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Amines are the derivatives of ammonia obtained by replacement of H atoms by any alkyl or aryl
groups. Replacement of one, two and three hydrogen atoms of ammonia produces primary,
secondary and tertiary amines respectively.

Methods of Preparation of Amines

1. By Alkylation of NH3

R — X + NH 3  
SN 2
→ R — NH 2 (Primary amine)

But usually we get a mixture of different amines due to further alkylation

R — X + RNH 2 
→ R 2 NH (Secondary amine)

R — X + R 2 NH 
→ R 3 N (Tertiary amine)

→ R 4 N + X – (quaternary ammonium salt)

R — X + R 3 N 

Further alkylation can be stopped and a pure primary amine can be obtained by alkylation
of Phthalimide (Gabriel Synthesis) followed by hydrolysis as below:
O O O

N K  → +2KOH
N:H 
KOH
– H2 O
→
R —X
– KX N —R →
– H2O
(SN 2)

O O O N-alkyl phthalimide
Phtha lim ide Salt
COO K
+ R − NH 2
COO K
Potassium phthalate

2. By Reduction of Nitro Compounds

NO2 NH3 NH2

→
Sn / HCl
 
base
→

If two nitro groups are present at meta positions to each other, one of them can be reduced
by selective reduction. For this purpose we use NH 4SH or (NH 4 )2 S or H 2S in NH 3

NO2 NH2


NH 4SH
→
NO2 NO2

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3. By Reduction of Nitriles and Isocyanides

R — C ≡ N LiAlH 4
→ RCH 2 — NH 2
(Primary amine)

R — N ≡ C  LiAlH 4
Ether
→ R — NH — CH 3
Methyl substituted amine

4. By Reduction of Oximes

C = NOH 
Na,ethanol
→ CH — NH 2

5. By Reductive amination of Carbonyl Compounds

R — CHO 
NH3
H 2 / Ni
→ R — CH 2 — NH 2

CH3CH 2 CHO 

CH3CH 2 NH 2
H 2 / Ni
→ CH3 — CH 2 — CH 2 — NH — CH 2 CH 3

H
C=O 
NH3
H 2 / Ni
→ C
NH 2

6. From Amides

Reduction of amides produces corresponding amines with same number of carbon atoms.

R C NH2 
LiAlH 4
→ RCH 2 NH 2
O

R C NH R 
LiAlH 4
Ether
→ R — CH 2 — NH — R
O

R C NR2 
LiAlH 4
Ether
→ R — CH 2 — NR 2

Hoffmann Bromide Reaction

Amines (only primary) can also be prepared by Hoffmann degradation. In this method the amine
will have one carbon atom less than the amide. The reaction proceeds via formation of nitrene.
O

R C NH2 + Br2 + 4KOH → RNH 2 + K 2 CO3 +2KBr + 2H 2 O

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Mechanism of above reaction has been proposed as given below:

→ K + O – Br + HBr
Br2 + KOH 

Mechanism

2NaOH + Br2 
→ NaOBr + NaBr + H 2 O

O O

R C NH2 + OBr 
–
→ R C N Br + OH –

H
N-bromoacetone

O O

R C N Br + OH –
– H2O
→R C N – Br + H 2 O

H Rearrangement

R — NH 2 + CO 2 ←
H2O
 R — N = C = O (Isocyanate)

Curtius, Schmidt and Lossen Rearrangement

These reaction are basically rearrangement reaction in which carbon migrates from carbon to
nitrogen with the formation of an isocyanate. In these migration i.e., 1, 2 shift, migrating group is
an alkyl or aryl group and leaving group may be

—Br in Hoffmann rearrangement

— N2 in curtius and Schmidt rearrangement

R C O
Lossen rearrangement
The isocyanate on hydrolysis gives amine.

Preparation of Amine
Curtius Reaction: Acid chloride on treatment with sodium azide give acid azides which on
pyrolysis gives isocyanates which on hydrolysis gives corresponding amines.
∆
RCON 3 
−N
→ R − N = C = O 
H2 O
− CO
→ R − NH 2
Acyl azide
2 Alkyl isocyanate 2
Alkyl amide

Mechanism

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RCOCl + NaN 3 
→ RCON 3 + NaCl

O O O

R C N N N ←
→ R C N N N ←
→R C N N2

R N N2 
→ R—N=C=O
C
alkyl isocyanate
O
H 2O

R N C OH ←
H 2O
 R N C O

OH OH
O

R NH C OH 
– CO2
→ R — NH 2 + CO 2

2. Schmidt Reaction: Carboxylic acid reacts with hydrozoic acid in presence of

concentrated H 2SO 4 to give isocyanates.
R – COOH + N3H →
H 2SO 4
R – NH2 + CO2 + H2O
Mechanism
O OH OH

R C + H + 
→ R C 
HN3
→R C OH
+
OH OH H N N N
–H 2 O

O
R C O H
– H+
R — N = C = O ←
R − N2
C ←
 +
isocyanate N N N
+
–H 2 O N N N

R — NH 2 + CO 2

3. Lossen Reaction: Hydroxylamine on treatment with acid chloride gives acyl

derivatives of hydroxyl amine. the acyl derivatives exist in two tautomeric form. keto
form called hydroxamic form and enol form called hydroximic acid. The hydroxamic
form.

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O
R −

OH
→ R − NH 2 + CO 2
NH
HO
Mechanism
O O

R + H2N OH R + HCl
Cl NH
HO
OH
O
R
R
N
NH
HO
HO
Hydroxamic acid (enol form)
(keto form)

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

R − NH 2 ←
H 2O
 R — N = C = O ←
R C N O C R
− CO 2

Basic Character of Amines

The +I effect of the alkyl group, which increases the electron density on N-atom, facilitates the
nitrogen atom to use its unshared pair of electrons for bond formation. Thus R— NH 2 is expected
to be more basic than NH3 . Going by the same arguments the basic strength of amines is
expected to increase with the increase in the number of alkyl groups attached to the nitrogen
atom.

R 3 N > R 2 NH > RNH 2 > NH3

This is indeed found to be the case when basic strength of amines is measured in non-aqueous
medium like chlorobenzene. However, this trend is not observed in aqueous medium. The
nitrogen atom in an amine shares its electron pair with H + ion from water to form alkyl
ammonium ion

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⊕
R — NH 2 + H 2O R — N H3 + OH –

The basic strength of the amine is expressed as equilibrium constant K b

[RNH 3+ ][OH – ]
Kb =
[RNH 2 ]
The greater the value of K b of an amine, the greater is its basicity.

