+ H2O + NO2
nitration:
1) HONO2 + 2 H2SO4
H3O+
2 HSO4- + NO2+
electrophile
2) + NO2+ RDS
resonance
NO2 H
NO2 H
NO2 H
NO2 H
1) HONO2 + 2 H2SO4
H3O+
2 HSO4- + NO2+
2)
NO2+
RDS
NO2 H
NO2 3) H
NO2
+ H+
RDS 2) + SO3
SO3H
3)
SO3H
SO3-
H+
4)
SO3- + H3O+
SO3H
+ H2O
1)
Cl2 + AlCl3
Cl-Cl-AlCl3
RDS 2) + Cl-Cl-AlCl3
Cl H
+ AlCl4-
Cl 3) H
AlCl4-
Cl
+ HCl + AlCl3
1)
R-X
FeX3
R RDS
FeX4R H
2)
+ R
R 3) H
+ FeX4-
HX
+ FeX3
1)
R-OH
2)
ROH2+
+ H2O RDS R H
3)
+ R
R 4) H
+ H+
RDS 2) + R
R H
R 3) H R +
H+
RDS 1) + Y+Z-
Y H + Z-
2)
Y H + ZY + HZ
increasing reactivity
ortho/para directors
meta directors
Why do substituent groups on a benzene ring affect the reactivity and orientation in the way they do?
electronic effects, pushing or pulling electrons by the substituent. Electrons can be donated (pushed) or withdrawn (pulled) by atoms or groups of atoms via:
Induction due to differences in electronegativities
H N H
R N H
unshared pair of electrons on the nitrogen resonance donating groups (weaker inductive withdrawal)
R N R R R N R
strong inductive withdrawal (no unshared pair of electrons on the nitrogen & no resonance possible
O H
O R
O H3C C N H
resonance donation
H3 C
inductive withdrawal
O C H
O C RO
N C
O N O
-NH2, -NHR, -NR2 -OH -OR -NHCOCH3 -C6H5 -R -H -X -CHO, -COR -SO3H -COOH, -COOR -CN -NR3+ -NO2
electron donating
increasing reactivity
electron withdrawing
Electron donating groups activate the benzene ring to electrophilic aromatic substitution.
1. electron donating groups increase the electron density in the ring and make it more reactive with electrophiles.
2. electron donation stabilizes the intermediate carbocation, lowers the Eact and increases the rate.
CH3
Electron withdrawing groups deactivate the benzene ring to electrophilic aromatic substitution.
1. electron withdrawing groups decrease the electron density in the ring and make it less reactive with electrophiles.
2. electron withdrawal destabilizes the intermediate carbocation, raising the Eact and slowing the rate.
NO2
Br2, Fe Br + ortho-
O O
Br2, Fe
O + orthoO Br
Y H
Y H
Y H
Y H
Y H ortho-attack
G Y H
G Y H
G Y H meta-attack
G para-attack H Y
H Y
H Y
G
Y H
H Y
If G is an electron donating group, these structures are especially stable.
Y H
Y H
Y H ortho-attack
G Y H
G Y H
G Y H meta-attack
G para-attack H Y
H Y
H Y
Electron donating groups stabilize the intermediate carbocations for ortho- and para- in EAS more than for meta-. The Eacts for ortho-/para- are lower and the rates are faster.
G Y H H Y
Y H
Y H
Y H ortho-attack
G Y H
G Y H
G Y H meta-attack
G para-attack H Y
H Y
H Y
Electron withdrawing groups destabilize the intermediate carbocations for ortho- and para- in EAS more than for meta-. The Eacts for ortho-/para- are higher and the rates are slower.
The halogen atom is unusual in that it is highly electronegative but also has unshared pairs of electrons that can be resonance donated to the carbocation.
Y H
Y H
Y H
Y H ortho-
X Y H
X Y H
X Y H meta-
X para-
H Y
H Y
H Y
H Y