Chlorine-sensitized Photooxidation of Chloroethanes and Chloroethylenes I -Competitive Reaction of Oxidation and Chlorination-

Abstract

ln the chlorine-sensitized photooxidation, chSoroethanes and chloroethylenes are chlorinated owing to the reactivity of ehiorine.
PreMsent paper is concerned with the effect of the Structure on this competitive reaction of chlorine and oxygen, The more Substituted with chiorine atoms, the faster the rate of oxidatien compared with that of chlorination. Relative reactivity was affected remarkably by the polar nature of the Substituent,
Judging from the structure of the oxidation productS, CHsCICHCI, CHsCICCIs and CHCIsCCI2were MpnaaS the radical intermediates which were formed by addition of a chlorine atom to vinyS chioride, 1, 1-dich1oroethylene and trichloroethylene reSpectively.
Trichioromethyl compoundS, such aS CCIgCHs and CCIsCH2Cl, were converted into unexpected aid ch1orideS. The results could be acounted for by isomerization of radicaE intermediates.