Chapter 2_4:

Aromatic Hydrocarbon
Prepared by:
Arbanah Muhammad
arbanah@micet.unikl.edu.my

TOPICS
Benzene
Naming benzene derivatives
Mono Substituted Benzene
Di substituted Benzene
Three Or More Substituents

Phenyl
Preparation of Benzene
Reaction of Benzene

P/S: IF more than one Lewis structure can be drawn, the molecule or ion
is said to have resonance

Kekule structure
Kekule suggested that the carbon atoms of
benzene ring are in the ring, bonded to each
other by alternating single and double bonds.
H
H

OR
H

Kekule
Structure

H
H

However,
benzene
reaction.

Kekule structure cant explain why

molecules are not undergoes addition

Resonance Structure
In 1930s , Linus Pauling introduced the concept
of hybrid orbital and resonance.
The real structure of benzene is the resonance
hybrid from two Kekul structure as shown below:

Hybrid resonance
structure

AROMATIC COMPOUNDS
Nomenclature of benzene
and its derivatives

Arenes = aromatic compounds:

the word aromatic has nothing to do with odour.

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
Common: toluene
IUPAC:
methylbenzene

MONO SUBSTITUTED BENZENE

Benzene is the parent name and the substituent
is indicated by a prefix.
Cl

fluorobenzene

Br

chlorobenzene
NO2

nitrobenzene

bromobenzene
CH2CH3

ethylbenzene

IUPAC rules allow some common names

to be retained.
CH3

OH

Toluene

NH2

phenol

COOH

benzoic acid

aniline

CHO

benzaldehyde

DISUBSTITUTED BENZENE
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

Br

2
3

1,2dibromobenzene
or
odibromobenzene

2
3
4

Br

1,3dibromobenzene
or
mdibromobenzene

Br
1,4dibromobenzene
or
pdibromobenzene

NO2

NO2
NO2

2
3

1,2dinitrobenzene
or
odinitrobenzene

1,3dinitrobenzene
or
mdinitrobenzene

NO2

NO2

2
3
4

NO2
1,4dinitrobenzene
or
pdinitrobenzene

DISUBSTITUTED BENZENE
Two Different Substituents

Select one of the substituent that give

new parent name and numbered as C1.
COOH
COOH

1
NO2

3
NO2
2nitrobenzoic acid
or
onitrobenzoic acid

COOH

3nitrobenzoic acid
or
mnitrobenzoic acid

NO2
4nitrobenzoic acid
or
pnitrobenzoic acid

THREE OR MORE SUBSTITUENTS

Position of substituents must be indicated by
numbers.
The substituents are listed alphabetically when
writing the name.
Cl

Br

2 Br
3
4

Br
1,2,4tribromobenzene

Br
I
2bromo1chloro3iodobenzene

C atom bearing the subtituent that define the

new parent name is numbered as C1.
OH

COOH

2 NO2
6
3

HO

NO2

OH

3,5dihydroxybenzoic acid

2,4dinitrophenol

Br

CH3

CH3

4bromo1,2dimethylbenzene

Keep in mind!
Br

CH3

CH3

4bromo1,2dimethylbenzene

correct

4bromoodimethylbenzene

o, m and p naming system is used for arenes with 2

substituents only!

PHENYL GROUP
Benzene ring as substituent.
If alkyl substituent is larger than the ring
(more than 6 C), the compound is named as
phenyl-substituted alkane.
1 CH2
2

CHCH2CH2CH2CH2CH3
2phenylheptane

Phenyl = C6H5 = Ph

If the chain is unsaturated (have CC or CC)

or contains important functional group, the
benzene ring is considered as
phenyl substituent.

