NEET Revision Notes

Chemistry
Amines

Introduction
Amines are organic compounds made composed of amino group and one or more
alkyl or aryl groups linked to the nitrogen atom. Amines have many functions in
living things, including bioregulation, neurotransmission, and predator defence.
Because of their high biological activity, several amines are used as medications
and therapies.
Alkaloids are a type of physiologically active amine produced by plants to defend
themselves against insects and other animals. While some alkaloids are used
medicinally (as pain relievers), they are all dangerous and can cause death if
ingested in large quantities.

Classification
One, two, or three alkyl or aryl groups are connected to nitrogen in primary,
secondary, and tertiary amines, respectively.
Type Examples

Primary (1 )
R - NH2

Image: Structure of cyclohexylamine and tert-butylamine

Secondary (2 )
R2 NH

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Image: Structure of n-ethylamine and piperidine

Tertiary (3 )
R3 N

Image: Structure of N,N-diethylaniline and Quinuclidine

In quaternary ammonium ions, four alkyl or aryl bonds join a nitrogen atom. The
nitrogen atom has a positive charge, much like in simple ammonium salts like
ammonium chloride. The following is an example of quaternary ammonium salt:

Image: Structure of tetraethylammonium iodide

Structure of Amines
Ammonia's tetrahedral geometry is slightly distorted. A single pair of nonbonding
electrons occupy one of the tetrahedral positions. In this geometry, the bulky lone
pair compresses the H  N  H bond angles to 107 from the "ideal" sp 3 bond
angle of 109.5 , which is represented by sp 3 nitrogen hybridization.
Trimethylamine has less compression because the bulky methyl groups extend
the angle slightly.

Image: Structure of ammonia and trimethylamine

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Non-superimposable is the mirror counterpart of a tetrahedral amine with three
different substituents (including a lone pair). We can't normally resolve such an
amine into two enantiomers since the enantiomers interconvert so quickly. During
this process, known as nitrogen inversion, the lone pair moves from one side of
the molecule to the other.

Since there is no lone pair to undergo nitrogen inversion in quarterary ammonium

salts with asymmetric nitrogen atoms, inversion of configuration is not possible.

Image: Structure of quaternary ammonium salts

Amines that can't establish the sp 2 -hybrid transition state for nitrogen inversion
also have chirality. If the nitrogen atom is confined in a small ring, it will be
unable to attain the 120 bond angles required for inversion.

Physical Properties
State
Lower aliphatic amines are odorless gaseous molecules that smell like fish.
Liquid primary amines have three or more carbon atoms, while solid primary
amines have more than three carbon atoms.
Aniline and other aryl amines are normally colourless, but they become coloured
over time owing to air oxidation.

Dipole Moment
Since 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.

Solubility
Hydrogen bonds can be formed by N  H bonds in primary and secondary
amines. Because they lack N  H bonds, pure tertiary amines cannot generate

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hydrogen bonds. However, hydrogen bonding from molecules with O  H or
N  H bonds can be accepted.

Image: Hydrogen bonding in primary, secondary and tertiary amines

Lower aliphatic amines are soluble in water due to their propensity to form
hydrogen bonds with water. However, as the molar mass of amines rises, the size
of the hydrophobic alkyl component grows larger, reducing solubility. Higher
amines are largely insoluble in water.

Boiling Point
Since nitrogen is less electronegative than oxygen, the N  H bond is less polar
than the O  H bond. As a result, hydrogen bonding between amines and
alcohols of identical molecular weights are weaker. Primary and secondary
amines have lower boiling temperatures than alcohols, but are higher than ethers
with similar molecular weights. Because they lack hydrogen bonds, tertiary
amines have lower boiling temperatures than primary and secondary amines with
comparable molecular weights.
Compound BP ( ° C) Type Molecular weight
(CH3 )3 N 3 Tertiary Amine 59
CH3  O  CH 2  CH3 8 Ether 60
CH3  NH  CH 2  CH3 37 Secondary Amine 59
CH3CH 2CH 2  NH 2 48 Primary Amine 59
CH3CH 2CH 2  OH 97 Alcohol 60

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Preparation of Amines

Image: Preparation of amines

Alkyl Halides
Hoffmann’s Ammonolysis Method
It's an ammonolysis case. An alkyl halide and an ethanolic ammonia solution are
heated to 100 C in a sealed tube.
(a) The process creates a combination of items.
(b) Because it forms an alkene, tertiary alkyl halide is not recommended.
(c) A bimolecular substitution (S N 2) sets the stage for the reaction.

Gabriel’s Phthalimide Synthesis

Alkyl phthalimide is made by heating potassium phthalimide with alkyl halide
after it has been treated with KOH. Only primary amine is produced by the
subsequent hydrolysis. Alkyl phthalimide is also treated with hydrazine to
enhance the yield of primary amine.

