新型直链淀粉类手性固定相的制备与手性拆分性能

发布时间：2018-09-04 20:35

【摘要】：通过对糖单元2-位进行选择性酯化以及6-位保护与去保护,运用区域选择性方法合成了5种新型直链淀粉类衍生物,分别为直链淀粉-2-苯甲酸酯-3-(4-氯苯基氨基甲酸酯)-6-(3,5-二甲基苯基氨基甲酸酯)、直链淀粉-2-苯甲酸酯-3-(4-氯苯基氨基甲酸酯)-6-(3,5-二氯苯基氨基甲酸酯)、直链淀粉-2-苯甲酸酯-3,6-二(4-氯苯基氨基甲酸酯)、直链淀粉-2-(4-氯苯甲酸酯)-3,6-二(3,5-二氯苯基氨基甲酸酯)和直链淀粉-2-(4-氯苯甲酸酯)-3,6-二(环己基氨基甲酸酯),并将其涂覆在氨丙基硅胶表面制备了HPLC手性固定相。利用核磁共振-氢谱(1H-NMR)和傅里叶变换红外光谱(FT-IR)技术对所合成衍生物的结构进行了表征和分析,并用HPLC法评价所合成衍生物的手性识别能力。与具有单一取代基直链淀粉类手性固定相的对比分析表明,所合成的新型直链淀粉类手性固定相对于某些对映体具有更为优异的拆分结果。进一步分析表明,2-、3-和6-位取代基的性能和引入位置对直链淀粉衍生物的手性识别能力均有较大的影响。
[Abstract]:Five new amylose derivatives were synthesized by selective esterification of 2-site of sugar unit and protection and deprotection of 6-site. Amylose -2-benzoate -3- (4-chlorophenyl carbamate) -6- (3o 5-dimethylphenyl carbamate), amylose -2-benzoate -3- (4-chlorophenyl carbamate) -6- (3o 5-dichlorophenyl carbamate), amylose -2-benzoic acid Ester -3- (4-chlorophenyl carbamate), amylose -2- (4-chlorobenzoate) -3- (3-triphenylcarbamate) and amylose -2- (4-chlorobenzoate) -3- (cyclohexylcarbamate), and coated with aminopropyl silica gel HPLC chiral stationary phase was prepared on the surface. The structures of the synthesized derivatives were characterized and analyzed by 1H-NMR and FT-IR. The chiral recognition ability of the synthesized derivatives was evaluated by HPLC method. The comparison with the chiral stationary phase of amylose with a single substituent group shows that the new type of amylose chiral fixation has better resolution results than some enantiomers. The further analysis shows that the properties and the introduced positions of the substituents of 2-O3- and 6- have a great influence on the chiral recognition ability of amylose derivatives.
【作者单位】：哈尔滨工程大学材料科学与化学工程学院超轻材料和表面技术教育部重点实验室高分子材料研究中心;日本名古屋大学;
【基金】：国家自然科学基金项目(21474024;51073046) 黑龙江省自然科学基金项目(B2015022) 中央高校基本科研业务费专项资金(HEUCFT1009)~~
【分类号】：O652.63;O636.12

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