UNIVERSITI TEKNOLOGI MARA ARAU, PERLIS.

FACULTY OF APPLIED SCIENCE

BACHELOR IN CHEMISTRY
AS 202
CHM 624 (ADVANCED ORGANIC CHEMISTRY)
EXPERIMENT 2 : PREPARATION OF 4-BROMOBENZOPHENONE BY
THE FRIEDEL-CRAFTS REACTION

NAME: NIK ABDUL AZIZ B. NIK ABD. RAHMAN

MATRIX NUMBER: 2012457828
LAB PARTNER :
COURSE : CHM 624 (ADVANCED ORGANIC CHEMISTRY)
GROUP: ASB5Bc
DATE OF EXPERIMENT WAS DONE : 17th MARCH 2014
LECTURER NAME : DR. PM. RAZALI

OBJECTIVES
To prepare 4-Bromobenzophenone by the Friedel-Crafts Reaction.
To measure the percentage yield of 4-Bromobenzophenone.

INTRODUCTION
Electrophilic aromatic substitution reactions feature an electrophile replacing a hydrogen
atom in an aromatic compound and can form a new carbon-carbon bond if done with an
electrophilic carbon species. Such reactions were discovered in 1877 by Charles Friedel and
Crafts and are collectively known as Friedel-Crafts reactions. The introduction of an acyl group
into an aromatic ring is accomplished by an electrophilic substitution by the acylium ion
(RCO+) generated by the reaction between an acyl halide and aluminum chloride.
In bromobenzene, the benzene is a deactivating and ortho, para-directing substituent.
However this reaction gives mainly the para-isomer, presumably ortho-substitution which might
also be expected is sterically less favoured. This electrophilic aromatic substitution aromatic
allows the synthesis of monoacylated products from the reaction between arenes and acyl
chlorides or anhydrides. The products are deactivated and do not undergo a second substitution.
Basically, a stoichiometric amount of the Lewis acid catalyst is required because both the
substrate and the product form complexes. The Friedel-Crafts alkylation may give polyalkylated
products. However, the Friedel-Crafts acylation is a valuable alternative.

EQUIPMENT AND INSTRUMENTS

Steam bath
Rotary evaporator
Infrared Spectroscopy (IR Spectroscopy)

MATERIALS

Bromobenzene (FW 157.0)

Benzoyl chloride (FW 140.6)
Anhydrous aluminum chloride, (AlCl3)
Sodium hydroxide, NaOH (10%)
Diethyl ether
Light petroleum (60-80C)
Magnesium sulfate, MgSO4
pH indicator paper

2.0 mL, 3.0 g (19 mmol)

3.3 mL, 4.0 g (30 mmol)
4.0 g (30 mmol)

PROCEDURES
Preparation of 4-Bromobenzophenone
2 mL of bromobenzene was mixed with 3.3 mL of benzoyl chloride in a 50 mL conical
flask. Then. 4.0 g of AlCl3 was added in three portions. Prior to the addition, the conical
flask was shaked and stirred to mix it.
The flask was heated for 20 minutes in a boiling water bath.
After heating done, the dark red liquid was cooled and poured onto ice and the remaining
contents was washed out by careful addition of 10% NaOH to the flask. (to dissolve any

benzoic acid present and also aluminum salts)

Then, the solution was reheated for a few minutes.
He solution was removed and the brown oily precipitated was collected.
The brown solid obtained was let dissolve in water with addition of NaOH and ether.
The mixture was extracted with ether for 3 times, the organic extract was dried over

MgSO4 and the ether was removed on the rotary evaporator.

4-Bromobenzophenone remained and recrystallized from light petroleum to give a
colorless solid.
The yield and melting point of the product were recorded.
The product was analyzed with IR spectroscopy.

