Two pathways of arenesulfonyl chlorides hydrolysis. Anionic intermediates in SAN-hydrolysis of 4-nitrobenzenesulfonyl chloride

Article abstract of DOI:10.1023/B:RUJO.0000043723.87836.9e

Arenesulfonyl chlorides undergo the hydrolysis in water and binary aqueous solvents along two pathways of S_AN mechanism involving cyclic intermediate with pentacoordinate sulfur atom (H₂O) _nSO₂(Cl)Ar and through anionic intermediate HO ^-SO₂(Cl)Ar(H₂ O)_n. The contribution of the process involving anionic intermediates grows with increasing σ_p constant and attained maximum value for 4- nitrobenzenesulfonyl chloride. In water and 17 water-dioxane mixtures the relation of apparent first-order rate constants and activation parameters to the molar fraction of dioxane in the mixture (0-0.25) are not monotonic, and the hydrolysis process is catalyzed by dioxane.

Full text of DOI:10.1023/B:RUJO.0000043723.87836.9e

Russian Journal of Organic Chemistry, Vol. 40, No. 5, 2004, pp. 733 -739. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 5, 2004,
pp. 766-772.
Original Russian Text Copyright Ó 2004 by Ivanov, Gnedin, Kislov.
Two Pathways of Arenesulfonyl Chlorides Hydrolysis.
Anionic Intermediates in S N-Hydrolysis
A
of 4-Nitrobenzenesulfonyl Chloride
S.N. Ivanov, B.G. Gnedin, and V.V. Kislov
Ivanovo State University, Ivanovo,1530 25 Russia
e-mail: isn@ivanovo.ac.ru
Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo,153045 Russia
ReceivedAugust 19, 2002
Abstract—Arenesulfonyl chlorides undergo the hydrolysis in water and binary aqueous solvents along two pathways
of S N mechanism involving cyclic intermediate with pentacoordinate sulfur atom (H O) SO (Cl)Ar and through
A
2
n
2
–
anionic intermediate HO SO (Cl)Ar(H O) . The contribution of the process involving anionic intermediates grows
2
2
n
with increasing s constant and attained maximum value for 4-nitrobenzenesulfonyl chloride. In water and 17 water-
p
dioxane mixtures the relation of apparent first-order rate constants and activation parameters to the molar fraction of
dioxane in the mixture (0–0.25)are not monotonic, and the hydrolysis process is catalyzed by dioxane.
The reaction series for hydrolysis of substituted arene-
sulfonyl chlorides in water and its mixtures with nonelec-
trolytes suffers significant deviations from the linear
Hammett’s plot for lgk of compounds containing substitu-
ents 4-NO , 4-CN, 4-F, and 4-CH O [1–4]. The hydroly-
nism suggests the presence of a linear correlation be-
tween Hammett’s s-constants and logarithms of appar-
ent constants of hydrolysis in water for meta-and para-
substituted benzenesulfonyl chlorides. According to
Haughton et al. [3] this relation may be regarded as
linear (C = –0.421± 0.014, r 0.965, n 13) on excuding
from the reaction series the rate constants of the above
mentioned substituted sulfonyl chlorides.
2
3
sis rates for sulfonyl chlorides containing 4-NO -, 4-CN-,
2
and 4-CH O-substituents considerably exceed the val-
3
ues appropriate for the s-constants. The largest devia-
tion in the lgk value observed in the case of 4-nitro-
benzenesulfonyl chloride (I) attracts great interest of re-
searchers to investigation of its hydrolysis [3–5].
Haughton et al. [3] regarded as the cause of devia-
tions of the log k–s plot from linear dependence a direct
polar conjugation of substituents 4-NO and 4-CN with
2
The reason of deviations resulting in the U-like form
of the log k–s plot was formerly attributed [1] to a con-
cept that with growing Hammett’s s-constants occurred
a transition from S 1 mechanism (C < 0) to S 2 one with
the sulfonyl chloride moiety; these substituents thus were
electron-donors with respect to strongly electron-deficient
sulfonyl atom. On the contrary, under the effect of 4-F
substituent that was considered to be incapable to enter
into a direct polar conjugation [3] the sulfonyl chloride
group hydrolyzed slower than would be predicted from
the s-constant of this substituent.
