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11-13-13
AMDG

Bromination of trans-stilbene

Results and Discussion

Figure 1. Addition reaction of Hydrobromic Acid with trans-stilbene to form 1,2-dibromo-1,2diphenylethane.

Figure 2. Half reactions showing the oxidation of Bromine and the Reduction of Hydrogen
Peroxide and then the overall oxidation-reduction reaction.
The bromination of compound 1 is an oxidation reaction that took place in a solution of ethanol.
When Hydrobromic acid and Hydrogen Peroxide were added to the solution successively, a
bright yellow precipitate formed to indicate the formation of the diatomic bromine in the
solution. Hydrogen Peroxide can be both a strong reducing and oxidizing agent. In this case it
was the catalytic oxidizing agent and was used as a Green reagent and was itself reduced to give
a byproduct of water.

Table I. Melting Point Analysis and Percent Recovery

Compound

MP(C)

Range

(1S, 2R) 1,2-Dibromo1,2-diphenylethane

232 C

230-231C

Percent Recovery
50.9%

After the experiment resulting in the bromination of compound 1, melting point analysis
was done to test the purity of the compound. When the dry product was observed it was a
crystalline white color but in melting the compound, a brown tinge was observed as the
temperature reached 200C. The brown tinge in the sample was attributed to the high
temperatures at which the compound was tested. The compound completely melted at 232C
(having a literature value of 241C). Although it could be concluded that the the compound was a
Meso product (by means of anti addition) the chemical reaction contains two products possible
due to the possibility anti addition. Even though the overall mechanism is indicative of anti
addition, the lower melting point could be attributed to a small period of syn addition that could
have taken place during the reaction process. The low yield of the compound (50.9%) was
determined from the theoretical yield calculated from stoichiometric values of the reactants in
the chemical equation. The low yield can be attributed to the experimental procedure error. The
procedure takes time and there were many rooms for error.

Figure 3. 13C NMR Spectral Data for compound 2

13C

NMR data of the compound displayed 4 peaks due to the line of symmetry that exists.

The most downfield peak correlates to the Carbons on the aromatic rings adjacent to the Carbon
bonded to the Bromine. The peaks upfield of this signal (~127-129 ppm) are indicative of the rest
of the Carbons on the aromatic ring, and the most upfield peak (~56ppm) correlates to the the
Carbon bonded directly to the Bromine. In comparing the NMR data of the Meso compound and
the dl Pair compounds, no difference was found. The signals were the same and should be
because there is no change in position of any of the substituents on the molecules, the orientation
of the Bromine and the Hydrogen is simply switched.

Figure 4. 1H NMR Spectral Data for Compound 2

1H

NMR presented 5 peaks (also due to its line of symmetry) but the most upfield peak

was disregarded as it was the peak that indicated the water in the deuterochloroform. The
downfield peaks (~7.40, 7.29, 7.27ppm) present downfield complex splitting due to their
location on the aromatic ring and their position next to the double bonds. The peak upfield of
those signals (~5.51ppm) correlate to the Hydrogen on the Carbon bonded to the Bromine.

In comparing both NMR spectral data for the Meso compound and the dl pair
compounds, it was seen that there was no difference in chemical shifts and it was concluded that
NMR spectral data could not, by itself, determine the stereochemical properties of enantiomeric
compounds. However, for diastereotopic protons a Deuterium test can be done by replacing a
diastereotopic with Deuterium and it should give different NMR signals.

Figure 5. The stepwise polar reaction mechanism for the addition of Br2 to cis-stilbene.
The above reaction does not occur in this experiment, but it can be seen that if cisstilbene was used in the reaction, rotation around the Carbon bonds would allow the same
compounds to be formed.

Conclusion
Out of the three experimental methods for analyzing the compounds, melting point was the most
useful. Carbon 13 and Proton NMR were not the best tools for identification of our product due
to the similar signals presented by enantiomeric products in the racemic mixture. Melting point
gave a very reliable indication of the identity of the compound because of the literature value of
melting point.Finally, Hydrogen Peroxide is a good Greene reagent to use. Instead of getting a
volatile byproduct, the byproduct was water.
4

Experimental
A round bottom 25-mL flask, equipped with a jacketed condenser and stir bar was assembled in
the fume hood. trans-stilbene (51g) was dissolved in ethyl alcohol (25-mL). Cool water was run
through the condenser and the flask was heated in a sand bath on medium heat until reflux. The
solution was removed from the heat and HBr (2.0 mL) was added dropwise with Pasteur pipette
and the solution. A yellow tint resulted due to the color of HBr. Hydrogen Peroxide (1mL) was
added dropwise and a bright yellow precipitate formed. The condenser was reattached and heated
in the sand bath (75 minutes). The flask was removed from heat and was left to cool to RT.
Sodium Carbonate (48 drops) was added to the cooled solution until neutral and the flask was put
into an ice bath (3 minutes) to cool. The precipitate was vacuum filtrated and titurated with hot
ethanol (20mL). When the ethanol started to boil the flask was removed from the hot plate and
refiltered to get the solid di-bromo-product. The sample was left to dry and the mass was
determined to be 0.49g. Melting points were taken in the Thomas-Hoover Melting point
apparatus and were determined to have a range of 230-231C and a melting point of 232C.
Some of the sample was weighed out (0.0142g) and prepared for NMR analysis. 1HNMR 7.40
(4H, dd), 7.29 (4H dd), 7.27 (2H, dd), 5.51 (2H, s), 1.4 (H2O and CDCl3). 13CNMR 138.3 (2C),
129.3 (8C), 128.9 (2C), 53.3 (2C).

References
Slough, Greg; Chemistry 210L Organic ChemistryI Lab Manual. 2013, pp. 51-55
ChemDraw, structures and 1HNMR analysis.
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