CHAPTER 2

Benzene and
Aromaticity
CHE 143
MADAM MUNIRAH ONN
 Content
CHAPTER 2: Benzene & Aromaticity

• 2.1 Structure
• 2.2 Nomenclature
• 2.3 Stability & physical properties
• 2.4 Aromatic character & Huckel’s Rule
• 2.5 Reactions – sulphonation, halogenation,
Friedel-Crafts
• Aromatic hydrocarbon is an organic
compound that contains a benzene ring in its
molecule.

• Benzene or arene is the simplest aromatic

hydrocarbon with the molecular formula
C6H6.

• C6H6, is a flat symmetrical molecule with a

structural formula that is often formalized

• Aromatic was used to described some

fragrant compounds in early 19th century
 Structure of Benzene

H
H C H
C C
Molecular formula: C6H6
C C
H C H
H
Common name of some aromatic compounds:

CH3 OH

toluene phenol
(methylbenzene) (hydroxybenzene)
Continue…

OCH3 NH2

anisole aniline
(methoxybenzene) (aminobenzene)
 Naming of
Aromatic Benzenes
 Monosubstituted Benzenes

• Some monosubstituted benzenes are

named by giving the name of the
substituent followed by the word
“benzene”.
Examples:

Br bromobenzene

NO2 nitrobenzene

CH 2CH3 ethylbenzene
 • Some common substituent change the
root name of the ring. IUPAC accepts
these as root names.

COOH SO3H CN CHO

benzoic acid benzene benzonitrile benzaldehyde

sulfonic
acid
 NH2 OCH3 CH3 OH

aniline anisole toluene phenol

Priority group
 Disubstituted Benzenes
• Rules 1-Some disubstituted benzenes are name
by using number or the prefixes ortho- for
C1,C2; meta- for C1,C3; and para- for C1,C4.

X
ortho 1
2 ortho
2
3
3 meta
meta 4
para
Example 1:

Br

Br

1,2-dibromobenzene
or ortho-dibromobenzene
Example 2:

Br Br

1,3-dibromobenzene
or meta-dibromobenzene
Example 3:

Br Br

1,4-dibromobenzene
or para-dibromobenzene
• Rules 2- If two substituents attached to
the benzene rings are different, their
name are listed in alphabetical order.

Br Bromine

CH2CH3CH3 Propyl

1-bromo-3-propylbenzene
Example 1:

Cl
1
6 2

3
5
4 I

1-chloro-3-iodobenzene
or meta-chloroiodobenzene
 • Rules 3-name a priority group as a
parent name.

Not 1-methoxy-3-methylbenzene

CH3
NH2
Br

OCH3
2-bromoaniline 3-methylanisole
Not 1-amino-2-bromobenzene
Example 2:

CH3
1 6
2
Cl 5

3 4

2-chlorotoluene
or ortho-chlorotoluene
Not 1-chloro-2-methylbenzene
Example 3:
NH2
1
6 2

5 3
4

NO2

4-nitroaniline
or para-nitroaniline

Not 1-amino-4-nitrobenzene
 Polysubstituted Benzenes

• If the benzene ring has more than two

substituents, the lowest possible number
for the substituents are used.

• The substituents are listed in alphabetical

order with their appropriate numbers.
Example 1:
1. Find lowest possible
number
NO2
1 Br
2
6

3
5
4

Cl

2-bromo-4-chloro-1-nitrobenzene
1. Name in
alphabetical order
Example 2:

Br
3 2
4 1
Cl OH
5 6

3-bromo-4-chlorophenol
Not 2-bromo-1-chloro-4-hydroxylbenzene
 Phenyl
• Phenyl (-C6H5) is used when the benzene
ring is considered as a substituent.
• When benzene is attached to an alkene with
a functional group or an alkane group of 7 or
more carbon atoms, benzene is usually
considered as substituent instead of the
parent.
• The structure of phenyl:

a phenyl group
Example 1:

1-phenyl 1-octene
2

2-phenyl ethanol
 Benzyl
• Benzyl (C6H5-CH2) is used when the benzene
ring is considered as a substituent.

• Structure of benzyl:

CH 2

a benzyl group
Example 1:

CH2Cl

benzyl chloride
or chloromethylbenzene
Example 2:

CH2OH

benzylalcohol or phenylmethanol
 Physical Properties
• Insoluble in water
• Good solvents for nonpolar material
• Less dense than water
• volatile
• Colorless
• Flammable liquid (burns with a sooty flame
due to incomplete combustion
• Several aromatic hydrocarbons are toxic
 Sources
• From high temperature distillation of coal tar.
At one time, coal tar the main source of
aromatic hydrocarbon but now its petroleum

• Heating petroleum at high temperature and

pressure over a catalyst
Reactions of
Benzene
 Aromatic Substitution Reactions

• Benzene is a highly unsaturated molecule

which contain three double bonds,
however the reaction of benzene is
different with alkene.

• Benzene undergoes electrophilic

aromatic substitution because it is
unreactive.
• Electrophilic aromatic substitution occurs
when an electrophile, E+, substitutes with
H atom on an aromatic ring.

