CHAPTER 6.

0
BENZENE AND ITS DERIVATIVES

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 6.1 Introduction

LEARNING OUTCOMES

• At the end of this topic, students should be able

to:
a) Describe aromaticity, Kekulé structure and
resonance structure of benzene.

2
 Benzene has strong
pleasant odour.

▪ Arenes = Aromatic compounds

▪ The word aromatic has nothing to do with odour.

Examples:

3
 Discovery of Benzene

1825: Michael Faraday

(British)

▪ Isolated a pure compound of

boiling point 80oC

▪ Empirical formula = CH

▪ Named “bicarburet of hydrogen”

4
 Discovery of Benzene

1866: Friedrich August Kekulé

(German)

▪ Proposed a cyclic
structure for benzene.

5
 Aromatic Compounds

▪ In earlier time, compounds are called aromatic

because of their pleasant odours.

▪ Today, we use the word aromatic to refer to

benzene and its structural relatives.

▪ Aromatic compound is a cyclic conjugated molecule

or ion that is stabilized by π electron delocalisation.

▪ It is characterised by substitution reactions.

6
 Kekulé’s Structure

▪ Kekulé was the first to formulate a reasonable

representation of benzene.

H C H
C
or
C C
H C H
H

▪ The Kekulé structure suggests alternating double

and single carbon-carbon bonds.
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 Resonance Structure

▪ Benzene is actually a resonance hybrid of the

two Kekulé structures.

equivalent to

Resonance hybrid

8
 The circle represents the six pi electrons,
distributed over the six atoms of the ring!

▪ The six pi/π electrons completely delocalised around the ring.

9
▪ All six C atoms and p orbitals are equivalent.
 The Criteria of Aromaticity

▪ 4 structural criteria must be satisfied for compound

to be aromatic.

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 Hückel’s Rule

Cyclic, planar and completely

conjugated compounds that
contain [4n +2] π electron
(n = 0,1,2…..) are said to be
aromatic.

Erich Hückel
(1896-1980)

▪ Planar monocyclic rings with 2, 6, 10, 14 and so forth

π electrons are aromatic.

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 Example of Aromatic Compounds

1. Aromatic compounds with a single ring

Benzene
Benzene is aromatic because:
✓ contains 6π electrons
(obeys Hückel’s Rule)
[4n + 2] π = 6 ✓ Cyclic
n=1 ✓ Planar
✓ has alternate double bonds in the ring.
(completely conjugated)
Aromatic
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2. Aromatic compounds with more than one ring

naphthalene
4n + 2 = 10
n=2
Aromatic

▪ Two benzene rings joined together forms naphthalene.

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3. Aromatic compounds in form of ions

It is a regular heptagonal,
planar, cyclic ion; as well, it
has 6 π-electrons (4n + 2,
where n = 1), which fulfils
Hückel’s Rule of aromaticity
 6.2 Nomenclature of Benzene
and Its Derivatives

LEARNING OUTCOMES
• At the end of this topic, students should be able to:
a) Draw structures and name benzene derivatives
according to the IUPAC nomenclature for:
i. monosubstituted benzenes
ii. disubstituted benzenes
iii. tri- and tetrasubstituted benzenes
b) Apply IUPAC rules to name compounds C6H5 – phenyl
or C6H5CH2 – benzyl as substituents.

16
 Naming Benzene Derivatives
• Many organic molecules contain a benzene ring
with one or more substituents.

• Many common name are

recognized by the IUPAC system.

Example:
CH3
IUPAC: methylbenzene
Common: toluene

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 I. Monosubstituted Benzene

▪ Benzene is the parent name and the substituent

is indicated by a prefix.

F Cl Br

fluorobenzene chlorobenzene bromobenzene

NO2 CH2CH3

nitrobenzene ethylbenzene 18
▪ IUPAC rules allow some common names to be retained.
CH3 OH NH2

toluene phenol aniline

OH H CH3

C O C O C O

benzoic acid benzaldehyde acetophenone

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 II. Disubstituted Benzene

a. Two Same Substituents

▪ Relative position of subsituents are indicated by
prefixes ortho, meta, and para ( o–, m–, and p–)
or by the use of number.
Br
Br Br 1
1 1 2
Br 2
2 3
3 4
Br Br
1,2–dibromobenzene 1,3–dibromobenzene 1,4–dibromobenzene
or or or
o–dibromobenzene m–dibromobenzene p–dibromobenzene

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 NO2 NO2
1
2 NO2 1
2
3
NO2

1,2–dinitrobenzene 1,3–dinitrobenzene
or or
o–dinitrobenzene m–dinitrobenzene
NO2
1
2

3
4
NO2
1,4–dinitrobenzene
or
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p–dinitrobenzene
 b. Two Different Substituents
▪ Select one of the substituent that give new parent
name and numbered as first carbon, C1.

