CONTENTS

S.NO. TOPIC PAGE NO

TOPIC PAGE NO.

1. INTRODUCTION 2

2. PREPARATION OF AMINES 2

3. PHYSICAL PROPERTIES 6

4. CHEMICAL PROPERTIES 7

5. DIAZONIUM SALTS 10

1
Amine

AMINE
1. INTRODUCTION
(i) Amines are called alkyl derivative of NH3.
(ii) If a hydrogen atom of NH3 is replaced by an alkyl group then it is called primary amine
and possess –NH2(amino) group.
(iii) If two hydrogen atoms of NH3 are replaced then it is called secondary amine and it
posses > NH (mino) group.
(iv) If all hydrogen atoms of NH3 are replaced then it is called tert. amine and has a nitrilo N
group.
(v) N is in sp3 hybridisation and tetrahedral geometry.
(vi) Bond angle increases from ammonia to 3º amines.
NH3 (107º) < RNH2 < R2NH < R3N

2. PREPARATION OF AMINES
(i) Reduction of nitro compounds

(ii)Ammonolysis of alkyl halides

The free amine can be obtained from the ammonium salt by treatment with a strong base:
 –  –
R – NH3 X  NaOH  R – NH2  H2O  Na X
primary amine is obtained as a major product by taking large excess of ammonia.
The order of reactivity of halides with amines is RI > RBr >RCl.
(iii) Reduction of nitriles

H 2 Ni
R –C  N R – CH2 – NH 2
Na (Hg )C3H 4OH

(iv) Reduction of amides

2
Amine
(v) Gabriel phthalimide synthesis

(vi) Curtius Reaction :

H2 O
RCON  
 R  N  C  O   R  NH 2
N CO
3 2 2
Acyl azide Alkyl isocyanate Alkyl amide

Mechanism :

RCOCl  NaN3 
 RCON3 NaCl

O O O

R C N N N  R C N N R
N  C N N2

R N N2 
 R—NCO
C alkyl isocyanate

O
H2 O

H2 O
R N C OH 
R N C O

OH OH
O

R NH C OH 
– CO
 R — NH 2  CO2
2

3
Amine
(vii) Schmidt Reaction : Carboxylic acid reacts with hydrozoic acid in presence of concentrated
H 2SO 4 to give isocyanates.

R – COOH + N 3H H2SO4  R – N2H + C2 O + H 2O

Mechanism :

O OH OH
R C  H  
R C H N3

R C OH
+
OH OH H N N N
–H2O

O
R C O H
C  
 H2
R — N  C  O   R  N2
+
isocyanate N N N
+
–H 2O N N N
R — NH2  CO2

(viii) Lossen Reaction : Hydroxylamine on treatment with acid chloride gives acyl derivatives of hy-
droxyl amine. the acyl derivatives exist in two tautomeric form keto form called hydroxamic form and
enol form called hydroximic acid. The hydroxamic form.

R OH 
 R  NH 2  CO 2

NH

HO

Mechanism :
O O

R  H2N OH R + HCl

Cl
NH
HO

O OH

R
R
N
NH

HO HO
Hydroxamic acid (enol form)
(keto form)

4
Amine
The hydroxamic form (keto form) forms o-acyl derivatives of hydroxamic form which on heating with
bases forms isocyanates and finally amines upon hydrolysis

H O H O

R C N OH  R C Cl 
R C N O C R

O O
O
H2 O
R  NH2   R — N  C  O  R C N O C R
CO2

(ix) Hoffmann bromamide degradation reaction : The reaction of amid with bromin in present of
base to form primary amine.

Mechanism:

2NaOH  Br2 
 NaOBr  NaBr  H 2O

O O

R C
–
 R
NH2  OBr  C N Br  OH –

H
N-bromoacetone

O O

R C N Br  OH –
–H 2 O
R C N – Br  H2O

H Rearrangement

H O
R — NH2  CO2 2  R — N  C  O (Isocyanate)

Ex.1 Compound (A) has molecular formula C9H14NCl. (A) gives an immediate precipitate with AgNO3. It is
very resistance to bromination in either acid or alkaline solution. It is also resistance to heat, nitration and
oxidation by KMnO4. Suggest structure for (A).
Sol. Since (A) (C9H14NCl) gives immediate precipitate with AgNO3, it must be an ionic compound. Further, it
is resistant to oxidation, heat, nitration etc. it must be a quanternary ammoinium salt. Therefore, possible
structure of (A) may be :

CH3 +
–
C6H5 – N – CH Cl, quaternary-salt
3

CH3
(A)
(C9H14NCl)
N,N,N-Trimethylaniliniumchloride

5
Amine
Ex.2 Identify (A) through (E) in the following sequence
– HCl NaOH EtBr H3 O 
PhSO2Cl  EtNH2  (A)  (B)  (C)  (D)  (E)

Sol. PhSO 2 NHEt PhSO2 N – Et Ph SO2 NEt2

(A ) (B) (C)

H 3O
 PhSO2OH Et2 NH2

(D) (E)

Ex.3 How the ethylamine is prepared from :

(a) Propanamide (b) Ethanamide (c) Nitroethane (d)Acetaldehyde
(e) Ethanol (on large scale) ?
Sol. (a) When propanamide is treated with Br2 and KOH, ethanamine is obtained.
CH3CH2CONH2 + Br2 + 4KOH  CH3CH2NH2 + K2CO3 + 2KBr + 2H2O
Ethanamine

(b) When ethanamide is reduced with lithium aluminium hydride, ethanamine is

LiAlH4
obtained. CH3CONH2 + 4[H]   CH3CH2—NH2+ H2O

Ethanamide

(c) Nitroethane can be converted into ethanamine by the reduction with Sn/HCl.
CH3CH2—NO2 + 6[H]  Sn / HCl
 CH3CH2NH2 + 2H2O
Ethanamine
Nitroethane

(d) When acetaldehyde is treated with ammonia, imine is formed whichonreduction gives ethanamine.
H H
| |
H 2 / Ni
CH 3 — C  O + NH3  
H2O
CH 3 — C  NH   CH 3 — CH 2NH 2
2[H]
Ethanal Acetaldimine Ethanamine
(e) When a mixture of ethanol and ammonia is passed over alumina at 723 K and high pressure,
than amine is formed.
CH3CH2OH + NH3 A723K
l2O3
 CH3 CH2 NH2  H2 O
Ethanamine

3. PHYSICAL PROPERTIES :
(i) Unlike other organic compounds, amines are much more soluble in water. Because All
amines form a stronger H- bond with water.
(ii) Like ammonia, amines are polar compounds and except 3º amines can form intermoleculer H-
bonds that’s why they have higher boiling points.
(iii) Boiling points of amines are lesser than alcohols and acids of comparable mol. weight.
Because H- bonding in amines is less pronounced in 1º and 2º than that in alcohols and
carboxylic acids. Because nitrogen is less electronegative than oxygen.
Thus every question regarding boiling point can be answered on the basis of H - bonding.
(iv) Boiling points of 1º, 2º and 3º amines follow the order.
1º > 2º > 3º amine.
(v) Solubility in water follow the order.
1º > 2º > 3º amine.
This is all due to H- Bonding.

6
Amine
4. CHEMICAL PROPERTIES :
Alkylation : Amines undergo alkylation on reaction with alkyl halides

R1
R1 X R2 X R3 X
|
RNH2 HX
RNHR1 HX
R -N -R 2 HX
R2 N R2 X¯
|
R3
(quartenary amm. salts.)

Acylation : 1º and 2º amines react with acetyl chloride or acetic anhydride to form acetyl derivatives.
R-NH2 + CH3COCl  RNHCOCH3 + HCl
R -NH2 + (CH3CO)2O  RNHCOCH3 + CH3COOH
(CH3)2NH + CH3COCl  (CH3)2N-COCH3 + HCl
Note : (a) Tertiary amines donot undergo this reaction because of absence of replacable H- atom.
(b) When Benzoyl chloride is used in place of acet yl chloride react ion is called
‘Schotten - Baumann’ reaction.

Benzoylation : WhenAmines react with benzoyl chloride (C6H5COCl).

