Dehydrochlorination of 3,4,6-tri-O-acetyl-2-chloro-2-deoxy-α-D-glucopyranosyl chloride with diethyl-amine yielded 3,4,6-tri-O-acetyl-2-chloro-D-glucal. The latter was further chlorinated to 3,4,6-tri-O-acetyl-2-deoxy-2,2-dichloro-α-D-ararbino-hexopyranosyl chloride, which on deacetylation provided the first example of a stable, free glycopyranosyl chloride.A 3,4,6-tri-O-acetyl-2-chloro-2-deoxymannopyranosyl chloride, also isolated in this work, was characterized by properties which correspond closely to the recently reassigned β anomer.