Furuhata K, Chang H S, Aoki N, Sakamoto M
Department of Organic and Polymeric Materials, Faculty of Engineering, Tokyo Institute of Technology, Japan.
Carbohydr Res. 1992 Jun 4;230(1):151-64. doi: 10.1016/s0008-6215(00)90518-4.
Microcrystalline cellulose was chlorinated with N-chlorosuccinimide-triphenylphosphine under homogeneous 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 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 chlorine, 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.
微晶纤维素在LiCl-N，N-二甲基乙酰胺的均相条件下用N-氯代琥珀酰亚胺-三苯基膦进行氯化。在反应初期，仅观察到6-羟基被氯取代，而3-羟基以较低的速率通过瓦尔登转化被取代。详细研究了反应条件对氯化程度的影响。每个葡萄糖残基需要超过两当量的氯化试剂才能实现氯的高取代度（ds），并且达到的最大ds为1.86。在温和条件下水解的氯代脱氧纤维素的水解产物中发现了氯化二糖，并通过质谱对其结构进行了研究。
