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Identification of the Stereochemical Configuration of the

Brominated Products of trans-Cinnamic Acid and trans-Stilbene

Joe Julian
CH:221:12
Tuesday, 1-4 PM
November 16, 2004
Abstract

Alkenes can from vicinal dihalides through the addition of halogens through the

displacement of a π bond. In alkenes where both carbons involved in the π bond have an equal

number of substituents, the halogen can attack either carbon, forming a racemic mixture. In this

experiment, trans-cinnamic acid and trans-stilbene underwent bromination. The goal was to

achieve as close to 100% yield as possible for both products. The configuration of the products

was determined by their melting points. The products were identified to be (±)-erytho-2,3-

dibromo-3-phenylpropanoic acid (from trans-cinnamic acid) and meso-1,2-dibromo-1,2-

diphenylethane (from trans-stilbene). The percent yield was found to be 122% for (±)-erytho-

2,3-dibromo-3-phenylpropanoic acid and 118% for meso-1,2-dibromo-1,2-diphenylethane. This

was attributed to water weight present in the products because they were not given enough time

to dry.

Introduction

Alkenes can form vicinal dihalides through the addition of halogens1. This is

accomplished by the nucleophilic addition of the π bond to a halide1. This reaction displaces a

halide ion and forms a halonium ion that is present in a three-membered ring with both carbons

that were involved in the π bond. Nucleophilic attack from the halide ion causes the highly

strained halonium ion ring to break1. This creates a product where the π bond has been broken to

form a vicinal dihalide product1. This type of reaction is classified as anti-addition because the

halogens must add to opposite sides of the π bond via a backside attack1. Racemization of the

product occurs because the halide ion has an even chance of attacking either carbon involved in

the halonium ion ring.

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In this experiment, trans-cinnamic acid and trans-stilbene underwent bromination to

form vicinal dihalide products (see Equations 1 and 2). The goal of this experiment was to

identify the stereochemistry of the product via the product’s melting point and to achieve as

close to 100% yield as possible for the product. To ensure that synthesis of product occurred, the

product was reacted with silver nitrate and checked for the presence of a precipitate.

(Equation 1)

(Equation 2)

Experimental Procedure

Preparation of trans-Cinnamic Acid2

A reflux apparatus was assembled, and in a 25mL round-bottom flask, 450mg of trans-

cinnamic acid, 6.0mL acetic acid, and 1.152g of pyridinium tribromide were placed. A magnetic

stir bar was added, and the flask was attached to the reflux apparatus.

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Preparation of trans-Stilbene2

A reflux apparatus was assembled, and in a 25mL round-bottom flask, 300mg of trans-

stilbene, 6.0mL of acetic acid, and 600mg of pyridinium tribromide were placed. A magnetic

stir bar was added, and the flask was attached to the reflux apparatus.

Bromination Process2

Both trans-cinnamic acid and trans-stilbene were subject to the same bromination

procedure. After the round-bottom flask was attached, the flow of water was started through the

condenser. The mixture was heated and gently refluxed for 20 minutes while stirred with the stir

bar. The round-bottom flask was removed from the heat source and the water source was turned

off after 20 minutes. The flask was allowed to cool for 5 minutes. The stir bar was removed

with a magnetic wand and 8.0mL of distilled water was added to the flask. An ice-water bath

was prepared by filling a 250mL beaker halfway with equal volumes of ice and water. The flask

was placed in the ice-water bath for 15 minutes.

A vacuum filtration apparatus was assembled using a Buchner funnel. The product was

filtered and the crystals were washed with distilled water. The product was allowed to sit in the

funnel for 15 minutes with the vacuum left on to facilitate drying. The product was then

weighed.

Product Identification2

The melting point of the product was recorded using a Hoover Uni-Melt device. The

product was then tested with silver nitrate. In a small test tube, about 10mg of the product was

dissolved in 0.5mL of 95% ethanol. To the resulting solution, 0.5mL of 2% ethanolic silver

nitrate was added and the tube was allowed to stand for 5 minutes. Any observations were

recorded.

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Results

The following results were tabulated from data acquired from the experiment. Table 1

showed the melting point of each product so it could be positively identified by comparing it to

the melting points of known compounds in Table 2.

Brominated Reactant Melting Point Product Identification

(±)-erytho-2,3-dibromo-3-
trans-cinnamic acid 197°C
phenylpropanoic acid

meso-1,2-dibromo-1,2-
trans-stilbene 233-236°C
diphenylethane

Table 1. The melting points of the synthesized products from each reactant that underwent

bromination. The products were able to be identified by the melting point.

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Compound Melting Point (°°C)

2,3-dibromo-3-phenylpropanoic acid

(±)-threo 94

(±)-erythro 203

(±)-1,2-dibromo-1,2-diphenylethane 110

meso-1,2-dibromo-1,2-diphenylethane 238

Table 2. 2 The melting points for possible products after bromination of trans-cinnamic acid and

trans-stilbene.

