金属卟啉聚合物的制备及在环加成反应上的应用

发布时间：2018-04-30 11:37

本文选题：药物中间体 + 金属卟啉聚合物　；参考：《河北科技大学》2016年硕士论文

【摘要】：碳酸丙烯酯是一种重要的药物中间体,主要用于合成碳酸二甲酯、碳酸二乙酯和替诺福韦等。替诺福韦是抗病毒药物富马酸替诺福韦脂的关键中间体,近年来广泛应用于艾滋病的治疗。新版本的《中国药典》将碳酸丙烯酯定为药用辅料,药剂中主要用作胶凝剂、溶剂和酸性气体净化剂。可用于外用制剂,也可用于内服制剂的制备。但是用于合成碳酸丙烯酯的催化剂大部分存在活性低、分离困难或合成路线复杂的问题。为此我们开发了多相催化剂金属卟啉聚合物,具有多相催化剂易于分离循环使用和均相催化剂活性高的优点。能够提高碳酸丙烯酯的收率,降低生产成本。本文介绍了一种用吡咯和对苯二甲醛在丙酸中回流合成卟啉聚合物[(Por)OP]的方法,通过(Por)OP和相应的金属醋酸盐发生配位反应制取金属卟啉聚合物[M(Por)OP(M=Zn,Co)],并使用XPS、FT-IR等方法进行表征,证明成功合成金属卟啉聚合物。实验中系统考察了M(Por)OP(M=Zn,Co)对CO_2和环氧丙烷(PO)的环加成反应的催化性能,M(Por)OP在反应中具有很高的活性和选择性,并且很容易从反应体系中分离出来循环使用。此外M(Por)OP(M=Zn,Co)还具有一个独特的优势就是它本身具有很密集的金属卟啉共价催化活性中心,在聚合物基体中具有高度发达的连接结构,使其具有良好的活性、稳定性、可循环使用且不溶于反应中常使用的溶剂。文献检索表明,这是首次介绍催化CO_2化学固定并且具有难溶性和循环使用等优点的金属卟啉有机聚合物。在最优的反应条件下,使用Zn(Por)OP作为催化剂、KI作为助催化剂,碳酸丙烯酯(PC)的产率能达到95%,转化频率可以达到3183molPCmolZn-1h-1。另外Zn(Por)OP作为一种多相催化剂可以循环使用至少六次。本文采用SiO_2和SMNP为载体,通过一步合成的办法将(Por)OP负载在上面合成SiO_2@Zn(Por)OP、Fe_3O_4@SiO_2@Zn(Por)OP,在获得较大比表面积的同时,催化剂活性和循环使用次数也有了较大突破。
[Abstract]:Propylene carbonate is an important intermediate for synthesis of dimethyl carbonate, diethyl carbonate and tenofovir. Tenofovir is a key intermediate of antiviral drug tenofovir fumarate, and has been widely used in the treatment of AIDS in recent years. The new version of the Chinese Pharmacopoeia defines propylene carbonate as a medicinal adjunct, which is mainly used as gelling agent, solvent and acid gas purifier. It can be used in the preparation of external preparation and oral preparation. However, most of the catalysts used in the synthesis of propylene carbonate have low activity, difficult separation or complex synthesis route. For this reason, we have developed a multiphase catalyst, metalloporphyrin polymer, which has the advantages of easy separation and recycling of heterogeneous catalyst and high homogeneous catalyst activity. It can improve the yield of propylene carbonate and reduce the production cost. In this paper, a method of synthesizing porphyrin polymer by refluxing pyrrole and p-benzaldehyde in propionic acid is introduced. The metalloporphyrin polymer (MGPS) is synthesized by the coordination reaction of porphyrin op and the corresponding metal acetate, and characterized by XPSFT-IR. It is proved that the metalloporphyrin polymer has been successfully synthesized. In the experiment, the catalytic performance of MCO_2 and POO in cycloaddition reaction was systematically investigated. MnPoroop has high activity and selectivity in the reaction, and it is easy to separate and recycle from the reaction system. In addition, it has a unique advantage: it has a very dense metalloporphyrin covalent catalytic active center, and has a highly developed junction structure in the polymer matrix, which makes it have good activity and stability. A solvent that is recyclable and insoluble in the reaction. Literature reviews show that this is the first time to introduce metalloporphyrin organic polymers that catalyze the chemical immobilization of CO_2 and have the advantages of insolubility and recycling. Under the optimum reaction conditions, the yield of propylene carbonate can reach 95% and the conversion frequency can reach 3183mol PCmol Zn-1h-1 with Zn(Por)OP as catalyst Ki as co-catalyst. In addition, Zn(Por)OP can be recycled for at least six times as a heterogeneous catalyst. In this paper, SiO_2 and SMNP are used as carriers, and SiO2ZnZN / POP\ +\ {\}\
【学位授予单位】：河北科技大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O634;TQ225.52

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