UNIT I 10 Hours

Benzene and its derivatives

A. Analytical, synthetic and other evidences in the derivation of

structure of benzene, Orbital picture, resonance in benzene, aromatic
characters, Huckel’s rule

B. Reactions of benzene - nitration, sulphonation, halogenation

reactivity,
• Friedel crafts alkylation- reactivity, limitations,
• Friedel crafts acylation.

C. Substituents, effect of substituents on reactivity and orientation of

Mono substituted benzene compounds towards electrophilic
substitution reaction
 Structure of benzene

• Kekule was the first to suggest a sensible structure for

benzene.
• When aromaticity is considered, the most commonly
encountered structure is benzene.
• The usual structural presentation of the benzene is a six
carbon ring which includes three double bonds.
• Each of the carbons represented by a corner is also bonded
to one other atom.
• In benzene, these atoms are hydrogens.
• The double bonds are separated by single bonds means it
involves conjugated system.
• An alternative system involves use of circle inside of
hexagon to represent the six pi electrons.
 H

H C H
C C

C C
H C H

H
Above and below the plane of the benzene ring there is a
cloud of  electrons. Because of resonance, these  electrons
are more involved in holding together carbon nuclei than are
the  electrons of a carbon-carbon double bond.
 Resonance in benzene:
• There were several other structures proposed for benzene, but a
much more satisfactory approach became possible when it was
understood that covalent bonds consist of pairs of electrons shared
between atoms.
• The difference between the two structures Kekule (1865) envisioned
(called Kekule structures) is only the difference between the locations
of three pairs of electrons.
• This is exactly the type of situation where resonance must be
involved. The hybrid or "average" of the two Kekule structures has
one sigma bond and one-half of a pi bond between each two carbon
atoms.
• Thus each carbon is joined to each of its neighbors by a one-and-half
bond.
• Each bond in the benzene ring has the same number of electrons and
is the same length.
H H

H H H H

means

H H H H

H H
 Benzene
• Aromatic was used to described some fragrant compounds in
early 19th century
• Current: distinguished from aliphatic compounds by electronic
configuration

6
6
7
 OH
NH2 OCH3 COC6H5
CHO

Phenol Aniline Benzaldehyde Benzophenone

Anisole

COCH3 CONH2 CN COCl COOH

Benzoic acid
Benzonitrile Benzoyl chloride
Benzamide
Acetophenone
Benzene (C6H6) is the simplest aromatic hydrocarbon
• Highly unsaturated
• Six-membered ring compound with alternative
single and double bonds between adjacent carbon
atoms
• Chemically unreactive compared to alkenes

In 1865, Kekule proposed

the structure of benzene:
The Stability of Benzene

Kekulé suggested that benzene was...

◼ Six-membered ring compound with

alternative single and double bonds
between adjacent carbon atoms
◼ 6 carbon ring with a hydrogen bonded
to each carbon
◼ It is planar.
◼ One electron from each carbon is free
to participate in a double bond
The Stability of Benzene

According to the Kekulé structure, there should be

two different 1,2-dibromobenzenes:

Only one 1,2-dibromobenzene has been found!!

 The Stability of Benzene

According to the Kekulé structure, benzene should

• undergo addition reactions readily
• it gave substitution reaction products rather than
addition reaction products

• All C-C bonds are identical

 Kekulé structure cannot explain the behaviour of benzene
•Experiments show that the Kekulé structure is not
correct.
•A correct description is given by resonance theory
or by orbital models – valence bond or molecular
orbital.
 Resonance Theory
1.Resonance forms are imaginary
◼ The resonance description of benzene consists of two
equivalent Lewis structures, each with three double
bonds that alternate with three single bonds.
◼ benzene has a single hybrid structure which
combines the characteristics of both resonance
forms.
Resonance forms

Hybrid structure
 Molecular Orbital
*  electron cloud delocalized all over the ring

* the resonance picture this helps to explain lack of reactivity of benzene

* great stability (substitution not addition )

Benzene - Resonance Energy
◼ One way to estimate the resonance
energy of benzene is to compare the
heats of hydrogenation of benzene and
cyclohexene.
◼ Heats of hydrogenation for both
cyclohexene and benzene are negative
(heat is liberated)
 Stability of Benzene

• Consider the heats of hydrogenation of cyclohexene, 1,3-cyclohexadiene

and benzene, all of which give cyclohexane when treated with excess
hydrogen in the presence of a metal catalyst.