Table 3 showed the percent yield of both products that were identified and Table 4 was the

results of the silver nitrate test, which tested for the presence of bromide.

Theoretical Yield Actual Yield Percent Yield

±)-erytho-2,3-dibromo-3-

0.935g 1.14g 122%
phenylpropanoic acid

meso-1,2-dibromo-1,2-
0.566g 0.67g 118%
diphenylethane

Table 3. The percent yield of 2,3-dibromo-3-phenylpropanoic acid and meso-1,2-dibromo-1,2-

diphenylethane based on the calculated theoretical yields for each compound.

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Product Observations

(±)-erytho-2,3-dibromo-3- Solution turned milky white with pale yellow


phenylpropanoic acid precipitate

meso-1,2-dibromo-1,2- Solution turned milky white with white


diphenylethane preciptitate

Table 4. The observations for each product were recorded upon the addition of 2% ethanolic

silver nitrate.

The following two figures were detailed mechanisms for the bromination of trans-

cinnamic acid and trans-stilbene.

Figure 1. Detailed mechanism for the bromination of trans-cinnamic acid. The configuration of

the product was dependent upon which carbon the bromide ion attacked.

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Figure 2. Detailed mechanism for the bromination of trans-stilbene. The same product resulted

regardless of which carbon was attacked by the bromide ion.

Discussion

The bromination of trans-cinnamic acid resulted in a product of (±)-erytho-2,3-dibromo-

3-phenylpropanoic acid. This was determined by the comparison of the melting point of the

product in Table 1 to the known melting point values for the possible products of the

bromination of trans-cinnamic acid in Table 2. Based on the melting point of 197°C, the

configuration of the products was determined to be (±)-erythro2. The stereochemical

configuration for 2,3-dibromo-3-phenylpropanoic acid was either (2R,3S) or (2S,3R) (see Figure

1). The two possible configurations were the result of the bromide ion attacking either carbon 2

or carbon 3. An attack on carbon 2 resulted in a configuration of (2S,3R) and an attack on

carbon 3 resulted in a configuration of (2R,3S). These two different attacks resulted in a racemic

mixture since both attacks were equally likely to happen.

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The bromination of trans-stilbene resulted in a product of meso-1,2-dibromo-1,2-

diphenylethane. This was determined by the comparison of the melting point of the product in

Table 1 to the known melting point values for the possible products of the bromination of trans-

stilbene in Table 2. Based on the melting point of 233-236°C, the configuration of the products

was determined to be (±)-erythro2. The stereochemical configuration for meso-1,2-dibromo-1,2-

diphenylethane was determined to be either (2R,3S) or (2S,3R), but either configuration resulted

in the same product. It did not matter which carbon was attacked by the bromide ion because

both carbons were attached to identical substituents. This gave an internally symmetric product

and a meso configuration (see Figure 2).

As Table 3 shows, the percent yield for both products was over 100%. The cause of this

error was not giving the product enough time to dry. The additional mass was most likely the

result of water weight. This could have prevented by giving the product more time to dry while

it was sitting in the Buchner funnel with the vacuum on. Another source of error for the

synthesis of (±)-erytho 2,3-dibromo-3-phenylpropanoic acid could have been the result of a

harsh reflux. Too harsh of a reflux would have caused the bromide to vaporize and lowered the

percent yield. However, since the product was very damp, it is hard to say how much of an

effect this had on the percent yield of the reaction.

The silver nitrate test was performed to test for the presence of halides3. A precipitate

formation showed that the bromide ion was indeed present and came from the product (see Table

4) 3. The product reacted with the nitrate either by elimination or substitution, freeing the

bromide from the product. The bromide was then able to form the precipitate silver bromide3.

Silver bromide was found to have a pale yellow or white color, which was consistent with the

results in this experiment3.

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Conclusion

The percent yield for both (±)-erytho-2,3-dibromo-3-phenylpropanoic acid and meso-1,2-

dibromo-1,2-diphenylethane was over 100%, which was the result of not giving the products

sufficient time to dry. The synthesis of these products was supported by the formation of a

precipitate when silver nitrate was added.

References

1. Wade, Jr., L.G. Organic Chemistry – 5th Edition. Pearson Education, Inc. New Jersey,

2003.

2. Rowland, A.T.; Allen K. Clark; Carl T. Wigal; Charles E. Bell, Jr.; Douglass F. Taber;

Frederick A. Bettelheim; Jan William Simek; Jerry Manion; Joe Jeffers; Joseph M.

Landesberg; Joseph W. LeFevre; L.G. Wade, Jr.; Louis J. Liotta; Moses Lee; Ronald

J. Wikholm; and William M. Loffredo. Organic Chemistry Laboratory Manual:

Susquehanna University. Thomson Learning: Ohio, 2003.

3. Glagovich, Neil. Central Connecticut State University. 2001.

http://www.chemistry.ccsu.edu/glagovich/teaching/472/qualanal/tests/agno3.html.

Accessed 23, Nov. 2004.

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