Amines

NITRO COMPOUNDS
y HNO2 exists in the following two tautomeric
forms
H–O–N=O
nitrite form

Concept Ladder

Organic compounds
y Alkyl derivatives of the nitrite form are called containing nitro as the
alkyl nitrites while the alkyl derivatives of functional group are
nitro form are called nitroalkanes called nitro compounds
Nitroalkanes containing
Alkyl Nitre (R–O–N=O) a-hydrogen atoms show
tautomerism.

Classification of Nitro Compounds

Structure of Nitro Compounds

The resonance hybrid structure (III) suggests Rack your Brain

that the two N—O bonds are equal. Bond length of
N—O bonds is 121 pm which lies in between N—O Will tertiary nitroalkanes show
single bond length of 136 pm and N=O double bond tautomerism?
length of 114 pm.
Amines

1.
 Methods of preparation of Alkyl nitrite
y Alkyl nitrite is prepared by adding concentrated Concept Ladder
H2SO4 to aqueous solution of sodium nitrite
and alcohol.
Nitro compounds act as
versatile building blocks
for the synthesis of
For example, pharmaceutically relevant
substances.

y Alkyl nitrite is also obtained by the reaction

of alkyliodide and potassium nitrite as follows Rack your Brain

For example, What is the hybridisation of

nitrogen in nitroalkanes and
nitroarenes?
y Alkyl nitrite can also be prepared by the
action of nitrogen trioxide on alcohol.
For example,

Physical Properties
Concept Ladder
y At ordinary temperature, ethyl nitrite is a
gas which can be liquefied on cooling into a Nitrite ion is an ambidient
colourless liquid (boiling point 290 K) having nucleophile since it has
a characteristic smell of apples. two sites (oxygen and
y Nitroalkanes are sparingly soluble in water nitrogen) through which it
while nitroarenes are insoluble. can attack an alkyl halide.
y 1° and 2° nitroalkanes dissolve in aq. NaOH to
form salts.
y It has an important property of dilating the
blood vessels so it reduces hypertension and
severe pain of angina pectoris.

Chemical properties Rack your Brain

Hydrolysis : Alkyl nitrite can be hydrolysed by Why nitro compounds are

water, dilute alkali or dilute acid forming alcohol. classified as explosophore
group?
RONO + 2H2O 
→ ROH + NH3 + H2O
Amines

2.
For example
C2H5ONO + 2H2O 
→ C2H5OH + NH3 + H2O Concept Ladder
Reduction : On reduction with Sn/HCl, it gives
alcohol, ammonia or hydroxyl amine. When higher alkanes
Sn+HCl
RONO + 6 H   → ROH + NH3 + H2O are nitrated, mixtures of
nitroalkanes including
Sn+HCl
RONO + 4 H   → ROH + NH2OH those formed by the rupture
of carbon-carbon bond are
For example, also obtained. This method
is widely used for the
Sn+HCl
C2H 5ONO + 6 H  → C2H5OH + NH3 + H2O commercial production of
nitroalkanes as the mixture
Sn+HCl
C2H 5ONO + 4 H   → C2H5OH + NH2OH of nitroalkanes formed
and can be separated by
Method of preparation of Nitro Alkanes fractional distillation.
From alkyl halide : When alkyl halides and
alcoholic silver nitrate solution react, nitroalkanes
are formed as follows:
∆
RX + AgNO2 → RNO2 + AgX
Rack your Brain
For example,
C2H5Br + AgNO2 
→ C2H5NO2 + AgBr Why a mixture of nitro and
nitrite compound is produced,
From a-Halo substituted acids
when alkyl halide is treated with
∆
ClCH2COOH + NaNO2 → O2NCH2COOH + NaCl sodium/potassium/silver nitrate?

∆
O2NCH2COOH → CH3NO2 + CO2

By nitration of paraffin : As nitration of paraffins

(alkanes) is quite difficult in comparison to
Concept Ladder
aromatic hydrocarbons so they can undergo
nitration only with fuming HNO3 in the vapour
Nitroalkanes are also
phase at 423–673K under pressure. Here due to
widely used as a propellent
cleavage of C–C bonds a mixture of Nitro alkanes in rockets i.e. nitromethane
is formed. It occurs by free radical mechanism. is a liquid propellant
∆
R – CH3 + HONO2 → RCH2NO2 + H2O and nitrocellulose gel in
nitroglycerine are used as
solid propellants.
Amines

3.
 For example,
400°C
CH3 − CH3 + HONO2  → CH3CH2NO2 + H2O + CH3NO2

400°C
CH3 − CH3 + HONO2  → CH3CH2NO2 + H2O + CH3NO2

NO2
funing HNO3
|
CH3 − CH2 − CH3 
673K
→ CH3 − CH − CH3 + CH3 − CH2 − CH2NO2 + CH3NO2 + C2H5NO

Physical properties
y Nitroalkanes are colourless liquids and have
a pleasant smell.
y These are partially soluble in water but readily
soluble in organic solvents.
y They have high value of boiling point due to Rack your Brain
their polar nature.
Why the higher nitroalkanes are
Chemical properties insoluble in water but readily
—NO2 group is a resonance hybrid of the soluble in organic solvents?
structures given below. In it, resonance is proved
by the fact that both the N—O bonds have the
same bond length.

Acidic character : These are slightly acidic due

to presence of α-hydrogen atom, so react with
strong alkali like aqueous NaOH to form salts.
Concept Ladder

The main reason for

the acidic character of
1° and 2° nitroalkanes
Due to a-H-atom Tautomerism exists are (i) strong electorn
withdrawing nature of the
nitro group and (ii) the
resonance stabilisation of
the carbanion of the salt
so produced.
Amines

4.
In presence of an alkali, mainly aci-form
dominates. Rack your Brain

During hydrolysis, how does the

aci-form of nitroalkanes acts like
- electrophile or nucleophile?
Reaction with nitrous acid : Primary nitroalkanes
react with nitrous acid to give nitrolic acid which
dissolves in NaOH to give a red solution of sodium
nitrolate.

For example,

Secondary nitroalkanes give pseudonitroles with

HNO2 which give blue colour in NaOH solution.

