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SUMMARY
Aromatic sulphonation and related reactions are of immense importance industrially having wide application in
dyestuff and pharmaceutical industries, as well as in tonnage chemical production such as in the manufacture of
detergents. Consequently, much of the published work on this subject comes from industrial laboratories, often as
patent specifications.
. This survey covers the direct sulphonation of benzene and many of its derivative, of naphthalene and of the simpler
aromatic heterocycles. Sections are also devoted to the topics of chlorosulphonation and sulphone formation, with a
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The“related reactions” have been taken as those reactions which occur concurrently with sulphonation. These include
desulphonation and sulphone formation. Also chlorosulphonation has been considered, as often the sulphonic acid is
Introduction
Aromantic sulphonation is an organic reaction in which in which a hydrogen atom on an aromatic molecule is replaced
There are a variety of reagents which are commonly used to introduce the – SO3H group into an aromatic molecule, the
most widely used being sulphur trioxide, oleum , sulphuric acid, chlorosulphonic acid complexes of sulphur trioxide.
The choice of sulphonating agent is important as in general ,side reactions such as sulphone formation, rearrangement,
and anhydride formation increases with increasing reaction temperature and sulphur trioxide content.
The properties of the various reagents are discussed in other literature . A comparative study of the sulphonation of
1-10
1,3,5, and 1,3,7 trichlorosulphonyl naphthalene at 150-1700c, and 1,5 dichloulphonyl naphthalene at 1000c showed that
the order of activity of the sulphonating agents was 55% Oleum > 73% Oleum > SO3> ClSO3H > H2SO4 11
The fact that oleum appears to be more reactive than sulphur trioxide is attributable to a solvation effect. Complexes of
sulphur trioxide were not studied but presumably would have been much less reactive than sulphur trioxide. These
complexes have been well reviewed 2,11 and most of the work with complexes has been in the in the sulphonation of
heterocyclic compounds, some of which may be sulphonated using sulphuric acid or oleum, but better yields are often
Mechanism
The mechanistic studies that have been carried out on sulphonations have usually been done on simple aromatic
hydrocarbons. The conclusions from these investigations are summarized below. Mechanistic features of the
sulphonation of heterocycles and ionic compounds such as phenols are given later.
Kort and Cerfontain 5 investigated the homogenous sulphonation of chlorobenzene in aqueous sulphuric acid and they
found a marked decrease in the substrate kinetic isotope effect on the acid concentration was increased from 95 to 97;,
the reaction rate also increased. This could be interpreted by a mechanism involving attack by sulphur trioxide
(perhaps solvated) to form a σ complex, typical of other electrophillic aromatic substitutions, followed by the base
assisted removal of a proton (This is partly rate determining at high acid concentrations).
Cl Cl
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ArSO3H + H2SO4
+ SO3
(or SO3H2SO4)
SO3H H
This is in agreement with earlier work on oleum, which proposed stepwise attachment of sulphur trioxide and a
proton followed by the loss of a proton from the benzene ring6, 12. A similar mechanism is indicated when
sulphur trioxide (in low concentrations) is used as the sulphonating agent. Thus Walsh and Davenport13 used
SO3. dioxan complex in excess of dioxan to sulphonate anisole, and obtained the rate expression.
This expression was explained by the fast addition of sulphur trioxide followed by a slow protonation and base assisted
hydrogen abstraction. Further evidence that sulphur trioxide attacks in this manner is given by the fact that the small
kinetic isotope effect has been determined for the sulphonation of benzene with sulphur trioxide in nitromethane
solvent14.
In high strength oleum and larger sulphur trioxide concentrations, the sulphonation reaction becomes second order in
sulphur trioxide, and the reaction shows no kinetic isotope effect. It has been proposed that in these cases, S zo6 is the
attacking electrophile; this is a cyclic dinner of sulphur trioxide15. However, the kinetics are more usually interpreted as
due to the rapid addition of sulphur trioxide as before to give an intermediate which then rapidly reacts with another
molecule of sulphur trioxide16,17. This new intermediate may then rapidly abstract a proton from the ring yielding a
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H
S
O
O
S
O
O O
The pyrosulphonic acid has never been isolated from the reaction mixture.
Sulphonations have proved to be extremely difficult to study kinetically because of the many competing reactions. In
the sulphonation of toluene, for example, oleum gives all three isomers of the monosulphonic acid, some
disulphonation, sulphone formation, anhydride formation and desulphonation as well as some breakdown of the
aromatic substrate. For these reasons, overall rate constants are of little use in elucidating mechanisms, and recently
there has been a tendency to calculate the partial rate factors for the positions on the aromatic ring. These give a useful
Workers have tended to use slightly deactivated substrates, such as chlorobenzene, for kinetic studies on sulphonations,
as these react slowly and smoothly to give little ortho or meta-sulphonation, and little desulphonation or sulphone
formation, and they are also stable to the strong reagents used.
Sulphonation is an electrophyllic substitution reaction, and shows the same dependence of rate of reaction to
substituents as do most other electroplules. Thus alkyl groups and fluorine increase the rate of sulphonation in
benzene, other halogens decrease the rate, and the metro group deactivates the ring completely7. In fact nitro-aromatic
compounds have been used as solvents in kinetic studies 14,18. Rate constants have been determined for most substituted
benzenes, but unfortunately there has been no uniformity in reaction conditions or reagent strengths, and so no
comparisons are likely to be meaningful. There have, however, been sufficient rate constraints determined in
nitrobenzene at 400c using sulphonic acid to compile the following table (19).(Table 1).
Table 1
Naplthalene 116.7
Meta-xylene 78.7
Toluene 26.1
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4-chloro toluene 15.5
Benzene 10.6
Chlorobenzene 9.5
Bromobenzene 6.7
4-nitrotoluene 1.0
Para-dichlorobenzene 0.98
Nitrobenzene 0.24
An early study(20) in the sulphonation of para nitro toleuene showed a large change in rate constant at 250c when the
reaction strength was varied between 99.4% acid to 2.4% oleum,the reaction being first order in aromatic concentration.
