Polymerization of 2-Oxazolines. IV. The Structure and the Reactivity of 2-Substituted-2-oxazolines and Oxazolinium Perchlorates

Abstract

Abstract In order to elucidate the structure and the stability of the growing cationic end in the polymerization of 2-oxazolines, the reactions of 2-bromoethylbenzamide with silver salts such as silver perchlorate, tetrafluoroborate, nitrate, nitrite, cyanate, and acetate were investigated. The reactions with silver perchlorate and tetrafluoroborate gave the 2-phenyl-2-oxazolinium salt (intramolecular O-alkylation product) quantitatively, whereas the reaction with silver nitrate gave the corresponding alkyl nitrate (staight-chain product). For the reactions with silver nitrite, cyanate and acetate, both products were obtained. In order to elucidate the ring-opening reactivity of the oxazolinium cation, the ring-opening addition reaction of N-methyl-2-oxazolinium perchlorates with pyridine was investigated. It was found that N-methyl-2-phenyl-2-oxazolinium perchlorate was more reactive toward the nucleophilic ring-opening reaction than was N-methyl-2-methyl-2-oxazolinium perchlorate. The mutual copolymerization of 2-phenyl-2-oxazoline with the other 2-substituted-2-oxazoline such as 2-methyl-, 2-isopropyl-, and 2-benzyl-2-oxazoline indicated that the monomer reactivity ratio r2 was much larger than unity, whereas r1 was very much smaller. Based on these results, the influence of the structure and the reactivity of the monomer and the growing cationic end of the polymerizability of 2-oxazolines are discussed.