COOH COOH COOH

1 1 1
NO2 2 2
2
3 3
NO2 4
NO2
2–nitrobenzoic acid 3–nitrobenzoic acid 4–nitrobenzoic acid
or or or
o–nitrobenzoic acid m–nitrobenzoic acid p–nitrobenzoic acid
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 The Priority to be the parent name
No. Substituents/functional group Name
1. -COOH Carboxylic acid
2. -SO3H Sulphonic acid
3. -CHO Aldehyde
4. -C≡N Cyano
5. -C=O Ketone
6. -OH Alcohol
7. -NH2 Amino
8. ROR Ether
9. C≡C Alkyne
10. C=C Alkene
11. R Alkyl
12. NO2 Nitro
13. X Halide
 III. Trisubstituted Benzene or More

▪ Position of substituents must be indicated by numbers.

▪ The substituents are listed alphabetically when

writing the name.

Br
1
Cl
Br 1
2 2
Br
3
4
3 I
Br
1,2,4–tribromobenzene 2–bromo–1–chloro–3–iodobenzene

24
▪ C atom bearing the substituent that define the
new parent name is numbered as first carbon, C1.

OH
COOH
1
2 NO2 1
6 2
3 5 3
4 OH
HO 4
NO2
2,4–dinitrophenol 3,5–dihydroxybenzoic acid

3
Br 4 2 CH3 4–bromo–1,2–dimethylbenzene
1 or
CH3 4–bromo–2–methyltoluene
25
 Keep in mind!!!

3
Br 4 2 CH3

1 CH3

4–bromo–1,2–dimethylbenzene correct

4–bromo–o–dimethylbenzene wrong

o–, m– and p– naming system is used

for arenes with 2 substituents only!
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 Phenyl Group (benzene as substituent)

▪ Phenyl = C6H5– = Ph
▪ If alkyl substituent is larger than the ring (more than 6 C),
the compound is named as phenyl-substituted alkane.

▪ Example:
1 CH3
2 3 4 5 6 7
CH–CH2–CH2–CH2–CH2–CH3

2–phenylheptane
27
▪ If the chain is unsaturated (have C═C or C≡C)
or contains important functional group, the
benzene ring is considered as phenyl substituent.

1 2 3 4 2 1
CH2–C C–CH3 CH2–CH2–OH
H H

1–phenyl–2–butene 2–phenylethanol

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 Benzyl Group
CH2—

benzyl group
Examples:

CH2Br CH2OH

IUPAC: (Bromomethyl)benzene IUPAC: phenylmethanol

Common: benzyl bromide Common: benzyl alcohol
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Exercise:

1. Write the IUPAC names for the following compounds:

a) Cl
2-chlorotoluene or o-chlorotoluene
CH 3

b) NH
2
4-nitroaniline or p-nitroaniline

NO 2

c) OH
2-ethylphenol or o-ethylphenol
CH CH
2 3
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 6.3 Chemical Properties of Benzene

LEARNING OUTCOMES
• At the end of this topic, students should be able to:
a) Explain the electrophilic aromatic substitution
reactions of benzene:
i. halogenation
ii. nitration
iii. Friedel-Crafts alkylation
iv. Friedel-Crafts acylation

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 LEARNING OUTCOMES
b) Illustrate the mechanism for electrophilic aromatic
substitution of benzene:
i. halogenation
ii. nitration
iii. Friedel-Crafts alkylation
iv. Friedel-Crafts acylation
c) Explain the following reactions of alkylbenzene:
i. oxidation with hot acidified KMnO4 or K2Cr2O7
ii. halogenation (free radical substitution)

32
 Unusual Reactions Of Benzene

Br2 / CH2Cl2 no addition of Br2

(no decolorization)

KMnO4 / H+ no oxidation
BENZENE
(no decolorization)
H2 / Ni, 300oC
slow addition at high
High pressure temperature and
pressure

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 Reaction Of Benzenes

▪ Involves the benzene ring itself:

- Electrophilic aromatic substitution reaction.
Br
FeBr3
+ Br2

benzene bromobenzene

▪ Involves substituents attached to the ring:

CH2CH2CH2CH3 KMnO /H+ COOH
4Δ

butylbenzene benzoic acid

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Electrophilic Aromatic Substitution Reaction

▪ Most characteristic reaction of benzene.