N
N
a “compressed” transition state (C > 0). Haughton et al.
3] presumed that hydrolysis of sulfonyl chlorides passed
[
through a stage of fast formation of intermediate with a
pentacoordinate sulfur followed by the cleavage of the
S–Cl bond in the course of a slow stage. The formation
of a pentacoordinate intermediate in keeping with addi-
Nowadays the arenesulfonyl chlorides hydrolysis is
regarded as synchronous S 2 process where the order
N
of S¼OH bond formation and S¼Cl bond cleavage
2
tion-elimination mechanism S N was assumed for reac-
within the transition state depends on the nature of the
substituent and on its position in the benzene ring [9, 10].
As the electron-withdrawing quality of the substituent
A
tions of arenesulfonyl fluorides [6], thiophenesulfonyl ha-
lides [7] with anionic and neutral nucleophiles, for hy-
drolysis of 2,4,6-trimethylbenzenesulfonyl chloride [8].
However this mechanism was rejected [9-13] due to the
lack of experimental proofs that this intermediate actu-
ally formed.At the same time the existence of this mecha-
grows, increases the order of the S¼OH bond in the
2
compressed transition state. This conception rationalizes
the absence of linear dependence and U-like form of the
plot ln k–s.
1070-4280/04/4005-0733Ó2004 MAIK “Nauka/Interperiodica”

734
IVANOV et al.
Beside the positive deviation of log k value from the
Table 1. Apparent rate constants of hydrolysis of sulfonyl chlo-
I
linear plot lnk–s the hydrolysis of compound I is distin-
guished by some other specific features: at growing con-
tent in binary mixture with water of dioxane (up to
30 vol% [1, 10, 11]), acetone, and acetonitrile (to 20 and
0 vol% respectively[5]) the apparent rate constants of
compound I hydrolysis do not first decrease as with the
differently substituted compounds but grow forming a flat
maximum; the hydrolysis of compound I is suppressed
on cationic micelles 4–5 times weaker, and its reaction
with carboxylate anions incorporated into the zwitter-ionic
micelles on the contrary is accelerated considerably stron-
ger than the corresponding reactions of, for example,
ride I in water-dioxane mixture with X 0.0806 at various tem-
2
peratures
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texp(1/2) is half-conversion time.
4
-bromobenzenesulfonyl chloride [13]. The sum of these
features of compound I hydrolysis did not find any com-
pelling explanations for none among them took into ac-
count the decisive factor of the medium
The different effect of solvent composition on the re-
activity of compounds I and II can be understood taking
into account the results of quantum-chemical calculations
In this connection the goal of this study was investiga-
tion of solvation effects in the hydrolysis of sulfonyl chlo-
ride I in water-dioxane mixtures. We presumed that the
results of the study would elucidate the specific features
of compound I hydrolysis and provide additional informa-
tion on the laws of arenesulfonyl halides hydrolysis.
[
15, 16], and also the concept [5] of general basic cataly-
sis of the hydrolysis of sulfonyl chloride group by a mol-
ecule of the nonaqueous component.
Quantum-chemical simulation of benzenesulfonyl chlo-
ride hydrolysis in a gas phase [15] and water clasters
[16] (PM3 method, supermolecular approximation) re-
–
1
Apparent hydrolysis rates k (s ) of compound I were
Ò
vealed that the hydrolysis of benzenesulfonyl chloride in
the form of hydrate (A) proceeded as a two-stage pro-
cess through a pentacoordinate intermediate
PhSO (H O)Cl (B) of low stability (Scheme 1).
