【摘要】：Beckmann重排反應(yīng)是碳正離子型重排反應(yīng)中最為人熟知和經(jīng)典的重排反應(yīng)之一，廣泛的應(yīng)用于有機(jī)合成和藥物合成之中，工業(yè)上大規(guī)模的合成環(huán)己內(nèi)酰胺就是利用Beckmann重排來(lái)完成的，因此，研究Beckmann重排反應(yīng)，豐富Beckmann重排反應(yīng)的條件具有重要的現(xiàn)實(shí)意義。我們?cè)谘芯窟^(guò)程中發(fā)現(xiàn)，利用全氟烷基磺酰氟（RfSO2F）在堿性條件下誘導(dǎo)Beckmann重排反應(yīng)不僅可以得到傳統(tǒng)的酰胺，，還可以利用不飽和酮肟為原料合成N-烯基酰胺，在已有的上市藥物中，存在很多N-烯基酰胺類(lèi)化合物。同時(shí)，由于我們的反應(yīng)體系呈堿性，可以對(duì)含有對(duì)酸敏感基團(tuán)的底物進(jìn)行Beckmann重排反應(yīng)。氟烷基磺酰氟在堿性條件下誘導(dǎo)Beckmann重排反應(yīng)成本低廉、條件溫和、操作簡(jiǎn)單、具有良好的實(shí)用性，極大地豐富了Beckmann重排反應(yīng)。 本文對(duì)Beckmann重排反應(yīng)條件、適用范圍和以及合成工藝進(jìn)行了全面的考察。全文共分為三章。 第一章，主要介紹了Beckmann重排反應(yīng)特點(diǎn)和研究進(jìn)展、全氟烷基磺酰氟的應(yīng)用研究綜述以及N-烯基酰胺的合成綜述。 第二章，全面研究了堿性條件下由氟烷磺酰氟誘導(dǎo)的Beckmann重排反應(yīng)的合成工藝，我們經(jīng)過(guò)全面的考察發(fā)現(xiàn)，Beckmann重排反應(yīng)在17℃下，RfSO2F/DBU/CH3Cl體系中達(dá)到了最佳的反應(yīng)效果。另外，底物: RfSO2F:DBU=1:1.5:3是最佳物料比。 第三章，選取不同的底物，利用RfSO2F/DBU/CH3Cl體系合成N-烯基酰胺以及酰胺類(lèi)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

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