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Kinetics and Catalysis

, Volume 45, Issue 6, pp 794–798 | Cite as

Effect of the structure of reactants on the reaction rate constants of aromatic nitroso oxides with olefins

  • E. M. Chainikova
  • S. L. Khursan
  • R. L. Safiullin
Peroxides-XI
  • 31 Downloads

Abstract

The reactivity of phenylnitroso oxide, (p-methylphenyl)nitroso oxide, (p-nitrophenyl)nitroso oxide, (m-nitrophenyl)nitroso oxide, and (p-bromophenyl)nitroso oxide toward a number of olefins in acetonitrile at room temperature was studied using flash photolysis. It was found that the reaction rate constant decreased with decreasing energy of a molecular orbital with a maximum contribution from the atomic orbitals of carbon atoms in the C=C bond of olefins. This, along with a positive slope of the Hammett function for the reactions of substituted phenylnitroso oxides with 1-hexene and styrene, suggest an electrophilic character of these species. The temperature dependence of the rate constant of the reaction of phenylnitroso oxide with 1-hexene was studied: log A = 7.9 ± 0.4 [l mol−1 s−1]; Ea = 38 ± 2 kJ/mol.

Keywords

Acetonitrile Styrene Photolysis Molecular Orbital Positive Slope 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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REFERENCES

  1. 1.
    Gritsan, N.P., Platz, M.S. 2001Adv. Phys. Org. Chem.36255Google Scholar
  2. 2.
    Liang, T.-Y., Shuster, G.B. 1987J. Am. Chem. Soc.1097803Google Scholar
  3. 3.
    Brinen, J.S., Singh, B. 1971J. Am. Chem. Soc.936623Google Scholar
  4. 4.
    Sawaki, Y., Ishikawa, S., Iwamura, H. 1987J. Am. Chem. Soc.109584Google Scholar
  5. 5.
    Ishikawa, S., Tsuji, S., Sawaki, Y. 1991J. Am. Chem. Soc.1134282Google Scholar
  6. 6.
    Ishikawa, S., Nojima, T., and Sawaki, S., J. Chem. Soc., Perkin Trans. 2, 1996, p. 127.Google Scholar
  7. 7.
    Chainikova, E.M., Khursan, S.L., Safiullin, R.L. 2003Dokl. Akad. Nauk390796Google Scholar
  8. 8.
    Safiullin, R.L., Khursan, S.L., Chainikova, E.M., and Danilov, V.T., Kinet. Katal., (in press).Google Scholar
  9. 9.
    Weissberger, A., Proskauer, E.S., Riddick, J.A., Toops, E.E. 1955Technics of Organic ChemistryWileyNew YorkGoogle Scholar
  10. 10.
    Lindsay, R.O., Allen, G.F. 1955Org. Synth.3710Google Scholar
  11. 11.
    Smith, P.A.S., Boyer, J.H. 1963Org. Synth.475Google Scholar
  12. 12.
    Maslennikov, S.I., Nikolaev, A.I., Komissarov, V.D. 1979Kinet. Katal.20326Google Scholar
  13. 13.
    Mogilevich, M.M., Pliss, E.M. 1990Okislenie i okislitel’naya polimerizatsiya nepredel’nykh soedineniiKhimiyaMoscow(Oxidation and Oxidizing Polymerization of Unsaturated Compounds)Google Scholar
  14. 14.
    Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T., Gordon, M.S., Jensen, J.H., Koseki, S., Matsunada, N., Nguyen, K.A., Su, S.J., Windus, T.L., Dupuis, M., Montgomery, J.A. 1993J. Comput. Chem.141347Google Scholar
  15. 15.
    Lias, G.G., Liebman, J.F., Levin, R.D., Kafafi, S.A. 1994NIST Standard Reference Database 19A. Positive Ion Energetics. Version 2.02National Institute of Standards and TechnologyGaithersburgGoogle Scholar
  16. 16.
    Gordon, J.G., Ford, R.A. 1972The Chemist’s CompanionWileyNew YorkGoogle Scholar

Copyright information

© MAIK “Nauka/Interperiodica” 2004

Authors and Affiliations

  • E. M. Chainikova
    • 1
  • S. L. Khursan
    • 2
  • R. L. Safiullin
    • 1
  1. 1.Institute of Organic Chemistry, Ufa Scientific CenterRussian Academy of SciencesBashkortostanRussia
  2. 2.Bashkortostan State UniversityBashkortostanRussia

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