Chapter 27

Amines
1. In the chemical reactions, 5. On heating an aliphatic primary amine with
chloroform and ethanolic potassium hydroxide, the
NH2 organic compound formed is [JEE (Main)-2014]
NaNO2 HBF4

HCl, 278 K
o A  oB (1) An alkanol
(2) An alkanediol
the compounds 'A' and 'B' respectively are (3) An alkyl cyanide
[AIEEE-2010]
(4) An alkyl isocyanide
(1) Nitrobenzene and chlorobenzene
6. Considering the basic strength of amines in
(2) Nitrobenzene and fluorobenzene
aqueous solution, which one has the smallest pKb
(3) Phenol and benzene value? [JEE (Main)-2014]
(4) Benzene diazonium chloride and fluorobenzene (1) (CH3)2NH (2) CH3NH2
2. In the chemical reactions (3) (CH3)3N (4) C6H5NH2
NH2 7. In the reaction
NaNO2 CuCN
A B, NH2
HCl, 278 K '
NaNO2/HCl CuCN/KCN
D '
E + N2 ,
The compounds A and B respectively are 0-5°C
[AIEEE-2011]
CH3
(1) Phenol and bromobenzene
(2) Fluorobenzene and phenol the product E is [JEE (Main)-2015]
(3) Benzene diazonium chloride and benzonitrile
COOH
(4) Nitrobenzene and chlorobenzene
3. A compound with molecular mass 180 is acylated (1)
with CH3COCl to get a compound with molecular
mass 390. The number of amino groups present CH3
per molecule of the former compound is
[JEE (Main)-2013]
(2) H3C CH3
(1) 2 (2) 5
(3) 4 (4) 6 CN
4. An organic compound A upon reacting with NH3
gives B. On heating, B gives C. C in presence of (3)
KOH reacts with Br2 to give CH3CH2NH2. A is
[JEE (Main)-2013] CH3
(1) CH3COOH (2) CH3CH2CH2COOH
CH3
(3) CH3 CH COOH (4) CH3CH2COOH
(4)
CH3

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8. In the Hofmann bromamide degradation reaction, 12. The major product obtained in the following reaction
the number of moles of NaOH and Br2 used per is
mole of amine produced are [JEE (Main)-2016] OH
(1) Four moles of NaOH and two moles of Br2 (CH3CO)2O/pyridine (1 eqv.)
room temp.
(2) Two moles of NaOH and two moles of Br2
(3) Four moles of NaOH and one mole of Br2
NH2
(4) One mole of NaOH and one mole of Br2 [JEE (Main)-2019]
9. W hich of the following compounds will form
significant amount of meta product during COCH3
OH
mono-nitration reaction? [JEE (Main)-2017]

NH2 NHCOCH3 (1)

NH2
(1) (2)
OCOCH3

OH OCOCH3 (2)
NH2
(3) (4)

10. The increasing order of basicity of the following

(3) NHCOCH3
compound is [JEE (Main)-2018]

(a) NH2 (b) NH

OH

NH2
(4)
(c) (d) NHCOCH3
NHCH3
NH
13. The major product of the following reaction
(1) (a) < (b) < (c) < (d) (2) (b) < (a) < (c) < (d)
O
(3) (b) < (a) < (d) < (c) (4) (d) < (b) < (a) < (c)
C
11. The tests performed on compound X and their NH2 (i) Br2/h Q
inferences are : (ii) KOH (dil)
Test Inference CH2 CH3

(a) 2,4-DNP test Coloured precipitate [JEE (Main)-2019]

(b) Iodoform test Yellow precipitate O
(c) Azo-dye test No dye formation
Compound ‘X’ is [JEE (Main)-2019] NH
(1) NH (2)

H 3C CH 3 H 3C CH3
N N CH 3

COCH 3 O
(1) (2)
CHO NH
(3) (4) NH
CH3

14. The major product formed in the reaction given

NH 2 OH NH2 below will be

(3) CH 3 (4) NH 2 NaNO 2

CHO
Aq.HCl, 0–5°C

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 [JEE (Main)-2019] 17. A compound ‘X’ on treatment with Br 2/NaOH,
NO 2 provided C3H9N, which gives positive carbylamine
OH test. Compound ‘X’ is [JEE (Main)-2019]
(1) (2)
(1) CH3CH2CH2CONH2
OH (2) CH3COCH2NHCH3
NO2
(3) (4)
(3) CH3CH2COCH2NH2
15. The correct structure of product ‘P’ in the following (4) CH3CON(CH3)2
reaction is 18. Coupling of benzene diazonium chloride with
NEt
Asn  Ser  (CH3 CO)2 O 
3
oP 1-naphthol in alkaline medium will give
(excess)
[JEE (Main)-2019]
[JEE (Main)-2019]
OCOCH 3
O O
|| ||
H
(1) H3C N || N OH
H O N
NHCOCH 3
(1) N
|| HO
O

O
||
NHCOCH 3
O O
|| ||
N
(2) H3C N || H OH
H O OH
OCOCH 3

OCOCH 3
O H O
|| || (2) N
N
H 3C N || OH N
(3) H O NH2
||
O

O
||
NH 2
O O
|| H ||
N
(4) H3C N || OH
H O
N
OCOCH 3
N
16. The correct match between Item I and Item II is
Item I Item II
(3)
(A) Ester test (P) Tyr
(B) Carbylamine test (Q) AsP OH
(C) Phthalein dye test (R) Ser
(S) Lys
[JEE (Main)-2019] OH
(1) (A) o (Q); (B) o(S); (C) o (P)
(2) (A) o (R); (B) o(Q); (C) o (P) (4)
N N
(3) (A) o (Q); (B) o(S); (C) o (R)
(4) (A) o (R); (B) o(S); (C) o (Q)

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19. Which of the following amines can be prepared by 23. Aniline dissolved in dilute HCl is reacted with
Gabriel phthalimide reaction? [JEE (Main)-2019] sodium nitrite at 0ºC. This solution was added
(1) Neo-pentylamine dropwise to a solution containing equimolar mixture
(2) n-butylamine of aniline and phenol in dil. HCl. The structure of
(3) t-butylamine the major product is [JEE (Main)-2019]
(4) Triethylamine
20. In the following compounds, the decreasing order
(1) N N OH
of basic strength will be [JEE (Main)-2019]
(1) NH3 > C2H5NH2 > (C2H5)2NH
(2) C2H5NH2 > NH3 > (C2H5)2NH
(3) (C2H5)2NH > NH3 > C2H5NH2 (2) N N NH2
(4) (C2H5)2NH > C2H5NH2 > NH3
21. The major product in the following reaction is
NH 2 (3) N N NH
N
N base
+ CH3I
N N
H (4) N N O
[JEE (Main)-2019]

NH 2 NHCH 3 24. Hinsberg’s reagent is [JEE (Main)-2019]

N N (1) C6H5SO2Cl
N N
(1) +
(2) (2) (COCl)2
N N N N
H (3) C6H5COCl
H CH 3
(4) SOCl2
NH 2 NH 2 25. The major product of the following reaction is :
N + N
NCH 3 N OH
(3) (4)
ethyl formate (1 equiv.)
N N N N CH3CHCH 2CH 2NH 2
triethylamine
H
CH 3
[JEE (Main)-2019]
22. The major product obtained in the following reaction (1) CH3CH==CH—CH2NH2
is:
OH
NH2 (i) CHCl /KOH 3
(2) CH 3—CH—CH==CH2
(ii) Pd/C/H2
O
CN O
[JEE (Main)-2019] O H

H (3) CH3CHCH 2CH2NH2

H
OH
NCH3 NCH3
(4) CH3CHCH 2CH2NHCHO
(1) (2)
26. Ethylamine (C 2 H 5 NH 2) can be obtained from
CN OH N-ethylphthalimide on treatment with :
H2N OH
[JEE (Main)-2019]
H
(1) NH2NH2
H
NCH3 NCHCl2 (2) NaBH4
(3) (4) (3) H2O

