M.Sc.

(Chemistry): IV Semester (Study Material)

By: Dr. Arti Vishwkarma
DDU Gorakhpur University, Gorakhpur

CHO-403; Unit-1-Aromaticity

Aromaticity is generally associated with the stability of certain completely conjugated cyclic
molecules. It depends upon the some criteria like bond length, resonance energies, induced ring
current etc. Benzene, benzenoid and some analogous species exhibit such features of
aromaticity.

 Bond length:
It has been experimentally proved that the average C-C bond length in aromatic
compounds is nearly 1.39 Å which does not fall in the range of single or double bond
length. The absence of bond length alteration provides strong support for aromaticity in a
compound.
1.39 1.42 1.359

1.39 1.395 1.395

1.37 N
Benzene Pyridine Naphthalene
(C-C bondlenght=1.39 Å)

 Resonance Energy:
According to VBT and MOT high delocalization energy is the cause of aromaticity in
planar cyclic compounds. Molecular overcrowding in non-benzenoid hydrocarbons and
related compounds can restrict aromaticity (ex. - [14] Annulene should be aromatic if it is
planar but due to overcrowding it is not aromatic). Therefore π-electrons of cyclic
conjugated system should be delocalised in π-bonding molecular orbitals so that
resonance energy is maximum.

 Induced Ring Current:

Aromatic compounds sustain an induced ring current which can be detected
experimentally by the use of nuclear magnetic resonance (NMR). Compound in which
outer protons are shielded while inner protons are deshielded is termed as paratropic
molecule and they are antiaromatic in nature. Compound in which outer protons are
deshielded while inner protons are shielded is termed as diatropic molecule and they are
aromatic in nature.
 According to Huckel molecular orbital theory following characteristics have been accepted as
essential criteria for aromaticity:

a) Molecule must be cyclic.

b) Planar i.e. sp2 hybridized.
c) Conjugated system
d) 4n+2 π electrons (where n= 0,1,2,3…).

Compounds which are cyclic, planar, conjugated and contains (4n+2) π electrons system are
termed as aromatic compounds. Some examples of aromatic compounds are given below.

Benzene Cyclopentadienyl anion Cyclopropenium cation

(n=1) (n=1) (n=0)
- -
6πe 6πe 2πe-

N
Naphthalene Tropylium cation Pyridine
(n=2) (n=1) (n=1)
- -
10πe 6πe 6πe-

Compounds which are cyclic, planar, conjugated and contain (4n) π electrons system are
known as antiaromatic compounds. Some examples of antiaromatic compounds are given
below.

Cyclopropenium anion Cyclobuta-1,3-diene Cyclopentadienyl cation Pentalene

(n=1) (n=1) (n=1) (n=2)
4πe- 4πe- 4πe- 8πe-
Compounds which do not follow Huckel’s rule (i.e. cyclic/acyclic, planar/nonplanar,
conjugated/nonconjugated system and number of electron is not certain) are termed as
nonaromatic compounds. Some examples of nonaromatic compounds are given below.

nonplanar acyclic nonconjugated acyclic

nonconjugated acyclic
cyclic, planar, conjugated
but n=3/4

Comparison between Aromatic, Nonaromatic and Antiaromatic Compounds

Aromatic Nonaromatic Antiaromatic

 Cyclic, planar,  Noncyclic or nonplanar  Cyclic, planar,

conjugated or not conjugated conjugated
 (4n+2)π e-s  (no of e-s are not  4n π e-s
(no of e-=2, 6, 10 ,14) definite) (no of e-= 4, 8, 12,16)
 Stable  Regular  Unstable
  
Ex- Cyclopropenyl cation Ex- Cyclopropene Ex- Cyclopropenyl anion
+ sp3 -
(nonplanar)

Cyclopentadienyl anion Cyclopentadiene Cyclopentadienyl cation

_ sp3 +
(nonplanar)

Stability Order: Aromatic > Nonaromatic >Antiaromatic

Aromaticity can also be explained with the help of Frost Circle which is applicable to monocyclic
planar conjugated system. A Frost circle is a circle drawn around all the vertex of a polygon
having one vertex pointing down. Each vertex touching the circle represents an energy level.
Electrons are arranged according to the Hund’s rule starting with the lowest energy orbital first.
Energy levels below the diameter are bonding MOs and above are anti-bonding MOs while MOs
situated on the diameter are non-bonding (Fig. 1). Two criteria for aromaticity on the basis of
Frost circle are as follows:

 Aromaticity is present when all the BMOs are filled and NBMOs are completely filled or
empty.
 Antiaromaticity is observed if electrons are filled in ABMOs or it has half filled
BMOs/ABMOs/NBMOs.

