Essential Organic Chemistry
Paula Yurkanis Bruice
Chapter 8
Aromaticity: Reactions of
Benzene and Substituted
Benzenes
8.1 Criteria for Aromaticity
Uninterrupted arrangement of p cloud
Cyclic molecule
Every atom in the ring must have a p
orbital
Molecule has to be planar
Total number of p-electron pairs is odd
(1,3,5)
Exceptionally stable molecules
8.2 Applying The Criteria for
Aromaticity
X
cyclobutadiene benzene
X
cyclooctatetraene
Cyclobutadiene: planar, cyclic, all atoms have p orbitals,
but 2 pairs of p electrons
Benzene: planar, cyclic, all atoms have p orbitals,
3 pairs of p electrons.
Cyclooctatetraene: nonplanar, cyclic, all atoms have p
orbitals, but 4 pairs of p electrons
Benzene
Benzene: planar, ring, all atoms have p
orbitals, 3 pairs of p electrons.
Cyclopentadiene
cyclopentadiene
cyclopentadienyl cation cyclopentadienyl anion
sp3
4 p electrons 4 p electrons 6 p electrons
planar nonplanar planar
aromatic
Cyclopentadienyl anion
Cyclopentadienyl anion
Resonance contributors.
Overall every C atom has the same amount of negative charge
charge equally
distributed
8.3 Aromatic Heterocyclic Compounds
A ring atom that is not carbon is called a
heteroatom.
Pyridine
The lone pair is not part
of the aromatic ring system.
Electrons are located
in sp2-hybrid orbital. N
Pyrrole
N H
N
H
Lone pair is part of p-system, N is sp2 hybridized
Pyrrole
Resonance contributors
N N N
H H H
N N
H H
pos. charge
Furan
Second lone pair is located in sp2-hybridized
Orbital.
Furan
Resonance contributors
O O O
O O
Bicyclic Heterocyclic Aromatics
N
N
N N
N N
H
H
quinoline indole purine
8.4 Nomenclature of Monosubstituted
Benzenes
State the name of substituent and add
the word benzene
Nomenclature
Many trivial names in use
Nomenclature
8.5 How Benzene Reacts
Electrophilic Aromatic Substitution
H E
+ E+ + H+
E
+ E+Nu-
Nu
Aromatic ring systems react with electrophiles
differently than alkenes.
We obtain a substitution rather than an addition product.
Mechanism
H
H
+ E+ EE
H
First, we get a carbocation intermediate.
At the carbon that adds the electrophile,
rehybridization (sp2 sp3) takes place.
Molecule loses aromatic character.
Mechanism
Carbocation is resonance stabilized.
H H H
EE EE EE
H H H
Mechanism
H Nu
H
Nu- E
H
EE +
B- E
H
+ HB
The electron-rich part of the reagent can
act either as nucleophile in an addition
reaction or as a base to remove a proton.
Mechanism
Energy Profile
8.6 General Mechanism for Electrophilic
Aromatic Substitution Reactions
8.7 Halogenation of Benzene
Halogenation of Benzene
Halogenation:
1st step is generating an electrophile:
FeBr3 is a Lewis acid that coordinates with Br2 and
polarizes it, generating an electrophilic Br+
Halogenation of Benzene
8.8 Nitration of Benzene
Nitration:
Nitration of Benzene
Nitration:
8.9 Sulfonation of Benzene
Sulfonation of Benzene
8.10 Friedel-Crafts Acylation of
Benzene
Friedel-Crafts Acylation of
Benzene
8.11 Friedel-Crafts Alkylation of
Benzene
Friedel-Crafts Alkylation of
Benzene
8.12 How Some Substituents on a Benzene
Ring Can be Chemically Changed
8.12 How Some Substituents on a Benzene
Ring Can be Chemically Changed
8.13 Nomenclature of Disubstituted
Benzenes
8.14 The Effect of Substituents on
Reactivity
Monosubstituted benzenes undergo
electrophilic aromatic substitution.
Substituents influence reactivity.
Substituents determine position of second
electrophilic substitution.
Substituents that increase electron density
increase reactivity.
Substituents that decrease electron
density decrease reactivity.
The Effect of Substituents on
Reactivity
Donating and Withdrawing
Electrons by Resonance
Electron-donating Substituents
CH3 H3C H3C
O O O
O CH3 O CH3
Resonance contributors increase electron density in ortho
and para positions. Overall electron density is bigger.
Donating and Withdrawing
Electrons by Resonance
Electron-withdrawing Substituents
O O O O O O
N N N
O O O O
N N
Resonance contributors decrease electron density in ortho and
para positions. Overall electron density is lower.
Substituent Effects
D W
CH3 O O
O N
Both types of substituents, electron Donating and electron Withdrawing,
act on the same positions, namely ortho and para, however, in opposite
directions.
Relative Reactivity of Substituted
Benzenes
Activating
Deactivating
Classification of Substituents
Activating Substituents
(ortho/para directing):
NH2 prim. Amines
Strongly
NHR sec. Amines activating
NR2 tertiary amines
OH phenolic OH
OR phenol ethers
O
NH CR' amides
phenolic esters weakly
O
O CR' activating
R alkyl substituents
halides deactivating
X
Classification of Substituents
Deactivating Substituents (meta directing):
O
+
CH aldehydes
O weakly
+
COR esters deactivating
O
+
COH
carboxylic acid
+
C N
nitrile
+
SO3H
sulfonic acid strongly
O
N O deactivating
nitro
NR3
ammonium
8.15 The Effect of Substituents on
Orientation
1. All activating substituents direct an incoming
electrophile to the ortho and para positions.
The Effect of Substituents on
Orientation
2. The weakly deactivating halogens also direct an
incoming electrophile to the ortho and para
positions.
The Effect of Substituents on
Orientation
3. All moderately deactiating and strongly deactivating
substituents direct an incoming electrophile to the
meta position.
8.15 The Effect of Substituents on
pKa