O (4) CaH2
CN CN OH
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27. Which of the following is NOT a correct method of 31. In the following reaction sequence:
the preparation of benzylamine from NH2
cyanobenzene? [JEE (Main)-2019]
(1) (i) SnCl2 + HCI(gas) Ac2O Br2
A B
AcOH
(ii) NaBH4
(2) H2/Ni CH3
(3) (i) LiAlH4 the major product B is: [JEE (Main)-2020]
(ii) H3O+ NHCOCH3 NHCOCH3
(4) (i) HCI/H2O Br
(ii) NaBH4 (1) (2)
28. Benzene diazonium chloride on reaction with Br
aniline in the presence of dilute hydrochloric acid CH3 CH3
gives : [JEE (Main)-2019]
NHCOCH3 NHCOCH3
(1) — N == N — NH — COCH3 Br
(3) (4)

(2) — N == N —
CH3 CH2Br
H2N
32. The major product Z obtained in the following
reaction scheme is
(3) — N == N — — NH2 NH2

NaNO /HCl Cu Br HNO

 2
o X 
2 2
o Y 3
oZ
(4) —— — NH2 273278 K H SO 2 4

Br
29. Arrange the following amines in the decreasing
[JEE (Main)-2020]
order of basicity [JEE (Main)-2019]
NO2 Br

O2 N
N N N (1) (2)
H H Br Br Br
I II III
Br
(1) III > II > I (2) I > III > II NO2
(3) III > I > II (4) I > II > III
30. Consider the following reaction: (3) (4) Br Br
Br
CH3 NO2
—
N + Na SO3
— —
N2 Cl NO2
CH3
–
33. Consider the following reactions,
OH
 o ' X'
The product ‘X’ is used [JEE (Main)-2020] (i) NaNO 2/HCl, 0-5 °C
(ii) E-naphthol/NaOH
(1) In acid base titration as an indicator
Colored Solid
(2) In protein estimation as an alternative to
ninhydrin
[P]
Br2/H2O
(3) In laboratory test for phenols C7H6NBr3
(4) As food grade colourant
The compound [P] is [JEE (Main)-2020]
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 NH2 NH2 CH2 NH2 NH2
NH2 (1)
CH2 CH3 , ,
CH3 CH3 CH2 CH3
(1) (2)

CH2 CH3 CH2 NHCH3 NH2

CH3
(2)
, ,
CH2 CH3
NHCH3 NH2 NH2

CH2CH3 NHCH2CH3 NH2

(3) (4)
(3) , ,
H2 N CH2CH3
CH3 CH3

34. The Kjeldahl method of Nitrogen estimation fails for NH2 CH2NHCH3 CH2CH3
which of the following reaction products? (4)
CH2CH3 , , HN
[JEE (Main)-2020] 2

NO2 36. In the following reaction sequence, [C] is

NH2
(a) Sn/HCl
(i) NaNO 2 + HCl, 0-5°C
[A]
(ii) Cu 2Cl2 + HCl

CN CH3
Cl Na  dry ether
(b) LiAlH4 
2
hQ
o [B]  o [C]
(Major Product)

[JEE (Main)-2020]
CH2CN

(c) (i)SnCl2 + HCl (1) Cl CH2 CH2 Cl

(ii)H2O

NH2 (2) Cl CH2 CH2 Cl

NaNO2
(d) HCl

(1) (a), (c) and (d) (2) (a) and (d) (3) CH2 CH2
(3) (c) and (d) (4) (b) and (c)
Cl Cl
35. Three isomers A, B and C (mol. formula C8H11N) give
the following results
(4) CH3 CH3
Diazotization
A and C o
37. The most appropriate reagent for conversion of
(i) Hydrolysis R (product of A)
P  Q o  C2H5CN into CH3CH2CH2NH2 is [JEE (Main)-2020]
(ii) Oxidation S (product of C)
(KMnO4  H ) (1) NaBH4

(2) CaH2
R has lower boiling point than S
(3) Na(CN)BH3
C H SO Cl
B 
6 5 2
o alkali-insoluble product
(4) LiAlH4
A, B and C, respectively are [JEE (Main)-2020]

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38. The final major product of the following reaction is [JEE (Main)-2020]
Me (1) (i)-(b), (ii)-(d), (iii)-(e), (iv)-(a)
(i) Ac 2O/Pyridine

o (2) (i)-(d), (ii)-(c), (iii)-(e), (iv)-(a)
(ii) Br2 , FeCl3
[JEE (Main)-2020] (3) (i)-(b), (ii)-(a), (iii)-(c), (iv)-(d)
(iii) OH / '
NH2 (4) (i)-(d), (ii)-(c), (iii)-(b), (iv)-(e)
41. The increasing order of pK b for the following
Br compounds will be
Me Me
(1) (2) N
Br NH2 CH NH CH3NHCH 3
NH2 (A) N NH (C)
NH2

(B)
Me Br
Me [JEE (Main)-2020]
(3) (4) (1) (B) < (C) < (A) (2) (B) < (A) < (C)
Br NH2 (3) (C) < (A) < (B) (4) (A) < (B) < (C)
NH2
42. The decreasing order of basicity of the following
39. Which of the following compounds can be prepared
in good yield by Gabriel phthalimide synthesis? amines is
[JEE (Main)-2020]
NH 2
N
NH2

(1) (I) (II)

O NH 2
CH2—C—NH2 N
H
(2) (IV)
(III)

[JEE (Main)-2020]
CH2NH2 (1) (III) > (I) > (II) > (IV)
(2) (II) > (III) > (IV) > (I)
(3) (I) > (III) > (IV) > (II)
(3)
(4) (III) > (II) > (I) > (IV)
43. The increasing order of basicity of the following
(4) CH3—CH2—NHCH3 compounds is
40. Match the following :
N
Test/Method Reagent
(i) Lucas Test (a) C6H5SO2Cl/
aq. KOH N N N
N
(ii) Dumas method (b) HNO3/ H H H
AgNO3 (A) (B) (C) (D)
(iii) Kjeldahl’s (c) CuO/CO2 [JEE (Main)-2020]
method (1) (B) < (A) < (D) < (C)
(iv) Hinsberg test (d) Conc. HCl (2) (D) < (A) < (B) < (C)
and ZnCl2 (3) (B) < (A) < (C) < (D)
(e) H2SO4 (4) (A) < (B) < (C) < (D)
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44. ‘A’ and ‘B’ in the following reactions are : (1) Formation of anilinium ion
(2) Low temperature
NH2
(3) –NO2 substitution always takes place at meta-
position
NaNO2/HCl SnCl2/HCl/H 3O+
(A) (B) (4) –NH2 group is highly meta-directive
KCN
46. What is the correct sequence of reagents used for
converting nitrobenzene into m-dibromobenzene?
[JEE (Main)-2021]
NO2 Br
+ –
N2CI CI

Br
(1) (A) : (B) :
[JEE (Main)-2021]

NaNO 2 HCl KBr H+

(1)
CN CHO
Sn/HCl Br2 NaNO 2 NaBr
(2)

(2) (A) : (B) : Sn/HCl KBr Br 2 H+

(3)

Br2/Fe Sn/HCl NaNO 2/HCl

(4)
+ –
N2CI CHO CuBr/HBr

47. The diazonium salt of which of the following

(3) (A) : (B) : compounds will form a coloured dye on reaction
with E-Naphthol in NaOH? [JEE (Main)-2021]

CH3
CN CI
N — CH3
(1)
(4) (A) : (B) :

CH2NH2
45. In the following reaction the reason why meta-nitro (2)
product also formed is :

