Experiment 5: Bromination of

E-Cinnamic Acid
Department of Chemistry, University of Ottawa, 10 Marie Curie Priv, Ottawa, Ontario,
K1N6N5
January 2024

ABSTRACT

Electrophilic halogenation of alkenes.

Introduction
Electrophilic halogenation of alkenes is a fascinating
reaction that involves the addition of molecular halogens,
like Br2 or Cl2, to the carbon-carbon double bond of alkenes. Figure 1. Illustration of the difference between
This reaction produces an alkane with two adjacent halogen stereoselectivity and stereospecificity.
atoms, known as a 1,2-dihalide or a vicinal dihalide
(Scheme 1).

Scheme 1. Overall transformation for the electrophilic

halogenation of alkenes.

As shown in Figure 1, let’s say a given reaction can lead

Stereoselectivity vs Stereospecificity
Notice in Scheme 1 the relative placement of the two
halogen atoms in the product: they are located on opposite
sides of the original  bond. This particular arrangement is a
consequence of the stereospecificity of the reaction
mechanism.
to the formation of two stereoisomers, A and B.
If the reaction is neither stereoselective nor
stereospecific, a racemic mixture of A and B are formed; in
other words, both isomers will be formed in equal amounts
(Figure 1a).
If the reaction is stereoselective, one stereoisomer is
formed preferentially: while both stereoisomers can form,
only one will be the major product (Figure 1b). As seen in
Experiment 4, this selectivity or preference for a particular
isomer is usually due to the presence of directing groups.
These are substituents that impede the directional attack of
the nucleophile, resulting in major/minor products.

Experiment 5 1
 In contrast, a stereospecific reaction is a reaction where
the mechanism itself results in the formation of specific
stereoisomers in the products (Figure 1c). In other words,
there is no major/minor disparity – only certain
stereoisomers will be obtained.
As described below, the electrophilic halogenation of
alkenes is a stereospecific reaction, resulting in the
formation of the anti addition products.
In organic chemistry, there are several terms used in
different contexts to describe the spatial arrangements of
substituents. You have already learned about the use of cis
and trans to describe disubstituted cycloalkanes and E and Z
for the geometry of alkenes. For addition reactions, we use
syn and anti to describe the relative positions of the two
added substituents in the final product with respect to the
main chain. The term syn refers to addition on the same face
of the molecule, whereas anti indicates that the groups were
added to opposite faces of the molecule, as shown in Scheme
2.
Scheme 2. Illustration of syn versus anti addition of
substituents to an alkene.
Reaction Mechanism
In this experiment, you will perform the electrophilic
addition of a molecular halogen to an alkene. This reaction
occurs via an unusual bridged-cation intermediate, known
generally as a halonium ion.
Scheme 3. Part one of the reaction mechanism, forming the
halonium ion intermediate.
Recall that the double bond in an alkene is quite electron-
rich. Thus, as the molecular halogen approaches the double
bond of the alkene, the electrons in the double bond repel the
electrons in the X2 molecule, creating an induced dipole. The
Experiment 5
next step in the mechanism is complex, involving several
transformations:
• the  electrons are used to form a covalent bond
between the closer, slightly electrophilic (+)
halogen atom and one carbon atom
• the slightly electrophilic halogen atom uses one of
its non-bonding pairs to form a second bond to the
other carbon atom
• the halogen-halogen single bond breaks
heterolytically, and the halogen atom further away
is released as a negatively charged halide anion
Since the exact sequence of these three individual changes
is unknown, all three are shown together simultaneously, in
what is called a concerted step. The result of this step is the
formation of the halonium ion, where one positively charged
halogen atom forms a ‘bridge’ between the two carbon
atoms of the original double bond. This concerted step is not
stereospecific; meaning, the halonium bridge can form
equally on either face of the alkene. Therefore, depending
on the nature of the alkene, two different halonium ion
intermediates may be possible.
Scheme 4. Part two of the reaction mechanism, showing the
anti-periplanar attack of the halide anion and the ring-
opening of the halonium ion, resulting in the anti-addition
product. Note: only one of the two possible halonium ions
from Scheme 3 is shown, for clarity.
The last step of the mechanism involves the nucleophilic
attack of the released halide anion and subsequent ring-
opening of the halonium ion to form the final anti vicinal
dihalide. This step is stereospecific: to successfully break the
 C-X bond and open the ring, the X– nucleophile must
attack from the direction on the opposite side of the bond
(the reasons for this requirement may be explained in further
detail in class). This is known as an anti-periplanar attack, as
illustrated separately in Scheme 5.
Scheme 5. Illustration of anti-periplanar attack. To break the
C–Z single bond, the nucleophile must attack from the
opposite direction.
2
 The alkene used in this experiment is E-cinnamic acid (E-
3-phenyl-2-propanoic acid) and the molecular halogen is
bromine. Since the alkene is unsymmetrical, addition of two
bromine atoms creates two chiral centres and therefore a
maximum of four possible stereoisomers (Scheme 6).

