Dr. J.
Muneer Ahamath
Dept. of Chemistry
AROMATICITY OF ORGANIC COMPOUNDS
Unit: 2.2 .#Definition of aromaticity -Huckel’s # and Craig's rules -
ring currents –( Non-aromatic compounds) Non-benzenoid aromatic
compounds - Aromatic character in 3,5 and 7 membered ring
compound - Anti-aromaticity - systems with 2, 4, 6, 8, 10, 14 & 18
electrons – Azulene -Annulenes -Sydnones and fullerenes -Alternant
and non-alternant hydrocarbons - Homoarmaticity.
Aromaticity compounds
The compounds which behave like benzene are called aromatic
compounds. An aromatic compound must satisfy the following
conditions.
i. Cyclic and planar structure
ii. Equal band lengths
iii. Chemical stability
iv. Ability to undergo substitution reaction
v. Ability to sustain an induced diamagnetic ring current
diatropic
vi. Conjugated system of π electrons with effective delocalisation
Huckel’s rule
An aromatic compound must contain a cyclic and planar
structure with (4n+2) π-electrons delocalising effectively throughout
the plane of the molecule
Thus, the cyclic and planar compounds containing
26,10,14,18 etc. π-electrons with effective delocalisation will have
aromatic character.
Ex. Benzene is an aromatic compound. The aromatic
behaviour of benzene is explained by the following
reasons:
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1. Benzene has a cyclic and planar structure with 6
carbon atoms
2. It has an equal bond length of 1.39 A0 between the
carbon atoms which is neither a single bond 1.54 A0
nor a double band 1.34 A0
3. It has resonance stabilisation energy of 150.6 kJ/mole
or 36 Kcal / mole.
4. It has (4n+2) π-electrons where n=1 with effective
delocalisation.
5. It has a closed loop of 6 electrons called aromatic
sextet.
6. It undergoes substitution reactions rather than
additions
7. It has an ability to sustain an induced diamagnetic ring
current and therefore it is diatropic
8. The PMR chemical shift of benzene protons appear at
downfield around 7-8 δ value.
Craig’s rules
➢ Craig proposed a set of rules called Craig's rules which are
based on the VB and other calculations of compounds such
as cyclobutadiene, pentalene, heptalene, and pyrene etc.
➢ Craig's rides can predict whether the VB wave function of
a compound is totally symmetric or not.
➢ These rules can be applied to molecules which are more
stable at their ground state, totally symmetric and contribute
a more number of Kekule structures.
➢ Thus Craig’s rules are applied to hydrocarbons which
contain at least two π -electron centres lying in a symmetry
axis that can convert one kekule structure to another.
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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

According to Craig’s rules .; Pentalene is a pseudo-aromatic compound.

❖ The π-electron centres of a compound should be labelled
Ex. 2 Heptalene
With the spin functions α and β such that the ends of each
double bond have different spins in both Kekule structures
and as few as possible of like spin adjoin.
❖ The total number of symmetricaly related π- centres except
those on symmetry axis is taken as ‘f’.
❖ The total number of inter conversion of α and β by rotation
about the axis is taken as ‘g’. f= 5, g = 0, f & g =5+ 0=5, Odd number
❖ If the sum of f & g is even, the VB ground state is totally .; Heptalene is a pseudo aromatic compound.
symmetric and the compound should have aromatic stability
and hence aromatic. Ex. 3: Cyclobutadiene or [4 ]annulene
❖ It the sum of f & g is odd, the VB ground state is non-
totally symmetric and the compound should not have
aromatic stability and symmetric hence pseudoaromatric (or)
Non-aromatic.
Ex. 1: Pentalene.

f =2; g = 2; therefour f + g = 2 + 2
= 4; Even number
It is an aromatic compound
Rotation about the vertical symmetry axis converts the Kekule
structure A into B
The pairs of π-electron centres 1 - 6, 2 - 5 & 3 - 4 are related
by the symmetry axis f = 3. Upon rotation, no inter Ex.4: Acenaphthylene:
conversion of α and β occur g = 0.
Hence f & g 3+0=3. Odd number

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

f =5; g = 0; therefore f + g= 5 +
0 =5; Odd number
f =5; g =1; f + g = 5 + 1 = 6; Even number.
It is an aromatic compound. It is a pseudo aromatic compound
Ex.7:
Ex. 5: pyrene

F
f = 6; g =0; f + g = 6 + 0= 6; Even number
It is an aromatic compound.
f = 4; g = 4; f + g = 4 + 4 = 8; Even number.
It is an aromatic compound.

