A novel method for the synthesis of alkoxyamine initiators for nitroxide-mediated radical polymerization using Mn(OAc)3 as electron-transfer reagent

Abstract

O-substituted hydroxylamines which are known to initiate and promote nitroxide-mediated radical polymerization were synthesized in high yield by a novel and facile synthetic approach. Using the favorable Mn(OAc)3 as electron transfer agent in the in situ generation of benzylic radicals and their trapping by nitroxide radicals provides a new powerful and more economic way to the desired alkoxyamine initiators for this controlled, living radical polymerization. TEMPO, TIPNO and the protected tris-hydroxy derivative of TTPNO were used to synthesize the appropriate alkoxyamines.