Proc. Natl. Acad. Sci.

USA
Vol. 74, No. 10, pp. 4121-4125, October 1977

Chemistry

Electrophilic mercuration and thallation of benzene and substituted

benzenes in trifluoroacetic acid solution*
(electrophilic substitution/selectivity)

GEORGE A. OLAH, IWAO HASHIMOTOt, AND HENRY C. LINtt

Institute of Hydrocarbon Chemistry, Department of Chemistry, University of Southern California, Los Angeles, California 90007; and the Department of
Chemistry, Case Western Reserve University, Cleveland, Ohio 44101

Contributed by George A. Olah, July 18, 1977

ABSTRACT The mercuration and thallation of benzene and

substituted benzenes was studied with mercuric and thallic
trifluoroacetate, respectively, in trifluoroacetic acid. With the
shortest reaction time (1 sec) at 00, the relative rate of mercuration of toluene compared to that of benzene was 17.5, with
the isomer distribution in toluene of: ortho, 17.4%; meta, 5.9%;
and para, 76.7%. The isomer distribution in toluene varied with
the reaction time, significantly more at 25 than at 00. The
competitive thallation of benzene and toluene with thallic trifluoroacetate in trifluoroacetic acid at 150 showed the relative
rate, toluene/benzene, to be 33, with the isomer distribution in
toluene of: ortho, 9.5%; meta, 5.5%; and para, 85.0%. With
increasingly higher reaction temperatures in both mercuration
and thallation reactions of aromatics, isomerization (both intramolecular and intermolecular) within the relevant ortho- and
para-metallated intermediate ions and/or of the isomers becomes more important. Competitive rates and isomer distributions of mercuration and thallation of benzene and substituted benzenes were also determined. The predominant para
substitution in both mercuration and thallation of methylbenzenes reflects, besides some steric factors, the strong stabilizing
effect of para methyl groups on the arenium ion intermediates.
Under predominantly kinetically controlled conditions, no
anomalous increase in the amount of meta substitution was
observed.

The mercuration of aromatic hydrocarbons with mercuric

trifluoroacetate in trifluoroacetic acid at 250 has been studied,
predominantly by Brown and coworkers (1-3). The rate ratio
of toluene to benzene (kT/kB) was found to be 9.89 and the
isomer distribution in toluene was: ortho, 12.2%; meta, 8.6%;
and para, 79.2%. From these results, as well as from their preceding studies in acetic acid solution with perchloric acid catalyst giving kT/kB = 3.6-7, and 12-16% meta isomer, it was
concluded that the relatively high meta isomer ratio observed
was due to the high electrophilic reactivity of the mercurating
agent causing the observed low selectivity substitutions. These
results were correlated by the so-called Brown selectivity relationship (for a review, see ref. 4).
It should be pointed out that, in their original paper on
mercuration of toluene and benzene, Brown and Nelson, (5)
extending the claimed quantitative selectivity relationship
governing isomer distributions in aromatic substitution, commented on the preceding work of Klapproth and Westheimer
(6) who found that, in glacial acetic acid with perchloric acid
as catalyst, toluene was mercurated by mercuric acetate at 250
to give 6% of the meta isomer. Brown and Nelson claimed to
have observed 12% meta isomer under similar conditions and
stated "we are, however, unable to account for the differences
between the values of the meta isomer." In the former case (6),
a precise radiochemical technique was used in establishing
orientation, whereas infrared analysis was utilized in the latter.
Comparison of the experimental sections of Brown and Nelson's
and Klapproth and Westheimer's papers, however, indicates
that the claim of reinvestigation "under similar conditions" is
incorrect. Klapproth and Westheimer carried out their exper4121

