【作者】 张浩；

【导师】 王喜存；

【作者基本信息】 西北师范大学 ， 有机化学， 2020， 硕士

【摘要】 菲并咪唑衍生物是一种含氮杂环共轭化合物,易于修饰、合成简单、具有较高的热稳定性、出色的电子传输能力和良好的电致发光性能。因此,研究者对其光学、电化学和热学性质进行了大量的研究,并将其应用于电致发光材料、荧光探针等各个方面。但是,菲并咪唑衍生物在有机合成中的催化性能报道很少。由于传统催化剂过于昂贵、不易回收、污染环境等一些挑战性问题,我们设计合成了两类菲并咪唑衍生物催化剂,并研究了它们在炔烃与二苯氧磷的自由基加成反应,Suzuki-Miyaura偶联反应和Mizoroki-Heck偶联反应中的催化活性及应用。主要的研究内容如下:第一部分为文献综述:（1）金属络合物和有机染料在光催化反应中的研究进展;（2）无磷配体-Pd催化剂在C-C偶联反应中的研究进展。第二部分合成了两类新型菲并[9,10-d]咪唑类催化剂,并研究了其催化活性及应用,主要包括:1.利用Debus-Radziszewski反应合成了五个结构新颖的菲并[9,10-d]咪唑衍生物。研究了他们在水溶液中光催化二苯氧磷与炔烃的自由基加成反应中的催化性能。探索了不同取代基对其光催化活性的影响,结果表明,三苯胺取代的菲并[9,10-d]咪唑化合物作为光催化剂时在炔烃与二苯氧磷的加成反应中展现出了高效的催化活性,该反应不但条件温和、底物普适性好、而且可以高产率得到一系列Z-烯基磷氧化合物。这一研究拓展了菲并[9,10-d]咪唑类化合物在有机光催化反应中的应用。2.在第一部分实验的基础上,进一步制备了一个结构新颖的菲并[9,10-d]咪唑亚胺类化合物,将其与醋酸钯配位得到钯（Ⅱ）固体催化剂,并通过HR-MS、FT-IR、XPS、EDS、TGA、SEM、TEM和ICP对产物的结构、形貌特征、热稳定性和孔结构进行了表征,并通过催化Suzuki偶联和Heck偶联反应对其催化活性进行了详细研究。结果表明:以十二烷基磺酸钠（SDS）作为相转移添加剂,以SDS临界胶束浓度的水溶液为反应溶剂时,高产率得到Suzuki偶联和Heck偶联反应产物,该反应不但条件温和,底物适应范围广,而且Pd催化剂（Z₄）在循环使用15次的情况下催化活性没有明显的降低,说明我们合成的催化剂具有结构稳定、催化性能好和回收利用率高等优点,有望在其他有机催化反应中得到广泛的应用。所有产物的结构都经¹H NMR、¹³C NMR、和HR-MS表征得到确认,个别化合物结构经¹⁹F NMR、³¹P NMR表征确认。更多还原

【Abstract】 The phenanthro[9,10-d]imidazole derivatives are a kind of nitrogen-containing heterocyclic conjugated compound,which are easy to modify and synthesize.Numerous optical,electrochemical and thermal research activities have been focused on phenanthro[9,10-d]imidazol derivatives due to their high thermal stability,excellent electron transport capability and good electroluminescence performance in electroluminescent materials and fluorescent probes.However,using phenanthro[9,10-d]imidazole derivatives as catalysts source is very rare.In our works,we have designed and synthesized two types of phenanthro[9,10-d]imidazole derivatives catalysts to overcome these deficiencies,such as the expensive,difficult to recycle and polluting the environment of traditional catalysts.Finally,their catalytic activities in the reaction of addition of diaryl phosphine oxides to alkynes,Suzuki-Miyaura and Mizoroki-Heck cross-coupling reactions were investigated.The main research contents of this thesis are as follows:The first part is the review of papers:（1）Research progress of metal complexes and organic dyes in photocatalytic reactions;（2）The progress of the synthesis of phosphine-free Pd-catalysts for the C-C coupling reactions.In the second part,two novel types of phenanthrene[9,10-d]imidazole catalysts were synthesized,and the catalytic performance were investigated.1.A series of novel phenanthrol[9,10-d]imidazole derivatives were synthesized by Debus-Radziszewski reaction.The catalytic performance in the reaction of addition of diaryl phosphine oxides to alkynes under water as solvent was studied.Meanwhile,we investigated the effect of different substituents on the catalytic activity of photocatalysts.The results showed that phenanthro[9,10-d]imidazole derivative substituted by triphenylamine group exhibited high-performance catalytic activity to synthesize Z-alkenylphosphine oxides.Mild reaction conditions and good substrate universality make these photocatalyst of great potential application value in organic photocatalytic reactions.In a word,this study expands the application of phenanthrol[9,10-d]imidazole derivatives in organic photocatalytic reactions.2.Based on the first part of the experiment,phenanthro[9,10-d]imidazole derivative was prepared,which was coordinated with palladium acetate to obtain a palladium（Ⅱ）solid catalyst,which was characterized by HR-MS,FT-IR,XPS,EDS,TGA,SEM,TEM and ICP.The Pd-catalyst exhibited high catalytic activity in Suzuki and Heck coupling reactions in an environmentally benign water medium.Meanwhile,Sodium dodecyl sulfonate（SDS）as a phase transfer additive.Further,the Pd-catalyst（Z4）can be reused for 15 times with little decrease of activity through simple and efficient recovery.These results proved that the Pd-catalyst has a stable structure and can be recycled many times,making these photocatalyst has great potential application value in organic catalytic reaction.It is expected to be widely used in other organic catalytic reactions.The structures of all the products were confirmed by ¹H NMR,¹³C NMR,and HR-MS.Individual compound structures were confirmed by ¹⁹F NMR,³¹P NMR.更多还原