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ACTIVATED RING
Nitration of Anisole
O CH3
O CH3
O CH3
+
HNO3 H2SO4
NO2
NO2
anisole
Reacts faster than benzene
ortho
para
= ACTIVATED
The -OCH3 group when it preexists on the ring gives only ortho and para products, and no meta. Substituents that cause this result are called o,p directors and they usually activate the ring.
DEACTIVATED RING
C OMe
NO2
meta
= DEACTIVATED
The -COOMe group when it preexists on the ring gives only meta, and no ortho or para products. Substituents that cause this result are called m directors and they usually deactivate the ring.
SUBSTITUENT CATEGORIES
Most ring substituents fall into one of these two categories:
G
o,p - directors activate the ring m- directors deactivate the ring
NITRATION OF ANISOLE
Nitration of Anisole
BENZENIUM ION INTERMEDIATES
O CH3
O N+ O
O CH3 H NO2 + H
O CH3 H + H NO2 H
O CH3 +
meta
para
H NO2
O CH3
orth o
O CH3 H NO2 + H
O CH3 H NO2 H
:O
CH3 H + NO2 H
+ O CH 3 H NO2 H
EXTRA!
meta
O CH3 H + H NO2
O CH3 H + H NO2
O CH3 H + H
NO2
para
+ H
O CH3
:O
+
CH3
+O CH 3
O CH3
H NO2
EXTRA!
Energy Profiles
NITRATION OF ANISOLE RECALL: HAMMOND POSTULATE benzenium intermediate
Ea
ortho-para director
BENZENIUM IONS GIVE ELIMINATION INSTEAD OF ADDITION ADDITION REACTION doesnt happen resonance would be lost
O CH3 H +
O CH3 H :B _
NO2
X
O CH3 H
B H NO2
addition
O CH3 H + NO2 :B _
NO2 elimination
C OMe
O O N+ O
C OMe H + NO2 H
C OMe H + H NO2 H
C OMe
deactivated ring
ortho
meta
para
H NO2
C OMe
NO2
orth o
O
C OMe H + NO2 H
C OMe H NO2 H
O +
C OMe H BAD! + NO
2
H
O C OMe H + H
meta
C OMe H + H NO2
C OMe H
+ H NO2 NO2
para
C OMe
O +
+
C OMe
C OMe
BAD!
+ H
+ H H NO2 H H NO2
H NO2
Energy Profiles
NITRATION OF METHYL BENZOATE
some benzenium resonance structures have a bad situation
meta director
PROFILE:
:X
+I Substituent These groups also activate the ring, or make it more reactive. CH3RThe +R groups activate the ring more strongly than +I groups.
+R Substituent
.. CH3-O.. ..
CH3-N-
.. -O-H ..
-NH2
..
PROFILE:
-I Substituent These groups also deactivate the ring, or make it less reactive.
R + N R R CCl3
-R Substituent
O C R O C OR O C OH C N
+O
N O
-SO3H
THE EXCEPTION
..
Halides represent a special case: They are o,p directing groups that are deactivating They are o,p directors (+R effect ) They are deactivating ( -I effect ) Most other other substituents fall into one of these four categories: 1) 2) 3) 4) +R / o,p / activating +I / o,p / activating -R / m / deactivating -I / m / deactivating
PREDICT !
CH3 NO2
o,p
O CH3
O C O CH3
o,p
O CH3 NO2
very little formed
O CH3
O2N
m-director HNO3 H2SO4
NO2
O CH3 NO2
When groups direct to the same positions it is easy to predict the product.
NO2
major product
GROUPS COMPETING
o,p-directing groups win over m-directing groups
O CH3 O2N NO2
O CH3
too crowded
HNO3 H2SO4
NO2
O CH3
NO2 NO2
O CH3
HNO3 H2SO4
O CH3 NO2
CH3
+I resonance effects are more important than inductive effects
CH3
major product
1) Activating (o,p) groups (+R, +I) win over deactivating (m) groups (-R,-I). 2) Resonance groups (+R) win over inductive (+I) groups. 3) 1,2,3-Trisubstituted products rarely form due to excessive steric crowding. 4) With bulky directing groups, there will usually be more p-substitution than o-substitution. 5) The incoming group replaces a hydrogen, it will not usually displace a substituent already in place.
NO2
NO2
CH3
CH2CH2CH2CH3