Thiosugars. XI. Further Studies on Thiolevoglycosans.

Abstract

2-Deoxy-1, 6-anhydro-1, 6-sulfide-β-D-glucopyranose (2-Deoxy-thiolevoglucosan) (IX), m.p. 189∼192°, [α]²²_D-71.7°, and 2-deoxy-1, 6-anhydro-1, 6-sulfide-3, 4-anhydro-β-D-altrose (2-Deoxy-3, 4-anhydro-thiolevoaltrosan) (XIV), m.p. 69∼72°, [α]²²_D-108°, were synthesized by starting with D-glucal (II), followed by treatment of the intermediate 2-deoxy-6-O-tosyl-3, 4-di-O-acetyl-β-D-glucopyranosyl ethylxanthate (VI) and 3-bromo-4-O-acetyl-6-O-tosyl-2, 3-dideoxy-β-D-glucopyranosyl ethylxanthate (XIII), respectively, with sodium methoxide. The preparation of 6-O-tosyl-3, 4-di-O-acetyl-D-glucal (III), m.p. 106∼107°, [α]²²_D+14°, which is a key intermediate in this paper, and the addition of hydrogen bromide upon III were also described.