4-Bromobenzophenone by Friedel-Craft Reaction

OBJECTIVE
1. To prepare 4-Bromobenzophenone by the Friedel-Craft reaction

2. To obtain the yield and melting point for product and analyse the product
using IR and NMR spectroscopy.
INTRODUCTION
Friedel-crafts acylation is defined when an acyl group is introduced
into a compound. Two common acyl groups are the acetyl group and the
benzoyl group. This reaction is an effective means of introducing an acyl group into
an aromatic ring. The reaction is often carried out by treating the aromatic
compound with an acyl halide. Unless the aromatic compound is one that is
highly reactive, the reaction requires the addition of at least one equivalent of a
Lewis acid such as AlCl 3 as well. The product of the reaction is an aryl ketone.
(Solomon, G. and Fryhle, G., 2002).Though the reaction has some limitations
which namely the potential for carbocation rearrangement limiting the types of
alkyl chains that can be substituted, its relative simplicity makes it an important
tool when dealing with aromatic syntheses.
Benzophenone (C13H10O) is the organic compound. Benzophenone is a

widely used building block in organic chemistry, being the parent
diarylketone. 4-bromobenzophenone(C13H9BrO) is obtained by the reaction
between bromobenzene and benzoyl chloride under Friedel-Crafts reaction.
The introduction of an acyl group into an aromatic ring is accomplished by an
electrophilic substitution by the acylium ion (RC≡O +) generated by the reaction
between an acyl halide and aluminium chloride. In bromobenzene, the benzene is
deactivating and ortho, para-directing substituent. However, the reaction mainly
gives para-isomer, presumably ortho-substitution which might also be
expected is sterically less favoured. Here is the general mechanism of the
experiment:
EQUIPMENTS AND INSTRUMENTS
Steam bath, rotary evaporator, IR spectroscopy
MATERIALS
Bromobenzene (FW 157.0) 2.0 mL, 3.0 g (19 mmol)
Benzoyl chloride (FW 140.6) 3.3 mL, 4.0 g (30 mmol)
Anhydrous aluminium chloride (FW 133.3) 4.0 g (30 mmol)
Sodium hydroxide (10%)
Diethyl ether
Light petroleum (60 - 80˚C)
pH indicator paper
PROCEDURE
2.0 mL of Bromobenzene and 3.3 mL of benzoyl chloride were placed in a 50
mL Erlenmeyer flask. The 4.0 g of anhydrous aluminium chloride was added in three
portions. The mixture was shaking and stirring in between additions, and then the
flask was heated on a boiling water bath for 20 min. 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. Make the combined solutions alkaline by the addition of
10% NaOH solution to dissolve any benzoic acid present and aluminium salts. The
combined solution was extracted with 2 x 25 mL of ether, the organic extract was
dried over MgSO4 and the ether was removed on the rotary evaporator. 4-
Bromobenzophenone remains and was recrystallized from light petroleum to give a
colourless solid. The yield and melting point of the product were recorded. The
purified material was analysed using NMR and IR spectroscopy.
RESULT AND OBSERVATON (PREDICTED RESULTS)

Observation:
1. When added the 10% NaOH solution, the solution produces white precipitate.
2. Aluminium chloride has been weighed in fumed hood because it is
hygroscopic which is tends to absorb moisture from the air.
Reagents Mass (g)

Bromobenzene 3.050
Benzoyl chloride 4.000
Aluminium chloride 4.000
Table 1. The mass of reagents used in the experiment
Erlenmeyer flask 10.2192g
Erlenmeyer flask + product 10.6736g
Product (4- 0.4544g

bromobenzophenone)
Melting point 83-85℃
Table 2. Mass and melting point of 4-bromophenone

O
Br
4 -B ro m o b e n z o p h e n o n e
Bond Vibration Literature Experimental

Wavenumber Wavenumber
CM-1 CM-1
C=C Stretching 1400- 1600 1578.29
(Aromatic)
C=O (Ketone) Stretching 1780-1 710 1728.72
C-Br Stretching 60 0-500 -
Table 3. IR spectrum of 4-bromobenzophenone
O
Hb H d
H c H e
Ha Hb Hd Br
H c H e
4 -B ro m o b e n z o p h e n o n e
H signal Theoretical chemical Experimental chemical

shift (ppm) shift (ppm)
Ha 6.0-8.5 7.56
Hb 6.0-8.5 7.10
Hc 6.0-8.5 6.89
Hd 6.0-8.5 7.32
He 6.0-8.5 7.29
Table 4. NMR spectrum of 4-Bromobenzophenone
DISCUSSION
The percentage yield obtained from the expriment is 8.96%. The yield was quite low
because some error might occurred during the experiment and also, the product that
we had obtained is a crude product, as we did not success in doing the
recrystallization process. The melting point that we obtained was in a range. The
melting point of the product is 83-85℃ where the theoretical melting point of 4-
bromobenzophenone is between 79-84℃. However, we cannot prove the true
product based on the melting point, so we doing the IR analysis in order to prove
more clearly the product that we obtained which was 4-bromobenzophenone.
Based on IR spectrum in table 3, shows the literature wavenumber and

experimental wavenumber for 4-bromobenzophenone shows the presence of band
peaks for aromatic C=C stretch at 1578.29 cm -1 experimental wavenumber. It also
shows peaks for C=O ketone stretch at 1728.72 cm -1. However, we did not found the
C-Br peaks in the spectrum where the literature wavenumber of C-Br peaks should
be at 600-500 cm-1. Supposedly, there are more functional groups detected.
However, due to some errors during handling the experiments not all the functional
groups of 4-bromobenzophenone was found in the spectrum. Then, from NMR
1
result, the product can be proven as 4-bromobenzophenone as all the signal H
appeared
There might be some errors happen during conducting the experiment.

