A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1968, 48, 18
DOI: 10.15227/orgsyn.048.0018
[2-Cyclohexen-1-ol, benzoate]
Submitted by Knud Pedersen, Preben Jakobsen, and Sven-Olov Lawesson1.
Checked by R. Schöllhorn and R. Breslow.
1. Procedure
Caution! This reaction should be carried out behind a safety screen. The solvent removal and product distillation steps should also be carried out behind a screen to minimize danger due to contamination of the product with undetected peroxides.
A 250-ml., three-necked, round-bottomed flask equipped with a sealed mechanical stirrer, a reflux condenser, and a pressure-equalizing dropping funnel is set up for conducting a reaction in an atmosphere of nitrogen by fitting into the top of the condenser a T-tube attached to a low-pressure supply of nitrogen and to a mercury bubbler. In the flask are placed 41 g. (0.50 mole) of cyclohexene and 0.05 g. (0.00035 mole) of cuprous bromide, and the mixture is heated in an oil bath at 80–82°. When the temperature of the mixture reaches that of the oil bath, 40 g. (0.21 mole) of t-butyl perbenzoate (Note 1) is added dropwise with stirring over a 1-hour period, during which the color of the now homogeneous solution becomes blue. Stirring and heating are continued for an additional 3.5 hours (Note 2). The cooled reaction mixture is washed with two 50-ml. portions of dilute aqueous sodium carbonate to remove benzoic acid (Note 3). The remaining organic phase is washed with water until neutral and dried over anhydrous sodium sulfate. The excess of cyclohexene is removed by distillation under reduced pressure, and the residue (Note 4) is distilled through a short Vigreux column to give 29–33 g. (71–80%) of 3-benzoyloxycyclohexene, b.p. 97–99° (0.15 mm.), n20D 1.5376–1.5387 (Note 5).
2. Notes
1. t-Butyl perbenzoate is supplied by Lucidol Division, Wallace and Tiernan, Inc., Buffalo 5, New York, or L. Light and Co., Ltd., Colorbrook, Bucks, England. The Lucidol product contains 98% t-butyl perbenzoate.
2. The progress of the reaction can most conveniently be followed by periodic examination of the infrared spectrum of the mixture (νC=O for peroxybenzoate: 1775 cm.−1). After all of the perester has been added, ca. 3 hours is required for its consumption.
3. After acidification of the aqueous phase 1.5–2 g. of benzoic acid can be isolated.
4. It is recommended that an infrared spectrum be run on the residue before the distillation to check for the absence of perester (Note 2).
5. The same yield is obtained when the scale is increased threefold.
3. Discussion
The procedure is that of Kharasch, Sosnovsky, and Yang.2
4. Merits of the Preparation
The reaction described is of considerable general utility for the preparation of benzoyloxy derivatives of unsaturated hydrocarbons.2,3,4,5,6,7,8 Reactions of t-butyl perbenzoate with various other classes of compounds in the presence of catalytic amounts of copper ions produce benzoyloxy derivatives. Thus this reaction can also be used to effect one-step oxidation of saturated hydrocarbons,9,10 esters,5,11 dialkyl and aryl alkyl ethers,12,13,14 benzylic ethers,11,15 cyclic ethers,13,16 straight-chain and benzylic sulfides,12,17,18,19 cyclic sulfides,11,19 amides,11 and certain organosilicon compounds.20 Reviews20,21 of these reactions are available.

References and Notes
  1. Department of Chemistry, University of Aarhus, 8000 Aarhus C., Denmark.
  2. M. S. Kharasch, G. Sosnovsky, and N. C. Yang, J. Am. Chem. Soc., 81, 5819 (1959).
  3. D. B. Denney, D. Z. Denney, and G. Feig, Tetrahedron Lett., No. 15, 19 (1959).
  4. A. L. J. Beckwith and G. W. Evans, Proc. Chem. Soc., 63 (1962).
  5. G. Sosnovsky and N. C. Yang, J. Org. Chem., 25, 899 (1960).
  6. B. Cross and G. H. Whitham, J. Chem. Soc., 1650 (1961).
  7. J. K. Kochi, J. Am. Chem. Soc., 84, 774 (1962).
  8. D. Z. Denney, A. Appelbaum, and D. B. Denney, J. Am. Chem. Soc., 84, 4969 (1962).
  9. M. S. Kharasch and A. Fono, J. Org. Chem., 23, 324 (1958).
  10. T. I. Wang, Ph.D. Thesis, University of Chicago, 1962.
  11. C. Berglund and S.-O. Lawesson, Arkiv Kemi, 20, 225 (1963).
  12. S.-O. Lawesson, C. Berglund, and S. Grönwall, Acta Chem. Scand., 15, 249 (1961).
  13. G. Sosnovsky, Tetrahedron, 13, 241 (1961).
  14. S.-O. Lawesson and C. Berglund, Arkiv Kemi, 17, 465 (1961).
  15. S.-O. Lawesson and C. Berglund, Arkiv Kemi, 16, 287 (1960).
  16. S.-O. Lawesson and C. Berglund, Arkiv Kemi, 17, 475 (1961).
  17. S.-O. Lawesson and C. Berglund, Acta Chem. Scand., 15, 36 (1961).
  18. G. Sosnovsky, Tetrahedron, 18, 15 (1962).
  19. G. Sosnovsky, Tetrahedron, 18, 903 (1962).
  20. G. Sosnovsky and S.-O. Lawesson, Angew. Chem., 76, 218 (1964).
  21. S.-O. Lawesson and G. Schroll, in S. Patai, "The Chemistry of Carboxylic Acids and Esters," Wiley-Interscience, London, 1969, p. 669.

Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

t-butyl perbenzoate

Cyclohexene (110-83-8)

sodium carbonate (497-19-8)

sodium sulfate (7757-82-6)

nitrogen (7727-37-9)

Benzoic acid (65-85-0)

cuprous bromide (7787-70-4)

2-Cyclohexen-1-ol, benzoate (3352-93-0)