iments at 250 and quenched the mixtures after 5 min, whereas

Brown and Nelson carried out the reaction for 6.5 hr. In subsequent work, in view of the importance of both the mechanistic
and practical implications of the orientation-rate correlation,
Brown and McGary (7), carried out a more detailed study of
the mercuration reaction. They concluded: "A redetermination
of the isomer distributions and relative rates indicates excellent
agreement with the linear relationship of orientation and relative rate." They recognized, however, that the isomer distributions change with time but still claimed that the corrected
meta isomer distribution in the mercuration of toluene is 9.5
+ 0.5% and remarked, "there remains a relatively minor disagreement with the values reported by Klapproth and Westheimer (6% meta) for which we are unable to account."
In preceding work (8) we have suggested that, regardless of
the substrate selectivity in electrophilic aromatic substitutions
(which generally can be most conveniently expressed by kT/kB
rate ratios), the regioselectivity (positional) of the reactions
remains high, with usually predominant ortho-para substitution, the amount of meta isomer being 2-5%.
We considered it possible that the reported relatively high
meta isomer ratio observed in preceding studies of mercuration
of toluene (as well as related alkylbenzenes) was still the result
of ongoing faster isomerization and/or disproportionation of
the ortho and para isomers, compared to the more stable meta
isomer (7) or related rearrangements in the a-complex intermediates of the reactions. These would fully explain the disagreements with Klapproth and Westheimer's work. Consequently, it appeared desirable to reinvestigate in detail the
mercuration of benzene and substituted benzenes under predominantly kinetically controlled conditions, minimizing the
possibility of isomerization and disproportionation affecting
the results.
The thallation of benzene and substituted benzenes with
thallium trifluoroacetate in trifluoroacetic acid, the mechanism
of which was considered to be similar to that of related mercurations (9-11), was also studied under similar conditions.
MATERIALS AND METHODS
Materials. Benzene, toluene, and alkylbenzenes were of
highest available purity. Trifluoroacetic acid (Cationics, Inc.)
was obtained in sufficient purity to be used without further
purification (boiling point 730). Mercuric and thallium trifluoroacetate were commercial materials (Aldrich Chemical Co.,
Inc.).
Abbreviation: kT/kB, ratio of reaction rates for toluene and benzene.
* Paper no. 40 in the series "Aromatic Substitution." Paper no. 39 was
Olah, G. A., Pelizza, F. Kobayashi, S. & Olah, J. A. (1976) J. Am.
Chem. Soc. 98,296.
t Visiting Scientist from the Wakayama Technical College, Japan.
* Senior Research Associate (1974-1975).

4122

Chemistry: Olah et al.

r

Proc. Natl. Acad. Sci. USA 74 (1977)

-

--

Table 1. Gas/liquid chromatographic parameters

Conditionst of
retention

~G

Quench

FIG. 1. Flow-quenching apparatus for the mercuration of

polymethylbenzenes. Two 50-ml syringes (A and B) are driven by a
syringe pump (C; Sage Instruments, model 351). The separate solutions came together via two flexible Teflon tubes (D and E, inside
diameter 1.4 mm; length, 60 cm), mix at F, react during passage G, and
are quenched at the end of G.

Competitive Mercuration of Benzene and Substituted

Benzenes. Mercuric trifluoroacetate (25 ml of 0.2 M solution
in trifluoroacetic acid) was added rapidly to 25 ml of 1 M solutions of the aromatics in the same solvent with vigorous stirring, both precooled and kept at 00. After specific time intervals, the reaction mixture was quenched with aqueous sodium
bromide, maintaining a bromide ion to mercuric ion ratio of
3:1. The precipitated arylmercuric bromides were filtered and
thoroughly dried under reduced pressure. Then, the mixture
of arylmercuric bromides was slowly treated with bromine in
chloroform at 00 until a permanent red color developed. Stirring was continued for 5 hr at 0 and then for an additional hour
at room temperature. Conversion of arylmercuric bromides to
the corresponding bromoarenes under these conditions was
found to be quantitative for all practical purposes (the slower
conversion of the parent phenylmercuric bromide without
raising the temperature to ambient is not always quantitative).
The reaction mixture was washed with sodium bisulfite solution
and water and then dried over sodium sulfate. Bromoarenes
were subsequently analyzed by gas/liquid chromatography.
Competitive Mercuration of Polymethylbenzenes. The
rates of mercuration of polymethylbenzenes are so fast that it
is difficult to carry out the reactions by the usual methods.
Therefore, a modified flow-quench apparatus (12) was used
to allow short reaction times (of the order of 1 sec) (Fig. 1).
Quenching was with aqueous sodium bromide surrounded by
ice. The quenched products were worked up, brominated with
bromine in chloroform, and then analyzed by gas/liquid

