Alkyl Halide Sheet Un Academy 1

ORGANIC CHEMISTRY
ALKYL HALIDE
CONTENTS
JEE MAINS
Exercise-I : 2 - 12
Exercise-II : 13 - 16
Exercise-III : 17 - 21
Exercise-IV : 22 - 32
JEE ADVANCE
Exercise-I : 33 - 35
Matrix : 36 - 41
Exercise-II : 42 - 46
Exercise-III : 47 - 49
Answer Key : 50 - 54
JEE MAINS
EXERCISE-I
SCQ :
K1
1. (i) CH3 – CH2 – Br + NaOH  CH3 – CH2 – OH + NaBr reaction –––– (i)
CH3
K2
(ii) CH3 – C – CH2 – Br + NaOH  (CH3)3 C – CH2 – OH + NaBr reaction –––– (ii)
CH3
K1 & K2 are rate constant for above reaction. Correct relation is

(A) K1 = K2 (B) K1 > K2 (C) K1 < K2 (D) K1 < < K2.
2. Free energy profile for given reaction is
Free
Energy
(A) (B)
VIBRANT ACADEMY reaction co-ordinate
(C) (D)
3. Rate expression for reaction given in Que.(2) is

(A) rate = K [CH3 – Br] (B) rate = K[HO] [CH3–Br]
(C) rate = K[HO]
unacademy (D) rate = K [HO]2 [CH3–Br]
4. NaI (A), Major-product (A) is

acetone
(A) (B) (C) (D)
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5. LiBr / acetone
   (A), Product (A) is
SN2 condition .
(A) (B)
(C) (D)
–
O SN2 –
O
6. 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
7.
VIBRANT ACADEMY
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
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.
O–CH3
unacademy
Which of following compound will not undergo acid catalysed hydrolysis ?
O–Ph O–CH2CH3
O
(A) (B) (C) (D)
10. Which of the following ethers is unlikely to be cleaved by hot conc. HBr?
O C 2H 5
(A) | (B) O (C) O (D) O
CH2
11. The reaction of CH3OC2H5 with one mole HI gives
(A) CH3OH (B) C2H5OH (C) CH3I + C2H5OH (D) C2H5I + CH3OH
O CH3
conc.HI
12. (excess)
Product of above reaction is
I & CH3OH OH & CH3I

(A) (B)
I & CH3I OH & CH3OH

(C) (D)
13.
VIBRANT ACADEMY
SN2 reactivity of these substrate, under identical conditions, will be in the order as
(A) I > II > III (B) III > II > I (C) III > I > II (D) II > III > I
14. A gem dichloride is formed in the reaction except:
(A) CH3CHO and PCl5 (B) CH3COCH3 and PCl5
OH O
(C) 2PCl5 (D) PCl
5

 
OH
15. From each of the following pairs select the compound that will react faster with sodium iodide in acetone.
(a) 2-Chloropropane or 2-bromopropane
I II
(b)
(A) (a)-I, (b)-I

unacademy
1-Bromobutane or
I
2-bromobutane
(B) (a)-I, (b)-II

II
(C) (a)-II, (b)-I (D) (a)-II, (b)-II
N S 2
16. + OH– 
 A
A is:
HO H HO CH3
(A) (B) (C) Both (D)
H CH3 H H
17. Which of the following nucleophile will show minimum reactivity towards SN2 reaction:
– – –
(A) Me3CO (B) MeO (C) (D) Me2CHO
18. KSH

(A) (B) (C) (D)
19. 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
20.
OCH3
Value of x in above reaction is

(A) 2 (B) 3 (C) 4 (D) 5
21.
VIBRANT ACADEMY OCH3
(x) conc. HI
OCH3
x = moles of HI consumed.
value of x is
(A) 2 (B) 4 (C) 5 (D) 6
22. Consider the reaction of HI with the following:
I
unacademy II
Which forms di-iodide on reaction with HI (excess)?

