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
SOME PROPOSED STRUCTURES OF BENZENE
adhere to these four rules:
The reaction of benzene with bromine in the
1. It has to be a ring.
presence of an iron catalyst eliminated most of the
proposed structures. This reaction produced only
2. It has to be planar (flat).
one monobromo product and three distinct dibromo
products (ortho, meta, and para).
3. Each atom of the ring needs to have a p
orbital that’s at a right angle to the plane of the ring.
Kekulé reasoned that ortho-dibromobenzene (1,2-
In other words, no atom on the ring can be sp3
dibromobenzene) existed in two forms that were in
hybridized.
rapid equilibrium and couldn’t be isolated.
4. The ring needs a Hückel number of pi
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 Kekulé’s proposed structures for 1,2-
have to determine which lone pairs are part of the pi dibromobenzene
system. First draw in any of the lone pairs on the
heteroatoms, and then follow these guidelines: PHYSICAL PROPERTIES OF BENZENE

- If the heteroatom is part of a double bond, it can’t Benzene is a typical nonpolar compound that, like
contribute its lone pairs to the pi system. • If the other nonpolar compounds, has a low solubility in
heteroatom is connected to the ring with only single water. It has a characteristic odor which most people
bonds, one of the lone pairs (but only one) goes into find unpleasant. It was widely used in academic labs
the pi system. Thus, no heteroatom can contribute as a solvent, but that use has been largely
more than two electrons to the pi system. discontinued since it was found that benzene may
be carcinogenic.
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.
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.
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
that compounds containing a benzene ring as part 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.