ORGANIC CHEMISTRY
CHM 207
CHAPTER 4:
AROMATIC COMPOUNDS
(BENZENE AND TOLUENE)
4.1 Nomenclature of aromatic compounds.
4.2 Structures and aromaticity
Delocalisation of electrons
Stability of benzene
Physical properties of benzene and toluene
4.3 Reactions of benzene (electrophilic substitution reactions):
Halogenation,
Nitration,
Sulfonation,
Friedel-Crafts Alkylation and Acylation,
Side-chain oxidation.
4.4 Effect of substituents on the reactivity and orientation of
electrophilic aromatic substitution.
4.5 Uses of benzene and toluene.
Aromatic compounds
• Organic compound that contains a benzene
ring in its molecule is known as an aromatic
compounds.
• Sometimes called arenes.
• Molecular formula: C6H6
• Represented as a regular hexagon containing
an inscribed circle.
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 theory: the structure of benzene is a resonance
hybrid structure of two Kekulé cononical forms.
• The hybrid structure is often represented by a hexagon
containing an inscribed circle.
represents a resonance hybrid between the two
• Hexagonal ring – 6 carbon-carbon bonds are
equal.
• Circle – delocalised electrons of the benzene
ring
CRITERIA OF AROMATIC COMPOUNDS
• Structure must be cyclic, containing some number of conjugated pi
bonds.
• Each atom in the ring must have an unhybridized p orbital. (The
ring atoms are usually sp2 hybridized or occasionally sp
hybridized).
• The unhybridized p orbitals must overlap to form a continuous ring
of parallel orbitals. The structure must be planar (or nearly planar)
for effective overlap to occur.
• Delocalization of the pi electrons over the ring must lower the
electronic energy.
* Antiaromatic compound: fulfills the first three criteria, but
delocalization of the pi electrons over the ring increase the
electronic energy.
Huckel’s rule
• Used to determine aromaticity for planar, cyclic organic
compounds with a continous ring of overlapping p-
orbitals.
• If the number of pi (π) electrons in the monocyclic
system is (4N+2), the system is aromatic. N is 0, 1, 2,
3…..
• Systems that have 2, 6 and 10 pi electrons for N = 0, 1, 2
is a aromatic.
• Systems that have 4, 8, and 12 pi electrons for N = 1, 2,
3 are antiaromatic.
Naming Aromatic Compounds
• A substituted benzene is derived by replacing one
or more of benzene’s hydrogen atoms with an
atom or group of atoms.
• A monosubstituted benzene has the formula
C6H5G where G is the group that replaces a
hydrogen atom.
• All hydrogens in benzene are equivalent.
• It does not matter which hydrogen is replaced by
G.
MONOSUBSTITUTED BENZENES
• Some monosubstituted benzenes are named by adding
the name of the substituent group as a prefix to the
word benzene.
• The name is written as one word.
nitro group ethyl group
nitrobenzene ethylbenzene
• Certain monosubstituted benzenes have special
names.
• These are parent names for further substituted
compounds.
hydroxy
methyl group group
toluene phenol
carboxyl group
amino group
benzoic acid
aniline
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.
ortho disubstituted benzene
substituents on adjacent carbons
ortho-dichlorobenzene
(1,2-dichlorobenzene)
mp –17.2oC, bp 180.4oC
meta disubstituted benzene
substituents on adjacent carbons
meta-dichlorobenzene
(1,3-dichlorobenzene)
mp –24.82oC, bp 172oC
para disubstituted benzene
substituents are on opposite sides
of the benzene ring
para-dichlorobenzene
(1,4-dichlorobenzene)
mp 53.1, bp 174.4oC
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
When one substituent corresponds to a
monosubstituted benzene with a special name, the
monosubstituted compound becomes the parent
name for the disubstituted compound.
toluene 3-nitrotoluene
TRI- & POLY-SUBSTITUTED
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.
• The numbering direction can be clockwise or
counterclockwise.
• Numbering must be in the direction that gives the
substituent groups the lowest numbers.
clockwise 6-chloro
numbering
1-chloro
6
5 1
4 2
4-chloro
3
1,4,6-trichlorobenzene
counterclockwise 2-chloro
numbering
chlorine 1-chloro
substituents
have lower 2
numbers 3 1
4 6
4-chloro
5
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
1 2
6 2 5 3
4
3
5
2,4,6-trinitrotoluene(TNT)
4
toluene
• When the hydrocarbon chain attached to the
benzene ring is small, the compound is named as
benzene derivative.
• Example:
CH2CH3
ethylbenzene
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
• Can write as “Ph” or “f” in place of “C6H5”.
• “Benzyl” refers to “C6H5CH2-”
CH=CH2 CH2Cl
phenylethene benzyl chloride
• 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
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 in water
• Boiling points depends on the dipole moments of
compounds.
REACTION OF BENZENE
ELECTROPHILIC SUBSTITUTION REACTIONS OF
BENZENE
stability of π-electron system is lost when benzene
undergoes addition reactions.
benzene and its derivatives undergo substitution
reaction rather than addition reactions.
product of substitution reactions: aromatic
compounds and not saturated compounds.
Mechanism of electrophilic substitution
of benzene
Step 1: Electrophilic addition of the benzene ring
H
+
E
E slow
arenium ion (a carbocation)
Step 2: Deprotonation of the arenium ion
H E
E
- fast
Nu H Nu
nucleophile
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
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
substituents, 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: the groups that tend to direct
electrophilic substitution to the C2 and C4 positions.
• Meta directors: the groups that tend to direct
electrophilic substitution to the C3 position.
Effects of substituent groups on
the benzene ring
Activating groups Deactivating groups
(electron donating) (electron-withdrawing)
-NH2 -R -F O
-OH -Cl C R SO3H
-OR -Br O
-NHCOCH3 -I C N
C OH
NO2
O
C OR NR3
ortho-para directors ortho-para meta directors
directors
Example:
CH2CH3 CH2CH3 CH2CH3 CH2CH3
Br
Br2
FeBr3 Br
-CH2 CH 3 = ortho and para directors Br
or tho 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
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.
Reactions
of toluene
Reactions of the Reactions of the
methyl group benzene ring
Electrophilic
substitutions
Substitution - Halogenation Addition reaction
Oxidation
-halogenation - Nitration -hydrogenation
- Friedel-Crafts reactions
- Sulfonation
SIDE-CHAIN REACTIONS
OXIDATION REACTION OFALKYLBENZENE
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
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
1. 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
2. Synthesis p-bromobenzoic acid starting from benzene
? COOH
Br
• Two substituents: -COOH (meta-directing) and –Br (ortho- and para-
directing)
• Cannot brominated benzioc 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.
• 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.