(A) I and II both (B) II only (C) I only (D) none
EtOH
23.   (A)
( SN1 )
Major- product (A) is
(A) (B) (C) (D)
CH3
SOCl 2
24. H OH   (A). Product (A) in
Et
CH3 Et CH3
H Cl H Cl
(A) (B) (C) Cl H (D)
Et CH3 Et
25. SN1 is a two-step reaction. For each step, there has to be a transition state. Which of the following struc-
tures represent correctly the transition state of first step

(A) R  .....L –  
(B) R   ........L  
(C) R  ........Nu   
(D) R  ........Nu  
H O
26. CH3 – CH2 – O – C = CH2 3  Products are
CH3
O
(A) + EtOH (B) O + EtOH
OH
OH
(C) + EtOH (D) +
O
27.
VIBRANT ACADEMY
Under identical conditions, solvolysis of which of the following substrates would lead to maximum recemization?
Et
(A) H Br (B) (C) (D)

CH3
H O
28. 3 
 X
unacademy
excess
Structure of X is
(A) (B)
(C) (D)
29. The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because
(A) Alkyl chlorides are immiscible with SOCl2
(B) The other products of the reaction are gaseous and escape out
(C) Alcohol and SOCl2 are soluble in water
(D) The reaction does not occurs via intermediate formation of an alkyl chloro sulphite
30. Which of the following alcohol shows fastest reaction with HI ?
(A) (B) (C) (D)
31. Which one of the following compounds will be most reactive for SN1 & SN2 reactions:
(A) (B) (C) (D)
32. Which one of the following compounds will give enantiomeric pair on treatment with HOH?
C2H5 CH 3 H C2 H5
| | | |
(A) C6 H 5  C  I (B) CH  C  Br (C) C 6 H 5  C  Br (D) C 2 H 5  C  Br
3
| | | |
C2H5 C2 H5 D CH 3
33. Arrange the following compounds in order of decreasing rate of hydrolysis for SN1 reaction:
(I) CH2–Br (II) H3C CH2–Br
VIBRANT ACADEMY
(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
R1 R1
| |
34. For the given reaction ; RC X HOH
 R  C  OH
| |
unacademy R2 R2
Which substrate will give maximum racemisation?
CH 3 CH 3
| |
(A) C H  C  Br (B) CH 2  CH  C  Br
6 5
| |
C2H 5 C2H 5
(C) (D)
35. In the given reaction : CH OH
 [X]
3
(A) (B) (C) (D)
36. 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
37. Which of the following compounds is most rapidly hydrolysed by SN1 mechanism.
(A) C6H5Cl (B) Cl–CH2–CH = CH2 (C) (C6H5)3CCl (D) C6H5CH2Cl
38. Which will give white ppt. with AgNO3?
39.
VIBRANT ACADEMY
(A) (B) (C)
When ethyl bromide is treated with moist Ag2O, main product is:
(A) Ether (B) Ethanol (C) Aldehyde
(D) Both A & C
(D) All of the above
40. NaOH
 A. A is:
excess
unacademy
(A) (B) (C) (D)
CH3
18 conc. HI
41. 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
CH2 – OH (x) HBr
42.
OH
Value of (x) is
(A) 1 (B) 2 (C) 3 (D) 4
CH3
43. 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
44. In the given reaction: CH 3  CH 2  S CH 2  CH 2  Br  [X] , [X] will be:
VIBRANT ACADEMY
(A)
*
CH 3  CH 2  S  CH 2  CH 2  OH
(C) 1 : 1 mixture of (A) and (B)
(B) CH 3  CH 2  S  CH 2  CH 2  OH
(D) 2 : 1 mixture of (A) and (B)
*
–
(i) SH (one equivalent)
45. In the given reaction CH 3  CH  CH 2  CH 2  CH  CH 3 [X] , [X] will be:
(ii) KOH
| |
OTs OTs
– – –
OTs S
unacademy
S S
| | | |
(A) CH3 – CH – CH2 – CH2 – CH – CH3 (B) CH3 – CH – CH2 – CH2 – CH – CH3
(C) (D)
18
O–CH3
Conc. HI
46. 
 Products are
18 OH
OH I I
18
(A) + CH3I (B) + CH3OH (C) + CH3I (D) + H2O
47. 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
48. Which of the following carbocation will undergo rearrangement ?
CH3
  
