Organic Syntheses, Coll. Vol. 3, p.416 (1955); Vol. 29, p.47 (1949).
A rapid stream of dry acetylene
is passed into approximately 1 l. of liquid ammonia
in a 2-l. three-necked flask equipped with a gas inlet tube and a mechanical stirrer
while 23 g. (1 gram atom) of sodium
is added over a period of 30 minutes (Note 1)
and (Note 2)
. The flow of acetylene
is then reduced (Note 3)
, and 98 g. (1 mole) of cyclohexanone
is added dropwise. When this addition, which requires about an hour, is completed, the reaction mixture is allowed to stand for about 20 hours to permit the evaporation of nearly all the ammonia (Note 4)
The solid residue is decomposed by adding approximately 400 ml. of ice and water, and the resulting mixture is carefully acidified with 50% sulfuric acid (Note 5)
. The organic layer is dissolved in 100 ml. of ether
and washed with 50 ml. of brine
. The original aqueous phase and the brine
wash are then extracted with two 50-ml. portions of ether
. The combined ethereal solutions are dried over anhydrous magnesium sulfate
and filtered, and the ether
is distilled. The product is then distilled under reduced pressure through a good column (Note 6)
. The yield of 1-ethynylcyclohexanol
is 81–93 g.
), b.p. 74°/14 mm.
1.4822 (Note 7)
The preparation of sodium acetylide
is based on the procedure of Vaughn, Hennion, Vogt, and Nieuwland.2
The blue color of dissolved sodium
is discharged so rapidly by the acetylene
that it seldom spreads through the entire mixture.
The flow of acetylene
may be terminated before the cyclohexanone
is added. This operation, however, is alleged to increase the formation of glycol.3
If all the ammonia
is allowed to evaporate and the residual solid is exposed to the air the yields may be decreased.
Upwards of 70 ml. is required. The amount depends upon the quantity of ammonia
The submitters and the checkers used a 15-cm. Vigreux column
The product may solidify to a colorless solid, m.p. 30°
This preparation is referenced from:
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