Solvolysis of 1‐tert‐Butyl‐1‐(4‐phenoxyphenyl) Methyl Bromide and Chloride. Further Example for Possible Contribution of Non‐canonical Resonance Structure in the Transition State

Abstract

AbstractThe solvolysis of 1‐tert‐butyl‐1‐(4‐phenoxy)methyl bromide (5b) and chloride (5c) in a variety of solvents were carried out. Limiting SN 1 mechanisms were suggested from the observation of linear relation ships using single‐parameter Winstein‐Grunwald type correlation between logarithm of rate constants with YxBnBr and YxBnCl scales, respectively. This result indicated positive charge delocalization over both arylrings and provided further evidence for possible contribution of non‐canonical resonance structure in the cationic transition state.