Ex.6

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

f = 3; g = 0; therefore f + g = 3 + 0 = 3 ; Odd number

It is a pseudo-aromatic compound

Ex. 10; 1,4 diphenyl benzopentalene

Ex. 8

f = 3; g = 0; f + g = 3 + 0 =3 Odd Number.
It is a pseudoaromatic compound.
F
EXCEPTION TO CRAIG'S RULES
f = 3; g=3; therefore f + g = 3 + 3 = 6: Even number
Aceheptalene derivative is a stable aromatic compound, but
It is an aromatic compound.
Craig's rules fails to explain this fact when the compound is assigned
Ex.9: pentalene-3,6-dione the following structure.

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

Let us consider a benzene molecule. The delocalised

f = 6; g =1; f + g = 6 + 1 = 7 Odd π -electrons in the benzene ring can move in either direction. When a
Number
magnetic field is applied perpendicular to the plane of the benzene
It must be pseudo aromatic ring, the π - electrons circulate in one direction only, thereby
compound. But actually it is a stable aromatic compound. producing a ring current. This ring current induces a magnetic field
perpendicular to the plane of the molecule. This induced magnetic
When the compound is assigned the following structure, it is
proved to be an aromatic compound. field opposes the applied magnetic field in the centre region of the
ring and assists the applied magnetic field in the outside region of the
ring.
Therefore the centre region of the ring is called shielding area
and the outer region of the ring is called
deshielding area. The protons present
in the shielding area are called diamagnetic
protons and the protons present in the
deshielding area are called
paramagnetic protons.

f = 6; g =0; f + g = 6 + 0 = 6: Even Number

It is an aromatic compound.
What is induced ring current?

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Dr. J. Muneer Ahamath
Dept. of Chemistry
Therefore the chemical shifts of hydrogen atoms which lie
inside tho ring or above and below the ring (shielding region) take
place at Upfield with lower values Similarly the chemical shifts of
peripheral hydrogen atoms which lie in the plane of the benzene ring
(deshielding region) occur at down field with higher values of 7-8 δ.
Non-aromatic compounds:
Some compounds may have cyclic structures with conjugated
double bonds but fail to have planar shapes. Such compounds do not
have any aromatic character and are called non-aromatic
compounds.
Ex 1. Cyclopropene
It is a cyclic and planar molecule with two π- electrons. But
the π- electrons do not involve in the delocalisation because of the
presence of saturated sp3hybrid carbon atom in the ring. Therefore
this is a non-aromatic compound.
Ex 2. Cyclopentadiene:
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It is a cyclic and planar molecule. it has 4 π- electrons which
does not obey Huckel's rule of aromaticity. The electrons do not
involve in the delocalisation due to the presence of saturated
sp3hybrid carbon atom in the ring. There this is a non-aromatic
compound.
Ex 3. Cycloheptatriene
It is a cyclic and planar molecule containing 6 π- electrons But
the π- electrons do not involve in the delocalisation due to the
presence of saturated sp3hybrid carbon atom in the ring Therefore it
is a non-aromatic compound.
Ex 4. Cyclooctatetraene:
It is a cyclic compound having conjugated system with all sp2
hybrid carbon atoms.This is not a planar but tub-shaped. Moreover, it
has only 8 π- electrons which does not obey Huckel's rule of
aromaticity. Therefore this is a non-aromatic compound.
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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

delocalised through the empty p-orbitals of the carbonium ion. Hence

Non-benzenoid aromatic compounds: it is an aromatic compound.
Compounds which do not have benzene like structures but
have aromatic character due to the presence of cyclic, planar and
conjugated systems with (4n+ 2)π- electrons delocalising effectively
in the ring are called non-benzenoid aromatic compounds.
c)
Such compounds sustain an induced diamagnetic ring current
c) Cyclobutenyl d-cation:
and are called diatropic.