(A) (B) (C) CH3 – CH – C = O (D) CH3 – NH – CH – CH – CH3 ]
 | |
CH3 CH3
49. 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.
O
||
H
50. (B) , Give structure of (B)
(A)
VIBRANT ACADEMY
O
(A) (B) (C) (D)

O
O
51. Arrange the following compounds in the increasing order of their densities.
Cl Cl Br
(a) (b) (c) (d)
unacademy Cl Cl
(A) (a) < (b) < (c) < (d) (B) (a) < (c) < (d) < (b) (C) (d) < (c) < (b) < (a) (D) (b) < (d) < (c) < (a)
52. EtOH SN1 + E1 Products.

s.
Cl
(A) 5 (B) 6 (C) 7 (D) 8
Br
Na
53. 
 (A)
D.E.
Br
(A) (B) (C) (D)
Br
Na
54. 

D.E.
Cl
(A) (B) (C) (D)
Br
Na Se
55. 
 (A) 
 (B)
D.E. 
Br
Product (B) will be.
Br
(A) (B) (C) (D)
2 Cl
56. n-Pentane  (A)
h
Mono-chloro product (including streoisomers) are :
(A) 2 (B) 3 (C) 4 (D) 5
57.
VIBRANT ACADEMY
CH 3
Cl Cl
CH3
Na
  ?
Dry ether
CH3
CH3 CH3 CH3 CH3
(A) CH3 (B) (C) (D)
CH3
58.
(B) is
unacademy

Br
2  ( A ) 
h..
 (B )
Na
DMF
(A) (B)
(C) (D) None of these
Na
59. * Cl   ? Possible products are :
Dry ether
(C = C14)
(A) ** (B)
* *
(C) * (D) All of these

*
Na Na
60. (I) 
 (II) 

Br D.E. F D.E.
Na Na
(III) 
 (IV) 

Cl D.E. I D.E.
Correct order of rate of reaction will be
VIBRANT ACADEMY
(A) IV > III > I > II (B) III > IV > I > II (C) IV > I > III > II (D) None of these
unacademy
EXERCISE-II
SCQ :
–
O +
1. 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
2. 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 –
3.
VIBRANT ACADEMY
(A) 1
Br
Value of x is
(x = No. of moles of NaNH2)
(B) 2 (C) 3 (D) 4

alc. KOH
4. CH3  CH2  CH  CH3   X (major)
| 
Br
(A) (B) (C) (D) None of these
5.
CH3 — CH — CH3
|
unacademy
The energy profile of the given reactions .
H

+
CH3 — CH — CH3
+|
+
CH3 — CH — CH3
–H
+
CH3 — CH = CH2
OH O
H H
(A) E (B) (C) E (D) E

E
rxn–coordinate rxn–coordinate rxn–coordinate

rxn–coordinate

6. H (X).

Major product (X) is
(A) (B) (C) (D)
7. 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
8. 2 
4  X, X is

(A) (B) (C) (D)
9.
VIBRANT ACADEMY
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
10. Among the given compounds, the correct dehydration order is :
(I) OH
(A) I < II < III < IV

unacademy
(II) OH
(B) II < III < IV < I

(III) OH
(C) I < III < IV < II

(IV) OH
(D) I < II < III = IV
conc.H2SO 4
11. HO OH  A
OH
Final product A is
(A) HO O (B) CH2 = C = CH2 (C) (D) HO

O
O
Conc . H SO
2
12..    4  A.

