發(fā)布時(shí)間：2018-04-30 11:37

  本文選題：藥物中間體 + 金屬卟啉聚合物�。� 參考：《河北科技大學(xué)》2016年碩士論文

【摘要】：碳酸丙烯酯是一種重要的藥物中間體,主要用于合成碳酸二甲酯、碳酸二乙酯和替諾福韋等。替諾福韋是抗病毒藥物富馬酸替諾福韋脂的關(guān)鍵中間體,近年來廣泛應(yīng)用于艾滋病的治療。新版本的《中國藥典》將碳酸丙烯酯定為藥用輔料,藥劑中主要用作膠凝劑、溶劑和酸性氣體凈化劑�？捎糜谕庥弥苿�,也可用于內(nèi)服制劑的制備。但是用于合成碳酸丙烯酯的催化劑大部分存在活性低、分離困難或合成路線復(fù)雜的問題。為此我們開發(fā)了多相催化劑金屬卟啉聚合物,具有多相催化劑易于分離循環(huán)使用和均相催化劑活性高的優(yōu)點(diǎn)。能夠提高碳酸丙烯酯的收率,降低生產(chǎn)成本。本文介紹了一種用吡咯和對(duì)苯二甲醛在丙酸中回流合成卟啉聚合物[(Por)OP]的方法,通過(Por)OP和相應(yīng)的金屬醋酸鹽發(fā)生配位反應(yīng)制取金屬卟啉聚合物[M(Por)OP(M=Zn,Co)],并使用XPS、FT-IR等方法進(jìn)行表征,證明成功合成金屬卟啉聚合物。實(shí)驗(yàn)中系統(tǒng)考察了M(Por)OP(M=Zn,Co)對(duì)CO_2和環(huán)氧丙烷(PO)的環(huán)加成反應(yīng)的催化性能,M(Por)OP在反應(yīng)中具有很高的活性和選擇性,并且很容易從反應(yīng)體系中分離出來循環(huán)使用。此外M(Por)OP(M=Zn,Co)還具有一個(gè)獨(dú)特的優(yōu)勢(shì)就是它本身具有很密集的金屬卟啉共價(jià)催化活性中心,在聚合物基體中具有高度發(fā)達(dá)的連接結(jié)構(gòu),使其具有良好的活性、穩(wěn)定性、可循環(huán)使用且不溶于反應(yīng)中常使用的溶劑。文獻(xiàn)檢索表明,這是首次介紹催化CO_2化學(xué)固定并且具有難溶性和循環(huán)使用等優(yōu)點(diǎn)的金屬卟啉有機(jī)聚合物。在最優(yōu)的反應(yīng)條件下,使用Zn(Por)OP作為催化劑、KI作為助催化劑,碳酸丙烯酯(PC)的產(chǎn)率能達(dá)到95%,轉(zhuǎn)化頻率可以達(dá)到3183molPCmolZn-1h-1。另外Zn(Por)OP作為一種多相催化劑可以循環(huán)使用至少六次。本文采用SiO_2和SMNP為載體,通過一步合成的辦法將(Por)OP負(fù)載在上面合成SiO_2@Zn(Por)OP、Fe_3O_4@SiO_2@Zn(Por)OP,在獲得較大比表面積的同時(shí),催化劑活性和循環(huán)使用次數(shù)也有了較大突破。
[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\ +\ {\}\
【學(xué)位授予單位】：河北科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O634;TQ225.52

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

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本文編號(hào)：1824408