What are Aromatic Compounds?

Aromatic compounds are chemical compounds that consist of

conjugated planar ring systems accompanied by delocalized pi-
electron clouds in place of individual alternating double and single
bonds.
They are also called aromatics or arenes. The best examples are toluene
and benzene .  Aromatics require satisfying  Huckel’s rule. 
Condition:
1. Planarity
2. Complete delocalization of the π electrons in the ring
3. Presence of (4n + 2) π electrons in the ring where n is an integer (n = 0, 1,
2, . . .)
Example
Properties of Aromatic Compounds
 Aromatic compounds have extremely high resonance energy.
 These are stable unsaturated compounds.
 They are generally non – polar and immiscible with water.
 They give a sooty yellow flame due to the high ratio of carbon to
hydrogen.
 Aromatic compounds undergo substitution reactions rather than
addition reactions.
 These have delocalized pi-electrons. 
 They show a coplanar structure.
 They are used as a solvent for non - polar compounds.
 They show electrophilic aromatic substitution and nucleophilic
aromatic substitution reactions. 

Arene and Aryl Groups

Students generally get confused between arene and aryl groups. Let us clear this
doubt here only. Arene is a compound containing one or more benzene rings.
While when we remove a hydrogen atom from an arene, the aryl group is formed.
It means benzene is an arene, but phenyl is an aryl group. All arenes are aromatic
compounds but it's not necessarily that all aromatic compounds are arenes.
Aromaticity
All aromatic compounds show aromaticity. The term aromaticity is used to
describe a property of a cyclic, planar molecule with a ring of resonance bonds that
exhibits more stability than other geometric or connective arrangements with the
same set of atoms. The word aromaticity comes from the word ‘aroma’ which
means fragrance or odor. Since most of the aromatic compounds are derivatives of
benzene and benzene gives a distinct odor so, the compounds were named aromatic
compounds. Although presently many non – benzene aromatic compounds have
been discovered which do not have any odor. The term aromatic was first used by
August Wilhelm Hofmann in 1855. Compounds must fulfill the following four
conditions to be an aromatic compound –
 The molecule must be cyclic. Example – Benzene and pyrrole are aromatic
in nature while acyclic compound C4H5NH2 is a non-aromatic compound. 
Structures are given below – (image)
  Every atom in the cyclic ring must be conjugated. As it will provide the
cyclic ring delocalized pi-electron system. Thus, we can say every atom in
the cyclic ring must have an empty p orbital and must be capable of
participating in resonance. 
Examples are given below – (image)
 Huckel’s Rule of Aromaticity: All compounds must obey Huckel’s Rule i.e.
molecule must have 4n+2 pi-electrons where n is an integer (i.e. n= 0, 1, 2,
3, 4…etc.). For example,  Benzene has 6 pi-electrons and (4×1)+2 = 6, thus
it obeys Huckel’s Rule while cyclooctatetraene has 8 pi-electrons 4n+2 ≠ 8,
thus it does not follow Huckel’s Rule. So, benzene is aromatic and
cyclooctatetraene is a non-aromatic compound.
 The molecule should be planar or flat. Those compounds which follow the
above 4 rules of aromaticity are generally flat as in that condition they
possess large enough potential energy. 
Huckel’s Rule of Aromaticity
Huckel’s rule states that only planar, fully conjugated monocyclic polyenes having
4n + 2 π electrons, where n is an integer, that is, n = 0, 1, 2, 3, 4, etc., should
possess aromatic stability. An aromatic compound must be planar and contain a
cyclic cloud of π electrons below and above the plane of the molecule. It contains
sp2 hybridized carbon atoms and must obey the Huckel rule.
According to this rule, the ring system must have (4n+2) π electrons, where n is
any whole number (0, 1, 2, 3, etc). On this basis the ring systems which have
2(n=0), 6(n=1), 10(n=2), 14(n=3) etc pi electrons are aromatic. Typical examples
of aromatic compounds are benzene, naphthalene, and anthracene.
S.
Aromatic Hydrocarbons Aliphatic Hydrocarbons
No.

These hydrocarbons contain These hydrocarbons contain carbon

carbon and hydrogen attached in and hydrogen attached in straight
1
a ring system with delocalized pi- chains, branched chains, or in non-
electrons aromatic ring forms

2. They show aromaticity. They do not show aromaticity.

All aromatic compounds follow It is not necessary that ll aliphatic

3.
Huckel's rule. hydrocarbons will follow Huckel's rule

In these compounds, the carbon In these compounds, the carbon to

to hydrogen ratio is low. hydrogen ratio is high.

These compounds generally burn These compounds burn with a non-

6.
with sooty flame (yellow). sooty flame.

These are unsaturated Aliphatic hydrocarbons can be

7.
compounds. saturated and unsaturated.

They have delocalized pi- They do not have delocalized pi-

8.
electrons.  electrons.

These are conjugated The majority of these compounds are

9.
compounds. not conjugated.

