Decomposition of ethyl diazoacetate in H2O + D2O mixtures

Abstract

The kinetics of the acid-catalyzed decomposition of ethyl diazoacetate have been measured in H₂O + D₂O mixtures. Accurate ratios of rate constants have been obtained using a differential method. The isotopic composition of the reactant and of the product has been measured. From the kinetic and product data the mechanism is shown to be A2 and a semi-quantitative measure of the degree of solvent nucleophilic participation is obtained. Limitations due to the breakdown of the rule of the geometric mean and the solvation of the various species are discussed.