金属化合物与胺共催化的炔—羰复分解反应合成芳香酮衍生物

发布时间：2018-06-13 21:17

本文选题：金属化合物催化剂 + 芳香酮　；参考：《兰州交通大学》2017年硕士论文

【摘要】：本论文主要包括以下两个部分内容:第一部分:金属化合物催化剂在复分解反应中的应用进展金属在生产生活中都扮演着极其重要的角色。金属化合物催化剂为化学反应做出了巨大的贡献。在烯烃复分解反应中,从一开始钼、钨类的金属卡宾应用到该领域,到现今流行使用的钌金属卡宾,即二代的Grubbs催化剂,在工业生产与实验室的研究中都发挥了巨大的作用。在2016年,三氯化铁(III)被运用到烯-羰复分解反应中,实现了金属化合物催化剂在该领域应用的重大突破。就铁而言,自然资源丰富而且环境友好,并且铁(III)化合物是一类优秀的催化剂。金属化合物催化剂也被运用在炔-羰复分解合成芳香酮的反应中。芳香酮在医药化学和材料科学方面有着重要的应用。因此,发展新的方法构建芳香酮是十分有意义的。第二部分:金属化合物与胺催化炔-羰复分解反应合成芳香酮的研究这一部分主要是实验内容。首先,以2,3-二甲氧基苯甲醛与三甲基乙烯为模板底物尝试分子间的烯-羰复分解反应。该反应的最优条件:三氯化铁(20 mol%)、温度为40°C、溶剂为二氯甲烷,但是该反应的普适性很差。接下来对反应进行了调整,以(E)-2-甲基-3-(2-(苯乙炔基)苯基)丙烯醛为模板底物尝试分子内的炔-羰复分解反应。该反应的最优条件:对甲苯磺酰胺(5 mol%)、三氟甲磺酸铁(10 mol%)、温度为120°C、溶剂为1,2-二氯乙烷,在此最优条件下预期产物的产率可达95%。在此最优条件下合成了一系列产率良好至优异的化合物。通过核磁共振与高分辨质谱对产物进行结构鉴定。
[Abstract]:This thesis mainly includes the following two parts: the first part: the application of metal compound catalyst in the double decomposition reaction. Metal plays an extremely important role in production and life. Metal compound catalysts have made a great contribution to the chemical reaction. From the initial application of molybdenum and tungsten metal carbene to the present popular ruthenium metal carbene, the second generation Grubbs catalyst has played an important role in industrial production and laboratory research. In 2016, ferric trichloride (III) was applied to the alkene-carbonylation reaction, which made a great breakthrough in the application of metal compound catalysts in this field. In the case of iron, natural resources are abundant and environmentally friendly, and iron II I) compounds are excellent catalysts. Metal compound catalysts are also used in the synthesis of aromatic ketones from acetylene to carbonyl. Aromatic ketones have important applications in medical chemistry and material science. Therefore, it is of great significance to develop a new method for the construction of aromatic ketones. Part two: the synthesis of aromatic ketones from metal compounds and amines catalyzed by acetylene-carbonyl decomposition. First of all, dimethoxybenzaldehyde and trimethyl ethylene were used as template substrates to study the reaction of alkene-carbonylation. The optimum conditions for the reaction are as follows: ferric chloride 20 mol / L, temperature 40 掳C, solvent dichloromethane, but the universality of the reaction is very poor. Then the reaction was adjusted to try the intramolecular acetylene-carbonylation reaction with Elae-2-methyl-3-(phenylethynyl)-phenyl) acrolein as the template substrate. The optimum reaction conditions are as follows: p-toluenesulfonamide 5 mol / L, iron trifluoromethyl sulfonate 10 mol / L, temperature 120 掳C, solvent 1 / 2-dichloroethane. Under the optimum conditions, the yield of the expected product can reach 95%. Under the optimum conditions, a series of compounds with excellent yields were synthesized. The products were characterized by NMR and high resolution mass spectrometry.
【学位授予单位】：兰州交通大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O625.42

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