钯催化炔烃环化以及C-H键活化合成多芳环化合物

发布时间：2018-09-08 18:58

【摘要】：随着现代信息显示技术的发展,有机光电材料的研究和应用越来越受到人们的重视。其中,材料得以实际应用的关键在于优越的材料性能及其低廉的成本。因此,对于有机光电材料的合成方法学研究与材料性能的研究犹如人的左右手一样缺一不可。从结构特点上来说,所有的有机光电材料具有一个共同的特性就是包含一个大π共轭体系来达到让电子流动的目的。因而多芳环类化合物一直是绝大多数有机光电材料首选结构。这类化合物不但因较大π共轭体系提供了刚性的平面结构,同时多种可供选择的合成方法又为材料性能的调控提供了巨大的空间,是一类极具发展前景的有机光电功能材料。这类化合物的合成方法多种多样,例如傅克反应,过渡金属催化的偶联等等,其中,过渡金属催化的反应不但具有良好的官能团兼容性,同时又具有的良好的合成效率及原子经济性等优点,为有机光电材料的合成提供了更多灵活、有效、简便的合成途径。本论文首先对多芳环化合物在有机光电材料中的应用和过渡金属催化的反应背景做了概述,综述了近些年通过过渡金属催化C-H键活化及炔烃环化合成芴及萘衍生物的方法学研究成果。并在这些工作的基础上提出了我们的研究思路,按照这个思路我们完成了以下几个方面的工作:1.成功实现以邻溴二苯甲烷为底物,以醋酸钯为催化剂,三环己基膦为配体,通过分子内的C-H键活化合成芴及其衍生物。此反应条件简单,而且不管是对吸电子基团还是供电子基团都有很好的兼容性。另外当底物为邻氯二苯甲烷时也能在此反应条件下合成相应的芴环化合物。该反应能够合成各种取代的芴衍生物,特别是传统方法难以合成的3,6位取代的芴衍生物,为芴衍生物的在有机光电材料领域的应用提供了更多的调控可能。2.本论文研究了以简单易得的溴苯和二苯乙炔作为底物,以醋酸钯为催化剂,四氟硼酸盐三叔丁基膦为配体一步合成多取代的萘环类化合物。该反应体系的主要优势是简化反应底物的同时反应条件也不需要加入贵重的银盐,一步来合成复杂的多芳环化合物体现了现在倡导的绿色化学的观念。此外对反应普适性研究的发现此反应提具有良好的官能团兼容性和反应效率。
[Abstract]:With the development of modern information display technology, people pay more and more attention to the research and application of organic optoelectronic materials. Among them, the key to practical application of materials lies in superior material properties and low cost. Therefore, it is necessary to study the synthesis methodology and properties of organic optoelectronic materials as well as the right hand. In terms of structural characteristics, all organic optoelectronic materials have a common property, that is, they contain a large 蟺 conjugate system to achieve the purpose of electron flow. Therefore, polyaromatic ring compounds have always been the preferred structure of most organic optoelectronic materials. This kind of compound not only provides rigid planar structure because of the large 蟺 conjugate system, but also provides a huge space for the control of material properties by a variety of alternative synthesis methods. It is a kind of organic optoelectronic functional materials with great development prospects. These compounds are synthesized in a variety of ways, such as Fourier reaction, transition metal-catalyzed coupling, and so on. Among them, transition metal-catalyzed reactions not only have good functional compatibility, At the same time, it has many advantages, such as good synthesis efficiency and atomic economy, which provides more flexible, effective and simple synthetic methods for the synthesis of organic optoelectronic materials. In this paper, the applications of polyaromatic compounds in organic optoelectronic materials and the reaction background of transition metal catalysis are summarized. Recent studies on the synthesis of fluorene and naphthalene derivatives by transition metal catalyzed C-H bond activation and cyclization of alkynes were reviewed. And on the basis of these work put forward our research ideas, according to this idea we have completed the following aspects of work: 1. The synthesis of fluorene and its derivatives was successfully achieved using o-bromodiphenylmethane as substrate, palladium acetate as catalyst and tricyclohexylphosphine as ligand through the activation of intramolecular C-H bond. The reaction conditions are simple and have good compatibility for both electron groups and donor groups. In addition, when the substrate is o-chlorodiphenylmethane, the corresponding fluorene ring compounds can also be synthesized under this reaction condition. All kinds of substituted fluorene derivatives can be synthesized by this reaction, especially those of 3 or 6 position substituted fluorene derivatives which are difficult to be synthesized by traditional methods, which provide more control possibilities for the application of fluorene derivatives in the field of organic optoelectronic materials. In this paper, the synthesis of polysubstituted naphthalene ring compounds by using simple and readily available bromobenzene and diphenylacetylene as substrates, palladium acetate as catalyst, tetrafluoroborate tri-tert-Ding Ji phosphine as ligand was studied. The main advantage of this reaction system is that the reaction conditions are simplified and the expensive silver salt is not needed. The synthesis of complex polyaromatic compounds in one step reflects the concept of green chemistry advocated at present. In addition, it is found that this reaction has good functional compatibility and reaction efficiency.
【学位授予单位】：南京邮电大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O625.15

【相似文献】