Organic Syntheses, Coll. Vol. 3, p.48 (1955); Vol. 21, p.8 (1941).
In a 2-l. round-bottomed flask
, bearing a reflux condenser
protected by a calcium chloride tube
, are placed 64 g. (2.37 gram atoms) of aluminum
shavings, 200 g. (254 ml., 2.7 moles) of dry tert-butyl alcohol
, and 5–10 g. of aluminum tert-butoxide (Note 1)
. After the mixture is heated to boiling on a steam bath
, approximately 0.4 g. of mercuric chloride
is added followed by vigorous shaking (Note 2)
. As the heating is continued the color of the reaction mixture gradually changes from clear to milky to black, and hydrogen
is evolved. When the mixture has become black, the heating is interrupted.
After the reaction has been allowed to proceed for an hour without heating, an additional 244 g. (309 ml., 3.3 moles) of dry tert-butyl alcohol (total quantity, 6 moles)
and 200 ml. of dry benzene
are added. The reaction will again set in upon gentle heating and will continue vigorously without further heating. After about 2 hours the reaction subsides and the mixture is refluxed for about 10 hours.
The solvent is removed by distillation from the steam bath, the final traces under 10–30 mm. pressure. The flask is allowed to cool with a calcium chloride tube attached, and the product is crushed with a spatula and transferred to bottles sealed against moisture. The yield is 394–418 g. (80–85%) of a white or slightly gray solid.
The use of larger amounts of mercuric chloride
increases the difficulty of getting the final product free from color. This difficulty may be avoided by previously amalgamating the aluminum
The mixture is shaken to distribute the mercuric chloride
and thus aid in an even amalgamation of the aluminum
The small amount of water introduced with the undried ether
forms aluminum hydroxide
which aids in the precipitation of the black suspended material. Shaking is essential to obtain the hydroxide formation throughout the solution.
The centrifuging may be carried out in 250-ml. stoppered bottles
at 2000 r.p.m. After centrifuging, the solution should be colorless or light tan. If it is still dark in color another 25-ml. portion of undried ether
should be added and the centrifuging repeated.
This preparation is referenced from:
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