I. A.

Aromaticity
Huckels rule:
An organic compound is aromatic, if
1. it is cyclic
2. it is conjugated
3. it is planar
4. it has 4n + 2 electrons, where n=0 or any positive integer (the pi electrons in an aromatic molecule will always
be found in the series 2, 6, 10, 14, 18 and so on.

I. B. Double Bond Equivalent (DBE) or Degree of Unsaturation or Index of Hydrogen

Deficiency
DBE the no. of molecules of H2 added to a molecule to convert all pi bonds to single bonds, and
all rings to acyclic
structure
1 DBE = 1 double bond, or 1 ring
2 DBE = 2 rings, 2 double bonds, 1 triple bond, or 1 double bond and 1 ring
To compute for DBE:

DBE = C - (H/2) + (N/2) + 1

where: C- no. of carbon atoms
H-no. of hydrogen atoms
N-no. of nitrogen atoms

Sample Problem
Compound A has the formula C6H10. It absorbs 2 equivalents of H2 on catalytic reduction
over a palladium catalyst to give an alkane product. It produced a dicarboxylic acid upon the
addition of acidic KMnO4. Predict the structure of A.
Ans: Cyclohexene

II. A. Electrophilic Aromatic Substitution of Benzene

Name of

Reagents

Electrophile. E+

Product

Reaction
Halogenation
(Chlorination /
Bromination)

Bromination:
Br2,
FeBr3
Chlorination:
Cl2,
FeCl3

Bromination:
Br+
Chlorination:
Cl+

HX

(X= Br or Cl)
bromobenzene or
chlorobenzene
Nitration

HNO3, H2SO4

NO2+
(nitronium ion)

Sulfonation

SO3, H2SO4

SO3H+
(sulfonium ion)

Friedel-Crafts
Alkylation

RCl, AlCl3

R+
carbocation
(can undergo
rearrangeme
nt to form a
more stable
carbocation)
RCO+
acylium ion

nitrobenzene

benzenesulfonic acid

Friedel Krafts
Acylation

RCOCl (acid
chloride),
AlCl3

+ HCl
alkylbenzene (arene)

+
HCl
aryl ketone

II. B. Mechanism of Electrophilic Aromatic Substitution

Resonance of carbocation:

III. Oxidation of Aromatic Side Chains

Benzene unaffected by strong oxidizing agents like KMnO 4 or H2CrO4.
Alkyl groups with at least 1 hydrogen attached to the benzene ring are readily oxidized to
a carboxyl group.
The benzylic carbon (carbon attached to the benzene ring) is oxidized to carboxyl group.

KMnO4
or H2CrO4

No reaction

No reaction

IV. Substituent Effects in Electrophilic Aromatic Substitution

Substituents affect the reactivity of the aromatic ring
Substituents affect the orientation of the reaction
3 types of substituents based on the site of reaction and reactivity
1. Ortho- and para-directing activators
-benzene with these activators react faster than benzene
-the substituents direct the E+ to ortho or para position
2. Ortho- and para-directing deactivators
-substituents: halogens
-benzene with halogens react faster than benzene
-the halogens direct the E+ to ortho or para position
3. meta-directing deactivators
-benzene with these deactivators react slower than benzene
-the substituents direct the E+ to meta position

Practice Exercises:
Electrophilic Aromatic Substitution effects (Brown and Poon, 5 th
edition)
9.26
Draw the structural formula for the major product formed on treating each compound
with Cl2/AlCl3:

(a)

Cl2

AlCl3

(b)

NO2

Cl2

Cl
Cl

Cl
NO2

AlCl3

(c)

Cl

Cl2
AlCl3

Cl

Cl
+

Cl

Cl

C(CH3)3

(d)

C(CH3)3

Cl2

AlCl3

Cl

Cl
sterically more f avorable

(e)

C(CH 3)3

O
Cl

Cl 2
AlCl 3

Cl2

AlCl3

(g)

Cl

Cl
O

OCH3

Cl2

Cl

OCH 3

AlCl3

(h)

O
Cl 2

Cl

AlCl 3

Cl
O

Cl2

AlCl3

NO2

NO2

Cl

NO2

Cl
Cl

CH3

Cl 2
AlCl 3

Cl

CH3

The chloro and methyl groups are both o/p directors, but the methyl
group is more activating than the chloro group.
9.28 Arrange the compounds in each set in order of decreasing reactivity (fastest to slowest)
toward electrophilic aromatic substitution.

Compound (A) has a strong activator. (B) has a moderate activator. (C) has a weak activator.

Fastest

Slowest

Compound (A) has a weak deactivator. Compound (B) has a moderate deactivator.

Fastest

Slowest

Compound (C) has a strong activator. Compound (A) has a weak activator. Compound (B) has a
moderate decativtor.

Fastest

Slowest

Compound (C) has a strong activator. Compound (B) has a weak activator. Compound (A) has a
weak decativtor.

Chemical Transformations (Brown and Poon, 5th edition)

9.48 Test your cumulative knowledge of the reactions learned thus far by completing the
following chemical transformations. Note: some will require more than one step.

(a)

OH

Cl

SOCl 2

CH3O

RCl

HNO3

AlCl 3

H 2SO4

H2

NO 2

(b)

benzene

NH2

Ni

CH3O

H2CrO4

AlCl 3

CH3O

COOH

RCl cannot be a tertiary alkyl halide. If a tertiary alkyl halide is used, the
product formed would not be oxidized by H 2CrO4.
(c)

HCl
NH 2

(d)

NH3 Cl

Cl

2Cl 2
AlCl 3

(e)

Cl 2

OH

Cl

NO2
NO2

HNO3

AlCl3

H2SO4

Cl

Br 2
FeCl3

Br

(g)

H2SO4

Cl

Cl

HNO3

Br

Cl

OH

1. K2CO3
2. propyl
chloride

Cl CH Cl
3

Cl

AlCl3

Cl

Cl 2
AlCl 3
Cl

(h)

HNO 3

NO2

H 2SO 4

H2
Ni

NH3 Br

HBr

CH 2Cl 2
AlCl 3

CH2Cl

benzene
AlCl3

NH 2

RCl

H2CrO4

AlCl3
O

HO

RCl cannot be a
tertiary alkyl halide

OH

Cl

(k)
Cl

(CH3)3COK

HCl

(CH3)3COH

NH 2

Br 2

Br

FeCl3

NH2

OH
Br

NH

(m)

R
RCl

HNO3

Cl 2

AlCl3

H2SO4

AlCl 3

NO2

COOH
Cl

NO2

(n)

OH

Cl

H2CrO4

RCl cannot be a
tertiary alkyl halide
NO2

ONa
NaOH

Cl

O
O