chemistry

amines
Sakshi Vora

IIT - Roorkee

10th, 12th CBSE State Topper

7+ Years of Teaching Experience

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Amines
Amines
Amines are derivative of ammonia where one or more hydrogen
atoms are replaced by alkyl or aryl groups.

Primary Amine :

Secondary Amine :

Tertiary Amine :
PREPARATION OF AMINES
By the ammonolysis of alkyl halide :

This method of preparation of amines involves nucleophilic

substitution by ammonia or an amine molecule on an alkyl halide
GABRIEL PHTHALIMIDE SYNTHESIS
Gabriel Phthalimide Synthesis :

Potassium phthalimide can be used to prepare primary amines by

the method known as Gabriel synthesis.
Important points

● It follows SN2 mechanism

● Alkyl halide must be primary or secondary only
● Only and only primary amines will be formed
HOFFMANN BROMAMIDE DEGRADATION
 By Hofmann Bromamide degradation reaction :

Primary amide react with solution of bromine or chlorine in

sodium hydroxide or potassium hydroxide to yield amines

Δ
R - C - NH2 + Br2 + 4 KOH R - NH2 + 2KBr + K2CO2 + 2H2O
Mechanism
#SVshortcut

This reaction is shown by primary amides or primary

imides only
Note :

● Intermediate products of this reaction is R - N = C = O

● Migration of alkyl group is the r.d.s

● No change takes place in the configuration of chiral carbon during

migration of alkyl group.

● Rearrangement is purely intramolecular

Practice Questions
A.

B.
[Sep. 06, 2020 (II)]

C.

D.
A.
B.
C. [April. 8, 2019 (I)]
D.
By the reduction of Nitriles and Isonitriles
By reduction of Nitro compounds :

Nitro alkanes are reduced catalytically to primary amine.

(a) By LiAlH4
(b) By Metal and acid (commonly used Sn + HCl or Fe + HCl)

reduction
RNO2 RNH2 + 2H2O
4H
A.

B.

C.

D.
[Sep. 05, 2020 (I)]
A.
B.

C. [2016]
D.
A.
[Adv. 2015]

B.

C.

D.
SCHMIDT REACTION
From Alkanoic acid (Schmidt Reaction):
#SVshortcut
Other methods of preparation
From Alkyl chloride :
Important note
Cu2O neutralises the evolved HCl in form of Cu2Cl2 + H2O otherwise HCl
forms additional salt with amines.
From Grignard reagent :

R - Mg - Cl + Cl - NH2 R - NH2 - MgCl2

From Alcohol :
R - OH + H + NH2 300o C R - NH2 + H2O
-H2O
CHEMICAL PROPERTIES
Alkylation reaction :

Aliphatic amines undergo alkylation on treatment with an alkyl halide in a

basic medium such as ammonia.
Hofmann elimination
Hofmann Elimination reaction

When a quaternary ammonium hydroxide is heated strongly, it

decomposes to yield water, a tertiary amine and an alkene.
Hofmann Elimination reaction
Reaction with grignard reagent
Reaction with Grignard reagent :

Since primary and secondary amines have active hydrogen, they on

reaction with Grignard reagent give alkanes.
Reaction with carbonyl compounds
Reaction with Aldehydes and Ketone :

RNH2 + CH3CHO RN = CHCH3 + H2O

Acylation reaction

1o and 2o amines react with acetyl chloride or acetic anhydride to form

acetyl derivatives.
Note :
(a) Tertiary amines do not undergo this reaction because of absence of
replaceable H-atom.
(b) When Benzoyl chloride is used in place of acetyl chloride reaction is
called ‘Schotten - Baumann’ reaction
Practise questions
A.

B.

[Jan. 09, 2020 (I)]

C.

D.
Oxidation reactions
Oxidation :

Oxidised to aldehydes and ketones.

