Synthesis and Reactions of Functional Polymers. XXXIV. Low Polymerization of Ethylene Oxide with Sodium N,N-Dimethyldithiocarbamate in Dipolar Aprotic Solvents

The low polymerization of ethylene oxide with sodium dimethyldithiocarbamate in a homogeneous system was studied. This reaction was verified as proceeding through a step-by-step addition mechanism, due to the enhanced nucleophilicity of the dithiocarbamate anion in dipolar aprotic solvents. The solvent effects and the catalyses of various dithiocarbamate salts were also examined. Epichlorohydrin was reacted with this salt in dimethylformamide to afford a polymer with a dithiocarbamate moiety through both ring-opening and substitution processes.