钯纳米颗粒负载在聚苯胺材料上制得催化Suzuki-Miyaura偶联反应的高效催化剂（英文）

发布时间：2018-07-06 12:08

本文选题：钯 + 多相催化剂　；参考：《催化学报》2017年03期

【摘要】：在最近的几十年里,金属钯催化的Suzuki-Miyaura偶联反应已经得到了越来越多的关注,被广泛应用于药物、天然产物以及新材料的合成.与此同时均相催化剂发展迅速,高效的配体和大量的设计被用于Suzuki-Miyaura偶联反应中,但是钯催化剂的配体通常很昂贵和难以合成,因此钯催化剂系统的回收是非常有价值的,不仅是经济上的原因,同时也避免了产品的污染,所以发展非均相催化剂是必要的.近年来,研究学者们致力于设计非均相的钯催化剂,如将钯纳米颗粒负载到金属有机骨架、介孔分子筛以及活性炭等多种材料上得到的非均相钯催化剂并应用于Suzuki-Miyaura偶联反应中.我们主要介绍了钯纳米颗粒被负载在含磷配体的交联的聚苯胺材料上制得负载的钯催化剂,首先通过钯催化的三(4-碘苯基)胺与金刚烷基膦的C P偶联,再由钯催化三(4-碘苯基)胺与对苯二胺的C N偶联,进而得到钯纳米颗粒负载在含金刚烷基膦的聚苯胺材料上的催化剂Pd@PAN-Ad-0.5(钯含量为0.58 wt%),同时我们对催化剂进行了一些表征,如TEM,SEM,XRD,EDX,XPS,FT-IR,ICP等.通过TEM分析,我们发现钯纳米颗粒在聚合物表面分布均匀,并且金属钯的平均粒径为2 3 nm;EDX检测显示催化剂含有C,N,P,Pd,I元素,说明钯负载到含金刚烷基膦的聚苯胺材料上的催化剂Pd@PAN-Ad-0.5已经形成,并被用于Suzuki-Miyaura偶联反应.我们对反应体系中的各种影响因素进行了优化,包括溶剂、碱、反应时间、催化剂加入量以及不同的催化剂的优化,最终确定了最佳反应条件;对于带有不同取代基(如腈基、甲氧基、醛基、酮基以及硝基)的氯代芳烃和溴代芳烃与苯硼酸的Suzuki-Miyaura反应,以较少的催化剂使用量(0.075 mol%Pd)就能获得较高的相应的联苯产物收率.此外,催化剂Pd@PAN-Ad-0.5在偶联反应中具有较高的反应活性的同时,还具有较好的回收使用能力(至少能够回收使用5次),循环使用4次以后还具有较高的催化活性.为了探索催化剂Pd@PAN-Ad-0.5在工业上的应用,由于4'-氯-2-硝基-1,1'-联苯是合成啶酰菌胺药物的重要中间体,因此我们使用催化剂Pd@PAN-Ad-0.5催化2-硝基氯苯与4-氯苯硼酸的偶联反应,目标产物4'-氯-2-硝基-1,1'-联苯的收率高达96%.我们相信这类催化剂应用于实验室或工业上合成联苯化学品具有较大的潜力.
[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.
【作者单位】：南京工业大学化工学院;
【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~~
【分类号】：O643.36

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