Oxidation of S-Phenylmercaptoacetic Acid by N-Chloronicotinamide: A Kinetic and Mechanistic Study

K. Sathiyanarayanan; R. Suseela; Chang Woo Lee

Journal of Industrial and Engineering Chemistry, Vol.12, No.2, 280-283, March, 2006

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Oxidation of S-Phenylmercaptoacetic Acid by N-Chloronicotinamide: A Kinetic and Mechanistic Study

K. Sathiyanarayanan^†, R. Suseela, and Chang Woo Lee¹

Vellore Institute of Technology, Vellore, 632 014, India
¹Korea Electrotechnology Research Institute, P.O.Box 20, ChangWon, 641-120, Korea

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The conversion of S-phenylmercaptoacetic acid to the corresponding sulfoxide was performed in 50% (v/v) water-acetic acid mixture in the presence of perchloric acid, the catalyst. The orders, with respect to S-phenylmercaptoacetic acid and the oxidant, were both one. The order with respect to perchloric acid was also one. The increase in acetic acid content in the solvent increasd the rate of the reaction. Ionic strength had a considerable influence on the rate of the reaction, indicating the involvement of a dipole in the rate-limiting step. The added acrylonitrile did not have any effect on the reaction, ruling out the possibility of participation of free radicals in the reaction. A suitable mechanism in consonance with the observed facts is proposed.

Keywords:kinetics;mechanism;rate law;catalyst;oxidation

[References]

Gopalakrishnan M, Ph. D. Thesis, Annamalai University (1988)
Srinivasan C, Pitchumani K, Bull. Chem. Soc. Jpn., 55, 289 (1982)
Srinivasan C, Pitchumani K, Indian J. Chem. Sect A-Inorg. Bio-Inorg. Phys. Theor. Anal. Chem., 17, 162 (1979)
Gurumurthy R, Sathiyanarayanan K, Gopalakrishnan M, Tetrahedron, 50, 13731 (1994)
Karunakaran K, Elango KP, J. Phys. Org. Chem., 9, 105 (1996)
Srinivasan C, Pitchumani K, Int. J. Chem. Kinet., 14, 789 (1982)
Panigrghi GP, Nayak RN, Curr. Sci., 49, 740 (1980)
Gurumurthy R, Sathiyanarayanan K, Gopalakrishnan M, Bull. Chem. Soc. Jpn., 65, 1096 (1992)
Gurumurthy R, Sathiyanarayanan K, Gopalakrishnan M, Int. J. Chem. Kinet., 24, 953 (1992)
Srinivasan NS, Venkatasubramanian N, Tetrahedron, 30, 419 (1974)
Gabriel S, Bernoulli, 12, 1939 (1879)

[Referenced By]

[Related Articles]

[1] Gopalakrishnan M, Ph. D. Thesis, Annamalai University (1988)

[2] Srinivasan C, Pitchumani K, Bull. Chem. Soc. Jpn., 55, 289 (1982)

[3] Srinivasan C, Pitchumani K, Indian J. Chem. Sect A-Inorg. Bio-Inorg. Phys. Theor. Anal. Chem., 17, 162 (1979)

[4] Gurumurthy R, Sathiyanarayanan K, Gopalakrishnan M, Tetrahedron, 50, 13731 (1994)

[5] Karunakaran K, Elango KP, J. Phys. Org. Chem., 9, 105 (1996)

[6] Srinivasan C, Pitchumani K, Int. J. Chem. Kinet., 14, 789 (1982)

[7] Panigrghi GP, Nayak RN, Curr. Sci., 49, 740 (1980)

[8] Gurumurthy R, Sathiyanarayanan K, Gopalakrishnan M, Bull. Chem. Soc. Jpn., 65, 1096 (1992)

[9] Gurumurthy R, Sathiyanarayanan K, Gopalakrishnan M, Int. J. Chem. Kinet., 24, 953 (1992)

[10] Srinivasan NS, Venkatasubramanian N, Tetrahedron, 30, 419 (1974)

[11] Gabriel S, Bernoulli, 12, 1939 (1879)