NH2 NH2 NH2 NH2

NH2
NO2
Conc. HNO3
+ +
(3)
Conc. H 2SO4, 288 K
NO 2
NO2
[A] [B] [C ] NH— CH3
51% 47% 2%
(4)
[JEE (Main)-2021]

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48. Match List - I and List - II. [JEE (Main)-2021]
List - I List - II (1) C only (2) B only
(3) A only (4) A and B
O
|| 51. Carbylamine test is used to detect the presence of
(a) R  C  Cl o R  CHO (i) Br2/NaOH primary amino group in an organic compound.
Which of the following compound is formed when
(b) R – CH2 – COOH o (ii) H2/Pd – BaSO4 this test is performed with aniline?
R  CH  COOH [JEE (Main)-2021]
|
Cl CONH2 CN
(1) (2)
O
NHCH 3 NC
(c) R – C – NH 2 o R – NH 2 (iii)Zn(Hg)/Conc. HCl (3) (4)
O
NH 2
(d) R – C – CH 3 o R – CH2 – CH 3 (iv) Cl2/Red P, H2O
52. HNO 3 , H2SO 4
Choose the correct answer from the options given
below: [JEE (Main)-2021] 288 K

(1) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii) NH 2 NH2 NH 2

(2) (a)-(ii), (b)-(iv), (c)-(i), (d)-(iii) NO 2
+ +
(3) (a)-(ii), (b)-(i), (c)-(iv), (d)-(iii)
NO 2
(4) (a)-(iii), (b)-(iv), (c)-(i), (d)-(ii)
NO2
49. The total number of amines among the following (A) (B) (C)
which can be synthesized by Gabriel synthesis is
_____. [JEE (Main)-2021] Correct statement about the given chemical
reaction is : [JEE (Main)-2021]
CH
(A) CH3 CH – CH2 – NH2 (B) CH CH NH (1) The reaction will form sulphonated product
3
3 2 2
instead of nitration.
CH2 NH2 NH2
(2) Reaction is possible and compound (B) will be
(C) (D)
the major product.
(3) Reaction is possible and compound (A) will be
50. Which of the following reaction/s will not give p-
major product.
aminoazobenzene?
:

(4) NH 2 group is ortho and para directive, so

NO 2
product (B) is not possible.
(i) Sn/HCl 53. An amine on reaction with benzenesulphonyl
A.
(ii) HNO 2 chloride produces a compound insoluble in alkaline
(iii) Aniline
solution. This amine can be prepared by
ammonolysis of ethyl chloride. The correct
NO 2 structure of amine is : [JEE (Main)-2021]

(i) NaBH 4 H
B.
(ii) NaOH (1) CH3 CH2 CH2 N — CH2 CH3
(iii) Aniline

(2) CH3CH2NH2
NH2 (3) CH3CH2CH2NHCH3
(i) HNO 2 NH — CH2 CH2CH3
C.
(i i) Anili ne, HCl
(4)

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54. A. Phenyl methanamine
N2+Cl–
B. N,N-Dimethylaniline
C. N-Methyl aniline (2) X - ; A - H 2O/NaOH
D. Benzenamine
Choose the correct order of basic nature of the
above amines. [JEE (Main)-2021] N+2 Cl–
(1) A > C > B > D (2) D > B > C > A
(3) D > C > B > A (4) A > B > C > D (3) X - ; A - H 2O/'

55. Ceric ammonium nitrate and CHCl3/alc. KOH are

used for the identification of functional groups
present in _____ and _____ respectively. NO 2

[JEE (Main)-2021]
(4) X - ; A - H 2O/'
(1) Alcohol, phenol (2) Amine, phenol
(3) Amine, alcohol (4) Alcohol, amine
58. Ammonolysis of Alkyl halides followed by the
56. Which of the following reaction DOES NOT involve treatment with NaOH solution can be used to
Hoffmann bromamide degradation? prepare primary, secondary and tertiary amines.
[JEE (Main)-2021] The purpose of NaOH in the reaction is

O [JEE (Main)-2021]
CH 2 – C – CH 3
+ CH2 – NH 2 (1) To remove basic impurities
i) Br2, NaOH/H
(1) ii) NH3 /'
iii) LiAlH 4/H2 O
(2) To activate NH3 used in the reaction
(3) To remove acidic impurities
CN NH2
i) KOH, H2O
(2) (4) To increase the reactivity of alkyl halide
ii) Br2, NaOH
59. Which of the following is least basic?
O
NH2 [JEE (Main)-2021]
Cl i) NH3 , NaOH
(3) xx
ii) Br2 , NaOH
(1) (CH3 CO)NHC 2H5
O
xx
CH2 – C – NH2 CH 2 – NH2 (2) (CH3 CO)2 NH
(4) Br 2, NaOH
xx
(3) (C 2H5 )2 NH
NH 2 OH
xx
NaNO2, HCl “A” (4) (C2H5 )3 N
57. “X”
273 - 278 K
Major Product
60. Which of the following reaction is an example of
ammonolysis? [JEE (Main)-2021]
In the above chemical reaction, intermediate “X”
and reagent/condition “A” are [JEE (Main)-2021] (1) C6H5 CH2Cl  NH3 
o C6H5CH2NH2

NO 2 
(2) C6H5NH2 
HCl
o C 6H5 NH3 Cl–
(1) X - ; A - H 2O/NaOH
(3) C6H5 COCl  C6H5NH2 
o C6H5 CONHC6H5

>H@
(4) C6H5 CH2 CN o C6H5 CH2CH2NH2

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61. Hoffmann bromamide degradation of benzamide 63. Primary, secondary and tertiary amines can be
gives product A, which upon heating with CHCl3 separated using [JEE (Main)-2021]
and NaOH gives product B.
The structures of A and B are: (1) para-Toluene sulphonyl chloride
NH 2 NH2 (2) Acetyl amide
CHO (3) Chloroform and KOH
(1) A – B–
(4) Benzene sulphonic acid

Br Br
NH 2
NH2 NC
NaNO 2, HCl
64. “X”
(2) A – B– 273K - 278 K (Major Product)

O O
NH2 NH2
H3 C CH3
CHO N
(3) A – B–

Br Br “Y”
(Major Product)
NH2 NH2
CHO
(4) A – B– Considering the above reaction, X and Y
respectively are [JEE (Main)-2021]
[JEE (Main)-2021]
OCH3 Cl
N
62. C7H7N2OCl + C2H5OH + N2 + “X” + “Y” and N
(A)
(1)
In the above reaction, the structural formula of (A), N
“X” and “Y” respectively are [JEE (Main)-2021] CH3
CH 3
N2+ OCH 3
O
–
, CH 3 C H , H2O N2+Cl
(1)
N
Cl N
(2) and
N2+ Cl – CH 3
N
O
, CH 3 C H , HCl CH3
(2)
OCH3
N2+Cl –
N2+ Cl –
N CH3
and N N
(3) CH3
(3) , H H , HO
2
H O H
OCH 3
Cl
N+
2 OCH 3 N CH3
and N N
(4) CH3
(4) , H H ,
HCl
H O H
Cl

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 NH 2 NH2 NH2 NH 2
NO 2 CH 3
65.
HNO3, H2SO 4
+ + N
288 K CH 3
NO 2
NO2 (3) HO 3S N=N
A B C

Consider the given reaction, percentage yield of :

[JEE (Main)-2021] CH 3
(4) HO 3S N
(1) C > B > A (2) C > A > B CH 3
(3) B > C > A (4) A > C > B
66. An organic compound “A” on treatment with O
benzene sulphonyl chloride gives compound B. B KOBr
is soluble in dil. NaOH solution. Compound A is NH2 A
69. (major product)
[JEE (Main)-2021]
(1) C6H5 — N — (CH3)2
Br
(2) C6H5 — CH2NHCH3

