Alkynylhalocarbenes 1. Generation of alkynylchloro- and alkynylbromocarbenes from alkynylchlorobromo- and alkynyldibromomethanes, their multiplicity and philicity

  • K. N. Shavrin
  • I. B. Shvedova
  • O. M. Nefedov
Organic Chemistry


The action of t-BuOK on alkynyldihalomethanes RC≡CCHBrX (I, R=Me, t-Bu, Ph; X= Br, Cl) in pentane at −20 to 0°C generates the corresponding alkynylhalocarbenes RC≡C\(\ddot C\)X (II; X=Br, Cl) which in the presence of olefins give alkynylhalocyclo-propanes (V) in 26–70% yield. It has been shown for the example of the reaction of (methylethynyl-) and (tert-butylethynyl)bromocarbenes with cis-butene-2 that the cycloaddition is fully stereospecific. The selectivity index for (methyl-ethynyl)bromocarbene was experimentally determined as 0.48 which is evident for electrophilic character in this carbene.


Pentane Carbene Selectivity Index Electrophilic Character 
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Literature cited

  1. 1.
    K. N. Shavrin and O. M. Nefedov, Izv. Akad. Nauk SSSR, Ser. Khim., No. 5, 1196 (1987).Google Scholar
  2. 2.
    W. Kirmse, Carbene Chemistry, Academic Press, New York (1971), pp. 205, 278.Google Scholar
  3. 3.
    M. B. D'Amore and R. G. Bergman, J. Am. Chem. Soc.,91, No. 20, 5694 (1969); R. G. Bergman and V. J. Rajadhyaksha, J. Am. Chem. Soc.,92, No. 7, 2163 (1970); P. J. Stang, Chem. Rev.,78, No. 4, 383 (1978).Google Scholar
  4. 4.
    H. Hauptmann, Tetrahedron,32, No. 11, 1293 (1976).Google Scholar
  5. 5.
    M. Franck-Neumann and P. Geoffroy, Tetrahedron Lett.,24, No. 17, 1779 (1983).Google Scholar
  6. 6.
    W. Kirmse, Carbene Chemistry, Academic Press, New York (1971), p. 136.Google Scholar
  7. 7.
    O. M. Nefedov, A. I. Ioffe, and L. G. Menchikov, Chemistry of Carbenes [in Russian], Khimiya, Moscow (1990), p. 138.Google Scholar
  8. 8.
    V. I. Faustov and A. I. Ioffe, in: Chemistry of Carbenes and Small-Sized Cyclic Compounds, O. M. Nefedov (ed.), Mir, Moscow (1990), p. 11.Google Scholar
  9. 9.
    P. S. Skell and R. C. Woodworth, J. Am. Chem. Soc.,78, No. 17, 4496 (1956).Google Scholar
  10. 10.
    P. S. Skell and A. Y. Garner, J. Am. Chem. Soc.,78, No. 20, 5430 (1956).Google Scholar
  11. 11.
    R. A. Moss, Acc. Chem. Res.,13, No. 2, 58 (1980).Google Scholar
  12. 12.
    P. J. Stang and T. E. Fisk, J. Am. Chem. Soc.,102, No. 22, 6813 (1980).Google Scholar
  13. 13.
    Organic Syntheses Coll., Vol. 3, John Wiley, New York-London-Sydney (1955), p. 731.Google Scholar
  14. 14.
    K. E. Schulte and K. P. Reiss, Chem. Ber.,87, No. 7, 964 (1954).Google Scholar
  15. 15.
    E. J. Corey and J. W. Suggs, Tetrahedron Lett., No. 31, 2647 (1975).Google Scholar

Copyright information

© Plenum Publishing Corporation 1992

Authors and Affiliations

  • K. N. Shavrin
    • 1
  • I. B. Shvedova
    • 1
  • O. M. Nefedov
    • 1
  1. 1.N. D. Zelinskii Institute of Organic ChemistryAcademy of Sciences of the USSRMoscow

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