BENZENE AND AROMATICITY

Prof. D. K. Kadam

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 Learning Outcomes
Upon completion of this unit the student shall be able to understand
1. the structure of benzene.
2. Hukel’s Rule for Aromaticity
3. resonance in benzene
4. Electrophilic Aromatic Substitution Reactions like Halogenation,
Nitration, Sulphonation, Friedel Crafts Alkylation, Friedel Crafts
Acylation,
5. Orientation and reactivity in mono substituted benzene.
6. Mechanism of nueleophilic aromatic substitution

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 UNIT I 10 Hours
CONTENTS

 Introduction and Structure: Evidences for derivation

 Orbital Picture
 Hukel’s Rule,
 Resonance in benzene and derivatives.
 Aromaticity
 Mechanism of electrophilic aromatic substitution:
 Halogenation,
 Nitration,
 Sulphonation
 Friedel Crafts Alkylation
 Friedel Crafts Acylation,
 Orientation and reactivity in monosubstituted benzene.
 Structure and uses of DDT, Saccharin, BHC and Chloramine
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 Benzene Cyclohexa-1,3,5-triene

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Molar mass 78.11 g·mol
Appearance White solid crystals/ flakes when freezed else low density liquid
Odour Strong odour
Melting point 5.5 °C
Boiling point 80.1 °C
Density 876.50 kg/m³
Hazard potential occupational carcinogen, flammable
Uses As a petrol additive, benzene increases the octane rating and reduces knocking
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 BENZENE
Introduction: Structure

 Benzene is an important organic chemical compound with the chemical formula C6H6.
 Its molecule is composed of 6 carbon atoms joined in a ring, with 1 hydrogen atom
attached to each carbon atom.
 Because its molecules contain only carbon and hydrogen atoms, benzene is classed as a
hydrocarbon.
 Historic benzene formulae (from left to right) by

Claus (1867), Dewar (1867), Ladenburg (1869), Armstrong (1887), Thiele (1899) and Kekulé (1865).
Thiele and Kekulé's structures are used today

Other proposed structures

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Structure of Benzene:
Kekule’s formula or structure I of benzene is most accepted
because the satisfactory answers it offers to various substitution
products as compared with other proposed structures.
Kekule proposed two structures having alternate single and
double bonds in a ring of six carbon atoms, each having one
hydrogen attached.

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Further, since benzene has alternate single and double bonds, two different C-C bond
distances should be there………..[ (C-C ) - 1.53 Å and (C=C) -1.33 Å].
Actual C-C bond length in benzene has been found to be 1.39 Å for all six C-C bonds.
In short it can be said that- “Benzene is a regular hexagon with identical angles 120°C
with molecular formula C6H6.
All six C-C bonds have same length i.e., 1.395 A, which is intermediate of sp2 – sp2 single
bonds 1.46 Å and double bond length 1.33 A “

Therefore, the structures of benzene can be shown as below; Benzene is an average of

the first two structures. The C-C bond is neither a double nor a single bond, but is
something in between

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 Orbital picture of Benzene:
Kekule’s structure of benzene suggests that each carbon atom
should be triagonal and therefore sp2 hybridised. This means that
each C atom has a 2p orbital and because the benzene molecule is
planner and axes of all six 2p orbitals of benzene are parallel,
these 2p orbitals can overlap the bonding π molecular orbitals of
lowest energy as shown below.

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Orbital overlap picture of benzene
(a) Each carbon of benzene has a p orbital.
(b) The overlap of the p-orbitals forms a cloud of electrons above and below
the plane of the benzene ring.
(c) The electrostatic potential map for benzene shows that all the carbon–
carbon bonds have the same electron density

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 Stability of Benzene: Resonance Energy:

Chemical reactivity of any compound is measured in terms of its standard heats

of formation ΔHof .
Benzene is a cyclohexatriene (cyclic)
The ΔHof for a double bond is 28.6 kcal/mol, so it is expected to have 28.6 × 3 =
85.8 kcal/mol (theoretical)
[As cyclohexene has Δ Hf = 28.6 kcal/mol;
cyclohexadiene has ΔHf = 55.4 kcal/mol.]
However, in practical (reality) it is only 49.8 kJ/mol.
85.8-49.8 = 36 less energy
Therefore, benzene is stable by 36 kcal/mol, or it contains 36 kcal/mol, less
energy.
This energy difference of 36 kcal/mol is called empirical resonance energy
(RE) of benzene.
RE is the energy by which benzene is stabilized and it is therefore, an energy
that benzene doesn’t have.
Let us understand more about what is resonance and aromaticity.

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Sometimes, multiple chemical structures in which electrons are shared between just two atoms can be used
to represent a single molecule. In these cases no single such structure is correct, and the molecule exhibits
special stability.
This phenomenon imparts special chemical properties, especially, for certain cyclic systems. The reasons lie
in the following two concepts.

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 ELECTROPHILIC AROMATIC SUBSTITUTION
Electron clouds below and above the aromatic ring shield it from the nucleophilic attack, but it is prone to
electrophilic attack.
Because of the delocalised electrons exposed above and below the plane of the rest of the molecule, benzene
is obviously going to be highly attractive to electrophiles -species which seek the electron rich areas in other
molecules. The electrophile will either be a positive ion, or the slightly positive end of a polar molecule.
Step 1: Formation of C+ ion
First an electrophile, X+ attacks benzene to form an
intermediate C+ ion (Benzonium ion or σ complex), the
rate limiting step.

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Thus the substituents are divided into three groups

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 Activating Groups- o- or p- directors
In the case of alkyl substituents, charge stabilization is greatest when the alkyl group is
bonded to one of the positively charged carbons of the benzenonium intermediate. This
happens only for ortho and para electrophilic attack, so such substituents favor formation
of those products. Interestingly, primary alkyl substituents, especially methyl, provide
greater stabilization of an adjacent charge than do more substituted groups (note the
greater reactivity of toluene compared with tert-butylbenzene).

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 Dectivating Groups- m- directors
Nitro (NO2), sulfonic acid (SO3H) and carbonyl (C=O) substituents have a full or partial positive
charge on the atom bonded to the aromatic ring. Structures in which like-charges are close to
each other are destabilized by charge repulsion, so these substituents inhibit ortho and para
substitution more than meta substitution. Consequently, meta-products predominate when
electrophilic substitution is forced to occur.

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Halogen (X), OR and NR2 substituents all exert a destabilizing inductive effect on an adjacent positive
charge, due to the high electronegativity of the substituent atoms. By itself, this would favour meta-
substitution; however, all these substituent atoms have non-bonding valence electron pairs which
serve to stabilize an adjacent positive charge by pi-bonding, with resulting delocalization of
charge. Consequently, all these substituents direct substitution to ortho and para sites. The balance
between inductive electron withdrawal and p-π conjugation is such that the nitrogen and oxygen
substituents have an overall stabilizing influence on the benzenonium intermediate and increase the
rate of substitution markedly; whereas halogen substituents have an overall destabilizing influence.

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 Orientation and Reactivity Effects of Ring Substituents

Deactivating
Activating Substituents Deactivating Substituents Substituents
ortho & para-Orientation meta-Orientation ortho & para-
Orientation
–O(–) –NH2 –NO2 –CO2H –F
–OH –NR2 –NR3(+) –CO2R –Cl
–OR –NHCOCH3 –PR3(+) –CONH2 –Br
–OC6H5 –R –SR2(+) –CHO –I
–OCOCH3 –C6H5 –SO3H –COR –CH2Cl
–SO2R –CN –CH=CHNO2

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If it is meta

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