Forty years later, Cowdery and Davies 21 working between 92% acid and 10% oleum, showed that in oleum the reaction
and they calculated the activation energy to be 18kcalmole-1. Kilpatrick et al22 investigated the sulphonation of benzene
in sulphuric acid and found that the reaction obeys the equation.Rate = K’ [Aromatic][H2SO4]2
aH 02
the appearance of the benzene sulphonic acid being followed by U.V absorption spectocopy. The same workers 23 have
studied the sulphonation of mestylane in 12-13.5molar sulphuric acid at 12.30c, and found that simultaneous
Kilpatrick and Meyer24 gave kinetic data for the sulphonation of toluene, ortho, meta- and para-xylenes, and 1,2,4 –
trimethyl benzene under conditions where the reaction goes to completion. Eaborn and Taylor25 have determined the
partial rate factors for the sulohonation of toluene with sulphuric acid containing tri fluoro acetic acid, they are f0 34, fm
42 and fp 112. In the same acid range at 250c, the partial rate factors for homogeneous sulphonation, have been
calculated to be f0 63.4, fm 5.7 and fp 25826. The homogeneous sulphonation of tert-butyl benzene in 86.3% sulphuric acid
at 250c gave partial rate factors calculated in fm 3.0 and fp 5327 . There was no otho-substitution. A comparison of the
partial rate factors for ortho-substitutions at 250c in 86.3% acid for toluene, ethyl benzene, isopropyl benzene and tert
butyl benzene showed the expcted decrease with increasing size of the alkyl group28.
Steric effects in the ortho position are also used to account for the difference in overall rate constants for the
homogeneous sulphnonations of toluene, ethyl benzene, and isopropyl benzene aat 25 0c in 75-95.9% sulphuric acid 29
First order rate constants have bveen calculated for the homogeneous sulphonation of benzene and toluene at 250c in
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82.9% sulphuric acid30 and they were found to be
The reaction rate was found to be first ordedr in aromatic hydrocarbon up to 98% conversion. Kort and Cerfontain 5
have determined the substrate isotope effect in the homogeneous sulphonation of chloro benzene at 250c with 83.4 –
99.6% sulphuric acid. Ko/KH varies from 0.8 in 95% acid to 0.4 in 97%.
In an important investigation into the sulphonation of several nitrated benzene derivatives, and halogenated benzenes,
with sulphur trioxide in nitrobenze, Hinshelwood et al31-33 found that the sulphonation reaction was second order with
respect to sulphur trioxide.Thi variation in kinetics between first order in sulphuric acd and second order in sulphur
In another competitive study, Cerfortain and Telder 14 determined the kinetic isotope effect in the sulphnonation
benzenes with sulphur trioxide in nitrobenzene at 250c as KH/Ko = 1.35 ± 0.16; in MeNo2 KH/Ko = 1.25 ± 0.01.
There has only been one study 34 in a flow system using sulphur trioxide; the reaction with benzene was extremely
rapid and complex. The rate equation was too complex to be useful mechanistically.
a. Benzene
Benzene has been mono sulphonated using all of the more reactive sulphonating agents, such as oleum, sulphur
trioxide, sulphuric acid and chlorosulphonic acid. Disulphonation is not easily brought about, and the yield of the
monosulphunic acid is quite good. Thus a 97% yield is obtained using sulphur trioxide35 and a 90% yield using oleum36.
The disulphonation of benzene is much less facile, and a catalyst is usually necessary in order for a good yield to be
obtained. Reasonable yields were obtained by simply treating benzene with a large excess of 98% sulphuric acid 36; but
a yield of 94% was obtained using trioxide in the presence of a HgO catalyst 38.
b. Aromatic amines
These are thought to react by two different routes, depending on the acid concentration. Media of high sulphur trioxide
concentration, give the sulphonate, which can often be isolated. These then re-arrange to give the ortho-acid para-
sulphonic acids. Thus aniline -2- sulphonic acid is prepared by sulphonating aniline with S03- pyridine in the presence
of excess pyridine at 150-2000C39. Presumably the sulphonate first rearranges to the 4-acid, which then further,
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Under less drastic conditions (i.e. below 800c) in the presence of excess acid or oleum, protonation of the amine occurs
giving a quarternary ammonium salt which is meta-directing with respects to elecrophillic reagents. Thus, sulphonation
of aniline gives a mixture of the 2-, 3- and 4- sulphonic acids, whereas N, N- dimethyl aniline gives a mixture of the 3-
and 4- acids40.
c. Phenols
As for anure, phenoes form sulphates with sulphur trioxide and other sulphonations. A study of the sulphonation of
ClSO3H
Since the activation energies for para-and other substitution only differ by 1.7 kcals mole-1 (para being the larger), both
Phenols may be sulphonated with vigorous reagents and are amenable to the same techniques for increasing sulphonic
acid yield as for benzene. Thus the water produced in the reaction with 93% sulphuric acid has been azeotroped using
ethylene dichloride 42 , but sulphur trioxide complexes give higher yields. Thus the sulphonation of para-
secalkylphenols with sulphuric acid gives 75% yield of the sulphuric acid, but with SO3- dioxan 90% yields were
obtained 43,44.
Careful choice of reagent and conditions make it possible to sulphonate one phenol selectively in a mixture. Thus
traces of phenol were removed from othochlorophenol containing less than 0.2% phenol 45.
Initially the sulphonic acid group is introduced ortho and para to the –OH group, but at high temperatures both
rearrange to give the thermodynamically more stable meta isomer. Thus the sulphonation of the ortho-cresol with
excess sulphuric acid gave only the para isomer at -100c, but at 150oc gave 87% of the meta sulphoric acid 46.
d. Halogen benzenes
Halogeno benzenes usually gives very little ortho-isomer in sulphonations, though both ortho-and para-isomers are
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expected. This may be due to steric or inductive effects. Thus at 250c, 83.4-99.6% sulphuric acid gave 98.8% para, 0.8%
ortho acid 0.4% meta sulphonic acid on chloro benzene 4. Similarly, lodo benzene gave 98.3% para, 1.41% ortho acid and
0.3% meta sulphonic acid with sulphur trioxide in sulphur dioxide 47. However, prolonged heating of chlorobenezene
with 94% acid in a sealed tube at 185-2380c gives 54% meta and 46% parachlorobenezene –sulphonic acid. This is
another example of the para acid rearranging to the more stable meta acid 48.
e. Other derivatives
As would be predicted, nitrobeneze is very difficult to sulphonate, and liquid sulphur trioxide at 100-1500c is used
industrially, yielding almost entirely the meta-isomer 49. This reaction did not respond to iodine catalysis70.
Benzene acid gives the sulphonate with sulphur trioxide in dichloroethane51, but oleum gives mainly the meta-
sulphonic acid. However, iodine catalysis is reported to give a 95% yield of the ortho-sulphonic acid at 17.5 – 1900c 50.
