Benzene

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 Definition
 Molecular structure
 Orbital picture
 Aromaticity
 Nomenclature
 Physical properties of benzene
 Preparation of benzene and its homologues
 Reactions of benzene
 Electrophilic Aromatic Substitution reactions
 Mechanism
 Reactivity
 orientation

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 Definition
 Aromatic compounds
Compounds that resemble benzene in
chemical behavior are known as aromatic
compounds.
 They possess a pleasant aroma and so
named aromatic compounds.
 Arenes: aromatic hydrocarbons

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Molecular structure of benzene

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 DERIVATION OF STRUCTURE
Molecular formula: elemental analysis, molecular weight
determination, C6H6.
This indicated benzene was a highly unsaturated compound.
(n-Hexane C6H14)

Straight chain structure not possible: not behave like alkenes or

alkynes.
(no decolorization with bromine in CCl4 or cold aq. KMnO4., no add
water in the presence of acids.)

Evidence of cyclic structure:

a)sub. Of benzene: benzene + Br2+ FeBr3= mono bromobenzene
1 monobromo product and no isomeric products.
so all 6 H atoms are identical.
This could be possible if it had a cyclic structure of 6 Cs and
to each C 1 H was attached.
b)Addition of hydrogen: benzene + 3H2 = cyclohexane
Cyclic structure and presence of 3 C=C.
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Kekule’s structure for benzene:
Benzene is a flat molecule with 6 carbons bonded in a planar ring.
Alternate double and single bond.
Each carbon is covalently joined to two other carbons and one
hydrogen. A total of three covalent bonds.
Benzene was 1,3,5- cyclohexatriene.
On bromination, 2 ortho isomer of dibromobenzene should exist.
But here, only 1 isomer exists. So benzene is a mixture of 2 forms.
In the Kekulé description, the bond between any two carbon
atoms is sometimes a single bond and sometimes a double bond.
These structures are known as Kekulé structures.

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 Resonance of benzene
Resonance: The phenomenon in which 2 or more structures can
be written for a substance which involve identical positions of
atom is called resonance.
Spectroscopic measurements show
 Benzene is a planar molecule
 C-C bonds are of equal length, 1.40 A. (C-C 1.54A, C=C 1.34A)
Resonance hybrid is more stable than any of its resonatic
structures.

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Orbital structure

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 All six C Atoms are sp2 Hybridized. The sp2 hybrid orbitals
overlap with each other and with s orbitals of the six H
atoms forming C-C and C-H sigma bonds.
 All Bond angles are 1200
 C-C bond length 1.40 A, all same.
 C-H bond length 1.08 A
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 Formation of p molecular orbital in benzene

(a) The unhybridized p orbital of C atom is perpendicular to the

plane of benzene ring. There are 6 unhybridized p orbitals
containing 6 electrons which produces a p molecular orbital.
(b) 2 clouds of electrones, 1 lying above and other lying below
the plane of benzene ring.
(c) This delocalization of p electrons makes benzene more
stable.
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 Aromaticity
 “A property of the sp2 hybridized planar rings in which p
orbitals allow cyclic delocalization of p electrons.”
 Benzene is a cyclic compound which has a planar
structure with a delocalized cloud of p electrons above and
below the plane of the ring.

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 Criteria for Aromaticity
There must be an uninterrupted ring of p orbital-bearing
atoms leading to a delocalized p cloud.

1. The molecule must be cyclic and planar.

2. The molecule must be planar.

3. The molecule must be completely conjugated

4. Huckel rule

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 [1] A molecule must be cyclic.

To be aromatic, each p orbital must overlap with

p orbitals on adjacent atoms.
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 [2] A molecule must be planar.

All adjacent p orbitals must be aligned so that the p

electron density can be delocalized.

Since cyclooctatetraene is non-planar, it is not aromatic,

and it undergoes addition reactions just like those of other
alkenes.

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 [3] A molecule must be completely conjugated.

Aromatic compounds must have a p orbital on every atom and

each must overlap with adjacent p orbitals.

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 [4] A molecule must satisfy Hückel’s rule, which
requires a particular number of p electrons.

Huckel rule

Benzene is aromatic and especially stable because it

contains 6 p electrons.

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 Cyclobutadiene is antiaromatic and especially unstable
because it contains 4 p electrons.

As the number of fused rings increases, the number of

resonance structures increases.
Ex. Naphthalene is a hybrid of three resonance structures
whereas benzene is a hybrid of two.

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Hückel’s Rule
Note that Hückel’s rule refers to the number of p electrons, not
the number of atoms in a particular ring.
No. of p electrons that
satisfy the rule.

