TARGET IIT-JEE

HALOALKANES

INDEX
EXERCISE-I ............................................ 2-12
EXERCISE-II.........................................13-21
EXERCISE-III .......................................22-32
EXERCISE-IV/V....................................33-44
 EXERCISE - I
1. Which of the following can not give SN1 reaction easily?
Br
Br Br Br

(A) (B) (C) (D)

2. Which of the following is most reactive toward SN1.

CH2–Cl CH2–Cl CH2–Cl CH2–Cl

(A) (B) (C) (D)

H CH3 OCH3 NO2

3. Which of the following characteristics are follows in Finkelstein reaction-

(A) Reaction of alkyl chlorides/bromides with NaI
(B) Reaction of alkyl chlorides/bromides with NaI in dry acetone
(C) Heating an alkyl chloride/bromide in presence of a metallic fluoride such as AgF, HgF2, CoF2 etc.
(D) All of these

4. SN1 & SN2 is not favourable in

(A) H2C = CH–Cl (B) Ph–CH2–Cl (C) Ph–Cl (D) A and C both

5. LiBr / acetone
   (A), Product (A) is
SN2 condition .

(A) (B)

(C) (D)

OCH3
(x) conc. HI
6.
OCH3

Value of x in above reaction is

(A) 2 (B) 3 (C) 4 (D) 5

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7. Which of following compound will not undergo acid catalysed hydrolysis ?
O–CH3 O–Ph O–CH2CH3

O
(A) (B) (C) (D)

8.

Which of the following orders is correct about leavability of these groups in nucleophilic substitutions?
(A) I > II > III (B) III > II > I (C) III > I > II (D) II > III > I

9. Which of following compounds will show NGP ?

Cl
SPh H H H H H
(A) (B) (C) (D)
H Cl PhS Cl Cl

OCH3
(x) conc. HI
10.
OCH3

x = moles of HI consumed.
value of x is
(A) 2 (B) 4 (C) 5 (D) 6

EtOH
11.   (A)
( SN1 )

Major- product (A) is

(A) (B) (C) (D)

12. In the given reaction : CH OH

 [X]
3

(A) (B) (C) (D)

13. Among the bromides I–III given below, the order of reactivity of SN1 reaction is:

(I) (II) (III)

(A) III > I > II (B) III > II > I (C) II > III > I (D) II > I > III

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 CH3
SOCl 2
14. H OH   (A). Product (A) in
Et
CH3 Et CH3

H Cl H Cl
(A) (B) (C) Cl H (D)
Et CH3 Et

15. When ethyl bromide is treated with moist Ag2O, main product is:
(A) Ether (B) Ethanol (C) Aldehyde (D) All of the above

16. Arrange the following compounds in order of decreasing rate of hydrolysis for SN1 reaction:

(I) CH2–Br (II) H3C CH2–Br

(III) CH3–CH2 CH2–Br (IV) CH CH2–Br

(A) II > III > IV > I (B) IV > III > II > I (C) III > IV > II > I (D) I > II > III > I

17. Which will give white ppt. with AgNO3?

(A) (B) (C) (D) Both A & C

18. NaOH
 A. A is:
excess

(A) (B) (C) (D)

CH3
18 conc. HI
19. CH3 – O – C – CH3

CH3

Products of above reaction is

CH3 CH3
18 18
(A) CH3 – I + CH3 – C – OH (B) CH3 – OH + CH3 – C – I

CH3 CH3
CH3 CH3
18
(C) CH3 – OH + CH3 – C – OH (D) CH3 – I + CH3 – C – I

CH3 CH3

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 CH3
20. Best method for preparation of CH3 – O – C – CH3 by williamson's ether synthesis is

CH3

CH3
(A) CH3O + CH3 – C – Br (B) CH3 – CH – O + CH3 – CH – Br
CH3 CH3 CH3

CH3 CH3
(C) CH3 – C – O + CH3 – Br (D) CH3 – C – OH + CH3 – Br
CH3 CH3

 * HOH
21. In the given reaction: CH 3  CH 2  S CH 2  CH 2  Br  [X] , [X] will be:

* *
(A) CH 3  CH 2  S  CH 2  CH 2  OH (B) CH 3  CH 2  S  CH 2  CH 2  OH
(C) 1 : 1 mixture of (A) and (B) (D) 2 : 1 mixture of (A) and (B)
–
(i) SH (one equivalent)
22. In the given reaction CH 3  CH  CH 2  CH 2  CH  CH 3 [X] , [X] will be:
(ii) KOH
| |
OTs OTs
– – –
OTs S S S
| | | |
(A) CH3 – CH – CH2 – CH2 – CH – CH3 (B) CH3 – CH – CH2 – CH2 – CH – CH3

(C) (D)

23. Which of the following carbocation is most stable.

 
(A) CH2 – CH = CH – O – CH3 (B) CH 2 – CH = CH – CH = CH 2
 
(C) CH3 – CH2 – CH – O – CH3 (D) CH3 – CH – CH2 – O – CH3

24. Which of the following carbocation will undergo rearrangement ?

CH3

  
(A) (B) (C) CH3 – CH – C = O (D) CH3 – NH – CH – CH – CH3 ]
 | |
CH3 CH3

25. A less stable carbonium ion rearranges to a more stable carbonium ion. During this rearrangement, the
migrating atom or group leaves as a
(A) Free radical (B) Carbene
(C) Positively charged ion (D) Negatively charged ion.

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26. Arrange the following compounds in the increasing order of their densities.

Cl Cl Br

(a) (b) (c) (d)

Cl Cl
(A) (a) < (b) < (c) < (d) (B) (a) < (c) < (d) < (b) (C) (d) < (c) < (b) < (a) (D) (b) < (d) < (c) < (a)

27. EtOH SN1 + E1 Products.

Cl
(A) 5 (B) 6 (C) 7 (D) 8

O
||
H
28. (B) , Give structure of (B)

(A)
O

(A) (B) (C) (D)

O
O
Br
Na
29. 

D.E.
Cl

(A) (B) (C) (D)

Br

Na
30. 
 (A)
D.E.

Br

(A) (B) (C) (D)

Br
Na Se
31. 
 (A) 
 (B)
D.E. 
Br
Product (B) will be.
Br

(A) (B) (C) (D)

Cl
n-Pentane  (A)
2
32.
h
Mono-chloro product (including streoisomers) are :
(A) 2 (B) 3 (C) 4 (D) 5
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 Na
33. * Cl   ? Possible products are :
Dry ether
(C = C14)

(A) ** (B) (C) * (D) All of these

* * *

CH 3 CH3
Na
34.   ?
Dry ether
Cl Cl

CH3 CH3 CH3

CH3 CH3
(A) CH3 (B) (C) (D)
CH3

Br Na
35. 
2  ( A ) 
 (B )
h.. DMF

(B) is

(A) (B) (C) (D) None of these

–
O
+
36. t-Bu OTs AcO NaO
(A)

Major-product (A) is
OAc

(A) t-Bu OAc (B) t-Bu

(C) t-Bu (D) t-Bu

OAc

37. In the acid catalyzed dehydration of alcohols to alkenes, the intermediate species formed is-
(A) Free radical (B) Carbocation (C) Carbanion (D) Carbene

Br
(x) NaNH2 – C Na
Ph – CH – CH2 Ph – C –
38.
Br (x = No. of moles of NaNH2)

Value of x is
(A) 1 (B) 2 (C) 3 (D) 4
alc. KOH
39. CH3  CH2  CH  CH3   X (major)
| 
Br

(A) (B) (C) (D) None of these

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40. The energy profile of the given reactions .
+ + +
H –H
CH3 — CH — CH3 CH3 — CH — CH3 CH3 — CH — CH3 CH3 — CH = CH2
| 
+|
OH O
H H

(A) E (B) (C) E (D) E

E

rxn–coordinate rxn–coordinate rxn–coordinate

rxn–coordinate


41. H (X).


Major product (X) is

(A) (B) (C) (D)

42. Which of the following alcohols would be most likely to undergo dehydration with rearrangement by a pro-
cess involving a methyl migration (methyl shift only) ?

