环己酮参与无过渡金属催化的N-芳基咔唑合成研究

发布时间：2018-03-19 22:17

本文选题：无过渡金属　切入点：环己酮　出处：《湘潭大学》2017年硕士论文　论文类型：学位论文

【摘要】：咔唑类化合物是一类重要的有机含氮杂环化合物,普遍存在于自然界中,在医药、染料和有机光电材料等领域中有着广泛地应用,在人类日常生活中具有重要的意义。发展高效绿色的咔唑合成方法成是有机合成的研究热点之一。廉价易得非芳香性的环己酮类化合物经“脱氢”芳构化可以作为潜在的芳基来源,并且已经被成功应用于有机合成中。在光电功能材料和药物合成中重金属污染与残留是必须考虑的问题之一,在无过渡金属参与条件下采用廉价易得的环己酮作为芳基来源构建咔唑骨架可以提供一条环境友好的新途径。本论文以环己酮为原料在无过渡金属催化下合成一系列非对称的N-芳基咔唑类化合物。主要研究内容如下:1、发展了一类以苯基脲类化合物与环己酮类化合物为原料在无过渡金属催化下合成非对称的N-芳基咔唑的方法。该方法无需使用过渡金属催化剂,官能团兼容性较好,咔唑骨架除氮原子外所有原子来源于非芳香性的环己酮。碘化钾与单质碘共同作为促进剂有效促进该反应的转化,具有中等至优良的产率。该反应为合成非对称的N-芳基咔唑提供了一条高效绿色的合成途径。2、发展了一类以苯胺类化合物与环己酮化合物或者与苯乙酮化合物合成咔唑类以及吡咯类化合物的方法。该方法在合成咔唑类化合物时,采用“一锅两步”,使用KI/I2作为促进剂,以廉价易得的芳香胺作为氮芳基的来源,合成一系列中等至良好产率的2,6-二取代-9-芳基咔唑。同时,KI单独存在时,以苯胺和苯乙酮为原料合成一系列1,2,4-三芳基吡咯。该方法以廉价易得的芳香胺与环己酮或苯乙酮为原料,为合成非对称的N-芳基咔唑或吡咯提供了一条新途径。
[Abstract]:Carbazole compounds are a kind of important organic heterocyclic compounds, which are widely used in the fields of medicine, dyes and organic optoelectronic materials. The development of efficient green carbazole synthesis method is one of the research hotspots in organic synthesis. Cyclohexanone compounds with low cost and easy to get non-aromatic can be used as aromatization by "dehydrogenation" of cyclohexanone. For potential aryl sources, And has been successfully used in organic synthesis. In photovoltaic functional materials and drug synthesis, heavy metal contamination and residue is one of the problems that must be considered. Using cheap and easily available cyclohexanone as aryl source to construct carbazole skeleton without transition metal participation can provide a new environmentally friendly approach. In this thesis, cyclohexanone was synthesized from cyclohexanone under the catalysis of transition metal. A series of asymmetric N-aryl carbazole compounds. The main contents of this study are as follows: 1. The synthesis of asymmetric N-aryl carbazole from phenylurea compounds and cyclohexanone compounds without transition metal catalysis was developed. Method. The method does not require the use of transition metal catalysts, The carbazole skeleton all the atoms except nitrogen come from non-aromatic cyclohexanone. Potassium iodide and simple iodine act as accelerators to promote the conversion of the reaction. The reaction provides an efficient green synthesis pathway for the synthesis of asymmetric N-aryl carbazole, and develops a class of aniline compounds with cyclohexanone or acetophenone compounds. A method for forming carbazole and pyrrole compounds. In the synthesis of carbazole compounds, Using "one pot and two steps", using KI/I2 as accelerator, using cheap and easily available aromatic amine as the source of nitrogen aryl, a series of 2C6-disubstituted -9-aryl carbazoles with medium to good yield were synthesized. Using aniline and acetophenone as raw materials, a series of 1'2'2'4- triarylpyrrole were synthesized. This method provides a new way for the synthesis of asymmetric N-aryl carbazole or pyrrole by using cheap and easily available aromatic amine and cyclohexanone or acetophenone as raw materials.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

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