Abstract
A new DL-polysaccharide having a regiospecific hydroxyl group in its repeating unit (3,4-dideoxy-(1→6)-α-DL-threo-hexopyranan) was synthesized from 3,4-dihydro-2H-pyran-2-carbaldehyde (acrolein dimer): A bicyclic acetal, 4(e)-benzyloxy-6,8-dioxabicyclo[3.2.1]octane (1), was prepared from the starting material via eight step reactions. The cationic ring-opening polymerization of 1 at −60°C with antimony pentafluoride, antimony pentachloride, and trifluoromethanesulfonic acid as initiators afforded stereoregular polyacetals (2) of relatively low molecular weights (Mn, 5800—8600). The subsequent removal of the protecting group of 2 with sodium in liquid ammonia gave a white fluffy polymer identified as 3,4-dideoxy-(1→6)-α-DL-threo-hexopyranan (3) by 13C NMR spectroscopy. The synthetic polysaccharide melting at 136—150°C was soluble in methanol, dimethyl sulfoxide, and dimethylformamide, but insoluble in water and other common organic solvents. The water sorption behavior of 3 was examined at different relative humidities from 43 to 97%, and compared with those of relevant natural and synthetic polysaccharides.
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Okada, M., Sumitomo, H. & Ogasawara, K. Chemical Synthesis of Polysaccharides III. A Synthetic Polysaccharide Having One Hydroxyl Group in Its Repeating Unit, 3,4-Dideoxy-(1→6)-α-DL-threo-hexopyranan. Polym J 15, 821–826 (1983). https://doi.org/10.1295/polymj.15.821
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DOI: https://doi.org/10.1295/polymj.15.821