富勒烯胺基衍生物的选择性合成
文献类型：学位论文
| 作者 | 孙涛 |
| 学位类别 | 硕士 |
| 答辩日期 | 2015-05 |
| 授予单位 | 中国科学院研究生院 |
| 授予地点 | 中国科学院长春应用化学研究所 |
| 导师 | 高翔 |
| 关键词 | 富勒烯 二聚体 亲核反应 胺基衍生物 选择性合成 |
| 中文摘要 | 富勒烯分子的发现使人们认识到了一个全新的碳材料世界，并立即引起了全世界科学家们的广泛关注，对富勒烯的研究热潮也由此拉开帷幕。富勒烯分子由于具有独特的三维空间结构和大π电子共轭体系，所以化学性质比平面的芳香族化合物更加丰富。自从C60能够被大规模的制备以来，科学家对富勒烯的研究不断深入，许多富勒烯衍生物在有机光电功能材料和生物医药等领域表现出了优异的性能。化学修饰一直是富勒烯的一个重要研究领域。在数目众多的富勒烯化学反应中，亲核反应，以其生成的产物结构易于控制、适用底物范围广，成为了富勒烯修饰中最常用的反应之一。为了满足富勒烯衍生物在各领域应用的需要，探索新的富勒烯化学反应以及合成具有特殊性质的富勒烯衍生物就成了研究的焦点。本论文重点研究了以单键连结的富勒烯二聚体为反应物，利用亲核反应，选择性合成 1,4-加成富勒烯胺基衍生物，主要研究内容如下： 以二聚体化合物PhCH2C60_C60CH2Ph为底物，利用亲核反应选择性合成单胺基化富勒烯衍生物1,4-(C6H5CH2) (NR2 )C60。通过具有强还原性的氢化钠拔去二级胺上的氢，生成胺基负离子亲核试剂。利用二聚体本身的空间位阻效应和特殊的电荷分布，当胺基负离子对二聚体PhCH2C60_C60CH2Ph进行亲核加成时，只能加成在苄基对位，产生1,4-加成结构衍生物。利用现场可见/近红外光谱对反应过程进行监测，提出了有别于与以往反应的反应机理, 结合理论化学计算研究了反应机理。利用二聚体与二级脂肪胺进行反应可以选择性得到单胺基化富勒烯衍生物，拓展了富勒烯与胺类化合物的反应。 |
| 英文摘要 | The discovery of fullerenes made people to realize a new world of carbon materials and attracted worldwide great attention. From then on, scientists show great interests in these cage-like molecules. Due to its unique three-dimensional structure and relatively free π-electron conjugated system, the chemical reactivity of fullerene is more plentiful than those planar aromatic compounds. Since the C60 became available in macroscopic quantities, the study of fullerene chemistry developed continuously. Many fullerene derivatives have exhibit excellent properties in the area of organic photoelectric material and biomedicine. The modification of fullerene is always an indispensable part in fullerene chemistry. Among various reactions, nucleophilic reaction is regarded as the most commonly used methods for functionalizing fullerene. This is due to its controllable products and extensive scope of substrates. In order to meet the needs of fullerene derivatives in various application area, explore the reactions of fullerene and synthesis of fullerene derivatives which have special property has became the focus of research. In this thesis, we have studied several nucleophilic reactions of singly bonded C60 dimers. By this method, 1,4-aminofullerenes could be regioselectively synthesized. The main works presented in this thesis are as the following: Taking single-bonded C60 dimers as starting materials, we could obtain 1,4-(C6H5CH2)(NR2)C60 selectively in one-pot through nucleophilic reaction. Anionic amine nucleophiles were produced as a result of reaction between NaH and secondary amine. Due to the effect of steric hindrance, only 1,4-addition pattern existed if nucleophilic attack reaction taken. Anionic amine can only attack at the para-carbon atom with respect to the benzyl. The reactions are monitored by in situ Vis–near IR spectroscopy, and possible mechanisms are proposed. Futhermore, the reaction mechanism were investigated by theoretical calculations.This is a novel mechanism which different from the traditional reaction. The preparation of monoamine functionalized fullerene derivatives are achieved via the reaction of PhCH2C60_C60CH2Ph and secondary amine. This work extends the chemical reaction of fullerene with amines. |
| 语种 | 中文 |
| 公开日期 | 2016-05-03 |
| 源URL | [http://ir.ciac.jl.cn/handle/322003/64466]  |
| 专题 | 长春应用化学研究所_长春应用化学研究所知识产出_学位论文 |
| 推荐引用方式 GB/T 7714 | 孙涛. 富勒烯胺基衍生物的选择性合成[D]. 中国科学院长春应用化学研究所. 中国科学院研究生院. 2015. |
入库方式： OAI收割
来源：长春应用化学研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。