Reactions of halogenoaliphatic acids with free radicals in aqueous solution. Part II. Reactions with aliphatic free radicals

Abstract

Dehalogenation of halogenoaliphatic compounds by aliphatic free radicals was investigated. The reactivity of the radicals studied followed the sequence BrCH₂·CH·OH ≃ ClCH₂·CH·OH > (CH₃)₂C·OH > CH₃·CH·OH > CH₂·OH CBr₂·CO₂H > CH₃·CBr·CO₂H > BrCH·CO₂H CH₃·CH·CO₂H ≃ CH₂·CO₂H. The last two radicals do not induce any dehalogenation. The reactivity of the substrates toward the radicals increases in the order ClCH₂·CH₂·OH < ClCH₂·CO₂H < BrCH₂·CO₂H < CBr₃·CO₂H. The results indicate a charge-transfer mechanism in these reactions rather than halogen abstraction.