chromatography.
Competitive Thallation of Benzene and Substituted
Benzenes. The thallations were carried out with exclusion of
light, in a manner similar to that for the mercurations. The
reaction mixture was quenched in aqueous sodium chloride,
and the solution was evaporated under reduced pressure until
a white solid remained. The bromination of arylthallium
chlorides was performed with bromine in carbon tetrachloride
according to the procedure described by Wright (13). Product
bromoarenes were analyzed by gas/liquid chromatography as
in the case of mercuration.
Analytical Procedure. All products were analyzed by gas/
liquid chromatography, with a Perkin-Elmer model 900 gas
chromatograph equipped with a hydrogen flame ionization
detector and either open tubular capillary columns or a packed
column. Peak areas were calculated with the Infortronics model
CRS-100 electronic printing integrator.
Characteristic retention times of bromo compounds along
with type of column and conditions are listed in Table 1. Authentic samples of pure substituted bromobenzene isomers were
available in our laboratory from previous work. A 12-ft 4,4'azoxyanisole-packed column was utilized at 1300 to achieve
complete separation of bromotoluene isomers (14).

Column* Column Time, min

D
I
5.9
I
D
10.0
I
D
11.0
D
I
12.3
D
I
10.3
D
I
12.0
D
I
14.2
D
I
11.7
D
I
13.8
p -Bromoisopropylbenzene
I
D
18.3
o-Bromo-tert- butylbenzene
D
I
16.2
m -Bromo-tert- butylbenzene
D
I
19.3
D
p -Bromo-tert-butylbenzene
I
22.3
I
C
2.9
4-Bromo-o-xylene
4-Bromo-m-xylene
C
I
2.7
I
3.0
2-Bromo-p-xylene
C
III
3.2
Bromoesitylene
C
4-Bromo-1,2,3-trimethylbenzene
I
5.1
C
5-Bromo-1,2,4-trimethylI
benzene
4.8
C
5-Bromo-1,2,3,4-tetramethylbenzene
II
C
4.5
4-Bromo-1,2,3,5-tetramethylII
benzene
4.5
C
Bromodurene
III
C
6.6
III
17.8
Bromopentamethylbenzene
C
o -Bromofluorobenzene
B
IV
12.2
B
IV
m-Bromofluorobenzene
9.8
B
IV
10.5
p-Bromofluorobenzene
B
V
o -Bromochlorobenzene
15.1
B
V
13.0
m -Bromochlorobenzene
B
V
13.2
p-Bromochlorobenzene
B
V
25.8
o -Dibromobenzene
B
V
m -Dibromobenzene
21.9
V
22.2
B
p -Dibromobenzene
VI
A
10.9
o-Bromoanisole
VI
A
9.6
m-Bromoanisole
VI
A
10.1
p-Bromoanisole
* A, stainless steel open tubular column, 150 ft X 0.01 inch, wall coated
with butanediol succinate; B, stainless steel open tubular column, 150 ft X 0.01 inch, wall coated with m-bis(m-phenoxyphenoxy)benzene modified with 20% Apiezon L grease; C, stainless steel
packed column, 12 ft X 1/8 inch, with solid support 80-100-mesh
Chromosorb W and liquid phase 1.75% butanediol succinate; D,
stainless steel packed column, 12 ft X 1/8 inch, with solid support
80-100-mesh Chromosorb W and liquid phase 15.0% 4,4'-dimethoxyazoxybenzene.
t Column conditions [column temperature, C (carrier gas, helium,
pressure (psi) or flow rate (ml/min)]: I, 130 (20 ml/min); II, 140 (20
ml/min); III, 145 (20 ml/min); IV, 950 (20 psi); V, 1300 (20 psi); VI,
1500 (20 psi).

Bromo compound
Bromobenzene
o-Bromotoluene
m-Bromotoluene
p -Bromotoluene
o-Bromoethylbenzene
m -Bromoethylbenzene
p-Bromoethylbenzene
o -Bromoisovronvlbenzene

The apparent decrease of kT/kB with time is accompanied

by an increase in the amount of the ortho and meta isomers at
the corresponding expense of the para isomer. The possible
isomerization (transmercuration) in the involved reaction intermediates, although not necessarily of the arylmercury trifluoroacetate products, was not fully recognized previously
when limited product isomerization was only considered. We
are forced to conclude that the higher proportions of the meta
(and ortho) isomer reported previously may be a result of the
isomerization (disproportionation) of the kinetically favored
initially formed para and ortho arenium ions, compared with
the thermodynamically more stable meta substituted ions.