Concept Ladder

For example
The C—N bond of the
primary and secondary
nitroalkanes are split by
strong mineral acid.
This method of hydrolysis
of nitroalkanes has
Tertiary nitroalkanes do not give this reaction due
been used for the
to absence of α-hydrogen atom.
industrial preparation of
This behaviour of HONO with 1o, 2o, 3o to R-NO
Hydroxylamine.
forms the basis of victor meyer test for alcohols.
Amines

5.
 Hydrolysis : Primary nitroalkanes undergo acidic
hydrolysis to give acids as follows Previous Year’s Questions
HCl
RCH2NO2 + H2O →
or
RCOOH + NH2OH
85%H2SO4
An organic compound (C3H9N)
For example, (A), when treated with nitrous
HCl
CH3CH2NO2 + H2O → CH3COOH + NH2OH acid, gave an alcohol and N2 gas
was evolved. (A) on warming
y Secondary nitroalkanes on hydrolysis give
with CHCl3 and caustic potash
ketones as follows:
gave (C) which on reduction gave
HCl
2R2CHNO2 → 2R2CO + N2O + H2O isopropylmethylamine. Predict the
structure of (A).
For example  [AIPMT-2012]
HCl
2 (CH3 )2 CHNO2 → 2 (CH3 )2 CO + N2O + H2O (1) (CH3)2–CH–NH2
(2) CH3CH2–NH–CH3
y Tertiary nitroalkanes do not show this reaction (3) (CH3)3–N
(4) CH3CH2CH2–NH2
Reaction with grignard reagent : Nitroalkane in
Aci-form gives alkanes with Grignard reagent as
follows:

For example,

Halogenation : Nitroalkanes undergo halogenation

at α-position.
For example,
Cl Cl
| |
Cl 2 −NaOH
CH3CH2NO2 → CH3 .CH.NO2 + CH3 — C — NO2
|
Cl
Cl +NaOH
CH3NO2 →
2
CCl 3 .NO2
nitromethane chloropicrin Rack your Brain
Cl Cl
| |
Cl 2 −NaOH
CH3 — CH — NO2 → CH3 — C — NO2 What is chloropicrin and why is it
| important?
Cl
Amines

6.
Reduction : Nitroalkanes undergo reduction as
follows:

Reduction by Sn+HCl or Zn/HCl or LiAlH4 gives

primary amine as follows: Rack your Brain
Sn+HCl
RNO2 + 6 H  
→ RNH2 + 2H2O
In mannich reaction, the aci
For Example, form act as - nucleophile or
Sn+HCl
C2H5NO2 + 6[H]  → C2H5NH2 electrophile?
Nitroethane Ethyl amine

Reduction with zinc dust and NH4Cl gives

hydroxylamines as follows:
Zn+NH Cl
RNO2 + 4 H 
4
→ RNHOH + H2O

For example
Zn+NH Cl
C2H5NO2 + 4 H 
4
→ C H NHOH + H2O
2 5
Ethyl hydroxyl Amine
Concept Ladder
y Reduction with SnCl2/HCl gives a mixture of
oxime and hydroxyl amine as follows: Primary and secondary
nitroalkanes undergo
SnCl /HCl
RCH2NO2 →
2
RCH2NHOH + RCH = NOH mannich reaction with
SnCl /HCl primary and secondary
CH3CH2NO →
2
CH3CH2NHOH + CH3CH = NOH
aliphatic amines and
formaldehyde, yielding
Mannich reaction : It involves the condensation nitroamines in high yield.
of nitroalkane, formaldehyde, primary amine and
hydrogen chloride as follows:

NO2 R
| |
R2CHNO2  HCHO  RNH2 .HCl 
 R2 C CH2 . NHHCl
.  H2O
For example
Amines

7.
 Effect of heat:
y On moderate heating below 300oC, Concept Ladder
nitroalkanes form alkenes.
300°C
RCH2CH2NO2  → RCH
= CH2 + HNO2 Nitro group can easily be
y On heating rapidly, explosion takes place. reduced to a variety of
For example, products, depending upon
∆ 1 3 the type of reagent and
CH3NO2 → CO2 + N2 + H2 the reaction conditions
2 2
used. but if the reaction
is allowed to completition
NITROARENES then the final product of
the reaction is primary
amines.
or C6H5NO2 (Nitrobenzene)

y It is called Oil of Mirbane and has a bitter,

almond like odour
Methods of preparation Rack your Brain

What is the best reagent for

carrying out the reduction of
nitroalkane in neutral medium to
hydroxylamines?

If temperature is above 100oC, further

nitration takes place and the product is meta-
dinitrobenzene.

Concept Ladder

Nitroarenes and chiefly

polynitroarenes are
Physical properties unstable and they
y It is a light brown coloured oily liquid with decompose with explosive
a boiling point of 210oC. violence, when heated.
y It is insoluble in water and volatile in steam.
Amines

8.
Chemical properties
Due to benzene ring: Concept Ladder
Nitro group deactivates the benzene ring,
therefore further substitution takes place only
If two or more nitro groups
at meta-position and the rate of electrophillic
are present in the benzene
substitution is much slower than that of benzene.
ring, it is possible to reduce
one of them without
Halogenation:
affecting the others. Such
reductions are called
selective reductions.

Previous Year’s Questions

Electrolytic reduction of
Nitration
nitrobenzene in weakly acidic
medium gives
 [AIPMT]
(1) N-phenylhydroxylamine
(2) nitrosobenzene
(3) aniline
(4) p-hydroxyaniline

Sulphonation:

Rack your Brain

What is TNT?
Amines

9.
 Friedel crafts reaction
Concept Ladder

Nitro group, due to its

electron-withdrawing
nature reduces the
electron density at the o-
Friedel Crafts reaction does not occur in any of and p-positions. Electron
the meta di-recting groups like —NO2, —CHO, — density is comparatively
COOH, —CX3, —SO3H, —COX etc more at the m-position,
i.e., the nitro group is
Reduction of nitro benzene m-directing.

Rack your Brain

Can nitroarenes go under

distillation?
In a strong acidic medium

In a neutral medium
Amines

10.
In basic medium

Concept Ladder
y Nitrosobenzene and Phenylhydroxylamine
further react to give following products
Different product can
depending upon reagent used. be obtained from nitro
y With Zinc dust/NaOH or sodium amalgam, benzene on reduction but
azobenzene and hydrazobenzene are formed. the nature of the product
y With sodium arsenite and NaOH, azoxybenzene depends upon the reducing
agent used.
is formed.

Q1 What is Baker-Mulliken’s test?

Sol. C6H5NO2 

4 2 Zn/NH Cl ,H O
 C6H5NHOH
Nitrobenzene Phenylhydroxy
ylamine

C6H5NHOH  2 [Ag(NH3 )2 ]  2 OH  C6H5N  O 2 Ag   4 NH3  2 H2O

Tollens' reagent Nitrosobe
enzene Silver
mirror
Amines

11.
 Electrolytic reduction:
Rack your Brain
In a weak acidic medium
Why nitrobenzene is used as a
solvent during Friedel-Craft’s
reaction?

In a strong acidic medium

Reaction with solid KOH :

It is an example of nuclephilic substitution Previous Year’s Questions
reaction.
Electrolytic reduction of
nitrobenzene in strongly acidic
medium gives
 [AIPMT]
(1) azobenzene
(2) aniline
(3) p-aminophenol
(4) azoxybenzene

Q2 Toluene is more easily nitrated than benzene. Explain.