Benzene, toluene, naphthalene,

Methane, ethane, propane, etc. are
10. etc. are examples of these
examples of these compounds.
compounds.
 What is Benzenoid

Benzenoid compounds are molecules that have at least one benzene ring in its
chemical structure. A benzene ring is a cyclic structure having six carbon atoms as
the ring members. It has three pi bonds (double bonds) and three sigma
bonds arranged in an alternative pattern. Therefore, we call this pattern
a conjugated pi system.

Since the molecule has double bonds due to benzene ring, the molecule is an
unsaturated compound with extra stability provided by the conjugated pi system.
What is Non Benzenoid?
Non benzenoid compounds are aromatic molecules that do not have benzene rings
in its chemical structure. Although a benzene ring is absent, these molecules have a
conjugated pi system. The ring structures of these compounds have around 5-7
carbon atoms.

The aromatic nature arises due to the presence of conjugated pi system. This
conjugated pi system provides the molecule with extra stability. Some common
examples include azulenes, Oxaazulanones, Pentafulvene, Tropones & Tropolones,
etc.
What are the Similarities Between Benzenoid and Non Benzenoid?
  Both are cyclic structures
 Benzenoid and Non Benzenoid are aromatic compounds with conjugated pi
systems
 Both Benzenoid and Non Benzenoid exhibit an extra stability
What is the Difference Between Benzenoid and Non Benzenoid?
Although both benzenoid and non benzenoid compounds are aromatic compounds,
they have few differences between them. The difference is the presence of a
benzene ring in these two compounds. In benzenoid compounds there are benzene
rings present that gives cause to its name whereas a benzene ring is absent in non
benzenoid compounds. These structural differences definitely affect the chemical
properties and reactivity of these compounds.
Molecular orbital structure of benzene:
The orbital structure of benzene: All the carbon atoms in benzene are
sp2 hybridised. The three sp2 hybrid orbitals are lying in one plane and oriented at
an angle of 120°. The fourth unhybridized p-orbital having two lobes is lying
perpendicular to the plane of the hybrid orbital. Two out of the three sp2 hybrid
orbitals of each carbon atom overlap axially with sp2 hybrid orbitals of the
neighbouring carbon atoms on either side to form carbon-carbon σ bonds. The
third hybrid orbital of each carbon atom overlaps axially with the half filled 1s-
orbital of the hydrogen atom to form carbon-hydrogen sigma bonds. Thus there is
six sigma C-C bonds and six sigma C-H bonds. There is still one unhybridized
2pz orbital on each carbon atom. This orbital consists of two lobes, one lying
above and the other below the plane of the ring.
The unhybridized 2pz orbital on each carbon atom can overlap sidewise with the
2pzorbital of the two adjacent carbon atoms in two different ways as shown below
giving rise to two sets of -bonds. Since 2pz orbital on any carbon atom can
overlap sideways with the 2pz orbital on adjacent carbon atom on either side
equally well, a continuous -molecular 3 orbitals will result which embraces all the
six p-electrons as shown:

The net result is that there are two continuous rings-like electron clouds, one above
and the other below the plane of atoms as shown. This delocalisation of π-electrons
imparts unique stability to the benzene molecule.

In benzene molecule all   and    are of 120° each and each C-C bond
length is 139 pm.
Four Key Rules For Aromaticity
There turn out to be 4 conditions a molecule must meet in order for it to be
aromatic.
It’s all or nothing. If any of these conditions are violated, no aromaticity is
possible.
  First, it must be cyclic.
 Second, every atom in the ring must be conjugated.
 Third, the molecule must have [4n+2] pi electrons (we’ll explain in depth
what that means, below)
 Fourth, the molecule must be flat (usually true if conditions 1-3 are met, but
there are rare exceptions)
Let’s go into more detail.
Some example:
Why pyridine is a aromatic compounds?
Pyridine is an example of a six-membered aromatic heterocycle and has an
electronic structure similar to benzene. In the bonding picture of pyridine the five
carbons and single nitrogen are all sp2 hybridized. All six of these atoms have a p
orbital perpendicular to the plane of the ring and each contains one pi electron
which allows the ring to be fully conjugated. This makes the pi electron count for
pyridine 6 pi electrons. In much the same fashion as benzene, the 6 pi electrons
follow the 4n + 2 rule and completely fill the bonding molecular orbitals which
fulfills the electronic requirement for aromaticity. The lone pair electrons on
pyridine's nitrogen are contained in a sp2 orbital that lies in the same plane as the
ring and does not overlap with the p orbitals of the ring. The lone pair electrons are
not part of the aromatic system and do not affect the p electron count. Pyridine's
electrostatic potential map shows that the lone pair electrons, shown in a
yellow/red color, are locked onto the nitrogen and not distributed around the ring.
Preparation of benzene from alkynes
Benzene is prepared from ethyne by the process of cyclic polymerization. In this
process, Ethyne is passed through a red-hot iron tube at 873 K. The ethyne
molecule then undergoes cyclic polymerization to form benzene.

