A kinetic study of acid-catalyzed hydrolysis of some arylsulfonyl phthalimides

Article abstract of DOI:10.1080/10426500802119655

The acid-catalyzed hydrolysis of arylsulfonyl phthalimides was studied in aqueous solutions of sulfuric, perchloric, and hydrochloric acid at 35.0 ± 0.1C. Analysis of the data by the excess acidity method and activation parameters, as well as substituent and solvent isotope effects, indicate hydrolysis by an A-2 mechanism at low acidity. At higher acidities, a changeover to an A-1 mechanism is observed.

Full text of DOI:10.1080/10426500802119655

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Phosphorus, Sulfur, and Silicon
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A Kinetic Study of Acid-
Catalyzed Hydrolysis of Some
Arylsulfonyl Phthalimides
Halil Kutuk a & Seyhan Ozturk a
a Ondokuz Mayis University, Faculty of Arts and
Sciences, Chemistry Department , Kurupelit,
Samsun, Turkey
Published online: 03 Feb 2009.
To cite this article: Halil Kutuk & Seyhan Ozturk (2009) A Kinetic Study of Acid-
Catalyzed Hydrolysis of Some Arylsulfonyl Phthalimides, Phosphorus, Sulfur, and
Silicon and the Related Elements, 184:2, 332-340, DOI: 10.1080/10426500802119655
To link to this article: http://dx.doi.org/10.1080/10426500802119655
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Phosphorus, Sulfur, and Silicon, 184:332–340, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802119655
A Kinetic Study of Acid-Catalyzed Hydrolysis of Some
Arylsulfonyl Phthalimides
Halil Kutuk and Seyhan Ozturk
Ondokuz Mayis University, Faculty of Arts and Sciences, Chemistry
Department, Kurupelit, Samsun, Turkey
The acid-catalyzed hydrolysis of arylsulfonyl phthalimides was studied in aqueous
solutions of sulfuric, perchloric, and hydrochloric acid at 35.0
0.1◦C. Analysis
of the data by the excess acidity method and activation parameters, as well as
substituent and solvent isotope effects, indicate hydrolysis by an A-2 mechanism at
low acidity. At higher acidities, a changeover to an A-1 mechanism is observed.
Keywords Acid-catalyzed hydrolysis; arylsulfonyl phthalimides; excess acidity; mech-
anism
INTRODUCTION
N-alkyl and N-arylsulfonyl phthalimides were prepared by Heller by
the reaction of potassium phthalimide with sulfonyl chlorides.1 Ear-
lier attempts by Evans and Dehn2 to prepare several N-aryl deriva-
tives and later by Scott and Lutz3 to prepare several N-alkyl deriva-
tives by this reaction were unsuccessful. More recently, potassium
phthalimide was reported to interact with p-toluenesulfonyl chlo-
ride at 140◦C or in dimethylformamide at 5◦C to 40◦C to yield N-
(p-tolylsulfonyl)phthalimide.4 The mechanisms of the acid catalyzed
hydrolysis of N-(p-substituted-arylsulfinyl)phthalimides 1 have been
studied in some detail in our laboratory.5 There has been a sys-
tematic study of the acid-catalyzed hydrolysis of sulfonylphthalim-
ides in highly acidic solutions. We now report a complementary
study of the acid-catalyzed hydrolysis of a series of N-(p-substituted-
arylsulfonyl)phthalimides (2a–c) in concentrated aqueous mineral
acids.
The rate of hydrolysis of 1 in acid solution at all temperatures is
much higher than that of 2 (Scheme 1).
Received 15 December 2007; accepted 8 April 2008.
Address correspondence to Assoc. Prof. Dr. Halil Kutuk, OMU Fen-Ed. Fakultesi,
Kimya Bolumu, 55139 Kuırupelit, Samsun/Turkey. E-mail: hkutuk@omu.edu.tr
332

