【作者】 周荣源；

【导师】 杨祥良； 万江陵；

【作者基本信息】 华中科技大学 ， 生物制药工程， 2007， 硕士

【摘要】 Salen金属催化剂特别是Jacobsen催化剂在催化不对称合成中应用十分广泛,如烃的不对称环氧化反应、外消旋环氧化合物的水解动力学拆分、Strecker反应、不对称氰硅烷化、消旋环氧化合物的不对称开环反应、Diels-Alder环加成反应、不对称环丙烷化反应等。本论文主要由以下三部分组成:(1) Jacobsen催化剂的合成。从消旋的环己二胺出发,通过酒石酸拆分分别得到(R,R)-1,2-环己二胺-(+)-酒石酸盐和(S,S)-1,2-环己二胺-(+)-酒石酸盐,然后与3,5-二叔丁基-2-羟基苯甲醛反应制得手性的Jacobsen催化剂,并通过紫外光谱、红外光谱、1H NMR、1C NMR等方法对其结构进行了表征。(2)在上述基础上,对环氧氯丙烷进行水解动力学拆分,系统的研究了反应温度、时间、催化剂浓度、催化剂的循环使用次数等各种因素对产品的产率和光学纯度的影响,为以后的工业化生产提供了一个可靠的依据。(3)丙酰左卡尼汀盐酸盐合成工艺的研究。以S-(+)-环氧氯丙烷为起始原料,经胺化、氰化、水解、酯化反应而得到丙酰左卡尼汀盐酸盐。其结构经过IR、MS、NMR以及元素分析确证。该工艺具有反应条件温和,易于操作,成本较低的优点。更多还原

【Abstract】 Salen metal catalysts,especially Jacobsen catalyst,have been widely used in catalytic symmetric reaction, such as asymmetric epoxidizing reaction of Olefine, hydrolytic kinetic resolution of meso epoxides, Strecker reaction, asymmetric cyanide silane, asymmetric ring opening of racemic terminal epoxides, racemic epoxides open-loop asymmetric reactions, the Diels-Alder cycloaddition, asymmetric cyclopropanation, and so on.This thesis consists of three parts:(1) Synthesis of Jacobsen catalyst. (R,R)-1, 2-diammoniumcyclohexane mono-(+)- tartrate salt and (S,S)-1, 2-diammoniumcyclohexane mono-(+)-tartrate are acquired through the resolution of cis/trans-1, 2-diammoniumcyclohexane, and react with 3, 5- Di-tert- butyl-2- Hydroxybensaldehyde and get Jacobsen catalyst in the end. Their structures are characterized by UV, IR, 1H NMR, 13C NMR.(2) Hydrolytic kinetic resolution of epihalohydrin. Systematic study of reaction temperature, time, concentrations of catalyst, and recycle times of catalyst on how to affect the yield and optical purity of production. This research can be provided a reliable basis for industrial production.(3) Synthesis of PLC. PLC is synthesized by amination, cyanidation, hydrolytic action and esterification with S- epihalohydrin as starting material, and identified by IR, MS, NMR as well as element analysis. This process has the advantages of mild conditions, convenient operations, besides low cost.更多还原