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Chemistry : Amines ®

Pre-Medical

Chapter No. 04

AMINES
S.No. Contents Page
01. Amines 133
02. Aniline 138
03. Nitro-benzene 142
04. Exercise-I (Conceptual Questions) 146
05. Exercise-II (Previous Years Questions) 150
06. Exercise-III (Analytical Questions) 155

NEET SYLLABUS
Amines : Nomenclature, classification, structure, methods of preparation, physical and chemical proeprties, uses,
identification of primary secondary and tertiary amines. Cyanides and Isocyanides (will be mentioned at relevant places)
Diazonium salt: preparation, chemical reactions and importance in synthetic organic chemistry.

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OBJECTIVES
After studying this unit, we will be able to :
 Describe amines as derivatives of ammonia having a pyramidal structure;
 Classify amines as primary, secondary and tertiary;
 Name amines by common names and IUPAC system;
 Describe some of the important methods of preparation of amines;
 Explain the properties of amines;
 Distinguish between primary, secondary and tertiary amines;
 Describe the method of preparation of diazonium salts and their importance in the
synthesis of a series of aromatic compounds including azo dyes.

"Learning gives creativity

Creativity leads to thinking
Thinking provides knowledge
Knowledge makes you great."

A.P.J. Abdul Kalam

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AMINES
Amines
Amines are derivatives of ammonia in which one or more hydrogen atoms are replaced by alkyl group(s).
Amines are classified as primary, secondary and tertiary depending on the number of alkyl groups attached
to nitrogen atom.
+R RNH2 +R R 2 NH +R R3N
NH3  →  →  →
−H
p − amine −H
sec. amine −H
tertiary amine
General formula (CnH2n+3N)

1° amine 2° amine 3° amine

General methods of preparation

(1) Ammonolysis of alkyl halides :
(a) From Ammonolysis of alkyl halides [Hofmann's ammonolysis] : When an aqueous
solution of ammonia is heated with alkyl halide all the three types of amines and quaternary
ammonium salt are formed.
⊕ 
NH3 R−X R−X R−X
R—X 
− HX
→ R—NH2 
− HX
→ R2NH 
− HX
→ R3N  → R4 N X

(Quaternary ammonium salt)

If ammonia is taken in excess, 1° amine is the main product.
(2) By reduction :
LiAIH
(a) With RCONH2 : RCONH2  4
or Na/C H OH
→ RCH2NH2
2 5

Na/C H OH
(b) With RCN : RCN + 4[H] 
2 5
→ RCH2NH2
This reaction (b) is called Mendius reaction.
The reduction of alkyl isocyanides gives secondary amines.
C H OH / Na
R—NC + 4[H] 
2 5
→ RNHCH3
Sn/HCl
(c) With RNO2 : RNO2 + 6[H] 
or Fe + HCl
→ RNH2 + 2H2O

Sn/HCl is used in laboratory preparation

(3) By hydrolysis of :
(a) R—NC : Alkyl isocyanide undergoes hydrolysis with mineral acid and forms alkyl amine.
HCl
R—NC + 2H2O  → RNH2 + HCOOH
(b) RNCO : Alkyl isocyanate undergoes hydrolysis on heating with KOH and forms alkyl amine.

KOH
RNCO + → RNH2 + K2CO3
KOH

(4) Hoffmann's bromamide degradation reaction : Amides on reaction with bromine, and NaOH or
KOH yield primary amines, having one C–atom less than the amides.

CH3CONH2 + Br2 + KOH(aq.) → CH3NH2 + KBr + K2CO3 + H2O

or (KOBr)

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Mechanism :
O –
O O
– Br–Br
KOH
CH3—C—N—H CH3—C—N—H CH3—C—N—Br
H H
–
KOH

O O
–
Rearrangement –Br
CH3—N=C=O CH3—C—N CH3—C—N—Br

2KOH (Acetylnitrene)

CH3—NH2+ K2CO3

(5) Gabriel phthalimide synthesis : Phthalimide is first treated with KOH to obtain potassium
phthalimide which is then treated with alkyl iodide. Then alkyl phthalimide on hydrolysis yields
alkylamine. This method is used in the formation of pure aliphatic primary amines.
CO KOH CO ⊕
NH → NK
–H2O
CO CO
RI
COOH 2H2O CO
R–NH2 +
→
NR
COOH CO

Phthalic acid
* Aniline is not formed by this reaction.

GOLDEN KEY POINTS

 Separation of 1°, 2° and 3° amines
⊕
1°, 2°, 3° amine + R4NX distillation
Mixture of 1°, 2°, 3° amine
⊕ 
R4NX does not undergo distillation
Mixture of 1°, 2°, 3° amine can be separated by following methods.
(i) Fractional distillation : The mixture of amines may be separated by fractional distillation because
their boiling points are quite different. It is used in industry.
(ii) Hinsberg method : In this method mixture of amines is seperated by using benzene sulphonyl
chloride (Hinsberg's reagent).
KOH
C6H5SO2Cl + 1° amine → Product → Soluble
(ppt.)
KOH
C6H5SO2Cl + 2° amine → Product → insoluble
(ppt.)
3° amine does not react with benzene sulphonyl chloride. (No ppt. formed)

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PHYSICAL PROPERTIES
(i) CH3NH2 is gas and C2H5NH2 is a volatile liquid.
(ii) Higher amines have fishy smell.
(iii) H –Bonding (weaker as compared to H—O —H).
R R R R R R
N—H N—H N—H N—H N—H N—H
H H H R R R
(1° amine) (2° amine)

In 3° amine (due to absence of H–atom) H–bonding is not possible.

(iv) Boiling point : Due to weak intermolecular H-bonding the B.P. of 1° and 2° amines are lower than
those of alcohols of comparable molecular weight. The boiling point of 3° amines which form no
H–bonds are near to those of alkanes of comparable molecular weight.
Boiling point α molecular weight
Order of B.P. : 1° amine > 2° amine > 3° amine
so order of volatility : 3° amine > 2° amine > 1° amine

(v) Solubility : Low molecular weight amines are soluble in water. The water solubility of amines
decreases with increasing size of alkyl group.
R
R H R R H R R H N—R
N—H O—H N—H N—H O—H N—H R—N H— O R
H H R R R
(1° amine) (2° amine) (3° amine)
Order of solubility → p– amine > s– amine > t– amine
Chemical properties
(i) Basic character of amines is due to the presence of lone pair of electrons on the N - atom.
(ii) Basic strength depends on electron donating tendency.
(iii) Order of basic character in aqueous solution : (CH3)2 NH > CH3 NH2 > (CH3)3 N > NH3
(C2H5)2 NH > (C2H5)3N > C2H5 NH2 > NH3
GOLDEN KEY POINTS
 Tertiary amine is less basic then secondary due to following reasons :
(i) Steric hindrance : In tertiary amines (R3N) , three alkyl groups attached to N are bulkier and as such
exert steric hindrance.
(ii) Decrease in hydration :
In tertiary amine In secondary amine
H
O
⊕ H H
⊕ H R2N
R3N H O H H
H O
Protonated t–amine can form H–bonding H
with water molecule only at one point Protonated s–amine can form H bonding with
[less stable]
water molecules at two points
(more stable)
Conjugate acid of 3° amine are less stable as compare to 2° amine due to low hydration so less basic.
 The basic strength of aniline is less than aliphatic amines as the lone pair of electron present on N– atom
interact with the delocalized π - orbital of benzene ring. Hence it is less available for protonation on N–atom.
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(1) Reactions showing basic nature :

It reacts with acids to form salts.

