Nitration of Methyl Benzoate

Yvonne Maranan

Allysha Milanes

Kimberly Anne Moscosa

Hazel Padua

De La Salle University-Dasmariñas
Dasmariñas, Cavite, Philippines

ABSTRACT

Aromatic Hydrocarbons are ac chemical substances, which are known by having molecular
structures, which are called benzene rings, which are a very stable type of compounds that’s why
they do not react with substances from any other reactions in alkanes, alkenes and alkynes. They
are electron rich compounds with many positively charged ions. These Aromatic Hydrocarbons are
electrophiles, meaning they are attracted to negatively charged ions, creating a Electrophilic
Aromatic Substitution. There are several types of Electrophilic Aromatic Substitution such as
arenium ion mechanism, which is also called “re-aromatization”, inductive effects, nitration, etc. In
this experiment Nitration will be used to determine the Electrophilic Aromatic Substitution in Methyl
Benzoate. In the experiment, also we will be determining the Melting Point data and use Thin-layer
Chromatography of the compound said to ensure that the product formed was only the necessary
product needed to be produced.

INTRODUCTION

Nitration of Methyl Benzoate (C6H5CO2CH3) illustrates Electrophilic Substitution, which is

shown in Figure 1. Aromatic nitro compounds are used in products ranging from explosives to
pharmaceutical synthetic intermediates. Methyl Benzoate is formed by condensation of methanol
and benzoic acid in the presence of a strong acid like Hydrochloric Acid (HCl) The electrophile in
nitration is the nitronium ion. The Nitronium Ion is generated from nitric acid (HNO3) by protonation
and loss of water, using sulfuric acid (H2NO4) as the nitrating agent. Upon the process, Nitration,
methyl m-nitrobenzoate will be synthesized from methyl benzoate and purified by recrystallization
with methanol. The reaction must strictly be controlled to avoid futher formation of other unnecessary
compounds. To ensure that only the necessary compound, which is the methyl m-nitrobenzoate was
formed. Melting point and Thin-layer Chromatograph must be determined. In melting point
determination using a capillary tube with your re-crystallized product, heating it using the provided
Melting point apparatus comparing the actual yield and theoretical yield of the compound and
computing the % yield. Thin layer chromatography is using a thin, uniform layer of silica gel coated
onto a piece of rigid plastic. The silica gel is the stationary phase. The stationary phase for thin layer
chromatography also often contains a substance, which fluoresces in UV light for reasons you will
see later. The mobile phase is a suitable liquid solvent or mixture of solvents. TLC is a method for
analyzing mixtures by separating the compounds in the mixture. TLC can be used to help determine
the number of components in a mixture, the identity of compounds, and the purity of a compound. By
observing the appearance of a product or the disappearance of a reactant, it can also be used to
monitor the progress of a reaction.

Figure 1: Mechanism of Electrophilic Aromatic Substitution

MATERIALS AND METHODS

Table1. Reagents and Materials used

Reagents Materials

Methyl Benzoate (C6H5CO2CH3) Medicine Dropper

Concentrated Sulfuric Acid (H2NO4) Conical Flask
Concentrated Nitric Acid (HNO3) Pasteur Pipet
5% Sodium Bicarbonate (NaHCO) Watch Glass
Methanol (CH3OH) Hot Plate
Hexane (C6H14) Wash Bottle
Ethyl Acetate (C4H8O2) Buchner Funnel
Distilled Water (H2O) Filter Flask
Rubber Tubing
50 mL beaker
Test Tube
Filter Paper
TLC Plate

Table 1 shows the reagents and materials that was used in the experiment performed. 10
drops of pre-weighed methyl benzoate was added to a conical flask that was then placed into an ice
bath. Slowly, drop-by-drop, 2 mL of concentrated 𝐻! 𝑆𝑂! was added to the conical flask while swirling
and was later set aside. 1 mL of concentrated 𝐻𝑁𝑂! and 1 mL of concentrated 𝐻! 𝑆𝑂! was prepared
as the nitrating agent, that was then added to the methyl benzoate solution. The addition of a few
drops of concentrated 𝐻! 𝑆𝑂! helped to make the mixture clear upon it occurring as cloudy. After the
melting of the crushed ice that was added to the mixture, a solid product was produced that was
washed with distilled water and 5% 𝑁𝑎𝐻𝐶𝑂! . The product will then be recrystallized by placing 2-3
drops of methanol to it, until the entire product is dissolved. Crystals were filtered using Buchner
funnel with a filter paper, transferred to a pre-weighed watch glass and later determined its mass
and percent yield. Melting point determination was done by placing the powdered sample into the
capillary tube and using the melting point apparatus. TLC profile on the other hand was determined
through the immersion of the Silica gel TLC plate into a hexane: ether solvent that was marked with
a spotting line.
Figure 2. Vacuum Filtration

