路易斯碱催化的活化环丙烷及环氧乙烷的开环反应研究

发布时间：2018-04-20 00:34

本文选题：路易斯碱 + 活化环丙烷　；参考：《东北师范大学》2016年硕士论文

【摘要】：活化的环丙烷和环氧乙烷在现代化学中,受到了许多学者的关注。活化的环丙烷及环氧乙烷能在路易斯酸或布朗斯特酸作用下发生开环反应；开环后的中间体可在亲核试剂的作用下发生环合或环加成反应。环合所得到的化合物基本骨架广泛存在于天然产物中,有重要的意义。有机催化是现代合成化学中较受关注的研究领域,近几年有机胺的催化较为常见,有机胺是一类拥有N原子和孤电子对的有机化合物,也是常见的有机合成中间体,它可与某些有机物生成较稳定的大分子化合物,增加分子的复杂程度。本文也对有机胺的催化做了探究。本文主要研究了活化环丙烷和环氧乙烷,在路易斯碱作用下的开环及开环中间体在有机合成中的应用。第一部分首先研究了1-乙酰基-1-酰胺基环丙烷及其衍生物在不同的路易斯碱作用下开环原位生成稳定的两性离子中间体,该中间体在适当的条件下容易被分离,可实现克级制备。并通过一锅煮法可使中间体与亲电试剂发生亲核反应,形成具有生物活性的含季碳中心的五元内酰胺化合物。在实验过程中,若将氢氧化钠的用量增加为2.5倍量,时间延长至12小时,产物会变成脱羰基的产物。在此基础上我们还研究了1-乙酰基-1-苯甲酰基环丙烷及其衍生物的开环反应,发现反应机理是先生成两性离子中间体,伴随着时间延长,温度增加,中间体会进一步生成2,3-二氢呋喃产物。与此同时1,1-二酯基环丙烷化合物在有机碱的作用下也可以开环,生成带有羧酸根的内盐。本文也对反应机理进行了推测。第二部分主要研究有机胺对活化环氧乙烷的开环反应。有机碱(如DABCO)的加入使得环氧乙烷的C-O键断裂,经过分子内氧环合形成新的三元含氧杂环中间体,随后发生酰基迁移,脱去有机碱形成多取代顺式烯酯化合物。烯酯既可以作为烯基、羰基的来源,也可以合成某些高分子聚合物。本文合成烯酯的方法具有原子利用率高,环境污染小,产率高,操作简便等优点。在实验中对产物的结构进行了核磁共振氢谱、核磁共振碳谱、质谱以及一些化合物X-ray单晶衍射的表征。
[Abstract]:Active cyclopropane and ethylene oxide have attracted much attention in modern chemistry. The active cyclopropane and ethylene oxide can undergo ring opening reaction under the action of Lewis acid or Brownst acid, and the intermediate after ring opening can take place cyclization or cycloaddition reaction under the action of nucleophilic reagent. The basic framework of the compounds obtained by cyclization exists widely in natural products, which is of great significance. Organic catalysis is an important research field in modern synthetic chemistry. In recent years, the catalysis of organic amines is more common. Organic amines are a class of organic compounds with N atoms and lone electron pairs, and are also common intermediates in organic synthesis. It can form more stable macromolecular compounds with some organic compounds, increasing the molecular complexity. The catalysis of organic amines is also discussed in this paper. In this paper, the applications of active cyclopropane and ethylene oxide, ring opening and ring opening intermediates under the action of Lewis base in organic synthesis were studied. In the first part, we studied the formation of stable amphoteric ion intermediates from 1-acetyl-1-amino-cyclopropane and its derivatives in situ under different Lewis bases. The intermediates are easily separated under suitable conditions. It can be prepared in gram level. The nucleophilic reaction between the intermediate and the electrophilic reagent can be carried out by one-pot cooking method to form a quaternary lactam compound with biological activity containing the quaternary carbon center. During the experiment, if the amount of sodium hydroxide was increased to 2.5 times and the time was prolonged to 12 hours, the product would become the product of decarbonylation. On this basis, we also studied the ring-opening reaction of 1-acetyl-1-benzoyl cyclopropane and its derivatives. The intermediate will further produce 2o 3-dihydrofuran products. At the same time, 1-diester cyclopropane compounds can also open rings under the action of organic bases to form internal salts with carboxylic acids. The reaction mechanism is also speculated. In the second part, the ring opening reaction of organic amine on activated ethylene oxide was studied. The addition of organic base (such as DABCO) breaks the C-O bond of ethylene oxide and forms a new ternary oxygen-containing heterocyclic intermediate through intramolecular oxygen cyclization. Then acyl group migration occurs and the organic base is removed to form polysubstituted cis-alkyl compounds. Alkenyl esters can be used as sources of alkenyl and carbonyl groups, and some polymers can also be synthesized. In this paper, the method of synthesizing alkenyl ester has the advantages of high atomic utilization ratio, low environmental pollution, high yield and easy operation. The structure of the product was characterized by nuclear magnetic resonance (NMR), nuclear magnetic resonance (NMR) carbon spectroscopy (NMR), mass spectrometry (MS) and X-ray single crystal diffraction.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.25

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