13

UNIT

AMINES

Syllabus
� Amines : Nomenclature, classification, structure, methods of preparation, physical and chemical
properties, uses, identification of primary, secondary and tertiary amines.
� Diazonium salts : Preparation, chemical reactions and importance in synthetic organic chemistry.

Trend Analysis
2018 2019 2020
List of Concepts
D/OD D OD D OD
1Q
IUPAC nomenclature of Amines – – – –
(1 mark)
Preparation and chemical proper- 2Q 2Q 2Q 1Q
–
ties of Amines (3 marks) (3 marks) (3 marks) (1 mark)
1Q 1Q 2Q 1Q
Basic strength of Amines –
(1 mark) (1 mark) (1 mark) (1 mark)
Relative order of boiling point, 2Q 1Q 1Q
– –
solubility etc. (1 mark) (1 mark) (3 marks)
Chemical Test of Amines & Give 1Q 1Q 1Q
– –
reasons (1 mark) (3 marks) (1 mark)
1Q 1Q
Benzene diazonium chloride – – –
(2 marks) (3 marks)

Revision Notes
 Amines : Amines are considered as amino derivatives of hydrocarbons or alkyl derivatives of ammonia. In these
compounds, one, two or three hydrogen atoms are replaced by alkyl or aryl groups. Aliphatic amino compounds
are called amino alkanes and aromatic amines are called amino arenes. e.g., CH3NH2, C2H5NH2, C6H5NH2, etc.
 Classification of amines :

 Structure of amine :

Pyramidal shape of trimethylamine

 Nitrogen orbitals in amines are sp3 hybridised and the geometry is pyramidal. Due to the presence of unshared
pair of electrons, the angle C—N—E is less than 109.5°.
 Nomenclature of some Alkylamines and Arylamines :
Amine Common name IUPAC name
CH3—CH2—NH2 Ethylamine Ethanamine
CH3—CH2—CH2—NH2 n-Propylamine Propan-1-amine

Isopropylamine Propan-2-amine

CH3—N—CH2—CH3
| Ethylmethylamine N-Methylethanamine
H

Trimethylamine N, N-Dimethylmethanamine

N, N-Diethylbutylamine N, N-Diethylbutan-1-amine

1 2 3
NH 2 — C H 2 — C H = C H 2 Allylamine Prop-2-en-1-amine

NH2—(CH2)6—NH2 Hexamethylenediamine Hexane-1, 6-diamine

NH2

Aniline Aniline or Benzenamine

NH2
CH3
o-Toluidine 2-Aminotoluene

NH2
4-Bromobenzylamine
p-Bromoaniline or
4-Bromoaniline
Br
N (CH3)2

N, N-Dimethylaniline N, N-Dimethylbenzenamine

 Preparation of Amines :
(i) By reduction of nitro compounds :
(a)

(b)

R — NO2 + 3H2 R — NH2 + 2H2O

(c) 1° amine
 (ii) By ammonolysis of alkyl halides :

R — X + NH3 RNH2 R2NH R 3N

(1°) (2°) (3°)

The free amine can be obtained from the ammonium salt by treatment with a strong base :
+ - + -
R — N H 3 X + NaOH → R — NH2 + H2O + N a X

(iii) By reduction of nitriles :

2H2 + R — C ≡ N Ni
→ R — CH2 — NH2

R — C ≡ N + 4 [H] Na(Hg)

/ C 2 H 5 OH
→ R — CH2 — NH2
or LiAlH 4

1° amine

Benzylamine

(iv) Gabriel phthalimide synthesis :
O O

C C
KOH
NH NK
C C

O O

+R–X

O O

C C
ONa
NaOH(aq)
+ R — NH2 N—R
ONa (1° amine)
C C

O O
(v) By reduction of amides :
O
(i)LiAlH4
R—C—NH2 R—CH2—NH2
(ii) H2O
Amide Amine
(vi) By Hoffmann bromamide degradation reaction :
O

R—C—NH2 + Br2 + 4NaOH R—NH2 + Na2CO3 + 2NaBr + 2H2O

amide 1° amine
 Physical properties :
(i) Lower members are combustible gases, members from C3 to C11 are volatile liquids and C12
onwards are gaseous. Lower aromatic amines are liquids.
(ii) Pure amines are colourless but develop colour on keeping in air for long time.
(iii) Boiling point increases with an increase in molecular weight. The order of boiling points of isomeric amines :
Primary > Secondary > Tertiary.
(iv) Lower members are readily soluble in water which decreases in water and increases in organic solvents with an
increase in molecular weight.
 Chemical properties :
Reactions due to alkyl group :
Basic Strength of Amines :
Amines are basic in nature because they can undergo protonation due to presence of lone pair of electrons on
nitrogen atom of —NH2 group.

Primary amine

Due to presence of the alkyl group, reaction of amines with proton helps to share the proton of the acid and
the ammonium ion formed is stabilized by dispersal of positive charge by +I effect of alkyl group. Thus,
alkylamines are stronger bases than ammonia. The basic nature of aliphatic amines should increase with
increase in the number of alkyl groups. The order of basicity of amines in the gaseous phase follows the
expected order :
Tertiary amine > Secondary amine > Primary amine > NH3.
The inductive effect, solvation effect and steric hindrance of the alkyl group decide the basic strength of alkyl
amines in the aqueous state. The order of basic strength in case of methyl substituted amines and ethyl substituted
amines in aqueous solution is as follows :
(C2H5)2 NH > (C2H5)3 N > C2H5NH2 > NH3
(CH3)2 NH > CH3NH2 > (CH3)3 N > NH3
As the —NH2 group is attached directly to the benzene ring in aryl amines, this results in the unshared
electron pair on nitrogen atom to be in conjugation with the benzene ring and thus making it less available
for protonation. Thus, proton acceptability or the basic nature of aniline or other aromatic amines would be
less than that of ammonia. In case of substituted aniline, it is observed that electron releasing groups like —
OCH3, —CH3 increase basic strength whereas electron withdrawing groups like —NO2, —SO3H, —COOH,
—X decrease it.
(i) Alkylation :
 (ii) Acylation :

N-substituted amide
O O
CH2 — CH3
(CH3 — CH2)2NH + CH3 — C — Cl CH3 — C — N + HCl
CH2 — CH3
Diethylamine Acetyl chloride
N, N—Diethylacetamide

Benzoylation :
CH3NH2 + C6H5COCl → CH3NHCOC6H5 + HCl
Methylamine Benzoyl chloride N-Methylbenzamide
(iii) Carbylamine reaction : Secondary and tertiary amines do not give this reaction. This reaction is used as a
test for primary amines.
R — NH2 + CHCl3 + 3KOH Heat
 → R — NC + 3KCl + 3H2O
(alc.)
NH2 NC

Heat
+ CHCl3 + 3KOH + 3KCl + 3H2O
(alc.)

(iv) Chemical properties :

(a) Reactions involving displacement of nitrogen :
(i) Replacement by halide or cyanide ion–
Cu2Cl2/HCl
ArCl + N2
Cu2Br2/HBr
ArBr + N2 Sandmeyer's reaction
+ – CuCN/KCN
ArN2X ArCN + N2
Cu/HCl
ArCl + N2 + CuX
Cu/HBr Gattermann's reaction
ArBr + N2 + CuX

(ii) Replacement by iodide ion–

(iii) Replacement by fluoride ion— (Balz-Schiemann reaction)

(a) ArN2+Cl– + HBF4 → ArN2+BF4–

+ −
(b) Ar N 2 B F4 ∆
→ Ar — F + BF3 + N2
 (iv) Replacement by H—

+ −
(a) Ar N 2 Cl + H3PO2 + H2O → ArH + N2 + H3PO3 + HCl

+ −
(b) Ar N 2 Cl + CH3CH2OH → ArH + N2 + CH3CHO + HCl

(v) Replacement by hydroxyl group–

+ −
D
Ar N 2 Cl + H2O ¾283K
¾¾ ® ArOH + N2 + HCl

Phenol
(vi) Replacement by fluoro group–
+ –
N2Cl N2BF4 F

NaNO2
+ HBF4 + BF3 + N2
Cu,

Fluoroboric Nitrobenzene
acid
(b) Reactions involving retention of diazo group :
(i) Coupling reaction : The reaction of diazonium salts with phenols and aromatic amines to form azo
compounds with the general formula, Ar — N = N — Ar is known as coupling reaction.

