Preparation of p-nitroacetanilide,

hydrolysis of p-nitroacetanilide,
preparation of p-nitroaniline
(Student's Handout)
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p-nitroacetanilide, p-nitroaniline, nitration of acetanilide, hydrolysis of p-nitroacetanilide, preparation of p-nitroaniline
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2. Electrophilic attach on the aromatic ring

H
N

CH 3
O

+
o-

HN

HN

NO 2

CH 3

CH 3
HN

HN

O
NO 2

CH 3
O

?
Resounance structures

NO 2

3. Deprotonation
CH 3
HN

CH 3
HN

NO 2
H
HSO 4

H
HSO 4

NO 2

H 2SO 4

H 2SO 4

o-nitroacetanilide

CH 3
HN

O
NO 2

CH 3
HN

O 2N

p-nitroacetanilide

O
NO 2
H

HN

O
NO 2
H

p- attach

HN

NO 2

NO 2

p-

CH 3

CH 3

CH 3
o- attach

Week (1) Procedure:

1. In a beaker, dissolve 5.0g of acetanilide in 5.0ml glacial
acetic acid. To this solution add 15.0 ml conc. H
2 SO4 with
stirring.
2. Immerse the flask in a cooling mixture of ice and salt to
o
bring the temperature to 0
C.
3. Prepare a solution of concentrated nitric acid 2.0 ml and
concentrated sulfuric acid 1.5ml.
4. Add drop wise (use dropping funnel or pipette) the
nitric/sulphuric mixture to the acetanilide (not the reverse).
Adjust the rate of
addition so that the temperature does not
rise above 10 o C.
5. After the addition is complete allow the beaker to stand at
room temperature for 30 minutes.
6. Pour the contents of the flask into 150g of crushed ice. [the
o-nitroacetanilide, being soluble, remains in solution while pnitroacetanilide precipitates out]
7. Filter the solid on a Bchner funnel.

Week (2): Hydrolysis of p-nitroacetanilide

Preparation of p-nitroaniline

O
H 3C

NH

1) H / H 2O

NH 2

2) OH
NO 2
p-nitroacetanilide

NO 2

p-nitroaniline

Week (1) Procedure:

Mechanism of the Reaction

1. In a beaker, dissolve 5.0g of acetanilide in 5.0ml glacial

acetic acid. To this solution add 15.0 ml conc. H
2 SO4 with
H 3C
H 3C
stirring.
H 3C
O
O
C OH
Oand salt C
+
2. ImmerseNH the flask
in
a
cooling
mixture
of
ice
toOH
H
N
NH
+
+
N
NH
o
bring the temperature to 0 O
C.
O
-

O
+
N
O

3.p-nitroacetanilide
Prepare a solution of concentrated nitric acid 2.0 ml and
H 3C
concentrated
sulfuric acid 1.5ml. H3C C OH
H3 C
-

C OH

O H
H

OH
C

+
+
NH
N
NHfunnel
4.N+ Add drop
wise (use dropping
or pipette)
theNH
N
O
O
O
nitric/sulphuricOmixture to the acetanilideHSO
(not
the reverse).
4
H of
H addition so that the temperature does not
Adjust the rate
rise above 10 o C.
-

O
H

O
5.N+ After theNHaddition
is complete allow
the beaker to stand at
+
+
2
N
NH 3 HSO 4
OH
H 3C
O
room temperature for 30 minutes.O
or

CH 3COO

6. Pour the- contents of the flask into 150g of crushed ice. [the
H 2O
O
NaOH
+
o-nitroacetanilide,
being
soluble,
in solution while p+
N
NH 2
NaHSOremains
4
O
CH 3 COONa
nitroacetanilide precipitates out]
7. Filter the solid on a Bchner funnel.

Week (2) Procedure:

Week (2): Hydrolysis of p-nitroacetanilide
1.

Place 2.5 g of p-nitroacetanilide and 13ml of 70% H

Preparation
of p-nitroaniline
a round-bottomed
flask.

SO4 in

2. Reflux the mixture for 20min.

O

3. pour the hot solution

into 250ml of cold water
taken in a
beaker
H 3C
NH
NH 2
1) H / H O
2

4. Neutralize with 10% NaOH.

2) OH

NOon
2
5. Cool and filter the
product
a Buchner
funnel. Wash it thoroughly with water.
NO 2crystalline
yellow

p-nitroacetanilide

p-nitroaniline

6
5

Mechanism of the Reaction

H 3C
O
+
N
O

O
NH

H 3C
O
+
N
O

C OH
NH

H 3C
O
+
N
O

C OH
NH

p-nitroacetanilide

H3 C

H3 C
O
+
N
O

C OH
NH

O
+
N
O

NH

NH 2

NaOH

O
+
N
O

H 3C

H 3C

O H
H

O
+
N
O

OH
C

NH

HSO 4

O
+
N
O

OH
C

OH

NH 2

O
+
N
O

NH 3

HSO 4
or
CH 3COO

H 2O
NaHSO 4
CH 3 COONa

Week (2) Procedure:

1.

Place 2.5 g of p-nitroacetanilide and 13ml of 70% H

a round-bottomed flask.

SO4 in

2. Reflux the mixture for 20min.

3. pour the hot solution into 250ml of cold water taken in a
beaker

4. Neutralize with 10% NaOH.

5. Cool and filter the yellow crystalline product on a Buchner
funnel. Wash it thoroughly with water.
6