OH
(A) (B) OH (C) OH (D)
OH

H SO
43. 2 
4  X, X is


(A) (B) (C) (D)

44. Rate of dehydration when given compound is treated with conc. H2SO4.

(P) (Q) (R) (S)

(A) P > Q > R > S (B) Q > P > R > S (C) R > Q > P > S (D) R > Q > S > P

45. Among the given compounds, the correct dehydration order is :

(I) OH (II) OH (III) OH (IV) OH

(A) I < II < III < IV (B) II < III < IV < I (C) I < III < IV < II (D) I < II < III = IV

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 conc.H2SO 4
46. HO OH  A
OH
Final product A is

(A) HO O (B) CH2 = C = CH2 (C) (D) HO

O
O

Conc . H SO
47..   
2
4  A.


Product A is:

(A) (B) (C) (D)

48. Which of these dehydrates most readily when reacts with conc. H3PO4.
OH OH OH
(A) (B) (C) OH (D)

CH3 CH3
| | H
49. CH3 — C — C — CH3  (P) (Major). Major product (P) is:
| | 
OH OH

O CH3 CH3 CH3

|| | | |
(A) CH3 — C — C — CH3 (B) CH2  C — CH — CH3
|
CH3
O O
CH3
||
(C) (D) CH3  C  CH3
CH3 CH3

Conc. H 2SO 4
50.     A, A is :


(A) (B)

(C) (D)

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 Me
H Et alc. KOH
51.    major product is :
Br Et 

Me
Me Me
Me Me Me Et H Et H Et
(A) (B) (C) (D)
Et Et Et Me
Me

52. Which of following halides gives fastest elimination reaction when it is treated with alcoholic KOH.
Br
Br Br
Br
(A) (B) (C) (D)

53. Which of following is dehydrating agent ?

(A) conc. H3PO4 (B) P2O5 (C) POCl3 (D) All

54. NaI (A), Major-product (A) is

acetone

(A) (B) (C) (D)

–
O SN2 –
O
55. Nu + C L [TS] Nu C + L

Which of the following figures represent correctly the structure of transition state in this reaction?
– –  
(A) [ Nu C L (B) [ Nu C L

(C) either (A) or (B) depending upon situation (D) none of these

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56. Free energy profile for given reaction is

Free
Energy
(A) (B)

reaction co-ordinate

(C) (D)

57. Which of the following reactions is not possible?

(A) R – OH + NaBr R – Br + NaOH (B) R – OH + HBr R – Br + H2O
(C) both reactions are possible (D) both reactions are not possible
58. Consider the given reaction:

H 3C  CH  CH  CH  CH 3  [P]
HBr
| SN1
OH
In the given reaction the product [P] is :
Br
|
(A) H 3C  CH  CH  CH  CH 3 (B) CH 3  CH  CH  CH 2
|
Br Br
|
(C) CH2=CH–CH=CH2 (D) CH 3  CH  CH 2  CH 2  OH

59. In the given pair in which pair the first compound is more reactive than second for SN1 reaction.

(A) Cl CH2Cl

Cl
(B)
Cl

(C)
Cl Cl

Cl Cl

(D)

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60. Which of the following compounds is most rapidly hydrolysed by SN1 mechanism.
(A) C6H5Cl (B) Cl–CH2–CH = CH2
(C) (C6H5)3CCl (D) C6H5CH2Cl

61. Which compound undergoes hydrolysis by the SN1 mechanism at the fastest rate?
CH3 CH3 Br CH3 Br CH3

(A) (B) (C) (D)

Br Br

62. Arrange the following compounds in decreasing order of their reactivity for hydrolysis reaction

(I) C6H5–CH2–Br (II) C6 H 5  CH  C 2 H 5 (III) (IV)

|
Br
(A) I > II > III > IV (B) IV > II > I > III (C) III > IV > II > I (D) IV > III > II > I

ANSWER KEY
1. C 2. C 3. B 4. D 5. C 6. A 7. B
8. A 9. A 10. C 11. B 12. A 13. A 14. A
15. B 16. A 17. D 18. B 19. B 20. C 21. C
22. C 23. A 24. B 25. D 26. A 27. B 28. B
29. C 30. B 31. B 32. C 33. D 34. D 35. B
36. B 37. B 38. C 39. A 40. C 41. A 42. A
43. D 44. C 45. A 46. C 47. D 48. B 49. A
50. B 51. B 52. A 53. D 54. C 55. A 56. B
57. A 58. A 59. C 60. C 61. B 62. B

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 EXERCISE - II
JEE MAINS / AIEEE PREVIOUS YEAR QUESTION
H2O
1. The reaction : (CH3)C – Br  (CH3)3 – C – OH [AIEEE-2002]
(A) elimination reaction (B) substitution reaction
(C) free radical reaction (D) displacement reaction

2. The correct order of the thermal stability of hydrogen halides (H – X) is [AIEEE-2005]

(A) HI > HBr > HCl > HF (B) HF > HCl > HBr > HI
(C) HCl < HF > HBr < HI (D) HI > HCl < HF < HBr
3. Tertiary alkyl halides are practically inert to substitution by SN2 mechanism because of [AIEEE-2005]
(A) insolubility (B) instability (C) inductive effect (D) steric hindrance
4. Elimination of bromine from 2-bromobutane results in the formation of- [AIEEE-2005]
(A) equimolar mixture of 1 and 2-butene (B) predominantly 2-butene
(C) predominantly 1-butene (D) predominantly 2-butyne

5. CH3Br + Nu–  CH3–Nu + Br– [AIEEE-2006]

The decreasing order of the rate of the above reaction with nucleophiles (Nu–) A to D is
[Nu– = (A) PhO–, (B) AcO–, (C) HO–, (D) CH3O–]
(A) D > C > A > B (B) D > C > B > A
(C) A > B > C > D (D) B > D > C > A
6. The structure of the major product formed in the following reaction [AIEEE-2006]

NaCN
 
 ? is
DMF

Cl CN Cl CN
(A) (B) (C) (D)
NC
CN I CN I
7. Reaction of trans-2-phenyl-1-bromocyclopentane on reaction with alcoholic KOH produces [AIEEE-2006]
(A) 4-phenylcyclopentene (B) 2-phenylcyclopentene
(C) 1-phenylcyclopentene (D) 3-phenylcyclopentene

