基于含铜配合物催化C-C键构筑的反应研究

发布时间：2018-04-25 12:25

本文选题：含铜配合物 + 异相催化　；参考：《山西师范大学》2016年硕士论文

【摘要】：近年来,在绿色化学理念的倡导下,寻求高效、简洁、廉价、绿色环保的有机合成方略受到化学家广泛的关注。过渡金属配合物的合成及其催化性能的研究已成为热点。本论文旨在研究含铜配合物在C-C键构筑反应中的催化性能,探讨反应条件对其催化性能的影响,进一步研究催化剂结构与其催化活性的关系,以期对今后的工作提供理论指导。论文的主要工作分为四部分:第一章简要介绍了含铜配合物的研究进展,并对本课题的选题意义及本研究所取得的进展进行了描述。第二章以1,3,5-苯三四唑与醋酸铜为原料,通过溶剂热方法构筑方钠石结构的含铜金属有机骨架材料[(Cu_4O_(0.27)Cl_(0.73)_3(H_(0.5)BTT)_8(H_2O)_(12)]·3MeOH·9DMF(1)。在配合物1结构中,存在以氧/氯为中心的平面正方形[Cu_4O]/[Cu_4Cl]单元,通过与BTT~(3-)配体相连接形成具有阴离子性、孔隙性的三维(3,8-链接的)方钠石的网络结构。与同构的M-BTT MOFs相比较,在Cu_4簇内μ_4-Cl被μ_4-O局部取代,有效地增强了金属中心的路易斯酸性,同时避免了大体积客体[M(DMF)6]2+阳离子对MOF孔道的占据,有效扩充孔道体积。配合物1经过脱水,形成具有不饱和配位Cu_2+中心的配合物1￠[(Cu_4O_(0.27)Cl_(0.73)_3(H_(0.5)BTT)_8]。以醛酮的氰硅化反应为模型,对其作为路易斯酸的催化性能进行探索。在1 mol%的催化剂用量下,成功地实现了异相催化的C-C键的构筑,合成了一系列氰醇类化合物。该反应无须任何碱及溶剂,且催化剂稳定性良好。此外,与Mn-BTT相比,仅仅是其用量的十一分之一,即可使苯甲醛的转化率高达96%。这一结果表明,我们成功地通过后合成修饰,增加了MOF 1的路易斯酸性,使Cu-BTT MOFs的催化活性得到显著提高。第三章以邻菲Up啉与硝酸铜为原料,构筑了三配位的平面双核铜配合物Cu_2(ophen)_2(2)和四核混合价的配合物[Cu_4(ophen)_4(tp)](3)。双核Cu(I)配合物2中配体是以脱质子的2-羟基-1,10-菲Up啉形式呈现,这说明在反应过程中伴随着邻菲Up啉的羟基化。基于已有文献报道,我们推测其具有活化分子氧的潜能,并分别通过需氧的芳基硼酸的自身偶联和格拉泽反应来对其的催化活性进行了研究。值得注意的是,在无毒无污染的绿色溶剂水为主要溶剂时,Cu_2(ophen)_2催化硼酸的自身偶联体系主产物依然是联苯而非酚类,这在以往的文献报道中是很难实现的。在此基础上,我们将这两种配合物应用于需氧的格拉泽反应,在绿色环保的水为溶剂、室温、空气/氧气氛围、无须任何碱,就可以成功地实现99%的高转化率。值得一提的是,配合物3在常规溶剂中溶解性较差,使其在该反应中以非均相的形式发挥作用,循环催化五次后,依然保持较高的催化活性。第四章对本论文的相关工作进行了总结,并对该课题的研究前景进行展望。
[Abstract]:In recent years, based on the idea of green chemistry, the strategy of organic synthesis with high efficiency, simplicity, low cost and green environment has been paid more and more attention by chemists. The synthesis of transition metal complexes and their catalytic properties have become a hot topic. The purpose of this paper is to study the catalytic performance of copper-containing complexes in C-C bond building reactions, to explore the effect of reaction conditions on their catalytic performance, and to further study the relationship between the structure of the catalysts and their catalytic activity, in order to provide theoretical guidance for future work. The main work of this paper is divided into four parts: the first chapter briefly introduces the research progress of copper-containing complexes, and describes the significance of the topic and the progress of the research. In the second chapter, the copper-containing organometallic organic skeleton material with the structure of sodium oblate was constructed by solvothermal method using 1 / 3 triazole and copper acetate as raw materials. [3MeOH 9DMF _ 1] 3MeOH 9DMF _ (1). In the structure of complex 1, there are planar square [Cu_4O] / [Cu_4Cl] units centered on oxygen / chlorine, which form anion, porosity and three-dimensional (3 ~ (38) -linked) sodium montmorillonite network structure by joining with BT-T _ (3) ~ (3) ligands. Compared with the isomorphic M-BTT MOFs, 渭 _ 4-Cl in the Cu_4 cluster is partially replaced by 渭 _ 4-O, which effectively enhances the Lewis acidity of the metal center, avoids the occupation of large volume [M(DMF)6] _ 2 cations to the MOF channels, and effectively expands the pore volume. Complex 1 is dehydrated to form a complex with unsaturated coordination Cu_2 centers. The catalytic activity of aldehydes and ketones as Lewis acid was investigated by using the cyanosilication reaction of aldehydes and ketones as a model. A series of cyanide alcohols were synthesized by constructing heterogeneous C-C bonds at the amount of 1 mol% catalyst. There is no need for any alkali or solvent in the reaction, and the catalyst is stable. In addition, compared with Mn-BTT, the conversion rate of benzaldehyde was as high as 96% when the amount of benzaldehyde was only 1/11. The results show that the Lewis acidity of MOF 1 is increased and the catalytic activity of Cu-BTT MOFs is improved significantly through the post synthesis modification. In chapter 3, a tri-coordinated planar binuclear copper complex, Cu _ 2O _ 2 / T _ 2 / C _ 2 / T _ 2 / Cu _ 4P _ p _ 4 / T _ 3, was constructed from o-phenanthroline and copper nitrate as raw materials. The ligand in binuclear CuNI) complex 2 is in the form of deprotonated 2-hydroxyl -1-10-phenanthroline, which indicates that the hydroxylation of o-phenanthroline is accompanied by the reaction process. Based on the previous reports, we speculated that it has the potential of activating molecular oxygen, and studied its catalytic activity by self-coupling of aerobic aryl boric acid and Glazer reaction respectively. It is worth noting that the main product of the self-coupling system for the catalytic reaction of boric acid is still biphenyl rather than phenols when the non-toxic and pollution-free green solvent water is the main solvent. This is difficult to achieve in the previous literature. On this basis, we have applied these two complexes to aerobic Glazer reaction. The high conversion rate of 99% can be successfully achieved by using green water as solvent, room temperature, air / oxygen atmosphere and no alkali. It is worth mentioning that the solubility of complex 3 in conventional solvents is poor, so that complex 3 acts in heterogeneous form in this reaction. After five cycles of cyclic catalysis, complex 3 still maintains high catalytic activity. The fourth chapter summarizes the related work of this paper, and prospects for the research of this topic.
【学位授予单位】：山西师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

【参考文献】