ALKYL HALIDES

Table of Contents

 Theory ................................................................................................................................... 3

 Exercise - 1 : Basic Objective Questions .............................................................................. 16

 Exercise - 2 : Previous Year JEE Mains Questions .............................................................. 26

 Exercise - 3 : Advanced Objective Questions ..................................................................... 30

 Exercise - 4 : Previous Year JEE Advanced Questions ........................................................ 43

 Answer Key .......................................................................................................................... 47

2 ALKYL HALIDES

THEORY
3 ALKYL HALIDES
4 ALKYL HALIDES
5 ALKYL HALIDES
6 ALKYL HALIDES
7 ALKYL HALIDES
8 ALKYL HALIDES
9 ALKYL HALIDES
10 ALKYL HALIDES
11 ALKYL HALIDES
12 ALKYL HALIDES
13 ALKYL HALIDES
14 ALKYL HALIDES
ALKYL HALIDES 15

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Physical and General Properties

Preparation of Alkyl Halides
1. In CH 3CH 2Br, % of Br is
7. Silver acetate + Br2 The main product of this
(a) 80 (b) 73 reaction is
(c) 70 (d) 7 (a) CH3 — Br (b) CH3COI
2. Which of the following is a primary halide (c) CH3COOH (d) None of these
(a) Isopropyl iodide (b) Secondary butyl iodide 8. Preparation of alkyl halides in laboratory is least preferred by
(c) Tertiary butyl bromide (d) Neo hexyl chloride (a) Treatment of alcohols

3. (b) Addition of hydrogen halides to alkenes

(c) Halide exchange

(d) Direct halogenation of alkanes

9. Which of the following organic compounds will give a mixture

Among these compounds, which one has shortest C—Cl
of 1-chlorobutane and 2-chlorobutane on hydrochlorination
bond ?
(HCl)
(a) I (b) II
(c) III (d) IV (a)

4. How many structural isomers of C3H6ClBr are possible and

how many of them are optically active respectively ?
(a) 5, 2 (b) 5, 3
(b)
(c) 4, 2 (d) 3, 2
(c)
5. Correct order of B.P. for the alkyl halide is
(a) C2H5Cl > C2H5Br > C2H5I (d)

(b) C2H5I > C2H5Br > C2H5Cl 10. Decreasing order of reactivity of HX in the reaction
ROH + HX  RX + H2O
(c) C2H5I > C2H5Cl > C2H5Br
(a) HI > HBr > HCl > HF
(d) C2H5Br > C2H5I > C2H5Cl
(b) HBr > HCl > HI > HF
6. The following reaction is known as
(c) HCl > HBr > HI > HF

(d) HF > HBr > HCl > HI

(a) Kharasch effect
11. C3H8 + Cl2 C3H7Cl + HCl is an example of which of
(b) Darzen’s procedure the following types of reactions
(c) Williamson’s synthesis (a) Substitution (b) Elimination
(d) Hunsdiecker synthesis reaction (c) Addition (d) Rearrangement
ALKYL HALIDES 16

12. What will be the product in the following reaction 17. obtained by chlorination of n-

butane will be :
(a) meso form (b) racemic mixture
(c) d-form (d) l-form
18. Analyse the following reaction and identify the nature of A
(a) (b) and B

HBr
B  HBr
peroxide  A

(c) (d) Br
(a) Both A and B are

13. 2, 6 - Dimethylheptane on monochlorination produces…….

derivatives (b) Both A and B are Br
(a) 5 (b) 6
Br
(c) 3 (d) 4
(c) A is & B is Br
14. Which of the following reagents could be used to convert
cyclohexanol to chlorocyclohexane ?

(a) Cl2, light (b) SOCl2 Br

(d) A is Br & B is
(c) PBr3 (d) none of these

15. The reaction

Peroxide
19. CH2 CH2 + HBr (A)

(A) is :

(a) CH3 CH2Br

proceed by the mechanism :
Br
(a) SN1 (b) SN 2

(c) SE (d) SNi (b) CH3 CH3

Br Br
16. Vinyl chloride reacts with HCl to form

(a) 1, 1- dichloro ethane (b) 1, 2- dichloro ethane Br Br

(c) Tetrachloro ethylene

(c) CH3 CH3
(d) Mixture of 1, 2 and 1, 1 – dichloro ethane

(d) BrCH2 CH2Br

ALKYL HALIDES 17

20. In the following reaction find the correct product : 25. Ethylene dichloride and ethylidene chloride are isomeric
compounds. The false statement about these isomers is
that they

(a) React with alcoholic potash and give the same product

(b) Are position isomers

(c) Contain the same percentage of chlorine

(d) Are both hydrolysed to the same product

26. Bottles containing C6H5I and C6H5CH2I lost their original

(a) (b) labels. They were labelled A and B for testing. A and B were
separately taken in test tubes and boiled with NaOH solution.
The end solution in each tube was made acidic with dilute
HNO3 and then some AgNO3 solution was added. Substance
B give a yellow precipitate. Which one of the following
statements is true for this experiment
(c) (d)
(a) A was C6H5I (b) A was C6H5CH2I

(c) B was C6H5I

21. Formation of free radical takes place with absorption of
minimum energy in the formation of : (d) Addition of HNO3 was unnecessary

27. What is the major product of the reaction ?

(a) (b)

(c) (d)

Reactions of Alkyl Halides : Elimination

22. When CH3CH2CHCl2 is treated with NaNH2 the product
formed is
(a)
(a) (b)

(c) (d)

Reactions of Alkyl Halides : Nucleophilic Substitution (b)

23. Ethyl bromide reacts with silver nitrite to form
(a) Nitroethane
(b) Nitroethane and ethyl nitrite
(c)
(c) Ethyl nitrite (d) Ethane
24. Which of the following are correct statements about C2H5Br
(a) It reacts with metallic Na to give ethane
(d)
(b) It gives nitroethane on heating with aqueous ethanolic
solution of AgNO2
(c) It gives C2H5OH on boiling with alcoholic potash
(d) It forms ethylacetate on heating with silver acetate
ALKYL HALIDES 18

28. Which of the following reactions is a good way to prepare 31. What is the product of the following reaction ?
methyl tert–butyl ether ?

(a) CH3O–Na+ + (CH3)3 CBr 



(b) (CH3)3CO– K+ + CH3I 



NaOH
(c) (CH3)3COH + CH3OH  

(d) CH3MgBr + (CH3)3COCl 



29. The product B of the following sequence, would be (a)

CH I
3  
2 Ag O
heat
 OH   B2

(b)

(c) Both (a) and (b)

(d) Neither (a) nor (b)
I II

32.

To make this ether which of the following reactions will be

III IV
most suitable ?

