Kinetic studies on the reaction of sulfinic acids with conjugated alkenes, v: Kinetics of the addition of arenesulfinic acids to 1-aryl-1-arylsulfonyl-2- nitroethenes

Article abstract of DOI:10.1080/10426500500366152

The addition of unsubstituted and substituted benzenesulfinic acids to 1-aryl-1-arylsulfonyl-2-nitroethenes has been studied kinetically by means of LC. The rection follows the second-order kinetics v = k [1-aryl-1-arylsulfonyl- 2-nitroethene].[sulfinic a

Full text of DOI:10.1080/10426500500366152

Phosphorus, Sulfur, and Silicon, 181:1593–1600, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500500366152
Kinetic Studies on the Reaction of Sulfinic Acids
with Conjugated Alkenes, V: Kinetics of the Addition
of Arenesulfinic Acids to 1-Aryl-1-arylsulfonyl-
2-nitroethenes
S. Ivanova
D. I. Aleksiev
Department of Organic Chemistry, University Prof. A. Zlatarov,
Bourgas, Bulgaria
The addition of unsubstituted and substituted benzenesulfinic acids to 1-aryl-1-
arylsulfonyl-2-nitroethenes has been studied kinetically by means of LC. The rection
follows the second-order kinetics v = k [1-aryl-1-arylsulfonyl-2-nitroethene].[sulfinic
acid]. The dependence of rate constants on the temperature and the influence of
p-substituents on the kinetic parameters have been investigated. The activation
energy and the enthalpy of the activation are calculated in the temperature range
288–308 K.
Keywords 1-Aryl-arylsulfonyl-2-nitroethenes; nucleophilic addition; sulfinic acid
INTRODUCTION
The 1-aryl-1,2-diarylsulfonyl-2-nitroethanes were obtained by the
nucleophilic addition of arenesulfinic acids to 1-aryl-1-arylsulfonyl-
2-nitroethenes.1−3 These products possess pesticide, fungicide, and
acaricide activity, and they are used as initial products for obtaining
biologically active substances.4−6 There are no systematic data avail-
able concerning the reactivity of 1-aryl-1-arylsulfonyl-2-nitroethenes
when reacting with nucleophilic reagents.
The aim of the present work was to determine quantitative pa-
rameters of the nucleophilic addition of arenesulfinic acids to hete-
roconjugated alkenes, as well as to draw conclusions about the ac-
tivity of the carbon–carbon double bond in the presence of different
substituents.
Received May 19, 2005; accepted August 18, 2005.
Address correspondence to S. Ivanova, Department of Organic Chemistry, University
of Prof. A. Zlatarov, Bourgas 8010, Bulgaria.
1593

1594
S. Ivanova and D. I. Aleksiev
RESULTS AND DISCUSSION
1-aryl-1-arylsulfonyl-2-nitroethenes were synthesized for the first time
by Scheme 1:
SCHEME 1 Ar = Ph, 4-MeC6H4, 4-NO2C6H4; Ar = Ph, 4-MeC6H4, 4-ClC6H4.
Products resulting from the addition of arenesulfinic acids to 2-
bromo-2-nitroethenylarenes were dehydrobromated in dioxane in the
presence of pyridine at a low temperature for 8 h. The composi-
tion and structure of the compounds obtained were confirmed by
elemental analysis and IR, UV, and 1H NMR spectroscopic data
(Table I).
The IR spectra of 1-aryl-1-arylsulfonyl-2-nitroethenes contain inten-
sive absorption bands of asymmetric and symmetric valence vibrations
of the nitro group at 1550–1530 cm−1 and 1380–1320 cm−1, and the sul-
fophenyl group at 1350–1300 cm−1. The absorption maximum at 890–
810 cm−1 confirms the presence of a triple-substituted double bond.
Absorption bonds corresponding to C-H aryl valence vibrations can be
seen at 3080–3000 cm−1 (a triplet). Skeleton vibrations of the aromatic
nucleus give rise to absorption maxima at 1630–1600, 1500–1490, and
1450–1400 cm−1. In some cases, the band at 1600 cm−1 is a doublet
with a second maximum at 1580 cm−1 resulting from the conjugation
1
of the benzene nucleus. The H NMR spectra of 1-aryl-1-arylsulfonyl-
TABLE I Analytical Data of Compound 3
Analysis (%) found (calcd.)
Compound Yield M.p.
Formula
mol. wt.
no.
%
◦C
C
H
N
S
3a
3b
3c
3d
3e
3f
89
189
C22H19NO6S2
445.36
C22H21NO6S2
459.37
C21H18ClNO6S2
479.81
56.64
4.27
3.15
14.40
(56.90) (4.07) (3.60) (13.95)
57.52 4.57 3.05 13.96
(56.90) (4.76) (2.80) (13.35)
52.57 3.75 2.92 13.37
(51.80) (3.27) (2.55) (12.97)
50.43 3.36 5.88 13.46
(49.60) (2.75) (5.97) (13.83)
51.44 3.67 5.71 13.08
(50.80) (3.45) (5.50) (13.21)
47.03 2.94 5.48 12.55
(46.85) (2.57) (5.50) (12.37)
73
84
89
77
85
177
174
180
183
179
C
20H16N2O8S2
476.36
C
21H18N2O8S2
490.37
C
20H15ClN2O8S2
510.81

