate of formation of acid. A method has been developed for measuring the rate of solvolysis of gaseous t-butyl chloride a t unit pressure in aqueous solution,56 and rates have been measured in a large number of electrolyte solutions.57 The formation of the transition state may be formulated, ButCl(g) (aq) + ButCP,,,,, so that
k,= RT Kt J1' The activity coefficient of t-butyl chloride does not appear Fh $
in this equation since its fugacity may be taken t o be equal t o its pressure. Hence kp/kpo = l/f t where the superscript O refers t o the reference state of pure water. It was thus possible to determine the variation of ft, the activity coefficient of the transition state, with electrolyte concentration. The activity coefficients of t-butyl chloride, f(g), in the same electrolyte solutions were also obtained from solubility measurements. Neither log f(g) nor log f t obeyed the expression obtained by Ingold and his co-workers 5 8 and based on the ion-atmosphere model, but specific salt effects were found. However, the effects of the electrolytes on the conventional rate constant, for unit concentration, do obey the ion-atmosphere treatment owing t o a cancellation of the specific salt effects on log f(B) and log ft. The view that the solvent-isotope effect kD,O/kH,O on the solvolysis of methyl halides results mainly from an initial-state difference 5 9 is incorrect. The solubility of each halide in light and heavy water is almost the same, such that the standard free-energy differences between the initial states are never greater than 60 cal. mole-1.60 Full details of much of the work of Grob and his co-workers on fragmentation reactions have now been published, 61 including the demonstration of fragmentation of a carbonium ion (90) (shown here as classical) generated by a Wagner-Meerwein rearrangement (88)+ (90). The steric course of the ring expansion of (- )-2-methylcyclohexanone with diazomethane t o give ( +)-3-methylcycloheptanone has been investigated . 6 2 Assigning configurations from the rotatory dispersion curves and
See ref. 2(a), pp. 196 et seq. G. Kohnstam in ref. 2(a), p. 179. 6 6 G. A. Clarke, T. R. Williams, a n d R. W. Taft, J . Amer. Chem. SOC., 1962, 84, 2292. 5 7 G. A. Clarke and R. W. Taft, J . Amer. Chem. SOC., 1962, 84, 2295. 68 L. C. Bateman, M. G. Church, E. D. Hughes, C. K. Ingold, a n d N. A. Taher, J., 1940, 979. 6 9 See R. C. Heppolette and R . E. Robertson, J . Amer. Chem. SOC., 1961,83, 1834,
54
65
and earlier papers.
C. G. Swain and E. R. Thornton, J . Amer. Chem. SOC.,1962, 84, 822. C. A. Grob and F. Ostermayer, Helw. Chim. Acta, 1962, 45, 1119; C. A. Grob, F. Ostermayer, and W. Raudenbusch, ibid., p. 1672; C. A. Grob, R. M. Hoegerle, and M. Ohta, ibid., p. 1823. For early work see Ann. Reports, 1958, 55, 185. 6 2 C. D. Gutsche a n d C. T. Chang, J. Amer. Chem. SOC., 1962, 84, 2263,
6o
61
CAPON A N D REES: REACTION MECHANISMS
219
the octant rule leads to the surprising conclusion that the ring expansion occurs with inversion of configuration. The Beckmann rearrangement of
(89)
9-acetyl-cis-decalinoxime (92) in concentrated sulphuric acid or polyphosphoric acid yields N - (trans-9-decaly1)acetamide(93), i.e., with inversion of configuration of the migrating
The methoxy-group has no activating influence in the solvolyses of 1bromomethyl-5-methoxy- and 2-bromomethyl-8-methoxy-naphthalene and only a small effect in the solvolyses of l-bromomethyl-7-methoxy- 2and bromomethyl-6-methoxy-naphthalene.6*A p-phenyl but not a p-methoxyor p-methylthio-substituent in cumyl chloride is more activating when constrained to a planar configuration by a methylene bridge.e5 It has been suggested that the faster reaction of benzyldimethylsulphonium toluene-psulphonate with phenoxide than with hydroxide ion may be explained by ancillary molecular bonding of the n-complex or charge-transfer type. 66 The mechanisms of the following reactions have also received attention : acetolysis of neopentyl-type toluene-p-sulphonates of ~ p i r a n sof~1-phenyl, ~ cycloalkylmethyl arenesulphonates,68 of cyclononyl 69 and cyclodecyl toluene-p-sulphonate,70 and of 4-substituted cyclohexyl toluene-p-sulphonates;71 solvolysis of y-branched alkyl toluene-p-sulphonates,7 2 and of the conjugate base of 4-p-hydroxyphenylbutyl p-bromobenzenesulphonate ;73 addition and solvolysis in the norbornane systems; 74 solvolysis, and reaction with iodide ion, of chloromethylethylmercury ; nucleophilic replacement reactions of benzyl halides ;'6 amine-catalysed chloroacetolysis of triphenylmethyl
R. K. Hill and U. T. Chortyk, J. Amer. Chem. SOC., 1962, 84, 1064. K. C. Schreiber and R. G. Byers, J. Amer. Chem. SOC., 1962, 84, 859. 6 5 H. C. Brown and T. Inukai, J. Amer. Chem. SOC.,1961, 83, 4825. 6 6 C. G. Swain and L. J. Taylor, J. Amer. Chem. SOC., 1962, 84, 2456. 6 7 A. P. Krapcho and M. Benson, J . Amer. Chem. Xoc., 1962, 84, 1036. 68 J. W. Wilt and D. D. Roberts, J. Org. Chem., 1962, 84, 3434. 6s V. Prelog, W. Kiigi, and E. M. White, Helv. Chim. Acta, 1962, 45, 1658. 7 0 V. Prelog, W. Kiing, and T. Tomljenovib, Helv. Chim. Acta, 1962, 45, 1352. 71 D. S. Noyce, B. N. Bastian, and R. S. Monson, Tetrahedron Letters, 1962, 863. H. Fischer, C. A. Grob, and W. Schwarz, Tetrahedron Letters, 1962, 25. R. Baird and S. Winstein, J. Amer. Chem. Soc., 1962, 84, 788; see Ann. Reports, 1957, 54, 161. 7 4 S. J. Cristol, W. K. Seifert, D. W. Johnson, and J. B. Jurale, J..Arner. Chem. SOC., 1962, 84, 3918. 75A. Ledwith and L. Phillips, J., 1962, 3796. 7 6 R. F. Hudson and G. Klopman, J., 1962, 1062; J. F. Bunnett and J. A. Reinheimer, J. Amer. Chem. SOC.,1962, 84, 3284; J. W. Hill and A. Fry, {bid., p. 2763; J. B. Stothers and A. N. Bourns, Canad. J . Chem., 1962, 40, 2007.
63
64
220
ORGANIC CHEMISTRY
chloride in carbon tetrachloride ; reaction of benzyldimethylanilinium ions with thiocyanate ions ;78 ethanolysis of N-benzyl-NN-dimethyl-p-toluidinium bromide;79 and isomerisation of bicyclo[2,1,0]pentane 80 and its 2-methyl derivative. 8 1 Ambidentate Nuc1eophiles.-Investigations of the influence of structure and environment on the position of covalent-bond formation in ambidentate anions (cf. ref. 82) continue. The proportions of 1- and 2-substituted pyrroles formed in the alkylation of lithium, sodium, and potassium derivatives of pyrrole with allyl, but-2-eny1, and benzyl halides have been measured for a variety of solvents, under homogeneous and heterogeneous conditions.83 N-Alkylation increases with the solvating power of the medium and decreases with the co-ordinating ability of the metal ion, as expected if dissociation of the pyrryl-metal ion-pair favours N-alkylation and association of the ionpair favours 2-alkylation. The transition states (94) and (95) are postulated, the latter providing for mutual stabilisation of charges on the departing cation and the halide anion which is important in poorly solvating media. Product ratios vary little from homogeneous to heterogeneous conditions and appear to depend predominantly on the concentration and precise state of the pyrrole derivative in solution.
C H ~R
(94)
>is-
(95)
Another system in which heterogeneity per se has no significant effect on the product ratio is the benzylation of sodium 2,6-dimethyl-4-t-bufylphenoxide suspended in toluene or dissolved in toluene-tetrahydrofuran. The ratio of C-alkylation, giving the ketone (96), t o O-alkylation in mixtures of these solvents and in the presence of varying amounts of the undissolved sodium salt and a quaternary ammonium salt are discussed, and other recent work on factors influencing the position of alkylation of phenoxide ions is reviewed;84 the importance of the state of ionic aggregation of the substrate is stressed. I n contrast t o the reactions of these pyrryl and phenoxide ions the position of alkylation of benzophenone oxime salts, on oxygen to give ethers (97) or on nitrogen t o give nitrones (98), is insensitive t o the nature of the cation. 8 5 I n methylation and benzylation, electron-withdrawing 4,4-substituents in the benzophenone increase O-alkylation whilst 4-substi77
78
79
L. J. Andrews and R. M. Keefer, J . Amer. Chem. Soc., 1962, 84, 941, 2886. S. D. Ross, M. Finkelstein, and R. C. Petersen, J. Org. Chem., 1961, 83, 4853. R. C. Petersen, M. Finkelstein, and S. D. Ross, J . Amer. Chem. SOC., 1962, 84,
M. L. Halberstadt and J. P. Chesick, J . Amer. Chem. SOC.,1962, 84, 2688. J. P. Chesick, J . Amer. Chem. SOC.,1962, 84, 3250. 8 2 H. B. Henbest, Ann. Reports, 1956, 53, 158. g3 C. F. Hobbs, C. K. McMillin, E. P. Papadopoulos, and C. A. VanderWerf, J . Amer. Chern. SOC.,1962, 84, 43. 8 4 D. Y. Curtin and D. H. Dybvig, J . Amer. Chem. Soc., 1962, 84, 225. 8 5 P. A. S. Smith and J. E. Robertson, J . Amer. Chem. SOC., 1962, 84, 1197.
go
2222.
81
221
tuents in benzyl bromide have very little effect on this ratio, as also has variation in the benzyl leaving group. It follows that the generalisation 82 that the development of greater carbonium-ion character in the alkylating agent favours reaction at the more electronegative end of the ambidentate anion does not apparently extend to oxime salts.
Ph2C= N OR o Ph2C= Y-R
(97)
' 0
(98)
Two examples where phenol, rather than the phenoxide ion, acts as an ambidentate nucleophile have appeared. I n an uncatalysed reaction with 5-chloro-2-methylpent-2-ene 150" phenol gave the products (99-101) of at attack by the oxygen atom and the ortho- and para-carbon atoms, respectively. The reaction occurs only at the primary carbon atom of the tertiary homoallylic cation (see p. 210) intermediate. 86 Phenol reacted with methyl
(99) Me Me
(100) Me Me
(I 02)
cc-D-glucoside-boron trifluoride complex in methylene chloride to give mainly the phenyl glucosides but also a small amount of the product of para-carbon glucosylation, p-glucosylphenol.S7 The reactions of @-diketonesat carbon and oxygen have been studied further. I n the presence of toluene-p-sulphonicacid, bimolecular alkylation of acetylacetone by diazomethane is accompanied by extensive formation of polymethylene without concomitant production of higher alkyl ethers, indicating that methylation of the diketone must involve either a concerted and C-methylmechanism or tightly bound ion-pairs ; occurrence of both 0ation is more readily explained by formation and collapse of the ion-pair (102).8e In the benzoylation of metal chelates of the /?-diketones, R*CO*CH,*COR', where R and R' are selected from n-propyl, isopropyl, and phenyl, the sodium, barium, copper, and nickel chelates give largely Cbenzoylation, and the zinc chelates give much less C-benzoylation; in terminal positions of the /?-diketone ligand phenyl groups decrease, and bulky alkyl groups increase, the amount of C-benzoylation. The sodium, barium, copper, and nickel chelates are considered to co-ordinate with the benzoyl chloride and then react through the transition state (103) or (104)
Ph
O . ', +. o
(103)
M
(104)
86
87 88
J. L. Corbin, H. Hart, and C. R. Wagner, J. Amer. Chenz. SOC., 1962, 84, 1741. T. G. Bonner, E. J. Bourne, and S. McNally, J . , 1962, 764. G . S. Hammond and R . M. TVilliams, J. Org. Chem., 1962, 27, 3775.
222
ORGANIC CHEMISTRY
t o give C- or O-substitution, respectively, in amounts controlled by steric interactions. It is claimed that the zinc chelates are denied this mechanism and formation of the benzoyl cation and the ambidentate enolate anion, and their reaction at the point of highest electronegativity of the latter (the oxygen atom) is proposed.89 Olefin-forming Eliminations.-This subject has been reviewed.90, 91 Both reviewers stress the occurrence of a continuous range of transition states between those for the limiting E-1 (105) and the limiting E-lcb (106) B H H mechanism. I I i l De Puy, Thurn, and Morris 92 have -c-c(105) -7-cj( I (106) shown that a series of trans-Z-aryl-cyclopentyl toluene-p-sulphonates (107) react readily with potassium t-hutoxide in t-butyl alcohol, yielding 1-arylcyclopentenes (108). The reactions are second-order and the p constant indicates that the transition states have less carbanionic character than those for the corresponding reactions of 2-arylethyl toluene-p-sulphonates. A concerted E-2 mechanism is therefore indicated. The rate of elimination of the phenyl compound is only 14 times slower than that of cis-2-phenylcyclopentyl toluene-p-sulphonate (log), whilst in the cyclohexyl series the correratio is greater than lo4. These results suggest that the sponding ktram/kci8
well-known preferential elimination of trans-groups is a facet of a more general rule. This may be stated as t h e plot of rate of elimination versus dihedral angle, 4, between hydrogen and departing anion will show maxima a t 180 and 0 and a minimum a t 90, i.e., coplanar transition states, whether cis or trans, are vastly preferred to non-coplanar ones. I n acid-catalysed deoxymercuration of oxymercurials (see Scheme 2) which has been intensively investigated by Kreevoy and his co-workers,93 dihedral
SCHEME2.
89
91
J. F. Bunnett, Angew. Chern., Internat. Edn., 1962, 1, 225. (Sir)C. K. Ingold, Proc. Chem. SOC.,1962; 265. 9 2 C. H. De Puy, R. D. Thurn, and G. F. Morris, J. Amer. Chem. SOC., 1962, 84,
H. D. Murdoch and D. C. Nonhebel, J., 1962, 2153.
1314.
93 M. M. Kreevoy, J. W. Gilje, L. T. Ditsch, W. Batorewicz, and M. A. Turner, J. Org. Chem., 1962, 27, 726; L. C. Schaleger, M. A. Turner, T. C. Chamberlin, and M. M. Kreevoy, ibid., p. 3421.
CAPON AND R E E S : REACTION MECHANISMS
223
angles 0" and 180" between the eliminating groups in the transition state appear also t o be favoured. Bunnett, Davis, and Hiroshi Tanida 94 have shown that sodium thioethoxide is a seven-fold more effective base than sodium methoxide in the bimolecular elimination reaction of acc-dimethylphenethyl chloride, i.e., the thioethoxide ion is the stronger base kinetically though weaker thermodynamically. Bunnett 90, 94 has argued convincingly that the kinetic behaviour of those reactions considered by some workers g5, 96 to proceed by the so-called merged mechanism for substitution-elimination may be explained satisfactorily by an E-2 mechanism. According to Hine and Ramsay 9 7 and contrary t o earlier estimates,98 the &-elimination of trans2-toluene-p-sulphonylcyclohexyl toluene-p-sulphonate with sodium hydroxide is not too fast for carbanion formation to be a plausible intermediate step. It appears 9 9 that there is no a-deuterium isotope effect in the bimolecular elimination reaction of dimethylphenethylsulphonium bromide with sodium hydroxide in water, but for the reaction of phenethyl bromide with sodium ethoxide in methanol JCH/kD = 1.17. This result is consistent with there being more unsaturation in the transition state for the second reaction. The results are complicated by the occurrence of deuterium-exchange a t C-1 of the dimethylsulphonium ion with solvent a t a rate comparable t o that of the elimination. The p-deuterium isotope effects, kH/lcD, in the pyrolytic elimination reactions of ethyl bromide, chloride, and acetate are all about 2 per hydrogen atom replaced by deuterium.lW These results suggest that some C,-H bond-stretching has occurred in the transition state. The olefin compositions from a number of reactions thought t o proceed through s-butyl cations have been determined.101 Colter and Johnson lo2 have found that, although there is a 90-fold variation in the rate of elirnination from a series of 1-methylbutyl arenesulphonates with ethanolic sodium ethoxide, the proportion of truns-pent-2-ene, cis-pent-2-ene, and pent-1-ene in the product varies only slightly. The base-catalysed elimination of malonodinitrile from 4,4-dicyano-3-p-nitrophenyl1-phenylbutan-1-one proceeds by an E-lcb mechanism.103 Wittig and Polster's lo4ylid mechanism (110) -+(112) for the reaction
9 4 J. F. Bunnett, G. T. Davis, and Hiroshi Tanida, J . Amer. Chem. SOC., 1962, 84, 1606. 95 S. Winstein, D. Darwish, and N. J. Holness, J . Amer. Chem. SOC., 1956, 78, 2915; E. L. Eliel and R . S. Ro, Tetrahedron, 1958, 2, 353; E. L. Elk1 and R . G. Haber, J . Amer. Chem. SOC., 1959, 81, 1249; see also ref. l(b), p. 165. 9 6 D. N. Kevill and N. H. Cromwell, J . Amer. Chem. SOC., 1961, 83, 3812; D. N. Kevill, P. H. Hess, P. W. Foster, and N. H. Crornwell, ibid., 1962, 84, 983. 9 7 J. Hine and 0. B. Ramsay, J . Amer. Chem. SOC., 1962, 84, 973. 98 F. G. Bordwell and R. J. Kern, J . Amer. Chem. SOC., 1955,77,1141; J. Weinstock, R. G. Pearson, and F. G. Bordwell, ibid., 1956, 78, 3468. 9 9 S. Agperger, N. Ilakovac, and D. Pavlovid, J . Amer. Chem. Soc., 1961, 83, 5032. loo A. T. Blades, P. W. Gilderson, and M. G. H. Wallbridge, Cunad. J . Chem., 1962, 40, 1526, 1533. l o l W. A. Smith and W. H. Watson, J . Amer. Chern. SOC., 1962, 84, 3174. I o 2 A. K. Colter and R. D. Johnson, J . Amer. Chem. SOC., 1962, 84, 3289. lo3 S. Patai, S. Weinstein, and Z. Rappoport, J., 1962, 1741. lo4 G. Wittig and R. Polster, Annulen, 1956, 599, 13.
224
ORGANIC CHEMISTRY
of alkyltrimethylammonium halides with phenyl-lithium to yield olefins is supported by the observations that deuterated lo5and tritiated l o 6 trimethylamine is obtained when the original alkyltrimethylammonium group has these isotopes in the @-position. The tritium isotope effect of less than 1-4 l o 6 is consistent with the formation of a highly reactive ylid of short life
( I 10.)
and of small selectivity for profium or tritium. Similar experiments show 10ia that the reactions of a number of alkyltrimethylammonium ions and of the dimethyl[~~-2H2]phenethyl~ulphonium ion with hydroxide ion do not involve an ylid intermediate. The mechanisms of the following eliminations have also received attention : dehydration of optically active neopentyl [2H]alcohol in the presence of bromoform and aqueous potassium hydroxide ; dehydrohalogenation pyrolysis of secondary and tertiary alkyl of a-halogeno-ketones ;96, acetates in the gas phase;logdehydration of butan-2-01catalysed by hydrogen bromide in the gas phase ;I10 acid-catalysed dehydration of p-aryl-p-hydroxypropionic acids ;ll1 Hofmann elimination of trimethyl-trans-2-phenylcyclohexylammonium hydroxide ;I12 thermal decomposition of the N-oxides and methohydroxides of cis- and trans-2-dimethylaminocyclohexanol, cis- and trans-2-dimethylaminocyclo-octanol,~~3 of the methohydroxide of N N and dimethylcyclopentylmethylamine ;114 decarboxylative elimination of cinnamic acid dibromides;ll5 and iodide-catalysed debromination of 1,1,2,2tetrabromoethane. 116 Additions to 0leb.-Addition of hypochlorous acid to allyl bromide and of hypobromous acid to allyl chloride, in the presence of perchloric acid, discloses an interesting example of neighbouring-group participation ;117 besides the normal addition products, 2-bromo-3- (287(,) and 3-bromo-2chloropropan-1-01 (>0.8%), respectively, are formed through the annexed rearrangement. I n the addition to allyl chloride (X = C1, Y = Br) there is
lo57
lo5 A. C. Cope, N. A. LeBel, P. T. Moore, and W. R. Moore, J . Amer. Chem. SOC., 1961, 83, 3861. 106 F. Weygand, H.Daniel, and H. Simon, AnnaZen, 1962, 654, 111. l ' (a) o G. Ayrey, E. Buncel, and A. N. Bourns, Proc. Chene. SOC., 1961,458; ( b ) W. H. Saunders and D. Pavlovid, Chem. and Ind., 1962, 180. 108 ( a ) W.A. Sanderson, and H. S . Mosher, J . Amer. Chem. SOC., 1961, 83, 5033; (b) G.. Coppens, D. N. Kevill, and N. H. Cromwell, J. Org. Chem., 1962, 27, 3299; F. J. Schmitz and W. S. Johnson, Tetrahedron Letters, 1962, 647. Io9 E. U. Emovon and A. Maccoll, J., 1962, 335. R. L. Failes and V. R. Stimson, J., 1962, 653. 111 D. S. Noyce and C. A. Lane, J . Amer. Chem. SOC., 1962, 84, 1635, 1641; D. S. Noyce, P. A. King, C. A. Lane, and W. L. Reed, ibid., p. 1638. 112 S. 6. Cristol and D. I. Davies, J . Org. Chem., 1962, 27, 293. 113 A. C. Cope, E. Ciganek, and J. Lazar, J . Amer. Chem. SOC., 1962, 84, 2591. 114 A. C. Cope, J. Lazar, N. A. LeBel, and D. L. Ross, J. Org. Chem., 1962, 27, 2627. 115 E. R. Trumbull, R. T. Finn, K. M. Ibne-Rasa, and C. K. Sauers, J . Org. Chem., 1962, 27, 2339. 116 W. G. Lee and S. I. Miller, J . Phys. Chem., 1962, 66, 655. 117 P. B. D. de la Mare, P. G . Naylor, and D. L. H. Williams, J., 1962, 443.
225
little, but in addition to ally1 bromide (X = Br, Y = C1) there is much more, rearrangement since neighbouring bromine can compete more effectively with chlorine for migration to the carbonium centre. Although the ratio of
non-rearranged bromochlorohydrinremains constant , the amount of bromine migration decreases markedly as the ionising power of the solvent is decreased, and hence also its ability to stabilise the intermediate carbonium ion?' I n the addition of trifluoroacetic acid to the hexenes and cycloalkenes the carbonium-ion intermediates apparently undergo less rearrangement, and less elimination of a proton, than do those formed in the corresponding solvolyses of toluene-p-sulphonates;l18 introduction of " remote " acetoxy- and trifluoroacetoxy-groups, in the 5-position of hex-1-ene, results in a 38- and 168-fold decrease, respectively, in the rate of this trifluoroacetic acid addition which is attributed to surprisingly large inductive effects.119 Bender and Connors l20 report the first investigation of a non-enzymic olefin hydration under neutral conditions in the kinetics of conversion of the monoanion of fumaric acid (113) into that of malic acid (115). The hydration is considered to proceed by concerted intramolecular catalysis involving both the carboxylic acid and the carboxylate groups and, on the basis of a variety of results, general acid-nucleophile-catalysed isomerisation to the lactonic acid (114) (which is rapidly hydrolysed) is favoured. The
bell-shaped pH-rate constant curve (see p. 249) agrees qualitatively with that of the enzymic reaction suggesting that a similar, but more efficient, assistance may be responsible for enzymic catalysis. Patai and Rappoport 121 have presented a general rationalisation of nucleophilic addition t o double bonds activated by electron-withdrawing substituents ;formation of widely different products, with the use of a variety of nucleophiles, always involve a carbanion intermediate. Among the reactions studied were the transfer of arylmethylene groups 121a (scheme 3), the uncatalysed hydrolysis of arylmethylene malononitriles (116) 121b to aldehydes and malononitrile, the base-catalysed hydrolysis of Ar.CH:CXY (X, Y = cyano, ethoxycarbonyl or carbamoy1),l2lc and the isomerisation of
P. E. Peterson and G. Allen, J . Org. P. E. Peterson and G. Allen, J . Org. l z o M . L. Bender and K. A. Connors, J . lZ1 S . Patai and Z. Rappoport, J . , 1962,
118
Chem., 1962, 27, 1505. Chem., 1962, 27, 2290. Amer. Chern. SOC., 1962, 84, 1980. (a)377, (6) 383, (c) 392, ( d ) 396.
226
ORGANIC CHEMISTRY
cis-ethyl a-cyano-p-o-methoxyphenylacrylate various nucleophiles.121d by The annexed mechanism (scheme 3) is typical.

pC ,N
AreCH =C, C0,Et -CH(CN),
. A
AreCH-C,
-FN
\
I COzEt CH(CN)z
p,CN AraCH-CH CL(CN);C02Et
Ar.CH=C(CN),
/
+
'CH (C N . C02Et )
(116)'
SCHEME 3.
Another novel nucleophilic addition is the condensation of salts of saturated carboxylic acids with ethylene in the presence of alkali metals, hydrides, or amides. The carbanion chain mechanism shown in scheme 4 is proposed.122 1 : 1 Addition of carboxylic acids and their derivatives t o unactivated double bonds, involving a free-radical chain mechanism, t o give
SCHEME 4.
high yields of homologous products, has also been reported.123 The reaction of butyl-lithium with 1,l-diphenylethylene, t o give the ion pair Bu*CH,*CPh,- Li+,a t higher concentrations, has been further investigated.124 The stereochemistry of a few additions t o olefins has been studied. Deuterium bromide and acenaphthylene yield more than 85% of the cisaddition product but it is not known if this results from a one-step concerted mechanism or the formation and rapid collapse of an ion-pair.125 Although the trifluoroacetic acid-catalysed reaction . s+ sof iodobenzene dichloride with olefins ins+li ':cl -.___ CI ____ H - 0 2C-CF3 volves direct attack by the dichloride, and 1 ._.__. c'''' I Ph not prior dissociation t o chlorine, it does (1'7) not lead t o exclusive cis-addition ; cyclohexene gives no cis-adduct; the transition state (117), akin t o a cyclic chloronium ion, which can decompose to give the trans-products, is proposed. The rates and stoicheiometries of the addition of diborane t o a variety of unsaturated hydrocarbons have been measured and the formation of the mono-, di-, or tri-alkylborane has been correlated with the degree of substitu-
c=
122L. Schmerling and W. G. Toekelt, J. Amer. Chem. SOC.,1962, 84, 3694. J. C. Allen, J. I. G. Cadogan, and D. H. Hey, Chem. and Ind., 1962, 1621. l24A. G. Evans and D. B. George, J., 1962, 141. lz5 M. J. X. Dewar and R. C. Fahey, J. Awaer. Chem. SOC.,1962, 84, 2012. lZ6 J. L. Coffer, L. J. Andrews, and R. M. Keefer, J. Anzer. Chem. Soc., 1962, 84, 793.
123
CAPON AND R E E S : REACTION MECHANISMS
227
tion a t the double bond;127 steric controlof the hydroboration of cholest-2-ene agrees with the results obtained with these simpler compounds.12* Steric control by the methyl group of the direction of attack of acetyl hypobromite and of perlauric acid on the double bond in 4-methylcyclopentene has been dem0n~trated.l~~ From the ratio of products formed in the sulphuric acid-catalysed addition of acetic acid to camphenilene (apoisofenchene) Me (118) (118) it appears that the difference between the elecMe tronic effect of a methyl group and a hydrogen atom a t position 6 of the norbornyl cation is small.130 of the direction and relative rates of attack of a A quantitative study series of stilbenes by trichloromethyl radicals has revealed that selective polar effects are not operative but that direction and rate of addition are governed by resonance-stability factors. Since addition of GCl, to 4-nitrotrans-stilbene gave radicals (119) and (120) in the ratio 3 : 2 it is concluded that the presence of a p-nitro-group in an already heavily stabilised benzyl radical does not greatly enhance the stability. Where such resonance stability is absent, polar effects in radical addition to olefins can be important
(119)
p-NO,*C,H,*~H*CHPh*CCl, p-NO2*C6H4*CH(CClS)-bHPh (120)
as has been shown,332a example, in the radical addition of methanethiol, for trifluoromethanethiol, and 2,2,2-trifluoroethanethiol perfluoropropene. to Further evidence for the striking stability of a-metallocenyl carbonium ions is provided by the rapid uncatalysed (MarkownikoE)addition of acetic acid to vinyl-ferrocene, -ruthenocene, and -osmocene, even at room temperat~re.132~ Diels-Alder Reaction.-Considerable effort is still being devoted to the solution of the subtle problems presented by this reaction and by its retrogression, related as these are by the microscopic-reversibility principle. The mechanisms of the formation, isomerisation, and decomposition of certain Diels-Alder adducts have been the subject of penetrating investigation by Berson and his co-workers. The first-order rate coefficients for the dissociation of the 9-phenylanthracene-maleic anhydride adduct in o-dichlorobenzene, as measured by spectrophotometric analysis of 9 -phenylanthracene, by exchange with [ 14C]maleicanhydride, and by racemisation, were identical.133 Thus isomerisation by an intramolecular mechanism is precluded, every molecular act of racemisation requiring decomposition of the adduct into kinetically identifiable fragments. The intramolecular mechanism previously demonstrated 34 for isomerisation of the cyclopentadiene-maleic
H. C. Brown and A. W. Moerikofer, J . Arner. Chem. SOC.,1962, 84, 1478. A. Hassner and C. Pillar, J. Org. Chern., 1962, 27, 2914. H. B. Henbest and J. J. McCullough, Proc. Chern. SOC., 1962, 74. 13* D. E. McGreer, Canad. J . Chern., 1962, 40, 1554. 131 J. I. G. Cadogan and E. G. Duell, J., 1962, 4154; J. I. G. Cadogan, E. G. Duell, and P. W. Inward, ibid., p. 4163; J. I. G. Cadogan and P. W. Inward, ibid., p. 4169. 132 (a) J. F. Harris and F. W. Stacey, J . Arner. Chern. SOC., 1961, 83, 840; ( b ) G. R. Buell, W. E. McEwen, and J. Kleinberg, ibid., 1962, 84, 40. 133 J. A. Berson and W. A. Mueller, J . Amer. Chem. SOC., 1961, 83, 4940. 13* J. A. Berson and R. D. Reynolds, J . Arner. Chem. SOC., 1955, 77, 4434; J. A. Berson, R. D. Reynolds, and W. M. Jones, ibid., 1956, 78, 6049.
127 128 129
228
O R G A N I C CHEMISTRY
anhydride adduct cannot now be attributed to a cage effect since the secondorder rate of recombination of cyclopentadiene and maleic anhydride is shown to be too slow by 6-9 powers of ten to be diffusion-controlled;if the internal mechanism for isomerisation does involve fragmentation of the adduct the fragments must be more tightly bound than a " caged aggregate " in the transition state.133 Although this internal isomerisation is thus not an invariable feature of Diels-Alder reactions it prompted a detailed study of the stereochemistry of the isomerisation of the optically active exo(eq)adducts (121) of cyclopentadiene with methyl acrylate and methyl methacrylate to the corresponding endo(ux)-isomers (122);135 this occurs with complete racemisation of the product and partial racemisation of the starting material. These results and previous kinetic data are very difficult to
(121; R = H or Me)
(122;RzH or Me)
reconcile with the diradical mechanism for the Diels-Alder reaction in which the first of the two distinct bond-formingsteps is rate-determining and leads to a triplet diradical (e.g., 123 from butadiene). Good evidence for this mechanism was apparently provided 136 by the effect of external pressure on the rate of the liquid-phase dimerisation of isoprene, which was interpreted in terms of a molar volume for the transition state substantially greater than that of the product, and hence incompatible with the simultaneous formation of both new bonds. However, a reappraisal 1 3 7 of this work suggests that since the Tait equation was not obeyed over the whole pressure range investigated 136 deductions about the volume of the transition state for this dimerisation are not justified. Berson and Remanick also argue persuasively against the Woodward and Katz " two-stage " mechanism 138 which they modify to the simple four-centre process with both dienedienophile bonds partially formed, though not necessarily t o the same extent -indeed a graded continuum between the extremes of a completely symmetrical four-centre mechanism and a fully developed two-step mechanism may be required to encompass all Diels-Alder reactions in spite of their great formal similarity. I n the reaction of 4-methylpenta-l,3-diene with tetracyanoethylene to give the adduct (124) the 1,Z-additionproduct (125) is also formed and, in striking contrast to the slight solvent effects characteristic of Diels-Alder additions, formation of this cyclobutane is over a hundred times faster in nitromethane than in tetrahydrofuran. Thus formation of both products (124) and (125) by the collapse, in either of two possible directions, of a common intermediate of the Woodward and Katz t y p e seems unlikely.139
J. A. Berson and A. Remanick, J. Amer. Chem. SOC., 1961, 83, 4947. C. Walling and J. Peisach, J . Amer. Chem. SOC., 1958, 80, 5819. 1 3 7 S. W. Benson and 5. A. Berson, J. Amer. Chem. SOC., 1962, 84, 152. 13* R. B. Woodward and T. J. Katz, Tetrahedron, 1959, 5 , 70. 139 C. A. Stewart, J. Amer. Chem. SOC., 1962, 84, 117.
135
229
The magnitude of the secondary deuterium isotope effects in the retrogression of the Diels-Alder adduct, 4-methyl-7- oxabicyclo[2,2,11hept -2- eneexo-5,6-dicarboxylic anhydride (126) in 2,ZY5-trimethylpentane a t 50,
(1 24)
( 1 25)
(126)
ka/k,, = 1.16 and k,/E, = 1.08, do not clearly distinguish between a oneor two-step process, but do suggest that if the latter is operative cleavage of the bond marked - - - is rate-determining.140 Second-orderrate constants for the addition in dioxan of maleic anhydride to a wide variety of dienes provide a quantitative measure of the greater reactivity of cyclic than of acyclic dienes and of the acceleration by electrondonating, and retardation by electron-withdrawing, substituents in the diene, especially when in the 9,lO-positions of anthracene. The large rate differences observed arise from differences in the activation energies, the low pre-exponential terms being fairly constant. 141 The customary r6les of the dienophile as the electron-deficient, and the diene as the electron-rich, partner are reversed in the reactions of hexachlorocyclopentadiene, the rate of addition to which is increased by electron-donating, and decreased by electron-withdrawing, substituents in the dienophile.l4 Determination 143 of the endo/exo product ratio in the kinetically controlled Diels-Alder addition of cyclopentadiene to methyl acrylate, methyl methacrylate, and methyl trans-crotonate at different temperatures in twelve solvents has shown that the Alder rule of " maximum accumulation of double bonds " is of minor importance; the rule was obeyed by the first and disobeyed by the second compound in all solvents? and obeyed by the third in polar but not in non-polar solvents. The solvent effects were correlated fairly well in quantitative terms by the Kirkwood-Onsager theory and their qualitative trend was explained by considering the interactions between the permanent dipoles of the diene and dienophile in the two transition states. A new empirical measure of solvent polarity, Q, is defined as the logarithm of the endo/exo product ratio for the cyclopentadiene-methyl acrylate addition;143it is linear in the other similar parameters 2 , 1 4 4 log kion for 2-p-methoxyphenyl-2,2-dimethyl ethyl toluene-p-~ulphonate~~~~ and l ~ should supplelog,,,, for the Curtius rearrangement of benzoyl a ~ i d e ,and ~ ment them particularly well in the non-polar solvent region. Other studies 146, 14' on the stereochemistry of Diels-Alder addition and an
S. Seltzer, Tetrahedron Letters, 1962, 457. J. Sauer, D. Lang, and A. Mielert, Angew. Chenz., Internat. Edn., 1962, 1, 268, 142 J. Sauer and H. Wiest, Angew. Chem., Internat. Ed n ., 1962, 1, 269. 143 J. A. Berson, Z. Hamlet, and W. A. Mueller, J . Amer. Chem. SOC., 1962, 84, 297. 144 E. M. Kosower, J . Amer. Chem. SOC., 1958, 80, 3253. 145 S. G. Smith, A. H. Fainberg, and S . Winstein, J . Amer. Chem. SOC., 1961, 83, 618. 146 H. P. Braendlin, A. Z. Zielinski, and E. T. McBee, J . Amer. Chem. SOC., 1962, 84, 2109. 1' H. P. Braendlin, G. A. Grindahl, Y. S. Kim, and E. T. McBee, J . Amer. Chem. 4 SOC., 1962, 84, 2112.
140 141
230
interesting related thermal intramolecular rearrangement 148 have been reported. Electrophilic Substitution at Saturated Carbon.-This subject was reviewed extensively last year and has also been reviewed by Kobrich.149 Investigations of reactions involving the formation and fission of carbonmetal bonds include those of Dessy 150 and Reutov 1 5 1 and their coworkers. Further investigations on the configurationalstability of a-sulphonyl carbanions have been reported 152 and tetramethylsulphamide, Me2N*S02*NMe2, a possible model for such ions, has been investigated by X-ray crystallograph^.^^^ a-Sulphinyl- and cc-phosphinoxy-groups stabilise the configurations of carbanions very much less than an a-sulphonyl and less even than an a-phenyl g r 0 ~ p . l The racemisation of optically active 2,2-di~~ phenylcyclopropyl cyanide (127) catalysed by sodium methoxide in methanol is 8080 times slower than deuterium exchange in methan[2H]ol, showing that the carbanion (128)has considerable configurational stability.155 The in rate of racemisation of ( +)-2-methyl-3-phenylpropionitrile dimethylsulphoxide-methanol containing sodium methoxide has been correlated with
the equilibrium basicity of the medium as measured by the H , function.15s The stereochemical course of several reactions with nitrogen leaving groups has been investigated.15' The mechanisms of the following reactions have also been investigated : deuterium exchange of 1-deutero-4-methyl-2,6,7trithiabicyclo[2,2,2]octane 1 5 8 and of a-deuterated toluenes ;159 protodetritylation of compounds of
148 149 150
J. A. Berson and J. W. Patton, J . Arner. Chem. SOC., 1962, 84, 3406. 1, 382. R. E. Dessy, W. L. Budde, and C. Woodruff, J . Amer. Chem. Soc., 1962, 84,
G. Kobrich, Angew. Chem., Internat. Edn., 1962,
1172.
lS1 0. A. Reutov, Khu Khun-ven, I. P. Beletzkaya, and T. A. Smolina, Zhur. Jiz. Khim., 1961, 35,.2424; I. P. Beletskaya, 0. A. Reutov, and T. A. Azizyan, Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Nauk, 1962, 223. 1 5 2 H.L. Goering, D. L. Towns, and B. Dittmar, J . Org. Chem., 1962, 27, 736; E. J. Corey, H. Konig, and T. H. Lowry, Tetrahedron Letters, 1962, 515; D. J. Cram 1962, 84, 1496. and A. S. Wingrove, J . Amer. Chem. SOC., lSs T. Jordan, W. Smith, and W. N. Lipscomb, Tetrahedron Letters, 1962, 37. lS4 D.J. Cram, R. D. Partos, S. H. Pine, and H. Jiiger, J . Amer. Chem. SOC., 1962, 84, 1742. 1 5 5 H. M. Walborsky, A. A. Youssef, and J. M. Motes, J . Amer. Chem. SOC., 1962, 84, 2465. 156 R. Stewart, J. P. O'Donnell, D. J. Cram, and A. B. Rickborn, Tetrahedron, 1962, 18, 917. lS7 D. J. Cram, J. S. Bradshaw, W. Lwowski, and G. R. Knox, J . Arner. Chem. Soc., 1962, 84, 2832. Is* Shigeru Oae, Waichiro Tagaki, and Atsuyoshi Ohno, J . Amer. Chem. SOC., 1961, 83, 5036. lSB A. Streitwieser, D. E. van Sickle, and W. C. Langworthy, J . Amer. Chem. SOC., 1962, 84, 244; A. Streitwieser and D. E. van Sickle, ibid., p. 249; A. Streitwieser, W. C. Langworthy, and D. E. van Sickle, ibid., p. 251 ; A. Streitwieser and D. E. van Sickle, ibid., p. 254; A. Streitwieser, D. E. van Sickle, and L. Reif, ibid., p. 258.
231
type Ph,C GHX, ;I60 base-catalysed isomerisation of olefins;I61 and sidechain halogenation of rnethylbenzenes.l6, Nucleophilic Substitution at Olefinic and Acetylenic Carbon.-Little mechanistic work has been reported. Miller and his co-workershave demonstrated 163 that, far from being inert to nucleophilic displacement as commonly assumed, halogen atoms attached to acetylenic carbon are very reactive towards thiophenoxide ions in dimethylformamide. The bimolecular reaction of sodium p-tolyl sulphide with l-chloro-2-phenylacetylene, having a half-life of several minutes at -25", is faster than that with n-butyl chloride under the same conditions; an addition-elimination mechanism is proposed :
Ph*@C*Cl
+ -SAr +-CPh:CCl.SAr
+P h - C d X 3 A r + C1-
With sodamide in liquid ammonia the bromine atom of N-(2-bromoallyl)n-propylamine (129) is displaced intramolecularly to give 2-methylene-lpropylaziridine (131); in tritium-enriched ammonia the reaction proceeds with incorporation of tritium in the product at the ring-methylene group only, suggesting the annexed elimination-addition mechanism that involves the allenic amine intermediate ( 130).16*
CH2=C*CH,.NHPr
(129)
Br I
--+- C H 2 = C = C H . N H P r
('30)
C H 2=C = C H - G P r
CH = c, H \C (13')
PNr
c -
CH~=C-CH
\
N Pr
Further examples of the ready displacement of vinylic halogen at the end of a conjugated system, through a stabilised intermediate anion, are provided by the conversion of 1,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene (132 ; R = R' = C1) into 1,2,3,-trichloro-4,5,5-trimethoxycyclopentadiene (132; R = C1, R' = OMe) and then into 2,3-dichloro-1,4,5,5-tetramethoxycyclopentadiene (132; R = R' = OMe),l65 and the conversion of
S. Patai and S. Dayagi, J., 1962, 726. A. Schriesheim and C. A. Rowe, J. Amer. Chem. SOC., 1962, 84, 3160; A. Schriesheim, R. J. Muller, and C. A. Rowe, ibid., p. 3164; A. Schriesheim and C. A. Rowe, Tetrahedron Letters, 1962, 405. 162 E. Baciocchi and G . Illuminati, Tetrahedron Letters, 1962, 637. 163 S. I Miller, C. E. Orzeck, C. A. Welch, G. R. Ziegler, and J. I. Dickstein, J. . Arnev. Chern. SOC., 1962, 84, 2020; A. K. Kuriakose and S. I. Miller, Tetrahedron Letters, 1962, 905. 164 A. T. Bottini and R. E. Olsen, J. Amer. Chem. SOC., 1962, 84, 195. E. T. McBee, D. L. Crain, R. D. Crain, L. R. Belohlav, and H. P. Braendlin, J . Amer. Chem. Xoc., 1962, 84, 3557.
160 161
232
ORGANIC CHEMISTRY
chloranil into trichlorohydroxy-p-benzoquinone in which the intermediate anion (133) is relatively stable a t high pH.le6 Aromatic Substitution.-EZectrop~~Zic substitution. Zollinger and his acid co-workers have shown that bromination of Z-naphthol-6,8-disulphonic (G-acid) involves the rapid reversible formation of a high concentration of an intermediate 0-complex which then decomposes slowly t o products.167 The rates of bromination with bromine and hypobromous acid are the same and are almost independent of pH (3-85-5-25) and of the concentration of whichever reactant is in excess. The presence of the intermediate is indicated by the ultraviolet and nuclear magnetic resonance spectra. The position at high field (z 3.66) of the signal from the l-proton and the absence of coupling of
this proton with the 3- and the 4-proton indicate that the structure of the intermediate is (134). Kinetic evidence indicates that a transient intermediate (135) of similar structure occurs in the iodination of p-nitrophenol. 16* Several more examples of high ortho/para ratios in nitrations which may be attributed to intramolecular assistance 169 have been reported 171 (see section 7). Nitration of aniline, 7 2 quinoline, and imidazole 1 7 3 and tritiodeprotonation of 2 , 4 , 6 - ~ o l l i d i n eall ~ ~ sulphuric acid solutions, proceed by way of , ~ in the conjugate acids. The measurement of partial rate factors 1759 176 continues, as do the arguments concerning the correct equation for their correlation. 176,177
1 7 0 9
J. W. Hancock, C. E. Morell, and D. Rhum, Tetrahedron Letters, 1962, 987. M. Christen and H. Zollinger, Helv. Chim. Acta, 1962, 45, 2057, 2066; M. Christen, W. Koch, W. Simon, and H. Zollinger, ibid., p. 2077. 168 E. Grovenstein and N. S. Aprahamian, J . Amer. Chem. SOC.,1962, 84, 212. lC9 See A. Lapworth and R. Robinson, M e m . Proc. Manchester Lit. Phil. SOC., 1928, 72, 43; Ann. Reports, 1961, 58, 162. 1 7 0 E. R. Ward and J. E. Marriott, Chem. and Ind., 1962, 507. 171 D. H. Hey, J. A. Leonard, and C. W. Rees, J . , 1962, 4579. 172 M. Brickman, S. Johnson, and J. H. Ridd, Proc. Chem. SOC., 1962, 228. 173 M. W. Austin, M. Brickman, J. H. Ridd, and B. V. Smith, Chem. and Ind., 1962, 1057. 174A. R . Katritzky and B. J. Ridgewell, Proc. Chem. SOC., 1962, 114. 175 H. C. Brown, M. Dubeck, and G. Goldman, J . Amer. Chem. SOC., 1962, 84, 1229; H. C. Brown and A. H. Neyens, ibid., p. 1233; H. C. Brown and G. Marino, ibid., p. 1236; H. C. Brown and L. M. Stock, ibid., p. 1238; H. C. Brown and G. Goldman, ibid., p. 1650; H. C. Brown and A. H. Neyens, ibid., p. 1655; H. C. Brown and G. Marino, ibid., p. 1658; R. Baker, C. Eaborn, and J. A. Sperry, J., 1962, 2382; P. A. S. Smith, J. H. Hall, and R. 0. Kan, J . Amer. Chem. SOC., 1962, 84, 485; A. Streitwieser and R. C. Fahey, J . Org. Chem., 1962, 27, 2352. 176 G. A. Olah, S. J. Kuhn, and S . H. Flood, J . Amer. Chem. SOC., 1962, 84, 1688, 1695; P. B. D. de la Mare and I. C. Hilton, J., 1962, 997; P. B. D. de la Mare, D. M. Hall, M. M. Harris, H. Hassan, E. A. Johnson, and N. V. Klassen, J., 1962, 3784; L. M. Stock and F. W. Baker, J . Amer. Chem. SOC.,1962, 84, 1661. 17 H. C. Brown and L. M. Stock, J . Amer. Chem. SOC., 1962, 84, 1242, 1668, 3298; see also R. C. Neuman, ibid., p. 3025; R. 0. C. Norman and G. K. Radda, Tetrahedron Letters, 1962, 125.
166 167
233
The mechanisms of the following reactions have also been investigated: bromination of fluorene 178 and naphthalene ;I79 chlorination of fluorene;Is0 halogenation of 8-hydroxyquinoline chelates;lS1 chlorination in acetonitrilenitromethane ;IS2 amination by hydroxylammonium salts ;lg3 nitration ;l4 S' Friedel-Crafts alkylation alkylation by aliphatic alcohols;184c phenylmercurideboronation of benzene-boronic acid reaction of aromatic compounds with 2-acetoxyalkylmercuric acetates ;I** formation of phosphine imides from bromoarylamines and triphenylphosphine ;184f and hydrogen isotope exchange of 1,3,&trimethoxybenzene. Nucleophilic substitution. The kinetics of the rather complex reactions of benzenediazonium fluoroborate with thiocyanate ions in water have led Lewis and Cooper 185 to propose a modified mechanism for the decomposition of arenediazoniuni ions :
Ar*N,+
+ Ar-N,+*
, t A r O H
B-
l----+ArB
+ N, + H+ + N,
The highly reactive and unselective intermediate, ArN, +*, can react rapidly with water or with the ambidentate thiocyanate ion, but can also revert to the diazonium ion; among possible structures considered for this intermediate is the charged cage pair Ar+N,. The kinetics of the bimolecular reactions of aniline in ethanol with various halogenonitro-benzenesand -naphthalenes and polynitrobenzenes have been studied by Parker and his co-workers.lS6 For the benzene compounds the ease of displacement of the leaving groups, NO, > F Br > C1> I, is considered to be best explained on the one-stage synchronous mechanism with a small amount of bond-stretching in the transition state, but the twostage mechanism is invoked to explain the greater reactivity of the corresponding naphthalene compounds. I n contrast to the halogenodinitrocompounds, 1,2,3-trinitrobenzeneis more reactive than 1,2,4-trinitrobenzene and this is attributed to steric acceleration. The one-stage mechanism is also favoured lS7 for the reactions of various anilines with cyano-, methyl-,
>
U. P. Zimmerman and E. Berliner, J . Amer. Chem. Xoc., 1962, 84, 3953. E. Berliner and B. J. Landry, J . Org. Chem., 1962, 27, 1083. lSo G. H. Beaven, P. B. D. de la Mare, E. A. Johnson, and N. V. Klassen, J . , 1962,
178 179
K. D. Maguire and M. M. Jones, J . Anzer. Chem. Xoc., 1962, 84, 2316. R. M. Keefer and L. J. Andrews, J . Amer. Chem. SOC.,1962, 84, 3635. P. Kovacic, R . P. Bennett, and J. L. Foote, J . Anaer. Chem. Soc., 1962, 84, 759. ( a )G. A. Olah and S. J. Kuhn, J . Amer. Chem. Xoc., 1962, 84, 3684; G. A. Olah, S. J. Kuhn, S . H. Flood, and J. C. Evans, ibid., p. 3687; L. L. Ciaccio and R. A. Marcus, ibid., p. 1838; K. R. Buck and R. S. Thomson, Chem. and I n d . , 1962, 822; J. F. Eastham, J. L. Bloomer, and F. M. Hudson, Tetrahedron, 1962, 18, 653; ( b ) S. H. Sharman, J . Amer. Chem. SOC.,1962, 84, 2945, 2951; (c) V. Gold and T. Riley, J . , 1962, 4183; ( d ) H. G. Kuivila and T. C. Muller, J . Amer. Chem. SOC., 1962, 84, 377; (e) Katsuhiko Ichikawa, Koichi Fujita, and Osuma Itoh, ibid., p. 2632; (f)H. Hoffmann and D. Michael, Chem. Ber., 1962, 95, 528; ( 9 ) A. J. Kresge and Y. Chiang, J . Amer. Chem. SOC.,1962, 84, 3976; see also W. M. Schubert and R. H. Quacchia, ibid., p. 3778; A. J. Kresge, G. W. Barry, K. R. Charles, and Y . Chiang, i b d . , p. 4343. E. S. Lewis and J. E. Cooper, J . Amer. Chem. SOC., 1962, 84, 3847. lE6 R. E. Parker and T. 0. Read, J., 1962, 9, 3149; D. H. D. Elias and R. E. Parker, J., 1962, 2616. N. B. Chapman, D. K. Chaudhury, and J. Shorter, J., 1962, 1975.
181
988.
lE2
234
ORGANIC CHEMISTRY
and nitro-substituted 2-chloropyridines these reactions and many others ; of metu- and puru-substituted anilines with chloro-compounds are characterised by a Hammett constant p = -3.1 to -3.5. The displacement of halogen from 2-chloro- and 2-iodo-5-nitropyridine by water in aqueous dioxan, acetic acid, and sulphuric acid is acid-catalysed and in the last case the rate is proportional to u~,o.188 I n a continuation of studies on bond cleavage in aryl toluenesulphonates by nucleophilic reagents, Bunnett and Bassett lS9have shown that with 4-methyl-2-toluene-p-sulphonyloxyquinoline position of cleavage is inthe sensitive to the nature of the reagent, in agreement with an explanation 190 of earlier results based on London forces. The rate of sulphur-oxygen fission by piperidine in nitrophenyl toluene-p-sulphonates was decreased only 4-8-fold by the introduction of two methyl groups ortho to sulphur; since this is attributable to electronic effects it was concluded that there was miserable (i.e., undetectable) steric hindrance to nucleophilic substitution at the sulphonate-sulphur, in contrast to the enormous hindrance to substitution at the carbonyl-carbon in the benzoic esters.lgl Nucleophilic disto placement by water a t an aromatic carbon atom is shown lg2 be involved in the very ready acid-catalysed cleavage of certain azoaryl esters (see ref. 193), the protonated azo-group, like the diazo-group and protonated heterocyclic nitrogen, being very strongly activating for aromatic nucleophilic substitution. The ready replacement of halogen in aryl halides by a variety of nucleophilic reagents by the use of cuprous salts in polar organic solvents has been noted; other metallic ions, metallic copper, and cupric salts were ineffective.194 The smooth conversion of 2-nitrobiphenyl-2-carboxylic acid (136) with base into 3,4.-benzocoumarin(137) and nitrite requires the displacement of a virtually unactivated nitro-group by the very weakly nucleophilic carboxylate anion, presumably the result of very favourable steric circumstances.lg5 Other recent kinetic studies of nucleophilic aromatic substitution have been concerned with the polar effects of 4-and 5-substituents in o-chloro-
188 J. D. Reinheimer, J. T. Gerig, R. Garst, and B. Schrier, J. Amer. Chem. SOC., 1962, 84, 2770. 189 J. F. Bunnett and J. Y. Bassett, J. Org. Chem., 1962, 27, 1887. 1 9 0 J. F. Bunnett and J. Y. Bassett, J . Amer. Chem. SOC.,1959, 81, 2104. 191 J. F. Bunnett and J. Y. Bassett, J. Org. Chem., 1962, 27, 2345. 192 J. F. Bunnett, E. Buncel, and K. V. Nahabedian, J. Amer. Chem. SOC., 1962, 84, 4136. 193 Ann. Reports, 1961, 58, 164. 194 R. G. R. Bacon and H. A. 0. Hill, Proc. Chem. SOC., 1962, 113. 195 D. H. Hey, J. A. Leonard, and C. W. Rees, J . , 1962, 4579.
235
nitrobenzene,196 the ortho/para ratio in the displacement of chlorine from 2,4-di~hloro-l-nitrobenzene,~~~ the various reactions of o- and p and with dinitrobenzene and akyl 2,4-dinitrophenyl ethers with hydroxide and alkoxide ions in aqueous methanol and ethan01.l~~ Investigations of the elimination-addition (aryne) mechanism have this year been largely concerned with new methods of generating arynes l99--2o1 (cf. section 7) and exploiting their reactivity, rather than with quantitative aspects. Benzyne and related intermediates have been reviewed.202 2,3-Pyridyne is generated from 3-bromo-2-chloropyridineand lithium amalgarny2O3 and 3,4-pyridine from 3-bromo-4-chloropyridine and from 3-diazoniopyridine-4-carboxylate treatment of 3-chloro- or S-bromo;204 pyridine with lithiopiperidine and piperidine gave 3- and 4-piperidinopyridine in nearly equal amounts.205 Intramolecular addition of side-chain nucleophilic centres to benzynes have led to carbocyclic 206 and heterocyclic systems.207 Radical substitution.* Severalnew methods for free-radicalarylation have appearedY2O*, two of which involve homolytic oxidation of aroic acids.209 209 Photolysis of aryl iodides in benzene to give arylbenzenes has been extended to a number of compounds containing radical- or light-sensitive functions.210 6Wo-y-radiolysisof aryl bromides 211 and iodides 212also gives aryl radicals. Aryl radicals from para-substituted benzoyl peroxides react with toluene in a manner consistent with a theory concerning polar influences on the reactivity of free radi~als.2~3 Previously reported anomalies in the reaction of benzoyl peroxide with anisole have been ascribed to the presence of traces of phenol in the a n i s ~ l e . ~ ~ ~ Oxygen intercepts the intermediate phenylcyclohexadienyl radical (138) formed when benzoyl peroxide decomposes in dilute solution in benzene, to
lg6 W. Greizerstein, R. A. Bonelli, and J. A. Brieux, J . Amer. Chern. SOC.,1962, 84, 1026. l g 7 W. Greizerstein and J. A. Brieux, J . Amer. Chem. SOC., 1962, 84, 1032. l g 8 E. Tommila and J. Murto, Acta Chem. Scand., 1962, 16, 53, 63. l g B E. LeGoff, J . Amer. Chern. SOC., 1962, 84, 3786. 200 J. A. Kampmeier and E. Hoffmeister, J . Amer. Chem. SOC.,1962, 84, 3787. 201 G. Wittig and R. W. Hoffmann, Chem. Ber., 1962, 95, 2718. 2 o z H. Heaney, Chem Rev., 1962, 62, 81. 203 R . J. Martens and H. J. den Hertog, Tetrahedron Letters, 1962, 643. 2 0 4 T. Kauffmann and F.-P. Boettcher, Chem. Ber., 1962, 95, 949. 2 0 5 T. Kauffmann and F.-P. Boettcher, Chem. Ber., 1962, 95, 1528. 2 0 6 J. F. Bunnett and J. A. Skorcz, J . Org. Chem., 1962, 27, 3836. 2 0 7 D. H. Hey, J. A. Leonard, and C. W. Rees, Chem. and Ind., 1962, 1025. 2 0 8 P. J. Bain, E. J. Blackman, W. Cummings, S. A. Hughes, E. R. Lynch, E. B. McCall, and R. J. Roberts, Proc. Chem. SOC.,1962, 186; J. I. G. Cadogan, J., 1962, 4257. 2 0 9 J. Russell and R. H. Thornson, J., 1962, 3379; W. H. Starnes, J . Amer. Chem. Soc., 1962, 84, 2270. 210 N. Kharasch, W. Wolf, J. J. Erpelding, P. G. Naylor, and L. Tokes, Chem. and I n d . , 1962, 1720; N. Kharasch and L. Gothlich, Angew. Chem., Internat. Edn., 1962, 1, 459. 211 A. F. Everard, J. D. Parrack, G. A. Swan, and P. S. Timmons, J., 1962, 905. 212 J. D. Parrack, G. A. Swan, and P. Wright, J., 1962, 911. 213 J. K. Hambling, D. H. Hey, and G. H. Williams, J., 1962, 487. 214B. Lynch and R. B. Moore, Canad. J . Chem., 1962, 40, 1461. M.
* The Reporters gratefully acknowledge the help of Dr. M. J. Perkins with this section.
236
ORGANIC CHEMISTRY
give biphenyl in yields as high as 1.5 moles per mole of per0xide.2~~ When the solvent is a monosubstituted benzene, the isomer composition of the biaryls formed does not change, however, from that observed when the reaction is carried out under nitrogen to give the biaryls in much lower yield. l6 Thus, surprisingly, the isomeric phenylcyclohexadienyl radicals must participate in different reactions to an equal extent, validating earlier quantitative studies of these reactions. Failure to observe phenylcyclohexadienes from the disproportionation of phenylcyclohexadienyl radicals (138) as products in the phenylation of benzene with nitrosoacetanilide or phenylazotriphenylmethane has been advanced as evidence that the reaction does not involve free radicals but occurs within a solvent ~age.2~'Partial rate factors, relative to benzene, for the phenylation of naphthalene and anthracene under the conditions of the Meerwein reaction have been determined and agree well with theoretical predictions for radical substitution.21s The bearing of results obtained by allowing " iso-octyl " radicals to react with anthracene on Szwarc's method for determining relative reactivities of aromatic compounds in terms of their " methyl affinities " has been discussed.219 The gas-phase reaction of trifluoromethyl radicals with benzene and toluene has been reported. 220 Hydroxyl radicals generated from Fenton's reagent are electrophilic in their reactions with substituted benzenes.221 The intermediate hydroxycyclohexadienyl radicals (139) have been observed spectroscopically in
pulse-radiolysis experiments,222as have arylcyclohexadienyl radicals, e.g., (138), in pulse-radiolysis of aromatic compounds.223 Aromatic Rearrangements.-Claisen and related rearrangements. The rates of rearrangement of seven ally1 meta-substituted phenyl ethers to the corresponding 5-substituted 2-allylphenols, calculated from the total rearrangement rate and the fraction of the 5-substituted isomer found by isotope dilution analysis, can be correlated by the Hammett equation most satisfactorily by using 6, +, not om+, constants indicating that meta-substituents interact with the reaction centre in the transition state to about the same extent as p a r a - s u b ~ t i t u e n t s . ~ ~ ~ unusual result is explained on This the basis of a previously postulated mechanism 225 involving simultaneous homolysis of the allyl-oxygen bond and homogenesis of the ortho-carbonM. Eberhardt and E. L. Eliel, J. Org. Chem., 1962, 27, 2289. R. T. Morrison, J. Cazes, N. Samkoff, and C. A. Howe, J . Amer. Chem. SOC., 1962, 84, 4152. 2 1 7 E. L. Eliel, M. Eberhardt, 0. Simamura, and S . Meyerson, Tetrahedron Letters, 1962, 749. 2 1 8 S. C. Dickerman and G. B. Vermont, J . Amer. Chem. SOC., 1962, $4, 4150. 2 1 9 A. L. J. Beekwith, J., 1962, 2248. 2 2 0 J. L. Holmes and K. 0. Kutschke, Trans. Faraday SOC., 1962, 58, 333. 221 R. 0. C. Norman and G. K. Radda, Proc. Chem. SOC., 1962, 138. 2 2 2 L. M. Dorfman, R. E. Biihler, and I. A. Taub, J. Chem. Phys., 1962, 36, 549. 223 A. MacLachlan and R. L. McCarthy, J . Amer. Chem. SOC., 1962, $4, 2519. 2 2 4 W. N. White and C. D. Slater, J. Org. Chenz., 1962, 27, 2908. 2 3 5 W. N. White and W. K. Fife, J . Amer. Chem. SOC., 1961, $3, 3846.
215
218
237
allyl bond giving a highly electron-deficientoxygen atom. Rearrangement of allyl m-tolyl ether gives a mixture of 53% of 2-allyl-3-methyl- and 47% of 2-allyl-5-methyl-phenolshowing the lack of a significant steric effect.226 The accelerating effect of pressure, in the range 1000-6000 kg./cm.2, on the rearrangement of allyl phenyl ether and the closely related Cope rearrangement of compound (140) to compound (141) is considered to be most consistent with a tightly bound cyclic transition state where formation of the new bond has developed further than breaking of the old
The simple Claisen rearrangement could not be extended to allyl phenyl sulphide. The mechanism of the '' abnormal " Claisen rearrangement has been considerably clarified. The formation of the " abnormal " product o-(1methylbut-2-eny1)phenol (145) from pent-2-enyl phenyl ether (142) is not
('42)
competitive with, but consecutive to, the normal rearrangement into o-(a-ethylally1)phenol(143) which more slowly isomerises to compound (145) possibly wia the spiro-compound ( 144).229 Similar formation of an abnormal product by thermal isomerisation of the normal product has been demonl-14C]but-2-ene into 3-(2strated for the conversion of cis-4-p-tolyloxy[ hydroxy-5-methylphenyl)-[4-14C] and thence -[1- 14C]-but - 1- ene. 30 The subtle question of the choice between 4-centre overlap in a chair-like transition state (146) or 6-centre overlap in a boat(roof)-liketransition state (147) in a Cope rearrangement where both are possible has been elegantly
D. S. Tarbell and S. S. Stradling, J . Org. Chem., 1962, 27, 2724. C. Walling and M. Naiman, J . Arner. Chern. SOC., 1962, 84, 2628. 2 2 8 H. Kwart and C. M. Hackett, J . Arner. Chern. SOC., 1962, 84, 1754. 2 2 9 E. N. Marvell, D. R. Anderson, and J. Ong, J . Org. Chem., 1962, 27, 1109. 2 s o A. Habich, R. Barner, R. M. Roberts, and H. Schmid, Helw. Chim. Acta, 1962, 45, 1943.
226
227
238
ORGANIC CHEMISTRY
solved by Doering and Roth. 231 meso-3,4-Dimethylhexa1,5-diene reand arranges to cis,trans-octa-2,6-dieneY the racemic isomer rearranges to transYtrans-octa-2,6-diene (90%) and cis,cis-octa-2,6-diene (9%); from this it follows that the chair-like transition state is kinetically favoured over the boat-like structure by a difference in free energy of activation of at least 5.7 kcal./mole. Benxidine and semidine rearrangements. The results of a new intensive investigation of these mechanisticallyelusive reactions have appeared 232-242 and detailed mechanistic interpretations will be eagerly awaited; for a preliminary discussion see ref. 243. The work has been mainly concerned with the identity and estimation of all products, and with the measurement of the rates and the solvent- and substrate-isotope effects in the perchloric 1,2-hydrazoacid-catalysed rearrangements of 1,l-hydrazonaphthalene,232 n a ~ h t h a l e n e , ~ 2,2-hydrazonaphthalene, and mixtures of t h e ~ e , ~ 3 ~ ~3 234 N -1-naphthyl-N-phenylhydrazine, N-2-naphthyl-N-phenylhydrazine,23 o-hydrazotoluene, and hydrazoben~ene,~3~ in aqueous dioxan, and 238 mostly the variations in these factors over a wide range of acid and total electrolyte concentration. The established quadratic dependence on hydrogen-ion concentration of the rate of rearrangement of hydrazobenzene, and the newly demonstrated linear dependence of this rate for 1,l- and 1,2-hydrazonaphthalene, are considered to define the two limiting kinetic forms of the benzidine rearrangement. Transitional kinetics, examples of which were known, begin to emerge with an order in acid of 1.15 in the slower rearrangement of 2,2-hydrazonaphthalene, and the transition from one kinetic extreme to the other for one substrate with changing acid concentration is clearly demonstrated for the rearrangement of N- -naphthyl-N-phenyl1 hydrazine; from to 10-3~-hydrogen-ion order in hydrogen-ion is 1.0 the and above this concentration it rises steadily to near 2, in good agreement with a theoretical suggestion 244 concerning non-integral orders in rearrangeand ments of this type. N-2-Naphthyl-N-phenylhydrazine o-hydrazotoluene show a similar gradation of order with acidity and in the latter case quantitative agreement with the requirements of two concurrent, independent rearrangements, one linear and the other quadratic in hydrogen-ion dependence, is demonstrated. These two reaction types were further characterised by two distinct sets of values for the solvent kinetic isotope
W. von E. Doering and W. R. Roth, Tetrahedron, 1962, 18, 67. D. V. Banthorpe, E. D. Hughes, and Sir Christopher Ingold, J., 1962, 2386. 233 D. V. Banthorpe and E. D. Hughes, J., 1962, 2402. 234D.V. Banthorpe, J., 1962, 2407. 235D. Banthorpe, J., 1962, 2413. V. 236 D. V. Banthorpe, E. D. Hughes, and S r Christopher Ingold, J., 1962, 2418. i 2 3 7 D , Banthorpe, J., 1962, 2429. V. 23* D. V. Banthorpe, Sir Christopher Ingold, J. Roy, and S. M. Somerville, J., 1962, 2436. 239 D. V. Banthorpe, E. D. Hughes, Sir Christopher Ingold, and J. Roy, J., 1962, 3294. 2 4 0 D. V. Banthorpe, E. D. Hughes, Sir Christopher Ingold, and R. Humberlin, J., 1962, 3299. 241 D. V. Banthorpe and E. D. Hughes, J., 1962, 3308. 242D. V. Banthorpe and E. D. Hughes, J., 1962, 3314. 2 4 3 S i r Christopher Ingold in ref. 2(a),p. 118. 2 4 4 D. A. Blackadder and S r Cyril Hinshelwood, J., 1957, 2898. i
231 232
239
effect:232g 239 238 replacement of water in the media by deuterium oxide accelerates the linearly acid-dependent rearrangements about 2-fold and the quadratically acid-dependent rearrangements about 4-fold, and by intermediate factors depending upon the acidi6y and thus on the kinetic order in acid in the transitional region. It is concluded from this that the protons, whether one or two, which catalyse these rearrangements are probably completely transferred in the respective transition states. Measurements of substrate-isotope effects, for 1,l-hydrazonaphthalene deuterated in the 2,2- and 4,4-positionsZ40 and for hydrazobenzene deuterated in the 4,4positions, and at all carbon atoms other than the 4,4-po~itions,~~l no show detectable difference in overall rates or, for the benzene compounds, product ratios and so, for the latter, aromatic proton loss must occur after the activation barrier for rearrangement has been surmounted and after the mechanism has branched towards the individual products. The specific hydrogen-ion, not general acid, catalysis of the rearrangement of hydrazobenzene has been confirmed;239 in this work the acidity function H , of perchloric acid in 60% aqueous dioxan with lithium perchlorate added to give constant total electrolyte has been established. In the absence of other electrolyte the acidity function in the system has been extended to lower acidities. The rearrangement of mixtures of pairs of the three hydrazonaphthalenes gave no crossed product but only the products of the individual rearrangements in the required proportions, thus establishing the intramolecular nature of the linearly acid-dependent rearrangements, similar t o that well-established for the quadratically acid-dependent rearrangements. m-Hydrazoaniline (148) specifically labelled with 15N in the hydrazolinkage has been rearranged Z45 to 00-diaminobenzidine (149) which was then converted into 2,7-diaminocarbazole (150); the difference in 15Ncontent of compounds (148) and (150) provides an ingenious measure of the 15N in the ortho-amino-groupsof the tetra-amine (149) and hence of the amount of coupling in the ortho- and para-positions of the benzidine (148); surprisingly this was found to vary with the acidity of the reaction mixture. The
results indicate that a metastable intermediate is formed in the rate-determining step and are compatible with the production of a system in which the four nitrogen atoms become equivalent on addition of the second proton. A dissociative mechanism, in which one half of the intermediate may rotate
245
G . S Hammond and J. S . Clovis, Tetrahedron Letters, 1962, 945. .
240
ORGANIC CHEMISTRY
relative t o the other, similar t o that proposed by D e ~ a r is suggested. , ~ ~ ~ This rearrangement shows a different acid-dependence from that of hydrazobenzene, and their mechanisms may be entirely different. On the basis of the geomehy of the starting materials, the types of products formed, and a reasonable reaction mechanism, the rapid, quantitative, acid-catalysed rearrangement of p-" quinamines " (e.g., 151)to p-aminodiphenyl ethers (e.g., 152) appears t o be of the benzidine type; it is of the first order in quinamine and in hydrogen-ion and is intramolecular. A radical-ion complex transition state, with the two aromatic rings approximately parallel, is considered to explain certain substituent effects most satisfactorily.24
Hiickel molecular-orbital computations to describe the benzidine rearrangement have been described.248 Other rearrangements. The nitramine rearrangement in aqueous perchloric acid is partly intermolecular and partly intramolecular ; when and mixtures of p-fl~oro-N-methyl-~~N-nitroaniline N-methyl-N-nitroaniline are rearranged 15N appears in the p-nitro-N-methylaniline although this is formed only from the N-methyl-N-nitroaniline and not from the fluorinated compound. 5 4 9 Other rearrangements which have been investigated mechanistically include : the Hofmann-Martius and Reilly-Hickinbottom reaction ;250 the Wallach rearrangement of azoxybenzenes t o 4-hydroxyazobenzenes ;251 conversion of fenchone into 3,4-dimethylacetophenone in sulphuric acid ;252 rearrangement of 4-amino-5-nitrosopyrimidinesinto 1,3,5-triazines;253 Fischer indole syntheses involving methyl migration ;254 aromatisation of 2,2-dimethyl-3-[14C]methylpentane to m-xylene and toluene;255 and disproportionation of ethyl[ 1-14C]benzene by aluminium bromide-hydrogen bromide. 256 The mechanisms of the water-promoted, aluminium halidecatalysed isomerisation of mono- and di-halogenobenzenes,halogenotoluenes, and terphenyls have been investigated in considerable detail by Olah and co-workers.257 Carbenes and Nitrenes.--Carbenes. Two ingenious methods of generating triplet-state methylene have been reported, in solution by the benzophenone2 4 6 M. J. S. Dewar, Kekul6 Symposium on Theoretical Organic Chemistry, Butterworths Scientific Publns., London, 1958, p. 198. 2 4 7 B. Miller, Tetrahedron Letters, 1962, 55. 2 4 8 L. C. Snyder, J. Amer. Chem. SOC., 1962, 84, 340. z 4 9 W. N. White and J. T. Golden, Chem. and Ind., 1962, 138. Z 5 O H. Hart and J. R. Kosak, J . Org. Chem., 1962, 27, 116. i.51 C.-S. Hahn and H. H. Jaff6, J. Amer. Chem. SOC., 1962, 84, 946. 2 5 2 R . P. Lutz and J. D. Roberts, J. Amer. Chem. Soc., 1962, 84, 3715. 253 E. C. Taylor and C. W. Jefford, J. Amer. Chem. SOC., 1962, 84, 3744. 2 5 4 R. B. Carlin and M. S. Moores, J. Amer. Chem. SOC.,1962, 84, 4107. 2 5 5 S. M. Csicsery and H. Pines, J. Amer. Chem. SOC., 1962, 84, 3939. 2 5 6 E. Unseren and A. P. Wolf, J . Org. Chem., 1962, 27, 1509. 2 5 7 G. A. Olah, W. 8. Tolgyesi, and R. E. A. Dear, J. Org. Chem., 1962, 2'7, 3441, 3449, 3455; G. A. Olah and M. W. Meyer, ibid., pp. 3464, 3682.
241
photosensitised decomposition of diazomethane 258 and in the gas phase by triplet mercury-photosensitised decomposition of keten, 259 the triplet state in both cases being characterised by non-stereospecific addition to cis- and trans-but-2-ene. I n contrast to the lY2-addition singlet-state methylene of to buta-1,3-diene, in the presence of a large excess of inert gas methylene adds to the 1,4-positions, giving cyclopentene;260 this is a typical radicaladdition reaction expected for triplet ground-state methylene formed by collision. The isoelectronic '' nitrene," NH, generated from hydroxylamineO-sulphonic acid and sodium methoxide, also undergoes 1,4-addition to butadiene, to give pyrroline.261 The initial step in the reaction of methylene, from the photolysis of diazomethane, with hydrogen and with methane is addition to form vibrationally excited methane and ethane, respectively.262 Photolysis of diazoethane produces ethylidene (methylcarbene), CH,*CH : , which rearranges rapidly to ethylene and appears to add to propene more specifically than does methylene, and to the butenes hardly at all.263 Photolysis of diazirine gives methylene which adds stereospecificallyto trans-but-2ene and is presumably in the singlet state ;264thermal decomposition (124174') of dimethyldiazirine in the gas phase to propene and nitrogen is a first -order homogeneous reaction in which dimethylcarbene is probably an intermediate.265 Ethylmethyldiazirine similarly (ax. 160") gives ethylmethylcarbene which rearranges to the same mixture of butenes and methylcyclopropane as is obtained in the alkaline decomposition of ethyl methyl ketone toluene- p-sulphonylhydrazone ; photolysis of ethylmet hyldiazirine, however, gave different product ratios, suggesting that the carbene is then vibrationally excited and that a " hot-radical " effect in intramolecular insertion is being observed.266 Franzen 2 6 7 has demonstrated the existence of difluorocarbene, independent of trifluoromethyl-lithium, with a life-time, in ether at room temperature, of between 5 x 10-4 and 10-3 sec. Competitive experiments show phenylcarbene, from the photolysis of phenyldiazomethane, to be about equally reactive towards the benzene ring and an aliphatic CH, group, about six times more reactive towards an aliphatic CH, than a CH, group, and to be inert towards aromatic CH bonds.268 To explain the unexpected observation that formation of diphenylcyclopropane in the reaction of dibromodiphenylmethane and methyl-lithium with an olefin is stereospecific,cc-metallation followed by concerted elimination of lithium bromide and addition to the double bond (see 153) is pr0posed.~6~ Several new carbenes have been proposed as reaction intermediates, and
2 5 8 K. R. Kopecky, G. S. Hammond, and P. A. Leermakers, J . Amer. Chem. Soc., 1962, 84, 1015. 2 5 9 F. J. Duncan and R. J. Cvetanovid, J . Amer. Chem. SOC., 1962, 84, 3593. 2 6 0 V. Franzen, Chem. Ber., 1962, 95, 571. 261 R . Appel and 0. Buchner, Angew. Chem., Internat. Edn., 1962, 1, 332. 2 6 2 J. A. Bell and G. B. Kistiakowsky, J . Amer. Chem. SOC., 1962, 84, 3417. 2 6 3 H. M. Frey, J., 1962, 2293. 2 6 4 H. M. Frey and I. D. R . Stevens, Proc. Chem. SOC., 1962, 79. 2 6 5 H. M. Frey and I. D. R. Stevens, J., 1962, 3865. 2 6 6 H. M. Frey and I. D. R. Stevens, J . Arner. Chem. SOC., 1962, 84, 2647. 2 ' . Franzen, Chem. Ber., 1962, 95, 1964. 6V 2 6 8 C. D. Gutsche, G. L. Bachman, and R. S. Coffey, Tetrahedron, 1962, 18, 617. 26B G. L. Closs and L. E. Closs, Angew. Chem., Internat. Edn., 1962, 1, 334.
242
ORGANIC CHEMISTRY
new or improved methods of generation and new reactions of carbenes have been described. Phenoxy- and various alkoxy-carbenes are formed by a-elimination of hydrogen chloride from chloromethyl ethers with butyl A lithium ;270 phenylthiocarbene is formed ~imilarly.2~1 carbene (phenylcarbene) formed from a sulphur ylid (154) (from benzyldiphenylsulphonium
Ph
tetrafluoroborate and butyl-lithium) has now been trapped with acenaphthylene, to give the adduct ( 155).272 Di(methylthio)carbene, (MeS),C:, is formed from methyl orthothioformate and potas~amide.~73 Carbonylcarbene, :C:C:O, is proposed 274 as an intermediate in the photolysis of isotopically labelled carbon suboxide in the presence of ethylene to explain the isotopic distribution in the major product, allene. The nucleophilic carbene (156), in which two electron-releasing groups are attached t o the bivalent carbon atom, has been studied in detai1;275 adds, for example, t o the elecit trophilic double bond in tetracyanoethylene in good yield.
Alkenylidenecarbenes ( 157) are formed from dialkylprop-2-ynyl chlorides and base (see also p. 216), and have been trapped with olefins:
R,CCI*C=CH
-+
R,CCl*CrC-
++ C R , * M -
R,C=C=C:
(157)
The dimethyl compound (157; R = Me) adds stereospecifically to cis- and trans-but-2-ene; competitive addition t o pairs of olefins shows it t o be electrophilic and about as selective as dibr~mocarbene.,~~ reaction of The allryl-lithiums with methylene chloride appears t o involve formation of monochlorocarbene, followed by combination of this with the lithium cornpound to give an alkylcarbene which rearranges t o an o l e h by hydrogenor alkyl-migration or gives a cyclopropane by intramolecular insertion. 7 The reported 7* insertion of dichlorocarbene, from chloroform and base, into the mercury-halogen bond of phenylmercuric halides is now shown to
U. Schollkopf, A. Lerch, and W. Pitteroff, Tetrahedron Letters, 1962, 241. U. Schollkopf and G. J. Lehmann, Tetrahedron Letters, 1962, 165. 2 7 2 V. J. Hruby and A. William Johnson, J. Amer. Chem. SOC., 1962, 84, 3586. 2 7 3 J. Kine, R . P. Bayer, and G. G. Hammer, J . Amer. Chem. SOC., 1962, 84, 1751. 2 7 4 R . T. Mullen and A. P. Wolf, J . Amer. Chem. Soc., 1962, 84, 3214. 2 7 5 H. W. Wanzlick, Angew. Chem., Internat. Edn., 1962, 1, 75. 2 7 6 H. D. Hartzler, J . Amer. Chem. SOC., 1961, 83, 4990, 4997. 2 7 7 G. L. Closs, J . Amer. Chem. SOC., 1962, 84, 809. 2 7 8 Ann. Reports, 1961, 58, 178.
20
271
243
be simple nucleophilic displacement of halide by the trichloromethyl anion ;279 decomposition of the resulting phenyl(trichloromethy1)mercury in boiling benzene provides a good source of dichlorocarbene.280 Dichlorocarbene has been inserted into the C-H bond of alkyl side chains of aromatic hydrocarbons.281 The conversion of diazoisofenchone (158) into the cyclopropane (159) in boiling benzene in the presence of a large excess of copper bronze is considered to proceed through the carbene formed by loss of nitrogen which rearranges by concerted endo-methyl migration and formation of the cyclopropane ring, i.e., by insertion of this carbene into a carbon-carbon bond. 282 Nitrenes. These electron-deficient neutral nitrogen species, RN: and RN*,isoelectronic with carbenes, are exciting considerable interest and have b e k proposed as intermediates in many photolytic and thermal reactions ; full details of their ingenious use in the synthesis of complex natural products are a~ailable.~83, Photolysis of aliphatic azides (160) gives activated 284 nitrenes (161) which may variously isomerise by lY2-hydrogen shift to imines, abstract hydrogen from the solvent to give amines, or, where structure permits, undergo intramolecular 1$-hydrogen shift followed by cyclisation to pyrrolidines (163).283 A diradical intermediate (162) is favoured for this cyclisation which proceeds with loss of optical activity a t the carbon terminus. The reactivity of carbenes and these nitrenes have been briefly compared.
..
..
Photolysis of (diterpenoid) acid azides gives, together with the corresponding isocyanates, y- or 8-lactams, e.g., (164) gives (165), according to structure and stereochemistry in an analogous manner through the diradical acylnitrenes. Under comparable conditions hexanoic azide gives only hexanamide by hydrogen abstraction.284 The nitrene intermediate Et0.CO.N:
formed in the photolysis of ethyl azidoformate has been efficiently trapped as the cyclohexene adduct (166) ; nitrogen evolution and disappearance of
D. Seyferth and J. M. Burlitch, J. Amer. Chern. SOC., 1962, 84, 1757. Seyferth, J. M. Burlitch, and J. K. Heeren, J. Org. Chem., 1962, 27, 1491. 281 E. K. Fields, J. Amer. Chem. Soc., 1962, 84, 1744. 2 8 2 P. Yates and S. Danishefsky, J. Arner. Chem. SOC., 1962, 84, 879. 283 D. H. R. Barton and L. R. Morgan, J., 1962, 622. 2a4 J. W. ApSimon and 0. E. Edwards, Canad. J. Chem., 1962, 40, 896. * For the reasons given in a footnote in ref. 285 the name nitrenes is preferred to azenes (cf. ref. 286).
279
z80D.
244
ORGANIC CHEMISTRY
the azide were simultaneous, thus the triazoline cycloaddition product is not formed ; furthermore, under the same conditions cyclohexane gave N-cyclohexylurethane in similar high yield. 2 8 5 The rates of thermal decomposition of various halogeno-, nitro-, methyl, and methoxy-substituted phenyl and 2-biphenylyl azides (the latter giving carbazoles in high yield) differed only by a factor of 17 between extremes, and were relatively insensitive to the nature of the solvent; from this and a consideration of the variation in A H $ and A S it is suggested 286 that all these azides, and possibly triarylmethyl azides also, undergo a similar initial cleavage to the nitrene. The same intermediate is probably involved in the conversion of 2-nitrosobiphenyl with triethyl phosphite in cold ben~ e n e , ~ and~possibly of 2-nitrobiphenyl with boiling triethyl p h ~ s p h i t e , ~ ~ ~ 87 into, carbazole in high yield. A study of the kinetics and products of the thermal decomposition of phenyl, p-methoxyphenyl, and cyclohexyl azide in a variety of inert solvents supports the idea of unimolecular decomposition of these azides to intermediates showing typical homolytic reactivity, presumably triplet-state nitrenes ; in unsaturated solvents, however, there is a different reaction, with a lower activation energy but large entropy requirement, which is considered t o involve formation and decomposition of a triazoline.288 The vapour-phase pyrolysis of the unsaturated azides (167) t o the azirines (168),where R = phenyl, o-tolyl, or n-butyl, may involve the respective nitrene intermediate^.^^^
Decomposition of benzenesulphonyl azide (cf. ref. 290) in boiling chlorobenzene saturated with anthracene gave 1- (55%), 2- (5-10%), and 9-benzenesulphonamidoanthracene (15%) rather than predominantly 9substitution expected for normal free-radical or electrophilic substitution; it is suggested that initial attack by Ph*SO,*N:is an addition to an aromatic double bond (mainly l,2),followed by rearrangement to the substitution products.291 The electron paramagnetic resonance observed when dilute solutions of pheny1, o- trichloromethylphenyl ,benzenesulphonyl , and toluene -p-sulphony1 azide are irradiated in polychlorotrifluoroethylene a t 77 O K indicates a ground-state triplet for the derived n i t r e n e ~ . ~ g ~ Reactions of Aldehydes, Ketones, and their Derivatives.-Transamination of alanine 2 9 3 and phenylglycine 294 with pyridoxal proceeds through the
W. Lwowski and T. M. Mattingly, Tetrahedron Letters, 1962, 277. P. A. Smith and J. H. Hall, J. Amer. Chem. SOC.,1962, 84, 480. 2 8 7 (a) P. J. Bunyan and J. I. G. Cadogan, Proc. Chem. Soc., 1962, 78; ( b ) J. I. G. Cadogan and M. Cameron-Wood, ibid., p. 361. 2 8 * P. Walker and W. A. Waters, J., 1962, 1632. 2 8 9 G. Smolinsky, J. Org. Chem., 1962, 27, 3557. 2 9 0 Ann. Reports, 1960, 57, 193. 291 J. F. Tilney-Bassett, J., 1962, 2517. 2 9 2 G. Smolinsky, E. Wasserman, and W. A. Yager, J. Amer. Chem. Xoc., 1962, 84, 3220. 2 9 3 B. E. C. Banks, A. A. D. Diamantis, and C. A. Vernon, J., 1961, 4235; G. M. Fleck and R. A. Alberty, J . Phys. Chem., 1962, 66, 1678. 2 9 4 T. C. Bruice and R. M. Topping, J. Amer. Chem. SOC., 1962, 84, 2448.
285
2s6
C A P O N ,4ND R E E S : R E A C T I O N M E C H A N I S M S
245
Schiffsbase, as (169) + (172), and the rate-limiting step, which for the reaction of alanine has been shown to be general acid-catalysed, is the interconversion of the isomeric Schiffs bases (170) and (171). The transamination of phenylglycine has been shown 29* t o be catalysed by imidazole buffers, but the nature of this catalysis has not yet been determined.
R*CH,O
R*CH(NH2).C02H
RCH=N*CHR.C02H
The pH-rate profile of the hydrolysis of NNN-trimethyl-p-( p-hydroxyphenyliminomethy1)anilinium chloride for the pH range 1-1 1.5 has been measured and the general-acid-catalysis by several buffers investigated.295 The first-order behaviour over the whole pH range and the equality of the rate of disappearance of Schiffsbase (measured spectrophotometrically) and the rate of formation of paminophenol (measured polarographically) at pH 7.36 argued against the incursion of an appreciable concentration of an intermediate. The results may, however, be explained by formation of an intermediate at a low steady-state concentration. The measured rate constant is then a complex function of the acid-dissociation constants of Schiffs base and intermediate and the rate constants for the formation and decomposition of the intermediate. The general acid-catalysis of semicarbazone formation has been investigated.296 Aniline is a nucleophilic catalyst for semicarbazone formation, the reaction proceeding through an intermediate Schiffs base :297
)C=NPh )C=O + Ph*NH2 )C=NPh + H 2 0 + + H2N.NH-CO*NH2 )C=N-NH.CO.NH, + PhoNH, + Slow Fast
Conditions can be found under which the semicarbazide traps all or nearly all of the Schiffs base and hence under these conditions the rate of semicarbazone formation is a measure of the rate of Schiffs base formation. The rates of formation of several Schiffs bases have been measured in this way and the mechanism of the reaction has been discussed.298 The reactivity for enolisation of cycloalkanones in hydrochloric acid90% acetic acid as a function of ring size is 6 > 8 > 5 > 7 > 4;that for enolisation by deuteroxide in dimethylformamide-deuterium oxide is 4 > 5 > 6 > 7.299 The reactivity of the acid-catalysed enolisation of cycloalkyl phenyl ketones is in the order 5 > 4 > 6 > 3 ; for base-catalysed enolisation 3 > 4 > 5 > 6.299 The reactivity sequences for the acidR. L. Reeves, J . Amer. Chem. SOC., 1962, 84, 3332. E. H. Cordes and W. P. Jencks, J . Amer. Chem. SOC., 1962, 84, 4319. 2 9 7 E. H. Cordes and W. P. Jencks, J . Amer. Chem. SOC., 1962,84, 826; Biochemistry, 1962, 1, 773. 2 9 8 E. H. Cordes and W. P. Jencks, J . Amer. Chem. SOC., 1962, 84, 832. 2 9 9 H. Schechter, M. J. Collis, R. Dessy, Yuzi Okuzumi, and A. Chen, J . Amer. 1962, 84, 2905; see also R. D. Campbell and H. M. Gilow, ibid., p. 1440. Chem. SOC.,
295
296
246
ORGANIC CHEMISTRY
catalysed reactions may be correlated with the steric and hybridisation requirements for the conversion of the a-carbon atom from tetrahedral to near-trigonal in the transition state, and for the base-catalysed reactions with the s-character of the carbon-orbital directed toward enolisable hydrogen. The keto-enol tautomerism of oxaloacetic acid has been investigated.300 However, it has been reported that the nuclear magnetic resonance spectrum of oxaloacetic acid in deuterium oxide indicates that at equilibrium 50% is present as the keto-, 8% as the enol, and the rest in some other form. 301 Several other keto-enol reactions have been investigated.302 The mechanism of the acid-catalysed ring expansion of the methyl xylo304 furanosides 303 and of methyl /?-D-ghcofuranoside to the pyranosides in methanol probably involves an acyclic intermediate. It is not possible to determine the steric course of these reactions because of preceding rapid anomerisation of the furanosides. The rates of acid-catalysed hydrolyses of a large number of glycopyranosides305and of two l-thioglucopyranosides 306 have been measured and the results analysed conformationally. It is diflicult to reconcile the positive catalysis by acid of the hydrolysis of aryl a-D-glucopyranosideswith the mechanism proposed by Rydon and his co-workers.307 Prior protonation of the ring-oxygen, as suggested by them, would be expected to hinder, and not to facilitate, the departure of the leaving aryloxy-group. Other reactions which have been investigated include : hydration of mesityl oxide and crotonaldehyde;308 hydration of pyruvic acid ;309 hydrolysis of ketimines ;310 thiosemicarbazone formation ;311 and reaction of hydroxylamine and O-methylhydroxylarninewith carvone.312 Reactions of Carboxylic Acid Derivatives.-Most interest in this field continues to be in the mechanisms of inter- and intra-molecularly catalysed rea~tions.~l3 Butler and Gold 314 have shown that the acetate-catalysis of the hydrolysis of p-nitrophenyl acetate must be mainly general-base-catalysis, and not nucleophilic catalysis with intermediate formation of acetic anhydride as originally thought.516 They showed that, under their reaction
300 301 302
K. Yates, J., 1962, 1927; A. Fischer, J. Packer, and J. Vaughan, ibid., p. 3318; R. P. Bell and R. R. Robinson, Proc. Roy. SOC., 1962, A , 270, 411. 303 C. T. Bishop and F. P. Cooper, Cunad. J. Chem., 1962, 40, 224. 304B. Capon, G. W. Loveday, and W. G. Overend, Chem. and Ind., 1962, 1537. 305 W. G. Overend, C. W. Rees, and J. Sequeira, J., 1962, 3429. 306 C. Bamford, B. Capon, and W. G. Overend, J., 1962, 5138. 3 0 7 A. N. Hall, S. Hollingshead, and H. N. Rydon, J., 1961, 4290; see Ann. Reports, 1961, 58, 176. 308 R. P. Bell, J. Preston, and R. B. Whitney, J., 1962, 1166. M. Eigen, K. Kustin, and H. Strehlow, 2. phys. Chem. (Frunkfurt), 1962, 31,
140.
s1o J. B. Culbertson,
W. D. Kumler, E. Kun, and J. N. Shoolery, J. Org. Chem., 1962, 27, 1165. T Riley and F. A. Long, J . Amer. Chem. Soc., 1962, 84, 522; R. P. Bell and .
B. E. C. Banks, J., 1962, 63; G. W. Kosicki, Cunud. J. Chem., 1962, 40, 1280.
D. Butterfield, 0. Kolewe, and R. Shaw, J. Org. Chem., 1962,
27, 729.
C. M. L. Bender and M. C. Neveu, ibid., p. 5388; (b) E. Gaetjens and H. Morawetz, ibid., 1960, 82, 5328.
311 I . Fiarman and J. D. Gettler, J . Amer. Chem. SOC., 1962, 84, 961. 312 G. Baddeley and K. Brocklehurst, Proc. Chem. Xoc., 1962, 145. 313M. Bender, Chem. Rev., 1960, 60, 53. 5l4 A. R. Butler and V. Gold, J., 1962, 1334. 315 ( a ) T. Bruice and R. Lapinski, J. Amer. Chem. SOC., 1958, 80, 2265;
D.
L.
247
conditions, if acetic anhydride were an intermediate, about 84% should be trapped to give acetanilide when the reaction is carried out in the presence of aniline. Since about 68% of the reaction was proceeding by an acetatecatalysed pathway, about 0.68 x 84% = 57% of the p-nitrophenyl acetate should be converted into acetanilide if all the acetate-catalysed reaction involved acetic anhydride as intermediate. I n fact, about 20y0of the original acetate was found as acetanilide and nearly all this can be accounted for as coming from direct attack of aniline on the ester. The hitherto puzzling difference 315b in the effects of substituents on the intramolecular carboxylate-catalysed hydrolyses of aryl hydrogen succinates and glutarates and the intermolecular acetate-catalysed hydrolyses of aryl acetates thus results from the former reactions being nucleophile-, and the latter general-basecatalysed. The use of the solvent-isotope effect to distinguish between nucleophilic and general base-catalysis has also been explored.316,3l7 According to Bender, Pollock, and Neveu,316 with imidazole and other nitrogen bases general-base-catalysis is associated with an isotope effect kHao/kD,o > 2 and nucleophilic catalysis with virtually no isotope effect. With catalysis by carboxylate ions the distinction is less marked, general-base-catalysed reactions showing a value of kH,O/kD,O > 2 and nucleophile-catalysed reactions a value of about 1.8. The latter effect is a secondary isotope effect and is considered to result from a difference in hydrogen bonding to solvent in the initial and the transition ~ t a t e . ~ l The solvent-isotopeeffect is there* fore not unambiguous in distinguishing between nucleophilic and generalbase-catalysis, but it may sometimes be of use. For instance, imidazole has been found to catalyse the hydrolysis of alkyl acetates (CH,*CO,R) in which the pK, of HOR is less than pKw.319 The solvent-isotope effects on the catalytic coefficients kH,O/kDtO are in the region 2 4 and hence general-base-catalysis is probably operative. Cysteine and other thiols are good nucleophilic catalysts for the hydrolysis of p-nitrophenyl acetate.320 Cysteine is, however, 830 times less effective than the enzyme ficin, the active site of which is thought to involve a thiol group. The pK, of the hydroxyl group of N-acetylserineamide is 13.60 -= 0-05 J a t 25,321 and the nucleophilic reactivity of the anion towards p-nitrophenyl acetate is not abnormally high 322 but can be correlated with those of a number of other alcoholate ions in a normal Brernsted relationship.321 The nucleophilic reactivities of some strongly basic alcoholate ions (e.g., MeO-) are, however, lower than predicted by this relation.323
316
M. L. Bender, F. J. Pollock, and M. C. Neveu, J . Amer. Chem. SOC., 1962, 84,

S. L. Johnson, J . Amer. Chem. SOC., 1962, 84, 1729. C. A. Bunton and V. J. Shiner, J . Amer. Chem. SOC.,1961, 83, 42, 3207,
595.
317
318
3214.
31B T. C. Bruice, T H. Fife, J. J. Bruno, and P. Benkovic, J. Amer. Chem. SOC., . 1962, 84, 3012. 320 J. R . Whitaker, J . Amer. Chem. SOC., 1962, 84, 1900. 321 T. C. Bruice, T. H. Fife, J. J. Bruno, and N. E. Brandon, Biochemistry, 1962, 1, 7. 322 B. M. Anderson, E. H. Cordes, and W. P. Jencks, J . Biol. Chem., 1961, 236, 45. s23 W. P. Jencks and M. Gilchrist, J . Amer. Chem. SOC.,1962, 84, 2910.
248
ORGANIC CHEMISTRY
In an important series of pa.pers Bender and his co-workers 324 have summarised previous work and provided much additional evidence which strongly supports the view that an acyl-enzyme intermediate is involved in the chymotrypsin- and trypsin-catalysed hydrolyses of specific and nonspecific substrates with good and poor leaving groups. Evidence is presented that in this intermediate a serine-hydroxyl group is acylated and that both its formation and its decomposition are general-base-catalysed,probably by an imidazole group. The effect of substituents in the deacylation rates of benzoyl-chymotrypsins has been measured.325 Butler and Golds mechanism 326 for the acetate-catalysed hydrolysis of acetic anhydride, which may be written as (a), has been subjected to kinetic
MeC, OH
0 Me*C< 0.
?-
fast
Products.
analysis by using the stationary-state hypothesis.a2 General-base-catalysis would only be observable if E2[AcOH] k1, if C-0 bond breaking i.e., is much faster than a proton transfer from oxygen to oxygen.326b A more probable mechanism is as scheme (b).327 The hydrolysis of pivalic anhydride is catalysed by pivalate ions in a similar manner to the catalysis of acetic anhydride hydrolysis by acetate ions.328 Pyridine, however, is at least a 400-fold weaker catalyst for the hydrolysis of pivalic anhydride than of acetic a n h ~ d r i d e . 3 These results illustrate the difference in steric ~~ requirements for nucleophilic and general-base-catalysis.329 The mechanism of the reaction of imidic esters (173) with amines has been investigated under conditions where the ratio of the concentration of
<
EtO*CR:NH+ R*NH,+EtO*CR(NH,)*NHR HN:CR*NHR + (173) (174)

3 2 4 M. L. Bender, G. R . Schonbaum, and B. Zerner, J. Amer. Chem. Soc., 1962, 84, 2540, 2562; M. L. Bender and B. Zerner, ibid., p. 2550; M. L. Bender and E. T. Kaiser, ibid., p. 2556; M. L. Bender and G . A. Hamilton, ibid., p. 2570; M. L. Bender and Kaname Nakamura, ibid., p. 2577; M. L. Bender, ibid., p, 2582; F. Kezdy and M. L. Bender, Biochemistry, 1962, 1, 1097. 32s M. Caplow and W. P. Jencks, Bzochemistry, 1962, 1, 883. 3 2 6 A .R. Butler and V. Gold, (a)J., 1961, 2305; ( b ) J . , 1962, 2212. 3 2 7 S. L. Johnson, J. Amer. Chem. SOC., 1962, 84, 1729.
328
329
A. R. Butler and V. Gold, J., 1962, 976. See V. Gold in ref. l(i), pp. 194 et seq.
249
amine to ester is high.330 The reaction has a pH-rate profile with a maximum. The measured rate constant is probably a complex function of equilibrium constants for the protonation of ester and amine and rate constants for the formation and decomposition of the tetrahedral intermediate (174). At low acidities the rate is controlled by the rate of attack of amine on the ester but with increasing acidity the rate of decomposition of the intermediate (174) makes an increasingly important contribution to the measured rate. The pH-rate profile for the imidazole-catalysed hydrolysis of 8-thiovalerolactone is a bell-shaped curve.331 Such curves are found with reactions whose rates depend on two protolytic equilibria which for this reaction are thought to be the protonation of imidazole and the protonation of a thiol group in an intermediate. The apparent pK, of the thiol group calculated from the pH-rate profile is 1.68 units less than the measured pK, of 6-thiolvaleramide. The suggested mechanism is shown in the annexed scheme; kinetic analysis of this shows that the apparent dissociation constant calculated from the pH-rate profile is not K,, but K,K4k4/k,, and hence
H N ~ N
u +
& .
6
0
L l +
the discrepancy is explained. Care should therefore be taken in identifying apparent pK,s determined from pH-rate profiles of complex organic and enzymic reactions with the pK,s of catalysing groups. A striking example of intramolecular nucleophilic catalysis has been observed by Bender and
,OH
OH
--.f.
OH-+
(175)
ac;/c=o
Me0
L+
f+ J
\.
--t
Products
c/
?o-
330 M. J. Hunter and M. L. Ludwig, J . Arner. Chern. SOC., 1962, 84, 3491; E. S. Hand and W. P. Jencks, ibid., p. 3505. 331 T. C. Bruice and J. J. Bruno, J . Amer. Chem. SOC., 1962,84,2128; also see F. H. Westheirner and M. L. Bender, ibid., p. 4908.
250
ORGANIC CHEMISTRY
S i l ~ e r ~ ~ 2 have shown that methyl o-formylbenzoate is hydrolysed in who alkaline solution lo5 times faster than expected. The hydrolysis is thought to involve attack of hydroxide ion on the formyl group to yield an intermediate (175) which then undergoes an intramolecular reaction. A similar mechanism has been suggested 333 for the hydrolysis of some methyl o-benzoylbenzoates but here the rate acceleration is much smaller. The high rate of reaction of 1'-m-hydroxybenzylferrocenecarboxylic acid with diphenyldiazomethane is thought t o result from intramolecular acid catalysis, the transition state being as ( 176).334
Ph -.C.-'Ph
( I :76)
The pH-rate profile for the hydrolysis of N - (o-carboxybenzoy1)anthranilic acid (177) is a bell-shaped curve, suggesting that one of the singly ionised forms is more reactive than the un-ionised or doubly ionised f 0 r m . ~ ~ 5 A singly ionised form would be expected t o undergo hydrolysis by a mechanism involving intramolecular bifunctional catalysis.336 The hydrolysis of y-hydroxybutyramide proceeds with intramolecular nucleophilic catalysis by the hydroxyl or ionised hydroxyl group [see scheme (c)] in neutral and alkaline 337 as well as in acid solution.338 The hydrolysis, in aqueous sulphuric acid, of o-benzamido-NN-dicyclohexylbenzamide (178) which is at
0
0
-0,
,Nt
least lo4 times faster than that of NN-dicyclohexylbenzamide must also involve intramolecular nucleophilic catalysis 339 [see (178) -+(lSl)]. Full details of Bruice and Fife's investigation on the intramolecular catalysis of ester hydrolysis have now been published.34o Several other examples of such catalysis have been rep0rted.340~ A general discussion of the aeid-catalysed hydrolysis of esters and amides
M. L. Bender and M. S. Silver, J. Amer. Chem. SOC., 1962, 84, 4589. M. S. Newman and Shinzaburo Hishida, J. Amer. Chem. Soc., 1962, 84, 3582. 334 W. F. Little and R. Eisenthal, J. Amer. Chem. Soc., 1961, 83, 4936. 335 H. Morawetz and J. Shafer, J. Amer. Chem. SOC., 1962, 84, 3783. 336 H. Morawetz and I. Oreskes, J . Amer. Chem. Soc., 1958, 80, 2591. 3 3 7 T. C. Bruice and F. H. Marquardt, J. Amer. Chem. SOC.,1962, 84, 365. 338 L. Ziirn, Annalen, 1960, 631, 56. 339 T. Cohen and J. Lipowitz, J . Amer. Chem. SOC., 1961, 83, 4866. 3 4 0 ( a ) T. C. Bruice and T. H. Fife, J. Amer. Chem. SOC., 1962, 84, 1973; see Ann. Reports, 1961, 58, 180; (b) S. M. Kupchan, P. Slade, R. J. Young, and G. W. A. Mane, Tetrahedron, 1962, 18, 499.
332
333
CAPON AND R E E S : R E A C T I O N M E C H A N I S M S
251
t: o
(I 78)
N (C ' 6~
,,,
HO' .'N(C6
(1'79)
aNyP
COZH (181)
in terms of Bunnett's w values 341 has been made by Martin.342 It seems likely that water functions both as a nucleophile and as a proton-transfer agent in these reactions.342 Bunnett 341 has derived for the generalised acid-catalysed reaction : S(H,O), H(H,O)n+* SH(H,O),+ (s n - p)H,O
+ + + equilibrium constant ( K s ~ + ) - l
( t - p)H,O
SH(H,O)p++
a $(H,O)t++Products rate constant k
the rate equation: Rate = k,[SIst
where kv = measured fist-order rate constant and [SIst = [S] [SH+]. Since for most reactions the variation of the activity coefficients of substrate and transition state with acid concentration are unknown, this equation must be simplified. This is done by assuming that the ratio of activity coefficients of species (including the transition state) of like charge is independent of the medium and by substituting for [H(H,O),+] in terms of H,. For a slightly protonated substrate the equation log kv H , = w log aH20 Constant H,) against log u H p O should be a is obtained and hence a plot of (log kv straight line the slope of which, w ,is identified with the difference in hydration of the transition and the initial state on a scale set by the "water balance " in protonation of an indicator base. Bunnett 341 has calculated w values for about 100 reactions and shown that they fall into three groups characteristic of mechanism. Hence Bunnett plots provide an additional empirical criterion of mechanism when Hammett plots are ambiguous (e.g., of non-unit slope) and have a stronger theoretical justification. Intending users should, of course, consult the original papers 341 but should note that Bunnett plots generally show considerably greater scatter than Hammett plots and that high acid concentrations are advisable (e.g., >4~-HC10,) since it is only then that the activity of water changes rapidly with acid concentration. The rates of hydrolysis and the activity coefficients of acetic anhydride
341
342
J. F. Bunnett, J. Amer. Chern. SOC.,1961, 83, 4956, 4968, 4973, 4978. R. B. Martin, J. Amer. Chern. SOC.,1962, 84, 4130.
252
ORGANIC CHEMISTRY
in aqueous electrolyte solutions have been determined.343 This enables the salt effects on the rates to be dissected into effects on the activity coefficients of initial and transition states. Both activity coefficients vary. The effects of a large number of added salts on the rates of hydrolysis of the conjugate acid of l-acetylimidazole and of the 1-acetyl-3-methylimidazoliwn cation have been determined.344 The rates are decreased by all the salts studied except sulphates and fluorides. Although, a t the concentrations used, variation of the activity of water is undoubtedly important, the salt effects cannot be explained by this alone, and effects on the activity coefficients of initial and transition states must be invoked. Partly protonated poly-(4-vinylpyridine) in an ethanol-water mixture is a more effective catalyst than 4-picoline or either non-protonated or highly protonated poly- (4-vinylpyridine) in the solvolysis of nitrophenyl acetates bearing a negatively charged substituent (e.g., It is a poorer catalyst than 4-picoline for the solvolysis of 2,4-dinitrophenyl acetate, an electrically neutral substance. These results suggest that there is a polymercounter-ion electrostatic interaction which increases the local concentration of anionic substrate in the region of the polymer coil. Introduction of t-butyl groups ortho to the hydroxyl group of p-hydroxybenzonitrile and p-hydroxybenzamide decreases the hydrolysis rates in alkaline solutions thirty-fold. 346 This is attributed to an increased density of negative charge a t the ring-carbon adjacent to the site of nucleophilic attack, resulting from steric hindrance to solvation a t the oxygen end of the phenoxide ambidentate ion. I n contrast t o the reactions of 1-substituted 2,4-dinitrobenzenes with piperidine in methanol 3 4 7 the reactions of benzoyl halides with morpholine in cyclohexane show a large " element " effect: 348
Benzoyl halide Ic, (1. mole-1 sec.-l)
F
1.06
c 1 2-64 X lo3
Br
6.66 X
lo4
I
2.39 x lo5
The rates of solvolyses of cycloalkyl chloroformates in formic acid and aqueous acetone which yield mixtures of cycloalkene and cycloalkanol are not very sensitive t o ring ~ i z e . ~ ( -)-l-Methylheptyl chloroformate gave ~9 (-)- l-methylheptanol with 90% retention of configuration. These results rule out a mechanism (d) involving an intermediate carbonium ion and are interpreted in terms of an intermediate acylium ion [cf. (e)].
-O*COCl+ R O H CO, HC1 (d) RO.COCl+ R+ -+ ( e ) ROCOCl +RO*CO+ C1- -+ RO. COOOH R O H
+ CO, + HCI
The rates of hydrolysis of carboximidoyl chlorides 350 in aqueous acetone show a strong common-ion retarding effect, are accelerated by electronreleasing substituents, and retarded by electron-withdrawing substituents,
C. A. Bunton, N. A. Fuller, S. G. Perry, and I. H. Pitman, J., 1962, 4478. S. Marburg and W. P. Jencks, J . Amer. Chem. SOC.,1962, 84, 232. R. L. Letsinger and T. J. Savereide, J . Amer. Chem. SOC., 1962, 84, 3122. 346 L. A. Cohen and W. M. Jones, J . Amer. Chem. SOC., 1962, 84, 1625. 347 J. F. Bunnett, E. W. Garbisch, and K. M. Pruitt, J . Amer. Chem. SOC., 1957, 79, 385. 3 4 8 M. L. Bender and J. M. Jones, J . Org. Chem., 1962, 27, 3771. 349 M. Green and R. F. Hudson, J., 1962, 1076. 3 5 0 I. Ugi, F. Beck, and U. Fetzer, Chem. Ber., 1962, 95, 126.
343 344
345
253
and increase rapidly with increasing water content of the solvent. The rate of liberation of chloride ion is increased by addition of amines and the falling off of the first-order rate constants is so reduced. These results were explained by a mechanism (f) involving ion pairs, but in the Reporters view they indicate that return from kinetically free ions is occurring.
(f) C1.CR:NH
+ [R*C%NH+Cl-] Products +
Ion pair
The von Braun reaction of an N-alkylamide with thionyl chloride or phosphorus pentachloride to yield the alkyl chloride and a cyanide, probably involves 351 the imidoyl chloride (182) as intermediate since this may be isolated under the reaction conditions and yields halide and cyanide on
RCO-NHR -+ R*CCl:NR+ROC=
(182)
+ RC1
further treatment. ( -)-N-cc-Methylbenzylacetamide yields an almost inactive chloride under non-racemising conditions.351 The mechanisms of the following reactions have also received attention : hydrolysis of 2-substituted 2-thiazolines and 2-methyl-2-oxazoline intra;352 molecular S-0 and S-N acetyl transfer ;353 acid-catalysed hydrolysis of N butyryl-y- butyrolactam ;35* hydrolysis of 2-dimethylaminoethyl hydrogen phthalate ;355 solvolysis of y-phenyltetronic acid enol esters ;3Fj6 hydrolysis of B-benzyl esters of N-benzyloxycarbonylaspartic amides and peptides ;357 reaction of substituted benzoic acids with diazodiphenylmethane;358 alkaline hydrolysis of methyl 2,4,6-tri-t-butylbenzoate;359 hydrolysis of (+)-4methyl-4-hexanolactone;360acid-catalysed hydrolysis of NN-diarylacetamidines ;361 and acetolysis of acetyl Other Reactions.-Lacl< of space has prevented discussion of certain topics, including important investigations of the steric course of a displacement reaction at a phosphoryl centre,363 of a free-radical Wagner-Meerwein rearrangement 364 and related reactions,365 of the occurrence 366 and nonoccurrence 30 of neighbouring-group participation in radical reactions, of
W. R. Vaughan and R. D. Carlson, J . Amer. Chem. SOC., 1962, 84, 769. R. B. Martin and A. Parcell, J . Amer. Chem. SOC., 1961, 83, 4830, 4835. 353 R. B. Martin and R. I. Hedrick, J . Amer. Chem. SOC., 1962, 84, 106. 3 5 4 R. L. Hansen and W. 0. Ney, J . Org. Chem., 1962, 27, 2059. 3 5 5 J. A. Shafer and H. Morawetz, J . Org. Chem., 1962, 27, 2269. 3 5 6 A. Kirkien-Konasiewicz and A. Maccoll, J., 1961,5421 ; A. Kirkien-Konasiewicz, J., 1961, 5430. 3 5 7 S . A. Bernhard, A. Berger, J. H. Carter, E. Katchalski, M. Sela, and Y. Shalitin, J . Amer. Chem. SOC., 1962, 84, 2421. 3 5 8 N. B. Chapman, J. Shorter, and J. H. P. Utley, J., 1962, 1824. 3 5 9 L. R. C. Barclay, N. D. Hall, and G. A. Cooke, Canad. J . Chem., 1962, 40, 1981; cf. Ann. Reports, 1961, 58, 181. 3 6 0 R. Sandberg, Acta Chem. Scand., 1962, 16, 1124. 361 R. H. De Wolfe and J. R. Keefe, J . Org. Chem., 1962, 27, 493. 362R. Howald, J . Org. Chem., 1962, 27, 2043. A. 363 M. Green and R. F. Hudson, Proc. Chem. SOC., 1962, 307. 3 6 4 J. A. Berson, C. J. Olsen, and J. S. Walia, J . Amer. Chem. SOC., 1962, 84, 3337. 3 6 5 J. A. Berson and C. J. Olsen, J . Amer. Chem. SOC., 1962, 84, 3178; M. M. Martin and D. C. De Jongh, ibid., p. 3526; S. J. Cristol, J. R. Douglass, W. C. Firth, and R. E. Krall, J . Org. Chem., 1962, 27, 2711. 366 W. G. Bentrude and J. C. Martin, J . Amer. Chem. SOC., 1962, 84, 1561 ; J. C. Martin, D. L. Tuleen, and W. G. Bentrude, Tetrahedron Letters, 1962, 229; J. C. Anderson and C. B. Reese, ibid., 1962, 1.
351
352
254
quantum-mechanical tunnelling in proton-transfer between acetic acid and the anion of 2,4,6-trinitrotoluene,36S and of nucleophilic rea~tivities.3~~ Attention may also be drawn to discussions of mechanisms of reactions in dipolar aprotic solvents,370 unexpected allylic rearrangement^,^^^ inhibition of autoxidation of organic and of the relation between stereochemistry and reaction mechanism of organosilicon compounds.373
4. GENERAL METHODS
B. C. C. W. R.
Reduction.-CataZytic hydrogenation. An improved procedure for selective hydrogenation of cyclohex-3-enecarboxaldehydeto cyclohexanecarboxaldehyde (81yo)involves untreated, commercial 5% palladium-charcoal. 1 Tetramethylthiourea is a particularly effective selective poison in the Rosenmund reaction. Contrary to general impression, 10% palladium-charcoal can be used to reduce pyridines to piperidines, and the catalyst is not readily poisoned by the base.3 Alternatively, 5% rhodium-charcoal may be used, provided that sufficient catalyst is employed to overcome poisoning by the piperidines.4 a-Substituted benzyl alcohols and their ethers yield the corresponding cyclohexane derivatives when hydrogenated over 5% rhodium-alumina ; other catalysts promote hydrogen~lysis.~ D-Mandelic acid is reduced to D -hexahydromandelic acid (94yo without racemisation. ) The inversion of configuration at position 3 when Sa-phenylcholestan3p-01 is converted into 3p-phenylcholestane with Raney nickel in boiling ethanol is now shown to involve the nickel catalyst, and at room temperature the reaction yields 3a-phenylcholestane. Ruthenium, rhodium, and platinum salts liberate hydrogen from aqueous or ethanolic sodium borohydride, yielding finely divided metals which are highly active catalysts for the hydrogenation of unsaturated compounds. I n the presence of active charcoal, supported catalysts are formed. With such a supported platinum catalyst, aromatic nitro-compounds are reduced to aromatic amines at room temperature and pressure. A simple apparatus is described for such catalytic reductions.' Platinum of even higher activity is obtained from hexachloroplatinic acid and trimethylsilane.8
C. Ruchardt and R. Hecht, Tetrahedron Letters, 1962, 957, 961. E. F. Caldin and E. Harbron, J., 1962, 3454. 36s R . F. Hudson, Chimia Switx., 1962, 16, 173; J. 0. Edwards and R . G. Pearson, J . Amer. Chem. SOC.,1962, 84, 16. * 3 7 0 A .J. Parker, Quart. Reviews, 1962, 16, 176. 371 W. G. Young, J. Chem. Educ., 1962, 39, 455. 372 K. U. Ingold, Chem. Rev., 1961, 61, 563. 373 L. H. Sommer, Angew. Chem., Internat. Edn., 1962, 1, 143. 1 H. E. Hennis and W. B. Trapp, J . Org. Chem., 1961, 26, 4678. S. Affrossman and S . J. Thomson, J., 1962, 2024. 3 G. N. Walker, J. Org. Chem., 1962, 27, 2966. 4M. Freifelder, R. M. Robinson, and G. R. Stone, J . Org. Chem., 1962, 27, 284. J. H. Stocker, J. Org. Chem., 1962, 27, 2288. E. W. Garbisch, jun., J. Org. Chem., 1962, 27, 3363. 7 H. C. Brown and C. A. Brown, J. Amer. Chem. SOC., 1962, 84, 1493, 1494, 1495, 2827, 2829; H. C. Brown and K. Sivasankararr, ibid., p. 2828. * R. W. Bott, C. Eaborn, E. R. A. Peeling, and D. E. Webster, Proc. Chem. SOC., 2962, 337.
367
368
B A R K E R A N D G R A Y : G E N E R A L METHODS
255
Hydroboronation. The quest for selective hydroboronating and reducing agents has led to further studies of hydroboronation of hindered 01efins.~ Methods for preparing the borines CHPriBut*BH, and CMe2BuS*BH2, dicyclohexylborine, bis-trans-2-methylcyclopentylborine, and bis- trans - 2methylcyclohexylborine are reported. Hydroboronation of 3,3,3-trifluoropropeneby diborane in the gas phase gives addition of boron mainly a t the 2-position, but the reaction is complicated by transfer of fluorine from carbon to boron.1 Amongst other products, 1 ,l-difluoropropene is obtained by the following process :
Apopinene is converted stereospecifically into trans-isonopinolby oxidation of the hydroboronation adduct formed with diborane. l1 Quantitative, homogeneoushydrogenation of cyclohexeneandoct-l-ene by hydrogen under pressure occurs at high temperatures in the presence of trithe n-butylborine. With cis-1,4-polybutadieneY method gives a high-density polyethylene. Monohydroboronation of simple aliphatic dienes occurs to only a limited extent under controlled conditions. Cyclic dienes undergo monohydroboronation more readily, and cyclohexa-l,3-diene gives 60-65y0 of cyclohex-2-en01and 3 5 4 5 % of ~yclohex-3-enol.~~ using bis-1,Z-dimethylBy propylborine for bishydroboronation of terminal dienes, the yield of am-diolis improved, as the formation of isomeric diols resulting from addition of the boron at a non-terminal carbon atom is limited.14 Butadiene gives 90% of butane-1,4-diol, compared with 65-76y0 obtained on using diborane. I n certain cases in which the double bonds have different environments, use of bis-l,2-dimethylpropylborine leads to monohydroboronation. Thus, penta-l,3-diene gives pent-3-en01in good yield.l* The conversion of -CH,*C:O into -CH:CH- is achieved via the hydroboronation adduct of the enol acetate. This undergoes elimination when heated with acetic anhydride. I n this way, a 60:/, yield of cholest-2-eneis obtained from cholestan-3-one.15 Hydroboronation of aliphatic and aromatic nitriles with trimethylamineH. C. Brown and A. W. Moerikofer, J . Amer. Chem. SOC.,1962, 84, 1478. J. R . Phillips and F. G . A. Stone, J . , 1962, 94. l1 Y . Chr&ien-Bessi&re, Compt. rend., 1962, 255, 943. l2 E. J. DeWitt, F. L. Ramp, and L. E. Trapasso, J . Amer. Chem. SOC., 1961, 83, 4672. l3 G. Zweifel, K. Nagase, and H. C. Brown, J . Amer. Chem. SOC., 1962, 84, 183. l4 G. Zweifel, K. Nagase, and H. C. Brown, J . Amer. Chem. Soc., 1962, 84, 190. l5 L. Caglioti, G. Cainelli, G . Maina, and A. Selva, Guzzetta, 1962, 92, 309.
lo
256
ORGANIC CHEMISTRY
t-butylborine yields products, R*CH:N*BHBut, which exist as nitrogenbridged, cyclic dimers. l6 A convenient route to amine-borines is as follows:17
B(OPh),
NEt + A1 + $Ha4H,B,NEt, + Al(OPh),.
The high yields (Me3N 99% ; Et3N 92% ; Ph-NMe, 60%) could facilitate the use of these compounds in preparing trialkylborines from olefins. An excess of trimethylamine-borine in acetic acid reduces Schiffs bases to acetylated secondary amines.l* Lithium aluminium hydride. Lithium aluminium hydride reduces 17a721-cyclicacetals, ketals, and orthoesters (1) of corticosteroids with the dihydroxyacetone side chain (2)to secondary alcohols (3), which are hydrolysed to 17a,20a,21-triols (4). I n this way, 17a,20a,21-trihydroxypregn-4en-3-one has been prepared quantitatively.19
Reduction of steroidal 12,20-diketones by lithium aluminium hydride in tetrahydrofuran yields predominantly the 12/3,20~-dihydroxy-derivatives ; a 12a-acetoxy-20-ketone gives mainly the 20/3-alcoho1.20 Lithium aluminium hydride reduces 18+20-lactones of pregnen-18-oic acids to the corresponding hemiacetals. From one of the reduction products, 21-deoxyaldosterone has been prepared. 2 1 The use of lithium aluminium hydride in conjunction with Lewis acids has been further investigated. With boron trifluoride-ether complex, 38acetoxy-steroids are reduced to 38-ethoxy-derivatives. 2 2 Extension of this reaction to d-lactones yields tetrahydropyran derivatives. Cyclic ethers are also produced from d-lactones by using diborane-boron trifluoride-ether,22 whereas diborane itself yields the cyclic hemiacetals. 23 Lithium aluminium hydride-aluminium chloride reduces acetals and ketals to ethers in high yield; in the absence of the Lewis acid, no reduction occurs.24 Aluminium hydride is a more selective reducing agent than lithium aluminium hydride. Systems such as Ph*CH:CH*CHOand Ph*CiC*CO,Meare selectively reduced by lithium aluminium hydride only by careful control of the reaction; aluminium hydride does not attack the multiple bond even
l6
l7 18 lB
2o 21
M. F. Hawthorne, Tetrahedron, 1962, 17, 117. E. C. Ashby and W. E. Foster, J. Amer. Chem. SOC.,1962, 84, 3407. J. H. Billman and J. W. McDowell, J. Org. Chem., 1962, 27, 2640. R. Gardi, R. Vitali, A. Ercoli, and W. Klyne, Tetrahedron Letters, 1962, 189.
C. R . Engel, S. Rakhit, and W. W. Huculak, Canad. J. Chem., 1962, 40, 921. K. Heusler and A. Wettstein, Helv. Chirn. Acta, 1963, 45, 347. 2 2 G. R. Pettit and T. R. Kasturi, J . Org. Chem., 1961, 26, 4553, 4557. 23 G. R. Pettit, T. R. Kasturi, B. Green, and J. C. Knight, J. Org. Chem., 1961, 26, 4773. 2 4 E. L. Eliel, V. G. Badding, and M. N. Rerick, J. Amer. Chem. SOC., 1962, 84, 2371.
BARKER A N D G R A Y : U E N E R A L METHODS
257
under vigorous conditions, and this may provide a useful pathway to unsaturated alcohols.25 Lithium dihydro-1-pyridylaluminium hydride reduces diary1 ketones more readily than dialkyl ketones, the reverse order to that shown by sodium borohydride ; differential reduction of the diketone ( 5 ) has been achieved.26
Li[C6H,NAlH,]
Ph-CO*C,H4*CH ,*COMe ,*CH

(5)
\% I&
Ph *CH (OH)*C,H,*CH ,*CH,-COMe Diol
Ph*CO*C,H,*CH,*CH,.CHMe*OH + Diol
Alkali borohydrides. The reduction of a-hydroxyimino-ketones t o a-hydroxyimino-alcohols is achieved more selectively and in better yield with potassium borohydride than with lithium aluminium hydride.27 The selectivity of reduction of steroid carbonyl groups by sodium borohydride may be altered by the solvent. Thus in anhydrous propan-2-01,progesterone is reduced to 3B-hydroxypregn-4-en-2O-oney whereas in pyridine 3/l-hydroxy5a-pregnan-20-oneis formed. However, with 21-fluoroprogesterone,sodium borohydride in pyridine brings about exclusive reduction of the 20-carbonyl gr0up.~8 The ratio of the cis- and trans-isomers of 3,3,5-trimethylcyclohexanol is also affected by the solvent in the reduction of 3,3,5-trimethylcyclohexanone with sodium borohydride.29 Sodium borohydride-boron trifhoride readily converts ethyl 2-naphthyl ketone and the corresponding alcohol into 2-pr0pylnaphthalene.~~ 10% Palladium-charcoal is a more convenient catalyst than bipyridylcobalt complexes for the reduction of aromatic nitro-compounds to aromatic amines by sodium borohydride. On average, the amines are obtained in 70% yield. The catalyst is without effect on lithium aluminium hydride which gives azobenzene from nitrobenzene.31 The stability of nitro-groups to sodium borohydride in the absence of a catalyst has been used to advantage in the reduction of certain polynitro-aromatic compounds to the polynitrocyclo-alkanes or -alkenes.32 The reducing properties of long-chain, quaternary ammonium borohydrides in hydrocarbon solvents have been investigated and, in general, found to be similar to those of alkali borohydrides in polar or oxygenated solvents.33 Other methods. The electrolytic reduction of organic compounds 34 and the use of hydrazine as a reducing agent for olefins have been reviewed.35
M. J. Jorgenson, Tetrahedron Letters, 1962, 559. P. T. Lansbury and J. 0. Peterson, J. Amer. Chem. Soc., 1962, 84, 1756. 2 7 S. S a m 6 and P. Freon, C m p t . rend., 1962, 254, 1643. 28D. Kupfer, Tetrahedron, 1961, 15, 193. H. Haubenstock and E. L. Eliel, J . Amer. Chem. Soc., 1962, 84, 2368. 30 G. R. Pettit, B. Green, and P. Hofer, Proc. Chem. SOC., 1962, 357. 31T. Neilson, H. C. S. Wood, and A. G. Wylie, J., 1962, 371. 32 T. Severin and R. Schmitz, Chem. Ber., 1962, 95, 1417. 3 3 E. A. Sullivan and A. A. Hinckley, J. Org. Chem., 1962, 27, 3731. 34 F. D. Popp and H. P. Schultz, Chem. Rev., 1962, 62, 19. 3 5 F. Aylward and M. Sawistowska, Chem. and Ind., 1962, 484.
25 26
258
ORGANIC CHEMISTRY
I n boiling ether, under pure nitrogen, reductive fission of olefins of the type Ph*CR:CRR occurs with sodium hydrazide. A nitrogen-free and a nitrogen-containing fragment are produced, e.g., styrene gives toluene (81yo). 36 . Arange of Wolff-Kishner reductions has been achieved at room temperature by using dimethyl sulphoxide as solvent.37 9,10-Dihydro-9,10- bi-iminoanthracene * and hydroxylamine-0sulphonic acid 39 appear to be alternative sources of di-imide for the cis-hydrogenation of certain multiple bonds. The view that reduction of cyclic ketones by sodium in alcohol or by lithium in liquid ammonia-alcohol gives almost exclusively the thermodynamically more stable equatorial hydroxyl group has been questioned. Among other examples, 12-oxocholanic acid and cholan-12-one give predominantly products containing the 12-axial hydroxyl group ; so caution is indicated in using the method to assign configurations.40 Sodium or lithium in liquid ammonia cleaves vinylic sulphides, giving olefins with greater than 90% retention of configuration, but cleavage with lithium in methylamine is not stereo~pecific.~~ Triethyl phosphite reduces 2-nitrosobiphenyl to carbazole under mild conditions; other related reductive cyclisations have been achieved starting with the nitro-compounds.42 A new, advantageous synthesis of N-monosubstituted hydroxylamines is provided by reducing the oxime with diborane in tetrahydr~furan.~~ Oxidation.-Liquid-phase oxidation by molecular oxygen,44 controlled gaseous oxidation of organic oxidation of organic compounds by metal ions and complexes,46 oxidation of olefins in the presence of palladium chloride,47 and recent developments in the oxidation of aromatic hydrocarbons 48 have been reviewed.
CH2:C:CH2
+
6
0 ,
HC-C?
II .o HC-CO
36
oc
co
oc
T. Kauffmann, H. Henkler, C. Kosel, E. Rauch, J. Schulz, and R. Weber, 1, 456. 37 D. J. Cram, M. R. V. Sahyun, and G. R. Knox, J. Amer. Chem. SOC., 1962, 84, 1734. 3 8 E. J. Corey and W. L. Mock, J. Amer. Chem. SOC., 1962, 84, 685. 39 R . Appel and W. Biichner, Annalen, 1962, 654, 1. 40 J. W.Huffman, D. M. Alabran, and T. W. Bethea, J. Org. Chem., 1962, 27, 3381. 41 W.E. Truce and J. J. Breiter, J . Amer. Chem. SOC., 1962, 84, 1623. 4 2 P . J. Bunyan and J. I. G. Cadogan, Proc. Chem. SOC.,1962, 78; J. I. G. Cadogan and M. Cameron-Wood, ibid., p. 361. 4 3 H.Feuer and l . F. Vincent, jun., J. Amer. Chem. SOC., 3 1962, 84, 3771. 4 4 G. H. Twigg, Chem. and Ind., 1962, 4. 4 5 C. F. Cullis, Chem. an,d I n d . , 1962, 23. 4 6 R . G. R . Bacon, Chem. and Ind., 1962, 19. 4 7 J. Smidt, W.Hafner, R. Jira, R . Sieber, J. Sedlmeier, and A. Sabel, Angew. Chem., Internat. Edn., 1962, 1, 80; J. Smith, Chern. and Ind., 1962, 54. 48R. Landau and R. W. Simon, Chem. and Ind., 1962, 70.
Angew. Chem., Internat. Edn., 1962,
B A R K E R AND G R A Y : G E N E R A L METHODS
259
Tetracyanoethylene is effective in dehydrogenating non-conjugated cycloalkadienes.49 Bromine is advantageous for aromatising certain octahydronaphthalene derivatives without loss of functional groups, thereby increasing the utility of the ready synthesis of such compounds from allene and a d i e n ~ p h i l e . ~ ~ A novel dehydrogenation of alcohols to aldehydes or ketones (25--.08y0) is achieved by lithium in ethylenediamine.51 The preparation of peracids of 93-99% purity in 85-97% yield by treating a slurry or solution of an aliphatic or aromatic carboxylic acid in methanesulphonic acid with 90-95y0 hydrogen peroxide is an advance on other methods. Peracetic acid oxidises alkylhydrazones or aromatic aldehydes to the cis-azoxy-compounds.53Unlike trifluoroperacetic acid, permaleic acid may be used in unbuffered solution for a variety of oxidation^.^^ Oxidation of 2-allylcyclohexanone (6) by benzonitrile-hydrogen peroxide gives the Beto-epoxide (7) when the reaction is carried out at pH 8, whereas more acidic conditions involving peracetic acid result in the formation of the lactone (8).55 The utility of this epoxidation technique is shown by the
Q
o
(1,O)
1, Ph*CN-H,O,.
2, AcOZH.
formation of the spiro-epoxide (9) in 73% yield from methylenecyclohexane. I n three cases, contractions of six- t o five-membered rings are achieved by heating 2-acylcyclohexanones (10) with hydrogen peroxide in t-butyl alcohol containing a trace of sulphuric acid. When R = R' = H, ring open-
.
I n n n ~ o \i
R=H.R'=
I
Me
Me
R=H, R'= Ph
R=Me,R'=
[a'v-al / u )
ing occurs and pentaiie-l,5-dicarboxylicacid is the main product. 2-Acetylcyclopentanone gives cc-methyladipic acid (93%) ; cyclobutanecarboxylic acid is not formed. Pentane-2,4-dione and its 3-methyl derivative do not undergo oxidative rearrangement , but 3,3-&methylpentane-2,4-dione gives pivalic acid (76%).56
D. T. Longone and G . L. Smith, Tetrahedron Letters, 1962, 205. 0. W. Webster and W. H. Sharkey, J . Org. Chem., 1962, 27, 3354. 61 S. Smith, R. Thompson, and E. 0. Woolfolk, J . Org. Chem., 1962, 27, 2662. 6 2 L. S. Silbert, E. Siegel, and D. Swern, J . Org. Chem., 1962, 27, 1336. 63 B. T. Gillis and K. F. Schimmel, J . Org. Chem., 1962, 27, 413. 6 4 R. W. White and W. D. Emmons, Tetrahedron, 1962, 17, 31. 6 6 G. B. Payne, Tetrahedron, 1962, 18, 763. 6 6 G. B. Payne, J . Org. Chem., 1961, 26, 4193.
49
6o
260
ORGANIC CHEMISTRY
Nickel peroxide oxidises primary alcohols in aqueous alkali to the carboxylic acids, whereas carbonyl compounds are obtained from primary and secondary alcohols in organic solvents.5 7 Sodium metaperiodate is of general utility for oxidising sulphides to sulphoxides, the lowest yield in thirteen cases being 65y0.58 Oxidation of salts of mononitroalkanesby neutral permanganate can have advantages over the acid-catalysed decomposition of such salts. 59 Oxidation of aldehyde or ketone hydrazones by iodine in a neutral medium gives azines, but in the presence of triethylamine, gem-di-iodides and vinyl iodides, respectively, are formed in a limited number of cases. The reaction is useful as part of a mild process for converting formyl into methyl groups.60 Lead tetra-acetate provides a useful means of converting half esters of malonic acid into a-acetoxy-esters,61 and of oxidising N-benzenesulphonyl1 - and -2-naphthylamine to 1- and 2-benzenesulphonamido-l,4-naphthaquinone. Olehs.-Olefin formation from stable phosphoranes, Ph,P:CR*CO,R', is achieved by Wittig reaction with unreactive, sterically hindered ketones in little or no solvent and a t 150".63 Alternatively, the reactions are carried out in sealed tubes between 100" and 170O.64 Me, ,Me The stereoselective synthesis of or-substituted ap-unsa,turated esters, R"R'C:CR*CO,R, where R' is larger ,c=c, H than R",is possible. Acetaldehyde and Ph,P:CMe*CO,Me (1 1) yield methyl tiglate (ll),and only 3.5% of the isomeric methyl angelate.65 m-Alkoxycarbonylalkylidenetriphenylphosphoranesand aldehydes give mainly the trans-product by a Wittig reaction. Use of Lewis bases such as lithium bromide or iodide in dimethylformamide leads to cis-unsaturated acids, Me*[CH,];CH :CH*[CH,];CO,H ;the method also makes available cis&-products such as linoleic and linolenic acid. However, stereochemical control of the reaction between these phosphoranes and ketones has not yet been achieved.66 Alkylidenetriphenylphosphoranes are acylated by acid chlorides and activated esters 67 and by N-acylimidazoles:68
R*COCl+ R'*CH:PPh,+R*COCR':PPh, (12)
The p-oxo-alkylidenetriphenylphosphoranes yield ketones, R*CO*CH,R', (12)

K. Nakagawa, R. Konaka, and T. Nakata, J. Org. Chem., 1962, 27, 1597. N. J. Leonard and C. R. Johnson, J. Org. Chem., 1962, 27, 282. 5 9 H. Schecter and F. T. Williams, jun., J. Org. Chem., 1962, 27, 3699. 6 o D. H. R. Barton, R . E. O'Brien, and S. Sternhell, J., 1962, 470. 6 1 M. Rouhi-Laridjani and M. Wilkas, Compt. rend., 1962, 254, 1090. 6 2 H. J. Richter and R . L. Dressler, J . Org. Chem., 1962, 27, 4066. 63 H. T. Openshaw and N. Whittaker, Proc. Chem. SOC., 1961, 454. 6 4 G. Fodor and I. Tomoskozi, Tetrahedron Letters, 1961, 579. 6 5 H. 0. House and G. H. Rasmusson, J. Org. Chem., 1961, 26, 4278. 6 6 Chem. Eng. News, 1962, 40, No. 30, 36 (report of work by M. M. Shemyakin, L. D. Bergelson, and V. A. Vaver). 6 7 H. J. Bestman and B. Arnason, Chem. Ber., 1962, 95, 1513. 6 s H . J. Bestman, Angew. Chem., Internat. Edn., 1962, 1, 270.
57
58
BARKER A N D G R A Y : GENERAL METHODS
261
on hydrolysis, and by Wittig reactions give cc-substituted ag-unsaturated ketones :67

R*CO*CR:PPh,+ R*CHO +R*CO*CR:CHR Ph,PO.
From the C-formyl derivatives, prepared by using 1-formylimidazole, aldehydes and c@-unsaturated aldehydes are obtained in the above reaction~.~~ An intramolecular Wittig synthesis is reported, 7* reaction apparently proceeding via the phosphorane (13) :
Ph*CO-[CHd ,-PPht Br-
NaOEt
EtOH
Ph-CO*[CHd3-CH:PPh3
Ph-C -[CHJ, CH
(3)
II
(24%)
The formation of vinylic bromides or iodides from phosphoranes, Ph,P :CHX, obtained from the bromomethyl- or iodomethyl-triphenylphosphonium halides and organometallic reagents has been investigated. 71 Stable halogenophosphoranes, Ph,P:CX-CORY where X = C1 or Br, and R = Ph, OEt, or Me, have been prepared and undergo normal Wittig reac1 tions with ben~aldehyde.~ Phosphoranes, Ph,P:CX, (X = C or Br), have been obtained, and with benzaldehyde yield the /?~-dihalogenostyrenes. 73 The reaction between alkylidenetriphenylphosphoranes and activated olefins can provide a useful synthesis of cyclopropane derivative^,^^ and the reaction of olefins with phosphorus trichloride and aluminium trichloride gives a new method of forming carbon-phosphorus bonds. 75 Metallation of mono- and bis-phosphonous and -phosphonic esters, as well as of phosphine oxides, followed by interaction with aldehydes or ketones, has been developed into a route to mono- and di-olefins:76
? I
>P-$-
--+
)P-OM
M0.7 + ;c=c,0 A method is described for the vinylation of /I-dicarbonyl compounds :7 7

