HINTS & SOLUTIONS

Single Option Correct Type Questions (01 to 49)

1. (A)
Sol:

2. (A)
δ+ δ–
Sol: Br − Cl , so Cl– will add at most stable carbocationic site.

3. (A)
Sol: I- Peroxide effect or kharash effect
II- Halogenation

4. (D)
Sol: H3O+ gives , i.e., Markownikov’s addition, through carbocation formation. formed by hydroboration
oxidation that gives anti-Markownikov’s product.

5. (C)
Sol:

6. (C)
2+
H2O Hg
Sol: CaO + C 
∆
→ CaC2  → C2 H 2 
H 2SO 4
→ CH 3CHO

7. (C)
Sol: Markownikov product.

8. (C)
Sol: KMnO4 cold gives syn hydroxylation.

9. (A)
Sol: Peroxy acid forms epoxy alkane on reaction with alkene
10. (D)

Sol:

11. (B)
Sol:

12. (B)
Sol:

(Zinc is not present hence CH3CHO first formed oxidised to CH3COOH)

13. (C)
Sol:

14. (C)
Sol: Triple bond is more reactive than double bond for hydrogenation.
Lindlar’s catalyst give nearly 100% cis isomer..

15. (B)
H2O
Sol: R − C ≡ CH + R ′MgX 
→ RH + R − C ≡ CMgX  → R − C ≡ CH

16. (A)
Sol: Double bond attached with ring cannot from cis-trans isomers. So, only cis-trans isomers are possible due to middle
double bond

17. (A)
Sol:
18. (C)
Sol:

19. (D)
Sol: Meso gives trans-2-butene Racemic mixture gives cis-2-butane

20. (B)
Sol: It is an example of intramolecular Wurtz reaction
Na 
→ Na ⊕ + eΘ

21. (A)
Sol: Bromine is more selective
∴ abstract that hydrogen which forms stable free-radical.

∴ (3º free-radical) is most stable.

22. (C)

Sol:

total 7 dichloro products are possible.

23. (B)

Sol:

24. (A)
Sol:

More the stable σ-complex, more will be rate of reaction.

25. (B)

Sol: (A) (B)

26. (D)
Sol: Between II and III, III (cis) is more reactive due to it less steric resistance to adsorption on the surface of metal
catalysis.

27. (B)
Sol:

28. (B)
Sol:

29. (D)
Sol: Catalytic hydrogenation occur with syn-orientation. Both ‘A’ and ‘C’ will resultant in meso product while
‘B’ will give achiral butane. ‘D’ will give racemic mixture due to equal probability of hydrogenation from the two
sides of plane of alkene

30. (D)
Sol: Rate of electrophilic addition ∝ Nucleophilicity of alkene ∝ stability of carbocation, so order IV > I > II > III.
31. (B)
Sol:

32. (C)

Sol:

33. (A)

Sol:

34. (B)
Sol: Because reagent is Li/NH3 [i.e. Li+ + eΘ and H – NH2] there will be trans addition at both the ≡ bonds.

35. (A)
Sol:

Total products are six and fractional distillation are five.

36. (D)

Sol:

37. (B)
Sol: Most stable radical is formed.

38. (A)
Sol: Example of nucleophilic addition to double bond.
39. (A)
Sol:

40. (B)
Sol:

41. (C)

Sol: Trans addition of –OH and 'D' at is taking place.

42. (D)
Sol: Highly rich π electron bond will be attacked first in electrophilic addition reaction.

43. (B)

Sol:

44. (D)
Sol:
45. (D)

Sol:

46. (A)

Sol:

47. (B)

Sol:

48. (C)
Sol:

49. (A)

Sol:

Multiple Choice Correct Type questions (50 to 81)

50. (A, C)
Sol:

51. (A, B, D)

Sol: On applying selectivity-reactivity principle, only has about 35% in the mixture. Others

have less than 35% in the mixture.

52. (A, B, C)

Sol:
O + HCHO

53. (A, B, C, D)
Sol: Either leaving group should be poor or base should be bulky.

54. (A, C)
Sol: Acetone will be the product of ozonolysis when the compound has as a structural unit.

55. (A, B, D)
Sol: In all molecule, one H2 molecule is added but only (A), (B) and (D) can give symmetrical diketone on reductive
ozonolysis, while (C) give only ketone.

56. (A, C)
Sol: A by E2 elimination, B by E1 elimination.
Alc. KOH will undergo dehydrohalogenation by anti elimination.

57. (A, B)

Sol:

58. (A, B)
Sol:

59. (A, B, C, D)
Sol: 1-4 addition dominates at high temperature and with excess of HBr both double bond give addition product.
1-2 addition dominates at low temperature.