Ex. 1: Systems with 2 π- electrons: n=0

a) Cyclopropenylcation:

It is a cyclic and planar ion with 2 π-electrons which are

delocalised through the empty p-orbitals of the two sp2 hybrid carbon
atoms of the system. Therefore it is aromatic.
Similarly tetraphenyl cyclobutenylfluoborate is also a stable
It is a cyclic & planar ion. It has 2 π-electrons which are aromatic 2 π-electron system.
involved in the delocalisation through the empty p-orbitals of sp2
hybrid carbon atom of the carbonium ion in the ring. Therefore, it is
aromatic.
b) Cyclopropenone:

Ex 2. Systems with 6 π-electrons; n=1

a) Cyclopentadenyl anion
Cyclopentadiene is a highly acidic compound it loses a proton
It is a cyclic and planar molecule with 2 π-electrons. since the to give cyclopentadienyl anion.
electronegative oxygen atom withdraws electrons towards itself, the
resulting ion is stabilised by resonance. The π-electrons are

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

Ex 3 Systems with 10 π-electrons; n=2

Cyclopentadienyl anion is a cyclic and planar on electrons.
The two of the negatively charged carbon atom are involved in the
delocalisation thereby forming a total of 6 electrons Therefore it is
diatropic and also aromatic It is stabilised by the following resonance
structures.
b) Cycloheptatrenyl cation:
Cycloheptatriene loses a hydride ion to form
cycloheptatrienyl cation called Tropylium ion.
Tropylium ion has a cyclic and planar structure with 6 The compounds which have cyclic, planar conjugated systems
π-electrons which are involved in the delocalisation through the
empty p-orbitals of the sp2 hybrid carbon atom of carbonium ion.
Therefore it is aromatic Cyclohepatrieny bromide is a known
compound having a tropylium cation structure.
Cyclooctatetraenyl di-anion:
Cyclooctatetraene when treated with potassium gives
cyclooctatetraenyl di-anion
cyclooctatetraenyl di-anion is a cyclic and planar ion having a total
number of 10 π-electrons delocalising effectively throughout the ring
Therefore it is aromatic.
Anti -aromatic compounds
Anti-aromatic compounds must satisfy the following conditions:
i. Cyclic and planar structure.
ii. Conjugated system of 4n- π electrons with effective
delocalisation.
iii. Sustain an induced paramagnetic ring current-
paratropic.
iv. Equal bond lengths.
v. Less chemical stability than acyclic analogues.
vi. Able to undergo substitution reactions.
with 4n- π electrons delocalising in the ring and are less stable than
the corresponding acyclic analogue are called antiaromatic
compounds
The antiaromatic compounds sustain an induced paramagnetic ring
Current and are paratropic The outer protons of the ring are shielded
and shifted to upfield with lower π-values while the inner protons are
deshielded and shifted to downfield with higher 8 values.

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Dr. J. Muneer Ahamath
Dept. of Chemistry
Ex. No.1: Systems with 4 π-electrons: (n=1)
a) Cyclopropenyl anion:
Cyclopropene molecule loses a proton to give cyclopropenyl anion.
Cyclopropene
This is a cyclic and planar ion. It has 4n- π electrons (n=1)
including the two electrons of the negatively charged carbon atom.
these 4π- electrons are involved in the effective delocalisation
throughout the molecule. It sustains an induced paramagnetic ring
current. It is an anti-aromatic compound. It stabilised by the following
resonance structures
b) Cyclobutadiene.
This is a cyclic, planar and conjugated system containing
4π-electrons. lt has low delocalisation energy and less stable and
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therefore it is highly reactive. Therefore it is an anti-aromatic
compound.
c) cyclopentadienyl cation:
Cyclopentadiene loses a hydride ion to give cyclopentadenyt cation.
This is a cyclic and planar ion. It has 4 π-electrons which are
delocalised through the empty p-orbital of the sp2hybrid carbon atom
of the carbonium ion in the ring. Therefore it is an antiaromatic
compound.
Ex. 2 Systems with 8 π- electrons; (n=2)
a) Cycloheptatrenyl anion:
This is a cylic and planar system with 8 π-electrons including
electrons of the negatively charged carbon atom. The π-
electrons are delocalised through the p-orbital of the carbanion.
Therefore is an anti aromatic compound.
Ex. 3: Systems with 12 π- electrons; (n=3)
a) Benzocycloheptatrienyl anion.
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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

This is a planar, bicyclic and conjugated system with

12 π-electrons which are delocalised throughout the molecule. All the
pheriperal protons are
Shielded and chemical shifts appear upfield at lower delta values.
This is an anti-aromatic ion.

b) Cyclocatadiene diynes:

Ex.4. system with 16 π - electrons: (n=4)