Sol. Nitration is an electrophilic substitution reaction and thus occurs more readily at a
site where the electron-density is more. Now in toluene, there is electron-donating
CH3 group. In other words, the electron-density in the toluene ring is much more
than in the benzene ring. As a result, toluene is nitrated more easily than benzene.
Amines

12.
 The –NO2 group is very firmly linked to
Benzene- nucleus, moreover partial double Concept Ladder
bond character devel- ops due to resonance so
nitrobenzene becomes inert and does not give Nitro group can easily be
reduced to a variety of
displacement reaction.
products, depending upon
In case any group like –X is present at o, p the type of reagent and the
positions to –NO2 group, it increases the chance reaction conditions used.
of nucleophillic substitution of this group.

Uses
y Nitrobenzene is used in the manufacture of
azodyes, aniline and as a perfume material in
shoe polish and soaps.
y A mixture of TNT (20%) and NH4NO3 (80%)
called amatol is used in coal mining.
y A mixture of TNT (15%), NH4NO3 (65%),
aluminium (17%) and charcoal (3%) is called Rack your Brain
ammonal and is used for blasting purposes.
y RDX (Research and Development Explosive) is What are the reagent used
also called cyclonite. for the partial reduction of
y RDX is prepared by controlled nitration of nitrobenzene?
hexamethylene tetraamine (obtained from
formaldehyde) with fuming nitric acid at 293
K.

AMINES

Previous Year’s Questions

The action of nitrous acid on an

y Amines are the alkyl or aryl derivatives of aliphatic p[rimary amine gives
ammonia.  [AIPMT]
y Amines have a general formula CnH2n + 3 N. (1) secondary amine
y Like NH3 an amine is also Pyramidal in shape (2) nitro alkane
(3bp + 1lp) with bond angle less than 109.5° (3) alcohol
There are three types of amines primary (4) alkyl nitrite
(RNH2), sec-ondary (R2NH) and tertiary (R3N).
Amines

13.
Amines

14.
y All the three types of amine are obtained
from ammonia by replacing H-atoms by alkyl
or aryl groups.

Amine Common name IUPAC name

Primary amines
CH3CH2CH2NH2 n-Propylamine 1-Propanamine
(CH3)2CHNH2 Isopropylamine 2-Propanamine

Secondary amines
CH3NHCH3 N-Methylaminomethane N-Methylmethanamine
CH3CH2NHCH3 Ethylmethylamine N-Methylethanamine

Tertiary amines
(CH3)3N N, N-Dimethylaminomethane N, N-Dimethylmethanamine
(C2H5)2NCH3 N-Ethyl-N-methylaminoethane N-Ethyl-N-methylethanmine

Aralkylamines
C6H5—CH2NH2 Phenylaminomethane Phenylmethanamine
C6H5—CH2CH2NH2 b-Phenylethylamine 2-Phenylethanamine

y Amines show functional, chain, position and

metamerism isomerism.
y Primary, secondary and tertiary amines are
functional isomers of each other.

Q3 Calculate the number of primary, secondary and tertiary amines in case of

C4H11N?
Amines

15.
 Sol. Cof H8. N
4 11
has 4-primary, 3-secondary and 1-tertiary amines, that is, a total

1. CH3CH2CH2CH2NH2 2.

3. 4.

5. C2H5 − NH − C2H5
6. CH3 − NH − CH2CH2CH3

7. CH3 − NH − CH CH3 ( )2 8.

Here (1, 2, 3, 4) w.r.t (5, 6, 7) and (8) are functional

isomers.
Here 1 is chain isomer w.r.t to 2 and 4. 1 and 3 are
position isomers 5, 6 or 7 are metamers. Concept Ladder

Methods of Preparation for all Types of Amines Amines are organic

By Hoffmann method : molecules that include
Alkyl halide is treated with alcoholic ammonia as a nitrogen atom. Amines
follows: show up in our bodies
∆
RX + NH3 → RNH2 + HX as neurotransmitters, in
plants as alkaloids, in our
RNH2 + RX 
→ R2NH + HX
DNA, and in manufacturing
R2NH + RX 
→ R3N + HX processes.
+ −
→ R4N X (quaternary ammonium salt)
R3N + RX 

R − N+H3 X− + NaOH 

→ R − NH2 + NaX + H2O

For Example,

C2H5Cl →
3 NH
C2H5NH2 
2 5
−HCl
C H Cl
→ (C2H5 )2 NH 
2 5
−HCl
→ C2H5
C H Cl
( ) 3
N
2° Amine 3° Amine

NH CH Cl CH Cl
C6H5CH2Cl →
3
C6H5CH2NH2 
3
→ C6H5CH2NHCH3 
3
→ C6H5CH2N(CH3 )2
Benzylamine
Amines

16.
17.
Amines
 N,N–Dimethyl phenyl methanamine or
benzylamine Concept Ladder
Reactivity order of halides with amines :
R–I > R –Br > R–Cl
Due to electron withdrawing
When NH3 is in excess then R–NH2 is the
nature of the nitro group
major product and when R–X is in excess,
it deactivates the ortho
quaternary ammonium salt is the major product.
and para position of the
This is called ammonolysis of alkyl halides. It is a
nitroarene ring towards
nucleophilic substitution reaction.
further electrophilic
By ammonolysis of alcohols:
substitution reaction. This
Here, vapours of alcohol and ammonia are
selective deactivation
passed over heated alumina or thoria at 350° C
leaves only one reactive
as follows:
site-meta, hence meta
Al O
ROH + NH3 
2 3
350°C
→ RNH2 + H2O substituted products are
obtained.
RNH2 + ROH 
→ R2NH + H2O

R2NH + ROH 

→ R3N + H2O
Separation of primary, secondary, and tertiary
amine and quaternary ammonium salt :
Rack your Brain
The mixture is first treated with aqueous KOH
where the quaternary halide forms quaternary
Which positions of nitrobenzene
ammonium hydroxide, a solid product. The are easily attacked by
mixture of primary, secondary and tertiary amines nucleophiles?
is then distilled, leaving salt residue in the flask.
The mixture of primary, secondary, tertiary amines
can be separated by any of the following methods:
By fractional distillation: The mixture is subjected
to fractional distillation by which all the three
Previous Year’s Questions
amines are separated. The method is applicable
only when the three amines differ considerably
The electrolytic reduction of
in their boiling points. By Hinsberg method: Here nitrobenzene in strongly acidic
the mixture of amines is treated with Hinsberg medium produces
reagent (benzene sulphonyl chloride). [AIPMT]
y Here only primary and secondary amines react (1) p-aminophenol
while tertiary does not react with the reagent. (2) azoxybenzene
y The mixture is distilled to remove unreacted (3) azobenzene
tertiary amine. (4) aniline
Amines

18.
y The remaining mixture is treated with aqueous
KOH, in which, the derivative of primary amine
becomes soluble and that of secondary amine
remains insoluble.

