Advertisement

Russian Chemical Bulletin

, Volume 67, Issue 12, pp 2241–2245 | Cite as

Reactions of the N-isopropyl-α-chloroketimines with PIV dithioacids

  • M. B. GazizovEmail author
  • R. A. Khairullin
  • Yu. S. Kirillina
  • S. Yu. Ivanova
  • Kh. R. Khayarov
  • O. D. Khairullina
Full Articles
  • 3 Downloads

Abstract

A primary iminium salt formed in the reaction of PIV dithioacids with N-isopropyl-α-chloroketimines is transformed into products of nucleophilic substitution of the chlorine atom by dithiophosphorus group (SN pathway), if the imine carbon atom is bonded to the donor and small-volume methyl group, or undergoes reduction of the CCl bond (C-Cl→C-H) (Red pathway), when it is bonded with the bulky acceptor phenyl group. The same effect of substituents was discovered, when replacing methyl group with phenyl one in the position 2 of N-tert-butyl-2-chloraldimines: SN: Red ratio is 1: 0 in the case of Me and 1: 9 in the case of Ph. The iminium salts were transformed into new type ketones containing a phosphor functionality.

Key words

N-isopropyl-α-chloroketimines PIV dithioacids iminium salt chlorine substitution reduction of iminium salt phosphorous-substituted ketones 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    R. A. Cherkasov, Stroenie i reaktsionnaya sposobnost´ organicheskikh soedinenii [Structure and Reactivity of Organic Compounds ], Nauka, Moscow, p. 107 (in Russian).Google Scholar
  2. 2.
    A. N. Pudovik, M. K. Sergeeva, Zh. Obshch. Khim. [Russ. J. Gen. Chem.], 1955, 25, 1759 (in Russian).Google Scholar
  3. 3.
    A. N. Pudovik, I. V. Guryanova, E. A. Ishmaeva, Reaktsii i metody issledovaniya organicheskikh soedinenii [Reactions and Study of Organic Compounds], Khimiya, Moscow, 1968, Vol. 19, 848 pp. (in Russian).Google Scholar
  4. 4.
    A. N. Pudovik, M. G. Zimin, Appl. Chem., 1980, 52, 989; DOI: 10.1351/pac198052040989.CrossRefGoogle Scholar
  5. 5.
    M. G. Zimin, N. G. Zabirov, R. A. Cherkasov, A. N. Pudovik, Zh. Obshch. Khim. [Russ. J. Gen. Chem.], 1978, 48, 1020 (in Russian).Google Scholar
  6. 6.
    I. V. Konovalova, L. A. Burnaeva, Reaktsiya Pudovika [The Pudovik Reaction], KGU, Kazan, 1991, 146 pp. (in Russian).Google Scholar
  7. 7.
    R. A. Khairullin, M. B. Gazizov, N. G. Aksenov, O. I. Gnezdilov, A. V. Il´yasov, Russ. J. Gen. Chem., 2014, 84, 2052; DOI: 10.1134/S1070363214100351.CrossRefGoogle Scholar
  8. 8.
    M. B. Gazizov, R. A. Khairullin, N. G. Aksenov, Russ. Chem. Bull., 2014, 2707; DOI: 10.1007/s11172-014-0803-4.Google Scholar
  9. 9.
    M. B. Gazizov, R. A. Khairullin, N. G. Aksenov, O. G. Sinyashin, Tetrahedron Lett., 2015, 56, 1175; DOI: 10.1016/j. tetlet.2015.11.095.CrossRefGoogle Scholar
  10. 10.
