The synthesis and substituent effect of the acid catalyzed hydrolysis of amidosulfites

Article abstract of DOI:10.1080/10426500500272186

The acid-catalyzed hydrolysis of 2-oxo-3-(p-substituted)-phenyl-5-methyl-1, 2,3-oxathiazolidines (1) have been studied in 60% (v/v) 1,4 dioxane-aqueous solutions of perchloric and hydrochloric acids at 10.0 ± 0.05°C. The analysis of the kinetic data by th

Full text of DOI:10.1080/10426500500272186

This article was downloaded by: [UOV University of Oviedo]
On: 15 October 2014, At: 01:15
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Phosphorus, Sulfur, and Silicon
and the Related Elements
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/gpss20
The Synthesis and Substituent
Effect of the Acid Catalyzed
Hydrolysis of Amidosulfites
Halil Kutuk a , Yunus Bekdemir a & Nalan Turkoz a
a Department of Chemistry , Ondokuz Mayis
University , Kurupelit, Samsun, Turkey
Published online: 15 Aug 2006.
To cite this article: Halil Kutuk , Yunus Bekdemir & Nalan Turkoz (2006) The
Synthesis and Substituent Effect of the Acid Catalyzed Hydrolysis of Amidosulfites,
Phosphorus, Sulfur, and Silicon and the Related Elements, 181:4, 931-937, DOI:
10.1080/10426500500272186
To link to this article: http://dx.doi.org/10.1080/10426500500272186
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.

This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Phosphorus, Sulfur, and Silicon, 181:931–937, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500500272186
The Synthesis and Substituent Effect of the Acid
Catalyzed Hydrolysis of Amidosulfites
Halil Kutuk
Yunus Bekdemir
Nalan Turkoz
Ondokuz Mayis University, Department of Chemistry, Kurupelit,
Samsun, Turkey
The acid-catalyzed hydrolysis of 2-oxo-3-(p-substituted)-phenyl-5-methyl-1,2,3-
oxathiazolidines (1) have been studied in 60% (v/v) 1,4 dioxane-aqueous solutions
of perchloric and hydrochloric acids at 10.0 0.05◦C. The analysis of the kinetic
data by the order of the catalytic effects of the acids, activation parameters, kinetic
solvent isotope effect, and substituent effect are all in agreement with an A-2 mech-
anism in the studied range.
Keywords Acid-catalyzed hydrolysis; amidosulfites; oxathiazolidines; substituent effect
INTRODUCTION
In the literature, the first reported amidosulfite was 2-oxo-1,2,3-
oxathiazolidine (2), which was prepared by J.A. Deyrup and C.L. Moyer
by the reaction of β-amino alcohols with thionyl chloride in the presence
of base in good to excellent yields.1 The structure of (2) constitutes the
first example of the 1,2,3-oxathiazolidine heterocyclic ring system.
In 1976, the 2-oxo-1,2,3-oxathiazolidines (2), were reported effec-
tively to inhibit the growth of Staphylococcus aureus and Escherichia
coli.2
The first kinetic study of the acid-catalyzed ring opening of this class
of compound on 3-tert-butyl-1,2,3-oxathiazolidine-2-oxide with up to
2.0 M aqueous mineral acids was studied by Cox and his colleagues
by using a stopped-flow spectrophotometer, and they suggested an A-2
mechanism in this range.3 The kinetics and mechanism of the hydrol-
ysis of 2-oxo-3-(p-substituted)-phenyl-5-methyl-1,2,3-oxathiazolidine
Received March 15, 2005; accepted April 12, 2005.
This work was supported by the Research Fund of Ondokuz Mayis University.
Address correspondence to Halil Kutuk, OMU Fen-Ed. Fakultesi, Kimya Bolumu,
55139 Kurupelit, Samsun, Turkey. E-mail: hkutuk@omu.edu.tr
931