+ – 273 – 278K, OH–

NaO3S N ≡ NCl + N(CH3)2

Diazonium salt of N, N-Dimethylaniline

Sulphanilic acid

(v) Importance of Diazonium salts : They are very good intermediates for the introduction of –F, –Cl, –Br, –I,
–CN, –OH, –NO2 groups into aromatic ring. Cyanobenzene can be prepared from diazonium salts.
 Synthesis of organic compounds form diazonium salts :

 Identification of primary, secondary and tertiary amines :

S.No. Test Primary amine Secondary amine Tertiary amine
(i) Reaction with nitrous Gives alcohol with Gives oily Forms nitrite in cold
acid. effervescence of N2 gas. nitrosoamine which soluble in water and
gives Liebermann's on heating gives
nitrosoamine test. nitrosoamine
(ii) Hinsberg Test: Gives N-alkyl benzene- Gives N, N-dialkyl No reaction.
Reaction with benzene sulphonamide which is benzene sulphonamide
sulphonyl chloride soluble in alkali. which is insoluble in
(Hinsberg's reagent). alkali.
(iii) Carbylamine test : Forms carbylamine or No reaction. No reaction.
Reaction with isocyanide (RNC) with
chloroform and characteristic unpleasant
alcoholic KOH. odour.
(iv) Hoffmann's mustard Forms N-substituted No reaction. No reaction.
oil reaction : Reaction isothiocyanate with
with CS2 and HgCl2. characteristic unpleasant
smell of mustard oil.
  Methods of preparation and reactions of ethylamine :

Mnemonics

• Concept: Diazonium Salts

• Mnemonic: Diazo and Cupro Came Barking to Sandy in CorNer.
• Interpretation: Sandmeyer’s reaction
Diazonium salt -® in presence of Cu (I)ion -® ArCl/ArBr/ArCN
Diazo -® Cupro -® Cl, Br, CN -® Sandmeyer’s reaction.

Know the Terms

 Zwitter ion: It contains both positive and negative ions. It contains acidic as well as basic groups in the same
molecule, e.g.
  Gabriel pthalimide synthesis: Phthalimide gives potassium salt with ethanolic KOH, which on heating gives
alkyl halide which in turn on alkaline hydrolysis gives primary amine. It is used for 1o amine synthesis.
 Hoffman Bromamide degradation: Treating amide with bromine in aqueous or ethanolic NaOH solution, results
in degradation of amide leading to formation of primary amine. 1o amine formed contains one carbon less than
the parent amide.
 Sandmeyer’s reaction: Introduction of nucleophiles Cl–, Br–, CN– to benzene ring in presence of Cu(I) ion.
 Gatterman reaction: Introduction of Cl–, Br– to benzene ring by treating diazonium salts with halogen acids.
 Schotten Baumann reaction : Benzoylation of amines with benzoyl chloride is known as Schotten Baumann
reaction.

Objective Type Questions (1 mark each)

[A] MULTIPLE CHOICE QUESTIONS : Explanation :

H2(excess)/Pt NH2
Q. 1. CH3CONH2 on reaction with NaOH and Br2 in
alcoholic medium gives : NH2
NO2 Fe/HCl
(a) CH3CH2NH2 (b) CH3CH2Br
(c) CH3NH2 (d) CH3COONa NH2
Sn/HCl
 U [CBSE, Delhi Set-1, 2020]

Ans. Correct option : (c) LiAlH4/ether
No reaction
Explanation :
∆ Q. 4. The correct increasing order of basic strength for
CH3CONH 2+ Br 2+ 4NaOH → CH 3 NH 2 + 2NaBr
the following compounds is __________.
Acetamide Methyl amine
(I) NH2   (II)   NH2 (III) NH2
+ Na 2CO3 + 2H 2O
Q. 2. Propanamide on reaction with bromine in
aqueous NaOH gives :
(a) Propanamine (b) Ethanamine
NO2 CH3
(c) N-Methyl ethanamine (d) Propanenitrile
(a) II<III< I (b) III < I < II
OR
(c) III < II < I (d) II < I < III A
IUPAC name of product formed by reaction of
Ans. Correct option : (d)
methyl amine with two moles of ethyl chloride
Explanation :
(a) N,N-Dimethylethanamine
(b) N,N-Diethylmethanamine NH2 NH2 NH2
(c) N-Methyl ethanamine
(d) N-Ethyl - N-methylethanamine
 U [CBSE, SQP, 2020-21]
Ans. (b) [CBSE SQP Marking Scheme 2020] NO2 CH3
II I III
Explanation :
∆ Electron withdrawing group decreases the
CH 3 CH 2 CONH 2 + Br2 +4NaOH  → CH 3 CH 2 NH 2 +2NaBr +Na 2 CO3 +2H
basic strength 2 Oelectron releasing groups
while
Propanamide increases the basic strength of aniline.
∆
CONH 2 + Br2 +4NaO
H  → CH 3 CH 2 NH 2 +2NaBr+Na 2 CO3 +2H 2 O Q. 5. The best reagent for converting 2–
Ethanamine phenylpropanamide into 2-phenylpropanamine
This is Hoffman Bromamide reaction. is _____.
OR (a) excess H2
(b) Br2 in aqueous NaOH
Correct option : (d)
(c) Iodine in the presence of red phosphorus
Explanation : By reaction of methyl amine
(d) LiAlH4 in ether R
with two moles of ethyl chloride, N-Ethyl -
Ans. Correct option : (d)
N-methylethanamine is formed. Explanation :
Q. 3. Which of the following reagents would not be a
good choice for reducing an aryl nitro compound
to an amine ?
(a) H2(excess)/Pt (b) LiAlH4 in ether
(c) Fe and HCl (d) Sn and HCl R
Ans. Correct option : (b)
 Q. 10. The correct IUPAC name for CH2 =
Q. 6. Aniline reacts with sodium nitrite and CHCH2NHCH3 is :
hydrochloric acid at 273-278K to give : (a) Allylmethylamine
(a) Benzene (b) 2-amino-4-pentene
(b) Benzene diazonium chloride (c) 4-aminopent-1-ene
(c) Chlorobenzene (d) N-methylprop-2-en-1-amine U
(d) o-chloroaniline U Ans. Correct option : (d)
Ans. Correct option : (b) Explanation : C 3H2 =C 2H C 1H2 NH CH3
Explanation : IUPAC name: N-methylprop-2-en-1-amine
+ –
C6H5 – NH2 NaNO2 + HCl
C6H5 – N2 Cl + NaCl +2H2O Q. 11. Which of the following is a 3° amine ?
273–278 K
Aniline Benzenediazonium (a) 1-methylcyclohexylamine (b) Triethylamine
chloride
(c) tert-butylamine (d) N-methylaniline
Q. 7. Hinsberg’s reagent which is used to test  R
amines is Ans. Correct option : (b)
(a) Benzene sulphonamide Explanation : Triethylamine [(C2H5)3N] is a 3° or
(b) Benzene diazonium chloride tertiary amine as nitrogen atom contains three
(c) Benzene sulphonyl chloride ethyl groups.
(d) Acetanilide R Q. 12. Methylamine reacts with HNO2 to form _________.
Ans. Correct option : (c) (a) CH3 — O — N = O (b) CH3 — O — CH3
(c) CH3OH (d) CH3CHO
Explanation : Hinsberg’s reagent which is used to OR
test amines is benzene sulphonyl chloride. The gas evolved when methylamine reacts with
nitrous acid is :
SO2 Cl (a) NH3 (b) N2
 (c) H2 (d) C2H6 A
Ans. Correct option : (c)
Q. 8. The best method for preparing primary amines Explanation : Methylamine reacts with HNO2 to
from alkyl halides without changing the number form CH3OH.
of carbon atoms in the chain is : CH 3 NH 2 + HNO2 

2 NaNO + HCl
→ CH 3 − N +2 Cl −
(a) Hoffmann Bromamide reaction methyl amine

(b) Gabriel phthalimide synthesis H
2O
→ CH 3 OH + N 2 + HCl
(c) Sandmeyer reaction
(d) Reaction with NH3 R OR
Correct option : (b)
Ans. Correct option : (b)
Explanation : Nitrogen gas is evolved.
Explanation : Gabriel phthalimide synthesis is used Q. 13. Arrange the following in increasing order of
to get primary amines from alkyl halides without basic strength :
changing the number of carbon atoms. Aniline, p-nitroaniline and p-toludine.
O O O (a) Aniline < p-Nitroaniline < p-Toluidine
(b) Aniline < p-Toluidine < p-Nitroaniline
—
—

KOH (alc) (c) p-Toluidine < p-Nitroaniline < Aniline

NH NK +R – X
(d) p-Nitroaniline < Aniline < p-Toluidine
—

O O Ans. Correct option : (d)

