Nonlinear structure–reactivity correlations. The hydrolysis of 2,4,6-trinitrophenyl acetate catalyzed by general bases

The hydrolysis of 2,4,6-trinitrophenyl acetate was studied in the presence of several carboxylic bases and tertiary amines. Carboxylic bases pyridine and imidazole react as nucleophilic catalysts, while 2,4-dimethyl and 2,4,6-trimethyl pyridine react as general-base catalysts. The nonlinear structure–reactivity correlations (log k_cat versus log k_OH and log k_cat versus pK of the leaving group) for the series of aryl acetates are discussed, and it is suggested that there is a change in transition-state structure along the series.