8. Which of the following is the correct order of decreasing SN2 reactivity? [AIEEE-2007]
(A) RCH2X > R3CX > R2CHX (B) RCH2X > R2CHX > R3CX
(C) R3CX > R2CHX > RCH2X (D) R2CHX > R3CX > RCH2X

9. The organic chloro compound, which shows complete stereochemical inversion during a SN2 reaction, is
(A) (C2H5)2CHCl (B) (CH3)3CCl (C) (CH3)2CHCl (D) CH3Cl [AIEEE-2008]

10. Which of the following on heating with aqueous KOH, produces acetaldehyde ? [AIEEE-2009]
(A) CH2 Cl CH2 Cl (B) CH3 CHCl2 (C) CH3 COCl (D) CH3 CH2 Cl

11. From amongst the following alcohols the one that would react fastest with conc. HCl and anhydrous ZnCl2,
is [AIEEE-2010]
(A) 2-Methylpropanol (B) 1-Butanol (C) 2-Butanol (D) 2-Methylpropan-2-ol

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12. Consider the following bromides : [AIEEE-2010]
Me Me
Me Br Me
Br Br
A B C
The correct order of SN1 reactivity is
(A) C > B > A (B) A > B > C (C) B > C > A (D) B > A > C

13. The main product of the following reaction is [AIEEE-2010]

conc.H SO
C6H5CH2CH(OH)CH(CH3)2   
2 
4 ?


C 6H 5 CH(CH3)2
(A) C=C (B) H5C6CH2CH2
C = CH2
H H H3C
H 5C 6 H
(C) C=C (D) C 6H5CH2 CH3
CH(CH3)2 C=C
H
H CH3

14. An unknown alcohol is treated with the “Lucas reagent” to determine whether the alcohol is primary, secondary
or tertiary. Which alcohol reacts fastest and by what mechanism : [JEE-Mains-2013]
(A) tertiary alcohol by SN2 (B) secondary alcohol by SN1
(C) tertiary alcohol by SN1 (D) secondary alcohol by SN2

15. A solution of (–) – 1 – chloro – 1 – phenylethane is toluene racemises slowly in the presence of a small
amount of SbCl5, due to the formation of : [JEE-Mains-2013]
(A) free radical (B) carbanion (C) carbene (D) carbocation

16. 2-chloro-2methylpentane on reaction with sodium methoxide in methanol yields : [JEE-Mains-2016]

CH3
(a) C2H5CH2C – OCH3 (b) C2H5CH2C = CH2 (c) C2H5CH = C – CH3

CH3 CH3 CH3

(A) All of these (B) (a) and (c) (C) (c) only (D) (a) and (b)

17. The reaction of propene with HOCl (Cl2 + H2O) proceeds through the intermediate : [JEE-Mains-2016]
(A) CH3 – CH+ – CH2 – OH (B) CH3 – CH+ – CH2 – Cl
(C) CH3 – CH(OH) – CH2 + (D) CH3 – CHCl – CH2+
18. Which one of the following reagents is not suitable for the elimination reaction ? [JEE-Mains-2016 (online)]
Br

(A) NaI (B) NaOH/H2O-EtOH (C) NaOH/H2O (D) NaOEt/EtOH

19. Bromination of cyclohexene under conditions given below yields : [JEE-Mains-2016 (online)]

Br2/h

Br
Br
Br Br

(A) (B) (C) (D)

Br Br
Br

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20. The major product of the following reaction is : [JEE-Mains Online -2017]

CH3
C6H5CH2 – C – CH2 – CH3 C2H5ONa
C2H5OH
Br

(A) C 6H 5CH = C – CH 2CH 3 (B) C6H5CH2 – C = CH2

CH3 CH2CH3

CH3
(C) C6H5CH2 – C – CH2CH3 (D) C 6H 5CH 2 – C = CH CH3
OC2H5 CH3

21. The major product of the following reaction is : [JEE-Mains Online -2017]

CH3CH CH2CH CH2CH 3 KOH, CH3OH

heat
Br Br
(A) CH2 = CHCH = CHCH2CH3 (B) CH3CH = CH – CH = CHCH3
(C) CH2 = CHCH2CH = CHCH3 (D) CH3CH = C = CHCH2CH3

22. The major product of the following reaction is : [JEE-Mains Online -2017]
OH
1. K2CO3
2. CH3I(1. eq.)
OH

OCH3 OH
O
OCH3

(A) (B) (C) (D)

OCH3 OH

23. The IUPAC name of the following compound is : [JEE-Mains Online -2017]

(A) 2-Ethyl-1,1-dimethylcyclohexane (B) 1-Ethyl-2,2-dimethylcyclohexane

(C) 1,1-Dimethyl-2-ethylcyclohexane (D) 2,2-Dimethyl-1-ethylcyclohexane

24. A mixture containing the following four compounds is extracted with 1M HCl. The compound that goes to
aqueous layer is : [JEE-Mains Online -2017]

H O
S N O

(I) (II) (III) (IV)

(A) (IV) (B) (II) (C) (I) (D) (III)

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25. Which of the following compounds is most reactive to an aqueous solution of sodium carbonate?
[JEE-Mains Online -2017]

(A) (B) (C) (D)

26. The increasing order of the boiling points for the following compounds is :
(I) C2H5OH (II) C2H5Cl (III) C2H5CH3 (IV) C2H5OCH3
[JEE-Mains Online -2017]
(A) (III) < (IV) < (II) < (I) (B) (IV) < (III) < (I) < (II)
(C) (II) < (III) < (IV) < (I) (D) (III) < (II) < (I) < (IV)

27. Which of the following compounds will show highest dipole moment? [JEE-Mains Online -2017]
O O
(I) O (II) (III) O (IV)
O
(A) (I) (B) (II) (C) (III) (D) (IV)

28. Which of the following, upon treatment with tert-BuONa followed by addition of bromine water, fails to decolourize
the colour of bromine? [JEE-Mains-2017]
O
O C6H5 O
(A) (B) (C) (D)
Br Br Br
Br
29. The increasing order of the reactivity of the following halides for the SN1 reaction is :[JEE-Mains-2017]

(I) CH3CHCH2CH3 (II) CH3CH2CH2Cl (III) p – H3CO – C6H4 – CH2Cl

Cl
(A) (II) < (III) < (I) (B) (III) < (II) < (I) (C) (II) < (I) < (III) (D) (I) < (III) < (II)

30. The major product obtained in the following reaction is [JEE-Mains-2017]

Br
H t
BuOK
C6H5

C6H5
(+)
(A) (–)C6H5CH(OtBu)CH2C6H5 (B) (±)C6H5CH(OtBu)CH2C6H5
(C) C6H5CH = CHC6H5 (D) (+)C6H5CH(OtBu)CH2C6H5

31. Which of the following molecules is least resonance stabilized? [JEE-Mains-2017]

(A) (B) (C) (D) N

O O

32. 3-Methyl-pent-2-ene on reaction with HBr in presence of peroxide forms an addition product. The number of
possible stereoisomers for the product is [JEE-Mains-2017]
(A) Four (B) Six (C) Zero (D) Two

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33. The major product formed in the following reaction is : [JEE-Mains-2018]

O HI
Heat
O

I OH I OH
(A) (B) (C) (D)
OH OH I I

34. The major product of the following reaction is : [JEE-Mains-2018]

Br NaOMe
MeOH

OMe OMe
(A) (B) (C) (D)

