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2
3
2
3
1
Calculated shapes for
the -molecular
orbitals of benzene...
Organic Chemistry OnLine 2000
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...
Organic Chemistry OnLine 2000
napthalene anthracene
phenanthrene
Some Polycyclic Aromatic Compounds...
Organic Chemistry OnLine 2000
napthalene anthracene
phenanthrene
O
DNA damage
Some Polycyclic Aromatic Compounds...
Organic Chemistry OnLine 2000
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...
Organic Chemistry OnLine 2000
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.
Organic Chemistry OnLine 2000
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
1. Monosubstituted benzene derivatives are names as other
hydrocarbons, using benzene as the parent name.
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
Organic Chemistry OnLine 2000
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
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
1. Monosubstituted benzene derivatives are names as other
hydrocarbons, using benzene as the parent name.
Organic Chemistry OnLine 2000
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.
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
1. Monosubstituted benzene derivatives are names as other
hydrocarbons, using benzene as the parent name.
Organic Chemistry OnLine 2000
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.
Organic Chemistry OnLine 2000
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
Organic Chemistry OnLine 2000
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
1-chloro-3-methylbenzene or
3-chlorotoluene
Organic Chemistry OnLine 2000
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
1-methyl-4-nitrobenzene or
4-nitrotoluene
1-chloro-3-methylbenzene or
3-chlorotoluene
Organic Chemistry OnLine 2000
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.
Organic Chemistry OnLine 2000
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
Organic Chemistry OnLine 2000
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-chloro-2-ethyl-4-nitrobenzene
1
2
4
1
2
4
2-chloro-1-ethyl-4-nitrobenzene
Organic Chemistry OnLine 2000
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
4-chloro-2-ethyl-1-nitrobenzene
1
2
4
1
2
4
1
2
4
Organic Chemistry OnLine 2000
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.
Organic Chemistry OnLine 2000
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
Organic Chemistry OnLine 2000
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
2-chloro-5-nitrotoluene
Organic Chemistry OnLine 2000
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
2-chloro-5-nitrotoluene
5-chloro-2-nitrotoluene
Organic Chemistry OnLine 2000
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.
Organic Chemistry OnLine 2000
4n + 2 Rule
2,3-Dimethylcyclobutadiene
2,3-Dimethylcyclobutadiene
Planar...
2,3-Dimethylcyclobutadiene
Planar...
4 electrons,
2,3-Dimethylcyclobutadiene
Planar...
4 electrons,
therefore not aromatic (antiaromatic)
2,3-Dimethylcyclobutadiene
Planar...
4 electrons,
therefore not aromatic (antiaromatic)
Organic Chemistry OnLine 2000
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
Organic Chemistry OnLine 2000
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
Organic Chemistry OnLine 2000
4 electrons
not aromatic
6 electrons
aromatic
8 electrons
not aromatic
4n + 2 Rule
Cyclopentadienyl Anion
Cyclopentadienyl Anion
Planar...
Cyclopentadienyl Anion
Planar...
6 electrons,
Cyclopentadienyl Anion
Planar...
6 electrons,
therefore aromatic
Cyclopentadienyl Anion
Planar...
6 electrons,
therefore aromatic
Organic Chemistry OnLine 2000
4 electrons
not aromatic
6 electrons
aromatic
8 electrons
not aromatic
6 electrons
aromatic
4n + 2 Rule
Cycloheptatrienyl Cation
+
Cycloheptatrienyl Cation
+
Planar...
Cycloheptatrienyl Cation
+
Planar...
6 electrons,
Cycloheptatrienyl Cation
+
Planar...
6 electrons,
therefore aromatic
Cycloheptatrienyl Cation
+
Planar...
6 electrons,
therefore aromatic
Organic Chemistry OnLine 2000
4 electrons
not aromatic
6 electrons
aromatic
4n + 2 Rule
Organic Chemistry OnLine 2000
4n + 2 Rule
Organic Chemistry OnLine 2000
N
N
N
N
NH
2
H
N O
O
CH
3
H
N
H
Adenine Uracil
4n + 2 Rule
Organic Chemistry OnLine 2000
N
N
N
N
NH
2
H
4n + 2 Rule
Organic Chemistry OnLine 2000
N
N
N
N
NH
2
H
4n + 2 Rule
Adenine:
10 electrons
Aromatic
Organic Chemistry OnLine 2000
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.
Organic Chemistry OnLine 2000
N
N
N
N
NH
2
H
Adenine:
10 electrons
Aromatic
4n + 2 Rule
N O
O
CH
3
H
N
H
Organic Chemistry OnLine 2000
N O
O
CH
3
H
N
H
N
N
N
N
NH
2
H
Adenine:
10 electrons
Aromatic
4n + 2 Rule
Organic Chemistry OnLine 2000
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
Organic Chemistry OnLine 2000
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
Organic Chemistry OnLine 2000
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
Organic Chemistry OnLine 2000
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
Organic Chemistry OnLine 2000
Buckminsterfullerene
C
60
with 31 double bonds
Buckminsterfullerene
Buckminsterfullerene
62 electrons, (4n + 2 with n = 15)
Buckminsterfullerene
62 electrons, (4n + 2 with n = 15)
not planar with considerable ring strain...
Buckminsterfullerene
62 electrons, (4n + 2 with n = 15)
not planar with considerable ring strain...
the molecule appears aromatic, but is much more
reactive than benzene.
Organic Chemistry OnLine 2000
Would you predict cyclodecapentaene to be an
aromatic compound?
Cyclodecapentaene
Organic Chemistry OnLine 2000
Would you predict cyclodecapentaene to be an
aromatic compound?
Cyclodecapentaene
...consider the
geometry of the
two central
hydrogens.
Organic Chemistry OnLine 2000
Cyclodecapentaene
H
H
Would you predict cyclodecapentaene to be an
aromatic compound?
Steric repulsion between the opposing hydrogens forces the
system out of planarity, therefore the molecule is not aromatic.
Organic Chemistry OnLine 2000
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.
Organic Chemistry OnLine 2000
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.
Organic Chemistry OnLine 2000
The two major (neutral) resonance forms for azulene...
Organic Chemistry OnLine 2000
The two major (neutral) resonance forms for azulene...
...and the very stable Zwiterionic form.
Organic Chemistry OnLine 2000
The two major (neutral) resonance forms for azulene...
...and the very stable Zwiterionic form.
cycloheptatriene
cation-like
Organic Chemistry OnLine 2000
The two major (neutral) resonance forms for azulene...
...and the very stable Zwiterionic form.
cycloheptatriene
cation-like
cyclopentadiene
anion-like
Organic Chemistry OnLine 2000