Aromaticity and Benzene

Organic Chemistry OnLine 2000
2000, Paul R. Young

University of Illinois at Chicago, All Rights Reserved
Aromaticity
Aromaticity: Derivatives of Benzene

H
H
H
H
H
H

very slow reaction
no reaction
no reaction
HCl
Br
2
/CCl
4
H
2
/Pt
Benzene has four degrees of unsaturation, but undergoes
none of the common reactions of alkenes...

H
2
/Pt
C
6
H
6
Heat of Hydrogenation
(energy released during reduction with H
2
/Pt)
Reactant Product H
Cyclohexene Cyclohexane 28.6 kcal/mole
1,3-Cyclohexadiene Cyclohexane 55.4 kcal/mole
Benzene Cyclohexane 49.8 kcal/mole

H
2
/Pt
86 kcal/mole expected; 50 kcal/mole observed
36 kcal/mole more stable than expected
Isomers of C
6
H
6

Ladenburg benzene
H
H
H
H
H
H
Kekul benzene
C
6
H
6
isomers as possible
structures for benzene...

4 isomers expected for
Kekul benzene
Br
Br
Br
Br
Br
Br
Br
Br
3 dibromo isomers
Br
2
/FeBr
3
Benzene

Br
Br
Br
Br
long bond short bond

Br
Br
Br
Br
Br
Br
...three dibromo isomers are predicted.
Ladenburg benzene

3 isomers expected
Br
Br
Br
Br
Br
Br
Br
Br
3 isomers
Br
2
/FeBr
3
identical
Benzene

Br
Br
Br
Br
Kekul suggested that the two possible 1,2-
isomers were in rapid equilibrium...

Br
Br
Br
Br

Br
Br
Br
Br
or
Br
Br
...today we recognize the two structures Kekul
drew as simple resonance forms.
The conjugated system in the benzene ring results in the
formation of a continuous -cloud, above and below the
plane of the ring.
An electrostatic potential map
of benzene showing enhanced
electron density above and
below the ring plane.

2

3
The six p-orbitals of benzene

combine to form six -molecular
orbitals of increasing energy.
The six bonding electrons
occupy the three lowest
energy molecular orbitals.
2

3
1
Calculated shapes for
the -molecular
orbitals of benzene...

H
H
H
H
H
H
CH
3
H
H
H
H
H
CH
3
H
CH
3
H
H
H
NH
2
H
H
H
H
H
OH
H
H
H
H
H
NO
2
H
H
H
H
H
benzene toluene meta-xylene
aniline phenol nitrobenzene
Representative Aromatic Compounds...

napthalene anthracene
phenanthrene
Some Polycyclic Aromatic Compounds...

napthalene anthracene
phenanthrene
O
DNA damage
Some Polycyclic Aromatic Compounds...

HO O CH
2
C
H
NH
2
COOH
I
I
I
I
Thyroxin
DDT

CH
C
Cl
Cl
Cl
Cl
Cl
Some Other Notable
Aromatic Compounds...

Br CH
2
CH
3
CH
3
bromobenzene ethylbenzene
methylbenzene
or toluene
Nomenclature
1. Monosubstituted benzene derivatives are names as other
hydrocarbons, using benzene as the parent name.
2. Disubstituted benzenes are named using ortho-, para- and
meta- to describe the substitution pattern (1,2 1,4 and 1,3
respectively) or simply by numbering the substituents.
Nomenclature

Br
Br
CH
2
CH
3
CH
2
CH
3
CH
3
H
3
C
ortho-dibromobenzene
or 1,2-dibromobenzene
meta-diethylbenzene
or 1,3-diethylbenzene
para-dimethylbenzene,
1,4-dimethylbenzene
or para-xylene
3. Substituents are numbered to give the lowest possible
number sequence at the first point of difference, assigning
priorities alphabetically if there is a tie.

CH
2
CH
3
CH
2
CH
3
Cl
1-chloro-3,5-diethylbenzene
1
3
5
Nomenclature
4. When a benzene ring is a substituent on another chain, it
is referred to as a phenyl group.

