过渡金属催化1-氯代炔烃的合成及炔腈吲哚、共轭烯炔衍生化研究

发布时间：2018-10-15 12:26

【摘要】：1-卤代炔烃一直都是有机合成的重要砌块。独特的C(sp)-X键同时具有可控的亲核及亲电性能,因而在参与化学反应过程中,炔卤灵活多变。炔氯是炔卤的一种,关于它的研究并不多见,原因为尚无良好的合成方法。炔腈作为拟卤素类型的炔卤,其独特的结构引人关注,双不饱和基以C(sp)-C(sp)共轭方式存在,在参与重要有机小分子构建中有着巨大的潜力。本文通过过渡金属催化末端炔烃氯代来提出一个简单易行的炔氯合成方法;以炔腈为原料合成吲哚、共轭烯炔腈等功能小分子。论文研究内容如下:1.直接以末端炔烃为原料,常见的N-氯代丁二酰亚胺为氯源,相对稳定易得的碳酸银作催化剂,同时加入碳酸钾作为碱,在惰性气体氛围下,高产率地制备了炔氯。该方法底物适用性良好,对大多数官能团都能兼容。相对于传统方法,该方法有着原料廉价易得,反应条件温和,操作简单,毒性小,相对环保的特点。2.炔腈和取代苯胺为原料,通过乙酸钯催化一锅合成吲哚杂环。该反应以氧气作为氧化剂,避免了其它高价金属氧化剂以及氧化性有机物可能带来的污染。另外,一锅法进行该反应避免了中间体的分离,简化了操作。通过实验对反应机理进行验证,可能为:钯插入烯胺的烯氢位置,与苯环发生关环,钯脱去形成吲哚环,被还原的零价钯则被氧气氧化成二价钯。3.在过量三乙胺存在条件下,5%的1,4-双(二苯膦基)丁烷二氯化钯催化剂能够有效促进炔腈和末端炔烃加成生成共轭烯炔腈。通过对分离产物的核磁谱图进行分析,证实该反应立体选择性良好,大部分生成单一构型的共轭烯炔腈。该反应条件简单,官能团兼容性好,有可能被用来合成多共轭烯炔腈,具备潜在的应用价值。
[Abstract]:1-halogenated alkynes have always been an important block in organic synthesis. The unique C (sp)-X bond has both controllable nucleophilic and electrophilic properties, so acetylene halides are flexible and changeable in the process of chemical reaction. Acetylene chloride is a kind of acetylene halides, but the research on it is rare, because there is no good synthetic method. As a halogen type acetylene halide, the unique structure of acetonitrile has attracted much attention. The double unsaturated group exists in the form of C (sp)-C (sp) conjugation, and has great potential to participate in the construction of important organic small molecules. In this paper, a simple and feasible method for the synthesis of acetylene chloride is proposed by using transition metal to catalyze the chlorination of terminal alkynes, and the functional small molecules such as indole and conjugated alkyne nitrile are synthesized from acetylonitrile. The research contents are as follows: 1. Using terminal alkynes as raw material, common N-chlorosuccinimide as chlorine source, relatively stable silver carbonate as catalyst and potassium carbonate as base, acetylene chloride was prepared in high yield under the atmosphere of inert gas. The method is suitable for most functional groups and is compatible with most functional groups. Compared with the traditional method, this method has the characteristics of cheap raw material, mild reaction conditions, simple operation, low toxicity and relative environmental protection. 2. Indole-heterocyclic compounds were synthesized from acetylonitrile and substituted aniline in one pot catalyzed by palladium acetate. Oxygen is used as oxidant in this reaction to avoid the pollution caused by other high-valence metal oxidants and oxidizing organic compounds. In addition, the one-pot reaction avoids the separation of intermediates and simplifies the operation. The mechanism of the reaction is verified by experiments. It is possible that PD intercalates enamine at the enhydrogen position, close the ring with benzene ring, remove palladium to form indole ring, and the reduced zero valence palladium is oxidized to divalent palladium by oxygen. In the presence of excessive triethylamine, 5% catalyst of 1 '4-bis (diphenylphosphino) butane dichloride palladium can effectively promote the addition of acetylene and terminal alkynes to conjugated enyne nitrile. Through the analysis of the NMR spectra of the separated products, it is proved that the reaction has good stereoselectivity, and most of the conjugated enyne nitriles with a single configuration are formed. The reaction condition is simple, the functional group compatibility is good, and it may be used to synthesize polyconjugated alkynylonitrile, which has potential application value.
【学位授予单位】：华中农业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626

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