CHM 217 Experiment # 9 :

Electrophilic Aromatic Substitution: Nitration of Methyl Benzoate

Objective

• To learn and understand electrophilic aromatic substitution.

• To synthesize methyl m-nitro benzoate by mono nitration of methyl benzoate.
• To identify the product by melting point determination.
Introduction

Electrophilic aromatic substitution is an organic reaction in which an atom that is

attached to an aromatic system (usually hydrogen) is replaced by an electrophile.
Common electrophilic substitution reaction include nitration, alkylation and
halogenation.
Each of these substitution involves two steps:
Step 1: Attack of The Electrophile (E+) by a Pi-bond of the aromatic Ring- This step
involves attack of the electrophile (E+, a seeker of an electron pair) by the π electrons
of the aromatic ring, yielding an arenium ion which is a hybrid of three major
resonance forms.

Fig 8.1 Resonance structures (Arenium ion).

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Step 2: Deprotonation of the Tetrahedral Carbon regenerates the Pi bond –In this
step, loss of a proton by breaking C – H bond and restore of aromaticity by forming
C – C (π) bond takes place.

Fig 8.2
If a benzene ring is already substituted, these substituent atom or group may direct
an incoming electrophile to either the ortho‐para positions or the meta position.
These substituent atoms/groups are categorized into activating groups and
deactivating groups.
Activating groups: The substituent atoms or groups (attached to the ring) that make
the benzene molecule more reactive towards electrophilic substitution by increasing
the ring's electron density (by donating electrons) are called activating groups.
Activating groups serve as ortho‐para directors when they are attached to a benzene

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ring, meaning that they direct an incoming electrophile to the ortho, para positions.
Most ortho-para directors activate the ring by making it more nucleophilic.
Deactivating groups: An atom or group (attached to the ring) that makes the benzene
molecule less reactive by removing (by withdrawing) electron density from the ring
acts as a deactivating group. Deactivating groups direct an incoming electrophile to
the meta position. All meta directors make the ring less nucleophilic.

Fig 8.3
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Mechanism of the reaction
If the substituent group is a deactivating group(electron withdrawing group), Meta
position will be comparatively more nucleophilic (electron rich). Refer
the resonance structures below showing ortho, para positions are with partial positive
charges (less nucleophilic) resulting into meta substituted compound (electron
seeking electrophile can only attack electron rich site which is meta position).

Fig 8.4
If the substituent group is activating group (electron donor), ortho and para positions
will be more nucleophilic (refer the resonance structures below showing ortho, para
positions are with partial negative charges) resulting into ortho and para substituted
compound (electron seeking electrophile can only attack electron rich sites which are
ortho and para positions).

Fig 8.5

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Examples of Ortho, Para, Meta directors :

Common Characteristic feature of ortho, para directing group - substituent atom

attached to the ring has one or more unshared pairs of electron. Eg: -NH2 in this
group ‘N’ is the atom attached to the ring which has unshared pair of electrons on it,
which will be donated to the ring (by resonance effect).

/ ↑
t ->
↓ ↓

Fig 8.6
Exceptions to above features are alkyl group such as -CH3, -C2H5 etc.. It is because
in the methyl group, carbon atom is more electronegative than hydrogen (to which it
is attached), and it attracts more share of electron density from the (C-H) covalent
bond and acquires partial negative charge which is available to be donated to an
adjacent atom.

Fig 8.7

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Common Characteristic feature of meta directing group – the substituent atom
attached to the ring is bonded to a more electronegative atom and the substituent
atom attain partial positive charge on it. Eg: -NO2 group, in this group ‘N’ is the
atom attached to the benzene ring which has partial positive charge on it as it is
attached to more electronegative atom ‘O’. So ‘N’ will withdraw electrons from the
ring.

Fig 8.8

Halogens are an exception of the deactivating group that directs the ortho or para
substitution. The halogens deactivate the ring by withdrawing electrons from the
ring, even though they have an unshared pair of electrons. The unshared pair
of electrons gets donated to the ring (resonance effect), and also electrons are pulled
away from the ring due to high electronegativity of the halogens. But resonance
effect predominates. That is why they are categorized as weakly deactivators, but are
ortho, para directors.

Fig 8.9

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Formation of the electrophile for Nitration: Nitration of benzene occurs with a
mixture of concentrated nitric and sulfuric acids. Here nitric acid accepts a proton
from a stronger sulfuric acid and protonated nitric acid dissociate to form nitronium
ion.

Fig 8.10
Formation of the electrophile for Alkylation: An aromatic ring can be alkylated
by an alkyl halide in the presence of a Lewis acid such as aluminum chloride ( This
reaction is named after its discoverers as Friedel- Craft Alkylation.) The Lewis acid
serves to generate a carbocation electrophile, R+.

