Benzene and Substitution Reactions - 2011

Benzene
and
Electrophilic
Aromatic
Substitution
1
1
New Way Chemistry for Hong Kong A-Level 3A

New Way Chemistry for Hong Kong A-Level Book 3A
Aromatic Hydrocarbons (Arenes)

Simplest member : Benzene, C6H6
Characteristic aroma
Alkylbenzene, Cn+6H2n+6
E.g.
CH3
C6H5CH3
2
2
C6H5C2H5


Generally less dense than water
Insoluble in water but soluble in many
organic solvents
3
3


PAHs : Polycyclic aromatic hydrocarbons
Fused aromatic rings
4
4


No heteroatoms
N
B
5
5
Not PAH


PAHs : Polycyclic aromatic hydrocarbons
Sources : - incomplete combustion of
wood, coal, diesel, fat, or tobacco
Q.38
6
6
benzocyclobutadiene

PAHs : Polyaromatic hydrocarbons
Toxic and carcinogenic

Benzo(a)pyrene : - first carcinogen discovered
Found in : - tobacco smoke,
- char-grilled food
- burnt toast,
- edible oils
7
7

Preparation of
Benzene
8
8

Destructive Distillation
Distillation of
of Coal
Coal
1.1. Destructive
9
9
Gives coal gas, ammoniacal liquor,

coal tar and coke as products
The coal tar produced is a mixture

of many organic compounds (mainly
aromatic ones)
benzene and methylbenzene can be

obtained by fractional distillation
Destructive Distillation
Distillation of
of Coal
Coal
1.1. Destructive
10
10
A laboratory
set-up of the
destructive
distillation of
coal
Industrial Preparation
2. Catalytic
Catalytic trimerization
trimerization of
of ethyne
ethyne
2.
organonickel catalyst
3 HC
11
11
CH
70oC, under pressure

Industrial Preparation
3. Catalytic
Catalytic Reforming
Reforming of
of Petroleum
Petroleum
3.
Converts alkanes and cycloalkanes

into aromatic hydrocarbons
C6H14
Pt
C6H6 + 4H2
500 oC, 10 20 atm
12
12

Laboratory Synthesis
Decarboxylation of
of Sodium
Sodium Salt
Salt of
of Benzoic
Benzoic Acid
Acid
1.1. Decarboxylation
When sodium benzoate is fused with

sodium hydroxide
the carboxylate group is removed
13
13
volatile
Benzene is separated by fractional distillation
2. Reduction
Reduction of
of Phenol
Phenol
2.
Passing phenol vapour over heated zinc

dust (reducing agent)
produce benzene and zinc(II) oxide
volatile
14
14
Benzene is separated by fractional distillation

Reactions of
Benzene
15
15

Reactivity of Benzene
Unreactive towards addition reactions due to
stabilization of the system by delocalization
of -electrons
16
16

Not oxidized by KMnO4
17
17

Br2 / HBr / H 2O
Resistant to electrophilic
addition at room
conditions
18
18

Resistant to catalytic
hydrogenation
19
19

Addition reactions occur only under drastic

conditions.
excess H2, high T&P
Ni or Pt or Pd
20
20

Incomplete combustion
due to high C content
Occur only under

drastic
conditions
No reaction when cold.

slow sulphonation when
heated.
Br2 / HBr / H 2O
No
reaction
21
21

The -electron cloud is susceptible to

electrophilic attack.
Substitution is preferred to addition since
the former retains aromaticity.
Electrophilic aromatic substitution (SE)
22
22

(Halogenation)
NO2
(Nitration)
conc. H2SO4 or fuming H2SO4

SO3H
(Sulphonation)
O
R
R
X : Cl, Br
(Alkylation)
X
O
(Acylation)
23
23

Electrophilic Aromatic Substitution

Reactions
E+ : electrophile
24
24

General Reaction
Reaction Mechanism
Mechanism
General
Step 1:
25
25
Rate determining step

