KINETICS AND MECHANISM OF THE OXIDATION OF DIOLS BY ETHYL N-CHLOROCARBAMATE

The kinetics of oxidation of five vicinal and four non-vicinal diets, and two of their monoethers by ethyl N-chlorocarbamate (ECC) have been studied. The vicinal diets yielded products arising out of the glycol bond fission while; the other diols yielded hydroxycarbonyl compounds . The reaction is first order-with respect to ECC, the diol, and hydro gen ions. Addition of ethyl carbamate and acrylonitrile has no effect on the reaction. The oxidation of [1,1,2,2-H-2(4)]ethanediol showed th e absence of a primary kinetic isotope effect. The values of solvent i sotope effect, k(H2O)/k(D2O), at 303 K for the oxidation of ethanedol, propane-1,3-diol and 3-methoxybutan-1-ol are 3.51, 2.21 and 1.98 resp ectively. An acyclic mechanism involving glycol bond fission has been proposed for the oxidation of the vicinal diols. The other diols are o xidized by a hydride-transfer mechanism as are monohydric alcohols.