Diastereoselective Bromination of trans-cinnamic

acid
C. Inao1
1
Institute of Chemistry, College of Science, University of the Philippines

Date Submitted: 7 November 2019

Instructor’s Name: M. Fajiculay

1. Using melting point data, determine

the major product formed. O
Br- H
Br O
H
Br O

Rationalize the difference in melting OH OH + OH

Br H H
points of the possible products. Br Br
2)

Answer to Question 1:

m
The bromination of trans-cinnamic acid

er as
There was no yield in the experiment,
will undergo anti-addition to form vicinal

co
however, the expected products are (2R,3S)
dibromides. The first step is the nucleophilic

eH w
and (2S, 3R) enantiomers of 2,3-dibromo-3-
attack of the pi bond in the acid to the
phenylpropanoic acid where the bromine was

o.
bromine molecule (Br-Br) which results to an
added via anti addition. Given that the
rs e expelled bromide and the formation of a the
expected products were formed, the melting
ou urc
bromonium ion. The next step is the
point should have been around 202 ° C -
nucleophilic backside attack of the bromide
204 ° C[1]. on the bromonium ion, leading to the
formation of a pair of erythro-2-3-dibromo-3-
o

Reference:
phenylpopanoic acid isomers with a melting
aC s

[1] Mayo, D., W., Pike, R., M., Forbes, D., C. point of around 204 ° C. [1]
v i y re

Microscale organic laboratory: with multistep

and multiscale synthesis, 5th edition. Wiley Reference:
Custom Services. 2011, 486. [1] Klein, D. Organic chemistry. 3rd ed. John
Wiley and Sons Inc, 2017, 363-366, 373-375.
ed d
ar stu

2. Explain the major product formed by

3. Draw the arrow-pushing reaction
drawing the arrow-pushing reaction
mechanism for the formation of the
mechanism. Discuss each step in the
minor product. Discuss each step in
mechanism.
sh is

the mechanism.
Th

Answer to Question 2:
Answer to Question 3:

1)
1)
O
O O H Br
OH

OH OH
+ Br Br Br O
Br Br
HO

2)

This study source was downloaded by 100000827071663 from CourseHero.com on 11-19-2021 23:59:41 GMT -06:00

https://www.coursehero.com/file/49885739/atq-11-diastereodocx/
 H Br
O H
Br O
H
Br O Why was it necessary to add
cyclohexene until the mixture turns
-
Br
OH
H
OH + H
OH

Br Br light yellow in color?

Answer to Question 5:

Cyclohexene reacts with Br2 though

The minor product of the reaction is formed
electrophilic addition. In the experiment,
through syn addition of bromine instead of
cyclohexene was added to react with excess
anti-addition. The first step is the electrophilic
Br2 and eliminating it. This is necessary
attack of the alkene double bond to the
because excess bromine in the solution can
bromine molecule, forming a carbocation
cause more impurities during the synthesis of
intermediate and free bromide. The bromide
the desired product. Moreover, glacial acetic
ion then attacks the carbocation
acid was used in the experiment to accelerate
intermediate, which lead to the formation of a
the rate of the bromination of trans-cinnamic
pair of threo-2-dibromo-3-phenylpropanoic
acid[1].
acid isomers with cis configurations[1].

Reference:
Reference:
[1] Young, S.D., and Berliner, E. ChemInform

m
[1] Klein, D. Organic chemistry. 3rd ed. John
Abstract: Kinetics of Halogenation of Olefins

er as
Wiley and Sons Inc, 2017, 363-366, 373-375.
and Acetylenes. 6. Bromination of trans-

co
Cinnamic Acid and Its Methyl Ester.

eH w
4. Why is the reaction stereoselective? Chemischer Informationsdienst. 1978, 44.

o.
How does it differ fromrs e
stereospecific reactions? 6. In an industrial or laboratory setting,
ou urc
discuss the distinct characteristics of
reactions using different halogens (F,
Answer to Question 4: Cl, Br, and I) in the halogenation of
alkenes.
o

In stereoselective reactions, there is a choice

aC s

of pathway under the same non-specific

v i y re

mechanism. The product major product

formed in the reaction is due to its pathway Answer to Question 6:
being more favored or yields a more stable Reference:
stereoisomer. In short, the reaction yields
ed d

multiple products but only one is considered [1] Solomons, G.T.W., Fryhle, C. B. Organic
as major. In stereospecific reactions, the Chemistry, 9th ed.; John Wiley: Hoboken, NJ,
ar stu

stereochemistry of the reactant specifies the 2008

stereochemistry of the product. There is no
other option, therefore, this reaction only
sh is

yields one stereoisomer[1].

The bromination of trans-cinnamic acid is a

Th

7. Liquid bromine is a known hazard in

stereoselective reaction because both syn the laboratory. Suggest milder
addition and anti-addition are possible, reagents for the bromination of
however, the product from anti-addition is the alkenes.
major product since this pathway is more
favored.

Reference: Answer to Question 7: A milder reagent that

can be used for the bromination of alkenes is
[1] Solomons, G.T.W.; Fryhle, C. B. Organic N-bromosuccinimide or NBS. It can serve to
Chemistry, 9th ed.; John Wiley: Hoboken, NJ, replace bromine in the formation of
2008 bromohydrins from reaction with alkenes. It is
much safer and easier to handle but can do
many of the same reactions as bromine.
5. Justify the use of glacial acetic acid Another possible option is Dibromoisocyanuric
and cyclohexene in the experiment. acid or DBI which is a mild and highly

This study source was downloaded by 100000827071663 from CourseHero.com on 11-19-2021 23:59:41 GMT -06:00

https://www.coursehero.com/file/49885739/atq-11-diastereodocx/
 effective brominating agent, with even better
brominating ability compared to NBS[1].

Reference:

[1] S. C. Virgil, in Encyclopedia of Reagents for

Organic Synthesis, ed. by L. A. Paquette, John
Wiley & Sons, Chichester, 2001, 1560.

8. Predict the stereoisomers formed

upon bromination of trans-stilbene
(1,2-diphenylethene)

Answer to Question 8:

m
er as
co
eH w
o.
rs e
ou urc
o
aC s
v i y re
ed d
ar stu
sh is
Th

This study source was downloaded by 100000827071663 from CourseHero.com on 11-19-2021 23:59:41 GMT -06:00

https://www.coursehero.com/file/49885739/atq-11-diastereodocx/
Powered by TCPDF (www.tcpdf.org)