CH 3 NH 2  C6 H5COCl  CH 3 NHCOC6 H5  HCl
Methanamine Benzoyl chloride NMethylbenzamide

Heat
Carbylamine reaction : R - NH 2  CHCl 2  3KOH  R - NC  3KCl  3H 2 O

Cl
R — NH2  CCl2 
 R HN C
Mechanism :
H Cl
-HCl

+
R — N  C 
 R N C Cl

7
Amine
Reaction with nitrous acid :
 -
NaOH2 HCl
R - NH 2  HNO 2  [R - N 2 Cl ] ROH  N 2  HCl
 -
NaNO2 2HCl
C6 H5 - NH 2   C6 H5 - N 2 Cl NaCl 2H 2O
Ani ln e Benzenedia monium
Chloride

Reaction with arylsulphonyl chloride : Benzenesulphonyl chloride (C6 H5 SO2 Cl), which is also known
as Hinsberg’s reagent, reacts with primary and secondary amines to form sulphonamides.
(i) The reaction of benzenesulphonyl chloride with primary amine yields N-ethylbenzenesulphonyl amide.

The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence of strong
electron withdrawing sulphonyl group. Hence, it is soluble in alkali.
(ii) In the reaction with secondary amine, N,N-diethylbenzenesulphonamide is formed. It is in soluble
alkali.

(iii) ter.Amine does not react with Hinsberg’s reagent it is present above solution.
Electrophilic substitution : Due to +M effect of -NH 2 genrate electron dencity at ortho and para
position hence, aniline active toward Electrophilic substitution
(i) Bromination: Aniline reacts with bromine water at room temperature to give a white precipitate of
2,4,6-tribromoaniline.

If we have to prepare monosubstituted aniline derivative, This can be done by protecting the -NH 2
group by acetylation with acetic anhydride, then carrying out the desired substitution followed by hy-
drolysis of the substituted amide to the substituted amine.

8
Amine
The lone pair of electrons on nitrogen of acetanilide interacts with oxygen atom due to resonance as
shown below:

Hence, the lone pair of electrons on nitrogen is less available for donation to benzene ring by
resonance. Therefore, activating effect of -NHCOCH 3 group is less than that of amino group.
(ii) Nitration: Direct nitration of aniline is not possible because in the strongly acidic medium, aniline is
protonated to form the anilinium ion which is meta directing.

However, by protecting the -NH 2 group by acetylation reaction with acetic anhydride, the nitration
reaction can be controlled and the p-nitro derivative can be obtained as the major product.

(iii) Sulphonation:

s
Ex.4 Consider the following reaction,
 H / H2O 
C 6 H 5 NH 2  CHCl 3  KOH   ( A)    (B)  (C )
Find the compounds (B) and (C).
C6 Hl5NH 2  CHCl3  3KOH 
 C6 H5 N  C  3Kl  3H 2 O
Sol. (A)


C6 H5 N  C  2H 2 O H C6 H5 NH2  HCOOH
(A) (B) (C )

9
Amine
Ex.5 Sulphanilic acid is insoluble in water and acid but soluble in caustic alkali. Comment.
Sol. Sulphanilic acid exist as a Zwitter ion and exhibits strong dipole-dipole interactions. Therefore, it is insoluble
in water. on adding acid, SO 3- fails to accept H + ion, thus sulphanilic acid is insoluble in acid. However,
+
when alkali is added, strongly basic hydroxyl ion can abstract a proton from —NH 3 to form soluble salt.

+ NH2
NH3

+ NaOH + H2 O

SO3Na
SO3-
Zwitter ion structure of sulphanilic acid Sodium p-aminobenzene sulphonate

Ex.6 How will you carry out the following conversions?

O

C NH2 NH CH3
(a) 


(b) NH2 
 NH2

C NH2 NC
NH2 Br2 / 
KOH
 CHCl3
 
Sol. (a) KOH

NH
LIAlH4  CH3

H 2SO K Mn 4O / H
NH NaNO 2 OH    
4   


(b) 2 HCl

COOH 
BaO
 O 
NH 
 
3
NH H2 / Pt
 NH 2

COOH

5. DIAZONIUM SALTS :
 - -
The diazonium salts have the general formula R N 2 X where R stands for an aryl group and X ion may
be Cl -, Br-, HSO 4-, BF -3, etc.
Resonance of benzene diazonium ion is

10
Amine
Method of Preparation of Diazonium Salts
 -
273-278K
C6 H5 NH 2  NaNO2  2HCl  C6 H5 N 2 Cl NaCl  2H 2O
Chemical Reactions
The reactions of diazonium salts can be broadly divided into two categories, namely (A) reactions
involving displacement of nitrogen and (B) reactions involving retention of diazo group.
(i) Reactions involving displacement of nitrogen
Diazonium group being a very good leaving group, is substituted by other groups such as
Cl-, Br- , I-, CN- and OH- which displace nitrogen from the aromatic ring.
(a) Replacement by halide or cyanide ion: The Cl-, Br- and CN- nucleophiles can easily be introduced at
the benzene ring in the presence of Cu(I) ion. This reaction is called Sandmeyer reaction.

Alternatively, chlorine or bromine can also be introduced byGatterman reaction.

 -
(b) Replacement by iodide ion: Ar N 2 Cl  KI  ArI  KCl  N 2
(c) Replacement byfluoride ion:
 -  -
Ar N 2 Cl  HBF4  Ar - N 2 BF4   Ar - F  BF2  N 2
 -
(d) Replacement by H: Ar N 2 Cl  H 3PO2  ArH  N 2  H3PO3  HCl
 -
Ar N 2 Cl  CH 3CH 2OH  ArH  N 2  CH 3CHO  HCl
 -
(e) Replacement by hydroxyl group: Ar N 2 Cl  H 2O  ArOH  N 2  HCl
(f) Replacement by –NO 2 group:

(ii) Reactions involving retention of diazo group coupling reactions

11
Amine
Ex.7 Provide structures for the products of the reaction of PhN 2with
(a) PhNMe2 (b) 2-naphthol (c) PhCH3.
Sol. ArN 2 is a weak electrophile that undergoes diazo couplignonly with rings activated by OH, NH2
,
NHR or NR 2 .

Ph N N NMe2
(a) N,N-dimethylaminoazobenzene
(butter yellow

N N Ph
OH

(b)
1-Phenylazo-2-naphthol

(c) No reaction. The substrate ring is insufficiently activated.

Ex.8 A weakly acidic medium is provided for coupling of benzene diazonium chloride with aniline.
Comment.

+ -
N2Cl +H NH2 pH 4-5 N=N NH2
Sol.
273-278 K
Benzene diazonium chloride -HCl p-Aminoazobenzene
Aniline

If the high conc. of H+ ions are used during these reactions, then protonation of aniline takes
place.

+
H+
NH2 H3 N

Aniline Anilinium ion

The positive charge on protonated amine exerts -I effect, thus coupling of amine with diazonium
salt is not favoured, at low pH (or high acid strength). Also, we know high pH is not desirable
for coupling reactions. Therefore, optimum pH for coupling reactions with amines is 4-5.

Ex.9 The end product (Z) of the following reaction is ?

N2Cl H  / H 2O
Cu / KCN
(X) (Y) NaOH
(Z)

N2Cl Cu / KCN

 CN
Sol.

12
Amine

SOL VED EXAMPLE

Ex.1 Account for the fact that 2-aminoethanoic acid (glycine) exists as a dipolar ion, as does p-
aminobenzenesulfonic acid (sulfanilic acid) but p-aminobenzoic acid does not.
Sol. The aliphatic NH 2 is sufficiently basic to accept an H from COOH. the COOH is not strong enough
to donate H to the weakly basic ArNH2 , but SO3H is a sufficiently strong acid to do so.
-
H3 N — CH 2COO p — H 2N — C 6H 4 — COOH p — H 3N  — C6 H4 — SO-3
Glycine pA min obenzoic acid Sulfanilic acid

Ex.2 Mixture oftwo aromatic compounds (A) and (B) was separated by dissolving in chloroform followed by
extraction with aqueous KOH solution. The organic layer containing compound (A), when heated with
alcoholic solution of KOH produced a compound (C) (C7H5N) associated with an unpleasant odour.
The alkaline aqueous on the other hand, when heated with chloroform and then acidified give a mixture of
two isomeric compounds (D) and (E) of molecular formula C7H6O2. Identify the compounds (A),
(B), (C), (D), (E) and write their structures.
Sol. (a) One of the compound A and B is soluble in aq.KOH and thus it must be acidic in nature whereas
another compound is soluble in chloroform is either basic or neutral in nature.
(b) The compound (A) on heating with alcoholic KOH solution (chloroform already present) produces
compound (C) (C7H5N) having unpleasant odour. The compound (C) is Phenylisocyanide and, therefore,
compound (A) must be aniline which is soluble in chloroform but insoluble in aq.KOH.
(c) The compound (B) must be phenol as it is soluble in aqueous KOH and produces isomers o-
hydroxybenzaldehyde (D) and p-hydroxylbenzaldehyde (E) on heating, with chloroform followed by
acidification.
The reactions are as follows :
NH2