Compound Frost circle Π-electron arrangement Aromaticity

ABMO

Aromatic

Cyclopropenium cation BMO

ABMO

NBMO Antiaromatic
Cyclobutadiene
BMO

ABMO

Aromatic
BMO
Cyclopentadienyl anion
BMO

ABMO
ABMO
Aromatic

BMO
Benzene
BMO
Figure: 1

(Where, BMO=Bonding Molecular Orbital; NBMO=Nonbonding Molecular Orbital;

ABMO=Antibonding Molecular Orbital)
Homoaromatic compounds

If a cyclic conjugated system can be formed by passing one or more than one sp 3 hybrid carbon
atom then it is termed as homoaromaticity. In comparison to the true aromatic systems, the net
stabilization in homoaromatic system may be low due to poor overlapping of orbitals.
Homotropylium ion (cyclooctatrienyl cation) is the best example of homoaromaticity. In this ion
an aromatic sextet is spread over seven carbons while eight carbon is sp3 carbon and it is not
involved in aromaticity.
Ha
Hb

H+

H
H
Ha
Cyclooctatetraene Homotropylium ion
Hb

Figure: 2

Aromaticity in Non-benzenoid Compounds

Compounds having at least one benzene ring are termed as benzenoid compounds whereas
non-benzenoid compounds are aromatic compounds with conjugated π-electron system but do
not contain benzene ring. Aromticity of non-benzenoid compounds can also be known according
to Huckel’s rule.

Some important non-benzenoid aromatic compounds are as follows:

1. Annulenes (Monocyclic Non benzenoid Neutral Compounds)

Monocyclic hydrocarbons having general formula (CH)2m that contain maximum number
of non-cumulated double bonds are known as annulenes. Compound having m=odd, then
(4n+2)π electron system and if m=even then it is (4n)π electron system. IUPAC nomenclature
of annulenes with 7 or more carbon atoms are named as [n]annulene (where n= no. of carbon
atoms in the ring). Some examples of annulenes are given below.

[4]Annulene [6]Annulene
[8]Annulene

[10]Annulene
[12]Annulene
Aromaticity of annulenes can be tabulated as follows:

Annulene Aromaticity

[4]Annulene/cyclobutadiene Antiaromatic
[6]Annulene/benzene Aromatic
[8]Annulene Nonaromatic
[10]Annulene Nonaromatic
[12]Annulene Weakly Antiaromatic
[14]Annulene Weakly aromatic
[16]Annulene Weakly antiaromatic
[18]Annulene Aromatic

Annulenes with (4n+2)π electrons are as follows:

[10]Annulene: [10]Annulene exists in three isomeric forms having (4n+2)π electrons but they
all are non-planar hence nonaromatic. The three isomers are given below.

H H H

di-trans-[10]annulene all-cis-[10]annulene mono-trans-[10]annulene

In di-trans-[10]annulene planarity is disturbed because of two internal hydrogens; while in other

two isomers are nonplanar due to angle strain and some other strains. Replacing two interacting
hydrogens in di-trans-[10]annulene yields 1,6-methano-[10]annulene in which the transannular
interactions are removed. The NMR spectrum of 1,6-methano-[10]annulene shows that it is a
diatropic molecule and hence is aromatic. 1,6-methano-[10]annulene generally undergoes
electrophilic substitution reactions.
1
directly linked Methylene bridge
between C1 and C6 H between C1 and C6
H
6
1,6-dimethano-
Naphthalene di-trans-[10]annulene [10]annulene
(aromatic)
(It showed diamagnetic
ring current in NMR and
its bond lenght pattern
is similar to naphthalene
hence aromatic)

1,6-methano-[10]annulene can be synthesized from naphthalene as shown in Fig. 3.

 CHCl3/BuOK Cl
Na/NH3 (l)
Cl

Naphthalene Isotetralene
Na/NH3 (l) or
Bu3SnH
Br Br

Br2
CH2Cl2

Br Br

KOH/MeOH DDO

1,6-methano-[10]annulene

Figure: 3

[14]Annulene:

[14]Annulene (Cyclotetradecaheptaene) has (4n+2)π electron system and all carbon-carbon

bonds are of equal length but due to four inner hydrogen it is not planar. This annulene is a
diatropic molecule hence it is aromatic although it is not planar. The aromaticity of [14]Annulene
is reduced due to the overlapping of Vander Waals radii of the four hydrogens. A number of
1,6:8,13 bridged [14] annulenes have been prepared with both carbon and heteroatom bridges.
Ex. – Syn-1,6:8,13-Bisoxio[14]annulene and Syn-1,6-methano-8,13-oxiodo[14]annulene

H H

H H

[14]Annulene
 O O O

Syn-1,6:8,13-Bisoxio[14]annulene Syn-1,6-methano-8,13-oxiodo[14]annulene

One of the scheme of preparation of [14]Annulene is shown in Fig. 4.

(i) Bu+OK
Bu+OH
Cu(OAc)2/Py C6H6
[14]Annulene
(ii) H/Pd

Figure: 4

2. Azulene

Azulene is an example of bicyclic nonbenzenoid aromatic compounds. Azulene is

isomeric with naphthalene (resonance energy= 77 kcal/mole) but in comparison it is less stable
as resonance energy of azulene is 49 kcal/mole. The dipole moment of azulene is 1.0 D while
the dipole moment of naphthalene is zero. The dipole moment of azulene indicates the
existence of charge separation in the molecule and that each ring approximately contains six π-
electron systems.

