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Kinetics and mechanism of the oxidation of some organic sulfides by morpholinium chlorochromate
Author(s) -
Malani Neha,
Baghmar Manju,
Sharma Pradeep K.
Publication year - 2009
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/kin.20372
Subject(s) - chemistry , sulfonium , steric effects , sulfur , sulfide , alkyl , solvent , delocalized electron , organic chemistry , medicinal chemistry , salt (chemistry)
The oxidation of organic sulfides by morpholinium chlorochromate (MCC) resulted in the formation of the corresponding sulfoxides. The reaction is first order with respect to both MCC and the sulfide. The reaction is catalyzed by toluene‐ p ‐sulfonic acid (TsOH). The oxidation was studied in 19 different organic solvents. An analysis of the solvent effect by Swain's equation showed that both the cation‐ and anion‐solvating powers of the solvents play important roles. The correlation analyses of the rate of oxidation of 34 sulfides were performed in terms of various single and multiparametric equations. For the aryl methyl sulfides, the best correlation is obtained with Charton's localized‐delocalized‐resonance and localized‐delocalized‐resonance‐steric equations. The oxidation of alkyl phenyl sulfides exhibited a very good correlation in terms of the Pavelich–Taft equation. The polar reaction constants are negative, indicating an electron‐deficient sulfur center in the rate‐determining step. A mechanism involving formation of a sulfonium cation intermediate in the slow step has been proposed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 65–72, 2009