N C

Warm
+ CHCl3 + 3KOH + 3KCl + 3H3O (carbylamine reaction)
Aniline (A) Phenyl isocyanide
(Soluble in chloroform) (C)

OH OH OH
CHO
CHCl3/KOH
H+ +
Phenol (B) Salicylaldehyde
(Soluble in KOH) (D) CHO
p-Hydroxybenzaldehyde
(E)
Ex.3 Aneutral compound (A) C 8H 9ON on treatment with sodium hypobromite forms an acid soluble sub-
stance (B), C7H9N. On addition of aqueous sodium nitrite to a solution of (B) in dil. HCl at 0 -5°C, an
ionic compound (C). C7H7N2Cl is obtained. (C) gives a red dye with alk  -naphthol solution. When
treated with potassium cuprocyanide, (C) yields a neutral substance (D), C8H7N. ON hydrolysis (D)
gives (E), C8H8O2. (E) liberates CO2 from aqueous sodium bircarbonate. (E) on permanganate
oxidation furnishes (F), C8H6O4 , (F) on nitration yields two isomeric mononitro derivatives (G) and (H)
having molecular formula, C 8H NO5
. Write the reaction involved in different steps.
6

13
Amine

CONH2 NH2 N2Cl CN

(A) : (B) : (C) : (D) :
CH3 CH3 CH3 CH3
Sol.
COOH COOH COOH COOH
(E) : (F) : (G) : (H) :
CH3 COOH COOH O2N COOH
NO2

Ex.4 An optically active amine (A) is subjected to exhaustive methylation and Hoffman elimination to yield on
alkene (B). (B) on ozonolysis gives an equimolar mixture of formaldehyde and butanol. Deduce the
structures of (A) and (B). Is three any structural isomer of (A), if yes draw its structure?

(A) : H3C CH CH2CH2CH3 (B) : H2C CHCH2CH2CH3

Sol.
NH2
NH 2 CH 2 CH 2 CH 2 CH 2 CH 3 is positional isomer of (A).

Ex.5 A mixture of two aromatic compounds (A) and (B) was separated by dissolving in chloroform followed
by extraction with aqueous KOH solution. Theorganic layer containing compound (A), when heated
with alcoholic solution of KOH produced a compound (C) (C 7H 5N) associated with an unpleasant
odour. The alkaline aqueous layer on the other hand, when heated with chloroform and then acidified
give a mixture of two isomeric compounds (D) and (E) of molecular formula C7H 6O 2. Identify the
compounds (A), (B), (C), (D) and (E).

NH2 OH N=C OH OH
CHO
Sol. (A) : (B) : (E) :

CHO

Ex.6 Compound (A), C14H10N2O whenheated with dilute sulphuric acid gives ammonium sulphate, com-
pound (B), C8H6O 4 and compound (C), C 6H 7N (as its sulphate). Compound (B) on heating gives (D),
C8H4O3 and on heating with sodalime gives benzene. Compound (C) with dilute H2SO 4/NaNO 2 in the
cold followed by heating with water gives (E), C 6H6O. Compound (E) on heating with Zn dust again
gives benzene. Identify (A), (B), (C) and (e) giving proper reactions?

CN
CO2H
dil. H2SO4
  (NH 4 ) 2 SO 4   C6 H5 NH 2
C NH (C)
CO2H
(B)
O H 2SO4
Sol. (A) O
(C6 H5 NH3 ) 2 SO 4
CO2H C
 
 O
- H 2O
CO2H C
(B) (D)
O

14
Amine
Ex.7 An organic compound (A) composed of C, H and O gives a characteristic colour with ceric
ammonium
nitrate. Treatment of (A) with PCl5 gives (B) which reacts with KCN to form (C). The reduction of (C)
with Na and C2H5OH produces (D) which on heating gives (E) with evolution of NH3. Pyridine is
Sol. obtained on treatment of (E) with nitrobenzene. Give the structures of (A) to (E) with proper reasoning.
(A) is an alcohol which gives characteristic red colour with ceric ammonium nitrate.
PCl5 Na+ 
ROH RCl KCN R -C  N R CH2NH2 -NH3
E Nitrobenzene
C2H5OH
(A) (B) (C) (D)
Start with propane-1, 3-diol
CH2OH CH2Cl
CH2 PCl5 CH2CN
CH2 2KCN
CH2 Na + C2H5OH
CH2OH CH2Cl CH2CN
(A) (B)
(C)

CH2CH2NH2  Nitrobenzene
CH2
CH2CH2NH2 -NH3 -6H
N
(D)
H
Piperidine
(Hexahydropyridine)
(E)

Ex.8 Glycine exists as a Zwitter ion but anthranilic acid does not. Comment.
Sol. -COOH group of glycine releases H+ ion which is accepted by -NH2 group. Thus glycine exist of a
Zwitter ion.
H H
+
H2N - C - COOH H3N - C - COO-
H H
Glycine Zwitter ion of glycine

NH2
COOH

In anthranilic acid,
Anthranilic acid
(2- Aminobenzoic acid)

Electron withdrawing -COOH and phenyl group reduces electron density of N of –NH 2 group,
therefore,
Ex.9 -NH2 fails to accept a proton. Thus anthranilic acid can not form Zwitter ion.
Write reactions of the final alkylation product of aniline with excess of methyl iodide in the presence of
sodium carbonate Sol.
+
Sol. H6H5NH2 + CH3I [C6H5NHCH3]I-
Aniline Methyliodide N-Methylanilinium iodide


2[C6H5 NH CH3]I- + Na2CO3  2C6 H 5 NHCH3  CO 2  2NaI
NMethylaniline

15
Amine

2CH I3
2C6H5 NH CH3   2C6H5N(CH3)2 + CO2 + 2NaI
Na 2CO 3

C6H5NHCH3 + CH3I [C6H5NH(CH3)] +I -

N.N.N-Trimethyl anilinium ioidide

 2-
[2C6H5 N (CH3)3] I- + Na2CO3  [C6 H5 N(CH3 )3 ]2 CO3  2NaI
N, N, NTrimethylanilinium Carbonate

Ex.10 What happens when

(a) Aniline is treated with sodium nitrate and dil. HCl at 273 K,
(b) Aniline is treated with Benzaldehyde,
(c) Ethylamine reacts withAgCl,
(d) Amixture of alcohol and ammonia is passed over heated aluminium oxide as catalyst.
(e) Sodium nitrite is added to a solution of ethylamine in dil. HCl at 273 K ?
Sol. (a) Benzenediazonium chloride is formed.
N NCl
NH2
NaNO2 + HCl
273 K

Aniline Benzenediazonium chloride

(b) Benzal aniline is formed.

H H

NH2 O C N C
H+

Benzaldehyde Benzalaniline
Schiff's base

(c) Soluble complex-Bis-(ethylamine) silver (I) chloride is formed

AgCl(s) + 2C2H5NH2(aq)  [Ag(C2H5NH2)2]Cl(aq)
Bis-(ethylamine) sliver (I) chloride (soluble)

(d) Primary amine is formed. If ammonia is taken in excess, a mixture of 1°, 2°, 3° amines and
quaternary ammonium salt is formed.
Al O
ROH + NH3  2
3  R — NH2 + H2 O
723K

1° alcohol 1° alcohol

(e) Ethyl alcohol is formed

NaNO2 + HCl  NaCl + HNO2
Nitrous acid

C2H5NH2 + HNO2  C2H5OH + N2 + H2O

Ex.11 Give one chemical test to distinguish between the following pairs of compounds :
(i) Methylamine and dimethylamine (ii) Secondary and tertiary amines
(iii) Ethylamine and aniline (iv)Aniline and benzylamine
(v) Aniline and N-methyl aniline

16
Amine
Sol. (i) Methyl amine, being a primary amine will give carbylamine reaction (offensive smell of isocyanide
when treated with CHCl3 + KOH) while dimethyl amine will not show any reaction with
CHCl3 + KOH (alc.)
CH3NH2 + CHCl3 + 3KOH (alc)  CH 3 NC  3KCl  3H 2 O
Methyl isocyanide
(offensive smell)

(ii) When secondary amine is treated with HNO2(NaNO2 + HCl), if forms yellow coloured oily compound
N-nitrosoamine, which on warming with a crystal of phenol and H2SO4 gives a green solution and on
further addition of aq KOH red solution(Libermann nitroso test). This test is not given by tertiaryanines.
(CH3)2 NH + HO—N O (CH3)2 N—N O + H2O
Secondary amine Nitric acid N-Nitrosodimethylamine

Phenol + H2SO4

KOH + Water
Red colour Green colour
(iii) When aniline is treated by NaNO2 + HCl at 273 K, benzenediazonium chloride is formed which on
treatment with b-naphthol gives a bright orange dye, 1-phenylazo-2-naphthol.

