LEC 19 Nomen-Culture and Structure of Benzene

Nomenclature and Structure of
Benzene
Dr. Muhammad Tahir Saddique
Assistant Professor (Chemistry)
Department of Applied Sciences
Contents
Nomenclature of Aromatic Compounds
(a) Naming of monosubstituted benzenes
(b) Naming of disubstituted benzenes
(c) Naming of polysubstituted benzenes
(d) Fused polycyclic arenes
Structure of benzene
Common and IUPAC of aromatic compounds.
(a) Naming of monosubstituted benzenes
Benzene is represented by regular hexagon with a circle
incribed in it. The monosubstituted derivatives of
benzene are those in hydrogen of the ring is replaced by
another substituent. These are named by prefixing the
name of substituent to the word benzene. e.g. Benzene
in which one of the hydrogen is replaced by chlorine (Cl)
is named as chlorobenzene. Here the chlorine atom may
occupy any of the six positions on the benzene ring.
Some benzene derivatives have common names which
are commonly accepted. e.g.
(C6H5CH3) Toluene, (C6H5OH) Phenol, (C6H5NH2 Aniline,
C6H5COOH Carboxylic acid
Sometimes, it is more convenient to name the benzene
ring as a substituent, the phenyl group. The phenyl
group is often symbolised as C6H5-, ph or Φ. Another
common aromatic substituent is Benzyl group which is
abbreviated as C6H5CH2-, phCH2-, or ΦCH2.
(b) Naming of disubstituted benzenes

If two substituents on the ring there positional
isomers are possible. Their relative positions are
indicated by prefixes Ortho (o-), Meta (m-) and
Para (p-) or by numbers. The three isomers of
dichlorobenzene are named as
o-Dibromebenzene (1,2-), m-Dibromebenzene
(1,3-), p-Dibromebenzene (1,4-)
When a common neme is used the substituent which
dresponsible for the name (CH3 in toluene, OH in phenol)
is considerd on carbon 1.
o-Chlorotoluene (2-Chlorotoluene), m-Chlorotoluene (3-
Chlorotoluene), p--Chlorotoluene (4-Chlorotoluene)
Naming of polysubstituted benzenes
When three or more substituents are placed on the
benzene ring, numbers must be used to designate their
positions. One of the substituent is put on the top of
hexagon and numbered 1. The naming of the
remaining positions is done clockwise or

anticlockwise, whichever gives lowest possible
group of numbers to the other substituents.
(d) Fused Polycyclic Arenes:
There are numerous polycyclic aromatic
hydrocarbons having one or more benzene rings
fused together in ortho positions.
e.g. Naphthalene, Anthrecene, Phenanthrene
Structure of Benzene
The structure of benzene has been derived as follows:
Molecular Formula Elemental analysis and molecular
weight determination indicated that benzene has
molecular formula C6H6. This was due to highly
unsaturated compound compare it with n - Hexane
C6H14.
Straight chain structure not possible It could be
constructed as straight chain or compound having C=C
or C≡C bonds. But benzene did not behave like
Structure of Benzene KMnO
4 
alkenes or alkynes. It did not decolourise bromine in

CCl4 or aqueous KMnO4. It did not add water in
presence of acids.
Benzene  
Br2 /CCl4
 No Reaction
Benzene   No Reaction
KMnO 4

/H 
Benzene  HO
2
  No Reaction
Evidence of Cyclic Structure Benzene reacted with
bromine in presence of FeBr3 as catalyst to form
monobromobenzene.
C6 H 6  Br2 FeBr
3  C6 H 5 Br  HBr
The fact that only one monobromo and no isomeric product
obtained indicated that all six hydogen atoms in benzene
were identical. This could be possible only if benzene had a
cyclic structure of six carbons and to each carbon was
attached one hydrogen.
C6H6 3H2 Ni 
,pressure
Addition of hydogen Benzene added three moles of

hydrogen in presence of Ni as catalyst to form cyclohexane.
C6H6 3H2  Ni, pressure
This confirmed the cyclic structure of benzene

and showed the presence of three C=C.
Kekule Structure for Benzene: Kekule suggested that benzene
consisted of a cyclic planar structure of six carbons with
alternate single and double bonds. To each carbon was
attached one hydrogen.
This was sample of 1,3,5-cyclohexatriene.
Objections (Two) If Kekule structure was correct, there should
exist two ortho isomers of dibromobenzene.
In other isomer the bromines should be on carbon connected by
a single bond.
In fact only one ortho dibromobenzene could be prepared.
Resonance Description of Benzene. The phenomenon in
which two or more structures can be written for a
substance which involve identical positions of atoms is
called Resonance. The actual structure of the molecule is
said to be Resonance hybrid of various possible alternative
structures. The alternative structures are referred to as
Resonance Structures or Contributing forms. A double
headed arrow (↔) between the resonance structures is
used to represent the resonance hybrid. Benzene structure
(1) and (2) represent resonance structures.
All single bonds in structure (1) are double bonds in
structure (2), they are considered a hybrid of them.
Spectroscopic measurements show that benzene is
planar and that all of its carbon-carbon bonds are of
equal length 1.40 oA. This value is in between the
carbon - carbon single bond length (1.54 oA) and carbon
- carbon double bond length (1.34 oA). Resonance
hybrid is more stable than any of its contributing
structures. For benzene, the stability due to resonance
is so great that pi bonds of the molecule
will normally resist breaking. This is due to lack of reactivity
of benzene towards addition.
Molecular Structur of Benzene:
All six carbon atoms in benzene are sp2 hybridized leaving one
p orbital unhybridised on each carbon atom. The sp2 hybrid
orbitals overlap with each other and with s orbitals of the six
hydrogen atoms forming C-C and C-H σ bonds. Since the σ
bonds result from the overlap of planar sp2 orbitals, all carbon
and hydrogen atoms in benzene lie in the same plane. All σ-
bonds in benzene lie one plane and all bond angles are 120o
lying at the corners of planar regular hexagon.
Pi Molecular Orbital Structures of Benzene
Benzene pocesses an unhybridized p orbital containing
one electron. These p-orbitals are perpendicular to the
plane of σ bonds. This overlap produces a pi molecular
orbital containing six electrons. One half of this pi
molecular orbital lies above and the other half lies below
the plane of σ bonds.
The six electrons of the p orbitals cover all the six carbon
atoms and are said to be delocalized. As a result of
delocalization is formed stronger pi bond and a more
stable molecule.
Thermodynamical data has actually shown that

stabilization energy of the delocalized pi molecular
orbital in benzene is 36 kcal/mol.The benzene gives
substitution reactions in which the stability of
benzene ring is retained.
There are three ways in which benzene can be
represented.
A common short hand representation of benzene is
simply hexagon with a circle inside. The circle
presents the pi molecular orbital.

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Nomenclature and Structure of

(b) Naming of disubstituted benzenes

remaining positions is done clockwise or

alkenes or alkynes. It did not decolourise bromine in

Addition of hydogen Benzene added three moles of

C6H6 3H2  Ni, pressure

This confirmed the cyclic structure of benzene

Thermodynamical data has actually shown that

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