932
H. Kutuk et al.
(1a–c) have been studied in 60% (v/v) 1,4-dioxane-aqueous solutions
of perchloric and hydrochloric acids at 10.0 0.05◦C.
There has been no systematic study of the acid-catalyzed hydroly-
sis of 1,2,3-oxathiazolidines in acidic solutions. We now report a com-
plementary study of the acid-catalyzed hydrolysis of a series of 2-oxo-
3-(p-substituted)-phenyl-5-methyl-1,2,3-oxathiazolidines (1a–c) in 60%
(v/v) 1,4-dioxane-aqueous solutions of mineral acids.
RESULTS AND DISCUSSION
The first-order rate coefficients, k1, for the hydrolysis of 2-oxo-3-
(p-methyl)-phenyl-5-methyl-1,2,3-oxathiazolidine (1a) in aqueous 60%
(v/v) dioxane solutions of mineral acids are shown in Figure 1, Scheme 1.
SCHEME 1
In all cases, the rate of hydrolysis increases continuously with in-
creasing acid concentration (Table I). Due to the high reactivity of the
oxathiazolidines, the hydrolysis proceeds very rapidly; therefore, it can-
not be followed in sulfuric acid by a UV spectrometer at 10.0 0.05◦C.
It also was difficult to follow the reaction above 0.6 M HCl and HClO4
at this temperature. The order of catalytic effectiveness of the added
acids observed for the hydrolysis of the amidosulfite was H2SO4 > HCl >
HClO4. Bunton and colleagues4 suggested that such an order is charac-
teristic of a bimolecular (A-2) mechanism, in which a developing positive
character in transition states being preferentially stabilized by anions
of high charge density such as Cl−, whereas the converse, is usually the
case for an unimolecular (A-1) mechanism (HClO4 > HCl > H2SO4).
The temperature dependence of the rate constants of the hydroly-
sis reaction was studied at different temperatures and analyzed by a
least-squares procedure using a computer program (Eyring equation).
Entropies of activation (ꢀS=) have been used as mechanistic criteria
for distinguishing between A-1 and A-2 mechanism;5,6 generally, an

Acid Catalyzed Hydrolysis of Amidosulfites
933
FIGURE 1 The acid-catalyzed hydrolyses of 2-oxo-3-(p-methyl)-phenyl-5-
methyl-1,2,3-oxathiazolidines in the presence of 60% dioxane-water (v/v) at
10.0 0.05◦C. ( , HCl; ꢁ, HClO )
ꢀ
4
A-1 mechanism is expected to have a more positive value than the cor-
responding an A-2 mechanism.
The calculated entropies of activation as shown in Table II also
support suggested an A-2 reaction mechanism of the hydrolysis
should be reaction mechanism for the hydrolysis of the amidosul-
fites. Values of the entropy of activation for the hydrolysis of the
(1a) (ꢀS= = −93.69, −94.23 JK−1 mol−1) for 0.10 M perchloric and
0.10 M hydrochloric acids, respectively. It is suggested that the
TABLE I Values of 102 k (s−1) for the Hydrolyses of 2-Oxo-3-
1
(p-substituted)-phenyl-5-methyl-1,2,3-oxathiazolidines in
the Presence of 60% Dioxane-Water (v/v) at 10.0 0.05◦C
1a
(HClO4)
1a
(HCl)
1b
(HClO4)
1b
(HCl)
1c
(HClO4)
1c
(HCl)
[H+](M)
0.10
0.20
0.30
0.40
0.50
0.60
0.54
0.78
0.87
0.90
1.02
1.26
0.56
0.91
1.27
1.53
2.47
–
2.58
5.66
10.1
14.7
20.7
29.8
1.85
4.30
7.53
10.7
15.9
24.8
1620
2900
3980
–
–
–
2503
3635
4287
–
–
–

