碱性条件下由全氟烷基磺酰氟诱导α,β-不饱和酮肟的贝克曼重排反应的研究
发布时间：2018-12-14 09:17
【摘要】：Beckmann重排反应是碳正离子型重排反应中最为人熟知和经典的重排反应之一，广泛的应用于有机合成和药物合成之中，工业上大规模的合成环己内酰胺就是利用Beckmann重排来完成的，因此，研究Beckmann重排反应，丰富Beckmann重排反应的条件具有重要的现实意义。我们在研究过程中发现，利用全氟烷基磺酰氟（RfSO2F）在碱性条件下诱导Beckmann重排反应不仅可以得到传统的酰胺，，还可以利用不饱和酮肟为原料合成N-烯基酰胺，在已有的上市药物中，存在很多N-烯基酰胺类化合物。同时，由于我们的反应体系呈碱性，可以对含有对酸敏感基团的底物进行Beckmann重排反应。氟烷基磺酰氟在碱性条件下诱导Beckmann重排反应成本低廉、条件温和、操作简单、具有良好的实用性，极大地丰富了Beckmann重排反应。 本文对Beckmann重排反应条件、适用范围和以及合成工艺进行了全面的考察。全文共分为三章。 第一章，主要介绍了Beckmann重排反应特点和研究进展、全氟烷基磺酰氟的应用研究综述以及N-烯基酰胺的合成综述。 第二章，全面研究了碱性条件下由氟烷磺酰氟诱导的Beckmann重排反应的合成工艺，我们经过全面的考察发现，Beckmann重排反应在17℃下，RfSO2F/DBU/CH3Cl体系中达到了最佳的反应效果。另外，底物: RfSO2F:DBU=1:1.5:3是最佳物料比。 第三章，选取不同的底物，利用RfSO2F/DBU/CH3Cl体系合成N-烯基酰胺以及酰胺类化合物。
[Abstract]:Beckmann rearrangement reaction is one of the most well-known and classical rearrangement reactions in carbon ion rearrangement reaction. It is widely used in organic synthesis and drug synthesis. The large-scale synthesis of cyclocaprolactam in industry is accomplished by Beckmann rearrangement. Therefore, it is of great practical significance to study Beckmann rearrangement reaction and enrich the conditions of Beckmann rearrangement reaction. In the course of our study, we found that Beckmann rearrangement reaction induced by perfluoroalkyl sulfonyl fluoride (RfSO2F) under alkaline conditions can not only produce traditional amides, but also synthesize N-alkenyl amides from unsaturated ketone oxime. There are many N-alkenyl amides among the available drugs on the market. At the same time, because our reaction system is alkaline, the substrate containing acid-sensitive groups can be rearranged by Beckmann. The rearrangement of Beckmann induced by fluoroalkyl sulfonyl fluoride under alkaline conditions is cheap, mild, easy to operate and has good practicability, which greatly enriches the rearrangement reaction of Beckmann. In this paper, the reaction conditions, application range and synthesis process of Beckmann rearrangement were investigated. The full text is divided into three chapters. In chapter 1, the characteristics and research progress of Beckmann rearrangement reaction, the application of perfluoroalkyl sulfonyl fluoride and the synthesis of N-alkyl amide are reviewed. In chapter 2, the synthesis process of Beckmann rearrangement induced by halothane sulfonyl fluoride under alkaline condition was studied. We found that the optimal reaction effect of Beckmann rearrangement reaction was achieved in RfSO2F/DBU/CH3Cl system at 17 鈩
本文编号：2378368
[Abstract]:Beckmann rearrangement reaction is one of the most well-known and classical rearrangement reactions in carbon ion rearrangement reaction. It is widely used in organic synthesis and drug synthesis. The large-scale synthesis of cyclocaprolactam in industry is accomplished by Beckmann rearrangement. Therefore, it is of great practical significance to study Beckmann rearrangement reaction and enrich the conditions of Beckmann rearrangement reaction. In the course of our study, we found that Beckmann rearrangement reaction induced by perfluoroalkyl sulfonyl fluoride (RfSO2F) under alkaline conditions can not only produce traditional amides, but also synthesize N-alkenyl amides from unsaturated ketone oxime. There are many N-alkenyl amides among the available drugs on the market. At the same time, because our reaction system is alkaline, the substrate containing acid-sensitive groups can be rearranged by Beckmann. The rearrangement of Beckmann induced by fluoroalkyl sulfonyl fluoride under alkaline conditions is cheap, mild, easy to operate and has good practicability, which greatly enriches the rearrangement reaction of Beckmann. In this paper, the reaction conditions, application range and synthesis process of Beckmann rearrangement were investigated. The full text is divided into three chapters. In chapter 1, the characteristics and research progress of Beckmann rearrangement reaction, the application of perfluoroalkyl sulfonyl fluoride and the synthesis of N-alkyl amide are reviewed. In chapter 2, the synthesis process of Beckmann rearrangement induced by halothane sulfonyl fluoride under alkaline condition was studied. We found that the optimal reaction effect of Beckmann rearrangement reaction was achieved in RfSO2F/DBU/CH3Cl system at 17 鈩
本文编号：2378368
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