Академический Документы
Профессиональный Документы
Культура Документы
The next few decades were characterized by intense activity in the building of the main
frame of aromatic chemistry.
could be converted, by way of bromobenzene, into the benzoic acid. This showed that
four positions were equivalent for a first substituent. And now it was known that two
of the hydroxybenzoic acids had this property namely, that each contained its hydroxyl
group in one of a pair of equivalent positions.
substituent must be preserved when the first is specialized to hydrogen, so that what
was the second substituent becomes the first, this result showed that the fifth and sixth
positions in benzene were each equivalent to any of the first four. In the same period,
the problem of determining the relative positions of substituents was solved in principle.
At first there was great confusion. Then Kekule proposed that all compounds
whose substituents were considered to be in the same relative positions as those of a
standard "ortho-compound" should be called "ortho-," and similarly for other such
designations.
Originally the designations were used without any accepted implication as to the
positional relations to which they corresponded. When later it was found that most
compounds which had been classified as ortho- had their substituents in 1,2-positions,
the prefix "ortho-" was reserved for 1,2-compounds, and similarly for the other prefixes.
The proposed principle of classification was simple.
substituents genetically connected with the carboxyl groups of phthalic acid are 1,2derives compounds.
reason was that some of the reactions which were used to establish genetic connection
, notably hydroxylations by treatments of sulphonic acids with alkali, and cyanisations
by the reaction of halogeno-nitro-compounds with alkali cyanides, frequently involved
rearrangements: (for reasons which are even now not fully understood): such
disturbances were at the outset difficult to recognize and locate. Then, in 1874, a secure
basis for the orientation of substituents in benzene compounds was offered by Griess,
Salkowsky, and Koyrner
between one substituted benzene and another, but between di- and-tri substituted
benzenes.
gave one diaminobenzene, while three gave another, and the remaining acid the third;
and therefore, the first diaminobenzene had to be ortho-, the second meta-, and the third
para.
In studying such relations one was not at the mercy of un recognized rearrangements.
Subsequent work on the orientation of substituents in benzene derivatives has been
based on this method.
Thus the two problems, of symmetry, and of orientation, were solved in the first decade
after the publication of Kekule's fundamental paper. In the same period the attack was
opened on the much greater problem, one which was to occupy chemists for many years
afterwards, namely, that of the actual disposition and function of the six carbon
valencies of benzene, which are not required to maintain the ring or to hold the hydrogen
atoms.
Kekule's assignment, in 1865, of the six valences to three double bonds was provisional:
for the symmetry question was then unsettled. In 1872, Kekule issued a supplementary
hypothesis to the effect that an oscillation occurred between the two possible
arrangements of double bonds.
His reason was that, as Ladenburg had already pointed out, the original formula
admitted unrealized possibilities of isomerism in benzene derivatives. It soon became
clear that the additional symmetry introduced by the oscillation hypothesis was
demanded by the observed extent of isomerism.
Subsequently to the original theory, but before its emendation, two other attempts were
made to represent the symmetry that seemed to be indicated by the observed isomerism.
One is expressed in the prism formula for benzene (below), first seriously advocated in
1869 BY Ladenburg. This formula requires the correct numbers of all the Different kinds
of substitution products. But the symmetry properties of the combining positions are
such that these positions have to be correlated with those of a simple ring formula as
indicated by the numbering:
having all substituents where they would be expected if benzene had the simple ring
structure. The other early formula of the requisite symmetry was the diagonal formula,
first advanced in 1867 by Claus.
Originally clause assumed that the para- and ortho bonds to have identical
properties, so that each carbon atom was bound to three others in exactly the same way.
(The difficulty of arranging for this in Euclidian space was not seriously felt at a time
when formulae were considered essentially as symbols of chemical relationships,
without much regards for any metrical properties the molecules might possess). But, in
1882 Claus suggested that the para-bonds should be regarded as radically differ from
all other bonds, thus taking the first step in admitting, by the use of a special symbol, a
difficulty insoluble in terms of already established concepts. Especially the new view
was represented more explicitly in the modified symbol known as the centric formula:
It was first used by Armstrong, was at once adopted by Baeyer as the best
symbolic representation of his results, and was finally accepted Claus as a suitable
expression of his ideas. Originally, the centric formula expresses by the symmetry of
the benzene, but was agnostic with respect to all other properties. However, in 1982
Bamberger used it in a discussion of stability.
