Citation: Ren Xiang, Zhang Xiaoping, Wang Yufen, Cao Jingyu, Cheng Yuanyuan, Feng Shouhua, Chen Huanwen. Intramolecular and Intermolecular Methyl Migration of Fenthion Studied by Electrospray Ionization Mass Spectrometry[J]. Acta Chimica Sinica, ;2019, 77(4): 358-364. doi: 10.6023/A18120505 shu

Intramolecular and Intermolecular Methyl Migration of Fenthion Studied by Electrospray Ionization Mass Spectrometry

a.
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012
b.
Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China Institute of Technology, Nanchang 330013

Corresponding author: Feng Shouhua, shfeng@jlu.edu.cn Chen Huanwen, chw8868@gmail.com
Received Date: 17 December 2018
Available Online: 25 April 2019
Fund Project: the Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation Open Fund JXMS201803Project of Jiangxi Provincial Department of Education GJJ160574the National Natural Science Foundation of China 21427802Project supported by the National Natural Science Foundation of China (No. 21427802), the National Natural Science Foundation of China (No. 21520102007, 21605017), Project of Jiangxi Provincial Department of Education (No. GJJ160574), and the Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation Open Fund (JXMS201803)the National Natural Science Foundation of China 21520102007the National Natural Science Foundation of China 21605017

Figures(9)