(a)

(a) I (b) II
(b)
(c) III (d) IV and V
30. Iodine from iodoethane can be substituted by cyanide
group in a number of ways. Which of the following is true
statement ?
(a) With either KCN or AgCN, EtCN is formed as major
product. (c)
(b) With either KCN or AgCN, EtNC is formed as major
product.
(d) both (b) and (c)
(c) With AgCN, EtCN and with KCN, EtNC is formed.
(d) With AgCN, EtNC while with KCN, EtCN is formed as
major product.
ALKYL HALIDES 19

Aq.KCN
33. CH3 – CH2 – CH2 – I 
EtOH
 P
 Major 
36.
P should be

(a) CH3 – CH2 – CH2 – CN

(b) CH3 – CH = CH2

(c) both (a) and (b) in equal proportions

(d) none of these P should be

34. CH 3  CH 2  NH 2  CH 3  I 
 P
 Excess   Major  (a) (b)

P should be
(c) both of these in equal proportions
(a) CH3 – CH2 – NH – CH3 (d) none of these
Reactions of Alkyl Halides : Metals
37. An alkyl bromide (X) reacts with Na to form 4,
(b) 5-diethyloctane. Compound X is
(a) CH3(CH2)3 Br (b) CH3(CH2)5 Br
(c) CH3(CH2)3CH.Br.CH3
(c) (d) CH3(CH2)2CH.Br.CH2CH3
1. Mg / Ether
(d) CH2 = CH2 38. A (C6H13Br) 
2. CH OH  n–hexane.
3

4, 5–diethyloctane
KCN Deduce the structure of ‘A’ :
35. 
H2O/ EtOH
 P
 Major 
(a) (b)

(a) (c) (d)

39. Which of the following cannot be obtained as the only

product in the Wurtz’s coupling reaction of halides with
sodium metal in ether solution ?

(b)
(a) (b)

(c) both (a) and (b) in equal proportions

(d) None of these

(c) (d)
ALKYL HALIDES 20

40. Corey-House synthesis is a much more convenient method
for making alkanes for which of the following reasons ?
(a) Two different alkyl halides can be use. From one alkyl
halide, R2 CuLi is prepared and then this is reacted
with another alkyl halide.
Reactions of Alkyl Halides : Grignard Reagent
44. The addition of the Grignard reagent, CH3MgBr to
acetaldehyde is a nucleophilic addition to the carbonyl
group. The nucleophile in this reaction is
(a) CH3CHO (b) CH3

(b) The reagent R2 CuLi can be prepared from 1°, 2° or 3° (c) Br (d) CH3
alkyl halide as well as from halobenzenes
3 H O
45. Ester A  C4H8 O2   CH3MgBr  C4H10 O
(c) both (a) and (b)  2 parts   Alcohol B 
(d) none of these
Alcohol B reacts fastest with Lucas reagent. Hence A and
41. Which of the following combinations of reactants is better B are :
for making propane ?

(a) (CH3 ) 2 CuLi  CH3CH 2 Br 

 CH 3CH 2 CH 3 (a)

(b) Et 2 CuLi  CH 3  Br 
 CH 3  CH 2  CH 3
(b)
(c) both of these
(d) none of these
(c)
42. Which of the following combinations of reactants is better
for making neopentane ?
(d)
3CH3MgBr
(a) 46.  C2H5O2 CO 
H O
 A. A is :
3
(a) (C2H5O)2CHOH (b) (CH3)3COH

(c) (d) (CH3)2CHOH

(b)
47.

(c) both (a) and (b)

(d) none of these

43. Na
CH3 – CH2 – CH2 – Br + CH3 – CH2 – Br  P D is :
ether

P is : (a) (b)
(a) P is mixture of three alkanes (n–hexane, n–butane and
n–pentane); none is formed in good yield
(b) P is a mixture of only two alkanes (n–hexane and n–
butane); both are formed in good yield.
(c) both (a) and (b) depending upon other conditions
(d) none of these (c) (d)
ALKYL HALIDES 21

53. In the given reaction

2CH3MgBr 3 H CMgBr
48.   A. The 
 Product
H / H2 O
product A formed can
(a) give iodoform test Find the product of reaction :

(b) further react with CH3MgBr/H3O to give t-butyl
(a) (b)
alcohols
(c) be obtained by the ozonolysis of 2, 3 dimethyl–2–
butene
(c) (d)
(d) all are correct
49. Alkyl halides react with Mg in dry ether to form
1. CH MgBr
3
54. 
2. NH Cl
P
(a) Magnesium halide (b) Grignard’s reagent 4

(c) Alkene (d) Alkyne

50. When phenyl magnesium bromide reacts with t-butanol, P should be

the product would be
(a)
(a) Benzene (b) Phenol

(c) t-butyl benzene (d) t-butyl phenyl ether

51. Which of the following compounds is not suitable solvent (b)

for Grignard reagent ?

(c) both (a) and (b)

(d) none of these
(a) (b)
55. The two optical isomers given below, namely
CH3 CH3
H Cl H Cl
Cl H H Cl
(c) (d)
C2H5 C2H5
(a) enantiomers
(b) geometrical isomers
PhMgBr  excess 
52.   (X); Product (X) is : (c) structural isomers
H3O
(d) diastereomers
56. Number of stereoisomers of the compound, 2-chloro-4-
methylhex-2-ene is
(a) (b)
(a) 2 (b) 4
(c) 8 (d) 16
57. The number of enantiomers of the compound
(c) (d) CH3CHBrCHBrCOOH is
(a) 1 (b) 2
(c) 3 (d) 4
ALKYL HALIDES 22

62. In addition-elimination pathway of nucleophilic aromatic

Preparation of Aryl Halides
substitutions, which of the following compounds is most
58. reactive ?

In the above process product A is (a) (b)

(a) Fluorobenzene (b) Benzene

(c) 1, 4-difluorobenzene (d) 1, 3-difluorobenzene

59. C6H5Cl prepared by aniline with

(a) HCl (b) Cu2Cl2

(c) Cl2 in presence of anhydrous AlCl3

(c) (d)
(d) HNO2 and then heated with Cu2Cl2

Reactions of Aryl Halides

60. The following transformation proceeds through
63. In addition-elimination pathway of nucleophilic aromatic
substitutions, which of the following compounds is most
reactive ?

(a) (b)

(a) benzyne intermediate

(b) oxirane
(c) electrophilic - addition
(d) nucleophilic aromatic substitution

(c) (d)

1. HO / 
61.  P
2. H

64. In addition elimination pathway of nucleophilic aromatic

This reaction follows
(a) SN1 pathway
(c) addition-elimination pathway
substitutions, a–NO2 groups is
(a) o, p–directing and activating
(b) o, p–directing and deactivating
(b) SN 2 pathway (c) m–directing and activating
(d) m–directing and deactivating

(d) none of these

ALKYL HALIDES 23

Polyhalogen Compounds
69. Iodoform can be used as
1. HO /  (a) Anaesthetic (b) Antiseptic
65.   P
2. H  Major  (c) Analgesic (d) Antifebrin
70. Which of the following is an anaesthetic
(a) C 2 H 4 (b) CHCl 3
Based on the above reacation, the major product would (c) CH 3 Cl (d) C 2 H 5 OH
be
71. An important insecticide is obtained by the action of
chloral on chlorobenzene. It is
(a) BHC (b) Gammexene
(c) DDT (d) Lindane

(a) (b) 72. Statement “Ozone in atmosphere is decreased by chloro-

fluoro-carbon (Cl 2 F2 C )
(a) Is true
(b) Is false
(c) both in equal proportions (d) none of these
66. Which of the following has the fastest rate of the reaction (c) Only in presence of CO 2
with NaOC2H5 ? (d) Only in absence of CO2
(a) p–fluoronitrobenzene (b) p–bromonitrobenzene 73. DDT is prepared by reacting chlorobenzene with
(c) p–chloronitrobenzene (d) p–iodonitrobenzene
67. How many isomers are possible with trisubstituted (a) CCl4 (b) CCl3 –– CHO
benzene with all the three groups same ? (c) CHCl3 (d) Ethane
(a) 3 (b) 4 74. A sample of chloroform being used as anaesthetic is tested
(c) 5 (d) 6 by
68. Which of the following reaction is called Wurtz-Fittig
reaction ? (a) Fehling solution
(b) Ammonical Cu2Cl2
(a)
(c) AgNO3 solution
(d) AgNO3 solution after boiling with alcoholic KOH
solution
75. Chloroform for anesthetic purposes is tested for its purity
with the reagent
(a) Silver nitrate
(b) Lead nitrate
(b)
(c) Ammoniacal Cu2Cl2 (d) Lead nitrate
76. Chloropicrin is obtained by the reaction of
(a) Chlorine on picric acid (b) Nitric acid on chloroform
(c) Steam on carbon tetrachloride
(d) Nitric acid on chlorobenzene
77. Haloforms are trihalogen derivatives of
(c) (a) Ethane (b) Methane
(c) Propane (d) Benzene
78. Number of –bonds present in B.H.C. (Benzene
hexachloride) are
(d) both (b) and (c) (a) 6 (b) Zero
(c) 3 (d) 12
ALKYL HALIDES 24

