水解動力學拆分環氧氯丙烷的研究

制藥工程論文編號:ZY062    論文字數:10040,頁數:34

目錄
摘要
英文摘要
目錄
1前言 1 1.1引言 1
 1.2研究現狀 2
 1.3 本章小結 6
2 實驗 7
 2.1 實驗試劑與儀器 7
 2.2 實驗步驟 8
 2.3 催化劑的紫外圖譜表征 13
3 結果與討論 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 催化劑的紫外圖譜表征結果 16
 3.5本章小結 26
4 結論與展望 27
致謝 28
參考文獻 29

摘要：手性環氧氯丙烷在立體控制合成有機化合物方面是一類極有價值的中間體。通過手性環氧氯丙烷為反應起始物，可以得到很多有用的高光學純度藥物中間體和天然產物。本文確定了用水解動力學拆分方法制備(S)-環氧氯丙烷。首先將(R，R)-l，2-環己二胺-(+)-酒石酸鹽與3，5-二叔丁基水楊醛縮合，得到手性Salen配體，再與Co(OAc)2絡合、氧化得到Salen Co(Ⅲ)手性催化劑，催化外消旋環氧化物水解動力學拆分，所得手性環氧化合物對映體過量最高分別可達99％。最后合成了新型的雙核salen催化劑[(salen)Co(Ⅱ)]2(AlCl3)，[(salen)Co(Ⅱ)]2(FeCl3)，結果表明這兩種新型的催化劑可以有效的對環氧氯丙烷進行拆分,并對(salen)Co(Ⅱ)與FeCl3，AlCl3，ZnCl2分別溶于CH2Cl2后的溶液進行紫外圖譜表征。

關鍵詞：Salen催化劑；水解動力學拆分；手性環氧氯丙烷；紫外吸收光譜

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