本文選題：苯乙烯 + 環(huán)氧化�。� 參考：《瀘州醫(yī)學院》2014年碩士論文

【摘要】：目的：手性環(huán)氧化合物具有重要的生理活性，許多重要的醫(yī)藥中間體可由其選擇性開環(huán)反應和官能團轉(zhuǎn)化獲得，其中備受關注的是作為醫(yī)藥和精細化工品中間體的手性環(huán)氧苯乙烷。對于手性環(huán)氧化物的測定通常采用手性高效液相色譜法或氣相色譜法，但應用于苯乙烯環(huán)氧化反應的分析檢測未見系統(tǒng)研究報道。本文對苯乙烯不對稱環(huán)氧化反應混合物的高效液相色譜分析和氣質(zhì)聯(lián)用分析法進行研究，建立苯乙烯不對稱環(huán)氧化反應的篩選方法，并結(jié)合正交試驗，篩選優(yōu)化苯乙烯不對稱環(huán)氧化反應的條件�；诒揭蚁┑牟粚ΨQ環(huán)氧化反應及建立的篩選方法，擴展不對稱環(huán)氧化反應的范圍，對肉桂醛和1-辛炔的不對稱加成反應及其產(chǎn)物的環(huán)氧化反應進行探索。方法：采用手性高效液相色譜法(HPLC)和氣質(zhì)聯(lián)用/選擇離子法(GC-MS/SIM)，，通過內(nèi)標法分析測定苯乙烯環(huán)氧化反應混合物，并利用正交實驗對苯乙烯環(huán)氧化反應進行篩選；同時，采用BINOL/Ti(OiPr)體系不對稱催化辛炔與肉桂醛的加成，并利用Sharpless環(huán)氧化催化體系對其加成產(chǎn)物進行環(huán)氧化反應研究。結(jié)果：利用HPLC法分析測定時，苯乙烯及(R)/(S)-環(huán)氧苯乙烷的標準曲線線性關系良好，相關系數(shù)分別為0.9983、0.9996、0.9995；方法檢測限低，分別為0.02、0.10和0.13μg/mL；該方法低、中、高三個濃度水平的回收率為100.2%~100.8%；以相對標準偏差表示的精密度分別為0.86%、1.52%和1.80%。采用氣質(zhì)聯(lián)用法分析測定時，苯乙烯及(R)/(S)-環(huán)氧苯乙烷標準曲線的相關系數(shù)分別為0.9997、0.9932和0.9963，檢測限為1.3、1.1和0.7μg/L；方法的低、中、高三個濃度水平的回收率為98.2%~116.1%；以相對標準偏差表示的精密度分別為3.57%、3.08%和2.80%。獲得了肉桂醛與1-辛炔的不對稱加成產(chǎn)物-烯丙醇類物質(zhì)，產(chǎn)率最高可達70%，對映異構體過量（ee值）為80%；對該烯丙醇進行環(huán)氧化反應，以20%的產(chǎn)率獲得了環(huán)氧化產(chǎn)物。結(jié)論：應用HPLC法和氣質(zhì)聯(lián)用/選擇離子法均能很好的分離苯乙烯及對映異構的環(huán)氧苯乙烷，且能實現(xiàn)環(huán)氧苯乙烷產(chǎn)率及(R)/(S)-環(huán)氧苯乙烷對映異構體過量的測定，兩種方法的準確度和精密度高，可應用于苯乙烯及同系物的不對稱環(huán)氧化反應混合物的分析測定及反應篩選。利用Sharpless環(huán)氧化反應體系可成功合成手性環(huán)氧醇，但其產(chǎn)率的提高及對映選擇性有待進一步探索。
[Abstract]:Objective: chiral epoxides have important physiological activity. Many important pharmaceutical intermediates can be obtained by selective opening reaction and conversion of functional groups. The most important thing is the chiral epoxide as the intermediate of medicine and fine chemicals. The chiral high performance liquid phase color is usually used for the determination of chiral epoxides. There is no systematic study on the analysis and detection of styrene epoxidation reaction by spectrum or gas chromatography. This paper studies the high performance liquid chromatography analysis and GC-MS analysis of styrene asymmetric epoxidation reaction mixture, and establishes a screening method for asymmetric epoxidation of styrene. The conditions of asymmetric epoxidation of styrene were optimized. Based on the asymmetric epoxidation of styrene and the screening method established, the range of asymmetric epoxidation was extended, the asymmetric addition reaction of Cinnamaldehyde and 1- ocyne and the epoxidation reaction of the products were explored. The reaction mixture of styrene epoxidation was determined by GC-MS / GC-MS/SIM, and the epoxidation reaction of styrene was screened by orthogonal experiment. At the same time, the addition of symoxyne with cinnamaldehyde was catalyzed by BINOL/Ti (OiPr) system, and the addition product of Sharpless epoxidation catalyst system was used. Study on the reaction of epoxidation. Results: the standard curve of styrene and (R) / (S) - Epoxy benzene ethane has good linear relationship, and the correlation coefficient is 0.9983,0.9996,0.9995, and the detection limit is low, 0.02,0.10 and 0.13 u g/mL respectively. The method is low, and the recovery rate of the middle and high levels is 100.2%~100.8% The relative coefficient of the standard curve of styrene and (R) / (S) - Epoxy ethylbenzene was 0.9997,0.9932 and 0.9963 respectively when the precision of the relative standard deviation was 0.86%, 1.52% and 1.80%. were determined by GC-MS. The detection limit was 1.3,1.1 and 0.7 mu g/L, and the recovery of the three concentrations of the method was 98.2%~116.1 %, the precision of the relative standard deviation was 3.57%, 3.08% and 2.80%. obtained the unsymmetrical addition product of Cinnamaldehyde and 1- ocyne - allyl alcohol, the highest yield up to 70%, the enantiomer excess (EE value) 80%, and the epoxidation of the allyl alcohol by 20% yield. Conclusion: application of HPL The C method and GC-MS / GC-MS can well separate styrene and enantiomer epoxide, and can determine the yield of epoxide and (R) / (S) - Epoxide enantiomer overdose. The accuracy and precision of the two methods are high, and can be applied to the asymmetric epoxidation of styrene and their homologues. The synthesis of chiral epoxy alcohols can be successfully synthesized by the Sharpless epoxidation reaction system, but the increase of the yield and the enantioselectivity of the enantiomer need to be further explored.
【學位授予單位】：瀘州醫(yī)學院
【學位級別】：碩士
【學位授予年份】：2014
【分類號】：R914

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