⊕  ∆
RNH2 + HCl → [RNH3]Cl 
High temp.
→ R—Cl + NH3

Alkyl ammonium chloride

(Acidic salt)

⊕
–2
 → (RNH3)2 SO4
H 2 SO 4
2RNH2 Alkyl ammonium sulphate

(2) Reaction with alkyl halides : Alkyl amine reacts with alkyl halides and form sec., ter. amines and
quaternary ammonium salt.

− HX RX RX ⊕
RNH2 + R—X → R2NH →
− HX
R3N  → R4NX

(3) Acetylation : Acetylation takes place when alkyl amine combines with acetyl chloride or acetic
anhydride.

RNH2 + ClCOCH3 → RNHCOCH3 + HCl

(N –alkyl acetamide)

RNH2 + (CH3CO)2O → RNHCOCH3 + CH3COOH

(N –alkyl acetamide)

(4) Benzoylation (Schotten Baumann reaction) :

COCl CONHR
NaOH
+ H–NH–R + HCl

Benzoylchloride N-alkyl benzamide

(5) Acidic nature : Amines are very weak acids only 1° and 2° amines show acidic nature with active
metals.

 ⊕ 1
R—NH2 + Na → RNHNa + H2
2
N– alkyl sodamide

(6) Reaction with aldehydes :

H
− H2 O
R NH2 + O = C – R  → RCH = NR (Schiff's base)

(7) Carbylamine Reaction (Isocyanide test) : When alkyl amine heated with chloroform and alc. KOH
alkyl isocyanide is formed which has very bad smell.

This test is also given by aniline . This is a test for p– amines.


R—NH2 + CHCl3 + 3 KOH → R—N = C + 3KCl + 3H2O

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(8) Hofmann's mustard oil test : When alkyl amine is heated with carbon disulphide and mercuric
chloride alkyl isothiocyanate is formed which has smell like mustard oil.
S S
HgCl
R—NH2 + C = S → R—NH — C — SH 
2
→ R – N = C = S + HgS + 2HCl
Alkyl isothiocyanate
S S
HgCl
R2NH + C = S → R2N—C — SH 
2
→ No reaction
S
R3N + C = S → No reaction.

(9) Reaction with HNO2 :

(a) Primary amines react with nitrous acid to produce nitrogen gas [seen as bubbles]
NaNO + HCl(aq.)
R—NH2 
2
→ R—OH + N2
or HNO2

HNO
CH3CH2—NH2 
2
→ CH3CH2—OH + N2
Mechanism :
⊕  ⊕ 
NaNO2 + HCl
CH3 CH2 — NH2  → CH3 CH2 — N2 Cl → CH3 CH2 + N2 + Cl
(Unstable)
H2O
CH3CH2–OH (major)

Cl CH3CH2–Cl
⊕ 
CH3CH2 O–N=O
CH3CH2–O–N=O + CH3–CH2–NO2
⊕ (side products)
–H CH2 =CH2

CH3–CH2–OH
CH3–CH2–O–CH2–CH3

Intermediate is carbocation so rearrangement may be possible.

Illustrations
NaNO2 + HCl
Illustration 1. CH3CH2CH2—NH2  → ?
Solution. Mechanism :
⊕  ⊕
NaNO2 + HCl
CH3CH2CH2—NH2  → CH3CH2CH2— N2 Cl → CH3 CH2 CH 2

 
HO ⊕ H shift
CH3–CH–CH3 CH3–CH–CH3
rearrangement
OH

HNO2
Exception : CH3–NH2 CH3–O–CH3

(b) R2 NH + HONO → R2 N—NO + H2O

Dialkylnitroso amine (Yellow oily layer)
⊕ 
(c) R3N + HONO → R3NHNO2 Trialkyl ammonium nitrite (Soluble in water)

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Points to Remember :
(i) Nitrosoamines are carcinogens (Cancer causing agents)
(ii) Amines can have chiral N-atom but cannot be resolved into enantiomeric forms because of rapid
inversion of one enantiomeric form into the other.
(iii) The Schiff's bases formed by reaction of 1°-amines and aldehyde/ketones are also called anils.
(iv) The mixture of 1°, 2°, 3° amines can be distinguished by Hofmann's test or Hinsberg's reagent or
nitrous acid test.
ANILINE (C6H5NH2)
General Methods of Preparation
(1) Lab method:
Sn + HCl
C6H5NO2 → C6H5NH2 + H2O
(2) Industrial method :
Fe + HCl
C6H5—NO2  → C6H5 —NH2 + H2O
(3) From benzamide (Hofmann's bromamide reaction):
C6H5CONH2 + Br2 + 4KOH → C6H5NH2 + K2CO3 + 2KBr + 2H2O
(4) From phenyl isocyanide :

C6H5N = C + 2H2O → C6H5NH2 + HCOOH
Physical Properties
(i) Fresh aniline is a colourless oily liquid. On standing the colour becomes dark brown due to action of air
and light.
(ii) It's B.P. is 183° C.
(iii) It is heavier than water.
(iv) It has characteristic unpleasent odour. It is toxic in nature.
Reactions due to —NH2 group
(1) Basic nature : Aniline is weak base but it forms salt with strong acids. It accepts a proton.
⊕
C6H5–NH2 + H+ → C6H5NH3 Anilinium ion

⊕ 
C6H5NH2 + HCl → C6H5NH3Cl Anilinium hydrochloride

⊕
2C6H5NH2 + H2SO4 → (C6H5NH3)2SO4 Anilinium sulphate

⊕
2C6H5NH2 + H2PtCl6 → (C6H5NH3)2PtCl6–2 Anilinium platinic chloride

Chloroplatinic acid
(2) Alkylation : Aniline reacts with alkyl halides forming secondary, tertiary and quaternary ammonium
salts depending on the concentration of alkyl halides.
C6H5NH2 + CH3I → C6H5—NH—CH3 + HI
(N–methyl aniline)
C6H5NH — CH3 + CH3I → C6H5N(CH3)2 + HI
(N,N–dimethyl aniline)
⊕
C6H5N(CH3)2 + CH3I → C6 H5 (CH3 )3 N I
(Trimethyl phenyl ammonium iodide)

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(3) Acylation : Aniline reacts with acid chlorides or anhydrides to form corresponding amides called
anilides. [The reaction of C6H5NH2 with benzoyl chloride is example of "Schotten Baumann
reaction"]
Base
C6H5–NH2+ Cl–C–CH3 C6H5–NH–C–CH3 (Acetanilide)