(3) C6H 5 — CH — NH2 O

CH3 LiAlH4
NH2 +
B
H 3O (major product)
(4) C6H5 — NHCH2CH3
67. In the reaction of hypobromite with amide, the
carbonyl carbon is lost as [JEE (Main)-2021] Br

(1) CO32 (2) HCO3 In the above reactions, product A and product B
respectively are [JEE (Main)-2021]
(3) CO2 (4) CO

NH2
NH2 NH2
(1)
,
NaNO2, HCl
68. A
273 - 278 K (major product) Br

SO3H NH2
NH2
CH 3 (2)
N ,
CH 3

B NH2
273 K NH2
(major product)
(3) ,
Consider the above reaction, compound B is :
Br
[JEE (Main)-2021]
CH 3
NH2
(1) HO 3S N=N N NH2
CH 3
(4) ,
CH3
(2) N=N N Br Br
CH3

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70. Compound A is converted to B on reaction with CHCl3 73. Given below are two statements, one is labelled as
and KOH. The compound B is toxic and can be Assertion (A) and other is labelled as Reason (R).
decomposed by C. A, B and C respectively are Assertion (A): Gabriel phthalimide synthesis
cannot be used to prepare
[JEE (Main)-2021] aromatic primary amines.
(1) Secondary amine, isonitrile compound, conc. Reason (R) : Aryl halides do not undergo
NaOH nucleophilic substitution reaction.
In the light of the above statements, choose the
(2) Secondary amine, nitrile compound, conc. correct answer from the options given below :
NaOH
[JEE (Main)-2021]
(3) Primary amine, isonitrile compound, conc. HCl (1) (A) is false but (R) is true
(4) Primary amine, nitrile compound, conc. HCl (2) Both (A) and (R) are true and (R) is correct
explanation of (A)
(3) (A) is true but (R) is false
N2 Cl– (4) Both (A) and (R) are true but (R) is not the
CH 2CH3 correct explanation of (A)
B, Anhyd. AlCl 3
+ A + H 2O 74. What is the major product “P” of the following
71.
reaction ?
Major Product
CH 3 (i) NaNO 2,HCl, 278 K
P
In the chemical reactions given above A and B (ii) H2O (major product)
NH 2
respectively are [JEE (Main)-2021]
[JEE (Main)-2021]
(1) CH3CH2Cl and H3PO2
OH CH 3
(2) H3PO2 and CH3CH2OH
(1) † – (2)
(3) H3PO2 and CH3CH2Cl N 2 Cl Cl

(4) CH3CH2OH and H3PO2 CH 3 CH 3

72. Which one of the following reactions does not (3) (4)
CH 3 OH
occur? [JEE (Main)-2021]
75. W hich one of the products of the following
NH2 NHCOCH 3 reactions does not react with Hinsberg reagent to
form sulphonamide? [JEE (Main)-2021]
(1) + (CH 3 CO)2O/Pyridine CN

C2H5OH
(1) + Na/Hg
NH2 NH2

NO2
+ AlCl3 + CH 3Cl
(2)
CN
CH3
(2) + SnCI2 + HCI
NH 2 NH2
CN
(3) + HNO 3/H 2SO4
H 3O
(3) + LiAIH 4
NO2
CHO
NH 2 NH2
CN

+ H 2SO4
(4) (4) + H2/Ni
CH3
SO3H
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 † – 79. The correct sequence of correct reagents for the
Sn + HCl C6H5N2Cl
76. C6H5NO2 “A” P following transformation is
†
H (Yellow coloured
Compound ) NO2 OH
Consider the above reaction, the Product “P” is :
[JEE (Main)-2021]

N=N Cl
(1)
[JEE (Main)-2021]
NH 2
(1) (i) Fe, HCl
H (ii) NaNO2, HCl, 0°C
|
N (iii) H2O/H+
(2) (iv) Cl2, FeCl3
(2) (i) Fe, HCl
(ii) Cl2, HCl
N=N NH 2
(iii) NaNO2, HCl, 0°C
(3)
(iv) H2O/H+
(3) (i) Cl2, FeCl3
H
| (ii) NaNO2, HCl, 0°C
N=N–N (iii) Fe, HCl
(4)
(iv) H2O/H+
(4) (i) Cl2, FeCl3
77. In gaseous triethyl amine the “– C – N – C –” bond
angle is _______ degree. [JEE (Main)-2021] (ii) Fe, HCl
78. What is A in the following reaction ? (iii) NaNO2, HCl, 0°C
[JEE (Main)-2021]
(iv) H2O/H+

NH 2
K
(CH 3CO)2O
80. P
NH2 (Major
product)
O
O
The major product in the above reaction is :
(1) NH
[JEE (Main)-2021]
O
NHCOCH3 NH 2
CH2OH
(2) (1) NH2
(2)
NHCOCH3

O O
O

NH — CH 2
(3) NH 3 CH3 COO
–
NHCOCH3

CH2NH2 (3) (4) NHCOCH3

NHCOCH3
(4) O O

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81. The major product of the following reaction is :
O

CH3 O (i) alcoholic NH 3 OH O CH3

(ii) NaOH, Br2
CH3 – CH – CH2 – CH2 – C – Cl
(iii) NaNO2, HCl
(iv) H2O A: , B:
(1)
Major product
NH2 NH2
[JEE (Main)-2021]

(1) CH3 – CH – CH2 – CH2 OH O O

CH3 O O
CH3 CH3

Br
(2) A : , B:
(2) CH3 – CH – CH – CH2OH
CH3 CH3
NH2 NH

(3) CH3 – CH – CH2 – CH2 – Cl O

CH3
OH OH O
(4) CH3 – CH – CH2 – CH 2 – CH2OH
CH3
CH3 (3) A : , B:

82. Which of the following is not a correct statement

NH2 NH2
for primary aliphatic amines?
[JEE (Main)-2021] OH OH
(1) Primary amines on treating with nitrous acid
solution form corresponding alcohols except (4) A : , B:
methyl amine.
(2) The intermolecular association in primary NH2 NH CH3
amines is less than the intermolecular
association in secondary amines. O

(3) Primary amines can be prepared by the 84. The major products A and B in the following set of
Gabriel phthalimide synthesis. reactions are [JEE (Main)-2021]
(4) Primary amines are less basic than the LiAlH4 OH H3O
+

A + B
secondary amines. H3O CN H2SO4

83. The correct structures of A and B formed in the

OH OH
following reactions are : (1) A = , B=
OH CHO

OH OH OH
O O (2) A = , B=
NH2 CHO
H2 /Pd O B
C 2H 5OH
A 1.0 eq.
OH
(3) A = , B= COOH
NO2
NH2

OH OH
[JEE (Main)-2021] (4) A = , B=
CHO CO2 H

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85. The total number of reagents from those given 87. Identify A in the following reaction.
below, that can convert nitrobenzene into aniline is [JEE (Main)-2021]
_____. (Integer answer) [JEE (Main)-2021]
NH2
I. Sn – HCl
K2Cr2O 7
II. Sn – NH4OH A
III. Fe – HCl
IV. Zn – HCl NO2 NO2

V. H2 – Pd (1) (2) H

VI. H2 – Raney Nickel

O
86. The major products A and B formed in the following
NH2
reaction sequence are : [JEE (Main)-2021]
(3) (4)
NH2
O O KO
O
O Br2 , CH3COOH
A Room Temperature
B 88. Which one of the following gives the most stable
Diazonium salt? [JEE (Main)-2021]

O O NHCH3
NH CH3 NH CH3
(1)

