Kinetics and correlation analysis of reactivity in oxidation of organic sulfides by hexamethylenetetramine-bromine

The oxidation of organic sulfides by hexamethylenetetramine-bromine (HABR) to the corresponding sulfoxides is first order with respect to HABR. Michae lis-Menten-type kinetics were observed with respect to the sulfide. It is p roposed that HABR itself is the oxidizing species. Correlation analyses of the rate of the oxidation of 34 sulfides were performed in terms of various single and multiparametric equations. The best correlation was obtained wi th Charton's LDR and LDRS equations, the polar regression coefficients bein g negative. The oxidation of alkyl phenyl sulfides exhibited a very good co rrelation in terms of the Pavelich-Taft equation. A mechanism involving the formation of a halosulfonium cation in the slow step is proposed. Copyrigh t (C) 2000 John Wiley & Sons, Ltd.