O O
(4) Carbyl amine reaction or isocyanide test : (Hoffman's carbylamine reaction)
3 CHCl + KOH
Primary–Amines (Aliphatic or Aromatic) 
→ Isocyanides
Isocyanides have unpleasant or offensive smell (Isocyanide test).
3 CHCl + KOH
R—NH2 
→ R—NC

Mechanism :
KOH → :CCl
CHCl3  2

(electrophile)
H Cl
.. ⊕  –2HCl
R–NH2 + :CCl2→ R – N – C R N C
Alkyl isocyanide
H Cl

CHCl3 + KOH
CH3CH2–NH2 → CH3CH2–NC

Ph–NH2
CHCl3 + KOH
→ Ph NC Reaction is given by only
primary amine
NH2 CHCl3 + KOH
NC
→

(5) Hoffmann's mustard oil reaction : When aniline is heated with alc. CS2 and excess of HgCl2 phenyl
isothiocyanate having a characteristic smell of mustard oil is formed.
HgCl
C6H5NH2 + S=C=S 
∆
2
→ C6H5N=C=S

Phenyl isothiocyanate
This is a test of aniline and other primary amines.
(6) Reaction with aldehydes : Aniline condenses with aldehydes to form schiff's base.

C6H5NH2 + H–C–C6H5 → =
C6 H5 N CHC6 H5 + H2 O
O Benzylidene aniline
(schiff ' s base)

(7) Reaction with Hinsberg's reagent :

− HCl
C6H5—SO2Cl + HNHC6H5  
→ C6H5SO2NHC6H5
(N– Phenylbenzene sulphonamide)
(8) Diazotisation :Diazotisation is a reaction in which ice cooled solution of aniline in an inorganic acid
reacts with sodium nitrite solution leading to the formation of diazonium salt.
°
0 −5 C °
C6H5NH2 + NaNO2 + HCl 
–H O
→ C6H5N2Cl
2

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Benzene diazonium chloride is a useful synthetic reagent. It is used in the preparation of many organic
compounds
Cu/HCl
→ C6H5Cl
∆
(Gattermann reactions)
Cu/HBr
→
∆ C6H5Br
Cu2Cl2/HCl
→ C6H5Cl + N2 + HCl
∆
Cu2Br2/HBr C6H5Br + N2 + HCl Sandmeyer
→
∆ reactions
Cu2(CN)2/HCN/∆
→ C6H5CN + N2 + HCl
or CuCN/KCN/∆
KI (aq.)
→ C6H5I + N2 + KCl
∆
NaBF4/∆
C6H5N2Cl → C6H5F + BF3 + NaCl Balz-Schiemann reaction
or HBF4/∆

H2O
→ C6H5OH
∆

C2H5OH C6H6 + CH3CHO + N2 + HCl

→

H3PO2 + H2O
→ C6H6 + H3PO3 + N2 + HCl

C H OH
→
6 5
C6H5N=N—C6H4OH
pH 8-10 Coupling
p-Hydroxy azobenzene (Orange dye)
reactions
C H NH
→
6 5 2
C6H5N=N—C6H4NH2
pH 4-5
p-Amino azobenzene (aniline yellow
or yellow dye)

(1) Halogenation : In polar and nonpolar medium Chlorine and bromine react with aniline and form
trichloro and tribromo aniline respectively.

NH2 NH2
NH2 Br Br Cl Cl
2 Polar solvent (H O) or
+ 3Br2 or 3Cl2 →
Br Cl
2,4,6-Tribromo aniline
(white ppt.)

NH2 NH2
Non polar solvent(CCl4 ) Br Br
+ Br2 
→

Br
2,4,6-Triboromoaniline

Note : However, monobromo or chloro derivative of aniline can be prepared if –NH2 group is first
protected by acetyl group. Here the reactivity decreases due less +M effect on benzene ring.

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NHCOCH3 NHCOCH3
NH2 NHCOCH3 Br
+
→
CH3 COCl
 Br 2
CH3 COOH
→
H2O Br
(Acetanilide) NH2 NH2
Br
+

Br
o– and p–Bromo aniline
(2) Nitration :
⊕ 
NH2 NH3HSO4 NH2
NH2 NH2
H SO ⊕
NO2

2

HNO
4
→ N O2
3
→
–H2 SO4
+ +
NO2
NO2
(47%)
(51%) (2%)
(3) Sulphonation : Aniline reacts with fuming H2SO4 to give sulphanilic acid.(p-Amino-benzene sulphonic
acid)
⊕  ⊕
NH2 NH3HSO4 NHSO3H NH2 NH3

–H2O Rearrangement
+ H2SO4 (Fuming)
180°C

SO3H SO3
Sulphanilic acid
 This process is called baking.
 Sulphanilic acid is an important intermediate in the manufacturing of dyes and drugs.
 The compounds in which both proton donating & proton accepting groups present are called
ampholite (dipolar ion).
⊕
NH2 NH3

(Zwitter ion)


SO3H SO3
(4) Catalytic hydrogenation : Aniline undergoes hydrogenation in presence of Ni at high temp. to form
cyclohexanamine.
NH2 NH2
Ni
+ 3H2
High Temp.
(5) Coupling reactions : Aniline couples with benzene diazonium chloride in mild acidic medium an
alkaline solution to form a dye- p-amino azobenzene (yellow dye).
+
H
N2Cl + NH2 → N N NH2 + Cl– + H2O

p-amino azobenzene (Yellow dye)

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Tests of Aniline
(i) Carbylamine test : Aniline gives carbylamine test or Isocyanide test.

C6H5NH2 + CHCl3 + KOH → C6H5NC

(Bad smelling)
(ii) On heating with bromine water, a white ppt. is formed.

BEGINNER'S BOX-1
1. Which one of following reaction is Schotten–Baumann reaction ?

(1) Acetylation of RNH2 (2) Acylation of RNH2

(3) Benzoylation of RNH2 (4) All of them

2. Which of the following pair will yield primary amine on hydrolysis ?

(1) CH3NCO, CH3NC (2) CH3CN, CH3NC

(3) (CH3)2NH, CH3—CH=NOH (4) None of the above

3. Methylamine on treatment with chloroform and ethanolic caustic alkali gives foul smelling compound, the
compound is

(1) CH3NCO (2) CH3CNO (3) CH3CN (4) CH3NC

NITRO BENZENE [C6H5NO2]

It is also called as artificial oil of bitter almonds or oil of mirbane as its odour is like that of bitter almonds.