determined by conductometric method at 6–7 various tem-
peratures within the range 284–322 K in water and 17
water-dioxane mixture with molar fraction of dioxane
X2 0–0.25. The solutions with a low dioxane content (X2
2
2
The rate constants of intermediate (B) formation and
transformation into reaction products proved to be of com-
parable value. This means that the apparent hydrolysis
0–0.05) were subjected to the most thorough investiga-
tions. Experimental values of k for one of the 17 solu-
Ò
tions are compiled in Table 1, and interpolated values of
k298 calculated with the use of quasithermodynamic acti-
vation parameters are given in Table 2. The plot of k298
constant of PhSO Cl is affected by both stages. The sharp
2
dependence of hydrolysis rate constants of compound II
on water concentration originates from the fact that the
partial reaction order with respect to water m in the
water-dioxane solution is close to three [14]. Therewith
the process is char-acterized by low values of activa-
as a function of X for hydrolysis of compound I is pre-
2
sented on Fig.1 (curve k ). For comparison analogous
I
curve (k ) is plotted for 2-methylbenzenesulfonyl chlo-
II
ride [14]. Different trends in variations of the apparent
rate constants with decreasing water content are very
-1 -1
tion entropy [–70... –120 J mol K , and the activa-
tion barrier to the stage of intermediate (B) decomposi-
tion through transition state (C) is the most decreased in
cyclic clasters [16] where water (H O) close a ring to
the structural fragment S–Cl (n is a number of H O mol-
ecules taking part in catalysis of the hydrolysis, n = m –
I
prominent: the k values go through a flat maximum at X2
~
0.05 (20 vol%) and afterwards weakly diminish, whereas
2
n+1
the k values sharply decrease with growing X within
II
2
2
the total concentration range.
Scheme 1.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 5 2004

TWO PATHWAYS OF ARENESULFONYL CHLORIDES HYDROLYSIS
735
Table 2. Activation parameters and interpolated rate constants (k298) for hydrolysisa of sulfonyl chloride I in water-dioxane mixture
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b
c
r is correlation factor for Arrhenius plot.
n is the number of rate constants used in the temperature relation.
DT is the temperature range where the kinetic measurements were done.
d
–3
–3
–3 –1
(
2.48 ± 0.02 )´10 [4], 2.62 ´ 10 [5], 2.45 ´ 10 s [13].
1
= 1 – 3). These facts correspond to a catalytic nucleo-
hydrolysis of benzenesulfonyl chloride is characteristically
subject to the general basic catalysis with triethylamine
[21]. Bentley et al [5] believe that for the sulfonyl chlo-
rides with electron-withdrawing substituents the general
basic catalysis occurs also involving molecules of non-
aqueous component of the solvent (acetone, acetonitrile,
philic substitution mechanism at the sulfonyl reaction cen-
ter [15, 16] with cooperative participation of n + 1 water
molecules in a cyclic transition states.
The n values for various sulfonyl halides in water-
dioxane solutions were found experimentally to be from
1
1,4-dioxane). In an earlier publication [22] Bentey suc-
to 2 [1, 9–11, 14]. The partial orders with respect to
cessfully described the hydrolysis of 4-nitrobenzoyl chlo-
ride (III) with equation (1), where account is taken of
the effect of one reactive water molecule and one mol-
ecule of nonaqueous component serving as catalyst:
“
free” water for hydrolysis of sulfonyl chloride II in sys-
tems water–i-PrOH and water– t-BuOH were deter-
mined experimentally [18], and with accounting for the
limiting hydrate numbers of 2-propanol and tert-butanol
0
(
N 7 and 13.5 respectively ) [19] these values were found
g
OQN ꢀ
at about 2 (consequently, n = 1).
We believe that the hydrolysis mechanism presented
on Scheme 1is valid also for the other arenesulfonyl ha-
lides with electron-donor substituents at the aromatic ring,
among them for methyl-substituted derivatives of
benzenesulfonyl chloride and benzenesulfonyl bromide
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[
14, 17, 20]. For instance, at growing dioxane concentra-
3
tion the fourth-order rate constants k /[H O] remain
II
2
ꢂꢁ
actually constant [14]. In keeping with Scheme 1 this fact
evidences that bimolecular hydrolysis of compound II is
catalyzed with two additional water molecules.
±
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Fig. 1. Plots of ln k vs molar dioxane fraction (x ) at 298 K for
hydrolysis of sulfonyl chlorides I (1) and II (2).
It is appropriate to consider now the special features
of catalysis of sulfonyl chloride group hydrolysis. The
i
2
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 5 2004

736
IVANOV et al.
