Synthesis of N , N ‐Disubstituted Methacrylamides Having Hydroxy Group and Their Radical Homopolymerization Behavior

In this study, we have synthesized N , N ‐disubstituted methacrylamides having hydroxy groups, and we have investigated their radical homopolymerization behavior. N , N ‐Disubstituted methacrylamide bearing two hydroxyurethane groups 2 and one with two hydroxyethyl groups 3 undergo radical homopolymerization in bulk. On the other hand, N , N ‐dimethylmethacrylamide 1 and N , N ‐disubstituted methacrylamide with two urethane groups 4 do not homopolymerize in bulk. These results suggest that the radical homopolymerizability in bulk of 2 and 3 is attributed to the hydroxy groups on the N ‐substituents. With the aim of disclosing the relationship between the radical homopolymerizability and the conjugation between C═O and C═C groups, we have measured carbon‐13 nuclear magnetic resonance ( 13 C NMR) spectra of 1–4 in bulk state, because the chemical shift of the β ‐carbon of methacrylamide reflects the efficiency of the conjugation. The β ‐carbon chemical shifts of 1–4 were observed in descending order as 2 > 3 > 4 > 1 , which was in good agreement with their radical polymerizability in bulk, i.e., 2 > 3 >> 4 , 1 .