The basic strength of an amine in aqueous medium is determined not only on the basis of +I
effect of the alkyl groups attached to the nitrogen atom but also the solvation of alkyl ammonium
ion formed by uptake of proton.

H OH2 H OH2 H OH2

R N H OH2 > R N R > R N R

H OH2 H OH2 R
The solvation of alkyl ammonium ion follows the above order. Both the +I effect and solvation
of amine make basic order of aniline in aqueous medium as 2° > 1° > 3° > NH3 .

Illustration 1: Arrange ethylamine, 2-amino ethanol and 3-amino-1-propanol in the order

of decreasing basicity and give your reason.

Solution: CH3CH 2 NH 2 > HO(CH 2 )3 NH 2 > HO(CH 2 ) 2 NH 2 . The electron withdrawing

inductive effect of the OH group decreases the electron density on nitrogen,
thus lowering the amine’s basicity. This effect diminishes with distance from
the amino group.

Aromatic Amines: In aromatic amines the nitrogen atom of — NH 2 group is directly

attached to the benzene ring. The unshared pair of electrons at the nitrogen atom is in resonance
with the benzene ring and hence not fully available for donation as in the case of aniline.

NH2 NH2 NH2 NH2 NH2

←
→ ←
→ ←
→ ←
→

If aniline is to function as a base, it has to use its unshared pair of electrons for donation at the
cost of resonance stabilization. Thus aniline is reluctant to function as a base. This is supported
by the pK b values of aniline in comparison to those of ammonia and cyclohexylamine.
NH3 C6 H5 — NH 2 C6 H11 — NH 2
pK b 4.75 9.38 3.32

General Chemical Properties of the Amines

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Reaction with Nitrous Acid

Primary Amines: Primary amines react with nitrous acid to produce diazonium ion as
follows.
→ Ar — N ⊕ ≡ N :
ArNH 2 + HNO2 
→ R — N⊕ ≡ N
R — NH 2 + HNO 2 

But the diazonium ions of aliphatic amines are very unstable and produces carbocation
immediately, which can produce different products.

R — N ⊕ ≡ N 
– N2
→ R + (Carbocation)
−
N
+
N 2 + Cl- + H3C CH2 
~ H (Hydride shift)
→ H3C CH3
H3C N Cl
H2O −H+ −H+ H O Cl−
Cl − 2

OH Cl
CH3 CH3
H3C H3C H3C CH2
propan-1-ol 1-chloropropane H3C
prop-1-ene H3C

OH Cl
2-chloropropane
propan-2-ol

This reaction of RNH 2 has no synthetic utility, but the appearance of N 2 gas signals the
presence of NH 2 .

Diazonium salts of aromatic amines are comparatively more stable and evolve nitrogen only on
heating. These diazonium salts can be isolated at low temperatures.

The diazonium salts are very important synthetic reagents, being the starting point in the
preparation of various aromatic compounds. Their reactions may be divided into two groups;
those which involve the liberation of N 2 by another univalent group and those in which the two
N-atoms are retained (coupling reactions).


H3 PO 2
→ Ar — H

KI
→ Ar — I

→
CuCl(CuBr )
ArCl /(ArBr) (Sandmeyer reaction)
Ar – N ⊕ ≡ N HBF4 or NaBF2 , ∆
 → Ar — F
+

H2O / H
→ Ar — OH


CuCN
→ Ar — CN (Sandmeyer reaction)


ROH
→ Ar — OR

Coupling reaction with primary amines

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1. Diazoniuim ions of aromatic amines also undergo coupling reaction with aromatic rings
having a strong activating group to form diazo compounds.

Ar — N ⊕ ≡ N + NH2 
→ Ar N N NH2

Ar — N ⊕ ≡ N + OH 
→ Ar N N OH

Couplings between arenediazonium cations and phenols take place most rapidly in
slightly alkaline solution. Under these conditions an appreciable amount of the phenol is
present as a phenoxide ion, ArO–, and phenoxide ions are even more reactive toward
electrophilic substitution than are phenols themselves (pH > 10). If the solution is too
alkaline, diazonium salt itself reacts with OH – ion to form a relatively unreactive
diazoate ion.
OH O

−

OH
← →

HA

phenol Phenoxide ion

(couples slowly) (couples rapidly)

+ − −
Ar N 
OH
← →
 Ar N 
OH
← →
 Ar N
HA HA

N N OH N O
Arenediazonium Diazohydroxide Diazotate ion
ion (couples) (does not couple) (does not couple)

Couplings between arenediazonium cations and amines take place most rapidly in slightly
acidic solutions (pH 5 – 7). Under these conditions the concentration of the
arenediazonium cation is at a maximum; at the same time an excessive amount of the
amine has not been converted to an unreactive aminium salt.
R
R R +
N R N H


HA
← →
– OH

Amine Aminium salt

(couples ) (does not couple)

If the pH of the solution is lower than 5, the rate of amine coupling is slow. With phenols
and aniline derivatives, coupling takes place almost exclusively at the para position if it is
open. If it is not, coupling takes place at the ortho position.

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OH
N OH
N
 →
+ -
+
NaOH
N2 Cl H2O

CH3
CH3
p-cresol
4-methyl-2-[(E)-phenyldiazenyl]phenol

Azo compounds can be reduced to amines by a variety of reagents including stannous

chloride (SnCl2).

Ar − N = N − Ar′ 
SnCl2
→ ArNH 2 + Ar ′NH 2

2. Secondary Amines

R 2 NH + HNO 2 
→ R2N — N = O
N − Nitrosoa min e
(insoluble in amine)

3. Tertiary Amines: When a tertiary aliphatic amine is mixed with nitrous acid, an
equilibrium is established among the tertiary amine, its salt, and an N-nitrosoammonium
compound.
+ – + ..
2 R3N : 
→ R 3 N H X + R 3 N — N = O X−
+ HX +N aNO 2 ←

Tertiary aliphatic A min e salt N − Nitrosoammonium compound
a min e

Tertiary arylamines react with nitrous acid to form C-nitroso aromatic compounds.
Nitrosation takes place almost exclusively at the para position if it is open and, if not, at
the ortho position. The reaction is another example of electrophilic aromatic substitution.

H3C H3C
8° C
N + HCl + NaNO 2 
→ H 2O
N N O
H3C H3C
p-Nitroso-N, N-dimethylaniline
(80–90%)

Tertiary amines except N, N-Dialkylaryl amines do not react with HNO2 .