General Methods of Preparation

(1) Lab method :

NO2

50–60°C
+ Conc. H2SO4 + Conc. HNO3

(2) From diazonium salt :

N2Cl NO2
(i) HBF4
+ N2 + NaBF4
(ii) NaNO2,Cu, ∆

Physical Properties
(i) Nitro benzene is light yellow oily liquid
(ii) It has smell of bitter almonds
(iii) It is steam voltile. It's vapours are poisonous in nature.
(iv) It is heavier than water
(v) It's B. P. is 211°C
(vi) Smell of nitro benzene and benzaldehyde is same

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Chemical Properties
Nitrobezene shows following chemical reactions –
(1) Reactions due to NO2 group.
(2) Reactions due to benzene ring : (A) Electrophilic substitution (B) Nucleophilic substitution

NO2 NO2
Conc. HNO3+
⊕
Conc. H2SO4 NO2
∆ NO2
NO2 O2N

NO2

Fuming H2SO4

SO3H
Electrophilic
Substitution
Reaction

NO2

Cl2/AlCl3

NO2 Cl
Fe/HCl or Sn/HCl
or H2/Pd
NH2
Nitro Benzene
Zn+NH4Cl
N–OH
H
REDUCTION

Fe/H2O
N=O

dil. H2SO4
Electrolytic NH2
reduction
Conc. H2SO4 rearrangement
N–OH HO NH2
H

LiAlH4
N=N (Azobenzene)

Test of Nitrobenzene

Mulliken Barker Test : Ethanolic solution of nitrobenzene is treated with zinc dust and NH4Cl solution.
The mixture is heated and filter in a test tube containing Tollen's reagent a grey or black precipitate
(Ag mirror) is formed.
Tollen's reagent
C6H5NO2 + Zn + NH4Cl → C6H5NH–OH → C6H5NO + Silver mirror (Ag↓)
Phenyl hydroxyl amine Nitroso benzene
Uses

(i) As a solvent
(ii) In manufacture of aniline and azo dye
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BEGINNER'S BOX-2
1. Nitration of which of the following compound is difficult :-

(1) Benzene (2) Nitrobenzene (3) Toluene (4) Phenol

Sn/HCl NaNO2 / HCl

2. C6H5NO2 → A  → B; To obtain benzene from B, the suitable reagent is :

(1) SnCl2 + HCl (2) H3PO2 (3) C2H5N2Cl (4) Methanol

3. Phenol reacts with benzenediazonium chloride solution to form a compound of the structure :-

(1) HO N=N Cl (2) N=N OH

(3) N—N (4) N=N Cl

OH Cl

ANSWER KEY
Que. 1 2 3
BEGINNER'S BOX-1
Ans. 4 1 4
Que. 1 2 3
BEGINNER'S BOX-2
Ans. 2 2 2

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NCERT POINTS
Two biologically active compounds, namely adrenaline and ephedrine, both containing secondary amino
group, are used to increase blood pressure. Novocain, a synthetic amino compound, is used as an
anaesthetic in dentistry. Benadryl, a well known antihistaminic drug also contains tertiary amino group.
Quaternary ammonium salts are used as surfactants.
Physical Properties
The lower aliphatic amines are gases with fishy odour. Primary amines with three or more carbon atoms are
liquid and still higher ones are solid. Aniline and other arylamines are usually colourless but get coloured on
storage due to atmospheric oxidation.
Lower aliphatic amines are soluble in water because they can form hydrogen bonds with water molecules.
However, solubility decreases with increase in molar mass of amines due to increase in size of the
hydrophobic alkyl part.
Primary and secondary amines are engaged in intermolecular association due to hydrogen bonding between
nitrogen of one and hydrogen of another molecule. This intermolecular association is more in primary
amines than in secondary amines as there are two hydrogen atoms available for hydrogen bond formation in
it. Tertiary amines do not have intermolecular association due to the absence of hydrogen atom available for
hydrogen bond formation. Therefore, the order of boiling points of isomeric amines is as follows:
Primary > Secondary > Tertiary
Intermolecular hydrogen bonding in primary amines is shown in Fig.
H R H
R–N–H N–H N–R
H H

H–N–R
H
Method of Preparation of Diazonium Salts
Benzenediazonium chloride is prepared by the reaction of aniline with nitrous acid at 273-278K. Nitrous
acid is produced in the reaction mixture by the reaction of sodium nitrite with hydrochloric acid. The
conversion of primary aromatic amines into diazonium salts is known as diazotisation. Due to its instability,
the diazonium salt is not generally stored and is used immediately after its preparation.
+ −
273 −278K
C6H5NH2 + NaNO2 + 2HCl  → C6H5 N2 Cl + NaCl + 2H2O
Physical Properties
Benzenediazonium chloride is a colourless crystalline solid. It is readily soluble in water and is stable in cold
but reacts with water when warmed. It decomposes easily in the dry state. Benzenediazonium fluoroborate is
water insoluble and stable at room temperature.
Importance of Diazonium Salts in Synthesis of Aromatic Compounds
From the above reactions, it is clear that the diazonium salts are very good intermediates for the introduction
of –F, –Cl, –Br, –I, –CN, –OH, –NO2 groups into the aromatic ring.
Aryl fluorides and iodides cannot be prepared by direct halogenation. The cyano group cannot be introduced
by nucleophilic substitution of chlorine in chlorobenzene but cyanobenzene can be easily obtained from
diazonium salt.
Thus, the replacement of diazo group by other groups is helpful in preparing those substituted aromatic
compounds which cannot be prepared by direct substitution in benzene or substituted benzene.

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EXERCISE-I (Conceptual Questions) Build Up Your Understanding

AMINE 8. The reaction : [C2H5Br + NH3] is in fact an
1. Among the following which one is not formed in example of
Hoffmann degradation (1) Ammonolysis only

(2) Nucleophilic substitution only
(1) RNCO (2) R − NH2 (3) Ammonolysis as well as nucleophilic substitution
 (4) None
(3) RCO NH Br (4) RNC HD0011
AM0001
9. Solubility of ethylamine in water is due to
NaOH
2. CH3CH2CONH2 
→ A, (1) Low molecular weight
Br2
(2) Ethyl group is present in ethyl alcohol
Aqueous solution of A
(3) Formation of H–bonding with water
(1) Turns blue litmus to red
(4) Being a derivative of ammonia
(2) Turns red litmus to blue
GC0013
(3) Does not affect the litmus
(4) Decolourise the litmus 10. The product obtained by the alkaline hydrolysis
AM0002 of C2H5—NCO when treated with t–butyl
3. Ethanamine can be obtained if the following magnesiumbromide, the compound obtained will
be
compound is heated with [KOH + Br2]
(1) Ethanamide (2) Methanamide (1) t–butylamine
(3) Propionamide (4) All the above (2) n–butylamine
AM0003 (3) Isobutane
(4) n–butane
PO
Na/EtOH
4. CH3CONH2 →
2 5
I A 
II → B AM0015
Reaction II is called
11. Reactants of reaction – I are :-
(1) Clemmensen
(2) Stephen CH3CONH2, KOH, Br2
(3) Mendius Reactants of reaction–II are
(4) Bouveault–Blanc reduction CH3NH2, CHCl3, KOH
CA0004
The intermediate species of reaction–I and
5. C2H5NH2 cannot be prepared by the reduction of reaction–II are respectively
(1) C2H5NO2 (2) CH3CH=NOH (1) Carbonium ion, carbene
(3) C2H5NC (4) CH3CN (2) Nitrene, carbene
AM0008 (3) Carbene, nitrene
6. Gabriel reaction for the synthesis of amines, (4) Carbocation, carbanion
involves the use of AM0021
(1) 1° amide (2) 2° amide 12. This compound does not respond to carbylamine
(3) Imides (4) Aliphatic amide reaction :-
AM0009 (1) CH3–CH–NH2 (2) C2H5–NH–C2H5
7. Gabriel phthalimide reaction is used in the CH3
synthesis of CH3
(1) Primary aromatic amines
(2) Secondary amines (3) CH3–C–NH2 (4) CH3–CH–CH2–CH3
(3) Primary aliphatic amines
CH3 NH2
(4) Tertiary amines
AM0010 AM0023

