2-CHLORO-2-DEOXY-D-GLUCOSE AND 2,2-DICHLORO-2-DEOXY-D-ARABINO-HEXOSE

Chlorination of 3,4,6-tri-O-acetyl-d-glucal in daylight afforded 3,4,6-tri-O-acetyl-2-chloro-2-deoxy-α-d-glucopyranosyl chloride (2) and 3,4,6-tri-O-acetyl-2-chloro-2-deoxy-β-d-mannopyranosyl chloride (3) in the ratio ca. 4:1. Hydrolysis of compound 2 with hydrochloric acid gave 2-chloro-2-deoxy-d-glucose in high yield, thereby providing a much-improved route to this compound. The mannosyl chloride 3 afforded 2-deoxy-d-arbino-d-hexose, with evolution of chlorine, on treatment with hydrochloric acid, and 3,4,6-tri-O-acetyl-d-glucal on treatment with sodium iodide in acetone. Dehydrohalogenation of the glucosyl chloride 2 with triethylamine afforded 3,4,6-tri-O-acetyl-2-chloro-1,2-dideoxy-d-arabino-hex-1-enopyranose, chlorination of which gave 3,4,6-tri-O-acetyl-2,2-dichloro-2-deoxy-d-arabino-hexosyl chloride. Hydrolysis of the trichloro derivative with hydrochloric acid yielded crystalline 2,2-dichloro-2-deoxy-d-arabino-hexose. © 1969.