發(fā)布時(shí)間：2018-03-27 07:44

  本文選題：硒　切入點(diǎn)：有機(jī)硒催化　出處：《揚(yáng)州大學(xué)》2017年碩士論文

【摘要】：脫肟反應(yīng)在藥物中間體的制備中有著重要作用。目前,已報(bào)道的脫肟方法大多使用當(dāng)量重金屬負(fù)載物作為催化劑,存在成本高、工藝繁復(fù)、重金屬污染等問(wèn)題。有機(jī)硒催化劑在氧化反應(yīng)中具有獨(dú)特的催化性能。且有機(jī)硒催化因不使用金屬元素,產(chǎn)物不會(huì)有金屬殘留,適用于對(duì)金屬殘留量要求嚴(yán)格的藥物合成領(lǐng)域。本文研究了一種新型氧化脫肟方法,以催化量的有機(jī)硒為催化劑,空氣條件下,過(guò)氧化氫氧化發(fā)生脫肟反應(yīng),并取得有意義的成果。主要內(nèi)容如下:1.本論文系統(tǒng)研究了溶劑、硒催化劑、溫度、過(guò)氧化氫加入量對(duì)苯甲醛肟氧化脫肟反應(yīng)的影響。獲得最優(yōu)反應(yīng)條件,目標(biāo)產(chǎn)物氣相產(chǎn)率最高達(dá)99%,選擇性達(dá)96%。此條件下,多種非供電子取代芳香醛肟經(jīng)過(guò)微調(diào)反應(yīng)條件得中等收率,強(qiáng)供電子取代芳香醛肟微調(diào)得到相對(duì)較好收率,苯乙酮肟的脫肟收率僅有17%。為此,下一步又對(duì)有機(jī)硒催化的酮肟脫肟反應(yīng)進(jìn)行調(diào)控研究。2.本論文系統(tǒng)研究了溶劑、溫度、過(guò)氧化氫加入量、反應(yīng)時(shí)間對(duì)苯乙酮肟氧化脫肟反應(yīng)的影響。獲得最佳的反應(yīng)條件,各種帶有吸電子取代基團(tuán)與供電子基團(tuán)的芳香酮肟均能得到較好的脫肟收率。放大實(shí)驗(yàn)中,有機(jī)硒催化劑循環(huán)5次時(shí)仍有相對(duì)較好的催化效果�；跈C(jī)理驗(yàn)證實(shí)驗(yàn)的實(shí)驗(yàn)現(xiàn)象與反應(yīng)結(jié)果,以及硒核磁實(shí)驗(yàn)的驗(yàn)證,我們對(duì)可能的反應(yīng)機(jī)理進(jìn)行了解釋。3.為適應(yīng)新型催化劑的發(fā)展要求,我們利用三聚氰胺摻雜非金屬硒經(jīng)燒制制得新型含硒催化劑。用于催化環(huán)己烯烯丙位氧化,生成2-環(huán)己烯醇和2-環(huán)己烯酮。論文部分對(duì)溶劑、含硒催化劑與加入量、反應(yīng)時(shí)間等進(jìn)行系統(tǒng)地探究。目前,2-環(huán)己烯醇和2-環(huán)己烯酮產(chǎn)率與選擇性還需進(jìn)一步研究。綜上,我們開(kāi)發(fā)了一種于空氣條件下,有機(jī)硒催化,過(guò)氧化氫氧化醛(酮)肟的脫肟反應(yīng)。其具有反應(yīng)條件溫和、催化劑用量少、不含金屬等優(yōu)點(diǎn),顯示了良好的實(shí)用價(jià)值。另外,本文制備了新型含硒催化劑,擴(kuò)展了含硒催化劑的應(yīng)用范圍。
[Abstract]:Deoxime reaction plays an important role in the preparation of pharmaceutical intermediates. At present, most of the reported deoxime methods use equivalent heavy metal supports as catalysts, which have high cost and complicated process. Organic selenium catalyst has unique catalytic performance in oxidation reaction, and organic selenium catalyst does not use metal elements, the product will not have metal residue, In this paper, a new oxidation deoxime method was studied, in which the catalytic amount of organic selenium was used as the catalyst, and the oxidation of hydrogen peroxide took place under the condition of air. The main contents are as follows: 1. The effects of solvent, selenium catalyst, temperature and the amount of hydrogen peroxide on the oxidative deoximation of benzaldehyde oxime were systematically studied. The gas phase yield of the target product is up to 99% and the selectivity is 96%. Under these conditions, a few non-electron-substituted aromatic aldoxime can be obtained in moderate yield, and a relatively good yield can be obtained by fine-tuning the strongly electron-supplied aromatic aldoxime. The yield of deoxime of acetophenone oxime is only 17%. Therefore, the next step is to control the ketoxime deoxime reaction catalyzed by organic selenium. The effect of reaction time on the oxidative deoximation of acetophenone oxime was studied. The optimum reaction conditions were obtained. The organic selenium catalyst still has a relatively good catalytic effect after 5 cycles. The experimental phenomena and reaction results are verified based on the mechanism and the verification of the selenium NMR experiment. In order to meet the requirements of the development of new catalysts, we prepared a new type of selenium-containing catalyst from melamine doped nonmetallic selenium, which was used to catalyze the allyl oxidation of cyclohexene. The synthesis of 2-cyclohexenol and 2-cyclohexenone was studied systematically in this paper. The yield and selectivity of 2-cyclohexenol and 2-cyclohexenone need further study. We have developed an organic selenium catalyzed and hydrogen peroxide oxidation of aldehydes (ketone) oxime deoxime reaction under air conditions. It has the advantages of mild reaction conditions, less catalyst dosage and no metal, which shows good practical value. In this paper, a new type of selenium-containing catalyst was prepared, and the application range of selenium-containing catalyst was expanded.
【學(xué)位授予單位】：揚(yáng)州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.251
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本文編號(hào)：1670644