【作者】 陈平；

【导师】 侯经国； 杨武；

【作者基本信息】 西北师范大学 ， 分析化学， 2003， 硕士

【摘要】 随着科学技术的发展，人们对不同旋光性药物所表现出来的不同的生理活性这一现象认识更加深入。在生物化学、药物化学及有机化学中的不对称合成和催化技术中，旋光异构体的分离与分析显得越来越重要。在众多的旋光异构体的分离与分析方法中高效液相色谱手性固定相直接拆分是一种具有快速，有发展潜力的方法之一。本文重点研究了多糖类衍生物手性固定相。本论文共分四部分： 第一章综述了高效液相色谱手性固定相，重点评述了多糖类衍生物手性固定相的发展、手性固定相的类型、拆分机理、分离范围及应用的最新进展。 第二章合成了手性填料纤维素-三（4-甲基苯甲酸酯），并涂敷于氨丙基硅胶上，制备成手性固定相。用高效液相色谱法，在此手性固定相上，对农药禾草灵外消旋体进行了拆分，考察了流动相组成，温度，醇效应对禾草灵对映体拆分及保留的影响，由实验结果对禾草灵对映体之间的-△_R，S△G^θ，△_R，S△H^θ，△_R，A△S^θ进行了计算，并对其在OJ柱上保留机理进行了讨论。 第三章近二十多年来，四面体原子簇化合物的合成方面研究已取得了很大的发展，但拆分四面体原子簇化合物来得到足够量的对映异构体是件很困难的事。我们用自制的纤维素-三（3，5-二甲基苯基氨基甲酸酯）手性固定相为手性填料，在正相条件首次成功地拆分了多种四面体金属簇化合物。系统地研究了以正己烷-醇为流动相，考察了流动相中醇的含量、醇链长度、醇的立体结构对手性拆分的影响。由实验结果提出了原子簇化合物与手性固定相的作用模式，解释了样品结构对手性拆分的影响。 第四章在OD柱和OJ柱上对外消旋体α-苯乙醇进行了拆分，选择了最佳的拆分条件，并将此方法应用于苯乙酮不对称催化还原产物的光学纯度的鉴定中，取得了较满意的结果。更多还原

【Abstract】 With the development of science and technology , people deeply realize the distinguish between enantiomers for optically active compounds. It is becoming important to separate optical active compounds in the fields of biochemistry , organic chemistry, pharmaceutical chemistry as well as asymmetric synthesis and catalysis. There are many methods to separate optically active compounds. Among them, the high performance liquid chromatography (HPLC-CSP) is one of the rapid, most prospect methods in chiral separation. In the thesis, we emphasize on cellulose derivatives chiral stationary phase coated on silica gel.This paper consists of four parts:In the first part (chapter 1), the importance and methods of enantioseparation for chiral compounds have been reviewed systematically. It is given emphasis to development and types of cellulose chiral stationary phases . Especially application in enantioseparation and mechanism of chiral recognition of cellulose chiral stationary phases are mainly reviewed in detail.In the second part (chapter 2), Cellulose tris (4-methylbenzoate) was synthesized by the reaction of microcrystalline cellulose with benzoyl chloride. A chiral stationary phase was prepared by coating cellulose tris (4-methylbenzoate) on the silica .On the cellulose tris (4-methylbenzoate ) chiral stationary phase (CTMB-CSP), diclofop-methyl was resolved in normal-phase system. The influence of the composition of the mobile phase and the column temperature was investigated. were calculated and retention mechanism was researched.The third part (chapter 3 ) The asymmetric catalysis induced by metal framework chirality, instead of phosphine ligands, is alluring and difficult task in the field of catalysis. Today, there is rapid progress in synthesis of chiral metal clusters(l). It is very important to separate the metal clusters in order to gain adequate optical isomers, which can be used in catalysis. Unfortunately, separation of metal clusters is very difficult. Cellulose tris (3,5-dimethylphenylcarbamate) was prepared and used to chiral separation for five novel chiral metal clusters. The influence of alcohol such as the length of alkyl chain, steric bulkand content of alcohol in mobile phases were systematically examined. Based on the experimental results, the mechanism of the chiral recognition was discussed.The fourth part (chapter 4 ) a -phenylethanol was resolved on CDMPC and CTMB in normal-phase system. The influence of the composition and flow rate of the mobile phase was investigated. We choose the best experimental condition and determinate the excess value of the reaction.更多还原