Scheme 6. The synthesis of Experiment 5.

The (2S,3S) and (2R,3R) enantiomeric pair has a melting
point of 93.5 – 95ºC, whereas the (2R,3S) and (2S,3R)
enantiomeric pair has a melting point of 202 – 204ºC. Thus,
you will determine the melting point of your final, purified
product mixture to confirm which enantiomeric pair has
formed (and thus also the stereospecificity of the reaction
mechanism).
How to set-up a reflux apparatus
Glassware for organic chemistry is designed to be
modular, interchangeable and to give an airtight seal
between parts. This is accomplished by the use of ground
glass joints. To work properly, the joints must be clean.
Always inspect them for dirt and dust before assembly. If
they are dirty, wipe with a paper towel.
Some experiments require the use of grease to prevent the
ground glass joints from locking together (this is called
seizing or freezing). This will be indicated in your manual,
or by your demonstrator. In these cases, use a small amount
of grease, lightly applied to the top of the male joints before
assembly.
Organic apparatus are easiest to set up if you work from
the bottom up. Start with your magnetic stirrer. Place the
appropriate sized heating mantle on top of the stirrer and
connect the heating mantle to the Variac. CAREFULLY
place a magnetic stir bar in your distilling flask by tipping
the flask on it’s side and GENTLY sliding the bar along the
inside of the flask. You should never drop a stir bar into a
flask. The distilling flask is then clamped so that it rests in
the heating mantle. Use an extension clamp on the neck of
the flask in the position indicated in the diagram below.
ALWAYS CLAMP FLASKS THAT WILL CONTAIN
CHEMICALS. Use solid extension clamps for flasks (2
finger clamp), they hold better than three-fingered universal
clamps. Clamp your flask so that the clamp holds just below
the top lip of the female joint.
Once your refluxing flask is set, it is easy to add the other
glassware. Work from what you have already set up, and add
pieces one at a time. Add clamps as necessary to hold the
apparatus solidly. The best place to clamp apparatus is at the
joints. Proper locations are indicated in the various
drawings. Once your set-up is complete, inspect it before
proceeding. The joints should be fully sealed and the
apparatus should be solidly clamped.
The condenser serves to cool the vapours which are then
collected, via the adapter, in the receiving flask. Cooling is
achieved by passing water through the jacket of the
condenser. Connect rubber hoses so that water enters the
bottom of the condenser and exits the top. In this way,
gravity will ensure that the water completely fills the cooling
jacket. This is important because the water must always be
in contact with the inner glass surface in order to keep this
surface cool.
When liquids are boiled, bubbles of vapour form in the
bulk liquid. These bubbles form around imperfections in the
vessel or solids suspended in the liquid. This process is
called nucleation. Laboratory glassware will usually not
contain enough “defects” to ensure proper nucleation, and so
heated liquids can sometimes superheat (heat above the
boiling point). Vapour bubbles can then form violently
forcing the liquid out of the apparatus. This potentially
dangerous event is called “bumping”. Bumping is easily
controlled by stirring the solution using a magnetic stir bar
and stirrer. When stirring solutions, the speed should be
controlled so that a small vortex is formed in the flask. Do
not stir too fast as this will splash the contents of the flask
onto the flask walls resulting in loss.
The Experiment
IMPORTANT!! – Due to potential side reactions,
acetone will not be used during this experiment!
Glassware should be rinsed/cleaned using ethanol!!
1. Place approximately 0.5 g of E-cinnamic acid (note
the mass precisely!) in a 25 mL round bottom flask.
2. Transfer 3.5 mL of dichloromethane to the flask and
carefully slide a small magnetic stir bar into your
flask.
3. Setup your reflux apparatus as follows:
a. Clamp your round bottom flask to the bars about
1/3 of the way up using an extension (2-finger)
clamp.