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13. Which one of the following amine compound 18. Which of the following amines give N–nitroso
gives alcohol with HNO2 ? derivative with NaNO2 and HCl ?
(1) N,N–Dimethylaniline
(1) C2H5NH2 (2) NH2
(2) Benzylamine
(3) N–methylaniline
R
(4) Aniline
AM0026 (3) N—H (4) NH2

ANILINE AM0034
Br2 /CCl4
14. C6H5NH2 
→ ? The product is :- 19. Which of the following does not reduce Tollen's
(1) Only o– bromoaniline reagent ?
(2) 2, 4, 6–triboromoaniline (1) CH3CHO (2) HCOOH
(3) o–and p–bromoaniline (3) C6H5NHOH (4) C6H5NH2
(4) Only p–bromoaniline PO0036
AM0028 20. Aniline on direct nitration produces :-
(1) o–Nitroaniline (2) m–Nitroaniline
15. Reaction C6H5NH2 + HAuCl4 → (3) p–Nitroaniline (4) All
⊕ 
[C6H5NH3]AuCl4 shows ... behaviour of aniline :- AH0038
(1) Acidic 21. Nitration of acetanilide followed by hydrolysis
gives
(2) Neutral (1) o–Nitroaniline only
(3) Basic (2) p–Nitroaniline only
(4) Amphoteric (3) o– & p–Nitroaniline
GC0031 (4) o–Nitroanilinium ion
AH0039
16. Aniline on treatment with bromine water yields
white precipitate of :- NaNO2 /HCl
22. C6H5NH2 
0 −5°C
→ A, Which is the
(1) o–Bromoaniline incorrect structure of the product 'A' ?
(2) p–Bromonailine ⊕  ⊕ 
(1) [C6H5–N=N]Cl (2) [C6H5N2]Cl
(3) 2, 4, 6–Tribromoaniline
⊕  ⊕ 
(4) m–Bromoaniline (3) [C6H5–N≡N]Cl (4) [C6H5–N≡N]Cl
AH0032 AM0040

17. Which compound does not show diazo coupling 23. Chloroform and ethanolic KOH is used as a
reaction ? reagent in the following reaction :-

(1) NH2 (a) Hoffmann carbylamine reaction

(b) Hoffmann degradation reaction
(2) H3C NH2
(c) Reimer–Tiemann reaction

(3) O2N NH2 (d) Hoffmann mustard oil reaction

Code is :-
(4) CH2–NH2 (1) Only for a (2) Only for a and b

AM0033 (3) Only for b and d (4) Only for a and c

AM0041

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24. Acetanilide when treated with bromine in acetic CH3
reduction
acid mainly gives :- 29. CH3–C–NC  → ?
CH3
(1) o–Bromoacetanilide
CH3
(2) N–Bromoacetanilide
(1) CH3–C–NH2
(3) p–Bromoacetanilide
CH3
(4) m–Bromoacetanilide
CH3
AH0042 (2) CH3–C–NH–CH3
25. Aromatic nitriles (ArCN) are not prepared by CH3

reaction CH3

(1) ArX + KCN (3) CH3–C–NH–CH2CH3

CH3
(2) ArN2+ + CuCN
(4) None
(3) ArCONH2 + P2O5 AM0049
(4) ArCONH2 + SOCl2 30. Reaction of RCN with sodium and alcohol leads
to the formation of :-
AM0043
(1) RCONH2 (2) RCOO–NH4+
NITRO GROUP, CYANIDE & ISOCYANIDE
(3) RCH2NH2 (4) R(CH2)3NH2
26. Aniline in a set of reactions yielded end product D
AM0050
NH2
Sn/HCl NaNO2 / HCl
NaNO2 + HCl
→
0–5ºC
CuCN
A  →B 31. C6H5NO2  → A 
0°C → B;
Benzene from B, is suitably obtained by using :-
H2
 → C 
HNO2
→ D (1) Ethanol (2) H3PO2
Ni
(3) Both the above (4) Methanol
The structure of the product D would be
AM0051
(1) C6H5CH2OH (2) C6H5CH2NH2
32. Which reagent is used to get iodo benzene from
(3) C6H5NHOH (4) C6H5NHCH2CH3 benzene diazonium hydrogen sulphate
[C6H5N2HSO4] :
AM0044 (1) CuBr, ∆ (2) Cu powder + HI
NaNO2 / HCl Water (3) KI, ∆ (4) None
27. φ—X → ∆ → φ—Y,
C6H5N2Cl 
AM0052
In the above sequence X and Y are :-
33. Which of the following is used as a solvent in the
(1) o–, p– and m–directing Friedel–Crafts reaction ?
(2) o–, p– and o–, p–directing (1) Toluene (2) Nitrobenzene
(3) m and m directing (3) Benzene (4) Aniline
(4) m and o, p directing AH0053
34. In the Sandmeyer's reaction, –N=N–X group of
AM0046 diazonium salt is replaced by :-
28. Which of the following compound gives an (1) Halide group (2) Nitro group
explosive on decarboxylation ? (3) –OH group (4) –NHNH2 group
AM0055
(1) 2,4, 6–Trinitrobenzoicacid
35. Which of the following when heated with KOH
(2) 2, 4–Dimethylbenzoicacid
and primary amine gives carbylamine test
(3) o–Aminobenzoicacid
(1) CHCl3 (2) CH2Cl2
(4) o–Hydroxybenzoicacid (3) CH3OH (4) CCl4
AM0047 AM0014

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36. Chloroform reacts with aniline and aqueous
KOH gives :-

(1) Ph–N = C (Phenyl isocyanide)
(2) Benzene
(3) Phenyl cyanide
(4) None of these
AM0020

EXERCISE-I (Conceptual Questions) ANSWER KEY

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. 4 2 3 3 3 3 3 3 3 3 2 2 2 2 3
Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans. 3 4 3 4 4 3 4 4 3 1 1 2 1 2 3
Que. 31 32 33 34 35 36
Ans. 3 3 2 1 1 1
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EXERCISE-II (Previous Year Questions) AIPMT/NEET

AIPMT 2014 5. Method by which Aniline cannot be prepared is:-
1. In the following reaction, the product (1) reduction of nitrobenzene with H2/Pd in
+ ethanol
N≡NCl¯ NH2
(2) potassium salt of phthalimide treated with
H + chlorobenzene followed by hydrolysis with
(A) + → (A) is :-
aqueous NaOH solution
Yellow dye
(3) hydrolysis of phenylisocyanide with acidic
(1) N=N–NH solution
(4) degradation of benzamide with bromine in
NH2
alkaline solution
(2) N=N
AM0073

