水解动力学拆分外消旋环氧氯丙烷

制药工程论文编号:ZY071    论文字数:12260,页数:39

目  录
摘要 I
Abstract II
目录 III
1. 绪论 1
 1.1  手性化合物拆分方法 1
 1.2 获得手性环氧氯丙烷的方法 4
 1.3 手性(Salen)Co催化剂的合成 6
 1.4 论文研究内容及意义 7
2. 实验部分 8
 2.1 实验仪器与试剂 8
 2.2 催化剂的合成 9
3. 结果与讨论 15
 3.1 (Salen)Co(III)(OAc) 水解动力学拆分的研究 15
 3.2 催化剂的表征  23
 3.3 催化剂的比较 29
4．总结与展望 31
    4.1总结 31
    4.2展望 31
致谢 32
参考文献 33

摘 要：通过对多种手性拆分方法进行比较，本文选择水解动力学拆分外消旋环氧氯丙烷。首先合成了(Salen)Co(III)(OAc)催化剂，并对催化剂进行表征，建立了快速可靠的气相色谱法来跟踪检测产物(S)-环氧氯丙烷的e.e.值（对映体过量值）。然后通过对拆分过程中e.e.值变化的跟踪分析，对反应条件进行单因素优化，发现反应在温度20℃，水用量为0.55当量，催化剂浓度为0.5mol%时，能够在10小时内得到e.e.值>99.5%的(S)-环氧氯丙烷。
 合成了几种双核催化剂，[(Salen)Co(II)]2(AlCl3)、[(Salen)Co(II)]2(SnCl4)、 [(Salen)Co(II)]2(SnCl2)、 [(Salen)Co(II)]2(ZnCl2)和[(Salen)Co(II)]2(FeCl3),并对催化剂进行表征。通过对不同Salen催化剂存在下的水解动力学实验研究，发现[(Salen)Co(II)]2(FeCl3)和[(Salen)Co(II)]2(ZnCl2)催化效果非常好，在得到的较优条件下反应，能够在10小时内得到e.e.值>99.5%的(S)-环氧氯丙烷。
关键词：水解动力学拆分；Salen催化剂；环氧氯丙烷

Abstract:Compared with many methods reported, the hydrolytic kinetic resolution (HKR) was choosed to resolute the racemic epichlorohydrin. Firstly, the (Salen)Co(III)(OAc) catalyst was synthesized and was characterized by IR. The e.e. (enantiomeric excess) of the (S)-epichlorohydrin was determined by GC analysis. Secondly, the optimization of the condition was investigated through the mono-factor’s experiment. Under the condition that the temperature was 20℃, the water was 0.55 equivalent, and the concentration of the catalyst was 0.5mol%, the e.e. of the (S)-epichlorohydrin would over 99.5% within 10 hours .
 Some new kinds of Salen catalysts were synthesized, such as [(Salen)Co(II)]2(AlCl3), [(Salen)Co(II)]2(SnCl4), [(Salen)Co(II)]2(SnCl2),   [(Salen)Co(II)]2(ZnCl2) and [(Salen)Co(II)]2(FeCl3). Through the comparative research on hydrolytic kinetic experiments with different Salen catalysts,  [(Salen)Co(II)]2(ZnCl2) and [(Salen)Co(II)]2(FeCl3) were good catalyses. Using these two catalysts, with good condition, (S)-epichlorohydrin whose enantiomeric excess value was over 99.5% in 10 hours was got.
 Keywords: Hydrolytic kinetic resolution; Salen catalyst; racemic epichlorohydrin