Solvent effect on the kinetics of arylsulfonation of benzhydrazide with 3-nitrobenzenesulfonyl chloride in aqueous-organic solutions

Article abstract of DOI:10.1023/B:RUGC.0000031865.01147.b4

A comparative study is made of the solvent effect on the kinetics of arylsulfonation of benzhydrazide with 3-nitrobenzenesulfonyl chloride in aqueous-organic solutions (water-2-propanol, water-dioxane, water- tetrahydrofuran, and water-acetonitrile) at 298 K. The arylsulfonation product can be obtained in nearly theoretical yield at the initial reactant concentrations of 0.1 M in the water-dioxane, water-MeCN, and water-THF mixtures containing above 30 wt % water.

Full text of DOI:10.1023/B:RUGC.0000031865.01147.b4

Russian Journal of General Chemistry, Vol. 74, No. 4, 2004, pp. 606 609. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 4, 2004,
pp. 664 668.
Original Russian Text Copyright
2004 by Kustova, Sundeeva.
Solvent Effect on the Kinetics of Arylsulfonation
of Benzhydrazide with 3-Nitrobenzenesulfonyl Chloride
in Aqueous-Organic Solutions
T. P. Kustova and N. A. Sundeeva
Ivanovo State University, Ivanovo, Russia
Received June 4, 2002
Abstract A comparative study is made of the solvent effect on the kinetics of arylsulfonation of benz-
hydrazide with 3-nitrobenzenesulfonyl chloride in aqueous-organic solutions (water 2-propanol, water di-
oxane, water tetrahydrofuran, and water acetonitrile) at 298 K. The arylsulfonation product can be obtained
in nearly theoretical yield at the initial reactant concentrations of 0.1 M in the water dioxane, water MeCN,
and water THF mixtures containing above 30 wt % water.
The capability of influencing the reaction rate
through association with reactants makes water
promising as a component of solvents used in aryl-
sulfonation of arenecarboxylic acid hydrazides with
arenesulfonyl chlorides. Therefore, in this work we
studied the kinetics of this reaction in aqueous-organic
binary solvents.
kh
II + H2O
3-NO2C6H4SO3H + HCl.
(3)
III
Therefore, the rate constant kh of hydrolysis of sul-
fonyl chloride II should be taken into account in
estimating the arysulfonation rate constant ka. As-
suming c0I = 2cI0I, the kinetic equation takes the form
Previously we reported on the reactivity of arene-
carboxylic acid hydrazides toward arenesulfonyl
chlorides in several aqueous-organic solvents [1, 2].
The goal of this work was to study the kinetics of
arylsulfonation of benzhydrazide I with 3-nitro-
benzenesulfonyl chloride II in water acetonitrile
(MeCN) and water tetrahydrofuran (THF) binary sol-
vents and also the effect of the water content in H2O
i-PrOH, H2O dioxane, H2O THF, and H2O MeCN
on the kinetics of this reaction at 298 K. Arylsulfona-
tion of arenecarboxylic acid hydrazides proceeds in
two stages: formation of arylsulfonation product [re-
action (1)] and binding of the liberated HCl [reac-
tion (2)]. However, since the latter reaction proceeds
practically instantly [its rate is higher by four orders
of magnitude than that of (1)], arylsulfonation of
arenecarboxylic acid hydrazides should be considered
as a single-stage reaction.
of Eq. (4).
kh
kh
ka = kh[e
(c I0I x) c I0I]/[2c 0II(c I0I x)(1
e
)]. (4)
Here x is the change in the sulfonyl chloride II con-
centration by time ; c0II, its initial concentration; and
c0I, initial concentration of benzhydrazide I.
The rate constants of the reaction under considera-
tion in H2O THF and H2O MeCN and also the rate
constants of hydrolysis of sulfonyl chloride II are
given in Table 1.
Table 1 shows that, as expected, in H2O THF, ka
increases with increasing water content w in the bi-
nary solvent. At water contents of 60 and 70% (here
and hereinafter, wt %), hydrolysis prevailed, and ka
could not be estimated. In the case of H2O MeCN, ka
changes irregularly with increasing water content,
slightly varying over the experimental w range. With
increasing w from 10 to 50%, ka increases by a factor
of about 1.5, while in H2O THF, the corresponding
factor is 3.
C6H5CONHNH2 + 3-NO2C6H4SO2Cl
I
II
ka
C6H5CONHNHSO2C6H4NO2-3 + HCl,
(1)
(2)
fast
For the reaction in aqueous THF, we studied the
temperature dependence of ka over the range 298
318 K. The activation characteristics of the reaction
were determined with a computer using an original
I + HCl
C6H5CONHNH2 HCl.
In aqueous-organic solvents, hydrolysis of sulfonyl
chloride II [reaction (3)] occurs as a side reaction.
1070-3632/04/7404-0606 2004 MAIK Nauka/Interperiodica