Chemistry: Olah et al.

Proc. Nati. Acad. Sci. USA 74 (1977)

Table 2. Variation of kT/kB for mercuration of benzene and

toluene and of isomer distribution in toluene with reaction
time at room temperature (22)*
Isomer distribution, %
Time,
Ortho
Meta
min
Para
kT/kB
0.15 sec
0.91 sec
1
2
3
6
15
160

15
15

21.3
23.7
23.3
26.6
30.0
30.2
32.5
37.4

14
13
11
10
10
8

* Concentrations: total

71.8
68.7
68.8
64.7
60.9
60.1
57.4
50.0

6.9
7.6
7.9
8.7
9.1
9.7
10.1
12.6

[ArH], 1.00 M; [Hg(OCOCF3)2], 0.10 M.

RESULTS AND DISCUSSION

Mercuration. We first restudied the competitive mercuration
of toluene and benzene with mercuric trifluoroacetate in trifluoroacetic acid at ambient room temperature (220). [The rates
of mercuration of monoalkyl- and polymethylbenzenes with
mercuric acetate in acetic acid have been determined (15).] The
products were precipitated as aryl mercuric bromides, filtered
off, and then converted by bromination into bromobenzene and
the corresponding bromotoluenes, which were analyzed by

gas/liquid chromatography.

Hg(OCOCF)
+

Hg(OCOCF3)2

riiiaq.NaBr
Br

HgBr
Br,

min CHC1.
Because the mercuration of benzene and alkylbenzene in
trifluoroacetic acid is fast, it was considered necessary to use
a flow-quenching apparatus (12) to allow proper mixing of the
reagents before reaction.
The relative rates and isomer distributions in the competitive
mercuration of toluene and benzene at 220, summarized in
Table 2, show the variation of the data with reaction time, as
well as the difficulties one can encounter due to the lack of kinetic control when intermolecular and/or intramolecular
isomerizations affect the data.
CH3