(1) A = , B=
Br
NH2

O O (2)
CH3
NH CH3 NH CH3

CH3
(2) A = , B=
(3) CH3 C NH2
H
Br
(4) CH3 — CH2 — CH2 — NH2
89. 1.86 g of aniline completely reacts to form
NH 2 NH2 acetanilide. 10% of the product is lost during
purification. Amount of acetanilide obtained after
Br Br purification (in g) is ______ × 10–2.
(3) A = , B= [JEE (Main)-2021]

COCH 3 COCH3 90. O

C
Cl + C6H5NHC6H5
NH 2 NH2

Br 0.140 g 0.388 g
(4) A = , B=
O
C6H5 – C – N – (C 6H5)2
COCH 3 COCH3
0.210 g

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 Consider the above reaction. The percentage yield 95. W hich statement is NOT correct for p-
of amide product is ____. (Round off to the Nearest toluenesulphonyl chloride?
Integer). [JEE (Main)-2022]
(Given : Atomic mass : C : 12.0 u, H : 1.0 u, N : (1) It is known as Hinsberg’s reagent
14.0 u, O : 16.0 u, CI : 35.5 u) (2) It is used to distinguish primary and
secondary amines
[JEE (Main)-2021]
(3) On treatment with secondary amine, it leads
91. A reaction of 0.1 mole of Benzylamine with to a product, that is soluble in alkali
bromomethane gave 23 g of Benzyl trimethyl (4) It doesn’t react with tertiary amines
ammonium bromide. The number of moles of
96. The final product ‘C’ in the following series of
bromomethane consumed in this reaction are
n × 10–1, when n = _____ reactions

(Round off to the Nearest Integer).

[Given : Atomic masses : C : 12.0 u, H : 1.0 u, N
: 14.0 u, Br : 80.0 u] [JEE (Main)-2021]
92. Which one of the following compounds will liberate
CO2, when treated with NaHCO3? [JEE (Main)-2022]
[JEE (Main)-2021]

(1) CH3NH2 (2) (CH3 )3NHCl

(1)
O
(3) CH3 —C—NH2 (4) (CH3 )4NOH

93. Phenol on reaction with dilute nitric acid, gives two

products. Which method will be most efficient for
large scale separation? (2)
[JEE (Main)-2022]
(1) Chromatographic separation
(2) Fractional crystallisation
(3) Steam distillation
(4) Sublimation (3)

94. The reaction of R C NH2 with bromine and KOH

O
gives RNH2 as the end product. Which one of the
(4)
following is the intermediate product formed in this
reaction?
97. Given below are two statements:
[JEE (Main)-2022]
Statement-I : In Hofmann degradation reaction, the
(1) R C NH Br migration of only an alkyl group takes place from
O carbonyl carbon of the amide to the nitrogen atom.
(2) R – NH – Br Statement-II : The group is migrated in Hofmann
(3) R – N = C = O degradation reaction to electron deficient atom.

(4) R C NBr 2 In the light of the above statements, choose the most
O appropriate answer from the options given below:

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 [JEE (Main)-2022] (A) o-Nitroaniline and p-nitroaniline are the
(1) Both Statement I and Statement II are correct predominant products.
(2) Both Statement I and Statement II are
incorrect (B) p-Nitroaniline and m-nitroaniline are the

(3) Statement I is correct but Statement II is predominant products.

incorrect
(C) HNO3 acts as an acid.
(4) Statement I is incorrect but Statement II is
correct (D) H2SO4 acts as an acid.

98. Identify the major product formed in the following Choose the correct option.

sequence of reactions: [JEE (Main)-2022]

(1) (A) and (C) are correct statements.
(2) (A) and (D) are correct statements.
(1)Br2 /H2O (3) (B) and (D) are correct statements.

(2)NaNO2 /HCl
o
(3)H3PO2 (4) (B) and (C) are correct statements.

[JEE (Main)-2022]
101.

Consider the above reactions, the product A and

(1) (2)
product B respectively are
[JEE (Main)-2022]

(3) (4) (1)

99. A primary aliphatic amine on reaction with nitrous

acid in cold (273 K) and there after raising
tem perature of reaction m ixture to room
temperature (298 K), gives (2)
[JEE (Main)-2022]
(1) nitrile (2) alcohol
(3) diazonium salt (4) secondary amine

100. With respect to the following reaction, consider the

(3)
given statements:

(4)

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102. In Friedel-Crafts alkylation of aniline, one gets 105. The correct sequential order of the reagents for the
[JEE (Main)-2022] given reaction is
(1) Alkylated product with ortho and para
substitution.
(2) Secondary amine after acidic treatment.
(3) An amide product.
(4) Positively charged nitrogen at benzene ring.
103. An organic compound ‘A’ on reaction with NH3
followed by heating gives compound B. Which on [JEE (Main)-2022]
further strong heating gives compound (1) HNO2, Fe/H , HNO2, KI, H2O/H+
+

C(C8H5NO2). Compound C on sequential reaction (2) HNO2, KI, Fe/H+, HNO2, H2O/warm
with ethanolic KOH, alkyl chloride and hydrolysis
(3) HNO2, KI, HNO2, Fe/H+, H2O/H+
with alkali gives a primary amine. The compound
(4) HNO2, Fe/H+, KI, HNO2, H2O/warm
A is :
106. Match List I with List II.
[JEE (Main)-2022]
List- I List-II

A. Benzenesulphonyl I. Test for primary

(1) (2) Chloride amines

B. Hoffmann bromamide II. Anti Saytzeff

reaction

C. Carbylamine reaction III. Hinsberg reagent

(3) (4)
D. Hoffmann orientation IV. Known reaction of
Isocyanates

104. Given below are two statements: one is labelled as Choose the correct answer from the options given
Assertion (A) and the other is labelled as Reason below:
(R).
[JEE (Main)-2022]
Assertion (A) : Experimental reaction of CH3Cl
(1) A-IV, B-III, C-II, D-I
with aniline and anhydrous AlCl3 does not give o
and p-methylaniline. (2) A-IV, B-II, C-I, D-II
Reason (R) : The -NH2 group of aniline becomes (3) A-III, B-IV, C-I, D-II
deactivating because of salt formation with (4) A-IV, B-III, C-I, D-II
anhydrous AlCl3 and hence yields m-methyl aniline
as the product. 107. Given below are two statements: one is labelled as
In the light of the above statements, choose the Assertion A and the other is labelled as Reason R
most appropriate answer from the options given
below : Assertion A : Aniline on nitration yields ortho,
[JEE (Main)-2022] meta & para nitro derivatives of aniline.
(1) Both (A) and (R) are true and (R) is the
correct explanation of (A). Reason R : Nitrating mixture is a strong acidic

(2) Both (A) and (R) are true but (R) is not the mixture.
correct explanation of (A).
In the light of the above statements, choose the
(3) (A) is true, but (R) is false.
correct answer from the options given below.
(4) (A) is false, but (R) is true.

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 [JEE (Main)-2022] + –
(1) Both A and R are true and R is the correct N NCl
explanation of A NaOH
110. + ‘A’ Product
(2) Both A and R are true but R is NOT the (Orange-red dye)
correct explanation of A
(3) A is true but R is false Which among the following represent reagent ‘A’?
(4) A is false but R is true [JEE (Main)-2022]
108. W hich among the following is the strongest
Bronsted base?
[JEE (Main)-2022]
(1) (2)

(1) (2)

(3) (4)

(3) (4)
111. The Hinsberg reagent is
[JEE (Main)-2022]

109.
(1) (2)

Consider the above reaction, the compound ‘A’ is:

[JEE (Main)-2022] O

= +
N K
(3) (4)
(1) O

112. Among the following structures, which will show

the most stable enamine formation?

