【作者】 董宁宁；

【导师】 宋毛平；

【作者基本信息】 郑州大学 ， 有机化学， 2013， 硕士

【摘要】 本论文合成了一系列己知的的含有不同中性离去配体的氮杂环卡宾钯化合物,并考察了这些氮杂环卡宾钯化合物在芳基氯化物的催化胺化反应中的应用。主要工作如下：一、氮杂环卡宾钯化合物的合成根据文献合成方法,本论文合成了一系列含有不同中性离去配体的氮杂环卡宾钯化合物。试验方法如下所示：以苊醌1为原料与2,6-二异丙基苯胺反应合成得到亚胺化合物2,然后,亚胺化合物2与氯甲基甲醚反应得到咪唑盐3(Scheme1)；在K2C03作用下,咪唑盐3与PdCl2、吡啶及其衍生物进行反应,可以得到氮杂环卡宾钯化合物6a-c(Scheme2)。其他氮杂环卡宾钯化合物6d-g须经氮杂环卡宾铜化合物作为转金属化试剂,从而形成氮杂环卡宾钯二聚体,然后解聚来制备(Scheme3)。以上合成的氮杂环卡宾钯化合物6a-g均为已知化合物,本论文通过’HNMR、13CNMR对其进行了表征。二、氮杂环卡宾钯化合物在氯代芳烃胺化反应中催化性能的研究本论文研究了氮杂环卡宾钯化合物催化芳基氯化物的胺化反应(Scheme4)。分别对催化剂、碱和溶剂进行了筛选和优化。最后得到较优的反应条件为：氮气条件下,0.05mo1%的催化剂6d,1,4-二氧六环为溶剂,t-BuOK为碱,80℃下反应24h。在此条件下,氮杂环卡宾钯化合物6d对一系列芳基、杂芳基氯化物与二级胺的偶联反应均取得了很好的催化效果,反应产率最高可达99%。提高催化剂用量至0.5mo1%,氮杂环卡宾钯化合物6d对一系列芳基氯化物与一级胺的偶联反应也能得到很好的催化效果,反应产率最高可达99%。更多还原

【Abstract】 In this thesis, some palladium NHC complexes with different neutral leaving group which had been reported were prepared. In addition, we investigated the catalytic ability of these complexes as precatalysts in the amination of aryl chlorides. The main resluts are shown as follows:1. The synthesis of palladium NHC complexesAccording to the methods of the literature, In this dissertation, we synthesized some palladium NHC complexes with different neutral leaving ligands which had been developed. The methods are shown as follows:the imine compound2prepared from acenaphthequinone1, then the Imine2reacted with the methoxy-(methyl)chloride to get IPr(BIAN) imidazolium chloride3(Scheme1). In the addition of K2CO3, the NHC-Pd complexes6a-c could be synthesized directly by imidazolium chloride3react with PdCl2and nitrogen-containing ligands, respectively (Scheme2). The NHC-Pd complexes6d-g were prepared by the other methods. Firstly, we had to synthesize the NHC-Cu complexex as a transfer metal reagent by the imidazolium chloride3. Then we got the NHC-Pd dimers from the NHC-Cu complex. finally, we could got the NHC-Pd complexes6d-g through the dissociation of the NHC-Pd dimers(Scheme3). All of these NHC-Pd complexes6a-g had been reported by Tu’s group. In this dissertation, all of them were characterized by1H NMR、13C NMR.Ⅱ. Studies on the catalytic ability of well-defined NHC-Pd complexes in the amination of aryl chlorideIn this dissertation, the well-defind NHC-Pd complexes6a-g were regarded as precatalysts in the amination of aryl chloride(Scheme4). We screened and optimized the catalyst, base and solvent respectively. The optimal reaction conditions were: under anhydrous and anaerobic conditions, the loading of catalyst6d is0.05mol%, 1,4-dioxane as solvent, t-BuOK as base, reaction24h at80℃.Under this conditions, the well-defind NHC-Pd complexex6d could effectively catalytic the coupling reaction of a series of (hetero)aryl chlorides with secondary amines, the yield could be up to99%.Increasing the amount of catalyst to0.5mol%, the well-defind NHC-Pd complexex6d could effectively catalytic the coupling reaction of a series of aryl chlorides with primary amines. But it was failed to achieve good results for the heteroaryl chlorides.更多还原