N,N–Dialkyl benzene sulphonamide (insoluble in

KOH)

Concept Ladder
From here the solid residue of 2° amine and
soluble salf of 1o are separated by filteration, which
Quaternary ammonium
on hydrolysis separately gives 2° and 1° amines.
salts have N-stereocentre,
The product formed is substituted sulphonamide
therefore it shows
which are stable solids and it is formed when
enantiomers.
p-Toluene sulphonyl chloride is prefered over
benzene sulphonylchloride. Product can be easily
purified by crystallization. By Hoffmann method
y Here, diethyl oxalate is heated with the
mixture of amines.
y By primary amines and secondary amines a
solid product and an oily product are formed
repectively, while it will not react with tertiary
amines.
Rack your Brain
y The mixture is distilled where by unreacted
tertiary amines distill out first, followed by
Write the metamer of
the oily product of secondary amine. The
diethylamine.
derivative of primary amine is left in the flask.
Amines

19.
 Concept Ladder

The major drawback of

Hoffman method is RX
limited to methyl and 1°
alkyl halides.

Methods of Preparation of Primary Amines By

reduction of cyanides
LiAlH
RCN + 4H  4
Na +alcohol
→ RCH2NH2
or
Raney Ni/H2

Example,

CH3CN + 4H 
LiAlH
4
→ CH3CH2NH2 Rack your Brain
Na +alcohol

Which species acts like a

C6H5 − CH2 −
LiAlH4
CN  → C6H5 − CH2 − CH2NH2 nucleophile in this reaction?
Na +alcohol
2−Phenyl ethanamine

By reduction of nitro alkanes

Sn/HCl
RCH2NO2 + 6H →
LiAlH
RCH2NH2 + 2H2O
2

Example,
Sn/HCl
CH3CH2NO2 + 6H →
LiAlH
CH3CH2NH2 + 2H2O
2

By reduction of amides
LiAlH
RCHONH2 + 4H  4
C H OH/Na
→ RCH2NH2 + H2O
2 5

Example, Concept Ladder

LiAlH
CH3CONH2 + 4H  4
C H OH/Na
→ CH3CH2NH2 + H2O
2 5
When NH3 is in excess 1°
By reduction of oximes amine is main product in
LiAlH ammonolysis of alcohol.
RCH
= NOH + 4H  4
Na/C H OH
→ RCH2NH2 + H2O
2 5
Amines

20.
Example,

CH3=
CH NOH + 4H  4 LiAlH
→ CH3CH2NH2 + H2O Previous Year’s Questions
Na/C H OH 2 5

From alkyl halides and alchols

The number of structural isomers
RX + NH3 
→ RNH2 + HX possible from the molecular
excess
formula C3H9N is
Al O
ROH + NH3 
2 3
350°
→ RNH2 + HO [AIPMT]
excess (1) 4 (2) 5
Example, (3) 2 (4) 3
C2H5Cl + NH3 
→ C2H5NH2 + HCl
Al O
C2H5OH + NH3 
2 3
350°
→ C2H5NH2 + H2O
excess
Concept Ladder
By Schmidt reaction
conc.
Aromatic 1° amines such
RCOOH + N2H  → RNH2 + N2 + CO2
H SO 2 4 as aniline, toluidines etc.
Example, cannot be prepared by
this method because aryl
conc. H SO
CH3COOH + N3H 
2 4
→ CH3NH2 + N2 + CO2 halides do not undergo
y In this reaction, acyl azide and alkyl isocyanate nucleophilic substitution
are the reaction intermediates and by using reaction with potassium
Curtius degradation method they give primary phthalimide under mild
amines as the final product. conditions.

By Gabriel phthalimide synthesis

R may be —CH3, —C2H5 etc.

Amines

21.
 The acidic/basic hydrolysis of N-alkylphthalimides
Rack your Brain
is often slow. Therefore, hydrazinolysis (cleavage
by hydrazine) of N-alkylphthalimides is a more
How can benzylamine be
convenient and efficient method for obtaining 1°
prepared by using benzyl
amines using Gabriel synthesis. For example,
chloride and glycine by using
ethyl chloroacetate in place of
ethyl iodide?

By the reaction of Azide with NaBH4

Concept Ladder
NaBH 4
R — X + NaN3 
→ RN3 →
HO
RNH2
2
sodiumazide alkyl azide
Cyanides on reduciton
For Example, with H2 and Raney Ni or
NaBH with LiAlH4 or with sodium
C2H5Cl + NaN3 
→ C2H5N3 
HO
4
→ C2H5NH2
sodium azide ethyl azide
2 and alcohol (Mendius
reaction) give aliphatic or
By Curtius Rearrangement aryl primary amines. While
isocyanides on reduction
R  C Cl  NaN3 
 R  C N3  NaCl with H2/Ni or LiAlH4 give
|| ||
O O secondary amines.

∆ R'OH
R — C — N3 →
−N2
R − N= C= O 
Hydrolysis, ∆
→ RNH2 + CO2 + R ' OH
||
O Alkyl isocyanide 1° Amine
Acid Azide

Methods of Preparation for secondary Amines

Platinum catalyzed reduction of Iso cyanides
Pt
R ≡ C + 4 H  → RNHCH Rack your Brain
3
sec ondary amine

Example, Which method is suitable for the

Pt
ascent of amines series?
C2H5N ≡ C + 4 H  → C2H5NHCH3
N−methyl
ethanamine
Amines

22.
Mannich reaction

O O
|| ||
R  C CH3  CH2O  RNH2 
 R  C CH2  CH2  NHR
Mannich base
LiAlH
R — CONHR + 4 H 
4
→ RCH2NHR + H2O

Example,
LiAlH
CH3 − CONHCH3 + 4 H 
4
→ CH3CH2NHCH3 + H2O
N−methyl ethanamine

Hydrolysis of Dialkyl cyanamide

+
H
R2N — CN + 2H2 O → R2NH + CO2 + NH3
Example, Concept Ladder
(CH3 )2 N − CN + 2H2O → ( CH3 ) NH + CO2 + NH3
+
H
2
N−methyl methanamine Amides are reduces to
Using Grignard reagent amines, product contains
same number of carbon
atoms as the original
amide.

Methods of Preparation for Tertiary Amines

Reduction of N, N-disubstituted amides
LiAlH
RCONR2 
4 H
4
→ RCH2NR2 + H2O
 

Example, Previous Year’s Questions

(
CH3CON CH3 )2 
LiAlH
4
4 H
→ CH3CH2N ( CH3 ) + H2O
2
N,N−dimethyl ethanamine Reactin of propanamide with
ethanolic sodium hydroxide and
By decomposition of tetraammonium hydroxides
bromine will give
∆
R4 NOH → R3N + Alkene + H2O [AIPMT]
(1) Ethylamine
Example,
(2) Methylamine
(3) Propylamine
(C2H5 )4 NOH 
∆
→ ( C2H5 ) N + C2H4 + H2O
Amines

3 (4) Aniline

23.
 Physical Properties of Amines
y The first 2 members of the amine family, ethyl Concept Ladder
amine and methyl amine– are gases while
the remaining members are either solids or
Reduction of nitro
liquids.
compounds can also be
y Amines tend to have a unpleasant and distinct
carried out with Sn/Fe in
odor.
HCl or with Na and alcohol.
y ⚫ Due to presence of hydrogen bonding
these are highly soluble in water. Solubility
is inversoly proportional to Molecular weight
therefore, the decreasing order of solubility
of amines is given as: CH3NH2 > C2H5NH2 >
C3H7NH2 > …… R–NH2 > R2 NH > R3N
y These are basic in nature and are inflammable.
y Amines have lower boiling points than
alcohols due to presence of weaker hydrogen
bonding, e.g.