1-phenylheptane
1
3. Substituents are numbered to give the lowest possible
number sequence at the first point of difference, assigning
priorities alphabetically if there is a tie.
Nomenclature

CH
3
H
H
NO
2
H
H
CH
3
CH
3
H
H
Br
H
CH
3
H
Cl
H
H
H
...provide IUPAC names for each of the molecules shown above.

CH
3
H
H
NO
2
H
H
CH
3
CH
3
H
H
Br
H
CH
3
H
Cl
H
H
H
4-bromo-1,2-dimethylbenzene

CH
3
H
H
NO
2
H
H
CH
3
CH
3
H
H
Br
H
CH
3
H
Cl
H
H
H
1-chloro-3-methylbenzene or
3-chlorotoluene

CH
3
H
H
NO
2
H
H
CH
3
CH
3
H
H
Br
H
CH
3
H
Cl
H
H
H
1-methyl-4-nitrobenzene or
4-nitrotoluene
1-chloro-3-methylbenzene or
3-chlorotoluene

CH
2
CH
3
Cl
H
NO
2
H
H
Cl
CH
2
CH
3
H
NO
2
H
H
Cl
H
CH
2
CH
3
NO
2
H
H
...provide IUPAC names for each of the molecules shown above.

CH
2
CH
3
Cl
H
NO
2
H
H
Cl
CH
2
CH
3
H
NO
2
H
H
Cl
H
CH
2
CH
3
NO
2
H
H
1
2
4
2-chloro-1-ethyl-4-nitrobenzene

CH
2
CH
3
Cl
H
NO
2
H
H
Cl
CH
2
CH
3
H
NO
2
H
H
Cl
H
CH
2
CH
3
NO
2
H
H
1
2
4
1
2
4

CH
2
CH
3
Cl
H
NO
2
H
H
Cl
CH
2
CH
3
H
NO
2
H
H
Cl
H
CH
2
CH
3
NO
2
H
H
2-chloro-1-ethyl-4-nitrobenzene 1-chloro-2-ethyl-4-nitrobenzene
1
2
4
1
2
4
1
2
4

CH
3
Cl
H
NO
2
H
H
Cl
CH
3
H
NO
2
H
H
Cl
H
CH
3
NO
2
H
H
...name as derivatives of toluene.

CH
3
Cl
H
NO
2
H
H
Cl
CH
3
H
NO
2
H
H
Cl
H
CH
3
NO
2
H
H
2-chloro-4-nitrotoluene

CH
3
Cl
H
NO
2
H
H
Cl
CH
3
H
NO
2
H
H
Cl
H
CH
3
NO
2
H
H

CH
3
Cl
H
NO
2
H
H
Cl
CH
3
H
NO
2
H
H
Cl
H
CH
3
NO
2
H
H
The resonance description of benzene will explain the
geometry of the molecule and the isomer distribution
of benzene derivatives, but does not explain the
unusual stability of benzene and its derivatives.
The stability of benzene is suggested to arise from the
fact that the conjugated system is planar and
contains 4n + 2 electrons (with n = 1), and it is
suggested that all compounds having planar,
conjugated systems containing 4n + 2 electrons will
share this stability. This property, described
originally by Hckel, is referred to as aromaticity.

4n + 2 Rule
2,3-Dimethylcyclobutadiene
Planar...
Planar...
4 electrons,
Planar...
4 electrons,
therefore not aromatic (antiaromatic)
Planar...
4 electrons,
therefore not aromatic (antiaromatic)

4 electrons
antiaromatic
4n + 2 Rule
Benzene
Benzene
Planar...
Benzene
Planar...
6 electrons,
Benzene
Planar...
6 electrons,
therefore aromatic
Benzene
Planar...
6 electrons,
therefore aromatic

4 electrons
not aromatic
6 electrons
aromatic
4n + 2 Rule
Cyclooctatetraene
Cyclooctatetraene
Not planar...
Cyclooctatetraene
Not planar...
8 electrons,
Cyclooctatetraene
Not planar...
8 electrons,
therefore not aromatic
Cyclooctatetraene
Cyclooctatetraene

