本文選題：鈀 + 多相催化劑　； 參考：《催化學(xué)報》2017年03期

【摘要】：在最近的幾十年里,金屬鈀催化的Suzuki-Miyaura偶聯(lián)反應(yīng)已經(jīng)得到了越來越多的關(guān)注,被廣泛應(yīng)用于藥物、天然產(chǎn)物以及新材料的合成.與此同時均相催化劑發(fā)展迅速,高效的配體和大量的設(shè)計被用于Suzuki-Miyaura偶聯(lián)反應(yīng)中,但是鈀催化劑的配體通常很昂貴和難以合成,因此鈀催化劑系統(tǒng)的回收是非常有價值的,不僅是經(jīng)濟(jì)上的原因,同時也避免了產(chǎn)品的污染,所以發(fā)展非均相催化劑是必要的.近年來,研究學(xué)者們致力于設(shè)計非均相的鈀催化劑,如將鈀納米顆粒負(fù)載到金屬有機骨架、介孔分子篩以及活性炭等多種材料上得到的非均相鈀催化劑并應(yīng)用于Suzuki-Miyaura偶聯(lián)反應(yīng)中.我們主要介紹了鈀納米顆粒被負(fù)載在含磷配體的交聯(lián)的聚苯胺材料上制得負(fù)載的鈀催化劑,首先通過鈀催化的三(4-碘苯基)胺與金剛烷基膦的C P偶聯(lián),再由鈀催化三(4-碘苯基)胺與對苯二胺的C N偶聯(lián),進(jìn)而得到鈀納米顆粒負(fù)載在含金剛烷基膦的聚苯胺材料上的催化劑Pd@PAN-Ad-0.5(鈀含量為0.58 wt%),同時我們對催化劑進(jìn)行了一些表征,如TEM,SEM,XRD,EDX,XPS,FT-IR,ICP等.通過TEM分析,我們發(fā)現(xiàn)鈀納米顆粒在聚合物表面分布均勻,并且金屬鈀的平均粒徑為2 3 nm;EDX檢測顯示催化劑含有C,N,P,Pd,I元素,說明鈀負(fù)載到含金剛烷基膦的聚苯胺材料上的催化劑Pd@PAN-Ad-0.5已經(jīng)形成,并被用于Suzuki-Miyaura偶聯(lián)反應(yīng).我們對反應(yīng)體系中的各種影響因素進(jìn)行了優(yōu)化,包括溶劑、堿、反應(yīng)時間、催化劑加入量以及不同的催化劑的優(yōu)化,最終確定了最佳反應(yīng)條件;對于帶有不同取代基(如腈基、甲氧基、醛基、酮基以及硝基)的氯代芳烴和溴代芳烴與苯硼酸的Suzuki-Miyaura反應(yīng),以較少的催化劑使用量(0.075 mol%Pd)就能獲得較高的相應(yīng)的聯(lián)苯產(chǎn)物收率.此外,催化劑Pd@PAN-Ad-0.5在偶聯(lián)反應(yīng)中具有較高的反應(yīng)活性的同時,還具有較好的回收使用能力(至少能夠回收使用5次),循環(huán)使用4次以后還具有較高的催化活性.為了探索催化劑Pd@PAN-Ad-0.5在工業(yè)上的應(yīng)用,由于4'-氯-2-硝基-1,1'-聯(lián)苯是合成啶酰菌胺藥物的重要中間體,因此我們使用催化劑Pd@PAN-Ad-0.5催化2-硝基氯苯與4-氯苯硼酸的偶聯(lián)反應(yīng),目標(biāo)產(chǎn)物4'-氯-2-硝基-1,1'-聯(lián)苯的收率高達(dá)96%.我們相信這類催化劑應(yīng)用于實驗室或工業(yè)上合成聯(lián)苯化學(xué)品具有較大的潛力.
[Abstract]:In recent decades, palladium catalyzed Suzuki-Miyaura coupling reactions have attracted more and more attention and have been widely used in the synthesis of drugs, natural products and new materials. At the same time, homogeneous catalysts have been developed rapidly, efficient ligands and a large number of designs have been used in Suzuki-Miyaura coupling reactions, but the ligands of palladium catalysts are usually expensive and difficult to synthesize, so the recovery of palladium catalyst systems is very valuable. Not only economic reasons, but also avoid product pollution, so the development of heterogeneous catalyst is necessary. In recent years, researchers have been working to design heterogeneous palladium catalysts, such as heterogeneous palladium catalysts supported on organometallic frameworks, mesoporous molecular sieves and activated carbon, and used in Suzuki-Miyaura coupling reactions. In this paper, we mainly introduce the preparation of supported palladium catalyst by supported on phosphorous ligand cross-linked Polyaniline material. Firstly, the tri-( 4-iodophenyl) amine catalyzed by palladium is coupled with C ~ (+) P of amantadine phosphine. After coupling of tris (4-iodophenyl) amine with p-phenylenediamine by palladium, the catalyst PdPAN-Ad-0.5 supported by palladium nanoparticles on Polyaniline material containing amantadine phosphine was obtained, and the catalyst was characterized. For example, TEM-SEMU XRDX EDX XPSFT-IRT ICP, etc. By TEM analysis, we found that the palladium nanoparticles distributed uniformly on the polymer surface, and the average particle size of palladium was 2 ~ 3 nm edX. The results show that the catalyst Pd@ PAN-Ad-0.5 supported by palladium on Polyaniline material containing amantadine phosphine has been formed and used in Suzuki-Miyaura coupling reaction. We optimized various factors affecting the reaction system, including solvent, alkali, reaction time, amount of catalyst and different catalyst. Finally, we determined the optimal reaction conditions with different substituents (such as nitrile group, for example, nitrile group, etc.). The chlorinated aromatics and bromoarenes of methoxy, aldehyde, ketone and nitro groups reacted with phenylboric acid Suzuki-Miyaura, and a higher yield of biphenyl products could be obtained with less amount of catalyst (0.075 mol PD). In addition, the catalyst Pd@ PAN-Ad-0.5 has high catalytic activity in the coupling reaction, at the same time, it also has good recovery ability (at least 5 times), and also has higher catalytic activity after 4 cycles of recycling. In order to explore the industrial application of the catalyst Pd@ PAN-Ad-0.5, we used the catalyst Pd@ PAN-Ad-0.5 to catalyze the coupling reaction of 2-nitrochlorobenzene with 4-chlorobenzene boric acid. The yield of the target product was 96%. We believe that these catalysts have great potential to be used in synthetic biphenyl chemicals in laboratory or industry.
【作者單位】： 南京工業(yè)大學(xué)化工學(xué)院;
【基金】：supported by the National Natural Science of Foundation of China(21676140) the fund from the State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201402) the Project of Priority Academic Program Development(PAPD) of Jiangsu Higher Education Institutions~~
【分類號】：O643.36

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