Chemistry of Heterocyclic Compounds

, Volume 47, Issue 11, pp 1430–1435 | Cite as

Reactions of 2-aza-1,3,5-trienes with superbases: competition between formation of thiazoles and azepines

  • N. A. NedolyaEmail author
  • O. A. Tarasova
  • O. G. Volostnykh
  • A. I. Albanov
  • B. A. Trofimov

For the case of 1-(allylsulfanyl)-2-methoxy-N-(1-methylethylidene)buta-1,3-dien-1-amine, obtained from α-lithiated methoxyallene, isopropyl isothiocyanate, and allyl bromide, it was shown that 5-ethylidene-2-(1-methoxyprop-2-enyl)-4,4-dimethyl-4,5-dihydro-1,3-thiazole and 6-methoxy-2-methyl-3H-azepine are formed competitively upon the action of the t-BuOK–THF–DMSO system.


azatrienes 3H-azepines dihydrothiazoles isothiocyanates methoxyallene deprotonation heterocyclization superbases 


  1. 1.
    G. R. Proctor and J. Redpath (editors), Chemistry of Heterocyclic Compounds. Vol. 56. Monocyclic Azepines: The Synthesis and Chemical Properties of the Monocyclic Azepines, Wiley, Chichester, New York, 1996.Google Scholar
  2. 2.
    R. K. Smalley, in: A. R. Katritzky and C. W. Rees (editors), Comprehensive Heterocyclic Chemistry, Elsevier, Oxford, 1984, vol. 7, p. 491.Google Scholar
  3. 3.
    D. J. Le Count, in: A. R. Katritzky, C. W. Rees, and E. F. V. Scriven (editors), Comprehensive Heterocyclic Chemistry II, Elsevier, Oxford, 1996, vol. 9, p. 1.Google Scholar
  4. 4.
    J. B. Bremner, S. Samosorn, in: A. R. Katritzky, C. A. Ramsden, E. F. V. Scriven, and R. J. K. Taylor (editors), Comprehensive Heterocyclic Chemistry III, Elsevier, Oxford, 2008, vol. 13, p. 1.Google Scholar
  5. 5.
    Y. Kubota, K. Satake, R. Ikui, H. Okamoto, and M. Kimura, Bull. Chem. Soc. Jpn., 76, 805 (2003).CrossRefGoogle Scholar
  6. 6.
    J. H. Rigby and F. C. Pigge, J. Org. Chem., 60, 7392 (1995).CrossRefGoogle Scholar
  7. 7.
    M. Decker and J. Lehmann, Arch. Pharm., 336, 466 (2003).CrossRefGoogle Scholar
  8. 8.
    S. Superchi, E. Giorgio, P. Scafato, and C. Rosini, Tetrahedron: Asymmetry, 13, 1385 (2002).CrossRefGoogle Scholar
  9. 9.
    V. Bisai and V. K. Singh, Synlett, 481 (2011).Google Scholar
  10. 10.
    T. Ooi, Y. Uematsu, M. Kameda, and K. Maruoka, Tetrahedron, 62, 11425 (2006).CrossRefGoogle Scholar
  11. 11.
    N. A. Nedolya, L. L. Dmitrieva, A. I. Albanov, L. V. Klyba, O. A. Tarasova, and I. A. Ushakov, Zh. Org. Khim., 42, 465 (2006).Google Scholar
  12. 12.
    N. A. Nedolya, O. A. Tarasova, O. G. Volostnykh, A. I. Albanov, and B. A. Trofimov, J. Organomet. Chem., 696, 3359 (2011).CrossRefGoogle Scholar
  13. 13.
    N. A. Nedolya, Novel Chemistry Based on Isothiocyanates and Polar Organometallics, Thesis, Utrecht University, Utrecht, The Netherlands, 1999.Google Scholar
  14. 14.
    L. Brandsma, Eur. J. Org. Chem., 4569 (2001).Google Scholar
  15. 15.
    L. Brandsma and N. A. Nedolya, Synthesis, 735 (2004).Google Scholar
  16. 16.
    N. A. Nedolya, Khim. Geterotsikl. Soedin., 1443 (2008). [Chem. Heterocycl. Comp., 44, 1165 (2008)].Google Scholar
  17. 17.
    L. Brandsma, Preparative Polar Organometallic Chemistry, Springer-Verlag, Berlin, 1990, Vol. 2, p. 108.Google Scholar
  18. 18.
    M. Piffl, J. Weston, W. Günther, and E. Anders, J. Org. Chem., 65, 5942 (2000).CrossRefGoogle Scholar
  19. 19.
    H. J. Reich and W. W. Willis, Jr., J. Org. Chem., 45, 5227 (1980).CrossRefGoogle Scholar
  20. 20.
    D. S. Tarbell and M. A. McCall, J. Am. Chem. Soc., 74, 48 (1952).CrossRefGoogle Scholar
  21. 21.
    C. C. Price and W. H. Snyder, J. Org. Chem., 27, 4639 (1962).CrossRefGoogle Scholar
  22. 22.
    D. S. Tarbell and W. E. Lovett, J. Am. Chem. Soc., 78, 2259 (1956).CrossRefGoogle Scholar
  23. 23.
    S. Hoff, L. Brandsma, and J. F. Arens, Recl. Trav. Chim. Pays-Bas, 87, 916 (1968).CrossRefGoogle Scholar
  24. 24.
    B. A. Trofimov, N. A. Nedolya, V. V. Gerasimova, and M. G. Voronkov, Sulfur Lett., 8, 73 (1988).Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2012

Authors and Affiliations

  • N. A. Nedolya
    • 1
    Email author
  • O. A. Tarasova
    • 1
  • O. G. Volostnykh
    • 1
  • A. I. Albanov
    • 1
  • B. A. Trofimov
    • 1
  1. 1.A. E. Favorsky Irkutsk Institute of Chemistry, Siberian BranchRussian Academy of SciencesIrkutskRussia

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