Diastereoselective Bromination of Trans-Cinnamic Acid

Sana, Joseph Timothy S.

Institute of Chemistry, University of the Philippines, Diliman, Quezon City
Date Performed: October 29; November 5, 2014
Date Submitted: November 12, 2014
ABSTRACT
The experiment aims to introduce concepts of stereochemistry via stereospecific
reactions and formation of optical isomers using trans-cinnamic acid as the main unsaturated
compound and bromine as the other reactant. Reflux set-up, maintained under 50 degreees
Celsius was used for addition of Bromine in acetic acid in trans-cinnamic acid and glacial
acetic acid. Recrystallization was repeatedly done using hot ethanol, water and gravity
filtration to obtain pure solid products to be weighed and classified by determining its melting
point. It was found out that the products melting point was 134-138 degrees Celsius
compared to a 204 degrees Celsius theoretical value. The percent yield was 11.34%.
Therefore, it can be concluded that the precipitate obtained was not pure erythro-2,3dibromophenylpropanoic acid. Deviations in procedure and contamination of reagents
possibly caused unwanted side reactions and low percent yield.

I.

INTRODUCTION

Organic
compounds
with
unsaturation such as alkenes and alkynes
react with bromine and give a positive
result of decolorization of the said reagent
usually from yellow to colorless solution
(Solomons & Fryhle, 2011). In this
experiment,
trans-cinnamic
acid,
a
carboxylic acid with an unsaturation
(double bond) in its second carbon and a
phenyl on its third carbon, is reacted with
bromine in a nonnucleophilic solvent in this
case, acetic acid.
The reaction mechanism is called
electrophilic addition of bromine to alkenes.
A cyclobromonium ion intermediate forms
due to attack of the bromide in the
electron-rich site of the trans-cinnamic
which is in this case, the double bond
(Trost, 1991). The now negatively charged
bromine atom attacks the intermediate via
trans, anti-addition to avoid steric strain as
shown in Figure 1.

+ Br2

+ Br-

Figure 1. Bromination of Trans-cinnamic

acid (w/ cyclobromonium intermediate)

The brominated product should have

two chiral centers, the second and third
carbons (counting the first carbon as the
carboxylic carbon). And thus, four optical
isomers can possibly be obtained as given
by:
number of isomers =2n
where n is the number of chiral carbons.
The bromination reaction of transcinnamic acid results to two enantiomers or
isomers whose mirror images are nonsuperimposable: (2R, 3R) and (2S, 3S); and
(2S, 3R) and (2R, 3S). Mesomers, which are
isomers that are superimposable on their
mirror images, can possibly be found too
therefore only three will be optically active.
With these things in regard, which
stereoisomers are produced based on the
measured melting point range measured?
Are they classified as diastereomers,
enantiomers or mesomers?
II.

METHODOLOGY

1.4800 grams of trans-cinnamic acid

was weighed using an analytical balance

and dissolved in 8 mL of acetic acid,

initially prepared by the instructor, in a 50mL round-bottom flask, as shown from
Figure 2:

temperature without any disturbances and

afterwards placed it in an ice bath for 10-15
minutes to crystallize.
The former clear solution, now with
crystals, in the Erlenmeyer flask, was
filtered using a pre-weighed 3:1 filter paper
and a receiving beaker. Then, cold distilled
water was added to the clear filtrate in the
beaker that produced a cloudy white
solution. The cloudy white filtrate was
filtered using the same pre-weighed 3:1
filter paper and the precipitate obtained
was air-dried in the locker until the next
meeting.
The melting point of the precipitate
was determined by using the melting point
apparatus shown in Figure 3:

Figure 2. Reflux Set-up

and was mixed by using a stirring bar under
a constant temperature of 50 degrees
Celsius.
The solution was placed in a
separatory funnel with 10 mL Bromine in
acetic acid above the condenser using an
iron ring. Br2 in CH3COOH was added
dropwise into the round-bottom flask with a
15-minute interval until the whole amount
was completely added and light orange
color persisted. Limonene was added
dropwise to the solution and a total of 6
pasteur pipettes was consumed. This
resulted to a cloudy yellow-orange solution
that
was
further
cooled
to
room
temperature and was placed in an ice bath
and afterwards filtered using a fluted 3:1
filter paper and a receiving beaker.
Since no precipitate formed after the
filtration of the yellow-orange solution,
distilled water was added to the filtrate in
the beaker that produced a cloudy white
precipitate. The original filtrate, now
containing a cloudy white precipitate, was
filtered using the same 3:1 filter paper. The
precipitate formed was then transferred
from the filter paper to an Erlenmeyer flask
and dissolved it in a hot 95% ethanol. Hot
ethanol was added continuously in the flask
until
all
precipitate
was
dissolved.
Afterwards, hot distilled water was added
until
cloudiness
appeared
and
an
appreciable amount of hot ethanol to
remove cloudiness and obtain a clear
solution. After dissolving all precipitate and,
the
solution
was
cooled
to
room

Figure 3. Melting Point Apparatus

III.