CH2C

3 4

CCH3

1phenyl2butene

CH2CH2OH

2phenylethanol

BENZYL GROUP
CH2

phenyl group

benzyl group

CH2Br

CH2OH

benzyl bromide

benzyl alcohol

PROPERTIES OF BENZENE
Physical Properties
Benzene is a colourless, volatile, highly flammable and
non-polar liquid.
Its physical properties include:

Molecular
weight
Melting point
Boiling point
Solubility

78.11
5C
80.1C
Slightly soluble in water
Very soluble in organic
solvents and oil

Preparation of Benzene

Reaction of Benzene
1.HALOGENATION, X2
2.NITRATION, NO3
3.FRIEDAL CRAFT AKYLATION,
RCl
4.FRIEDAL CRAFT ACYLATION,
RC=0Cl

X2, FeX3
(X = Cl Br)

HNO3

X
+ HX

NO2

H2SO4

RCl , AlCl3

+ H2O

nitration

+ HCl

Friedel-Crafts
Alkylation

(R can rearrange)
O
RCCl , AlCl3

halogenation

O
CR
+ HCl

Friedel-Crafts
Acylation

1. Halogenation
The reaction occurs in the presence of Lewis acid
catalyst such as Fe, FeX3,AlX3 ( X is Cl or Br)
The catalyst polarized the halogen molecule & acts as
an electrophile
X

+ X2

Fe or FeX3

EXAMPLE: Bromination rxn

Br

+ Br2

FeBr3

+ HBr + FeBr3

2. Nitration
Reagents used for nitration of benzene are conc.
nitric acid and conc. sulphuric acid as catalyst.
The rxn mixture is heated to yield nitrobenzene.

+ HNO3

H2SO4 (conc.)
Heat (50-55C)

NO2

+ H2O

3. Friedel-Crafts Alkylation
This rxn used Lewis acid as a catalystsuch as AlCl 3.
R

+
Benzene

RX

AlX3

+ HX

Alkyl halides

Alkylbenzene

EXAMPLE:
CH2CH3

+ CH3CH2Cl
Benzene

Chloroetane

AlCl3

+ HCl
Ethylbenzene

4. Friedel-Crafts Acylation
Introducing acyl group R

O
Two common acyl groups are the acetyl group and the
benzoyl group

O
CH3C
acetyl group
(ethanoyl group)

O
C
Benzoyl group

In the presence of anhydrous aluminium chloride, benzene

react with acyl group to form ketone.

For example:

CH3C Cl

acetyl chloride

AlCl 3
80C

C CH3
ketone

HCl

Effect of substituents group on

the benzene ring
1. A substituted group that is already present will have
the following effects on the subsequent
substitutions
on the ring.
Change the reactivity of benzene ring @ rate of
rxn
The orientation of the incoming substituents.

Group that effect the reactivity

of benzene ring
1. Activating group
is the electron donating group
that cause the ring to be more
reactive than benzene.

2. Deactivating group
is the electron withdrawing group
that cause the ring to be less
reactive than benzene.

Group that effect the orientation

1. Ortho-para director
The group that directs an electrophile to
the ortho-para position.

2. Meta director
The group that directs an electrophile to
the meta position

Common substituent groups and their effect on

increasing reactivity

Electrophilic Aromatic Subtituent:

-NH2, -NHR, -NR2

-OH
-OR
-NHCOCH3
-C6H5
-R
-H
-X
-CHO, -COR
-SO3H
-COOH, -COOR
-CN
-NR3+
-NO2

ortho/para directors

meta directors

Groups

Activating

Ortho-para
director
-NH2, -NHR,
-NR2,
-OH,
-OR,
C6H5-, R-

Deactivating Halogen

Meta director

-NO2,
-COOH, -CN,
-COOR, -SO3H,
-CHO, -COR

EXAMPLE:
What is the products of the rxn if these given
Compound goes nitration process?
CH3
CH3

NHO3 / H2SO4

methylbenzene
Ortho-para director

NO2

heat

CH3
and
NO2

NO2
NO2
nitrobenzene
meta director

NHO3 / H2SO4
heat

NO2

ADDITIONAL PROBLEMS
1. Write structural formulas for each of the following;
CH3

Br

OH

Br

O 2N

3,5-dinitrophenol

o-dibromobenzene

Br

NO2

p-bromotuluene
H3C

CH2Br

Benzyl bromide

CH3
CH3

tert-buthylbenzene