79. CCl4 cannot give precipitate with AgNO3 due to 83. Consider the following sequence of reaction
(a) Formation of complex with AgNO3 CH CH MgBr
3 2 3 PBr
  A  B
(b) Evolution of Cl2 gas HO 3
(c) Chloride ion is not formed The product B is :
(d) AgNO3 does not give silver ion
80. The formula of freon-12 is :
(a) CClF3 (b) CH2Cl2 (a) (b)
(c) CCl2F2 (d) CH2F2
Conversions/Roadmaps
81. In the following sequence of reactions (c) (d)

84. What is the major product of the reaction sequence ?

The product (C) is
(a) Propan – 2 – ol (b) Propan – l – ol
(c) Propyne (d) Propene

(a) (b)

NBS KCN
82. 
(2Mole)
 A  B; Product B
1Mole (c) (d)

85. Consider the following reactions,

is :
Br / FeBr
2 3  P 
2 H ,Ni
 Q

2NaNO  HCl CuCl


05C
R 
S
(a) (b)
The end product ‘S’ is :

(a) (b)

(c) (d)

(c) (d)
 25 ALKYL HALIDES

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS

1. On mixing a certain alkane with chlorine and irradiating it 7. Alkyl halides react with dialkyl copper reagents to give
with ultraviolet light, it forms only one monochloroalkane. (2005)
This alkane could be (2003) (a) alkenyl halides (b) alkanes
(a) propane (b) pentane (c) alkyl copper halides (d) alkenes
(c) isopentane (d) neopentane 8. (2006)
2. The compound formed on heating chlorobenzene with The decreasing order of the rate of the above reaction with
chloral in the presence of concentrated sulphuric acid is –
nucleophile (Nu ) A and D is
(2004) – – – –
[Nu = (A) PhO , (B) AcO , (C) HO , (D) CH3O ]
(a) gammexane (b) DDT (a) D > C > A > B (b) D > C > B > A
(c) freon (d) hexachloroethane (c) A > B > C > D (d) B > D > C > A

3. Reaction of one molecule of HBr with one molecule of 1,

3-butadiene at 40°C gives predominantly (2005) 9.

(a) 1-bromo-2-butene under kinetically controlled conditions

(b) 3-bromobutene under thermodynamically controlled

conditions
The alkene formed as a major product in the above
(c) 1-bromo-2-butene under thermodynamically controlled
elimination reaction is (2007)
conditions

(d) 3-bromobutene under kinetically controlled conditions (a) (b) CH 2 CH2

Me
4. Elimination of bromine from 2-bromobutane results in the
formation of (2005) Me Me

(a) predominantly 2-butyne (b) predominantly 1-butene (c) (d)

(c) predominantly 2-butene

10. Trans-2-phenyl-1-bromocyclopentane on reaction with
(d) equimolar mixture of 1 and 2-butene
alcoholic KOH produces (2006)
5. Of the four isomeric hexanes, the isomer which can give two (a) 4-phenylcyclopentene (b) 2-phenylcyclopentene
monochlorinated compounds, is (2005)
(c) 1-phenylcyclopentene (d) 3-phenylcyclopentene
(a) 2-methylpentane (b) 2, 2-dimethylbutane
11. HBr reacts with under anhydrous
(c) 2, 3-dimethylbutane (d) n-hexane
conditions at room temperature to give (2006)
6. 2-methyl butane on reacting with bromine in the presence of (a) CH3CHO and CH3Br
sunlight gives mainly (2005)
(b) BrCH2CHO and CH3OH
(a) 1-bromo-3-methylbutane (b) 2-bromo-3-methylbutane
(c)
(c) 2-bromo-2-methylbutane (d) 1-bromo-2-methylbutane
(d)
 ALKYL HALIDES 26
12. Which of the following reactions will yield 2, 17. The decreasing order of nucleophilicity among the
2-dibromopropane ? (2007) nucleophiles (2005)

(a) (A) (B)

(b)

(c) (C)

(d)
(D)
13. The treatment of CH3MgX with produces

(2008)
(a) (C), (B), (A), (D) (b) (B), (C), (A), (D)
(a) (b) (c) (D), (C), (B), (A) (d) (A), (B), (C), (D)
18. Tertiary alkyl halides are practically inert to substitution by
SN2 mechanism because of (2005)
(c) (d) (a) steric hindrance (b) inductive effect
(c) instability (d) insolubility
14. The organic chloro compound, which shows complete
19. Which of the following is the correct order of decreasing
stereochemical inversion during an SN2 reaction is (2008)
SN2 reactivity ? (2007)
(a) (C2H5)2CHCl (b) (CH3)3CCl (a) RCH2X > R3C X > R2CH X

(c) (CH3)2CHCl (d) CH3Cl (b) R CH2X > R2CHX > R3C X
(c) R3C X > R2CH X > RCH2 X
15. Following reaction (2002)
(d) R2CH X > R3C X > RCH2 X
(CH3)3CBr + H2O  (CH3)3COH + HBr is an example of
(X = a halogen)
(a) elimination reaction (b) free radical substitution 20. The major organic compound formed by the reaction of
1, 1, 1– trichloroethane with silver powder is : (2014)
(c) nucleophilic substitution (a) Ethene (b) 2-Butyne
(d) electrophilic substitution (c) 2-Butene (d) Acetylene
21. The product of the reaction given below is : (2016)
16. SN1 reaction is feasible in (2002)

(a)

(b) (a) (b)

(c)
(c) (d)

(d)
 27 ALKYL HALIDES
22. The reaction of propene with HOCl 2. In a nucleophilic substitution reaction:
(Cl2 + H2O) proceeds through the intermediate : (2016) DMF
R  Br  Cl   R  Cl  Br  ,
(a) CH3  CH  CH2  Cl Which one of the following undergoes complete inversion
of configuration ? Online 2014 SET (1)
(b) CH3  CH(OH)  CH2 (a) C6H5CHC6H5Br (b) C6H5CH2Br
(c) C6H5CH2CH3Br (d) C6H5CCH3C6H5Br
(c) CH3  CHCl  CH2
3. Conversion of benzene diazonium chloride to chloro
benzene is an example of which of the following reactions?
(d) CH3  CH  CH2  OH
Online 2014 SET (3)
23. The increasing order of reactivity of the following halides
(a) Claisen (b) Friedel-craft
for the SN1 reaction is (2017)
(c) Sandmeyer (d) Wurtz
(I) CH3CH(Cl)CH2CH3 (II) CH3CH2CH2Cl
4. In the presence of peroxide, HCl and HI do not give
(III) p-H3CO–C6H4 – CH2Cl anti-Markownikoff’s addition to alkenes because:
Online 2014 SET (3)
(a) (III) < (II) < (I) (b) (II) < (I) < (III)
(a) HCl is oxidizing and the HI is reducing
(c) (I) < (III) < (II) (d) (II) < (III) < (I)
(b) All the steps are exothermic in HCl and HI
24. The major product of the following reaction is : (2018)
(c) Both HCl and HI are strong acids
(d) One of the steps is endothermic in HCl and HI
5. The major product formed when 1, 1, 1 trichloro–propane
is treated with aqueous potassium hydroxide is :
Online 2014 SET (4)
(a) 2–Propanol (b) Propyne
(c) Propionic acid (d)1–propanol
(a) (b) 6. The gas evolved on heating CH3MgBr in methanol is :
Online 2016 SET (1)
(a) HBr (b) Methane
(c) Ethane (d) Propane
7. Bromination of cyclohexene under conditions given below
(c) (d)
yields : Online 2016 SET (2)