R Cl + AlCl3 R+ + Cl AlCl3

Fig 8.11
Formation of the electrophile for halogenation: Bromine combines with FeBr3 to
form a complex that dissociates to form a positive bromine ion(electrophile) and
FeBr4-.

Br Br + FeBr3 Br+ + Br FeBr3

Fig 8.12

[
In this experiment students carry out an electrophilic aromatic substitution (aromatic
nitration) on a monosubstituted benzene (methyl benzoate). The electrophile in
aromatic nitration is the nitronium ion (NO2+). Nitration is the substitution of an
NO2 group for one of the hydrogen atoms on a benzene ring.

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The reaction for the conversion of methyl benzoate to methyl meta nitro benzoate

Procedure :
• Transfer 7.0mL of Concentrated Sulfuric acid to a clean, dry
100mLErlenmeyer flask.
• Cool the above flask in an ice bath.
• Measure 3.2mL of Methyl benzoate in a 10mL measuring cylinder and
transfer to the above flask in small increments using a dropper. Stir the
mixture for every addition.
• Measure 5.0mL of the icecold mixture of Nitric acid and Sulfuric acid in the
same measuring cylinder and transfer to the methyl benzoate-sulfuric acid
solution drop by drop over a period of 5 mints. Stir the mixture for every
addition (temperature of the mixture should be below 10°C before every
addition to avoid multi substitution)
• When the addition is completed, remove the solution from the ice bath
and allow it to attain room temperature for 10mints, with occasional stirring.
• Pour the mixture with stirring over 30g of crushed ice in a 150mL beaker.
• Make sure to transfer all the solution to the ice from the Erlenmeyer flask by
rinsing with ice cold water.
• By now the product should have solidified, wait until the ice melts.
• Collect the solid by suction filtration, wash the product by ice cold water
several times to remove all the acids (in the video washing liquid is tested for
the presence of acid using litmus paper)
• Finally wash the product with 5mL portion of icecold Methanol (Methanol
being volatile, can be evaporated off easily without melting away the product.)
• Transfer the filter paper and the product to the petri dish and dry it in the oven

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 for 5 mints (this step is optional as methanol will dry the product effectively,
and can be evaporated off easily. If needed, oven should be set at 60°C as the
melting point of the compound is 78-80°C whereas boiling point of methanol is
60°C).
• Determine the yield and melting point of the compound.
• Show the product to the instructor.

Caution
• Both conc. sulfuric acid and conc. nitric acid are very potent and will cause
severe burns. Use gloves to handle and droppers to transfer these chemicals.
• At higher temperatures there is a greater chance of getting more than one
nitro group substituted onto the ring.

Waste disposal:
• Discard the product and filter paper into a given solid organic waste
container.
• Discard all used capillary tubes in the waste beaker.

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 Experiment # 9: Electrophilic Aromatic Substitution: Nitration of
Methyl Benzoate
PRE_- LABORATORY QUESTIONS
Name: _ AUS ID#:

Date: Lab Instructor: _ Lab Section:

1. Give the mechanism to generate nitronium ion and explain the role of sulfuric acid.

2. Show how the ester group (-COOCH3) is a meta director.

3. Explain with the resonance structures the activity of electron withdrawing and electron
donating groups present on the benzene ring towards electrophilic substitution reaction.

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 CHM 217 Experiment # 9 :
Laboratory Report : Electrophilic Aromatic Substitution:
Nitration of Methyl Benzoate

Name: AUS ID

Date: Lab Section: Lab Instructor:

Reagent Molecular weight(g/mol) Volume(mL) Mass(g) Moles

Methyl benzoate

HNO3

H2SO4

(Given: specific gravity HNO3 = 1.42, H2SO4 = 1.84)

The Limiting reactant for the reaction: ……………………………

Molecular weight of the product: ................................................... g/mol

Theoretical yield of the product: .................................................... g

Actual (Experimental Yield) : ......................................................... g

Percentage yield:............................................................................... %

Name and structure of the product:

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 Questions

1. Write the detailed mechanistic step of conversion of methyl benzoate to methyl

meta nitro benzoate.

2. What is the purpose of washing the product using methanol during vacuum
filtration?

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3. Care is taken to maintain very low temperature throughout the experiment.
Explain why?

4. Indicate whether each of the following substituents is o,p or a m- director

-NO2 ………………….. -N=O ……………………

-NH2…………………… -SCH3 ……………………

-C2H5………………….. –SO3H ………………….

5. Write structural feature of o,p and meta directing groups.