DETERMINING AROMATICITY, ANTI-

AROMATICITY, OR NONAROMATICITY OF
RINGS

Being able to predict which ring systems will be

stable (and aromatic) and which will be unstable
(and anti-aromatic) is an important part. For a
molecule to be stable and aromatic, it needs to
adhere to these four rules:
SOME PROPOSED STRUCTURES OF BENZENE
1.   It has to be a ring.
The reaction of benzene with bromine in the
2.   It has to be planar (flat). presence of an iron catalyst eliminated most of the
proposed structures. This reaction produced only
3.   Each atom of the ring needs to have a p one monobromo product and three distinct dibromo
orbital that’s at a right angle to the plane of the products (ortho, meta, and para).
ring. In other words, no atom on the ring can be sp3
hybridized. Kekulé reasoned that ortho-dibromobenzene (1,2-
dibromobenzene) existed in two forms that were in
4.   The ring needs a Hückel number of pi rapid equilibrium and couldn’t be isolated.
electrons, following the 4n + 2 rule (a pi electron is
an electron occupying an orbital made from the
side-by-side overlap of p orbitals). That is, if you set
4n + 2 equal to the number of pi electrons in the
ring, n must be an integer. If n isn’t, the ring system
has a non-Hückel number of electrons.

If the ring has a heteroatom (such as O, S, or N),

you have to determine which lone pairs are part of
the pi system. First draw in any of the lone pairs on
the heteroatoms, and then follow these guidelines:
- If the heteroatom is part of a double bond, it can’t
contribute its lone pairs to the pi system. • If the
heteroatom is connected to the ring with only single
bonds, one of the lone pairs (but only one) goes
into the pi system. Thus, no heteroatom can
contribute more than two electrons to the pi system.
If the ring meets the first three criteria but has a
non-Hückel number of pi electrons following the
equation 4n, then the ring is considered anti-
aromatic. However, if the molecule doesn’t meet
the first three criteria, the ring is simply nonaromatic
— it’s neither exceptionally stable nor unstable.
 
Benzene is a hugely important compound in
organic chemistry. It consists of six carbon atoms
joined together in a ring, with a hydrogen atom
bonded to each carbon; by replacing one or more
of these hydrogen with a functional group, a large
number of different compounds can be formed.
This graphic looks at a selection of the most
common simple derivatives which can be obtained
in this manner.
Compounds that contain benzene rings in their
structures are commonly referred to as ‘aromatic
compounds’. This terminology derives from the fact
that they are often have a pleasant and
sweet fragrance (although benzene itself does not),
but the more modern definition of the word relates
to the structure of molecules. Put simply, it refers to
cyclic arrangements of bonded carbons that are
conjugated – that is, they are joined by alternating
double and single bonds.
FIGURING OUT BENZENE’S STRUCTURE
 Benzene was first isolated in 1825 from coal tar.
Later, chemists determined that it had the
molecular formula C6H6. Further investigation of its
chemical behavior showed that benzene was unlike
other hydrocarbons in both structure and reactivity.
Kekulé’s proposed structures for 1,2-
dibromobenzene
PHYSICAL PROPERTIES OF BENZENE
Benzene is a typical nonpolar compound that, like
other nonpolar compounds, has a low solubility in
water. It has a characteristic odor which most
people find unpleasant. It was widely used in
academic labs as a solvent, but that use has been
largely discontinued since it was found that
benzene may be carcinogenic.
The table above compares the melting and boiling
points of benzene to those of cyclohexane, which
indicates some differences found in aromatic
compounds. The values for benzene are higher
than the corresponding values for cyclohexane. In
most other situations, when dealing with
compounds with similar structures, the lower
molecular-weight compound has the lower melting
and boiling point; however, when comparing
benzene to cyclohexane, you see that the reverse
is true. This is because of the delocalization of the
electron pairs in benzene.
PROPERTIES OF AROMATIC COMPOUNDS
Arenes are mostly nonpolar and non-miscible in
water. These compounds are usually unreactive
and are used as solvents for various other nonpolar
compounds. Their carbon to hydrogen ratio is high
therefore, they are characterized by sooty yellow
flame.
CLASSIFICATION OF AROMATIC COMPOUNDS
The classification of arenes is based on the position
of the functional group. They are classified into two
and we have discussed below:

1. NUCLEAR SUBSTITUTED COMPOUNDS
In any aromatic compound whenever any
substituent or functional group, is directly linked to
the benzene ring, it is known as a nuclear-
substituted compound.  that compounds containing a benzene ring as part
2. SIDE CHAIN SUBSTITUTED COMPOUNDS
In any aromatic compound if the functional group is
available in the side chain of the ring then it is
known as a side chain substituted compound.
These compounds are named as the phenyl
derivatives of the relative aliphatic compounds.
NOMENCLATURE OF THE AROMATIC FAMILY
The nomenclature (naming) of aromatic
compounds begins with numbering the ring
positions. This numbering is similar to the
numbering of cycloalkane systems. The key group
is at the number one position. Older usage uses
ortho (o-) in place of 1,2-numbers, meta (m-) in
place of 1,3-numbers, and para (p-) in place of 1,4-
numbers.
Two examples demonstrating different ways of
naming aromatic compounds
Substituted benzenes are named using –
benzene as the parent. No number is needed for
monosubstituted benzenes because all the ring
positions are identical.
Many substituted aromatic compounds have
common names in addition to their systematic
names. For example, methylbenzene is familiarly
known as toluene, hydroxybenzene as phenol,
aminobenzene as aniline, and so on, as shown
below.
More complex benzene-based molecules have
applications in medicine; paracetamol, which has
the chemical name acetaminophen, is commonly
used as an analgesic to relieve pain and
headaches. In fact, a large number of medicinal
compounds are likely to feature a benzene ring
somewhere in their structure, though these
compounds are often more complicated than those
shown here.
On a final note, benzene is a well known
carcinogenic molecule. However, this doesn’t mean
of their structure are also carcinogenic. It’s a
common misconception that, if a compound is used
to produce a certain chemical product, the risks
associated with it remain the same. In fact, when
benzene is reacted to produce different derivatives,
it ceases to be the compound benzene, and the
chemical properties of the products can often be
completely different. So, the presence of a benzene
ring in the structure of a compound isn’t an
automatic cause for concern – in fact, a large
number of compounds found in our food contain a
benzene ring somewhere in their structure.
 
BENZENE REACTIONS - SULFONATION,
NITRATION AND HALOGENATION
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.

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.

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.