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NR2 NR2


HNO 2
→ (attack by NO + )

N O

Illustration 2: Provide structures for the products of the reaction of PhN +2 with
a) PhNMe2 b) 2-naphthol c) PhCH3.

Solution: ArN +2 is a weak electrophile that undergoes diazo coupling only with rings
activated by OH, NH 2 , NHR or NR 2 .
a)
Ph N N NMe2
N,N-dimethylaminoazobenzene
(butter yellow)

b) N N Ph
OH

1-Phenylazo-2-naphthol
c) No reaction. The substrate ring is insufficiently activated.

Illustration 3: Suggest a structural formula for a chiral compound (A) C8H11N has 4° of
unsaturation, that dissolves in dilute HCl and releases N2 with HNO2.

Solution: The compound has 4° of unsaturation indicating it has a benzene ring (a

saturated carbon with eight carbon would have the formula C8 H19 N ). (A) is a
1° amine since it dissolves in HCl and emits N 2 with HNO2 . The two
remaining carbons and the NH 2 must account for the chirality. So, the
structure of (A) is PhCH(NH 2 )CH3 .

Carbylamine Reaction

RNH 2 + CHCl3 + 3KOH 

→ R — NC + 3KCl + H 2 O
an isocyanide
(foul smelling)

Nucleophilic RNH 2 attacks electrophilic intermediate [: CCl2 ] dichlorocarbene. This reaction is

used for the detection of primary amines.

Mechanism

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[Type text]

Cl
R — NH 2 + CCl2 
→R HN C

H Cl
–HCl

+
R — N ≡ C ←
 R N C Cl

Reaction with Carboxylic Acid Derivatives

R ′COCl R ′CONHR + HCl

(R ′CO) 2 O
RNH 2 R ′CONHR + R ′COOH

R ′COOR ′′ R ′CONHR + R ′′OH

Reaction with Other Electrophilic Reagents

R ′CH = O + RNH 2 

– H 2O
→ R ′CH = NR (Schiff base)

O O

Cl C Cl + RNH 2 
→ 2HCl + RNH C NHR (symmetrical disubstituted urea)

O H O
+
R ′ — N = C = O + H 2 NR 
→ R —N C N → R ′HN
R  C NHR
isocyanate (unsymmetrical
H disubstituted urea)

R ′ — N = C = S + H 2 NR 
→ R ′ HN C NHR (a thiourea)
isothiocyanate

Reactions of Quaternary Ammonium Salts

1. Formation of 4° Ammonium Hydroxides

2R 4 N + X – + Ag 2 O + H 2 O 
→ 2R 4 N + OH – + 2AgX
very strong
bases like NaOH

2. Hofmann Elimination of Quaternary Hydroxides

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∆
[(CH 3 )3 NCH(CH 3 )CH 2 CH 3 ]+ OH –  →(CH 3 )3 N + H 2 C = CHCH 2 CH 3 + H 2 O
s − Butyltrimethylammonium hydroxide 1− Butene

This E2 elimination gives the less substituted alkene (Hofmann product) rather than the
more substituted alkene (Saytzeff product). The alkyl group having maximum β -
hydrogen gives the major alkene if R groups attached to nitrogen are different.

Ring Reactions of Aromatic Amines

NH 2 — NHR and – NR 2 strongly activate the benzene ring toward electrophilic substitution.

1. Halogenation

For monohalogenation, — NH 2 is first acetylated, because

H3 C C N

O H

is only moderately activating and is o and p-directing in nature

NH2 NH2 NHCOCH3 NHCOCH3 NH2

Br Br
←
Br2
H2O
 
Ac 2 O
→ →
Br2

H2O
OH –
→

Br Br Br

2. Sulfonation
+ - +
NH2 NH3 HSO4 NHSO3H NH3


H 2SO 4
→ 
180° C
H2O
→ 
180° C
3 hours
→

Anilinium Sulfate Sulfamic acid -

SO 3
Sulfanilic acid
(a dipolar ion)

The dipolar ion structure of sulfanilic acid account for its (a) high melting point, (b)
insolubility in H2O and organic solvents, (c) solubility in aqueous NaOH, (d) insolubility
in aqueous HCl.

H2N CO2H

will not exists as a dipolar ion since, –COOH is too weakly acidic to transfer an H+ to the

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weakly basic –NH2 attached to the electron withdrawing benzene ring. When attached to
an aliphatic C, the NH2 is sufficiently basic to accept H – from COOH.
O O

NH2 HN CH3 HN CH3 NH2

HNO3 ⋅ H 2SO 4
 →
−

(CH3 CO) 2 O
→ 
OH
heat
→

N-phenylacetamide
aniline
NO2 NO2
4-nitroanilin
N-(4-nitrophenyl)acetamide
e

Aniline-X Rearrangements
H X
N NH2 NH2
X

→ and

i) Fischer - Hepp
NO H
Ph N 
ii) OH-
→
i) H +
N N
R O R
N-Ntroso-N- (neutralize N-methyl-N-(4-nitrosophenyl)amine
alkylaniline salt)

ii) Phenylhydroxylamines
H

 →
+
i) H
Ph N ii) OH-
HO NH2

OH 4-aminophenol

+
PhNO 2 
Zn 3 NH 4
→ Ph NH
OH

iii) Sulfamic Acid

Ph NH
+
SO3H →
heat
O3 S NH3

Sulfanilic acid

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The Hinsberg Test: This test can be used to demonstrate whether an amine is primary,
secondary or tertiary. Primary amines react with benzenesulfonyl chloride to form N-substituted
benzenesulfonamides. These, in turn, undergo acid-base reactions with the excess potassium
hydroxide to form water-soluble potassium salt. Acidification of this solution will, cause the
water-soluble in the next stage, cause the water-insoluble N-substituted sulfonamide to
precipitate.
Acidic hydrogen

H O H O
OH −
R N + Cl S →( − HCl)
N S
R O
H O
1° amine
KOH

K+
H O O
N S ←
HCl
N S
R O R O
Water insoluble salt
Water soluble salt
(precipitate)
(clear solution)

Secondary amines react with benzenesulfonyl chloride in aqueous potassium hydroxide to form
insoluble, N-N-disubstituted sulfonamides that precipitate after the first stage. N,N-Disubstituted
sulfonamides do not dissolve in aqueous potassium hydroxide.

