Subject Chemistry
Paper No. and Paper 1: ORGANIC CHEMISTRY- I (Nature of
Title Bonding and Stereochemistry)
Module No. and Module 8: Aromaticity of fused rings
Title
Module Tag CHE_P1_M8
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
TABLE OF CONTENT
1. Learning Outcomes
2. Introduction
3. Classification of fused ring systems
4. Aromaticity in fused ring systems
4.1. Aromaticity of some benzenoid fused systems
4.1.1. Naphthalene
4.1.2. Anthracene
4.1.3. Phenanthrene
4.1.4. Resonance energy of fused ring systems
4.2. Aromaticity of some non-benzenoid fused systems
4.2.1. Azulenes
4.2.2. Oxaazulenaones
5. Other fused ring systems
5.1. Phenalene
5.2. Benzo cyclobutadiene
5.3. Ferrocene
6. Summary
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
1. Learning Outcomes
After studying this module, you shall be able to:
Learn about the fused rings
Understand that how fused rings are classified
Learn about the aromaticity of the fused rings
Understand aromaticity in the benzenoid and non-benzenoid fused ring systems
Learn about some other special cases
2. Introduction
As you are already aware that the aromatic compounds apparently contain alternate double and
single bonds in a cyclic structure and resemble benzene in chemical behavior. Up till now we
have discussed the aromaticity in monocyclic rings. In this module, we shall discuss about the
aromaticity of fused rings.
So, before starting with the aromaticity of fused rings first we should know what fused rings are.
A fused aromatic ring is one which shares one side of the ring. These are monocyclic rings that
shares their connecting bond. Such type of molecules which contain these kind of fused rings
(e.g. phenanthrene or anthracene) are generally referred to as linear or angular polyacenes. For
example: acenes are a class of organic compounds and polycyclic aromatic hydrocarbons made
up of linearly fused benzene rings.
Some of the examples are given below:
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
3. Classification of fused ring systems
Fused ring systems are classified into two categories depending on the number of atoms and
bonds shared by the rings. These are as follows:
i. Ortho-fused rings –If the two rings of the fused system that have only two atoms and one
bond is common between the rings then it is said to be ortho-fused rings as in case of
naphthalene.
As shown in the figure of naphthalene two rings are ortho-fused.
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
ii. Ortho and peri fused rings – If three atoms are common between the first ring and the
other two rings then it is said to be ortho and peri fused rings. This type of fused rings is
generally present in the polycyclic rings where the ring is ortho fused with two different
sides of two rings which themselves are ortho fused. For Example, in case of phenalene.
4. Aromaticity in fused ring system
As we have discussed in the previous module, a molecule is said to be aromatic if all the
following conditions are fulfilled:
1. It is cyclic, planar and has continuous delocalization of electrons (electrons in p orbitals)
with or without the participation of lone pair(s)/- charge/ + charge (i.e., having electrons or
vacant p orbital).
2. The delocalized -electron cloud must contain a total of (4n+2) electrons, where n is a
whole number (i.e., n =0,1,2,3 and so on). Putting n= 0 in (4n+2) we get 2 electrons,
similarly putting n=1, we get 6 electrons; n= 2 gives 10 electrons; n= 3 gives 14 electrons
and so on.
The criteria for the aromaticity in the fused rings also follows the same rule as applied to the
monocyclic systems. If the above two conditions are followed, then only, the compound is
aromatic. For example, the aromaticity of naphthalene and phenanthrene are shown below:
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
Aromaticity in above benzenoid structures is well accounted for, but few non benzenoid
structures also tend to show aromatic stabilization.
Note:
a. The p-orbitals in which the electrons are delocalizing must be parallel to each other so that a
continuous overlap of electrons is possible along the ring.
b. The selection of closed loop should be such that all the p-orbitals which are parallel to each
other are present in that loop.
4.1 Aromaticity of some benzenoid fused rings
4.1.1 Naphthalene
It is the simplest polycyclic aromatic compound which contain two benzene rings fused together
at the ortho bond.
It is easily seen to have a closed loop of p orbitals hosted on a set of coplanar carbon atoms.
