CHAPTER 5

BENZENE
&
AROMATIC
COMPOUNDS
 OUTLINES
1. Structure and nomenclature : IUPAC and common names
2. Reaction and Mechanism: Electrophilic substitution
i. Halogenation
ii. Nitration
iii. Sulphonation
iv. Friedel-craft Alkylation
v. Friedel-craft Acylation
3. Effect of substituents on the reactivity and orientation
i. Activating group – ortho-para directing effect
ii. Deactivating group – meta directing effect
4. Reaction of side chain on arenes
i. Substitution (halogenation)
ii. Oxidation (hot, concentrated KMnO4,H+)
5. Uses
 INTRODUCTION
✓Benzene (C6H6) is the simplest aromatic hydrocarbon.

✓Benzene is a highly unsaturated hydrocarbon.

✓Unsaturated hydrocarbons such as alkenes, alkynes and

dienes: addition reactions.
✓Benzene does react with bromine, but only in the presence
of FeBr3 (a Lewis acid), and the reaction is a substitution, not
an addition.

C
H+B
r F
e
B
r3 C
HB
r+H
B
r
+ F
e
B
r
6
6 2 6
5 3
STRUCTURE OF BENZENE

Resonance Kekulé
NOMENCLATURE
MONOSUBSTITUTED

RING AS
DISUBSTITUTED
SUBSTITUENT

TRISUBSTITUTED
 ✓ MONOSUBSTITUTED
➢To name a benzene ring with one substituent, name the substituent
and add the word benzene.
COMMON ROOT
 DISUBSTITUTED
➢Three ways:
✓Ortho
✓Meta
✓Para
 CONTINUE..
➢If the two groups on the benzene ring are different,

✓If one substituent is part of a common root,

➢Use as parent.
IF NOT
✓Number according to alphabetical
 CONTINUE..
USING COMMON ROOT
 CONTINUE..
USING ALPHABETICAL
 TRISUBSTITUTED
1. For three or more substituents on a benzene ring:

i. Number to give the lowest possible numbers around the

ring.

ii. Alphabetize the substituent names.

iii. When substituents are part of common roots, name the

molecule using common root. The substituent that
comprises the common root is located at C1.
CONTINUE..
CONTINUE..
 CONTINUE..

chloro
RING AS A SUBSTITUENT

PHENYL BENZYL
EXAMPLE..
REACTION OF BENZENE I
➢ELECTROPHILIC SUBSTITUTION

Friedel-Crafts
Nitration Halogenations
Acylation

Friedel-Crafts
Sulphonation
Alkylation
REACTION 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.
 GENERAL MECHANISM FOR
ELECTROPHILIC SUBSTITUTION
Step 1: Attack on the electrophile form the sigma complex

Step 2: Loss of a proton gives the substitution product

GENERAL REACTION
 ELECTROPHILIC
SUBSTITUTION REACTION
 HALOGENATION

➢Reagents: Cl2 or Br2

➢Catalyst: Lewis acid catalyst - AlCl3, FeCl3 or FeBr3.
 MECHANISM

Step 1: Formation of electrophile

Cl Cl
Cl Cl Al Cl Cl + AlCl4-
Cl Cl + Al Cl electrophile
Cl Cl

or

Cl2 + AlCl3 Cl + AlCl4-

Step 2: Formation of Arenium Ion

Step 3: Loss of Proton

 NITRATION
Reagents: a mixture of conc. HNO3 & conc. H2SO4
 MECHANISM

Step 1: Formation of Electrophile

 CONTINUE..
Step 2: Formation of Arenium Ion

Step 3: Loss of a Proton

SULFONATION

➢Reagents: SO3 + H2SO4

 MECHANISM

Step 1: Formation of Electrophile

 CONTINUE..
➢Step 2: Formation of Arenium Ion

➢Step 3: Loss of Proton

FRIEDEL-CRAFT ALKYLATION

➢Reagents: Haloalkane, RX, X=Br, Cl (eg: CH3Cl)

➢Catalyst: AlCl3, FeCl3 or FeBr3.

 MECHANISM

➢Step 1: Formation of Electrophile

 CONTINUE..
➢Step 2: Formation of Arenium Ion

➢Step 3: Loss of Proton

FRIEDEL-CRAFT ACYLATION

➢Reagent: Acid chloride (RCOCl)

➢Catalyst: AlCl3, under anhydrous conditions is formed.

 CONTINUE..