JEE MAINS ONLINE QUESTION

1. For the compounds
CH3Cl, CH3Br, CH3I and CH3F, the correct order of
increasing C – halogen bond length is:

Online 2014 SET (1)

(a) (b)
(a) CH3F < CH3Cl < CH3Br < CH3I

(b) CH3F < CH3Br < CH3Cl < CH3I

(c) CH3F < CH3I < CH3Br < CH3Cl

(d) CH3Cl < CH3Br < CH3F < CH3I (c) (d)
 ALKYL HALIDES 28

8. Which one of the following reagents is not suitable for 13. Which of the following will most readily given the
the elimination reaction ? Online 2016 SET (2) dehydrohalogenation product. Online 2018 SET (1)

(a) NaOH /H2O (b) NaOEt /EtOH (a) (b)

(c) NaOH /H2O  EtOH
(d) NaI
9. Fluorination of an aromatic ring is easily accomplished by
treating a diazonium salt with HBF4 . Which of the (c) (d)
following conditions is correct about this reaction ?
Online 2016 SET (2)
(a) Only heat (b) NaNO2 / Cu 14. The total number of optically active compounds formed
in the following reaction is : Online 2018 SET (2)
(c) Cu2O / H2O (d) NaF/Cu
10. Which of the following compounds will not undergo
Friedel Craft’s reaction with benzene ?
Online 2017 SET (1)

(1) Two (2) Four

(a) (b)
(3) Six (4) Zero
15. The major product of the following reaction is :
(c) (d) Online 2019 SET (2)

11. The major product of the following reaction is :

Online 2017 SET (1)

(a) CH2 = CHCH2CH = CHCH3
(a) (b)
(b) CH2 = CHCH = CHCH2CH3
(c) CH3CH = C = CHCH2CH3
(d) CH3CH = CH – CH = CHCH3
12. The major product of the following reaction is
Online 2017 SET (2) (c) (d)

16. Increasing order of reactivity of the following compounds

for SN1 substitution is : Online 2019 SET (3)

(A) (B)

(a) (b)
(C) (D)

(a) (B) < (C) < (D) < (A) (b) (A) < (B) < (D) < (C)
(c) (B) < (A) < (D) < (C) (d) (B) < (C) < (A) < (D)
(c) (d)
 ALKYL HALIDES 29

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

1. All questions marked “S” are single choice questions
2. All questions marked “M” are multiple choice questions
3. All questions marked “C” are comprehension based questions
4. All questions marked “A” are assertion–reason type questions
(A) If both assertion and reason are correct and reason is the correct explanation of assertion.
(B) If both assertion and reason are true but reason is not the correct explanation of assertion.
(C) If assertion is true but reason is false.
(D) If reason is true but assertion is false.
5. All questions marked “X” are matrix–match type questions
6. All questions marked “I” are integer type questions

Physical and General Properties 5. (A) Assertion : The carbon halogen bond in an aryl halide is
shorter than the carbon halogen bond in an alkyl halide.
1. (S) Which of the following is liquid at room temperature ? 3
Reason : A bond formed of an sp orbital should be
2
(a) CH3I (b) CH3Br shorter than the corresponding bond involving an sp
orbital.
(c) C2H5Cl (d) CH3F
(a) A (b) B
2. (S) Which of the following represents the correct order of (c) C (d) D
densities ?
Preparation of Alkyl Halides
(a) CCl4 > CHCl3 > CH2Cl2 > CH3Cl > H2O
6. (S) The conversion of 2, 3-dibromobutane to 2-butene with
Zn and alcohol is
(b) CCl4 > CHCl3 > CH2Cl2 > H2O > CH3Cl
(a) -Elimination
(c) H2O > CH3Cl > CH2Cl2 > CHCl3 > CCl4
(b) Redox reaction
(d) CCl4 > CHCl3 > H2O > CH2Cl2 > CH3Cl
(c) Both -elimination and redox reaction
3. (S) Which of the following has the highest normal boiling
(d) -Elimination
point ?
7. (A) Assertion : Alkyl iodide can be prepared by treating alkyl
(a) iodobenzene (b) bromobenzene
chloride/bromide with NaI in acetone.
(c) chlorobenzene (d) fluorobenzene
Reason : NaCl/NaBr are soluble in acetone while NaI is
4. (S) Which of the following are arranged in the decreasing not.
order of dipole moment ?
(a) A (b) B
(a) CH3Cl, CH3Br, CH3F (c) C (d) D
8. (S) The number of possible enantiomeric pairs that can be
(b) CH3Cl, CH3F, CH3Br
produced during monochlorination of 2-methyl butane
(c) CH3Br, CH3Cl, CH3F is :
(a) 3 (b) 4
(d) CH3Br, CH3F, CH3Cl
(c) 2 (d) 1
ALKYL HALIDES 30

(b) Symmetrical cis alkene gives 2 products on reaction

Br  H O wit Br2/CCl4
2 2 

9. (S) Product :
(c) Trans alkenes give erythro product
(d) Cis alkenes gives threo product

(a) (b)

Cl 1Mole
2
11. (C) 

CCl4

(c) (d)

Comprehension
Addition of X2 on alkene is electrophilic addition reaction. (a) (b)
Reaction proceed through the formation of 3-membered
cyclic halonium ion. Nucleophile X– attacks from backside
of cyclic halonium ion hence total reaction is anti addition
reaction. If this reaction proceed in polar solvent then
solvent itself acts as nucleophile.

(c) (d)

Mechanism :

2 3Cl ,CH OH
12. (C)  Major product :

(a) (b)

10. (C) Which of the following statements is incorrect ?

(c) (d)
(a) Symmertical trans alkene gives 2 products on reaction
with Br2/CCl4
ALKYL HALIDES 31

13. (I) How many of the following reactions, leads to the 15. (X) Column I Column II
formation of diastereomers.
(A) CH3CH = CH2 
HBr , RCOOR
 (p) Side chain substitution

HCl
(a)   (B) CH3CH = CH2 
HBr
 (q) Anti-Markovnikov’s
CCl4

addition

NBS , h
(C) C6 H5CH3   (r) Aromatic Substitution
HBr
(b)  
CCl4
Br2 / FeBr3
(D) C6 H5CH3   (s) Markovnikov’s addition

HBr 16. (M) Which of the following reactions involve free radical as
(c)  
CCl4 intermediate ?

