Lecture by: Dotsha J.

Raheem Assistant Lecturer Department of Chemistry College of Science University of Salahadin 2010

Week (1): Nitration of Acetanilide

1.

Preparation of Acetanilide
O NH2 + H3C O O O O H3C CH3 Acetanilide OH + H3C HN CH3 O OH

Aniline

Acetic anhydride

Acetic acid

2.
O HN

Nitration of Acetanilide
O CH3 HNO3 / H2SO4 HN CH3 NO2 + NO2 o-nitroacetanilide p-nitroacetanilide "Major product" HN O CH3

Acetanilide

3.

Hydrolysis of Acetanilide
H H H

1) Hydrolysis H ,H ) H

-nitroacetanilide

-nitroaniline

Importance of Acetanilide
m-director o,p-director
NH2 + Aniline HNO3 / H2SO4 Anilinium ion NH3 HNO3 H2SO4 meta substitution

So, acetylation protects aniline from protonation, charring and oxidation

Charring and oxidation of aniline

This lab.:

/

c ta ili - itr ac ta ili - itr ac ta ili " a r r ct"

Q/
The major product is para, but why not ortho? This is mainly due to steric effect.

ortho-nitroacetanilide

para-nitroacetanilide

ortho-nitroacetanilide

para-nitroacetanilide

Notes on the Experiment
Nitration of acetanilide is an exothermic reaction ; the temperature must be carefully controlled by chilling, stirring, and the slow addition of reagents. The reaction is conducted below 0Û C to maintain selectivity by preventing less favorable reactions from occurring [o- and 2,4dinitro products require higher energy]

Notes on the Experiment
Glacial acetic acid is used because it is a polar solvent capable of dissolving acetanilide, and the acetate ion is a poor nucleophile so no substitution is possible. A mixture of concentrated nitric and sulfuric acids is used as the nitrating mixture.

Notes on the Experiment
To prevent dinitration of the acetanilide, the nitrating mixture is added in small portions to the acetanilide solution (and not vice versa) so that the concentration of HNO3 is kept at a minimum. After the addition is complete the beaker is allowed to stand at room temperature for 30 minutes [more than that will lead to the formation of 2,4-dinitroacetanilide].

Notes on the Experiment
o-nitroacetanilide has higher solubility in the aqueous solution than p-nitroacetanilide.

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