NaNO2/HCl
NH2 273 K
N N Cl

OH
OH

N N

(iv) Benzyl amine on treatment with NaNO2 and HCl forms benzyl alcohol with the evolution of N2 gas
while aniline froms benzene drazonium chloride which gives organe dye with alkaline b-naphthol.

(v)Aniline, being a primary amine, gives carbylamine reaction while N-methyl aniline (sec. amine) will
not give this rest.

NH2 + CHCl3 + 3KOH(alc) NC + 3KCl + 3H2O

Phenyl isocyanide
(offensive smell)

17
Amine

EXERCISE-I
Q.1 Arrange the following :
(i) In decreasing order of the pK values:
b
C2H5NH2, C6H5NHCH3 , (C2 H5 )2 NH and C6 H5 NH2
(ii) In increasing order of basic strength:
C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH 3NH 2
(iii) In increasing order of basic strength:
(a)Aniline, p-nitroaniline and p-toluidine
(b) C6H5NH2, C 6H 5NHCH 3 , C6H5CH2NH2.
(iv) In decreasing order of basic strength in gas phase:
C2H5NH2, (C2H5) 2NH, (C 2H 5) 3N and NH 3
(v) In increasing order of boiling point:
C2H5OH, (CH3) 2NH, C 2H 5NH 2
(vi) In increasing order of solubility in water:
C6H5NH2, (C2H5) 2NH, C 2H 5NH 2.
Q.2 Describe a method for the identification of primary, secondary and tertiary amines.Also write chemical
equations of the reactions involved.
Q.3 Explain Hofmann Bromanide reaction with Mechanism ?
Q.4 Why cannot aromatic primary amines be prepared by Gabriel phthalimidesynthesis?
Q.5 Write the reactions of (i) aromatic and (ii) aliphatic primary amines with nitrous acid.
Q.6 Write one chemical reaction each to illustrate the following
(i) Hofmann Bromanide reaction.
(ii) Garbriel Phthalimide reaction.
Q.7 Assign a reason for the following statements
(a)Alkylamines are stronger bases than arylamines.
(b) How would you convert methylamine into ethylamine ?
Q.8 Illustrate the following with an example of reaction in each case :
(i) Sandmeyer reaction (ii) Coupling reaction
Q.9 Write the chemical reaction equations for one example each of the following
(a)Acoupling reaction
(b) Hofmann's bromamide reaction
(c)Acetylation
Q.10 Account for the following :
(i)Aniline is weaker base than methylamine.
(ii)Aryl cyanides cannot be formed by the reaction of aryl halides and sodium cyanide.
Q.11 Describe tests to distinguish between : Secondary amine and tertiary amine.

18
Amine
Q.12 Account for the following observations :
(i) pKb for aniline is more than that for methylamine.
(ii) Methylamine solution in water reacts with ferric chloride solution to give a precipitate of ferric
hydroxide.
(iii)Aniline does not undergo Friedel Crafts reaction.

Q.13 State the reactions and reaction conditions for the following conversions
(i) Benzene diazonium chloride to nitrobenzene.
(ii)Aniline to benzene diazonium chloride.
(iii) Ethyl amide to methylamine.

Q.14 Write the physical property of aniline ?

Q.15 Write the method of formation of benzene diazonium chloride ?

Q.16 Account for the following:
(i) pKb of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv)Although amino group is o- and p- directing in aromatic electrophilic substitution reactions, aniline
on nitration gives a substantial amount of m-nitroaniline.
(v)Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.
Q.17 How willyou convert:
(i) Ethanoic acid into methanamine (ii) Hexanenitrile into 1-aminopentane
(iii) Methanol to ethanoic acid (iv) Ethanamine into methanamine
(v) Ethanoic acid into propanoic acid (vi) Methanamine into ethanamine
(vii) Nitromethane into dimethylamine (viii) Propanoic acid into ethanoic acid ?
Q.18 Write short notes on the following:
(i) Carbylamine reaction (ii) Diazotisation
(iii) Hofmann’s bromamide reaction (iv) Coupling reaction
(v)Ammonolysis (vi)Acetylation
(vii) Gabriel phthalimide synthesis.
Q.19 Accomplish the following conversions
(i) Nitrobenzene to benzoic acid (ii) Benzene to m-bromophenol
(iii) Benzoic acid to aniline (iv)Aniline to 2,4,6-tribromofluorobenzene
(v) Benzyl chloride to 2-phenylethanamine (vi) Chlorobenzene to p-chloroaniline
(vii)Aniline to p-bromoaniline (viii) Benzamide to toluene
(ix)Aniline to benzyl alcohol.
Q.20 Write the equation of curtius reaction with mechanism ?
Q.21 Complete the following reactions:
(i) C6H5NH2 CHCl3 alc.KOH  (ii) C6H5N2Cl H3PO2 H 2O 
(iii) C 6H5NH2 H2SO4 (conc.)  (iv) C6H5N2Cl C2H5OH 
(v) C6 H5NH2 + Br2(aq)  (vi) C6H5NH2 + (CH3CO) 2O 
( i)H B F4
(vii) C6H5N2 Cl (ii)NaNO
   
/ Cu.
2

19
Amine
Q.22 Give plausible explanation for each ofthe following:
(i) Whyare amines less acidic than alcohols of comparable molecular masses?
(ii) Whydo primaryamines have higher boiling point than tertiaryamines?
(iii) Whyare aliphatic amines stronger bases than aromatic amine?
Q.23 Write the reaction and conditions for the following conversions
(i)Aniline to benzene (ii) Methylamine to methyl cyanide
(iii) Propanenitrile to ethylamine (iv) m-Bromoaniline to m- bromophenol
(v) Nitrobenzene to 2, 4, 6-tribromoaniline.
Q.24 Write the method of formation of zwitter ion ?
Q.25 Explain nitration of aniline ?
Q.26 Why aniline do not give fridel craft reaction ?
Q.27 What is Gabriel phthalimide synthesis ? For what purpose is it used ? Give equation only to explainyour
answer.
Q.28 Write the equation of carbyl amine reaction with mechanism ?
Q.29 How will you convert 4-nitrotoluene to 2-bromobenzoic acid ?
Q.30 Draw the structure of trimethylamine and tell the shape of the molecule. Show the angle between two
methyl groups.

20
Amine

EXERCISE-II
Q.1 Aspartame, an artificial sweetener, is a peptide and has the following structures :
NH2 CH2C6H5
HOOC - CH2CH - CONH - CH - COOCH3
(a) Identify the four functional groups.
(b) Write the zwitterionic structure
(c) Write the structures of the amino acids obtained from the hydrolysis of aspartame.
(d) Which of the two amino acids is more hydrophobic ?

Q.2 Compound ofA(molecular formula C9H11NO) gives a positive Tollen’s test and is soluble in dilute HCl.
It gives no reaction with benzene sulphonyl chloride or with NaNO2 and HCl at 0ºC. (A), upon oxidation
with KMnO4 gives an acid (B). When (B) is heated with soda-lime, compound (C) is formed which
reacts with NaNO2 and HCl at 0 - 5ºC. What is (A) ?

Q.3 An organic compoundA, when treated with nitrous acid yields an alcohol B, C4H10O with the evolution
of N2. B on careful oxidation yields a substance C of vapour density 36 which forms oxime; B can react
with NaHSO3 but does not reduce Fehling solution. Identify compoundAand write the structural formulae
of the isomeric compounds that behave with HNO2 in the same manner.

Q.4 An organic compound (A), C6H4N2O4, is insoluble in both dilute acid and base and its dipole, moment
is zero. Deduce the structure of (A).

Q.5 Explain the following observations :

(1) Aniline dissolves in aqueous HCl.
(2) The amino group in ethylamine is basic whereas that in acetamide it is not basic.
(3) Dimethylamine is a stronger base than trimethylamine.
(4) Sulphanilic acid although has acidic as well as basic group, it is soluble in alkali but insoluble in
mineral acids.