[0] H2O
RCH2NH2 R-CH = NH R-CHO + NH3
KMnO4 aldimine aldehyde

[0] H2O
R2CHNH2 R2C = NH R2C = O + NH3
KMnO4 ketone
Ketimine
Secondary Amine :

[0]
2R2NH R2N - NR2
KMnO4
(tetra - alkyl hydrazine)

R2NH caro’s acid R2N - OH

(dialkyl hydroxylamine)
Tertiary Amine :
Resistant to KMnO4 but oxidised by neutral and aqueous H2O2 in cold to
form trialkyl amine oxide.
POC OF AMINES
ISOCYANIDE TEST/CARBYLAMINE TEST
Isocyanide test or Carbylamine reaction :

Primary amines when heated with chloroform and KOH solution, alkyl
isocyanides is produced which have characteristic foul smell.

RNH2 + CHCl3 + 3KOH RNC + 3KCl + 3H2O

Mechanism
Note:

● Attacking electrophile is DCC

● Interaction of amine with DCC is rds
● Rate of reaction ∝ nucleophilicity of amine
● Used to identify primary amine
A. B.
C. D.

[Jan. 11, 2019 (II)]

Practise questions
A.
B.
C. [Jan. 9, 2019 (I)]

D.
A.
[April. 15, 2018 (I)]
B.
C.
D.
A. C.

[Main 2017]
B. D.
DIAZOTIZATION REACTION
Diazotization reaction
Used for distinction between AROMATIC and ALIPHATIC PRIMARY
AMINES
Mechanism
Important points
● Nitrosonium ion is the attacking electrophile
● Diazotization is carried out by primary amines only
● Carbocation intermediate is formed
● Rearrangement is possible
● With sec amine, yellow oily liquid of N-Nitroso amine is obtained
Important points
Reaction with Nitrosyl chloride
(TILDEN’S REAGENT)

R - NH2 + NOCl ⟶ R - Cl + N2 + H2O

Practise questions
A. [Sep. 04, 2020 (II)]

B.

C.

D.
 [Jan. 09, 2020 (I)]
A. B.

C. D
.
 [Jan. 09, 2020 (II)]

A. B. C. D
.
 [Jan. 07, 2020 (II)]

A. C.

B. D.
 [April. 15, 2018 (II)]

A.
B.
C.
D.
HINSBERG REAGENT
Reaction with Hinsberg reagent

This is a method for separation of 1o, 2o and 3o amines Hinsberg

Reagent is

C6H5 - SO2 - Cl . (Benzene sulphonyl chloride)

RNH2 + Cl - SO2 - C6H5 ⟶ R - NH - SO2 - C6H5 + HCl

A. Primary amines form N - Alkyl benzene sulphonamide

B. Secondary amines form N, N - dialkyl benzene sulphonamide

C. Tertiary amines do not react because they do not process a

replaceable Hydrogen atom.
BECKMANN’S REARRANGEMENT
The beckmann Rearrangement
The acid catalysed conversion of ketoximes to N - substituted
amides
Acid catalysts used are proton acids (H2SO4, HCl, H3PO4) and
Lewis acids (PCl5, SOCl2, PhSO2Cl, RCOCl, SO3, BF3 etc.
The beckmann Rearrangement
BASIC CHARACTER OF AMINES
Basic Character of compounds
Basic Character of compounds
Basic Character of compounds
Basic Character of compounds
Practice Questions
 [Sep. 06, 2020 (I)]
A.
B.
C.
D.
 [Sep. 05, 2020 (I)]
A.
B.
C.
D.
 [Jan. 09, 2020 (II)]

A.
B.
C.
D.
 [Jan. 11, 2019 (II)]

A. C.

b. D.
 [Jan. 9, 2019 (I)]

A.

B.

C.
D.
 [Jan. 9, 2019 (I)]

A.
B.
C.
D.
 [Jan. 07, 2020 (I)]

A.
B.
C.
D.
 [April. 9, 2017]

A.
B.

C.
D.
 [Adv. 2017]
A.
B.
C.
D.
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SAKSHI SAKSHI