Experiment 4
Synthesis of Methyl m-Nitrobenzoate
Objectives
1. To study the electrophilic aromatic substitution (EAS) reaction.
2. To illustrate the preparation of aromatic nitro compound.
Introduction
Electrophilic aromatic substitution (EAS) reaction is generally a second order process which
occurs in three steps; generation of electrophile, electrophillic attack on aromatic system, and re-
aromatization. EAS is a very useful method for putting many different substituents on a benzene
ring even though there are other substituents already present (regioselectivity).
Nitration of aromatic compounds is one of the most important examples of EAS reaction. Apart
from being used mainly as powerful explosives or booster charges (TNT, Tetryl), aromatic nitro
compounds are also important as intermediates for the preparation of aromatic amino
compounds. By way of diazonium salts, this class of compounds can be easily converted into
other desired derivatives with -OH, -CN, -I, and -H. Nitrobenzene, which is the product of the
benzene nitration, is a suitable solvent for organic substances as well as for many inorganic
compounds like AlCl3 and ZnCl2. It is used occasionally as a reaction medium and also as a
solvent for re-crystallization. Most nitro compounds, either aromatic or aliphatic, are very toxic
and must be handled with great care.
In this experiment, a nitro group will be added on the benzene ring, which already has an ester
group attach to it. The electrophile in this reaction will be generated in situ using concentrated
nitric acid and concentrated sulfuric acid. Alternatively, nitronium fluoroborate (NO 2+BF4-) can
be used to generate electrophilic nitronium ion. The selection of suitable nitrating agents and the
reaction conditions depend upon the reactivity of the compound to be nitrated, its solubility in
the nitrating medium, and the ease of isolation and purification of the product.
Materials and Method
Glassware and Apparatus
Erlenmeyer flasks; 2 x 125mL
Ice-water bath
Buchner funnel
Stirring rod
Thermometer; 0-50°C
Pasteur pipette
Beaker; 150 mL
Graduated cylinders; 10 mL
Vacuum pump
Filter paper
Chemicals
Concentrated sulfuric acid
Concentrated nitric acid
Methyl benzoate
Distilled water
Methanol
Procedure
Warning: All nitro compounds are poisonous and must be handled very carefully. If
any nitro compound comes in contact with the skin, wash with ethanol followed by soap,
and a large amount of water.
1. Place 25 g (14.5 mL) of concentrated sulfuric acid in an Erlenmeyer flask, and chill
the acid in an ice-water bath.
2. Add with swirling, 0.05 mole (6.8 g, 6.2 mL) of methyl benzoate to the acid.
Continue to cool the mixture in the ice-water bath to reduce the heat, which is
produced in the reaction.
3. Prepare a mixture of 9 g (5 mL) of concentrated sulfuric acid and 0.085 mole (7 g, 5
mL) of concentrated nitric acid, and cool it in an ice-water bath. While maintaining
the internal reaction temperature at 5-15oC, add (with swirling) the cold acid mixture
drop-wise to the previous methyl benzoate solution. Continue to cool and swirl the
reaction mixture for 10 minutes until all the acid has been added.
4. Pour the reaction mixture upon about 50 g of ice cubes contained in a 150 mL beaker,
with stirring to precipitate the crude methyl m-nitrobenzoate which contains a small
amount of the ortho isomer and a trace of the para form.
5. Isolate the solid product by vacuum filtration through a Buchner funnel. Wash the
product thoroughly with two or three portions of 15 mL water to remove excess nitric
and sulfuric acids. (For effective washing, stop the suction, mix the material
thoroughly with water using a spatula, then apply suction while pressing the crystals
firmly). Finally, wash the product with two portions of 5 mL chilled methanol and
air-dried the product. Recrystallise from methanol.
6. Determine the weight and the melting point of the product.
Results and conclusion:
1. Calculate the percentage yield from the weight of the product obtained.
2. Write the reaction equation and mechanism for the nitration of methyl benzoate.
3. Compare the melting point of your product with that given in the reference. Give
comment on the purity of your product.
4. What is the purpose of chilled methanol washing in the above procedure?
5. The ease of nitration depends on the nature of the substituents present on the
aromatic ring. Explain.
6. Discuss the regioselectivity for EAS reaction.
7. Why dinitro products are not formed in this reaction?
Questions
1. List several important reactions of aromatic compounds that can be used to
differentiate aromatic compounds from aliphatic ones.
2. What is the product formed when nitrobenzene is reduced in the presence of acids?
3. Give the structures for picric acid, TNT, and Tetryl.
4. Give the major product(s) formed when each of the following substances is nitrated:
phenol, acetanilide, toluene, benzaldehyde, benzonitrile, benzoic acid, and phenylacetic
acid.