General Reaction
Reaction Mechanism
Mechanism
General
Stabilized by delocalization of
electrons
26
26

General Reaction
Reaction Mechanism
Mechanism
General
Step 2:
The carbocation loses a hydrogen ion

forms the substitution product
27
27

Halogenation
1.1. Halogenation
Cl
No
apparent
reation
(slow)
HBr
(fast)
Br
Catalysts : AlCl3, FeCl3 or FeBr3
28
28
HCl

Halogenation -- Mechanism
Mechanism
1.1. Halogenation
Step 1:
The catalyst (FeBr3) combines with
bromine to give a complex
Br
29
29
Br
FeBr3

Br [FeBr4]
Step 2:
Formation of carbocation intermediate
Rate determining step

+
30
30
Br [FeBr]
Br
Br
Br
Stabilized by delocalization of -electrons

Step 3:
The catalyst (FeBr3) is regenerated
Fumes of HBr(g) are produced, indicating

substitution rather than addition has occurred.
31
31

2. Nitration
Nitration
2.
32
32
Benzene reacts readily with a mixture

of conc. HNO3 and conc. H2SO4
Conc. H2SO4 increases the rate of

reaction by increasing the concentration
of the electrophile, NO2+
H2SO4
acid
HO
base
O
O
H2O
electrophile
2HNO3
33
33
NO3 + H2O + NO2+

NO2
NO2
conc. HNO3
conc. H2SO4, 95oC
NO2
NO2
NO2
conc. HNO3
conc. H2SO4, 110oC
NO2
Optional
34
34
O2N
NO2
meta-directing

Q.39
H2SO4 + HNO3
NO2+ + H2O + HSO4

O
35
35
O
N

O
N
36
O
N
O
N
HSO4
NO2
N
H
+ H2SO4
37
3. Sulphonation
Sulphonation
3.
(H2SO4 + SO3)
Benzene reacts with fuming sulphuric
acid at room temp
form benzenesulphonic acid
38
38

3. Sulphonation
Sulphonation
3.
Sulphonation is a reversible process
By heating an aqueous solution of

benzenesulphonic acid to above 100 oC
benzene and sulphuric acid are formed
heat
39
39

Q.40
H2SO4 + H2SO4
SO3 + H3O+ + HSO4

O
S
O
40
40
O
H

O
O
O
H
41
O
O
O
H
O
H
HSO4
O
O
SO3H
SO3
H+
+ H2SO4
42
4. Friedel-Crafts
Friedel-Crafts Alkylation
Alkylation
4.
When benzene is warmed with a

haloalkane in the presence of AlCl3 as a
catalyst
alkylbenzene is formed
43
43

4. Friedel-Crafts
Friedel-Crafts Alkylation
Alkylation
4.
Important starting step in the manufacture
of styrene, phenol and detergents
The alkyl group introduced activates the ring
towards further alkylation by +ve I-effect.
Friedel-Crafts alkylation is not a good way
to prepare alkylbenzene.
44
44

deactivating
R
Cl
AlCl3
Friedel-Craft
acylation
45
45
CH2
Hg/Zn
conc. HCl
Clemensen
reduction

Devise a reaction pathway of not more than

four steps for the following conversion.
CH3
COOH
6B 09/07/2011
46
46
O
COOH
C
C
sodalime
fusion
Cl
AlCl3
CH3
47
47
Chlorination
Bromination or Friedel-Craft reaction
Soda lime to absorb

HBr or HCl fumes
Br2, RCl or RCOCl
or AlCl3
48
48

Q.41
electrophile
CH3Cl + AlCl3 [CH3]+[AlCl4]
49
49

AlCl4
H
CH3
H
C
H
two more structures
CH3
+ HCl + AlCl 3
50
Q.42(a)
2C6H6 + X
AlCl3
C6H5CH2C6H5 + 2HCl
X : CH2Cl2
51
51

