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Chemistry form 6

organic chemistry
chapter 3 :
benzene and its compound

3.0
Introduction
 Organic compounds which contain benzene are categorise as aromatic
compounds (arene)
 For most of simple aromatic compounds, it will end with benzene.
 There are basic type of aromatic compounds, structural formula, common
name and IUPAC name
Structural formula

Molecular formula

Common name

IUPAC name

C6H6

Benzene

Benzene

C7H8

Toluene

Methylbenzene

C8H10

Ortho-xylene

1,2-dimethylbenzene

C6H5OH

Phenol

Phenol

Structural formula

Molecular formula

Common name

IUPAC name

C6H5NO2

Nitrobenzene

Nitrobenzene

C6H5COOH

Benzoic acid

Benzenecarboxylic
acid

C6H5COH

Benzaldehyde

Phenylmethanal

C6H5NH2

Aniline

Phenylamine

C10H8

Naphthalene

Naphthalene

3.1





Nomenclature of aromatic compounds


For simple aromatic compound, it is as describe in the table above
Benzene can also be considered as a branched group.
Branched benzene is called as phenyl (C6H5)
When there are 2 or more substituents on benzene ring, 3 structural
isomers are possible. The substituents may be located by numbering the
atoms of the ring, or may be indicates by prefixes of ortho, meta, or para
Position of the 2 substituents in benzene ring
1,2-position [ortho (o)]
1,3-position [meta (m)]
1,4-position [para (p)]

1,2 dichlorobenzene
ortho-dichlorobenzene

1,3 dichlorobenzene
meta-dichlorobenzene

1,4 dichlorobenzene
para-dichlorobenzene

1,2-dinitrobenzene
o-dinitrobenzene

2-nitrophenol

2-bromotoluene

1,3-dinitrobenzene
m-dinitrobenzene

3-nitrophenol

3-hydroxybenzoic acid

1,4-dinitrobenzene
p-dinitrobenzene

4-nitrophenol

4-methylbenzaldehyde

When 3 or more groups are on benzene ring, a numbering system must


be used to name them. Usually a smaller number of groups will be C1
and the other will be numbered accordingly.
If there are 3 different groups, the one which have a common name will be
given priority. The other 2 will be name and numbered base on
alphabetical order.

2,3-dichlorotoluene

2,4,6-tribromonitrobenzene

5-bromo-3-nitrotoluene

4-chloro-2-ethylphenol

2-hydroxy-5-methylbenzoic
3-chloro-2-phenylbutane
acid

3.2
Reaction of Benzene
 Even though in benzene contain 3 double bonds, but as explained in
Kekules structure, it give an extra stability due to delocalised
electrons in the ring and the resonance structure.
 Thus, benzene usually undergoes substitution reaction instead of
addition reaction.
 The substitution reactions of benzene with an electrophilic reaction
include :
1. Halogenation
2. Alkyation
3. Acylation
4. Nitration
5. Sulphonation
Name of reaction

Reagent used
and condition

Halogenation

Chlorine gas, Cl2 with


AlCl3 as halogen
carrier (catalyst)
----------------Bromine gas, Br2
with FeBr3 as
halogen carrier
(catalyst)

Equation

benzene

halogen

halobenzene

Name of reaction

Friedel Crafts
Alkylation

Friedel Crafts
Acylation

Nitration

Sulphonation

Reagent used
and condition
Haloalkane (R X)
with AlCl3 as
halogen carrier
(catalyst)
Acyl chloride
with AlCl3 as
halogen carrier
(catalyst)
Concentrated
Nitric acid (HNO3)
catalysed by
concentrated
sulphuric acid and
reflux at 55oC

Equation

benzene

haloalkane

benzene

acyl chloride

benzene nitric acid

Concentrated
sulphuric acid
(H2SO4) and heat at
55oC under reflux benzene sulphuric acid

alkylbenzene

nitrobenzene

benzenesulphonic acid

3.2.1
Halogenation
 Chlorine react with benzene under aluminium chloride as catalyst under
room condition

 Bromine reacts with benzene only under the presence of catalyst iron (III)

bromide and some hear

 The mechanism of halogenation of benzene


 Step 1 : Formation of halogen ion (X+) as electrophile using

heterolytic fission reaction. In chlorine, aluminium chloride (electron


deficient compound) is readily to receive lone pair electron (act as
Lewis acid) from chlorine

 Step 2 : Electrophilic attack on benzene ring to form a carbocation.

Cl+ ion attack the benzene ring and the delocalise -electron form a CCl
bond in benzene. This will result a carbocation formed as intermediate and
disturb the ring (cause benzene ring become unstable)

 Step 3 : Proton lost from carbocation. Carbocation transfers a

proton to [AlCl4] and the benzene ring is stabilised back. This results in
the formation of chlorobenzene and HCl.

