Chapter 22

Hydrocarbons
1. Answer (2) 7. Answer (2)
5-keto-2-methylhexanal is
H H
OH O O O
CH3 CH3
H
CH2–CH–CH CH2–CH–CH H
CH3 CH3

CH3 O3 Zn
O O
+
CH—CH– C H
H
H (A) (B) H CH3
CH3 8. Answer (1)
(A)
CH = CH–CH +
CH3 CH2 – CH – CH3
Extension of conjugation +
(More stable) CH2=CH – CH3 + Cl Cl More stable intermediate
? Major product +
CH3 CH2 – CH – CH3
(B)
CH2–CH = C Cl
(Minor) CH3
–
+
2. Answer (4) CH2 – CH – CH3 OH
CH2 – CH – CH3
(i) O3 Cl Cl OH
CH3 CH CH CH3 CH3 CHO
(ii) Zn-H2O
44 amu 9. Answer (3)
3. Answer (1)
Na/liq. NH3 CH3 H
4. Answer (1) CH3 – C { C – CH3 C=C
5. Answer (3) H CH3
Trans alkene
So, option (3) is correct.
Cl
Ag 10. Answer (1)
2Cl—C—CH3 CH3C { CCH3 + 6AgCl
Cl OH
O
1, 1, 1-trichloroethane
CH3
+ O AlCl3
6. Answer (1)
For geometrical isomerism doubly bonded carbon
must be bonded to two different groups which is
OH OH
only satisfied by 1 - Phenyl - 2 - butene.
CH3 CH3
H H H CH3
C=C C=C O
Ph – CH2 CH3 Ph – CH2 H O
AlCl3O
cis trans

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11. Answer (4) 15. Answer (1)

is aromatic as it has 2Se– in complete

conjugation
Contain 6Se– in complete conjugation and are
aromatic.
and are antiaromatic.

is anti-aromatic as it has 4Se – in

is non aromatic
complete conjugation.
12. Answer (2)
16. Answer (1)

MeO
CH2–Cl Cl
HO HO
AlCl3
(1) HCl

MeO +
MeO
+ AlCl3

HO +
HO
+ AlCl4–

MeO (Major product)

Para attack will form major product because at

13. Answer (1) ortho position steric crowding is applicable.
hQ 17. Answer (1)
CH3 – CH2 – CH CH2  Br2 
o
In general, polarity increases the intermolecular
CH3 – CH– CH CH2 force of attraction and as a result increases the
| melting point.
Br
18. Answer (1)
14. Answer (2)

N HNO3
 o
| Conc. H SO
2 4
H

Activated Deactivated
ring ring
19. Answer (3)
? Major product will be formed as per activating
group.
HBr
CH3O CH == CH — CH3
? Product formed is O2N Excess
O

N
| HO CH — CH2 — CH3
H
Br

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25. Answer (2)

20. Answer (3)
OCH3 CH3 Cl CN
CH 3
CH3 > > >
CH2
+
HCl C (+M) (+H) (–I > +M) (–M, –I)
26. Answer (4)
CH3
CH3 group when bonded to benzene increases the
Cl
– electron density of benzene by +I and hyper
conjugation effects and hence makes the
CH3
compound more reactive towards EAS. Cl group
C Cl decreases the electron density of benzene by –I
effect, and CH3CO group strongly decreases the
CH3 electron density of benzene by –I and –R effects.
Therefore, correct increasing order the given
compounds towards EAS is
21. Answer (2) COCH 3 Cl CH 3

< <
O (III) (I) (II)
Cl O
C 27. Answer (1)
(i) AlCl3, Heat
+ O (ii) H2O Angle strain is not present in acyclic compounds.
22. Answer (1) Cl C 28. Answer (1)
O HO
O O O
CF 3 – CH = CH 2 AlCl 3
Cl :
H+

+ + 29. Answer (4)

CF 3 – CH – CH 3 + CF 3 – CH2 – CH 2
(More stable) Cl 2
–I CH3 – CH = CH 2 CH 3 – CH — CH 2
H 2O
(Less stable +
Cl – Cl
due to –I effect
of –CF3) CF 3 – CH2 – CH 2 – Cl +
H2O, –H
anti-Markovnikov

CH 3 – CH – CH2
23. Answer (4)
Polysubstitution is a major drawback in Friedel OH Cl
Craft’s alkylation. 30. Answer (2)
24. Answer (1)
KMnO 4
CH3 – CH = CH – CH 3 2CH3COOH
OH–, '
DCl
CH3 – C { C – H CH3 – C = CH
1 eq
31. Answer (1)
Cl D EtOK /EtOH
Ph Ph (X)
DI Cl
(CH3COO)2Hg + H2O + NaBH4
OMDM
I D
CH3 – C – CH OH
3
Cl D 4 1 Ph Product
2
1-phenylbutanol
Both addition follow Markownikov’s rule.