Product A is:
(A) (B) (C) (D)
13. Which of these dehydrates most readily when reacts with conc. H3PO4.
OH OH OH
(A) (B) (C) OH (D)
CH3 CH3
| | H
14. CH3 — C — C — CH3  (P) (Major). Major product (P) is:
| | 
OH OH
O CH3 CH3 CH3 O O

|| | | | CH3
||
(A) CH3 — C — C — CH3 (B) CH2  C — CH — CH3 (C) (D) CH3  C  CH3
| CH3
VIBRANT ACADEMY
CH3
CH3
Conc. H 2SO 4
15.     A, A is :

(A) (B)
(C)
unacademy (D)
Me
H Et alc. KOH
16.    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
17. Which of following halides gives fastest elimination reaction when it is treated with alcoholic KOH.
Br
Br Br
Br
(A) (B) (C) (D)
18. Which of following is dehydrating agent ?

(A) conc. H3PO4 (B) P2O5 (C) POCl3 (D) All
Comprehension (Q.19 to Q.22)
(A) Cl (B) Cl (C) (D) CH3 – Cl

Cl
19. Most reactive towards SN1 reaction 20. Most reactive towards SN2 reaction ?
21. Most reactive towards E2 reaction ? 22. Most reactive towards E1 reaction ?
VIBRANT ACADEMY
unacademy
EXERCISE-III
Choose the correct option. Only one is correct
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.
VIBRANT ACADEMY
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
unacademy
(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
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 ?
VIBRANT ACADEMY
(A)
H3C CH2Br
(B)
H3C Br
CH3
(C)
CH2Br
CH3
(A) A (B) B
(C) C (D) None (all can undergo an E2 reaction)
10. Major product of the reaction is
(A) Butene-1
unacademy (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)
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
3 CH OH
16. CH3O – CH = CH2  
 product formed is
H
(A) Acetal (B) Hemiacetal (C) Alcohol (D) aldehyde
CH3
17.
Cl
Total number of SN1 products of given compound are
VIBRANT ACADEMY
(A) 3
Br
(B) 4 (C) 5 (D) 6
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
19.
CH3 OH
H
CH3 – C – CH – CH3 
unacademy
 ( A ) ;

OH
H 
 (B) ;


OH H
 ( C)


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
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 reactive
Cl Cl Cl Cl Cl Cl
Cl Cl Cl
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).
VIBRANT ACADEMY
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
unacademy
(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 NMe3

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
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
29.
VIBRANT ACADEMY
OH
(A) 12  H
Con.H2SO4
  major product having H
(B) 8 H (C) 4  H (D) 11  H
unacademy
EXERCISE-IV
PREVIOUS YEAR AIEEE QUESTIONS
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
VIBRANT ACADEMY
[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
 

DMF
is
(A)
Cl
unacademy
(B)
NC
CN
(C)
Cl
(D)
CN
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
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]
2 4 ? conc.H SO
C6H5CH2CH(OH)CH(CH3)2    

C 6H 5 CH(CH3)2
(A) C=C (B) H5C6CH2CH2
C = CH2
H H H3C
H 5C 6 H
VIBRANT ACADEMY
(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
16.
(A) free radical
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amount of SbCl5, due to the formation of :
(B) carbanion (C) carbene
2-chloro-2methylpentane on reaction with sodium methoxide in methanol yields :

[JEE-Mains-2013]
(D) carbocation
[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
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
VIBRANT ACADEMY
(C) C6H5CH2 – C – CH2CH3
OC2H5
(D) C 6H 5CH 2 – C = CH CH3
CH3
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. unacademy
The major product of the following reaction is :
OH
[JEE-Mains Online -2017]
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)
25. Which of the following compounds is most reactive to an aqueous solution of sodium carbonate?
(A) (B) (C) (D)
26. In the following structure, the double bonds are marked as I, II, III and IV
II
VIBRANT ACADEMY I
III
IV
Geometrical isomerism is not possible at site (s) : [JEE-Mains Online -2017]