The above is extent of H–bonding in water in

decreasing order and stability of Ions by solvation
Chemical Properties
Basic nature:
In amines, nitrogen atom has one lone pair of Previous Year’s Questions
electrons to donate, hence they are are basic in
nature. So they form salts with acids. Which of the following reactions
+ − is appropriate for converting

RNH + HCl 
→ R NH3 Cl
2 acetamide to methanamine?
+ [NEET-2017]

R — NH → R NH3 + OH−
+ H2O 
2 (1) Hoffmann hypobromamide
Due to formation of OH aqueous solution of reaction
amines is basic in nature (2) Stephens reaction
(3) Gabriels phthalimide
 synthesis
2 R  NH2  H2PtCl6 
(RNH3 )2 PtCl 62 (4) Carbylamine reaction
Amines

Chloroplatinate
24.
Chlaroplatinates are used to determine molecular
and equivalent masses of amines. Previous Year’s Questions

Basic nature orders of amines

Acetamide is treated with the
following reagents sparately.
Which one of these would yield
methyl amine?
[AIPMT]
y R3N > R2NH > R – NH2 (1) NaOH/Br2
(2) Sodalime
(3) Hot conc. H2SO4
In gas phase or in non-aqueous solvents
(4) PCl5
y C6H5N(CH3)2 > C6H5–NHCH3 > C6H5NH2

Reaction with nitrous acid (HNO2):

A primary amine on reaction with nitrous acid
gives an alcohol, while a secondary amine on
reacting with it gives a nitroso amine. Trialkyl
ammonium nitrate is formed by tertiary amine.

Concept Ladder

Phthalic acid can again be

converted into phthalimide
and can be used again and
again.

Reaction with NOCl:

A primary amine on reaction with NOCl gives Rack your Brain
an alkyl halide whereas a secondary amine on
reacting with it gives an oily product; a tertiary
Can we form aryl amines by
amine does not react with NOCl.
Gabriel synthesis?
Amines

25.
 Concept Ladder

Leucart reaction occurs

by reductive amination,
This reaction is called Nitrosation using an ammonium
salt or an amide at high
Libermann’s nitroso test: temperatures, usually in
When nitroso amine in the presence of sulphuric the presence of catalysts.
acid, is heated with phenol, there is formation of
red coloured product takes place, which changes
to blue and finally green. This test is used to
detect both Aromatic and Aliphatic sec. amines.

y N-Nitrosoamines are cancer producing agents

i.e carcinogens.

Rack your Brain

Reaction with COCl2:
This reaction is given by primary and secondary What is leaving group in Curtius
amines only. reaction?

2 RNH2  COCl 2  RNH  CO  NHR  2 HCl

Sym-disubstituted urea

2 R2NH  COCl 2 

 R2N  CO  NR2  2 HCl

Acetylation or reaction with CH3COCl:

The presence of NH2 group is confirmed by using Concept Ladder

this reaction.
Curtius, Schmidt and
CH3COCl + RNH2 
→ CH3CONHR + HCl Lossen Rearrangement
are basically rearrngement
reactinos in which carbon
Carbylamine reaction: migrates from carbon to
nitrogen with the formaion
It is a test for primary amines. Here, isocyanide of an isocyanate. i.e., 1, 2
having pungent, bad smelling, is formed. The shift, migrating group is
reaction intermediate is dichloro carbene. an alkyl or aryl group and
leaving group.
Amines

26.
 alc . KOH
RNH2  CHCl 3  3 KOH  RNC  3 KCl  3 H2O
Isocyanide

Example,
alc. KOH
CH3NH2 + CHCl 3 + 3KOH 
→ CH3NC + 3KCl + 3H2O
methyl isocyanide(MIC)

alc.KOH
C6H5NH2 + CHCl 3 + 3KOH  → C6H5NC + 3KCl + 3H2O
phenyl isocyanide

Oxidation:
Amines can be distinguished by oxidation Rack your Brain
process as on oxidation it gives aldimine, which
on hydrolysis gives an aldehyde. What is Hofmann elimination
reaction and what are its uses?
For example,

A secondary amine on oxidation gives ketamine

which on hydrolysis gives ketone.

A secondary amine on oxidation by Caro’s acid or

H2O2 gives dialkyl hydroxylamine as follows

HO
R2NH 
2 2
H SO
 R2N  OH
2 5

N  Hydroxyl amines Previous Year’s Questions

Tetraalkyl hydrazine is formed by when secondary

Phenyl isocyanides are prepared
amine in oxidised by KMnO4 as follows by which of the following
KMnO
R2NH →
4
R2N − NR2 + H2O reaction?
[AIPMT]
y A tertiary amine on oxidation by Fenton’s (1) Reimer-Timann reaction
reagent or Caro’s-acid gives tertiary amine (2) Carbylamine reaction
(3) Rosenmund’s reaction
oxide.
(4) Wurtz reaction
HO + −
R3N + [O] 
2 2
O
→ R3NO 
→ R3 NO
Amines

27.
 Hoffmann mustard oil reaction:
Primary amine is examined by this reaction. The
product alkyl isothiocyanate having mustard oil-
like smell is formed by primary amine as follows

Hoffmann exhaustive methylation and Rack your Brain

degradation:
By following Hoffman rule, this process involves Why N-Nitrosoamines are
formation of alkene where less stable alkene will powerful carcinogens?
be the major product. For example,

According to Hoffmann rule, the above elimination

can be explained as, the carbon containing more
hydrogen atoms can eliminate b-hydrogen atom,
i.e. there is formation of less stable alkene.

Previous Year’s Questions

Which of the following statements

y In commercial preparation, Fe + HCl is used. about primary amines is false?
[AIPMT]
Aromatic Amines
(1) Alkyl amines are stronger
From chlorobenzene bases than aryl amines
(2) Alkyl amines react with
nitrous acid to produce alcohols
(3) Aryl amines react with nitrous
acid to produce phenols
(4) Alkyl amines are stronger
bases than ammonia
From phenol
Amines

28.
 Concept Ladder

The basic strength of an

amine is determined by
its basicity constant, Kb
From phenyl magnesium bromide Greater the value of Kb,
stronger is the base.

Schmidt reaction Rack your Brain

Which is more basic 2° amine or

ammonia?

From benzoic acid

The conversion of benzamide into aniline is

referred to as Hoffmann bromamide reaction.

Q4 How can you convert an amide into an amine having one carbon atom less
than the starting compound?

Sol. By Hoffmann-bromamde reaction, i.e., by heating a 1° amide with Br2 and KOH.

