Sucrochemistry. Part XII. Reaction of sucrose with sulphuryl chloride

Abstract

Reaction of sucrose with sulphuryl chloride at –78° afforded, after dechlorosulphation, a mixture of 6′-chloro-6′-deoxysucrose and 6,6′-dichloro-6,6′-dideoxysucrose, which were obtained, after chromatographic fractionation, in a combined yield of 72%. At room temperature, a complex mixture of products was formed from which 4,6-dichloro-4,6-dideoxy-α-D-galactopyranosyl 3′,4′-anhydro-1′,6′-dichloro-1′,6′-dideoxy-β-D-ribo-hexulofuranoside 2,3-sulphate was isolated in 17% yield. At 50°, a mixture of greater complexity arose and in addition to the foregoing anhydro-derivative a 4,6-dichloro-4,6-dideoxy-α-D-galactopyranosyl 1′,4′,6′-trichloro-1′,4′,6′-trideoxy-β-D-hexulofuranoside 2,3-sulphate and 4,6-dichloro-4,6-dideoxy-α-D-galactopyranosyl 1′,4′,6′-trichloro-1′,3′,4′,6′-tetradeoxy-β-D-glycero-hex-3′-enulofuranoside 2,3-sulphate were isolated, all in rather low yields. The structures of these products were assigned on the basis of n.m.r. and mass spectrometry.