▪ one H atom is replaced by an electrophile.

H E
+ E+ + H+
electrophile

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 X2, FeX3 X
(X = Cl or Br) + HX Halogenation

conc. HNO3, conc. H2SO4 NO2

50-55oC + H2O Nitration

RCl , AlCl3 R
Friedel-Crafts
(R can rearrange) + HCl Alkylation

O O
RCCl , AlCl3 C–R Friedel-Crafts
+ HCl Acylation
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 General Mechanism
STEP 1 Formation of arenium ion.

H
H H E+

H H
H

H H H
E E E
H + H H H
H
H

H H H + H H + H
H H arenium ion H 37
STEP 2 Loss of H+

H H
E
H H E
+ H
+ H+
H H H H
H H

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 1. HALOGENATION

▪ Reactant: Benzene
▪ Reagent: Halogen (Cl2 or Br2).
▪ Catalyst: Lewis acid (AlCl3, FeCl3 or FeBr3)

+ Br2 no reaction
(decolorization not observed)

Br
FeBr3
+ Br2 + HBr

bromobenzene
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 Function Of Lewis Acid

▪ Increase polarity of halogen molecules.

▪ Produce positive halogen ions (Br+ or Cl+) as electrophile.
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 Mechanism for aromatic chlorination

STEP 1: Formation of electrophile

.. .. .. . .+ -
:Cl + FeCl 3
.. Cl:
.. :Cl Cl FeCl 3
.. ..
Chlorine reacts with :
iron(III) chloride to form
a chloronium ion, Cl+
.. -
Cl+ + :Cl-FeCl
.. 3
41
STEP 2: Electrophile attacks & Formation of Arenium ion

H Cl H Cl H Cl

+ Cl+

The chloronium ion, Cl+

attacks benzene to
form an arenium ion

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 STEP 3: Lost of H+

.. -
+ H . FeCl3
: .Cl ..
.. Cl
..:
Cl
..: + HCl + FeCl3

A proton, H+ is
removed from the
arenium ion to
regenerate the
aromatic ring
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 2. NITRATION

▪ Reactant: Benzene
▪ Reagent: Concentrated HNO3
▪ Catalyst: Concentrated H2SO4
▪ Condition: Temperature 50-55oC

Conc. H2SO4 NO2

+ Conc. HNO3
50-55OC
Nitrobenzene
(yellowish oil)

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 Mechanism for nitration

STEP 1: Formation of nitronium ion (NO2+)

H
..
H-O-NO2 +
.. H-OSO3H .. +-NO2 + HSO4–
H-O

Proton, H+ transfer from

sulphuric acid to the OH group
of nitric acid. H2O + NO2+
Nitric acid dissociates (loss of
water) to form a nitronium ion. nitronium ion

45
STEP 2: Electrophile attacks & Formation of Arenium ion

H NO2 H NO2 H NO2

+ NO2+

The nitronium ion,

NO2+ attacks
benzene to form
an arenium ion

46
STEP 3: Lost of H+

+ HSO4- NO2
H
NO2 + H2SO4

A proton, H+ is
removed from the
arenium ion to
regenerate the
aromatic ring 47
 3. FRIEDEL–CRAFTS ALKYLATION

▪ Reactant: Benzene
▪ Reagent: Haloalkane
▪ Catalyst: Lewis acid (AlCl3, FeCl3 or FeBr3)

R
AlCl3
+ R–Cl + HCl

alkylbenzene

▪ Alkylation =Substitution an alkyl group to benzene.