SOLVENT EFFECT ON THE KINETICS OF ARYLSULFONATION
607
Table 1. ka and kh in H2O THF and H2O MeCN (298 K)
consideration is characterized by relatively low activa-
tion energy and entropy. With increasing water
content in H2O THF, the activation characteristics
change only slightly (to within the experimental error).
H2O THF
ka 102, kh 104,
H2O MeCN
ka 102, ka 104,
w(H2O),
%
Previously [1] we studied the kinetics of the reac-
tions of benzhydrazide I with 4-nitrobenzenesulfonyl
chloride and sulfonyl chloride II in H2O i-PrOH and
H2O dioxane, respectively.
1
1
1
1
l mol 1 s
s
l mol 1 s
s
10
20
30
40
50
60
70
3.47 0.07 2.11 0.04 19.7 0.20 0.57 0.01
5.29 0.34 2.53 0.04
7.18 0.71 2.62 0.02 23.3 0.20 1.51 0.01
8.29 0.95 3.58 0.01 22.3 0.20 2.13 0.03
10.40 0.57 4.79 0.01 32.6 0.40 2.84 0.06
4.73 0.01 21.1 0.40 3.89 0.03
7.14 0.10
The kinetic parameters of reaction (1) in H2O
MeCN, H2O i-PrOH, H2O dioxane, and H2O THF
are given in Table 3 for various water contents. As
seen, ka increases with increasing water content in
aqueous-organic solvents. The highest ka was obtained
in the H2O MeCN system. The lack of a linear cor-
relation between ka and the Kirkwood function for the
reaction of benzhydrazide I with sulfonyl chloride II
in the aqueous-organic solvents studied (see figure)
suggests that specific solvation plays a dominant role
in this process, while nonspecific interactions con-
tribute only insignificantly.
code. The results are given in Table 2 along with data
on ka.
As seen, ka grows insignificantly with increasing
temperature (as the temperature increases by 10 C, ka
grows by a factor of about 1.5 for all the compositions
of the H2O THF binary solvent). The reaction under
The observed noticeable differences in the kinetics
Table 2. Kinetic and activation parameters of arylsulfonation of benzhydrazide I with sulfonyl chloride II in H2O THF
(298 318 K)
1
1
1
1
1
w(H2O), % T, K ka 102, l mol 1 s
kh 104, s
Ea, kJ mol
S , J mol 1 K
H , kJ mol
10
20
30
40
50
298
303
308
313
318
298
303
308
313
318
298
303
308
313
318
298
303
308
313
318
298
303
308
313
318
3.47 0.07
3.57 0.28
4.20 0.65
4.76 1.08
5.87 0.90
5.29 0.34
6.11 0.27
6.95 0.86
8.43 0.01
9.39 0.56
7.18 0.71
8.17 0.31
9.59 0.65
11.13 0.50
12.13 1.12
8.29 0.95
9.83 0.15
12.20 0.54
13.47 0.58
14.03 0.17
10.40 0.57
12.27 0.48
13.88 0.60
15.23 0.50
2.11 0.04
2.15 0.04
3.00 0.10
3.22 0.10
3.48 0.10
2.53 0.04
2.79 0.03
4.03 0.10
4.74 0.10
6.34 0.04
2.62 0.02
3.55 0.02
4.87 0.03
6.44 0.03
8.45 0.03
3.58 0.01
4.78 0.01
6.59 0.01
8.79 0.02
11.70 0.01
4.79 0.01
6.13 0.01
9.08 0.02
11.90 0.02
16.00 0.01
21.0 3.0
211 9
18.5 2.9
23.2 1.0
21.4 1.0
21.7 2.9
19.7 1.6
200 3
204 3
201 9
206 5
20.6 1.0
18.9 1.0
19.1 2.9
17.2 1.6
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 4 2004