H
M
R\
H2C:CH /c
69
,C02Et C02Et
H. A. Staab and N. Sommer, Angew. Chem., Internat. Edn., 1962, 1, 270. Bieber and E. H. Eisman, J . Org. Chem., 1962, 27, 678. 71 D. Seyferth, J. K. Heeren, and S. 0. Grim, J . Org. Chem., 1961, 26, 4783; G . Kobrich, Angew. Chem., Internat. Edn., 1962, 1, 51. 7 2 D. B. Denney and S. T. Ross, J . Org. Chem., 1962, 27, 998. 7 3 R. Rabinowitz and R. Marcus, J . Amer. Chem. SOC., 1962, 84, 1312; F. Ramirez, N. B. Desai, and N. McKelvie, ibid., p. 1745. 7 4 H. J. Bestman and F. Seng, Angew. Chem., Internat. Edn., 1962, 1, 116.
70T. I.
5 E. Jungermann, J. J. McBride, jun., R. Clutter, and A. Mais, J . Org. Chem., 1962, 27, 606; J. J. McBride, jun., E. Jungermann, J. V. Killheffer, and R. J. Clutter, ibid., p. 1833. 6 L. Homer, H. Hoffmann, W. Klink, H. Ertel, and V. G . Toscano, Chem. Ber., 1962, 95, 581. 7 7 M. Seefelder, Annalen, 1962, 652, 107.
262
ORGANIC CHEMISTRY
Benzylcyclo-octyldimethylammonium bromide and sodamide in liquid ammonia yield cis- cyclo-octene, whereas cyclo-octyltrimethylammonium iodide with potassium amide in liquid ammonia gives the trans-isomer. 7 8 Selective epoxidation of non-terminal olefins makes possible the purification of terminal olefins. Treatment of the pure products with thiolacetic acid (Me*CO*SH) yields thiolacetates, which are oxidised by hydrogen peroxide-acetic acid t o the pure terminal sulphonic acids.79 Carbons1 Compounds.-Under controlled conditions, excellent yields of either 9-acetyl- or 1,5-diacetyl-anthracene are obtained by a Friedel-Crafts reaction on anthracene in chloroform.80 1-Acyl- or 1-aroyl-imidazoles with Grignard reagents give ketones in good yield (50-90%). Decomposition of the complexes from Grignard reagents and nitriles with anhydrous methanol instead of with ammonia gives better yields of ketimines and makes available hitherto unobtainable ketimines, e.g., Et,C:NH.82 Carboxylic esters with di-isobutylaluminium hydride in toluene or hexane at -70" and with sodium di-isobutylaluminium hydride in ether a t -70" give good yields of aldehydes.83 Aliphatic nitriles are hydrogenated by Raney nickel and phenylhydrazine; pressure is not necessary and the yields of aldehyde are Aldehydes are also obtained from nitriles by using sodium hypophosphite and Raney nickel, reduction taking place a t room temperature and pressure.85 Reduction of l-acylaziridines 8 6 and 1 -acyl- and l-aroyl-imidazoles 87 with lithium aluminium hydride provides other satisfactory routes to aldehydes, and the scope of the following preparation of aldehydes from p - N N dimethylaminophenylcarbinols has been studied for R = alkyl, aryl, or alkenyl :8 8
~-R*CH(OH)*C,H~*NMO, p-+Nz*C,H4*SO,---+ R-CHO H0,S~C,H4~N:N.C,H4.NMez.
H+
The sodium enolate of pinacolone, in 1,2-dimethoxyethaneY with methyl or ethyl pivalate yields 60-70y0 of dipivaloylmethane. The method may be general for hindered p-diketones not readily available by other means.89 Symmetrical p-diketones are readily prepared from methyl esters and ketones by using sodium hpdride as base and dimethyl sulphoxide as solvent. Carboxylic Acids.-Excellent yields of acids, R CH, *CO,H, are obtained
C. L. Bumgardner, J. Org. Chem., 1962, 27, 1035. J. S. Showell, J. R. Russell, and D. Swern, J. Org. Chem., 1962, 27, 2853. 8 0 H. F. Bassilios, M. Shawky, and A. Y. Salem, Rec. Trav. chim., 1962, 81, 679. 81 H. A. Staab and E. Jost, Annalen, 1962, 655, 90. 8 2 P. L. Pickard and T. L. Tolbert, J. Org. Chem., 1961, 26, 4886. 8 3 L. I. Zakharkin and I. M. Khorlina, Tetrahedron Letters, 1962, 619. 84A. Gaiffe and R . Pallaud, Compt. rend., 1962, 254, 496. 8 5 0. G . Backeberg and B. Staskun, J., 1962, 3961. 8 6 H. C. Brown and A. Tsukamoto, J . Amer. Chem. SOC., 1961, 83, 4549. 8 7 H. A. Staab and H. Braiinling, Annalen, 1962, 654, 119. 8 8 A. Sisti, J. Burgmaster, and M. Fudim, J. Org. Chem., 1962, 27, 279. K. R. Kopecky, D. Nonhebel, G. Morris, and G. S. Hammond, J. Org. Chem., 1962, 27, 1036. J. J. Bloomfield, J. Org. Chem., 1962, 2'7, 2742.
79
263
by heating b-keto-esters, MeCO*CHR*CO,Et,with an excess of absolute ethanol containing catalytic amounts of alkoxide under carefully controlled ~onditions.~~ Aliphatic and aromatic aldoximes give good yields of carboxylic acids when heated with potassium hydroxide and diethylene and aromatic aldehydes yield the nitriles if heated a t the b.p. in acetic acid containing hydroxylamine hydrochloride and sodium acetate. 93 Further examples of the desulphurisation of selected derivatives of thiophen t o give hydroxyalkanoic acids and hence alkanoic acids are reported 94 and suitable thiophen ketoximes yield amino-acids. Thus, the derivative (14)gives 9-aminodecanoic acid.95 A 52% yield of '' monofluorocitric acid " (1-fluoropropane-l,2,3-tricarboxylic acid) has been obtained as the barium salt.96 The previous best method gave a 12% Me.$ H23 3. COzH yield of very impure material. H0.N Primary and secondary carboxylic acids are (1 4) decarboxylated when heated with lead tetraacetate and iodine in carbon tetrachloride; iodides are formed in high yield.97 A general synthesis of arylsulphur trifluorides has been developed :98
LJ T
ArS-SAr
+ 6AgF, -3 2ArSF, + 6AgF.
Phenylsulphur trifluoride has advantages over sulphur tetrafluoride 99 for converting carbonyl compounds and carboxylic acids into difluoro- and trifluoro-methylene derivatives, respectively.98 Sulphur tetrafluoride converts the carboxyl group of amino-acids into trifiuoromethyl in the presence of hydrogen fluoride which protects the amino-group, and the optical activity of the amino-acid is retained.loO Small amounts of hydrogen fluoride catalyse reaction between the carbonyl group and sulphur tetrafluoride, but 20% of hydrogen fluoride is essential for successful fluorination (-CO,H --+ -CF3; -CHO +-CHF,) of a variety of steroids.101 Basic cupric salts of benzoic and toluic acid a t 200-220" yield the corresponding o-hydroxy-carboxylic acid.l o 2 Acid amides are conveniently obtained under mild conditions from the acid chloride by stirring it with ammonium acetate in acetone.lo3 The light-induced addition of formamides to olefins has been successful in a number of cases :lo4
R.CH:CH,
91
92
+ H-CO-NHR'+RCH,*CH,*CO*NHR'.
J. J. Ritter and T. J. Kaniecki, J. Org. Chem., 1962, 27, 622. H. Rapoport and W. Nilsson, J. Org. Chem., 1962, 27, 629. 93 J. H. Hunt, Chem. and Ind., 1961, 1873. g 4 J. F. McGhie, W. A. ROSS, D. Evans, J. E. Tomlin, J., 1962, 350; K. E. Miller, C. R. Haymaker, and H. Gilman, J. Org. Chem., 1961, 26, 5217. 9 5 J. F. McGhie, W. A. ROSS, and D. H. Laney, J., 1962, 2578. 9 6 P. J. Brown and B. C. Saunders, Chem. and Ind., 1962, 307. 9 7 D. H. R. Barton and E. P. Serebryakov, Proc. Chem. SOC., 1962, 309. g 8 W. A. Sheppard, J. Amer. Chem. SOC., 1962, 84, 3058. 9 g W. C. Smith, Angew. Chem., Internat. Edn., 1962, 1, 467. loo M. S. Raasch, J. Org. Chem., 1962, 27, 1406; F. Weygand, W. Steglich, and H. Tanner, Annalen, 1962, 658, 128. lol D. G. Martin and F. Kagan, J. Org. Chem., 1962, 2'7, 3164. lo2 W. W. Kaeding and A. T. Shulgin, J. Org. Chem., 1962, 2'7, 3551. lo3 P. A. Finan and G. A. Fothergill, J., 1962, 2824. lo4 D. Elad, Chem. and Ind., 1962, 362.
264
ORGANIC CHEMISTRY
Alkylation.--Sodium 2,6-dimethyl-4-t-butylphenoxidealkylated either is at the oxygen atom or at an ortho-position, the latter reaction giving 6-benzy1-2,6-dimethy1-4-t-buty1cyc1ohexa-2,4-~enone (15). The ratio of 0- C-alkylation varies with the organic medium, but to heterogeneity of the reaction mixture per se has no effect Me CH 2Ph on the ratio. lo5 Selective alkylation of 4-hydroxybenzyl Me alcohol to the alkyl4-hydroxybenzyl ether is achieved by B~~ (15) using the required alcohol and a cation-exchange resin at room temperature.106 Two further instances of control of the site of alkylation by using dianions are reported. The monoanion from 2,3,3-triphenylpropionitrile gives the 2-alkyl derivative, whereas the dianion gives the 3-alkyl derivative,l07 and formation of the dianion from 2-formyl-1 -decalone permits the introduction of an angular methyl group.lo*
1, ZKNH, i liquid NH,. n
2, MeI.
The readily introduced and readily removed n-butylthiomethylene group is an effective blocking group for achieving monomethylation of ketones and permits angular methylation of the derivative (16).log Naphthalene sodium is an effective metallating agent for the a-carbon atom of aliphatic nitriles, and alkylation of these sodium derivatives gives pure products; two different alkyl groups can be introduced without isolation of the monoalkyl compound.l10 Exceptionally good results in the Wurtz synthesis, e.g., bibenzyl (90%) from benzyl chloride, are obtained by using naphthalene sodium.111 The system methyl iodide-ButOH-ButOK, used extensively in the alkylation of A4-3-keto-steroids and simple bicyclic compounds, favours formation With methyl chloride, dialkylation is of the 4,4-dimethyl-A5-3-ketone. (40y0), 4,4restricted, cholest-4-en-3-onegiving 4-methylcholest-4-en-3-one dimethylcholest-5-en-3-one (12%),and starting material
D. Y. Curtin and D. H. Dybvig, J. Amer. Chem. SOC.,1962, 84, 225. F. H. C. Stewart, J . Org. Chem., 1962, 27, 2662. lo' W.G. Kofron, W. R. Dunnavant, and C. R. Hauser, J . Org. Chern., 1962, 2'4,
loS
lo6
2737.
T. R. 110 L. lllH. 112 H.
lo8 log
M. Harris and C. R. Hauser, J . Amer. Chem. SOC., 1962, 84, 1750. E. Ireland and J. A. Marshall, J . Org. Chem., 1962, 27, 1615. Horner and H. Gusten, Annalen, 1962, 652, 99. Gusten and L. Horner, Angew. Chem., Internat. Edn., 1962, 1, 455. J. Ringold and S. K. Malhotra, J . Amer. Chern. SOC.,1962, 84, 3402.
265
16-Dehydropregnenolone acetate in tetrahydrofuran is alkylated and deacetylated by using lithium in liquid ammonia and methyl iodide. Reacetylation yields 25% of 17a-methylpregnenolone acetate. More usual conditions with methyl iodide-ButOK give a complex crystalline mixture. 113 Alkylation of active methylene groups has been achieved by alkyl halides in liquid ammonia without a condensing agentY1l4 and by radical-initiated By addition of the methylene compound to a suitable 01efin.l~~ controlling the amount of ethanol present, the salt (17) may be alkylated to give excellent yields of either the alkyl-substituted CO 2Et adipate or the alkyl-substituted cyclopentanone.116 Acetamide with acetal or 2,2-dimethoxypropane in 0 (1 7) acetic acid reacts with hydrogen in the presence of palladium-charcoal and sulphuric acid giving N-ethyl- or N-isopropyl-acetamide in good yield.l17 The methylene-transfer reagents,118 dimethylsulphonium methylide (IS) and dimethylsulphoxoniummethylide (19),react with aldehydes and ketones t o give oxirans. The sulphonium ylide yields oxirans even with aB-unsaturated carbonyl compounds, whereas the sulphoxonium ylide gives the cyclopropane derivative. The sulphonium ylide is the more powerful and selective transfer reagent, yielding cyclopropane derivatives with olefins, and aziridines with anils. The sulphoxonium ylide does not react with 1,l-diphenylethylene, and with benzylideneaniline gives lY2-diphenylaziridine and acetophenone anil.
LAa
R-CO-R'
CH2:SMez
(18)
__f
Ph*CH:CH-COPh Ph2C: CH2
Me2S:CHz
__5
RI, c/ YH 2. R/ ' 0
H C I >CHPh Ph-CO-HC
PhCH:NPh
CH2:SMe2
CH2 / \ PhHC NPh
Organometallic Compounds.-Further instances are recorded of the formation of Grignard reagents in hydrocarbon media.llg Isopropylmagnesium bromide rearranges to n-propylmagnesium bromide in the presence of small amounts of titanium tetrachloride. Rearrangement proceeds via propene and Me*[CH,],*TiCl,,and the reaction provides a means
113 114 K.
115 116 117
R. Deghenghi and R. Gaudry, Tetruhedron Letters, 1962, 489. Shimo, S. Wakamatsu, and T. Inoue, J . Org. Chem., 1961, 26, 4868.
J. C. Allen, J. I. G. Cadogan, B. W. Harris, and D. H. Hey, J . , 1962, 4468. L. Nicole and L. Berlinguet, Cunad. J . Chem., 1962, 40, 353. H. E. Johnson and D. G. Crosby, J . Org. Chem., 1962, 27, 2205. 11* E.J. Corey and M. Chaykovsky, J . Amer. Chem. SOC., 1962, 84, 866, 867, 3782; V. Franzen, H.-I. Joschek, and C. Mertz, Annulen, 1962, 654, 82; V. Franzen and H.-E. Driessen, Tetrahedron Letters, 1962, 661. 11 L. I. Zskharkin, 0. Yu. Okhlobystin, and B. N. Strunin, Tetrahedron Letters, 1962, 631.
266
ORGANIC CHEMISTRY
of preparing Grignard reagents, R*CH,*CH,*MgBr,from terminal olefins, R*CH:CH,, and available Grignard reagents. Thus, hexan-1-01 (45%) is obtained from pent-l-ene, n-propylmagnesiumbromide, and titanium tetrachloride, after treatment of the reaction mixture with formaldehyde. Styrenes give a mixture of cc-methylbenzyl- and phenethyl-magnesium bromide. Internal double bonds and vinylidene groups are unaffected, making it possible to prepare unsaturated Grignard reagents.120 Catalysis by cuprous halides of addition of Grignard reagents to the a@-doublebond of ag-unsaturated ketones is improved in the presence of cupric acetate in tetrahydrofuran.lZ1 An excess of methylmagnesium bromide with an alkyl 3P-hydroxy-17amethylandrost-5-ene-l7@-carboxylate boiling anisole yields the sterically in hindered 17a-methylpregnenolone(70%) and the corresponding diol (20%); steric control is even greater with ethylmagnesium bromide, no diol being formed.lZ2 Interaction of Grignard reagents and acetals is simplified by preparing the Grignard reagent in a boiling solution of the acetal in an aromatic hydrocarbon. Good yields of ethers are obtained in several cases.123 Exchange between phenyl- or n-butyl-lithium and tetra-allyltin, or between phenyl-lithium and allyltriphenyltin, gives excellent yields of allyllithium.124 Increased ease of metallation in tetrahydrofuran compared with ether is exemplified by the improved yield of 2,2'-dilithiodiphenyl ether from diphenyl ether and n-buty1-lithi~m.l~~ Triphenylaluminium and diphenylacetylene give benzene and the heterocycle (20). The organometallic compound (21) has also been prepared.lZ6
Diazonium Compounds.-Nitrosation of N-arylphosphoramidates yields diazonium phosphates by rapid rearrangement of the N-nitrosophosphoramidates,127 and solid diazonium hydrogen sulphates free from sodium hydrogen sulphate are obtained by treating aromatic amines in acetic acid with nitrosylsulphuric acid (HNO, SO,) in acetic acid.12* Decomposition of the water-insoluble diazonium hexafluorophosphates is an alternative method of preparing aryl fluorides, and in some cases a marked improvement over the decomposition of the tetrafluoroborate is realised.1 2 9 Addi-
l Z o H . Finkbeiner and G. D. Cooper, J. Org. Chem., 1961, 26, 4779; 1962, 27, L. 1493, 3395. lZ1 A. J. Birch and M. Smith, Proc. Chern. SOC.,1962, 356. 12*R. Deghenghi and R. Gaudry, J . Amer. Chem. Soc., 1961, 83, 4668. lZ3 C. Blomberg and A. D. Vreugdenhil, Rec. Tmv. chim., 1962, 81, 238. lZ4 D. Seyferth and M. A. Weiner, J. Org. Chem., 1961, 26, 4797. 125 H. Gilman and W. J. Trepka, J. Org. Chem., 1961, 26, 5202. lZ6 J. J. Eisch and W. C. Kaska, J . Amer. Chern. Soc., 1962, 84, 1501. lZ7 P. J. Bunyon and J. I. G. Cadogan, J., 1962, 1304. 1 2 * M. R. Piercey and E. R. Ward, J., 1962, 3841. lZ9 K. G. Rutherford, W. Redmond, and J. Rigamonti, J . Org. Chem., 1961, 26, 5149.
BARKER AND GRAY: GENERAL METHODS
267
tion of acetic acid to diazonium tetrafluoroborates in tetracarbonylnickel yields the arenecarboxylic acids (25-75%). 130 Smooth arylation of benzene in good yield is achieved under homogeneous conditions by warming an aromatic amine, benzene, and pentyl nitrite, without acid (no reference is made to hydrocarbons other than benzene),131 Further work has been reported on the homologation of a/3-unsaturated ketones with diazomethane in the presence of boron trifluoride or tetrafluorboric acid :l 3 2
)C:C*C:O
I 1
+ )C:C*CH,*C:O
Arylaminium tetrafluoroborates with diazoacetic ester yield N-arylglycine esters. 133 Diazopropyne has been obtained from N-acetylpropargylamine; its solutions in ether or methylene dichloride are quite stable at room temperature.134 Miscellaneous.-Further developments in the photolysis of organic nitrite esters are reported 135 and the subject has been reviewed.136 Photolysis of appropriate 1,2-diketones gives 2-hydroxycyclobutanones with striking selectivity and remarkable yields ; e.g., decane-5,6-dioneyields 2-butyl-3-ethyl-2-hydroxycyclobutanone.l3 Alkyl and aryl isocyanates give high yields of carbodi-imides under mild conditions when a phospholen oxide catalyst is used, of which the most 1~~ active was 1-ethyl-3-methyl-3-phospholen 0 ~ i d e . l Reaction between thioureas and acylated aliphatic carbodi-imidesis a general method for preparing pure carbodi-imides in high yield.139 I n acid conditions, carbodiimides promote numerous esterification reactions under very mild conditions.140 The principle of Friedel-Crafts acylation has been extended to the nitration of aromatic compounds, Even deactivated systems such as halogenobenzenes and benzotrifluoride are nitrated by nitryl halides, by nitrogen pentoxide, and by nitrogen tetroxide, when appropriate Lewis acids are added. Nitronium tetrafluoroborate is a particularly effective nitrating
J. C. Clark and R. C. Cookson, J., 1962, 686. J. I. G. Cadogan, J., 1962, 4257. W. S. Johnson, 31. Neeman, S. P. Birkeland, and N. A. Fedorak, J . Arner. Chem. SOC.,1962, 84, 989. 133 E. Miiller and H. Huber-Emden, Annalen, 1961, 649, 70. 134H. Reimlinger, Angew. Clzem., Internat. Edn., 1962, 1 216. , 135 A. L. Nussbaum, R. Wayne, E. Yuan, 0. Zagneetko, and E. P. Oliveto, J . Amer. 1962, 84, 1070; P. Kabasakalian, E. R. Townley, and M. D. Yudis, ibid., Chem. SOC., pp. 2716, 2718; P. Kabasakalian and E. R. Townley, ibid., p. 2723; P. Kabasakalian and E. R. Townley, J . Org. Chem., 1962, 27, 2918, 3562; A. L. Nussbaum, E. P. Yuan, C. H. Robinson, A. Mitchell, E. P. Oliveto, J. M. Beaton, and D. H. R. Barton, ibid., p. 20; A. L. Nussbaum, F. E. Carlon, E. P. Oliveto, E. Townley, P. Kabasakalian, and D. H. R. Barton, Tetrahedron, 1962, 18, 373. 136 A. L. Nussbaum and C . H. Robinson, Tetrahedron, 1962,17, 35; see also P. Gray, ibid., 18, 879. 1 ' W. H. Urry and D. J. Trecker, J . Amer. Chern. SOC., 3 1962, 84, 118. 13* T. W. Campbell and J. J. Monagle, J . Arner. Chern. SOC., 1962, 84, 1493; T. W. Campbell, J. J. Rlonagle, and V. S . Foldi, ibid., p. 3673; J. J. Monagle, J . Org. Chem., 1962, 27, 3851. 139 K. Hartke, Angew. Chem., 1962, 1, 212. 140 A. Buzas, C. Egnell, and P. FrBon, Compt. rend., 1962, 255, 945.
130
131 132
268
ORGANIC CHEMISTRY
agent under these conditions, and the reactions are conveniently carried out in tetramethylene sulphone (tetrahydrothiophen dioxide).I41 Tri-isopropylamine is obtained in 54% yield from aa-di-isopropylaminopropionitrile and methylmagnesium chloride in ether.
C. C. B. G . W. G.
5 . ALIPHATIC COMPOUNDS
Acetylenes.-General. A further new synthesis of the acetylenic bond has been reported :l diethyl vinyl phosphates (1) on treatment with sodamide in liquid ammonia at -70" furnish the corresponding acetylenes in high yield. The reaction lends some support to a proposed biogenetic pathway
R*CO.CH,R' --+R*C:CHR'
-+ R*CiC*R'
O*PO(OEt),
(1)
(R
Aryl, R'
H, Aryl, or C0,Et)
involving enol phosphates.2a However, if the reaction is performed at -33", the a/?-acetylenicesters and'amides then formed undergo cleavage as shown,
Ph*C:C*CO-NH,
+ NH, +Ph-CiCH + NH,*CO*NH,,
whilst ag-acetylenic carboxylic acids having a y-hydrogen atom rearrange quantitatively to the corresponding allenic acids.3 Japanese workers,4 in an independent study, employing diphenyl vinyl phosphates [e.g., Ph*CO*CH:CPh-O*PO( OPh),] derived from /?-dicarbonyl systems, have shown that cleavage can be avoided by employing sodium t-butoxide as base in benzene at room temperature. Treatment of an enol p-bromobenzenesulphonate with aqueous baseZa shows promise as a general route to conjugated enyne acids R *[CH:CH];CiC*CO,H, but not to polyacetylenic acids since tetronic acids are formed instead. 2b
p-Br*C,H,*SO,*O*CR:C(CO,Et)
+R-CiCCO,H.
The triphenylphosphorane route2' to the triple bond has been examined further, and ag-acetylenic acids are now available by mild (80") alkaline treatment of a chloro-intermediate: +PPh,*C(C0,Me) :CR -0- + +PPh3*C ,Me) :CR Cl]C1- --+ ROC *C ,H . [ (CO iC 0
PC15
141 S. J. Kuhn and G . A. Olah, J . Amer. Chem. SOC., 1961, 83, 4564; G . A. Olah, S. J. Kuhn, and S. H. Flood, ibid., pp. 4571, 4581. l42 F. Kuffner and W. Koechlin, Monatsh., 1962, 93, 476.
J. Cymerman Craig and M. Moyle, Proc. Chem. Xoc., 1962, 149. ( a ) Ann. Reports, 1961, 58, 210; (b) I. Fleming and J. Harley-Mason, Chem. and Ind., 1962, 560, 561. J. Cymerman Craig and M. Moyle, Proc. Chem. SOC., 1962, 283. M. Nakagawa, G . Nakaminami, F. Ogura, and H. Ono, Bull. Chem. SOC. Japan, 1962, 35, 1485, 1488; G. Nakaminami, ibid., p. 1629. G. Markl, Angew. Chem., 1962, 74, 217.
EGLINTON
: ALIPHATIC COMPOUNDS
269
A new synthesis (50-60% yield) of arylacetylenes requires irradiation (2537 A) of 1-iodoarylacetylenes in benzene for 12 hours :6
Ar-CjCI+Ar*CjC*Ar.
Irradiation of a hexane solution of diphenylacetylene results in a mixture of several intriguing substances, notably " octaphenylcubane " (section 6) and hexaphenylbenzene. Palladium chloride complexes also effect similar reactions.8 A crystalline 1 : 1 complex formed by 1-methylpyrrolidone and diacetylene has been used in the isolation of the latter.g There is now a considerable range of data relating to the acidity of the ethynyl hydrogen of terminal acetylenes which should be invaluable in reaction studies.l o The 1 : 1 complex formed by cuprous chloride and the bidentate ligand, Me,N*CH,-CH,*NMe,, is claimed to be the most effective catalyst yet discovered for the oxidative coupling of ethynyl compounds. Even an alk-lyne will couple quite rapidly at room temperature when shaken with oxygen in an acetone solution containing a small quantity of the catalyst.11 Another example of a highly strained cyclic dimer derived by the coupling of an o-diethynyl compound has been recorded,12and the literature relating to cyclic acetylenes has been ably reviewed.13 The formation of both conjugated and non-conjugated vinylacetylenes has received further attention.14 Carbene can be inserted 15a into the ethynyl C-H bond, e.g.:
PhCiCH ---+ Ph*CjC*CH,(29%)
and zinc stearate is an effective catalyst at 180" for the vinylation of #Micarbonyl systems,15b e.g. :
HCjCH
+ B u ~ * C H ( C O ~ E ~CH,:CH*CBun(CO,Et), (75%) + )~
The hydration of stearolic acid has been re-investigated and is now said to result in approximately equal amounts of the 9- and the 10-keto-acid.16 Catalytic hydrogenation of the triple bond sometimes produces substantially trans-olefins.l 7 Several ready cyclisations involving the triple bond have been described : these include a radical-induced cyclisation of E-acetylenic
N. Kharasch and L. Gothlich,Angew. Chem., 1962, 74,651 ;N. Kharasch, W. Wolf, T. J. Erpelding, P. G. Naylor, and L. Tokes, Chem. and Id., 1962, 1720. G. Buchi, C. W. Perry, and E. W. Robb, J . Org. Chem., 1962, 27, 4107. A. T. Blomquist and P. M. Maitlis, J. Amer. Chem. SOC., 1962, 84, 2329. 9 N . Shachat, J . Org. Chem., 1962, 27, 2928. l o W. Drenth and A. Loewenstein, Rec. Trav. chim., 1962,81, 635; H. B. Charman, D. R. Vinard, and M. M. Kreevoy, J. Amer. Chem. SOC., 1962, 84, 347; R. E. Dessy, Y. Okuzumi, and A. Chen, J . Amer. Chem. SOC.,1962, 84, 2899. l l A . 5. Hay, J . Org. Chem., 1962, 27, 3320. l 2 M . Morimoto, S. Akiyama, S. Misumi, and M. Nakagawa, Bull. Chem. Soc. Japan, 3.962, 35, 857. R. Kolinskii, Russ. Chem. Rev., 1961, 30, 309. R. F. Garwood, E. Oskay, and B. C. L. Weedon, Chenz. and Id., 1962, 1684; P. Kurtz, Annalen, 1962, 658, 6. l5 ( a ) L. Vo-Quang, P. Cadiot, and A. Willemart, Compt. rend., 1962, 255, 950; (b) M. Seefelder, Annalen, 1962, 652, 107. l 6 J. C. Smith and P. D. Thickbroom, Chem. and Ind., 1962, 695. l 7 N. A. Dobson, G . Eglinton, M. Krishnamurti, R . A. Raphael, and R. G. Willis, Tetrahedron, 1961, 16, 16.
270
ORGANIC CHEMISTRY
cyano-esters,ls butenolide formation by prop-2-ynylidenemalonic and related acids, l9 condensation of ethynylcarbinols with isocyanates to give oxazoles,20
0
HO*CMe2-CICH
+ p - C1*C,H4-
and conversion of oct-6-en-l-yne at 400" into an isomeric cyclopentane derivative.21 Useful, or potentially useful, acetylenic intermediates examined during the year include dicyanoacetylene,22 cyanoiodoacetylene,23 propargyl cyanide,24 monoflu~roacetylene,~~ derivatives of By-acetylenic aldeand hydes.26 The first conjugated alkoxyethynyl ketone (2) to be prepared has
MeOCjCCH(0H)CH:CHMe
-+ MeOCiC.COCH:CHMe
trans
(2)
been used in the key step of an ingenious, stereospecific, total synthesis of griseofulvin;27the reagent used in preparation of the ketone was neutral manganese dioxide. Recent kinetic measurements 28 conducted in dimethylformamide solution show that 1-chlorophenylacetyleneundergoes more rapid substitution than n-butyl chloride by certain nucleophiles (e.g., p-C,H,@e*SNa), a finding which augurs well for future synthetic applications. h e n s and his colleagues 29 continue to explore the chemistry of acetylenic ethers and related compounds. Representative of the types recently examined are the compounds (3)-(8), where R = H or alkyl; in some cases (e.g., 3 and 4,R = H) the substances either could not be isolated or were very
(3) R-CiC-0-CiC*R
( 5 ) RO*CjC*[CH,],.CjC.OR
(7)
RO*CiC*SR
R*CiC*S*CjC*R (4) R*CiC*X*CH:CH, (6) (X = 0, S, or Se) R-CjC-O*[CH,],*O*CjC*R (8)
unstable. Acetylenic sulphides, selenides, and tellurides (9) can be conveniently prepared by direct addition of the particular element to a suspension of sodium alkynide in liquid ammonia:29
R*CjCNa + R*CjC*XNa+ R*CiC*XR' (9)
ISM.
X*
R'Br
(50-75%)
Julia and C. James, Compt. rend., 1962, 255, 959. J. Bosch, J. Castells, and J. Pascual, Anales real SOC. espa6. Pi&. Quim., 1961, 57, B, 469; G. Belil, J. Castella, J. Castells, R. Mestres, J. Pascual, and F. Serratosa, ibid., p. 617. ao N. R . Easton, D. R. Casssdy, and R. D. Dillard, J. Org. Chem., 1962, 27, 2927. 21 W. D. Huntsman and R. P. Hall, J . Org. Chem., 1962, 27, 1988. 2 2 R. C. Cookson and J. Dance, Tetrahedron Letters, 1962, 879. E. Kloster-Jensen, Chem. and Ind., 1962, 658. 2 4 G. S. Reddy, L. MandeI1, and J. H. Goldstein, J . Amer. Chem. SOC., 1961, 83, 4729. 25H. Viehe and E. Granchimont, Chem. Ber., 1962, 95, 319. G. 2 6 M. H. Durand, Bull. SOC. chim. France, 1961, 2396. 1962, 84, 310. 2 7 G. Stork and M. Tomasz, J . Amer. Chem. SOC., 2 8 A. K. Kuriakose and 8. I. Miller, Tetrahedron Letters, 1962, 905. z 9 L. Brandsma and J. F. Arens, Rec. Trav. chim., 1962, 81, 510, 617; J. R. Nooi and J. F. h e n s , ibid., p. 533; L. Brandsma and J. F. Arens, ibid., p. 539; B. Rosebeek and J. F. Arens, ibid., p. 549; L. Brandsma, H. Wijers, and J. F. Arens, ibid., p. 635.
Is
ECLINTON : ALIPHATIC C O M P O U N D S
271
Natural products. Many new polyacetylenic compounds have been characterised,30, 31 most of them from higher plants, by Bohlmann and his colleagues.31 Careful examination of the stems, leaves, and roots of numerous individual species belonging to the genera Coreopsis, Centuurea, Bidens, Xantolinu, Anthemis, Artemisia, Achillea, Chrysanthemum, Hatricaria, and Tanacetum (Compositae) has revealed several novel types of polyacetylene, but the underlying biogenetic relations are, in fact, becoming clearer as the full pattern of unsaturation, oxygenation, cyclisation, etc., emerges. Chain lengths range from C,, to C14 but the variety is evident from the recently isolated 309 31 compounds (10-25) with a C13 skeleton.
(10) CH,*[CjC],*[CH:CH],*H
CH,*[C{C],*CH-CH*[CH:CH] (11) ,*H
\/
0
( 12)
CH,.[CiC]**CH:CHCH-CH 2
v 0
CH,*CH:CH*[CiC] ,*CH:CH*CH-CH 2
v 0
( 13)
(14) CH,*CH:CH*[CiC],*CH:CH*CHX*CH,Yx and y = OH, O A ~ or ,

(15)
CH,*CH:CH*[C~C]2.[CH:CH]2.CHX*CH2Y (not combinations) (16) CH,:CH=[C~C],*CH:CH*CHO

AcO
c l
(23)
R = -CHZ*[C=C],Me
( 2 4 ) R = -C0.[CEC]2Me
Me0
a n d CH ( OAc ) [ P C 2Me C ]
Me-[CCiC],KH:CH.CH2*OH
(26)
The common origin of fatty acids, polyacetylenes, and acetate-derived phenols has now been demonstrated 32 by the finding that labelled diethyl malonate is incorporated specifically as carbons C-1 to C-8 of a C,,
S. L. Jensen and N. A. Sorensen, A c t a Chem. Scand., 1961, 15, 1885. F. Bohlmann, W. Sucrow, H. Jastrow, and H. J. Koch, Chem. Ber., 1961, 94, 3179; F. B o h h n n , P. Herbst, C. Amdt, H. Schonowsky, and H. Gleinig, ibid., p. 3193; F. Bohlmann and K.-M. Klehe, Chem. Ber., 1962, 95, 39; F. Bohlmann and K.-M. Kleine, ibid., p. 602; F. Bohlmann, C. Amdt, H. Bornowski, and K.-M. Kleine, ibid., p. 1315; F. Bohlmann, C. Amdt, H. Bornowski, H. Jastrow, and K.-M. Kleine, ibid., p. 1320; F. Bohlmann, H. Bornowski, and H. Schonowsky,ibid., p. 1733; F.Bohlmann and H. Jastrow, ibid., p. 1742. 32 J. D. BuLock and H. M. Smalley, J., 1962, 4662.
30 31
272
poly acetylene, dehydromatriacarianol (26). The pathway envisaged is as follows:32
+ malonyl-CoA *
Acyl thiolester
Acylmalonyl thiolester
Enol derivative
--CO etc.
Polyacetylenes
Allenes.--a-Allenic acids are available by prototropic rearrangement of q3-acetylenic acids, induced by sodamide in liquid ammonia.3 A spontaneous, internal rearrangement of alk-2-ynyl phosphites to alka-172-dienyl phosphonates has also been encountered:33
HCiC*CH,*O *P(OEt) -+ H,C:C:CH*PO (OEt), . The cuprous chloride-catalysed reaction between 1-bromoprop-2-yne and
its derived di-Grignard reagent furnishes a separable mixture of octa-l,7diyne, octa-1,2-dien-7-yne7 and octa-172,6,7-tetraene(biallene) .34 The addition of bromine and of hydrogen bromide to unsymmetrical allenes is subject to allylic shifts.35 The reduction of a-allenic ketones, R*CO*CR:C:CH,, where R = alkyl and R = H or alkyl, has been described.36 Further attention has been paid to the problem of absolute configuration in allenes. Thus, (+)-glutink acid has been assigned the structure (27) by forming the Diels-Alder adduct with cyclopentadiene and converting this into the Z74-dinitrophenylhydrazone (+)-norcamphor of of established configuration.37
HO2C \
H
RH c :c :c. ,
p-CI*C H
(27)
-.C02H
4c:c:c:c:c..
/
C,H,CI But
-p
But
(28)
The stereochemistry of (-)-3-hydroxy-3,4,4-trimethylpent-l-yne has been established as (R) and that of the derived (+)-allene, 1-chloro-3,4,4trimethylpenta-172-diene, considered t o be the same in view of the reaction is mechanism involved.38 The first resolution of a pentatetraene (e.g., 28) has been claimed : substituted pentatetraenes and propadienes are said to have similar optical stabilities, much in excess of the geometrical stability found for the butatriene system,39 but these reports await substantiation. The chemistry of cumulenes has been and prototropic rearrangements to acetylenes have been reported.41 Olefinic Compounds.-General. Reviews of the Chugaev reaction 42 and of the methods of preparation of vinyl ethers and vinyl sulphides 43 have appeared. Two chemical determinations appear to substantiate earlier physical
V. Mark, Tetrahedron Letters, 1962, 281. G. Peiffer, Bull. SOC. chim. France, 1962, 776. 35A. V. Fedorova and A. A. Petrov, J . Gen. Chem. U.S.S.R., 1961, 31, 3273. 3 6 M. Betrand and J. Le Gras, Compt. rend., 1962, 255, 1305. 3 7 W. C. Agosta, J. Arner. Chem. SOC., 1962, 84, 110. 1962, 182. 3 8 R. J. D. Evans and S. R . Landor, Proc. Chem. SOC., M. Nakagawa, K. Shingu, and K. Naemura, Tetrahedron Letters, 1961, 802. 4 0 P . Cadiot, W. Chodkiewicz, and J. Rauss-Godineau, Bull. SOC. chim. France, 1961, 2176. 41 R. Kuhn and H. Fischer, Chem. Ber., 1961, 94, 3060. 4 2 H. R. Nace, Org. Reactions, 1962, 12, 57. 4 3 M. F. Shostakovskii, E. P. Gracheva, and N. K . Kulborskaya, Buss. Chem. Rev., 1961, 30, 207.
33
34
EGLINTON : ALIPHATIC COMPOUNDS
273
evidence that the s-cis-conformerof butadiene is present only to the extent of some 5%. The method used depends on the retention of molecular geometry on the part of a short-lived free radical generated by addition of a methyl radical.44 A new convenient, four-step synthesis makes trunshexa-1,3,5-triene available in 60% overall yield from crotonaldehyde and sodium acetylide.45 The interesting tetraene, 3,4-methylenehexa-1 5-diene, is obtainable by pyrolysis of the appropriate t e t r a - a ~ e t a t e . ~ ~ The isomerisation and rearrangement of olefinic systems continue to attract attention. Thus, a photochemically-induced equilibrium involving acyclic trienes and the corresponding cyclic dienes has been demonstrated : some polymer is formed in a d d i t i ~ n . ~ 'Kinetic studies of olefin isomerisations in the presence of potassium t-butoxide in dimethyl sulphoxide point
ca.
90%
ca.
10%
to a transition state with a preferred conformation consisting of base, solvent, and 0lefin.48 The same catalyst so speeds up the conjugation-isomerisation of the " skipped " polyene chains of linseed oil that the reaction is complete within a short time at room temperat~re.~Q Solvolysis of alk-3-enyl halides in aqueous potassium carbonate results in mixtures of the expected alcohols and of cyclopropanecarbinols, while pyrolysis of either cis- or truns-hex-3enedioic acid gives pent-4-en-1-oic acid (cu. 7oy0), presumably by way of cyclic transition states.50 The pair of isomeric alcohols derived by anionotropic rearrangement of hexa-1,4-dien-3-01are now believed to be formed concurrently rather than consecutively as proposed earlier :51
CH,*CH:CH*CH( 0H)CH:CH
+ CH,.CH(OH)*CH:CH*CH:CH, 89 % + CH,*CH:CH.CH:CH*CH,-OH 11%
H+
A light-catalysed addition of formamide to olefins, and to certain conjugated acetylenic bonds, has been described.52 Carotenoids.-The full stereochemistry of capsorubin has been dehed, and its optically inactive form and that of epicapsorubin have been synthe~ i s e d . The oxygen substituents on the five-membered ring are now said ~~ to be trans- 53 rather than ci~-oriented.~4 The configurations of capsanthin and zeaxanthin have also been provisionally assigned.53
W. B. Smith and J. L. Massingill, J. Amer. Chem. SOC.,1961, 83, 4301. J. M. Shackelford, W. A. Michalowicz, and L. H. Schwartzman, J . Org. Chem., 1962, 2'7, 1631. 4 6 W. J. Bailey and N. A. Nielsen, J . Org. Chem., 1962, 27, 3088.
44
45
G . J. Fonken, Tetrahedron Letters, 1962, 549. A. Schriesheim and C. A. Rowe, jun., Tetrahedron Letters, 1962, 405. 4 9 J. Ugelstad, B. Jenssen, and P. C. Mork, Acta Chem. Scand., 1962, 16, 323. s o S. Julia, M. Julia, and L. Brasseur, Bull. SOC. chim. France, 1962, 1634; F. Benington and R . D. Morin, J. Org. Chem., 1961, 26, 5210. 51 J. M. Shackelford and L. H. Schwartzman, J. Org. Chem., 1962, 2'7, 1047. 6 2 D. Elad, Chem. and Ind., 1962, 362; Proc. Chem. SOC., 1962, 225. 5 3 R. D. G . Cooper, L. M. Jackman, and B. C. L. Weedon, Proc. Chem. Xoc., 1962, 215. 5 4 H. Faigle and P. Karrer, Helv. Chim. Acta, 1961, 44, 1904.
47
48
274
ORGANIC CHEMISTRY
The cyclopropyl methyl ketone route for the stepwise elaboration of isoprenoid chains has been described in detail in relation to the synthesis of the C,, and derived acids.55 The Basle group, in a series of four papers, give details of their more recent synthetic studies, culminating in a full account of the spectral properties of vitamin A, and its stereoisomers.56 p-Carotene is obtainable from vitamin A in 28% yield by the route shown.
Vitamin A
t r a n s -/3
-Carotene
A complete scheme has been proposed for the biogenesis of spirilloxanthin via lycopene and five intermediate structures.57 The distribution of carotenoid pigments in the leaves of Acer phtanoides has been related to autumnal colour changesYa8 a similar analytical approach made to the and carotenoid content of the different anatomical parts of the flower of Delonix regia.69 Fatty Acids and Related Compounds.-Natural acids. The naturallyoccurring hydroxy-acids,60and the reactions ~ - 6 3 and synthesis 62, 63 of a wide variety of lipid substances, have been reviewed. The full impact of the newer physical methods for separation and structural analysis is being felt. I n the lipid field gas-liquid, thin-layer, and column partition chromatography, coupled with spectroscopic, particularly mass-spectrometric, measurements, are the techniques of choice, and it is now apparent that fatty acids almost invariably occur in Nature as complex mixtures of homologues and simply related acids. These findings are fortunately matched by an increased understanding of the biosynthetic pathways and enzyme specificities. Thus, the iso- (29) and anteiso-acids (30), which are major constituents of the lipid fractions of certain bacteria and other rnicro-~rganisrns,~~ are believed to be derived from starter units
Me,CH*[CH,],*CO,H Me-CH,*CMe*[CH,],CO ,H (29) (30) Me ,CH*[CH,],*CH:CH*CH,CO ,H
(31)
M. Julia and C. Descoins, Bull. SOC. chim. France, 1962, 1938. 5 6 U. Xchwieter, G. Saucy, M. Montavon, C. von Planta, R. Ruegg, and 0. Isler, Helv. Chim. Acta, 1962, 45, 517; U. Schwieter, C. von Planta, R. Ruegg, and 0. Isler, ibid., pp. 528, 541; C. von Planta, U. Schwieter, L. Chopard-dit-Jean, R. Ruegg, M. Kofler, and 0. Isler, ibid., p. 548. 5 7 H. J. Bestmann and 0. Kratzer, Angew. Chem., 1961, 73, 757; S. L. Jensen, G. Cohen-Bazire, and R. Y . Stanier, Nature, 1961, 192, 1168. 5 8 W. Eichenberger and E. C. Grob, Helv. Chim. Acta, 1962, 45, 974. 5 9 F. B. Jungalwala and H. R. Cama, Biochem. J., 1962, 85, 1. 6 o D. T. Downing, Rev. Pure Appl. Chem. (Australia), 1961, 11, 196. 61H J. Harwood, Chem. Rev., 1962, 62, 99. . 6 2 C. Paquot, Bull. Soc. chim. France, 1962, 213. 63 D. Swern, E. S. Rothman, L. S. Silbert, and J. S . Showell, Chem. and Ind., 1962, 1304. 6 4 M. Kates, D. J. Kushner, and A. T. James, Canad. J. Chem., 1962, 40, 83; M. G. MacFarlane, Biochem. J., 1962, 82, 40; M. Keeney, I. Katz, and M. J. Allison, J. Amer. O l Chemists SOC., i 1962, 39, 198.
65
EGLINTON
275
other than acetyl-CoA. An iso-acid (31)is claimed as the fatty acid portion of the antibiotic glumamycin65 and there are many iso- and anteiso-acids amongst the sixty-four acids so far detected in the saponified portion of cows m i l k . 6 6 Odd-numbered straight-chain acids are no longer a curiosity, as they are widely distributed minor components ascribed to the incorporation of propionyl-CoA starters. The complex mixture of branched acids of the tubercle bacillus has received further study. Chromyl acetate in carbon tetrachloride has been used to attack specifically the y-position of the phthienoic and it is now suggested that a series of phthienoic acids (32) ranging from C,, to C,, is present and that the trans-C,, major component 6 8 is probably accompanied by two other C,, ag-unsaturated acids. Further examples of this type of polybranched acid, involving chain extension by methylmalonyl Co*A units, are provided by the mycoceranic acids 6 9 (33; m = 2, n = 18, 19, 20, and 22; m = 3, n = 21,22, and 23) and the acids (33; m = 3, n = 1 and 2) which, when esterified with octadecan1-01, make up the major part of the liquid wax in the preen gland of the goose.70 An entirely different kind of polybranched acid (34)with a terpenoid skeleton has been isolated in 0.05% yield from butter fat.7l
Me.[CH ,],*CHMe.CH ,.CHMe.CH:CMe.CO ,H Me*[C H ,],*[CHMeCH ,],.CHMe-CO ,H H*[CH,*CHMe.CH ,CH ,],*CH,*CHMeCH,.CO ,H Me*CH,.CH:CH.CH,*CH,*CH( ) *CH,*CH:CH*[CH,],*CO ,H OH cis cis
(32) (33)
(34)
(35)
Among the unsaturated acids now filling out the pattern of straightchain fatty-acid biosynthesis are trans-octadec-16-enoic acid from butter fat (0-2y0), octadeca-trans-9,trans-11,cis-13-trienoic acid, which consti72 tutes the third naturally occurring geometrical isomer of elaeostearic acid,73 from Catalpa ovata seed oil, and, also from a seed oil, the related octadecacis-8,trans-lO7cis-l2-trienoic 71 An unusual hydroxy-fatty acid (35), acid. analogous to ricinoleic acid, is a major constituent of Lesquerellct densipila seed oil 7 5 and three skipped polyene acids have been isolated from canine adrenal lipids.76 The polar lipids of tubercle bacilli contain both 10-hydroxy- and 10-oxo-octadecanoicacid. 7 7
M. Inoue, Bull. Chem. SOC. Japan, 1962, 35, 1249, 1255. P. Magidman, S. F. Herb, R. A. Barford, and R. W. Riemenschneider,J . Amer. Oil Chemists SOC.,1962, 39, 137; S. F. Herb, P. Magidman, F. E. Luddy, and R. W. Riemenschneider, ibid., p. 142. 6 7 J. Cason, P. Tavs, and A. Weiss, Tetrahedron, 1962, 1 , 437. 8 6 8 R. Ryhage, S. Stiillberg-Stenhagen, and E. Stenhagen, Arlciv Kemi, 1962, 18, 179. 6 s N . Polgar and W. Smith, Chem. and Ind., 1961, 1958. 7 0 K. E. Murray, Austral. J . Chem., 1962, 1 , 510. 5 l W. Sonnevald, P. H. Begemann, G. V. van Beers, R. Kerning, and J. C. M. Schogt, J . Lipid Res., 1962, 3, 351. 7 2 R. P. Hansen and N. J. Cook, Biochem. J., 1961, 81, 233. 73 C. Y. Hopkins and M. J. Chisholm, J., 1962, 573. 7 4 M. J. Chisholm and C. Y . Hopkins, J . Org. Chern., 1962, 27, 3137. 7 5 C. R. Smith, jun., T. L. Wilson, R. B. Bates, and C. R. SchoEeld, J . Org. Chern., 1962, 27, 3112. 7 6 Ta-Chuang Lo Chang and C . C . Sweeley, J. Lipid Res., 1962, 3 170. , 7 7 N. Polgar and W. Smith, J., 1962, 4262.
65 66
276
ORGANIC CHEMISTRY
The absolute configuration (36) of prostaglandin Fz-17 of a group of one closely related, intensely potent, smooth-muscle stimulants isolated from seminal fluids, has been established by a full X-ray analysis;8 one possible derivation would require cyclisation of a C,, straight-chain acid precursor.
..., ..
H
I
Me .[CH2] Me.[CH;],-
,- C-CH:CH 1\1 C - CH :CH

OH OH
,o,
f~~
(36)
Synthesis. The desulphurisation of 2,ti-disubstituted thiophens has been extensively used during the year for the synthesis of long-chain fatty acids and related compounds, and several reviews of the method have appeared. 79 Some interesting examples are the synthesis of specifically labelled [9-14C]straight chain acids (37),80 hydroxy-acids (38),*l of individual enantioof of mers of polybranched acids (39),82 of iso- and anteiso-a~ids,~~the and D-isomer of 21-methylhexatriacontan-3-one7~4 of a partially fluorinated alkane (40).85a A somewhat analogous chain-lengtheningprocedure, which involves alkylation in the 5-position of a 2-substituted furan, acid-catalysed ring-opening, and reduction of the resulting ketone groups, has been employed in the synthesis of dihydrohydnocarpic and dihydrochaulmoogric acid. 85b
BaC03
R*?OCI
R?-) -O(-
[CH;];C02Me I
1, Friedel-Crafts. 2, Huang-Minlon. 3, Raney nickel. R*[CH,]s*CH(OH)~[CH,]8*C0,H Me*[CH2] ,,fCHMeCH,],CHMeCO ,H

(38)
C3F7
( 0
C3F7*C0
(39)
CH( OH) .FH2I3*CH3
C,FT*COCI
JI
C3F 7 .[CH2]
, CH,
(40)
Acetylenic routes to skipped polyenoids continue to be exploited, and further syntheses include those of the four stereoisomers of linoleic acid,86, 8 7 vernolic acid (41),87and y-linolenic acid.87 The Cadiot-Chodkie7 8 S. Abrahamsson, S. Bergstrom, and B. Samuelsson, Proc. Chem. Soc., 1962, 332. 7 9 G. R. Pettit and E. E. van Tamelen, Org. Reactions, 1962, 12, 356; Y. L. Goldfarb, B. P. Fabrichnyi, and I. F. Shaluvina, Tetrahedron, 1962, 18, 21; H. Hauptmann and W. F. Walter, Chem. Rev., 1962, 62, 347. s o J. D. BuLock, G. N. Smith, and C. T. Bedford, J., 1962, 1405. 81 K. E. Miller, C. R. Haymaker, and H. Gilman, J . Org. Chem., 1961, 26, 5217. s 2 N . Polgar and W. Smith, Chem. and Ind., 1961, 1959. 83 J. F. McGhie, W. A. Ross, D. Evans, and J. E. Tomlh, J., 1962, 350. 8 4 R. Toubiana, Compt. rend., 1961, 253, 2989. 8 5 ( a ) S. Portnoy and H. Gisser, J. Org. Chem., 1962, 27, 3331; (b) E. Buchta and F. Fuchs, Annulen, 1962, 655, 81. s 6 M. Gaudemaris and P. Arnaud, Bull. SOC. chim. France, 1962, 315. e7 J. M. Osbond, J., 1961, 5270.
EGLINTON : ALIPHATIC COMPOUNDS
277
wiez procedure has been used for conjugated systems such as hexadeca8,lO-dienoic acid 88 and octadeca-trans-13,trans-l5-diene-9,1 l-diynoic acid.8 9 CH,fCH,]4*CH:CH*CH,*CiC*[CH,],*C0,H +
cis
CH,.[CH&*CH-CH*CH ,*CH:CH*[CH,],*CO (4 ) 2 H 1
\/
0
Cis
The natural insecticide, affinin, has properties indistinguishable from those of synthetic N -isobutyldeca-t r m s -2 ,cis- 6,trans-8-trienamide. Further structural and synthetic studies centred on the principal acid of royal jelly, 10-hydroxy-trans-dec-e-enoic have a p ~ e a r e d . ~ l Cycloacid, -~~ octanone has been used as starting material for the intermediate, 8-hydroxyoctanal,92 and related hydroxy-a/kmsaturated acids have been synthesised and te~ted.~33 An extensive paper 95 gives details of the work which 94 pioneered the isolation, characterisation, and synthesis of the " queen substance," 9-oxodec-trans-2-enoicacid. A further synthesis of this acid has been reported 9sa and a complete account given 93b of the Wittig route which makes it available in ca. 15% overall yield from glutardialdehyde. Natural derivatives. The distribution of fatty acids in natural glycerides,96 and the synthesis,97 properties,97 and polymorphism 98 of glycerides, have been reviewed. An increasing number of papers describe extended analyses of complex natural mixtures, usually with the aid of gas-liquid chromatography. For example, the long-chain alkanes, acids, and alcohols derived from brown coal-wax have been detailed,99and eicosyl and eicosenyl palmitate together with cholesterol derivatives have been shown to be important components of human skin wax.1oo The alkane fractions of plant lo1 and insect lo2 waxes are often complex but the complexity itself may have taxonomic value : thus, in some species of Crassulaceae, isoalkanes are major constituents l o l and there have been attempts to correlate the chain-length distributions of the n-fatty acids and n-alkanes in recent sediments in relation to the problem of the origin of petroleum.lO3 Long-chain
*SF. Gunstone and P. J. Sykes, J., 1962, 3055, 3058, 3063. D. 8 9 L. Crombie and J. C. Williams, J., 1962, 2449. L. Crombie and A. H. A. Krasinski, Chem. a n d Ind., 1962, 983. 9 1 S. A. Barker, A. B. Foster, D. C. Lamb, and L. M. Jackman, Tetrahedron, 1962, 18, 177. 9 2 U. Schmidt and P. Grafen, A n n a l e n , 1962, 656, 97. 93 ( a ) K. Sisido, M. Kawanisi, K. Kondo, T. Morimoto, A. Saito, and N. Hukue, J. Org. Chem., 1962, 27, 4073; (b) K. Eiter, A n n a l e n , 1962, 658, 91. g 4 W. H. Brown, E. E. Felauer, and M. V. Smith, Canad. J. Chem., 1962, 40, 1882. 9 5 C. G. Butler, R. K. Callow, and N. C. Johnston, Proc. Roy. SOC., 1961, B, 155, 417. 9 6 F. D.Gunstone, Chem. and I n d . , 1962, 1214; M. M. Rapport and W. T. Norton, Ann. Rev. Biochem., 1962, 21, 103. 97 R. H. Mattson and R. A. Volpenhein, J . L i p i d Res., 1962, 3, 281. 9 8 D. Chapman, Chenz. Rev., 1962, 62, 433. 9 9 V. Wollrab, M. Streibl, and F. Siirm, Chem. and I n d . , 1962, 1762. looE. 0. A. Haahti and E. C. Horning, A c t a Chem. Scand., 1961, 15, 930. lol G. Eglinton, A. G. Gonzalez, R. J. Hamilton, and R. A. Raphael, Phytochemistry, 1962, 1, 89; G. Eglinton, R. J. Hamilton, and M. Martin-Smith, ibid., p. 137. l o 2 S. J. Louloudes, D. L. Chambers, D. B. Mayer, and J. H. Starkey, Ann. E n t . SOC.Amer., 1962, 55, 442. l o 3J. E. Cooper, N a t u r e , 1962, 193, 744.
278
ORGANIC CHEMISTRY
alcohols, such as those present in the mixture of nocardols (42) from Nocardia asteroid@ lo4and of diols lo5 from apple a,nd carnauba waxes, are receiving increased attention. CH3*[CH,],-l,*CH:[C,4H453CH2].CH(OH)*CH2*[CH2]n*CH3n = 13, 15) f (42;
CH3-[CH,],,CO*CH,*CO*[CH2],,*CH3 (43)
CH3.[CH,16*CH=CH*C~CH*CH= CH,*OAc
trans
CH*CO,H
(44)
Long-chain @-diketones(e.g., have been reported for the first time as 43) natural products: they are major components, up t o 50% or more, in the leaf and stem waxes of certain Eucalyptus, Acacia, and other species.106 Another biogenetically interesting constituent of leaf coatings is the novel, lo7 unsaturated, branched acid (44). Miscellaneous findings are that non-l-eno has been isolated from a member of the Composit~,los that the fragrant lactone in the essential oil of jasmine is tetrahydro-5-cis-pent-2-enylpyran-2-one,109 hex-3-en-1-01is that a termite attractant, and that 2-methylpent-2-enal is one of the odoriferous compounds liberated enzymically in crushed onions. ll1 Considerable further progress has been made in the study of insect sexattractants. The extremely potent attractant secreted by the female Gypsy moth as a lure for the male has been identified by degradation and synthesis as (+)-lO-acetoxy-cis-hexadec-7-en-l-o1(45). Rather surprisingly, both enantiomers are equally effective (at a level of ca. pg!). Several related compounds were also prepared and tested for biological potency. 112 Full details have now appeared 113 of the elegant studies which have culminated in the identification and synthesis, by several routes, of bombykol (trans,cis-hexadeca-lO,lZ-dienol), sex-attractant of the silk moth. the CH,*[CH,],-CH(OAc)*CH,*CH:CHfCH,],*CH,-OH (45)
cis
The structure (46) of the antibiotic fungichromin, which may possibly be identical with lagosin, has been determined and the absolute configuration
OH OH OH O H
OH
OH OH
(46)
Me
lo4 G. lo5 P. lo6 D. lo P. 108 T.
OH
Michel and E. Lederer, Bull. SOC. chim, France, 1962, 651. Mazliak, Phytochemistry, 1962, 1, 79. H. S . Horn and J. A. Lamberton, Chem. and Ind., 1962, 2036. R. Jefferies and J. R. Knox, Austral. J . Chem., 1961, 14, 628. Kurihara, M. Takase, and N. Iino, J . Pharrrt. SOC. Japan, 1962, 82, 1070. Ion Winter, G. Malet, M. Pfeiffer, and E. Demole, HeZv. Chim. Acta, 1962, 45, M. 1250; E. Demole and M. Winter, ibid., p. 1256. 110 H. Verron and M. Barbier, Compt. rend., 1962, 254, 4089. 111 C. G. Spare and A. I. Virtanen, Acta Chem. Scand., 1961, 15, 1280. 112 M. Jacobson, M. Beroza, and W. A. Jones, J . Amer. CJbem. SOC., 1961, 83, 4819; M. Jacobson and W. A. Jones, J . Org. Chem., 1962,27, 2523; M. Jacobson, ibid., p. 2670. l l s A . Butenandt, E. Hecker, M. Hopp, and W. Koch, Annalen, 1962, 658, 39; E. Truscheit and K. Eiter, ibid., p. 65.
EGLINTON
279
established at two of the 12 asymmetric centres.114 An interesting paper discusses the structures of the bydroxy-acids obtained by fermentation of fatty acids and of hydrocarbons.l15 Nitrogen Derivatives.-Syntheses of aliphatic nitro-compounds 116 and of aminoguanidine and related compounds 117 have been reviewed. Crystalline derivatives (47) can now be obtained from nitroalkanes by a Mannichtype condensation,ll8 and 1-nitroalkanes undergo Michael condensation with one or two mol. of acrylic acid derivatives in liquid ammonia.llg
p-C6H4Me.NR, CH,O +
+ CHRRoNO, --+ p-C,H,Me*NH*CH,-CRR-NO, (47)
Interest continues in the chemistry of cyano-compounds. The salts of tricyanomethane are readily accessible from malononitrile,120 basically substituted malonitriles (48) have been prepared,l21 and several useful reactions have been reported.122u For example, amidines result 122a in
Me,N*CH( CN)
(48)
Me*C (OEt):C( CN)*CS*NH,

(49)
(But) ,NO
(50)
70--80% yield from pressure treatment of nitriles with ammonia and ammonium halides at 125-150, and addition of hydrogen sulphide to a substituted methylenemalonitrile furnishes l 2 Z b the thioamide (49). A new group of stable, aliphatic, nitrogen-containing free radicals, the di-t-alkyl nitroxides, has been rep0rted.1~3 Di-t-butyl nitroxide (50) is a remarkably stable, red liquid, formed in 22% yield by reduction of 2-nitro2-methylpropane with sodium at 20.l 2 3 The special steric properties of the t-butyl group have also been utilised in the following sequence proceeding via pernitrosopinacolone (51).124
MeButC:N*OH + MeButC:N*NO
1
,7 MeButCH-NH-NO ,
(51)
1, Nitrosation. 2, Reduction with KBH,.
Sulphur Derivatives.-Cyclic sulphides have been reviewed.125 Isothiocyanates RNCS with branched alkyl substituents [Pri, (8)-s-butyl, and (8)-2-rnethylbutyl], and the related compound (52), are present in an enzymic(52) ally hydrolysed seed oi1.126
i:<rs
114A. C. Cope, R. K. Bly, E. P. Burrows, 0. J. Ceder, E. Ciganek, B. T. Gillis, R. F. Porter, and H. E. Johnson, J. Amer. Chem. SOC., 1962, 84, 2170. 115A. P. Tulloch, J. F. T. Spencer, and P. A. J. Gorin, Canad. J. Chem., 1962, 40, 1326. 116 N. Kornblum, Org. Reactions, 1962, 12, 101. 117 F. Kurzer and L. E. A. Godfrey, Chem. and Ind., 1962, 1584. 118 M. B.Winstead,R. G. Strachan,andH. W.Heine, J. Org.Chem., 1961,26,4116. 119 S. Wakamatsu and K. Shimo, J. Org. Chem., 1962, 27, 1609. 1 2 0 S. Trohenko, E. L. Little, jun., and H. F. Mower, J. Org. Chem., 1962,27,433. 121 H. Gold and 0. Bayer, Chem. Ber., 1961, 94, 2594. 122 (a) F. C. Schaefer and A. P. Krapcho, J. Org. Chem., 1962, 27, 1255; ( b ) M. A. &Call, ibid., p. 2433; (c) E. N. Zilberman, N. K. Taikova, N. A. Rybakova, and K.L. Feller, Zhw. obshchei Khim., 1961, 31, 2040 (J. Gen. Chem., 1961, 13, 1908). 123 A. K. Hoffmann and A. T. Henderson, J. Amer. Chem. SOC., 1961, 83, 4671. 124 J. P. Freeman, J. Org. Chem., 1961, 26, 4190. 1 2 5 Yu. K. Yurev and E. G. Rozantsev, Russ. Chem. Rev., 1962, 31, 87. 1 2 6 A. Kjaer and P. Friis, Acta Chem. Scand., 1962, 16, 936.
280
ORGANIC CHEMISTRY
Ethylene monothiolcarbonate is at suitable reagent for the mercaptoethylation of amines.lZ7 Routes t o epithio-acids have been examined,l28 a mechanism has been proposed for the oxidative rearrangement (at 5 " ) of
CH,:C(OEt).SPh
+PhS*CH,*CO,Et
(54%)
vinylic sulphide~,l2~ the products derived from the addition of thiols to and diacetylene have been discussed.130 Certain disulphides interact with nucleophiles [e.g., P(0Et)3, CN-] to form monosulphides.l 3 l The thiolate ion-disulphide exchange has been
examined,
[Me,S *NH,]X-, and the corresponding sulphidimine, Me,S :NH. 133 Sulphonic acids may be obtained from alk-l-enes by free-radical addition of Me GO-SH and then oxidation,l34 while chlorinated methanesulphonyl chlorides add similarly to olefins and thereby provide a new route to a range 135 of polychloroalkanes. Miscellaneous.-Useful reviews dealing with enol phosphates 136 and carbenes 13' have been published. Several new and ingenious methods for the generation of carbenes and similar unstable intermediates have been devised. Thus, alkylcarbenes are formed as a result of the interaction of methylene chloride with alkyl-lithiums,13* of treatment of alkyl diphenyland sulphonium salts, [Ph,S*CH,R]BF,-, with bases.l 3 9 Dichlorocarbene is cited as an intermediate in the preparation 140 of a thioformamide, Bu",N*CHS, and in the reaction between the ester, CCl,*SO*OMe,and an olefin in the presence of potassium t-butoxide.141 Difluorocarbene has also been disc~ssed.l4~ Two interesting and reactive intermediates derived from dimethyl
1 ' D. D. Reynolds, M. K. Massad, D. L. Fields, and D. L. Johnson, J. Org. Chem., 2 1961, 26, 5109; D. D. Reynolds, D. L. Fields, and D. L. Johnson, ibid., pp. 5119, 5122, 5125, 5130. 128 J. F. McGhie, W. A. Ross, F. J. Julietti, and B. E. Grimwood, J., 1962, 4638. 129 W. E. Truce and R. J. Steltenkamp, J. Org. Chem., 1962, 27, 2816. 130 E. N. Prilezhaeva, L. V. Tsymbal, and M. F. Shostakovskii, J. Qen. Chem. (U.S.S.R.), 1961, 31, 2487; M. E. Shostakovskii, E. N. Prilezhaeva, L. V. Tsymbal, R. Ya. Tolchinskaya, and N. G. Starova, ibid., p. 2496. 131 C. G. Moore and B. R. Trego, J., 1962, 4205. 132 C. G. Moore and A. A. Watson, Tetrahedron, 1962, 18, 219. 133 R. Appel and W. Buchner, Chem. Ber., 1962, 95, 849, 855. 134 J . S. Showell, J. R. Russell, and D. Swern, J. Org. Chem., 1962, 27, 2853. 135 H. Goldwhite and C. Harris, Chem. and Ind., 1962, 1721. 136 F. W. Lichtenthaler, Chem. Rev., 1961, 61, 607. 13' P. Miginiac, Bull. SOC. chim. France, 1962, 2001. 138 G. L. Closs, J. Arner. Chem. SOC., 1962, 84, 809. 139 V. Franzen, H.-J. Schmidt, and C. Mertz, Chem. Ber., 1961, 94, 2942. 140 W. Walter and G. Maerten, Angew. Chem., 1961, 73, 755. l r l U . Schollkopf and P. Hilbert, Angew. Chem., 1962, 74, 431. 142 S. Andreades, Chem. and Id., 1962, 782.
and dimethyl sulphide converted into sulphiminium salts
O V E R T O N : ALICYCLIC C O M P O U N D S
281
sulphoxide have been described : dimethylsulphoxonium methylide, Me#( :0):CH,, is a selective methylene-transfer agent, and the system, methylsulphinyl carbanion, [MeS(*O)GH,]-- dimethyl sulphoxide, is an extremely powerful base. 143
G. E.
6. ALICYCLIC COMPOUNDS
Small, Medium, and Large Rings.-Diphenylcarbene from dibromodiphenylmethane and methyl-lithium adds stereospecificallyto olefins, to form diphenylcyclopropanes. Methylenecyclopropane is formed in 60% yield from allene and diazomethane ;2 it undergoes normal olefinic addition^.^ Alkenylidenecyclopropanes (1)are obtained from ethynyl carbinyl chlorides and olefins in presence of a base via alkenylidene carbenes (2). The stereo.CHZ
( I)
R HCL'C =c =c R 2 I
:c=C=CR;
(2)
chemical factor in cyclopropyl conjugation has been discussed for cc-cyclopropyl- and orb-unsaturatedy-cyclopropyl-alkylketones. Di- and tri-propylcyclopropenyl cations (3; R = H or Pr) have been prepared 6 and their aromaticity has been discussed. Solvolysis of diphenylcyclopropenyl toluene-p-sulphonate proceeds through an ion written as (4);'the rate is not affected by the presence of the double bond. Several papers deal with the
infrared,*, ultra~iolet,~ nuclear magnetic resonance spectra 9-11 of and cyclopropane derivatives. ( )-trans-Chrysanthemic acid (5) has been synthesised l2 from (+)-pyrocin (6). The formation of cyclobutane derivatives by thermal cycloaddition has been reviewed.l3 Tetracyanoethylene adds 14 to 4-methylpenta-1,3-dieneY forming the cyclobutane (7) (69%) and the Diels-Alder adduct (8) (llyo). Irradiation of sterically favourable dienes gives 15 cyclobutenes in good yield ;
143
G. L. Gloss and L. E. Gloss, Angew. Chem., 1962, 74, 431. A. T. Blomquist and D. J. Connolly, Chem. and Ind., 1962, 310. B. C. Anderson, J. Org. Chem., 1962, 27, 2720. H. D. Hartzler, J . Amer. Chem. SOC.,1961, 83, 4990, 4997. E. M. Kosower and M. Ito, Proc. Chem. SOC.,1962, 25. R. Breslow, H. Hover, and Hai Won Chang, J. Amer. Chern. SOC.,1962, 84,
3168.
E J. Corey and M. Chaykovsky, J. Amer. Chem. SOC., . 1962, 84, 866, 867, 3782.
G. Gassman, Chem. and Ind., 1962, 740. H. Weitkamp, U. Hasserodt, and F. Korte, Chem. Ber., 1962, 95, 2280. l o J. D. Graham and M. T. Rogers, J . Amer. Chem. SOC., 1962, 84, 2249. l l H . M. Hutton and T. Schaefer, Canad. J. Chem., 1962, 40, 875. l 2 M. Matsui and M. Uchiyama, Agric. and B o . Chem. (Japan), 1962, 26, 532. il l 3 J. D. Roberts and C. M. Sharts, Org. Reactions, 1962, 12, 1. l4 C. A. Stewart, jun., J. Amer. Chern. SOC., 1962, 84, 117. l 6 K. G. Crowley, Proc. Chem. Soc., 1962, 334.
' R. Breslow, J. Lockhart, and A. Small, J. Amer. Chem. SOC.,1962, 84, 2793.
282
ORGANIC CHEMISTRY
myrcene gives 54% of the diene (9). Irradiation of cyclo-octa-1,3-diene gives rise to the bicyclic compound (10) as the sole product.16
Me,C=CH
(7)
I;:::
@N12
( W 2
; L
(8)
(9)
J f
(10)
1,2,5,6-Tetrabromocyclo-octanegives benzocyclobutene (as does the concomitantly formed cyclo-octatetraene) with potassium t-butoxide a t l2OO.17 Benzocyclobutene is cleaved l8 in reaction with maleic anhydride,
(13;
R = Br)
(15; R = CN, n = 4 ) ( I 6 ; R E CHO, n - 3 )
(14; R = O A c )
giving the adduct (11)and with sulphur dioxide gives the sulphone (12); at 200" it dimerises to dibenzocyclo-octadiene. The halide (13) reacts with potassium cyanide to give the all-trans-compound (15),19 and with lithium aluminium hydride the acetate (14)gives the all-trans-olefinicaldehyde (16).20 The preparation of the symmetrical aromatic dianion (17) has been published in full.21 A crystalline salt of the tetraphenylcyclobutenium cation (18) has been prepared.22 Treatment of the dichloride (19)with silver hexafluoroantimonate appears to give 23 the ion (20)instead of the expected (18a).
2-
. *
.....
(1 71
*. .
RpJR
R R (1 9 )
(18; R=Ph)
(18a; R = M e )
CI
+C I
(20)
Attempts to prepare cyclobutadiene and its derivatives have been reviewed.24 These are so far unsuccessful and there is no convincing evidence for their appearance as intermediates. Tetramethylenecyclobutane results 25 from pyrolysis of the tetranitro-compound (21; X = NO,), and its octaphenyl derivative 26 from light-induced dimerisation of tetraphenylbutal6 S. F. Chappell, tert., and R. F. Clark, Chem. and Ind., 1962, 1198; W. G. Dauben and R. L. Cargill, J. Org. Chem., 1962, 27, 1910. l7 G. Eglinton, R. A. Raphael, and R. G. Willis, Proc. Chem. Soc., 1962, 334. l8 F. R. Jensen, W. E. Coleman, and A. J. Berlin, Tetrahedron Letters, 1962, 15. l9 H. Hoever, Tetrahedron Letters, 1962, 255. 2 o R. Anet, Tetrahedron Letters, 1961, 720. 21 J. D. Park, S. Cohen, and J. R. Lacher, J. Amer. Chem. SOC., 1962, 84, 2919. 2 2 H. H. Freedman and A. M. Frantz, J. Amer. Chem. SOC.,1962, 84, 4165. 23 T. J. Katz, J. R. Hall, and W. C. Neikam, J. Amer. Chem. SOC., 1962, 84, 3199. 2 4 R. Griegee, Angew. Chem., 1962, 74, 703. 2 5 G . E. Griflfin and L. I. Peterson, J . Amer. Chem. SOC., 1962, 84, 3398. 26 R. 0. Uhler, . Xhechter, and G . V. D. Tiers, J . Amer. Chem. SOC., 1962, 84, 3397.
OVERTON : A L I C Y C L I C C O M P O U N D S
283
triene. The tin derivative (22) gives 27 on irradiation 1,2,3-triphenylazulene (23), possibly by way of tetraphenylcyclobutadiene. The structure of the cyclobutadiene dimer (24) derived from the halide (25) and phenyllithium has been determined 28 by X-rays. Diphenylacetylene and phenylmagnesium bromide give 29 the octaphenyl dimer (26) and not " octaphenylcubane. " Convincing evidence has been obtained 30 for the structure
"""K:::
Ph XH2C
(21)
Ph
/ \ Me
I -Sn
a
Ph Ph
Me
(22)
Ph T
(23)
ph]j--ff-ii'::
Ph
(24;
C : n
F
(25)
Ph Ph
''
Ph
g
Ph..:..!hi
h Ph Ph
R=F)
R-Ph)
(27)
(26;
of " octaphenylcubane " (27) (octaphenylpentacycl0[4,2,0,0~~~,0~~~,0 octane) previously prepared and an improved synthesis has been de~cribed.~' 4-Substituted cyclopentenes can be made 32 by condensation of cis-l,4dihalogenobut -2- enes with ethj-1 malonat e. Mercury-sensitised p hot olysis of cyclopentene gives vinylcyclopropane as the major product, 33 but the reverse reaction occurs thermally. 4-Methylcyclopentene adds acetyl hypobromite stereoselectively; with perlauric acid it gives a mixture of cc- and B-ep~xide,~* and cyclopent-3-en0135 behaves similarly with this reagent. Photo-induced dimerisation of cyclopentadiene gives 36 the dienes (28), (29), and (30) in equal amounts, in contrast t o thermal dimerisation.
The first pentalene derivative free from fused rings (31) has been synthesised. 37 I n reaction with acetylenedicarboxylic ester its ring expands to give the szulene (32). Pyrolysis 38 of isodicyclopentadiene (33) and treatH. H. Freedman, J . Org. Chem., 1962, 27, 2298. C. Fritchie, jun., and E. W. Hughes, J. Amer. Chem. SOC.,1962, 84, 2257. 2B M. Tsutsui, Chem. and Ind., 1962, 780. H. Freedman and D. R. Petersen, J . Amer. Chem. SOC.,1962, 84, 2837. 31P. Maitlis and F. G. A. Stone, Proc. Chem. SOC.,1962, 330. M. 3 2 K. C. Murdock and R. B. Angier, J . Org. Chem., 1962, 27, 2395; J. Meinwald, P. G. Gassman, and J. K. Crandall, ibid., p. 3366. 33 W. A. Gibbons, W. F. Allen, and H. E. Gunning, Canad. J . Chem., 1962, 40, 668. 84 H. B. Henbest and J. J. McCullough, Proc. Chem. Soc., 1962, 74. s 5 A. C. Darby, H. B. Henbest, and I. McClenaghan, Chem. and Id., 1962, 462. B 6 N. J. Turro and G. S . Hammond, J . Amer. Chena. Soc., 1962, 84, 2841. E. le Goff, J . Amer. Chem. SOC.,1962, 84, 3975. s8 T. J. Katz and M. Rosenberger, J . Arner. Chem. SOC., 1962, 84, 865.
27
28
284
ORGANIC CHEMISTRY
ment of the product with butyl-lithium gives the pentalenylidene dianion (34). Photodimerisation of cyclopentenone 39 gives the cis- (35) and the
Ph P
/
Ph a Ph Ph
Ph Ph
Ph
Ph R C02Me (32; R = Ph or COzMe

R= C02Me or Ph)
[ =I2-
R Q -o n
W
(34)
(37)
R = H2, R= 0 )
(35; R = 0 , R= H2)
(36;
trans-ciimers (36). The carbonyl group of the unexcited partner is unnecessary since cyclopentene condenses with cyclopentenone. Diels-Alder addition of t-butylketen to cyclopentadiene gives 40 the ketone (37). Cyclopent-2-enylmethylamine (38; R = NH,) with nitrous acid, and the corresponding t oluene-p- sulphonate with :methanol, give, respectively, the bicyclo[3,1,0]hexanes (39; R = H) and (39; R = Me).
(40)
The smooth-muscle stimulant prostaglandin F2, 2 frommammalian sperm, 4 has been shown t o have structure (40) by X-ray investigation; on ozonolysis it gives (R)-2-hydroxyheptanoic acid. The mechanism of oxidation of monocyclic cyclohexanols by chromic acid has been the subject of argument.43 The chemical shifts in the nuclear magnetic resonance spectra of axial and equatorial cyclohexanols have been discussed.4 4 A novel annelation 4 5 results from irradiation of cycloalkenes with acetylacetone and cyclisation of the initial product. Cyclohexene gives the enones (41) and (42) via the dione (43).
P. E. Eaton, J . Amer. Chem. Soc., 1962, 84, 2344, 2454. W. Rellensmann and K. Hafner, Chem. Ber., 1962, 95, 2579. 4 1 3 1 . Hanack and H. J. Schneider, Angew. Chem., 1962, 74, 388. 4 2 X. Abrahamsson, S. Bergstrom, and B. Samuelsson, Proc. Chem. SOC., 1962, 332; S. Bergstrom, R. Ryhage, B. Samuelsson, and J. Sjovall, Acta Chem. Xcand., 1962, 16, 501. 43H. Kwart, Chem. and Ind., 1962, 610; J. C. Richer, L. A. Pilato, and E. L. Eliel, ibid., 1961, 2007. 44 E. L. Eliel, M. H. Gianni, T. H. Williams, and J. B. Stothers, Tetrahedron Letters, 1962, 741. 4 5 P. de Mayo, H. Takeshita, and A. B. M. A. Sattar, Proc. Chem. SOC., 1962, 119.
39
4O
O V E RT O N : A L I C Y C L I C C O M P O U N D S
285
Evidence 46 for a non-classical cyclohexenyl cation (44)or (45) has been obtained.
COzMe
But
(44)
(45)
(46)
(47)
(48)
Light-induced reversal of the well-known photolysis of 1,3-cyclohexadienes to acyclic trienes has been observed.47 Diazomethane-sensitised phototautomerisation 48 of the diene (46) gives a bicyclic ester (47) [cf. (170)l. The Dewar-benzene derivative (48) has probably been obtained 49 by irradiation of the corresponding tii-t-butylbenzene. A pyrolytic synthesis of the toluene isomer (50) has been reported.50 Only axial 2-phenylcyclohexanoneshave intense n ---+ n* bands; the sign of the Cotton curve is predictable.51 The cyclohexadienone (51)photolyses 5 2
H02C. CH2. CO. COLH H01C.H2C, ,GH2-COMe CH C I
(50)
Me
CHCI2
Me
/ \
0
H
153)
CHCI
HO
(52)
(51)
t o the open-chain ketone (52). The configuration of prephenic acid (53) accords with its postulated biogenesis; progress towards its synthesis has been reviewed.53 Conjugated cycloheptadienes result 54 from 1&addition to tropone and y-tropolone methyl ether. Under irradiation the products undergo valency tautomerisation to bicyc10[3,2,0]hept-6-enes.~~ Treatment of the product (54) from dichlorocarbene and ethoxycyclohexane with base and then acid
e6
4'
SOC.,1962, 84, 1498; G. A. Olah and W. S. Tolgyest, ibid., 1961, 83, 5031.
48
N. C. Deno, H. G. Richey, J. D. Hodge, and M. J. Wisotsky, J. Amer. Chem.
G. J. Fonken, Tetrahedron Letters, 1962, 549. H. Prinzbach and J. H. Hartenstein, Angew. Chem., 1962, 74, 651. 4 9 E. E. van Tamelen and S. S. Pappss, J. Amer. Chew,. $oc., 1962, 84, 3789. 5 0 W. J. Bailey and R. A. Baylouny, J. Org. Chem., 1962, 27, 3476. 5 1 R . C. Cookson and J. Hudec, J., 1962, 429. 5 2 E. E. van Tamelen, K. Kirk, and G. Brieger, Tetrahedron Letters, 1962, 939. 53 H. Plieninger, Angew. Chem., 1962, 74, 48, 423. 5 4 0. L. Chapman, D. J. Pasto, and A. A. Griswold, J. Amer. Chem. SOC., 1962, 84, 1213; 0. L. Chapman, D. J. Pasto, G. W. Borden, and A. A. Griswold, ibid., p. 1220.
286
ORGANIC CHEMISTRY
readily gives cyclohepta-3 5-dienone. The heptaphenylcycloheptatrienyl anion (55) is a singlet and not a triplet.56
The first optically active cyclic trans-olefin, (+)- and (-)-cis-trans-cycloocta-lY5-diene, been prepared.57 Moreover, trans-cyclo-octeneitself has has been resolved.57b Pariser-Parr calculations for cyclo-octatetraene 58 show that it has an alternating bond structure; and II: for the interconversion of mesomers has been e ~ t i m a t e d . The dianion is planar and quasi~~ aromatic.58, 60 The nuclear magnetic resonance spectrum of the product from cyclooctatetraene, antimony pentachloride, and hydrogen chloride supports 6 1 cypher (56) as the structure of the cation. The first optical resolution of a
<C
Ph
(57)
(58)
substituted cyclo-octatetraene has been effected.62 Cyclo-octyne has been prepared 6 3 and trapped as the adduct (57); cyclo-heptyne, -hexyne, and -pentyne were formed in decreasing yields.63 Independent chemical and X-ray studies have established the constitution and stereochemistry of two members of a new class of natural product, the nonadrides: ( 6 0 ) glauconic acid (58) and byssochlamic acid (59).64 Crystal-structure analysis of trans- and cis-cyclodecanelJ6-diamine di-
D
55
R. Breslow and Hai Won Chang, J . Amer. Chem. SOC.,1962, 84, 1484. ( a ) A. C. Cope, C. F. Howell, and A. Knowles, J . Amer. Chem. SOC., 1962, 84, 3190; ( b ) A. C. Cope, C. R . Ganellin, and H. W. Johnson, jun., ibid., p. 3191. 5 8 N. L. Allinger, J . Org. Chem., 1962, 27, 443. 5 g F. A. L. Anet, J . Amer. Chem. SOC., 1962, 84, 671. 6 o P. G. Farrell and S. F. Mason, 2. Natur-orsch., 1961, 16b, 848. 61 J. L. von Rosenberg, jun., J. E. Mahler, and R. Pettit, J . Amer. Chem. Soc., 1962, 84, 2842. 6 2 K. Mislow and H. D. Perlrnutter, J . Amer. Chem. SOC., 1962, 84, 3591. 63 G. Wittig and A. Krebs, Chem. Ber., 1961, 94, 3260; G. Wittig and R. Pohlke, ibid., p. 3276. 6 4 J. E. Baldwin, D. H. R. Barton, J. L. Bloomer, L. M. Jackman, L. RodriguezHahn, and J. K. Sutherland, Experientia, 1962, 18, 345; G. Ferguson, G . A. Sim, and J. M. Robertson, Proc. Chern. Soc., 1962, 385; T. Hamor, I. Paul, J. M. Robertson, and G. A. Sim, Experientia, 1962, 18, 352.
56 67
84, 1755.
W. E. Parham, R. W. Soeder, and R. M. Dodson, J . Amer. Chem. SOC., 1962,
OVERTON
: ALICYCLIC COMPOUNDS
287
hydrochloride defines the preferred conformation of cyclodecane as (60).6 5 Cyclononyl and cyclodecyl toluene-p-sulphonate are solvolysed 66 by nonclassical transannular paths, which can be rationalised by using their established conformations. Bromine adds in transannular positions to cyclononene and cyclodecene. The stereochemistry of many-membered rings has been reviewed.6 8 1,2-Cyclodecanedionecyclises 69 under irradiation to give the bicycle (61)
OH
in 83% yield, probably through a six-ring transition state. I n the Barton photolysis of alkylcyclohexyl nitrites, the nitroso-dimer is formed 7 0 only where a six-ring intermediate is possible, as in (62). The stereoelectronic requirements of the conversion of the ketol (63) into its isomer (64) have been discussed.71 The interpolation of two carbon atoms 7 2 as in (65)+(66) may be general for compounds of type (67). Mercury-sensitised photolysis of norcamphor gives,73 amongst other products, bicyclo[2,1,l]hexane, bicyclo[2,2,0]hexane, and nortricyclene. Thermal decomposition of the diazo-compound (68) gives 74 the ketone (69) possibly by way of a bivalent radical. Hydration of endo- or exo-isocamphene (70) gives 7 5 the same mixture of isoborneol (71) and (72) by a series of 2,6hydride shifts and Wagner-Meerwein rearrangements. The epoxide (73) rearranges 76 in acid to the lactone (74), possibly by the mechanism shown in scheme (75). The infrared spectra of nortricyclenes 7 7 and the nuclear
6 5 E. Huber-Buser, J. D. Dunitz, and K. Venkatesan, Proc. Chem. SOC., 1961, 463; E. Huber-Buser and J. D. Dunitz, Helv. Chim. Acta, 1961, 44, 2027; J. D. Dunitz and K. Venkatesan, ibid., p. 2033. 6 6 V. Prelog, H. H. Kagi, and E. H. White, Helv. China. Acta, 1962, 45, 1658; V. Prelog, W. Kung, and T. Tomljenovic, ibid., p. 1352. 6 7 J. Sicher, Zhvada, and M. Svoboda, Coll. Czech. Chem. Comm., 1962, 27, 1927. 6 8 J. Sicher, Progress in Stereochemistry, ed. W. Klyne and P. B. D. de la Mare, Butterworths Scientific Publns., London, 1962, Vol. 1 1 p. 202. 1, 6 9 W. H. Urry, D. J. Trecker, and D. A. Whey, Tetrahedron Letters, 1962, 609; W. H. Urry and D. J. Trecker, J . Amer. Chem. Soc., 1962, 84, 118. 7 0 P. Kabasakalian and E. R. Townley, J . Amer. Chem. SOC., 1962, 84, 2724. l Y. Mazur and M. Nussim, Tetrahedron Letters, 1961, 817. 72 S. Swaminathan, J. P. John, and S. Ramachandran, Tetrahedron Letters, 1962, 729. 73 R. Srinivasan, J . Arner. Chem. SOC., 1961, 83, 4923. 7 4 P. Yates and S. Danishefsky, J . Amer. Chem. SOC., 1962, 84, 879. 7 5 S. Beckmann and B. Geiger, Chem. Ber., 1962, 95, 2101. 7 6 J. Meinwctld and B. C . Cadoff, J. Org. Chem., 1962, 27, 1539. 7 7 G. E. Pollard, Spectrochim. Acta, 1962, 18, 837.
Jr:
288
ORGANIC CHEMISTRY
magnetic resonance spectra of bicyclo[2,1,1Ihexane 7 8 derivatives have been examined.
Quadricyclene is obtained 7 9 by irradiation of norbornadiene; tricyclo[2,2,2,22,5]decane(" twistane ") (76), the boat isomer of adamantane, has been synthesised;sOand the hydrocarbon (77) has been obtained from the perchloro-compound.81
Syntheses in the tetracycline series have been reviewed.82 The first total synthesis of a natural tetracycline antibiotic, (-+)-6-demethyl-6-deoxytetracycline (78), has been achieved;s3and an effective procedure for completing
the synthesis of 6-oxygenated tetracyclines has been devised.84 7-Chlorodehydrotetracycline (79) has been obtained in good yield by photo-oxygena78
K. B. Wiberg, B. R. Lowry, and B. J. Nist, J . Amer. Chem. SOC., 1962, 84,
1594.
7 9 W. G. Dauben and R. L. Cargill, Tetrahedron, 1961, 15, 197; G. S. Hammond, N. J. Turro, and A. Fischer, J. Amer. Chem. SOC.,1961, 83, 4674. SOH. W. Whitlock, jun., J. Amer. Chem. Xoc., 1962, 84, 3412. 81 E. T. McBee, W. L. Dilling, and H. P. Braendlin, J. Org. Chem., 1962, 27, 2704. 8 2 H. Muxfeldt, Angew. Chem., 1962, 74, 443. 83 L. H. Conover, K. Butler, J. D. Johnston, J. J. Korst, and R. B. Woodward, J . Amer. Chem. SOC., 1962, 84, 3222. s 4 A . I. Scott and C. T. Bedford, J. Amer. Chem. SOC.,1962, 84, 2271.
O V E B T O N : ALICYCLIC COMPOUNDS
289
tion of anhydro-7-chlorotetracycline (7923). Eurther, the absolute configuration of the tetracyclines has been established 8 5 as in (79). This subject is further reviewed in section 7. Monoterpenes.-The absolute configurations of (8)-( )-linalool (80) and its enantiomer are supported s6 by their pyrolytic formation from the diastereomeric pinan-2-01s (81) of known configuration. Photocyclocitral A (82) is a major product 87 when citral (83) is irradiated. T i ,interestingly, hs has the iridolactone carbon skeleton. The conformations of iridomyrmecin
(811
PHO K
ff*OH (83) COzH 187)
(84)
61
C02Me
(82)
(84) and isoiridomyrmecin (85) have been established 88 by X-ray crystallography. Oleuropeic acid (86) [not (87)]has been synthesised 89 by way of the ketal (88). The [a]= of a-phellandrene is temperat~re-dependent,~O indicating an equilibrium between the conformers (89) and (90). The product from sodioeucamone and triphenylmethyl chloride is the ketone (91) and not the norcaradiene (92).91 p-Pinene (93) has been photosynthesised 92 in 9% yield from myrcene
Mob
V. N. Dobrynin, A. I. Gurevich, M. G. Karapetyan, M. N. Kolosov, and M. M. Shemyakin, Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Nauk, 1962, 1697; Tetrahedron Letters, 1962, 901. 8 6 G. Ohloff and E. Klein, Tetrahedron, 1962, 18, 37. 8 7 R. C. Cookson, J. Hudec, S. A. Knight, and B. Whitear, Tetralzedron Letters, 1962, 79. 8 8 J. F . McConnell, A. McL. Mathieson, and B. P. Schoenborn, Tetrahedron Letters, 1962, 445; B. P. Schoenborn and J. F. McConnell, Acta Cryst., 1962, 15, 779. 8 9 R. Mechoulam, N. Danieli, and Y. Mazur, Tetrahedron Letters, 1962, 709. H. Ziffer, E. Charney, and U. Weiss, J . Amer. Chem. SOC., 1962, 84, 3961. 91 W. von E. Doering and M. R. Willcott, tert., Tetrahedron Letters, 1962, 663. 9 2 K. J. Crowley, Proc. Chem. Soc., 1962, 245.
I (
290
(94), its supposed progenitor. a-Pinene, biosynthesised in Pinus nigra from [2-14C]mevalonicacid, gives norpinic acid (95), retaining all the radioacti~ i t y .This~ accords with the formation of cc-pinene from geranyl pyro~ phosphate through the intermediate (96). Pure epicamphor (97) (and the derived epiborneol and epi-isoborneol) has been prepared 94 by reduction of camphorquinone. (+)-Sabinene 95 (98) and (-)-urnbelldone 96 (99) have been converted into or-isopropyl-a-methylsuccinic acids of known configuration, from which follow the absolute configurations of thujone (100) and the thujane group.
(97)
The biosynthesis of thujone by way of the intermediate (101) and stereospecific oxidation is supported 97 by the fact that the oxidation product (102) &om labelled thujone retains the whole radioactivity.
Labelling studies 98 with the (mono)terpenoid chain of mycelianamide (103) suggest that the terminal gem-methyl groups of the chain remain distinct in the linking of isoprenes, as is the case with suitable cyclic terpenoids in which this point has been investigated. Sesquiterpenes.-Pure humulene has been isolated and shown 99 to have the constitution (104), in contradiction of previous assignments.
ppa
(104)
Q
(107)
(1 05)
(106)
Isobisabolene, from vetiver oil, has 100 the structure (105) and the synthesis of (&)-cuparene has been published in full.lol 8-Elemene (isopropylgeijerene) (106) and cogeijerene (107) are further
W. Sandermann and W. Schweers, Tetrahedron Letters, 1962, 257. W. Huckel and 0. Fechtig, Annalen, 1962, 652, 81. 9 5 T. Norin, Actca Chem. Xcand., 1962, 16, 640. 9 6 H.E. Smith and A. W. Gordon, J. Amer. Chem. SOC., 1962, 84, 2840. g 7 W. Sandermann and W. Schweers, Tetrahedron Letters, 1962, 259. g s A. J. Birch, M. Kocor, N. Sheppard, and J. Winter, J . , 1962, 1502. 9 9 M. D. Sutherland and 0. J. Waters, Austral. J . Chem., 1961, 14, 596. P. S. Kalsi, K. K. Chakravarti, and S . C. Bhattacharyya, Tetrahedron, 1962, 18, 1165. 1 0 1 W. Parker, R. Ramage, and R . A. Raphael, J., 1962, 1558.
g3
94
OVERTON
291
examples 102 of optically inactive natural products containing asymmet'ric centres. It is suggested that the precursor may lack asymmetry, and that cyclisation may be non-enzymic. Stereospecific routes lo3 to (&-)-p-santalene (108) and (&)-epi-/l-santalene (log), confirming their previously assigned stereochemistry, have been described. An X-ray examination 104 of 2-bromo-a-santonin (110) shows that the
I-epi-(108)
0
(110)
(Ill)
O40
H02CyH.
..
stereochemistry at C-13 (a-Me)is opposite to that previously accepted. This is further borne out by the X-ray investigation of bromodihydroisophoto-asantonolactone and the conversion105 of a-santonin by way of hyposantonin (111) into (+)-benzoylalanine (112). The constitutions of two interesting photo-products derived from santonin have also been established: irradiation lo6 of the homoannular dienone (113) derived from ysantonin afforded the expected acid (114); photosantoninic acid (obtained by irradiation of santonin or treatment of lumisantonin with base) is the 15), presumably produced by intermolecular Michael addition of dimer (1 lumisantonin ; lumi-6-epi-and 6-epi-#?-santonin unchanged when treated are with base.
0
(119; R = O H )
Gough, V. Powell, and M. D. Sutherland, Tetrahedron Letters, 1961, 763. J. Corey, R. Hartmann, and P. A. Vatakencherry, J . Amer. Chem. Soc., 1962, 84, 2611. 1 0 4 J. D. M. Asher and G. A. Sim, Proc. Chem. SOC., 1962, 335. l o 5 M . Nakazaki and H. Arakawa, Proc. Chem. SOC.,1962, 151. lo6W. G. Dauben, D. A. Lightner, and W. K. Hayes, J . Org. Chem., 1962, 27,
lo2 J. l o 3E.
1897.
107
I. Satoda and E. Yoshii, Tetrahedron Letters, 1962, 331.
292
ORGANIC CHEMISTRY
Vulgarin lo8 (tauremisin A) has the constitution (116); the stereochemistry follows from its conversion into santanolide C obtainable from santonin. Atractylon log (117) is autoxidised to a mixture of lactones (118) and (119), related to the naturally occurring ivalin 110 (120) whose constitution rests on its conversion into tetrahydroalantalactone. Scabiolide ll1 is
CH2.OAc
the cyclodecenolide (121) related to cnicin. (+)-Occidol has 1 1 2 the configuration (122) from its interrelation with ( -)-santonin. (+)-Occidentalol (123) which occurs in the same oil has been postulated as a biogenic precursor. Evidence has been obtained mathat valeranone has structure (124), and not the isomeric (125) as previously proposed 113b for jatamansone (valeranone). Calarene (126) has been interrelated with aristolone (127), thus confirming its independently established 114b constitution.
gxf
0
(124; R = H,R=Pri) (125 ; R = Pri, R= H)
q qo
(126)
(127)
The furanodecalins (128), (129), (130), and the related butenolides (131) and (132) have been isolated 115from the rhizomes of Petasites species. Polygodial 116 (133)is a new bicyclofarnesol derivative. (&)-Widdrol (134) has been synthesised.l17 The structure of hinesol (135) and its configuration a t C-4 have been confirmed.ll* Bulnesol(l36)has been converted 119under acidic conditions
lo8 T.A. Geissman and G. A. Ellestad, J . Org. Chem., 1962, 27, 1855; K. S. Rybalko and L. Dolej8, Coll. Czech. Chem. Comm., 1961, 26, 2909. lo9 H. Hikino, Y. Kikino, and I. Yoshioka, Chem. and Pharm. Bull. (Japan), 1962, 10, 641. 110 W. Herz and G. Hogenauer, J . Org. Chem., 1962, 27, 905. ll1 M. Suchj., V. Herout, and F. sorm, Coll. Czech. Chem. Cornm., 1962, 27, 1905. 112 M. Nakazaki, Bull. Chem. SOC. Japan, 1962, 35, 1387. 113 (a) J. K?epinskjr, M. Romafiuk, V. Herout, and F. Sorm, Tetrahedron Letters, 1962, 169; (b) T. R,. Govindachari, B. R. Pai, K. K. Purushothaman, and S. Rajadurai, Tetrahedron, 1961, 12, 105. 114 ( a ) G. Buchi, F. Greuter, and T. Tokoroyama, Tetrahedron Letters, 1962, 827; ( b ) S. Furukawa, J . Pharm. SOC. Japan, 1961, 81, 570. 115 J. HochmannovB, L. Novotnf, and V. Herout, COX Czech. Chem. Comna., 1962, 27, 1870; L. Novotnf, J. Jizba, V. Herout, and F. Sorm, ibid., p. 1393; L. Novotnj., V. Herout, and F. sorm, ibid., p. 1400. 116 C. S. Barnes and J. W. Loder, Austral. J . Chem., 1962, 15, 322; J. W.Loder, ibid., p. 389. 11 C. Enzell, Tetrahedron Letters, 1962, 185. 118 W. Z. Chow, 0. Motl, and F. Sorm, COX Czech. Chem. Comm., 1962, 27, 1914. 119 R. B. Bates and R. C. Slagel, J . Amer. Chem. SOC., 1962, 84, 1307.
OVERTON
293
into guaiol (137), 6-guaiene (138), and an isomeric hydrocarbon (139) which can be converted 119 into patchouli alcohol (140). The compound (139) has
R
(128; R = H, R= H R= Me) , (129; R = H R=O, R= Me) ,
R
R
R
(131; R = H)
(130; R=O-CO-CMe:CHMe, R= H2, R= CH2-OH)
(132; R = O*CO-CMe:CHMe)
(1 33)
(134)
(135)
been synthesised 120 from homocamphor and this constitutes a synthesis of patchouli alcohol. Bromogeigerin acetate has been shown 121 to possess the
OH
oq
. I
(141; R = I a - B r ) (142; R =
Ip
-H)
0 (143; R = H, R= OAC) (145; R=OAC,R=H)
O Q
(144)
constitution and stereochemistry (141) by an X-ray study. The remaining uncertainty a t position 1 in geigerin has been resolved 122 by a striking synthesis of geigerin acetate (142) from 8-epi-isophotoartemesolactone(143). The a-santonin -+ isophotosantonolactone conversion is perfectly general 128
Biichi and W. D. Macleod, jun., J. Amer. Chem. SOC.,1962, 84, 3205. A. Hamilton, A. T. McPhail, and G. A. Sim, J., 1962, 708. 122 D. H. R. Barton, T. Miki, J. T. Pinhey, and R. J. Wells, Proc. Chem. SOC., 1962, 112. 123 D. H. R. Barton, J. E. D. Levisalles, and J. T. Pinhey, J . , 1962, 3472.
lZo G. 121 J.
294
OEQANIC CHEMISTRY
and highly stereospecific,and this has been turned to excellent account 124 in a synthesis of (-)-epicyclocolorenone (144), starting from acetylisophotosantonolactone (145), thereby establishing the previously undefined stereochemistry of cyclocolorenone. The constitution and stereochemistry of isophotosantonolactone follow independently from that of the bromodihydrolactone (146), established by an X-ray The constitution of zierone has been independently established as (147) by two groups.126 Parthenin (148) has been correlated 12' with ambrosin
and both have been shown not to be guanolides as previously supposed. Helenalin, tenulin, and balduilin probably also belong to this new class of sesquiterpenoids. Helminthosporal has 12* the novel constitution (149). Its proposed biogenesis from an isoprenoid precursor (150),as shown, is supported !28b by labelling experiments. The biogenetic route to longifolin previously proposed is in accord 129 with its biosynthesis from labelled acetate.
Further experiments 130 corroborate the constitution previously proposed of shellolic acid. The stereochemistry (151) proposed 131 on the basis of nuclear magnetic resonance data has now been confirmed by an X-ray crystallographic study of the bromo-lactone. Diterpenes.-The previously assigned (13R)-configurationin manool and sclareol has been withdrawn l 3 2 in favour of the (13&')-configuration, since (+)-halo01 has been shown to have the (&')-configuration. However
G. Buchi and H. J. E. Loewenthal, Proc. Chem. Soc., 1962, 280. J. D. M. Asher and G. A. Sim, Proc. Chem. SOC., 1962, 111. l a s A. J. Birch, D. J. Collins, A. R. Penfold, and J. P. Turnbull, J., 1962, 792; D. H. R. Barton and G. S. Gupta, J., 1962, 1961. 127 W. Herz, H. Watanabe, M. Miyazaki, and Y. Kishida, J . Amer. Chem. Soc., 1962, 84, 2601. 128 ( a ) P. de Mayo, E. Y . Spencer, and R. W. White, J . Amer. Chem. SOC., 1962, 84,494; ( b ) P. de Mayo, J. R. Robinson, E. Y . Spencer, and R. W. White, Eqerientiu, 1962, 18, 359. 120 W. Sandermann and K. Bruns, Chem. Ber., 1962, 95, 1863. 130 W. Carruthew, J. W. Cook, N. A. Glen, and F. D. Gunstone, J . , 1961, 5251; R. C. Cookson, N. Lewin, and A. Morrison, Tetrahedron, 1962, 18, 547. 131 R. C. Cookson, A. Melera, and A. Morrison, Tetrahedron, 1962, 18, 1321. 138 D.B. Bigley, N. A. J. Rogers, and J. A. Barltrop, Chem. and Id., 1962, 1570.
124
125
O V E R T O N ; ALICYCLIC C O M P O U N D S
295
degradation 133 of sclareol to the lactone of 4-hydroxy-4-methylhexanoic acid, also obtained from the ( -)-dihydro-derivative of (R)-linalool, shows that manool and sclareol have the (13R)-configuration. 12-Hydroxy-13-epimanoyloxide (152)has been isolated 134 from Turkish tobacco, and the configurations previously assigned to manoyl oxide and its 13-epimer have been sustained.
The C,, ketone colensenone 135 (153) is a biogenetically interesting relative of 2-oxomanoyl oxide, to which it has been related. The contraction of ring A which generates the p-hydroxy-acid system of ceanothic acid (see p. 300) leads here via oxidation and decarboxylation to a cyclopentanone. The structure and stereochemistry of communic acid (154) have been established 136 by conversion of the acid into a degradation product of agathenedicarboxylic acid. Grindelic acid (155)and the minor related acids (156)and (157) have been isolated 13 from the resin of Grindelia robusta. Labdane-80cYl5-diol occurs 138
133M. Soucec and P. Vlad, Chern. and Ind., 1962, 1946. J. A. Giles, J. N. Schumacher, S. S. Mims, and E. Bernasek, Tetrahedron, 1962, 18, 169. 136 P. K. Grant and ( n part) R. M. Carman, J., 1962, 3740. i 136V. Arya, H. Erdtman, and T. Kubota, Tetrahedron, 1961, 16, 255. P. 13 L. Panizzi, L. Mangoni, and M. Belardini, Gazzetta, 1962, 92, 522; L. Mangoni and M. Belardini, Atti Accad. naz. Lincei, Rend. Classe Sci. Jis. mat. nat., 1961, 31, 436. 13* A. J. Baker, G . Eglinton, A. G . Gonzalez, R. J. Hamilton, and R. A. Raphael, J., 1962, 4705.
18*
296
ORGANIC CHEMISTRY
as a major constituent of the leaf-gum of Aeonium Zindbeyi. A further paper has appeared 139on the structure of andrographolide. Full details have been published l40 of the chemical and X-ray crystallographic studies on clerodin. The most interestingly related cascarillin from Croton elutherea has been assigned 141 the provisional structure and stereochemistry (158). Two important communications have appeared 142 which define the structure and stereochemistry of isopimaric acid as in (159); and two total syntheses of (-J-)-dehydroabietic acid have been r e ~ 0 r d e d . l ~ ~ In
(163; R = OH,R'= H)
(164; R + R'= 0)
R R""'
R&;R=H21
(166;
R = 0)
one synthesis ring A is added to the isopropyltetralone (160) by standard reactions. In the second 143b the enone (161) is cleaved t o (162), which is cyclised and degraded. The structure and configuration of hinokiol and hinokione have been revised 144 t o (163) and (164), respectively. Totarol and totarolone are represented 145 by (165) and (166). The diterpene quinone royleanone (167) and the related 6,7-dehydro-
II
139M. P. Cava, W. R. Cahn, L. J. Haynes, L. F. Johnson, and B. Weinstein, Tetrahedron, 1962, 18, 397. 1 4 0 D. H.R. Barton, H. T. Cheung, A. D. Cross, L. M. Jackman, and M. MartinSmith, J., 1961, 5061; I. C. Paul, G. A. S h , T. A. Hamor, and J. M. Robertson, J., 1962, 4133. 1 4 l J. X. Birtwistle, D. E. Case, P. C. Dutta, T. G. Halsall, G. Mathews, H. D. Sabel, and V. Thaller, Proc. Chem. SOC.,1962, 329. 1 4 2 W. Antkowiak, J. W. ApSimon, and 0. E. Edwards, J . Org. Chem., 1962, 2 9 ', 1930; R. E. Ireland and J. Newbould, ibid., p. 1931. ( a )G. Stork and J. W. Schulenberg, J . Amer. Chem. SOC., 1962,84, 284; (b)R. E. Ireland and R. C. Kierstead, J . Org. Chem., 1962, 27, 703. 1 4 4 Yuan-Lang Chow and H. Erdtman, Acta Chena. Scand., 1962, 16, 1296. 145 Yuan-Lang Chow and H. Erdtman, Acta Chem. Scand., 1962, 16, 1305.
OVERTON
: ALICYCLIC C O M P O U N D S
297
and 7-acetoxy-derivative have been isolated 146 from Inula royleana. Podototarin (168), the h e r obtained on oxidative coupling of totarol, has been isolated from Podomrpus totura and synthesised lP7 Ullmann coupling by of 12-bromototaryl methyl ether. Levopimaric acid, unlike a-phellandrene (see p. 289), has a fixed conformation, since its [a]= not temperature-dependent. 148 Its Cotton curve is is antipodal 18 to t' at of 2,4-cholestadiene, and this is supposed to arise 4' from the conformation (169) with a left-handed helix. Measurements on confirm these conclusions. Ultraviolet unimolecular surface films 1 4 ~ irradiation 149 of levopimaric acid gives the bicyclo[2,2,0]hexene derivative (170). The position of the carboxyl group in steviol and isosteviol proposed previously is supported 152 by its pKmcsand mass spectrum. An important X-ray structural study of bromoepoxynorcafestanone (171) shows 153 that, contrary to previous deductions, cafestol (172) has a 9B-H configuration and hence the normal trans-anti-backbone of tri- and
tetra-cyclic diterpenoids. This conclusion can be anticipated 153 on the basis of circular dichroism studies. A novel tetracyclic diterpene skeleton which readily fits into the accepted biogenetic scheme has been encountered in three related compounds from ti'pirostachys africana, 154 namely, stachenone (173) and the derived a-ketol
R' R
(173: R = H l , R ' = O )
(174; R = O , R ' z
$
H,OH)
146
@
H0 o g
(I 75.)
C H 2 0 * CO
ZH:CHPh
HO
HO-HC '
(1 7 6 )
1' 4
0. E. Edwards, G. Feniak, and M. Los, Canad. J. Chem., 1962, 40, 1540. R. C. Cambie, J. W. R. Simpson, and L. D. Colebrook, Chem. and Ind., 1962,
1757.
148 ( a ) U . Weiss, H . Ziffer, and E. Charney, Clzem. and Ind., 1962, 1286; ( b ) A. W. Burgstahler, H . Ziffer, and U. Weiss, J. Amer. Chem. SOC., 1961, 83, 4660; ( c ) U. Weiss and N. L. Gershfeld, Experientia, 1962, 18, 355. 149 W. H. Schuller, R. N. Moore, J. E. Hawkins, and R. V. Lawrence, J. Org. Chem., 1962, 27, 1178. 152 V. P. Arya, J. Sci. Ind. Res., India, 1962, 21, B , 93 (see Ann. Reports, 1961, 55, 256). A. I. Scott, G . A. Sim, G. Ferguson, D. W. Young, and F. McCapra, J. Amer. Chem. SOC.,1962, 84, 3197. 154 W. H. Baarchers, D. H . S. Horn, and Le R. F. Johnson, J., 1962, 4046.
298
ORGANIC CHEMISTRY
(174) and diosphenol(175), and in beyerol(l76) from Beyeria ZeschenauZtii.155 The A/B stereochemistry related to (-)-kaurene is indicated by molecular rotation differences and optical rotatory dispersion measurements. An X-ray structure determination 156 of the bromo-ketone (177) obtained from gibberellic acid with pyridine bromide perbromide shows the complete stereochemistry of gibberellic acid to be as in (178), when combined with the previous assignment of absolute configuration at C-3. The 4bp-H configuration shows that the l0a-methyl group of the precursor must be removed without prior migration to C-9(4b).
(179; R = Me) (180; R = CH2.
I; R = CHO)
( I8 2 ; R = C02H)
oC -6
Four new metabolites have been isolated from Gibberelk fujikuroi. These are 7-hydroxykaurenolide (179), 7,18-dihydroxykaurenolide (180), fujenal(181), and fujenoic acid (182). The oxidative modifications of ring B present interesting prior stages to the contracted B ring of gibberellic acid.
HO
(185)
14
OH
-OH
The structural elucidation of these compounds also supports the previously assigned stereochemistry of (-)-kaurene, and this has now been confirmed by a total synthesis.15* A total synthesis of (&)-gibberic acid (183), the major acid degradation product of gibberellic acid, through condensation of the oxoindanecarboxylic ester (184) with methyl vinyl ketone has been described.lS9 The full evidence on which the Kyoto group based the pre1 viously published structures of grayanotoxins I, 11, and I 1 has now been pub1ished.l6O Their stereochemistry has been the subject of two
155 P.R.Jefferies, R. S. Roisich, D. E. White, and M. C . Woods, Austral. J . Chem., 1962, 15, 521. 156 F. McCapra, A. I. Scott, G. A. Sim, and D. W. Young, Proc. Chem. SOC., 1962, 185. 157 B. E. Cross, R . H. B. Galt, J. R. Hanson, and W. Klyne, Tetrahedron Letters, 1962, 145. 158 R. A. Bell, R . E. Ireland, and R. A. Partyka, J . Org. Chem., 1962, 27, 3741. 159 H. J. E. Loewenthal and S . K. Malhotra, Proc. Chem. Soc., 1962, 230. 160 J. Iwasawa, Z. Kumazawa, and M. Nakajima, Botyu-Kagakw, 1962, 27, 22.
O V E R T O N : ALICYCLIC COMPOUNDS
299
from publications.161,1 6 2 The more complete assignment (185) differs that of the Tokyo group l62 at C-14. Pleuromutilin (186), a metabolite of Pleurotus mutiZis,l63 has the most extensively modified carbon skeleton yet encountered among diterpenes. Its proposed biogenesis by rearrangement of a normal labdane type (as 187) is supported by preliminary experiments.
OH
Cembrene 1 6 4 (thunbergene) (188) is the first 14-carbonring compound to be found in Nature. Ibamarin 165 from ITberis amura and samaderin C 166 from Xamadera indicu may well be members of the quassin group of diterpenoids. Two alternative structures (189) and (190) have been proposed 167 for
HO
OH
the complex diterpenoid ryanodol. On the basis of extensive degradations,l68 " the somewhat remarkable structures (191) and (192) must be regarded as serious possible representations of O-cinnamoyltaxicin-I," derived from taxine-I, the major yew alkaloid. The synthesis of di- and tri-terpenoids has been reviewed.169
161
H. Kakisawa, M. Yanai, T. Kozima, K. Nakanishi, and H. Mishirna, Tetrahedron Letters, 1962, 215. D. Arigoni, CTazzetta, 1962, 92, 884. 164 W. G. Dauben, W. E. Thiessen, and P. R. Resnick, J . Amer. Chem. Soc., 1962, 84, 2015; E. Xobayashi and S. Akiyoshi, Bull. Chem. Sm. Japan, 1962, 35, 1044. 166 J. B.-Son Bredenberg and R. Gmelin, Acta Chern. S a n d . , 1962, 16, 649. J. Polonskg and J. Zeibler, Bull. SOC. chim. France, 1962, 1715. 1 ' Z. Valenta and K. Wiesner, Experientia, 1962, 18, 111; see also ibid., p. 549. 6 168 B. W. Langley, B. Lythgoe, B. Scales, R. M. Scrowston, S. Trippett, and D. Wray, J., 1962, 2972. 169 N. A. J. Rogers and J. A. BarItrop, Quart. Rev., 1962, 16, 217.
W. H. Tallent, J . Org. Chem., 1962, 27, 2968.
300
ORGANIC CHEMISTRY
!L'riterpenes.-Full details have appeared 170 for the previously disclosed constitution of ceanothic acid (emmolic acid). The earlier stereochemical assignments 1 7 0 for ring A have received independent supp0rt.1~1 The C,, acid, ceanothenic acid, also from Ceanothus americanus, has structure (193),172 The cucurbitacins have probably now received their definitive constitutions 173with placement of the ring c ketone group a t position 12. In view of the previous interrelation of cucurbitacins ByD, E, and I, the group may now be represented as in (194-196). 2-Epicucurbitacin B has been isolated from Luau ~ r n a r a . ~ ~ ~
C u c u r b i t a c i n A : R = CH,.OH; R'= Ac; C u c u r b i t a c i n B : R = Me,R'= A c ; Cucurbitacin D R = M~,R'=H. (Elatericin A )
Cucurbitacin E Cucurbitacin I ( E l a t e r i c i n B) } R = H
/\
Cucurbitacin C
The C,, antibiotic fusidic acid has been assigned 175 the provisional structure (197). Four new cyclopropanoid triterpenes (198-201) have been isolated 1 7 6 from Spanish moss. Arnidiol and faradiol are 1 7 7 taraxestene3,12-diols and thus among the rare 12-oxygenated triterpenoids: both can be converted into taraxastane-3,12-dione (202). The constitution and stereochemistry of two tetranortriterpenoids of the limonin class have been elucidated by X-ray studies. These are gedunin (203) (as dihydrogedunol
1 7 O P . de Mayo and A. N. Starratt, Canad. J. Chem., 1962, 40, 788; J. H. Boyer, R. A. Eade, H. Locksley, and J. J. H. Simes, Austral. J. Chem., 1958, 1 , 237. 1 1 7 1 R . A. Eade, G. Kornis, and J. J. H. Simes, Chem. and Ind., 1962, 1195. 1 7 2 P. de Mayo and A. N. Starratt, Canad. J. Chern., 1962, 40, 1632. 173 D. Lavie, Y . Shvo, 0. R. Gottlieb, and E. Glotter, Tetrahedron Letters, 1961, 615; W. T. de Koch, P. R. Enslin, K. B. Morton, D. H. R. Barton, B. Sklarz, and A. A. Bothner-By, ibid., 1962, 309. 174 D. Lavie, T. Shvo, 0. R. Gottlieb, R. B. Desai, and M. L. Khorana, J., 1962, 3259. 175 W. 0. Godfredsen and S. Vangedal, Tetrahedron, 1962, 18, 1029. 176 C. Djerassi and R. McCrindle, J., 1962, 4034. 177 J. 0. Santer and R. Stevenson, J. Org. Chem., 1962, 27, 3204.
OVERTON : ALICYCLIC COMPOUNDS
301
iodoacetate 178) and cedrelone (204) (as the iodoacetate 179). Some interesting chemical transformations of cedrelone have been reported. 179
(198; R = H)
&* ;
D
( 1 9 9 ; R = Me)
(200;R = 0 )
(201 ; R = H * O H )
c.
K
HO
HO
.HO
R
(205; R = Me, R'= C02H)
(206;
R = COzH, R' = Me)

C02H ; 19-OH
( 2 0 7 j R = CHZ.OH, R ' =
Variously oxygenated derivatives of B-amyrin continue to come to light. (206), Recent examples include maslinic acid 180 (205), commic acid (C) tomentosic acid 182 (207) aegiceradiol 183 (208) barringtogenol D (209), and the C,, compounds nor-echinocystadienol1 8 5 (210) and albigenin 186
S. A. Sutherland, G. A. Sim, and J. M. Robertson, Proc. Chem. SOC., 1962, 222. I. G. Grant, S. A. Hamilton, T. A. Hamor, R. Hodges, S . G. McGeachin, R. A. Raphael, J. M. Robertson, and G . A. Sku, Proc. Chem. SOC.,1961, 445. lSo L. Caglioti, G. Cainelli, and F. Minutilli, Gazzetta, 1961, 91, 1387. lS1 A. F. Thomas, Tetrahedron, 1961, 15, 212. lS2 L. R. Row and G . S. R,. Subba Rao, Tetrahedron, 1962, 18, 827. 183 K. V. Rao and P. K. BOW,Tetrahedron, 1962, 18, 461. lS4 S K. Chacraborti and A. K. Barua, Ezperientia, 1962, 18, 66. . lS5 K. V. Rao and P. H.Bose, J . Org. Chem., 1962, 27, 1470. lS6 A. K. Barua and S . P. Raman, Tetrahedron, 1962, 18, 155.
178 179
302
(211). Maslinic acid (205) has been partially synthesised 18' by a method including hydroboration of the enol acetate of oleanonic ester. Cornmic (212) and (E) 188 (213) are probably derived from or-amyrin. acids (D) The 2,3-seco-oleanene (214), previously obtained from oleanolic acid, occurs 189 in Burseru gruveolens and is the first naturally occurring compound
a
k
HO
HOiC
(212;
R = H)
(213; R=OH)
of this type. The previous partial structure of the quinonoid triterpenes pristimerin and celastrol has now been expanded l 9 0 to the full structure (215). Triterpene synthesis has been reviewed.lG9 Two bicyclic intermediates for the construction of the onocerane skeleton
have been synthesised, the keto-acid (216) 1 9 l from the decalone (217), and the alcohol (218) lg2 from the Diels-Alder adduct of butadiene and quinone. A possible precursor (219) for the c/D-rings of /3-amyrin has been synthesised 1 9 3 in 23% yield from the readily available ketol(220). A synthesis of the oleanane skeleton has been recorded.lg4 The condensation product of the bromide (221) from sclareol and the ketone (222) was transformed into the tetracyclic compound (223). Acid-induced cyclisation led, after gas-liquid chromatographic examination, to a small yield of mixed crystals of (-)-olean-13( 18)-ene and (+)-1S-a-olean-12-ene. Selective oxidation of the terminal double bonds in squalene has been
L. Caglioti and G. Cainelli, Tetrahedron, 1962, 18, 1061. A. F. Thomas, K. Heusler, and J. M. Muller, Tetrahedron, 1961, 16, 264. 189 K. 5 Crowley, Proc. Chem. SOC., . 1962, 27. l g o . Harada, H. Kakisawa, S. Kobayashi, M. Musya, K. Nakanishi, and Y. R Takahashi, Tetrahedron Letters, 1962, 603. l g l R. F. Church, R. E. Ireland, and J. A. Marshall, J . Org. Chem., 1962, 27, 1118. l u 2 R. E. Ireland and J. A. Marshall, J . Org. Chem., 1962, 27, 1620. lBs R. F. Church, R. E. Ireland, and D. R. Shridhar, J . Org. Chem., 1962, 27, 707. l g 4 A. Barltrop, J. D. Littlehailes, J. D. Rushton, and N. A. J. Rogers, Tetrahedron J. Letters, 1962, 429.
lE8
O V E R T O N : ALICYCLIC COMPOUNDS
303
realised 195 as a model for oxidative cyclisation. N-Bromosuccinimide in aqueous glycol methyl ether added hypobromous acid terminally in 81% yield. A detailed study has been made of the mechanism of contraction of ring A in triterpenoids and 4,4-dimethyl-19-nor- steroids.l96 A n extensive mass-
HO
spectrometric study of a- and /3-amyrin derivatives has been made;Ig7some well-defined features are observable in their fragmentation patterns. It is possible to assign 198 characteristic nuclear magnetic resonance signals to the methyl groups (other than those of ring A) in the lupane series. The stereochemistry of terpenoid double bonds of the type -CH,*CMe:CH*CH,X can be deduced l99 by nuclear magnetic resonance spectroscopy when X is OH, an isoprene residue, or a variety of other groups. Steroids.*-!$, 19-and 6B,19-Cyclosteroidsare formed 200 by solvolysis of e.g., suitable 19-methanesulphonyloxy-derivatives, (224)-+ (225); (226)-+ (227). 14~,18-Cyclosteroidsresult from deamination of 18-amino-compounds [(228)--+ (229?)+(230)].201 12,18 Cyclosteroidshavebeen made 202 by treating 18-chloro(or trimethylammono)-ll-oxo-steroids with base [(231)--+ (232)J. 17-Keto-steroids have been transformed 204 into (234)l. D-nor-steroids by photolysis of the a-diazo-ketones [e.g., (233)--+
2039
Letters, 1962, 121. Ourisson, Bu71. SOC. chim. France, 1962, 330; J.-F. Biellmann and G. Ourisson, ibid., p. 331; J.-F. Biellmann, D. Kucan, and G. Ourisson, ibid.,p. 337; J.-F. Biellmann and G. Ourisson, ibid., p. 341. l B 7 C. Djerassi, H. Budzikiewicz, and J. M. Wilson, Tetrahedron Letters, 1962, 263. lg8 J.-M. Lehn and G . Ourisson, BUZZ. SOC. chim. France, 1962, 1137. l g 9 R. B. Bates, R. H. Carnighan, R. 0. Rakutis, and J. H. Schauble, Chem. and Ind., 1962, 1020. * Prepared with the kind assistance of Drs. C. J. W. Brooks, J. Elks, and Professor W. Klyne. See Introduction (Section 1). J. J. Bonet, H. Wehrli, and K. Schaffner, HeZv. Chim. Acta, 1962, 45, 2615. 201 W. G. Dauben and P. Laug, Tetrahedron Letters, 1962, 453; J. Hora, V. Cerny, and F. germ, ibid., p. 501. 2 0 2 V. Georgian, J. F. Kerwin, M. E. Wolff, and F. F. Owings, J . Amer. Chem. SOC., 1962, 84, 3594. 203 J. Meinwdd, G. G. Curtis, and P. G . Gassman, J . Amer. Chem.SOC., 1962, 84, 116; M. P. Cava and E. Moroz, ibid., p. 115.
l g 5 E. E. van Tamelen and T. J. Curphey, Tetrahedron lS6 J.-F. Biellmann, D. Kucan, M. Rajic, P. Witz, and G.
304
O @
(232)
@OMe (234)
HO
(233)
Structure (235) is proposed 205 as an intermediate when cholesta-3,5-diene is photolysed in ethanol to the ethers (236) and (237). Photolysis of a simple enone, cholest-4-en-3-one, leads 206 t o lumicholestenone (238), presumably
@
(235)
H @
(236)
OAc
H CH2.OEt
OEt
(237) d
A. Hassner, A. W. Coulter, and W. S. Seese, Tetrahedron Letters, 1962, 759. W. G. Dauben and F. G. Willey, Tetrahedron Letters, 1962, 893. 2 0 6 W. W. Kwie, B. A. Shoulders, and P. D. Gardner, J . Arner. Chern. SOC., 1963, 84, 2268.
204
205
OVERTON : ALICYCLIC C O M P O U N D S
305
by a path that differs fundamentally from that followed by cross-conjugated (239) has been dienones. The photolysis of O-acetyl-l-dehydrotestosterone studied in detail. Among the interesting products formed 207 in non-polar solvents are (240-243). I n acetic acid the spirocyclopentenones (244) and (245) are formed.g The cyclopropane (242) has been transformed 209 into lox-testosterone. Oxidation of 6b-hydroxy-steroids by lead tetra-acetate with 210 or without 211 iodine gives the 6pJ19-ethersin good yield [(246)+(247)]. 48- and 2p-Hydroxy-steroids are converted 212 into the 19-hemiacetals, e.g., (249), and pregnan-20-01s213 into the 18 3 20 hemiacetals (250). 19-Nor-steroids have been made from 5x-halogeno-6#l-hydroxy-compounds. (3-19is oxidised either by lead tetra-acetate *14 or by nitrite photolysisJ215and subsequently eliminated as in (248)+ (251) + (252). The
Ac 0
& ?@
R
Ac 0
CI
(247 ; R = H )
(249)
( 2 4 8 ; R = Hal)
(251; R = C 0 2 H )
0 ( 2 5 2 ; R = H)
alternative route to 19-nor-steroids, involving oxidation at (2-19 by photolysis of an ll#l-nitrite, has been published in Recent developments in the photochemistry of (mostly steroidal) organic nitrites have been reviewed.217 The first synthesis 218 of a natural cardenolide, digitoxigenin (253) from
2 0 7 H. Dutler, C. Ganter, H. Ryf, E. C. Utzinger, K. Weinberg, K. Schaffner, D. Arigoni, and 0. Jeger, Helv. Chim. Acta, 1962, 45, 2346. 208 C. Ganter, E. C. Utzinger, K. Schaffner, D. Arigoni, and 0. Jeger, Helv. Chim. Acta, 1962, 45, 2403. 20B R. Wenger, H. Dutler, H. Wehrli, K. Schaffner, and 0. Jeger, Helv. Chim. Acta, 1962, 45, 2420. 210K. Heusler, J. Kalvoda, C. Meystre, G . h e r , and A. Wettstein, Helv. Chim. Acta, 1962, 45, 2161. 211 A. Bowers, E. Denot, L. C. Ibanez, M. E. Cabezas, and H. J. Ringold, J . Org. Chern., 1962, 27, 1862. 212 K. Heusler, J. Kalvoda, P. Wieland, G. Anner, and A. Wettstein, Helv. Chim. Acta, 1962, 45, 2575. 213 C. Meystre, K. Heusler, J. Kalvoda, P. Wieland, G. Anner, and A. Wettstein, Helv. Chim. Acta, 1962, 45, 1317. 214 K. Heusler, J. Kalvoda, C. Meystre, H. Ueberwasser, P. Wieland, G. Anner, and A. m7ettstein, Experientia, 1962, 18, 464; A. Bowers, R. Villotti, J. A. Edwards, E. Denot, and 0. Halpern, J . Amer. Chem. Xoc., 1962, 84, 3204. 215 M. Akhtax and D. H. R. Barton, J . Amer. Chem. Xoc., 1962, 84, 1496. 216 D. H. R. Barton and J. M. Beaton, J . Amer. Chem. SOC., 1963, 84, 199. 217 A. L. Nussbaum and C. H. Robinson, Tetrahedron, 1962, 17, 35. 218 N. Danieli, Y. Mazur, and F. Sondheimer, J . Amer. Chem. Xoc., 1962, 84, 875.
306
R
ORGANIC CHEMISTRY
2
(255; X = O )
(256; X = NH)
(254; R =
C0,Me)
the ester (254), and the first microbiological hydroxylation 219 of a steroidal sapogenin, diosgenin (255) (at C-7 and C-4), have been reported. Diosgenin acetate has been converted into the alkaloid solasodine (256) in three steps.220 Two stereospecific total syntheses of racemic connessine have been published,221 as have the details of its partial photochemical synthesis.222 Three total syntheses of cestrone 223-225 and syntheses of 19-norD-homotestosterone 225 and 18-noroestrone 226 have been recorded. The Grignard /?-alkylation of steroidal A@-ketonesis efficiently catalysed by cupric ion. 2 2 7 Steroidal 6a-methyl-4-en-3-ones are formed 228 by reaction of the 3-en01 ether of a 4-en-3-one with the Vilsmeier reagent. The factors influencing mono- and di-a-methylation of ctb-unsaturated ketones have been e ~ a m i n e d . 2 ~ ~ A procedure for deconjugation of A4-, but not Alp4- or A4,6-, 3-ketosteroids has been devised.230 The alkaline hydrolysis of a-glycol monoesters is facilitated 231 by the free hydroxyl group. Mass spectra have been recorded and discussed 232 for the eleven possible nuclear steroidal ketones. The helicity rules for cisoid dienes 233 can be extended to aB-unsaturated ketone chromophores, whose helicity (absolute conformation) can be deduced from their K-band Cotton effects. K. H. 0.
S. Hayakawa and Y. Sato, J. Org. Chem., 1962, 27, 704. F. C. Uhle, J. Org. Chem., 1962, 27, 656. J. A. Marshall and W. S. Johnson, J. Amer. Chem.SOC., 1962,84, 1485; G. Stork, S. D. Darling, I. T. Harrison, and P. S. Wharton, ibid., p. 2019. 222D. H. R. Barton and L. R. Morgan, J., 1962, 622. 2 2 3 J. E. Cole, W. S. Johnson, P. A. Robins, and J. Walker, J., 1962, 244. 2 2 4 D. J. Crispin and J. S. Whitehurst, Proc. Chem. SOC., 1962, 456. 2 2 5 S. N. Ananchenko, V. Y. Limanov, V. N. Leonov, V. N. Puzheznikov, and I. V. Torgov, Tetrahedron, 1962, 18, 1355. 2 2 6 W. L. Meyer, D. D. Cameron, and W. S. Johnson, J. Org. Chem., 1962, 27, 1130. 2 2 7 A. J. Birch and M. Smith, Proc. Chem. SOC., 1962, 356. 228D. Burn, B. Ellis, P. Feather, D. N. Kirk, and V. Petrow, Chem. and Ind., 1962, 1907. 2 2 9 H. J. Ringold and S. K. Malhotra, J. Amer. Chem. SOC., 1962, 84, 3402. 230 H. J. Ringold and S. K. Malhotra, Tetrahedron Letters, 1962, 669. 2 3 1 S. M. Kupchan, P. Slade, R. J. Young, and G. W. A. Milne, Tetrahedron, 1962, 18, 499. 2 3 2 H. Budzikiewicz and C. Djerassi, J. Amer. Chem. SOC., 1962, 84, 1430. 2 3 3 C. Djerassi, R. Records, E. Bunnenberg, K. Mislow, and A. Moscowitz, J. Amer. Chem. Soc., 1962, 84, 870.
219
22*
221
R E I D : AROMATIC COMPOUNDS
307
7. AROMATIC COMPOUNDS
A DISTINCTION has been drawn between, on the one hand, aromaticity and, on the other, aromatic reactivity and stability. The term aromaticity is used to refer to such ground-state properties of a molecule as its ability to sustain an induced ring-current of n-electrons and uniformity of bond lengths, whereas reactivity is dependent upon the free-energychange in going from the groundstate to the transition state for the chemical reaction invo1ved.l It has also been stressed that the " aromaticity " predicted by Huckel's rule refers to a particularly effective contribution by n-electron delocalisation to the total molecular stability.2 A series of constants has been calculated for some elements in terms of the effective charge of an atom of the element, its covalent radius, and the number of n-electrons which it contributes to a delocalised cyclic n-electron system. Summation of the constants of ring members gives an Aromaticity Constant which expresses the overall tendency of the ring to be more or less nucleophilic or electrophilicthan b e n ~ e n e . ~ Two benzene derivatives have been converted into their thermodynamically less stable alicyclic isomers. Ultraviolet irradiation of 1,2,4-tri-tbutylbenzene gave the electronically isomeric hydrocarbon (1) whose ultraviolet spectrum shows end absorption only and which is reconverted into 1,2,4-tri-t-butylbenzene on being briefly heated at 200 O . 4 The hydrocarbon (1) is the first compound known to contain the bicyclo[2,2,0]hexadiene structure proposed ninety-six years ago by Sir James Dewar as an alternative to the Kekul6 structure for benzene. Pyrolysis of the ester ( 2 ) at 360" gave 5-methylene-l,3-cyclohexadiene stable at -80" but rapidly (3), isomerising i the liquid state at room temperature t o toluene.6 The longn known thermochromism of 2,3-epoxy-2,3-diphenylindan-l-one is due t o (4) a reversible electronic isomerisation into the red compound (5). 7
Ph
Benzene Derivatives and Benzenoid Polycyclic Compounds.-Formation.

Treatment of sodium cyclopentadienidewith chloroform gives chlorobenzene, doubtlessly through the intermediate (6).8 Carbenes have also been utilised
Y. Amiel, F. Sondheimer, and R. Wolovsky, J . Amer. Chern. Soc., 1962, 84, 281; L. M. Jackman, F. Sondheimer, Y. Amiel, D. A. Ben-Efraim,Y. Gaoni, R . Wolov. sky, and A. A. Bothner-By, ibid., p. 4307. H. W. Chang, H. Hover, and R. Breslow, J . Amer. Chern. SOC., 1962, 84, 3168. S A . T. Balaban, Tetrahedron, 1962, 18, 315. S. P. Pappas and E. E. van Tamelen, J . Amer. Chem. Soc., 1962, 84, 3789. (Sir) J. Dewar, Proc. Roy. Soc. Edinburgh, 1866, 84. W. J. Bailey and R. A. Baylomy, J . Org. Chem., 1962, 27, 3476. J. E. Milks and E. F. Ullman, J . Amer. Chern. Soc., 1962, 84, 1315. A. F. Bickel and A. P. ter Borg, Rec. Trav. chim., 1961, 80, 1217.
'
308
ORGANIC CHEMISTRY
in the preparation of benzene derivatives by insertion into side-chains,Dthe use of dichlorocarbene being illustrated by the conversion of isopropylbenzene into the derivative (7) by means of sodium trichloroacetate in di-
methylformamide. Organometallic compounds are proving increasingly useful in synthetic work. The trimerisation of diphenylacetylene in nonhydroxylic solvents catalysed by di(benzonitri1e)palladium chloride gave hexaphenylbenzene,1and passage of acetylene into a solution of the monoadduct of di-t-butylacetylene and octacarbonyldicobalt in hot dimethylformamide gave o-di-t-butylbenzene.1l O-Phenylhydroxylamine, a rather unstable oil, has been synthesised by two methods,l2, 13 most conveniently by the electrophilic amination of potassium phenoxide with hydroxylamineO-sulphonic acid .I2 Arenediazonium fluoroborates react with nickel carbonyl to form aromatic carboxylic acids.14 A new transformation of heterocyclic compounds into benzene derivatives consists of treating pyrylium salts with Wittig reagents according to the annexed ~cheme.1~
*
R'
6 - Q - 6R3
R2
R'\*
R3
R'
R3
x-
C-R4
II Ph -jP
R4
2 Ph,P= CHR4
Ph,PO
ph3;.CH2R4
X'
The formation of the acid (9; R = C02H)and the corresponding hydrocarbon (9; R = H) on the attempted Wolff-Kishner reduction of the indanone derivative.(8) is one of thefew recorded ring-expansionsof indane into naphthalene derivatives.16 Desulphurisation of the thiepin (10) with Raney nickel appears to involve the diradicaI(l1) ; use of a catalyst saturated with hydrogen gave 2,2'-dimethylbipheny1 but with a catalyst of reduced hydrogen content ring-closure of the diradical (11)gave additionally 9,lO-dihydrophenanthrene and phenanthrene.17 The direct formation of 2,3-dibenzoylnaphthalene on alkali-catalysed condensation of o-phthalaldehyde with diphenacyl sulphide is one of several unusually ready sulphurextrusion reactions.18 The anthracene-diethyl azodiformate adduct (12 ; R = CO,Et), on careful hydrolysis, gave the thermally unstable compound (12; R = H) whose most interesting property is its ability to effect cislo
E. K. Fields, J. Amer. Chem. Soc., 1962, 84, 1744. A. T. Blomquist and P. M. Maitlis, J. Amer. Chem. SOC.,1962, 84, 2329.
E. 35. Arnett and M. E. Strem, Chem. and Ind., 1962, 2008. C. L. Bumgardner and R. L. Lilly, Chem. and Ind., 1962, 559. l3 J. S. Nicholson and D. A. Peak, Chem. and Ind., 1962, 1244. l4 J. C. Clark and R. C. Cookson, J., 1962, 686. l5 G . MErkl, Angew. Chem., 1962, 74, 696. l6 N. Campbell and H. G . Heller, J., 1962, 3006. l7 G. M. Badger, P. Cheuychit, and W. H. F. Sasse, J., 1962, 3241. I * J. D. Loudon and A. D. B. Moan, J., 1962, 3262.
l1
l2
309
hydrogenation of olehs.19 Pyridinium salts in the Michael reaction give addition products that are readily cyclised to polycyclic hydrocarbons ; thus the salt (13), obtained from benzylpyridinium bromide and benzylideneacetophenone, on treatment with zinc chloride a t 200" gave 1,3-diphenylna.phthalene O .
Ph
Br-
Benzo[blbiphenylene has been synthesised by a conventional route. 21 The photodimer (14) of lY4-naphthaquinone isomerised by alkali to the is tetrahydroxydibenzo[b,h]biphenylene (15; R = OH) which affords a tetramethyl ether (15; R = OMe).22 In contrast, enolisation of the cis-photodimer (16) of 2,3-dimethylbenzoquinnone involved only one of the sixmembered rings and gave compound (17), which was oxidised with silver oxide to the dihydro-diquinone ( 1 q . 2 3 Preparation of the dibenzo[b,h]biphenylene (15; R = Ph) is reported.24 The hydrocarbon (19) has been synthesised and, like other recently synthesised members of the cyclopentenoindane series, shows the characteristic properties of a compound containing a strained non-p1ana.r benzene ring.25
E. J. Corey and W. L. Mock, J . Amer. Chern. SOC., 1962, 84, 685. F. Krohnke and W. Zecher, Angew. Chern., 1962, 74, 811. 21 W. Baker, J. W. Barton, J. F. W. McOmie, and R. J. G. Searle, J., 1962, 2633. 2 2 J. M. Bruce, J., 1962, 2782. 2 3 R . C. Cookson, D. A. Cox, and J. Hudec, J., 1962, 1717. 2 4 3%. Avram, I. 0. Dinulescu, G. Mateescu, and C. D. Nenitzescu, Annalen, 1962,
l9
2o
653, 79. 2 5 B. L. McDowell, H. Rapoport, and G. Smolinsky, J . Amer. Chem. SOC., 1962, 84, 3531.
310
Substitution and mechanistic studies (cf. section 3). A composite review of nitrosation, diazotisation, and deamination has appeared.26 Exclusive formation of 2-nitrobiphenyl-2-carboxylic in the nitration of biphenyl-2acid carboxylic acid with nitrogen pentoxide is due to prior interaction between a substituent and the reagent. When concentrated nitric acid was the reagent the ortho/para-ratio was abnormally high, and partial or complete formation of the protonated mixed anhydride (20)is suggested (see p. 234).27Important results are emerging from studies of the mechanisms of aromatic hydroxylation. Isomer distribution determinations and comparisons of overall reactivities of substi OH tuted benzenes by competitive methods demonstrate the I electrophilic character of hydroxyl radicals generated by Fentons reagent. Hydroxylation by oxygen in the (20) presence of ferrous ion and ascorbic acid, however, has / the characteristics of a radical reaction, involving possibly the perhydroxyl radical HO-00,and is more akin to biological aromatic hydroxylation.28 Electrophilic hydroxylation of chalcone with concurrent ring-closure, by means of trifluoroperoxyacetic acid, is a new method of formation of the 3-hydroxyflavylium cation. The annexed scheme is envisaged. Polymethoxychalcones underwent ring-closure without hydroxylation, to give anthocyanidins.
XE+
Further examples of the ready nucleophilic substitution of polfluorinated aromatic compounds 30 have appeared. The fluorine atom in the 4-position of octafluorotoluene 31 and in the 2-position of octafluoronaphthalene 32 is the most easily displaced. Heating 2-nitrobiphenyl-2-carboxylic acid in quinoline, or its potassium salt alone, gives benzo[c]coumarin 2 7 (cf. p. 234). Studies have been made of the Kolbe electrolysis of o-benzoylbenzoic acids with a view to preparing radicals of the type involved in the Pschorr phenanthrene synthesis. Complex mixtures of products were 0btained.~3 Oxidation of the anions of aromatic carboxylic acids with persulphate gives arylcarboxy and thence aryl radicals which undergo the usual inter- and intra-molecular reactions.34 The unstable indazole (21) has been prepared 35 and behaves as required
J. H. Ridd, Quart. Rev., 1961, 15, 418. D. H. Hey, J. A. Leonard, and C. W. Rees, J., 1962, 4579. 28 R. 0. C. Norman and G . K. Radda, Proc. Chern. Soc., 1962, 138. 2 0 B. R. Brown, A. J. Davidson, and R. 0. C. Norman, Chern. and Ind., 1962, 1237. 30 See Ann. Reports, 1961, 58, 230. 31D. J. Alsop, J. Burdon, and J. C. Tatlow, J., 1962, 1801. a3 B. Gothing, C. R. Patrick, and J. C. Tatlow, J., 1962, 186. 33P. J. Bunyan and D. H. Hey, J., 1962, 324, 2771. 3 4 J. Russell and R. H. Thomson, J., 1962, 3379. 3 5 E. F. Ullman and E. A. Bartkus, Chem. and Ind., 1962, 93.
26 27
31 1
of a postulated intermediate in the von Richter reaction.36 A mechanism has been proposed for the acid-catalysed Wolff aromatisation of otp-unsaturated keto~imes.~'
Benxyne intemediates. Recent developments in benzyne chemistry (see also section 3) have been summarised 38 and a review has appeared.39 New methods of formation of benzyne include photolysis of phthaloyl peroxide 40 and of o-di-iodobenzene, thermal decomposition of diphenyliodonium-241 carb0xylate,4~and spontaneous decomposition at room temperature of benzo-1,2,3-thiadiazole 1,l-dioxide (22) whose preparation is described.43 The reversibility of benzyne formation from ortho-metallated aryl halides [step (a) of annexed scheme] has been elegantly d e m ~ n s t r a t e d . ~ ~ Decomposition of the precursor (22) in the presence of lithium chloride, bromide, or iodide gave, after hydrolysis, the corresponding halogenobenzene. Competition experiments gave an order of nucleophilic reactivity of halide ion towards benzyne of I : Br : C1= 65 : 8 : 1, in agreement with known nucleophilic reactivity values for these ions in SN2 reactions.45 The reversibility of the metallation [step (b)] has already been established.*6
The formation of tetrafluorobenzyne 47 and 9,lO-phenanthryne 48 has been demonstrated in trapping experiments with furan and other dienes. The acetylene (23) is apparently formed when the ketone (24) is treated with potassium t-butoxide ; it gave adducts with furan and tetraphenylcyclopentadienone.4 9 A mechanistically interesting reaction is the formation of the spirodienone (27) in the reaction of the halides (25; R = H, R' = Br) and ( 2 5 ;R = Br, R' = H) with potassium amide in liquid ammonia, involving the common benzyne intermediate (26).50 I n a new route to heterocyclic
R. T. Conley, Experientia, 1962, 18, 497. G. Wittig, Angew. Chem., 1962, 74, 479. 39 H. Heaney, Chem. Rev., 1962, 62, 81. 4 0 G. Wittig and H. F. Ebel, Annalen, 1961, 650, 20. 41 E. Hoffmeister and J. A. Kampmeier, J . Amer. Chem. SOC., 1962, 84, 3787. 4 2 E. L e Goff, J . Amer. Chem. Soc., 1962, 84, 3786. 4 3 G. Wittig and R. W. Hoffmann, Chem. Ber., 1962, 95, 2718. 4 4 G. Wittig and R. W. Hoffmann, Chem. Ber., 1962, 95, 2729. 4 5 C. G. Swain and C. B. Scott, J . Arner. Chem. SOC., 1953, 75, 141. 4 6 G. E. Hall, R. Piccolini, and J. D. Roberts, J . Amer. Chem. SOC., 1955, 77, 4540; L. A. Carlsmith, J. D. Roberts, D. A. Semenov, and H. E. Simmons, ibid., 1956, 78, 601. 4 7 P. L. Coe, R. Stephens, and J. C. Tatlow, J., 1962, 3227. 4 8 G. Wittig, W. Uhlenbrock, and P. Weinhold, Chem. Ber., 1962, 95, 1692. 4 s W. Tochtermann, Angew. Chem., 1962, 74, 432. D. H. Hey, 4. A. Leonard, and C . W. Rees, Chem. and Id., 1962, 1025.
30
36 37
See Ann. Reports, 1960, 57, 226.
312
ORGANIC CHEMISTRY
compounds benzyne behaves as a 1,3-dipolarophile,reacting for example with ethyl diazoacetate to give ethyl indazole-3-carboxylateand with phenyl azide to form 1-phenylbenzotriazole.51
Aromatic 1 0 1 ~and Radicals.4utions. Triphenylmethyl perchlorate reacts with diazomethane to give triphenylethylene and 1,2,3-triphenylpropene, in accordance with simple carbonium-ion behaviour.52 The doubly charged cations (28; R = Me or H) have now been isolated as the stable dark red bis-fluor~borates.~~ There has been much interest recently in the preparation of new cyclic cations and the examination of their properties in the light of predictions based on molecular orbital theory. The brick-red salt (29), prepared by the sequence shown herewith, is stable to light and dry air, resembles the triphenylmethyl cation spectrally, and is irreversibly hydrolysed by water.54 In contrast, reaction of the dichloride
Me
"0;.
* CCI
(28)
Me
;)$;
Ni
Ph Ph
6Br Br
PhmPhS"C,:Ph Ph
Ph
(29)
Br'
'Br
1, Pyridinium hydrobromide perbromide. 2, SnC1,.
(30)with silver hexafluoroantimonatein liquid sulphur dioxide a t -70" gave the cation (31) and not the tetramethylcyclobutadiene d i - ~ a t i o n . ~ ~ Full details of the preparation and properties of the di-n-propylcyclopropenylium and tri-n-propylcyclopropenylium cations are now available.2 The heat of formation of the cyclopropenyl cation is identical with those of the cations derived by loss of an electron and a hydrogen atom from allene and m e t q l acetylene and the interesting suggestion is made that all three species have the same cyclopropenylium structure.56 Support is accumulating for
51
53 54 55
R. Huisgen and R. Knorr, Naturwiss., 1961, 48, 716.
52H. Whitlock, J. Amer. Chem. Xoc., 1962, 84, 2807. W.