CH2Cl
CH2Cl2
CH2
AlCl3
AlCl3
(excess)
-CH2Cl deactivate the ring

Susceptibility to SE reaction :
52
52

CH2Cl
>
Q.42(b)
3C6H6 + Y
AlCl3
(C6H5)3CH + 3HCl
Y : CHCl3
53
53

CHCl2
CHCl3
CHCl
AlCl3
AlCl3
(excess)
AlCl3
C
54
54

Q.42(c)
2C6H6 + Z
AlCl3
C6H5CH2CH2C6H5 + 2HCl
Z : CH2ClCH2Cl
55
55

ClH2C
ClH2C
CH2Cl
AlCl3
AlCl3
(excess)
56
56

Industrial preparation of toluene

CH3
1.
Coal tar
Fractional
distillation
CH3
2.
57
57
Petroleum
Fractional
distillation
CH3
catalyst
high T & P

3H2
Laboratory Preparation of Methylbenzene

1. Friedel-Crafts acylation of benzene
followed by Clemensen reduction.
2.Friedel-Crafts alkylation of benzene is not
recommended as further alkylation will
take place giving a mixture of
alkylbenzenes that are difficult to be
separated.
58
58

Reactions of methylbenzene and Other

Alkylbenzenes
1. Electrophilic aromatic substitution rxs
more susceptible to electrophilic attacks
alkyl groups activate the ring by positive
inductive effect.
59
59
2. Reactions of the side chain

(a) Free radical substitution vs
electrophilic substitution at the ring
CH2Cl
CH3
CHCl2
CCl3
+
CH3
CH3
Cl
Electrophilic
substitution
Cl
60
60
Free radical
substitution

Benzylic hydrogens are much more susceptible

to free radical substitution than hydrogens at
other positions.
Br
CH
H2C
Br
Br
CH3
CH3
Major
products
CH3
H2C
CH2Br
H2C
CHBr2
61
61

H2C
CBr3
(b)
Oxidation at the benzylic carbon

R
CH3
CH
COOH
H2
C
CR3
Absence of
benzylic H
62
62

If alkaline KMnO4 is used, the resulting

mixture must be acidified in order to obtain
the benzoic acid.
CH3
COO-
KMnO 4 / OH-
COOH
H+
heat
Or,
CH3
COOH
1. KMnO 4 / OH-, heat

2. H+
63
63

Structural determination of isomeric alkylbenzene

H3C
CH3
CH3
CH2CH3
CH3
b.p. 144oC
b.p. 139oC
alkylbenzenes
with very close
boiling points
CH3
b.p. 138oC
b.p. 136oC
CH3
COOH
COOH
C8H10
COOH
COOH
COOH
m.p. 231 C
m.p. 348 C
COOH
acids with
different
melting points
m.p. 300oC
m.p. 122oC
COOH
64
64

Structural determination of isomeric alkylbenzene

H3C
CH3
CH3
CH2CH3
CH3
b.p. 144oC
b.p. 139oC
CH3
alkylbenzenes
with very close
boiling points
b.p. 138oC
b.p. 136oC
CH3
COOH
COOH
COOH
COOH
COOH
m.p. 231 C
m.p. 348 C
COOH
acids with
different
melting points
m.p. 300oC
m.p. 122oC
COOH
65
65

Q.43(a)
O
COOH
1. MnO4- / OH2. H+
66
66

C
HO
CH3
Q.43(b)
Terminal alkene gives CO2

COOH
1. MnO4- / OH-
2. H+
COOH
COOH
1. MnO 4- / OH2. H+
COOH
COOH
1. MnO 4- / OH2. H+
67
67
HOOC

+ H 2O
CO2
Q.43(b)
-
1. MnO4 / OH
2. H+
68
68

COOH
Q.43(b)
COOH
1. MnO4- / OH2. H+
COOH
1. MnO 4- / OH2. H+
69
69

COOH
COOH
Q.43(b)
1.
MnO 4-
COOH
/ OH
2. H+
1. MnO4 / OH
2. H+
70
70

COOH
Q.43(c)
1. MnO4- / OH2. H+
71
71

CO2
+ H2 O
The END
72
72

29.2 Nomenclature of the Derivatives of Benzene (SB p.191)

Back
Draw the structural formula for each of the

following compounds:
(a) 1,3,5-Trichlorobenzene
(b) 2,5-Dibromophenol
(c) 2,4-Dinitrobenzoic acid
(a)
73
73
(b)
Answer
(c)

