CHAPTER 4:
AROMATIC COMPOUNDS
(BENZENE AND TOLUENE)
Aromatic compounds
Organic compound that contains a
benzene ring in its molecule is known
as an aromatic compounds.
Sometimes called arenes.
Structure of Benzene
Can be represented in two abbreviated ways.
The corner of each hexagon represents a carbon
and a hydrogen atom.
Kekulé Structure of Benzene
Molecular formula is C6H6
All the hydrogen atoms are equivalent
Each carbon atom must have four covalent bonds.
Resonance Structure
• Resonance structure of benzene is a hybrid
resonance from two Kekulé structure as shown
below:
represents a resonance hybrid between the two
The hybrid structure is often represented by a
hexagon containing an inscribed circle.
Hexagonal ring – 6 carbon-carbon bonds are equal.
Circle – delocalised electrons of the benzene ring
Naming Aromatic
Compounds
• A substituted benzene is derived by
replacing one or more hydrogen atoms of
benzene with an atom or group of atoms.
• A monosubstituted benzene has the
formula C6H5G where G is the group that
replaces a hydrogen atom.
a) Monosubstituted Benzenes
Benzene as the parent name and the
substituent as a prefix.
The name is written as one word.
nitro ethyl
group group
nitrobenzene ethylbenzene
• Certain monosubstituted benzenes have
special names.
• These are parent names for further substituted
compounds.
methyl hydroxyl
group group
toluene phenol
carboxyl
group
benzoic acid amino
group
aniline
b) Disubstituted Benzenes
• Three isomers are possible when two
substituents replace hydrogen in a benzene
molecule.
• The prefixes ortho-, meta- and para- (o-, m- and p-)
are used to name these disubstituted benzenes.
substituents on
adjacent carbons
meta-dichlorobenzene
ortho-dichlorobenzene (1,3-dichlorobenzene)
(1,2-dichlorobenzene) mp –24.82oC, bp 172oC
mp –17.2oC, bp 180.4oC
substituents
are on opposite
sides of the
benzene ring
para-dichlorobenzene
(1,4-dichlorobenzene)
mp 53.1, bp 174.4oC
• When two substituents attached to a benzene ring are
different, the numbering system is based on the parent
name of the benzene derivative.
• The carbon atom containing functional group is
designated C1.
• Numbering such that lowest possible numbers are
used and substituents are listed alphabeticallly when
writing the name.
4-chloronitrobenzene
When one substituent corresponds to a
monosubstituted benzene with a special name,
the monosubstituted compound becomes the
parent name for the disubstituted compound.
phenol 3-nitrophenol
toluene 3-nitrotoluene
c) Tri- and Polysubstituted Benzenes
• When a benzene ring has three or more
substituents, the carbon atoms in the ring are
numbered.
• Numbering starts at one of the substituent
groups.
• Named by using the lowest possible numbers
and alphabetically order of the substituent.
6 2
1 3 1
5
4
4 2 wrong 6 correct
3 5
1,4,6-trichlorobenzene 1,2,4-trichlorobenzene
• When a compound is named as a
derivative of the special parent compound,
the substituent of the parent compound is
considered to be C-1 of the ring.
1
6
2
5 3
4
Naming compounds that cannot be
easily named as benzene derivatives
Benzene named as a substituent on a molecule with
another functional group as its root by the prefix
phenyl.
diphenylmethane
4-phenyl-2-pentene
The phenyl group, C6H5-
CH2
phenyl benzyl
CH=CH2 NH2 CH2Cl
common phenylethene phenylamine benzyl chloride
name
If the hydrocarbon chain contains more than
three carbon atoms, phenyl is used as part of the
name.
Examples:
CH3
CH2(CH2)5CH3 C CH2 CH3
Br
1-phenylheptane 2-bromo-2-phenylbutane
Physical
Properties of
Benzene and Its
Derivative
PHYSICAL PROPERTIES OF BENZENE
AND ITS DERIVATIVES
Benzene derivatives tend to be more symmetrical
than similar aliphatic compounds, and pack better
into crystals and have higher melting points.
Density:
- Slightly dense than non-aromatic analogues, but
still less dense than water.
- halogenated benzenes are denser than water.
Insoluble or slightly in water but very soluble in
organic solvent and oil.
Boiling points depends on the dipole moments of
compounds.