60. (A, B, C)
Sol:

61. (A, C)
Sol: (A) Friedel Craft alkylation
(C) Friedel Craft decarbonylation

62. (A, C)
Sol: (A) and (C) on E2 elimination give new π bond formation but (B) can’t give E2 elimination.

63. (A, B)

Sol:

64. (A, B, D)
Sol: A, B, D gives Hofmann product
(A) Hindered base
(B) ElCb (stable conjugate base)
(D) Hofmann elimination

65. (C, D)
Sol:

66. (A, C)

Sol:

67. (A, B, C, D)

Sol: (i)

(ii)

68. (B, D)
Sol: (B) Hofmann elimination
(D) Hindered base

69. (B, C)

Sol:
70. (A, D)
Sol: NaBH4 reduces 2° and 3° halides but fail to reduce 1° halide. LiAlH4 reduces both 1° and 2° halides to alkane but 3°
alkane undergo elimination reaction to give alkene (C).

71. (A, D)

Sol:

72. (B, D)

Sol:

73. (A, B, C, D)
Sol: 1-butyne is a terminal alkyne, has an acidic hydrogen, gives H2(g) with Na/∆ or NaH. With NaNH2, NH3 (g) and
with CH3MgBr, CH4(g) are evolved.

74. (A, B, C)
Sol:
75. (A, B, D)

Sol:

76. (A, B)
Sol: Free radical mechanism give three type of alkyl radicals.

77. (A, B, C, D)
Sol: (A) Pyrolysis of esters, syn 1, 2 Elimination

(B) Cope elimination of Trialkyl amine oxides,

(C) Hofmann elimination of quaternary ammonium hydroxide

(D) Hofmann elimination of sulphonium hydroxide

78. (A, B, D)
Sol:
79. (A, B, C, D)
Sol: (A) Product R–CH 2 − CH 3 (B)

(C) Product (D)

80. (A, B, C, D)
Sol: All the given alkynes will give corresponding alkene on reaction with sodium in liquid ammonia due to partial
hydrogenation of triple bond.
Note: If we use NaNH2, then only CH3CH2C ≡ CH and PhC ≡ CH containing acidic hydrogen will react.

81. (C, D)
Sol: CH 3 MgX + CH 3 ≡ CH 
→ CH 4 + CH 3C ≡ C− MgX

Numerical /Integer Value Type Questions (82 to 102)

Part-I : Numerical Type (82 to 92)

82. (4.00)

Sol:

83. (6.00)

Sol:

84. (6.00)
Sol:

85. (130.00)
Sol:

86. (7.00)

Sol:

87. (2.00)

Sol:

88. (4.00)
Sol:

89. (2.00)

Sol:

90. (5.00)
Sol: From molar mass, it can be derived that alkene is C6H12.
 All this upon catalytic hydrogenation gives the same 3-methyl pentane. Moreover, I has a chiral carbon, hence its
pair of enantiomers exists. II has two geometrical isomers.

91. (8.00)
Sol:

92. (5)
Sol:

93. (3)
Sol:
94. (3)
Sol:

95. (6)
Sol: One unhybridized orbital on each carbon involved in double bond and two on each carbon involved in triple bond.

96. (9)
Sol: Reaction-1:

x1 = 2
Reaction-2:

,
x2 = 3-Optically active products

Reaction-3:

R = 2 Products.
Reaction-4:

x4 = 2-Optically active products.

x1 + x 2 + x 3 + x 4 = 2 + 3 + 2 + 2 = 9
97. (6)

Sol:

98. (0)
Sol: The reaction is

99. (3)
Sol:

(TS = Transition state)

100. (4)

Sol:

Minimum 4 carbons are required

101. (2)
Sol: One Br2 is added at double bond and one at triple bond.

Due to fixed trans configuration at double bond in the product, only a pair of enantiomers are formed.

Matrix Match Type Questions (102 to 111)

Part I List type Questions (102 to 106)

102. (D)
Sol: I- R; II- P; III- Q; IV- Q, S
Chlorination in presence of hν is a free radical reaction. Bromination of alkene proceeds through cyclic transition
state and undergoes anti addition. Hydration involves carbocationic mechanism, carbocation formed in this case will
not undergo rearrangement. Elimination (E1) proceeds through carbocation, which has tendency of rearrangement.

