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solvable with gas chromatography. Experimental procedures for the reactions appear in a number of organic
chemistry laboratory texts (4).
H Br
Br2
H
H Br
meso
mesostereoisomer
stereoisomerififsyn
synaddition
addition
()
() stereoisomer
stereoisomerififanti
antiaddition
addition
H Br
Br2
H Br
() stereoisomer
stereoisomerififsyn
synaddition
addition
()
meso
mesostereoisomer
stereoisomerififanti
antiaddition
addition
Scheme I
To round out the experiment, the remaining isomer
1,1-diphenylethylene is also considered and reacted with
bromine under the same conditions. It is used to emphasize the importance of experimental design in testing a
mechanism and, of course, for its unexpected results.
Thus, one third of the class works with 1,1-diphenylethylene, one third works with cis-1,2-diphenylethylene,
and one third works with trans-1,2-diphenylethylene.
The products are analyzed with GC-MS, rather than by
melting point.
Results
Students starting with trans-1,2-diphenylethylene
observe meso-1,2-diphenyl-1,2-dibromoethane as the
major product (with about 5% of the () stereoisomer by
GC). This observation is consistent either with formation of the more stable product or with anti addition. Students starting with cis-1,2-diphenylethylene observe ()1,2-diphenyl-1,2-dibromoethane as the major product
(about 5% meso by GC, after filtration). This is also consistent with anti addition and rules out the possibility
that the more stable product is always being formed. The
reaction is highly stereoselective. Students propose a bromonium ion (like the mecurinium ion in oxymercuration
of alkenes) to explain the observations. They are told that
this is the normal course of action for bromine addition
to alkenes but they are also warned of cases where the
stereoselectivity of the reaction is not maintained (e.g.,
dihydropyran and cis-di-tert-butylethylene are exceptions listed in common textbooks) (5). This leads us into
the discussion of surprise results when 1,1diphenylethylene is reacted with bromine.
109
In the Laboratory
The explanation for the formation of 1,1-diphenyl2-bromoethylene from 1,1-diphenylethylene, under the
same conditions, is less obvious. A common student response is to propose that the substitution proceeds via
free radicals (as they have seen with alkanes and Br2).
Arguments against this idea are readily made and it is
abandoned. Students are instructed to see if they can
modify the established mechanism for bromine addition
rather than come up with an entirely new one. The revised mechanism describes the substitution as an addition, followed by an elimination (Scheme II). It is speculated that the phenylphenyl interaction on going from
sp2 to sp3 hybridization, makes bromonium ion formation and subsequent addition of Br{ a less likely process
than elimination. The students are told that they are
likely to encounter this reaction again whenever steric
interactions make addition less likely or, more importantly, when there is a strong driving force to re-form
the -bond (e.g., electrophilic aromatic substitution).
BrBr
Br+H
Br
Br
Avoid contact with the pyridinium bromide perbromide. Ether should be disposed as a toxic waste. Acetic acid and methanol should be burned in an incinerator.
Br
Acknowledgments
Br
+ HBr
Scheme II
Conclusion
Pooling the results obtained from the reaction between bromine and the 1,2-diphenylethylenes allows students to discover the mechanism of anti addition, which
is common to most situations. Expansion of this experiment to include 1,1-diphenylethylenes allows students
the opportunity to discover the electrophilic substitution
reaction. This sets the stage for electrophilic aromatic
substitution.
110
Br2
?
Experimental Procedure
We would like to acknowledge support from the National Science Foundation (USE-8852774 and USE9052318) and from the College of the Holy Cross. We
would like to thank Paul D. McMaster for incorporating
and testing this experiment in his course.
Literature Cited
1. Ricci, R. W.; Ditzler, M. A. J. Chem. Educ. 1991, 68, 228231.
2. Jarret, R. M.; McMaster, P. D. J. Chem. Educ. 1994, 71, 10291031.
3. Jarret, R. M.; New, J.; Patraitis, C. J. Chem. Educ. 1995, 72, 457
459.
4. (a) Lehman, J. W. Operational Organic Chemistry; Allyn & Bacon:
Boston, 1988; (b) Nimitz, J. S. Experiments in Organic Chemistry;
Prentice Hall: Englewood Cliffs, NJ, 1991.
5. Kemp, D.; Vellaccio, F. Organic Chemistry; Worth: New York, 1980.
6. Buckingham, A., Ed. Dictionary of Organic Compounds, 5th ed.;
Chapman and Hall: New York, 1982; Vol. 1, p 795.