Inductive and field effects in aromatic substitution. Part II. Nitration of benzotrichloride and βββ-trichloroethylbenzene

Abstract

The products of nitration of PhCCl₃ and PhCH₂·CCl₃ have been determined for reaction under homogeneous conditions. The corresponding partial rate factors have been determined by competitive experiments in which the reactivities of these substrates are related to those of the ions Ph(CH₂)_n[graphic omitted]Me₃. From these results and those for the nitration of PhCF₃, it is concluded that hyperconjugative electron-withdrawal is probably unimportant for the CCl₃ substituent but may give rise to ca. 17% of the free energy of activation for para-substitution to the CF₃ substituent.