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.
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