934
H. Kutuk et al.
TABLE II Arrhenius Parameters for the Hydrolysis of
2-Oxo-3-(p-substituted)-phenyl-5-methyl-1,2,3-
oxathiazolidines in the Presence of 60% Dioxane-Water
(v/v) at 10.0 0.05◦C
ꢀH=
ꢀS=
Compound
Acid
[H+]/M
(kJmol−1
)
(JK−1 mol−1
)
R2
1a
HClO4
HCl
HClO4
0.10
0.10
0.10
0.30
0.10
0.30
55.29
55.06
51.94
48.98
55.05
56.47
−93.69
−94.23
−92.43
−91.78
−84.09
−67.55
0.997
0.998
0.992
0.996
0.995
0.999
1b
HCl
negative values of ꢀS= for an A-2 mechanism is a reflection of
the loss of rotational and translational freedom of water molecules
in the transition state, where a water molecule acts as a nucle-
ophile. The acid-catalyzed hydrolysis of esters and amides6 pro-
ceeding by an A-1 mechanism have ꢀS= ≈ 0 to −41.8 JK−1 mol−1
,
while those proceeding by an A-2 mechanism have ꢀS= ≈ −62.8 to
−125.5 JK−1 mol−1
.
The value obtained for the deuterium Kinetic Solvent Isotope Effect
(KSIE) (kD1 O/kH1 O) for the sulfuric acid-catalyzed hydrolysis of 2-oxo-
3-phenyl-5-methyl-1,2,3-oxathiazolidine is 1.12 (Table III). The values
of KSIE for the hydrolysis of amidosulfites are comparable to those of
2
2
3-chloropropyl-p-toluenesulfinate7 (kD O/kH O = 1.78 in 1.0 M HCl) and
2
2
p-nitrophenyl-N-aroyl-p-tolueneiminosulfonate8 (kD O/kH O = 1.63 in
2
2
3.0
M
HClO4) and N-(4-substituted-arylsulfinyl)phthalimides9
(kD O/kH O = 1.02 in 1.0 M H2SO4), which hydrolyze by a normal A-2
2
2
mechanism.
TABLE III Deuterium Solvent Isotope Effect for the Hydrolysis
of 2-Oxo-3-phenyl-5-methyl-1,2,3-oxathiazolidine in 60%
Dioxane-Water (v/v)
Acid
solutions
102 k1
Temperature (◦C)
10.0 0.05
102 k1(s−1
)
average (s−1
)
k1D2O/k1
H
O
2
0.1 M H2SO4
0.1 M D2SO4
2.47
2.47
2.46
2.78
2.76
2.47
2.77
1.12
10.0 0.05

Acid Catalyzed Hydrolysis of Amidosulfites
935
FIGURE 2 The plot of log k1 versus Hammett σ values for the acid-catalyzed
hydrolyses (0.30 M HClO4) of 2-oxo-3-(p-substituted)-phenyl-5-methyl-1,2,3-
oxathiazolidines in the presence of 60% dioxane-water (v/v) at 10.0 0.05◦C.
In the studied acidity range, electron-withdrawing substituents pro-
duce the highest rate of hydrolysis, and the substituent effects are
well correlated by a satisfactory Hammett plot [at 0.30 M HClO4,
ρ = 9.27 (corr. 0.978) and 0.30 M HCl, ρ = 3.79 (corr. 1.00)] as
shown in Figures 2 and 3 respectively. Clearly at these acidities, an
electron-withdrawing substituent increases the positive charge on a
sulfur atom, and water can attack rapidly to the sulfur atom in the
rate-limiting step for an A-2 mechanism. There is no direct evidence
concerning the site of the protonation of amidosulfites; however, the
protonation of sulfinamides10,11 and sultams12 occur preferentially at
the nitrogen atom.
FIGURE 3 The plot of log k1 versus Hammett σ values for the acid-
catalyzed hydrolyses (0.30 M HCl) of 2-oxo-3-(p-substituted)-phenyl-5-methyl-
1,2,3-oxathiazolidines in the presence of 60% dioxane-water (v/v) at 10.0
0.05◦C.

