“金属试剂导向的有机合成”和“绿色化学”是当今有机化学研究中的两大重要主题，遵从这两大主题，本论文研究了过渡金属促进的苯胺及其衍生物的氧化形成C-C/C-N/N=N键的反应。具体工作包括两个部分：一、硫酸铈促进的苯胺衍生物的水相氧化偶联反应；二、氯化亚铜催化的苯胺类物质的空气氧化反应。 一、苯胺低聚物的研究起源于1907 年。随着聚苯胺研究的深入, 人们合成了不同结构的苯胺低聚物, 作为聚苯胺的模拟物,用以阐明与聚苯胺相关的理论问题。本文报道了采用硫酸铈作为氧化剂与2，6-二取代苯胺之间的水相反应，成功的由2，6-二取代苯胺制取了苯胺的二聚、三聚、四聚以及八聚产物。在硫酸铈的水溶液中，2，6-二取代苯胺能够发生氧化偶联反应。此反应对苯胺2，6位带有不同的取代基的底物表现出很强的选择性。对于2，6-二甲基及2，6-二乙基苯胺主要得到苯胺的二聚、四聚甚至八聚产物；对带有较大位阻基团的2，6-二异丙基苯胺主要得到二聚及三聚产物；而对2，6-二氯苯胺及2，6-二溴苯胺这种带有吸电子基团的底物产物主要为二聚及三聚产物。并且通过各种手段对这个反应的机理进行了较为详细的探索，提出了自由基反应的机理。在一定程度上揭示了苯胺氧化聚合的反应机理。 二、我们发现了一种采用空气中的氧气直接作为氧化剂的苯胺及其衍生物的氧化偶联反应。即：在氯化亚铜的催化下，乙腈溶剂中，苯胺衍生物能够被空气中的氧气氧化得到偶氮类化合物以及苯胺的二聚物。对于苯环上面只带有一个取代基的苯胺，反应的选择性表现为生成偶氮类化合物；而对于苯胺的2，6位同时带有取代基的苯胺类物质则表现出不同的反应特性，将会得到C-N偶联的苯胺二聚物。且通过不同的后处理手段可以得到亚胺式二聚物及酮式二聚物。通过变换大量的底物及反应条件等手段对反应的适用性进行了系统的研究。同时也通过X-射线光电子能谱等手段对此反应的机理进行了较为系统的探索，提出了自由基反应的机理。
Metallic-reagents oriented organic synthesis and green chemistry are two important topics in organic chemistry. Following these topics, this dissertation studied on the transition-metal promoted oxidative coupling of aniline derevatives and C-C/C-N bond formation. The research work included two parts. Part I: Ce(SO4)2-mediated oxidative coupling of primary aromatic amines in water; Part II: CuCl-catalyzed aerobic oxidative reaction of primary aromatic amines. Part I: The research of aniline oligomer originated in 1907. With the in-depth study of polyaniline, different structures of aniline oligomer were synthesized as a simulation of polyaniline material to clarify the relevant theoretical issues. In this thesis we will report the oxidative coupling reaction of aniline derivatives by cerium sulfate in water. Through this reaction dimer, trimer, quartermer and octmer of anilines were synthesized successfully. Cerium sulfate can reacte with aniline derivatives in water and it show a strong selectivity according to different substitutes on the two otho-positions of aniline. For 2,6-dimethyaniline and 2,6-dienthyaniline, dimer, quartermer and octmer were obtained. And for 2,6-diisopropyalaniline, 2,6-dichloroaniline and 2,6-dibromoaniline, dimer and trimer were obtained. A free radical reaction mechanism was proposed which can reveale the mechanism of oxidative polymerization of aniline in some extent. Part II: A coupling reaction of primary anilines oxidized directly by the oxygen in air using cuprous chloride as catalyst was reported. Azobenzenes and the dimer of anilines were formed by this reaction. For one substituted anilines the reaction selectivity show the favorable of the generation of azo compounds. For 2,6-disubstitued anilines, different selectivity is showed and the C-N formation reaction is prefered. If the reaction is quenched by HCl or saturated K2CO3, imines and ketones are obtained respectively. A large number of substrates were tried to study the applicability of this reaction system. X-ray photoelectron spectroscopy was used to study the mechanism and a free radical reaction mechanism was proposed.
