Nucleophilic substitution at bivalent sulphur. Part II. Trans-sulphenylation reactions of γ-hydroxyalkyl 2-nitrobenzenesulphenates

Abstract

Treatment of 3-hydroxy-1-methylpropyl 2-nitrobenzenesulphenate with sodium hydride in dioxan gives a mixture of 3-hydroxybutyl 2-nitrobenzenesulphenate, starting material, butane-1,3-diyl bis-(2-nitrobenzenesulphenate), and decomposition products. Under similar conditions 3-hydroxybutyl 2-nitrobenzenesulphenate gives only decomposition products. The trans-sulphenylation reactions are best interpreted in terms of a series of intermolecular substitution reactions at the sulphenyl sulphur atom rather than in terms of an intramolecular reaction, which would involve a non-linear transition state for the reaction at the sulphenyl sulphur atom.