有机硒催化的脱肟反应

发布时间：2018-03-27 07:44

  本文选题：硒　切入点：有机硒催化　出处：《扬州大学》2017年硕士论文

【摘要】：脱肟反应在药物中间体的制备中有着重要作用。目前,已报道的脱肟方法大多使用当量重金属负载物作为催化剂,存在成本高、工艺繁复、重金属污染等问题。有机硒催化剂在氧化反应中具有独特的催化性能。且有机硒催化因不使用金属元素,产物不会有金属残留,适用于对金属残留量要求严格的药物合成领域。本文研究了一种新型氧化脱肟方法,以催化量的有机硒为催化剂,空气条件下,过氧化氢氧化发生脱肟反应,并取得有意义的成果。主要内容如下:1.本论文系统研究了溶剂、硒催化剂、温度、过氧化氢加入量对苯甲醛肟氧化脱肟反应的影响。获得最优反应条件,目标产物气相产率最高达99%,选择性达96%。此条件下,多种非供电子取代芳香醛肟经过微调反应条件得中等收率,强供电子取代芳香醛肟微调得到相对较好收率,苯乙酮肟的脱肟收率仅有17%。为此,下一步又对有机硒催化的酮肟脱肟反应进行调控研究。2.本论文系统研究了溶剂、温度、过氧化氢加入量、反应时间对苯乙酮肟氧化脱肟反应的影响。获得最佳的反应条件,各种带有吸电子取代基团与供电子基团的芳香酮肟均能得到较好的脱肟收率。放大实验中,有机硒催化剂循环5次时仍有相对较好的催化效果。基于机理验证实验的实验现象与反应结果,以及硒核磁实验的验证,我们对可能的反应机理进行了解释。3.为适应新型催化剂的发展要求,我们利用三聚氰胺掺杂非金属硒经烧制制得新型含硒催化剂。用于催化环己烯烯丙位氧化,生成2-环己烯醇和2-环己烯酮。论文部分对溶剂、含硒催化剂与加入量、反应时间等进行系统地探究。目前,2-环己烯醇和2-环己烯酮产率与选择性还需进一步研究。综上,我们开发了一种于空气条件下,有机硒催化,过氧化氢氧化醛(酮)肟的脱肟反应。其具有反应条件温和、催化剂用量少、不含金属等优点,显示了良好的实用价值。另外,本文制备了新型含硒催化剂,扩展了含硒催化剂的应用范围。
[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.
【学位授予单位】：扬州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
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本文编号：1670644