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 With regard to aromaticity, a compound can be
classified in one of three ways:

1. Aromatic: A cyclic, planar, completely

conjugated compound with 4n + 2 p electrons.
2. Antiaromatic: A cyclic, planar, completely
conjugated compound with 4n p electrons.
3. Nonaromatic: A compound that lacks one (or
more) of the following requirements for
aromaticity: being cyclic, planar and completely
conjugated.

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Note the relationship between each compound type and a similar
open-chained molecule having the same number of p electrons.

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 Annulenes
A completely conjugated, monocyclic
hydrocarbon is called an annulene
(not necessarily aromatic).
To name an annulene, indicate the
number of atoms in the ring in
brackets and add the word annulene.

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 nonaromatic
 It is cyclic but not plan
ar(tub shaped)
 8 p electrons
 4n+2=8, 4n=6, n=1.5
(not integer)

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 Aromaticity
 The criteria for aromaticity also can be applied
to polycyclic hydrocarbons
 Naphthalene (n=2, 5 pairs of p electrons),
phenanthrene (n=3, 7 pairs of p electrons), and
chrysene (n=4, 9 pairs of p electrons) all are
aromatic.

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 Heterocyclic Compounds
• Heterocycles containing oxygen, nitrogen or
sulfur, can also be aromatic.
• With heteroatoms, one must determine
whether the lone pair is localized on the
heteroatom or part of the delocalized p
system.

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 Pyrrole

5 parallel p orbitals containing 6 ele. Form a

delocalised p molecular orbital.
It is aromatic since it is cyclic, planar, completely
conjugated, and has 4n + 2 p electrons. 27
 Heterocyclic Compounds

 In furan and thiophene there are 2 pairs of

unshared electrons - one is an sp2 hybrid orbital
and one pair is in a p orbital, like pyrrole (3 pairs
of p electrons, aromatic)

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6 parallel p orbitals containing 6 ele. Form a delocalized
p molecular orbital.
Unused sp2 orbital of N containing 2 nonbonding ele.
Remains as such.
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 Heterocyclic Compounds

 Quinoline, indole, imidazole,

purine, and pyrimidine also are
aromatic heterocyclic compounds
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Both negatively and positively charged ions can be
aromatic if they possess all the necessary elements.

One can draw five equivalent resonance structures for the

cyclopentadienyl anion.
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• Thus, although five resonance structures can also be
drawn for the cyclopentadienyl cation and radical, only
the cyclopentadienyl anion has 6 p electrons, a
number that satisfies Hückel’s rule.

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 Nomenclature of Benzene Derivatives
• Alkyl benzene: To name a benzene ring with one
substituent, name the substituent and add the word
benzene.

• Common names used for monosubstituted benzenes:

Toluene, Phenol, Aniline

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 • There are three different ways that two groups can be
attached to a benzene ring, so the prefixes: ortho, meta,
or para are used to designate the relative position of the
two substituents.

ortho-dibromobenzene meta-dibromobenzene para-dibromobenzene

or or or
o-dibromobenzene m-dibromobenzene p-dibromobenzene
or 1,2-dibromobenzene or 1,3-dibromobenzene or 1,4-dibromobenzene
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• If the two groups on the benzene ring are different,
alphabetize the names of the substituents preceding
the word benzene.
• If one substituent is part of a common root, name the
molecule as a derivative of that monosubstituted
benzene.

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For three or more substituents on a benzene
ring:
1. Number to give the lowest possible numbers
around the ring.
2. Alphabetize the substituent names.
3. When substituents are part of common roots,
name the molecule as a derivative of that
monosubstituted benzene. The substituent
that comprises the common root is located at
C1.
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• Other common monosubstituted benzenes:
benzaldehyde, benzoic acid, acetophenone & styrene
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 • A benzene substituent is called a phenyl group, and
it can be abbreviated in a structure as “Ph-”.

• Therefore, benzene can be represented as PhH, and

phenol would be PhOH.

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 • The benzyl group, another common substituent
that contains a benzene ring, differs from a
phenyl group.

• Substituents derived from other substituted aromatic rings

are collectively known as aryl groups.

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 Physical properties
Colourless liquid

Solubility
 Insol. In water
 Miscible with alcohol, ether and chloroform
 Good solvent for many inorganic and organic substances like fat, resin,
sulphur, iodine
 With polar grp: moderately sol. In water ex. Benzoic acid
 More than 1 OH grp: sol. In water ex. Resorcinol
Density
 Less dense than water
 Halogenated benzenes are denser than water
M.p.
 High m.p. than alkane as they are more symmetrical
 Para has high m.p. than ortho and meta
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 Physical properties
Vapors: highly toxic which on inhalation produce loss of
consciousness.
It burns with a luminous sooty flame. Alkanes and alkenes: burn with a
bluish flame
B.p. 80.1
 ortho has high b.p. than meta (low dipole moment) and para
(symmetrical) as ortho has high dipole moment.

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