Org. Synth. 1936, 16, 39
DOI: 10.15227/orgsyn.016.0039
[Enanthic acid]
Submitted by John R. Ruhoff
Checked by C. R. Noller and M. Patt.
1. Procedure
In a 5-l. flask, fitted with a mechanical stirrer and cooled in an ice bath, are placed 2.7 l. of water and 350 cc. (644 g.) of concentrated sulfuric acid (sp. gr. 1.84). When the temperature has fallen to 15°, 342 g. (403 cc., 3 moles) of heptaldehyde (Note 1) is added, followed by 340 g. (2.15 moles) of potassium permanganate in 15-g. portions. The permanganate is added at such a rate that the temperature does not rise above 20° (Note 2). When the addition of the permanganate is complete, sulfur dioxide is passed through the solution until it becomes clear (Note 3). The oily layer is separated, washed once with water, and distilled from a modified Claisen flask having a 30-cm. fractionating side arm. The fore-runs are separated from any water and distilled again; this is followed by a redistillation of the high-boiling fractions. The yield of material boiling at 159–161°/100 mm. is 296–305 g. (76–78 per cent of the theoretical amount) (Note 4). This product is sufficiently pure for many purposes; titration indicates a purity of 95–97 per cent.
For further purification the product is dissolved in a solution of 140 g. (3.5 moles) of sodium hydroxide in 700 cc. of water and steam-distilled from a 2-l. flask until a test portion of the distillate is free of oil. The solution remaining in the flask is cooled to room temperature and acidified with 375 cc. (4.5 moles) of concentrated hydrochloric acid. The heptanoic acid is separated and distilled from a Claisen flask with fractionating side arm. The recovery of acid boiling at 155–157°/80 mm. is 85–90 per cent of the weight of impure material used. Titration indicates it to be 100 per cent pure.
2. Notes
1. Freshly distilled heptaldehyde boiling at 85.5–87.5°/90 mm. was used.
2. The stirring must be vigorous. About two hours is required for the addition of the permanganate.
3. Sulfur dioxide, in the presence of sulfuric acid, reduces the precipitated manganese dioxide to the soluble sulfate; the removal of this large quantity of flocculent material greatly facilitates separation of the heptanoic acid. The addition of sulfur dioxide requires about two hours; an excess is to be avoided. Sodium bisulfite may be used if sulfur dioxide is not available.
4. Occasionally the heptanoic acid has a yellow color which cannot be removed by fractionation.
3. Discussion
Heptanoic acid has been prepared by the oxidation of heptaldehyde with nitric acid,1 with potassium permanganate in alkaline aqueous solution2 or in acetone solution,3 or with potassium dichromate and sulfuric acid;4 and by carbonating the reaction product of sodium and 1-chlorohexane.5

References and Notes
  1. Tilley, Ann. 67, 107 (1848); Mehlis, ibid. 185, 360 (1877); Krafft, Ber. 15, 1717 (1882).
  2. Fournier, Bull. soc. chim. (4) 5, 921 (1909).
  3. Rogers, J. Am. Pharm. Assoc. 12, 503 (1923) [C. A. 18, 152 (1924)].
  4. Grimshaw and Schorlemmer, Ann. 170, 141 (1873).
  5. Morton, LeFevre, and Hechenbleikner, J. Am. Chem. Soc. 58, 754 (1936).

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

sulfuric acid (7664-93-9)

hydrochloric acid (7647-01-0)

sodium hydroxide (1310-73-2)

nitric acid (7697-37-2)

potassium permanganate (7722-64-7)

sulfur dioxide (7446-09-5)

sodium bisulfite (7631-90-5)

acetone (67-64-1)

sodium (13966-32-0)

manganese dioxide (1313-13-9)

potassium dichromate (7778-50-9)

Enanthic acid,
Heptanoic acid,
n-HEPTANOIC ACID (111-14-8)

1-chlorohexane (544-10-5)

heptaldehyde (111-71-7)