2
v = ki (1)ci·c13 + k c ·c ·c
2 1
2
k /c = k III (1) + k III (2)·c /c
(2)
III
1
2
(1)
i (2) i
-1
Here c is concentration of sulfonyl chloride(i)(moll );
i
Here kIII is apparent rate constant of compound III
ki (1) and ki (2) are catalytic fourth-order rate constants
accounting for catalysis of compound I hydrolysis (i) with
molecules of water and dioxane respectively in cyclic
activated complexes forming from solvation complexes
(A) and (D). Taking into account expression (2) equation
hydrolysis; kIII (1) and k III (2) are catalytic third-order rate
constants accounting for catalysis of compound III hy-
drolysis with molecules of water and nonaqueous com-
ponent respectively; c , c are consentrations of water
1
2
-1
and nonaqueous component respectively (mol l ).
(3) can be written that is more convenient to be presented
However for hydrolysis of compound I in mixtures of
water with aprotic solvents (acetone, acetonitrile, and
,4-dioxane) Bentley et al. [5] considered the correlation
in form (4):
3
2
ki = ki (1)·c + k ·c ·c
2
(3)
(4)
1
i (2)
1
1
ki/c13 = ki (1) + ki (2)·c /c1
according to equation (1) not sufficiently good, especially
2
*
at the use of water-dioxane solution. The main reason
3
According to equation (4) the k /c should be in linear
i
1
of the insufficiently good correlation is apparently the
neglecting in [5] of the involvement of an additional wa-
ter molecule in the activated complexesof the sulfonyl
chlorides hydrolysis.
dependence on the molar ratio of the components of the
binary solvent c /c = [dioxane]/[H O]. The treatment
2
1
2
3
of linear relations k /c1 = f(c /c ) presented on Fig. 2
i
2
1
provided rate constants k(I)1 and k(I)2 for hydrolysis of
compound I.
For the assumed in [5] overall third order of the reac-
tion [substrate + H O + dioxane (C H O )] the solvation
2
4
8
2
3
–8
–8
k /c = (0.83 ± 0.22) ´ 10 + (43.8 ± 1.7) ´ 10 c /c
1
(
I)
1
2
complex (E) should include a four-membered ring that
according to calculations [16, 23, 24] is energetically un-
favorable. To form more stable six-membered ring as in
complex (D) an additional water molecule is necessary.
r 0.989, N17, SD 0.662
The sharp difference in relations (4) for compounds I
and II (a strong acceleration of compound I hydrolysis
and virtually unchanging hydrolysis rate constant of com-
pound II) at increse in dioxane concentration obviously
indicates dissimilar mechanisms of hydrolysis process for
these sulfonyl chlorides.
The formation of solvation complexes of (D) type with
a cycle having water bridges of two H O molecules is as
2
feasible from the thermodynamical viewpoint as forma-
tion of solvation complexes of (A) type with bridges of
three water molecules. This conclusion is consistent with
that of [25] where the clasters of phenol with two mol-
ecules of water having cyclic structure like water trimer
were stated to be the most stable.
It should be noted that the reaction mechanism shown
on Scheme 1 does not rationalize the positive sign of the
resonance sensitivity constant r 3.01 that we have found
R
In keeping with the above reasoning the following
equation can be written for the hydrolysis rate of sulfonyl
chlorides:
by statistical processing of kinetical data on hydrolysis
in water medium of meta- and para-substituted ben-
zenesulfonyl chlorides [12]. Large positive r value as
R
distinct from the “normal” negative constants r = –0.78
and rR = –4.44 indicates that in the hydrolysis of sulfo-
ꢀ
I
+
ꢀ
ꢁꢂ
nyl chlorides alongside the processes occurring in com-
pliance to Scheme 1 the hydrate complexes
ArSO Cl·nH O may be converted into the reaction prod-
ꢃꢄꢂ
ꢃꢀꢂ
ꢂꢂꢅꢂ
ꢂꢂꢆꢂ
ꢂꢂꢁꢂ
2
2
–
ucts via a stage of formation of intermediate anions HO
SO (Cl)Ar·nH O [12] (Scheme 2).
