Nucleophilic substitution at sulphur. Part 3. The alkaline hydrolysis of some cyclic and open-chain sulphonate esters

Abstract

The rates of alkaline hydrolysis of a number of aryl cyclic and open-chain sulphonate esters have been studied at various temperatures. The enthalpies and entropies of activation have been determined. The difference in reactivity between the five-membered sultone and other cyclic and open-chain analogues is shown to arise from a combination of both enthalpy and entropy strain. The detailed mechanism of alkaline hydrolysis of sulphonate esters and the cause of ring strain in sultones are discussed in some detail.