Methyl transfer reactions are of great significance in the field of synthetic chemistry and life sciences. So far, most of the reported methyl migration reactions have occurred between different types of molecules. Therefore, it is of certain value to search for new methyl transfer reactions. In this study, fenthion, a most common insecticide in the environment, was selected as the studied object, and electrospray ionization mass spectrometry (ESI-MS) was used as the analytical tool to conduct highly sensitive analysis of the reaction system, so as to explore the possibility of methyl transfer reaction in fenthion molecules under the condition of trifluoroacetic acid and nanometer titanium dioxide. Other than m/z 279 (protonated fenthion), some new product ions (m/z 293 and m/z 265) could be observed in the fingerprint MS of fenthion reaction solution. Tandem MS experiments showed that the intensity of product ion m/z 231 (elimination of CH₃SH) in the dissociation of m/z 279 from fenthion reaction solution were different from that from protonated fenthion standard. This indicated that the methyl in the fenthion could transfer from oxygen atom to unsaturated sulfur atom via 1, 3-methyl transfer, forming isomer a2, which led to the high intensity of product ion m/z 231 in the dissociation of m/z 279 from fenthion reaction solution. Under the assistance of acid, the methyl cation continued to transfer from sulfur atom in a2 to the unsaturated sulfur atom in another fenthion molecule, forming a3 (m/z 293) and a4 via intermolecular methyl transfer reaction, which was verified by tandem MS experiments of ions at m/z 293 and m/z 265. In addition, density functional theory (DFT) calculations were carried out to confirm the mechanism of intramolecular and intermolecular methyl transfer reactions of fenthion. In order to observe the phenomenon of methyl transfer more intuitively, the effects of different acids, metal oxides, reaction time and reaction temperature on the signal intensities of ions at m/z 265 and m/z 293 of intermolecular methyl transfer reactions of fenthion were investigated. It could be concluded that under the conditions of trifluoroacetic acid and nanometer titanium dioxide, and 60℃ ultrasound reaction for 6 h, the proportion of intermolecular methyl transfer reactions of fenthion was the highest. In this study, intramolecular and intermolecular methyl transfer reactions were both discovered and investigated in fenthion, which can not only provide a method to study methyl transfer reactions, but also propose a new idea for the study of degradation of fenthion.
- fenthion,
- intramolecular methyl transfer,
- intermolecular methyl transfer,
- electrospray ionization mass spectrometry,
- trifluoroacetic acid,
- nanometer titanium dioxide
1. [1]
  Dakternieks, D.; Lim, A. E. K.; Lim, K. F. Chem. Commun. 1999, 15, 1425.
2. [2]
  Shekar, S.; Brown, S. N. J. Org. Chem. 2014, 79, 12047. doi: 10.1021/jo501888r
3. [3]
  Schmidt, T.; Schwede, T.; Meuwly, M. J. Phys. Chem. B 2014, 118, 5882. doi: 10.1021/jp5028564
4. [4]
  Lukinavicius, G.; Lapiene, V.; Stasevskij, Z.; Dalhoff, C.; Weinhold, E.; Klimasauskas, S. J. Am. Chem. Soc. 2007, 129, 2758. doi: 10.1021/ja0691876
5. [5]
  Khaskin, E.; Zavalij, P. Y.; Vedernikov, A. N. J. Am. Chem. Soc. 2008, 130, 10088. doi: 10.1021/ja804222c
6. [6]
  Shekar, S.; Brown, S. N. Organometallics 2013, 32, 556. doi: 10.1021/om301028c
7. [7]
  Jones, P. A.; Takai, D. Science 2001, 293, 1068. doi: 10.1126/science.1063852
8. [8]
  Klose, R. J.; Bird, A. P. Trends Biochem. Sci. 2006, 31, 89. doi: 10.1016/j.tibs.2005.12.008
9. [9]
  Finnegan, E. J.; Peacock, W. J.; Dennis, E. S. Curr. Opin. Genet. Dev. 2000, 10, 217. doi: 10.1016/S0959-437X(00)00061-7
10. [10]
  Xiong, L.; Ping, L.; Yuan, B.; Wang, Y. J. Am. Soc. Mass Spectrom. 2009, 20, 1172. doi: 10.1016/j.jasms.2009.02.014
11. [11]
  Hughes, R. M.; Waters, M. L. J. Am. Chem. Soc. 2005, 127, 6518. doi: 10.1021/ja0507259
12. [12]
  Callahan, B. P.; Wolfenden, R. J. Am. Chem. Soc. 2003, 125, 310. doi: 10.1021/ja021212u
13. [13]
  Zhang, X.; Wang, H.; Liao, Y.; Ji, H.; Guo, Y. J. Mass Spectrom. 2010, 42, 218.
14. [14]
  Kshirsagar, U. A.; Argade, N. P. Tetrahedron 2009, 65, 5244. doi: 10.1016/j.tet.2009.04.088
15. [15]
  Zhang, X. J. Mol. Struc.-Theochem. 2010, 955, 91. doi: 10.1016/j.theochem.2010.06.008
16. [16]
  Zhang, X.; Yao, S.; Guo, Y. Int. J. Mass Spectrom. 2008, 270, 31. doi: 10.1016/j.ijms.2007.11.007
17. [17]
  Reepmeyer, J. C. Rapid Commun. Mass Spectrom. 2010, 23, 927.
18. [18]
  Gao, X.; Zhu, G.; Zeng, Z.; Chen, W.; Lin, Z.; Liu, Y.; Xu, P.; Zhao, Y. Rapid Commun. Mass Spectrom. 2011, 25, 1061. doi: 10.1002/rcm.4955
19. [19]
  Ammal, S. C.; Yamataka, H.; Aida, M. A.; Dupuis, M. Science 2003, 299, 1555. doi: 10.1126/science.1079491
20. [20]
  Kitamura, S.; Kadota, T.; Yoshida, M.; Jinno, N.; Ohta, S. Comp. Biochem. Phys. C 2000, 126, 259.