(2) (Where Me is –CH3)

[JEE (Main)-2022]

(3) (1) (2)

(3) (4)
(4)

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113. The correct stability order of the following [JEE (Main)-2022]
diazonium salt is
(1) (A) > (B) > (C) > (D)

(2) (A) > (C) > (D) > (B)

(3) (C) > (A) > (D) > (B)

(4) (C) > (D) > (B) > (A)

‰‰‰

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Chapter 27
Amines
+ +
1. Answer (4) NH2 NH2 NH2

NH2 N { NCl F
NaNO2 HBF4 +
HCl , 278 K
NH2 NH2
'

Benzene diazonium Fluorobenzene

chloride

Out of (CH3)3N, CH3NH2, (CH3)2NH . (CH3)2NH is

2. Answer (3)
+ – most basic due to +I effect and hydrogen bonding
NH2 N2Cl CN in H2O.
NaNO2 CuCN
HCl ' +I effect
CH3
3. Answer (2)
N
R  NH2  CH3COCl o RNHCOCH3  HCl
M M 42 H3C H
+I effect
If the increase in molecular mass is 42, the O
reactant has one NH2 group. Hydrogen H H
Actual increase in molecular mass = 390 –180 bonding

= 210
210 7. Answer (3)
Number of NH2 groups 5
42 NH2
+
N 2Cl
–
CN
4. Answer (4)
NaNO2/HCl CuCN/KCN
0°C - 5°C '
+ N2
CH3CH2COOH + NH3 CH3CH2CO2NH4
(A) (B) ' CH3 CH3 CH3
KOH + Br2
CH3CH2NH2 CH3CH2CONH2 + H2O (D) (E)
(C)
8. Answer (3)
5. Answer (4)
CHCl3 /KOH R – C – NH2 + Br2 + 4NaOH o
R – CH2 – NH2 
C2H5OH
o R– CH – NC
2
O
6. Answer (1)
RNH2 + Na2CO3 + 2NaBr + 2H2O
Among C6H5NH2, CH3NH2, (CH3)2NH,
From the reaction it can easily be said 4 moles of
(CH3)3N . C6H5NH2 is least basic due to resonance. NaOH and 1 mole of Br2 is used in this reaction.

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9. Answer (1) 12. Answer (4)

NH2 NH3 OH
O
H+ NO2
NH2 CH3—C—O—C—CH

O
NH3 NH3 NH3 Nitrogen is
more nucleophilic
NO2 OH
+ +
NO2 + CH3COOH
(51%) (2%) NH
NO2
(47%) O==C—CH
10. Answer (3) 13. Answer (1)
NH2 Protonation NH3
(a) 3 O O
1° & sp

NH Protonation
NH2
C – NH2 C – NH2
Br2
(b) 2 O hQ
O
sp CH2 – CH3 CH – CH3

–
NH2 NH2
+
NH2 Br
Protonation
OH –
+
(c) NH NH2 NH2
O
O
[Equivalent resonance] C – NH
–
O NH O
Protonation
CH – CH3
(d) NHCH3 NH2–CH3

–
CH3
2° & sp3 Br
? Correct order of basicity : b < a < d < c
11. Answer (1) 14. Answer (4)
H3C CH3 H3C CH3
N N NaNO2 (+)
O CH2
|| NH2
C C N —NH aqHCl
||

CH3 |
2,4-DNP CH3 NO2 ring
expansion

I2 / NaOH
NO2
CH3 OH
H3C (+)
N
O
||
C
O –Na+
+ CHI 3 15. Answer (4)

H
N(CH3)2 Asn Ÿ NH2 – C – CH2 – C – COOH
COCH3 O NH2
will not give positive dye test, due

to the presence of an electron withdrawing group.

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 H 19. Answer (2)
Ser Ÿ HO – CH2 – C – COOH Primary amines are prepared by Gabriel pthallimide
NH2 synthesis.
Asn – Ser CO CO
NK + C 4H 9Cl N – C4H9
H CO CO
Ÿ NH2 – C – CH2 – C – C – N – C – CH2 – OH Pot. pthallimide NaOH(aq)
O NH2 O COOH
COONa
Excess(CH3CO)2O + n-C4H9NH2
COONa
20. Answer (4)
H H
NH2 – C – CH2 – C – C – NH – C – CH2 – O – CO –CH3 Correct order of Kb value

O CH3CONH O COOH <<

(C2H5 )2 N > (C2H5 )3N > NH3
16. Answer (1)
In aqueous medium sec. amines are most basic.
3°amines are more basic than NH3 as +I factor
dominate over steric factor.
21. Answer (4)
(P) NH2 NH2
N N
N Base N CH3 – I
XN2
N N N N
(–)
(Q) AsP – –CH2–COOH – Ester test (A)
H
(R) Ser – –CH2–OH – Ester test (A) NH2
(S) Lys – –(CH2)4–NH2 – Carbylamine test (B) N
N
17. Answer (1)
N N
C3H9N gives carbylamine test.
? C3H9N is primary aliphatic amine. CH3
In the given compound, H-atom attached to
X + Br2 + NaOH 
o C 3H 9N
Primary amine secondary N-atom is more acidic. The base
removes the more acidic H-atom and the conjugate
? X is acid amide having formula base of the given compound attacks at CH3 group
O to give the final product shown above.
22. Answer (1)
CH 3 — CH2— CH2 — C — NH 2
NH2 NC
CHCl3, KOH
18. Answer (3) O O
CH3
+
N Cl
2
–
OH OH CN O CN O

OH
–
H2/Pd C
+
NH CH3
Coupling reaction N = N—C 6 H5 O

OH
H2N

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23. Answer (2) 27. Answer (4)
O
In acidic medium aniline is more reactive than
CN C—NH 2 COOH
phenol that’s why electrophilic aromatic substitution
HCl
or
+ H 2O
of Ph  N2 takes place with aniline (depending upon
temperature )
NaBH 4
NH2 N==N XX
28. Answer (3)
24. Answer (1) + –
N2 Cl NH2
Hinsberg’s reagent is benzenesulphonyl chloride. +
H
+
SO2Cl

N=N NH2

p-aminoazobenzene
25. Answer (4)
29. Answer (3)
OH O
..
CH3 CH CH2 CH2 NH2 + H C O C2 H5

–
N most basic
OH O
+ H
CH3 CH CH 2 CH2 NH C O C 2H5

H H (C 2H 5)3N

OH O lone pair is not involved in resonance but

N
CH3 CH CH 2 CH2 NH C H + C2 H5OH
N atom is sp2 hybridsed.
The acylation of NH2 group takes place and not of
OH group due to lower electronegativity of N-atom.
26. Answer (1) N
lone pair of nitrogen is involved in
N-ethyl phthalimide on treatment with
H
NH2—NH2 gives ethylamine.
– aromaticity.
O O +
: NH2 NH NH2
C C
30. Answer (1)
H
N C2H 5 + NH 2
..

