Synthesis of a series of SG1 2‐[N‐tert‐butyl‐N‐(1‐diethoxyphosphoryl‐2,2‐dimethylpropyl)aminoxyl] based alkoxyamines, SG1‐CH(Me)CO2R, and measurement of the homolysis rate constants of the CON bond

During nitroxide‐mediated polymerization, the polymerization time decreases with an increasing rate constant of the cleavage of the NOC bond of dormant alkoxyamines. Thus, knowledge of the factors influencing this cleavage is of considerable interest. We have prepared a series of SG1 2‐[N‐tert‐butyl‐N‐(1‐diethoxyphosphoryl‐2,2‐dimethylpropyl)aminoxyl] based alkoxyamines [SG1‐CH(Me)CO2R] with various R groups (alkyl or aryl) and measured the homolysis rate constants (kd). kd decreases with the bulkiness and increases with the polarity of the R group.