Abstract
Four derivatives of 2-alkenyl cyclic imino ethers were reacted with fluorosulfonic and with trifluoromethanesulfonic acids. 2-Isopropenyl-2-oxazoline (1b) and 2-isopropenyl-5,6-dihydro-4H-1,3-oxazine (1d) formed the stable N-protonated salts at 0°C. Whereas, 2-vinyl-2-oxazoline (1a) and 2-vinyl-5,6-dihydro-4H-1,3-oxazine (1c) were polymerized on protonation (spontaneous polymerization) at the same temperature to give polymers consisting of two kinds of units; one was formed by the opening of vinyl group and the other was derived by a proton transfer. By a low temperature reaction of 1a with fluorosulfonic acid at −20°C, the N-protonated salt was successfully isolated, but the corresponding salt of 1c was not obtained by the same procedure. For these three salts isolated, base-catalyzed polymerization was examined with pyridine and triethylamine as initiators at a temperature below 20°C. The salt of 1b gave a polymer consisting exclusively of the proton transferred unit. On the contrary, the salt of 1d was not polymerized at all. As a reference salt, the N-methyl salt of 1d, i.e., 3-methyl-2-isopropenyl-5,6-dihydro-4H-1,3-oxazinium salt, was prepared by the reaction of 1d with methyl trifluoromethanesulfonate, which was not polymerized, too. On the basis of these findings the reactivity of N-methyl and N-protio salts of 2-alkenyl cyclic imino ethers were discussed.
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Miyamoto, M., Sano, Y. & Saegusa, T. Reactivity of Cyclic Imino Ether Salts Having Vinyl Group V. Spontaneous and Base-Catalyzed Polymerization of N-Protio Salts of 2-Alkenyl-2-oxazolines and 2-Alkenyl-5,6-dihydro-4H-1,3-oxazines. Polym J 19, 557–566 (1987). https://doi.org/10.1295/polymj.19.557
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DOI: https://doi.org/10.1295/polymj.19.557