(A) III (B) I (C) I and III (D) III and IV
Br2 / h
unacademy Br
Br
Br
(A) (B) (C) (D)
Br
Br
28. The increasing order of the boiling points for the following compounds is : [JEE-Mains Online -2017]
(I) C2H5OH (II) C2H5Cl (III) C2H5CH3 (IV) C2H5OCH3
(A) (III) < (IV) < (II) < (I) (B) (IV) < (III) < (I) < (II)
(C) (II) < (III) < (IV) < (I) (D) (III) < (II) < (I) < (IV)
29. 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)
30. Among the following compounds, the increasing order of their basic strength is :
NH2 CH3
(I) (II) (III)
N (IV)
N NH2
H
(A) (I) < (II) < (IV) < (III) (B) (I) < (II) < (III) < (IV)
(C) (II) < (I) < (IV) < (III) (D) (II) < (I) < (III) < (IV)
31. 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
32. 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)
33.
VIBRANT ACADEMY
The major product obtained in the following reaction is
Br
H
C6H5
t
BuOK
[JEE-Mains-2017]

C6H5
(+)
(A) (–)C6H5CH(OtBu)CH2C6H5 (B) (±)C6H5CH(OtBu)CH2C6H5
(C) C6H5CH = CHC6H5 (D) (+)C6H5CH(OtBu)CH2C6H5
34. Which of the following molecules is least resonance stabilized? [JEE-Mains-2017]
(A)
O
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(B) (C)
O
(D) N
35. 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
36. 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
37. The major product of the following reaction is : [JEE-Mains-2018]
Br NaOMe
MeOH
OMe OMe
(A) (B) (C) (D)
(i) KOH (alc.)

(2) Free radical
Cl Cl polymerisation
CH3 CH3
n n
n
n
(A) (B) (C) (D)

Cl
OH
OH Cl
39.VIBRANT ACADEMY
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)
40.
unacademy
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
Br
KOH alc (excess)

Ph
Br
(A) (B) (C) (D)

Ph Ph
Ph Ph
42. For the following reactions [JEE-Mains Online -2020]
k s on
CH3CH2CH2Z + Br
ti
ub stitu
CH3CH2CH2Br + Z S
eli
mi
k e ion
na
t
CH3CH=CH2+HZ + Br
where,
CH3
Z = CH3CH2O (A) or H3C—C—O (B)
CH3
ks
ks and ke, are, respectively, the rate constants for substitution and elimination, and  = k , the correct
e
option is
(A) A > B and ke(B) > ke(A) (B) B > A and ke(A) > ke(B)
(C) A > B and ke(B) > ke(B) (D) B > A and ke(B) > ke(A)
43. Consider the following reaction : [JEE-Mains Online -2020]

2 4 conc.H SO alc.KOH
(a) (CH3)3CCH(OH)CH3   (b) (CH3)2CHCH(Br)CH3 

(d) (CH3)2C CH2  CHO
(CH3)3O K
(c) (CH3)2CHCH(Br)CH3
VIBRANT ACADEMY

OH
Which of these reaction will not produce Saytzeff product ?
(A) (c) only (B) (d) only (C) (a), (c) and (d) (D) (b) and (d)
44. The major product [B] in the following reactions is : [JEE-Mains Online -2020]
CH3
| H2SO4
HI
CH3—CH2—CH—CH2—OCH2—CH3 [A] alcohol [B]
Heat
CH3
(A) CH2 = CH2
CH 3
|
unacademy |
(B) CH 3—CH=C—CH 3
(C) CH 3—CH 2—C = CH 2 (D) CH3—CH2—CH = CH—CH3
45. The mechanism of SN1 reaction is given as : [JEE-Mains Online -2020]
R–X R X R || X Y R–Y + X
Ion pair Solvent
Separated ion
pair
A student writes general characteristics based on the given mechanism as :