Experiment 5 3
 b. Attach water hoses to your condenser – they
should be firmly attached but do not push so hard
that the rubber splits.
c. Insert your condenser in the top of the round
bottom flask and clamp it loosely around the
center of the condenser using a 3 finger
(universal) clamp.
d. Water should enter from the bottom of the
condenser and exit from the top (why?). The end
of the exit hose should be weighted with a clamp
and placed carefully in the drain. Turn the water
on and ensure that the outlet hose remains in the
drain and the jacket of the condenser fills with
water.
e. Place a lab jack underneath your round bottom
flask.
f. Place a stir plate on top of the lab jack. The stir
plate can be plugged directly into the power outlet
in the fumehood.
g. Place a heating mantle on top of the stir plate and
raise the lab jack slowly until the round bottom
flask is nested comfortably inside the heating
mantle.
h. Plug the heating mantle into the VARIAC to
control the temperature of the mantle. Then plug
the VARIAC into the power outlet of the
fumehood.
4. Turn on your stir plate to ensure gentle mixing of
your reagents.
5. Set your heating mantle to 30 – 40 % initially and
then adjust by increasing as needed to ensure that the
dichloromethane just boils.
6. Once the solution begins refluxing, obtain 2 mL of
the 10% bromine solution from your TA. Add the
bromine solution using a plastic disposable pipette
through the top of the condenser (reflux apparatus).
(Once the bromine is added, the solution should turn
bright orange).
7. Place the vial in which you obtained the bromine
solution and the disposable pipette you used to
dispense it in the labelled container in the waste
fumehood.
8. Allow the solution to reflux for 30 minutes. If the
orange colour fades before 30 minutes, see your TA
to obtain a small additional volume of bromine
solution.
9. While your solution is refluxing, place a beaker
containing 15 mL of dichloromethane in an ice bath.
It will be used to rinse your product.
10. Once the reflux is complete, if the mixture still has an
orange colour, add cyclohexene dropwise (allow a
few seconds of mixing between the addition of each
drop) until the colour fades to a pale yellow.
11. Turn off the heating mantle (by reducing the
VARIAC to zero and then turning it off) and the stir
plate. Lower the lab jack so that your reaction can
begin cooling.
Experiment 5
12. Once the glassware is cool to the touch, place your
round bottom flask in a 150 mL beaker of ice water
and allow it to chill for 10 minutes.
13. Use manual vacuum filtration to separate your
products from the mother liquor. Rinse your round
bottom flask and product with the cold
dichloromethane (use three 2 mL aliquots or
portions). This is the crude product.
14. Keep a small quantity of the crude product to perform
TLC and melting point analyses.
15. Recrystallize your crude product using the following
procedure.
a. Transfer your rinsed product into a 50 mL
Erlenmeyer flask.
b. Add 2 mL of ethanol to your flask and heat on a
hot plate until your solid dissolves completely.
c. In a dropwise manner, add warm distilled water
to your flask (to a maximum of 2 mL) until you
just see precipitate forming and continue heating
until all the solid dissolves completely.
d. Once no solid is visible, carefully remove the
Erlenmeyer flask from the heat and allow it to
cool undisturbed.
e. Place a wash bottle filled with distilled water in
an ice bath to use for rinsing your product.
f. Once the glassware is cool to the touch, place
your flask in a 150 mL beaker of ice water and
allow it to chill for another 10 min. If you do not
see any crystal formation when your flask is in the
ice water, gently scratch the inside of the flask
using a Teflon stir rod until you see precipitate
begin to form. Begin timing (10 min) from the
time you see the first crystals form.
g. Using manual vacuum filtration, filter your
product washing it with three portions of 2 mL of
ice-cold water.
16. Once you have dried the crystals as much as possible,
carefully transfer the filter paper and product into a
150 mL beaker whose mass you have already
measured. Place the beaker containing the product
and filter paper into the oven and allow it to dry for
20 to 30 minutes.
17. Determine the mass of your purified product. Ask
your TA to visually confirm the appearance and mass
of your product.
18. Perform a melting point analysis of the crude and
purified product.
19. Perform a TLC analysis of the crude and purified
product. Obtain the starting material reference from
your TA. Dissolve a small amount of your product in
ethanol. Develop your TLC plate using 1:3
ethanol:hexane.
4
 Questions
1. Draw a scheme showing the 4 possible
stereoisomers of 2,3-dibromo-3-phenylpropanoic
acid, indicating which pairs are enantiomers which
pairs are diastereomers. In your scheme, label each
isomer as (2S,3S), (2R,3R), (2R,3S) and (2S,3R).
2. In step 9, what is the purpose of adding
cyclohexene?
3. Can you explain why the (2R,3S) and (2S,3R)
enantiomeric pair has a melting point that is over
100ºC higher than the (2S,3S) and (2R,3R)
enantiomeric pair?

Report Notes
Refer to the instructions early in the lab manual
regarding the preparation of reports. Be sure to
explain all the steps of your experiment, paying
attention to the workup/purification. Add
mechanisms as necessary. Based on your
understanding of the reaction mechanism, predict,
and explain the major and minor products of the
reaction. The reaction mechanism and molecular
structures are the only parts that can be drawn by
hand. Everything else must be done on the computer
(without an electronic pen or stylus). If submitted
work is illegible or if the file cannot be opened or
read, the grade for that work will be zero.

Experiment 5 5