Title: Nitration of Methyl Benzoate

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

Introduction:
Nitration is chemical process that introduces the nitro-group into an organic compound.
There are many major industrial applications of nitration in the strict sense; the most
important by volume are for the production of nitro-aromatic compounds such
as nitrobenzene. They are of wide importance as chemical intermediates and precursors.
In this experiment, the methyl-3-nitrobenzoate prepare from nitration of methyl benzoate
with the reagents such as nitric acid and sulphuric acid.



The nitration of methyl benzoate is a typically electrophilic aromatic substitution.
Electrophilic aromatic substitution is an organic reaction in which an atom that is
attached to an aromatic system is replaced by an electrophile. The position of the nitro-
groups attach is determined by the other functional group that already attached to the ring.
In this experiment, a nitro (NO
2
) group on a benzene ring which already has an ester
group is attached to it (methyl benzoate). The actual electrophile in the reaction is the
nitronium ion (NO
2
+
), which is generated in situ ("in the reaction mixture" HNO
3
/H
2
SO
4
)
using concentrated nitric acid and concentrated sulfuric acid.

HONO
2
+ H
2
SO
4
H
2
ONO
2
+
+ HSO
4
-

H
2
ONO
2
+
NO
2
+
+ H
2
O
H
2
O + H
2
SO
4
H
3
O
+
+ HSO
4
-

Overall reaction: HO-NO
2
+ H-HSO
4
NO
2
+
+ HSO
4
-
+ H
2
O
Apparatus and Materials:
Beaker, Glass rod, Test tubes, Pasteur pipette, Buchner funnel, Thermometer, Melting
point apparatus, Methyl benzoate, Concentrated sulphuric acid, Concentrated nitric acid,
Methanol, Mixture of methanol:water(1:1), Ice

Experimental Procedure:
6mL of concentrated sulphuric acid was added into a 100 mL beaker. The beaker was
cool in an ice bath (0C) for 5-10 minutes. 2.8 mL of methyl benzoate was added to the
cold sulphuric acid in the beaker, mix well and cool again to 0C for about 5 minutes. 2
mL of concentrated sulphuric acid and 2 mL of concentrated nitric acid are added in a
small test tube to prepare H
2
SO
4
/HNO
3
mixture. The acid mixture was cooled in an ice
bath (0C). The H
2
SO
4
/HNO
3
mixture was slowly added (drop-by-drop) to the
H
2
SO
4
/methyl benzoate mixture (in the beaker) by using pasteur pipette. The mixture was
swirled after each acid addition. The reaction beaker was kept in the ice bath during the
addition. When the addition is complete (all the H
2
SO
4
/HNO
3
mixture has been added),
the mixture was allowed to warm to room temperature. The reaction mixture was
standing for an additional 15 minutes to allow reaction to proceed to completion. The
reaction mixture was poured onto about 10 g of crushed ice in a beaker. The product was
isolated by vacuum filtration. The solid was rinsed with a tiny amount of ice-cold 50%
methanol (mixture1:1 methanol-water). The crude product was recrystallised by using
methanol as recrystallization solvent. The product yield and melting point were recorded.









Result:

Weight of product yield + weight of filter paper = 3.4304g
Weight of filter paper = 0.5050g
Weight of product yield = 2.9254 g
Melting point = 80 - 83C

Calculation:
C
6
H
5
CO
2
CH
3
+ HNO
3
C
6
H
4
CO
2
CH
3
NO
2
+ H
2
O
Density of methyl benzoate = 1.08 g/mL
Mass of methyl benzoate, C
6
H
5
CO
2
CH
3
= 3.0240g
Molar mass of C
6
H
5
CO
2
CH
3
= 136.1487 g/mol
No. of mole of C
6
H
5
CO
2
CH
3

= 0.0222 mol

1 mole of C
6
H
5
CO
2
CH
3
needed to produce 1 mole of C
6
H
4
CO
2
CH
3
NO
2

0.0222 mole of C
6
H
5
CO
2
CH
3
needed to produce 0.0222 mole of C
6
H
4
CO
2
CH
3
NO
2

Molar mass of C
6
H
4
CO
2
CH
3
NO
2
= 181.1463 g/mol
The theoretical yield of C
6
H
4
CO
2
CH
3
NO
2

= 0.0222 mol 181.1463 g/mol
= 4.0214 g

Percentage yield
=



=


100%
= 72.75%





Discussion:
In this experiment, the nitration of methyl benzoate undergoes electrophilic aromatic
substitutions. This reaction is involved the removal of hydrogen ion (proton) and replace
by the nitronium ion, NO
2
+
(electrophile) to become a substituent.


Figure 1: The mechanism of nitration of methyl benzoate

The sulphuric acid protonate the methyl benzoate to produce the resonance stabilised
arenium ion intermediates. The electrophile is attack by the protonated intermediate at the
meta-position of the aromatic ring. The reaction take place at the meta-position due to the
ester group on the aromatic ring is meta-deactivator. The ortho and para positions are
destabilised by the adjacent positive charge on the resonance structure. Lastly, the
methyl-3-nitrobenzoate is formed as a major product due to the carboxyl and nitro groups
towards the aromatic ring for both being powerful electron withdrawing groups.

In the experiment, the methyl benzoate is being nitrated by using nitric acid, HNO
3
and
sulphuric acid, H
2
SO
4
. During the process, the reagent was added slowly because the
reaction will be vigorous if added very fast. The temperature of the reaction also keep or
maintained at very low to avoid the formation of dinitro product. An activation energy is
needed for the substituted of nitro group on the aromatic ring. The increase of
temperature will increasing the heat energy for activation where another nitro group will
be have a higher activation energy than the first substitution of nitro group to the ring.
Thus, high temperature of this reaction increases the chance of forming of dintro product.

Figure 2: An example of dinitro product - Methyl 3,5-dinitrobenzoate.

The percentage yield of methyl 3-nitrobenzoate is 72.75% in which the weight of product
obtained experimentally is 2.9254g while the theoretical yield is 4.0214g.

Figure 2. methyl m-nitrobenzoate (white solid)

The loss of product may due to the transfer of compounds e.g. the evaporation happened
if liquid involved or the equilibrium system in the reaction is reached. The melting point
of the methyl 3-nitrobenzoate that obtained in this experiment is 80 - 83C. Although the
value we got is close to the literature melting point of methyl m-nitrobenzoate with 78 -
80C but that still have a slightly different value which may due to the product contain
the impurities or contaminator.

There are several safety precaution should be taken in this experiment. Nitric acid and
sulfuric acid are toxic and oxidizing. They can cause severe burns. Thus, safety goggles
gloves, and lab coat should be wear. Next, the reaction of concentrated sulfuric acid
between nitric acid is a highly exothermic reaction which the hot acid mixtures may
bump and cause acid burns. So, make certain the acids are cold before mixing.



Conclusion:
The methyl m-nitrobenzoate was prepared. The theoretical yield is 4.0212g while the
actual yield is 2.9254 g so we get the percentage yield is 72.75%. The melting point of
our product is 80-83C. From the given physical constant we know that the literature
melting point of methyl m-nitrobenzoate is 78-80C, so we can conclude that the product
we get is methyl m-nitrobenzoate.


References:

Nitration .2014. [online] Available at: http://en.wikipedia.org/wiki/Nitration [Accessed 5 July
2014]
Pahlavan/Cherif. Nitration of Aromatic Compounds: Preparation of methyl-m-
nitrobenzoate. [ pdf ] Available at: http://swc2.hccs.edu/pahlavan/2425L3.pdf. [Accessed
5 July 2014].