2 Cl  FeCl
3
(a) 

HCl
(d)  
CCl4
(b) 2Br / hv


(c) NBS


(d) 2Br /CCl

4


HCl 17. (A) Assertion : Chlorination of allylic hydrogen is difficult

(e)  
CCl4
than vinylic hydrogen.
Reason : Allyl radical is stabilised by resonance.
(a) A (b) B
(c) D (d) D

Acetone
HCl 18. (A) Assertion : CH3 – CH2 – Cl + NaI 

(f)  
CCl4
CH3 – CH2 – I + NaCl 
Reason : Acetone is polar protic solvent and solubility
order of sodium halides decreases dramatically in order
14. (S) When but –3-en -2- ol reacts with aq. HBr, the product NaI > NaBr > NaCl. The last being virtually insoluble in
formed is this solvent and a 1° and 2° chloro alkane in acetone is
(a) 3 - bromobut - 1- ene completely driven to the side of Iodoalkane by the
precipitation reaction.
(b) 1 - bromobut - 2- ene
(a) A (b) B
(c) A mixture of both a and b (c) C (d) D
(d) 2 - bromobut - 2 - ene
ALKYL HALIDES 32

22. (S) A compound ‘A’ has molecular formula C5H9Cl. It does not
Cl2  H2O react with bromine in CCl4. On treatment with strong base, it
19. (S)  Major product :
produces single compound ‘B’ (C5H8) and reacts with Br2
(aq). Ozonolysis of ‘B’ produces a compound C5H8O2.
Which of the following is structure of A ?
(a)

(a) (b)

(b)

(c) (d)

(c)

23. (M)

(d)
Mark out the possible product.

Cl
(a)
2 

20. (S) CCl4

(b)

Stereochemistry of the product are :

(a) diastereomers (b) meso
(c)
(c) racemic mixture
(d) pure enantiomers
Reactions of Alkyl Halides : Nucleophilic Substitution
21. (S) An organic compound C3H7Br(A) with alcoholic KOH
(d)
forms C3H6 which decolorises Br2 in CCl4 but does not
gives a white precipitate with ammonical AgNO3. (A) on
reaction with KCN forms a product which on reduction
with Na/C2H5OH produces n-butyl amine. Hence, the 24. (M) Which of the following pair is correctly matched ?
compound (A) is Reaction Product
(a) n-propyl bromide (a) RX + AgCN RNC
(b) isopropyl bromide (b) RX + KCN RCN
(c) 1, 1–dibromopropane
(d) none of these
(c) RX + KNO2

(d) RX + AgNO2
ALKYL HALIDES 33

25. (A) Assertion : Treatment of chloroethane with a saturated X and Y are respectively
solution of AgCN gives ethyl isocyanide as the major
(a) both nitroethane
product.
Reason : Cyanide (CN– ) is an ambident nucleophile. (b) both ethyl nitrite (EtONO
(a) A (b) B (c) X = EtONO and Y = EtNO2
(c) C (d) D
26. (S) Choose the correct statement(s) about the following (d) X = EtNO2 and Y = EtONO
reaction.
Reactions of Alkyl Halides : Metals
CH OH
3

 29. (S) Alkyl halides react with dialkyl copper reagents to give

I. The major product of the reaction is butyl-methyl (a) Alkenes

ether.
II. The major product of the reaction is 1-butene. (b) Alkyl copper halides

III. The major product is formed by SN 2 reaction (c) Alkanes

mechanism.
(d) Alkenyl halides
IV. The major product is followed by E2 reaction
mechanism. 30. (S) What would be the product formed when 1-Bromo-3-
(a) I + III (b) II + IV chloro cyclobutane reacts with two equivalents of metallic
(c) I + IV (d) IV sodium in ether
27. (S) The major substitution product of the following reaction
is Cl

(a) (b)
Br
KSH



(c) (d)

31. (M) Which of the following alkanes cannot be synthesized

by the Wurtz reaction in good yield ?
(a) (b)

(a) (b)

(c) (d)
(c) (d)
32. (S) Which of the following alkyl halides is not suitable for
Corey-House synthesis of alkanes ?
28. (S) Consider the following reaction
(a) CH3I (b)

(c) (d)
ALKYL HALIDES 34

33. (X) Match the column :  3  

i CH MgBr 2 mol conc. H SO
2 4 
 A 
37. (S) CH3CN 
 ii  H O B,
Column-I Column-II 3

Wurtz reaction Number of A and B are

dimerization
product

Na
(A) CH 3  Cl  (p) 5
dyether (a)

Na
(B) CH 3  Cl  CH 3  CH 2  Cl  (q) 6
dryether

(b)
(C) CH3 – Cl + CH3 – CH2 – Cl (r) 3

Na
(c)
+ CH3 – CH2 – CH2 – Cl 
dryether

(d)
(D) H2C = CH – CH = CH – CH2 – Cl (s) 1

Na 38. (S) End product of the following sequence of reaction is

+ CH3 – CH2 – Cl 
dryether


34. (A) Assertion : Wurtz’s coupling reaction of alkyl halide is

not suitable for an alkane containing an odd number of
carbons in the parent chain.
NBS Mg /ether 3 CH CN
Reason : Wurtz’s coupling reaction involves heating of     
 
H3O
alkyl halides with sodium metal in ethereal solution.
(a) A (b) B
(c) C (d) D
35. (I) If an etheral solution containing 2–chloropentane and
chloroethane is heated with sodium, how many different
alkanes would result through Wurtz’s reaction ? (a) (b)
Reactions of Alkyl Halides : Grigand Reagent

36. (S)

(c) (d)

(a) (CH3)2CHCOCH3
39. (S) Which of these do not form Grignard reagent
(b)
(a) CH3F (b) CH3Cl

(c) (CH3)2CHCOCH(CH3)2
(c) CH3Br (d) CH3I

(d)
ALKYL HALIDES 35

40. (S) Identify (Z) in the following reaction

Cl (b) CH3MgBr and

+ Mg THF CO2 H
(X) (Y) (Z)
1 mole
(c) CH3MgBr and
Br

Cl COOH (d) CH3CH2MgBr and

ether
43. (M) R – X + Mg  CH3OH
R –MgX 
(a) (b)  n-butane
What can be R in the above reaction sequence ?
(a) n–propyl (b) n–butyl
COOH COOH
(c) sec–butyl (d) Isopropyl

COOH COOH
(1) 'X'RMgX
44. (I) 
NH Cl
 3° Alcohol. Find
4
(c) (d) out value of ‘X’.
45. (M) Which of the following compounds give alcohol on
Br reaction with RMgX ?

41. (M) In the given reaction,

(a) O2 (b)
H / H O
2  3° Alcohol
(X) + R MgX (excess) 
(X) may be :
(c) R – O – H (d)

(a) (b)
PhMgBr  excess
46. (S) 
  Product :
H3 O

(c) (d)
42. (M) Which of the following combinations give
(a) (b)

(c) (d)

(a) PhMgBr and

ALKYL HALIDES 36

49. (I) Total number of RMgX are consumed in the following

reaction
47. (S)

(a)

(b)

(c) (d) Comprehension

Grignard reagent is usually prepared by
48. (X) Match the Column
Et O
2  RMgX
R  X  Mg 
Column-I Column-II
Grignard reagent
(Reactant) (Reactant)
Et O
2  ArMgX
Ar  X  Mg 
(A) PhMgBr +
Grignard reagent
Grignard reagent acts as a strong base. Grignard reagent
carry out nucleophilic attact k in absence of acidic
(A) 1° alcohol (p) hydrogen. Grignard reagent form complex with its ether
solvent. Complex formation with molecule of ether is an
(B) PhMgBr + important factor in the formation and stability of Grignard
reagent.
50. (C) What is the correct order of reactivity of halides with
(B) 2° alcohol (q) magnesium ?
(a) R – Cl > R – Br > R – I
(C) PhMgBr +
(b) R – Br > R – Cl > R – I
(c) R – I > R – Br > R – Cl