Give the IUPAC name for each of the following

compounds:
(a)
(a) 1,2-Dimethylbenzene
(b) 1-Methyl-2-nitrobenzene or 2nitrotoluene
(b)
74
74

Answer

Back
Give the IUPAC name for each of the following

compounds:
(c)
(c) 3-Bromo-5-chlorobenzoic acid

(d) 4-Bromo-2,6-dinitrophenol
(d)
75
75

Answer
29.3 Structure of Benzene and Aromaticity (SB p.195)
The basic structural requirement for aromatic

compounds is that the molecule must be planar,
cyclic and with (4n + 2) electrons delocalized in
the ring. n must be a natural number (i.e. n = 1, 2, 3, and
so on).
There are aromatic compounds without benzene ring.
An example is the 1,3-cyclopentadienyl anion. Can you
draw its structure and explain its aromaticity?
Answer
76
76

29.3 Structure of Benzene and Aromaticity (SB p.195)

Back
Cyclopentadienyl anion is an aromatic anion. It has six

electrons delocalized over a completely conjugated planar
monocyclic system of five sp2 hybridized carbon atoms.
Cyclopentadienyl anion
77
77

29.4 Physical Properties of Aromatic Hydrocarbons (SB p.197)
PAHs are formed from partial combustion and pyrolysis

of aromatic compounds. They are in common occurrence
in our environment. List some important uses of
aromatic hydrocarbons and how they release PAHs to
our environment.
Answer
78
78

29.4 Physical Properties of Aromatic Hydrocarbons (SB p.197)
Aromatic hydrocarbons are the raw materials for the manufacture of

monomers and plasticizers in polymers, commonly used as
solvents and important constituents of lead-free gasoline.
Incomplete combustion and pyrolysis process favour the production
of PAHs. These compounds are encountered abundantly in the
atmosphere, soil and elsewhere in the environment from sources
that include engine exhaust, wood stove smoke, cigarette smoke
and charbroiled food. Coal tar and petroleum residues such as road
and roofing asphalt have high levels of PAHs.
Back
79
79

29.6 Reactions of Benzene (SB p.203)

Back
Complete each of the following by supplying the

missing reactant or product as indicated by the
question mark:
(a)
(a)
(b)
(b) conc. H2SO4, conc. HNO3

(c) fuming H2SO4
(c)
Answer
80
80

(a) One mole of benzene reacts with three

moles of chlorine under special conditions.
What are the conditions required for the
reaction?
Answer
(a) UV radiation or diffuse sunlight must
be present for the free radical addition
reaction to take place.
81
81

(b) Draw the structure of the reaction product

in (a).
Answer
(b)
82
82

(c) Methylbenzene undergoes two different

types of chlorination reaction by different
mechanisms. Compare the two different
types of chlorination reaction in terms of
reaction conditions as well as the products
formed.
Answer
83
83


Back
(c) The two different types of chlorination reaction of methylbenzene

are:
Type I: free radical substitution reaction
Type II: electrophilic aromatic substitution reaction
84
84

Comparison of some reactions of cyclohexane,

cyclohexene and methylbenzene
Reaction Cyclohexane Cyclohexene (an Methylbenzen
(a saturated
unsaturated
e (an aromatic
alicyclic
alicyclic
hydrocarbon)
hydrocarbon)
hydrocarbon)
Action of
bromine in
1,1,1trichloroethane (in
dark)
85
85
No reaction
Bromine is
decolourized and
no hydrogen
bromide is evolved

No reaction
with bromine
alone. In the
presence of
iron(III)
bromide,
bromine is
decolourized
and hydrogen
bromide fumes
are evolved

