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离子液体在有机合成中的应用

The Application of Ionic Liquids in Organic Synthesis

【作者】 张磊

【导师】 苏策;

【作者基本信息】 兰州理工大学 , 化学工艺, 2008, 硕士

【摘要】 离子液体的研究是近年来绿色化学领域的研究热点之一。室温离子液体(Room temperature ionic liquids,RTILs)是一类特殊的液体熔融盐,具有优良的物理化学性质及可修饰、调变的阴阳离子结构,且可循环使用,被认为是替代常用挥发性有机溶剂的新型绿色溶剂。近几年来,离子液体作为一种绿色溶剂及催化剂在有机合成中发挥了独特的作用,受到人们越来越多的关注。本论文研究了离子液体在有机合成中的应用。论文主要由以下三个部分组成。第一部分系统地概述了离子液体的分类;离子液体的合成方法和性质;离子液体在电化学、化学分离、有机合成等方面的应用,并列举了大量反应实例引证了离子液体在有机合成应用方面具备的优势。第二部分开展了室温下在离子液体[bmim]Br和水构成混合溶剂中硼氢化钠还原醛、酮的反应研究。实验结果表明,[bmim]Bf/水混合溶剂体系能顺利的还原醛和酮,以良好产率合成相应的醇,和传统溶剂相比,[bmim]Br/水混合溶剂体系能加快反应速度,提高反应产率。[bmim]Br在该体系中起着双重作用,既是相转移催化剂又是反应介质。第三部分开展了室温下在离子液体[bmim]PF6中DMSO-Ac2O体系氧化醇的反应研究。实验结果表明,[bmim]PF6比[bmim]BF4和[bmim]Br更适合作为DMSO-Ac2O氧化醇的反应介质。DMSO-Ac2O体系在离子液体[bmim]PF6中可以顺利的氧化醇为相应的醛和酮,芳香族的伯醇比仲醇和脂肪醇的氧化效果显著。和传统方法相比,离子液体中DMSO-Ac2O体系可以加快反应速度,提高反应产率。总之,上述反应均具有条件温和、产率高、环境友好、操作简单、离子液体可以循环利用等优点,该研究工作扩展了离子液体在有机合成中的应用范围,也同时发展了一些简单高效的合成方法。

【Abstract】 Ionic liquids is already to become one of the international chemistry research front edge nowadays. Ionic liquids possess super-ordinary physical chemistry property and easy to be modified the structure of anions and cations. Ionic liquids were considered the replacement of the commonly used volatile organic solvent. Recently, ionic liquids as a kind of green solvent and catalyst have drawn much attention due to the important roles they played in organic synthesis.Herein, we studied the applications of ionic liquids in organic synthesis. The three parts are involved in this dissertation.The first part is an introduction. The summary includes:the classification of ionic liquid; the synthesis and quality of ionic liquid; the application of ionic liquid to organic synthesize, there are lots of reaction examples to illustrate the incomparable merits of ionic liquid in organic synthesis.In part two, ionic liquid [bmim]Br/H2O system promoted reduction of aldehydes and ketones at room temperature were investigated. The results indicated that aldehydes and ketones were conveniently transformed to the corresponding alcohols in the Ionic liquid [bmim]Br/H20 system in excellent yields, compared with the traditional solvents, Ionic liquid [bmim]Br/H20 system can accelerate the reaction and improve the yieds. The ionic liquid play dual effects as phase transfer and media.In part three, oxidation of alcohols to ketones and aldehydes in ionic liquid [bmim]PF6 by DMSO-Ac2O at room temperature were investigated. As the solvents of reaction, compared with the ionic liquid [bmim]Br and [bmim]BF4, [bmim]PF6 showed to be optimal. The results indicated that a series of alcohols were conveniently transformed to the corresponding aldehydes and ketones in the ionic liquid [bmim]PF6, compared with the benzylic secondary alcohols and allylic alcohols, the benzylic primary alcohols were oxidized into the corresponding aldehydes in excellent conversions and yields, satisfactory results obtained. The DMSO-AC2O system in the ionic liquid [bmim]PF6 can accelerate the oxidation reaction and improve the conversions and yieds.In summary, the reactions mentioned above have advantages of mild reaction conditions, environmental benignity, easy to handle and simple manipulation, recycling of the ionic liquids and high yields. In this study, we extended the range of application of ionic liquids [bmim]Br, [bmim]BF4 and [bmim]PF6 in organic synthesis, developed some simple efficient synthetic methods.

【关键词】 绿色化学离子液体还原氧化醛酮
【Key words】 Green ChemistryIonic LiquidsReductionOxidationAlcoholsaldehydes and ketones
  • 【分类号】O621.3
  • 【被引频次】6
  • 【下载频次】1127
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