Reaction of Benzene
Halogenation
Nitration
Electrophilic
Sulphonation
substitution
Friedel-Crafts Alkylation
Friedel-Crafts Acylation
ELECTROPHILIC SUBSTITUTION REACTIONS
a) Halogenation
H X
X2 H2SO4 HX
or FeX3
halobenzene
b) Nitration
H NO2
H2SO4 2H2O
HNO3
nitrobenzene
c) Sulphonation
H SO3H
H2SO4
SO3
benzenesulphonic acid
ELECTROPHILIC SUBSTITUTION REACTIONS
d) Friedel-Crafts alkylation
H CH3
AlCl3
CH3Cl HCl
toluene
e) Friedel-Crafts acylation O
H C CH3
O AlCl3
HCl
CH3CCl
acetophenone
Reagents, electrophiles and catalysts in
electrophilic substitution reactions
Reactions Reagents Catalysts Electrophiles
Halogenation Cl2 or Br2 AlCl3, AlBr3, Cl , Br
FeCl3 or FeBr3
Nitration HNO3 H2SO4 NO2
Alkylation RCl AlCl3 R
RCH=CH2 H2SO4 RCH-CH3
Acylation RCOCl AlCl3
RCO
Sulphonation SO3 H2SO4 SO3H
HALOGENATION OF BENZENE
a)Chlorination
Cl
AlCl3 HCl
Cl2
chlorobenzene
b)Bromination
Br
FeBr3
Br2 HBr
bromobenzene
c) Iodination
I
1/2I2 HNO3 NO2 H2O
iodobenzene
MECHANISM: BROMINATION OF BENZENE
Step 1: Formation of a stronger electrophile
Br Br FeBr3 Br Br FeBr3
Br2.FeBr3 intermediate
(a stronger electrophile than Br2)
Step 2: Electrophilic attack and formation of the sigma complex
H H H H
Br Br Br
H H H H H H H H
Br Br FeBr3
H H H H H H H H
H H H H
sigma complex
FeBr4-
Step 3: Loss of a proton gives the products
H -
Br FeBr4 H
H H
H Br
HBr FeBr3
H H
H H
H
H
MECHANISM: NITRATION OF BENZENE
Step 1: Formation of the nitronium ion, NO2+
HO SO3 H HO NO2 + -
H2O + NO2 + HSO4
Step 2: Formation of an arenium ion as a result of electrophilic addition
H NO2
+ slow
NO2
nironium ion arenium ion
Step 3: Loss of a proton gives the products
H NO2 NO2
-
HSO4 fast H2SO4
MECHANISM: FRIEDEL-CRAFTS ALKYLATION
Step 1: Formation of electrophile
H H
CH3 C Cl AlCl3 CH3 C -
AlCl4
CH3
CH3
carbocation (electrophile)
Step 2: Formation of an arenium ion
H H CH(CH3)2
C CH3
CH3
arenium ion
Step 3: Loss of a proton
H CH(CH3)2
CH(CH3)2
-
AlCl4 HCl + AlCl3
MECHANISM: FRIEDEL-CRAFTS ACYLATION
Step 1: Formation of electrophile
O O
-
CH3 C Cl AlCl3 CH3 C AlCl4
Step 2: Formation of an arenium ion
O
O H C CH3
CH3 C
Step 3: Loss of a proton
O O
H C CH3 C CH3
AlCl4-
HCl + AlCl3
Ortho-Para and Meta Directing
Substituents
When substituted benzenes undergo further
substitution, the substituent group present in
the benzene derivative will influence
electrophilic substitution in 2 ways which
are:
i) Reactivity
ii)Orientation
EFFECTS OF SUBSTITUENTS ON THE
REACTIVITY OF ELECTROPHILIC
AROMATIC SUBSTITUTION
Substituent group present in the benzene ring
can influence the rate of reaction of further
substitutions.
Electron-donating groups make the ring more
reactive (called activating groups) thus influence
the reaction become faster.
Electron-withdrawing groups make the ring less
reactive (called deactivating groups) thus
influence the reaction become slower.
EFFECTS OF SUBSTITUENTS ON THE
ORIENTATION OF ELECTROPHILIC
AROMATIC SUBSTITUTION
A substituents group already in the ring
influences the position of further electrophilic
substitution whether at ortho, meta or para
position.
Ortho-para directors: electrophilic substitution
to the C2 and C4 positions.
Meta directors: electrophilic substitution to
the C3 position.