Benzaldelyde is sensitive to oxidation, but oleum gives a reasonable yield of the meta sulphonic acid 52.
A great deal of work has been done on the sulphonation of toluene. Generally, all three isomers are produced with an
increase in temperature favouring the para and to a lesser extent the meta isomer, at the expense of the ortho isomer.
An increase in reagent strength decreases the para yield. Thus Spryskov and Gredin53 showed that the para yield
By careful control of the reaction conditions, therefore, it is possible to obtain a high yield of the para-sulphonic acid.
Thus the sulphonation of toluene with sulphur trioxide in liquid sulphur dioxide gave 96.2% para isomer compared to
91.5% for the usual batch process. Carefully controlled conditions can also give an ortho yield of up to 50%, but for this
a vigorous reagent is needed, such as 98% acid, and this leads to much sulphone formation.
Vigorous conditions, such as high temperature and long reaction times lead to rearrangements via a desulphonation –
resulphonation reaction to give the meta-acid. Thus heating toluene -2, 4- disulphonic acid for 25 hours at 1970c gave a
The action of liquid sulphur dioxide to give such good yields of para-sulphonic acid with sulphur trioxide is not yet
clear, perhaps in some way the dioxide conplexes the trioxide, thus reducing its activity. The low temperature used (-
100c) is not sufficient to account for the great para-dominance. Isomer distributions using sulphur trioxide on tolueme
may shed light on thispoint, but as yet the data is not available.
The sulphonation of toluene is a heterogenous reaction, and apparently when sulphuric acid is used as the
sulphonating agent, most of the sulphonation occurs in this phase, though the possibility that there may be some
sulphonation by sulphur trioxide in the organic phase has not been discounted 55.
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The isomer distributions obtained in sulphonations of toluene are summarized in table 2.
The xylenes have been purified by sulphonation with 80% acid, which sulphonates the meta-isomers almost
exclusively. Extraction with water followed by desulphonation leads to almost pure mexa-xylene 56,57.
Xylene sulphonic acids may also be obtained by the sulphonation of the corresponding acetyl derivative with 85% acid
g. Napthalene
Much work has been carried out into the sulphonation of naphthalene because of the importance of the napthalene
sulphonic acid as dyestuffs intermediates. The usual sulphonating agents are oleum or sulpuric acid, and the attack is
usually on the more election rich 1- position. However, at temperatures above 1000c and with time, the 1- acid
rearranges to the thermodynamically more stable 2- acid 62 . The 1- acid does not rearrange at an appreciable rate at
300c63.
Reagents Temple O P M
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SO3 in CHCl3 53 20 - - 95
The isomer distribution obtained in the sulphonation of naphthalene with chlorosulphonic acid in dicholoroethone is
given in table 3.
-35 5 74 1.8
-25 4 75 4.4
-20 4 85 6.5
-15 3 88 9.3
-10 1 51 10.9
0 2 73 12.0
The pure sodium salt of naphthalene sulphonic acid has been prepared by carrying out the sulphonation in chloro
sulphonic acid in dicholoroethane at -300c with a molar ratio of 1.25 acid : 1 napththalene: 0.5 solvent – under this very
mild conditions; no 2- sulphonic acid is made65. Cerfortain and Telder 66 attribute this preference for 1-substitution to the
difference in enthalpy of activation of the two possible isomers. The difference in partial rate factors decreases with
increasing acid concentration. The same study showed that the sulpho group deactivates the ring to which it is attached
more effectively than the adjacent ring. For this reason, disulphonation leads to a sulphonic acid group in each ring .
67
1- naphthylamine can be tri-sulphonated, the ring carrying the amino group also carrying two of the sulphur groups68.
Hydrolysis leads to the removal of just one sulpho group, and gives a mxture of disulphonic acid.
Similarly, the disulphonation of 2-napththol leads 2- napththol -3, 6- disulphonic acid 69.
The presence of a nitro group in the napththalene ring deactivates the ring to which it is attached. Thus, 1- nitro-
napththalene sulphonates to give a mixture of the 1, 5, 1, 6- and 1, 7- nitro napththalene sulphonic acids 70.
The rules for the poly sulphonation naththalene have been stated by Gilbert 2 as (i) the second sulpho group will not go
ortho, para to the existing sulphno group, and (ii) the second sulpho group renters the unslphonated ring.
Sulphone formation occurs with the sulphonation of naphthalenne 71 as would be expected by analogy with benzene.
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SULPHONATION OF HETEROCYCLES
Pyridine and many of its derivatives cannot be sulphonated at tempetatures below 2000c because of the formation of a
sulphur trioxide complex, but at these higher temperatures the complex rearranges to the 3- sulphonic acid. The
reaction is probably intermolecular. Thus, in a typical reaction, pyridine was sulphonated directly by sulphur trioxide
at 225-2350c in the presence of HgSO4 catalyst to give pyridine -3- sulphonic acid 72 .
An improvement on this procedure is to use excess sulphur trioxide using a mercury catalyst, at 170-180%; the
pyridine:: sulphur trioxide complex first formed (I) is sulphonated in the 3- position by the excess sulphur trioxide. The
N-sulpho group is then removed by hydrolysis to give the pyridine -3- sulphonic acid in good yield 73.
SO3H SO3H
SO3 H2O
+ SO3
+ H2SO4
N N N N
SO3 SO3
II
Pyridine – N- oxide, 2- methyl pyridine and quinoline can be similarly sulphonated. Pyridine – N- oxide has also been
sulphonated with 21% oleum, again using a mercury salt as a catalyst. Refluxing for 22 hours at 220c gives the pyridine
– N – oxide – 3 – sulphonic acid74. Canonical forms such as ( III) indicate that 4- substitution would be expected; the 3-
substitution is explained by prior protonation of the N- oxide, which destroys the resonance with the ring 75.
N N N
O O OH
III
It has been shown that at 3300c pyridine -3- sulphonic acid rearranges to give the thermodynamically more stable 4-
acid 76 . Drastic conditions are required because the reaction probably involves a desulphonation – resulphossnation
process, and both these processes are hindered by the electron withdrawing inductive effect of the ring nitrogen.
