烯基环丙烷的自由基反应合成多取代二氢萘衍生物的研究
发布时间：2018-08-13 17:07
【摘要】：自由基反应是一类重要的反应类型。由于自由基活泼,反应性强,能够快速反应生成稳定分子等诸多优点,一个世纪以来备受化学研究者的关注。各种自由基反应方法相继报道,并普遍用于化学合成、医药和农药等领域。但就可持续发展而言,研究新型自由基反应仍然具有重要意义。本文的研究内容包含以下两部分:(1)FeCl_2催化条件下实现了烯基环丙烷类底物的三氟甲基化反应,考察了23种不同类型的底物,以最高可达到96%的收率获得了含三氟甲基的二氢萘衍生物。该方法具有反应条件温和、催化剂廉价易得、反应时间短等优点。随后我们将三氟甲基化产物进行还原和脱羧衍生化转化。最后为验证可能的反应机理,设计对照实验,证明该反应可能是自由基反应。(2)非金属催化的条件下实现了烯基环丙烷类底物的叠氮化反应,考察了20种不同类型的底物,以最高可达到88%的收率获得了含叠氮基的二氢萘衍生物,该方法反应条件温和、反应原料廉价易得、反应时间短等优点。最重要的是该反应无需金属催化剂。随后进行叠氮化产物的衍生化实验,分别进行与炔烃的点击反应和还原氨化反应。最后设计对照实验,对反应机理进行研究,表明该反应可能是自由基反应
[Abstract]:Free radical reaction is an important type of reaction. Because of the active free radicals, strong reactivity, rapid reaction to produce stable molecules and many other advantages, it has attracted the attention of chemical researchers for a century. Various free radical reaction methods have been reported and widely used in chemical synthesis, medicine and pesticides. However, as far as sustainable development is concerned, it is still of great significance to study new free radical reactions. The main contents of this paper are as follows: (1) trifluoromethylation of allyl cyclopropane substrates was carried out under the condition of FeCl_2, and 23 different substrates were investigated. The derivative of dihydronaphthalene containing trifluoromethyl was obtained in 96% yield. The method has the advantages of mild reaction conditions, cheap catalyst and short reaction time. The trifluoromethylation products were then reduced and decarboxylated. Finally, in order to verify the possible reaction mechanism, a controlled experiment was designed to prove that the reaction may be a free radical reaction. (2) the azide reaction of allyl cyclopropane substrates was realized under the condition of non-metal catalysis, and 20 different substrates were investigated. The dihydronaphthalene derivatives containing azide group were obtained in a yield of up to 88%. The reaction conditions were mild, the raw materials were cheap and easy to obtain, and the reaction time was short. The most important thing is that the reaction does not require a metal catalyst. Then the azide products were derivatized and the click-down reaction and reductive ammoniation reaction with alkynes were carried out respectively. Finally, a controlled experiment was designed to study the reaction mechanism, which indicates that the reaction may be a free radical reaction.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
，
本文编号：2181636
[Abstract]:Free radical reaction is an important type of reaction. Because of the active free radicals, strong reactivity, rapid reaction to produce stable molecules and many other advantages, it has attracted the attention of chemical researchers for a century. Various free radical reaction methods have been reported and widely used in chemical synthesis, medicine and pesticides. However, as far as sustainable development is concerned, it is still of great significance to study new free radical reactions. The main contents of this paper are as follows: (1) trifluoromethylation of allyl cyclopropane substrates was carried out under the condition of FeCl_2, and 23 different substrates were investigated. The derivative of dihydronaphthalene containing trifluoromethyl was obtained in 96% yield. The method has the advantages of mild reaction conditions, cheap catalyst and short reaction time. The trifluoromethylation products were then reduced and decarboxylated. Finally, in order to verify the possible reaction mechanism, a controlled experiment was designed to prove that the reaction may be a free radical reaction. (2) the azide reaction of allyl cyclopropane substrates was realized under the condition of non-metal catalysis, and 20 different substrates were investigated. The dihydronaphthalene derivatives containing azide group were obtained in a yield of up to 88%. The reaction conditions were mild, the raw materials were cheap and easy to obtain, and the reaction time was short. The most important thing is that the reaction does not require a metal catalyst. Then the azide products were derivatized and the click-down reaction and reductive ammoniation reaction with alkynes were carried out respectively. Finally, a controlled experiment was designed to study the reaction mechanism, which indicates that the reaction may be a free radical reaction.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
，
本文编号：2181636
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