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Org. Synth. 1962, 42, 14
DOI: 10.15227/orgsyn.042.0014
2-ALLYLCYCLOHEXANONE
[Cyclohexanone, 2-allyl-]
Submitted by W. L. Howard and N. B. Lorette1.
Checked by Melvin S. Newman and W. S. Gaugh.
1. Procedure
A solution of 196 g. (1 mole) of cyclohexanone diallyl acetal (Note 1), 150 g. of toluene, and 0.10 g. of p-toluenesulfonic acid is distilled through a good fractionating column (Note 2). In about 3 hours, 110 g. of distillate boiling at 91–92° (Note 3) is obtained and the temperature in the head then rises abruptly. The residue in the distilling flask is cooled and washed with 5 ml. of aqueous potassium carbonate to remove the acid. The remaining solution is passed through a filter containing anhydrous powdered magnesium sulfate and returned to the still. Most of the remaining toluene is removed by distillation at 100 mm. pressure (b.p. 52°). The receiver is changed, the pressure is reduced to 15 mm., and the last of the toluene is collected in a cold trap. The residual oil is rapidly vacuum-distilled to separate the product from a higher-boiling residue. Redistillation yields 117–126 g. (85–91%) of 2-allylcyclohexanone, b.p. 86–88°/15 mm., nD25 1.4670.
2. Notes
1. The preparation of cyclohexanone diallyl acetal is described on p. 292.
2. A 14-in. helices-packed column is sufficient.
3. This distillate is the azeotrope of toluene and allyl alcohol whose composition is about 50% allyl alcohol by weight.2
3. Discussion
2-Allylcyclohexanone has been prepared from the sodium derivative of cyclohexanone by alkylation with allyl bromide3 or with allyl iodide,4 and by ketonic hydrolysis of ethyl 1-allyl-2-ketocyclohexanecarboxylate.5,6
4. Merits of Preparation
This procedure, when combined with the preparation of allyl ketals (p. 292), provides a general method for obtaining allyl substitution alpha to a carbonyl group. A discussion of some of these applications, as well as the vinyl allyl ether rearrangement which is involved, has been given by Hurd and Pollack.7 Also, the procedure can be repeated to allow the introduction of more than one allyl group.

References and Notes
  1. The Dow Chemical Company, Texas Division, Freeport, Texas.
  2. L. H. Horsley and co-workers, Advances in Chem. Ser., No. 6, Azeotropic Data, American Chemical Society, Washington, 1955, p. 83.
  3. C. A. VanderWerf and L. V. Lemmerman, Org. Syntheses Coll. Vol. 3, 44 (1955).
  4. R. Cornubert, Ann. Chim., [9] 16, 145 (1921).
  5. A. C. Cope, K. E. Hoyle, and D. Heyl, J. Am. Chem. Soc., 63, 1848 (1941).
  6. R. Grëwe, Ber., 76, 1075 (1943).
  7. C. D. Hurd and M. A. Pollack, J. Am. Chem. Soc., 60, 1905 (1938).

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

sodium derivative of cyclohexanone

potassium carbonate (584-08-7)

Allyl bromide (106-95-6)

Allyl alcohol (107-18-6)

allyl iodide (556-56-9)

toluene (108-88-3)

magnesium sulfate (7487-88-9)

2-Allylcyclohexanone,
Cyclohexanone, 2-allyl- (94-66-6)

ethyl 1-allyl-2-ketocyclohexanecarboxylate

Cyclohexanone diallyl acetal (53608-84-7)

p-toluenesulfonic acid (104-15-4)