Fe、Cu盐催化的芳烃C-H键烷基化及胺化反应的研究

发布时间：2018-05-20 02:30

  本文选题：芳香烃 + 对甲苯磺酸铁　； 参考：《合肥工业大学》2017年硕士论文

【摘要】：芳烃以及杂环芳烃是一类很重要的有机化学成分中间体,它们被广泛地应用于医药、农药、纺织和精细化学品等中。对芳香化合物的研究一直受到化学工作者的重视,新的研究领域不断地被开拓,传统的合成方法也不断地被改进、创新,从而发展为更加简单高效的合成方法来合成更加复杂的化合物,C-H键直接官能团化是近年来研究比较热的研究领域并取得了很好的成果。通过对芳环上的C-H键活化直接官能团化来在芳环上引入其他官能团的研究将具有非常重要的研究意义。本文以过渡金属为催化剂,对芳香烃的sp2 C-H键进行活化烷基化以及胺化反应进行了研究。经过条件优化,筛选确定了最佳的反应条件,在最优条件下对底物进行了拓展,并对实验结果进行了相关讨论。本文第一部分是以对甲苯磺酸铁为催化剂,以过氧酰作为烷基化试剂,催化芳香烃以及杂环芳烃的C-H键进行活化烷基化反应,合成了一系列的芳烃烷基化产物。通过反应条件的优化,筛选出了最佳优化条件是:在氮气保护条件下,反应温度为100℃,0.5 mmol过氧酰,5 mL芳香烃,2.5 mol%对甲苯磺酸铁,反应时间为5小时。实验结果表明此反应条件更适宜于吸电子基的芳香烃的烷基化反应,与传统的傅克烷基化反应形成互补,反应更倾向于生成邻位取代产物。本文第二部分是以溴化铜作为催化剂,醋酸碘苯作为氧化剂,N-氯代酞酰亚胺作为氮源,进行芳烃的C-H键活化官能团化反应,实现了芳烃的C-H键的胺化,合成了一系列的氨基芳烃。通过反应条件的优化,筛选出了最佳优化条件是:0.5 mmol N-氯代酞酰亚胺、2mL芳烃(既作为反应底物,又作为溶剂),10mol%溴化铜、2 mmol醋酸碘苯,温度为130℃,反应时间为8小时。实验结果表明此反应中芳香烃取代基的电子效应对反应有很重要的影响,反应条件更适合于富电子基的芳香烃的胺化反应。
[Abstract]:Aromatic hydrocarbons and heterocyclic aromatic hydrocarbons are important organic chemical intermediates, which are widely used in medicine, pesticides, textiles and fine chemicals. The study of aromatic compounds has been paid attention to by chemists, new research fields have been continuously developed, and traditional synthetic methods have been continuously improved and innovated. It is a hot research field in recent years to develop a more simple and efficient synthesis method to synthesize more complex compounds such as C-H bond direct functionalization and has achieved good results. The introduction of other functional groups to aromatic rings by activation of C-H bonds on aromatic rings will be of great significance. The activation alkylation and amination of sp2 C-H bonds of aromatic hydrocarbons were studied using transition metal as catalyst. The optimum reaction conditions were determined by optimizing the conditions, the substrate was expanded under the optimal conditions, and the experimental results were discussed. In the first part of this paper, a series of aromatics alkylation products were synthesized by using ferric p-toluenesulfonate as catalyst and peroxy as alkylation reagent to catalyze the C-H bond of aromatic hydrocarbons and heterocyclic aromatics. By optimizing the reaction conditions, the optimum conditions were as follows: under the condition of nitrogen protection, the reaction temperature was 100 鈩，

本文编号：1912813