NITRATION

LEARNING OBJECTIVES

 Introduction
 Nitrating Agents
 Mechanism For Nitration
 Kinetics of Aromatic Nitration
 Equipments For Nitration Processes
 Industrial Application

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NITRATION???

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 INTRODUCTION
The reaction between a nitrating agent and an
organic compound that results in one or more nitro
( --NO2) groups becoming chemically bonded to an
atom in the organic compound.

A process in which a nitro group (--NO2) becomes

chemically attached to a carbon, oxygen, or
nitrogen atom in an organic compound.

A hydrogen or halogen atom is often replaced by

the nitro group.
 INTRODUCTION (CONTD)
Three general reactions summarize nitration chemistry
1. C nitration, in which the nitro group attaches itself to a
carbon atom to form a nitroaromatic or nitroparaffinic
compound.

2. O nitration (an esterification reaction), in which an ON

bond is formed to produce a nitrate ester.

3. N nitration, in which a NN bond is formed,

nitramine is formed
 NITRATING AGENTS

A variety of reagents can be used to effect nitration.

These include:

 Concentrated fuming and aqueous nitric acid

 Mixtures of nitric acid with sulfuric acid, acetic
anhydride, acetic acid, phosphoric acid and
chloroform.
 N2O5 and N2O4
 MECHANISM
 Nitrations are highly exothermic, i.e. 126 kJ/mol (30
kcal/mol). However, the heat of reaction varies with
the hydrocarbon that is nitrated.

 The mechanism of a nitration depends on the

reactants and the operating conditions.
 The reactions usually are either

1. Ionic or
2. Free-radical.
 MECHANISM (CONTD)
 Ionic nitrations are commonly used for aromatics;
many heterocyclics; hydroxyl compounds, e.g., simple
alcohols, glycols, glycerol, cellulose and amines.

 Nitration of paraffins, cycloparaffins, and olefins

frequently involves a free-radical reaction.
IONIC NITRATION REACTIONS

 Acid mixtures containing nitric acid and a strong acid,

e.g., sulfuric acid, perchloric acid, selenic acid,
hydrofluoric acid, boron trifluoride can be used as the
nitrating feedstock for ionic nitrations.
 These strong acids are catalysts that result in the
formation of nitronium ions, NO+2.

 Sulfuric acid is almost always used industrially since it

is both effective and relatively inexpensive.
 IONIC NITRATION REACTIONS
 Most ionic nitrations are performed at 0-120°C. For
nitrations of most aromatics, there are two liquid
phases: an organic and an acid phase.

 Sufficient pressure, usually slightly above atmospheric,

is provided to maintain the liquid phases. A large
interfacial area between the two phases is needed to
expedite transfer of the reactants to the interface and of
the products from the interface.

 The site of the main reactions is often at or close to the

interface. To provide large interfacial areas, a
mechanical agitator is frequently used.
IONIC NITRATION REACTIONS
(CONTD)

 NO+2 attacks an aromatic compound (ArH) as

follows:
 IONIC NITRATION
REACTIONS (CONTD)
 For an alcohol, glycol, or glycerol, or for amines,
the reaction may be represented:
 IONIC NITRATION
REACTIONS (CONTD)
 When sulfuric acid is present in the mixed acids,
the following ionization reactions occur. These
ionic reactions are rapid, and equilibrium
concentrations of NO+2 are likely to be present at
all times in the acid phase. NO+2 concentrations
depend mainly on the composition of the mixed
acids but decrease to some extent as the
temperature increases.
 CHEMISTRY OF
ELECTROPHILIC AROMATIC
SUBSTITUTION
• Generation of the electrophile in nitration requires
strong acid.
• An electrophile is a chemical species that forms bonds
with nucleophiles by accepting an electron pair.

• A Lewis acid is any substance, such as the H+ ion, that

can accept a pair of nonbonding electrons. In other
words, a Lewis acid is an electron-pair acceptor.

• A Lewis base is any substance, such as the OH- ion,

that can donate a pair of nonbonding electrons. A
Lewis base is therefore an electron-pair donor.

• Because electrophiles accept electrons, they are

Lewis acids.
 Electrophilic Aromatic Substitution

• The characteristic reaction of benzene is electrophilic

aromatic substitution—a hydrogen atom is replaced by an
electrophile.
• Benzene does not undergo addition reactions
like other unsaturated hydrocarbons, because
addition would yield a product that is not
aromatic.
• Substitution of a hydrogen keeps the aromatic
ring intact.
• Regardless of the electrophile used, all electrophilic aromatic
substitution reactions occur by the same two-step mechanism
—
• addition of the electrophile E+ to form a resonance-stabilized
carbocation,
• followed by deprotonation with base.
Many substituted benzene rings undergo
electrophilic aromatic substitution.
Each substituent either increases or decreases the
electron density in the benzene ring, and this affects
the course of electrophilic aromatic substitution.
• Consider toluene—Toluene reacts faster than
benzene in all substitution reactions.
• The electron-donating CH3 group activates the
benzene ring to electrophilic attack.
• Ortho and para products predominate.
• The CH3 group is called an ortho, para director.