Zhang Zhiping, Gong Xiaoyun, Zhang Sichun, Yang Haijun, Shi Youmin, Yang Chengdui, Zhang Xinrong, Xiong Xingchuang, Fang Xiang, Ouyang Zheng
School of Chemistry and Chemical Engineering, Xi'an Shiyou University, Xi'an 710065 (China).
Sci Rep. 2013 Dec 11;3:3481. doi: 10.1038/srep03481.
Selective activation of benzene has been mainly limited to the C-H activation. Simple replacement of one carbon in benzene with another atom remains unresolved due to the high dissociation energy. Herein, we demonstrate a direct breakage of the particularly strong C = C bond in benzene through ion-molecule reaction in a low-temperature plasma, in which one carbon atom was replaced by one atomic nitrogen with the formation of pyridine. The mechanism for the formation of pyridine from benzene has been proposed based on the extensive investigation with tandem mass spectrometry. The reaction pathway also works to other aromatics such as toluene and o-xylene. This finding provides a new avenue for selective conversion of aromatics into nitrogen-containing compounds.
苯的选择性活化主要局限于C-H活化。由于高解离能，用另一个原子简单取代苯中的一个碳的问题仍未解决。在此，我们展示了通过低温等离子体中的离子-分子反应直接打破苯中特别强的C = C键，其中一个碳原子被一个氮原子取代，形成了吡啶。基于串联质谱的广泛研究，提出了由苯形成吡啶的机理。该反应途径对其他芳烃如甲苯和邻二甲苯也有效。这一发现为芳烃选择性转化为含氮化合物提供了一条新途径。
