利用新型手性铑催化剂催化芳烃上碳氢键活化研究

发布时间：2018-04-10 05:42

  本文选题：Rh催化剂　切入点：氨基酸　出处：《齐齐哈尔大学》2017年硕士论文

【摘要】：现如今,过渡金属在催化碳氢键活化的反应中被用来作为催化剂的研究越来越广泛,在合成天然产物方面已经取得了快速的发展,并且为功能分子合成的方法提供了高效直接的新途径。尤其突出的是新型的三价铑催化剂,在C-H键活化构造C-C键、C-O键和C-N键的方面有很大的应用。此类催化剂不但有很高的催化活性同时在立体选择性方面也有很大的优势,所以,利用新型的铑催化剂进行催化芳烃的研究受到科研人员的高度关注。本课题选取水杨醛和苯乙炔为实验材料,利用含有不同氨基酸配体的铑催化剂催化氧化偶联反应,合成了2-苯基-1,4-苯并哌喃酮。对不同氨基酸配体的新型铑催化剂进行合成与表征。并以Rh(cod)(L-Phe),Rh(cod)(L-Pro),Rh(cod)(L-Val),[Rh(cod)Cl]2,Rh(cod)(L-Ala)五种含有不同配体的Rh催化剂催化水杨醛与苯乙炔进行氧化偶联反应。对比五种催化剂催化活性的高低,证明Rh(cod)(L-Phe)的催化活性最好。同时提出了铑催化剂的催化机理,由于Rh(cod)(L-Phe)中苯取代基团的存在,其Rh-N键易于断裂与水杨醛形成中间体而促进反应的进行,令其催化效果达到最佳。利用红外光谱(FT-IR)分析、核磁碳谱(13C-NMR)分析、核磁氢谱(1H-NMR)分析、元素分析以及气相色谱分析(GC)对2-苯基-1,4-苯并哌喃酮进行表征,并确定其化学结构,测试结果显示在铑催化剂的作用下首次合成了2-苯基-1,4-苯并哌喃酮。对目标产物2-苯基-1,4-苯并哌喃酮的合成产率的影响因素进行考察,优化其工艺条件。对比等温度、等时间的情况下2-苯基-1,4-苯并哌喃酮的收率,同时讨论其催化活性,得到最优催化方案为Rh(cod)(L-Phe)为催化剂在120℃的条件下油浴中反应5.5小时。
[Abstract]:Nowadays, transition metals have been widely used as catalysts in the catalytic reactions of hydrocarbon bond activation, and have made rapid progress in the synthesis of natural products.It also provides a new and efficient way for the synthesis of functional molecules.In particular, a new type of trivalent rhodium catalyst is widely used in C-H bond activation to form C-C bond, C-O bond and C-N bond.This kind of catalyst not only has high catalytic activity but also has a great advantage in stereoselectivity. Therefore the research of using new rhodium catalyst to catalyze aromatics is highly concerned by researchers.In this paper, salicylic aldehyde and phenylacetylene were used as experimental materials to synthesize 2-phenyl-4-benzoperazone by using rhodium catalyst with different amino acid ligands as catalyst for oxidative coupling reaction.New rhodium catalysts with different amino acid ligands were synthesized and characterized.Five Rh catalysts containing different ligands were used to catalyze the oxidative coupling of salicylic aldehydes with phenylacetylene.By comparing the catalytic activity of the five catalysts, it is proved that Rhcodanl-Phe) has the best catalytic activity.At the same time, the catalytic mechanism of rhodium catalyst was put forward. Because of the existence of benzene substituent group in Rhcodine L-Phe), the Rh-N bond of rhodium catalyst was easy to break down with salicylic aldehyde to form intermediate, which promoted the reaction, and the catalytic effect was the best.The chemical structures of 2-phenyl-1H-NMRs were characterized by FT-IR, 13C-NMRs, 1H-NMRs, elemental analysis and gas chromatographic analysis.The results showed that 2-phenyl-1-4-Benzooperazone was synthesized for the first time under the action of rhodium catalyst.The factors influencing the synthetic yield of the target product 2-phenyl-1 and 4-Benzooperazone were investigated and the technological conditions were optimized.Compared with the same temperature and time, the yield and catalytic activity of 2-phenyl -1n 4-Benzooperazone were discussed. The optimum catalyst was Rhcodcodonium L-Phe) for 5.5 hours in oil bath at 120 鈩，

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