Kinetics of Hydrolysis of Arylsulfonyl Phthalimides
333
O
C
O
O
S
O
S
C
N
N
R
R
C
O
C
O
O
1 (R = CH3 , H , Cl )
2 a: R = H
b: R = CH3
c: R = Br
SCHEME 1
Compounds 2 have two oxygen atoms bonded to the sulfur atom,
and a water molecule attacks the sulfur atom in the rate-determining
step at low acid concentrations. When compared with compounds 1, it is
more difficult for a water molecule to attack the sulfur atom in 2 because
of steric hindrance. At high acid concentrations, the sulfur atom of
the sulfinylium cation is less positive than that of the sulfonium ion.
Therefore, under these conditions, the more stable sulfinylium cation
forms more easily than the sulfonium cation.
RESULTS AND DISCUSSION
The first-order rate coefficients, k1, for the hydrolysis of N-
(phenylsulfonyl)phthalimide 2a in aqueous solutions of mineral acids
are shown in Figure 1. It is evident that with increasing concentra-
tion of sulfuric and perchloric acid up to 7.00 M, the rate of hydroly-
sis decreases, while at acid concentrations above 8.00 M the rate in-
creases, and there is no indication of a rate maximum even at fairly
high acidity. In all cases, the rates of hydrolysis decrease continuously
with increasing concentration of hydrochloric acid (Table I). Values of
k1 for the perchloric acid catalyzed hydrolysis of 2a–c are shown in
Figure 2.
The order of catalytic effectiveness of the acids observed for the hy-
∼
drolysis of 2a was HCl H SO > HClO . Similar behavior has been ob-
=
2
4
4
served for the acid-catalyzed hydrolysis of p-toluenesulfinamide.6 Bun-
ton et al. suggested that such an order is characteristic of a bimolecular
mechanism, transition states of positive character being preferentially
–
stabilized by anions of high charge density such as Cl , whereas the op-
posite is usually the case for A-1 reactions.7,8 The kinetic data in Table
I were also analyzed by the excess acidity treatment of Cox and Yates.9
A simplified version of their relationship for mainly unprotonated

334
H. Kutuk and S. Ozturk
8
6
4
2
0
0
5
10
15
20
[Acid] / M
FIGURE 1 Plots of k1 for the acid catalyzed hydrolysis of 2a in aqueous acid
r
solutions at 35.0◦C; :H SO , ꢁ:HCl, :HClO4.
ꢀ
2
4
TABLE I Values of 104k (s−1) for the Hydrolyses of N-(p-substitued
1
arylsulfonyl)-phthalimides at 35.0◦C
Acid
(M)
2a
2a
2a
2b
2b
2b
2c
2c
2c
H2SO4 HClO4 HCl H2SO4 HClO4 HCl H2SO4 HClO4 HCl
0.50
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
6.55
5.74
5.10
3.73
2.51
1.66
1.13
0.87
0.54
0.50
0.49
0.65
0.78
1.13
1.81
2.39
2.94
—
2.31
1.40
0.78
0.49
0.23
0.18
0.10
0.11
0.17
0.29
—
—
5.35
4.31
3.30
2.79
2.21
1.87
1.53
1.23
1.03
0.83
—
—
10.30
6.00
4.10
2.98
1.49
1.39
0.80
0.63
0.75
1.07
1.23
1.40
1.60
2.46
—
—
1.97
1.00
0.56
0.36
0.22
0.17
0.15
0.16
0.24
0.43
—
—
7.15
5.62
3.60
2.66
1.86
1.36
0.98
0.83
0.93
1.18
—
—
—
—
—
—
—
—
—
17.3
3.24
0.45
0.35
0.60
1.10
1.26
—
—
3.07
2.15
1.30
0.57
0.30
0.23
0.08
0.09
0.10
0.20
—
—
—
—
—
—
—
30.3
5.04
2.07
1.17
1.26
—
—
—
—
—
9.00
10.00
11.00
12.00
13.00
14.00
15.00
16.00
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—

