Polymeric protecting groups, 4. Amino‐protection with tert‐butoxycarbonyl‐analogous comblike methacrylic polymers by aminolysis of activated carbonates

The synthesis of highly amino-sensitive activated carbonates based on tert-butoxycarbonyl(BOC)-modified monomers was performed by reaction of phthalimido chloroformate and phenyl chloroformate with the free OH groups of N-(2-hydroxy-2-methylpropyl)methacrylamide (1), N-(3-hydroxy-3-methylbutyl)methacrylamide (2) and N-(2-hydroxy-2-methylpropyl)-6-methacrylamidohexanamide (6), respectively. The monomeric carbonates were radically homo- and copolymerized with methyl methacrylate (MMA). The kinetics of aminolysis of these polymers with hexanamide was followed by UV and NMR spectroscopy. Differences between phthalimide- and phenyl-containing systems, neighbouring group effects, influence of different comonomers and spacer groups on the reactivity of the activated carbonates are discussed.