Importance of hydrogen bonding in base-catalyzed transesterification reactions with vicinal diols

The transesterification reaction kinetics of 2-(benzoyloxy)ethyl benzoate with various alcohols (ethylene glycol, 1,3-propanediol, 1-butanol, propylene glycol and 1,2-butylene glycol) using various cyclic amidine catalysts were investigated. For transesterification with excess glycol (glycolysis), the rate was nearly zero order in diester and glycol concentration, which is substantially different from classical transesterification kinetics with monoalcohols. The measured kinetic parameters during glycolysis are consistent with a reaction path that is kinetically limited by the decomposition of the reaction intermediate formed from the alkoxide and diester. The DFTcalculated reaction energy and activation barrier for decomposition of this intermediate reveal a critical role of intramolecular hydrogen-bond stabilization made possible by the vicinal -OH of the glycol that effectively increases the concentration of the intermediate during reaction resulting in acceleration of the overall transesterification rate. These findings indicate the nature of both the alcohol solvent and the catalyst influence transesterification rate, and results suggest they are also important in the deconstruction of carbonyl-containing condensation polymers.