R H O R' O
N + Cl S OH −
→
( − HCl)
N S
R O R O
Water insoluble
salt (precipitate)

If the amine is a tertiary amine and if it is water insoluble, no apparent change will take place in
the mixture as we shake it with benzenesulfonyl chloride and aqueous KOH. When we acidify
the mixture, the tertiary amine dissolves because it forms a water soluble salt.

Oxidation of Amines

1. Primary secondary and tertiary amine, primary amines are oxidized by H2O2 to give
aldoximes via the nucleophile displacement by the amine on peroxide.
− H2O
R O OH  → R 
H2O2
→ R − H2O
 → R
− H2O

NH2 H NH OH N OH N OH
HO
R R

NH 
H 2 O2
→ N OH + H2O
R R

2. Tertiary amine can be oxidized clearly to tertiary amine oxides.

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[Type text]

O
R O R
H 2 O 2 or R R
OH
N R R 3 N — OH + OH 
+
→ R 3 N — O + H2O
– + –
N
+

R
R O

A tertiary amine oxide

Tertiary amine oxides undergo a useful elimination reaction as tertiary amine oxides
undergo the elimination of a dialkylhydroxylamine when they are heated. This reaction is
called the cope elimination.
O HO
R R
+ + N CH3
N CH3 
150° C
→ CH2
H3C
CH3
A tertiary amine oxide An alkene N,N-Dimethylhydroxylamine

The cope elimination is a syn elimination and proceeds through a cyclic transition state:
R CH3

CH3 
→ R + N
+
H N CH2 H O CH3
O
CH3

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Solved Problems
Objective

Problems 1: The correct order of increasing basicity for the following compounds is

NH2 CH3 CN

(I) (II) (III) (IV)

N N N N
(a) IV < I < III < II (b) I < II < III < IV
(c) IV < III < II < I (d) II < IV < I < III
Solution: (a)

Problems 2: How many primary amines are possible for the formula C4H11N
(a) 1 (b) 2
(c) 3 (d) 4

Solution: (d)

Problem 3: When aniline is treated with benzene diazonium chloride at low temperature
in weakly acidic medium, the final product obtained is

(a) NH2 (b)

N N NH2
N N

(c) (d) NH2

N N NH

N N

Solution: Dazonium cation reacts with aniline in weakly acidic medium resulting in N,
N-coupling rather than C-coupling.
+
N N + HN 
–H
→ N N NH
H
∴ (c)

Problem 4: The end product (Z) of the following reaction is

+
N2Cl 
CuCN
→ (X) 
H / H 2O
→ (Y) 
NaOH
CaO, ∆
→ (Z)
(a) a cyanide (b) a carboxylic acid

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[Type text]

(c) an amine (d) an arene.

Solution:
N2Cl  →
+
CuCN
CN 
H / H2O
→ COOH 
Soda lim e
→
∆

∴ (d)

Problem 5: Phenyl cyanide on reduction with Na/C2H5OH yields

(a) C6 H 5 CH 2 NH 2 (b) C6 H 5 NHCH 3

(c) NH2 (d) C6 H 5 NH 2 .

CH3

Solution: C6 H 5 — C ≡ N 
Na / C2 H5 OH
→ C6 H 5 — CH 2 NH 2
∴ (a)

Problem 6: Consider the following reaction,

+
∆
C6 H 5 NH 2 + CHCl 3 + KOH  → ( A) 
H / H 2O
→ ( B ) + (C )
The compounds (B) and (C) are:
(a) C6 H 5 COOH and NH 3 respectively
(b) C6 H 5 NH 2 and HCOOH respectively
(c) C6 H 5 NH 2 and H 2 O respectively
(d) None of these.

Solution: C6 H 5 NH 2 + CHCl3 + 3KOH 

→ C6 H 5 N C + 3KCl + 3H 2 O
(A)
+
C6 H 5 N C + 2H 2 O 
H
→ C6 H5 NH 2 + HCOOH
(A) (B) (C)

∴ (b)

Problem 7: Which of the following would react with ozone to form an isocyanate?
(a) CH 3 — CN (b) C6 H 5 — CN
(c) CH 3 — NC (d) C6 H 5 — NH 2 .

Solution: Isocyanides react with O 2 to form isocyanates

CH 3 — N = C + O3 
→ CH 3 N = C = O + O 2
∴ (c)

Problem 8: When benzamide is heated with thionyl chloride, the main product of the
reaction is
(a) C6 H 5 CN (b) C6 H 5 COCl
S

(c) C6 H 5 NH 2 (d) C6H5 C NH2.

[Type text]
[Type text]

Solution: SOCl 2 here can only act as a dehydrating agent.

O

C6 H 5 C NH2 + SOCl 2 
→ C6 H 5 — CN + SO2 + 2HCl
∴ (a)

Problem 9: Consider the following ions

(I) + (II) +
Me2N N N O2N N N

(III) + (IV) +
H3C O N N H3C N N

The reactivities of these ions in azo-coupling reactions (under similar

conditions) will be such that
(a) (I) < (IV) < (II) < (III) (b) (I) < (III) < (IV) < (II)
(c) (III) < (I) < (II) < (IV) (d) (III) < (I) < (IV) < (II).

Solution: (b)

Problem 10: In the reaction O + CH 3 CH 2 NH 2 

H 2 / Ni
→ (X) .
The product (X) is
(a) (b) OCH3
O CH2 NH2

CH2NH2
(c) (d)
NCH2CH3 NHCH2CH3

Solution: (d)

> N − R 3 forms nitroso amines when the substitutents are

R1
Problem 11: The compound R2
(a) R1 = CH3, R2 = R3 = H (b) R1 = R2 = H, R3 = C2H5
(c) R1 = H, R2 = R3 = CH3 (d) R1 = CH3, R2 = C2H5, R3 = C3H7
[Roorkee 1999]
Solution: (c) R1 = H and R2 = R3 = CH3
R2 > N − R 3 = CH3 > N − CH 3
R1 H

sec. Amine reacts with Nitrous acid to form nitroso amine yellow liquid.

