可见光催化剂和过渡金属协同催化的有机反应

发布时间：2019-01-30 11:52

【摘要】：由于C H键活化具有反应条件简单,底物广谱性优良,反应选择性好等优点,使其成为有机合成研究领域中最实用且不可替代的合成手段。C H键活化反应也因此成为有机化学研究的热点之一。随着绿色化学概念的提出,化学家们构想如何促使C H键活化向环境友好、绿色环保的方向发展。近年来,可见光促进的有机合成反应发展迅速使得它成为有机化学研究领域中的热点之一。基于以上两点的认识,本论文主要以可见光催化剂和过渡金属协同催化的有机反应为重点。具体研究工作包括以下两方面:(1)以乙酰苯胺和苯甲酰甲酸为原料,利用可见光诱导,过渡金属Pd和光催化剂eosin Y协同催化的方式来实现对乙酰苯胺C2位的酰基化反应。本实验在室温条件下,绿光LED灯为可见光的来源,将有机染料光催化eosin Y与过渡金属钯催化剂相结合,在温和条件下实现了乙酰苯胺与α-酮酸类化合物的脱羧偶联反应。值得一提的是,在此反应体系中以染料eosin Y为光催化剂更加环境友好而且无需添加倍量氧化剂即可完成可见光催化剂和过渡金属催化剂的双循环。通过控制实验以及电子顺磁共振(ESR)等方法对该反应机理进行了系统研究。该实验条件温和,底物广谱性良好,产率良好。(2)以N-甲氧基苯甲酰胺为底物,过渡金属Pd与光催化剂Ru(phen)3(PF6)2共同催化的方法实现了脲类化合物的合成。经过验证,反应机理可能经历异氰酸酯,重排的过程,研究正在进行中。该反应以蓝光LED灯为光源反应20小时即可完成,条件较为温和,产率良好。
[Abstract]:The activation of C-H bond has the advantages of simple reaction conditions, good broad-spectrum of substrate and good selectivity. It has become the most practical and irreplaceable synthetic method in the field of organic synthesis. Therefore, the activation of C-H bond has become one of the hotspots in organic chemistry. With the introduction of the concept of green chemistry, chemists have proposed how to promote the activation of C-H bond to the direction of environmental friendly and green. In recent years, the development of organic synthesis reaction promoted by visible light makes it one of the hotspots in the field of organic chemistry. Based on the above two understandings, this thesis focuses on the organic reaction of visible light catalyst and transition metal co-catalysis. The specific research work includes the following two aspects: (1) Acetanilide C2 site acylation reaction was realized by using visible light induction, transition metal Pd and photocatalyst eosin Y co-catalysis with acetanilide and benzoyl formic acid as raw materials. In this experiment, the organic dye photocatalytic eosin Y was combined with transition metal palladium catalyst to realize the decarboxylation of acetanilide with 伪 -ketoacid at room temperature and green LED lamp as the source of visible light. It is worth mentioning that the dye eosin Y as photocatalyst is more environmentally friendly in this reaction system and the double cycle of visible light catalyst and transition metal catalyst can be completed without adding double amount of oxidant. The mechanism of the reaction was systematically studied by means of control experiment and electron paramagnetic resonance (ESR). The experimental conditions are mild, the substrate has good broad-spectrum property and the yield is good. (2) the transition metal Pd and photocatalyst Ru (phen) _ 3 (PF6) _ 2 co-catalyze the synthesis of ureates using N-methoxybenzoamide as substrate. It has been proved that the reaction mechanism may undergo the process of isocyanate, rearrangement, and the research is in progress. The reaction can be completed by using blue LED lamp as light source for 20 hours. The reaction conditions are mild and the yield is good.
【学位授予单位】：淮北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251;O644.1

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