Revision Notes

Class - 12 Chemistry

Chapter 13 – Amines

Introduction

Amines are ammonia-based organic compounds that have one or more alkyl or aryl
groups attached to the nitrogen atom. Amines play a variety of roles in living
creatures, including bioregulation, neurotransmission, and predator protection.
Many amines are employed as pharmaceuticals and treatments because of their great
biological activity.

Alkaloids are a class of physiologically active amines that are primarily produced
by plants to protect them from insects and other animals. Although some alkaloids
are used medicinally (as pain relievers), they are all poisonous and can lead to death
if consumed in high amounts.

Classification

Primary, secondary, and tertiary amines have one, two, or three alkyl or aryl groups
linked to nitrogen, respectively.

Type Examples

Primary (1 )

R  NH 2

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Secondary (2 )

R2 NH

Tertiary (3 )

R3 N

Four alkyl or aryl bonds connect a nitrogen atom in quaternary ammonium ions. Just
like in simple ammonium salts like ammonium chloride, the nitrogen atom has a
positive charge. An example of quaternary ammonium salt is as follows:

Structure of Amines

The tetrahedral geometry of ammonia is slightly deformed. One of the tetrahedral

sites is occupied by a single pair of nonbonding electrons. The bulky lone pair
compresses the H  N  H bond angles to 107 from the "ideal" sp3 bond angle of
109.5 in this geometry, which is represented by sp3 hybridization of nitrogen.
Because the bulky methyl groups expand the angle slightly, trimethylamine shows
less compression.

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The mirror counterpart of a tetrahedral amine with three distinct substituents
(including a lone pair) is non-superimposable. However, because the enantiomers
interconvert rapidly, we cannot usually resolve such an amine into two enantiomers.
The lone pair transfers from one face of the molecule to the other during this
conversion, which is called nitrogen inversion.

Inversion of configuration is not conceivable in quarterary ammonium salts with

asymmetric nitrogen atoms because there is no lone pair to undergo nitrogen
inversion.

Amines that are unable to achieve the sp2 -hybrid transition state for nitrogen
inversion exhibit chirality as well. If the nitrogen atom is enclosed in a tiny ring, for
example, it is unable to achieve the 120 bond angles that allow inversion to occur.

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Physical Properties

1. State

Lower aliphatic amines are gaseous compounds with a fishy odour. Primary amines
with three or more carbon atoms are liquid, while those with more than three carbon
atoms are solid.

Aniline and other aryl amines are generally colourless, but due to air oxidation, they
become coloured over storage.

2. Dipole Moment

Because the significant dipole moment of the lone pair of electrons contributes to
the dipole moments of the C  H and H  N bonds, amines are highly polar.

3. Solubility

N  H bonds in primary and secondary amines allow them to create hydrogen bonds.
Pure tertiary amines cannot form hydrogen bonds because they lack N  H bonds.
They can accept hydrogen bonds from molecules that have O  H or N  H bonds,
though.

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As a result of their ability to establish hydrogen bonds with water, lower aliphatic
amines are soluble in water. However, when the molar mass of amines increases,
solubility decreases due to the increased size of the hydrophobic alkyl component.
Higher amines are essentially water insoluble.

4. Boiling Point

The N  H bond is less polar than the O  H bond because nitrogen is less
electronegative than oxygen. As a result, amines and alcohols with similar molecular
weights form weaker hydrogen bonds. The boiling temperatures of primary and
secondary amines are lower than those of alcohols, but higher than those of ethers
with equal molecular weights. Tertiary amines have lower boiling temperatures than
primary and secondary amines with equal molecular weights because they lack
hydrogen bonds.