(a) The reaction is favoured by weak nucleophiles.
(b) R would be easily formed if the substituents are bulky.
(c) The reaction is accompanied by racemization.
(d) The reaction is favoured by non-polar solvents.
Which observations are correct ?
(A) (a) and (b) (B) (a) and (c) (C) (a), (b) and (c) (D) (b) and (d)
46. Consider the reaction sequence given below : [JEE-Mains Online -2020]
OH
Br H2O
OH + Br (1)
rate = k[t-BuBr]
CH3
OH
C2H5OH + HOH + Br (2)
H2C CH3
rate = k[t-BuBr][OH]
Which of the following statements is true :
(A) Changing the base from OH to OR will have no effect on reaction (B)
(B) Changing the concentration of base will have no effect on reaction (A)
(C) Doubling the concentration of base will double the rate of both the reactions.
(D) Changing the concentration of base will have no effect on reaction (B).
47. Which of the following compounds will show retention in configuratoin on nucleophic substitution by OH–
ion? [JEE-Mains Online -2020]
Br
(A) CH3 – CH – Br (B) CH3 – C – H (C) CH3 – CH – Br (D) CH 3 – CH – CH2Br
C6H13 C6H5 C 2H 5
VIBRANT ACADEMY
CH3
48. The major product obtained from E2-elimination of 3-bromo-2-fluoropentane is :
Br
(A) CH3 CH2 CH CH CH2 (B) CH3 CH2 CH C F
F Br
CH3
(C) CH3 CH CH CH CH3 (D) CH3 CH2 C CH CH3
49. The decreasing order of reactivity of the following compounds towards nucleophilic substitution (SN2)
is : [JEE-Mains Online -2020]
CH2Cl
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CH2Cl CH2Cl CH2Cl
NO2
NO2
NO2 O2N NO2
NO2
(I) (II) (III) (IV)
(A) (II) > (III) > (I) > (IV) (B) (II) > (III) > (IV) > (I) (C) (III) > (II) > (IV) > (I) (D) (IV) > (II) > (III) > (I)
50. The major product in the following reaction is: [JEE-Mains Online -2020]
t-BuOH
Heat
Ot-Bu
(A) (B) (C) (D)
51. When neopentyl alcohol is heated with an acid, it slowly converted into an 85 : 15 mixture of alkenes A
and B, respectively. What are these alkenes? [JEE-Mains Online -2020]
H3C CH2 H3C CH3 H3C CH3 H3C CH3

(A) and (B) and
H3C CH2 H3C CH2
CH3 H3C CH3 H3C CH2

CH3 CH3 CH2
(C) (D) and
and
H2C H3C
CH2 CH3
HO CH2CH3
H2SO4
O
CH2CH3 CH2CH3 CH = CH2 CHCH3
VIBRANT ACADEMY
(A) (B) (C) (D)
O O O O
53. What is 'X' in the given reaction ? [JEE-Mains Online -2021]
CH 2OH
210ºC
+ oxalic acid X
(major product)
CH 2OH
CH2 OH CH — OH CHO CH2

(A) | (B) || (C) | (D) ||
54.
CHO
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Identify A in the given reaction
CH2 CHO CH 2
OH
SOCl2
A (Major Product)
HO CH2OH
OH OH Cl Cl
(A) (B) (C) (D)
Cl CH2Cl OH CH2Cl Cl CH2Cl OH CH2OH
CH3 CH
55. What is the major product formed by HI on reaction with C CH2 ?
CH3
CH3
CH3 CH3
(A) CH3—C—CH—CH3 (B) CH3—C—CH—CH2I
I CH3 CH3H
CH3
(C) CH3—CH—CH—CH2—CH3 (D) CH3—C—CH—CH3
CH3 I CH3 I
56. The correct order of the following compounds showing increasing tendency towards nuceophilic substitution
reaction is : [JEE-Mains Online -2021]
Cl Cl Cl
Cl
NO 2 O 2N NO2
VIBRANT ACADEMY
(i) (ii) (iii) (iv)
NO 2 NO 2 NO2
(A) (iv) < (i) < (ii) < (iii) (B) (iv) < (i) < (iii) < (ii) (C) (iv) < (iii) < (ii) < (i) (D) (i) < (ii) < (iii) < (iv)
57. Identify A and B in the chemical reaction . [JEE-Mains Online -2021]