Problem 12: Aniline when diazotized in cold and then treated with dimethyl aniline gives an
coloured product. Its structure would be

(a) (CH3)2N N N

[Type text]
[Type text]

(b) (CH3)2N NH

(c) CH3NH N N NHCH3

(d) CH3 N N NH2

[CBSE PMT 2004]

Solution: (a)

Problem 13: Indicate which nitrogen compound amongst the following would undergo
Hofmann’s reaction (i.e. reaction with Br2 and strong KOH) to furnish the
primary amine (R – NH2)
O O
|| ||
(a) R - C - NH.CH3 (b) R – C − O.NH4
O O
|| ||
(c) R - C - NH2 (d) R - C - NHOH

Solution: (c) Hofmann degradation of amide

R – CONH2 + Br2 + 4KOH → R – NH2 + 2KBr + K2CO3 + 2H2O
primary amine
HNO3/H2SO4 Sn/HCl
Problem 14: Intermediate
Heat
NH2 NH2

(a) (b)
NH2
NH2
NO2
(c)
(d)
NH2 NH2
[BHU 1995]
Solution: (b)
NO2 NH2
HNO3/H2SO4 Sn/HCl

Nitrobenzene Aniline

Problem 15: Which of the following would be least reactive towards nitration
(a) Benzene (b) Nitro benzene
(c) Toluene (d) Chloro benzene

[Type text]
[Type text]

[AMU 2000; UPSEAT 2002]

Solution: (b)
Nitro group deactivates the benzene ring.

Problem 16: Aniline reacts with acetaldehyde to form

(a) Schiff’s base (b) Carbylamine
(c) Immine (d) None of these
[MHCET 2004; AFMC 2004]

Solution: (a)
NH2 N CH CH3

Trace of an acid.
+ CH3 - CHO + H2O

Schiff's base
NO2 X
Sn + HCl
Problem 17:

In the above reaction ‘X’ stands for

(a) NH2 (b) SnCl2
(c) Cl (d) NH4+Cl−
[CPMT 1986, 2001]
Solution: (a)
NO2 NH2

Sn/HCl + 2H2O
+ 6[H]

Nitrobenzene Aniline

NH2

Problem 18: + CHCl3 + KOH ?

(a) Phenyl isocyanide (b) Benzyl amine

(c) Benzyl chloride (d) none of these
[BHU 2000; Pb PMT 2000]
Solution: (a)
C6H5 – NH2 + CHCl3 + 3KOH → C6H5NC + 3KCl + 3H2O

Problem 19: The refluxing of (CH3)2NCOCH3 with acid gives

(a) 2CH3NH2 + CH3COOH (b) 2CH3OH + CH3COOH
(c) (CH3)2NH + CH3COOH (d) (CH3)2NCOOH + CH4
[KCET 1996]

[Type text]
[Type text]

Solution: (c)
(CH3 ) 2 NCOCH3 + HCl/H 2 O
↓
(CH3 ) 2 NH + CH3COOH

Problem 20: RNH2 reacts with C6H5SO2Cl in aqueous KOH to give a clear solution. On
acidification a precipitate is obtained which is due to the formation of
H
|
(a) R - N + - SO2C6H5OH− (b) [R – N− SO2C6H5]K+
|
H
(c) R – NHSO2C6H5 (d) C6H5SO2NH2
[CPMT 1989]
Solution: (c)
C6H5SO2Cl + RNH2 → RNHSO2C6H5 
KOH
→ [R – N− SO2C6H5]K+

HCl
→ R – NHSO2C6H5

Problem 21: CH3 CH 2 NH 2 is soluble in

(a) dilute HCl (b) CuSO4 solution
(c) AgNO3 (d) dil. H2SO4

Solution: Amines being basic in nature dissolve in dilute HCl and dil. H2SO4. They can
also coordinate with Cu 2 + and Ag + ions to form soluble complexes as they can
act as good ligands.
∴ (a, b, c, d)

Problem 22: Which of the following can give Hoffmann’s degradation reaction
O O
|| ||
(a) CH3 – C – NH – Ph (b) Ph – C – NH2
O O
|| ||
(c) C2H5 – C – N – Ph (d) C2H5 – C – NH2
|
Me
Solution: (b, d)

Problem 23: Which of the following reactions give RCONH2

(a) R − C ≡ N + H2O  
HCl
→ (b) RCOONH4  Heat
→
(c) R − COCl + NH3  → (d) All of these

Solution: (b, c)

Problem 24: p-chloroaniline shows -

(a) Carbylamine test (b) diazotisation reaction
(c) Reaction with AgNO3 (d) None of these

[Type text]
[Type text]

Solution: (a, b)

Problem 25: Which of the following reaction gives are RCH2NH2

KOH + Br2
(a) R – CN LiAlH 4
→ (b) RCONH2  →
+
(c) R – CH = N - OH 
LiAlH 4
→ (d) RCH2NC 
H 3O
→

Solution: (a, c, d)

Problem 26: Match the following

Column – I (Basic Compound) Column II (pKa of ammonium ions)
(p) 4.63
(a) NH2

(b) NH3 (q) 5.25

(r) 9.26
(c) NH

(s) 11.27
(d) N

Solution: (a - p), (b - r), (c - s), (d - q)

Write-Up - I
A cyclic optically active naturally occurring toxic liquid C8H17N (X), in hemlock that was said to
cause Socrates death dissolves in aq. HCl and gives no gas will nitrous acid. It gives a precipitate
with benzenesulphony chloride in presence of NaOH.

1. What conclusion you will draw when we say that the original compound does not give
any precipitate with C6H5SO2Cl in presence of NaOH ?
(a) It may be 10 amine (b) It may be 30 amine
(c) Either of the two (d) Neither of the two

2. The formation of a compound Z take place from the compound X, when X treated with
nitrous acid , Z contains
(a) nitro group (b) nitroso group
(c) amino group (d) none of these

Solution: 1. (c) 2. (b)

Write-Up - II
Primary aliphatic amines also react with nitrous acid to yield aliphatic diazonium salts.
However, aliphatic diazonium salts are quite unstable and decompose spontaneously, even at low

[Type text]
[Type text]

temperatures, by losing nitrogen to form carbocations (hence the reaction is commonly known as
deamination). The carbocations, in turn, produce a mixture of alkenes, alcohols, and alkyl
halides.
CH3CH2CH2CH2  HONO
HCl
→ [CH3CH2CH2N2+Cl−]  → CH3CH2CH2+ + N2 + Cl−
+ +
−H −H
CH3CH = CH2 ←  CH3CH2CH2+ 
→ CH3+CHCH3  → CH3CH = CH2
Propene

1. The reaction of CH3CH2CH2NH2 with nitrous acid is used in detecting the presence of –
NH2 group in amino acids and proteins because this test is based on the fact
(a) a green colour is obtained
(b) a red colour is obtained in the final stage
(c) a characteristic change in colour is observed
(d) nitrogen is evolved quantitatively

2. Which of the following product is also formed in the above reaction ?

(a) CH3CH2CH2Cl (b) CH3CHOHCH3
(c) CH3CHClCH3 (d) All the three

3. Which type of product is likely to be formed when CH3CH2CH2NH2 in the above case it
replaced by C6H5CH2NH2 ?
(a) An alkene (b) An alcohol
(c) Both (a) and (b) (d) None of the two

Solution: 1. (d) 2. (d) 3. (c)

Subjective

Problem 1: Draw the structures of A and B.