21. [21]
  Bai, C. L.; Qiao, C. B.; Zhang, W. D.; Chen, Y. L.; Qu, S. X. Biomed. Environ. Sci. 1990, 3, 262.
22. [22]
  Ben Amara, I.; Sefi, M.; Troudi, A.; Soudani, N.; Boudawara, T.; Zeghal, N. Indian J. Biochem. Bio. 2014, 51, 293.
23. [23]
  Cheke, R. A.; Mcwilliam, A. N.; Mbereki, C.; Van Der Walt, E.; Mtobesya, B.; Magoma, R. N.; Young, S.; Eberly, J. P. Ecotoxicology 2012, 21, 1761. doi: 10.1007/s10646-012-0911-6
24. [24]
  Celik, I.; Isik, I.; Ozok, N.; Kaya, M. S. Toxicol. Ind. Health 2011, 27, 357. doi: 10.1177/0748233710387009
25. [25]
  Eckstein, F.; Gish, G. Trends Biochem. Sci. 1989, 14, 97. doi: 10.1016/0968-0004(89)90130-8
26. [26]
  Frey, P. A.; Sammons, R. D. Science 1985, 228, 541. doi: 10.1126/science.2984773
27. [27]
  Wilkins, E.; Carter, M.; Voss, J.; Ivnitski, D. Electrochem. Commun. 2000, 2, 786. doi: 10.1016/S1388-2481(00)00122-3
28. [28]
  Chen, P. S.; Huang, S. D. Talanta 2006, 69, 669. doi: 10.1016/j.talanta.2005.10.042
29. [29]
  Salm, P.; Taylor, P. J.; Roberts, D.; Silva, J. D. J. Chromatogr. B 2009, 877, 568. doi: 10.1016/j.jchromb.2008.12.066
30. [30]
  You, Z.-S.; Wen, Y.-J.; Jiang, K.-Z.; Pan, Y.-J. Chin. Sci. Bull. 2012, 57, 1183.
31. [31]
  Zhang, J.; Chai, Y. F.; Wang, W.; Shang, W.; Pan, Y. J. Chinese J. Chem. 2012, 30, 2383. doi: 10.1002/cjoc.201200610
32. [32]
  Chai, Y.-F.; Gan, S.-F.; Pan, Y.-J. Acta Chim. Sinica 2012, 70, 1805.
33. [33]
  Yin, X.-C.; Jiang, Y.; Chu, S.-Y.; Weng, G.-F.; Fang, X.; Pan, Y.-J. Acta Chim. Sinica 2018, 76, 436. doi: 10.11862/CJIC.2018.053
34. [34]
  Zhang, X. P.; Chen, H. H.; Ji, Y.; Jiang, K. Z.; Chen, H. W. J. Am. Soc. Mass Spectrom. 2018, doi.org/10.1007/s13361-018-2098-4.
35. [35]
  Newman, M. S.; Karnes, H. A. J. Org. Chem. 1966, 31, 3980. doi: 10.1021/jo01350a023
1. [1]
  Shanghua Li , Malin Li , Xiwen Chi , Xin Yin , Zhaodi Luo , Jihong Yu . 基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑. Acta Physico-Chimica Sinica, 2025, 41(1): 2309003-. doi: 10.3866/PKU.WHXB202309003
2. [2]
  Rui Li , Huan Liu , Yinan Jiao , Shengjian Qin , Jie Meng , Jiayu Song , Rongrong Yan , Hang Su , Hengbin Chen , Zixuan Shang , Jinjin Zhao . 卤化物钙钛矿的单双向离子迁移. Acta Physico-Chimica Sinica, 2024, 40(11): 2311011-. doi: 10.3866/PKU.WHXB202311011
3. [3]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
4. [4]
  Ruiqing LIU , Wenxiu LIU , Kun XIE , Yiran LIU , Hui CHENG , Xiaoyu WANG , Chenxu TIAN , Xiujing LIN , Xiaomiao FENG . Three-dimensional porous titanium nitride as a highly efficient sulfur host. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 867-876. doi: 10.11862/CJIC.20230441
5. [5]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
6. [6]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
7. [7]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
8. [8]
  Caixia Lin , Zhaojiang Shi , Yi Yu , Jianfeng Yan , Keyin Ye , Yaofeng Yuan . Ideological and Political Design for the Electrochemical Synthesis of Benzoxathiazine Dioxide Experiment. University Chemistry, 2024, 39(2): 61-66. doi: 10.3866/PKU.DXHX202309005
9. [9]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
10. [10]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
11. [11]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191
12. [12]
  Wei HE , Jing XI , Tianpei HE , Na CHEN , Quan YUAN . Application of solar-driven inorganic semiconductor-microbe hybrids in carbon dioxide fixation and biomanufacturing. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 35-44. doi: 10.11862/CJIC.20240364
13. [13]
  Dongqi Cai , Fuping Tian , Zerui Zhao , Yanjuan Zhang , Yue Dai , Feifei Huang , Yu Wang . Exploration of Factors Influencing the Determination of Ion Migration Number by Hittorf Method. University Chemistry, 2024, 39(4): 94-99. doi: 10.3866/PKU.DXHX202310031
14. [14]
  Jiayu Tang , Jichuan Pang , Shaohua Xiao , Xinhua Xu , Meifen Wu . Improvement for Measuring Transference Numbers of Ions by Moving-Boundary Method. University Chemistry, 2024, 39(5): 193-200. doi: 10.3866/PKU.DXHX202311021
15. [15]
  Weihan Zhang , Menglu Wang , Ankang Jia , Wei Deng , Shuxing Bai . 表面硫物种对钯-硫纳米片加氢性能的影响. Acta Physico-Chimica Sinica, 2024, 40(11): 2309043-. doi: 10.3866/PKU.WHXB202309043
16. [16]
  Zhiwen HUANG , Qi LIU , Jianping LANG . W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 79-87. doi: 10.11862/CJIC.20240184
17. [17]
  Shicheng Yan . Experimental Teaching Design for the Integration of Scientific Research and Teaching: A Case Study on Organic Electrooxidation. University Chemistry, 2024, 39(11): 350-358. doi: 10.12461/PKU.DXHX202408036
18. [18]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-. doi: 10.3866/PKU.WHXB202406012
19. [19]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
20. [20]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(1605)
HTML views(155)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142