N Me + –
C C C2 H5 N
— –
+ Cl N2
— —
SO3 Na+
Me
O O
OH–
O O

C NH C NH Me
NH
.. 2 – +
N =N
N= SO3 Na
— — — —
+
NH Me
C NH C2 H5 C
.. H
–O NH C 2H5 Formed product is methyl orange and it is used as
O
an indicator in acid base titrations.
O
31. Answer (2)
C NH
+ C2H5 NH2
NH
NH2 NHAc NHAc
C Br
Ac2O Br2
O
AcOH
Note: In place of NH2NH2, H2O can also be used
in presence of H+ or OH– as a catalyst. CH3 CH3 CH3

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32. Answer (3) Nitro and diazo compounds do not give Kjeldahl
estimation of Nitrogen.
NH2
+
N2 Cl
– 35. Answer (4)
NH2 CH2CH3
+ Diazotization
NaNO2 + HCl
CH2CH3 NH
273 - 278 K 2
Cu 2Br2
(A) (C)
Br Br + +
Hydrolysis N2 N2
+
Br Br CH2CH3 H CH C
3 2

HNO 3, Conc. H2 SO 4
+
OH OH KMnO4/H
+
Br Br CH2CH3 H CH C
3 2
NO2

33. Answer (4) OH OH

+
NH 2 NH 2 HOOC COOH
(S) (R)
Br Br
Br2 (B) gives insoluble product with C6H5SO2Cl. Hence
H2O
CH3 CH2NHCH3
CH3 (B) is
(P) Br
NaNO 2 , HCl (0 – 5 °C) 36. Answer (2)
+ –
NH2 N2 Cl Cl

(i) NaNO 2 + HCl, 0 – 5 Cu 2Cl 2

+N2 HCl

CH3 CH
H3 CH3
[A]
CH3
Cl Cl
OH
Cl 2 Na + dry ether
(E-naphthol)
hQ
OH
CH3 CH2 – Cl
[B]
N=N
( Coloured Solid ) Cl CH2 – CH2 Cl

CH3 [C]

34. Answer (3) 37. Answer (4)

NO2 NH2 C2H5CN o
LiAlH4 C2H5CH2NH2
Sn/HCl
38. Answer (2)
Me Me
AC2O/Pyridine

CN CH2 – NH2

LiAlH4
NH2 NH COCH3
Br2/FeCl3
CH2CN CH2 – CHO
Br Br
(i) SnCl2 + HCl Me – Me
OH/'
(ii) H2O

NH2 NHCOCH3
NH2 N 2 39. Answer (3)
NaNO2 Gabriel phthalimide synthesis gives 1° amine in
HCl good yield.

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40. Answer (2) 44. Answer (2)
Lucas reagent – Conc. HCl/ZnCl2
Dumas method – CuO/CO2
Kjeldahl’s method – H2SO4
Hinsberg test – C6H5SO2Cl/aq. KOH
41. Answer (2)
pKb = –logKb
So, as Kb increases, pKb decreases

N
NH 2– CH = NH CH 3– NH – CH 3
(A) N NH (C)

(B)
Kb : (B) > (A) > (C)
45. Answer (1)
pKb : (B) < (A) < (C) Aniline itself is strong ortho/para director but on
42. Answer (4) addition of acid it becomes anilinium ion which is
a meta director.
3
sp †
:NH2 sp 2 :NH2 H NH2 NH 3
:

N N
:

> > > H+

Most Aromatic
basic
So the answer should be 1.
? Correct order : III > II > I > IV 46. Answer (4)
43. Answer (1)
NO2 NO2 NH2
N
Br2/Fe Sn/HCl

N N N Br Br
N
H H 3 H
sp NaNO2 HCl
sp
2 lone pair lone pair
hybridized involved involved + –
'N' in resonance in resonance Br N2Cl
N
CuBr/HBr
< < <
N N Br Br
N N
H H H
(B) (A) (D) (C)

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47. Answer (3) 50. Answer (2)
+ – p-aminoazobenzene
NH2 N2Cl

NaNO2/HCl N=N NH2

OH
+
NO 2 NH2 N2

OH (A)
Sn/HCl HNO 2

N N + HCl NH 2

(Orange colour dye)

N=N NH2
48. Answer (2)

O (B)
||
H2 /Pd NO 2 NH2
(a) R  C  Cl 
BaSO 4
o R  CHO (Rosenmund's
reduction) NaBH 4 NaOH
No fo
ormation of
p-aminoazobenzene
Cl2 /Red P, H2 O
(b) R  CH2 COOH o R  CH  COOH
| NH2
Cl
(Hell - volhard -zelinsky (C)
reaction)
NH 2

O (i) HNO 2
N=N NH 2
|| (ii) Aniline, HCl
Br2 /NaOH
(c) R  C  NH2  o R  NH2 (Hoffmann
bromamide) 51. Answer (4)

NH 2 NC
O
||
Zn(Hg)
+ CHCl3 + 3KOH ' + 3KCl + 3H 2O
(d) R  C  CH3  o R  CH2 CH3
Con HCl
(Clemmensen reduction) aniline

52. Answer (3)

49. Answer (3)
A will be the major product.
Only aliphatic primary amines can be synthesised
NH 2
by Gabriel phthalimide synthesis.
HNO 3 , H2SO 4
Out of the given amines the following amines can 288 K
be synthesised by Gabriel synthesis. NH 2 NH2 NH 2
NO 2
CH
(1) CH3 CH – CH2 – NH2 + +
3
NO 2
(2) CH3CH2NH2 NO2
(51)% (47%) (2%)
CH2 NH2 A B C
(3) In strongly acidic medium aniline is protonated to

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 form anilinium ion which is a meta directing. That 56. Answer (1)
is why besides the ortho para derivatives,
significant amount of meta derivatives is also O
formed. CH2 – C – CH 3
Br 2, NaOH
53. Answer (1)
Given amine on reaction with PhSO2Cl produces O
a compound insoluble in alkaline solution it means – +
CH2 – C – ONa
it is a 2º amine.
CHBr3 +
' It is prepared by ammonolysis of C2H5Cl, it
must contain an ethyl group
H+

H CH2COOH
|
C H3CH2CH2N — CH2CH3 is a 2° amine as well
as it contain ethyl group.
54. Answer (4) CH2COOH CH 2CONH 2
NH 3, '

LiAlH 4/H 2O
NH2
CH 2CH2NH 2
(A) Phenyl methanamine pK b = 4.7

H 3C CH 3
N 57. Answer (3)
+ –
(B) N, N-Dimethylaniline pK b = 8.92 NH2 N2Cl OH

NH – CH3 NaNO2 , HCl H 2O/ '

273 - 278 K

(C) N-Methyl aniline pK b = 9.3

58. Answer (3)
NH2 W ith each substitution reaction, acidic
( D) Benzenamine pK b = 9.38
concentration increases in reaction mixture
1
pK b v
Basicity
R – NH2 + R ´– X R – N – R ´ + HCl
H
(A) > (B) > (C) > (D) So to remove acidic impurities , NaOH is added.
55. Answer (4) 59. Answer (2)
Ceric ammonium nitrate is used for the Basic strength vavailability of lone pair.
identification of alcohol. O O
..
CH3 – C – N – C – CH3
2R — OH  (NH4 )2 Ce(NO3 )6 
o (ROH)2 Ce(NO3 )4  2NH4NO3
H
Alkoxy cerium ion IV
Compound
..
Pink or Red colour In this case lone pair of N is highly participating
in resonance.
CHCl3/KOH is used for the identification of primary
60. Answer (1)
amines.
Ammonolysis of alkyl halides is the reaction of
warm alkyl halide with NH 3 which leads to the
R  NH2  CHCl3  3KOH(alc) 
o
preparation of amines.
R — NC  3KCl  3H2 O
C6H5 CH2Cl  NH3 
o C6H5CH2NH2

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61. Answer (2) 66. Answer (3)
O
CONH 2 NH2 NC
C6H5 — CH — NH2 + Cl — S O
Br2 + KOH CHCl3 +
NaOH CH3

(A) (B)

Hoffmann bromamide degradation of benzamide O

gives aniline (A) which upon heating with CHCl3 and
NaOH gives phenyl isocyanide (B). C6H5 — CH — NH — S O
62. Answer (2) NaOH CH3

N+
2 Cl
– OCH3
Soluble in NaOH due to
presence of acidic hydrogen
+ C2H5OH + N2 + CH 3CHO + H 2O
O
OCH3 –
C6H5 — CH — N — S O
(A)
Na+
C2H5OH behaves as mild reducing agent and itself CH3
gets oxidised to ethanal.
63. Answer (1) 67. Answer (1)
Hinsberg test is used to distinguish 1°, 2° and 3° O
amines.
Reagent used is (PhSO2Cl). R — C — NH2 + BrO–

So, para-toluene sulphonyl chloride can be used.

