Reactions of Carbenes with Unsaturated Polymers

Abstract

The literature has a limited amount of data on chain reactions of unsaturated polymers, in particular diene polymers. The appearance of a paper dealing with addition of dichlorocarbene to polyisoprene and to polybutadiene has impelled us to publish results of studies we made on reactions of unsaturated polymers with carbenes, which have made it possible for the first time to obtain polymers containing in the main chain, or in the side chains, cyclopropane groups with polar substituents. Addition of carbenes to cis-1, 4-polyisoprene, trans-1, 4-polyisoprene, 1, 4-polybutadiene, and 1, 2-polybutadiene was accomplished through decomposition reactions of diazoacetic esters catalyzed by copper salts (for carbethoxycarbene and carbomethoxycarbene) and the reaction of the ethyl ester of trichloroacetic acid with sodium methylate (for dichlorocarbene).