CH3
i) CH3Cl (excess) Heating
A B
ii) Ag 2O
N
H

Solution:
H 3C

A = B =
+ CH2
N OH N

H 3C CH3 H 3C CH3

Problem 2: Explaining the mechanism of Hoffmann Bromamide reaction on cyclic

amide.

[Type text]
[Type text]

(i) Br 2
NH ?
KOH
(ii) H 2O/H
+
O
O O
NH2
+ -
K OH Br2/KOH
NH2
Solution: NH
O K+ O K+

O O O
+
H H2O

HO
H2N O

Problem 3: How would you bring about the following conversion (in 3 steps) ?
Aniline 
→ Benzylamine

NaNO 2 + HCl
Solution: PhNH 2 
0–5° C
→ PhN 2+ Cl – 
CuCN
→ PhCN 
H 2 / Ni
→ PhCH 2 NH 2

Problem 4: Complete the following reactions with appropriate reagents.

O I
NH C CH3 
?
→ 
?
→ 
?
→ 
?
→ NO2

I
Solution: (Conversion of – NH 2 to – NO2 )
O
+
NH C CH3 
H 3O
→ NH2 
NaNO 2 / HBF4
→ N 2+ BF4–
NaNO 2

N +2 BF4–
I 2 / HgO or HNO3
I

NO2

Problem 5: Write all the intermediates in the synthesis of m-bromotoluene from p-

toluidine.

[Type text]
[Type text]

Solution: CH3 CH3 CH3 CH3 CH3


(CH3CO )2 O
→  (1) Br2
( 2) OH – , H O
→ 
H 2SO 4 , NaNO 2
H2O
→ 
H 3PO 2
H 2O
→
2
heat 0 –5° C 25° C
Br Br Br
NH2 NH NH2 N2 m-Bromotoluene
p-toluidine (85% from 2-bromo-4-
COCH3 (65% from p-toluidine) methylaniline)

Problem 6: Prepare
a) PhD from PhNH 2
b) Optically active sec butyl benzene from an amine intermediate.

Solution: a) C6 H 5 NH 2 
HNO2
0–5° C
→ C6 H 5 N +2 
D3 PO2
→ C6 H5 D
b) C6 H 6 + CH3CH 2 CH(CH 3 )Cl 
AlCl3
→ PhCH(CH 3 )CH 2 CH3
(A)

(A) is a hydrocarbon which is not reactive at all. To make it resolvable, we need

to follow the given pathway.
PhCH(CH 3 )CH 2 CH 3 →
1. HNO3 / H 2SO 4
2. Sn / HCl
rac. p – H 2 NC6 H 4 CH(CH3 )CH 2 CH3
3. OH –

which is resolved with an optically active carboxylic acid such as tartaric acid.
Then deaminate via diazonium salt and H 3 PO 2 .

Problem 7: Identify (A) through (E) in the following sequence

H 3O+
PhSO2 Cl + EtNH 2 – HCl
→(A) 
NaOH
→(B) 
EtBr
→(C)  →(D) + (E)

Solution: PhSO2 NHEt 

NaOH
→ PhSO 2 N – Et 
EtBr
→ PhSO2 NEt 2
(A) (B) (C)
+

H3O
→ PhSO 2 OH + Et 2 NH 2+
(D) (E)

Problem 8: 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.

Solution: 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 ArNH 2 , but
SO3 H is a sufficiently strong acid to do so.
–
H 3 N + — CH 2COO p — H 2 N — C6 H 4 — COOH p — H 3 N + — C6 H 4 — SO3–
Glycine p − A min obenzoic acid Sulfanilic acid

Problem 9: How will you carry out the following conversions?

[Type text]
[Type text]

a) O

C NH
NH2 CH3

→

b)
NH2 
→ NH2

Solution: a) O

C NH2 NC
NH2

Br2 / KOH
→ →CHCl3
KOH

NH
CH3

LIAlH 4
→
b)
NH2 
NaNO2
→ OH 
H 2SO 4
→
–
HCl ∆ →
KMnO 4 / H
∆

COOH 
BaO
→ O 
NH 3
→ NH 
2
→
H / Pt
NH2
COOH ∆ ∆

Problem 10: A mixture of two 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 layer on the other hand, when heated with chloroform and
then acidified, gives a mixture of two isomeric compounds (D) and (E) of
molecular formula C7H6O2. Identify the compounds (A), (B), (C), (D) and (E).

Solution: NH2 OH N=C OH OH

CHO
(A) : (B) : (C) : (D) : (E) :

CHO

[Type text]
[Type text]

KVPY

1. Azobenzene will be obtained as a major product when nitrobenzene is treated with (2007)
(A) Sn and HCl (B) Raney Nickel/H2 (C) Zn/NaOH (D) Pb-C/H2

2. The products X and Y in the following reaction sequence are: (2012)

(A) (B)

(C) (D)

Answer Key

1:C 2:B

ASSIGNEMENT

SECTION – I Single Choice Questions

Level - I

1. The number of resonating structures of aniline is

(a) 2 (b) 3
(c) 4 (d) 5

2. CH3 CH 2 NH 2 is soluble in
(a) dilute HCl (b) CuSO4 solution
(c) AgNO3 (d) All of these.

3. How many isomeric amines with formula C7 H 9 N contain a benzene ring?

(a) two (b) three
(c) four (d) five.

4. Isopropylamine can be obtained by

[Type text]
[Type text]

(a) (CH 3 ) 2 CHO + NH 2 OH → ? 

LiAlH 4
→
(b) (CH 3 ) 2 CHO + CH 3 NH 2 
∆
→ ? 
H 2 / Ni
→

(c) H3C
CHOH + CH3NH2
H3C
(d) All of these.

5. Amines are highly soluble in:

(a) CCl4 (b) Diethyl ether
(c) benzene (d) Water.
6. The bromination of aniline in presence of water produces
(a) 2-bromoaniline (b) 4-bromoaniline
(c) 2,4,6-tribromoaniline (d) 2, 6-dibromoaniline.