35. Increasing order of reactivity of the following compunds for SN1 substitution is :[JEE-Mains Online -2019]
CH3
CH2 – Cl Cl Cl
H3C Cl
CH3
H3CO
(i) (ii) (iii) (iv)
(A) (ii) < (i) < (iv) < (iii) (B) (ii) < (iii) < (i) < (iv) (C) (i) < (ii) < (iv) < (iii) (D) (ii) < (iii) < (iv) < (i)

36. Heating of 2-chloro-1 phenylbutane with EtOK/EtOH gives X as the major product. Reaction of X with Hg
(OAc)2/H2O followed by NaBH4 gives Y as the major product . Y is : [JEE-Mains Online -2019]

OH OH

(A) Ph (B) Ph (C) Ph (D) Ph

OH
37. The major product of the following reaction is : [JEE-Mains Online -2019]
Br
KOH alc (excess)

Ph
Br

(A) (B) (C) (D)

Ph Ph
Ph Ph

38. Which hydrogen in compound (E) is easily replaceble during bromination reaction in presence of light?
CH3—CH2—CH=CH2
    (2019 Main, 10 Jan I)
(E)

(A)  -hydrogen (B)  –hydrogen (C)   hydrogen (D)   hydrogen

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39. In SN2 reactions, the correct order of reactivity for the following compounds ? (2014 Main)
CH3Cl, CH3CH2Cl, (CH3)2CHCl and (CH3)3CCl is
(A) CH3CH2Cl > CH3Cl > (CH3)2CHCl > (CH3)3CCl
(B) CH3Cl > (CH3)2CHCl > CH3CH2Cl > (CH3)3CCl
(C) (CH3)2CHCl > CH3CH2Cl > CH3Cl > (CH3)3CCl
(D) CH3Cl> CH3CH2Cl > (CH3)2CHCl > (CH3)3CCl

40. The synthesis of alkyl fluorides is best accomplished by (2015 Main)

(A) Free radical fluorination
(B) Sandmeyer's reaction
(C) Finkelstein reaction
(D) Swarts reaction

41. The major product of the following reaction is (2019 Main, 12 Jan II)

(i) KOH alc.

CH3CH2CH—CH2
(ii) NaNH2
Br Br in liq NH3

(A) CH3CH=CHCH2NH2 (B) CH3CH2CH—CH2

NH2 NH2

(C) CH3CH2CCH (D) CH3CH=C=CH2

42. Which hydrogen in compound (E) is easily replaceble during bromination reaction in presence of light?
CH3—CH2—CH=CH2
    (2019 Main, 10 Jan I)
(E)

(A)  -hydrogen (B)  –hydrogen (C)   hydrogen (D)   hydrogen

43. The major product in the following conversion is (2019 Main, 12 Jan II)

HBr(excess)
CH3O CH=CH—CH3
Heat

(C) HO CH—CH2—CH3 (D) HO CH2—CH—CH3

Br Br

(A) CH3O CH—CH2—CH3 (B) CH3O CH2—CH—CH3

Br Br

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44. The major product of the following reaction is (2019 Main, 12 Jan II)

CH2CH3
NaOEt
H3C C Cl

COOCH2CH3

CH2CH3 OCH2CH3

(A) H3C C OCH2CH3 (B) H3CH2C C CO2CH2CH3

COOCH2CH3 CH3

CO2CH2CH3
CH3CH2C=CH2
(C) (D) CH3C=CHCH3
CO2CH2CH3
45. Which of the following potential energy (PE) diagrams represents the SN1 reaction?
(2019 Main, 9 April II)

PE PE
(A) (B)
Progress of reaction Progress of reaction

PE PE
(C) (D)
Progress of reaction Progress of reaction

46. The major product of the following reaction is (2019 Main, 10 April I)

CH3
CH3
CH3 C CH CH3
(A) CH3 C = CH CH3 (B)
H OCH3

CH3 CH3

(C) CH3 C CH2CH3 (D) CH3 C CH = CH2

OCH3 H

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47. Heating of 2-chloro-1-phenyl butane with EtOK / EtOH gives X as the major product. Reaction of X with
Hg(OAc)2/H2O followed by NaBH4 gives Y as the major product. Y is (2019 Main, 12 April II)

OH OH
Ph
(A) (B) (C) (D) Ph
OH Ph Ph

48. Which one of the following likely to give a precipitate with AgNO3 solution? (2019 Main, 12 April II)
(A) CH2 = CH – Cl (B) CCl4 (C) CHCl3 (D) (CH3)3CCl

49. The major product 'Y' in the following reaction is (2019 Main, 10 April II)

Cl
EtONa HBr
X Y
Heat

Br Br HO
(A) (B) (C) (D)
Br

50. 1-methyl ethylene oxide when treated with an excess of HBr produces (2020 Main, 7 Jan I)

Br Br Br
Br
CH3
(A) (B) (C) Br (D)
CH3 Br CH3

51. The mechanism of SN 1 reaction is given as: (2020 Main, 3 Sep I)


R  X  R X  R || X 
Y
 R  Y  X
Ion pair Solvent
Separted ion
pair

A student writes genreal charascteristics based on the given mechanism as

(a) The reaction is favoured by weak nucleophiles.
(b) R  would be easily formed if the susbtituents are bulky
(c) The reaction is accompanied by recemisation
(d) The reaction is favoured by non-polar solvents.
Which observation are correct?
(A) (a) and (b) (B) (a) and (c) (C) (a), (b) and (c) (D) (b) and (d)

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 ANSWER KEY
1. B 2. B 3. D 4. B 5. A 6. D 7. D
8. B 9. D 10. B 11. D 12. C 13. C 14. C
15. D 16 C 17. B 18. A 19. B 20. A 21. B
22. D 23. A 24. B 25. C 26. A 27. A 28. B
29. C 30. C 31. A 32. A 33. A 34. C 35. A
36. A 37. D 38. C 39. D 40. D 41. C 42. C
43. C 44. D 45. D 46. C 47. C 48. D 49. C
50. A 51. C

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 EXERCISE - III
Single Choice Question:

1.

Identify all possible product obtained by E2 reaction ?

(A) CH3 – CH2 – CH2 – C = CH2 (B)

CH3
(C) both (A) and (B) (D) none of these


H Br2
2.  ( A ) 
  (B)
OH  major CCl4

Product (B) is
(A) meso (B) Racemic (C) Diastereomer (D) optically active single product.

3.

This reaction is a case of

(A) -elimination (B) -elimination (C) - elimination (D) none of these

4. Most reactive towards acid-catalyzed hydrolysis is

OEt
(A) (B) OEt (C) EtOEt (D) EtOH
OEt

Br
5. C – CH2 – CH3

CH2 – CH2 – CH3

Total number of products obtained when this substrate is subjected to E2 reaction will be (including
streoisomer).
(A) 3 (B) 4 (C) 5 (D) 6

6.

The major products obtained when this substrate is subjected to E2 reaction will be

(A) (B) (C) both (A) and (B) (D) none of these

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7.

