Addition of sulfinic acids to methacrylic derivatives

Article abstract of DOI:10.1080/10426501003776947

The kinetics of the addition of arenesulfinic acids to methacrylic derivatives were studied. The reactions were found to be second order over a range of concentrations from 0.01 to 0.10 M. For pH values ranging from 4 to 8, the following rate constants were obtained pH the methylacrylate, chloromethylacrylate, and bromomethylacrylate with benzenesulfinic acids (278 K) were investigated: 2.37 (± 0.2).10^-4 M^-1s ^-1, 2.60 (± 0.1).10^-4 M^-1s^-1, 3.15 (± 0.3).10^-4 M^-1s^-1. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426501003776947

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Addition of Sulfinic Acids to Methacrylic
Derivatives
S. Ivanova a & D. Aleksiev a
a Department of Organic Chemistry , University “Prof. Asen
Zlatarov” , Bourgas, Bulgaria
Published online: 13 Jan 2011.
To cite this article: S. Ivanova & D. Aleksiev (2010) Addition of Sulfinic Acids to Methacrylic
Derivatives, Phosphorus, Sulfur, and Silicon and the Related Elements, 186:1, 38-43, DOI:
10.1080/10426501003776947
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Phosphorus, Sulfur, and Silicon, 186:38–43, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426501003776947
ADDITION OF SULFINIC ACIDS TO METHACRYLIC
DERIVATIVES
S. Ivanova and D. Aleksiev
Department of Organic Chemistry, University “Prof. Asen Zlatarov”,
Bourgas, Bulgaria
GRAPHICAL ABSTRACT
Y
ArSO2H
2
ArSO2CH2(Y)COOCH3
3
+
C
CH2
COOCH3
1
Abstract The kinetics of the addition of arenesulfinic acids to methacrylic derivatives were
studied. The reactions were found to be second order over a range of concentrations from 0.01
to 0.10 M. For pH values ranging from 4 to 8, the following rate constants were obtained
pH the methylacrylate, chloromethylacrylate, and bromomethylacrylate with benzenesulfinic
acids (278 K) were investigated: 2.37 ( 0.2).10−4 M−1s−1, 2.60 ( 0.1).10−4 M−1s−1, 3.15
(
0.3).10−4 M−1s−1
.
Keywords Methacrylic derivatives; nucleophilic addition; sulfinic acids
INTRODUCTION
The salts of sulfinic acids and sulfinic acids themselves, when reacting with α,β-
unsaturated compounds, behave like typical nucleophilic compounds.1,2 No matter what
the pH of the medium is, sulfinic acids and α,β-unsaturated compounds react in equimo-
lar quantities, with the corresponding sulfones being obtained. When there is a halogen
at the double bond, the reaction depends on the pH of the medium: additive compounds
are obtained in acidic medium, and unsaturated sulfones are obtained in alkaline medium.
The interaction of the sodium salts of sulfinic acids with acrylonitrile, α-chloroacrylonitrile,
methyl-, ethyl-, and butyl-esters of acrylic acids was studied.3,4 Achmatowicz and Michalski
studied the addition of sulfinic acids to acrylic compounds such as acrylonitrile, methy-
lacrylate, ethylacrylate, amide of acrylonitrile, and vinilpyridine.5,6
The aim of the present study is to obtain some new sulfones by a nucleophilic addition
of benzene-, toluene-, and 4-chlorobenzenesulfinic acids to methylacrylate, α-chloro-, and
α-bromomethylacrylate, as well as to determine the kinetic parameters of these reactions.
Received 11 February 2010; accepted 15 March 2010.
Address correspondence to S. Ivanova, Department of Organic Chemistry, University “Prof. Asen Zlatarov”,
8000 Bourgas, Bulgaria. E-mail: viperorg@abv.bg
38

