Experiment: Nitration of Methyl Benzoate

Objective : To prepare methyl-3-nitrobenzoate from the nitration of methyl benzoate

Introduction:
This is an electrophilic aromatic substitution reaction, which is due to the high density of the
benzene ring. Nitration of the benzene ring is addition of a nitrate (-NO 2) group to the
existing benzene ring, which is generated from the protonation of nitric acid and loss of water
by using sulphuric acid as a dehydrating agent.

HNO3 + 2H2SO4  NO2+ + H3O+ + 2HSO4-

The nitro group will be added to the benzene ring which initially has an ester group attached
to it, which acts as a meta deactivating group that is why the reaction conditions need to be
modified in order for the reaction to occur. The reaction is highly exothermic and hence
should be kept in control by cooling the mixture in ice water bath.

The product is easily isolated by filtration and then recrystallized by heating the product in
methanol before recrystallizing it again and filtering it to obtain the final pure product.
Apparatus :
Beaker, Glass rod, Test tubes, Pasteur pipette Buchner funnel, Vacuum pump, Thermometer,
Melting point apparatus

Chemicals/Reagents:
Methyl Benzoate, Concentrated sulphuric acid, Concentrated nitric acid, methanol, 50%
methanol (1:1 methanol: water), ice.

Procedure :
(1) 6mL of concentrated sulphuric acid was added into a 100 mL beaker and was cooled
in an ice bath for 5-10 minutes.
(2) Then, 2.8mL of methyl benzoate was added to the cold sulphuric acid, mixed well and
cooled in the ice bath. Meanwhile, 2mL of concentrated sulphuric acid was added to 2
mL of concentrated nitric acid to prepare the HNO3/H2SO4 mixture and was cooled in
an ice bath as well.
(3) The HNO3/H2SO4 was then added to the H2SO4/methyl benzoate drop wise with
constant swirling. After the addition of the HNO3/H2SO4 was completed, the mixture
was warmed to room temperature and left to stand for 15 minutes.
(4) The reaction mixture was then poured into a beaker containing about 10g of crushed
ice. Then, the product was isolated by vacuum filtration and was rinsed with a small
amount of 50% methanol. The product was then heated with methanol until it
dissolved.
(5) The redissolved product was cooled in an ice bath to recrystallize it. The
recrystallized product was filtered by vacuum filtration to obtain the purified product.
(6) The pure product was weighed and its melting point determined.

Results and Calculations:

Amount of methyl benzoate used (mL) 2.8
Mass of the plastic bag (g) 0.5271
Mass of plastic bag + product (g) 2.6029
Amount of pure methyl m-nitrobenzene 2.0758
obtained (g)
Melting point of methyl nitrobenzene (°C) 86
Literature melting point of methyl m- 77-81
nitrobenzene (°C)
Density of methyl benzoate = 1.094 g/mL
Weight of methyl benzoate = 2.8ml x 1.094 g/mL
= 3.0632 g
Molecular weight of methyl benzoate = 136.15 g/mol
Mols of methyl benzoate = (3.0632 g / 136.15 g/mol)
= 0.0225 mols

1 mol of methyl benzoate produces 1 mol of methyl m-nitrobenzene

Hence 0.0225 mols of methyl benzoate used will produce 0.0225 mols of methyl m-
nitrobenzene.

Molecular weight of methyl m-nitrobenzene = 181.14 g/mol

Theoretical weight of methyl m-nitrobenzene = (0.0225 mols x 181.14 g/mol)

= 4.08g

Yield = (2.49/4.08) x 100%

= 61.03%
Discussion:
Nitration is the introduction of the nitro group (-NO2) into the chemical compound, in this
case methyl benzoate. Methyl benzoate was used because the desired end product was a Meta
position of the nitro group, and the methyl group is a meta-deactivating group, which allows
for a greater degree of control in exchange for a slower reaction. The reagents were added
drop wise to avoid a vigorous reaction and the temperature kept extremely low in order to
control the reaction even more to avoid the formation of a dinitro product at both meta
positions.

Electrophilic aromatic substitution involves the replacement of a proton on the

aromatic ring with an electrophile that ends up becoming the substituent. Sulphuric acid
solvates the methyl benzoate, protonating it and creating a resonance stabilized arenium ion
intermediate. The electron deficient nitronium ion then reacts with the protonated
intermediate in the meta position. This happens because the ester group is a meta deactivator
and the ortho and para positions are destabilized by adjacent positive charges on the
resonance structure. The major product is at nitrobenzene at the meta position due to the nitro
group being a powerful electron withdrawing group.
 The actual amount of pure methyl m-nitrobenzene obtained was 2.49g versus a
theoretical amount of 4.08g, a yield of 61.03%. This discrepancy may be due to loss of
product stuck to the filter paper or the sides of the beaker or even been slightly dissolved
back into the filtrate by improper washing.
The melting point obtained was 86°C as compared to a literature melting point of 78-
80°C and the difference may be due to improper reading of the apparatus or some impurities
present in the purified product such a slight amounts of water. The precautions steps taken in
the experiment includes handling both sulphuric and nitric acid with added care and while
wearing gloves to avoid spillage on skin and it was also ensured that the nitration waste and
methanol waste was not discarded into the same waste bottle. This was to avoid the formation
of an explosive material, nitromethane.

Conclusion:
The amount of pure methyl m-nitrobenzene obtained was 2.49g with a yield of 61.03%. The
melting point obtained was 86°C.

References

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3. Pubchem. (2018, 06 27). Methyl Benzoate. Retrieved from PubChem - Open
Chemistry Database:
https://pubchem.ncbi.nlm.nih.gov/compound/methyl_benzoate#section=Top
4. PubChem. (2016, 06 27). Nitromethane. Retrieved from PubChem - Open Chemistry
Database: https://pubchem.ncbi.nlm.nih.gov/compound/6375
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