过渡金属的邻、对位羟基吡啶配合物：合成、结构及催化研究
发布时间：2018-10-21 18:17
【摘要】：在化学反应中,为了使反应更加的高效,催化剂的加入显得尤为重要,超过80%的反应都需要加入催化剂,而其中使用金属催化占一半以上。在过去,人们在均相催化反应中使用大量传统催化剂,但是传统催化剂有着许多弊端。为解决传统催化剂催化性能不佳,产物不环保等缺点,研究学者开始研究经过修饰的传统催化剂,以提高过渡金属催化剂的稳定性,提高其催化反应的效率与选择性。本文设计构建合成了多种带有邻、对位羟基吡啶配体的新型过渡金属配合物,通过核磁氢谱、核磁碳谱、X射线晶体衍射等手段对其结构进行了表征,并对其催化性能进行了系统的考察。催化性能的研究首先是利用上述配合物催化酮类化合物的氢转移反应并表现出了优异的催化效果,通过反应时间、反应温度、碱的种类、催化剂的种类以及碱和催化剂的用量等方面进行优化实现了多种催化剂催化苯乙酮到1-苯乙醇的反应,我们所合成出的催化剂转化率都在90%以上,甚至可实现99%的转化。其次,本文设计合成出的经修饰的过渡金属催化剂还可以有效催化以邻苯二胺及环氧化合物为原料合成2-苯基-1,2,3,4-四氢喹喔啉的新型反应,通过反应时间、反应温度、催化剂的种类以及酸和催化剂的用量的不断优化和摸索,我们发现过渡金属催化剂表现出良好的催化性能,比简单合成和其他催化剂的合成效果优秀多倍,在该反应体系中可以实现50%左右的产率。通过研究我们发现加入经修饰的过渡金属催化剂可以实现反应无污染、原子利用率高、反应安全温和,实现了绿色化学的目标,为催化剂领域又提供了新的思路和想法。通过本文的研究,我们可以发现经过修饰的过渡金属催化剂具有结构稳定、选择性好、底物丰富、产物洁净、反应安全、操作简单等优点。因此,我们认为经过修饰的过渡金属催化剂具有广阔的研究领域,深远的研究价值,本文的研究可以实现绿色化学的目标,实现原子经济性,在未来可以广泛应用于医药等领域。
[Abstract]:In chemical reaction, in order to make the reaction more efficient, the addition of catalyst is particularly important. More than 80% of the reactions need to add catalyst, and metal catalyst is used in more than half of the reactions. In the past, a large number of traditional catalysts were used in homogeneous catalytic reactions, but the traditional catalysts had many disadvantages. In order to solve the shortcomings of traditional catalysts such as poor catalytic performance and environmental protection, researchers have begun to study modified traditional catalysts to improve the stability of transition metal catalysts and improve the efficiency and selectivity of their catalytic reactions. In this paper, a variety of novel transition metal complexes with p-hydroxypyridine ligand were designed and synthesized, and their structures were characterized by nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and X-ray crystal diffraction. The catalytic performance of the catalyst was systematically investigated. First of all, the above mentioned complexes are used to catalyze the hydrogen transfer reaction of ketone compounds and show excellent catalytic effect by reaction time, reaction temperature, kinds of alkaloids. The kinds of catalysts and the amount of alkali and catalyst were optimized to realize the reaction of acetophenone to 1-phenylethanol. The conversion of the catalysts was above 90% or even 99%. Secondly, the modified transition metal catalyst can also effectively catalyze the synthesis of 2-phenyl-1- (2-trihydroquinoxaline) from o-phenylenediamine and epoxy compounds. The reaction temperature and reaction time are determined. The kinds of catalysts and the amount of acid and catalyst were optimized and groped. We found that the transition metal catalysts showed good catalytic performance, which was many times better than that of simple synthesis and other catalysts. The yield of about 50% can be achieved in this reaction system. It is found that the modified transition metal catalyst can achieve no pollution, high atomic utilization rate, safe and mild reaction, achieve the goal of green chemistry, and provide new ideas and ideas for the field of catalyst. Through the research in this paper, we can find that the modified transition metal catalyst has the advantages of stable structure, good selectivity, abundant substrate, clean product, safe reaction, simple operation and so on. Therefore, we think that the modified transition metal catalysts have a wide range of research fields and far-reaching research value, the research in this paper can achieve the goal of green chemistry, achieve atomic economy, In the future can be widely used in medicine and other fields.
【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;O643.36
本文编号：2285947
[Abstract]:In chemical reaction, in order to make the reaction more efficient, the addition of catalyst is particularly important. More than 80% of the reactions need to add catalyst, and metal catalyst is used in more than half of the reactions. In the past, a large number of traditional catalysts were used in homogeneous catalytic reactions, but the traditional catalysts had many disadvantages. In order to solve the shortcomings of traditional catalysts such as poor catalytic performance and environmental protection, researchers have begun to study modified traditional catalysts to improve the stability of transition metal catalysts and improve the efficiency and selectivity of their catalytic reactions. In this paper, a variety of novel transition metal complexes with p-hydroxypyridine ligand were designed and synthesized, and their structures were characterized by nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and X-ray crystal diffraction. The catalytic performance of the catalyst was systematically investigated. First of all, the above mentioned complexes are used to catalyze the hydrogen transfer reaction of ketone compounds and show excellent catalytic effect by reaction time, reaction temperature, kinds of alkaloids. The kinds of catalysts and the amount of alkali and catalyst were optimized to realize the reaction of acetophenone to 1-phenylethanol. The conversion of the catalysts was above 90% or even 99%. Secondly, the modified transition metal catalyst can also effectively catalyze the synthesis of 2-phenyl-1- (2-trihydroquinoxaline) from o-phenylenediamine and epoxy compounds. The reaction temperature and reaction time are determined. The kinds of catalysts and the amount of acid and catalyst were optimized and groped. We found that the transition metal catalysts showed good catalytic performance, which was many times better than that of simple synthesis and other catalysts. The yield of about 50% can be achieved in this reaction system. It is found that the modified transition metal catalyst can achieve no pollution, high atomic utilization rate, safe and mild reaction, achieve the goal of green chemistry, and provide new ideas and ideas for the field of catalyst. Through the research in this paper, we can find that the modified transition metal catalyst has the advantages of stable structure, good selectivity, abundant substrate, clean product, safe reaction, simple operation and so on. Therefore, we think that the modified transition metal catalysts have a wide range of research fields and far-reaching research value, the research in this paper can achieve the goal of green chemistry, achieve atomic economy, In the future can be widely used in medicine and other fields.
【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;O643.36
【参考文献】
相关硕士学位论文 前1条
1 郭培江;铜催化C-N交叉偶联合成四氢喹喔啉类化合物[D];成都理工大学;2012年
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