Explanation : The increasing order of basic strength
O O is given as below :
—

NaOH/H 2O OH
N–R + R–NH2
OH
—

O
—

Primary
 O amine < <
Q. 9. Write IUPAC name of the following compound :

p-Nitroanline Aniline p-Toluidine

−I effect of − It does not +I effect of CH3
(a) N,N-Dimethylpropanamine NO2 group contain −I or +I group increases
(b) 1,1-Dimethylbutanamine decreases the group. the electron
(c) N- Methylpentan-1-amine electron density density on the
(d) N,N-Dimethylbutan-1-amine U on N-atom of − nitrogen atom
Ans. Correct option : (d) NH2 group, so, it of −NH2 group,
does not undergo so, it undergo
Explanation : protonation protonation
4 3 2 1
CH3 easily and hence, easily and hence,
CH
CH 3 −3−CH
CH 2 −2−CH
CH 2 −2−CH
CH 2 2−−N
N it is least basic it is most basic
CH3 amine. amine.
IUPAC name: N, N – Dimethyl butan-1-amine [1]
Q. 14. W hich of the following species are involved in [B] ASSERTIONS AND REASONS:
the carbylamine test ? In the following questions a statement of assertion
(a) R—NC (b) COCl2 followed by a statement of reason is given. Choose the
(c) NaNO2 + HCl (d) All of the above A correct answer out of the following choices :
Ans. Correct option : (a) (a) Assertion and reason both are correct statements
Explanation : In the carbylamine test, a primary and reason is correct explanation for assertion.
amine reacts with chloroform and KOH to form alkyl (b) Assertion and reason both are correct statements
isocyanide (i.e. R–NC) having unpleasant smell. but reason is not correct explanation for assertion.
Q. 15. Which of the following amines can be prepared (c) Assertion is correct statement but reason is
by Gabriel synthesis ? wrong statement.
(a) Isobutyl amine (b) Toluene (d) Assertion is wrong statement but reason is
(c) N-methylbenzylamine (d) Aniline U correct statement.
Ans. Correct option : (a) Q. 1. Assertion : Acylation of amines gives a
Explanation : Gabriel phthalamide synthesis monosubstituted product whereas alkylation of
cannot be used for preparation of aromatic amines,
amines gives poly substituted product.
as aromatic halides do not undergo nucleophilic
substitution by salt formed by phthalamide Reason : Acyl group sterically hinders the
Q. 16.Which of the following should be most volatile ? approach of further acyl groups.
(i) CH3CH2NH2   (ii) (CH3)3N Ans. Correct option : (c)
Explanation : In alkylation, an amine can react
CH3CH2
with alkyl halide to form next higher class of amine
(iii) NH   (iv) CH3CH2CH3 caused by the presence of electron pair on nitrogen
which makes amine to behave as nucleophile and
CH3 alkyl halide thus undergo nucleophilic substitution
(a) (ii) (b) (iv) reaction. When primary and secondary amines react
(c) (i) (d) (iii) A with acid chlorides, anhydrides and esters to give
Ans. Correct option : (b) monosubstituted amides as products. Acylation is
Explanation : Primary and secondary amines form carried out in the presence of a base stronger than
hydrogen bonds and hence are less volatile than the amine like pyridine which causes the shift of the
corresponding alkanes. equilibrium to the right side.
Q. 17. 
Identify the compound Y in the following Q. 2. Assertion : Acetanilide is less basic than aniline.
reaction : Reason : Acetylation of aniline results in decrease
+ –
NH2 of electron density on nitrogen.
N2Cl
Na NO2+HCl Cu2Cl2 Ans. Correct option : (a)
273 – 278K Y+N2 Explanation : Acetanilide is less basic than aniline as
Cl in amides the carbonyl group (C=O) is a stronger
dipole than N-C dipole. Therefore, the ability of
(a) (b) N-C group to act as H-bond acceptor (as a base) is
restricted in the presence of a C=O dipole.
Cl Q. 3. Assertion : N, N-Diethylbenzene sulphonamide is
Cl insoluble in alkali.
Reason : Sulphonyl group attached to nitrogen
(c) (d)  U
atom is strong electron withdrawing group.
Ans. Correct option : (a)
Cl Cl Explanation : N, N-Diethylbenzene sulphonamide
Ans. Correct option : (a) is insoluble in alkali because it has no acidic
Explanation : When a primary aromatic amine hydrogen. Sulphonyl group attached to nitrogen
is dissolved or suspended in cold aqueous atom is electron withdrawing group.
mineral acid and treated with sodium nitrite, Q. 4. Assertion : Aromatic 1° amines can be prepared by
a diazonium salt is formed. When this freshly Gabriel Phthalimide synthesis.
prepared diazonium salt is mixed with cuprous Reason : Aryl halides do not undergo nucleophilic
chloride, diazonium group is replaced by Cl. Then substitution with anion formed by phthalimide.
chlorobenzene is formed which is Y in this reaction. Ans. Correct option : (d)
+–
NH3 N2Cl Cl Explanation : Aromatic 1° amines cannot be
NaNO2+HCl Cu2Cl2
273–278 K (Sandmeyer
+N2 prepared by Gabriel Phthalimide synthesis
reaction) (Y) because aryl halides do not undergo nucleophilic
substitution with anion formed by phthalimide.
[C] VERY SHORT ANSWER TYPE QUESTIONS : Q.6. Arrange the following in increasing order of
base strength in gas phase :
Q. 1. Write the IUPAC name of .
(C2H5)3N, C2H5NH2, (C2H5)2NH

 U [CBSE Delhi Set-2 2020]

 [CBSE, Delhi Set - 2, 2019]
Ans. N, N – dimethylbenzenamine Ans. C2H5 NH2 < (C2H5)2N < (C2H5)3N
Q. 2. Out of (CH3)3N and (CH3)2NH, which one
 [CBSE Marking Scheme, 2019]
is more basic in aqueous solution?
 [CBSE Delhi Set-3 2020]
Detailed Answer :
Ans. (CH3)2NH = Secondary amine Base strength is the ability to donate lone pair. Due
(CH3)3–N = Tertiary amine to inductive effect of C 2 H 5 , the negative charge
 Secondary amines are more basic than tertiary density on nitrogen atom increases. Therefore, lone
amines in aqueous solution due to steric factor. So, pair is easily available for donation.
(CH3)2NH is more basic in aqueous solution.
C 2 H 5 NH 2 < (C 2 H 5 )2 NH < (C 2 H 5 )3 N
Q.3. W
 rite an isomer of C3H9N which gives foul smell of
isocyanide when treated with chloroform and etha- OR
nolic NaOH.
Ans. Isomer of C3H9N is CH3CH 2CH 2 NH 2 , gives foul
Propan-1-amine
smell of isocyanides. (because primary amine gives
carbylamine reaction.)
 [Topper’s Answer 2019]
Commonly Made Error
 Some students get confused and give the structure Commonly Made Error
of secondary amine in place of primary amine.
 Sometimes, students give wrong order of base
strength of amines in gas phase.
Answering Tip
 Always remember that only primary amines give Answering Tip
carbylamine reaction and form isocyanides when
treated with chloroform and ethanolic NaOH.  Learn and understand inductive effect for explanation
of basic strength of amines in gas phase.
Q.4. Write an isomer of C3H9N which does not react
with Hinsberg reagent. Q.7. 
Arrange the following in decreasing order of
 [CBSE, Outside Delhi, set 3, 2020] solubility in water:
Ans. Isomer of C3H9N which does not react with
(CH3)3N,(CH3)2NH,CH3NH2
Hinsberg reagent is (CH3)3N i.e. tertiary amine.
 U [CBSE, Delhi Set - 3, 2019]
 − CH + C H SO Cl → No reaction
CH 3 − N 3 6 5 2
Ans. CH3NH2 > (CH3)2NH > (CH3)3N
| Hinsberg 
 [CBSE Marking Scheme 2019]
CH 3 reagent
Q.8. Arrange the following in decreasing order of the
Trimethylamine basic character :
  C6H5NH2, (CH3)3N, C2H5NH2
Commonly Made Error
 Some students give the structure of primary or  [CBSE, Outside Delhi Set - 1, 2019]
secondary amine. Ans. (CH3)3N > C2H5NH2 > C6H5NH2
 [CBSE Marking Scheme 2019]
Answering Tip
 Always remember the Hinsberg reagent test that Detailed Answer :
tertiary amines do not react with this reagent. C6H5NH2 is least basic due to presence of I-group
i.e. – C6H5 group which withdraws unshared pair
Q.5. A
 rrange the following in increasing order
of boiling points. of electrons present on N-atom of –NH2 group due
to which it does not undergo protonation easily;
(CH3)3N, C2H5OH, C2H5NH2
whereas (CH3)3N is most basic due to strong +I effect
 U [CBSE, Delhi Set - 1, 2019]
of –CH3 groups which release their bonding electrons
Ans. (CH3)3N < C2H5NH2 < C2H5OH towards N-atom and it undergoes protonation easily.
 [CBSE Marking Scheme, 2019] Hence, the decreasing order of the basic character is -
(CH3)3N > C2H5NH2 > C6H5NH2
Q.9. 
Arrange the following in increasing order of pK6 part (hydrophobic) which retards the formation of
values : hydrogen bonding. [1]
C6H5CH2NH2, C6H5NHCH3, C6H5NH2 Q.11. Write IUPAC name of the following compound :
 U [CBSE, Outside Delhi Set - 2, 2019] (CH3CH2)2NCH3

