Bromine Addition to Trans-Cinnamic Acid

Jonathan Sneller, Dominic Lammers, Carson McKelvey and Paul Smolenyak

Department of Chemistry, Yavapai College, Prescott, AZ 86301, 22 November 2015

Introduction

2,3-dibromo-3-phenylpropanoic acid was synthesized from the reaction of trans-cinnamic acid and
bromine. Product was obtained by adding a solution of bromine in glacial acetic acid to trans-cinnamic
acid. Alternately, the bromine solution was added to trans-cinnamaldehyde. Both products were
purified and characterized, and outcomes were compared.

O H Br O H Br O

OH OH OH
Br H Br H

H Br O H Br O

O
Br H Br H

Figure 1. The addition of bromine to trans-cinnamic acid or to trans-cinnamaldehyde yields a racemic

mixture of 2,3-dibromo-3-phenylpropanoic acid and 2,3-dibromo-3-phenylpropanal.

Figure 1. The addition of bromine to trans-cinnamic acid to form 2,3-dibromo-3-phenylpropanoic acid1

Figure 2. **show alternate mechanism** The addition of bromine to **name** to form ???

Experimental Methods

Experimental methods were outlined by Smolenyak1. The trans-cinnamaldehyde or the trans-cinnamic

acid reacted in a 1-1 ratio with excess bromine. Vacuum filtration was used to isolate the 2,3-dibromo-
3-phenylpropanoic acid, which is a solid at room temperature. The 2,3-dibromo-3-phenylpropanal was
isolated using liquid-liquid extraction. The 1H NMR and IR spectra were collected to characterize the
products23.

The alternate reaction consumed 3.00 mL of trans-cinnamaldehyde. Two NMR spectrums for similar
products prepared and isolated by the same synthetic methods were obtained3,4.

Experimental Methods

The melting point range was 200-203for product obtained via

Results

The addition of bromine to trans-cinnamic acid gave an average of 63.5% percent. The addition
of bromine to trans-cinnamaldehyde also resulted in formation of product, 3.7472g from 3.15g, but
further analysis would be required to isolate and purify the product.

Table 2 – The mass of the starting material (trans-cinnamic acid or trans-

cinnamaldehyde). The experimental yield along with the calculated theoretical yield
and percent yield.
Mass of trans- Moles of trans- Theoretical Experimental Percent
cinnamic acid (g) cinnamic acid yield (g) yield (g) yield (g)
2.9430 0.0199 6.1174 3.4841 57%
2.9673 0.0200 6.1679 4.2922 70%
Mass of trans- Moles of trans- Experimental
cinnamaldehyde (g) cinnamaldehyde yield (g)
3.15 0.0238 3.7472

Figure 3. NMR spectrum of 2,3-dibromo-3-phenylpropanoic acid synthesized from trans-cinnamic acid4

Table 1. Weight of reactant, purified product, and theoretical product and percent yield

The NMR spectrum of the 2,3-dibromo-3-phenylpropanoic acid produced spectrum indicative of

a benzene ring, two hydrogens attached to carbons with bromine, and a hydrogen on a carboxylic acid.
This is exactly the spectrum expected for 2,3-dibromo-3-phenylpropanoic acid. The IR spectrum also
indicates bromine substitution from the strong IR absorbance in the 500-600 cm-1 range.4 The IR of the
product of trans-cinnamaldehyde and bromine showed similar absorbance’s in 500-600 cm-1 range
indicative of bromine-carbon bonds.

CKM19D-3.SK

0.10
Normalized Intensity

0.05

4.69 0.66 2.00

7.5 7.0 6.5 6.0 5.5 5.0

Chemical Shift (ppm)

Figure 4 – The 1H NMR for 2,3-dibromo-3-phenylpropanoic acid.

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55

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25

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400 0 350 0 300 0 250 0 200 0 150 0 100 0 500

W av enu mber s ( c m- 1)

Figure 1 – The IR spectrum of 2,3-dibromo-3-phenylpropanoic acid in

KBr.

Discussion

The product obtained had a higher weight than the reactants, indicating the successful addition of
bromine to trans-cinnamic acid and trans-cinnamaldehyde. Analyses of the transmittance peaks in the
product’s IR spectrum in figure 2 were found to be consistent with those in the known IR spectrum for
2,3-dibromo-3-phenylpropanoic acid displayed in Figure 3. The melting point of 200°C -203°C is
consistent with the melting point of the (2R,3S) and the (2S,3R) enantiomers of 2,3-dibromo-3-
phenylpropanoic acid5. The narrow melting range indicates that the products were pure. The melting
point range for the product formed from trans-cinnamaldehyde and bromine had a melting point range
of 56°C to 61°C. This product is likely a mixture of 2,3-dibromo-3-pheylpropanoic acid and 2,3-dibromo-
3-phenylporpanal, which would account for the much lower melting point; aldehydes have weaker
intermolecular forces due to the decreased hydrogen bonding. The peak form and integration of the
NMR spectrum in figure. 4, for a product prepared by identical synthetic methods, was consistent with
the values expected for 2,3-dibromo-3-phenylpropanoic acid. The data collected indicates the
successful synthesis of (2R,3S) and (2S,3R) enantiomers of 2,3-dibromo-3-phenylpropanoic acid.

1. 2. "α,β-Dibromohydrocinnamic Acid." Nist.gov. National Institute of Standard and Technology,

2011. Web. 23 Nov. 2014. http://webbook.nist.gov/cgi/cbook.cgi?ID=C6286302&Mask=80

5. J. W. Lehman, Operational Organic Chemistry, 3rd Ed., pp. 175 – 181, Prentice Hall, Upper Saddle
River, NJ, 1999
1
Smolenyak, P.E. Organic Chemistry Laboratory 1, 2015, Yavapai College, Prescott, Arizona
2
Anasazi Eft-60 NMR http://aiinmr.com

3
Thermo Scientific Nicolet 380 FTIR http://www.thermoscientific.com

4
"Infrared Spectroscopy Correlation Table." Wikipedia. Wikimedia Foundation, n.d. Web. 10 Dec. 2015.

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95

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%T

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400 0 350 0 300 0 250 0 200 0 150 0 100 0 500
W av enu mber s ( c m- 1)

IR from Dominic L. of solid product in KBr

Notes:
- The things I highlighted in red I though should be removed and the things in blue I thought might need
revision or deletion but I wanted your opinion.
- The figure captions are wrong but I though you may be adding data so I’ll let you sort them all out  
- I put the IR of my product in case you wanted to use it. I didn’t think it was important.
- All of Carson’s data is in the tables.
- Let me know if you need anything else