Effects of substituent groups on the benzene
ring
Activating groups Deactivating groups
(electron donating) (electron-withdrawing)
-NH2 -F O
-OH -Cl
C R SO3H
-OR -Br
O
-NHCOCH3 -I C N
C OH
-R NO2
O
C OR NR3
ortho-para directors ortho-para meta directors
directors
Example:
CH2CH3 CH2CH3 CH2CH3 CH2CH3
Br
Br2
FeBr3 Br
-CH2CH3 = ortho and para directors Br
ortho position para position meta position
major products minor product
Example:
NO2 NO2 NO2 NO2
Br
Br2
FeBr3 Br
Br
-NO2 = meta director meta position ortho position para position
major product
minor products
ii) REACTIONS OF BENZENE
DERIVATIVES
Alkylbenzene such as toluene (methylbenzene)
resembles benzene in many of its chemical
properties.
It is preferable to use toluene because it is less
toxic.
The methyl group activates the benzene
nucleus.
Toluene reacts faster than benzene in all
electrophilic substitutions.
Reaction in the side chain and benzene nucleus of
benzene
REACTIONS
OF TOLUENE
Reactions of the
Reactions of the
methyl group
benzene ring
(side chain)
Electrophilic
Substitution substitutions
Oxidation
-halogenation - Halogenation
- Nitration
- Friedel-Crafts
reactions
SIDE-CHAIN REACTIONS
a) Oxidation Reaction of Alkylbenzene
O
+
CH2 R hot, conc., KMnO4/H C OH
reflux
examples:
O
+
hot, conc., KMnO4/H
CH3 C OH
reflux
O
+
CH2 CH3 hot, conc., KMnO4/H C OH
reflux
hot, conc., KMnO4/H+
CH3 COOH
reflux
CH3 COOH
b) Halogenation Of Toluene
Side chain substitution
CH3 CH2 Cl
uv light
Cl2 HCl
(chloromethyl)benzene
CH2 Cl CHCl2
uv light
Cl2 HCl
(dichloromethyl)benzene
CHCl2 CCl3
uv light
Cl2 HCl
(trichloromethyl)benzene
* Bromination of toluene takes place under similar
conditions to yield corresponding bromine derivatives.
SYNTHESIZING A SUBSTITUTED
AROMATIC COMPOUNDS
i) Synthesis m-chloronitrobenzene starting from benzene
NO2
?
Cl
• Two substituents: -NO2 (meta-directing) and –Cl (ortho- and
para-directing)
• Cannot nitrate chlorobenzene because the wrong isomer (o-
and p-chloronitrobenzenes) would formed.
Cl HNO3, H2SO4
chlorobenzene
NO2
NO2
Cl
Cl2, FeCl3 m-chloronitrobenzene
nitrobenzene
TWO STEPS: NO2
NO2
HNO3 Cl2
H2SO4 FeCl3
Cl
benzene nitrobenzene m-chloronitrobenzene
ii) Synthesis p-bromobenzoic acid starting from benzene
? COOH
Br
• Two substituents: -COOH (meta-directing) and –Br (ortho-
and para-directing)
• Cannot brominated benzoic acid because the wrong isomer
(m-bromobenzoic acid) would formed.
• Oxidation of alkylbenzene side chains yields benzoic acids.
• Intermediate precursor is p-bromotoluene
CH3 COOH
KMnO4
Br Br
Immediate precursor of p-bromotoluene:
i) Bromination of toluene
or
ii) Methylation of bromobenzene
CH3
Br2 CH3 CH3
FeCl3
Br Br
or separate the isomer
CH3Cl CH3 CH3
Br AlCl3
Br Br
separate the
isomer
Immediate precursor of toluene:
i) Benzene was methylated in a Friedel-Crafts reaction
CH3Cl CH3
AlCl3
benzene toluene
Immediate precursor of bromobenzene:
i) Bromination of benzene
Br2
FeBr3 Br
benzene bromobenzene
TWO WORKABLE ROUTES FROM BENZENE TO
p-BROMOBENZOIC ACID
Br2 CH3Cl
FeBr3 AlCl3
Br
CH3 COOH
KMnO4
benzene CH3 Br
CH3Cl Br2 Br
AlCl3 FeBr3
USES OF BENZENE AND TOLUENE
Benzene:
- as solvent for oils and fats
- starting material for making other chemicals.
For example, benzene is used in the cumene
process to produce phenol.
- making organic compounds such as
phenylethene (styrene) and nitrobenzene. These
organic compounds are then used to make
plastics (polystyrene), dyes and nylon.
USES OF BENZENE AND TOLUENE
Toluene:
- A common solvent, able to dissolve paints,
paint thinners, silicone sealants, many chemical
reactants, rubber, printing ink, adhesives
(glues), lacquers, leather tanners and
disinfectants.
- As a solvent to create a solution of carbon
nanotubes.
- Dealkylation to benzene (industrial uses).
- As an octane booster in gasoline fuels used in
internal combustion engines.
-As a coolant in nuclear reactor system loops.