發(fā)布時(shí)間：2018-06-19 09:09

  本文選題：苯乙烯 + 環(huán)氧化�。� 參考：《瀘州醫(yī)學(xué)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(kāi)環(huán)反應(yīng)和官能團(tuán)轉(zhuǎn)化獲得，其中備受關(guān)注的是作為醫(yī)藥和精細(xì)化工品中間體的手性環(huán)氧苯乙烷。對(duì)于手性環(huán)氧化物的測(cè)定通常采用手性高效液相色譜法或氣相色譜法，但應(yīng)用于苯乙烯環(huán)氧化反應(yīng)的分析檢測(cè)未見(jiàn)系統(tǒng)研究報(bào)道。本文對(duì)苯乙烯不對(duì)稱(chēng)環(huán)氧化反應(yīng)混合物的高效液相色譜分析和氣質(zhì)聯(lián)用分析法進(jìn)行研究，建立苯乙烯不對(duì)稱(chēng)環(huán)氧化反應(yīng)的篩選方法，并結(jié)合正交試驗(yàn)，篩選優(yōu)化苯乙烯不對(duì)稱(chēng)環(huán)氧化反應(yīng)的條件�；诒揭蚁┑牟粚�(duì)稱(chēng)環(huán)氧化反應(yīng)及建立的篩選方法，擴(kuò)展不對(duì)稱(chēng)環(huán)氧化反應(yīng)的范圍，對(duì)肉桂醛和1-辛炔的不對(duì)稱(chēng)加成反應(yīng)及其產(chǎn)物的環(huán)氧化反應(yīng)進(jìn)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(guò)內(nèi)標(biāo)法分析測(cè)定苯乙烯環(huán)氧化反應(yīng)混合物，并利用正交實(shí)驗(yàn)對(duì)苯乙烯環(huán)氧化反應(yīng)進(jìn)行篩選；同時(shí)，采用BINOL/Ti(OiPr)體系不對(duì)稱(chēng)催化辛炔與肉桂醛的加成，并利用Sharpless環(huán)氧化催化體系對(duì)其加成產(chǎn)物進(jìn)行環(huán)氧化反應(yīng)研究。結(jié)果：利用HPLC法分析測(cè)定時(shí)，苯乙烯及(R)/(S)-環(huán)氧苯乙烷的標(biāo)準(zhǔn)曲線(xiàn)線(xiàn)性關(guān)系良好，相關(guān)系數(shù)分別為0.9983、0.9996、0.9995；方法檢測(cè)限低，分別為0.02、0.10和0.13μg/mL；該方法低、中、高三個(gè)濃度水平的回收率為100.2%~100.8%；以相對(duì)標(biāo)準(zhǔn)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(cè)定時(shí)，苯乙烯及(R)/(S)-環(huán)氧苯乙烷標(biāo)準(zhǔn)曲線(xiàn)的相關(guān)系數(shù)分別為0.9997、0.9932和0.9963，檢測(cè)限為1.3、1.1和0.7μg/L；方法的低、中、高三個(gè)濃度水平的回收率為98.2%~116.1%；以相對(duì)標(biāo)準(zhǔn)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(duì)稱(chēng)加成產(chǎn)物-烯丙醇類(lèi)物質(zhì)，產(chǎn)率最高可達(dá)70%，對(duì)映異構(gòu)體過(guò)量（ee值）為80%；對(duì)該烯丙醇進(jìn)行環(huán)氧化反應(yīng)，以20%的產(chǎn)率獲得了環(huán)氧化產(chǎn)物。結(jié)論：應(yīng)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(duì)映異構(gòu)的環(huán)氧苯乙烷，且能實(shí)現(xiàn)環(huán)氧苯乙烷產(chǎn)率及(R)/(S)-環(huán)氧苯乙烷對(duì)映異構(gòu)體過(guò)量的測(cè)定，兩種方法的準(zhǔn)確度和精密度高，可應(yīng)用于苯乙烯及同系物的不對(duì)稱(chēng)環(huán)氧化反應(yīng)混合物的分析測(cè)定及反應(yīng)篩選。利用Sharpless環(huán)氧化反應(yīng)體系可成功合成手性環(huán)氧醇，但其產(chǎn)率的提高及對(duì)映選擇性有待進(jìn)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(xué)位授予單位】：瀘州醫(yī)學(xué)院
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類(lèi)號(hào)】：R914

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