4 electrons
not aromatic
6 electrons
aromatic
8 electrons
not aromatic
4n + 2 Rule
Cyclopentadienyl Anion
Planar...
Planar...
6 electrons,
Planar...
6 electrons,
therefore aromatic
Planar...
6 electrons,
therefore aromatic

4 electrons
not aromatic
6 electrons
aromatic
8 electrons
not aromatic
6 electrons
aromatic
4n + 2 Rule
Cycloheptatrienyl Cation
+
+
Planar...
+
Planar...
6 electrons,
+
Planar...
6 electrons,
therefore aromatic
+
Planar...
6 electrons,
therefore aromatic

4 electrons
not aromatic
6 electrons
aromatic
4n + 2 Rule

4n + 2 Rule
N
N
N
N
NH
2
H
N O
O
CH
3
H
N
H
Adenine Uracil
4n + 2 Rule
N
N
N
N
NH
2
H
4n + 2 Rule
N
N
N
N
NH
2
H
4n + 2 Rule
Adenine:
10 electrons
Aromatic
N
N
N
N
NH
2
H
Adenine:
10 electrons
Aromatic
4n + 2 Rule
The lone pairs on the
nitrogens are orthogonal to
the -system and do not
participate in the
molecular orbital.
N
N
N
N
NH
2
H
Adenine:
10 electrons
Aromatic
4n + 2 Rule
N O
O
CH
3
H
N
H
N O
O
CH
3
H
N
H
N
N
N
N
NH
2
H
Adenine:
10 electrons
Aromatic
4n + 2 Rule
N O
O
CH
3
H
N
H
N
N
N
N
NH
2
H
Adenine:
10 electrons
Aromatic
4n + 2 Rule
Uracil:
6 electrons
Aromatic
CH
2
CH
3
CH CH
2
CH
3
CH CH
2
H
3
C
H
3
C
CH
2
N
N N
N
CH
2
CH
2
COOH COOH
Fe
Heme
4n + 2 Rule
CH
2
CH
3
CH CH
2
CH
3
CH CH
2
H
3
C
H
3
C
CH
2
N
N N
N
CH
2
CH
2
COOH COOH
Fe
4n + 2 Rule
CH
2
CH
3
CH CH
2
CH
3
CH CH
2
H
3
C
H
3
C
CH
2
N
N N
N
CH
2
CH
2
COOH COOH
Fe
4n + 2 Rule
Heme: 22 electrons; Aromatic (n = 5)
Heme
Heme
Planar...
Heme
Planar...
22 electrons,
Heme
Planar...
22 electrons,
therefore aromatic
Buckminsterfullerene
C
60
with 31 double bonds
62 electrons, (4n + 2 with n = 15)
not planar with considerable ring strain...
not planar with considerable ring strain...
the molecule appears aromatic, but is much more
reactive than benzene.
Would you predict cyclodecapentaene to be an
aromatic compound?
Cyclodecapentaene
aromatic compound?
Cyclodecapentaene
...consider the
geometry of the
two central
hydrogens.
Cyclodecapentaene

H
H
aromatic compound?
Steric repulsion between the opposing hydrogens forces the
system out of planarity, therefore the molecule is not aromatic.

Azulene, C
10
H
8
, is a deep blue hydrocarbon with a large dipole
magnetic moment.
a. is azulene aromatic using the Hckel definition?
b. utilize resonance forms for azulene to explain the large
dipole moment.
10 -electrons
Aromatic
Azulene, C
10
H
8
, is a deep blue hydrocarbon with a large dipole
magnetic moment.
a. is azulene aromatic using the Hckel definition?
b. utilize resonance forms for azulene to explain the large
dipole moment.

The two major (neutral) resonance forms for azulene...

...and the very stable Zwiterionic form.

cycloheptatriene
cation-like

cycloheptatriene
cation-like
cyclopentadiene
anion-like

The contribution from the Zwitterionic resonance form

leads to the presence of a large dipole moment, which
is associated with color in conjugated molecules.