(C) 3° alcohol (r) (d) R – I = R – Br = R – Cl

(D) PhMgBr +
51. (C)
1 xRMgX
 3° alcohol. Value of
 2 NH4Cl
x is :
(D) (s)
(a) 2 (b) 3
(c) 4 (d) 5
Match the missing reagent A, B, C, D
ALKYL HALIDES 37

55. (S) Propyl benzene reacts with bromine in presence of light

or heat to give
52. (C)

(a)
1 x PhMgBr 

 2 H ,

Value of x is :
(b)
(a) 2 (b) 3
(c) 4 (d) 5

Reactions of Aryl Halides

(c)
53. (S) Replacement of Cl of chlorobenzene to give phenol
requires drastic conditions but chlorine of 2, 4-
dinitrochlorobenzene is readily replaced because

(a) NO2 make ring electron rich at ortho and para

(d)
(b) NO2 withdraws e– from meta position

(c) denotes e– at meta position 56. (S) The reaction of 4-bromobenzyl chloride with NaCN in
ethanol leads to
(d) NO2 withdraws e– from ortho/para positions
(a) 4-bromo-2-cyanobenzyl chloride
54. (S) Which chloroderivative of nitrobenzenes among the
(b) 4-cyanobenzyl cyanide
following would undergo hydrolysis, most readily with
(c) 4-cyanobenzyl chloride
aqueous NaOH ?
(d) 4-bromobenzyl cyanide
O2N NO2 NO2 57. (A) Assertion : The presence of nitro group facilitates
nucleophilic substitution reaction in aryl halides.
(a) Cl (b) O2N Cl Reason : The intermediate carbanion is stabilized due to
the presence of the nitro-group.
O2N NO2 (a) A (b) B
(c) C (d) D
O2N O2N 58. (X) Column I Column II

(A) Sandmeyer reaction (p) C 6 H 5 COOAg, Br 2 /CCl 4 ,

(c) O2N Cl (d) Cl heat

(B) Balz-Schiemann reaction (q) CH3CH2CH2Br, KI,

O2N O2N Cl
acetone, heat

(C) Hunsdiecker reaction (r) C6H5N2Cl, HBF4, heat

(D) Finkelstein reaction (s) C6H5N2Cl, CuCl/HCl, heat

ALKYL HALIDES 38

59. (X) Match the column 61. (S) Which is the major product of the reaction of 2, 4–
Column - I Column - II dinitrochlorobenzene with methylamine ?

(A) (p) Nucleophilic

substitution
(a) (b)

3 AlCl
 Ph  CH 2  Cl 

(B) (q) Electrophilic

substitution

(c) (d)

(C) KOH  aq. (r) Cation


intermediate 62. (S) Arrange the following in increasing order of reactivity in
aromatic nucleophilic substitution reaction.

(D) 2Br , hv (s) Free radical


substitution
(I) (II)

60. (S) Which of the following is (are) true regarding

intermediate in the addition-elimination mechanism of
the reaction below ?
(III) (IV)

(a) I < IV < III < II (b) IV < III < I < II
NaOCH (c) I < IV < II < III (d) IV < I < II < III
3  intermediate 
  63. (M) p–nitrofluorobenzene is more reactive than its meta isomer
in SNAr reaction with CH3ONa because
(a) nitro group from para position is in resonance with
lone pair of fluorine.
(b) nitro group from para position stabilizes the benzene
I. The intermediate is aromatic. carbanion intermediate.
II. The intermediate is resonance stabilized anion. (c) nitro group from para position exert greater
III. Electron withdrawing group on the benzene ring electronwithdrawing inductive effect than from meta
position
stabilize the intermediate
(a) I only (b) II only (d) nitro group from para position gives less steric
hindrance than from meta position to the attack of
(c) I and III (d) II and III
nucleophile.
ALKYL HALIDES 39

64. (M) Consider the following SNAr treaction 67. (A) Assertion : A dichlorobenzen is slightly more reactive
than chlorobenzene towards an aromatic nucleophilic
substitution reaction.
Heat Reason : Chlorine has electron withdrawing effect on
+ CH3 ONa  
aromatic ring.
(a) A (b) B
The correct statement is (are) (c) C (d) D
(a) Cl will be substituted because it is a better leaving Polyhalogen Compounds
group. 68. (S) Use of chlorofluoro carbons is not encouraged because
(b) F will be substituted because nitro from para position (a) They are harmful to the eyes of people that use it
facilitate this.
(b) They damage the refrigerators and air conditioners
(c) after substitution of one halogen, substitution of the
(c) They eat away the ozone in the atmosphere
second halogen would become further more difficult.
(d) They destroy the oxygen layer
(d) first chlorine and then fluorine would be substituted
69. (S) The use of the product obtained as a result of reaction
subsequently.
between acetone and chloroform is
65. (M) Consider the following chlorofluorobenzene undergoing
(a) Hypnotic (b) Antiseptic
nucleophilic aromatic (SNAr) substitution reaction with
(c) Germicidal (d) Anaesthetic
KCN
70. (S) B.H.C. is used as
(a) Insecticide (b) Pesticide
(c) Herbicide (d) Weedicide

KCN 71. (S) In fire extinguisher, pyrene is


Heat 
(a) CO 2 (b) CCl 4

(c) CS 2 (d) CHCl 3

The correct statement(s) is/are :
(a) substitution by a chlorine at ‘1’ will promote
substitution of fluorine by CN–.
(b) substitution by a nitro group at ‘2’ will promote
substitution of fluorine by CN–.
72. (S) The commercial uses of DDT and benzene hexachloride
are
(a) DDT is a herbicide, benzene hexachloride is a fungicide
(b) Both are insecticides

(c) substitution by a cyano group at ‘1’ will promote (c) Both are herbicides
–
substitution of chloro by CN .
(d) DDT is a fungicide and benzene hexachloride is a
(d) substitution by a methoxy group at either ‘1’ or ‘2’ herbicide
will discourage the reaction as a whole.
66. (A) Assertion : p-nitrochlorobenzene is more reactive than 73. (S) Which plastic is obtained from CHCl 3 as follows
m-nitrochlorobenzene towards aromatic nucleophilic
substitution reaction. HF 800 o C Polymerisa tion
CHCl 3 
 X   Y     
 Plastic
SbF 3
Reason : Nitro group from para and meta positions has
opposite effect in aromatic nucleophilic substitution
(a) Bakelite (b) Teflon
reaction.
(a) A (b) B (c) Polythene (d) Perspex
(c) C (d) D
ALKYL HALIDES 40

74. (S) What is the reagent used for testing fluoride ion in water

(a) Alizarin - S (b) Quinalizarin

(c) Phenolphthalein (d) Benzene

O (b) Product D is
75. (S) CCl4 is a well known fire extinguisher. However after
using it to extinguish fire, the room should be well
ventilated. This is because :

(a) it is inflammable at higher temperatures (c) Product E is

(b) it is toxic

(c) it produces phosgene by reaction with water vapours

at higher temperatures

(d) it is corrosive (d) Product F is

76. (S) When CHCl3 is boiled with NaOH, It gives

(a) Formic acid (b) Trihydroxy methane 79. (S) Which of the following is missing reagent in the following
(c) Acetylene (d) Sodium formate reaction sequence ?

77. (A) Assertion : Chloral reacts with phenyl chloride to form

DDT.