Q.6 Explain, why ?

(1) Glycine exists as H3N+CH2COO- while anthranilic acid, p-NH2.C6H4.COOH does not exist
as dipolar ion.
(2) Benzenesulphonic acid is a stronger acid than benzoic acid.
(3) Aweakly basic solution favours coupling with phenol.
(4) It is difficult to prepare pure amines by ammonolysis of alkyl halides.

Q.7 Explain with reason ?

(1) Although trimethylamine and n-propylamine have same molecular weight, the former boils at a
lower temperature (3ºC) than the latter (49ºC).
(2) Dimethylamine is a stronger base than methylamine but trimethylamine is a weaker base
than both dimethylamine and methylamine.
(3) Although trimethylamine and n-propylamine have same molkecular weight, the former boils at
a lower temperature (3ºC) than the latter (49ºC). Explain.
(4) Silver chloride dissolves in aqueous solution of methylamine. Explain.

21
Amine
Q.8 Explain it ?
(1) An aqueous solution of ethylamine gives a red precipitate with ferric chloride. Explain.
(2) Tertiary amines do not undergo acetylation. Comment
(3) 2, 6-Dimethyl -N N-dimethylaniline, although has a free p-position, does not undergo coupling
with benezenediazonium chloride. Comment.
(4) In the following compounds :
O

N N N
H N = H
(I) (II) (III) (IV)

The order of basicity is I > III > II > IV. Explain.

Q.9 Explain it with reason ?

(1) tert-Butylamine cannot be prepared by the action of NH3 on tert-butyl bromide.
(2) Isocyanides are hydrolysed by dilute acids but not by alkalies to form amine and formic acid.
(3) How will you explain the acidic nature of 1º and 2º nitroalkanes ?
(4) Aniline does not undergo Friedal Craft’s reaction ?
(5) Although borontrifluoride adds on trimethylamine, it does not add on triphenylamine.
Comment.
Q.10 Complete the following reactions :
PCl5 NH3 P2O5 H2/Hi
(1) C6H5COOH [C] [D] C6H5CN [E]
P2O5 H+
(2) CONH2 F 
G
KOH
(3) EtNH2 + KCN + Br2 KBr + H

(4) — N(CH3)2 + HNO2 I

(i) NaNO2/HCl, 5ºC
(5) 2, 4-Dinitroaniline (ii) anisole
(J)
Oleum NaOH NaOH
(6) C6H6 (K) (L) heat (M)
SO3H OH

(7) 1
CHCl3/NaOH
N

(8) — SO3H fuming O

(i) NaOH fuse
P
H SO (ii) H+
2 4

Et2SO4 HCN, HCl PhNH.NH2

(9) Phenol NaOH (Q) AlCl3 (R) (S)
Br2, Fe
(10) CH3CONHC6H5 T+U
(A)
(11) C6H5N2Cl HCl
(V) Gattermann reaction

22
Amine
Q.11 Give structures for the compounds (A) to (I) :
NaNO2/HCl KCN
C8H11N B C
0-5ºC CuCN
(A)
Hot H2SO4

Heat to Hot
I m.p. G D
aq. KMnO4
CH3OH Cl2, 2 moles u.v.
at 30ºC
E
H
F
Q.12 When 2.25 g of an unknown amine was treated with nitrous acid, the evolved nitrogen, corrected to
S.T.P. measured 560 ml. The alcohol isolated from the reaction mixture gave a positive iodoform reaction. What is
the structural formula of the unknown amine ?
Q.13 The aqueous solution of a nitrogen and chlorine containing organic compound (A) is acidic towards litmus.
(A) on treatment with aqueous NaOH gives a compound (B), containing nitrogen, but not chlorine.
Compound (B) on treatment with C6 H 5SO 2Cl in the presence of NaOH gives an insoluble product
(C), C13H13 NO 2S. give the structures of compounds (A) and (B).

Q.14 An organic compound (A) composed of C, H and O gives characteristic colour with ceric ammonium
nitrate. Treatment of (A) with PCl5 gives (B), which reacts with KCN to form (C). the reduction of (C)
with warm Na/ C 2 H5OH produces (D), which on heating gives (E) with evolution of ammonia Pyridine
is obtained on treatment of (E) with nitrobenzene. Give structure of compounds (A) to (E) with proper
reasoning.

Q.15. One mole of bromoderivative (A) and mole of NH 3 react to give one mole of an organic compound (B).
(B) reacts with CH 3I to give (C). Both (B) and (C) react with HNO 2 to give compounds, (D) and (E)
respectively. (D) on oxidation and subsequent decarboxylation gives 2-methoxy-2-methyl propane.
Give structures of compounds (A) to (E) with proper reasoning.
Q.16 What happens with cyclopentanoen reacts with
(a) CH3CH2 NH2 (1° amine)
(b) (CH3CH 2 )2 NH (2° amine)

Q.17 Cyclohexylamineis a stronger base than aniline. Why?

Q.18 How does the formation of 2° and 3° amines can be avoided during the preparation of 1° amines by
alkylation?
Q.19 It is necessary to acetylate aniline first for preparing bromoaniline. Why?
Q.20 Dimethylamienis a stronger base than methylamine but trimethylamine is a weaker base than both
dimethyl amine and methylamine. Why?
Q.21 From analysis and molecular weight determination, the molecular formula of (A) is C3H 7 NO . the
compound gave following reactions.
(i) On hydrolysis it gives an amine (B) and a carboxylic acid (C)
(ii)Amine (B) reacts with benzene sulphonjyl chloride and gives a product which is insoluble in aqueous
sodium hydroxide solution.
(iii)Acid (C) on reaction with Tollen’s reagent gives a silver mirror when areA, B and C. Explain the
reactions.

23
Amine
Q.22 An optically active amine (A) is subjected to exhaustive methylation and Hofmann elimination to yield an
alkene (B). (B) on ozonolysis gives an equimolar mixture of formaldehyde and butanal. Deduce the
structures of (A) and (B). Is there any structural isomer to (A), if yes draw its structure.
Q.23 An aromatic compound (a) having molecular formula C7 H 7 NO 2 dissolves in NaHCO3 to evolve CO2 and
when reacted with NaNO 2 / HCl forms (b), C7 H 6O3 . (B) dissolves in NaHCO3 and gives colour reaction
with FeCl3 and can be prepared by the action of CCl 4 and NaOH on phenol. When (B) is reacted with
excess HNO3 , it forms (C), C6 H 3 N 3O 7 . (C) undergoes acetylation and decomposes NaHCO3 to evolve
CO 2 . On reaction with PCl5 . (C) is converted to (D), C6 H 5 N 3O6 Cl which when reacted with water gives
back (C). Identify compounds (A) to (D).
Q.24 Compound (A) having M.F. C8 H8O on treatment with NH 2OH.HCl gives (B) and (C). (B) and (C)
rearrange to give (D) and (E), respectively on treatment with acid. Compounds (B), (C), (D) and (E)are
all isomers of molecular formula C8 H 9 NO . When (D) is boiled with alcoholic KOH, an oil (F) C6 H 7 N
separated out. (F) reacts rapidly with CH 3COCl togive back (D). On the other hand, (E) on boiling
with alkali followed by acidification gives a white solid (G), C7 H 6O 2 . Identify the compounds (A) to
(G).

Q.25 An aromatic compound (A), having M.F C7 H5 NO 2Cl2 on reduction with Sn/HCl gives (B), which on
reaction with NaNO 2 / HCl gives (C). Compound (B) is unable to forma dye with  -naphthol. However,
(C) gives red colour with ceric ammonium nitrate and on oxidation gives an acid (D), having equivalent
weight 191. Decarboxylation of (D) gives (e) which forms a single mononitro derivative (F), on nitration. Give
the structures of (A) to (F) with proper reasoning.
Q.26 An organic compound (A) of molecular weight 135, on boiling with NaOH evolves a gas which gives white
denso fumes on bringing a rod dipped in Hcl near it. The alkaline solution thus obtained on acidification
gives the precipitate of a compound (B) having molecular weight 136. Treatment of(A)with
HNO 2 also yields (B), whereas it treatment with Br2 / KOH gives (C). Compound (C) reacts with
cold HNO 2 to gives (D), which give red colour with ceric ammonium nitrate. On the other hand, (E) an
isomer of (A) on boiling with dilute HCl gives an acid (F), having molecular weight 136. On oxidation
followed by heating, (F) gives an anhydride (G), which condenses with benzene in the presence of
anhydrous AlCl3 to give anthraquinone. Give the structures of (A) to (G) with proper reasoning.