608
KUSTOVA, SUNDEEVA
1
Table 3. ka 102 (l mol 1 s ) in aqueous-organic solvents (298 K)a
w(H2O), %
H2O THF
H2O dioxane
H2O MeCN
19.7 0.20
H2O i-PrOH
10
20
30
40
50
60
70
3.47 0.07
5.29 0.34
7.18 0.71
8.29 0.95
10.40 0.57
1.19 0.16
3.50 0.06
3.61 0.17
4.79 0.40
6.72 0.19
8.49 0.30
12.86 0.17
6.05 0.03
9.39 0.03
11.29 0.06
25.10 0.12
23.3 0.20
23.3 0.20
32.6 0.40
21.1 0.40
a
Constant k was estimated using the correlation equation from [1].
a
of arylsulfonation of benzhydrazide I with sulfonyl
chloride II in various solvents can be attributed, in
our opinion, to the formation of heteromolecular
associates (clusters) between the components of the
aqueous-organic solvents [3]. Increase in the content
of the organic component can distort the water struc-
ture, which, evidently, is responsible for the observed
differences in the rate constants of reaction (1).
alcohol systems. As a result, the highest ka was ob-
tained just in the H2O MeCN system. Taking the
resultant effect of the solvent polarity and factors
controlling the specific solvation into consideration,
we can conclude that the interaction between the
components of a binary solvent is the weakest in
aqueous acetonitrile.
The H2O THF and H2O dioxane binary solvents
are similar in the nature of an organic component:
both THF and dioxane are cyclic ethers. Therefore, it
should be expected that the kinetic parameters of reac-
tion (1) in these solvents will be similar. This assump-
tion was well supported by the experiment (Table 3).
The rate constants of arylsulfonation in H2O THF and
H2O dioxane were found to be nearly equal at the
same water contents.
Molecules of many solvents are involved in solva-
tion through hydrogen bonding and donor acceptor
interaction. In aqueous-alcohol solvents, both solvent
components and solutes can be involved in hydrogen
bonding. It is known [4] that H complexes of alcohols
with amines are mostly more reactive as compared to
the initial reactants. In contrast to alcohols, MeCN
contains no hydrogen atom capable of forming hydro-
gen bonds with water molecules and reactants. There-
fore, MeCN can participate in solvation only via
donor acceptor interaction. Evidently, the reactivity
of the resulting molecular complexes is higher than
that of the complexes reactant solven formed in H2O
Since hydrolysis (3) is the side reaction in arylsul-
fonation of benzhydrazide I in aqueous-organic sol-
vents, acid III will always be contained in the system
in addition to the main product. The yields of the
main and side products
and
were estimated by
a
analysis of the experimental kinethic data (Table 3). A
system of differential equations (5) and (6) was solved
by the fourth-order Runge Kutta method. The results
for the case of full completion of the reaction are
given in Table 4.
logka
2.0
1
1.6
d
d
a/d = 2kacI0I(1
h/d = kh(1
h)2,
(5)
(6)
a
1.2
h) .
a
0.8
2
The results suggest that the solvents H2O THF,
H2O MeCN, and H2O dioxane with the water content
above 30% are more favorable for reaction (1), since
in these binary mixtures the yield of the main product
was obtained to be above 91% at the initial reactant
concentrations of 0.1 M. The solvent H2O i-PrOH
(50 70% H2O) can also be used, but in this case the
yield of the arylsulfonation product is lower (83 87%).
0.4
0.472 0.476 0.480 0.484 0.488 0.492
(
1)/(2 + 1)
Logarithm of the rate constant k of arylsulfonation of
benzhydrazide I with sulfonyl chloride II in (1) H O
i-PrOH and (2) H O MeCN vs. the Kirkwood function.
a
2
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 4 2004

SOLVENT EFFECT ON THE KINETICS OF ARYLSULFONATION
609
Table 4. Yield
w(H2O), %
of arylsulfonation of benzhydrazide I with sulfonyl chloride II in aqueous-organic solvents at 298 K
a
a, %
c 0II, M
H2O THF
H2O dioxane
H2O MeCN
H2O i-PrOH
10
20
30
40
50
60
70
0.01
0.1
0.01
0.1
0.01
0.1
0.01
0.1
0.01
0.1
0.01
0.1
0.01
0.1
55.73
55.73
60.66
91.02
65.90
92.66
62.68
91.67
61.41
91.26
93.85
99.05
26.68
72.67
40.70
82.52
36.24
79.90
38.77
81.43
41.40
82.90
43.93
84.22
50.33
87.15
90.80
98.51
89.40
98.26
87.49
97.89
89.89
98.35
88.67
98.14
85.43
97.44
86.15
97.63
77.21
95.67
EXPERIMENTAL
REFERENCES
1. Kustova, T.P., Kuritsyn, L.V., and Sedova, A.O., Izv.
Vyssh. Uchebn. Zaved., Ser. Khim. Khim. Tekhnol.,
1998, vol. 41, no. 1, p. 44.
Benzhydrazide I (chemically pure grade) was pu-
rified by triple recrystallization from water. Sulfonyl
chloride II was synthesized by the procedure de-
scribed in [5] and recrystallized from benzene. THF
(chemically pure grade) was distilled on a column at
the ambient pressure. MeCN (chemically pure grade)
was dried over P2O5 and distilled on a column. The
kinetics of arylsulfonation of benzhydrazide I and
hydrolysis of sulfonyl chloride II was studied by the
conductivity method using an E7-14 immittance meter.
The errors of determination of the constant ka were
estimated by the standard statistical procedure at a
0.95 confidence level [6].
2. Kustova, T.P. and Kuritsyn, L.V., Zh. Obshch. Khim.,
1999, vol. 69, no. 2, p. 291.
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rastvorakh (Thermodynamics of Ionic Processes in
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1972.
6. Johnson, K.J., Numerical Methods in Chemistry, New
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 4 2004