New rate–product correlations for general-base catalysed reactions in alcohol–water mixtures

Abstract

Selectivities (S) for solvolyses of p-nitrobenzoyl chloride (1), p-nitrobenzenesulfonyl chloride (2), p-nitrobenzyl chloride (3 Z = NO₂) and p-methoxybenzyl chloride (3; Z = OMe) in alcohol–water mixtures are consistent with third-order terms in the rate law, including terms for nucleophilic attack and general-base catalysis by water and/or alcohol. The results document new rate–product correlations and new reactivity–selectivity relationships, which help to define ‘normal’ behaviour from which deviations can be identified for further investigations.