Xu Xia, Zhao Xuyang, Tang Jie, Duan Yixiang, Tian Yong-Hui
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an, Shaanxi, 710027, China.
State Key Laboratory of Transient Optics and Photonics, Xi'an Institute of Optics and Precision Mechanics of CAS, Xi'an, Shaanxi, 710119, China.
Angew Chem Int Ed Engl. 2022 Jun 13;61(24):e202203680. doi: 10.1002/anie.202203680. Epub 2022 Apr 11.
Nitrogen fixation is industrially realized by mass production of ammonia, the principal intermediate nitrogen source for N-containing organic molecules. Instead, direct C-N bond formation from dinitrogen (N ) is of great interest but remains a challenge. Here, by virtue of unique plasma-liquid interactions, we developed an environmentally benign one-pot approach to directly couple benzene and N , two naturally abundant yet chemically inert molecules, into value-added arylamines. Under the optimal conditions, an amination yield of 45 % was rapidly achieved, far better than the reported benzene amination efficiency using ammonia. A tentative reaction mechanism was proposed involving the long-lived N (A ) and N species, as evidenced by the key intermediates detected. With a deeper mechanistic understanding and by further optimizing the plasma reactor, the realization of cost-effective electrical amination of benzene with N could become reality.
工业上通过大规模生产氨来实现固氮，氨是含氮有机分子的主要中间氮源。相反，由氮气（N₂）直接形成C-N键备受关注，但仍然是一个挑战。在此，借助独特的等离子体-液体相互作用，我们开发了一种环境友好的一锅法，可将苯和N₂这两种天然丰富但化学惰性的分子直接偶联成增值芳胺。在最佳条件下，迅速实现了45%的胺化产率，远高于报道的使用氨进行苯胺化的效率。提出了一个初步的反应机理，涉及长寿命的N(¹A₁)和N₂物种，检测到的关键中间体证明了这一点。随着对机理的更深入理解以及进一步优化等离子体反应器，利用N₂实现苯的经济高效电胺化可能会成为现实。