RESULTS AND DISCUSSION

The theoretical reaction mechanism

is that the bromide reacts with the double
bond in the trans-cinnamic acid. The
phenyl group in the said acid remains
stable due to resonance, thus the site
where the double bond is, will be the site
of attack for the bromide. The electron
density of the pi electrons from the
double bond repels the electron density
of the closer bromine atom and makes
it partially positive. Then the double
bond donates a pair of electron to it,
causing a displacement of the farther
bromine atom and formation of the
cyclobromonium
ion
intermediate
(Solomons & Fryhle, 2011). The
negative bromine atom attacks the
cyclobromonium atom (refer to Figure
1) and produces a erythro-2,3-dibromophenylpropanoic acid as shown in
Figure 3:

The computed melting point was

significantly
lower
probably
due
to
impurities in the reagents. Bromine is also
a very light-sensitive chemical and a slight
difference in lighting can produce unwanted
results. Deviations in the original procedure
such as using limonene instead of
cyclohexene and using gravity filtration
instead of vacuum filtration, using of cold
distilled water for production of precipitate
might also contribute to low percentage
yield and significant decrease in theoretical
melting point of the erythro- product/s.
IV.

CONCLUSIONS
RECOMMENDATIONS

Based on the determined melting

point, bromination of trans-cinnamic acid
was not successful. The 23.57 % yield was
not very high too.
For better obtained results, reagents
must be of higher purity, or be of less
impurity, and be kept and maintained in
conditions that favor stability. As much as
possible, the procedure should be followed
strictly. Glasswares and other equipment
should be cleaned properly to avoid more
contamination. Temperature should also be
at approximately 50 degrees Celsius at all
times. And finally, all data should be
recorded
accordingly
and
computed
without bias.
V.

APPENDIX
A. Raw Data

Figure 4. Bromination of Trans-cinnamic (w/

ertyhtro- product and its melting point)
One enantiomer of the product is
shown in Figure 3. The brominated product
has a melting point of 204 degrees Celsius
and is significantly higher than the transcinnamic acid melting point of 133 degrees
Celsius. This is due to the larger molar
mass of two bromine atoms.

The reaction yielded a white

precipitate weighing 0.3488 grams and
this white precipitates melting point
range was determined to be 134 138
degree Celsius for two trials. The percent
yield calculated was 23.57%.

AND

Weight of trans- 1.4800 g

cinnamic acid:
Weight of pre- 2.2051 g
weighed
filter
paper:
Weight of filter 2.5539 g
paper + ppt:
Melting point (For 134-138
both trials):
degrees C

B. Calculations

Weight of ppt: (weight of filter paper

+ ppt ) - (weight of pre-weighed filter
paper)
= 2.5539 2.2051 = 0.3488 g

% yield: Actual yield / Theoretical

Yield x 100 %
= (0.3488 g / 1.4800 g) x 100% =
23.57 %

*Analytical balance for weighing o

filterpaper and precipitate; Top-loading
balance for trans-cinnamic crystals

REFERENCES:

1. Carey, F. A., & Sundberg, R. J.

(2007). Advanced organic chemistry:
Part B. New York, NY: Springer.
2. Olah,
G.
A.,
&
Molnar,
A.
(2003). Hydrocarbon
chemistry.
Hoboken, N.J: Wiley-Interscience
3. Solomons, T. W. G., & Fryhle, C. B.
(2011). Organic chemistry. Hoboken,
N.J: Wiley.
4. Trost, B. M. (1991). Comprehensive
organic
synthesis:
Selectivity,
strategy & efficiency in modern
organic chemistry : in 9 volumes.
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5. (Figure 1) Retrieved from:
http://http://www.sigmaaldrich.com/c
ontent/dam/sigmaaldrich/structure8/185/mfcd0000436
9.eps/_jcr_content/renditions/mediu
m.png
6. (Figure 2) Retrieved from:
http://webapps.utsc.utoronto.ca/che
mistryonline/reflux.php
7. (Figure 3) Retrieved from:
what-when-how.com/wpcontent/uploads/2011/06/tmp30116_
thumb1.png
8. (Figure 4) Retrieved from:
http://http://chemconnections.org/org
anic/chem226/Labs/Bromination/bro
min-a-08.jpg