CH3

CH3
etc.
~~~~~~H

~~

__

HAHgOCCF3

X+
HgOCCF3

0~~~~

HgOCCF,
0

The ready mercury shifts in arenemercurenium ions was

previously demonstrated in our studies under stable long-lived
ion conditions.
Because of the changing isomer distributions encountered
in the mercuration of benzene or toluene at 220, we next studied
the reaction at 0 (the lowest practical temperature attainable)
to slow down the isomerization processes.
The amount of meta isomer in the mercuration of toluene
was 5.9% with the shortest reaction time (1 sec) studied at 00,
compared to the lowest proportion of meta isomer, 6.9% ob-

4123

Table 3. Competitive mercuration of monosubstituted benzenes

with mercuric trifluoroacetate in trifluoroacetic acid at 00
with 2-sec reaction time*
Isomer distribution, %
Ortho
Meta
Para

ArH
kArH/kB
Benzene
1
Toluene
18
20.6
6.4
73.0
Ethylbenzene
15
2.3
3.5
94.2
14
Isopropylbenzene
5.4
0.6
93.9
tert-Butylbenzene
10
0
8.4
91.6
Fluorobenzene
0.24
27.6
0.2
72.2
Chlorobenzene
0.03
27.3
0.1
72.6
Bromobenzene
0.2
18.7
1.7
79.6
Anisole
0.2
860
18.8
81.1
* Concentrations: total [ArH], 1.0 M; [Hg(OCOCF3)2], 0.1 M.

served at 220 (kT/kB = 18; 17.4% ortho, 5.9% meta, and 76.7%
para). There was no significant variation of kT/kB and only a
small variation of the isomer distribution (particularly of the
ortho/para ratio) with reaction times of up to 60 min, when
kT/kB = 18 with an isomer distribution of 25.6% ortho, 7.7%
meta, and 67.2% para.
Consequently, in further studies the mercuration of monosubstituted benzenes with mercuric trifluoroacetate in trifluoroacetic acid was carried out at 00 in order to minimize the
possible effect of isomerization (disproportionation) on the
isomer distributions and kT/kB, and the competitive experiments were performed with the shortest feasible reaction times
(2 sec). The data obtained are summarized in Table 3.
In the mercuration of monoalkylbenzenes, a decreasing order
of the relative reactivities (Me > Et > i-Pr > t-Bu) was observed, accompanied by an increase of meta substitution and
a decrease of ortho/para isomer ratio.
The mercuration of polymethylbenzenes was also studied
by the competitive method with reaction times of 2 sec at 00.
The data were compared with the relative stabilities of
the corresponding ir- and a-complexes in order to show a
comparable trend indicative of the rate-determining step (16).
The relative mercuration rates and corresponding ir- and
a-basicities of benzene and methylbenzenes are shown in Table
4.
The rate of mercuration of polymethylbenzene was so fast
that competitive mercuration of polymethylbenzenes and
benzene could not be directly evaluated. Therefore, the competitive mercurations of 1,2-, 1,3-, and 1,4-dimethylbenzenes
were measured against toluene, those of 1,2,3-, 1,2,4-, and
1,3,5-trimethylbenzenes against 1,3-dimethylbenzene, and
those of 1,2,3,4-, 1,2,3,5-, and 1,2,4,5-tetramethylbenzenes and
pentamethylbenzenes against 1,3,5-trimethylbenzene. From
these data and the kT/kB value, the relative reactivity of each
polymethylbenzene with respect to that of benzene was obtained. It is significant to note the low reactivity of 1,4-dimethylbenzene and particularly of 1,2,4,5-tetramethylbenzene.
An unsubstituted ring position para to a methyl group seems
to be necessary in order to achieve high substrate reactivity.
The correlation coefficient between the logarithms of the
relative mercuration rates and the logarithms of the corresponding ir- and c-basicities of methylbenzenes is 0.82 for
ir-complexes and 0.89 for a-complexes.
In an attempt at more quantitative treatment of the results
on monosubstituted benzenes, both the Hammett-Brown c++p
linear relationship and the improved multiparameter Yukawa-Tsuno relationship (17), taking into consideration both
conjugative and inductive effects of substituents, were used.
The Hammett-Brown treatment gave a p value of -6.31 and

4124

Chemistry:

Olah et al.

Proc. Natl. Acad. Sci. USA 74 (1977)

Table 4. Relative rates of mercuration of benzene and

polymethylbenzenes at 00 with reaction time of 2 sec and
comparison with r and a basicities*

ArH
Benzene
Toluene
1,2-Dimethylbenzene
1,3-Dimethylbenzene
1,4-Dimethylbenzene
1,2,3-Trimethylbenzene
1,2,4-Trimethylbenzene
1,3,5-Trimethylbenzene
1,2,3,4-Tetramethylbenzene
1,2,3,5-Tetramethylbenzene
1,2,4,5-Tetramethylbenzene

Relative
Relative 7r-complext
mercuration stability
with HCl
rates*
1
18
335
362
41

1.0
1.5
1.8

Relative
a-complex$
stability
with HF-BF3

Table 5. Variation of relative rate and isomer distribution with

temperature in thallation of benzene and toluene
in trifluoroacetic acid*
Temp.,
C

Time,
min

10
15