48
49
• Example:

I. CH3CHCH3

Cl
AlCl3
+ CH3CHCH3 + HCl

CH3
II. CH3CCH3

Br
FeBr3
+ CH3CCH3 + HBr

CH3
50
 Mechanism of alkylation
STEP 1: Formation of Carbocation (electrophile)

CH3 CH3 CH3

CH3C Cl + AlCl3 CH3C Cl AlCl3 CH3C + AlCl4
H H H

Reaction of alkyl
halide with aluminium
chloride to form a
carbocation

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STEP 2: Electrophile attacks & Formation of Arenium ion

CH3 CH3 CH3

H CHCH3 H CHCH3 H CHCH3

+ CHCH3

CH3

The carbocation,
R+ attacks
benzene to form
arenium ion
52
 STEP 3: Lost of H+

CH3

CH3CHCH3
H3CHC H

+ Cl AlCl3 + HCl + AlCl3

A proton, H+ is
removed from the
arenium ion to
regenerate the
aromatic ring 53
 4. FRIEDEL–CRAFTS ACYLATION

▪ Reactant: Benzene
▪ Reagent: Acyl chloride
▪ Catalyst: Lewis acid (AlCl3, FeCl3 or FeBr3)

Example:
O
O
CCH3
+ CH3C—Cl AlCl3
+ HCl
acetyl chloride
acetophenone

54
 Acyl Group

O
RC—
acyl group

Example: O
O
–C—
CH3C—
acetyl group benzoyl group

▪ Acylation = substitution an acyl group to benzene.

55
 Mechanism of acylation

STEP 1: Formation of acylium ion

:O: :O:
..
R–C– Cl: + AlCl3 R–C–Cl–AlCl3
..

Acyl chloride
reacts with
aluminium
: :
R–C+═O R–C≡O+ + AlCl4–
chloride to form
acylium ion
an acylium ion

56
 STEP 2: Electrophile Attacks & Formation of arenium ion

O O O

H C R H C R H C R

+ C O

The acylium ion

attacks benzene to
form arenium ion

57
STEP 3: Lost of H+

O O

R C H C R

+ Cl AlCl3 + HCl + AlCl3

A proton is removed
from the arenium ion
to regenerate the
aromatic ring 58
 Oxidation Of Alkylbenzene
▪ Reactant: Benzene with benzylic H
▪ Reagent: Strong oxidizing agent such as
acidified KMnO4 or Na2Cr2O7
▪ Condition: Heat
▪ Benzylic hydrogen is the hydrogen that attached to
the carbon on a benzene ring.
Observation :
Acidifed KMnO4
benzylic H
– purple to colourless
CH3 Acidified Na2Cr2O7
– orange to green
CH3
CH3 CH(CH3)2
C CH3
CH3
No benzylic H 59
 Example:
CH3 COOH
KMnO4 /H+
∆
toluene benzoic acid

Na2Cr2O7/H+
O2N CH3 O2N COOH
∆
p–nitrotoluene p–nitrobenzoic acid

KMnO4/H+
CH3 CH(CH3)2 HOOC COOH
∆
isopropyl toluene Benzendioic acid 60
 KMnO4/H+
CH3 CH(CH3)2 HOOC COOH
∆

▪ Alkyl group, regardless their chain length are

converted to –COOH.

▪ Compounds without a benzylic H are inert to oxidation.

KMnO4 /H+
CH3 C(CH3)3 HOOC C(CH3)3
∆
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 Halogenation of Alkylbenzene

▪ Reactant: Benzene with alkyl group as substituent

▪ Reagent: Halogen (Cl2 or Br2)
▪ Condition: UV (high temperature)
▪ Mechanism: free–radical substitution.
- Cl or Br replaces H atom of alkyl group.

Example: (dichloromethyl)benzene
CH3 CH2Cl CHCl2 CCl3
Cl2 Cl2 Cl2
UV UV UV

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toluene benzyl chloride (trichloromethyl)benzene
 Carcinogenic Effect

CH3

benzene toluene

▪ Many aromatic compounds are carcinorgenic

and toxic.
▪ Example: benzene, benzo[a]pyrene.
63
▪ At one time, benzene was widely used as solvent.
▪ Studies revealed benzene is carcinorgenic
(can cause cancer).
▪ Replaced by toluene.
64
 benzo[a]pyrene

▪ Benzo[a]pyrene is found in cigarette smoke, automobile

exhaust, and the fumes from charcoal grills.
▪ When ingested or inhaled, it oxidised to carcinogenic
products.
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66
 12.5-20

▪ Benzoic acid, the simplest organic acid, prevent

the growth of many organism. 67
▪ widely used as a food preservative.
68
▪ Fresh wild berries
69