Ans. C6H5CH2NH2 < C6H5NHCH3 < C6H5NH2 [1]  U [CBSE, Delhi Set - 1, 2017]
 [CBSE Marking Scheme 2019]
Ans. N-Ethyl–N–methylethanamine. [1]
Detailed Answer: [CBSE Marking Scheme, 2017]
Greater the basic nature of amine, lesser will be Q.12. Write IUPAC name of the following compound :
the pK6 value of amine. Since, C6H5CH2NH2 is CH3NHCH(CH3)2

most basic, so, it possesses least pK6 value, while,
 U [CBSE, Delhi Set - 2, 2017]
C6H5NH2 is least basic, so, it possesses highest pK6
value. Hence, the increasing order of pK6 values is
Ans. N-Methylpropan-2-amine. [1]
C6H5CH2NH2 < C6H5NHCH3 < C6H5NH2 [1]
[CBSE Marking Scheme, 2017]
Q.10. Arrange the following in decreasing order of
solubility in water : Q.13. Write IUPAC name of the following compound :
(C2H5)2NH, C2H5NH2, C6H5NH2 (CH3)2N — CH2CH3

 U [CBSE, Outside Delhi Set 3, 2019]
 U [CBSE, Delhi Set 3, 2017]
Ans. C2H5NH2 > (C2H5)2NH > C6H5NH2 [1]
 [CBSE Marking Scheme 2019] Ans. N, N-Dimethylethanamine [1]
[CBSE Marking Scheme, 2017]
Detailed Answer: Q.14. Complete the following reaction equation :
(C2H5)2NH and C2H5NH2 are aliphatic amines C6H5N2Cl + H3PO2 + H2O → .......................
and C6H5NH2 is aromatic amine. Lower aliphatic
amines can form hydrogen bonds with water  R [CBSE Comptt. Delhi 2015]
molecules. Therefore, such amines are soluble in + –
water. When number of alkyl groups (hydrophobic) Ans. ArN2Cl+ H3PO2 + H2O → ArH + N2 + H3PO3
increases then molar mass of amines increases. Benzene
This usually results in a decrease in its solubility + HCl (where Ar is C6H5) [1]
in water. Hence, C2H5NH2 is more soluble in water [CBSE Marking Scheme 2015]
than (C2H5)2NH. Whereas, aromatic amines are
insoluble in water because of large hydrocarbon

Short Answer Type Questions-I (2 marks each)

Q. 1. Write the chemical equations involved in the following reactions :

(i) Hoffmann-bromamide degradation reaction,
(ii) Carbylamine reaction. R [CBSE Outside Delhi Set 1, 2 and 3, 2016]

O
||
Ans. (i) Ar/R — C — NH2 + Br2 + 4NaOH —→
Ar/R—NH2 + Na2CO3 + 2NaBr + 2H2O [1]
∆
(ii) Ar/R—NH2 + CHCl3 + 3KOH 
→ Ar/R—NC + 3KCl + 3H2O [1]
(where R = alkyl group, Ar = aryl group) [CBSE Marking Scheme, 2016]

Detailed Answer :
(i) Hoffmann – bromanide degradation reaction : When an amide is treated with bromine in aqueous or
ethanolic solution fo sodium hydroxide, a primary amine with one carbon atom less than the origin amide is
produced. This degradation is known as Hoffmann bromamide degradation reaction.
 O
||
R — C — NH2 + Br2 + 4NaOH → R — NH2 + Na2 + Na2CO3 + 2NaBr + 2H2O
(Aqueous or alcoholic) 1° Amine
Example,

 [1]
(ii) Carbylamine reaction : It is used as a test for detection of primary amines. When aliphatic or aromatic
primary amines are heated with chloroform and alcoholic potassium hydroxide, carbylamines or isocyanides
having foul smell are formed. Secondary and tertiary amines do not respond to this test.

 [1]

Commonly Made Errors

 Hoffmann’s degradation reaction : Some students are not able to write this equation correctly. On the product
side, only alkyl amine was written in several cases; all the products formed were not mentioned by candidates.
 A number of students do not mention alcoholic KOH. Some give incomplete equations and some do not mention
by products.

Answering Tip
 Write complete, balanced equations. Practice by writing all the named reaction equations.

Q.2.   Give reasons : (ii) 

Aniline does not undergo Friedel Crafts
(i)   Electrophilic substitution in aromatic amines reaction.
takes place more readily than benzene. Ans. (i)
+ –
NH2 N2Cl OH
(ii)   CH3CONH2 is a weaker base than CH3CH2NH2.
 U NaNO2 /HCl H2O /H+
Ans. (i) —NH2 group of aromatic amines strongly 273–278 K
activates the aromatic ring through delocalization Aniline Bemene Phenol
Aniline Bazene Phenol
of the lone pair of electrons of the N-atom over the diawnium
diazonium
aromatic ring. Due to the strong activating effect chloride
cloride (B)
of the —NH2 group, aromatic amines undergo (A)
(A) (B)
electrophilic substitution reactions readily than (ii) A Friedel–Crafts reaction is carried out in the
benzene. [1] presence of anhydrous AlCl3. But AlCl3, used as
(ii) Due to resonance, the lone pair of electrons on catalyst is acidic in nature i.e., Lewis acid whereas
the nitrogen atom in CH3CONH2 is delocalized aniline is a strong Lewis base. Thus, aniline reacts
over the keto group. with AlCl3 to form a salt.

As a result, electron density on the N-atom
in CH3CONH2 decreases. On the other hand,
in C2H5NH2, due to +I effect of the ethyl group,
the electron density on the N-atom increases
consequently, CH3CONH2 is a weaker base than
CH3CH2NH2. [1] Due to the positive charge on the N–atom,
electrophilic substitution in the benzene ring is
Q.3.   Give reasons :
deactivated. Hence, aniline does not undergo
(i) Identify ‘A’ and ‘B’:
Friedel–Crafts reaction. [1]
Q.4.   Why does acetylation of —NH2 group of aniline
reduce its activating effect ? U
Ans. Direct nitration of aniline is not possible on account
of –NH2 group present. However, nitration can
be carried out after protecting the –NH2 group by

 acetylation to give acetanilide which is then nitrated Ans. (i) Cyclohexylamine is more basic than aniline
and finally hydrolysed to give o- and p-nitroanilines. because aniline is a resonance hybrid of various
The acetyl group being electron withdrawing resonance structures. As a result, in aniline
attracts the lone pair of electrons of the N - atom the electron donating capacity of nitrogen for
towards carbonyl group. protonation is considerably decreased.[1]
As a result, the activation effect of –NH2 group (ii) Ammonolysis of alkyl halides does not give
is reduced, that is, that lone pair of electrons on single amine but gives a mixture of primary,
nitrogen is less available for donation to benzene secondary and tertiary amines.
ring by resonance. Therefore, activating effect NH / 343 K C H I
2 5
C2H 5I  → C2H 5NH 2
3  →
of NHCOCH3 group is less than that of NH2 - HI - HI

group. [2] C 2H 5) 2NH 

C2 H5 I 2 5
→ (C H ) N ¾¾¾¾
C H I
®
- HI 2 53
Q.5.   Give reasons : [(C2H5)4N+]I – 
[1]
(i) Aniline is a weaker base than cyclohexylamine. Q.6.   
Give two chemical tests to identify primary,
(ii) It is difficult to prepare pure amines by ammo­ secondary and tertiary amines. R
nolysis of alkyl halides. A
Ans. Identification of primary, secondary and tertiary amines :

S.No. Test Primary amine Secondary amine Tertiary amine

(i) Reaction with nitrous acid Gives alcohol with Gives oily Forms nitrite in cold
effervescence of N2 gas.
nitrosoamine which soluble in water and on
gives Liebermann's heating gives nitrosoamine
nitrosoamine test.
(ii) Reaction with benzene Gives N-alkyl benzene- Gives N, N-dialkyl No reaction.
sulphonyl chloride sulphonamide which is benzene sulphonamide
(Hinsberg's reagent). soluble in alkali. which is insoluble in
alkali.

