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A new approach to the synthesis of strained cyclic systems: II. Mass spectrometric study of 2-dialkylamino-3-phenylthiophenes and their structural isomers, iminothietanes and iminocyclobutenes

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Abstract

Triads of isomeric N-alkyl-N-methyl-3-phenylthiophen-2-amines, N-methyl-3-alkyl-4-methylidene-3-phenylthietan-2-imines, and N-methyl-4-alkylsulfanyl-2-phenylcyclobut-2-en-1-imines (Alk = Me, Et, Bu) were synthesized from 1,3-dilithio-3-phenylpropyne, methyl isothiocyanate, and alkyl halides, and their fragmentation under electron impact was studied. Primary decomposition of the molecular ions of 2-aminothiophenes is determined by the localization of a radical cation center on the nitrogen atom, and it follows a path typical of alkyl(aryl)amines with elimination of hydrogen atom or methyl or propyl radical from the α-carbon atom in the N-alkyl substituent. Fragmentation of the iminothietanes involves cleavage of the four-membered ring in half to give neutral MeNCS molecule and 1-alkyl-1-phenylallene radical cation. Alkylsulfanyl(imino)-cyclobutenes undergo cleavage at the sulfur-containing side chain according to general relations holding in the fragmentation of alkyl sulfides.

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Authors and Affiliations

  1. Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, ul. Favorskogo 1, Irkutsk, 664033, Russia

    L. V. Klyba, O. A. Tarasova, N. A. Nedolya & K. B. Petrushenko

  2. Utrecht University, Utrecht, The Netherlands

    L. Brandsma

Authors
  1. L. V. Klyba
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  2. O. A. Tarasova
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  3. L. Brandsma
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  4. N. A. Nedolya
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  5. K. B. Petrushenko
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Original Russian Text © L.V. Klyba, O.A. Tarasova, L. Brandsma, N.A. Nedolya, K.B. Petrushenko, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42, No. 7, pp. 1023–1033.

For communication I, see [1].

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Klyba, L.V., Tarasova, O.A., Brandsma, L. et al. A new approach to the synthesis of strained cyclic systems: II. Mass spectrometric study of 2-dialkylamino-3-phenylthiophenes and their structural isomers, iminothietanes and iminocyclobutenes. Russ J Org Chem 42, 1003–1014 (2006). https://doi.org/10.1134/S107042800607013X

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  • DOI: https://doi.org/10.1134/S107042800607013X

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