A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1936, 16, 41
DOI: 10.15227/orgsyn.016.0041
Submitted by G. Bryant Bachman
Checked by C. R. Noller and W. S. Woon.
1. Procedure
In a 2-l. three-necked, round-bottomed flask, fitted with a liquid-sealed mechanical stirrer, a 250-cc. dropping funnel, and a reflux condenser to which is attached a calcium chloride tube, are placed 30 g. (1.25 gram atoms) of magnesium turnings, 50 cc. of dry ether, and a small crystal of iodine. Stirring is started, and 5 cc. (6 g.) of n-amyl bromide is added (Note 1). As soon as the reaction has started, 300 cc. of dry ether is added and then, more slowly, a solution of 183 g. (total, 189 g.; 1.25 moles) of n-amyl bromide in 150 cc. of dry ether. If external cooling is provided, all the alkyl halide may be added within half an hour; the solution is refluxed gently for another half-hour to complete the reaction. The heat is removed, the flask cooled to 50°, and 148 g. (1 mole) of ethyl orthoformate (Org. Syn. Coll. Vol. I, 1941, 258) is added during the course of fifteen to twenty minutes. The mixture is refluxed for six hours (Note 2); at the end of this time the condenser is arranged for distillation and the ether is removed completely with the aid of a steam bath.
The reaction mixture is cooled and treated carefully with 750 cc. of chilled 6 per cent hydrochloric acid. The contents of the flask are kept cool by the occasional addition of ice while the acid is being introduced. As soon as all the solid has dissolved (Note 3), the upper oily layer of hexaldehyde acetal is separated. The acetal is hydrolyzed by distilling it with a solution of 100 g. (55 cc.) of concentrated sulfuric acid in 700 cc. of water. The free aldehyde distils rapidly, and the distillation is complete when a sample of fresh distillate contains 5 per cent or less of immiscible oil. The distillate is collected in a solution of 100 g. (1 mole) of sodium bisulfite in 300 cc. of water. The mixture is shaken vigorously for several minutes; the oily layer remaining undissolved in the bisulfite solution is principally n-amyl alcohol and is discarded. To remove the remainder of the amyl alcohol and other impurities the bisulfite solution is steam-distilled until 200 cc. of distillate has been collected.
The residual aldehyde-bisulfite solution is cooled to 40–50°, a suspension of 80 g. of sodium bicarbonate in 200 cc. of water is added carefully, and the free aldehyde is removed by steam distillation. The upper layer of the distillate is separated, washed with three 50-cc. portions of water (Note 4), dried with 20 g. of anhydrous sodium sulfate, and distilled through a 20-cm. column. The yield of n-hexaldehyde b.p. 126–129° , is 45–50 g. (45–50 per cent of the theoretical amount).
2. Notes
1. The n-amyl bromide was prepared according to the general procedure in Org. Syn. Coll. Vol. I, 1941, 25, and distilled at 127–129°.
2. Sometimes a white precipitate begins to form immediately, but more often it does not appear until after twenty to thirty minutes of refluxing. If this period of heating is materially decreased, a sudden exothermic reaction occurs when the ether is removed and the yield may be seriously reduced. Longer periods of heating do not increase the yield of hexaldehyde.
3. Solution takes place slowly and is hastened considerably by the use of a mechanical stirrer.
4. The aldehyde dissolved by the wash water may be recovered by steam distillation, but this is scarcely worth while since hexaldehyde is not very soluble in water.
3. Discussion
Hexaldehyde has been prepared from caproic acid by passing it over zinc dust at 300°,1 by reaction with amylene at 300° in the presence of thorium oxide,2 by passing it over manganous oxide at 300–360° with two volumes of formic acid,3 and by distillation of the calcium salt with calcium formate.4 It has also been prepared by heating α-hydroxyheptoic acid or, better, α-acetoxyheptoic acid,5 and by the procedure described above.6

References and Notes
  1. Mailhe, Chem. Ztg. 33, 243 (1909).
  2. Mailhe, ibid. 34, 1174 (1910).
  3. Sabatier and Mailhe, Compt. rend. 158, 986 (1914).
  4. Lieben and Janecek, Ann. 187, 130 (1877).
  5. Bagard, Bull. soc. chim. (4) 1, 313 (1907).
  6. Bachman, J. Am. Chem. Soc. 55, 4281 (1933).

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

hexaldehyde acetal


α-hydroxyheptoic acid

α-acetoxyheptoic acid


sulfuric acid (7664-93-9)

hydrochloric acid (7647-01-0)

ether (60-29-7)

sodium bicarbonate (144-55-8)

magnesium turnings (7439-95-4)

sodium sulfate (7757-82-6)

formic acid (64-18-6)

sodium bisulfite (7631-90-5)

thorium oxide

iodine (7553-56-2)

zinc (7440-66-6)

Caproic acid (142-62-1)

Ethyl orthoformate


amyl alcohol,
n-amyl alcohol (71-41-0)


manganous oxide

calcium formate (544-17-2)

n-amyl bromide (110-53-2)