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Pyridines which are disubstituted in the 2- and 6- positions with bulky groups cannot form a complex with sulphur
trioxide; thus it is not surprising that 2, 6- di-tertbutyl pyridine is found to sulphonate under very wild conditions
(sulphur trioxide in liquid sulphur dioxide at -100c) to give the 3 – sulphonic acid 77 (22). This is almost the only case of a
sulphonation leading to the introduction of the –SO3H group next to such a large alkyl group. Even the introduction of
a chlorine in the 4- position does not prevent sulphonation in the 3 – position (in about 12% yield) 78. This is surprising
as 4- chloro -2, 6-, lutidine gives only a trace of 3- sulphonic acid after treatment with 21% oleum for 24 hours at 1900c 74.
It might have been expected that 2, 6, ditertbutyl pyridine – 3- sulphur acid would rearrange to the 4- acid under much
milder conditions than required for pyridine – 3- sulphonic acid, because of the steric crowding. However,
sulphopnation of 2, 6 ditert butylpyridine with sulphur trioxide in a sealed tube at 240 – 2500c for 15 hours gives none
Me3C N
Me Me
IV
As would be would be expected, quinoline is sulphonated in the benzene ring than the hetero cyclic ring, as the electron
–withdrawing inductive effect of the nitrogen is increased further by its protonation by the oleum used for the
sulphonation. Qunoline -5- sulphonic acid is the product except in the presence of certain mercury salts, when the 8-
sulphonic acid is formed. 80 3 – methyl – isoquinoline similarly yields the 5 – acid when treated with 50% oleum 81.
4, 4’ – bipyridyl gives a 20% yield of 4, 4’ – bipyridyl – 3,3’, 5,5’ – tetra sulphonic acid when subjected to a drastic
sulphonation (concentrated suphuric acid at 3000c) 82. Similar conditions on 3,3’ bipyridyl gives an 84% yield of 3,3’
Little work has been done as the sulphonation of pyrimidine, but some of its derivatives have been sulphonated and
chlorosulphonated with chlorosulphonic acid 84. The results are summaried in Table 4.
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2-NH2-4-CH3 125 5-sulphonic acid -
b. Pyrrole
Pyrole is more acid resistant than furan, and 2-accetyl – pyrrole can be sulphonated in good yield using 6% oleum 85 but
SO3. pyridine, the reaction being carried out in a sealed tube at 1000c over 5-10hours. At lower temperatures with this
complex, pyrrole gives the unstable N-sulphonic acid 86 which rearranges at higher temperatures to give pyrrole –2-
sulphonic acid.
Sulphonation of pyrrole occurs preferentially in the 2- and 5- positions and, as with furan and thiophene, when these
positions are blocked sulphonation proceeds in the 3- and 4- postions with SO3.pyridine . This contradicts an earlier
87
paper by the same workers 86 where 2, 5 dimethyl pyrrole was stated to be inert to SO3. pyridine even at 1500c.
Indole is similarly acid sensitive and is usually sulphonated with SO3.pyridine to give the 2-sulphonic acid. If this
position is blocked, then sulphonation is difficult to achieve; thus 2- methylindole will not sulphonate with
SO3.pyridine at 1100c 88 which is surprising as 2-phenyl indole gives the 3- sulphonic acid in 95% yield with the same
The preliminary step in these sulphonations appears to be the formation of the N- sulphur derivative, followed by
rearrangement 88 ..
Carbazole is quite stable to strong sulphonating reagents, and ca be sulphonated with oleum. Polysulphonation is quire
common, with up to two sulpho groups in each benzene ring. Again the first stage appears to be the formation of a
sulphanate 90.
Borodkin91 has used chlorosulphonic acid to sulphonate and separate a synthetic mixture of carbazole and anthracene,
the carbazole being more easily sulphonated. Data on the sulphonation of indole and carbazole derivatives are given in
Table 6.
c. Furan
Furan and many of its derivatives are sensitive to acid conditions, and direct sulphonation has been possible only with
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Derivatives Reagent Temp (0c) Products Yield %
- 3.4-(-SO3H)2 11.6
- 3.4-(-So3H)2 12
3,5,(SO3H)2
Derivatives
Indole 88
1-acetyl-indoline93
2-Phenyl 89
IJOARTReagent
Py.SO3
Cl SO3H
Py.SO3
Temp (0c)
120
50-60
120-130
Products
2-SO3H
4-SO3cl
3-SO3H
Yield %
90
54
95
(SO3H)4
PhNme2+ClSO3H - 9-SO3H 86
Thus in one study 96 both furan and coumarone gave only a resinous polymer with sulphuric acid, and tars are the
only product when 2-acetyl furan is treated with sulphuric acid of sulphur trioxide in dichloro-ethane 97.
A thorough investigation has been made of sulphonating agents for furan98. Sulphuric acid gives only tars, while
DMF – Sulphuric acid and pyridine – sulphuric acid complexes do not react, even at 1200c, while excess acid causes
tar formation. Sulphur trioxide yields tars, with traces of sulphonic acids, even when acetic onlydride is used as a
solvent. SO3.pyridine only sulphopnates furan when the two compounds are exactly in a 1:.1 molar ratio; excess
pyridine or traces of sulphur trioxide hinder the reaction.SO3.trimethylamine gives only 15% of furan sulponic acid
after treatment at 1000c for 2 hours, whilst SO3 dioxan is too reactive and only gives tars wth traces of sulphonic
2- furoic acid is remarkable in that it may be sulphonated with sulphur trioxide or chloro sulphonic acid to give 5-
sulpho – 2-furoic acid 99. This indicates that the aromatic ring is very deactivated towards elecetro phillic attack,
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O
H
Furfural, however, shows the usual sensitivity to strong sulphonating agents, and can only be sulphonated in poor
yields by SO3. Pyridine which must be pure 97. Traces of sulphuric acid inhibit the reaction, showing that it is not
simply an electron-withdrawing effect of the carbonyl group that is responsible for the stability of 2-furoic acid.
In general, furan derivatives have to be sulphonated using SO3. pyridine. The complex and the furan deriviative
are heated together in a sealed tube at 1000c, usually for about 10 hours100-102. These sulphonations are summarized
in Table 7.
Table 7:.
acids
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Coumarone 101 Py.SO3 100 2-SO3H -
d. Thiophene
Thiophene is very much more stable to acid conditions than either pyrrole or furan, and has consequently been studied
far more than those heterocycles. However, sulphuric acid still cannot be used as a resinous polymer in formed 96
thiophenes have been sulphonated using fluoro-sulphonic acid, chlorosulphonic acid, sulphur trioxide and various
complexes of the latter, in good yields. With chlorosulphonic acid the stable sulphonyl chloride is usually formed.
