Russian Journal of Organic Chemistry

, Volume 46, Issue 10, pp 1493–1502 | Cite as

Rearrangements and Hydration of 2-Ethynylisoborneol and 2-Ethynylisocamphanol

  • S. S. Koval’skaya
  • N. G. Kozlov
  • E. A. Dikusar
Review

Abstract

The reaction of 2-ethynylisoborneol with acetic acid in the presence of boron trifluoride-diethyl ether complex gave 4-ethynylisobornyl acetate as a result of successive skeletal rearrangements. Under the Kucherov reaction conditions 2-ethynylisoborneol underwent Meyer—Schuster rearrangement leading to (2-bornylidene)acetaldehyde. The hydration product of 2-ethynylisoborneol, 2-acetylisoborneol, was obtained by the action of mercury(II) acetate in dioxane under mild conditions. The Nieuwland reaction of 2-ethynylisoborneol afforded 4-acetylisoborneol acetate. 2-Ethynylisocamphanol in the presence of formic acid gave rise to a mixture of Rupe and Meyer—Schuster rearrangement products, stereoisomeric 2-(isocamphylidene)acetaldehydes and 2-acetylisocamphene. Mixtures of acetyl-substituted acetates having a camphane, isocamphane, and bicyclo[3.2.1]octane skeleton were obtained in the reaction with acetic acid in the presence of BF3-Et2O. Under the Nieuwland reaction conditions 2-ethynylisocamphanol underwent hydration and rearrangement with ring expansion, yielding a mixture of endo-2-hydroxy-2,6,6,7-tetramethylbicyclo[3.2.1]octan-3-one and the corresponding acetate.

Keywords

Boron Trifluoride Acetoxy Group Hydroxy Ketone Acetylenic Alcohol Isoborneol 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Bondar’, N.F., Koval’skaya, S.S., Skupskaya, R.V., Pashkovskii, F.S., Dikusar, E.A., Kozlov, N.G., and Lakhvich, F.A., Russ. J. Org. Chem., 2001, vol. 37, p. 23.CrossRefGoogle Scholar
  2. 2.
    Bondar’, N.F., Koval’skaya, S.S., Skupskaya, R.V., Pashkovskii, F.S., Dikusar, E.A., Kozlov, N.G., and Lakhvich, F.A., Russ. J. Org. Chem., 2000, vol. 36, p. 1607.Google Scholar
  3. 3.
    Koval’skaya, S.S., Kozlov, N.G., and Dikusar, E.A., Russ. J. Org. Chem., 2009, vol. 45, p. 185.CrossRefGoogle Scholar
  4. 4.
    Koval’skaya, S.S., Kozlov, N.G., and Dikusar, E.A., Russ. J. Org. Chem., 2010, vol. 46, p. 1121.CrossRefGoogle Scholar
  5. 5.
    Hasbrouch, R.W. and Andersen, A.D., J. Org. Chem., 1973, vol. 38, p. 2103.CrossRefGoogle Scholar
  6. 6.
    Koval’skaya, S.S., Kozlov, N.G., and Dikusar, E.A., Russ. J. Org. Chem., 2000, vol. 36, p. 379.Google Scholar
  7. 7.
    Baer, H.H., Kienzle, F., and Rajabalee, F., Can. J. Chem., 1968, vol. 46, p. 80.CrossRefGoogle Scholar
  8. 8.
    Kozlov, N.G., Koval’skaya, S.S., and Kalechits, G.V., Russ. J. Gen. Chem., 1993, vol. 63, p. 785.Google Scholar

Copyright information

© Pleiades Publishing, Ltd. 2010

Authors and Affiliations

  • S. S. Koval’skaya
    • 1
  • N. G. Kozlov
    • 1
  • E. A. Dikusar
    • 1
  1. 1.Institute of Physical Organic ChemistryNational Academy of Sciences of BelarusMinskBelarus

Personalised recommendations