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
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1.
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