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The kinetics and stereochemical aspects of the thermal decomposition of aralkyl carbonates, thiocarbonates, and carbamates were examined. The rates for the decompositions as well as the rates of loss of optical activity followed first-order kinetics. The decompositions appear to involve the heterolysis of the aralkyl–oxygen bond followed by the breakdown of the subsequent ion pair via a cyclic mechanism. However, it was found that this ion pair could return to covalency without completely decomposing to products leading to the racemization of the starting materials. This type of racemization occurred more readily in the case of the carbamates than in the thiocarbonates and carbonates. The dependence of the decomposition rates and the loss of optical activity on the nature of the hetero atom of the anionic fragment of the starting material is discussed.

Anisylic phenyl carbonates decomposed at elevated temperatures to give CO2and the corresponding anisylic phenyl esters. The decomposition follows first order kinetics very similar to those found for alkyl chloroformates. The decompositions involve the heterolysis of the aralkyl oxygen bond followed by the breakdown of the subsequent ion pair via a cyclic mechanism. The dependence of the decomposition rates on the nature of the solvent and structural changes of the starting carbonates is discussed.