Chlorination of cellulose with methanesulphonyl chloride in N,N dimethylformamide and chloral

Treatment of hardwood dissolving sulphate pulp with N,N-dimethylformamide, chloral, and methanesulphonyl chloride at 75° effective rapid and selective chlorination, initially at the primary positions. When most of the primary hydroxyl groups had been replaced, reaction occurred at HO-3 to give 3,6-dichloro-3,6-dideoxy-D-allose residues. 4,6-Dichloro-4,6-dideoxy-D-galactose residues, derived from non-reducing end-groups were detected only in highly chlorinated cellulose. The degradation of cellulose during chlorination was investigated by gel-permeation chromatography.