J. S. Fleming and H. Hart, Tetrahedron Letters, 1962, 983. A. M. Frantz and H. H. Freedman, J. Amer. Chem. SOC.,1962, 84, 4165. J. R. Hall, T. J. Katz, and W. C. Neikam, J. Amer. Chem. Soc., 1962, 84, 3199. W. J. Bartley and K. B. Wiberg, J. Amer. Chem. SOC., J962, 84, 3980.
56
313
Winstein's concept of " homoaromaticity." 5 7 The properties of solutions of the lactone (32) in concentrated sulphuric acid are best interpreted in terms of the structure (33).58 Especially convincing are the preparation and nuclear magnetic resonance spectral properties of the stable yellow homotropylium hexachlorantimonate (34), obtained by treatment of 7chlorocyclo-octa1,3,5-triene with antimony pentachloride.59 Significant features of the nuclear magnetic resonance spectrum of the salt (34), or,
0
MG:;
M e Me
(30)
I ( 3 3 ) COzH
(34)
equivalently, of cyclo-octatetraene in sulphuric acid, are the occurrence of the 2-H to 6-H signals in the aromatic region, the abnormally low position of the l-H and 7-H signals indicating the participation of C-1 and C-7 in the cyclical conjugation, and the high shielding of H, by ring-currents owing to its position above the ring. A re-investigation 6 0 of the reaction of cycloheptatriene with phosphorus pentachloride shows that the product is probably the double salt C7H7 +C1-,C7H,+PCl,-, and not tropylium chloride as previously supposed. Tropylium salts are formed in good yield on autoxidation of cycloheptatriene in acetic acid containing strong acids.61 The formation of a green phenyltribenzotropylium cation in solution is reported. 62 Anions. The anion (35) has been isolated as its air-sensitive black tetrapotassium salt.63 Members of several new classes of polymethine carb-
J. Sonnenberg and S . Winstein, J . Arner. Chem. SOC., 1961, 83, 3244, 3248. R. R. Sauers, Tetrahedron Letters, 1962, 1015. 5 9 J. E. Mahler, R. Pettit, and J. L. von Rosenberg, J . Arner. Chenz. SOC., 1962, 84, 2842. 6 o D. Bryce-Smith and N. A. Perkins, J., 1962, 1339. 61 A. F. Bickel, A. P. ter Borg, and R. van Helden, Rec. Trav chirn., 1962, 81, 164. 6 2 G. Wittig, E. Hahn, and W. Tochtermann, Chern. Ber., 1962, 95, 431. 63 H. Y . Niu and R. West, J . Arner. Chern. SOC., 1962, 84, 1324.
57
58
314
ORGANIC CHEMISTRY
anionic dyes have been prepared as the alkali-metal salts, e.g., (36),64(37),65 and (38).65 The diamagnetic purple potassium salt of the heptaphenylcycloheptatriene anion has been prepared and examined in solution by two groups of workers.ss The pentalene dianion (39), isoelectronic with naphthalene and azulene, has been isolated as the stable colourless di-lithium salt.67 Radicals. Flash-photolysis of ditropyl gave a product whose ultraviolet spectrum is attributed to the tropyl radical.68 Although attempts to isolate this radical have been unsuccessful the russet paramagnetic heptaphenyltropyl radical has been prepared in solution,66 and the deep red tropyl derivatives (40; R = H or Ph) are formed reversibly when their dimers are heated.62 Tropones and Related Compounds.-A useful new synthesis 69 of tropones (cycloheptatrienones) consists in the reaction of 2,5-dihydroanisoles with dihalogenocarbenes, followed by hydrolysis with hot aqueous silver nitrate of the adducts which result from preferential addition at the enol ether double bond.
(R = H, OMe.)
(R = H,OH)
Tropones undergo I ,&addition with Grignard reagents and lithium aluminium hydride, giving (2-substituted) 3,5-cycloheptadienones. 71 If 70, 2-chlorotroponesare used initially, dehydrochlorination of the addition products affords 2-substituted tropones.71 Tropolones react with 2-alkoxy-l,3dioxa-2-boroles to form stable yellow tropovinylene spiroborates, e.g., (41), a new class of ~ w i t t e r i o n s . ~ ~ heterocycle (42) is the simplest of The the few aza-analogues of tropones yet synthesised ; its infrared spectrum reveals an abnormally highly polarised carbonyl group and the nuclear magnetic resonance spectrum indicates a ring-current and hence aromaticity. 73 While heptafulvene (43; R = R = H) is extremely reactive and exists only in solution, placing strongly electron-withdrawing substituents on the methylene-carbon atom stabilises the assembly, and the compounds (43; R = R = CN or C0,Et) a,nd (43; = CN, R = CO,Et) have been isolated R
K. Goliasch and K. Hafner, Angew. Chem., 1062, 73, 118. H. Amschler and C. Jutz, Angew. Chem., 1962, 73, 806. 6 6 M. A. Battiste, J . Amer. Chenz. Soc., 1962, 84, 3781; R. Breslow and H. W. Chang, ibid., p. 1484. G 7 T. J. ICatz and M. Rosenberger, J . Anzer. Chem. Soc., 1962, 84, 864. 1962, 339. 6 8 B. A. Thrush and J. J. Zwolenik, Proc. Chem. SOC., 6 9 A. J. Birch, J. M. H. Graves, and F. Stansfield, Proc. Chem. SOC., 1962, 282. 7 0 0. L. Chapman, A. A. Griswold, and D. J. Pasto, J. Amer. Chem. SOC., 1962, 84, 1213. 71 A. F. Bickel, A. P. ter Borg, and R. vaa Helden, Rec. Trav. chim., 1962, 81, 691. 7 2 R. Antonescu, A. T. Balaban, P. T. Frangopol, and G. Mihai, Tetrahedron, 1961, 16, 68. 73 E. Bullock, B. Gregory, and A. W. Johnson, J . Amer. Chem. Soc., 1962, 84, 2260.
64
65
REID: AROMATIC COMPOUNDS
315
stable red solids.74 Treatment of 2,6-dimethylphenol with two equiconverted valents of tropylium salts gives the stable orange-red salts (44), by base into the somewhat unstable purple ketone (45).75
@4fj OH Me
(44)
X.-
(X = CI,C104-,
or B F 4 )
(45)
Eeptalene and PentaJenes.-Combined theoretical and spectral studies indicate that the heptalenium ion is n ~ n - p l a n a r . ~ ~ highly substituted Two (46) forms pentalenes have been prepared. 1,2,3-TriphenyIbenzopentalene green crystals, stable to heat and air, and insoluble in 85% phosphoric acid
but rapidly attacked by nucleophiles.77 Hexaphenylpentalene, stable brown to needles, results from the Michael addition of 1,2,3-triphenylpropen-l-one 1 ,2,3-triphenylcyclopentadiene with concomitant ring-closure, and subsequent bromination-dehydrobromination ;it gives a blue solution in trifluoroacetic acid and with dimethyl acetylenedicarboxylate undergoes ring-expansion to the azulene (47;R = Ph, R' = CO&e or vice wer~a).~* Azdenes.-The key step in a new and interesting, but preparatively useless, azulene synthesis is the photochemical ring-contraction of the diazoketone (48)to the hexahydroazulene (49 or double-bond isomer), which is
" 0 'H ' O

7 4 T.Mukai, T. NOZOB, Osaka, and N. Shishido, Bull. Chem. Soc. Japan, 1961, K. 34, 1384. 7 b A. F. Bickel, A. P. ter Borg, and R. van Helden, Rec. Trav. chim., 1962, 81,
599.
77
E. Heilbronner, W. Meier, and D. Meuche, H d v . Chim. Acta, 1962, 45, 2628. E. Le Goff, J. A m r . Chem. Soc., 1962, 84, 1505. 7 a E .Le Goff,3. Amer. Ohem. Soc., 1962, 84, 3975.
'13
316
ORGANIC CHEMISTRY
converted by standard steps into methyl azulene-2-carboxylate. Applica79 tion of the Friedlander synthesis to 2-amino-1-formylazulenegave derivatives of the new pyrido[3,2-a]azulene system, e.g., (50), use of acetylacetone on and (51) on use of diethyl malonate.80 Proton magnetic resonance studies confirm the finding that monoprotonation of alkylazulenes in strong acids occurs at an unsubstituted 1- or 3-position.81 Interestingly, protonation of l-nitro-4,6,8-trimethylazulene gives the 4,6,8-trimethyl-l-nitro-lHazulenium cation owing, it is suggested, to the accompanying relief of steric The strain,82 while l-nitroazulene gives the cation ( ~ i 2 ) . 8 ~ long-wave absorption bands of azulenium ions are charge-transfer bands.84 Hafner et al. have now published details of the preparation and reactions of 1-alkylideneazulenium salts,85studies and synthetic applications of the acidity of 4- and 6-methyl groups in azulenes,86and the reactions of azulenes with organolithium reagents 8' and carbonium ions.88 Vilsmeier formylation of 1,3dialkylazulenes occurs preferentially a t position 2, lY3-dimethylazulene giving exclusively 2-formyl-l,3-dimethylazulene, changes to position 5 but with increase in size of the alkyl groups. Alkyl-displacement also occurs with increasing ease and, while 1,3-di-isopropylazulene gave a mixture of 2- and 5-formyl-l,3-di-isopropylazulene with l-formyl-3-isopropylazulene, 1,3-di-t-butylazulene gave 5-formyl-1,3-di-t-butylazulene l-formyl-3-tand butylazulene.89 Ready group-displacement was also observed in acetylation 88, 89 and diazo-coupling studies.88 Halogen in position 1 is stable to nucleophiles, but in position 6 it is smoothly repla~ed.~O Macrocyclic Compounds.-Annulenes. Full details l, 92 are now available of the preparation of the annulenes [CHI, where 7t is 18,20, 24, or 30, and of dehydroannulenes used as their precursors. Two new dehydroannulenes are a hexadehydro[36]annulene 93 and a bi~dehydro[l2]annulene.~*The chemistry of [18]annulene alone has been studied in some detail.l, 91 It is unstable t o air and light, gave no recognisable nitration, sulphonation, or Friedel-Crafts acetylation product, and did not form complexes with trinitrobenzene or trinitrofluorenone, but added hydrogen catalytically, as well as bromine and maleic anhydride. Although it thus showed no aromatic reactivity [18lannulene shows aromaticity in its planarity, in its ability to sustain an induced ring-current of n-electrons, and in the non-alternation
L. Horner and K. H. Weber, Chem. Ber., 1962, 95, 1227. K. Kikuchi and T. Nozoe, Chem. and I n d . , 1962, 358. 81 S. S. Danyluk and W. G. Schneider, Canad. J . Chern., 1962, 40, 1777. 8 2 F. A. Long and J. Schulze, Proc. Chem. SOC., 1962, 364. 83 E. Heilbronner and D. Meuche, Helv. Chim. Acta, 1962, 45, 1965. 8 4 E. Heilbronner, W. Meier, and D. Meuche, Helv. Chim. Acta, 1962, 45, 2628. 8 5 K. Hafner, H. Pelster, and J. Schneider, Annalen, 1961, 650, 62. 8 6 K. Hafner, H. Patzelt, and H. Pelster, Annalen, 1961, 650. 80. 8 7 C. Bernhard, K. Hafner, and R. &Idler, Annalen, 1961, 650, 35. 8 8 C. Bernhard, K. Hafner, and A. Stephan, Annalen, 1961, 650, 42. S 9 K. Hafner and K. L. Moritz, Annalen, 1962, 656, 40. 9 0 K. Hafner, H. Kaiser, and H. Patzelt, Annalen, 1962, 656, 24. 9 1 Y. Arniel, F. Sondheimer, and R. Wolovsky, J . Amer. Chem. SOC., 1962, 84,
79 8o
274.
Y. Gaoni and F. Sondheimer, J . Amer. Chem. SOC., 1962, 84, 3520. F. Sondheimer and R. Wolovsky, J . Amer. Chem. SOC., 1962, 84, 260; Y. Amiel, Y. Gaoni, and F. Sondheimer, ibid., p. 270. 9 4 F. Sondheimer and R. Wolovsky, J . Amer. Chern. SOC., 1962, 84, 2844.
92
93
R E I D : AROMATIC C O M P O U P J D S
317
of its bond lengths which is in line with its conformation to Hiickel's rule (n = 4). [14]Annulene, although conforming to the rule, does not sustain an induced ring-current and possesses the geometric configuration of the periphery of pyrene.95 A test of Hiickel's rule is whether or not aromaticity is shown by annulenes not conforming to it. [24]Annulene shows the absence of aromaticity, probably on this account. An interesting problem is the possibility of an annulene displaying stereoisoaromaticity and variable aromatic reactivity, depending on its existence in more than one stereochemical form. It is not certain whether the [20]- and [30]-annulenes are homogeneous or mixtures of such stereoisomers, and whether the same [30]annulene is obtained in different syntheses.92 ParacycZophanes. A promising new approach to the paracyclophanes has its prototype in the preparation of [8]paracyclophane-4-carboxylic acid (53) by photochemical ring-contraction of the diazo-ketone (54).96 A nonaromatic route to [2,2]paracyclophanes is illustrated here for the synthesis of the 2,5,3',6'-tetramethyl derivative (55).97
CCH2I4' g i""02H
\
[CH2]41
C=NI
1. H2C 1 H2C .
p &
P 2 1 3
( 5'3 )
P 2 1 3
J .
0
\Ii
CH2.I CH2
(54)
''
Me
H2:O:H2
H2c
H2C
(55)
1, KOH-MeOH.
2 Isomerisation. 3, Dimerisation. ,
Phenols, Quinones, and Naturally Occurring Aromatic Compounds.Acenaphthenequinone is ring-enlarged by diazoalkanes to 3-alkyl-2hydro~yphenalenones.~~ structure of the mould metabolite atroThe venetin has been revised to (56)as a result of X-ray crystallographic studies;g9
95
96 O7
ss
99
J. Bregman, Nature, 1962, 194, 679. N. Allinger and L. A. Freiberg, J . Org. Chem., 1962, 27, 1490. D. T. Longone and C. L. Warren, J. Amer. Chem. Sac., 1962, 84, 1507. B. Eistert and A. Schonberg, Chem. Ber., 1962, 95, 2416. G. A. Morrison, I. C. Paul, and G. A. Sim, Proc. Chem. SOC.,1962, 352.
318
ORGANIC CHEMISTRY
and trimethylherqueinone Bya derivative of the related herqueinone, possesses structure (57).loo Otobain, the major component of otoba fat, has the structure (58).lo1 " Xylindein," the green pigment first isolated by Dobereiner in 1813 from wood infected with Chlorociboria aeruginosa, is a mixture of closely related substances. The na,me " xylindein " is retained (see section 8). The naphthaquinone (59) has for the major component lo2 been recognised as a toxic component of teak and synthesised.lo3 The yellow pigment of the root of the Himalayan plant InuZa royleana D.C. is a mixture of a new group of diterpenoid quinones named royleanones, whose major components are royleanone and acetoxyroyleanone (see p. 296) .lo4 Three members of a new group of naturally occurring quinones, called dalbergiones, have been isolated and identified.lo5 An interesting feature of their chemistry is that the parent dalbergione (60; R = H) has opposite stereochemistry to the other two members (60; R = OH and OMe).
Two new syntheses lo% of the antibiotic griseofulvin (see section 7) lo7 have been developed. A review 108 has been given of the synthesis and biologically active degradation products of the tetracyclines by Muxfeldt who has reported a partial synthesis of terramycin (61; R1 = H, R2 = Me, R3= OH) l o 9 and a synthesis of ( -j) -decarboxamidodedimethylamino-6,12a,-dideoxytetracycline. 1l0 A total synthesis of 6-demethyl-6-deoxytetracycline, fully biologically the active prototype of the tetracycline series,lll and a determination of the absolute configuration of the natural tetracyclines by optical rotatory dispersion studiesY1l2 have been reported (see p. 288). Notable progress has been made in biosynthetic studies. Evidence is adduced that the C-methyl and C-dimethylamino-groups in the tetraloo
J. Cason, J.
Gilchrist, R. Hodges, and A. L. Porte, J . , 1962, 1780. G. M. Blackburn, A. H. Neilson, and Lord Todd, J . , 1962, 327. W. Sandermann and M. H. Simatupang, Angew. Chem., 1962, 74, 782. lo4 0. E. Edwards, G. Feniak, and M. Los. Canad. J . Chem., 1962, 40, 1540. I o 5 W. B. Eyton, 0. R. Gottlieb, L. M. Jackman, M. T. Magalhaes, W. D. OIlis, and I. 0. Sutherland, Proc. Chem. SOC., 1962, 301. lo6 C. H. Kuo, D. Taub, and N. L. Wendler, Chem. and Ind., 1962, 1617. lo' G. Stork and M. Tomasz, J . Amer. Chem. SOC., 1962, 84, 310. lo*H. Muxfeldt, Angew. Chem., 1962, 74, 443. l o oH. Muxfeldt, Angew. Chem., 1962, 74, 825. H. Muxfeldt, W. Rogalski, and K. Striegler, Chem. Ber., 1962, 95, 2581. l l 1 K. Butler, L. H. Conover, J. D. Johnston, J. J. Korst, and R. B. Woodward, 1962, 84, 3222. J . Amer. Chem. SOC., 112 V. N. Dobrynin, A. I. Gurevich, M. G. Karepetyan, M. N. Kolosov, and M. M. Shemyakin, Tetrahedron Letters, 1962, 901.
lol T.
18, 839.
lo2 lo3
s. Correia, R. B. Hutchison, and R. F. Porter, Tetrahedron,
1962,
ACHESON
: HETEROCYCLIC COMPOUNDS
319
cyclines are derived from methionine, and that the main skeleton is largely, but not entirely, built by head-to-tail linkage of acetic acid units.113 The final two steps in the biosynthesis of the tetracyclines involve oxidative hydroxylation of 5aY6-anhydrotetracyclines t C-6 and reduction of the a
resulting 5a,l la(5,5a)-dehydrotetracyclineY exemplified by the formation of 7-chlorotetracycline (61; R1 = C1, R2 = Me, R3 = H) from its precursor (62).114 The hydroxylation step has been simulated in vitro by the photoperoxidation of compound (62) and subsequent mild catalytic hydrogenation of the product (63) to 7-chloro-5,5a-dehydtetracycline (64).l15 The stereochemistry of the synthetic material is that of the natural product. D. W. R.
COMPOUNDS Reviews.-New books which have appeared include a new edition of a general textbook, volumes dealing with compounds possessing bridgehead nitrogen atomsy2pyridinesY3 pyrimidinesy4industrial nitrogenous heterocyclics, pyrazolone and pyrazolidinediones, and flavonoids. Heterocyclic
8. HETEROCYCLIC
A. J. Birch, J. F. Snell, and P. J. Thomson, J . , 1962, 425. N. Arnold, S. Johnson, J. R. D. McCormick, P. A. Miller, and N. 0. Sjolander, J . Arner. Chem. SOC., 1962, 84, 3023. 115 C. T. Bedford and A. I. Scott, J . Arner. Chem. SOC., 1962, 84, 2271. R. M. Acheson, An Introduction to the Chemistry of Heterocyclic Compounds, Interscience-Wiley, New York, revised edn., 1962. W. L. Mosby, Heterocyclic Compounds with Bridgehead Nitrogen Atoms, Vol. XV, Chemistry of Heterocyclic Compounds, Part I (1961) and Part I1 (1962), Interscience-Wiley, New York. E. Klingsberg, Pyridine and its Derivatives, Vol. XIV, Chemistry of Heterocyclic Compounds, Part I (1960), Part I1 (1961), and Part I 1 (1962), Interscience1 Wiley, New York. D. J. Brown, The Pyrimidines, Vol. XVI, Chemistry of Heterocyclic Compounds, Interscience-Wiley, New York, 1962. M. J. Astle, A.C.S. Monograph, No. 150, Industrial Organic Nitrogen Compounds, Reinhold Publ. Co., N ~ w York. W. Krohs and 0. Hersel, Pyrazolone und Dioxopyrazolidine, Editio Cantor, Wiirtemburg, Germany, 1961. The Chemistry of the Flavonoid Compounds, ed. T. A. Geissman, Pergamon Press, Oxford, 1962.
113 114
320
ORGANIC CHEMISTRY
boron derivatives, urotropine and other heterocyclic compounds based on adamantane, and Diels-Alder syntheses with heteroatomic compounds including and leading to heterocyclic derivatives l o have been reviewed. Discussions of organic sulphur compounds in edible plants,ll desulphurisation by Raney nickel,l2 non-mercurial diuretics,13 and psychotomimetic substances l4 involve many heterocyclic compounds. Other reviews deal with chemical syntheses of nucleosides,15the synthesis of purines from pyrimidines,16 triazine herbicides,17 syntheses with azolides,l8 naturally occurring xanthones,19 rearrangements of aziridines,20 2-amino-1,3,4-oxadiazoles,21 chemistry of thiamine,22 and the photothe chemistry of ribofla~ine.~s Three- and Four-membered Rings.-Aziridine combines with aliphatic aldehydes, yielding aminohydrins (1) which isomerise to oxazolidines in refluxing ether,24and benzenediazonium chloride and sodium acetate give 25 l-phenylazoaziridine (2). This gave the triazoline (3) with sodium iodide,
have been deand similar ring expansions of 2-1-aziridinylquinoxalines scribed.26 Tracer studies z7 suggest that l-benzenesulphonyl-2-bromomethylaziridine, aluminium chloride, and benzene yield N-(3,3-diphenylpropy1)benzenesulphonamide through the intermediary of the azetidine (4). Aziridine with the very mild nitrosating agent, 3-nitro-9-nitrosocarbazole, yields ethylene and nitrous oxide,28 possibly through 1-nitrosoaziridine,and (5).29 Tetrawith a-mercapto-ketones gives 3,4-dihydro-2H-thiazines min, the broad-spectrum anti-neoplastic agent obtained from 2-vinyloxiran and aziridine, is a 2 : 1 mixture of the aziridines (6) and (7).30 Substituted
P. M. Maitlis, Chem. Rev., 1962, 62, 223. H. Stetter, Angew. Chem., 1962, 74, 361. l o S. B. Needleman and M. C. C. Kuo, Chem. Rev., 1962, 62, 405. l 1 A. I. Virtanen, Angew. Chern., 1962, 74, 374. l 2 H Hauptmmn and W. F. Walter, Chem. Rev., 1962, 62, 347; G. R. Pettit and . E. E . van Tamelen, Org. Reactions, 1962, 12, 356. 13E. Schlittler, G. de Stevens, and L. Werner, Angew. Chem., 1962, 74, 317. l 4 D. F. Downing, Quart. Rev., 1962, 16, 133. l 5 T. L. V. Ulbricht, Angew. Chem., 1962, 74, 767. l o J. H.Lister, Rev. Pure AppZ. Chem. (Australia), 1961, 11, 178. l 7H. Gysin, Chem. and Ind., 1962, 1393. H. A. Staab, Angew. Chem., 1962, 65, 407. l9 J. C. Roberts, Chem. Rev., 1961, 61, 591. 2 O H. W. Heine, Angew. Chem., 1962, 74, 772. 21 G. Blankenstein and K. Mockel, 2. Chem., 1962, 2 69. , 2 2 Various authors, ed. H. M. Wuest, Ann. New York Acad. Sci., 1962, 98, 383. 23 G. Ostler, J. S . Bellin, and B. Holmstrom, Experientia, 1962, 18, 249. 2 4 W. J. Rabourn and W. L. Howard, J . Org. Chem., 1962, 27, 1039. 2 5 H. W. Heine and D. A. Tomalia, J . Amer. Chem. Soc., 1962, 84, 993. 2 6 H. W. Heine and A. C. Brooker, J . Org. Chem., 1962, 27, 2943. 2 7 W. F. Gensler and W. R. Koehler, J . Org. Chem., 1962, 27, 2754. 2 8 C. L. Bumgardner, K. S . McCallum, and J. P. Freeman, J . Amer. Chenz. SOC., 1961, 83, 4417. 2 9 F. Asinger, F. J. Schmitz, and S. Reichel, Annalen, 1962, 652, 50. 30 A. T. Bottini and V. Dev, J . Org. Chem., 1962, 27, 968.
ACHESON : HETEROCYCLIC COMPOUNDS
321
azirines are obtained 31 by vapour-phase pyrolysis of a-alkyl- or or-aryl-aazidoethylenes.
R'
"CS)
N
The acid-hydrolysis of 1-alkyldiaziridines (e.g., 8) to the alkylhydrazine and carbonyl compound is a fist-order reaction.32 Reduction of this diaziridine (8) with lithium aluminium hydride gives N-n-propylcyclohexylamine and ammonia, and hydrogenation over Raney nickel yields cyclohexylamine and n-propylamine. Diazirine (9) is a colourless gas, b.p. -14", p 1-59& 0 0 D , which can be obtained by reaction of formalde.6 ~ ~ hyde, chloramine, and ammonia followed by oxidation in situ with chromic acid,x4 or directly 35 from difluoramins and 2,2,4-trimethylpentylazomethine in carbon tetrachloride. Its molecular dimensions (C-N 1.482, N-N 1-288, C-H 1-07 8 ; angle H-C-H 117") were deduced 33 from microwave data. Diazirine is more stable than diazomethane and can be stored in glass. It is stable t o t-butoxide in t-butyl alcohol and is decomposed relatively slowly by sulphuric acid. Photolysis 36 yields nitrogen and carbene which is more selective in its reactions than the carbene obtained similarly from " linear " diazomethane. The thermal decomposition of dimethyldiazirine is a true first-order homogeneous reaction yielding nitrogen and propene.37 Many aldehydes and ketones with dimethylsulphoxoniummethylide (1l), from sodium hydride and trimethylsulphoxonium halides yield oxirans ( 10) and dimethyl sulphoxide.38
(' 2)
Thiirans (e.g., 12) are obtained from diaryldiazomethanes and sulphur at room t e m p e r a t ~ r e . ~ ~ Cyclic carbonates (e.g., 13) of 1,Z- and 1,3-diols with potassium thiocyanate yield thiirans (e.g., 14) and thietans, respecwith iodine tively.40 Desulphurisation of cis- and trans-2,3-dimethylthiiran
0
31
32
95, 1759, and preceding papers. L. Pierce and V. Dobyns, . J . Amer. Chem. Soc., 1962, 84, 2651. 3 4 E. Schmitz and R. Ohme, Chem. Ber., 1962, 95, 795. 35 W. H. Graham, J. Amer. Chem. Xoc., 1962, 84, 1063. 36 13. M. Frey and I. D. R. Stevens, Proc. Chem. SOC., 1962, 79. 37 H. M. Frey and I. D. R. Stevens, J., 1962, 3865. 38 E. J. Corey and M. Chaykovsky, J . Amer. Chem. SOC., 1962, 84, 867. 39 N. Latif and I. Fathy, J. Org. Chem., 1962, 27. 1633. 4 0 S. Searles, H. R. Hays, and E. F. Lutz, J. Org. Chem., 1962, 27, 2828, 2832.
33
G. Smolinsky, J. Org. Chem., 1962, 27, 3557. C. Szantay and E. Schmitz, Chem. Ber., 1962,
322
ORGANIC CHEMISTRY
in benzene proceeds stereospecifically yielding cis- and trans-butene, respectively.41 The first three-membered rings containing silicon and germanium have been ~ynthesised.~~ Diphenylacetylene and either dichlorodimethylsilane with sodium, or polydimethylsilicon, give low yields of 1,l-dimethyl-2,3diphenylsiliren ( 15). Similarly germanium di-iodide with hot acetylene or diphenylacetylene gives 1,l-di-iodogermiren or its 2,3-diphenyl derivative (16) which undergoes the reactions indicated. It is suggested that these compounds may be stabilised by ppp- or ppd-conjugation.
(16)
The early claim 43 that azetidine, the preparation of which has been improved,44with nitrous acid yields 1-nitrosoazetidine has been confirmed by nuclear magnetic resonance studies.28 The nitroso-compound with trifluoroperoxyacetic acid gives 1-nitroazetidine. The highly strained azetidinone (17) undergoes a fascinating series of transformation^,^^ some of which are outlined in the annexed scheme.
Ph
Y +
NH2
Ac
Ph
fi
N-NH
Bz
1, KOH-MeOH.
2, BzCl. 3, AcOH. 4, MeOH-BzOH-NaOBz. 5, MeOH-HCO,-. 6, HCl.
Many new penicillins have been prepared 46 by the acylation of 6-aminopenicillanic acid which has been synthesised.47 Methanesulphonyl chloride and triethylamine with keten acet a1 give 3,3-diethoxythietan 1 , l - d i o ~ i d e .Attempts to convert t'nietan-3-01into ~~ thiete (thiocyclobutene)gave p0lymers,~9 oxidation 5 O yielded thietan-3but
G. K. Helmkamp and D. J. Pettit, J. Org. Chem., 1962, 27, 2942. M. E. Volpin, Yu. D. Koreshkov, V. G . Dulova, and D. N. Kursanov, Tetrahedron, 1962, 18, 107. 4 3 C. C. Howard and W. Marckwald, Ber., 1899, 32, 2032. W. R. Vaughan, R. S. Klonowski, R. S. McElhinney, and B. B. Millward, J . Org. Chem., 1961, 26, 138. 4 5 J. A. Moore, F. J. Marascia, F. W. Medeiros, and E. Wyss, J . Amer. Chern. SOC., 1962, 84, 3022. 413F. P. Doyle, K. Hardy, J. H. C. Nayler, M. J. Soulal, E. R. Stove, and H. R. J. Waddington, J., 1962, 1453, and earlier papers. 4 7 J. C. Sheehan and K. R. Henery-Logan, J . Amer. Chenz. SOC., 1962, 84, 2983. 4 8 W. E. Truce, J. J. Breiter, D. J. Abraham, and J. R. Norell, J . Amer. Chem. SOC., 1962, 84, 3030. 4 9 M. E. Christy, Dim. Abs., 1961, 22, 69: D. C. Dittmer and M. E. Christy, J . Amer. Chern. Soc., 1962, 84, 399. 5 0 H. Prinzbach and G. von Veh, 2. Naturforsch., 1961, 16b, 763.
41 42
323
one which has also been obtained 51 from 1,3-dibromoacetone dimethyl acetal and sodium sulphide with subsequent mild acid hydrolysis. Thietan%one, m.p. 63.5 gives a semicarbazone and a 2,4-dinitrophenylhydrazone. Thiete 1,l-dioxide formed an adduct with anthracene, and treatment with sodium borohydride and lithium aluminium hydride yielded thietan 1 , l dioxide and propane-1-thiol, respe~tively.~~ The first dithiet (18) to be prepared, a yellow liquid, b.p. 95-96", was obtained 52 in 80% yield from hexafhorobut-2-yne and sulphur. Some complex derivatives of 1,2-thiazetidine have been made.63 The fourmembered phosphorus heterocycle (19), obtained from 2,4,4-trimethylpentene, phosphorus trichloride, and aluminium trichloride, is stable t o hot nitric or sulphuric acid and to aqueous sodium hydroxide.54
O,
Five-membered Rings and Condensed Derivatives.-Pyrroles. Pyrrolidine is obtained 5 5 from putrescine and Raney nickel in an inert solvent. Hydroxylamine-0-sulphonic acid with sodium ethoxide and butadiene gave some 2,5-dihydr0pyrrole.~6 A new synthesis of pyrroles 5 7 which may have general application is outlined, as annexed. Syntheses of aminopyrroles (20)
fioMe OH + /CH2*C02Et
Tos*NH
[Tos
- dce,.
P205_
Tos
N Tos
r YrJ:: J e
NaH -+-
CO2Et
N
H
= p-C6H4Me-S02]
from a-amino-ketones and malonodinitrile,5 8 of the triaminopyrrole (21) from tetracyanoethylene and hydrazine hydrate, 5 9 and of complex pyrrolines and pyrroles from nitrile ylides,60 have been described. The nuclear magnetic resonance spectra of pyrroles are simplified by addition of piperidine which eliminates coupling involving the 1-hydrogen atom.61 Photo-oxidation of pyrrole in the presence of eosin gives the
61 s2
82, 1515.
R. Mayer and K. F. Funk, Angew. Chem., 1961, 73, 678. C. G. Krespan, B. C. McKusick, and T. L. Cairns, J . Amer. Chem. Soc., 1960,
sa B. J. R. Nicolaus, E. Bellasio, and E. Testa, Helv. Chim. Acta, 1962, 45, 717.
&* J. J. McBride, E. Jungermann, J. V. Killheffer, and R. J. Clutter, J. Org. Chem., 1962, 27, 1833. 5 5 K. Kindler and D. Matthies, Chem. Ber., 1962, 95, 1992. 56R. Appel and 0. Buchner, Angew. Chem., 1962, 65, 430. s 7 A. H. Jackson, G. W. Kenner, and W. G. Terry, Tetrahedron Letters, 1962, 921 ; cf. A. V. Robertson, J. E. Francis, and B. Witkop, J . Amer. Chem. Soc., 1962, 84, 1709. K. Gewald, 2. Chem., 1961, 1, 349. 5 9 C. L. Dickinson, W. J. Middleton, and V. A. Engelhardt, J. Org. Chem., 1962, 27, 2470. 6 O R. Huisgen, H. Stangl, H. J. Sturm, and H. Wagenhofer, Angew. Chem., 1962, 74, 31. 61 S. Gronowitz, A.-B. Hornfeldt, B. Gestblom, and R. A. Hoffman, Arkiw Kenai, 1962, 18, 133.
324
ORGANIC CHEMISTRY
dihydropyrrole (22), oxidation of which with manganese dioxide provides a simple synthesis of maleimide.62 The pyrolysis of several alkylpyrroles
(20)
NH2 (21)
(22)
has been investigated ;63 1-n-butylpyrrole at about 500 O yields 2-n-butylpyrrole which equilibrates with the 3-is0rner.~~ cyclisation of (2-pyrrylThe thio)acetic acid by polyphosphoric acid to compound (24) is believed 6 5 to proceed through the cation (23), and a similar rearrangement occurs in the thiophen series.66 The dithiocyanatopyrrole thought f i s t to be the 3,4derivative 6 7 is in fact the 2 , 5 - i ~ o m e r . ~ ~ 2-Diazopyrroles, obtained from the parent pyrroles with buffered nitrous acid,68are more reactive and less stable than their 3-isomers. The hydrazide (25) with sodium ethoxide and an
(25)
excess of hydrazine gave 2,3,5-trimethylpyrrole in 45% yield.69 Pyrrole-2carboxylic acid and p-dimethylaminobenzaldehydein 1 : 1 ratio in hydrochloric acid yield compound (26), but in 2 : 1 ratio give the more complex derivative (27) which is also the product from N-acetylneuraminic acid and Me ,N
HOZC
aL
Qp
Ehrlich's reagent. ' 0 2,5-Dihydro-3,4-dimethyl-2-oxopyrrole, structure of the which has been proved by spectral measurements, has a reactive methylene group at position 5 and gives 2-ethoxy-3,4-dimethylpyrrole with ethyl sulphate. 71 1-Methylpyrroleand dimethyl acetylenedicarboxylate give 72 the indoles (29) and (31). An initial Diels-Alder reaction could lead to the system (28), which then combines with a second mol. of the ester as indicated, yielding
P. de Mayo and S. T. Reid, Chern. and Ind., 1962, 1576. J. M. Patterson and P. Drenchko, J . Org. Chem., 1962, 2'9, 1650; J. M. Patterson, J. Brasch, and P. Drenchko, ibid., p. 1652. 6 4 I. A. Jacobson and H. B. Jensen, J . P h p . Chem., 1962, 66, 1245. 6 5 S. Gronowitz, A.-B. Hornfeldt, B. Gestblom, and R. A. Hoffman, Arkiw Kemi, 1962, 18, 151. 6 6 S. Gronowitz and P. Moses, Acta Chem. S a n d . , 1962, 16, 155. 6 7 Ann. Reports, 1961, 58, 264. 6 8 J. M. Tedder and B. Webster, J., 1962, 1638. 6 9 E. Baltazzi, Compt. rend., 1962, 254, 702. 'OL. R. Morgan and R. Schunior, J . Org. Chem., 1962, 27, 3696. 71 H. Plieninger, H. Bauer, and A. R. Katritzky, Annalen, 1962, 654, 165. 7 2 R. M. Acheson and J. M. Vernon, J., 1962, 1148.
6a
63
325
the product (29); alternative combination across the 6,7-positions (cf. 28) and subsequent dehydrogenation account for the second product (31), which was degraded to methyl l-methylindole-6-carboxylate.Pyrolysis of the product (29) gave a mixture of trimethyl 1-methylindole-2,3,4-tricarboxylate and the dihydroindole (32).73 This is the f i s t recorded 1,2-shift of an ester group and may occur through the zwitterion (30). The dihydroindole (29) with hot dimethyl acetylenedicarboxylate gave methyl prehnitate and tri72 methyl 1-methylpyrrole-2,3,4-tricarboxylate.
4-Methyleneproline OCCUTS in the seeds of Eriobotrya japonim. 74 Prodigiosin (33) has been synthesised.75 Coporphyrins, formed from monopyrroles with acid, are random mixtures 76 contrary to previous claims. Reductions of porphyrins go through three distinct stages leading to hexahydro-derivatives.77 The y - and 6methine-bridge hydrogen atoms of the chlorins are remarkably susceptible to electrophilic attack 78 and the &methine hydrogen of chlorophyll a is exchanged in methanol.79
IndoZes. Refluxing cis- and trans-2-nitrostilbeiie with triethyl phosphite yields 2-phenylindole,go and similar cyclisations of o-nitrophenyl derivatives have given carbazole, phenazine, and benzocinnoline. The radical (34) may be an intermediary, and its formation in the cyclisation of Z-azidobiphenyls to carbazoles accounts well for kinetic data. 81 a-Chloro-aadiphenylacetanilide and sodium hydride gives 2,2-diphenylindoxyl, 3,3diphenyloxindole, and a trace of 1,3-diphenylo~indole,8~ instead of a lactam
73
74 75
76
77
78 79
R. M. Acheson and J. M. Vernon, Proc. Chem. SOC., 1962, 277. D. 0. Gray and L. Fowden, Nature, 1962, 193, 1285. H. Rapoport and K. G. Holden, J. Amer. Chent. SOC.,1962, 84, 635. I. T. Kay, Proc. Nut. Acad. Sci. U . S . A . , 1962, 48, 901. D. Mauzerall, J. Amer. Chem. Soc., 1962, 84, 2437. R. B. Woodward and V. Skaric, J. A.mer. Chem. SOC., 1961, 83, 4676. J. J. Katz, M. R. Thomas, and H. H. Strain, J. Amer. Chem. SOC., 1962, 84, J. I. G. Cadogan and M. Cameron-Wood, Proc. Chem. SOC.,1962, 361. P. A. S. Smith and J. H. Hall, J. Amer. Chent. SOC., 1962, 84, 480. J. C. Sheehan and J. W. Frankenfeld, J. Amer. Chem. SOC., 1961, 83, 4792.
3587.
81
82
326
ORGANIC CHEMISTRY
claimed earlier. Nuclear magnetic resonance and ultraviolet absorption spectral studies 83 suggest that indoles generally accept a proton at position 3. A new route to 5- and 7-substituted indoles follows from the discovery 84
0 3 S O 3 N a .
AC
Q$HC'z
(36)
(3 5)
(37)
that indole adds sodium hydrogen sulphite across the 2,3-positions, and treatment with acetic anhydride subsequently gives the product (35). Electrophilic substitution now occurs at position 5 or 7 and alkaline hydrolysis of the product yields the substituted indole. 2,3-Dimethylindole with chloroform and base gives a mixture of the quinoline (36) and the 3H-indole (37) which must be formed by different mechanisms as their ratio varies with the strength of the base used.85 A general reaction of certain types of indole has been recognisedYss leading to substitution in a 2-side chain.
OJ
I
H
CHR'R''
+x'-$
CHR'R" R
QJ3R
/
;tR1'
3,3-Dimethyl-2-phenyl- and 2,3-dimethyl-3-phenyl-3H-indole form an -7 : 3 equilibrium mixture in polyphosphoric acid at; 150", but below this temperature no appreciable rearrangement occurs. Indolmycin (38) is an antibiotic from Streptomyces albus, of a new struc-
Me-N
Me
oTi
H
83
(38)
7;k
:erNH .i0
H (39)
R. L. Hinman and E. .B. Whipple, J . Amer. Chem. SOC.,1962, 84, 2534. J. Thesing, G . Semler, and G. Mohr, Chem. Ber., 1962, 95, 2205. 8 6 C. W. Rees and C. E. Smithen. Chem. and I;nd.. 1962, 1022. 86 I. Taylor, Proc. Chem. Soc.; 1962, 247. F. J. Evans, G. G. Lyle, J. Watkins, and R. E. Lyle, J. Org. Chem., 1962, 27, 1553.
w.
ACHESON
327
tural type.88 Echinulin (39) is obtained from moulds of the AspergiZZzLs glaucus group and the racemic form has been synthesised.*S Its relation a to 4 4 3-methylbut-2-enyl)tryptophan, precursor of the ergo$ and clavin alkaloids,g0is of interest. Great progress has been made with elucidation of the structure of betanin, the red-beet pigment. The aglucone, betanidin, with alkali in the absence of oxygen gave a mixture of 4-methylpyridine-2,6-dicarboxylic acid, 2,3dihydro-5,6-dihy&oxyindole-2-carboxylic acid, and formic acid, which account for all the carbon atoms of the original molecule. Betanidin trimethyl ester hydrochloride gave on acetylation the optically active ester (40) which cannot be reconverted into betanidin and is of an isomeric structural type. I n a nuclear magnetic resonance study all the protons of compound (40) and its cation have been accounted for. The nuclear magnetic resonance spectra of the betanidin derivatives examined are poorly resolved but show the presence of a dihydropyridine ring and structures (41) and (42) are offered as a basis for discussion of b e t a n i d i ~ ~ . ~ ~
S
Me
IY
H02C( N ))COzH
Indolizines accept a proton at position 3 in accord with recent L.C.A.O. calculations.92 Indolizine-1-carboxylic acid is readily decarboxylated.93 Furam. The complete structure of furan has been deduced from its microwave spectrum,g* and its nuclear magnetic resonance spectrum has been fully worked o ~ t . 9The ketone (43)has been detected as an inter~ mediate in the acid conversion of hexoses into fur an^.^^ co-Diazoacetophenone and diphenylketen, in a reaction first examined by Staudinger, by give the dihydrofuranone (44).97 The oxidation of esters (45) selenium dioxide to dihydrofuranones (46) a key stage in the first total synthesis of is digitoxigenin.98 Some 3-hydroxyfurans appear to exist predominantly as
8g
s s M . S. von Wittenau and H. Els, J . Amer. Chern. Soc., 1961, 83, 4678. G. Casnati, A. Quilico, and A. Ricca, Gazzetta, 1962, 92,!129, and preceding
papers. 9 0 H. Plieninger, R. Fischer, and V. Liede, Angew. Chem., 1962, 74, 430. 91 H. Wyler and A. 5. Dreiding, Helv. Chim. Acta, 1962, 45, 638; T. J. Mabry, H. Wyler, G. Sassu, M. Mercier, I. Parikh, and A. S. Dreiding, {bid., p. 640. 9 2 M. Fraser, A. Melera, B. B. Molloy, and D. H. Reid, J., 1962, 3288. 93 D. R. Bragg and D. G. Wibberley, J., 1962, 2627. g 4 B. Bak, D. Christensen, W. B. Dixon, L. Hansen-Nygaard, J. R. Andersen, and M. Schottlander, J . Mol. Spectroscopy, 1962, 9, 124. 9 5 G . S. Reddy and J. H. Goldstein, J . Amer. Chern. SOC., 1962, 84, 583. 9 6 E. F. L. J. b e t , Chem. and Ind., 1962, 262. O 7 W. Reid and H. Mengler, Annalen, 1962, 651, 54. g * N. Danielli, Y. Mazur, and F. Sondheimer, J . Amer. Chem. Xoc., 1962, 84, 875.
328
ORGANIC CHEMISTRY
the k e t o - t a u t ~ m e r s . ~ ~ are stable towards acids and being vinylogous They esters do not form normal semicarbazones, etc.
(43)
(44)
(45)
(46)
?he benzophenone-photosensitisedaddition of furan to dimethylmaleic anhydride yields loo cyclobutane (47), and furan rather unexpectedly gives a quinMichael-type adducts (e.g., 48) with 2-acetyl- and 2-alkoxycarbonylones.lol 3,4-Dicyano- and tetracyano-furan have been synthesised and their reactions investigated.lO2 2-Acylfurans on azeotropic distillation with
secondary amines, benzene, and acetic acid yield crude enamines (49),which on direct distillation isomerise to hydroxyanilines (5O).lo3 The formation of 3-lithiofuran from 3-iodofuran and butyl-lithium at -70" offers a new route t o 3-substituted furans. lo4 Chlorination of tetrahydrofuran at -30 O gives 2-chloro- and subsequently 2,5-dichloro-tetrahydrofuran 5 a t room ;lo temperature the 2-chlorofuran loses hydrogen chloride and adds chlorine, forming 2,3-dichlorotetrahydrofuran. Further work l o 6 on a metabolite obtained from several Actinomyces strains has shown that it is the tetralactone (51) of racemic nonactic acid. Condensed ficrans. Racemic griseofulvin (52) has been obtained lo' in a
- 4
P o
(5 3)
C. H. Eugster, K. Allner, and R. E. Rosenkranz, Chimia (Switz.), 1961, 15, 516. G. 0. Schenck, W. Hartmann, S.-P. Mannsfeld, W. Metmer, and C. H. Krauch, Chem. Ber., 1962, 95, 1642. l o l C. H. Eugster and R. Good, Chimia, 1962, 16, 343, and earlier papers. lo2C. D. Weis, J . Org. Chem., 1962, 27, 3693, 3520, 3514. l o 3 L . Birkofer and G. Daum, Chem. Ber., 1962, 95, 183. lo4 . Gronowitz and G. Sorlin, Acta Chem. Scand., 1961, 15, 1419. S lo5 M. Kratochvil and J. Hort, Coll. Czech. Chem. Comm., 1962, 27, 52; H. Gross, Chem. Ber., 1962, 95, 83. lo6 J. Dominguez, J. D. Dunitz, H. Gerlach, and V. Prelog, Helv. Chim. Acta, 1962, 45, 129. lo' G. Stork and M. Tomasz, J . Amer. Chem. Soc., 1962, 84, 310.
99
loo
329
remarkable manner from 7 - chloro-4,6-&methoxycoumaran-3- one and met hoxyethynyl prop-l-enyl ketone in presence of potassium t-butoxide. Structure (53) is now favoured for sterigmatocystin.lo* Pisatin (54) is obtained from garden peas inoculated with a fungus, and a partial synthesis of
"eo%o>
0 ' 0
%r O
/
(54)
(5 5)
RI
racemic pisatin from pterocarpin has been carried Two new corn. pounds (-J-)-neotenone (55; R = OMe, R' = H) and (5)-dolichone (55; R-R' = CH202)have been isolated from Neoratanenia pseudopachyrrhixus. 110 A revised structure (56) for cyanomaclurin is proposed on nuclear magnetic resonance evidence.ll1 The second pyrethrum synergist, sesangolin, obtained from Sesamum angolense oil, is denoted by formula (57).l12
(56)
Thiophens. The structure of thiophen has been deduced unambiguously from microwave data and it is concluded that the sulphur atom is a far less efficient electron-trap than is the oxygen atom of furan.l13 A variety of butadiynes with hydrogen sulphide and weak alkali cyclise to thiophens at 20-80", yields being good except in the case of thiophen itself (20%). Substituents examined include alkyl, aryl, carboxyl, and arylethynyl, and it is suggested that thiophens present in plants are formed in this way.114 New examples of plant thiophens include compounds (58) and (59).l15
(se) (5 9) (60) The initial attack of phenyl radicals on thiophen occurs 116 mostly at position 2. Vacuum-pyrolysis of 3,4-bisacetoxymethyltetrahydrothiophen
E. Bullock, J. C. Roberts, and J. G. Underwood, J., 1962, 4179. A. J. Birch, B. Moore, S. K. Mukerjee, and C. W. L. Bevan, Tetrahedron Letters, 1962, 673; D. D. Perrin and D. R. Perrin, J . Amer. Chem. Soc., 1962, 84, 1922, and earlier papers. 110 L. Crombie and D. A. Whiting, Tetrahedron Letters, 1962, 801. ll1 G. Chakravarty and T. R. Seshadri, Tetrahedron Letters, 1962, 787. 112 W. A. Jones, M. Beroza, and E. D. Becker, J. Org. Chem., 1962, 27, 3232. 113 B. Bak, D. Christensen, L. Hansen-Nygaard, and J. Rastrup-Andersen,J. MoZ. Spectroscopy, 1961, 7, 58. 11* K. E. Schulte, J. Reisch, and L. Homer, Chem. Bey., 1962, 95, 1943. 115 F. Bohlmann, H. Bornowski, and H. Schonowsky, Chem. Be?., 1962, 95, 1733. 116 J. Degani, M. Pallotti, and A. Tundo, Ann. Chim. (Italy), 1961, 51, 434.
l08
log
330
ORGANIC CHEMISTRY
yields 3,4-dimethylthiophen with small amounts of the dimethylene compound (60). 117 Passing the toluene-p-sulphonatesof several 2-thienyl ketone oximes down an alumina column caused Beckmann rearrangement to the thiophen-2-carboxyamides.This method 118may have general application as it avoids the strong acids normally used to catalyse this rearrangement. 3-Thienyl-lithium 119 is stable only at -70". The first optically active 3,3'-bithienyl has been prepared.120 The biotin derivative (61)is involved in the carboxylation of 18-methylcrotonyl-coenzyme A.121 Benzo[c]thiophen (62) has been obtained 122 by vapour-phase dehydrogenation of its lY3-dihydro-derivative. It resembles naphthalene in odour and a t -30" under nitrogen is stable for only one day. With maleic anhydride it gives the expected adduct which with sodium hydroxide yields naphthalene-2,3-dicarboxylic acid. 5-Acetamido-3-bromobenzo[b]thiophen with an excess of nitric acid in acetic acid unexpectedly gave the nitrodiazo-oxide (63).Z 3 l
Axoles. The resonance energies of pyrazole and imidazole, calculated from combustion data, are 29.3 and 14.2 kcal. rnole-1, respectively.124 Molecular-orbital calculations have been applied to these compounds.125 Pyrazoles have been obtained from sydnones and acetylenes,l26 and from dienes with sodium hydrazide in hydrazine.127 Cyclisation of #I-amino-oximeswith NN'dicyclohexylcarbodi-imide constitutes a new synthesis of pyrazolines.128 The fist authentic 1-pyrazoline (64) isolated was obtained from styrene and phenyldiazomethane; it gave the 2-pyrazoline with dilute acid.129 Diazomethane adds to methyl tiglate and angelate, yielding methyl 3,4-dimethyl-l-pyrazoline-3-carboxylates of corresponding geometry, and the configurations were retained in photochemical, but not thermal; decomposition of these pyrazolines to cyclopropanes.lS0 The formation of some of the original esters in the photodecomE. J. Fetter, Diss. Abs., 1962, 22, 2985. J. C. Craig and A. R. Naik, J. Amer. Chem. Soc., 1962, 84, 3410. ll9 P. Moses and 8. Gronowitz, Arkiv Kemi, 1962, 18, 119. 1 2 0 S. Gronowitz and H. Frostling, Acta Chem. Scand., 1962, 16, 1127. 121 J. Knappe, K. Biederbick, and W. Briimmer, Angew. Chem., 1962, 74, 432. 122 R. Mayer, H. Kleinert, S. Richter, and K. Gewald, Angew. Chem., 1962, 74, 118. 123 I. Brown, M. Martin-Smith, S. T. Reid, C. C. Scott, and G. A. Sim, Chem. and Ind., 1962, 982. 12*A. F. Bedford, P. B. Edmondson, and C. T. Mortimer, J., 1962, 2927. 125 H. Harnano and 13. F. Hameka, Tetrahedron, 1962, 18, 985. 12* R. Huisgen, R. Grashey, H. Gotthardt, and R. Schmidt, Angew. Chem., 1962, 74, 29. 12' T. Kauffmann, H. Muller, and C. Kosel, Angew. Chem., 1962, 74, 248. 12* A. Hassner and M. J. Michelson, J. Org. Chem., 1962, 27, 298. 12D G. C. Overberger and J.-P. Anselme, J. Amer. Chem. SOC., 1962, 84, 869. 1962, 84, 3736. lSo T. V. van Auken and K. L. Reinhart, J. Amer. Chem. SOC.,
117
118
ACHESON : HETEROCYCLIC C O M P O U N D S
331
positions is noteworthy as the elements of diazomethane must be eliminated. The pyrazole ring can be enlarged by ~ 0 d a m i d e . l ~ ~ Indazolin-3-one is oxidised by lead tetra-acetate in acetonitrile to a deep red solution containing 3-indazol-one (65) which has been suggested as an intermediate in the von Richter reaction. Addition of ethanolic potassium cyanide caused instant loss of nitrogen with the formation of benzoic acid; the tricyclic adduct (66) was formed with butadiene.132
Aldehydes and ketones can be regenerated in good yield from hydrazones possessing one N-H atom by treatment with acetylacetone and weak acid, a 3,5-dimethylpyrazole being formed.133 The products from 2-ethyl-l-methylimidazole and dimethyl acetylenedicarboxylate have been investigated. 134 5-Amino-l-~-~-ribofuranosylimidazole-4-carboxylic acid 5-O-phosphate, which is involved in purine biosynthesis, has been synthesised unambiguously.135 4-Phenylurazole and t-butyl hypochlorite below -50 O give 4-phenyl1,2,4-triazoIine-3,5-dione which is an extremely powerful dieneophile 136 and adds to butadiene instantly at -78. Five-membered rings containing different heteroatoms. Annuloline (67), from seedling roots of Lolium multijlorum, is the first oxazole found in Nature and its structure has been proved by degradation and synthesis.137 Enzymic hydrolysis of the glucoside (68) from Sisymbrium austriacum Jacq. yields the oxazolidine (69),138a Beckmann type of rearrangement having taken place.
0
SO?
A theoretical study suggests that isoxazole is scarcely a,romatic. 139 The radical halogenation of isoxazoles has been studied. 140 4-Amino-3,5-dimethylisoxazole with nitrous acid and potassium dicyanocuprate gave
131 A. M. Simonov, B. K. Martsokha, and F . T. Pozharski, Zhur. obshchei Khim., 1962, 32, 2388. 1 3 2 E. F. Ullman and E. A. Bartkus, Chem. and Ind., 1962, 93. 134 W. Reid and G. Miihle, Annalen, 1962, 656, 119. l s 4 A . Crabtree and A. W. Johnson, J . , 1962, 1510. 136 G. Shaw and D. V. Wilson, J., 1962, 2937. 136 R. C. Cookson, S. S . H. Gilani, and I. D. R. Stevens, Tetrahedron Letters, 1962, 615. 13 R. S. Karimoto, B. Axelrod, J. Wolinsky, and E . D. Schall, Tetrahedron Letters, 1962, 83. l s e A . Kjaer and B. Christensen, Acta Chem. Scand., 1962, 16, 71. 1 3 0 G. D. Re, J., 1962, 3324. 140 N. K. Kochetkov, S. D. Sokolov, and N. M. Vagurtova, Zhur. obshchei Khim., 1962, 32, 325.
332
ORGANIC CHEMISTRY
4-acetyl-&methyl-1- (3,5-dimethylisoxazol-4-y1)1,2,3-triazole. 141 Further studies of isoxazolone tautomerism have been made. 142 1,2,4-Oxadiazoles and 1,3,4-dioxazoles have been synthesised by 1,3dipolar additions. 143 X-Ray crystallographic studies on 5-chlorobenzofuroxan 144 prove that the bicyclic structure (as in 70) is correct. Nuclear magnetic resonance studies have confirmed this result,145and also show that the half-life of the tautomers of (70)is w. sec. at 45". Nitration of 5-methylbenzofuroxan gives the 4-nitro-derivative; heating caused isomerism through ring-opening and -closing in the alternative direction to the less hindered 7-methyl-4nitrobenzofuroxan, which was also obtained by nitrating 7-methylbenzofur0xan.1~6 4-Chloro-2-nitro-l-nitrosobenzene 4-chloro-l-nitro-%nitroand sobenzene are not identical, so the benzofurazan 1,3-dioxide structure is excluded although oxygen transfer through this type of intermediate is likely when the compounds equilibrate to a 1 : 1 mixture in about 10 min. in refluxingtetrachloroethane. 147 o-Nitronitrosobenzeneforms the expected adduct (71) with butadiene.14*
Isothiazole has been synthesised by passing propene, sulphur dioxide, and ammonia at 200" over alumina,149 and from ammonia and the acraldehyde derivative (72; R = S-SO,Na or SCN) which were obtained from propynal and, respectively, sodium thiosulphate or thiocyanic acid.150 Isoselenazole (73),a colourless liquid with a pyridine-like odour, was obtained from the aldehyde (72; R = SeCN) and ammonia.151 3-Bromopropynesand thiourea yield 2-amino-4-methylthiazoles through the intermediary of methylene derivatives (74).152 Partial acid hydrolysis 153 of the antibiotic thiostrepton gives the thiazole (75), but other conditions lead to 4-acetyl-8-hydroxyquinoline-2-carboxylic 154 Bacitracin F is acid.
141A. J. Boulton and A. R. Katritzky, J., 1962, 2083. A. R. Katritzky, S. Oksne and, i part, A. J. Boulton, Tetrahedron, 1962, 18, n 777. 143 R. Huisgen, W. Mack, and E. Anneser, Tetrahedron Letters, 1961, 587; R. Huisgen and W. Mack, ibid., p. 583. 144 D. Britton and W. E. Noland, J. Org. Chem., 1962, 27, 3218. 145 G. Englert, 2. Elektrochem., 1961, 65, 854; P. Diehl, H. A. Christ, and F. B. Mallory, Helv. Chim. Acta, 1962, 45, 504. 146 A. J. Boulton and A. R. Katritzky, Proc. Chem. Soc., 1962, 257. 1' F. B. Mallory, K. E. Schueller, and C. S. Wood, J. Org. Chem., 1961, 26, 3312. 4 148 J. Hamer and R. E. Bernard, Rec. Trav. chim., 1962, 81, 734. 149F. Hubenett, F. H. Flock, and H. Hofmann, Angew. Chem., 1962, 74, 653. 150 F. Wille, L. Capeller, and A. Steiner, Angew. Chem., 1962, 74, 467. 151 F. Wille, A. Ascherl, G . Kaupp, and L. Capeller, Angew. Chem., 1962, 74, 753. 152Y. Yura, Chem. and Pharm. Bull. (Japan), 1962, 10, 372, 376, 382. 153 M. Bodanszky, J. Alicino, C. A. Birkhimer, and N.J. Williams, J. Amer. Chem. SOC., 1962, 84, 2003. 1 5 4 C. N. C. Drey, G. W. Kenner, H. D. Law, R. C. Sheppard, M. Bodanszky, J. Frid, N. J. Williams, and-J. T. Sheehan, J . Amer. Chem. SOC., 1961, 83, 3906.
142
ACHESON
: HETEROCYCLIC CONPOUNDS
333
acid. a polypeptide derived from 2-a-methylbutyroylthiazole-4-carboxylic 155 " Hector's bases " are now regarded as 1,2,4-thiadiazolidines (76).lS6 The four nitro-l,2,3-benzothiadiazoles have been oriented.157 lY2,3-Benzothiadiazole with carbon disulphide at 200" gives 1,3-ben~odithiole-2-thione.~~~
MisceZZaneous. The 1,2-dithiolinium cation 159 is of the aromatic type according to theoretical calculations.160 The 1,3-dithioliniurn cation ( 7 7 ) has now been obtained by the oxidation of 1,3-dithiole-2-thionewith peracetic acid.161 Violet dyes (e.g., 78)are obtained from both of these aromatic cations with dimethylaniline.162
Ph
(77)
(78)
Ph
(79)
1,2,5-Triphenylphosphole , obtained from 1,4-diphenylbutadiene and (79) phenylphosphonouschloride, is stable in air and gives an oxide with hydrogen peroxide. With dimethyl acetylenedicarboxylate dimethyl 3,6-diphenylphthalate is formed.163 The heat of combustion of pentaphenylphosphole has been measured.164 Silacyclopentadieneforms a 1 : 1 adducti with hexachlorocyclopentadiene, and with potassium gives potassium silacyclopentadienide (80) which closely resembles potassium cyclopentadienidein absorption spectrum.l G 5 Derivatives of 1,2-~elenathiole have been made. 166 Triphenylaluminium and diphenylacetylene at 200 O give compound (82) ,
W. Konigsberg and L. C. Craig, J . Org. Chem., 1962, 27, 934. F. Kurzer and P. M. Sanderson, Chem. and Ind., 1962, 1681; C. P. Joshua, V. K. Verma, and K. S. Suresh, Tetrahedron Letters, 1961, 663. 1 ' E. R. Ward, W. H. Poesche, P. Higgins, and D. D. Heard, J., 1962, 2375. 5 168 R. Huisgen and V. Weberndorfer, Experientia, 1961, 17, 566. 15g Ann. Reports, 1961, 58, 270. l60 G. Bergson, Arkiv Kemi, 1962, 19, 181. 161 E. Klingsberg, J . Amer. Chem. Soc., 1962, 84, 3410. 162 E. Klingsberg and A. M. Schreiber, J . Amer. Chern. SOC., 1962, 84, 2941. 163 I. G. M. Campbell, R. C. Cookson, and M. B. Hocking, Chern. and Ind., 1962, 359. 164 A. F. Bedford, D. M. Heinekey, I. T. Millar, and C. T. Mortimer, J., 1962, 2932. 165 R. A. Benkeser, R. F. Grossman, and G. M. Stanton, J . Amer. Chern. SOC., 1961, 83, 5029. 166 G. Bergson, Arkiv Kerni, 1962, 19, 75.
155
156
334
ORGANIC CHEMISTRY
the first derivative of aluminole (81). It is decomposed by water to benzene and triphenylethylene, and iodine cleaves it to the triphenylethylene (83) and iodobenzene.167 Six-membered Rings and Condensed Derivatives.-Pyridines and piperidines. The geometry of pyridine hydrochloride has been ascertained from an X-ray study.168 The nuclear magnetic resonance spectra of many pyridines 169show that the coupling constants are affected little by substituents excepting strong electron-donors at position 3. The effect of Co-y-radiation on aqueous pyridine has been examined.170 Malonyl chloride is being used as a building block for various heterocyclic systems 171 and with monosubstituted acetonitriles at room temperature yields pyridines (84) while at 100" an alternative reaction leads to more complex products (85). fhHydroxyglutaronitriles and glutacononitriles
n
L V
CH2 (COCI),
I""
cyclise with anhydrous hydrogen bromide or iodide to 2-amino-6-halogeno~ y r i d i n e s . 1Aromatic aldehydes condense with piperidine acetate, giving ~~ lY3,5-tribenzylpyridinium acetates. The reaction is thought to proceed as
CH2Ph-PhH2C
CH2Ph
CH Ph
CH2Ph
CH2Ph
CH2Ph
CHzPh r?
indicated in the annexed formulae.173 The pyridine ring opens in its reaction with benzoyl chloride and methyl cyanoacetate,l7*yielding an imine (86); products from indole and benzoyl chloride with pYwidine,quinoline, isoquinoline, and phenanthridine are of type (87).17*
Many pyridines are hydrogenated to the corresponding piperidines in acetic acid over 10% palladium-charcoal at 70-80"/3-4 atm.; no reducJ. J. Eisch and W. C. Kaska, J . Amer. Chem. Soc., 1962, 84, 1501. C. Rerat, Acta Cryst., 1962, 15, 427. W. Briigel, 2. Elektrochem., 1962, 66, 159. 170 S. A. Safarov, Kinetika i Kataliz, 1962, 3, 449. 171 S. J. Davis, J. A. Elvidge, and A. B. Foster, J., 1962, 3639, and earlier papers. 172 F. Johnson, J. P. Panella, A. A. Carlson, and D. H. Hunneman, J. Org. Chem., 1962, 27, 2473. R. J. Poirier, R . D. Morin, A. M. M c K h , and A. E. Bearse, J. Org. C h m . , 1961, 26, 4275; E. P. Burrows, R. F. Hutton, and W. D. Burrows, ibid., 1962, 27, 316. 17* H. von Dobeneck and W. Goltzsche, Chem. Ber., 1962, 95, 1484.
167
168
335
tion occurs a t room temperature and benzene rings are unaffected.176 Kinetic studies show that the cation rather than the free base is reduced in On the hydrogenation of pyridine in aqueous acid over p 1 a t i n ~ m . l ~ ~ a rhodium-carbon catalyst some pyridines give piperidines at 55-60' in the absence of acids.177 Michael additions to pyridinium salts have been reviewed.178 l-Vinylpyridinium perchlorate does not add bromine but is hydrogenated to l-ethylpiperidine; it; is stable to acid but polymerises with base.179 Pyridinium fluoroborates are alkylated on the nitrogen atom by diazomethane. lSo The reduction of 1-substituted pyridinium salts with sodium borohydride yields first the 1,2-dihydropyridine (88), as is the case with l-phenylpyridinium salts in the presence of base,lS1and this then adds a proton (or a deuteron) a t position 3 or 5, yielding an enamine (89) which is further reduced to the tetrahydropyridine (90).l S 2 Electroreduction of 1-alkylpyridinium salts give
stable free radicals.183 Diethyl 1,4-&hydro-2,6-&- and -1,2,6-tri-methylpyridine-3,5-dicarboxylatereduce the double bond of l-phenyl-4,4,4-trifluorobut-2-en-l-oneby direct transfer of the 4-hydrogen atom to position 3 of the ketone.184 Chromic acid oxidises 2-amino-5-hydroxyhexanoic acid to 2,3,4,5-tetrahydropyridine-2-carboxylic acid.185 Piperidine reacts surprisingly fast with chloroform to give 1-dichloromethylpiperidine which, if water is present, is hydrolysed t o 1-formylpiperidine. lS6 The plausibility of 2,3- and 3,4-pyridyne as reaction intermediates is suggested by the formation of quinoline 1' and isoquinoline lS8 8 from lithium amalgam with 2- and 4-chloro-3-bromopyridine, respectively, and by other reactions.lS9 Some methylpyridines and condensed derivatives give substantial amounts of acetic acid on Kuhn-Roth oxidation.190 The phototropism of
175 G. N. Walker, J . Org. Chem., 1962, 27, 2966. 1'6R. M. Skomoroski and A. Schriesheim, J . Phys. Chem., 1961, 65, 1340. 177 M. Freifelder, R. M. Robinson, and G. R. Stone, J. Org. Chem., 1962, 27, 284. 1 7 8 F. Krohnke, W. Zecher, D. Dreschler, K. PAeghar, K. E. Schnalke, and W. Weis, Angew. Chem., 1962, 74, 811. 1 7 9 I. N. Duling and C. C. Price, J . Amer. Chem. SOC., 1962, S4, 578. 1 8 0 R. Daniels and C. G. Kormendy, J . Org. Chern., 1962, 27, 1860. 181M. Saunders and E. H. Gold, J. Org. Chem., 1962, 27, 1439. 182 R. E. Lyle, D. A. Nelson, and P. S. Anderson, Tetrahedron Letters, 1962, 553. lE3 W. M. Schwarz, E. M. Kosower, and I. Shain, J . Arner. Chem. SOC., 1961, 83, 3164. l 8 4 B. E. Norcross, P. E. Klinedinst, and F. H. Westheimer, J . Arner. Chem. Soc., 1962, 84, 797. 186 K. Hasse, P. Homann, K. Schiihrer, and A. Wieland, Annalen, 1962, 653, 114. A. Pierce and M. M. Joullie, J . Org. Chem., 1962, 27, 2220. 187 R. J. Martens and H. J. den Hertog, Tetrahedron Letters, 1962, 643. lS8 T. Kauffmann and F.-P. Boettcher, Chem. Ber., 1962, 95, 949. M. J. Pieterse and H. J. den Hertog, Rec. Trav. chim., 1961, 80, 1376; T. Kauffmann and F.-P. Boettcher, Chem. Ber., 1962, 95, 1528. loo B. Franck and J. Knoke, Chem. Ber., 1962, 95, 579.
336
ORGANIC CHEMISTRY
2-(2,4-dinitrobenzyl)pyridine and similar compounds including 2,4-dinitrotoluene which are colourless in the dark but become blue on exposure to light has been investigated lgl by flash-photolytic techniques and it appears that the colourless form (91) is isomerised to the blue tautomer (92).
R-H2C
NO2
RO C, ,-N = . ( J
O2N
H+-O-N
( 9 1)
J.
(92)
An acid-catalysed hydrogen exchange at position 3 of some pyridines has been dem0nstrated.l Bromine and ammonium thiocyanate introduce the thiocyanate group a t positions 3 and 5 of 2,6-diaminopyridine,lg3instead of forming thiazolopyridines as believed earlier. Magnesium viologen (93), which is formed from pyridine, magnesium, and iodine, introduces magnesium into porphyrins, chlorins, and phthalocyanin. l9* Strict second-order kinetics are followed in reactions of 2-chloropyridines with anilines.195 The chlorine atoms of 2-, 3-, and 4-chloropyridine l-oxide are displaced by aqueous sodium sulphite, giving the corresponding sodium sulphonates, while no replacement of chlorine occurs with 3-chloropyridine
and only partial replacement with the 2- and the 4-~hloro-isomer.~g~ Bromination of pyridine l-oxide in fuming sulphuric acid effects 3-substitution but with bromine and silver sulphate in 90% sulphuric acid a mixture of the 2- and 4-bromopyridine l-oxide is formed;lg7this is attributed to the formation of a species (94) only in the fuming acid. Pyridine l -oxide is mercurated mostly a t positions 2 and 6.1g8 2- and 4-Methylpyridine l-oxide react with acetic anhydride by different mechanisms.199 It is concluded from experiments involving oxygen-labelled acetic anhydride that a species (95) is formed from the second oxide and is attacked by an acetate anion, leading to 3-acetoxy-4-methylpyridine and 4-acetox ymethylpyridine. 2o0 Pyridin e l-oxides have been deoxygenated by triethyl phosphite,201sulphur,202 and ferrous oxalate. 203 Pyridine-2-selenoneresembles 2-pyridone in structure. 204
Ig1 G.Wettermark, J. Amer. Chem. SOC., 1962,84,3658; J. A. Sousta and J. Winstein, J . Org. Chem., 1962, 27, 3155. lg2 A. R. Katritzky and B. J. Ridgewell, Proc. Chem. Soc., 1962, 114. 1 g 3 J. A. Baker and S. A. Hill, J., 1962, 3464. lg4 P. E. Wei, A. H. Corwin, and R. Arellano, J. Org. Chem., 1962, 27, 3344. l g 5 N . B. Chapman, D. K. Chaudhury, and J. Shorter, J., 1962, 1975. l g 6 R . F. Evans and H. C. Brown, J . Org. Chern., 1962, 27, 1329. 1' M. van Ammers, H. J. den Hertog, and B. Haase, Tetrahedron, 1962, 18, 227. 9 l9* M. van Ammers and H. J. den Hertog, Rec. Traw. chim., 1962, 81, 124. l g 9 Ann. Reports, 1961, 58, 272. 2 0 0 S. Oae, T. Kitao, and 1 Kitaoka, J. Amer. Chem. SOC., ' . 1962, 84, 3362. 2 0 1 T. R. Emerson and C. W. Rees, J., 1962, 1917, 1923. 2 0 2 D. I. Relyea, P. 0. Tawney, and A. R. Williams, J. Org. Chem., 1962, 27, 477. 203 R. A. Abramovitch and K. A. H. Adams, Canad. J. Chem., 1961, 39, 2134. 2 0 4 H . G. Mautner, S.-H. Chu, and C. M. Lee, J. Org. Chem., 1962, 27, 3671.
337
The photodimer of l-methyl-2-pyridonewhich was formulated last year as a cyclobutane derivative has in fact structure (96) and may be formed by dimerisation of a 1,$-diradical.205 1,3-Additions of acetylenic esters to pyridine l-imide and condensed derivatives have been described.206 The dihydropyridine (97) with cold potassium cyanide rearranges to the azepine (98) which with alkali yields the pyrrole (99) and ethyl acrylate. Hot cyanide will also convert the dihydropyridine (97) into the pyrrole (99).207 New synbheses of pyridoxine are based on the Diels-Alder addition of 5-ethoxy-4-methyloxazole dienes, to
or<:6z: Et
MeN EtOzC Me
(96)
H CN E tMe 2 C D O COlEt H Me (98) EtO2C Men:;
Me
(97)
(99)
including methyl maleate which gives an epoxide (100). Ethanolic hydrochloric acid then gives the pyridine (101) which is converted into pyridoxine by normal routes.208
COzMe EtOf$CO2Ne Me
(100)
\
? 9
~
EtO fi:L2Me Me
\
HN
NH Me Me
(102)
(101)
Condensed pyridines. 5H-l-Pyrindine contains 0.1% of the 1H-tautomer. 209 The results of variable electronegativity self-consistent field calculations for quinoline and isoquinoline confirm those of the Huckel method and account for electrophilic substitution a t position 3 of quinoline through an addition-elimination sequence involving a 1,4-dihydroquinoline.210Heat ing the equimolar complex from quinoline and bromine, which can be approximately formulated as l-bromoquinolinium bromide, gives S-bromoquinoline.211 Quinoline-2- and -4-aldehyde and potassium cyanide give the corresponding quinoloins but reduction to the diols occurs in situ.212
2 0 5 G. Slomp, F. A. MacKellar, and L. A. Paquette, J . Amer. Chem. Soc., 1961, 83, 4472; W. A. Ayer, R. Hayatsu, P. de Mayo, S. T. Reid, and J. B. Stothers, Tetrahedron Letters, 1961, 648; E. C. Taylor, R. 0. Kan, and W. W. Paudler, J . Amer. Chem. SOC., 1961, 83, 4484. 206 R. Huisgen, R. Grashey, and R. Krischke, Tetrahedron Letters, 1962, 387. 2 0 7 E. Bullock, B. Gregory, A. W. Johnson, P. J. Brignell, U. Eisner, and H. Williams, Proc. Chem. SOC., 1962, 122. 2 0 8 E. E. Harris, R. A. Firestone, K. P h t e r , R . R. Boettcher, F. J. Cross, R. B. Currie, M. Monaco, E. R. Peterson, and W. Reuter, J . Org. Chem., 1962, 27, 2705. 2 0 9 C. B. Reese, J . Amer. Chem. SOC., 1962, 84, 3979. 210 R . D. Brown, B. A. W. Coller, and R. D. Harcourt, Austral. J . Chem., 1961, 14, 643. 211 J. J. Eisch, J . Org. Chem., 1962, 27, 1318. 212 H. Andrews, S. Skidmore, and H. Suschitzky, J., 1962, 3827.
338
ORGANIC CHEMISTRY
Reactions of bromine and nucleophilic reagents with 1-cyanoquinolinium salts have been examined.213 The reduction of quinaldine under different conditions gives the " dimeric " derivatives (102) 214 and (103).215 Reissert compounds are readily obtained in a water-methylene dichloride system.21a Hofmann degradation of 1,2,3,4-tetrahydro-l-methylquinoline usually regenerates this quinoline but up to 48% of NN-dimethyl-oallylaniline can be obtained.217 o-Anilinobenzamide gives biphenyl and phenanthridone with potassamide. 218
Isoquinoline 219 and phenanthridine 220 with 2 mol. of dimethyl acetylenedicarboxylate yield quinolizines, and in the latter case a new type of adducb (104) is also formed. Pyridine-2-aldehyde diethyl acetal and chloroacetone give a quaternary salt which cyclises with hydrobromic acid, giving a new synthesis of 3-hydroxyquinolizinium bromide.221 The stereochemistry of quinolizidine and its alkyl derivatives has been investigated in detai1.222 Axines. The resonance energies of pyridazine, pyrimidine, and pyrazine, calculated from combustion data,223are 12-3, 8-0 and, 8-1 kcal. moled1, respectively. Oxidation of 2,3,4,5-tetrahydro-3,5-dioxopyridazine yields 3,6-dihydro-3,6-dioxopyridazine (pyridazine-3,6-dione)which is an extraordinarily reactive d i e n e ~ p h i l e . The~nitration and spectra of benzo[c]~~ cinnolines have been investigated.225 New syntheses of pyrimidines from friazines 2 2 6 and from dicyandiamideswith ketones,22' and a novel rearrangement of 4-amino-5-nitrosopyrimidines 2-amino-4-cyanoto lY3,5-triazines 228
213
214
215
M. D. Johnson and J. H. Ridd, J., 1962, 291, and earlier papers. H. Dunathan, I. W. Elliott, and P. Yates, Tetrahedron Letters, 1961, 781. I. W. Elliott, E. S. McCaskill, M. S. Robertson, and C. H. Kirksey, Tetrahedron
Letters, 1962, 291. 216 F. D. Popp, W. Blount, and A. Soto, Chem. and Ind., 1962, 1022. 217 D. A. Archer and H. Booth, Chem. and I n d . , 1962, 894. 218 G. W. Kenner, M. J. T. Robinson, C. 3 .B. Tylor, and B. R . Webster, J., 1962, 1 1756. 219 R. M. Acheson and F. Hole, J . , 1962, 748. 2 2 0 R. M. Acheson and A. 0. Plunkett, J., 1962, 3758. 221 E. Schraufstatter, Angew. Chem., 1962, 74, 874. 2 2 2 T. M. Moynehan, K. Schofield, R. A. Y. Jones, and A. R. Katritzky, J., 1962, 2637: S. V. Kessar, Experientia, 1962, 18, 56; K. Winterfeld, W. Hiking, and P. Schmialek, Arch. Phurm., 1962, 295, 24. 2 2 3 T. Tjebbes, Acta Chem. Scund., 1962, 16, 916. 2 2 4 T. J. Kealey, J . Amer. Chem. Xoc., 1962, 84, 966; R. A. Clement, J . Org. Chem., 1962, 27, 1115. 2 2 s J. W. Barton and M. A. Cockett, J., 1962, 2454; J. F. Corbett, P. F. Holt, A. N. Hughes, and M. Vickery, J., 1962, 1812. 2 2 6 F. C. Schaefer, K. R. Huffman, and G. A. Peters, J . Org. Chem., 1962, 27, 548. 2 2 7 E. J. Modest, S. Chatterjee, and H. Kangur, J . Org. Chem., 1962, 27, 2708. 2 2 8 E. C. Taylor and C. W. Jefford, J . Amer. Chem. SOC., 1962, 84, 3744.
ACHESON
339
have been described. 6-Chloro-2-chloromethyl-4-phenylquinazoline -oxide 3 expands to the diazepine (105) with alkali.229 New naturally occurringpyrimidines include the plant amino-acidwillardine (106),z3Oand the antibiotics bacimethrin (107) 23l and amicetin (a complex 4-amino-2-hydroxypyrimidine derivative) .232 Saxifolin, the paralytic shell-fish poison, has been degraded 233 to the pyrrolidinopyrimidine derivative (108).
0
The adducts of 2,3-dimethylquinoxaline with maleic anhydride and l-phenylmaleimide have structures (109) and (110), respectively, but the so-called benzoquinone adduct is only a molecular complex of the quinoxaline with quino1.234 Oxidation of 2,2'-diaminodiphenylamineby nitrobenzene ~ields l-aminophena~ine.2~5 Toxoflavine (lll),the cause of the mass fatal food-poisonings in Japan, has been synthesised.236
0 ; ; d N P h
:yy-Ij
N
O
fQH
6")cH;o
(I 1 3 j
N CH*NH2
0
(119)
(Ill)
(112) OH
Electron densities of the purine molecule calculated by a semi-empirical self-consistent molecular orbital method differ from those reported earlier and account for the correct order of electrophilic and nucleophilic substitution. z37 Pteridine undergoes a reversible acid- and base-catalysed hydration yielding the alcohol (112); in water alone an equilibrium is attained. The cation of this hydrate slowly gives the pyrazine (113) which cyclises on neutralisation. Many examples are now known of this type of covalent hydration.238 Oxygen and sulphur heterocycles. 4H-Pyran (115) is a colourless liquid which quickly becomes brown in air; it has been obtained by vapour-phase 239 pyrolysis of 2-acetoxy-3,4-dihydro-ZfI-pyran and from glutardialdehyde
8 2 9 S. C. Bell, T. S. Sulkowski, C. Gochrnan, and S. J. Childress, J . Org. Chem., 1962, 27, 562. 230 J. H. Dewar and G. Shaw, J., 1962, 583. S 3 l H. C. Koppel, R. H. Springer, R. I .Robins, and C. C. Cheng, J . Org. Chem., ( 1962, 27, 3614. 232 C. L. Stevens, K. Nagarajan, and T. H. Haskell, J . Org. Chem., 1962, 27, 2991. 233 W. Schuett and H. Rapoport, J . Amer. Chem. Soc., 1962, 84, 2266. 2 3 4 C. W. Bird and G. W. Cheeseman, J . , 1962, 3037. 2 3 5 G . Gaertner, A. Gray, and F. G. Holliman, Tetrahedron, 1962, 18, 1105. 236 D. Daves, R. K. Robins, and C. C. Cheng, J . Amer. Chem. Soc., 1962, 84, 1724. 237 R . L. Miller and P. G . Lykos, Tetrahedron Letters, 1962, 493. 238 Y . Inoue and D. D. Perrin, J., 1962, 2600, and earlier papers. 239 S. Masamure and N. T. Castellucci, J . Amer. Chem. Soc., 1962, 84, 2452.
340
0 R G A N IC C H E M I Y T R Y
by conversion into the ether (114) with hydrogen chloride in methylenedichloride, followed by treatment with dimethylaniline.240 4H-Thiopyran mas prepared similarly.240
Ph
The 2-pyrone ring is opened by lithium aluminium hydride 2 4 1 and by sodium ~yanide.2~2 2,3-Epoxy-2,3-diphenylindan-l-one (1 16) is thermochromic, yielding the red compound (117) when heated; a dimer of compound ( 1 17) and an adduct with dimethyl acetylenedicarboxylate are also described.2 4 3 The photoisomerisation of coumarin, sensitised by benzophenone, yields the cis-head-to-head adduct (118), but a mixture of similar trans-head-to-head and head-to-tail adducts is obtained in the absence of ~ensitiser.~~~ Pyrylium borofluorides and triphenylphosphine methide yield benzene derivatives. 24 A chromatographic and oxidative procedure for the identification of anthocyanins has been worked It depends partially on the fact that the 3-glycosides7but not 5- or 7-glycosides, are oxidised by hydrogen peroxide. The structures of the leucoanthocyanidins of the Acacia species and the configurations of optically active flavonoids have been reviewed. 2 4
MP
MeHN
nu"
2 4 0 J. Strating, J. H. Keijer, E. Holenaar, and L. Brandsma, Angew. Chem., 1962, 74, 465. 241 L. E. Morgan, jun., J . Org. Chem., 1962, 27, 343; G. Vogel, Chem. and Ind.,
1962, 268. 2 4 2 G. Vogel, Chern. and Ind., 1962, 1829. 2 4 3 E. F. Ullman and J. E. Milks, J . Anzer. Chem. SOC., 1962, 84, 1315. 2 4 4 G. 0. Schenck, I. Wilucki, and C. H. Krauch, Chem. Ber., 1962, 95, 1409. 2 4 5 G. Markl, Angew. Chern., 1962, 74, 696. 2 4 8 B. V. Chandler and K. A. Harper, Austral. J . Chem., 1962, 15, 114. 2 4 7 J. W. Clark-Lewis, Rev. Pure Appl. Chem. (Australia), 1962, 12, 32, 97.
341
Digicitrin, 3,5-dihydroxy-4,5,6,7,8-pentamethoxyflavone, been isolated has from leaves of the red foxglove and is the richest natural oxygen-containing flavone so far described.248 Isoartocarpin (119) is the first flavone found in Nature 249 possessing a dimethylallyl (4-methylbut-2-enyl) ether group. The structures of flavasperone (120), a metabolite of Aspergillus ~ z i g e r , 2 ~ 0 actonospectacin (121), the broad-spectrum antibiotic from Actinomyces ~pectabiZis,~~l xylindein (122), the green pigment of the fungus ChZuroand ciboria a e r g ~ i n o s a have~been ascertained. ,~~ Thialen (123) has been obtained as an unstable blue-violet oil by the vapour-phase dehydrogenation of its hexahydro- and octahydro-derivative. z53 2,4,G-Triphenylthiapyrylium perchlorate with Grignard reagents
gives deep purple solutions of thia(rv)benzenes (e.g., 124) which rearrange a t room temperature giving, in the case mentioned, a mixture of the 2- and 4-methyl-2,4,G-triphenylthi0pyran;Z~~ l-thia(rv)naphClialenederivatives be55 have ~imilarly.~ lY3,5-Trithians appear to possess a rapidly oscillating chair structure with the axial and equatorial positions indistinguishable.256 Miscellaneous.-The cis-azide (125) cyclised, when heated, to give the azepine (126).257 Treatment of the perchlorates (127; X = 0 or S) with diazomethane gave the corresponding dibenzepins ( 128).258 The main product from 10-methylacridinium perchlorate was 9-iodomethyl-10-methylacridan, but this with silver perchlorate yielded the azepine (128 ;X = m e ) .
a a
(204-
P7
RNL,,NR
(129)
(127)
(128)
Several azacycloheptadiene (azatropone) derivatives have been made ;259 they do not react with 2,4-dinitrophenylhydrazine. Products from ethyleneW. Meier and A. Fiirst, Helv. Chim. Acta, 1962, 45, 232. K. G. Dave, S. A. TeIang, and K. Venkataraman, Tetrahedron Letters, 1962, 9. 2 5 0 B. W. Bycroft, T. A. Dobson, and J. C. Roberts, J., 1962, 40. 251 H. Hoebema, A. D. Argoudelis, and P. F. Wiley, J . Amer. Chem. Soc., 1962, 84, 3212. 2 5 2 G. M. Blackburn, A. H. Neilson, and Lord Todd, Proc. Chem. SOC., 1962, 327. 2 5 3 R. Meyer, J. Franke, V. Horhk, I. Hanker, and It. Zahradnik, Tetrahedron Letters, 1961, 289. 2 5 4 G. Suld and C. C. Price, J . Amer. Chem. Soc., 1962, 84, 2090, 2094. 2 5 5 A. Luttringhaus, N. Englehard, and A. Kolb, Annalen, 1962, 654, 189. 2 5 6 E. Campaigne, N. F. Chamberlain, and B. E. Edwards, J . Org. Chem., 1962, 27, 135. 2 5 7 E. Vogel and R. Erb, Angew. Chem., 1962, 74, 76. 2 5 8 H. W. Whitlock, Tetrahedron Letters, 1961, 593. 2 5 9 R. B. Johns and K. R. Markham, J., 1962,3712; W. Paterson and G. R. Proctor, J., 1962, 3468.
248 249
342
ORGANIC CHEMISTRY
diamines and formaldehyde are 1,4,6,9-tetra-azatricyclo[4,4,1 ,l]dodecanes.260 Primary amines, hydrogen sulphide, and formaldehyde yield compounds of type (129), and not thiazetidines as earlier supposed.261 The first borazarene (131) has been synthesised by the desulphurisation of the compound (130),and other boron heterocycles have been made.262
The compound (131)has an aromatic type of ultraviolet absorption spectrum and shows considerable stability to acids and bases. The boron derivative (132) is a powerful di~retic.2~3 Silanthrene 264 (133) and phosphanthrene derivatives (134) have been
Ph Aik
Et
(133)
(134)
made. The latter molecule is folded about the P-P axis, and two compounds corresponding to the alternative two positions for the ethyl groups have been isolated.265 o-Dibromobenzenewith alkali-metal amalgams gives mixtures 266 containing the mercury heterocycles (135) and (136).
R. M. A.
9. ALKALOIDS
Biogenesk-Feeding experiments on Datura stramonium with both DL[2-14C]ornithine and [l-WIacetate have .led to unsymmetrically labelled hyoscyamine, with the activity restricted to one of the two ring-carbon atoms a to the nitrogen.l, 2 As the biogenesis from [l-14C]acetateprobably proceeds through [1,5-14C,]ornithineit is probable that the two experiments gave the alkaloid labelled on opposite sides of the ring.1 Lupanine and
G . Volpp, Chem. Ber., 1962, 95, 1492. N. J. Leonard, K. Conrow, and A. E. Yethon, J. Org. Chem., 1962, 27, 2019. 2 6 2 M. J. S. Dewar and P. A. Marr, J . Amer. Chem. SOC., 1962, 84, 3782, and earlier papers. 2 6 3 H. L. Yale, F. H. Bergeim, F. A. Sowinski, J. Bernstein, and J. Fried, J. Amer. Chem. SOC.,1962, 84, 689. 264H. Gilman, E. A. Zuech, and W. Steudel, J . Org. Chem., 1962, 27, 1836. 265M. Davis and F. G . Mann, Chem. and Ind., 1962, 1639. s 6 6 G . Wittig, E. Hahn, and W. Tochtermann, Chem. Ber., 1962, 95, 431. E. Leete, J . Amer. Chern. SOC.,1962, 84, 55. A. A. Bothner-By, R. S. Schutz, R . F. Dawson, and M. L. Salt, J. Amer. Chem. SOC.,1962, 84, 52.
260
261
BENTLEY: ALKALOIDS
343
f0Ziw.3
hydroxylupanine have been obtained from [1,5-14C,]cadaverinein L.angwtiBattersbys work on the biogenesis of papaverine and the morphine alkaloids has been published in detail,4, and berberine and narcotine have also been shown to arise from ~~-[Z-l~C]tyrosine labelling only a t with C-1 and (3-3; the last-named base has been obtained also from [l-14C]norlaudanosoline;6 tyrosine has also been shown to be incorporated unequally into the two halves of hydrastine but or-dopamine is incorporated only into the isoquinoline part of this alkaloid.* These results agree with the generally accepted hypotheses of the biogenesis of the isoquinoline alkaloids. Norbelladine and its monomethyl ether labelled at more than one position have been found to be incorporated intact into galanthamine, galanthine, and hzemanthine, and the methylenedioxy-group of the last-named base has been found to be derived directly from the methoxyl group of norbelladine methyl ether rather than by demetjhylation and reaction with formaldehyde. The incorporation of tyrosine into one part of the molecules of haemanthamine and tazettine has also been reported.1 Mevalonic acid has been proved to act as a precursor of lysergic acid,ll but not of the Senecio alkaloids, in which retronecic acid has been shown to be derived from four acetate units. l2 Some interesting theories of the biogenesis of the indole alkaloids have been advanced. Wenkert l 3 postulates their origin from the secopre). phenate-formaldehyde grouping (1 Mannich condensation of this with an oxidation product of glycosylideneanthranilic acid to give an intermediate (2) could lead either to a strychnine (3) or a uleine ( 4 )precursor; the Aspidosperma and Iboga bases are assumed to arise through a variant (5) by a reversed Michael fission of the material (3), whereas if such a fission occurs in the conventional secoprephenate-tryptamine complex a flavopereirine type of structure will be the end-product. Several plant products are now known to be derivatives of secoprephenate,including a number of monoterpenes, and Wenkert considers the possibility that the indole bases are derived by way of monoterpene units from acetic and mevalonic acid, in which case the yohimbine structure would appear a t the very end rather than at; the beginning of the biosynthetic development. Hendrickson and Silva l4 reported condensation of 2-hydroxytryptamine with homoveratraldehyde in a simulated cell medium to give a single base (6), the stereochemistry of which is identical with that of strychnine; this base condenses
H. R. Schutte, E. Nowaki, and C. Schafer, Arch. Pharm., 1962, 295, 20. A. R. Battersby and B. J. T. Harper, J., 1962, 3426. A. R. Battersby, R . Binks, and B. J. T. Harper, J . , 1962, 3534. I. D. Spenser and J. R. Gear, Proc. Chem. SOC., 1962, 228. A. R. Battersby and D. J. McCaldin, Proc. Chem. SOC., 1962, 365. I. D. Spenser and J. R. Gear, J . Org. Chem., 1962, 27, 1059. D. H. R. Barton, G. W. Kirby, J. B. Taylor, and G. M. Thomas, Proc. Chem. SOC., 1962, 179; D. H. R. Barton, G. W. Kirby, and J. B. Taylor, ibid., p. 340; W. C. Wildman, H. M. Fales, R. J. Highet, S. W. Breuer, and A. R. Battersby, ibid., p. 180. l o W. C. Wildman, H. M. Fales, and A. R. Battersby, J . Amer. Chem. SOC., 1962, 84, 2997; P. W. Jeffs, Proc. Chern. SOC.,1962, 80. l1 R. M. Baxter, S. I. Kandel, and A. Okamy, J . Amer. Chem. SOC., 1962, 84,2997. l2 C. Hughes and F. L. Warren, J., 1962, 34. l3 E. Wenkert, J . Amer. Chem. SOC., 1962, 84, 98. l4 J. B. Hendrickson and R. A. Silva, J . Am,er. Chem. SOC., 1962, 84, 643.
344
ORGANIC CHEMISTRY
with formaldehyde to give compound (7), very similar to the Mitragyna bases. On the basis of these reactions plausible routes to the Strychnos and Mitragynu alkaloids through the shikimic acid condensation product (8) are postulated, in which the reactions spontaneously take the correct steric course without the intervention of an enzyme system.l4
(7)
OMe
Pyridine Group.-The alkaloid anaferine, from Withunia sornnijera Dunal, has been shown to be 1,3-&-2-piperidylacetone, and a synthesis of the base (prepared from 2-picolylhas been achieved through 1,3-di-2-pyridylacetone lithium and ethyl chloroformate). The configuration of carpaine (with l5 all the substituents of the piperidine ring cis 16), anabasine, and anatabine l7 have been determined, and the isomers of skytanthine have been prepared from the isomers of nepetalic acid (9), the natural alkaloid being shown in this way to have the configuration (10).l8 A total synthesis of nupharidine
Me
NMe
(1)
l5
Me
(2)
A. Rotter, J. M. Bobbitt, and A. E. Schwarting, Chem. and Ind., 1962, 654. M. Tichgi and J. Sicher, Tetrahedron Letters, 1962, 511. l7 R. Lukes, A. Arojan, J. Kovar, and K. Blaha, Coll. Czech. Chem. Comm., 1962, 27, 751. E. J. Eisenbraun, A. Bright, and H. H. Appel, Claenz. and Ind., 1962, 1242; I. Kawasaki, Nippon Kagaku Sasshi, 1960, 81, 154.
l6
BENTLEY: ALKALOIDS
345
(11) has been completed ; condensation of ethyl y(5-methyl-2-piperidyl)valerate with 3-furoyl chloride and cyclisation of the product gave 3-dehydrodeoxynupharidine, which on reduction, resolution, and N-oxidation gave the natural alkaloid,19 the absolute stereochemistry of which has also been determined.2O A novel hydrogen transfer reaction has been observed with tropine and benzoyl chloride, which in base give benzaldehyde and tropinone; the reaction does not occur with y-tropine or N-benzoylnortropine, and intramolecular hydrogen transfer in the quaternary salt (12) is the suggested mechanism.21 Lupin Alkaloids.-A partial synthesis of angustifoline (13) has been achieved from tetrahydrocytisine by N-chlorination, dehydrochlorination, and reaction of the resulting imine with allylmagnesium bromide; the same sequence of reactions starting with cytisine, followed by condensation of the ally1 compound with formaldehyde, afforded epibaptifoline.Z2 13-HydroxyluDanine has been dehydrogenated to the derivative (14) and this on reducA
0
tion and then oxidation with nitric acid and with alkaline ferricyanide gave thermopsine (15); an analogous lactam was obtained by omission of the reduction stage.22 Retamine is probably an axial 12- or 14-hydroxysparteine, since it is not identical with 7-, 8-, or 9-hydroxysparteine, but apparently contains a five-membered hydrogen-bond system between nitrogen and oxygen.23 The preparation of the ab-unsaturated lactam ( -) -sophocarpine from matrine by chlorination, reduction, and dehydrochlorination indicates that this alkaloid has the structure (16); sophoramine, which is obtained by the dehydrogenation of sophocarpine, is the abydunsaturated la~tarn.~4 Pmolizidine Group.-An 1l-stage stereospecific synthesis of (-+)-refronecine (21), through the intermediates (17)-(20), has been achieved;25 retronecine is the basic unit in indicine, a new hepatotoxic alkaloid from Heliotropium indicium, in which it is esterified on the primary hydroxyl group by (-)-trachelanthic acid, which forms a racemate with the (+)-acid from supinine.26 Renardine has been found to be the senecic ester of
l9 M. Kotake, I. Kawasaki, S. Matsutani, S. Kusumoto, and T. Kaneko, Bull. Chem. SOC. Japan, 1962, 35, 698. 2 o I. Kawasaki and T. Kaneko, Bull. Chem. SOC. Japan, 1962, 35, 697, 1335. 21 B. J. Calvert and J. D. Hobson, Proc. Chem. SOC., 1962, 19. 2 2 F. Bohlmann, E. Winterfeldt, H. Overwien, and H. Pagel, Chem. Ber., 1962, 95, 944. 2 s F . Bohlmann, E. Winterfeldt, D. Schumann, U. Zarnack, and P. Wandrey, Chem. Ber., 1962, 95, 2365. 2 4 S. Okuda, H. Kamata, K. Tsuda, and I. Mukaroski, Chem. and Ind., 1962, 1326. 2 5 T. A. Geissman and A. C. Waiss, J. Org. Chem., 1962, 27, 139. 2 6 A. R. Mattocks, R. Schoental, H. C. Crowley, and C. C. J. Culvenor, J., 1961,
5400.
346
otonecine, the necine obtained from ~ t o s e n i n e . ~ ~ (&)-Isoretronecanol28 (22) and trachelanthamidine 29 have been synthesised, the former from pyrrolizidin-3-one through the cyanohydrin, a-hydroxy-acid, ap-unsaturated ester, and ethyl pyrrolizidine-3-carboxylate. ( -)-l-Blethylenepyrrolizidine has been found in Crotolaria damarensis Engl., and the partially racemised base has also been found in C. ~ n a g y r o i d e s . ~ ~total synthesis of the raceA mate has been rep0rted.~1
HO
-c-
CO2Et
4--
0-co
CH2.OH
EtO2CYcoiEt
EtO2C+N
C02Et
(22)
(17)
- &cI:2:t
(18)
1, OEt-, then H,-Pt.
2, -H,O,
then LiAlH,.
Quinoline Group.-Condensation of N-methyl-o-anisidine with diethyl but -2-enylmalonafe gives 3-but -2'-enyl-4-hydroxy-8-mef hoxy-2- quinolone, and this has been hydrated with diborane and alkaline hydrogen peroxide to a product that on methyla,tion with diazomethane gives (&)-lunacrine (23), which has been cyclised to ( & ) - l ~ n a r i n e .Reduction of haplohyll~~
Me0
Me0
HO Me
Me0 A O M e
. .-
'OMe
*'AOMe
27
81, 3815.
A. V. Danilova, N. I. Karetskaya, and L. M. Utkin, Zhur. obshchei Khirn., 1961,
2 8 N. K. Kochetkov, A. M. Likhosherstov, and A. S. Lebedeva, Zhur. obshchei Khim., 1961, 31, 3461. 2 9 0. (jlervinka, K. Pelz, and I. Jirkovskjr, Coll. Czech. Chem. Comm., 1961, 26, 3116. ao C. C. J. Culvenor and L. W. Smith, Austral. J. Chern., 1962, 15, 318. 3 1 A . M. Likhosherstov, A. M. Kritsyn, and N. K. Kochetkov, Zhur. obshchei Khim., 1962, 32, 2377. 3aE. A. Clarke and M. F. Grundon, Chem. and Ind., 1962, 556.
B E N T L E Y : ALKALOIDS
347
idine, followed by oxidation, gives propionic acid but no y-fagarinic acid or aldehyde can be obtained from the base, and it is accordingly concluded that the second methoxyl group in this alkaloid is not a t position 8, the probable structure for the base being (25).33 Fabianine, from Fabiana irnbricah, has been found t o be 5,6,7,8-tetrahydro-9-(l-hydroxy-l-methylethyl)2,5-dimethylquinoline, and a second base from the same source is 5,6,7,8tetrahydro-2,5-dimethylquinoline ; presumably these bases are related to the terpenes.34 Isoquinoline Group.--Syntheses of (&)-~alycotamine,~5(-J-)-isocorydine,36 and tetrahydropalmatrubine 37 have been accomplished by general methods previously reported. The asymmetric carbon atom in (-)-armepavine has been shown to have the (R)-configuration by the correlation of ( +)-armepavine with (+)-la~danidine.3~ Absolute configurations in the aporphine series have been determined by optical rotatory dispersion studies,39 and the relation between configuration and ring substituents has been determined.40 All four possible stereoisomers of 2-dehydroemetine have been prepared by cyclisation of the 3,4-dimethoxyphenethylamide from the acid (26), the (-)-form of which has the stereochemistry An alternative route to the same bases has been explored, namely, cyclisation of the unsymmetrical base (27 ;R = CH,Ph) to compound (28 ;R = CH,Ph), followed by dehydration, thioketal formation, and reduction.42 Use of the symmetrical base (27; R = CH,*CH,Ac) provided a stereospecific route to (-J-)-emetine and (&)-isometine, by way of the base (29; R = CH,*CH,*CHMe*OH), which on Oppenauer oxidation affords the desired bases by a retro-Michael fission of the intermediate ketone (29;
33
T. T. Shakirov, G. P. Sidyakin, and S. Yu. Yunusov, Doklady Akad. Nauk
Uz. S.S.R., 1961, No. 8, 47.

3&
35
0. E. Edwards and N. F. E h o r e , Canad. J . Chem., 1962, 40, 256. A. Chatterjee and N. Adityachaudhury, J . Org. Chem., 1962, 27, 309. A. M. Kuck and B. Frydman, J . Org. Chem., 1961, 26, 5253. N. L. Dutta and C. K. Bradsher, J. Org. Chem., 1962, 27, 2213. 3 8 C. Ferrari and V. Deulofeu, Tetrahedron, 1962, 18, 419. 3g.C.Djerassi, K. Mislow, and M. Shamma, Experientia, 1962, 18, 53. 40M. Shamma, Experientia, 1962, 18, 64. 41 A. Brossi and F. Burkhardt, Experientia, 1962, 18, 211.
4B
J. H. Chapman, P. G. Holton, A. C. Ritchie, T. Walker, G. B. Webb, and E. Whiting, J., 1962, 2471; D. E. Clark, P. G. Holton, R. F. K. Meredith, A. C. Ritchie, T. Walker, and K. D. E. Whiting, J., 1962, 2479.
I .D. (
348
ORGANIC CHEMISTRY
= CH,*CH,AC).~~ number of other synthetic N-substituted deriva-4 tives of emetine, isometine, and dehydroemetine have been prepared by this general method.44 A new synthesis of C-bisnor-rubremetinium salts from 3,4-dihydro-l-methylisoquinoline has been developed, involving a Knorrtype pyrrole synthesis and cyclisation of the 3,4-dimethylphenethylamide of the resulting pyrrole-1-carboxylic acid.45 I n the bisbenzylisoquinoline group structures have been assigned to sepeerine 46 and hernande~ine,~ a synthesis of (&)-dihydro-N-methyland menisarine by conventional methods has been reported.48 Pilocereine, previously believed to be a bisbenzylisoquinoline, has proved to be a Orimeric alkaloid, and the constitution (30), most likely on biogenetic grounds, has been conflrmed by the isolation of 7-hydroxy-1-isobutyl-6-methoxy-Z-methylisoquinoline, together with previously known fission fragments, on lithiumammonia fission of the base. Piloceredine is also trimeric and is probably a stereoisomer of pilocereine. The formerly accepted structure for pilocereine has been assigned to isopilocereine, a dimeric fission fragment of the alkaloid.49 I n the morphine group the bromination of ketones has been carefully studied and found to involve reaction at position 7 rather than at position 5 as previously assumed. The mechanism of the 4,5-oxide ring closure in the bromo-ketones has been studied and the first pentacyclic structure with it trans-fusion of rings B and C, trans-1-bromodihydrocodeinone, been prehas pared by base-catalysed cyclisation of trans-1,7-dibromodihydroe;thebainone. It should be possible now to prepare a number of interesting derivatives of the trans-series, including trans-morphine itself. 5O Amaryllidaceae Group.-Ismine, a new base from a number of Ismene species, has been proved by oxidation to N-methylmethylenedioxyphenanthridone to be 6-o-dimethylamin0phenylpiperonaldehyde.~1 stereoA specific synthesis of DL-p-lycoranehas been reported, 5 2 and an unambiguous synthesis of isoanhydrofalcatine lactam, in which the methoxyl group is a t position 11 and which is not identical with falcatine lactam, indicates that falcatine must be 8-methoxycaranine,53 the position of the methoxy-group being the same as that recently demonstrated in the powellane Two new bases of this series, (+)-epibuphanisine and coranicine, have been isolated from Ammocharis coranica.55 The action of mineral acids on galanthamine has been studied in detail: the first product of the reaction is
D. E. Clark, R. F. K. Meredith, A. C. Ritchie, and T. Walker, J., 1962, 2490. A. C. Ritchie, D. R. Preston, T. Walker, and K. D. E. Whiting, J., 1962, 3385. 4 5 Y. Ban and M. Terashima, Tetrahedron Letters, 1961, 796. 4 6 M. F. Grundon and J. E. B. McGarvey, J., 1962, 2077. 4 7 J. Padillrc and J. Herran, Tetrahedron, 1962, 18, 427. 4 8 M. Tomita, S. Ueda, and A. Teraoka, Tetrahedron Letters, 1962, 635. 4 9 C. Djerassi, H. W. Brewer, C. Clarke, and L. J. Durham, J . Arner. Chem. Xoc., 1962, 84, 3210. 5 0 M. Gates and M. S. Shepard, J. Amer. Chem., SOC., 1962, 84, 4125. 5 1 R. J. Highet, J. Org. Chem., 1961, 26, 4767. 5 2 J. A. Joule and L. J. Loeffler, Chem. and Ind., 1962, 1573. 5 F Benington and R. D. Morin, J . Org. Chem., 1962, 27, 142. 3 . 5 4 H. A. Lloyd, E. A. Kielar, R . J. Highet, S. Uyeo, H. M. Fales, and W. C. Wildman, J . Org. Chem., 1962, 27, 373. 5 5 H. Hauth and D. Stadacher, Helv. Chirn. Acta, 1962, 45, 1307.
43 44
BENTLEY
ALKALOIDS
349
4,5-epoxy-2-hydroxy-6-O-methylapogalanthamine, which is transformed into apogalanthamine 6-methyl ether before h a 1 production of apogalanthamine ; apogalanthamine 6-methyl ether is identical with the alkaloid nivalidine from Galanthus nivalis. 5t3 Indole Group.-This group of alkaloids has received special attention during the year, and it has been possible to assign structures to numerous bases as a result of the very rapid accumulation of knowledge of the mode of fission of these alkaloids in the mass spectrometer. A new study of the bases of Peganum harmah has revealed a new base (harmidine) distinct from the previously reported harmaline. Harmidine has the composition C,,H,,N,O and is reducible to tetrahydroharmine and convertible into harmidol, C,,H,,N,O; harmaline was not found in the plant.57 Harman and norharman have been isolated from cigarette smoke.m Dehydrogenation of tuberostemmonine affords tuberostemmonan (31),the structure of which was determined by ozonolysis and further degradation t o the base (32), which mas then synthesised by reduction of the lactam produced from 5,7-diethyll-tetralone by the Schmidt rea~tion;~g these results support the structure
(33), or the alternative (in which the lactone ring involves the other twocarbon substitutent) previously suggested for the alkaloid.60 Ellipticine has been synthesised by it modified Pommeranz-Fritzsch process from 1,4-dimethylcarbazole-3-aldehydey61 olivacine by dehydroand genation of the product of combined Beckmann transformation and cyclisation of the oxime of l-methyl-2-3-oxobutylcarbazole, the product of itself an eight-stage synthesis.62 Chimonanthine, a base from Chimonanthus fragrans Lindle, on reduction with zinc and acetic acid gives 3-2-methylaminoethylindole, and the NN-dimethyl compound on Hofmann degradation gives the known base (34); the alkaloid must therefore belong to the calycanthine group;e3the structure (35; R = R = H) for the base has been proved by X-ray studies.64 Calycanthidine is the mono-N(a)-methyl derivative (35; R = Me, R = H),65 folicanthine is the bis-N(a)-dimethyl and
L. Bubeva-Ivanova, Chem. Ber., 1962, 95, 1348. S. Siddiqui, Chem. and Ind., 1962, 356. 58E. Poindexter and R. D. Carpenter, Chem. and Ind., 1962, 176. 1. 5 9 T. Shingu, Y. Tsuda, S. Uyeo, Y. Yamato, and H. Harada, Chem. and Ind., 1962, 1191. 6 o M. Gotz, T. Bogri, and A. Gray, Tetrahedron Letters, 1961, 707. 61P. Cranwell and J. E. Saxton, Chem. and Ind., 1962, 45; J . , 1962, 4582. A. 6 2 E. Wenkert and K. G. Dave, J . Arner. Chem. SOC., 1962, 84, 94. 63 H. F. Hodson, B. Robinson, and G. F. Smith, Proc. Chem. SOC.,1961, 465. 6 4 I. J. Grant, T. A. Hamor, J. M. Robertson, and G. A. Sim, Proc. Chem. SOC., 1962, 148. 6 5 J. E. Saxton, W. G . Bardsley, and G. F. Smith, Proc. Chem. SOC., 1962, 148.
56
57
350
O R G A N I C CH E MIST RY
compound (35; = R' = Me).63 A synthesis of calycanine (36) by heating R o-aminoacetophenone and o-nitrophenylpyruvic acid with zinc chloride and decarboxylating the resulting mixture of calycaninecarboxylicacid and the acid (37; R = C0,H) has been recorded; the nitro-compound (37; R = H) is a by-product of the reaction.66
Flavocarpine, a new alkaloid from Pleiocarpa mutica Benth., has been identified as a zwitterion related to fla~opereirine,~~these two ba~es,~7# and 68 sempervirine,6 8 and alstoniline 69 have been synthesised by quaternisation of a suitably substituted 2-chloro-pyridine or -quinoline with 3-2'-bromoethylindole, cyclisation, and dehydrogenation; and flavopereirine has also been synthesised together with tetrahydroflavopereirine by a modification of this general process.70 I n the yohimbine series hexadehydroyohimbane has been synthesised by reduction of 2-(2-3'-indolyl-2-oxoethyl)isoquinoline iodide with lithium aluminium hydride, 71 and the absolute stereochemistry of yohimbine (previously determined 72) has been confirmed by conversion of the alkaloid into dihydrocorynantheane which has already been related to dihydr~cinchonine.~~ previous assignment of a trans-fusion of rings The D and E in tetrahydroalstonine, aricine, reserpinine, and 3-isoreserpi1iney and of a C~S-D/E fusion in ajmalicine, raumitorine, and tetraphylline, has been reversed as a result of a study of the rates of quaternisation of these and of the conversion of tetrahydroalstonine info ajmaliciol and 19-isoajmaliciol by way of 19-corynantheidol, 19-corynantheidone-ZOX,and 19corynantheidone-20/3,the last-named being the more stable of the two epimeric ketones.75 These revised structural assignments have been supported by spectral studies.76 Akuammigine has been shown to be identical with
T. G. 84, 3393. 68Y. 6 9 Y. 7 0 E. 71 D.
66 67
Kobayashi and R. Kikumoto, Tetrahedron, 1962, 18, 813. Buchi, R. E. Manning, and F. A. Hochstein, J. Amer. Chem. SOC.,1962,
Ban and M. Seo, Tetrahedron, 1961, 16, 5 . Ban and M. Seo, J. Org. Chem., 1962, 27, 3380. Wenkert and J. Kilzer, J. Org. Chem., 1962, 27, 2283. R. Liljegren and K. T. Potts, J . Org. Chem., 1962, 27, 377. 72Y. and 0. Yonemitsu, Chem. and Ind., 1961, 948. Ban 73 Y. Ban and 0. Yonemitsu, Tetrahedron Letters, 1962, 181. 74M. Shamma and J. B. Moss, J . Amer. Chem. SOC.,1961, 83, 5038. 7 5 E. Wenkert, B. Wickberg, and C. L. Leicht, J. Amer. Chem. Xoc., 1961, 83, 5037. 7 6 M. Shamma and J. B. Moss, J . Arner. Chern. SOC., 1962, 84, 1739.
BEXTLEY: ALKALOIDS
351
3-isotetrahydroalstonine. Hunterburnine, from Hunteria eburnea Pichon, 75 has by X-ray studies been assigned the structure (38), in which the absolute configuration is based on the uniformity of configuration a t (2-16 in the yohimbine bases ; it occurs with the methochloride of hydrocorynantheol from which base it is theoretically derivable by scission and recyclisation.77
(40)
MeOzChO
The bases of the yohimbine group have been rearranged by treatment with t-butyl hypochlorite and heating of the resulting chloro-compounds with aqueous methanol a t pH 6, and this is a general method for the conversion of indole bases into their oxindole analogues. I n this way, ajmalicine, dihydrocorynantheine, yohimbine, and yohimbane have been converted into pairs of isomeric oxindoles, namely, mitraphylline (40) and isomitraphylline, rhyncophylline and an isomer, yohimbine oxindole A and R, and yohimbane oxindole A and B, respectively. The pairs of isomeric bases doubtless have the partial structures (39a) and (39b).78 Mayumbine has been related in this way to 19-isoakuammigine, and formamosine is the 7-epimer of mayumbine ;79 uncarine-A is the 4,15-epimer of mitraphylline, while isornitraphylline is the 7-epimer; and corynoxine is the 15,20-epimer of rhyncophylline.80 Mossambine has been found t o undergo reactions analogous to those of akuammicine, and a direct comparison of the mass spectra of these to bases has shown mossambine t o be 14-hydroxy-( -)-ak~ammicine.~l Massspectral studies have also shown that echitamidiiie has the akuammicine skeleton with a CHMe*@Hgroup where the latter has :CHMe.82 A new group of bases differing from those of the akuammicine group in the position of the ethylidene group has been discovered; of these, aspidospermatine has been assigned the structure (41; R = R' = H) on the basis of its mass spectrum and the formation of 3-ethylpyridine on distillation with zinc dust. A number of derivatives of nspidospermatine with R = H, Me, or Ac and R' = H or OMe accompany the parent alkaloid in Aspidosperm quebrachoi7
J. D. M. Asher, J. 31. Robertson, G. A. Sim, 11. F. Bartlett, R. Sklar, and
W. I. Taylor, Proc. Chenb. Soc., 1962, 72.

7 8 N. Finch and W. I. Taylor, J . Anter. Chena. SOC., 1962, 84, 1318; J. Shave1 and H. :innes, ibid., p. 1320. * 7 9 E. Wenkert, B. Wicltberg, and C. Leicht, Tetrahedron Letters, 1961, 823. Li0 J. B. Hendrickson, J . Anier. Cheni. SOC., 1962, 84, 650. 81 X. Monseur, R. Goutttrol, J. Le Men, J. M. Wilson, M. Budzikiewicz, and C. Djerassi, Bull. SOC. chinz. France, 1962, 1088. 8 2 C. Djerassi, Y . Pl'akag,zwa, H. Budzikiewicz, J. M. Wilson, J. Le Men, J. Poisson, and M.-M. Janot, Tetrahedron Letters, 1962, 663.
352
ORGANIC CHEMISTRY
blanco. 83 Condylocarpine is an a@-unsaturatedester and can be converted into aspidospermatine by acid and lithium aluminium hydride, and on the basis of these facts and the mass spectrum of its Clemmenssn reduction prostemmadenine contains a duct the alkaloid is given the structure (42);84 hydroxymethyl group, the position of which is revealed by dehydrogenation to the base (43), and is dihydro-a-hydroxymethylcondylocarpine.8~ The co-occurrence of condylocarpine and norff uorocurarine suggests that these two bases have a common precursor.
has The mass spectrum of deoxydihydro-0-methylsnrpagine been found to be almost identical with that of the Wolff-Kishner reduction product of deoxyajmalal from ajmaline, apart from a shift in the mass numbers due to the presence of different substituents, and accordingly sarpagine has been assigned the structure of hydroxynormacusine-B(44; R = H, R' = OH).85 Other alkaloids in this sub-group have been given structures on the basis of their mass spectra its follows:polyneuridine is the 16-epimerof akuammidine (44; = CO,Me, R' = H), and akuammidine is identical with rhazine;B698' R vincamedine has been related to polyneuridine by oxidation with chromic acid and reduction with potassium borohydride, and voachalotine is N methylpolyneuridine.8 8 Vellosiminol and tombozine are identical with normacusine-B (44; R = R' = H), and vellosimine is the corresponding aldehyde.89 Vomeniline (45) has been related to ajrnaline by reduction to N(~)-demethy1-4~-ajmaline 17-O-acetate, and has also been rearranged to perakine (46).90 The absolute configurations of ajmaline and isoajmaline
83
K. Biemann, M. Friedmann-Spiteller, and G. Spiteller, Tetrahedron Letters, 1961,
485.
8 4 A. Sandoval, F. Walls, J. N. Shoolery, H. Budzikiewicz, and C. Djerassi, Tetrahedron Letters, 1962, 409; K. Biemann, A. L. Burlinghame, and D. Stauffacher, Tetrahedron Letters, 1962, 527. 8 5 K. Biemann, J . Amer. Chem. SOC., 1961, 83, 4801. 86 L. D. Antonaccio, N. A. Pereira, B. Gilbert, H. Vorbrueggen, H. Budzikiewicz, 5. M. Wilson, L. J. Durham, and C. Djerassi, J . Amer. Chem. SOC., 1962, 84, 2161. 8' A. Chatterjee, C. R. Ghoshal, and N, Adityachaudhury, Chem. and Ind., 1962, 266. 8 8 M.-M. Janot, J. Le Men, J. Gosset, and J. Levy, Bull. SOC. chim. France, 1962, 1079; Proc. Nat. Acad. S i U.S.A., 1962, 48, 113. c. 89H. Rapoport, and R . E. Moore, J . Org. Chem., 1962, 27, 2981. W. I. Taylor, A. J. Frey, and A. Hofmann, Helv. Chim. Acta, 1962, 45, 611.
BENTLEY: ALKALOIDS
353
have been established by the conversion of the O-toluene-p-sulphonatesi t no ( -)-cisand ( )-trans-2,3-diethyl- ,Z73,4-tetrahydro1 12-methylindolo[ 2,3-a]quinolizinium perchlorate, which were in turn derived, respectively, from corynantheidine and corynantheine, thus establishing the absolute configuration also of the last two bases and, indirectly, of ~ a r p a g i n e . ~ ~ applicaThe tion of mass-spectra in the determination of the structures of alkaloids of the Iboga group has been studied and the structures previously assigned to ibogaine, ibogamine, ibogaline, iboxygaine, and tabernanthine have been confirmed in this way.92 I n the aspidospermine sub-group mass spectra and nuclear magnetic resonance studies have shown that the periwinkle bases vincadifformine93 and vindoline 9 4 have the structures (47) and (48), respectively, and that
tabersonine is 6,7-dehydrovincadifformine.95 Cylindrocarpine, from A . cylindrocarpon Muel1.-Arg., contains both an amide and an ester group, and on hydrolysis affords methanol, cinnamic acid, and cylindrocarpinic acid. Lithium aluminium hydride reduces the base to an alcohol dihydrocylindrocarpol, oxidation of which to the aldehyde followed by Wolff-Kishner reduction gives deacetylaspidospermine. Cylindrocarpine thus must have the structure (49); cylindrocarpidine is the corresponding N-acetyl compound.96 Pyrifolidine is a methyl ether 9 7 of aspidocarpine (50) and is identical with 96 16-methoxy-( )-aspidospermine, and its occurrence with cylindrocarpine [which belongs to the (-)-aspidospermine series] suggests that both bases arise by stereospecific ring closures of the (+)-and the (-)-form of a quebrachamine-like base containing only one asymmetric centre.96 Also related to aspidocarpine are aspidolimine, which is N-deacetyl-N-propionyl-
91 M. F. Bartlett, R. Sklar, W. I. Taylor, E. Schlittler, R. L. S. Amai, P. Beak N. V. Bringi, and E. Wenkert, J . Amer. Chem. SOC., 1962, 84, 622. 9 2 K. Biemann and M. Friedmann-Spiteller, J . Amer. Chem. Soc., 1961, 83, 4805. C. Djerassi, H. Budzikiewicz, J. M. Wilson, J. Gosset, J. Le Men, and 14.-M. Janot, Tetrahedron Letters, 1962, 235. s4 M. Gorman, N. Neuss, and K. Biemann, J . Amer. Chem. SOC., 1962, 84, 1058. 9 5 M. Plat, J. Le Men, M.-M. Janot, J. M. Wilson, H. Budzikiewicz, L. J. Durham, Y. Nakagawa, and C. Djerassi, Tetrahedron Letters, 1962, 271. 96 C. Djerassi, A. P. G . Archer, T. George, B. Gilbert, and L. D. Antonsccio,
Tetrahedron, 1961, 16, 212. 9 7 S. McLean, K. Palmer, and L. Marion, Canad. J . Chem., 1960, 38, 1547.
M
354
ORGANIC CHEMISTRY
aspidocarpine,98 spegazzinidine ( 16-0-demethy1-3-hydroxyaspidocarine), and spegazzinine (16-demethoxy-3-hydroxyaspidocarpine) Dhe structures ,99 of all these bases being determined by mass and nuclear magnetic resonance spectral studies. A series of bases closely related to aspidospermine and aspidocarpine is provided by the alkaloids aspidofractine 100 (51; R = CHO, R = C02Me),refractidine 100 (17-methoxyaspidofractine), kopsinine,lol, l o 2 (51; R = H, R = C02Me), pleiocarpine lo2,lo3 (51; R = R = CO,Me), pleiocarpinine lo2, (51; R = Me, R = C02Me),and kopsine lo5(52), the lo4 structures of which were determined by mass and nuclear magnetic resonance spectral studies and by interconversions within the group. Pyrifoline (51; R = Ac, R = H; 6,17-dimethoxy) and refractidine (51;R = CHO, R = H ; 6-methoxy) have also been shown by mass spectrometry to belong to this general group.lo6 Two bases, vincamine (53)and 11-methoxyvincamine, closely related t o eburnamine, have been discovered and their structures have been elucidated mainly by mass spectra and nuclear magnetic resonance studies. lo y-Akuammigine has been proved to be deoxyakuammine, and both these bases have been shown to contain a carbinolamine ether system closely
n
Me02C
(54)
M. Pinar and H. Schmid, Helv. Chim. Acta, 1962, 45, 1283. C. Djerassi, H. W. Brewer, H. Budzikiewicz, 0. 0. Orazi, and R. A. Corral, Experientia, 1962, 18, 113. 100 C. Djerassi, T. George, N. Finch, J. F. Lodish, H. Budzikiewicz, and B. Gilbert J . Amer. Chem. SOC.,1962, 84, 1489. 101 W. G. Kump and H. Schmid, Helv. Chim. Acta, 1961, 44, 1503. 102 W. G. Kump, D. J. Le Count, A. R. Battersby, and H. Schmid, Helv. Chim. Acta, 1962, 45, 854. 103 A. R. Battersby and D. J. Le Count, J . , 1962, 3245. 1 0 4 C. Kump and H. Schmid, Helv. Chim. Acta, 1962, 45, 1090. lo5 T. R. Govindachari, B. R. Pai, S. Rajappa, N. Viswanathan, W. G. Kump, K. Nagajaran, and H. Schmid, Helv. Chim. Acta, 1962, 45, 1146; A. Chatterjee, A. Bhattacharaya, and A. Deb, Naturwiss., 1962, 49, 279. lo6 B. Gilbert, J. M. Ferreira, R. J. Owellen, C. E. Swanholm, H. Budzikien-icz, L. J. Durham, and C. Djerassi, Tetrahedron Letters, 1962, 59. lo M. Plat, D. D. Manh, J. Le Men, M.-M. Janot, H. Budzikiewicz, J. 3 . Wilson, 1 L. J. Durham, and C. Djerassi, Bull. SOC.chim. France, 1962, 1082.
98 99
BENTLEY: ALKALOIDS
355
associated with an ester group in such a way that in acid they are converted into apo-bases containing a y-lactone ring and a free primary alcoholic group ; only partial structures have so far been allotted to these bases.lo8 The structures of several bases containing two indole units have been elucidated. Vincaleucoblastine and leurosine are both cleaved by acids, the latter to cleavamine (53) and the former to velbenamine, which is believed to be dihydrohydroxycleavamine; the second product from both bases is deacetylvindoline (48; OH in place of OAc); under the same conditions leurocristine affords velbenamine and deacetylde-N(a)-methylvindoline. Cleavamine (53) is obtained from catharanthine (54) under the same acid conditions, and on this evidence the structure ( 5 5 ; R = Me) is assigned to vincaleucoblastine and (55; R = CHO) to leurosine, the precise points of attachment of the vindoline unit and the hydroxyl group (probably 3,4) being unestablished ; leurosine may well be the 3,4-anhydro-analoge of vincaleucoblastine.109 Geissolosimine is also composed of two indole units and on acid fission is converted into vellosimine (44; R = R = H; CHO in place of CH,*OH) and geissoschizoline, and from this reaction and the reformation of the base from these two fragments in acetic acid and from a study of the nuclear magnetic resonance spectrum the alkaloid has been given the structure (56).110 Steroid Group.-The bases of the kurchi group have been further studied and the following structural assignments made: kurchamine (57; R = H, R = Me), kurchimine (57; R = Me, R = H), conkuressine (57 ; R = R = Me with a 7,S-double bond). The positions of the double bonds in these alkaloids have been determined by ozonolysis and by spectral studies.11l Two total syntheses of (&)-conessine have been recorded; these have little in common, although in both ring D is contracted from six- to five-membered by ozonolysis of a double bond and recyclisation of the resulting 1,6-diketone. Marshall and Johnsons route involves the h a 1 construction of ring E and maintains the correct stereochemistry throughout,l12 whereas in the work of Stork et aL113 an asymmetric centre is inverted at a late stage, after the construction of ring E but before the closure of ring A. Conessine has been converted into conessimine by way of the mono-N-oxide and by means of a von Braun demethylation; the di-N-oxide, on pyrolysis, affords N-demethyl-N-hydroxyapoconessinemefhine.ll4 Holaphyllamine (38aminopregn-5-en-20-one)and holamine (3a-aminopregn-5-en-20-one) have been synthesised from the corresponding 3-azides.115 New bases of the steroid group discovered include malouphylline (3/l-acetamido-20-dimethylJ. A. Joule and G . F. Smith, J . , 1962, 312. N. Neuss, M. Gorman, H. E. Boaz, and N. J. Cone, J . Amer. Chem. SOC., 1962, 84, 1509. 110 H. Rapoport and R. E. Moore, J. Org. Chem., 1962, 27, 2981. ll1 R. Tschesche and P. Otto, Chem. Ber., 1962, 95, 1144. J. A. Marshall and W. S. Johnson, J . Amer. Chem. SOC.,1962, 84, 1485. G. Stork, S. D. Darling, I. T. Harrison, and P. S. Wharton, J . Amer. Chern. Soc., 1962, 84, 2018. 114 P. K. Bhattacharaya, B. D. Kulkarni, S. Kanthamani, and C. R. Narayanan, Chem. and Ind., 1962, 1337. 115 R. Goutarel, A. Cave, L. Tan, and M. Lebmuf, BUZZ. SOC. chim. France, 1962, 646.
lo8 log
356
ORGANIC CHEMISTRY
amino-5cc-pregnan18-al), l6holafebrine (20cc-aminopregn-5-en-3~-01), and latifoline (5-conanen-3B-01)118 the last-named has been prepared by partial ; synthesis from conessine by way of conessimine.ll8 The alkaloid samandaridine (58) has also been shown to be based on a steroid skeleton, modified.119 I n the Solanurn group secondary and tertiary bases have been shown to be accessible by partial synthesis from 16@-hydroxy-steroids, in this way and dihydrosolasodine and dihydrotomatidine have been prepared. Of these, dihydrotomatidine has been converted through the related diketone into demissidine, and the latter has been further transformed into solanidine,
(59 )
thus completing the total synthesis of solanidine, y-solanine, and y-chaconine.120 The oximes of the pseudo-acetyl derivatives of solasodine and tomatidine have been found to undergo abnormal Beckmann transformation into amido-nitriles hydrolysable to 38,16/?-dihydroxy-5bisnorcholenic and allobisnorcholanic acid 22+16-lactone. lZ1 Isojervine, produced by the action of methanolic hydrogen chloride on jervine, has been proved to have the structure (59) by chemical and spectral studies ; the triacetyl-5,6,8,9tetrahydro-base affords an epoxide convertible by alumina into a 17-hydroxyA13,(17a)-compound that may be dehydrated and dehydrogenated to triacetyl-5,6-dihydro-ll-oxoveratramine and may also be converted into 5,6-dihydrojervisine1 7 - a ~ e t a t e . l ~ ~ Veralkamine has been assigned the strucmainly on ture of 20-(5-methyl-2-piperidy1)-17~-pregn-5-ene-3~,18-diol, spectroscopic and optical rotation evidence.lZ3 Lycopodium Bases.-As a result of interconversionsamong the bases and their derivatives and correlation of some of these with lycopodine, the fol116 E. Woodson, M.-M. Janot, F. Laine, and R. Goutarel, Bull. Soc. chim. France, 1962, 648. 117 G . Don, M.-M. Janot, X. Monseur, C. Conreur, and R. Goutarel, Bull. SOC. chim. France, 1962, 285. 118 M.-M. Janot, Q. Khuong-Hu, and R. Goutarel, Compt. rend., 1962, 254, 1326. l19 G. Habermehl, Angew. Chern., 1962, 74, 154. 120 K. Schreiber and G. Adam, Experientia, 1961, 1 7 490; I<. Schreiber and H. ', Ronsch, Experientia, 1961, 17, 491. lZ1 Y. Sat0 and N. Ikekawa, J . Org. Chenz., 1961, 26, 5058. 122 0. Wintersteiner and M . Moore, Tetrahedron Letters, 1962, 795. 123 J. Tomko and I. Benik, Coll. Czech. Chenz. Comm., 1962, 27, 1404.
BENTLEY: ALKALOIDS
357
lowing structures have been assigned in this group: fawcettine (60; R = Ac, R =H),isofawcettine (60 ; R =H, R =Ac), base K (60 ; R =R =Ac), lofoline (13-epimer of fawcettine), clavolonine (60; R = H ; 7-carbonyl group) and annofoline (60; R = H ; 13-carbonyl group), the absolute stereochemistry being determined by optical rotatory dispersion studies.l Z 4 Lycofoline and acrifolinol are obtained together by reduction of acrifoline with sodium borohydride in alkaline solution, and therefore lycofoline must be an epimer of acrifolinol and have the structure (60; R = R = H ; 3,4double bond).125 Flabelliformine, which may be reduced to lycopodine and
Me OR H - - H +
HO
dehydrated to an ap-unsaturated ketone must be one of the epimers of 8hydroxylycopodine,126 and lycodoline (Lycopodium base L-8) is 4-hydroxy1ycop0dine.l~~ a-Obscurine must have the structure (61), since it can be converted into the amino-keto-acid (62) by N-nitrosation and vigorous acid hydrolysis, and the lactam related to this acid gives lycopodine on reduction with lithium aluminium hydride ;b-obscurine is the cc/3y&unsaturatedlactam corresponding to (61).12* Terpene Group.-Hetisine has been shown 1 Z 9 by X-ray examination to have the constitution (63). The alkaloid gives a normal methiodide and a methine base containing two double bonds,l3* but on vigorous quaternisation it forms an isomeric methiodide which on Hofmann degradation gives a methine base containing only one double bond.131 These abnormal derivatives contain an extra C-methyl group and the methiodide is formulated as the quaternary salt of the hemiketal corresponding to the ketoalcohol (64), which is believed to arise from hetisine as shown in formula (62).l3O The absolute configurations of hetisine, atisine, veatchine,
R. H. Burnell and D. R. Taylor, Tetrahedron, 1961, 15, 173. A. L. Anet, M. Ahmad, and N. H. Kahn, Canad. J. Chem., 1962, 40, 236. 1 2 6 M. Curcumelli-Rodostamoand D. B. MacLean, Canad. J. Chem., 1962, 40, 1068. lZ7 W. A. Ayer and G. G. Iverach, Tetruhedron Letters, 1962, 87. 12* W. A. Ayer, J. A. Berezowsky, and G. G . Iverach, Tetruhedron, 1962, 18, 567. lZ9 M. Przybylska, Canad. J. Chem., 1962, 40, 566. l3O K. Wiesner, Z. Valenta, and L. G. Humber, Tetrahedron Letters, 1962, 621. 131 W. A. Jacobs and C. F. Heubner, J. Biol. Chem., 1947, 170, 189.
124
lz5 F.
358
garryine, and cuauchichicine have been deduced from previous data.132 By means of a new photochemical reaction,133podocarpoyl azide has been converted into the amide (@), which is the mirror image of a phenol obbainable from a t i ~ i n e . l ~ ~ Denudatine has been assigned the structure (66),135and hypaconitine has been shown to be probably N-demethyldeoxy-N-ethylaconitine.ls6 Miscellaneous Bases.-Securinine, from Securinega suffrutiwsa Rehd., can be hydrogenated to a lactam carbinol which on dehydrogenation gives 2-o-tolylpyridine,and this, together with spectral evidence and the production of phthalic acid on oxidation and p-toluidine on zinc-dust distillation of the base, has led to assignment of strueture (67) to the alkaloid.137 Virosecurinine,from#. virosa Pax. et Hoffm., is very probably the enantiomorph
@ &(6 YH ,
YH
(66)
(68)
CH NH
$H NH
of securinine.138 A new base of the phenanthroindolizidinegroup, tylocrebh e , is the 2,3,5,6-tetramethoxy-analogue tylophorine, and the racemic of base has been synthesised by conventional methods.139 The absolute configuration of a-erythroidine has been determined by degradation of this base to ( )-o-ethylphenyl tetrahydro-3-fury1 ketone, and the synthesis of this ketone from (+)-tetrahydro-3-furoic acid, which in turn has been related to ( )-methylsuccinicacid.140 By degradation and synthesis annuloline, from Lolium muZti$orum, has been shown to be 2-(3,4-dimethoxystyryl)-5-p-methoxyphenyloxazole. The structure previously assigned 141 to chaksine 142 has been confirmed by nuclear magnetic resonance studies.143 Acanthoidine has been identified as the formamidine derivative (68), and has been synthesised from 1-(3,4-dimethoxyphenethyl)tetramethylenediamine.144 Leonurine has been proved to be N-4-hydroxybutyl-N'-(4hydroxy-3,5-dimethoxybenzoyl)guanidine. 145 The taxines have been
+ +
133
133
W.B. Whalley, Tetrahedron, 1962, 18, 43.
J. ApSimon and 0. E. Edwards, Proc. Chem. SOC.,1961, 461. J. ApSimon and 0. E. Edwards, Canad. J. Chem., 1962, 40, 896. 1 3 5 N . Singh, A. Singh, and M. S. Malik, Chern. and Ind., 1961, 1009. 136 R . E. Gilman and L. Marion, Canad. J. Chem., 1962, 40, 1713. 1 3 7 S. Saito, K.Kodera, N. Sugimoto, 2. Horii, and Y . Tamura, Chern. and Ind., 1962, 1652. 138T. Nakano, T. H.Yang, and S. Erao, Chem. and Ind., 1962, 1651. 1 3 9 E. Gellert, T. R . Govindachari, M. V. Lakshmikanatham, I. 8 . Ragade, R. Rudzats, and N. Viswanathan, J., 1962, 1008. 1 4 0 R. K. Hill and W. R. Scheaver, J . Org. Chem., 1962, 27, 921. 141 R. S. Karimoto, B. Axelrod, J. Wolinsky, and E. D. Schall, Tetrahedron Letters, 1962, 83. 142K. Wiesner, Z. Valenta, B. S. Hurlbert, F. Bickelhaupt, and L. R. Fowler, J . Amer. Chem. SOC., 1958, 80, 1521. 1 4 3 L. R. Fowler, Z. Valenta, and K. Wiesner, Chem. and Ind., 1962, 95. 1 4 4 B. Frydman and V. Deulofeu, Tetrahedron, 1962, 18, 1063. 1 4 5 T. Goto, N. Kato, and Y. Hirata, Tetrahedron Letters, 1962, 545.
134
HONEYMAN : CARBOHYDRATES
359
studied and found to be nitrogen-free polyhydric alcohols (taxicins) esterified with one molecule of #l-dimethylamino-#l-phenylpropionic and one or acid more molecules of acetic acid. A partial structure has been assigned to O-cinnamoyltaxicin-I, from the major alkaloid taxine-I. 146 K. W. B.
10. CARBOHYDRATES
Monosaccharides.-GenemZ. X-Ray crystallography has shown that crystalline p-lyxose has the expected conformation, with one hydroxyl group (on (2-2)in the axial position.1 Circularly polarized light causes a change in optical rotation of solutions of D-galactose.2 The normally accepted assignment of a and /? to the anomers of D-glucose and D-mannose have been questioned.3 Infrared absorption spectra show that although D-gluco- and D-manno-heptdose do not mutarotate their solutions contain more than one form. For a wide range of sugars the equilibrium mixture in water contains a carbonyl-containing isomer.4 By a method in which an extremely active ,&D-fructofuranosidase is used the optical rotation of #l-D-fructofuranose has been mea~ured.~ I n a study of some sugars and sugar acids, trailing during paper chromatography is shown to be caused by adsorption.6 Correlations exist between mobility on paper and structure of some y-lactones.' Sugar and inositol acetates may be separated by thin-layer chromatography on silica gel ; because of their hydrophobic nature the positions of some of the acetates may be detected by spraying with water.* I n column chromatography an isotope effect has been noticed during the countercurrent distribution of ~ - [ l - ~ ~ C ] a r a b h o s e , labelled form moving more slowly, but the correthe sponding D-xylose and D-ribose compounds do not show this e f f e ~ t . The ~ presence of a small amount of formic acid in the eluate greatly improves the separation of a series of oligosaccharides on charcoal-Celite. lo Gas-liquid chromatography has been used successfully to separate polyol acetates, l1 including those from amino-sugars,l2and also carbohydrate acetals, including esters thereof.12 The relative mobilities of a series of trimethylsilyl ethers of carbohydrates have been found to be different from those of the corresponding acetates; the effect of molecular shape on mobility is discussed.13 The
146 J. N. Baxter, B. Lythgoe, B. Scales, R. M. Scrowston, and S. Trippett, J., 1962, 2964; B. W. Langley, B. Lythgoe, B. Scales, R. M. Scrowston, S. Trippett, and D. Wray, J., 1962, 2972. A. Hordvik, Acta Chem. Scand., 1961, 15, 1781. %P. Corriez, Compt. rend., 1962, 254, 1986. J. Blom and J. A. Christiansen, Acta Chem. Scand., 1962, 16, 1519. R. S. Tipson and H. S. Isbell, J . Res. Nut. Bur. Stand., 1962, 66, A , 31. B. Andersen and H. Degn, Acta Chem. Scand., 1962, 16, 215. sR.A. Schwane and G. N. Kowkabany, Analyt. Chem., 1962, 34, 325. R. J. Ferrier, J. Chromatog., 1962, 9, 251. E. Tate and C. T. Bishop, Canad. J. Chem., 1962, 40, 1043. L. M. Marshall and R. E. Cook, J . Amer. Chem. SOC., 1962, 84, 2647. lo P. M. Taylor and W. J. Whelan, Chem. and Ind., 1962, 44. l1 S. W. Gunner, J. K. N. Jones, and M. B. Perry, Canad. J . Chem., 1961, 39, 1892. la H. G . Jones, J. K. N. Jones, and M. B. Perry, Canad. J. Chem., 1962, 40, 1559. l3 R. J. Ferrier, Tetrahedron, 1962, 1 , 1149. 8
360
ORGANIC CHEMISTRY
paper electrophoresis of sugars with cetyltrimethylammonium borate at pH 9.6 gives mobilities different from those in potassium borate, making additional separations p0ssible.1~ Use of sulphonated phenylboronic acid allows electrophoresis to be done in neutral solution with a range of mobilities wider than obtained with borate or germanate s01utions.l~ New syntheses of DL-arabhose l6 and of DL-ribose l7 have been described. The addition of 2,4-0-ethylidene-~-erythrose 1,3-dihydroxyto acetone gives the 5,7-0-ethylidene derivatives of D-ghCO-, manno no-, and D-aztro-heptulose. l8 The configuration of apiose has been confirmed by synthesis. KetoD-fructose 1,3,4,5,6-penta-acetate was converted by diazomethane in dry penta-acetate (1) which ether into 2-deoxy-2,2-methyleneoxy-~-arabo-hexitol by deacetylation, periodate oxidation, and hydrolysis gave apiose (2).l9 L-Hamamelose (3) has been synthesized by a rather similar method.2* The biosynthesis of noviose (4) from isotopically labelled D-glucose suggests that the hexose skeleton may be used directly but that several epimerizations and oxidation-reduction stages may be involved.21
CH2 * OAC AcO - C - H H-C-OAC 1 H-C-OAc I (1) CHz'OAc CH2. OH
HO-C-H
H - CI
I
CH-OH HO-C-CH2.OH HO-C-H
CH2.OH
CHO (2)
I I
(3)
(4)
A simple synthesis of 5-acetamido-5-deoxy-~-arabinose the comgave pound in two forms, the major one having the furanose ring system. The other was also cyclic but had a six-membered ring with nitrogen as the heteroatom.22 The analogous D-xylose derivatives have also been isolated, although in this case the major product had the nitrogen in the ring.23 These are the first examples of compounds of this type. Additional derivatives containing the thiapyrmose ring have been described.24 The primary effects of y-radiation on deaerated solutions of D-mannose are similar to those observed in the presence of oxygen, however different the final products may be. The primary processes yield D-mannonic acid,
R . Piras and E. Cabib, J . Chromatog., 1962, 8, 63. P. J. Garegg and B. Lindberg, Acta Chem. Scand., 1961, 15, 1913. l6 I. Iwai and K. Tomita, Chem. and Pharm. Bull. (Japan), 1961, 9, 976. l7 I. Iwai and T. Iwashige, Chem. and P h r m . Bull. (Japan), 1961, 9, 316. lS R. Schaffer and H. S. Isbell, J. Org. Chem., 1962, 27, 3268. l9 A. Khalique, J., 1962, 2515. 2 o J. S. Burton, W. G. Overend, and N. R. Williams, Proc. Chem. Soc., 1962, 181. 21 A. J. Birch, P. W. Holloway, and R. W. Rickards, Biochim. Biophgs. Acta, 1962, 57, 143. J. K. N. Jones and J. C. Turner, J., 1962, 4699. 2 3 H. Paulsen, Angew. Chem., 1962, 74, 685; ibid., Internat. Ed., 1962, 1, 597. 2 4 C. J. Clayton and N. A. Hughes, Chem. and Id., 1962, 1795; R. L. Whistler, M. 8. Feather, and D. L. Ingles, J . Amer. Chem. SOC., 1962, 84, 122; M. S. Feather and R . L. Whistler, Tetrahedron Letters, 1962, 667.
l4
lS
HONEYMAN:
CARBOHYDRATES
361
D-glucosone, D-erykhrose, and three- and two-carbon fragments.25 With D-ribose the main reactions are end-group oxidation and chain-scission.26 Formaldehyde and 1,3-dihydroxyacebonehave been obtained by the y-irradiation of D-glUCOSe, D-fructose, and maltose.27 The mechanism of the formation of acidic polymers by the prolonged y-irradiation of deaerated aqueous D-glucose has been investigated with model compounds.2s Sugars containing 14C are best stored as frozen dilute aqueous solutions from which they may be recovered by freeze-drying. The decomposition of solid samples is mainly caused by attack from hydrogen atoms and hydroxyl radicals produced from the small quantities of water also present.29 Simple degradative processes for locating in sugars the positions occupied by 14C have been described.30 Oxidations. Double-labelling with radioactive isotopes has shown that in the oxidation of D-glucose with iodine the rate-determining step is the abskraction of the hydrogen atom on C - l . 3 l The mechanism of the oxidation of aldoses with bromine has been discussed in Mercuric acetate in methanol is suggested as a reagent for oxidizing secondary hydroxyl groups in the presence of primary ones. I n this way ribitol has slowly been partly converted into erythro-3-pentulose and DLerythro-2-pentulose. 33 I n the catalytic oxidation of inositols with oxygen or air monoketones (inoses) are obtained by attack of an axial hydroxyl Similar treatment of methyl a-D-ghcopyranoside leads mainly, but not entirely, to the uronic acid.35 Manganese dioxide appears to oxidize D-fructose in aqueous solution without formation of keto- or enediol groups. Some D-glucosone is produced but the reagent is rather unspecific in its action.36 Oxidation with chromium trioxide in benzene and glacial acetic acid of the one free hydroxyl group in a substituted D-arabitol gives a good yield of the ketose derivative.37 This oxidizing agent preferentially attacks axial hydroxyl groups.38 The mechanism of the oxidation of free sugars by periodate has been examined. The chief attack affects the pyranose ring form although early release of formaldehyde shows that the furanose or abdehydo-forms are also involved. The first product from D-glucose is 4-O-formyl-~-arabinose which
G. 0. Phillips and W. J. Criddle, J., 1962, 2733. G. 0. Phillips and W. J. Criddle, J., 1962, 2740. 2 7 S. V. Starodubtsev, M. P. Tikhomolova, E. L. Aizenshtat, and K. Tashmukhamedova, Zhur. obshchei Khim., 1961, 31, 3115. 2 8 A. J. Bailey, S. A. Barker, I. R. L. Lloyd, and R. H. Moore, Radiatio)z Res., 1961, 15, 532; A. J. Bailey, S. A. Barker, and M. Stacey, ibid., p. 538. 2 9 G. 0. Phillips, W. J. Criddle, and G. J. Moody, J., 1962, 4216. 30 H. Simon and J. Steffens, Chem. Ber., 1962,95, 358; J. D. Anderson, P. Andrews and L. Hough, Biochem. J., 1962, 84, 140. 31 H. S. Isbell, L. T. Sniegoski, and H. L. Frush, Analyt. Chem., 1962, 34 982. 32 H. S. Isbell, J . Res. Nut. Bur. Stand., 1962, 66, A , 233. 33 R. J. Stoodley, Canad. J. Chern., 1961, 39, 2593. 3 4 G. G. Post and L. Anderson, J. Amer. Chenb. SOC., 1963, 84, 471. 35 D. B. Easty, J. Org. Chenz., 1962, 27, 2102. 36 G. J. Moody, Nature, 1962, 195, 71. 37 D. H. Rammler and C. A. Dekker, J. Org. Chenz., 1961, 26, 4615. 38 6. Blom, Acta Chem. Scand., 1961, 15, 1667.
25 26
362
ORGANIC CHEMISTRY
is then oxidized mainly in the open-chain modification. The same principle holds during the oxidation of D-mannose and ~-galactose.39 I n partial oxidations of methyl D-aldopyranosides with periodic acid any cis-a-glycol system present is attacked prefer en ti all^.^^ The polyaldehydes obtained by periodate oxidation of a number of glycosides and oligosaccharides are shown t o be hydrated; that from melibiose is exceptional in containing one free aldehyde A colorimetric method for the determination of such polyaldehydes has been described,42as well as one for the detection of malondialdehyde produced during oxidation^.^^ A spectroscopic method for following oxidations with lead tetra-acetate in dilute solutions enables fast reactions t o be studied; the data are consistent with the formation of a five-membered cyclic lead complex.44 Glycol fission has been used for degrading hexose derivatives t o pentose ones.45 Glycosides. The course of formation of the methyl D-xylosides from D-XylOSe involves the initial formation of furanosides followed by their isomerization to the corresponding pyranosides. If the sugar is substituted at C-2 or C-3 the equilibrium mixture contains more of the furanosides.46 Some of the details of the mechanism proposed have, however, been conbenzyl-~-ribosyl bromide with methanol tested. 47 Treatment of 2,3,5-tri-0and silver carbonate gives mainly the methyl a-D-ribofuranoside because the benzyl group does not have a neighbouring-group effe~t.~S Reaction of mercuric acetate and methanol with D-glucal rapidly yields what is probably the product of diaxial addition, methyl 2-acetoxymercuri-2-deoxy-a-~mannopyranoside, which is reduced by borohydride t o methyl %deoxy-a-~glucopyranoside. The same sequence with D-glucal triacetate gives the same product, together with a larger amount of the /I-an~rner.~Q initial The product from D-glUCal is, however, claimed to be methyl 2-acetoxymercuri2-deoxy-~-~-mannoside, whereas from D-glucal triacetate the corresponding glucoside triacetate is formed.50 Phenyl D-glucosidesare obtained by action of the phenol on methyl or-D-glucoside-boron trichloride. Direct glucosylation of benzene was achieved with the same reagent in the presence of a small amount of aluminium chloride.51 The optical rotations of o-nitrophenyl a- and p-D-glucopyranosides are unusually temperature-dependent, probably because of electronic interaction between the nitro-group and the sugar.52
S. J. Angyal and J. E. Klavins, Austral. J . Chem., 1961, 14, 577. M. Guernet, Bull. SOC. chim. France, 1961, 1752. 41M. Guernet and A. Juardo-Soler, Compt. rend., 1962, 254, 2985. 42 A. Juardo-Soh and M. Guernet, Compt. rend., 1962, 254, 2586. 43 P. Mesnard and G. Devaux, Chim. analyt., 1962, 44, 287. 44 A. S. Perlin and S. Suzuki, Canad. J . Chem., 1962, 40, 1226. 4 5 K. Antonakis, A. Dowgiallo, and I Szabb, Bull. SOC. , . chim. France, 1962, 1355; G . Rembarz, Chem. Ber., 1962, 95, 1565. 4 6 C . T. Bishop and F. P. Cooper, Canad. J . Chem., 1962, 40, 224. 4 7 B. Capon, G. W. Loveday, and W. G. Overend, Chem. and Ind., 1962, 1537. 48 R. Barker and H. G. Fletcher, jun., J . Org. Chem., 1961, 26, 4605. 49 G. R. Inglis, J. C. P. Schwarz, and (in part) L. McLaren, J., 1962, 1014. 6 0 P. T. Menolopoulos, M. Mednick, and N. N. Lichtin, J . Amer. Chem. SOC., 1962, 84, 2203. 51 T. G. Bonner, E. J. Bourne, and S. McNally, J . , 1962, 761. 5zB. Capon, W. G. Overend, and M. Sobell, J., 1961, 5172.
39 4O
H O N E Y M A N : CARBOHYDRATES
363
Degradations. Starch, sucrose, and D-glucose have each been converted into 5-hydroxymethyl-2-furfuraldehyde (yields about 45%) by the combined action of a weak acid and a weak base.63 Unsaturated osones have been shown to be formed during the conversion of D-fructose into 5-hydroxymethyl-2-furfuraldehyde 64 and in the preparation of S-deoxy-~-erythro6 hexosone from di-D-fructosylglycine.5 The presence of the ring-oxygen atom is essential for the alkaline hydrolysis of diethylsulphonylglycopyranosylmethanes to the lower aldose.56 Although the 1-deoxy-l-nitroheptitols undergo cyclizations and dehydrations similar to those of the diethylsulphonylglycopyranosylmethanes they are not similarly degraded by mild Cyclic derivatives. Further evidence emphasizes the importance of hydrogen bonding in the reactions of polyhydric alcohols with aldehydes. Use of nuclear magnetic resonance spectroscopy has enabled the conformations to be determined for l ,3-0-benzylidene-erythritol diacetate (5),the
H
H
I
Ph
(9)
(9)
analogous L-threitol derivative which appears to be conformationally unstable (6, 7), and 173:2,4-di-0-benzylidene-erythritol and its L-threitol (8) analogue ( 9 ) . 5 8 The stability to acid of the benzylidene group in a series of methyl 4,6-0-benzylidene-aldohexosidesnot much affected by structure. 59 is Treatment of inositols with 2,2-diethoxypropane in the presence of acid has been found to be a good method for making O-isopropylidenederivatives. Even trans-pairs of hydroxyl groups may react.60 When attached to a six-memberedring in the chair conformation a single O-isopropylidenegroup deforms the chair only slightly, but if two such groups are attached to two pairs of cis-hydroxyl groups the cyclohexane ring assumes the skew conformation, or possibly something between boat and skew forms.61 The
5 3 M . L. Mednick, J . Org. Chern., 1962, 27, 398. 6 4 E. F. L. J. Anet, Chem. and Ind., 1962, 262. 5 5 E. F. L. J. b e t , Austral. J. Chem., 1962, 15, 503. 5 6 L. Hough and A. C. Richardson, J., 1962, 1019, 1032. 5 7 L. Hough and S. H. Shute, J., 1962, 4633. 5 8 A. B. Foster, A. H. Haines, J. Homer, J. Lehmann, and L. F. Thomas, J., 1961, 5005; A. B. Foster, A. H. Haines, and J. Lehmann, ibid., p. 5011. 5 9 B. Capon, W. G. Overend, and M. Sobell, Tetrahedron, 1961, 16, 106. 6 o S. J. Angyal and R. M. Hoskinson, J., 1962, 2985. 6 1 S. J. Angyal and R. M. Hoskinson, J., 1962, 2991.
364
ORGANIC CHEMISTRY
five-membered ring of some O-isopropylidene sugars in solution is shown by nuclear magnetic resonance evidence t o be in a partially staggered nonplanar form. 6 2 Ethers. Reducing sugars may be completely methylated in one treatment with methyl iodide and silver oxide in dimethylformamide. From L-arabinose, D-xylose, D-mannose, and D-glUCOSe the more stable of the pyranose forms is the main product, but with D-fructose, D-galactose, and D-gdaCtUrOniC acid furanose isomers predominate. 63 Partial methylation of sugar dithioacetals with methyl iodide and silver oxide in tetrahydrofuran has shown that for D-galactose the 2-, 3-, and 6-positions are equally react i ~ ewhereas for ~ - x y l o s position 2 is twice as reactive as 3 which is , ~ ~ e~~ ten times as reactive as 6. Under these conditions the dithioacetals of D-glucose and L-arabinose are methylated chiefly at position 2. Addition of sodium methoxide t o the appropriate sugar a-nitro-olefin is a simple 67 method for preparing 2-O-methyl-D-ribose and -D-mannose. Vinyl ethers may be prepared by treating the sugar with vinyl chloride and sodium hydroxide in tetrahydrofuran,68 with a~etylene,~*-~Owith or butyl 7O or isobutyl 7l vinyl ether in the presence of a catalyst. The major products obtained by the direct trimethylsilylation of mutarotated D-xylose are the fully substituted anomeric pyranose compounds.72 Esters. Sugars have been completely acetylated by heating them with acetic anhydride and a small amount of an acidic ion-exchange resin.73 Even a suspension of acetic anhydride in aqueous sodium hydroxide can be used in suitable cases.74 The racemization that occurs when 6-deoxy-6-iodo-aEdehydo-~-galactose 2,3,4,5-tetra-acetate is converted by acetic anhydride and zinc chloride into aldehydo-DL-galactose1,1,2,3,4,5,6-hepta-acetate has been shown to occur 75. also with the wglucose and D-mannose isomers.76 On use of [l-14C]sugars it became clear that the label remained a t C-1 on racemization. Hexoses acetylated a t position 6 do not undergo the conversion and the initial step is probably ionization of iodine, leaving a carbonium ion a t position 6 t o which the 5-acetyl group migrates, leaving in turn an ion a t position 5 which may racemize t o give the two possible isomers. This process may then recur
6 2 R. J. Abraham, K. A. McLauchlan, L. D. Hall, and L. Hough, Chem. and Ind., 1962, 213. 63 H. G. Walker, jun., M. Gee, and R. M. McCready, J. Org. Chem., 1962, 27, 2100. 6 4 G. G. S. Dutton and Y . Tanaka, Canad. J. Chem., 1962, 40, 1146. 6 5 G. G. S. Dutton and Y. Tanaka, Canad. J . Chem., 1962, 40, 1899. 6 6 G. G. S. Dutton and K. Yates, Canad. J. Clzem., 1958, 36, 550; G. G. S. Dutton and Y. Tanaka, ibid., 1961, 39, 1797. 6 7 J. C. Sowden, M. L. Oftedahl, and A. Kirkland, J . Org. Chem., 1962, 27, 1791. 6 8 A. J. Deutschman, jun., and H. W. Kircher, J . Amer. Chem. SOC.,1961, 83, 4070. 6 9 R. L. Whistler, H. P. Panzer, and J. L. Goatley, J. Org. Chem., 1962, 27, 2961. 7 0 S. A. Barker, J. S, Brimacornbe, M. R. Harnden, and M. Stacey, J., 1961, 5256. 71 W. A. P. Black, E. T. Dewar, and D. Rutherford, Chem. and Ind., 1962, 1624. 7 2 R . J. Ferrier and M. F. Singleton, Tetrahedron, 1962, 18, 1149. 73 G. M. Christensen, J. Org. Chem., 1962, 27, 1442. 74A. Aszalos and V. Prey, Starke, 1962, 14, 50. 7 5 F. Micheel, H. Ruhkopf, and F. Suckfull, Ber., 1935, 68, 1523. 7 6 F. >lichee1 and R. Bohm, Tetrahedron Letters, 1962, 107.
HONEYMAN
: CARBOHYDRATES
365
along the carbon chaim76 A rather similar type of transformation has been described for cyclitols.7 7 Treatment of D-glucal triacetate with silver benzoate and iodine in dry benzene gives the equimolecular mixture of 1-0-benzoyl-2-deoxy-2-iodo-ccD-glucopyranosetriacetate and the D-mannose isomer expected on mechanistic grounds.78 Crystalline 5-deoxy-5ethylthio-Larabinose diet hyl dithioacetal resulted from reaction of cc-L-arabinopyranosetetra-acetate with ethanethiol-boron trifluoride followed by deacetylstion. 79 The 2- and 6-hydroxyl groups may be preferentially esterified in S-deoxys1 D-mannose diethyl dithioacetal and in methyl cc-D-glucopyranoside. I n 1,6-anhydro-~-~-glucopyranose2- and the 4-position are the most the reactive. 82 For characterization of sugars, the p-p'-nitrophenylazobenzoates have been suggested.83 The 6-chloroformate of a D-galactose derivative has been converted into the 6-fluoroformate which has resisted attempts to decarboxylate it.84 Sulphur trioxide in pyridine has been used for preparing the 2-sulphate from methyl 4,6-0-benzylidene-cc-~-glucoside and also D-galactose 4-sul85 phate which is probably present in algal polysaccharides.86 Under mild conditions sulphuryl chloride converts free sugars into chloro-sulphate esters also containing chloro-deoxy-groups. I n this way 4,6-dichloro-4,6-dideoxyD-galactopyranosyl chloride 2,3-dichloro-sulphatehas been obtained from D-galactose, and the 4-chloro-4-deoxy-analogue from L-arabinose. 87 Phosphate groups have been shown to be capable of migration.88 have been isolated Deoxy-sugars. D-Rhamnose and 6-deoxy-~-talose froin a natural polysaccharide.89 Among deoxy-sugars that have been synthesized are 6-deoxy-~-idose,gO l-deoxy-~-psicose,~~ 3,6-&deoxy-~-galact ~ s e and ~ , ~ 4-deoxy-~-g~ucose.~~ Chalcose and mycinose, obtained from chalcomycin, are 4,6-dideoxy-3-0-methyl-~-glucose 6-deoxy-2,3-di94 and 0-methyl-D-allose, respectively. Mycarose, found in magnamycin and as 95
S. J. Angyal, P. A. J. Gorin, and M. Pitman, Proc. Chem. Soc., 1962, 337. R. U. Lemieux and S. Levine, Canad. J . Chent., 1962, 40, 1926. 7 9 M. L. Wolfrom and T. E. Whiteley, J . Org. Chem., 1962, 27, 2109. G. Rembarz, Chem. Ber., 1962, 95, 830. 81 A. K. Mitra, D. H. Ball, and L. Long, jun., J . Org. Chem., 1962, 27, 160. 8 2 R. W. Jeanloz, A. M. C . Rapin, and S. Hakomori, J . Org. Chem., 1961,26,3939. 83 El S. Amin, J., 1961, 5544. 84V. Welch and P. W. Kent, J., 1962, 2266. A. a s K . B. Guiseley and P. M. Ruoff, J . Org. Chem., 1962, 27, 1479. 8 6 J. R. Turvey and T. P. Williams, J., 1962, 2119. 8 7 H. J. Jennings and J. K. N. Jones, Canad. J . Chem., 1962, 40, 1408: 8 8 P. Rivaille and L. Szab6, Compt. rend., 1962, 254, 3705; T. Ukita and K. Nagasawa, Chem. and Pharm. Bull. (Japan), 1961, 9, 544. A. Markovitz, J . Biol. Chem., 1962, 237, 1767. 31. L. Wolfrom and S. Hanessian, J . Org. Chent., 1962, 27, 1800, 2107. 91 E. J. Reist, P. A. Hart, B. R. Baker, and L. Goodman, J . Org. Chem., 1962, 27, 1722. 9 2 H. Zinner, B. Ernst, and F. Kreienbring, Chent. Ber., 1962, 95, 821. 93 M. Dahlgard, B. H. Chastain, and Ru-Jen Lee Han, J . Org. Chem., 1962, 27, 929. 9 4 P. W. K. Woo, H. W. Dion, and L. F. Johnson, J . Amer. Chem. SOC., 1962, 84, 1066; P. W. I . Woo, H. W. Dion, and Q. R. Bartz, ibid., p. 1512. ( 95 H. W. Dion, P. W. K. Woo, and Q. R. Bartz, J . A m e r . Chern. SOC., 1962, 84, 880.
77
366
ORGANIC CHEMISTRY
its 4-acetate in leucomycin B,96 2,6-dideoxy-3-C-methyl-~-xylohexose,97 is and cladinose, from erythromycin, is its 3-methyl ether.ss L-Lyxose, d-O-methyl-~-fucose, and an unidentified dideoxyaldohexose have been isolated from c u r a m y ~ i n . The carbohydrate portion of the cardiac glyco~~ side, gomphoside, is derived from a 4,6-dideoxyhexosone. loo An anhydroderivative of a branched-chain trideoxyoctose has been isolated from an antibiotic. l01 Amino-sugars. Acetamido-deoxy-ketoses having the nitrogen atom attached to the terminal position remote from the keto-group have been made by oxidizing 1-acetamido-l-deoxy-pentitols -hexitols with Acetoor bacter suboxydans.lo2 The eight 3-amino-3-deoxy-~-aldohexoses now been synthesized; have the method based on treatment of a suitable dialdehyde with nitromethane has been particularly helpful.lo3 Sodium azide has been used to open the nnhydro-ring of a 2,3-anhydro-~-alloside derivative, so giving mainly the with diaxial 2-azido-2-deoxy-~-altroside a small amount of the 3-azido-3deoxy-D-glucoside. Similar treatment of a 2,3-anhydro-~-mannoside gives only the 3-azido-3-deoxy-~-altroside. Conversion of the 2-azido-2-deoxy-~altroside derivative into the 3-toluene-p-sulphonate,followed by treatment with sodium azide and then reduction, has given the 2,3-diamino-2,3-dideoxy~-mannoside.l~* Another example of the synthesis of an amino-sugar involving replacement of a methanesulphonate group by azido has been p~b1ished.l~~ Magnesium methoxide in methanol has been found to be the best reagent for de-O-acetylating acetylated amino-sugars. Magnesium-dried methanol may cause deacetylation and should be purified by distillation from 2,4,6trinitrobenzoic acid when necessary.106 By use of nuclear magnetic resonance spectra and by synthetic methods mycaminose has been shown to be 3,6-dideoxy-3-dimethylamino-~-glucose~~ whereas similar spectra and degradation provide evidence that desosamine is 3,4,6trideoxy-3-dimethylamino-D -xylohexose.lo
T. Watanabe, T. Fujii, and K. Satake, J. Biochem. (Japan), 1961, 50, 197. A. B. Foster, T. D. Inch, J. Lehmann, L. F. Thomas, J. M. Webber, and J. A. Wyer, Proc. Chem. SOC.,1962, 254. 9 8 A. B. Foster, T. D. Inch, J. Lehmann, and J. M. Webber, Chenz. and Ind., 1962, 1619. 9 9 0. L. Galmarini and V. Deulofeu, Tetrahedron, 1961, 15, 76. 100 R. G. Coombe and T. R. Watson, Proc. Chem. SOC.,1962, 214. 101 J. S. Webb, R. W. Broschard, D. B. Cosulich, J. H. Mowat, and J. E. Lancaster, J . Amer. Chem. SOC.,1962, 84, 3183. 102 J. K. N. Jones, M. B. Perry, and J. C. Turner, Canud. J. Chem., 1961, 39, 2400; 1962, 40, 503; J. C. Turner, ibid., p. 826. 103 H. H. Baer, J. Amer. Chem. SOC., 1962, 84, 83; A. C. Richardson, J., 1962, 373; A. C. Richardson and ( n part) K. A. McLauchlan, ibid., p. 2499. i 1 0 4 R. D. Guthrie and D. Murphy, Chem. and Ind., 1962, 1473. 1 0 5 E. J. Reist, R. R. Spencer, B. R. Baker, and L. Goodman, Chem. and Ind., 1962, 1794. 106 D. R. Whitaker, M. E. Tate, and C. T. Bishop, Canad. J . Chem., 1962,40, 1885. 1 0 7 W. Hofheinz and H. Grisebach, 2. Naturforsch., 1962, 17b, 355; A. B. Foster, T. D. Inch, J. Lehmann, M. Stacey, and J. M. Webber, Chem. and Id., 1962, 142; J., 1962, 2116; A. C. Richardson, ibid., p. 2758. l 0 8 W. Hofheinz and H. Grisebrtch, Tetrahedron Letters, 1962, 377; P. W. K. WOO, H. W. Dion, L. Durham, and H. S. Mosher, ibid., p. 735; C. H. Bolton, A. B. Foster, M. Stacey, and J. M. Webber, J., 1961, 4831.
g6
97
HONEYMAN
CARBOHYDRATES
367
Glucosamine has been converted into its l-thio- log and 6-thio-analogues. Di- and Oligo-saccharides.-Polymerization of 1,6-anhydro-~-~-glucopyranose by the action of concentrated hydrochloric acid gives isomaltose, gentiobiose, and a little cellobiose as well as tri- and higher oligo-saccharides, 111 whereas thermal polymerization leads to a mixture containing the 1,6-anhydro-derivatives of maltose, cellobiose, kojibiose, and sophorose.112 By heating D-glucose with a cation-exchange resin a mixture was obtained which differed from that obtained in aqueous solution by reversion mainly in the absence of maltose and the presence of larger amounts of isomaltose and nigerose.113 Treatment of D-glucose with methyl a-Dglucoside-boron trichloride in nitrobenzene containing silver oxide gave a t least eight of the D-glucopyranose disaccharides, the lxc,6-linkagebeing formed most readily.51 The chief products from the action of a commercial emulsin on D -galactose were 3- 0- and 6-0-/3 -galactopyranosyl-D -galac-D tose. 114 The low yields often obtained in the Konigs-Knorr synthesis of disaccharides have been shown to be in part caused by the decomposition of the glycosyl halide through reaction with silver oxide. The side reactions are greatly affected by the type of silver oxide used and are retarded when iodine is present ;all methods tried in order to remove water were ineffective. The by-products obtained from D-mannopyranosyl bromide tetra-acetate include D-mannose 2,3,4,6-tetra-acetate, a dimeric orthoacetate, and an orthoester of high molecular weight.115 The influences of conformation, solvent, and neighbouring groups largely decide which anomer is obtained. 116 A marked increase in yield of the naturally occurring /?-D-ribofuranosyl /?-D-ribofuranoside resulted from the addition of silver perchlorate 117t o the Konigs-Knorr reaction mixture.118 Identification of the position of the link in disaccharides may be helped by use of spray reagents on paper chromat~grams,l~~ sodium periodor of ate, 120 or by degradation with manganese dioxide.121 Exposure of sucrose to X-rays leads to reduction of hydroxyl content.122
lo9 D. Horton and M. L. Wolfrom, J . Org. Chem., 1962, 27, 1794; W. M. Zu Reckendorf and W. A. Bonner, ibid., 1961, 26, 4596. 110 T. Ito, Agric. and Biol. Chem. ( J a p a n ) , 1961, 25, 585; W. M. Zu Reckendorf and W. A. Bonner, J . Org. Chem., 1961, 26, 5241. l l 1 L. Reichel and H. Xchiweck, Naturwiss., 1961, 48, 696. 112 M. L. Wolfrom, A. Thompson, R. B. Ward, D. Horton, and R. H. Moore, J . Org. Chem., 1961, 26, 4617. l13P. S. OColla, E. E. Lee, and D. McGrath, J . , 1962, 2730. l14A. M. Stephen, S. Kirkwood, and F. Smith, Canad. J . Chem., 1962, 40, 151. 115 H. R. Goldschmid and A. S. Perlin, Canad. J . Chem., 1961, 39, 2025. 116 P. A. J. Gorin and A. S. Perlin, Canad. J . Chem., 1961,39, 2474; P. A. J. Gorin, ibid., 1962, 40, 275. 11 H. Bredereck, A. Wagner, G. Faber, H. Ott, and J. Rauther, Chem. Ber., 1959, 92, 1135. 11* E. Rosenberg and S. Zamenhof, J . Riol. Chem., 1962, 237, 1040. 119 R. W. Bailey, J . Chrmatog., 1962, 8, 57. lao I<. Takiura and K. Koizumi, Chem. and Pharm. Bull. (Japan), 1962, 10, 134. 121 J. L. Bose, A. B. Foster, N. Salim, M. Stacey, and J. M. Webber, Tetrahedron, 1961, 14, 201. lZ2 H. Shields and P. Hamrick, J . Chem. Phgs., 1962, 37, 202.
368
ORGANIC CHEMISTRY
Incompletely substituted O-alkyloxycarbonylsucroses were obtained on treating the sugar with alkyl chloroformates in the presence of aqueous resulted after further reaction in alkali, but octa-O-ethoxycarbonylsucrose pyridine. The more highly substituted derivatives, although readily hydrolysed by alkali, are unexpectedly stable to acid. Cross-linkedpolymers result from heating the esters with alkaline catalysts.123 Reaction of sucrose with vinyl ethers and with cyclic enol ethers such as 2,3-dihydropyran readily yields a variety of a ~ e t a l s . 1 ~ ~ An unsaturated aldobiuronic acid, produced by an enzyme from Bacillus polymyxn acting on pectic acid, is shown to be 4-0-(4,5-didehydro-a-~galacturonosyl)-D -galacturonic acid. l2 Branched trisaccharides have been synthesized 126 and panose, isomaltotriose, and 3-O-a-isomaltosyl-~-glucose have been isolated from hydrol, produced by the incomplete acid hydrolysis of starch.f27 A homologous series of sucrose D-galactosides has been isolated from carnation roots. 12* Acidic hydrolysis of a modified heparin gives D-glucose, D-glucosamine, and 4-0a-~-g~ucopyranosy~-2-amino-2-deoxy-D-g~ucose. 129 Disaccharide derivatives containing D-glucosaminehave been synthesized.l 3 O New sugars isolated from human blood-group A substance include S-O-B-~-galactopyranosyl-2-acetamido-2-deoxy-~-galactose,~~~ 3-0-(2-acetamido-2-deoxy-aD-galactosy1)-D-galactose, and 4-0-~-~-ga~actosyl-2-acetamido-2-deoxy 3D-glucose, and 2-acetamido-2-deoxy-a-~-galactosy~-( 1 +3)-~-D-galaCtOSyl(1 +3)-2-acetamido-2-deoxy-~-glucose.~~~ Po~saccharides.-CeZluZose. The increased reactivity and the change in crystal structure to cellulose I 1 that results when cellulose I is treated with 1 ethylamine have been confirmed.133 The accessibility of cellulose has been measured by observing the exchange that occurs between cellulose and tritiated water.134 However, there is some alteration in the proportion of ordered material during the interaction. 135 Because of greater molecular order cellulose is less reactive than starch. Hydroxyethylation of cellulose proceeds at a reasonable rate within a comparatively limited range of sodium hydroxide concentration. Nevertheless, slight regular hydroxyethylation disrupts the crystal structure of cellulose
123 124
R. S. Theobald, J . , 1961, 5359, 5366. S. A. Barker, J. S. Brimacombe, J. A. Jarvis, and J. &I. Williams, J . , 1962,
S. Hasegawa and C. W. Nagel, J . Biol. Chem., 1962, 237, 619. A. Klemer and K. Homberg, Chem. Ber., 1961, 94, 2747; I. J. Goldstein and
3158.
125 126
B. Lindberg, Acta Chem. Scand., 1962, 16, 383. 127 A. Sato, Y.Ito, and H. Ono, Chem. and lnd., 1962, 301; A. Sato and H. Ono, ibid., p. 1536. 128 J. E. Courtois and U. Ariyoshi, Bull. SOC. Chim. biol., 1962, 45, 23. M. L. Wolfrom, J. R. Vercellotti, and D. Horton, J . Org. Chem., 1962, 27, 705. 130 K. Onodera, S. Kitaoka, and H. Ochiai, J . Org. Chem., 1962, 27, 156. 131 T. J. Painter, I. A. F. L. Cheese, and W. T. J. Morgan, Chem. and Ind., 1962, 1535. 132 G. Schiffman, E. A. Kabat, and S. Leskowitz, J . Amer. Chem. SOC., 1962, 84, 73. T. P. Nevell and S. H. Zeronian, Polymer, 1962, 3 187; H. Spedding, ibid., , pp. 195, 211. 134 0 Sepall and S. G. Mason, Canad. J . Chem., 1961, 39, 1934. . lS5 0.Sepall and S. G. Mason, Canad. J . Chem., 1961, 39, 1944.
HONEYMAN: CARBOHYDRATES
369
so that subsequent reaction is as rapid as in ~ t a r c h . l 3 ~ Chitin is less reactive than cellul0se.~~7 Investigation of the distribution of substituents in cellulose ethers has established the relative reactivities shown in the Table
j
Reagent
c-2 3 3.5 5 4.5 1.2 2 C-3 1 1 q 1
I
~
C-6
10 2 2
1.5
I Ethylene oxide Dimethyl sulphate