16
 Stability of Benzene

• The low heat of hydrogenation of benzene means that benzene is

especially stable—even more so than conjugated polyenes. This
unusual stability is characteristic of aromatic compounds.
• Benzene’s unusual behavior is not limited to hydrogenation.
Benzene does not undergo addition reactions typical of other
highly unsaturated compounds, including conjugated dienes.
• Benzene does not react with Br2 to yield an addition product.
Instead, in the presence of a Lewis acid, bromine substitutes for a
hydrogen atom, yielding a product that retains the benzene ring.

17
The Stability of Benzene
• Benzene is more stable than Kekulé structure
• The energy difference for the stabilization of benzene
is called resonance energy of benzene
The Stability of Benzene

The Resonance Explanation of the Structure of Benzene

From X-ray crystallography,

In benzene, the actual bond length (1.39 Å) is intermediate between the
carbon—carbon single bond (1.53 Å) and the carbon—carbon double bond
(1.34 Å).
The Stability of Benzene

All carbon atoms in benzene are sp2-hybridized

The side-way overlap of unhybridized 2p
orbitals on both sides gives a delocalized 
electron cloud above and below the plane of the
ring
The Stability of Benzene

The delocalization of  electrons gives benzene extra stability and determines

the chemical properties of benzene
The Stability of Benzene
Structural formula of benzene:

The circle represents the six electrons that are delocalized about the six
carbon atoms of the benzene ring

Molecules for which you can write resonance structures

have an greater stability due to the electron
delocalization.
Aromaticity: cyclic conjugated organic compounds such as benzene, exhibit special
stability .
 Conditions for aromaticity:

1. Compound should be cyclic and planar

2. It should contain sp2 hybridized carbon
3. It should show continuous delocalization of
pi electrons
4. It should follow Huckel rule
5. It should have conjugated system of p-
orbitals
 Huckel rule of aromaticity / Huckel
magic number
• It state that “any cyclic compound containing
4n+2 delocalized pi electrons are aromatic in
nature in which n=0, 1, 2, 3, 4, 5, 6 i.e. whole
integer”.
The Criteria for Aromaticity—Hückel’s Rule
Four structural criteria must be satisfied for a compound to be aromatic.

[1] A molecule must be cyclic.

To be aromatic, each p orbital must overlap with p orbitals on adjacent atoms.

25
The Criteria for Aromaticity—Hückel’s Rule
[2] A molecule must be planar.

All adjacent p orbitals must be aligned so that the  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.

26
The Criteria for Aromaticity—Hückel’s Rule

[3] A molecule must be completely conjugated.

Aromatic compounds must have a p orbital on every atom.

27
The Criteria for Aromaticity—Hückel’s Rule

[4] A molecule must satisfy Hückel’s rule, and contain

a particular number of  electrons.

Hückel's rule:

Benzene is aromatic and especially stable because it contains 6  electrons.

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

28
The Criteria for Aromaticity—Hückel’s Rule
Note that Hückel’s rule refers to the number of  electrons, not the number of atoms in a
particular ring.

29
Benzene
Benzene Anion
Cyclobutadiene
Cyclopentadiene
cation
Pyrrole
Pyrrole Conjugate Acid
Pyridine
Thiophene
Electrophilic Aromatic
Substitution
The characteristic reactions of benzene involve substitution

Above and below the plane of the benzene ring there is a

cloud of  electrons. Because of resonance, these  electrons
are more involved in holding together carbon nuclei than are
the  electrons of a carbon-carbon double bond.
Still, in comparison with  electrons, these 
electrons are loosely held and are available to a
reagent that is seeking electrons.

In its typical reactions the benzene ring serves as a

source of electrons, that is, as a base.

