ORGANIC CHEMISTRY
CHM 207
CHAPTER 4:
AROMATIC COMPOUNDS
(BENZENE AND TOLUENE)
NOR AKMALAZURA JANI
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.
Kekul 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 Kekul
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 sp 2
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.
Huckels
rule
Used to determine aromaticity for planar,
cyclic organic compounds with a
continous ring of overlapping p-orbitals.
If the number of pi () 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.
NamingAromatic
Compounds
A substituted benzene is derived by
replacing one or more of benzenes
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
nitrobenzen ethylbenzen
e e
Certain monosubstituted benzenes
have special names.
These are parent names for further
substituted compounds.
hydroxy
methyl group group
toluene phenol
carboxyl group
benzoic amino group
acid
aniline
DisubstitutedBenzenes
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
TriandPolysubstituted
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
counterclockwi 2-chloro
se numbering
chlorine 1-chloro
substituent
2
s have
lower 3 1
numbers
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 2
1
6 2 5 3
4
5 3
4
toluene 2,4,6-
trinitrotoluen
e
(TNT)
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.
diphenylmethan
e
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 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 -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
Nu- fast
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
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
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.
Effetcs 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
-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
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 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
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
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
SYNTHESIZING A SUBSTITUTED
AROMATIC COMPOUNDS
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
Immediate precursor of toluene:
i)Benzene was methylated in a Friedel-Crafts reaction
CH3Cl CH3
AlCl3
toluene
Immediate precursor of bromobenzene:
i)Bromination of benzene
Br2
FeBr3 Br
bromobenzene
TWO WORKABLE ROUTES FROM BENZENE TO
p-BROMOBENZOIC ACID
Br2 CH3Cl
FeBr3 AlCl3
Br
CH3 COOH
KMnO4
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.
