After Being Kept Standing Overnight

overnight, the mixture was poured into ice-water, a syrupy product was produced, which was solidified on standing for several hours. This was filtered off and washed with water, and air dried; yielding was 14.1g. in 60% of theory. After several recrystallizations from CHCl3-EtOH, it melted at 201~202°;〔 α〕20D -35.6°(c=0.92, CHCl3), reported, m.p. 194°, 25) 199~200°, 26) 202~204°8);〔 α〕D -36.4°.8) Anal. Calcd. for C27H22O8: C, 68.35; H, 4.67. Found: C, 68.06; H, 4.66. 1, 6-Anhydro-β-D-glucopyranose (II) Asolution of 5.6g. of 1, 6-anhydro-2, 3, 4-tri-O-acetyl-β -n-glucose in 50cc. of 0.01N MeONa in MeOH was allowed to stand in refrigerator overnight. After a removal of the solvent, the residues were recrystallized from AcOEt to afford 2.8g. of (II), m.p. 178°;〔 α]20D -66°(c=0.9, H2O), reported,25) m.p. 178°and〔 α〕D -66.5°in water. Anal. Calcd. for C6H10O5: C, 44.44; H, 6.22. Found: C, 44.52; H, 6.32. Phenylosazone of 3, 6-anhydro-D-glucose 10g. of 6-deoxy-6-iodo-1, 2, 3, 4-tetra-O-acetyl-α-Dglucopyranose (IV)23) was treated with 3.5g, of MeONa (1.5g. of Na in 30cc. of MeOH) in the same manner described in (I). As compared with β-anomer, the reaction mixture was deepen in its color. After being kept standing overnight in refrigerator, the mixture was neutralized with AcOH and the solvent was removed under reduced pressure. The residues dissolved in water were passed through a column of Amberlite IR-120 (H+) and then a column of Amberlite IR-45 (OH-) successively. The effluent was treated with charcoal and concentrated under reduced pressure to slightly colored syrup, which reduced the Fehling's solution, yielding was 3g. 1.0g. of syrup, 2.0g. of freshly distilled phenylhydrazine and 2cc. of 50% AcOH were dissolved in 30cc. of water and heated on a steambath for 30min. After cooling, yellow precipitates were filtered off and washed with a small amount of cold water. Recrystallization from EtOH gave yellow needles, m.p. 190°(decomp.);〔 α〕20D -84.4~-37.5°(after 24hr .) (c=1.28, pyridine) reported27) m. p, 187~188°and〔 α〕D -146°in MeOH. Anal. Calcd. for C18H20O3N4: C, 63.51; H, 16.46. Found: C, 63.66; H, 5.86; N, 16.55.