The [16] annulene exists in an equilibrium of the following
two structures. At a temperature of above -500 c, the conformational
mobility occurs resulting in the magnetic equivalence of all protons,
These are planar, bicyclic and tricyclic conjugated systems
but at a temperature of -1300 c, the compound is paratropic. The four
with effective delocalisation of 12 and 16 π-electrons respectively
inner protons are deshielded and appear downfield at 10.56 δ and the
therefore, these compounds are anti-aromatic.
twelve outer protons are shielded and appear upfield at 5.35 δ.
c) Simple [12] annulene & its derivatives
Simple [12] annulene is not planar molecule due to non-
bonding interaction of inner hydrogen atoms and therefore it is not an
aromatic compound. But the derivatives of [12] annulene namely 5-
bromo- 1, 9- didehydro [12] annulene, cycl [3, 3.3] azine and 1,7
methano [12] annulene are planar molecules and therefore they are
paratropic and antiaromatic.The inner protons of the bromo
compound are deshielded and appear downfield at 16.4 δ in the pmr The structure (I) has a non-planar conformation due to the
spectra of the compound. non-bonded interaction of the four inner protons. Therefore it is non-
aromatic. The structure (ll) has a planar conformation with effective
delocalisation of π -electrons. Therefore it is paratropic and hence
aromatic.

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

(i) Cis-trans-cis-cis trans form

ANNULENES

The monocyclic hydrocarbons with altermate single and

double bonds are called annulenes. The annulenes have an even
number of carbon atoms. The ring sizes of annulenes are indicated by
a number in brackets. Examples.
This form not a planar molecule due to the non-bonded
interaction between the hydrogen atoms of 1 and 6 positions.
Therefore the delocalisation of π-electrons is not possible and hence
it is not aromatic eventhough it has 10 π-electrons.
(ii) All cis-form

This form contains 10 π-electrons but the angle of each

Aromaticity of large ring annulenes
Aromaticity of large ring annulenes depends on whether the
molecule can adopt the planar conformation or not.
carbon atom has been devitated from 1200 to 1440. Therefore the
molecule is not a planar and the delocalisation of t electrons will not
occur in the molecule. Moreover, the PMR spectrum of this structure
indicates that all the protons lie in the olefinic region. Hence it is not
aromatic.
(iii) Mono-trans form

Ex. 1: Cyclodecapentene [10]Annulene: (n=2)

[10] Annulene exists in the folowing
three forms:

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

This form contains 10 π-electrons but this structure has some

angle strain Therefore the molecule is not a planar and the
delocalisation of π-electrons is not possible. Hence it is not aromatic
Ex. 2: 1, 6-methano [10]annulene
Ex 3 [12] Annulene (n=3) & [16] Annuene (n= 4)

These two compounds have only 4n π-electrons such as

12 (n=3) and 16 (n=4). They are not planar molecules due to the non-
bonding interaction of inner protons .therefore they are neither
aromatic nor antiaromatic.

Ex. 4: [14 ]annulene

This compound is a cyclic planar, diatropic and stable due to

the presence of bridged -CH2 - group between 1 and 6 carbon atoms.
The aromatic character of this compound is confirmed by two sets of
protons in its NMR spectra. The eight peripheral protons are
dishielded and appear downfield at 7.10 value whereas the bridged
-CH2- protons are shielded and appear upfield at-0.50 value.
Therefore this compound is aromatic. This compound 14 π-electrons (n=3)but not aromatic and
Note: Similarly its oxygen or nitrogen bridged analogue compounds highly unstable. Due to the steirc hindrance of the four internal
are also aromatic due to their planarity, datropic and stable nature. hydrogen atoms , the planarity of the molecule is twisted and the
delocalisation of π-electrons is not possible and hence it is not
aromatic.

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

Ex.5. monodehydro [14] annulene

Ex.7.[18]annulene; (n=4)

This compound has a cyclic and planar structure with

14 π-electrons (n=3). The two of the π-electrons of the triple bond are
not involved in the delocalisation but remains as localised π-
electrons. Therefore it is an aromatic compound.
Ex. 6: trans-15, 16-dimethyl dihydropyrenr: (n=3)

This is a cyclic and planar molecule with 18 π-electrons (n=4)

which are involved in effective delocalisation . the 12 outer protons
This is a cyclic and planar appear downfield at 9.0 δ value and the 6 inner protons appear upfield
molecule with 14 π- electrons at -3.0 δ value in pmr spectra of the compound.
(n=3)which are involved in effective Ex. 8: [22] annulene & dehydro [22] annulene
delocalisation. The NMR spectra of 10
pheriperal Protons are deshielded
and appear at 8.0 δ value whereas the
inner 6 protons of the two methyl groups are shielded and appear at
4.0 δ value. Therefore it is an aromatic compound

