RATE CONSTANTS FOR REACTIONS OF (PERHALOALKYL)PEROXYL RADICALS WITH ALKENES IN METHANOL

A number of halogenated peroxyl radicals were produced in methanolic s olutions through the radiolytic reduction of halocarbons in the presen ce of oxygen. Rate constants for the reactions of these radicals with unsaturated organic compounds were measured by competition kinetics wi th chlorpromazine as the reference compound. The rate constants were i n the range 5 x 10(4) to 2 X 10(8) L mol(-1) s(-1) and generally incre ased with increasing fluorine substitution on the peroxyl radical and increasing substitution of alkyl groups about the double bond in the a lkene. Limits on the rate constants with increasing substitution, howe ver, suggested an additional effect of steric hindrance. Similar resul ts were found for the oxidation of chlorpromazine by several of these haloperoxyl radicals.