NH2 NEET-II 2016

(3) N=N
6. Which one of the following nitro-compounds
does not react with nitrous acid ?
(4) N=N NH2 H3C
(1) H C–C–NO
AM0069 3 2
H3C
2. Which of the following will be most stable CH3

diazonium salt RN+2 X − ? C

(2) H3C H NO2
(1) CH3 N+2 X − (2) C6H5 N+2 X − O
H2
(3) CH3CH2 N+2 X − (4) C6H5CH2 N+2 X − C
(3) H3C NO2
AM0070 C
H2
AIPMT 2015
H2
C
3. The electrolytic reduction of nitrobenzene in (4) H3C NO2
CH
strongly acidic medium produces :- H3C
(1) Azoxybenzene (2) Azobenzene AM0075
(3) Aniline (4) p-Aminophenol 7. A given nitrogen-containing aromatic compound
AM0071
(A) reacts with Sn/HCl, followed by HNO2 to
RE-AIPMT 2015
give an unstable compound (B). (B), on treatment
4. The following reaction with phenol, forms a beatiful coloured compound
H (C) with the molecular formula C12H10N2O. The
NH2 N
NaOH structure of compound (A) is :-
+ Cl
O
O CN CONH2
is known by the name : (1) (2)
(1) Acetylation reaction
(2) Schotten-Baumann reaction NH2 NO2
(3) Friedel–Craft's reaction (3) (4)
(4) Perkin's reaction
AM0076
AM0072
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NEET(UG) 2017 NEET(UG) 2019 (ODISHA)

8. Which of the following reactions is appropriate 11. The amine that reacts with Hinsberg's reagent to
for converting acetamide to methanamine ? give an alkali insoluble product is :-

(1) Hoffmarnn hypobromamide reaction (1) CH3–CH–NH–CH–CH3

(2) Stephens reaction CH3 CH3

(3) Gabriels phthalimide synthesis CH2CH3

(4) Carbylamine reaction (2) CH3–CH2–N–CH2CH3
AM0078 NH2

NEET(UG) 2019 (3) CH3–C–CH2CH2CH3

CH3
9. The major product of the following reaction is :
CH3
COOH strong heating
+ NH3 (4) CH3–C—–CH–NH2
COOH CH3 CH3

AM0108
O
COOH NEET(UG) 2020
(1) (2) NH
CONH2 12. Which of the following amine will give the
O carbylamine test?
NHC2H5
COOH NH2
(3) (4) (1)
NH2 NH2
NH2
AM0107
(2)
10. Among the following, the reaction that proceeds
through an electrophilic substitution is : NHCH3
⊕
Cu Cl (3)
(1) N2Cl → 2 2
Cl + N2

N(CH3)2
AlCl
(2) + Cl2 → 3
Cl + HCl
(4)
Cl Cl
AM0130
UV light
(3) + Cl2 → Cl Cl NEET(UG) 2020 (COVID-19)
Cl Cl 13. Reaction of propanamide with ethanolic sodium
hydroxide and bromine will give
(4) CH2OH + HCl →
heat CH2Cl + H2O
(1) Ethylamine (2) Methylamine
AH0089 (3) Propylamine (4) Aniline
AM0131

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NEET(UG) 2021 NEET(UG) 2022
14. Identify the compound that will react with 17. Given below are two statements :
Hinsberg's reagent to give a solid which dissolves Statement I :
in alkali :
Primary aliphatic amines react with HNO2 to give
CH2
(1) unstable diazonium salts.
CH3 NO2
Statement II :

(2) CH2 CH3 Primary aromatic amines react with HNO2 to

CH3 NH form diazonium salts which are stable even above
300 K.
CH2
(3) In the light of the above statements, choose the
CH3 NH2
most appropriate answer from the options
CH2 CH2 given below :
(4) CH3 N CH3 (1) Both Statement-I and Statement-II are
CH3 incorrect.
(2) Statement-I is correct but Statement-II is
AM0132
15. The reagent ‘R’ in the given sequence of incorrect.
chemical reaction is : (3) Statement-I is incorrect but Statement-II is
+ – correct.
NH2 N2 Cl
Br Br Br Br Br Br (4) Both Statement-I and Statement-II are
NaNO2,HCl R
O–5°C correct.
AM0135
Br Br Br
(1) H2O (2) CH3CH2OH 18. The product formed from the following reaction

(3) HI (4) CuCN/KCN sequence is

AM0133
CN (i) LiAlH4, H2O
NEET (UG) 2021(Paper-2) (ii) NaNO2+ HCl
(iii) H2O
16. A mixture of organic compound A and B when
dissolve in NaOH, A is soluble and its residue B ⊕ 
N2Cl
gives positive test with Zn/NH4Cl followed by (1)
AgNO3 + NH4OH, (Mulliken's-Barker test).
Identify A and B Cl
(2)
OH NO2 OH NH2

(1) (2) OH
, , (3)

NH2 COOH COOH OH

O

(3) (4) (4) NH2

, ,

AM0134 AM0136

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19. Which of the following is suitable to synthesize Re-NEET(UG) 2022
chlorobenzene ? 22. Match List - I with List - II :
(1) Phenol, NaNO2, HCl, CuCl
List - I List - II
(Reaction) (Product fromed)
(2) , HCl
(a) Gabriel synthesis (i) Benzaldehyde
NH2 (b) Kolbe synthesis (ii) Ethers

(3) , HCl, Heating (c) Williamson synthesis (iii) Primary amines

(d) Etard reaction (iv) Salicylic acid
(4) Benzene, Cl2, anhydrous FeCl3 Choose the correct answer from the options
HD0080 given below :
NEET(UG) 2022 (Overseas) (1) (a) - (iii), (b) - (i), (c) - (ii), (d) - (iv)
20. Match List-I with List-II : (2) (a) - (ii), (b) - (iii), (c) - (i), (d) - (iv)
List-I List-II (3) (a) - (iv), (b) - (iii), (c) - (i), (d) - (ii)

(Amines) (pKb values) (4) (a) - (iii), (b) - (iv), (c) - (ii), (d) - (i)
AM0139
(a) N-methylmethanamine (i) 9.30
(b) Ammonia (ii) 9.38 23. The product formed from the following reaction
(c) N-methylaniline (iii) 4.75 sequence is
(d) Benzenamine (iv) 3.27 NH2
Choose the correct answer from the options (i) (CH3CO)2O, pyridine
(ii) LiAlH4
given below :
(iii) H2O
(1) (a)-(iv), (b)-(iii), (c)-(i), (d)-(ii)
(2) (a)-(iii), (b)-(iv), (c)-(i), (d)-(ii)
(3) (a)-(i), (b)-(iv), (c)-(iii), (d)-(ii) H
N CH3
(4) (a)-(iv), (b)-(ii), (c)-(i), (d)-(iii)
(1)
AM0137
21. The major product (P) formed in the following
reaction sequence is
NO2 NH2
(i) Sn, HCl, ∆
(2)
(ii) (CH3CO)2O, Pyridine (P)
(iii) Br2, CH3COOH Major Product
(iv) OH
– OH