• The  electrons in the benzene makes

the benzene ring rich in electrons and
behaves as nucleophile attack the
electrophile.
H E

+ E+ + H+
General Mechanism Reaction of Benzene

+ E A

E
H + A-

Step 1: Electrophile attacks benzene to

produce arenium ion.
 E
H -
+ A

E
+ HA

Step 2: Nucleophile removes a proton from

arenium ion and form a product.
• There are four types of substitution
reactions of benzene:

a) Halogenations
b) Nitration
c) Sulfonation
d) Friedel-Crafts Reactions; Friedel-Crafts
alkylation and Friedel-Crafts acylation.
 a) Halogenations of Benzene
General reaction:

H
X
H C H
C C FeX3
+ X2 room temp. + HX
C C
H C H
H

Lewis acid acts as a catalyst

Example: Cl

Cl2/FeCl3 + HCl

When a benzene ring reacts with chlorine, chlorobenzene and hydrogen chloride is produced.

When a benzene ring reacts with bromine, bromobenzene and hydrogen bromide is produced.
 Mechanism Halogenations of Benzene
These reactions involve electrophilic substitution where a hydrogen is substituted with a halogen.

Step 1st-Generating the electrophile Br+ ion. To get the positive ion needed for the
reaction, a halogen carrier is required. The catalysts and co-reagents react to generate a
strong electrophilic species.
Step 2nd-Electrophile Br+ , attacks benzene to produce arenium ion (an intermediate).
Step3rd- Halide ion is lost to give aromatic ring. Loss of proton from arenium ion and
form a bromobenzene.
b) Nitration of Benzene

NO2

H2SO4
+ HNO3 50-55oC + H2O
 Mechanism for the nitration of benzene ring
Nitric acid accepts a proton from a stronger acid (H2SO4) and form a protonated nitric acid. The
protonated nitric acid dissociates to form a nitronium ion (NO2+)

Loss of H+

NO2+ which is the electrophilic species will be attacked by the electron-rich benzene ring /
Electrophile will interacts with benzene to form a cyclohexadienyl cation which is known as
arenium ion.
c) Sulfonation of Benzene

SO3H

H2SO4
+ H2O
reflux
Mechanism on Sulfonation of Benzene

• 1-Produce electrophile sulfonium ion (SO3+) in concentrated H2SO4.

• 2-SO3 is the electrophile that reacts with benzene to form an arenium ion.
• 3.A proton is removed from the arenium ion by hydrogensulphate ion to form the
benzenesulfonate ion.
d) Friedel-Crafts Alkylation of Benzenes

General reaction:

AlCl3
+ R-Cl + HCl
room temp.

alkylbenzene
Example:

AlCl3
+ CH3CH2Cl
room temp.
chloroethane
CH2CH 3

+ HCl

ethylbenzene
 Generation of electrophilic R+

Mechanism of Alkylation

51
 d) Friedel-Crafts Acylation of Benzenes

General reaction:

O
C R
O
AlCl3
+ R-C Cl + HCl
80oC
Example:

O C CH3
AlCl3
+ CH3C Cl
80oC
ethanoyl chloride + HCl

2-phenylethanone
Mechanism of Friedel-Crafts Acylation
 Hückel's Rule
• Benzene, the most widely recognized aromatic
compound with six delocalized electrons.
• Huckel’s Def.– an aromatic is a planar cyclic
molecule with alternating double and single
bonds, has aromatic stability if it has 4n+ 2
electrons (n is 0,1,2,3,4) and must be sp2
hybridized.
• Hückel's rule estimates whether a planar ring
molecule will have aromatic properties or not.
Use formula 4n + 2
Aromatic molecules have the following
characteristics:
“is this
molecule
aromatic?”

• They are cyclic.

• They are conjugated all around the ring.
• The molecule has 4n+2 = π electrons (n=0 or
any positive integer)
• The molecule must be flat with SP2
hybridized.
 How does the 4n+2 Rule Work?
• To apply the 4n+2 rule, first count the number of
π electrons in the molecule. Then, set this
number equal to 4n+2 and solve for n. If is 0 or
any positive integer (1, 2, 3, 4...), the rule has
been met. For example, benzene has six π
electrons:
4n + 2 = 6
4n = 4 Therefore, n = 1
• For benzene, we find that n=1, which is a positive
integer, so the rule is met.
“is this molecule
aromatic or not?”

n equal to 6 pi
electrons so it is
aromatic

n equal to 4 pi
electrons so it is anti
aromatic
 Reactions
Mechanism
of Aromatic
Compound
 Oxidation of Alkyl Benzene

• An alkyl group bonded to a benzene ring can

be oxidized to a carboxyl group.

• Alkyl side chains can be oxidized to COOH by

strong reagents such as KMnO4 and
Na2Cr2O7 if they have a C-H next to the ring

• Benzene ring is so stable, therefore, it will

not be oxidized, only the alkyl group is
oxidized.
Example:

CH3
KMnO4/H+
reflux

COOH
+ H2O
 • Alkyl substituent will be oxidized to a
carboxylic group if hydrogen is bonded to
the benzylic carbon.

