Oxymetalation. Part I. The peroxymercuration of monosubstituted ethylenes; a synthesis of secondary alkyl peroxides

Abstract

In the presence of mercury(II) acetate, t-butyl hydroperoxide reacts with monosubstituted ethylenes in dichloromethane to yield 2-t-butylperoxyalkylmercury(II) acetates together with 15–20 mole% of 2-acetoxyalkylmercury(II) acetates formed by competitive reaction with the liberated acetic acid. The peroxides may be isolated in a pure state by chromatography on silica gel; cleavage of the carbon–mercury bond with sodium borohydride then provides secondary alkyl t-butyl peroxides in high yields.