Chapter 3: Synthesis of Nitroxides and Alkoxyamines

The persistent radical effect (PRE) established in the presence of a nitroxide has been widely investigated for the preparation of macromolecules with narrow molar mass distribution through radical polymerization (both in a bi-molecular fashion employing a nitroxide and radical initiator, and uni-molecularly using a thermally unstable alkoxyamine to supply both fragments). This chapter examines synthetic techniques available for designing both nitroxide free radicals as well alkoxyamines—the key mediating species in uni-molecular, nitroxide mediated polymerization. In both sections, a number of literature examples will be highlighted, with the aim being to provide the reader with a workable selection of design tools for the modification of both nitroxide and R-group moieties.