GENERAL CHEMISTRY – IV 12UCH04 UNIT 3 PART 1

UNIT 3 (ii) the 20 amine forms dialkyloxamic ester which is an oily

liquid.
Aliphatic Amines

Amines are derivatives of ammonia in which one or

more hydrogen atoms have been replaced by alkyl groups.

The amines are classified as primary, secondary or

tertiary amines according as one, two or three hydrogen atoms (iii) the 30 amine does not react as it does not contain a

in the ammonia molecule have been replaced by alkyl groups. replaceable hydrogen atom on nitrogen.

Thus the general formula of primary, secondary and The reaction mixture is now fractionally distilled. The

tertiary amines may be written RNH2, R2NH and R3N and each is 30 amine distils over and forms the first fraction. This is

characterized by the presence of the amino group –NH2, the followed by dialkyloxamic ester which forms the second

iminogroup , and the tertiary nitrogen atom , fraction. The dialkyloxamide remains behind in the distillation

respectively. flask.

Separation of Amines by Hofmann Method The dialkyloxamide and the dialkyloxamic ester

separated as above are hydrolysed with KOH to generate the

The given mixture of 10, 20 and 30 amines is heated with
free amines.
diethyl oxalate, when

(i) the 10 amine forms a dialkyloxamide which is crystalline

solid.

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GENERAL CHEMISTRY – IV 12UCH04 UNIT 3 PART 1

Separation of Amines by Hinsberg Method The remaining mixture is filtered and the filtrate on

acidification gives the sulphonamide of the 10 amine, while the

The given mixture of three amines is treated with
solid residue is the sulphonamide of the 20 amine.
benzenesulphonyl chloride and then alkalified with aqueous

sodium hydroxide. The two sulphonamides thus isolated are hydrolysed

with hydrochloric acid to generate the individual 10 and 20

(i) 10 amine forms N-alkyl-benzenesulphonamide which is soluble
amines which are fractionally distilled.
in base.

(ii) 20 amines forms N,N-dialkyl-benzenesulphonamide which is Dimethylamine,

insoluble in NaOH solution.
Preparation

Dimethylamine can be prepared in a pure stste by the

hydrolysis of p-nitroso-N,N-dimethylaniline with NaOH solution.

(iii) 30 amine does not react with benzenesulphonyl chloride.

The reaction mixture obtained after treatment with

benzenesulphonyl chloride in the presence of NaOH is now

distilled.

The tertiary amines passesover first.

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GENERAL CHEMISTRY – IV 12UCH04 UNIT 3 PART 1

Properties

Properties

Trimethylamine,

Preparation

It is prepared by heating a solid mixture of ammonium

chloride and paraformaldehyde.

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GENERAL CHEMISTRY – IV 12UCH04 UNIT 3 PART 1

Ethylenediamine,

Preparation

It is prepared by heating, under pressure, ethylene

dibromide with a large excess of ammonia.

Properties

It forms piperazine when its hydrochloride is heated.

Hexamethylenediamine,

Preparation

It is prepared by the catalytic hydrogenation of

adiponitrile prepared from adipic acid.

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GENERAL CHEMISTRY – IV 12UCH04 UNIT 3 PART 2

Acetanilide N-Methylaniline,

Preparation Preparation

It is prepared by heating aniline with acetyl chloride. It is prepared by heating aniline and methyl alcohol
together with sulphuric acid under pressure.

Properties Properties

1. It reacts with nitrous acid to form a pale-yellow

It is hydrolysed by strong acids or alkalies to aniline.
nitrosoamine which gives LibermannNitroso reaction.

2. When its hydrochloride is heated, the methyl group migrates

to the para position of the ring, forming p-toluidine
hydrochloride.

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GENERAL CHEMISTRY – IV 12UCH04 UNIT 3 PART 2

N,N-Dimethylaniline, 2. It condenses with carbonyl chloride to form diphenylmethane

derivatives.

Preparation

It is prepared by the direct methylation of aniline. 3. When its hydrochloride is heated to 300 0C under pressure, one

or both methyl groups migrate from the N atom to the para

position, and if it is already blocked, to the ortho position.

Properties

1. N,N-dimethylaniline reacts with nitrous acid to form p-

nitrosodimethylaniline.

This reaction is known as Hofmann-Martius rearrangement.

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GENERAL CHEMISTRY – IV 12UCH04 UNIT 3 PART 3

Diazonium Compounds

Amines when treated with nitrous acid in cold mineral

acid solution, yield a very important class of compounds known Step 3

as diazonium compounds or diazonium salts.
Nitrosoaniline undergoes rearrangement followed by

dehydration to form diazonium ion.

The formation of a diazonium compound by the

interaction of sodium nitrite, an inorganic acid and a primary

aromatic amine, in an ice-cold solution is known as Diazonium ion as a weak electrophile

diazotization.
Diazonium ion has the structure:
Mechanism of Diazotization

Step 1

Nitrous acid furnishes nitrosonium ion in presence of

acid. Diazonium ion prepared from aryl primary amines

acts as a weak electrophile, because the nucleophilicity of the

amino nitrogen is reduced by partial withdrawal of the

unshared electron pair on nitrogen into the nucleus.

Step 2

Nitrosonium ion combines with aniline to form

nitrosoaniline.

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GENERAL CHEMISTRY – IV 12UCH04 UNIT 3 PART 3

Diazoacetic ester (Ethyldiazo acetate) 3. Preparation of heterocyclic compounds

Preparation Ethylene and acetylene react with diazoacetic ester to

give heterocyclic compounds.

It is prepared by treating an ie cold solution of

hydrochloride of ethylamino acetate with ice cold ice cold

sodium nitrite solution.

Synthetic applications

1. Preparation of halogenated acids

Diazoacetic ester reacts with conc.hydrochloric acid to

give ethyl chloroacetate which on hydrolysis gives chloroacetic

acid. 4. Preparation of glycine ester

Reduction of diazoacetic ester with zinc and acetic acid

gives glycine ester.

2. Preparation of glycollic acid

Diazoacetic ester is boiled with dilute.HCl, ethyl

5. With compounds containing active hydrogen atom
glycollate is obtained. It is hydrolysed to get glycollic acid.

Diazoacetic ester reacts with compounds containing an

active hydrogen atom such as acetic acid it gives

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GENERAL CHEMISTRY – IV 12UCH04 UNIT 3 PART 3

acetylglycollic ester. With ethanol it gives ethyl ether of 2. Formation of ethers

glycollic ester.
Diazomethane methylates alcohols and phenols and

give ethers.

Diazomethane

Preparation

Methylamine is treated with ethyl chloroformate to

give N-methylurethan. This on treatment with nitrous acid in

ether gives N-methyl-N-nitrosourethan. This on warming with

3. Formation of tertiary amine
methanolic KOH gives diazomethane.

Methyl aniline reacts with diazomethane to give

dimethyl aniline.

Synthetic Applications

1. Formation of methyl esters

Diazomethane reacts with acids to give methyl esters.

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GENERAL CHEMISTRY – IV 12UCH04 UNIT 3 PART 3

4. Conversion of an aldehyde to ketone

Aldehydes react with diazomethane to give methyl

ketones.

5. Formation of heterocyclic compounds

Diazomethane adds to alkenes and alkynes to form

heterocyclic compounds.

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