新型直链淀粉类手性固定相的制备与手性拆分性能

Preparation and enantioseparation property of novel amylose-based chiral stationary phases for high performance liquid chromatography

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。

Five new amylose derivatives, namely amylose 2-benzoate-3-（ 4-chlorophenylcar- bamate ） -6- （ 3,5-dimethylphenylcarbamate ） , amylose 2-benzoate-3- （ 4-chlorophenylcarbamate ） - 6-（ 3, 5-dichlorophenylcarbamate ）, amylose 2-benzoate-3, 6-bis （ 4-chlorophenylcarbamate ） , amylose 2-（ 4-chlorobenzoate ）-3, 6-bis （ 4-chlorophenylcarbamate ） and amylose 2-（ 4-chloro- benzoate）-3,6-biscyclohexylcarbamate, were synthesized by a series of regioselective process. These derivatives were then coated on the surface of aminopropyl silica gels, and used as chiral stationalw phases （CSPs） for high performance liquid chromatography （HPLC）. These deriva- tives were characterized by ~H-nuclear magnetic resonance （1H-NMR） and Fourier transform infrared （FT-IR） spectroscopies, and their chiral recognition abilities were evaluated using nine raeemates by HPLC. Compared with other amylose derivatives, some racemates were better resolved on the new CSPs. The obtained results indicate that the property and position of sub- stituents at 2-, 3- and 6-positions of glucose unit have great influence on the chiral recognition abilities of the amylose derivatives.