Compound BP ( C ) Type Molecular

weight
(CH3 )3 N 3 Tertiary Amine 59

CH3  O  CH 2  CH3 8 Ether 60

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CH3  NH  CH 2  CH3 37 Secondary Amine 59

CH3CH 2CH 2  NH 2 48 Primary Amine 59

CH 3CH 2CH 2  OH 97 Alcohol 60

Preparation of Amines

Alkyl Halides

Hoffmann’s Ammonolysis Method

It's a case of ammonolysis. In a sealed tube, an alkyl halide and an ethanolic

ammonia solution are heated to 100 C .

(a) A combination of goods is produced by the method.

(b) Tertiary alkyl halide isn't recommended because it produces an alkene.
(c) The reaction is initiated by a bimolecular substitution ( S N ) .
2

Example 1:

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Gabriel’s Phthalimide Synthesis

After treating phthalamide with KOH, alkyl phthalamide is produced by heating

potassium phthamide with alkyl halide. The hydrolysis that follows generates
only primary amine. To improve the yield of primary amine, alkyl phthalamide
is also treated with hydrazine.

Example 2:

Grignard Reagent

The primary amine is obtained using the Grignard reagent or a trialkyl borane after
chloramine treatment.

RMgX  ClNH 2  R  NH 2  MgXCl

Alcohols

Sabatier Reaction

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Under pressure, alcohols and ammonia are heated in the presence of a catalyst, such
as copper chromite or alumina. It is possible to obtain a blend of items.

Example 3:

Carbonyl Compounds

Reductive Amination

In the presence of ammonia, a number of aldehydes and ketones are reduced to

amines.

The reduction process can be catalysed (hydrogen 20-150 atm over Raney nickel
40 150 C or by use of sodium cyanohydridoborate, NaBH3CN ).

Example 4:

Example 5:

Example 6:

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Example 7:

Carboxylic Acids and Derivatives

Schmidt Reaction

Primary amine is produced by treating a mixture of carboxylic acid and hydrazoic

acid with cold concentrated sulphuric acid.

RCOOH  N 3 H 
Cold conc .
H 2 SO4
 RNH 2  CO2  N 2

Example 8:

Curtius Reaction

The acyl azide is pyrolyzed to create isocyanates in this process. As a result of the
following hydrolysis, amine is produced.

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Example 9:

Example 10:

Hofmann’s Degradation of Amides

Bromine and a strong aqueous KOH or NaOH solution are used to warm the amide.

(a) The product is a primary amine with one less carbon than amide.
(b) The intermediate is alkyl isocyanate, and the rearrangement is intramolecular.

Example 11:

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Hydrolysis of Amides and Isocyanides

Primary amine is given on the hydrolysis of N-substituted amide and isocyanide.

Example 12:

Example 13:

R  NC 
KOH , H 2O

 R  NH 2  HCOOK

Hydrolysis of Isocyantes also yields amines.


R  N  C  O 
H 3O

 R  NH 2

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Decarboxylation of Amino Acids

When amino acids are heated with barium hydroxide, primary amine is produced. If
there is no  -hydrogen in the alkyl group, quaternary ammonium hydroxide
decomposes into alcohol on heating, but if there is  -hydrogen, Hofmann
elimination occurs.

Nitrogen Compounds

Reduction of Cyanides, Isocyanides, Oximes, Imines

Nitrile (CN ) , oxime ( NOH ) , imine ( NH ) , enamine etc, on catalytic reduction

with H 2 , nickel gives corresponding amine.

Example 14:

Example 15:

Example 16:

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Example 17:

Example 18:

Reduction of Nitro Compounds

NItroalkanes are commonly converted to amines using tin and hydrochloric acid or
lithium aluminium hydride. For such a reduction, H 2 and a catalyst are also used.

Example 19:

Example 20:

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Example 21:

Example 22:

Example 23:

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Reactions of Amines

Sulphonylation – Hinsberg Test

Treatment with benzene sulphonyl chloride (Hinsberg reagent) or p-toluene

sulphonyl chloride.

(a) The reaction is used to separate the amine mixture.

(b) 1 and 2 amine, due to the presence of active hydrogen react and give
corresponding sulphonamide while 3 amine does not react.

