脂肪酶介导氧化反应及其在有机合成中的应用

发布时间：2018-05-20 02:08

本文选题：催化非专一性 + 脂肪酶　；参考：《吉林大学》2017年硕士论文

【摘要】：酶是具有生物催化功能的大分子物质,具有催化效率高、专一性强、反应条件温和、生物可降解、对环境友好等优点,符合绿色化学和原子经济的要求。随着酶学研究的不断发展,许多酶被报道能催化多种类型的反应,这种特性称为酶催化非专一性。酶催化非专一性的研究,为绿色化学的发展提供一条有效的新途径。脂肪酶是一种商品化程度高、稳定性强、底物作用范围广的酶制剂,也是酶催化非专一性领域中研究较为深入的一类酶。本文主要研究脂肪酶介导的氧化反应及其在有机合成中的应用。主要研究内容和结果如下:研究脂肪酶催化的Knoevenagel-Epoxidation串联反应,为α-氰基环氧化合物的合成提供一条绿色高效且温和的合成路线。我们对该反应的条件进行优化和筛选:包括酶源、酶的用量、溶剂,进而确定了该反应最适体系。本节研究结果表明:在50oC条件下,300 U Novozym 435、1.5 mmol过氧化脲(UHP)催化1 mmol底物在N,N-二甲基甲酰胺(DMF)/乙酸乙酯(EA)为2/3体系中具有最佳产率。研究脂肪酶介导的氧化偶氮苯类化合物及其衍生物的合成。氧化偶氮苯类化合物具有广泛的应用,可作为染料、化学稳定剂、药物中间体,是一种非常重要的化合物。经研究本反应的最适条件为:在室温条件下,脂肪酶(300U),苯胺(2mmol),过氧化脲(2.5 mmol),乙酸乙酯(5 m L),反应时间1 h。值得关注的是底物分子取代基的电子效应对氧化偶氮苯化合物产率的影响并不大,但是其位阻效应对反应产率具有明显的影响。研究双酶(葡萄糖氧化酶与脂肪酶)体系共催化N-杂环化合物和三级胺的N-氧化合物的氧化合成。本反应通过对葡萄糖氧化酶与脂肪酶的比例以及用量、反应体系中磷酸盐缓冲液与乙酸乙酯的比例、反应时间等因素进行优化,在较温和件下即可获得很高产率。通过放大实验以及底物适用性研究,证实该双酶体系具有较高的工业应用价值。
[Abstract]:Enzyme is a macromolecular material with biocatalytic function, which has the advantages of high catalytic efficiency, strong specificity, mild reaction conditions, biodegradable and environment-friendly. It meets the requirements of green chemistry and atomic economy. With the development of enzymology, many enzymes have been reported to catalyze many kinds of reactions, which is called enzymatic non-specificity. The study of enzyme-catalyzed non-specificity provides an effective new way for the development of green chemistry. Lipase is a kind of enzyme preparation with high degree of commercialization, strong stability and wide range of substrate action. It is also a kind of enzyme which has been studied deeply in the field of enzymatic catalysis. This paper focuses on lipase-mediated oxidation and its application in organic synthesis. The main contents and results are as follows: the lipase-catalyzed Knoevenagel-Epoxidation series reaction provides a green efficient and mild synthetic route for the synthesis of 伪 -cyanoepoxy compounds. We optimized and screened the reaction conditions, including enzyme source, amount of enzyme, solvent, and then determined the optimal reaction system. In this section, the results show that 1 mmol substrate catalyzed by 300U Novozym 435N 1.5 mmol UHP) under 50oC conditions has the best yield in the system of N- (N-dimethylformamide) DMFU / ethyl acetate (EAA) = 2 / 3. The synthesis of oxidized azobenzene compounds and their derivatives mediated by lipase was studied. Oxidized azobenzene compounds are widely used as dyes, chemical stabilizers and pharmaceutical intermediates. The optimum reaction conditions were as follows: lipase 300 U, aniline 2 mmol / L, urea peroxide 2.5 mmol / L, ethyl acetate 5 mL / L, reaction time 1 h. It is worthy of attention that the electronic effect of the substituents of the substrates has little effect on the yield of oxidized azobenzene compounds, but its steric resistance effect has a significant effect on the yield of the reaction. The oxidation synthesis of N-heterocyclic compounds and N-oxide compounds with tertiary amine catalyzed by two enzymes (glucose oxidase and lipase) was studied. By optimizing the ratio and dosage of glucose oxidase to lipase, the ratio of phosphate buffer to ethyl acetate, the reaction time and so on, the yield of high yield could be obtained under mild conditions. It is proved that the double enzyme system has high industrial application value through the experiments of magnification and the study of substrate applicability.
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.3;Q55

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