三唑金络合物的设计合成与应用研究

发布时间：2018-09-01 07:38

【摘要】：金催化剂因其特有的催化特性而备受关注,被认为是有机合成中最有前途的研究领域之一。然而金催化剂普遍存在着不稳定、易分解的缺陷;另外,伴随金催化剂所生成的絮状沉淀AgX能加速活性金催化剂的分解。三唑配体由于具有较强的δ-donor和较低的LUMO反键轨道,容易形成较为牢靠的金属反馈π键,因此具备较强的配位能力,与金配位后在很大程度上能提高金催化剂的稳定性。因此,本课题设计合成了以三唑为配体的金络合物并对其性能进行研究。(1)首先,本文合成了新型含氮羧酸配体,通过与无机金盐反应制备出三唑骨架金络合物。实验表明,本文合成的三唑羧酸金络合物经过仪器表征为所设计的络合物,热稳定性测试表明这类络合物的热稳定性得到了很大的提高。催化性能测试表明此络合物具有良好的性能,对于炔丙醇的水解起到了优秀的催化作用。(2)其次,本文在三唑羧酸配体的基础上,通过引入天然丙氨酸分子,设计合成了三唑丙氨酸配体,随后,利用该配体与金催化剂进行配位络合,得到了以三唑丙氨酸为骨架的金络合物。热重实验证明,该络合物具有非常不错的热稳定性。最后,将此络合物应用到联烯的合成中,实验发现,原位生成的催化剂具有和预先制备的催化剂一样的催化活性。因此,我们采用原位生成催化剂的方法进行底物拓展实验,发现该络合物具有非常好的底物适应性。与此同时,本文还发现该催化体系对于不同取代基的炔烃水解同样具有较好的活性。(3)与三唑相比,吡啶的配位能力也不错,为了获得更为稳定的金络合物,同时也为了比较检验吡啶和三唑对金的稳定作用,本文设计合成了吡啶三唑金(I)络合物并利用核磁和单晶衍射表征确定了其结构,同时研究发现三唑更容易与金配位。热稳定实验表明该络合物在空气和甲苯溶剂中均具有很高的稳定性;另外,炔丙酯/炔丙醚的重排反应表明该络合物具有很好的催化活性。(4)之后,结合金(Ⅲ)的四配位方式,本文利用此配体又成功制备出吡啶三唑金(Ⅲ)络合物,该络合物的结构也经过了表征并确定。通过对其热稳定性和催化活性进行测试发现,该络合物不仅热稳定性好,还能够以中等到优秀的产率实现烯基碘衍生物的合成,同时,本文还首次通过金催化实现烯基氯代物的合成。(5)最后,本文利用三唑酯配体以很高的产率制备出三唑酯金络合物。同样,该三唑酯金络合物通过相关仪器表征证实为所设计的结构,随后通过TG实验对其热稳定性进行检测。随后,将此络合物应用到伯胺的N-烷基化。实验结果表明,三唑酯金络合物对借氢反应同样有较好的催化活性。
[Abstract]:Gold catalyst is one of the most promising research fields in organic synthesis due to its unique catalytic properties. However, the gold catalyst is unstable and easy to decompose. In addition, the flocculation precipitate AgX produced with the gold catalyst can accelerate the decomposition of the active gold catalyst. Because of its strong 未 -donor and low LUMO antibond orbital, triazole ligands are easy to form solid metal feedback 蟺 bond, so they have strong coordination ability and can improve the stability of gold catalyst to a great extent after coordination with gold. Therefore, the gold complex with triazole as ligand was designed and synthesized and its properties were studied. (1) first, a novel nitrogen-containing carboxylic acid ligand was synthesized, and triazole skeleton gold complex was prepared by reaction with inorganic gold salt. The experimental results show that the gold complex of triazole carboxylic acid synthesized in this paper is characterized by the instrument as the designed complex, and the thermal stability test shows that the thermal stability of the complex has been greatly improved. The catalytic performance test shows that the complex has good performance and plays an excellent catalytic role in the hydrolysis of propargyl alcohol. (2) secondly, on the basis of triazole carboxylic acid ligands, natural alanine molecules are introduced. Triazole alanine ligand was designed and synthesized, and then the gold complex with triazolanine as skeleton was obtained by using this ligand to coordinate with gold catalyst. Thermogravimetric experiments show that the complex has very good thermal stability. Finally, the complex was applied to the synthesis of diene. It was found that the in-situ catalyst had the same catalytic activity as the pre-prepared catalyst. Therefore, the substrate expansion experiments were carried out by in-situ catalyst formation, and it was found that the complex had very good substrate adaptability. At the same time, it is also found that the catalytic system has good activity for the hydrolysis of alkynes with different substituents. (3) compared with triazole, the coordination ability of pyridine is also good, in order to obtain a more stable gold complex, In order to compare and test the stability of pyridine and triazole on gold, the (I) complex of pyridine-triazole gold was designed and synthesized, and its structure was determined by NMR and single crystal diffraction. It was also found that triazole is more easily coordinated with gold. The thermal stability experiment shows that the complex has high stability in both air and toluene solvent, in addition, the rearrangement reaction of propargyl ester / propargyl ether shows that the complex has good catalytic activity. (4) after 4), the complex is combined with the four coordination mode of gold (鈪，

本文编号：2216543