The 1,2-Addition of Arenesulfinic Acids
1595
2-nitroethenes contain shifts of aromatic multiplets in a comparatively
wide range of 7.16–8.04 ppm. Shifts for aromatic protons tend to shift
toward a weaker field, and so does the shift for the vinyl proton since
the carbon atoms are bound to acceptor substituents. The shift for the
vinyl proton in the spectra of these compounds is at 8.21–8.25 ppm. The
UV spectra of the synthesized compounds show that the polarization of
the double bond is inessential because of the centrofugal effect of the
sulfophenyl and nitro groups.
1-aryl-1,2-diarylsulfonyl-2-nitroethanes were synthesized by
Scheme 2.
SCHEME 2 Ar = 4-MeC6H4 (1a); Ar = 4-NO2C6H4 (1b); Ar = Ph (2a); Ar =
4-MeC6H4 (2b); Arꢀ = 4-ClC6H4 (2c); Ar = 4-MeC6H4, Arꢀ = Ph (3a); Ar = Arꢀ =
4-MeC6H4 (3b); Ar = 4-MeC6H4, Arꢀ = 4-ClC6H4 (3c); Ar = 4-NO2C6H4, Ar = Ph
(3d); Ar = 4-NO2C6H4; Arꢀ = 4-MeC6H4 (3e); Ar = 4-NO2C6H4, Arꢀ = 4-ClC6H4
(3f).
The chromatographic separation of 1-aryl-1-diarylsulfonyl-2-
nitroethanes shows that the amount of one of the isomeric forms
was prevalent. If the type of the substituents and their position
to each other are taken into consideration, it could be supposed
that the percentage of isomers will be greater (Table II). Such as
interpretation of data obtained is based on Newman projections of
1-aryl-1,2-diarylsulfonyl-2-nitroethanes. These formulas show that
the voluminous and electronacceptor substituents ( SO2Arꢀ) in the
TABLE II Isomer Composition of 1-Aryl-1-Arylsulfonyl-
2-Nitro-1-Phenylsulfonylethanes
Isomer composition, %
Product
Threo
Erythro
3a
3b
3c
3d
3e
3f
55
52
53
69
66
64
45
48
47
31
34
36

1596
S. Ivanova and D. I. Aleksiev
FIGURE 1
threo-isomers are as far from each other as possible, and, therefore,
this is the most favorable structure from energy points of view. The
composition and structure of synthesized substances were determined
by instrumental methods (Figure 1).
The IR spectra of 1-aryl-1,2-diarylsulfonyl-2-nitroethanes contain in-
tensive absorption bands corresponding to asymmetric and symmetric
valence vibrations of nitro- and sulfogroups at 1560–1510, 1355–1340,
1340–1320, and 1145–1120 cm−1. Absorption bands due to C-H aryl vi-
brations can be seen at 3070–3020 cm−1. What is characteristic of these
bands is that they are in the form of a triplet with decreasing intensity.
Skeleton vibrations of the aromatic nucleus result in absorption bands
at 1640–1460 cm−1. p-Derivatives are characterized by higher wave
frequencies, the shortest wave frequency being shifted to 1640 cm−1
.
The off-plane C-H aryl deformation vibration at 830–800 cm−1 proves
the presence of p-substituted benzenes. Characteristic absorption max-
ima can also be seen at 1360–1335 and 1170–1160 cm−1, showing that
there are diarylsulfonyl groups in the compounds under study. The
1H NMR spectra contain shifts of aromatic multiplets in the interval
7.10–7.88 ppm. There are two doublets at 5.11 and 6.20 ppm, and their
integrals show the presence of one proton for each doublet. The dif-
ference in the chemical shift of the two methane protons is due to the
asymmetry. The resonance shift for the aromatic protons at 8.04 ppm
is due to the presence of a nitro group.
Kinetic parameters of the interaction of arenesulfinic acids with 1-
aryl-1-arylsulfonyl-2-nitroethenes were determined. Interactions are
second order reactions, but they are first order regarding each reagent.
The overall reaction order was determiend by using the van’t Hoff
method and the half-time method in the concentration interval 0.05–
10 M. The overall reaction order for the nucleophilic addition of ben-
zenesulfonic acid to 1-phenylsulfonyl-1-(4-tolyl)-2-nitroethene was cal-
culated to be 1.88 (Table III). These calculations can also be proved
by the line as dependence 1/[1-aryl-1-arylsulfonyl-2-nitroethene]=f (τ).

