Regioselectivity of the methanolysis of polychlorinated biphenyls

Abstract

Regioselectivity of the methanolysis of lower polychlorinated biphenyls with sodium methoxide in a mixture of methanol and DMSO at 100–130°С was studied. It was found that 2,4,4'-tricholobiphenyl is much more reactive than 2,4-dichlorobiphenyl. This results in different mechanisms of substitution. 2,4-Dichlorobiphenyl reacts with sodium methoxide by the elimination–addition mechanism to form four monosubstitution products in comparable quantities. 2,4,4'-Trichlorobiphenyl reacts with the methodixe ion by the classical SNAr mechanism, with preferential substitution of the 2-chlorine atom.