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Oxidative cleavage of S‐Arylmercaptoacetic acids by pyridinium chlorochromate: Kinetic and correlation analysis
Author(s) -
Kabilan S.,
Girija R.,
Rajagopal V.
Publication year - 1999
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1999)31:10<683::aid-jck1>3.0.co;2-9
Subject(s) - chemistry , steric effects , pyridinium chlorochromate , thiophenol , intramolecular force , pyridinium , reaction rate constant , kinetics , oxidative cleavage , medicinal chemistry , protonation , organic chemistry , stereochemistry , computational chemistry , catalysis , physics , quantum mechanics , ion
Kinetics of oxidation of 24 S‐Arylmercaptoacetic acids (SAMA) by pyridinium chlorochromate (PCC) have been studied in acidmedium. The product of oxidation is the corresponding thiophenol. The rate data of meta‐ and para‐substituted acids have been correlated well with σ I , σ R o values and the meta‐compounds correlate well with F,R values. The reaction constants are negative and of smaller magnitudes. Further, the ortho‐substituted acids show a good correlation with triparametric equation involving Taft's σ I and σ R o and charton's steric parameter v . There is no considerable steric contribution to the total orthosubstituent effect. Based on these observations, the mechanism involving the formation of protonated arylsulfinylacetic acid intermediate, followed by an intramolecular rearrangement leading to the product thiophenol has been proposed. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 683–688, 1999