本文關(guān)鍵詞： 有機(jī)鋅試劑 芳基硼酸 Suzuki偶聯(lián)反應(yīng) 芳基硼酸酯　出處：《蘭州交通大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

【摘要】：芳基硼酸在空氣中比較穩(wěn)定,對濕氣不太敏感,可以長期保存而且反應(yīng)活性很高,使得各種取代的芳環(huán)硼酸成為重要的有機(jī)合成中間體以及醫(yī)藥、化工、農(nóng)藥中間體[1-2],是Suzuki交叉偶聯(lián)反應(yīng)的重要原料[3],可以形成C-O鍵、C-N鍵、C-S鍵也可以與含α,β不飽和鍵的羧基化合物進(jìn)行共軛加成反應(yīng)[4],以及合成染料,合成液晶顯示材料中間體,生物傳感器以及除草劑,在有機(jī)化學(xué)方面應(yīng)用非常廣泛。由于它具有毒性低和最終降解成為對環(huán)境友好的硼酸,所以取代芳基硼酸被認(rèn)為是綠色化合物。由于有機(jī)鋅試劑具備良好的官能團(tuán)兼容性,很高的化學(xué)區(qū)域和立體選擇性等,本課題以有機(jī)鋅試劑作為親核試劑,硼酸三甲酯作為親電試劑,在室溫?zé)o氧的條件下反應(yīng)合成了各種官能團(tuán)化的芳基硼酸,并且進(jìn)行了表征�？疾炝朔磻�(yīng)溫度,反應(yīng)時(shí)間,物料配比等主要因素對合成反應(yīng)產(chǎn)率的影響,并且對其最重要的應(yīng)用Suzuki偶聯(lián)反應(yīng)進(jìn)行了研究。本論文分為三部分:第一部分:總結(jié)了取代芳基硼酸的應(yīng)用,芳基硼酸的三種合成方法:有機(jī)鋰試劑法;格氏試劑法;鈀催化氧硼基化法;以及有機(jī)鋅試劑的應(yīng)用和制備方法。第二部分:用有機(jī)鋅試劑制備芳基硼酸。本文對有機(jī)鋅試劑制備芳基硼酸的合成過程,合成路線進(jìn)行了說明,以及反應(yīng)條件進(jìn)行了優(yōu)化,并進(jìn)行底物拓展,得到了一系列芳基硼酸,并通過1HNMR、13CNMR等對產(chǎn)物進(jìn)行了表征,使得該方法的可行性得到了驗(yàn)證,而且此方法產(chǎn)率高,選擇性好,條件溫和,是一種合成芳基硼酸的新途徑。第三部分:Suzuki偶聯(lián)反應(yīng)利用芳基硼酸酯不經(jīng)水解直接“一鍋法”和鹵代烴發(fā)生Suzuki偶聯(lián)反應(yīng),利用芳基硼酸酯避免了部分苯硼酸發(fā)生脫硼作用,還有部分脫水形成酸酐,來減少反應(yīng)過程中硼酸的損失。而“一鍋法”芳基硼酸酯不經(jīng)提純直接用于Suzuki反應(yīng),該反應(yīng)操作簡便,反應(yīng)速度快,豐富了Suzuki反應(yīng)的合成方法。
[Abstract]:Aryl boric acid is stable in air, is not very sensitive to moisture, can be preserved for a long time and has high reaction activity, making various substituted aromatic boric acids become important organic synthetic intermediates, as well as medicine and chemical industry. Pesticide intermediate [1-2], an important raw material for Suzuki cross-coupling reaction, can form C-O bond, C-N bond, C-S bond and conjugate addition reaction with carboxyl compounds containing 偽, 尾 unsaturated bonds [4], as well as synthetic dyes to synthesize intermediate of liquid crystal display materials. Biosensors and herbicides are widely used in organic chemistry because of their low toxicity and eventual degradation into environmentally friendly boric acid. Therefore, substituted aryl boric acid is considered as a green compound. Due to the good functional compatibility, high chemical region and stereoselectivity of organic zinc reagents, organic zinc reagents are used as nucleophilic reagents. Trimethyl borate was used as an electrophilic reagent to synthesize aryl boric acid with various functional groups at room temperature and without oxygen. The reaction temperature, reaction time and reaction time were investigated. The effect of material ratio on the yield of the synthetic reaction was studied, and the most important application of Suzuki coupling reaction was studied. This paper is divided into three parts: the first part: the application of substituted aryl boric acid is summarized. Keywords three synthetic methods of aryl boric acid: organic lithium reagent method; Grignard reagent method; palladium catalyzed boronylation method; And the application and preparation methods of organic zinc reagent. Part two: preparation of aryl boric acid from organic zinc reagent. In this paper, the synthesis process, synthesis route and reaction conditions of aryl boric acid prepared from organic zinc reagent are described, and the reaction conditions are optimized. A series of aryl boric acid was obtained by substrate expansion, and the product was characterized by 1HNMR-13CNMR. The feasibility of the method was verified, and the yield of the method was high, the selectivity was good, and the conditions were mild. It is a new way to synthesize aryl boric acid. Part 3: Suzuki coupling reaction takes place Suzuki coupling reaction between aryl borate ester and halogenated hydrocarbon without hydrolysis, and aryl borate ester avoids partial boric acid deboration. Some of them were dehydrated to form anhydride to reduce the loss of boric acid in the reaction process, while "one-pot" aryl borate was directly used in Suzuki reaction without purification. The reaction was simple, rapid and enriched the synthetic method of Suzuki reaction.
【學(xué)位授予單位】：蘭州交通大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O621.25

【參考文獻(xiàn)】

相關(guān)期刊論文 前7條

1 劉國權(quán);王閃閃;梁九娣;李秋武;韓建榮;;5-三氟甲基-2-氯-4-吡啶硼酸的合成研究[J];河北科技大學(xué)學(xué)報(bào);2014年04期

2 趙昊昱;;5-氟-2-甲氧基苯硼酸的合成[J];化學(xué)試劑;2013年02期

3 劉國權(quán);宋金然;張家瑞;梁九娣;;2-呋喃硼酸的合成研究[J];河北科技大學(xué)學(xué)報(bào);2012年02期

4 徐丹;褚良銀;;苯硼酸及其衍生物在醫(yī)藥與化工領(lǐng)域的應(yīng)用研究進(jìn)展[J];化工進(jìn)展;2006年09期

5 郭孟萍;周麗;何仁;;P,N配位的環(huán)鈀配合物催化Suzuki偶聯(lián)合成含氟液晶化合物的研究[J];分子催化;2006年03期

6 李英奇;伍佑華;彭雨春;;芳基硼酸在有機(jī)合成中的應(yīng)用[J];精細(xì)化工中間體;2006年01期

7 陳新兵,安忠維;新穎的納米鎳催化芳基硼酸與芳基溴的偶聯(lián)反應(yīng)[J];化學(xué)通報(bào);2002年01期

，

本文編號：1503710