Organic Syntheses, Coll. Vol. 2, p.323 (1943); Vol. 16, p.41 (1936).
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
, is 45–50 g.
per cent of the theoretical amount).
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
Solution takes place slowly and is hastened considerably by the use of a mechanical stirrer.
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.
has been prepared from caproic acid
by passing it over zinc dust
by reaction with amylene
at 300° in the presence of thorium oxide
by passing it over manganous oxide
at 300–360° with two volumes of formic acid
and by distillation of the calcium salt with calcium formate
It has also been prepared by heating α-hydroxyheptoic acid
or, better, α-acetoxyheptoic acid
and by the procedure described above.6
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