The major product obtained when this substrate is subjected to E2 reaction under the treatment of potas-
sium tert-butoxide will be

(A) (B) (C) both in equal proportions (D) none of these

CH3 CH3

8. I II III
Br Br

CH3
Ease of -dehydrobromination among these substrates under the treatment of strong base will be in the order
as
(A) I > II > III (B) III > II > I (C) II > I > III (D) II > III > I

9. Which of the following cannot undergo an E2 reaction ?

H3C CH2Br H3C Br CH2Br

CH3 CH3
(A) (B) (C)

(A) A (B) B
(C) C (D) None (all can undergo an E2 reaction)

10. Major product of the reaction is

(A) Butene-1 (B) Trans-2-butene (C) cis-2-butene (D) Butyne-1

11. Which of the following expression is the experimentally observed rate law for an E2 reaction of an alkyl halide
?
(A) Rate = k[RX] (B) Rate = k[RX]2
(C) Rate = k[RX] [base] (D) Rate = k[base]

12. Which alkyl bromide will yield only one alkene upon E2 elimination ?

(A) (B) (C) (D)

13. Which alkyl bromide will yield-3-methyl-1-hexene as the major product upon treatment with potassium t-
butoxide in t-butyl alcohol (solvent) ?

(A) (B) (C) (D)

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14. In order to accomplish the following conversion, what reagent and conditions would be required?

(A) Cold sodium hydroxide (B) Hot conc. sodium hydroxide

(C) Potassium t-butoxide and heat (D) Hot water

15.

Which is most easily dehydrohalogenated ?

(A) I (B) II (C) III (D) All with same ease

CH OH
CH3O – CH = CH2    product formed is
3
16. 
H

(A) Acetal (B) Hemiacetal (C) Alcohol (D) aldehyde

CH3

17.
Cl
Total number of SN1 products of given compound are
(A) 3 (B) 4 (C) 5 (D) 6

Br
18. CH3–CH2–CH2–C–CH2–CH3
CH3
Total number of SN1 + E1 products obtained will be -
(A) 5 (B) 6 (C) 7 (D) 8

CH3
H   OH H
19. CH3 – C – CH – CH3 
 ( A ) ; H

 (B) ; 
 ( C)
  
CH3 OH OH
Stability of product (A), (B), (C) is
(A) C > B > A (B) A > B > C (C) B > C > A (D) C > A > B

CH3
20.
Br

CH3
The major product obtained when this substrate is subjected to E2 reaction will be

(A) (B) (C) both (A) and (B) (D) none of these

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21. Which of the following isomeric hexachlorocyclohexanes is least reactive in -dehydrochlorination on treat-
ment with strong base ?
Cl Cl Cl
Cl Cl Cl Cl Cl Cl
(A) (B) (C) (D) all three are equally reac-
Cl Cl Cl Cl Cl Cl
Cl Cl Cl
tive

22. If the following E2 reaction proceeds through an anti-periplanar transition state, what product or products
are expected ?

(A) Only 3-methylcyclohexene

(B) Only 1-methylcyclohexene
(C) The major product is 3-methylcyclohexene and the minor product is 1-methyl cyclohexene
(D) The major product is 1- methylcyclohexene and the minor product is 3-methyl cyclohexene

23. The nitrogen atom in each of the following tertiary amines may be removed as trimethyl amine by
repeatedHofmann eliminations (exhaustive methylation followed by heating with AgOH).
Which of the amines requires the greater number of Hofmann sequences to accomplish this ?

(A) (B) (C) (D) .

24. Correct order of yield of Hofmann alkene in following reaction will be

CH 3CH 2CHCH 3 X may be F, Cl, Br or I
|
X
(A) F > Cl > Br > I (B) I > Br > Cl > F (C) Cl > F > Br > I (D) I > Br > F > Cl

25.  ? major product is:

Br 2

(A) (B) (C) both (A) & (B) (D) none of these

EtONa
26. CH 3  CH 2  CH  CH 3 alc
. KOH
 X ; CH 3  CH 2  CH  CH 3   Y
Major  Major
| |
Br NMe 3

Product (X) & (Y) respectively is
(A) 1-butene, trans-2-butene (B) 1-butene, cis-2-butene
(C) cis-2-butene, 1-butene (D) trans-2-butene, 1-butene
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27. Predict the major product of the following reaction :
H2SO4
CH3CH2CHCH2OH
heat
CH3
CH3

(A) CH3CH2C = CH2 (B) CH3CH = C(CH3)2

(C) CH3CH = CHCH2CH3 (D) (CH3)2 CHCH = CH2

CH3

28.
Br
CH3
The major product obtained when this substrate is subjected to E1 reaction will be

(A) (B) (C) (D) none of these

 major product having H

29. Con.H2SO4
 
OH
(A) 12  H (B) 8 H (C) 4  H (D) 11  H

One or more than one correct :

CH3
| NaCN
30. Consider the given reaction : H  C  OTs   CH3 CH2CH  CN
| |
C2H5 (S) CH3
Which of following statements are correct for above reaction.
(A) Product formation takes place due to the breaking of O–Ts (B) The reaction is S
N2
(C) The reaction is S 1 (D) Configuration of product is (R)
N
31. Rate of SN2 will be negligible in

(A) (B) (C) (D)

32. Which are possible products in following

moist Ag O
  2

SN1

CH3 OH

(A) (B) (C) (D)

33. SN1 & SN2 product are same in (excluding stereoisomer)

Cl
H
(A) (B) (C) (D) Ph  CH  CH  CH3
| |
CH3 Cl

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34. Statement 1: On moving 1° to 3° alkyl halide rate of E2 increases while rate of SN2 decreases
Statement 2: E2 reaction give elemental effect with respect to halogen.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

PCl5
35. CH3 – CH2 – O – CH3  
Products are :
(A) CH3 – Cl (B) Et – Cl (C) Cl (D) Cl
O
36. || PCl5 product are
Ph – C – CH3 
Cl
| Cl
(A) Ph – C – CH3 (B) Ph – CH – CH 2 (C) Ph – CH 2 – CH (D) Ph – CH2 – CH2
| | | Cl
Cl Cl Cl

37. Zndust
(p)   
compound (p) is
CH3 CH3
H Br H Br Br Br
(A) (B) (C) Br (D)
H Br Br H Br
CH3 CH3

CH3
H Br Zndust
38.    (p). The product (p) is
Br H
CH3

(A) (B) (C) (D)

Paragraph for Question Nos. 39 to 41 (3 questions) :

Dehydration require an acid catalyst to protonate the hydroxy group of the alcohol and convert it into good
leaving group. Loss of water followed by a loss of a proton, given the alkene an equilibrium is established
between reactants and products.
OH
+
H CH –CH=CH
3 2

Mechanism

H
 
OH + H2SO4 O CH3–CH–CH 2
(r.d.s)
HSO4 H
H
H2O :


CH3–CH=CH2 + H3O

39. To improve the yield of above reaction which of following is correct.

(A) High temperature (B) Distillation (C) Addition of H2O (D) Both (A) and (B)

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 OH
H H 
40. (i) 
 (A) Major (ii)  (B) Major
 
OH

OH

H
(iii) 
 (C) Major


total number of -hydrogen in A + B + C is

(A) 23 (B) 25 (C) 37 (D) 29
41. Which alcohol is most reactive towards dehydration of alcohol in acid catalyzed reaction.
OH OH OH
OH
(A) (B) (C) (D)

Match the Column :

