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Pricles B. Alves
BENZENO E AROMATICIDADE
1. Isolamento e Estrutura do benzeno
2. Compostos aromticos naturais e sintticos
3. Critrios de aromaticidade para um composto
4. Reatividade
4.1. Mecanismo geral da reao de substituio eletroflica
em aromticos:
5. Reaes dos substituintes no benzeno
6. O efeito dos substituintes na reatividade
7. O efeito dos substituintes na orientao da substituio
8. Reaes de oxidaes; Reaes de redues
HO
MeO
Anetol
"Extrato erva doce"
CH 3 O
CHO
Vanilina
CH 3 O
CHO
HO
Eugenol
OH
Cinamaldedo
(-)-Mentol
Aromaticidade
HIDROCARBONETOS
Alifticos
alcanos
alcenos
Aromticos
alcinos
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II
(Dewar)
CH2 CH C
C CH
V
III
(Ladenburg)
CH2
CH3
IV
CH3
VI
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II
(Dewar)
CH2 CH C
C CH
V
CH2
III
(Ladenburg)
CH3
IV
C
VI
CH3
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Hohidrogenao
Reagente
Produto
(kJ/mol)
(kcal/mol)
ciclohexeno
ciclohexano
-206
-28,2
1,3-ciclohexadieno
ciclohexano
-230
-55,0
benzeno
ciclohexano
-118
-49,2
KMnO4
COOH
COOH
H3O+
OH
ciclohexeno
HCl
Cl
H3O+
no reage
no reage
benzeno
HCl
no reage
Ring Currents
Aromatic ring oriented perpendicular to a strong magnetic
field, delocalized electrons producing a small local
magnetic field
Opposes applied field in middle of ring but reinforces
applied field outside of ring
1H
1H
phenyl-H stretching
Espectrometria
aromticos
de
massas
de
compostos
Erich Hckel
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Non-aromatic
Cyclooctatetraene has four double bonds, reacting with Br2,
KMnO4, and HCl as if it were four alkenes
Distorts out of plane so C=Cs behave like ordinary alkenes
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1,3-Cyclopentadiene
contains conjugated C=Cs
joined by a CH2 that blocks
delocalization
Removal of H+ at the CH2
produces a cyclic 6 esystem, which is stable
H-
Removal of
or H
generate nonaromatic 4
and 5 electron systems
Antiaromatic
(unstable)
Antiaromatic
(unstable)
Aromatic
(very stable)
Cycloheptatrienyl Cation
3 conjugated C=Cs
joined by a CH2
Removal of H-
leaves the cation
The cation has 6e-s
and is aromatic
Aromatic
(stable)
Antiaromatic
(unstable)
Antiaromatic
(very unstable)
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Reao de Substituio
Aromtica (SEA):
Eletrofilica
SEA: Bromao
SEA ocorre em dois passos: Adio seguido de Eliminao
FeBr3 acts as a catalyst to polarize the bromine reagent and
so make it more positive (more electrophilic)
The electrons of the aromatic ring act as a nucleophile
toward the now more electrophilic Br2 (in the FeBr3 complex)
Chlorine and iodine (but not fluorine, which is too reactive) can
produce aromatic substitution products
Chlorination
requires FeCl3
Iodine must be
oxidized (with
Cu+ or peroxide)
to form a more
powerful I+
species
Halogenao
In halogenation, benzene reacts with Cl2 or Br2 in the presence of a Lewis acid
catalyst, such as FeCl3 or FeBr3, to give the aryl halides chlorobenzene or
bromobenzene respectively.
Analogous reactions with I2 and F2 are not synthetically useful because I2 is too
unreactive and F2 reacts too violently.
Sulfonao
Nitrao
The combination of nitric acid and sulfuric acid produces NO2+
(nitronium ion)
The reaction with benzene produces nitrobenzene
Um procedimento conveniente
Desvantagens da alquilao:
Produtos de
rearranjos
Produtos
polialquilados
Produtos rearranjados:
CMe2CH2Me
Me3CCH2Cl/ AlCl3 +
Me3C
CH3
Me2C
CH2Me
Alquilao de FriedelFriedel-Crafts
intramolecular para gerar anis fundidos;
sendo anis de 6 mais fceis de formar que
anis de 5
Charles Friedel
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Similar to alkylation
Reactive electrophile: resonance-stabilized acyl cation
An acyl cation does not rearrange
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Efeito do Substituente
+
E+
Efeito do Substituinte
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Contrasting Effects:
Effects: Inductive vs Resonance
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Resonance effects are only observed with substituents containing lone pairs or
bonds.
An Explanation of Substituent
Effects
Activating groups donate electrons to the ring
ring,,
stabilizing the Wheland intermediate (carbocation
carbocation))
OH, OR, NH2 and R
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Meta--Directing Deactivators
Meta
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With the NO2 group (and all meta directors) meta attack occurs
because attack at the ortho and para position gives a destabilized
carbocation intermediate.
NO2
Fe, H3 O+
NH2
OH
NO2
SnCl2 , H3O+
NH2
OH
NO2
H2 , Pd/C
NH2
EtOH
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Disubstituted Benzenes
1.
When the directing effects of two groups reinforce, the new substituent is
located on the position directed by both groups.
2.
If the directing effects of two groups oppose each other, the more powerful
activator wins out.
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3.
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1.
2.
3.
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