为制备新型手性分离材料,用含不同取代基的苯甲酰氯修饰壳聚糖,合成了壳聚糖-二(4-甲基苯甲酸酯)-(4-甲基苯甲酰胺)、壳聚糖-二(苯甲酸酯)-(苯甲酰胺)、壳聚糖-二(3,5-二甲基苯甲酸酯)-(3,5-二甲基苯甲酰胺)和壳聚糖-二(4-氯苯甲酸酯)-(4-氯苯甲酰胺)4种新的衍生物,以N,N-二甲基甲酰胺为溶剂,将壳聚糖衍生物涂敷于大孔的3-氨丙基硅胶上,制得相应的手性固定相.测试了固定相的手性识别性能,结果表明这些固定相均有较好的对映体选择性.涂覆量为16%的固定相比涂覆量为20%的固定相有更好的手性分离性能,以壳聚糖-二(3,5-二甲基苯基甲酸酯)-(3,5-二甲基苯基甲酰胺)制备的固定相有最强的手性识别性能,以壳聚糖-二(4-甲基苯甲酸酯)-(4-甲基苯甲酰胺)制备的固定相对手性化合物有最大的分离度.
In order to develop novel chiral stationary phases (CSPs), chitosan was modified by benzoyl chlorides with various substituents, successively using methylsulfonic acid and N, N-dimethylaeetamide as the solvents. In this way, new derivatives of chitosan bis (benzoate)-( benzamide ), chitosan bis (4- methylbenzoate ) - ( 4-methylbenzamide ) , ehitosan bis ( 3,5 -dimethylbenzoate ) - ( 3,5 -dimethylbenzamide ) and chitosan bis ( 4-ehlorobenzoate )-( 4-chlorobenzamide ) were synthesized. The corresponding CSPs were prepared by coating the chitosan derivatives on porous 3-aminopropyl silica gel employing N, N- dimethylforamide as the solvent. The chiral recognition capability of the CSPs was evaluated towards structurally various chiral compounds in normal phase conditions, and the results showed that these CSPs possessed satisfactory enantioselectivity. The CSP prepared from chitosan bis (4-methylbenzoate)-( 4- methylbenzamide) with a coating ratio of 16% exhibited better chiral recognition capability than that prepared from the same derivative with a coating ratio of 20%. The C SP based on ehitosan bis (3,5-dimethylbenzoate)- (3,5-dimethylbenzamide) showed stronger chiral recognition capability than the CSPs based on the other derivatives. Meanwhile, the CSP derived from chitosan bis (4-methylbenzoate) - (4-methylbenzamide) separated the chiral compounds with highest resolutions. This feature is similar to that of the CSP derived from cellulose tris (4-methylbenzoate), and different from that of the CSP prepared from amylose tris (4-methylbenozate) that bear poor chiral recognition capability. The reason may be related to the similarity of chitosan and cellulose in which the repeating units are all connected by β-1,4-glycosidic bond, other than or-1,4-glycosidic bond in amylose. In addition, the CSPs generally demonstrated better resolutions in the mobile phases simultaneously containing ethanol and methanol.