Displacement of a substituent in the sulphononation reaction is not common, but a tert-butyl group is displaced in the
sulphonation of 3-tertbutyl thiophene with sulphur trioxide in dichloroethane 105 . 2,5-ditert butyl thiophene
sulphonotes in the 3-position in 75% yield with sulphur trioxide in dichnoethane. The 5-position is sterically very
crowded. Rather surprisingly, this reaction also occurs with SO3.pyridine, a relatively mild sulphonating agent.
Table 8:.
+Disproportionation
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2,5- dimethyl109 Py.SO3 130 3- SO3H 75
ClCH2CH2Cl
*D.SO3 = Dioxan.SO3
**Py.SO3 = Pyridine.SO3
Desulphonation
The desulphonation reaction is not well understood .Industrially, the reaction is widely used, the sulphonic acid group
being removed by boiling with water under pressure, and with acid catalysis. The process involves desulphonation-
resulphonation. Thus, high temperatures and having something to solvate the sulphur dioxide (thereby reducing its
An early study by Baddeley, Holt and Kenner 117 on the desulphonation of meta-cresol sulphonic acid concentration,
proportional to the hydrogen ion activity of the solution, and independent of the nature of the inorganic anion. They
SO3
ArSO3 + H3O Ar H Ar-H + H2OSO3
H O
H
equation (1)
Spryskov and Ovsyuankina118 agree with Baddeley proposing that protodesulphonation proceeds via the ion sulphonic
A more recent study 119 on the desulphonation of benzene sulphonic acid and the toluene sulphonic acid also agrees
with the findings of Baddeley et al, but proposed that the dependence of desulphonation rate upon acid concentration
was more compatible with the protronating species being H3SO+4 instead of H3+O as above.
Both sets of workers agree that the reaction must go via a Wheland-type intermediate such as found in equation (1).
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Partial rate factors had been determined for the protodesulphonation of the toluene sulphonic acid and tert butyl-
benzenesulphoric acid 119. These, indicate that for a particular ethyl group, fo> fp>> fm.
Spryskov and kachurin 120 attempted to find a medium in the rate of protodesulphonation of orthochloro benzene
sulphoric acid using S35 labelled sulphoric acid, but disulphonation interfered with the study, and thus, a well defined
Sulphone formation
The formation of sulphones (compounds of the general formula ArSO2Ar) from the sulphonation of aromatic
hydrocarbons with vigorous reagents in the most troublesome side reaction encountered industrially. Simple diaryl
sulphones are often valueless industrially, and so their formation, and separation from the sulphoric acid, represents a
substantial economic loss. If diaryl sulphones are required, they may be manufactured in very good yield by refluxing
an aromatic sulphonyl chloride with our aromatic hydrocarbon in the presence of a Friedel-Crafts catalyst such as ferric
chloride121,122 . Aluminum trichloride121,123, Titanium tetrachloride122, Bismuth trichloride 124 or Antimony pentachloride
124. This method permits the formation of mixed diaryl sulphones.
Mechanism
In a study on the sulphonation of benzene with sulphur trioxide, Cerfontain and his co-workers16 showed that the ratio
of diphenyl sulphone to benzene sulphonic acid increased with an increase in the initial sulphur trioxide : benzene
ratio. This led to the proposed mechanism in equation (2) with a pyrosulphonate as an intermediate:
H
SO3 H [I]
ArH + SO3 Ar ArSO3SO3H
SO3 Ar
SO3SO3
ArH
equation (2)
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This is in agreement with an earlier paper15 which suggests a similar pyrosulphonate mechanism. The evidence for such
a pyrosulphonic acid intermediate such on( I) in equation (2) is very convincing; for example;: Jolly et al 17 prepared
highly reactive compounds of the type ArSO3 SO3Na (Ar = 4- chlorophenyl or paratolyl) by a peculiar insertion
These pyrosulphonate esters, which cannot lose sulphur trioxide as easily as free pyrosulphonic acid, react readily with
This insertion reaction has also been used to prepare methyl chloropyrosulphonate by the reaction of methyl chloride
with two moles of sulphur trioxide125. This reacts with aromatic compounds to yield sulphones of the general formula
Jolly et al17 suggested that the pyrosulphonic aid cleaves to give a sulphonium ion, which then leads to the sulphone in
equation (3)
ArH
Sulphone
………….. equation (3)
In this case, one might expect sulphone formation to be first order with respect to pyrosulphonic acid, and hence with
the aryl sulphonic acid. However, a careful kinetic study has not yet been undertaken. An investigation on a semi-batch
scale126 indicated that the reaction is indeed first order with respect to the sulphonic acid. Further support for a
sulphonium ion mechanism comes from a study of the reactions of ArSO2OCOCF3127 a mixed anhydride made by
reacting an arylsulphonic acid with trifluoroacetic acid. The anhydride reacts with aromatic hydrocarbons to give
sulphones, probably by the prior loss of CF3COO- but one can not rule out the possibility of a bimolecular reaction in
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which the extremely electron-deficient sulphur atom acts as an electrophyllic centre, and the last step is the loss
CF3COO-.
Just as there is more than one mechanism leading to aromatic sulphonation with sulphur trioxide, so sulphone
formation is similarly complicated. Thus Christen Sen128 has provided tracer evidence for a pyrosulphonic acid
intermediate in sulphone formation in the sulphonation of iodobenzene with sulphur trioxide, but also puts forward
evidence indicating that the sulphonic anhydride also present leads to sulphone formation. The proposed mechanism is
R
R
O
SO2 SO2
O + SO3 RSO2 + RSO3SO3H
O S
SO2 S O O O
R R
O
………………..(5)
Reaction in equation (4) also probably proceeds via a short lived pyrosulphonate intermediate.
This proposal that sulphone formation may go via the sulphonic acid anhydride is supported by the fact that benzene
sulphonic anhydride, benzene and aluminum trichlorodride when refluxed together gave diphenyl sulphone in good
yield129
Tukenaka 126 has calculated the apparent activation energy for the sulphonation of benzene with sulphuric acid in the
temperature range 170-2100c to be 14.8 Kcals mole-1, and that of sulphone formation to be 16.2 kcals mole-1 under the
same conditions. Thus it may be expected that high temperatures would favour sulphone formation and that low
temperatures would favour sulphonation. Diphenyl sulphone has in fact been made industrially by sulphonating
benzene with 95% acid using benzene vapour in a column at 2600c 130.