He attempted to correlate stability in different aromatic types by means of the
assumption that the six-fold character of the centric valency group was the essential
factor of stability. Since, he argued, pyridine could form a sextuple valency group
without employing the salt forming valencies of its nitrogen atom, while pyrrole could
do so only by making use of all its nitrogen valencies, one could understand why
pyridine has the basic properties of the tertiary amines, while pyrrole was practically
non-basic:
As far as it goes this is completely correct: reading electrons valencies, it is what
we should say today. Quite the most advanced of the early attempts to interpret aromatic
stability, while still satisfying the symmetry condition, was that made in 1898 by Thiele.
Through a general study of unsaturation, he had been led to assume the reactive
valencies of double bonds to be in principle continuously divisible, and to exist in most
circumstances partly bound and partly in the free state; and he had shown how in a chain
of alternate single and double bonds, the possibilities of division could lead to what he
called "conjugation" between the double bonds, that is, a more even spread of affinity
over the double bonds and intervening single bonds, so that the main opportunities for
reaction appeared at the ends of the chain, where un-neutralized free affinity was
available.
conjugation is cyclic: there being no ends, there can be but little additive reactivity.
The symmetry condition was fulfilled by starting with either of Kekule's oscillating
structures, and allowing the affinity redistribution to proceed equally to coincidence, so
that all ring bonds became equivalent:
The outstanding merit of this theory was that it dealt with aromatic stability on
the basis of concepts developed outside the aromatic series. The main general
characteristics of aromatic systems with which a structural theory should be concerned
are its symmetry, its stability, and its transformations.
the symmetry, and is not inconsistent with the stability. Thiele's formula expresses the
symmetry, and interprets the stability.
But any consideration of the modes in which benzenoid systems are disrupted,
indicates appeal to Kekule's formula, of course, in association with his dynamic
hypothesis in
destroy the aromatic system, without opening the ring, produce either addition products,
or ortho-quinonoid, or para-quinonoid, derivatives; and all such conversions are more
easily understood in terms of Kekule's formula than of the others. Thus it came about
that the last of the pre - electronic attempts to make a theory of benzene structure took
the form of an expansion of Kekule's dynamic hypothesis.
At a very early date Dewar had proposed, as a possibility, the bridged formula
of benzene: as a static formula, it was quite unacceptable, lacking the necessary
symmetry. In 1922 the writer revived it, interpreting the para-bond as qualitatively
problem was not dealt with, except through the undeveloped idea that the inter
conversion of forms might be rapid enough to restrict reaction in any one form. This
was the apparent cul de sac to which classical chemical considerations led: the
symmetry condition could be fulfilled in various ways; but no one way satisfactorily
interpreted both the stability and the transformations.
characteristics was taken as guide, either of two roads would be followed; and,
historically, they ended in different places, the one in Thiele's theory, the other in the
expanded dynamic hypothesis.
electronic theory of chemical binding brought about the reconciliation that had seemed
invisibly distant, showing that the two theories could be considered to represent
complementary aspects or appearances of the same interior physical situation.
The second method, which Huckel himself invented, is known as the valencybond treatment. It goes to the other extreme, over-emphasizing the covalent character
of the binding; and, for that very reason, it appears particularly easily in the role of an
interpretation of valency concepts. The technique of this method was simplified by
Pauling and Wheland, who applied it to benzene and other aromatic hydrocarbons.
In setting up the problem, Huckel, and likewise Pauling and Wheland assumed that each
carbon atom of benzene supplies one electron in an atomic p orbital, having its
symmetry axis at right angles to the molecular plane, to form a molecular group of six
electrons. The remaining electrons are left to hold, with single bonds, the regular
hexagonal frame of six CH carbonium-ionic centers.
Each electron is then considered as moving in the combined potential field of
the framework and the smoothed-out field of the remaining electrons. It is easily
shown that the plane of the atomic nuclei is a nodal plane for all the electrons, which
together must produce a charge-density distribution having total hexagonal symmetry,
as illustrated in Figure.
The common object of these techniques is to compute the mesomeric energy or
aromatic resonance energy, that is, the extra stability that arises from not confining the
electrons to three static double bonds, as in a Kekule formula. The answer depends on
the assumptions made about the extra motion permitted to these electrons.
They are, indeed, bonds having the internal energies and mutually repulsive interactions
of two-electron bonds. But they are mobile bonds, always changing among the positions
between which they were assumed to move in the earlier dynamical representations of
benzene. It was found necessary to include not only the Kekule but also the Dewar
structures, in defining the limits of mobility of the mobile bonds: no other structures are
involved, because bonds cannot cross.
The wave-function M of the normal mesomeric state is therefore constituted from
those of Kekule and Dewar structures, K and D, taken with two and three orientations,
respectively, as is required by symmetry. Pauling and Wheland's coefficients for them
are as indicated in the following equation:
M = 0.625(K1 + K2) + 0.271 (A + D2 + D3)
They show that the Kekule structures are more important than the Dewar
structures, but that the latter are not negligible, in the composition of the mesomeric
state. The Dewar structures contribute about 20% of the calculated mesomeric energy.