Product that we obtained from the experiment is just a crude product which it might
affect the IR results. Other than that, during removing the alkaline solution in order to
collect the brown oily precipitate. The solution was not completely removed and
would be used in the next steps. Next is during extraction process with ether
because the mixture was not separated very well. Finally, the use of contaminated
apparatus would affect the end result to be analysed. Therefore, some precaution
step should be taken in order to minimize the error and obtain the accurate result.
During removing the alkaline solution, ensure that all of it must be remove
completely, only leaving one layer, which is the brown oily precipitate. In extraction
process, the mixture in the presence of ether must be shake properly and again
remove the unwanted layer carefully. The use of clean apparatus is important
because the addition of contaminants into the mixtures or chemical would affect the
result of the product obtained in terms of yield, melting point and IR analysis.
CONCLUSION
In conclusion, 4-bromobenzophenone was synthesized by using Friedel-
Crafts reaction. The percent yield and the melting point of the product is 8.96% and
83-85℃ repectively. There were only two bond was detected from the IR spectra
which is C=O bond of ketone and C=C aromatic ring at 1728.72 cm -1 and 1578.29
cm-1 experimental wavenumber respectively. However, C-Br bond was not found.
The product of 4-bromobenzophenone can be proven from NMR result.
QUESTIONS
Suggest syntheses of the following from benzene
Answer,
Answer,
Answer,
REFERENCES
Friedel-Crafts Acylation. (n.d.). Retrieved April 18, 2020, from https://www.organic-
chemistry.org/namedreactions/friedel-crafts-acylation.shtm
Manrose. (n.d.). ADVANCED ORGANIC CHEMISTRY (CHM 624 EXPERIMENT 2
TITLE 4-BROMOBENZOPHENONE BY THE FRIEDEL-CRAFTS
REACTION. Retrieved April 22, 2020, from
https://www.coursehero.com/u/file/39610065/Experiment-2docx/?
justUnlocked=1#doc/qa
Organic Chemistry- 10 Edition. (2011). Retrieved April 18, 2020, from
https://www.academia.edu/34297512/Solomons_Fryhle_-
_Organic_Chemistry_-_10_Edition.pdf
APPENDIX
Calculations:
Mass(g)
Mol of bromobenzene = g
Molar Mass( )
mol
3.05 g
=
157.01 g/mol
= 0.0194 mol
Mass(g)
Mol of Benzoyl chloride = g
Molar Mass( )
mol
4.0 g
=
140.57 g /mol
= 0.0285 mol
⸫ Thus, the limiting reagent is bromobenzene
Calculation of the theoretical yield of 4-bromobenzophenone
Molar mass of 4-bromobenzophenone = 261.12 g/mol
Mol of 4-bromobenzophenone = mol of bromobenzene

= 0.0194 mol
Theoretical yield of 4-bromobenzophenone
= mol x molar mass
= 0.0194 mol x 261.12 g/mol
= 5.0724 g
Actual mass
% yield = x 100%
T h eoretical yield
0.4544 g
= x 100%
5.0724 g
= 8.96 %
PRE-LABORATORY PREPARATION

4-Bromobenzophenone by Friedel-Craft Reaction

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What is the objective of the experiment?

What is the objective of the experiment?

What is the predicted product of the reaction?

What is the predicted product of the reaction?

OBJECTIVE

1. To prepare 4-Bromobenzophenone by the Friedel-Craft reaction

Benzophenone (C13H10O) is the organic compound. Benzophenone is a

RESULT AND OBSERVATON (PREDICTED RESULTS)

Reagents Mass (g)

Erlenmeyer flask 10.2192g

Erlenmeyer flask + product 10.6736g

Product (4- 0.4544g

Melting point 83-85℃

Table 2. Mass and melting point of 4-bromophenone

Bond Vibration Literature Experimental

C=O (Ketone) Stretching 1780-1 710 1728.72

C-Br Stretching 60 0-500 -

Table 3. IR spectrum of 4-bromobenzophenone

H signal Theoretical chemical Experimental chemical

Based on IR spectrum in table 3, shows the literature wavenumber and

There might be some errors happen during conducting the experiment.

Suggest syntheses of the following from benzene

⸫ Thus, the limiting reagent is bromobenzene

Calculation of the theoretical yield of 4-bromobenzophenone

Molar mass of 4-bromobenzophenone = 261.12 g/mol

Mol of 4-bromobenzophenone = mol of bromobenzene

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