[1+1]

Short Answer Type Questions-II (3 marks each)

Q.1. Give reasons :

(i) 
Aniline does not undergo Friedal-Crafts atom whereas the electron releasing tendency
reaction. of amines becomes more than that of ammonia.
(ii) Aromatic primary amines cannot be  [1]
prepared by Gabriel’s phthalimide Q.2. Arrange the following compounds as directed :
synthesis. (i) In increasing order of solubility in water :
(iii) Aliphatic amines are stronger base than (CH3)2NH, CH3NH2, C6H5NH2
ammonia. U [CBSE, Delhi Set - 1, 2020] (ii) In decreasing order of basic strength in aqueous
Ans. (i) Aniline does not undergo Friedal-Crafts solution :
reaction because aniline being a Lewis base (CH3)3N, (CH3)2NH, CH3NH2
forms a complex with AlCl3 which is a Lewis
(iii) In increasing order of boiling point :
acid. The amino group is not in a position to
activate the benzene ring towards electrophilic (C2H5)2NH, (C2H5)3N, C2H5NH2
substitution. Therefore the reaction is not  A [CBSE, Outside Delhi Set - 1, 2020]
possible.
Ans. (i) Increasing order of solubility in water :

  C6H5NH2 < (CH3)2 NH < CH3NH2  [1]
 C6 H 5 NH 2  AlCl 3 
C6 H 5 NH 2  AlCl 3 
(ii) Decreasing order of basic strength in aqueous
[1] solution :
(ii) Aromatic primary amines can not be prepared
(CH3)2NH > (CH3)3 N > CH3NH2 [1]
by Gabriel’s phthalimide synthesis because (iii) Increasing order of boiling point :
haloarenes have to react with potassium (C2H5)3 N < (C2H5)2 NH < C2H5NH2 [1]
phthalimide and they are little reactive. So the
Detailed Answer :
bond cleavage does not take place. [1]
(i) CH3NH2 and (CH3)2NH are aliphatic amines.
(iii) Aliphatic amines are stronger bases than
Aliphatic amines are soluble in water because
ammonia because the alkyl group in aliphatic they can form hydrogen bonds with water.
amines has +I effect. So the alkyl group tends When number of alkyl group (hydrophobic)
to increase the electron density on the nitrogen increases, molar mass laso increases which
 tends to decrease in solubility in water. (iii) 
Greater the extent of hydrogen bonding,
So, CH3NH2 is more soluble in water than greater will be the boiling point of amine.
(CH3)2NH. Whereas, C6H5NH2 is an aromatic Primary amines have highest boiling point
amine which is insoluble in water due to more due to presence of two hydrogen atoms on
hydrphobic part which renders the formation N-atoms as more H-bonding takes place in
of H-bond. Hence, increasing order of solubility primary amines. Hence, increasing order of
in water: boiling point is:
C6H5NH2 < (CH3)2NH < CH3NH2[1]
(C2H5)3N < (C2H5)2 NH < C2H5NH2[1]
(ii) 
Greater the +I effect, greater will be the
basic nature of amine in aqueous solution. Commonly Made Error
However, tertiary amine also exhibits
 Some students cannot write correct order of the
steric hindrance due to the presence of three
properties of the compounds.
bulky (–CH3) group due to which its basic
strength is lower than secondary amine. Hence, Answering Tip
decreasing order of basic strength in aqueous
solution is:  Learn and understand the reason to explain the
(CH3)2NH > (CH3)3N > CH3NH2 [1] properties of the compounds.

Q.3. An aromatic compound ‘A’ on heating with Br2 and KOH forms a compound ‘B’ of molecular formula C6H7N
which on reacting with CHCl3 and alcoholic KOH produces a foul smelling compound ‘C’. Write the structure and
IUPAC names of compound A, B and C. R [CBSE Delhi Set - 1, 2019]

Ans.

 [CBSE Marking Scheme, 2019] [½ × 6]

Detailed Answer :

 [3]
Q.4. Write the structures of main products when
benzene diazonium chloride reacts with the CN
following reagents.
(i) CuCN Ans. (i) (ii)
(ii) CH3CH2OH
(iii) KI R [CBSE Delhi Set 2, 2019] I
[1 × 3]
(iii)
 [CBSE Marking Scheme, 2019]
Q.5. Write equations of the following reactions:
(i) Acetylation of aniline (ii) Coupling reaction (iii) Carbylamine reaction

R [CBSE Delhi Set - 3, 2019]

Ans. (i)C6H5 N H + CH3 C O C CH3 C6 H5 N C CH3 +CH3COOH[1]

H O O H O
 (ii)
OH
N+ NCl + H OH N N OH +Cl + H2O

p-hydroxyazobenzene (orange dye)

H+
N+ NCl + H NH2 N N NH2+Cl + H2O

[1]
 (any one)

Heat
(iii) R - NH2 + CHCl3 + 3 KOH R - NC + 3 KCl + 3H2O [1]
 [CBSE Marking Scheme 2019]
Q.6. Complete the following reactions :
CN
(a) H2 /Ni

CH3
Br
H3 PO2+ H2O
(b)

N+
2Cl
–

CH2 – NH2
(c) Ethanolic KOH
+ CHCl3

CH2NH2 CH3
Br CH2 NC
Ans. (a)  (b) (c)  

(or any other suitable method) [CBSE Marking Scheme 2019]

Detailed Answer :
CN CH2NH2

(a) H2 /Ni

(b)
CH3 CH3
Br Br
H3 PO2+ H2O
+ N2 + H3 PO3 +HCl

N+
2Cl
–

(c) CH2 – NH2 CH2 NC

Ethanolic KOH
+ CHCl3 + 3KCl + 3H2O
Q. 7. How do you convert the following :
(a) N-phenylethanamide to p-bromoaniline
(b) Benzene diazonium chloride to nitrobenzene
(c) Benzoic acid to aniline U [CBSE, Outside Delhi Set - 2, 2019]

Ο Ο
|| ||
H– N – C – CH3 H– N – C – CH3 NH2

Ans. (a)  Br2 OH– or H+ [1]

CH3COOH

Br Br

+ – + – NO2
N2Cl N2BF4

(b)
NaNO2 [1]
+ HBF4
Fluoro
boricacid

NH2
COOH CONH2
∆ Br2+KOH
(c) 
+ NH3 [1]
−H2O
 (or any other suitable method)
 [CBSE Marking Scheme 2019]
Detailed Answer :
(a) N-pheny lethanamide to p-bromoaniline :
Ο
||
NH – C – CH3 NHCOCH3 NH2

Br2 aq. NaOH

CCl4 ∆

N-phenylethanamide
Br Br
(b) Benzene diazonium chloride to nitrobenzene :
+ – + –
N2Cl N2BF4 NO2

NaNO2
+ HBF4 + N2 + NaBF4
Cu,
Benzene Fluoroboric Nitrobenzene
diozonium acid
chloride
(c) Benzoic acid to aniline:
COOH COCl CONH2 NH2

SOCl2 NH3 Br2 /NaOH

Benzoic Benzoyl Benzamide Aniline

acid chloride [3]
 Q.8. Give reasons :
(i) Acetylation of aniline reduces its activation effect.
(ii) CH3NH2 is more basic than C6H5NH2.
(iii) Although –NH2 is o/p directing group, yet aniline on nitration gives a significant amount of m-nitroaniline.
 U [CBSE, Delhi Set - 1, 2017]

Ans. (i) Due to the resonance, the electron pair of nitrogen atom gets delocalised towards carbonyl group /
resonating structures. [1 ]
(ii) Because of +I effect in methylamine electron density at nitrogen increases whereas in aniline resonance
takes place and electron density on nitrogen decreases / resonating structures. [1 ]
(iii) Due to protonation of aniline / formation of anilinium ion. [CBSE Marking Scheme, 2017] [1]

Detailed Answer :
(i) The lone pair of nitrogen will get involved in resonance with the carbonyl group. Hence it will reduce the
activity of benzene ring in aniline. The resonance involved is as under :
O O–
H— —+
—

—
N — C — CH3 — N = C — CH3[1]
—
(ii) Aromatic amines are far less basic than aliphatic amines. This can be explained as follows :
Resonance stabilization is there in aniline. It can be regarded as a resonance hybrid of these structures :

Hence, the lone pair of electrons on the nitrogen atom gets delocalized over benzene ring and thus is less
available for protonation. The electron density on the nitrogen atom is increased by electron-donating
inductive effect of the alkyl groups. As a result, aliphatic amines are much stronger bases than aniline. [1]
(iii) Nitration is usually carried out with a mixture of concentrated HNO3 and concentrated H2SO4. In the

presence of these acids, most of aniline gets protonated to form anilinium ion. Therefore, in presence of
acids, the reaction mixture consists of aniline and anilinium ion. Nitration of aniline due to stearic hindrance
at ortho position, mainly gives para nitroaniline and the nitration of anilinium ion gives m-nitroaniline. In
actual practice, approximately 1:1 mixture of p-nitroaniline and m-nitroaniline is obtained.
NH2 NH2 NH2
—

— NO2
NO+
2

–H+
+
—

o-Nitroaniline (2%)
NO2
–H+ +H+ p-Nitroaniline (51%)

+ +
NH3 NH3 NH2
—

+
NO2 NH4OH
+
–H —
—

NO2 NO2
Anilinium ion m-Nitroaniline (47%)
Thus, nitration of aniline gives a substantial amount of m-nitroaniline due to protonation of the amino group.
 [1]
 OR

 [3]
[Topper's Answer, 2017]

Q.9. Write the structures of compounds A, B and C NO2

in the following reactions : [½]
(b) (A)
NH3 /D
(a) CH3 — COOH ¾¾¾¾ ®
Br2 /KOH (aq) CHCl3 + alc. KOH
A ¾¾¾¾¾¾ ® B ¾¾¾¾¾¾¾ ® C NH2
NaNO2 /Cu [½]
(b) C6H5N+2BF4– ¾¾¾¾¾ ® (B)
D

CH3 COCl / pyridine

A ¾Fe/HCl
¾¾¾ ® B ¾¾¾¾¾¾¾¾ ® C
(C)
 R + U [CBSE, Outside Delhi Set 1, 2017]
[½]
Ans. (a) (A) CH3CONH2 [½]
(B) CH3NH2 [½]
(C) CH3NC [½] [CBSE Marking Scheme, 2017]
Detailed Answer :
(a) NH3/∆ Br2/KOH(aq)
CH3COOH CH3 — CONH 2 CH3NH2
Acetamide Methylamine
(A) (B)

CHCl3 + alc. KOH

CH3 — NC
[1½]
Methyl isocyanide
(C)
+ – NaNO2/Cu Fe/HCl CH3COCl/Pyridine
(b) C6H5 N2 BF4 C6H5NO2 C6H5NH2 C6H5NHCOCH3
∆
Nitrobenzene Aniline N-phenyl ethanamide [1½]
(A) (B) (C)

Q.10. Write the structures of A, B and C in the following :

Br / aq.KOH NaNO +HCl KI
(a) C6H5 — CONH2  2
→ A 
0 − 5°C
→ B → C .
2

CHCl + alc.KOH
®C .
KCN LiAIH
(b) CH3 — Cl ¾¾¾® A ¾¾¾¾
® B ¾¾¾¾¾¾¾ 4 3

 R + U [CBSE, Outside Delhi Set 1,2&3, 2016]

Ans. (i) C6H5NH2, C6H5N2+Cl–, C6H5I  [½ + ½ + ½ ]

(ii) CH3CN, CH3CH2NH2, CH3 CH2NC
[½ + ½ + ½]
 [CBSE Marking Scheme, 2016]
Detailed Answer :
Br /KOH NaNO + HCl Kl
(a) C6H5 – CONH2 
2
→ C6H5NH2[A] 
2
→ C6H5N2+Cl–[B] → C6H5I[C][½×3]
KCN LiAlH CHCl + KOH
(b) CH3Cl 
→ CH3CN[A] 
4
→ CH3CH2NH2[B] 
3
∆
→ CH3CH2NC[C] [½×3]

Q.11. Give reasons for the following :

(i) Aniline does not undergo Friedal-Crafts reaction, Due to the positive charge on the N—atom,
(ii) (CH3)2 NH is more basic than (CH3)3 N in an electrophilic substitution in the benzene ring is
aqueous solution, deactivated. Hence, aniline does not undergo
(iii) Primary amines have higher boiling point Firedel—Crafts reaction.
than tertiary amines. (ii) (CH3)2 NH is more basic than (CH3)3N in

an aqueous solution. + I effect will increase
 + U [CBSE, Outside Delhi Set - 1, 2 & 3 2016] in alkyl group that results in increasing the
Ans. (i) Aniline is a Lewis base while AlCl3 is lewis case of donation of lone pair electron. Amine
acid. They combine to form a salt.  [1] accepts a proton and from cation which will
(ii) Due to combined + I and solvation effects. [1] be stabilised in water by solvation. Higher the
(iii) Due to presence of H-bonding in primary solvation by hydrogen bonding, higher will
amines.  [1] be the basic strength.
 [CBSE Marking Scheme, 2016]
Detailed Answer :
(i) A Friedel Crafts reactions is carried out in the [1]
presence of AlCl3. But AICl3 is used as catalyst
and is acidic in nature whereas aniline is a Therefore, with increase in methyl group,
strong base. Thus, aniline reacts with AICl3 to hydrogen bonding and stabilisation by
form a salt. solvation decreases. This net effect results in
decreases of basic strength from secondary to
+ –
NH2 NH2 AlCl
tertiary amine.
(iii) In tertiary amines, there are no H-atoms

+ AlCl whereas in primary amines, two H-atoms
are present. Due to the presence of
H-atoms, primary amines undergo extensive
Aniline Salt  [1] intermolecular H-bonding.
 H H H

—
N—H N—H N—H

—
R R R
Primary amine       [1]
(iii) Butan-1-ol
R Alcohol forms stronger hydrogen bonds
—
with water than formed by amine due to
N—R higher electronegativity of O in alcohol than
N in amine. [1]
—

[CBSE SQP Marking Scheme 2020]

R
Tertiary amine
Q.14. How will you convert the following :
As a result, extra energy is required to separate (i) Nitrobenzene into aniline,
the molecules of primary amine. Therefore, (ii) Ethanoic acid into methanamine,
primary amines have higher boiling point than (iii) Aniline to N-phenylethanamide.
tertiary amines. [1] (Write the chemical equations involved.)
Q.12. Arrange the following in increasing order of Q. 15 Give the structure of A, B and C in the following
property specified: reactions :
(i) Aniline, ethanamine, 2-ethylethanamine HNO2
KCN LiAlH4
(i) CH3Br A B 273 K C
(solubility in water) NH3
Br2+KOH CHCl3+NaOH
(ii) Ethanoic acid, ethanamine, ethanol (boiling (ii) CH3COOH ∆ A B C
point)  U+ R
(iii) Methanamine, N, N- dimethylmethanamine Ans. (i) Nitrobenzene into aniline
and N- methylmethanamine (basic strength NO2 NH2
in aqueous phase)
Ans.  (i) Aniline, N-ethylethanamine, Etanamine [1] Sn/HCl
[1]
(ii) Ethanamine, ethanol, ethanoic acid [1]
(iii) N, N dimethylmethanamine, methanamine,
N-methylmethanamine [1] Ans. (ii) Ethanoic acid into methanamine
Q.13. (i) Give a chemical test to distinguish between
N-methylethanamine and N,N-dimethyl CH3COOH NH3 CH3CONH2 +KOH
 Br2
CH3NH2
ethanamine. [1]
(ii) Write the reaction for catalytic reduction of Ans. (iii) Aniline N-Phenylethanamide
nitrobenzene followed by reaction of product
so formed with bromine water. O
(iii) Out of butan-1-ol and butan-1-amine, which
NH2 NH—C—CH3
will be more soluble in water and why?
 U+ [CBSE, SQP, 2020–21] (CH3CO)2O
(iii)  [1]
Ans. (i) 
N-methylethanamine is a secondary
amine. When it reacts with benzene OR
sulphonyl chloride, it forms N- Ethyl
KCN LiAlH4
-N methyl sulphonamide and N, N-di- (i) CH3Br CH3CN
methyl ethanamine is a tertiary amine it (A)
does not react with benzenesulphonyl HNO2
CH3CH2NH2 CH3CH2OH
chloride. [1] (B)
273K
(C)
 [½ + ½ + ½]
NH3 Br2+KOH
(ii) (ii) CH3COOH ∆
CH3CONH2
(A)
CHCl3+NaOH
CH3NH2 CH3NC
(B) (C)
 [½ + ½ + ½]
 Long Answer Type Questions (3 marks each)

Q.1. (a) Write the reactions involved in the following : (b) Give reasons :
(i) 
Hoffmann bromamide degradation (i) (CH3)2NH is more basic than (CH3)3N in
­reaction an aqueous solution.
(ii) Diazotisation (ii) Aromatic diazonium salts are more sta-
(iii) Gabriel phthalimide synthesis ble than aliphatic diazonium salts.
 R + U [CBSE, Delhi/Outside Delhi, 2018]

Ans. (a) (i) Ar/ R-CONH2 + Br2 + 4 NaOH ® Ar/ R-NH2 + 2NaBr + Na2CO3 + 2 H2O [1]
273 - 278 K

(ii) C H NH + NaNO + 2 HCI
6 5 2 2 ¾¾¾¾® C6 H 5 N +2 -
Cl + NaCI + 2 H 2 O [1]
(or any other correct equation)

(iii)

[1]

(b) (i) Because of the combined factors of inductive effect and solvation or hydration effect [1]
(ii) Due to resonance stabilisation or structural representation / resonating structures. [1]
 [CBSE Marking Scheme, 2018]

Detailed Answer :
H
(b) (i) .. ⊕
CH3 – N – H + H CH3 – N – H
CH3 CH3
(2° amine) (acidic) (Salt)
More stable

.. CH3
⊕
(CH3)3 – N + H CH3 – N – H
⊕
(3° amine) (acidic)
CH3
(Salt)
Less stable
2° amine salt form are more stable than 3° amine due to inductive effect and higher degree of hydration.

Therefore, higher the stability of salt, greater will be the reactivity of corresponding compound.
(ii) A
 romatic diazonium salts are more stable than aliphatic diazonium salts due to dispersion of positive
charge over the benzene ring caused by resonance. This is not found in aliphatic diazonium salts.
+ + — + — + — +
N——N N=N N=N N=N N——N

+ +

[2]

+ 
 Q.2. (a) Write the structures of the main products of the following reactions :
NH2

(i) (CH3CO)2O
Pyridine

(ii) SO2Cl (CH3)2 NH

+ –
N 2Cl
CH3CH2OH
(iii)

(b) Give a simple chemical test to distinguish between aniline and N,N-dimethylaniline.
(c) Arrange the following in the increasing order of their pKb values :
C6H5NH2, C2H5NH2, C6H5NHCH3
 R [CBSE, Delhi/Outside Delhi, 2018]

Ans. (a) (i) C6H5NHCOCH3 1

(ii) C6H5SO2N(CH3)2 1
(iii) C6H6 1
(b) Add chloroform in the presence of KOH and heat, Aniline gives a offensive smell while N, N dimethylani-
line does not. (or any other correct test) 1
(c) C2H5NH2< C6H5NHCH3< C6H5NH2 [CBSE Marking Scheme, 2018] 1

Detailed Answer :
O
NH2
NH–C–CH3
O
(CH3CO)2O
(a) (i) + CH3–C–CH3
Pyridine
Acetanilide
SO2Cl O
S–N–CH3
(ii) (CH3)2 NH
O CH3

N, N-dimethyl benzene sulphonamide

+ –
N 2Cl
CH3CH2OH
(iii) + N2 + HCl + CH3CHO

Benzene [3]
(b) Carbylamine Test :
∆
C6H5NH2 + CHCl3 + 3KOH       C6H5NC + 3KCl + 3H2O
Aniline Phenyl isocyanide
In this reaction, aniline gives a offensive smell due to formation of phenyl isocyanide.
∆
C6H5N(CH3)2 + CHCl3 + 3KOH       No reaction
N, N-dimethylaniline does not give carbylamine test as no hydrogen is present on nitrogen atom. [1]
(c) Greater the basic strength of amine, lesser will be the pK6 value. Alkyl amines are more basic than arylamines
due to presence of +I effect of alkyl group.
So, the increasing order of their pK6 values :
C2H5NH2 < C6H5NHCH3 < C6H5NH2 [1]
 Ans.

 [3]
[Topper's Answer 2018]
Q. 3. Write the structure of A, B, C, D and E in the following reactions :
Sn / HCl (CH3CO)2O HNO3 + H2SO4 OH– or H+
C6H5NO2 A B C D
Pyridine 288 K

H2SO4

E  U+ R
Ans. Ans. CONH2 NH2 N2Cl
Br2 NaNO2 , HCl
, KOH(aq) 0°C

(A) (B) (C)

Br2 H2O CH3CH2OH

NH2
Br Br
+ CH3CHO + N2 + HCl

Br
(E) (D)

(½ × 5 marks for structure and ½ × 5 for writing equations)

Q.6. (i) Write the structures of main products when
aniline reacts with the following reagents :
(a) Br2 water
Q. 4. Predict the reagent or the product in the fol-
(b) HCl
lowing reaction sequence :
(c) (CH3CO)2O / pyridine
CH3 CH3 CH3
(ii) Arrange the following in the increasing order of
1 (CH3CO)2O HNO3 2 their boiling point :
Pyridine H2SO4

C2H5NH2, C2H5OH, (CH3)3N

NO2 NH2 NHCOCH3
3 (iii) 
Give a simple chemical test to distinguish
CH3 CH3
between the following pair of compounds :
5 NaNO2/HCl
4 (CH3)2NH and (CH3)3N
NO2 NO2
NH2 A + U [CBSE Delhi 2015]
NH2 NH2
 U+ R Br Br
Ans. Ans. (i) (a) Br2 /H2O
[1]

Br
2,4,6-Tribromoaniline

(b) –

[1]


(c)

[1]
Q. 5. An organic compound A’ with molecular
formula C7H7NO reacts with Br2/aq. KOH to
give compound B’, which upon reaction with ( CH3 )3 N < C2 H 5 NH 2 < C 2 H 5OH
(ii)
NaNO2 & HCl at 0°C gives C’. Compound C’ on increasing order of b. p.
heating with CH3CH2OH gives a hydrocarbon D’. This order is due to H-bonding. [1]
Compound B’ on further reaction with Br2 water (iii) (CH3)2NH reacts with nitrous acid to form an oily
gives white precipitate of compound E’. Identify layer of N-nitrosaemines which is insoluble in
the compound A, B, C, D & E; also justify your aqueous mineral acids.
answer by giving relevant chemical equations.
CH3 CH3 (a) H3PO2 + H2O
N H + HO NO N – N = O + H2O (b) CuCN/KCN
CH3 CH3
(c) H2O
N-nitrosamine (ii) Arrange the following in the increasing order of
(yellow ppt) their basic character in an aqueous solution :
Whereas (CH3)2NH reacts with nitrous acid to form C2H5NH2, (C2H5)2NH, (C2H5)3N
soluble nitrite salts with no ppt.
CH3 (iii) G
ive a simple chemical test to distinguish
⊕ – between the following pair of compounds :
CH3 N + HONO (CH3)3 NH ONO
CH3 C6H5 – NH2 and C6H5 – NH – CH3
Trimethyl ammonium
nitrite [1]
 A + U [CBSE OD 2015]
Commonly Made Error CN
Ans. (i) (a) (b)
 Some students only mention the reagents but the
observations are not given.
OH
Answering Tip
 When giving a test for differentiation, always (c) [1 + 1 + 1]
write the key reagents, products, differentiable
observations to give a complete answer.
(ii) C2H5NH2 < (C2H5)3N < (C2H5)2NH
[1]
Q.7. (i) Write the structures of main products when
benzenediazonium chloride reacts with the (iii) Add CHCl3 and alc. KOH, C6H5–NH2 gives foul

following reagents : smell of isocyanide whereas C6H5–NH–CH3
does not (or any other correct test). [1]

Visual Case-based Questions (4 marks each)

Q. 1. Read the passage given below and answer the (i) Assertion: (CH3)2NH > CH3NH2 > (CH3)3N
following questions : (1 × 4 = 4) > NH3 is the order of basic strength in case
Greater is the stability of the substituted ammonium of methyl substituted amines.
cation, stronger should be the corresponding amine as Reason: The inductive effect, solvation
a base. Thus, the order of basicity of aliphatic amines effect and steric hindrance of the alkyl
group decides the basic strength of alkyl
should be: primary > secondary > tertiary, which is
amines in the aqueous state.
opposite to the inductive effect based order. Secondly,
(ii) Assertion: (C2H5) 2NH > (C2H5) 3N >
when the alkyl group is small, like –CH3 group, there C2H5NH2 > NH3 is the order of basic
is no steric hindrance to H-bonding. In case the alkyl strength in case of ethyl substituted amines.
group is bigger than CH3 group, there will be steric Reason: The change of nature of the alkyl
hinderance to H-bonding. Therefore, the change of group, does not result in change of the
nature of the alkyl group, e.g., from –CH3 to –C2H5 order of basic strength.
results in change of the order of basic strength. (iii) Assertion: Greater is the stability of the
In the following questions a statement of assertion substituted ammonium cation, stronger is
followed by a statement of reason is given. Choose the corresponding amine as a base.
the correct answer out of the following choices. Reason: The order of basicity of aliphatic
amines is: primary > secondary > tertiary.
(a) Assertion and reason both are correct statements
and reason is correct explanation for assertion. (iv) Assertion: Amines behave as a Lewis base.
Reason: Amines have an unshared pair of
(b) Assertion and reason both are correct
electrons on nitrogen atom.
statements but reason is not correct explanation
OR
for assertion.
Assertion: Solubility of amines in water
(c) Assertion is correct statement but reason is decreases with increase in molar mass.
wrong statement.
Reason: Intermolecular H bonds formed by
(d) Assertion is wrong statement but reason is the higher amines are weaker.
correct statement.
 Ans. (i) Correct option : (a) (b) Assertion and reason both are correct statements
Explanation : (CH3)2NH > CH3NH2 > but reason is not correct explanation for
(CH3)3N > NH3 is the order of basic strength assertion.
in case of methyl substituted amines as the (c)  Assertion is correct statement but reason is
inductive effect, solvation effect and steric wrong statement.
hinderance of the alkyl group decides the basic
(d)  Assertion is wrong statement but reason is
strength of alkyl amines in the aqueous state.
correct statement.
(ii) Correct option : (c) (i) Assertion: Benzene ring is aniline is highly
Explanation : (C2H5)2NH > (C2H5)3N deactivated.
> C2H5NH2 > NH3 is the order of basic strength Reason: In aniline, the sharing of lone pair of
in case of ethyl substituted amines. The change nitrogen with the ring increases the electron
of nature of the alkyl group, results in change of density on the ring.
the order of basic strength.
(ii) Assertion: In aniline –NH2 group facilitates
(iii) Correct option : (c) the electrophilic attack.
Explanation : Greater is the stability of the Reason: It is due to decrease in electron
substituted ammonium cation, stronger is the density on the ring.
corresponding amine as a base but the inductive (iii) Assertion: In aniline, the substitution mainly
effect, solvation effect and steric hinderance of takes place at ortho and para positions.
the alkyl group decides the basic strength of
Reason: The electron density is more at ortho
alkyl amines in the aqueous state.
and para positions.
(iv) Correct option : (a) (iv) Assertion: The amino group of aniline is
Explanation : Amines behave as a Lewis base acetylated before bromination.
as they have an unshared pair of electrons on Reason: It is due to the strong deactivating
nitrogen atom. effect of –NH2 group.
OR Ans. (i) Correct option: (d)
Correct option : (c) Explanation : Benzene ring in aniline is highly
activated. [1]
Explanation : Lower aliphatic amines are soluble in
water because they can form hydrogen bonds with (ii) Correct option: (c)
water molecules. However, solubility decreases with Explanation : In aniline, –NH2 group facilitates the
increase in molar mass of amines due to increase in electrophilic attack because the sharing of lone pair
of nitrogen with the ring increases the electron
size of the hydrophobic alkyl part.
density on the ring. [1]
Q. 2. Read the passage given below and answer the (iii) Correct option: (a)
following questions : (1 × 4 = 4) Explanation : In aniline, the electron density is more
Benzene ring in aninline is highly activated. This at ortho and para positions than meta position, so,
is due to the sharing of lone pair of nitrogen with the substitution mainly takes place at ortho and para
the ring which results in increase in the electron positions.
density on the ring and hence facilitates the
electrophilic attack. The substitution mainly takes
place at ortho and para positions because electron
density is more at ortho and para positions. On
reaction with aqueous bromine all the ortho
and para positions get substituted resulting in
the formation of 2,4,6-tribromoaniline. To get
a monobromo compound, the amino group is
acetylated before bromination. After bromination,
the bromoacetanilide is acid hydrolysed to give the
desired halogenated amine. The above resonating structures of aniline show more
electron density at the ortho and para positions.[1]
In the following questions, a statement of (iv) Correct option: (c)
assertion followed by a statement of reason
Explanation: –NH2 group of aniline is acetylated
is given. Choose the correct answer out of the
before bromination due to the strong activating
following choices :
effect of –NH2 group.[1]
(a) Assertion and reason both are correct statements
and reason is correct explanation for assertion. ll
 Self Assessment Test - 13
Time : 1 Hour Max. Marks : 25

Q.1. 
Read the passage given below and answer the Q.5. The source of nitrogen in Gabriel synthesis of
following questions : (1 × 4 = 4) amines is _____________.
Lower aliphatic amines are gases, primary amine with
(a) Sodium azide, NaN3
more than two carbon atoms are liquid and higher
amines are solids. Lower amines are readily soluble in (b) Sodium nitrite, NaNO2
water and solubility in water decreases and inorganic (c) Potassium cyanide, KCN
solvents like alcohol, ether, benzene etc increases with (d) Potassium phthalimide, C6H4(CO)2N–K+ R
an increase in molecular weight. Amines are soluble In the following questions (Q No. 6–7), a Statement
in organic solvents. Boiling point of 1° amine is higher
of Assertion followed by a statement of Reason
than 3° amine because of the presence of two H-atoms
attached directly with N-atom in 1° amines resulting is given. Choose the correct answer out of the
in hydrogen bonding. Boiling points of amines are following choices:
lower than that of alcohols of almost similar molar (a) Both assertion and reason are correct statements,
mass. Amines show basic character, aliphatic amines and reason is the correct explanation of the
are stronger bases than aromatic amines while less
assertion.
basic than ammonia.
The following questions are Multiple Choice (b) Both assertion and reason are correct statements,
Questions. Choose the most appropriate answer: but reason is not the correct explanation of the
assertion.
(i) Which of the following amines exist as gas ­under
standard conditions? (c) Assertion is correct, but reason is wrong
(a) methyl amine (b) butyl amine statement.
(c) ethyl amine (d) both a and c (d) 
Assertion is wrong, but reason is correct
(ii) Which of the following amines possess highest statement.
boiling point? Q.6. Assertion (A): Hoffmann’s bromamide reaction is
(a) Methyl amine (b) Dimethyl amine given by primary amides.
(c) Trimethyl amine (d) None of these Reason (R): Primary amines are less basic than
(iii) Choose the most basic amine: secondary amines.
(a) Aniline (b) Methyl amine Q.7. 
Assertion (A): Only a small amount of HCl is
(c) Ethyl amine (d) Diphenyl amine required in the reduction of nitro compounds with
iron scrap and HCl in the presence of steam.
(iv) Which of the following amines is highly soluble
in water? Reason (R): FeCl2 formed gets hydrolysed to release
(a) Methyl amine (b) Ethyl amine HCl during the reaction.
(c) N-propyl amine (d) N-butyl amine The following questions (Q No. 8–9) are short
The following questions (No. 2–5) are Multiple answer Type – I and carry 2 marks each.
Choice Questions carrying 1 mark each. Q.8. How will you convert:
(i) Aniline into Fluorobenzene.
Q.2. Amine that cannot be prepared by Gabriel-
phthalimide synthesis is (ii) Benzamide into Benzylamine. R
(a) ethyl amine (b) methyl amine Q.9. Write the structures of A and B in the following:
(c) benzyl amine (d) isobutyl amine -
(i) CH 3 CH 2 CN ¾¾¾¾¾¾ OH
®A NaOH+Br2
¾¾¾¾® B
Q.3. Tertiary amines have lowest boiling point amongst Partial hydrolysis

isomeric amines because : (ii) CH 3CH 2 Br 

i)KCN
ii)LiAlH 4
→A HNO2

0°C
→B  U
(a) they have highest molecular mass
Questions (No. 10–11) are Short Answer Type – II
(b) they do not form hydrogen bond
and carry 3 marks each.
(c) they are more polar in nature
(d) they are most basic in nature Q.10. An aromatic compound ‘A’ on treatment with
Q.4. Primary and secondary amines are distinguished by aqueous ammonia and heating forms compound
(a) Br2/ROH ‘B’ which on heating with Br2 and KOH forms a
(b) HClO compound ‘C’ of molecular formula C6H7N. Write
(c) HNO2 the structures and IUPAC names of compounds A,
(d) NH3 B and C. A
Q.11. An organic aromatic compound ‘A‘ with the (b) Distinguish between the following pair of
molecular formula C6H7N is sparingly soluble compounds:
in water. ‘A’ on treatment with dil HCl gives a
(i) Aniline and Benzylamine.
water soluble compound ‘B’. ‘A’ also reacts with
chloroform in presence of alcoholic KOH to (ii) Methylamine and Dimethylamine.
form an obnoxious smelling compound ‘C’. ‘A’ (c) Complete the following:
reacts with benzene sulhponyl chloride to form
and alkali soluble compound ‘D’. ‘A’ reacts with  A
NaNO2 and HCl to form a compound ‘E’ which OR
on reaction with phenol forms an orange dye ‘F’.
(a) Account for the following:
Elucidate the structures of the organic compounds
from ‘A’ to ‘F’. A (i) Direct nitration of aniline yields significant
No. 12 is a Long Answer Type carrying 5 marks. amount of meta derivative.
Q.12. (a) Identify A-D (ii) Primary aromatic amines cannot be
prepared by Gabriel phthalimide synthesis.
CH2Cl CH2NO2
(b) Carry out the following conversions:
—

NaOH(aq)/Br2 (i) Ethanoic acid into methanamine.

A Sn/HCl
B C (ii) Aniline to p-Bromoaniline.
D (c) Arrange the following in increasing order of
basic strength:
CH2NC Aniline, p-nitroaniline and p-toludine.
—

A&E + A + U

ll