The chromic acid oxidation of aliphatic secondary alcohols—substituent effects and the mechanism

  • N. Venkatasubramanian
  • G. Srinivasan


The mechanism of the chromic acid oxidation of a number of substituted propan-2-ols has been studied in aqueous acetic acid medium. Electron withdrawing substituents retard the reaction considerably while electron-releasing substituents accelerate the reaction. A good correlation exists between the rate and σ* values. The ρ* value is −1.60. The results are interpreted in terms of a rate-determining abstraction of the secondary hydrogen as a hydride anion.


HOAc Benzhydrol Chromic Acid Oxidation Secondary Carbon Atom Secondary Hydrogen 
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  1. 1.
    Stewart, R...Oxidation Mechanisms, Benjamin, W. A., New York, 1964.Google Scholar
  2. 2.
    Waters, W. A...Mechanisms of Oxidation of Organic Compounds, Methuen and Co., Ltd., London, 1964.Google Scholar
  3. 3.
    Wiberg, K. B...Oxidation in Organic Chemistry, Academic Press, N.Y., London, 1965.Google Scholar
  4. 4.
    Westheimer, F. H. and Graham, G. T. E.J. Amer. Chem. Soc., 1958,80, 3030 and references cited therein.CrossRefGoogle Scholar
  5. 5.
    Rocek, J. and Krupicka, J.Collection Czech. Chem. Communs., 1958,23, 2068.Google Scholar
  6. 6.
    Roček, J...Ibid., 1960,25, 1052.Google Scholar
  7. 7.
    Kwart, H. and Francis, P. S.J. Amer. Chem. Soc., 1955,77, 4907.CrossRefGoogle Scholar
  8. 8.
    —..Ibid., 1959,81, 2116.CrossRefGoogle Scholar
  9. 9.
    Stewart, R. and Lee, D. G.Ibid., 1964,86, 3051.Google Scholar
  10. 10.
    —..Can. J. Chem., 1964,42, 439.CrossRefGoogle Scholar
  11. 11.
    Venkatasubramanian, N. and Anantakrishnan, S. V.Proc. Ind. Acad. Sci., 1960,53, 80.Google Scholar
  12. 12.
    Roček, J., Westeimer, F. H., Eschenmoser, A., Moldovanyi, L. and Schreiber, J.Helv. Chim. Acta, 1962,45, 2554.CrossRefGoogle Scholar
  13. 13.
    Wiberg, K.B. and Schafer, H.J. Amer. Chem. Soc., 1967,89, 455.CrossRefGoogle Scholar
  14. 14.
    Stewart, R. and Lee, D. G.J. Org. Chem., 1967,32, 2868.CrossRefGoogle Scholar
  15. 15.
    Venkatasubramanian, N...J. Sci. Industr. Res., 1961,20, 385, 541.Google Scholar
  16. 16.
    Kläning, U...Acta Chem. Scand., 1958,12, 576.CrossRefGoogle Scholar
  17. 17.
    Buncel, L. E. and Bourns, A. N.Can. J. Chem., 1960,38, 2457.CrossRefGoogle Scholar
  18. 18.
    Bell, R. P...Disc. Farad. Soc., 1965,39, 16.CrossRefGoogle Scholar
  19. 19.
    Sundaram, S...Ph.D. Thesis, University of Madras, India, 1967.Google Scholar
  20. 20.
    Venkatasubramanian, N. and Srinivasan, G.Proc. Ind. Acad. Sci., 1967,65, 30.Google Scholar
  21. 21.
    Burstein, S. H. and Ringold, H. J.J. Amer. Chem. Soc., 1967,89, 4722.CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 1970

Authors and Affiliations

  • N. Venkatasubramanian
    • 1
  • G. Srinivasan
    • 1
  1. 1.Department of ChemistryVivekananda CollegeMadras-4

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