Rearrangement, addition, and substitution reactions of arylsulphenate esters

Abstract

Aryl esters of 2-nitrobenzenesulphenic acid rearrange on being heated in an inert solvent in the dark, or upon being set aside in the dark at room temperature, to give the appropriately substituted hydroxyphenyl 2-nitrophenyl sulphides together with di-2-nitrophenyl disulphide. The methyl ester gives substituted phenyl 2-nitrophenyl sulphides on prolonged heating with alkyl- or alkoxybenzenes. 2-Nitrobenzenesulphenyl chloride gives a similar reaction. In the products from these rearrangement and substitution reactions the 2-nitrophenylthio-group is orientated ortho/para to the more electron-releasing substituent. Methyl arylsulphenates add to alkenes after prolonged heating in methanol solution in the dark to give β-methoxyalkyl aryl sulphides.