Kinetics of Hydrolysis of Arylsulfonyl Phthalimides
335
40
30
20
10
0
0
2
4
6
8
10
12
[HClO4] / M
FIGURE 2 Plots of k1 for the perchloric acid catalyzed hydrolysis of 2a–c at
r
35.0◦C; : p-CH , : p-H, ꢂ: p-Br.
ꢀ
3
substrates was used:
log k1 − log CH+ − log Cs/(Cs + CSH+
)
= m∗m=X + rlog aNu + log (k0/KSH+
)
(1)
Because of the extremely low basicity of the sulfonyl phthalimides stud-
ied, the protonation correction term [log Cs / (Cs + CSH+)] can be ne-
glected. Values of X for the aqueous solution of the acid were used.10,11
Where m∗ is obtained from protonation studies, m= is the slope pa-
rameter and characteristic of the type of reaction; r log aNu for the A-2
reaction represents the nucleophilic activity, where r is the number of
water molecules involved in forming the transition state.
A plot of logk1- logC+H versus X is shown in Figure 3 for the hydrolysis
of 2a in sulfuric acid solution. A similar graph was observed for 2a–c
in perchloric acid solution. Initially, all such graphs for the arylsulfonyl
phthalimides in the low acidity region exhibit downward curvature
typical of A-2 reactions involving water.12
These changes with increasing acidity to an upper linear region are
characteristic of an A-1 process. Similar behavior has been observed
for the hydrolyses of sulfinylphthalimides,5a number of esters,13 and
benzohydroxamic acids.14 This suggests that a gradual changeover in
mechanism from A-2 to A-1 occurs with increasing concentration of the
acid.

336
H. Kutuk and S. Ozturk
-3
-4
-5
-6
0
2
4
6
8
X
FIGURE 3 Plots of logk1−logCH+ versus excess acidity for the sulfuric acid
catalyzed hydrolysis of 2a at 35.0◦C.
The temperature dependence of the rate constants of the hydrolysis
reaction was analyzed by a least-squares procedure using a spread-
sheet program (Eyring equation). The values at different acidities are
shown in Table II. Acid-catalyzed hydrolyses of esters and amides15
proceeding by an A-1 mechanism have ꢀS= of about 0 to –41.8 JK−1
mol−1, while those proceeding by an A-2 mechanism have ꢀS= of –62.8
to –125.5 JK−1 mol−1. Values of ꢀS= for the acid-catalyzed hydrolysis of
(p-methoxybenzoyl)-p-tolueneiminosulfonate were reported by Kutuk
and Tillett13 (–92.3 JK−1 mol−1 in 3.00 M and +17.2 JK−1 mol−1 in 8.00
M sulfuric acid, –57.8 JK−1 mol−1in 3.00 M perchloric acid, and +9.6
JK−1mol−1 in 6.50 M perchloric acid, respectively). They suggested an
A-2 mechanism at low acid concentration and an A-1 mechanism at
high acid concentration. Over the range 5.00–13.00 M sulfuric acid,
the values of ꢀS= changed from –76.86 to –23.67 JK−1 mol−1 for the
hydrolysis of 2a. Values in perchloric acid varied in a similar way, as
expected.
The kinetic solvent isotope effect (kD/ kH) observed for the hydrolysis
of 2a is shown in Table III. The increasing values of the kinetic solvent
isotope effect with acidity [e.g., for 2a, k1D2O/k1H2O = 1.19 (3.00 M
H2SO4) and 2.38 (14.00 M H2SO4)] are also consistent with a change
from A-2 to A-1.16
In the acidity range studied, electron-donating substituents cause
the highest rate of hydrolysis (2b > 2c), and the substituent effects are
well correlated by a satisfactory Hammett ρσ plot [at 9.00 M HClO4,

