Acyl Transfer Reactions of 2,4-Dinitrophenyl Furoates: Comparative Effects of Nucleophiles and Non-Leaving Groups

Abstract

This study investigated the acyl group transfer reactions of 2,4-dinitrophenyl 5-substituted-2-furoates, promoted by 4-substituted phenoxides/phenols in a 20 mol% DMSO aqueous solution at 25 °C. The reactions yielded nucleophilic substitution products and displayed second-order kinetics, with βacyl values ranging from −2.24 to −2.50, ρ(x) values between 3.18 and 3.56, and βnuc values of 0.81 to 0.84. These findings indicate an addition–elimination mechanism where the initial step is rate-determining. Comparative analysis with previous data revealed that the transition state structure remained largely consistent when altering the non-leaving group from thienyl to furyl under similar conditions. Notably, a shift in the rate-determining step was observed when changing the nucleophile from secondary amines/ammonium ions to 4-substituted phenoxides/phenols, highlighting the significant impact of nucleophile selection on the reaction kinetics and mechanisms in acyl transfer reactions.

Keywords

• acyl transfer reaction
• Brönsted and Hammett plots
• stepwise and concerted mechanism