毕业论文--铜催化卤代芳烃氨基化反应研究.docVIP

铜催化卤代芳烃氨基化反应研究 摘 要 含氮杂环化合物因其具有生物活性在制药以及农药工业领域具有重要的地位。例如喹唑啉酮、二氢喹唑啉酮和苯并咪唑及其衍生物等含氮杂化合物已经展现出各种优越的生物药物活性，如镇静催眠、抗惊厥、止咳、抗菌、利尿、抗抑郁等。目前，这些含氮杂环化合物的合成大多依赖2-氨基苯甲酸、2-氨基苯甲酰胺或1，2-二氨基苯衍生物，但是此类芳香胺的制备方法并不容易。 幸运的是我们开发出了一种简单的铜催化卤苯胺化反应，可以很好的解决这个问题。我们用NaN3为氨源，在乙醇中，用铜催化邻位取代卤苯发生Ullmann反应，生成产率较好的2-氨基苯甲酸、2-氨基苯甲酰胺和N-（2-氨基苯基）乙酰胺衍生物。这个Ullmann类反应大致经历了邻位取代卤苯与NaN3偶联得到邻取代叠氮苯，之后被乙醇还原的过程。其中乙醇既是溶剂也是还原剂[4]。 此方法具有经济性和实用性，而且，合成的芳胺类产物可以广泛的被应用于含氮杂环类化合物的合成中。 关键词：铜催化;Ullmann反应;NaN3;芳胺化 COPPER CATALYZED REACTION OF HALOGEATED AROMATIC AMINE ABSTRACT Nitrogen-containing hetrocyclic compound in the formation of biologically active drugs or agents play an important role in the pharmaceutical and agrochemical industries. For example, quianzolinone derivatives，dihydroquinazolinones and benzimidazoles al e now known to show various useful biological and medicinal activities，such as hypnotic，sedative，analgesic，anticonvulsant，antitussive，antibacterial，diuretic，antihistamine，antidepressant and so on．At present,their preparation depends on the availability of the requisite 2-aminobenzoic acid derivatives,2-aminobenzamide derivatives and 1,2-diaminoarene derivatives．But the previous preparation methods of thosearylamines are not convenient． Fortunately,we have developed a simple copper-catalyzed amination of o-functionalized haloarenes using NaN3 as the amino source in ethanol，and the corresponding 2-aminobenzoic acid，2-aminobenzamide,and N-(-2aminophenyl) acetamide derivatives were obtained in good to excellent yields．The protocol undergoes one-pot Ullmann-type coupling of ortho-functionalized haloarenes with NaN3 to give orthofunctionalized azidoarenes，followed reduction with ethanol，and ethanol acted as solvent and reductive agent. The method is of economical and practical advantages，and the synthesized compounds can be widely used in the synthesis of various nitrogen-containing heterocyclic compounds． KEY WORDSCopper catalyst;Ullmann reaction;Sodium Azide;Amination  目 录 1.引 言 1 2.Ullmann反应 3 2.1 Ullmann反应的发展