The compounds with which it reacts are deficient in

elections, that is, are electrophilic reagents or acids.

So the typical reactions of the benzene ring are

electrophilic substitution reactions.
Electrophilic aromatic substitution

Electrophilic aromatic substitution reactions

These reactions are of the general type
shown below;

E
+ E+
+ H+

ArH + E+ Ar-E + H+

E+-------Electrophilic reagent
Electrophile: “electron-loving” reagent

The term electrophile literally means ‘electron-loving’, and is an

electron deficient species that can accept an electron pair.

Electrophilic substitution reactions are those where an

electrophile displaces another group, usually a hydrogen.
Electrophilic substitution occurs in aromatic compounds.

Electrophilic aromatic substitution is a reaction where a hydrogen

atom in an aromatic system, e.g. benzene, is replaced by an
electrophile.

Some of the important electrophilic substitution reactions are

Friedel–Crafts alkylation and acylation, nitration, halogenation and
sulphonation of benzene.
• Benzene undergoes following types of
electrophilic substitution reactions (ESR).
• Halogenation- i) Chlorination. ii) Bromination
• Sulfonation
• Nitration
• Friedel Craft alkylation
• Friedel Craft acylation
Electrophilic aromatic substitution
reactions.
X2, FeX3 X

(X = Cl, Br) + HX Halogenation

¯

HNO3
NO 2
H 2SO4 + H 2O Nitration

SO 2
S O 3H
H2SO4 Sulfonation

RCl, AlCl3 R Friedel-Crafts Alkylation

(R can rearrange) + HCl ¸ -
O
O

RC-Cl, AlCl3 R

Friedel-Crafts Acylation
-
 Nitration:
• It is an EAS(ESR) in which nitro group get
substituted in benzene ring in presence of conc.
sulfuric acid to form nitrobenzene.
• Nitration in the benzene ring is an electrophilic
substitution reaction, and the electrophile
involved here is the nitronium ion, NO2+.
Sulphuric acid being a stronger acid than nitric
acid facilitates easy generation of NO2+ by
protonating the latter.
• H2SO4 + HNO3 = NO2+ + HSO4- + H2O
 NO2

Conc H2SO4
+ HNO3 H2O
 Mechanism:
• Step-1: Generation of nitronium ion as an
electrophile.
HNO3 + 2 H2SO4 NO2 + H3O + 2 HSO4-

• Step-2: Attack of nitronium ion on pi electrons

of benzene ring to form arenium ion.

NO2
NO2

Arenium ion
• Step-3: Attack of bisulfite ion on arenium ion
to form nitrobenzene by loss of proton.

H
NO2
NO2
HSO4- H2SO4
 Concentrated sulfuric acid increases
the rate of the reaction by increasing
the concentration of the electrophile-
the nitronium ion (NO2+)
O
+
H O NO2 + HSO4-
Step 1 H O N + HOSO3H

Lewis base O H
Lewis acid
ÖÊ×Ó»¯ÏõËá

+ +
Step 2 H O NO2 + H2SO4 NO2 + H3O+ + HSO4-
Nitronium ion
H Ïõ»ùÕýÀë×Ó
 Sulfonation
• It is an EAS(ESR) in which benzene reacts with
fuming sulfuric acid i.e. sulfuric acid rich in
sulfur trioxide to form benzene sulfonic acid.
• It is a reversible reaction.
O

O
S OH
concd H2SO4
+ S
25 oC O
O O
Sulfur trioxide
Benzenesulfonic acid
±½»ÇËá
(56%)
 The mechanism of sulfonation
Step 1 2 H2SO4 SO3 + H3O+ + HSO4-

H
O
Slow SO3-
Step 2 +
S +
O O
Sulfur trioxide
H
SO3-
SO3- HSO4-
Step 3 Fast
+ H2SO4
+

SO3- SO3H
Step 4 + H3O+ fast + H2O

Benzenesulfonic acid
We may remove the sulfonic acid
group by desulfonation

SO3H

+ H2O + H2SO4

Benzenesulfonic acid
 Halogenation:
• It is an EAS in which halogens such as chlorine
or bromine get substituted in benzene ring in
presence of Lewis acid such as anhydrous
aluminium chloride to form halobenzene.
X

AlCl3
+ X2 HX
 Mechanism:
• Step-1: Generation of halonium ion as an
electrophile.