RESULT
Mass of weighing paper

0.1636 g

Mass of product + weighing paper

0.6007 g

Mass of product

0.6007 g 0.1636 g
0.4371 g

Observation: Solid form (crystal), brown in color

CALCULATIONS

Mol of bromobenzene=

mass
molar mass

3.0 g
157.0 g/mol

0.0191 mol(limiting reactant)

Mol of benzoyl chloride=

mass
molar mass

4.0 g
140.6 g/mol

0 . 0284 mol

Product name
Molecular formula
Molar mass
Melting point
Actual yield

4-Bromobenzophenone
C13H9BrO
261.11 g/mol
82C
0.4371 g

Theoretical yield=

261.11 g
0.0191mol
mol

4 . 9872 g

Percentage yield=

actual yield
100
theoretical yield

0.4371 g
100
4.9872 g

8 .76

DISCUSSIONS
In this experiment, 4-bromobenzophenone, was successfully obtained from the FriedelCrafts acylation reaction when bromobenzene was reacted with benzoyl chloride with presence
of a strong Lewis acid AlCl3.

Acylation of Bromobenzene

The percentage yield calculated from the reaction was 8.76% which is very small. This
was lower due to the fact that many of the crystals stick in the flask and could not remove it for
weighing. Besides that, the lower percentage yield is maybe due to loss during extraction with
ether or the extraction process was not complete. In addition, this experiment was supposed to
use rotary evaporator to remove the solvent but in the lab, the rotary evaporator was not
functioning well due to mechanical problems. So, we used conventional method to remove the
solvent by setup the water bath using hot plate and measured the temperature to the specific
temperature that we believe all the solvent will escape out. We assume, after reached the
temperature, all the solvent are fully escaped out and only product left in the flask. This is not the
proper way and inefficient in removing of the solvent. Due to this limitation, we believe this is
the main reason of why our yield is too little. Other than that, heating process must be enclosed
to avoid the evaporation of the product itself because the melting point of 4Bromobenzophenone is lower than the boiling point of water.
In this experiment, we using boiling water bath instead of rotary evaporator, which we
already know the temperature is 100C. The rotary evaporator is a motor-driven device that is
designed for rapid evaporation of solvents, with heating while minimizing the possibility of
bumping. Through this device, solvents are evaporated under reduced pressure. Based on the
observation, the physical appearance of the product is in the form of solid (crystal) and the color
was brown. Meanwhile, the observed melting point of the product was around 80C which is
considerably lower than the literature value of 82C. This is may be a result of the product still
being wet when the melting point was taken.
Besides that, it may also be due to impurities in the product. Most likely, there is still
some solvent present in the product that we didnt evaporate. In the future, maybe we need to let
our product to dry in the fume hood for a couple of days. As a result, some of the solvent, even
trace amounts of it, may still have been present in the product and this would have caused the
observed melting point become harder and thus lower than the literature value, as we observed.
From the literature, the 4-bromobenzophenone was expected to be in white color. However, we
only manage to obtain the product in brown color. This is due to the inefficient drying process
during the removal of diethyl ether. Supposedly, the removal process was done with the rotary
evaporator, but, there is some mechanical problem with the instrument.

So, we use the normal heating process using hot plate to remove or evaporate the diethyl ether.
Maybe this technique is not suitable and because of that we did not manage to completely
remove the ether. This can be proved by the IR spectra which shown that there is a presence of
ether (alcohol) in the product. Ketone supposed to have IR absorption at range of 1680-1750 cm 1

but the absorption was around 1650-1700 cm-1. So, we assumed the product obtained has a

functional group of ketone and small peak in the spectra was assumed to belong to it. The peak
obtained is very small due to small percentage of product obtained. Please see the IR spectra
attached together with this report for a detailed interpretation of the spectrum.

Conclusion:
From the experiment, the product obtained was 4-bromobenzophenone. The percentage yield
calculated was 8.76% and the melting point observed was about 80C.

REFERENCES
Pavia, Lampman, Kriz, Engel, Introduction to Organic Laboratory Techniques A Smale
Scale Approach, Thomson Brooks/Cole Publishers, 3nd ed., 2009.
http://webbook.nist.gov/cgi/cbook.cgi?ID=C1075496&Mask=80#IR-Spec
Engel R. G., Kriz G. S., Lampman G. M., Pavia D. L., Introduction to Organic
Techniques- A Small Scale Approach, 3rd Ed., Brooks/Cole Cencage Learning , Canada,
2011.