R  CONH2  Br2  4 KOH 


 R  NH2  K2CO3  2 KBr  2 H2O
1 Amide 1 A min e
Amines

29.
 By the hydrolysis of Isocyanide and Isocyanate
Concept Ladder

Nitrous acid (HNO2

or HONO) reacts with
aliphatic in a fashion that
provides a useful test for
distinguishing, primary,
secondary and tertiary
amines.

From benzene sulphonic acid Rack your Brain

Find out the electrophile

generated during the reaction
which reacts with amines to give
products.

Physical Properties
y Pure aniline is colourless oily liquid, but due
Previous Year’s Questions
to the action of light and air it becomes dark
brown.
y Its B.P. is 183°C. The correct increasing order of
y It is volatile in steam and soluble in water. basic strength for the following
y It can be purified by steam distillation. compounds is

Chemical Properties
Reactions due to benzene ring

Electrophilic substitution:
NH2 group in aniline is highly ring activating as
there is increase in electron density at ortho and
para positions because of delocalization of lone [NEET-2017]
pair of electrons present on the nitrogen atom. (1) III < I < II (2) III < II < I
(3) II < I < III (4) II < III < I
Amines

30.
Decrease in basicity of aniline is also confirmed
and it is due to delocalisation of pi electrons.
Concept Ladder
Halogenation
The mechamism of the
carbylamine reaction
involves the addition of
amine to dichlorocarbene
which is a reactive
intermediate generated by
the dehydrohalogenation of
chloroform. There are two
successive base-mediated
Nitration int the dehydrochlorination
of chloroform that result
in the formation of an
isocyanide.

Amines

31.
 y Nitric acid is a strong oxidizing agent so it
oxidizes NH2 group also hence direct nitration Concept Ladder
cannot be carried out. Therefore NH2 group is
protected by acetylation before carrying out
nitration. Controlled nitration with
a mixture of conc. HNO3 +
conc. H2SO4 at 293 K gives
m-nitroaniline as the major
product.

Arylation:
Diphenyl aniline is formed when aniline reacts
with chlorobenzene or phenol.

Previous Year’s Questions

Aniline is reacted with bromine

Friedel crafts reaction:
Aniline fails to give Friedel Crafts reaction, as
aniline acts as a Lewis base, so AlCl3 being an

electrophile forms salt with it, that is, C6H5 NHAlCl 3
(—NH3AlCl3– is a strong deactivating group)
Amines
water and the resulting product is
treated with an aqueous solution
of sodium nitrite in presenc eof
dilute hydrochloric acid. The
compound so formed is converted
into a tetrafluoroborate which is
subsequently heated to dry. The
final product is
[AIPMT]
(1) p-bromoaniline
(2) p-bromofluorobenzene
(3) 1,3,5-tribromobenzene
(4) 2,4,6-tribromofluorobenzene

32.
Reaction due to NH2 group
Salt formation Rack your Brain

How would a tertiary amine

would react with KMnO4?

Acylation
Concept Ladder

Due to strong activating

effect of the amino group,
aromatic amines undergo
electrophilic substitution
reactions readily. To
stop the reaction at the
monosubstitution stage,
the reactivity of the
amino group is reduced by
protection.
Benzylation (Schotten bauman reaction)

Reduction

Rack your Brain

What is black insoluble

precipitate formed during the
reaction?
Amines

33.
 Carbylamine reaction:
It is a test of chloroform and primary amines. Here Rack your Brain
dichlorocarbene is the reaction intermediate and
What is the drawback of
pungent, bad smelling isocyanites are formed.
carbylamines reaction?

With HNO2 :
When aniline is reacted with a mixture of
hydrogen chloride and sodium nitrite in cold,
benzene diazonium chloride is formed. This is
called diazotization reaction.

Oxidation :
Aniline gives different products on oxidation as Previous Year’s Questions
follows :

Which of the following is more

basic than aniline?
[AIPMT]
(1) Benzylamine
(2) Diphenylamine
(3) Triphenylamine
(4) p-Nitroaniline

With benzene chlorosulphonic acid

Rack your Brain

DIAZO COMPOUNDS
Diazonium comopunds or diazonium salts are Why less stable alkenes are
a group of organic compounds with the general mirror product in the Hoffman
Amines

methylation?

34.
molecular structure R-N2+X-, where R may be
any alkyl or aryl group and X may be halogens, Concept Ladder
hydrogen sulphate etc. Aryl diazonium salts have
frequently been used as intermediates in organic
Being an electron
synthesis.
deficient species benzene
Diazonium salt shows a
Benzene Diazonium chloride
coupling reaction with an
electron rich species such
as phenol and amines.

Diazotization
The process of diazotization is used for the
production of benzene diazonium chloride, when
an aromatic primary amine is treated with HCl
and nitrous acid between 0°C – 5°C. The reaction
is called as diazo reaction and the process is
called as diazotization.

Synthetic applications
y The solution of benzene diazonium chloride
can be used for various synthetic applications.
For the introduction of –CN, –X, –OH, –NO2
group in the benzene ring, it acts as a very good
intermediate. The preparation of synthesis of
those compounds that can not be obtained Rack your Brain
by direct substitution in benzene can be done
by the substitution of diazo group by these
Why aniline is toxic in nature?
groups. A few examples are as follows:
y Synthesis of Benzene

y Synthesis of Phenol
Amines

35.
 y Sandmayer reaction
Previous Year’s Questions

Method by which aniline cannot

y Cyanobenzene on reduction gives benzyl be prepared is
amine and on hydrolysis, gives benzoic acid [NEET-2015]
as follows (1) Hydrolysis phenyl isocyanide
with acidic solution
(2) Degradation of benzamide
with bromine in alkaline solution
(3) Reduction of nitrobenzene
with H/Pd in ethanol
(4) Potassium salt of phthanlimide
treated with chlorobenzene
followed by the hydrolysis
aqueous NaOH solution
y Gattermann reaction

y Gomberg reaction

y Synthesis of Iodo benzene

y Synthesis of C6H5F
Concept Ladder

Aniline is a stronger base

than diphenylamine which
It is called Balz-Schiemenn Reaction. in turn is a much stronger
y Synthesis of Nitro benzene base than triphenyl amine.
Thus, C6H5NH2 > (C6H5)2NH
> (C6H5)3N
Amines

36.
y Synthesis of Aniline

y Synthesis of phenyl hydrazine

Rack your Brain

Why the para product is the

major product in the nitration of
Coupling Reactions aniline?
On condensation with phenol or aniline, benzene
diazonium chloride gives dyes as follows:

With Anisole

y The presence of aromatic p-amino group can

be confirmed by the formation of an orange
red dye with alkaline solution of b–naphthol.
y If a compound does not form a dye even when
b–naphthol reacts with HNO2, the compound
may contain NH2 group in the side chain.
Cyanides and isocyanides
They are two series of isomeric compounds
which are derivatives of HCN. These have
following Tautomeric structures
R − C ≡ N  R −N→
= C
Cyanides (R – C ≡ N)
These are named as alkane nitriles. For example,
CH3 – CH2 – CH2 — CN butane nitrile
Concept Ladder
Basic character of o-, m-
and p-nitroanilines relative
to aniline is in the following
order (effect of electron-
withdrawing substituents).
Aniline (Kb = 4.2 × 10-10) >
m-nitroaniline (Kb = 2.9 ×
10-12) > p-nitroaniline (Kb =
1.0 × 10-13) > o-nitroaniline
(Kb = 6 × 10-15).
Amines

37.
 y Carbo- is added before the suffix name of the
functional group, when carbon atom of the Previous Year’s Questions
functional group is not counted,. e.g.