CH2CH3 COOH
KMnO4/H+
reflux + H2O

CHCH3 COOH
CH3
1-ethyl-3-isopropylbenzene benzene,1,3-dicarboxylic acid
 • If alkyl group lack of hydrogen, the
oxidation reaction will not occur because
the first step in the oxidation reaction is
removal of hydrogen from the benzylic
carbon.

CH3 K2Cr2O7/H+
C
NO reaction
CH3
CH3

No H attach to this C
• The same reagents that oxidize alkyl
substituent will oxidize benzylic alcohol to
benzoic acid.

K2Cr 2O7/H+
CHCH3 COOH
OH
 Halogenation of Alkyl Benzene

• Substitution of free radical also occur for

alkylbenzene side chain as in alkane.

• Side-chain chlorination of toluene occurs in

the presence of UV light.

• For bromine, side chain of bromination can

occurs from presence of UV light or a radical
catalyst and reagent which is a sources of
bromine radical.
Example:

H H
H C H H C Cl

Cl2
+ HCl
uv light

toluene benzylchloride
Bromination of Alkylbenzene Side
Chains
• Reaction of an alkylbenzene with N-bromo-
succinimide (NBS) and benzoyl peroxide (radical
initiator) introduces Br into the side chain

69
 Mechanism of NBS (Radical) Reaction

• Abstraction of a benzylic hydrogen atom generates

an intermediate benzylic radical
• Reacts with Br2 to yield product
• Br·radical cycles back into reaction to carry chain

Step2

Br2 produced from

Step1 reaction of HBr with
NBS
70
 Reduction of Aromatic Compounds

• Aromatic rings are inert to catalytic hydrogenation

under conditions that reduce alkene double bonds
• Reduction of an aromatic ring requires more powerful
reducing conditions (high pressure or rhodium
catalysts)

71
 Reduction of Aryl Alkyl Ketones

• Aromatic ring activates neighboring carbonyl group

toward reduction
• Ketone is converted into an alkylbenzene by catalytic
hydrogenation over Pd catalyst

1st- Acylation
2nd Hydrogenation

72
 Effect of Substituents on Reactivity
and Orientation

• The substituent already attached to the

benzene ring determines the reactivity
and the location of the new substituent.

• Substituents that will make the benzene

ring to be less reactive is called the
deactivating group. Example is –NO2
compound. It is a meta directing group.
• Substituents that will make the benzene
ring more reactive is called the activating
group. Examples are -OH and –CH3. They
are ortho-para directing groups.

• Substituents which are classify as weakly

deactivating group (examples:
fluorine,amine, chlorine, bromine and
iodine) is ortho-para directing groups.
 Ortho- and Para-Directing
Activators: Alkyl Groups
• Alkyl groups activate: direct further substitution to positions
ortho and para to themselves
• Alkyl group is most effective in the ortho and para positions

75
 Ortho- and Para-Directing
Activators: OH and NH2
• Alkoxyl, and amino groups have a very strong
activators, Most pronounced at the ortho and para
positions

76
 Ortho- and Para-Directing
Deactivators: Halogens
• Halogen is a weak deactivating group
• Resonance effect is only at the ortho and para positions,
stabilizing carbocation intermediate

77
Compounds with ortho-para Director

R X OH
4th
2nd

alkyl group halogens group phenol

OR NH2
1st
3rd

alkoxy group amino benzene

Example:
CH3

Br 2/FeBr 3

methylbenzene CH3 CH3

Br
+

2-bromotoluene Br
(ortho)
4-bromotoluene
(para)
Example:
Br

Cl2/FeCl3

bromobenzene Br Br
Cl
+

1-bromo-2-chlorobenzene
(ortho) Cl
1-bromo-4-chlorobenzene
(para)
 Compounds with Meta Director

CHO COOH
3rd 4th
5th (Most
deactivating)

benzaldehyde benzoic acid

COOR CONH2

2nd benzamide
1th (weak deactivating)
Example:

NO2 NO2

Cl2/FeCl3

Cl
nitrobenzene
3-chloronitrobenzene
(meta)
 Meta-Directing Deactivators
• Inductive and resonance effects reinforce each other
• Ortho and para intermediates destabilized by
deactivation of carbocation intermediate
• Resonance cannot produce stabilization

83
Summary Table: Effect of Substituents
in Aromatic Substitution

84
 Trisubstituted Benzenes:
Additivity of Effects
• If the directing effects of the two groups are the same, the
result is additive

85
 Substituents with Opposite
Effects
• If the directing effects of two groups oppose each
other, the more powerful activating group decides the
principal outcome
• Usually gives mixtures of products

86
Meta-Disubstituted Compounds
• The reaction site is too hindered
• To make aromatic rings with three adjacent
substituents, it is best to start with an ortho-
disubstituted compound

87
 Uses of Benzene
• Gasoline additive
• Industrial solvent
• Rubber manufacturing
• Spot remover
• Detergents
• Drugs
• Pesticides
• Paint, lacquer, spray paint
• dyes