多环芳烃衍生物的选择性直接芳基化反应研究

发布时间：2018-07-05 06:02

本文选题：多环芳烃 + C-H官能团化　；参考：《吉林大学》2017年硕士论文

【摘要】：多环芳烃是有机光电材料、有机高分子材料等多种功能材料的重要构成片段。研究多环芳烃衍生物的选择性C-H键转化方法对于功能材料的合成与应用有重要的促进作用。本文对多环芳烃萘和菲的衍生物进行了区域选择性直接芳基化的方法探究。第一部分我们研究了过渡金属Pd催化的N,N-二甲基氨基甲酰-2-萘胺的远程芳基化反应;第二部分我们研究了9-菲甲醚与多环芳烃衍生物的交叉脱氢偶联反应。1、在室温条件下,我们以Pd(OAc)_2(5 mol%)作催化剂,1.0 equiv.Cu(OAc)_2·H_2O和2.0 equiv.Ph CO_3t-Bu共同做氧化剂,1.0 equiv.Ts OH·H_2O作添加剂,醋酸作溶剂,实现了N,N-二甲基氨基甲酰-2-萘胺的间位芳基化,通过与苯基脲邻位芳基化的反应结果对比,我们提出了芳香性对sp2C-H键直接芳基化的位置选择性有决定性的影响。2、在室温下,我们以K_2S_2O_8为氧化剂,TFA\CH_2Cl_2作溶剂实现了多环芳烃衍生物9-菲甲醚与多环芳烃衍生物的交叉脱氢偶联反应,表现出良好而特别的区域选择性。这种方法在合成复杂多环芳烃以及光电材料方面具有广泛的应用前景。通过以上研究,我们发现多环芳烃衍生物与苯衍生物相比,在C-H键直接芳基化的位置选择性方面、反应机理方面表现出明显的差异。在这种反应性质差异的发现为我们进一步研究多环芳烃衍生物的反应研究奠定了基础。
[Abstract]:Polycyclic aromatic hydrocarbons (PAHs) are important components of organic optoelectronic materials, organic polymer materials and other functional materials. The study of selective C-H bond transformation of polycyclic aromatic hydrocarbons has an important role in promoting the synthesis and application of functional materials. In this paper, a regioselectivity aromatization of polycyclic aromatic naphthalene and phenanthrene derivatives was carried out in this paper. In the first part, we studied the long-range aromatization of N, N- two methyl amino formyl -2- naphthalamines catalyzed by transition metal Pd; the second part, we studied the cross dehydrogenation coupling reaction of 9- phenanthrene and polycyclic aromatic hydrocarbons (.1). At room temperature, we used Pd (OAc) _2 (5 mol%) as catalyst, 1 equiv.Cu (OAc). O and 2 equiv.Ph CO_3t-Bu are used as oxidants together with 1 equiv.Ts OH. H_2O as additives and acetic acid as a solvent to realize the interposition of N, N- two methyl carbamyl -2- naphthalene. By comparing with the reaction of benzylurea ortho arylation, we suggest that aromatic property has a decisive influence on the position selectivity of the direct arylation of sp2C-H bonds. .2, at room temperature, we use K_2S_2O_8 as the oxidant and TFACH_2Cl_2 as the solvent to realize the cross dehydrogenation coupling reaction of polycyclic aromatic derivatives 9- phenanthrene ether and polycyclic aromatic hydrocarbon derivatives, showing good and special regional selectivity. This method has a wide application prospect in the synthesis of complex polycyclic aromatic hydrocarbons and optoelectronic materials. Through the above study, we found that the polycyclic aromatic hydrocarbons (PAH) derivatives have obvious differences in the reaction mechanism of the direct arylation of C-H bonds compared with benzene derivatives. The discovery of the difference in the properties of the polycyclic aromatic hydrocarbons has laid a foundation for our further study on the reaction of polycyclic aromatic hydrocarbons.
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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