I
Methyl chloride Ethyl chloride Diazomethane Monochloroacetic Acid
2.5
for the different hydroxyl The relative acidities of the different hydroxyl groups have been measured.139 The grafting of other polymers on to cellulose has been achieved by using diazonium groups attached to the polysaccharide,lgoceric ions,141 or yradiation,142 as initiators. Starch and gZycogen. Different amyloses have been separated into fractions ranging in degree of polymerization (DP) from 550 to 1840 by a method depending on the fact that the higher fractions form complexes with iodine at lower concentrations. Many carefully prepared starches have been fractionated into amylose and amylopectin by the thymol method. Recrystallization with butanol has given amyloses ranging in DP (determined by viscosity) from 1000 (wrinkled pea) to 4400 (parsnip). The molecular weights (by light scattering) of the amylopectins were extremely high (e.g., for broad-bean and banana, 10s).lg4 Electrodialysis gave pure amylose and amylopectin fractions from potato starch. 145 I n dilute aqueous solution amylose molecules are probably highly associated deformed helices.146 Oligosaccharides as small as maltotetraose form I,- c0mplexes.14~ By application of methods used with monosaccharides (3,6-anhydroamylose has been prepared and shown to have a, more stable glycosidic link than amy10se.l~~ Reaction of monosodio-starch with methyl iodide gives a methyl ether having about half of the glucose units unsubstituted. The
136
E. D. Klug, Starke, 1961, 13, 429.
S. N. Danilov, E. A. Plisko, and E. A. Pyaivinen, Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Nauk, 1961, 1500. 138 I Croon, Svensk Papperstidn., 1960, 63, 247. . 139 V. A. Derevitskaya, G. S. Smirnova, and Z. A. Rogovin, Doklady Akad. Nauk S.S.S.R., 1961, 141, 1090. 140 G . N. Richards, J. Appl. Polymer Sci., 1961, 5, 553. 1 4 1 G. N. Richards, J . Appl. Polymer Sci., 1961, 5, 539, 558. 142 R. J. Demint, J. C. Arthur, jun., A. R. Markezich, and W. F. McSherry, Textile Res. J., 1962, 32, 918; U.Azizov, Tr. Tashkentsk, Konf PO Mirnomu .Ispolz A t . Energii Akad. Nauk Uz.S.S.R., 1; Y. Hachihama and 8. Takamuru, Technol. Reports Osaka Univ., 1961, 11, No. 485, 431. 1 4 3 J. Ho116 and J. Szejtli, Starke, 1962, 14, 75. 144 C. T. Greenwood and J. Thomson, J., 1962, 222. 145 M. Richter and M. Ulmann, Kolloid Z . , 1961, 176, 98. 146 T. Kuge and S. Ono, Bull. Chem. SOC. Japan, 1961, 34, 1264. 14 J. A. Thoma and D. French, J . Phys. Chern., 1961, 65, 1825. 148 R . L. Whistler and S. Hirase, J. Org. Chem., 1961, 26, 4600.
l37
370
ORGANIC CHEMISTRY
relative amounbs of substitution at positions 2, 3, and 6 are 2.6 : 1 : 1-2.149 A method for finding the average chain-length of glycogen in 10-50 mg. samples is based on the use of salivary a-amylase. The results agree with those obtained by periodate oxidation.150 Concanavalin A, a globulin from jack-bean meal, is a convenient reagent for distinguishing between glycogen, limit dextrins, and amylopectin on a milligram scale.151 MisceZZaneous. I n a sample of laminarin having about half of the molecules terminated by a mannitol residue it has been shown that the mannitol is attached only through C-1.152 A water-soluble laminarin isolated from the seaweed Eisenia bicycZis has a molecule free from mannitol and consisting of about 20 D-glucose units linked 1,3 and 1,6 in the proportion of about 2 : 1. At least three of the 1,6-linked units are present in a block.153 Confirmation that lichenin is a linear /?-D-glucopyranosepolymer with .1,3- and 1,4-links has been obtained by enzymic hydrolyses.154 An electrophoretically homogeneous mannan obtained in the mediumsupporting growth of PeniciZZium chcrrlesii G. Smith has eight D-manno~~ pyranose units joined 1,2 except for a 1 , 6 - b r a n ~ h . l Another mannan, from the green coffee bean, is essentially linear and has about 45 pyranose units joined by l P , 4 - l i n k ~ . I ~ ~ The glucomannan from Pinus silvestris L. has an acetyl content of about 6% whereas the glucurono-arabinoxylan is almost free from acety1.157 Glucomannans from Pinus densiJlora, Acer sacchurum, Larix decidw, and the bark of Abies amabilis have been isolated and examined. The 1P,4link predominates. 15* The presence of 1,4-linked L-guluronic acid in alginic acid has been confwmed. The reason for the high proportion of D-mannuronic acid residues in the polymer that are not attacked by periodate is not yet k n 0 ~ n . 1 ~ 9 Although 2,3-di-O-methyl-~-lyxose has been isolated during structural studies of wood hemicelluloses it is an artifact produced by the ready epimerization by alkali of the D-xylose ether.l60 Kinetic measurements of the rate of decarboxylation of uronic acids has emphasized the care that is necessary to avoid decarboxylation during the isolation of pectic substances. Extractions should not be done with hot ammonium oxalate and oxalic acid; even prolonged treatment with hot 70% ethanol causes some decarboxylation. 149 B. J. Bines and W. J. Whelan, J., 1962, 4232.
D. J. Manners and A. Wright, J., 1962, 1597. D. J. Manners and A. Wright, J., 1962, 4592; 0. Kjolberg and D. J. Manners, {bid., p. 4596. 16aW. D. Annan, E. L. Hirst, and D. J. Manners, Chem. and Ind., 1962, 984. 153 N. Handa and K. Nisizawe, Nature, 1961, 192, 1078. 154 A. S. Perlin and S. Suzuki, Canad. J . Chern., 1962, 40, 50. 1 5 5 L. Hough and M. B. Perry, J., 1962, 2801. 1 5 6 M. L. Wolfrom, M. L. Laver, and D. L. Patin, J. Org. Chem., 1961, 26, 4533. 157 H . Meier, Acta Chem. Scand., 1961, 15, 1381. 158 T. Koshijima, Agric. and Biol. Chem. (Japan), 1961, 25, 706; G. A. Adams, Canad. J . Chem., 1961, 39, 2423; G. 0 Aspinall, R. Begbie, and J. E. McKay, J., 1962, . 214; T. E. Timell, Svensk Papperstidn., 1961, 64, 744. 150 D. W. Drummond, E. L. Hirst, and E. Percival, J., 1962, 1208. 160 G. G. S. Dutton and T. G. Murata, Canad. J. Chem., 1961, 39, 1995; G. G. S. Dutton and S. A. McKelvey, {bid., p. 2582. 1 6 1 D . M. W. Anderson, A. M. Bews, S. Garbutt, and N. J. King, J., 1961, 5230.
150 161
U L B R I C H T : NUCLEIC ACIDS
37 1
I n porphyran from the red seaweed, Porphyra umbiliuzlis, the sulphate ester is attached mainly to C-6 of L-galactose units that are linked to other residues through positions 1,2 or 1,4. The other units are mainly l6 1,3-linked. The chief repeating unit of the mucopolymccharide of bovine cornea 163 is shown below (10).
CHI*OH
I
.--*H
n
OH
D 0
0..
FH,.O*S03H
....
NHAc
(10)
J. H.
11. NUCLEIC ACIDS
IT has been noted that in the ten years after 1947 the nucleic acid entries in Chemical Abstracts showed a logarithmic growth with a doubling of the number every 2.7 years.1 The Annuul Reviews of Biochemistry devoted one chapter to nucleic acids in 1948-57, two in 1958-60, three in 1961, and four chapters, totalling 122pages, in 1962,2anindication of the current importance of this field. Since the last reviews in these ReportsY3 considerable progress has been made in the organic chemistry of nucleic acids, but there is no doubt that the most notable advances have been on the biochemical side. Bases.-There has been great interest in the effect of radiation (ultraviolet, unless otherwise stated) on the nucleic acid bases. Beukers and Berends * found that adenine, guanine, and thymine are not affected in aqueous solution, whereas uracil and cytosine are hydrated at the 4,5-double bond. Irradiation of frozen solutions of thymine or uracil gives rise to the formation of dimers with a cyclobutane structure; the thymine dimer is regarded as having structure (1) or that with the methyl groups on the same side of the cyclobutane ring. It is supposed that dimer formation occurs in frozen solutions because of the longer life-time 0 of triplet-state radicals. The hydration can be reH H Me 0 (1) versed by a change in pand heat. I n dirnerisation there is an equilibrium whose position depends on the concentration of paramagnetic substances, dimerisation being diminished by dissolved molecular
D. A. Rees, J., 1961, 5168. S. Hirano, P. Hoffman, and K. Meyer, J. Org. Chem., 1961, 26, 5064. R. F. Steiner and R. F. Beers, Polynucleotides, Elsevier, Amsterdam, 1961. L. F. Cavalieri and B. H. Rosenberg, Nucleic Acids: Molecular Biology of DNA, Ann. Rev. Biochem., 1962, 31, 247; E. S. Canellakis, Metabolism of Nucleic Acids, Ann. Rev. Biochem., 1962, 31, 271; M. Grunberg-Manago, Enzymatic Synthesis of Nucleic Acids, Ann. Rev. Biochem., 1962, 31, 301; M. V. Simpson, Protein Biosynthesis, Ann. Rev. Biochem., 1962, 31, 333. A. 3%.Miehelson, Ann. Reports, 1960, 57, 294; J. N. Davidson, {bid., p. 352. R. Beukers and W. Berends, Biochtim. Biophys. Acta, 1960, 38, 573; 1960, 41, 550; 1961, 49, 181.
162
163
HLB
372
ORGANIC CHEMISTRY
oxygen and transition-metal ions. It is suggested that this dimerisation reaction is responsible for the biological effects of ultraviolet radiation on deoxyribonucleic acid (DNA).4 Wackers group have shown that the thymine dimer is formed in DNA when bacteria are irradiated and that the same product is obtained by irradiating dilute aqueous solutions of thymine.5 Similar dimers can be obtained from uridine and thymidine,6 dimethyluracil,7 and dimethylthymine,s and a mixture of uracil and thymine gives a mixed dimer.9 I n the dinucleotide guanyloyl-5,3-uridine, uracil was the hydrated but no dimer was formed.9 The action spectrum for the reversal of the dimerisation of thymine after thawing has a shape similar to that of the ultraviolet-absorption curve of the dimer itself; the intensity is very low at 300 m p and increases as the wavelength decreases.1 The dimerisation of thymine and thymine nucleotides is an equilibrium depending on the wavelength; the equilibrium is on the side of the monomer at 235 mp, and on the side of the dimer at 285 mp.ll The rate of killing of Escherichia coli on ultraviolet irradiation is proportional to the amount of thymine dimer formed;l2 also consistent with the view that thymine dimer formation is responsible for the biological effects of ultraviolet radiation on DNA are the fhdings that incubation of irradiated DNA with photoreactivating enzyme from bakers yeast in light destroys over 90% of the thymine dimer formedY13 that incorporation of the thymine analogue azathymine into and the DNA of bacteria increases their resistance to ultraviolet irradiation. l4 ?-Irradiation of deaerated aqueous solutions of thymine gives quite different products, namely, 5-hydroxymethyluracil,thymine cis- and trans-glycol, and dihydrothymine.l5 Previous evidence 16 which had indicated that the site of protonation in the nucleic acid bases and their nucleosides was N-1 in cytosine and adenine and N-7 in guanine has been confirmed by the X-ray diffraction of 9-methyladenine dihydrobromide (H on N-1 and N-7) and 3-methylcytosine hydrobromide (H on N-1) 1 7 and by a study of the infrared spectra of protonated and deprotonated nucleosides, in which the site of protonation was found to be at N-1 in cytidine and adenosine, and at N-7 in guanosine.ls Results from the alkylation of bases and nucleosides are not always as clear-cut, since this may depend on the reaction conditions. Thus adenine gives
A. Wacker, H. Dellweg, and D. Weinblum, Naturwiss., 1960, 47, 477. 8 A . Wacker, H. Dellweg, and E. Lodemann, Angew. Chem., 1961, 73, 64; A. Wacker, L. Trager, and D. Weinblum, ibid., p. 65. S. Y. Wang, Nature, 1961, 190, 690. 8 n. L. Wulff and G. Fraenkel, Biochim. Biophys. Acta, 1961, 51, 333. A. Wacker, D. Weinblum, L. Triiger, and Z. H. Moustafa, J. Mol. Biol., 1961, 3, 790. 1 0 R. Setlow, Biochim. Biophys. Acta, 1961, 49, 237. 11 H. E. Johns, S. A. Rapoport, and M. Delbriick, J. Mol. Biol., 1962, 4, 104. 1 2 A. Wacker, H. Dellweg, and D. Jackerts, J. Mol. Biol., 1962, 4, 410. l3 D. L. WuW and C. S. Rupert, Biochem. Biophys. Res. Comm., 1962, , 237. 7 14A. Wacker and D. Jackerts, J. Mol. Biol., 1962, 4, 413; H. L. Giinther and W. H. Prusoff, Biochim. Biophys. Acta, 1962, 55, 778. l5 B. Ekert, Nature, 1962, 194, 278. l6 C. A. Dekker, Ann. Rev. Biochem., 1960, 29, 463. 1 7 R . F. Bryan and K. Tomita, Nature, 1961, 192, 812. ISM. Tsaboi, Y. Kyogoku, and T. Shhanouchi, Biochirn. Biophys. Acta 1968, 55, 1.
U L B R I C H T : NUCLEIC A C I D S
373
adenine 1-oxide l9 but is alkylated a t N-3,20321 whereas adenosine 22 and deoxyadenosine 23 are alkylated a t N-1, cytosine and cytidine at N-1,24 and guanine a t N-7 and bhen at N-9.20, 25 The base analogue 2-aminopurine, which is highly mutagenic, was found to be incorporated to a small extent (O-lyo thymine) into DNA.26 of The occurrence of 5-hydroxymethylcytosine (HMC) in place of cytosine in the T-even bacteriophages of E. coli has led to many studies of this interesting system. Lehman showed that in T2, 25% of the 5-hydroxymethylcytosine has no glucose attached t o the hydroxymethyl group, 70% has one molecule, and 5% has two molecules of glucose attached, the first being bound by an a-linkage, and the second to the first by a @-linkage. I n T4, every molecule of hydroxymethylcytosine has one molecule of glucose, of which 70% is in the a- and 30% in the b-linkage. I n T6 the linkages are as in T2 but the percentages of 0, 1, and 2 molecules of glucose are 25, 3, and 72, respectively.27 The DNA of T6 has been shown t o contain gentiobiose ; hence the full structure of the hydroxymethylcytosine nucleoside is
CH2 - 0 CH>*OH
OH
HO
HO ' as shown (2).2* The reaction leading to the glucosylation of hydroxymethylcytosine-DNA has been investigated and it has been shown that in T2 and T6 there is an enzyme transferring glucose from uridine diphosphate-glucose t o give a-glucosyl-HMC-DNA,but T4 contains two enzymes, the glucosyl linkage produced being a with one enzyme and @ with the other.29 Infection of E . coli by T-even bacteriophage leads to the synthesis of new enzymes, such as those just discussed, and to an increase in the activity of various other enzymes associated with DNA biosynthesis. It has been found that, at
ISM. A. Stevens and G. B. Brown, J . Amer. Chem. SOC.,1960, 82, 2759. 2o J. W. Jones and R. K. Robins, J. Amer. Chem. SOC., 1962, 84, 1914. 21 B. C. Pal, Biochemistry, 1962, 1, 558; N. J. Leonard and R. A. Laursen, J. Org. Chem., 1962, 27, 1778; N. J . Leonard and J. A, Deymp, J . Amer. Chem. SOC.,1962, 84, 2148. Z2P. Brookes and D. Lawley, J., 1960, 539. 2 3 A. Codington, Biochim. Biophys. Acta, 1962, 59, 472. Brookes and D. LawIey, J., 1962, 1348. 2 5 P. Brookes and D. Lawley, J., 1961, 3923. 2 6 A. Wacker, S. Kirschfeld, D. Hartmann, and D. Weinblum, J. Mol. Biol., 1960. 2, 69; A. Wacker, S. Kirschfeld, and L. Trager, ibid., p. 241; H. Gottschling and E. Freese, 2. Naturforsch., 1961, 16b, 515. 2 7 I. R . Lehman and E. A. Pratt, J. Biol. Chent., 1960, 235, 3254. 2 8 S. Kuno and I. R. Lehman, J. Biol. Chem., 1962, 237, 1266. 2 9 S. R. Kornberg, S. B. Zimmerman, and A. Kornberg, J. Biol. Chem., 1961, 236, 1487; S. B. Zimmerman, S. R. Kornberg, and A. Kornberg, ibid., 1962, 237, 512; J. Josse and A. Kornberg, ibid., p. 1968.
374
least in the cases of thymidylate kinase 30 and DNA p o l y m e r a ~ e these ,~~ are new enzymes, different from those present in the uninfected host. 5-Hydroxymethylcytosine has not been found in any other DNA, and until recently it was the only case of a normal base completely replaced by an analogue, but it has now been found that the DNA of bacteriophage SP8 of Bacillus subtiEis contains 5-hydroxymethyluracil in place of thymine. 32 The synthesis of this compound has been previously reported,33 and its structure confirmed by a study of its infrared spectrum.34 The antibiotic bacimethrin has been identified as the 2-methyl ether of 5-hydroxymethylcytosine 35 and is an analogue of the pyrimidine portion of thiamine and of the biologically active corresponding 2-methylthio-compound, m e t h i ~ p r i m . ~ ~ There has been further work on the minor bases in ribonucleic acid (RNA). 6-Methylaminopurine is produced by the alkaline rearrangement of l-methyladenine; acid hydrolysis of RNA shows that only E. coli actually contains this base, whereas yeast and liver RNA contain 1-meth~ladenine.~ The methyl groups of the methylated purines and of RNA-thymine are derived from methionine 38 (the methyl group of DNA-thymine is derived from formate or serine via folic acid) and it appears that an enzyme exists in E. coli which can methylate the base components of soluble (transfer) RNA (s-RNA) when the latter are already in polynucleotide form.39 The reaction of reduced vitamin B,, with s-adenosylmethionine gives methylcobalamin, conceivably the actual biological methylating agent .40 I n a study of the proton mobility of substituted uracils it was reported 41 that the lability of the N(3,-protonof thymine does not differ significantly from that of uracil, and the lability of N(3)-protonof 6-azauracil falls in the same range, though slightly more so, as do the N(3,-protonsof thymine and uracil. Nuc1eosides.-The synthesis of nucleosides has been reviewed 42 and it has been pointed out that the direct synthesis of 2-deoxynucleosides, e.g., 2-deoxycytidine,4 3 from pyrimidine mercury salts, probably involves an O+N-glycosyl rearrangement ;42 O+N-alkyl rearrangements are readily brought about in pyrimidine~.~4 Reaction of the silver salt of N-acetyl3 0 L. J. Bello, M. J. V. Bibber, and M. J. Bessman, Biochim. Biophys. Acta, 1961, 53, 194. 31H. V. Aposhian and A. Kornberg, J. Biol. Chem., 1962, 237, 519. 3 2 R. G. Kallen, M. Simon, and J. Marmur, J. Mol. Biol., 1962, 5, 248. 33 R. E. Cline, R. M. Fink, and K. Fink, J. Amer. Chem. SOC., 1959, 81, 2521. 3 4 T. L. V. Ulbricht, Naturwiss., 1958, 45, 416.
35 H. C. Koppel, R . H. Springer, R. K. Robins, and C. C. Cheng, J . Org. Chem., 1962, 27, 1492. 313 T. L. V. Ulbricht and J. S. Gots, Nature, 1956, 178, 913; R . Guthrie, M. E. Loebeck, and M. J. Hillman, Proc. SOC. Exp. Biol. Med., 1957, 94, 792. 37 D. B. Dunn, Biochim. Biophys. Acta, 1961, 46, 198. 38 L. R. Mandel and E. Borek, Biochem. Biophys. Res. Comm., 1961, 4, 14; 1961, 6, 146; B. B. Biswas, M. Edmonds, and R . Abrams, ibid., p. 146. 39 E. Fleissner and E. Borek, Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 1199. 4 0 W. Friedrich and E. Konigk, Biochenz. Z . , 1962, 336, 444. 41 J. P. Kokko, L. Mandell, and J. H. Goldstein, J. Amer. Chem. SOC., 1962, 84, 1042. 4 2 T. L. V. Ulbricht, Angew. Chem., Internat. Ed., 1962, 1, 476. 43 J. J. Fox, N. C. Yung, I. Wempen, and M. Hoffer, J. Amer. Chem. SOC., 1961, 83, 4066. 4 4 T. L. V. Ulbricht, J., 1961, 3345.
ULBRICHT: NUCLEIC ACIDS
375
cytosine with a glycosyl halide gives an O-glycoside, which rearranges to the N-glycoside with mercuric br0mide.~5 The finding that a similar rearrangement can occur in an O-glycoside of 2-hydroxypyridine but not of 4-hydroxypyridine 4 6 supports a suggested mechanism in which the key step is the formation of a mercuric complex on the nitrogen atom ortho to the O-glycoside group :45 it is hardly consistent with a mechanism involving ionisation to give a glycosyl c a t i ~ n , ~ e particularly as these reactions are carried out in non-polar solvents. The yield in the synthesis of 4(6)-azauridine can be raised from 14% 4 7 to 25% 48 by using an azauracil with a protecting group on N-1 (the most acidic position-in uracil it is N-3), but six steps are required in place of two. A general synthesis of pyrimidinyl B-D-arabinosides has been rep~rted.~g 3-Deoxyadenosine can be synthesised by the reaction of the corresponding p-nitrobenzenesulphonic ester with iodide ion and subsequent reduction since a cyclonucleoside cannot be involved as an intermediate, this synthesis shows that by using a more reactive secondary sulphonyl ester nucleophilic displacement can be achieved. An alternative synthesis of 3-deoxyadenosine has also been reported. 51 The reaction of 0,2-cyclouridine with iodide ion in the presence of acid 52 has been extended to the synthesis of 2-fluoro-, 2-chloro-, and 2-bromodeoxyuridine;53 the mechanism of these reactions is strictly analogous to that of the dealkylation of alkoxypyrimidines by iodide ion in the presence of acid.44 Uridine and cytidine on treatment with polyphosphoric acid give, not only the expected diphosphates of the above nucleosides, but also those of spongouridine and of 3- B- D - arabofuranosylcytosine.54 0,2-Cyclonucleosides are intermediates and can be isolated. The ultraviolet spectra of the The uric acid riboside from beef blood suggest that it is the 3-rib0side.~~ structure of the vitamin B,, co-enzyme has been reported;56 in it, the 5methylene group of the ribose is directly linked to cobalt. A partial synthesis, analogous to cyclonucleoside formation, is achieved by reaction of fully reduced hydroxocobalamin and 2,3-isopropylidene-5-tosyladenosine. The structure of pseudouridine has been confirmed by syntheses 4 2 , 5 8 by using a pyrimidine-lithium intermediate, as previously suggested for
T. L. V. Ulbricht, Proc. Chem. SOC., 1962, 298. G. Wagner and H. Pischel, Arch. Pharm., 1962, 295, 373. 4 7 R. E. Handschumacher, J . Biol. Chem., 1960, 235, 764. 4 8 M. Prystas, J. Gut, and F. Sorm, Chem. and Ind., 1961, 467. 4 0 E. J. Reist, J. H. Osiecki, L. Goodman, and B. R. Baker, J . Amer. Chem. Soc., 1961, 83, 2208. 5 0 Sir Alexander Todd and T. L. V. Ulbricht, J., 1960, 3275. 51 W. W. Lee, A. Benitez, C. D. Anderson, L. Goodman, and B. R. Baker, J . Amer. Chem. Soc., 1961, 83, 1906. s 2 D. M. Brown, D. B. Parihar, and Sir Alexander Todd, J., 1958, 4242. 5 3 J. F. Codington, I. Doerr, D. Van Praag, A. Bendich, and J. J. Fox, J . Amer. Chem. SOC.,1961, 83, 5030. 54 E. R. Walwick, W. K. Roberts, and C. A. Dekker, Proc. Chem. Soc., 1959, 84. 5 5 D. Hatfield and H. S. Forrest, Biochim. Biophys. Ada, 1962, 62, 185. 6 6 P. G. Lenkert and D. C. Hodgkin, Nature, 1961, 192, 937. 5 7 K. Bernhauer, 0. Miiller, and G. Muller, Biochem. Z.,1962, 336, 102; E. L. Smith, L. Mervyn, A. W. Johnson, and N. Shaw, Nature, 1962, 194, 1175. 5 8 R. Shapiro and W. Chambers, J . Amer. Chem. SOC.,1961, 83, 3921.
45 46
376
ORGANIC CHEMISTRY
making pyrimidinyl C-glycosides,59and by its conversion into the 06,5-cyClonucleoside.60 The biosynthetic pathway is not yet clear, but probably involves uridine and possibly 3,5-diribo~yluracil.~l curious finding is that A a PeniciZZium species contains enzymes which catalyse the conversion of pseudouridine into pseudoisocytidine.62 The mutagenic activity of hydroxylamine 63 has led to investigations of its chemical reaction with pyrimidine nucleosides. The reaction with uridine or uridylic acid causes ring fission with formation of 5-isoxazolone and ribose oxime 64 and is fastest at pH 10, whereas the optimum pH for reaction with cytidine is 6. A t this pH or in anhydrous hydroxylamine, cytosine derivatives react by addition of one molecule of hydroxylamine to the 45double bond followed by exchange a t N-6, the final product being an N(6) hydroxycytosine derivative.65 The compound responsible for the blue colour in the Dische reaction used for estimating deoxyribose has been shown to be p-acetylacraldehyde.66 Nucleotides and Polynuc1eotides.-Details have been published of the synthesis of nucleotides by use of 2-cyanoethyl phosphate 67 and pyrophosphoryl chloride 68 as phosphorylating agent. A new synthesis of nucleotides involves 2,3-di-0benzoyl-5- diphenoxyphosphinyl-D -ribofuranosyl bromide as the key intermediate.69 Two syntheses of coenzyme A have appeared.709 71 That by Moffatt and Khorana 70 yields a mixture with isocoenzyme A requiring a difficult separation as the last step; Michelsons synthesis 71is an example of a general method for nucleotide anhydrides, by anionic displacement of diphenyl phosphate from an intermediate triesterified pyrophosphosphate) P2P2-diphenylpyrophosphate. 72 PI-Adenosine 5-(2,3-cyclic phate with pantethine 4,4-bisphosphate gave the 2,3-cyclic phosphate of oxidised coenzyme A, which was cleaved by takadiastase ribonuclease T, to the 3-phosphate exclusively. Conversion into the thiol form and chromatographic purification gave the lithium salt of coenzyme A in an overall yield of 63% from adenosine diph0sphate.7~ In another synthesis of nucleotide anhydrides, 73 nucleotide-imidazole compounds are used : adenosine monoT. L. V. Ulbricht, Tetrahedron, 1959, 6, 225. W. E. Cohn and A. M. Michelson, Biochemistry, 1962, 1, 490. J. B. Hall and F. W. Allen, Biochim. Biophys. Actu, 1960, 39, 557; 1960, 45, 163; A. W. Lis and F. W. Allen, ibid., 1960,44,224;P . W. Robbins and J. B. Hammond, J . B o . Chem., 1962, 237, PC 1379; J. K. Pollak and H. R. V. Arnstein, Biochim. il Biophys. Acta, 1962, 55, 798. 6 2 A. W. Lis and F. W. Allen, Biochim. Biophys. Acta, 1962, 61, 250. 63 E. Freese, E. Bautz, and E. B. Freese, Proc. Nut. Acad.Sci. U.S.A., 1961,47,845. 6 4 H. Schuster, J. Mol. Biol., 1961, 3, 447; D. W. Verwoerd, H. Kohlhage, and W. Zillig, Nature, 1961, 192, 1038. G 5 D. M. Brown and P. Schell, J. Mol. B o . 1961, 3, 709. il, G 6 L. Birkofer and R . Dutz, Annulen, 1962, 657, 94. 6 7 G . M. Tener, J. Arner. Chem. SOC., 1961, 83, 159.
59
6o
W. Koransky, H. Grunze, and G . Miinch, 2. Natzcrforsch., 1962, U b , 291. T. Ukita and H. Hayatsu, J. Amer. Chem. SOC.,1962, 84, 1879. 7 0 J. G . Moffatt and H. G . Khorana, J. Amer. Chem. SOC.,1961, 83, 663. 71 A. M. Michelson, Biochim. Biophys. Acta, 1961, 50, 607. 7 2 A. M. Michelson, Colloquium on Nucleic Acids and Polyphosphates, Strasbourg, July 1961 (Editions C.N.R.S., Paris, 1962, p. 39). 73 F. Cramer and G . Weimann, Chem. Ber., 1961,94,996; F. Cramer, H. Neunhoffer, K. H. Scheit, G . Schneider, and J. Tennigkeit, Angew. Chem,, Internat. Ed., 1962, 1, 331.
68
377
phosphate (AMP)reacts with imidazole and trichloroacetonitrile to give a n AMP-imidazole which gives adenosine diphosphate (95%) with orthophosphate, and flavin adenine nucleotide (62%) with riboflavin 5-phosphate, Similarly, uridine monophosphate-imidazole reacts with glucose 1-phosphate to give uridine diphosphate-glucose (67%). New syntheses of adenyloyl ~ulphate,7~ thymidine diphosphate glu~ose,~ uridine diphosphateof and glucuronic acid 74 have been accomplished. A large number of new nucleotide anhydrides of the nucleoside diphosphate-sugar type have been isolated. Chemical synthesis of specifically 3,5-linked ribonucleotides and of polynucleotides has made little progress since a recent review.76 A number of 3,5-linked dinucleotides have been synthesised in 25--40y0yield,77but the methods lack the simplicity essential if polynucleotides are to be prepared by them. Cohn and his colleagues 78 have continued work on the cleavage of the phosphate of periodate-oxidised 5-nucleotides, which proceeds at pH < 8 after formation of an amine addition product at pH > 10; the method is very useful for determining sequences of short oligonucleotides. The catalytic oxidation of the hydroxymethyl group in nucleosides 7 9 has been developed into a method 8 0 which may be applicable to the stepwise degradation of deoxyribopolynucleotides. Thymidinyl-5, 3-thymidine mas oxidised to the carboxylic acid and converted into the amide (3) which undergoes base-catalysed elimination to thymidine-5 phosphate (97%), thymine (69%), and what may be anhydrothpmidine uronic acid (23%).
PrHN*CO /O,
Thymine
n
un
( R = 5-Thymidinyl)
The key intermediate in the metabolic conversion of nucleotides into deoxynucleotides remains to be determined. Reichard has shown that with cytidine-5 phosphate, conversion into the pyrophosphate is necessary, followed by a reduction requiring adenosine triphosphate, Mg2f, and lipoic acid. The incorporation of [2-14C]cytidine-[H3]ribosylinto the deoxycytidine of DNA without significant loss of tritium from the sugar S 2 indicates that the reduction does not involve loss of hydrogen from the 2-position.
A. M. Michelson and F. Wold, Biochemistry, 1962, 1, 1171. R. Okazaki, T. Okazaki, J. L. Strominger, and A. M. Michelson, J . BioZ. Chem., 1962, 237, 3014. 13 A. M. Michelson, Ann. Rev. Biochem., 1961, 30, 130. 7 7 J. Smart and F. so-, CoZE. Czech. Chem. Comm., 1962, 27, 86; D. H. Rammler and H. G. Khorana, J . Amer. Chem. SOC., 1962, 84, 3112. 7 8 W. E. Cohn and J. X. Khym, Colloquium on Ribonucleic Acids and Polyphosphates, Strasbourg, July 1961 (Editions C.N.R.S., Paris, 1962, p. 217). 7 9 C. B. Reese, K. Schofield, R. Shapiro, and Sir A. Todd, Proc. Chern. SOC., 1960, 261. J. P. Vizsolyi and G. M. Tener, Chem. and Ind., 1962, 263. *l P. Reichard, J . Biol. Chem., 1962, 237, 3513. 8 2 R. Y . Thompson, G. T. Scotto, and G. B. Brown, J . Biol. Chem., 1962, 237, 3510.
74 75
378
ORGANIC CHEMISTRY
A natural copolymer of deoxyadenylic and thymidylic acid has been isolated from the DNA of a marine crab, Cancer borealis, by chromatography on kieselguhr impregnated with methylated albumin. It constitutes 30% of the total DNA 83 and has alternating adenine and thymine residues, with a guanine and cytosine content of 3%.84 Synthesis of a polymer of deoxyguanylate and deoxycytidylate has now been achieved from the triphosphates by using the DNA polperase from E. coli, in the absence of added primer, and after an extended lag period.s5 A synthetic trinucleotide of deoxyguanosine appears to be highly aggregated in 0.25~1-phosphate buffer a t pH 6.8, having Tm = 58" and = 10-12.s6 The synthesis of polyriboguanylic acid by means of polynucleotide phosphorylase has now been accomplished with low concentrations of guanosine diphosphate and Mg2f and a high concentration of enzyme ;87 previous failures to synthesise polyguanylic acid may have been due to an inhibition of the enzyme by a multistranded helical form of guanosine oligonucleotides. There is an excellent recent survey of nucleic acid biosynthesis by Grunberg-Manago.2 Physical chemistry. A very important paper is that of Spencer, Fuller, Wilkins, and G. L. Brown 88 on the X-ray diffraction of crystalline s-RNA which indicates that it has a helical structure similar to that of DNA type A. It consists of a single strand folded back on itself, the two halves of the chain being anti-parallel. The region where the strand folds back forms it loop in which the bases (perhaps three in number) are unpaired. Other physical properties of s-RNA also indicate that it has a highly asymmetric, relatively rigid secondary structure, more like DNA than like high-molecular-weight RNA. 89 There is also evidence suggesting that pseudouridine and the methylated bases are concentrated in the central region of S-RNA,~O and on this basis a model of s-RNA has been proposed 91 which is very like the structure proposed by Spencer et al. except that the loop is thought to contain about 20 residues. Doty 92 has reviewed the physical chemistry of polynucleotides and nucleic acids. The base composition of DNA can be determined by a number of purely physical measurements:the &260/&280 ratio a t pH 3,93 the buoyant density in czesium chloride,g4and, perhaps most accurately, the denaturation temperature. 95 Electron micrographs of deoxyribonucleoproteinfrom M . lysodeikticus show a tangled skein without free ends,96 and autoradiography of labelled DNA obtained from E. coli
83 N. Sueoka and T. Cheng, J. Mol. Bwl., 1962,4, 161 ; Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 1851. 8 4 M. N. Swartz, T. A. Trautner, and A. Kornberg, J . Biol. Chem., 1962, 237, 1961. 8 5 C. M. Radding, J. Josse, and A. Kornberg, J . BioE. Chern., 1962, 237, 2869. 86 R. K. Ralph, W. J. Connors, and H. G. Khorana, J . Amer. Chem. SOC., 1962, 84, 2265. 87 J. R. Fresco and D. Su, J . BioZ. Chem., 1962, 237, P C 3305. 8 8 M. Spencer, W. Fuller, M. H. F. Wilkins, and G. L. Brown, Nature, 1962, 194, 1014. 8 9 S . W. Luborsky and G. ,L. Cantoni, Bwchim. Biophys. Acta, 1962, 61, 481. 9 0 T. Nihei and G. L. Cantoni, Biochim. Biophys. Acta, 1962, 61, 463. 01 K. S. McCully and G. L. Cantoni, J . MoZ. Biol., 1962, 5, 497. 9zP. Doty, J . Polymer Sci., 1961, 55, 1. 93 A. Fredericq, A. Oth, and F. Fontaine, J . Mol. BioZ., 1961, 3, 11. 9 4 C. L. Shildkraut, J. Marmur, and P. Doty, J. MoZ. Biol., 1962, 4, 430. 95 J. Marmur and P. Doty, J . Mol. Biol., 1962, 5, 109. OeA. Kleinschmidt, D. Lang, and R. K. Kahn, 2. Nuturforsch., 1961, 16b, 730.
379
by gentle lysis is consistent with a length of at least 400 p and a molecular weight of I09 or more,97suggesting that bacterial DNA may exist as a single molecule. The usual methods of extraction probably break molecules by shearing. Effective and mild methods of denaturing DNA in solution (breaking hydrogen bonds) are the addition of high proportions of glycol and of glycerol, which increase the relative absorbance a t 260 mp at room temperature,98 and of formamide; measurements of the infrared spectra 99 of sodium salts of nucleic acids treated with formamide and of the optical rotatory dispersion 100 indicate that nucleic acids have no secondary structure in this solvent. Further studies of the DNA of bacteriophage $X 174, which appears to be single-stranded, show that the replicative form has several properties similar to those of double-stranded DNA, and that the normal, singlestranded form, when undegraded, probably has a covalently linked ring structure. lo1 The Genetic Code and Protein Synthesis.-Only a few of the results recently obtained in this, by far the most active, area of currenti nucleic acid research can be mentioned here, and attention is directed to other reviews for further detailsa2* Jacob and Monod,lo3 in their theory of protein lo2 synthesis, postulated the existence of a special form of RNA, short-lived, and with a base-composition complementary to that of DNA, which carries the necessary information from the nucleus to the ribosomes, where protein synthesis takes place. High turnover in a minor RNA fraction after phage infection of E . coli, this fraction having a nucleotide composition corresponding to that of phage DNA, had already been d e m 0 n ~ t r a t e d . l ~ ~ Further experiments with E . coli showed that, after infection with T2-bacteriophage, no new ribosomes can be detected, and a fraction corresponding in properties to messenger RNA is found to be added to pre-existing ribosomes.lo5 The technique of pulse-labelling has been of great value in connexion with these experiments; that is, after addition of the DNA primer to the system (which may be a living cell, or an in vitro system containing RNA polymerase), labelled RNA precursors are made available for a very short time only. It is then found that a fraction with the postulated properties of messenger RNA is labelled first ; only subsequently is ribosomal RNA labelled. In this manner it has been possible to synthesise an RNA with a base composition complementary to that of the priming DNA used with an RNA polymerase from E. coli in vitro,lo6and similarly to show the formation of an RNA
J. Cairns, J . MoZ. Biol., 1962, 4, 407. E. L. Duggan, Biochem. Biophys. Res. Comm., 1961, 6, 93. O D Y. Kyogoku, M. Tsuboi, T. Shknanouchi, and I. Watanabe, J . MoZ. BWZ. 1961, , 3, 741. loo P. 0. P. TsO, G. K. Helmkamp, and C . Sander, Biochim. Biophys. A c h , 1962, 55, 584. lol R. L. Sinsheimer, B. Starman, C. Naylor, and S . Guthrie, J . Mol. BioZ., 1962, 4, 142; W. Fiers and R . L. Sinsheimer, ibid., 1962, 5, 424. lo2 P. C. Zamecnik, Biochem. J., 1962, 85, 257. lo3 F. Jacob and J. Monod, J . MoZ. BioZ., 1961, 3, 318. lo*E. Volkin and L. Astrachan, Virology, 1956, 2, 149. lo5 S. Brenner, F. Jacob, and M. Meselson, Nature, 1961,190, 576; F. Gros, H. Hiatt, W. Gilbert, C. G. Kurland, R. W. Risebrough, and J. D. Watson, ibid., p. 581. log M. Chamberlain and P. Berg, Proc. Nut. Acud. Sci. U.S.A., 1962, 48, 81.
O7
98
380
ORGANIC CHEMISTRY
complementary to DNA in ~ i ~ 0 . 1 0 7Many authors have reported similar results-DNA-dependent synthesis of an RNA of the messenger type-in mammalian systems, lo8and messenger RNA has also been demonstrated in pea seedlings.loD Specific hybrid formation has been shown to occur between T2-DNA and the RNA synthesised in E . coli infected withT2,110 and T4-specific RNA has been separated from E. coli RNA by chromatography on columns of cellulose linked t o T4-DNA.l11 Hybrid formation has also been shown to occur between ribosomal RNA and homologous DNA from E. C O Z ~ ,indicating that there is a sequence in DNA complementary ~ ~ ~ t o its ribosomal RNA although, as a whole, they are not complementary. All these results are consistent with the theory that DNA is the fundamental source of information in living systems which is passed on by a template mechanism in the formation of RNA. Japanese workers have made important contributions. 113,114 Ribosomal RNA appears to be first; formed on DNA and finally built into a complete ribosomal particle by sequential intermediate steps, including a DNA-RNA complex in which the RNA is not complementary to DNA but has the composition of ribosomal RNA.l13 Development of a method for the isolation of undegraded messenger RNA from E. coli 114 has made it possible to show that it is heterogeneous, consisting of four main components of differing sedimentation coefficients. There is not, however, a precursorproduct relationship among them. Chloramphenicol specifically inhibits the synthesis of the highest-molecular-weight messenger RNA (23 to 305) which is the only one found t o associate with 708 ribosomes (active in protein synthesis) in vitro. The discovery, reported in a classic paper by Nirenberg and Matthaei,l15 that, in a protein-synthesising system, addition of polyuridylic acid led t o the synthesis of polyphenylalanine from phenylalanine, initiated a period of frenzied activity devoted to " cracking the genetic code," the latest results being reported in the New York Times. By assuming a non-overlapping triplet code 116 (three adjacent nucleotide residues coding for one amino-acid) it was soon possible t o propose a complete code on the basis
M. Takai, N. Kondo, and S. Osawa, Biochim. Biophys. Acta, 1962, 55, 416. P. Cheng, Biochim. Biophys. Actu, 1961, 53, 232; A. Sibatani, S. R. de Kloet, V. G. Allfrey, and A. E. Mirsky, Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 471; H. H. Hiatt, J. MoZ. BioZ., 1962, 5, 217; P. A. Marks, C. Willson, J. Kruh, and F. Gros, Biochem. Biophys. Res. Comm., 1962, 8, 9. log U. E. Lohning, Nature, 1962, 195, 467. 110 B. D. Hall and S. Spiegelmann, Proc. Nat. Acad. Sci. U.S.A., 1961, 4'7,
107
los
137.
E. K. F. Bautz and B. D. Hall, Proc. Nut. Acad. Sci. U.S.A., 1962, 48,
S. A. Yankovsky and S. Spiegelmann, Proc. Nat. Acad. Sci. U.S.A., 1962, 48,
400.
112
1069.
113 E. Otaks, S. Osawa, Y. Oota, A. Ishima, and H. Mitsui, Biochim. Biophys. Acta, 1962, 55, 310. 114 A. Ishima, N. Mizuno, M. Takai, E. Otaka, and S. Osawa, J. Mol. BioZ., 1962, 5, 251. 115 M. W. Nirenberg and J. H. Matthaei, Proc. Nut. Acad. Sci. U.S.A., 1961, 47, 1588. 116 F. H. C. Crick, L. Barnett, S. Brenner, and R. J. Watts-Tobin, Nature, 1961, 192, 1227.
381
of these results.11' All the triplets contained uracil and Chargaff 118 calculated that messenger RNA for bovine ribonuclease would have to have the following composition: adenine, 16-9; guanine, 15.9; cytosine, 20-7; and uracil, 46.5%;which appeared very unlikely, to say the least. An investigation of satellite tobacco necrosis virus indicated that 60% of its RNA chain would be required to code for its protein and that the uracil content was such that all of it would have to be in this portion of the chain if the code were correct; also the maximum number of nucleotide residues between two uracils cannot exceed four in the coding part. Analysis of the oligonucleotides obtained by the action of pancreatic ribonuclease showed that these requirements were not fulfilled.119 It seems that 6he requirementi for uracil is an accident of the experimental system, uracil conferring some desirable property on the polynucleotide chain; it has been noted above that even a trinucleotide of deoxyguanosine has a complex secondary structure and this may well explain the failure to achieve incorporation of amino-acids with polymers containing high proportions of guanylic acid. Some of the coding assignments made have depended on the assumption that the composition of the polynucleotide is the same as that of the mixture of monomers from which it was prepared; this has been strongly criticised by Bretscher and Grunberg-Manago 120 who determined the exact ratios in the polymers they used and found them to be often very different from the original ratio of diphosphates. The same authors consistently found incorporation of small amounts of leucine with polyuridylic acid in addition to phenylalanine; since triplets are assigned on the basis of the ratio of incorporation of the amino-acid to that of phenylalanine as standard, they point out that assignments on the basis of small amounts of incorporation may be incorrect. They also obtained some incorporation of amino-acids with polycytidylicadenylic acid. The general conclusion now appears to be that the code is degenerate. Similar incorporations of amino-acids stimulated by added polynucleotides have been obtained in other systems.121 I n other tests of the universality of the genetic code, it has been found that tobacco-mosaicvirus-RNA directs the synthesis of a protein similar to this virus-protein in an E. coli system,122 and that addition of ribosomal RNA from E . coli cells induced to form /?-galactosidaseled to the synthesis of this enzyme when added to a homologous (E. coli) cell-free system; when this RNA was added to a heterologous system (Pseudomonus pyocyuneus) protein synthesis occurred but enzyme was not produced.123
1 ' P. Lengyel, J. F. Speyer, and S. Ochoa, Proc. Nut. Acad. Sci. U.S.A., 1961, 1 47, 1936; J. F. Speyer, P. Lengyel, C. Basilio, and S. Ochoa, ibid., 1962, 48, 63, 282, 441; C. Basilio, A. J. Wahba, P. Lengyel, J. F. Speyer, and S. Ochoa, ibid., p. 613; J. H. Matthaei, 0. W. Jones, R. G. Martin, and M. W. Nirenberg, ibid., p. 666. 118 E. Chargaff, Nature, 1962, 194, 86. 119 M. E. Reichmann, M. W. Rees, R. H. Symons, and R. Markham, Nature, 1962, 195, 999. l Z o M. S. Bretscher and M. Grunberg-Manago, Nature, 1962, 195, 283. lZ1 E. S. Maxwell, Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 1639; H. R. V. Arnstein, R. A. Cox, and J. A. Hunt, Nature, 1962, 194, 1042. l Z 2 A. Tsugita, H. Fraenkel-Conrat, M. W. Nirenberg, and J. H. MatLhaei, Proc. V a t . Acad. Xci. U.S.A., 1962, 48, 846. 1 2 3 B. R. Chatterjee and R. P. Williams, Biochem. Biophys. Res. Comm., 1962 $9,72.
382
ORGANIC CHEMISTRY
Of the theoretical and speculative papers on the nature of the genetic code, that by Woese is worthy of note.124 He suggests a degenerate triplet code, in which one member of the triplet codes according t o its 2 position only, a second codes according to its 6 position only, while the third codes according to positions 2 and 6. This gives a code of 24 sets of triplets and is in good agreement with experimental results;l17 perhaps even more interesting is that it accounts for the wide variation in guanine-cytosinecontent which is found in bacterial DNA. Many authors have " tested " the code by applying it to amino-acid replacement data, but Hendler,125 with good reason, has questioned the conclusions reached. Statistical analysis of the probabilities involved (e.g., that code designations of two amino-acids will be related by only a single nucleotide difference)shows that a considerably larger number of correlations is required. The findings that DNA-primed RNA synthesis in mouse fibroblasts can be inhibited by actinornycin D without significant interference with the production of an infectious RNA virus,126 and that RNA-primed RNA nucleotidyl-transferase activity is increased in Krebs I1 ascites tumour cells on infection with EMC virus,127 suggest that replication of some RNA viruses may be dependent on RNAand not on DNA-primed synthesis of RNA. Work on the fractionation and purification of s-RNA, which transfers the amino-acids to the ribosomes, has involved a variety of methods, including counter-current distribution.12* It has been found that E . coEi contains two leucine-acceptor s-RNA's, which are separable by this technique. Ribosomal incorporation of leucine attached to one of these is stimulated by polyuridylic-cytidylicacid, the other by polyuridylic-guanylic acid,129 explaining the degeneracy observed in coding experiments with leucine 117 and incidentally confirming the view that coding specificity is carried by s-RNA. This had already been shown by an ingenious experiment in which cysteine attached to its s-RNA was treated with Raney nickel to give alanine-s-RNA(cysteine). This was found to be active in an incorporating system in which cysteine-s-RNA( cysteine) is active but alanines-RNA-(alanine) is inactive.l 3 0 The nucleotide sequence in s-RNA, next to the common terminal sequence cytidylic-cytidylic-adenylic, varies and is different in isoleucine- and leucine-specific s-RNA.131 Studies of the actual transfer process indicate 132 that in the course of
C. R. Woese, Nature, 1962, 194, 1114. R . W. Hendler, Proc. Nut. Acad. Sci. U.X.A., 1962, 48, 1402. . E. Reich, R. M. Franklin, A. J. Shatkin, and E. L. Tatum, Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 1.238. 1 2 7 R . Eason, M. J. Cline, and R. M. S. Smellie, Biochim. Biophys. Acta, in the press. 1 2 8 J. Agar, R. W, Holley, and S. H. Memill,, J. Biol. Chem., 1962, B , 7 796; 3%.L. Stephenson and P. C. Zamecnik, Biochern. Biophys. Res. Comm., 1962, 7, 91; M. Tsda, M. Schweiger, and H. G. Zachau, 2. physiol. Chem., 1962, 328, 85; G. Zubay, J. Mol. Biol., 1962, 4, 347. 1 2 9 B. Weisblum, 5. Benzer, and R. W. Holley, Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 1449. 1 3 0 F. Chapeville, F. Lipmann, G. Van Ehrenstein, B. Weisblum, W. J. Ray, jun., and S. Benzer, Proc. Nut. Acad. Sci. U.X.A., 1962, 48, 1086. 131 U.Lagerkvist and P. Berg, J. Mol. Biol., 1962, 5,-139; P. Berg, U. Lagerkvist, and M. Dieckmann, ibid., p. 159. 1 3 2 M. Takanami, Biochim. Biophys. Acta, 1962, 55, 132.
124 125
ULBRICHT:
NTJCLEIC A C I D S
383
amino-acid transfer to ribosome, the s-RNA itself is also transferred, a process requiring guanosine triphosphate and occurring whether an amino-acid is attached at the acceptor end or not, provided the terminal sequence cytidyliccytidylic-adenoylic-apparently necessary for the binding of s-RNA to ribosome-is intact. This has been confkmed ; stimulation by adenosine triphosphate is due to restoration of the terminal sequence.133 It appears that one molecule of guanosine triphosphate is degraded for each molecule of amino-acid transferred from s-RNA to protein. 134 Finally, attention is drawn to Lord Todds addresses to the Chemical Society, in which some problems in the field of Nucleic Acid Chemistry are considered in a wider context. 135
T. L. V. U. R. &I.ACHESON. G. C. BARKER. K. W. BENTLEY. C. J. W. BROOKES. B. CAPON. L. CROMBIE. G. EGLINGTON. J. ELKS. V. GOLD.
G. W. GRAY. J. HONEYMAN.
D. J. IMILLEN. K. H. OVERTON. C. W. REES. D. H. REID. T. L. V. ULBRICHT. R. F. M. WHITE.
w. KJLYNE.
133 H. Bloemendal, F. Huizinga, M. de Vries, and L. Bosch, Biochim. Biophys. Acta, 1962, 61, 209; L. Bosch, F. Huizinga, and H. Bloemendal, ibid., p. 220. 13* G. Webster and S. L. Whitman, Biochim. Biophys. Acta, 1962, 61, 316. 135 (Sir)A. Todd, Proc. Chen?,. SOC., 1961, 187; Lord Todd, Proc. Chent. SOC., 1962, 190.
BIOLOGICAL CHEMISTRY
1 INTRODUCTION .
IT has now been established that d-aminolaevulic acid contributes all the carbon and nitrogen atoms of the haem of haemoglobin, myoglobin, cytochromes, peroxidase, and catalase as well as those of the dihydroporphyrin of chlorophyll and of the tetrahydroporphyrin of bacteriochlorophyll. Recent work also shows that d-aminolaevulicacid is incorporated intact into the corrin ring of vitamin BIZ,but a number of additional carbon atoms, in the form of methyl groups, are provided by methionine. The paramount position of 6-aminolaevulicacid was already recognised when the last Report was presented,l and in the intervening years much has been learned of the enzymes involved in its formation and in its conversion into porphyrins. These studies have also brought t o light certain inhibitory processes, which could exert control over porphyrin biosynthesis. Of particular interest is the finding that protohaemin I X is a powerful inhibitor of 6-aminolaevulic acid synthetase, thus indicating the possibility of control by the negative feed-back effect of the final product on the first enzymic step. Studies of vitamin B,, have been concerned less with its biosynthesis than with its metabolic r61e and this remains somewhat enigmatic. It seems unlikely that the vitamin or its coenzyme derivatives play a very important part in one-carbon metabolism-a possibility which has been extensively investigated. In spite of many observations which point to a function in the biosynthesis of deoxyribonucleosides, clear-cut evidence of the importance of such a r61e is lacking and thymidine is ineffective in the treatment of pernicious anzmia. An important break-through may have been made by the finding that vitamin B,, coenzymes function in isomerase systems involving the migration of carboxyl groups, in particular that causing conversion of methylmalonate into succinate. I n man, in vitamin B,, deficiency, the level of methylmalonate in the urine is always higher than normal and is reduced when the vitamin is administered. This raises the question whether the neurological symptoms of pernicious anaemia could be due t o an accumulation of methylmalonate. Investigations of the biological and chemical properties of nicotinamideadenine dinucleotide analogues have shed light on the structural requirements for coenzymic activity. They have revealed the expediency of the carbamoyl group attached t o the pyridine ring and that of the ribose portion as against one of deoxyribose. I n certain of the dehydrogenase enzymes considerable variation in the structure of the purine portion seems to be permissible. The apoenzymes have aroused considerable interest as a result of the recognition of the existence of isozyrnes-enzymes of the same activity and from a single species which differ from one another in the structures of their sub-units. This is reminiscent of the behaviour of the haemoglobins and it may transpire that the structures of the sub-units are under genetic
Ann. Reports, 1954.
51, 311.
MARKS: T H E B I O S Y N T H E S I S O F P O R P H Y R I N S
385
control. The year has been marked by an outstanding contribution t o the stereochemistry of nicotinamide-adenine dinucleotide in its function as a coenzyme. The absolute alignment, relative to the pyridine ring, of the hydrogen atom transferred between coenzyme and substrate has been established for each of two classes of enzymes in which it was known that hydrogen transfer occurred on one side only of the pyridine ring. Cholesterol, itself formed from acetate, is now known to be the source of many steroid compounds and for the adrenal cortex, at least, it has been established that pathways not involving it are of minor importance. The complexity of the situation is shown, however, by the number of different routes which can lead to any one substance, such as cortisol and the various estrogens; the relative importance of these pathways is not, in general, known. Much has been learned of the processes involved in the aromatisation of ring A. Steroid conjugates, rather than being mere excretory products, may, in some instances, be of considerable importance-a suggestion which has been made on account of the high metabolic activity of some of them.
D. F. E.
2 THE BIOSYNTHESIS OF PORPHYRINS .
WHENthis subject was last reviewed in these Reports eight years agoY1
the key r61e played by 6-aminolzvulic acid and porphobilinogen in the biosynthesis of porphyrins was reported. At that time, it was considered likely that uroporphyrin and coproporphyrin were intermediates in the biosynthesis of hzm and chlorophyll although there was no experimental support for this idea. The recent recognition that uroporphyrinogen and coproporphyrinogen, the colourless reduced forms of uroporphyrin and coproporphyrin, respectively, containing six extra hydrogen atoms, are the true intermediates has been an important advance. Succinyl-CoA has been confirmed as an intermediate in porphyrin biosynthesis and an enzyme, 6-aminolaevulicacid synthetase, has been isolated from various sources which can form 6-aminolzvulic acid from succinyl-Cod and glycine ; pyridoxal phosphate is the only co-factor required. The first two steps in the conversion of protoporphyrin into bacteriochlorophyll have been shown to be protoporphyrin --+ magnesium protoporphyrin -+ magnesium protoporphyrin monomethyl ester. There has been considerable progress in the isolation and purification of the enzymes responsible for porphyrin biosynthesis and studies on the mechanism of control of porphyrin biosynthesis have appeared. Several interesting reviews on porphyrin biosynthesis have been published in recent years, vix., on the metabolism of ham and chlorophyll,2 the biosynthesis of protochlorophyll,3 the biosynthesis of porphyrins and
C. Rimington, Ann. Reports, 1954, 51, 311. S. Granick and D. Mauzerall, i Metabolic Pathways, ed. D. M. Greenn berg, Academic Press Inc., New York, 1961, Vol. 11, p. 525. L. Bogorad, in Comparative Biochemistry of Photoreactive Systems, ed. M. B . Allen, Academic Press Inc., New York, 1960, p. 237.
N
386
B I O L O G I C A L CHEMISTRY
chlorophyll^,^ haem pigments and porphyrin~,~ porphyrins and hzemoand proteins.6 Formation of 6-Aminolaevulic Acid.-In 1953 it was shown 8 that 6-aminolmulic acid could replace succinate and glycine for porphyrin bio: synthesis. This finding led to the proposal that d-aminolaevulic acid was formed from glycine and an asymmetrical succinyl derivative, probably succinyl-CoA, by condensation of these two substances to form a-amino-poxoadipic acid, which is subsequently decarboxylated to d-arninolaevulic acid. That pyridoxal phosphate and coenzyme A were required for this condensation was indicated by the studies of Lascelles 9 on porphyrin synthesis in Tetrahymena vorax and by the studies of Schulman and Richert l o on vitamin B, and pantothenic acid-deficient ducklings. Recently the enzyme which catalyses this reaction, 6-aminolaevulic acid synthetase, has been found in a variety of cells. Gibson et aZ.ll found that a preparation of freeze-dried particles obtained from erythrocytes of anemic chickens synthesised 6-aminolaevulic acid from succinyl-CoA and glycine; pyridoxal phosphate was the only co-factorrequired. This reaction has also been demonstrated with particle-free extracts of Rhodopseudmonas spheroides and Rhodospirillium rubrurn, and the enzyme catalysing the reaction has been purified 60--80-fold from extracts of the former organism.l2 The work of Lascelles 13 indicated that biotin might be involved in the production of 8-aminolevulic acid and recently it has been shown that the activity of 6-aminolaevulicacid synthetase is reduced in biotin-deficientorganisms 14,l5 whereas a number of other enzymes are not affe~ted.1~ This is not, however, a specific effect of biotin, since other growth conditions which are unfavourable t o bacteriochlorophyll synthesis also cause a fall in the activity of 6-a,minolaevulic acid synthetase.14 On the basis of their experimental evidence Kikuchi et aZ.I2 have suggested that a stabilised carbanion (1)is formed from glycine and pyridoxal phosphate by loss of a proton and that this reacts with the electrophilic carbonyl-carbon atom of succinyl-CoA (2). The latter reaction may then proceed in one of two ways: decarboxylation occurs by a concerted attack (pathway b) or the product of condensation is a-amino-p-oxoadipicacid (3) which loses carbon dioxide (pathway a) to yield 8-aminolaevulic acid (4). Because decarboxylation of a-amino-8-oxoadipicacid is virtually instantaneous at room temperature 16 its isolation from a biological system is pre' 9
K. D. Gibson, M. Matthew, A. Neuberger, and G. H. Tait, Nature, 1961, 192,
204.
C. Rimington, Ann. R v Biochem., 1957, 30, 561. e. E. Margoliash, Ann. Rev. Biochem., 1961, 30, 549. D. Shemin and C. S. Russell, J . Amer. Chem. Soc., 1953, 7'5, 4873. * A . Neuberger and J. J. Scott, Nature, 1953, 172, 1093. 9 J. Lascelles, Biochem. J., 1957, 66, 65. l o M. P. Schulman and D. A. Richert, J. BioZ. Chem., 1957, 226, 181. 11 K. D. Gibson, W. G. Laver, and A. Neuberger, Biochem. J., 1958, 70, 71. l 2 G. Kikuchi, A. Kumar, P. Talmage, and D. She&, J . Biol. Chem.., 1958, 233,
13
1214.
14 K. Gibson, A. Neuberger, and G. 16 J. Lascelles, J . Qen. MicrobioZ., 1960,

l6
H. Tait, Biochem. J., 1962, 83, 539. 23, 499. W. G. Laver, A. Neuberger, m d J. J. Scott, J., 1959, 1474, 1483.
J. Lascelles, Biochem. J., 1956, 62, 78.
D.
MARKS: THE BIOSYNTHESIS O F PORPHYRINS
387
cluded and there is no information as to whether it is a free intermediate. A similar overall scheme has been put forward by Neuberger.17 The enzyme preparations obtained by Gibson et aE.ll and by Kikuchi et ~ 1 . 1 2 not specific for succinyl-CoA. Propionyl-CoA, glutaryl-CoA, and are acetyl-CoA also serve as substrates but the reactions are slower. Aminoacetone has been identified as the product with the latter substrate, and products reacting as amino-ketones have been obtained with the other two substrates. From recent experiments by Granick and Urata l8 it seems likely that these reactions, utilising different acyl-CoA substrates, are not catalysed by a single enzyme but that several specific synthetases are present in these preparations. These authors have shown that normal animal liver mitochondria form aminoacetone readily from glycine and pyruvate but only traces of 6-aminolzevulicacid from glycine and a-keto-glutarate. After induction of a chemical porphyria with diethyl 1,4-dihydrocollidine-3,5dicarboxylate the isolated liver mitochondria had the capacity to form large amounts of d-aminolaevulic acid from glycine and citrate. Furthermore, frozen and thawed preparations of these mitochondria have acquired the ability to synthesise 6-aminolzevulic acid from succinyl-CoA and glycine. The synthetase for 6-aminolaevulic acid differs from that for aminoacetone in distribution, in greater sensitivity to penicillamine, and in looser binding of pyridoxal phosphate. No other major change in protoporphyrin biosynthesis is observed in the liver of these porphyric animals. The synthesis of 6-aminolzevulicacid is markedly inhibited by aminomalonate and kinetic investigation has shown this inhibition to be of the competitive type with respect to glycine. Several specific inhibitors of d-aminolaevulic acid synthetase occur naturally. As yet unidentified components of egg-white and of Rps. spheroides l 2 have a specific inhibitory effect on this enzyme and Kikuchi et a2.l2 have suggested that the inhibitor from Rps. spheroides may play an important r61e in the control of porphyrin biosynthesis. They point out that the energy requirement for d-aminolzevulic acid formation would make this step a likely place for the cellular control of porphyrin synthesis. Protohzemin IX has been shown l9 to be a relatively potent inhibitor of d-aminolamlic acid synthetase, causing about 50% inhibition at a concentration of 1 0 - 5 ~ . This inhibition, which is reversible,l9 is quite specific for protohaemin IX, since other metal-porphyrin complexes and the corresponding free porphyrins have little inhibitory action. This is an example
49
l7
A. Neuberger, Biochem. J., 1961, 78, 1. S . Granick and G. Urata, Fed. Proc., 1968, 21, 150. I D B. F. Burnham, Biochem. J., 1962, 84, 15P.
388
of inhibition through a negative feed-back mechanism in which the final product in a metabolic sequence inhibits the first enzymic step leading exclusively to the end product. It is thought that this mechanism may operate in the control of porphyrin biosynthesis. I n earlier investigations Lascelles 13, 2o showed that Bps. spheroides, when cultured in the light under iron-deficient conditions, accumulated large quantities of porphyrin in the medium. The addition of iron resulted in a decreased production of porphyrin, an effect which seemed t o be due to the catalytic action of iron and not to the formation of stoicheiometric amounts of haemin. From the above inhibition experiments it appears that iron added to deficient cultures exerted its catalytic influence on porphyrin formation after incorporation into protohaemin IX, which directly inhibits the activity of Q-aminolaevulic acid synthetase. Succinate-Glycine Cycle.-In an attempt to unify the reactions of glycine Shemin 21 postulated a series of reactions, called the succinate-glycine cycle. According to this postulate, 6-aminolaevulicacid, in addition t o its utilisation for porphyrin synthesis, can be further metabolised in such a manner that its &carbon atom (originally the a-carbon atom of glycine) is utilised for the synthesis of the ureido-group of purines, the #&carbonatom of serine, and methyl groups ; the remaining 4-carbon residue is reconverted into succinate. Although certain experimental results support the existence of this cycle,21, 22 its general metabolic significance remains to be evaluated. Enzyme studies have been restricted to the first reaction in this cycle, wix., the conversion of 6-aminolaevulic into y 6-dioxovaleric acid. An enzyme catalysing this reaction has been demonstrated in mammalian tissues, 23 Bacterium diphtheriae,z4 and Rhodopseudomonas spheroides.l4 It has been suggested that this reaction might provide a control mechanism for the synthesis of h z m and chlorophyll. I n recent work with Rhodopseudomonus spheroides it has been found more convenient t o study the reverse reaction, vix., the conversion of yd-dioxovaleric acid into 6-aminolaevulicacid, because the equilibrium appears t o be in favour of the production of 6-aminolaevulic acid and a sensitive method is available for estimating the amino-ketone. The enzyme catalysing this reaction has been purified thirty-fold 25 and L-alanine found to be the specific amino-group donor. Formation of Porphobilin0gen.-The enzyme catalysing the condensation of two molecules of 6-aminolaevulic acid to porphobilinogen ( 5 ) has been found t o be widely distributed in animal tissues, plants, and bacteria, and has been considerably purified. Bogorad has summarised the properties of several purified 6-aminolaevulic acid dehydrase preparations. Since this is a rare case of an enzyme catalysing a reaction between two identical substrate molecules, Granick and Mauzerall 26 have made a detailed kinetic
2 o J. Lascelles, J . Gen. Microbiol., 1960, 23, 487. 2 l D. Shemin, i Ciba Foundation Symposium on Porphyrin Biosynthesis and n Metabolism, ed. G. W. Wolstenholme, J. and A. Churchill, London, 1955, Vol. IV. 22A. M. Nerneth, C. S. Russell, and D. Shemin, J . Biol. Chern., 1957, 229, 415. 23 E. Kowalski, A. M. Dancewicz, and Z. Szot, Bull. Acad. Polon. Sci., 1957, 11, 5, 223. 2 4 M. Bagdasarian, Natzwe, 1958, 181, 1399. z 5 A. Neuberger and J. M. Turner, personal communication. 2 6 S Granick and D. Mauzerall, J . Biol. Chem., 1958, 232, 1119. .
MARKS: THE BIOSYNTHESIS OF PORPHYRINS
389
investigation of the reaction. On the basis of their data they suggest that both molecules of 6-aminolzevulic acid form complexes with Q-aminolzevulic acid dehydrase, one molecule being held more tightly than the other. Formation of Uroyorphyrinogen III.-The next step in porphyrin biosynthesis is the enzymic conversion of porphobilinogen ( 5 )into uroporphyrinogen I 1 (6). It is clear from the work of Tarlton et aL2' that great care 1
A c* @p H
NH
HN
(6)
is needed in establishing the purity of uroporphyrin isomers. Uroporphyrin I 1 methyl ester cannot be distinguished from a mixture of isomers contain1 ing it by m.p.s, infrared spectra, or X-ray powder photographs so that it is probable that various workers have handled mixtures of uroporphyrin isomers which they have assumed to be uroporphyrin I 1 (7). 1
It has been known for some time that porphobilinogen 28-30 may be converted into a porphyrin by heating it in acid solution and, in view of the difficulty in establishing the purity of uroporphyrin isomers, reports have appeared in the literature that this porphyrin is uroporphyrin III.31 For this reason it has been assumed that the enzyme merely accomplished what acid did and that the mechanisms of the enzymic and the acidic conversions of porphobilinogen into uroporphyrin are closely related. That this assumption is not necessarily correct is clear from the following considerations. (i) Whereas isoporphobilinogen (8) is converted into a mixture of uroporphyrinogen isomers by heating it in acid, the enzyme preparation is without action upon it.32 (ii) W H 2 0 is incorporated into the porphyrinogen
2 i E. J. Tarlton, S. F. MacDonald, and E. Baltazzi, J. Arner. Chem. SOC., 1960, 82, 4389. 2 8 J. Waldenstrom and B. Vahlquist, 2. physiol. Chem., 1939, 260, 189. 29 R. G. Westall, Nature, 1952, 170, 614. 30 G. H. Cookson and C. Rimington, Biochem. J., 1954, 57, 476. 31 E. Bullock, A. W. Johnson, E. Markham, and K. B. Shaw, J., 1958, 1430. 3 2 A. T. Carpenter and J. J. Scott, Biochim. Biophys. Acta, 1961, 52, 195.
390
formed from porphobilinogen by heating it in acid solution in the presence of labelled f ~ r m a l d e h y d e34~ ~ ~ not into the porphyrinogen formed , but enzymically from porphobilinogen in the presence of labelled formaldeh ~ d e . * ~ (iii) Condensation of porphobilinogen in acid solution is a ~ random process as regards the isomers formed, since the product porphyrinogen isomerises rapidly in hot acid solution.36 T i isomerisation has been hs used to demonstrate the thermodynamic stability of the cyclised macrocycle over the linear polypyrrylmethanes. The ratio of isomers formed is the random mixture: 1/8 I, 1/8 11, 1/2 111, l/4 IV. The enzyme, on the other hand, produces uroporphyrinogen I11
Isomer I
PA-PA-PA-PA
I1 I11
PA-AP-P A - ~ k
+A-PA-PA-~b
+A-PA-AP-A~
IV
When porphobilinogen is heated in acid solution 33 in the presence of formaldehyde the relative amounts of uroporphyrinogen isomers remain the same as in the absence of formaldehyde and considerable incorporation of formaldehyde takes place. Furthermore, when any uroporphyrinogen isomer is heated 36 in acid solution in the presence of formaldehyde the same random ratio of isomers is obtained and considerable incorporation of formaldehyde takes place. Consequently neither the isomer ratios nor the formaldehyde incorporation can be used to explain the mechanism of condensation of porphobilinogen in acid solution as has been attempted previously. I n neutral and alkaline solution, however, uroporphyrinogen neither isomerises nor incorporates formaldehyde, and the results of condensing porphobilinogen under these conditions can be interpreted more readily. When porphobilinogen is heated under neutral conditions the isomer ratio found is: 1/2 I, 1/2 (I11 IV) and under alkaline conditions 3/4 I, l/4 (I11 IV). I n the presence of formaldehydeincorporation of formaldehyde into the uroporphyrinogen occurred and an approximately random mixture of isomers was obtained. These observations in neutral and alkaline solution have been explained by Mauzerall using a general mechanism first suggested by Cookson and Rimingt0n.3~ Considerableexperimental evidence has accumulated regarding the details of the enzymic conversion of porphobilinogen to uroporphyrinogen 111. Bogorad and Granick showed that a preparation from ChZoreZZa formed uroporphyrinogen I11 from porphobilinogen but, after it had been heated to 60,only uroporphyrinogen I was formed. This observation indicated that
82, 2605. W. H. Lockwood and A. Benson, Biochem. J., 1960, 75, 372. 3 5 L. Bogorad and G. S. Marks, J . Biol. Chem., 1960, 235, 2127. 36 D. Mauzerall, J . Amer. Chem. Soc., 1960, 82, 2601. 37L. Bogorad, J . Bwl. Chem., 1968, 233, 610. 3 8 L. Bogorad and S. Granick, Proc. Nut. Acad. Sci. U.X.A., 1953, 89, 1176.
ss D. Mauzerall, J . Amer. Chem. SOC., 1960,
34
MABKS: THE BIOSYNTHESIS O F PORPHYRINS
391
a t least two enzymes participate in the synthesis of uroporphyrinogen 1 1 1 from porphobilinogen and that the two enzymes differ in their susceptibility to heat. This has been confirmed by subsequent experiment. Thus from aqueous extracts of acetone powders of spinach leaf tissue an enzyme, uroporphyrinogen I-synthetase, was isolated 39 and purified,which converted porphobilinogen into uroporphyrinogen I. The yields approach 100yo when the reaction proceeds anaerobically. The second enzyme, uroporphyrinogen III-cosynthetase, was isolated from aqueous extracts of wheat germ 40 and shown to have no capacity for catalysing porphobilinogen consumption when incubated alone with this substrate. However, when incubated together with uroporphyrinogen I-synthetase and porphobilinogen it brought about the production of uroporphyrinogen I 1 instead of the I isomer. 1 Uroporphyrinogen I is not a substrate for the cosynthetase.26, 409 4 1 Similar results have been obtained with extracts from Rhodopseudomoms spheroid@.4 2 The key to the clarification of the mechanism of uroporphyrinogen I 1 1 formation is the identification of the substrate or substrates of uroporphyrinogen III-cosynthetase. It appears likely either (i) that the substrate is a product (9, 10, or 11) of the linear condensation of porphobilinogen by uroporphyrinogen I-synthetase; or (ii) that the substrates are one of these
(9)
A H2N.CHl c l C H 2
H
\. -1
< l
H
P CH2 N H CH2
k j
N H
(J1 )
substances and porphobilinogen. Recently Bogorad 43 has been able to accumulate an intermediate in the conversion of porphobilinogen into uroporphyrinogen I whose properties are consistent with those of a dipyrrylmethane. It is possible that this intermediate may be a substrate for the cosynthetase. Synthesis of the possible substrates (9-1 1) would be helpful in clarifying the mechanism of this reaction, and an approach in this direction has been made.44 The more readily synthesised dippylmethanes (12-14) have been prepared,44,4 5 but none of these compounds is concepned in the biosynthesis of uroporphyrinogen I or III.39 32, 4 6 Mathewson and Corwin 47 recently suggested that the substrate of the cosynthetase is a linear tetramer (15)formed by the action of uroporphyrinogen I-synthetase on porphobilinogen. This tetramer differs from the tetra39 L. Bogorad, J. Biol. Chem., 1958, 233, 501. 40 L. Bogorad, J. Biol. Chem., 1958, 233, 510. 41L. Bogorad and G. S. Marks, Biochim. Biophys. Acta, 1960, 41, 356.
&2H.Heath
45
44 45
82, 4384.
4'
and D. S. Hoare, Biochem. J., 1959, 72, 13. L. Bogorad, Fed. Proc., 1962, 21, 400. G. P. Arsenault and S. F. MacDonald, Canad. J. Chem., 1961, 39, 2043. G. P. Arsenault, E. Bullock, and S . F. MacDonald, J. Arner. Chem. Soc., 1960,
46H. Heath and D. S. Hoare, Biochim. Biophys. Acta, 1960, 39, 167.
J. H. Mathewson and A. H. Corwin, J . Amer. Chem. SOC.,1961, 83, 135.
392
pyrrylmethane (1 1) by retention of a-hydrogen atoms after successive selfcondensations of porphobilinogen, allowing sufficient flexibility for cyclisation to uroporphyrinogen 111. It is thought that the cosynthetase catalyses an attack by the CH,*NH,+ group, on the " occupied " position of pyrrole a, followed by rearrangement of this cyclic structure to uroporphyrinogen 1 1 1.
I n the absence of the cosynthetase the linear tetramer (15) is assumed to cyclise to uroporphyrinogen I. This hypothesis accounts for all the observations with enzyme systems, and experiments designed to test it are awaited with interest. According to an earlier h y p o t h e s i ~ ,49 ~ , cosynthetase is assumed to ~ the catalyse the condensation of opsopyrroledicarboxylic acid (16) with the tetrapyrrylmethane (11) which is presumably produced by the action of uroporphyrinogenI-synthetase on porphobilinogen. The resulting pentamer (17) is thought to be ruptured at the bond indicated by the dotted line, with
U r o p o r p h y r i n o g e n I11
Opsopyrrole dicarboxy I i c acid
regeneration of opsopyrroledicarboxylic acid and cyclisation of the tetramer t o an isomer of series 1 1 The opsopyrroledicarboxylic acid, which would 1. need to be present in catalytic quantities only, would act as a coenzyme of uroporphyrinogen III-cosynthetase. I n experiments designed to test this hypothesis opsopyrroledicarboxylic acid (synthesised by MacDonald et al. 5O) was found not to be incorporated 3 during the enzymic synthesis of uropor1 phyrinogen I 1 from porphobilinogen, nor was 14C-labelledopsopyrroledicarboxylic acid incorporated 48 during the enzymic formation of haem from
4 s A . T. Carpenter and J. J. Scott, Biochem. J . , 1959, 71, 325. 4 9 A. H. Jackson and S. F. MacDonald, Cunad. J . Chem., 1957, 35, 715. 5'3D. M. MacDonald and S. F. MttcDonald, Cunad. J. Chem., 1955, 3 , 573. 3
M A R K S : THE BIOSYNTHESIS O F PORPHYRINS
393
glycine and succinic acid in lysates of fowl red cells. Further experiments have shown 32 that isoporphobilinogen (synthesised recently by Arsenault et aZ.44),considered as a possible coenzyme of uroporphyrinogen I11 cosynthetase, is also not concerned with the enzymic formation of uroporphyrinogen I or 111. The availability of purified enzyme preparations has permitted a quantitative investigation of the possible participation of formaldehyde in the enzymic synthesis of uroporphyrinogen I and I11 from porphobilinogen. It was found that formaldehyde was neither a product 34 nor a reactant 35 in the enzymic synthesis, thus excluding several hypotheses on the mechanism of enzymic formation of uroporphyrinogen I11 from porph~bilinogen.~~, 52 Several other mechanisms for the biosynthesis of uroporphyrinogen I11 from porphobilinogen have been suggested 3, 31, 35, and these are summarised by Bogorad. Prodigiosin, the red pigment of Serratia mrcescens, was wrongly assigned 54 the tripyrrylmethene structure (18) in 1934 and on this basis a tripyrrylmethene was suggested as an intermediate in porphyrin biosynthesis.55 Prodigiosin has recently been synthesised 56 and its structure shown to be that of a pyrryldipyrrylmethene (19). 8-Aminolaevulicacid is not a precursor of this compound.57
349
519
Formation of Coproporphyrinogen IU.-The finding that uroporphyrinogen I11 rather than uroporphyrin I11 is the true precursor 26, 58, 59 of coproporphyrinogen I11 [hexahydro-derivative of (26)l has resolved the somewhat contradictory evidence concerning the intermediates in hzm synthesis from porphobilinogen. Recently, an enzyme, uroporphyrinogen decarboxylase, which catalyses the conversion of uroporphyrinogen I11 into coproporphyrinogen I11 has been isolated 26 from rabbit reticulocytes by zone electrophoresis on starch. All the hexahydro-derivatives (porphyrinogens) of the uroporphyrin isomers (I-IV) recently synthesised by MacDonald and his co-workers 60, 61 are decarboxylated by this enzyme and the yield of coproporphyrinogenfrom the various isomers is I11 > IV > I1 > I.62 The
279
C. S. Russell, and T. Abramsky, J . Biol. Chem., 1955, 215, 613. A. Treibs and W. Ott, Annalen, 1958, 615, 137. 5 3 J. Wittenberg, Nature, 1959, 184, 876. 5 4 F. Wrede and A. Rothhaas, 2. physiol. Chem., 1934, 226, 95. 5 5 W.J. Turner, J. Lab. Clin. Med., 1940, 26, 323. 5 6 H. Rapoport and K. G . Holden, J. Amer. Chem. SOC., 1960, 82, 5510. 5 7 G. S. Marks and L. Bogorad, Proc. Nat. Acad. Sci. U.S.A., 1960, 46, 25. 5 8 R. A. Neve, R. F. Labbe, and R. A. Aldrich, J. Arner. Chem. SOC., 1956,78,691. 5 9 L. Bogorad, J . B o . Chem., 1958, 233, 516. il 6 o S F. MacDonald and R. J. Stedman, Canad. J . Chem., 1954, 32, 896. . 61 S. F. MacDonald and J. Michl, Canad. J . Chern., 1956, 34, 1768. 6 a D. Mauzerall and S. Grrrtnick, J . Biol. Ch.em., 1958, 232, 1141.
5 D Shemin, 1 .
52
394
enzyme contains essential thiol groups, has a pH optimum of 6.8 and K , of < 5 x An enzyme preparation with similar properties has recently been isolated from Rps. spheroid@ by Hoare and Heath,63 who have evidence for the requirement of a heat-stable co-factor in this conversion. When 6-aminolzevulic acid or porphobilinogen was incubated with whole blood or supernatant liquid from normal rabbits and humans, an intermediate heptacarboxylic acid designated phyriaporphyrin I11 was isolated.64 Evidence has'been presented 6 5 that this heptacarboxylic acid is a' normal intermediate, following uroporphyrinogen I11 in the metabolic pathway of protoporphyrin I X biosynthesis. This heptacarboxylic acid is identical with pseudouroporphyrin 136 and with " porphyrin 208 " which is present in significant quantities in the urine of patients with porphyria hepatica. Recent preparations of natural coproporphyrin I11 6 7 have higher melting points than Fischer's synthetic specimens. This brought the purity of both into question, and to resolve these differences the syntheses of coproporphyrin I11 and IV have been repeated.68 By this means it has been shown that the natural and synthetic material are identical and data relevant to the identification of coproporphyrin have been corrected and extended. Biosynthesis of Protoporphyrin IX and Haem.-The enzyme coproporphyrinogen oxidase removes two hydrogen atoms and a carboxyl group from each of the two propionic acid side chains in rings A and B of coproporphyrinogen, and at the same time six hydrogen atoms are removed from the ring system to give protoporphyrin IX (25). The enzyme was first
(20 ; R = R' = CHMe*OH\
(21; R = R ' =
COMe) CH:CH.C02H)
HI
Me
(22; R = R ' = (23; R=R'=

(24; R=R'= (25; =
PN
p
HN<
HC
CHZCH2) Et)
R"&
d C : e
p
(26; R=R'=
CH2-CH2.C02H)
(27)
demonstrated in a frozen-thawed Euglena preparation 69 and in hEmolysed chicken erythrocyte^.^^ Subsequently this enzyme has been found 71 in a variety of tissues and in particularly high concentration in liver, bone marrow, and small intestine. The enzyme present in beef-liver mitochondria was purified twenty-fold by solubilising it with thioglycollate at pH 9 and isolating it in the 40-70% -saturated ammonium sulphate fraction. Oxygen
73, 679. A. M. del C. Battle and M. Grinstein, Biochim. Biophys. Acta, 1962, 57, 191. G 6 A. M. del C. Battle and M. Grinstein, Biochim. Biophys. Acta, 1962, 62, 197. 6 6 J. E. Falk, E. I. B. Dresel, A. Benson, and C. Knight, Bioch.em.J . , 1956, 63, 87. 6 7 C. H. Gray and L. B. Holt, Biochem. J., 1948, 43, 191. 6 a F. Morsingh and S. F. MacDonald, J . Amer. Chem. SOC., 1960, 82, 4377. e 9 S. Granick and D. Mauzerall, Fed. Proc., 1958, 17, 233. 7 0 S. Granick and D. Mauzerall, Ann. N . Y . A d . Sci., 1958, 75, 115. 7l S. Sano and S. Granick, J . Biol. Chem., 1961, 236, 1173.
c3 D. S. Hoare and H. Heath, Biochem. J., 1959,
64
M A R K S : THE BIOSYNTHESIS O F PORPHYRINS
395
was the only oxidant found to be used by this enzyme. I n contrast to the decarboxylation of all four isomers of uroporphyrinogen by uroporphyrinogen 1. decarboxylase this enzyme is specific for coproporphyrinogen 1 1 During the enzymic reaction, an intermediate porphyrin that has one vinyl and three propionic acid groups appears and then disappears. The finding in 1953 that haematoporphyrin IX (20) and monohydroxyethylmonovinyldeuteroporphyrin I X accumulate in cultures of ChZoreZZa mutant W,B-17 729 7 3 suggested that these two compounds might be intermediates in the conversion of coproporphyrinogen I11 into protoporphyrin IX, and that a series of steps similar to that found in fatty acid oxidation might be necessary in this conversion.3 However, the following two observations show that this idea is incorrect. (i) Frozen and thawed Chlorella preparations which can catalyse the formation of protoporphyrin I X from porphobilinogen fail to utilise haematoporphyrin IX, haematoporphyrinogen IX, diacetyldeuteroporphyrin IX (21), or diacetyldeuteroporphyrinogen IX.74 (ii) Hydroxylamine and semicarbazide do not inhibit the reaction, indicating that the oxidation does not involve an intermediate containing a carbonyl g r o ~ p . ~ 7 1, Another possible course for this reaction would be g through deuteroporphyrin I X 2,4-diacrylic acid (22) or its hexahydro75 This compound (22), first synthesised by Fischer and Beer,76has recently been prepared by Sparatore and Mauzerall 7 5 by a more satisfactory procedure. However, neither this nor its hexahydro-derivative served as substrates for coproporphyrinogen oxidase.7 1 This suggests that the reaction is concerted, oxidation and decarboxylation occurring simultaneously;2, 71 evidence for this has been obtained from a study of the enzyme reaction in tritiated water.2 Sano and Graniclr 71have pointed out that, whereas coproporphyrinogen oxidase and the enzymes connected with the synthesis of 6-aminolaevulic acid are localised in cellular particulates, the enzymes catalysing the conversion of 6-aminolaevulic acid into coproporphyrinogen are present in the cytoplasm. It appears that this acid, synthesised in mitochondria, leaks into the cytoplasm, to be converted into coproporphyrinogen,which migrates back into the mitochondria, to be transformed into protoporphyrin. It is suggested 71 that this localisation might permit permeability to play a part in control of porphyrin synthesis by the cell. An enzyme catalysing the chelatiun of iron by protoporphyrin to form protohaemin I X has been found in several tiss~es.~7-83With a partially
L. Bogorad and S. Granick, J. Biol. Chem., 1953, 202, 793. S. Granick and L. Bogorad, J. Amer. Chem. SOC., 1953, 75, 3610. 7 4 G. S. Marks and L. Bogorad, 1958, unpublished work. 7 5 F. Sparatore and D. Mauzerall, J. Org. Chem., 1960, 25, 1073. 7 6 H. Fischer and L. Beer, 2. physiol. Chem., 1936, 244, 54. 7 7 R . F. Labbe and N. Hubbard, Biochem. Biophys. Acta, 1960, 41, 185. 78R. Labbe and N. Hubbard, Biochim. Biophys. Acta, 1961, 52, 130. F. 7 9 H. Oyarnrt, Y. Sugita, Y. Yoneyama, and H. Yoshikaya, Biochim. Biophys. Acta, 1961, 4'7, 413. so R. C. Krueger, I. Melnick, and J. R. Klein, Arch. Biochem. Biophys., 1956, 64, 302. s l A . Goldberg, B i . J. Haematol., 1959, 150, 5. rt s 2 H. C. Schwartz, G. E. Cartwright, E. L. Smith, and M. M. Wintrobe, Blood, 1959, 14, 486.
73
73
396
purified preparation from duck erythrocytes 79 the stoicheiometry of this reaction has been demonstrated. The solubilised enzyme from rat liver is activated by reducing agents and exhibits numerous properties of an enzyme requiring a thiol group for activity. With the liver enzyme, no evidence for more than one component has been obtained,77 while the chicken erythrocyte preparation has been divided into two heat-labile, non-dialysable fractions.83 The enzyme obtained from rat liver 78 and from duck erythrocytes 79 is relatively unspecific with respect to the porphyrin requirement, and with the latter preparation haems are formed from deuteroporphyrin (23), mesoporphyrin (24), and haematoporphyrin. The enzyme preparations were, however, more selective with respect to their metal requirement. Labbe and Hubbard 7 8 attribute this to the fact that the enzyme is presented in vivo with only one porphyrin, namely, protoporphyrin, while it has to select the Fe2+ion from a variety of metal ions in order to form hsm. Cfiochromes and Haem Enmes.-It is now generally accepted that the haems of catalase, peroxidase, and the various cytochromes are derived in the same manner as the haem of haemoglobin. Cytohaemin (haem a), the prosthetic group of cytochrome-a, and of cytochrome-a, has been degraded t o ~ytodeuteroporphyrin~84 the latter has been shown85 to be 8-deand methyldeuteroporphyrin I X (27; R = R = R = H). I n recent work on haem a it has been shown S6 that R = CHO and evidence has been presented regarding the nature of the substituents a t R and R.87,88 An improved method of isolation of haem a has recently been reported which will be valuable in further structural studies.89 It is clear that the structure of haem a differs markedly from that of protohzmin IX, and a study of its biosynthesis will be of considerable interest. It has been claimed that a streptomycin-resistant variant of Micrococcus pyogenes can use protohaemin as a source for the production of haem a, but no experiments with labelled protohaemin have yet been carried Sano and Granick 71 have recently shown that protoporphyrinogen IX reacts readily with cysteine t o form a porphyrin C-type compound.g1 This interesting finding has led these authors to suggest that cytochrome-c may be formed by the interaction of the thiol groups of the apocytochrome-c peptide with protoporphyrinogen during its oxidation. The coupling of protohaemin to the catalase apoprotein, synthesised by the cell, is a CoAlinked enzymic process. A 1 : 1 ratio between CoA and haemin is needed in the coupling reaction.02 It has been suggested 93 that the haem apoen83 H. C. Schwartz, R. L. Hill, G . E. Cartwright, and M. M. Wintrobe, Fed. Proc., 1959, 18, 545. 8 4 0. Warburg and H. S. Gewitz, 2. physiol. Chem., 1953, 292, 174. 8 5 G;. S. Marks, D. K. Dougall, E. Bullock, and S. F. MacDonald, J. Amer. Chem. Soc., 1960, 82, 3183. 8 6 M. Piatelh, Tetrahedron, 1960, 8, 266. 8 7 M. Morrison, J. Connelly, J. Petix, and E. Stotz, J . Biol. Chem., 1960, 235, 1202. D. B . Morrel, J. Barrett, and P. S. Clezy, Biochem. J., 1961, 78, 793. 8 9 W. S. Caughey and J. L. Yorlr, J. Biol. Chem., 1962, 237, PC 2414. M. Kiese, H.rcKurz,and E. Thofern, Biochem. Z.,1958, 330, 541. The Enzymes, ed. J. B. Sumner and K. Myrback, Academic 9 l K . G. Paul, Press Inc., New York, 1951, Vol. 11, p. 357. O 2 J. Jensen, J. Bacteriol., 1957, 73, 324. 9 3 J. Jensen, Biochem. Biophys. Res. Comm., 1962, 8, 271.
MARKS: THE BIOSYNTHESIS O F PORPHYRINS
397
zymes synthesised by Staphlococcus aureug JT/52 (a mutant strain) in the absence of hem act as inhibitors of the enzymes catalysing the conversion o porphobilinogen into uroporphyrinogen. f Hzmophilus species comprise a group of organisms with absolute requirements for hemin and/or pyridine nucleotide. It has been shown that the enzymes required for hem synthesis are present in four hem-independent species but are absent from three distinct haem-requiring species.94 Chlorophyll Biosynthesk-The discovery by Granick in 1948 of a Chlorella mutant which produced no chlorophyll but accumulated protoporphyrin I X instead 95 established the biosynthetic relation between
fH2
several steps I-I02C*CH2*CH2
c. .,
I -c=o
Mg Protoporphyrin IX monomethyl e s t e r
H - C02Me
(28)
Mg Vinylphaeoporphyrin
PhytoIJ Protochlorophyll Light \Light
a ,
+ 2H
+ 2H
Chlorophyllide JPhytoI
Chlorophyll A Bacteriochlorophyll
protoporphyrin I X and bacteriochlorophyll. I n subsequent work magnesium protoporphyrin IX and magnesium vinylpheoporphyrin a5 (29) were isolated from ChZoreZZa mutants.96, 9 7 Recently protoporphyrin monomethyl ester and magnesium protoporphyrin monomethyl ester (28) have been isolated from a Chlorella mutant No. 60-A and from barley seedlings treated with
9 4 D. C White, New York Branch American SOC. . for Microbicl., 97th Meeting, January, 1962. 9 5 S. Granick, J . Biol. Chem., 1948, 172, 717. 9 6 S. Granick, J . Biol. Chem., 1948, 175, 333. 9 i S. Granick, J . Biol. Chem., 1950, 183, 713.
398
b-aminolaevulic acid.98 On the basis of these findings the annexed biosynthetic pathway was postulated. Further clarification of the biosynthetic pathway has come from the studies of Gibson et aLg9 who found that 10-4M-ethionine and 10-3~threonine almost completely inhibited bacteriochlorophyll synthesis by Rhodopseudomoms spheroides and at the same time markedly increased excretion of copro- and uro-porphyrin into the medium in which the organism was illuminated. At these concentrations there was little inhibition of protein synthesis or growth. The effects of both ethionine and threonine were reversed by addition of methionine or homocysteine thiolactone, and homoserine reversed the effect only of threonine. These results suggested that methionine might be the direct precursor of the methyl ester group of bacteriochlorophyll. To test this, organisms were illuminated in the presence of [Me-14C]methionine, and highly radioactive bacteriochlorophyll was isolated and degraded. Radioactivity was found to be almost exclusively in the methyl group, showing that the methyl group of methionine was the specific precursor of the porphyrin ester-carbon atom. Less specific utilisation of formate for the methyl group of chlorophyll had been shown in earlier work of Green et aZ.lW Recently threonine has been shown lol to inhibit synthesis de novo of methionine in this organism by competitivelyinhibiting homoserine dehydrogenase, which explains why threonine and ethionine exert similar effects on the biosynthesis of bacteriochlorophyll and on the accumulation of porphyrins. The mechanism by which methionine provides the methyl ester group of bacteriochlorophyll has recently been elucidated. Chromatophores from Rhodopseudomoms spheroides, when incubated with magnesium protoporphyrin and X-adenosylmethionine, form magnesium protoporphyrin monomethyl ester.102 The enzyme catalysing this synthesis (S-adenosylmethionine-Mg-protoporphyrinmethyl transferase) has been extensively studied. 13 It has optimal activity at pH 8-4 and is stable to freeze-drying of the chromatophores. Acetone-dried chromatophores contained 33% of the original activity but attempts to solubilise the enzyme from such preparations have been unsuccessful. S-Adenosyl-ethionine and -homocysteine were found to be competitive inhibitors with respect to S-adenosylmethionine, so that in methyl-group deficiency the rate of synthesis of Mg protoporphyrin monomethyl ester may be low, both because of a low concentration of X-adenosylmethionineand a relatively high concentration of X- adenosylhomocysteine. The specificity of the enzyme for other porphyrins and metalloporphyrins was examined. Magnesium deuteroporphyrin and magnesium mesoporphyrin exhibited about a fifth of the activity, and zinc protoporphyrin about
S . Granick, J . Biol. Chem., 1961, 236, 1168. K. D. Gibson, A. Neuberger, and G. H. Tait, Biochem. J . , 1962, 83, 550. l o oM. Green, K. T. Altman, J. E. Richmond,.and K. Salomon, Nature, 1957, 179, 375. l o l K. D. Gibson, A. Neuberger, and G . H. Tait, Biochem. J., 1962, 84, 483. loa G. H. Tait and K. D. Gibson, Biochim. Biophys. Acta, 1961, 52, 614. lo3 K. D. Gibson, A. Neuberger, and G. H. Tait, personal communication.
O0
M A R K S : T H E B I O S Y N T H E S I S OF P O R P H Y R I N S
399
half the activity, of magnesium protoporphyrin; ferrous and ferric protoporphyrin were inactive. Of the metal-free porphyrins tested, protoporphyrin was the best substrate, exhibiting -10% of theactivity of magnesium protoporphyrin, and other dicarboxylic porphyrins, meso-, deutero-, and hzmato-porphyrin were much less active. The tetracarboxylic acid porphyrin, coproporphyrin, was inactive, as was protoporphyrinogen. Of the porphyrins tested as inhibitors of the methylation, hzmatoporphyrin was the most potent and of the metalloporphjTins ferrous, ferric, and manganese protoporphyrin were active inhibitors. It has been suggested that under some conditions of growth the inhibition caused by hzem may be of physiological importance. Since protoporphyrin is only one-tenth as active as magnesium protoporphyrin as a substrate for enzymic methylation it was concluded that the first two steps in the conversion of protoporphyrin into bacteriochlorophyll are protoporphyrin -+ Mg protoporphyrin -+ Mg protoporphyrin monomethyl ester. The further conversion of magnesium protoporphyrin monomethyl ester into magnesium vinylphzoporphyrin a5 must involve several intermediate steps and further understanding of this conversion awaits detailed enzymic studies.
Me. CH Me.:H.OH_,O H
Me
Me w Hi ft t EE
Me. C
/ H
On the basis of recent evidence lo4 chlorophyll d is thought to be 2-devinyl-2-formylchlorophyll A chlorophyll isolated from Chbrobium a. thiosulphatophilum possesses several novel features ;it does not give a positive Molisch phase test and the alcohol component of the ester linkage to the propionic acid group is trans,trans-farnesol.lo5 The proposed structure for this compound logis that of a derivative of 2-devinyl-2-l-hydroxyethyl6-methylpyrophzophorbide (30), and a study of the biosynthesis of this compound will be of considerable interest. G . S. M.
104 A. S. Holt and H. V. Morley, in Comparative Biochemistry of Photoreactive Systems, ed. M. B. Allen, Academic Press Inc., New York, 1960, p. 169. lo5 If. Rapoport and H. P. Hamlow, Biochem. Biophys. Res. Comm., 1961, 6, 134. lo6 A. S. Holt, D. W. Hughes, H. J. Kende, and J. W. Purdie, J . Amer. Chem. SOC.,1962, 84, 2835.
400
3. VITAMIN B I Z
INthis Report consideration is given primarily to the structure, function, and mechanism of action of the recently discovered cobamide coenzymes and to the impact which this new knowledge has had on the question of the metabolic role of vitamin B12. The biosynthesis of cobamides will also be discussed. The Isolation and Structure of the Cobamide Coenzmes.-The investigations by which H. A. Barker and his co-workers have recently revolutionised the field of vitamin B,, chemistry and biochemistry began during a study of cell-free extracts from Clostridium tetanomorphum which were able to convert L-glutarnate (1) into mesaconate (3) via an isomerisation to L-threop-methylasparate (2).
1 2
C0,H CH*NH, CH,
1 2
7 2
C0,H CH-NH,
1 3
=$
1 2 H O 2C-CH
I5
I I
4 C.CO,H
3
CHCH, COOH (2)
4 CH,
6
CH,
C0,H
(1)
(3)
The isomerisation required a factor which could be removed from the cell-free extract by absorption on charcoal.2 Partial purification of the factor, after extraction from whole cells with boiling 80% ethanol, showed i t t o be orange-red, with absorption maxima a t 263, 303, 374, and 475 mp. Light inactivated it and produced spectral changes to give maxima a t 261,
R' ( d )
,o
'0
I
O&
OH
I
(f
2 Y(1) Cobyrinic acid: (2) Cobinamide: (3) Cobamide :
2 OH, R = O H NH,, R = NH.CH,-CHMe*OX, X 2 R1= NH,, R2= NH.CH,*CHMe*OX'

R = 1 R = 1
H. A. Barker, R. D. Smyth, E. J. Wawszkiewicz, M. N. Lee, and R. M. Wilson, Arch. Biochem. Biophys., 1958, 78, 468; A. Munch-Petersen and H. A. Barker, J. Biol. Chem., 1958, 230, 649. H. A. Barker, H. Weissbach, and R. D. Smyth, Proc. Nat. A d . S i U.S.A., c. 1958, 44, 1093.
W H I T E : V I T A M I N B12
401
351, 407,and 495 mp. The last set of maxima was reminiscent of that of the cobalamins. Alkaline potassium cyanide inactivated the factor, changed its colour to reddish-purple, and produced a change to a spectrum characteristic of cobinamide dicyanide (2; Y = CN). Hydrolysis of the factor with acid yielded adenine and on this and other evidence it was concluded that the compound under investigation was the coenzyme form of pseudovitamin B12. After more extensive purification in which the solubility of the coenzyme in ethanol (80%),its solubility in phenol, and its retention on cation-exchangers at pH < 5.5 were utilised, the structural hypothesis was confirmed.3 However, it now became apparent that there were two molecules of adenine to each atom of cobalt and it was suggested that the " extra " adenine occupied the site usually taken by cyanide in pseudovitamin Bz2. The ribonucleotide adenine, present also in pseudovitamin B1,,was readily removed by mild acid hydrolysis with consequent loss of coenzymic activity but without gross alteration of spectral properties. The " extra " adenine was more resistant to removal by acid but could be readily displaced by alkaline cyanide with resultant loss, by the coenzyme, of its biological activity and a change in its spectrum to conform with that of pseudovitamin B,,.4 A t the same time as the structure of pseudovitamin B,, coenzyme was being established, the synthetic ability of C. tetanomorphum was utilised to incorporate 5,6-dimethylbenzimidazole into the coenzyme form of vitamin B,, i t ~ e l f . Also the coenzyme of vitamin B,, was successfully isolated 6 ~ from Propioniibacterium shermanii without addition of dimethylbenzimidazole to the growth medium. Further chromatographic and electrophoretic evidence for the existence of an extra adenine molecule in the vitamin B,,
CH-0
-P-,
oJ
P I L
H C- - C
/A
I \
r---N
'Me
HO*H,;
' 0
(4)Cyanocobalamin (vitamin B 2) (5,6-dimethylbenzimidazolyl cobamide cyanide) (5) I n pseudovitamin B,, (adenylcobamide cyanide) adenine replaces 5,6-dimethylbenzimidazo3e) (6) I n cobamide coenzymes, cyanide is replaced by adenosine.
H. A. Barker, R. D. Smyth, H. Weissbach, A. Munch-Petemen, J. I. Toohey, J. N. Ladd, B. E. Volcani, and R. M. Wilson, J. Biol. Chem., 1960, 235, 181. H. Weissbach, J. N. Ladd, B. E. Volcani, R. D. Smyth, and H. A. Barker, J. Bid. Chem., 1960, 235, 1462. ti H. Weissbach, J. Toohey, and H. A. Barker, Proc. Nut. Acad. Sci. U.S.A., 1959, 45, 521. H. A. Barker, R . D. Smyth, H. Weissbach, J. I. Toohey, J. ItT. Ladd, and B. E. Volcani, J. B o . Chem., 1960, 235, 480. il
402
coenzyme was obtained, thus giving a, clear structural distinction between vitamin B,, [a-(5,6-dimethylbenzimidazolylcobamide)cyanide] (5) and vitamin B,, coenzyme [a'(5,6-dimethylbenzimidazolyl)cobamidecoenzyme] (7). Adenine picrate was later isolated from the products of the cyanideinduced decomposition of the coenzyme.' The nature of the products resulting from photolysis of adenylcobamide coenzyme and acid hydrolysis (O-h-HCl, loo", 90 minutes) of dimethylbenzimidazolylcobamide coenzyme indicated that the " extra adenine is linked to a sugar. The results could not be rationalised, however, until X-ray crystallographic analysis showed that adenine is present as. its riboside and that the riboside is, surprisingly, linked directly to cobalt at C-5'. Presumably erythro-2,3dihydroxypent-4-enal lowhich can be obtained by mild acid hydrolysis and by cyanide treatment of the coenzyme is a degradation product of ribose after rupture of the Co-C bond; and the identification,ll under similar degradative conditions, of adenosine-5'-carboxylic acid, a cyclic riboside, and adenosine-5'-aldehyde is in agreement with the X-ray crystallographic work. Magnetic-susceptibilitymeasurements indicate that vitamin B,, coenzyme is paramagnetic in solution,12 and the magnetic moment l3 of a solution of the coenzyme form of cobinamide indicated the presence of an octahedral bivalent cobalt complex. Johnson and Shaw also consider the solid coenzyme to be paramagnetic, but Bernhauer et aZ.12 consider it to be diamagnetic, like cyanocobalamin. A compound which has close spectral affinity with the bivalent cobalt-containing vitamin B12r is produced on photolysis of the coenzyme under anaerobic conditions, and aquocobalamin is formed quantitatively, immediately after the admission of oxygen.l4 However, measurement of the oxygen uptake l 5 with the oxygen electrode mol. of oxygen per during this process indicated the consumption of 0-75 mol. of coenzyme instead of 0.25 mol. necessary for the conversion of cobalt(rr) into cobalt(m). Also, during anaerobic photolysis in the presence of 2,6-dichlorphenol-indophenolone equivalent of dye per mol. of coenzyme is reduced without causing the oxidation of the B,, state to that which exists in aquocobalamin.16 Thus, the photolytic conversion of coenzyme into vitamin may involve an oxidative process in the peripheral part of the coenzyme molecule.15 Thus the true valency state of cobalt in the coenzyme is not clear, neither is the state of conjugation in the chromophore. Apart from the microbial sources mentioned above, the cobamide coenzymes have also been isolated from Clostridium sticklandii,16 C. per)'
A. W. Johnson and N. Shaw, Proc. Chem. Soc., 1960, 420. C. Hogenkamp, and H. A. Barker, Biochem. Biophys. Res. Cornm., 1960, 2, 143. P. G. Lenhert and D. C. Hodgkin, Nature, 1961, 192, 937. l o H . P. C. Hogenkamp and H. A. Barker, J . Biol. Chem., 1961, 236, 3097. l1 H.P. C. Hogenkamp, J. N. Ladd, and H. A. Barker, J. Biol. Chem., 1962, 237, 1950; A. W. Johnson and N. Shaw, J., 1962, 4608. l2 K. Bernhauer, P. Gaiser, 0. Miiller, and F. Gunter, Biochem. Z . , 1961, 333, 560. l3 L. Nowicki and J. Pawelkiewicz, Bull. Acad. polon. Sci., Ser. Sci. Chim. et Biol., 1960, C1. 11, 8, 433. l4 R. 0 . Brady and H. A. Barker, Biochem. Biophys. Res. Comm., 1961, 4, 373. l5 H.A. Barker, 2nd European Symposium on Vitamin B12, Ferdinand Enke Verlag, Stuttgart, 1962, p. 99. l6 T. C. Stadtman, J . Bact., 1960, 79, 904.
* 5. N. Ladd, H. P.
WHITE: VITAMIN Bla
403
fringens,lT Bacillus rnqaterium,lg Escherichia coli 113-3, Xtreptomycesfradiae, and Aerobacter aerogenes.17 The coenzymes probably occur also in the acraldehyde-forming lactobacillus 2O8-A.l9 The isolation of the coenzyme from the nodules of a number of legumes, from alder, and from Rhixobium melitoti has gone some way towards explaining the essential nature of cobalt in nitfogen fixation.,O Mammalian sources of vitamin B,, coenzyme include rabbit, chicken, sheep, and human liver.21 @-MethylasparateIsomerisation.-The isomerase has been isolated only from Clostridium tetanomorphum 2 and no metabolic significance for this reaction in mammals has yet been found. Attempts to do so have been stimulated mainly by the possibility of a biosynthetic route to thymine ribose phosphate involving the carbamoylation of p-methylaspartic acid.,, However, DL-threo-p-methylaspartic acid is a competitive inhibitor of L-aspartic acid for the growth of E. .coZi strain B 23 and, moreover, in the same organism, no radioactivity is incorporated into thymine from tritiated /I-methylaspartic acid 24 or ~ ~ - t h r e o - [ M e 14C]-#?-methylaspartic acid.25 L-threo-#?-Methylaspartic acid is not a growth factor for the vitamin B,,-requiring protozoon Ochromoms malhamensis, 26 but it has been reported to stimulate the growth of Poteriochromonas stipitata in the absence of cyanocobalamin. However, even here, the growth stimulation is nevef equivalent to that of vitamin B1,,and it falls off as the level of /I-methylaspartic acid in the medium rises from 0.1% to 0.6%. [Me-14C]Methylaspartic acid is not incorporated into the thymine of regenerating rat liver.28 While these results on the metabolism of p-methylaspartic acid do not present a completely unified picture it seems unlikely that this compound is in fact a component of thymine biosynthesis. MethyImalonyl-coenzyme A Isomerisation.-H. R. Marston g9 suggested in 1959 that inability to utilise propionic acid was the main metabolic lesion in vitamin B,,-deficient sheep, and subsequently it was shown that in deficient rats the activity of the liver enzyme catalysing the isomerisation of methylmalonyl-CoA to succinyl-CoA was much less than in controls.30
R. H. Abeles and H. A. Lee, J. Biol. Chem., 1961, 236, 2347. B. E. Volcani, J. I. Toohey, and H. A. Barker, Arch. Biochem. Biophys., 1961, 92, 381. Is K. L. Smiley and M. Sobolov, Arch. Biochem. Biophys., 1962, 97, 538. 2o M. Kliever and H. J. Evans, Nature, 1962, 194, 108. z1 J. I. Toohey and H. A. Barker, J. Biol. Chem., 1961, 236, 560; H. R. Marston, S. H. Allen, and R. M. Smith, Nature, 1961, 190, 1085. 22E. Seifter and E. Manson, Amer. Chem. SOC. Meeting, Abs., 1959, NO. 41. D. W. Woolley, J. Biol. Chem., 1960, 235, 3238. 2 4 I. H. Koehelik and D. W, Woolley, Biochem. Biophya. Res. Comm., 1961, 6, 279. 2 6 T. Abramsky, L. P. Rowland, and D. Shemin, J. BioZ. Chem., 1962, 237, PC265. 2 6 H. A. Nathan and H. B. Funk, Proc. SOC. Ezp. Biol. Med., 1962, 109, 213. 2 7 H. D. Isenberg, E. Seifter, and J. I. Berkman, Biochim. Biophys. Acta, 1960, 39, 187. naR. E. Webb, S. Kirschfeld, and B. C. Johnson, 2nd European Symposium on Vitamin BIZ,Ferdinand Enke Verlag, Stuttgart, 1962, p. 198. 2 s H. R. Marston, Med. J. Australia, 1959, 2, 105. s o R . M. Smith and K. J. Monty, Biochem. Biophys. Res. Comm., 1959, 1, 105.
l7
404
Propionyl-CoA was already known t o be directly carboxylated t o methylmalonyl-CoA 31 and thus Marston's results could be explained. Smith and Monty 30 also pointed out the similarity between the isomerisations of p-methylaspartic acid and methylmalonic acid, indicating that the vitamin B,, coenzymes might be coenzymes for methylmalonyl-CoA isomerase. This prediction was correct. Methylmalonyl-CoAisomerase activity in an extract of acetone-dried rat-liver mitochondria from vitamin B,,-deficient animals is restored by dimethylbenzimidazolylcobamide coenzyme,32 and similarly the activity of a partially purified isomerase from ox liver was enhanced by the coenzyme.33 The separation of apoenzyme and coenzyme proved cWEcult when the holoenzyme, which could not be inactivated by light or charcoal, was derived from sheep kidney. The apoenzyme had to be precipitated from an ammonium sulphate solution with acid,34 and methylmalonyl-CoA isomerase activity was restored by dimethylbenzimidazolylcobamide coenzyme or benzimidazolylcobamide coenzyme but not by adeninylcobamide coenzyme.34 Isomerase activity in cell-free extracts of Propioniibacterium shermanii is eliminated by treatment with charcoal and restored with pure vitamin B , coenzyme.s5 , The enantiomorph of methylmalonyl-CoA which is the immediate product of the action of HC0,- and biotin on propionyl-CoA is subjected to the action of a racemase before its isomerisation t o succinyl-CoA. The racemase has been partially purified from Propioniibacteria 36 and from an extract of sheep liver.37 The racemisation appears t o occur by movement of the hydrogen atom attached t o the tertiary carbon. This has been shown by exchange studies in T 2 0 37 and by proton magnetic resonance studies.36 Present evidence supports the migration of the intact thioacylated carto boxyl group during the isomerisation of methylmalonyl-CoA (4) succinylCoA ( 5 ) , as originally suggested by Stern and Friedman:33
CH,*CH,CO*S*CoA
fBiotin
HC0,-
/lCo*S*CoA CH3*2CH \3C0,H (4)
f - -
B,* _____,
Coenzyme
W H ,CO*S*CoA 3CH,*C0,H
(5)
Thus, [2-14C]methylmalonyl-CoA gives rise t o [3-14C]succinyl-CoA38 and form enzymically synthesised [ 1- 14C]- and [3-14C]-methylmalonyl-CoA
M. Flavin, P. J. Ortiz, and S. Ochoa, Nature, 1955, 1'76, 823. S. Gurmnani, S. P. Mistry, and B. C. Johnson, Biochim. Biophys. Actu, 1960, 38, 187. 33 J. R. Stern and D. L. Friedman, Biochem. Biophys. Res. Comm., 1960, 2, S2. 3 4 D. Lengyel, R. Mazumder, and 8. Ochoa, Proc. Nut. Acad. Sci. U.S.A., 1960, 46, 1312. S 5 E. R. Stadtman, P. Overath, H. Eggerer, and F. Lynen, Biochenz. Biophys. Res. Comm., 1960, 2, 1; R. Stjernholm and H. G. Wood, Proc. Nut. Acad. Sci. U.S.A., 1961, 47, 303; P. Overath, E. R. Stadtman, G. M. Kellerman, and F. Lynen, Biochem. Z.,1962, 326, 77. 315 P. Overath, G. M. Kellerman, and F. Lynen, Biochem. Z.,1962, 335, 500. 3 7 R. Mazumder, T. Sasakawa, Y . Kaziro, and S. Ochoa, J . Biol. Chem., 1962, 237, 3065. 38 H. Eggerer, E. R. Stadtman, P. Overath, and F. Lynen, Biochem. Z.,1960,
31 32
333, 1.
405
[1 - 14C]- and [4-1*C]-succinyl-CoA, respe~tively.~~suggestion which agrees A with the above labelling results but would require the isomerisation to be an intermolecular rearrangement has been put forward independently by Marston, Miles, and Smith 39* and by Hegre, Miller, and Lane.39a 2,5-Dioxocyclohexane-1,4-dicarboxylic acid (succinosuccinic acid) (6) is suggested as
COzH
oc
COZH
I
CHZ- CH2 SCoA SCoA O
CHz-CHZ
/
COZH
COzH
+ 2CoASH
an intermediate. However, it was not possible to label a pool of this acid 39b from [14C]succinyl-CoA,and further evidence supporting an intramolecular rearrangement has been forthcoming.4* An equal mixture of methyl-[carboxyZ-13C]- and -[thi0ester-~3C]-malonyl-CoA utilised for the was isomerisation. Analysis by mass spectrometry of the succinate produced gave a 13C enrichment in accord with that calculated for an intramolecular rearrangernent.4Oa Similar results were obtained by Kellermeyer and Free carbon monoxide 4 1 is not released during the isomerisation, nor is there release of a free proton. Sheep and other ruminants utilise propionate produced in the rumen, through methylmalonyl-CoA and succinyl-CoAas an energy source. Vitamin B,, deficiency thus deprives the animal of energy and increases the level of circulating methylmalonic acid. This increased level perhaps accounts for the fact that the animals feel unwell and die of inanition, and it may also be the cause of the neurological disease in sheep known as swayback. These matters have been discussed recently.42 Evidence supporting the existence of methylmalonyl-CoA isomerase in man has been reported. Thus vitamin B,, deficiency always raises the level of excreted methylmalonic acid.43 During the reticulocyte response resulting from the administration of folic acid to patients with pernicious anzemia in relapse, the level of excreted methylmalonic acid remained unchanged. It is noteworthy that, whereas the neurological symptoms of pernicious anzemia are alleviated by vitamin B,,, they are not brought into remission by folic acid. It is tempting to suggest, therefore, by analogy, that in man also the rise in tissue levels of methylmalonic acid is responsible for the neurological symptoms of vitamin B,, deficiency. Vitamin B1,-deficient Ochromonas malhamensis, a protozoon with a cannot isomerise requirement for the vitamin similar to that of rnarnma1~,~4
39 ( a ) C. R. Hegre, S. J. Miller, and M. D. Lane, Biochim. Biophys. Ada, 1962, 56, 538; ( b ) H. R . Marston, J. A. Mills, and R . M. Smith, Nature, 1962, 193, 240. 4 0 ( a ) E. F. Phares, M. V. Long, and S. F. Carson, Biochem. Biophp. Res. Comm., 1962, 8, 142; ( b ) R. W. Kellermeyer and H. G . Wood, Biochemistry, 1962, 1, 1124. 4 1 M. Flavin and C. Slaughter, J . Amer. Chem. SOC., 1961, 83, 397. 4 2 H. R . Marston, S. H. Allen, and R. M. Smith, Nature, 1961, 190, 1085. 4 3 A. M. White, Biochem. J . , 1962, 84, 41P; E. V. Cox and A. M. White, Lancet, 1962, 853. 4 4 3 % . E. Coates and J. E. Ford, Biochem. SOC. Symposium, 1955, No. 13, p. 36.
406
methylmalonyl-CoA t o succinyl-CoA. However, the metabolic lesion is alleviated, not only by cyanocobalamin, but also by the methylamide 45 of vitamin B,, which is a specific antagonist of vitamin B,, for the growth of the organism. Methylmalonic acid is not a growth factor for Ochromonas maZhamensis.26 The view was therefore expressed 45 that the growthpromoting reaction mediated by vitamin B,, does not involve methylmalonyl-CoA isomerase. Similar results have been obtained with a marine bacterium. 46 In view of the effect of vitamin B,, on propionate metabolism, interest in its possible effect on general lipid metabolism has been rekindled. This topic has been discussed, particularly with relation t o the chick embryo, by Moore and Doran.* Metabolism of One-carbon Units,-The demonstration of a coenzymic r61e for vitamin B,, in the general oxidation-reduction of one-carbon units which appeared at one time t o be highly probable 4s has not m a t e r i a l i ~ e d . ~ ~ However, work on certain aspects of methionine synthesis in Escherichia coZi has been more fruitfu1.50 Methionine appears t o be synthesised in E. COG by two pathways, only one of which involves vitamin B12. The experimental evidence rests on work with strains 113-3 and 121/176 (methionine/cyanocobalamin auxotrophs) and PA 15 (a glycine/serine auxotroph) which has recently been summarised.50 The pathways from serine are shown in the annexed scheme.51
Serine Pyridoxal p h o s p h v w o x a l phosphate PtHdG PtH,G, NWO-Methylene PtH4G NSNIo-MethylenePtH,GI
NS-MePtHIG Hornocysteine NaDH2
NS-MePtH,G3 VHornocy steine
Methionine PtH,G
FAD, ATP Cobarnide enzyme
PtH4G3
c.
Methionine
PtH4G = Tetrahydropteroylglutamate N6N10-MethylenePtH,G = Tetrahydro-NSN1O-methylenepteroylglutamate N5-MePtH,G = Tetrahydro-N5-methylpter~ylgl~tamate N6N1O-MethylenePtH4G, = Tetrahydro-N5N10-methylenepteroyltriglutamate N6-MePtH,G, = Tetrahydro-N6-methylpteroyltriglutamate 53 FAD = Flavin-adenine dinucleotide = Reduced nicotinamide-adenine dinucleotide NADH, ATP = Adenosine 5-triphosphate
H. R. V. Amstein and A. M. White, Biochem. J., 1962, 83, 264. W. A. Ayers, Arch. Biochem. Biophya., 1962, 96, 210. 4 7 J. H. Moore and B. M. Doran, Biochem. J., 1962, 84, 506. 48 H. R. V. Amstein, 4th Internat. Congress Biochemistry, Pergamon Press, 1960, Vol. XI, p. 286; Biochem. J., 1960, 74, 616; J. 8. Dinning and R. S. Young, J. BioE. Chem., 1959, 234, 3241. 49 A. M.White and H. R. V. Amstein, 2nd European Symposium on Vitamin Bla, Ferdinand Enke Verlag, Stuttgart, p. 186. 6 0 J. R. Guest and D. D. Woods, ref. 49, p. 686. 61 F. T. Hatch, S. Takeyama, R. E. Cathou, A. R. Larrabee, and J. M. Buchanan, J. Amer. Chem. Soc., 1959, 81, 6525; F. T. Hatch, A. L. Larrabee, R. E. Cathou, and J. M. Buchanan, J . Biol. Chem., 1961, 236, 1095.
46
46
407
The 150-fold purification of the cobamide-containing enzyme has been accomplished from strain PA 15.S4 The cobamide derivative does not become available as a growth factor for Escherichia coli 113-3 64b or Lactobacillus Zeichmunii until released by heat,54 digestion with papain,54b or extraction with hydrogen ~ y a n i d e . 5 ~ ~ While ultraviolet light destroys the activity of the cobamide enzyme, visible light or activated charcoal is without effect.54 Dimethylbenzimidazolylcobamide coenzyme can replace cyanocobalamin for the formation of the cobamide enzyme in cell-free extracts but it does not possess cobamide enzyme activity for methionine synthesis in vitr0.54~ What is almost certainly the same cobamide containing enzyme has been isolated from Escherichia coli 113-3.55 However, in the in vitro systems used here dimethylbenzimidazolylcobamide coenzyme was found not to be a precursor. The spectrum of the cobamide enzyme from E. coli 113-3 55 is similar to that of vitamin B12r. Release of the prosthetic group was achieved with warm alcohol (80%) but insufficient material was available for complete characterisation.55 The possibility that the methyl analogue (methyl replacing adenosine) of dimethylbenzimidazolylcobamidecoenzyme may be an intermediate in the formation, or may itself be the prosthetic group, of the cobamide enzyme has been explored.66 The rate of the spontaneous reaction which occurs between the methyl analogue and homocysteine in the presence of mercaptoethanol could be increased up to 10-fold by the purified cobamide enzyme. The [Me-14C]-coenzyme analogue gave methionine with unchanged specific activity in the methyl group, As the authors 66 are aware, the results are open to a number of interpretations but they are not in conflict with the original hypothesis. While it is unlikely from a nutritional point of view that inability to synthesise methionine is the main lesion in vitamin B,, deficiency, and in fact no requirement for vitamin B,, has been found in cell-free methioninesynthesising systems from mammalian sources,57 the possibility remains that other methyl groups may require vitamin B,, for their synthesis. The identification of the cobamide enzyme substrate, tetrahydro-N5-methylpteroylmonoglutamate, in various mammalian tissues,58 including human supports this view, as does the accumulation of serum Lactobacillus cmei activity in patients with pernicious anzmia.59 It should be pointed
5 2 A. R. Larrabee, S. Rosenthal, R . Cathou, and J. M. Buchanan, J. A m e r . Chem. SOC., 1961, 83, 4094; W. Sakami and I. Ustkins, J. B o . Chem., 1961, 236, PC50. il 5 s J. R. Guest, S. Friedman, and M. A. Foster, Biochem. J., 1962, 84, 93P. 5 4 (a) R. J. Kisliuk, J. B o . Chem., 1961, 236, 817; (b) M. A. Foster, K. M. Jones, il and D. D. Woods, Biochem. J., 1961, 80, 519. 65 S. Takeyama, F. T. Hatch, and J. M. Buchanan, J. B o . Chem., 1961, 236, il 1102; S. Takeyama and J. M. Buchanan, J. Biochem. T o k y o , 1961, 49, 578. 5 6 J. R. Guest, S. Friedman, D. D. Woods, and E. L. Smith, Nature, 1962,195, 340. 5 7 A. Nakao and D. M. Greenberg, J. Biol. Chem., 1958, 230, 603; A. Stevens and W. Sakami, ibid., 1959,234,2063; W. Wilmans, B. Rucker, and L. Jaenicke, 2. physiol. chem., 1960, 322, 283. 5 8 (a) L. Jaenicke, 2. physiol. chem., 1961, 326, 168; K. 0.Donaldson and J. C. Keresztesy, Biochem. Biophys. Res.Comm., 1961,5,289; (b) V. Herbert and R. Zalusky, J. Clin. Invest., 1962, 41, 1263. s D D. L. Mollin, A. H. Waters, and E. Harris, 2nd European Symposium on Vitamin BIZ,Ferdinand Enke Verlag, Stuttgart, p. 737.
408
B I O L O G I C A L CHEMISTRY
out that tetrahydro-N5-methylpteroylmonoglutamate unique in that it is possesses growth-promoting activity for Lactobacillus casei.59 Hitherto only triglutamates have been thought to possess this property. The incorporation of [14C]formate into DNA thymine in chick bonemarrow preparations was 2.2 times that obtained when the preparation was from vitamin B,,-deficient chicks. A similar effect was observed when vitamin B12 or the coenzyme was added in vitro.60 No effect was observed when either [14C]formaldehyde or [3-14C]serine was used as one-carbon source.6o Similar stimulation of thymine biosynthesis by vitamin B,, was obtained with Lactobacillus Zeichmanii rendered deficient by growth on deoxyribosides.61 However, a recent attempt to confirm the effect of vitamin B,, on thymine biosynthesis from [14C]formatein LactobaciZZus Zeichmanii was unsuccessfu1,62 and Floyd and Whitehead 63 presented evidence indicating that the uracil deoxyriboside level is the limiting factor in this organism in vitamin B,, deficiency. Thymine biosynthesis from [3-14C]serine,in rats, was shown to be slightly stimulated by vitamin B12, but when [14C]formatewas the precursor vitamin B,, caused a slight reduction in incorporation.49 Only slight stimulation of thymine synthesis (maximum four-fold) was brought about by vitamin B,, in deficient Ochrom o w m~lhamensis.~~ contrast to Dinnings recently repeated 6 4 interIn pretation of his results, Arnstein and White take the view that thymine biosynthesis would have been affected to a much greater extent, if not completely blocked, in deficient O c h r o m o w , if vitamin B,, were in fact a coenzyme for its synthesis. However, the possibility that thymine may be synthesised by alternative routes cannot be ruled out, although in this does not appear to connection tetrahydro-N5-methylpteroylmonoglutamate be involved.65 Dehydration of Glycols and Lysine Fermentation.-Anaerobically grown cultures of Aerobacter aerogenes (ATCC 8724) convert propane-l,2-diol into propionaldehyde, ethylene glycol into acetaldehyde, and glycerol into 3-hydroxypropionaldehyde.66 I n cell-free preparations the ability of the
system to carry out these conversions can be removed if they are treated with activated charcoal, and activity for metabolism of propane-l,2-diol and ethylene glycol is restored by addition of dimethylbenzimidazolylcobamide coenzyme, adenylcobamide coenzyme, and benzimidazolyl6 0 J. S. Dinning and R. S . Young, J . Biol. Chem., 1959, 234, 1199; J. S. Dinning, Proc. SOC. Exp. Biol. Med., 1960, 104, 431. J. S. Dinning and R. S. Young, J . Biol. Chern., 1959, 234, 3241. 6 2 D. Roberts and C. A. Nichol, J . Biol. Chem., 1962, 237, 2278. 13~ K. W. Floyd and R. W. Whitehead, Biochern. Biophys. Res. Cornm., 1960,3, 220. 6 4 J. S. Dinning, Physiol. Rev., 1962, 42, 169. 6 5 Friedkin, quoted by W. S. Beck, New England J . Med., 1962, 206, 708. 6 6 R. H. Abeles, A. M. Brownstein, and C . H. Randles, Biochem. Biophys. Acta, 1960, 41, 530.
409
cobamide coenzyme.67 A 200-fold purification of the enzyme accepting propane-l,2-diol or ethylene glycol has been achieved.s8 The mechanism of the rearrangement has to some extent been elucidated by carrying it out in D,0.6@ No exchange with the solvent occurs, thus suggesting an intramolecular rearrangement. Support for the concept of vitamin B,, coenzyme as part of a transition state, in which it carries a hydride ion, is claimed 68 from the observation that w , , . for the conversion of [1-2H]propane-1,2-diolis only one-tenth of that of the non-deuterated substrate. While the synthetic coenzyme 7 0 is active in the Aerobacter aerogenes system a number of other synthetic coenzyme analogues 7 1 besides cyanocobalamin are powerful competitive antagonists of the coenzyme. These analogues are not inhibitory for the growth of chicks or Ochromonus malhamensis. 71 A glycerol dehydrase which requires dimethylbenzimidazolylcobamide coenzyme, from an acraldehyde-forming Lactobacillus, has also been identified.l9 The similarity between the production of aldehydes by the dehydration of vicinal glycols and formation of deoxyribose from ribose is striking. However, convincing proof in a cell-free system of the existence of a cobamide-requiring dehydrase (or reductase) for ribotides is still lacking. Work has been mainly concerned with the metabolism of intact Lactobacillus leichmanii after establishment of the nutritional fact that, in the absence of vitamin B,,, growth requirements for the organism can be met by any deoxynucleoside.72 Thus when Lactobacillus leichmanii is grown in the presence of [l*C]thymidinebut in the absence of vitamin B,, the deoxyribose from DNA is obtained with undiluted specific activity. I n the presence of the vitamin there is a 10-50-fold decrease in specific activity of the four deoxynucleosides, due presumably to increased synthesis from non-radioactive sources in the growth medium.73 Similarly the incorporation of [l-14C]ribose into deoxyribose is not apparent when cells are grown on deoxycytidine, but can be stimulated when vitamin B,, is added to the growth medium.74 Further evidence of a similar nature continues to a c c ~ m u l a t e7.5~ The observation that the DNA content of cells grown on ~~ vitamin B,, is twice that in cells grown on deoxyrib~sides,~~ although disp ~ t e dhas been confirmed and extended by others. Thus cultures of the ,~~ same turbidity contain three times the number of cells when grown with optimal concentrations of vitamin B,, than when grown with thymidine, and the RNA: DNA ratio of the cell mass is 6.9 with vitamin B,, and
07R.
6B
69
70
A. M. Brownstein and R. H. Abeles, J. Biol. Chem., 1961, 236, 1199. E. Lester Smith, L. Mervyn, A. W. Johnson, and N. Shaw, Nature, 1962, 194,
R. H. Abeles and H. A. Lee, Fed. Proc., 1962, 21, 253.
H. Abeles and H. A. Lee, J. Biol. Chem., 1961, 236, PC1, 2347.
E. Lester Smith and L. Mervyn, Biochem. J., 1963, 86, 2P. J. Lascelles and M. J. Cross, Biochem. SOC. Symposium, 1955, No. 13, p. 109. 73 M. Downing and B. S. Schweigert, J. Biol. Chem., 1956, 220, 521. 7 4 W. H. Spell and J. S. Dinning, J. Amer. Chem. SOC., 1959, 81, 3804. 7 5 L. A. Manson, J. Biol. Chem., 1960, 235, 2955; A. Wacker, S. Kirschfeld, and L. Triiger, 2. Naturforsch., 1959, 14b, 145. 7 6 A . Wacker, D. Pfahl, and I. Schroder, 2. Naturforsch., 1957, 12b, 510. 7 7 G. D. Birnie and G. W. Crosbie, Biochim. Biophys. Acta, 1961, 46, 397.
71
72
1175.
410
16.0 with thymidine. Vitamin B,, and deoxyriboside limitation operate in an apparently identical manner to produce non-viable filaments of the type associated with defective DNA synthesis in other organisms. I n these filaments the RNA: DNA ratio rises to 34.1 in the case of vitamin BI2restricted organisms and 41.1 in thymidine-restricted cells.78 Addition of an excess of vitamin B,, to previously limited ciiltures of Lactobacillus Zeichmanii increases the concentration of DNA and the ratios DNA : RNA and DNA : protein. The concentration, per mg. of protein, of acid-soluble deoxyribonucleotides is also increased 3-4 times in 60 minutes.79 The suggestion has been made that the megaloblast is in its own way similar to these filamentous forms of Lactobacillus Zeichmanii and is in a state of impaired deoxyribonucleotide biosynthesis.80 However, attempts to cure pernicious anEmia with thymidine have not proved successful 81 although it has been suggested that this failure may have been due to the absence of tram-N-deoxyribosidase in human tissue.65 The incorporation of [14C]cytidineinto deoxycytidine in liver minces from deficient chick embryos is not stimulated by cyanocobalamin.82 In contrast, synthesis of deoxyribose containing substances in a cell-freeextract, containing ATP, AMP, and TPNH, of a murine leukaemic cell L-5178Y is reduced to about a third of the original by treatment with charcoal, and synthesis is generally restored to about two-thirds of the original level by addition of cyanocobalamin in vitro : in one case, 100%restoration of activity was obtained. Restoration of activity is not accomplished with folic acid derivatives.83 It would be interesting to know the effect of the Barker coenzyme on these mammalian deoxyribotide-synthesisingsystems. Soluble extracts of an Equadorian clostridium have been obtained which are capable of degrading lysine to butyrate and acetate when supplemented with DPN.8* After treatment with charcoal the enzyme preparation exhibited a requirement for boiled extract of fresh cells. The indications are that, besides iron(=) and pyruvate, another component of the boiled extract which is necessary for lysine fermentation is the coenzyme of vitamin BI2. Pyruvate-CO, Exchange.-The requirement for dicyanocobinamide in aerobic incubations designed to show C0,-pyruvate exchange 8 5 in cell-free extracts of Clostridium acidi urici and C. butyricum has been further examined 86 with LC strain 1, an aerobe with a pyruvate-oxidising system closely resembling C. butyricum. A specific requirement for a high concentration (100 pmoles/ml.) of mercaptoethanol was demonstrated 86 and it was observed 86 that the requirement for vitamin B,, derivatives was eliminated when carbon dioxide exchange was conducted under nitrogen ;
W. S. Beck, S. Hook, and B. 1. Barnett, Biochim. Biophys. Acta, 1962, 55, 455. W. S . Beck, M. Goulian, and S. Hook, Biochim. Biophys. Acta, 1962, 55, 470. W. S. Beck, J . Clin. Invest., 1961, 40, 1024. G. . Spray and L. J. Wills, Lancet, 1958, 2, 869. 1 ti2 A. Bolinder and P . Reichard, J. Biol. Chem., 1959, 234, 2723. B3L. A. Manson, 2nd European Symposium on Vitamin BIZ,Ferdinand Enke Verlag, Stuttgart, 1962, p. 191. 8 4 T. C. Stadtman, J . Biol. Chem., 1962, 237, PC2409. s 5 J. C. Rabinowitz, J . Biol. Chem., 1960, 235, PC50. 8 6 J. L. Peel, J. Biol. Chem., 1962, 237, PC263.
78
79
W H I T 3 : V I T A M I N B, ,
41 1
much lower thiol concentrations also sufficed. Derivatives of vitamin B, , are efficient catalysts for the autoxidation of mercaptoethanol :86, 4HO*CH,*CH,*SH 0, ---+ 2H20 2(HO*CH,*CH,*S*),; and thus it has been suggested 86 that vitamin B,, and the thiol act as oxygen-scavenger in the original aerobic system.85 Bioswthesis of Coba,mides.-This topic has been the subject of reviews,g8u, as has been the guided biosynthesis in Propioniibacteria. g8c &Amino[1 ,4-14C,]l~wlicacid 8 9 and [14Clporphobilinogen90 are incorporated intact into microbidly synthesised cobamides, and thus it appears that the biosynthesis of the corrin ring follows a similar pattern to that of the porphyrin residue. The extra methyl groups a t positions 2, 5, 7, 12, and 15 are derived from the methyl group of methionine.91 The closure of the corrin nucleus between rings A and D probably takes place simultaneously with introduction of the cobalt The aminopropanol residue is derived from threonine,93 but it has recently been shown 94 that cobyrin-abcdeg-hexa-amide f-N-DL-threonine phosphate cannot be utilised by Propioniibacteriurn shermanii for the biosynthesis of cobamides; nor can it replace vitamin B,, for the growth of Escherichia coli 113-3.g4 Thus the decarboxylation of threonine probably occurs before its condensation with cobyrin-abcdeg-hexa-amide during the formation of cobinamide. The succession of straightforward biosynthetic reactions between cobinamide and the cobamide ion, postulated by Dellweg et aLg5 and later amp15ed,88unamely, Cobinamide -+ Cobinamide phosphate
Cobamide ion t- Cobinakide ribose phosphate has had to be modified. The guanosine 5-pyrophosphoric acid ester of cobinamide (ribose linked to N-9 of guanine) can be isolated from cobamideproducing strains of Nocardia rugosa 96 and it was shown that the specific activity of the cobamide (isolated as cyanocobalamin)with S2Pincorporated was reduced when cobinamide pyrophosphoryl guanosine was included in the growth medium.97 The annexed scheme was considered to be most likely for the biosynthesis of the cobamide ion:96,97
J. L. Peel, Biochem. J . , 1962, 85, 17R. (a) S. K. Kon and J. Pawelkiewicz, Proceedings 4th Internat. Congress of Biochemistry, Vol. XI, Pergamon Press, 1960, p. 115; (a) K. Bernhauer, 0. Miiller, and F. Wagner, 2nd European Symposium on Vitamin B12,Ferdinand Enke Verlag, Stuttgart, 1962, p. 37; (c) D. Perlman, J. M. Barrett, and P. W. Jackson, op. cit., p. 58. D. Shemin, J. W. Corcoran, C. Rosenblum, and I. M. Miller, Science, 1956, 124, 272. OO J. W. Corcoran and D. Shemin, Biochiina. Biophys. Acta, 1957, 25, 661. O1 R. Bray and D. Shemin, Biochim. Biophys. Acta, 1958, 30, 647. O 2 R. Bonnet, J. R. Cannon, A, W. Johnson, I. Sutherland, and A. R. Todd, Nature, 1955, 176, 328. O3 A. I. Krasna, C. Rosenblum, and D. B. Sprinson, J . BioE. Chem., 1957, 225, 745. 04K. Bernhauer and F. Wagner, Biochem. Z . , 1962, 335, 325. O 6 H. Dellweg, E. Becker, and K. Bernhauer, Biochem. Z., 1956, 327, 422. O 6 R. Barchielli, G . Boretti, A. DiMarco, P. Julita, A. Migliacci, A. Mmghetti, and S. Spalla, Biochem. J., 1960, 74, 382. O 7 G. Boretti, A. DiMarco, L. FUOCO, P. Marnati, A. Migliacci, and C. Spalla, M. Biochim. Biophys. Acta, 1960, 37, 379.
87
88
412
Cobinamide ;
.
ADP
Cobinamide phosphate
Cobinarnide pyrophosphoryl guanosine

