Professional Documents
Culture Documents
Chapter 5 Aromatic
Chapter 5 Aromatic
Chapter 5 Aromatic
AROMATIC COMPOUNDS
(BENZENE AND TOLUENE)
1
Aromatic compounds
2
Structure of Benzene
Any structure for benzene must account for the following facts:
1. It contains a six-membered ring and three additional degrees of
unsaturation.
2. It is planar.
3. All C—C bond lengths are equal.
The Kekulé structures satisfy the first two criteria but not the third,
because having three alternating π bonds means that benzene
should have three short double bonds alternating with three longer
single bonds.
5
The Structure of Benzene
• In benzene, the actual bond length (1.39 Å) is intermediate between the carbon—
carbon single bond (1.53 Å) and the carbon—carbon double bond (1.34 Å).
6
Delocalization and Resonance Structures Rules
7
Delocalization and Resonance Structures Rules
8
Resonance Structure
• Resonance theory: the structure of benzene is a resonance
hybrid structure of two Kekulé cononical forms.
9
• Hexagonal ring – 6 carbon-carbon bonds are
equal.
• Circle – delocalised electrons of the benzene
ring
10
CRITERIA OF AROMATIC COMPOUNDS
13
Naming Aromatic
Compounds
14
• A substituted benzene is derived by replacing one
or more of benzene’s hydrogen atoms with an
atom or group of atoms.
• A monosubstituted benzene has the formula
C6H5G where G is the group that replaces a
hydrogen atom.
• All hydrogens in benzene are equivalent.
• It does not matter which hydrogen is replaced by
G.
15
Monosubstituted
Benzenes
16
Nomenclature of Benzene Derivatives
• To name a benzene ring with one substituent, name the substituent and add the
word benzene.
• Many monosubstituted benzenes have common names which you must also
learn.
17
• Some monosubstituted benzenes are
named by adding the name of the
substituent group as a prefix to the word
benzene.
• The name is written as one word.
nitrobenzene ethylbenzene
18
• Certain monosubstituted benzenes have special
names.
• These are parent names for further substituted
compounds.
hydroxy
methyl group group
toluene phenol
19
carboxyl group
amino group
benzoic acid
aniline
20
Disubstituted Benzenes
21
• Three isomers are possible when two substituents
replace hydrogen in a benzene molecule.
22
Nomenclature of Benzene Derivatives
• There are three different ways that two groups can be attached to a benzene ring,
so a prefix—ortho, meta, or para—can be used to designate the relative position
of the two substituents.
ortho-dichlorobenzene
(1,2-dichlorobenzene)
mp –17.2oC, bp 180.4oC
24
meta disubstituted benzene
substituents on adjacent carbons
meta-dichlorobenzene
(1,3-dichlorobenzene)
mp –24.82oC, bp 172oC
25
para disubstituted benzene
substituents are on opposite sides
of the benzene ring
para-dichlorobenzene
(1,4-dichlorobenzene)
mp 53.1, bp 174.4oC
26
When one substituent corresponds to a monosubstituted
benzene with a special name, the monosubstituted
compound becomes the parent name for the
disubstituted compound.
phenol 3-nitrophenol
27
When one substituent corresponds to a
monosubstituted benzene with a special name, the
monosubstituted compound becomes the parent
name for the disubstituted compound.
toluene 3-nitrotoluene
28
Tri- and Polysubstituted
Benzenes
29
• When a benzene ring has three or more
substituents, the carbon atoms in the ring are
numbered.
• Numbering starts at one of the substituent groups.
• The numbering direction can be clockwise or
counterclockwise.
• Numbering must be in the direction that gives the
substituent groups the lowest numbers.
30
clockwise 6-chloro
numbering
1-chloro
6
5 1
4 2
4-chloro
3
1,4,6-trichlorobenzene 31
counterclockwise 2-chloro
numbering
chlorine 1-chloro
substituents
have lower 2
numbers 3 1
4 6
4-chloro
5
1,2,4-trichlorobenzene 32
• When a compound is named as a derivative of
the special parent compound, the substituent of
the parent compound is considered to be C-1 of
the ring.
33
1
6 2
1
6 2 5 3
4
5 3
4
toluene
2,4,6-
trinitrotoluene
(TNT) 34
• When the hydrocarbon chain attached to the
benzene ring is small, the compound is named as
benzene derivative.
• Example:
CH2CH3
ethylbenzene
35
Naming compounds that cannot be easily
named as benzene derivatives
diphenylmethane
4-phenyl-2-pentene
36
The phenyl group, C6H5-
CH2
phenyl benzyl
CH3
CH2(CH2)5CH3 C CH2 CH3
Br
1-phenylheptane 2-bromo-2-phenylbutane
38
PHYSICAL PROPERTIES OF BENZENE AND ITS
DERIVATIVES
• Benzene derivatives tend to be more symmetrical than
similar aliphatic compounds, and pack better into
crystals and have higher melting points.
• Density:
- Slightly dense than non-aromatic analogues, but still
less dense than water.
- halogenated benzenes are denser than water.
• Insoluble in water
• Boiling points depends on the dipole moments of
compounds.