The 1,2-Addition of Arenesulfinic Acids
1597
TABLE III Experimental Proof of the Benzenesulfinic Acid Addition
Order to 1-Aryl-1-Arylsulfonyl-2-Nitroethenes by the Methods of Van’t
Hoff and Half-Time in the Concentration Range 0.005–10 M, T = 298 K
Concentration
Range C, M
0.005–0.01
1.84
0.01–0.1
1.88
0.1–1
1.91
1–10
1.94
Order value by
van’t Hoff method
Order value by
half-time method
1.85
1.88
1.87
1.90
Slopes of the straight lines for these dependencies were used to calculate
rate constants for five different temperatures. The activation energy
and the enthalpy of activation were determined using the Arrhenius
equation.
Second rate constants for the addition of benzenesulfinic acid to
2-nitro-l(4-tolyl)-1-phenylsulfonylethene at 288, 293, 298, 303, and
308 K are 6.15.10−5, 8.30.10−5, 10.17.10−5, 13.50.10−5, and 15.65.10−5
M
−1s−1. The rate constants of the reaction of 2-nitro-1(4-nitrophenyl)-
1-phenylsulfonylethene with benzenesulfinic acid at 288, 293, 298,
303, and 308 K are 7.20.10−3, 11.20.10−3, 14.80.10−3, 17.35.10−3, and
20.70.10−3 M−1s−1. The activation energy and the enthalpy of activation
for the reaction of 2-nitro-1(4-toeyl)-1-phenylsulfonylethene are calcu-
lated as 64.35 and 61.80 kJ/mol. The result for the reaction of 2-nitro-
1(4-nitrophenyl)-1-phenylsulfonylethene were 50.75 and 40.20 kJ/mol.
The influence of various substituents in the benzene nucleus on the
nucleophilic activity of sulfinic acids was studied (Table IV). As far as
the activity of the double bond in 1-aryl-2-nitro-1-phenylsulfonylethene
toward the nucleophilic reagents is concerned, it can be said that the
presence of a nitro group in the benzene nucleus favors a faster addition
reaction than in the case of 2-nitro-1-phenyl-1-phenylsulfonylethene.
The introduction of a methyl group in the para-position leads to a de-
crease in the rate of nucleophilic addition reactions.
EXPERIMENTAL
Methods
Melting points were determined on a Melt-Temp apparatus and are
uncorrected. Mcroanalyses were obtained using an elemental Ana-
lyzer −1104 (Carlo Erba). IR and UV spectra were obtained using
a Bruker and Specord UV-VIS. 1H NMR (chemical shifts measured
in deuterated solvents are given in ppm from TMS) spectra were
recorded with a Bruker 350 MHz spectrometer, using CDCl3 solutions.

1598
S. Ivanova and D. I. Aleksiev
TABLE IV The Substituent Effect on the Rate Constants
and Activation Parameters at Different Temperatures
k·105
E,
ꢀH=
Temp.
K
Nucleophile
Substrate
M
−1s−1
KJ·mol−1
KJ·mol−1
2b
1
288
293
298
303
308
288
293
298
303
308
288
293
298
303
308
288
293
298
303
308
7.35 0.7
10.20 0.9
13.45 0.9
18.70 1.1
19.50 1.0
4.28 0.4
5.95 0.6
8.15 0.5
10.05 0.4
12.67 0.4
10.25 0.9
16.50 0.9
18.40 1.1
21.05 1.0
24.70 0.8
3.15 0.4
5.80 0.3
7.72 0.6
9.85 0.5
12.08 0.4
59.20
75.50
46.40
53.10
56.60
71.70
44.30
51.90
2c
2b
2c
1
2
2
HPLC was performed using a Series-4-apparatus (Perkin-Elmer) and
a programmable multiwaveenght detector. The typical procedure for
the prepration of 1-aryl-1-arylsulfonyl-2-nitroethenes 1: to 1-aryl-1-
arylsulfonyl-2-bromo-2-nitroethenes (0.001 mol) in dioxane was added
pyridine (0.001 mol). The reaction mixture was kept standing at 8◦C
Vo2 to yield the substituted 1-aryl-1-arylsulfonyl-2-mitroethenes. The
crystals obtained were filtered and recrystallized from toluene.
Selected Data for 1a
Yield 67%, m.p. 117◦C. Found: C, 59.42; H, 4.29: N, 4.62; S, 10.57;
Calcd. for C15H13NO4S: C, 59.20; H, 3.80; N, 4.20; S, 10.80. IR (υ, cm−1
,
KBr): 1530–1330 (υNO2); 1310–1150 (υSO2); 1090 (υs-Ar); 890 (γ CH);
1
UV (λmax(EtOH), lgε): 211 (2.54); 271 (2.95); H NMR (δ, CDCl3): 2.40
(s, 3Hꢀ CH3); 7.20–7.60 (m, 9H, Ar-H); 8.20 (s, 1H, CH).
Selected Data for 1b
Yield 71%, m.p. 188◦C. Found: C, 50.31; H, 2.99; N, 8.38; S, 9.59;
Calcd. for C14H10N2O6S: C, 49.75; H, 2.67; N, 8.55; IR (υ, cm−1, KBr):

