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.