CHEM 331-Lab

Organic Chemistry

Experiment 8
Electrophilic Aromatic Substitution:
Nitration Reaction

Department of Chemistry - Faculty of Science

Beirut Arab University
Fall 2020-2021
 Aim of the Experiment

Understanding the concept of Electrophilic Aromatic

Substitution (EAS) by studying the specific generation
of nitronium ion onto a chlorobenzene ring.

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 Electrophilic Aromatic Substitution Definition
 Is an organic reaction in which an atom that is attached to an aromatic system (usually hydrogen) is
replaced by an electrophile.
 The arene system contains an electron rich C=C system which react with electrophiles via a
substitution pathway (to preserve aromaticity) via what is known as electrophilic aromatic
substitution (EArS).

Electrophilic Aromatic Substitution

Presence of an electrophile Aromatic system, presence Implies that a group

(E+), which is an electron of double bond in the usually hydrogen) is
poor species (cation) which benzene ring which reacts replaced by another group
reacts with an electron rich as supplier of π-e- to an
species Nucleophile (Nu-). electrons seeking reagent.

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 EAS includes:
Reaction Reagents Electrophile Product Comments
O O-
N+
E+ formed by loss of
Nitration HNO3/H2SO4 NO 2
+

water from nitric acid

SO3H

Sulfonation H2SO4 or SO3 / H2SO4 SO3 Reversible

E+ formed by Lewis
Cl2/Fe or FeCl3 Cl+ Cl

acid removing Cl-

Halogenation
E+ formed by Lewis
Br2/Fe or FeBr3 Br+
acid forming Br-
Br

E+ formed by Lewis
Alkylation R-Cl/AlCl3 R+
R acid removing Cl-

E+ formed by Lewis
Acylation RCOCl/AlCl3 RCO+
R C
O
acid removing Cl-

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 Reaction mechanism
 In the first step of the reaction mechanism for this reaction, the electron-rich aromatic ring, which in

the simplest case is benzene (suppliers of electrons), attacks the electrophile E + ≡ A. This step leads

to the formation of a positively charged cyclohexadienyl cation, also known as benzenonium ion.

This carbocation is unstable, owing both to the positive charge on the molecule and to the

temporary loss of aromaticity where the activation energy is high, so this step will be the rate

determining stepbecause of disruption of aromaticity.

 However, the benzenonium ion is partially stabilized by resonance, which allows the positive

charge to be distributed over three carbon atoms situation (EArS):

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 Nitration Reaction
 Nitration of Benzene: The source of the nitronium ion is through the protonation of nitric acid
by sulfuric acid, which causes the loss of a water molecule and formation of a nitronium ion.

 Sulfuric acid acts as a catalyst, allowing the reaction to be faster and at lower temperatures let
HNO3 and H2SO4 to react together to form the electrophile of the reaction, the nitronium ion
(NO2+).

 Sulfuric acid is used instead of hydrochloric acid, sine sukfuric acid can act as dehydrating
agent, has the ability to absorb the water formed but hydrochloric does not posses dehydrating
ability.
 Because the nitronium ion is a good electrophile, it is attacked by benzene to produce
Nitrobenzene.

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 Nitration Reaction Mechanism
Step 1: Generation of E+≡NO2

Step 2: Formation of intermediate-RDS

NO2 NO2 NO2

H H H

NO2

Step 3: Loss of proton to gives nitrobenzene

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 Regiochemistry of EAS
Why do substituent groups on a benzene ring affect the reactivity and orientation in the way
they do?
 Electronic effects, “pushing” or “pulling” electrons by the substituent.
 Electrons can be donated (“pushed”) or withdrawn (“pulled”) by atoms or groups of
atoms via:
 Induction – due to differences in electronegativity
 Resonance – delocalization via resonance

e--withdrawing: e--donating:
Deactivates the benzene ring towards EAS. Activates the benzene ring towards EAS. E+ reacts more at
Directs substitution to the meta- position. the center which is more negatively charged.
Directs substitution to the ortho- & para- positions.

m-position
o-position p-position

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 Groups Reactivity in EAS

Common substituent groups and their effect on reactivity in EAS:

-NH2, -NHR, -NR2

-OH
-OR
-NHCOR Electron donating /activate (faster than benzene)
Increasing reactivity

-C6H5 ortho- & para- direction

-R
-H
-X
-CHO, -COR
-SO3H
-COOH, -COOR Electron withdrawing / deactivate (slower than benzene)
-CN meta- direction
-NR3+
-NO2

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 Halogens are deactivators
 Halogens are deactivators, they are weakly deactivating
groups since they react slower than benzene, but halogens are
ortho, para-directors because of two properties:
1. They are highly electronegative atoms and can withdraw
electron-density along the ϭ-bonds by Inductive effects.

2. They have lone pairs that can stabilize the sigma complex
by resonance, can donate electrons-density through the π-
bonding. (Resonance donation).

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 How to draw resonance structure

Y Y
H

Y Y
H H

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 Halogens ortho/para-directors: reaction mechanism
 Mechanism
ortho-attack

Cl Cl Cl Cl
NO2 NO2 NO2
+ NO2+ H H H

Formation of tertiary carbocation

Cl Cl
NO2
-H+ NO2
H

o-nitrochlorobenzene

 Consider the nitration of chlorobenzene: para-attack

Cl Cl Cl Cl

H NO2 H NO2 H NO2

+ NO2+
Formation of tertiary carbocation
Cl Cl
-H+

H NO2
NO2

p-nitrochlorobenzene

meta-attack

Cl Cl Cl Cl

+ NO2+ Y
Y Y
H H H

All are secondary carbocation

Cl Cl
-H+

NO2 NO2
H

m-nitrochlorobenzene

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 Electron withdrawing group on ring

 If the group on the ring is electron withdrawing group:

X O
X O X O X O

 Positively charged on the ortho and para positions, are

interactive sites for positively charged electrophile to
react, so it will drive to meta position

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 Conclusion
H Y
 Electron donating groups

 Activate the benzene ring to electrophilic aromatic substitution.

CH3

 Increase the electron density in the ring and make it more reactive with
electrophiles.

 Stabilizes the intermediate carbocation, lowers the activation energy and increases
H Y
the rate.

 Electron withdrawing groups

NO2

 deactivate the benzene ring to electrophilic aromatic substitution.

 decrease the electron density in the ring and make it less reactive with electrophiles.

 destabilizes the intermediate carbocation, raising the activation energy and slowing
the rate.

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 Safety Precautions

As in all laboratory exercises:

• Safety glasses, mask, and gloves must be worn at all
times.
• Avoid skin and eye contact with any chemical reagent.
• In case of skin contact, rinse the area with water for
several minutes.
• For eye contact, flush eyes with water and seek
immediate medical advice.

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 Procedure

1. Add drop by drop 1.5 mL

chlorobenzene to the mixed acids.
2. Shake well after each addition
Cool the mixture 3. When all chlorobenzene has been
added, shake well and allow to
stand for 15 minutes.
4. Pour the mixture over 25 g ice,
stir until all ice melts.
1. Put 100 mL beaker in an ice
stainless bath.
2. Mix 4 mL conc. H2SO4+ 4 mL
conc. HNO3

5) Collection of crystals
by vacuum filtration
1. Recrystallize from ethanol
2. Dry the crystals.
3. Weigh the mass and
6) Wash the crystals calculate the percent yield.
with 2 mL cold water.

Para product can be isolated from the other

isomer by its higher m.p and lower solubility in
alcohol.
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