Nucleophilic substitution at sulphinyl sulphur. Kinetics and oxygen-18 tracer studies of the alkaline hydrolysis of some sulphinate esters

Abstract

The rates of alkaline hydrolysis of some simple aliphatic sulphinate esters have been studied at various temperatures. The enthalpies and entropies of activation have been determined. The main difference in reactivity between the five- and six-membered rings is shown to be due to entropy strain. Oxygen-18 experiments demonstrate that 1,2-oxathiolan 2-oxide does not undergo ¹⁸O exchange with solvent during hydrolysis.