Contrast the electron density map of azulene with that of

napthalene, which has no significant Zwitterionic component.


stable very unstable
2
Account for the differences in reactivity between pentalene (an
unknown compound) and the well-known pentalene dianion:
8 -electrons;
not aromatic
10 -electrons;
aromatic

2
Reactions of Aromatic Sidechains
1. Oxidation with neutral MnO
4
-
2. Allylic bromination with NBS
Oxidation with
Neutral MnO
4
-

CH
3
CH
2
CH
2
CH
3
MnO
4
-
/H
2
O, heat
MnO
4
-
/H
2
O, heat
MnO
4
-
/H
2
O, heat

CH
3
CH
2
CH
2
CH
3
MnO
4
-
/H
2
O, heat
MnO
4
-
/H
2
O, heat
MnO
4
-
/H
2
O, heat
COOH
...benzylic carbon
must have at least
one hydrogen.

MnO
4
-
/H
2
O, heat
CH
3
CH
3
MnO
4
-
/H
2
O, heat

MnO
4
-
/H
2
O, heat
COOH
COOH
CH
3
CH
3
MnO
4
-
/H
2
O, heat
COOH
COOH

MnO
4
-
/H
2
O, heat
COOH
COOH
CH
3
CH
3
MnO
4
-
/H
2
O, heat
COOH
COOH

NBS/CCl
4
"radical initiator"

NBS/CCl
4
"radical initiator"
NBS/CCl
4
"radical initiator"
CH
2
CH
2
CH
3
CH
3
Free Radical
Bromination of Alkyl
Side-Chains
O
O
O
O
Benzoyl Peroxide (PhCO
2
)
2 N Br
O
O
N-bromo-
succinimide
Br
CH
2
H
CH
2
HBr +
NBS
CH
2
Br
O
O
2

Br

NBS/CCl
4
"radical initiator"

NBS/CCl
4
"radical initiator"
NBS/CCl
4
"radical initiator"
CH
2
CH
2
CH
3
CH
3
Free Radical
Bromination of Alkyl
Side-Chains

NBS/CCl
4
"radical initiator"

NBS/CCl
4
"radical initiator"
NBS/CCl
4
"radical initiator"
CH
2
CH
2
CH
3
CH
3
Br
CHCH
2
CH
3
Br
CH
2
Br

NBS/CCl
4
"radical initiator"

NBS/CCl
4
"radical initiator"
NBS/CCl
4
"radical initiator"
CH
2
CH
2
CH
3
CH
3
Br
CHCH
2
CH
3
Br
CH
2
Br

NBS/CCl
4
"radical initiator"

NBS/CCl
4
"radical initiator"
NBS/CCl
4
"radical initiator"
CH
2
CH
2
CH
3
CH
3
Br
CHCH
2
CH
3
Br
CH
2
Br
Dissolving Metal Reduction of Benzene Derivatives
The Birch Reduction

Li/NH
3

Li/NH
3
CH
3
Li/NH
3
CH
3
OCH
3
Li/NH
3
OCH
3
With substituted arenes,
the Birch Reduction will
proceed to place the
double bond on a ring
carbon which is attached
to electron donating
substituents...
The Birch Reduction

Li/NH
3
CH
3
Li/NH
3
CH
3
OCH
3
Li/NH
3
OCH
3
The Birch Reduction

Li/NH
3
CH
3
Li/NH
3
CH
3
OCH
3
Li/NH
3
OCH
3
The Birch Reduction

MnO
4
-
/H
2
O
Predict the products of the following reactions.
Li/NH
3
NBS/CCl
4
"radical initiator"

Br
Br
MnO
4
-
/H
2
O
Li/NH
3
NBS/CCl
4
"radical initiator"

COOH
HOOC
Br
Br
MnO
4
-
/H
2
O
Li/NH
3
NBS/CCl
4
"radical initiator"

COOH
HOOC
Br
Br
MnO
4
-
/H
2
O
Li/NH
3
NBS/CCl
4
"radical initiator"

Aromaticity and Benzene

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Aromaticity and Benzene

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Organic Chemistry OnLine 2000

2000, Paul R. Young

The six p-orbitals of benzene

The contribution from the Zwitterionic resonance form

Contrast the electron density map of azulene with that of

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