Naphthalene contains 5 C=C bonds in the closed loop. Naphthalene contain 10 electrons. So,
according to Hückel’s Rule (n=2) naphthalene obeys (4n+2) electron rule. It shows that
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
naphthalene is aromatic. As in this case it contains a central double bond which makes it
different from the other two canonical forms which are equivalent to each other.
In naphthalene, the reactivity of the ring system is greater than that of the benzene. This has been
explained by considering one of the naphthalene rings as aromatic and the other as a butadiene.
As in naphthalene if one ring is to have six electrons other must have four electrons. So, the
reactivity of the fused rings is generally more than benzene.
4.1.2. Anthracene
Anthracene is another example of aromatic fused system which contain three ortho fused
benzene rings. It is colorless solid which shows blue fluorescence in ultraviolet light. It is the
component of coal tar. Anthracene contains 7 C=C bonds in the closed loop Anthracene contain
14 electrons. So, according to Hückel’s Rule (n=3) Anthracene obeys (4n+2) electron rule.
Anthracene shows four canonical forms.
4.1.3. Phenanthrene
Phenanthrene are the polycyclic aromatic hydrocarbons containing three aromatic rings. As
discussed earlier it is an ortho and peri fused ring. It is composed of one phenyl and one
anthracene ring.
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
Phenanthrene contain 7 C=C bonds in the closed loop. Phenanthrene also contain 14 electrons.
So, according to Hückel’s Rule (n=3) phenanthrene obeys (4n+2) electrons rule. It shows that
phenanthrene is aromatic. The resonance structures of phenanthrene are shown below:
Resonance energy of fused benzenoid rings
The resonance energies of these systems increase as the principal canonical form increases. For
benzene, naphthalene, anthracene and phenanthrene the principal canonical form formed are two,
three, four and five respectively having resonance energy 36,61,84 and 92 kcalmol-1. This can be
explained by taking the example of naphthalene which contain two benzene rings fused together.
So,
Expected resonance energy of naphthalene = 2 x 36 = 72 kcalmol-1
Observed resonance energy of naphthalene = 61 kcalmol-1
In this case the total number of π electrons are 10 not 12 which indicates that two benzene rings
share a pair of electrons and therefore delocalization energy per ring is decreased. This decrease
in resonance energy reduces the aromaticity. Due to this reason in general condensed polycyclic
hydrocarbons have relatively less aromatic character which result in higher reactivity.
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
Some other examples of benzenoid fused ring systems
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
4.2. Aromaticity of some non-benzenoid fused rings
4.2.1. Azulenes (C10 H8 ) . Bicyclo[5.3.0] decapentaene
Azulenes is an isomer of naphthalene and one of the few benzenoid structure which show
significant aromatic stabilization. It is a deep blue compound with the structure as shown and the
name is derived from the Spanish word ‘Qzul’ meaning Blue. It is a fused cyclo-heptatriene and
cyclopentadiene system.
Azulene
The compound shows the dipole moment of 0.80. In contrast to the fact that cyclopentadiene and
cycloheptatriene independently possess antiaromatic characteristics which are responsible for
their instability. But, this fused compound is aromatic and is stable.
Charged resonating structures shows the –ve charge on the five-membered ring, making it
equivalent to 6e cyclopentadienyl anion and seven membered ring bearing +ve charge is
similar to 6e tropylium cation, giving it an aromatic character.
In order to achieve the aromatic stabilization one electron from the seven-membered ring is
transferred to the five-membered ring. The main contributing structures to the hybrid show a
charge separation which is responsible for the observed dipole moment.
4.2.2. Oxaazulanones
Just like azulene oxaazulanones are also made up of one seven membered ring fused with a furan
ring. These are also the non-benzenoid compounds aromatic compounds. 5-Isopropyl-3-
(methoxycarbonyl)-2H-cyclohepta[b]furan-2-one and 3-(Methoxycarbonyl)-2H-
cyclohepta[b]furan-2-one are the examples of oxaazulanones shown below:
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
a) 5-Isopropyl-3-(methoxycarbonyl)-2H-cyclohepta[b]furan-2-one
b) 3-(Methoxycarbonyl)-2H-cyclohepta[b]furan-2-one
In case of oxaazulanones, these are aromatic rings but does not contain benzenoid structure.