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32. Answer (4) 37. Answer (4)

H
H Hc29°
H a b c
Trans config. Trans config. Cis config.
120° around both around one around both
Hcc H double bond double bond double bond

? Angle between Hc and Hcc = 120° + 29° = 149° Order of stability : a > b > c
33. Answer (1) Order of heat of combustion : c > b > a
Vinyl halide and aryl halide do not give Friedel 38. Answer (2)
Craft’s reaction. The reactions which are possible Each carbon atom is sp2 hybrid
are :
? 3 sp 2 hybrid orbitals are formed by each
carbon atom
Total sp2 orbitals = 6 × 3 = 18
(b) 39. Answer (3)

H 3C CH = CH 2 H3C CH – CH 3
+
H 3O
(d)

Rearrangement .

34. Answer (4)

Peroxide generates a radical that abstracts
H-atom from the C-atom adjacent to CN group to
40. Answer (3)
give more stable radical

CN Peroxide x CN
' LiNH2 /ether –
CH
H CH CH
H
[A]
Br
[A] attacks 1-pentene to give 2° radical that picks
up H-atom to give [B]
HgSO4
+ CN CN CH
H3 — CH
H — CH(CH3)2 CH
H3 — CH
H — CH(CH3)2
H2SO 4

O ==
=C C
[B]
35. Answer (4) CH3 CH
NaBH4
O OH
+
conc.¬H 2SO 4
+ CH
H3 — CH
H — CH(CH3)2 '
H3O
CH
H — OH
CH3 CH3 CH3
Product is aromatic
36. Answer (4) C(CH3) 2
+
Aniline and phenol form complex with Lewis acid. CH
H3 — C CH
H3 — C — CH(CH3 )2
? Highest yield in Friedel Craft reaction among C2 H5 CH2CH3
Cl

given species is for chlorobenzene i.e.

(after Hydride shift)

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41. Answer (1) 45. Answer (4)

2+ +
Hg /H
C C OCH3 H2 O
Hydration
O O of alkyne

O2N
O: AlCl3 OH
+ (A)
HO CH C OCH3

O O
O 2N
Tautomerisation
Zn – Hg/HCl

O
H3 PO 4 O2N CH2 C OCH3

HO

O O Ethers are least reactive and their cleavage takes

(B) place under drastic conditions.
46. Answer (3)
O
42. Answer (4) (C 6H5 CO) 2
+ HBr (A)
CH3CH == CHCH(CH3 )2 Br
+
H
H + HBr Br (B)
CH3
+
CH3CH2 – CH – C Br
CH + HBr (C)
Hydride
shift
Boiling point decreases with branching
CH3 ? order of B.P. is A > C > B
+
CH3– CH2 – CH2 – C 47. Answer (13.00)
–
CH3
Br

Br Red hot Cu tube

CH3 3 H–C {C–H
CH3– CH2CH2 – C (Lowest molecular
weight alkyne)
CH3 (B)
(A)
43. Answer (3)
H H
H
H C
CH3 CH 3 H CH3 Cl(1 eq.)
t
KO Bu/ '
CH 3 – CH – CH – CH 3 CH3 – CH – CH = CH 2 Anhyd AlCl3
H H
(ii) O3/H 2O2
OSO2CH3
(oxidative
ozonolysis)
H
(C)
CH3

CH3 – CH – COOH + HCOOH Number of atoms in one plane = 13

48. Answer (80)

44. Answer (1) NO2

CH3 CH3 CH3
Br Br HNO3
HBr HBr H2SO 4

Br
3.9
NO2 NO2 NO2 Number of moles of C6H6 = = 0.05
78

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Theoretical moles of nitrobenzene = 0.05 52. Answer (4)

Actual number of moles of nitrobenzene CH3 – CH2 – CHO (Propanaldehyde) cannot be
4.92 prepared by addition of water on alkyne in the
= = 0.04 presence of HgSO4 and H2SO4.
123
Percentage yield of nitrobenzene O
H2O
0.04 C { CH C CH3
= u 100 Hg , H
2+ +