Reason : It is an electrophilic substitution reaction

(a) A (b) B

(c) C (d) D (a) (CH3)3CO–K+ , Br2 (b) (CH3)3CO–K+, HBr

(c) (CH3)3CO–K+, Br2/H2O

Conversions/Roadmaps (d) H2SO4, Br2

80. (S)

78. (M)

Which of the following is the structure of A ?

(a) (b)

(a) Product C is
(c) (d)
ALKYL HALIDES 41

SOCl Mg,  (a) (b)

81. (S)  2   
Pyridine Et O 2

Product
Product of reaction is :
(c) (d)
(a)

83. (S) Which of the following sequence of reagent is best suited

for the reaction shown below ?

(b)

(c) (a) (i) CH3MgBr, H3O+ (ii) H+/ (iii) HBr/H2O2

(b) (i) CH3MgBr, H3O+ (ii) H+/ (iii) HBr
(c) (i) CH3MgBr, H3O+ (ii) HBr
(d) (i) HBr/ROOR (ii) CH3MgBr, H3O+
84. (S) The major product of the following reaction is
(d)
Na / Ether 2 Br ,hv
Alc.KOH
    

(a) (b)
Br2 / hv
Mg
82. (S) A  B 
Et 2O 

Conc.H SO Zn / H O (c) (d)

2 4
D  2 
E 


Find out the structure of ‘A’ :

 ALKYL HALIDES 42

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION

1. Which of the following has the highest nucleophilicity ? 9. HBr reacts fastest with (1986)
(2000) (a) 2-methyl propan-2-ol (b) propan-1-ol
– –
(a) F (b) OH
(c) propan-2-ol (d) 2-methyl propan-1-ol
(c) CH3 (d) NH 2
10. The reaction conditions leading to the best yield of C2H5Cl
2. An SN2 reaction of an asymmetric carbon of a compound are (1986)
always gives (2001)
(a) an enantiomer of the substrate UV light
(a) C2H6 (excess) + Cl2  
(b) a product with opposite optical rotation
(c) a mixture of diastereomers Dark
(b) C2H6 + Cl2 (excess) 
room temp.
(d) a single stereoisomer
3. Among the following, the molecule with the highest dipole UV light
(c) C2H6 + Cl2 (excess)  
moment is (2003)
(a) CH3Cl (b) CH2Cl2 UV light
(d) C2H6 + Cl2  
(c) CHCl2 (d) CCl4
4. Write the structure of all the possible isomers of 11. n-propyl bromide on treatment with ethanolic potassium
dichloroethene. Which of them will have zero dipole hydroxide produces (1987)
moment ? (1985)
(a) propane (b) propene
5. Draw the stereochemical structures of the products in the
following reactions (c) propyne (d) propanol

12. Chlorination of toluene in the presence of light and heat

followed by treatment with aqueous NaOH gives (1990)

(a) o-cresol (b) p-cresol

(c) 2, 4-dihydroxy toluene

6. Write down the structures of the stereoisomers formed when
cis-2-butene is reacted with bromine. (1995) (d) benzoic acid
7. Chlorobenzene can be prepared by reacting aniline with
13. 1-chlorobutane on reaction with alcoholic potash gives
(1984)
(1991)
(a) hydrochloric acid
(b) cuprous chloride (a) but-1-ene (b) 1-butanol
(c) chlorine in presence of anhydrous aluminium chloride
(c) but-2-ene (d) 2-butanol
(d) nitrous acid followed by heating with cuprous chloride
8. The compound which reacts fastest with Lucas reagent at 14. (CH3)3CMg Cl on reaction with D2O produces (1997)
room temperature is (1981)
(a) (CH3)3CD (b) (CH3)3COD
(a) butan-2-ol (b) butan-1-ol
(c) 2-methyl propan-1-ol (c) (CD)3CD (d) (CD)3COD
(d) 2-methyl propan-2-ol
 43 ALKYL HALIDES
15. Identify the set of reagents/reaction conditions X and Y in (a) mixture of (K) and (L)
the following set of transformations (2002) (b) mixture of (K) and (M)
(c) only (M) (d) only (K)
19. When phenyl magnesium bromide reacts with t-butanol, the
product would be (2005)
(a) X = dilute aqueous NaOH, 20°C, Y = HBr/acetic acid, (a) benzene (b) phenol
20°C
(c) t-butyl benzene (d) t-butyl phenyl ether
(b) X = concentrated alcoholic NaOH, 80°C, Y = HBr/acetic
20. The major product of the following reaction is (2008)
acid, 20°C
(c) X = dilute aqueous NaOH, 20°C, Y = Br2/CHCl3, 0°C
(d) X = concentrated alcoholic NaOH, 80°C, Y = Br2/CHCl3,
0°C
16. How many structures of F is possible ? (2003)

(a) 2 (b) 5
(c) 6 (d) 3 (a) (b)

17. (2003)

(c) (d)
(a) C6H5OC2H5 (b) C2H5OC2H5
(c) C6H5OC6H5 (d) C6H5I
18. The following compound on hydrolysis in aqueous acetone
will give (2005) 21. List-I contains reactions and List-II contains major products.
(2018)
List-I List - II

(P)  1.

(Q) 2.
(K)

(R) 3.

(L)
(S) 4.

5.
(M)
Match each reaction in List-I with one or more products in
List-II and choose the correct option.
(a) P - 1,5; Q - 2; R - 3; S - 4 (b) P - 1,4; Q - 2; R - 4; S - 3
(c) P - 1,4; Q - 1, 2; R - 3,4; S - 4 (d) P - 4,5; Q - 4; R - 4; S - 3,4
 ALKYL HALIDES 44
22. Statement–I : Aryl halides undergo nucleophilic
substitution with ease. (1991)
Statement–II : The carbon-halogen bond in aryl halides
has partial double bond character.
23. Statement–I : Benzonitrile is prepared by the reaction of
chlorobenzene with potassium cyanide.
(1998)
– (a) Compound IV undergoes inversion of configuration
Statement–II : Cyanide (CN ) is a strong nucleophile.
(b) The order of reactivity for I, III and IV is : IV > I > III
24. Aryl halide are less reactive towards nucleophilic
(c) I and III follow SN1 mechanism
substitution reaction as compared to alkyl halide due to
(d) I and II follow SN1 mechanism
(1990)
29. The halogen which is most reactive in the halogenation of
(a) the formation of less stable carbonium ion
alkanes under sunlight is ... (1981)
(b) resonance stabilization
30. The starting material for the manufacture of polyvinyl
(c) longer carbon halogen bond
chloride is obtained by reacting HCl with ... (1983)
(d) the inductive effect
2 31. Carbon tetrachloride burns in air when lighted to give
(e) sp -hybridised carbon attached to the halogen phosgene. (1983)
25. The compounds used as refrigerant are (1990) 32. Carbon tetrachloride is inflammable. (1985)
(a) NH3 (b) CCl4 (c) CF4 33. The reaction of vinyl chloride with hydrogen iodide to give
1-chloro-1-iodoethane is an example of anti-Markownikoff’s
(d) CF2Cl2 (e) CH2F2
rule. (1989)
26. The products of reaction of alcoholic silver nitrite with ethyl
34. Photobromination of 2-methyl propane gives a mixture of
bromide are (1991) 1-bromo-2-methyl propane and 2-bromo-2-methyl propane
(a) ethane (b) ethene in the ratio 9 : 1. (1993)
(c) nitroethane (d) ethyl alcohol 35. Show by chemical equations only, how would you prepare
(e) ethyl nitrite the following from the indicated starting materials. Specify
the reagents in each step of the synthesis. (1979)
27. The correct statements for the following addition reactions
is (are) (2017) (i) Chloroform from carbon disulphide.
(ii) Hexachloroethane (C2Cl6) from calcium carbide.
36. Chloroform is stored in dark coloured bottles. Explain in not
more than two sentences. (1980)
37. Write down the reaction involved in the preparation of
Br2 /CHCl3
  M and N following using the reagents indicated against in
parenthesis. (1984)
“Ethyl benzene from benzene.”
[C2H5OH, PCl5, anhyd. AlCl3]
38. Arrange the following in order of their (1992)
(i) Increasing basicity
– –
Br2 /CHCl3
H2O, OH , CH3OH, CH3O
 O and P