The 1,2-Addition of Arenesulfinic Acids
1599
1550–1380 (υNO2); 1310–1135 (υSO2); 1085 (υS-Ar); 850 (γ = CH); UV
1
(λmax, nm (EtOH); lgε): 212 (2.42); 260 (3.10); 280 (2.55); H NMR (δ,
CDCl3): 7.25–7.65 (m, arom. 9H); 8.24 (s, 1H, CH).
The Typical Procedure for the Preparation
of 1-Aryl-2-arylsulfonyl-2-nitro-1-phenylsulfonylethanes 3a–f
To 1-aryl-2-nitro-1-phenylsulfonylethenes (0.001 mol) in 95% ethanol
was added sulfinic acid (0.001 mol). The reaction mixture was kept
standing at 20◦C for 16 h to yield substituted 1-aryl-2-arylsulfonyl-2-
nitro-1-phenylsulfonylethanes. The crystals obtained were filtered and
recrystallized from ethanol/dioxane, 10:1.
Selected Data for 3a
IR (υ, cm−1, KBr): 1555–1360 (υNO2); 1300–1145 (υSO2); 1080 (υS-Ar); 810
(υAr-H); 1H NMR (δ, CDCl3): 2.40 (s, 3H, CH3); 5.15 (d, 1H, CH); 6.20 (d,
1H, CH); 7.10–7.65 (m, 13H, Ar-H).
Selected Data for 3b
IR (υ, cm−1, KBr): 1540–1350 (υNO2); 1350–1150 (υSO2); 1090 (υS-Ar); 815
(δAr-H); 1H NMR (δ, CDCl3): 2.42 (s, 3H, CH3); 5.11 (d, 1H, CH); 6.15 (d,
1H, CH); 7.15–7.70 (m, 13H, Ar-H).
Selected Data for 3c
IR (υ, cm−1, KBr): 1150–1365 (υNO2); 1310–1140 (υSO2); 1090 (υS-Ar); 800
1
(δAr-H); H NMR (δ, CDCl3): 2.44 (s, 3H, CH3); 6.19 (d, 1H1, CH); 5.19
(d, 1H, CH); 7.20–7.60 (m.13 H, Ar-H).
Selected Data for 3d
IR (υ, cm−1, KBr): 1555–1360 (υNO2); 1300–1140 (υSO2); 1085 (υS-Ar); 710
(δAr-H); 1H NMR (δ, CDCl3): 5.19 (d, 1H, CH); 6.18 (d, 1H, CH); 7.20–7.90
(m, 13H, Ar-H).
Selected Data for 3e
IR (υ, cm−1, KBr): 1540–1370 (υNO2); 1310–1150 (υSO2); 810 (υAr-H); 1H
NMR (δ, CDCl3): 2.43 (s, 3H, CH3); 5.12 (d, 1H, CH); 6.21 (d, 1H, CH);
7.15–8.04 (m, 13H, Ar-H).

1600
S. Ivanova and D. I. Aleksiev
Selected Data for 3e
IR (υ, cm−1, KBr): 1540–1365 (υNO2); 1310–1145 (υSO2); 1090 (δAr-H); 1H
NMR (δ, CDCl3): 5.20 (d, 1H, CH); 6.22 (d, 1H, CH); 7.20–8.00 (m, 13H,
Ar-H).
Rate Measurement
Purified sulfinic acid (0.001 mol) was added to 1-aryl-2-nitro-1-
phenylsulfonylethene (0.001 mol) in ethanol (50 mL). Aliquots were
taken out at requeat intervals of time and diluted with ethanol. Flow
concentrations of reagents during the reaction were determined by liq-
uid chromatographic analysis. Second-order constants, the activation
energy, and the enthalpy of activation were calculated according to the
literature.
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[2] L. F. Cason and L. C. Wanser, J. Am. Chem. Soc., 73, 142 (1951).
[3] S. D. Ivanova and I. Aleksiev, Phosphorus, Sulfur, and Silicon, 177, 1015 (2002).
[4] N. G. Clark, A. F. Hans, and B E. Leggetter, Nature, 12, 171 (1963).
[5] M. Pianka, J. Sci. Food Agric. 14, 48 (1963).
[6] R. L. Wain, W. Sobotka, and D. M. Spencer, Ann. Appl. Biol., 51, 445 (1963).