CHE232

Aromatic Compounds
 Aromaticity 2

• Benzene, C6H6 is the parent hydrocarbon of the especially stable

compounds known as aromatic compounds.

Kekule's structures of benzene

H H
H H H H

H H H H
H H

*6 C atoms located at the corners of a regular hexagon, each C bonded to one

H atom. The double and single bonds alternate around the ring, this exchange is
so rapid that benzene cannot undergo same reactions as alkenes and alkynes, eg
permangnate test, bromine test etc.
 3
Aromaticity cont…
Kekule’s structure not entirely correct, there are no single or double bonds
in benzene.

H H
H H H H

H H H H
H H

Benzene is planar, each C atom is at the corner of a regular hexagon. All the C-
C bond lengths are identical, 1.39 Å.

Orbital theory:
Each C atom is sp2 hybridized, two sp2 orbitals overlap with similar orbitals of
adjacent C atoms to form  bonds of the hexagonal ring. The 3rd sp2 orbital
overlap with 1s orbital of H atom. The remaining p orbital (containing one
electron) is perpendicular to the plane of the three sp2 orbitals.
The six p orbitals can overlap laterally to form  orbitals that create a cloud of
electrons above and below the plane of the ring.
 Aromaticity cont.. 4

Two criteria for aromaticity are:

1. The compound must have an uninterrupted cyclic cloud of  electrons above

and below the plane of the molecule; i.e. the molecule must be cyclic, each
atom on the cyclic structure should have a p orbital that can overlap with
other p orbitals on either side of it, therefore, the molecule must be planar.
2. The  cloud must contain an odd number of of pairs of  electrons.

Which of the following compounds are aromatic ?

a. b.

c. d. H2C C C C C CH2
H H H H
 Aromaticity cont.. 5

Two criteria for aromaticity are:

1. The compound must have an uninterrupted cyclic cloud of  electrons above

and below the plane of the molecule; I.e the molecule must be cyclic, each
atom on the cyclic structure should have have a p orbital that can overlap
with other p orbitals on ether side of it, therefore, the molecule must be
planar.
2. The  cloud must contain an odd number of pairs of  electrons.

Which of the following compounds as aromatic ?

N N O S
H
pyridine pyrrole furan thiopene
 6
Nomenclature of Aromatic Compounds

Common names for benzene derivatives accepted by IUPAC

CH3 OH OCH3

benzene toluene phenol anisole

O H O CH3
NH2 C C CO2H

aniline benzaldehyde acetophenone benzoic acid

H3C H CH3 H2C

C CH

cumene styrene
 7
Nomenclature of Aromatic Compounds

Monosubstituted benzenes are named as derivatives of benzene

Br Cl NO2

bromobenzene chlorobenzene nitrobenzene

CH2CH3 CH2CH2CH3

ethylbenzene propylbenzene
 8
Nomenclature cont…

When two susbtituents are present, three isomeric structures are

possible; ortho-, meta-, and para- usually abbreviated as o-, m- and p-

X
O O

m m
p

Cl
Cl Cl
Cl

Cl Cl
ortho-dichlorobenzene meta-dichlorobenzene para-dichlorobenzene
or or or
1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene
 9
Nomenclature cont…

NO2

Cl CH CH2

CH3
meta-nitrotoluene
para-chlorostyrene
or
or
1-methyl-3-nitrobenzene 1-chloro-4-vinylbenzene

OH
NH2
CH3CH2

Cl
m-chlorophenol
ortho-ethylaniline or
or 3-chlorophenol
2-ethylaniline
 10
Nomenclature cont…

CH2

or C6H5 or Ph
or C6H5CH2- or bnz
phenyl
benzyl

CH3CHCH2CH2CH3 Ph Ph

phenylcyclopropane
Ph
2-phenylpentane or
cyclopropylbenzene 1,3,5-triphenylbenzene

OH
CH2Br NO2
CH2

CH2OH

benzylbromide m-nitrobenzyl alcohol o-benzylphenol

or
2-benzylphenol
 11
Reactions of Benzene
The most common reactions of aromatic compounds are electrophilic
aromatic substitutions, i.e. the electrophile susbtitute one of the H atoms
in the ring.

H H
H H H Y
+ Y
+ H
H H an electrophile H H
H H
 12
Reactions of Benzene
General mechanism:

B
H H H
Y Y Y
slow Y fast
+ Y

+
HB
 Halogenation of Benzene 13

Bromination Br
+ Br2 FeBr3

Mechanism:

Br Br + FeBr3 Br Br FeBr3
better electrophile
B
H
Br Br
+ Br Br FeBr3

+
+
HB
FeBr4

Chlorination: Same mechanism as above.