Nitration of aniline in strong acidic

medium also gives m-nitroaniline
because
[NEET-2018]
(1) In spite of substituents
nitro group always goes to only
y Cyanides are the functional isomers of m-position
isocyanides. (2) In electrophilic substitution
reactions amino group is meta
→
−C ≡ N and − N = C directive
y From alkyl halide: Cyanide is formed when (3) In absence of substituents
alkyl halides reacts with alcoholic NaCN or nitro group always goes to only
KCN. m-position
(4) In acidic (strong) medium
RCN
RX + KCN  → +KX aniline is present as anilinium ion
For example,

CH3Cl + KCN 

→ CH3CN + KCl
From grignard reagent: Rack your Brain
Also cyanides can be formed when grignard
reagent reacts with cyanogen chlorids Why isocyanides are not
RMgX + ClCN 
→ RCN + X − Mg − Cl hydrolysed by bases?

For Example,

CH3MgCl + ClCN 

→ CH3CN + MgCl 2

Tertiary alkyl cyanides can be prepared easily by

Concept Ladder
this method.
By the dehydration of amides:
Alkyl cyanides act as
Dehydrating agents are P O , POCl SOCl etc.
2 5 3 2
both nucleophile and
PO
RCONH2 
2 5
∆
→ RCN + H2O electrophile. cyanide
provides a synthetic
For example
root for tepping up in a
PO
CH3CONH2 
2 5
→ CH3CN + H2O particular series.
∆
Amines

38.
By the dehydrogenation of primary amines
Rack your Brain
Cu,500°C
RCH2NH2  → RCN + 2H2
For example, What is the disadvantage of the
Cu,500°C
method dehydration of amides?
CH3CH2NH2 → CH3CN + 2H2
From oximes
(CH CO) O
RCN
= NOH 
3
∆
2
→ CH3CN + H2O
acetaldehyde
oxime

Physical Properties
y These have bitter almond like smell, are
neutral polar liquids and poisonous in nature.
They have higher B.P and more dipole moment
than that of isocyanides.
y They are soluble in organic solvent as well
as in water but solubility decreases with the
Concept Ladder
increase of molar mass.

Chemical Properties
If this reaction is carried
Hydrolysis:
out at ordinary temperature
Cyanides can be hydrolyzed easily by both bases
then phenol is obtained.
and acids .An amide is formed on partial hydrolysis
with H2O2, whereas on complete hydrolysis, an
acid is formed.
HO
R — C ≡ N 
2 2
→ RCONH2
HO
R — C ≡ N 
2 2
→ RCONH2
H O+
R — C= N 
3
2H O
→ RCOOH + NH3
2

For example,
H O+
CH3 — C ≡ N 
3
2H O
→ CH3COOH + NH3
2

Reduction:
Rack your Brain
Cyanides after get reduced by LiAlH4 or Na/
C2H5OH, give primary amines.
Why nitrous acid used in reaction
4H
R — C ≡ N 
Na +C H OH or
→ RCH2NH2 is freshly prepared?
2 5
LiAlH4
Amines

39.
 Example,
Rack your Brain
4H
CH3 — C ≡ N 
Na +C H OH or LiAlH
→ CH3CH2NH2
2 5 4

Stephen’s reduction: Why stephen’s reduction is

Aldehyde are formed when cyanides are reduced known as partial reduction?
by SnCl2/HCl followed by hydrolysis process.
SnCl 2 + 2HCl 
→ SnCl 4 + 2[H]
SnCl /HCl
R — C ≡ N →
2
2[H]
RCH = NH.HCl
imine hydrogen chloride

HO
→
2
RCHO + NH4Cl
Aldehyde
Concept Ladder
Example,
Aniline is used in the
manufacture of Schiff
base (anti-oxidant in
rubber industry) and some
sulphadrugs.
Aniline in sulphuric acid
Alcoholysis: with K2Cr2O7 first gives
Esters are formed when cyanides reacts with a red coloured product
alcohol and dry HCl, followed by hydrolysis, which ultimately changes
HO
its colour to deep blue.
R — C ≡ N + ROH + HCl →
2
RCOOR + NH4Cl

Example,
HO
CH3 — C ≡ N+ C2H5OH + HCl →
2
CH3COOC2H5 + NH4Cl
ethyl acetate

Rack your Brain

What is the reactive species in

the diazotization?
Amines

40.
With Grignard reagent

Isocyanides
(R  N  C)
y These are named as alkyl carbylamines or
Concept Ladder
alkyl isonitrile.
Diazonium salts of alkanes,
For ex. CH3NC methyl carbylamine or methyl
alkenes and alkynes
isonitrile.
are not at all stable at
C2H5NC ethyl carbylamine or ethyl isonitrile.
room temperature while
benzene Diazonium salts
Preparation of RNC
are stable to some extent
Carbylamine Reaction :
due to delocalization of
Here, isocyanides are formed when primary amines
the positive charge in the
react with chloroform and alcoholic KOH as follows
benzene ring.
RNH2 + CHCl 3 + 3KOH 
→ RNC + 3KCl + 3H2O
Example,

C6H5NH2 + CHCl 3 + 3KOH 

→ C2H5NC + 3KCl + 3H2O

From alkyl halides

Alkyl isocyanide is formed as major product when
an alkyl halide reacts with alcoholic solution of
silver cyanide.

RX + AgCN 
→ RNC + AgX
Concept Ladder
Example,

C2H5Cl + AgCN 

→ C2H5NC + AgCl Replacement of diazonium
group by hydrogen, thereby
By the dehydration of N-substituted firnanudes effecting the overall
removal of amino group is
POCl →
R — NH — C — H  3
pyridine
→ R — N= C + H2O known as deamination.
||
O
Amines

41.
 Physical Properties
y They are soluble in organic solvents but Concept Ladder
soluble in water.
y These have highly poisonous nature and The reaction involves
colourless liquids with a pleasant smell. treatment of diazonium
y Their B.P. are lower than the corresponding salt solution with a solution
cyanides. of copper (I) cyanide
in aqueous potassium
Chemical Properties cyanide.
Hydrolysis :
Isocyanides undergo acidic undergo acidic
hydrolysis to give primary amine as follows:
H O+
R — NC 
3
→ RNH2 + HCOOH
Example,
H O+
CH3 − NC 
3
→ CH3NH2 + HCOOH
Reduction :
Isocyanides on reduction with LiAlH4 or Na/ Rack your Brain
alcohol give secondary amine as follows
4H In the synthesis of phenol, the
R — NC  → RNHCH3
Na/alc diazo group has been replaced
Example, by which group or atom?
4H
C2H5 — NC 
Na/alc
→ C2H5NHCH3
n−methyl ethanamine

