J&K Sainik School Manasbal

Chemistry Project

Topic:
Nucleophilic Aromatic Substitution

Submitted by: Shahid Shaban

Submitted to: Abdul Hamid Bhat
Nucleophilic Aromatic Substitution

Introduction

Nucleophilic Aromatic Substitution

Nucleophilic aromatic substitution is a classical reaction in

which a nucleophile displaces a leaving group on an aromatic
ring. The presence of the electron-withdrawing group increases
the rate of nucleophilic aromatic substitution. The nucleophilic
compound doesn’t give substitution reaction easily, but some
aromatic compounds were found to undergo nucleophilic
aromatic substitution successfully.

● Nucleophilic aromatic substitution does not follow the SN2

reaction mechanism, as the substitution takes place at the
trigonal carbon atom having sp3 hybridisation.
● Nucleophilic aromatic substitution does not follow the SN2
reaction mechanism because of the steric hindrance of the
benzene ring.
● Nucleophilic aromatic substitution may follow the SN1
reaction mechanism in the presence of an excellent
leaving group.
● SN1 reaction would involve elimination of the leaving
group and formation of aryl carbocation.
● Generally, Nucleophilic aromatic substitution follows the
elimination addition or addition elimination pathway.

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Nucleophilic Aromatic Substitution

Conditions of Nucleophilic Aromatic Substitution

● The nitro group is generally used as an

electron-withdrawing group to activate the aromatic ring
for nucleophilic aromatic substitution.
● Ortho or Para position of the electron-withdrawing group to
the leaving group supports the resonance stabilisation of
the negative charge in the transition state.
● –OH, –OR, –NH2, –SR, NH3, and other amines are
nucleophiles that generally show nucleophilic aromatic
substitution.
● Alike SN1 or SN2 greater the halogen atoms
electronegativity, the more readily it will leave.

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Nucleophilic Aromatic Substitution

Examples of Nucleophilic Aromatic Substitution

● The para nitro fluoro benzene reacts with sodium

methoxide yields a nucleophilic aromatic substitution
product, i.e. para nitro methoxy benzene and sodium
fluoride.
● The ortho bromo acetophenone reacts with ethanethiol
yields a nucleophilic aromatic substitution product.

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Nucleophilic Aromatic Substitution

Mechanism of Nucleophilic Aromatic

Substitution

SNAr Mechanism

● It is also known as the elimination addition or addition

elimination mechanism.
● The presence of an electron-withdrawing group makes an
aromatic ring prone to a nucleophilic attack.
● It is similar to electrophilic substitution except that an
anionic intermediate is formed rather than a cationic
intermediate.
● Substitution between the leaving group and a nucleophile
takes place.
● The electron-withdrawing group’s ortho or Para position to
the leaving group is preferred as resonance stabilised.
● In contrast, meta is stabilised by the inductive, but no
resonance.
● Thus ortho or para position concerning
electron-withdrawing group is preferred.

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Nucleophilic Aromatic Substitution

SN1 Mechanism

This mechanism is encountered with diazonium salts

and nucleophiles. The rate depends on the strength of
nitrogen molecule bonding.

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Nucleophilic Aromatic Substitution

Benzyne Mechanism

Aryl halides with no activating group proceed through the

benzyne mechanism.

Aryl halide reacts with a strong base to yield benzyne

intermediate, which reacts with a nucleophile to give
regioisomers.