The mesomeric energy is expressed in terms of an energy quantity called : in principle,
represents the energy effect of allowing two adjacent atomic p electrons to undergo
exchange, as in the formation of the component of a static double bond; in practice
is a disposable constant, chosen to give the best fit with experimental data. The
calculated energies for benzene, naphthalene, anthracene, and phenanthrene, are
1.1, 2.04 , 3.09 , and 3.15 . respectively, the last two values involving a minor
algebraic approximation.
If is chosen as 35 kcal./mole. Again however, we have the position that, not only do
the "calculated" values depend heavily on empirical data, but also the "observed" values
depend in part on inter pretative assumption.
Observed
Energy
Calculated
Hydrogenation M.O. method V.B. method
Constant
(with = 20)
(with = 35)
Benzene
37
36
40
39
Naphthalene
75
74
71
Anthracene
105
106
108
Phenanthrene
110
109
110
The valency-bond method has since been considerably refined within its own
framework, though it has not yet proved possible to eliminate its dependence on a
disposable constant. (To calculate non-empirically would be a heavy task.) What was
inadequate in the earlier applications of the method was the specification of
mesomerism exclusively in terms of fully covalent structures: and what is needed is the
inclusion of dipolar structures: in general, the more that are included, the better the
results should be. There are two types of singly dipolar structures with adjacent charges,
A with 12 orientations, and B with 12 and three types with non-adjacent charges, P with
6, Q with 24, and R with 6 orientations, as well as doubly and trebly dipolar types, to
cite them in the probable order of diminishing importance:
The work on the inclusion of such polar structures in the valency bond treatment was
initiated by Sklar, and has been developed by Craig, who has solved the problem, with
inclusion, besides the five non-polar structures K and D, of the twenty-four adjacentcharge structures A and B. His wave-function for the normal mesomeric state is as
follows:
M = 0.39(K1 + K2) + 0.17(D1 + D2 + D3) + 0.07(A1 + Az + ...A12) + 0.03(B1 + B2+ .. B12)
The energy is calculated to lie 17 kcal./mole below Pauling and Wheland's normal
mesomeric state. This shows that quite large un-certainties are involved in the treatment
based on non-polar structures only; but it suggests that higher approximations would
shift the energy by only a few kcal./mole further. However, for the present any really
close agreement with experiment must remain dependent on making the final result of
calculation partly dependent on experiment.
The molecular orbital method has been developed, not entirely within its original
framework, in ways which are theoretically interesting, in as much as they constitute,
in principle, a technique for the non-empirical evaluation of the energies of electron
states. At the moment, the numerical accuracy of the calculations is insufficient to give
quantitative agreement with experimental values; but the treatment of benzene does give
a qualitatively satisfactory account of its energy levels, and has been of value in
classifying some of its spectroscopically known, excited electronic states. The original
steps were taken by Goeppert-Mayer and Sklar.
First, they formed the product wave-functions, as calculated by simple molecular orbital
theory, into "antisymmetric" additive combinations, thereby placing the motion of the
electrons under the restriction that not more than two could be together in the same
atom, so satisfying Pauli's principle in the atoms. Then, having assigned the electrons
in pairs to the three lowest orbitals, and made the wave-functions totally antisymmetric
to satisfy Pauli's principle fully, they allowed for the energy of mutual repulsion of the
electrons by averaging it over the orbitals. The necessary energy terms were nonempirically evaluated by Sklar and Lyddane and Parr and Crawford.
The next step, carried through by Craig, involves allowing for the circumstance that the
interaction energy of the electrons will change their motions, so that it is not correct
to average it over motion assumed undisturbed.
among all the orbitals, changing the total electronic wave-function, as in every
resonance problem, until the energy is minimized.
In principle this method, which is described as allowing for "configuration interaction,"
and was first developed in its molecular applications by Craig, gives molecular wave
functions as good as any that could be formed by the initial use of only p atomic wavefunctions.
It will easily be understood why, despite the mesomerism of the aromatic nucleus,
valency-bond formulae, particularly those of the relatively stable Kekule structures,
retain their usefulness for the interpretation of the transformations of the aromatic
nucleus, why, for instance, we attach the curved-arrow signs to Kekule formulae, even
though such formulae could not by themselves account for the stability of the nucleus.
