Selective one-pot synthesis of trithiocarbonates, xanthates, and dithiocarbamates for use in RAFT/MADIX living radical polymerizations

We report a facile route for the production of chain transfer agents for reversible addition fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations, via a one-pot reaction. 1,1'-Thiocarbonyl diimidazole (TCDI) undergoes controlled monosubstitution when reacted with secondary thiols or alcohols. The intermediate S/O-esters of imidazole-N-thionocarboxylic acid react efficiently with a range of primary thiols, alcohols, and amines to form asymmetrical dithiocarbonates, trithiocarbonates, and dithiocarbamates, respectively. The synthesis provides a facile approach to the controlled radical polymerization of vinyl monomers through the reversible addition-fragmentation chain transfer (RAFT) mechanism.