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Chapter Scopes

CHAPTER 4

IUPAC nomenclature / naming

Influence of delocalised electrons on
structure and properties
Electrophiles substitution
Oxidation reaction of side-chain
Importance of benzene and its
derivatives

ARENES
(Aromatic
Hydrocarbon)

Arenes

Objectives
To understand the influence of
delocalized electrons on structure
and properties.
To explain the electrophiles
substitution and oxidation reaction of
side-chain for arene.
To know the importance of benzene
and its derivatives.

Aromatic hydrocarbons.
Aromatic indicates good smell & a
particular sort of delocalised bonding.
The arenes are based on benzene rings.
Benzene is the simplest arenes.

or

or

Benzene ring (C6H6)

Structure of Benzene
a planar molecule containing a ring of six
C atoms each with a H atom attached.
Each C atom is sp2 hybridised.
The six C atoms form a perfectly regular
hexagon. All the carbon-carbon bonds
have exactly the same lengths somewhere between single & double
bonds.

Each of the 6 C atoms has a p orbital that

can overlap equally well with neighboring p
orbitals on both sides.
The e- are shared around the ring in 2
doughnut-shaped clouds
H

H
C
H

C
C

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C
C

C
H

C
H

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Delocalised Electrons
There are delocalised electrons above
and below the plane of the ring.
Delocalised
electron

the circle represents the

delocalized electrons

Resonance Structure
of Benzene

The delocalised electron make the

benzene ring to be stable & resist
__________________.

Nomenclature of
Monosubstituted Benzenes
Benzene is the parent name for some
monosubstituted benzenes; the
substituent name is added as a prefix.

OH

hydroxybenzene

NH2

CH3

aminobenzene

Nomenclature of benzene
as a substituent
When the benzene ring is considered as a
substituent, the name phenyl (fen-nil) is
used for C6H5 & the name benzyl is used
for C6H5CH2 group
CH2

methylbenzene

Examples:
Benzene as A Substituent
CHO
phenylmethanal

CH2OH
phenylmethanol

Phenyl (-C6H5)

Benzyl (C6H5CH2-)

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Common Names of
Aromatic Compounds

Nomenclature of
Disubstituted Benzenes
CN

Benzonitrile
CHO

When 2 substituents are present, their

position may be indicated by the:
prefixes:
1,2 disubstituted ortho (o),
1,3 disubstituted meta (m) &
1,4 disubstituted para (p)
corresponding numerical positions (the
lowest possible no.)

Benzaldehyde

For the nitrobenzoic acids:

Nomenclature of
Trisubstituted Benzenes

Nomenclature of benzenes with

two/more functional groups
When 2 or more functional groups are
present, no. 1 is given to the principal
functional group.
Usual order for choosing the principal
functional group:
carboxylic > acid halide > amide >
aldehyde > cyanide > ketone > alcohol >
phenol > amine

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Physical Properties of
Benzene

H3C

Cl

C6H6
A colourless liquid
Inflammable & burn with a smoky flame
due to its high C content
Melting point 5.5 C
Boiling point 80 C
Have a peculiar smell

4-chloromethylbenzene

Physical Properties
1.Boiling Points
Benzene boils at 80 C, higher than other
hydrocarbons of similar size due to the
______________ dipoles between the
delocalised electrons besides the Van der
Waals force between benzene molecules.
Methylbenzene boils at 111 C since it is a
bigger molecule & have a small
______________dipole caused by methyl
group.

3. Solubility in water
The arenes are ______________ in water
since the arenes molecules are quite large
compared to a water molecule.
This would require to break down a lot of
existing hydrogen bonds between water
molecules to dissolve an arene molecule.

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2. Melting point
Benzene melts at 5.5 C.
Methylbenzene melts at -95 C. It is
________ than benzene because the
molecules are not as closely packed as
benzene due to methyl group. This makes
the m.p. falls.

4. Reactivity
Benzene is resistant to addition reactions
since this will use up the delocalized
electrons to form bond.
Methylbenzene react more quickly than
benzene itself.

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Electrophilic Aromatic
Substitution (EArS) Reactions
The arene system undergoes substitution
reaction instead of addition.
The electron rich C=C system will react
with electrophiles via a substitution
pathway to preserve aromaticity.
H
H

E
H

+ E+
H

H
H

+ H+
H

What does EArS imply?

Electrophile (E+), an e- ________ species
that will react with nucleophile, an e__________ species (aromatic ring).
Aromatic because the reaction is
characteristic of aromatic systems.
A substitution implies that a group is
replaced (usually substitutes for 1 H of
benzene ring).

H
H

3 Fundamental Components
to an EArS Reaction
1) formation of the new bond from a
C=C in the arene nucleophile
2) removal of the proton by breaking
the C-H bond
3) reforming the C=C and restoring
aromaticity

The result is a resonance stabilized

nonaromatic carbocation / arenium ion.