The direction of the addition is also very important in general; the addition of the hydrocarbon to sulphur trioxide gives
half as much sulphone as the verse procedure 131. This is explained by applying the law of mass action to equation (5).
Industrially, the most important method of reducing sulphone formation is the addition of ionic sulphates or
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bisulphates to the reaction mixture. These have the effect of reversing the decomposition of the pyrosulphonic acid by a
The addition of 0.05 mole % of solid anhydrous sodium sulphate per mole of benzene, for example: reduced sulphate
formation from 24% to 3.5% when sulphur trioxide was used as the sulphonating agent132. It is clear that the anion
rather than the camion is inhibiting sulphone formation, as in the sulphonic acid-sulphonation or benzene. Sodium
bisulphate, potassium sulphate and lithium sulphate all had a marked effect but sodium benzene sulphonate had ion
effect on the amount of benzene formed 126. The effect of addition of sodium sulphate is clearly seen in Table 9133.
Table 9
No of moles of
Of C6H6
0 90 3 24.2
0.001 90 3 21.3
0.05 90 3 15.1
0.10 90 1 9.8
0.25 90 1 5.5
0.50 90 3 1.7
0.50 160 3 17
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*The sulphone is diphenyl sulphone -3,3’ disulphonic acid.All the above results are for 2.5 moles So3 per mole of C6H6.
In sulphonations, many sulphur trioxide, much smaller amounts of sodium sulphate are needed to reduce sulphone
formation than for 65% oleum-sulphonations 132. Thus it may be that sulphone formation occurs mainly in the organic
phase and it is the sulphate ion concentration in this phase which is important in reducing sulphone formation. In the
case of oleum sulphonations, the sulphate ion would be ,mainly in the acid phase.
Rueggeberg and his co-workers131 have shown that organic aids considerably decrease sulphone formation. They
Steps 7(a) and (c) are thought to be more important..It is known that sulphur trioxide reacts with acetic acid at below 00c
to form acetyl sulphate compounds analog to RCOOSO3H in equation (7)134 and that the readily sulphonates aromatic
No systematic study to correlate sulphone formation with the strengths of sulphur trioxide complexes has been carried
out. The more reactive of these complexes, for example, those with DMF or bis – (2-chloroethyl) ether may prove to be
useful in keeping sulphone formation down because of their easily regulated reactivity.
Heterocyclic compounds do not yield sulphones as by-products of sulphonations. This may be because only mild
reagents can be used to sulphonate them. So the sulphur trioxide concentration is never high enough to allow
pyrosulphonate formation; this is because all the sulphur trioxide in the system is rapidly removed by the formation of
Chloro sulphonation
The chloro sulphonations of aromatic compounds is of great industrial importance, for instance, sulphonyl chlorides
are used in the preparation of sulphonates and sulphones; many of which have medicinal uses.
The usual reagent used to introduce the – SO2Cl group is chlorosulphonic acid which has the advantage of being cheap.
Mechanism
Equimolar quantities of chlorosulphonic acid and the aromatic compound yield the sulphonic acid in good yield,
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especially at low temperatures. It is likely, therefore, that in the preparation of aromatic sulphonyl chlorides by using at
least two moles of chlorosulphonic per mole of aromatic compound,the sulphonic acid is formed as an intermediate.
Harding135 proposed the following mechanism for the reaction with toluene in equations (8) and (9)
Equation (8) might be expected to go to completion as the HCl should be evolved. However, it is quite common for a
solvent to be used to facilitate easy stirring and HCl is soluble in many organic solvents. Equation (9) is an equilibrium
which may be disturbed. Lukashevich 8 proposed a mechanism which involve a pyrosulphonate intermediate, as in the
sulphonatiopn of aromatic compounds with sulphur trioxide. He proposed the reaction scheme found in equations
10 – 13.
It was found that the addition of sulphonic acid or hydrochloric acid reduced the yield sulphonyl chloride and
sulphones, which was explained by suggesting the pyrosulphonate intermediate, ArSO3SO3H, was decomposed by
strong acid, thereby hindering reaction in equations (12) and (13). Harding135 would have explained this by saying the
Lukashevich also found that sulphonic acid anhydrides were formed in the reaction of chlorosulphonic acid and with
halogenated aromatic hydrocarbon; this may provide a second mechanism whereby sulphonates are formed in these
chlorosulphonation reactions . The work of Christen Sen refers128 Sulphonic acid anhydrides tend to be stable in
strongly acid media and this would explain why one gets less sulphone formation when acids are added.
The reaction in equation (9), being an equilibrium reaction has attracted much interest in the possibility of distutrbing
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the equilibrium to achieve higher yields of sulphonyl,halides. This would be more economical than increasing the
chlorosulphonic acid concentration. Two methods have been used to remove sulphoric acid produced. In one of these136
, carbon tetrachloride is added to the reaction mixture; this is oxidised by sulphuric acid to give phosgene in equation
(14)
This method has the obvious disadvantage that phosgene is highly toxic. The second method is to add sodium chloride
or sodium sulphate 7. The sodium chloride reacts with the sulphoric acid to give sodium sulphate and HCl, and the
sodium sulphate gives sodium bisulphate. Using 0.1 mole sodium chloride as an additive, 2.6 moles of 92%
chlorosulphoric acid on 1 mole of toluene gave a total yield of 87% ortho-and para-toluene sulphonyl chlorides137.
However, the reaction took a total of 24 hours, far longer than is economial industrially.
de Jong 138 has increased the yield of sulphonyl chloride by extracting it with a haloalkane or cycloalkane as it is
formed. Thus by agitatig orthotoluene sulphoric acid with chlorosulphonic acid in carbon tetrachloride for 1 hour at
400c, and separating the organic and aqueous layers and further extracvting the aqueous phase; and finally distilling the
carbom tetrachloride off under reduced pressure, an 89% yield of ortho toluee sulphonyl chloride waso btained.
Using 2.5 moles of chlorosulphonic acid per mole of sodium para toluene sulphonate, the maximum yield of sulphonyl
chloride was only 80% 139 and it may be worthwhile industrially to consider other methods of chlorinating sulphonic
acids. For instance, DMF catalyses chlorination with thionyl chloride ,and generally this method gives excellent yields
of sulphonyl chlorides in one or two hours. In a patent140 describing the use of DMF, sulphur trioxide to sulphonate
toluene, a yield of 70% para toluenesulphyonyl coloride was obtained and the total yield of sulphonyl chlorides was
not stated.