103. (C)
Sol: I-S; II-P; III-R; IV-Q

6 ×1 6
(A) Cl %= × 100 = × 100 = 20.54%
6 × 1 + 3 + 4 × 3.8 + 5 29.2

5 × 100
(B) %= = 17.12%
Cl 29.2

7.6
(C) %= × 100 = 26.0%
29.2
Cl

Cl 3
(D) %= × 100 = 10.27%
29.2

104. (B)
Sol: I-Q, R, S; II-Q; III-P, S; IV-S
H

(A) Very acidic hydrogen so reacts with base it is allylic hydrogen which will be substituted by Cl2 /hν.

Presence of double bond will make it react with Br2 water.

(B) Acidic hydrogen H—CH2—O—H

(C) → Undergoes nitration with (HNO3 + H2SO4) as well as free radical addition with Cl2 /hν.

(D) → free radical substitution with Cl2 /hν

105. (A)
Sol: I-S; II-P; III-Q; IV-R
 (I)

(II)

(III)

(IV)

106. (D)
Sol: I-S; II-P, Q, T; III-P, T; IV-R
⇒ Corey-house reaction used to prepared symmetrical or unsymmetrical alkane but not methane.
⇒ Wurtz reaction used to prepared only symmetrical alkane but not methane.
⇒ As the s-character increases in hybrid orbital, acidity increases.

Part II : Matrix Match Questions (107 to 111)

107. I-P, Q, S; II-P, R, S, T; III-P, Q, S; IV-P, R, S, T

Sol: Non terminal alkyne can form trans-alkene with Na/Liq.NH3 and does not react with ammonical AgNO3 while
terminal alkynes do not form trans-alkene with Na/Liq.NH3 but reacts with ammonical AgNO3.

108. I-P, S, T; II-P, R, T; III-R, T; IV-Q, T

H 2O tautomerisation
Sol: (A) CH3 — C ≡ C — H 
HBO
→ CH3 — CH = CH — OH ← → CH3 — CH 2 CHO
OH O
OMDM tautomerisation
(B) H 3C C CH H 3C C CH 2 H 3C C CH 3

(C) Oxymercuration demercuration involves addition of H2O giving Markownikov’s product.

(D) Oxo process.
109. I-P, Q, R; II-P, R; III-P, S, T; IV-P, R, T
Sol: (A) Stable carbocation intermediate due to rearrangement and stable Saytzeff product.
(B) 3° stable carbocation
(C) E2 elimination
(D) Unimolecular elimination

110. I-P, S; II-Q, T; III-P, R, S; IV-R,T

Sol: (I)

(II) Reaction proceeds through carbocation intermediate.

3 CH3 (i )BH3.THF H3C CH3

(III)
(ii) OH/H2O (syn addition)
CH2 CH2 CH2 CH3

(IV) Addition of Br2 is trans addition

111. I-Q, R, S, T; II-Q, R, S, T; III-P, Q, R, S, T; IV-Q, R, S, T

Sol: (A) A gives ketone with H3O+ and HgSO4 and by HBO also undergo ozonolysis to form bicarbonyl compounds
(B) Alkene give ozonolysis and HBO reaction
OH O
(C)
PCC

OH OH
Zn/H 2O
+ O3
O
O

OH OH
HBO
(D)
OH

O3
Zn/H2O

O
O
Comprehension Type (112 to 135)
Comprehension-1

112. (D)

Sol:

113. (B)

Sol: gives addition reaction and decolourise Br2 water.

Comprehension-2
114. (D)

Sol: (ii) H 2O,NaBH 4NaOH

115. (C)

Sol:

116. (A)

Sol:

Comprehension-3
117. (B)
118. (C)
119. (B)
Sol:
 Comprehension-4
120. (B)

Sol:

The addition of BH3 to double bond resulting in the formation of four membered transition state in which more
electronegative H-atom is bonded to benzylic C-atom.

121. (A)

Sol:

Comprehension-5
122. (D)

Sol:

123. (C)

Sol:

Comprehension-6
124. (A)
Sol: Diel’s alder reaction involves (4 + 2) cycloaddition.

125. (B)

Sol:

126. (C)
Sol:

Comprehension-7
127. (D)
Sol: Alkenes are more reactive towards electrophilic addition reactions but when product formed is conjugated diene
alkynes give this reaction first.

128. (A)
Sol: Alkenes are more reactive for electrophilic addition reaction.

129. (A)
Sol: Alkenes are less reactive for hydrogenation.

Comprehension-8
130. (B)
Sol:

O3
H2 O

131. (A)

Sol:

132. (C)

Sol:

Comprehension-9
133. (D)
Sol: Sodium metal releases an electron during reaction. Therefore, act as reducing agent

134. (C)
Sol:
135. (B)

Sol: (A) (B)

(C) (D)

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