~ ~ ~ ~ ~ ~ ~ riboside ~ , ~ " ~ i ~ i ~ -
5,6-Dimethyl benzimidazolylcobarnide ion
Convincing evidence concerning the fhal step has only recently become available.98,99 A benzimidazole-requiring strain of Nocardia rugosa which produces cobamides in the presence of 5,6-dimethylbenzimidazoleor its riboside, was shown to incorporate the riboside into the cobamide ion with negligible exchange of the riboside part with [14C]ribose present in the medium.98 Fudher, analogues of benzimidazole were not interchangeable with 5,6-dimethylbenzimidazole, that cobamide analogues could not be so pr0duced.~8 The accumulation by Propioniibacterium shermunii (in both the presence and the absence of cobalt) of 5,6-dimethylbenzimidazole riboside 99 supports these results, but is in conflict with work based on the relative ease of uptake of the base, as compared with its riboside and ribotide in Escherichia coli 95 and Propioniibacterium shermunii. loo However, permeability problems were doubtless involved here.88 It seems unlikely that the finer points of cobamide biosynthesis will be settled until more work is done on cell-free systems. I n this connexion extracts of acetone powders from E. coli 113-3 have been obtained which incorporate 5,6-dimethylbenzimidazole 101 into cobamide derivatives. All the biosynthetic intermediates mentioned above have been isolated by methods which would destroy an organometallic bond of the type present in the coenzyme. However, it has been possible t o isolate from Nocurdia rugosa 466 cobyrin-abcdeg-hexa-amide,a, precursor of cobinamide, linked to an adenine-containing group.102 From Propioniibacterium shermnii, lightsensitive derivatives of cobinamide and related compounds have been isolated.13, 103 It seems highly probable, therefore, that the organometallic bond is formed early in the biogenesis of cobamides. Conversion of Cyanocobalamin into the Coenzyme.-Besides some preliminary results in which cell-free extracts of Propioniibacterium shermanii were shown to require Mg2f and ATP for the conversion of 5,6-dimethylBarbieri, G. Boretti, A. DiMarco, A. Magliacci, and C. Spalla, Biochim. Biophys. Acta, 1962, 57, 599. g g H. C. Friedman and D. L. Harris, Biochem. Biophys. Res. Cornm., 1962, 8, 164. loo K. Bernhauer, E. Becher, and G. Wilharm, Arch. Biochem. Biophys., 1959, 83, 248. lol J . Pawelkiewicz and B. Bartosinski, Bull. Acad. polon. Sci., Ser. Sci. Biol., C1. 11, 1960, 8, 5. l o 2 A. Migliacci and A. Rusconi, Biochim. Biophys. Acta, 1961, 50, 370; K. Bernhauer, F. Wagner, and D. Wahl, Biochem. Z., 1961, 334, 279. lo3L. Nowicki and J. Pawelkiewicz, Bull. -4cad. polon. Sci., Ser. Sci. Biol., C1. 11, 1960, 8, 123.
FAWCETT: T H E NICOTINAMIDE COENZYMES
413
benzimidazole aquocobamide into the coenzyme,lo4more detailed work has recently appeared. The co-factor requirements for the conversion of 5,6dimethylbenzimidazolylcobamidecyanide or hydrate into the coenzyme in cell-free extracts of Propioniibacterium shermanii include DPNH, GSH, Mn2+, ATP, and FAD,lO5 and confirmation has been obtained lo7of an earlier finding 106 for similar systems from C. tetanomorphum that the cobalt-bound adenosine in the coenzyme is derived intact from ATP. It also appears that 5,6-dimethylbenzimidazolylhydroxocobamideis an intermediate in the formation of the coenzyme from ~yanocoba1amin.l~~ Recently, reduction to the BIzr state was not observed with a more highly purified enzyme system than previously used, and this is not considered an obligatory intermediate in the enzymic conversion of cyanocobalamin into the coenzyme.los A. M. W.
4. THE NICOTINAMIDE COENZYMES AND THEIR APOENZYMES
SEVERAL surveys of this field have appeared during the period from 1959 to 1961,1--s although only one related review has previously been presented in Annual The present Report deals with the chemical and biological properties of the nicotinamide coenzymes and of some of the wellcharacterised enzymes. The Coenzymes.-In recent reviews of the chemist,ryof the coenzymes,2a the addition compounds formed between nicotinamide adenine dinucleotide (NAD+) (1) and various nucleophiles are formulated either as covalent compounds or charge-transfer complexes, and this lack of definition is also associated with many explanations of the biological processes in which the nicotinamide coenzymes are involved. New methods have appeared for the microestimation of the coenzyme which involve using enzymic-cycling and fluorescent techniques, and for
lo*J. Pawelkiewicz, B. Bartosinski, and N. Walerych, Acta Biochem. Polon., 1961, 8, 131; K. Bernhauer, P. Gaiser, 0. Muller, and 0. Wagner, Biochem. Z.,1960, 333, 106. lo6R. 0. Brady and H. A. Barker, Biochem. Biophys. Res. Comm., 1961, 4, 464. l o *A. Peterkofsky, B. Redfield, and H. Weissbach, Biochem. Biophys. Res. Comm., 1961, 3, 213. lo R. 0. Brady, E. G. Castanera, and H. A. Barker, J . Biol. Chem., 1962, 237, 2325. lo8H.Weissbach, B. G. Redfield, and A. Peterkofsky, J . Biol. Chem., 1962, 237, 3217. Ciba Foundation Study Group No. 2, Steric Course of Microbiological Reactions, J. & A. Churchill Ltd., London, 1959. (u)N. 0. Kaplan, in The Enzymes, ed. P. D. Boyer, H. A. Lardy, and K. Myrback, Academic Press, New York and London, 1960,2nd edn., Vol. 111, p. 105; E. M. Kosower, op. cit., p. 171; ( b ) B. L. Vallee, op. cit., p. 225. Sulphur in Proteins, ed. R. Benesch et al., Academic Press, New York, 1959, Section IV. S. Shifrin and N. 0. Kaplan, Adv. Enzymol., 1960, 22, 337. S. F. Velick, in Light and L f , ed. W. D. McElroy and B. Glass, The Johns ie Hopkins Press, Baltimore, 1961, p. 10s. E. M. Kosower, Molecular Biochemistry, McGraw-Hill Book Co. Inc., New York. 1962. Ann. Reports, 1958, 55, 343. 0. H. Lomy J . V. Passoneau, D. W. Schultz, and M. K. Rock, J. Biol. Chem., 1961, 236, 2746.
414
the separation of all fhe four coenzymes by chromatography on diethyl. aminoethylcellulose. The enzymic preparation of NADH has been further modified to give a more active product.lO The low resistance of all the coenzymes to acid and alkaline treatment has been re-investigated l1and should lead t o the realisation that the oxidised and the reduced nicotinamide dinucleotides must not be exposed t o high or low pH. The complex series of reactions which NADH undergoes in acid solution has been considerably clarified. llC On spectrophotometric grounds, the initial product is thought dinucleotide (2) as had pret o be the tetrahydro-6-hydroxynicotinamide viously been claimed from reactions of model compounds l2 although one report claimed that 5-hydroxylation had occurred. l3 A second hydroxyl group is then introduced at position 2 (3), giving a product which can exist in tautomeric acyclic forms and which eventually liberates the dialdehyde (4) detected previ0usly.1~
HO
OrNH
F H
R
CO.NH2
( R = ADP- R i b o s e )
N
R
I
OH
The nature of the mysterious NADH-X remains uncertain. This is formed from NADH enzymically with 3-phosphoglyceraldehyde dehydrogenase in the presence of inorganic phosphate 15 or, more slowly, in a solution
E. J. Pastore and M. Friedkin, J . Bwl. Chern., 1961, 236, 2314. Dalziel, Biochern. J . , 1962, 84, 240. 11 ( a ) 0. H. Lowry, J. V. Passoneau, and M. K. Rock, J . Biol. Chem., 1961, 236, 2756; ( 6 ) I. G. Fels, Science, 1961,134,280; Nature, 1962,195, 704; (c) A. Stock, E. Sam, and G. Pfleiderer, Annalen, 1961, 647, 188. 12A. G. Anderson and G. Berkelhammer, J . Arner. Chem. SOC., 1958, 80, 992. 13 R. Segal and G. Stein, J., 1960, 6254. 1 4 R. M. Burton, ref. 99 quoted in ref. 2a. 15 S. Chaykin. J. 0. Meinhart, and E. G. Krebs, J . B i d . Ohem., 1956,220,811, 821.
9 l o K.
F A W C E T T : THE NICOTINAMIDE COENZYMES
415
of high phosphate concentration.16 Its formation via a labile tetrahydro-6phosphonicotinamide dinucleotide has been postulated. 110 Thia intermediate 6-phospho-derivative must be closely related to the new phosphorylated NAD derivative which accumulates when NAD f, inorganic phosphate, and succinate are incubated with mitochondriaY17 it is reported that the as new compound decomposes to NAD+ and phosphate and also to a compound similar to the primary acid decomposition product of NADH. Details of the oxidation state of the intermediate are not clear. The existence of this type of intermediate was postulated in 1951 in a scheme involving a pyridone dinucleotide,l8 since when several reports of its existence have appeared 19 cumulating in the isolation of the compound mentioned above. The existence of still more compounds related to, or derived from, NADH has been revealed by the discovery of the appearance of a potent inhibitor of several dehydrogenase enzymes in frozen concentrated solutions of NADH or in solid samples exposed to a moist atmosphere, and even in fresh commercial samples.20 The initial suggestion that it was in fact adenosine &phosphate ribose, a breakdown product of both NAD+ and NADH, was excluded because of its weak inhibitory properties. The kinetic treatment of the situation in which a competitive inhibitor is present in constant molar proportion to the coenzyme shows that the decrease in reaction velocity is given by the ratio of K , for the coenzyme to K I rather than by KI alone. Thus a very small amount of inhibitor could have a surprisingly large effect when NADH judged to be pure by its absorbency ratio at 260 and 340 mp is used, as has been found.lo Some light may have been shed on this situation by the detection of small amounts of hydrogen peroxide in NADH solutions.21 The level of peroxide rose greatly on irradiation at 365 mp, or a t higher pH, and in the latter case storing the frozen solution caused a further increase in peroxide content. It remains to be seen whether the peroxide giving rise to the inhibitor, is formed simultaneously, or is, in fact, at all related to it. Further work on the chemical properties of pyridine derivatives continues to give information concerning the mechanism of the enzyme-catalysed reaction and has been recently reviewed.22 By using l-alkoxynicotinamide compounds it has been shown that the dielectric constant of the solvent significantlypromotes addition of cyanide to the 6-positionof nicotinamide.23 Interesting descriptions of the participation of model compounds
G. Pfleiderer and A. Stock, Biochem. Z . , 1962, 336, 66. D. E. GrifKths and R. A. Chaplain, Biochem. Biophys. Res. Comnm., 1962, 8, 497, 501. N. 0. Kaplan, in Phosphorus Metabolism, ed. W. D. McElroy and B. Glass, The Johns Hopkiris Press, Baltimore, 1951, Vol. I, p. 428. l D G. B. Pinchot, PTOC. Nat. Acud. Sci. U.S.A., 1960,46, 929; J. L. PurviS, Biochim. Biophys. Acta, 1960, 38, 435; G. B. Pinchot and M. Hormanski, Proc. Nat. Acad. Sci. U.S.A., 1962, 48, 1970. 2 o K. Dalziel, Biochem. J., 1961, 80, 440; C. P. Fawcett, M. M. Ciotti, and N. 0. Kaplan, Biochim. Biophys. Acta, 1961, 54, 210; P. E. Strandjord, K. J: Clayson, and E. F. Freier, Fed. Proc., 1962, 21, 239. 21 M. I . D o h , Biochim. Biophys. Acta, 1962, 63, 219. 2 2 F. H. Westheimer, Adv. Enzymol., 1962, 24, 441. 2 s Y . Kagawa, J . Biochem. (Japan), 1960, 47, 104.
l6 l7
416
in oxidation and reduction reactions include the reduction of an olefinic double bond,24analogous to the enzymic hydrogenation of androstenedione to androstanedione by NADPH;25 the reduction of sulphite to hydrogen sulphide involving addition to the nicotinamide 6-position, and a brief 26 report on the complex stereochemistryinvolved in a model transhydrogenase system in which hydrogen is transferred from dihydro-1-propylnicotinamide to NAD+.27 The relation of ring substitution and electron affinity of a pyridine ring to the wavelength of maximal absorption of the charge-transfer band of alkylpyridinium iodides has been investigated.28 The suggestion that the broad absorption band observed when NAD+ is bound to glycersldehyde 3-phosphate dehydrogenase may be due to a charge-transfer complex 29 has received new experimental support ;3O the criticism 31 of earlier evidence 32 remains valid as it emphasises the dangers of observing artificial spectra when difference spectra of concentrated solutions are measured. Coenzyme modi$cations. There now exists a series of enzymically prepared coenzyme analogues containing various 3-substituted pyridine groups in place of ni~otinamide.~~ general, their chemical properties and bioIn logical activities can be correlated with the ability of the 3-substituent to conjugate with the pyridine ring, as is shown in the respective l-methylpyridinium bases,34 although these model compounds do not duplicate the inductive effect on the pyridine ring in a riboside 5-phosphate. The activity shown by these analogues indicates that the 3-amidegroup in the coenzyme represents a convenient biological adaptation of the nicotinic acid precursor, to give a small unreactive carbonyl group contributing to the overall electron distribution of the nicotinamide ring, in both oxidised and reduced forms, requisite for its coenzymic r81e. These analogues have proved to be valuable tools in studies on dehydrogenase differentiation and evolution.35 Additions to this series include the Fi-amino-, &methyl-, and 4-methyl-nicotinamide analogues,36 all of which are inactive as coenzymes. Several other adenine dinucleotides have been prepared containing tertiary bases other
24 B. E. Norcross, P. E. Klinedist, jun., and F. H. Westheimer, J. Amer. Chem. Soc., 1962, 84, 797. 2 5 J. S. McGuire and G. M. Tomkins, Fed. Proc., 1960, 19, 29. 2 6 K. Wallenfels and D. Hofmann, Tetrahedroh Letters, 1962, 151. 2 7 J. Ludoweig and A. Levy, Fed. Proc., 1962, 21, 239. 28 E.M. Kosower, J. A. Skorcz, W. M. Schwarz, jun., and J. W. Patton, J. Amer. 1 Chem. Soc., 1960, 82, 2188; E. M. Kosower and J. A. Skorcz, ibid., p. 2195; E. 3 . Kosower, D. Hofmann, and K._Wallenfels, ibid., 1962, 84, 2755. 2 g E .M. Kosower, J. A m e r . Chem. SOC.,1956, 78, 3497. 30G. Cilento and P. Tedeschi, J. Biol. Chem., 1961, 236, 907; F. Ungar and S. G. A. Alivisatos, Biochim. Biophys. Acta, 1961, 51, 361. 31 C. Remily and R. G. Wolfe, Biochem. Biophys. Res. Comm., 1960, 3, 457. 3 2 G. Cilento and P. Giusti, J. Amer. Chem. SOC., 1959, 81,3801; S. G. A. Alivisatos, G. A. Mourkides, and A. Jibnil, Nature, 1960, 186, 718. 33 ( a ) N. 0. Kaplan and M. M. Ciotti, J. Biol. Chem., 1956, 221, 823; ( b ) B. M. Anderson, C. J. Ciotti, and N. 0. Kaplan, ibid., 1959, 234, 1219; ( c ) B. M. Anderson and N. 0. Kaplan, ibid., p. 1226. 3 4 M. R. Lamborg, R. M. Burton, and N. 0. Kaplan, J. Amer. Chem. Soc., 1957, 79, 6173. 3 5 N. 0. Kaplan, M. M. Ciotti, M. Hamolsky, and R . E. Bieber, Science, 1960, 131, 392. 36 P. Walter, Fed. Proc., 1962, 21, 240.
FAWCETT : THE NICOTINAMIDE COENZYMES
417
than pyridine derivatives, such as imidazoles 3 7 and t h i a d i a z ~ l e s . ~ ~ An exciting application of this type of compound is the coupling of the 4-methyl5-2-hydroxyethylthiazole adenine dinucleotide to horse-liver alcohol dehydrogenase.39 This was accomplished by opening the thiazole ring under alkaline conditions and forming a disulphide bridge with a thiol group of the enzyme. Evidence from the method of formation and the inhibition by NADf indicate that the enzyme-thiol group involved in the dinucleotide disulphide is normally responsible for coenzyme binding, and isolation of the appropriate peptide fragments after hydrolysis may lead to identification of the primary structure a t part of the coenzyme binding site. It is certainly remarkable that the molar ratio of the adduct (if maximal) approached the number of coenzyme-binding sites per mole of enzyme (two). In view of the number of free thiol groups in this enzyme, demonstration of the absence of disulphide formation between the thiazole analogue and thiol groups of a protein other than a dehydrogenase seems desirable. Further modifications of NAD + have been made in the adenine nucleotide part of the molecule in an attempt to discover the r81e of this portion in enzyme-coenzyme association and, indeed, in any nucleotide-protein interaction. These new nicotinamide dinucleotides contain 2-deoxyadeno42 1-2~ine~~O-42 hypoxanthine,43 guanine,42, 44 cytosine,42 hydroxyethyladenosine,4 5 6- 2-hydroxyethylaminopurine, and 6-mercaptop~rine.~6 Exact comparison of the coenzymic activities of these compounds is diEicult owing to differences in assay conditions, but some fundamental facts arise concerning the requirements of the better-known dehydrogenases, Horse-liver alcohol dehydrogenase shows little sensitivity to replacement or modification of adenine unless the assay is carried out at a pH which causes positive or negative charges on the new residue. I n contrast, the yeastalcohol dehydrogenase is inactive with analogues containing modifications in the adenosine part of the coenzyme except a t the extranuclear amino-group. In HO OH ---..-N> N NH2 general, the requirements of the lactic and the glutamic dehydrogenase lie between the extremes of the two alcohol dehydrogenases. The greatly decreased activity of the 2-de- H 0 . W (5) oxyadenosine analogue is surprising and points to a conformational difference between adenosine and 2-deoxy-
c% ? :
37 S. G. A. Alivisatos, L. Lamantia, and B. L. Matijevich, Biochim. Biophys. Acta, 1962, 58, 201, 209. 38 M. M. Ciotti, N. 0. Kaplan, A. Goldin, and S. R. Humphreys, Proc. Amer. Assoc. Cancer Res., 1958, 2, 287. 39 J. van Eys, R. Kretszchner, W. S. Tseng, and L. W. cunningham,jun., Biochem. Biophys. Res. Comm., 1962, 8, 243. 4 0 H. Klenow and B. Anderson, Biochim. Biophys. Acta, 1957, 23, 92. 41 C. P. Fawcett and N. 0. Kaplan, J . Biol. Chem., 1962, 237, 1709. 4 2 M . Honyo, Y. Furukawa, H. Moriyama, and K. Tanaka, Chem. and Pharm. B d l . ( J a p a n ) , 1962, 10, 73. 43 F. Schlenk, F. Hellstrom, and H. von Euler, Ber., 1938, 71, 1471; N.0. Kaplan, S. P. Colowick, and M. M. Ciotti, J . Biol. Chem., 1952, 194, 579. 4 4 M. R. Atkinson, J. F. Jackson, and R. K. Morton, Nature, 1961, 192, 946. 4 5 H. G. Windmueller and N. 0. Kaplan, J . Biol. Chem., 1961, 236, 2716. 4 6 M. R. Atkinson, J. F. Jackson, and A. W. Murray, Nature, 1962, 198, 35.
418
adenosine, possibly due to hydrogen-bond interaction between the 2hydroxyl and N-3 of adenine ( 5 ) , as was previously suggested.47 I n addition, differences in the nuclear magnetic resonance spectra of ribonucleosides and 2-deoxyribonucleosides also indicate considerable varia tion in the pentose ring.48 Inhibition of dehydrogenase activity by coenzyme analogues has so far been reported t o occur only with some of the dinucleotides containing nicotinamide variations 33c, 4 9 and not with those modified in the adenosine group. Evidence for a folded conformation of NADH and its implications has been discussed elsewhere;2a,5 evidence for a similar shape in the NAD+ molecule has been obtained from the electronic interactions in the h m i n o nicotinamide adenine dinucleotide, as shown by its fluorescent properties.36 The influence of the folded conformation of NADH is seen in its nuclear magnetic resonance spectrum where the resonance position of the 4-hydrogen atoms is shifted when compared with that of the l-benzylnicotinamide model.50 The equivalent resonance of the two hydrogen atoms was, taken t o mean that the dihydronicotinamide ring is either planar or undergoing rapid interconversion between two boat forms. Further evidence for planarity of the ring comes from a study of 1,4-dihydropyridines in which the inherent stabilisation of their n-electrons lowers their basicity compared with that of other reduced trimethylpyridine compound^.^^ The use of the fluorescence of NADH t o measure its binding to enzymes and for kinetic studies S2 has been extended t o measurement of polarisation of coenzyme fluorescence for following complex formation between enzyme and c0enzyme;~3and it has been adapted for studying the behaviour of reduced nicotinamide nucleotides in suspensions of cellular preparations 5 4 and in tissues in viv0.55 The phenomenon of the shift towards lower wavelengths and intensification of the coenzyme fluorescence in the presence of enzyme has now been observed with lactic,5Oa rnalic,5@ and isocitric dehydrogena~es.5~~ Of exceptional interest is the determination of the absolute stereochemical configuration at the nicotinamide 4-position in NADH. Comparison of the optical rotatory dispersion curves of the deuterosuccinic acids obtained by degradation of two samples of NADH deuterated at the 4-position on side A and side B, with the curve obtained from a sample prepared independently and of known absolute configuration, decided between the alterP. C. Zamecnik, Biochem. J., 1962, 85, 257. C. D. Jardetsky, J. Amer. Chem. SOC., 1960, 82, 229; R. U. Lemieux, Canad. J . Chem., 1961, 39, 116. 4 9 P. Walter, personal communication. 5 0 W. H. Meyer, H. R. Mahler, and R. H. Ba.ker, jun., Biochim. Biophys. Acta, 1962, 64, 353. 5l E. M. Kosower and T. S. Sorensen, J. Org. Chem., 1962, 27, 3764. 5 2 H. Theorell and A. D. Winer, Arch. Biochem. Biophys., 1959,83,291; H. Theorell, A. P. Nygaard, and R. Bonnichsen, Acta Chem. Scand., 1955, 9, 1148. 5 3 G . Weber, Adv. Protein Chem., 1953, 8, 415; S. F. Velick, J. B o .Chem., 1958, il 233, 1455. 5 4 B. Chance and H. Baltchefsky, J. B o . Chem., 1958, 233, 736; Y. Avidor, il J. M. Olson, M. D. Doherty, and N. 0. Kaplan, ibid., 1962, 237, 2377; P. Estabrook, Analyt. Biochem., 1962, 4, 231. 5 5 B. Chance, P. Cohen, F. Jobsis, and B. Schoener, Science, 1962, 136, 325. 5 6 ( a ) A. Carlstrom, Acta Chem. Scund., 1961, 15, 2049; ( b ) H. Theorell and T. A. Langan, ibid., 1960, 14, 933; (c) T. A. Langan, ibid., p. 936.
47
48
FAWCETT : THE NICOTINAMIDE COENZYMES
419
'
natives for sides A and B of the ring and enabled the following rule to be stated: " When an enzyme of class A transfers hydrogen from a substrate to a nicotinamide nucleotide, the hydrogen is added to that side of the nicotinamide ring on which the ring atoms 1 to 6 appear in anticlockwise order." 57 Different Forms of the Enzymes.-While detailed consideration of this phenomenon is outside the scope of this Report, attention is drawn to the evidence that an NAD+-dependent reaction of a given substrate can be catalysed by different enzyme molecules. These enzymes have been collectively referred to as heteroenzyme~~5~ are obtained from unrelated and sources. Differences between the heteroenzymes have been proved both for 59 structure and catalytic acti0n.~5, A discrete source is, of course, of paramount importance in obtaining a supposedly pure enzyme; however, a further complication arises from the heterogeneity of even crystalline enzymes obtained from one tissue of a single species.58, 59 The micro-components have been termed isozymes.60 The differences between the isozymes are more subtle than between the heterozymes and until recently were demonstrable solely by electrophoresis on paper or on solid supporting media. These techniques 6 1 are much used in the search for isozymes, although artificial enzyme heterogeneity, due to charge differences caused by association of metal ions 62 or a foreign protein,63 has been demonstrated. There have also been reports of misleading observations of heterogeneity when dehydrogenase detection was carried out by coupling the enzymic reaction to dye formation,64a nzethod often used on electropherograms of rather crude preparations. Differences in the amino-acid composition of the lactic dehydrogenase isozymes have recently been reported, thus proving that they are not preparative artefacts, and confirming previous reports of differences in physical and kinetic characteristics. The relations established between the isozymes are more significant than their differences, as has already been suggested. After the order in a given series of isozyrnes has been established on the basis of charge differences,it has been found that without exception each of the properties studied changes in a regular way throughout that isozyme pattern.5s, 6 5 The isozymes of a given lactic dehydrogenase have been shown to have the same molecular weight 66 and to be dissociable into four subunits, also of equal molecular weight but possibly of two different charge types, by the action of guanidine hydrochloride.67 Immunological evidence
6 7 J. W. Cornforth, G. Ryback, G. PopjBk, C. Donninger, and G . Schroepfer, Biochem. Biophys. Res. Comm., 1962, 9, 371. 6 8 T. Wieland and G. Pfleiderer, Angew. Claem., 1962, 74, 261; Internat. Edn., 1962, 1 169. , 5 s Several papers i Ann. N . Y . A c d . Sci., 1961, 94, Article 3, p. 655. n 6 o C. L. Markert and F. Moller, Proc. Nut. Acad. Sci. U.S.A., 1959, 45, 753. 6 1 0. Smithies, A d v . Protein Chew., 1959, 14, 65. 6 2 D. C. Watts and C. Donninger, Analyt. Biochem., 1962, 3, 489. 63 G. W. Schwert, D. B. S. Millar, and Y. Takenaka, J. Biol. Clzem., 1962, 237, 2131. 6 4 E. S. Vesell and A. G. Bearn, J. Gen. Physiol., 1962, 45, 553. 6 6 R. D. C a b , N. 0. Kaplan, L. Levine, and E. Zwilling, Science. 1962, 136, 962. 8 6 E. Appella and C. L. Markert, Fed. Proc., 1962, 21, 253. 6 7 E. Appella and C. L. Markert, Biochem. Biophys. Res. C m m . , 1961, 6, 171.
420
and studies with coenzyme analogues indicated two extreme types of activity with three intermediate types in a pattern of five isozymes.65 These findings led to proposals that each of the five is a hybridised tetrad of two types of subunit. Much of the above discussion a t present applies only t o the lactic dehydrogenases, although isozymes have also been detected of malicY6* isocitric,69 and glutamic dehydrogenases. 70 It therefore seems that selection of an enzyme for chemical study must be preceded either by demonstration of the absence of isozymes or their separation by the recommended meth0ds.6~~ 71 6gb, Horse-liver alcohol dehydrogenase. The standard commercially available preparation of this enzyme is used by most investigators for preliminary or qualitative work although further purification by chromatography has been described. 72 Complete amino-acid composition is not yet available although 3-2 molecules of tryptophan 73 and 28 free thiol groups have been determined per molecule of enzyme.72 While multiple forms of this enzyme have not been detected, a second alcohol dehydrogenase has been found in liver. Unlike the standard preparation this enzyme is capable of oxidising 2-fluoroethanolY7* it thus seems t o be important t o demonstrate by using the and chromatographically purified enzyme that the dismutation and isomerisation activities attributed t o horse-liver alcohol dehydrogenase are in fact due t o the same protein. The enzyme thiol groups have received further attention from several viewpoints. The use of optical rotatory dispersion techniques has shown that previous observations of inactivation and inhibition of coenzyme binding by p-chloromercuribenzoate is caused by alterations in protein tertiary structure, which is normally maintained, at least in part, by thiol groups.76 The appearance of a Cotton effect during the titration of enzyme with coenzyme mas used t o determine that 2 moles of coenzyme are bound per mole of enzyme. This was confirmed by fluorescence titration of the enzyme and coenzyme in the presence of an excess of isobutyramide, although attention was drawn t o the diaculty experienced in determining an accurate value of enzyme c ~ n c e n t r a t i o n . ~ ~ binding of zinc is thought to involve The a dimercaptide structure,78 and it has been suggested that an enzyme thiol group may add t o the nicotinamide 6-position in the enzyme-coenzyme complex.77 The enzyme shows an unusual pH-independence in its reac6 8 ( a )E. S. Vesell and A. G. Beam, Ann. N . Y . Acad. Sci., 1958,75,286; ( b )H. Boser and G. Pawelke, Naturwiss., 1961, 48, 572. 6 D J. L. Bell and D. N. Barron, Biochem. J , , 1962, 82, 5P. 7 0 H J. van der Helm, Nature, 1962, 194, 773. . 7 1 B. Hess and 8. I. Walter, Klin. WoschenschriJt,1960, 38, 1080; J. S. Nisselbaum, Fed. Proc., 1962, 21, 253. 7 a K. Dalziel, Biochem. J., 1961, 80, 440. 73P. M. Harrison and T. Hofman, Biochem. J., 1961, 80, 38P. 7 4 D. H. Treble, Biochem. J., 1962, 82, 129. 7 5 R. H. Abeles and H. A. Lee, jiin., J. Biol. Chem.., 1960, 235, 1499; J. van Eys, J . B i d . Chem., 1961, 236, 1531; N. K. Gupta and W. G. Robinson, Fed. Proc., 1962, 21, 251. 7 6 T. K. Li, D. D. Ulmer, and B. L. Vallee, Biochemistry, 1962, 1, 114. 7 7 J. S. McKinley-McKee, Biochern. J., 1962, 84, 70P. 7 8 R . Druyan and B. L. Vallee, Fed. Proc, 1962, 21, 247.
FA4WCETT: T H E N I C O T I N A M I D E C O E N Z Y M E S
421
tion with iodoacetate which is probably due to special properties of its thiol groups.'9 The correlation of the changes in optical rotation, fluorescence, and activity of the enzyme caused by heat and urea has emphasised the importance of secondary and tertiary protein structure to dehydrogenase function and coenzyme binding.80 Fluorescence enhancement also gave evidence for a ternary complex between enzyme, coenzyme, and urea which was possibly of the type observed with isobutyramide 81 and previously noted in kinetic experiments.82 Considerable effort has been devoted to determining the validity of the Theorell-Chance mechanism for this enzyme. This describes a compulsory initial association of enzyme and coenzyme followed by.instantaneous interconversion of the ternary complexes formed with substrate.83 A series of theoretical relations between the kinetic parameters has been derived for By this mechanism,84and subjected to experimental v e r i f i ~ a t i o n . ~ ~ - ~ ' comparing data from kinetic experiments with two different substrates it has been shown that the values of certain of the kinetic coefficients are independent of substrate, suggesting steps common to the two reactions. These could be only the formation and breakdown of the enzymecoenzyme complexes, and accordingly their dissociation velocities have been shown to control the maximum rate. Good agreement had also been obtained between the dissociation constants for enzyme and coenzyme, and the equilibrium constant for the overall process, when calculated from the results of kinetic experiments together with the theoretical relations for the simple mechanism, and when determined by direct measurement. Kinetic discrepancies led to the consideration of other mechanisms involving alternate pathways with enzyme-substrate intermediates and the formation of inactive enzymecoenzyme complexes. The observation of an isotope effect on the binding constant for NADH labelled at position 4 suggested an interaction between the hydrogen to be transferred and the enzyme.s7c Attempts to demonstrate this revealed an apparent exchange of the label from reduced coenzyme t o alcohol firmly bound to the enzyme.88 This probably occurred through minute contamination of NADH by NAD+ which would then initiate a cyclic process. This order of contamination of coenzymes by their opposite form or by breakdown products seems almost impossible to overcome and has been invoked to explain other experimental discrepancies such that the Theorell-Chance mechanism is now considered valid for this enzyme.89
L. Genevois and J. Larroqu&ne, Compt. rend., 1962, 255, 2523. L. Brand, J. Everse, and N. 0. Kaplan, Biochemistry, 1962, 1, 423. 81 H Theorell and J. S. McKinley-McKee, Acta Chem. Scand., 1961, 15, 1811. . 8 2 K.V. Rajopalan, I. Fridovich, and P. Handler, J. Biol. Chem., 1961, 236, 1059. 83 H. Theorell and B. Chance, Acta Chem. Xcand., 1951, 5, 1127. 8 4 K. Dalziel, Acta Chem. Xcand., 1957, 11, 1706. 8 5 H. Theorell and J. S. McKinley-McKee, Nature, 1961, 192, 47; Acta Chem. Scand., 1961, 15, 1797. K . Ddziel, Ezochem. J., 1962, 84, 244. (a) R. H. Baker, jun., and H. R. Mahler, Biochemistry, 1962, 1, 35; ( b ) R. H. Baker, jun., ibid., p. 41; ( c ) H. R. Mahler, R. H. Baker, jun., and V. J. Shiner, ibid., p. 47. 8 8 V. P. Fernandez, H. R. Mahler, andV. J. Shiner, jun., Biochemistry, 1962, 1, 259. 8 9 K. Dalziel, Biochem. J., 1962, 84, 69P.
79 8o
422
The structure of the transient ternary complex has been described in several ways differing froin one another mainly on the r61e of ~ i n c . 2 ~ Competitive experiments with metal-binding inhibitors have been interpreted to show that zinc binds either the coenzyme 87c or the coenzyme and substrate (6).91 Observations of inhibition by inorganic ions and other monodentate ligands are best explained by the latter theory.91, 92 The
(Reproduced, by permission, from Acta Chem. Scand., 1961, 15, 1863.)
opinion that zinc is not concerned in binding the coenzyme pyrophosphate group depends on the observation that the enzyme is not inhibited by pyrophosphate,93 which is quite a different ion from that of the coenzyme. An analogy for the binding r61e of zinc is shown by the ease of formation g4 of and the complex salt [Pyridinium]+Zn2+[PO4]3--, in the existence of 1 : 1 chelates between tetrahedral Zn2+ and adenosine 5-phosphate, involving purine and phosphate gr0ups.9~ It should be pointed out, however, that the residual charge on the zinc is not known and may be zero if the metal is tightly bound to the protein as a d i m e r ~ a p t i d e . ~ ~
(7) (Reproduced, by permission, from Biochim. Biophys. Acta, 1962, 56, 477.)
B. L. Vallee and T. L. Coombs, J. Biol. Chern., 1959, 234, 2615. g l R . A. Plane and H. Theorell, Acta Chem. Scand., 1961, 15, 1866. g 2 H. Theorell and J. S. McKinley-McKee, Acta Chena. Scand., 1961, 15, 1834. g3 K. Wallenfels and H. Sund, Biochem. Z., 1957, 8, 329. H. Buss,H. W. Kohlschutter, and W. Ploger, 2. Naturforsch., 1962, 17b, 420. g 6 M. M. Taqui Khan and A. E. Martell, J . Amer. Cheni. SOC., 1962, 84, 3307.
Q*
FAWCETT: T H E NICOTINAMIDE COENZYMES
423
There have been two proposals that quaternary amino-groups are involved in binding substrate and coenzyme. Evidence for substrate binding depends on inhibition of enzyme action by Roussins salt, purported to react specifically with such groups,96 and on equilibrium dialysis studies with s p thetic p0lymers.9~ Evidence for distant interaction between coenzyme and a positively charged amino-group depends on the comparison of the spectral shift observed in the enzyme-NADH complex with that caused by the presence of a quaternary nitrogen atom near an ap-unsaturated ketone system. Postulated zinc-nicotinamide interactions through the amide group have been criticised on the grounds of the direction of the spectral shift, and a transition complex has been proposed in which substrate and coenzyme are held in juxtaposition by quaternary ammonium group (7).98 Yeast-alcohol dehydrogenuse. The r81e of zinc in this enzyme is rather more complex and has been discussed at length The observation that rapid inactivation by metal-chelating agents was retarded by addition of NAD, supported its coenzyme-binding function. Subsequently a slower inactivation by 1,lo-phenanthroline, not reversed by coenzyme, has been demonstrated and shown to be accompanied by dissociation into four s u b ~ n i t s . ~Similar results were obtained for the action of silver ion and Q p-chloromercuribenzoate, namely, instantaneous inhibition followed by dissociation.loo,78 This phenomenon of dissociationinto inactive subunitsis now common among the larger dehydrogenases, and has also been brought about by the action of the detergent, sodium dodecyl sulphate, on this enzyme.lo1 Optical rotatory dispersion has been used to distinguish between the type of denaturation caused by urea or alkali and the inhibition caused by 1,lOphenanthroline.lo2 The resistance of this enzyme t o heat and to treatment with urea has been found to be sigdicantly less than that of the horse-liver enzyme,80but it is not known whether this is connected with the dissociation phenomenon. Further studies on the properties of the thiol groups of this enzyme have revealed that four, out of a total of twenty-four, are particularly reactive to iodoacetamide. The rate of enzyme inactivation caused by iodoacetamide was found to be independent of pH over a surprisingly wide range (cf. ref. 79) ;moreover, it was found to be retarded by the coenzymes, yet accelerated by acetaldehyde alone. These findings were incorporated into a novel reaction mechanism for alcohol dehydrogenases involving the covalent association of NADH with a thiol group whose nucleophilicity is enhanced by hydrogen bonding to an imidazole. It is proposed that the same imidazole is involved in acetaldehyde binding.103 Lactic acid dehydrogenase. Beef heart is the most common source of this enzyme, and further details have appeared of its purification by chromatoA. D. Duclaux, Biochim. Biophys. Acta, 1960, 39, 33, 44. A. D. Duclaux, Biochim. Biophys. Acta, 1961, 54, 76, 84. O * E. M. Kosower, Biochim. Biophys. Acta, 1962, 56, 474. s a F. L. Hoch, R. J. P. Williams, and B. L. Vallee, J . Biol. Chem., 1958, 232, 453; J. H. R. Kagi and B. L. Vallee, ibid., 1960, 235, 3188. loo P. J. Snodgrass, B. L. Vallee, and F. L. Hoch, J . BioZ. Chem., 1960, 235, 504. lol R. T. Hersh, Biochim. Biophys. Acta, 1962, 58, 353. lo2 D. D. Ulmer and B. L. Vallee, J . BioZ. Chem., 1961, 236, 730. lo3 B. R. Rabin and E. P. Whitehead, Nature, 1962, 196, 658.
O6 O7
424
graphy on h y d r ~ x y p a t i t e . ~ ~ method yields a preparation claimed to This have a monomeric unit with a molecular weight of 72,000 which undergoes dimerisation, dependent on ionic strength and protein concentration.1 0 4 Electrophoretically obtained lactic dehydrogenase isozymes have a molecular weight of twice this figure and, as mentioned above, are dissociated into four subunits by the action of guanidine hydrochloride and high urea concentrat i ~ n .6~ ~The enzyme was found not to be protected from denaturation by , 7 urea or from chymotryptic digestion by the presence of coenzyme, although fluorescencemeasurements indicated protection against the action of trypsin and nagarse.lo5 The effects of increasing urea concentration on the sedimentation, diffusion,and optical rotatory properties of the pig-heart enzyme have been interpreted in terms of an initial aggregation which is then reversed as denaturation occurs. The aggregation is thought to be due to greater opportunity for intermolecular hydrogen bonding during the gradual opening of the molecule caused by changes in electrostatic interactions.l o 6 This may be contrasted with interpretations of the effect of dimethylformamide on 3-phosphoglyceraldehydedehydrogenase. It is suggested that loosening of the molecule is due to increased solvation of apolar side chains.lo7 Thirteen thiol groups per unit of molecular weight 115,000 have been reported for the pig-heart enzyme, of which only three are essential for activity; these three also have the ability to transfer p-chloromercuribenzoate to other nonessential thiol groups.lo8 The results of kinetic studies, by product-inhibition methods, on the enzyme from rabbit muscle supported a mechanism of the alcohol-dehydrogenase type.lo9 Workers using deuterated NADH have found an isotope effect on the kinetic constants relating to maximum rate which cannot be explained on the basis of this mechanism, as rate is supposedly determined by the final dissociation of the coenzyme, a step which does not involve the isotope. lo Ultracentrifugal studies have verified that enzyme inhibitors related to the substrate can form links t o the enzyme only if coenzyme is first bound, and then in molar ratio.1ll The design of inhibitors of lactic dehydrogenase for chemotherapeutic purposes has been used in another exploration of the active site. The inhibitors, also related to the substrate, are modified in size and stereochemistry so that an outline of the site may be constructed.112 Finally, mention should be made of the novel use of photooxidation with Methylene Blue of histidine and tryptophan residues in lactic dehydrogenase and its effect on coenzyme binding.ll3
D. 13. S. Millar, J. Biol. Chern., 1962, 237, 2135. R. H.McKay and N. 0. Kaplan, Biochim. Biophys. Acta, 1961, 52, 156. lo6 R. Jaenicke, G. Pfleiderer, and T. Wieland, Biochem. Z., 1962, 336, 107. lo' P. Elodi, Acta Physwl. Acad. Sci. Hung., 1961, 20, 311. 1 0 8 W. Gruber, K. Warzecha, 0. Pfleiderer, and T. Wieland, Biochem. Z., 1962, 336, 107. 1 0 9 V. Zewe and H. J. Fromm, J . Biol. Chem., 1962, 237, 1668. l 1 0 J. F. Thomson and J. J. Darling, Biochem. Biophys. Res. Cmm., 1962, 9, 334. l l 1 W. B Novoa and G. W. Schwert, J . B o . Chem., 1961, 236, 2150. . il 112 B.R. Baker, W. W. Lee, W. A. Skinner, A. P. Martinez, and E. Tong, J . Mediciiz. Pharmaceut. Chem., 1960, 2, 633. 1 1 3 D. Robinson and D. Stollar, Fed. Proc., 1962, 21, 232; D. B. S. Millar and
lo4 lo5
G. W. Schwert, ibid., p. 233.
FAWCETT: THE NICOTINAMIDE COENZYMES
425
MaZic dehydrogenase. It has been reported that the properties of pigheart enzyme preparations vary as a result of certain treatments normally incorporated in standard procedures for enzyme isolation. Evidence has been presented that the changes are due to modifications in the tertiary structure of the enzyme.ll* The protein is also thought to have a particularly high content of a-helix.115 Some disagreement exists concerning the nature of the malic dehydrogenase obtained from other tissues. Homogenates of beef heart and rat liver each yield two enzymes differing in catalytic properties and composition, and a previous report of conversion from one to the other by butanol-extraction was not confirmed when characteristic inhibition properties were examined, although a decrease in molecular weight was noted,ll6' Similarities in composition and in kinetic properties were found during a detailed survey of malic dehydrogenases from different sources.116b Studies of the kinetic mechanism of the pig-heart enzyme show that it also involves initial binding of the coenzyme, whose final dissociation then appears to determine the overall rate. It was pointed out that variation in kinetic constants with pH can be due both to participation of hydrogen ion as a reactant and to the effects due to ionisation of groups on the enzyme.l17 GEutamic dehydrogenme. It is now considered that the value of lo6 obtained for the molecular weight of the beef-liver enzyme represents a tetramer. This form is associated with maximum glutamic dehydrogenase activity 118 although one report has appeared to the contrary.l19 The chicken-liver enzyme has a molecular weight of about 0.5 x lo6 and is less able to undergo aggregation.120 The beef enzyme appears to have an innate ability to catalyse oxidative deamination of structurally related aminoacids,121although its substrate specificity may also be influenced by its state of aggregation.llsb This phenomenon is not well understood at present. The aggregation is influenced by many factors including enzyme concentration and even the presence of the reduced coenzyme. Great care must accordingly be observed when results of different experiments are compared, as the number and type of binding sites are thought to be changed by this aggregation.122 The influence of 1,lO-phenanthrolineon the state of aggregation was originally interpreted on the basis of its zinc-chelatingproperties ; a similar effect can be brought about, however, by other polycyclic compounds such as steroid hormones and phenanthridine, known to be incapable
B. K. Joyce and S. Grisolia, J . Biol. Chem., 1961, 236, 725. B. Jirgensons, Photochem. Photobiol., 1962, 1, 59. (a) 1. Siege1 and S. Englard, Biochim. Biophys. Acta, 1961, 54, 67; F. G. Grimm ; and D. G. Doherty, J . Biol. Chem., 1961, 236, 1980; ( b ) C. J. R. Thorne, Biochim. Biophys. Acta, 1962, 59, 624. 1' D. N. Raval and R. G. Wolfe, Biochemistry, 1962, 1, 263, 1112, 1118. 1
114 115 116
(a) H. Kubo, M. Iwatsubo, H. Watari, and T. Soyama, J . Biochem. ( J a p a n ) , 1959, 46, 1171; C. Frieden, J . Biol. Chem., 1962, 237, 2396; ( b ) G. M. Tomkins, K. L. Yielding, and J. Curran, Proc. N u t . Acad. Sci. U.S.A., 1961, 47, 270; S. Grisolia, M. Fernandez, R. Amelunxen, and C. L. Quijada, Biochem. J., 1962, 85, 568. 119 H.F. Fisher, D. G. Gross, and L. L. McGregor, Nature, 1962, 196, 895. lZo C. Frieden, Biochim. Biophys. Acta, 1961, 63, 421. 121 J. Struck and I. W. Sizer, Arch. Biochem. Bwphys., 1959, 86, 260.. l z 2 C. Frieden, Biochim. Biophys. Acta, 1961, 47, 428; G. M. Tompkins, K. L. Yielding, and J. F. Curran, J . Biol. Chem., 1962, 237, 1704.
426
of zinc-chelation and having an effect not destroyed by addition of zinc but destroyed by addition of ADP,123as is the dissociation brought about by thyroxine and tri-iod0thyr0nine.l~~The levels of the hormones required to promote dissociation make it unlikely that their effects are of physiological significance; nevertheless the effect 05 ADP, the stimulation of activity by other a m i n o - a ~ i d s and ~ , ~ ~ the inhibition by guanosine nucleot i d e ~ , 1 ~ ~may yield clues to the metabolic control of this enzyme. Present 126 3 explanations of these observations visualise activating and inhibiting sites for nucleotides as well as the catalytic site. Irreversible dissociation of this enzyme into many subunits has been achieved by severe physical treatment such as heat, urea, detergent,11sa9 1243 1 2 7 and extremes of pH,128 to disturb the inter-chain bonds.
C. P. F.
5. METABOLISM OF STEROID HORMONES
THEpathways of steroid anabolism and catabolism have been investigated extensively over the last few years, and the general pattern now seems fairly well established. However, much is still to be learned concerning the details of the various stages, and the quantitative aspects of alternative pathways. Further, little is known about the details of steroid metabolism in the foetus and new-born. Considerable interest also attaches to the elucidation of metabolic errors, and studies of aberrations in biosynthetic mechanisms have yielded information of both clinical and fundamental value. For several years much endocrine research has had the aim of assessing the hormonal status of patients with endocrine or other disease: extensive studies of urinary steroid metabolites have been made, and some progress has been achieved. Administration of labelled hormones offers the possibility of revealing specific urinary metabolites and of assessing their rate of secretion of various steroids by endocrine tissues. A complementary approach arose from the concept that metabolic activity may be related to plasma concentration of hormonally active compounds, and considerable efforts have been made to determine quantitatively the minute concentrations of circulating steroids. The problem originally posed, of relating biological activity to some parameter such as secretion rate, peripheral concentration, or rate of formation of an active material, remains a t least partly unsolved, as indeed is the related matter of the intimate r81e of steroid and other hormones in intermediary metabolism. General.-The scope of a recent conference on hormonal steroids indicates the very broad range of interest in this field. Several useful accounts
L. Yielding and G. M. Tomkins, Biochirn. Biophys. Acta, 1962, 62, 327. J. Wolf, J . Biol. Chem., 1962, 237, 230, 236. K. L. Yielding and G. M. Tomkins, Proc. Nat. Acad. Sci. U.S.A., 1961, 47, 983. 126 C. Frieden, B i o c h k . Biophys. Acta, 1962, 59, 484. 12 B. Jirgensons, J . Amer. Chem. Soc., 1961, 83, 3162. 12* H. F. Fisher, L. L. McGregor, and U. Power, Biochem. Biophys. Res. Comnt., 1962, 8, 402; H. F. Fisher, L. L. McGregor, and D. G. Gross, Biochim. Biophys. Acta, 1962, 65, 175. Exerpta Medica, 1962, 52, 1.
123 K.
124 125
J A M E S : METABOLISM O F STEROID HORMONES
427
of various aspects of steroid metabolism are now available, dealing with steroids in blood,2 general and clinical aspects of adrenal steroids,3 cestrogens,4 rneth~dology,~ steroid chromatography.6 Binding of steroids to and proteins, the control of adrenocortical secretion,g and the biosynthesis of steroid hormones 9 have also been reviewed. Bios~thesis.-C2, Steroids. It now seems highly probable that pathways not involving cholesterol play a minor r61e in corticosteroid biosynthesis by the adrenal cortex. Werbin and Chaikoff 1 0 fed [ 14C]cholesterol to guinea-pigs for a time sufficient to achieve uniform labelling of the cholesterol pool, and the specific activities of the blood cholesterol, adrenal cholesterol, and urine cortisol were then determined. The results indicated that 60% of the adrenal-gland cholesterol were derived from the blood, and also, since the specific activities of the adrenal cholesterol and urinary cortisol were practically identical, the latter must be formed principally from the cholesterol in the adrenal gland. No alteration of specific activity was observed after administration of corticotrophin, suggesting that the trophic hormone does not alter the biosynthetic pathways. Further evidence that cholesterol is the main precursor of cortisol is offered by studies l1 of the labelling of the individual carbon atoms of cortisol biosynthesised from [l*C]acetate, which show a distribution of radioactivity identical with that found in cholesterol derived from [14C]acetate. Mevalonate is an established intermediate in cholesterol biosynthesis, and has been reported as a precursor of (3-19 steroids in wivo;l2 surprisingly, however, it was not incorporated into corticosteroids by an adrenal h0m0genate.l~ The sequence cholesterol-+ pregnenolone (1)+progesterone (2) -+ 17a-hydroxyprogesterone (3)is established as an important major pathway in the synthesis of cortisol (4). Under some circumstances, however, an alternative pathway, cholesterol +pregnenolone (1)+ 3p,17a-dihydroxypregn-5-en-20-one ( 5 ) ---+17a-hydroxyprogesterone (3), may assume importance. Normal, hyperplastic, and neoplastic adrenal glands all convert 3~,17a-dihydroxypregn-5-en-ZO-one cortisol l4 and in some instances into
a H. N. Antoniades, Hormones in Human Plasma, J. A. Churchill, London, 1960; C. H. Gray and A. L. Bacharach, Hormones in Blood, Academic Press, Inc., New York, 1961. L. J. Soffer, R. I. Dorfman, and J. L.Gabrilove, The Human Adrenal Gland, Henry Kimpton, London, 1961; F. T. G. Prunty, Brit. Med. Bull., 1962, 18, No. 2. 4 E. Diczfalusy and C. Lauritzen, Ostrogene h i m Menschen, Springer, Berlin, 1961; H. Breuer, Vitamins and Hormones, 1962, 20, 285. M. F. Jayle, Analyse des Steroides Hormonaux, Masson, Paris, 1961; R. I. Dorfman, Methods in Hormone Research, Academic Press, London, 1962, Vol. I. R. Neher, Chromatog. Rev., 1959, 1 99; I. E. Bush, The Chromatography of , Steroids, Pergamon Press, London, 1961. W. H. Daughaday, Physiol. Rev., 1959, 39, 885. F. E. Yates and J. Urquhart, Physiol. Rev., 1962, 42, 359. A. Wettstein, Experientia, 1961, 17, 329: l o H. Werbin and I. L. Chaikoff, Arch. Bzochern. Biophys., 1961, 93, 476. l l E . Caspi, R. I. Dorfman, B. T. Khan, G. Rosenfeld, and W. Schmid, J . Biol. Chem., 1962, 237, 2085. l 2 S. Burstmein and R. I. Dorfman, Acta Endocrinol., 1962, 40, 188. l3 M. J. Bryson and M. L. Sweat, Arch. Biochem. Biophys., 1962, 96, 1. l4 M. B. Lipsett and B. Hokfelt, Experientia, 1961, 17, 449; P. J. Mulrow, G. L. Cohn, and A. Kuljian, J . Clin. Invest., 1962, 41, 1584; I. Weliky and L. L. Engel, J. Biol. Chem., 1962, 237, 2089.
428
Cholesterol
BIOLOGICAL CHEMISTRY Acetate
this precursor was superior t o progesterone as a substrate. The relative importance of these pathways and the extent t o which they may operate under different conditions in viwo remains t o be defined. It seems likely are that small amounts of 3/3,17a-dihydroxypregn-5-en-20-one secreted by the normal adrenal cortex, since a metabolite of this compound, namely, pregn-5-ene-3,!3,17~,2Oa-triol, occurs regularly in human urine.15 C,, Steroids. The suggestion, based on experiments in vitro, that the sequence, cholesterol -+ pregnenolone + progesterone -+ l'l-hydroxyprogesterone -+ androst-4-ene-3,17-dione -+ testosterone (7), operates in (6) the synthesis of testicular androgens is supported by the detection of the last three of these compounds in bull spermatic vein blood.16 A similar pathway probably exists in adrenal tissue since it has now been demonstrated that hornogenates of normal human adrenal tissue convert progesterone and 17-hydroxyprogesterone into androstenedione and testosterone. l7 It is improbable, however, that an appreciable quantity of testosterone is secreted by the normal adrenal, since this steroid has not yet been demonstrated in normal adrenal glands or in adrenal vein blood, although it has been isolated from an adrenal tumour.18 Since androstenedione is well established as an adrenal secretory product (cf. Short 19), the h a 1 conversion, of androstenedione into testosterone, seems to be characteristic of testicular tissue.
l5 K. Fotherby, Biochem. J., 1959, 69, 596; H. Wilson, M. B. Lipsett, and D. W. Ryan, J . Clin. Endocrinol., 1961, 21, 1304. H. R. Lindner, J. Endocrinol., 1961, 2 , 139. 3 l7 N. Kase and J. Kowal, J . Clin. Endocrinol., 1962, 22, 925. R. Anliker, 0. Rohr, and M. Marti, Helv. Chirn. Acta, 1957, 39, 1100. l9 R. V. Short, Biochem. Soc. Symposia, 1960, Vol. XVIII, p. 59.
J A M E S : M E T A B O L I S M O F STEROID HORMONES
429
The alternative pathway, pregnenolone --+ 3/3,17x-dihydroxypregn-5en-20-one+ dehydroepiandrosterone (8) --+ androstenedione, appears to proceed in both testis and the adrenal gland. The first two stages have been demonstrated with homogenates of both bovine adrenal and testicular tissue,20and the dihydroxypregnenone was found in bovine adrenal glands.21 Dehydroepiandrosterone has been detected in bovine testes,21 and there is indirect evidence for its gonadal secretion.22 Here again, the quantitative significance of these alternative routes is not known, but it seems necessary to assume that the pathway to dehydroepiandrosterone must be of considerable importance in the adrenal cortex (see below). C, S e o d . The conversion of acetate, cholesterol, and progesterone , tris into estrogens by human ovaries in yields of 0.02%, 0-1%,and lo%, respectively, has been d e m ~ n s t r a t e d . ~ ~ progressive increase in yield is in The accordance with a biosynthetic route in the ovary which is similar to those for adrenocortical and testicular steroids. It is necessary in these, as in 'all experiments in uitro, to accept that results with tissues outside the body, and thus under artificial conditions, reflect processes occurring in vivo. I n this instance, a preparation that was active in vitro was obtained by administration of follicle-stimulating hormone before surgical removal of the ovaries. There is also further evidence to show that C,, neutral steroids are intermediates in the conversion of progesterone into estrogens.24 Androst-4ene-3,17-dionehas been isolated from human ovarian follicles and corpora lutea,25and ovarian biosyntheses of this compound from acetate 24 and from progesterone 26 have been demonstrated. Testosterone has been detected in the follicular fluid of the cow 27 and in ovarian tumour tissue,28 and testosterone biosynthesis from various precursors by normal 29 and abnormal ovarian tissue 30 has been shown. Dehydroepiandrosterone occurs in equine follicular fluid 30a and in cystic human ovaries.31 I n appropriate conditions all three C,, steroids may serve as precursors for estrogen.32 The final stages of estrogen formation, in which ring A of the steroid nucleus is aromatised, requires oxidation at (3-19, and both 19-hydroxyandrost-4-ene3,17-dione (9) and androst-4-ene-3,17,19-trione (10) are converted into estrone (11) and cestradiol (12) in good yield by placental microsomes;
F. W. Kahnt, R. Neher, K. Schmid, and A. Wettstein, Ezperientia, 1961, 17, 19. R. Neher and A. Wettstein, Acta Endocrinol., 1960, 35, 1. 2 3 S. Lieberman, P. Macdonald, and R. L. Vandewiele, Exerpta Medica, 1962,51, 16. 23 K. J. Ryan and 0. W. Smith, J . Biol. Chem., 1961, 236, 705, 710, 2204. 2 4 K. J. Ryan and 0. W. Smith, J . Biol. Chem., 1961, 236, 2207. 2 5 J. J. Zander, J . Biol. Chem., 1958, 232, 117. 2 6 M. L. Sweat, D. L. Berliner, M. J. Bryson, C. Nabors, J. Haskell, and E. G. Holmstrom, Biochim. Biophys. Acta, 1960, 40, 289. 2 7 R. V. Short, J . Endocrinol., 1962, 23, 401. 2 8 R. Anliker, 0. Rohr, and L. Ruzicka, Annalen, 1957, 603, 109. 2 s N. Kase, E. Forchielli, and R. I. Dorfman, Acta Endocrinol., 1961, 3 7 19. ', 3 0 K. Savard, M. Gut, R. I. Dorfman, J. L. Gabrilove, and L. J. Soffer, J . Clin. Endocrinol., 1961, 21, 165; A. A. Sandberg, W. R. Slaunwhite, J. E. Jackson, and T. F. Frawley, ibid., 1962, 22, 929; V. B. Mahesh and R. B. Greenblatt, ibid., p. 441. 30aR. V. Short, J . Endocrinol., 1961, 23, 277. 31 R. V. Short, J . Endocrinol., 1962, 24, 359. 32K. Ryan, J . Biol. Chem., 1959, 234, 268; C. D. West and A. H. Naville, J. Biochemistry, 1962, 1, 645.
2o
21
430
Androstenedione Testosterone
D e h y d r o e p i androsterone
OH
OH
..OH
HO.H2C
0
&
J,
J,
HO
other possible intermediates, including 19-nortestosterone or androsta-1,4diene-3,17-dione,were only poor substrates.33 The mechanism of aromatisation appears to involve trans-diaxial elimination of (7-19 and la-hydr0gen.3~ There is some evidence, however, that free 19-hydroxyandrostenedionemay not participate in the reaction.35 The route to oestriol (13) via 16-hydroxytestosterone (14) 36 may be of significance in placental tissue, since the latter compound was the most abundant steroid detected in placental extracts.37 Catabolism.-C,, Steroids. (i) Aldosterone. The preparation of [7-3H]aldosterone of high specific activity has made possible the study of the catabolism of this hormone at physiological concentrations.38 About 14% of the secreted hormone appears in urine as the 3-oxo-conjugate. The structure of this compound is unknown, and the term 3-oxo-conjugate implies only that the A4-3-oxo-groupingis not irreversibly reduced. The major metabolites of aldosterone are excreted as glucuronides (55% of the dose). Original studies of the structure of the major metabolite sugbut gested formulation as 3~,18,21-trihydroxy-5~-pregnane-ll,20-dione,39 this material was later shown t o be a mixture of 3a,l8,21-trihydroxy-5833 C. Gual, T. Morato, M. Hayano, M. Gut, and R. I. Dorfman, Endocrinology, 1962, 71, 921. 3 4 L. R. Axelrod and J. W. Goldzieher, J . CZin. EndocrinoZ., 1962, 22, 537. 35 N. Hollander, Endocrinology, 1962, 71, 723. 36 K.J. Ryan, J. BioZ. Chem., 1959, 234, 2006. 8 7 R. Neher and G. Stark, Experientia, 1961, 17, 510. 5 8 C Flood, D. S. Layne, S . Ramcharan, E. Rossipal, J. F. Tait, and S . A. S. . Tait, Acta Endocrinol., 1961, 36, 237. 3 9 S. Ulick and 5. Lieberman, J . Amer. Chem. Soc., 1957, 79, 6567.
J A M E S : METABOLISM O F STEROID H O R M O N E S
431
pregnane-11,2O-dione (derived from corticosterone) and 3a,l1/?,21-trihydroxy-20-oxo-5~-pregnan- (tetrahydroaldo~terone).~~ latter com18-a1 The pound accounts for about 40% of the total urinary metabolites. Other compounds, isolated after the administration of very large quantities of aldosterone, were identified as 11,18,20-cyclicdiacetalsY41 some 3p- and and 5a-compounds were found.42 Only small and highly variable quantities of aldosterone are secreted by the adrenal cortex. The mean value for a small number of normal subjects was 138 ,~g./day.~3 Measuring the concentration of aldosterone in peripheral blood is very difficult because of the low values involved, and great skill is required (proceduresare reviewed by Tait and Tait 44). Bojesen and Degn 4 5 have reported concentrations of 2 4 x g. per 100 ml. g. per 100 ml. was in the peripheral plasma of dogs, and up to 2.5 x found by Bojesen in human plasma (cf. ref. 44). (ii) Cortisol. The major paths involved in the catabolism of cortisol are now well established. Reduction of the A4-3-0x0-groupingin ring A proceeds to a major extent and is largely stereospecific, yielding a 3aY5/lstructure [tetrahydrocortisol (15)]. Oxidation at C-11 of alcohol to ketone also occurs, producing tetrahydrocortisone (16). A proportion of the steroid is reduced further, at C-20, to give the hexahydro-metabolites (17) ( corto1 ) and (18) ( cortolone ). After administration of [14C]cortisol to human subjects, these four compounds accounted for 90% of the activity in the neutral extract obtained after treatment of the urine with glucuronidase, followed by acid.46 A minor mode of metabolism involves removal
40 41 42 43
W. G . Kelly, L. Bandi, and S. Lieberman, Biocherniutry, 1962, 1, 792. J. N. Mills, Brit. Med. Bull., 1962, 18, No; 2, 170. 4 4 S. A. S. Tait, J. F. Tait and R. I. Dorfman, Methods in Hormone Research, Academic Press, London, 1962, Vol. I, p. 265. 4 5 E. Bojesen and H. Degn, Acta Endocrinol., 1961, 37, 541. 4 6 D. K. Fukushima, M. L. Bradlow, L. Hellman, B. Zumoff, and T. F. Gallagher, J . Biol. Chem., 1960, 235, 2246.
1, 172.
S. UIick, K. Kusch, and J. T. August, J. Amer. Chem. Xoc., 1961, 83, 4482. W. G . Kelly, L. Bandi, J. N. Shoolery, and Sf Lieberman, Biochemistry, 1962,
432
of the steroid side chain t o yield 17-oxo-steroids, and these compounds together with other minor metabolites probably account for all the residual activity in the extract. A small proportion (7-28%) of the excreted radioactivity remained in the urine after hydrolysis and extraction and presumably represents metabolites of cortisol which resist known methods of hydrolysis, or compounds which are not extracted by the usual organic solvents. These compounds may become quantitatively more important a t higher secretion rates, since Gold 47 was unable to account completely for the metabolites of administered cortisol when 200 mg./day were given. The amount of cortisol or corticosterone which is excreted unchanged is extremely small. After administration of large doses of these compounds some conjugation at C-21 with sulphuric acid is rep0rted.~8 Other minor metabolites of cortisol are 5a-cortol and 5a-cortolone, isolated after administration of 500 mg. of cortisone acetate.46 Hydroxylation at C-6 also occurs t o a small extent but may be increased when normal metabolic routes are impaired 49 or in the metabolism of synthetic steroids.50 C, Steroids. Although dehydroepiandrosterone was among the first steroids to be isolated from human urine and there is unequivocal evidence available that this compound or its precursor originates from the adrenal cortex, it is still not known in what form it is secreted or whether it results from peripheral degradation of another compound. The poor conversion in wivo of administered 38,17a-dihydroxypregn-5-en-20-one suggests this is an unlikely peripheral source of urinary dehydroandrosterone.51 I n an attempt to study this problem further, Liebermans group administered [7-3H]dehydroepiandrosteroneto a series of normal subjects. Androsterone, aetiocholanolone, and dehydroepiandrosterone were then isolated from the urines, and their specific activities were determined : all three metabolites had almost the same specific activity.52 This implies that these three compounds arise from the same precursor, i.e., dehydroepiandrosterone, and that no other precursor contributes t o a large extent t o the urinary androsterone and ztiocholanolone. Dehydroepiandrosterone thus assumes considerable importance as the major precursor of the C,, steroids in human urine. This finding was unexpected since it has been difKcult to detect dehydroepiandrosterone regularly in adrenal vein blood, and because of the implication that compounds such as testosterone and androstenedione must therefore be secreted in very small amounts. From the dilution of the administered isotope, it was calculated 52 that the production of dehydroepiandrosterone ranged from 12 to 50 mg./day in the subjects studied. Unfortunately, this simple interpretation does not appear t o be valid in all cases, since Brooks and Prunty 53 reported that in four out of five
N. I. Gold, J . Clin. Invest., 1962, 41, 1871. J. R. Pasqualini, Contribution B llhude Biochimique des Corticosteroides, Foulon, Paris, 1962. 4 9 F. H. Katz, M. M. Lipman, A. G. Frantz, and J. W. Jailer, J . Clin. Endocrinol., 1962, 22, 71. 5 0 J . R . Florini, L. L. Smith, and D. A. Buyske, J . Biol. Chem., 1961, 236, 1038. 5 1 S. Solomon, A. C. Carter, and S. Lieberman, J . Bicl. Chem., 1960, 235, 351. 5 2 R. L. Vandewiele, P. C. MacDonald, E. Bolte, and S. Lieberman, J. Clin. Endocrinol., 1962, 22, 1207. 53R. Brooks and F. T. G. Prunty, Exerpta Medica, 1962, 51, 174. V.
47
48
J A M E S : METABOLISM O F S T E R O I D HORMONES
433
cases studied by the same method the specific activity of the urinary dehydroepiandrosterone was lower than that of the urinary aetiocholanolone and androsterone : in this situation some other precursor of urinary dehydroepiandrosterone must be involved. Clarification of this problem revolves around the composition of normal adrenal venous effluent; it is by no means clear to what extent the detection of dehydroepiandrosterone and androstenedione in adrenal vein blood represents the situation in the normal subject, since the majority of observations have been made in conditions where the adrenal gland has been stimulated either endogenously or exogenously with corticotrophin. The matter is further complicated by Baulieu's observations 54 that, whereas no free dehydroepiandrosterone could be detected in an adrenal tumour or in the venous blood from the tumour, dehydroepiandrosterone sulphate was detected in both, and in higher concentration than in peripheral blood. The possibility therefore exists that dehydroepiandrosterone is secreted as its sulphate also under normal conditions. Studies of the metabolism of dehydroepiandrosterone sulphate have already shown that it is converted into aetiocholanoloneglucuronide and androsterone glucuronide,55 thus implying that dehydroepiandrosterone and its sulphate are interconvertible in vivo. It may therefore be necessary to reassess the concept that compounds such as dehydroepiandrosterone sulphate represent inactive end-products of steroid metabolism, and it has been reported 56 that administration of either dehydroepiandrosterone or androstenedione leads to increased levels of plasma testosterone. Testosterone secretion rates have been estimated by administering [ 14C]testosteroneand subsequently measuring the specific activity of the urinary test~sterone.~'This method led to estimates of secretion rates of 3-8 mg./day in normal adult males and 0.5-2 mg./day in normal females. (218 Steroids. Administration, to two female subjects, of [17-3H]cestradiol provided confirmation that its direct hydroxylation is a minor pathway to oestriol. The urinary oestriol isolated contained only minimal radioactivity and must therefore be formed by the route, oestradiol-+ oestrone --+ oestriol.58 The conversion of oestrone into oestriol probably involves initial hydroxylation at position 16. Studies of the metabolism of 16~-hydroxyoestrone have demonstrated significant conversion into oestriol in vivo 59 and to a smaller extent into 16-epiestriol and 17-epioestriol (for structures see the chart).60 16/I-Hydroxyoestrone was converted into oestriol and 16-epioestriol, 16,17-epioestriol being a minor product.60 Both the ketols can thus serve as precursors of oestriol, reduction of the 17-ketone proceeding largely to yield the 17/?-alcohol. However, epimerisation at C-16 also occurs, which suggests that a 16-ketone is an intermediate in this conversion.
s 4 E . E. Baulieu, J. Clin. Endocrinol., 1962, 22, 501. 5 5 K. D. Roberts, R. L. Vandewiele, and S. Lieberman, J. Bid. Chem., 1961, 236, 2213; A. E. Kellie, J. Endocrinol., 1961, 22, i. 5 6 V. B. Mahesh and R. B. Greenblatt, Acta Endocrinol., 1962, 41, 400. 5 7 B. Hudson, Public Lecture at St. Mary's Hospital, London, May 31st, 1962. 5 8 J. Fishman, H. L. Bradlow, B. Zumoff, L. Hellman, and T. F. Gallagher, Acta Endocrinol., 1961, 37, 57. 5 9 J. B. Brown and G. F. Marrian, J . Endocrinol., 1957,. 15, 307. 6 o W. Nocke, H. Breuer, and R. Knuppen, Acta Endocrznol., 1961, 36, 393.
434
BIOLOGICAL C H E M I S T R Y
OEstradiol Gstrone
0
J l
JI
OH
OEstriol
16-Ep ice s t r i o I
All the compounds shown in the chart have been detected in human urine, although the majority appear to be relatively minor metabolites in relation to estrone and estriol. A further metabolic route yields the Z-methoxyderivatives of estrone, estradiol, and estriol, probably through the 2-hydroxy-compounds. Although the picture is still incomplete, it is likely that a fair proportion of the total estrogen metabolites can now be accounted for. It is not clear what is the scale of faecal elimination but in some cases it appears to be considerable.61 Peripheral conversion of other steroids into estrogens is probably of minor importance in relation to endogenous estrogen production, but may be significant where the latter is decreased, e.g., after endocrine surgery for malignant disease. 11-Hydroxylated estrogens have been isolated after administration of cortisone acetate although, surprisingly, cortisol was not similarly converted.62 Studies of estrogen metabolism in pregnancy indicate that conversion of radioactive estradiol into estrone and cestriol is similar to that found in non-pregnant subjects. In pregnancy, however, the specific activity of the urinary cestriol is considerably lower than that of the other two metabolites;619 63 this accords with the view that the placental-foetal compartment produces oestriol directly, but it may be also an expression of different metabolic routes for estrogen in the fetus. Foetal metabolism of estrogens has been studied extensively by Diczfalusy and his co-workers, and their work reveals a remarkably high degree of conjugation by a variety of tissues. Work both in vivo and in vitro demonstrated that fetal lungs, liver, kidney, adrenals, and intestine are major sites of estrogen c0njugation.6~
61 J. Fishman, J. B. Brown, L. Hellman, B. Zumoff, and T. F. Gallagher, J . Biol. Chem., 1962, 237, 1489. E. Chang and T. L Dao, J . Clin. Endocrinol., 1961, 21, 624; Biochim. Biophys. . Acta, 1962, 57, 609. 63 E. Gurpide, M. Angers, R. L. Vandewiele, and S. Lieberman, J . Clin. Endocrinol., 1962, 22, 935. 6 4 E. Diczfalusy, 0. Cassmar, C. Alonso, M. de Miquel, and B. Westin, Acta Endocrinol., 1961, 37, 516.
JAMES: METABOLISM O F STEROID HORMONES
435
This picture contrasts markedly with the situation in the adult, where the liver is probably the major site of steroid metabolism, and implies, the authors suggest, a r6!e for conjugated steroids other than that of detoxification products. V. H. T. J.
D. F. ELLIOTT. C. P. FAWCETT. V. H. T. JAMES. G. S. WRKS. A. M. WHITE.
ANALYTICAL CHEMISTRY
1. INTRODUCTION
SOME twenty years ago it was remarked that the analytical laboratory was regarded as the bottle-neck of production in metallurgical work. This must have found a heartfelt echo in many other industries, and it is, of course, the perennial opinion of research workers in any field. Since then much has been done to improve matters. In these Reports there is recurring emphasis on methods which decrease time without sacrificing accuracy, although perhaps they are not so widely adopted as to exclude some twinges of envy at the mention, in the following pages, of a complex industry in which no analysis takes more than 24 hours. Part of the improvement in the last two decades has been due to the refinement of classical methods and the spread of neo-classical ones such as solvent extraction and complexometric titrimetry, but most of it is clearly due to the adoption by the analyst of agreat variety of instrumental methods, mostly borrowed from the fields of structural investigations. Their advantage lies not so much in speed of measurement (a titration is as quick as most of them) but in standardisation of measurement so that it can be done as a routine and, above all, in the elimination of involved chemical separations which control the time and often the accuracy. Their disadvantage is that many of them survive with little or no change from their versatility as fundamental tools, and so the analyst is paying for a complexity, a degree of invention, and often (dare we say?)an instability which he could in most cases do without. He may need the first two qualities, and have to put up with the third, if he is developing an analytical method from first principles, but he is usually the first to progress beyond this and to simplify the machine to routine requirements. Seldom does the manufacturer do this. There are happy exceptions, but manufacturers might be more generally persuaded at an early stage in the development of an instrument, and in consultation with the analytical chemist, to produce a not-too-abridged paper-back edition which could spread his development costs and open new horizons to the less wealthy laboratories. The era of the pocket n.m.r. or X-ray fluorescence spectrometer is not yet, but strange things happen in analysis, and manufacturers should be thinking of it. More analytical papers have been published, in more and more journals. The first volume of AnaZyticaZ Abstracts,2 published in 1954, contained about 3000 references. Last year there were 5000, and this rose in 1961 to 5500. No analytical chemist could find his way among such a wide coverage of journals without their guidance, and your Reporters record their thanks to the Abstracts Editors, and their apologies t o the multitude of authors whose worthy papers have had to be excluded.
1E.
2
J. Vaughan, Roy. Imt. Chem. Monograph, 1941. Analytical Abstracts, Society for Analytical Chemistry.
CARTWRIGHT, WESTWOOD, AND W I L S O N
437
The arrangement of the Report is: (1) Introduction. (2) General. (3) Basic operations and apparatus. (4) Qualitative analysis. ( 5 ) Methods of separation. (6) Gravimetric and titrimetric analysis. (7) Instrumental end-point determinations. (8) Determination of elements in organic compounds. (9) Spectroscopic analysis. (10) Electrical methods. (11) Thermal methods.
2. GENERAL
Although the seventh Bernard Dyer Memorial Lecture to the Society for Analytical Chemistry dealt with the broad field of research in BritainY3 the analytical chemist will find pertinent and illuminating this account of the economic backpound to the contributions of industry, research associations, universities, and Government research stations. The early development of analytical chemistry has been reviewed by G r e e n a ~ a y , ~ and accounts of modern progress in general fields have been published. Babko has described new reactions and their applications in inorganic analysis, with corresponding developments in theory, and an account by G. den Boef deals mainly with advances in non-instrumental titrimetry. This year it is the turn of fundamental developments in analysis to receive attention in the annual reviews in AnaZyticaZ Chemistry. Under 38 headings, they cover significant advances made during 1960-61, and with a total of some 12,000 references they are clearly essential material for the analyst. A number of review papers have comprehensively described the state of more limited fields of analysis. Cockbill * has given a critical account of classical and instrumental methods for determining niobium and tantalum, and has proposed a general method based on isolating these metals together from hydrofluoric acid solution on a cellulose column or strip, with subsequent separation and determination according to the proportions present. The analysis of high-purity gold has been t'he subject of a symposium, and critical reviews of methods of determining gold and a large number of metallic impurities have subsequently been published. These papers underline the development and applications of such methods as emission and atomic absorption spectroscopy, flame photometry, and polarography. Modern methods of paint analysis have been described by Lamprecht 1 0 who indicates the increasing use of instrumental methods such as potentiometric titrations for pigments and infrared absorption for solvents. An account has been given of the detailed processes adopted in the French uranium industry for the control of quality and of safety.11 All analyses are completed in 24 hours, and to this end automation has been widely
D. W. Hill, Analyst, 1962, 87, 334. F. Greenaway, Endeavour, 1962, 21, 91. 5A.K. Babko, Zavodskaya Lab., 1962, 28, 773. G. den Boef, Chem. Weekblad, 1962, 58, 21. Annual Reviews, Analyt. Chem., 1962, 34, No. 5. * M. H. Cockbill, Analyst, 1962, 87, 611. J . S . African Inst. Mining Met., 1962, 62, 700. l o W. Lamprecht, Parbe u. Lack, 1961, 67, 560. l1 J. Pruguard, Chinz. analyt., 1962, 44, 143.
438
adopted, and i n s t m e n t a l methods predominate over chemical. Examples have been given of modern analytical techniques with a description of how they can best be co-ordinatedin industrial research.12 Methods of analysing peroxy-acids and hydrogen peroxide in presence of each other have been compared,13and a review has been given of the analysis of glass by methods which gain in speed without loss of accuracy.14 Analytical applications of the mercury electrode have been discussed in a review l5 which covers reduction processes with and without external control of electrode potential, coulometric determinations a t controlled current, and amalgamometry (where formation of an amalgam is put to direct analytical use for quantitative separation or determination). Other reviews which have direct bearing on the individual topics of this Report are mentioned in their appropriate section.
3. BASIC OPERATIONS AND APPARATUS
The dissolution of samples and the oxidation of organic material have received attention. Weisz has described a method for treating a sample with successive solvents on platinum foil, each solution being in turn absorbed on filter paper for ring-oven analysis. Metallic samples containing traces of boron can be dissolved without loss of boron l7by using anhydrous methanol with gradual addition of sulphuric or phosphoric acid solutions in methanol; volatile boron compounds are trapped in a sodium hydroxide solution in aqueous glycerol. Beyermann lS has examined the analytical behaviour of micro-quantities of chromium. He determined losses incurred in dissolving and in evaporating the sample, and the effectiveness of oxidation, extraction, volatilisation, and co-precipitationprocedures, and reported on the chromium content of 14 reagents. For oxidation of organic material, in particular celluloses, Monk l9 has advised altering the usual perchloric acid procedure by adding a nitric acid solution of the material in small portions to a boiling 72% perchloric acid solution; this is claimed to avoid hazards due t o accumulation of resistant organic matter in the perchloric acid solution. Volatilisation of a number of trace elements during oxidation of organic matter in the presence of some inorganic chlorides has been investigated by Gorsuch 2o using radiochemical methods. Heating with sodium chloride did not cause losses with antimony, chromium, iron(m), lead, and zinc. With ammonium chloride there was substantial loss of antimony and zinc, and some loss of lead. Loss of zinc was small with magnesium chloride, substantial with calcium chloride, but negligible with barium chloride. Methods of preventing loss of halogens,
1 2 R . C. Chirnside, Svenslc kern. Tidskr., 1961, 73, 265. l3 B. D. Sully and P. L. Williams. Analyst, 1962, 87, 653. l4 H. Lattermann, Silikat Tech., 1962, 13, 50. l5 J. A. Page, J. A. Maxwell, and R. P. Graham, Analyst, 1962, 87, 246. l6 H. Weisz, Mikrochim. A d a , 1962, 922. l7 L. R. Pitwell, Analyst, 1962, 87, 684. l8 K. B6Y6rman11, 2. analyt. Chem., 1962, 190, 4. R. G. Monk, Analyst, 1962, 87, 64. 2 o T. T. Gorsuch, Analyst, 1962, 87, 112.
C A R T W R I G H T , W E S T W O 0 D ; -4N D W I L S O N
439
phosphorus, and sulphur during oxidation of organic compounds have also been described.21 Revisions have been made in the values at various temperatures of each of the seven pH standards recommended by the National Bureau of Standards. The preparation, properties, and uses of the standards are given.22 Duval has continued his investigations,23usig thermogravimetric and infrared absorption methods, of the thermal stabilities of a number of standards used in analysis. A list of analytical standards in use in Czechoslovakia has been published.24 The applications and limitations of silicones in such diverse laboratory rbles as heat exchangers, molecular weight solvents, glass treatment, and lubricants have been discussed.25 Attention has been drawn to the analytical uses of exfoliated vermiculite. Holland 2 6 has recommended it as a general analytical aid in the absorption of water from samples before extraction of oils and fats with organic solvents, claiming easier and more complete extraction. Smith and Diehl 2 7 have described the properties of a highly efficient desiccant, prepared from vermiculite and phosphorus pentoxide, which remains granular in use. The regeneration of magnesium perchlorate desiccant in the laboratory is claimed 28 to be facilitated by vermiculite. Modifications have been made to methods and apparatus for determining water. A simple apparatus has been described 29 which enables the Karl Fischer determination to be carried out with 0-2-3 mg. water, and the determination of total water in rocks by a simplified diffusion method 30 facilitates the heating of the sample and the collection and weighing of the water produced. Methods have been recommended for testing laboratory glassware for resistance to chemical attack 3 l and to thermal sh0ck,~2 and standards have been issued for a range of graduated pipettes calibrated for delivery or content.33 Errors involved in using graduated cylinders for delivery instead of content have been investigated and procedures for minimising them discussed.34 Recent trends in the design of analytical balances have been described,35 and a quartz-beam microbalance has been produced 36 which electrically registers on a meter or recorder with variable sensitivity down to 1PA. = 1 pg. It has a capacity of 1 to 2 g. and is particularly suited to follow changes in weight even at high temperatures and low pressures.
D. Pristavka, Chem. Zvesti, 1961, 15, 865. R. G. Bates, J . Res. Nat. Bur. Stand., 1962,. A , 66, 179. 23 C. Duval, Mikrochim. Acta, 1962, 268, 947. 2 4 V. Mayer, Hutn. Listy, 1961, 895. 2 5 W. Simmler, Glas.-Instrum.-Technik, 1962, 6, 101. 26 G . J. Holland, A n d y s t , 1962, 87, 797. 2 7 G. F. Smith and H. Diehl, Talanta, 1962, 9, 84. 2 8 G. F. Smith, Talanta, 1962, 9, 65. 2 9 A. Dirscherl and F. Erne, Mikrochim. Acta, 1962, 794. 3 0 A . D. Wilson, Analyst, 1962, 87, 598. 31 B.S. 3473: 1962, British Standards Institution. 32 B.S. 3517: 1962, British Standards Institution. 33 B.S. 700: 1962, British Standards Institution. 3 4 G . A. Dean, Analyst, 1962, 87, 503. 3 5 D. Patterson, R <f: D, 1962, 34. 36 Bias.-Instrzcm.-Technik, 1962, 6, 196.
21
22
440
An increase in the precision of ebulliometric molecular weight determination is given by a differential method. Problems in ebulliometry have been disc~ssed,~' together with the design of a differential apparatus using a sensitive a.c. bridge, which gives a precision of &0-77% on a molecular weight of less than 500. Among apparatus which may fulfil some of the varied requirements of the analyst are it vacuum evaporator for completion of solvent removal,38 a thermistor device for controlling rate of evaporation in fractional distillat i ~ na, simple addition to a micrometer-syringe burette which enables it ~ ~ t o be used for occasional determinations with air-sensitive solutions,40 and a tapless polyethylene separatory funnel for small-scale work, in which the separation of aqueous and organic phases is cleanly performed by filter paper which may be silicone treated.41 Causes of variation in the performance of a continuous automatic analyser have been investigated,42 the determination of streptomycin being used as the control. Garmon and Reilley 43 have discussed the possibility of simultaneously determining two components of a mixture by their differing rates of reaction with a single reagent. From measurements of a property of the reaction made at two intervals of time, and known reaction rates, concentrations may be calculated. Doerffel 44 and Youden 45 have given accounts of errors and accuracy in analysis, and the interpretation of analytical results.
4. Q U A L I T A T I V E ANALYSIS
Inorganic.-SeveraI papers of general interest have been published and these will be reviewed before dealing with examples of more specific tests. Some analytical reactions of polyhydric phenols have been studied 46 and certain of them have been used 4 7 for the detection of iron(m), titanium(Iv), , vanadium(v), niobium(v), uranium(vI), molybdenum(vI), cerium(1v) and chromium(v1). The masking action of 20 complexans on the course of tests used in qualitative inorganic analysis has been studied,48 and an investigation has been made of the use of Variamine Blue in spot-test analysis.49 Chlorpromazine hydrochloride has been suggested as a spot-test reagent for gold, cerium, iron, chromate, bromate, iodate, nitrite, bromide, iodide, manganate, platinum, and palladium.50 A qualitative test for sodium in the presence of heavy metals by precipitation as antimonate is of interest
37 38
F. Trowell, H. G. Taylor, and W. I. Brown, Analyst, 1962, 87, 677. M. H. Coleman, Lab. Practice, 1962, 11, 543. E. C. Kuehner and R. T. Leslie, Analyt. Chem., 1962, 34, 1155. 40 A. D. Wilson and G. A. Sergeant, Analyst, 1962, 87, 152. 41 H.Marchart, Mikrochim. Acta, 1962, 913. 4 2 W. H. C. Shaw and I. Fortune, Analyst, 1962, 87, 187. 4 3 R. G. Garmon and C. PIT. Reilley, Analyt. Chem., 1962, 34, 600. 4 4 K. Doerffel, 8. analyt. Chem., 1962, 185, 1. 4 5 W. J. Youden, J. Assoc. Ofic. Agric. Chemists, 1962, 45, 169. 4 6 L. Sommer, 2;. analyt. Chem., 1962, 187, 7. 4'L. Sommer, 2. analyt. Chem., 1962, 187, 263. 4 8 W.Hoyle, I. P. Sanderson, and T. S. West, Analyt. Chi.m. Acta, 1962, 26,290. 4 9 L. Erdey and I. Buzbs, Mikrochim. Acta, 1962, 340. K. T. Lee, Analyt. Chim. Acta, 1962, 26, 285.
CARTWRIGHT, WESTWOOD, AND WILSON
441
since interference by many other metals may be overcome by the masking action of a mixture of EDTA and dihydr~xyethylglycine.~~ A new selective catalytic reaction for copper has been proposed involving aqueous ammonia and alcoholic guaiacol valerate solutions.5 2 Isatin 3-pnitrophenylhydrazone forms a blue acid-soluble lake which may be used for the detection of magnesium in alkaline s0lution,5~ and 3-hydroxy-l-onitrophenyl-3-phenyltriazenhas been suggested for the detection of zinc and nickel.5 4 Aluminium may be detected by using Eriochrome Cyanine (C.I. Mordant Blue 3),55 also by the inhibiting effect of the formation of an aluminiumand alizarin complex on the catalysed oxidation of alizarin by hydrogen peroxide.56 A new micro-test for gallium has been described which makes use of the colour reaction between gallium and Xylenol Orange at pH 1.0 in the presence of triethanolamine and ammonium fluoride.57 It has been reported that p-sulphanilic acid is fairly specific for the detection of cerium(Iv), giving a red colour with more than 6 p.p.m. of the metal. 68 A sensitive test for nitrate has been described 59 and a method has been developed for the detection of nitrate and nitrite by the formation of a violet-purple colour with N - 1-naphthylethylenediamine and concentrated sulpliuric acid.60 The method can be used for the detection of nitrate or nitrite in the absence of one or the other, or for the detection of nitrate in the presence of nitrite after destruction of the latter by sulphamic acid. Vanadium(v) may be detected by the violet colour produced with a 1% solution of maltol (3-hydroxy-2-methylpyan-4-one) in 40% phosphoric acid medium.61 The selective detection of niobium using Methyl Thymol Blue has been described.O2 The addition of an ethanolic solution of resacetophenone oxime to solutions of uranium(vI) in weak mineral acids produces a reddish-brown colour which may be used for the detection of the metal. Uranium(Iv),aluminium, zirconium, and thorium do not interfere, but tervalent iron gives a deep purple colour.63 Organic.-Microgram quantities of ethanol may be detected by oxidation at the boiling point to acetaldehyde. Nitrogen and air are passed through the solution and the acetaldehyde is detected on a paper strip by using the nitroprusside-morpholine reagent. 6 4 Formation of adducts
S . Takamoto, Japan Analyst, 1960, 9, 281. M. Y . Shapiro, Zhur. analit. Khim., 1962, 17, 248. 5 3 D. Goldstein and E. Libergott, Mikrochim. Acta, 1962, 352. 5 4 I. P. Khazova, Sb. Nauch. Trud. Magnito gorsk. Gorno metallurg. Inst., 1961, 98; Ref. Zhur. Khim., 1962, Abs. No. 7D45. 6 5 H. Gamsjilger and E. Schwarz-Bergkampf, Mikrochim. Acta, 1962, 194. 5 6 J. Laszlovsky, Mikrochim. Acta, 1962, 441. 5 7 R. Pzibil and M. Kopanica, Mikrochim. Acta, 1962, 29. 5 8 P. L. Sarma, Analyt. Chim. Acta, 1962, 27, 370. 5 9 G. de Vries and A. A. A. M. Brinkman, Analyt. Chim. Acta, 1962, 26, 498. 6 o A . Irudayasamy and A. R. Natarajan, Analyst, 1962, 87, 236. 61 L. Sommer, Z . analyt. Chem., 1962, 185, 263. E. Lassner, Chemist-Analyst, 1962, 51, 14. 6 3 C. Rama Rao, Talanta, 1962, 9, 81. 8 4 A. Dirscherl, Mikrochim. Acta, 1962, 155.
51
52
442
between various alcohols and vanadium 8-hydroxyquinoline complexes has been studied and the best conditions for detecting alcohols by this reaction have been ~ o n s i d e r e d . ~ ~ investigation has been made of methods for An the detection of alcohols by colour reactions with a number of addition a.gents. Feigl and Libergott have described a spot-test for phloroglucinol based on pyrolytic a m i n a t i ~ n . ~ ~ Pyrogallol and benzene-1,2,4-triol do not interfere since they are not aminated under the conditions of the test. The identification of a number of nitrogen compounds by reaction with a silver-manganese reagent has been investigated, 68 and a new sensitive colour reaction for the detection of secondary amines by use of methanolic phenothiazine solution and methanol-bromine solution has been described.69 -4 procedure has been given for the detection of a-amino-alcohols and 1,2diamines involving the production of iodic acid by reduction of potassiuni periodate in sulphuric acid solution followed by precipitation of silver iodate with silver nitrate in nitric acid solution.70 Organic disulphides and diselenides are selectively reduced in the presence of Raney alloys in alcoholic hydrochloric acid to give thiols and selenols which may be detected by the iodine-azide reaction. 71 The detection of thiocyanates in organic compounds has been studied by Feigl and Haguenauer-Castro, taking ethylene dithiocyanate and 2,4-dinitro-l-thiocyanatobenzene as model substances. 72 Cysteine can be detected in the presence of cystine, methionine, and taurine by reduction in an aqueous solution of osmium tetroxide t o give a pink or reddish-brown colour ; glutathione interferes. 73 N-Halogenosulphonamides can be detected by the violet colour produced when their aqueous solutions are spotted on t o paper impregnated with a 2% ethereal solution of p h e n ~ t h i a z i n e . ~ ~ study has been made of the A use of potassium p-phenylazophenoxide for the identification of organic halogen compounds. The reagent reacts with primary and secondary halides, straight- and branched-chain halogen esters, halogenohydrins, halogeno-ketones and -ethers, and chloroformates.75 I n a method for the detection of ferrocenes the sample is first mixed with water and extracted with chloroform; the extract is then treated with acetic acid and aqueous potassium ferricyanide t o give a green colour or a dark blue precipitate depending upon the concentration of ferrocene present. 76 A spot-test for the detection of arylmercury nitrate and other arylmercury salts has been described.7' The sample is heated t o 160" with
R. Montequi, A. Doadrio, and J. Serrano, Inf. Quim. Anal., 1962, 16, 31. G . M. Christensen, Analyt. Chem., 1962, 34, 1030. 6 7 F. Feigl and E. Libergott, Microchem. J., 1962, 6, 17. 6 8 M. Pesez, J. Bartos, and J.-C. Lampetaz, BuZ7. SOP. chim. France, 1962, 719. 6 0 H. Bro11 and G. Fischer, Mikrochim. Acta, 1962, 249. 'O T. S. M and H. MOSS, a Mikrochim. Acta, 1962, 111. 71 V. Anger and G. Fischer, Milcrochim. Acta, 1962, 501. 7 2 F. Feigl and D. Haguenauer-Castro, Milcrochim. Acta, 1962, 701. 73 W. Wawrzyczek, 2. analyt. Chem., 1962, 185, 446. 7 4 F. Feigl and D. Hagusnauer-Castro, Chemkt-Analyst, 1962, 51, 7. 7 6 E. 0. Woolfolk, E. Donaldson, and M. Payne, J . Org. Chem., 1962, 27, 2653. 7 6 J. D. Behun, Talanta, 1962, 9, 83. 7 7 F. Feigl, Chemist-Analyst, 1962, 51, 4.
e6
68
C A R T W R I G H T , W E S T W O O D , A N D WILSON
443
benzoin, and the nitrous acid formed is detected with a filter-paper treated with Griess reagent.
5. METHODS OF SEPARATION
Solvent Extraction.-As a method of separating metals which is usually selective and can sometimes be made specific, and which with very simple procedures can concentrate traces in a form suitable for direct instrumental determination, solvent extraction provides an inviting substitute for a variety of tedious chemical operations. It is only to be expected, therefore, that there is a great volume of published work; and probably to be expected, too, that a proportion of it is repetitive and inessential. Morrison and Ffeiser 78 have provided a valuable table of recently published data for a large number of metals, and have reviewed extraction systems employing the main chelating agents used in solvent extraction: dithizone, pyridylazonaphthol, the oximes, l-nitroso-2-naphthol, and cupferron and its analogues, together with other chelating and ion-association reagents. The use of paper chromatography to indicate if solvent extraction is feasible in given circumstances has been suggested 79 as a result of correlation found when tributyl phosphate was used as a developing medium in paper chromatography, and as an extractive solvent for iron(m), cobalt, and copper, at varying concentrations of hydrochloric acid. Formulae for the efficiency of extraction have been derived8O from a study of metal complex-solvent systems, and supported by a study of the extraction of radiocadmium from water into chloroform with 18 different chelating agents. The use of trifluorothenoylacetone as an extractive solvent has been reviewed 81 and optimum conditions have been tabulated for extraction of 40 metals. Selective extraction of 35 metals has provided the basis for a scheme of qualitative cation analysis,82and published information on the partition between water and organic solvents of 42 metal-oxine complexes a t varying pH values has been critically d i s c u ~ s e d . ~ ~ batch extraction The of dithizone complexes in chloroform with silica gel as a supporting solid phase has been described, with particular investigation of the separation of mercury. Most of the transition metals and many of the main-group metals have been the subject of solvent-extraction studies; only a few of the most interesting applications can be mentioned. Neptunium(IV) can be separated from other transuranic elements and from fission products by extraction with tri-iso-octylamine in xylene from dilute nitric acid solution ; s 5 satisfactorily quantitative results can only be obtained, however, by a second extraction, with trifluorothenoylacetone in xylene. Uranium can be extracted with tri-n-butyl phosphate, but traces remain; these can be removed
79
G. A. G. A. 8 2 G. 8 3 F. ** T. 8 5 R.
H. Morrison and H. Freiser, Analyt. Chem., 1962, 34, 65R. Musil, W. Haas, and G. Weidmann, Mikrochim. Acta, 1962, 833. K. Schweitzer and D. R. Randolph, Analyt. Chim. Acta, 1962, 26, 567. K. De and S. M. Khopkar, J . Sci. I n d . Res., I n d i a , A , 1962, 21, 131. Tolg, 2. analyt. Chem., 1962, 190, 161. Umland, 2. analyt. Chem., 1962, 190, 180. B. Pierce and P. F. Peck, Analyt. Chhn. Acta, 1962, 26, 557. A. Schneider, Analyt. Chem., 1962, 34, 522.
444
by a second extraction, with oxine.s6 An acidified trioctylphosphine oxide cyclohexane system has been used in the separation of zirconium, hafnium, niobium, and tantalum, 87 and zirconium can be quantitatively extracted from concentrated hydrochloric acid with trioctylamine, with direct colorimetric determination possible in the organic phase.s* A simple method for determining chromium in corrosion products involves extraction of the tetrabutylammonium chromate into isobutyl methyl ketone.89 Iron has been separated from zirconium, and from the large number of elements which do not form anionic chloro-complexes, by extraction from hydrochloric acid into a solution of a tertiary amine such as tribenzylamine.90 When small quantities of iron are extracted from aluminium chloride solutions, the use of isobutyl methyl ketone at low acidities overcomes difficulties of emulsion formation. With solutions of higher acidity a mixture of isobutyl methyl ketone and benzene is re~ommended.~~ Copper may be extracted from boiler feed-water into chloroform as the yellow dibenzyldithiocarbamate complex, with no appreciable interference from other likely constituents. 92 Tributyl phosphate has been used to extract mercury from very dilute hydrochloric acid solutions containing other metals ;93 the efficiency of the separation with varying concenhration of hydrochloric acid was studied by using radioactive tracers. Nowadays the term solvent extraction brings to mind almost exclusively procedures for metals, such as those described above. It should not be forgotten that it still applies to the simple extraction of organic compounds which was its former province. I n this connexion dimethyl sulphoxide has been recommended as an extractant for polynuclear and highly chlorinated hydrocarbons,9* with applications in the food and pesticide fields. Chromatography.-Many methods overlap the borders between chromatography, electrophoresis, and ion exchange, particularly where ion-exchange materials are used in column separations or are incorporated into chromatographic or electrophoretic papers or films. Nevertheless, for convenience electrophoresis and ion exchange, together with gas chromatography, are considered separately, and this section deals only with conventional liquid chromatographic separations on columns, papers, gels, and thin films. CoEumn chrmtography. Among the continuing investigations into fundamental principles are the correlation of chromatographic behaviour with the surface energy and gel structure of the adsorbent, and the r6les of activation and deactivation in selection of the best column perforrnan~e,~~ and an attempt to connect pH gradient and ionic-strength gradient in a col~11~1.96An investigation has been made of the factors which influence
T. Athavale, R. L. Bhasin, and B. L. Jangida, Analyst, 1962, 87, 217. Hideo Saisho, Bull. Chem. SOC. Japan, 1962, 35, 514. 8 8 E. Cerrai and C. Testa, Analyt. Chim. Acta, 1962, 26, 204. W. J. Maeck, M. E. Kussy, and J. E. Rein, Analyt. Chem., 1962, 34, 1602. A. V. Baeckmann and 0. Glemser, 2. analyt. Chem., 1962, 187, 429. 9 1 H. Jackson and D. S. Phillips, Analyst, 1962, 87, 712, 718. 9 2 A. L. Wilson, Analyst, 1962, 87, 884. 9 3 D. F. C. Morris and J. H. Williams, Talanta, 1963, 9, 623. 94 E. 0. Haenni, J. W. Howard, and F. L. Joe, jun., J . Assoc. O B c . Agric. Chemists, 1962, 45, 67. 9 5 P. D. Klein, Analyt. Chem., 1962, 34, -733. 9 6 6. M. Reiner and B. Reiner, Anal. Bzochem., 1962, 4, 1.
SSV.
87
CARTW-RIGHT, W E S T W O 0 D , A N D WILSON
445
the elution of rock and sediment organic matter containing components of high molecular ~ e i g h t . 9 ~ The preparation and uses of various types of silica gel have been described 98 and a method of preparing a uniformly absorbent gel is detailed.99 A device for gradient elution which permits complex but predictable gradients, or alternatively step-wise elution, depends on the relative heights of a series of containers which feed into a common line.100 I n another method lol the gradient is controlled by means of solenoid-operated clips. For many inorganic separations, column chromatography has been replaced by more convenient and more selective solvent-extraction methods. It has, however, maintained its position in a wide range of organic separations, as is shown by the large number of published methods in which it plays a part. Paper chromatography. The various paper techniques retain their popu larity in both inorganic and organic work because of the speed of elution and ease of identification of the separated spots. Only a few of the interesting applications can be reported. The general procedures of paper chromatography, ascending, descending, horizontal, and circular, have been reviewed ; a comparison for particular separations showed that a modified circular technique gave better separations and was simpler than the ascending or descending method.lo2 The use of a laboratory centrifuge for radial paper chromatography has been described; the solvent is applied to the centre from a burette.lo3 The relative merits of using transmitted and reflected light on dry and transparent papers has been investigated. For the copper-dithio-oxamide complex the best results were given by reflectance measurements on dry paper, and a method was developed for the determination of copper.104 By using commercial photographic copy-paper, spots which absorb ultraviolet light can readily be recorded.105 Other simple methods for recording chromatograms are described in the section on thin-layer techniques. Concentration of material in a chromatogram spot to such an extent that a solid or crystalline aggregate may be obtained is achieved by cutting out the spot so that a tail of paper is formed, clamping the spot between two microscope slides so that the tail protrudes, and allowing solvent to rise between the slides.los A general method for detecting inorganic ions depends on spraying the paper chromatogram with benzidine solution in acetic acid and then exposing it to furfuraldehyde vapour, whereupon characteristic colours are developed by many elements.lo7 Four phosphorus acids have been resolved by development on paper with an isopropyl alcohol-isobutyl alcohol-waterP. Hamway, M. Cefola, and B. Nagy, Analyt. Chem., 1962, 34, 43. J . Pitra, Chem. Listy, 1962, 56, 495. g D J. Pitra and J. StGrba, Chem. Listy, 1962, 56, 544. loo N. G. Anderson, H. E. Bond, and R. E. Canning, Anal. Biochem., 1962, 3, 472. lol R. A. Teekell, W. H. Boling, W. A. Lyke, and J. Chiriboga, J . Chromatog., 1962, 7, 424. l o 2 A. Grune, Riechstoffe u. Aromen, 1962, 12, 42, 104. lo3 G. M. Christensen and R. Swor, J. Chem. Educ., 1962, 39, 347. lo4 R. B. Ingle and E. Minshall, J. Chromatog., 1962, 8, 369, 386. lo5 A. S. Milton, J. Chromatog., 1962, 8, 417. lo6 I. Davis, C. A. Dubbs, and W. S. Adams, Analyt. Chem., 1962, 34, 175. ? lo' T. G h t i and E. NovAk, Magyar K6m. Folydirat, 1962, 68, 293.
97
98
446
ammonia system, the spots being located by treatment with ammonium molybdate and reduction by hydrogen sulphide to Molybdenum Blue.108 Separation of the elements between actinium and americium has been achieved by elution with acidified methanol, ethanol, propanol, or acidified butanol. 1099 110 Five elution systems were compared for the resolution of a synthetic mixture of 32 amino-acids. The best, butanol-acetic acid-water and phenolwater, separated 29 spots, of which 4 were mixed.ll1 The separation of 12 free phenolic acids in cigarette smoke and tobacco was carried out by using a two-dimensional descending technique, the spots being identified by ultraviolet light and by staining.l12 Optical brighteners, stripped from textiles, have been characterised by separation on paper and observation under ultraviolet light.l13 Microgram quantities of the more important chlorinated insecticides and of some of their metabolites have been separated by reverse-phase paper chromatography, with liquid paraffin as the fixed phase and aqueous acetone as the mobile pha~e.11~ Thin-layer chromatography. Advantages of speed, sharpness, and versatility inherent in this method have been widely appreciated. A review of the principles and techniques, with mention of a large number of applications, has been published.115 Work with microgram quantities of materials on microscope slides as supports has advantages in rapid preparation of the film and elution of the material.116-118 The relation between the area of the spot and weight of material present has been investigated, and a comparison made of the accuracy of graphical and algebraic methods of determining quantities. 119 Sideways diffusion of thin-layer chromatograms can be reduced by using ridged glass plates.lZ0 The cautious use of sodium dichromate or potassium permanganate in sulphuric acid is advocated for the general location of spots of oxidisable materials in thin-layer chromatograms,121and permanent records of chromatograms can be made by using a commercial photo-copier 122 or xerographic copier.123 Layers made by spreading a paste of cellulose powder and water on plates and drying them quickly in an oven have allowed speedy separations of dyes to be made,124 and a separation typical of hundreds in the literature is that of methoxypiperonylic acids on silica-gel layers, with development with ethyl acetate-hexane-acetic acid, and, after evaporation
lo8 M. Ebert and A. Varhanikovit, loo C. Keller, J. Chromatog., 1962, 110 F. Clanet, J. Chromatog., 1962, 111 Wei-Hsien Chang, Bull. Assoc.
112
7, 535. 7, 373.
Chem. prumysl, 1962, 12, 192.
Agric. Chem. Nut. Taiwan Univ., 1961, 10, 32. Chao-Hwa Yang and 5. H. Wender, J. Chromatog., 1962, 8, 82. 113 L. Meckel, Textil-Praxis, 1961, 16, 737. 11* W. H. Evans, Analyst, 1962, 87, 569. 115 C. A. Teijgeler, Pharm. Weekblad, 1962, 97, 43, 401. 116 R. Wasicky, Analyt. Chem., 1962, 34, 1346. 117 A. F. Hofmann, Anal. Biochem., 1962, 3, 145. 118 J. J. Peifer, Mikrochim. Acta, 1962, 529. 119 S. J. Purdy and E. V. Truter, Analyst, 1962, 87, 802. 120 A. Gamp, P. Studer, 13. Linde, and K. Meyer, Experientia, 1962, 18, 292. 121 H. Ertel and L. Homer, J. Chromatog., 1962, 7, 268. 122 H. R. Getz and D. D. Lawson, J. Chromatog., 1962, 7, 266. J. Hilton and W. B. Hall, J. Chromatog., 1962, 7, 266. 1 2 4 P. Wollenweber, J. Chromatog., 1962, 7, 557.
447
of the solvent, identification by spraying with an acid solution of chroizlotropic acid and heating. Electrophoresis.-The organic applications to such materials as serum constituents, amino-acids, and sugars and their derivatives heavily outweigh the ionophoresis of inorganic materials. Advances have been directed more to the improvement of apparatus than to new uses. A review of starch-gel electrophoresis, with 163 references, has been published and a technique for making starch gel transparent, for ease of location of zones, has been described.12' Polymerised acrylamide gel has been used as a medium in a vertical cell for resolution of serum components. * A micro-electrophoresis apparatus needing only 12 ml. of buffer solution, and allowing separations in 30 minutes, has been described,129and at the other end of the scale is a preparative apparatus in which electrophoresis is carried out on slabs of starch gel in which grooves are cut to carry an eluting buffer solution that removes the fractions as they reach the gr00ve.l~~ An automatic apparatus has been described which controls the duration of electrophoresis, removes the paper from the electrolyte, dries the chromatogram and switches itself 0ff.131 The dual advantage of providing cooling and uniform pressure on the paper is afforded by an inflatable rubber bladder through which can be passed a stream of air or More compact spots are claimed to result if the sample solution is applied to a circle removed with a cork-borer from the sheet, and re-inserted when the run is about to start.l33 Ion Exchange.-In a review of the subject 134 it is stated that ionexchange procedures have been devised for separations involving every element in the Periodic Table, except the inert gases. A great variety of exchange materials is now available, and desired properties of cross-linking and particle size are easier to obtain; characteristics of 370 resins have been listed. 135 The obvious overlap of ion-exchange procedures with chromatography is extending by introduction of more modified celluloses and papers loaded with ion-exchangeresins. Another overlap, this time into solvent-extraction procedures, is provided by liquid ion exchangers such as alkylamines and quaternary ammonium compounds for anions, and organophosphorus acids for cations; an account of their merits and a considerable list of representative applications have been given.136 Typical of inorganic uses of ion exchange have been separations of the rare-earth elements from anion-exchange columns by using acid-methanol
M. Beroza and W. A. Jones, Analyt. Chem., 1962, 34, 1029. c. Altaner, Chem. Listy, 1962, 56, 334. E. Vahvaselkii, Nature, 1962, 193, 474. lZ8 S. Raymond, Masumi Nakamichi, and B. Aurell, Nature, 1962, 195, 697. lZ9 J. Fischl, Clinica Chim. Acta, 1962, 7, 537. 130 K . Murray, Ar,alyt. Biochem., 1962, 3 415. , 131 J. Hrdina, M. Pechman, and J. Skoda, COIL Czech. Chem. Comm., 1962, 27, 969. 132 S. W. Bailey and R. H. Hackman, J . Chromatog., 1962, 8, 52. 133 J. Popowicz, J. Chromatog., 1962, 7, 271. 134 R. Kunin and F. X. McGarvey, Analyt. Chem., 1962, 34, 48R, 101R. 135 M. Marhol, Chem. Listy, 1962, 58, 728. 136 C. F. Coleman, C. A. Blake, jun., and K. B. Brown, Talatata, 1962, 9, 297.
lz5
lZ6
lZ7
448
elution,137 and elution of their complexes with EDTA 138 and sulphosalicylic acid;139 the removal of cations and anions before determining silica;l40 separations of very many small groups of metals; and extension of the lower limits of detection of metals by using particles of resin as a support for spot tests: nanogram quantities of iron have thus been identified.141 I n many fields of organic analysis, and particularly in biochemistry, ion exchange has proved its worth, as, for example, in the separation of hydroxyacids,lP2 aldonic acids, and sugars,le3 amino-acids,lP4~ and mixtures 145 of barbiturates many of these separations are performed on treated papers. Gas Chromatography.-The number of papers continues to increase, both on the development of theoretical principles and on applications. Negri 1 4 7 has reviewed advances in technique, includingthe use of different adsorbents in parallel and in series, temperature regulation of the thermistor and the column, phases suitable for high-temperature work, improvements in detectors, the use of capillary columns, and the reaction of the test substance immediately before chromatography. Maier and Karpathy 148 have attempted, with results sufficiently accurate for most practical problems, to systematise the choice of column and conditions in terms of charts of data. A mathematical survey of the factors affecting efficiencyof gas chromatography for analysis, with a brief review of techniques, has been published,149 and applications have been described to work in nuclear technology, including the advantages of temperature programming and the use of molecular sieves. O Comparative investigations have been made of the merits of various support materials; performance with a non-polar, a polar, and a strongly polar stationary phase was studied,151and, with the criteria for an ideal support in view, the practical characteristics of a number of materials were investigated.152 Discontinuity of the liquid phase can affect to an unpredictable extent the values of retention times and volumes, and if the support is uncovered a t any point spurious peaks are produced; this subject has been discussed in detai1.153 The behaviour of 10 inorganic gases on halogenated hydrocarbon columns, with hydrogen as carrier and thermal-conductivity detecJ. P. Faris and J. W. Warton, Analyt. Chem., 1962, 34, 1077. Minczewski and R. Dybczyliski, J. Chromatog., 1962, 7, 98, 568. J. S. Fritz and T. A. Palmer, Talanta, 1962, 9, 393. 140 L. H. Andemson, Arkiv Kemi, 1962, 19, 223. 141 Masatoshi Fujimoto and Yukio Nakatsukasa, Analyt. Chim. Acta, 1962, 26,
137
13* J.
427.
142
143
144
145A.B. Svendsen and E. Brochmann-Haussen, J. Pharm. Sci., 1962, 51, 514. 146 H. V. Street and S. K. Niyogi, J. Pharm. Sci., 1962, 51, 666. 147 R. C. Negri, dfinidad, 1961, 18, 383. 14* H.J. Maier and 0. C. Karpathy, J . Chromatog., 1962, 8, 308. 149 M. A. Khan, Lab. Practice, 1962, 11, 120. l z 0A. D. Horton, Nucl. Sci. Engng., 1962, 13, 103. 151 R. Staszewski and J. Janak, Coll. Czech. Chem. Comm., 1962, 27, 532. 1 5 2 D. T. Sawyer and J. K. Barr, Analyt. Chem., 1962, 34, 1518. 153 R. A. Keller, R. Bate, B. Costa, and P. Forman, J. Chromatog., 1962, 8, 157.
B. Alfredsson, L. Gedda, and 0. Samuelson, Analyt. Chim. Acta, 1962, 27, 63. 0. Samuelson and R. Simonson, Svemk Papperstidn., 1962, 65, 363. C. S. Knight, J. Chromatog., 1962, 8, 205.
CARTWRIGHT, WESTWOOD, A N D WILSON
449
tors, has been investigated,154and ionisation detectors have been used to detect trace quantities of permanent gases.155 A considerable volume of useful papers has been concerned with establishing in a practical manner the best column materials and operating conditions for particular separations. Among these are separations of isomeric aliphatic alcohols,156 isomeric disubstituted benzenes,l57 methylsilanes,15* high-boiling amine~,l5~ dissolved gases in aqueous solution,l 6 0 and the and determination of atmospheric pollutants 161 and blood-alcohol.162
6. GRAVIMETRIC AND TITRIMETRIC ANALYSIS
Gravimetric Analysis.-Instrumental analysis is nowadays so much to the fore that many analysts may understandably ask, whither gravimetry ? It may well be that gravimetric methods will be finally relegated to occasional use for reference purposes, but for the moment there is still considerable activity to report in the field of inorganic analysis. General. I n experiments to determine the weight constancy of porcelain filter crucibles Braddock 163 found that the crucibles used maintained constant weight after being heated to various temperatures in the range 135-SOO", and that weights were not affected by the use of either water or ethanol wash liquids. Increasing interest has been shown in the use of masking agents t o effect separations of metal ions, and Hulanicki 164 has described the derivation of a new term, the masking coefficient, to predict whether masking or precipitation occurs. The reactions of aliphatic mercapto-alcohols and mercapto-acids with inorganic cations have been investigated,l65 and methods have been developed for the determination by precipitation of silver, cadmium, lead, and thallium(1) and for the qualitative detection of other elements. Inorganic. A study has been made of the influence of certain foreign ions on the determination of potassium as the tetraphenylborate.166 High results were obtained in the presence of sodium persulphate and low values in solutions containing sodium periodate ; no appreciable errors were caused by the presence of sodium perchlorate. has Embelin (2,5-dihydroxy-3-undecyl-l,4-benzoquinone) been found to give insoluble complexes with copper and cadmium in the pH ranges 2-5-65
H. G. B. 15'A.
154 155 156
Runge, 2. analyt. Chem., 1962, 189, 111. Gnauck, 2. analyt. Chem., 1962, 189, 124. Drews, H. Specht, and G . Offer, 2. analyt. Chem., 1962, 189, 325. E. Habbousch and B. 0. C. Norman, J . Chromatog., 1962, 7, 438. 158 T. Garzb, F. Till, and I. Till, Magyar Kim. Polydirat, 1962, 68, 327. 159 J. Vessman and G. Schill, Svensk farm. Tidslcr., 1962, 66, 601. 160 J. W. Swinnerton, V. J. Linnenbom, and C. H. Cheek, Analyt. Chem., 1962, Bellar, J. E. Sigsby, C. A. Clemons, and A. P. Altshuller, Analyt. Chem., 763. Machata, Mikrochinz. Acta, 1962, 691. I. Braddock, Chemist-Analyst, 1962, 51, 79. Hulanicki, Talanta, 1962, 9, 549. E. Casassas and F. Buscarbns, Chinz. analyt., 1962, 44, 20. J. D. R. Thomas, Analyst, 1962, 87, 151.
34, 483. 161 T. 1962, 34, lSZ G. 163 L. 16* A.