(c) 1 amine product N-alkyl benzene sulphonamide is soluble in KOH forming a

water-soluble salt.

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Acylation

N-substituted amide is formed when primary and secondary amines react with acid
halide or anhydride. The reaction is used to protect the ring in aniline.

Example 27:

Example 28:

Example 29:

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Hofmann’s Exhaustive Methylation and Elimination

With damp Ag 2O , quaternary ammonium iodides are transformed to hydroxides.

Heat causes the hydroxide to be eliminated, resulting in tertiary amines and alkenes.
The fact that the least substituted alkene is the primary product is a significant
component of this elimination. Hofmann's Elimination is the name given to this
process.

Example 30:

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Example 31:

Metal Ions

Amines form coordination compounds with metal ions.

Example 32:

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Preparation of Aromatic Amines

Besides the methods in the preparation of aliphatic amines, following methods can
also be used.

Reduction of Nitro Compounds

Vapour – Phase Reduction

The reducing agents used were: CuO on SiO2 or V  Pt Catalyst.

Example 33:

Catalytic Hydrogenation

The reducing agents used were H 2 , Pd  C / Et  OH

Ammonolysis of Aryl Halides

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Phenol and Ammonia

Reduction of Azo Compounds

Reactions of Aromatic Amines

Diazonium Salt and Reactions

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Oxidation

Depending on the conditions, aromatic amines are easily oxidised to a variety of

compounds. Aniline is converted to p-benzoquinone through controlled oxidation
with Na2Cr2O7 and H 2 SO4 . In fact, p-benzoquinone is generated when a substance
is exposed to air.

If oxidation is not controlled, aniline black, a black dye, is produced.

Halogenation

The amine group ( NH 2 ) is a powerful activator and ortho/para director. On typical

bromination in H 2O , it generated 2,4, 6-tribromo aniline.

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The  NHCOCH3 group is a mild ortho and para director, and it can be used to make
ortho and para derivatives by reducing the activating power of amino groups by
acetylation of aniline.

Example 34:

Nitration

Because the nitrating mixture is oxidising and NH 2 is a strong activating group,

typical nitration of aniline is not done. Furthermore, at 288 K, aniline is protonated
to generate the meta-directing anilinium ion. As a result, in addition to ortho and
para derivatives, a considerable number of meta derivatives are generated.

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The nitration reaction can be regulated and the p-nitro derivative obtained as the
primary product by shielding the  NH 2 group with an acetylation reaction with
acetic anhydride.

Sulphonation

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Note: Normally, the  NH 2 group linked to benzene is incapable of forming the
zwitter ion, but  SO3 H is extremely acidic. As a result, sulphanilic acid produces
the zwitter ion. When the  NH 2 group is linked to benzoic acid in any location, for
example, no zwitter ion is generated.

Analysis of Amines

Amines are distinguished primarily by their basicity. An amine is nearly often a

water-insoluble chemical that dissolves in cold dilute hydrochloric acid or a water-
soluble compound whose aqueous solution colours litmus blue. The Hinsberg test is
the best way to determine whether an amine is primary, secondary, or tertiary. In the
presence of aqueous potassium hydroxide, the amine is shaken with benzenesulfonyl
chloride. Substituted sulfonamides are formed by primary and secondary amines,
but not by tertiary amines. A primary amine's monosubstituted sulfonamide has an
acidic hydrogen linked to nitrogen. This amide is converted to a soluble salt by
reacting with potassium hydroxide. Because there is no acidic hydrogen in the
disubstituted sulfonamide from a secondary amine, it is insoluble in the alkaline
reaction mixture. The way an amine reacts to nitrous acid can help determine its
classification. Primary aromatic amines, in particular, have a distinct behaviour:

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treatment with nitrous acid transforms them to diazonium salts, which generate
brightly coloured azo compounds when treated with beta-naphthol.

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