A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1955, 35, 1
DOI: 10.15227/orgsyn.035.0001
[Ketone, 1-hydroxycyclohexyl methyl]
Submitted by Gardner W. Stacy and Richard A. Mikulec1.
Checked by John C. Sheehan, George A. Mortimer, and Norman A. Nelson.
1. Procedure
In a 1-l. three-necked round-bottomed flask, equipped with a sealed stirrer, a reflux condenser, a thermometer, and a dropping funnel, is dissolved 5 g. of mercuric oxide (Note 1) in a solution of 8 ml. of concentrated sulfuric acid and 190 ml. of water. The solution is warmed to 60°, and 49.7 g. (0.40 mole) of 1-ethynylcyclohexanol (Note 2) is added dropwise over a period of 1.5 hours. After the addition has been completed, the reaction mixture is stirred at 60° for an additional 10 minutes and allowed to cool. The green organic layer which settles is taken up in 150 ml. of ether, and the aqueous layer is extracted with four 50-ml. portions of ether (Note 3). The combined ethereal extracts are washed with 100 ml. of saturated sodium chloride solution (Note 4) and dried over anhydrous sodium sulfate. The drying agent is removed, the ether is evaporated, and the residue is distilled under reduced pressure through a 15-cm. column packed with glass helices. The 1-acetylcyclohexanol is collected at 92–94°/15 mm. as a colorless liquid, n25D 1.4670, d254 1.0248 (Note 5). The yield is 37–38 g. (65–67%).
2. Notes
1. Mallinckrodt mercuric oxide red (analytical reagent or N.F. 1x grade) was used.
2. 1-Ethynylcyclohexanol is available commercially. It may be prepared as reported by Saunders.2
3. To facilitate subsequent extractions, the solid material remaining after separation of as much of the aqueous phase as possible should be removed by gentle suction filtration and washed with 25 ml. of ether.
4. The sodium chloride solution removes the green color from the ether extract, leaving a yellow solution.
5. The checkers found b.p. 100°/21 mm., nD25 1.4662–1.4665, d425 1.0235–1.0238. Others have reported b.p. 92–94°/12 mm., d020 1.0256;3 b.p. 91°/11 mm., nD11 1.4726, d411 1.1033;4 b.p. 88.0–88.6°/12 mm., nD28 1.4712.5
Establishing a criterion for the purity of the product is of particular importance because of the known tendency of ethynylcarbinols to undergo rearrangement.5,6 The authors have reported that consecutive small fractions of the distillate possess a constant boiling point and refractive index. Furthermore, representative fractions, treated with periodic acid and subsequently with 2,4-dinitrophenylhydrazine, give cyclohexanone 2,4-dinitrophenylhydrazone in 83% over-all yield in a high state of purity.
3. Discussion
1-Acetylcyclohexanol has been prepared by the hydrolysis of 1-bromo-1-acetylcyclohexane3 and of 1-acetoxy-1-acetylcyclohexane oxime,7 by the hydration of 1-ethynylcyclohexanol,4,5,8,9,10,11,12 by the treatment of 1-hydroxycyclohexanecarboxylic acid with methyllithium13,14 and by the hydrolysis of 1-(isopropoxyethoxy)-1-(1-iminoethyl)cyclohexane.15 and 1-(2-tetrahydropyranoxy)-1-(1-iminoethyl)cyclohexane.16 The present procedure is based upon that of Stacy and Mikulec for the preparation of 1-acetylcyclopentanol.6

References and Notes
  1. State College of Washington, Pullman, Washington.
  2. Org. Syntheses Coll. Vol. 3, 416 (1955).
  3. Favorskii, J. Russ. Phys. Chem. Soc., 44, 1339 (1912) [C. A., 7, 984 (1913)].
  4. Locquin and Wouseng, Compt. rend., 176, 516 (1923).
  5. Newman, J. Am. Chem. Soc., 75, 4740 (1953).
  6. Stacy and Mikulec, J. Am. Chem. Soc., 76, 524 (1954).
  7. Wallach, Ann., 389, 191 (1912).
  8. Bergmann, Brit. pat. 640,477 [C. A., 45, 1622 (1951)]; U. S. pat. 2,560,921 [C. A., 46, 3072 (1952)].
  9. Stacy and Hainley, J. Am. Chem. Soc., 73, 5911 (1951).
  10. Newman (to Ohio State University Research Foundation), U. S. pat. 2,853,520 [C. A., 54, 345 (1960)].
  11. Papa, Ginsberg, and Villani, J. Am. Chem. Soc., 76, 4441 (1954).
  12. Hennion and Watson, J. Org. Chem., 23, 656 (1958).
  13. Billimoria and MacLagan, Nature, 167, 81 (1951); J. Chem. Soc., 1951, 3067.
  14. MacLagan and Billimoria, Brit. pat. 742,571 [C. A., 50, 16845 (1956)].
  15. Tchoubar, Compt. rend., 237, 1006 (1953).
  16. Elphimoff-Felkin, Bull. soc. chim. France, 1955, 784.

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

sulfuric acid (7664-93-9)

ether (60-29-7)

sodium chloride (7647-14-5)

sodium sulfate (7757-82-6)

mercuric oxide (21908-53-2)

2,4-Dinitrophenylhydrazine (119-26-6)

1-Ethynylcyclohexanol (78-27-3)

Ketone, 1-hydroxycyclohexyl methyl (1123-27-9)

periodic acid

cyclohexanone 2,4-dinitrophenylhydrazone (1589-62-4)


1-acetoxy-1-acetylcyclohexane oxime

1-hydroxycyclohexanecarboxylic acid

Methyllithium (917-54-4)