[As extra note, benzene also react with chlorine in the presence of UV and
some heat to form 1,2,3,4,5,6-hexachlorocyclohexane (addition reaction)]

FriedelCrafts reaction
 Similar to halogenation, Friedel Crafts reaction also required a halogen
carrier to act as catalyst
 Depending on the type of haloalkane used, the halogen carrier is also
different.
 If chloroalkane (RCl) is used, the halogen carrier will be aluminium
chloride (AlCl3)
 If bromoalkaane (RBr) is used, the halogen carrier will be iron (III)
bromide (FeBr3)
3.2.2
Alkylation of Benzene
 When chloroethane (CH3CH2Cl) react with benzene with the presence of
AlCl3, ethylbenzene is produced (C6H5CH2CH3) under room temperature

The mechanism of alkylation is very similar in ways of how halogenation


occur.
Step 1 : Formation of electrophile by heterolytic fission

Step 2 : Electrophile attacking the benzene ring to form carbocation

Step 3 : Proton lost from the unstable carbocation formed earlier.

3.2.3
Acylation of Benzene
 When ethanoyl chloride (CH3COCl) reacts with benzene under the presence of
AlCl3, phenylethanone is produced (C6H5COCH3) at 80oC.

 The mechanism of acylation

Step 1 : Formation of electrophile by heterolytic fission

Step 2 : Electrophile attacking the benzene ring to form carbocation

Step 3 : Proton lost from the unstable carbocation formed earlier

 For nitration and sulphonation of benzene, halogen carrier is not used, as

the reagent used for the reaction is an acid. The mechanism of nitration
and sulphonation are also nearly similar to each other.
3.2.4
Nitration of benzene
 Concentrated nitric (V) acid, HNO3 will only react with benzene under the
presence of a little concentrated sulphuric acid (H2SO4) at 55oC heated
under reflux, to produce nitrobenzene

 The mechanisms of nitration are explained below

Step 1 : Production of nitronium ion, NO2+. In nitration of benzene,


nitric (V) acid act as Bronsted-Lowry base where it accept a proton
donated by sulphuric acid

Step 2 : Electrophile attacked benzene ring to form carbocation.


NO2+ ion attack the benzene ring and delocalise -electron form a CNO2
bond in benzene. This will result a carbocation formed as intermediate and
disturb the ring (cause benzene ring become unstable)

Step 3 : Proton lost from carbocation. Carbocation transfers a proton to


HSO4 and the benzene ring is stabilised back. This results in the formation
of nitrobenzene and H2SO4 (catalyst)

 When nitration is carried out at higher temperature (above

200oC), a 1,3,5-trinitrobenzene can be formed where :

3.2.5
Sulphonation of benzene
 The mechanisms occur for sulphonation of benzene is more or less the
same with nitration of benzene. Unlike nitration, sulphonation does not
required a catalyst as the reagent used, sulphuric acid (H2SO4) act as a
catalyst itself

 Step 1 : Formation of electrophile from sulphuric acid. The

protonation of sulphuric acid when it received one H+ (Bronsted-Lowry


base) from another sulphuric acid

Step 2 : Electrophile attacked benzene ring to form carbocation.

Step 3 : Proton lost from carbocation

Other chemical reaction of benzene


 Unlike alkene, benzene is stabilised by the delocalised electrons. So, it
does not react easily as in alkene. For example, if benzene react with
acidified potassium manganate (VII), KMnO4 (H2SO4)

 When react with hydrogen gas with presence of nickel as catalyst at 180oC,

it form cyclohexane. The reaction is an additional reaction.

benzene
cyclohexane
 Benzene also reacts with propene to give isopropylbenzene (well known as
cumene) which is a starting material to synthesis phenol. Concentrated
H3PO4 serve at catalyst under 250oC

3.3


Influence of Substitution Group on Reactivity and


Orientation of Substituted Benzene
When benzene ring contained a substituents M, the reaction of C6H5M
may be faster / slower compare to benzene

Group of M
Effect of
groups

Ring activating groups


(ortho, para directing)
Cause ring more reactive (
increase rate)

Ring deactivating groups


(meta directing)
Cause ring less reactive (
decrease rate)

CH3

NH2

OH

NO2

COOH

COH

CH2CH3

NH2R

OR

SO3H

COR

X (Cl, Br)

Examples

Type of director
ortho director

para director

meta director

Properties of ring activate group


 Electron donating groups have positive inductive effect (+I)
 When electrophile attacked the benzene ring, carbocation is formed.
 Since a more stable carbocation form faster than a less stable one, when
electrophile attacked at ortho & para position.