Oxygen in the cyclic structure is sp2 hybridized because one of the two lone pairs occupies a pz
orbital, allowing oxygen to contribute to the continuous loop of pz orbitals and ultimately
completes the closed loop for electron delocalization.
5. Other special cases
Not all fused systems can be fully aromatic. This can be completely explained by taking some
examples:
5.1. Phenalene
In case of phenalene the double bond cannot be distributed in such a way so that each carbon has
one single and one double bond so it is not aromatic. But it is acidic in nature so reacts rapidly
with potassium methoxide to give the corresponding anion as shown. The anionic form of
phenalene is completely aromatic.
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
Phenalene
5.2. Benzo cyclobutadiene
Benzo cyclobutadiene is a fused ring which is composed of one benzene ring and the other is
cyclobutadiene. The two structures of benzo cyclobutadiene are shown below
If we consider the two rings of Benzo cyclobutadiene separately as shown in the diagram. In
structure (1) benzene ring portion contain six electron and cyclobutadiene portion contain two
electrons. So, both the rings are aromatic whereas in structure (2) benzene ring portion is
aromatic as it contains 6 electrons and cyclobutadiene is antiaromatic as it contains 4
electrons.
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
But If we consider a closed loop in Benzo cyclobutadiene it contains total of 8 electrons so it
does not obey the Hückel’s Rule of (4n+2) electrons. So, it is not aromatic rather it is
antiaromatic.
5.3. Ferrocene (bis s - cyclopentadienyl) ions
Molecular formula Fe (C5H5 )2 is a metallocene an organometallic compound containing of Fe2
ions sandwiched between two cyclopentadienyl anions on the opposite sides and held to each
other by complexation.
There are no C-Fe bonds as the two rings are free to state. The x-ray crystallographic studies
point towards the staggered conformation of the two rings as the most stable one, in the
condensed phase due to crystal packing while the gas phase electron diffraction studies point
towards the stable conformation to be eclipsed in the gas phase.
Ferrocene consists of the ion center in the +2 oxidation state (full valence shell of 18e , six of its
own, present in its five 3d AO’S) and six from each cyclopentadienyl anion (Each
cyclopentadienyl ring is then allocated a negative charge bringing the number of e each ring
to be six and hence making it aromatic) These twelve electrons (six from each ring) are shared
covalently with the metal ion having six d electrons on Fe2 with complex attaining stability and
aromaticity with 18 electron configuration.
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
6. Summary
A fused aromatic ring is one which shares one side of the ring. These are monocyclic
rings that shares their connecting bond.
Fused ring systems are classified into two categories depending on the number of atoms
and bonds shared by the rings.
Ortho-fused rings –If the two rings of the fused system that have only two atoms and one
bond is common between the rings.
Ortho and peri fused rings – If three atoms are common between the first ring and the
other two rings then it is said to be Ortho and peri fused rings.
The criteria for the aromaticity in the fused rings also follows the same rule as applied to
the monocyclic systems
1. It is cyclic, planar and has continuous delocalization of electrons (electrons in p
orbitals) with or without the participation of lone pair(s)/- charge/ + charge (i.e., having
electrons or vacant p orbital).
2. The delocalized -electron cloud must contain a total of (4n+2) electrons, where n
is a whole number (i.e., n =0,1,2,3 and so on).
Aromaticity of some benzenoid fused rings like naphthalene, anthracene and
phenanthrene
The resonance energy of fused system is generally less than of the number of benzene
ring present in that system.
Aromaticity of some non-benzenoid fused rings like azulene and oxaazulanones.
Aromaticity of some special molecules like phenalene, ferrocene and benzo
cyclobutadiene.
CHEMISTRY PAPER 1: ORGANIC CHEMISTRY- I(Nature of Bonding and
Stereochemistry)
MODULE 8: Aromaticity of fused rings
