文章基本信息

标题：Gas-phase amination of aromatic hydrocarbons by corona discharge-assisted nitrogen fixation
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作者：Shanshan Shen ; Yunfeng Chai ; Qirong Shen 等
期刊名称：Scientific Reports
电子版ISSN：2045-2322
出版年度：2021
卷号：11
期号：1
页码：2841
DOI：10.1038/s41598-021-82190-8
出版社：Springer Nature
摘要：Abstract This paper reports on the gas-phase amination reaction of aromatic hydrocarbons occurring under corona discharge conditions with N 2 gas as the nitrogen source. The corona discharge device within an atmospheric pressure chemical ionization source was employed to achieve the plasma-assisted N 2 fixation, and the coupled ion trap mass spectrometer (IT-MS) was used to detect positively charged product ions. In the model case, under APCI conditions, unusual product ions, [M 16] and [M 14] , were observed. Based on the high resolution MS data and tandem mass spectrometric information, [M 16] was confirmed to be protonated p -toluidine and [M 14] was confirmed to be p -methylphenylnitrenium ion. According to the experimental results of the isotopic labelling and substituent effect, one feasible mechanism is proposed as follows. Firstly, N 2 is activated by plasma caused via the corona discharge and then electrophilically attacks toluene, yielding the key intermediate, p -methylphenylnitrenium; secondly, the intermediate undergoes double-hydrogen transfer reaction to give rise to the final product ion, protonated p -toluidine. This study may provide a novel idea to explore new and green method for the synthesis of anilines.
其他摘要：Abstract This paper reports on the gas-phase amination reaction of aromatic hydrocarbons occurring under corona discharge conditions with N 2 gas as the nitrogen source. The corona discharge device within an atmospheric pressure chemical ionization source was employed to achieve the plasma-assisted N 2 fixation, and the coupled ion trap mass spectrometer (IT-MS) was used to detect positively charged product ions. In the model case, under APCI conditions, unusual product ions, [M 16] and [M 14] , were observed. Based on the high resolution MS data and tandem mass spectrometric information, [M 16] was confirmed to be protonated p -toluidine and [M 14] was confirmed to be p -methylphenylnitrenium ion. According to the experimental results of the isotopic labelling and substituent effect, one feasible mechanism is proposed as follows. Firstly, N 2 is activated by plasma caused via the corona discharge and then electrophilically attacks toluene, yielding the key intermediate, p -methylphenylnitrenium; secondly, the intermediate undergoes double-hydrogen transfer reaction to give rise to the final product ion, protonated p -toluidine. This study may provide a novel idea to explore new and green method for the synthesis of anilines.