A Simple Experiment
Illustrating the Preparation and Properties
of Isobutylene (2-Methylpropene)
CHARLES BARKENBUS and JERRY B. KELLEY
University of Kentucky, Lexington, Kentucky
A LL laboratory manuals of organic chemistry have
an experiment illustrating the preparation and
properties of alkenes and, in the majority of cases, the
alkene made has been ethylene although a few manuals
give directions for making petene-2. In the last few
years isobutylene, because of the ease of polymerization
and alkylation, has become one of the outstanding
compounds of the petroleum industry. For this reason
it bas been thought worth while to substitute this im-
portant alkene for the time-worn examples used in the
average organic laboratory manuals. Isobutylene has
other advantages, such as ease of preparation and
greater reactivity, which make i t superior to ethylene.
Isobntylene bas been made by the dehydration of
tert-butyl alcohol with concentrated sulfuric acid.'
Tertiary butyl alcohol is smoothly dehydrated with 30
per cent sulfuric acid a t 98°C. with no frothing, car-
bonization, or production of sulfur dioxide. Noms2
found that tertiary alcohols do not form alkyl acid sul-
fates with dilute sulfuric acid. Since tert-butyl alcohol
boils a t 82.g°C. it is necessary to use a condenser on the
generator to prevent the rapid volatilization of the alco-
hol. Many variations in the experimental procedure
were tried in an attempt to eliminate the use of a con-
denser but in all cases the loss of tert-butyl alcohol was
too great to conduct the experiment without one.
The following procedure has been used on the lecture
table and by classes in the laboratory, and offers no
difficulty or hazard. The apparatus is simple and the
experiment can be readily carried out in a minimum of
approximately two hours. The wash bottles used were
made from 8-inch test tubes fitted with rubber stoppers
and were furnished the students.
In a 200-ml. round-bottom flask attached to a reflux
condenser were placed 10 ml. of tert-butyl alcohol and 20
ml. of approximately 30 per cent sulfuric acid made by
diluting 7 ml. of 95 per cent sulfuric acid with 14 ml.
of water. The flask is placed in a water bath and the
end of the condenser connected by a bent glass tube and
rubber tubing to a 125-ml. distilling flask which is sur-
rounded with ice. The distilling flask acts as a safety
flask and also condenses some tert-butyl alcohol which
may come over. The side neck of the flask is con-
- all careful attention to details and makes the experiment
~ K I ~ T I A K OG~. ~
B.,KBT
Y ,AL., I . Am. Chem. Sac. 57, 879
(1935).
2 N ~J. F.
~. AND
~ J.~M.~JOUBERT,
, ibid., 49, 873 (1927).
35 6
nected by rubber tubing to an 8-inch test tube wash
bottle containing 10 ml. of acidified dilute potassium
permanganate solution. This solution is made by
diluting 1 ml. of 2 per cent potassium permanganate
solution with 9 ml. of water and adding 1 ml. of 40 per
cent sulfuric acid. This wash bottle is then connected
to another wash bottle surrounded with ice containing
3 ml. of bromine and 5 ml. of water, the water being
added to cut down the volatilization of the bromine. A
delivery tube runs from the outlet of this wash bottle
to a pneumatic trough where samples of the gas can be
collected if desired. While displacing the air in the ap-
paratus a small amount of bromine vapors escape which
are absorbed in the water of the trough. About 30
minutes are required to assemble the apparatus.
The water bath is brought to gentle boiling and a
steady flow of isobutylene is generated. The gas starts
coming off slowly a t 50°C. and at the boiling point of
water a steady flow results. No further attention to
temperature control is necessary, which is a definite
advantage.
About 15 minutes are required to heat the bath, and
a t that time most of the air has been displaced and com-
plete absorption of isobutylene by the two wash bottles
is observed. The potassium permanganate solution is
decolorized in about four minutes and the bromine in
seven minutes. When the bromine is decolorized, the
test tube is replaced by one containing 3 ml. of 95 per
cent sulfuric acid and the gas is allowed to bubble into it
for five minutes. An insoluble layer of di-isobutylene
and higher polymers separates which bas a pronounced
gasoline-like odor. This tube is then replaced by one
containing 3 ml. of 60 per cent sulfuric acid, and the gas
is passed in for 5 minutes. The contents of this tube
when diluted with water have a definite odor of tert-
butyl alcohol. Sufficient isobutylene can still be gen-
erated to collect'several100-ml. bottles for running tests
on inflammability, diffusion, and explosive mixtures
with air.
This experiment well illustrates the ease of dehydrat-
ing tertiary alcohols with dilute sulfuric acid. The
smoothness with which the gas is generated eliminates
especially free of difficulties. The reduction of the per-
(Continued on page 363)
 .-\ SIMI'Lli EXI'EKTlIENT ILLL'STR.YI'IN(; T H E PI<EPAR.ZI'IOS I\NI)
I'ROPliRTIES 01: JSOBL'TYJ.ESli
(Continued from page 356)

manganate ion to the colorless manganous ion vividly
shows the ease of oxidation of alkenes in the cold, and
the formation of the insoluble oil and loss of color in the
bromine tube illustrates clearly the addition type of
reaction. I t is unfortunate that bromine reacts with
isobutylene to give a mixture of mono-, di-, and tri-
substituted bromobutane~.~ For this reason the result-
ing oil cannot be conveniently used for the preparation
of 1,2-dibromo-2-methylpropane.
The polymerization of isobutylene by concentrated
sulfuric acid to di-isobutylene and higher polymers
illustrates the alkylation reaction of the petroleum in- '
dustry, and the pronounced gasoline-like odor as well
XOMAREWSKI,
V., ET AL., I . Am. Chem. Soc., 56,2705 (1934).
as the insolubility in water of the product make this
experiment a simple example of this important indus-
trial reaction. The absorption of isobutylene in dilute
sulfuric acid with the formation of tert-butyl alcohol
illu~tratesthe industrial preparation of alcohols from
alkenes.
Comparison of this reaction with the action of con-
centrated sulfuric acid makes an excellent example of
the effect of conditions on the products formed during a
reaction. This simple experiment along with appropri-
ate questions clearly covers the chemistry of alkenes
and the utilization of this chemistry by the petroleum
industry. Very few experiments are available which
can be run so easily and cheaply and illustrate so many
facts

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