Org. Synth. 1928, 8, 50
DOI: 10.15227/orgsyn.008.0050
tert.-BUTYL CHLORIDE
[Propane, 2-chloro-2-methyl-]
Submitted by James F. Norris and Alanson W. Olmsted.
Checked by Henry Gilman and L. L. Heck.
1. Procedure
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).
2. Notes
1.
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.
2.
The chloride is very slowly hydrolyzed by cold water.
3.
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).
3. Discussion
tert.-Butyl chloride 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;
2 and from the
alcohol and
thionyl chloride.
3 Procedures have also been described for the isomerization of
isobutyl chloride to
tert.-butyl chloride,
4 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:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
alcohol (64-17-5)
calcium chloride (10043-52-4)
hydrogen chloride,
hydrochloric acid (7647-01-0)
thionyl chloride (7719-09-7)
sodium bicarbonate (144-55-8)
Propane, 2-chloro-2-methyl-,
tert.-BUTYL CHLORIDE (507-20-0)
isobutyl chloride (513-36-0)
butene (106-98-9)
tert.-butyl alcohol (75-65-0)
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