(a saturated
unsaturated
e (an aromatic
alicyclic
alicyclic
hydrocarbon)
hydrocarbon)
hydrocarbon)
Action of
hydrogen
(with
nickel
catalyst)
86
86
No reaction
One mole of
cyclohexene
reacts with one
mole of hydrogen
at room
temperature

One mole of
methylbenzene
reacts with
three moles of
hydrogen at
high
temperature

(a saturated
unsaturated
e (an aromatic
alicyclic
alicyclic
hydrocarbon)
hydrocarbon)
hydrocarbon)
Action of
acidified
potassium
manganat
e(VII)
87
87
No reaction
Acidified
potassium
manganate(VII)
solution is
decolourized

No reaction

(a saturated
unsaturated
e (an aromatic
alicyclic
alicyclic
hydrocarbon)
hydrocarbon)
hydrocarbon)
Action of
concentrat
ed nitric
acid and
concentrat
ed
sulphuric
acid
88
88
No reaction
Cyclohexene is
oxidized and the
colour darkens

A yellow liquid
is formed

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Benzene

New Way Chemistry for Hong Kong A-Level 3A

Aromatic Hydrocarbons (Arenes)

New Way Chemistry for Hong Kong A-Level 3A

Aromatic Hydrocarbons (Arenes)

New Way Chemistry for Hong Kong A-Level 3A

Aromatic Hydrocarbons (Arenes)

New Way Chemistry for Hong Kong A-Level 3A

Aromatic Hydrocarbons (Arenes)

New Way Chemistry for Hong Kong A-Level 3A

Aromatic Hydrocarbons (Arenes)

New Way Chemistry for Hong Kong A-Level 3A

PAHs : Polyaromatic hydrocarbons

Toxic and carcinogenic

New Way Chemistry for Hong Kong A-Level 3A

New Way Chemistry for Hong Kong A-Level 3A

Gives coal gas, ammoniacal liquor,

The coal tar produced is a mixture

benzene and methylbenzene can be

70oC, under pressure

New Way Chemistry for Hong Kong A-Level 3A

Converts alkanes and cycloalkanes

500 oC, 10 20 atm

New Way Chemistry for Hong Kong A-Level 3A

When sodium benzoate is fused with

Passing phenol vapour over heated zinc

Benzene is separated by fractional distillation

New Way Chemistry for Hong Kong A-Level 3A

New Way Chemistry for Hong Kong A-Level 3A

Not oxidized by KMnO4

New Way Chemistry for Hong Kong A-Level 3A

New Way Chemistry for Hong Kong A-Level 3A

New Way Chemistry for Hong Kong A-Level 3A

Addition reactions occur only under drastic

New Way Chemistry for Hong Kong A-Level 3A

Occur only under

No reaction when cold.

New Way Chemistry for Hong Kong A-Level 3A

The -electron cloud is susceptible to

New Way Chemistry for Hong Kong A-Level 3A

conc. H2SO4 or fuming H2SO4

New Way Chemistry for Hong Kong A-Level 3A

Electrophilic Aromatic Substitution

New Way Chemistry for Hong Kong A-Level 3A

Rate determining step

New Way Chemistry for Hong Kong A-Level 3A

New Way Chemistry for Hong Kong A-Level 3A

The carbocation loses a hydrogen ion

New Way Chemistry for Hong Kong A-Level 3A

Catalysts : AlCl3, FeCl3 or FeBr3

New Way Chemistry for Hong Kong A-Level 3A

New Way Chemistry for Hong Kong A-Level 3A

Formation of carbocation intermediate

Rate determining step

Stabilized by delocalization of -electrons

The catalyst (FeBr3) is regenerated

Fumes of HBr(g) are produced, indicating

New Way Chemistry for Hong Kong A-Level 3A

Benzene reacts readily with a mixture

Conc. H2SO4 increases the rate of

NO3 + H2O + NO2+

New Way Chemistry for Hong Kong A-Level 3A

NO2+ + H2O + HSO4