Kinetics of Hydrolysis of Arylsulfonyl Phthalimides
337
TABLE II Arrhenius Parameters for the Hydrolysis of
N-(p-substituted arylsulfonyl)-phthalimides
ꢀH=
(kJ/mol)
ꢀS=
(J/molK)
Temperature
Range (◦C)
Acid
(M)
r2
2a H2SO4
5.00
9.00
74.30 0.95
87.28 0.86
–76.86 3.10
–44.51 2.80
–23.67 4.33
25–40
25–40
25–40
25–40
30–45
30–45
25–40
25–40
25–40
25–40
30–45
30–45
25–40
30–45
30–45
0.9994
0.9997
0.9995
0.9995
0.9997
0.9993
0.9992
0.9993
0.9997
0.9997
0.9992
0.9994
0.9996
0.9998
0.9991
13.00 91.61 1.33
HClO4
2b H2SO4
HClO4
2.00
5.00
9.00
5.00
9.00
56.98 0.71 –134.34 2.32
76.10 0.68
82.68 1.17
74.07 1.28
81.24 1.18
–87.47 2.17
–68.68 3.75
–78.25 4.18
–60.73 3.85
–34.51 2.55
13.00 87.46 0.78
2.00
5.00
9.00
2.00
5.00
9.00
63.75 0.57 –115.39 1.87
70.64 1.10 –105.76 3.55
80.38 1.02
59.94 0.76 –121.25 2.47
72.80 0.62
86.18 1.62
–73.27 3.26
2c
HClO4
–95.87 2.00
–61.35 5.19
ρ = –0.955 (corr. 0.9959)]. Clearly at these acidities, electron-donating
substituents both facilitate protonation of the substrate and stabilize
the sulfonium cation in the case of an A-1 mechanism. At lower acidi-
ties, however [e.g., 2.00 M HClO4, ρ = 0.848 (corr. 0.9997)], 2c hy-
drolyzes more rapidly than 2b, consistent with a predominantly A-2
mechanism, in which substituent effects on the protonation and slow
step operate in opposite directions. There is no direct evidence concern-
ing the site of protonation of sulfonyl phthalimides; however, protona-
TABLE III Deuterium Solvent Isotope Effect
for the Hydrolysis of 2a in Sulfuric Acid
Solutions at 35.0 0.1◦C
Acid (mol dm−3
3.00 M D2SO4
)
104k1(s−1
)
104kave.(s−1
)
kD2O/kH2O
4.47
4.45
3.74
3.72
4.30
4.32
1.82
1.80
4.46
1.19
3.00 M H2SO4
14.00 M D2SO4
14.00 M H2SO4
3.73
4.31
1.81
2.38

338
H. Kutuk and S. Ozturk
tion of sulfinamides,6,17sultams,18 and cyclic sulfamate esters19occurs
preferentially at the nitrogen atom.
In the light of the overall evidence, we propose that the acid-
catalyzed hydrolysis of arylsulfonyl phthalimides occurs according to
an A-2 mechanism at lower acidities and an A-1 mechanism at higher
acidities, as shown in Schemes 2 and 3, respectively.
O
C
O
C
O
S
O
S
H
N
R
N
H2O
R
+
+
H3O+
C
O
C
O
O
O
Slow H2O
O
C
O
H
O
S
O
C
N
δ+
N
R
S
R
OH2
H
C
O
δ+
C
O
O
O
H
H
O
O
S
H+
+
R
OH
O
SCHEME 2
EXPERIMENTAL
Materials
Arylsulfonyl phthalimides 2a–c were prepared from the correspond-
ing arylsulfonyl chlorides by reaction with potassium phthalimide in
refluxing acetonitrile, as described by Heller.1 Phthalimide was ob-
tained from Aldrich, and p-toluenesulfonic acid was prepared as de-
scribed in the literature.20 1H NMR spectra were recorded on a Bruker
AC 200 MHz spectrometer using TMS as the internal standard. All
melting points were obtained using an electrothermal digital melting
1
point apparatus. 2a: m.p. 202–203◦C (lit.[1]202.5–203.5◦C); H NMR
(d6-DMSO): δ = 7.5–8.1 (m, 9H, arom-H); 2b: m.p. 240–241◦C (lit.1
239–240◦C); 1H NMR (d6-DMSO): δ = 1.8 (s, 3H, CH3), 7.4–8.0 (m, 8H,

