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Mass Spectra of New Heterocycles: XXIII. Electron Impact and Chemical Ionization Study of 5-[(Cyanomethyl)sulfanyl]- and 5-[(1,3-Dioxolan-2-ylmethyl)sulfanyl]-1H-pyrrol-2-amines

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Abstract

The fragmentation of 5-[(cyanomethyl)sulfanyl]- and 5-[(1,3-dioxolan-2-ylmethyl)sulfanyl]-1H-pyrrol-2-amines under electron impact (70 eV) and chemical ionization with methane as reactant gas has been studied for the first time. Electron impact ionization of 5-[(cyanomethyl)sulfanyl]-substituted pyrroles generates low-stability molecular ions {M+·, Irel 4–22%; cf. Irel 16–69% for 5-[(1,3-dioxolan-2-ylmethyl)sulfanyl] analogs} whose primary fragmentation involves cleavage of the C–S bond with expulsion of NCCH2 radical. Other fragmentation pathways of the molecular ions include formation of [M – CHR4]+· ions (R4 = CN) and substituent decomposition products. The mass spectra of 5-[(1,3-dioxolan-2-ylmethyl)sulfanyl]pyrroles characteristically show [M – SCH2R4]+ ion peak. The most intense ion peaks in the chemical ionization mass spectra of 5-[(cyanomethyl)sulfanyl] derivatives are those of M+· (Irel 18–69%) and [M + H]+ (Irel 34–100%). Both 5-[(cyanomethyl)sulfanyl]- and 5-[(1,3-dioxolan-2-ylmethyl)sulfanyl]pyrroles decompose mainly through cleavage of the CH2–S and C5–S bonds with the formation of stable [M – CH2R4]+ (Irel 92–100%), [M + H – CH2R4]+· (Irel 22–75%), and [M + H – SCH2R4]+· ions (Irel 6–25%).

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ACKNOWLEDGMENTS

This study was performed using the equipment of the Baikal joint analytical center (Siberian Branch, Russian Academy of Sciences).

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Authors and Affiliations

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

    L. V. Klyba, N. A. Nedolya, E. R. Sanzheeva & O. A. Tarasova

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  1. L. V. Klyba
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Correspondence to L. V. Klyba.

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Translated from Zhurnal Organicheskoi Khimii, 2021, Vol. 57, No. 12, pp. 1669–1683 https://doi.org/10.31857/S0514749221120028.

For communication XXII, see [1].

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Klyba, L.V., Nedolya, N.A., Sanzheeva, E.R. et al. Mass Spectra of New Heterocycles: XXIII. Electron Impact and Chemical Ionization Study of 5-[(Cyanomethyl)sulfanyl]- and 5-[(1,3-Dioxolan-2-ylmethyl)sulfanyl]-1H-pyrrol-2-amines. Russ J Org Chem 57, 1901–1912 (2021). https://doi.org/10.1134/S1070428021120022

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