OCH3
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HCl Nal
[A] [B]
dry acetone
(major) (major)
NO2
OCH3 I OCH3 I
Cl Cl
(A) A = B= (B) A = B=
Cl Cl
NO2 NO2 NO2 NO2
OCH3 OCH3 OCH3 OCH3

Cl Cl I
(C) A = B= (D) A = B=
Cl
NO2 NO2 NO2 NO2
H3C OH H3C Cl
– +
20% H3PO4 (CH3)3CO K
58. "A" "B"
358 K
(Major Product) (Major Product)
The products “A” and “B” formed in above reactions are : [JEE-Mains Online -2021]
CH2 CH2 CH3 CH3
(A) A - , B- (B) A - ,B-
CH3 CH2 CH2 CH3
(C) A- ,B- (D) A- ,B-
59. Main Products formed during a reaction of 1-methoxy naphthalene with hydroiodic acid are :
I OH
VIBRANT ACADEMY
(A)
OH
and CH3OH (B)
I
and CH3I
(C) and CH3OH (C) and CH3I
60. Given below are two statements : [JEE-Mains Online -2021]
unacademy
Statement I : C2H5OH and AgCN both can generate nucleophile.
Statement II : KCN and AgCN both will generate nitrile nucleophile with all reaction conditions.
Choose the most appropriate option :
(A) Statement I is true but statement II is false.
(B) Both statement I and statement II are true.
(C) Statement I is false but statement II is true.
(D) Both statement I and statement II are false.
61. Match List - I with List - II : [JEE-Mains Online -2021]
List - I (Chemicals) List - II (Use / Preparation / Consituent)
(a) Alcoholic potassium hydroxide (i) electrodes in batteries
(b) Pd / BaSO4 (ii) obtained by addition reaction
(c) BHC (Benzene hexachloride) (iii) used for - elimination reaction
(d) Polyacetylene (iv) Lindlar’s Catalyst
(a) (b) (c) (d)
(A) ii i iv iii
(B) iii iv ii i
(C) iii i iv ii
(D) ii iv i iii
JEE ADVANCE
EXERCISE-I
Choose the correct option. One or more than one are correct
1. Which of the following compound will not undergo Nucleophilic substitution reaction.
Cl Cl Br
(A) (B) (C) (D)

Cl
CH3
| NaCN
2. 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
3. Rate of SN2 will be negligible in
VIBRANT ACADEMY
(A) (B) (C) (D)
4. Which are possible products in following
moist Ag O
  2

SN1
(A)
unacademy (B)
CH3 OH
(C) (D)
5. SN1 & SN2 product are same in (excluding stereoisomer)
Cl
H
(A) (B) (C) (D) Ph  CH  CH  CH3
| |
CH3 Cl
6. 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
7. CH3 – CH2 – O – CH3  
Products are :
(A) CH3 – Cl (B) Et – Cl (C) Cl (D) Cl
O
8. || 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
9. 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
10.
VIBRANT ACADEMY
H
Br
CH3
Br
H
Zndust
   (p). The product (p) is
(A) (B) (C) (D)
Paragraph for Question Nos. 11 to 13 (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
OH
H CH –CH=CH
+
unacademy
between reactants and products.
3 2

Mechanism
H
 
OH + H2SO4 O CH3–CH–CH 2
(r.d.s)
HSO4 H
H
H2O :