(ii) Increasing reactivity in nucleophilic substitution
reactions
CH3F, CH3I, CH3Br, CH3Cl
(a) (M and O) and (N and P) are two pairs of enantiomers
39. Write the structure of the major organic product expected
(b) Bromination proceeds through trans-addition in both
from each of the following reactions (1992)
the reactions
(c) O and P are identical molecules (i)
(d) (M and O) and (N and P) two pairs of diastereomers
28. For the following compounds, the correct statements with
respect to nucleophilic substitution reaction is (are)
(ii)
 45 ALKYL HALIDES
40. Identify the major product in the following reaction
(1993) (b)

48. What would be the major product in each of the following

reactions ? (2000)

41. Aryl halides are less reactive than alkyl halides towards
nucleophilic reagents. Give reason. (1994) (i)
42. Optically active 2-iodobutane on treatment with NaI in
acetone gives a product which does not show optical
activity. Explain briefly. (1995)
43. Predict the structure of the product in the following reaction
(1996)
(ii)

49. How would you synthesize 4-methoxyphenol from

bormobenzene in NOT more than five steps ? State clearly
44. How will you prepare m-bromoiodobenzene from benzene the reagents used in each step and show the structures of
(in not more than 5-7 steps) ? (1996) the intermediate compounds in your synthetic scheme.
45. Complete the following, giving the structures of the principal (2001)
organic products (1997) 50. Cyclobutylbromide on treatment with magnesium in dry ether
forms an organometallic compound (A). The organometallic
reacts with ethanal to give an alcohol (B) after mild
acidification. Prolonged treatment of alcohol (B) with an
equivalent amount of HBr gives 1-bromo-1-
46. Each of the following reactions gives two products. Write methylcyclopentane (C). Write the structures of (A), (B) and
the structures of the products (1998) explain how (C) is obtained from (B). (2001)

Alc.KOH, heat
(i) C6H5CH2CHClC6H5  


(ii) (CH3)2CH––OCH3  
HI excess
heat  51. (2004)
47. Explain briefly the formation of the products giving the
structures of the intermediates. (1999)

(a) (i)

Identify A to D.

(ii)
ALKYL HALIDES 46

Answer Key
EXERCISE - 1 : (Basic Objective Questions)

1. (b) 2. (d) 3. (a) 4. (b) 5. (b) 6. (b) 7. (a) 8. (d) 9. (d) 10. (a)
11. (a) 12. (a) 13. (b) 14. (b) 15. (b) 16. (a) 17. (b) 18. (c) 19. (d) 20. (c)
21. (d) 22. (b) 23. (a) 24. (bd) 25. (d) 26. (a) 27. (c) 28. (b) 29. (a) 30. (d)
31. (d) 32. (d) 33. (a) 34. (c) 35. (b) 36. (a) 37. (d) 38. (c) 39. (ad) 40. (c)
41. (c) 42. (b) 43. (a) 44. (d) 45. (a) 46. (b) 47. (a) 48. (d) 49. (b) 50. (a)
51. (c) 52. (c) 53. (c) 54. (b) 55. (d) 56. (b) 57. (d) 58. (a) 59. (d) 60. (d)
61. (c) 62. (a) 63. (c) 64. (a) 65. (b) 66. (a) 67. (a) 68. (b) 69. (b) 70. (b)
71. (c) 72. (a) 73. (b) 74. (cd) 75. (a) 76. (b) 77. (b) 78. (b) 79. (c) 80. (c)
81. (a) 82. (b) 83. (c) 84. (a) 85. (b)

EXERCISE - 2 : (Previous Year JEE Mains Questions)

1. (d) 2. (b) 3. (c) 4. (c) 5. (c) 6. (c) 7. (b) 8. (a) 9. (b) 10. (d)
11. (d) 12. (a) 13. (d) 14. (d) 15. (c) 16. (a) 17. (b) 18. (a) 19. (b) 20. (b)
21. (a) 22. (a) 23. (b) 24. (d)
JEE Mains Online
1. (a) 2. (b) 3. (c) 4. (d) 5. (c) 6. (b) 7. (b) 8. (d) 9. (a) 10. (b)
11. (d) 12. (b) 13. (d) 14. (b) 15. (b) 16. (c)

EXERCISE - 3 : (Advanced Objective Questions)

1. (a) 2. (b) 3. (a) 4. (b) 5. (c) 6. (c) 7. (c) 8. (c) 9. (b) 10. (a)
11. (b) 12. (d) 13. (0004) 14. (c) 15. (A – q; B – s; C – p, D – r) 16. (bcd) 17. (d)
18. (c) 19. (a) 20. (c) 21. (a) 22. (b) 23. (ab) 24. (ab) 25. (b) 26. (a) 27. (d)
28. (c) 29. (c) 30. (d) 31. (a, c, d) 32. (d) 33. (A – s; B – r; C – p; D – q) 34. (b) 35. (0006)
36. (b) 37. (d) 38. (b) 39. (a) 40. (a) 41. (a, b, c) 42. (a, b, d) 43. (b, c)
44. (0003) 45. (a, b, d) 46. (a) 47. (d) 48. (A – s; B – r; C – q; D – p) 49. (0007) 50. (c)
51. (b) 52. (b) 53. (d) 54. (b) 55. (b) 56. (d) 57. (a) 58. (A – s; B – r; C – p; D – q)
59. (A – q, r; B – q, r; C – p; D – s) 60. (d) 61. (c) 62. (b) 63. (bd) 64. (bc) 65. (bcd) 66. (c)
67. (a) 68. (c) 69. (a) 70. (a) 71. (b) 72. (b) 73. (b) 74. (a) 75. (c) 76. (d)
77. (a) 78. (abcd) 79. (a) 80. (c) 81. (d) 82. (c) 83. (a) 84. (b)

EXERCISE - 4 : (Previous Year IIT Questions)

1. (c) 2. (d) 3. (a) 4. cis isomer & trans isomer. Trans isomer has zero dipole moment.

5. 6. 7. (d) 8. (d) 9. (a)

10. (a) 11. (b) 12. (d) 13. (a) 14. (a) 15. (b) 16. (d) 17. (b)
18. (a) 19. (a) 20. (a) 21. (b) 22. (d) 23. (d) 24. (b, e) 25. (a, d)
47 ALKYL HALIDES

26. (c, e) 27. (a,b,d) 28. (a,d) 29. fluorine 30. C2H2 31. F 32. F 33. F
34. F 36. chloroform reacts with O2.

37. 38. (i) > > CH3OH > H2O ; (ii) CH3F < CH3Cl < CH3 Br < CH3I

39. (i) (ii) 40.

42. Formation of a racemic mixture. 45.

46. (i) (ii)

48. (i) (ii)

50. A : B: C:

51. A : B:

C: D:

Dream on !!