Kinetics of Hydrolysis of Arylsulfonyl Phthalimides
339
O
C
O
C
O
S
O
S
H
N
R
N
H2O
R
+
+
H3O+
C
O
C
O
O
O
Slow
O
C
O
S
O
S
Fast
H2O
R
OH2
H
N
+
R
C
O
O
O
O
S
H+
+
R
OH
O
SCHEME 3
1
arom-H); 2c: m.p. 249–250◦C (lit.1 247–248◦C); H NMR (d6-DMSO):
δ = 7.5–8.0 (m, 8H arom-H).
Kinetic Studies
The rates of hydrolysis of arylsulfonyl phthalimides were followed spec-
trophotometrically at 230–250 nm using a GBC Cintra 20 Model UV-
VIS spectrometer with a thermostatted cell compartment ( 0.05◦C).
Good first-order behavior was observed with clean isosbestic points.
Values of k1 were calculated from the standard equation using a least-
squares procedure. All kinetic measurements were duplicated and the
average deviation from the mean was <3%.
Product Analysis
The products of hydrolysis were determined by comparing the UV
spectrum obtained after completion of the kinetic experiment with
the spectrum of the expected products at the same concentration
and under the same conditions. Thus for the hydrolysis of N-(p-
toluenesulfonyl)phthalimide, the UV spectrum recorded at the end of

340
H. Kutuk and S. Ozturk
the reaction was identical with that of a 1:1 mixture of phthalimide
and p-toluenesulfonic acid.
REFERENCES
[1] M. S. Heller, J. Chem. Eng. Data, 15, 351 (1970).
[2] T. W. Evans and W. M. Dehn, J. Am. Chem. Soc., 51, 3651 (1929).
[3] R. B. Jr. Scott and R. E. Lutz, J. Org. Chem., 19, 830 (1954).
[4] G. H. L. Nefkens, G. I. Tesser, and R. J. F. Nivard, Rec. Trav. Chim., 79, 688 (1960).
[5] H. Kutuk, Y. Bekdemir, and Y. Soydas, J. Phys. Org. Chem., 14, 224 (2001).
[6] H. Asefi and J. G. Tillett, J. Chem. Soc. Perkin Trans., 2, 1579 (1979).
[7] C. A. Bunton, J. H. Crabtree, and L. Robinson, J. Am. Chem. Soc.,90, 1258 (1968).
[8] C. A. Bunton and J. H. Fendler, J. Org. Chem., 31, 3764 (1966).
[9] R. A. Cox and K. Yates, J. Am. Chem. Soc., 57, 2944 (1979).
[10] R. A. Cox and K. Yates, J. Am. Chem. Soc., 100, 3861 (1978).
[11] R. A. Cox, Adv. Phys. Org. Chem., 35, 1 (2000).
[12] K. Yates and R. A. McCelland, J. Am. Chem. Soc., 89, 2686 (1967).
[13] H. Kutuk and J. Tillett, Phosphorus, Sulfur, and Silicon, 85, 217 (1993).
[14] K. K. Ghosh and S. Ghosh, J. Org. Chem., 59, 1369 (1994).
[15] L. L. Schaleger and F. A. Long, Adv. Phys. Org. Chem., 1, 1 (1963).
[16] J. G. Pritchard and F. A. Long, J. Am. Chem. Soc., 80, 4162 (1958).
[17] B. Bujnicki, J. Drabowicz, M. Mikolajczyk, A. Kolbe, and L. Stefaniak, J. Org. Chem.,
61, 7593 (1996).
[18] Y. Bekdemir, J. G. Tillett, and R. I. Zalewski, J. Chem. Soc., Perkin Trans., 2, 1643
(1993).
[19] Y. Bekdemir, H. Kutuk, S. Celik, and J. G. Tillett, Phosphorus, Sulfur, and Silicon,
177, 973 (2002).
[20] A. I. Vogel, Textbook of Practical Organic Chemistry (Longmans, London, 1989) 5th
ed., Chap. 6, pp. 874–875.