3 resonance forms of nonaromatic

carbocation intermediate

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Mechanism of EArS Reaction

Reaction of the electrophile, E+ with the

arene is a slow step since it results in the
loss of aromacity.

Electrophilic
Substitutions Reactions
1)
2)
3)
4)
5)
6)

Alkylation (R)
Nitration (NO2)
Sulphonation (SO3H)
Halogenation (X2)
Acylation (COR)
Hydrogenation (H2)

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1. Friedel-Crafts Alkylation
of Benzene
Substitute an alkyl group (-R) to benzene
in the presence of a catalyst (e.g.
aluminum trichloride, AlCl3)
benzene undergoes electrophilic
substitution with an alkyl halide (R-X) to
form alkylbenzene (Ar-R)

Mechanism of Friedel-Crafts
Alkylation
AlCl3

Electrophilic species: Carbocation

AlCl4-

Happens when one (or more) of the H

atoms on the benzene ring is replaced by
a nitro group, NO2.

AlCl4-

Loss of proton gives

the neutral alkylated
substitution product
4.

CH3

2. Nitration: Benzene

CH3
H
+

+ HCl

1. CH3Cl + AlCl3 CH3+ + AlCl4-

2.

3.

CH3

CH3Cl

CH3

Reagent: conc. HNO3 & conc. H2SO4

yellow oily ________________ is formed.
Overall reaction:
NO2

+ HCl + AlCl3

+ HNO3

H2SO4

+ H2O

Catalyst

Mechanism of Nitration
HNO3 + H2SO4 NO2+ + HSO4- + H2O
Nitronium ion

At higher T, there is greater chance of

getting more than one nitro group
substituted onto the ring.

NO2

+ NO2+

H
+

NO2
H

NO2

+ HSO4-

1,3-dinitrobenzene
+ H2SO4

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Nitration: Methylbenzene

3. Sulphonation: Benzene

Reacts faster than benzene

Methyl groups direct new groups into
the _____& _____ positions on the ring
(assuming the methyl group is in the 1position).
Product: contains mainly two isomers.

Substitute one of the H on a benzene ring

with sulphonic acid group, -SO3H.
Sulphonating benzene:

Warm C6H6 with fuming H2SO4

CH3
+ HNO3

H2SO4

SO3 + H2SO4 SO3H+ + HSO4Reactive electrophile

H
+ SO3

H2SO4
catalyst

SO3H

benzenesulphonic acid

Sulphonation: Methylbenzene
Methyl groups 2- and 4- positions
director
Product: contains mainly two isomers

H2SO4

SO3

Reaction:

+ X2

FeX3
catalyst

Reagent: normally the halogen X2 (e.g.

Br2) with a Lewis acid catalyst.
Electrophilic species: the halonium ion
(i.e. X+) formed by the removal of a halide
ion by the Lewis acid catalyst.

FeX3 + X2 FeX4- + X+ (electrophile)

4. Halogenation

X
+ HX

5. Friedel-Crafts Acylation of
Benzene
Substitution of an acyl (RCO) group to
form aromatic ketone (Ar-COR).
Reagents: normally the acyl halide (e.g.
RCOCl) with AlCl3, a Lewis acid catalyst.

Observation: The halogens,

X2 are decolourized & acidic
fumes of HX are formed

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6. Hydrogenation
Vapourized benzene will react with H2
with the presence of the Ni / Pt / Pd
catalyst at 150C.
Cyclohexane will be produced.
Ni / Pt / Pd

+ 3H2

Alkylbenzene
Benzene ring with an alkyl group attached
to it.
Example : methylbenzene
Easily oxidized by an alkaline solution of
potassium manganate (VII) to benzoic
acid.

Side-chain Oxidation in
Alkylbenzenes

Methylbenzene is oxidized to benzoic

acid by heating it under reflux with
KMnO4 made alkaline with Na2CO3.

The purple colour of KMnO4 is eventually

replaced by a dark brown precipitate of
MnO4-.
The mixture is finally acidified with dilute
H2SO4.

Importance of Benzene
and its derivatives

Summary

1) Benzene as a gasoline additive.

2) Styrene is used to make polymers &
plastics.
3) Phenol for resins & adhesive.
4) Benzene are used to make some types
of rubbers, lubricants, dyes, detergents,
drugs, explosives & pesticides.

Able to explain the influence of

delocalized electrons on structure and
properties.
Able to understand the electrophiles
substitution and oxidation reaction of
side-chain for arene.
Able to identify the importance of
benzene and its derivatives.

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NO
O

C-R
Acylation
(
COR )

Nitration
(
NO2)
Halogenation
(
X)

Hydrogenation
(H2)

Alkylation
(R )
Sulphonation
SO3H)
(

SO3H

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