NH2 NH2 NH2

Br Br (3)
(1) (2)
Br
Br OH

NH2 HNCOCH
NH2
(3) (4) (4)
OH

Br Br OH
AM0138
AM0140
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24. Which one of the following reaction sequence is 27. Complete the following reaction :
incorrect method to prepare phenol ? OH conc.H SO
O HCN 2 4
[C]
(1) Aniline, NaNO2 + HCl, H2O, heating CN ∆
(2) Cumene, O2, H3O+ [A] [B]

Cl [C] is _____.
(3) , NaOH, STP condition
(1) COOH

(4) , oleum, NaOH, H3O

+

(2) CHO
AE0255
NEET(UG) 2023
(3) COOH
25. Identify the product in the following reaction :

(4) OH
(i ) Cu2Br2 /HBr
(ii ) Mg/dry ether

→ Product
(iii ) H2O
AM0258

NEET(UG) 2023 (Manipur)

(1) (2)
28. Choose the correct sequence of reagents in the
conversion of 4-nitrotoluene to 2-bromotoluene.
(1) NaNO2/HCl; Sn/HCl; Br2; H2O/H3PO2
(2) Sn/HCl ; NaNO2/HCl; Br2;H2O/H3PO2
(3) (4) (3) Br2;Sn/HCl;NaNO2/HCl;H2O/H3PO2
(4) Sn/HCl;Br2;NaNO2/HCl;H2O/H3PO2
AM0256
26. Which of the following reactions will NOT give AM0259
primary amine as the product?
(i) LiAlH4
(1) CH3CN  ⊕→ Product
(ii) H3O

(i) LiAlH4
(2) CH3NC  ⊕→ Product
(ii) H3O

(i) LiAlH4
(3) CH3CONH2  ⊕→ Product
(ii) H3O

Br2 /KOH
(4) CH3CONH2 
→ Product
AM0257

EXERCISE-II (Previous Year Questions) ANSWER KEY

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. 4 2 4 2 2 1 4 1 2 2 1 2 1 3 2
Que. 16 17 18 19 20 21 22 23 24 25 26 27 28
Ans. 1 2 3 4 1 3 4 1 3 1 2 3 3
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EXERCISE-III (Analytical Questions) Master Your Understanding

CO
1. NH3
A  ∆
→ B  Br2 + KOH
→ C → CH3 CH2 NH2 (i) KOH H3O⊕
4. NH A B+C
(ii) C2H5Br
A is :- CO

(1) CH3COOH B and C in the above sequence are

(2) CH3CH2CH2COOH (1) Benzoic acid + aniline

(3) CH3–CH–COOH (2) Phthalic acid + ethylamine

(3) Phthalic acid + aniline
CH3
(4) Benzoic acid + ethylamine
(4) CH3CH2COOH AM0087
AM0083
5. The end–product in the reaction sequence would
2. The final product C, obtained in this reaction be :
would be HNO2
Ethyl amine PCl5
→ A NH3
→ B →C
NH2 (1) Ethyl cyanide (2) Ethyl amine
Ac2O Br2 H2O (3) Methyl amine (4) Acetamide
A B C
CH3COOH H+ AM0088
CH3
6. A compound of mol. wt. 180 gm is acetylated to
NH2 COCH3 give a compound of mol. wt. 390. The number
COCH3 Br of amino groups in the compound are :-
(1) 2 (2) 4 (3) 5 (4) 6
(1) (2) AM0090
CH3 CH3

NH2 NHCOCH3 7. Which one of the following tests can be used to

Br Br identify primary amino group in a given organic
compound

(3) (4) (1) Iodoform test

CH3 CH3
(2) Victor Meyer's test
AH0085
(3) Carbylamine reaction
AgCN H3 O + (4) Libermann's reaction
3. C2H5Br  → A  → HCOOH + B;
PO0092
CHCl Re duction
B 3
→ A  → C
KOH 8. Which of following will not gives only primary
A, B, C respectively in the above sequence are amine
3( )NH Alc
(1) Ethane amine, methane nitrile and diethyl (1) C2 H5 X →
( ) Na Hg
amine (2) CH3 − CN 
C2 H5 OH
→
(2) Carbyl amino ethane, ethane amine and O
( i ) LiAlH
primary amine (3) CH3 – C – NH2 
( ii ) H2 O →
4

(3) Ethyl isocyanide, ethyl amine and methyl O

isocyanate ⊕  (i) R-X
(4) NK
(4) Carbylamino ethane, ethanamine and ethyl (ii) NaOH (aq)
methyl amine O
AM0086 AM0111
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9. Basic nature of amine in aqueous medium can be 13. Which of following can be use to distinguish
explained by :- primary, secondary and tertiary amine?
(1) Inductive effect (2) Solvation effect (1) Carbyl amine reaction
(3) Steric hinderance (4) All of these (2) Reaction with Nitrous acid
AM0112 (3) Reaction with Hinsberg's reagent followed by
10. Which of following is correct regarding basic NaOH
nature ? (4) Both 2 & 3
(1) R – NH2 > R2NH > R3N (Gaseous phase) PO0118
(2) CH3NH2 > (CH3)2NH > (CH3)3N (Aqueous 14. Which of following is insoluble in alkali?
solutions) O
(3) (C2H5)2NH > (C2H5)3N > C2H5–NH2 > NH3
(1) H5C6–S–N–C2H5
(Aqueous solutions)
(4) (C2H5)2NH > PhNH2 > Ph – NH – CH3 O C2H5
(Aqueous solution) O
GC0113 (2) H5C6–S–N–CH3
11. What is decreasing order of H-bonding in water OH
for alkyl substituted ammonium cation ? O
⊕ ⊕ ⊕
(1) R NH3 > R 2 NH2 > R 3 NH (3) H5C6–S–N–C2H5
⊕ ⊕
(2) R 3 NH > R 2 NH2 > R NH3
⊕
OH
(4) All of these
⊕ ⊕ ⊕
(3) R 2 NH2 > R 3 NH > R NH3 AM0119
⊕ ⊕ ⊕ 15. These days benzene sulphonyl chloride replaced
(4) R 2 NH2 > R NH3 > R 3 NH
by which compound in Hinsberg test :-
AM0114 O
12. Which of following is not correct match? (1) CH2–S–Cl
O
O
(1) H5C2NH2 + CH3–C–Cl → SO2Cl
O CH3
(2)
H5C2–NH–C–CH3+HCl
(Acylation) SO2Cl

O
(3)
(2) H5C2NH2 + H5C6–C–Cl →
CH3
O

H5C2–NH–C–C6H5+HCl (4) SO3H

(Benzoylation)
AM0120
(3) (H5C2)2 NH + CHCl3 + 3KOH → 16. Which of following is water insoluble and stable
H5C2 – NC + 3KCl + 3H2O at room temperature ?
(Carbyl amine reaction)
(1) C6H5N2⊕Cl
(4) H5C2 – NH2 + CH3COOH →
⊕ (2) C6H5N2⊕BF4
H5 C2 NH3 CH3 COO –
(3) C6H5N2⊕HSO4
(Salt formation or
Neutralisation) (4) All
AM0117 AM0123
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17. Which of following reaction do not displace N2 22. Identify incorrect match in the following -
from benzenediazonium salt? ⊕ 
⊕ − Cu2 Cl2 / HCl N2X Cu2X2
(1) ArN Cl →
2 (1) ESR
⊕ − Cu / HCl
(2) ArN Cl 
2 →