Q.27 An organic compound (A) having M.F C7 H 9 N on treatment with NaNO 2 and HClat room temperature
forms another compound (B), C7 H 8O . When (A) or (B) is treated with bromine water, they form
dibromo derivatives, When (A) is reacted with chloroform and alkali, it forms (C) having the molecular
formula C8 H 7 N . Hydrolysis of (C) followed by reaction with NaNO2 and HCl at low temperature and
subsequent reaction with HCN in the presence of Cu(D), which is isomeric to (C). (D) on hydrolysis
followed by oxidation gives a dibasic acid, which on halogenation forms only one monohalo derivative.
Identify the compounds (A) to (E).

24
Amine
Q.28 An optically active compound (A), C3H7O2 N forms a hydrochloride but dissolves in water to give a
neutral solution. On heating with soda lime (A) yields (B) C 2 H 7 N . Both (A) react with NaNO2 and
HCl, the former yielding a compound (C) C3H 6O , which on heating is converted to (D), C6 H 8O 4 while
the latter yields (E), C2 H 6O .Account for the above reactions and suggest how (A) may be synthesized.

Q.29 An optically inactive acid (A), C5H 8O5 , on being heated lost CO 2 to give an acid (B), C 4 H 8O 3
capable of being resolved. On action of sulphuric acid, B gave an acid C whose ethyl ester gave (D) on
the action of hydrogen and platinum. (D) with conc. NH 3 gave E, C 4 H9OH which with Br2 and KOH
solution gave (F), C3H9 N . F with HNO 2 gave G. (G) on mild oxidation gave H. BothAand H gave the
iodoform reaction. Elucideate the reaction mechanism and suggest a synthesis of (C).

Q.30 Aneutral compound (A) C8 H 9OH on treatment with NaOBr forms an acid soluble substance C7 H 9 N.
On addition of aqueous NaNO2 to a solution of B in dilute HCl at 0-5°C an ionic compound (C)
C7 H7 N 2Cl is obtained. (C) gives a red dye with alkaline  -napththol solution. When treated with
potassium cuprocyanide (C) yields a neutral substance (D) C8 H7 N . ON hydrolysis (D) gives E
(C8 H8O 2 ) . E liberates CO 2 from aqueous NaHCO3 . (E) on permanganate oxidation furnishes (E)
C8 H 6O 4 . (F) onnitration yields two isomeric mononitro derivatives (G and H) having molecular formula
C8 H5 NO 6 . Write the reactions involved in different steps.

25
Amine

EXERCISE-II
Q.1 When aniline is treated with fuming sulphuric acid at 475K, it gives
(a) Sulphanilic acid
(b)Aniline sulphate
(c) o-aminobenzenesulphonic acid
(d) m-aminobenzenesulphonic acid.
Q.2 When nitrobenzene is treated with Br2 in presence of FeBr3, the major product formed is m-
bromonitrobenzene. Statements which are related to obtain m-isomer are:
(a) The electron-density on meta carbon is more than that on ortho and para positions
(b) The intermediate carbonium ion formed after initial attack of Br+ at the meta position is least
destablilzed
(c) Loss of aromaticity, when Br+ attacks at the ortho and para positions, and not at meta position
(d) Easier loss of H+ to regain aromaticity from the meta position than from the ortho and para positions.
Q.3 Examine the following two structures for the anilinium ion and choose the correct statement from the ones
given below.

(a) II is not an acceptable canonical structure, because carbonium ions are less stable than ammonium
ions
(b) II is not an acceptable canonical structure, because it is non aromatic
(c) II is not an acceptable canonical structure, because the nitrogen has 10 valence electrons
(d) II is an acceptable canonical structure.
Q.4 The correct order of basic strength of in CCl4
(1) NH3 (2) RNH2 (3) R2NH (4) R3N
Where R is CH3 group is
(a) 3 > 2 > 1 > 4 (b) 2 > 3 > 4 > 1 (c) 3 > 2 > 4 > 1 (d) None of these
Q.5 Place the following in the decreasing order of basicity.
(1) Ethylamine (2) 2-aminoethanol (3) 3-aminopropan-1-ol
(a) 1 > 3 > 2 (b) 1 > 2 > 3 (c) 2 > 1 > 3 (d) None of these
Q.6 Which of the following will give a positive carbylamine test ?
1. H3CNH2 2. H3C-NH-CH3 3. (CH3)3N 4. C6H5NH2
Select the correct answer using the codes given below.
(a) 1 and 3 (b) 2 and 4 (c) 3 and 4 (d) 1 and 4.
Q.7 Match the compounds in list I with the appropriate test that will be answered by each one of them inlist
II from the combinations shown.
Selects the correct answer using the codes given below the list .
List I List II
(A) Propyne 1. Reduces Fehling’s solution
(B) Ethyl benzoate 2. Forms a precipitate withAgNO3 in ethanol
(C) Acetaldehyde 3. Insoluble in water, but dissolves in aqueous NaOH upon heating
(D) Aniline 4. Dissolves in dilute HCl in the cold and is reprecipitated by the
addition of alkali
(a) A-3, B-2, C-1, D-4 (b) A-2, B-3, C-1, D-4
(c) A-2, B-3, C-4, D-1 (d) A-1, B-3, C-2, D-4

26
Amine

Q.8 In the following 2- reaction sequence R-CH = CH2 + H2SO4 R-CH-CH3 the end product would be
|
SO4H
NaOH

(Where R = C14 H29) R-CH-CH3

|
SO4– Na+

useful as
(a)Afertilizer (b)An explosive (c)Adetergent (d) None of these
Q.9 The basic strength of amines (ethyl) and ammonia in H2O is
(a) NH3 > p > s > t (b) p > s > t > NH3 (c) s > p > t > NH3 (d) None of these
Q.10 Which of the following will have highest Kb
value.
NH2 NH2

(a) (b) (c) (d)

N
N Me Cl
H
Q.11 Activation of benzene ring by — NH2 in aniline can be reduced by treating with
(a) Dilute HCl (b) Ethyl alcohol (c)Acetic acid (d)Acetyl chloride
Q.12 Dipolar ion structure for amino acid is
(a) H2N CH COOH (b) H3N CH COO

R R
(c) H3N CH COO (d) None of these.

Q.13 - NH2 group shows acidic nature while reacts with reagent.
(a) Na (b) CS2 (c) Br2  NaOH (d) Water
Q.14 Which of the following does nto give ethylamine on reduction
(a) methyl cyanide (b) Ethyl nitrile (c) Nitro ethane (d)Acetamide
Q.15 In the reaction,
excess CH Cl 
CH3 NH2 
3
 (X) (Y) (Z) the final product (Z) is
(a) (CH3 )3 N (b) (CH3 )4 N Cl - (c) (CH3 )4 N OH - (d) (CH3 )2 NH

Q.16 The product not obtained in the following reaction, CH3 — NO2  Cl 2  NaOH  
is
(a) ClCH 2 NO2 (b) Cl 2CHNO2 (c) Cl3CNO2 (d) CH3 NH 2
Q.17 Asequential reaction may be performed as represented below:
SO 2 Cl 2 NH3
R — CH 2 CO 2 H  (1)
 R — CH 2 COCl 
( 2)

 R — CH 2 CONH 2 



(3)
 R — CH2 NH 
( 4)
R — CH2 OH 
(5)
 R — CO2 H
The appropriate reagent for step (3) is
(a) NaBr (b) Bromine and alkali (c) HBr (d) P2 C5

27
Amine
Q.18 Which of the following amine form N-nitroso derivative when treated with NaNO2 and HCl?

(a) H3C NH2 (b) NH2

(c) N(CH3)2 (d) NH(CH3)

Q.19 The strongest base among the following is

H2N H2N H2N H2N
(a) C NH (b) C NH2 (c) C O (d) CH OH
H2N H2N H2N H2N

Q.20 Identify compound (A) in the following oxidation reaction.

K Cr O , H S O
(A)   2 2
7 
2 4
O O

NH2 OH OH

(a) (b) (c) (d)All of these.

