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.