Ketone Functionalized Nitroxides: Synthesis, Evaluation of <i>N</i>-Alkoxyamine Initiators, and Derivatization of Polymer Termini

Abstract

Two ketone-bearing N-alkoxyamines have been prepared and evaluated as initiators in nitroxide-mediated polymerization. N-(1-Phenethyloxy)-5,5,8-trimethyl-7-phenyl-azanonan-2-one (1) forms polymers with excellent control of molecular weight and low polydispersities, whereas N-(1-phenethyloxy)-5,8-dimethyl-5,7-phenyl-azanonan-2-one (2) does not effect controlled polymerization at 125 °C. Polymers prepared from initiator 1 retain the ketone functionality on the nitroxide terminus. Near-quantitative functionalization is demonstrated via hydrazone formation.