水解動力學拆分外消旋環氧氯丙烷

制藥工程論文編號:ZY071    論文字數:12260,頁數:39

目  錄
摘要 I
Abstract II
目錄 III
1. 緒論 1
 1.1  手性化合物拆分方法 1
 1.2 獲得手性環氧氯丙烷的方法 4
 1.3 手性(Salen)Co催化劑的合成 6
 1.4 論文研究內容及意義 7
2. 實驗部分 8
 2.1 實驗儀器與試劑 8
 2.2 催化劑的合成 9
3. 結果與討論 15
 3.1 (Salen)Co(III)(OAc) 水解動力學拆分的研究 15
 3.2 催化劑的表征  23
 3.3 催化劑的比較 29
4．總結與展望 31
    4.1總結 31
    4.2展望 31
致謝 32
參考文獻 33

摘 要：通過對多種手性拆分方法進行比較，本文選擇水解動力學拆分外消旋環氧氯丙烷。首先合成了(Salen)Co(III)(OAc)催化劑，并對催化劑進行表征，建立了快速可靠的氣相色譜法來跟蹤檢測產物(S)-環氧氯丙烷的e.e.值（對映體過量值）。然后通過對拆分過程中e.e.值變化的跟蹤分析，對反應條件進行單因素優化，發現反應在溫度20℃，水用量為0.55當量，催化劑濃度為0.5mol%時，能夠在10小時內得到e.e.值>99.5%的(S)-環氧氯丙烷。
 合成了幾種雙核催化劑，[(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),并對催化劑進行表征。通過對不同Salen催化劑存在下的水解動力學實驗研究，發現[(Salen)Co(II)]2(FeCl3)和[(Salen)Co(II)]2(ZnCl2)催化效果非常好，在得到的較優條件下反應，能夠在10小時內得到e.e.值>99.5%的(S)-環氧氯丙烷。
關鍵詞：水解動力學拆分；Salen催化劑；環氧氯丙烷

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