If, in a chemical transformation affecting an aromatic nucleus, or in the transition state
of such a transformation, the electron pairs are regarded as largely localized, then it is
convenient, for the purpose of following the reaction mechanism, to think of those
electron pairs as having immediately come from localized positions.
Such a concept
saturated compounds, so that the whole of the energy of mesomerism has not to be
supplied, in order to complete process (a), before process (b) can commence.
But the activation energy of any process which permanently, or temporarily,
breaks up the mesomeric system will be increased by the mesomerism, even if not by
the full amount of the mesomeric energy. Thus does the theory of mesomerism fulfil
the three main requirements in the problem of aromatic nuclei, namely, to interpret their
symmetry, their stability, and their transformations.
The theory of benzene provides a basis for modification to give a qualitative
pattern for that of pyridine. But the possibilities of a satisfactory quantitative calculation
of the energy states of pyridine are very much reduced by the need, created by the
hetero-atom, for new but unknown energy integrals.
Observation shows that the introduction of the hetero-atom does not much change the
size and shape of the molecule, or those properties, chiefly the mesomeric energy, and
exaltation of diamagnetic susceptibility,
which
arise primarily
from electron
delocalization.
The hetero-atom does, however, create a dipole moment, -2.26 D in pyridine,
the negative sign meaning that, as one should expect, the electrons have concentrated
towards the electronegative nitrogen atom. On the basis of our analysis of the dipole
moments of simple alkylamines, and of the effects of carbon chain extension, a moment
of only about 1.0D would be expected to arise from the effect of the electronegativity
that a moment of 1.2 D arises from a displacement of the electrons of the shell, an
average displacement of 0.04 A, several times more than the average from the
electrons.
Quinoline has a moment of -2.29 D, and isoquinoline -2.73 D. These moments are
also due to the electronegativity of the nitrogen atom, which in isoquinoline acts
appreciably on the electrons of the more remote ring.
There are also 39 non-polar structures with trans-annular bonds, and many more polar
structures. The whole system is so complicated that one is tempted to see whether any
useful considerations can be set down after simplification on very drastic lines.
The
most drastic approximation that one can make is to neglect the bridged and polar
structures completely, in spite of their large numbers. If we do this, there still remains
the problem of weighting the A- and B-type Kekule structures in the mixed wavefunction; but, after what has been done, it is an insignificant further step to take these
weights as equal the interesting conclusion then follows that the multiplicity of the l, 2bonds of naphthalene is 5/3, and is greater than that of the other bonds, all of which
have the multiplicity 4/3:
From this it appears that the 1,2-bonds of naphthalene should be more like double
bonds than any of the bonds of benzene; and also that the whole 1,2,3,4-system in
naphthalene should be somewhat similar to buta-l,3-diene, and probably still more
similar to 1,4 diphenylbuta-l,3-diene.
These conclusions bring to mind much general chemical experience 2-Naphthol
halogenates and diazo-couples in the 1-position, as if its phenolic system preferred to
resemble an phenolic system with a double bond in the 1,2-position, rather than one
having its double bond located in the 2,3-position. Naphthalene adds chlorine, not as
easily as an olefm would, but much more readily than benzene. Naphthalene is reduced
by sodium dissolving in alcohol, just as 1,4-di-phenylbutadiene is, and the two added
hydrogen atoms appear in the 1,4-positions, in naphthalene, leaving an un attacked
double bond in the 2,3-position exactly as in the case of 1,4-diphenylbutadiene. Metrical
evidence supporting the above distribution of bond multiplicities will be mentioned
later. Phenanthrene is another example in which these simple considerations lead to
chemically reasonable results. Phenanthrene has five Kekule-like structures, which are
of four different types, two structures differing only in orientation. If we weight all five
equally, the bond multiplicities work out as follows:
The 9,10 - bond has the multiplicity 9/5, and therefore should be closely similar to a
double bond. The non-angular bonds of the lateral rings show alternating multiplicities,
as in naphthalene, though the alternates are less pronounced than those of naphthalene.
The conclusion concerning the 9,10-bond certainly agrees with its chemistry.
Phenanthrene adds bromine in the 9,10-positions; it is readily reduced to give a 9,10dihydro-derivative; and it is easily in the 9,10-positions (to give phenanthraquinone
and di-phenic acid). In all these properties the 9,10-bond resembles fairly closely the
double bond of stilbene. Anthracene lies on the reverse side of the picture.
If we work out the bond multiplicities from the four Kekule-like structures, which are
of two types, each type having two orientations, we obtain, allowing all the structures
equal weight, the following values:
They suggest that the additive reactivity of the lateral rings, in which the bond
multiplicities alternate, as in naphthalene but more strongly, should completely
overshadow that of the central ring, in which the bonds of the CH-groups are as in
benzene.