X X AlCl3 X X AlCl3 X AlCl3 X

Complex Halonium
ion

Step-2: Attack of halonium ion on pi electrons of

benzene ring to form arenium ion.
H H
H

X
X

Arenium ion
• Step-3: Attack of AlCl4- on arenium ion to form
halogenated benzene by loss of proton.

H
X
X
AlCl3 X HX AlCl3
 Chlorination:
• It is an ESR in which chlorine get substituted in
benzene ring in presence of Lewis acid such as
anhydrous aluminium chloride to form
chlorobenzene.
Cl

AlCl3
+ Cl2 HCl
 Mechanism:
• Step-1: Generation of chloronium ion as an
electrophile.

Cl Cl AlCl3 Cl Cl AlCl3 Cl AlCl4

Complex Chloronium
ion

• Step-2: Attack of chloronium ion on pi

electrons of benzene ring to form arenium ion.
H

Cl
Cl

Arenium ion
• Step-3: Attack of AlCl4- on arenium ion to form
chlorobenzene by loss of proton.
H
Cl
Cl
AlCl4 HCl AlCl3
 Friedel Craft alkylation:
• It is an ESR in which benzene reacts with halo
alkane in presence of catalyst like Lewis acid
to form alkyl benzene.
CH3

AlCl3
+ CH3X HX

X=Cl / Br / I
 Mechanism:
• Step-1: Generation of methyl carbocation ion
as an electrophile.

H3C Cl AlCl3 H3C Cl AlCl3 CH3 AlCl4

Complex Methyl
carbocation

• Step-2: Attack of methyl carbocation on pi

electrons of benzene ring to form arenium ion.
H

CH3
CH3

Arenium ion
• Step-3: Attack of AlCl4- on arenium ion to form
methyl benzene by loss of proton.

H
CH3
CH3
AlCl4 HCl AlCl3
 Drawbacks/Limitations
of Friedel Craft alkylation:
• Formation of poly alkylated product: Alkyl
group is electron donating group, hence it
increases electron density in benzene ring and
activates ring for further ESR which leads to
formation of poly alkylated product.
CH3 CH3 CH3
CH3

AlCl3
+ CH3Cl

CH3
 Drawbacks/Limitations
of Friedel Craft alkylation:
• Formation of un-expected product:
• Friedel Craft alkylation proceeds through
formation of carbocation which may
rearranges itself to more stable carbocation
which leads to formation of non-expected
product. CH2CH2CH3

Expected product
(Propyl benzene)
AlCl3
+ CH3CH2CH2Cl CH3
1-chloro propane
CH
CH3

Unexpected product
(Isopropyl benzene)
Limitations of Friedel-Crafts reactions
Form the more stable carbocation.
AlCl3
CH3CH2CH2CH2 Br CH3CH2CH2CH2 Br----AlCl3

Hydride shift +
+
CH3CH2CHCH2 CH3CH2CHCH3
[H-]Ç⸺Àë×ÓÖØÅÅ
1o C+ 2o C+
H

(-AlCl3) (-AlCl3)
(-HBr) (-HBr)

CH3CH2CHCH3
CH3CH2CH2CH2

Butylbenzene
(32-36% of mixture)

sec-Butylbenzene
( 64-68% of mixture)
2. Friedel-Crafts reactions do not occur when
powerful electron-withdrawing groups are
present on the aromatic ring or when the ring
bears an –NH2, -NHR, or –NR2 group
NO2 + N(CH3)2 COOH

COR CF3
No Friedel-Crats reactions
SO3H

Electron-withdrawing groups make the ring

less reactive
The amino groups, -NH2, -NHR, and –NR2,
are changed into powerful electron-
withdrawing groups by the Lewis acids
used to catalyze Friedel-Crafts reactions

-
+ NH2AlCl3
NH2 (-NHR, -NR2)

+ AlCl3 Does not undergo a

Friedel-Crafts reaction

Lewis base Lewis acid salt

Aryl and vinylic halides can not be used
as the halide component because they
do not form carbocations readily.
Cl

AlCl3
no Friedel-Crafts reaction

C C Cl
C C

Cl
+
AlCl3
+ AlCl4-
 Friedel Craft acylation:
• It is an ESR in which benzene reacts with acid
chloride in presence of catalyst like Lewis acid
to form acylketone.