Example:

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Image: Reaction of Gabriel’s Phthalimide Synthesis

Grignard Reagent
After chloramine treatment, the primary amine is produced using the Grignard
reagent or a trialkyl borane.
RMgX  ClNH 2  R  NH 2  MgXCl
Alcohols

Sabatier Reaction
Alcohols and ammonia are heated under pressure in the presence of a catalyst like
copper chromite or alumina. A mixture of goods is possible to gain.
Example:

Image: Example of Sabatier reaction

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Carbonyl Compounds
Reductive Amination
A number of aldehydes and ketones are converted to amines in the presence of
ammonia.
Hydrogen 20  150 atm over Raney nickel 40  150 C or sodium cyano hydrido
borate, NaBH3CN , can catalyse the reduction process.

Carboxylic Acids and Derivatives

Schmidt Reaction
A mixture of carboxylic acid and hydrazoic acid is treated with cold concentrated
sulphuric acid to form primary amine.
RCOOH  N3 H 
Cold conc.
H SO
RNH 2  CO2  N 2
2 4

Example:

Image: Schmidt reaction

Curtius Reaction
In this procedure, the acyl azide is pyrolyzed to produce isocyanates. Amine is
formed as a result of the following hydrolysis.
Example:

Image: Curtius reaction

In the first step nitrogen gas evolves and carbon dioxide is produced along with
the amine in the second step.

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Hofmann’s Degradation of Amides
The amide is warmed with bromine and a strong aqueous KOH or NaOH solution.
(a) The final product is a primary amine with one fewer carbon atoms than
amide.
(b) Alkyl isocyanate is intermediate, and the rearrangement is intramolecular.
Example:

Image: Reaction of Hofmann degradation

Hydrolysis of Amides and Isocyanides

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

Image: Hydrolysis of amides

Example:
R  NC 
 R  NH 2  HCOOK
KOH , H 2 O

Hydrolysis of Isocyantes also yields amines.
H 3O 
R  N  C  O 

 R  NH 2

Decarboxylation of Amino Acids

Primary amine is formed when amino acids are heated with barium hydroxide.
On heating, quaternary ammonium hydroxide decomposes into alcohol if there is
no  -hydrogen in the alkyl group, but if there is, Hofmann elimination occurs.

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Image: Degradation reaction of amino acids

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:

Image: Reaction of cyanide

Example:

Image: Reaction of oxime

Example:

Image: Reaction of imine

Reduction of Nitro Compounds

Tin with hydrochloric acid or lithium aluminium hydride are widely used to
convert nitroalkanes to amines. H 2 and a catalyst are also utilised in this
reduction.

Reactions of Amines
Sulphonylation – Hinsberg Test

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Treatment with benzene sulphonyl chloride or p-toluene sulphonyl chloride
(Hinsberg reagent).
(a) The reaction is used to separate the amine mixture.
(b) Primary and secondary amines react to generate matching sulphonamides
in the presence of active hydrogen, while tertiary amine does not.
(c) The main amine product, N-alkyl benzene sulphonamide, dissolves in
KOH and creates a water-soluble salt.

Image: Hinsberg test

Nitrous Acid Test

(a) When a primary amine interacts with HNO3, alcohol is frequently the
result. As an intermediate, diazonium salt is generated due to the reaction.
(b) Secondary amine produces nitrosoamine, a yellow oily liquid.
(c) A soluble salt forms when the tertiary amine is dissolved in cold HNO2 .
Example:
CH3CH 2 NH 2   CH3CH 2OH  N 2  H 2O
HNO 2

Example:
 CH3 2 NH 
HNO
  CH3 2 N  N  O  H 2O
2

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Carbylamine Reaction
When primary amine is treated with chloroform and alcoholic KOH, it creates
pungent alkyl carbylamine vapours that are unpleasant or pungent.
The reaction is referred to as a primary amine test:

Image: Reaction between chloroform and alcohol

Treatment with CS2 / HgCl2

(a) Dithiocarbamic acid is generated when primary amine is heated with
carbon sulphide which is subsequently destroyed by mercuric chloride to
produce alkyl isothiocyanate. Hofmann's Mustard Oil Reaction is the name
of the reaction.
(b) Mercuric chloride does not degrade dithiocarbamic acid, which is produced
by secondary amine.
(c) Carbon sulphide has no effect on the tertiary amine.

Image: Reaction of carbon sulphide with primary, secondary and tertiary amine

Acylation
When primary and secondary amines react with acid halide or anhydride, N-
substituted amide is produced. In aniline, the reaction is employed to protect the
ring.