15

2
3
60

25
25
50
50
73
73
73
73
73

3
60
3
60
30
60
180
360
1440

kT/kB
34
35
34
33
33

Isomer distribution, %
Para
Ortho
Meta

8.8
9.5
9.0
9.1
9.7
9.3
10.6
12.6
12.2
15.0
19.6
25.8
28.6

5.1
5.5
5.7
5.9
5.8
6.2
7.5
7.8
8.3
10.7
17.0
27.2

86.1
85.0
85.6
85.0
84.6
84.6
81.9
79.7
79.4
74.3
63.4
47.0
25.4

1.6

1
7.9 X 102
7.9 X 103
106
3.2 X 103

2 X 104

2.4

2 X 106

1 X 103

2.2

2 X 106

5.7 X 104

2.6

6.3 X 108

2.3 X 105

2.6

2 X 107

* Concentrations: total [ArH], 1.00 M; [Tl(OCOCF3)3], 0.10 M.

1.35 X 105

2.7

2 X 109

67

2.8

107

the reaction was carried out up to approximately 60% completion. There was no significant variation in the isomer distributions observed, and thus there is no evidence for diarylthallium compounds.
No significant variation of the relative rate and of isomer
distributions of thallation with time was observed at 15.
Therefore, under the experimental conditions used, isomerization and disproportionation of the isomeric reaction products
in the thallation of toluene may be considered insignificant.
In order to study further the influence of reaction temperature on the isomer distribution, the competitive thallation of
toluene and benzene was also carried out at higher temperatures. The relative rates and isomer distributions are summarized in Table 5.
At higher reaction temperatures, specifically at 730 (the boiling point of trifluoroacetic acid), a marked decrease in kT/kB
was observed and the ortho and meta isomers increased at the
expense of the kinetically favored para isomer. These results
mean that aromatic thallation under the more severe reaction
conditions is an increasingly reversible electrophilic aromatic
substitution, accompanied by rapid isomerization and transthallation.
Because no isomerization (transthallation) was apparent in
the thallation of toluene below 15', the thallation of substituted
benzenes was also carried out at 100 with reaction times of 2
min. The relative reactivities and the isomer distributions are

2,0

Pentamethylbenzene 4.4 X 105

2 X 109
*
Concentrations: total [ArH], 1.0 M; [Hg(OCOCF3)2], 0.1 M.

t Andrews, L. J. & Keefer, R. M. (1964) Molecular Complexes in

Organic Chemistry (Holden-Day, San Francisco, CA), and references quoted therein.
Mackor, E. L., Hofstra, A. & van der Waals, J. H. (1958) Trans.
Faraday Soc. 54, 66, 187, and references given in ref. 7, p. 241.

a correlation coefficient of 0.95. The Yukawa-Tsuno treatment

gave an n-value of 0.69, p = -5.82, and a correlation coefficient
of 0.98. These results suggest that the transition state of highest
energy in mercuration of methylbenzenes is predominantly of
a-complex nature. It also should be noted that a large primary
kinetic hydrogen isotope effect was observed in aromatic
mercuration (kH/kD = 6.0 + 0.1 at 250) (18). Consequently,
proton elimination can at least be partially rate determining
and a relatively slow process gives rise to a significant isotope
effect. Intramolecular rearrangements in a relatively long-lived
a-intermediate ion prior to deprotonation are thus quite fea-

28
21
19
18
14
8
4
2

46.1

sible.
Thallation. The competitive thallation of benzene and toluene with thallium trifluoroacetate was studied in trifluoroacetic acid in a manner similar to the mercurations described
above. Thallated aromatics were isolated by precipitation with
summarized in Table 6.
aqueous sodium chloride, brominated in carbon tetrachloride
The results in Table 5 show that the relative reactivities of
to form the corresponding bromoarenes, and then analyzed as
the thallation of halobenzenes are in the order F > Cl > Br,
such by gas/liquid chromatography.
Br
TlCl2
Tl(OCOCF3)2
+

Tl(OCOCF3X3 [

In order to establish whether the studied thallations indeed

involved real competition of the substrates, variation of the
concentration of toluene and benzene in the competitive thallation experiments was carried out at 150. Varying the toluene/benzene concentration ratio from 1:1 to 1:8 caused no
apparent change in the kT/kB ratio, 35. The isomer distribution
also remained constant (9% ortho, 5% meta, and 86% para).
To determine whether diarylthallium complex formation
(9) had any influence on the data, the molar ratio of toluene to
thallium trifluoroacetate was also varied from 1:1 to 10:1 and

Br,
G
aq. NaCI

(~

in aq. KBr + CC14

accompanied by a decrease of the ortho substitution in the

above order. The thallation of monoalkylbenzenes under the
same experimental conditions gave the order of reactivities: Me

< Et < i-Pr < t-Bu. This order is the reverse of that of the
mercuration of the same monoalkylbenzenes. However, the
ortho isomer obtained in the thallation of ethylbenzene was only
