Maci Mullins

CHEM2130-001
10/9/2017

Stereochemistry of Bromine Addition to trans-Cinnamic Acid

Statement of Problem:
What is the stereochemistry for the bromination of trans-cinnamic acid, and how is it
formed?

Hypothesis:
Two forms of stereochemistry can form product for the bromination of trans-cinnamic
acid. Cis addition, also known as syn addition, is one way of forming product. This form of
stereochemistry allows for the components of the reagent to add to the same side of the double
bond. Trans, also known as anti addition, is the second form of addition that can create product
for this experiment. Tran stereochemistry occurs when the components of the reagent add to
opposite sides of the double bond. In this experiment, the formation of either erythro-2,3-
dibromo-3-phenylpropanoic acid (trans/anti-R,S or S,R) or threo-2,3-dibromo-3-
phenylpropanoic acid (cis/syn-R,R or S,S) was expected to occur.

Supporting Paragraphs:
The literature values of erythro-2,3-dibromo-3-phenylpropanoic acid and threo-2,3-
dibromo-3-phenylpropanoic acid were provided in the laboratory experiment text. Erythro-2,3-
dibromo-phenylpropanoic acid held a melting point of 204C, while threo-2,3-dibromo-3-
phenylpropanoic acid held a melting point of 95C. These two products had vastly different
melting point values, which made it clear to observe the product created at the end of the
experiment. Once the product was determined due to comparison of melting points, the
stereochemistry could be identified and understood. Trans-cinnamic acid adds bromine through
the process of carbocation rearrangement. During this arrangement bromine can add from either
the top, resulting in cis/syn addition, or from the bottom, which would result in trans/anti
addition. The bromine ion mechanism used to give my product was trans addition. If the bromine
ion mechanism of cis addition were to have been used, the threo product would have been
created.
In this reaction, one mole of trans-cinnamic acid (0.148g) was mixed with 0.8mL of
glacial acetic acid. It was then heated until most of the cinnamic acid had dissolved. The reaction
period took approximately fifteen minutes to complete. Once dissolved, the bromine in acetic
acid was added, which when observing in mechanism, the bromonium bridge would form
(shown in Figure 1). The bridge forms because of the nucleophilic attack on the neutrally
charged bromine. The second bromine then breaks off as the negatively charged bromine,
resulting in the bromonium bridge. At this point of the mechanism, the ion pulls from the bonds
connecting it to the carbon, resulting in a bit more balance with a slightly less positive charge.
The solution was then heated until the bromine tint slightly faded. The cause of color change was
due to the evaporation of bromine through heat. The product was then placed into a vial to
crystalize over a one-week period. This one-week period allowed for the product to dry
completely, which allowed for a melting point to be taken immediately going into lab the
following week.
 Entering lab for the second week, the product had completely dried and analysis was
ready to be performed. Literature melting point values were known and compared to the melting
points that were collected from the product created the prior week. A sharp melting point was
recorded of 190C-192C. Since this melting point was not extremely broad, or larger than either
of the literature values, it was clear to identify the product that was created. The recorded melting
point was much closer to that of the erythro-2,3-dibromo-3-phenylpropanoic acid rather than that
of the threo-2,3-dibromo-3-phenylpropanoic acid.

Figure 1: Addition of Bromine in Acetic Acid to form Bromine Bridge

Conclusion:
Since the melting point of the product created was approximately 10C less than the
literature value of the erythro-2,3-dibromo-3-phenylpropanoic acid, it was obvious that the
product created in this experiment was in fact a pure erythro-2,3-dibormo-3-phenylpropanoic
acid product. The stereochemistry for the erythro product consists of trans/anti addition (shown
in Figure 2a). This form of addition allows for the components of the reagents to add on the
opposite sides of the carbon to carbon double bond. If the recorded melting point of the product
in this experiment had been a value closer to 90C, the product would have obviously been the
threo-2,3-dibromo-3-phenylpropanoic acid. This would have resulted in cis/syn addition (shown
in Figure 2b), which is when the components of the reagent add to same side of the carbon
double bond. My hypothesis does agree with the results and theory of the experiment. A pure
product could be created, and the proper associated stereochemistry was able to be identified.

Figure 2a: Trans/Anti Addition of Bromine to Trans-Cinnamic Acid

Figure 2b: Cis/Syn Addition of Bromine to Trans-Cinnamic Acid