Test of 10, 20 and 30 amines. (nitrous acid test)

The three classes of amines react differently with nitrous acid.

Nitrous acid is a source of electrophilic nitrosonium ion (O = N+), which reacts with amines. Nitrous acid being unstable is generated in situ from a mineral acid and sodium nitrite.

Primary aromatic amine reacts with nitrous acid to form a diazonium salt which is stable but low temperatures.

On reaction with phenol, an aromatic diazonium salt undergoes a coupling reaction to form a dye.

coupling reaction

formation of dye

Primary aliphatic amines form diazonium salts which are unstable and liberate nitrogen to form a carbonium ion which in aqueous reaction medium forms an alcohol or on proton elimination gives an alkene.

formation of alkene from aliphatic amines

So primary amines liberate N2 with nitrous acid unlike 2o and 3o amines. So this can be used to distinguish 1o amines from 2o and 3o amines.

Secondary amines, both aliphaptic and aromatic on reaction with nitrous acid give yellow colored oily N-nitrosoamines which unlike amines are insoluble in aqueous mineral acids. This is used as a test for 2o amines.

test for presence of secondary amine

Aliphatic tertiary amines form water soluble salts with nitrous acid.

action of aliphatic tertiary amines with nitrous acid

Aromatic tertiary amines on reaction with nitrous acid, undergo electrophilic substitution with nitro sonium ion at the p-position of the phenyl ring.

action of aromatic tertiary amines with nitrous acid

Test

Primary amine

Secondary amine

Tertiary amine

Action of CHCl3 and alcoholic KOH. (Carbylamine test)

Bad smelling carbylamine (Isocyanide) is formed.

No action.

No action.

Action of CS2 and HgCl2. (Mustard oil test)

Alkyl isothiocyanate is formed which has pungent smell like mustard oil.

No action.

No action

Action of nitrous acid.

Alcohol is formed with evolution of nitrogen.

Forms nitrosoamine which gives green colour with phenol and conc. H2SO4(Liebermann's test).

Forms nitrite in cold which on heating gives nitrosoa- mine which responds to Liebermann's test.

Action of acetyl chloride.

Acetyl derivative is formed.

Acetyl derivative is formed.

No action.

Action of Hinsberg's reagent.

Monoalkyl sulphonamide is formed which is soluble in KOH.

Dialkyl sulphonamide is formed which is insoluble in KOH.

No action.

Action of methyl iodide.

3 molecules (moles) of CH3I to form quaternary salt with one mole of primary amine.

2 moles of CH3I to form quaternary salt with one mole of secondary amine.

One mole of CH3I to form quaternary salt with one mole of tertiary amine.

1 comment:

Naval Pareek said...

why alkene can also formed when reacting nitrous acid with primary amine