Cl
Cl2 FeCl3
+
 Halogenation of Benzene 14

I
I2 FeI3 too slow to be
+
practical

F
+ F2 FeF3
too vigorous
difficult to
control

Iodination and fluorination of benzene can be achieved by using

diazonium salt synthesis. REFER TO SLIDE 38
 Nitration of Benzene 15
NO2
+ HNO3 H2SO4
+ H2O

Mechanism:

HO NO2 + H OSO3H HO NO2 NO2 + H2O

H nitronium ion

B
H
NO2 NO2
+ NO2
+
HB
 Sulfonation of Benzene 16
SO3H
+ H2SO4 + H2O

Mechanism:

HO SO3H + H OSO3H HO SO3H SO3H + H2O

H sulfonium ion

B
H
SO3H SO3H
+ SO3H
+
HB
 Friedel-Crafts Acylation of Benzene 17
O
O
AlCl3 R + HCl
+
R Cl

Mechanism:
O
+ AlCl3
R C O + AlCl4
R Cl
acylium ion
an acyl chloride

B
H R O

R
+ R C O O

+
HB
Example
O
O
AlCl3 CH3 + HCl
+
H3C Cl
 Friedel-Crafts Alkylation of Benzene 18

R
+ RCl AlCl3 + HCl

Mechanism:
+ AlCl3
R R + AlCl4
Cl
a carbocation
an alkyl halide

B
H
R R
+ R
+
HB

Example
CH2CH3
+ CH3CH2Cl AlCl3 + HCl
 Alkylation of Benzene by an alkene 19

CH3
CH2CH3
+ CH3CH CHCH3 HF

Mechanism:
CH3CH CHCH3 H F CH3CH CH2CH3

CH3

CH2CH3
CH3CH CH2CH3 H
F

CH3

CH2CH3
Chemical changes on some benzene substituents 20

Clemenson
reduction
O Zn-Hg/ HCl
CH2CH3
CH3 H2,Pd/C
+

NH2-NH2
OH-
Wolfkishner

H2
NO2 NH2
Pd/C
OR
1. SnCl2/ HCl

2. NaOH/H2O

SO3H O-Na+ OH

NaOH 200 oC H+
+
 Chemical changes on some benzene substituents 21
CH3 COOH
H2CrO4
heat

CH3
COOH
CH2CH3 H2CrO4
heat

CH2CH2CH3

COOH
CH3 H2CrO4
heat
CH3

The alkyl side chain will be oxidised to the carboxylic

Group (COOH) regardless of the alkyl chain length.
 Chemical changes on some benzene substituents 22

CH3

CH H2CrO4 No reaction
CH3 3
heat

If there are no benzylic H’s then the oxidation reaction does not take place.
This is because the first step of the oxidation reaction involves the removal of
benzylic H.
 Substituents effects on reactivity 23

Substituents not only affect the position of substitution, they also affect
the rate of substitution.

1. When a monosusbstituted benzene undergoes eletrophilic aromatic

substitution reaction there are three possible isomeric products; I. e. o-
, m- and p-. The three products are formed depending on the nature of
the substituents already present on the benzene ring.

2. Some susbtituents make the aromatic ring more reactive than

benzene, while some make the ring less reactive than benzene.
 Substituents effects on reactivity 24

All activating substituents are able to donate electrons to the benzene ring,
thereby stabilizing the carbocation intermediate. Aromatic rings with
electron donating groups are more reactive toward electrophiles than
benzene.

All deactivating groups withdraw electrons from the aromatic ring, thereby
destabilizing the carbocation intermediate, therefore, aromatic rings
with electron withdrawing groups are less reactive toward electrophilic
aromatic substitution reactions than benzene.

Substituents withdraw or donate electrons in two ways:

1. By inductive effect
2. By resonance effect
 Substituents effects on reactivity 25

Inductive Effects:

-are due to the intrinsic electronegativity of atoms and to bond polarity in

functional groups. Atoms/groups withdraw/donate electrons through
the  bonds, e.g. halogens: F, Cl, Br, I, whereas carbonyl, cyano and
nitro groups inductively withdraw electrons because of polarity of the
bonds.
Alkyl groups donate electrons through inductive effect.

