水解动力学拆分环氧氯丙烷的研究

论文编号:ZY062    论文字数:10040,页数:34

摘要：手性环氧氯丙烷在立体控制合成有机化合物方面是一类极有价值的中间体。通过手性环氧氯丙烷为反应起始物，可以得到很多有用的高光学纯度药物中间体和天然产物。本文确定了用水解动力学拆分方法制备(S)-环氧氯丙烷。首先将(R，R)-l，2-环己二胺-(+)-酒石酸盐与3，5-二叔丁基水杨醛缩合，得到手性Salen配体，再与Co(OAc)2络合、氧化得到Salen Co(Ⅲ)手性催化剂，催化外消旋环氧化物水解动力学拆分，所得手性环氧化合物对映体过量最高分别可达99％。最后合成了新型的双核salen催化剂[(salen)Co(Ⅱ)]2(AlCl3)，[(salen)Co(Ⅱ)]2(FeCl3)，结果表明这两种新型的催化剂可以有效的对环氧氯丙烷进行拆分,并对(salen)Co(Ⅱ)与FeCl3，AlCl3，ZnCl2分别溶于CH2Cl2后的溶液进行紫外图谱表征。

关键词：Salen催化剂；水解动力学拆分；手性环氧氯丙烷；紫外吸收光谱

Abstract: Chiral epichlorohydrin was a very important synton in organic synthesis. It was very common and easy to start with chiral epichlorohydirn for the generation and manufacturing of optically active compounds.Compared with some other methods, the hydrolytic kinetic resolution (HKR) was chosen for the production of (S)-epichlorohydrin. Condensation of (R,R)-1,2-Diammoniumcyclohexaneono-(+)-tartrate with 5-di-tert-butylsalicylaldehyde gave the chiral Salen ligand，which reacted with cobalt acetate and then oxidized to give the (Salen) Co(III) catalysts，which catalyzes the asymmetric ring-opening of racemic epoxides to afford epoxides with the ee up to 99％．Finally, three kinds of salen catalysts were synthesized, such as [(salen)Co(Ⅱ)]2(AlCl3)，[(salen)Co(Ⅱ)]2(FeCl3), [(salen)Co(Ⅱ)]2(ZnCl2). It was turned out that this two new kinds of catalysts can catalyzes epichlorohydrin availability, UV-vis absorption Spectra (Salen) Co(Ⅱ) and FeCl3, AlCl3and ZnCl2 which were measured mixing in CH2Cl2.

Keywords: Chiral epichlorohydrin; Hydrolytic Kinetic Resolution (HKR); Salen Catalyst; UV-vis absorption Sperctra 
目录
摘要
英文摘要
目录
1前言 1 1.1引言 1
 1.2研究现状 2
 1.3 本章小结 6
2 实验 7
 2.1 实验试剂与仪器 7
 2.2 实验步骤 8
 2.3 催化剂的紫外图谱表征 13
3 结果与讨论 14
 3.1 [（salen）Co(Ⅱ)]2(AlCl3)的催化效果 14
 3.2 [（salen）Co(Ⅱ)]2(FeCl3)的催化效果 14
 3.3[（salen）Co(Ⅱ)]2(ZnCl2)的催化效果 15
 3.4 催化剂的紫外图谱表征结果 16
 3.5本章小结 26
4 结论与展望 27
致谢 28
参考文献 29