Studies on the Oxidation of some Sulfides with Pyridinium Dichromate in Acetonitrile medium

Abstract

The kinetic behaviours of oxidation of dialkyl, alkyl aryl and diphenyl sulfides are quite different with pyridinium dichromate in acetonitrile medium; studies indicate the involvement of a sulfur cation free radical intermediate in diphenyl sulfide oxidation; electron releasing and withdrawing groups retard the reactivity of aryl methyl sulfides; the observed non-linear concave downwards type Hammett plot is well explained by assuming shifts in the rate-limiting step within the same overall reaction pathway.