Colloque

The Mechanism of Solvolysis of Chloroformates in Water

A. Queen

Membre a labase

A. Queen

Résumé du colloque

The rate sequence PhO-CO-Cl > MeO-CO-Cl > EtO-CO-Cl > i-PrO-CO-Cl for hydrolysis in pure water indicates a change of mechanism for the latter reaction. The enthalpies and entropies of activation support this conclusion. The solvent deuterium isotope effects indicate that pre-equilibrium with water is important for the hydrolyses of the first three compounds but not for isopropyl chloroformate. The heat capacities of activation (ΔCp*) have been determined and have been used in determining the operative mechanisms.