Kinetics of the base-catalysed oxidation of sulphoxides with 1-methyl-1-phenylethyl hydroperoxide

Abstract

The kinetics of the base-catalysed oxidation of dialkyl sulphoxides with 1-methyl-1-phenylethyl hydroperoxide have been studied in mixtures of benzene and protic solvents. The reaction rate is expressed as v=k[RSOR][PhCMe₂O·ONa][protic solvent]^–n, where n increases with increasing acidity of solvent. The rate of oxidation changes with solvent in the order n-butyl alcohol > isopropyl alcohol > 1-methyl-1-phenylethyl hydroperoxide > t-butyl alcohol. A positive ρ* value of +2·8 has been obtained. A probable mechanism which explains these results is discussed.