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