In this set up, the methyl m-nitrobenzoate that was produced by the Electrophile Aromatic
Substitution will be re-crystallized and purified through the vacuum filtration. Thus crystals that will
be used to test the melting point and TLC profile will be the product.

RESULTS AND DISCUSSION

Figure 3. Formation of Nitronium Ion

Figure 3 shows how the Nitrating Agent, the Nitronium Ion, was produced from
combination of Sulfuric Acid and Nitric Acid.

Figure 4. Nitration of Methyl Benzoate

Figure 4 shows how the combined Nitrating agent helps to produce Methyl m-
nitrobenzoate from Methyl Benzoate.

 A. Percentage Yield of Methyl m-nitrobenzoate

1. Mass of Conical Flask 92.4 g

2. Mass of methyl benzoate and conical flask 92.7 g

3. Mass of methyl benzoate 0.3 g

4. Mass of re-crystallized methyl m-nitrobenzoate 1.65 g

5. % yield 41.40%

B. Melting Point

1. Melting point of re-crystallized methyl m-nitrobenzoate 124˚C

2. True Melting Point of methyl m-nitrobenzoate 78-80˚C

3. % Difference 62.90%

C. Thin-layer Chromatography

Rf value:

Y/X (always ≤ 1)
Y X
2.1cm / 2.37cm

= 0.89

D. Calculation

% yield

(Actual yield/theoretical yield) * 100

(1.65 g / 3.98 g) * 100

= 41.40 %
Guide Questions:

1. Show the complete mechanism for the synthesis of methyl m-nitrobenzoate.

2. Why is it necessary that the reaction condition be maintained at a very low temperature and
all reagents be added very slowly?

Methylbenze reacts faster than benzene whereas in nitration, the react is about 25
times faster thus it is a must that the reaction condition be maintained at a very low
temperature to prevent more than one nitro group being substituted.

3. What are the possible side products formed in the nitration of methyl benzoate?

The possible side products that may form in the nitration of methyl benzoate are
small quantities of the ortho and para isomers and less of a dinitrated product.

4. Give the nitration product formed if phenyl benzoate is used.

The major product of nitration if phenyl benzoate is used will be p-nitrophenol

benzoate because the ortho position is partially blocked by the large COPh group.
CONCLUSION

We therefore concluded that even though the process of the experiment was not completed,
we have been given a chance to ensure that methyl m-nitrobenzoate was formed. The methyl m-
nitrobenzoate was prepared. The melting point and TLC profile were then determined to ensure the
formation of methyl m-nitrobenzoate.

RECOMMENDATION

In this experiment, it is needed to control the reaction conditions carefully to avoid the
formation of other by-product. Hence, it is recommended that upon performing this experiment, the
procedure must be done precisely. The contact with the acids used shall be avoided as well. To
prevent contact with the skin, eyes or clothing, it is also advisable to work inside the fume hood.
Because the reaction is highly exothermic, vigorous reaction will occur if the acid mixture is added
too rapidly to the methyl benzoate that may cause the acid to spill. In case this happens, acid spill
can be neutralized using solid carbonate or bicarbonate. It is therefore important to have adequate
knowledge on the harm that may be caused by the reagents involved to those who will be
performing the experiment.

REFERENCES

(1) http://www.chemguide.co.uk/analysis/chromatography/thinlayer.html
(2) http://www.chem.umass.edu/~samal/269/tlc.pdf
(3) https://www.chegg.com/study
(4) https://www.scribd.com/document/79657620/Nitration-of-Methyl-Benzoate
(5) http://www.labx.com/melting-point-apparatus
(6) https://www.uk.answers.yahoo.com