Abstract
A new DL-polysaccharide containing one hydroxyl group in its repeating unit, 3,4-dideoxy-(1→6)-α-DL-erythro-hexopyranan, was synthesized by the cationic ring-opening polymerization of 4(a)-benzyloxy-6,8-dioxabicyclo[3.2.1]octane (1), followed by debenzylation. The bicyclic acetal 1 was prepared from 3,4-dihydro-2H-pyran-2-carbaldehyde via six step reactions. Ring-opening polymerization of 1 was initiated by antimony pentafluoride, antimony pentachloride, and trifluoromethanesulfonic acid to give polyacetal (2) with number average molecular weights of 6700—13500 at −60°C or below. Boron trifluoride etherate, a highly effective initiator for stereospecific polymerization of 6,8-dioxabicyclo[3.2.1]octane, was practically ineffective in initiating the polymerization of 1. Debenzylation of 2 with sodium metal in liquid ammonia afforded a white powdery polymer identified as 3,4-dideoxy-(1→6)-α-DL-erythro-hexopyranan (3) by 13C NMR spectroscopy. The synthetic polysaccharide 3 having number average molecular weights of 4300—7800 was soluble in dimethyl sulfoxide, N,N-dimethylformamide, and methanol, and insoluble in other common organic solvents and water. It melted at 130—140°C and decomposed in air at 280—300°C. Water sorption of 3 was measured at different relative humidities and compared with that of natural dextran having an analogous structure.
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Okada, M., Sumitomo, H. & Ogasawara, K. Chemical Synthesis of Polysaccharides I. Synthetic Polysaccharide Having One Hydroxyl Group in Its Repeating Unit, 3,4-Dideoxy-(1→6)-α-DL-erythro-hexopyranan. Polym J 14, 815–821 (1982). https://doi.org/10.1295/polymj.14.815
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DOI: https://doi.org/10.1295/polymj.14.815