42. Column I Column II
Primary alkyl bromide SN2 relative rate
(A) CH3 – CH2 – Br (P) 10–5
(B) Me – CH2 – CH2 – Br (Q) 10–2

(C) Me – CH – CH2 – Br (R) 0.8

|
Me

Me

(D) Me – C – CH2 – Br (S) 1

Me

43. Column I Column II

Alkyl–P–toluene sulfonate Ethanolysis relative rate (50°C)
(A) CH3 – CH2 – OTs (P) 1010
(B) H2C = CH – CH2 – OTs (Q) 105
(C) Ph – CH2 – OTs (R) 400

(D) Ph – CH – OTs (S) 35

Ph
(E) Ph3C – OTs. (T) 1

44. Substrate E2 elimination SN2– substitution

(A) CH3 – CH2 – Br (P) 1 (W)  0
(B) (CH3)2 CH – Br (Q) 80 (X) 20
(C) (CH3)3 CBr (R) 100 (Y) 90

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45. Reaction Relative rate of reaction

(A) (P) 1

(B) (Q) 200

(C) (R) 10,000

(D) (S) 30,000

46. Column I Column II

Alkyl-bromide Relative rate of SN1

(A) (P) 1

(B) (Q) 11.6

(C) CH3–CH2–Br (R) 1,200,000

47. Column I Column II

Solvent Relative rate of SN1
(A) 100 % water (P) 1200
(B) 80% water + 20% ethanol (Q) 400
(C) 50% water + 50% ethanol (R) 60
(D) 20% water + 80% ethanol (S) 10
(E) 100% ethanol (T) 1
48. Match List-I with List-II for given SN2 reaction & select the correct answer from the codes given below
– –
Z–CH2Br + CH 3 O  Z–CH2–OCH3 + Br
List-I List-II (relative reactivity)
(A) H– (P) 0.1
(B) CH3 – (Q) 3
(C) C2H5 – (R) 1

(D) (S) 100

49. Match List I with List II and select the correct answer from the codes given below:
List I List II
–
(A) CH3–O–SO2CH3 + C2 H5 O (1) CH3–CH2–PH2
(B) CH3–CH2–I + PH3 (2) CH3–O–C2H5
– +
(C) HC  C Na + CH3–CH2–Br (3) CH3–O–CH3
–
(D) CH3–Cl + CH3– O (4) CHC–CH2–CH3

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50. Column-I and Column-II contains four entries each. Entries of column-I are to be matched with one entry of
column-II. single choice question.
(one to one matching)

Column-I Column-II

(A) EtOH
 (P) SN2 reaction

CH 3
| EtO 
(B) CH 3  CH  CH 2 Br  
EtOH
(Q) E1 reaction

CH OH
(C) 3
 (R) E2 reaction


CH 3 O
| ||
CH3 CO
(D) CH 3  CH  Cl     (S) SN1 reaction

51. Nu + Me–OTs DMF

 Me–Nu + TsO
sO
25
This is a SN2 reaction where nucleophile attack Me–OTs in the rate determining step to give the product.
Rate of this reaction increases with concentration as well as nucleophilicity of the nucleophile. Match the
column I with column II for the above reaction
Column I Column II
(Nucleophile) (Relative rate)
(A) (P) 3.25
(B) (Q) 6.25
(C) (R) 1.0
(D) (S) 7.75

52. Match List-I with List-II (no. of structural isomers produced in -E2 elimination) and select the correct answer.

List-I List-II

(a) (i) Three

Br

(b) H3C CH3 (ii) Zero

CH3

(c) (iii) One

(d) (iv) Two

(a) (b) (c) (d) (a) (b) (c) (d)

(A) (i) (ii) (iv) (iii) (B) (iv) (iii) (i) (ii)
(C) (iv) (iii) (ii) (i) (D) (i) (iii) (iv) (ii)
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53. Match the column

+
O – CH2– CH3 H3O
(A) (W) One of product is Ph – OH

+
H3O
(B) O (X) One of product is CH3 – CHO

+
H3O
(C) O (Y) One of product is 2° alcohol

+
H3O
(D) O (Z) No-reaction

54. Column-I Column-II

CH 3 CH3
(A) H (P) Pinacol fashion reaction
C—C 

CH 3 CH3
O

CH3 CH3
| |
H2SO4
(B) CH3 — C — C — CH3  (Q) Pinacolic Diazotization reaction

| |
OH OH

CH3 CH3
| | NaNO 2
(C) CH3 — C — C — CH3    (R) Pinacol-Pinacolone reaction
| | HCl
OH NH2

O
||
TsCl
(D)    (S) Product formed is CH3 — C — CH — CH3
Pyridine
OH OH CH3

(T) Semipinacol reaction

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55. Column-I Column-I
(A) Best leaving group (P) F
(B) Best nucleophile in polar protic solvent (Q) Cl

(C) Best nucleophile in polar aprotic solvent (R) Br

(D) Weakest base (S) I

ANSWER KEY
1. C 2. A 3. B 4. A 5. C 6. B 7. A
8. D 9. A 10. B 11. C 12. B 13. D 14. C
15. A 16. A 17. B 18. C 19. D 20. D 21. B
22. A 23. A 24. A 25. A 26. D 27. B 28. B
29. B 30. BD 31. ABC 32. AB 33. BC 34. B 35. AB
36. A 37. A 38. B 39. D 40. D 41. A
42. AS ; BR; C Q ; DP 43. AT;B  S ; C  R ; D  Q ; E P
44. A  P,Y ; B  Q, X ; C  R,W 45. AS ; BR; CQ ; DP
46. AR ; BQ; CP 47. AP ; BQ;CR;DS ;ET
48. AS ;BQ; C R ; DP 49. A  2, B  1, C  4, D  3
50. AS,BR,CQ, DP 51. AS ,BQ, CP , DR
52. B 53. A  W ; B  XY ; C  WY ; D  Z
54. A  P ; B  R ; C  Q ; D T ; 55. A  S ; B  S ; C  P ; D S
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 EXERCISE - IV
IIT - JEE / ADVANCED PREVIOUS YEAR QUESTION
1. Ethyl alcohol is heated with conc. H2SO4. The product formed is [IIT 1980]
(A) H3C – C – OC2H5 (B) C2H2 (C) C2H4 (D) C2H6
O

2. The compound which reacts fastest with Lucas reagent at room temperature is [IIT 1981]
(A) butan-2-ol (B) butan-1-ol
(C) 2-methyl propan-1-ol (D) 2-methyl propan-2-ol

3. Diethyl ether on heating with conc. HI gives two moles of [IIT 1983]

(A) ethanol (B) iodoform (C) ethyl iodide (D) methyl iodide

4. When propyne is treated with aqueous H2SO4 in presence of HgSO4, the major product is
(A) propanal (B) propyl hydrogen sulphate [IIT 1983]
(C) acetone (D) propanol

5. HBr reacts fastest with [IIT 1986]

(A) 2-methyl propan-2-ol (B) propan-1-ol (C) propan-2-ol (D) 2-methyl propan-1-ol

6. Alcoholic solution of KOH is a specific reagent for [IIT 1990]

(A) Dehydration (B) Dehydrogenation
(C) Dehydro halogenation (D) Dehalogenation

7. 1-Chlorobutane on reaction with alcoholic potash gives:

(A) 1-butene (B) 1-butanol (C) 2-butene (D) 2-butanol [IIT 1991]

8. The products of reaction of alcoholic AgNO2 with ethyl bromide are [IIT 1991]
(A) Ethane (B) Ethyl nitrite (C) Nitroethane (D) Ethyl alcohol

*9. The ether O–CH2 when treated with HI produces [IIT 1999]

(A) CH2I (B) CH2OH (C) I (D) OH

10. In the reaction OCH3 

HBr
 the products are [IIT 2000]

(A) Br OCH3 and H2 (B) Br and CH Br

3

(C) Br and CH3OH (D) OH and CH3Br

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11. The order of reactivity of the following alkyl halides for a SN2 reaction is: [IIT 2000]
(A) RF > RCl > R–Br > R–I (B) R–F > R–Br > R–Cl > R–I
(C) R–Cl > R–Br > RF > RI (D) R–I > RBr > R–Cl > R–F

12. Identify the set of reagents / reaction conditions 'X' and 'Y' in the following set of transformation:
X Y
CH3 – CH2 – CH2Br  Product  CH3  CH  CH3 [JEE 2002]
|
Br
(A) X = dilute aqueous NaOH, 20°C; Y = HBr / acetic acid, 20°C
(B) X = concentrated alcoholic NaOH, 80°C; Y = HBr/ acetic 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

OH
–
OC H
13. + C2H5I   

2 5
[IIT 2003]
anhyd. C2H5OH

(A) C6H5OC2H5 (B) C2H5OC2H5 (C) C6H5OC6H5 (D) C6H5I

14. Benzamide on treatment with POCl3 gives [IIT 2004]

(A) aniline (B) benzonitrile (C) chlorobenzene (D) benzyl amine

15. The best method to prepare cyclohexene from cyclohexanol is by using [IIT 2005]
(A) conc. HCl + ZnCl2 (B) conc. H3PO4 (C) HBr (D) conc. HCl

16. 1–bromo–3–chlorocyclobutane when treated with two equivalents of Na, in the presence of ether which of the
following will be formed? [IIT ‘2005]

(A) (B) (C) (D)

17. The following compound on hydrolysis in aqueous acetone will give : [IIT 2005]

CH3 CH3 CH3

CH3–O NO2

H Cl CH3

CH3 CH3 CH3 CH3 CH3 CH3

(K) CH3–O NO2 (L) CH3–O NO2

H OH CH3 OH H CH3
CH3 CH3 CH3

(M) CH3–O NO2

H CH3 OH
(A) mixutre of (K) and (L) (B) mixture of (K) and (M)
(C) only (M) (D) only (K)

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18. The reagent(s) for the following conversion,
Br , is/are [IIT 2007]
Br ? H H
(A) alcoholic KOH (B) alcoholic KOH followed by NaNH2
(C) aqueous KOH followed by NaNH2 (D) Zn / CH3OH

19. The correct stability order for the following species is [JEE 2008]

  
O O 
(I) (II) (III) (IV)
(A) II > IV > I > III (B) I > II > III > IV (C) II > I > IV > III (D) I > III > II > IV

20. The major product of the following reaction is [IIT 2008]

Me Br
- +
F PhS Na
dimethylformamide

NO2

Me SPh Me SPh Me Br Me SPh

F F SPh SPh
(A) (B) (C) (D)

NO2 NO2 NO2 NO2

21. In the following carbocation, H/CH3 that is most likely to migrate to the positively charged carbon is
H H
|
1 + | 5
2 4
H3C — C — C — C — CH3
| | | [JEE 2009]
HO H CH3
(A) CH3 at C-4 (B) H at C-4 (C) CH3 at C-2 (D) H at C-2

22. The synthesis of 3-octyne is achieved by adding a bromoalkane into a mixture of sodium amide and an
alkyne. The bromoalkane and alkyne respectively are – [IIT 2010]
(A) BrCH2CH2CH2CH2CH3 and CH3CH2CCH
(B) BrCH2CH2CH3 and CH3CH2CH2CCH
(C) BrCH2CH2CH2CH2CH3 and CH3CCH
(D) BrCH2CH2CH2CH3 and CH3CH2CCH

23. The bond energy (in kcal mol–1) of a C–C single bond is approximately [JEE 2010]
(A) 1 (B) 10 (C) 100 (D) 1000

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24. The major product of the following reaction is : [IIT 2011]

O
C
(i) KOH
NH
C (ii) Br CH2Cl
O

O O
C C
(A) N – CH2 Br (B) N CH2Cl
C C
O O

O O

C C

N N
(C) (D)
C C

O – CH2 Br O CH2Cl

25. The major product of the following reaction is [JEE 2011]

RCH2 OH
  
H ( anhydrous )

(A) a hemiacetal (B) an acetal (C) an ether (D) an ester

26. K in acetone, undergoes SN2 reaction with each of P, Q, R and S. The rates of the reaction vary as
O
||
Cl
H3C – Cl Cl Cl [JEE-Advance 2013]
P Q R
S
(A) P > Q > R > S (B) S > P > R > Q (C) P > R > Q > S (D) R > P > S > Q

27. The acidic hydrolysis of ether (X) shown below is fastest when [IIT Advance - 2014]

(A) one phenyl group is replaced by a methyl group.

(B) one phenyl group is replaced by a para-methoxyphenyl group.
(C) two phenyl groups are replaced by two para-methoxyphenyl groups.
(D) No structural change is made to X.

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28. Compound(s) that on hydrogenation produce(s) optically inactive compound(s) is(are)
[IIT Advance - 2015]

(A) (B)

(C) (D)

29. The major product of the reaction is : [IIT Advance - 2015]

H3 C CO2H
NaNO2 , aqueous HCl
0°C
CH3 NH2
H3C NH2 H3C CO2H
(A) (B)
CH3 OH CH3 OH
H3C CO2H H3C NH2
(C) (D)
CH3 OH CH3 OH

30. For the following compounds, the correct statement(s) with respect to nucleophilic substitution reaction
is(are) [IIT Advance - 2017]
CH3
CH3
Br Br
H3C – C – Br Br

CH3
I II III IV
(A) I and II follow SN2 mechanism (B) The order of reactivity for I, III and IV is IV > I > III
(C) I and III follow SN1 mechanism (D) Compound IV undergoes inversion of configuration

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31. In the following reaction sequence, the correct structure(s) of X is (are) : [IIT Advance - 2018]

Me N3
(1) PBr3,Et2O
X
(2)NaI,Me2CO
(3) NaN3,HCONMe2
enantiomerically pure

Me OH Me OH
(A) (B)

(C) Me (D) Me
OH OH

32. LIST-I contains reactions and LIST-II contains major products. [IIT Advance - 2018]
LIST-I LIST-II

P. + 1.
ONa Br OH

Q. + HBr 2.
OMe Br

R. + NaOMe 3.
Br OMe

S. + MeBr 4.
ONa
O
5.
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

ANSWER KEY
1. C 2. D 3. C 4. C 5. A 6. C 7. A
8. C 9. AD 10. D 11. D 12. B 13. A 14. B
15. B 16. D 17. A 18. B 19. D 20. A 21. D
22. D 23. C 24. A 25. B 26. B 27. C
28. BD 29. C 30. ACD or ABCD 31. B 32. B

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 EXERCISE - V SUBJECTIVE PROBLEMS

1. Chloroform is stored in dark coloured bottles. Explain in not more than two sentences. [IIT 1980]
2. The halogen which is most reactive in the halogenation of alkanes under sunlight is ______ .[IIT 1981]
3. Carbon tetrachloride burns in air to give phosgene. ( TRUE / FALSE ) [IIT 1983]
4. Carbon tetrachloride is inflammable. ( TRUE / FALSE ) [IIT 1985]
5. How may be the following transformation be carried out (in not more than six steps)? [IIT 1986]
"Ethyl alcohol to vinyl acetate".

