【作者】 江琳琳；

【导师】 李亚明；

【作者基本信息】 大连理工大学 ， 分析化学， 2010， 硕士

【摘要】 二芳胺和三芳胺类化合物广泛应用于染料、药物和光电材料等领域中。铜催化的Ullmann反应是合成这类化合物的经典方法,然而它常常需要高温以及化学计量的铜试剂,适用的底物范围也很有限。近年来,温和条件下铜催化的C-N键的形成受到了广泛的关注。本课题组在研究铜催化C-N偶联反应时发现邻氨基酚具有加速反应的性质：以Cu(Ⅰ)为催化剂碱性体系中,在不加入配体的情况下,邻氨基酚和碘苯即可在温和的条件下发生N-芳基化和N,N-二芳基化反应,生成含有邻位羟基的二芳胺和三芳胺产物。本论文对影响邻氨基酚与卤代芳烃反应的铜盐、碱、溶剂、温度、原料摩尔比等因素进行研究,发现在以碘化亚铜为催化剂,磷酸钾或碳酸铯为碱,通过调节邻氨基酚与卤代芳烃的摩尔比和反应温度,可以选择性地得到邻氨基酚的N-芳基化和N,N-二芳基化产物。在N-芳基化反应的最佳的反应条件下,邻氨基酚及其衍生物的N-芳基化产物分离收率为63～92%。该反应具有广泛的官能团容忍性,可以容忍甲基,甲氧基,硝基,乙酰基甚至是游离的氨基和羟基。当对溴碘苯与邻氨基酚反应时,几乎专一性地生成2-(4-溴苯基氨基)苯酚,显示出该反应良好的化学选择性。在N,N-二芳基化反应的最佳条件下,反应得到了46-87%的邻羟基三芳胺类产物。底物范围的测试表明,该反应对甲基,甲氧基,乙酰基等有良好的容忍性；位阻效应对N,N-二芳基化反应的影响比较明显。在邻氨基酚与硝基取代的卤代芳烃偶联反应中发现了邻氨基酚同时存在着N-芳基化和O-芳基化反应。通过在对温度、溶剂、反应时间等条件进行研究,成功控制了邻氨基酚的N-芳基化和O-芳基化的选择性,反应的收率分别为86%和74%。苯酚、苯胺的混合物与对硝基氯苯的竞争性反应结果表明,N-芳基化是被邻氨基酚所导向的催化过程,O-芳基化是SNAr过程；碘苯与氨基酚类衍生物的偶联反应的结果表明,只有取代的氨基和羟基处于邻位才有明显的自催化效应。根据以上实验结果,推测了邻氨基酚自催化的反应机理：在碱的作用下邻氨基酚负离子与CuI形成稳定的五元环过渡态催化C-N键生成。本文利用邻氨基酚的自催化效应,开发了一种直接、高效、选择性的合成带有邻羟基取代基的二芳胺和三芳胺类化合物的途径,并对硝基卤代芳烃为底物时N-芳基化和O-芳基反应进行了研究。更多还原

【Abstract】 Di-and triarylamines are important building blocks in dyes, pharmaceuticals and photoelectric function materials. As one of the traditional methods to assemble these compounds, Ullmann reaction is limited by the harsh reaction condition, substrate scope and the moderate yield. Recently, much attention has been paid on Cu-catalyzed formation of C-N bonds.In our previous work, we found o-aminophenol derivatives promoting Cu-catalyzed C-N bond formation. In further investigation, o-aminophenol could couple with iodobenzene in the Cu-catalyzed system without ligand which indicated their self-accelerating effect.In this thesis, by investigating the effect facts in the reaction of o-aminophenol and aryl halides, such as copper, base, solvent and molar ratio of raw materials, we developed a ligand free system for selective N-arylation and N,N-diarylation. With the optimal reaction condition of N-arylation, o-aminophenol coupled with aryl halides to get diarylamines in 63-92%yields. The reaction also showed favorable functional group tolerance, such as methyl, methoxyl, acetyl, nitro, especially free hydroxyl and amine group. The different reactivity between iodides and bromides allowed us to obtain the 2-(4-bromophenyl-amino) phenol selectively. With the optimal reaction condition of N,N-diarylation, triarylamines could be obtain in the yield of 46-87%. Compared with N-arylation, the steric effect of N,N-diarylation was significant.When o-aminophenol coupled with p-nitro aryl halides, N-arylation product and O-arylation product were obtained simultaneously. By investigating the reaction conditions, o-aminophenol could transforme to N-or Oarylation product selectively.The results of further investigations indicated that self-accelerating effect occured in the condition of hydroxyl and amino group in ortho position.Utilizing the dramatic self-accelerating effect of o-aminophenols, we developed a Cu-catalyzed system for the selective synthesizing di-and triarylamines. In addition, the N-and O-arylation products of o-aminophenol could be obtained when nitro aryl halides severed as substrates.更多还原