Solvolysis of 1-aryl-2,2,2-trihalogenoethyl toluene-p-sulphonates. Generation of carbocations destabilized by trichloro- or tribromo-methyl groups

Abstract

The kinetics of solvolysis of the title compounds, leading to the formation of carbocations destabilized by a CCl₃ or a CBr₃ group, have been studied in various solvents. Destabilization by the CX₃ group increases with the electronegativity of the halogen X. Plots of log k vs. Y_OTs, for the 1-(p-methoxyphenyl)-2,2,2-trihalogenoethyl p-toluenesulphonates yield m_OTs values which are indicative of some deviation from a pure k_c process, probably due to anchimeric assistance by the halogen substituents.