Professional Documents
Culture Documents
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
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
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
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
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)
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)
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
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 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
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
When react with hydrogen gas with presence of nickel as catalyst at 180oC,
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
Group of M
Effect of
groups
CH3
NH2
OH
NO2
COOH
COH
CH2CH3
NH2R
OR
SO3H
COR
X (Cl, Br)
Examples
Type of director
ortho director
para director
meta director
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)
If temperature increases to 200oC, then, even the H inside benzene ring may
be substituted by Cl.
3.4.2
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
Formation of aniline
benzene.
1.
2.
3.
4.
5.
6.
7.
8.