The reverse is the case. Anthracene is reduced by sodium amalgam to 9,10dihydroanthracene. Chlorine, bromine, and nitrating agents substitute anthracene, first
in the 9- and then in the 10-position; but by nitration in acetic acid an intermediate
addition compound, 9-nitro-9,10-dihydroanthryl-10-acetate, can be isolated, which
readily under goes further conversion to 9-nitroanthracene. 9-Anthranol and 9-anthrone
are separately isolable, but easily interconvertible, tautomers; and so also are 9,10anthrahydroquinone and 9-hydroxy-10-anthrone.
It is desirable thus to test the qualitative reliability of so simple an approach as
that of mixing all and only Kekule structures equally. But having tested it, we should
accept the answer, viz., that it is not' only unsound in theory, as we knew, but also
untrustworthy in practice This approach should not be used, as it has on occasion been,
as a foundation on which to build an argument.
Attempts have been made to calculate electron distributions in polycyclic
aromatic systems quantitatively. Such calculations are sometimes qualitatively
suggestive, but none commands confidence in its quantitative validity, in as much as
the uncertainties introduced by the approximations made are nearly always of the order
of magnitude of the quantities being calculated.
The general relationships between benzene and pyridine are expected to apply
as between napthalene and quinoline or isoquinoline, or as between anthracene and
acridine, and so on.
electron shells of an atom. Filled shells would occur with two electrons (ethylene),
with six (benzene), and, in general, with 4n + 2 electrons, but not with 4 electrons
(cyclo butadiene), with
eight
Thus, the benzene group of six electrons, the aromatic sextet, should be the first pi
electron group to show closed shell stability through double-bond de-localization.
The idea of a Stable bonding group of six electrons, a bonding sextet, implying the
tendency of a system which starts with somewhat fewer than six to build up six such
electrons, is immediately acceptable, going back, as it does in its empirical aspect, with
all the weight of his incorporation, on essentially that basis, of the five-membered
heterocyclic in the aromatic family.
Huckel rationalized the idea. Huckel's 4n+2 rule applies only to monocyclic electron
systems though some authors have applied it to polycyclic systems, to which in view of
its derivation, it can have no direct relevance.
the rule that it does not predict the stability of acenaphylene which has twelve
electrons.
and, in view of the simple nature of the theory from which it was derived, we should
probably not expect much more from it. Cyclobutadiene is too unstable to be kept.
Cyclo- octatetraene can be kept, but it is a highly reactive,
Monocyclic closed-conjugated
non-planar polyolefin.
known, but for these rings it would seem that the Huckel principle is not the dominating
factor in their stability, or lack of it.
Huckel's classification of pi electron systems was based on elementary molecular orbital
theory-, which in the next stage of refinement should be made to take account of inter
electronic repulsion. In attempting this, Coulson and Rushbrooke were led to another
useful classification, in which pi electron systems are classed as "alternant" Inter science
of formulae below.
known, and their mesomeric energies are not abnormally low. Alternant character in
short, is not closely associated with aromaticity. The annexed illustrations show these
two classifications, together with a third, described below.
The
Although such
calculations are feasible only in the simplest cases, Craig was led by this study to
suggest a more general criterion, based on symmetry, for recognizing the circumstances
in which only small mesomeric energies arise, and thus to propose at a classification
of pi electron systems, which is aimed specifically at the conditions for aromaticity.
This criterion is limited to molecules with at least one two-fold rotational axis of
symmetry passing through at least two pi electron centers. The rule can be followed
with the aid of any of the above diagrams. The molecule
is first
spin-labelled, as
described already with the added condition (fulfilled in the diagrams) that any
avoidable break in alternation is set at a single bond in a Kekule- type structure.
A two-fold axis through atoms (vertical or horizontal in the diagrams) is then selected,
and the molecule is imagined to be turned over by rotation around it. One now counts
the resulting number of interchanges of pi centers, and the number of such inter changes
which reverse spin-labels. If the sum of these two numbers is odd, the molecule is
classed as "pseudo-aromatic.
If the sum is even, the molecule is aromatic" This classification bears no relation to
the number of pi electrons or to the number of rings.
in calculations on
pseudo-aromatic
molecules are always of a different symmetry class, viz., the truly aromatic molecules
the symmetry test is applicable only if the necessary symmetry is present in a molecular
model.
typically aromatic, nor to the stable non-olefinic diphenylene, nor to the typically
diolefinic dibenzopentalene; for none of these molecules has a two-fold axis through
atoms. The last two of these compounds are formulated below.