Hofmann’s Exhaustive Methylation and Elimination

Quaternary ammonium iodides are converted to hydroxides by Ag2O . The
hydroxide is removed by heat, resulting in tertiary amines and alkenes. The fact

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that the least substituted alkene is the major product is a key factor in this process.
This procedure is known as Hofmann's Elimination.
Example:

Image: Hofmann elimination reaction

Metal Ions
Amines form coordination compounds with metal ions.
Preparation of Aromatic Amines
In addition to the methods for making aliphatic amines, the following methods
can be employed.

Reduction of Nitro Compounds

Vapour – Phase Reduction
The reducing agents used were: CuO on SiO2 or V  Pt Catalyst.
Example:

Image: Vapour phase reduction

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

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Image: Catalytic hydrogenation

Ammonolysis of Aryl Halides

Image: Ammonolysis of aryl halide

Reduction of Azo Compounds

Image: Reaction of azo compounds

Reactions of Aromatic Amines

Diazonium Salt and Reactions

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Image: Reaction of aromatic amine

Image: Reaction of diazonium salt

Oxidation
Aromatic amines can be quickly oxidised to a range of chemicals depending on
the conditions. Through controlled oxidation using Na2Cr2O7 and H 2 SO4 ,

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aniline is transformed to p-benzoquinone. When a chemical is exposed to air, p-
benzoquinone is produced.
Aniline black, a black dye, is produced if oxidation is not controlled.

Image: Oxidation reaction of aniline

Halogenation
( NH 2 ) is a strong activator and ortho/para director. It produced 2,4, 6-tribromo
aniline after normal bromination in H 2O

Image: Halogenation reaction

By lowering the activating effect of amino groups by acetylation of aniline, the

 NHCOCH3 group can be exploited to produce ortho and para derivatives.

Nitration
Typical aniline nitration is not done because the nitrating mixture is oxidising and
NH 2 is a strong activating group. Aniline is also protonated at 288 K to produce
the meta-directing anilinium ion. As a result, a large number of meta derivatives
are produced in addition to ortho and para derivatives.

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Image: Nitration reaction
By shielding the  NH 2 group with an acetylation reaction with acetic anhydride,
the nitration reaction can be controlled and the p-nitro derivative obtained as the
main product.

Image: Reaction of aniline with pyridine

Sulphonation

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Image: Sulphonation reaction

Note:
The  NH 2 group attached to benzene is normally incapable of producing the
zwitter ion, whereas SO3H is highly acidic. Sulphanilic acid forms the zwitter
ion as a result. There is no zwitter ion produced when the  NH 2 group is coupled
to benzoic acid in any place.

Analysis of Amines
Amines is distinguished primarily by their basicity. An amine is a water-insoluble
chemical that dissolves in cold dilute hydrochloric acid or a water-soluble
molecule that turns litmus blue in an aqueous solution. The best approach to tell
if an amine is primary, secondary, or tertiary is to use the Hinsberg test. The amine
is shaken with benzenesulfonyl chloride in the presence of aqueous potassium
hydroxide. Primary and secondary amines, but not tertiary amines, create
substituted sulfonamides. The monosubstituted sulfonamide of a primary amine
has an acidic hydrogen connected to nitrogen. By interacting with potassium
hydroxide, this amide becomes a soluble salt. The disubstituted sulfonamide from
a secondary amine is insoluble in the alkaline reaction mixture because it lacks
an acidic hydrogen. The way an amine reacts with nitrous acid can aid in
classifying it. Primary aromatic amines, in particular, have a unique behaviour:
when they are treated with nitrous acid, they become diazonium salts, which
when combined with beta-naphthol produce vividly coloured azo compounds.

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Image: Hinsberg test

Solved examples:
1. The best reagent for converting-2-phenylpropanamide into 1-
phenylethanamine is.
 A  excess H 2 / Pt
 B  NaOH / Br2
 C  NaBH 4 / methanol
 D  LiAlH 4 / ether
Correct Answer: Option (B)
Explanation:
The Hoffmann bromamide reaction, also known as the degradation reaction,
begins with the treatment of the primary amide group with halogen (Br), and then
the halogen substituted amide product is converted to primary amine with the
release of carbon dioxide gas.
The reaction is shown below.

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Image: 1-phenylethanamine
Thus, option (B) is correct.

2. Which of the following compounds will not undergo azo coupling reaction
with benzene diazonium chloride?
(A) Aniline
(B) Phenol
(C) Anisole
(D) Nitrobenzene
Correct Answer: Option (D)
Explanation:
A weak electrophile, such as Diazonium cation, readily reacts with electron-rich
compounds, such as hydroxyl groups and amine groups. They do not react with
electron removing groups such as nitro groups. As a result, nitrobenzene will not
undergo azo coupling with benzene diazonium chloride. Thus, option (d) is
correct.

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