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9
Rate and Regioselectivity in
Electrophilic Aromatic Substitution
A substituent already present on the ring
can affect both the rate and regioselectivity
of electrophilic aromatic substitution.
Effect on Rate
Methyl Group
CH3
Trifluoromethyl Group
CF3
(Trifluoromethyl)benzene
undergoes nitration 40,000
times more slowly than benzene .
A trifluoromethyl group is a
deactivating substituent.
Effect on Regioselectivity
Nitration of Toluene
CH3
CH3
CH3
CH3
NO2
HNO3
acetic
anhydride
+
NO2
NO2
63%
3%
34%
Nitration of (Trifluoromethyl)benzene
CF3
CF3
CF3
CF3
NO2
HNO3
H2SO4
NO2
NO2
6%
91%
m-nitro(trifluoromethyl)benzene comprises
91% of the product
a trifluoromethyl group is a meta director
3%
12.10
Rate and Regioselectivity
in the
Nitration of Toluene
CH3
H
NO2
+
H
gives ortho
H
H
CH3
CH3
H
+
H
H
NO2
gives para
H
H
NO2
gives meta
CH3
H
NO2
CH3
H
+
H
NO2
gives para
more stable
H
gives ortho
CH3
H
NO2
gives meta
less stable
CH3
H
+
H
NO2
H
H
CH3
H
+
H
NO2
H
H
CH3
NO2
H
+
H
H
H
CH3
H
+
H
NO2
H
H
CH3
NO2
CH3
H
+
H
H
H
NO2
H
H
H
this resonance
form is a
tertiary
carbocation
CH3
H
+
H
NO2
H
H
CH3
NO2
CH3
H
+
H
H
H
NO2
H
H
CH3
H
H
+
H
H
NO2
CH3
H
CH3
H
+
H
H
NO2
H
H
NO2
this resonance
form is a tertiary
carbocation
CH3
H
CH3
H
CH3
H H
+
H
H
H
NO2
H H
H
NO2
this resonance
form is a tertiary
carbocation
H
H
NO2
CH3
H
CH3
H
CH3
H H
+
H
H
H
NO2
H H
H
NO2
H
H
NO2
CH3
H
H
H
H
H
NO2
CH3
H
H
H
CH3
H
H
NO2
H
NO2
CH3
H
H
CH3
H
H
NO2
CH3
H
H
NO2
H
+
H
H
H
all the resonance forms of the rate determining intermediate in the meta nitration
of toluene have their positive charge on a
secondary carbon
H
NO2
42
42
2.5
2.5
58
H 3C
42
42
4.5
2.5
2.5
58
CH3
4.5
3
75
Generalization
12.11
Rate and Regioselectivity
in the
Nitration of (Trifluoromethyl)benzene
A Key Point
H 3C
C+
F 3C
C+
CF3
H
NO2
+
H
gives ortho
H
H
CF3
CF3
H
+
H
H
NO2
gives para
H
H
NO2
gives meta
CF3
H
NO2
CF3
H
+
H
CF3
H
+
H
H
H
gives ortho
less stable
NO2
gives para
H
H
NO2
gives meta
more stable
CF3
H
+
H
NO2
H
H
CF3
H
+
H
NO2
H
H
CF3
NO2
H
+
H
H
H
CF3
H
+
H
NO2
H
H
CF3
NO2
CF3
H
+
H
H
H
NO2
H
H
H
this resonance
form is
destabilized
CF3
H
+
H
NO2
H
H
CF3
NO2
CF3
H
+
H
NO2
H
H
CF3
H
H
+
H
H
NO2
CF3
H
CF3
H
+
H
H
NO2
H
H
NO2
this resonance
form is destabilized
CF3
H
CF3
H
CF3
H H
+
H
H
H
NO2
H H
H
NO2
this resonance
form is destabilized
H
H
NO2
CF3
H
CF3
H
CF3
H H
+
H
H
H
NO2
H
+
H H
H
NO2
H
one of the resonance forms of the ratedetermining intermediate in the para
nitration of (trifluoromethyl)benzene is
strongly destabilized
H
NO2
CF3
H
H
H
H
H
NO2
CF3
H
H
H
CF3
H
H
NO2
H
NO2
CF3
H
H
CF3
H
H
NO2
CF3
H
H
NO2
H
+
H
NO2
H
H
H
none of the resonance forms of the rate-determining
intermediate in the meta nitration of
(trifluoromethyl)benzene have their positive charge
on the carbon that bears the CF3 group
Nitration of (Trifluoromethyl)benzene:
Partial Rate Factors
CF3
4.5 x 10-6
4.5 x 10-6
67 x 10-6
67 x 10-6
4.5 x 10-6