6. The compounds used as refrigerant are [IIT 1986]

(A) NH3 (B) CCl4 (C) CF4 (D) CF2Cl2
(E) CH2F2

7. Fill in the blanks:

(a) Butan nitrile can be prepared by heating _____with alcohalic KCN. [IIT 1992]

(b) Amongst three isomers of nitrophenol, the one that is least soluble in water is_____ [IIT 1992]

8. Identify the major product in the following reaction. [IIT 1993]

H
Alc.KOH
C6H5—CH2 CH3   ? HBr
 ?


Br
9. Aryl halides are less reactive than alkyl halides towards nucleophilic reagents. Give reason.
[IIT 1994]
10. Write down the structure of the stereoisomers formed when cis-2-butene is reacted with bromine.
[JEE 1995]

11. Arrange the following compounds in order of increasing dipole moment [IIT 1996]
Toluene m-dichlorobenzene o-dichlorobenzene p-dichlorobenzene
I II III IV
(A) I < IV < II < III (B) IV < I < II < III (C) IV < I < III < II (D) IV < II < I < III

12. An alkyl halide X of formula C6H13Cl on treatment with potassium tertiary butoxide gives two isomeric
alkenes Y and Z (C6H12). Both alkenes on hydrogenation give 2,3–dimethylbutane. Predict the structures
of X, Y and Z. [IIT 1996]

13. Predict the structure of the intermediates/products in the following reaction sequence – [IIT 1996]

NaI

 C
Acetone

14. A compound D (C8H8O) upon treatment with alkaline solution of iodine gives a yellow precipitate. The
filtrate on acidification gives a white solid E (C7H6O2). Write the structures of D, E and explain the
formation of E. [JEE 1996]
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15. Complete the following reaction with appropriate structures of products/reagents. [IIT 1998]

Br2 ( i ) NaNH ( 3 equi.)

 (A)   2  
  (B)
( II ) CH 3I

16. (a) Write a chemical test of distinguish between: [CBSE 2013]

(i) Chlorobenzene and Benzyl chloride
(ii) Chloroform and Carbon tetrachloride
(b) Why is methyl chloride hydrolysed more easily than chlorobenzene?

17. Give reasons for the following: [CBSE 2013]

C–X bond length in halobenzene is smaller than C–X bond length in CH3–X.

18. Write the mechanism of the following reaction : [CBSE 2014]

CH3CH2OH 
 CH3CH2Br + H2O
HBr

19. Which halogen compound in each of the following pairs will react faster in SN2 reaction :
[CBSE 2014]
(i) CH3Br or CH3I (ii) (CH3)3C–Cl or CH3 – Cl

20. What happens when [CBSE 2015]

(i) ethyl chloride is treated with NaI in the presence of acetone.
(ii) chlorobenzene is treated with Na metal in the presence of dry ether.
(iii) methyl chloride is treated with KNO2?
Write chemical equations in support of your answer.

21. Which of the following two reactions in SN2 and why ? [CBSE 2016]
C2H5 C2H5
(i) H 
Y
 H
X CH3 Y
CH3
C2H5 C2H5
(ii) H 
 Y
H
X Y CH3
CH3

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 ANSWER KEY
1. 2CHCl3 + O2  2COCl2 + H2O
Phosgene (Poisonous gas)
2. Fluorine
3. False
4. False

conc. H 2SO 4 Br2 alc.KOH

5. CH3CH2OH    CH2= CH2  CH 2  CH 2   H–CC–H
NaNH 2
 | |
Br Br

Hg
(CH 3COO ) 2
  CH 2  CH  OCOCH 3
CH 3COOH vinyl acetate

6. AD

7. (a) propyl chloride, (b) ortho

H
Alc.KOH
8. C6H5—CH2 CH3   C6H5–CH=CH–CH3 HBr
 C6 H 5  CH  CH 2  CH 3
 |
Br Br
+
X X

9.

aryl halide

Due to the above resonance phenomena, C–X bond acquire partial double bond character and becomes
difficult to break in the rate determining step of SN2 reaction.

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 10. + Br2 

11. B

CH 3 CH 3 CH 3 CH 3
| | | |
12. (X): CH 3  C — CH  CH 3 ; (Y) : CH 2  C — CH  CH 3 ; (Z) : CH 3  C  C  CH 3
| | |
Cl CH 3 CH 3

13. (NGP due to MeO, so retention of configuration)

14. E = C6H5COOH ( benzoic acid)

O
|| I2
 C6 H 5  C  CH 3 
NaOH
C6H5–COONa + CHI3

(A) NaNH ( liq .) CH 3I

15.  2   (B)

16. (a) (i) Benzyl chloride undergoes nucleophilic substitution via resonance stabilized benzyl
carbocation and hence undergoes substitution readily.
+ CH2 CH2 CH2 CH2 + CH2
+ +

+
On the other hand, C–Cl bond in benzene has partial double bond character due to
resonance and hence is difficult to cleave. Therefore, benzyl chloride undergoes
nucleophilic substitution much more easily than chlorobenzene.

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 (ii) By partial reduction of carbon tetrachloride with iron fillings and water.
Fe / H 2O
CCl4 + 2[H]    CHCl3 + HCl
Heat
Chloroform manufactured by this method is used as a solvent as it is not of required
purity for its use as an anaesthetic agent.

+
Cl Cl


17. 
 due to formation of

= bond B/W carbon & halogen atom bond length  cress thats why C—X bond length in halo benzene
is smaller than C—X bond lengths in CH3—X.

18. Step - 1 : Protonation of alcohol

 
: :

CH3–CH2–O–H + H CH3–CH2–O–H
H
Step - 2 : Dehydration to form carbocation and attack of nucleophile.


CH3–CH2–O–H + Br CH3–CH2–Br + H2O
H

19. (i) CH3 – I (ii) CH3 – Cl

(i) CH3–CH=CH2  CH3 – CH – CH3

oxymercuration demercuration
20. Hg(OOCCH 3 )/H 2 O
|
OH

Br Br
Br Br


COCH3
(ii)
 
H 2SO 4 /SO3
 SO3H

CH3COCl
AlCl3 (anhyd)

SO3H

Desulphonation


COCH3

CH3 – CH – CH2 – CH3

(iii) | 
alc. KOH
 CH3 – CH = CH – CH3
Br
OR

(i) CH3CH2Cl 

NaI
Acetone
CH3CH2I + NaCl

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(ii) PhCl 
Na
ether
 Ph–Ph, Fittig Reaction

(iii) CH3Cl 

KNO 2
 CH3– O – N = O

21. (i) Due to inversion of configuration.

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