【摘要】：甲基化反應(yīng)是構(gòu)建C-C鍵的重要手段之一,對于有機(jī)合成包括制藥工業(yè)非常重要,因此甲基化反應(yīng)一直都是化學(xué)家們研究的重點(diǎn)。光催化反應(yīng)因?yàn)榉磻?yīng)條件溫和、簡單高效、綠色環(huán)保等優(yōu)點(diǎn)逐漸成為有機(jī)合成研究領(lǐng)域的熱點(diǎn)。因此研究可見光催化的甲基化反應(yīng)很有意義。本文主要分為三個(gè)部分:第一章:綜述了常見的甲基化反應(yīng)類型,包括常見的非自由基歷程甲基化反應(yīng)和自由基歷程的甲基化反應(yīng),過渡金屬催化的甲基化反應(yīng)和光催化的甲基化反應(yīng)。第二章:可見光催化的苯磺酰甲基化反應(yīng)研究。該反應(yīng)條件溫和,以廉價(jià)易得的溴代苯甲砜作為原料。反應(yīng)過程中通過可見光催化循環(huán),溴代苯甲砜發(fā)生單電子轉(zhuǎn)移,生成苯磺酰甲基自由基,該自由基不僅會與芳香雜環(huán)發(fā)生分子間自由基加成反應(yīng),實(shí)現(xiàn)雜環(huán)的苯磺酰甲基化,還能與N-芳基丙烯酰胺衍生物發(fā)生自由基串聯(lián)反應(yīng),生成苯磺酰甲基化的吲哚酮類化合物。第三章,可見光催化的脫苯磺酰基反應(yīng)研究。該章闡述了兩種不同的可見光催化脫苯磺�；姆桨�,一種方案是在體系內(nèi)引入叔丁醇鉀參與反應(yīng),生成雜環(huán)亞甲基自由基,然后在氫供體參與下,達(dá)到脫苯磺�；哪康�;另一種方案是底物中富電荷的苯環(huán)參與光催化循環(huán),發(fā)生單電子轉(zhuǎn)移,從而引發(fā)苯環(huán)與磺酰基的C-S鍵均裂,釋放一分子二氧化硫,實(shí)現(xiàn)脫苯磺�；哪康�。但是這兩種方案都沒能取得預(yù)想的結(jié)果。
[Abstract]:Methylation reaction is one of the most important methods to construct C-C bond, which is very important for organic synthesis, including pharmaceutical industry, so methylation reaction is always the focus of chemists. Photocatalytic reaction has become a hotspot in the field of organic synthesis because of its mild reaction conditions, simple and efficient, green environmental protection and so on. Therefore, the study of visible light-catalyzed methylation is of great significance. This paper is mainly divided into three parts: chapter 1: review the common types of methylation reactions, including the common non-radical process methylation reaction and free radical process methylation reaction. Transition metal catalyzed methylation and photocatalytic methylation. Chapter 2: visible light catalyzed benzene sulfonyl methylation. The reaction conditions were mild and the easily available brominated benzyl sulfoxide was used as the raw material. In the process of reaction, a single electron transfer of brominated benzyl sulfoxide occurs in the process of reaction by visible light catalysis. The radical can not only react with aromatic heterocycles to produce intermolecular radical addition, but also realize the benzyl sulfonyl methylation of heterocyclic compounds. It can also react with N-aryl acrylamide derivatives in series to form benzenesulfonyl methylated indole ketones. In chapter 3, visible light catalyzed debenzenesulfonyl reaction was studied. In this chapter, two different schemes of visible light catalyzed desulfonylation of benzenesulfonyl groups are described. One scheme is to introduce potassium tert-butanol into the system to form heterocyclic methylene free radicals, and then debenzenesulfonyl groups can be achieved with the participation of hydrogen donors. Another scheme is that the charge-rich benzene ring in the substrate participates in the photocatalytic cycle, resulting in a single electron transfer, which leads to the splitting of the C-S bond between the benzene ring and the sulfonyl group, and the release of a molecule of sulfur dioxide to achieve the purpose of removing benzenesulfonyl group. But neither of these schemes has produced the desired results.
【學(xué)位授予單位】：蘇州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O621.25

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 裴文;苯磺�；�,β─不飽和酮的合成[J];延邊大學(xué)學(xué)報(bào)(自然科學(xué)版);1997年02期

2 黃志平;張鳴;項(xiàng)豐順;周黎明;;溴化氫的冰乙酸溶液脫除苯磺�；难芯縖J];廣東化工;2009年05期

3 陳文華;張正;;含對硝基苯磺�；摩�,β-不飽和砜的合成[J];精細(xì)化工;2007年01期

4 陳田;楊運(yùn)泉;楊彥松;陳健;劉文英;;反式-1-苯磺�；�-2-甲基-4-羥基-2-丁烯的合成[J];石油化工;2007年04期

5 蔣淑艷;合成對甲苯磺酰基甲基異腈生產(chǎn)中成品及其中間體分析[J];陜西化工;1997年01期

6 黎其萬,王繼良;6-(3-甲基-4-對甲苯磺�；�-2-丁烯基)-2,3,4,5-四甲氧基甲苯的合成[J];精細(xì)化工;2003年11期

7 陳海生;N，O，O′─三（對甲苯磺酰基）雙（2─羥乙基）胺的合成[J];化學(xué)試劑;1995年03期

8 匡春香,楊青,潘鑫;4-氨基-3-溴-苯磺�；宜峒叭玖系暮铣珊兔擊妊芯縖J];染料工業(yè);1997年06期

9 賴鵬翔;苯磺�；柞６孵パ苌锏难芯縖J];黃渤海海洋;2001年01期

10 林京都;鄭云峰;李景華;;三氟甲磺酸鹽在(E)-6-(3-甲基-4-苯磺酰基-2-丁烯基)-2,3,4,5-四甲氧基甲苯合成中的應(yīng)用[J];浙江工業(yè)大學(xué)學(xué)報(bào);2007年02期

相關(guān)碩士學(xué)位論文 前3條

1 劉飛;可見光催化的苯磺酰甲基化及脫苯磺�；磻�(yīng)研究[D];蘇州大學(xué);2016年

2 邵越水;苯磺�；〈摩粒�-不飽和酮的合成及其在不對稱催化Diels-Alder反應(yīng)中的研究[D];浙江工業(yè)大學(xué);2004年

3 門紅榮;輔酶Q_（10）的合成[D];河北師范大學(xué);2006年

，

本文編號：2219838