Nitration of Methyl Benzoate

COOH COOCH3
CH3OH

H2SO4

COOCH3 COOCH3
HNO3, H2SO4

NO2
 Multistep Synthesis

50% 50%
A B C

Yield = 25%
Ortho Meta Para

X Ortho

Meta
Para
 Number Ring

6 X 2

5 3

4
 Nucleophilic Aliphatic Substitution
HCl
(CH3)3COH (CH3)3CCl

Electrophilic Aromatic Substitution

H NO2
+
NO2 +
 ARENE SUBSTITUTION

E
E+
+ H+

The electrophile REPLACES H +

 Mechanism

H E-Y
 Mechanism
H E-Y

H E H E H E
+ +

+
E

+ H+
Charge o and p
Energy Diagram
Nitration of Benzene
NO2
HNO3
H2SO4

Nitrobenzene
 Nitration Reagent

HONO2 + 2 H2SO4 NO2+ + H3O+ + 2 HSO4-

Nitronium Ion
 Nitration Mechanism
H H NO2
NO2+
+

NO2

+ H+
 Multiple Substituents
G

G G

Second Group. Where go? How fast?

Nitration of Toluene
CH3
HNO3

CH3 CH3 CH3

NO2

NO2
NO2
63% 3% 34%
ORTHO Compare
CH
o, m, p CH3
3
NO2 NO2
+ H H
+ +
META CH3 CH3 CH3

+ +
NO2 NO2 NO2
H H
+ H

PARA CH3 CH3

+
+ +
H H NO2
NO2
 Electron Donating Groups
Favor: ORTHO and PARA.

Electron
Donating G
Ortho

Para
 Nitration of
trifluoromethylbenzene
CF3
HNO3

H2SO4

CF3 CF3
CF3

NO2
NO2
NO2

6% 91% 3%
Electron Withdrawing Groups

CF3 + charge
here bad
Ortho Compare o, m, p CF3
CF3 CF3
H H H
+
NO2 NO2
+ NO2 +

Meta
CF3 CF3
+ +
H H

+ NO2 NO2

Para
+
+ +
 Electron Withdrawing Groups
Meta Directors and DEACTIVATING
Electron
Withdrawing Z
Group

Meta Product
 Ortho-Para Directors
-NH2 Very Activating
-NHR
-OH
-OR
O
-NHCR
O
-OCR
 Ortho-Para Directors

-R Activating

-Ar Activating

-Halogens Deactivating
Meta Directors
O
-SO3H
-CR
O -NO2
-COH
-CN
Main Reaction
COOCH3 COOCH3
HNO3, H2SO4
meta
NO2

Side Products
COOCH3 COOCH3
COOCH3
NO2

O2N NO2
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.