In such cases we can only try to judge which simpler and more symmetrical "parent"
will control the stability of the derivative. In the two molecules formulated, we assume
control by the benzene rings: that is, we assume that the benzene rings are not strongly
conjugated with each other through the intervening rings.
trans-annular non-bonding pressures between atoms which are attached to the rings and
find themselves turned inwards in rings of a certain size.
Cyclobutadiene has not been isolated in a free state, but it has, as, some derivatives
have, been obtained in the form of metal complexes, such as (C4H4) Fe(CO)3.
On attempting to liberate the hydrocarbon one obtains only products of its
polymerization or addition reactions. These are stereospecific enough to show that
Cyclobutadiene has a singlet ground state, i.e., that it is not a di-radical.
Cyclo-octatetraene was first prepared by Willstatter, who obtained it from pseudopelletierin by reactions which included removal of the nitrogen bridge in two steps of
exhaustive methylation. Its properties, those of a highly reactive polyolefin, were a
surprise to everyone; and accordingly Willstatter's work was repeatedly, though never
justifiably, called in question. Then Rappe obtained the substance by polymerization
of acetylene in the presence of nickel cyanide in tetrahydrofuran, a method allowing the
production of large quantities.
Rappe confirmed
properties
and
chemical
electron delocalization. Heats of formation and reaction allow it only a little mesomeric
energy, less than would be expected for an open-chain, normally conjugated, tetra-ene.
It is a yellow liquid, but its visible color arises only because the long vibrational of an
absorption band, centered well up in the ultraviolet, encroaches on the visible region
of the spectrum.
Cyclo-octatetraene is isomerized by heat to styrene, and is converted by numerous
reagents to benzene derivatives, for instance, by chromic oxide to terephthalic acid. It
is reduced catalytically in the expected stages to cyclo-octane. It is reduced by alkali
metals, and adds hydrogen halides, and halogens. Willstatter had noticed ring-bridging
during additions, and Reppe and Cope have carefully elucidated some of these
processes. The underlying phenomenon of intra-annular valency tautomerism is shown
by Anet and by Roberts and their coworkers by the method of nuclear magnetic
resonance that in cyclo-octatetraene itself, and in various of its simple substitution
products, such as the fluoro- and deutero-carbethoxy-derivatives, the double bonds
move round the ring; but that, because nuclear deformations are involved, an activation
For cyclo-octatetraene itself, the energy of activation of the cyclic bond shift is 13.7
kcal./mole, the lives of the successive stable con formations being of the order of a
centisecond at 0. In some substitution products the barriers are somewhat higher, and
the individual conformers may live for several seconds at that temperature.
Several closed-conjugated large rings have been prepared, by Sondheimer and his
coworkers, by the general method of oxidative cyclizing, or cyclically polycondensing,
alkane or alkene di ynes, and subjecting the formed cyclic
poly-ynes to
graduated prototropic re arrangements and reductions. C14H14 and C18H18, [14]annulene and [18]-annulene, as they are called, are the best known. They are 4n + 2
hydrocarbons. Their nuclear magnetic resonance spectra show that they attain, and
retain, the flat conformations represented below, at sufficiently reduced temperatures,
60 for [14]-annulene and room temperature for [18]-annulene. At higher
temperatures, for instance, room temperature for [14]-annulene and + 60 for [18]annulene, these conformations become unstable. We can understand this, and also the
greater stability of the flat conformation of [18]-annulene, inasmuch as the interior
hydrogen atoms must be under a mutual compression which is strong in flat [14]annulene, and appreciable in flat [18] annulene.
The mesomeric energy by heat of combustion of the latter is 100 kcal./mole. [24]Annulene is of the 4n, series, but [30]-anntilene is a 4n+2 hydrocarbon, and both are
declared as unstable. Probably Huckel's rule loses some of its force in such attenuated
electron systems as these very large rings present. Pentalene and benzodipentadiene
are so far unknown, despite many attempts to synthesize them, though heptalene has
been obtained as a colored, unstable, readily polymerising polyolefin.
Azulene is well known and is, indeed, the parent of a great series of compounds, having
a wide natural distribution in essential oils. Azulene is a blue solid, and an X-ray
analysis of the crystal has shown that the molecule is flat, and has the bond lengths
given below:
The average bond length is as in benzene, 1.40 A, but the bridge-bond, which is
single in both Kekule structures (above), though it becomes double in some polar
structures, is considerably longer, 1.48 A. Azulene has a dipole moment equal to 1.0 D;
and measurements on 2 chloro-, 2-bromo-, and 2-cyano-azulene show that the electron
dis placement in the parent hydrocarbon is from the seven-membered to the fivemembered ring. Azulene has an exaltation of diamagnetic susceptibility almost equal to
that of its isomer naphthalene.