COCH3

AlCl3
+ CH3COCl HCl
Acetyl chloride
Acetophenone
 Mechanism:
• Step-1: Generation of methyl acylium ion as
an electrophile.
O O

H3C C Cl AlCl3 H3C C AlCl4

Acylium ion

• Step-2: Attack of acylium ion on pi electrons

of benzene ring to form arenium ion.
H
O

COCH3
H3C C

Arenium ion
• Step-3: Attack of AlCl4- on arenium ion to form
acetophenone by loss of proton.

H
COCH3

COCH3
HCl AlCl3
AlCl4
• Friedel craft acylation can also be carried out
using acetic anhydride.
COCH3

AlCl3
+ (CH3CO)2O CH3COOH

• Synthetic application of Friedel craft acylation:

COCH2CH3 CH2CH2CH3

AlCl3 Zn-Hg/HCl
+ CH3CH2COCl
Clemmensen
Propanoyl Reduction
chloride
Propanoyl benzene Propyl benzene
 Orientation in Monosubstituted
benzene
• Orientation:
– Certain substituents direct preferentially to ortho
& para positions; others to meta positions.
– Substituents are classified as either ortho-para
directing or meta directing toward further
substitution.
• Rate
– Certain substituents cause the rate of a second
substitution to be greater than that for benzene
itself; others cause the rate to be lower.
– Substituents are classified as activating or
deactivating toward further substitution.
 Substituent effects
• All activators also direct incoming electrophiles to
the ortho- and the para-positions.

• Most deactivators direct incoming electrophiles to

the meta position. The exceptions are the halogens,
which are weakly deactivating yet ortho-para
directing.
 Some important points
• Electron donating groups show +R & +I effect and are ring
activators and ortho/para (o/p directors). Ortho directing group
means that group directs an incoming electrophile to ortho
position of benzene ring while para directing group means that
group directs an incoming electrophile to para position of
benzene ring.
• Electron withdrawing groups show -R & -I effect and are ring
deactivators and meta (m) directors. Meta directing group
means that group directs an incoming electrophile to meta
position of benzene ring.
• But above statements are exception for halogens like –Cl, -Br, -I,
-F which are electron donating groups showing +R & -I effect but
weak ring deactivators& o/p directors.
 Strongly

:
:

:
activating N H2 N HR N R2 OH OR
Ortho-para Directing

:
:
O O O O
Moderately

:
:

:
activating N HCR N HCAr OCR OCAr

:
Weakly
activating R

Weakly
:

:
:
deactivating F: Cl : Br : I:
:

:
O O O O
Meta Directing

CH CR COH COR
Moderately
deactivating O
CNH 2 SO 3 H C N
Strongly +
deactivating N O2 N H3 CF3 CCl3
 Activating-Deactivating
• Any resonance effect, such as that of -NH2, -
OH, and -OR, that delocalizes the positive
charge on the cation intermediate lowers the
activation energy for its formation, and has an
activating effect toward further EAS.
• Any resonance or inductive effect, such as that
of -NO2, -CN, -C=O, and -SO3H, that decreases
electron density on the ring deactivates the
ring toward further EAS.
 Activating-Deactivating
• Any inductive effect, such as that of -CH3 or
other alkyl group, that releases electron
density toward the ring activates the ring
toward further EAS.
• Any inductive effect, such as that of halogen,
-NR3+, -CCl3, or -CF3, that decreases electron
density on the ring deactivates the ring
toward further EAS.
 Activating-Deactivating
– For the halogens, the inductive and resonance
effects run counter to each other, but the former
is somewhat stronger.
– The net effect is that halogens are deactivating
but ortho-para directing.

