Nitration of Methyl Benzoate

COOH

COOCH3
CH3OH
H2SO4

COOCH3

COOCH3

HNO3, H2SO4
NO2

Multistep Synthesis

50%

50%

Yield = 25%

Ortho Meta Para

Ortho
Meta

Para

Nomenclature

3
4

Nucleophilic Aliphatic Substitution

HCl

(CH3)3COH

(CH3)3Cl

Electrophilic Aromatic Substitution

H
+

NO2

NO2

ARENE SUBSTITUTION

E
E+

+ H+

The electrophile REPLACES H

Mechanism

E-Y

E-Y

Mechanism
H

+
E

+ H+

Charge o and p

Reaction Coordinate

Nitration of Benzene
NO2
HNO3
H2SO4

Nitrobenzene

Nitration Reagent
HONO2 + 2 H2SO4

NO2+ + H3O+ + 2 HSO4-

Nitronium Ion

NO2+

NO2
+ H+

Multiple Substituents
G

Second Group. Where go? How fast?

Nitration of Toluene
CH3

HNO3

CH3

CH3

CH3
NO2

NO2

NO2

63%

3%

34%

ORTHO

CH3

CH3

NO2

+
META

CH3
NO2

CH3

NO2

NO2
H

H
CH3

CH3

+
H

CH3

PARA

NO2

NO2

+
H

NO2

Electron donating groups favor

reaction ORTHO and PARA.
Electron Donating
G

Para

Ortho

Nitration of
(trifluoromethyl)benzene
CF3

HNO3
H2SO4
CF3

CF3

CF3

NO2
NO2

6%

91%

NO2

3%

Electron Withdrawing group

CF3

+ charge
here bad

Ortho

CF3

CF3

CF3

H
NO2

NO2

NO2

Meta

CF3

CF3

+
+

NO2

NO2

Para
+

+
+

Electron Withdrawing Groups are Meta

Directors and DEACTIVATING
Electron
Withdrawing
Group

Meta Product

Ortho-Para Directors
-NH2
-NHR
-OH
-OR
O
-NHCR
O
-OCR

Very Activating

Ortho-Para Directors
-R

Activating

-Ar

Activating

-Halogens Deactivating

Meta Directors

O
-CR
O
-COH
-CN

-SO3H
-NO2

Main Reaction
COOCH3

COOCH3
HNO3, H2SO4

meta
NO2

Side Products
COOCH3

COOCH3

COOCH3

NO2

NO2

O2N

NO2

Procedure
1. Dissolve methyl
benzoate in H2SO4
2. Mix HNO3 and
H2SO4 at 0oC
3. Add HNO3 / H2SO4
dropwise to methyl
benzoate at 0oC

Procedure
4. Let stand at room
temperature 10
minutes

5. Pour onto ice

Filter

Wash
Recrystallize from
methanol
Dry
Weigh
m.p.