>350 C

Azulene Naphthalene

Azulene may be regarded as a grouping of aromatic cycloheptatrienyl cation and

cyclopentadienyl anion (Fig. 5). The dipolar form of azulene arises due to the tendency of
electrons to be transformed from the seven membered ring to five membered ring as it satisfies
the Huckle rule and it is aromatic in nature.

Figure: 5
Scheme for synthesis of azulene is given below (Fig. 6):

O
O

(i) O3 Na2CO3
(ii) Zn/H2O

O
9-Octalin OH

O
HO

LiAlH4

Pd-C

Azulene

Figure: 6

Some characteristics of azulene are as follows:

(i) It does not get polymerized.

(ii) Under normal circumstance, it does not act as a diene in Diels-Alder reactions.
(iii) Azulene undergoes electrophilic substitution reaction in five membered ring as it is
electron rich in dipolar structure and incoming substituent first goes to position-1 and the
second incoming group enters at position 3.
(iv) Azulene undergoes nucleophilic substitution reaction in seven membered ring as it act
like cycloheptatrienyl cation.
Azulene forms azulenium cation in presence of strong acid.
H
H

Azulenium cation

3. Tropolone

Tropolone is a seven memebered cyclic ketone with hydroxyl group at position-2. It was
first of all found in some natural products. Its aromaticity and stability is more than tropone due
to presence of OH group as lone pair of oxygen is involved in the conjugation with the pi-bonds
and also because of hydrogen bonding. The dipole moment of tropolone is 3.60 D while its
resonance energy 36 kcal/mole. The resonance hybrid clearly reveals the presence of six π-
electrons in the seven membered ring, hence tropolone is an aromatic compound.

OH

Tropolone

O O H
O O
OH OH
OH O

Resonance hybrid structures of tropolone

Synthesis of tropolone from benzene is given in Fig. 7.

CH2N2
H Electrocyclic ring opening
hv
H

KMnO4

OH O

O O

Figure: 7

Alternate and Non-alternate Hydrocarbons

Aromatic hydrocarbons can be classified as alternate and non-alternate hydrocarbons.

(i) Alternate Hydrocarbons:

An alternate hydrocarbon is any conjugated hydrocarbon
system which does not have an odd-membered ring. An alternate system is one in which
the atoms can be divided into two sets such that the atoms are of one set are bonded
only to atoms of the other set. It may be of two types:

a) Even alternate hydrocarbons:

The hydrocarbons containing even number of
conjugated atoms (i.e no. of one set of atoms= no. of the other set of atoms) are
known as even alternate hydrocarbons. Ex. – benzene, naphthalene, 1,3-
butadiene, 1,3,5-hexatriene etc.
Aliphatic and aromatic even alternate hydrocarbons contain only bonding and
antibonding molecular orbitals (no. of BMO = no. of ABMO) (Fig. 8).
 

 

   
  
 
(n=m=2) (n=m=3) (n=m=3) (n=m=5)
{Where, n = no. of starred atoms; m = no. of atoms of unstarred atoms}

Examples of even alternate hydrocarbons

1,3-butadiene Benzene
Energy levels in even alternate hydrocarbons

Figure: 8

b) Odd alternate hydrocarbons:

The hydrocarbons containing odd number of
conjugated atoms (i.e no. of one set of atoms ≠ no. of the other set of atoms) are
known as odd alternate hydrocarbons. Carbocation, carbanion or free radicals
may be the example of odd alternate hydrocarbons and it contain all bonding,
antibonding as well as nonbonding molecular orbitals (BMO will always be equal
to ABMO) (Fig. 9).
 CH2 

 CH2 

 

(n=2; m=1) (n=4;m=3)

{Where, n = no. of starred atoms;
and m = no. of atoms of unstarred atoms}

Examples of odd alternate hydrocarbons

 E

Cation Free radical Anion

Allyl System

Energy levels in odd alternate hydrocarbons

Figure: 9

(ii) Non-alternate Hydrocarbons:

Non-alternate hydrocarbons are those hydrocarbons in
which the conjugated atoms, whose number may be even or odd, are divided into two
sets in a such a manner that two atoms of same set is connected to each other. Cyclic
non-alternate hydrocarbons contain at least one ring with odd number of carbon atoms.
Non-alternate hydrocarbons may be aromatic, non-aromatic or antiaromatic.


CH2




    


 


Examples of non-alternate hydrocarbons

References:

1. Advanced Organic Chemistry by Dr. Jagdamba Singh and L. D. S. Yadav,

Pragati Prakashan, 2010.
2. March’s Advanced Organic Chemistry: Reactions, Mechanisms and Structure, 7th
Edition, 2013.