Aromatic Assignment

BRIAN OWEGI NYAMWAYA
SCT-251-O37/2020
AROMATIC AND HETEROCYCLIC (CHE 2402)
ASSIGNMENT 1
MULTIMEDIA UNIVERSITY OF KENYA.
1. Describe the stability of benzene using molecular orbital theory
The stability of benzene can be explained using molecular

orbital theory which describes the electronic structure and bonding in molecules.
Benzene's exceptional stability is primarily attributed to its aromaticity, a concept
rooted in molecular orbital theory. Here's how the stability of benzene is explained:
π Molecular Orbitals: In benzene, there are six carbon atoms arranged in a planar
hexagonal ring, with one hydrogen atom attached to each carbon. Each carbon atom
contributes one valence electron for a total of six electrons. These electrons can be
used to form π (pi) bonds.
Localized vs. Delocalized π Bonds: In a simple view, if benzene were to have three
alternating double bonds (localized π bonds) and three single bonds, it would not be
particularly stable. However, molecular orbital theory shows that the six π electrons in
benzene are not confined to specific double bonds but are instead delocalized over the
entire ring.
Aromatic Ring and Resonance: In benzene, the π electrons are spread out evenly in a
cloud above and below the ring. This results in a stable, continuous π electron cloud,
which gives rise to a set of molecular orbitals known as the π molecular orbitals. This
phenomenon is called resonance or delocalization.
Bonding in Benzene: The molecular orbital theory explains that benzene has three π
molecular orbitals that are formed from the combination of six atomic p orbitals.
These π orbitals result from constructive interference of the atomic p orbitals and have
lower energy than the individual atomic p orbitals. Additionally, there are three σ
(sigma) bonds formed by head-on overlap of the carbon-carbon sigma bonds.
Aromaticity: Benzene is considered aromatic because it satisfies Huckel's rule, which

states that an aromatic compound must have a continuous ring of p orbitals with (4n +
2) π electrons, where n is an integer. For benzene, n = 1, so it has (4n + 2) = 6 π
electrons, fulfilling the requirement for aromaticity.
Enhanced Stability: Aromatic compounds like benzene are exceptionally stable due to
their low energy, which results from the delocalization of π electrons. This stability is
manifested in various ways, such as resistance to addition reactions and the lack of
reactivity toward electrophilic attacks on the ring
Bing
Benzene, a cyclic hydrocarbon with the molecular formula

C6H6, is known for its exceptional stability. The stability of
benzene can be explained using molecular orbital theory.
According to molecular orbital theory, benzene's stability arises from the
delocalization of its π electrons. The six carbon atoms in benzene form a planar
hexagonal ring, with each carbon atom contributing one p orbital to the π system.
These p orbitals overlap to form a series of molecular orbitals.
In benzene, the π molecular orbitals are filled with a total of six π electrons. All the
bonding molecular orbitals are filled, indicating a highly stable molecule. The lowest
energy molecular orbital of benzene, known as π1, has six stabilizing
bonding interactions. This delocalization of electrons across the entire ring contributes
to the stability of benzene.
The exceptional stability of benzene is a characteristic shared by all aromatic
compounds. Aromaticity refers to the special resonance stabilization observed in
compounds like benzene.
For more detailed information on the molecular orbitals and stability of benzene, you
can refer to the following resources:
● [Pi Molecular Orbitals of Benzene - Chemistry LibreTexts](^1^)
● [Resonance and the Molecular Orbitals of Benzene - Chemistry LibreTexts]
(^2^)
● [Benzene’s Unusual Stability - Chemistry LibreTexts](^3^)
2. Make notes on details on nucleophilic aromatic substitution
A nucleophilic aromatic substitution is a substitution reaction in organic chemistry in which

the nucleophile displaces a good leaving group, (Rohrbach et al., 2019)such as a halide, on an
aromatic ring. Aromatic rings are usually nucleophilic, but some aromatic compounds do
undergo nucleophilic 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.
N/B:
 It does not follow the SN2 reaction mechanism, as the substitution takes place at the
trigonal carbon atom having sp3 hybridization.
 It does not follow the SN2 reaction mechanism because of the steric hindrance of the
benzene ring.
 It 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.
 It follows the elimination addition or addition elimination pathway.
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 stabilization of the negative charge in the transition state.
 –OH, –OR, –NH2, –SR, NH3, and other amines are nucleophiles that generally show
nucleophilic aromatic substitution.
 Like SN1 or SN2 greater the halogen atom's electronegativity, the more readily it will
leave.
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.
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.
Nucleophilic aromatic substitution (S_NAr) is a type of chemical reaction in organic

chemistry where a nucleophile replaces a leaving group on an aromatic ring. This reaction is
an important mechanism in the synthesis of various organic compounds and plays a crucial
role in the functionalization of aromatic compounds. Here are some key notes on nucleophilic
aromatic substitution.
Nucleophilic Aromatic Substitution (NAS)
In many ways, nucleophilic aromatic substitution is the mirror opposite of electrophilic

aromatic substitution.
 In Nucleophilic Aromatic Substitution, an electron-poor aromatic ring is attacked by

a nucleophile, resulting in a substitution reaction
 The reaction proceeds through a negatively charged (carbanion) intermediate
 The reaction is accelerated by the presence of electron-withdrawing groups on the
aromatic ring
 The placement of electron withdrawing groups ortho- or para- to the leaving group results
in faster reactions than does the placement of electron withdrawing groups meta- to the
leaving group
 Fluorine can act as a leaving group (!) in nucleophilic aromatic substitution reactions,
since it is quite electron-withdrawing and C-F bond breakage is not the rate-limiting step.

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BRIAN OWEGI NYAMWAYA

AROMATIC AND HETEROCYCLIC (CHE 2402)

MULTIMEDIA UNIVERSITY OF KENYA.

1. Describe the stability of benzene using molecular orbital theory

The stability of benzene can be explained using molecular

Aromaticity: Benzene is considered aromatic because it satisfies Huckel's rule, which

Benzene, a cyclic hydrocarbon with the molecular formula

2. Make notes on details on nucleophilic aromatic substitution

A nucleophilic aromatic substitution is a substitution reaction in organic chemistry in which

Conditions of Nucleophilic Aromatic Substitution

Examples of Nucleophilic Aromatic Substitution

 It is also known as the elimination addition or addition elimination mechanism.

Nucleophilic aromatic substitution (S_NAr) is a type of chemical reaction in organic

Nucleophilic Aromatic Substitution (NAS)

In many ways, nucleophilic aromatic substitution is the mirror opposite of electrophilic

 In Nucleophilic Aromatic Substitution, an electron-poor aromatic ring is attacked by

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