0.6% and in the cases of isopropylbenzene and tert-butylbenzene, no ortho isomer was formed. These results indicate that
the thallation reaction evidently has larger steric requirements
and also seems to be in accord with Arnett and Abboud's (19)

Chemistry: Olah et al.

Proc. Nati. Acad. Sci. USA 74 (1977)

Table 6. Competitive thallation of monosubstituted benzenes

with thallium trifluoroacetate in trifluoroacetic acid at 100
with 2-min reaction time*

Isomer distribution, %
Ar

kAr/kB

Benzene
Toluene
Ethylbenzene
Isopropylbenzene
tert-Butylbenzene
Fluorobenzene
Chlorobenzene
Bromobenzene
Anisole

1
34
70

Anisole

90
200
0.14
0.03
0.02
270
1900t

Ortho

Meta

Para

8.8
0.6
0
0
4.5
1.8
1.6
8.0
14.0

5.1
2.2
2.1
0.5
0.1
0.9
1.8
0.1
0.6

86.1
97.2
97.9
99.5
95.3
97.4
96.7
91.9
85.5

*
Concentrations: total [ArH], 1.0 M; [Tl(OCOCF3)3], 0.1 M.
t Reaction temperature, -200.

recent conclusion that the Baker-Nathan effect is substantially

of steric origin.
The thallation of polymethylbenzenes with thallium trifluoroacetate was also carried out in trifluoroacetic acid at 00 with
2-min reaction time (Table 7). The correlation coefficients
between the logarithms of the relative rates of the thallation of
polymethylbenzenes and the logarithms of either the 7r- or
a-basicities of the corresponding polymethylbenzenes are 0.97
for ir-complexes and 0.95 for a-complexes. The HammettBrown y+p equation gave a p value of -6.92 and a correlation
coefficient of 0.96, whereas the Yukawa-Tsuno treatment gave
,y = 0.44 with p = -8.34, and a correlation coefficient of 0.98.
The similar values of both -r- and a-correlation coefficients
in thallations per se would not allow differentiation of the nature of the transition state of highest energy in the thallation
of polymethylbenzenes. Primary kinetic hydrogen isotope effects in the thallation of both heavy benzene and toluene (kH/kD
= 3.7 for benzene and 3.6 for toluene) (20), however, seem to
support the a-complex nature of the transition state of highest
energy.

Competitive thallation of polymethylbenzenes and benzene

could not be directly evaluated because the rates of thallations
of polymethylbenzenes were too fast compared with that of
benzene. Therefore, competitive thallation of 1,2-, 1,3-, and
1,4-dimethylbenzenes with toluene, of 1,2,3-, 1,2,4-, and
1,3,5-trimethylbenzenes with 1,3-dimethylbenzene, and of
1,2,3,4-, 1,2,3,5-, and 1,2,4,5-tetramethylbenzenes and pentamethylbenzenes with 1,3,5-trimethylbenzene was determined. From these results and the kT/kB the relative reactivities
of polymethylbenzenes with respect to benzene were established.
The leveling off of the value of the relative reactivities in
thallation can be explained by the fact that the activation energy of the reactions in trifluoroacetic acid must be relatively
lower than that of mercuration or other electrophilic aromatic
substitions of higher selectivity (7).
The predominant para substitution observed in the mercuration and thallation of methylbenzenes reflects, besides some
steric factors, also the strong stabilizing effect of para-methyl
groups on the arenium ion intermediates. Isomer distributions
were somewhat affected by intramolecular rearrangements
within the reaction intermediates or by the reversibility of the
systems, but meta substitution, under predominant kinetic
control, stayed low (i.e., 5-6% or less), in good agreement with
Klapproth and Westheimer's (6) report of 6% in the mercuration of toluene. In contrast, the higher meta values reported by
Brown and McGary (21) are, in our view, due to thermody-

4125

Table 7. Relative rates of thallation of benzene and

polymethylbenzenes at 100 with 2-min reaction time*
ArH
kApjkB
Benzene
1
Toluene
34
1,2-Dimethylbenzene
145
1,3-Dimethylbenzene
1500
1,4-Dimethylbenzene
33
1,2,3-Trimethylbenzene
7200
1,2,4-Trimethylbenzene
1550
1,3,5-Trimethylbenzene
7750
1,2,3,4-Tetramethylbenzene
6300
1,2,3,5-Tetramethylbenzene
6350
1,2,4,5-Tetramethylbenzene
2300
Pentamethylbenzene
7500
* Concentrations: total [ArH], 1.0 M; [Tl(OCOCF3)3], 0.1 M.

namically controlled intramolecular or intermolecular processes

affecting primarily the ortho/para metallated derivatives and
not to enhanced meta substitution. The discrepancy thus can
be resolved by pointing out that in the latter case the necessity
to differentiate kinetic from thermodynamically controlled
processes, when considering substrate and regioselectivities in
aromatic substitution, was not fully taken into account.
Support of our work by the National Science Foundation is gratefully
acknowledged.
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