39
REACTION OF BENZENE
ELECTROPHILIC SUBSTITUTION REACTIONS OF
BENZENE
40
Mechanism of electrophilic substitution
of benzene
Step 1: Electrophilic addition of the benzene ring
H
+
E
E slow
41
ELECTROPHILIC SUBSTITUTION REACTIONS
a) Halogenation
H X
X2 H2SO4 HX
or FeX3
halobenzene
b) Nitration
H NO2
H2SO4 2H2O
HNO3
nitrobenzene
c) Sulphonation
H SO3H
H2SO4
SO3
benzenesulphonic acid 42
ELECTROPHILIC SUBSTITUTION REACTIONS
d) Friedel-Crafts alkylation
H CH3
AlCl3
CH3Cl HCl
toluene
e) Friedel-Crafts acylation O
H C CH3
O AlCl3
HCl
CH3CCl
acetophenone
43
Reagents, electrophiles and catalysts in
electrophilic substitution reactions
bromobenzene
c) Iodination
I
45
iodobenzene
MECHANISM: BROMINATION OF BENZENE
Step 1: Formation of a stronger electrophile
Br Br FeBr3 Br Br FeBr3
Br2.FeBr3 intermediate
(a stronger electrophile than Br2)
FeBr4-
H NO2
slow
NO2+
H NO2 NO2
H H
CH3 C Cl AlCl3 CH3 C -
AlCl4
CH3
CH3
carbocation (electrophile)
Step 2: Formation of an arenium ion
H H CH(CH3)2
C CH3
CH3
arenium ion
O
O H C CH3
CH3 C
50
EFFECTS OF SUBSTITUENTS ON THE
REACTIVITY OF ELECTROPHILIC
AROMATIC SUBSTITUTION
• Substituent group present in the benzene ring can
influence the rate of reaction of further substitutions.
• Electron-donating groups make the ring more reactive
(called activating groups) thus influence the reaction
become faster.
• Electron-withdrawing groups make the ring less reactive
(called deactivating groups) thus influence the reaction
become slower.
51
EFFECTS OF SUBSTITUENTS ON THE
ORIENTATION OF ELECTROPHILIC
AROMATIC SUBSTITUTION
52
Effetcs of substituent groups on the benzene ring
53
Example:
54
Example:
major product
minor products
55
REACTIONS OF BENZENE
DERIVATIVES
• Alkylbenzene such as toluene (methylbenzene)
resembles benzene in many of its chemical
properties.
• It is preferable to use toluene because it is less
toxic.
• The methyl group activates the benzene nucleus.
• Toluene reacts faster than benzene in all
electrophilic substitutions.
56
Reactions
of toluene
Electrophilic
substitutions
Substitution - Halogenation
Addition reaction
Oxidation
-halogenation - Nitration -hydrogenation
- Friedel-Crafts reactions
- Sulfonation
57
58
SIDE-CHAIN REACTIONS
59
OXIDATION REACTION OF ALKYLBENZENE
O
+
CH2 R hot, conc., KMnO4/H C OH
reflux
examples:
O
+
hot, conc., KMnO4/H
CH3 C OH
reflux
O
+
CH2 CH3 hot, conc., KMnO4/H C OH
reflux
(chloromethyl)benzene
CH2 Cl CHCl2
uv light
Cl2 HCl
(dichloromethyl)benzene
CHCl2 CCl3
uv light
Cl2 HCl
(trichloromethyl)benzene
* Bromination of toluene takes place under similar conditions to yield
61
corresponding bromine derivatives.
SYNTHESIZING A SUBSTITUTED AROMATIC
COMPOUNDS
NO2
?
Cl
NO2
Cl
Cl2, FeCl3 m-chloronitrobenzene
nitrobenzene
63
SYNTHESIZING A SUBSTITUTED AROMATIC
COMPOUNDS
Synthesis p-bromobenzoic acid starting from benzene
? COOH
Br
CH3 COOH
KMnO4
Br Br 64
Immediate precursor of p-bromotoluene:
i) Bromination of toluene
or
ii) Methylation of bromobenzene
CH3
Br2 CH3 CH3
FeCl3
Br Br
or separate the isomer
separate the
isomer
65
Immediate precursor of toluene:
i) Benzene was methylated in a Friedel-Crafts reaction
CH3Cl CH3
AlCl3
benzene toluene
Immediate precursor of bromobenzene:
i) Bromination of benzene
Br2
FeBr3 Br
benzene bromobenzene
66
TWO WORKABLE ROUTES FROM BENZENE TO
p-BROMOBENZOIC ACID
Br2 CH3Cl
FeBr3 AlCl3
Br
CH3 COOH
KMnO4
benzene CH3 Br
CH3Cl Br2 Br
AlCl3 FeBr3
67
USES OF BENZENE AND TOLUENE
• Benzene:
- as solvent for oils and fats
- starting material for making other chemicals. For
example, benzene is used in the cumene process to
produce phenol.
- making organic compounds such as phenylethene
(styrene) and nitrobenzene. These organic compounds
are then used to make plastics (polystyrene), dyes and
nylon.
68
USES OF BENZENE AND TOLUENE
• Toluene:
69
Interesting Aromatic Compounds
70
Figure 17.5
Selected drugs that
contain
a benzene ring
71
Stability of Benzene
72
Stability of Benzene
• The low heat of hydrogenation of benzene means that benzene is
especially stable—even more so than conjugated polyenes. This
unusual stability is characteristic of aromatic compounds.
• Benzene’s unusual behavior is not limited to hydrogenation. Benzene
does not undergo addition reactions typical of other highly
unsaturated compounds, including conjugated dienes.
• Benzene does not react with Br2 to yield an addition product. Instead,
in the presence of a Lewis acid, bromine substitutes for a hydrogen
atom, yielding a product that retains the benzene ring.
73
Buckminsterfullerene—Is it Aromatic?
74
75
76