The proton inventory technique in a dual mechanistic system: the spontaneous hydrolysis of ethyl formate^†

Abstract

Ethyl formate undergoes spontaneous hydrolysis through two parallel mechanistic pathways: water catalysis and specific hydrogen-ion catalysis. The proton inventory of the water reaction at 37.0 ( degrees )C was determined from the overall conversion curves, in H(2)O/D(2)O mixtures of deuterium atom fraction n, resulting in k(1)(n)=(2.1+/-0.1)x10(-5) s(-1) (1-n+0.42 n) (1-n+0.83 n)(2), in agreement with the results of six other cases of carboxylic acid derivatives. This result contributes to the validation of the accuracy of the proton inventory technique.

A comparative study on the hydrolysis of acetic anhydride and N,N-dimethylformamide: Kinetic isotope effect, transition-state structure, polarity, and solvent effect

“…Proton inventory techniques play a crucial role in elucidating mechanisms by identifying the number and types of hydrogens involved in the transition‐state structures. Proton inventory studies, which have been well discussed by Mata‐Segreda, indicate that esters undergo hydrolysis through parallel water catalysis and specific hydrogen ion catalysis.…”