Synthesis of Polysaccharide Derivatives Having Optical Resolving Ability and Their Application for Liquid Chromatography

纤维素可与取代苯甲酰氯化物或取代苯基异氰酸酯反应生成相应的苯甲酸纤维素或苯基氨基甲酸酯纤维素。每个纤维素衍生物被吸附在硅胶上作为高效液相色谱的手性固定相。具有供电子取代基的三苯甲酸纤维素衍生物比具有吸电子取代基的衍生物具有更好的光学分辨能力。纤维素三（3-甲基苯甲酸酯）提供了一个有用的固定相，可以溶解相当广泛的外消旋化合物。用同样的方法评价了30种纤维素三苯氨基甲酸酯衍生物的光学分辨能力。这些适应性与氨基甲酸酯基团的极性和衍生物的高阶结构有关。结果表明，三（3,5-维苯氨基甲酸酯）、三（4-t-丁基苯氨基甲酸酯）和三（3,5-二氯苯氨基甲酸酯）具有较高的降解能力。特别是，前两种方法可以溶解许多药物，并提供实际有用的手性包装材料，将得到广泛的应用。还制备了15种直链淀粉三苯氨基甲酸酯衍生物，并将其用作手性固定相。取代基的光学分辨能力在很大程度上取决于取代基，三（3,5-二甲基苯基氨基甲酸酯）表现出与同类纤维素衍生物不同的高光学分辨能力，直链淀粉衍生物能分辨纤维素三（3,5-二甲基苯基氨基甲酸酯）上不能分离的许多对映体。这些三（3,5-二甲基苯基氨基甲酸酯）也被负载在更大直径的硅胶上作为固定相用于制备分离。所得到的固定相被发现对大规模分离是有用的。

Cellulose was allowed to react with substituted benzoyl chlorides or substituted phenyl isocyanates to afford corresponding cellulose benzoates or cellulose phenylcarbamates. Each cellulose derivative was adsorbed on silica gel to be used as chiral stationary phase for high-performance liquid chromatography. Cellulose tribenzoate derivatives having an electron-donationg substituent exhibited better optical resolving ability than the derivatives having an electron-eithdrawing substituent. Cellulose tris(3-methylbenzoate) afforded a useful stationary phase which could resolve rather wide range of racemic compounds.Optical resolving abilities of 30 cellulose trisphenylcarbamate derivatives were ecaluated in the same manner. The adilities were associated with the polarity of the carbamate group and high-order structure of the derivatives. The derivatives which showed a high ability were tris(3,5-dimenthylphenylcarbamate),tris(4-t-butylphenylcarbamate) and tris(3,5-dichlorophenylcarbamate). Particularly, the first two could resolve many drugs and afforded practically useful chiral packing materials which will be employed widely.Fifteen amylose trisphenylcarbamate derivatives were also prepared and used as chiral stationary phases. Optical resolving abilities depended greatly on the substituents and tris(3,5-dimethylphenylcarbamate) exhibited high optical resolving ability which was different from that of the same derivative of cellulose, the amylose derivative resolved many enantiomers which could not be separated on cellulose tris(3,5-dimethylphenylcarbamate). These tris(3,5-dimethylphenylcarbamate)s were also supported on the silica gel with a greater diameter to be used as stationary phases for preparative separation. The resulting stationary phases were found to be useful for a large-scale separation.