EFFECT OF AROMATIC STABILIZATION ON REACTIONS

OF BENZENE (and other aromatic compounds)

ADDITION
Bonds Bonds
2
2
No reaction
Br
Br
exothermic
would be
Br
broken made
Br
bond
(65 kcal/mol))
2 C-Br
Br-Br
(2 x 70
(50 kcal/mol)
kcal/mol)
bond 2 C-Br
Br-Br bond
endothermic
also would
loose AROMATIC
STABILIZATION
INSTEAD - SUBSTITUTION
3
/
2
FeBr Br
Br
p
p
Aromatic compounds like benzene undergo SUBSTITUTION
Instead of ADDITION
For bromination E
+
= Br-Br + FeBr
3
Energy Diagram for Bromination
ELECTROPHILIC SPECIES IN EAS
Br
2
/FeBr
3
Br
HNO
3
/H
2
SO
4
NO
2
D
2
O/D
2
SO
4
D
O
R
Cl
AlCl
3
R Cl
O
AlCl
3
OR Cl
2
/AlCl
3

for
Cl
FeBr
3
Br Br
O N O
D
R
O
R
O
ELECTROPHILE
nitronium ion
deuterium ion
carbocation
acylium ion
+
Nitronium O=N=O
Benzene
+
Acylium CH
3
C=O
Summary of Directing Effects
Four categories:
I. Strongly activating, ortho/para directing (eg. -OMe)
II. Weakly activating, ortho/para directing (eg. -CH
3
)
III. Weakly deactivating, ortho/para directing (eg. -Cl,)
IV. Deactivating, meta directing (eg. -NO
2
)
I. Strongly activating, ortho/para directing (LP electrons)
(eg. -OMe, Inductive and Resonance effects)
NH
2
OMe
Anisole Aniline
I. Strongly activating, ortho/para directing
(eg. -OMe, Consider inductive and resonance effects)
II. Weakly activating, ortho/para directing
(eg. -CH
3
Consider inductive effects)
Stability of Intermediate defines outcome
Intermediate is
more stable if
nitration occurs
at the ortho
or para position.
Carbocation
stability!
II. Weakly activating, ortho/para directing (eg. -CH
3
inductive)
III. Weakly deactivating, ortho/para directing
(eg. -Cl, Inductive/Resonance)
(
III. Weakly deactivating, ortho/para directing
eg. -Cl,Consider inductive and resonance effects)
IV. Deactivating, meta directing (eg. -NO
2
, inductive effects)
NO
2
NO
2
O
2
N
IV. Deactivating, meta directing (eg. -NO
2
, inductive)
SYNTHETIC STRATEGIES WITH AROMATIC COMPOUNDS
STERIC EFFECTS IN ELECTROPHILIC AROMATIC
SUBSTITUTION