Nitration of Methyl Benzoate

By
Simi Kaur

Purpose: The objective of this experiment was to subject Methyl Benzoate to a nitration process
in order to observe electrophilic substitution reaction in creating methyl m-nitrobenzoate.

Reactions:

Mechanism:
Procedure:

About 1.26mL of methyl benzoate was added to a 25mL round bottom flask. Then,
2.7mL of concerted sulfuric acid was added to the round bottom flask as well as a spin vane. An
air condenser was attached to keep the round bottom in place. Then, an ice bath was prepared in
a 250mL beaker using a mixture of both ice and water. The condenser and round bottom flask
apparatus was clamped to allow the round bottom flask to be submerged in the ice bath. The
entire apparatus was placed above a heat plate with only the spin vane magnet turned on so as
allow stirring to occur. While the mixture stirred, a cooled mixture of 0.9mL of concentrated
sulfuric acid and 0.9mL of concentrated Nitric Acid was slowly added via the condenser over a
period of 15minutes. After all the acid was added, the mixture in the round bottom flask was
allowed to warm to room temperature by removing it from the ice bath and submerging it in a
250mL beaker full of room temperature water. The mixture was allowed to warm for 15 minutes
without stirring. Then, using a Pasteur pipette the mixture was transferred to a 20mL beaker
containing about 12.0g of crushed ice. After the ice melted away, the product was isolated using
vacuum filtration in a Hirsh Funnel. The product was washed with 1.0mL portions of cold water
and then two 1.8mL portions of ice-cold methanol. Due to no product formation, the oily lipid
formed was separated from water and left to dry overnight. The next day, the product was exactly
same and tested for reactivity via an IR. No melting point could be done as there was no product
formation.
Data Analysis:

Physical Data Table

Compound MW mmol wt. Den. Vol. M.P. C B.P. Hazards
(g/mol (g) (g/mL) (mL) C
)
Methyl 136.15 1.678 - 1.088 0.210 -15 199.6 Irritant
Benzoate flammable
Concentrated 98.1 11.25 - 1.840 0.60 10 290 corrosive
Sulfuric Acid irritant
Concentrated 63.02 3.36 - 1.41 0.15 -42 83 irritant
Nitric Acid

Data Observations:
The reaction mixture inside the round-bottom flask after being allowed to warm up and placed in
the ice bath creating a separate lipid-like product. Once the ice melted, there was a clear
distinction of water and lipid product. The lipid was then separated from the water as possible via
decanting of the water. The collected lipid production was allowed to dry overnight in hope of
finding a product. Unfortunately, the product was not created. To test for reactivity, this lipid was
put through infrared spectroscopy. Consequently, an IR was taken of the original solution of
methyl benzoate. The peaks were seen to be practically the same and hence concluded that the
experiment resulted in a no reaction.
Data Analysis/Discussion:
The reaction did not occur as expected as there was no actual product fomration. This
was not an isolated occurrence with myself but with the entire class conducting this experiment.
The lipid formation was the only result of the experiment. The final product should have been
isolated as a white solid powder. Because this experiment involves nitrating the m-ring, most of
us experienced difficulties as the solid was most likely trapped in a lipid. There was no success
in isolating the product [(m)-nitrobenzoate] from the lipid. To confirm that there was no actual
product formed, I compared the IR of the lipid and the IR of the original methyl benzoate used.
The peaks of the two were compared. The comparison revealed very similar peaks and did not
match that of the spectrum shown in the book for methyl m-nitrobenzoate. This aided in the
conclusion that this experiment yielded in no reaction. The issue could have been in the
laboratory preparation of the reactants or perhaps the concentrations or amounts of the reagents
were created off scale as throughout the lab the scale changed from the one written in the lab
notebook to create a suitable amount of product. Another issue could have been in the technique
of adding the acid to the mixture in the round bottom flask. This could have led to the reaction
not being created. As such, no melting point was taken of this lipid and the lab was concluded in
this manner. The molecular modeling done on the next day was used to prove the position of the
Nitro group would be in the meta position.
The nitration of methyl benzoate is a typical electrophilic aromatic substitution reaction.

Three positional isomers are possible, but they are never formed in equal amounts. All electron-
donating (activating) groups give predominantly to the ortho- and Para isomers as products. All
strongly electron-withdrawing (deactivating) groups give predominantly the meta-isomer as
product. The weakly deactivating halogens give predominantly the ortho- and para- isomers as
product. The electron donation of activating groups is greatest for the ortho- and para-
intermediates (and transition states). The electron withdrawal of deactivating groups is greatest
for the ortho- and Para intermediates (and transition states), thus making the meta pathway
lowest energy and is what is seen in the purpose of this lab experiment.

Conclusion:
With the comparison of the Infrared Spectrums, it was concluded that the experiment yielded a
no reaction result.

Post Lab Questions:

I. Why is methyl m-nitrobenzoate formed in this reaction instead of the ortho or para
isomers?

Methyl m-Nitrobenzoate is formed in this reaction rather than that of the

ortho/para isomers because of the ester group of the starting product of
methylbenzoate. The functional group of ester is an electron withdrawing group
causing nitrobenzene (NO2) to become in the meta position. Thus NO2 is a
deactivating group causing itself to be a meta director. Basically you look at the
substituents that are attached to the starting benzene ring in order to figure out
whether your reaction with be ortho/para directors or meta directors. If the
substituents are electron withdrawing groups, then you will be left with meta as
your product but if your substituents are electron donating groups then your
product will be ortho/para.

II. Why does the amount of the dinitration increase at high temperature?

When nitro groups are added onto the aromatic ring of methyl benzoate, as with
all chemical reactions, there is an activation energy needed to substitute the NO2
group onto the ring. Adding a second NO2 group will have a higher activation
energy than the first. Hence, higher temperatures = more available heat (energy)
for activation.