Reactive comb‐like polymers. Kinetic studies of the Diels‐Alder reaction of furan‐containing comb‐like polymers with dimethyl butynedioate by means of 1H NMR spectroscopy

The syntheses of some novel furan‐containing monomers, N[ω‐(furfurylcarbamoyl)alkyl]‐methacrylamide (2) and N‐furfurylmethacrylamide (3), and their corresponding polymers are described. Time‐conversion measurements of their Diels‐Alder reactions with dimethyl butynedioate by means of 1H NMR spectroscopy showed a deviation from pseudo‐first‐order kinetics. The influence of spacer length on the reaction velocity is explained by steric hindrance and neighboring group effects. No deviations from pseudo‐first‐order kinetics were observed during the Diels‐Alder reaction of the low‐molecular‐weight model compounds N [ω‐(furfuryl‐carbamoyl)alkyl]isobutyramide (8) and N‐furfurylisobutylamide (9) under the same reaction conditions.