INTRODUCTION

Aromaticity in annulenes has been a subject of extensive

study in the field of organic chemistry, spanning
theoretical, experimental, and computational
investigations. This literature review provides an overview
of key findings and contributions in the understanding of
aromaticity in annulenes, highlighting its significance and
applications.

Theoretical Foundations: Hückel's rule, proposed in 1931,

laid the theoretical groundwork for understanding
aromaticity in annulenes. This rule predicts that cyclic,
planar molecules with 4n+2 π electrons exhibit aromatic
character. Subsequent theoretical developments, including
quantum mechanical calculations and computational
simulations, have provided deeper insights into the
electronic structure and aromatic behavior of annulenes.

Experimental Observations: Experimental techniques,

such as spectroscopy, crystallography, and chemical
synthesis, have been employed to characterize aromatic
annulenes and elucidate their properties. Notable
examples include the isolation and structural
determination of benzene, which served as a prototype for
aromatic compounds, and the synthesis of novel
annulenes with tailored aromaticity.
Chemical Reactivity

Aromatic annulenes display unique chemical reactivity,

including resistance to addition reactions and preferential
substitution reactions. Electrophilic aromatic substitution,
aromaticity-induced reactions, and aromatic stabilization
energies have been extensively studied to understand the
factors governing chemical reactivity in annulenes.

Applications:

The aromaticity of annulenes has practical implications in

various fields, including drug discovery, materials science,
and environmental chemistry. Aromatic compounds serve
as building blocks for pharmaceuticals, polymers, and
organic electronic materials, with their stability and
reactivity driving their utility in diverse applications.

Computational Methods:

Theoretical and computational chemistry play a pivotal

role in studying aromaticity in annulenes. Density
functional theory (DFT), ab initio methods, and molecular
modeling techniques are employed to calculate electronic
structures, aromatic stabilization energies, and reactivity
descriptors, providing valuable insights into the behavior of
annulenes.

In conclusion, the literature on aromaticity in annulenes

reflects a rich and multifaceted field of study,
encompassing theoretical foundations, experimental
observations, chemical reactivity, applications, and
computational methods. Further research in this area
promises to deepen our understanding of aromaticity and
its implications across scientific disciplines.

Aromaticity is a fundamental concept in organic

chemistry that describes the special stability and
reactivity observed in certain cyclic, planar molecules.
Annulenes, specifically, are a class of molecules
composed of carbon and hydrogen atoms arranged in a
ring structure with alternating single and double bonds.
The concept of aromaticity in annulenes originates from
Hückel's rule, proposed by Erich Hückel in 1931.
According to Hückel's rule, cyclic, planar molecules with
4n + 2 π-electrons (where n is an integer) exhibit aromatic
character.

This rule predicts that annulenes with 4n + 2 π-electrons

will possess unique stability due to the delocalization of
electrons throughout the π-system, resulting in a lower
overall energy state compared to non-aromatic
compounds. This enhanced stability makes aromatic
annulenes resistant to chemical reactions that would
typically occur in non-aromatic compounds.

Furthermore, aromatic annulenes exhibit distinctive

chemical reactivity and properties. They often undergo
electrophilic aromatic substitution reactions, where an
electrophile replaces one of the hydrogen atoms on the
aromatic ring.

Examples of aromatic annulenes include benzene, which

has 6 π-electrons (n = 1), andcyclopentadiene, which has
6 π-electrons (n = 1) These molecules display high
stability and reactivity consistent with aromatic behaviour
[1] monocyclic conjugated systems annulenes having
general formula (CH)2m The number of carbon atoms in
the ring being denoted by prefixed number in brackets.
Annulenes are grouped into two series:
m odd , (4n+2)π electrons

m even,(4n)π electrons
● Cyclobutadiene or [4]-annulene
4 electrons (even number of pairs; 4n, n = 1)
Cyclic, planar, uninterrupted ring of p orbital bearing atoms
(conjugation)
Antiaromatic
Being antiaromatic, cyclobutadiene is unstable. It can be
isolated only under controlled
conditions such as in Argon matrix or using trapping
agents such as dienes. Studies show that it
has a rectangular structure rather than a square, with C-C
bond length of 1.567 Å and C=C bond lenght of about 1.3
angstrom

Benzene [6]-Annulene.
A perfect example of cyclic planar molecule with
uninterrupted ring of p orbital bearing
atoms; 6 electron system (4n+2, n = 1)
Aromatic

8 membered ring, Cyclooctatetraene or [8]-annulene

[2]
8 π electron system;
If completely planar, this molecule will become
antiaromatic
(bond angle for planar structrure = 135°
which can give considerable
angle strain in a cyclic structure involving sp2
carbon atoms);
The molecule is actually boat shaped and nonaromatic.
(Nonaromatic form is more stable than an antiaromatic
form)

Aromaticity in higher annulenes

[10]-annulene

[3] [10]annulene also possesses 10 π electrons, however,

it does not exhibit any strong aromatic character. The
planar all-cis structure suffers from bond-angle strains.
Different out-of-plane conformations with more natural
bond angles
have been suggested in the literature based on the
measured proton nuclear magnetic resonance (1H NMR )
spectra and compu-
tational data. The energy differences and the barriers
between the conformations are very small because the
potential energy surface of [10]annulene is flat.
The planarity of the [10]annulene core can be forced.
for example, by introducing a methylene bridge,
forming1,6-methano[10]annulene.
5,10,11 Peaks of aromatic protons
were found in the 1H NMR spectrum of the bridged
bicyclic molecule.