H + H
: :
: :

+
:Cl + E :Cl + :Cl
E

:
E
Summary Table: Effect of Substituents in
Aromatic Substitution
Why do substituent groups on a benzene ring affect the
reactivity and orientation in the way they do?

→ electronic effects, “pushing” or “pulling” electrons by

the substituent.

Electrons can be donated (“pushed”) or withdrawn

(“pulled”) by atoms or groups of atoms via:
Induction – due to differences in electronegativities
Resonance – delocalization via resonance
H
N
H

R
N unshared pair of electrons on the nitrogen
resonance donating groups
H
(weaker inductive withdrawal)

R
N
R

R strong inductive withdrawal

R N (no unshared pair of electrons on the
R nitrogen & no resonance possible
 resonance donation
O (weaker inductive withdrawal)
H

resonance donation
O (weaker inductive withdrawal)
R

O
H3C C N resonance donation
(weaker inductive withdrawal)
H
 resonance donation

inductive donation
H3C sp3 sp2 ring carbon

X— inductive withdrawal
O
C
H

O
C
R
resoance withdrawal and
inductive withdrawal
O
C
HO

O
C
RO
N C resonance and
inductive withdrawal

O resonance and
N inductive withdrawal
O
 Common substituent groups and their effect on reactivity in EAS:

-NH2, -NHR, -NR2

-OH
-OR
-NHCOCH3 electron donating
-C6H5
increasing reactivity

-R
-H
-X
-CHO, -COR
-SO3H
-COOH, -COOR electron withdrawing
-CN
-NR3+
-NO2
Electron donating groups activate the benzene ring to
electrophilic aromatic substitution.

1. electron donating groups increase the electron density

in the ring and make it more reactive with electrophiles.
2. electron donation stabilizes the intermediate
carbocation, lowers the Eact and increases the rate.
H Y

CH3
 Effect of o/p directors:
• Electron releasing groups are o/p-directors as they
show +R & +I effect i.e. these groups directs the
incoming electrophile to ortho and para position of
the benzene ring.
• Consider an example of methyl benzene: In methyl
benzene, attack of electrophile may occur at ortho or
meta or para position but only ortho and para attack
is favored which can be understood from the
following stability concept of carbocation.
Ortho Attack
CH3 CH3 CH3 CH3
E E E

E+ H H H

Meta Attack (I)

(II) (III)
(Extra stability)

CH3 CH3 CH3 CH3

E
E+ E E

H H H
(I) (II) (III)
Para Attack
CH3 CH3 CH3 CH3

E+

E H E H E H

(I) (II) (III)

(Extra stability)
Electron withdrawing groups deactivate the benzene ring to
electrophilic aromatic substitution.

1. electron withdrawing groups decrease the electron density

in the ring and make it less reactive with electrophiles.
2. electron withdrawal destabilizes the intermediate
carbocation, raising the Eact and slowing the rate.
H Y

NO2
 Effect of meta directors
• Electron withdrawing groups are m-directors as
they should show
• -R & -I effect i.e. these groups directs the incoming
electrophile to meta position of the benzene ring.
• Consider an example of nitro benzene: In nitro
benzene, attack of electrophile may occur at ortho
or meta or para position but only meta attack is
favoured which can be understood from the
following stability concept of carbocation.
 NO2 NO2 NO2 NO2
Ortho Attack E E E

E+ H H H

(I) (III)
(Most unstable) (II)

Meta Attack
NO2 NO2 NO2 NO2

E
E+ E E

H H H
(I) (II) (III)
Para Attack

NO2 NO2 NO2 NO2

E+

E H E H E H

(I) (II) (III)

(Most unstable)
 Effect of halogens in ESR
• Halogens are electron donating in nature so they
are o/p-directors. But though they are electron
donating, they are not ring activators instead
they are weak ring deactivators as they show +R
& -I effect.
• Consider an example of halo benzene: In halo
benzene, attack of electrophile may occur at
ortho or meta or para position but only o/p
attack is favoured which can be understood from
the following stability concept of carbocation.
Ortho Attack X X X X X
E E E E