936
H. Kutuk et al.
SCHEME 2
In the light of the overall evidence, we propose that the acid-
catalyzed hydrolysis of 2-oxo-3-(p-substituted)-phenyl-5-methyl-1,2,3-
oxathiazolidines in 60% (v/v) 1,4-dioxane-aqueous solutions occurs by
the an A-2 mechanism, as shown in Scheme 2. In this first step, a rapid
preequilibrium protonation of 2-oxo-3-(p-substituted)-phenyl-f-methyl-
1,2,3-oxathiazolidine takes place. It is assumed that the protonation
occurs on nitrogen atom and a water molecule attacks to sulfur atom
as nucleophile in the rate determining step.
EXPERIMENTAL
Materials
2-oxo-3-(p-substituted)-phenyl-5-methyl-1,2,3-oxathiazolidines (1a–c)
were prepared from the corresponding N-sulfinyl-p-substituted ani-
lines with propylene oxide in the presence of LiCl in DMF as de-
scribed by Nishiyama and Yamada.13 This involved the reaction of
thionyl chloride with (p-substituted)-aniline in benzene to give the N-
sulfinyl-p-substituted anilins.14 1a, had m.p. 85◦C (lit13., 83.2–85◦C);
1H NMR (acetone-d6), δ 1.16–1.63 (dd, 3H), 2.27 (s, 3H), 3.66 (t,
1H), 3.93 (q, 1H), 4.98 (m,1H), 6.59–7.14 (m,4H); 1b, had m.p. 58◦C
1
(lit13., 59.3–59.8◦C); H NMR (acetone-d6), δ1.58 (d, 3H), 3.40 (t, 1H),
4.02 (q, 1H), 5.43 (m, 1H), 6.58–7.37 (m, 5H); 1c, m.p. 92◦C (lit13.,
91.8–92.6◦C).

Acid Catalyzed Hydrolysis of Amidosulfites
937
Kinetic Procedure
The rates of the acid-catalyzed hydrolysis of 2-oxo-3-(p-substituted)-
phenyl-5-methyl-1,2,3-oxathiazolidines were followed spectrometri-
cally at 190–400 nm using a GBC Cintra 20 Model UV-VIS spectropho-
tometer with a thermostatted cell compartment (10 0.05◦C). 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 <5%.
Product Analysis
The product of the hydrolysis was determined by comparing the UV
spectrum obtained at the completion of the kinetic experiment with
the spectrum of the expected product which was run at the same
concentration and under the same conditions. The UV spectra of the
hydrolysis of 2-oxo-3-(p-chloro)-phenyl-5-methyl-1,2,3-oxathiazolidine
(1c) were shown to be identical to that of the corresponding 1-
(4-cholorophenylamino)-propane-2-ol, which was prepared from 4-
chloroaniline with propylene oxide in ethanol. 1-(4-chlorophenylamino)-
propane-2-ol, m.p. 40–41◦C; (Found: C, 58.63; H, 6.74; N, 7.49. Calc. for
C9H12NOCl: C, 58.22; H, 6.53; N, 7.55%).
REFERENCES
[1] J. A. Deyrup and C. L. Moyer, J. Org. Chem., 34, 175 (1969).
[2] H. U. Stracke and G. Koppensteiner, German patent DE 2456874 (1976), Chem.
Abstr., 85, 112656e (1976).
[3] S. Cox, O. M. H. El Dusouqui, W. Mc. Cormack, and J. G. Tillett, J. Org. Chem., 40,
949 (1975).
[4] C. A. Bunton, H. J. Crabtree, and L. Robinson, J. Am. Chem. Soc., 90, 1258 (1968).
[5] R. W. Taft, J. Chem. Soc., 74, 5374 (1952).
[6] L. L. Schaleger and F. A. Long, Adv. Phys. Org. Chem., 1, 1 (1963).
[7] H. Kutuk, Doctoral Thesis, Department of Chemistry, University of Essex, England
(1994).
[8] H. Kutuk and J. Tillett, Phosphorus, Sulfur, and Silicon, 85, 217 (1993).
[9] H. Kutuk, Y. Bekdemir, and Y. Soydas, J. Phys. Org. Chem., 14, 224 (2001).
[10] H. Asefi and J. G. Tillett, J. Chem. Soc., Perkin Trans., 2, 1579 (1979).
[11] B. Bujnicki, J. Drabowicz, M. Mikolajczyk, A. Kolbe, and L. Stefaniak, J. Org. Chem.,
61, 7593 (1996).
[12] Y. Bekdemir, J. G. Tillett, and R. I. Zalewski, J. Chem. Soc., Perkin Trans., 2, 1643
(1993).
[13] T. Nishiyama and F. Yamada, Bull. Chem. Soc. Japan, 44, 3073 (1971).
[14] S. Rajagopalan, B. G. Advani, and C. N. Talaty, Organic Syntheses cell, 5, 504 (1973).