Org. Synth. 1928, 8, 50
Submitted by James F. Norris and Alanson W. Olmsted.
Checked by Henry Gilman and L. L. Heck.
In a 500-cc. separatory funnel are placed 74 g. (95 cc., 1 mole) of tert.-butyl alcohol (Note 1) and 247 cc. (3 moles) of c.p. concentrated hydrochloric acid (sp. gr. 1.19). After shaking, the layers are allowed to separate (fifteen to twenty minutes) and the upper layer is drawn off and washed first with a 5 per cent sodium bicarbonate solution, then with water until neutral to moist litmus paper (Note 2) and (Note 3). The chloride is treated with 10 g. of calcium chloride and shaken thoroughly, then transferred to a 125-cc. distilling flask. It is then distilled, using a long water condenser. The fraction boiling at 49.5–52° weighs 72–82 g. (78–88 per cent of the theoretical amount).
As it is difficult to prepare tert.-butyl alcohol
free from water, 84 g. of the constant-boiling mixture of the alcohol and water
can be used. This mixture boils at 80°, contains 88.24 per cent alcohol
when the distillation is carried out at 760 mm., and can be readily obtained by distilling a sample of the dilute alcohol.
The chloride is very slowly hydrolyzed by cold water.
It is suggested that calcium chloride
be added to the saturation point after the tert.-butyl alcohol
and hydrochloric acid
are mixed in order to salt out the tert.-butyl chloride
and to concentrate the hydrochloric acid
(W. W. Hartman, private communication).
can be prepared by passing hydrogen chloride
into the alcohol
kept cold in a freezing mixture;1
by distilling a mixture of the alcohol
and a large excess of concentrated hydrochloric acid
and from the alcohol
and thionyl chloride
Procedures have also been described for the isomerization of isobutyl chloride
to tert.-butyl chloride
and for the preparation of tert.-butyl chloride
by the catalyzed addition of hydrogen chloride
to the butene
fraction from cracking gases.5
This preparation is referenced from:
Chemical Abstracts Nomenclature (Collective Index Number);
calcium chloride (10043-52-4)
hydrochloric acid (7647-01-0)
thionyl chloride (7719-09-7)
sodium bicarbonate (144-55-8)
tert.-BUTYL CHLORIDE (507-20-0)
isobutyl chloride (513-36-0)
tert.-butyl alcohol (75-65-0)
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