Kinetics of the uncatalysed transesterification of malonates

Abstract

The role of the enolic hydrogen in the uncatalysed transesterification of malonates was examined. Equilibrium and kinetic measurements were made for the alcoholysis of diethyl malonate and a series of substituted malonates. The requirement for an enolic hydrogen, the first-order dependency of the rate upon the malonate, and the large negative values of entropy of activation are consistent with the uncatalysed transesterification proceeding through a cyclic enolate intermediate.