NH2 NH2 OH

Q.21 Aniline is a weaker base than ethyl amine because

(a) Phenyl gp in aniline is a +R gp
(b) Ethyl gp in ethyl amine decreases the electron density on nitrogen atom
(c) The lone pair of electron on nitrogen atom in aniline is delocalized over aniline
(d)Aniline is less soluble in water than ethylamine
Q.22 Diazonium coupling reaction with aniline should be carried out in
(a) Weakly basic medium (b) Weakly acidic medium
(c) Strongly basic medium (d) Strongly acidic medium
Q.23 For CH3CHO, CH3NO2, CH3COOH
(a)All have same chemical property (b)All have one common chemical behaviour
(c) All are basic (d) None of these
Q.24 Bromine in CS2 reacts with aniline to give
NH2 NH2 NH2
Br Br Br
(a) (b) (c) (d) Both (a) and (b)

Br Br

Q.25 RNC cannot undergo

(a)Acidic hydrolysis (b) Electrophillic, nucleophillic, addition on carbon
(c) Base hydrolysis (d) Both (b) & (c)

28
Amine
NH2
Q.26 + phosgene X. Here X is

O N=C=O Cl
NH - C - Cl CH - C - H
(a) (b) (c) (d) None of these
Cl

Q.27 Ethylamine undergoes oxidation in the presence of KMnO4 to give

(a) CH3COOH (b) CH3CH2OH (c) CH3CHO (d) N-oxide
Q.28 Baker Mulliken’s test is used to detect the presence
(a) -COOH gp (b) -NO2 (c) -OH (d) -NH2
Q.29 t-amines with different alkyl gp has a chiral nitrogen atom still it is optically inactive because
(a) Chiral N-atoms cannot rotates plane polarized light
(b) The lone pair prevents the rotation of plane polarized light
(c) Both of these
(d) None of these
Q.30 In CH3NO2 we can observe
(a) H-bonding (b) -halogenation reaction
(c) Tautomerism (d)All of these
Q.31 The reaction:
O
O || ||
C
NH
KOH C :N:K + n-BuBr
C C
|| ||
O O
O
||
C 1. aq.NaOH
N Bu-n 2. H O+ n-BuNH2 + is called
C 3
||
O
(a) Carbylamine reaction (b) Hofmann reaction
(c) Gabriel phthalimide synthesis (d) Cope reaction .
Q.32 The conjugate acid of HO(CH2)3 NH2 is
+ + - +
(a) H2O(CH3)3NH2 (b) HO(CH2)3NH3 (c) O(CH2)3NH2 (d) HO(CH2)3NH
Q.33 Consider the following compounds :
1. H2C = CHCH2NH2 2. CH3CH2CH2NH2 3. HC  CCH2NH2
The increasing order of basicity is
(a) 3 < 1 < 2 (b) 3 < 2 < 1 (c) 2 < 1 < 3 (d) None of these

NH2
Q.34 During the conversion of with HNO2 at high temperatures the following substances or

entermediates are formed.

 -
N2 Cl OH
1. N2O3 2. 3. 4. C6H5NH - N = O

(a) 1 only (b) 1, 2, 4 only (c) 2, 4 only (d)All of these

29
Amine
Q.35 Match list I (condition of reaction of nitrobenzene) with list II (products formed ) and select thecorrect
answer using the codes given below.
List I List II
(A) Sn and HCl 1. Hydrazobezene
(B) Zn and NH4Cl 2. Azoxybenzene
(C) Methanolic NaOMe 3. Phenyl hydroxylamine
(D) Zn and KOH 4. Aniline
(a) A-2, B-1, C-3, D-4 (b) A-4, B-3, C-2, D-1
(c) A-1, B-4, C-2, D-3 (d) A-1, B-3, C-2, D-4

Q.36 The increasing order of basicity of RCN, RCN = NR and RHN2

is
(a) RCN < RCH = NR < RH 2 N (b) RNH 2 < RCN < RCH = NR
(c) RCH = NR < RNH 2 < RCN (d) RH 2 N < RCH = NR < RCN.

(i ) N H
Q.37 CH3 — CO — COOH ( 3 (A). What is (A) ?
ii ) H /

Pd 2
(b) CH3 — CO — CONH2
(a) CH 3CONH 2 (d) CH 3CH(NH 2 )COOH .
(c) CH 3CH 2CONH 2
Q.38 How many isomeric amines with that formula C7 H9 N contain a benzene ring?
(a) two (b) three (c) four (d) five.
Q.39 Isopropylamine can be obtained by
LiAlH4 H 2 / Ni
(a) (CH3 )2 CHO  NH 2OH  ?  (b) (CH3 )2 CHO  NH3  ?  
H3C
CHOH  NH3 

(c) (d)All of these.
H3C

Q.40 Reaction of RCONH 2 with a mixture of Br2 and KOH gives RNH2 as the main product. The interme-
diate involved in the reaction is
O O
Br
(a) R C NHBr (b) R—NHBr (c) R C N (d) R—C = N = O.
Br
Q.41 Amines are highly soluble in:
(a)Alcohol (b) Diethyl ether (c) benzene (d) Water.
Q.42 Which of the following reagents can convert benzene diazonium chloride into benzene?
(a) Water (b)Acid
(c) Hypophosphorous acid (d) HCl.
Q.43 The bromination of aniline produces
(a) 2-bromoaniline (b) 4-bromoaniline (c) 2,4,6-tribromoaniline (d) 2, 6-dibromoaniline.
Q.44 The compound, which on reaction with aqueous nitrous acid at low temperature produces an oily ni-
trosoamine is
(a) Methyl amine (b) Ethylamine (c) Diethylamine (d) Triethylamine

30
Amine
Q.45 Carbylamine test is performed in alcoholic KOH by heating a mixture of
(a) Chloroform and silver powder
(b) Trihalogenated methane and a primary amine
(c)An alkyl halie and a primary amine
(d)An alkyl cyanide and a primary amine.
Comprehension :
Arenediazonium salts are more stable than alkanediazonium salts due to dispersal of the positive charge
on the benzene ring. Obviously electron donating groups favour diazotisation by retarding the
decomposition of diazonium salts to phenyl cation. The high reactively of arenediazonium salts isdue to
the excellent leaving ability of the diazo group as N2 gas. Therefore, diazonium salts undergo a number
of substitution reactions in which the diazo group is replaced by a monovalent atom/group such as H(by
H3 PO2 in presence of Cu+ ions, CH3 CH2OH, NaBH4 etc.), OH (by boiling in presence of mineral
acids), OCH3 (by heating with CH3OH) Cl (by CuCl/HCl or Cu/HCl), Br (by CuBr/HBr or Cu/HBr)
I (by KI in presence of Cu+ ions), F (by first converting into N 2F 4 followed by heating), CN (by first
neutralizing with Na2 CO3 and then reacting with KCN/CuCN), NO2 (by first neutralizing with Na2CO3
and then treating with NaNO2) phenyl or substituted phenyl (by treating with benzene or substituted
benzene in presence of NaOH) etc.
Diazonium salts also couple with phenols and aromatic amines to form coloured azo dyes. The reactivity
of diazonium salts towards coupling reactions is favoured by presence of electron withdrawing groups;
the reactivity of 2, 4, 6-trinitrobenzenediazonium chloride is so high that it even couples with reactive
hydrocarbons such as mesitylene.
Q.46 Consider the following ions:

I. Me2N N+  N II. O2N N+  N

III. CH3O N+  N IV. CH3 N+  N

The reactivity of these ions towards azo coupling reactions under similar conditions is
(a) I < IV < II < III (b) I < III < IV < II (c) III < I < II < IV (d) III < I < IV < II
Q.47 Which of the following diazonium salts when boiled with dil. H2 SO4 gives the corresponding phenol most
readily?
OMe