0.05
= 80% H2O
49. Answer (78) HC { CH 2+ +
CH3 – CHO
Hg , H
COO H COO H
O
FeBr3 H2O
+ Br 2 + HBr CH3 – C { CH 2+ +
CH3 – C – CH3
Hg , H
Br
53. Answer (2)
mass 6.1 g 7.8 g
in gram CH3

CH2 CH3 CH3

6.1 Mo2O3
moles 0.05
122 773 K, 10-20 atm
CH2 CH (Aromatisation)
1 mol of benzoic acid give 1 mol of CH2 CH3 (A)
m-bromobenzoic acid. 0.05 mol of benzoic acid will
give 0.05 mol of m-bromobenzoic acid. 54. Answer (7)
So, percentage yield is
7.8 u 100 (1) Red hot Fe tube
% yield = 77.61% CH { CH
0.05 u 201 873 K

| 78%
50. Answer (78) (2) CO, HCl, AlCl3

CH3 CHO

10
10 g of C6H6 = moles All the 7-carbon-atoms in product are sp 2
78
hybridised.
moles of methylbenzene should be obtained
55. Answer (2)
10
= mole
78
NO 2 NO 2
10 H 2SO 4
= × 92 g
78
†
9.2
% yield = u 78 u 100 78% NO 2
NO 2
10 u 92
51. Answer (1) + H
†
†
+
H

1, 2 methyl
NO 2
shift

–
I
I (Major)

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56. Answer (2) 62. Answer (4)

Carbocation B is more stable as it is secondary
(i) NaNH 2 carbocation having more number of D-hydrogens
CH3 – CH = CH – Br and having greater +I effect.
(ii) Red hot iron
tube, 873 K ? Carbocation B formed at a faster rate than
CH3 carbocation A.
63. Answer (2)
Alkanes having tertiary H can be oxidised to
H3 C CH 3 corresponding alcohols by KMnO4.
KMnO4
Mesitylene

2-methyl butane OH
So the correct option should be (2).
whereas ordinary alkanes resist oxidation.
57. Answer (2)
64. Answer (1)
CH2 C CH  CH3 x Alc. KOH causes elimination
sp2 sp sp2 sp3 x Pd / BaSO4 – Lindlar’s catalyst
x BHC is obtained by the addition reaction of Cl2
Hybridization of carbon 1, 2, 3 and 4 respectively are with benzene in presence of U.V.
sp2, sp, sp2 and sp3
x Thin film of polyacetylene can be used as
58. Answer (4) electrode in batteries.
65. Answer (1)
CH2 CH3

(1) Zn/HCl KMnO4 COOH

(2) Cr 2 O3 , 773 K H2SO4, ' COOH
O 10 - 20 atm
(A)
59. Answer (2)
Partially deactivated palladised charcoal is called OH
KMnO4
as Lindlar’s catalyst.
H2O, 273 K
60. Answer (2)
(B) OH
In presence of U.V. light, free radical substitution
reaction occurs, at allylic position. 66. Answer (1)
In the nitration of benzene using nitrating mixture,
Cl
HNO3 acts as a base and H2SO4 acts as an acid
Cl2 to generate NO2+ ion.
U.V.
H2 SO4 o H  HSO4
Cl
+ + +
HO N O + H H2O N O H2O + NO2
61. Answer (3)
O O
+ NO2 NO2
H+ +
CH 3 –H
+
CH3 CCl 4 +
+ NO2
Br
Br–
CH 3 67. Answer (2)
CH 3
KMnO4/ H+ O
(A)
2-methylpropene (A) (B)
The reaction involves the formation of 2° carbocation
Ozonolysis O
followed by methanide shift to give 3° carbocation.
Br– ion attacks the 3° carbocation to give the major
2-methylpropene (A) (B)
product.

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68. Answer (2) 72. Answer (1)

Br

H 3C H H3C H
C CCl 4 C
+ Br2
C C
H 3C H H 3C H
Br
(+ ) P

Addition of Br2 to alkene is anti addition.

