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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

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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.

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  1. Faworsky Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, 664033, Russia

    L. V. Klyba, N. A. Nedolya, O. A. Tarasova, E. R. Zhanchipova & O. G. Volostnykh

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  1. L. V. Klyba
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  2. N. A. Nedolya
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  3. O. A. Tarasova
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  4. E. R. Zhanchipova
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  5. O. G. Volostnykh
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Correspondence to N. A. Nedolya.

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Original Russian Text © L.V. Klyba, N.A. Nedolya, O.A. Tarasova, E.R. Zhanchipova, O.G. Volostnykh, 2009, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 2, pp. 224–231.

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Klyba, L.V., Nedolya, N.A., Tarasova, O.A. et al. 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. Russ J Org Chem 46, 218–225 (2010). https://doi.org/10.1134/S1070428010020132

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