Russian Chemical Bulletin

, Volume 49, Issue 8, pp 1332–1337 | Cite as

Oxidation of alcohols by dimethyldioxirane

  • S. A. Grabovskii
  • E. S. Suvorkina
  • N. N. Kabal'nova
  • S. L. Khursan
  • V. V. Shereshovets
Physical Chemistry

Abstract

The kinetics of oxidation of a series of monoatomic alcohols (methanol, 2-propanol, 2-butanol, 2-methyl-1-propanol, 2-chloroethanol, 1,3-dichloro-2-propanol, benzyl alcohol), hydroxyacetic acid, and 1,3-butandiol (ROH) by dimethyldioxirane (1) was studied. The reaction kinetics obeys the second order equationw=k[ROH][1]. The rate constants were measured in the range of 7–50†C, and the activation parameters were found. To describe the reaction rate constants as a function of the ROH structure, the two-parametric Taft equation was used, which takes into account both the polar and resonance substituent effects. Alcohol oxidation produces the corresponding carbonyl compounds,viz., ketones from secondary alcohols and aldehydes from primary alcohols, in yields of at least 80%. The results were explained by the competition of the molecular (oxenoid) and radical mechanisms. The introduction of electron-withdrawing substituents into the alcohol molecule increases the contribution of the radical channel of the reaction.

Key words

dimethyldioxirane alcohols rate constants free radicals 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    R. Mello, L. Cassidei, M. Fiorentino, C. Fusco, W. Hummer, V. Jager, and R. Curci,J. Am. Chem. Soc., 1991,113, 2205.CrossRefGoogle Scholar
  2. 2.
    F. Kovac and A. L. Baumstark,Tetrahedron Lett., 1994,35, 8754.CrossRefGoogle Scholar
  3. 3.
    R. Curci, L. D'Accolti, A. Detomaso, and C. Fusco,Tetrahedron Lett. 1993,34, 4559.CrossRefGoogle Scholar
  4. 4.
    L. D'Accolti, A. Detomasco, C. Fusco, A. Rosa, and R. Curci,J. Org. Chem., 1993,58, 3600.CrossRefGoogle Scholar
  5. 5.
    P. Bovicelli, A. Sanetti, and P. Lupattelli,Tetrahedron, 1996,52, 10969.CrossRefGoogle Scholar
  6. 6.
    W. Adam, C. R. Saha-Moller, and C. -C. Zhao,Tetrahedron: Asymmetry 9, 1998, 4117.CrossRefGoogle Scholar
  7. 7.
    W. Adam and L. Hadjiarapoglou,Top. Curr. Chem., 1993,164, 45.Google Scholar
  8. 8.
    R. W. Murray and R. Jeyaraman,J. Org. Chem., 1985,50, 2847.CrossRefGoogle Scholar
  9. 9.
    Laboratorni Technika Organiké Chemie, Ed. B. Keil, Nakladatelsti Ceskoslovenske Akademie ved, Praha, 1963, 751 pp.Google Scholar
  10. 10.
    D. V. Kazakov, A. I. Voloshin, V. P. Kazakov, V. V. Shereshovets, and N. N. Kabal'nova,Khimiya i khemilyuminestsentsiya dioksiranov [Chemistry and Chemiluminescense of Dioxiranes]. Nauka, Moscow, 1999, 165 pp. (in Russian).Google Scholar
  11. 11.
    V. B. Kogan, V. M. Fridman, and V. V. Kafarov,Spravochnik po rastvorimosti [Handbook on Solubility], Izd-vo Akad. Nauk SSSR, Moscow, 1961,1, Book 1 (in Russian).Google Scholar
  12. 12.
    Yu. A. Zhdanov and V. I. Minkin,Korrelyatsionnyi analiz v organicheskoi khimii [Correlation Analysis in Organic Chemistry], Izd-vo Rostovskogo Univ., Rostov, 1966, 490 pp. (in Russian).Google Scholar
  13. 13.
    R. A. Jackson,Introduction to the Study of Organic Reactions Mechanism, Eds., R. W. Atlins, J. S. E. Holker, and A. K. Holliday, Clarendon Press, Oxford, 1972, 192 pp.Google Scholar
  14. 14.
    F. Schwager, E. Marand, and R. M. Davis,J. Phys. Chem., 1996,100, 19268.CrossRefGoogle Scholar
  15. 15.
    N. M. Emanuel', G. E. Zaikov, and Z. K. Maizus,Rol'sredy v radikal'no-tsepnykh reaktsiyakh okisleniya organicheskikh soedinenii [The Role of the Medium in the Radical-Chain Oxidation Reactions of Organic Compounds], Nauka, Moscow, 1973, 279 pp. (in Russian).Google Scholar
  16. 16.
    I. B. Afanas'ev,Zh. Org. Khim., 1975,11, 1146 [J. Org. Chem. USSR, 1975,11 (Engl. Transl.)].Google Scholar
  17. 17.
    A. L. Baumstark, F. Kovac, and P. C. Vasaquez,Can. J. Chem., 1999,77, 308.CrossRefGoogle Scholar
  18. 18.
    E. T. Denisov,Kinetika gomogennykh khimicheskikh reaktsii [Kinetics of Homogeneous Chemical Reactions], Vyssh. Shkola, Moscow, 1978, 367 pp. (in Russian).Google Scholar
  19. 19.
    G. V. Shustov and A. Rauk,J. Org. Chem., 1998,63, 5413.CrossRefGoogle Scholar
  20. 20.
    R. W. Murray and H. Gu,J. Phys. Org. Chem., 1996,9, 751.CrossRefGoogle Scholar
  21. 21.
    I. B. Afanas'ev,Int. J. Chem. Kin. 1981,13, 173.CrossRefGoogle Scholar
  22. 22.
    D. Cremer, E. Kraka, and P. G. Szalay,Chem. Phys. Lett., 1998,292, 97.CrossRefGoogle Scholar
  23. 23.
    Ya. Yu. Akhadov,Dielectricheskie svoistva binarnykh rastvorov [Dielectric Properties of Binary Solutions], Nauka, Moscow, 1977, 345 pp. (in Russian).Google Scholar
  24. 24.
    E. G. E. Hawkins,Organic Peroxides. Their Formation and Reactions, F. F. Spon Ltd., London, 1961.Google Scholar
  25. 25.
    D. V. Kazakov, N. N. Kabal'nova, S. L. Khursan, and V. V. Shereshovetz,Izv. Akad. Nauk. Ser. Khim., 1997, 694 [Russ. Chem. Bull. 1997,46, 663 (Engl. Transl.)].Google Scholar

Copyright information

© Kluwer Academic/Plenum Publishers 2000

Authors and Affiliations

  • S. A. Grabovskii
    • 1
  • E. S. Suvorkina
    • 1
  • N. N. Kabal'nova
    • 1
  • S. L. Khursan
    • 1
  • V. V. Shereshovets
    • 1
  1. 1.Institute of Organic ChemistryUfa Research Center of the Russian Academy of SciencesUfaRussian Federation

Personalised recommendations