Study on the Oxidation Behavior of N, N-Dimethylaniline Compounds in Microdroplets

被引：0
|
作者：
Li J.-L. [1 ]
Zhang X.-P. [1 ]
Hu P.-H. [1 ]
Zheng M.-Y. [1 ]
Zhang X.-L. [1 ]
Hu L.-Y. [2 ]
Su R. [2 ]
Chen H.-W. [1 ,3 ]
机构：
[1] Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation» East China Institute of Technology, Nanchang
[2] State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun
[3] School of Pharmacy, J iangxi University of Chinese Medicine, Nanchang
来源：
Journal of Chinese Mass Spectrometry Society | 2024年 / 45卷 / 01期
关键词：
fragmentation mechanism; mass spectrometry; N; N-dimethylaniline; oxidation reaction; radical cation;
D O I：
10.7538/zpxb.2023.0055
中图分类号：
学科分类号：
摘要：
Microdroplets have many unique features such as small size and high electric field, therefore they can be accelerated to initiate chemical reactions and even promote some reactions that cannot be carried out in liquid phase. N, N-Dimethylaniline (DMA) is commonly used in medicine as a raw material for the synthesis of pharmaceutical intermediates. At present, the study involving in the detection of DMA is mainly focused on quantitative detection, and there is few reports on oxidation reaction and gas phase dissociation reaction of DMA. In this paper, the oxidation behavior and dissociation reaction of DMA and related compounds were studied by microdroplet spray mass spectrometry and tandem mass spectrometry. It was found that the ultra-high electric field spontaneously generated by microdroplets at the air-water interface can enable the oxidation reaction of DMA and related compounds to form abundant radical cation DMA+'. By changing the reaction distance, carrier gas pressure, injection velocity, sample concentration and substituent groups, the influence of experimental conditions and sub-stituent modes on the generation of DMA+' was explored. The result showed that the presence of electron donor groups is benefit for the stability of radical cations. After the dissociation of DMA+', the main product ions were generated by elimination of hydrogen radical and a successive elimination of HC: N via methyl migration reaction. In addition, when the electron-donating CH3 group was connected with DMA, the intensity of related radical cation increased obviously, indicating that the electron-donating groups promoted the migration reaction. In conclusion, the stable transient intermediate DMA+' that is difficult to prepare by other means, was obtained by microdroplet reaction in this study. This method is helpful to deepen the understanding of the chemical promoted oxidation reaction characteristics of water droplets and enriches the rearrangement reaction types of aniline compounds in gas phase dissociation. It is expected that the prepared active species such as high reactivity radical cations will be applied to chemical industry or pharmaceutical fields in the future. © 2024 Chinese Society for Mass Spectrometry. All rights reserved.
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页码：174 / 182
页数：8
相关论文
共 28 条
  • [1] GRONERT S., Mass spectrometric studies of organic ion/molecule reactions, Chemical Reviews, 101, pp. 329-360, (2001)
  • [2] PEI Jiying, HOU Zhuanghao, Research progress on electrochemistry-induced and corona discharge-induced redox reactions in electrospray ionization mass spectrometry, Journal of Instrumental Analysis, 37, 12, pp. 1508-1513, (2018)
  • [3] ZHANG Xiaoping, ZHONG Dacai, CHEN Honghan, CHEN Huanwen, Characteristic frag-mentationg behavior of N, N-diethylaniline compounds by extractive electrospray ionozationg tandem mass spectromtry, Journal of Chinese Mass Spectrometry Society, 41, 6, pp. 529-534, (2020)
  • [4] YANG Guoping, WU Xiaofeng, HUANG Keke, LIU Kun, CHEN Huanwen, FENG Shouhua, Instrumentation for nanoscale molecular assembly, Journal of Chinese Mass Spectrometry Society, 41, 2, pp. 191-200, (2020)
  • [5] ZHANG X, BARRAZA K M, UPTON K T, BEAUCHAMP J L., Time resolved study of hydroxyl radical oxidation of oleic acid at the air-water interface, Chemical Physics Letters, 683, pp. 76-82, (2017)
  • [6] LI Ke, FAN Lijing, MI Dongbo, GAO Xiaofei, CHEN Huanwen, Study on the gas-phase structure of water dimer radical cation using sass spec-trometry, Journal of Chinese Mass Spectrometry Society, 42, 6, pp. 1139-1144, (2021)
  • [7] XING D, MENG Y, YUAN X, JIN S, SONG X, ZARE R N, ZHANG X., Capture of hydroxyl radicals by hydronium cations in water microdro-plets, Angewandte Chemie International Edition, 61, 33, (2022)
  • [8] QIU L, PSIMOS M D, COOKS R G., Spontaneous oxidation of aromatic sulfones to sulfonic acids in microdroplets, Journal of the American Society for Mass Spectrometry, 33, 8, pp. 1362-1367, (2022)
  • [9] LIANG Chiyu, ZHANG Xinxing, Spontanneous oxidation and hydration of aromantic aldenhydes in microdroplets and its atmospheric implications, Journal of Chinese Mass Spectrometry Society, 44, 2, pp. 242-250, (2023)
  • [10] WANG M, GAO X F, SU R, HE P, CHENG Y Y, LI K, MI D, ZHANG X, ZZHANG X, CHEN H, COOKS R G., Abundant production of reactive water radical cations under ambient conditions, CCS Chemistry, 4, 4, pp. 3559-3566, (2022)
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