This means that cyclic electron delocalization is approximately as good in
azulene as it is in naphthalene. Azulene has a large, though not yet closely agreed,
mesomeric energy. It has been estimated as being 30 kcal./mole less than that of
naphthalene, and this, along with Pauling's figure for the latter molecule, would give 45
kcal./mole to azulene; but an independent measurement by hydrogenation has given the
value 31 kcal./mole.
It can probably be said that the uncorrected mesomeric energy of azulene must be
approximately one-half that of naphthalene: and to the uncorrected value, a term of the
order of 10 kcal./mole for the strain in the azulene ring would have to be added, in order
to reach an estimate of the mesomeric energy in azulene.
Azulenes undergo most of the typical electrophilic aromatic substitutions,
Friedel-Crafts acylations, nitrations, sulphonations, and diazo-couplings, though
sometimes the conditions have to be carefully regulated, for the molecule is somewhat
sensitive to drastic reagents. The substitutions occur successively in the 1- and 3positions; that is they occur, as they should, in the five-membered ring, which we know
to carry the negative dipole charge of the hydrocarbon; indeed, they occur where
maxima of pi electron densities have been placed by calculation the physical properties
of acenaphthylene seem not yet to have been studied.
But it is a very stable hydrocarbon, formed in numerous high-temperature
reactions, including the pyrolytic
loss
of
hydrogen,
above
700,
from
its
dihydro -derivative acenaphthene (with a. CH2. CH2. bridge); and it is also formed from
the latter by mild oxidizing agents.
It is produced, with an abnormal loss of hydrogen, when various acenaphthenesulphonic and disulphonic acids are desulphonated with alkali. The .CH: CH.
Bridge in acenaphthylene, rather like the -CH: CH- bridge in Phenanthrene, is mainly
a center of additions, as of halogens; and substituted derivatives are formed only after a
subsequent elimination.
polynuclear aromatic compound." Nearly all its known reactions are normal
electrophilic aromatic substitutions. It can be halogenated, nitrated, and with mixed acid
dinitrated, acetylated, and with excess of reagents diacetylated, and disulphonated.
The first substituent enters the 2-position only, and the second the 6-position only, as
far as is known. 1, 2: 4, 5-Dibenzopentalene, described by Blood and Linstead, is a
compound of a very different type. Its known reactions are all of the central butadiene
residue.
These structures allow the pi electrons to circulate completely round the ring, but one
pair of electrons remains continuously unshared. Thus the clockwise electron
movement,
Shifts the unshared pair one step anticlockwise; and the process can be continued as
indicated by the arrows in the second formula. This means that, in the mesomeric state,
the unshared electrons are spread all round the ring, so that the carbon atoms are partly
anionic, and the nitrogen atom is, to a considerable extent, cationic. The same theory
applies to other five-membered aromatic nuclei, such as those of thiophen, furan,
glyoxaline, oxazole, etc., and to the five-membered components of condensed systems,
such as those of indole, carbazole, thionaphthen, purine, etc. Pyrrole has a large
mesomeric energy, but it is smaller than that of benzene or pyridine; and the same
difference runs through a comparison of analogous polynuclear compounds, as of indole
with naphthalene or quinoline; and the distinction shows in heterocyclic molecules with
other hetero atoms, molecules such as furan and thiophen.
The exaltation of diamagnetic susceptibility of pyrrole seems not to have been
measured; but for furan the exaltation is large though smaller than for benzene or
pyridine. For thiophen the exaltation is as large as for benzene and pyridine. Pyrrole
has the dipole moment +1.80 D, in the opposite direction to the dipole moment of
pyridine. The pyrrole moment can be approximately analyzed as below. The analysis
shows that a moment of +2.3 D arises from a mesomeric transfer of nitrogen electrons
to the ring, spreading negative charges round the carbon atoms of the ring and leaving
the nitrogen atom with a positive charge, as the above polar valency structures would
indicate:
Electroneg. 2
Mesomeric 3
1.3
-0.8 X 2.3
2.3
= - 1.8
Although pyridine, quinoline, and acridine are bases, of the same order of basic strength
as aniline, their odd-ring analogues, pyrrole, indole, and carbazole, are practically
non basic. The theory of their mesomerism explains this, somewhat in the same way
as Bam berger's theory did: the unshared nitrogen electrons are fundamentally involved
in the aromatic system. The imino-hydrogen atoms pyrrole, indole and carbazole
are distinctly acidic, like the imino hydrogen atoms of succinimide and phthalimide.
The theory account for this also: in each case, mesomerism confers a positive charge on
the nitrogen atom.
