XJIPC OpenIR  > 资源化学研究室
Thesis Advisor卢崇道
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Name硕士
Degree Discipline有机化学
Keyword己内酰胺铑 叔丁基过氧化氢 甲醇 氧化 1 3-二羰基化合物 双1 3-二羰基化合物

铑是目前在世界上用作催化剂的三大贵金属(Pt、Pd、Rh)之一。常见的铑配合物有:一价铑、二价铑、三价铑配合物。己内酰胺铑[Rh2(cap)4]是一种典型的二价酰胺铑(II)配合物。Rh2(cap)4/TBHP 体系主要用于催化氧化,如:苄位氧化、烯丙位氧化、炔丙位氧化、酚的氧化、伯胺的氧化、仲胺的氧化、胺氧化-Mannich 加成等反应。由于己内酰胺铑催化重氮化合物分解可以生成环丙烷,而环丙烷结构在天然产物中广泛存在,所以己内酰胺铑在全合成中亦有重要应用。对此酰胺铑催化剂的反应性研究,对于其今后的应用性扩展具有重要的借鉴意义。本论文研究了Rh2(cap)4/TBHP 体系对醇的氧化反应。设计了以己内酰胺铑催化氧化甲醇,而后用1,3-二羰基化合物捕捉生成的甲醛的反应。通过对反应涉及的溶剂、催化剂用量、温度、氧化剂用量等的条件筛选,得到反应的最优条件:1 mmol 的1,3-二羰基化合物,1 mol% Rh2(cap)4,3 mmol TBHP,1.2 mmol 的DIPEA,于室温反应直至原料1,3-二羰基化合物消耗完。反应首先原位氧化作为溶剂的甲醇,生成甲醛,而后被体系中的1,3-二羰基化合物捕捉,高效的生成了双-1,3-二羰基化合物。该反应具有反应条件温和,操作简便,产率高等优点。此研究内容丰富了己内酰胺铑催化剂的应用范围,对于己内酰胺铑催化剂的进一步研究具有一定的借鉴意义。

Other Abstract

The rhodium is one of noble metals (Pt, Pd, Rh) widely used as catalyst in the world. Common rhodium complexes are: a monovalent rhodium, divalent rhodium complex, trivalent rhodium complex. Dirhodium(II) caprolactamate[Rh2(cap)4] is a typical divalent amide rhodium (II) complex. Rh2(cap)4/TBHP system is mainly used for catalytic oxidation, such as: oxidation of the benzylic, allylic oxidation, propargylic oxidation,oxidation of the phenol, oxidation of the primary amine, secondary amine oxidation, the amine oxidation-Mannich reactions. Since dirhodium(II) caprolactamate can catalyzed decomposition of diazo compounds and produced cyclopropane, cyclopropane structure is very importent in natural products, so there are huge applications in total synthesis. Research of this amide rhodium catalyst’s application have important values. This paper studies the alcohol oxidation reaction used the Rh2(cap)4/TBHP system. Designed the dirhodium(II) caprolactamate catalytic oxidation of methanol, then use 1,3 - dicarbonyl compounds to capture the produced formaldehyde. Through optimizing the reaction conditions such as: solvent, catalyst level, temperature, dosage of oxidant, get the optimal reaction conditions are: 1 mmol of 1,3 - dicarbonyl compounds, 1 mol % Rh2(cap)4, 3 mmol TBHP, 1.2 mmol of DIPEA, reaction at room temperature until the raw material 1,3 - dicarbonyl compounds is depleted. First, in situ oxidative the methanol to produce formaldehyde, and then 1,3 - dicarbonyl compounds captured the formaldehyde to produce bis-1,3-dicarbonyl compound. This reaction has a mild reaction conditions, simple operation, high yield. This research enriches the application scope of dirhodium(II) caprolactamate, and provide reference for future research.

Document Type学位论文
Recommended Citation
GB/T 7714
赵建平. 己内酰胺铑催化合成双-1,3-二羰基化合物反应研究[D]. 北京. 中国科学院大学,2014.
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