Two stereoisomers are formed in the given reaction. 73. Answer (1)
69. Answer (3)
+ Br2
hQ Br +
(T = 125°C)
Br
+
OH OH2 Major Minor
Excess
+
H 3PO4 Bromination is highly selective, reactivity order –
120°C
3° >> 2° > 1
74. Answer (3)

OH
(BH 3)2 HBr
–
H 2O 2, OH
H 2O (excess)
(P) (A)

70. Answer (1)

O
OH O +
+ Br
H
H3C OCH3
H 3C OCH3 –H 2O

(Major product)

O O
75. Answer (2)
CH3 OCH 3 CH3 OCH 3
Br– + O O
Br
Br2
(Major) AlBr3, ether

71. Answer (2) Br

Ketones are meta directors.

Br2 + AlBr3 o AlBr4– + Br +

O O

+ Br+ +

Br H
Arenium ion

O AlBr 4–

Br

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76. Answer (3)

+
O O AlCl 3

••
Given mass
Mole = AlCl3
Molar mass O O

Given volume (at STP in L)

= O O
22.4
+
1.53 448 u 10 3 O AlCl 3 –
Cl3Al O
O
Molar mass 22.4 O O
1.53 u 22.4
Molar mass = = 76.5 g mol–1 O
448 u 103
There can not be more than one chlorine atom per O
O
molecule because molar mass 76.5. One of the
possible compounds is Cl – CH2 – CH = CH2. O– AlCl 3
Cl – CH2 – CH CH2
Zn/Hg
(i) O3 HCl

(ii) Zn/ ACOH
o ClCH2 – CHO  HCHO
OH
77. Answer (1)
O
Br (B)
Br
(A) : CH3–CH = CH 2 H 2O CH3 –CH–CH2 80. Answer (2)
2

OH
+
Br
Br2
(R) : CH3–CH = CH 2 CH3 –CH–CH2

..
H 2O
..

CH3–CH – CH 2–Br

OH
78. Answer (4)

NO 2
conc. HNO3
conc. H 2SO4
' 81. Answer (2)
(A)
Cl2
Anhyd. AlCl3

NH2 NO 2
Fe
HCl

Cl Cl
(C) (B)
Number of sp2 hybridised carbon atoms = 2
79. Answer (4)
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82. Answer (1) 86. Answer (1)

The S-bond present is alkenes is weaker than V-
bond present in alkanes. That makes alkenes less
stable than alkanes. Therefore, statement-I is
correct.
Carbon-carbon double bond is stronger than Carbon-
carbon single bond because more energy is required
to break 1 sigma and 1 pi bond than to break 1 87. Answer (4)
sigma bond only. Therefore, statement-II is also
correct.
83. Answer (2)

88. Answer (1)

Oxymercuration-demercuration follows

The given reaction undergoes nucleophilic Markovnik ov’s addition of water without

substitution by SN2 mechanism at room rearrangement.

temperature
? No. of S electrons present in P = 2
84. Answer (2) 89. Answer (3)

Both products are meta with respect to –CH3.

90. Answer (4)

85. Answer (1143)

CH3–CH2–CH2–CH = CH2 + Br2
p
Br
|
CH3  CH2  CH2  CH CH2
|
Br
5 5
moles of pentene will react with moles of
70 70
Br2

5
u 160
70
= 11.43 g

1143 u 102 g (B) should be 1-methylcyclopent-1-ene.

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91. Answer (3) 97. Answer (6)

Total number of hydrogens are 6.

Hence correct option is (3). 98. Answer (1) and (2)
92. Answer (3)

and are not benzenoid

compounds, since benzenoid compound contains

benzene ring.
99. Answer (2)
93. Answer (4)

94. Answer (3)


Initially CH — CH — CH2 is formed. On
3 2


rearrangement CH3 — CH— CH3 stable

carbocation is formed.
95. Answer (4)

100. Answer (2)

* Ants produces formic acid in their venom gland.

96. Answer (4)

101. Answer (3)

? in option (3) different products are produced.

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102. Answer (3) Molar mass of 1,1,2,2-tetrabromopropane = 360 g

Mass of 1,1,2,2-tetrabromopropane

1 1 27
u u u 360 g
2 160 100

2 moles Br2 {1 mole 1,1,2,2-tetrabromopropane | 3×10–1 g

103. Answer (2)
1
mole Br2 The correct order of reactivity towards nitration is
160

1 1
{ u mole 1,1,2,2-tetrabromopropane
2 160
But yield of reaction is only 27%
Moles of 1,1,2,2-tetrabromopropane

1 1 27
= u u as electron releasing groups on benzene ring
2 160 100
facilitate the nitration at benzene ring.

‰‰‰

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