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芳香羧酸的交叉脫氫偶聯(lián)反應(yīng)及菲啶合成新方法研究

發(fā)布時(shí)間:2018-06-27 19:06

  本文選題:交叉脫氫偶聯(lián) + 銠催化。 參考:《湘潭大學(xué)》2016年碩士論文


【摘要】:綠色化學(xué)的宗旨是盡量使用廉價(jià)易得的化合物作為原料;盡量縮短反應(yīng)步驟;盡量減少副產(chǎn)物的產(chǎn)生,提高原子經(jīng)濟(jì)性;盡量使用溫和的反應(yīng)條件。因此發(fā)展新的合成方法和使用溫和的反應(yīng)條件顯得越來(lái)越重要,這些反應(yīng)可以提高資源效率,能源效率和化學(xué)選擇性。本文以此為出發(fā)點(diǎn),開(kāi)展了以下兩部分工作:1、首次利用銠催化劑實(shí)現(xiàn)了簡(jiǎn)單芳香羧酸的交叉脫氫偶聯(lián)反應(yīng)。該反應(yīng)以羧基作為導(dǎo)向基團(tuán),直接由兩個(gè)C-H鍵活化構(gòu)建C-C鍵,反應(yīng)底物不需要預(yù)先官能團(tuán)化,縮短了反應(yīng)步驟。該反應(yīng)區(qū)域選擇性好,偶聯(lián)反應(yīng)發(fā)生在羧基的鄰位。另外,該反應(yīng)以水作為反應(yīng)介質(zhì),對(duì)空氣不敏感,是一類環(huán)境友好和高效合成非對(duì)稱的2,2'-聯(lián)芳二羧酸化合物的方法。2、發(fā)展了一類非過(guò)渡金屬催化的2-(2-氨基苯基)苯甲醇類化合物為原料制備菲啶的方法。該反應(yīng)體系簡(jiǎn)單,通過(guò)分子內(nèi)的氨基和醇縮合成環(huán),以氫氧化鉀作為堿,甲苯作為溶劑,在100℃空氣氛圍下反應(yīng)24小時(shí)得到了較好的產(chǎn)率。
[Abstract]:The aim of green chemistry is to use cheap and easily available compounds as raw materials; to shorten the reaction steps; to minimize the production of by-products and to improve atomic economy; and to use mild reaction conditions as far as possible. Therefore, it is more and more important to develop new synthesis methods and to use mild reaction conditions, which can improve resource efficiency, energy efficiency and chemical selectivity. In this paper, the cross dehydrogenation coupling reaction of simple aromatic carboxylic acids with rhodium catalyst was carried out in the following two parts: 1. The C-C bond was directly activated by two C-H bonds with carboxyl group as the guiding group, and the reaction substrate did not need prefunctional group, which shortened the reaction step. The coupling reaction takes place in the ortho position of carboxyl group. In addition, the reaction takes water as the reaction medium and is not sensitive to air. It is an environmentally friendly and highly efficient method for the synthesis of asymmetric 2'2'2'- biarboxylic acid compounds. A method for the preparation of phenanthroline from a class of non-transition metal catalyzed 2- (2-aminophenyl) benzyl alcohol compounds has been developed. The reaction system is simple. The ring is synthesized by the condensation of amino and alcohol in the molecule, potassium hydroxide as base, toluene as solvent, and the reaction temperature is 100 鈩,

本文編號(hào):2074974

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