✓ Acyl chloride is used in place of alkyl chloride.

✓ The product is a phenyl ketone that is less reactive than benzene.
 MECHANISM

➢ Step 1: Formation of Electrophile

 CONTINUE..
➢ Step 2: Formation of Arenium Ion

➢ Step 3: Loss of proton to give the product

REACTION OF BENZENE II

Substituents

Orientation Reactivity
 REACTIVITY
Substituent group present in the benzene ring can influence
the rate of reaction of further substitutions.

ELECTRON ELECTRON
DONATING WITHDRAWING
ELECTRON DONATING GROUPS

• Make the ring more reactive (activating groups)

• Influence the reaction become faster

• Example:
✓-NH2 is more electropositive compared to benzene and
acts as ED.
✓The electron density of inside benzene ring will increase
(Resonance donating effect)
✓making it more readily to undergo electrophilic
substitution reactions.
ELECTRON WITHDRAWING GROUPS
• Make the ring less reactive (deactivating groups).
• Influence the reaction become slower.
• Examples:
✓NO2 is more electronegative compared to benzene and
acts as EW.
✓The electron density of inside the benzene ring will
decrease, making it less readily to undergo electrophilic
substitution reactions.
✓Halogens are deactivating because they are
electronegative and can withdraw electron density from
the ring along the sigma bond – inductive effect.
CONTINUE..
 EXERCISE..
Which of these compounds reacts faster with the mixture of
nitric acid and sulphuric acid?

Benzene reacts faster than nitrobenzene because:

✓ Nitrobenzene has a deactivator group

✓ NO2 will deactivate the benzene ring
✓ So, reaction is slower as compared to benzene
 EXERCISE..
In the reaction for electrophilic substitution of benzene ring, the amino group
(-NH2) is considered as the activator, while the halogen group (-X) is
considered as the deactivator. Explain why.

Amino group (-NH2) Halogen

✓ Is more electropositive ✓ Is more electronegative
compared to benzene ring compared to benzene ring

✓ Acts as ED ✓ Acts as EW

✓ Electron density of inside ✓ Electron density of inside

benzene ring will increase benzene ring will decrease

✓ Making more readily to undergo ✓ Making less readily to undergo

electrophilic substitution electrophilic substitution
reactions. reactions.
 ORIENTATION

Ortho-para Meta
director director
 CONTINUE..

➢Ortho – para director

✓Will direct the second substituent to C2 (ortho) and C4

(para) positions
 CONTINUE..
➢Meta director

✓Will direct the second substituent to C3 (meta) position

 Ortho/Para-Directing Activators:
Alkyl Groups

➢Alkyl groups activate by induction: direct further

substitution to positions ortho and para to themselves.

➢Alkyl group has most effect on the ortho and para positions
because their resonance structures include one tertiary
carbocation.
Ortho and Para-Directing Activators:
OH and NH2
➢Hydroxyl, and amino groups have a strong, electron-
donating resonance effect.

➢Most pronounced at the ortho and para positions.

➢Any substituent that has a lone pair of electrons on the

atom directly bonded to the aromatic ring
✓allows an electron-donating resonance interaction to
occur
✓make the ortho and para intermediates more stable
✓reacts more faster and will form product more faster
Ortho and Para-Directing Deactivators:
Halogens

➢Electron-withdrawing inductive effect outweighs weaker

electron-donating resonance effect.

➢Resonance effect is only at the ortho and para positions,

stabilizing carbocation intermediate.
SIDE-CHAIN REACTIONS OF
BENZENE DERIVATIVES
Free Radical Oxidation of
Substitution Reaction Alkylbenzene
• Halogenation of • side chain oxidation
alkylbenzene
 HALOGENATION OF
ALKYLBENZENE
➢Involving halogens such as Cl2 / Br2 in the presence of an
ultraviolet light (uv) or high temperature.
➢% monohalogenation product: 3o > 2o > 1o haloalkane
MECHANISM
 OXIDATION REACTION OF
ALKYLBENZENE
➢Alkylbenzenes are oxidized to benzoic acid by heating in
acidic KMnO4 or heating in Na2Cr2O7/H2SO4.

➢The benzylic carbon will be oxidized to the carboxylic acid

 CONTINUE..
➢In order for alkylbenzene to be oxidised,
✓it must posses ONE benzylic hydrogen
❑ hydrogen atom bonded to C atom which is bonded
directly to benzene ring).
EXAMPLE..
 USES OF 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 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.

THE
END..