磁性金属—有机骨架催化剂的制备及其在有机合成中的应用

发布时间：2018-02-27 21:02

本文关键词： 金属-有机骨架磁性二氢吡咯呋喃酮 VA嗪　出处：《河北师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：金属-有机骨架材料(Metal-Organic Frameworks,MOF_s)作为有潜在用途的多孔结晶材料已经引起了广泛的关注,它是由一种金属或金属团簇与有机配体相互结合而成的具有三维多孔结构的化合物。由于MOF_s具有较大的比表面积、孔径较易调整、较多的活性位点、较高的热稳定性和较强的酸碱催化活性、以及易于功能化等优良性能,已经广泛的应用于储氢、分离、化学传感器、薄膜器件、发光、药物载体和生物医学成像等领域。目前,MOF_s作为非均相催化剂在有机化学的领域中有广泛的应用,但MOF_s作为催化剂时,在催化剂的分离和回收上还存在一些问题,因此将MOF_s和磁性载体复合在一起使其具有MOF_s本身优异的性能同时赋予其磁性的研究是十分必要的。基于此,我们制备出了三种磁性金属有机骨架催化剂:CoFe_2O_4@SiO_2@IRMOF-3、CoFe_2O_4@SiO_2@MOF-5、CoFe_2O_4@SiO_2@Cu-BTC,并且通过SEM、TEM、XRD、FT-IR、N_2吸附/脱附、TG和VSM等方法对催化剂进行了表征,并且分别评价了这三种催化剂在二氢吡咯衍生物的合成中、呋喃酮衍生物的合成中、VA嗪衍生物的合成中的催化性能,考察了一些条件对催化剂性能的影响,由此我们得到以下实验结果:在二氢吡咯衍生物的合成中,我们以丁炔二酸二甲酯/乙酯,胺和甲醛为原料,CoFe_2O_4@SiO_2@IRMOF-3作为催化剂,甲醇为溶剂室温下进行反应。在该反应中催化剂展示出了较高的活性、缩短了反应时间、易于回收、而且产率较高。在呋喃酮衍生物的合成中,我们以丁炔二酸二甲酯/乙酯,胺和芳香醛为原料,CoFe_2O_4@SiO_2@MOF-5为催化剂,水作为溶剂室温下进行反应,为了检测该条件的适用范围,我们对底物进行拓展,可喜的是我们得到了想要的化合物,并且该方法条件温和、反应时间短、产率高。在VA嗪衍生物的合成中,我们以丁炔二酸二甲酯/乙酯、胺和甲醛为原料,CoFe_2O_4@SiO_2@Cu-BTC为催化剂,乙醇作为溶剂室温下进行反应。该方法新颖,而且符合绿色化学的概念,反应时间短并且产率较高。
[Abstract]:Metal-Organic frameworks (MOFCs), as potential porous crystalline materials, have attracted wide attention. It is a compound composed of metal or metal clusters combined with organic ligands with three-dimensional porous structure. Because MOF_s has a large specific surface area, the pore size is easy to adjust, and there are more active sites. It has been widely used in hydrogen storage, separation, chemical sensors, thin film devices, luminescence, and other excellent properties, such as high thermal stability, strong acid-base catalytic activity, and easy functionalization. In the field of drug carrier and biomedical imaging, MOFs are widely used in the field of organic chemistry as heterogeneous catalysts. However, when MOF_s is used as catalyst, there are still some problems in the separation and recovery of catalysts. Therefore, it is necessary to combine MOF_s with magnetic carriers to make them possess excellent properties of MOF_s and endow them with magnetic properties. We have prepared three kinds of magnetic organometallic skeleton catalyst: CoFe2O4SiO2Snaphe @ IRMOF-3 / CoFeTip _ 2O _ 4SiO _ 2R _ 2O _ 4SiO _ 2OC, and have characterized the catalysts by means of SEMTEMTEMTEMDFT-IRN2 adsorption / desorption TG and VSM, respectively, and have evaluated the three catalysts in the synthesis of dihydropyrrole derivatives, and have evaluated the three catalysts in the synthesis of dihydropyrrole derivatives, respectively, and have evaluated the three catalysts in the synthesis of dihydropyrrole derivatives. Catalytic performance of furanone Derivatives in the Synthesis of Dihydropyrrole Derivatives. The effects of some conditions on the catalytic properties of the catalysts were investigated. The following experimental results are obtained: in the synthesis of dihydropyrrole derivatives, The reaction was carried out with dimethyl succinic acid / ethyl ester, amine and formaldehyde as raw materials, CoFe2O4SiO2IRMOF-3 as catalyst and methanol as solvent at room temperature. The catalyst showed higher activity, shortened reaction time, and was easy to be recovered. In the synthesis of furanone derivatives, we used dimethyl butynediate / ethyl ester, amine and aromatic aldehydes as raw materials and CoFe2O4SiO-2 @ MOF-5 as catalyst. Water was used as solvent to react at room temperature. In order to determine the scope of application of this condition, We expanded the substrate, and the good thing is that we got the desired compound, and this method is mild, the reaction time is short, the yield is high. In the synthesis of VAZine derivatives, we use dimethyl butyronate / ethyl ester, CoFe2O4Fe2O4SiOK2Cu-BTC was used as catalyst, ethanol was used as solvent for the reaction at room temperature. The method was novel, conformed to the concept of green chemistry, and the reaction time was short and the yield was high.
【学位授予单位】：河北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36

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