An approach towards identification of product precursors in the solvolyses of diarylmethyl p-nitrobenzoates in ethanol–water solvents

Abstract

The product ratios, ether: alcohol, for the solvolyses of the title compounds in ethanol–water solvent mixtures have been measured, and have been compared with ratios of the same products generated from the reactions of the corresponding diaryldiazomethanes in the same solvents. The ratios are similar although not always identical, and disparities are ascribed to solvation differences. The question of ‘selectivities’ of intermediates towards ethanol and water is addressed, and it is concluded that product ratios can be used as selectivity measures only when a single intermediate yields stable products. The present results thus throw little light on the reality or otherwise of stability–selectivity relationships in the present series. Internal return is suggested as an important component in the unassisted solvolysis of the esters.