R — NH 2 + CO23 – + Br–
64. Answer (3)
Carbonyl carbon is lost as CO32 .
NH2 N+2 Cl– 68. Answer (1)
NaNO2, HCl NaNO2 + HCl +
HO3S NH2 HO3S N N
273 K – 278 K 273 – 278 K

X (A)
CH3
+ – +
C6H5N2Cl + N(CH 3)2 HO3S N N + N
CH3

C6H5 – N = N N(CH 3)2

CH3
65. Answer (1) HO3S N N N
CH3
(B)
NH 2 NH2 NH2 NH 2 69. Answer (4)
NO 2
HNO3, H2SO 4 O
+ +
288 K NH2
NO 2 NH2 KOBr
NO2
A B C
2% 47% 51% Br Br
O
In strongly acidic medium aniline is protonated to
NH2 LiAlH4 NH2
form anilinium ion making it m-directing but +
H3O
p-derivative is also formed in significant amount
which is a major product. Br Br

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70. Answer (3) Rest of the reactions give amine group containing
product. So, they can react with Hinsberg reagent
CHCl3
R NH2 R N C + 3KCl + 3H2O
KOH O
Primary amine isonitrile O
Poisnous R–NH2 + Ph–S–Cl Ph–S–NH–R
product
O O
71. Answer (3) Hinsberg N-alkylbenzenesulphonamide
reagent (Soluble in alkali)

+ 76. Answer (3)

N2

+ H3PO2 + H 2O –
Sn + HCl C6H5N+2Cl
CH3CH2Cl, C6H5NO2 C6H5 NH2
Anhyd. AlCl3 (A)
CH2CH3
N N NH2

72. Answer (2)

Diazonium cation attacks at the para position of
Aniline does not give Friedel craft reactions
aniline to form azo compound.
73. Answer (2)
Gabriel phthalimide synthesis cannot be used to 77. Answer (108)
prepare aromatic primary amines because aryl
halides do not undergo nucleophilic substitution
with the anion formed by phthalimide.
unshared
electron
74. Answer (4) pair

CH3

CH3 NaNO2, HCl

CH3 H2O CH 3
278 K + –
NH2 N Cl
2
CH 3
108°
CH3 OH
+ Pyramidal shape of trimethylamine
OH CH3
(P)

78. Answer (4)

In this reaction major product (P) is a tertiary

alcohol formed due to rearrangement of
carbocation. But option (4) is one of the products
formed though it is not the major product.

75. Answer (2)

CN HC=NH CHO

SnCl 2 H3O+
HCl

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79. Answer (4) 81. Answer (1)

CH3 O
NO2 NO2 NH2 alc. NH3
CH3 – CH – CH 2 – CH2 – C – Cl
Cl 2, FeCl3 Fe, HCl

Cl Cl CH3 O
NaOH, Br2
NaNO2, HCl CH3 – CH – CH 2 – CH2 – C – NH2
0°C
OH
+
N2 Cl
– CH3
NaNO2, HCl
H2 O/H
+ CH3 – CH – CH 2 – CH2 – NH2

Cl Cl CH3
H2O
CH3 – CH – CH 2 – CH2 – N2 Cl

80. Answer (1) CH3

CH3 – CH – CH 2 – CH2 – OH
O (Major product)

NH2 NH – C – C H3

(CH3 – CO)2 O 82. Answer (2)

NH2 NH2 Intermolecular association due to H-bonding in
primary amines is more than in secondary amines
O O
because primary amines have more number of H-
NH2 atoms bonded to N-atom.
O O
83. Answer (4)
+ CH3 – C – O – C – CH 3
NH2 OH OH OH
O O
O H 2/Pd O
O– O C 2H 5OH (1 eq)

CH3 C O C CH3
NO2 NH2 NH CH3
NH2
(A) O
(N is more (B)
NH2 basic than O)
(Major)
O CH3
C O 84. Answer (3)
Intermediate
NH
OH LiAlH4 OH
–CH 3COOH H3O+
CN CH2–NH2
NH2
(A)
O
+
H
H
..
OH H3O
+
OH
H2SO4
CN COOH
–H2O

COOH (B)

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85. Answer (5) 89. Answer (243)

NH2 NHCOCH3
NH2

H2/Pd + CH3COCl
or H2/ Raney Ni

NH2 NO2 NH2

1.86
No. of moles of aniline = 0.02
Zn + HCl Sn + HCl 93

Moles of acetanilide formed = 0.9 × 0.02

Fe + HCl
= 0.018
Mass of acetanilide formed (ing)
= 0.018 × 135 = 243 × 10–2

NH2 90. Answer (77)

86. Answer (2) O

NH2 NHCOCH 3 O
O O
Cl
+ C6H5NHC 6H5 C6H5 – C – N(C6H 5)2
O
Mass 0.140 g 0.388 g 0.210 g (Observed
yield)

Moles  10–3 2.3 × 10

–3
Theoretical yield
–3
Br 2, CH3COOH (Limiting = 10 × 273
Room temperature Reagent) = 0.273 g

NHCOCH 3
0.210
? % yield = u 100 | 77%
0.273

91. Answer (03)

Br +
–
CH2–NH 2 CH2–N(CH 3)3Br
87. Answer (3)

NH2 O + 3CH3 –Br

K2 Cr2 O7
Number of moles of benzyl trimethyl ammonium

O 23
bromide formed = 0.1
230
K2Cr2O7 is oxidizing agent.
88. Answer (2) ? No. of moles of bromomethane consumed
1° aromatic amines give the most stable diazonium
= 3 × 0.1
salt
= 3 × 10–1
92. Answer (2)
+ –
(CH3)3NHCl } contains strong conjugate acid

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93. Answer (3) 98. Answer (3)

o-Nitrophenol and p-Nitrophenol can be easily

separated by steam distillation.
94. Answer (3)

99. Answer (2)

100. Answer (3)

95. Answer (3)

alc. KOH

96. Answer (3)

Hence H2SO4 acts as an acid

101. Answer (3)

97. Answer (4)

Hofmann bromamide degradation
In this degradation, the migration of the alkyl/aryl
group occurs to the electron deficient nitrogen
(nitrene).
Statement (I) is not absolutely correct as it mentions
only the alkyl group, whereas migration of aryl
groups may also occur depending on migratory
aptitude.
Statement (II) is correct as migration occurs to
electron deficient atom.

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102. Answer (4)
(A) Benzene sulphonyl chloride is also known as
Hinsberg reagent.

(B) Hoffmann bromamide reaction involves conversion

of amide to amine having one C-atom less. This
reaction involves isocyanate as intermediate.
103. Answer (3)
(C) Carbylamine reaction is a test given by all
primary amines.

(D) Hoffmann orientation refers to the addition of

molecules to unsymmetrical alkenes according
to anti Saytzeff’s rule.

Correct match is

A – III; B – IV; C – I; D – II

All the given reactions can be explained if organic 107. Answer (1)
compound (1) is phthalic acid.
104. Answer (3)

Aniline does not undergo Friedel Craft reaction

because the reagent AlCl3 being electron deficient
acts as a Lewis acid.
105. Answer (2)

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108. Answer (4) 111. Answer (1)
Hinsberg reagent is :

is the strongest base among the given

compounds due to the maximum +I effect and the

lone pair of N is not in dynamic state so it can be
donated easily.
112. Answer (3)
109. Answer (3)
The most appropriate option is (3) as one group is
far enough from –COOH group.

113. Answer (2)

Diazonium salt containing aryl group directly linked

to electron donating group is most stable due to
resonance. The +M ef fect stabilizes the
intermediate whereas Electron withdrawing group
on benzene destabilizes the intermediate at para
position.

110. Answer (1)

Order will be A > C > D > B.

‰‰‰

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