    M. B. Gazizov, R. A. Khairullin, N. G. Aksenov, R. Z. Musin, Tetrahedron Lett., 2015, 56, 4993; DOI: 10.1016/j. tetlet.2015.11.095.CrossRefGoogle Scholar
  11. 11.
    R. A. Khairullin, M. B. Gazizov, N. G. Aksenov, Kh. R. Khayarov, Russ. J. Gen. Chem., 2015, 85, 2099; DOI: 10.1134/ S1070363215090133.CrossRefGoogle Scholar
  12. 12.
    M. B. Gazizov, R. A. Khairullin, A. I. Perina, A. A. Minnikhanova, N. G. Aksenov, O. I. Gnezdilov, A. V. Il´yasov, Kh. R. Khayarov, Russ. J. Gen. Chem., 2016, 86, 499; DOI: 10.1134/S1070363216030014.CrossRefGoogle Scholar
  13. 13.
    R. A. Khairullin, M. B. Gazizov, Yu. S. Kirillina, N. Yu. Bashkirtseva, Russ. J. Gen. Chem., 2017, 87, 2313; DOI: 10.1134/S1070363217100115.CrossRefGoogle Scholar
  14. 14.
    M. B. Gazizov, R. A. Khairullin, Yu. S. Kirillina, N. Yu. Bashkirtseva, K. S. Gazizova, S. Yu. Ivanova, in Advances in Chemistry Research, Ed. J. C. Taylor, Nova Sci. Publishers, New York, 2017, Vol. 41, p. 1–90.Google Scholar
  15. 15.
    R. A. Cherkasov, G. A. Kutyrev, A. N. Pudovik, Tetrahedron, 1985, 41, 2567; DOI: 10.1016/S0040-4020(01)96363-X.CrossRefGoogle Scholar
  16. 16.
    S. Oae, T. N. Tzuymoto, A. Nakanishi, Bull. Chem. Soc. Jpn., 1973, 46, 535; DOI: 10.1246/bcsj.46.535.CrossRefGoogle Scholar
  17. 17.
    G. A. Kutyrev, V. A. Lyagin, R. A. Cherkasov, A. N. Pudovik, Zh. Obshch. Khim. [Russ. J. Gen. Chem.], 1983, 53, 1009 (in Russian).Google Scholar
  18. 18.
    S. Oae, A. Nakanishi, N. Tzuymoto, Tetrahedron, 1972, 28, 2981; DOI: 10.1016/0040-4020(72)80012-7.CrossRefGoogle Scholar
  19. 19.
    A. Nakanishi, S. Oae, Chem. Ind., 1971, 960.Google Scholar
  20. 20.
    A. G. Liakumovich, V. Kh. Kadyrova, N. A. Mukmenova, S. V. Bukharov, Zh. Obshch. Khim. [Russ. J. Gen. Chem.], 1991, 61, 260.Google Scholar
  21. 21.
    M. B. Gazizov, R. A. Khairullin, N. G. Aksenov, Yu. S. Kirillina, A. Yu. Bandikova, Russ. Chem. Bull., 2016, 1119; DOI: 10.1007/s11172-016-1422-z.Google Scholar
  22. 22.
    M. B. Gazizov, R. A. Khairullin, N. G. Aksenov, Tetrahedron Lett., 2016, 57, 272; DOI: 10.1016/j.tetlet.2015.11.095.CrossRefGoogle Scholar
  23. 23.
    M. I. Kabachnik, T. A. Mastryukova, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1953, 2, 145; DOI: 10.1007/BF1188249.CrossRefGoogle Scholar
  24. 24.
    Wm. A. Higgins, P. W. Vogel, W. G. Craig, J. Am. Chem. Soc., 1955, 77, 1864.CrossRefGoogle Scholar
  25. 25.
    N. De Kempe, R. Verhe, L. De Buyck, L. Moens, N. Schamp, Synth. Commun., 1982, 12, 43.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • M. B. Gazizov
    • 1
    Email author
  • R. A. Khairullin
    • 1
  • Yu. S. Kirillina
    • 1
  • S. Yu. Ivanova
    • 1
  • Kh. R. Khayarov
    • 1
  • O. D. Khairullina
    • 1
  1. 1.Kazan National Research Technological UniversityKazanRussian Federation

Personalised recommendations