165
lS6
450
and 6.0-6-5, respectively. 167 The precipitates are suitable for gravimetric purposes and the method can be used for the separation of the two metals. Copper is precipitated a t pH 2.5-3.0 and the complex is ignited to oxide; cadmium is precipitated in the filtrate at pH 6.0-6-5. Copper can also be quantitatively precipitated by NN'-disalicylidene-ethylenediamine,168and weighed after drying a t 100-120". A method has been described for the separation of strontium and calcium by precipitation of strontium with an ethanolic solution of rhodizonic acid in the presence of N -hydroxyetliylethylenediaminetriacetic acid as a chelating agent. A double precipitation is necessary when large amounts of calcium are present. A new method has been proposed for the determination of scandium and its separation from rare earths and thorium by precipitation with mandelic acid.170 Satisfactory results were obtained over the pH range 1.8-3.2, but a t higher pH values coprecipitation of thorium took place. The precipitate was ignited at 800" and weighed as Sc,O,. Lanthanum ferrocyanide has been shown to be quantitatively precipitated from solution by the addition of an excess of potassium ferrocj-anide.171 The precipitate may be weighed as LaKFe(CN), or the lanthanum can be determined by titrating the excess of potassium ferrocyanide solution. The determination of cerium(1v)and its separation from rare earths with 1-hydroxy-3-methoxy9-xanthone has been described.172 I n an investigation of the influence of alkali metals and ammonium ions on the precipitation of thallium dichromate it has been found that potassium, rubidium, czesium, and ammonium, but not lithium or sodium, are ~ o p r e c i p i t a t e d . ~ ~ ~ may be overcome to This some extent by precipitation from hot acid solution, but reprecipitation of the thallium dichromate is necessary when the concentration of the interfering ions is high. Germanium has been precipitated as the tetraphenylarsonium germanomolybdate complex 174 having the formula Ge(Mo,O,,),[ (C6H5)BA~]I, a and study has been made of interfering ions. The use of N-benzoylphenylhydroxylamine(BPHA) for the determination of zirconium and its separation from iron, aluminium, chromium, titanium, niobium, and tantalum has been described.175 The precipitate can be weighed as Zr(BPHA), which is stable up t o 240", or as ZrO, after heating to above 500". Two new reagents, tartrazine and flavazine, have been proposed for the precipitation of zirconium.176 The reagents were found to be more sensitive than mandelic acid and the precipitates settled more rapidly. Zirconium has also been quantitatively precipitated in the
167 C. Bheemasankara Rao, V. Venkateswara Rao, and V. Venkateswarlu, 2. analyt. Chem., 1962, 185, 216. 168 B. R. Singh and S. Kumar, 2. analyt. Chem., 1962, 185, 259. 1 6 9 L. Hainberger and S. C. Shnchez, Mikrochim. Acta, 1962, 760. I 7 O I. P. Alimarin and Shen Han-Si, Talanta, 1962, 9, 1. 1 ' 1 5. N. Gaur, 2. analyt. Chem., 1962, 185, 357. 172 B. Dev and R. D. Jain, Proc. Indian Acad. Xci., 1962, 55, A , 213. 173 N. I. .Bashilova, Zhur. analit. Khim., 1962, 17, 190. 1'4 J. P. LabbB, Mikrochim. Acta, 1962, 283. 1 7 5 I. P. Alimarin and Tze Yung-Schaing, Talanta, 1962, 9, 9. 1 7 6 G . Popa, F. Popea, D. Cluceru, and G. Baiulescu, Analyt. Chim. Acta, 1962, 26, 434.
C A R T W RIG H T
, W E S T W 0 0D , A N D
W I L S0 N
451
p H range 1 4 by the addition of diammonium indigo-5,5-disulphonate. l7 Iron, titanium, aluminium, beryllium, uranium, cerium(rn), nickel, and cobalt do not interfere. The separation and gra.vimetric determination of thorium and cerium(Ir1) with vanillin has been described. 178 A study has been made of the gravimetric determination of uranium(v1)by . precipitation with N -benzoyl-N-phenylhydroxylamineI 79 The precipitate may be weighed directly or as U308 after ignition. Cerium(In), thorium, lead, and bismuth may be masked with magnesium-EDTA complex. Iron(m), titanium(Iv), zirconium, molybdenum(vI), and small amounts of aluminium may be removed before the determination of uranium by precipitating them with the reagent in more acid solution, but fluoride, carbonate, and organic acids interfere. Uranium has also been determined by precipitation with hexaminecobalt nitrate.Is0 Fluoride does not interfere and the method is said t o be suitable for the determination of uranium in uranium fluoride and uranium alloys. Palladium can be quantitatively precipitated in acid solution by the addition of a 1 yo solution of quinolinimide (pyridine-2,3-dicarboximide).181 Interference by tin may be prevented by the addition of citric acid, but the presence of oxalate, tartrate, or EDTA causes incomplete precipitation. Precipitation from homogeneous solution. Reference has been made in previous Reports t o the r61e of nucleation in precipitation from homogeneous solution, but this aspect does not appear t o have received much recent attention, and the published papers deal mainly with the application of the technique t o the precipitation of specific compounds with occasional references t o nucleation. An account of precipitation from homogeneous solution has been given by Dams71g2and Williams 1 8 3 has reviewed recent advances in the field. I n further studies of precipitation at constant pH by cation release from metal-EDTA complexes consideration has been given to the importance of complex stability and the solubility of the precipitate.184 An example has been given of the use of EDTA as a masking agent in the separation of calcium and barium. EDTA has also been used as a masking agent in the homogeneous precipitation of sulphides by hydrolysis of thioacetamide. l g 5 The fractional precipitation of lanthanum praseodymium iodate, involving double complex-formation and replacement, has been described. lS6 Equal amounts are complexed by [(carboxymethylamino)di(ethy1eneimino)ltetraacetic acid and N-(carboxymethyl)-N-2-hydroxyethyl-~~-ethylenediglycine, and iodate is added. Lanthanum is released by slow dropwise addition with stirring of cadmium chloride solution.
D. Jain and J. J. Singh, J. Less-Common Metals, 1962, 4, 145. D. Jain and J. J. Singh, Analyt. Chim. Acta, 1962, 27, 359. Das and S. C. Shome, Analyt. China. Acta, 1962, 27, 58. V. Vinogradov and R. M. Apirina, Zhur. analit. Khirn., 1962, 17, 222. lS1 A. K. Majumdar and S. P. Bag, Z. analyt. Chem., 1962, 188, 347. Is2 R. Dams, Mededel. vlmm. chem. Ver., Nr. 3, 1961, 65. la3 M. Williams, I n d . Chem., 1962, 38, 134, 186. lS4 P. F. S. Cartwright, Analyst, 1962, 87, 163. lS5 G. C. Krijn, Chem. Weekblad, 1962, 58, 127. lS6 F. H. Firsching, Analyt. Chem., 1962, 34, 1696.
177
178
B. B. J. lSo A.
179
452
Continued interest is shown in methods involving the formation of the precipitant in situ. The reaction between salicylaldehyde and hydroxylamine hydrochloride in the presence of copper ions has been used t o preA dense precipitate was obtained cipitate copper s a l i ~ y l a l d o x i m . ~ ~ ~ which was dried to constant weight a t 110". A study has been made of the hydrolysis of 8-acetoxyquinoline,lS8and the method has been used for the precipitation of magnesium 8-hydroxyquinoline. lS9 A good separation from sodium, potassium, and barium was obtained a t pH 10.0, but it was found necessary also to cool the solutions in an ice-bath, and to add the 8-acetoxyquinoline slowly with stirring t o obtain a satisfactory rate of hydrolysis. Precipitation usually occurred when the last of the reagent had been added. The hydrolysis of 8-acetoxyquinoline has also been investigated by Weiss and Shipman l g owho have applied the method to the study of co-crystallisation of ultramicro-quantities of iron and other elements. The reaction between biacetyl and hydroxylamine t o form dimethylglyoxime has been used to precipitate nickel dimethylglyoximate. l91 During the investigation evidence was found of the existence of a complex between nickel and biacetyl monoxime. The persistent supersaturation with respect t o dimethylglyoximate which was found to be present in the system was considered t o be the explanation of the incomplete precipitation of small amounts of nickel with dimethylglyoxime. It has been reported that niobium and tantalum can be precipitated from their solutions in hydrogen peroxide and nitric acid by thermal decomposition of the soluble peroxide ;I92 coprecipitation of titanium is negligible. When thermal decomposition is carried out in slightly alkaline medium, niobium, tantalum, and titanium are precipitated with only low coprecipitation of tungsten. Molybdenum has been precipitated as sulphide by hydrolysis of thioacetamide.193 The precipitate was ignited a t 500-550" and weighed as the trioxide. A nuclear magnetic resonance method has been used to study the precipitation of manganese sulphide from homogeneous solution. lg4 Titrimetric Analysis.-This Report is divided, as in previous years, according to the class of titrimetric determination. A new section has been added dealing with photometric titrations and certain papers have been included which appear t o be of fundamental interest but were omitted in earlier Reports. General. Reviews have been published describing the applications of vanadate as an oxidimetric reagent l g 5and the use of quinol (hydroquinone)
18' la8
R. F. Pietrzak and L. Gordon, Talanta, 1962, 9 327. , D. Elliot, L. C. Howick, B. G. Hudson, and W. K. Noyce, Talanta, 1962, 9,
723.
, J. T. Corkins, R . F. Pietrzak, and L. Gordon, Talanta, 1962, 9 49. H. V. Weiss and W. H. Shipman, Analyt. Chem., 1962, 34, 1010. l91 E. D. Salesin, E. W. Abrahamson, and L. Gordon, Talanta, 1962, 9, 699. 192 R. Dams and J. Hoste, Talanta, 1962, 9 86. , l93 F. Burriel-Marti and A. Maciera Vidan, Analyt. Chirn. Acta, 1962, 26, 163. 194 R. L. Causey and R. M. Maza, Analyt. Chem., 1962, 34, 1630. 195 A. Berka, J. Vulterin, and J. Zfka, Chemist-Analyst, 1962, 51, 24.
189 190
CARTWRIGHT, W E S T W O O D , AND WILSON
453
as a reductimetric reagent in titrimetric analysis.lg6 Two neutral mixed ligand complexes, dicyanobis-(1,10-phenanthroline)iron(rr) and dicyanobis(e,Z-bipyridyl)iron(n), have been used as indicators for the titration of various weak bases in non-aqueous solvents and also for certain redox titrations in aqueous solution.lS7 It has been recommended that morpholinium 3-oxapentamethylenedithiocarbamate a suitable primary subis stance for the preparation of standard solutions of acids.lg8 Bishop and Jennings have continued their investigations of the use of chloramine-T and have published papers describing titrations in hydrochloric acid media with iodine monochloride as a reaction intermediate,lS9 the chloramine-T-antimony reaction,200 the chloramine-T-hydrazine reactionY2O1 the chloramine-T-thallium and -thiocyanate reactions.202 and Halogen titrations. A study of the titration of silver with halide or thiocyanate ions has shown that satisfactorily sharp end-points may be obtained at pH 4 5 by using p-ethoxychrysoidine as an adsorption indicator. 203 Magnesium may be precipitated as magnesium ammonium arsenate, the precipitate dissolved in sulphuric acid, and the resulting arsenic acid titrated iodimetrically.20* The method has been found to be more rapid and to give more reproducible results than determination by precipitation as 8-hydroxyquinoline complex. A similar technique has been proposed for the rapid determination of thorium after precipitation of thorium hydrogen ar~enate.~O5 A rapid method for the determination of persulphate has been described, based on the reaction between persulphate and thiosulphate in the presence of copper ions.206 An excess of thiosulphate is added and the excess is titrated with standard iodine solution. A bromometric method has been used for the determination of formates by oxidation with bromine,207 and hydrazine in 35% hydrazine solutions has been determined by titration with potassium iodate after acidification with hydrochloric acid.208 Other redox titrations. Bishop has discussed the precise calculation of data for redox titration curves 209 and the influence of absolute concentration on the parameters of redox titrimetry.210 The use of Variamine Blue as a redox indicator in the determination of thiocyanate and mercury(n)
A. Berka, J. Vulterin, and J. Z$ka, Ghemist-Analyst, 1962, 51, 88. A. A. Schilt, Analyt. Chim. Acta, 1962, 26, 134. W. Haas, Mikrochim. Acta, 1962, 738. ls9 E. Bishop and V. J. Jennings, TaZanta, 1962, 9, 581. 2oo E. Bishop and V. J. Jennings, Talanta, 1962, 9, 593. 201 E. Bishop and V. J. Jennings, Talanta, 1962, 9, 603. 2 0 2 E. Bishop and V. J. Jennings, Talanta, 1962, 9, 679. 2 0 3 K. N. Tandon and R. C. Mehrotra, Analyt. Chim. Acta, 1962, 27, 15. 204 G . 13. Shakhtakhtinskz and G . A. Aslanov, Azerb. Khim. Zhur., 1961, 63; Ref. Zhur. Khim., 1962, Abs. No. 5D51. 2051. Mamedov and G . B. Shakhtakhtinskii, Azerb. Khim. Zhur., 1961, 99; A. Ref. Zhur. Khim., 1962, Abs. No. 4D99. 2 0 6 C. D. Bisht and S. P. Shrivastava, 2. analyt. Chem., 1962, 188, 23. 2 0 7 R . M. Verma and S. Bose, J . I n d i a n Chern. Soc., 1962, 39, 329. 2 0 8 U.K.A.E.A. Report PG 342(W), 1962. 2 0 9 E. Bishop, Analyt. Chirn. Acta, 1962, 26, 397. 210 E. Bishop, Analyt. Chirn. Acta, 1962, 27, 253.
lS6
lS7 lS8
454
ANALYTICAL C H E M I S T R Y
ions has been investigated.2ll Thiocyanate may be determined by titrating with mercuric nitrate, or mercuric ions can be determined by adding a known volume of potassium thiocyanate solution and titrating the excess. Vanadium(1v) can be determined by titration with cerium(1v) sulphate by using Rhodamine 6G as a fluorescent indicator;212the fluorescence is suddenly quenched by a slight excess of oxidant. A method has been described for the determination of niobium in the presence of tantalum.213 Niobium(v) is reduced in a Jones reductor to niobium(m) which is collected in ammonium ferric sulphate solution to produce ferrous iron equivalent to the niobium present. The ferrous iron is then determined by titration with dichromate solution. Iron, uranium, or plutonium can be determined by titration with cerium(1v) solution in nitric acid media.214 Ammonium hexanitratocerate(1v) has been used for the titration of oxalic and mandelic acids in nitric acid or hydrochloric acid by using ferroin indicator, 215 and a volumetric method for the determination of quinol (hydroquinone) using ferric alum and potassium dichromate has been described.216 MisceZZaneous. The determination of fluorine by titration, with aluminium nitrate solution, arsenazo I (see below) being used as the indicator, has been investigated. Tungstate has been determined by direct titration with lead nitrate solution with 6,13-dihydro-6,13-dihydroxy1,4:8,11-pentacenediquinone-2,9disulphonic acid as indicator.218 Chebtometric titrations. Lindstrom and Stephens 219 have suggested the use of magnesium iodate tetrahydrate as a standard for the preparation of EDTA solutions for calcium and magnesium titrations. The use of metallic copper as a primary standard for EDTA has also been studied.220 PFibil and Veseljr 2 2 1 have reported the use of a new titrimetric reagent, triethylenetetramine-NNNNNN-hexa-acetic acid (TTHA). The application of two arsono-type indicators has been studied.Z22 The first, 3-(2-arsonophenylazo)-4,5-dihydroxynaphthalene-2,7-disulphonic (arsenazo I), can acid be used for the determination of thorium(Iv), lanthanum(m), cerium(m), yttrium(m), and erlsium(1n) in acid solution, and magnesium in alkaline solution. The second, 4-(2-arsonophenylazo)-3-hydroxynaphthalene-2,7-disulphonic acid disodium salt (thoron I),may be used to determine thorium in acid solution.
Z. Gregorowicz, F. Buhl, and B. Piwowarska, 2. analyt. Chem., 1962, 188, 2. G. G. Rao and L. S. A. Dikshitulu, Talanta, 1962, 9, 289. J. B. Headridge and M. S. Taylor, Analyst, 1962, 87, 43. J. Corpel and F. Regnaud, Analyt. Chim. Acta, 1962, 27, 36. 215 G. G. Rao, P. V. K. Rao, and K. S. Murty, Talanta, 1962, 9, 835. 216 K. B. Rao, 2. analyt. Chem., 1962, 185, 286. 217 V. M. Brodskaya, A. F. Kutelnkov, and G. A. Lanskoi, Byull. Nauch.-Tekh. Inform., Min. Geol. i Okhran N d r . , S.S.S.R., 1961, 104; Ref. Zhur. Khim., 1962, Abs. No. 9D93. 218 H. Brantner, Mikrochirn. Acta, 1962, 125. 219 F. Lindstrom and B. G. Stephens, Analyt. Chem., 1962, 34, 993. 2 2 0 T. Iwamoto and K. Kanamori, Analyt. Chim. Acta, 1962, 28, 167. 221 R. PFibil and V. Veself, Talanta, 1962, 9, 939. 2 2 2 0. Gimesi, G. R&dy, and L. Erdey, Period. Polytech., 1962, 6, 15.
211 212 213
CARTWRIGHT,
WESTWOOD, A N D WILSON
455
A procedure has been given for the determination of copper in the presence of manganese and iron,223and a new chelatometric determination of mixtures of silver and lead has been described.224 Barium EDTA has been used in new methods for the determination of mixtures of zinc and chromium(m) and of zinc and aluminium.225 Considerable attention has been given t o the determination of aluminium. Pfibil and Vesely 226 have studied the use of 1,2-diaminocyclohexanetetraacetic acid which reacts almost instantaneously with aluminium in the cold. Aluminium is determined by adding an excess of reagent and back-titrating with lead nitrate solution, Xylenol Orange being used as indicator. From a comparison of three methods for the determination of aluminium, Malissa and Kotzian 227 have concluded that a method due to PFibil et was to be preferred. Other papers have described the determination of aluminium in uranium metal 229 and in aluminosilicates.230 The direct chelatometric determination of gallium with EDTA is possible by using 8-hydroxy-7- 1-napht hylazo quinoline-5-sulphonic acid as indicator in the pH range 2.2-5; calcium, magnesium, cadmium, and zinc do not interfere, and interference by aluminium can be avoided by the addition of fluoride.231 Thallium may be determined with EDTA with 8-hydroxy7-2-pyridylazoquinoline as indicator.232 The selective determination of titanium in the presence of niobium and tantalum by a back-titration of an excess of diaminocyclohexanetetraacetic acid with copper in the presence of hydrogen peroxide and PAN as indicator has been improved by the use of Methyl Calcein or Methyl Calcein Blue as metal fluorochromic indicator.233 Reduction of chromium(VI) with sodium hydrogen sulphite in the presence of a slight excess of EDTA leads to the quantitative formation of chromium(n1)-EDTA complex.234 Chromium can be determined by back titrating the excess of EDTA with thorium solution a t pH 2-5-3-5. Chelatometric methods have been used to a limited extent in the determination of organic compounds. Hennart has described the titrimetric determination of alkylmagnesium halides, 235 the determination of sulp h ~ n a r n i d e s ,and ~ determination of purine-6-thi01.~~~ ~ ~ the
D. A. Doornbos, G. Ab, and J. S. Faber, Phama. Weekblad, 1962, 97, 257. F. Sierra and J. Heriiandez Caiiavate, Anales real Xoc. espa6. P s QuiTn., i. 1962, 58, B , 219. 2 2 6 F. Sierra [and C. Sanchez Pedreno, Anales real SOC.espaii. Fi8. Quim., 19B2, 58, B , 223. 2 2 6 R. P?ibil and V. Veself, Talanta, 1962, 9, 23. 2 2 7 H. Malissa and H. Kotzian, Analyt. Chim. Acta, 1962, 26, 128. 2 2 8 R. Piibil et al., Chem. Listy, 1957, 51, 2135. 2 2 9 U.K.A.E.A. Report PG 293(S), 1962. 230 H. Bennett, W. G. Hawley, and R. P. Eardley, Trans. Brit. Ceram. SOC., 1962, 61, 201. 231 A. I. Busev, L. L. Talipova, and L. M. Shrebkova, Zhur. analit. Khirn., 1962,
223
226
17, 180.
232 A. I. BUSBV, L. Talipova, and V. M. Ivanov, Zhur. Vsesoyuz. Khirn. obshch. im. L. D. I. Mendeleeva, 1961, 6, 598; Ref. Zhur. Khim., 1962, Abs. No. 9D58. 233 E. Lassner and R. Scharf, Chernwt-Analyst, 1962, 51, 49. 2 3 4 D. A. Aikens and C. N. Redly, Analyt. Chem., 1962, 34, 1707. 2 3 5 C. Hennart, Chim. analyt., 1962, 44, 7. 2 3 6 C. Hennart, Chim. analyt., 1962, 44, 8. C. Hennart, Talanta. 1962, 9, 97.
456
Spectrophotometrictitrations. Many, but not all, of the methods discussed in this section are chelatometric; all have in common the use of photometric methods for the determination of end points. Some references are given t o papers which appeared last year and were not reported, but which are now mentioned because of their particular interest. The theory of chelatometric titrations with a photometric end-point has been discussed,238and the construction of a simple photometric titrator has been described.239 Details have been given of an instrument having increased sensitivity which embodies two photocells that simultaneously register both colours of the indicator.240 The use of differential spectrophotometric methods for determining the end points in aqueous and nonaqueous acid-base titrations and in chelatometric titrations has been reported.241 The method has been applied t o the titration of phosphoric acid, acetic acid, L-phenylalanine, L-leucine, and DL-alaninewith sodium hydroxide in aqueous solution, t o the titration of sodium acetate and o-chloroaniline with perchloric acid in glacial acetic acid, and t o the determination of magnesium with EDTA. The consecutive titration of calcium and magnesium has been investigated.242 Calcium was first titrated a t pH 10 by using ethyleneglycolbis(aminoethy1)tetra-acetic acid with murexide indicator, followed by titration of magnesium with EDTA and Eriochrome Black T indicator to a photometric end point. The chelatometric determination of submicrogram amounts of calcium and magnesium has also been described.243 Cadmium has been determined in the presence of zinc by titration to a photometric end point with 1,Z-di-(2-aminoethoxy)ethane-NNNN-tetraacetic acid and ammoniacal copper solution as indicator. 244 Titanium has been determined in the presence of aluminium,245and thorium, in amounts as low as 10 micrograms, has been determined by titrations with EDTA, @-SNADNS-6being the indicator.246 The chelatometric determination of plutonium in reactor-fuel processing plant solutions has been described ;z47 after suitable extraction, an excess of EDTA is added and the remaining EDTA is titrated with zinc chloride solution, dithizone being used as indicator. Microgram amounts of fluoride have been determined by titration with thorium nitrate solution t o which sodium alizarinmonosulphate indicator is added.248 Flaschka and Ganchoff have described the selective chelatometric determination of cobalt, using a photometric method for the detection of the end point. 249
H. Flaschka, Talanta, 961, 8, 381. H. Flaschka and P. Sawyer, Talanta, 1961, 8, 521. 2 4 0 J. Fog and E. Jellum, Analyst, 1962, 87, 302. 241 S. Bruckenstein and M. M. T. K. Gracias, Analyt. Chem., 1962, 34, 975. 2 4 2 H. Flaschka and J. Ganchoff, TuZuntu, 1961, 8, 720. 2 4 3 H. Flaschka and P. Sawyer, T u h n t a , 1962, 9, 249. 2 4 4 H. Flaschka and J. Ganchoff, Taluntu, 1962, 9, 76. 2 4 5 L. Giuffre and F. M. Capizzi, Ann. Chim. (Italy), 1962, 52, 398. 2 4 6 S. K. Datta and S. N. Saha, Chemist-Analyst, 1962, 51, 49. 2 4 7 D. G. Boase, J. I<. Foreman, and J. L. Drummond, Talanta, 1962, 9, 53. 2 4 8 W. P. Pickhardt, Analyt. Chem., 1962, 34, 863. 2 4 9 H. Flaschka and J. Ganchoff, Talantu, 1961, 8, 885.
238
23s
457
Non-aqueous titrations and functional-group determinations. The theoretical basis of titration in non-aqueous media has been reviewed,250and a general study has been made of the influence of cation structure on the titration characteristics of quaternary ammonium titrants 251 and of factors affecting the stability of non-aqueous quaternary ammonium tit rant^.^^^ The purification of pyridine for use in non-aqueous titrations has been described,253 and details have been given of the preparation of non-aqueous titrants by reaction of quaternary ammonium chlorides with potassium hydroxide in isopropyl alcohol solution.2 5 4 Cerimetric methods in non-aqueous media have been applied to the oxidation and determination of ascorbic acid.255 The semimicro-determination of the neutralisations equivalents of higher fatty acids has been studied and the method has been applied to the determination of lauric, myristic, palmitic, elaidic, stearic, oleic, and linoleic NN'-Disubstituted p-phenylenediamines have been determined by neutralisation with perchloric acid,257 and the determination of codeine and phenobarbitone by titration with perchloric acid in dioxan has been described.2 5 8
7 INSTRUMENTAL END-POINT DETERMINATIONS .
General.-Under this heading conductometric, amperometric, coulometric, potentiometric, and high-frequency methods have been grouped. Probably because of its simplicity, direct potentiometry has continued to be the most popular technique and a very large number of papers have appeared on its applications. Only those of particular interest to analysts can be considered in this Report. Chronopotentiometry has been developing, though little work appears to have been done in this country. New work has appeared on differential electrolytic potentiometry, which is capable of application with accuracy t o extremely dilute solutions and nanogram quantities. Applications of amperometric titration methods have continued to increase and several novel procedures have been reported. Conductometric and high-frequency methods have only found occasional new uses, and interest in them has generally declined, probably owing to their lack of specificity. Coulometric methods, on the other hand, have continued to develop and there has been an increasing volume of papers on theory and practical applications. Completely automatic titrators have been devised, some of which can be used for continuous recording. Conductometric-Interest in this technique has continued to decline and
A. P. Kreshkov, Zhur. analit. Khim., 1962, 17, 6. G. A. Harlow, Analyt. Chem., 1962, 34, 1482. 2 5 2 G. A. Harlow, Analyt. Chem., 1962, 34, 1487. 2 5 3 W. M. Banick, jun., Analyt. Chem., 1962, 34, 296. 2 5 4 G. A. Harlow and G. E. A, Wyld, Analyt. Chem., 1962, 34, 172. 2 5 5 G. P. Rao and A. R. V. Murthy, 2. analyt. Chem., 1962, 187, 96. 2 5 6 R. D. Tiwari, K. C. Srivastava, and J. P. Sharma, 2. analyt. Chem., 1962, 187, 161. 2 5 7 0. Lorenz and C. R. Parks, Analyt. Chem., 1962, 34, 394. 258 R . Vasiliev, V. Scintee, and E. Sisman, Rev. Chim. ( R o u m a n i a ) , 1962, 13, 56.
250
251
458
ANALYTICAL C H E M I S T R Y
few significant developments have occurred since the last Report. A general review by Pungor, giving principles and applications t o precipitation, complex formation, and redox titrations, has been and reviews have appeared recording the use of this method in non-aqueous titrations.260s261 A four-cell conductivity bridge has been used as a continuous detector for the eluents from a chromatographic column. The peak heights measured on a recorder were correlated with the amount of sample with a standard deviation of k0.25 pmole. A frequency of 10 kc.sec.-l was used, with silver tubes for cells, and peak height-concentration graphs were linear for sodium nitrate.262 The carbon content of the atmosphere has been measured by using a special absorption cell and recorder, giving values in close agreement with those by other, more time-consuming, methods.263 With use of a special cell with a very large cell constant, conductometric titrations have been carried out in the presence of a considerable excess of an indifferent electrolyte. Titrations of dilute hydrochloric acid in 5~-sodium chloride and dilute alkali in 7~-sodium nitrate have been de~cribed.26~ Small amounts of bicarbonate have been determined in an excess of carbonate by a similar meth0d.2~5 Barium has been determined by titration with potassium tellurite as titrant in aqueous solution. I n the presence of 40-50% alcohol the end points were quite sharp; the reverse titration was also satisfactory.266 As part of a fundamental study of silicosis the rates of dissolution of various silica powders in 0.1M-hydrofluoric acid were studied. An increase in conductance occurred owing t o formation of fluorosilicic acid. Evidence was adduced against the " solubility theory " of silicosis.267 Weak inorganic acids and ammonium salts in aqueous solution containing an excess of ammonia have been titrated with lithium hydroxide. The method relied on the fact that the acid strength increased since the reaction AH NH,+ A- NH,+ occurred t o a greater extent than AH H 2 0+ A,Of. The Bronsted acid NH,+ is neutralised by alkali. Among 16 compounds titrated were germanium, arsenic, osmium, and chromic oxides, and boric, selenious, sulphurous, and pyrophosphoric acids. I n most cases excellent end points were obtained.268 Sulphate has been determined by titration with barium acetate in an acetic acid medium; and, as an alternative, an excess of barium acetate was added and the excess back-titrated with perchloric acid. Both methods gave good end points though the presence of sulphates of potassium and nickel produced poor results ;.ferric sulphate, however, caused no interference.269 Carbon has been determined in the less common metals and in stainless steels by absorption of the dioxide evolved, after combustion
E. Pungor, J. Electroanalyt. Chem., 1962, 3 289. , J. T. Stock and W. C. Purdy, Lab. Practice, 1962, 11, 21. C. A. Streuli, Analyt. Chem., 1962, 34, 302R. 2 6 2 C. Duhne and 0. S. De Ita, Analyt. Chern., 1962, 34, 1074. 263 H Malissa and G . Wagner, Mikrochim. Acta, 1962, 332. . 2 6 4 H. L. Kies and S. H. Tan, 2. analyt. Chem., 1962, 186, 201. 2 6 5 Z. HoBklek and F. Kutek, Chem. pumysE, 1962, 12, 128. 2 6 6 S. Prasad and B. L. Khandelwal, J. Indian Chem. SOC., 1962, 39, 84. 213'1. Bergman, J. Appl. Chem., 1962, 12, 336. 2 6 8 F. Gaslini and I. Z. Nahum, J. Electroanalyt. Chem., 1962, 3, 85. , 2139 G. Goldstein, D. L. Manning, and H. E. Zittel, Analyt. Chem., 1962, 34, 1169.
259
260
261
C A R T W R I G H T , WESTWOOD, A N D WILSON
459
in a high-frequency furnace, in 2% sodium hydroxide solution. Calibration was made by absorption of known weights of carbon dioxide in the absorp~~ tion cell and the construction of a conductance-time g r a ~ h . 2 Carbon has also been determined in organic compounds by oxidation in the presence of Co30, and absorption of the CO, in barium hydroxide solution with measurement of change of conductivity. The method was claimed t o be rapid, with a mean error within &0.22y0 of carb0n.2~1 A complete investigation of a modified Unterzaucher method for the determination of oxygen in organic compounds has been carried out, a conductometric detection of the end point being used. It was applicable t o oxygen contents from 0.02 to 50% in samples containing halogens, nitrogen, and A method has been described for the determination of hydrogen in organic compounds in which the conventional water absorption tube was replaced by a conductometric cell containing sulphuric acid. This utilised the fact that, over the concentration range 99-83 t o 99.75% w/v of sulphuric acid, a linear change in conductance occurred. A reproducibility of &0.19 pg. was ~lairned.~~3 Fluorosulphuric acid in acetic acid behaved as a stronger acid than perchloric acid, and titrations were carried out with diethylaniline, pyridine, and cc-picoline with good end points. The results were checked with potentiometric and visual titrations.274 Epoxyethane was determined by addition of an excess of hydrochloric acid and back-titration with sodium acetate in aqueous-alcoholic solution. Appreciable amounts of methacrylic acid and ferric chloride caused no interference.275 Trimethylaluminium has been titrated conductometrically with isoquinoline, and the method has been claimed suitable for routine control of the purity of this compound.276 Amperometric.-There has been a continued interest in this technique during the last year. Laitinen has again reviewed the method with its applications in oxidation-reduction and ion-combination reactions and reactions involving organic reagents.277 The use of electrochemical indicators in electrometric analysis, particularly amperometric titrations with ferric, mercuric, and zincate ions as indicators, has also been reviewed.278 A potentiostat has been devised for studying reaction kinetics amperometrically. The change in potential of a solution as ions are reduced was balanced by the automatic anodic regeneration of similar ions, so that the redox potential of the solution remained constant. The current consumed in the electrolysis was then directly proportional t o the reaction rate. A separate indicator and reference electrode were used to ensure that the redox potential of the bulk solution rather than that of the working electrode was
I. R. Green, J. E. Still, and R. C. Chirnside, Analys.t, 1962, 87, 530. M. VeEera, J. Lakomf, and L. Lehar, Coll. Czech. Chem. Comm., 1962, 27, 1033. F. Salzer, Mikrochim. Acta, 1962, 835. 273 S. Greenfield and R. A. D. Smith, Analyst, 1962, 87, 875. 2 7 4 R . C. Paul, S. K. Vasisht, K. C. Malhotra, and S. S. Pahil, Analyt. Chem., 1962,
270
271
272
34, 820.
275
1962, 35, 2 7 6 R. 2 7 7 H. 278 G .
T. A. Khudyakova, L. I. Namtseva, and M. A. Balandina, Zhur. priklad. Khirn., 824. E. Bonitz and W. Huber, Z . analyt. Chem., 1962, 186, 206. A. Laitinen, Analyt. Chem., 1962, 34, 307R. Charlot and B. Trhrnillon, J. Electroanalyt. Chem., 1962, 3, 1.
460
recorded.279 Preliminary work on a mercury-film electrode has shown it t o be suitable for amperometric measurements a t very low concentrations.280 Cadmium and nickel in alkaline accumulator liquid have been determined by a double-titration method. The solution was made ammoniacal and after addition of an excess of dimethylglyoxime cadmium was titrated with EDTA. A few drops of cadmium were then added to ensure there was no excess of EDTA and the nickel was determined by titrating the excess of dimethylglyoxime with nickel solution. 281 Cobalt has been determined down t o 0-lmM-concentration in 0.h-potassium chloride by reaction with tungstate a t -1.5 v (s.c.e.).282 Separation and determination of thorium in monazite sand has been carried out by precipitation as oxalate and titration with ammonium paramolybdate. Details of interferences and methods of dealing with these were investigated. Good results were claimed, and the methods were stated t o have advantages of simplicity and speed.283 Thorium has also been determined as selenite a t pH 6.2-6.4 in an acetate solution containing 60-70y0 of alcohol. The pH and alcohol concentration were critical, but good end points were attained. Nitrate and sulphate were without influence, but chlorate produced a precipitate. Appreciable excesses of ceric and mercuric ions were also tolerated.284 Vanadium, as vanadyl sulphate, has also been determined with selenite solution a t pH 5.35-5 and a t -1.10 v (s.c.e.); 5-30 mg. of vanadium were determined with an error of <0.09%.285 Copper and zinc in cyanide electrolytes were determined by a double titration. After removal of the cyanide with acid, sulphite was added and the copper was determined with 0.1M-thiocyanate a t -0-5 v (s.c.e.). Another aliquot part was titrated a t -1-2 v with thiocyanate in the presence of pyridine to give the total of copper and zinc.2s6 Copper has also been determined by titration with o-(toluene-p-sulphonamido)-aniline at pH 7.5 in a tartrate medium, and the method has been used for the analyses of brasses and tested on alloys NBS 37E and NBS 63C. Appreciable amounts of cadmium, lead, or zinc gave no interference. 287 Tetraethylenepentamine has also proved t o be an excellent titrant for copper a t pH 4.1 in acetate buffer. Only mercury(I1) and cyanide gave any trouble.288 Amperometric titrations using two polarised electrodes have been applied to determine cobalt with EDTA in acid solution with 100 mv between the electrodes,2*9and nickel with iodine in the presence of dimethylglyoxime in ammoniacal solution, the redox potential of the Ni2+-Ni3+system being lowered by complex formation.290 Thallium has also been titrated
J. M. Matsen and H. B. Linford, Analyt. Chem., 1962, 34, 142. S. A. Moros, Analyt. Chem., 1962, 34, 1584. 2 8 1 E . G. Novakovskaya, Zavodskaya Lab., 1962, 28, 28. 2 8 2 V. D. Anand, G. S. Deshmukh, and A. Joseph, Bull. Chem. SOC. Japan, 1962, 35, 1. 2 8 3 J. J. Burastero and R. W. Martres, Analyt. Chem., 1962, 34, 378. 2 8 4 G. S. Deshmukh and 0. P. Asthana, Z. analyt. Chem., 1962, 187, 81. 2 8 5 G. S. Deshmukh, 0. P. Asthana, and V. 8. N. Pillai, 2. analyt. Chem., 1962, 185, 429. 2 8 6 A. T. Marunina, Zavodskaya Lab., 1962, 28, 25. 2 8 7 T. R. Williams and F. G. Burton, Analyt. Chzm. Acta, 1962, 27, 351. 2 * 8 E. Jacobsen and K. Schroder, Analyt. Chim. Acta, 1962, 27, 179. 2 8 9 A. Varma, J . Sci. I n d . Res. India, 1962, 21, B, 142. 2 9 0 D. Singh and A. Varma, 2. analyt. Chem., 1962, 188, 6.
279
280
461
with this electrode system by using ceric sulphate solution; only chromic ions interfered. The end point was sharp, well-defined, and accurate t o _+ly0.291 A similar determination was performed with bromine as oxidant and involving back-titration of the iodine liberated from potassium iodide with thiosulphate solution; it was rapid and accurate for 1 0 - 2 ~t-o 10-4~-solutions, where ordinary indicator methods were unsatisfactory.292 The square-wave polarograph has been adopted as a detecting device for carrying out the amperometric titration of indium with EDTA and used t o determine indium in mixtures with cadmium or lead over wide molar ratios. I n 1iw-sodiumbromide at pH 1t o 1.5, the peak current being read at -0.580 V (s.c.e.), indium was determined down t o 8 x 1 0 - 6 ~ the presence of in cadmium and in lM-potassium chloride a t -0.600 v in the presence of lead.293 A number of metals have been determined with EDTA by using iron(n) as indicator ion in a medium of pH 2-5. Provided that the stability constant of the complex formed was greater than 1017,the method was suitable. Thorium was thus determined in the presence of uranium or zirconium. Sulphate and fluoride caused no interference.294 Anodic chelon waves have been used in the amperometric titrations of metals. EDTA, HEDTA, DTPA, DCYTA, trien, and tetren have all been used, and have been applied t o the determination of calcium, magnesium, zinc, cadmium, nickel, copper, bismuth, and lead, singly and in mixtures. Procedures have been worked out for various combinations and are claimed t o be more rapid and selective than methods given heretofore.295 Nitrite ions have been determined a t 1 0 - 3 ~ sulphuric acid a t +1.1 v in (s.c.e.) by a permanganometric titration and gave sharp end points, but the method was not specific.296 The rotating platinum electrode was applied t o the determination of cyanide ions and was used t o study the magnitude of the formation constant of the Ag(CN)(OH)- ion and the best conditions for cyanide determination. By working in OalM-sodium sulphite a t -0.20 v (s.c.e.), interference from chloride or bromide was avoided, and a t -0.85 v from iodide or ~ u l p h i d e . ~ ~ Dissolved oxygen in boiler feed water was determined by trapping in water containing sodium hydroxide and potassium iodate and iodide to which manganese sulphate was added. On acidification, free iodine was produced and an excess of thiosulphate was immediately added. The excess was then titrated with O.O2~-potassiumiodate. The method was applicable t o waters containing 0.003-0.03 p.p.m. of oxygen. 298 I n a similar method chromous chloride was the titrant and this was used t o check the efficiency of various methods for deoxygenating aqueous solutions. Inorganic ions produced no difficulties but benzoic acid and benzoates caused discrepancies.299
291
292
293
294
D. R. R. G.
Shgh and V. S. Agarwala, J. Sci. Ind. Res. India, 1962, 21, B, 212. Bhatnagar, M. L. Bhatnagar, and N. K. Mathur, Talanta, 1962, 9, 455. E. Hamm and C. T. Furse, Analyt. Chem., 1962, 34, 219. Goldstein, D. L. Manning, and H. E. Zittel, Analyt. Chem., 1962, 34,
358.
R . T. Campbell and C. N. Reilley, Talanta, 1962, 9, 153. J. T. Stock and R. G . Bjork, Microchem. J., 1962, 6, 219. 2 9 7 F. Shinozuka and J. T. Stock, AnaZyt. Chenz., 1962, 34, 926. 298 U.K.A.E.A. Report PG 335(W), 1962. 2 9 9 G. P. Gilroy and J. E. 0. Mayne, J. Appl. Chem., 1962, 12, 382.
295
296
462
The phosphorus content of organic substances has been determined by decomposition with potassium and oxidation of the phosphide formed to phosphate. Amperometric titration of the phosphate was carried out with uranyl acetate in acid solution. No interference was caused by nitrogen, sulphur, or silicon, and an accuracy of -+0.3% was claimed.300 Mercaptogroups in ascorbic acid oxidase and other proteins have been estimated by titration with 10-3~-silver nitrate. As little as 0.01 pmole of mercaptogroup has been measured.301 Aldrin has been determined in fertilisers following a simple extraction with a nitric acid-methanol mixture. The extract was burnt in oxygen and the chlorine determined by a '' dead-stop " amperometric titration with silver nitrate; the method was claimed to be rapid and accurate.302 Organosilicon compounds containing the zSiH group were determined in benzenemethanol solution containing 0+3~-lithium chloride by titration with mercuric chloride. The method relied on the formation of the rSiCl group: diH 2HgC1, = %iCl+ Hg2C12 HC1. Only 0.07 g. of sample was required, and the procedure was rapid.303 Coulome.tric.-A considerable development of this method has occurred since the last Report, particularly in instrumentation. Comprehensive reviews of methods of measurement of net charge transfer, coulometry with controlled potential and current, and the development of continuous analysis methods have appeared. 304, 305 Other reviews have concerned coulometric applications of the mercury electrode,306 titrations in non-aqueous solvents,261 current i n t e g r a t i ~ n , ~ ~ ' determination of trace m e t a l ~ . ~ O ~ and A number of completely automatic coulometric titration units, suitable for continuous determinations, have appeared. A device for determining sulphur dioxide in gases from 0 1 t o 1 0 0 ~ o based on oxidation of the . was sulphite formed in alkali solution by the Br3- ion generated anodically from bromide in acid solution. The quantity of electricity consumed was linearly related t o the sulphur dioxide content and was automatically recorded. 309 A rotating platinum electrode was used as the generating electrode and only 5 ml. of gas were required. I n another apparatus potassium bromide flowed at a controlled rate through a generating cell and passed to a titration cell where it was mixed with a stream of the test liquid. A platinum-saturated calomel electrode pair monitored the bromide concentration and controlled the output current of the generating cell. Full details of the apparatus, circuit, and theory of operation were given;310the optimum conditions for working and the relationship between current and concentration of the test
M. N. Chwnachenko and V. P. Burlaka, Izzvest. Akad. Nauk S.S.S.R., 1962, 560. G. R. Stark and C. R. Dawson, J . Biol. Chem., 1962, 237, 712. H. N. Wilson and M. Phillipson, Analyst. 1962, 87, 441. 303 A. P. Kreshkov, V. A. Bork, and L. A. ShvTrkova, Zhur. unalit. Khim., 1962, 17, 359. 3 0 4 H. L. Kies, J . Xlectroanalyt. Chem., 1962, 4, 257. 3 0 5 A. J. Bard, Analyt. Chem., 1962, 34, 57R. 306 J. A. Page, J. A. Maxwell, and R. P. Graham, Analyst, 1962, 87, 245. 307 C. Schoedlei, J . Electroanalyt. Chem., 1962, 3, 390. 308 J. J. Engelsman, Chern. Weekblad, 1962, 58, 113. 309 E. Barendrecht and W. Martens, Analyt. Chem., 1962, 34, 138. 310 T. Tekahashi, E. Niki, and H. Snkurai, J . Electroanalyt. Chem., 1962, 3, 373.
300
301
3oa
463
species were evaluated.311 Continuous analyses of the chlorine content of bleach solutions over the range 20 p.p.m. t o 3% were carried out by using the cathodic generation of ferrous ions ; detecting electrodes monitored the redox potential of the solution and the signal operated a control unit which regulated the current .312 A continuous Karl Fischer unit similarly determined the moisture content of organic liquids from 0.002 t o l*Oyo,using iodine being generated at a rotating platinum electrode. 313 Other automatic coulometric titrators reported include an instrument suitable for sample checking in plant operations, in which the coulometric generation of the titrant occurred in an external ~ e l l . ~ l 4 This was very rapid, and an accuracy of -J=0-2% was claimed ; full details of current integrator, end-point detection, sequence controller, and calibration were given. An assembly for constant-current coulometry used an electronic device for current integration and adapted a conventional titrator controller to decrease the current a t a pre-set potential. Determinations of chromium with electrogenerated Fez+ and C1- with Ag + were described.315 A simplified multivibrator circuit has been used t o provide a pulse technique for coulometry and was applied t o the determination of arsenic(m) and 8-hydroxyquinoline with electrogenerated br0mine.3~6 By a slight modification of a polarographic circuit which involved the use of solid electrodes and a standard resistance across the cell, a simple manual apparatus was devised and applied to solutions of 0-5-2.0 x 1 0 - 3 ~with an accuracy comparable with that of the polarographic method.317 Other developments include an I-& recorder, a where the length of chart was a measure of the number of fully transistorised p o t e n t i o ~ t a tand a coulometer based on a voltage-to,~~~ frequency conversion, which was tested on silver a t a concentration of 25 pequiv., and was claimed to be capable of measuring 2 x 10-7 coulombs.320 The use of a dropping-mercury electrode employing a constant-current microcoulometric technique has been fully examined; the method was applied to the determination of the number of electrons involved in reduction processes. Consistent values were obtained for cobalt, lead, nickel, thallium, l-nitroso2-naphthol, and maleic acid.321 I n a study of the current efficiency of electrogenerated chromium(rr) as a coulometric titrant, copper(I1) was determined quantitatively. A medium of 0-lw-chromic sulphate and 0-lnn-potassium chloride with a mercury cathode was found t o be most effective; the presence of appreciable chlorideT. Takahashi and H. Sakurai, J. Electroanalyt. Chem., 1962, 3, 381. E. L. Eckfeldt and E. R . Kuczynski, J. Electrochem. Soc., 1962, 109, 427. 313 E. Barendrecht and J. G. F. Doornekamp, 2. analyt. Chem., 1962, 186, 176. 314 K. Jeffcoat and M. Akhtar, Analyst, 1962, 87, 455. 315 P. G. W. Scott and T. A. Strivens, Analyst, 1962, 87, 356. 316 Q. Fernando, M. A. V. Devanathan, J. C. Rasiah, J. A. Calpin, and K . Nakulesparan, J. Electroanalyt. Chem., 1962, 3, 46. 3 1 7 A. L. Beilby and A. L. Budd, Analyr. Chena., 1962, 34, 493. 318 S. Hanamura, Talanta, 1962, 9, 901. 319 J. E. Harrar, F. B. Stephens, and R. E. Pechacek, Analyt. Chem., 1962, 34, 1036. 3 2 0 A. J. Bard and E. Solon, Analyt. Chem., 1962, 34, 1181; R . Ammann and J. Desbarres, J. Electroandyt. Chem., 1962, 4, 121. 321 H. B. Mark, E. M. Smith, and C. N. Reilley, J . ElectroanaZyt. Chem., 1962, 3, 98.
311 312
464
ion concentration was essential. 322 A Booman potential-controlled coulometer being used, gold was determined in the milligram range by deposition on t o a platinum cathode from a solution of 0-5~-hydrochloric acid a t +0.48 v (s.c.e.). No corrections were necessary and there was no interference from oxygen. Only iridium(Iv),ruthenium(Iv), silver, and vanadium(v) interfered. 323 Iridium has been similarly determined as chloroiridate in hydrochloric acid solution a t -0.20 v (s.c.e.), controlled potential being used; again, the presence of chloride ion was essential. Sulphuric acid and perchlorate media gave inconsistent results.324 Uranium has been reduced quantitatively a t a silver gauze electrode a t a voltage extending from +0-150 t o -0.150 v (s.c.e.) in a sulphuric acid medium, but bismuth, copper, molybdenum, and-mercury interfered. Methods of removing these were discussed.325 Lead, cadmium, and zinc were determined in glass, by means of a stirred mercury cathode and platinum anode, in the milligram range. Arsenic and antimony were both tolerable in appreciable concentrations.326 Controlled-potential coulometry has been applied to the determination of pg. quantities of iron in sulphuric and hydrochloric acid media. The sulphuric acid solution was preferred except for solutions of high calcium content where hydrochloric acid was more satisfactory. The method was applied t o analyses of ferrous and non-ferrous alloys, in standard silicate rocks G.1 and W.l, and in fluorspar, dolomite, limestone, and magnesite.327 Iron in water has also been determined by a continuous coulometric method in which electrogenerated bromine is used in an acetate buffer with platinum and calomel indicating electrodes.328 Electrogenerated tin@) is a suitable titrant for ceric ions, iodine, and bromine. At -0.3 t o -0.4 v (s.c.e.), 0.814-21.275 mequiv. of cerium(1v) were determined with <2y0 e r r 0 r . 3 ~ ~ Antimony has been titrated by two procedures a t controlled potential. The first involved reduction of antimony(rr1) a t a mercury cathode a t -0.28 v (s.c.e.) in a 0*4~-tartaric 0-lwhydrochloric acid medium, and the second reduction of antimony(v) t o antimony(n1) in 0.4M-tartaric 6M-hydrochloric acid a t -0.21 v (s.c.e.). Both valency states in a solution could thus be evaluated and an accuracy of 0670 a t the 5 mg. level was ~ l a i m e d . 3 ~ ~ Several elements have been determined by a microcoulometric method involving the generation of EDTA by electrolysis of its mercury chelate ;procedures involved either ammoniacal solutions a t pH 10.5 or acetate buffers a t pH 5.5 and used end-point detection for 0.0250.5 pequiv. of the elements. Full details of the cell and working conditions were given.331 Zinc and cadmium were evaluated in a fused lithium chloridepotassium chloride melt a t 450, a bismuth-pool electrode being used. An ; accuracy of & 1Yo was claimed in the 10-4~-rangecadmium was deposited
322
323
324
A. J. Bard and A. G. Petropoulos, Analyt. Chim. Acta, 1962, 27, 44. J. E. Harrar and F. B. Stephens, J. Electroanalyt. Chem., 1962, 3, 112.
J. A. Page, Talanta, 1962, 9, 365. G. W. C. Milner and J. W. Edwards, A.E.R.E. Report, 3951, 1962. P. R. Segatto, J. Amer. Ceram. SOC.,1962, 45, 102. 327 G. W. C. Milner and J. W. Edwards, Analyst, 1962, 87, 125. 32t3 T. Takahashi and H. Sakurai, Talanta, 1962, 9, 195. 329 T. Takahashi and H. Sakurai, Talanta, 1962, 9, 7 4 . 330 L. B. Dunlap and W. D. Shults, Analyt. Chem., 1962, 34, 499. s31 R. G . Monk and K. C. Steed, Analyt. Chim. Acta, 1962, 28, 305.
325
326
CARTWRIOHT, W E S T W O O D , A N D W I L S O N
465
at -1.11 v and zinc at -1.41 v (vs. P t - e l e ~ t r o d e ) . A~ ~ ~ coulometric method for determining water in liquid ammonia relied on passing the ammonia through potassium. This reacted with the water present and a rapid change in conductance occurred at the endpoint. This was used to cut off the electrolysis current. A sensitivity of 1 p.p.m. was claimed and the method was suitable up to 100 p.p.m. of water.333 Water was also determined in organic liquids by passage through a cell having a film of phosphoric oxide as reacting medium and was applicable to the range 1.0-4.5 x Results in close agreement with those of the Karl Fischer method were ~tated.3~4 Hydrogen peroxide and hydroxylamine have been determined by a constant-current coulometric procedure based on the reduction of iron(@ to iron(n). The latter was reoxidised by electrogenerated cerium(1v). A 0-OlN-ceroussulphate 0-OlN-ferricsulphate lw-sulphuric acid solution was used with 10 mA. imposed across the platinum electrodes.335 In the organic field, olefins have been evaluated in vapours over the range 20-1000 p.p.m. by absorption in an acetic acid-ethanol-water-potassium bromide solution. Constant-current conditions were used and electrogenerated bromine was the oxidant. A series of propenes, propadienes, butenes, butadienes, and pentenes was investigated, and an accuracy comparable with those of colorimetric methods was claimed.336 p-Benzoquinone dioxime has been determined with electrogenerated titanium@) as titrant in the milligram range; the method was stated to be rapid and ac~urate.~3' Phenol has been determined by a bromination procedure involving a constant-current pulse technique. Solutions containing to 7 x 1 0 - 6 ~ phenol were determined with an accuracy of &1%. The kinetics of the bromination were also studied by this method. 338 Anti-cholinesterase, and organophosphoruscompounds such as systox, sarin, parathion, and malathion, have been evaluated in the pg. range by a constant-current method based on the enzymic hydrolysis of butyrylthiocholine iodide by cholinesterase. Catalytic activity by the above compounds directly affected the depolarisation rate.339 Reserpine has been assayed in tablets after a simple acetic acid extraction. Oxidation was carried out by electrogeneration of chlorine from 3% hydrochloric acid solution and an accuracy of &l.3y0was claimed on 0.2 mg. of reserpine.340 Various organomercurials and mercury-containing of compounds have been determined by using a O-O5~-solution mercuric thioglycollate solution buffered at pH 5 as generating solution. Thioglycollic acid was produced in electrolysis. A maximum potential between a platinum electrode and the mercury electrode signalled the end point. The method was rapid but un~elective.~4'
J. D. van Norman, Analyt. Chem., 1962, 34, 594. W. C. Klingelhoefer, Analyt. Chem., 1962, 34, 1751. 334 J. SouEok, M. Pfibil, and K. Nov&k, Coll. Czech. Chem. Comm., 1962, 27, 400. 335 T. Takahashi and H. Sakurai, Talanta, 1962, 9, 189. 3 3 6 A. P. Altshuller and S. F . Sleva, Analyt. Chem., 1962, 34, 418. 337 S. L. Dobychin and A. P . Zozulya, Zhur. analit. Khim., 1962, 17, 148. 338 G. S. Kozak and Q. Fernando, Analyt. Chim. Acta, 1962, 26, 541. 339 G. G. Guilbault,D. N. Kramer, and P. L. Cannon, Analyt. Chem., 1962,34,1437. 3 4 0 Z . E. Kalinowska and J. Bartnik-Kurzawinska,Acta Polon. Pharm., 1962,19,45. 341 F . H. Merkle and C. A . Discher, J . Pharm. Sci., 1962, 57, 117.
332
333
466
Potentiometric.-This technique has still remained the most p o p u h ~ method for electrometric determination of end points and the volume of published work is still increasing. A comprehensive review by Murray and Reilley has covered the theoretical developments, apparatus, and applicat i o n ~ .Other~ ~ ~ reviews have described the application of the mercury elect r ~ d e , ~ the antimony-antimony oxide electrode,343 titrations in nonO~ aqueous and the use of electrochemical indicators.344 The calculation of data for redox titration curves 209 and the effect of concentration on the parameters for redox titrimetry have been discussed theoretically.210 A study of the buffer capacity of solutions during acid-base and redox titrations has also been made.345 Forecasting end points in titrations has been achieved by a simple and rapid method which involves a few preliminary measurements and calculations; it has been applied with success to the titration of manganese(I1)by permanganate, chloride by silver nitrate, and iron@) by chromate, vanadate, or ~ e r a t e . ~ ~ G An automatic recording titration apparatus suitable for use with slow reactions has been reported. Titrant was delivered over a period of 30180 minutes and the rate could be varied. The chart- and burette-drive were geared so that the same length of chart always represented the same volume of titrant. Full details of circuits and mode of operation were given.347 Circuit details of a fully-transistorised automatic titrator have been reported which incorporated end-point anticipation and a device for switching from a fast to a slow rate of delivery.348 A simple pH-stat incorporating a special burette control has been devised with a claim of constancy to &0.01 pH.349 Considerableinterest has been shown in glass electrodes responsive to sodium and potassium. A study of two special glasses, BH 68 and BH 104, has been made over a range 1 0 - 5 ~ to 1M-sodium-ionconcentration. The effects of pH , other cations, anions, and temperature have been recorded. Reproducibilities were similar to those for pH glass electrodes but the response time was somewhat longer. The BH 68 glass was considered suitable for plant use and the BH 104 for more accurate laboratory use.35o Silver, lithium, and thallium also affected the BH 68 glass, and indeed pAg values could be obtained over a range of silver-ion concentration^.^^^ Other sodiumand potassium-selective glasses have been investigated especially for measuring changes in concentration of these ions in biological work. A capillary flow and a probe-type electrode were deveIoped.352 Lithium aluminium silicate glasses have also been tested for sodium response. Potassium and lithium, however, caused difliculties and so did pH, but alkaline-earth metals
R . W. Murray and C. N. Reilley, Analyt. Chern., 1962, 34, 313R. J. T. Stock and W. C. Purdy, Lab. Practice, 1962, 11, 290. 3 4 4 C. Schoedler, J . Electroanalyt. Chem., 1962, 3, 390. 3 4 5 F. L. Hahn, Analyt. Chim. Acta, 1962, 26, 258. 3 4 6 J. F. Herringshaw, Analyst, 1962, 87, 463. 3 4 7 L. R . Leake and G. F. Reynolds, Talanta, 1962, 9, 421. 3 4 8 J. T. Stock, Analyst, 1962, 87, 908. 3 4 9 L. Josefsson, C. E. Ryberg, and R. Svensson, Analyt. Chem., 1962, 34, 173. 3 5 0 G . Mattock, Analyst, 1962, 87, 930. 351 G. Mattock and R. Uncles, Analyst, 1962, 87, 977. 3 5 2 H . D. Portnoy, L. M. Thomas, and E. S. Gurdjian, Talanta, 1962, 9, 119.
342
343
467
did not.353 Second-order electrodes of the silver-silver halide and silversilver thiocyanate type have been shown t o be suitable for determinations of bromide, iodide, and thiocyanate ions in the concentration range 10-tlo-4~ with an accuracy comparable with that of the usual potentiometric rneth0d.35~ A simple cell with silver cathode and cadmium anode in 5 ~ potassium hydroxide was used for detecting oxygen in argon. The current produced in the cell, measured as a p.d. by means of a millivoltmeter, gave a direct measure of oxygen concentration; a range of 1-500 p.p.m. for oxygen concentration was claimed.355 Nitromethane has been tested as a solvent for constant-current voltammetry with platinum electrodes. Anodic oxidation of iodine occurred in two steps, and reduction of ferric chloride, benzoquinone, and a nurnber of chlorinated organic compounds gave good res~lts.35~ Tetramethylguanidine has been recommended as a preferable solvent for titration of weak acids with pyridine, and this was successfully applied t o the titration of @-naphthol,benzoic acid, and several halogenated phenols with tetrabutylammonium hydroxide. Up to 3% of water could be tolerated without spoiling the inflections in the potential-titre curves.357 A considerable number of oxidation-reduction titrations have been reported. Titrimetric analyses with chloramine-T as oxidant have been thoroughly investigated by Bishop and Jennings and applied t o the study of reactions with arsenic, antimony, thallium, hydrazine, and thiocyanate. Optimum conditions were established and the addition of a little iodine monochloride as reaction intermediate was essential for accurate work. 3MHydrochloric acid was found t o be the best medium for antimony and thallium, and 5 for arsenic and 4 M for thallium.199 More detailed studies of M the antimony system showed that good results could also be obtained in a tartrate medium a t p H 6.5-7-5,200 and for thallium in the presence of O . l ~ - b r o m i d e . Lead tetra-acetate has been used as oxidant in the deter~~~ mination of molybdenum(II1)in strongly acid solution,359 and of uranium-(m) or -(Iv) by oxidising with iron(1rc) and back-titrating the iron(I1) formed potentiometrically. 360 Oxidations with ceric sulphate have been popular. Vanadium(1v) in an orthophosphoric acid-sulphuric acid medium has been titrated with this reagent and gave a sharp end point, and iron also gave good results down to 0-293 m M - ~ o l u t i o n . ~ ~similar investigation into the A ~ valency states of vanadium on polyolefin catalysts utilised the same oxidant.362 Tungsten was determined in the (v) state after reduction with bismuth amalgam and oxidation in concentrated hydrochloric acid. The method was successfully applied to the analysis of a standard Plutonium has also been determined in a sulphuric acid medium after reduc353
354
355 356
s57
358 359
J. E. Leonard, Analyser, 1962, 3, 5. J. 0. Frohliger and R. T. Pflaum, Talanta, 1962, 9, 755. K. Noviik and V. Slavik, Chern. prurnysl, 1962, 12, 193. J. D. Voorhies and E. J. Schurdak, Analyt. Chem., 1962, 34, 939. T. R. Williams and J. Cuter, Talanta, 1962, 9, 175. E. Bishop and V. J. Jennings, Talanta, 1962, 9, 679. A. Berka, J. Doleial, I. NBmec, and J. Zfka, J . Electroanalyt. Chew.., 1962, 3,
278.
361
A. Berka, J. Doleial, I. Nr?mec, and J. Zgika, Analyt. Chim. Acta, 1962, 26, 148. L. S. A. Dikshitulu and G. G. Rao, Talanta, 1962, 9, 857. 362 J. E. Barney, Analyt. Chirn. Ada, 1962, 27, 320. 363 A. S. Witwit and R . J. Magee, Analyt. Chirn. Acta, 1962, 27, 366.
468
-4 N A L Y TI C A L C H E M I S T R Y
tion to the (111) state with chromous chloride. Iron tended to interfere but corrections could be a ~ p l i e d . ~ 6 ~ Tervalent cerium has been oxidised quantitatively by periodate in a bicarbonate buffer solution. The method was unaffected by many metals, but bismuth, cobalt, iron, chromium, copper, nickel, and zinc gave trouble at high concentration^.^^^ Tin(I1) has been determined by an indirect procedure involving ferric ion and titration of the ferrous ion formed with d i ~ h r o m a t e .Manganese in glasses has been deter~~~ mined after dissolution in a n acid solution by titration with permanganate in a chloride-pyrophosphate medium a t pH 6-8 with a platinum-silver electrode system.367 Ascorbic acid has found applications as a reductant and been used in estimating thallium(II1) in the range 60-120 mg. with an accuracy of &0-6%,368 and gold in a mixture containing platinum and palladium in sulphuric acid.369 The reducing power of iron(=) was markedly increased by working in concentrated phosphoric acid solution ; uranium(VI) was quantitatively reduced in this way a t room temperature in a medium of 11~0-13~5~-orthophosphoric acid.370 Thallium(rr1) and antimony(v), produced by oxidation of the lower-valency states with bromine, have been determined simultaneously in hydrochloric acid by using vanadium(I1). The first break in the potential was due to thallium, and after addition of strong Thallium was also deteracid a second break occurred due to mined with hydrazine in sulphuric acid by using a platinum-carbon electrode system. The titration was rapid, reversible, and free from interference by s large number of cations and anions. Only halides, molybdate, tungstate, vanadate, and chromate gave difficulties.3 7 2 A high-precision assay of uranium metal was carried out by dissolution in phosphoric acid to produce uranium(Iv), which was oxidised by excess of dichromate and back-titrated with standard iron(=) solution ; difEculties from iron, chromium, molybdenum, and vanadium were avoided by aerial oxidation. The method was tested with standard 99.99% uranium. 3 7 3 Several analyses have involved complex formation. Nickel, after separation with dimethylglyoxime, was decomposed with nitric-sulphuric acid, the pH adjusted to 10-10-5 with ammonia, and the solution titrated with O~O~M-EDTA, a mercury-mercuryEDTA electrode being Thorium has been titrated with the tetraacetic acid derivatives of 1,2- di-(2- aminoethoxy )ethane and 2,2' -diaminodiethyl ether and the methods were used to determine the metal in natural and artificial monazites. A simplified procedure was worked out for the element.375 The iron(m)-l ,lo-phenanthroline complex has been used to oxidise cobalt(I1) down to 10-4y0 and the method has been applied to
U.K.A.E.A. Report, PG 309(W), 1962. J. Doleial, S. Rossler, and J. Zfka, CoZZ. Czech. Chem. C m m . , 1962, 27, 1031. 366 R. W. Collins and W. H. Nebergall, AnaZyt. Chem., 1962, 34, 1151. 3 6 7 M. PaleEek, Skcilr'. a. Kerum., 1962, 12, 6. 368 R. Bhatnagar and M. L. Bhatnagar, J. Sci. Ind. Res. India, 1962, 21, B, 44. 369 N. K. Pshenitsyn, S. I. Ginsburg, and I. V. Prokof'eva, Z h w . analit. Khim., 1962, 17, 343. 3 7 0 G. G. Rao and S. R. Sagi, Talunta, 1962, 9, 715. 371 S. I. Gusev and L. A. Ketova, Zhur. analit. Khim., 1962, 17, 137. 3 7 2 A. Berka and A. I. Bmev, Analyt. Chim. Acta, 1962, 27, 493. 373 J. A. Duckitt and G. C. Goode, Analyst, 1962, 87, 121. 3 7 4 N. M. Silverstone, Metallurgia, 1962, 65, 99. 3'5 P. E. Wenger and I. Kapbtanidis, Milcrochim. Acta, 1962, 400.
364
365
469
determination of cobalt in sodium meta1.376 Uranium has been determined with this reagent and the efficiency checked c ~ l o r i m e t r i c a l l y . ~ ~ ~ Thioglycollic acid has been used as a titrant for silver and good end points were obtained. Determination of zinc, cadmium, mercury, and lead showed that 1 : 1 complexes were f0rmed.37~ Other mercapto-acids and thiodiglycol were similarly useful for silver. The stabilities of a number of metal complexes were also studied. Chelates of PAN and PAR with manganese, cobalt, nickel, and zinc were examined potentiometrically in dioxanwater. All gave metal : ligand ratios of 1 : 2 and the order of stability was Ni > Co > Zn > Mn. Values for the stability constants were worked out. 379 Metal-dye stability constants for Solochrome Violet R with copper, nickel, zinc, lead, magnesium, calcium, and aluminium by combined spectrophotometric procedures were evaluated.380 The sulphosalicylic acid coniplexes of manganese, cobalt, nickel, and copper have been titrated with sodium hydroxide, a glass electrode being used ;two potential breaks occurred corresponding to a 1 : 1 and a 1 : 2 metal : complex ratio. Stability constants were derived for these systems.381 A similar study was made with some azo- and azomethine dyes.382 A few potentiometric precipitation reactions have appeared. Potassium has been determined in silicates by a procedure involving precipit,ation as tetraphenylborate. 383 Mercury has been determined with thioacetamide in the presence of other metals after complex-formation with EDTA. Only silver interfered and this had to be allowed for.384 Potentiometric acid-base titrations in molten potassium nitrate a t 370 have been carried out with potassium dichromate as the acid and potassium hydroxide as the base. Very large potential changes occurred a t the end point. An oxygen-platinum and a silver-silver ion electrode were used as the indicating and reference electr0des.3~ -4 potentiometric method for determining bromide-ion concentration has been described utilising a silver-silver bromide electrode which was suitable over the range 10-1 to 1 0 - 4 ~ . The method was applied to the determination of the solubility of lead bromide, and a pBr scale established.3s6 10 P.p.m. of fluoride was determined by using cerium as titrant in a deadstop end-point method.387 Dead-stop methods were also applied to the determination of sulphide, polysulphide, and thiosulphate in mixtures. The sulphide was determined by ammoniacal silver nitrate, thiosulphate with mercuric chloride, and polysulphide by conversion into thiosulphate and a second titration. Results comparable with those obtained by chemical
O
F. Vydra and R . Psibil, 2. analyt. Chem., 1962, 188, 273. F. Vydra and R. Psibil, Talanta, 1962, 9, 1009. 378 A. M. Cabrera and T. S. West, Talanta, 1962, 9, 730. 379 A. Corsini, I. Mai-Ling-Yih, Q. Fernando, and H. Freiser, Analyt. Chem., 1962, 34, 1090. 380 E. Coates and B. Rigg, Trans. Paraday. SOC.,1962, 58, 2058. 3 8 1 V. S. K. Nair, Talanta, 1962, 9, 27. 382 W. J. Geary, G. Nickless, and F. H. Pollard, Analyt. Chim. Acta, 1962, 27, 71. 383 M. Huka and Z . Valnj., SklQr. a. Keram., 1962, 12, 21. 3 8 4 M. Piazzi, Ann. Chim. (Italy), 1962, 52, 45. 3 8 5 A. M. Shamseldin, Electrochim. Acta, 1962, 7, 285. 386 R. T. Pflaum, J. 0. Frohliger, and D. G. Berge, Analyt. Chem., 1962, 34, 1812. 3 8 7 T. A. ODonnell and D. F. Stewart, Analyt. Chem., 1962, 34, 1347.
376
377
470
oxidation methods were obtained.3s8 Nitrite has been determined by titration with lead tetra-acetate. The method was rapid and accurate : 2.35 mg. of NO,- were determined t o within &0-17%, and the method was capable of application to 0.1 mg. ; nitrate caused no interference and the method was applied t o the control of crude Chile salt pet re^.^^^ Traces of oxygen in gases or liquids have been determined by using the aluminium electrode. Purified hydrogen was passed through the solution to constant potential. Water, saturated with the gas or containing the sample t o be analysed, was added and the potential change was noted. The volume of a standard oxygen solution required t o produce a similar change was also recorded and the original oxygen content calculated.390 Hydrazine has been titrated with chloramine-I: and the conditions for satisfactory determination have been worked out. The presence of iodine monochloride was essential for analytically useful applications. Bromide a t 0 . 1 ~ was found desirable and the concentrations of hydrochloric acid must be greater than 0*5~.2Ol A number of organic systems have been investigated in aqueous solution. Primary alcohols were determined by acetylation and back-titration with sodium hydroxide; to avoid difficulties arising a t the end point the titration was carried out to a pH of 7.6.391A number of acid alcohols, glycol, and glycerol were oxidised quantitatively with an excess of lead tetra-acetate in a dilute acetic acid medium. The excess was then back-titrated with quinol (hydroquinone). Oxidation was in some cases, e.g., citric acid, rather Pyruvic acid has been titrated with vanadium(v) in concentrated sulphuric acid solution; a large change of voltage occurs a t the end point.393 A study of an acid-base titration of nitrocellulose in acetone-water solutions has been made. An optimum condition of 0.5% of nitrocellulose in 99.5% acetone solution was required to avoid difficulties. A higher concentration of nitrocellulose spoiled the glass electrode and higher water contents caused less satisfactory potential-titre curves. Under the above conditions results comparable with more tedious procedures were obtained. 394 Triphenylmethane dyes have been titrated after conversion into the carbinol bases with cerium(Iv), and the method was applied successfully to Crystal Violet, Ethyl Violet, and Magenta.Sg5 Thiourea and its organic derivatives have been successfully estimated with iodine monochloride in acid solution and checked with amylose as indicator; an acidity of a t least 3 M was required.396 of The 2,4-dinitrophenylhydrazones a large set of ketones have been determined by titrations in sulphuric acid containing a high concentration of tetrahydrofuran by means of sodium nitrite. The results were good unless there was a carbonyl or benzyl group or a hydrogen atom adjacent to the C=N group.397
S. A. Kiss, 2. analyt. Chem., 1962, 188, 341. A. Morales and J. Zfka, Coll. Czech. Chem. Conam., 1962, 27, 1029. 390 E. Scarano, J . Electroanalyt. Chem., 1962, 3, 304, 368. 391 J. J. Quattrone and T. Choy, Microchem. J . , 1962, 6, 259. 392 A. Berka, V. DvoFBk, and J. Zfka, Mikrochim. Acta, 1962, 541. 3 9 3 K. S. Panwar and J. N. Gaur, J . Electroanalyt. Chem., 1962, 3, 348. 3 9 4 L. R. Leake and G. F. Reynolds, Talanta, 1962, 9, 413. 395G. G. Rao and N. V. Rao, 2. analyt. Chem., 1962, 188, 89. 3 9 6 B. Singh, B. C. Verma, and XI. S . Saran, J . Indian Chem. SOC., 1962, 39, 211. S 9 7 J. G. Baldinus and I. Rothberg, Analyt. Chem., 1962, 34, 924.
389
47 1
A number of determinations have been carried out in purely non-aqueous media. Several of these refer to the titrations of weak acids or bases. Tetrabutylammonium hydroxide has been found to be particularly suitable as titrant for acids,398 and t-butyl alcohol was shown to be especially good for phenols and very weak acids and gave better results than ~ y r i d i n e . ~ ~ Carboxyl groups in polyhexanolactam (polycaprolactam) were determined in 2,6-xylenolwith ethanolic potassium hydroxide at a much lower temperaA ture than in other methods and obviated oxidation diffic~lties.~~Osimilar determination was made for polyamide fibres in propargyl alcohol, tetramethylammonium hydroxide being used as titrant. 4 0 1 Ascorbic acid has been accurately determined by ammonium cerinitrate in methyl cyanide by using a glass or antimony indicating electrode.255 NN'-Disubstituted p-phenylenediamines have been determined in rubber compounds by oonversion into the Wurster salts by oxidation with chloranil. These were stronger bases than the original diamines and were titrated with perchloric acid in acetic acid, methyl cyanide, or acetone to give satisfactory end points.257 Acylamides were determined in pyridine with tetrabutylammonium hydroxide as the best titrant.402 Substituted phenylureas, which behaved as acids in butylamine, were determined with the same titrant.403 A number of heterocyclic N-oxides have been determined in acetic anhydride with perchloric acid.404 Phenols have been directly titrated in glacial acetic acid by bromine, pyridine being used as a catalyst; a high accuracy was claimed.405 Alkylaluminiums were determined in heptane or benzene with pyridine bases by using platinum-silver electrodes; a change of 250-400 mv occurred a t the end point.406 Differential Electrolstic Potentiometry.-This new technique originated by Bishop has continued to develop. Argentometric precipitation reactions for C1-, Br-, CNS-, and I- and mixtures have been studied in detail. Optimum conditions for current values and ballast resistances have been evaluated.407 Acid-base titrations have also been studied by using antimony electrodes,408 the interpretation of current, potential, and temperaand ture relationship for antimony in neutral solution has been discussed.409 The titration of nanogram amounts of halides has been achieved in various media by use of silver or silver-silver halide electrodes. Full operational details were reported.410 A theoretical discussion on the effect of pH and the relationship between E A and AI has been given.411
3 9 8 L. W. Marple and J. S. Fritz, Analyt. Chem., 1962, 34, 796; G. A. Harlow, Analyt. Chem., 1962, 34, 1482, 1487. 399 J. S. Fritz and L. W. Marple, AnaZyt. Chem., 1962, 34, 921. 4 0 0 M. J. Maurice, Analyt. Chim. Acta, 1962, 26, 406. 401 S. Wolf and B. Itlobus, 2. analyt. Chem., 1962, 186, 194. 4 0 2 B. H. Beggs and R . D. Spencer, Analyt. Chem., 1962, 34, 1590. 4 0 3 M. L. Cluett, Analyt. Chenz.., 1962, 34, 1491. 4 0 4 D. C. Wimer, Analyt. Chem., 1962, 34, 873; C. W. Muth, R. S. Darlak, W. H. English, and A. J. Hamner, ibid., p. 1163. 4 0 5 C. 0. Huber and J. M. Gilbert, Analyt. Chem., 1962, 34, 247. 4 0 6 L. Nebbia and B. Pagani, Chimica e Industria, 1962, 44, 383. 4 0 7 E. Bishop and R . G. Dhaneshwar, Analyst, 1962, 87, 207. 4 0 8 E. Bishop and G . D. Short, Analyst, 1962, 87, 467. 4 0 9 G. D. Short and E. Bishop, Analyst, 1962, 87, 724. 410 E. Bishop and R . G. Dhaneshwar, Analyst, 1962, 87, 845. 411 G. D. Short and E. Bishop, Analyst, 1962, 87, 860.
472
Chronopotentiometw.-Theoretical studies of this technique have been published. A mathematical treatment of a system where the current flow was a power of time was considered and was applied to reversible and nonreversible processes.412 Application of potential-time process at constantcurrent to molten salt systems was used with silver nitrate, lead nitrate, lead chloride, and cadmium nitrate in potassium chloride-lithium chloride and sodium nitrate-potassium nitrate melts.413 An apparatus for these studies was described. A saw-tooth generator producing current pulses has been applied t o chronopotentiometric analysis. The advantages claimed were more sharply defined transition times, shorter transition times suitable for kinetic studies, and the ability to determine several elements simultaneously. 414 The chronopotentiometry of uranium a t platinum electrodes has been investigated, and determinations of uranium based on conversion of uranium into uranium(1v) and the oxidation of uranium-(Iv) to -(vI)have been worked out. Iron, iodine, titanium, nitrate, and acetate caused trouble, but not, chromium or vanadium. The medium used was 1.0M-perchloric acid.415 Vanadium(v) was reduced a t a platinum electrode. The process was reversible and quantitative provided that the pIatinum had not been stripped of oxides before ~ ~ 8 A slide rule based on the fundamental equation of . ~ 1 ~ chronopotentiomefry and useful for calculating transition times, concentrations, and diffusion coefficients has been described.417 High-frequency Potentiometry.-Once again relatively few accounts of this technique have appeared. I n a review of instrumental methods by Stock and Purdy details of cell design, circuitry, and titrations in glacial acetic acid, benzene-ethanol, and o-cresol-chloroform-acetone mixtures have been discussed.260 A comprehensive review of oscillometry and conductometry has shown the close relation between the two techniques.259 A new cell design has been reported which is capable of a sensitivity, at approximately 1Mc./sec., only attainable by conventional cells a t much higher frequencies; this consists of two metallic tubes coated on the inside with epoxy-varnish t o reduce the reactance of the insulating wall and connected to a circulating pump and beaker containing the electrolyte. It was success~ further fully checked with sulphuric acid over the range 0 . 0 0 1 - - 5 ~ . ~A ~ application of the Blake zone detector has been carried out to locate the separated zones when mixtures of sodium fluoride, chloride, bromide, and iodide were subjected to paper chromatography. High-frequency measurements of the aqueous extracts from the zones gave a quantitative determination of the amounts of each present.419 Macro-amounts of fluoride, particularly in the presence of small amounts of aluminium, have been determined by steam-distillation from an 85%
lr12R. W. Murray and C. N. ReilIey, J . Electroanalyt. Chern., 1962, 3, 64. lr13 D. Inman and J. OMara Bockris, J. Electroanalyt. Chern., 1962, 3, 126. lrllrH.Hoffmann and W. Jaenicke, 2. anaZyt. Chem., 1962, 186, 93. *15 D. G. Davis, Analyt. Chim. Acta, 1962, 27, 26. lr16 F. C. Anson and D. M. King, Aiaalyt. Chem., 1962, 34, 362. 417 A. J. Bard, Analyst, 1962, 87, 911. lr18 A. H. Collins, Analyst, 1962, 87, 733. lrlSJ. A. Broomhead and N. A. Gibson, Analyt. Chinz. Acta, 1962, 26, 265.
CARTWRIGHT
, W E S T W 00D , A N D
W IL S 0 N
473
phosphoric acid solution. The high-frequencytitration was carried out with lanthanum acetate after buffering to pH 4.5. A precision of &O.Ol mg. of F- was possible. Using perchloric or sulphuric acid in place of phosphoric acid gave poor recoveries.420 Lewis acid-base titrations with an oscillator at 5 Mc./sec. have been carried out with aluminium chloride in acetonitrile as titrant. Dimethylaniline, diphenylguanidine, tri-n-butylamine, pyridine, quinoline, and p-toluidine gave good end points. The shapes of the titration curves showed that formation of a soluble adduct of the AB type was followed by an insoluble adduct of the AB2 type. The method was rapid and ~ensitive.~21 Samples of natural waters have been analysed for C1-, SO,2-, alkalinity, and total hardness at 5 and 130 Mc./sec. by using conventional titrants and EDTA for total hardness.422 Methylglucamine has been proposed as a standard weak base for titrations of acids. It gave very good end points with hydrochloric, acetic, and oxalic acid at 130 Mc./sec. and was easily obtained pure.423 I n the organic field melamine has been titrated with 0-15y0 cyanuric acid in aqueous solution. Ammeline, ammelide, dicyandiamide, and urea caused no interference. The titration was carried out equally satisfactorily in the reverse direction.4 2 4 Hexaethyl-lead in tetraethyl-lead has been determined by a slow titration with permanganate in acetone solution. A calibration curve from known mixtures permittsed ready evaluation of the hexaethyl-lead content of test samples.425
8. DETERMINATION OF ELEMENTS I N ORGANIC COMPOUNDS
Elemental organic analysis is included in a review of developments in organic microanalysis by Ma and Gutterson.426 Specifications for reference substances used in organic microanalysis have been published ; the charact,eristics of 34 compounds which can be used as standards in element and group analysis are described and methods are given for testing each compound for Similar specifications for 29 reagents, first published ten years ago, have been revised 428 and brought into line with manufacturing difliculties as well as users requirements. The efficiency of various catalysts in the combustion of organic compounds has been investigated by a number of ~orkers.429-~31Some novel combustion procedures have been advocated. Pfab, adapting a macromethod, vaporised the sample in a slow stream of nitrogen and then burned
R. C. Calkins, Analyt. Chem., 1962, 34, 837. E. T. Hitchcock and P. J. Elving, Analyt. Chim. Acta, 1962, 27, 501. 4 2 2 L. Erdey, E. Gegus, and M. T. Vhdorffy, Magyar K i m . Lapja, 1962, 17, 277. 4 2 3 L. BalAzs and E. Pungor, Milcrochim. Acta, 1962, 309. 4 2 4 I. A. Guriev, L. G. Urusovskays, and V. A. Zarinskii, Zhur. analit. Khim., 1962, 17, 376. 4 2 5 A. L. Goldshtein, N. P. Lapisova, and L. M. Shtifman, Zhur. analit. Khim., 1962, 17, 143. 4 2 6 T. S. Ma and M. Gutterson, Analyt. Chem., 1962, 34, 111R. 4 2 7 Microchemistry Group, Analyst, 1962, 87, 304. 4 2 8 Microchemistry Group, Analyst, 1962, 87, 400. 4 2 9 M. K. Zacherl, Chim. analyt., 1961, 4 , 535. 3 4 3 0 J. HorAEek, V. Pechanec, and J. Korbl, Coll. Czech. Chem. Comm., 1962, 27, 1254. 431 G. Kainz and H. Horwatitsch, Mikrochim. Acta, 1962, 7.
420
421
474
it in a fast jet of oxygen; there were difliculties, and a catalyst was req ~ i r e d .Another method was to use nitrogen Containing electrolytically~~~ generated oxygen.433 Gleit and Holland 434 used oxygen excited by a radiofrequency discharge, and found that temperatures of less than 100" could be used to decompose a wide variety of compounds. The dependence of completeness of oxidation on the proportion of the organic vapour in a gas stream passing through an oxidising tube has been investigated.435 Instrumental methods to replace the gravimetric finish in determining carbon and hydrogen have attracted considerable attention, and Zacherl 4 z 9 reviews some of them. Greenfield and Smith 436 replace the water-absorption tube by a conductivity cell containing sulphuric acid, and, beyond a drying tube, use a smaller conductivity cell containing potassium hydroxide for the determination of carbon. Unfortunately, lead dioxide must be used in place of manganese dioxide for absorbing oxides of nitrogen. A short survey of methods for determining water vapour in a continuous gas stream has been published, and Keidel's method receives particular mention. 437 For carbon, absorption of the carbon dioxide in barium hydroxide with measurement of change in conductivity has again been advocated.288 Water has been determined by c o u l ~ m e t r y and ~ electrolysis (with conversion of carbon , ~ ~ by dioxide also to water by reaction with lithium hydroxide, and further electrolysis 439 to determine carbon), and by removal of water vapour and carbon dioxide in conjunction with measurements on a pair of katharomet ers. 4 O Some modifications of the more conventional methods for carbon and hydrogen have been advocated. VeEefa 441 speeds up equilibration and replacement of the absorption tubes by placing them permanently inside the balance room. A fully automatic method for carbon and hydrogen has been discussed step by step and described in detai1,442and the physical and chemical factors affecting removal of oxides of nitrogen by manganese dioxide have been i n ~ e s t i g a t e d . ~ ~ 3 For the determination of nitrogen a simple but readily controllable catalytic generator for oxygen has been described.444 By heating the sample in a closed capillary with oxygen, copper, and potassium hydroxide, and measuring the weight of mercury displaced by the resulting nitrogen, Kirsten and Hozumi 445, 446 have evolved a direct method for determining nitrogen which is applicable on the micro- or ultramicro-scale.
W. Pfab, 2. analyt. Chem., 1962, 187, 354; 190, 414. T. Mitsui, K. Yoshikawa, and C. Furuki, Mikrochim. Acta, 1962, 385. 4 3 4 C. E. Gleit and W. D. Holland, Analyt. Chem., 1962, 34, 1454. 4 3 5 G. Kainz and H. Horwatitsch, 2. analyt. Chem., 1962, 187, 87. 4 3 6 S. Greenfield and R. A. D. Smith, Analyst, 1962, 87, 875. 4 3 7 Anon., Chern. WeekElad, 1962, 58, 299. 4 3 8 J. Sodek, Coll. Czech. Chem. Comm., 1962, 27, 1024. 4 3 9 H. S. Haber and K. W. Gardner, Microchem. J., 1962, 6, 83. 4 4 0 P. F. Sommer, W. Sauter, J. T. Clark, and W. Simon, Helv. Chim. Acta, 1962, 45, 595. 4 4 1 M. VeEeYa, Mikrochim. Acta, 1962, 891. 4 4 2 W. Simon, P. F. Sommer, and G. H. Lyssy, Microchem. J . , 1962, 6, 239. 4 4 3 G. Kainz and J. Mayer, Mikrochim. Acta, 1962, 241. 4 4 4 R. McGillivray, Analyst, 1962, 87, 833. 4 4 5 K. Hozumi and W. J. Kirsten, Mikrochim. Acta, 1962, 434. 4 4 6 W. J. Kirsten and K. Hozumi, Mikrochim. Acta, 1962, 777.
432 433
475
Jacobs 447 has modified the indanetrione hydrate method for determining small quantities of nitrogen by carrying out the digestion in sealed tubes without a catalyst, and by altering the spectrophotometric determination. These changes make the method more sensitive and more widely applicable. The flask-combustion technique has established itself for determining a wide variety of other elements in organic compounds. Complications creep in, such as electrical firing and ja~keting,4~8 the method generally, whatbut ever the finishes, remains simple, speedy, and reliable. Mention must, however, be made of a number of methods of determining mercury simultaneously with carbon and hydrogen, based on adsorption of the mercury on silver.449, 4 5 0
9. SPECTROSCOPIC ANALYSIS
As in previous Reports this section is divided into emission spectroscopy and absorption spectroscopy, the former including flame photometry, fluorimetry, and X-ray methods, and the latter ultraviolet and visual absorption, atomic absorption, infrared absorption, and nuclear magnetic resonance met hods. Emission Spectroscopy.-Emission spectroscopic methods for the analysis of solutions have been critically reviewed by Matherny 451 and by Young.452 The latter has mentioned many of the advantages to be gained by working with solutions, but has pointed out that many of the methods that have been proposed are of limited application, and that considerable further investigation may be required before these methods can be extended to wider concentrations of the elements sought, or to other materials. The use of the rotating-disc electrode has been said to result in a ten-fold increase in sensitivity in the determination of volatile elements in ores.453 I n the analysis of rocks spectrographic methods have been described for the determination of gallium, barium, nickel, cobalt, and and of small amounts of germanium, indium, and thallium.455 A rapid method has been described for the determination of small amounts of vanadium in petroleum, petroleum products, and other organic substances.456 The influence of titanium, thorium, and zirconium on the accuracy of the spectrographic determination of small amounts of uranium has been investigated.457 Many papers have been published describing modifications of spectrographic methods determining trace elements and trace impurities. A concentration method involving the use of chelating agents such as quinok-8-01,
S . Jacobs, Analyst, 1962, 87, 53. E. 'weir, Microchem. J . , 1962, 6, 109. 4 4 9 V. Pechanec and J. HorbEek, Coll. Czech. Chern. Comm., 1962, 27, 232. 4 5 0 A. I. Lebedeva and K. S. Kramer, Izvest. Akad. Nauk S.S.S.R., OtdeE. khim. NaurE, 1962, 1305. 4 5 1 M. Matherny, Chem. Analit., 1962, 7, 7 5 . 4 5 2 L. G. Yoang, Analyst, 1962, 87, 6. 4 5 3 I. MihBlka, Acta Chirn. Acad. Sci. Hung., 1962, 30, 359. 4 5 4 A. SpaEkova, Acta Chirn. Acad. Sci. Hung., 1962, 30, 341. 4 5 5 L. I. Pavlenko and Z. M. Davydova, Zhur. analit. Khim., 1962, 17, 199. 4 5 6 P. BunEak, Chem. Analit., 1962, 7 , 269. 4 5 7 T. M. Moroshkina, Vestnik. Leningrad. Univ., Ser. Fiz. i Khirn., 1962, 152.
447
448H.
476
tannic acid, and thionalide has been used for the determination of traces of aluminium, cobalt, chromium, copper, iron, gallium, germanium, manganese, nickel, titanium, vanadium, bismuth, lead, molybdenum, cadmium, zinc, and beryllium in natural water.458 Procedures have been described for the determination of up t o 60 elements as trace impurities in gra~hite,~59 for the determination of silicon and other impurities in gallium arsenide,460 and for the determination of impurities in refined tin.461 A method ha,s been given for the preparation of standard samples of lead, and their use in determining impurities in lead has been described.462 FEame photometry. A hollow light guide constructed from aluminium tubing has been used for the examination of various regions of flames and is said to improve the signal-to-background ratio of many emission lines and t o double signal ~trength.~63 The determination of lithium in water and the effects of the presence of other ions has been studied;464 small amounts of strontium interfere with the determination. Rubidium and caesium in micas and other materials can be determined by using an oxy-hydrogen flame.465 Sodium and potassium interfere seriously, but chloride, sulphate, iron, calcium, vanadium, and lithium have little influence. Interference from phosphorus in the determination of calcium can be eliminated when the concentration of phosphate is less than 20 p.p.m. by atomising the solution in the presence of 2% of I n a study of the flame-photometric determination of lead in lead alloys from 4% t o 85% of lead has been determined with an accuracy and reproducibility of &5y0 of the amount present.467 An investigation of the determination of titanium has shown that most of the elements present in the hydrated oxide precipitate of the group-separation scheme enhance the titanium emission, as also do magnesium and sodium.468 The method can thus only be applied to relatively pure titanium solution in which case better results may be obtained by colorimetric methods. A study has been made of the emission spectra of arsenic, antimony, and bismuth from acetylene-oxygen flames and it was concluded that the flamephotometric determination of these elements was fea~ible.~69 Fluorimetry. I n a timely review article Parker and Rees have given thorough attention t o the subject of fluorescence spectrometry.47o It is to be hoped that their plea for the production of instruments that will record
W. D. Silvey and R. Brennan, Analyt. Chem., 1962, 34, 784. J. A. Goleb, J. R. Faris, and B. H. Meng, Appl. Spectroscopy, 1962, 16, 9. 4 6 0 J. H. Oldfield and D. L. Mack, Analyst, 1962, 87, 778. 461 M. Berecka, Chem. Analit., 1962, 7 , 223. 4 6 2 S. Witkowska and W. Filasiewicz, Chem. Analit., 1962, 7, 211. 4 6 3 W. J. Carnes and J. A. Dean, Analyst, 1962, 87, 748. 1962, 54, 228. 4 6 4 M. J. Fishman, J . Amer. Water Works ASSOC., 4 6 5 Z . Rez&ii and J. Dvor&k, Acta Chirn. Acad. Xci. Hung., 1962, 30, 375. 4 6 6 H. B. Heeney, G. M. Ward, and A. F. Wilson, Anaylst, 1962, 87, 49. 4 6 7 C. L Chakrabarti, R. J. Magee, W. F. Pickering, and C. L. Wilson, Talanta, . 1962, 9, 145. 4 6 8 C. L. Chakrabarti, W. F. Pickering, and C. L. Wilson, Talanta, 1962, 9, 451. 4 6 9 J. A. Dean and W. J. Carnes, Analyst, 1962, 87, 743. 4 7 O C. A . Parker and W. T. Rees, Analyst, 1962, 87, 83.
45a
459
C A R T W R I G H T , W E S TW 00 D
, AND
W IL S 0N
477
directly the true emission and excitation spectra, so that analytical chemists can readily record and publish data in a form that will be of most value t o themselves and t o other workers, will not go unheeded. Parker and Hatchard 4 7 1 have pointed out that the essential difference between phosphorescence and fluorescence is in the duration of the emission after the exciting light is cut off. They have described modifications t o a spectrofluorimeter t o measure weak phosphorescence spectra, and have applied it t o the measurement of simple organic compounds in rigid media a t the temperature of liquid nitrogen. Small amounts of aluminium have been determined by measuring the fluorescence of aluminium oxinate solutions 4 7 2 and the fluorescence of the chelate compound formed by aluminium with salicylaldehyde formylhydrazone. 73 The fluorimetric determination of submicrogram quantities of thorium, morin being used in an alkaline solution of diethylenetriaminepenta-acetic acid has been reported.474 A study of the luminescence of some piazselenols has shown that 2,3-diaminonaphthalene is more sensitive and more convenient for the fluorimetric determination of selenium than the previously recommended 3,3-diaminobenzidine. 75 The use of sodium trimetaphosphate in place of phosphoric acid for the fluorimetric determination of uranium is said t o give greater sensitivity.476 I n the field of organic analysis a-keto-acids have been determined by converting them into the corresponding substituted quinoxalines by reaction with o-phenylenediamine and measurement of their fluorescent properties.477 X-Ray methods. Several papers have described the application of X-ray fluorescence methods t o the determination of trace metals in various substances. A theoretical study has been made of the determination of heavy elements in which calibration curves for zinc, copper, nickel, chromium, and vanadium have been tested for accuracy by analysing two samples of silicate rock of known composition.478 The determination of traces of several metals in organic mineral materials and rocks after extraction has been described,479and also the determination of uranium, thorium, and lead in zircons.48* A rapid automatic method has been applied to the determination of zirconium, zinc, thorium, cerium, neodymium, praseodymium, and lanthanum in magnesium alloys.481 I n the biological field X-ray fluorescence methods have been applied to
C. A. Parker and C. G. Hatchard, Analyst, 1962, 87, 664. W. T. Rees, Analyst, 1962, 87, 202. 4 7 3 Z. Holzbecher and P. Pblkrab, Coll. Czecla. Chenz. Comm., 1962, 27, 1142. 4 7 4 C. W. Sill and C. P. Willis, Analyt. Chem., 1962, 34, 954. 4 7 5 C. A. Parker and L. G . Harvey, Anulyst, 1962, 87, 558. 4 7 6 T. S. Dobrolyubskaya, A. V. Davydov, and A. A. Nemodruk, Zhur. analit. Khim., 1962, 17,70. 4 7 7 J . E . Spikner and J. C. Tome, Analyt. Chem., 1962, 34, 1468. 478Z. H. Kalman and L. Heller, Analyt. Chem., 1962, 34, 946. 4 7 g J. Ottemann and G. Friese, Geochim. et Cosmochim. Acta, 1962, 26, 599. 4 8 0 A. Buchs, Helv. Chim. Acta, 1962, 45, 741. 481 G. A. Stoner, Anulyt. Chena., 1962, 34, 123.
471
472
478
the determination of calcium and potassium in plant materials,482and to the determination of zinc, copper, and iron in biological tissues.483 Other papers of general interest have described the determination of the six major components of Portland cement by fluorescence X-ray spectrography 4 8 4 and the analysis of bauxite by a photographic X-ray method.485 Absorption Spectroscopy.-The papers reviewed in this section are considered in the order ultraviolet and visible absorption, atomic absorption, infrared absorption, and nuclear magnetic resonance methods. Ultraviolet and visible absorption. A few papers of general interest have been selected from the vast amount of work that has been published in this field. Some practical considerations in the search for new reagents for absorptiometry have been discussed by West,486and Cheng 4 8 7 has discussed the masking action of EDTA with particular reference t o its use in the selective determination of copper. A critical comparison has been made of the available methods for the spectrophotometric determination of micro-amounts of copper in textiles 4 8 8 and the determination of copper in some foodstuffs, by means of 2,9dimethyl-1,lo-phenanthroline, has been d e ~ c r i b e d . ~ ~ g Magnesium in uranium has been determined after removal of the uranium by measurement of the colour given with 8-hydroxyquinoline in the presence of diethylene glycol monobutyl ether.490 An investigation has been made of the boron-curcumin complex in the determination of traces of boron.491 Conditions for the formation of the complex were studied, including the choice of acid needed for protonation of the curcumin, and the choice of solvent for it. Some evidence was found for the existence of a complex having a 1 : 3 ratio of boron t o curcumin. A boron oxalate-curcumin complex has been used for the spectrophotometric determination of boron in sea water 492 and the boron-curcumin complex has also been used for the determination of boron in z i r ~ a l o y . ~ ~ ~ A method has been developed for the determination of antimony based on the reaction between chloroantimonate ions and Brilliant Green.494 Main interference arises from gold and thallium. Determinations have been described of chromium using 1,2-diaminocyclohexanetetra-acetic acid,495 of molybdenum using alloxantinY4g6 of and uranium using isopropyltropolone and pyridine. 4 9 7
482
483
484
G. V. Alexander, Analyt. Chem., 1962, 34, 951. H. Uchikawa and Y. Inomata, J. Ceram. Assoc. Japan, 1962, 70, 16. 485 A. Bezjak, T.Frig-Gabega, V. Uzelac, and I. Arapovi6, Croat. Chem. Actu, 1962, 4 8 T . 8. West, Analyst, 1962, 87, 630. ~ 34, 51. 4 8 7 K. L. Cheng, Analyt. Ckern., 1962, 34, 1392. 488 A. G. Kempton, M. Greenberger, and A. M. Kaplan, Textile Res. J., 1962, 32, 128. 489 P. D. Jones and E. J. Newman, Analyst, 1962, 87, 637. 490 V. T. Athavale, R. L. Bhasin, and B. L. Jangida, Analyst, 1962, 87, 217. 4 9 1 M . R. Hayes and J. Metcalfe, Analyst, 1962, 87, 956. 492 R. Greenhalgh and J. P. Riley, Analyst, 1962, 87, 970. 49s M. Freegarde and J. Cartwright, Analyst, 1962, 87, 214. 494 R. E. Stanton and A. J. McDonald, Analyst, 1962, 87, 299. 495 A. R. Selmer-Olsen, Analyt. Chim. Actu, 1962, 26, 482. 496 Yag Dutt and R. P. Singh, Proc. Indiun Acad. Sci., A , 1962, 55, 195. 49'D. Dyrssen and S. Ekberg, Actu Chem. Scand., 1962, 16, 785.
D. F. Ball and D. F. Perkins, Nature, 1962, 194, 1163.
CARTWRIGHT,
WESTWOOD, AND W l L S O N
479
The direct spectrophotometric determination of fluoride can be achieved by means of the lilac-blue complex formed when fluoride reacts with the wine-red chelate of cerium(II1) and alizarin c o m p l e ~ o n e . * ~ ~ sensitivity The is increased by using a 2% acetonitrile or acetone medium instead of water alone. Fluorides may also be determined by means of the bleaching effect of the fluoride ion on a thorium-Xylenol Orange complex.499 Chlorine and its oxides have been found to give ultraviolet absorption spectra in carbon tetrachloride which can be used for their determination, 500 and iodide ions can be determined by means of the complex formed with thallic ions a t pH 2-S.501 Iron can be determined spectrophotometrically by means of the blue colour formed by the reaction of iron(I1) with quinisatin oxine in a buffered solution containing ethyl alcohol and a small amount of dimethylformamide ; cobalt and nickel interfere.502 Iron has also been determined by means of the complex formed with l-hydroxy-9-xanthone in soy0ethanol. 503 The applicability and limit'ations of the dithio-oxamide method for the determination of cobalt have been investigated. 504 Spectrophotometric methods have been described for the analysis of mixtures of ethyltoluene isomers 505 and for the determination of water in organic solvents other than those containing nitrogen. 506 Atmic absorption spectroscopy. Recent work in atomic absorption spectroscopy has been reviewed 507 and the applications of the technique to chemical analysis have been discussed.5 0 8 Franswa has reviewed the theoretical background of atomic absorption spectroscopy 509 and has also discussed the determination of a large number of metals. 510 I n a study of the factors affecting the determination of strontium in biological materials and soil extracts it has been found that calcium and phosphate together depress absorption, but neither calcium nor phosphate separately has serious effect. Interference from aluminium is eliminated by the presence of an excess of ~alciurn.51~ n the determination of small I amounts of magnesium in iron, interference by aluminium may be suppressed by the addition of str0ntium,5~~ in the determination of magnesium in and electronic nickel and nickel alloys interference by aluminium and silicon is overcome by the presence of ni~kel.5~3 Heavy metals such as lead, mercury, bismuth, and nickel present in urine
S. S. Yamamura, M. A. Wade, and J. H. Sikes, Analyt. Chem., 1962, 34, 1308. Z. RezG and J. Ditz, 2. analyt. Chem., 1962, 186, 424. 6 o o Z. Spurn$, Talanta, 1962, 9, 885. 501 D. Betteridge and J. H. Yoe, Analyt. Chim. Acta, 1962, 27, 1. 5 0 2 G. H. Ayres and M. K. Roach, Analyt. Chim. Acta, 1962, 26, 332. 5 0 3 Brahm Dev and B. D. Jain, J . I n d i a n Chem. SOC., 1962, 39, 247. 5 0 4 R. Bondivenne, G. Beau, N. Busch, and R. Y. Mauvernay, Chim. Analyt., 1962, 44, 114. 5 0 5 I. N. Diyarov and M. S. Pevzner, Zhur. analit. Khim., 1962, 17, 102. 5 0 6 R. C. R. Barreto and H. S. R. Barreto, Analyt.. Chim. Acta, 1962, 26, 494. 5 0 7 J. E. Allan, Spectrochirn. Acta, 1962, 18, 605. 5 0 8 G. Milazzo, Chimica e Industria, 1962, 44, 493. 5 0 9 C. E. M. Franswa, Ghem. Weekblad, 1962, 58, 177. 510 C. E. M. Franswa, Chem. Weekblad, 1962, 58, 189. 511 D. J. David, Analyst, 1962, 87, 576. 5 1 2 C. B. Belcher and H. M. Bray, Analyt. Chim. Acta, 1962, 26, 322. 5 1 3 T. R. Andrew and P. N. R. Nichols, Analyst, 1962, 87, 25.
498 49@
480
can be determined after extraction with ammonium pyrrolidinedithiocarbamate and methyl n-pentyl ketone by vaporising the solutions in the flame of an atomic absorption spectrometer;514zinc and cadmium can be determined by the direct spraying of urine into the flame. Infrared absorption. The use of silicone rubber gaskets in the construction of demountable leak-proof sodium chloride cells has been described,515 and details have been given 516 of a low-temperature gas cell capable of being used for measurements down to -60". The determination of sulphur trioxide has been described, use being made of a Pyrex-glass cell fitted with '' Irtan 2 " end plates which are only slowly attacked by the material under t e ~ t . 5 ~ 7 Traces of water may be determined by conversion into acetylene with calcium carbide. The acetylene is transferred with a dry carrier gas into the infrared cells and measured in solution in carbon tetrachloride.518 In organic analysis, aliphatic formates have been determined by infrared spectrophotometry 519 and the technique has also been applied to the determination of technical hexachlorobenzene.520 Nuclear magnetic resonunce. The application of nuclear magnetic resonance to analytical chemistry has been reviewed 521 and a new type of spectrometer having a high differentiation capacity has been de~cribed.5~~ A study has been made of the nuclear magnetic resonance spectra of butadiene-isoprene copolymers and the method has been applied to their determination.523
10. ELECTRICAL METHODS
General.-Electrodeposition, polarography, radiochemistry and mass spectrometry have been considered in this section. Polarography accounts for most of the work published on electroanalytical techniques, and this is still increasing. The review by Wawzonek,52*covering 1960 and 1961, contains 860 references to organic systems alone, and comparable developments have taken place during 1962. Much which is of interest or even important must therefore be omitted in any restricted survey of this field. Cathoderay polarographic methods are steadily becoming more popular and a number of applications of the square-wave polarograph have appeared, particularly in the field of metallurgical analysis. Radiochemical applications have been very prolific and many of these have appeared in non-analytical journals as part of wider projects. Only
5. B. Willis, Analyt. Chem., 1962, 34, 614. B. M. Mitzner, Appl. Spectroscopy, 1962, 16, 25. 516 H. W. Myers and W. W. Martin, Analyt. Chem., 1962, 34, 1038. 517 R . Bent, W. R. Lander, K. S. Pankhurst, and B. D. Waite, Nature, 1962, 193, 62. 518 J . W. Forbes, Analyt. Chem., 1962, 34, 1125. 519 R. M. Powers, M. T. Tetenbaum, and Han Toi, Analyt. Chenz., 1962, 34, 1132. 5 2 0 V. I. Kolbasov, S. B. Bardenshhh, and R. V. Dzhagatspanyan, Zawodskaya Lab., 1962, 28, 446. 5 2 1 J. Delmau, Bull. Soc. chim. Frame, 1962, 1. 5 2 2 J. Dadok and 0. Knessl, Chem. Listy., 1962, 56, 295. 5 2 3 Hung Y u Chen, Analyt. Chem., 1962, 34, 1134. 5 2 4 S. Wawzonek, Analyt. Chem., 1962, 34, 182R.
514 515
48 1
those in which analysis is directly concerned have been considered here. In radioactivation analysis a greater interest has been shown in short-lived products and high-energy neutrons produced by high-voltage generators. Combinations of techniques have become more widespread, and ion-exchange methods are frequently used to separate active constituents. The number of applications of electrodeposition has continued to decline as it is displaced by more rapid and sensitive techniques. Special mention must be made of a new voltammetric method termed coulostatic analysis. This involves providing a current impulse to an electrode which is at a potential corresponding to the base of a polarographic wave. The double layer is thereby charged to a potential at which a faradaic process can occur corresponding to the plateau of the wave. Electrochemical oxidation or reduction then occurs and a faradaic current flows which decays with time and the voltage falls correspondingly. The decay rate is related to the concentration of the electroactive species and the method has been claimed to be suitable for determinations in the concentration range 10-'M. Publication of the method appeared almost simultaneously by Delahay 525 and R e i n m ~ t h and~a~ simple apparatus for measuring the ,~ voltage change has been described.5gi Electrodeposition. In a review on electroanalysis, details of the progress in controlled potential analyses and applications of internal electrolysis during 1960-61 have been de~cribed.~05 They were few in number, and comparatively little new work on electrodeposition methods has been published during the last year. The analysis of lead- and tin-base alloys has been studied by controlledpotential electrolysis. Details of separation of tin from antimony, and copper from lead in tartrate solutions, and methods of avoiding interference from bismuth were described. The methods were applicable to lead-tinantimony-bismuth alloys.5 2 8 Copper has been determined in aluminium alloys by deposition from solutions of HN03-HBF, and HN03-HF-HBF,. Tin, if present, forms a complex and dpes not interfere, but bismuth causes trouble and is removed by co-deposition with lead at the an0de.52~ Nickel and molybdenum have been determined when present together. At pH 4-4-2, the molybdenum is deposited as 2Mo,o3,13H,0. Copper, if present, is co-depositedwith it and must be allowed for. After the solution has been made alkaline with ammonia, nickel is deposited.530 The method of internal electrolysis has been applied to a number of separations. Gold can be separated from lead, bismuth, antimony, and copper in hydrochloric or nitric acid solution by using a silver anode and sodium chloride as anolyte, and the method has been applied to the determination of the element in silvercopper-gold alloys. Bismuth was also separated from antimony, lead, and. copper in nitric acid-thiourea solution, by using a zinc or magnesium anode
I. Delahay, Analyt. China. Acta, 1962, 27, 90; Analyt. Chem., 1962, 34, 1267. ? W. H. Reinmuth, Analyt. Chem., 1962, 34, 1272. 5 2 7 P. Delahay and Y. Ide, Analyt. Chem., 1962, 34, 1580; P. Delahay, Analyt. Chim. Acta, 1962, 27, 400. 5 2 8 B. Alfonsi, Analyt. Chim. Acta, 1962, 26, 316.
525 526
629
630
S. Bertoldi and A. Tartari, Alluminio, 1962, 31, 127. G. P. Protsenko and P. M. Kovalenko, Zavodskaya Lab., 1962, 28, 23.
Q
482
in B sulphate anolyte, and antimony has been separated from tin in a fluoride
medium. 5 3 1 Electrodeposition has also been used as an adjunct in other methods of analysis. Iron has been removed and determined by electrolysis of a pyridine-thiocyanate solution at a mercury cathode before determining vanadium by spectrophotometric means.632 Polaromaphy.--With the exception of potentiometry, polarography now accounts for more published research than any other electroanalytical method. A general review on recent developments in both classical and oscillographic polarography has appeared.533 Wawzonek has again reviewed organic applications 524 and so has Z ~ r n a n .Other reviews have covered ~~~ inverse polarography,535 principles and applications of Tast polarography,536 non-aqueous media,537 continuous polarographic a n a l y ~ i s , 5effects of ~~ adsorption 539 and formate media.S40 A new Tast polarograph possessing greater voltage stability and a smaller capacitative current component has been described.541 Portable polarographs suitable for rapid determination of dissolved oxygen have been reported. In one device a gold cathade is used with the current read on a voltmeter ;w2 in another a wide-bore dropping-mercury electrode maintained at -1.5 v (vs. Ag-AgC1 electrode) is used.543 A cell suitable for continuous measurements uses a rotating indicator electrode with a device for depolarising anodically and washing of the electrode in rapid succession.~4 An elaborate electrode assembly permitted the simultaneous evaluation of m, t, h, w, and drop count.645 U-Shaped vibrating mercury capillary electrodes have been claimed to be suitable for oscillographic polarography.M6 Teflon dropping-mercury electrode capillaries have been tested in media which corrode glass ; it was claimed that such electrodes were satisfactory and gave greater reproducibility from drop to drop than glass; they were recommended for general use.547 Rotating-disc electrodes have been found t o be suitable for polarography with solid electrodes. Good results were obtained with 0.2-1-0 x 10-3~-feryocyanide,548 anodic oxidation of and MV"'dimethylaniline.649 A simple technique for measuring a current transient a t a known interval after the inception of a drop involved measuring
Deschamps and Y . Bonnaire, Mikrochim. Acta, 1962, 463. G. H. Ayres and L. E. Scroggie, Analyt. Chim. Acta, 1962, 26, 470. 633 D. N. Hume, Analyt. Chem., 1962, 34, 172R. 5 3 4 P. Zuman, J . Electroanalyt. Chew., 1962,3, 157; Magyar Kim. Lapja, 1962,17, 8. 6 3 5 R. Neeb, Angew. Chem., Int. Ed., 1962,1,196; Ya. I. Tur'yan and V. F. Romanov, Zavodskaya Lab., 1962, 28, 5 ; H.W.Niirnberg, Z . analyt. Chem., 1962, 186, 1. 636 P. 0. Kane, J . Polarog. Soc., 1962, 8, 10. 6 3 7 G. Schober, V. Gutmann, and E. Nedbalek, 2. analyt. Chem., 1962, 186, 115. 638 W. J. Parker, Metal Ind., 1962, 100, 82, 105. 63D H. W. Nurnberg and M. von Stackelberg, J . Electroanalyt. Chem., 1962, 4, 1. 6 4 0 G. S. Deshmukh, J . Sci. Ind. Res. India, 1962, 21, B, 144. K. Kronenberger and W. Nickels, Z . analyt. Chern., 1962, 186, 79. 5 4 2 A. H. Meyling and G . H. Frank, Analyst, 1962, 87, 684. 6 4 3 R. Briggs and W. H. Mason, Lab. Practice, 1962, 11, 36. 6 4 4 Y a . I. Tur'yan, Zuvodskaya Lab., 1962, 2.8, 98. 6 4 5 H. P. Raaen and H. C. Jones, Anulyt. Chem., 1962, 34, 1594. 6 4 6 J. Horyna and V. JehliEka, Co11. Czech. Chem. Cmrn., 1962, 27, 1326. 6 4 7 H. P. Raaen, Analyt. Chem., 1962, 34, 1714. 6 4 8 S. Azim and A. C. Riddiford, Analyt. Chem., 1962, 34, 1023. 649 Z. Galus, C. Olson, H. Y. Lee, and R. N. Adams, Analyt. Chem., 1962, 34, 164.
631 P.
632
483
oscillographically the potential generated across a series resistance. The method was claimed to be suitable for the range 10-5-10-6~.550 Benzyltriethylammonium chloride has been stated to be especially suitable for determining the alkali metals; the hydroxide was also useful for such determinations in the presence of heavy-metal ions.551 Normal polarograms were obtained for lead and a number of nitro-, nitroso-, and azo-compounds, the ammoniate of sodium iodide being used as solvent.652 A number of metal trace impurities have been determined in alloys. Antimony in cast iron has been measured by a rapid procedure which involved dissolution in an oxidising acid and addition of ascorbic acid. A wave for antimony a t -0.11 v (mercury pool) was used for analysis; molybdenum, titanium, and copper caused no interference, but bismuth and arsenic gave trouble.553 Cadmium was determined in aluminium alloys by derivative polarography. Simple dissolution in hydrochloric acid followed by electrolysis gave a wave at -0.72 v (s.c.e.). Copper caused some interference but this was compensated for by deliberate addition of copper. The method was suitable for 0.1-0-35% of cadmium.554 Molybdenum in steels was determined by employing a citric acid base electrolyte a t pH 2, the waves at -0-27 and -0.65 v (s.c.e.)being used for measurement purposes.666 Lead and copper were determined in tellurium and tellurium concentrates ; antimony, if present, was removed by distillation with hydrobromic acid bromine. The solution was deoxygenated with sulphite, lead was determined at -0.6 V, and copper after addition of tartrate a t -0-33 v ( S . C . ~ . ) . ~ ~ ~ A phosphate medium has been found to be suitable for a number of analyses. Uranium has been measured in a tripolyphosphate medium by anodic oxidation of the (IV) valency state at -0.19 v (s.c.e.) at pH 9. Only iron(@ causes any serious tro~ble.5~'Thallium also has been determined in this medium; the E, values depend on the pH which had to be >4 to avoid interference from iron(m), bismuth(m), and copper(=); an optimum value of pH 7 was found. Addition of 0.1% of camphor displaced most interfering ions to appreciably more negative values. Thallium was determined at the 5 x 1 0 - 5 level in the presence of 400 times as much lead.555" Several deter~ minations have used ion-exchange columns to separate reducible species before analysis. Uranium was separated from thorium and bismuth by using a Dowex 1-X8 column, eluted with a methanol-nitric acid solution, and determined directly. A mean error of only &l.9% was obtained on 10-2000 pg. of u r a n i ~ m . ~ 5 ~new selective-ion exchange medium based A on a phenylfluorenonederivative was applied to the separation of a number of metals, and procedures for the selective separation and polarographic determination of copper, zinc, cadmium, gallium, indium, tin, arsenic,
H. B. Mark and C. N. Reilley, J . Electroanalyt. Chem., 1962, 3, 54. G. S. Supin, Zhur. analit. Khim., 1962, 17, 258. 5 5 2 D. E. Sellers and G. W. Leonard, Analyt. Chem., 1962, 34, 1457. 5 5 3 R. C. Rooney, J . Polarog. Soc., 1962, 8, 20. 5 c 4 R. A. Hine and J. F. Bates, Metallurgia, 1962, 65, 101. 5 5 5 K. Grasshoff and H. Hahn, 2. analyt. Chem., 1962, 186, 147. 556R. Pats and T. V. Semochkina, Zavodskaya Lab., 1962, 28, 800. G. 5 5 7 H .E. Zittel and L. B. Dunlap, Analyt. Chem., 1962, 34, 1757. 5 5 8 P. S. Shetty, P. R. Subbaraman, and J. Gupta, AnaZyt.Chim. Acta, 1962,27,429. 55B J . Korkisch and F. Tera, 2. analyt. C h m . , 1962, 186, 290.
550
551
484
bismuth, uranium, manganese, cobalt , and nickel were given.560 Selenium was determined in glass after fusion, removal of silicon with strong acid, and treatment on an acid exchange resin. The percolate was made ammoniacal and polarographed from -0-6 to 1-0 V, the selenium being determined by standard addition. 5 6 Complex formation has been applied to several procedures. Gallium has been evaluated by a method based on the displacement of cadmium from its complex with 1,2-diarninocyclohexane-iVNNiV-tetra-acetic acid. After a check for free cadmium the mixture was polarographed in an acetate buffer. Interference by aluminium was avoided by addition of fluoride. Other to 3 x l o - 5 ~ metals were removed by an extraction procedure and 3 x gallium was determined in this way t o &2.570.562 The exchangeability of the cobalt(I1) ion with the complexes of the alkaline-earth metals with EDTA has been used t o separate them. Barium, strontium, and calcium were separated by a simple procedure and then made to exchange with the silver complexonate, thereby liberating silver ions; the change in the concentration of these, determined polarographically, was a measure of the metal c0ntent.5~~ Manganese and iron give complexes with 2-[di-(2hydroxypr opyl)aminolethanol and 2-[di-(2-hydroxybutyl)aminolethanol and the products which were anodically oxidised in sodium hydroxide solution. Manganese gave a wave at a more positive potential than iron, so that both elements could be determined in the presence of each other ; manganese was thus determined in a manganese ore and in side rite^.^^^ AluminiGm has been determined in alumino-organo-siloxanes decomposition with acid by fluoride followed by sodium carbonate fusion. The residue was dissolved in a n acetate buffer and complexed with Acid Chrome Dark Blue K and the solution was polarographed over the range 0 to -0.8 v (mercury Traces of selenium were evaluated in a slightly acid sodium tartrate or lithium citrate solution and the method was adaptable t o <I0 , ~ g . / m l . ~ ~ ~ T ~ ( I vformed pyrogallol complexes giving a two-stage reduction in a per) 04 chloric acid-perchlorate medium; the steps a t -0-28 v and - . 1 v (s.c.e.) were well suited to analytical purposes and the diffusion current was linear with concentration up t o l m ~ . 5 ~ Silver gave a wave in a cyanide medium from which the excess of cyanide was removed by nickel ions. None of the common cations or anions interfered, except thallium and lead. The latter was removed by addition of excess of EDTA.56S A study of the complex formed between copper(I1) and mono-, di-, and tri-ethanolamine showed that the monocomplex Cu(MEA),(OH), was formed above pH 9, the dicomplex Cu(DEA),(OH),frompH 9 to l l , and the tricomplex Cu(TEA),(OH), from pH 7 t o 11.5. Details of the media used were given.569 The formaJ. Seidl, J. Stamberg, and E. HobkovB, J . Appl. Chem., 1962, 12, 500. Z. Habermann, SklciP. a. Keram., 1962, 12, 9. 5 6 2 M. Kopanica and R. Pfibil, Coll. Czech. Chem. Comm., 1962, 27, 17. 663 A. Tockstein and V. NovGk, M;krochim. Acta, 1962, 142. 6 6 4 J. Doleial, V. Petrus, and J. ZJike, J . Electrounalyt. Chem., 1962, 3, 169. m5 E. A. Terenteva, Zav&kaya Lab., 1962, 28, 807. 6 6 6 R. Bock and H. Kau, 2. analyt. Chern., 1962, 188, 28. 6 6 7 A. J. Bard, Analyt. Chem., 1962, 34, 266. 5 6 8 R. M. Dagnall and T. S. West, Tulanta, 1962, 9, 925. 5 6 9 J. F. Fisher and J. L. Hall, Analyt. Chem., 1962, 34, 1094.
560
561
C A R T W R I G H T , W E S T WO 0 D
, AND
WILSON
485
tion of molybdophosphoric acid has been shown t o be suitable for determining small amounts of phosphorus. Three waves were given by the complex acid, with E , values dependent on pH and composition of base solution. A preliminary separation of the corresponding arsenic complex was necessary. 670 Nickel soaps were analysed by forming the pyridine complexes of nickel myristate and palmitate. Lithium chloride in benzene-methanol and potassium chloride in ethanediol were used as base solutions.671 Other studies of complex formation and stability constants have included cadmium with oxine,572 nickel with 4-carboxy-l,2-cyclohexanedione i ~ x i r n eand~ ~ d ,~ chromium with Solochrome Violet R.574 A simple procedure for the determination of arsenic in rocks involved distillation as arsenic trichloride, after acid decomposition, into an ammonium sulphate-potassium chloride base solution, and polarography over the range -0.3 t o -1.0 v ( s . c . ~ . ) . ~Determination of uranium in monazite '~ sand involved a simple ion-exchange extraction followed by polarography in a 0-Oh-nitric acid solution. The height of the wave a t -1.05 v was A direct determination of zinc in foodstuffs involved decomposition with perchloric acid and sodium chloride and addition of hydrochloric acid; the method was suitable for 10 pg./ml. of the element.s77 Copper, zinc, and manganese were determined simultaneously in plant materials by low-temperature ashing and dissolution in a base electrolyte of ammonia and ammonium ohloride. No difficulty arose from nickel. Leaf samples from conifers, sunflowers, and fruit trees were examined and preliminary experiments indicated that the method was suitable for milk, blood, and other biological materials. 578 A polarographic study of dissolved oxygen has indicated that the first wave approximated to a reversible reaction but the second was a definitely irreversible one. Both were diffusion-controlled and the diffusion currents were proportional to concentration up to 8 p.p.m. of dissolved oxygen; diffusion coefficients were calculated, and the mechanisms involved discussed.679 Measurement of the total wave height for oxygen in a 0.05% potassium chloride solution was made the basis of a production control method for determining oxygen when mixed with nitrogen. Tests of standard mixtures showed the accuracy to be within 1%.580 Micro-amounts of chloride ion have been analysed a t a stationary mercury drop by using a mercury-mercurous sulphate reference electrode. Electrolysis a t zero volts was carried out for 5 minutes and the potential was then made cathodic a t 300 mv per minute. A peak current was obtained and the peak height was proportional t o chloride-ion concentration, the method being
K. Grasshoff and H. Hahn, 2. analyt. Chem., 1962, 187, 328. W. U. Malik and R. Hague, Nature, 1962, 194, 863. 5 7 2 R. D. Whealy and B. J. Bland, Talanta, 1962, 9, 823. 5 7 3 C. V. Banks and J. P. Laplante, Analyt. Chim. Acta, 1962, 27, 101. 5 7 4 E. Coates and B. Rigg, Trans. Faraday. Soc., 1962, 58, 88. 5 7 5 A. I. Kalinin, Zhur. analit. Khim., 1962, 17, 390. 6 7 6 F. Habashi, Metallurgia, 1962, 65, 255. 5 7 7 J. Deshusses and J. Vogel, Pharm. Acta H l . 1962, 37, 401. ev, 5 7 8 J. C. Sirois, Analyst, 1962, 87, 900. 5 7 9 V. S. GrSths and M. I. Jackman, Talanta, 1962, 9, 205, 871. 5 8 0 W. Heimann and K. Wisser, 2. analyt. Chem., 1962, 185, 266.
570
571
486
applicable over the range 5 x 10+ to 1.8 x 10-4~.581Nitrites were determined alone and in the presence of nitrates, nitroparaffins, aldehydes, or ketones by reaction with semicarbazide. A wave at -1.2 v (s.c.e.) was suitable for analysis at pH 1 - 4 . Nitroparaffins must be extracted, but nitrite and acetone can both be determined at pH 3 - 6 4 when the waves are well separated from that of the semi~arbazone.6~~ iodine content of The iodised salt was evaluated in a phosphoric acid base electrolyte, a platinum electrode being used and the currents being measured at -0.2 and -0.6 v (s.c.e.). The difference in current gave a measure of the iodide content, and 2.5 p.p.m. of iodine were thus determined.583 A very large amount of organic polarography has been described. Acenaphthylene in 92% methyl alcohol containing a quaternary iodide gave a well-defined wave which was useful for analysis in the range 0.2-1.7 MM, and styrene did not interfere with this.584 Aliphatic carbonyl compounds in low-boiling hydrocarbons were absorbed in an acetate buffer containing semicarbazide, the resulting semicarbazones giving a wave between -0.95 and -1.4 v (s.c.e.) which was used for the determination of total carbonyl content. 585 a-Amino-acidsresulting from protein hydrolysates were determined, after separation by ion exchange, as their copper complexes in an acetate buffer solution. An automatic amino-acid analyser was developed for this purpose.586 Carbon tetrachloride, chloroform, and dichloromethane, respectively, present in mixtures gave waves at -0.76, -1.75, and -2.65 v in a quaternary ammonium hydroxide solution in 75% ethanol. The method was applied to the analysis of hydrochloric acid arising from carbon tetrachloride manufacture.587 Methylpentoses were determined by conversion into acetaldehyde with periodate. A lithium hydroxide base was suitable for the aldehyde evaluation and other sugars did not interfere.588 Aldose oximes and semicarbazonesgave single well-definedwaves at pH 1.64.6 suitable for analysis with a linear relationship between diffusion current Picric acid has been and concentration over the range 2-50 x 10-4~.589 determined in mixtures of nitrobenzenes, nitrophenols, and nitrocyclohexane resulting from the nitration of cyclohexane, in a medium of 0 . 1 ~ sodium hydroxide in 40% methanol. The first wave was used in the determination and a preliminary removal of the nitrobenzenes was required.590 The effects of dodecyltrimethylammonium chloride on the half-wave potentials of aromatic compounds and the analytical use of the reagent have been described. Suppression of maxima and separation of the reduction waves took place.591 A full study of the reduction of dimethylglyoxime has been
Kh. Z. Brainina and E. M. Roizenblat, Zavodskaya Lab., 1962, 28, 21. J. Armand and P. Souchay, Chim. Analyt., 1962, 44, 239. 683 V. PlGka, P&mysl. Portravin., 1962, 13, 157. m 4 V. D. Bezuglyi, V. N. Dmitriev, and T. A. Batovskaya, Zhur. analit. Khim.,
581
583
1962, 17, 109. 5 8 6 A. V. Khoroshin, Zavodskaya Lab., 1962, 28, 420. 6 8 6 M. C. Corfield and A. Robson, Biochem. J . , 1962, 84, 146. 6 8 7 M .M. Filimonova, M. I. Levinskii, and Zh. D. Gudzenko, Zavodskaya Lab., 1962, 20, 424. 688A. Wardi and Z. P. Stary, Analyt. Chem., 1962, 34, 1093. H. 6 8 D J. W. Haas, J. D. Storey, and C. C. Lynch, Analyt. Chem., 1962, 34, 146. liD0 Ya. I. Turyan and P. M. Zaitsev, Z h u ~ analit. Khim., 1962, 17, 231. . 6 D 1 D. J. Pietrzyk and L. B. Rogers, Analyt. Chem., 1962, 34, 936.
487
made. An 8-electron reduction to 2,3-diaminobutane occurred and this W M confirmed by controlled potential electrolysis. A well-defined wave was obtained over a range of pH.592 Chloropicrin has been determined in air by &.direct method; a well-defined wave was obtained in a solution of 80% methanol containing 0.08N-nitric acid, and no interference was shown by 100 times its weight of carbon tetrachloride, methyl bromide, ethylene dichloride and dibromide, or chloroform over the potential range +0.2 to -0.8 v (silver chloride ele~trode).5~~ precision of the method varied The from &l-1to 5.0% over the range 4-27 x to 1.22 x 1 0 - 5 ~ . The polarographic behaviour of mercaptoalkyl compounds of disubstituted guanidines, ethylamines, and ethanols and their disulphides have been studied for their possible determination in radiation-protection drugs. Over the range pH 5-4-11.6 the wave corresponded to the formation of RSHg. The disulphides gave a linear relationship with concentration and current 2-Mercaptoimidazole has over the range 6-7 x 10-5 to 3-2 x 1 0 - 4 ~ . 5 9 4 been studied in perchloric and sulphuric acid media. There was a linear to 2 x 10-3~.5g5 current-concentration relationship over the range 8 x Several determinations have been carried out in wholly non-aqueoue media. Ethyl acrylate has been determined in mixtures with casein as part of a study of polymerisation reactions involving them. A wave was obtained in a dioxan-methanol solution with tetramethylammonium iodide as base electrolyte at -1.6 to -1.7 v, which was suitable for analysis.596 1,2,4Benzothiadiazine and related compounds were examined in anhydrous dimethylformamide. Structural factors and polarographic behaviour were correlated with a view to their determination.597 Vinyl cyanide has also been examined in this solvent and gave satisfactory waves at E, = -1.72 v to 1 x 1 0 - 4 ~ .They (mercury pool) over the concentration range 5 x were suitable for analytical determinations. 598 Procedures for a number of pharmaceuticals have been reported. Analyses for acetazolamide, chlorothiazide, and nitrofurantoin in tablets have been published.599 Gentisic and homogentisic acid have been determined together in a phosphate or carbonate buffer solution at pH 7-8 by means of their anodic waves which were well separated.600 Histamine solutions have been standardised by reaction with formaldehyde to give an imine reducible at -1.4 v (s.c.e.). Good results were obtained in the range 0.481-1.443 mm601 Quinicine has been evaluated in the presence of a thousand-fold excess of quinine in injection and cinchona preparations. After extraction with an alkaline ethanolic solution of m-dinitrobenzeneand chloroform, and adjustment to pH 4.4 in acetate buffer, the quinicine was
M. Spritzer and L. Meites, Analyt. Chim. Acta, 1962, 26, 5 8 . B. Berck and J. Solomon, Analyt. Chem., 1962, 34, 574. 6 9 4 W. Stricks, J. K. Frischmann, and R . G. Mueller, J . Electrochem. SOC., 1962, 109, 518. 6 9 5 R . A. F. Bullerwell, J . Polarog. Soc., 1962, 8, 2. 6 9 6 J. G6her and G. V&go, Magyar Kim. Folydirat, 1962, 68, 181. 6 s 7 A. I. Cohen, B. T. Keeler, N. H. Coy, and H. L. Yale, Analyt. Chem., 1962, 34, 216. 6 e e A . S. Gorokhovskaya and B. E. Geller, Zavodskaya Lab., 1962, 28, 809. A. F. Summa, J . Pharm. Sci., 1962, 51, 474. O o 0 M. Jirlra, Clinica Chim. Acta, 1962, 7 , 737. Ool D. E. Sellers, K. L. Breenlee, and R. E. van Atta, Analyt. Chem., 1962, 34, 441.
692
693
488
determined polarographically. 602 Purines and pyrimidines and their derivatives were examined with a view t o their determination, and a number of procedures have been recorded for individual determinations.603
Alternating-current, Cathode-ray and Other Polarographic Methods.These new methods have continued t o develop. A recent review has surveyed the developments in theory and the practical applications to date.533 Applications of cathode-ray methods t o metallurgical analysis have also been reviewed. 604 A Leeds and Northrup electrochemograph has been converted to a recording A.C. polarograph by a small external adjustment in circuitry. This involved injection of a small A.C. and measurement across a series resistance shunted by an amplifier and rectifier. 605 The high background due to charging of the double layer in an A.C. polarograph has been minimised by a simple capacity-inductance network, thus giving an improved current peak and enhanced sensitivity with a narrow band amplifier. An increased signal-to-noise ratio was obtained, giving a sensitivity increase of 10 t o 20 times.606 Lead and cadmium were determined at the 0.1 pg. level t o within 3%.GO7 A new cell assembly involving identical dropping-mercury electrodes has been tested with the differential cathode-ray polarograph. Results have shown that the coefficient of variation can be as low as 0 ~ 0 4 ~ 0 . 6 0 8 Several determinations involving linear-sweep polarography have been recorded. Traces of antimony, copper, and lead have been estimated in ferromanganese. Simple procedures for these elements, suitable for routine control purposes, were described.609 Aluminium has been determined in thorium after electrolytic separation of other metals, as the Superchrome Garnet Y complex a t pH 5.75 in an acetate buffer.610 The lead content of standard rocks G . l and W.l has been evaluated oscillographically after removal of silica, iron, and fluoride.611 Copper, nickel, arsenic, cobalt, zinc, and cadmium have been determined in uranium-acid-lead solutions after separation from each other on an anion-exchange column. Details of the various procedures were recorded.612 Zinc was determined in blood by a simple procedure involving preliminary extraction as the dithizone complex.613 Azin-phos-methyl residues in fruits and vegetables were determined by cathode-ray polarography after removal of interfering substances on an exchange column. An accuracy of 0.1 p.p.m. was claimed.614 Applications of alternating-current polarography have included determinations of cadmium and thallium in products of non-ferrous metallurgy,615
602
603
321.
M. Girard and F. Rousselet, Ann. Pharm. franc., 1962, 20, 109. D. L. Smith and P. J. Elving, Analyt. Chem., 1962, 34, 930. 6 0 4 P. H. Scholes, R & D, 1962, 38. 6 0 5 J. W. Hayes and G. H. Aylward, Analyt. Chern., 1962, 34, 1039. 6 0 6 N . Lordi, Analyt. Chem., 1962, 34, 1832. G. 6 0 7 R. Neeb, 2. analyt. Chem., 1962, 186, 5 3 . H. I. Shalgosky and J. Watling, Analyt. China. Acta, 1962, 26, 66. 6 o o A. G . C. Morris, Analyst, 1962, 87, 478. 610 T. M. Florence, Analyt. Chem., 1962, 34, 496. 611 V. V. Zhirova, Geokhimiya, 1962, 542. 612 L. Jarman and M. Matic, TaZanta, 1962, 9, 219. 613 J. Vogel, D. Monnier, and W. Haerdi, J . Electroanalyt. Chem., 1962, 3 ,
614
61s
J. A. R. Bates, Analyst, 1962, 87, 786. R. G. Pats, Zavodskaya Lab., 1962, 28, 18.
CARTWRIGHT, W E S T W O O D , A N D WILSON
489
the use of Solochrome Violet R for the determination of traces of iron,61s a study of the copper-mannitol complex,617 and the analysis of drugs in animal feeding stuffs. 618 Square-wave polarography has been used for several metallurgical analyses. Cadmium in silicate rocks has been determined after separation as its dithizone complex, and the method has been applied to standard rocks G.l and W.l, results consistent with other techniques being obtained.61g Bismuth, copper, indium, and gallium were determined in gallium arsenide in the 1 p.p.m. range by using 1M-hydrochloric acid as the base electrolyte.620 Small amounts of uranium, down to 0.5 p.p.m., were determined in hafnium, zirconium, and zircaloy-2. Good agreement with the fluorometric method was claimed.621 A series of determinations of copper, lead, molybdenum, tungsten, and zinc in zirconium and hafnium has also been reported. 6 2 2 Niobium was determined in steels in EDTA solution.623 Anodic stripping techniques have been used to determine tin and indium in binary all0ys,~~4 traces of tin in steels.625 and Radiochemisb.-With rapid growth of this technique, the Reporters select examples from diverse fields which are of analytical interest. Uses of isotopic tracers are very considerable and are still growing but novel and less time-consuming methods have appeared. Activation methods have rapidly increased and several new procedures involving very short irradiation times with no chemical separation have simplified determinations. High-energy neutron irradiations from particle accelerators or Van der Graaf generators have been increasingly applied and have provided rapid and convenient alternatives to pile irradiations. Reviews have appeared on nucleonics,626 activation analysis for trace metals in reactor materials,627general chemistry,628 activation by neutrons, photons, and deuterons and their applications in metallurgy, biochemistry, and medicine,629 isotope dilution analysis in inorganic and trace analysis,630 and radiometric titration and ,&reflection methods in analysis. 631 A number of modifications for scintillation counting have been published including the use of suspensions of finely divided silica, which a t a 4% concentration in the scintillator gives a transparent gel capable of producing stable suspensions of Bal*CO, and a higher counting efficiency than under infinite
R. C. Rooney and P. J. McIver, Analyst, 1962, 87, 895. T. Takahashi and H. Shirai, J . Electroanalyt. Chem., 1962, 3, 330. 618 A. C. Daftsios and E. D. Schall, J . Assoc. Offic. Agric. Chemists, 1962, 45, 278. 610 R. E. Stanton, A. J. MacDonald, and I. Carmichael, Analyst, 1962, 87, 134. 6 2 0 V. J. Jennings, Analyst, 1962, 87, 548. 621 D. F. Wood and R . H. McKenna, Analyt. Chim. Acta, 1962, 27, 446. 6 2 2 D. F. Wood and R. T. Clark, Analyst, 1962, 87, 342. 6 2 3 M. H. Cockbill, Analyst, 1962, 87, 611. 6 2 4 R. D. De Mars, Analyt. Chem., 1962, 34, 259. 6 2 6 S. L. Phillips and I. Shain, Analyt. Chem., 1962, 34, 262. 6 2 6 G. W. Leddicotte, Analyt. Chem., 1962, 34, 143R. 6 2 7 M. RakoviE, Jadernci Energie, 1962, 8, 127. 628 R. A. Bailey, U.S. Atom. Energy Comm. Rep., NAS-NS. 3106, 1962. 6 2 9 J. Hoste, Chem. Weekblud, 1962, 58, 106. 6 s o 5. Ruzidka, Chem. Listy, 1962, 56, 783. 631 I. Porubszky and D. Hegedus, Magyar Kim. Lapja, 1962, 17, 90.
616
490
thickness conditions.632 The use of a two-phase system of detergentanthracene has been claimed to be suitable for a- and p-radiation counting and to have a high efficiency. It was checked on solutions of compounds of 35S, 32P, 137Cs,90Sr, 210Po,45Ca, Be, and 3H a t the 10-3-10-4~ An apparatus for the heterogeneous counting of weak p-emitters has been described in which the sample containing 3H 14Cin solution was or run through a 1 ml. spiral cell contained in a jacket holding silicone oil and suspended anthracene crystals. It was claimed to be suitable for biological samples and continuous recording of chromatographic effluents.634 Another device involved passing the radioactive solution through a glass tube packed with anthracene crystals and situated between two G.M. tubes in a coincidence circuit ; this was claimed to be suitable for continuous-flow recording.635 The ring-oven method has been developed for investigations of solutions of radioactive materials of the order of nanocuries by a technique known as ring-chronoautoradiography. Details of the apparatiis,636 and its 638 applications to 6oCo, 137Cs,Q5Zr,90Sr, 144Ce, and 106R~,637, have been described. The copper spark method has been applied to the determination of 1311, 32P,and 35S solutions down to 0-05 ,ug./ml. leve1.639 Difficulties in arose, however, due to other ions, especially those of alkali metals, and careful control of conditionswas essential. A radio-respirometerhas been devised by attaching a G.M. tube to the absorption cup of a Warburg apparatus to record the 14C02 fl0w.640 Activation methods have increased considerably in number. Ruthenium has been determined in platinum, by using the 103Ruisotope for /3-counting a t the 0.83-1.78 p.p.m. leve1,6*1and arsenic and antimony in platinum by y-counting after separation as metal and s~lphide.6~2 Antimony from o-03y0to 1% has been estimated in lead, gold being used as a standard to avoid self-shielding difliculties; the ratio of the heights of the 0.40 Mev and 0.56 Mev y-photopeaks for l98Au and 122Sb, respectively, were used for calculating the antimony c0ntent.6~3 Similarly, the antimony and cobalt content have been determined in magnesium base alloys containing 0.001 to 0.1 p.p.m. of these elements;6**tin and uranium tended to interfere with the antimony if present a t more than 2 and 50 p.p.m., respectively, and nickel interfered with cobalt above 0.03 p.p.m Several applications to trace metals in steels have been described. Manganese was easily determined without chemical separation by a 3-second irradiation at 4 x 10l2neutrons cm.-2/sec.-1 with measurement of the 840 kev y-photopeaks, and arsenic and
H. J. Cluley, Analyst, 1962, 87, 170. L. S. Myers and A. H. Brush, Analyt. Chern., 1962, 34, 342. m4 E. Schram and R. Lombaert, Ann. Biochem. Ezp. Med. (India), 1962, 3 68. , 6 3 5 E. Rapkin and J. A. Gibbs, Nature, 1962, 194, 34. 6313L. J. Ottendorfer and H. Weisz, Mikrochim. Acta, 1962, 725. 6 3 7 H. Weisz arid L. J. Ottendorfer, Mikrochim. Actu, 1962, 818. 638 H. Malissa and F. Loley, AnaZyt. Chim. Acta, 1962, 27, 381. 639 J. F. Jalkowski and A. Zelle, Acta Chim. Acud. Sci. Hung., 1962, 30, 321. 6 4 0 J. Goksoyr, Ann. Biochem. Exp. Med. (India), 1962, 3, 439. 6 4 1 R. A. Killick and D. F. C. Morris, Tulanta, 1962, 9, 349. 6 4 2 R. A. Killick and D. F. C. Morris, Talanta, 1962, 9, 879. 6 4 3 F. Adams and J. Hoste, Tulanta, 1962, 9, 827. 6 4 4 R. Todd, G. Cuthbert, and R. Dickinson, U.K.A.E.A. Report PG 337(S), 1962.
632
633
491
cobalt could be measured in the same sample after 10 minutes and 1 weeks irradiation, respectively, the peaks at 560 kev and 1.33 Mev being used, after chemical ~eparation.6~5 scheme for the determination of 16 elements A in a nickel-base high-alloy steel after irradiation has been put forward with details of the complications and interferences which O C C U F . ~ * ~ Sulphur and phosphorus have also been determined in steels by a double-irradiation method involving different fast-to-slow neutron flux ratios, and the method has given good results on a range of B.C.S. standard steels.s47 Tantalum was determined in tungsten, without separation, by measuring the 1.2 MeV y-photopeak for 182Ta after a 3-second i r r a d i a t i ~ n . ~ ~ g Sodium was determined in rocks and silicate minerals by irradiation for periods of 10 seconds t o 1minute a t 5 x 1012 neutrons cm.-2/sec.-1 and measuring the 24Naphotopeak. To simplify measurement, only y-rays above 2.6 Mev were accepted by the counter. Gallium and lanthanum interfered only if their content was high.G49 Molybdenum, tin, tantalum, and tungsten were determined by thermal-neutron irradiation followed by solvent extraction of the tantalum as fluoride with isobutyl methyl ketone. The tin and molybdenum were converted into sulphides and the tungsten into the benzoin a-oxime complex; the various elements were then determined by Aluminium has been determined in natural diamonds in the range 0.120 p.p.m. by irradiation in DIDO at 5 x 10l2neutrons cm.-2/sec.-l for 10 minutes followed by measurement of the 2.27-minute half-life of 28A1. Irradiation in DIDO rather than BEPO avoided the Z8Si( 28A1reaction n,p) which complicates the meth0d.~5l A further method for aluminium in rocks and minerals relied on the 3 MeV beam from a Van der Graaf generator. When this struck a gold target Bremsstrahlung were produced which induced the 9Be(y,n)8Bereaction in beryllium. Irradiation for 1 minute by the neutrons was sufficient to determine O.lyoto 10% of a l ~ m i n i u m . ~ 5 ~ A similar sequence was used for the determination of beryllium. I n this case a tungsten target was used with X-ray generation of fast neutrons. After striking beryllium-containing material, these were moderated to thermal values by polyethylene and were used to irradiate a silver disc. The decay of the lo8Agwas measured by its 2.1 &levy-photopeak and from this the beryllium content was ~alculated.6~~ activation of silver to The produce lo8Ag can be brought about by Bremsstrahlung, protons, or neutrons and this has been used to determine rapidly the silver content of solders in the range 1-667(0.654 Traces of hafnium and zirconium 655 and iridium 656 in meteorites have been determined by irradiation followed by
S. May and G . Pinte, Bull. SOC.chim. France, 1962, 287. I. J. Graverman and W. A. Henninger, Analyt. Chem., 1962, 34, 1680. 6 4 7 P. Bouten and J. Hoste, Analyt. Chim. Acta, 1962, 29, 315. 6 4 8 R. Corth, Analyt. Chem., 1962, 34, 1607. 6 4 9 G. L. Schroeder and J. W. Winchester, Analyt. Chem., 1962, 34, 96. 6 5 0 H .Hamaguchi, R. Kuroda, T. Shimizu, I. Tsukahara, and R. Yamamoto, Geochim. Cosmochim. Acta, 1962, 26, 503. 651 E. C. Lightowlers, Analyt. Chem., 1962, 36, 1398. 6 5 2 D. F. Rhodes and W. E. Mott, Analyt. Chem., 1962, 34, 1507. 6 5 3 C. A. Levine and J. P. Suds, Analyt. Chern., 1962, 34, 1614. 6 5 4 L. I. Bilefield, Analyst, 1962, 87, 504. E 5 5 E. Merz, Qeochim. Cosmochim. Acta, 1962, 26, 347. 6 5 6 P. R. Rushbrook and W. D. Ehmann, Qeochim. Cosmochim. Ada, 1962, 26, 649.
645
492
precipitation methods and use of y-ray spectrometry; 0.006-0.57 p.p.m. of iridium was determined with high overall chemical yields. A number of metals present in biological materials have been determined by activation procedures. Molybdenum in the region of 0.9 p.p.m. has been determined in clover. Both the 9 0 M ~ and the lolMo isotopes were used, but in the latter case the irradiation time was only 20 minutes.657 By solvent extraction, after isotopic dilution, with tri-n-octylamine in kerosene, the molybdenum was obtained in good chemical yield. Sodium and potassium were determined in tissues by irradiation and direct measurement of the y-photopeak for sodium. Potassium, however, required separation as the dipicrylamine or tetraphenylborate, with p-counting. Reproducibility was claimed t o be within 10% and the time for analysis was much shorter than with any other method.65s Manganese was determined in biological materials in the range 0-14-37.4 pg. per g. by irradiation followed by precipitation as tetraphenylarsonium permanganate which avoided interference from chromium.659 Residual bromine, at the 0.05 pg. level, in agricultural crops 660 and citrus fruits 661 involved irradiation for 30-60 minutes followed by measurement of the activity of the 82Br isotope without any separation. Several determinations of oxygen by fast neutrons have been reported. I n one method 14.5 Mev neutrons were produced by irradiation of a tritiated zirconium target with 250 kev deuterons. Only 10 seconds' irradiation time was necessary for the 160(n,p)16Nreaction. The shortlived 16N was measured by counting the pulses from y-photons of energy > 3 6 Mev and a limit of 10 p.p.m. was possible. Only boron and fluorine interfered.662 A new method of activation involving 3He as the bombarding particle has been developed. Owing t o the low binding energy of the particle the reactions undergone were usually exoergic and the isotopes produced had very high energies. Nuclides up to 48Cawere investigated with short irradiation times and the method was non-destructive. It was particularly suitable for the determination of oxygen down to p.p.b.663 Solvent-extraction procedures for separating and determining radioisotopes have increased in popularity. The extraction of 5lCr a,s chromate into diphenylcarbazide-isopentyl alcohol mixtures, and 56Mnas the diethyldithiocarbamate complex or as tetraphenylarsonium permanganate into chloroform gave excellent recoveries.664 Chromium was isolated from fission products and stainless-steel corrosion products by extraction of the Cr(vI) tetrabutylammonium ion complex into isobutyl methyl ketone. Chemical yield was determined spectrophotometrically, and the 51Cr content ob~5 tained from the 320 kev y - ~ h o t o p e a k . ~ Cerium, after oxidation t o the quadrivalent state, was determined in fission products after extraction as
B. Van Zanten, D. Decat, and G. Leliaert, Talanta, 1962, 9, 213. J. Pijck and J. Hoste, Clinica Chim. Acta, 1962, 7 , 5 . 6 6 9 H. Smith, Analyt. Chem., 1962, 34, 190. 6 6 0 V. P. Guinn and J. C. Potter, J . Agric. Food Chem., 1962, 10, 232. 661 C. E. Castro and R. A. Schmitt, J . Agric. Food Chem., 1962, 10, 236. s s a R .F. Coleman, Analyst, 1962, 87, 590; E. L. Steele and W. Wayne-Meinke, Analyt. Chem., 1962, 34, 185; D. J. Neal and C. F. Cook, ibid., p. 178. 663 S. S. Markowitz and J. D. Mahony, Analyt. Chem., 1962, 34, 329. 8 6 4 G. Dinstl and F. Hecht, Mikrochim. Acta, 1962, 321. 6 6 5 W. J. Mmck, M. E. Kussy, and J. E. Rein, Analyt. Chem., 1962, 34, 1602.
c5'
G5*
493
the tetra-n-propylammonium nitrocerate complex into nitroethane. Only fluoride interfered and this was avoided by the addition of aluminium.666 Zirconium and niobium were separated from aqueous solutions by acetylacetone-chloroform mixtures. The niobium was extracted a t pH 2-5, and the zirconium was removed a t pH 5-8.667 Molybdenum was determined in fission products by extraction as the a-benzoin complex into chloroform from acid fluoride solution and /3- or y-counting of the g 9 M ~ . Only tungsten Ruthenium was interfered in the extraction, but not in the extracted almost quantitatively from other metals by carbon tetrachloride a t pH 4 in the form of RuO, and was /I- or y-c0unted.66~ A series of solvent separations for metals involved extraction of iron with isopentyl acetate and zinc with dioctylamine in ~ y l e n e . ~ ~ O Cobalt was determined in the presence of large excesses of mercury, silver, copper, bismuth, lead, or thallium by extraction with diethyldithiocarbamate in chloroform after removal of other metals by mercury(I1) and cyanide treatment. Cobalt down t o 0.1 pg. has been determined.671 Alternatively the cobalt was extracted with a fixed amount of the zinc complex in chloroform. The excess of reagent and complexes of foreign metals were removed by exchange with 203Hg(11). The 20sHgremaining in the chloroform layer acted as a measure of the cobalt content. Lead has been similarly determined after addition of thallium diethyldithiocarbamate complex and counting of the residual 204Tl; 0.06 pg. of lead in the presence of large excess of other metals and anions has been estimated with accuracy.672 A highly efficient extraction of copper with dithizone in carbon tetrachloride allowed a rapid determination at pH 3.55.0 in the presence of thirteen other elements and was applied t o the determination of copper in water and urea. A limit of 10-10 g./ml. was ~laimed.~'3 Cobalt has been determined in a standard alloy (N.B.S. 157) and in ingot iron (N.B.S. 55e) by using 6oCoas tracer and extracting the 2-nitroso-l-naphthol complex in chloroform. A value of 0.006% of cobalt in the latter was in close agreement with the official value.674 A number of chromatographic methods have also been used t o separate and determine radioactive species. A rapid and effective separation of 9OSr from 'its daughter product on filter-paper impregnated with Amberlite IR-120 resin from a citrate medium a t pH 3.8, was produced, and the element was measured by a /I-recording densitometer. Similar separations were possible with Amberlite IR-4B with water or cellulose phosphate with N - H C ~ . ~ separation between these elements was also effected by an A ~~ anion-exchange resin by forming the rhodizonates. Yttrium was retained but strontium was Tervalent iron was strongly held on a cation666
667
S. F. Marsh, W. J. Maeck, G. L. Booman, and J. E. Rein, Analyt. Chem., 1962,
34, 1406.
N. Suzuki and T. Umori, Bull. Chem. SOC.Japan, 1962, 35, 595. 6 6 8 L. Wish, Analyt. Chem., 1962, 34, 625. 6 6 9 J. W. T. Meadows and G. M. Matlack, Analyt. Chem., 1962, 34, 89. J. Pijck, J. Hoste, and J. Gillis, Mikrochim. Actu, 1962, 76. 671 P. C. van Erkelens, Analyt. Chim. Acta, 1962, 26, 46. 6 7 2 P. C. van Erkelens, Analyt. Chim. Acta, 1962, 26, 32. 6 7 3 J. RhZibka and J. Starj., Talanta, 1962, 9, 617. 6 7 4 W. D. Ralph, T. R. Sweet, and I. Mencis, Anulyt. Chem., 1962, 34, 92. 6 7 6 P. C. Stein, Analyt. Chem., 1962, 34, 352. 6 7 6 A. A. K. Al-Mahdi and T. Schonfeld, Mikrochim. Acta, 1962, 254.
494
exchange resin and only slowly eluted by a buffered citrate solution at pH 2-9-32, thus giving a good separation from most other metals. The efficiency of the method was checked with 59Fe.677 Zinc was determined in effluent waters, after removal of the lead by co-precipitation with strontium sulphate, by passing the water through a column of cellulose acetate impregnated with dithizone at pH 4.5.67s Several separations of fission products have been made. The rare earths have been separated and determined by using cation-exchange columns. After scavenging with zirconium phosphate and barium sulphate and finally elution with a-hydroxybutyrate solutions of pH 4.2 and 3.4,individual rare earths could be determined.679 Descending paper chromatography was used to separate plutonium and americium with butanol-nitric acid mixtures. It was possible to separate Pu(m) from Pu(r~).llO Separation of iodide ions by means of 1311on an Amberlite IR-400 resin, followed by elution with 4~-ammonium chloride and p-counting, was found to be suitable for low-level detection and determination. 680 The separation of 1311-labelled thyroxine and tri-iodothyronine from blood serum was effected on ion-exchange resin, an acetic acid-formic acid medium being used. Separation from other components of the serum was efficient and more rapid than extraction methods hitherto used.681 Similar separations have been possible by paper chromatography in a phosphate buffer at pH 8.5 6S2 and a trichloroacetic acid medium.683 By use of a column of alumina it was possible to separate and determine labelled sulphur, tetramethylthiuram disulphide, and dimorpholinyl disulphide in a toluene extract of vulcanisates. Liquid scintillation counting of the eluate was possible in spite of some quenching.684 Tritium assay by proportional counting after gas-chromatography has advantages over other methods and the difficulties arising from coincidence losses a t high count rates and interferences from other peaks have been s t ~ d i e d . ~ The separation of ~5 octadecane, phenanthrene, and similar compounds labelled with 14C was efficiently carried out on an alumina column. When applied to their determination in asphaltic bitumens and marine sediments some difficulties arose from other components of high molecular weight and separation was harder.686 Paper Chromatography has been applied to several biochemical assays by using 14C-labelled materials. The methyl esters of 14C-labelled bile acids have been effectively separated by descending chromatography on paper impregnated with aluminium hydroxide, the solvents being petroleumCholic, deoxycholic, and methanol and petroleum-benzene-methanol. lithocholic acid were determined in the range 0.6-3.0 pg.687 Pyridoxal
D. A. Knyazev and A. I. Mikhailichenko, Zhur. priklad. Kh,im., 1962, 35, 66. B. A. Loveridge and A. F. Owens, A.E.R.E. Report AERE-R 3945, 1962. K. Wolfsberg, Analyt. Chem., 1962, 34, 518. 6 8 0 M. Lesigang and F. Hecht, Mikrochim. Acta, 1962, 327. 6 8 1K. Muller, H. Skrube, and H. Spitzy, Mikrochim. Acta, 1962, 1144. 6 8 a A. Taurog, Biochim. Biophys. Acta, 1962, 60, 197. 683 S. Lissitzky, J. Torresani, A. Pinchera, and M. Andreoli, Clinica Chim. Acta, 1962, 7, 13. 6 8 4 H. I . Pedersen, Acta Chem. Xcand., 1962, 16, 870. ; 6 8 5 J. K. Lee, E. K. C. Lee, B. Musgrave, Yi-Noo Tang, J. W. Root, and F. S. Rowland, Analyt. Chern., 1962, 34, 741. 6 8 6 P. Hamway, M. Cefola, and B. Nagy, Analyt. Chern., 1962, 34, 43. 6 8 ' B. P. Smirnov, R. A. Popova, G. P. Danilova, and R. A. Niskanen, Biokhimiya, 1962, 27, 197.
6ii
6'8
6i9
CARTWRIQHT, WESTWOOD, A N D WILSON
495
phosphate in blood has also been estimated after separation of plasma and conversion by enzyme into tyramine.688 An automatic scanning method was used for measuring the activity. Gas-liquid chromatography has been used to determine 14C-labelled lipids. The effluents from the column were condensed directly into cartridges filled with anthracene crystals and silicone oil, and the activity measured directly by scintillation counting.OSg A considerable number of papers have been published on isotopic tracer and carrier methods involving precipitation of active species. Sodium has been determined in sea water by scavenging with lanthanum hydroxide followed by precipitation of sodium chloride by hydrogen chloride and followed by 4n proportional counting of 24Na. Sulphur has also been determined by precipitation as barium sulphate with a low-background!-counter to determine the 3%. Full details of interferences and their treatment were worked out. 090 Strontium was determined in bone after addition of carrier by ashing and y-counting after removal of the daughter product and precipitation as nitrate.691 -A rapid procedure for the determination of cobalt in fission products involved separation of the hydroxide and conversion into Co[Hg(SCN)*]; separation from other products was almost coniplete.692 Other fission products determined by precipitation methods included silver as iodide after scavenging and r e p r e c i ~ i t a t i o ncalcium as ,~~~ oxalate after removal of strontium as nitrate and scavenging with ferric hydr0xide,~94 yttrium and promethium as iodates after preliminary purification stages,695 and antimony as meta1.696 The use of thionalid for cocrystallisation of ultramicroscopic quantities of elements has been applied to 27 elements. Of these, 16 showed very high recoveries and the method was applied to the determination of silver in sea water by using lloAg as tra~er.6~'A rapid method for determining small concentra.tions of iodine involved addition of sodium iodide, liberation of iodine, and precipitation as silver iodide.698 Radio-assay of methanethiol containing 35S or 14C was effected by precipitation of the mercuric salt from a mercuricyanide solution. The /?-radiation was measured by a thin-window gas-flow counter ; good reproducibility was obtained after correction for self-absorpti0n.6~~ A number of novel procedures have been reported. Manganese has been isolated by distillation as permanganic acid from a solution of concentrated sulphuric and nitric acids and iodate, 54Mnbeing used as tracer. Recovery was excellent and the method was applied to the determination of the element in iron cyclotron targets. ' 0 A method for determining radon in waters
A. Hamfelt, Clinica Chirn. Acta, 1962, 7 , 746. A. Ksrmen, L. Giuffrida, and R. L. Bowman, J . Lipid Res., 1962, 3, 44. 6 9 0 D. L. Love and D. Sam, Analyt. Chem., 1962, 34, 336. 691 H. Foreman and M. B. Roberts, Talanta, 1962, 9, 559. 6 9 2 S. F. Marsh and W. J. Maeck, Talanta, 1962, 9, 285. 693 G. J. Hunter, G. F. Marshall, and M. Perkins, A.E.R.E. Report AERE-AM 89, 1962. 6 9 4 U.K.A.E.A. Report PG 311(W), 1962. 6Q6 M. E. Pruitt, R. R . Rickard, and E. I. Wyatt, Analyt. Chem., 1962, 34, 283. 6 9 6 J. W. Arden, G. J. Hunter, and M. PeIkins, A.E.R.E. Report AERE-AM 87,1962. 6 9 7 M. G. Lai and H. V. Weiss, Analyt. Chem., 1962, 34, 1012. 6 9 8 U.K.A.E.A. Report P G 334(W), 1962. R. H. Herber, Analyt. Chern., 1962, 34, 340. ' 0 J. Pijck and J. Hoste, Analyt. China. Acta, 1962, 26, 501.
688
689
496
was based on the equilibrium between 214Bi and its parent radon. By use of an inert carrier, the bismuth was precipitated as bismuth n-propyl gallate which was B-counted in the usual way. A limit of 20 picocuries/l. was claimed.701 A rapid method for determining active indium involved an amalgam-exchange reaction in hydrobromic acid solution. After acquiring activity, the amalgam was back-extracted with inert indium solution and the activity of the aqueous solution was measured. The possible interference of 19 other elements was tested but contamination was < O - l % . 7 0 2 Dissolved oxygen has been determined in pure and natural waters by its quantitative oxidation of 204Tl deposited on copper turnings. The water containing dissolved oxygen was passed through a column containing the turnings and the TI+ liberated was detected by a G.M. tube; the method was claimed to be suitable for the range 0.2-3 p.p.m. on use of a linear calibration curve.7o3 A simple method for determining the isotope effect on reaction rate has been applied t o D-glucose by double labelling. By following the rate and e of oxidation of a- or ~ - [ 6 - ~ ~ C , l - ~ H ] g l u c o sa- or ~-[l-~*C,6-~H]glucose, information on the importance and position of the isotope in the molecule was obtained. Since the ratio of activities only was required, separation of the individual species was not necessary. 704 MMS Spectrometry.-A recent comprehensive review has described the developments in methodology and analytical applications which have occurred during the years 1960 and 1961, particularly in the United States of America,and the U.S.S.R.705 I n another review of methods for determining interstitial elements in metals, mass spectrometry was claimed to be highly successfulfor oxygen, giving a possible precision of &O.OOOl% on a 1g. sample.706 New instruments reported include the SMU 50OY7O7 modified a instrument including a battery-operated emission regulator, which is particularly suitable for isotope ratio analyses and has been successfully applied t o 13C/12C ratios;708and a time-of-flight instrument with two collectors, one of which collects the total ion current and the other records the mass spectrum. 709 A modified filament arrangement has been described in which the centre filament is vertical and parallel to the side filaments, permitting simultaneous analysis of two samples and the measurement of abundance differences smaller than is possible with the normal filament arrangement. 710 A modified radio-frequency spark-source has been applied to determination of amino-acids and their ~ a l t s . 7 ~ 1 Other devices include an all-glass heated inlet for injecting samples into the stream feeding the spectrometer,712 an
J. R. W. Kerr, D. I. Coomber, and D. T. Lewis, Analyst, 1962, 87, 944. R. R. Ruch, J. R. De Voe, and W. W. Meinke, Talanta, 1962, 9, 33. 7 0 5 H. G. Richter and A. S. Gillespie, Analyt. Chem., 1962, 34, 1116. 7 0 4 H. S. Isbell, L. T. Sniegoski, and H. L. Frush, Analyt. Chem., 1962, 34, 982. 7 0 5 R. M. Reese, Analyt. Chem., 1962, 34, 243R. ' 0 6 M. W. Mallett, Talanta, 1962, 9 133. 7 0 7 D. Charles, Chim. analyt., 1962, 44, 49. ?OsA. 0. Nier, W. R. Eckelmann, and R. A. Lupton, Analyt. Ckmn., 1962, 34, 1368. 7 0 9 R. S . Gohlke, Analyt. Chem., 1962, 34, 1332. H. Patterson and H. W. Wilson, J . Sci. Instr., 1962, 39, 84. ' 1 W. L. Baun and D. W. Fischer, Analyt. Chem., 1962, 34, 294. 1 'la L. Peterson, Analyt. Chem., 1962. 34, 1850.
701
70a
497
inlet for injecting samples directly from a gas-chromatography column,713 and a molecular-sieve device for separating volatile compounds from large excesses of carbon dioxide and water, with subsequent removal of adsorbed materials for analysis.714 The plutonium-uranium ratio in feed solutions for reactor separation plants has been determined by using an MS 5 spectrometer. The concentrations of 235U, 238U, 239U were determined by using 233U a tracer, and and as those of 24OPu, 248Pu, and 244Pu by using 242Pu as tracer.'15 A check by mass spectrometry on the effectiveness of chemical precipitation of rubidium and strontium showed that separation of strontium as sulphate after removal of traces of iron and aluminium is more rapid and efficient than by ionexchange techniques,716 though the latter can be shown to give products which are pure enough for mass-spectrometric analysis.717 Analysis of a number of ferrocenes has shown that little or no fragmentation occurs at low voltages, and the peak intensities of the spectra are quantitative measures of the quantity of material.7ls Silver has been determined in meteorites by a wet method followed by chromatography and precipitation as sulphide which was examined on a tantalum filament in a mass spe~trometer.~lg The lSO content of sugars and glycogen has been determined by oxidising them in the presence of mercuric cyanide to yield carbon dioxide, followed by massspectrographic analysis of the latter.720 Most applications have, of course, been associated with organic materials, especially in the petroleum industry. Analyses of gasolines and other motor fuels have produced calibration data for 13 aromatic, 2 olefin, and 4 saturated hydrocarbon types in the c6412 range with a reproducibility of 0.2%. The aromatics included alkylated benzenes, indanes, and naphthalenes. 721 Similar analyses of light catalytic cycle stocks (b.p. range 622-625"~), within the formula range CnHBne16 and CnH2n-18, showed that the former range was largely alkylfluorenes and the latter contained a high percentage of phenanthrenes and anthracenes, 7 2 2 and compounds of the CnH2n--14 type were tetrahydroanthracenes, tetrahydrophenanthrenes, and benzindanes. Catalytically cracked furnace oils have shown the presence of paraffins, condensed and uncondensed polycycloalkanes, alkylbenzenes, indanes, tetralins, indenes, naphthalenes, acenaphthylenes, fluorenes, and acenaphthenes. Infrared data and elution methods were used to assist the interpretations.724 The ratio of branched to normal hydrocarbons up to C,, has been determined
7 1 3 V. A. Cirillo, D. J. Skahan, B. Hollis, and H. Morgan, Analyt. Chem., 1962, 34, 1353; C. BrunnBe, L. Jencld, and K. Kronenberger, 2 analyt. Chem., 1962. 189, 50. .
M. L. Bazinet and C. Merritt, Analyt. Chern., 1962, 34, 1143. U.K.A.E.A. Report PG 340(W), 1962. 716 W. G. Deuser, Geochim. Cosmochim. Acta, 1962, 26, 515. 717 P. W. Gast, Geochim. Cosmochim. Acta, 1962, 26, 927. '18 D. J. Clancy and I. J. Spilners, Analyt. Chem., 1962, 34, 1839. 7 1 9 V. R. Murthy, Geochim. Cosmochim. Acta, 1962, 26, 481. 7 2 0 J. S. Lee, Analyt. Chem., 1962, 34, 835. 721 D. M. G. Lawrey and J. F. Paulson, Analyt. Chem., 1962, 34, 538. 7 2 2 K. W. Bartz, T. Aczel, H. E. Lumpkin, and F. C. Stehling, Analyt. Chem., 1962, 34, 1814. 7 3 3 T Aczel, K. . W. Bartz, H. E. Lumpkin, and F. C. Stehling, Analyt. Chem.., 1962, 34, 1821. 7 2 4 M. E. Fitzgerald, V. A. C r l o andF. J. Galbraith, AnaZyt. Chcm., 1962,34,1276. iil,
?14
716
498
in Fischer-Tropsch products by u s h g a molecular-sieve technique.725 Nitrites have been identified in petroleum products after removal of the nitrogen bases with hydrochloric and perchloric acid and separation by formation of complexes with ferric chloride and zinc chloride. Dicyanobenzene, cyanoindene, cyanohexane, cyanonaphthalene, and cyanobiphenyl derivatives were identified. 726 A number of papers have been published on correlations for classes of compounds : 103 monohalogenated aliphatic compounds have been investigated and degradation paths shown t o be characteristic of the electronegativities of the halogen atom. The cleavage mainly occurs in the carbonhalogen bond and, as expected, the ease of breakdown follows the order I > Br > C1 > B'. There is some tendency for iodine and bromine atoms t o form, but with the other halogen compounds only hydrogen chloride and fluoride are found. If the carbon bond adjacent t o the halogen is branched then the cleavage follows the order C1 > B > I.727 r When aromatic compounds were tested, the major ion degradation paths were shown t o be a combination of effects found previously for aromatic hydrocarbons and aliphatic halogenated compounds, with the former predominating for the aromatic fluorides and the latter for the aromatic iodides. Poor ring halogen compounds, other than fluorides, the loss of halogen gave a major ion, but when the halogen was on a side chain cleavage of the bond 9 t o the group , containing the halogen atom was highly favoured : 88 compounds in all were tested. 728 Aliphatic nitriles gave significant amounts of the molecular ion in their mass spectra and cleavage of the a-bond t o the functional group was quite insignificant. /?-Bond cleavage with rearrangement gave the base peak up t o C, but became less important a t higher molecular weights or with , chain-branched compounds. The ion of mass M 1, however, was significant and useful for molecular-weight identification in many cases.729 With amines the molecular ion peak decreased rapidly as the molecular weight increased. Those compounds which were not substituted on the a-carbon atom underwent /?-bond cleavage to produce the most abundant ion. With a-substitution an a-p rearrangement of groups took place t o form the most abundant ion.730 The mass spectra of a number of methyl and beiizyl substituted benzoate also gave useful data for analytical purposes. 731 Deuterium has been determined in organic compounds by combustion followed by reduction of the H,O and D,O t o H, and D, and analysis of the resultant gases. With the use of small-scale built-in apparatus the method was rapid and reliable.732 By low-temperature ionisation the parent peaks of 30 steroids have been obtained and have provided a method for their molecular-weight determina-
's6
A. G. Sharkey, J. L. Schultz, and R . A. Friedel, Anulyt. Chem., 1962, 34,

K. Hartung and D. M. Jewell, Analyt. Chi,m. Actu, 1962, 27, 219. W. McLafferty, Analyt. Chern., 1962, 34, 2. W. McLafferty, Analyt. Chem., 1962, 34, 16. W. McLafferty, Analyt. Chem., 1962, 34, 26. S. Gohlke and F. W. McLafferty, Alzalyt. Chem., 1962, 34, 1281. Aczel and H. E. Lumpkin, Analyt. Chem., 1962, 34, 33. Tamiya, Bull. Chem. Soc. Japan, 1962, 35, 863.
826. G. F. 7 2 8 F. 720 F . 7 3 0 R. 7 3 1 T. 732 N .