ADDITION OF SULFINIC ACIDS TO METHACRYLIC DERIVATIVES
39
RESULTS AND DISCUSSION
Synthesis and Structure
A series of aryl–β-carbomethoxyethyl sulfones and aryl–β-halogenocarbo-
methoxyethyl sulfones were obtained by the reaction shown in Scheme 1.
Y
CH2 = C
+ ArSO2H
2a - c
ArSO2CH2CH(Y)COOCH3
3a - i
COOCH3
1a - c
Y = H (1a); Y = Cl (1b);Y= Br (1c); Ar = Ph (2a); Ar = 4-MeC6H4 (2b);
Ar = 4-ClC6H4 (2c); Y = H, Ar = Ph (3a); Ar = H , Ar = 4-MeC6H4 (3b);
Y = H, Ar = 4-ClC6H4 (3c); Y =Cl, Ar = Ph (3d); Y =Cl, Ar = 4-MeC 6H4 (3e)
Y =Cl, Ar = 4-ClC6H4 (3f); Y =Br, Ar = Ph (3g); Y =Br, Ar = 4-MeC H4 (3h)
6
Y =Br, Ar = 4-ClC6H4 (3i)
Scheme 1
These are available concerning some of these compounds, namely 3a, 3c, 3e,
and 3f.3 The synthesized aryl β-carbomethoxyethyl sulfones and aryl β-halogenocarbo-
methoxyethyl sulfones are white crystalline substances, stable at long storage. All newly
formed compounds were analyzed by analytical and instrumental methods (Tables 1
and 2).
The IR-spectra of aryl β-carbomethoxyethyl sulfones and aryl β-halogenocarbome-
thoxyethyl sulfones contain intense bands of asymmetric and symmetric valence vibration
due to the sulfonyl groups at 1315–1305 cm−1 and 1145–1130 cm−1. There are absorption
maxima characteristic of the valence vibrations of C O at 1300–1100 cm−1. The valence
vibrations at 1740–1725 cm−1 prove the presence of C O groups. The characteristic bands
at 3100–3000 cm−1 correspond to valence C H aryl vibrations. Skeleton vibrations of
the arene nucleus can be seen at 1640–1600 cm−1 and 1480–1450 cm−1. The absorption
bands due to the monosubstituted benzene nucleus are at 700 cm−1, and those for the
p-disubstituted benzene nucleus are at 810–800 cm−1. The presence of a methylene group
is proven by the absorption maximum for the valence asymmetric and symmetric vibrations
at 2900–2840 cm−1, and the deformation vibrations at 1470–1450 cm−1
.
The 1H NMR spectra of the synthesized compounds contain shifts corresponding to
aromatic multiplets at 7.27–7.82 ppm. The doublets that prove the presence of methine
protons are centered at 2.72–2.85 ppm, and the chemical shift corresponding to methylene
protons (a triplet) is at 3.38–3.47 ppm. Shifts due to the methyl protons of the methoxygroup
can be seen at 3.65 ppm.
Kinetic Study
The main kinetic parameters of the nucleophilic addition of sulfinic acids to methy-
lacrylate and its halogenoderivatives were determined by UV spectroscopy. The absorption
maxima of sulfinic acids and the final aryl halogenocarbomethoxyethyl sulfones overlap, so
the change in their concentration is difficult to estimate. That is why a method suggested by
Ogata et al.7 modified by the present authors was used to determine the kinetic parameters
of the reaction. In the course of the interaction, the change in the concentration of sulfinic