ꢁ
ꢀ
–
2
2
Thus the arenesulfonyl halides can undergo hydrolysis
±
ꢆꢂ
ꢁ
ꢂꢂꢂꢂꢂꢂꢂꢂꢃꢁꢁꢂꢂꢂꢂꢂꢂꢀꢁꢁꢂꢂꢂꢂꢂꢇꢁꢁꢂꢂꢂꢂꢂꢂꢆꢁꢁꢂꢂꢂꢂꢂꢈꢁꢁꢂ
ꢊF ꢋF ꢉuꢃꢁ ꢂ
Fig. 2. Dependence of k /c on the ratio c /c for hydrolysis of
in water along two parallel pathways where the solvation
complexes (A) transform either into intermediates (B)
(Scheme 1), or into intermediates (F) (Scheme 2). The
rates ratio of these two processes depends on the
character of substituent attached to benzene ring. In the
hydrolysise of benzenesulfonyl halides containing
electron-donating substituents at the ring dominates
3
i
1
2
1
compounds I (1) and II (2) in aqueous dioxane.
*
In [5] were used the data on water-dioxane mixed solvents of early
publications [1] (up to 30% of dioxane) and [3] (50–90% of diox-
ane).
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 5 2004

TWO PATHWAYS OF ARENESULFONYL CHLORIDES HYDROLYSIS
737
Scheme 2.
$
U
$U
ꢀ
ꢁ
ꢁ ꢁ
ꢀ
+ 2 62 &OꢁꢂꢂQꢂ+ 2
ꢀ+2 62 &OꢁꢂꢂQꢂ+ 2ꢂꢂꢄꢂꢂ+
$U62 2+ꢂꢂꢄꢂꢂ&Oꢂꢄꢂꢂ+ ꢂꢄꢂꢂQ+ 2
Uꢂ!ꢂꢃ
$
)
pathway 1, and the part of pathway 2 in the overall
process grows with increasing electron-attracting
character of the substituent attached to the benzene ring.
The electron-withdrawing substituents are capable of
Scheme 3.
$
U
ꢀ
+ 2 62 &OꢂꢁꢁꢀQꢁ ꢁꢃꢂꢁ+ 2ꢁꢁ+.
'
–
delocalizing the negative charge OH and thus of
$U
ꢀ
ꢁ
B
stabilizing the intermediate anion (F). As a result the
equilibrium of anion (F) formation shifts to the right [14].
The most spectacular example of a process taking pathway
ꢀ
+2 62 &OꢂꢁꢁꢀQꢁ ꢁꢃꢂꢁ+ 2ꢁꢁ+.ꢁꢁꢅꢁꢁ+
Uꢁ!ꢁꢄ
*
ꢂ ꢁ
2
is the hydrolysis of compound I. The electron-donating
*
$U62 2+ &OꢁꢅꢁꢀQꢁ ꢁꢃꢂꢁ+ 2ꢁꢅꢁ+.ꢁꢅꢁ+
substituents destabilize anion (F). The acceleration of
compound I hydrolysis by dioxane (and the other
nonaqueous components: acetone, acetonitrile, methanol,
ethanol [5]) evidences that the molecules of nonaqueous
components playing the role of general bases shift the
equilibrium 1–3 (Scheme 3) even more to the right.
Interestingly, in the hydrolysis of sulfonyl chloride I in
the range of water-dioxane mixtures (X 0–0.025)
2
although the k does not strongly decrease with the
I
growing dioxane concentration, the nonmonotonic
character of k –X relation is quite clear (the changes in
I
2
In the water-acid medium the ratio of pathways 1
and 2 strongly changes in favor of the first one. It is seen
from the ratio of values k /k that in water is 0.66, in
kI largely exceed the possible measurement errors). In
the hydrolysis in the same medium of chloride II and
I
II
1
2% H SO 0.43, and in 50% H SO 0.10 [26].
2 4 2 4
The above rationalization of results is consistent with
ꢋDꢌꢀ
ꢀꢁꢀ
conclusions of [13] where has been carried out an attempt
to elucidate the sign of charges on transition states in
hydrolysis of para-substituted benzenesulfonyl chlorides
by comparison of process inhibition on micelles of cationic
and anionic type. The hydrolysis of arenesulfonyl
chlorides is decelerated less on cationic than anionic
micelles, and also at growing electron-attracting properties
of substituent. These facts [13] testify to anion-like
character of the transition states in the synchronous
ꢀ
ꢂꢁꢀ
ꢀ
ꢃꢁꢀ
ꢀ
ꢄꢁꢀ
ꢀ
ꢊꢁꢀ
ꢁꢀ
ꢂꢀ
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢅꢁꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢆꢁꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢇꢁꢀ
ꢁ
mechanism S 2 where the processes of bonds O¼S
N
formation dominate over processes of bond S¼Cl rupture.
