Organic Syntheses, Coll. Vol. 4, p.755 (1963); Vol. 33, p.68 (1953).
Caution! This preparation should be conducted in a hood
to avoid exposure to ammonia
A solution of sodium amide in liquid ammonia
is prepared according to a procedure previously described (Note 1)
in a 3-l. three-necked round-bottomed flask
equipped with a cold-finger condenser
(cooled with Dry Ice) attached through a soda-lime tower to a gas-absorption trap
a mercury-sealed stirrer
, and an inlet tube
. Anhydrous liquid ammonia (1 l.)
is introduced from a commercial cylinder through the inlet tube, and 1 g. of hydrated ferric nitrate
is added, followed by 80.5 g. (3.5 g. atoms) of clean, freshly cut sodium (Note 1)
and (Note 2)
. The inlet tube is replaced with a 250-ml. dropping funnel
, and the mixture is stirred until all the sodium
is converted into sodium amide
, after which 120.5 g. (1 mole) of tetrahydrofurfuryl chloride3 (Note 3)
is added over a period of 25 to 30 minutes. The mixture is stirred for an additional period of 1 hour, after which 177 g. (3.3 moles) of solid ammonium chloride
is added in portions at a rate that permits control of the exothermic reaction. The flask is allowed to stand overnight in the hood while the ammonia
evaporates. The residue is extracted thoroughly with ten 250-ml. portions of ether
, which are decanted through a Büchner funnel (Note 4)
. The ether
is distilled, and the residue is fractionated at a reflux ratio of about 5 to 1, through a column containing a 20-cm. section packed with glass helices
yielding 63–71 g.
) of 4-pentyn-1-ol
, b.p. 70–71° /29 mm.
1.4443 (Note 5)
More liquid ammonia
should be added through the inlet tube if vaporization reduces the liquid volume to less than 750 ml.
extraction of the solid must be thorough or the yield will be reduced. A large Soxhlet extractor
may be used if desired.
Others have reported b.p. 154–155°
A sample purified through the silver derivative had b.p. 77° /37 mm.
1.4464. The α-naphthylurethan of 4-pentyn-1-ol
crystallized as needles from 60–80° petroleum ether
; m.p. 79–80°.
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