The carbon positions in the pyrrole nucleus are enormously more reactive than those of
the pyridine nucleus, or of benzene. As one standard text-book of organic chemistry
remarks "The great reactivity of the methine hydrogens in pyrrole quite remarkable.
They can be replaced by the most diverse atoms and groups with the same facility as
the imine hydrogen, or even more." This is just what should be concluded from the
theory that unshared nitrogen electrons are spread all round the ring.
To give one
example, the action of halogens on pyrrole is extremely energetic, and in order to secure
sufficient control for preparative purposes, it is usual to work in very dilute solution:
even then, in general, four or five hydrogen atoms are replaced.
course, completely different from that of benzene and much more different from that of
pyridine.
It has been shown that 2, 5-dimethylpyrrole and 1, 2, 5-trimethyl-Pyrrole, on ozonolysis,
give both glyoxal and methylglyoxal. This shows clearly that carbon unsaturation is
not localized in the 2, 3- and 4 5-bonds, but is distributed all-round the ring as the
preceding formulae illustrate.
The capacity of cyclopentadiene to yield stable sodium and other alkali metal salts (the
property used to separate it from the light fraction from coal tar) is evidently associated
with the same type of mesomerism.
The free hydrocarbon is not aromaticits mesomeric energy is about the same as that
of buta-l,3-diene. But the anion is aromatic, in the same way as is pyrrole. And thus the
anion is much less unstable than hydrocarbon anions usually are. The valency structures
are shown below, the anionic charge being equally divided between the five carbon
atoms in the mesomeric state:
Indene and fluorine also form alkali metal salts. When an aqueous solution of a,
quaternary 9-fluorenylammonium salt, or of a 9-fluorenyl-sulphonium salt, is made
alkaline, highly colored, somewhat unstable compounds are produced. The colored
substance from dimethyl-9-fluorenylsulphonium salts has been investigated in some
detail, and shown to be dimethylsulphonium-9-fruorenylide.
The reason for its formation is evidently that the anionic center is stabilized by
mesomerism of the cyclopentadienide -ion type. The large dipole moment of the
compound shows that the unshared carbon electrons are not absorbed into the sulphur
atom to a predominating extent, even though the latter has unoccupied orbitals.
Krollpfeiffer and Schneider prepared the corresponding pyridinium-'ylide, and Wittig
and his coworkers have made the trimethylammonium-. trimethylphosphonium-,and
trimethylarsonium-'ylides:
iron derivative, ferrocene, (C5H6)2Fe, first prepared by Kealy and Pauson, has the
configuration of a pentagonal antiprism, with the iron atom at the center of symmetry.
The extent of observed isomerism among derivatives of ferrocene has created the
impression that no large barrier exists to rotation of the separate rings around the
pentagonal axis. The substance is volatile, and stable to heat, sensitive to oxidising
agents, but stable towards reducing agents. It is not prone to additions, but can undergo
some electrophilic substitutions, for instance,
sulphonations
and
Friedel- Crafts
acylations. In these reactions, the first two substituents enter one in each ring. But an
alkyl substituent, already in one ring, in part attracts an entering acyl group to the 2and 3-positions of the same ring. All this suggests a considerable degree of aromaticity.
But just how the iron atom absorbs the anionic charges without seriously impairing their
delocalization is not completely clear, though it is obvious that the 3d orbitals of the
iron atom must be involved cycloheptatriene (tropilidene) is a polyolefm of no very
special stability. But, as Doering and Knox showed, it adds Br2, and the adduct losses
HBr, to give the ionic bromide of the cycloheptatrienylium ion, an outstandingly stable
carbonium ion.
The tropylium ion should have full heptagonal symmetry, with a delocalized sextet,
to which several sets of seven equivalent valency structures can be assigned, the
unbridged set being as shown below.
Most carbonium ions are destroyed instantly and irreversibly by water, and indeed by
any basic substance, neutral or anionic. But the tropylium ion has considerable stability
in water, reacting with it reversibly, and qualitatively in the manner of the cation of a
pseudo-base, but here only to a small equilibrium extent, to form pseudo-basic
cycloheptatrienol (tropenol):
Even in dilute solution, the tropylium ion is the more stable species; and, in view of the
strong contrast with the properties of carbonium ions in general, this is a striking
illustration of the stabilizing effect of a delocalized six-electron shell.
It is obvious that a whole series of seven-membered hetero-aromatic systems, typified
by boratropylene and beryllatropylene, the electron deficient counterparts of pyrrole
and furan, remain undiscovered the present time:
References:
[1]. Structure and Mechanism in Organic Chemistry; Second Edition; C.K.INGOLD