【摘要】：金催化劑因其特有的催化特性而備受關(guān)注,被認(rèn)為是有機(jī)合成中最有前途的研究領(lǐng)域之一。然而金催化劑普遍存在著不穩(wěn)定、易分解的缺陷;另外,伴隨金催化劑所生成的絮狀沉淀AgX能加速活性金催化劑的分解。三唑配體由于具有較強(qiáng)的δ-donor和較低的LUMO反鍵軌道,容易形成較為牢靠的金屬反饋π鍵,因此具備較強(qiáng)的配位能力,與金配位后在很大程度上能提高金催化劑的穩(wěn)定性。因此,本課題設(shè)計(jì)合成了以三唑?yàn)榕潴w的金絡(luò)合物并對(duì)其性能進(jìn)行研究。(1)首先,本文合成了新型含氮羧酸配體,通過(guò)與無(wú)機(jī)金鹽反應(yīng)制備出三唑骨架金絡(luò)合物。實(shí)驗(yàn)表明,本文合成的三唑羧酸金絡(luò)合物經(jīng)過(guò)儀器表征為所設(shè)計(jì)的絡(luò)合物,熱穩(wěn)定性測(cè)試表明這類絡(luò)合物的熱穩(wěn)定性得到了很大的提高。催化性能測(cè)試表明此絡(luò)合物具有良好的性能,對(duì)于炔丙醇的水解起到了優(yōu)秀的催化作用。(2)其次,本文在三唑羧酸配體的基礎(chǔ)上,通過(guò)引入天然丙氨酸分子,設(shè)計(jì)合成了三唑丙氨酸配體,隨后,利用該配體與金催化劑進(jìn)行配位絡(luò)合,得到了以三唑丙氨酸為骨架的金絡(luò)合物。熱重實(shí)驗(yàn)證明,該絡(luò)合物具有非常不錯(cuò)的熱穩(wěn)定性。最后,將此絡(luò)合物應(yīng)用到聯(lián)烯的合成中,實(shí)驗(yàn)發(fā)現(xiàn),原位生成的催化劑具有和預(yù)先制備的催化劑一樣的催化活性。因此,我們采用原位生成催化劑的方法進(jìn)行底物拓展實(shí)驗(yàn),發(fā)現(xiàn)該絡(luò)合物具有非常好的底物適應(yīng)性。與此同時(shí),本文還發(fā)現(xiàn)該催化體系對(duì)于不同取代基的炔烴水解同樣具有較好的活性。(3)與三唑相比,吡啶的配位能力也不錯(cuò),為了獲得更為穩(wěn)定的金絡(luò)合物,同時(shí)也為了比較檢驗(yàn)吡啶和三唑?qū)鸬姆�(wěn)定作用,本文設(shè)計(jì)合成了吡啶三唑金(I)絡(luò)合物并利用核磁和單晶衍射表征確定了其結(jié)構(gòu),同時(shí)研究發(fā)現(xiàn)三唑更容易與金配位。熱穩(wěn)定實(shí)驗(yàn)表明該絡(luò)合物在空氣和甲苯溶劑中均具有很高的穩(wěn)定性;另外,炔丙酯/炔丙醚的重排反應(yīng)表明該絡(luò)合物具有很好的催化活性。(4)之后,結(jié)合金(Ⅲ)的四配位方式,本文利用此配體又成功制備出吡啶三唑金(Ⅲ)絡(luò)合物,該絡(luò)合物的結(jié)構(gòu)也經(jīng)過(guò)了表征并確定。通過(guò)對(duì)其熱穩(wěn)定性和催化活性進(jìn)行測(cè)試發(fā)現(xiàn),該絡(luò)合物不僅熱穩(wěn)定性好,還能夠以中等到優(yōu)秀的產(chǎn)率實(shí)現(xiàn)烯基碘衍生物的合成,同時(shí),本文還首次通過(guò)金催化實(shí)現(xiàn)烯基氯代物的合成。(5)最后,本文利用三唑酯配體以很高的產(chǎn)率制備出三唑酯金絡(luò)合物。同樣,該三唑酯金絡(luò)合物通過(guò)相關(guān)儀器表征證實(shí)為所設(shè)計(jì)的結(jié)構(gòu),隨后通過(guò)TG實(shí)驗(yàn)對(duì)其熱穩(wěn)定性進(jìn)行檢測(cè)。隨后,將此絡(luò)合物應(yīng)用到伯胺的N-烷基化。實(shí)驗(yàn)結(jié)果表明,三唑酯金絡(luò)合物對(duì)借氫反應(yīng)同樣有較好的催化活性。
[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，

本文編號(hào)：2216543