Heating effect or isomerization

Isocyanides isomerizes into cyanides on heating
for a long time.
250°C
R — NC ← →R — C ≡ N
Concept Ladder
Addition reactions
Isocyanides undergo addition reaction with O3,
Gatterman reaction is a
sulphur, HgO as follows:
modification of Sandmeyer’
→ s reaction and instead of
R —=
N C + O3 
→ R −=
N =
C O + O2
cuprous salts, finely divided
→ copper or copper bronze is
N C + 1 S8 
R —= → R −=
N =
C S
8 used for the decomposition
of diazonium salt solution.
→
R —=
N C + 2HgO 
→ R −=
N =
C O + Hg 2O
Amines

42.
 Q5 The correct IUPAC name for CH2=CHCH2NHCH3 is
(a) Allylmethylamine (b) 2-amino-4-pentene
(c) 4-aminopent-1-ene (d) N-methylprop-2-en-1-amine

Sol. N-methylprop-2-en-1-amine

Q6 Benzylamine may be alkylated as shown in the following equation :

C6H5CH2NH2 + R—X → C6H5CH2NHR
Which of the following alkyl halides is best suited for this reaction through SN1
mechanism?
(a) CH3Br (b) C6H5Br (c) C6H5CH2Br (d) C2H5Br

Sol. C6H5CH2Br

Q7 The best reagent for converting, 2-phenylpropanamide into 1- phenylethanamine

is __________.
(a) excess H2/Pt (b) NaOH/Br2
(c) NaBH4/methanol (d) LiAlH4/ether

Sol. NaOH/Br2

Q8 Hoffmann Bromamide Degradation reaction is shown by __________.

(a) ArNH2 (b) ArCONH2 (c) ArNO2 (d) ArCH2NH2

Sol. ArCONH2

Q9 Acid anhydrides on reaction with primary amines give ____________.

(a) amide (b) imide (c) secondary amine (d) imine

Sol. Amide
Amines

43.
 Q10 Under which of the following reaction conditions, aniline gives p-nitro derivative
as the major product?
(a) Acetyl chloride/pyridine followed by reaction with conc. H2SO4 + conc. HNO3
(b) Acetic anhydride/pyridine followed by conc. H2SO4 + conc. HNO3
(c) dil. HCl followed by reaction with conc. H2SO4 + conc. HNO3
(d) Reaction with conc. HNO3 + conc.H2SO4

Sol. Option (a) and (b) are the correct answer.

Q11 What is the role of HNO3 in the nitrating mixture used for nitration of benzene?

Sol. Nitrating mixture is used for the nitration of organic compounds and it is the
mixture of 1:1 solution of HNO3 and H2SO4. It provides electrophile in the nitration
process of benzene.

Q12 Why is NH2 group of aniline acetylated before carrying out nitration?

Sol. To control the nitration reaction and tarry oxidation products and nitro derivatives
products formation, the NH2 group of aniline is acetylated before carrying out
nitration. Here, the major product is p-nitroaniline.

Q13 Give the structure of ‘A’ in the following reaction.

Sol.

3-Methylnitrobenzene is the product formed due to this chemical reaction.

Amines

44.
 Q13 Why is benzene diazonium chloride not stored and is used immediately after
its preparation?

Sol. Benzene diazonium chloride can not be stored because of its unstability.It is highly
soluble in water at high temperature and is itself very stable at low temperature.

Q14 Why does the acetylation of —NH 2

group of aniline reduce its activating effect?

Sol. It is because the lone pair of electrons on the N atom of acetanilide interacts with
O atom due to resonance.

Q16 Write the structures of A, B, C, D and E in the following reaction :

Sol.

Amines

45.
 Q17 Write chemical equations for the following reactions:
(i) Reaction of ethanolic NH3 with C2H5Cl.
(ii) Ammonolysis of benzyl chloride and reaction of amine so formed with two
moles of CH3Cl.

Sol. (i)

(ii)

Q18 Write chemical equations for the following conversions:

(i) CH3–CH2–Cl into CH3–CH2–CH2–NH2
(ii) C6H5–CH2–Cl into C6H5–CH2–CH2–NH2

Sol. (i)

(ii)
Amines

46.
 Q19 Write structures and IUPAC names of
(i) the amide which gives propanamine by Hoffmann bromamide reaction.
(ii) the amine produced by the Hoffmann degradation of benzamide.

Sol. (i) Propanamine contains three carbons. Hence, the amide molecule must contain
four carbon atoms. Structure and IUPAC name of the starting amide with four
carbon atoms are given below:
CH3–CH2–CH2–CO–NH2 Butanamide

(ii) Benzamide is an aromatic amide containing seven carbon atoms. Hence, the
amine formed from benzamide is aromatic primary amine containing six carbon
atoms.
C6H5–NH2 Aniline or benzenamine

Q20 ArrangeCthe following in decreasing order of their basic strength:

H NH , C H NH , (C H ) NH, NH
6 5 2 2 5 2 2 5 2 3

Sol. The decreasing order of basic strength of the above amines and ammonia
follows the following order:
(C2H5)2NH > C2H5NH2 > NH3 > C6H5NH2

Q21 How will you convert 4-nitrotoluene to 2-bromobenzoic acid ?

Sol.

Amines

47.
 Summary

y Methyl isocyanate (MIC) CH3N=C=O was responsible for Bhopal gas tragedy in
December 1984.
y CN– and NO2– are ambident nucleophiles.
y Amatol is NH4NO3 + TNT (trinitro toluene) and is used as blasting material.
y Sweet spirit of nitre is 4% alcoholic solution of ethyl nitrite and is used as
diuretic.
y Benzaldehyde and nitrobenzene both case smell of bitter almond.
y Order of basicity among amines
(i) in aqueous solution : 2° > 1° > 3°
(ii) in gas state (or non-aqueous solution) : 3° > 2° > 1°.
y o-substituted amines are weaker base than aniline irrespective of nature of
substituent (due to ortho effect)
y Among p-substituted anilines the order of basic strength is as follows :

y Mixture of 1°, 2° and 3° amines is separated by Hinsberg reagent and Hoffmann

method.
y Aniline on nitration gives m-nitroaniline through — NH2 group is ortho,
paradirecting.
y In diazotizaiton of arylamines with NaNO2 — HCl excess of HCl is used to supress
concentration of free aniline available for chlorination.
y Carbylamine test is given by 1° aromatic and 1° aliphatic amines both.
y Gabriel phthalimide synthesis is done to prepare 1° aliphatic amines only.
y Libermann’s nitroso test is given by 2° amines only.
y Hoff mann mustard oil reaction :

HgCl
RNH2  CS2 2
R  N  C  S
or
HgCl
ArNH2  CS2 
2
 Ar  N  C  S
Amines

48.