Russian Journal of Organic Chemistry

, Volume 46, Issue 2, pp 218–225 | Cite as

Mass spectra of new heterocycles: IX. Main fragmentaion laws of 7-methyl-2-(methylsulfanyl)-3-(1-ethoxyethoxy)-4,5-dihydro-3H-azepine and its structural isomers (2,3-dihydropyridine, pyrrole, thiophene) under electron impact

  • L. V. Klyba
  • N. A. Nedolya
  • O. A. Tarasova
  • E. R. Zhanchipova
  • O. G. Volostnykh
Article

Abstract

Mass spectra were investigated for the first time of four structural isomers of heterocycles, formerly inavailable 7-methyl-2-(methylsulfanyl)-3-(1-ethoxyethoxy)-4,5-dihydro-3H-azepine, 2,2-dimethyl-6-(methylsulfanyl)-5-(1-ethoxyethoxy)-2,3-dihydropyridine, 1-isopropyl-2-(methylsulfanyl)-3-(1-ethoxyethoxy)pyrrole, and N-isopropyl-N-methyl-3-(1-ethoxyethoxy)-2-thiophenamine prepared from a single linear precursor, adduct of α-lithiated 1-(1-ethoxyethoxy)allene and isopropyl isothiocyanate. All compounds formed a molecular ion (I rel 1–6%) whose primary fragmentation at the electron impact (70 eV) occurs in two principal directions related to the cleavage of the C-O bonds in the 1-ethoxyethoxy-substituent: with a simple rupture of the bonds C-OEt and C-O(heterocycle) and with the elimination of an ethoxyethene molecule. In the spectra of 4,5-dihydro-3H-azepine and 2,3-dihydropyridine the first fragmentation channel of [M] dominates. The second direction prevailes at the fragmentation of pyrrole and thiophene molecular ions leading to an odd-electrons ion with m/z 171. Further fragmentation of this ion is characteristic of each isomer and resulted in the formation of diagnostic ions providing a possibility of identification of these isomers by mass spectrometry.

Keywords

Pyrrole Thiophene Sulfanyl Methylsulfanyl Primary Fragmentation 

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Copyright information

© Pleiades Publishing, Ltd. 2010

Authors and Affiliations

  • L. V. Klyba
    • 1
  • N. A. Nedolya
    • 1
  • O. A. Tarasova
    • 1
  • E. R. Zhanchipova
    • 1
  • O. G. Volostnykh
    • 1
  1. 1.Faworsky Institute of Chemistry, Siberian BranchRussian Academy of SciencesIrkutskRussia

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