Shen Jun, Li Pengfei, Liu Shuangyan, Shen Xiande, Okamoto Yoshio
Polymer Materials Research Center, College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China.
Chirality. 2011 Nov;23(10):878-86. doi: 10.1002/chir.21000. Epub 2011 Sep 20.
The regioselectively substituted amylose derivatives bearing a 4-tert-butylbenzoate or 4-chlorobenzoate group at 2-position, and 3,5-dichlorophenylcarbamate and a small amount of 3-(triethoxysilyl)propylcarbamate groups at 3- and 6-positions were synthesized by a two-step process based on the esterification of 2-position of a glucose unit. The obtained derivatives were effectively immobilized onto macroporous silica gel by intermolecular polycondensation of triethoxysilyl groups. Their chiral recognition abilities were evaluated as chiral packing materials (CPMs) for high-performance liquid chromatography. These CPMs showed high chiral recognition as well as the conventional coated-type CPM, and can be used with the eluents-containing chloroform and tetrahydrofuran. With the extended use of these eluents, improvement of chiral recognition and reversed elution orders were realized. For some racemates, the immobilized CPM exhibited ability comparable or better to the commercial immobilized amylose- or cellulose-based columns, Chiralpak IA, IB, and IC.
基于葡萄糖单元2位的酯化反应，通过两步法合成了在2位带有4-叔丁基苯甲酸酯或4-氯苯甲酸酯基团、在3位和6位带有3,5-二氯苯基氨基甲酸酯和少量3-(三乙氧基甲硅烷基)丙基氨基甲酸酯基团的区域选择性取代直链淀粉衍生物。通过三乙氧基甲硅烷基的分子间缩聚反应，将所得衍生物有效地固定在大孔硅胶上。作为高效液相色谱的手性固定相（CPM），对它们的手性识别能力进行了评估。这些CPM表现出与传统涂覆型CPM一样高的手性识别能力，并且可以与含有氯仿和四氢呋喃的洗脱剂一起使用。随着这些洗脱剂的广泛使用，实现了手性识别的改善和洗脱顺序的反转。对于一些外消旋体，固定化CPM表现出与市售的基于直链淀粉或纤维素的固定化柱Chiralpak IA、IB和IC相当或更好的能力。
