Abstract
A new DL-polysaccharide (1→6) α-DL-glucopyranan (DL-dextran, 3) was synthesized by the cationic ring-opening polymerization of 1,6-anhydro-2,3,4-tri-O-benzyl-β-DL- glucopyranose (1) followed by debenzylation of the resulting polymer (2). The anhydrosugar derivative 1 was prepared from 3,4-dihydro-2H-pyran-2-carbaldehyde (acrolein dimer, 4) via eight reaction steps. Polymerization of 1 was undertaken using o-fluorotoluene, dichloromethane, and 1-nitropropane as solvents and phosphorus pentafluoride, antimony pentachloride, and tantalum pentachloride as initiators at different temperatures ranging from −78 to −45-°C. The diad tacticities of 2 and 3 were evaluated from their 13C NMR spectra. The isotactic diad content varied from 55 to 72% depending upon the reaction conditions, being higher for the polymers prepared in a less polar solvent at lower temperature. DL-Dextran 3 having a number average molecular weight up to 3.6×104 was soluble in dimethyl sulfoxide and water, did not show a melting point and began to decompose at ca. 260°C. Water sorption and enzymatic hydrolysis of 3 were measured and compared with those of natural dextran.
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Okada, M., Sumitomo, H., Hirasawa, T. et al. Chemical Synthesis of Polysaccharides VI. Synthesis of (1→6) α-DL-Glucopyranan (DL-Dextran) by the Ring-Opening Polymerization Method. Polym J 18, 601–611 (1986). https://doi.org/10.1295/polymj.18.601
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DOI: https://doi.org/10.1295/polymj.18.601