The value of the negative charge on the transition state
grows with the electron-withdrawing character of
substituent and is maximum in hydrolysis of compound I.
ꢍꢀꢎꢀ
ꢋEꢌꢀ
ꢂꢀ
ꢃꢁꢀ
ꢀ
According to [11] replacement of H O by D O in
2
2
ꢁꢀ
hydrolysis ofArSO Cl with the following R substituents
ꢊꢁꢀ
ꢀ
2
at the benzene ring: 2,4,6-i-Pr , 4-t-Bu, H, 4-Br, 4-NO2
3
in 70% and 40% aqueous dioxane (X in these mixtures
2
ꢆꢁꢀ
was 0.32 and 0.12 respectively) the reaction constant r
diminished and not increased as it was expected in keeping
with the concept of more “compressed” transition state
ꢁꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢁꢂꢅꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢁꢂꢆꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢁꢂꢇꢀ
in the case of D O. This observation may be understood
2
as resulting from reduction of the contribution from the
pathway through intermediates (G) in the hydrolysis of
sulfonyl chlorides at replacement of H O by D O.
Fig. 3. Dependence of activation enthalpy (a) and contribution
Ñ (b) on the molar fraction of dioxane for hydrolysisa of
compounds I (1) and II (2).
2
2
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 5 2004

738
IVANOV et al.
other methyl-substituted benzenesulfonyl halides similar
dependences are more smooth (Fig. 1). The main cause
pH of the mixtures insignificantly changed in the course
of experiments. We did not use buffer mixtures for the
dependence of apparent rate constants of arenesulfonyl
chlorides hydrolysis on pH in acid media [2, 9, 29].
of weak alteration of k values and of decreasing
I
activation parameters in the all range of concentrations
studied is the catalysis of the process along pathway 2
effected by dioxane molecules (Scheme 3).
REFERENCES
The dependences of activation parameters on the
medium composition for hydrolysis of sulfonyl chlorides I
and II are nonmonotonic (Fig. 3) with extrema at virtu-
ally the same values of X (in the region of small X val-
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3
4
5
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2
2
ues 0–0.05 they go nearly parallel). In the range X 0–
2
¹
¹
0
.13 the relations DH > DH and J < J (meaning
DS > DS , for J are fractions expressed in percents of
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I II I II
¹
¹
I
II
¹
¹
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Perkin, Trans. II, 1994, p. 753.
X > 0.13 these relations acquire a reverse sense. The
2
¹
frontier concentration X dividing the regions DH >>
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I
¹
¹
¹
II
I
II
the critical concentration of hydrophobic interaction for
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2
served general trend in diminishing of the activation pa-
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¹
¹
the solvent [14]. More steep decrease in DH and DS
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–
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2
fonyl chlorides I and II, and they have been thoroughly
discussed before [14, 17, 18, 20].
11. Rubleva, L.I., Maksimenko, N.N., and Vizgert, R.V., Kinetika
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1
996, vol. 2, p. 716.
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was 79–80°C (publ.: mp 80.5°C [28]). Water solutions of
dioxane were prepared as described in [14, 20]. The rate
constants were determined by conductometric method
1
1
14. Ivanov, S.N., Kislov, V.V., and Gnedin, B.G., Zh. Obshch.
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[
17, 20]. The measurements were carried out in a cell of
3
volume ~5 cm with platinum electrodes using an
a.c.impedance bridge P-5030. The reagent was charged
into the cell with a micropipet as a drop of a concentrated
solution in dioxane preliminary kept at the temperature
required for the experiment. The first-order rate constants
were calculated by Guggenheim procedure. The initial
concentration of sulfonyl chloride in the water-dioxane
1
1
–
4
–5
-1
solvent was of the order of magnitude 10 –10 mol l .
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 5 2004

TWO PATHWAYS OF ARENESULFONYL CHLORIDES HYDROLYSIS
739
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RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 5 2004