7. Maximum basic in gas phase is?

(a) NH3 (b) CH3CH2NH2
(c) (CH3CH2)NH (d) (CH3CH2)3N

8. Examine the following two structures for the anilinium ion and choose the correct
statement from the ones given below:
NH3 NH3

(I) (II)

(a) II is not acceptable canonical structure because carbonium ions are less stable than
ammonium ions
(b) II is not an acceptable canonical structure because it is nonaromatic
(c) II is not an acceptable canonical structure because nitrogen has 10 valence electrons
(d) II is an acceptable canonical structure

9. Benzenediazonium chloride on reaction with phenol in weakly basic medium gives

(a) diphenyl ether (b) p-hyroxyazobenzene
(c) chlorobenzene (d) benzene
10. Hydrazobenzene can be obtained by reducing nitrobenzene with
(a) Sn + HCl (b) Zn + NH 4 Cl
(c) Na 3 AsO3 + NaOH (d) Zn + NaOH.

11. The reduction of a nitrile by LiAlH4 produces

(a) primary amine (b) secondary amine
(c) tertiary amine (d) amide

[Type text]
[Type text]

12. Which of the following compounds will dissolve in an alkali solution after it has
undergone reaction with Hinsberg reagent ?
(a) (C2H5)2NH (b) (CH3)3N
(c) CH3NH2 (d) C6H5NHC6H5

13. Which of the following is Sandmeyer reaction ?

(a) 2C6H5Cl Cu 2 Cl2 /HCl
→ C6H6 + Cl2
(b) C6H5N2Cl → C6H5Cl + N2
Cu 2 Cl2 /HCl

(c) C6H5OH  Zn dust

→ C6H6 + ZnO
(s) C6H5NO2 + 6[H]  Sn/HCl
→ C6H5NH2 + 2H2O

14. A positive carbylamine test is given by

(a) N, N-dimethylaniline (b) 2, 4-dimethylaniline
(c) N-methyl-o-methylaniline (d) p-methylbenzylamine

15. The product (D) in the following sequence of reactions is,

Na + C2 H 5OH
CH3COOH  NH 3
→ (A)  Heat
→ (B) P2O5
→ (C)  → (D)
(a) ester (b) amine
(c) acid (d) alcohol

16. Ethyl amine reacts with nitrosyl chloride (NOCl) to form :

(a) ethyl chloride (b) ethyl alcohol
(c) ethyl nitrite (d) nitro ethane

17. Treatment of ammonia with excess of ethyl chloride will yield:

(a) diethyl amine (b) methyl amine
(c) tetraethyl ammonium chloride (d) ethane

18. Gabriel phthalimide sysnthesis is used in the preparation of :

(a) primary amine (b) secondary amine
(c) tertiary amine (d) all of these

19. A colourless, odourless and non-combustible gas is liberated when ethylamine reacts
with:
(a) NaOH (b) CH3COCl
(c) NaNO2 + HCl (d) H2SO4

20. The hydrolysis of isocyanide produces

(a) acid (b) amide
(c) amine (d) ester

Level - II

[Type text]
[Type text]

1. 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 halide and a primary amine
(d) an alkyl cyanide and a primary amine

2. Heating of [CH3CH2CH2CH(CH3)N+(CH3)3]OH− gives, the major product

(a) CH2 = CH2 (b) CH3CH2CH2CH = CH2
(c) CH3CH2CH = CHCH3 (d) CH2 = CHCH2CH = CH2

3. Secondary amine forms yellow oily liquid with nitrous acid, which on warming with
phenol and conc. H2SO4 gives a brown or red colour and which at once changes into blue-
green. This reaction is called as :
(a) Carbyl amine reaction (b) Liebermann’s nitroso reaction
(c) Gabriel phthalimide reaction (d) Hofmann’s mustard oil reaction

4. The compound that will react most readily with NaOH to form methanol is :
+
(a) (CH3)4 NI- (b) CH3OCH3
(c) (CH3)2 S (d) (CH3)3CCl

5. Which of the following orders regarding the basic strength of substituted aniline is correct?
(a) p-methylaniline > p-chloroaniline > p-aminoacetophenone
(b) p-methylaniline > p-aminoacetophenone > p-chloroaniline
(c) p-aminoacetophenone > p-methylaniline > p-chloroaniline
(d) p-aminoacetophenone > p-chloroaniline > p-methylaniline

6. Consider the following reaction,

C6 H 5 NH 2 + CHCl3 + KOH  Δ
→ (A) →
H + /H 2 O
(B) + (C)
The compounds (B) and (C) are:
(a) C6 H 5COOH and NH3 respectively (b) C6 H 5 NH 2 and HCOOH respectively
(c) C6 H 5 NH 2 and H2Orespectively (d) None of these.
7. When aniline is treated with benzene diazonium chloride at low temperature in weakly
acidic medium, the final product obtained is

(a) NH2 (b)

N N NH2

N N

(c) (d) NH2

N N NH

N N

[Type text]
[Type text]

8. The end product (Z) of the following reaction is

+
N2Cl 
Cu / KCN
→ (X) 
H / H2 O
→ (Y) 
NaOH
CaO, ∆
→ (Z)
(a) a cyanide (b) a carboxylic acid
(c) an amine (d) an arene.

9. The increasing order of basicity of RCN, RCN = NR and RNH 2 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.

10. The compound, which on reaction with aqueous nitrous acid at low temperature produces
an oily nitrosoamine is
(a) Methyl amine (b) Ethylamine
(c) Diethylamine (d) Triethylamine.

SECTION – II More Than One Choice

1. Which of the following statements is correct?

(a) Replacement of halogen by NH2 in alkyl halide is a nucleophilic substitution reaction
(b) Ary halides show more reactivity as compared to alkyl halides in the replacements of
halogen by the NH2 group
(c) During the replacement of halogen by —NH2 group, ammonia is taken in large excess
so as to avoid the formation of 2° and 3° amines
(d) Tertiary alkyl halide generally produces alkene instead of the replacement of halogen
by NH2 group.

2. Which of the following statements is correct?

(a) Primary amines show intermolecualr hydrogen bonding
(b) Secondary amines show intermolecular hydrogen bonding
(c) Tertiary amines show intermolecular hydrogen bonding
(d) Amines have lower boiling points as compared to those of alcohols and carboxylic
acid of comparable molar masses.