Resonance effects:

-Operate by withdrawing or donating electrons through  bonds, by overlap

of a p orbital on the substituent with a p orbital on the aromatic ring.
E.g carbonyl, cyano and nitro groups withdraw electrons by resonance
effects.
 Substituents effects on reactivity 26

O O O O
N N N N
O O O O

NB: Effect felt most strongly at o- and p- positions

Conversely, hydroxyl, methoxyl and amino substituents activate the

aromatic ring by resonance effects. The electrons flow from the
substituent to the aromatic ring, thereby stabilizing the carbocation
intermediate.

R R R R
O O O O

NB: Effect felt most strongly at o- and p- positions

 Orientation: Ortho-Para directors 27
In addition to affecting the reactivity of the aromatic ring, substituents
can influence the position of further electrophilic aromatic susbstitution.
Some groups show strong ortho-para directing effect, for example alkyl,
hydroxyl, methoxyl and amino susbstituents, whereas others show strong
meta-directing effect; e. g.cyano, nitro, carbonyl etc.

O-p directors activate the aromatic ring at all positions, its just that o- and
p- positions are acivated more than the m- position.

Example: nitration of toluene gives three isomeric products in the ratios

shown, WHY?

CH3 CH3 CH3 CH3

NO2
HNO3
H2SO4 rt NO2
63% 3% NO2 34%
 Orientation: Ortho-Para directors 28

For ortho and para positions, the positive charge is placed directly on the C
atom carrying the methyl group, i.e. 3 carbocation, the most stabilized
carbocation intermediate, hence, o- and p- intermediates are lower in energy
than the m- intermediate. No such structure is possible for the m-
carbocation intermediate.
 Orientation: Ortho-Para directing activators 29
OH and NH2 groups stabilize the carbocation intermediate through resonance
electron donating effect which is more pronounced at o- and p- positions.
 Orientation: Ortho-Para directing deactivators 30
Halogens deactivate the aromatic ring due their strong electron withdrawing inductive
effect. The o- and p- positions are deactivated less than the m- position. How do they
o- and p- direct? Halogens also have electron donating resonance effect, because
they have filled p-orbitals (lone pairs) which can overlap with the p orbital of the
aromatic ring thereby stabilizing the carbocation intermediate. The effect is most felt
at the o- and p-positions.
 Orientation: Meta directing deactivators 31
All positions in the aromatic ring will be deactivated, but the effect is most felt at the
o- and p- positions.

For o- and p- positions, the positive charge is placed directly on the C atom
carrying the deactiavting group, hence o- and p- products formation is
disfavoured.
 Synthesis of disubstituted benzene derivatives 32
What are the products of the following reactions?

CH2CH2CH3 Br

a. HNO3 b.
HNO3
H2SO4 rt H2SO4 rt
O H SO3H

c. d. HNO3
HNO3
H2SO4 rt
H2SO4 rt

COOH

e. HNO3 HNO3
f.
H2SO4 rt H2SO4 rt
 Synthesis of disubstituted benzene derivatives 33
How would you synthesize the following compounds starting with benzene?

NO2
a.

Cl

NO2

b.

Cl

CH2CH3
c.

SO3H
 Synthesis of disubstituted benzene derivatives 34
The nitroso group, -N=O, is one of the very few nonhalogens that is o- and p-directing
deactivating group. Draw resonance structures of intermediates in o, m and p
electrophilic attack on nitrosobenezene and explain why o and p attack intermediates
are favoured over the the intermediate from meta attack.

O
N
HNO3
H2SO4 rt
 Synthesis of disubstituted benzene derivatives 35
Using benzene or toluene as the only aromatic organic starting material, devise the
synthesis for each of the following:

NO2 CH2CH3
a. b.

Br NO2

CH3 CO2H

c. d.

SO3H
 Diazotization reaction and its Uses 36
Primary aromatic amines react with nitrous acid (HONO) to give a stable
arenediazonium salts.

nitrous acid
NH2 HONO N Cl
N

NaNO2/ HCl
+ 2 H2O
0-5 oC

diazonium salt

Arenediazonium salts are useful in synthesis because the diazonio group (N2+ ) can be
replaced by nucleophiles.
Diazotization reaction and its Uses 37
 Diazotization reaction and its Uses 38

Aryldiazonium ions react with strongly activated aromatic rings to give azo
compounds. All azo compounds are coloured.

N N OH N N OH
+ OH

p-hydroxyazobenzene
yellow leaflets

Problem: How would you synthesize methyl orange from p-aminobenzenesulfonic

acid and N,N-dimethylaniline?

H3C
N N N SO3-Na+
H3C

Methyl orange