726
727
C A R TWRIG HT
, W E STWO 0 D , A N D
W IL S 0N
499
tion.733 The method is claimed t o be rapid. Highly substituted pregnanes and pregnenes gave similar results.734
11. T H E R I A L METHODS
Early work from 1893 t o 1940 on thermogravimetric analysis has been reviewed by Duva1,735 and more recent developments by B&rta.736 The importance of close attention t o conditions of operation and state of the sample in obtaining reproducible results continues t o be stressed. Berlin and Robinson 737 have derived a relation between final decomposition temperature, the size and physical condition of the sample, and the rate of heating, which was in agreement with published data on the decomposition of a number of compounds, and in reasonable agreement with apparent activation energies calculated for the decompositions. From e.m.f. values obtained in thermogravimetry, Soulen 738 has used an electronic digital computer t o calculate temperature, weight, loss of weight, and rate of loss of weight. A number of papers have described modifications t o or refinements of thermogravimetric apparatus, including automatic temperature control and registration of temperature and change of ~ e i g h t , ~ 3 9 a new method of temperature regulation with a transistorised thermobalance,740 a n automatic thermobalance for use with a vacuum,741 and modifications t o allow safe operation in a hydrogen atmosphere. 742 A useful review of differential thermal analysis by Mackenzie and Mitchell 7 4 3 lists 297 references. I n addition t o an account of the historical development, principles, and technique of the method, it describes the growing applications, not only to clays and minerals, where much of the development work was done, but also t o a much wider field of inorganic, organic, and organometallic compounds. Barrall and Rogers 744 discuss the applications to organic compounds, and the merits of employing a diluent, which may, for some analytical work, advantageously react with the sample. Other work has been concerned with chelates of the oxines,745 melting and and boiling points and other phase transitions in organic materials with components of high vapour pressure in an apparatus which permits rapid cycling over a small temperature range.747 The combination of results from thermogravimetric and differential
L. Peterson, Chem. and Ind., 1962, 264. L. Peterson, Analyt. Chem., 1962, 34, 1781. 7 3 5 C. Duval, China. analyt., 1962, 44, 191. i 3 6 R. Barta, Silikcity, 1962, 6, 125. 7 3 7 A. Berlin and R. J. Robinson, Analyt. Chirn.. Acta, 1962, 27, 50. i 3 8 J. R. Soulen, Analyt. Chern., 1962, 34, 136. 739 P. Imrig, Silikdty, 1962, 6, 91. 7 4 0 Z. Formanek and J. Dykast, Silikcity, 1962, 6, 113. 5 4 1 0. brnjr, Silikcity, 1962, 6, 81. 7 4 2 H. J. Isensee, 2. analyt. Chem., 1962, 186, 357. 7 4 3 A. C. Mackenzie and B. D. Mitchell, Analyst, 1962, 87, 420. 7 4 4 E. M. Barrall I1 and L. B. Rogers, Analyt. Chem., 1962, 34, 1101. 7 4 5 W. W. Wendlandt and G. R. Horton, Analyt. Chern., 1962, 34, 1098. 7 4 6 D. A. Vassallo and J. C. Harden, Analyt. Chem., 1962, 34, 132. 7 4 7 D. B. Gasson, J. A& ! Instr., 1962, 39, 78.
i33
734
500
thermal analyses has shown advantage in work on phosphor raw materials,74s 750 into the practice and and there have been more investigations advantages of simultaneously registering both sets of results. P. F. S. CARTWRIGHT.
7499
J. V. WESTWOOD. D. W. WILSON.
R. C. Ropp and M. A. Aia, Analyt. Chem., 1962, 34, 1288. L. Erdey, G. Liptay, G. Svehla, and F. Paulik, Talanta, 1962, 9, 489. 7 5 0 A. Blaiek and J. Halousek, Silikhty, 1962, 6, 100.
748
749
CRYSTALLOGRAPHY
1. GENERAL
THIS Report is concerned with papers on crystal-structure analysis and allied topics which were published in 1962. A few papers from earlier yeam, whose inclusion now seems appropriate, are also mentioned, but as usual the reader may find that something of importance has been overlooked, probably one of his o w n publications in fact! Because of indisposition of a contributor the section on inorganic structures has been held over until next year. 1962 was the 50th anniversary of the discovery of X-ray diffraction by von Laue, Friedrich, and Knipping, and the occasion was celebrated by a meeting in Munich in July. This took the form of a commemorative session, lectures describing the development of the subject, and a symposium on " Recent Advances in Experimental and Theoretical Methods of Crystal Structure Research" during which some 65 papers were presented. The year has also been marked by the award of two Nobel prizes, in Chemistry and in Medicine, to five research workers who are (among other things) X-ray crystallographers: M. F. Perutz, J. C. Kendrew, F. H. Crick, J. D. Watson, and M. H. Wilkins. Recent spectacular progress in protein crystallography and biomolecular structures was reviewed in these Reports two years ago, and, although 1962 might seem the occasion, it was felt that the time was not yet ripe for another review. There has been no diminution in the number of papers dealing with (relatively!) simple crystal structures ; indeed, the X-Ray Analysis Group of the Institute of Physics has thought it worth while to produce a list of crystal-structure investigations in progress, to prevent duplication of effort. Experimental Techniques.-A metal cryostat of simple construction, which can be oscillated or rotated, and was designed for the study of single crystals or powders at temperatures down to 4" K , has been described.l Streib and Lipscomb have described their equipment for crystal growth and investigation a t temperatures in the helium-nitrogen range. Apparatus for making X-ray investigations at high pressures is coming into use in a number of laboratories, and a simple device capable of producing a quasihydrostatic pressure of 150 kbar has been described.3 A suggestion for modelling a counter diffractometer on a Seeman-Bohlin focusing camera has been p ~ b l i s h e d . ~ Other improvements in diffractometer design include a simplified three-circle X-ray goniometer.5 X-ray image intensifiers and secondary electron image intensifiers can be used for direct observation and recording of diffraction patterns; in fact the signal strength can be made such that cinefilm running at standard speed can record the changing pattern
* W. E. Streib and W. N. Lipscomb, Proc. Nat. Acad. Sci., Wash., 1962, 48, 911. * J. C. Jamieson and A. W. Lawson, J. AppZ. Phys., 1962, 33, 776.
ti R.
K. L. Chopra, Cryogenics, 1962, 2, 167.
E. R. Pike, J . S i Instr., 1962, 38, 205. c. W. H. Small and S . Travers, J . Sci. Instr., 1961, 38, 205.
502
CRYSTALLOGRAPHY
from a rotating crystal.6 Polaroid film promises t o be particularly useful in recording neutron diffraction patterns. Most of us will regard as belated the discovery 8 that a counter and scaler can be used to measure integrated intensity. It is perhaps not inappropriate to mention under this heading the progress that has been made in accurate measurement of lattice parameters, Knowles reports new diffraction measurements bearing on the factor for conversion of X-units into Angstroms, and gives this factor as 1.002049 0.000036. A single-crystal method has been used t o give the unit cell dimensions for seven pure materials to six significant figures,l0 while a new analysis l1 of data published by Bond l 2 has given the unit cell dimension of silicon to about the same accuracy. Otte l3 has discussed the effect of specimen condition on the precise determination of lattice parameters. Theory and Practice of Structure An&&.-Progress in the last ten years or so in the field of X-ray and electron diffraction by molecules and crystals has been reviewed.14 An interesting paper l5 discusses the possibilities for direct structure analysis by a computer when stereochemical information can be utilised. Users of crystallographic computers may find a recent conference report l 6 of interest. Crystallographers have long speculated on whether it might not be possible to circumvent the phase problem by experimental measurement of the relative phases of diffracted X-ray beams. Such a measurement has now been reported,17 in which a highly perfect crystal of germanium is used, but it is likely to remain merely an interesting demonstration. Steady progress continues in the theory of structure analysis; methods may still be roughly classified as Patterson function or direct. New methods for locating the replaceable atoms in a pair of isomorphous crystals have been described. l8 The number of structurally identical units within a cell may exceed the number of general positions. The angular relation between two such units unrelated by space-group symmetry may in principle be found by a Patterson-function method. Applications in protein crystallography are being made.lg The possibility of improving the resolution in electron-density maps of protein crystals by making use of phase relations between structure factors has been investigated.20 Vector sets, related to the Patterson function, may be generalised t o give so-called image sets which are related t o the result of convoluting
-+
G. W. Goetze and A. Taylor, Rev. Sci. Instr., 1962, 33, 353. H. G. Smith, Rev. Sci. Instr., 1962, 33, 128. 8 Y. Z . Nozik and I. I. Yamzin, KristallograJiya, 1962, 7, 123. J. W. Knowles, Canad. J. Phys., 1962, 4 , 257. 0 l o A. S. Cooper, Acta Cryst., 1962, 15, 578: I I K . E, Beu, F. J. Musil, and D. R. Whitney, Acta Cryst., 1962, 15, 1292. 12 W. L. Bond, Acta Cryst., 1960, 13, 814. 13H. M. Otte, J. A p p l . Phys., 1961, 32, 1536. l4 M. Roux and M. Cornille, Cahiers de Phys., 1962, 16, 45. I5 H. J. Milledge, Proc. Roy. SOC., 1962, A., 207, 566. V. G. Petrov, KristallograJya, 1962, 7, 163. l7 M. Hart and A. R. Lang, Phys. Rev. Letters, 1961, 7, 120. lev. R. Sarma and R. Srinivasan, Acta Cryst., 1962, 15, 457; S. Raman and W. N. Lipscomb, 2. Krist., 1961, 116, 314. 19 M. G. Rossmann and D. M. Blow, Acta Cryst., 1962, 15, 24. 2 O W. Hoppe, Acta Cryst., 1962, 15, 13.
C O C H R A N : GENERAL
503
two different functions ; these sets may have crystallographic applications.21 Possible improvements have been suggested22 in the use of Buergers minimum function. An investigation of the symmetries of vector superposition diagram8 has been made.23 Examples of structure determinations made by such methods are those for thiamine hydrochloride (vitamin B,) and for the synthetic peptide tosyl-~-prolyl-~-hydroxyproline.~~ The authors of the latter investigation have made an interesting comparison of a number of related methods.26 A connexion between Patterson-function and direct methods has been discussed by Hauptman and Karle.26 The conversion of these authors to this point of view is welcomed! A general theory of ineq~alities,~ based on earlier work by Karle and Hauptman,28 has been worked out. Successful applications of direct methods have been made in determining the structures of deoxyanisoin, ( )-S-methyl-L-cysteine is sulphoxide, and rubrofusarin. 29 The last named (Cl5HI2O5) probably the largest molecule whose structure has been determined by the use of sign relations between structure factors. An interesting feature of the analysis is that an incorrect set of signs gave a plausible structure which could not be refined despite the fact that atoms differed from their correct positions by only 0.25A on average.30 It is becoming almost standard practice t o determine the absolute configuration of organic molecules containing bromine or iodine by making use of the phenomenon of anomalous dispersion. Recent examples include the investigations of himbacine hydrobromide, N-methylgelsemicine hydriodide, and codeine hydr~bromide.~lBijvoet 32 has investigated the effect on the theory of the method of having in the unit cell several atoms which scatter anomalously. Some interesting developments have taken place in optical analogue methods for structure determination. Harburn and Taylor 33 have shown how three-dimensional Fourier transforms can be derived optically, and a similar experimental technique has been used to obtain non-centrosymmetric Fourier projections. The structure determination 34 of 9,lO-anthraquinol dibenzoate provides a good example of the use of optical methods. Accurate Structure Anslysis.-A useful survey of the accuracy obtainable in intensity measurements, when a three-circle counter dsractometer is used, has been published.35 Sources of error in intensity measurements, to which 2 1 M. J. Buerger, 2. Krist., 1961, 116, 430. 2 2 S. Raman, Acta Cryst., 1962, 15, 283.
23
24
E. Subramanian, 2. Krist., 1961, 116, 182.
J. Kraut and H. J. Reed, Acta Cryst., 1962, 15, 747; J. Fridrichsons and A. McL. Mathieson, ibid., p. 569. 2 5 J. Fridrichsons and A. McL. Mathieson, Acta Cryst., 1962, 15, 1065. 2 6 H. Hauptman and J. Karle, Acta Cryst., 1962, 15, 547. 2 7 S. Naya, Acta Cryst., 1962, 15, 69. 2 8 J. Karle and H. Hauptman, Acta Cryst., 1950, 3, 181. 2 9 H. G. Norment and I. Karle, Acta Cryst., 1962, 15, 873; R. Hine, ibid., p. 635; G. H. Stout and L. H. Jensen, ibid., p. 451. 30 G. H. Stout and L. H. Jensen, Acta Cryst., 1962, 15, 1060. 31 J. Fridrichsonsand A. McL. Mathieson, Acta Cryst., 1962,15,119; M. Przybylska, ibid., p. 301; G . Kartha, F. R. Ahmed, and W. H. Barnes, ibid., p. 326. 32 J. M. Bijvoet, Acta Cryst., 1962, 15, 620. 33 G. Harburn and C. A. Taylor, Proc. Roy. SOC.,1961, A , 264, 339; G. Harburn and C. A. Taylor, Nature, 1962, 194, 764. 3 4 J. Iball and K. J. H. Mackay, Acta Cryst., 1962, 15, 148. 35 L. E. Alexander and G. S. Smith, Acta Cryst., 1962, 15, 983.
504
CRYSTALLOGRAPHY
very little attention has been paid, include simultaneous diffraction (Umweganregung) and the contribution of thermally-scattered radiation close t o the Bragg peak. The possible importance of simultaneous diffraction is strikingly demonstrated by recent measurements on germanium, and the fact that it is prone to occur when equi-inclination geometry is used has been pointed 0 ~ t . ~ 6A means of correcting for the effect of thermal scattering has been worked and is claimed t o be of general application. Accurate determinations of the electron distribution and of thermal parameters in lithium hydride 3s and in a-quartz 39 have been reported. Organic molecules for which structure determinations have been made with considerable accuracy (standard deviations of bond lengths about 0.005 8) include monofluoroacetamide and N-a~etylglycine.~~ Jensen 41 has reexamined the problem of systematic deviations in bond lengths, involving hydrogen atoms, as determined by X-ray diffraction, and suggests that systematic errors are more likely t o be in the refinement procedure than in the experimental data. The electron distribution in diamond has been calculated by the Thomas-Fermi method and by the method of orthogonalised plane waves.42 Both methods give results in fairly good agreement with X-ray mewurements. A theoretical estimate of the magnitudes of aspherical contributions t o the atomic scattering factors of certain atoms, particularly in relation t o the accuracy of experimental measurements and scaling procedures, has been made by D a ~ s o n . ~ ~ Thermal Effeds in Crystals.-Lonsdale 44 has given a survey of the topics of atomic movements in crystals, phase changes, and solid-state reactions. Methods of measuring the Debye-O and results for cubic crystals have been reviewed by Herbsteim4s The allegedly anisotropic temperature factors of certain cubic crystals have not been confirmed by a careful r e - i n ~ e s t i g a t i o n . ~ ~ The influence of anharmonic effects on the temperature factor has been worked out, and may be appreciable in certain circumstance^.^^ Such effects are, however, unlikely ever t o assume importance in structure analysis. The Debye temperatures of germanium, as determined from X-ray or from specific-heat data, differ by as much as 20%, but this is t o be expected from the frequency distribution of the modes of thermal vibration.48 Measurements of the temperature factors of perfect crystals have given results which
36 H. Cole, F. W. Chambers, and H. M. Dunn, Acta Cryst., 1962, 15, 138; H. L. Yokel and I. Fankuchen, ibid., p. 1188. 37 S. Annaka, J . Phys. SOC. Japan, 1962, 17, 846. 2 3 R. S. Calder, W. Cochran, D. GIifEths, and R. D. Lowde, J . Phys. und Chem. Solids, 1962, 23, 621. 39 R. A. Young and B. Post, Acta Cryst., 1962, 15, 337. 4 0 D. 0. Hughes and R. W. H. Small, Acta Cryst., 1962, 15, 933; J. Donohue and R. E. Marsh, ibid., p. 941. 41 L. H. Jensen, Acta Cryst., 1962, 15, 433. 4 2 H. C. Bolton and J. W. Heaton, Proc. Phys. SOC., 1961, A, 72,239; L. Kleinman and J. C. Phillips, Phys. Rev., 1962, 125, 819. 4 3 B. Dawson, Actu Cryst., 1961, 14, 1271. 4 4 K. Lonsdale, Nature, 1962, 194, 5. 4 5 F. H. Herbstein, Adv. Phys. (Phil. Mag. Supplement), 1961, 10, 313. 4 6 R. W. Cahn and R. Feder, Acta Cryst., 1962, 15, 322. 4 7 M. A. Krivoglaz and E. A. Tekhonova, Kristallografya, 1961, 6, 496. 4 8 B. W. Batterman and D. R. Chipman, Phys. Rev., 1962, 127, 690.
COCHRAN: GENERAL
505
are not entirely in accord with the theory.49 A one-dimensional model for the lattice vibrations of molecular crystals has been i n ~ e s t i g a t e d . ~ ~ A neutron diffraction study of ferrous fluorosilicate hexahydrate has shown that the thermal motion can be accurately described in terms of rigid-body translations and librations. 51 As already reported,S2 the coherent inelastic scattering of neutrons by a single crystal can be analysed t o give information about lattice vibrations. The inelastic scattering of neutrons by hydrogenous materials is mainly incoherent, and neutron studies of powder specimens of organic materials may yet develop into a new spectroscopic technique; an example is provided by an investigation of hexamethylenetetramine. 63 A number of similar studies are described in a conference report.54 S m e b and Geometrical Crystallography.-Papers dealing with these topics are not likely t o attract more than passing attention from structural crystallographers. Quite often, however, the ideas reported in them eventually turn out t o have practical applications. For example, the question of how simple mosaics representing plane groups can be fitted on t o the surfaces of polyhedra 5 5 may have importance for virus structures, since the protein layer surrounding the ribonucleic acid centre is made up of identical units packed in a symmetrical way. The symmetry of irregular polyhedra in a non-lattice array has applications t o the theory of liquid crystals.56 Many papers in the Russian literature also deal with " black and white " and " colour " symmetry. The subject has been reviewed by Neronova and Be10v.~' I n a later paper the same authors discuss colour antisymmetry mosaics,58 and other papers in KristuZZograJiyu deal with allied topics such as symmetry and antisymmetry groups of finite strips, infinite black and white ribbon groups,59and the two-dimensional Shubnikov groups.6o The subject has not been neglected in the German literature. It has been shown 61 how two-sided two-coloured band groups can be described by Hermann-Manguin type symbols. The concept of point-group symmetry has been generalised 62 by attributing a variable quality t o the points of a point group. The 32 crystallographic point groups thus give rise t o 139 cryptosymmetry or colour symmetry point groups for which symbols have been devised.*3 The problem of the general classification of groups involving change of side, sign, or colour has been treated from a strictly geometrical
B. W. Batterman, Phys. Rev., 1962, 126, 1461; 127, 686. E. Sandor, Acta Cryst., 1962, 15, 463. 51 W. C. Hamilton, Acta Cryst., 1962, 15, 353. 5 2 Ann. Reports, 1960, 57, 470. 53 L. N. Becka, J . Chem. Phys., 1962, 37, 431. 5 4 " Symposium on the inelastic scattering of neutrons in solids and liquids," International Atomic Energy Agency, Vienna, 1963. 6 5 G. S. Pawley, Acta Cryst., 1962, 15, 49. 5 6 G. S. Pawley, 8. Krist., 1961, 116, 1. 5 7 N. N. Neronova and N. F. Lelov, Kristallografiya, 1961, 6, 3 ; see also Ann. Reports, 1960, 57, 466. 5 8 N. N. Neronova and N. V. Belov, Kristallqrafiya, 1961, 6, 831. A. V. Shubnikov, Kristallografiya, 1962, 7 , 3, 186. 6 o A. M. Zamorzaev and A. F. Palistrant, Kristallografiya, 1961, 6, 163. 6 1 A. Pabst, 2. Krist., 1962, 117, 128. 6 2 A. Niggli and H. Wondratschek, 2. Krist., 1950, 114, 215; H.Wondratschek and A. Niggli, ibid., 1961, 115, 1. 63 0. Wittke, 8. Krist., 1962, 117, 153.
49 50
606
CRYSTALLOGRAPHY
point of view.64 Finally, we may note that even the equivalent in reciprocal (or Fourier) space of coloured or otherwise complex groups in crystal apace has been considered.6 5 The combination of results of morphological measurements with knowledge of the space-group can give information about the arrangement of bonds in the structure, as has been shown by an example.66 Kitaigorodski's work has been &ended 67 by the development of a graphical method of determining close-packed two-dimensional arrays of identical figures, with special reference t o the structures of organic crystals. Loeb has published a further paper 6 8 on a modular algebra for the description of the location and environment of crystal elements which is suitable for storage in computers and may provide a useful system of classification.
w. c.
2. ORGANIC STRUCTURES
67 A. I. Kitaigorodski, Kr&stallograJya, 1957, 2, 456; P. M. Zorkii and M. A. P o d Koshits, ibid., 1961, 6, 655. 6 8 A. L. Loeb, Acta Cryet., 1962, 15, 219. 6 0 P. A. Akishin, L. V. Vilkov, and N. I. Mochalova, Zhur. strztlct. Khim., 1961, 2, 545. 7OA. Turner-Jones and C. W. Bunn, Acta Cryst., 1962, 15, 105. 71 R. L. Sass and R. F. Scheuerman, Acta Cryst., 1962, 15, 77. 7 2 D. 0. Hughes and R. W. H. Small, Acta Cryst., 1962, 15, 933. 73 L. H. Jensen, Acta Cryst., 1962, 15, 433.
containing conjugated double-bond systems may be non-planar as a result of steric hindrance. An electron diffraction study has shown that, whereas methylglyoxal (Me-COCHO) is planar, a-chloroacraldehyde [CH,:CCl*CHO] is n ~ n - p l a n a r . I n~the latter, ~ the rotation angle of the C=O and C=C bonds from the trans- and cis-configuratim is 57" and 41" for the two rotational isomers, which are in the ratio 2 : 1. The chain configurations in poly(ethylene adipate) and poly(ethylene suberate) are similar, and their packing and the angle B are determined by interaction between the C=O dipoles and neighbouring chains.70 I n a new study of sodium bi~arbonate,'~ C-0 distances are 1-346, the 1.264 and 1.263AYand the hydrogen bond between adjacent bicarbonate ions is 2.595A. Each sodium is surrounded by six oxygen atoms a t an average distance of 2.438 Lf in a slightly distorted octahedral arrangement. All the atoms, apart from the hydrogens, in monofluoroacetamide (CH,F*CO*NH,) are closely planar. 72 Of the molecular dimensions, the C-C bond of 1.533 & 0.006 if is longer than expected for sp3 and s p 2 hybridised atoms, but L(0-CN) = 124", which is consistent with values in other amides of known structure. The two N-He-0 bonds [d(N-.O) = 2.955 and 2.878 Lf] are non-linear, with L(H-N-0) = 11" and 26". The fluorine atom does not participate in intermolecular hydrogen bonds but may bond intramolecularly with the amide nitrogen or hydrogen atom. Average dimensions in the CC chain of NN'-hexamethylenebispropionamide (Et*CO*NH-[CH,],-NH*CO*Et} d(C-C) = 1.529 -= 73 are j 0-002 A, L(C-C-C) = 112.8 0.7", and L(H-C-H) = 109 & 1". W. T. Holser, Acta Cryst., 1961, 14, 1236. 6 6 A. Bienenstock and P. P. Ewald, Acta Cryst., 1962, 15, 1253. 6 6 J. D. H. Donnay and G. Donnay, KristaUograJiya, 1961, 6, 840.
Acyclic Compounds.-Molecules
SUTOR: ORGANIC STRUCTURES
507
The SC:(NH,), group in thiourea dioxide [(NHs;)zC:S0,],74 the lowtemperature form of thiourea,75 studied by electron diffraction, and in S-methylisothiourea sulphate ([MeS:C(NH,),], + SO,,-} 76 is planar or very nearly so. Thiourea dioxide has a pyramidal arrangement of carbon and oxygen atoms about the sulphur atom, and the length of the C-S bond (1.85 0.02 8, cf. 1.79 and 1.74 both & 0.01 8 in S-methylisothiourea sulphate) accounts for the ease with which it is broken. Each molecule forms eight hydrogen bonds with neighbouring molecules. I n thiourea, weak N-H--S hydrogen bonds have dimensions d(N-S) = 3-45, and 3.38 8, and d(H-S) = 2-20 and 2.39 8. There is a preliminary report of the structure of the compound Me,N*SO,*NMe,.5 7 Triethyl~carpane,~~ formed by the addition of carbon disulphide to triethylphosphine, is a zwitterion of a quaternary phosphonium derivative of dithioformate, Et,P +CS,-. The phosphorus atom forms four nearly tetrahedral bonds of average length d(P-C) = 1-80 A. Other dimensions are: d(C-S) = 1.69 & 0.03 8 and L(S-C-S) = 128 & 2". I n potassium 00-dimethyl phosphorodithioate 79 [KS,P(OMe),], each potassium ion is surrounded by six sulphur and two oxygen atoms, forming a distorted tetragonal anti-pyramid. The P-0 distance of 1-648 is comparable with the single-bondvalue in metaphosphates. Aromatic and Other Cyclic Molecules.-As in o-chlorobenzoicacid, molecular overcrowding in o-bromobenzoic acid 8 0 is reduced by a twist (18O) of the carboxyl group out of the aromatic plane, and by a sideways and outof-plane displacement of exocyclic carbon and bromine atoms away from each other. There are in-plane displacements of exocyclic C-C and (341 bonds away from each other in 2-chloro-5-nitrobenzoicacid.*l Buttressing of the hydrogen atom at position-6 by the nitro-group (which is twisted only 7" out of the aromatic plane) may cause a relayed steric effect resulting in the somewhat larger rotation (23") of the carboxyl group. Both acids occur in centrosymmetrical dimers linked by hydrogen bonds of length 2.64 and 2.61 8, respectively. I n the potassium salt of o-nitrophenol hemihydrate,82 the anion is planar with a short non-bonded intramolecular distance of 2.64A between the nitro- and phenol groups. Each potassium ion is co-ordinated by seven oxygen atoms at distances of 2.69-2.94 8, but the system has no apparent symmetry. I n the structure of m-bromonitrobenzene,s3 each bromine atom forms two charge-transfer bonds, with d ( B r 4 ) = 3-388. The chain of nitrogen atoms in the p-dibromoderivative of diazoaminobenzene (BrC,H,*N:N*NH*C,H,Br) is non-hear.* The apparent equality of the two N-H bonds (1.23 and 1.25 8) may result from a true or statistical transfer of the hydrogen atom. Molecules are 7 4 R. A. L. Sullivan and A. Hargreaves, Acta Cryst., 1962, 15, 675.
-+
76
76
C. H. Stam, Acta Cryst., 1962, 15, 317. T. Jordan, W. Smith, and W. N. Lipscomb, Tetrahedron Letters, 1962, 37. 7 8 T. N. Margulis and D. H. Templeton, J. Chem. Phys., 1962, 36, 2311. 7 0 Ph. Coppens, C. H. MacGillavry, S. G. Hovenkamp, and H. Douwes, Acta Cryst., 1962, 15, 765. G . Ferguson and G . A. Sim, Acta C y s t . , 1962, 15, 346. 81 G . Ferguson and G. A. Sim, J . , 1962, 1767. 8 a J. P. G. Richards, 2. KriSt., 1961, 116, 468. T. L. Charlton and J. Trotter, Proc. Chem. Soc., 1962, 221. 8 4 Yu. D. Kondrashev, Kristallograjiya, 1961, 6, 515.
77
V. F. Dvoryankin and B. K . Vainshtein, Kristallografiya, 1961, 6, 949.
508
CRYSTALLOGRAPHY
linked in infinite spirals by hydrogen bonds between nitrogen atome. Orthorhombic aniline hydrobromide 8 5 crystallises in a distorted cesium chloridetype structure consisting of bromine and anilinium ions. I n di-(p-chloropheny1)amine 86 the valency angle of the nitrogen atom is 134". Molecules of tetrachloroquinol are almost planar, and ring dimensions are intermediate between those for a benzenoid and a quinonoid structure. The position of the hydrogen atom suggests that the two intermolecular dis1 tances [d(O.-O) = 2-92, d(O-C1) = 3.29 8 constitute a bifurcated hydrogenbond system. A three-dimensional analysis of chloranil (tetrachloro-pbenzoquinone), the molecules of which adopt the quinonoid form and are very nearly planar, has been published.88 The structure of bis-m-bromobenzoylmethane 89 (1) has been accurately determined by using three-dimensional scintillation-counter data. Symmetry requires equivalence of the two C-0 groups [d(C-0) = 1.306 & 0-015 8 1 and the intervening C-C bonds [d(C-C) = 1.393 0.015 8 of the enol form 1 in which these /I-diketones primarily exist, and thermal parameters support
Br
0 C O * c H 2 * C O
0
Br
0C H 2 * C O a O M e
('1
(2)
the interpretation that this equivalence is real rather than statistical. The molecule has a short intramolecular hydrogen-bond distance, with d ( 0 - 0 ) = 2.464 0.015 8. Strong repulsion between the oxygen atoms, possible if the hydrogen bond is bent, may result in displacement of these atoms from the molecular plane and account for the high thermal parameters normal t o the ring. The determination of the structure of deoxyanisoin (2), and a refinement of that of 4,4'-dimethoxybenzophenone,show that molecular dimensions are closely similar.90 I n the former, carbonyl and methoxygroups are coplanar with adjacent benzene rings, and planes through the rings are inclined a t 62" to each other. I n the latter, methoxy-groups are also coplanar with adjacent benzene rings. The carbonyl group is not centrally located between the planes of the adjacent benzene rings which are inclined a t about 55". I n chloro- and bromo-diphenylar~ine,~~ rotation of both phenyl rings from their ideal positions is such that only one ring can interact with the arsenic lone-pair. Pentaphenylantimony 9 2 has a square-pyramidal structure with the antimony atom lying in the pyramid about 0.5 A above the base, and a two-fold axis coinciding with the axial Sb-Ph bond. The oxygen atoms deviate from the plane of the anthracene ring in 9,lO-anthraquinol dibenz0ate.3~ The planes of the benzoate groups are
86
I. Nitta, T. WatanabB, and I. Taguchi, J . Chem. SOC. Japun, 1961, 34, 1405. K. Plieth and G. Ruban, 2. Krist., 1961, 116, 161. 8 7 T. Sakurai, Acta Cryst., 1962, 15, 443. 8 8 S S. C. Chu, G. A. Jeffrey, and T. Sakurai, Acta Cryst., 1962, 15, 661. . a 0 D. E. Williams, 1 7 L. Dumke, and R. E. Rundle, Actu Cryst., 1962, 15, 627. 4. S O H . G. Norment and I. L. Karle, Acta Cryst., 1962, 15, 873. 0 1 J. Trotter, Can&. J . Chern., 1962, 40, 1590; J . , 1962, 2567. J. Wheatley and G. Wittig, Proc. Chem. SOC.,1962, 251.
s5
509
inclined to this plane at 110". I n 1,5-dichloro- and 1,5-dibromo-anthraquinone,93 the anthraquinone nucleus has a " chair "-like shape. Only the two aromatic rings and the atoms attached directly to them are coplanar in rubrofusarin (3).94 There is a preliminary report of the structure of ~elebixanthone,~~a two-dimensionalrefinement of that of biphenylene,96 and The aromatic rings in 1,2-~yclopentenophenanthrene are slightly twisted, (4)
F .
Ph-C-C
I1
I
I
-C-CI
F . I
Ph
Ph-C-f:-$-C-Ph
I ,
I1
Ph Ph
(6)
(5).
H 2 o H c c 2
and the five-membered ring is non-planar, the two atoms attached to the aromatic nucleus lying below the mean plane and the third lying above.97 Molecular strain in 4,12-dimethyl-(2,2)metacyclophane is relieved by (5) a lengthening of the CH2-CH, bonds [d(C-C) = 1.573 & 0.003 A] and by a step-wise displacement of the two benzene rings and their distortion to a " boat ''-shape.9* Rotation of the methyl groups which appear stationary may be strongly hindered. I n the dimer of fluorotriphenylcyclobutadiene (6), the angles between the plane of the cyclobutane ring and the planes of the cyclobutene rings are about 112 & 2", with a trans-configuration about the cyclobutane ring.99 The fluorine atoms are also trans with regard to the same ring. Full details of the structure of azulene are now available,loO and a threedimensional refinement of that of 2,3-dihydro-2,3-methylene1,4-naphthaquinone has produced changes in molecular dimensions.lol There is a preliminary report of the work on cyclotetradecaheptaene which is shown to correspond to a distorted pyrene structure.lO2 Heterocyclic Compounds.-Three-dimensional refinements of the structures of furan-, thiophen-, and selenophen-2-carboxylicacid (7), and a lowtemperature study of the thiophen acid, are reported.103 The increase in
L. A. Chetkina, G. A. Gol'der, and G. S. Khdanov, Kristallografiya, 1961, 6, 628. G. H. Stout and L. H. Jensen, Acta Cryst., 1962, 15, 451. 9 5 G. H. Stout, V. F. Stout, M. J. Welsh, and L. H. Jensen, Tetrahedron Letters, 1962, 541. 9 6 T. C. W. Mak and J. Trotter, J., 1962, 1. 9 7 R. F. Entwistle and J. Iball, 2. Krist., 1961, 116, 251. 9 8 A. W. Hanson, Acta Cryst., 1962, 15, 956. D9 C. Fritchie and E. W. Hughes, J. Amer. Chem. SOC., 1962, 84, 2257. loo M. Robertson, H. M. M. Shearer, G. A. Sim, and D. G. Watson, Acta Cryst., J. 1962, 15, 1. lol W. K. Grant and J. C. Speakman, Acta Cryst., 1962, 15, 292. loa J. Bregman, Nature, 1962, 194, 679. lo3 P. Hudson, Acta cry&., 1962, 15, 919; M. Nardelli, G. Fava, and G. Giraldi, ibid., p. 737; P. Hudson and J. H. Robertson, ibid., p. 913.
93
94
510
CRYSTALLOGRAPHY
size of the heavy atom causes larger displacements from the molecular plane (0, 0.03, 0.06A for 0, S, and Se) and a decrease in the angle centred on this atom (log", 92", and 87"), but apparently does not modify the ring C-C distances. I n 2-furoic acid, the carboxyl OH group is trans with respect
(8)
CH2.CH2Me
to the hetero-atom, as compared with the &-arrangement in the other two, but reversal of the relative sizes of angles C-C-0 probably still permits some attraction between the carboxyl group and ring oxygen atom. The exocyclic C-C bond of 1.41A in 2-furoic acid is remarkably short ; corresponding values for the sulphur and selenium compounds are 1-48 and 1-44A. According to an accurate structure analysis, molecules of maleic anhydride l o 4 are non-planar, the ring hetero-atom lying 0.03 A from the molecular plane. Exocyclic C-C bonds average 1.21 8 (corrected for thermal motion); other average distances, d(C=C) = 1.303 and d(C-0) = 1.388, both & 0.005 8, are shorter than the double-bond and the single-bond value respectively. I n N-p-bromophenylsuccinimide 105 and N-methylpyrrole, the nitrogen atom forms three coplanar bonds. The five-membered ring of pyrazoline hydrochloride lo7 lies in a mirror plane with d(C=N)= 1.255 & 0*009, d(N-N) = 1.468 & 0.007, d(C-N) = 1.498 & 0.008, and d(C-C) = 1.473, 1.472 (both 0.010 A), and molecules are linked by hydrogen bonds with d(N-H.41) = 3-092 & 0.005 8. Similar bonds occur in pyridine hydrochloride lo* [d(N-H-Cl) = 2.95 8 and in the substituted triazolopyri1 midine lo9 (8) where d(N-H.-Cl) = 3.18 and 3-30A. The latter molecule is planar and has two structural features reminiscent of purines, namely short C-C and C-N bonds in the pyrimidine ring, and molecular dimensions inexplicable in terms of simple resonance theory. I n 5-carboxymethylcytosine (9), exocyclic atoms deviate significantly from the plane of the pyrimidine ring.110 A feature of the crystal structure is a transfer of the
A
H02C. [CHJ 3-N-N.[CH2]
COzH
carboxyl proton to a pyrimidine nitrogen atom in half the molecules (which therefore correspond to zwitterions). As a result, a proton is shared by a pair of nitrogen atoms related by a centre of symmetry, and another proton is similarly shared by a pair of oxygen atoms. The hydrogen bonds
I04
Io6
R. E. Marsh, E. Ubell, and H. E. Wilcox, Acta Cryst., 1962, 15, 35. J. Barassin, G. Tsoucarb, and H. Lumbroso, Compt. rend., 1961, 253, 2546. lo6L. V. Vilkov, P. A. Akishin, and V. M. Presnyakovs, Zhur. Ptrukt. Khim., 1962,
3, 5.
M. Nardelli and G. Fava, Acta Cryst., 1962, 15, 214. C. RBrat, Acta Cryst., 1962, 15, 427. l o 9P. G. Owston and J. M. Rowe, A d a Cryst., 1962, 15, 231. I1o R. E. Marsh, R. Bierstedt, and E. L. Eichhorn, Acta Cryst., 1962, 15, 310.
S U T O R : ORGANIC STRUCTURES
511
formed are only statistically symmetrical since the protons appear randomly distributed between sites closer to one or other atom in each pair. links Unusual hydrogen bonding in piperazine-l,4-dibutyricacid (10) hydroxyl oxygen atoms to ring nitrogen atoms of adjacent molecules with d(0-H-N) = 2.60 & 0.01 (cf. that in meso-l,4-diaziridin-l'-ylbutane2,3-diol l12). There is a preliminary report of the structure of isoquinoline chlorohydrate,113 and two independent investigations show that benzofuroxan 114 has the benzofurazan 1-oxide structure (11 ). I n 9,10-dihydro-9-hydroxy-9 -phosphaphenanthrene 9-oxide ( 12),115 the two benzene rings are not conjugated [d(C-C) = 1.57 0.05 a]. The two
OH
P-C bonds are 1.79 and 1-80 8. C-S bondsin2-methylthiobenzothiazole (13) are 1.73, 1.77, 1.78, and 14328, the last corresponding to the S-Me distance.116 I n merocyanine (14),the two cyclic sulphur atoms are in the
trans-position.117 The rhodanine ring is planar but the two methylene carbon atoms deviate from the plane of the other ring. Methyl metadithiophosphonate (15) is a dimer of crystallographic symmetry 2/m.llS The P-S distances, 2-14&0-02 for a cyclic and 1.94&0.02 8 for an exocyclic bond, correspond to the single and the double bond value respectively. I n tetramethyl-NN'-bistrimethylsilylcyclodisilazane,119 there is no significant difference between cyclic and exocyclic Si-N bonds, which average 1.719 8. A puckered eight-membered ring of alternate phosphorus and nitrogen atoms occurs in tetrameric phosphonitrilic dimethylamide 120 and metastable phosphonitrilic chloride;121 d(P-N) = 1-58 and 1.57 A respectively. I n the former compound exocyclic P-N bonds of 1.67 and 1.69 A are considerably shorter than the single bond value. Addition Compounds.-In the 1 : 3 addition compounds formed by iodoll1 Potter, Nature, 1962, 112 Ann. Reports, 1961, 475.
R.
F. Genet, Compt. rend., 1962, 254, 2389. D.Britton and W. E. Noland, Chem. and Ind., 1962, 563; R . Hulme, ibid., p. 42. l15P. J. Wheatley, J . , 1962, 3733. 11* P. J. Wheatley, J . , 1962, 3636. 11' G. Germah., P . Piret, M. van Meerssche, and J. de Kerf, Acta Cryst., 1962, 15, 373. 11* P. J. Wheatley, J . , 1962, 300. l l * P . J. Wheatley, J . , 1962, 1721. l * O G. J. Bullen, J., 1962, 3193. 121 R. Hazekamp, T. Migchelsen, and A. Vos, Acta Cryst., 1962, 15, 539.
11*
58,
193, 673.
512
CRYSTALLOGRAPHY
form with sulphur 122 (CH13,3S,) and with quinoline 123 each iodine atom is linked to a sulphur atom and t o a quinoline nitrogen atom by chargetransfer bonds of length 3-50 and 3.05 & 0.03 8, respectively. The values of ,/(C-I-X), 178" and 177", where X = S and N, indicate a linear arrangement of these atoms. The sulphur and selenium atoms in the iodine complex of 1,4-selenothian (C4H,SSe,21,) are disordered, 124 each site being filled by 3Se is. As the iodine atoms in the iodine complexes of 1,4-dithian and lY4-diselenanare bonded t o the sulphur and t o the selenium atoms of the six-membered ring in the equatorial and axial positions, respectively, there are several possibilities for the present compound. The arrangement adopted is the equatorial one. A refinement of the chloranil-hexamethylbenzene complex 1 2 5 indicates a coplanar structure for the two molecules, instead of the puckering and non-planarity observed previously but thought not t o be significant. The complex of cupric chloride and 1,2,4-triazole 126 consists of a distwo torted octahedral co-ordination group of two nitrogen atoms a t 1.98 8, chlorine atoms at 2.34 8,and two chlorine atoms at 2.77 8 about each copper atom. The infinite chains of octahedral groups joined by sharing edges are linked by triazole molecules. Natural Products and Related Compounds.-Again this year, this section contains a high proportion of the organic molecules studied. A refinement of the structure of codeine hydrobromide dihydrate, using three-dimensional data, and the absolute configuration of the molecule are r e ~ 0 r t e d . l ~ 'Complete structure analyses of ( -)-N-methylgelsemicine hydriodide 128 and calycanthine 129 are now available. I n the latter paper, an intermolecular distance with d(C-0) = 3-18 8 is compared with similar values in other alkaloids. X-Ray work on chimonanthine,130 an isomer of calycanthine, has shown which of two chemically feasible structures is correct. Like calycanthine, the molecule adopts the cis-configuration (16). I n casimiroedine 131 (17) the nitrogen atom attached equatorially to the ,&glucose ring
Me
T. Bjorvatten, Acta Chem. Scand., 1962, 16, 749. T. Bjorvatten and 0. Hassel, Acta Chem.. Scand., 1962, 16, 249. 1 2 4 H.Hope and J. D. McCullough, Acta Cryst., 1962, 15, 806. 1 2 5 N. D. Jones and R. E. Marsh, Actu Cryst., 1962, 15, 809. 126 J. A. J . Jarvis, Acta Cryst., 1962, 15, 964. 1 2 7 G. Kartha, F. R. Ahmed, and W. H. Barnes, Acta Cryst., 1962, 15, 326. li8 M. Przybylska, Acta Cryst., 1962, 15, 301. l Z Q A. Hamor and J. M. Robertson, J., 1962, 194. T. 1 3 0 I. J. Grant, T. A. Hamor, J. M. Robertson, and G. A. Sim, Proc. Chem. SOC., 1962, 148. 13l S . Raman, J. Reddy, W. N. Lipscomb, A. L. Kapoor, and C. Djerassi, Tetrahedron Letters, 1962, 357.
122
lZ3
513
forms three coplanar bonds and in the dichloride studied is not protonated. The CH,*CH,*NHMe chain is somewhat extended. There are preliminary reports of work on isophotosantonic lactone, 132 hunterburnine,l33 hetisine hydrobromide, and gedunin. 135 The positions of the substituents in hetisine hydrobromide differ from those suggested from chemical evidence. The structure deduced for gedunin by analogy with limonin and the structures of al-bromopicrotoxinin 136 and bromogeigerin acetate 137 are confirmed. Samandarine,138 one of the salamander alkaloids, the only genuine alkaloids so far known in animals, has a sterol skeleton like that of EiB-androstane, with the same cis-trans-trans-junction between the four rings. From the empirical formula, the structure of himbacine hydrobromide a t -150" has been defermi11ed.1~9 The planarity of the lactone group and the shortening of the C-0 bond adjacent t o the keto-group, observed in
Me
the dibromolactone from jacobine,lgOhave been demonstrated in this compound and in shellolic bromolactone hydrate lgl (lactone plane not calculated), and in iridomyrmecin (18) and its epimer isoiridomyrmecin ( 19).142 The difference in biological activity of the last two may be related to their different stereochemistry. I n iridomyrmecin, the cyclopentanoid ring is endo, in the epimer it is exo t o the six-membered ring. A preliminary report of a-D-glucose monohydrate l g 3has shown that the pyranose ring is " chair "-shaped with molecular dimensions fairly similar t o those in a-D-glucose. I n the crystal, there is a very short intermolecular distance, with d ( C - 0 ) = 2.61 8. The pyranose ring in methyl-3,4,6-tri-glucopyranoside 4 4 is also " chair "O-acetyl-2- chloromercuri-2-deoxy-b-~ shaped with substituents attached equatorially. I n an accurate three-dimensional analysis of E-lysine monohydrochloride dihydrate,145 the following average distances have been found : d(C-NH3+)= 1.482 & 0.004,d(C-C) = 1.524 & 0.003 A, L(C-C-C) = 111.7"
J. D. M. Asher and G. A. Sim, Proc. Chern. SOC.,1962, 111. J. D. M. Asher, J. M. Robertson, G. A. Sim, M. F. Bartlett, R . Sklar, and W. I. Taylor, Proc. Chem. SOC.,1962, 72. 134 M. Przybylska, Canad. J . Chem., 1962, 40, 566. 135 S. A. Sutherland, G. A. Sim, and J. M. Robertson, Proc. Chsm. $oc., 1962, 2 2 2 . 136 B. M. Craven, Acta Cryst., 1962, 15, 387. 1 ' J. A. Hamilton, A. T. McPhail, and G. A. Sim, J., 1962, 708. 3 G. Weitz and E. Wolfel, Acta Cryst., 1962, 15, 484. 139 J. Fridrichsons and A. McL. Mathieson, Acta Cryst., 1962, 15, 119. 140 Ann. Reports, 1961, 58, 478. 141 E. J. Gabe, Acta Cryst., 1962, 15, 759. 142 J. F. McConnell, A. McL. Mathieson, and B. P. Schoeborn, Tetrahedron Letters, 1962, 445; B. P. Schoeborn and J. F. McConnell, Acta Cryst., 1962, 15, 779. 14s R. C . G. Killean, W. G. Ferrier, and D. W. Young, Acta Cryrt., 1962, 15, 911. 144 H.W. W. Ehrlich, J., 1962, 509. 145 D. A. Wright and R . E. Marsh, Acta Cryst., 1962, 15, 54.
132 133
514
CRYSTALLOGRAPHY
(cf. those in NN'-hexamethylenebispropionamide p. 506). All hydrogen atoms belonging t o nitrogen atoms and water molecules participate in hydrogen bonds and one proton a.ttached to a nitrogen atom forms a bifurcated bond. N-acetylglycine 146 has also been refined in three dimensions, and bond lengths and angles are very similar t o those reported earlier. The determination of the absolute configuration a t the asymmetric sulphur atom in ( +)-8-methyl-L-cysteine sulphoxide may represent the first of its kind.147 The crystal structure consists of pairs of sheets of molecules held together by hydrogen bonds between the nitrogen atom of one molecule and surrounding oxygen atoms of different molecules. Di(histidino)zinc(n) dihydrate 149 consist of zinc pentahydrate 1 4 8 and di-(L-histidino)zinc(II) atoms approximately tetrahedrally co-ordinated by two or-amino- and by two imidazole-nitrogen atoms. Two carbonyl oxygens can also be considered loosely co-ordinated. A small twist of the peptide group between the prolyl and hydroxyproline groups, and a flexibility in the proline ring observed in the synthetic peptide t oluene-p- sulphonyl-L-prolyl-Lhydroxyproline m ~ n o h y d r a t emay ~ of importance in the construction of mole, ~ ~ be cular models of peptides and proteins. I n vitamin B, (thiamine hydrochloride) (20) 151 the planes of the thiazolium and pyrimidine rings make a dihedral angle of 76" and are twisted so that the amino-group in the latter ring and the CH-group in the former ring are close. Parts 111, IV, and V of the structure of vitamin B,, describe the work in Oxford and Princeton on the vitamin.152 Parameters for ninetythree atoms of the molecule, fifteen water molecules, and seven less well defined water molecules are given. The latest difference maps have small maxima which confirm the identification of the various single-atom substituents in the nucleus as methyl groups. D. J. S.
W. COCHRAN. D. J. SITTOR.
J. Donohue and R. E. Marsh, Acta Cryst., 1962, 15, 941. R. Hine, Acta Cryst., 1962, 15, 635. 14* M. M. Harding and S. J. Cole, Proc. Chern. SOC., 1962, 178. 149 R. H. Kretsinger, R. F. Bryan, and F. A. Cotton, Proc. Chem. Soc., 1962, 177. lSo J. Fridrichsons and A. McL. Mathieson, Acta Cryst., 1962, 15, 569. 15l J. Kraut and H. J. Reed, Acta Cryst., 1962, 15, 747. 152 J. G. White, Proc. Roy. SOC., 1962, A , 266, 440; D. C. Hodgkin, J. Lindsey, M. Mackay, and K. N. Trueblood, ibid., p. 475; D. C. Hodgkin, J. Lindsey, R. A. Sparks, K. N. Trueblood, and J. G. White, ibid., p. 494.
146
14'
I N D E X OF AUTHORS NAMES
Ab, G., 455. Abel, E. W., 142, 145. Abeles, R. H., 403, 408, 409, 420. Abell, P. L., 49. Abraham, D. J., 322. Abraham, M. H., 143. Abraham, R. J., 201, 202, 364. Abrahamson, E. W., 452. Abrahamsson, S., 276, 284. Abramovitch, R. A., 336. Abrams, R., 374. Abramsky, T., 393, 403. Acheson, R. M., 319, 324, 325, 338. Ackerman, M., 119, 120. Acquista, A., 121. Aczel, T., 199, 497, 498. Adam, G., 356. Adams, D. M., 173. Adams, F., 490. Adams, G. A., 370. Adams, J. Q., 49. Adams, K. A. H., 336. Adams, R. N., 48, 52, 482. Adams, R. W., 60. Adams, W. S., 445. Adamson, A. W., 171. Addison, C. C., 178. Adema, E. H., 47. Adityachaudury, N., 347, 352. Adrian, F. J., 48, 57, 58, 205. Ae Im, Y., 175. Affrossman, S., 254. Affsprung, H. E., 95. Agar, J., 382. Agarwala, V. S., 461. Agirbiceanu, I., 120. Agosta, W. C., 272. Ahearn, A. J., 120. Ahmad, M., 357. Ahmed, F. R., 512, 533. Ahuja, H. S., 145. Aia, M. A., 500. Aikens, D. A., 455. Aizenshtat, E. L., 361. Akerlind, L., 106, 127. Akhren, A. A., 197. Akhtar, M., 305, 483. Akishin, P. A., 506, 510. Akiyama, S., 269. Akiyoshi, S., 299. Ahbran, D. M., 258. Alberty, R. A., 244. Alcock, N. W., 151. Alder, B., 65. Alder, B. J., 97. Alderman, P. R. H., 178. Aldrich, R. A., 393. Alekseeva, D. P., 165. Alexander, C. A., 153. Alexander, G. V., 478. Alexander, L. E., 503. Alfonsi, B., 481. Alfredsson, B., 448. Alicino, J., 332. Alimarin, I. P., 450. Alivastatos, S. G. A., 416. Alivisatos, S. G. A., 417. Allan, J. E., 479. Allardt, H. D., 161. Allegra, G., 151. Allen, A. D., 164. Allen, E., 159. Allen, E. R., 37. Allen, F. W., 376. Allen, G., 225. Allen, J. C., 226, 265. Allen, S. H., 403, 405. Allen, W. F., 283. Allendorf, H. D., 37. Alleston, D. L., 143. Alley, S. K., 84. Allfrey, V. G., 380. Allinger, A. L., 196. Allinger, N., 317. Allinger, N. L., 198, 286. Allison, M. J., 274. Allner, K., 328. Allred, A. L., 66. Al-Madhi, A. A. K., 493. Almenningen, A., 190. Alonso, C., 434. Alpert, D., 8, 9. Alsop, D. J., 310. Altaner, C., 447. Altman, K. T., 398. Altshuller, A. P., 449, 465. Amai, R. L. S., 353. Amaya, K., 95, 96. Amberger, E., 145, 147. Amdur, I., 88, 89. Amelunxen, R., 425. Amiel, Y., 198, 307, 316. Amin, El. S., 365. Amma, E. L., 166, 169. Ammann, R., 463. Amschler, H., 314. Amster, R. L., 137. Ananchenko, S. N., 306. Anand, V. D., 460. Anantaraman, A. V., 96. Andersen, B., 359. Andersen, J. R., 202. Anderson, A. G., 414. 515 Anderson, B., 417. Anderson, B. C., 281. Anderson, B. M., 247, 416. Anderson, C. D., 135, 375. Anderson, D. L., 84. Anderson, D. M. W., 370, Anderson, D. R., 237. Anderson, J. C., 253. Anderson, J. D., 361. Anderson, J. H., 54. Andersen, J. R., 327. Anderson, L., 361. Anderson, M. M., 66. Anderson, N. G., 445. Anderson, P. S., 335. Anderson, R., 76, 83, 84. Anderson, R. S., 53, 109, 205. Anderson, S., 170. Andersson, L. H., 448. Andreades, S., 280. Andreev, N. S., 190. Andreoli, M., 494. Andresen, H. G., 46. Andrew, T. R., 479. Andrews, H., 337. Andrews, L. J., 82, 217, 220, 226, 233. Andrews, P., 361. Andrianov, K. A., 141. Anet, E. F. L. J., 327, 363. Anet, F. A. L., 192, 286, 357. Anet, R., 282. Angelici, R. J., 177. Anger, V., 442. Angers, M., 434. Angier, R. B., 283. Angus, W. R., 125. Angyal, S. J., 362, 363, 365. Anisonyan, A. A., 27. Anliker, R., 428, 429. Annaka, S., 504. Annan, W. D., 370. Anner, G., 305. Anneser, E., 332. Anselme, J.-P., 330. Anson, F. C., 472. Antipova-Karataeva, I. I., 154. Antkowiak, W., 296. Antonaccio, L. D., 204, 352, 353. Antonakis, K., 362. Antonescu, R., 314. Antoniades, H. N., 427. Apirina, R. M., 451. Aposhian, H. V., 374. Appel, H. H., 344.
516
INDEX OF AUTHORS' NAMES
Appel, R., 145, 148, 241, 258, 280, 323. Appella, E., 419. Aprahamian, N. S., 232. ApSimon, J., 358. ApSimon, J. W., 243, 296. Arai, S., 51. Arakawa, H., 291. Arapovid, I., 478. Archer, A. P. G., 353. Archer, D. A., 338. Arden, J. W., 495. Ardon, M., 158, 178. Arellano, R., 336. Arens, J. F., 270. Argoudelis, A. D., 341. Arigoni, D., 299, 305. Ariyoshi, U., 368. Arm, H., 95. Armand, J., 486. Arnason, B., 260. Arnaud, P., 276. Arndt, C., 271. Arnett, E. M., 308. Arnold, N., 319. Arnstein, H. R. V., 376, 381, 406. Arojan, A., 344. Aroney, M., 192. Aroney, M. J., 190, 191. Arotsky, J., 150, 151. Arsonault, G. P., 391. Arthur, J. C., jun., 369. Arthur, J. R., 12. Arya, V. P., 295, 297. Asaba, T., 20. Asatiani, Ya. V., 131. Ascherl, A., 332. Ashby, E. C., 133, 137,256. Asher, J. D. M., 291, 294, 351, 513. Ashmore, P. G., 24. Ashworth, A. J., 91. Asinger, F., 320. Aslanov, G. A., 453. Asperger, S., 223. Aspinall, G. O., 370. Asprey, L. B., 154. Asthana, 0. P., 460. Astle, M. J., 319. Astraclian, L., 379. Asundi, R. K., 128. Aszalos, A., 364. Athavale, V. T., 444, 478. Atherton, N. M., 51, 59. Atkim, P. W., 54, 55, 56. Atkinson, M. R., 417. Atsuyoshi, O., 230. Aubrey, D. W., 133, 136. Augl, J. M., 176. August, J. T., 431. Aurell, B., 447, Avidor, Y., 418. Avram, M., 309. Avramerko, L. I., 21, 42, 43, 44.
Axelrod, B., 331, 358. Axelrod, L. R., 430. Axford, D. W. E., 27. Ayer, W. A., 337, 357. Ayers, W. A., 406. Aylward, F., 257. Aylward, G. H., 488. Ayres, G. H., 479, 482. Ayrey, G., 224. Ayscough, P. B., 53. Azarnooth, A., 98. Azatyan, V. V., 25. Azim, S., 482. Azizov, U., 369. Azizyan, T. A., 230. Bazcrchers, W. H., 297. Babaeva, A. V., 165. Babel, D., 164. Babko, A. K., 437. Bacharach, A. L., 427. Bachman, G. L., 241. Baciocehi, E., 231. Backeberg, 0. G., 262. Bacon, R. G. R., 234, 258. Baddeley, G., 217, 246. Badding, V. G., 256. Badger, G. M., 308. Baeckmann, A. V., 444. Baer, H. H., 366. Bafus, D. A., 130, 206. Bag, S. P., 451. Bagdasarian, M., 388. Bagnall, K. W., 153. Baikov, V. I., 128. Bailar, 5.C., jun., 165, 171. Bailey, A. J., 361. Bailey, N., 47. Bailey, R. A., 489. Bailey, R. W., 367. Bailey, S. W., 447. Bailey, W. J., 273, 285, 307. Bain, P. J., 235. Bains, M. S., 156. Baird, J. C., 53, 54. Baird, R., 219. Baird, S. L., 62. Baiulescu, G., 450. Bak, B. 195 199 202, 327, 329. Baker, A. E., 157. Baker, A. J., 295. Baker, B. R., 365, 366, 375, 424. Baker, C. H., 99. Baker, E. B., 132. Baker, F. W., 232. Baker, J. A., 336. Baker, R., 232. Baker, R. H., jun., 418,421. Baker, W., 309. Baker, W. A., 154. Balaban, A. T., 307, 314. Balandina, M. A., 459. Balhzs, L., 473. Baldeschwieler, J. B., 144.
Baldinus, J. G., 470. Baldwin, J. E., 286. Baldwin, M. E., 194. Baldwin, R. R., 22, 23, 24, 25. Ball, D. F., 478. Ball, D. H., 365. Ball, J. J., 121. Ballard, R. E., 169. Balthausen, C. J., 45, 46, 128, 157. Baltazzi, E., 324, 389. Baltchefsky, H., 418. Bamford, C., 246. Bamford, C. H., 49. Ban, Y., 348, 350. Bandi, L., 431. Banick, W. M., jun., 457. Banister, A. J., 148. Banks, B. E. C., 244, 246. Banks, C. V., 170, 485. Banthorpe, D. V., 238. Barabanova, A. S., 157. Baranova, L. I., 165. Barassin, J., 510. Barber, M., 32. Barbier, M., 278. Barbieri, P., 412. Barchielli, R., 411. Barclay, G. A., 163. Barclay, L. R. C., 253. Bard, A. J., 462, 463, 464, 472, 484. Bardenstein, S. B., 480. Bardsley, W. G., 349. Barendrecht, E., 462, 463. Barford, R. A., 275. Barger, R. L., 102. Barker, H. A., 400, 401, 402, 403, 413. Barker, J. A., 89, 95. Barker, R., 362. Barker, S. A., 277, 361, 364, 368. Barltrop, J. A., 294, 299, 302. Barnard, J. A., 37. Barner, R., 237. Barnes, C. S., 200, 292. Barnes, W. H., 503, 512. Barnett, B. H., 410. Barnett, L., 380. Barney, J. E., 467. Barnum, D. W., 169. Barr, J. K., 448. Barrall, E . M., 1 , 499. 1 Barrens, J., 194. Barreto, R. C. R., 479. Barrett, J., 396. Barrett, J. M., 411. Barron, D. N., 420. Barrow, R. F., 101, 102, 106, 107, 119, 121, 124, 126, 127, 128. Barry, G. W., 233. BBrta, R., 499.
I N D E X O F AUTHORS N A M E S
517
Bartelink, H. J. M., 47. Bartell, L. S., 189. Bartels, H., 150. Barth-Wehrenalp, G., 170. Bartkus, E. A., 310, 331. Bartky, I. R., 128. Bartlett, M. F., 351, 353, 513. Bartlett, N., 130, 161, 165. Bartlett, R. K., 134. Bartley, W. J., 312. Bartnik-Kurzawinska, J., 465. Bartocha, B., 137. Barton, D. H. R., 243, 260, 263, 267, 286, 293, 294, 296, 300, 305, 306, 343. Barton, J. W., 309, 338. Bartos, J., 442. Bartosinski, B., 412, 413. Bartz, K. W., 497. Bartz, Q. R., 365. Barua, A. K., 301. Bashilova, N. I., 450. Basilio, C., 381. Basolo, F., 163, 175, 177. Bass, A. M., 102, 127. Bassett, J. Y., 234. Bassilios, H. F., 262. Bastiansen, O., 190. Bastien, B. N., 219. Bate, R., 448. Bateman, L. C., 218. Bates, J. A. R., 488. Rates, J. F., 483. Bates, R. B., 200, 275, 292, 303. Bates, R. G., 439. Batorewicz, W., 222. Batovskaya, T. A., 486. Battersby, A. R., 343, 354. Batterman, B. W., 504,505. Battiste, M. A., 314. Battle, A. M. del C., 394. Bauer, H., 324. Bauer, L., 202. Bauer, R., 131, 182. Bauer, V. J., 196. Baulieu, E. E., 433. Baumgardner, C. L., 308. Baumgarter, F., 183, 184. Baun, W. L., 496. Bautz, E., 976. Bautz, E. K. F., 350. Baxter, J. N., 359. Baxter, R. M., 343. Bayard, R. T , 8. Bayer, O., 279. Bayer, R. P., 242. Baylis, E. K., 217. Baylouny, R. A., 285, 307. Bazinet, M. L., 497. Beachell, H. C., 132. Beak, P., 353. Beard, C., 197. .Beam, A. G., 419, 420.
Bearse, A. E., 334. Beaton, J. M., 267, 305. Beattie, I. R., 138, 141, 142, 155. Beau, G., 479. Beaudet, R. H., 195. Beaven, G. H., 233. Bbcart, M., 112. Beck, F., 252. Beck, W. S., 410. Becka, L. N., 505. Becke-Goehring, M., 145, 146, 148. Beckel, C. L., 114. Beckel, C., 115. Beclser, E., 411, 412. Becker, E. D., 329. Becker, J. A., 12. Beckers, H. G., 146. Beckmann, S., 287. Beckwith, A. L. J., 236. Bedford, A. F., 330, 333. Bedford, C. T., 276, 288, 319. Bedford, G. G., 192. Beech, J. A,, 32. Beenakker, J. J. M., 86, 87. Beer, L., 395. Beers, R. F., 371. Beg, M. A. A., 143. Begbie, R., 370. Begemann, P. H., 275. Beggs, B. H., 471. Behrens, H., 149, 177. Behun, J. D., 442. Beider, S. Ya., 27. Beilby, A. L., 463. Belardini, M., 295. Belcher, C. B., 479. Beletskaya, I. P., 230. Belgorskii, I. M., 31. Belil, G., 270. Bell, C. L., 202. Bell, E. A., 194. Bell, H. M., 210. Bell, J. A., 241. Bell, J. L., 420. Bell, K. M., 43. Bell, R. A., 298. Bell, R. P., 246. Bell, S. C., 339. Bell, T. N., 147. Bellar, T., 449. Bellasio, E., 323. Bellemans, A., 95. Bellig, E., 163. Bellin, J. S., 320. Bello, L. J., 374. Belohlav, L. R., 231. Belousov, V. P., 97. Belov, N. V., 505. Belova, V. I., 165. Ben Aim., R, 37, 38. Bender, M. L., 225, 246, 247, 248, 249, 250, 252. Bendich, A., 375.
Ben-Efraim, D. A., 198,307. Benesi, H. A., 82. Benik, I., 356. Benington, F., 273, 348. Benitez, A., 375. Benjamin, B. M., 212. Benjamin, L., 97. Benkeser, R. A., 333. Benkovic, P., 247. Bennett, H., 455. Bennett, M. J., 185. Bennett, R., 201. Bennett, R. G., 110. Bennett, R. P., 233. Benson, A., 390, 394. Benson, G. C., 97. Benson, M., 219. Benson, R. E., 52. Benson, S. W., 228. Bent, R., 480. Bentrude, W. G., 253. Benz, R., 153. Benzer, S., 382. Berck, B., 487. Berecka, M., 476. Berends, W., 371. Berezowsky, J. A., 357. Berg, P., 379, 382. Berg, R. A., 127. Berge, D. G., 469. Bergeim, F. Ip., 342. Bergelson, L. D., 260. Berger, A., 253. Berger, J. G., 197. Rergman, I., 458. Eergman, J., 317. Bergson, G., 333. Bergstrom, X., 276, 284. Berka, A., 452, 453, 467, 468, 470. Berkelhammer, G., 414. Berkman, J. I., 403. Berlin, A., 499. Berlin, A. J., 196, 282. Berlin, A. M., 155. Berliner, D. L., 429. Berliner, E., 233. Berlinguet, L., 265. Bernal, I., 47, 51, 163, 175, 178. Bernard, R. E., 332. Bernasek, E., 295. Bernhard, C., 316. Bernhard, S. A., 253. Bernhauer, K., 375, 402, 411, 412, 413. Bernheim, R. A., 66. Bernstein, H. J., 64. Bernstein, J., 342. Beroza, M., 278, 329, 447. Berson, J. A., 211, 227, 228, 229, 230, 253. Bertoldi, S., 481. Bertrand, R. R., 89. Bessman, M. J., 374. Bestian, H., 185.
518
INDEX
OF AUTHORS NAMES
Bestman, H. J., 260, 261. Bestmann, H. J., 274. Bethea, T. W., 258. Betrand, M., 272. Betteridge, D., 479. Beu, K. E., 502. Beukers, R., 371. Beutner, H., 177. Bevan, C. W. L., 329. Bews, A. M., 370. Beyermann, K.: 438. Bezjak, A., 478. Bezuglyi, V. D., 486. Bhatnager, M. L., 461, 468. Bhatnagar, R., 461, 468. Bhasin, R. L., 444, 478. Bhattacharaya, A., 354. Bhattacharaya, P. K., 355. Bhattacharyya, S. C., 290. Bhattacharyya, S . N., 96. Bheernasankara Rao, C., 450. Bibber, M. J. V., 374. Bickel, A. F., 307, 313, 314, 315. Bickelhaupt, F., 358. Bieber, R. E., 416. Bieber, T. I., 261. Biellmann, J.-F., 303. Bielstein, H. O., 135. Biemann, K., 194,204, 352, 353. Bienenstock, A., 506. Bierderbick, K., 330. Bierstedt, R., 510. Bigley, D. B., 294. Bigorajski, G., 38. Bijvoet, J. M., 503. Bilefield, L. I., 491. Billig, E., 175. Billman, J. H., 256. Bills, D. G., 102. Bines, B. J., 370. Bingel, W. A., 114. Binkowski, B. B., 138. Binks, R., 343. Biordi, J., 217. Birch, A. J., 266, 290, 294, 306, 314, 319, 329, 360. Bird, C. W., 339. Bird, R. B., 88. Birkeland, S. P., 267. Birkhimer, C. A., 332. Birkofer, L., 328, 376. Birnie, G. D., 409. Birnkraut, W., 144. Birtwistle, J. S., 296. Bishop, C. T., 246,359,362, 366. Bishop, E., 453, 467, 471. Bishop, E. O., 64. Bisht, C. D., 453. Biswas, B. B., 374. Bittler, K., 183. Bittrich, H. J., 95, 96. Bjerrum, J., 174.
Bjork, R. G., 461. Bjorvatten, T., 512. Black, W. A. P., 364. Blackadder, D. A., 238. Blackburn, G. M., 318, 341. Blackie, M. S., 66, 67. Blackman, E. J., 235. Blades, A. T., 223. Blaha, K., 344. Blake, A. R., 40. Blake, C. A., jun., 447. Bland, B. J., 485. Blankenstein, G., 320. Blanks, R. F., 92. Blatter, H. M., 198. Blay, N. J., 131. Blaiek, A., 500. Blight, M. M., 172. Block, B. P., 170. Blodgett, K. B., 15. Bloembergen, N., 66. Bloemendal, H., 383. Blom, J., 359, 361. Blomberg, C., 266. Blomquist, A. T., 183, 269, 281, 308. Bloomer, J. L., 233, 286. Bloomfield, J. J., 262. Blount, W., 338. Blow, D. M., 502. Blumberg, E. A., 39. Blundell, A., 35. Bly, R. K., 279. Blyholder, G., 14. Boase, D. G., 456. Boaz, H. E., 355. Bobbitt, J. M., 204, 344. Bock, H., 143, 144, 177. Bock, R., 484. Bockris, J. OM., 167. Bodanszky, M., 332. Bode, H., 151. Boden, N., 145. Bogri, T., 349. Bohm, R., 364. Bohme, D., 99. Boenicke, H., 140. Boesman, E., 55. Boeters, H., 145, 147. Boettcher, F.-P., 235, 335. Boettcher, R. R., 337. Bogdanova, A. A., 141. Bogorad, L., 385, 391, 392, 393, 395. Bogoyavlenskaya, M. L., 26. Bohlmann, F., 271, 329, 345. Bojesen, E., 431. Bolinder, A., 410. Boling, W. H., 445. Bolte, E., 432. Bolton, C. H., 366. Bolton, H. C., 504. Bolton, J. R., 50, 51,52, 58, 60, 206.
Bond, H. E., 445. Bond, W. L., 502. Bondivenne, R., 479. Bonelli, R. A., 235. Bonet, J. J., 303. Bonham, R. A., 192. Bonitz, R. E., 459. Bonnaire, Y., 482. Bonner, T. G., 221, 362. Bonner, W. A., 212, 367. Bonnet, R., 411. Bonnichsen, R., 418. Boocock, G., 44. Boomer, G. L., 493. Booman, K. A., 54. Boone, J. L., 135. Boord, C. E., 32. Booth, D., 25. Booth, G., 173, 178. Booth, H., 338. Bor, G., 177. BorEib, S., 209. Borden, G. W., 285. Bordwell, F. G., 223. Borek, E., 374. Boretti, G., 411, 412. Borisov, A. E., 147. Bork, V. A., 462. Bornowski, H., 271, 329. Borodin, P. M., 69. Borowitz, I. J., 201. Bos, H., 47. Bosch, J., 270. Bosch, L., 383. Bose, 5 L., 367. . Bose, P. K., 301. Bose, S., 453. Boser, H., 420. Boss, C. R., 46. Boston, J. L., 181. Bothner-By, A. A., 192, 198, 300, 307, 342. Bott, R. W., 254. Bottei, R. S., 170. Bottini, A. T., 193, 231, 320. Bottomley, G. A., 91. Bouben, N. Ya., 52. Boulton, A. J., 332. Bouquet, G., 176. Bourne, E. J., 221, 362. Bourns, A. N., 219, 224. Bouten, P., 491. Bowers, A., 305. Bowers, V. A., 48, 56, 57,
58, 205.
Bowman, R. L., 495. Boyer, J. P., 300. Braddock, L. I., 449. Bradford, J. L., 134. Bradley, D. C., 131, 156, 157, 168, 170. Bradley, J. N., 19. Bradley, M. J., 153. Bradlow, M. L., 431. Bradlow, H. L., 433.
INDEX OF AUTHORS NAMES
519
Bradshaw, J. S., 230. Bradsher, C. K., 347. Brady, D., 142. Brady, R. O., 402, 413. Braendlin, H. P., 229, 231, 288. Bragg, D. R., 327. Brahm, Dev., 479. Bminina, E. M., 156. Brainina, Kh. Z., 486. Bramley, R., 199. Brand, L., 421. Brandon, N. E., 247. Brandon, R. W., 60. Brandsma, L., 270, 340. Brantner, H., 454. Brasch, J., 324. Brasseur, L., 273. Bratten, D., 22. Braunling, H., 262. Brauer, G., 161. Bray, H. M., 479. Bray, R., 411. Bredereck, H., 367. Breenlee, K. L., 487. Bregman, J., 509. Breig, E. L., 195. Breiter, J. J., 258, 322. Bremond, M., 128. Brenet, J., 161. Brennan, G. L., 132. Brennan, R., 476. Brenner, S., 379, 380. Breslow, D. S., 176. Breslow, R., 210, 281, 286, 307, 314. Bretscher, M. S., 381. Breuer, H., 433. Brewer, F. M., 138. Brewer, H. W., 348, 354. Brewer, L., 100, 127, 128. Brey, W. S., jun., 196. Brickman, M., 232. Brieger, G., 285. Briegleb, G., 82. Brieux, J. A., 235. Briggs, R., 482. Bright, A., 344. Brignell, P. J., 337. Brigorghe, M., 176. Brimacombe, J. S., 364, 368. Bringi, N. V., 353. Brinkman, A. A. A.M., 441. Brisdon, B. J., 159. Britton, D., 511. Brivati, J. A., 51, 55, 56. Brochmann-Haussen, E., 448. Brocklehurst, K., 246. Brocklehurst, P., 199. Brodskaya, V. M., 454. Brody, J. K., 101, 128. Briill, H., 442. Broida, H. P., 102,107, 116, 127.
Bromels, E., 132. Bromley, D. A., 101. Brook, M., 125. Brooker, A. C., 320. Brookes, P., 373. Brooks, C. T., 24. Brooks, R. V., 432. Broomhead, J. A., 472. Broschard, R. W., 366. Brossi, A., 347. Brotherton, R. J., 135. Brown, A. C., 97. Brown, B. R., 310. Brown, C. A., 132, 254. Brown, D., 153. Brown, D. A., 185. Brown, D. H., 160. Brown, D. J., 319. Brown, D. M., 375, 376. Brown, G. B., 373, 377. Brown, G. L., 378. Brown, G. M., 98. Brown, H. C., 132,207,210, 219, 227, 232, 254, 255, 262, 336. Brown, H. W., 51. Brown, I., 95, 330. Brown, J. B., 433, 434. Brown, K. B., 447. Brown, M., 210. Brown, M. R., 46. Brown, P. J., 263. Brown, R. D., 165, 337. Brown, T. H., 66. Brown, T. L., 130, 206. Brown, T. M., 158. Brown, W. B., 84, 88, 99. Brown, W. H., 277. Brown, W. I., 440. Brownstein, A. M., 408, 409. Brownstein, S., 197. Bruce, J. M., 309. Bruckenstein, S., 456. Brugel, W., 202, 334. Briimmer, W., 330. Bruer, S. W., 343. Bruice, T. C., 244, 246, 247, 249, 250. Bruin, F., 51. Bruin, M., 51. Brunnhe, C., 497. Bruno, J. J., 247, 249. Bruns, K., 294. Brush, A. H., 490. Brush, S. G., 94. Brushmiller, J. G., 169. Bryan, R. F., 372, 514. Bryce-Smith, D., 313. Bryson, M. J., 427, 429. Brzostowski, W., 93. Bubeva-Ivanova, L., 349. Bubnov, Yu. N., 135. Buc, H., 65. Buchanan, J. M., 406, 407. Buchi, G., 269, 350.
Buchner, W., 148, 280. Buchs, A., 477. Buchta, E., 276. Buchwald, H., 146. Buck, K. R., 233. Buckingham, A. D., 133, 185. Budd, A. L., 463. Budde, W. L., 230. Budge, A. H., 83. Budb, A., 118. Budzikiewicz, H., 200, 201, 204, 205, 303, 306, 352, 353, 354. Budzikiewicz, M., 351. Buchi, G., 292, 293, 294. Buchner, O., 241, 323. Buchner, W., 258. Biihler, R. E., 236. Buell, G. R., 227. Buerger, M. J., 503. Buffagni, S., 162. Buhl, F., 454. Bukun, N. G., 129. Bullen, G. J., 511. Bullerwell, R. A. F., 487. Bullock, E., 314, 329, 337, 389, 391, 396. Bu Lock, J. D., 271, 276. Bumgardner, C. L., 262, 320. BunEa.k, P., 475. Buncel, E., 224, 234. Bunn, C. W., 506. Bunnenberg, E., 197, 306. Bunnett, J. F., 219, 222, 223, 234, 235, 251, 252. Bunton, C. A., 247, 252. Bunyar, P. J.,244,258,266, 310. Burastero, J. J., 460. Burch, J. E., 206. Burdon, J., 310. Burg, A. B., 144. Burger, T. F., 185. Burgess, A. R., 39. Burgmaster, J., 262. Burgstahler, A. W., 297. Burkhalter, J. H., 109. Burkhardt, F., 347. Burlaka, V. P., 462. Burlingame, A. L., 204, 352. Burlitch, J. M., 243. Burn, D., 306. Burn, I., 86. Burnell, R. H., 357. Burnham, B. F., 387. Burriel-Marti, F., 452. Burrows, E. P., 279, 334. Burrows, W. D., 334. Burstein, S., 427. Burton, F. G., 460. Burton, J. S., 360. Burton, R. M., 414, 416. Buscarhs, F., 449. Busev, A. I., 455, 468.
520
Busch, D. H., 173, 174, 175. Busch, N., 479. Buss, H., 168, 422. Butcher, S., 195. Butenandt, A., 278. Butler, A. R., 246, 248. Butler, C. G., 277. Butler, K., 288, 318. Butterfield, D., 246. Buyske, D. A., 432. Buzas, A., 267. BUZ&S, 440. I., Bycroft, B. W., 341. Byers, R. G., 219. Byham, G., 152. Cabana, A., 203. Cabannes, F., 31. Cabezas, M. E., 305. Cabib, E., 360. Cadist, P., 269, 272. Cabrera, A. M., 469. Cadoff, B. C., 287. Cadogan, J. I. G., 226, 227, 244, 258, 265, 266, 267, 325. Cady, G. H., 150. Caglioti, L., 255, 301, 302. Cahn, R. D., 419. Cahn, R. W., 504. Cahn, W. R., 296. Cainelli, G., 255, 301, 302. Cains, T. L., 52. Cairns, J., 379. Cairns, T. L., 323. Calder, R. S., 504. Calderazzo, F., 176. Caldin, E. F., 254. Caldow, G. L., 127. Calkins, R. C., 473. Calloman, J. H., 100. Callow, R. K., 277. Calov, U., 147. Calpin, J. A., 463. Calvert, B. J., 345. Calvert, J. G., 33, 40, 43. Calvin, M., 62. Cama, H. R., 274. Cambie, R. C., 297. Cambio, R., 76, 84. Cameron, D. D., 306. Cameron-Wood, M., 244, 258, 325. Campaigne, E., 204, 341. Campbell, I. G. M., 333. Campbell, N., 308. Campbell, R. D., 245. Campbell, R. T., 461. Campbell, T. W., 267. Canellakis, E. S., 371. Canill, P., 195. Canjar, L. N., 95. Canning, R. E., 445. Cannon, J. R., 411. Cannon, P. L., 465.
Cantoni, G. L., 378. Capeller, I. 332. ,, Capizzi, F. M., 456. Caplow, M., 248. Capon, B., 246, 362, 363. Carasino, F. P., 162. Cargill, R. L., 282, 288. Carleton, N. P., 102, 110, 112. Carlin, R. B., 240. Carlin, R. L., 169. Carlon, F. E., 267. Carlsmith, L. A., 311. Carlson, A. A., 334. Carlson, R. D., 253. Carlstrom, A., 418. Carman, R. M., 295. Carmichael, I., 489. Carmichael, J. L., 97. Carnell, P. J. H., 157. Carnes, W . J., 476. Carnighan, R. H., 200, 303. Carpenter, A. T., 392. Carpenter, R. D., 349, 389. Carrington, A., 47, 49, 50, 51, 58, 59, 60, 68. Carrington, K., 206. Carrington, T., 110. Carroll, A. P., 145. Carroll, P. K., 101, 107, 121, 123. Carroll, T., 103. Carruthers, W., 294. Carson, R. C., 167. Carter, A. C., 432. Carter, D. G., 156. Carter, J. H., 253. Cartledge, J., 35. Cartwright, G. E., 395, 396. Cartwright, J., 478. Cartwright, P. F. S., 451. Casassas, E., 449. Case, D. E., 296. Case, J. R., 149, 150. Caserio, M. C., 208. Casnati, G., 327. Cason, J., 275, 318. Caspi, E., 204. Cass, R. C., 136. Cassady, D. R., 270. Cassimatis, D., 155. Cassmar, O., 434. Castanera, E. G., 413. Castells, J, 270. .' Castellucci, N. T., 339. Castro, C. E., 492. Cathon, R. E., 406. Cattanach, J., 185. Catterall, R., 63. Caughey, W. S., 396. Causey, R. L., 452. Cava, M. P., 296, 303. Cavalca, L., 164. Cavalieri, L. F., 371. Cave, A., 355. Cavell, R. G., 157.
Cazes, J., 236. Ceder, 0. J., 279. Cefola, M., 445, 494 CermBk, V., 123. Cernf, o., 499. Cerny, V., 303. Cerrai, E., 444. Gervinka, O., 346. Chacraborti, S. K., 301. Chadwick, J. R., 138. Chaikoff, I. L., 427. Chakrabarti, C. L., 476. Chakravarti, K. K., 290, 329. Chamberlain, M., 379. Chamberlain, N. F., 204, 341. Chamberlin, T. C., 222. Chambers, D. L., 277. Chambers, F. W., 504. Chambers, R. D., 185. Chambers, W., 375. Chamboux, J., 38. Chance, B., 418, 421. Chandler, B. V.,340. Chandler, J. A., 155. Chang, C. T., 218. Chang, E., 434. Chang, H. W., 307, 314. Chantry, G. W., 55, 56. Chao-Hwa Yang, 446. Chapeville, F., 382. Chaplain, R. A., 415. Chapman, D., 148, 277. Chapman, J. H., 347. Chapman, N. B., 233, 253, 336. Chapman, 0. L., 198, 285, 314. Chappelenr, P. S., 98. Chappell, S. F., tert., 282. Chargaff, E., 381. Charles, D., 496. Charles, K. R., 233. Charlot, G., 459. Charlton, T. L., 507. Charman, H. B., 269. Charney, E., 289, 297. Chastain, B. H., 365. Chatt, J., 160,162, 164, 171, 178, 179, 185, 186. Chatterjee, A., 347, 352, 354, 381. Chatterjee, S., 338. Chaudhury, D. K., 233, 336. Chaykin, S., 414. Chaykovsky, M., 265, 281, 321. Cheaney, D. E., 27. Cheek, C. H., 449. Cheese, I. A. F. L., 368. Cheeseman, G. W., 339. Chen, A., 245, 269. Cheng, C. C., 339, 374. Cheng, K. L., 478.
52 1
Cheng, P., 380. Cheng, T., 378. Cheng Wu-Chieh, 103. Chernyaev, I. I., 153, 154. Chernyak, N. Ya., 22. Chesick, J. P., 220. Chesnut, D. B., 61, 70. Chetkina, L. A., 509. Cheung, H. T., 296. Cheuychit, P., 308. Chia-Tsun Liu, 96. Chiang, Y., 233. Chibber, S. S., 210. Chien, J. C. W., 46. Childress, S. J., 339. Chipman, D. R., 504. Chiriboga, J., 445. Chirnside, R. C., 438, 459. Chisholm, M. J., 275. Chiswell, B., 172. Chiurdoglu, G., 195, 196, 198. Chkheidze, I. I., 52. Chodkiewicz, VI.,272. Chopard-Dit-Jean, L., 274. Chopra, K. L., 436. Chortyk, U. T., 219. Chow, W. Z., 292. Choy, T., 470. Chr&ien-Bessi&re, Y., 255. Christ, H. A., 202, 332. Christen, M., 232. Christensen, B., 331. Christensen, D., 195, 199, 202, 327, 329. Christensen, G. M., 364, 442, 445. Christenson, S . H., 62. Christian, S. D., 95. Christiansen, J., 195. Christiansen, J. A., 359. Christy, M. E., 322. Chu, K.-Y., 97. Chu, S.-H., 336. Chu, S . S. C., 508. Chumachenko, M. N., 462. Chumaerskii, N. A., 206. Chun, C. Lin., 195. Church, M. G., 218. Church, R. F., 302. Churchill, J. A., 427. Ciaccio, L. L., 233. Ciampolini, M., 162, 164, 233. Ciganek, E., 224, 279. Cilento, G., 416. Ciotti, M. M., 415, 416, 417. Cipollini, E., 206. Cirillo, V. A., 497. Claassen, H. H., 130. Clancy, D. J., 497. Clanet, F., 446. Clark, D. E., 347, 348. Clark, H. C., 142, 143, 157, 165. Clark, J. C., 267, 308, 474.
Clark, R. F., 282. Clark, R. T., 489. Clarke, C., 348. Clarke, E., 128. Clarke, E. A., 346. Clarke, G. A., 218. Clarke, R. L., 201. Clarke, W. G., jun., 197. Clark-Lewis, J. W., 340. Class, E., 150. Clauss, K., 185. Clayson, K. J., 415. Clayton, C. J . , 360. Clement, R. A., 338. Clementi, E., 111. Clemons, C. A., 449. Clezy, P. S., 396. Cline, M. J., 382. Clin6, R. E., 374. Clinton, W. L., 114. Clippinger, E., 214. Cloney, R. D., 114. Closs, G. E., 241. Closs, G. L., 60, 242, 280. Closs, L. E., 241. Clovis, J. S., 239. Cluceru, D., 450. Cluett, M. L., 471. Cluley, H. J., 490. Clutter, R., 261, 323. Coates, E., 469, 485. Coates, G. E., 130, 162, 165, 182, 185. Coates, M. E., 405. Cobb, G. C., 120. Cockbill, M. H., 437, 489. Cochran, E. L., 48, 56, 57, 58, 205. Cochran, W., 504. Cockerell, L., 170. Cockett, M. A., 338. Codington, A., 373. Codington, J. F., 375. Coe, P. L., 311. Coeffier, G., 161. Coffer, J. L., 226. Coffey, C. E., 181. Coffey, R. S., 241. Coffman, D. D., 201. Cohen, A. I., 487. Cohen, B., 149. Cohen, D., 154. Cohen, E. G. D., 94. Cohen, L. A., 252. Cohen, P., 418. Cohen, S., 282. Cohen, T., 250. Cohen-Bazire, G., 274. Cohn, G. L., 427. Cohn, W. E., 376, 377. Colburn, C. B., 144. Colburn, C. F., 54. Cole, H., 504. Cole, J. E., 306. Cole, S. J., 514. Cole, T., 54, 55, 56.
Coleman, C. F., 447. Coleman, M. H., 440. Coleman, R. F., 492. Coleman, W. E., 282. Coles, B. A., 46. Colin, R., 124, 127. Coller, B. A. W., 337. Collins, A. H., 472. Collins, C. J., 212. Collins, D. J., 294. Collis, M. J., 245. Collins, R. W., 468. Collman, J. P., 170, 173. Colowick, S. P., 417. Colter, A. K., 223. Cone, N. J., 355. Conley, R. T., 311. Connelly, J., 396. Connick, R. E., 67, 68, 69, 70. Connolly, D. J., 281. Connolly, J. F., 91, 97. Connolly, J. W., 140. Connors, K. A., 225. Connors, W. J., 378. Conover, L. H., 288, 318. Conreur, C., 356. Conrow, K., 342. Cook, C. D., 164. Cook, C. F., 492. Cook, D., 194. Cook, J. W . , 294. Cook, N. J., 375. Cook, R. E., 359. Cook, R. J., 53. Cooke, D. W., 174, 175. Cooke, G. A., 253. Cookson, G. H., 389. Cookson, R. C., 197, 267, 270, 285, 289, 294, 308, 309, 331, 333. Coombe, R. G., 366. Coomber, D. I., 496. Coombs, T. L., 422. Cooper, A. S., 502. Cooper, C. D., 120. Cooper, F. P., 246, 362. Cooper, G. D., 266. Cooper, J. E., 233, 277. Cooper, M. K., 160. Cooper, R. D. G., 273. Coopes, I. H., 91. Cope, A. C., 210, 224, 279, 286. Coppens, G., 224. Coppens, Ph., 507. Coppinger, G. M., 83. Corbett, J. D., 147, 167. Corbett, J. F., 338. Corbin, J. L., 221. Corcoran, J. W., 411. Cordes, E. H., 245, 247. Corey, E. J., 230, 258, 265, 281, 291, 309, 321. Corfield, M. C., 486. Corkins, J. T., 452.
522
Corney, N. S., 24. Cornforth, J. W., 419. Cornille, M., 502. Cornwell, C. D., 195. Corpel, J., 454. Corral, R. A., 354. Correia, J. S., 318. Corriez, P., 359. Corse, J., 207, Corset, J., 63. Corsini, A., 469. Corss, R. J., 185. Corth, R., 491. Corwin, A. H., 336, 391 Costa, B., 448. Costain, C. C., 193. Cosulich. D. B.. 366. Cotton, *F. A.; 129, 160, 161, 162, 163, 172, 176, 514. Coulson, C. A., 115, 127. Coulter, A. W., 304. Courtney-Pratt, J. S., 101. Courtois, J. E., 368. Cowe, D. W., 25. Cowen, J. A., 55. Cowie, J. M. G., 97. Cox, D. A., 309. Cox, E. F., 208. Cox, E. V., 405. Cox, G. F., 130. Cox, P. F., 66. Cox, R. A., 381. Coy, N. H., 487. Crabtree, A., 331. Craig, A. D., 139. Craig, L. C., 333. Crain, D. L., 231. Crain, R. D., 231. Cram, D. J., 190,230, 258. Cramer, F., 376. Cramer, R., 179. Cramer, R. M. R., 60, 148. Crandall, J. K., 283. Cranwell, P. A., 349. Craven, B. M., 513. Crawford, T. H., 191. Crayton, P. H., 156. Crick, F. H. C., 380. Criddle, W. J., 361. Crispin, D. J., 306. Cristol, S. J., 219, 224, 253. Croll, I. M., 81. Crombie, L., 200, 277, 329. Cromwell, N. H., 223, 224. Croon, I., 369. Crosbie, G. W., 409. Crosby, D. G., 265. Cross, A. D., 296. Cross, B. E., 298. Cross, F. J., 337. Cross, M. J., 409. Crossweimer, L. I., 62. Crosswhite, H. M., 101. Crouch, E. A. C., 166. Crowley, H. C., 345.
Crowley, K. J., 281, 289, 302. Cruickshank, A. M., 168. Cruickshank, A. J. B., 73. Cruickshank, D. W. J., 138. Csicsery, S. M., 240. Culbertson, J. B., 246. Cullis, C. F., 32, 36, 39. Culvenor, C. C. J., 345, 346. Cummings, F. E., 136. Cummings, W., 235. Cumper, C. W. N., 203. Cunningham, J., 55. Cunningham, L. W., jun., 417. Curcumelli-Rodostamo, M., 357. Curl, R. F., 191. Curphey, T. J., 303. Curran, C., 164. Curran, J. F., 425. Currie, R. B., 337. Curtin, D. Y., 196,220,264. Curtis, G. G., 303. Curtis, N. F., 172. Curtiss, C. F., 88. Cusachs, L. C., 114. Cusin, F., 26. Custer, J., 467. Cuthbert, G., 490. Cuthbert, J., 32. Cvetanovid, R. J., 21, 43, 44, 241. Cymcrman Craig, J., 268. Dadok, J., 480. Dalme, W., 130. Daftsios, A. C., 489. Dagnall, R. M., 484. Dahl, L. F., 138, 181. Dahlbom, R., 194. Dahlgard, M., 365. Dahne, W., 161. Daiber, J. W., 111. Dailey, B. P., 195. Dalby, F. W., 110. Dalgarno, A., 89. Dalziel, K., 414, 415, 420, 421. Damany-Astoin, N., 123. Dams, R., 451, 452. Danby, C. J., 131. Dance, J., 270. Dancewicz, A. M., 388. Daniel, H., 224. Danieli, N., 289, 305, 327. Daniels, R., 335. aanilov, S. N., 369. 3anilova, A. V., 346. Danilovs, G. P., 494. Danishefsky, S., 243, 287. Dankleff, M., 168. Danon, F., 89. Danyluk, S. S., 200, 316. lao, T. L., 434. larby, A. C., 283.
Darlak, R. S., 471. Darling, J. J., 424. Darling, S. D., 306, 355. Darooge, M. A., 198. Darwent, B. de B., 42. Darwish, D., 223. Das, J., 451. da Silva, J. J. R. F., 170. Dathe, C., 147. Datta, S. K., 456. Dauben, W. G., 282, 288, 291, 299, 303, 304. Daughaday, W. H., 427. Daum, G., 328. Dave, K. G., 341, 349. Davenport, A. J., 99. Daves, D., 339. David, D. J., 479. Davidson, A. J., 310. Davidson, E. R., 114. Davies, A. G., 143. Davies, D., 153. Davies, D. A., 27. Davies, D. I., 224. Davis, A,, 27. Davis, D. G., 472. Davis, F., 445. Davis, G. L., 138. Davis, G. T., 223. Davis, M., 342. Davis, R. E., 132. Davis, S. J., 334. Davis, S. P., 100, 101, 119. Davison, A., 176. Davydov, A. V., 477. Davydova, Z. M., 475. Dawson, B., 504. Dawson, C. R., 462. Dawson, J. W., 133. Dawson, R. F., 342. Dayagi, S., 231. De, A. K., 443. Deacon, G. B., 168. Dean, G. A., 439. Dean, J. A., 476. Deane, A. M., 153. Dear, R. E. A., 240. Dearman, H. H., 46. Deb, A., 354. Debo, A., 146. le Boer, E., 51. Decat, D., 492. Degmi, J., 329. Deghenghi, R., 265, 266. Degn, H., 359, 431. le Graaf, W., 88. Deguchi, Y., 57. 3e Ita, 0. S., 458. 3e Jongh, D. C., 253. ie Kerf, J., 511. Dekker, C. A., 361, 372, 375. le Kloet, S. R., 380. IeKluiver, H., 120. ie Koch, W. T., 300. lelahay, P., 481.
523
de la Mare, P. B. D., 224, 232, 233. Delbruck, M., 372. Della Porta, P., 13. Dellweg, H., 372, 411. Delmas, G., 99. Delmau, J., 189, 480. de Mars, G. A., 46. De Mars, R. D., 489. de Mayo, P., 284, 294, 300, 324, 337. de Miquel, M., 434. Demint, R. J., 369. Demole, E., 278. den Boef, G., 437. den Hertog, H. J., 235, 335, 336. Denney, D. B., 261. Deno, N. C., 209, 285. Denot, E., 305. De Puy, C. H., 222. Derevitskaya, V. A., 369. Dersin, H.-J., 148. Derwish, G. A. W., 206. Desai, N. B., 261. Desai, R. B., 300. Desbarres, J., 463. Deschamps, P., 482. Descoins, C., 274. Deshmukh, G. S., 460, 482. Deshusses, J., 485. Dessy, R. E., 230, 245, 269. do Stevens, G., 320. Deulofeu, V., 347, 358, 366. Deuser, W. G., 497. Deutsch, E. W., 127. Deutsch, J. L., 101, 107, 124. Deutschman, A. J., jun., 364. Dev, B., 450. Dev, V., 320. Devanathan, M. A. V., 463. Devaux, G., 362. De Voe, J. R., 496. de Vries, G., 441. de Vries, M., 383. Dewar, E. T., 364. Dewar, J., (Sir), 307. Dewar, J. H., 339. Dewar, M. J. S., 83, 207, 226, 240, 342. De Witt, E. J., 255. De Wolfe, R. H., 253. Deyrup, J. A., 373. Dhaneshwar, R. G., 471. Dharmatti, S. S., 203. Diamentis, A. A. D., 244. Diaz-Peiia, M., 94. Dickens, B., 181. Dickerhorf, D. W., 130,206. Dickerman, S. C., 236. Dickinson, C. L., 323. Dickinson, R., 490. Dickson, R. S., 155. Dickstein, J. I., 231.
Diczfalusy, E., 427, 434. Dieckmann, M., 382. Diehl, H., 439. Diehl, P., 202, 332. Dieke, G. H., 101, 107, 109, 127. Dikshitulu, L. S. A., 454, 467. Dillard, R. D., 270. Dilling, W. L., 288. Diluzio, J. W., 178. Di Marco, A., 411, 412. Din, F., 86. Dinning, J. S., 406, 408, 409. Dinstl, G., 492. Dinulescu, I. G., 309. Dion, H. W., 203, 365, 366. Diorio, A. F., 130. Dirscherl, A., 439, 441. Discher, C. A., 465. Ditchburn, R. W., 107, 111. Ditsch, L. T., 222. Dittmar, B., 230. Dittmer, D. C., 322. Ditz, J., 479. Dixon, R. N., 101, 118. Dixon, W. B., 199, 202, 327. Diyarov, I. N., 479. Djerassi, C., 190, 197, 199, 200, 201, 204, 205, 300, 303, 306, 347, 348, 351, 352, 353, 354, 512. Dmitriev, V. N., 486. Doadrio, A., 442. Dobrolyubskaya, T. S., 477. Dobrott, R. D., 131. Dobrynin, V. N., 289, 318. Dobson, G. R., 175, 176. Dobson, X. A., 269. Dobson, T. A., 341. Dobychin, S. L., 465. Dobyns, V., 201, 321. Dodgen, H. W., 68. Dodson, R. M., 286. Doehaerd, T., 195. Doerffel, K., 440. Doering, W. von E., 200, 238, 289. Doerr, I., 375. Doherty, D. G., 425. Doherty, M. D., 418. Dokoupil, 2, 79, 92, 98. Dolan, E., 63. Dolej3, L., 292. Doleial, J., 467, 468, 484. Dolin, M. I., 415. Domange, L., 136. Dominguez, J., 328. Don, G., 356. Donaldson, E., 442. Donaldson, K. O., 407. Donoghue, J. T., 168. Donohue, J., 504, 514. Donnay, G., 506. Donnay, J. D. H., 506.
Donninger, C., 419. Doornbos, D. A., 455. Doornekemp, J. G. F., 463. Dorain, P. B., 46. Doran, B. M., 406. Doran, P., 22, 23. Dorfman, L. M., Dorfman, R. I., 427, 429, 430. Dorokhov, V. A., 133, 136. Doran, V. F., 171. dos Santos-Veiga, J., 50, 51, 52, 206. Doty P., 378. Dougall, D. K., 396. Douglas, A. E., 101, 107, 109, 118, 127. Douglas, B. E., 169. Douglass, J. R., 253. Douglass, R. M., 153. Douwes, H., 507. Dowell, J. T., 103. Dowgialls, A., 362. Dowling, J. M., 193. Downing, D. F., 320. Downing, D. T., 274. Downing, M., 409. DOWS, A., 173. D. Doyle, F. P., 322. Doyle, W. T., 62. Drttgo, R. S., 107, 155. Drake, J. E., 139, 141. Dravnieks, F., 49, 50, 68. Dreger, L. H., 196. Dreiding, A. S., 327. Dreizler, H. D., 195. Drenchko, P., 324. Drenth, W., 269. Dreschler, D., 336. Dresel, E. I. B., 394. Dressler, R. L., 260. Drever, D. F., 40. Drews, B., 449. Drey, C. N. C., 332. Driesel, E. I. B., 394. Driessen, H.-E., 265. Drillat, J., 37. Droege, J. W., 21. Drowart, J., 100, 119, 120, 124, 128. Drummond, D. W., 370. Drummond, J. L., 456. Druyan, R., 420. Drye, D. J., 157. Dubbs, C. A., 445. Dubeck, M., 232. Dubovitskii, V. A., 155. Duc Dohkac Manh, 205. Duckitt, J. A., 468. Duckworth, M. W., 156, 157. Duclaux, A. D., 423. Dudani, P. G., 139. Duell, E. G., 227. During, G., 95, 96. Duffy, C., 143.
524
I N D E X OF A U T H O R S N A M E S
Duggan, E. L., 379. Duhart, P., 131. Duhne, C., 458. Duling, I. N., 335. Dulova, V. G., 322. Dumke, W. I., 508. Dunathan, K., 338. Duncan, A. B. F., 100. Duncan, F. J., 241. Dunford, H. B., 107. Dunitz, J. D., 287, 328. Dunlap, L. B., 464, 483. Dunlap, R. D., 92, 97. Dunn, D. B., 374. Dunn, H. M., 504. Dunn, T. M., 162, 163. Dunnavant, W. R., 264. Dunne, T. G., 172. Dunstan, I., 132. Dupont, J. A., 131, 132. Durand, M. H., 270. Durham, L., 203, 366. Durham, L. J., 204, 205, 348, 352, 353, 354. Durie, R. A., 101, 108. Durrant, B., 129. Durrant, P. J., 129. Dutler, H., 305. Duts, M., 195. Dutta, N. L., 347. Dutta, P. C., 296. Dutton, G. G. S., 364, 370. Dutz, R., 376. Duval, C., 198, 439, 499. Dvoritk, J., 476. DvoPQk,V., 470. Dvoryankin, V. F., 507. Dyatkina, M. E., 153. Dybczyliski, R., 448. Dybvig, D. H., 220, 264. Dykast, J., 499. Dyke, D. E. L., 81. Dymova, T. N., 130. Dyrssen, D., 478. Dzhagatspanyan, R. V., 480. Dzierzynski, M., 30, 31, 34.
Eckelmann, W. R., 496. Eckert, J. M., 201, 203. Eckfeldt, E. L., 463. Edgell, W. F., 206. Edmonds, M., 374, Edmondston, P. B., 330. Edwards, A. J., 15% Edwards, B. E., 204, 341. Edwards, D. A., 159. Edwards, J. A., 305. Edwards, J. O., 168, 254. Edwards, J. W., 464. Edwards, 0. E., 243, 296, 297, 318, 347, 358. Efremov, V. Y., 33. Egerton, A. C. (Sir), 28. Eggerer, H., 404. Eglinton, G., 269, 277, 282, 295. Egnell, C., 267. Ehmann, W. D., 491. Ehrlich, G., 11, 12, 13, 14. Ehrlich, H. W. W., 513. Ehrlich, P., 155. Eichenberger, W., 274. Eichhorn, E. L., 510. Eichler, S., 179, 181. Eickermann, R., 157. Eigen, M., 246. Eisch, J. J., 138, 266, 334, 337. Eisenbraun, E. J., 344. Eisenhauer, G., 148. Eisenthal, R., 250. Eisinger, J., 12, 13. Eisman, E. H., 261. Eisner, U., 337. Eistert, B., 317. Eiter, K., 277, 278. Ekberg, S., 478. Ekert, B., 372. Elad, D., 263, 273. Elias, D. H. D., 233. Elias, H., 136. Elias, L., 21. Eliel, E. E., 196. Eliel, E. L., 207, 223, 236, 256, 257, 284. Eliseev, S. S., 159. Eaborn, C., 232, 254. Elisesva, N. G., 130. Eade, R. A., 300. Ellert, G. V., 154. Eardley, R. P., 455. Ellestsd, G. A., 292. Eargle, D. H., 59. Elliot, D., 452. Eason, R., 382. Elliott, B., 182. Eastham, J. F., 233. Elliott, I. W., 338. Eastman, J. W., 62. Elliott, T., 197. Easton, N. R., 270. Ellis, B., 306. Easty, D. B., 361. Ellis, R. B., 132. Eaton, D. R., 52. Ellison, F. O., 108. Eaton, P. E., 284. Elmore, N. F., 347. Ebel, H. F., 311. Elodi, P., 424. Eberhardt, M., 236. Els, H., 327. Eberhardt, W. H., 103. El Sayed, M. F. A., 175. Ebert, M., 446. Ebsworth, E. A. V., 140, Elvidge, J. A., 334. EIving, P. J., 473, 488. 150. Emanuel, N. M., 39. Ecke, H., 146.
EmelBus, H. J., 138, 146, 150, 177. Emerson, T. R., 336. Emmons, W. D., 259. Emons, H.-H., 140. Emovon, E. U., 224. Emsley, J. W., 145. Engel, C. R., 256. Engel, L. L., 427. Engel, W., 155. Engelbrecht, A., 150. Engelhardt, V. A., 323. Engelsma, G., 62. Engelsman, J. J., 462. England, D. C., 131. England, S., 425. Englehard, N., 341. Englert, G., 332. English, W. H., 471. Enikolopyan, N. S., 28, 29, 30, 31, 32. Enslin, P. R., 300. Entwistle, R. F., 509. Enzell, C., 292. Erao, P., 358. Erb, R., 341. Ercoli, A., 256. Erdey, L., 440, 454, 473, 500. Erdos, E., 95. Erdtman, H., 296, 296. Erickson, C. E., 133. Erkovich, S. P., 111. Erne, F., 439. Ernst, B., 365. Erpelding, J. J., 235. Erpelding, T. J., 269. Ertel, K., 261, 446. Eskananzi, It., 172. Estabrook, P., 418. Essen, L. N., 165. Ettinger, R., 71, 131. Eugster, C. H., 328. Evans, A. G., 182, 226. Evans, D., 263, 276. Evans, F. J., 326. Evans, H. J., 403. Evans, J. C., 233. Evans, R. F., 336. Evans, R. J. D., 272. Evans, W. H., 446. Everard, A. F., 235. Everett, D. H., 73, 91. Evers, E. C., 129. Everse, J., 421. Ewald, P. P., 506. Ewart, G., 145. Ewing, G. J., 161. Eyring, H., 17. Eyton, W. B., 318. Faber, G., 367. Faber, J. S., 455. Fabricand, B. P., 65. Fabrichnyi, B. P., 276. Fackler, J. P., 165.
INDEX
OF AUTHORS' NAMES
525
Fahey, R. C., 226, 232. Field, B. O., 155. Faigle, H., 273. Fields, D. L., 280. Failes, R. L., 224. Fields, E. K., 243, 308. Fainberg, A. H., 229. Fierce, W. L., 144. Fairbrother, F., 157. Fiers, W., 379. Falconer, J. W., 22, 32. Fife, T. H., 247, 250. Falconer, W. E., 21, 35. Fife, W. K., 236. Fales, H. M., 343, 348. Figgins, P. E., 173. Falk, J. E., 394. Figgis, B. N., 143, 171. Fallon, R. J., 113, 114. Filasiewicz, W., 476. Fan, C. Y., 101. Filimonova, M. M., 486. Fankuchen, I., 504. Filippova, L. F., 26, 27. Farber, M., 135. Finan, P. A., 263. Faris, J. P., 448, 476. Finch, A., 135, 206. Farmer, J. B., 56, 60. Finch, N., 204, 351, 354. Farrell, P. G., 286. Findlay, T. J. V., 96. Fateley, W. G., 195. Fine, D. A., 162. Fathy, I., 321. Finegold, H., 197. Faulhaber, G., 177. Fink, K., 374. Faulkner, J. E., 121. Fink, R. M., 374. Fava, G., 164, 509, 510. Fink, W., 140. Favin, S., 20. Finkbeiner, H. L., 266. Fawcett, C. P., 415, 417. Finkelstein, M., 220. Fay, R. C., 169. Finn, E. J., 114. Feakins, D., 145. Finn, R. T., 224. Feather, M. S., 360. Firestone, R. A., 337. Feather, P., 306. Firsching, F. H., 451. Fechtig, O., 290. Firth, W. C., 253. Feder, R., 504. Fischer, A., 240, 288. Fsdorak, N. A., 267. Fischer, D. W., 496. Fedorova, A. V., 272. Fiecher,E. O., 180,183, 184. Feeney, J., 143, 145. Fischer, G., 442. Feigl, F., 442. Fiecher, H., 52, 219, 272, Felauer, E. E., 277. 395. Feller, K. L., 279. Fischer, J., 143. Fellman, W., 183. Fischer, J. F., 484. Fels, I. G., 414. Fischer, R., 327. Feltham, R. D., 46. Fischl, J., 447. Fender, B. E. F., 88. Fish, A., 32, 36, 39. Feniak, G., 297, 318. Fisher, H. F., 425, 426. Fenimore, C. P., 20, 21. Fisher, I. P. 31. Fensham, P. J., 146. Fisher, M. E., 94. Fenske, M. R., 37. Fishman, J., 433, 434. Fenske, R. F., 171. Fishman, M. J., 476. Ferguson, G., 286, 297, 507. Fitzgerald, M. E., 497. Ferguson, H. I. S., 101. Fitzsimmons, B. W., 145. Ferguson, R. E.,' 32. Flahaut, J., 136. Fergusson, J. E., 160, 161. Flaschka, H., 456. Fernandez, M., 425. Flavin, M., 404, 405. Fernandez, V. P., 421. Fleck, G. M., 244. Fernando, Q., 166, 463, 465, Fleissner, E., 374. 469. Fleming, I., 268. Ferrari, C., 347. Fleming, J. S., 312. Ferreira, J. M., 204, 354. Fleming, M. A., 135. Ferrier, F. J., 359. Fletcher, A. N., 154. Ferrier, R. J., 359, 364. Fletcher, H. G., jun., 362. Ferrier, W. G., 513. Flock, F. H., 332. Ferris, L. M., 153. Flood, C., 430. Ferrus, R., 152. Flood, S. H., 232, 233, 268. Fetter, E. J., 330. Florence, T. M., 488. Fetter, N., 137. Flores, S. E., 204. Fetzer, U., 252. Florini, J. R., 432. Fessenden, R. W., 48, 51. Floyd, K. W., 408. Feuer, H., 258. Fluck, E., 145, 146, 149. Fiarman, I. D., 246. Fluendy, M. A. D., 94. Fichtel, K., 183. Flygare, W. H., 192.
Fock, W., 95. Fodor, G., 260. Forster, T., 100. Foex, M., 153. Fog, J., 456. Foldi, V. S., 267. Folt, V. L., 192. Foner, S. N., 35, 56, 57. Fonken, G. J., 273, 285. Fontaine, F., 378. Fontana, P. R., 118. Foord, S. G., 29. Foote, J. L., 233. Forbes, J. W., 83, 480. Forchielli, E., 429. Ford, J. E., 405. Foreman, H., 495. Foreman, J. K., 456. Forman, A., 50. Forman, A. G., 213. Forman, J. C., 98. Forman, P., 448. Formbnek, Z., 499. Forrest, H. S., 375. Forsen, S., 198. Forster, R. G., 194. Forstner, J. A., 145. Fort, A. W., 215. Fort, R., 27. Fortune, I., 440. Foss, O., 150. Fossen, S., 150. Foster, A. B., 277, 334, 363, 366, 367. Foster, E. W., 118. Foster, J. F., 21. Foster, P. W., 223. Foster, R. E., 148. Foster, W. E., 133, 256. Fotherby, K., 428. Fothergill, G. A., 263. Fowden, L., 325. Fowler, L. R., 358. Fowles, G. W. A., 129, 156, 157, 159. Fox, J. J., 374, 375. Frackowiak, M., 127. Fraenkel, G. K., 50, 51, 58, 372. Fraenkel-Conrat, H., 381. Fraga, S., 113, 12:. Francis, J. E., 323. Francis, K. E., 153. Franck, B., 335. Frangopd, P. T., 314. Frank, G. H., 482. Franke, J., 341. Frankenfeld, J. W., 325. Franklin, J. L., 102. Franklin, R. M., 382. Franklin, T. C., 164. Franswa, C. E. M., 479. Frantz, A. G., 432. Frantz, A. M., 282, 312. Franzen, V.,241, 265, 280. Fraser, M., 203, 327.
526
INDEX OF A U T H O R S ' N A M E S
Fraser, R. R., 200. Fraser, R. T. M., 174. Frawley, T. F., 429. Frazer, J. W., 133, 151. Fredericq, A., 378. Freed, J. H., 58. Freedman, H. H., 282, 283, 312. Freegerde, M., 478. Freeman, E. S., 54. Freeman, J. P., 279, 320. Freeman, P. I., 98, 99. Freeman, R., 71. Freese, E., 373, 376. Freese, E. B., 376. Freiberg, L. A., 196, 198, 317. Freidlina, R. Kh., 156. Freier, E. F., 415. Freifelder, M., 254, 335. Freiser, H., 443, 469. French, D., 369. FrBon, P., 257, 267. Frkre, P., 157. Fresco, J. R., 378. Frese, E., 148. Freund, H., 158. Frey, A. J., 352. Frey, H. M., 241, 321. Freymann, M., 67. Freymann, R., 67. Frid, J., 332. Fridsvich, I., 421. Fridrichsons, J., 503, 513,
Frost, D. C., 122. Frostling, H., 330. Frush, H.L., 361, 496. Fry, A., 219. Fry, P. W., 124. Frydman, B., 347, 358. Fuchs, F., 276. Fudim, M., 262. Fiirst, A., 341. Fujii, T., 366. Fujimoto, M., 448. Fujimoto, S., 19. Fujishiro, R., 80, 81. Fujita, J., 172, 173. Fujita, K., 233. Fukuchi-Thibaut, Y., 31 Fukui, K., 83. Fukushima, D. K., 431. Fuller, N. A., 252. Fuller, W., 378. Funk, H., 160. Funk, H. R., 403. Funk, K. F., 323. FUOCO, 411. L., Furse, C. T., 461. Furukawa, S., 292. Furukawa, Y., 417. Furuki, C., 474.
514.
Friebolin, H., 204. Fried, J., 342. Fried, V., 94. Friedel, R. A., 498. Frieden, C., 425, 426. Friedkin, M., 414. Friedl, W., 120. Friedman, D. L., 404. Friedman, H. C., 412. Friedman, S., 407. Friedmann-Spiteller, M., 352, 353. Friedrich, W., 374. Friend, J. A., 93. Friese, G., 477. Friis, P., 279. Frisch, M. A., 196. Frischmann, J. K., 487. Frig-GaLega, T., 478. Fristom, R. M., 20, 21. Fritchie, C., 509. Fritchie, C., jun., 283. Fritz, G., 137, 140. Fribz, H. P., 183. Fritz, J. S., 448, 471. Fritzsche, H., 82. Frohlich, H.-O., 166. Frohliger, J. O., 467, 469. Fromm, H. D., 139. Fromm, H. J., 424. Frost, A. A., 114.
Garton, W. R. S . , 102. Gamin, D., 127. Garwood, R. F., 269. Garz6, T., 449. Gaslini, F., 458. Gasser, R. P. H., 71. Gassman, P. G., 213, 281, 283, 303. Gasson, D. B., 499. Gast, P. W., 497. Gate, S. H., 147. Gates, M., 348. Gatz, C., 123. Gaudemaris, M., 276. Gaudry, R., 265, 266. Gaur, J. N., 450, 470. Gayden, A. G., 100, 112. Gear, J. R., 343. Geary, W. J., 469. Gedda, L., 448. Gee, G., 99. Gee, M., 364. Gegus, E., 473. GBher, J., 487. Geichman, J. R., 159. Geiger, B., 287. Geissmrtn, T. A., 292, 345. Geldard, J. F., 172. Geller, B. E., 97, 487. Gabe, E. J., 513. Gellert, E., 358. Gabrilove, J. L., 427, 429. Genet, F., 511. Gaertner, G., 339. Genevois, L., 421. Gaetjens, E., 246. Gen-Ichi Tsuchihashi, 213. Gaiffe, A., 262. Gensler, W. F., 320. Gaiser, P., 402, 413. George, D. B., 226. Gal, D., 34. George, T., 204, 353, 354. Galbraith, F. J., 497. Georgian, V., 303. Galinos, A. G., 137. Gerace, P. L., 170. Gallagher, T. I?., 431, 433, Gerds, A. F., 153. Gerig, J. T., 234. 434. Galmarini, 0. L., 366. Gerken, R., 157. Galt, R. H. B., 298. Gerlach, H., 328. Galus, Z., 52, 482. Gerloch, M., 185. Gamp, A., 446. Germain, G., 511. Germain, J. E., 31. Gamsjiiger, H., 441. Gamson, B. W., 98. Gernert, F., 130. Ganchoff, J., 456. Gero, L., 1'07. Ganellin, C. R., 286. Gerrard, W., 133, 136, 206. Ganter, C., 305. Gershfeld, N. L., 297. Gersmann, H. R., 58. Ghnti, T., 445. Gaoni, Y., 198, 307, 316. Gerson, F., 51. Gerstenberg, B., 156. Garbisch, E. W., 252, 254. Geschwind, S., 46. Garbutt, S., 370. Garcia-Fernandez, H., 129. Geske, D. H., 50, 57. Gardi, R., 256. Gesser, H., 143. Gardiner, W. C., 19. Gestblom, B., 201, 202, 323, Gardner, A. L., 123. 324. Gardner, C. L., 60. Gething, B., 310. Gettler, J. D., 246. Qardner, K. W., 474. Getz, H. R., 446. Gardner, P. D., 304. Gewald, K., 323, 330. Garegg, P. J., 360. Gewitz, H. S., 396. Garland, J. H. N., 143. Ghosh, A. K., 141. Garman, R. G., 440. Ghoshal, C. R., 352. Garner, C. S., 174. Gianni, M. H., 196, 284. Garst, R., 234. Giasto, M. B., 139. Garton, G., 138.
527
Gibb, T. R. P., 129. Gibbard, F., 95. Gibbons, W. A., 283. Gibbs, J. A., 490. Gibson, J. F., 48, 189. Gibson, K. D., 386, 397, 398. Gibson, N. A., 472. Gibson, T., 138. Giguere, P. A., 23, 97. Gilani, S. S. H., 331. Gilbert, B., 204, 352, 353, 354. Gilbert, J. M., 471. Gilbert, W., 379. Gilchrist, M., 247. Gilchrist, T., 201, 318. Gilderson, P. W., 223. Giles, J. A., 295. Gilje, J. W., 222. Gilles, P. W., 100, 135. Gillis, B. T., 259, 279. Gillis, J., 493. Gillespie, A. S., 496. Gillespie, R. J., 64, 149. Gilman, H., 263, 266, 276, 342. Gilman, R. E., 358. Gilow, H. M., 245. Gilroy, G. P., 461. Gimesi, O., 454. Ginman, R. F. A., 203. Ginsberg, A. P., 186. Ginsburg, S. I., 468. Ginter, M. L., 106. Giraldi, G., 509. Girard, M., 488. Girdhar, H. L., 83. Gissane, W. J. M., 119. Gisser, H., 276. Giuffre, L., 456. Giuffrida, L., 495. Glarum, S. H., 56. Glasner, A., 152. Glass, M. A. W., 107, 199. Glasstone, S., 17. Gleinig, H., 271. Gleit, C. E., 474. Glemser, O., 147, 444. Glen, N. A., 294. Glew, D. N., 82, 179. Glocking, F., 141. Glockling, F., 166. Glonek, M. D., 164. Gloss, G. L., 281. Gloss, L. E., 281. Glotter, E., 300. Glukhov, I. A., 159. Gmelin, R., 299. Gnatz, G., 157. Gnauck, G., 449. Goates, J. R., 83, 94. Goatley, J. L., 364. Gobbett, E., 131. Gochman, C., 339. Godfredsen, W. O., 300.
Godfrey, L. E. A., 279. Golles, F., 97. Goering, H. L., 213, 214, 230. God, R., 148. Gothlich, L., 235, 269. Gotz, M., 349. Goetze, G. W., 502. Goetzee, W., 146. Gohlke, R. S., 496, 498. Gohring, J., 155. Goksoyr, J., 490. Gold, E. H., 335. Gold, H., 279. Gold, N. I., 432. Gold, V., 66, 67, 233, 246, 248. Goldberg, A., 395. Goldberg, S., 65. Goldsby, J. D., 173. Golden, J. T., 240. Golder, G. A., 509. Goldfarb, T. D., 207. Goldfarb, Y. L., 276. Goldfinger, P., 100, 120, 127. Goldin, A., 417. Golding, R. M., 46, 184. Goldman, G., 232. Goldschmid, H. R., 367. Goldshtein, A. L., 473. Goldstein, D., 441. Goldstein, G., 458, 461. Goldstein, I. J., 368. Gqldstein, J. H., 270, 327, 374. Goldstein, M., 206. Goldwhite, H., 280. Goldzieher, J. W., 430. Goleb, J. A., 476. Goliasch, K., 314. Golightly, D. S., 162. Golovnya, V. A,, 153, 154. Goltzsche, W., 334. Gomel, M., 193. Gomer, R., 10. G6mez-IbQiiez, J., 96. Gonzalez, A. G., 277, 295. Good, C. D., 132. Good, R., 328. Goode, G. C., 468. Goodgame, D. M. L., 160, 162, 163. Goodgame, M., 160, 162, 163. Goodman, G. L., 47. Goodman, L., 365,366,375. Gordon, A. W., 290. Gordon, G., 153. Gordon, L., 452. Gordon, R. D., 128. Gordy, W., 53, 109, 205, 206. Goring, D. A. I., 97, 279, 365, 367. Gorman, M., 204, 353, 355.
Gorokhovskaya, A. S., 487. Gorsich, R. D., 177. Gorsuch, T. T., 438. Gosset, J., 352. Goto, T., 358. Gots, J. S., 374. Gottbrath, J. A., 132. Gotthardt, H., 330. Gottlieb, 0. R., 300, 318. Gottschling, H., 373. Goubeau, J., 139. Goudmand, P., 102. Gough, J., 291. Goulian, M., 410. Gouterel, R., 205, 351, 355, 356. Gover, T. A., 82. Govil, G., 203. Govindachari, T. R., 292, 354, 358. Gracheva, E. P., 272. Gracias, 31. &I.T. K., 456. Graddon, D. P., 167. Grafer, P., 277. Graham, J. D., 194, 281. Graham, R. P., 438, 462 Graham, W. H., 321. Graig, J. C., 330. Granchimont, E., 270. Grandmontagne, R., 114. Granick, S., 385, 387, 388, 390, 393, 394, 395, 397, 398. Grant, I. G., 301. Grant, I. J., 349. Grant, P. K., 295. Grant, L. R., jun., 144. Grant, W. K., 509. Grashey, R., 330, 337. Grasshoff, K., 483, 485. Grau, A., 206. Graves, J. M. H., 314. Graverman, I. J., 491. Gray, A., 339, 349. Gray, C. H., 394, 427. Gray, D. O., 325. Gray, H. B., 46, 47, 157, 159, 163, 175. Gray, J., 42. Gray, J. A., 94. Gray, P., 267. Graybill, B. M., 132, 133. Green, B., 256, 257. Green, I. R., 459. Green, J. A., 20. Green, M., 252, 253, 398. Green, M. L. H., 183. Green, S. I. E., 130. Greene, F. T., 135. Greene, R. E., 154. Greenaway, F., 437. Greenberg, D. M., 407. Greenberger, M., 478. Greenblast, R. B., 429, 433. Greenfield, S., 459, 474.
528
Greenhalgh, R., 478. Greenwood, C. T., 369. Greenwood, N. N., 137. Gregorowicz, Z., 454. Gregory, B., 314, 337. Greizerstein, W., 235. Greuter, F., 292. Griegel, R., 282. Griffin, G. E., 282. Griffith, H. O., 61. Griffith, W. P., 152, 160. Griffiths, D., 504. G r S t h s , D. E., 415. Griffiths, J. E., 140, 142. Griffiths, J. H. E., 46. Griffiths, J. V., 132. Griffiths, T. R., 61. Griffiths, V. S., 206, 485. Grimm, F. G., 425. Grim, S. O., 261. Grimes, R. N., 132. Grimwood, B. E., 280. Grinberg, A. A., 168, 175. Grindahl, G. A., 229. Grinstein, M., 394. Grisebach, H., 366. Grisolia, S., 425. Griswold, A. A, 198, 285, 314. Griswold, E., 161. Gritter, R. J., 174. Grob, C. A., 218, 219. Grob, E. C., 274. Grobe, J., 177. Gronowitz, S., 201, 202, 323, 324, 328, 330. Gros, F., 379, 380. Gross, D. G., 425, 426. Gross, H., 328. Grossman, R. F., 333. Grovenstein, E., 232. Gruber, W., 424. Gruen, D. M., 152, 164. Grune, A., 445. Gruenfelder, C., 20. Grun, H., 196. Grunberg-Manago, M., 37 1, 381. Grundon, M. F., 346, 348. Grunwald, E., 207. Grunze, H., 376. Gual, C., 430. Guarino, J. P., 63. Gudzenko, Zh. D., 486. Guenebaut, H., 62. Gunther, H. L., 372. Guernet, M., 362. Guest, J. R., 406, 407. Giisten, H., 264. Guggenheim, E. A., 88, 90, 92, 94. Guilbault, G. G., 465. Guinn, V. P., 492. Guiseley, K. B., 365. Guisset, J.-L., 95. Guisti, P., 416.
Gunderloy, F. C., 133. Gundry, P. M., 14. Gunner, S. W., 359. Gunning, H. E., 283. Gunstone, F. D., 277, 294. Gunter, F., 402. Gupta, B. K., 111. Gupta, G. S., 294. Gupta, J., 483. Gupta, N. K., 420. Gurdjian, E. S., 466. Gurevich, A. I., 289, 318. Guriev, I. A., 473. Gurmnani, S., 404. Gurpide, E., 434. Gusev, S. I., 468. Gut, J., 375. Gut, M., 429, 430. Gut, R., 152, 164. Guthrie, R., 374. Guthrie, R. D., 366. Guthrie, S., 379. Gutmann, V., 171, 482. Gutowslry, H. S., 66, 71, 192. Gutsche, C. D., 218, 241. Gutterson, M., 473. Guttman, L., 94. Guy, R. G., 179. GUZZO, V., 46. A. Gwina, W. D., 149. Gwinn, W. D., 192. Gysin, H., 320.
Haahti, E. 0. A., 277. Haake, P., 165, 175. Haas, J. W., 486. Haas, W., 443, 453. Haase, B., 336. Habashi, F., 485. Habbousch, A. E., 449. Haber, H. S., 474. Haber, R. G., 223. Habermann, Z., 484. Habermehl, G., 356. Hebich, A., 237. Hachihama, Y., 369. Hackett, C. M., 237. Hackman, R. H., 447. Haendler, H. M., 157. Haenni, E. O., 444. Haerdi, W., 488. Hliring, W., 338. Hafner, K., 284, 314, 316. Hafner, W., 258. Hague, R., 485. Haguenauer-Castro, D., 442. Hahn, C.-S., 240. Hahn, E., 313, 342. Hahn, F. L., 466. Hahn, H., 138, 483, 485. Haiduc, I., 168. Haight, G. P., jun., 159. Kaim, A., 173, 174. Hainberger, L., 450.
Haines, A. H., 363. Hai Won Chang, 281, 286. Hakomori, S., 365. H&la,E., 94. Halberstadt, M. L., 220. Hall, A. N., 246. Hall, B. D., 380. Hall, D. M., 232. Hall, G. E., 311. Hall, J. R., 376. Hall, J. H., 232, 244, 325. Hall, J. L., 63, 484. Hall, J. R., 282, 312. Hall, L. D., 201, 204, 364. Hall, N. D., 253. Hall, R. P., 270. Hall, W. B., 446. Halmann, M., 143, 217. Halousek, J., 500. Halpern, O., 305. Halsall, T. G., 296. Halsey, G. D., 88. Hamaguchi, H., 491. Hamans, H., 330. Hambling, J. K., 235. Hambly, A. N., 199. Hameka, H. F., 103, 330. Hamfelt, A., 495. Hamer, J., 332. Hamill, W. H., 63. Hamilton, G. A., 248. Hamilton, J. A., 293, 513. Hamilton, R. J., 377, 295. Hamilton, S. A., 301. Hamilton, W. C., 505. Hamlet, Z., 229. Hamlow, H. P., 399. Hamm, R. E., 461. Hammaker, G. S., 163. Hammer, G. G., 242. Hammond, G. S., 221, 239, 241, 262, 283, 288. Hammond, J. B., 376. Hamner, A. J., 471. Hamolsky, M., 416. Hamor, T., 286. Hamor, T. A., 296,301,349, 512. Harnrick, P., 53, 367. Hamway, P., 445, 494. Hanack, M., 284. Hanamura, S., 463. Hanania, G. I. H., 175. Hancock, J. W., 232. Hand, C. W., 20. Hand, E. S., 249. Handa, N., 370. Handschumacher, R. E., 375. Handler, P., 421. Hanessian, S., 365. Hanker, I., 341. Hannan, H. H., 151. Hansen, R. L., 253. Hansen, R. P., 275. Hansen, R. S., 12.
IN
EX OF AUTHORS NAMES
529
Hansen-Nygaard, L., 195, 199, 202, 327. 329 Hanson, A. W., 509. Hanson, J. R., 298. Hanst, P. L., 33. Hansing, C. E., 141. Han Toi, 480. Harada, H., 349. Harada, R., 302. Harbron, E., 254. Harburn, G., 503. Harcourt, R. D., 337. Harden, J. C., 499. Harding, A. J., 27. Harding, M. M., 514. Hardy, C. J., 155. Hardy, F. R. F., 32. Hardy, K., 322. Hare, C. R., 47, 159. Hargreaves, A., 507. Hargreaves, M. K., 189. Harley-Mason, J., 268. Harlow, G. A., 457, 471. Harman, K. H., 136. Harnden, M. R., 364. Harper, B. J. T., 343. Harper, K. A., 340. Harrar, J. E., 463, 464. Harris, B. W., 265. Harris, C., 280. Harris, C. M., 164, 166. Harris, D. L., 412. Harris, J. F., 201, 227. Harris, J. J., 134. Harris, E., 407. Harris, E. E., 337. Harris, M. M., 232. Harris, T. M., 264. Harrison, E. C. P., 188. Harrison, I. T., 200, 306, 355. Harrison, P. M., 420. Harrison, S. E., 47. Hart, F. A., 162, 164. Hart, H., 209, 221, 240, 312. Hart, M., 502. Hart, P. A., 365. Hart, P. B., 167. Hartenstein, J., 148. Hartenstein, J. H., 285. Hartke, K., 267. Hartley, J. G., 161. Hartley, F. R., 152. Hartman, C. D., 12. Hartmann, D., 373. Hartmann, H., 94. Hartmann, R., 291. Hartmann, W., 328. Hartung, G. K., 498. Hartzler, H. D., 242, 281. Harvey, L. G., 477. Harwood, H. J., 274. Haschke, J., 166. Hasegawa, H., 201. Hasegawa, S., 368. Haselden, G. G., 98.
Haskell, J., 429. Haskell, T. H., 339. Hassan, H., 232. Hasse, K., 335. Hassel, O., 82, 512. Hasserodt, U., 195, 281. Hassner, A., 227, 304, 330. Hatch, F. T., 406. Hatchard, C. G., 477. Hatfield, D., 375. Hatfield, W. E., 163. Hathaway, B. J., 167, 171. Hattori, K., 147. Haubenstock, H., 257. Hauge, S., 150. Hauptmann, H., 276, 320, 503. Hauser, C. R., 264. Hausser, K. H., 52. Hauth, H., 348. Hawkins, C. J., 166. Hawkins, J. E., 297. Hawley, W. G., 455. Hawthorne, M. F., 131,132, 256. Hawtin, P., 37. Hay, A. S., 269. Hayakawa, S., 305. Hayano, M., 430. Hayatsu, H., 376. Hayatsu, R., 337. Hayes, J. W., 488. Hayes, M. R., 478. Hayes, W., 46. Hayes, W. K., 291. Hayman, H. J. G., 82. Haymaker, C. R., 263, 276. Haynes, L. J., 296. Hays, H. R., 321. Hayter, R. G., 165, 186. Hazekamp, R., 51 1. Hazell, A. C., 148. Headridge, J. B., 454. Heaney, H., 311. Heard, D. D., 333. Heath, D. C., 101. Heath, D. F., 107. Heath, H., 391, 394. Heaton, B. G., 217. Heaton, J. W., 504. Heavey, H., 235. HBbert, G. R., 112. Hecht, I?., 492, 494. Hecht, H. G., 47. Hecht, R., 254. Heck, R. F., 176. Hecker, E., 278. Hedrich, G. W., 196. Hedrick, R. I., 253. Keeney, H. B., 476. Heeren, J. K., 261. Hegedus, D., 489. Hegre, C. S., 405. Heilbronner, E., 315, 316. H e h a n n , W., 485. Hein, F. R., 185.
Heine, H. W., 279, 320. Heinecke, K., 178. Heinekey, D. M., 333. Heinemann, G., 216. Heintz, E. A., 158. Heinz, W. D., 152. Helbig-Neubauer, M., 163. Heldt, W. Z., 161. Helfferich, F., 171. Heller, C., 57, 205. Heller, H. G., 308. Heller, L., 477. Hellman, L., 431, 433, 434. Hellstrom, F., 417. Helmholz, L., 46. Helmkamp, G. K., 322,379. Helvenston, E. P., 163. Henbest, H. B., 220, 227, 283. Henderson, A. T., 279. Hendler, R. W., 382. Hendra, P. J., 203, 206. Hendrickson, J. B., 343,351. Hendrickson, Y. G., 196. Henery-Logen, K. R., 322. Henkler, H., 258. Hennart, C., 455. Henninger, W. A., 491. Hennis, H. E., 254. Heppolette, R. C., 218. Herb, S. F., 275. Herber, R. H., 169, 495. Herberich, G. E., 183. Herbert, V., 407. Herbst, P., 271. Herbstein, F. H., 504. Herman, J. I., 178. Herman, L., 101, 120, 123, 127. Herman, R., 120, 123. Herman, Z., 123. Hermans, J. J., 93. Hermsen, R. W., 97. Heriiandez Caiiavate, J., 455. Herout, V., 292. Herringshaw, J. F., 466. Herrington, T. M., 86. Herran, J., 348. Herrman, G., 179. Hersel, O., 319. Hersh, R. T., 423. Hershaft, A., 147. Hertz, H. G., 65, 71, 73. Herz, W., 200, 292, 294. Herzberg, G., 99, 100, 101, 106, 107, 108, 109, 116, 119. Herzog, S., 152, 156, 158. Heslop, R. B., 129. Hess, B., 420. Hess, P. H., 223. Hesselbarth, H., 137. Heubner, C. F., 357. Heusler, K., 256, 302, 305. HewIett, C., 145.
530
I N D E X OF AUTHORS NAT ES
Heying, T. L., 135. Hey, D. H., 226, 232, 234, 235, 265, 310, 311. Hiatt, H. H. 379, 380. Hickling, A., 143. Hickmott, T. W., 13. Hicks, W. T., 128. Hieber, W., 176, 177, 178. Higgins, P., 333. Higginson, W. C. E., 142, 157, 171, 173. Highet, R. J., 343, 348. Hijmans, J., 93. Hikino, H., 292. Hikita, T., 20. Hilbert, P., 280. Hildebrand, J. H., 73, 74, 78, 79, 81, 82. Hill, D. W., 437. Hill, H. A. O., 234. Hill, J. A., 143. Hill, J. W., 219. Hill, R. K., 219, 358. Hill, R. L., 396. Hill, S. A., 336. Hiller, M. A., 152. Hillman, M.J., 374. Hilton, I. C., 232. Hilton, J., 446. Hinckley, A. A., 132, 257. Hindman, J. C., 65. Hine, J., 207, 223, 242. Hine, R., 503, 514. Hine, R. A., 483. Hines, T., 68. Hinman, R. L., 326. Hinshelwood, Sir C. N., 27, 238. Hirano, S., 371. Hiraoka, H., 78. Hirase, S., 369. Hirata, Y., 358. Hirota, E., 192. Hirota, N., 53, 57, 58, 61. Hirschfelder, J. O., 88, 114, 126. Hirst, E. L., 370. Hishida, S., 250. Hitchcock, E. T., 473. Ho, J. C. K., 94. Hoare, D. E., 23, 27, 41, 42. Hoare, D. S., 391, 394. Hobbs, C. F., 220. Hobkova, E., 484. Hobson, J. D., 345. Hobson, J. P., 9, 10. Hoch, F. L., 423. Hocking, M. B., 333. Hockings, E. F., 47, 178. Hochmannovit, J., 292. Hochstein, F. A., 350. Hodge, J. D., 209, 285. Hodge, N., 151. Hodges, R., 201, 301, 318. Hodgkin, D. C., 402, 375, 514.
Hodson, H. F., 349. Hogenauer, G., 292. Hoegerle, R. M., 218. Hokfelt, B., 427. Hoeksema, H., 341. Hollerer, G., 139. Koppner, K., 142. Horner, L., 329. Hornfeldt, A.-B., 201, 202, 323, 324. Hoever, H., 282. Hover, H., 307. Hofer, P., 257. Hoffer, M., 374. Hoffman, P., 371. Hoffman, R. A., 201, 202, 323, 324. Hoffmann, A. K., 279. Hoffmann, C. J., 144. Hoffmann, D., 416. Hoffmann, D. E., 132. Hoffmann, H., 233, 261, 472. Hoffmann, R., 131. Hoffmann, R . W., 235, 311. Hoffmeister, E., 235, 311. Hofheinz, W., 366. Hofman, T., 420. Hofmann, A., 352. Hofmann, A. F., 446. Hofmann, H., 332. Hogenaner, G., 200. Hogenkamp, H. P. C., 402. Holah, D. G., 171. Holder, B. E., 151. Holder, G. A., 96. Holden, K. G., 325, 393. Hole, F., 338. Holenaar, E., 340. Holland, G. J., 439. Holland, W. D., 474. Hollander, N., 430. Holleman, Th., 93. Holley, R. W., 382. Holliday, A. M.,136, 143. Holliman, F. G., 339. Hollinghead, S., 240. Hollis, B., 497. Ho116, J., 369. Holloway, H., 170. Holloway, P. W., 360. Holm, R. H., 165. Holmes, J. L., 236. Holmes, R. R., 145. Holmstrom, B., 320. Holmstrom, E. G., 429. Holness, N. J., 223. Holser, W. T., 506. Holt, A. S., 399. Holt, L. B., 394. Holt, P. F., 338. Holton, P. G., 201, 347. Holzbecher, Z., 477. Homann, P., 335. Homberg, K., 368. Homer, J., 363.
Honyo, M., 417. Hook, S., 410. Hooton, K. A., 141, 166. Hope, H., 512. Hopkins, C. Y., 275. Hopp, M., 278. Hoppe, R., 130, 153, 161. Hoppe, W., 502. Hora, J., 303. HorGek, J., 473, 475. Horitk, V., 341. Hordvik, A., 359. Horii, Z., 358. Horl, W., 182. Hormanski, M., 415. Horn, D. H. S., 278, 297. Horner, L., 261, 264, 316, 446. Horner, S. M., 159. Horning, E. C., 277. Horsfield, A., 53, 54, 55, 56, 57. Horst, R. B., 54. Hort, J., 328. Horton, A. D., 448. Horton, D., 367, 368. Horton, G. R., 499. Horwatitsch, H., 473, 474. Horyna, J., 482. Hoskins, B. F., 163. Hoakinson, R. M., 363. HoBialek, Z., 458. Hoste, J., 452, 489, 490, 491, 492, 493, 495. Hougen, J. T., 118. Hough, L., 201, 204, 361, 363, 364, 370. Houk, N. B., 122. House, D. A., 172. House, H. O., 260. Houser, J. J., 209. Hovenkamp, S. G., 507. Hover, H., 281. Howald, R. A., 253. Howard, C. C., 322. Howard, E., jun., 146. Howard, J. W., 444. Howard, W. L., 320, Howe, C. A., 236. Howe, L. L., 100, 101. Howell, C. F., 286. Howick, L. C., 452. Hoyle, W., 440. Hozumi, K., 474. Hrdina, J., 447. Hristidu, Y., 183. Hruky, V. J., 242. Hubbard, N., 395. Hubbard, W. N., 196. Huber, C. O., 471. Huber, K. P., 116, 125. Huber, W., 459. Huber-Buser, E., 287. Huber-Emden, H., 267. Huculak, W. W., 256. Huckel, W., 290.
INDEX
OF A U T H O R S NAMES
53 1
Hudda, F. G., 11, 12. Hudec, J., 197,285,289,309. Hudson, B., 433. Hudson, B. G., 452. Hudson, F. M., 233. Hudson, G. H., 90. Hudson, H. R., 133. Hudson, P., 509. Hudson, R. F., 219, 252, 253, 254. Hudson, R. L., 35. Hubernett, F., 332. Hubner, L., 171. Huttner, W., 192. Huffman, K. R., 338. Huffman, J. W., 258. Hughes, A. N., 338. Hughes, C., 343. Hughes, D. O., 504, 506. Hughes, D. W., 399. Hughes, E. D., 218, 238. Hughes, E. W., 283, 509. Hughes, N. A., 360. Hughes, R. H., 101. Hughes, S. A., 235. Hugo, T. J., 106. Huisgen, R., 312, 323, 330, 332, 333, 337. Huitric, A. C., 196, 197. Huka, M., 469. Hukue, N., 277. Hulanicki, A., 449. Huizinga, F., 383. Hulburt, H. M., 114. Hulme, R., 51, 142, 511. Hulthhn, E., 100, 104. Humber, L. G., 357. Humberlin, R., 238. Hume, D. N., 482. Humphreys, S. R., 417. Hung Yu Chen, 480. Hunneman, D. H., 334. Hunt; J. A., 381. Hunt, J. H., 263. Hunt, 5. P., 68. Huntsman, W. D., 270. Hunter, G. J., 495. Hunter, M. J., 249. Hurley, A. C., 113, 121. Hurlbert, B. S., 358. Hurst, G. L., 138. Hurst, J. J., 213. Hurst, P., 37. Hurzeler, H., 125. Hush, N. S., 175. Hutchinson, D. A., 56. Hutchison, C. A., 60. Hutchison, C. A., jun., 63. Hutchison, R. B., 318. Hutton, D. G., 37. Hutton, H. M., 281. Hutton, R . F., 334. Hyde, A. J., 160. Hyde, J. S., 54. Hylton, T. A., 165. Hyne, J. B., 217.
Iball, J., 503, 509. Ibanez, L. C., 305. Ibers, J. A., 47, 163, 179. Iberson, E., 164. Ibne-Rasa, K. M., 224. Ichimescu, A., 120. Ide, Y., 481. Idris Jones, J., 137. Iino, N., 278. Ikekawa, N., 356. Ikenoue, K., 126. Ilakovac, N., 223. Ilin, V. T., 30. Illuminati, G., 231. Imamura, A., 83. Imri;, P., 499. Inch, T. D., 366. Inghram, M. G., 125. Ingle, R. B., 455. Ingles, D. L., 360. Inglis, G. R., 362. Ingold, C. K. (Sir), 207,218, 222, 238. Ingold, K. U., 199, 254. Ingraham, L. L., 187, 207. Ingram, D. J. E., 47. Inman, D., 167, 472. Innes, K. K., 106. Inomata, Y., 478. Inoue, M., 275. Inoue, T., 265. Inoue, Y., 339. Inukai, T., 219. Inward, P. W., 227. Ireland, R. E., 264, 296, 298, 302. Irudayasamy, A., 441. Irvine, D. H., 175. Irving, H., 170. Isbell, H. S., 359, 360, 361, 496. Isenberg, H. D., 403. Isenberg, I., 62. Isensee, H. J., 499. Ishima, A., 380. Isler, O., 274. Issleib, K., 140, 163, 166. Ito, J., 71. Ito, K., 165. Ito, M., 281. Ito, T., 367. Ito, Y., 368. Itoh, K., 57, 206. Ivanov, 0. A., 24. Ivanov, V. M., 455. Ivanova, T. M., 97. Ivanov-Emin, B. N., 138, 152. Iverach, G. G., 357. Ives, D. J. G., 97. Iwai, I., 360. Iwamoto, R . T., 167. Iwamoto, T., 454. Iwasawa, J., 298. Iwashige, T., 360. Iwatsubo, M., 425.
Izsak, D., 191, 192. Jaccard, C., 55. Jackerts, D., 372. Jackman, L. M., 198, 273, 277, 286, 296, 307, 318. Jackman, M. I., 485. Jackson, A. H., 323, 392. Jackson, H., 444. Jackson, J. A., 67. Jackson, J. E., 429. Jackson, J. F., 417. Jackson, P. W., 411. Jacob, F., 379. Jacobs, G. D., 192. Jacobs, S., 475. Jacobs, W. A., 357. Jacobsen, E., 460. Jacobson, I. A., 324. Jacobson, M., 278. Jacques, J. K., 121. Jager, H., 230. Jaenicke, L., 407. Jaenicke, R., 424. Jaenicke, W., 472. Jaff6, H. H., 240. Jailer, J. W., 432. Jain, B. D., 450, 451, 479. Jain, D. C., 112, 114, 116. Jalkowski, J. F., 490. James, A. T., 274. James, C., 270. James, H., 26. James, M. R., 94. James, T. C., 113. Jamieson, J. C., 501. Janak, J., 448. Jander, J., 143, 151. Jangida, 13. L., 444, 478. Janot, M.-M., 204, 205, 351, 352, 353, 354, 356. Janssen, M. J., 142. Janzen, E. G., 49. Jardetzky, C. D., 205, 418. Jardetzky, O., 71. Jarlsiiter, N., 104. Jarmain, W. R., 111, 112, 113. Jarman, L., 488. Jarvis, J. A., 368. Jarvis, J. A. J., 512. Jaseja, T. S., 53, 205. Jastrow, H., 271. Jayle, M. F., 427. Jeanloz, R. W., 365. Jeannin, Y., 155. Jeffcoat, K., 463. Jefferies, P. R., 278, 298. Jefford, C. W., 240, 338. Jeffrey, G. A., 508. Jeffs, P. W., 343. Jeger, O., 305. JehliEka, V., 482. Jellum, E., 456. Jen, C. K., 57. Jen, M., 191.
532
Jenc, E., 113. Jenckel, L., 497. Jencks, W. P., 245, 247, 248, 249, 252. Jenkins, D. R., 207. Jenkins, F. A., 101. Jenkins, R. W., 209. Jennings, H. J., 365. Jennings, V. J., 453, 467, 489. Jensen, F. R., 196, 282. Jensen, H. B., 324, Jensen, J., 396. Jensen, L. H., 503,504,506, 509. Jensen, S. L., 271, 274. Jenssen, B., 273. Jere, G. V., 155. Jeunehomme, M., 127. Jewell, D. M., 498. Jha, N. K., 161. Jibnil, A., 416. Jira, R., 258. Jirgensons, B., 425, 426. Jirka, M., 487. Jirkovskjr, I., 346. Jizba, J., 292. Job, B. E., 192. Jobsis, F., 418. Joe, F. L., jun., 444. Jorgensen, C. K., 164. Johannesen, 1.-J.,150. Johannesen, W., 150. Johansson, N., 100, 104. John, J. P., 287. John, K., 145. Johns, H. E., 372. Johns, J. W. C., 101, 121. Johns, R. B., 341. Johnson, A. W., 314, 331, 337, 375, 389, 402, 409, 411. Johnson, B. C., 403, 404. Johnson, B. F. G., 178. Johnson, C. M., 109. Johnson, C. R., 260. Johnson, D. L.,280. Johnson, D. W., 219. Johnson, E. A., 232, 233. Johnson, F., 334. Johnson, F. A., 54, 144. Johnson, 0. A., 42. R. Johnson, H. E., 265, 279. Johnson, H. W., jun., 286. Johnson, L. F., 203, 296, 365. Johnson, Le R. F., 297. Johnson, M. D., 207, 338. Johnson, R. C., 175. Johnson, R. D., 223. Johnson, R.W., jun., 196. Johnson, S., 139, 232, 319. Johnson, 5. L., 247, 248. Johnson, W. S., 196, 224, 267, 306, 355. Johnston, G. A. R., 210.
Johnston, J. D., 288, 318. Johnston, N. C., 277. Jolly, W. L., 139, 141, 148. Jones, D., 184. Jones, G. R. H., 44. Jones, G. W., 20, 21, 373. Jones, H. C., 482. Jones, H. G., 359. Jones, J. H., 37. Jones, J. K. N., 359, 360, 365, 366. Jones, J. M., 252. Jones, K., 142. Jones, M., jun., 200. Jones, M. M., 233. Jones, M. R., 88. Jones, M. T., 60. Jones, N. D., 512. Jones, 0. W., 381. Jones, P. D., 478. Jones, R. A. Y., 64, 189, 203, 338. Jones, R. C., 51. Jones, R. H., 170. Jones, R. L., 193. Jones, R. N., 191. Jones, W. A., 278, 329, 447. Jones, W. M., 227, 252. Jongerius, H. M., 120. Jordan, J., 161. Jordan, T., 230, 507. Jorgensen, C. K., 46. Jorgenson, M. J., 257. Jortner, J., 63. Joschek, H.-I., 265. 3osefsson, L., 466. Joseph, A., 460. Josephson, R. R., 214. Joshi, K. C., 119. Joshi, K. K., 177, 183. Joshua, C. P., 333. Josse, J., 373, 378. Jost, E., 262. Joule, J. A., 348, 355. Joullie, M.M., 335. Joyce, B. K., 425. Joyner, T. B., 163. Juardo-Soler, A., 362. Julia, M., 270, 273, 274. Julia, S., 273. Julietti, F. J., 280. Julita, P., 411. Jungalwela, F. B., 274. Jungermann, E., 261, 323. Jurale, J. B., 219. Jursa, A. S., 123. Jutz, C., 314. Kabasakalian, P., 267, 287. Kabat, E. A., 368. Kabuss, S., 204. Kacmarczyk, A., 131. Kacmarek, A. J., 147. Kader, A. R., 216. Kaeding, W. W., 263. Kagi, W., 219.
Kagan, F., 263. Kagan, G. I., 190. Kagawa, Y., 415. Kagi, H. H., 287. Kagi, J. H. R., 423, Kahn, N. H., 357. Kahn, R. K., 378. Kahnt, F. W., 429. Kainz, G., 473, 474. Kaiser, E. T., 248. Kaiser, H., 316. Kakihara, N., 20. Kakisawa, H., 290, 302. Kalinin, A. I., 485. Kalinowska, Z. E., 465. Kallen, R. G., 374. Kalman, Z. H., 477. Kalsi, P. S., 290. Kalvoda, J., 305. Kamal, M. R., 95. Kamata, H., 345. Kambara, S., 155. Kampmeier, J. A., 235, 311. Kan, R. O., 232, 337. Kanamori, K., 454. Kanda, T., 68. Kandalic, G. A,, 97. Kandel, S. I., 343. Kandler, J., 164. Kane, P. O., 482. Kanekar, C. R., 203. Kaneko, T., 345. Kanjpr, H., 338. Kaniecki, T. J., 263. Kanthamani, S., 355. Kapallo, W., 96. Kapbtanidis, I., 468. Kaplan, A. M., 478. Kaplan, J., 125. Kaplan, N. O., 413, 415, 416, 417, 418, 419, 421, 424. Kapoor, A. L., 512. Karabatsos, G. J., 194, 217. Karapetyan, M. G., 289, 318. Karetskaya, N. I., 346. Karimoto, R. S., 331, 358. Karle, I. L., 503, 508. Karle, J., 503. Karlbn, B., 194. Karmalkar, P. K., 82. Karmen, A., 495. Karmilova, L. V., 28, 29, 30. Karpathy, 0. C., 448. Karplus, M., 50. Karrer, P., 273. Kartha, G., 503, 512. Kasai, P. H., 62. Kase, N., 428, 429. Kaska, W. C., 266, 334. Kasteleyn, P. W., 94. Kasturi, T. R., 256. Katayama, M., 53, 206.
533
Katayama, T., 97. Katchalski, E., 253. Kates, M., 274. Kats, N., 358. Katritzky, A. R., 64, 189, 203, 232, 324, 332, 336, 338. Katsuhiko Ichikawa, 233. Katti, M. R., 114. Katz, F. H., 432. Katz, I., 274. Katz, J. J., 325. Katz, T. J., 228, 282, 283, 312, 314. Kau, H., 484. Kauer, E., 96. Kauffmann, T., 235, 258, 330, 335. Kaufman, F., 43. Kaupp, G., 332. Kawai, K., 175. Kawanisi, M., 277. Kawasaki, I., 345. Kawazoe, Y., 201. Kay, I. T., 325. Kay, J. G., 102. Kaziro, Y., 404. Kealey, T. J., 338. Keefe, J. R., 253. Keefer, R. M., 82, 217, 220, 226, 233. Keeler, B. T., 487. Keeler, R. N., 89. Keen, N., 65, 56. Keeney, M., 274. Kehlen, H., 95. Keijer, J. H., 340. Keller, C., 446. Keller, H. J., 183. Keller, R. A., 448. Kellerman, G. M., 404. Kellermeyer, R. W., 405. Kellie, A. E., 433. Kelly, H. C., 139. Kelly, W. G., 431. Kempton, A. G., 478. Kende, H. J., 399. Kende, I., 34. Kenner, G. W., 323, 332, 338. Kenney, M. E., 137. Kenney, T. E., 190. Kent, P. W., 365. Kenty, C., 123. Keresztesy, J. C., 407. Kern, R. J., 223. Kerr, J. R. W., 496. Kerwin, J. F., 303. Kerwin, L., 128. Kesser, S. IT., 338. Ketova, L. A., 468. Ketteringham, J. M., 126. Kettle, S. F. A., 177. Keuning, R., 275. Kevill, D. N., 223, 224. Kewley, R., 207.
Kezdy, F., 248. Khabibullin, B. M., 72. Khachishvili, V. I., 131. Khalique, A., 360. Khan, B. T., 427. Khan, M. A., 127, 448. Khan, I. A., 177. Khandelwal, B. L., 458. Khanna, B. N., 128. Kharasch, N., 188,235,269. Khazanova, N. E., 98. Khazova, I. P., 441. Khdanov, G. S., 509. Khetrapel, C. L., 203. Khodeeva, S. M., 98. Khopkar, S. M., 443. Khorana, H. G., 376, 377, 378. Khorana, M. L., 300. Khorlina, I. M., 262. Khoroshin, A. V., 486. Khudyakovg, T. A., 459. Khu Khun-ven, 230. Khuong-Hu, Q., 356. Khym, J. X., 377. Kibbel, H. U., 136. Kibly, C. K., 132. Kida, S., 172. Kidd, R. G., 171. Kiefer, E. F., 210. Kielar, E. A., 348. Kielich, S., 92. Kierstead, R. C., 296. Kies, H. L., 458, 462. Kiese, M., 396. Kiess, N. H., 116. Kihara, T., 89. Kikino, Y., 292. Kikuchi, G., 386. Kikuchi, K., 316. Kikumoto, R., 350. Killean, R. C. G., 513. Killheffer. J. V.. 261. 323. Killick, R. A., 490. ' Kilzer, J., 350. Kim, Y. S., 229. Kindler, K., 323. King, A. B., 123. King, A. D., 92. King, D. M., 472. King, G. W., 128. King, N. J., 370. King, P. A., 224. King, W. R., 95. Kingston, A. E., 89. Kingston, W. R., 169. Kinsey, J. L., 19. Kirby, G. W., 343. Kircher, H. W., 364. Kirei, G. G., 207. Kirk, A. D., 31. Kirk, D. N., 306. Kirk, K., 285. Kirkien-Konasiewicz, 253. Kirkland, A., 364.
Kirksey, C. H., 338. Kirkwood, J. G., 84. Kirkwood, S., 367. Kirschfeld, S., 373, 403, 409. Kirschner, S., 171. Kirsten, W. J., 474. Kishida, Y., 294. Kiss, S. A., 470. Kister, A. T., 98. Kistiakowsky, G. B., 19, 20, 241. Kitaigorodski, A. I., 506. Kitao, T., 336. Kitaoka, S., 368. Kitaoka, Y., 336. Kiuvila, H. G., 233. Kivelson, D., 58, 59. Kjaer, A., 279, 331. Kjerlberg, O., 370. Klanberg, F., 137. V., Klassen, hT. 232, 233. Klavins, J. E., 362. Klein, E., 289. Klein, J. R., 395. Klein, M. J., 147. Klein, O., 113. Klein, P. D., 444. Kleinberg, J., 181, 227. Kleine, K.-M., 271. Kloinert, H., 330. Kleinfetter, D. C., 209. Kleinman, L., 604. Kleinschmidt, A., 378. Kleman, B., 106, 119. Klemer, A., 368. Klemm, W., 161. Klenow, H., 417. Klesper, E., 151. Kliever, M., 403. Klinedinst, P. E., 335. Klinedist, P. E., 214. Klinedist, P. E., jun., 416. Kling, O., 158. Klingelhoefer, W. C., 465, Klingsberg, E., 319, 333. Klink, W., 261. Klonowski, R. S., 322. Klopman, G., 219. Kloster-Jensen, E., 270. Klug, E. D., 369. Klyne, W., 197, 256, 298. Klynning, L., 127. Knaap, H. F. P., 86, 87. Knappe, J., 330. Knessl, O., 480. Knight, C., 394. Knight, C. S., 448. Knight, H. T., 128. Knight, J. C., 256. Knight, S. A., 289. Knipmeyer, H. E., 196. Knipple, W. R., 176. Kniseley, R. N., 193. Knobler, C. M., 87. Knobler, C., 103.
534
Knoester, M., 87. Knoke, J., 335. Knorr, R., 312. Knoth, W. H., 131. Knowles, A., 286. Knowles, J. W., 502. Knowles, P., 157. Knox, G. R., 230, 258. Knox, J. H., 22, 31, 32, 33, 34, 35. Knox, J. R., 278. Knox, K., 46, 158. Knuppen, R., 433. Knyazev, D. A., 494. Kobayashi, H., 299. Kobayashi, S., 302. Kobayashi, T., 350. Koch, H. J., 271. Koch, W., 232, 278. Kochetkov, N. K., 331, 346. Kocor, M., 290. Kodera, K., 358. Kobrich, G., 230, 261. Koechlin, W., 268. Koehelik, I. H., 403. Koehler, W. R., 320. Konig, H., 230. Konlg, K., 142. Konigk, E., 374. Koffman, L., 100, 104. Kofler, M., 274. Kofman, A. N., 98. Kofron, W. G., 264. Kogan, E. A., 97. Kohler, F., 90. Kohlhage, H., 376. Kohlschutter, H. W., 136, 168, 422. Kohn, J. P., 98, 99. Kohnstan, G., 214,217, 218 Koizumi, K., 367. K o j h a , T., 195. Kokeritz, P., 199. Kokko, J. P., 374. Kokot, E., 166. Kolat, R. S., 152. Kolb, A., 341. Kolbasov, V. I., 480. Kolbe, A,, 95. Kolbin, N. I., 161. Kolditz, L., 147. Kolesnikova, R. V., 43, 44. Kolewe, O., 246. Kolinskii, R., 269. Kolos, W., 113. Kolosov, M. N., 318. Kolysko, L. E., 91, 95. Kompa, K. L., 144. Kon, S. K., 411. Konaka, R., 260. Kondo, K., 277. Kondo, N., 380. Kondrashev, Yu. D., 507. Kondratiev, V. N., 25, 26. Konereva, G. P., 32. Konf PO Mirnomu, 369.
Konigsberg, W., 333. Konowalow, D. D., 126. Kopanica, M., 441, 484. Kopecky, K. R., 241, 262. Kopp, I., 127, 128. Koppel, H. C., 339, 374. Kopple, K. D., 174. Koransky, W., 376. Korbl, J., 473. Koreshkov, Yu. D., 322. Korkisch, J., 483. Kormendy, C. G., 335. Korn, J. K., 136. Kornberg, A., 373,374, 378. Kornberg, S. R., 373. Kornblum, N., 279. Kornis, G., 300. Korte, F., 195, 281. Korst, J. J., 288, 318. Korving, J., 86. Korwar, V. M., 112. Kosak, J. R., 240. Kosel, C., 258, 330. Koshijima, T., 370. Kosicki, G. W., 246. Koski, W. S., 205. Kosower, E. M., 187, 229, 281, 335, 413, 416, 418, 423. Koster, G. F., 46. Kotake, M., 345. Kotera, K., 198. Kotzian, H., 455. Koubeck, E., 186. Kovacic, P., 233. KOVACS, 107, 117, 118. I., Kovalenko, P. M., 481. Kovalskii, A. A., 26. Kovar, J., 344. Kowkabany, G. N., 359. Kowal, J., 428. Kowalski, E., 388. Kozak, G. S., 465. Kozima, T., 299. Krall, R. E., 253. Kramer, D. N., 465. Kramer, K., 139. Kramer, K. S., 475. Krapcho, A. P., 219, 279. Krasinski, A. H. A., 277. Krasna, A. I., 411. Kratochvil, M., 328. Kratzer, O., 274. Krauch, C. H., 328, 340. Kraus, J. W., 179. Krauss, H.-L., 157, 159. Kraut, J., 503, 514. Krebs, A., 286. Krebs, E. G., 414. Kreevoy, M. M., 222, 269. Kreibach, A., 166. Kreienbring, F., 365. KFepinskjr, J., 292. Kresge, A. J., 233. Kreshkov, A. P., 457, 462. Krespan, C. G., 323.
Kretsinger, R. H., 514. Kretszchner, R., 417. Krichevskii, I. R., 98. Krijn, G. C., 451. Krilrorian, 0. H., 128. K r h m , S., 192. Krischke, R., 337. Krishnamurti, M., 269. Kritsyn, A. M., 346. Krivoglaz, M. A., 504. Krohnke, F., 309, 335. Kroger, C., 38. Kroh, J., 49. Krohs, W., 319. Kronenberger, K., 482,497. Kruck, T., 177. Kruger, C. R., 140. Krueger, P. J., 193. Krueger, R. C., 395. Kruh, J., 380. Krumholz, P., 175. Kruse, F. H., 154. Kruseman Aretz, F. E. J., 94. Kubo, H., 425. Kubo, M., 165. Kubota, T., 295. Kucan, D., 303. Kuchen, W., 146. Kuck, A. M., 347. Kuckertz, H., 140. Kuczynski, E. R., 463. Kuebler, N. A., 102. Kuehner, E. C., 440. Kung, W., 219. Kiinzel, O., 182. Kuffner, F., 268. Kuge, T., 369. Kugel, L., 143. Kuhn, R., 272. Kuhn, S. J., 232, 233, 268. Kukushkin, Yu. N., 175. Kulanek, M., 95, 96. Kulba, F. Ya., 138. Kulborskaya, N. K., 272. Kuljian, A., 427. Kulkarni, B. D., 355. Kumar, A., 386. Kumar, S., 153, 450. Kumazawa, Z., 298. Kumler, W. D., 193, 194, 246. Kump, C., 354. Kump, W. G., 354. Kun, E., 246. Kunchur, N. R., 168. Kung, W., 287. Kunin, R., 447. Kunkel, W. B., 123. Kuno, S., 373. Kuo, C. H., 318. Kuo, M. C. C., 320. Kupchan,, S. M., 250, 306. Kupfer, D., 257. Kuri, Z., 51. Kuriakose, A. K., 231, 270.
I N D E X OF AUTHORS N A T ES
535
Langan, T. A., 418. Langford, C. H., 162. Langford, P. O., 162. Langley, B. W., 299, 359. Langworthy, W. C., 230. Lansbury, P. T., 257. Lanskoi, G. A., 454. La Paglia, S. R., 107. Lapinski, R., 246. Lapisova, N. P., 473. Laplante, J. P., 485. Laporte, H., 175, 182. Lapp, M., 110. Lappert, M. F., 131, 133, 142, 156. Lapworth, A., 232. Larionova, L. E., 138, 152. Larkin, J. A., 93, 95. Larkworthy, L. F., 143. Larrabee, A. R., 406, 407. Larroqube, J., 421. Lascelles, J., 386, 388, 409. Lassner, E., 441, 455. Laszlovsky, J., 441. Lathan, R., jun., 155. Latif, N., 321. Latscha, H. P., 148. Lattermann, H., 438. Labbe, R. F., 393, 395. Laubengayer, A. W., 137. LabbB, J. P., 450. Laug, P., 303. Lacher, J. R., 282. Laune, J., 196. Lack, R., 201. Lauritzen, C., 427. Ladd, J. N., 401, 402. Laursen, R. A., 373. Ladd, M. F. C., 169. Laver, M. L., 370. Ladeinova, L. V., 155. Laver, W. G., 386. Laffitte, P., 37. Lavie, D., 300. Lagerkvist, U., 382. Law, H. D., 332. Lagerqvist, A., 101, 106, Law, J. T., 13. 116, 124, 128. Law, P. A., 209. Lai, M. G., 495. Lawley, D., 373. Laidler, K. J., 17. Lawrence, R. V., 297. Laine, F., 356. Lawrey, D. M. G., 497. Laitinen, H. A., 459. Lawson, A. W., 501. Lakom9, J., 459. Lawson, D. D., 446. Lakshmikanthan, M. IT., Layne, D. S., 430. Layton, R., 165. 358. Lamantia, L., 417. Lazar, J., 224. Lamb, D. C., 277. Lazarova-Girsamof, V., Lambert, M., 86. 128. Lamberton, J. A., 278. Leake, L. R., 466, 470. Lamborg, M. R., 416. Learner, R. C. M., 113, 116. Lampetaz, J.-C., 442. Le Bargy, R. C., 124. Lamprecht, W., 437. Lebedeva, A. I., 475. Lamyaeva, V. N., 184. Lebedeva, A. S., 346. Lancaster, J. E., 366. Lebedeva, E. S., 98. Landau, R., 258. LeBel, N. A., 224. Lander, A., 185. LeBel, R. G., 97. Lander, W. R., 480. Leboeuf, M., 355. Landor, S. R., 272. Leckie, A. H., 125. Landry, B. J., 233. Lecomte, J., 198. Lane, A. P., 145. Le Count, D. J., 354. Lane, C. A., 224. Leddicotte, G. W., 489. Lane, M. D., 405. Lederer, E., 278. Laney, D. H., 263. Ledwith, A., 219. Lang, A. R., 502. Lee, C. C., 213. Lang, D., 229, 378. Lee, C. M., 193, 336. Kurihara, T., 278. Kurita, Y., 165. Kurland, C. G., 379. Kuroda, R., 491. Kursanov, D. N., 322. Kurtz, P., 269. Kurz, H., 396. Kurzer, F., 279, 333. Kusch, K., 431. Kushner, D. J., 274. Kusomoto, S., 345. KUSSY, E., 444, 492. M. Kustin, K., 246. Kuteinkov, A. F., 454. Kutek, F., 458. Kutschke, K. O., 40, 236. Kutsenko, Yu. I., 154. Kutzelnigg, W., 194. Kuwama, T., 60. Kuzel, P., 183. Kuznetsova, N. L., 44. Kuzyakov, Yu. Ya., 127. Kwart, H., 197, 237, 284. Kwie, W. W., 304. Kydd, P. H., 20. Kyogoku, Y., 372, 379. Kyryacos, G., 32.
Lee, E. E., 367. Lee, E. K. C., 494. Lee, H. A., 403, 409. Lee, H. A., jun., 420. Lee, H. Y., 482. Lee, J. K., 494. Lee, J. S., 497. Lee, K. T., 440. Lee, M. N., 400. Lee, W. G., 224. Lee, W. H., 169. Lee, W. W., 375, 424. Leermakers, P. A., 241. Leete, E., 342. Lefebvre, C., 95. Lefebvre-Brion, H., 113. Le Fkvre, R. J. W., 190, 191, 192, 199, 201, 203. Le Goff, E., 235, 283, 311, 315. Legrand, M., 200. Le Gras, J., 272. Lehar, L., 459. Lehman, I. R., 373. Lehmann, G. J., 242. Lehmann, H.-A., 137. Lehma.nn, J., 363, 366. Lehmann, W. J., 132, 135. Lehn, J.-M., 200, 303. Lehr, W., 146. Leibnitz, E., 34. Leicht, C. L., 350, 351. Leies, G. M., 115. Leigh, G. J., 141, 155. Leigh, K., 197. Leigh, R. T., 142. Leland, T. W., 98. Leliaert, G., 492. Lelov, N. F., 505. Le Men, J., 204, 205, 351, 352, 353, 354. Lemieux, R. U., 365, 418. Lemons, J. F., 67. Lengnick, G., 137. Lengyel, P., 381, 404. Lenkert, P. G., 375, 402. Lenzer, S. L., 166. Leonard, G. W., 483. Leonard, J. A., 232, 234, 235, 310, 311. Leonard, J. E., 467. Leonard, N. J., 260, 342, 373. Leonov, V. N., 306. Lepard, D. W., 190. Lerch, A., 242. Lerwill, B. R., 142. Lesigang, M., 494. Leskowitz, S., 368. Leslie, R. T., 440. Lesnevskaya, L. S., 98. Lester Smith, E., 409. Letort, M., 30, 31. Letsinger, R. L., 252. Levenson, L. L., 9. Lever, A. B. P., 162.
536
INDEX OF AUTHORS N A
ES
Levelt, J. M., 88. Levin, P. L., 32. Levine, C. A., 491. Levine, I. N., 194. Levine, L., 419. Levine, S., 365. Levinskii, M. I., 486. Levisalles, J., 200. Levisalles, J. E. D., 293. Levitan, I. O., 198, 200. Levitus, R., 172. Lewandowski, K. M., 208. Lewin, A. H., 197. Lewin, N., 294. Lewis, C. H., 139. Lewis, D. T., 496. Lewis, E. S., 233. Lewis, J., 154, 158, 162, 167. Levy, A., 21, 416. Levy, J. F., 213. Levy, J., 352. Li, T. K., 420. Libergott, E., 441, 442. Lichten, W., 118. Lichtenthaler, F. W., 280. Lichtin, N. N., 362. Lide, D. R., 121, 1189, 190, 191, 193. Lide, D. R., jun., 190. Liebe, W., 153. Lieberman, S., 429, 430, 431, 432, 433. Lieberman, S. L., 434. Liede, V., 327. Liehr, A. D., 168. Lieser, K. H., 136. Lightner, D. A., 291. Lightowlers, E. C., 491. Likhosherstov, A. M., 346. Liljegren, D. R., 350. Lilly, R. L., 308. Limanov, V. Y., 306. Lindberg, B., 360, 368. Lindberg, J. J., 97. Linde, H., 446. Lindgren, B., 127. Lindner, E., 176, 178. Lindner, H. R., 428. Lindqvist, S., 119. Lindsey, J., 514. Linevsky, M. J., 103. Linford, H. B., 460. Linnenbom, V. J., 449. Linnett, J. W., 100, 114, 131. Linstrom, F., 454. Lions, F., 172. Lipman, M. M., 432. Lipmann, F., 382. Lipowitz, J., 250. Lippincott, E. R., 113, 114, 130, 190. Lipscomb, W. N., 131, 132, 181, 230, 501, 502, 507, 512.
Lipsett, M. B., 427, 428. Liptay, G., 500. Liptay, W., 82. Lis, A. W., 376. Lischlre, G., 34. Lisitsa, M. P., 207. Lissitzky, S., 494. Lister, J. H., 320. Little, E. L., jun., 279. Little, W. F., 250. Littlehailes, J. D., 302. Liu, I. D., 23. Livingston, R., 47, 55. Livingstone, J. G., 185. Livingstone, S. E., 165, 172. Ljunglin, J. J., 95. Llewellyn, F. J., 164. Lloyd, H. A., 348. Lloyd, I. R. L., 361. Lobaneva, 0. A., 162. Lock, C. J. L., 160. Lockhart, J., 210, 281. Lockhart, J. C., 135. Locksley, H., 300. Lockwood, W. H., 390. Lockyer, T. N., 166. Lodemann, E., 372. Loder, J. W., 292. Lodish, H. F., 204, 354. Loeb, A. L., 506. Loebeck, M. E., 374. Loeffler, L. J., 348. Loewenstein, A., 269. Loewenthal, H. J. E., 294, 298. Lofthus, A., 122. Loginov, G. M., 156. Lohmann, D. H., 130, 165 Lohning, U. E., 380. Loley, F., 490. Lombaert, R., 490. Long, F. A., 246, 316. Long, L., jun., 365. Long, L. H., 185. Longo, J., 161. Longone, D. T., 200, 258, 317. Longuet-Higgins, H. C., 47, 59, 81. Lonsdale, K., 504. Lontz, R. J., 53. Lord, R. C., 195. Lordi, N. G., 488. Lorentso, R. V., 21. Lorenz, M. R., 138. Lorenz, O., 457. Los, M., 297, 318. Lott, K., 47. Loubser, J. H. N., 192. Loudon, J. D., 308. Louloudes, S. J., 277. Love, D. L., 495. Loveday, G. W., 246, 362. Loveridge, B. a., 494. Lovins, R. E., 217. Low, D. I. R., 96.
Lowde, R. D., 504. Lown, J. W., 200. Lowry, B. R., 288. Lowry, 0. H., 414. LOW~Y, W., 413. 0. LOW~Y, H., 230. T. Lu, B. C.-Y., 94. Luborsky, S. W., 378. Lucas, J., 154. Lucquin, M.,38. Luddy, F. E., 275. Ludoweig, J., 416. Ludwig, M. L., 249. Ludwig, P., 48, 60. Luttringhaus, A., 204, 341. Lui, J. S., 209. Luijten, J. G. A., 142. Lukas, S., 133. Lukes, R., 344. Lukyanychev, Yu. A., 154. Lumbroso, H., 192, 193, 206, 510. Lumpkin, H. E., 199, 497, 498. Lund, E., 197. Lupton, 3 . A., 496. 3 Lust, W. A., 145. Lutz, E. F., 321. Lutz, R. P., 240. Luxmoore, A. R., 181. Lwowski, W., 230, 244. Lyke, W. A., 445. Lykos, P. G., 339. Lyle, G. G., 326. Lyle, R. E., 326, 335. Lynch, B. M., 235. Lynch, C. C., 486. Lynch, E. R., 235. Lynden-Bell, R. M., 61. Lynen, F., 404. Lynen, P., 404. Lyon, R. K., 20. Lyssy, G. H., 474. Lythgoe, B., 299, 359. Ma, J. C. N., 200. Ma, T. S., 442, 473. Mabry, T. J., 327. McAfee, K. B., jun., 142. McBee, E. T., 229, 231, 288. McBride, D. W., 177, 180. McBride, J. J., jun., 261, 323. McCaffery, A. J., 169. McCaldin, D. J., 343. McCall, E. R., 235. McCall, M. A., 279. McCallum, K. S., 320. McCapra, F., 297, 298. McCarley, R. E., 158. McCarthy, R. L., 236. McCarty, M., 102. McCaskill, E. S., 338. McClenaghan, I., 283. McCleverty, J. A., 185.
537
McCloskey, A. L., 135. McCloskey, J. A., 194, 204, Maccoll, A., 224, 253. McConnell, H. M., 46, 51, 61. McConnell, J. F., 289, 513. McCormick, J. R. D., 319. McCoubrey, J. C., 90. McCready, R. M., 364. McCrindle, R., 300. McCullough, J. D., 512. McCnllough, J. J., 227, 283. MeCully, K. S., 378. MacDiarmid, A. G., 139, 141, 149. McDonald, A. J., 478, 489. Macdonald, P., 429. MacDonald, P. C., 432. MacDonald, S. F., 389, 391, 392, 393, 394, 396. McDonald, W. S., 134, 137. McDonough, J. M., 147. McDowell, B. L., 309. Macdowell, C. A., 43, 51, 56, 60, 122. McDowell, J. W., 256. McElhinney, R. S., 322. McEwen, W. E., 227. MacFarlane, M. G., 274. McFarlane, W., 176. McGarvey, B. R., 47, 71. McGarvey, J. E. B., 348. McGarvey, J. J., 101. McGarvey, F. X., 447. McGeachin, S. G., 301. McGhie, J. F., 263, 276, 280. MacGillavry, C. H., 507. McGillivray, R., 474. McGlashan, M. L., 73, 74, 76, 83, 88, 90, 91, 93, 94, 95. McGlothlin, R. E., 146. McGrat,h, D., 367. McGrath, W. D., 101. McGreer, D . E., 201, 227. McGregor, A. T., 112. McGregor, L. L., 425, 426. McGuire, J. S., 416. Machata, G., 449. Machida, K., 193. Machin, D. J., 154. Maciera-Vidan, A., 452. McIver, P. J., 489. Mack, D. L., 476. Mack, W., 332. McKay, J. E., 370. Mackay, K. J. H., 503. Mackay, M., 514. McKay, R. H., 424. MacKellar, F. A., 201, 337. McKellar, J. F., 42. McKelvey, S. A., 370. McKelvie, N., 261. McKenna, R. H., 489. Mackenzie, A. C., 499.
Mackenzie, J. D., 147. McKetta, J. J., 75, 98. Mackey, J. L., 152. McKim, A. M., 334. McKinley-McKee, J. S., 420, 421, 422. Mackor, E. L., 51. McKusick, B. C., 323. McLachlan, A. D., 51, 60, 61, 236. MeLafferty, F. W., 498. McLane, C. K., 23. McLaren, L., 362. McLauchlan, K. A., 201, 202, 204, 364, 366. MacLean, D. B., 357. McLean, S., 353. McLellan, A. L., 82. MacLeod, W . D., jun., 293. McMahon, P. E., 192. McMillan, J. A., 55, 58, 167. McMillin, C. K., 220. McNally, S., 221, 362. McNeal, R. J., 156. McOmie, J. F. W., 309. McPhail, A. T., 293, 513. McQuillan, G. P., 142. McSherry, W . F., 369. MacVicar, K., 165. McWhinnie, W. R., 162. Maeck, W. J., 444, 492, 493, 495. Markl, G., 308. Maerten, G., 280. Magalhaes, M. T., 318. Magee, R. J., 467, 476. Maggio, F., 162. Magidman, P., 275. Maguire, K . D., 233. Mahesh, V. B., 429, 433. Rlahler, H. R., 418, 421. Mahler, J. E., 180, 286, 313. Mahony, J. D., 492. Maier, H. J., 448. Maier, L., 146. Maier, W., 189, 204. Mai-Ling-Yih, I., 469. Maina, G., 255. Mais, A., 261. Maish, W . G., 113, 114. Maitlis, P. M., 183, 184, 269, 283, 308, 320. Maizus, Z. I<., 39. Majumdar, A. K., 451. Majumdar, K., 119. Maiumdar, M. K., 133. Mak, T. C. W., 509. Makarov, S. Z., 155. Makashev, Yu. A., 138. Maki, A. H., 47, 50, 52, 57, 58. Maki, H., 56, 58. Malet, G., 278. Malhotra, K. C., 459.
Malhotra, S. K., 264, 298, 306. Malik, M. S., 358. Malik, W . U., 485. Malissa, H., 455, 458, 490. Mallett, M. W., 496. Mallory, F. B., 202, 332. Malm, J. G., 130. Mamedov, I. A., 453. Manastyrskyj, S., 180. Mandel, L. R., 374. Mandelkern, L., 130. Mandell, L., 270. Mandlsberg, C. J., 153. Mangoni, L., 295. Mangum, B. W., 46. Manh, D. D., 354. Mann, D. E., 103, 121, 190. Mann, F. G., 342. Manners, D. J., 370. Mannerskantz, H. C. E., 176. Manning, D. L., 458, 461. Manning, R. E., 350. Mannsfeld, S.-P., 328. Manolopoulos, P. T., 362. Manson, E., 403. Manson, L. A., 409, 410. Marais, D. J., 190. Marascia, F. J., 322. Marburg, S., 252. Marchart, H., 440. Marckwald, W., 322. Marcus, R., 261. Marcus, R. A., 233. Margoliash, E., 386. Margrave, J. L., 100, 130, 196. Margulis, T. N., 507. Marhol, M., 447. Mari, R., 30, 31. Marino, G., 232. Marion, L., 353, 358. Mark, H. B., 463, 483. Mark, V., 272. Markert, C. L., 419. Markevich, A. M., 26, 27, 38. Markezich, A. R., 369. Markham, E., 389. Markham, J. J., 62. Markham, K. R., 341. Markham, R., 381. Markl, G., 268, 340. Mark6, B., 177. Mark6, L., 177. Markov, V. P., 153. Markovitz, A., 365. Markowitz, S. S., 492. Marks, G. S., 391, 393, 395, 396. Marks, P. A., 380. Marmet, P., 128. Marmur, J., 374, 378. Marnati, M. P., 411. Maroudas, A., 93.
538
Marple, L. W., 471. Marpy, K., 150. Marquardt, F. H., 250. Mmr, P. A., 342. Marrian, G. F., Marriott, J. E., 232. Marsh, R. E., 504, 510, 512, 513. Marsh, S. F., 493, 495. Marshall, G. F., 495. Marshall, J. A., 264, 302, 306, 355. Marshall, L. M., 359. Marshall, R. L., 170, 173. Marshall, W., 46. Marsigny, L., 123, 128. Marston, H. R., 403, 405. Martell, A. E., 173, 422. Martens, R. J., 235, 335. Martens, W., 462. Marti, M., 428. Martin, B., 162. Martin, D. F., 174. Martin, D. G., 263. Martin, D. S., jun., 171. Martin, G., 65, 192. Martin, J. C., 253. Martin, M. M., 253. Martin, R., 34. Martin, R. B., 251, 253. Martin, R. G., 381. Martin, W. W., 480. Martin-Smith, M., 277, 296, 330. Martinez, A. P., 424. Martres, R. W., 460. Martsokha, B. K., 331. Marty, T., 194. Marunina, A. T., 460. Marvell, E. N., 237. Masamure, S., 339. Maslen, V. W., 121. Mason, E. A., 113, 114. Mason, R., 185. Mason, S. F., 82, 169, 198, 286. Mason, S. G., 368. Mason, W. H., 482. Massad, M. K., 280. Masschelein, W., 196. Massey, A. G., 148, 150. Massingill, J. L., 273. Masuda, Y., 68. Mateescu, G., 309. Matherny, M., 475. Matheson, M. S., 55. Mathews, G., 296. Mathewson, J. H., 391. Mathieson, A. McL., 289, 503, 513, 514. Mathis, R., 194. Mathot, V., 88. Mathur, N. K., 461. Matic, M., 488. Matijevich, B. L., 417. Matlack, G. M., 493.
Matschki, D. E., 98. Matsen, J. M., 460. Matsubara, I., 195. Matsui, M., 281. Matsutani, S., 345. Mattauch, H., 130. Matten, J., 146. Matthaei, J. H., 380, 381. Matthew, M., 386. Matthies, D., 323. Mattingly, T. M., 244. Mattock, G., 466. Mattocks, A. R., 345. Mattson, R. H., 277. Maulbecker, D., 136, 168. Mauret, P., 198. Maurice, M. J., 471. Mautner, H. G., 336. Mauvernay, R. Y., 4'79. Mauzerall, D., 325,385,388, 390, 393, 394, 395. Mavel, G., 65. Mawby, R. J., 160. Maxwell, E. S., 381. Maxwell, J. A., 438, 462. May, P., 491. Mayer, B. E., 158. Mayer, D. B., 277. Mayer, J., 474. Mayne, J. E. O., 461. Mayer, R., 323, 330. Mayer, V., 439. Mayling, A. H., 482. Mays, M. J., 140. Mayor, L , 22, 23. Maza, R. M., 452. Mazliak, P., 278. Mazumder, R., 404. Mazur, Y., 287, 289, 305, 327. Meadows, J. W. T., 493. Meakin, J. E., 126. Mecke, R., 194. Meckel, L., 446. Mechoulam, R., 289. Medeiros, F. W., 322. Mehra, V. S., 98. Mehrotra, R. C., 155, 453. Mehta, M. L., 156. Meiboom, S., 66. Meier, H., 370. Meier, W., 315, 316, 341. Meineker, F. W., 51. Meinhart, J. O., 414. Meinke, W. W., 496. Meinnel, J., 192. Meinwald, J., 213, 283, 287, 303. Meister, W., 133. Meites, L., 487. Melchior, M. T., 52. Melera, A., 203, 327. Melnick, I., 395. Melson, G. A., 174. Menapace, H. R., 32. Mencis, I., 493.
Meng, B. H., 476. Mengler, H., 327. Mercier, M., 327. Meredith, R. F. K., 347, 348. Merer, A. J., 128. Merkle, F. H., 465. Merrill, S. H., 382. Merritt, C., 497. Mertz, C., 265, 280. Mervyn, L., 375, 409. Merz, E., 491. Meselson, M., 379. Mesirov, M. E., 209. Mesnard, P., 362. Mestres, R., 270. Metcalfe, J., 478. Metzner, W., 328. Meuche, D., 315, 316. Meuwsen, A., 148. Meyer, B., 103. Meyer, K., 371, 446. Meyer, M. W., 240. Meyer, R., 341. Meyer, W. H., 418. Meyer, W. K., 151. Meyer, W. L., 306. Meyerson, S., 236. Meystre, C., 305. Michalowicz, W. A., 273. Michael, D., 233. Micheel, F., 364. Nichel, G., 278. Michels, A., 88, 120. Michelson, A. M., 371, 376, 377. Michelson, M. J., 330. Michl, J., 393. Middleton, W. J., 323. Mielert, A., 229. Miescher, E., 116, 124, 125. Migchelsen, T., 511. Miginiac, P., 280. Migliacci, A., 411, 412. Mihai, G., 314. Mihfika, I., 475. Mikawa, Y., 191. Mikhailichenko, A. I., 494. Mikhailov, B. M., 133, 135. Mikhailov, Yu. N., 153. Miki, T., 293. Milazzo, G., 479. Miliotis, J. A., 137. Milks, J. E., 307, 340. Millar, D. B. S., 419, 424. Millar, I. T., 333. Milledge, H. J., 502. Millen, D. J., 193, 195. Miller, B., 240. Miller, F. A., 195. Miller, H. C., 131. Miller, I. M., 411. Miller, J. G., 191. Miller, J. M., 186. Miller, J. R., 164. Miller, K. E., 263, 276.
539
Miller, P. A., 319. Miller, R. L., 339. Miller, R. R., 174. Miller, S. I., 224, 231, 270. Miller, S. J., 405. Miller, V. B., 32. Milleron, N., 9. Milligan, D. F., 54. Mills, I. M., 100. Mills, J. A., 405. Mills, J. N., 431. Millward, B. B., 322. Milne, G. W. A., 250, 306. Milner, G. W. C., 464. Milton, A. S., 445. Milton, E. R. B., 107. Mims, S. S., 295. Minczewski, J., 448. Minghetti, A., 411. Minkoff, G. J., 18, 28. Minshall, E., 445. Minutilli, F., 301. Mironov, V. E., 138. Mirsky, A. E., 380. Mishima, H., 299. Mishra, H. C., 47, 151, 161. Mislow, K., 189, 197, 199, 205, 286, 306, 347. Missen, R. W., 96. Mistry, S. P., 404. Misumi, S., 269. Mitchell, A., 267. Mitchell, B. D., 499. Mitchell, D. W., 158. Mitchell, P. C. H., 158. Mitra, A. K., 365. Mitsui, H., 380. Mitsui, T., 474. Mitzner, B. M., 480. Miyazaki, M., 294. Mizuno, N., 380. Mochalova, N. I., 506. Mock, W. L., 258, 309. Modest, E. J., 338. Mobus, B., 471. Mockel, K., 320. Moeller, T., 145, 152. Moelwyn-Hughes, E. A., 96, 217. Moerikofer, A. W., 227,255. Moffatt, J. G., 376. Mohaupt, G., 160. Mohr, G., 326. Molin, N. Yu., 52. Moller, F., 419. Mollin, D. L., 407. Molloy, B. B., 203, 327. Molodkin, A. K., 153. Monaco, M., 337. Monaghan, J. J., 89. Monagle, J. J., 267. Monfila, A., 100, 116, 119. Monk, R. G., 438, 464. Monnier, D., 488. Monod, J., 379. Monseur, X., 205, 351, 356.
Monson, R. S., 219. Montavon, M., 274. Montequi, R., 442. Monty, K. J., 403. Moody, G. J., 361. Mooney, E. F., 133, 136, 206. Moore, B., 329. Moore, C. G., 280. Moore, J. A., 322. Moore, J. H., 406. Moore, M., 356. Moore, P. T., 224. Moore, R. B., 235. Moore, R. E., 352, 355. Moore, R. H., 361, 367. Moore, R. N., 297. Moore, W. R., 224. Moores, M. S., 240. Morachevsky, A. G., 97. Morales, A., 470. Moran, P. R., 62. Morato, T., 430. Morawetz, H., 246, 250, 253. Morcom, K. W., 74, 93. Morell, C. E., 232. Morgan, E., 128. Morgan, H., 497. Morgan, L. O., 59, 66. Morgan, L. R., 243, 306, 324. Morgan, L. R., jun., 340. Morgan, W. T. J., 368. Mori, B., 155. Moriarty, R. M., 210. Morimoto, M., 269. Morimoto, T., 277. Morimoto, Y., 173. Morin, R. D., 273, 334, 348. Morita, S., 191. Moritz, A. G., 193, 199. Moritz, K. L., 316. Moriyama, H., 417. Mork, P. C., 273. Morley, H. V., 399. Moros, S. A., 460. Moroshkina, T. M., 475. Moroz, E., 303. Morozov, I. S., 154. Morrel, D. B., 396. Morris, A. G. C., 488. Morris, D. F. C., 444, 490. Morris, G., 262. Morris, G. F., 222. Morrison, A., 294. Morrison, G. A., 317. Morrison, G. H., 443. Morrison, J. D., 125. Morrison, M., 396. Morrison, R. T., 236. Morse, B. K., 207. Morse, P. M., 114. Morsingh, F., 394. Mortimer, C. T., 330, 333.
Morton, J. R., 53, 54, 55, 56, 57, 101. Morton, K. B., 300. Morton, R. K., 417. Mosby, W. L., 319. Moscowitz, A., 197, 306. Moser, C., 113. Moses, P., 202, 324, 330. Mosher, H. S., 203,224,366. Moss, H., 442. Moss, J. B., 205, 350. Motl, O., 292. Motes, J. M., 230. Mott, W. E., 491. Moulton, W. G., 194. Mourkides, G. A., 416. Moustafa, 2. H., 372. Mowat, J. H., 366. Mower, H. F., 279. Moyle, M., 268. Moynehan, T. M., 203, 338. Mozdokeli, T. G., 131. Mrazek, R. V., 94. Miihle, G., 331. Miiller, E., 267. Miiller, G., 375. Muller, H., 330. Mi.iller, K., 192, 494. Muller, O., 375, 402, 411, 413. Muller, R., 147, 182. Mueller, R. G., 487. Muller, R. J., 231. Mueller, W. A., 227, 229. Mueller, W. H., 92. Miinch, G., 376. Muetterties, E. L., 70, 131, 142, 152. Mujagawa, I., 57, 206. Mukai, T., 315. Mukaroski, I., 345. Mukerjee, S. K., 329. Mullen, R. T., 242. Muller, J. M., 302. Muller, R., 316. Muller, T. C., 233. Mulliken, R. S., 82, 100, 106, 107, 109, 110, 117, 122, 123, 128, 190. Mulrow, P. J., 427. Munch-Petersen, A., 400, 401. Munday, L., 167. Munn, R. J., 90. Munster, G., 159. Murata, T. G., 370. Murdoch, H. D., 181, 222. Murdock, K. C., 283. Murphy, D., 366. Murphy, J., 66. Murray, A. W., 417. Murray, K., 447. Murray, K. E., 275. Murray, R. W., 60,466,472. Murrell, J. N., 51, 64, 82. Murthy, A. R. V., 457.
540
Natta, G., 151. Naville, A. H., 429. Naya, S., 503. Nayler, J. H. C., 322. Naylor, C., 379. Naylor, P. G., 269. Neal, D. J., 492. Nebbia, L., 471. Nebergall, W. H., 468. Nedbalek, E., 482. Neeb, R., 482, 488. Needleman, S. B., 320. Nbel, J., 65. Neeman, M., 267. Neff, L. D., 14. Negri, R. C., 448. Neher, R., 427, 429, 430. Neikam, W. C., 282, 312. Neilson, A. H., 318, 341. Naar-Colin, C., 192. Nabivanets, B. I., 154, 156. Neilson, T., 257. Neiman, M. B., 32, 33. Nabors, C., 429. Neiman, R., 58. Nace, H. R., 272. Nelson, D. A., 335. Nachbaur, E., 144. Nelson, I. V., 167. Naemura, K., 272. Nelson, L. S., 102. Nagarajan, K., 339, 354. Nemec, I., 467. Nagasawa, K., 365. Nemeth, A. M., 388. Nagase, K., 255. Nemodruk, A. A., 477. Nagata, C., 83. Nenitzescu, C. D., 309. Nagel, C. W., 368. Neparko, E., 95. Nagy, B., 445, 494. Neronova, N.N., 505. Nagy, P. L. I., 183. Nesbet, R. K., 113. Nahabedian, K. V., 234. Nesmeyanov, A. N., 147, Nahum, L. Z., 458. 155, 156. Naik, A. R., 330. Neuberger, A., 386, 387, Naiman, M., 237. 388, 397, 398. Nair, V. S. K., 469. Nakagawa, M., 268,269,272. Neugebauer, F. A., 204. Neuman, R. C., 232. Nakagawa, K., 260. Nakagawa, Y., 204, 351, Neumann, C. L., 198. Ncumann, W. P., 142. 353. Neunhoffer, H., 376. Nakajima, M., 298. News, N., 204, 353, 355. Nakamichi, M., 447. New, R. A., 393. Nakaminami, G., 268. Nevell, T. P., 368. Nakamoto, K., 173. Neveu, M. C., 246, 247. Nakamura, D., 165. Neville, R. G., 144. Nakamura, K., 248. Newbould, J., 296. Nakanishi, K., 299, 302. Newitt, E. J., 39. Nakano, T., 358. Newman, E. J., 478. Nakao, A., 407. Newman, M. S., 250. Nakata, T., 260. Newmann, G., 166. Nakazaki, M., 291, 292. Newnham, I. E., 154. Nakulesparan, K., 463. Nalbandyan, A. B., 24, 25, Newns, G. R., 143. Ney, W. O., 253. 27, 28, 29, 30, 38, 42. Neyens, A. H., 232. Nambury, C. N. V., 202. N g u y h , D., 191. Namioka, T., 123. Nichol, C. A., 408. Namtseva, L. I., 459. Nicholls, D., 129. Naqui, N., 166. Nicholls, R. W., 101, 102, Narath, A., 192. 111, 112. Narayanan, C. R., 355. Nardelli, M., 164, 509, 510. Nichols, P. N. R., 479. Nicholson, J. S., 308. Nash, C. P., 193. Nickels, W., 138, 482. Nast, R., 163, 182. Nickless, G., 469. Natarajan, A. R., 441. Nicksic, S. W., 49. Nathan, H. A., 403. Niclause, M., 30, 31. Natsuma, M., 201. Murthy, N. S., 112. Murthy, V. R., 497. Murti, P. S., 96. Murto, J., 235. Murty, K. S., 454. Musgrave, B., 494. Musgrave, W. K. R., 185. Musil, A., 443. Musil, F. J., 502. Musulin, B., 114. Musya, M., 302. Muth, C. W., 471. Muxfeldt, H., 288, 318. Myers, A. L., 89, 92. Myers, D. B., 84. Myers, H. W., 480. Myers, L. S., 490.
Niclause, N., 34. Nicolaus, B. J. R., 323. Nicole, L., 265. Niedenzu, K., 133. Nielsen, N. A., 273. Nier, A. O., 496. Niermann, H., 142. Nigam, R. K., 83. Niggli, A., 505. Nightingale, R., 142. Nihei, T., 378. Niki, E., 462. Nikolaev, N. S., 154. Nikoleti6, M., 209. Nilsson, M., 198. Nilsson, W., 263. Nirenberg, M. W., 380, 381. Niselion, L. A., 138, 152. Nishikawa, H., 162. Nisizawa, K., 370. Niskanen, R. A., 494. Nisselbaum, J. S., 420. Nist, B. J., 288. Nitta, I., 52, 508. Niu, H. Y., 313. Nixon, J. F., 157. Niyogi, S. K., 448. Noack, K., 191. Noble, G. A., 62. Nocke, W., 433. Noth, H., 133,134,139,147. Noggle, J. H., 144. Nogina, 0. V., 155. Noland, W. E., 332, 511. Nolle, A. W., 59. Nonhebel, D., 262. Nonhebel, D. C., 222. Nooi, J. R., 270. Norcross, B. E., 335, 416. Norell, J. R., 322. Norin, T., 290. Norman, B. 0. C., 449. Norman, R. 0. C., 48, 232, 236, 310. Norman, J. J., 194. Norment, H. G., 503, 508. Norrish, R. G. W., 20, 27, 29, 30, 42, 101. Norton, F. J., 10. Norton, W. T., 277. Novtik, E., 445. Novak, K., 465, 467. Novtik, V., 484. Novakovskaya, E. G., 460. Novikova, N. V., 147. Novoa, W. B., 424. Novoselova, A. V., 130. Novotn9, L., 292. Nowaki, E., 343. Nowicki, L., 402, 412. Noxon, J. F., 109. Noyce, D. S., 196, 219, 224. Noyce, W. K., 452. Nozik, Y. Z., 502. Nozoe, T., 315, 316. Niirnberg, H. W., 482.
541
Nugent, L. J., 190, 195. Nukada, K., 191. Nussbaum, A. L., 200, 267, 305. Nussbucker, B., 147. Nussim, M., 287. H., Nuttall, R,. 166. Nygaard, A. P., 418. Nyholm, R. S., 154, 158, 160, 162, 163, 167, 171. Nyman, F., 149. Nfvlt, J., 95.
Oae, S., 336. OBrien, R. E., 199, 260. OBrien, R. J., 165. Ochiai, H., 368. Ochoa, S., 381, 404. OColla, P. S., 367. Ocone, L. R., 170. Odabashyan, G . V., 150. ODonnell, J. P., 230. ODonnell, T. A., 159, 469. Ofele, K., 180, 183. Offer, G., 449. Oftedahl, M. L., 364. Ogawa, M., 106, 107, 125, 126. Ogle, P. R., 159. OGrady, B: V., 199. Ogura, F., 268. Ohlman, G., 34. Ohloff, G., 289. Ohme, R., 321. Ohnishi, S., 52. Ohta, M., 218. Okamoto, T., 201. Okamy, A., 343. Okazaki, R., 377. Okazaki, T., 377. Okhlobystin, 0. Yu., 266. Oksne, S., 332. Okuda, S., 345. Okuzumi, Y., 245, 269. Olah, G. A., 232, 233, 240, 268, 285. Olcott, R. J., 175. Oldenberg, O., 102, 110, 123. Oldershaw, G. A., 101. Oldfield, J. H., 476. Oliveto, E. P., 267. Ollis, W. D., 318. Olsen, C. J., 253. Olsen, R. E., 231. Olson, C., 482. Pabst, A., 505. Olson, J. M., 418. Pace, R. J., 131. Omar, M. H., 79, 92, 98. Pachler, K., 204. OMara Bockris, J., 472. Packer, J., 246. Onak, T. P., 132. Packer, K. J., 146, 150. Onken, U., 96. Paddock, N. L., 144. Ono, H., 268, 368. Padilla, J., 348. Ono, S., 369. Pagani, B., 471. Onodera, K., 368. Page, J. A., 438, 462, 464. Onyszchuk, M., 142. Pagel, H., 345. Oota, Y., 380. Pahil, S. S., 459.
Opalovskii, A. A., 154. Openshaw, H. T., 260. Opitz, H. P., 171. Oranskaya, M. A., 156. Orazi, 0. O., 354. OReilly, D. E., 45, 63. Oreskes, I., 250. Orgel, L. E., 50, 176, 184. Origlio, S., 13. Orioli, P. L., 164. Ortenberg, F. S., 112. Ortiz, P. J., 404. Orzech, C. F., 217. Orzeck, C. E., 231. Osaka, K., 315. Osawa, S., 380. Osbond, J. M., 276. Osborne, A. G., 177. Osborne, B. P., 159. Osiecki, J. H., 376. Oskam, H. J., 120. Oskay, E., 269. Ostermayer, F., 218. Ostermeier, J., 149. Ostler, O., 320. Osuma Itoh., 233. Otaka, E., 380. Oth, A., 378. Otomo, Y., 62. Ott, H., 367. Ott, J. B., 83, 94. Ott, w., 393. Otte, H. M., 502. Ottemann, J., 477. Ottendorfer, L. J., 490. Otting, W., 204. Ottinger, R., 198. Otto, P., 355. Ourisson, G., 200, 303. Ovenall, D. W., 55. Overath, P., 404. Overberger, G. C., 330. Overend, W. G., 246, 360, 362, 363. Overwien, H., 345. Owellen, R. J., 204, 354. Owen, A. J., 132. Owen, E. D., 182. Owen, J., 46. Owen, J. E., 137. Owens, A. F., 494. Owings, F. F., 303. Owston, P. G., 178, 510. Oyama, II., 395.
Pai, B. R., 292, 354. Painter, T. J., 368. Pal, B. C., 373. Palebek, M., 468. Palistrant, A. F., 505. Palit, S. R., 96. Pallaud, R., 262. Pallotti, M., 329. Palm, C., 183, 184. Palmer, J. W., 66. Palmer, K., 353. Palmer, T. A., 448. Panella, J. P., 334. Pa#nizzi,L., 295. Pankhurst, K. S., 480. Pannetier, G., 102, 123, 128. Panwar, K. S., 470. Panzer, H. P., 364. Panzer, R. E., 154. Pasletti, P., 164. Papadopoulos, E. P., 220. Papaliolios, C., 112. Pappas, S. S., 285, 307. Paquette, L. A., 337. Paquot, C., 274. Paraskevopoulos, G. C., 96. Parcell, A., 253. Parham, W.E., 286. Parihar, D. B., 375. Parikh, I., 327. Park, J. D., 196, 282. Parks, C. R., 457. Parker, A. J., 254. Parker, C. A., 476, 477. Parker, R. E., 233. Parker, W., 290. Parker, W. J., 482. Parkin, R. A., jun., 196. Parkin, C., 182. Parkinson, W. H., 101, 102. Parraclr, J. D., 235. Parry, R. W., 135. 131, 148, Parshall, G. W., 180. Parsonage, N. G., S6,88, 95. Parsons, C. R., 164. Partington, E. J., 91. Partos, R. D., 230. Partyka, R. A., 298. Pascual, J., 270. Paslo, D. J., 198. Pasqualini, J. R., 432. Passoneau, J. V., 413, 414. Pasternak, R. A., 13. Pasto, D. J., 285, 314. Pastore, E. L., 414. Patai, S., 223, 225, 231. Patel, C. C., 155. Paterson, W., 341. Patin, D. L., 370. Patmore, E. L., 174. Patrick, C. R., 310. Pats, R. G., 483, 488. Patterson, A., 71. Patterson, D., 99, 439. Patterson, H., 496.
542
Patterson, J. M., 324. Patton, J. W., 230, 416. Patzelt, H., 316. Paudler, W. W., 337. Paul, I., 286. Paul, I. C., 296, 317. Paul, K. G., 396. Paul, R. C., 459. Paulik, F., 500. Paulsen, H., 360. Paulson, J. F., 497. Paulus, K. F., 51. Pauson, P. L., 177,183,184. Pavlenko, L. I., 475. Pavlovid, D., 223, 224. Pawelke, G., 420. Pawelkiewicz, J., 402, 411, 412, 413. Pawley, G. S., 505. Payne, D. S., 145. Payne, G. B., 259. Payne, M., 442. Peach, M. E., 136, 151. Peacock, R. D., 159. Peak, D. A., 308. Pearn, E. J., 206. Pearson, R. G., 66,175,223, 254. Pearson, R. K., 133. Pechacek, R. E., 463. Pechanec, V., 473, 475. Pecherskaya, Yu. I., 27. Pechman, M., 447. Peck, P. F., 443. Pecsok, R. L., 154. Pedersen, H. C., 494. Pedinoff, M. E., 196. Peel, J. L., 410, 411. Peeling, E. R. A., 254. Peifer, J. J., 446. Peiffer, G., 272. Peisach, J., 228. Pelster, H., 316. Peltier, D., 193. Pelz, K., 346. Penfold, A. R., 294. Penneman, R. A,, 154. PQrano, J., 82. Percival, E., 370. Perego, G., 151. Pereira, N. A., 204, 352. Pefilova, I. L., 156. Perkins, D. F., 478. Perkins, M., 495. Perkins,N. A., 313. Perlin, A. S., 362, 367, 370. Perlman, D., 411. Perlmutter, H. D., 286. Perrin, D. D., 166,203,329, 339. Perrin, D. R., 203, 329. Perry, C. W., 269. Perry, M. B., 359, 366, 370. Perry, S. G., 252. Person, W. B., 82, 83. Pesez, M., 442.
Peterkofsky, A., 413. Petrow, V., 306. Peters, G. A., 338. Petersen, D. R., 283. Petersen, R. C., 220. Peterson, E. R., 337. Peterson, J. O., 257. Peterson, L., 496, 499. Peterson, L. E., 201. Peterson, L. I., 282. Peterson, P. E., 210, 225. Petit, G. S., 154. Petix, J., 396. Petrissans, J., 198. Petropoulos, A. G., 464. Petrou, A. A., 206. Petrov, A. A., 272. Petrov, A. D., 150. Petrov, V. G., 502. Petrus, V., 484. Petterson, A. V., 127. Pettit, D. J., 322. Pettit, G. R., 256, 257, 276, 320. Pettit, R., 180, 286, 313. Pevzner, M. S., 479. Peyron, M., 107. Pfab, W., 474. Pfahl, D., 409. Pfeiffer, M., 278. Pfister, K., 337. Pflaum, R. T., 467, 469. Pflegher, K., 335. Pfleiderer, G., 414,415,419, 424. Phillips, D. J., 167. Phillips, D. S., 444. Phillips, G. O., 361. Phillips, J. C., 504. Phillips, J. G., 100, 255. Phillips, L., 219. Phillips, S. L., 489. E'hillips, W. D., 52, 61, 70, 152. Phillipson, M., 462. E'hilpot, J. L., 101. Piatak, D. M., 204. Piatelli, M., 396. Piazzi, M., 469. k'iccolini, R., 311. Pick, J., 94. Pickard, P. L., 262. ?ickering, W. F., 476. ?ickhardt, W. P., 456. lidcock, A., 170. lierce, A., 335. ?ierce, L., 201, 321. lierce, T. B., 443. liercey, M. R., 266. lieterse, M. J., 335. lietilii, I., 97. 'ietrzak, R. F., 452. ?ietrzyk, D. J., 486. 'iette, L. H., 48, 49, 54, 60. 'ijck, J., 492, 493, 495. ?ike, E. R., 501.
Pike, M. A., 95. Pilato, L. A., 196, 284. Pillai, M. G. K., 194. Pillai, V. S. N., 460. Pillar, C., 227. Pillow, M. W., 113. Pilsater, U., 100, 104. Pimentel, G. L., 82. Pinar, M., 354. Pinchas, S., 199, 204. Pinchera, A., 494. Pinchot, G. B., 415. Pine, S. H., 230. Pines, H., 240. Pinhey, J. T., 293. Pink, R. C., 49. Pinte, G., 491. Piper, T. S., 107, 169, 172. Piras, R., 360. Piret, P., 511. Pisarevskii, Yu. P., 111. Pischel, H., 375. Pitcher, E., 176, 180, 185. Pitman, I. H., 252. Pitman, M., 365. Pitochelli, A. R., 131, 132. Pitra, J., 445. Pitteroff, W., 242. Pitts, J. N,, 60. Pitwell, L. R., 438. Pitzer, K. S., 89. Piwowarska, R., 454. Plane, R. A., 422. Plat, M., 204, 205, 353, 354. Platz, G. M., 147. Plieninger, H., 285, 324, 327. Plieth, K., 508. Pliev, T. N., 198. Pliska, V., 486. Plisko, E. A., 369. Ploger, W., 422. Plowman, R. A., 176. Plunkett, A. O., 338. Plust, H. G., 139. Pocker, Y., 207. Poesche, W. H., 333. Poschl, G., 114. Pohlke, R., 286. Poindexter, E. H., 349. Poirier, R. J., 334. Poisson, H., 204. Poisson, J.,351. Polak, R. J., 135. ?olger, N., 275, 276. Pollak, J. K., 376. ?ollak, V. L., 63. ?ollard, F. H., 469. ?ollard, Gt. E., 196, 287. ?ollock, F. J., 247. lolonsky, J., 299. lolster, R., 223. ?oltorak, V. A., 34. lonomarenko, V. A., 150. lool, R. A. H., 86. 'ooley, D., 61.
543
Popa, G., 450. Popea, F., 450. Popjtik, G., 419. Pople, J. A., 64. Popov, E. M., 190. Popova, R. A., 494. Popowicz, J., 447. Popp, F. D., 257, 338. Poppenburg, G., 140. Porai-Koshits, M. A., 506. Porte, A. L., 145, 201, 318. Porter, G., 20, 82. Porter, R. F., 124, 125, 279, 318. Porter, T. L., 119. Porterfield, W. W., 46. Portnoy, H. D., 466. Portnoy, S., 276. Porubszky, I., 489. Post, B., 504. Post, G. G., 361. Postnikov, L. M., 42. Potter, D. J. B., 91. Potter, J. C., 492. Potter, R., 511. Potts, K. T., 350. Powell, D. B., 166, 203. Powell, H. M., 161. Powell, J. E., 152. Powell, V., 291. Power, U., 426. Powers, R. M., 480. Poulson, R. E., 69, 70. Povyshev, L. V., 97. Pozharski, F. T., 331. Prasad, K., 112. Prasad, S., 153, 458. Prasad, S. S., 112. Pratt, E. A., 373. Pratt, L., 176, 184. Prausnitz, J. M., 76, 83, 84, 89, 90, 92, 97. Prelog, V., 219, 287, 328. Prengle, H. W., 95. Presnyakova, V. M., 510. Preston, D. R., 348. Preston, J., 246. Prey, V., 364. Pzibil, M., 465. Pribil, R., 441, 454, 455, 469, 484. Price, C. C., 335, 341. Price, R., 150. Price, W. C., 100. Prigogine, I., 84. Prilezhaeva, E. N., 280. Prinzbach, H., 285, 322. Pristavka, D., 439. Pritchard, J., 15. Proctor, G. R., 341. Prohaska, C. A., 191. Prokhorov, A. M., 46. Prokofeva, I. V., 468. Proll, P. J., 162. Protheroe, J. B., 23, 27. Protsenko, G. P., 481.
Prout, C. K., 161. Prue, J. E., 64. Pruett, R. L., 180. Pruguard, J., 437. Pruitt, K. M., 252. Pruitt, M. E., 495. Prunty, F. T. G., 427, 432. Prusoff, W. H., 372. Pryor, W. A., 207. Prystas, M., 375. Przybylska, M., 357, 503, 512, 513. Pshenitsyn, N. K., 468. Ptichkin, I. I., 26. PiilkrBb, P., 477. Pullman, B. J., 147. Pump, J., 140. Punqor, E., 458, 473. Purdie, J. W., 399. Purdy, S. J., 446. Purdy, W. C., 458, 466. Puri, D. M., 155. Purushothaman, K. K., 292. Purvis, J. L., 415. Putkey, T. A., 212. Pyaivinen, E. A., 369. Pysz, J. F., jun., 168.
Ramp, F. L., 255. Ramsay, D. A., 100, 101, 102, 128. Ramsay, 0. B., 223. Ramayne, M. R., 63. Randall, E. W., 47. Randic, M., 173. Randles, C. H., 408. Randolph, D. R., 443. Rank, D. H., 109. Ransil, B. J., 113, 121. Rao, B. S., 109. Rao, D. V. G. L. N., 53,205, 206. Rao, G. G., 454, 467, 468, 470. Rao, G. P., 457. Rao, G. V., 96. Rao, K. B., 454. Rao, K. S., 109. Rao, K. V., 301. Rao, N. V., 470. Rao, P. K., 101. Rao, P. M., 128. Rao, P. T., 127, 128. Rao, P. V. K., 454. Rao, T. A. P., 128. Rao, V. V., 450. Quacchia, R. H., 233. Rao, Y. V., 127. Quagliano, J. V., 164, 172. Raphael, R. A., 290, 295, Quattrone, J. J., 470. 301. Queen, A., 214. Rapin, A. M. C., 365. Quijada, C. L., 425. Rapkin, E., 490. Quilico, A., 327. Rapoport, H., 263,309,325, 339, 352, 355, 393, 399. Raaen, H. P., 482. Rapoport, S. A., 372. Raasch, M. S., 263. Rappoport, Z., 223, 225. Rabin, B. R., 423. Rasburn, J. W., 217. Rabinowitz, R., 261, 410. Raschig, F., 139. Rasish, J. C., 463. Rabourn, W. J., 320. Rabovik, Ya. I., 138. Raskovan, J., 172. Rachman, A., 199. Rasmusson, G. H., 260. Radda, G. K., 232, 236, Rastogi, R. P., 83. 310. Rastrup-Andersen, J., 195, Radding, C. M., 378. 199, 202, 329. Radford, H. E., 116. Rathjens, G. W., jun., 196. RBdy, G., 454. Ratnam, A. V., 96. Ragade, I. S., 358. Rauch, E., 258. Rahn, R., 46. Raudenbusch, W., 218. Rajaratnam, A., 102. Rauther, J., 367. Rajadurai, S., 292. Raval, D. N., 425. Rajappa, S., 354. Ray, N. H., 150. Rajic, M., 303. Ray, W. J., jun., 382. Rajopalan, K. V., 421. Raymond, S., 447. Rakhit, S., 256. Razuvaen, G. A., 184. Rakovic, M., 489. Re, G. D., 331. Rakutis, R. O., 200, 303. Read, S. H., 113, 114. Ralph, R. K., 378. Read, T. O., 233. Ralph, W. D., 493. Reamer, R. H., 98. Rama Rao, C., 441. Records, R., 197, 306. Ramage, R., 290. Reddy, G. S., 327. Raman, S., 502, 503, 512. Reddy, J., 512. Raman, S. P., 301. Redfield, B., 413. Ramcharan, S., 430. Redford, D. G., 203. Ramirez, F., 261. Redhead, P. A., 13. Rammler, D. H., 361, 377. Redlich, O., 98.
544
I N D E X OF AUTHORS N A M E S
Redmond, W., 266. Redpath, C. R., 194. Reed, T. M., 90. Reed, W. L., 224. Reed, H. J., 514. Reed, H. J., 503. Rees, A. L. G., 113. Rees, D. A., 371. Rees, C. W., 232, 234, 235, 246, 310, 311, 326, 336. Rees, M. W., 381. Rees, W. T., 476, 477. Reese, C. B., 253, 377. Reese, R. M., 496. Reeves, E. M., 101. Reeves, L. W., 79. Reeves, R. L., 245. Regnaud, F., 454. Reich, E., 382. Reichard, P., 377, 410. Reichel, L., 367. Reichel, S., 320. Reichle, W. T., 147. Reichmann, M. E., 381. Reid, D. H., 203, 327. Reid, R. C., 34. Reid, S. T., 324, 330, 337. Reid, W., 327, 331. Reif, L., 230. Reilley, C. N., 440,455,461, 463, 466, 472, 483. Reimlinger, H., 267. Rein, J. E., 492, 493. Rein, J. S., 444. Reinberg, A. R., 62. Reiner, B., 444. Reiner, J. E., 135. Reiner, J. M., 444. Reinhart, I<. L., 330. Reinheimer, J. A., 219. Reinheimer, J. D., 234. Reinhold, H., 140. Reinisch, R. M., 149. Reinmuth, W. H., 481. Reisch, J., 329. Reisse, J., 198. Reist, E. J., 365, 366, 375. Reitz, D. C., 50. Remanick, A., 228. Rembmz, G., 362, 365. Remeikrt, J. P., 46. Remily, C., 416. Relyee, D. I., 336. Renner, H., 103. RBrat, C., 334, 510. Rerick, M.N., 256. Resnick, I?. R., 299. Reuter, W., 337. Reutov, 0. 217, 230. A., Reynolds, G. F., 466, 470. Reynolds, R. D., 227. Reynolds-Warnhoff, P., 211. &m56, Z., 476, 479. Rhodes, D. F., 491. Rhum, D., 232.
Ribar, T., 214. Ricca, A., 327. Richards, G. N., 369. Richards, J. P. G., 507. Richards, L. W., 19. Richards, R. E., 71, 73, 170. Richards, W. G., 127. Richardson, A. C., 363, 366. Richardson, E., 147. Richardson, J. M., 92. Richardson, 0. W., 118. Richert, D. A., 386. Richey, H. G., 209. Richmond, J. E., 398. Richter, H. G., 496. Richter, H. J., 260. Richter, M., 369. Richter, S., 330. Rickard, R. R., 495. Rickards, R. W., 360. Rickborn, A. B., 230. Riddiford, A. C., 482. Ridd, J. H., 232, 310, 338. Riddle, F. C., 209. Ridgewell, B. J., 232, 336. Rieger, P. H., 51. Rieke, C. A., 110. Riemschneider, R., 204. Rigamonti, J., 266. Rigg, B., 469, 485. Riley, J. P., 478. Riley, T., 233, 246. Rimai, L., 46. Rimington, C., 385, 386, 389. Ringold, H. J., 264, 305, 306. Ringstrom, U., 116. Rink, J. P., 128. Risebrough, R. W., 379. Ritchie, A. C., 347, 348. Ritter, J. J., 263. Rivaille, P., 365. Rizzo, H. F., 135. Ro, R. S., 223. Roach, M. K., 479. Robbins, P. W., 376. Roberts, D., 408. Roberts, D. D., 208, 219. Roberts, E. R., 166. Roberts, H. L., 149, 150. Roberts, .J. C., 320, 329, 341. Roberts, J. D., 189, 208, 210, 217, 240, 311. Roberts, K. D., 433. Roberts, L. E. J., 153. Roberts, L. R., 98. Roberts, M. B., 495. Roberts, R. M., 237. Roberts, R. J., 235. Roberts, R. W., 13. Roberts, W. K., 375. Robertson, A. V., 201, 202, 323. Robertson, E. W., 121.
Robertson, J. E., 220. Robertson, J. H., 509. Robertson, J. M., 296, 301, 349, 351, 609, 512, 513. Robertson, M. S., 338. Robertson, R. E., 218. Robertson, W. W., 92. Robins, P. A., 306. Robins, R. K., 339, 373, 374. Robinson, B., 349. Robinson, B. H., 161. Robinson, C. H., 267, 305. Robinson, D., 112, 424. Robinson, E. A., 146, 149. Robinson, G. W., 102. Robinson, J. R., 294. Robinson, M. J. T., 338. Robinson, P. L., 129. Robinson, R., 232. Robinson, R. J., 499. Robinson, R. M., 254, 335. Robinson, R. R., 246. Robinson, W. G., 420. Robson, A., 486. Rocholl, M. G., 140. Rochow, E. G., 140. Rock, M. K., 413, 414. Rodgers, H., 83. Rodder, K.-M., 130, 153. Roehrscheid, F., 184. Rsmming, Chr., 82. Rossler, S., 468. Rogalski, W., 318. Rogan, J. B., 210. Rogers, L. B., 486, 499. Rogers, M. T., 151, 193. Rogers, N. A. J., 294, 299, 302. Rogovin, Z. A., 369. Rohr, O., 428, 429. Roisich, R. S., 298. Roitman, J., 168. Roizenblat, E. M., 486. Rollinson, C. L., 159. Romand, J., 123. Romanov, V. F., 482. RomaAuk, M., 292. Ronsch, H., 356. Rooney, J. J., 49. Root, J. W., 494. Rooney, R. C., 483, 489. Roothaan, C. C. J., 113. Roper, W. R., 161. Ropp, R. C., 500. Rosen, N., 114. Rosenberg, B. H., 371. Rosenberg, E., 367. Rosenberger, M., 314. Rosenblum, C., 411. Rosenfeld, G., 427. Rosenkranz, R. E., 328. Rosenthal, S., 407. Rosevear, D. T., 162. Ross, D. L., 224. Ross, S. D., 220.
I N D E X OF A U T H O R S N A M E S
646
Ross, S. T., 261. ROSS, A., 263. W. Rossipal, E., 430. Rossmann, M. G., 502. Roth, W. R., 238. Rothaas, A., 393. Rothberg, I., 470. Rother, A., 204, 344. Rother, M., 96. Rothschild, W. G., 195. Rouhi-Laridjani, M., 260. Rousselet, F., 488. Routly, P. M., 118. ROUX, 502. M., Row, L. R., 301. Rowe, C. A., 231. Rowe, G. A., 160. Rowe, J. M., 178, 180, 510. Rowland, F. S., 494. Rowland, L. P., 403. Rowlands, J. R., 51, 53, 54. Rowlinson, J. S., 73, 81, 84, 88, 91, 92, 98, 99. Roy, J., 238. Ruamps, J., 119. Ruban, G., 508. Rubins, R. S., 46. Ruch, R. R., 496. Rucker, B., 407. Rudin, V. Ya., 97. Rudner, B., 134. Rudolph, H. D., 195. Rudorff, W., 164. Rudzats, R., 358. Ruchardt, C., 254. Ruedenberg, K., 17 1. Ruff, J. K., 133, 137. Ruherwein, R. A., 19. Ruhkopf, H., 364. Ru-Jen Lee Han, 365. Rundle, R. E., 508. Runge, H., 449. Ruoff, P. M., 365. Rupert, C. S., 372. Ruppert-Mesche, H., 163. Rusconi, A., 412. Rushbrook, P. R., 491. Rushton, J. D., 302. Russell, C. S., 386, 388, 393. Russell, G. A., 49. Russell, J., 235, 310. Russell, J. R., 262. Rutenburg, A. C., 67. Rutherford, D., 364. Rutherford, K. G., 266. Rutkin, P., 199. RBiiEka, J., 489, 493. Ruzicka, L., 429. Ryan, D. W., 428. Ryan, K. J., 429, 430. Ryback, G., 419. Rybalko, K. S., 292. Ryberg, C. E., 466. Rydberg, R., 113. Ryder, G. A., 95. Rydon, H. N., 246.
B
laran, M. S., 470. Sarma, P. L., 441. Sarma, V. R., 502. Sasakawa, T., 404. sass, R. L., 506. sabel, A., 258. 3abe1, H. D., 296. 3asse, W. H. F., 308. Sacco, A., 163. Sassu, G., 327. sacconi, L., 162, 164. Satake, K., 366. Sato, A., 368. Sackman, H., 95. Sato, S., 43. Safarov, 8. A., 334. Yato, Y., 201, 305, 356. Safronov, V., 130. Yatoda, I., 291. Sage, B. H., 98. Sattar, A. B. M. A., 284. Sagi, S. R., 468. Satterfield, C. N., 23, 34. Sah, P., 116. Saha, S. B., 456. Saucy, G., 274. Sahyun, M. R. V., 258. Sauer, J., 229. Said, A., 159. Sauers, C. K., 224. Sauers, R. R., 313. Saisho, H., 444. Saito, A., 277. Saunders, B. C., 263. Saito, S., 358. Saunders, M., 335. Sakami, W., 407. Saunders, W. H., 224. Sakurai, H., 462, 463, 464, Sauter, W., 474. 465. Savage, C. A., 165. Sakurai, T., 508. Savard, K., 429. Savereide, T. J., 252. Sala, O., 175. Salem, A. Y., 262. Saville, G., 86. Salesin, E. D., 452. Sawistowska, M., 257. Salim, N., 367. Sawyer, D. T., 448. Salmon, G. A., 42. Sawyer, P., 456. Salmon, J. E., 160. Saxby, J., 190. Salomon, K., 398. Saxton, J. E., 349. Salooja, K. C., 28. Scales, B., 299, 359. Salsburg, Z. W., 84, 88. Scarano, E., 470. Salt, M. L., 342. Scatchard, G., 74. Salzer, F., 459. Schaefer, F. C., 279, 338. Sam, D., 495. SchSifer, K., 96. Samkoff, N., 236. Schaefer, T., 281. Samn6, S., 257. Schgfer, W., 147. Samsonov, G. V., 144. Schaeffer, R., 132. Samuel, D., 204. Schafer, C., 343. Samuelson, O., 448. Schafer, H., 157. Samuelsson, B., 276, 284. Schaffer, R., 360. SAnchez, S. C., 450. Schaffner, K., 303, 305. Sanchez Pedreno, C., 455. Schaleger, L. C., 222. Sandalova, L. Yu, 98. Schall, E. D., 331, 358, Sandberg, A. A., 429. 489. Sandberg, R., 253. Scharf, R., 455. Sander, C., 379. Schatzki, T. F., 88. Sandermann, W., 290, 294, Schauble, J. H., 200, 303. 318. Scheaver, W. R., 358. Sanders, R. N., 46. Schechter, H., 245, 260. Sanderson, I. P., 440. Scheel, H., 185. Sanderson, P. M., 333. Scheer, M. D., 27. Sanderson, W. A., 224. Scheit, K. H., 376. Sandler, S., 32. Schell, P., 376. Sandner, W. J., 144. Schellenberg, M., 182. Sandor, E., 505. Schenck, G. O., 328, 340. Sandorfy, C., 203. Schenk, P. W., 143. Sendoval, A., 352. Scheuerman, R. F., 506. Sandri, J. M., 209. Schiff, H. I., 21, 44. Sann, E., 414. Schiffman, G., 368. Sano, S., 394. Schill, G., 449. Sanson, L., 123. Schilt, A. A., 453. Santaram, C. V. V. S. N. K., Schiltz, J., 119. 127. Schimmel, K. F., 259. Santer, J. O., 300. Schiweck, H., 367. Ryf, H., 305. Ryhage, R., 191. Rzheznikov, V. N., 306.
546
I N D E X OF AUTHORS N A M E S
Schlafer, H. L., 154, 168, 171. Schlenk, F., 417. Schlesinger, A. H., 210. Schleyer, P. von R., 209. Schlittler, E., 320, 353. Schmerling, L., 226. Schmialek, P., 338. Schmid, H., 237, 354. Schmid, K., 429. Schmid, R. F., 107. Schmid, W., 427. Schmidbaur, H., 141. Schmidt, H.-J., 280. Schmidt, M., 140, 141, 148. Schmidt, R., 330. Schmidt, U., 277. Schmidtke, H.-H., 94. Schmitt, R. A., 492. Schmitz, E., 321. Schmitz, F. J., 224, 320. Schmitz, R., 257. Schmitz-Dumont, O., 157. Schmutzler, R., 146. Schnalke, K. E., 335. Schneider, G., 86, 376. Schneider, H. J., 284. Schneider, I., 158. Schneider, J., 316. Schneider, R. A., 443. Schneider, W. G., 64, 200, 316. Schnoes, H. K., 204. Schober, G., 171. Schober, G., 482. Schoeborn, B. P., 513. Schoedler, C., 462, 466. Schollkopf, U., 242, 280. Schoen, L. J., 103. Schonberg, A., 148, 317. Schoenborn, B. P., 289. Schoener, B., 418. Schonfeld, T., 493. Schonowsky, H., 271, 329. Schoental, R., 345. Schottlander, M., 202, 327. Schofield, K., 203, 338, 377. Schogt, J. C. M., 275. Scholes, P. H., 488. Scholfield, C. R., 275. Schon, H., 172. Schonauer, G., 175. Schonbaum, G. R., 248. Schott, G., 136. Schott, G. L., 19. Schriigle, W., 134. Schram, E., 490. Schram, E. P., 136. SchraufstQtter, E., 338. Schrauzer, G. N., 135, 179, 181, 183. Schreiber, A. M., 333. Schreiber, K., 356. Schreiber, K. C., 207, 210, 219. Schreurs, J. W. H., 59.
Schrier, B., 234. Schriesheim, A., 231, 273, 335. Schroder, I., 409. Schroder, K., 460. Schroeder, G. L., 491. Schroeder, H., 135. Schroepfer, G., 419. Schubert, W. M., 233. Schuberth, H., 94, 98. Schiihrer, K., 335. Schueler, K. E., 332. Schuett, W., 339. Schuit, G. C. A., 169. Schulenberg, J. W., 296. Schuler, R. H., 48. Schuller, W. H., 297. Schulman, M. P., 386. Schulte, K. E., 329. Schultz, D. W., 413. Schultz, H. P., 257. Schultz, J. L., 498. Schulz, G. J., 103. Schulz, J., 258. . Schulze, J , 316. Schumacher, J. N., 295. Schumacher, R. T., 63. Schumann, D., 345. Schumann, H., 148. Schunior, R., 324. Schurdak, E. J., 467. Schuster, H., 376. Schuster, R., 156. Schutte, H. R., 343. Schutz, R. S., 342. Schwabe, K., 94, 96. Schwane, R. A., 359. Schwarting, A. E., 204, 344. Schwartz, H. C., 395, 396. Schwartzman, L. H., 273. Schwarz, J. C. P., 362. Schwarz, W., 219. Schwarz, W. M., 335. Schwarz, W. M., jun., 416. Schwarz-Bergkampf, E., 441. Schwatzenbach, G., 182. Schweers, W., 290. Schweiger, M., 382. gchweigert, B. S., 409. Schweitzer, G. K., 443. Schwendeman, R. H., 192. Schwenker, G., 195. Schwert, G. W., 419, 424. 3chwieter, U., 274. Scintee, V., 457. Scott, A. I., 288, 297, 298, 319. Scott, C. B., 311. Scott, C. C., 330. Scott, J. J., 386, 389, 392. Scott, P. G. W., 463. Scott, R. L., 73, 74, 76, 77, 78, 81, 84, 92, 93, 95, 97. 3cotts, G. T., 377. Scroggie, L. E., 482.
Sederholm, C. IF., 196. Sedlmeier, J., 258. Seefelder, M., 261, 269. Seel, F., 144. Seese, W. S., 304. Segal, R., 414. Segatto, P. R., 464. Seidl, J., 484. Seifert, H.-J., 156. Seifert, W. K., 219. Seifter, E., 403. Sela, M., 253. Selen, H., 199. Selig, H., 130. Selin, L.-E., 104, 119. Sellers, D. E., 483, 487. Selmer-Olsen, A. R., 478. Seltzer, S., 229. Selva, A., 255. Semenenko, K. N., 130. Semenov, D. A., 311. Semenov, I N., 161. . Semler, G., 326. Semmler, H., 144. Semochkina, T. V., 483. Sen, S., 160. Seng, F., 261. Seo, M., 350. Sepall, O., 368. Sequeira, J., 246. Serber, R., 103. Serdyuk, N. K., 33. Serebryakov, E. P., 263. Sergeant, G. A., 440. Serrano, J., 442. Serratosa, F., 270. Seshadri, T. R., 329. Setlow, R., 372. Settine, R. L., 196. Severin, T., 257. Seyferth, D., 129, 185, 243, 261, 266. Shachat, N., 269. Shackelford, J. M., 273. Shafer, J., 250. Shafer, J. A., 253. Shafi, M., 115. Shain, I., 335, 489. ShakhtakhtinskKG. B., 453. Shakirov, T. T., 347. Shalgosky, H. I., 488. Shalitin, Y., 253. Shaluvina, I. F., 276. Shamma, M., 205, 347, 350. Shamseldin, A. M., 469. Shanin, M., 40. Shapfro, I., 132, 135. Shapiro, M. Y., 441. Shapiro, R., 375, 377. Sharf, B., 63. Sharif, L. E., 163.
Scroweton, R. M., 299, 359. Seakins, M., 33. Searcy, A. W., 100, 129. Searle, R. J. G., 309. Searles, S., 321.
INDEX
OF AUTHORS NAMES
547
Sharkey, A. G., 498. Sharkey, W. H., 258. Sharma, D., 106. Sharma, J. P., 457. Sharman, S. H., 233. Sharp, D. W. A., 166, 181. Sharp, J. H., 60. Sharpless, R. L., 126. Sharts, C. M., 281. Shatkin, A. J., 382. Shatkina, T. N., 217. Shavel, J., 351. Shaw, B. L., 179, 180. Shaw, G., 331, 339. Shaw, K. B., 389. Shaw, N., 375, 402, 409. Shaw, R., 246. Shaw, R. A., 145. Shaw, W. H. C., 440. Shawky, M., 262. Shcherbakov, V. A., 64, 65. Shchukarev, S. A., 156,161, 162. Shearer, H. M. M., 509. Shechter, H., 282. Sheehan, J. C., 322, 325. Sheehan, J. T., 332. Sheldon, J. C., 158. Sheline, R. K., 175, 176. Shemin, D., 386, 388, 393, 403, 411. Shemyakin, M. M., 260,289, 318. Shen Han-Li, 450. Shepard, M. S., 348. Sheppard, N., 64, 190, 290. Sheppard, R. C., 332. Sheppard, W. A., 149, 263. Sheridan, J., 192. Shetty, P. S., 483. Shida, J., 51. Shields, B. D. C., 86. Shields, H., 53, 367. Shifrin, S., 413. Shigeru Oae, 230. Shihren Hu, 196. Shildkraut, C. L., 378. Shilov, A. E., 47. Shim, J., 99. Shimanouchi, T., 372, 379. Shimizu, T., 491. Shimo, K., 265, 279. Shiner, V. J., 216, 247, 421. Shiner, V. J., jun., 421. Shingu, K., 272. Shingu, T., 349. Shinoda, K., 80, 81. Shinozuka, F., 461. Shipman, J. J., 192. Shipman, W. H., 452. Shirai, H., 489. Shishido, N., 315. Shoemaker, D., 55. Sholette, W. P., 136.
Shome, S. C., 451. Shoolery, J. N., 65, 246, 352, 431. Shoppee, C. W., 201, 210. Short, G. D., 471. Short, R. V., 428, 429. Shorter, J., 233, 253, 336. Shostakovskii, M. F., 272, 280. Shoulders, B. A., 304. Showell, J. S., 262,274,280. Shrebkova, L. M., 455. Shreeve, J. M., 150. Shridhar, D. R., 302. Shrivastava, S. P., 453. Shriver, D. F., 137. Shtern, V. Ya., 22. Shtifman, L. M., 473. Shubnikov, A. V., 505. Shulgin, A. T., 263. Shulman, R. G., 45, 46. Shults, W. D., 464. Shukla, R. C., 114. Shute, S. H., 363. Shvo, Y., 300. Sh;yrkova, L. A., 462. Sibatani, A., 380. Sicher, J., 287, 344. Siddiqui, S., 349. Sidyakin, G. P., 347. Sieber, R., 258. Siegel, E., 259. Siegel, L., 425. Sierra, F., 455. Sievers, R. E., 171. Sigsby, J. E., 449. Sikes, J. H., 479. Silbert, L. S., 259, 274. Silsbee, R. H., 62. Silva, R. A., 343. Silver, H. B., 136. Silver, M. S., 208, 250. Silverstone, N. M., 468. Silvey, W. D., 476. Sim, G. A., 286, 291, 293, 294, 296, 297, 298, 301, 317, 330, 349, 351, 607, 509, 512, 513. Simamura, O., 236. Simatupang, M. H., 318. Simes, J. J. H., 300. Simkin, J., 170. Simmler, W., 430. Simmons, H. E., 311. Simmons, R. F., 24. Simmons, W. C., 135. Simon, H., 224, 361. Simon, M., 86, 374. Simon, R. W., 258. Simon, W., 232, 474. Simonov, A. M., 331. Simonson, R., 448. Simpson, M. V., 371. Simpson, W. R. J., 297. Singh, A., 217, 358. Singh, B., 470.
Singh, B. R., 450. Singh, D., 460, 461. Singh, J. J., 451. Singh, J. L., 114. Singh, N., 358. Singh, N. L., 112, 114. Singh, R. P., 478. Singleton, M. F., 364. Sinsheimer, R. L., 379. Sirois, J. C., 485. Sisido, K., 277. Sisler, H. H., 145. Sisman, E., 457. Sisti, A., 262. Sitaram, P., 109. Sitdykova, N. S., 130. Sivasankaran, K., 254. Sizer, I. W., 425. Sjoberg, B., 190, 194. Sjolander, N. O., 319. Sjovall, J., 284. Skahan, D. J., 497. Skaric, V., 325. Skeil, P. S., 216. Skidmore, S., 337. Skinner, G. B., 19. Skinner, W. A., 424. Skirrow, G., 35, 37. Sklar, R., 353. Sklarr, R., 351, 513. Sklarz, B., 300. Skoda, J., 447. Skoludek, H., 154. Skomoroski, R. M., 335. Skorcz, J. A., 235, 416. Skripov, F. I., 69. Skripov, V. P., 97. Skrube, H., 494. Slade, P., 250, 306. Slagel, R. C., 292. Slater, C. D., 236. Slaughter, C., 405. Slaunwhite, W. R., 429. Slavik, V., 467. Sleight, A. W., 161. Sleva, S. F., 465. Sloan, A. D. B., 308. Sloan, H., 185. Slomba, A. F., 109. Slomp, G., 201, 337. Small, A., 210, 281. Small, R. W. H., 159, 501, 504, 506. Smaller, B. O . , 55, 58. Smalley, H. M., 271. Smallwood, S. E. F., 113. Smart, J., 377. Smellie, R. M. S., 382. Smidt, J., 47, 258. Smiley, K. L., 403. Smirnov, B. P., 494. Smirnova, G. S., 369. Smith, B. C., 145. Smith, B. R., 208. Smith, B. V.,232. Smith, C. R., jun., 275.
548
I N D E X OF AUTHORS' NAMES
Smith, D. L., 181, 488. Smith, E. A., 159. Smith, E. B., 74, 75, 81, 94. Smith, E. L., 375, 395, 407. Smith, E. M., 463. Smith, F., 95, 367. Smith, F. T., 123. Smith, G. F., 349, 355, 439. Smith, G. L., 258. Smith, G. N., 276. Smith, G. S., 503. Smith, H., 492. Smith, H. E., 290. Smith, H. G., 502. Smith, J., 258. Smith, J. A. S., 194. Smith, J. C., 269. Smith, J. D., 137. Smith, J. H., 168. Smith, L. L., 432. Smith, L. W., 346. Smith, M., 266, 306. Smith, M. V., 277. Smith, N. L., 145. Smith, 0. W., 429. Smith, P. A., 244. Smith, P. A. S., 220, 232, 325. Smith, P. W., 158. Smith, R. A., 84. Smith, R. A. D., 459, 474. Smith, R. M., 403, 405. Smith, S., 259. Smith, S. G., 213, 229. Smith, W., 230, 275, 276, 507. Smith, W. A., 223. Smith, W. B., 273. Smith, W. C., 149, 263. Smith, W. V., 109. Smithen, C. E., 326. Smithies, O., 419. Smolina, T. A., 230. Smolinsky, G., 60,244, 309, 321. Smolyar, B. Ya., 131. Smyth, R. D., 400, 401. Snavelly, F. A., 202. Sneen, R. A., 208,209,214. Snell, J. F., 319. Sniegoski, L. T., 361, 496. Snodgrass, P. J., 423. 'Snow, R. L., 94. Snowden, P., 98. Snowden, F. F., 27. Snyder, L. C., 56, 60, 240. Snyder, R. G., 179. Sobell, M., 362, 363. Sobolov, M., 403. Soderberg, R. H., 163. Soeder, R. W., 286. Soderberg, B., 104. Sorensen, N. A., 271. Sorlin, G., 328. Soffer, L. J., 427, 429. Sokoleva, N. A., 38.
Sokolov, S. D., 331. Soler, A. J., 362. Solliday, N., 216. Sollott, G. P., 146. Solomon, I. J., 147. Solomon, J., 487. Solomon, S., 432. Solon, E., 463. Somcynsky, T., 99. Somerville, S. M., 238. Sommer, L., 440, 441. Sommer, L. H., 207, 254. Sommer, N., 261. Sommer, P. F., 474. Son Bredenberg, J. B., 299. Sondheimer, F., 198, 305, 307, 316, 327. Sonnenberg, J., 313. Somevald, W., 275. Sorenson, T. S., 418. fiorm, F., 277, 292, 303, 375, 377. Sorokin, M. I. 44. ?, Sosey, A. D., 52. Soto, A., 338. SouEek, J., 465, 474. Souchay, P., 486. Souciec, M., 295. Soulal, M. J., 322. Soulen, J. R., 499. Sousta, J. A., 336. Sowden, J. C., 364. Sowerby, D. B., 137, 149. Sowinski, F. A., 342. Soyama, T., 425. fipaEkovB, A., 475. Spalla, C., 411, 412. Spalthoff, W., 65. Spanier, E. J., 139. Sparatore, F., 395. Spare, C. G., 278. Sparks, R. A., 514. Speakman, J. C., 509. Specht, H., 449. Spees, S. T., 171. Spell, W. H., 409. Spence, R., 27. Spencer, E. Y , . 294. Spencer, I. D., 343. Spencer, J. F. T., 279. Spencer, M., 378. Spencer, R. D., 471. Spencer, R. R., 366. Sperry, J. A., 232. Speyer, J. F., 381. Spiegelmann, S., 380. Spikner, J. E., 477. Spilners, I. J., 497. Spinks, J. W., 49. Spinner, E., 203. Spinner, I. H., 94. Spiteller, G., 204, 352. M., Spiteller-Friedmann, 204. Spitzy, H., 494. Sponer, H., 100.
Spray, G. H., 410. Springer, R. H., 339, 374. Sprinson, D. B., 411. Spritzer, M., 487. spumy, z., 479. Srinivasan, R., 287, 502. Srivastava, K. C., 467. Srivastava, T. N., 142. Straab, H. A., 261, 262, 320. Stacey, F. W., 227. Stacey, M., 361, 364, 366, 367. Stadtman, E. R., 404. Stadtman, T. C., 402, 410. Stgllberg-Stenhagen, S., 191, 275. Stafford, F. E., 119, 120. Stafford, S. L., 177. Staiff, D. C., 197. Stam, C. H., 507. Stamberg, J., 484. Stammreich, H., 175. Stamper, J. G., 121, 122. Stangl, H., 323. Stanier, R. Y., 274. Stanko, V. I., 135. Stansfield, F., 314. Stanton, G. M., 333. Stanton, R. E., 478, 489. Staples, C. E., 191. Starer, I., 216. Stark, G., 355, 430. Stark, G. R., 462. Starkey, J. H., 277. Starman, B., 379. Starnes, W. H., 235. Starodubtsev, S. V., 361. Starova, N. G., 280. Starratt, A. N., 300. Stary, J., 493. Stary, Z. P., 486. Staskun, B., 262. Staszewski, R., 448. Statz, H., 46. Stauffacher, D., 348, 352. Staum, M. M., 212. Staveley, L. A. K., 88. Stedman, R. J., 393. Steed, K. C., 464. Steele, D., 113, 114. Steele, E. L., 492. Steffens, J., 361. Steglich, W., 263. Stehling, F. C., 497. Stein, G., 414. Stein, P. C., 493. Stein, T. W., 23. Steinberg, D. H., 199. Steinberg, M., 152. Steinbrecher, M., 96. Steiner, A., 332. Steiner, R. F., 371. Steinert, H., 34. Steltenkamp, R. J., 280. Stenhagen, E., 191, 275. Stephan, A., 316.
549
Stephen, A. M.,367. Stephens, B. G., 454. Stephens, F. B., 463, 464. Stephens, R., 311. Stephenson, M. L., 382. StBrba, J., 445. Stern, E. W., 179. Stern, J. R., 404. Sternbech, B., 141. Sternhell, S., 260. Sterlicht, H., 61. Sterlyadkina, Z. K., 130. Stetter, H., 320. Steudel, W., 342. Stevens, A., 407. Stevens, C. L., 339. .Stevens, I. D. R., 241, 321, 331. Stevens, M. A., 373. Stevenson, D. P., 83. Stevenson, R., 300. Stevenson, R. W. H., 46. Steward, E. G., 167. Stewart, C. A., 228. Stewart, C. A., jun., 281. Stewart, D. F., 159, 469. Stewart, F. H. C., 264. Stewart, R., 230. Stiddall, T. H., tert., 191. Stiddard, M. H. B., 177. Still, J. E., 459. Stimson, V. R.. 224. Stirling, C. J. M., 216. Stjernholm, R., 404. Stock, A., 414, 415. Stock, D. I., 170. Stock, J. T., 458, 461, 466. stock, L. M., 232. Stocker, J. H., 254. Stoicheff, B., 190. Stoicheff, B. P., 189, 190, 195. Stollar, D., 424. Stolz, I. W., 175, 176. Stone, A. J., 47. Stone, E. W., 56, 58. Stone, F. G. A., 176, 177, 180, 184, 185, 254, 255, 283. Stone, G. R., 335. Stone, T. J., 48. Stone, W., 90. Stoner, G. A., 477. Stoodley, R. J., 361. Storey, J. D., 486. Stork, G., 201, 270, 296, 306, 318, 328. Storms, E. K., 156. Storonkin, A. V., 97. Storr, A., 137. Storr, R., 143. Stothers, J. B., 219, 284, 337. Stotz, E., 396. Stout, G. H., 503, 509. Stout, V. F., 509.
Stove, E. R., 322. Stover, E. D., 67. Strachan, R. G., 279. Stradling, S. S., 237. Strain, H. H., 325. Strandjord, P. E., 415. Strating, J., 340. Strauss, H. L., 50. Street, H. V., 448. Streib, W. E., 501. Streibl, M., 277. Streitwieser, A., 207, 214, 230, 232. Strehlow, H., 246. Strem, M. E., 308. Streuli, C. A., 458. Stricks, W., 487. Striegler, K., 318. Strivens, T. A., 463. Strohmeier, W., 130, 175, 182. Strolenberg, K., 146. Strom, E. T., 49. Strominger, J. L., 377. Strong, R. L., 82. Struck, J., 425. Strunin, B. N., 265. Stuart, R., 46. Stubbs, W. H., 184. Stubley, D., 92, 99. Studer, P., 446. Sturm, B. J., 158. Sturm, H. J., 323. Stutz, A. I., 141. Style, D. W. G., 27. Su, D., 378. Subbaraman, P. R., 483. Subba Rao, G. S. R., 301. Subbaratham, N. R., 40. Subramanian, E., 503. Such$, M., 292. Sucrow, W., 271. Sueoka, N., 378. Sueur, R., 31. Sugano, S., 46. Sugden, T. M., 20, 100,207. Sugimoto, N., 358. Sugita, Y., 395. Sui, C. W., 477. Suld, G., 341. Sulkowski, T. S., 339. Sullivan, E. A., 132, 257. Sullivan, P. J., 205. Sullivan, R. A. L., 507. Sullivan, R. J., 83. Sully, B. D., 438. Summa, A. F., 487. Sund, H., 422. Sundaram, A., 191, 199. Sundaram, K. M. S., 199. Sundermeyer, W., 138, 140, 151. Sung Moon, 210. Sunjaraman, M. G., 170. Sunko, D. E., 209. Supin, G. S., 483.
Suresh, K. S., 333. Surls, J. P., 491. Suschitzky, H., 337. Sustmann, R., 139. Susz, B. P., 155. Sutcliffe, L. H., 145, 162. Sutherland, I., 411. Sutherland, I. O., 318. Sutherland, J. K., 286. Sutherland, M. D., 290,291. Sutherland, S. A., 301, 513. Suttle, J. F., 154. Sutton, G. J., 158, 160, 167. Suydam, F. H., 202. Suzuki, I., 193. Suzuki, M., 19. Suzuki, N., 493. Suzuki, S., 362, 370. Svehla, G., 500. Svendsen, A. B., 448. Svensson, R., 466. Svoboda, M., 287. Swain, C. G., 213, 218, 219, 311. Swalen, J. D., 47, 58. Swaminathan, K., 165, 174. Swaminathan, S., 287. Swan, G. A., 235. Swanholm, C. E., 204, 354. Swartz, M. N., 378. Sweat, M. L., 427, 429. Sweeley, C. C., 275. Sweeney, D. M. C., 190. Sweet, T. R., 493. Swern, D., 259, 262, 274, 280. Swift, T. J., 68. Swinnerton, J. W., 449. Swor, R., 445. Sykes, A. G., 173. Sykes, P. J., 277. Symons, M. C. R., 45, 47, 48, 49, 51, 54, 55, 56, 57, 58, 61, 63, 68, 150, 151, 161, 171. Symons, R. H., 381. Syrkin, Ya-K., 165. Szab6, L., 362, 365. Szabo, Z. G., 82. Szantay, C., 321. Szejtli, J., 369. Szkrybalo, W., 198. Szot, Z., 388. Ta-Chuang Lo Chang, 275. Tada, M., 382. Taft, It. W., 218. Taguchi, I., 508. Taha, I. A. I., 208. Taher, N. A., 218. Taikova, N. K., 279. Tait, G. H., 386, 397, 398. Tait, J. F., 430, 431. Tait, S. A. S., 430, 431. Takahashi, T., 462, 463, 464, 465, 489.
550
I N D E X OF AUTHORS' NAMES
Takahashi, Y., 302. Takai, M., 380. Takamoto, S., 441. Takamuru, S., 369. Takanami, M., 382. Takase, M., 278. Takenaka, Y., 419. Takeoka, Y., 196. Takeshita, H., 284. Takeyama, S., 406. Takiura, K., 367. Talipova, L. L., 455. Tallent, W. H., 299. Tallmann, R. L., 130. Talmage, P., 386. Talrose, V. L., 24. Tamiya, N., 498. Tamres, M., 82. Tamura, Y., 358. Tan, L., 355. Tan, S. H., 458. Tanaka, K., 417. Tanaka, Y., 106, 107, 123, 125, 126, 364. T a n a w v , I. V., 154. Tandon, K. N., 453. Tanei, T., 52. Tanida, H., 223. Tanner, H., 263. Tao, L. C., 94. Tao, R. C. C., 197. Taqui Khan, M. M., 422. Tarbell, D. S., 237. Tarlton, E. J., 389. Tarrant, P., 196. Tartari, A., 481. Tashkentsk, Tr., 369. Tashmukhamedova,K.,361. Tate, D. P., 176. Tate, M. E., 359, 366. Tatievskii, V. M., 127. Tatlow, J. C., 310, 311. Tatum, E. L., 382. Taub, D., 318. Taub, I. A., 236. Taube, H., 67, 153. Taurog, H., 494. Tavs, P., 275. Tawde, N. R., 112. Taylor, A., 502. Taylor, B., 154. Taylor, C. A., 503. Taylor, D. R., 357. Taylor, E. C., 240, 337, 338. Taylor, F. B., 136. Taylor, H. G., 440. Taylor, J. B., 343. Taylor, L. J., 219. Taylor, M. S., 454. Taylor, P. M., 359. Taylor, R. C., 137. Taylor, W. I., 326, 351, 362, 353, 513. Tedder, J. M., 324. Tedeschi, P., 416. Teekell, R. A., 445.
Teijgeler, C. A., 446. Tekhonova, E. A., 504. Telang, S. A., 341. Teller, E., 114. Temperley, H. N. V., 94. Templeton, D. H., 507. Tener, G. M., 376, 377. Tengler, H., 178. Tennigkeit, J., 376. Tenseldam, C. A., 120. Tera, F., 483. Teraoka, A., 348. Terashima, M., 348. ter Borg, A. P., 307, 313 314, 315. Terent'eva, E. A., 484. Ter Haar, G., 135. Terry, W. G., 323. Testa, C., 444. Testa, E., 323. Tetenbaum, M. T., 480. Thacker, R., 81. Thaller, V., 296. Thayer, J. S., 140. Theal Stewart, E., 113. Theobald, R. S., 368. Theorell, H., 418, 421, 422 Thesing, J., 326. Theubert, F., 177. Thickbroom, P. D., 269. Thiessen, W. E., 299. Thierig, D., 135. Thilo, E., 146. Thodos, G., 98. Thofern, E., 396. Thoma, J. A., 369. Thomaes, G., 90. Thomas, A. F., 301, 302. Thomas, G. M., 343. Thomas, I. M., 157. Thomas, J. D. R., 449. Thomas, J. R., 53. Thomas, L. F., 363. Thomas, L. M., 466. Thomas, M. R., 325. Thomas, S. S., 43. Thompson, A., 367. Thompson, A. R., 97. Thompson, H. M., 126. Thompson, L. C., 152. Thompson, M. C., 173. Thompson, R., 259. Thompson, R. Y., 377. Thomson, C., 53. Thomson, J., 369. Thomson, J. F., 424. Thornson, P. J., 319. Thornson, R. H., 235, 310. Thomson, R. S., 233. rhomson, S. J., 254. I'hornley, J. H. M., 46. rhornton, E. R., 218. rhorp, N., 78. rhrush, B. A., 20,102,121, 314. rhurmond, C. J., 120.
Thurn, R. D., 222. Thyret, H., 183. Tichf, M., 344. Tidy, D., 217. Tiers, G. V. D., 282. Tietz, T., 114. Tighe, J. J., 21. Tjebbes, T., 338. Tikhomirova, N. N., 47. Tikhomolova, M. P., 361. Till, F., 449. Till, I., 449. Tilney-Bassett, J. F., 244. Timell, T. E., 370. Timmons, P. S., 235. Tipper, C. F. H., 18, 31, 35, 37. Tipson, R. S., 359. Titkov, Yu. V., 144. Titova, V. A., 97. Tiwari, R. D., 457. Tobe, M. L., 174. Tobias, I., 113, 114. Tochtermann, W., 311,313, 342. Tockstein, A,, 82, 484. Todd, Lord, 318, 375, 377, 383, 341, 411. Todd, R., 490. Toekelt, W. G., 226. Tolg, G., 443. Tomoskozi, I., 260. Tokes, L., 235, 269. Tokoroyama, T., 292. Tolbert, T. L., 262. Tolchinskaya, R. Ya., 280. Tolgyesi, W. S., 240. Tolgyest, W. S., 285. Tolles, W. C., 149. Tolmacheva, T. A., 156. Tolnas, E. L., 120. Tomalia, D. A., 320. Tomasz, M., 270, 318, 328. Tomita, K., 360, 372. Tomita, M., 348. Tomko, J., 356. Tomlin, J. E., 263, 276. Tomljenovi6, T., 219, 287. Tommila, E., 235. Tompkina, F. C., 14, 15. Tomkins, G. M., 425, 416, 426. Tong, E., 424. Tooney, J. I., 401, 403. Toporowski, P. M., 97. Topping, G., 193. Topping, R. M., 244. Toptygina, G. M., 154. Torgov, I. V., 306. Torresani, J., 494. I'oscano, V. G., 261. roubiana, R., 276. Toussaint, A., 198. rowe, R. H., 185. Tome, J. C., 477. rownley, E. R., 267,287.
551
Towns, D. L., 230. Townsend, M. G., 48, 82. Trager, L., 372, 373, 409. Traetteberg, M., 190. Trager, W. F., 196. Trahanovsky, W. S., 202. Trajmar, S., 127. Traore, K., 161. Trapasso, L. E., 255. Trapnell, B. M. W., 13. Trapp, W. B., 254. Trautner, T. A., 378. Travers, S., 501. Travis, D. N., 101,119,121. Treanor, C. E., 126. Treanor, C. T., 111. Treble, D. H., 420. Trecker, D. J., 267, 287. Tregellas-Williams, J., 194. Trego, B. R., 280. Treiber, A., 183. Treibs, A., 393. Treichel, P. M., 176. Trkmillon, B., 459. Trenczek, G., 137. Trepka, W. J., 266. Trevalion, P. A., 55, 171. Trifan, D. S., 209. Tripathi, J. B. P., 143. Tripp, T. B., 92. Trippett, S., 299, 359. T r o h e n k o , S., 279. Trombe, I., 153. Trond, S. S., 159. Trotman-Dickenson, A. F., 35. Trotter, J., 161, 507, 508, 509. Trowell, F., 440. Trozzolo, A. M., 60. Truce, W. E., 258,280,322. Trueblood, K. N., 514. Trumbull, E. R., 224. Truscheit, E., 278. Truter, E. V., 446. Truter, M. R., 181. Tsaboi, M., 372. Tsapkina, I. V., 153. Tschesche, R., 355. Tseng, W. S., 417. Tsiklis, D. S., 98. Tsinsius, V. M., 156. TsO, P. 0. P., 379. G., Tsou~aris, 510. Tsuboi, M., 379. Tsuchida, R., 162. Tsuda, K., 201. Tsuda, S., 345. Tsuda, Y., 349. Tsugita, A., 381. Tsukahara, I., 491. Tsukamoto, A., 262. Tsunakawa, S., 191. Tsutsui, M., 283. Tsymbal, L. V., 280. Tiirk, G., 161.
Tuleen, D. L., 253. Tulloch, A. P., 279. Tundo, A., 329. Tunitskii, L. N., 127. Turco, A., 160. Turnbull, A. H., 166. Turnbull, J. P., 294. Turner, D. W., 36. Turner, H. S., 134. Turner, J. C., 360, 366. Turner, J. M., 388. Turner, M. A., 222. Turner, W. J., 393. Turner-Jones, A,, 506. Turova, N. Ya., 130. Turro, N. J., 283, 288. Turvey, J. R., 365. Turyan, Ya. I., 482, 486. Tuttle, T. R., 50. Twigg, G. H., 258. Tyler, B. J., 24. Tyler, C. M. B., 338. Tyree, S. Y., jun., 159. Tyte, D. C., 123. Tze Yung-Schaing, 450.
Ushakaova, N. I., 165. Ustkins, I., 407. Utkin, L. M., 346. Utley, J. H. P., 253. Utzinger, E. C., 305. Uyeo, S., 348, 349. Uzelac, V., 478.
VBgo, G., 487. Vagurtova, N. M., 331. Vahlquist, B., 389. Vahvaselkii, E., 447. Vainshtein, B. K., 507. Vainshtein, E. E., 154. Valenta, Z., 299, 357, 358. Valentin, P., 31. Valiev, K. A., 72. Vallee, B. L., 413, 420, 422, 423. Valnf, Z., 469. Van Ammers, M., 336. van Atta, R. E., 487. van Auken, T. V., 330. van Beers, G. V., 275. Vance, R. N., jun., 166. Vandenheuvel, W. J. A., Ubell, E., 510. 210. Uchikawa, H., 478. van der Helm, H. J., 420. Uchiyama, M., 281. van der Kerk, G. J. M., 142. Ud-Din, B., 165. Vanderslice, J. T., 113, 114. Ueberwasser, H., 305. van der Waals, J. H., 93. Ueda, S., 348. van der Want, G. M., 143. Onseren, E., 240. Vanderwerf, C. A., 220. Ugelstad, J., 273. Vandewiele, R. L., 429,432, Ugi, I., 252. 433, 434. Uhle, F. C., 306. Vhndorffy, M. T., 473. Uhlenbrock, W., 311. Vane, F. M., 194. Uhler, R. O., 282. van Egmond, J. C., 142. TJhler, U., 127. Van Ehrenstein, G., 382. Uhlig, E., 172. van Erkelens, P. C., 493. Ukafi, T., 192. van Eys, J., 417, 420. Ukita, T., 365, 376. Vangedal, S., 300. Ukshe, E. A., 129. . van Heijningen, R. J. J , Ulbricht, T. L. V., 320, 86, 87. 374, 375, 376. van Helden, R., 313, 314, Ulick, S., 430. 315. Ullman, E. F., 307, 310, van Koeveringe, J. L., 120. 331, 340. van Meerssche, M., 511. Ulm, K., 183. van Ness, H. C., 94, 95. Ulmann, M., 369. van Norman, J. D., 465. Ulmer, D. D., 420, 423. Van Praag, D., 375. Umland, F., 135, 443. van Sickle, D. E., 230. Umori, T., 493. van Steenwinkel, R., 90. Undes, R., 466. van Tamelen, E. E., 276, Underhill, A. E., 167, 171. 285, 303, 307, 320. Underwood, J. G., 329. van Tiggeln, A., 21. Undheim, K., 190. Van Zanter, B., 492. Ung, A. Y. M., 44. Varga, L. P., 158. Ungar, F., 416. Varhenikovh, A., 446. Uno, T., 193. Varma, A., 460. Urata, G., 387. Varshni, Y. P., 114. Urenovitch, J. V., 139. Vasedeve Murthy, A. R., Urquhart, J., 427. 149. Urry, G., 136, 140. Vasilevskii, K. P., 128. Urry, W. H., 267, 287. Vasiliev, R., 457. Urusovskaya, L. G., 473. Vasisht, S. K., 459.
552
Vaska, L., 178, 186. Vassalls, D. A., 499. Vatakencherry, P. A., 291. Vaughan, E. J., 436. Vaughan, J., 246. Vaughan, W. R., 253, 322. Vaver, V. A., 260. Vdovenko, V. M., 65. VeEeFa, M., 459, 474. Velasco, R., 121. Velick, S. F., 413, 418. Venanzi, L. M., 160, 161, 165, 170. Venkataraman, K., 341. Venkatesan, K., 287. Venkateswarlu, P., 127. Venkateswarlu, V., 450. Vercellotti, J. R., 368. Verderame, F., 191. Vereikina, L. I,., 144. Verhaegen, G., 119, 120, 128. Verhoek, F. H., 163. Verkade, J. G., 172. Verma, B. C., 470. Verma, R. D., 101,106,128. Verma, R. M., 453. Verma, V. K., 333. Vermont, G. B., 236. Vernon, C. A., 244. Vernon, J. M., 324, 325. Verron, H., 278. Verwoerd, D. W., 376. Vesell, E. S., 419, 420. Vesety, V., 454, 455. Vessman, J., 449. Vetter, H. J., 147. Vickery, M., 338. Viehe, H. G., 270. Viennet, R., 200. Vilfm, O., 94. Vilkov, L. V., 506, 510. Villotti, R., 305. Vinard, D. R., 269. Vincent, B. F., jun., 258. Vinogradov, A. V., 451. Virmani, Y. P., 203. Virtanen, A. I., 278, 320. Viswanathan, N., 354, 358. Vitali, R., 256. Vizsolyi, J. P., 377. Vlad, P., 295. Vodar, B., 123. Voevodskii, V. V., 24, 25, 34, 52. Vogel, A. I., 203. Vogel, E., 341. Vogel, G., 130, 340. Vogel, J., 485, 488. Vogler, A., 183. Vogt, F., 145. Voitovich, B. A., 157. Volcani, B. E., 401, 403. Volkenshtein, M. V., 198, 200. Volkin, E., 379.
Volpenhein, R. A., 277. Volpin, M. E., 322. Volpp, G., 342. von Dobeneck, H., 334. von Euler, H., 417. Von Hobe, D., 175, 182. von Planta, C., 274. von Rosenberg, J. L., 313. von Rosenberg, J. L., jun., 286. von Stackelberg, M., 482. von Veh, G., 322. von Witteneu, M. S., 327. Voorhies, J. D., 467. Vo-Quang, L., 269. Vorbrueggen, H., 204, 352. Vos, A., 511. Vreugdenhil, A. D., 266. Vriassen, C. H., 47. Vu, H., 103. Vulterin, J., 452, 453. Vydra, F., 469. Vyshinskaya, L. I., 184. Wacber, A., 372, 373, 409. Wade, K., 137. Wade, M. A., 479. Waddington, H. R. J., 322. Waddington, T. C., 136, 151. Waelbroeck, F., 91. Wagener, S., 13. Wagenhofer, H., 323. Wagner, A., 367. Wagner, C. R., 221. Wagner, F., 411, 412. Wagner, G., 375, 458. Wagner, O., 413. Wagner, R. I., 134. Wagner, R. P., 145. Wahba, A. J., 381. Wahl, D., 412. Waichiro Tagaki, 230. Waind, G. M., 162. Waiss, A. C., 214, 345. Waite, B. D., 480. Wakamatsu, S., 265, 279. Walborsky, H. M., 230. Waldenstrom, J., 389. Walerych, N., 413. Waley, S. G., 187, 207. Walia, J. P., 253. Walker, G. N., 254, 335. Walker, H. G., jun., 364. Walker, J., 306. Walker, P., 244. Walker, R. W., 24, 25. Walker, T., 347, 348. Walkiewitz, D., 142. Walkley, J., 74, 75, 81, 82. Wallace, L., 123, 127. Wallace, R. M., 179. Wallbridge, M. G. H., 137, 223. Wallenfels, K., 416, 422. Walling, C., 228, 237.
Wallis, E. S., 210. Walls, F., 352. Walrafen, G. E., 150. Walsh, A. D., 23, 27, 42, 55. Walsh, P. N., 102. Walter, P., 416, 418. Walter, P. H. L., 161. Walter, S. I., 420. Walter, W., 280. Walter, W. F., 276, 320. Walton, H. F., 170. Walvekar, A. P., 112. Walwick, E. R., 375. Wampler, D. L., 138. Wandrey, P., 345. Wang, 1.-C., 69, 71. Wang, R. H., 98. Wang, S. Y., 372. Wannagat, U., 140. Wanzlick, H. W., 242. Wasicky, R., 446. Wasserman, E., 60, 244. Warburg, O., 396. Ward, C. H., 206. Ward, E. R., 232, 266, 333. Ward, G. M., 476. Ward, J. C., 49. Ward, L. G. L., 139. Ward, R., 161. Ward, R. B., 367. Ward, R. L., 51, 53, 57. Wardi, A. H., 486. Waris, A., 39. Warne, R. J., 134. Warren, C. L., 200, 317. Warren, F. L., 343. Warton, J. W., 448. Warwicker, E. A., 32, 39. Warzecha, K., 424. Watanabe, H., 294. Watanabe, I., 379. Watanabe, K., 125. Watanabe, T., 366, 508. Watari, H., 425. Waters, A. H., 407. Waters, E. L., 47. Waters, J. M., 164. Waters, 0. J., 290. Waters, W. A., 48, 244. Watkins, J., 326. Watling, J., 488. Watson, A. A., 280. Watson, D. G., 509, Watson, H. R., 164, 171. Watson, J. D., 379. Watson, J. S., 42. Watson, T. R., 366. Watson, W. H., 223. Watt, G. W., 154, 163,165. Watton, E. C., 167. Watts, D. C., 419. Watts, D. W., 174. Watts-Tobin, R. J., 380. Wawrzyczek, W., 442. Vlfawszkiewicz, E. J., 400. Wawzonek, S., 480.
553
Wayne, R., 267. Wayne-Meinke, W., 492. Webb, G. B., 347. Webb, J. S., 366. Webb, R. E., 403. Webb, W. E., 194. Webber, J. M., 366, 367. Weber, G., 418. Weber, K. H., 316. Weber, M. J., 46. Weber, R., 258. Weberndorfer, V., 333. Webster, B., 324. Webster, B. R., 338. Webster, D. E., 254. Webster, G., 383. Webster, 0. W., 258. Weedon, B. C. L., 269, 273. Wehrli, H., 303, 305. Wei, P. E., 336. Weidler, A. M., 190. Weidmann, G., 443. Wei-Hsien Chang, 446. Weil, J. A., 47. Weimann, G., 376. Weinberg, K., 305. Weinblum, D., 372, 373. Weiner, H., 214. Weiner, M., 130. Weinhold, P., 311. Weinstein, B., 296. Weinstein, S., 223. Weinstock, J., 223. Weir, H. E., 475. Weis, C. D., 328. Weis, W., 335. Weisblum, B., 382. Weiss, A., 275. Weiss, E., 181. Weiss, H. G., 132. Weiss, H. V., 452, 495. Weiss, J., 199. Webs, U., 289, 297. Weissbach, H., 400, 401, 413. Weiss-Broday, M., 204. Weissman, S. I., 45, 50, 53, 58, 59, 60, 61, 136. Weisz, D., 147. Weisz, H., 438, 490. Weitkamp, H., 195, 281. Weitz, G., 513. Welch, C. A., 231. Welch, V. A., 365. Welcman, N., 146, 150. Weliky, I., 427. Wellington, C. A., 41. Wells, A. F., 129. Wells, C. H. J., 34. Wells, R. J., 293. Welsh, H. L., 190. Welsh, M. J., 509. Welti, D., 191, 195. Weltner, W., 102. Wempen, I., 374. Wender, S. H., 446.
Wendlandt, W. W., 166, 499. Wendler, N. L., 318. Wenger, P. E., 468. Wenger, R., 305. Weniger, S., 118. Wenkert, E., 343, 349, 350, 351, 353. Werbin, H., 427. Werhagen, E., 106. Werner, D., 144. Werner, H., 184. Werner, L., 320. Werner, R. P. M., 180. Wertheim, G. K., 169. Wertz, J. E., 50, 68, 71. West, B. O., 147, 155, 162, 168. West, C. D., 429. West, R., 130,138, 140, 313. West, T. S., 440, 469, 478, 484. Westall, R. G., 389. Westenberg, A. A., 20. Westerlund, B., 106, 124. Westheimer, F. H., 249, 335, 415, 416. Westin, B., 434. Weston, J. F., 91. Wettermark, G., 336. Wettstein, A., 256, 305, 427, 429. Weygand, F., 224, 263. Whalley, E., 96. Whalley, W. B., 358. Wharton, P. S., 306, 355. Whealy, R. D., 485. Wheatley, P. J., 140, 144, 508, 511. Wheeler, D. H., 71. Whelan, W. J., 359, 370. Whiffen, D. H., 53, 54, 55, 56, 57. Whipple, E. B., 326. Whistler, R. L., 360, 364, 369. Whitaker, D. R., 366. Whitaker, J. R., 247. White, A. M., 405, 406. White, D., 103. White, D. C., 397. White, D. E., 298. White, E. H., 287. White, E. M., 219. White, J. C. B., 203. White, J. G., 514. White, R. C., 159. White, R. F. M., 64. White, R. W., 259, 294. White, W. N., 236, 240. Whitear, B., 289. Whitehead, E. P., 423. Whitehead, R. W., 408. Whitehurst, J. S., 306. Whiteley, T. E., 365. Whitham, G. H., 210.
Whiting, D. A., 329. Whiting, K. D. E., 347, 348. Whitley, A., 165. Whitlock, H. W., 312, 341. Whitlock, H. W., jun., 288. Whitman, S. L., 383. Whitney, D. R., 502. Whitney, R. B., 246. Whittaker, D., 191, 195. Whittaker, N., 260. Wibberley, D. G., 327. Wiberg, K. B., 288, 312. Wiberg, N., 139. Wickberg, B., 350, 351. Wieber, M., 140, 141. Wieland, A., 335. Wieland, K., 102. Wieland, P., 305. Wieland, T., 419, 424. Wiesendanger, H. U. D., 13. Wiesener, K., 94, 96, 299, 357, 358. Wiest, H., 229. Wigen, P. E., 55. Wiggins, T. A., 109. Wilcox, C. F., 209, 210. Wilcox, H. E., 510. Wilcox, W. S., 132. Wilde, G., 163. Wildman, W. C., 343, 348. Wiley, P. F., 341. Wilharm, G., 412. Wilhelm, G., 86. Wilkas, M., 260. Wilke, G., 179. Wilkins, C. J., 160. Wilkins, M. H. F., 378. Wilkins, R. G., 174. Wilkinson, G., 129, 160, 176, 180, 181, 184. Wilkinson, P. G., 100, 106, 107, 109, 122. Willcott, M. R., tert., 200, 289. Wille, F., 332. Willemert, A., 269. Willey, F. G., 304. Willey, G., 145. Willey, R. H., 191. William Johnson, A., 242. Williams, A., 35. Williams, A. A., 179. Williams, A. R., 336. Williams, D. E., 508. Williams, D. L. H., 224. Williams, F. T., jun., 260. Williams, G. H., 235. Williams, H., 337. Williams, J. C., 277. Williams, J. H., 444. Williams, J. M., 368. Williams, M., 451. Williams, M. J., 111. Williams, N. R., 360. Williams, N. J., 332. Williams, P. L., 438.
554
I N D E X O F A U T H O R S NAME S
Williams, R., 163. Williams, R. E., 132. Williams, R. G., 156. Williams, R. J. P., 158, 423. Williams, R. L., 131. Williams, R. M.,221. Williams, R. P., 381. Williams, T. H., 284. Williams, T. P., 365. William, T. R., 218, 460, 467. Williams, W. L., 62. Williamson, A. G., 74, 84, 93, 95. Williamson, S. M., 150. Willis, C. J., 142. Willis, C. P., 477. Willis, H. A., 206. Willis, J. B., 480. Willis, R. G., 269, 282. Willner, D., 211. Wills, L. J., 410. Wills, R., 217. Willson, C., 380. Wilmans, W., 407. Wilmarth, W. K., 173, 174. Wilson, A. D., 439, 440. Wilson, A. F., 476. Wilson, A. L., 444. Wilson, C. L., 476. Wilson, C. O., jun., 135. Wilson, D. V., 331. Wilson, E. B., 189, 195. Wilson, H., 428. Wilson, H. N., 462. Wilson, H. W., 496. Wilson, J. M., 200,204,205, 303, 351, 352, 353, 354. Wilson, J. W., 216. Wilson, R. M., 400, 401. Wilson, T. L., 275. Wilson, W. B., 153. Wilt, J. W., 208, 219. Wilucki, I., 340. Whner, D. C., 471. Winchester: J. W., 491. Windmueller, H. G., 417. Winer, A. D., 418. Winey, D. A., 287. Wingrove, A. S., 230. Winkler, C. A., 143. Winnewisser, M., 192. Winstead, M. B., 279. Winstein, J., 336. Winstein, S., 107, 207, 209, 210, 214, 219, 223, 229, 313. Winter, J., 290. Winter, M., 278. Winterfeld, K., 338. Winterfeldt, E., 345. Wintersteiner, O., 356. Wintrobe, M. M., 395, 396. Wion, J. W., 203. Wise, H., 123. Wise, J. H., 151.
Wish, L., 493. Wisotsky, M. J., 209, 285. Wisser, K., 485. Witkop, B., 202, 323. Witkowski, A., 116. Witkowska, S., 476. Witt, W. P., 102. Wittenberg, J., 393. Wittig, G., 144, 223, 235, 286, 311, 313, 342, 508. Wittke, O., 505. Wittstruck, T. A., 204. Witwit, A. S., 467. Witz, P., 303. Wolfel, E., 513. Woese, C. R., 382. Woessner, D. E., 66. Wojtowicz, P. J., 84. Wold, F., 377. Wolf, A. P., 240, 242. Wolf, J., 426. Wolf, L., 190. Wolf, S., 471. Wolf, W., 188, 235, 269. Wolfe, R. G., 416, 425. Wolff, M. E., 303. Wolfrom, M. L., 365, 367, 368, 370. Wolfsberg, K., 494. Wolinaky, J., 331, 358. Wollenweber, P., 446. Wollrab, V., 277. Wolovsky, R., 198, 307, 316. Wondratschek, H., 605. Wonkka, R. E., 217. Woo, P. W. K., 203, 365, 366. Wood, C. S., 332. Wood, D., 51. Wood, D. F., 489. . Wood, H. C. S , 257. Wood, H. G., 404, 405. Wood, S. E., 94. Woodbrey, J. C., 193. Woodruff, C., 230. Woods, D. D., 406, 407. Woods, M. C., 298. Woodson, E., 356. Woodward, R. B., 228,288, 318, 325. Woolley, D. W., 403. Woolley, H. W., 114. Woolfolk, E. O., 259, 442. Worden, E. F., 151. Wray, D., 299, 359. Wrede, F., 393. Wright, A., 139, 370. Wright, A. N., 143. Wright, C. V., 101,106, 121. Wright, D. A., 513. Wright, F. J., 32, 37. Wright, J., 150. Wright, P., 235. Wulfert, P., 152. Wulff, D. L., 372.
Wuller, J. E., 155. Wurster, W. H., 111, 126. Wuscherpfennig, V., 204. Wyatt, E. I., 495. Wyer, J. A., 366. Wyld, G. E. A., 457. Wyler, H., 327. Wylie, A. G., 257. Wylie, A. W., 152. Wyman, G. M., 133. Wyss, E., 322. Yag Dutt, 478. Yager, W. A., 60, 244. Yakovleva, T. V., 206. Yakubov, I. T., 112. Yale, H. L., 342, 487. Yamada, S., 162, 163. Yamagata, Y., 71. Yamaguchi, K., 51. Yamamoto, A., 155. Yamamoto, R., 491. Yamamura, S. S., 479. Yamato, Y., 349. Yamzin, I. I., 502. Yanai, M., 299. Yang, T. H., 358. Yankovsky, S. A., 380. Yarym-Agaev, N. L., 97. Yasaitis, E., 55. Yates, F. E., 427. Yates, K., 246, 364. Yates, P., 243, 287, 338. Yeadon, R. E., 99. Yen, L. C., 75. Yethon, A. E., 342. Yielding, K. L., 425, 426. Yi-Noo Teng, 494. Yoe, J. H., 479. Yoke, J. T., tert., 163, Yokel, H. L., 504. Yokeley, C. R., 32. Yoneda, Y., 20. Yonemitsu, O., 350. . 395. Yoneyama, Y , Yonezawa, T., 83. York, J. L., 396. Yorke, B. A., 73. Yoshii, E., 291. Yoshikawa, K., 474. Yoshikaya, H., 395. Yoshioka, I., 292. Youden, W. J., 440. Young, D. M., 135. Young, D. W., 297, 298, 513. Young, J. A., 88. Young, J. F., 160. Young, L. G., 475. Young, M. A., 134. Young, P. A., 107, 111. Young, R. A., 123, 126, 504. Young, R. J., 250, 306. Young, R. S., 406, 408. Young, W. G., 254.
INDEX
OF AUTHORS NAMES
555
Young, W. L., 170, 173. Youssef, A. A., 230. Yuan, E., 267. Yuan-Lang Chow, 296. Yudis, M. D., 267. Yukio Nakatsukasa, 448. Yung, N. c., 374. Yunusov, s. Yu., 347. Yura, Y., 332. Yurev, Yu. K., 279. Zaalishvili, Sh. D., 91, 95. Zabolotny, E. R., 143. Zachau, H. G., 382. Zacherl, M. K., 473. Za eetko, O., 200, 267. Z a g a n , A., 51. Zahradnik, R., 341. Zaitsev, P. M., 486. Zaikov, G. E., 39. Zakharkin, L. I., 135, 262, 265. Zalewski, K., 115. ZaIubas, R., 100. Zalusky, R., 407. Zambelli, A., 151.
Zamecnik, P. C., 379, 382, 418. Zamenhof, S., 367. Zamorzaev, A. M., 505. Zander, J. J., 429. Zandstra, P. J., 59. Zarinskii, V. A., 473. Zarnack, U., 345. ZBvada, J., 287. Zavgorodnii, V. S., 206. Zecher, W., 309, 335. Zeetenberg, A. P., 32. Zeeman, P. B., 119. Zefirova, A. K., 47. Zeibler, J., 299. Zeil, W., 192. Zeiss, H., 185. Zeldes, H., 47, 55. Zelle, A., 490. Zerner, B., 248. Zeronian, S. H., 368. Zewe, V., 424. Ziegler, G. R., 231. Zielinski, A. Z., 229. Ziffer, H., 289, 297. Zilborman, E. N., 279. Zillig, W., 376.
Zimmerman, S. B., 373. Zimmerman, U. P., 233. Zingaro, R. A., 146. Zinner, H., 365. Zinnes, H., 351. Zittel, H. E., 458, 461, 483. Zizlsberger, H., 177. Zhadanov, A. A., 141. Zhigunov, I. S., 97. Zhirova, V. V., 488. Zollinger, H., 232. Zorkii, P. M., 506. Zozulya, A. P., 465. Zubay, G., 382. Zueeh, E. A., 342. Zurn, L., 250. Zuman, P., 482. Zumoff, B., 431, 434, 453. Zu Reckendorf, W. M., 367. Zu Stolberg, U. G., 139. Zverev, G. M., 46. Zweifel, G., 255. Zwilling, E., 419. Zwolenik, J. J., 314. Zjrka, J., 452, 453, 467,468, 470, 484.
INDEX OF SUBJECTS
Abbreviations used in this Index: = biosynthesis biosyn. confign. = configuration conformn. = conformation dtmn. = determination identn. prepn. 8.s.r. n.m.r.
= identification = preparation
= election spin resonance = nuclear magnetic resonance
Acanthoidine, identn. of, 358. Alkaloids, steroid, 355. Acenaphthenequinone, ring enlargement terpene, 357. of, 317. Alkylation, control of site of, 264. Acetanilide, spectrum of, 193. Alkyl radicals, gas-phase oxidation of, 39. ( )- l0-Acetoxy-cis-hexadec-7-en-l-ol, Uenes, 272. synthesis of, 278. Alstoniline, synthesis of, 350. j-Acetylacraldehyde, identn. of, 376. Aluminium hydride, use as reducing Acetylenes, 268. agent, 256. Acetylene complexes, reaction of with -nitrogen compounds, prepn. of, 137. metals, 182. Aluminole, derivatives of, 334. Acetylene, t-butyl-, spectrum of, 190. Ambidentat 8 nucleophiles, 220. Acetylenic acids, a and B, prepn. of, 268. Americium, quadrivalent, stabilisation of, Acetylenic carbon, nucleophilic substi154. tution at, 231. Amidines, formation of, 279. 9-Acetyl-cis-decalin oxime, rearrangement 8-Aminolaevulicacid, conversion of, 388. of, 219. synthesase, identn. of, 386. N-Acetylglycine, structure of, 514. use i biosyn., 385. n N-Acetylmethionone, structure of, 206. 2 -Amino- 4-methylthiazole, synthesis of, Acids, fatty and related compounds, 274. 332. long-chain, synthesis of, 276. Ammonium ozonide, prepn. of, 147. in natural glycerides, 277. Anaferine, synthesis of, 344. unsaturated, biosyn. of, 275. Analytical apparatus, 438. Actinides, 153. Analytical balances, design of, 439. Actonospectacin, structure of, 341. Analytical results, accuracy of, 440. Acyclic compounds, structure of, 506. Analytical standards, 439. Acyclic imides, confign. of, 193. Androstenedione, biosyn of, 429. Adsorption, chemical, 14. Androst-4-ene-3,17-dione, isolation of, 429. migration in, 15. Angstroms, conversion of X-units into, physical, 14. 502. process of, 13. Angustifoline, partial synthesis of, 345. rate of and desorption, 16. Anions, aromatic, prepn. of, 313. AfEnin, properties of, 277. Annulenes, prepn. of, 316. Ajmaline, confign. of, 352. spectra of, 198. Akuammigine, identn. of, 350. Annuloline, synthesis of, 331, 358. Alanine, spectrum of, 206. Anthocyanins, identn. of, 340. Alcohols, dehydrogenation of, 259. 9,lO-Anthraquinol dibenzoate, planarity gas-phase oxidation of, 39. of, 508. Antimony Aldehydes, gas-phase oxidation of, 38. prepn. of, from nitriles, 262. Antimonic acid, polymeric forms of, reaction of, 244. 147. Aldosterone, tetrahydro-, structure of, 431. Homotropylium hexachloroantimonate, [7-SH]Aldosterone, prepn. of, 430. prepn. of, 313. Pentaphenylantimony, structure of, Alicylic compounds, 281. Aliphatic compounds, 190, 268. 508. Apiose, Bynthesis of, 360. Alkali borohydrides, uses of, 257. Aromatic compounds, 307. Alkanes, gas-phase oxidation of, 32. hydroxylation, mechanism of, 310. Alkaloids, Amaryllidaceae group, 348. ions and radicals, 312. biogenesis of, 344. indole, 349. reactivity, definition of, 307. isoquinoline, 347. Aromatic molecules, planarity of, 507. Aromatic substitution, electrophilic, 232. lupin, 345. lycopodium, 356. nucleophilic, 233. pyridine group, 344. radical, 235. pyrrolizidine , 345. Aromaticity, definition of, 307. Arsenic quinoline, 346. Bromodiphenylarsine, rotation of, 508. Solanum, 356. 556
I N D E X O ' 3UBJECTS B
557
Ar~enic, Chlorodiphenylarshe, rotation of, 508. Diarsine, prepn. of, 146. Dimethyl-3-methylthiopropyl arsine, reaction of, 172. Trisilylarsine, prepn. of, 146. Arylazopyrazolones, spectra of, 202. Arylsulphur trifluorides, synthesis of, 263. Aspidocarpine, structure of, 354. Aspidospermantine, structure of, 351. Aspidospermine, structure of, 354. Atractylon, autoxidation of, 292. Atrovenetin, structure of, 317. Azines, synthesis of, 338. Aziridine, combination of, 320. Azoles, synthesis of, 330. Azulene, structure of, 509. Azulenes, synthesis of, 315. 1,2,3-Triphenylazulene, formation of, 283. Bacimethrin, identn. of, 339, 374. Balances, analytical, design of, 439. Benzene derivatives, formation of, 307. Benzenoid polycylic compounds, formation of, 307. 3,4-Benzocoumarin, formation of, 234, 310. Benzofurazan oxide, spectrum of, 202. Bendonitriles, spectra of, 199. Benzophenone, spectrum of, 199. 1,2,3-Benzothiadiazole, reactions of, 333. Benzyne, formation of, new methods, 31 1. intermediate, chemistry of, 311. Beryllium, reaction of, 130. Betanidin, reactions of, 327. Beyerol, structure of, 298. Biaryls, optically active, spectra of, 199. Bicyclo[2,2,0]hexadiene, structure of, 307. Biogenesis of alkaloids, 342. Biosynthesis of chlorophyll, 397. cholesterol, 427. hzem, 394. porphyrins, 385. protoporphyrin IX, 394. steroids, 427. Biphenyl-2-carboxylic acid, nitration of, 310. Bis-m-bromobenzoylmethane, structure of, 508. Bismuth monochloride, structure of, 147. Blood group A, isolation of new sugar in, 368. Bond distances and angles, 189. Boron, prepn. of, 131. reactions of, with oxygen, 135. Boron hydrides, formula of, 131. subhalides, chemistry of, 136. Amine borines, synthesis of, 256. " Borazorene," synthesis of, 342. Borazynes, prepn. of, 134. Diborane, reactions of, 132. Nitronium tetrafluoroborate, as nitrating agent, 267. Boron-nitrogen ring compounds, 133.
o-Bromobenzoic acid, planarity of, 507. m-Bromonitrobenzene, charge transfer bonds of, 507. Butadiene, dtmn. of, 273. spectrum of, 190. Butadieneiron carbonyls, prepn. of, 181. Butene, cis- and tram-, formation of, 322. Byssochlamic acid, structure of, 286. Cadmium, 167. Cafestol, confign. of, 297. Calarene, constitution of, 292. Calycanine, synthesis of, 350. Calycanthidine, structure of, 349. Camphor. Norcamphor, photolysis of, 287. Capsorubin, stereochemistry of, 273. Carbazole, reduction of 2-nitrosobiphenyl to, 258. Carbene, dichloro-, formation of, 243. difluom-, formation of, 241. Carbenes, formation of, 280. generation of, 240. Carbohydrates , 359. amino-derivatives of, 366. cyclic derivatives of, 363. degradations of, 363. deoxy-derivatives of, 365. esters of, 364. ethers of, 364. oxidation of, 361. Carbon-13 resonance study of, 71. Carbon monoxide, gas-phase oxidation of, 26. Carbonium ions, transient, 207. Carbonyl, butadieneiron, prepn. of, 181. compounds, Friedel-Crafts reaction, 262. cyclopentadiene-metal, prepn. of, 183. cyclopentadienyl cations, prepn. of, 183. Carbonyls, molecular-orbital energy-level scheme for, 175. Raman spectra of, 175. Carboxylic acids, prepn. of, 262. reactions of, 246. p-Carotene, 274. Carotenoids, 273. Cascarillin, structure of, 296. Catabolism of CIS,433. Ci9, 432. CZ1,430. Cations, aromatic, reactions of, 312. Ceanothenic acid, structure of, 300. Cedrelone, stereochemistry of, 301. Celastrol, structure of, 302. Cellulose, crystal structure of, 368. ethers, relative reactivities of, 369. Cembrene, structure of, 299. Cerium(m) chloride alcoholates, composition of, 152. Chalcose, synthesis of, 365. Charge-transfer complexes, study of, 60. Chelates, octahedral, photoracemisation of, 171. Chimonanthine, reduction of, 349. structure of, 511. Chloranil, analysis of, 508.
558
I N D E X OF SUBJECTS
Chloranil-hexamethylbenzene complex, planarity of, 512. Chlorine-35 resonance, study of, 70. 6-Chlorobenzofuroxan, crystal structure of, 332. 2 -Chloro- 5-nitrobenzoic acid, planarity of, 507. Chloroform, spectrum of, 191. Chlorophyll, biosyn. of, 397. Cholestanones, phenyl-, transition of, 197. Cholesterol, biosyn of, 427. (+) -tram-Chrysanthemic acid, synthesis of, 281. Chromatography, column, 444. gas, 448. paper, 445. thin-layer, 446. for dtmn. of radioactive species, 493. Chromium, 158. diperoxide, magnetic moment of, 160. Cladinose, identn. of, 366. Cleavamine, prepn. of, 355. Cobalt, 1El. acetylacetonates, spectra of, 169. Hydroxoamminecobalt(II1) complexes, isomerisation of, 174. Nitroso (dimethyldithio-carbamato)cobalt, structure of, 178. Tetramethylammonium tetranitratocobaltate(II), prepn. of, 192. Cobamide coenzymes, structure of, 400. Cobamides, biosyn. of, 411. Coenzyme A, synthesis of, 376. Coenzyme, cobamide, isolation of, 400. dehydrogenases, 417. modifications, 416. NAD+, 413. NADH, 414. NADH-X, 414. NADPH, 416. Methylmalonyl-coenzyme A isomerisation, 403. Cogeijerene, optical inactivity of, 290. Colensenone, correlation of, 295. Communic acid, structure of, 295. Complexes, donor-acceptor, 81. inorganic, acetylene, 182. mechanisms of reaction, 173. o l e h , 179. with aromatic systems, 174. tetrahedral, formation from bicyclic bases, 172. hydroxoamminecobalt(II1) isomerisat ion of, 174. Condylocarpine structure of, 352. (&)-Conessine, synthesis of, 355. Copper, 166. Coproporphyrinogen 111, formationof, 393. Cortisol, catabolism of, 431. synthesis of, 427. 5cr-Cort01, isolation of, 432. 5a-Cortolone, isolation o , 432. f Coulostatic analysis, 481. Coumarin, photoisomerisation o , 340. f Coumarins, spectra of, 203. Cryostat, construction of, 501.
Crystallography, experimental techniques i , 501. n symmetry and geometrical, 505. Crystals, thermal effects in, 604. isomorphous, replaceable atoms in, 502. perfect, temperature factors in, 504. Cubane, octaphenyl-, prepn. of, 269. structure of, 283. Cucurbitacins, structure of, 300. Curves, rotary dispersion, of inorganic complexes, 169. Cyanocobalamin, conversion into the coenzyme, 412. Cyanogen, synthesis of, 144. Cyanomaclurin, structure of, 329. Cyclic dibasic acid anhydrides, spectra of,
191.
Cyclic molecules, planarity of, 507. Cyclodkanones, enolisation of, 245. trans-4-Chlorocyclohexanol, stability of,
196.
Cyclodecane, conformn. of, 287. Cyclohexane, conversion of, 196. Cyclo-octatetraenein carbonyls, Mossbauer spectra of, 168. cis-Cyclo-octene, formation of, 262. trans-Cyclo-octene, formation of, 262. Cyclopentadiene, dimerisation of, 283. -metal carbonyls, prepn. of, 183. 1,2-Cyclopenbanophenanthrene,planhrity of, 509. Cyclopentene, spectrum of, 196. Cylindrocarpidine, structure of, 353. Cylindrocarpine, structure of, 353. Cytochromes, formation of, 396. Dalbergiones, isolation of, 318. Dehydroepiandrosterone, detection of,
429.
isolation of, 432. occurrence of, 429. Dehydrogenases, activity of, 417. glutamic, 425. horse liver-alcohol, 420. lactic acid, 423. malic acid, 425. NADH, folded conformn. of, 418. NADH, stereochemistry of, 418. yeast-alcohol, 423. Dehydrogenation of alcohols, 259. Denudatine, structure of, 358. Desoamine, identn. of, 366. Deuteroformyl radicals, spectrum of, 205. Dewar-benzene derivative, prepn. of, 285. Diagrams, phase, 97. Di-t-alkyl nitroxides, prepn. of, 279. Diatomic molecules, spectroscopy of, 99. Diazirine, photolysis of, 241. prepn. of, 321. structure of, 201. Ethylmethyldiazirhe, rearrangement of,
241.
Diazoaminobenzene, pp-dibromonitroderivative of, 507. Diazoisofenchone, conversion of, 243. Diazonium compounds, prepn. of, 266.
559
Dibenzocyclo-octadiene, dimerisation of, 282. 1-Dichlosomethylpiperidine,formation of, 335. Di-(p-chlorophenyl)amine, valency angle of, 508. Diels-Alder reaction, mechanisms of, 227. Diethyl oxalate, spectrum of, 191. Differential thermal analysis, 499. 1 ,l-Difluoropropene,synthesis of, 255. Digicitrin, isolation of, 341. 9,10-Dihydro-9-hydroxy-9-phosphaphenanthrene 9-oxide, structure of, 511. AT- Dimet hylethylenediamine hydro chloride, 194. 4,12-Dimethyl(2,2)metacyclophane, molecular strain in, 509. ~ R S - 3,4-Dim& yl hexa-1,5-diem, re O h arrangement of, 238. Dimethyl sulphoxide, solvates with transition-metal halides, 171. Dinitrogen tetrafluoride, reactions of, 144. y8-Dioxovaleric acid, prepn. of, 388. Diphenyl ether, spectrum of, 199. 2,2-Diphenylindoxyl,prepn. of, 325. 3,3-Diphenyloxindole, prepn. of, 325. Disaccharides, Konigs-Knorr synthesis of, 367. Diterpenes, confign. of, 294. Dithiet, prepn. of, 323. 1,2-Dithiolinium cation, identn. of, 333. ( f)-Dolichone, isolation of, 329. Donor-acceptor complexes, 81. Drying, for analysis, 439. Durosemiquinone, spectrum of, 206.
Energy, potential, curves, 113, 115. vibrational, 114. Enzymes, different forms of, 419. Enzyme studies, in succhte-glycine cycle, 388. Epibaptifoline, synthesis of, 345. ( -)-Epicyclocolorenone,synthesis o , 294. f. 2,3-Epoxy-2,3-diphenylindan1-one, 1somerism of, 307. reactions of, 340. Erbium oxalates, stabilisation of, 152. Erythritol, 1,3-O-benzylidene-, n.m.r. of diacetate, 363. conformn. of, 1,3 : 2,4-di-O-benzylidene-, 363. Escherichia w li., methionine synthesis h , 406. Esters, carboxylic, polarisability of, 191. gas-phase oxidation of, 39. phosphorus, spectra of, 191. Ethane, spectrum of, 190. Ethane-1,2-dithiol, spectrum of, 195. Evaporated metal films, uses of, 13. Excess functions, measurement of, 94. Fabianine, composition of, 347. Falcatine, structure of, 348. Flash-filament experiments, 12. Flavasperone, structure of, 341. Flavocarpine, identn. of, 350. Flavopereirine, identn. of, 350. Fluorine-19 resonances, study of, 68. Fluorotriphenylcyclobutadiene, dimer of, 509. Folicanthine, structure of, 349. Formaldehyde, slow oxidation of, 26. Formaldoxime, structure of, 194. Formamide, spectra of, 193. Formyl radicals, spectrum of, 205. Free radicals, 48. Furans, structure of, 327. Furan-2-carboxylicacid, structure of, 509. Furanodecalins, isolation of, 292. Fusidic acid, provisional structure of, 300. Gallium halides, reaction of, 138. Gas-phase oxidation, 18. Gedunin, stereochemistry of, 300. Geigerin acetate, synthesis of, 293. Geissolosimine, structure of, 355. Genetic code, review of, 380. Germanium, prepn. of, 141. Germyl cyanide, spectrum of, 207. 1,l-Di-iodogermiren,formation of, 322. Gibberellic acid, stereochemistry of, 298. Glass, analysis of, 438. Glassware, resistance to chemical attack, 439. Glauconic acid, structure of, 286. W D - G ~ U Cmonohydrate, structure of, OS~ 513. D-G~UCOSB, oxidation of, 361. (+)-Glutinic acid, structure of, 272. Glycine, spectrum of, 194. N-Carbamoylglycine, spectrum of, 206. Phenylglycine, tramamination of, 245.
Echinulin, synthesis of, 327. Echitamidine, spectra of, 351. Electrodes, mercury, uses of, 438. Electrodeposition, 481. Electron distribution, accurate dtmn. of, 503. dtmn., in N-acetylglycine, 504. in diamond, 504. in lithium hydride, 504. in monofluoroacetamide, 504. in cc-quartz, 504. Electron spin resonance (e.s.r.), 45. transfer reactions of, 59. trapped, 62. Electrophoresis, improvements in apparatus, 447. &Elemme, optical inactivity of, 290. Elimination-addition mechanism, 215. Ellipticine, synthesis of, 349. (-f )-Emetine, synthesis of, 347. End point dtmn., amperometric, 459. chronopotentiometric, 472. conductometric, 457. coulometric, 462. differential electrolytic potentiometric, 471. high frequency potentiometric, 472. potentiometric, 466. Energy, form of pair-interaction, 88. molecular, levels, 113.
560
INDEX OF SUBJECTS
Glycols, dehydration of, 408. Glycosides, 362. Gold, 166. dtmn. of, 437. Goniometer, three-circle X-ray, design of, 501. Gravimetric analysis, 449. Grignard reagents, formation in hydrocarbon media, 265. Griseofulvin, antibiotic, synthesis of, 318. racemic, formation of, 328. Hsem, biosyn. of, 394. enzymes, isolation of, 396. Hafnium, 154. Halides, alkyl, rotational isomerism of, 192. transition-metal, reactions with dimethyl sulphoxide, 171. Haplohyllidine, reduction of, 346. Hectors bases, identn. of, 333. Helminthosporal, constitution of, 294. Heptalenium ion, spectrum of, 315. Heterocyclic compounds, 319. Heteroenzymes, structure of, 419. Hetisine, constitution of, 357. NN-Hexamethylenebisproprionamide, structure of, 506. Hexaphenylbenzene, formation of, 308. prepn. of, 269. Hexaphenylpentalene, synthesis of, 315. trans-Hexa-1,3,5-triene, synthesis of, 273. Holamine, synthesis of, 355. Holsphyllamine, synthesis of, 355. Homocyclic compounds, spectrum of, 195. Hinesol, structure of, 292. Hinokiol, structure of, 296. Hinokione, structure of, 296. Humulene, pure, isolation of, 290. Hunterburnine, structure of, 351. 1,3-Hydride shifts, 216. Hydroboronation, 2 55. Hydrocarbons, higher, gas-phase oxidation of, 34. spectra of, 190. Hydrogen chloride, use as a solvent, 151. Hydrogenation, catalytic, 254. 3-Hydroxyflavylium, formation of cation of, 310. Hydroxymethylcytosine nucleoside, structure of, 373. trans-Hydroxy-L-proline, spectra of, 202. 3-Indazolone, formation of, 331. Indicine, prepn. of, 345. Indium, halides, prepn. of, 138. Indoles, synthesis of, 324. reactions of, 325. Indolizines, structure of, 327. Indolmycin, structure of, 326. Inorganic complexes, mechanisms of reactions of, 173. Intensities, absolute, of electronic transitions, 109 relative, measurement of, 111.
Iodine dioxide, structure of, 151. monobromide, spectrum of, 103. monochloride, spectrum of, 103. Periodate, use in oxidation of sugars, 361. Periodic acid, spectrum of, 151. Ion-exchange, metal-amine complexes in, 170. uses of, 447. Ion-pair return, 213. Ion-pairing, study of, 56. Ionization gauge, X-ray limit of, 8. Iridium, 161. Iridomyrmecin, conformn. of, 289. Iron, 161. Butadieneiron carbonyls, prepn. of, 181. Cyclo-octatetraeneiron carbonyls, Mossbauer spectra of, 168. Ferrous fluorosilicate hexahydrate, diffraction study of, 505. Ismine, prepn. of, 348. Isoajmaline, confign. of, 352. Isoartocarpin, structure of, 341. Isobisabolene, structure of, 290. Isoenzymes, definition of, 419. Isoiridomyrmecin, conformn. of, 289. Isojervine, structure of, 356. Isopilocereine, structure of, 348. Isopimaric acid, structure of, 296. Isoquinoline, structure of, 337. ( f)-Isoretronecanol, synthesis of, 346. Isoselenazole, formation of, 332. Isothiazole, synthesis of, 332. Isotopic tracers, use in radiochemistry, 495. Isoxazoles, halogenation of, 331. Ivalin, constitution of, 292. Jasmine, composition of, oil of, 278. Ketones, reactions of, 244. Konigs-Knorr synthesis of disaccharides, 367. Kurchamine, structure of, 355. Kurchimine, structure of, 355. Lathyrine, spectrum of, 194. Lattice theory of mixtures, 92. Lead Trimethylplumbane, structure of, 143. Leonurine, structure of, 358. Leurosine, structure of, 355. Lsvopimaric acid, conformn. of, 297. Ligand, 2-2-hydroxyethylpyridine 172. as, Ligand exchange, use in chromatography, 171. (i)( t +)-Linalool, confign. of, 289. Lithium aluminium hydride, use of, 256. Ethyl-lithium, spectrum of, 206. structure of, 130. t-Butyl-lithium, structure of, 130. Lumicholesterone, photolysis of, 304. (-f)-L-unacrine, synthesis of, 346. Lutetium oxalate, stabilisation of, 152. Lysine fermentation, 408. 22-Lysine monohydrochloride dihydrate, StNCtUre Of, 573.
561
8-Lyxose, conformn. of, 359. Magnesium hydride, prepn. of, 130. viologen, formation of, 336. Magnetic resonance, of carbon- 13, 7 1. of chlorine-35, 70. of fluorine-19, 68. of oxygen-17, 67. of solute nuclei, 68. of solvent nuclei, 64. Maleimide, synthesis of, 324. Manganese, 160. Manganese(1v) fluoride, prepn. of, 160. Tricarbonyl- a-pyrrolylmanganese, formation of, 183. Mass spectrometry, 496. Mercury, 167. electrodes, uses of, 438. Mercuric acetate, as oxidising agent for carbohydrates, 361. Methane, slow oxidation of, 26, 28. Methionine, synthesis of, 406. Methyl formate, spectrum of, 191. Methyl metadithiophosphonate, symmetry of, 511. 8-Methylaspartate isomerisation, 403. 5-Methylbenzofuroxan, nitration of, 332. trans-5-Methylcyclohex-2-enol, isomerisation of, 214. ( )-S-Methyl-L-cysteinesulphoxides, confign. of, 514. Methylcyclohexane, spectrum of, 196. 1,l-Methylenedi- (4-hydroxyiminopyridinium) halides, isomerisation of, 194. 3,4-Methylenehexa-l,5-diene, formation of, 273. ( - ) -N-Methylgelsemicine hydriodide, structure of, 511. 2-Methylpent-2-ena1, enzyme liberation of, 278. 3-Methyl-5-phenylpenta - 2,4- dienoic acid, spectrum of, 191. N-Methylthioacetamide, spectrum of, 193. 2-Methylthiobenzothiazole, structure of, 511. N-Methylthioformamide, spectrum of, 193. 4-Methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2]octane, 172. Microscopy, field-emission, 10. Mixtures, lattice theory of, 92. Molecular energy levels, 113. theory, of solutions, 84. Molecular weight dtmn., differential method, 440. Molecule, aromatic, planarity of, 507. cyclic, planarity of, 507. Molybdenum, 158. Monofluoroacetamide, planarity of, 506. Monofluorocitric acid, synthesis of, 263. Monosaccharides, 359. Monoterpenes, 289. Morphine, structure of, 348. Mossambine, spectrum of, 351. Mossbauer spectra, of organic compounds, 168. of cyclo-octatetraeneiron carbonyls, 168.
Mycaminose, identn. of, 366. Mycarose, synthesis of, 365. Mycinose, synthesis of, 365. Natural products, review of, 271. Neighbouring-group participation, 217. ( f)-Neotenone, isolation of, 329. Neptunium, spectrum of, 154. Nickel, 164. Bis(triphenylphosphine)ethylenenickel, formation of, 179. Nicotinamide apoenzymes, 413. coenzymes, 413. dinucleotides, structure of, 417. Niobium, 156. dtmn. of, 437. Nitration, of aromatic compounds, by Friedel-Crafts principle, 2 67. Nitrene, isoelectronic, generation of, 241. Nitrenes, use in synthesis, 243. Nitroalkanes, crystalline derivatives of, 279. l-Nitroazetidine, prepn. of, 322. 2-Nitrobiphenyl-2-carboxylic acid, rearrangement of, 234. 5-Nitrobornene, confign. of, 200. Nitrogen, active, reactions of, 143. o-Nitrophenol hemihydrate, potassium salt of, structure, 507. 2-Nitrosobiphenyl, reduction of, 258. Nitrosyls, gas-phase reaction with halides, 178. molecular-orbital energy-level scheme for, 175. Noviose, biosyn. of, 360. Nuclear magnetjc resonance in electrolyte solutions, 63. Nucleation in precipitation, role of, 451. Nucleic acid bases, dimerisation of, 371. effect of radiation on, 371. Nucleic acids, 371. genetic code, 380. protein synthesis of, 379. Nucleophilic substitution a t saturated carbon, 207. Nucleosides, synthesis of, 374. Nucleotides, physical chemistry of, 378. synthesis of, 376, Nupharidine, synthesis of, 344. Obscurine, a- and j3-,structure of, 357. (+)-Occidol, confign. of, 292. Octaphenylcubane, prepn. of, 269. structure of, 283. (Estrone, conversion into astriol, 433. Olefin complexes, of transition metals, 179. Olefin-forming eliminations, 222. Olefhic carbon, nucleophilic substitution at, 231. compounds, 272. Olefins, additions to, 224. formation of, 260. gas-phase oxidation of, 35. Oleuropeic acid, synthesis of, 289.
562
Organic chemistry, 187. material, oxidation of, 438. structure, 189. Organometallic compounds, 265. Osmium, 161. Otobain, structure of, 318. Oxidation, gas-phase, 18. hydrogen-oxygen reaction, 22. organic, 26, 28, 32, 34, 35, 37, 38, 39. shock tubes and flames, 19. liquid-phase, 258. Oxirans, formation of, 321. Oxygen-17 resonances, study of, 67. Oxygen atoms, reactions of, with organic compounds, 43. Paint, analysis of, modern methods, 437. Pair interaction energy, form of, 88. Palladium, 164. Tetraphenylcyclobutadienepalladium(I1) chloride, prepn. of, 182. Paracyclophanes, prepn. of, 317. Parameters, lattice, accurate measurement of, 502. Parthenin, correlation of, 294. Patchouli alcohol, synthesis of, 293. spectrum of, 191. trans-Pent- 3-en-2-0~~0, Perchromate ion, basic formula of, 160. Peroxy-compounds, dipole moments of, 191. Phase diagrams, 97. O-Phenylhydroxylamine,synthesis of, 308. 4-phenyl-1,2,4-triazoline-3,5-&one, prepn. of, 331. Phosphorus, compounds of, 144. Fluorophosphanes, 146. Phosphanthrene, prepn. of, 342. Phosphazenes, 145. Phosphonitrilic bromides, prepn. of, 145. chlorides, prepn. of, 145. dimethylamide tetramer, 61I. Phosphoranes, olefin formation from, 260. Potassium 00-dimethyl phosphorodithioate, structure of, 507. Silylphosphines,synthesis of, 140. Triferrocenylphosphine, prepn. of, 146. Picramide, spectrum of, 199. Piloceredine, structure of, 348. Piperazine-1,4-dibutyricacid, structure of, 511. Pisatin, partial synthesis of, 329. spectrum of, 203. Platinum, 164. Dioxygenyl hexafluoroplatinate, identn. of, 165. Pleuromutilin, structure of, 299. Plutonium(rv) complex halides, prspn. of, 153. fluoride, identn. of, 153. Podototarin, synthesis of, 297. Polarography, 482. alternating current, 488. cathode ray, 488.
i mfor Polaroid f l , recording neutron diffraction, 502. Polyacetylenic compounds, naturally occurring, 271. Polygodial, isolation of, 292. Polymerisation, degree of, of metal oxide alkoxides, 170. Polynucleotides, synthesis of, 376. Polyriboguanylic acid, synthesis of, 378. Porphobilinogen, use of in biosyn., 385. formation of, 388. conversion of, 389. Porphyrins, biosyn. of, 385. reduction of, 325. Coproporphyrin, structure of, 385. Phyriaporphyrin 111, isolation of, 394. Protoporphyrin, conversion of, 385. Protoporphyrin IX, biosyn. of, 394. Potent iometry, 466. differential electrolytic, 471. high frequency, 472. Praseodymium fluoride, prepn. of, 153. Prephenic acid, corfign. of, 285. Pristimerin, structure of, 302. Properties, equilibrium, of liquid mixtures, 73. Propyl fluoride, spectrum of, 192. Prostglandin F2-1, confign. of, 276. F,, structure of, 284. Protein synthesis, review of, 379. Protohaemin IX, inhibitor in biosyn., 387. Pseudouridine, structure of, 375. Pseudovitamin B,, coenzymes, structure of, 401. Pteridine, hydration of, 339. 4H-Pyran, formation of, 339. Pyrazoline hydrochloride, planarity of, 510. Pyrazolines, synthesis of, 330. Pyridine, 2-2-hydroxyethyl-, as ligand, 172. Pyridine hydrochloride, bond linkage in, 510. Pyridines spectra, of, 334. Pyrido[3,2-a]azulene,synthesis of, 316. 2-Pyridone7l-methyl-, structure of, 337. Pyridoxine, synthesis of, 337. 1-2-Pyridyl- - 2-pyridylmethylene2 hydrazine, complexes of, 172. 2,3-Pyridyne, formation of, 235. 3,4-Pyridyne, formation of, 235. reaction as intermediate, 335. Pyrimidines, synthesis of, 338. (+)-Pyrocin, use in synthesis, 281. Pyrroles, synthesis of, 323. Pyrrolines, spectra of, 201. Pyruvate-C 0, exchange, 410.
Qualitative analysis, inorganic, 440. organic, 441, 473. Quaternary amino-groups, in enzyme action, 423. Quinaldine, reduction of, 338. Quinoline, structure of, 337. Quinolizidine, spectrum of, 203. Quinolizines, formation of, 338.
INDEX O F SUBJECTS
563
Radicals, alkyl, gas-phase oxidation of, 39. aromatic, prepn. of, 314. free, e.s.1. of, 48. aromatic, in solution, 8.s.r. of, 50. carbon 7 ~ - , 8.s.r. of, 52. u-, 8.s.r. of, 55. Radioc hemistry, 489. activation methods in, 490. Rare earths, 152. Reaction mechanisms, 207. Rearrangements, aromatic, 236. Claisen, 237. benzidine 238. semidine, 238. Regular solutions, 73. excess free energies of, 76. separation into two liquid phases, 80. solubilities of, 78. solubility equations of, 76. volume changes on mixing, 8 1. Retamine, structure of, 345. (-J-)-Retronecine, synthesis of, 345. Rhenium, 160. Rhodium, 161. Rhodium(Ir1) acetylacetonates, spectra of, 169. Dinitrosylrhodium chloride, reaction of, 178. Ribonucleic acid, reactions of, 374. Royleanone, diterpene quinone, isolation of, 296. Ruthenium, 161. Saccharides, acetylation of, 364. di-, 367. methylation of, 364. oligo-, 367. POly-, 368. Samandaridine, structure of, 356. Samples, analytical dissolution of, 438. Sarpagine, structure of, 352. Saturated carbon, electrophilic substitution at, 230. nucleophilic substitution at, 207. Saxifolin, degradation of, 339. Securinine, structure of, 358. Selenium compounds, prepn. of, 150. Selenophen-2-carboxylic acid, structure of, 509. Semicarbazones, formation of, by acid catalysis, 245. Sempervirine, synthesis of, 350. Sesquiterpenes, 290. Shellolic acid, constitution of, 294. Silicon, multiple bonding of, 138. halides, reaction of, 140. monoxide, prepn. of, 140. 1 , l -Dimethyl-2,3-diphenylsiliren, prepn. of, 322. Disilane, prepn. of, 139. synthesis of, derivatives, 139. Potassium silacyclopentadienide, spectrum of, 333. Silane, conversion into higher silanes, 139. Silazides, prepn. of, 139.
Silicones, as heat exchangers for analysis, 439 Silver, 166. Skytanthine, prepn. of, 344. Sodium bicarbonate, C-0 distances, study of, 506. Sodium metaperiodate, use as oxidising agent, 260. Solanum group, synthesis of, 356. Solasodine, synthesis of, 306. Solutions, molecular theory of, 84. regular, 73. Solvent extraction, for dtmn. of radioisotopes, 492. in analysis, 443. (- )-Sophocarpine, prepn. and structure, 345. Sophoramine, prepn. of, 345. Spectra of dkali-metal compounds, 121. of carbonmonoxide andlead telluride,l23 of chlorine and iodine, 127. of doubly charged positive ions, 120. effect of fine structure on, 118. effect of isotopes on, 119. effect of predissociation on, 117. of halides, 129. of hydrides, 127. of hydrogen halides, 121. of magnetic rotation, 103. of mercury and rare-gas compounds, 120. of new inter-metallic compounds, 119. of nitric oxide, 124. of nitrogen, 122. of oxides, 128. perturbations of, 116. of phosphorus, monofluoro-, 127. of sulphur: disulphur, 126. Spectroscopic analysis, 475. Spectroscopy, absorption, 478. atomic absorption, 479. of diatomic molecules, 99. emission, 475. flame, 476. fluorimetry, 476. infrared, 480. nuclear magnetic, 480. techniques of, 100. ultraviolet and visible, 478. uses of, for new species, 119. X-ray, methods, 477. Stachenone, structure of, 297. Standards, pH for analysis, 439. analytical, 439. Starch and glycogen, 369. Stemmadenine, structure of, 352. Sterigmatocystin, structure of, 329. Steroid hormones, metabolism of, 426. Steroids, 303. spectra of, 200. C18, 429. C,,, 428. CZ1,427. Structure, analysis of, by computer, 502. dtmn. of, by optical analogue methods, 503. in organic molecules, 504.
664
I N D E X OF S U B J E C T S
Succinate-glycine cycle, reactions in, 388. enzyme studies in, 388. Succinonitrile, conlign. of, 195. Succinyl-Co A, as intermediate in porphyrin biosyn., 385. Sugars, acetylation of, 364. acetylated amino-, de-O-acetylation of, 366. amino-, reactions of, 366. deoxy-, synthesis of, 365. reducing, methylation of, 364. Sulphaniloylguanidine, structure of, 195. Sulphides, oxidation to sulphoxides, 260. Sulphonium ylides, use as tmnsfer agents, 265. Sulphur, compounds of, 148. derivatives of, 279. halides synthesis, of, 149. Disulphur monoxide, prepn. of, 149. Tetrasulphur tetranitride, prepn. of, 148. Trisul hur dinitrogen tetroxide, prepn. of, f48. Tabersonine, structure of, 353. Tantalum, 156. dtmn. of, 437. Tartaric acid, spectrum of, 205. Taxines, structure of, 358. Technetium, 160. Tellurium complexes, 150. Terpenes, spectra of, 200. Testosterone, biosyn. of, 429. synthesis of, 428. secretion of, 433. Tetrachloroquinol, planarity of, 508. Tetracyclines, biosyn. of, 319. synthesis of, 288. Tetramethylene sulphite, cyclic, spectrum of, 204. Tetramin, spectrum of, 320. Thallium, complexes of, 138. Theorell-Chance, mechanism for enzyme reaction, 421. Thermal effects in crystals, 504. methods of analysis, 499. parameters in lithium hydride, 504. parameters in a-quartz, 504. scatter, correction for, 504. Thermogravimetric analysis, 499. Themopsine, synthesis of, 345. Thia(Iv)benzenes, prepn. of, 341. Thialen, formation of, 341. Thiamine hydrochloride, planarity of, 514. Thietans, formation of, 321. Thiete 1,l-dioxide, reactions of, 323. Thiirans, formation of, 321. Thiophens, structure of, 329. Thiophen-2-carboxylic acid, structure of, 509. 4H-Thiopyran, prepn. of, 339. Thiourea dioxide, planarity of, 507. Thorium chloride, reactions of, 153. Thujone, conlign. of, 290. Thunbergene, see Cembrene, 299.
Tin, detection of, 142. Titanium, 154. complexes, prepn. of, 155. Hexafluorotitanates, prepn. of, 154. Titrations, chelatometric, 454. functional group dtmn., 457. halogen, 453. non-aqueous, 457. redox, 453. spectrophotometric, 456. Titrimetric analysis, 452. 6-Toluene-p-sulphonyloxyisophorone, rearrangement of, 215. Totarol, structure of, 296. Totarolone, structure of, 296. Toxoflavine, synthesis of, 339. quadrupole and magnetic dipole, 108. Transition elements, 152. molecular hydrides of, 185. organometallic compounds, 184. perfluoroalkyl derivatives, 184. Transition-metals, 0.s.r. spectra of, 46. Transitions, electric dipole, 105. Triazolopyrimidine, structure of, 510. Triethylscarpane, formation of, 507. Trimet hylher queinone B, structure of, 318. 1,2,3-Triphenylbenzopentalene, prepn. of, 315. Triphenylethylene, formation of, 312. 1,2,5-Triphenylphosphole, reactions of, 333. 1,2,3-Triphenylpropene, formation of, 312. Triterpenes, constitution of, 300. 1,3,5-Trithian, spectrum of, 204. structure of, 341. a-Trithioacetaldehyde, spectrum of, 204. a-Trithiobenzaldehyde, spectrum of, 204. Tropones, synthesis of, 314. Tropovinylene spiroborates, synthesis of, 314. Tropyl derivatives, formation of, 314. Tropylium salts, formation of, 313. Tubercle bacillus, study of acids of, 275. Tuberostemmonine, dehydrogenation of, 349. Tungsten, 158. Tungsten-(In) and -(Iv) bromides, 158 Twistane, synthesis of, 288. Ultra-high vacua, 7. experimental methods, 8. theoretical approach to, 9. getter-ion pumps for, 9. Uranium chlorides, prepn. of, 154 monocarbide, hydrolysis of, 153. quality and safety control of, 437. Ammonium diuranate, composition of, 153. Uranium (IV) oxide, reactions of, 153. Uroporphyrinogen, structure of, 385. Uroporphyrinogen decarboxylase, isolation of, 393.
INDEX O F SUBJECTS
566
Uroporphyrinogen I synthetase, isolation of, 391. Uroporphyrinogen 111, formation of, 389. Uroporphyrinogen I11 cosynthetase, isolation of, 391. Valeranone, structure of, 292. Vanadium, 156. tetrabromide, prepn. of, 156. Vanadium(m), oxidation by iron(m), 173. Vector, superposition diagram, symmetry of, 503. Veralkamine, structure of, 356. Vermiculite, analytical uses of, 439. Vincadifformine, structure of, 353. Vincalencoblastine, structure of, 355. Vincamine, structure of, 354. Vindoline, structure of, 353. Virial coefficient, second, 88. Vitamin B,, planarity of, 514. Vitamin BI2,400. Vulgarin, constitution of, 292.
Water, dtmn. of, 439. Willardiine, identn. of, 339. Xenon difluoride, prepn. of, 130. hexfluoroplatinate, prepn. of, 130. tetrafluoride, prepn. of, 130. Xylindein, composition of, 318. spectrum of, 341. Yeast alcohol dehydrogenase, r61e of zinc in, 423. Yohimbine, synthesis of, 350. Zierone, constitution of, 294. Zinc, r61e in enzyme action, 422. Di-L-histidinozinc(11)dihydrate, structure of, 514. Zirconium, 154. iodide, reduction of, 154. Zonemelting, low-temperature application of, 171.
P R I N C I P A L R E F E R E N C E S USED I N CHEMICAL SOCIETY PUBLICATIONS A LIST of the principal references used in this and other Chemical Society publications was given on page 557 of the 1960 issue of Annual Reports. A similar list can also be found in each January issue of Current Chemical Pupers, in the Societys Handbook for Chemical Society Authors, and in the brochure Presentation of Papers.
Printed in Great Britain by Butler ik Tamer Ltd, Frome and London
C0
The Chemistry of Nucleic Acids