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

This compound are also cyclic, planar and diatropic with

22 π- electrons which are in effective delocalisation. Hence they are
aromatic
Aromaticity of Polycyclic compounds
Ex. 1: Azulene

Azulene is a bicyclic compound containing 10 π-electrons

(n 2) which are effectively delocalised through out the molecule.
Therefore it is an aromatic compound.
Azulene is considered as the combination of cycloheptatrienyl cation
and cyclopentadienyl anion The molecule exists as a dipolar structure
with a dipole moment of 1.0 Debye unit.
AZULENE
The seven membered ring has 7π- electrons and the five
membered ring has 5π-electrons Two π-electrons are common to both
the rings. If one π- electrons is transferred from the seven membered
ring to the five membered ring. Then the molecule will have a dipolar
structure as given below.

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

Homoarmaticity
Compounds which contain one or more sp3shybridised
carbon atoms in otherwise conjugated cyclic system are called
homoaromatic compound. In these compounds, the Sp2 hybrid
SYDNONES
orbitals overlap effectively when the sp3 hybrid atoms are forced to
Sydnones are cyclic, planar and stable aromatic compounds
lie almost vertically above the plane of the aromatic carbon.
containing 6 π-electrons (n=1) with effective delocalisation. They
undergo aromatic substitution reaction when R is a hydrogen atom.
Ex. When cyclooctetraene is dissolved in conc.H2SO4, one
Sydnones are more stable due to the following resonance structures.
proton adds on to one of the double bond to form the homotropylium
ion. The aromatic sextet is spread over all the seven carbon atoms.
The eighth carbon is a sp3 hybrid carbon and is present vertically
above the plane of the remaining aromatic carbon atoms.

SYNTHESIS

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

Structure And Properties

NMR spectra of the compound shows the presence of diatropic ring
current effect. The Ha appears downfield at 5.1 δ and Hb appears up
field at -0.3 δ value. Therefore is a homoaromatic ion.
Fullerenes are large carbon cage molecules considered to be
three-dimensional analogues ofbenzene. The most abundant form of
fullerenes is Buckminster fullerene (C60) with 60 carbon atoms
marranged in a spherical structure. The shape of themolecule, known
as truncated icosahedron 2, resembles that of a soccer ball, which
contains 12 pentagons and 20hexagons.

Fullerene
Fullerene is a molecule of carbon in the form of a hollow
sphere, ellipsoid, tube, and many other shapes. Spherical fullerenes,
also referred to as Buckminsterfullerenes or buckyballs, resemble the
balls used in association football. Cylindrical fullerenes are also
called carbon nanotubes (buckytubes). Fullerenes are similar in
structure to graphite, which is composed of stacked graphene sheets
of linked hexagonal rings. Unless they are cylindrical, they must also
contain pentagonal (or sometimes heptagonal) rings.
Fullerenes have been extensively used for several biomedical
applications including the design of high-performance MRI contrast
agents, X-Ray imaging contrast agents, photodynamic therapy and
drug and gene delivery, summarized in several comprehensive
reviews.

Fullerene

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Dr. J. Muneer Ahamath Jamal Mohamed College (Autonomous)
Dept. of Chemistry Tiruchirappalli20.

(i) Alternant hydrocarbons

In alternant hydrocarbons, the conjugated carbon atoms can
be divided into two sets such that any two atoms of the same set are
not directly linked.
For convenience to understand, one set of carbons is starred.
Ex. Naphthalene
The bonding and anti-bonding orbitals occur in pairs alternant
hydrocarbons. For every bonding orbital with an energy -E there is an
antibonding orbitat with energy +E.
The alternant hydrocarbons are of two types
a) Even alternant hydrocarbons have an even number of
conjugated atoms. They have an equal number of starred and
unstarred atoms.
Ex. Naphthalene:
b) odd-alternant hydrocarbons have not only an equal and
opposite bonding and anti-bonding orbitals but also have non-bondng
orbitals of zero energy.
Ex. Allyl system.
Alternant and Non-Alternant Hydrocarbons (ii) Non- alternant hydrocarbons
In non-alternant hydrocarbons, the conjugated carbon atoms
can be divided into two sets such that any two atoms of the same set
are directly linked.
Ex. Azulene.

Aromatic
hydrocarbons are classified into two types namely
(i) Alternant hydrocarbons
(ii) Non-alternant hydrocarbons For non-alternant hydrocarbons, the energies of the bonding
and antibonding orbitals are not equal and opposite and the charge
distributions are not the same in cations, anions and radicals.

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