E+ H H H H

(I) (III) (IV)

(-I effect) (II) (+R effect)

Meta Attack
X X X X

E
E+ E E

H H H
(I) (II) (III)
Para Attack

X X X X X

E+

E H E H E H E H
(I) (II) (III) (IV)
(-I effect) (+R effect)
• Halogens are electron releasing in nature due to
+R effect, hence they releases electrons towards
ring and stabilizes the carbocation which favors
attack of electrophile at o/p position.
• At the same time halogens are electron
withdrawing in nature due to –I effect, hence
they withdraws electrons from the ring and
destabilizes the carbocation. So +R effect is
compensated by –I effect. Hence halogens are
o/p directors but ring deactivators.
 Summary of Substituent Effects
• When the substituent is R (alkyl) or Ar (aryl), the resonance hybrid cation
intermediate has three resonance forms. For attack of the electrophile at
the ortho or para positions, one of these is a 3º carbocation, which is
especially stable. This lowers the energy of the intermediate, thus
facilitates (speeds) the substitution reaction at the o- and p- positions.
• When the substituent has a lone pair of electrons, such as the halogens,
oxygen or nitrogen, the resonance hybrid for attack of the electrophile at
the ortho and para positions has four resonance forms. This lowers the
energy of the those intermediates, thus facilitates (speeds) the
substitution reaction at the o- and p- positions.
 Summary of Substituent Effects…
• When the substituent has a multiple bond
conjugated with the ring, and the second
atom from the ring is more electronegative
than the first, the substituent deactivates the
ring and directs incoming electrophiles meta.
It does this by raising the energy of the
carbocation intermediates from ortho and
para attack by an electrophile even more than
it raises the energy of the intermediate
resulting from meta attack.
 Classification of substituents
Ortho-para directors (ÁÚ-¶Ôλ¶¨Î»»ù£© Meta Directors (¼äλ¶¨Î»»ù)

Strongly Activating Strongly Deactivating

-NH2, -NHR, -NR2, -OH, -O- -NO2, -NR3+, -CF3, -CCl3

Moderately Activating Moderately Deactivating

-NHCOCH3, -NHCOR, -OCH3, -OR -CN, -SO3H, -COOH, -COOR,

-CHO, -COR
Weakly Activating

-CH3, -CH2CH3, -R, -C6H5

Weakly Deactivating

-F, -Cl, -Be, -I

 Questions
1. Explain resonance and Kekule’s structure of Benzene
2. Explain Huckel rule of aromaticity with suitable examples.
3. Explain orientation of electrophilic substitution reaction in
monosubstituted benzene.
4. What are electrophilic substitution reactions? Explain mechanism involved
in Friedel Craft alkylation and sulfonation of benzene.

5. Halogens are electron donating but they are ortho/para directors in

aromatic electrophilic substitution reaction. Discuss.

6. What is Huckel rule of aromaticity? Explain aromatic electrophilic

substitution reaction with respect to sulfonation and halogenation.

7. Define activating and deactivating group with examples.

8. Explain in detail Friedel Craft alkylation and acylation reactions.

9. What are substitution reactions? Explain mechanism involved in Friedel

Craft alkylation and acylation reactions.
10. Explain mechanism involved in Friedel Craft alkylation and nitration of
benzene.
11. Methyl group in toluene is ortho para directing. Explain.
11. Electron donating groups are ortho para
directing in electrophilic aromatic
substitution. Discuss.
12. Define ortho and para directors with
examples.
13. Apply Huckel rule to following compounds
OH
OH
15. Explain the directive effect of following groups towards
electrophilic substitution on benzene
i) –OH, ii) –CH3, iii) –COOH, iv) –NO2

16. Discuss sulfonation and nitration reaction giving mechanism

and examples.

17. Explain the directing effect of following groups towards

electrophilic substitution on benzene
i) –NH2, ii) –CH3, iii) –CHO, iv) –NO2.

18. What are aromatic electrophilic substitution reactions?

Write mechanism of halogenation and nitration of benzene.
What is role of conc. sulfuric acid in nitration?