Preparation of benzene from aromatic acids

Benzene can be prepared from aromatic acids through decarboxylation reaction. In this process, the
sodium salt of the benzoic acid (sodium benzoate) is heated with soda lime to produce benzene
along with sodium carbonate.

Preparation of benzene from phenol

Benzene can be prepared from phenols too through their reduction. In this process vapours of
phenol are passed over heated zinc dust. Zinc dust reduces them to form benzene.
Addition reactions of benzene
Addition reactions occur under more drastic conditions(higher temperatures, higher
pressures) because extra stability of the delocalised Π electrons.

Addition of hydrogen(catalytic hydrogenation)

Benzene reacts with hydrogen in the presence of nickel or platinum catalyst at
2000C, 3000C under pressure to form cyclohexane.
Addition of halogens
Benzene reacts with chlorine(Cl2) or bromine(Br2) in the presence of sunlight to
form hexachloride (BHC).

Ozonolysis
Substitution reactions of benzene
One or more hydrogen atoms in benzene ring get replaced by other atoms or
groups. These substitution reactions are occurred through electrophilic substitution
reaction.

 Halogenation
 Nitration
 Alkylation or friedel craft alkylation
 Acetylene or friedel craft acylation

Halogenation of benzene
A hydrogen atom in the benzene ring is replaced by a halogen atom(F, Cl, Br, I) is
called halogenation. Lewis acids such as ferric chloride(FeCl3) or aluminium
chloride (AlCl3) are used as catalyst and they acts as the halogen carrier. This
reaction occurs through a electrophilic substitution mechanism.
benzene and chlorine with AlCl3

benzene and bromine with FeBr3

Alkylation or friedel crafts alkylation - Alkyl halides and benzene reaction

Alkyl halides react with benzene in the presence of anhydrous AlCl3, and gives
alkyl benzene as a product. A hydrogen atom in the benzene ring is replaced by
alkyl group.
benzene and chloromethane with anhydrous aluminium chloride
benzene and chloromethane react in the presence of anhydrous AlCl3 to give
methylbenzene / toluene.

benzene and bromoethane with anhydrous aluminium chloride

benzene and bromoethane react in the presence of anhydrous AlCl3 to give
ethylbenzene.

Acylation or friedel craft acylation - benzene and acid

chloride reaction
Benzene reacts with acid chloride or acid anhydride and give acyl benzene in
the presence of anhydrous AlCl3.
Benzene and ethanoyl chloride with anhydride aluminium chloride

Benzene and with Acetic anhydride with aluminium chloride

Nitration - concentrated nitric and sulfuric acids with

benzene reaction
A hydrogen atom in the benzene ring is replaced by a nitro(-NO2) group is
called the nitration. this reaction is carried out by heating benzene with the
nitrating mixture of concentrated nitric ans sulfuric acids at 500C.

Nitration of Benzene
Benzene reacts with concentrated nitric acid at 323-333k in the presence of concentrated sulphuric
acid to form nitrobenzene. This reaction is known as nitration of benzene.
The mechanism for nitration of benzene:
Step 1: Nitric acid accepts a proton from sulphuric acid and then dissociates to form nitronium ion.

Step 2: The nitronium ion acts as an electrophile in the process which further reacts with benzene to
form an arenium ion.

Step 3: The arenium ion then loses its proton to Lewis base forming nitrobenzene.
Sulfonation of Benzene
Sulfonation of benzene is a process of heating benzene with fuming sulphuric acid (H2SO4 +SO3) to
produce benzenesulfonic acid. The reaction is reversible in nature.

The mechanism for Sulfonation of benzene

Due to higher electronegativity, oxygen present in sulphuric acid pulls an electron towards itself,
generating an electrophile. This attacks the benzene ring, leading to the formation of
benzenesulfonic acid.
Halogenation of Benzene
Benzene reacts with halogens in the presence of Lewis acid like FeCl3, FeBr3 to form aryl halides.
This reaction is termed as halogenation of benzene.

Halogenation of benzene

The mechanism for halogenation of benzene:

Step 1: Being a Lewis acid, FeBr3 helps in the generation of electrophile bromine ion by combining
with the attacking reagent.

Generation of bromine ion

Step 2: The bromine ion acts as an electrophile in the process which further reacts with benzene to
form arenium ion which finally converts to bromobenzene.
The Ortho-Para Ratio
In addition, the ortho and para are not formed in an equal amount either. In
general, the para product is more favorable because of the steric strain
between the closer located ortho substituents. And the larger the groups, the
higher the strain, therefore the higher the regioselectivity:

Meta Directors
Deactivating groups slow down electrophilic aromatic substitutions and direct
the substituents to the meta position. The only exceptions are the halogens
that deactivate the aromatic ring yet directing the electrophile to
the ortho and para positions. There is a separate post about this which you can
check here.
Let’s why the nitration of nitrobenzene occurs mainly at the meta position:
As usual, go ahead and draw the complete mechanism with the resonance
structures. We will use E instead of NO2 as a general mechanism: