12

CHAPTER
Organic
compounds
containing
Nitrogen
Syllabus
¾¾ Amines : Nomenclature, classification, structure, methods of preparation, physical and chemical
properties, uses, identification of primary, secondary and tertiary amines.
¾¾ Cyanides and isocyanides - will be mentioned at relevant places in text.

am
¾¾ Diazonium salts : Preparation, chemical reactions and importance in synthetic organic chemistry.

Chapter Analysis

gr
2016 2017 2018

le
List of Topics
D OD D OD D/OD
IUPAC Name 1Q
(1 mark)
– te 1Q
(1 mark)
1Q
(1 mark)
–
al
Name Reaction 1Q 1Q 1Q
– –
ci

(2 marks) (2 marks) (5 marks)*

Properties 1Q
ffi

– – – –
(5 marks)*
_o

Writing the structure of

1Q 1Q
compounds/products in a – – –
(3 marks)* (5 marks)*
ha

reaction
Give reason 1Q 1Q 1Q 1Q
–
tS

(3 marks) (3 marks) (3 marks)

(5 marks)*
Chemical test to 1Q
– – – –
ke

distinguish between (5 marks)

 * One question of 5 marks with two choices was asked. First choice has a question of 3 marks
i
An

on Name Reactions and a question of 2 marks of give reason. Second choice has a question of
3 marks on writing the structure of main products in the reactions, a question of 1 mark on
chemical test to distinguish between pair of compounds and a question of 1 mark on arranging
given compounds in their increasing order of pKb values.
On the basis of above analysis, it can be said that from exam point of view, IUPAC name, Name
reactions, writing the structure of products for the reactions and give reason are the most important
types of questions from the chapter.

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 :

— NH2 — NH —N—
Primary Secondary Tertiary
(1°) (2°) (3°)
Organic compounds containing Nitrogen [ 287
 Structure of amines :
Unshared
electron pair

— CH3 — — CH3 —

108°

CH3

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 :

am
Amine Common name IUPAC name

CH3—CH2—NH2 Ethylamine Ethanamine

gr
CH3—CH2—CH2—NH2

le
n-Propylamine Propan-1-amine

CH3—CH—CH3 te
al
| Isopropylamine Propan-2-amine
NH2
ci

CH3—N—CH2—CH3
ffi

| Ethylmethylamine N-Methylethanamine
_o

CH3—N—CH3
ha

| Trimethylamine N, N-Dimethylmethanamine
CH3
tS

1 2 3 4
ke

C2H5—N—CH2—CH2—CH2—CH3
N, N-Diethylbutylamine N, N-Diethylbutan-1-amine
C2H5
i
An

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
288 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

N(CH3)2

N, N-Dimethylaniline N, N-Dimethylbenzenamine

 Preparation of Amines :
(i) By reduction of nitro compounds :
NO2 NH2
(a) H2/Pd
Ethanol

NO2 NH2
(b) Sn + HCl
or Fe + HCl

Ni
(c) R — NO2 + 3H2 → R — NH2 + 2H2O

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

gr
+ -
R–X + NH3 → RNH2 RX
→ R2NH RX
→ R3N RX
→ R 4 N X

le
(1°) (2°) (3°)
Quaternary
te
ammonium salt
The free amine can be obtained from the ammonium salt by treatment with a strong base :
al
+ - + -
R — N H 3 X + NaOH → R — NH2 + H2O + N a X
ci
ffi

(iii) By reduction of nitriles :

_o

2H2 + R — C ≡ N Ni
→ R — CH2 — NH2
ha

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

1° amine
tS

C≡N CH2 — NH2

ke

LiAlH4
i

+ 4[H]
An

Benzylamine

(iv) Gabriel phthalimide synthesis :
Organic compounds containing Nitrogen [ 289
(v) By reduction of amides :

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

O

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

1° amine
CONH2 NH2

+ Br2 + 4 KOH + K2CO3 + 2KBr + 2H2O

Benzamide Aniline

am
 Physical properties :
(i) Lower members are combustible gases, members from C3 to C11 are volatile liquids and C12 onwards are

gr
gaseous. Lower aromatic amines are liquids.

le
(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. te
al
(vi) Lower members are readily soluble in water which decreases in water and increases in organic solvents with an
increase in molecular weight.
ci

 Chemical properties :
ffi

Reactions due to alkyl group :

_o

+ –
R—NH2 + HX R—NH3 X (Salt)
ha

acid
+ –
NH2 NH3Cl
tS

+ HCl
ke

Aniline Anilinium chloride

i
An

+ – – –
RNH3 X + OH RNH2 + H2O + X
Amine salts Base Parent 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 decides 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.
290 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

(i) Alkylation :

(ii) Acylation :
O O

R — NH2 + R ′ — C — Cl R — NH — C — R′ + HCl
N-substituted amide
O O
CH2 — CH3
(CH3 — CH2)2NH + CH3 — C — Cl CH3 — C — N + HCl
CH2 — CH3

am
Diethylamine Acetyl chloride
N, N—Diethylacetamide

gr
le
te
al
ci

C6H5 — N — H + CH3 — C — O — C — CH3 C6H5 — N — C — CH3 + CH3COOH

ffi
_o

H O O H O
Benzenamine Ethanoic anhydride N-Phenylethanamide
ha

or Acetanilide
Benzoylation :

tS

CH3NH2 + C6H5COCl → CH3NHCOC6H5 + HCl

Methlamine Benzoyl chloride N–Methylbenzamide
ke

(iii) Carbylamine reaction : Secondary and tertiary amines do not give this reaction. This reaction is used as a
test for primary amines.
i
An

R — NH2 + CHCl3 + 3KOH Heat

 → R — NC + 3KCl + 3H2O
(alc.)
NH2 NC

Heat
+ CHCl3 + 3KOH + 3KCl + 3H2O
(alc.)
(iv) Reaction with nitrous acid :
+ -
H O
R — NH2 + HNO2 NaNO 2 + HCl
→ [R — N 2 Cl]  → ROH + N2 + HCl
2

1° amine
R2NH + HNO2 → R2N—N = O + H2O
2° amine N-Nitrosamine
R3N + HNO2 → R3NHNO2
3° amine Trialkyl ammonium nitrite
NaNO + 2 HCl + -
C6H5 — NH2  2
273 - 278 K
→ C6H5 — N 2 Cl + NaCl + 2H2O

Aromatic amine Benzenediazonium

chloride
Organic compounds containing Nitrogen [ 291
(v) Reaction with arylsulphonyl chloride :
O O

S — Cl + H — N — C2H5 S — N — C2H5 + HCl

O H O H
Benzenesulphonyl chloride Primary N-Ethylbenzenesulphonamide
(Hinsberg's reagent) amine (soluble in alkali)

O O

S — Cl + H — N — C2H5 S — N — C2H5 + HCl

O C2H5 O C2H5
Secondary N- N-Diethylbenzenesulphonamide
amine
Tertiary amines do not react with benzenesulphonyl chloride.
(vi) Bromination :

am
gr
le
NH2
O

NH — C — CH3
te O

NH — C — CH3 NH2
al
ci

(CH3CO)2O Br2 OH–

ffi

Pyridine CH3COOH or H+
_o

Aniline Aniline
Br Br
(Major) p-Bromoaniline
ha

(vii) Nitration :
tS

NH2 NH2 NH2 NH2

NO2
ke

HNO3, H2SO4, 288K

+ +
i
An

NO2
Aniline
NO2
(51%) (47%) (2%)
p-nitroaniline m-nitroaniline o-nitroaniline
(viii) Preparation of monosubstituted aniline derivative by acetylation of —NH2 group :
NH2 NHCOCH3 NHCOCH3 NH2

(CH3CO)2O HNO3 / H2SO4, 288K OH– or H+

Pyridine

Acetanilide NO2 NO2

p-Nitroacetanilide p-Nitroaniline

(ix) Sulphonation :
+ – +
NH2 NH3HSO4 NH2 NH3

Conc.H2SO4 453–473K

SO3H SO3–
Anilinium
Sulphanilic acid Zwitter ion
hydrogensulphate
292 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) due to salt formation with aluminium
chloride.
(x)
Ammonolysis : Alkyl halide reacts with ammonia to form primary amine. The reaction of ammonia with
alkyl halide is known as ammonolysis.
NH / 343 K
C 2H 5I 
3
- HI
→ C 2H 5NH 2 
C2 H5 I
→ (C 2 H 5 ) 2 NH
C H I
2 5
 → (C2H5)3N 
C2 H5 I
→ [(C H ) N+]I–
2 5 4
- HI - HI

(xi) Gabriel phthalimide synthesis : In Gabriel phthalimide synthesis, pure primary aliphatic amines can be
prepared by this process. In this process, phthalimide is reacted with alcoholic KOH to get potassium
phthalimide which reacts with alkyl halide to form N-alkyl phthalimide which on basic hydrolysis gives
primary amine.

am
gr
le
te
(xii) Nitrosation : Nitrosation is a process of reacting aromatic amines with nitrous acid to introduce nitroso group
in it. e.g.,
al
ci
ffi
_o

(xiii) Zwitter ion formation : Zwitter ion is the ion which contains both positive and negative ions. It contains
ha

acidic as well as basic groups in the same molecule e.g.,


tS

H3N SO3–
ke

(xiv) Diazotisation : Diazotisation is a process of treating primary aromatic amines with nitrous acid at 273 – 278 K
to get diazonium salts which are very useful compounds.
i
An

NH2 N2+Cl–

273 – 278K
+ NaNO2 + 2HCl + 2H2O + NaCl

Aniline Benzene diazonium

chloride
(xv) Friedel-Crafts reaction : Aniline does not undergo Friedel-Crafts reaction as it forms a salt with AlCl3 which is a

Lewis acid.
 Diazonium salts :
+ −
(i) General formula : R N 2 X where R stands for an aryl group and X– ion may be Cl–, Br–, HSO4–, BF4– etc.

(ii) Stability of diazonium salts : Arenediazonium salts are more stable than alkyl diazonium salts due to the

dispersal of the positive charge over the benzene ring.

N≡N: N=N: N=N: N=N: N≡N:

Organic compounds containing Nitrogen [ 293

(iii) Preparation of diazonium salts :
NH2 N2X

273–278K
+ NaNO2 + 2HX + NaX + 2H2O

Aniline Benzene
diazonium salt
(iv) Chemical properties :
(a) Reactions involving displacement of nitrogen :
(i) Replacement by halide or cyanide ion–
CuCl/HCl
ArCl + N2
CuBr/HBr
ArBr + N2 Sandmeyer's reaction
+ – CuCN/KCN
ArN2X ArCN + N2
Cu/HCl
ArCl + N2 + CuX
Cu/HBr Gattermann's reaction

am
ArBr + N2 + CuX
(ii) Replacement by iodide ion–

gr
+ −
Ar N 2 Cl + KI → ArI + KCl + N2

le
Benzene Iodobenzene
diazonium chloride
(iii) Replacement by fluoride ion– te
al
(a) ArN +Cl– + HBF → ArN +BF–
2 4 2 4
ci

+ −
(b) Ar N 2 B F4 ∆
→ Ar — F + BF3 + N2
ffi

(iv) Replacement by H—
_o

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

ha

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

(v) Replacement by hydroxyl group–
ke

+ −
∆
Ar N 2 Cl + H2O  → ArOH + N2 + HCl
i

An

Phenol

(vi) Replacement by — NO2 group—(Balz-Schiemann reaction)

(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– –
N ≡ NCl + OH N=N OH + Cl + H2 O
(pH 9 – 10)

Phenol
Benzene diazonium p–Hydroxyazobenzene
chloride (Orange dye)
294 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

+ – 273 – 278K, H+ –
N ≡ NCl + NH2 N=N NH2 + Cl + H2O
(pH 4 – 5)

Benzene diazonium Aniline p–Aminoazobenzene

chloride (Yellow dye)
+ – –
273 – 278K, OH
NaO3S N ≡ NCl + N(CH3)2

Diazonium salt of N, N–Dimethylaniline

Sulphanilic acid
CH3
NaO3S N =N N + HCl
CH3

Methyl orange
(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.

am
 Synthesis of organic compounds form diazonium salts :

gr
le
te
al
ci
ffi
_o
ha
tS
i ke
An
Organic compounds containing Nitrogen [ 295
 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) 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.
(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

am
with CS2 and HgCl2. characteristic unpleasant
smell of mustard oil.
 Methods of preparation and reactions of ethylamine :

gr
le
te
al
ci
ffi
_o
ha
tS
i ke
An
296 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

Know the Terms

 Gomberg-Bachmann reaction : In the alkaline medium of sodium hydroxide, benzene diazonium chloride reacts
with aromatic compound like benzene. When the diazo group is replaced by phenyl or aryl group. The reaction
is called Gomberg-Bachmann reaction.
 Baker-Mulliken test : The hydroxyl amines when warmed with Tollen’s reagent convert it to metallic silver. This
reaction is used as a test for nitro compound and known as Baker-Mulliken test.
 Schotten Baumann reaction : Benzoylation of amines with benzoyl chloride is known as Schotten Baumann
reaction.
 Cope elimination : It is quite useful to determine the structure of tertiary amines. It involves the treatment of a
tertiary amine in which one of the alkyl group contains at least one β-hydrogen atom with hydrogen peroxide to
get an amine oxide which later upon heating forms an alkane and a dialkyl hydroxyl amine.

Very Short Answer-Objective Type Questions (1 mark each)

am
A. Multiple choice Questions: Ans. Correct option : (b)
Q. 1. Which of the following is a 3° amine? Explanation :
(a) 1-methylcyclohexylamine NH2

gr
H2(excess)/Pt
(b) Triethylamine

le
NH2
(c) tert-butylamine NO2 Fe/HCl
(d) N-methylaniline
U [NCERT Exemp. Q. 1, Page 180]
te Sn/HCl
NH2
al
Ans. Correct option : (b) LiAlH4/ether
No reaction
ci

Explanation :
CH3 Q. 4. In order to prepare a 1° amine from an alkyl halide
ffi

(a) (b) with simultaneous addition of one CH2 group in

NH
_o

the carbon chain, the reagent used as source of

CH3CH2 CH2CH3 nitrogen is ___________.
ha

CH2CH3 (a) Sodium amide, NaNH2

l-Methyl cyclohexylamine Triethylamine
(2˚amine)     (3˚amine) (b) Sodium azide, NaN3
tS

H3C H
(c) CH3 (d) (c) Potassium cyanide, KCN
N
(d) Potassium phthalimide, C6H4(CO)2N-K+
ke

C
CH3 NH2
CH3 R [NCERT Exemp. Q. 7, Page 181]
i

tert-Butylamine Ans. Correct option : (c)

An

(1˚amine)       N-methylaniline

Explanation : KCN is used to increase number of
Q. 2. The correct IUPAC name for CH2=CHCH2 NHCH3 carbon atoms.
is
RX + KCN → R − CN + KX
(a) Allylmethylamine
H / Raney Ni
(b) 2-amino-4-pentene R − CN + 4 H 
2
→ R − CH 2 NH 2
(c) 4-aminopent-1-ene
(d) N-methylprop-2-en-1-amine Q. 5. The source of nitrogen in Gabriel synthesis of
amines is _____________.
A [NCERT Exemp. Q. 2, Page 180]
Ans. Correct option : (d) (a) Sodium azide, NaN3
Explanation : (b) Sodium nitrite, NaNO2
3 2 1 * (c) Potassium cyanide, KCN
CH2 CHCH2 NH2
(d) Potassium phthalimide, C6H4(CO)2N–K+
CH3 R [NCERT Exemp. Q. 8, Page 181]
N-Methylprop-2-en-1-amine Ans. Correct option : (a)
Q. 3. Which of the following reagents would not be a Explanation : Potassium phthalimide is the source
good choice for reducing an aryl nitro compound of nitrogen in Gabriel synthesis.
to an amine?
(a) H2(excess)/Pt (b) LiAlH4 in ether
(c) Fe and HCl (d) Sn and HCl
R [NCERT Exemp. Q. 6, Page 181]
Organic compounds containing Nitrogen [ 297
Q. 6. The correct increasing order of basic strength for Ans. Correct option : (b)
the following compounds is __________.
Explanation : Hoffmann Bromamide degradation
(I) NH2   (II)   NH2 (III) NH2
reaction is shown by ArCONH2 by which amide is
converted into amine via undergoing intramolecular
migration of phenyl group.
O NH2
NO2 CH3 Br2/KOH
NH2 + K2CO3 + KBr + 2H2O
(a) II<III< I (b) III < I < II
Benzamide Aniline
(c) III < II < I (d) II < I < III
U [NCERT Exemp. Q. 13, Page 182]
Ans. Correct option : (d) Q. 10. Acid anhydrides on reaction with primary amines
Explanation : give ____________.
(a) amide (b) imide
NH2 NH2 NH2
(c) secondary amine (d) imine
R [NCERT Exemp. Q. 19, Page 183]
Ans. Correct option : (a)

am
Explanation :
NO2 CH3
II I III C2H5NH2+(CH3CO)2O CH3CONHC2H5+CH3COOH

gr
N-Ethylacetamide
Electron withdrawing group decreases the basic B. Match the following :

le
strength while electron releasing groups increases Q. 1. Match the species given in Column I with those
the basic strength of aniline.
Q. 7. The best reagent for converting 2–
tementioned in Column II.
S S.
al
phenylpropanamide into 2-phenylpropanamine is Column I Column II
_____. No. No.
ci

(i) Ammonolysis (a) Amine with lesser

(a) excess H2
ffi

number of carbon
(b) Br2 in aqueous NaOH atoms
_o

(c) Iodine in the presence of red phosphorus (ii) Gabriel (b) Detection test for
phthalimide primary amines
ha

(d) LiAlH4 in ether

synthesis
U [NCERT Exemp. Q. 10, Page 182]
tS

Ans. Correct option : (d) (iii) Hoffmann (c) Reaction of

Bromamide phthalimide with
Explanation :
ke

reaction KOH and R—X

(iv) Carbylamine (d) R e a c t i o n of
i
An

reaction alkylhalides with NH3

[NCERT Exemp. Q. 66, Page 191]
Ans. (i) → (d), (ii) → (c), (iii) → (a), (iv) → (b)
Q. 8. The best reagent for converting, Explanation :
2-phenylpropanamide into 1- phenylethanamine
Column I Column II
is ____.
(i) Ammonoly- (d) Reaction of alkyl halides
(a) excess H2/Pt (b) NaOH/Br2
sis with NH3
(c) NaBH4/methanol (d) LiAlH4/ether
R - X ® RNH2 + HCl
R [NCERT Exemp. Q. 11, Page 182]
Ans. Correct option : (b) (ii) Gabriel (c) Reaction of phthalimide
phthalimide with KOH and R—X
Explanation : O O
Br2/NaOH synthesis
CH3 – CH – CONH2 CH3 – CH – NH2 KOH OH
(Hofmann's bromamide NH
reaction)
R–X OH
C6H5 C6H5
2-Phenylpropanamide 1-Phenylethanamine O O

Q. 9. Hoffmann Bromamide Degradation reaction is (iii) Hoffmann (a) Amine with lesser
shown by __________. Bromamide number of carbon atoms
(a) ArNH2 (b) ArCONH2 reaction + NaOX
RCONH 2 Br → RNH 2 2

(c) ArNO2 (d) ArCH2NH2

(iv) Carbylamine (b) Detection test for primary
R [NCERT Exemp. Q. 12, Page 182] reaction amines
298 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

C. Answer the following: Ans. N, N–dimethylbutan-1-amine 1

Q. 1. Write IUPAC name of the following compound:  [CBSE Marking Scheme 2017]
(CH3CH2)2 NCH3  A [CBSE Delhi Set-1 2017] Q. 4. Write IUPAC name of the following compound:
Ans. N–Ethyl–N-methylethanamine. 1
 [CBSE Marking Scheme 2017]
Q. 2. Write IUPAC name of the following compound:
(CH3)2 N–CH2CH3 A [CBSE Delhi Set-3 2017]

Ans. N,N–Dimethylethylamine 1 A [CBSE Comptt. Delhi Set 1, 2, 3 2017]

Q. 3. Write IUPAC name of the following compound: Ans. 2, 3–dinitro phenol 1
 [CBSE Marking Scheme 2017]


 A [CBSE Comptt. OD Set 1, 2, 3 2017]

Q. 5. Write IUPAC name of the given compound:

am
 A [CBSE OD Set-2 2017]

gr
Ans. N–Methyl-2-Methylpropan-1-amine 1
OR

le
te
al
ci
ffi

1
_o

 [Topper’s Answer 2017]

Q. 6. Give the IUPAC name of H2N — CH2 — CH2 — Q. 10.Arrange the following in increasing order of basic
ha

CH = CH2. A [CBSE Comptt. Delhi 2013] strength : Aniline, p-Nitroaniline and p-Toluidine
tS

Ans. But-3-en-1-amine. 1 U [CBSE Comptt. OD 2015]

[CBSE Marking Scheme 2013] Ans. p-Nitroaniline < Aniline < p-Toluidine. 1
ke

Q. 7. Write the IUPAC name of the given compound : [CBSE Marking Scheme 2015]
NH2
Q. 11. Arrange the following in the decreasing order of
i
—
An

Br— Br their basic strength in aqueous solutions :

—
CH3NH2, (CH3)2NH, (CH3)3N and NH3
U [CBSE Delhi 2012]
—

Ans. (CH3)2NH > CH3NH2 > (CH3)3N > NH3. 1

Br
[CBSE Marking Scheme 2012]
A [CBSE Delhi 2016]
Q. 12. Complete the following reaction equation :
Ans. 2, 4, 6 – Tribromoaniline / 2, 4, 6 –
C6H5N2Cl + H3PO2 + H2O → .......................
Tribromobenzenamine. 1
R [CBSE Comptt. Delhi 2015]
[CBSE Marking Scheme 2016] + –
Q. 8. The conversion of primary aromatic amines into Ans. ArN2Cl+ H3PO2 + H2O → ArH + N2 + H3PO3
diazonium salts is known as ........ . Benzene
R [CBSE OD 2014] + HCl (where Ar is C6H5) 1
Ans. Diazotisation reaction. 1 [CBSE Marking Scheme 2015]
Q. 9. Give the IUPAC name and structure of the amine
Commonly Made Error
obtained when 3-chlorobutanamide undergoes
Hoffmann-bromamide reaction.  Some students only write benzene. All the products
formed are not mentioned.
A [CBSE SQP 2016]
Ans. 3-Chloropropanamine, CH3CH(Cl)CH2NH2. 1
Organic compounds containing Nitrogen [ 299

Short Answer Type Questions (2 marks each)

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

Zn–Hg/HCl
(i) Clemmensen
C=O reduction CH2O
(ii) Cannizzaro reaction R [CBSE Delhi Set-3 2017]
Zn–Hg/HCl
Ans. (i) C=O CH2O 1

H H H O
(ii) C = O + C = O + conc. KOH ∆D 1
H – C – OH + H – C
H H H K
H H H O
CommonlyCMade Error ∆
=O+ C = O + conc. KOH H – C – OH + H – C
 H H reduction, the correct condition for the reaction is not
For Clemmensen’s K given by many students.
H
Q. 2. Write the chemical equations involved in the following reactions :

am
(i) Hoffmann-bromamide degradation reaction,
(ii) Carbylamine reaction. R [CBSE OD 2016; Delhi 2012]

gr
Ans. (i) Hoffmann-bromamide degradation reaction : When an amide is treated with bromine in aqueous or
ethanolic solution of sodium hydroxide, a primary amine with one carbon atom less than the original amide is

le
produced. This degradation is known as Hoffmann bromamide degradation reaction.

R
O
||
¾ C ¾ NH + Br + 4NaOH → R—NH + Na CO + 2NaBr + 2H O
te
al
2 2 2 2 3 2
(Aqueous or alcoholic) 1° Amine 1
ci

Example,
ffi

O
||
_o

CH3—CH2— C —NH2 + Br2 + 4NaOH → CH3—CH2—NH2 + Na2CO3 + 2NaBr + 2H2O

Propanamide (Aqueous or Ethanamine
ha

alcoholic)
(ii)
Carbylamine reaction : It is used as a test for detection of primary amines. When aliphatic or aromatic primary
tS

amines are heated with chloroform and alcoholic potassium hydroxide, carbylamine or isocyanides having
foul smell are formed. Secondary and tertiary amines do not respond to this test.
ke

∆
R—NH2 + CHCl3 + 3KOH  → R—NC + 3KCl + 3H2O
(Alcoholic) Alkyl
i
An

isocyanide 1
 [CBSE Marking Scheme 2016]

Commonly Made Errors

 (i) 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.
 (ii) A number of students do not mention alcoholic KOH. Some give incomplete equations and some do not
mention by products.
Q. 3. Explain the following reactions :
(i) Gabriel phthalimide reaction
(ii) Coupling reaction R [CBSE Comptt. Delhi 2013]
Ans. (i) Gabriel’s phthalimide synthesis : Phthalimide when treated with alcoholic potassium hydroxide is easily
converted into potassium phthalimide which on treatment with alkyl halide followed by hydrolysis with acid or
alkali yields phthalic acid and a primary amine.
O O

C C
KOH   RX
NH N—K
–H2O
C C

O O
Phthalimide Potassium
phthalimide
300 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

     1
(ii) Coupling reaction : It involves the reaction of benzene diazonium salts with phenols or aryl amines.
Coupling of phenol takes place in mild alkaline solution while with aromatic 1° amines in mild acidic
medium.
OH–
N2Cl + OH N=N OH + HCl
273K – 278K

p-Hydroxy azobenzene
(Orange dye) 1

am
Q. 4. Give chemical tests to distinguish between the following pairs of compounds :
(i) Aniline and Ethylamine

gr
(ii) Ethylamine and Dimethylamine A [CBSE Comptt. Delhi 2013]

le
Ans. (i) Aniline forms diazonium salt with NaNO2/HCl which gives orange red dye with β-naphthol. Ethylamine does
not give this test.

NH2 + NaNO2 + HCl

273-278K te + –
N2Cl + NaCl + H2O
al
ci
ffi
_o
ha

b
tS

1
ke

(ii) Ethylamine gives foul smelling ethyl isocyanide on heating with chloroform and potassium hydroxide solution.
Dimethylamine does not give this test. 1
i

C2H5NH2 + CHCl3 + 3KOH → C2H5NC + 3KCl + 3H2O

An

Commonly Made Errors

 Some students give those chemical tests which are given by both the compounds hence the compounds could not
be distinguished.
 In several cases, only the name of the test is given, the reagents used and the observations are not written.

Q. 5. Give reasons : NH / 343 K

C2H 5I 
3
→ C 2H 5NH2  → (C 2 H 5 ) 2 NH
C2 H5 I
- HI - HI
(i) Aniline is a weaker base than cyclohexylamine.
C H I
2 5
 → (C2H5)3N 
C2 H5 I
→ [(C H ) N+]I–
2 5 4
(ii) It is difficult to prepare pure amines by - HI 1
ammonolysis of alkyl halides.
Q. 6. Give reasons :
A&E [CBSE Comptt. OD 2013]
(i) Electrophilic substitution in aromatic amines takes
Ans. (i) Cyclohexylamine is more basic than aniline place more readily than benzene.
because aniline is a resonance hybrid of various
resonance structures. As a result, in aniline (ii) CH3CONH2 is a weaker base than CH3CH2.NH2.
the electron donating capacity of nitrogen for A&E [CBSE Comptt. OD 2013]
protonation is considerably decreased. 1 Ans. (i) —NH2 group of aromatic amines strongly
(ii) Ammonolysis of alkyl halides does not give single activates the aromatic ring through delocalization
amine but gives a mixture of primary, secondary
of the lone pair of electrons of the N-atom over the
and tertiary amines.
aromatic ring. Due to the strong activating effect
Organic compounds containing Nitrogen [ 301
of the —NH2 group, aromatic amines undergo Q. 7. A primary amine, RNH2 can be reacted with
electrophilic substitution reactions readily than CH3—X to get secondary amine, R—NHCH3
benzene. 1 but the only disadvantage is that 3° amine and
(ii) Due to resonance, the lone pair of electrons on the quaternary ammonium salts are also obtained as
nitrogen atom in CH3CONH2 is delocalized over side products. Can you suggest a method where
the keto group. RNH2 forms only 2° amine?
–
O O C [NCERT Exemp. Q. 54, Page 189]
+ Ans.
CH2 — C — NH2 CH3 — C = NH2
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, Carbylamine reaction is shown by 1° amine only
the electron density on the N-atom increases which results in the replacement of two hydrogen
consequently, CH3CONH2 is a weaker base than atoms attached to nitrogen atom of NH2 group
CH3CH2NH2. 1 by one carbon atom. On catalytic reduction, the
isocyanide will give a secondary amine with one

am
methyl group. 2

gr
Long Answer Type Questions-I (3 marks each)

le
Q. 1. Write the structures of A, B and C in the following :
Br2 / aq.KOH
→ A NaNO 2 +HCl
→ B KI
te KCN
(ii) CH3Cl → CH3CN [A] LiAlH
 4
→
(i) C6H5–CONH2   → C
al
0 -5°C CHCl + KOH
CH3CH2NH2 [B] 
3

∆
→ CH3CH2NC [C]
ci

(ii) CH3 – Cl KCN LiAIH

→ A 
CHCl +alc.KOH
→ B 
4
→C .
3
[CBSE Marking Scheme 2016] 1½
ffi

A [CBSE Delhi 2016; DDE]

Q. 2. Give the structures of A, B and C in the following
reaction : A [CBSE SQP 2016]
_o

Ans. (i) C6H5 – CONH2 Br (i) C6H5NO2 Fe / HCl

→ A HNO2 ;273K
→ B C
6 H 5 OH
→C
2 /KOH
 → C6H5NH2
ha

(ii) C6H5N2Cl CuCN

+
H2 O / H NH 3 ; ∆
[A] NaNO 2 +HCl
+ – → A  → B  →C
 → C6H5N2 Cl [B] KI
→ C6H5I [C]
Ans. (i) A—C6H5NH2, B— C6H5N2+Cl–, C— C6H5–N2
tS

1½ —C6H4–OH ½+½+½
ke

(ii) A—C6H5CN, B— C6H5COOH, C— C6H5CONH2

½+½+½
i
An

Q. 3. Give the structure of A, B and C in the following reactions :

NaNO +HCl H O
(i) C6H5NO2 Sn+HCl
 → A 
2
273 K
→ B 
2
→C

H O/H+ NH Br +KOH
(ii) CH3CN 
2
→ A 
∆
3
→ B 
2
→C A [CBSE Delhi 2014]

NaNO + HCl
Ans. (i) C6H5NO2 Sn + HCl
 2
→ C6H5NH2  → C6H5N+2Cl– H
2 O→ C H OH
6 5 1½
273K
(A) (B) (C)

O
—

NH
H 2 O/H+ 3→
→ CH3 — C — OH 
(ii) CH3CN  ∆ CH3CONH2 Br2 + KOH
 → CH3NH2 1½
(A) (B) (C)

Q. 4. Give the structure of A, B and C in the following reactions :

LiAlH HNO
(i) CH3Br KCN
 → A 
4
→ B 
273 K
2
→C

NH Br +KOH CHCl +NaOH

(ii) CH3COOH 
∆
3
→ A 
2
→ B 
3
→C A [CBSE Delhi 2014]
302 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

KCN LiAlH HNO

→ CH3CN 
Ans. (i) CH3Br  4
→ CH3CH2NH2 
273 K
2
→ CH3CH2 — OH ½+½+½

(A) (B) (C)

NH3 Br2 + KOH CHCl 3 + NaOH
(ii) CH3COOH 
∆
→ CH3CONH2 
→ CH3NH2 → CH3NC ½+½+½

(A) (B) (C) [CBSE Marking Scheme 2014]

Q. 5. Identify A, B and C in the following reactions:

(i)

(ii)
 A [CBSE Comptt. OD Set-1, 2, 3 2017]
Ans. (i)A: CH3—CH2CN; B CH3—CH2—CH2—NH2; C: CH3—CH2—CH2—NH—COCH3 ½×3
(ii)

am
gr
 ½×3
 [CBSE Marking Scheme 2017]

le
Q. 6. Identify A, B and C in the following:

(i) te
al
ci

(ii)
ffi

 A [CBSE Comptt. Delhi Set-1, 2, 3 2017]

_o

Ans. (i) A: CH3- CH2CN; B CH3- CH2- CH2 NH2 ; C: CH3-CH2- CH2-NH-COCH3 ½×3
ha
tS
ke

 ½×3
 [CBSE Marking Scheme 2017]
i
An

Q. 7. Write the structures of A, B, C in the following reactions:

(i)

(ii)
 A [CBSE OD Set-2 2016]

 3
 [Topper’s Answer 2016]
Organic compounds containing Nitrogen [ 303
Detailed Answer: COOH
Ans. A– —
(i) A ⇒ C6H5–CO–NH2
½+½
B ⇒ C6H5–NH2
C ⇒ C6H5–NH–CO– CH3 Benzoic acid
(ii) A ⇒ C6H5– NO2 —
CONH2
B–
B ⇒ C6H5– NH2 ½+½
C ⇒ C6H5– N≡C 3
Benzamide
Q. 8. An aromatic compound ‘A’ on treatment with
C– NH2
aqueous ammonia and heating forms compound

—
‘B’ which on heating with Br2 and KOH forms a
compound ‘C’ of molecular formula C6H7N. Write
the structures and IUPAC names of compounds A,
B and C. A [CBSE Comptt. Delhi 2015]
Aniline ½+½
[CBSE Marking Scheme 2015]
Q. 9. An organic aromatic compound ‘A‘ with the molecular formula C6H7N is sparingly soluble in water. ‘A’ on

am
treatment with dil HCl gives a water soluble compound ‘B’. ‘A’ also reacts with chloroform in presence of
alcoholic KOH to form an obnoxious smelling compound ‘C’. ‘A’ reacts with benzene sulhponyl chloride to
form and alkali soluble compound ‘D’. ‘A’ reacts with NaNO2 and HCl to form a compound ‘E’ which on

gr
reaction with phenol forms an orange dye ‘F’. Elucidate the structures of the organic compounds from ‘A’ to ‘F’.

le
 A [CBSE SQP 2017]
Ans.

–
C te
al
NH2 NH3 Cl N+
ci
ffi

A B C
_o

+
ha

O N Cl
NH S = O
tS

D E F HO N
N
ke

 ½ each
i
An

[CBSE Marking Scheme 2017]

Q. 10. Do as directed :
(i) Arrange the following compounds in the increasing order of their basic strength in aqueous solution :
CH3NH2, (CH3)3N, (CH3)2NH.
(ii) Identify ‘A’ and ‘B’ :
+
C 6 H5NH2 NaNO 2 / HCl: 273 K
 → A H
2O / H
→B
(iii) Write equation of carbylamine reaction. U + A + R [CBSE Comptt. Delhi/OD 2018]
Ans. (i) (CH3)3N < CH3NH2 < (CH3)2NH 1
(ii) A : C6H5N2+Cl– B : C6H5OH 1
Heat
(iii) RNH 2 + CHCl 3 + 3KOH 
→ R − NC + 3KCl +3H 2O 1

[CBSE Marking Scheme 2018]

Q. 11. 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 give a significant amount of m-nitroaniline.
 A&E [CBSE OD/Delhi Set-1, 2, 3 2017]
304 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

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

Answering Tip
 Draw the resonating structures and chemical reactions to support the answer wherever necessary.
OR

am
gr
le
te
al
ci
ffi
_o
ha
tS
i ke
An

3
[Topper’s Answer 2017]

Detailed Answer:
(i) Acetylation of aniline reduces its activation effect as it decreases the electron density on nitrogen. Because of
resonance, the electron pair of nitrogen atom gets delocalised towards carbonyl group thereby reducing the
activation effect.
(ii) Due to +I effect in CH3NH2, electron density in methylamine at nitrogen increases whereas in C6H5NH2
resonance takes place and electron density on nitrogen decreases.

(iii) Nitration of aniline occurs in an acidic medium i.e, in the presence of a mixture of concentrated HNO3 and
concentrated H2SO4. In acidic medium, aniline is protonated to give anilinium ion. As anilinium ion is meta-
directing, it forms a significant amount of m-nitroaniline.
Organic compounds containing Nitrogen [ 305

Aniline Anilinium m-Nitroaniline 3

 ion   (47%)
Q. 12. How will you convert the following : (ii) (CH3)2 NH is more basic than (CH3)3 N in an aqueous
(i) Nitrobenzene into aniline, solution. +I effect will increase in alkyl group that
(ii) Ethanoic acid into methanamine, results in increasing the ease of donation of lone
(iii) Aniline to N-phenylethanamide. pair electron. Amine accepts a proton and form
(Write the chemical equations involved.)
cation which will be stabilised in water by solvation.
 A [CBSE Delhi 2014]
Higher the solvation by hydrogen bonding, higher
NO2 NH2
will be the basic strength.
Ans. (i) + –
Sn/HCl
1 NH2 NH2AlCl3

—
am
Br2
(ii) CH3COOH NH
→ CH3CONH2  → + AlCl3
3 +KOH

gr
CH3NH2 1

le
O Aniline Salt
NH2 R R
(iii) NH—C—CH3
te
—

—
R—N—H > R—N—R
al
(CH3CO)2O
1
Therefore, with increase in methyl group, hydrogen
ci

bonding and stabilisation by solvation decreases.

Q. 13. Give reasons for the following : This net effect results in decrease of basic strength
ffi

(i) Aniline does not undergo Friedel-Crafts reaction, from secondary to tertiary amine. 1
_o

(ii) (CH3)2NH is more basic than (CH3)3N in an (iii) In tertiary amine there are no H-atoms whereas in
aqueous solution, primary amines, two H-atoms are present. Due to
ha

(iii) Primary amines have higher boiling point than the presence of H-atoms, primary amines undergo
tertiary amines. A&E [CBSE OD 2016; Delhi 2014] extensive intermolecular H-bonding.
tS

H H H R
Ans. (i) A Friedel–Crafts reaction is carried out in the
—

—
presence of AlCl3. But AlCl3 used as catalyst is acidic
ke

N—H N—H N—H N—R

in nature i.e., Lewis acid whereas aniline is a strong
—

—
Lewis base. Thus, aniline reacts with AlCl3 to form a
i

R R R R
An

salt. Primary amine Tertiary amine

Due to the positive charge on the N–atom, As a result, extra energy is required to separate the
electrophilic substitution in the benzene ring is molecules of primary amine. Therefore, primary
deactivated. Hence, aniline does not undergo amines have higher boiling point than tertiary
Friedel–Crafts reaction. 1 amine. 1

Long Answer Type Questions-II (5 marks each)

Q. 1. (i) Write the structures of main products when Ans. (i) (a)
aniline reacts with the following reagents : NH2 NH2
(a) Br2 water
Br Br
(b) HCl Br2/H2O
(c) (CH3CO)2O / pyridine
(ii) Arrange the following in the increasing order
of their boiling point :
Br
C2H5NH2, C2H5OH, (CH3)3N
2,4,6-Tribromoaniline1
(iii) Give a simple chemical test to distinguish
between the following pair of compounds :
(CH3)2NH and (CH3)3N
A + U [CBSE Delhi 2015]
306 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

+ Q. 2. (i) Write the structures of main products when

(b)
benzenediazonium chloride reacts with the
following reagents :
(a) H3PO2 + H2O
1 (b) CuCN/KCN

(c) NH2 NHCOCH 3 (c) H 2O

(CH3CO)2 (ii) Arrange the following in the increasing order

Pyridine of their basic character in an aqueous solution :

1
Acetanilide C2H5NH2, (C2H5)2NH, (C2H5)3N

( CH3 )3 N < C2 H 5 NH 2 < C 2 H 5OH (iii) Give a simple chemical test to distinguish
(ii) between the following pair of compounds :
increasing order of b. p.

This order is due to H-bonding. 1 C6H5 – NH2 and C6H5 – NH – CH3

(iii) (CH3)2NH reacts with nitrous acid to form an oily A + U [CBSE OD 2015]

am
layer of N-nitrosamines, which are insoluble in Ans. (i) (a)
CN
(b)
aqueous mineral acids.

gr
CH3 CH3
N H + HO NO N – N = O + H2O OH

le
CH3 CH3
N-nitrosamine
(yellow ppt) te (c) 1+1+1
al
Whereas (CH3)3N reacts with nitrous acid to form
soluble nitrite salts with no ppt. (ii) C2H5NH2 < (C2H5)3N < (C2H5)2NH 1
ci

CH3
(iii) Add CHCl3 and alc. KOH, C6H5–NH2 gives foul
ffi

⊕ –
CH3 N + HONO (CH3)3 NH ONO
smell of isocyanide whereas C6H5–NH–CH3
_o

CH3 Trimethyl ammonium does not (or any other correct test). 1
nitrite 1
ha

Commonly Made Error

Commonly Made Error  (ii) Some students give incorrect sequence of
tS

 Some students only mention the reagents but the compounds.

observations are not given.
ke

Q. 3. Write the structure of A, B, C, D and E in the following reactions:

i

(CH3CO)2O HNO3 + H2SO4 OH– or H+

An

Sn / HCl
C6H5NO2 A B C D
pyridine 288 K

H2SO4

E A
OR
(i) Write the structures of the main products when benzene diazonium chloride reacts with the following reagents:
(a) CuCN
(b) CH3CH2OH
(c) Cu / HCl
(ii) Arrange the following in the increasing order of their basic strength:
CH3NH2, (CH3)2NH, C6H5NH2, C6H5CH2NH2
(iii) Write one chemical test to distinguish between Aniline and Ethyl amine.
A + U [CBSE Foreign Set-1, 2, 3 2017]
Organic compounds containing Nitrogen [ 307
Ans.
O

NH2 NHCOCH3 HN CH3

A B C

NH2 NH3HSO4

D E

NO2
 1 × 5=5
OR
i) ii) iii)
(i) (a) (b) (c)
CN Cl

am
gr
 1+1+1

le
(ii) C6H5NH2 <C6H5CH2NH2 <CH3NH2 < (CH3)2 NH 1
(iii) Add NaNO2+ HCl to both the compounds at 273K followed by addition of phenol. Aniline gives orange dye.1
 te
(Or any other correct test) [CBSE Marking Scheme 2017]
al
Commonly Made Error
ci

 Students write just the name of the test and not the reagent i.e., NaOH and I2.
ffi

Answering Tips
_o

 Specify the reagents involved in distinguishing each compound followed by the response of each.
 Be careful while writing the structures, as the answer must correspond to the question.
ha

Q. 4. An aromatic compound ‘A‘ of molecular formula C7H7ON undergoes a series of reactions as shown below.
tS

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

i ke
An

A [CBSE Delhi 2015]

Ans. Benzene
CH
(C) 6 6
CH3CH2OH
Br2 + KOH NaNO2 + HCl
C6H5CONH2 C6H5NH2 C6H5N2Cl (B)
Aniline 273 K
(A) KI
CuCl3 + NaOH
Benzamide
C6H5I
C6H5NC (E)
(D) Phenyl
Phenyl isocyanide iodide 5
OR
Q. 5. (i) Account for the following:
(a) CH3CHO is more reactive than CH3COCH3 towards reaction with HCN.
308 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

(b) 2-Fluorobutanoic acid is a stronger acid than 3-Fluorobutanoic acid.

