CHLORINATION OF CELLULOSE WITH N-CHLOROSUCCINIMIDE-TRIPHENYLPHOSPHINE UNDER HOMOGENEOUS CONDITIONS IN LITHIUM CHLORIDE-N,N-DIMETHYLACETAMIDE

Microcrystalline cellulose was chlorinated with N-chlorosuccinimide-triphyenylphosphine under homogenous conditions in LiCl-N,N-dimethylacetamide. At the early stage of the reaction only replacement of the 6-hydroxyl groups with chlorine was observed, and at 3-hydroxyl groups were replaced at a lower rate with Walden inversion. The effects of reaction conditions on the extent of chlorination were studied in detail. More than two equivalents of chlorination reagents per glucose residue were necessary to attain a high degree of substitution (ds) by chloride, and the maximum ds attained was 1.86. Chlorinated disaccharides were found in the hydrolyzates of chlorodeoxycelluloses hydrolyzed under mild conditions, and their structures were studied by mass spectrometry.