Conclusion
There are well over a thousand importance publications on this work this century, with the result that this
survey has had to be very selective and concentrated on those papers of theoretical or great industrial
importance. For this reason indirect methods of introducing the sulphonic acid group such on the oxidation of
sulphides or the use of diazoniun salts have not been considered.
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1. Flint, G, in Kirk and Othman (Eds) Encyclopedia of Chemical Technology, 13 501 (interscience, New York) (1954)
2. Gilbert, E.E in “sulphonation and related reactions”, interscience, New York (1965)
5. Kort, C.W.F and Cerfontain, H., Rec. Tran. Chim, 86, 865, (1967)
7. Bradley, J.A., Perkins, P., and Polisin, J.J., 138th meeting, A.C.S., New Yotrk (1960).
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8. Lukashevich, V.O., Doklady Akad. Naut. SSSR, 112, 872 (1957)
9. McCarter, W.S.W., in Kirk and Othman (Eds), Encyclopedia of Chemical Technology, 6, 734, interscience, New
York (1951)
11. Spryskov, A.A, Sb. Statei Obshc. Khim. 2 878 (1953) From chem. Abstr. 49 6894 (1955)
13. Walsh, J.A., and Davenport, D.A, Abs., 134th metting A.C.S., (1958).
14. Cerfontain, H, and Telder, A., Rec. Trav. Chim. 84, 1613 (1965)
15. Michael, A, and Weiner N., J. amer. Chem. Soc., 58, 294 (1936)
16. CeRfontain, H, Telder, A, and Vollbracht, Rec. Tran. Chim,, 83 1103. (1964)
17. Joly R, Bucourt, R., and Mathew, J., Rec. Trav. Chim., 78, 527 (1959)
18. Kachurin, 0.1 and Spryskov, Tr. Vses. Mezhruz, Nauchn. Techn. Konf. po Vopr. Sintezza i Primeneniya Organ.
19. Stubbs, F.J., Williams. C.D., and Hinshelwood C.N, J. Chem. Soc 1065 (1948)
21. Cowdrey, W.A and Davies, D.S, J. Chem. Soc., 1871 (1949)
22. Kilaptric, M..; Meyer M.W and Kilpatrick, M, J. Phys. Chem 64 1433 (1960)
IJOART
24. Kilpatric, M., and Meyer, M.N; J. Phys. Chem. 65, 530 (1961)
26. Vollbracht, L., Cerfontain, H, and Sixma, F.L.J., Rec. Trav. Chim. 80, 11 (1961)
27. Arends, J.M and Cerfontyain H., Rec. Trav. Chim., 85, 93 (1966)
28. De Vries, H., and Cerfontain H, Rec. Trav. Chim. 85, 93 (1966)
29. Kaandorp, A.W, Cerfontain H, and Sixma, F.L.J., Rec. Trav. Chim. 82, 113 (1963)
32. Vicary, D.R., and Hinshelwood, C., J. Chem. Soc., 1372 (1939)
33. Wadsworth , K.D and Hinshelwood, C.N, J. Chem. Soc., 469, (1940)
35. Leiserson, L., Best, R.W and L:e Baron, R, Ind. Eng. Chem., 40 508 (1948)
IJOART
40. Alexander, E.R., “Principles of Ionic Organic reactions,” Wiley, New York (1950)
43. Romadane, I. and Kochetkava E.A, Latijas PSR Zinatnu Akad. Vestis Khim. Ser., 51 (1964) reported in Chem. Abstr
46. Tatibouet, F, and Setton. R, Bill. Soc. Chim. France, 382 (1952)
48. Spryskov, A.A., Zh. Obshch. Khim., 30, 2449 (1960) reported in Chem. Abtr., 55 , 12336 (1961)
49. Gilbert, E.E., in “sulphonation and related reactions,” Interscience,New York, 82 (1965
50. Ray., J.N, and Dey M.L, J. Chem. Soc., 1405 (1w920)
53. Spryskov, A.A ad Gredin, B.G., Zh. Obshch. Khim., 33, 1082 (1963) reported in Chem. Abstr., 59 (1963)
54. Potapova, T.I and Spryroskov A.A., Izv. Vyssh. Ucheb. Zaved. Khim. Tekhnol., 10 885 (1967) reported in Chem.
55. Cerfontain, It., Sixma, F.L.J., and Vollbracht, L., Rec. Trav. Chem., 83 226 (1964)
IJOART
56. Ger. Pat., 811,834, (1951)
58. Cerfontain, H., Sixma F.L.J., and Vollbtracht, Rec. Trav. Chim., 82. 659, (1963)
59. Wanders, A.C.M and Cerfontain. H, Pro. Chem. Soc., 174 (1963).
60. Klaver and Oda, R.J. Prekt. Chem., 143, 139 (1935)s
62. Spryskov,A.A., J. Gen. Chem. USSR, 16, 2126, reprted in Chem Abstr. 42, 894 (1948)
63. Ito, A., Kogyo Kagoku Zasshi, 62 549 (1959) reported in Chem abstr. 57, 8512 (1962)
64. Gredin, B.G, Spryskov. A.A ad Loksino, E.G, Izu,Vy ssh. Vcheb. Zavedg. Khim. Khim. Tekhnol. Inst. 10, 774 (1967),
66. Cerfontain H., and Telder, A, Rec. Trav. Chim., 86r, 527 (1967
67. Fierz-David, H.E and Richter, C., Helv. Chim. Acta., 28,257 (1945)
69. Hashimoto, S, and Kotone, A, Doshisha Diagaku Kenkyu Hopkoku, 7, 89 (1966). Reoported in Chem. Abstr., 67,
3067 (1967)
70. Karavaev, B.I. and Paramonovova, V,V Izu. Vyssh. Vcheb. Zaved. Khim. Khim. Tekhnol. Inst., 10, 57 (1967),
IJOART
71. Ito, A., Kogyo Kagaku Zasshi, 62, 844 (1909), reported in Chem. Abstr. 57, 8512 (1962)
74. Evans, R.F and Brown, C., J. Org. Chem., 27, 1329 (1962)
75. Moshe, H.S, and Welch, F.J, J. Amer. Chem. Soc., 77, 2902 (1955)
76. den Hartog, H.J, van der Plas, H.C and Buurman, D.J., Rec. Trav. Chim., 77, 963 (1958)