(ii) Write the chemical equation to illustrate the following name reactions:
(a) Etard reaction. (b) Rosenmund’s reaction.
(iii) Give the mechanism of cyanohydrin formation when carbonyl compounds react with HCN in the presence of
alkali. A&E + R + A [CBSE SQP 2017]
CH3and electronic factor.
Ans. (i) (a) Steric CH(OCrOHCl2)2 CHO ½+ ½
— — —
(b) Inductive effect decreases with
CS2distance and hence the conjugate base O+2-Fluorobutanoic acid is more stable. 1
H3of
(ii) (a) + CrO2Cl2
CH CH(OCrOHCl2)2 CHO
Toluene— 3 Chromium
— complex Benzaldehyde
—
CS2 H 3 O+
+ CrO2Cl2

Toluene Chromium complex Benzaldehyde

 1
(b) O H2 O
Pd-BaSO4
R Cl R H
O H2 O aldehyde

am
acyl chloride primary  1
– –
Pd-BaSO
(iii) HCN + R
OH Cl : CN +4H2O R H

gr
acyl chloride primary aldehyde
–
-
O

le
+ δ
δ
– H+ CN
C = O + : CN C C

Nucleophile
CN te
OH

Cyanohydrin
al
Tetrahedral
ci

intermediate  1
ffi

 [CBSE Marking Scheme 2017]

_o

Commonly Made Error

(ii) Students write only the reaction taking place.
ha

(iii) Write incorrect shifting of electron.

tS

Answering Tip
(iii) Show the electron transfer through arrows.
ke

Detailed Answer :
i

(i) (a) CH3COCH3 is more sterically hindered than CH3CHO because of the presence of alkyl group on both the sides
An

of carbonyl carbon, making it less reactive due to -I effect. 1

(b) Because the electronegative fluorine atom closer to the –COOH group is exerting stronger inductive effect. 1
Q. 6. (a) Write the reactions involved in the following :
(i) Hoffmann bromamide degradation reaction
(ii) Diazotisation
(iii) Gabriel phthalimide synthesis
(b) Give reasons :
(i) (CH3)2NH is more basic than (CH3)3N in an aqueous solution.
(ii) Aromatic diazonium salts are more stable than aliphatic diazonium salts. R + A&E
OR
(a) Write the structures of the main products of the following reactions :

(i)

(ii)

(iii)
Organic compounds containing Nitrogen [ 309
(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 A + U [CBSE Delhi/OD 2018]
Ans. (i) Ar/R–CONH2 + Br2 + 4NaOH ® Ar/R–NH2 + 2NaBr + Na2CO3 + 2H2O 1
(ii) C6H5NH2 +NaNO2 + 2HCl 273-278k
C6H5N2 Cl+NaCl+2H2O (or any other correct equation) 1
O= O O

=
(iii)
— C— KOH — C— R–X — C—
— N–H — NK — N–R
—C —C —C
=

=
O O O
O O
=

=
– +
—C — C — ONa
—

NaOH(aq)
N–R – +R–NH2 1
— — C — ONa+
=—

=
O
O
(b) (i) Because of the combined factor of inductive effect and solvation or hydration effect. 1

am
(ii) Due to resonance stabilisation or structural representation/resonating structures. 1
OR

gr
(a) (i) C6H5NHCOCH3 1
(ii) C6H5SO2N(CH3)2 1

le
(iii) C6H6 1
(b) Add chloroform in the presence of KOH and heat, Aniline gives a offensive smell while N, N dimethylaniline does
not. (or any other correct test)
(c) C2H5NH2 < C6H5NHCH3 < C6H5NH2
te 1
1
al
 [CBSE Marking Scheme 2018]
ci

Q. 7. (a) Identify A-D

ffi

CH2Cl CH2NO2
—

_o

A Sn/HCl NaOH(aq) Br2

B C
ha

D
tS

CH2NC
ke

—
i
An

(b) Distinguish between the following pair of compounds:

(i) Aniline and Benzylamine.
(ii) Methylamine and Dimethylamine.
(c) Complete the following:
A

OR
(a) Account for the following:
(i) Direct nitration of aniline yields significant amount of meta derivative.
(ii) Primary aromatic amines cannot be prepared by Gabriel phthalimide synthesis.
(b) Carry out the following conversions:
(i) Ethanoic acid into methanamine.
(ii) Aniline to p-Bromoaniline.
(c) Arrange the following in increasing order of basic strength:
Aniline, p-nitroaniline and p-toludine. A&E + A + U [CBSE SQP 2018-2019]
Ans. (a) A = AgNO2 ½
CH2–NH2

B=
½
310 ] Oswaal CBSE Chapterwise & Topicwise Question Bank, Chemistry, Class – XII

O
CH2–C–NH2 ½

C=

D=CHCl3+KOH, Heat. ½
(b) (i)
Experiment Aniline Benzylamine
Azo dye test : A brilliant orange red dye is No dye is formed.
1
Dissolve the amine in HCl, cool observed.
it and then add cold aqueous
solution of NaNO2 and then
solution of b-naphthol
(ii)
Experiment Methylamine Dimethylamine

am
Carbylamine test : A foul smelling substance No dye is formed.
1
To the organic compund add (isocyanide)

gr
chloroform and ethanolic po-

le
tassium hydroxide and heat
(or any other suitable test)
(c) A = CH3CH2CH2NH2
B = CH3CH2CH2OH
te ½
½
al
OR
ci

(a) (i) In strongly acidic medium, aniline is protonated to form the anilium ion which is meta directing. 1
ffi

(ii) Aryl halides do not undergo nucleophile substitution with the anion formed by phathalimide.
Ñ 1
NH3, NaOH + Br2 1
_o

(b) (i) CH3–COOH CH3–CO–NH2 CH3NH2

NH2 NHCOCH3 NHCOCH3 NH2
ha

– –
(CH3CO)2O Br2 OH or H
(ii) 1
tS

Pyridine CH3COOH
ke

Br
(c) p-Nitoraniline < Aniline < p-Toludine. 1
i
An

[CBSE Marking Scheme 2018]

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