新型纤维素邻乙酰水杨酸酯类手性固定相的合成及评价

Preparation and Evaluation of New Cellulose Acetylsalicylate Chiral Stationary Phase

以纤维素和邻乙酰水杨酰氯为原料,合成了纤维素邻乙酰水杨酸酯类手性固定相,考察了其手性拆分能力,与Chiralcel OJ手性色谱柱进行了比较,并研究了流动相的组成以及衍生物中双酯羰基的结构对其拆分效果的影响。以红外光谱技术、热重分析等检测手段对获得的纤维素衍生物进行结构表征和分析。在对4种流动相：正己烷-异丙醇、正己烷-乙醇、正己烷-甲醇-异丙醇、正己烷-甲醇-1,2-二氯乙烷进行比较筛选后,以正己烷-异丙醇（90∶10~80∶20,V/V,0.1%DEA或TFA）体系作流动相,在正相色谱模式下,对儿茶酚胺类及酰胺类手性药物进行了手性拆分,结果表明,三氟乙酸和二乙胺的最佳使用量均为0.1%,双酯羰基结构的氢键、偶极作用和苯环的π-π作用相互协同确实有助于该类固定相手性拆分作用的形成。

Cellulose acetylsalicylate chiral stationary phase was synthesized by using cellulose and O-acetylsalicylryl chloride, and evaluated by HPLC. In this work, Chiralcel OJ was also evaluated for comparison. The effects of mobile phase composition and double ester carbonyls of derivative on enantioseparation were investigated. The structure of the obtained derivative was characterized by infrared spectroscopy and thermogravimetric analysis. Hexane-isopropanol （90： 10-80：20, 0.1% DEA or TFA） was selected by comparison of four mobile phases ： namely hexane-isopropanol, hexane-ethanol, hexane-methanol- isopropanol and hexane-methanol-dichloroethane. Seven racemates of catecholamine and amide were used to evaluate its chiral recognition ability in normal phase elution mode and the regularity and characteristics of the novel chiral stationary phase were explored. Based on the chromatographic results, cellulose acetylsalicylate exhibited high enantioseparation ability for catecholamines and some racemates with amide group due to the carbonyls of acetylsalicylate and the optimum amount of DEA or TFA is 0.1%.