Thermolyses of NN-dimethylcarbamates and the implications for thermal β-elimination reaction mechanisms

Abstract

Ethyl NN-dimethylcarbamate, isopropyl NN-dimethylcarbamate, and t-butyl NN-dimethylcarbamate undergo β-elimination during gas-phase thermolysis; the influence of structure on rates and activation energies shows that the reactions which are unimolecular involve heterolytic rather than homolytic bond fission and support an unsymmetrical transition state.