Advertisement

Russian Chemical Bulletin

, Volume 42, Issue 3, pp 466–468 | Cite as

ESR study of free radicals formed upon UV irradiation of nitropentafluoroacetone in various solvents

  • B. L. Tumanskii
  • V. I. D'yachenko
  • Yu. I. Lyakhovetskii
  • N. N. Bubnov
  • S. P. Solodovnikov
  • A. F. Kolomiets
Physical Chemistry
  • 22 Downloads

Abstract

The formation of CF3C(O)CF2N(O.)O2CF2C(O)CF3 free radicals upon the UV irradiation of nitropentafluoroacetone (1) in toluene and mesitylene is established by ESR. The most likely cause of their formation is the one-electron oxidation of the solvents by photoexcited1 followed by decay of the radical anion formed from1 with the expulsion of an NO2 anion and attachment of the radical to a molecule of original1. The irradiation of 1 in triethylsilane results in the elimination of a fluoride ion and fixation of a CF3COCFN(O)O' radical. UV irradiation of ketone1 in pentane results in the abstraction of a hydrogen atom from the solvent and the formation of a CF3COCF2N(OH)O ' radical.

Key words

nitropentafluoroacetone, radical anion, photooxidation ESR, fragmentation, solvent dependence 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    P. J. Krusic, K. S. Chen, P. Meakin, and J. K. Kochi,J. Phys. Chem., 1974,78, 2036.Google Scholar
  2. 2.
    B. L. Tumanskii, S. P. Solodovnikov, N. N. Bubnov, S. A. Postovoi, and Yu. V. Zeifman,Izv. Akad. Nauk SSSR, Ser. Khim., 1989, 1926 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1989,38, 1771 (Engl. Transl.)].Google Scholar
  3. 3.
    E. T. Strom and A. L. Bluhm,Chem. Commun., 1966, 115.Google Scholar
  4. 4.
    W. D. Blackley,J. Am. Chem. Soc., 1966,88, 480.Google Scholar
  5. 5.
    A. K. Hoffman,J. Am. Chem. Soc., 1961,83, 4671.Google Scholar
  6. 6.
    V. V. Bukhtiyarov and N. N. Bubnov,Teor. Eksp. Khim., 1968,IV, 267 [Theor. Exp. Chem., 1968,IV (Engl. Transl.)].Google Scholar
  7. 7.
    C. M. Camaggi, L. Lunazzi, and G. Placucci,J. Org. Chem., 1974,39, 2425.Google Scholar
  8. 8.
    P. P. Shorygin and A. V. Topchiev,Zh. Obshch. Khim., 1935,5, 549 [J. Gen. Chem. USSR, 1935,5 (Engl. Transl.)].Google Scholar
  9. 9.
    A. I. Titov,Zh. Obshch. Khim., 1936,6, 1855 [J. Gen. Chem. USSR, 1936,6 (Engl. Transl.)].Google Scholar
  10. 10.
    A. I. Titov,Zh. Obshch. Khim., 1949,19, 258 [J. Gen. Chem. USSR, 1949,19 (Engl. Transl.)].Google Scholar
  11. 11.
    P. P. Shorygin and A. V. Topchiev,Zh. Obshch. Khim., 1937,7, 193 [J. Gen. Chem. USSR, 1937,7 (Engl. Transl.)].Google Scholar
  12. 12.
    S. L. Taylor, D. Y. Lee, and J. C. Martin,J. Org. Chem., 1983,48, 4157.Google Scholar
  13. 13.
    Z. N. Parnes, Yu. I. Lyakhovetskii, N. N. Bubnov, N. M. Vilkova, S. A. Gabrielyan, and D. I. Kursanov,Mekhanismy geteroliticheskikh reaktsii [Mechanisms of Heterolytic Reactions], Nauka, Moscow, 1976 (in Russian).Google Scholar

Copyright information

© Plenum Publishing Corporation 1994

Authors and Affiliations

  • B. L. Tumanskii
    • 1
  • V. I. D'yachenko
    • 1
  • Yu. I. Lyakhovetskii
    • 1
  • N. N. Bubnov
    • 1
  • S. P. Solodovnikov
    • 1
  • A. F. Kolomiets
    • 1
  1. 1.A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussian Federation

Personalised recommendations