+
(a) N N (b) MeO N+  N

(c) Me N+  N (d) N+  N

31
Amine
Q.48 Which of the following arylamines undergoes diazotisation most readily?

(a) NO2 NH2 (b) Cl NH2

(c) CH3O NH2 (d) CH3 NH2

Q.49 The product formed when bromobenzene reacts with benzenediazonium chloride in presence of NaOH
is
(a) Diphenyl (b) p-Bromodiphenyl
(c) p, p´-Dibromodiphenyl (d) p-Bromoazobenzene
Q.50 Benzendiazonium chloride on reaction with phenol in weakly basic medium gives:
(a) Diphenyl ether (b) p-Hydroxyazobenzene
(c) Chlorobenzene (d) Benzene
Assertion and Reason :
Each of the questions given below consists of two statements, an assertion (A) and reason (R).
Select the number corresponding to the appropriate alternative as follows
(a) If both A and R are true and R is the correct explanation of A, then mark (a)
(b) If both Aand R are true but R is not the correct explanation of A, then mark (b)
(c) If Ais true but R is false, then mark (c)
(d) If both Aand R are false, then mark (d)
Q.51 A. Benzyl amine is more basic than aniline.
R. Positive inductive effect of phenyl group creates high electron density around N atom.
Q.52 A. White precipitate of silver chloride get dissolved in NH4OH soln.
R. NH3 reacts withAgCl to form a solution complex with formula [Ag(NH3)2]Cl.
Q.53 A: o-nitrophenol is more acidic than p-nitrophenol.
R: Nitro group has +M and -I effect.
Q.54 A: 3° amine is proved to be less basic in aq. solution.
R: Conjugate acid of 3° amine is poorly solvated in aq. solution.
Q.55 A: In order to convert R-Cl to pure R-NH , Gabriel-phthalimide
2
synthesis can be used.
R: With proper choice of alkyl halides, phthalmide synthesis can be used to prepare 1°, 2° and 3°
amines.
Q.56 A: 4-Nitrochlorobenzene undergoes nucleophilic substitution more readily than chlorobenzene.
R: Chlorobenzene undergoes nucleophilic substitution by elimination-addition mechanism while
4-nitrochlorobenzene undergoes nucleophilic substitution byaddition-elimination mechanism.
Q.57 A: 1° amides react with Br2 + NaOH to give 1° amines with one carbon atom less than the parent
amide.
R: The reaction occurs through intermediate formation of acylnitrene.
Q.58 A: Acetamide reacts with Br 2 in presence of methanoic CH 3ONa to form methyl
N-methylcarbonate.
R: Methyl isocyanate is formed as an intermediate which reacts with methanol to form methyl N-
methylcarbamate.

32
Amine

ANSWER KEY
EXERCISE - II
Q.1 The hydrolysed products are aspartic acid and phenylalanine.
CHO COOH
N(CH3)2

Q.2 A= B= C=
N(CH3)2 N(CH3)2

Q.3 CH3  C H  C 2 H3 , The other isomers should be p-amines only

|
NH 2

NO2

Q.4

Q.10 (1) C = C6H5COCl D = C6H5CONH2 E = C6H5CHNH2

(2) F = C6H5CN G = C6H5COOH
N(CH3)2

(3) H = EtNHBr (4) I=

NO

NO2
(5) J = O2 N -N = N - Me

(6) K = C6H5SO3H L = C6H5SO3Na M = C6H5OH

OH
CHO
(7) I = NaOH N=

SO3H OH

(8) O= P=
SO3 H OH

OEt

(9) Q = Ph - O - Et R= S = EtO CH = N- NH- Ph

CHO

(10) T = CH3 - C - NH + para isomer

O Br

Cl
(11) A = Cu Powder V= + N2

33
Amine


NH2 NH2 Cl CN COOH
Q.11 A B C D
Et Et Et E

COOH COOH COOH COOH

(E) C - CH 3
(F) (G) (H)
C - CH 3 COOH C - OMe
Cl Cl O O

O
C
(I) O
C
O

Q.12 C2H5NH2

CH3 — N H 2 Cl - CH3-NH
Q.13

(A) (B)
CH2 OH CH2Cl CH2 CN CH2 CH2NH2 CH2 CH2
Q.14 H2 C H2 C H2 C H2 C H2 C NH
CH2 OH CH2Cl CH2 CN CH2 CH2NH2 CH2 CH2
(A) (B) (C) (D) (E)

OCH3 OCH3 OCH3

Cl C CH2CH2Br H3 C C CH2CH2NH2H3C C CH2CH2NH-CH3

CH3 CH3 CH3

(A) (B) (C)

OCH3 OCH3 CH3

Q.15 H3C C CH2CH2OH H3C C CH2 CH2 N CH3

CH3 CH3
(D) (E)

CH2CH3 CH2CH3
Q.16 a O  CH3 CH2 NH 2 
 N Tauto
mer ise N

H

CH2CH3 CH2CH3
+
b O  (CH3 CH 2 )2 NH 
 N -
 H
N
CH2CH3 CH2CH3
H H

24
Amine
Q.17 Aniline is a weak base than cyclohexylamine because of resonance.
Q.18 Use of excess ammonia reduces chances of reaction of 1° amine with alkyl halide to form 2° and 3°
amines.
Q.19 Amino group, being activating group, activates bromination of aniline and forms tribromoaniline.
Q.20 Dimethyl amine is stronger base because of inductive effect. Trimethyl amine is a weaker base because
positive charge on nitrogen could be stabilized and due to crowding by alkyl groups around the
nitrogen atom protonation cannot take place.
CH3
(A) NOCH (N, N  dim ethyl formamide)
CH3
Q.21
CH3

(B) HN
CH3

C HCOOH
NH2

(A) H3C CH3

Q.22
(B) H2C
CH3

OH Cl
COOH COOH
OH O2N NO2 O2 N NO2
NH2
Q.23
(A) (B)
Anthranilic acid salicylic acid NO2 NO2
(C) (D)
picric acid Picryl chloride

C 6 H5 HC OH H3C
C O C N C N
H3C C6H 5 C6H 5 OH
(A) (B) (C)
Q.24 Acetophenone E-Acetophenone oxime Z-Acetophenone oxime
O O

C6H5 NH C CH3 C 6 H5 C NH CH3 C6H5 NH2 C6H5 COOH

(D) (E) (F) (G)
Acetanilide N-methyl benzamide Aniline Benzoic acid

35
Amine

Cl Cl Cl Cl Cl Cl
CH2NO2 CH2NH2 CH2OH COOH NO2
Q.25

Cl Cl Cl Cl Cl Cl
(A) (B) (C) (D) (E) (F)

CH2CONH2 CH2COOH CH2NH2 CH2OH O

CONH2 COOH C
Q.26 O
(A) (B) (C) CH3 CH3 C
(D) (E) (F) (G)
O

NH2 OH NC CN COOH

Q.27

CH3 CH3 CH3 CH3 COOH

(A) (B) (C) (D) (E)

Q.28 Degree of unsaturation ofA= 2.

Since Aforms hydrochloride and dissolves in water to give a neutral solution, it contains both a basic and
an acidic functional group. It is likely to be amino acid as the molecular formula contains one N and 2
O- atoms. On decarboxylation it forms an amine B. Degree of unsaturation of B = 0.
Therefore, B is a saturated amine. B reacts with NaNO2 and dilute HCl forming (E) C 2 H5OH . Thus, B
is CH 3CH 2 — NH 2 . Aalso reacts with NaNO 2 and dilute HCl forming C, a hydroxyl acid, which
forms a cyclic diester on heating.All the reactions can be given as

H3C CH COOHNaOH
CaO
 CH3 CH2 - NH2 N
aNO 2  HC l
   CH3 CH2 -OH
(B) ( E)

NH2
(A)

NaNO2  HCl

H3C CH COOH

OH
(C) O CO
 
H3 C2 CH COOH  CH 3HC
-2 H2 O CHCH
3

OH O O

P / Br NH3
2
CH3CH2 — COOH  H3C2 CH COOH  H3C2 CH COOH

Br NH2

36
Amine

CH2OH CH2OH CH2

Q.29 A = H3C C CO2H B = H3C C CO2H C = H3C C CO2H

CO2H H

D  (CH 3 )2 CHCO2 C2 H 5 E  (CH3 )2 CHCONH 2 F  (CH3 )2 CHNH 2 G  (CH3 )2 CHOH

H  CH 3COCH 3

CONH2 NH2 N2 Cl
A= B= C=
CH3 CH3 CH3

CN CO2H COOH
Q.30 D= E= F=
CH3 CH3 COOH

CO2H CO2H
G, H are
CO2H O2 N CO2H

NO2

EXERCISE - III
Q.1 a Q.2 (a, b) Q.3 c Q.4 d Q.5 b Q.6 d Q.7 b
Q.8 c Q.9 d Q.10 a Q.11 d Q.12 c Q.13 c Q.14 b
Q.15 c Q.16 d Q.17 b Q.18 d Q.19 a Q.20 d Q.21 c
Q.22 b Q.23 b Q.24 c Q.25 c Q.26 b Q.27 d Q.28 b
Q.29 d Q.30 d Q.31 c Q.32 b Q.33 a Q.34 d Q.35 b
Q.36 a Q.37 c Q.38 b Q.39 a Q.40 a Q.41 d Q.42 c
Q.43 c Q.44 c Q.45 b Q.46 b Q.47 a Q.48 c Q.49 b
Q.50 b Q.51 c Q.52 a Q.53 d Q.54 a Q.55 c Q.56 b
Q.57 a Q.58 a

37