77. Brown, R.C and Kanner, B.,J. Amer. Chim. Soc., 75, 3 865 (1953)
78. Van der Plas, H.C, and den Hartog, Tetrahedron Letters, 13 (1960)
79. Van der Plas, H.G, and Crawford, T.H, J.Org.Chem., 26 2611 (1961)
81. Elder field, R.C., Lagowski, J.M, McCurdy, O.L, and Wythe, S.L, J.Org. Chem., 23, 435 (1958)
82. Ostroshchenko, O..S., Sadykov, A.S., and Ziyaeu, A.A., Zhur. Obshch khim., 31, 678 (1961)
83. Ostroshchenko, O.S., Kurbatov, O.S, and Sadykov, A.S, Nauch. Tr. Taskent. Gos, Univ., No 286, 88 (1966), reported
84. Khromov, N.V, and Karlinskaya, R.S., Zhur. Obshch. Khim., 24 2212, (1954) reported in Chem. Abstr., 50, 355 (1956)
85. Terent’ev, A.P and Yanovskaya, Zhur. Oshch. Khim., 19, 2118 (1949), reported on Chem. Abstr., 44, 3973, (1950).
86. Ibid, 19 538 (1949) reported in Chem. Abstrf., 43, 7015, (1949)
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87. Ibid, 19 1365 (1949), reported in Chem. Abstr., 44, 1095 (1950)
88. Ibid, 19, 781 (1949), reported in Chem. Abstr., 44, 1095 (1950)
89. Ibid, 21, 1295 (1951), reported in Chem. Abstr., 46, 2048 (1952)
90. Borodkin, V.F., J. Applied Chem USSR, 23, 803, (1950) reported in Chem. Bstr., 46, 8089 (1952)
92. Terent’ev, A.P and Yanovaskaya, I.A., Zhur. Oshch. Khim. 21, 281 (1951) reported in Chem. Abstr., 45, 7025 (1951)
93. Terent’ev, A.P and Preobrazhenskaya, M.N, Zhur. Oshch. Khim., 30, 1218 (1960), reported in Chem. Abstr., 55, 511
(`1961)
94. Karpukhin, P.P and Levochenko, O.I, Kghim. Piom. Namu. Tekhol. Zb., 18 (1963), treported in BCem Abs5tr., 59,
7461 (1963)
95. Borodkin, V.F, and Mal’kova, T.L, Zhur. Priklad. Khim. 21, 849 (1948), reported in Chem. Abstr., 43, 6205 (1949)
96. Jurusek, A, and Kovak, J , Sb. Prac. Chem. Fak. SVST, 41, (1961)0 rerported oin Chem. Abstr., 58, 2420 (1963)
97. Terent’ev, A.P, Kazitsyna, L.A. and Turouskaya, A, Vestrik Moskou. Uniu., 3, 159 (1948) reported in Chem. Abstr,
44 5862, (1950).
98. Terent’ev, A.P, Kazitsyna, L.A. and Suvorova, S.E. Zhur. Obshch. Khim., 19, 1951 (1949), see in Chem. Abstr., 44,
1954, (1950)
100. Terent’ev, A.P, Kazitsyna, L.A. and Suvorova, S.E. Zhur. Obshch. Khim., 18, 723 (1948) reported in Chem. Abstr., 43
215 (1949).
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101. Ibid, 19, 531, (1949)s reported in Chem. Abstr., 43, 7015 (1949)
102. Kazitsyna, L.A, Vestnik. Moscov.UMV., 109 (1947) repoted in Chem. Abstr., 42, 3751 (1948).
103. Jurasek, A., Kovac, J, Kada, R., and Frim, R., Chem Zvesti. 18 214 (1964) repoeted in Chem. Abstr., 61, 3054 (1964)
104. Wenland, R.T and Smith, C.H., Proc. North Dakota Acad. Sci., 2, 40 (1949) reported in Chem. Abstr., 43, 5021, (1949)
105. Gol’dfarb, Y.L., Antik, L.V and Konstatinov, P.A., Izvest. Akad. Nauk. SSSR Otdel. Khim Nauk, 624 (1956),
106. Blatt, A.H, Bach, s and Kresch, L.W., J. Org. Chem., 22, 1694 (1957)
108. Terent’ev, A.P, and Kadatskii, Zhur. Obshch. Khim., 22,153 (1952) reported in Chem. Abstr., 46, 11178 (1952).
109. Ibid, 23, 251 (1953), reported in Chem. Abstr, 146, 11178 (1952).
111. Terent’ev, A.P, and Kadatskii, G.M., Zhur. Obshch. Khim., 12, 21, 1524 (1951) reported in Chem. Abstr., 46, 2536
(1952).
113. Truce, W.E, Lotspeich, F.J., J. Amer. Chem. Soc., 77, 3410 (1955)
114. Buzas, A, and Teste, J, Bull. Soc. Chim. France, 793 (w1960)
115. Lew, H.Y. and Nolter, C.R., J. Amer. Chem. Soc., 72, 5715 (1950)
IJOART
116. Sone, C, and Natsuki, Y, Nippon Kagaku Za schi, 83, 496, 1962 reorted in Chem. Abstr, 59, 3862 (1963)
117. Badddley, G, Holt, G, and Kenner, J., Natyure, 154, 361 (1944)
118. Spryskov, A.A., and Ovysyankina, Sb. Statei Obshch. Khim., 2, 882 (1953), reported in Chem. Abstr., 49, 6894 (1955)
119. Wanders, A.C.M and Cerfontain, H, Rec. Trav. Chim., 86, 1199 (1967)
120. Spryskov, A.A, and Kachurin, O.I, J. Gen. Chem. VSSR, 28 1693 (1958)
123. Sen, A.B, and Roy, A.K, J. Ind. Chem. Soc., 33, 687 (1956)
126. Takenaka, J., Kogyo Kugaku Zasshj, 70 483 (1967) reported in Chem. Abstr., 67, 7682 (1967)
127. Bourne, E.J., Stacey, M., Fatlow, J.C./, and Tedder, J.M., J. Chem. Soc., 718 (1951)
131. Rueggeberg, W.H.C., sauls, T.W., and Norwood, S.L., J. or g Chem., 20 455 (1955)
IJOART
133. Shestov, A.P and Osipova, N.A., J. Gen. Chem. USSR, 29 591 (1959)
137. Kissin, B., and Pomeratsev, Khim, Nauka ; Prom, 2,809, (1957) reported in Chem. Abstr., 52, 11770 (1958)
139. Shivjiana, B.H and Shah, R.C., J. In. Chem. Soc., Ind. and News Ed., 17, 127 (1954)