By D. 0.Jordon.
I960 100 illustrations
358 pages
605.
Seventh International Conference on Coordination Chemistry

International Union o Pure and Applied Chemistry f
I963 44 illustrations 123 pages
305.
Crystallization
By].
1961
w. Mullin, BSc., Ph.D.,

I22 illustrations
F.R.I.C.,
M.I.Chem.E.
268 pages
605.
Gas Chromatography Edited by M. van Swaay.

I962 I72 illustrations
I962
41 I pages
1005.
Naturally Occurring Oxygen Ring Compounds By F. M. Dean, B.Sc., Ph.D.

1205.
Practical Mathematics for Chemists

By F. H. C. Kelley, D.Sc.(Tas.), M.Sc.(Melb.), A.Melb.T.C.,
F.R.A.C.I., A.Aust.1.M.M.
I963
9 illustrations
156 pages
Progress in Medicinal Chemistry 3 Edited by G P. Ellis, B.Sc., Ph.D., F.R.I.C., . and G B. West, B.Pharm., D.Sc., Ph.D. .
205.
Progress in Organic Chemistry Progress in Stereochemistry

1962 76 illustrations
Edited b y j . W. Cook, D.Sc., F.R.S., and W. Carruthers, D.Sc. 1961 8 illustrations 180 pages 505. Edited by P. B. D. de /a Mare, Ph.D., D.Sc., F.R.I.C., w. K/yne, M.A., D.Sc., Ph.D.
368 pages
-5
805.
-3
and
755.
XVlllth International Congress of Pure and

Applied Chemistry
International Union o Pure and Applied Chemistry f
I962 I46 illustrations 758 pages
755.
BUTTERWORTHS 4 & 5 Bell Yard, London, W.C.2

O
G 0
Chemical Analysis: The Working Tools

Volumes I, I . , and III
Edited by c . R. N. STROUTS,
R . T. PARRY-JONES H . N . W I L S O N and
Assited by
J. H. GILFILLAN
Second edition Illustrated Three volumes
$7 7s net
Diffuse X-ray Reflections from Crystals

W . A . WOOSTER
35s net
Neutron Diffraction
G . E. BACON
Second edition Illustrated
55s net
Data for Biochemical Research

Second impression with corrections
Editedby
w.
R . M. c . DAWSON, DAPHNE H . ELLIOTT and K . M . J O N E S
c . ELLIOTT,
63s net
Mechanisms of Organic and Enzymic Reactions

S . G . WALEY Illustrated 70s net
Oxide Magnetic Materials

K. J . ST A N D L E Y
30s net
OXFORD UNIVERSITY PRESS
JAMES BURROUGH LIMITED

Established 18!20
4 Vauxhall S t r e e t , London, SE1 I ..
Telegrams; Burrocale, Souphone, London Telephone No. Reliance 3301
iii
F o
DARTON & Coo LTD.

Established I834
WATFORD, ENGLAND
Distant Recording Thermograph
MAKERS OF
M E R C U R I A L BAROMETERS MANOMETERS HYGROMETERS BAROGRAPHS H Y G R O G R A P H S T HE R MO G R A P H S Available through your Laboratory Supplier
iv
DICTIONARY OF CHEMISTRY AND CHEMICAL TECHNOLOGY

In English, German, Polish, and Russian
English Editors: H. STEPHEN and T. STEPHEN Invaluable to those who require an authoritative guide to modern terms in chemistry. The dictionary contains over 12,000English terms from all branches of theoretical and applied chemistry, chemical engineering, chemical and related technologies, as well as essential scientific terms frequently .encountered in the literature. An alphabetical index in each language quickly enables the user to find the corresponding term in the other languages. 724 pages 10 net
SOLUBILITIES OF tNORGANIC AND ORGANIC COMPOUNDS

Volume I, BINARY SYSTEMS, Parts D and 2
Edited by H. STEPHEN and T. STEPHEN The first of two volumes which together comprise a comprehensive work of reference, compiled from published data on the solubilityof elements, inorganic compounds, metallo-organic and organic compounds in ternary, binary and multicomponent systems. This volume, which is in two parts, details the solubilities of inorganic and organic compounds in binary systems, The information is presented in the form of tables, numbered consecutively and arranged systematically for easy reference. In every case, a reference number supplies details of the source from which the information was obtained. f 10 net P r 1 964 pages at Part 2 to be published in July
CHEMISTRY OF ORGANIC FLUORINE COMPOUNDS

M. HUDLICKY, Research Institutefor Pharmacy and Biochemistry,Prague Presents a comprehensivepicture of the rapidly expanding field of organic fluorine chemistry. Analytical methods and practical applications are included, together with valuable lists of physical and biological properties Ef the wide range of fluorocarbons. . . it should be on every scientists bookshelf.-Science Progress Every worker in the fluorine field should be in possession of this most useful book.-Idustrial Chemist 536 pages 43 illustrations 60s. net
Any volume sent on 30 days approval without obligation. Please quote this journal when ordering
PERGAMON PRESS
HEADINGTON HILL HALL, OXFORD
Press Books are distributed in the Western Hemisphere and the Philippines by t -a hl n Company, 60 F f h Avenue, New YoFk 11, N.Y., and Collier-MacmiUan it (Canada) Ltd., 132 Water Street South, Galt, Ontario, Canada.
011
d S K
THE CHEMICAL SUPPLY CO LTD
for details of the many new products they are mruurfacturing
Ester Solvents Alkyl & Aryl Ester Plasticisers Formaldehyde & Hexamine
Special Plastic Grades
Cadmium Colours Aromatic Chemicals Molybdic Products Copper Fungicides

Full technical details and samples will be sent on request
THE CHEMICAL SUPPLY CO LTD

7 IDOL LANE, EASTCHEAP, LONDON EC3
Tel: Mansion House 6854 Grams: Kemsupply, Phone London
Supplements to MELLORS COMPREHENSIVE TREBTISE ON INORGBNIC AND THEORETICAL CHEMISTRY

Al three supplements to Volume I1 have now been published, l
VOLUME 11 SUPPLEMENT I VOLUME 11 SUPPLEMENT 11
I
bringing this part of the work completely up to date. The Halogens (1956) A 1 I .o.o The Alkali Metals part I Sodium and Lithium (1961) E18.o.o VOLUME 11 SUPPLEMENT 111 The Alkali Metals part 2 Potassium, Rubidium, Caesium, Francium and the radio-chemistry of the alkali metals (1963) L15.0.0 Other supplements are in preparation Volume VIII Supplement I Nitrogen part I Volume VIII Supplement I1 Nitrogen part 2
BOOKS
SCIENTIFIC & TECHNICAL
LARGE STOCK O F BOOKS on the Biological, Physical,
Chemical and Medical Sciences supplied from stock, or obtained to order.
FOREIGN DEPARTMENT. Books not in stock obtained to

order with the least possible delay.
LENDING LIBRARY
SCIENTIFIC A N D TECHNICAL Annual Subscription from &2 5s. THE LIBRARY CATALOGUE, revised to December, 1956, containing a classified Index of Authors and Subjects, to Subscribers, EI 5s. net; to Non-Subscribers, ,cIz 2s.net; postagezs. 6d. Supplement to December 1959. To Subscribers, 5s. net, to Non-Subscribers, 10s. 6d. net., postage gd. Prospectus post free on application. Bi-monthly list of New Books and New Editionsadded to the Library sent post free to any address regularly.
H. K. LEWIS & CO. LTD.
136, Gower Street, WCI. EUSton 4282
Annual Reports on the Progress of Chemistry

1 11
I
Back Numbers (less certain volumes now out of print) are available-
~1
11
~
Volumes I (1904) to LVIII (1961)

Also
Collective Index of Volumes I to XLVI
Inquiries are invited by:
I
I 'I
THE CHEMICAL SOCIETY Burlington House .London, W.1

--
~~
__
__
- -
viii
Two Catalogues for You

30 Pages (list M-4) of Ultra-pure Elements, Single Crystals and
Inorganic Compounds I 3 0 Pages (list L-20) of 7,000 Organic Chemicals including
BIOCHEMICALS ENZYMES ALKALOIDS STEROIDS PHOTOSENSITIZING DYES VENOMS MOLECULAR MODELS & STENCILS
Containing 1,000 new materials, a few of which are listed below Write for your copy
Trimesic Acid 15/- H 4-(p-Chlorobenzoyl)-pyridine Butane-2,3-Diol 24/- K 3-Azabicyclo-(3,2,2)-nonane 2-Amino-Chrysene 40/- H 4-(2-Thenoyl)-butyric acid Cycloocta-l,3-diene 15/- D 2-Chlo~o-cyclopentanone 4,4'-Thiodiresorcinol p-Amino-thioanisole 36/- H Cyclododecene(94%) 85/- H Quinoline-2-carbiOol 60/- H Syringic aldehyde 3,5-Dicyano-pyridine Caryophyllenic Alcohol 75/- H Benzoic anhydride Sphingomyelin (puriss) 82/- d 3-Sulpholanol N, N-Dimethyl-piperazie 28/- H Thioxanthene 2-Cyclohexyl-cyclohexanone 25/- H Crotonitrile Benz0-3~4-dihydro-2-pyrone 45/- H 3-Pyrrohe Dichloro-tetrafluoro-acetone lo/- D dl-talitol N-Acetylneuraminicacid (synth) 154/- d Sclareol
62/- H 70/- H 60/- D 197/- H 89/- H 180/- H loo/- D 23/- H 20/- D 18/- D 40/- H 126/- D 45/- G 180/- H
1 LIGHT & CO. LTD. .

Colnbrook, Bucks, ENGLAND
i x
Engineering Equipment Users Association Handbooks

The principal objects of the Association are to assist i t s members t o promote a common policy for the standardization of engineering materials equipment and stores. The w o r k of the Association is entirely complementary t o that of the British Standards Institution w i t h whom close liaison and collaboration are always maintained.
3 Surface Preparation, Protection and Finish Painting o Steelwork f 15s 6 Chemical Resistant Linings for Pipes and Vessels 30s 30s 8 Steam Trapping and Condensate Removal Agitator Selection and Design 21s 9 18s II Vacuum Producing Equipment 30s I 2 Thermal Insulation of Pipes and Vessels f 15 Pneumatic Handling o Powdered Materials 40s (including FIuidization) 6s 6d I6 Factory Seating 17 Installation and Commissioning o A.C. and D.C. f
Rotating Electrical Machines (excluding Flameproof Types) for Use in the United Kingdom o r Overseas 12s 6d
published by Constable

Chemistry (Annual Reports - Vol.59-1962)

Загружено:

Сведения о документе

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Chemistry (Annual Reports - Vol.59-1962)

Загружено:

Авторское право:

Доступные форматы

Annual Reports

On The Progress Of Chemistry

Deputy Editor L. C CROSS, Ph.D., A.R.C.S., F.R.I.C. .

J. H. KNOX, B.Sc., Ph.D.

M. L. MCGLASHAN, Ph.D., D.Sc., F.R.I.C.

B. CAPON,B.Sc., Ph.D. P. F. S. CARTWIUQHT, M.Sc., Ph.D.,

THE CHEMICAL SOCIETY

THE CHEMICAL SOCIETY

E. W. SYRES, M.A., D.Phil. J, W. LINNETT, M.A., D.Phil., F.R.S.

129 130 152

9. SPECTROSCOPIC ANALYSIS 10. ELECTRICAL METHODS 11. THERMAL METHODS

449 457 473

CRYSTALLOGRAPHY 1. GENERAL.By W. Cochran . 2. ORGANICSTRUCTURES. D. J. Sutor By INDEX OF AUTHORS INDEX O F SUBJECTS

NOTE ON PRINCIPAL REFERENCES USED

GENERAL AND PHYSICAL CHEMISTRY

e _ _ _ _ -- _ _ .exp ( & / k T ) fads.

The Theory of Rate Processes,

KNOX: GAS-PHASE OXIDATION

+ C,H2 = C,H, + H + C2H2= H,O + C,H.

Kistiakowsky and Richards

have measured the vacuum ultraviolet

GENERAL AND PHYSICAL CHEMISTRY

KNOX: GAS-PHASE OXIDATION

+ H,O, = H,O + OH O H + H20, = H,O + HO,

which is kinetically equivalent.

If reaction (14) occurs we have

GENERAL AND PHYSICAL CHEMISTRY

OH rather than HO,.

+ H, = O H + H + Wall = Destruction + Wall = Destruction

(3) (21) (22)

GENERAL AND PHYSICAL C H E M I S T R Y

and the explosion limit is given by

Markevich and Pecherskaya 51 have found that, in a molybdenum-glass

GENERAL A N D PHYSICAL CHEMISTRY

GENERAL AND PHYSICAL CHEMISTRY

R. G. W. Norrish, Proc. Roy. SOC.,1935, A, 150, 36.

KNOX: GAS-PHASE OXIDATION

(CH,),C*CH, XH (CH3),C*CH2.O, (CH,),CH*CHO CH,O.

1, 345 (transl. 319).

2 postulate ~the following scheme . ~

--+ + CO,. CH,O

KNOX: GAS-PHASE OXIDATION

+CH,*CHCH ,*CH,*CH*CH 2*CH3+ I

CH,*CH*CH,.CH,CH*CH2CH2*CH3 +CH,*CH*CH2*CH,.CH*CH ,CH I I I I

GENERAL A N D PHYSICAL CHEMISTRY

+ 0,- \c-0 + o=<. -/-

(CH,),C*CH,*OH (CH,),C*CH,.OH= (CH,),CO

However, an equally plausible scheme, involving H02, can be written

+ H 0 2 = (CX3),C*CH2 (CH3),C0 + CH2*OH =

GENERAL A N D PHYSICAL CHEMISTRY

(CH,),CH*OH X(H0,) = (CH,),C(OH) XH(33-20,) (CH,),C(OH) 0 , = (CH,)&O Hop

GENERAL A N D PHYSICAL CHEMISTRY

KNOX: GAS-PHASE OXIDATION

+ KOz = CH,-O*OH + 0,.

CH, + 0 , = CH,*O*O* 4 CH,*O.OH + 0, + M = CH,*O*O + M +CH,*O.OH.

Their rate constant is then k8 while that of other workers is k,

+ HO, = C,H,*O.OH + 0,.

GENERAL A N D PHYSICAL CHEMISTRY

7coc12 + c1, kco + 2c1,.

k = 2.0 x 1O1O exp [ -4500/1.987T] mole-1

The rate constant of the reaction is

x l o l l exp [ -3100/1.987T] r n o l e - l ~ m .sec.-l. ~

SYMONS: ELECTRON S P I N RESONANCE

x l o l l exp [ -2750/1.987T] mole-1

(CH,),CCH, XH (CH3),CCH2.O, (CH,),CH*CHO CH,O.

+CH,CHCH ,CH,CHCH 2*CH3+ I

CH,CHCH,.CH,CHCH2CH2CH3 +CH,CHCH2CH,.CHCH ,CH I I I I

(CH,),CCH,OH (CH,),C*CH,.OH= (CH,),CO

+ H 0 2 = (CX3),CCH2 (CH3),C0 + CH2OH =

CH, + 0 , = CH,OO* 4 CH,O.OH + 0, + M = CH,OO + M +CH,O.OH.