In the Laboratory
A Safe Simple Halogenation Experiment W
Hilton M. Weiss* and Lara Ganz
Department of Chemistry, Bard College, Annandale-on-Hudson, NY 12504
Most introductory organic chemistry courses begin with
the chemistry of alkanes. Their relatively unreactive nature,
however, makes it difficult to find appropriate laboratory
experiments for these early weeks. Many halogenation experi-
ments have been suggested (1), but they often suffer from
the need for complicated techniques or equipment, long
reaction times, or the presence of functional groups that
diminish the relevance of the reaction. In addition, the organic
products of some halogenations are volatile and dangerous.
We have developed a simple halogenation experiment
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that can be performed quickly in an open vessel at room tem-
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perature with visible light. The product is a solid and can be
isolated by a simple filtration, permitting the entire experiment
to be completed within one hour. The reaction is also easily
adapted to microscale. We use NMR in this experiment to
identify the product and to introduce some simple NMR
analysis. The reaction is shown below:
Br2
CH3 CH CH CH3
light
CH3 CH3
Br Br Br
CH3 C CH CH3 + CH3 C C CH3
CH3 CH3 CH3 CH3
The bromination of 2,3-dimethylbutane is performed
with a large excess of hydrocarbon in an open test tube. Be-
cause HBr is generated in the reaction, we have done these
reactions in a well-ventilated hood under a 200-watt light bulb
or outside in an open area under direct sunlight (and careful
supervision). The high selectivity of the bromine atom insures
substitution of the tertiary over the more prevalent primary
hydrogen atoms. The question of monobromination versus
dibromination of the alkane is left for the student to determine
by NMR and melting point. The NMR pattern of an isopro-
pyl group may be found by running a sample of the starting
material. The dibrominated product has a single NMR peak
(δ = 2.02 ppm) and a relatively high melting point deriving
from its highly symmetrical structure and the resulting well-
packed crystal structure.
The requirement for light in these brominations may be
demonstrated by wrapping the reaction vessel with aluminum
foil. The bromine color will remain for hours. The relative
unreactivity of secondary hydrogens may be demonstrated
by using 2,2-dimethylbutane, n-hexane, or cyclohexane as
the alkane. Why the dibrominated product is formed remains
W Supplementary materials for this article are available on JCE
Online at http://JChemEd.chem.wisc.edu/Journal/issues/1999/
Apr/abs534.html.
*Email: weiss@bard.edu .
534 Journal of Chemical Education • Vol. 76 No. 4 April 1999 • JChemEd.chem.wisc.edu
a matter of some conjecture (2), and this open-ended ques-
tion can stimulate student interest.
The reaction may be monitored by gas chromatography,
which will show the initial formation of the monobromo
product followed by its rapid conversion to the dibromo-
hexane. Kinetic modeling of this sequence indicates that the
monobrominated alkane is approximately 103 times as reactive
as the starting dimethylbutane. The high reactivity of the
monobrominated intermediate may also be shown by the
competitive bromination of a 2% solution of 2-bromo-2,3-
dimethylbutane in 3-methylpentane and GC analysis of the
resulting alkyl halide mixture.
Experimental Procedure
WARNING: Bromine causes severe burns and should be
dispensed by the instructor wearing chemical-resistant gloves.
A 10% solution of sodium thiosulfate should be kept nearby
in case of a spill or skin contact. Only after the reaction is
complete (bromine color gone) are students allowed to contact
the reaction vessel. Care must still be given to the remaining
HBr fumes and the alkyl halides produced in the reaction.
Into a wide 50-mL test tube or centrifuge tube is placed
10 mL of 2,3-dimethylbutane followed by 1.0 mL of bromine.
Care is needed in handling bromine; we have the instructor
dispense the bromine from a tilting dispenser. The reaction
mixture is swirled briefly and the test tube is propped up in
a 400-mL beaker pointed toward the light source. After a
few minutes, copious amounts of “HBr” can be seen and the
bromine color eventually fades to a light yellow. When the
reaction is complete, the test tube should be loosely corked to
diminish water condensation as ice is added to the surrounding
beaker. Cooling the solution to 0 °C will precipitate a white
solid, which can be collected by suction filtration. This should
be done in the hood, since there will still be some HBr in the
solution. The product should be air-dried for a few minutes
on the filter paper before taking its melting point and its
NMR spectrum. The reported melting point of 2,3-dibromo-
2,3-dimethylbutane is 169 °C (sealed tube) (3). Student yields
are usually more than 50% and melting points are within a
few degrees of the literature value when taken in sealed tubes.
Literature Cited
1. Landgrebe, J. A. Theory and Practice in the Organic Laboratory;
Heath: Lexington, MA, 1973. Roberts, R. M.; Gilbert, J. C.;
Rodewald, L. B.; Wingrove, A.S. Modern Experimental Organic
Chemistry, 4th ed.; Saunders: Philadelphia, 1985. Fieser, L. F.;
Williamson, K. L. Organic Experiments, 7th ed.; D. C. Heath:
Lexington, MA, 1992.
2. March, J. Advanced Organic Chemistry, 4th ed.; Wiley: New York,
1992, p 681 and references therein.
3. Shriner, R. L.; Fuson, R. C.; Curtin, D. V. The Systematic Identi-
fication of Organic Compounds: A Laboratory Manual, 4th ed.;
Wiley: New York, 1956.