As discussed earlier, 3o carbocation is more stable than 2o carbocation.


Using resonance, it is possible for cation to reside at 3o carbon.
Since ortho / para position are more activated when a 30 carbocation
formed, it increase the rate of reaction




Properties of ring deactivate group


Electron withdrawing groups have negative inductive effect (I)
+
Under (I) effect, C M, carbon had already bear partial positive charge
+




Unlike electron donating group, when the cation is placed at the directing
group of electron withdrawing group, it will tend to become unstable
So attacking at meta position is more stable than in ortho / para position.
Still, since in react much slower than in benzene, so electron
withdrawing group is to say deactivate benzene ring and cause the rate
of reaction decrease.

3.4
Reaction of methylbenzene
 Methylbenzene resemble with benzene in many ways. As methylbenzene is
less toxic, is often used as reagent instead of benzene. Moreover, methyl
(CH3) is ring activate group, it react faster and required lesser effort
(lower temperature, concentration electrophile) compare to benzene.
 Unlike benzene, methylbenzene contain an aliphatic (CH3) and aromatic
(C6H6). In other words, methylbenzene undergoes 2 distinctive type of
reaction :
reaction of the methyl group
reaction of the benzene ring
3.4.1 Reaction of the methyl group in methylbenzene

Name of
reaction

Reagent used
and condition

Equation

Acidified
potassium
manganate
(VII)
*Observation : (1) purple colour of potassium manganate
KMnO4 / H2SO4
(VII) decolourised when react with toluene
Oxidation of
methylbenzene
Acidified
potassium
dichromate (VI)
+ H2
K2Cr2O7 /
*Observation : Green colour of potassium dichromate (VI)
H2SO4
changed to orange colour

Chlorination
of
methylbenze
ne

Chlorine gas
under UV light
at room
temperature
* side product of reaction is HCl (g)

 Methylbenzene reacts with strong oxidising agent such as acidified potassium

manganate (VII) [KMnO4 / H+] or acidified potassium dichromate (VI) [K2Cr2O7


/ H+] to form benzoic acid. This is a method to distinguish between
benzene and methylbenzene.
 Under room temp, only H in methyl is substituted by Cl atom.
Step 1 : Initiation Formation of Cl (radical)
Step 2 : Propagation Radical attack methylbenzene to form multiple form of
radical

Step 3 : Termination chlorine radical react and methylbenzene radical

 If temperature increases to 200oC, then, even the H inside benzene ring may

be substituted by Cl.

3.4.2

Reaction of methylbenzene in the benzene ring

Name of
reaction

Reagent used
And condition

Halogenation

Cl2 / AlCl3
or
Br2 / FeBr3

Equation

o-chlorotoluene p-chlorotoluene

Friedel Crafts
Alkylation

CH3Cl / AlCl3
o-xylene

Friedel Crafts
Acylation

p-xylene

CH3COCl / AlCl3
o-ethanoyltoluene p-ethanoyltoluene

Nitration

Conc. HNO3 +
conc. H2SO4
o-nitrotoluene

Sulphonation

p-nitrotoluene

Concentrated
H2SO4
o / p - methylbenzenesulphonic acid

Other types of alkylbenzene synthesis and reaction


 Formation of phenol

 Formation of aniline

 Practice : Suggest the methods of how to synthesis these products from

benzene.
1.

2.

3.

4.

5.

6.

7.

8.

Step 1 :H2SO4 + HNO3  NO2+ + HSO4- + H2O [1]

 Reaction I is oxidation [1], where acidified potassium manganate (VII) [1]

under reflux [1]


 Reaction II is free radical substitution reaction [1], where bromine gas [1]
under the presence of sunlight [1] is required
 Reaction III is electrophilic aromatic substitution reaction [1], where bromine
gas react under the presence of iron (III) bromide [1]

A : chlorine gas under the presence of AlCl3 as catalyst


B : chlorine gas under the presence of UV

Reagent : Using acidified potassium manganate (VII)


Observation : A will decolourised purple colour of acidified KMnO4, while B wont
Equation :

HNO3 catalysed by H2SO4 under reflux


Acidified KMnO4 under reflux
HCl under Sn as catalyst

Step 1 :H2SO4 + HNO3  NO2+ + HSO4- + H2O [1]

Reagent : Using acidified potassium manganate (VII)


Observation : methylbenzene will decolourised purple colour of acidified KMnO4, while
benzene will not.
Equation :
Reagent : Using nitric acid catalysed by concentrated sulphuric acid under reflux
Observation : benzene will turn from colourless to yellow liquid while cycloalkane will
remain colourless
Equation :