(3) ArN2⊕ Cl − + KI → CH3

(2) X2/Fe ESR
⊕ − Room dark
(4) ArN Cl + HBF4 
2 → temperature
CH2CH3
AM0124 (3) Br2/hν FRSR
or heat
18. Which of following group can not be introduced O2N
in the benzene ring by sandmeyer reaction? CH2OH
(1) –Cl (2) –Br (3) –CN (4) –I
HCl
AM0125 (4) heat
NSR
19. Formation of benzene from C6H5N2⊕Cl– by use of
OH
C2H5OH is example of :-
HD0074
(1) Redox reaction
23. Which of the following reactions will not lead to
(2) Electrophilic substitution reaction
(3) Nucleophilic substitution reaction a phenol :-
(4) Elimination reaction (1) C6H5SO3Na + NaOH →
i) Fuse / ∆
ii) H +
AM0126
Boil
Room NaNO2
(2) C6H5N2Cl + H2O  →
20. A + HBF4 Temprature
B Cu,∆
C
NaOH
Fe/HCl (3) C6H5ONa + RX 
Heat

→
A
E H⊕
D OH
Heat
(4) + NaOH(CaO)  →
What is "E"
COONa
(1) N = N – Ph HD0150
24. Intermediates formed during reaction of
(2) NH – N = N – Ph
R–C–NH2 with Br2 and KOH are:
O
(3) Ph–N=N NH2
(1) RCONHBr and RNCO
NH2 (2) RNHCOBr and RNCO
(3) RNH—Br and RCONHBr
(4)
(4) RCONBr2

Ph AM0165
NaCN Ni/H2 Acetic
AM0127 25. CH3CH2Cl  → X → Y
anhydride
→ Z

21. Diazo coupling reaction can be use to distinguish Z in the above reaction sequence is :–
(1) Aniline and Benzyl amine (1) CH3CH2CH2NHCOCH3
(2) Ethylamine and N-methyl aniline (2) CH3CH2CH2NH2
(3) Aniline and Phenol
(3) CH3CH2CH2CONHCH3
(4) All of these
(4) CH3CH2CH2CONHCOCH3
AM0128
CA0166

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26. CH3CH2CH2–C≡N 
3

→ A  3
→B H O⊕ NH 30. In a reaction of aniline a coloured product C was
∆

Product 'B' is :- obtained.

(1) CH3–CH2CH2–C–OH CH3

NH2 NaNO2/HCl N
O CH3
0° to 5°C
B C
(2) CH3CH2CH2–C–H
The structure C would be :
O

(3) CH3CH2CH2–NC CH3

NH–NH N
(4) CH3CH2CH2–C–NH2 (1) CH3

O
CH3
CA0170 N=N N
(2)
27. Which of the following reaction sequence does CH3

not give phenol ? N=N–CH2–N

(3)
Cl NaOH, 623K CH3
(1) HCl
300 atm
CH3 CH3
N=N
(2) oleum 1.NaOH, ∆
(4)
2.H+

NH2
(3) NaNO2 H3PO2 AM0058
HCl H2O

31. Predict the product :

(4) O2 H+ NHCH3
H2 O + NaNO2 + HCl → Product

AE0222 OH

28. In a set of reactions propionic acid yielded a N–CH3

(1)
compound (D) ;
SOCl NH CH3
CH3CH2COOH (A) 
2
→ (B) 
∆
3
→ (C)
N–N=O
KOH
→
Br (D), What is the structure of (D) (2)
2

(1) CH3CH2CH2NH2 (2) CH3CH2CONH2 CH3

(3) CH3CH2NHCH3 (4) CH3CH2NH2 N–NO2
(3)
CA0056

29. Which one of the following on reduction with NHCH3 NHCH3

NO
LiAlH4 yields a secondary amine ? +
(4)
(1) Methyl isocyanide (2) Acetamide
NO
(3) Methyl cyanide (4) Nitro ethane
AM0059
AM0057

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32. Which of the following statements about primary 35. In a set of reactions m-bromobenzoic acid gave a
amines is 'False' ? product D. Identify the product D

(1) Alkyl amines are stronger bases than COOH

ammonia SOCl2 NH3 NaOH
B C D
Br2
(2) Alkyl amines are stronger bases than aryl Br
A
amines

(3) Alkyl amines react with nitrous acid to SO2NH2 COOH

produce alcohols

(4) Aryl amines react with nitrous acid to produce (1) (2)
Br Br
phenols
NH2 CONH2
AM0060

33. Acetamide is treated with the following reagents (3) (4)

Br Br
separately. Which one of these would yield
methyl amine ? CA0092
36. An organic compound 'A' on treatment with NH3
(1) PCl5
gives 'B' which on heating gives 'C'. 'C' when
(2) NaOH/Br2 treated with Br2 in the presence of KOH
(3) Sodalime produces ethylamine. Compound 'A' is :-

(4) Hot conc. H2SO4 (1) CH3CH2COOH

AM0061 (2) CH3COOH

(3) CH3CH2CH2COOH
34. What is the product obtained in the following
NO2 (4) CH3–CHCOOH
Zn
reaction :  → ....... ? CH3
NH4 Cl

CA0094
NHOH
(1) 37. An organic compound C3H9N (A), when treated
with nitrous acid, gave an alcohol and N2 gas was
N evolved. (A) on warming with CHCl3 and caustic
N
(2) potash gave (C) which on reduction gave
isopropylmethylamine. Predict the structure of
O¯ (A):
N=N
+ (1) CH3–N–CH3
(3)
CH3

NH2 (2) CH3CH2CH2–NH2

(4)
CH3
(3) CH–NH2
CH3
AM0063
(4) CH3CH2–NH–CH3

AM0064

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NO2 NO2 39. Nitrobenzene on reaction with conc. HNO3/

A H2SO4 at 80-100°C forms which one of the

38. In the reaction A is
Br Br
following products ?
⊕N2 Cl
(1) 1, 2, 4-Trinitrobenzene
+
(1) H /H2O (2) HgSO4/H2SO4
(2) 1, 2-Dinitrobenzene
(3) Cu2Cl2 (4) H3PO2 and H2O
(3) 1, 3-Dinitrobenzene
AM0065
(4) 1, 4-Dinitrobenzene

AH0066

EXERCISE-III (Analytical Questions) ANSWER KEY

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. 4 3 4 2 2 3 3 1 4 3 1 3 4 1 3
Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans. 2 4 4 1 3 4 1 3 1 1 4 3 4 1 2
Que. 31 32 33 34 35 36 37 38 39
Ans. 2 4 2 1 3 1 3 4 3
160