40

ADDITION OF SULFINIC ACIDS TO METHACRYLIC DERIVATIVES
41
Table 2 Spectra of the newly synthesized compounds
Spectral data
Compound no.
3b
IR (υ, cm−1, KBr): 1310, 1145 (SO2); 1110, 1725 ( COOCH3)
1H NMR (δ, ppm, CDCl3): 2.72 (t, 2H, CH2), 3.38 (t, 2H, CH2), 3.65 (s, 3H, OCH3),
2.46 (S, 3H, CH3), 7.72–7.82 (m, 4H, C6H4), J(CH CH)7.2 Hz.
3g
3h
3e
IR (υ, cm−1, KBr): 1300, 1135 (SO2); 1115, 1730 ( COOCH3)
1H NMR (δ, ppm, CDCl3): 2.75 (d, 2H, CH2), 3.38 (t, 1H, CH), 3.62 (s, 3H, OCH3),
2.46 (S, 3H, OCH3), 7.30–7.77(m, 5H, C6H5), J(CH CH)7.4 Hz.
IR (υ, cm−1, KBr): 1300, 1140 (SO2); 1125, 1730 ( COOCH3)
1H NMR (δ, ppm, CDCl3): 2.78 (d, 2H, CH2), 3.47 (t, 1H, CH), 3.65(s, 3H, OCH3),
2.45 (S, 3H, CH3), 7.26–7.820 (m, 4H, C6H4), J(CH CH)7.3 Hz.
IR: (υ, cm−1, KBr): 1310, 1140 (SO2); 1130, 1740 ( COOCH3)
1H NMR (δ, ppm, CDCl3): 2.81 (d, 2H, CH2), 3.45 (t, 1H, CH), 3.60 (s, 3H, OCH3),
7.28–7.84 (m, 4H, C6H4), J(CH CH)7.4 Hz.
acid was studied, making use of the fact that the acid turns into dihydroxybenzosulfone
when a standard solution of benzoquinone is added to it.
The concentration of dihydroxybenzosulfones (and therefore the concentration of
sulfinic acid) was determined at 324 nm. The data concerning the reaction order of the
addition of benzenesulfinic acid to methylacrylate, chloro-, and bromomethylacrylate are
presented in Table 4. Using straight lines for the reactions under study it is possible to
calculate the bimolecular rate constants. Having in mind that the nucleophilic addition of
sulfinic acids corresponds to a second order kinetic reaction, the most probable reaction
scheme can be suggested, as shown in Scheme 2.
+ H2O
- H2O
-
Y
C = O
ArSO2CH2CH = C - O
+ ArSO2
CH2 = C
Y
OCH3
OCH3
ArSO CH CH - C -
OCH3 + OH
2
2
Y
O
Scheme 2
Table 3 Experimental values of the benzenesulfinic acid addition order to methacrylate, chloro-, and bro-
momethacrylate by methods of Van’t Hoff and half-time at 298 K
Concentration range C, M
0.01–0.025
0.025–0.05
0.05–0.075
0.075–0.1
Order value by Van’t Hoff method 1a and 2a
Order value by half- time method 1a and 2a
Order value by Van’t Hoff method 1b and 2a
Order value by half- time method 1b and 2a
Order value by Van’t Hoff method 1c and 2a
Order value by half- time method 1c and 2a
1.63
1.65
1.70
1.72
1.68
1.69
1.60
1.64
1.68
1.70
1.66
1.71
1.66
1.67
1.73
1.72
1.60
1.66
1.68
1.65
1.70
1.72
1.64
1.66

42
S. IVANOVA AND D. ALEKSIEV
Table 4 Rate coefficient and activation parameters for the reaction of methacrylic derivatives with sulfinic acids
Methacrylic
derivatives
Sulfinic
acids
T, K
k .104 M−1,, s−1
Ea (kJ/mol)
ꢀ H= (kJ/mol)
63.25
1a
1a
1a
1b
1b
1b
1c
1c
1c
2a
2b
2c
2d
2b
2c
2a
2b
2c
278
288
298
278
288
298
278
288
298
278
288
298
278
288
298
278
288
298
278
288
298
278
288
298
278
288
298
2.37 0.2
2.45 0.2
2.59 0.2
2.51 0.1
2.70 0.09
2.89 0.1
1.80 0.25
1.95 0.1
2.12 0.2
2.60 0.1
2.75 0.2
2.90 0.2
2.93 0.3
3.15 0.25
3.30 0.35
2.12 0.2
2.56 0.2
2.85 0.3
3.15 0.3
3.30 0.25
3.52 0.3
3.27 0.25
3.47 0.3
3.60 0.3
2.80 0.25
3.10 0.3
3.20 0.3
65.02
60.75
73.83
62.30
58.25
66.80
60.80
55.70
62.45
58.50
71.25
60.55
55.70
64.75
58.35
52.65
60.15
Our studies on the reactivity of α,β-unsaturated compounds regarding sulfinic acids
show that the activity of the double carbon–carbon bond changes depending on the activity
of the electron-acceptor substituent at the α-position. The interaction between nitroethene
and sulfinic acids takes place at a high rate and very low temperatures,8 while acrylonitrile
is less active regarding nucleophilic reagents. According to their reactivity, the unsaturated
substrates can be divided into three groups: nitroethene is the most active of all, and
acrylonitrile is the least reactive. The nitrile group has a stronger induction effect and gives
off fewer electrons than the electronegative carbomethoxy group. However, the resonance
effect prevails in these α,β-unsaturated systems, which is confirmed by the polarized forms:
+
+
C - C = C - N
C - C = C - O
Hence it might be expected that the resonance polarization would be more powerful
for the acrylate due to the greater electronegative character of the oxygen as compared to
the nitrogen atom.
CONCLUSION
1. The reaction of nitroolefins with sulfinic acids takes place at a higher rate than the one
with methacrylic derevatives.