3. Which of the following statements is correct?

(a) Aliphatic amines are stronger bases than ammonia
(b) Aromatic amines are stronger bases than ammonia
(c) The alkyl group in alkyl ammonium ion more stabilizes the ion relative to the amine
(d) The aryl group in aryl ammonium ion less stabilizes the ion relative to the amine

4. Reaction of RCONH2 with a mixture of Br2 and KOH gives RNH2 as the main product.
The intermediates involved in the reaction are
O
(a) (b) R—NHBr
R C NHBr

[Type text]
[Type text]

O Br
(c) R—N=C=O (d) R C N
Br

5. Identify compound (A) in the following oxidation reaction.

(A)   →O
K 2 Cr2 O7 , H 2SO 4
O

(a) NH2 (b) OH

NH2 NH2
(c) OH (d) None of these.

OH

6. Primary and secondary amiens can be distinguished by the action of:

(a) CS2/HgCl2 (b) NaNO2/HCl
(c) CHCl3/ KOH (d) NaOH

7. Pimary amines may be obtained by :

(a) the reduction of nitroalkanes (b) the reduction of alkyl isocyanide
(c) the decarboxylation of amino acids (d) the hydrolysis of alkyl isocyanate

8. Tertiary amines may be obtained by :

(a) Gabriel phthalimide synthesis
(b) heating an alcoholic solution of ammonia with excess of RX
(c) the hydrolysis of dialkyl cyanamide
(d) thermal decomposition of quaternary ammonium hydroxide

9. C4H11N (X) + HNO2  → C4H10O (30 alcohol) hence, X will give :

(a) Carbylamine reaction (b) Hofmann mustard oil reaction
(c) Diazonium salt (as the intermediate) (d) Hofmann’s bromamide reaction

10. The products obtained in the following reaction,

CH3 — NO 2 + Cl 2 + NaOH  →?
(a) ClCH 2 NO 2 (b) Cl2 CHNO 2
(c) Cl3CNO 2 (d) CH3 NH 2 .

SECTION – III Comprehension Type Questions

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Write-up I

Diazonium salt formation and coupling reactions: When a reaction mixture of phenyl
amine and nitrous acid is kept below 10°C, a diazonium salt is formed. This reaction is
called diazotization reaction.

NH2 + HNO 2 + HCl 

→
+
N2 Cl + 2H 2 O

Phenyl diazobnium
chloride

The diazonium ion, − N +2 , is rather unstable and decomposes readily to nitrogen.

However, delocalization of the diazonium from π-bond electron over a benzene ring
stabilizes phenyl diazonium sufficiently for it to form at low temperatures.
The phenyl diazonium on behaves as an electrophile, and will attack another arene
molecule such as phenol. Electrophilic substitution takes place at the 4 position,
producing 4-hydroxy phenyl azobenzene. The reaction is known as coupling reaction.

N2
+
+ OH 
→ N
N OH + H+

The compound formed is an energetically stable, yellow azo dye (the azo group is
– N = N –). The stability is due to extensive delocalisation of electrons via the nitrogen –
nitrogen double bonds.

1. The azo dye obtained on reacting 4-aminophenol with nitrous acid (in dilute hydrochloric
acid) below 10°C and coupling the resulting diazonium salt with phenol is:

N N
(a) N
(b) N OH

HO N H2N N
(c) N OH
(d) N OH

2. Benzene diazonium chloride on reaction with phenol with weakly basic medium gives
(a) diphenyl ether (b) p-hydroxy azobenzene
(c) chlorobenzene (d) benzene
3. HO

The product HO N N which is a red azodye obtained on reacting

benzene diazonium chloride with one of the following compounds.

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OH

(a) OH (b)

OH
HO OH

(c) (d)

Write-up II

Amines are derivatives of ammonia and are classified as 1°, 2°, and 3°. Primary and
secondary (but not tertiary amines) form intermolecular hydrogen bonds and thus they
boil at higher temperatures than expected. Like ammonia, all amines are basic, although
they differ in their basic nature. As amines are considered as derivatives of ammonia,
quaternary ammonium salts are considered as derivatives of ammonium salts. Only the
quaternary ammonium salts can show optical activity.
4. Which of the following statement is correct?
(a) All classes of amines form hydrogen bonds with each other
(b) Only primary and secondary amines form hydrogen bonds with water
(c) All classes of amines can form hydrogen bonds with water
(d) All amines are completely soluble in water
5. When nitrogen is bonded to three different groups
(a) The molecule is optically inactive
(b) The molecule is tetrahedral structure
(c) The molecule is not superimposable on its mirror image
(d) The amine boils at nearly similar b.p as the 1° and 2° amine of comparable molecular
weight.

6. Which of the following shows configurational isomerism?

(a) Diethyldimethylammonium iodide
(b) Methylethylpropylamine
(c) Methylallylphenylbenzyl ammonium bromide
(d) None of these

7. Methylethylpropyl amine is optically inactive because

i) It is not tetrahedral
ii) Its molecule is superimposable on its mirror image
iii) The enantiomers are rapidly interconverted
iv) The nitrogen is sp2 hybridized
Which of the above statements(s) is (are) true?
(a) Only (i) (b) Only (iii)
(c) and (iii) (d) All the four

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Write-up III

Consider the two sequence of reaction

NH2

I. (H2 C)5 H+ Se
A B
NH2

COOH NaNO2 / HCl

NaOH
∆ ∆
II. 
→ D  →E
NH2

8. The compound B may be

(a) Pyridine (b) Piperidine
(c) Pyrrole (d) All

9. The Hybridisation of N in compound A is

(a) sp2 (b) sp3
(c) sp (d) None of these

10. The product E is

OH
(a) (b)

(c) Acetone (d)

11. The intermediate D is

(a) Benzene (b) Benzyne
(c) C2H2 (d) CH2

SECTION - I

Level - I

1. (d) 5. (d) 9. (b) 13. (b) 17. (c)

2. (d) 6. (c) 10. (d) 14. (d) 18. (a)
3. (d) 7. (d) 11. (a) 15. (b) 19. (c)
4. (a) 8. (c) 12. (c) 16. (a) 20. (c)

Level - II

1. (b) 2. (b) 3. (b) 4. (a) 5. (a)

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6. (b) 7. (c) 8. (d) 9. (a) 10. (c)

SECTION - II

1. (a, c, d) 2. (a, b, d) 3. (a, c, d) 4. (a, c)

5. (a, b, c) 6. (a, b, c) 7. (a, c, d) 8. (b, d)
9. (a, b, c) 10. (a, b, c)

SECTION –III

1. (c) 2. (b) 3. (b) 4. (c)

5. (c) 6. (c) 7. (b) 8. (a)
9. (b) 10. (d) 11. (b)

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