ADDITION OF SULFINIC ACIDS TO METHACRYLIC DERIVATIVES
43
2. The interaction of a halogen atom at the α-position regarding the cyano group results in
an increase in the activity of the ethylene system in the nucleophilic addition reaction.
3. The nucleophilic activity of sulfinic acids increases with the introduction of electron-
donor substituents and degreases in the presence of an electron-withdrawing group.
EXPERIMENTAL
Methods
Melting points were determined on a Melt-Temp apparatus and are uncorrected.
Microanalyses were obtained using an Elemental Analyser (Carlo-Erba), and IR and UV
1
spectra were obtained using a Bruker and Specord UV-Vis. H NMR (chemical shifts
measured in solvents are given in ppm from TMS) spectra were recorded on a Bruker 250
MHz spectrometer, using CDCl3 solution.
General Procedure for Compounds 1–6
Sulfinic acids, methylacrylate, chloro-, and bromomethylacrylate were obtained and
purified by known methods.3,9
Sulfinic acids (0.01 mol) were dissolved in water (10 mL). Acetic acid (0.1 mol) and
halogenoacrylate (0.15 mol), which were initially dissolved in ethanol (10 mL), were added
to that solution, and the new mixture was stabilized by a catalytic quantity of hydroquinone.
The flask containing the reaction mixture was sealed and allowed to stand for 24 h, and
then recrystallized.
Rate Measurement
Purified sulfinic acid (0.01 mol) was added to an acetate buffer containing methacrylic
derivatives (0.01 mol). Aliquots were taken out at regular intervals of time and diluted with
ethanol. Then excess aqueous p-benzoquinone was added to the solvent to convert the
remaining sulfinic acids to dihydroxyphenylsulfone, which were determined by means of
UV spectroscopy. Since a large excess of methacrylic derivatives was used, the rate is
pseudo–first order with respect to arylsulfinic acids, the rate is estimated as dihydrox-
yphenylsulfone. The second order rate constants were calculated by (pseudo–first order
rate constants)/methacrylic derivatives.
REFERENCES
1. Katritzky, A. R.; Abdel-Fathah, A.; Wang, M. M. J. Org. Chem. 2003, 68(4), 1443.
2. Gredersen, B. A.; Lopes, X.; York, D. M. J. Am. Chem. Soc. 2003, 125, 7178.
3. Michailova, V. N.; Filipova, A. N. Russ. J. Org. Chem. 1965, 1, 1621.
4. Michailova, V. N.; Borisova, N.; Stankevich, D. Russ. J. Org. Chem. 1966, 2, 1437.
5. Achmatowicz, O.; Michalski, J. Roczniki Chemii 1956, 30, 243.
6. Achmatowicz, O.; Michalski, J. Roczniki Chemii 1955, 29, 1029.
7. Ogata, Y.; Sawaki, Y.; Isono, M. Tetrahedron 1970, 26, 3045.
8. Valeva, R.; Aleksiev, D.; Ivanova, S. Proceedings of the International Conference “Stara Zagora
2005,” 2–3 June, Stara Zagora Union of Scientists, Bulgaria; ed. B. Bancov; 2005, 1, 354.
9. Ogata, Y.; Sawaki, Y.; Isono, M. Tetrahedron 1969, 25, 2715.