CH3–CH=CH2 + H3O
11. 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)

OH 
H H
12. (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
13. Which alcohol is most reactive towards dehydration of alcohol in acid catalyzed reaction.
OH OH OH
OH
(A) (B) (C) (D)
VIBRANT ACADEMY
unacademy
Matrix
1. 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
Alkyl–P–toluene sulfonate Ethanolysis relative rate (50°C)
(A) CH3 – CH2 – OTs (P) 1010
(B) H2C = CH – CH2 – OTs (Q) 105
VIBRANT ACADEMY
(C) Ph – CH2 – OTs (R) 400
(D) Ph – CH – OTs (S) 35

Ph
(E) Ph3C – OTs. (T) 1
3. Substrate E2 elimination SN2– substitution

(A) CH3 – CH2 – Br (P) 1 (W)  0
(B) (CH3)2 CH – Br (Q) 80 (X) 20
4.
(C)
Reaction
(CH3)3 CBr
unacademy (R) 100 (Y) 90
Relative rate of reaction
(A) (P) 1
(B) (Q) 200
(C) (R) 10,000
(D) (S) 30,000
Alkyl-bromide Relative rate of SN1
(A) (P) 1
(B) (Q) 11.6
(C) CH3–CH2–Br (R) 1,200,000
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
7. Match List-I with List-II for given S reaction & select the correct answer from the codes given below
N2
VIBRANT ACADEMYList-I
Z–CH2Br + CH 3 O
–
 Z–CH2–OCH3 + Br
List-II (relative reactivity)

–
(A) H– (P) 0.1

(B) CH3 – (Q) 3
(C) C2H5 – (R) 1
(D) (S) 100
unacademy
8. 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
9. 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
VIBRANT ACADEMY
(D) CH 3  CH  Cl     (S) SN1 reaction
10. 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
(A)
(B)
(Nucleophile)
unacademy (Relative rate)
(P)
(Q)
3.25
6.25
(C) (R) 1.0
(D) (S) 7.75
11. 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
VIBRANT ACADEMY
(A)
(C)
(a) (b) (c) (d)
(i) (ii) (iv) (iii)
(iv) (iii) (ii) (i)
(B)
(D)
(a) (b) (c) (d)
(iv) (iii) (i) (ii)
(i) (iii) (iv) (ii)
12. Match the column
+
O – CH2– CH3 H3O
(A) (W) One of product is Ph – OH
+
H3O
(B) O
unacademy (X) One of product is CH3 – CHO
+
H3O
(C) O (Y) One of product is 2° alcohol
+
H3O
(D) O (Z) No-reaction
(A) O H O (P) No-reaction

3 

CH3 CH3
| |
H O
(B) CH3  C  O  CH  CH3 3 
 (Q) CH3  C  OH
| | |
CH3 CH3 CH3
is one of the product of the reaction
CH3 OH

(C) O C CH3 
H3 O
 (R)
CH3
CH3
VIBRANT ACADEMY
O – CH H O CH3  CH  OH
(D) 3 
 (S) |
CH3
CH3
14. Column-I Column-II
CH 3 CH3
(A) H (P) Pinacol fashion reaction
C—C 

CH 3 CH3
O
CH3 CH3
| |
unacademy
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
15. 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
16. Substitution Logistics :

You were asked to run a series of reactions in the lab with different experimental conditions. Based on the
experimental observations you gathered (listed below), indicate which mechanism this evidence supports.
(Check the appropriate box to correspond to your answer.)
S.No. Observation SN1 SN2 Both

1 The rate of the reaction decreased when the concentration of the Nu is decreased.
2 The rate of the reaction increased when the concentration of the RX was increased.
3 The rate increased when the X was changed from Cl to I.
4 The products showed a skeletal rearrangement.
5 The product showed inversion of configuration.
6 The Nu was changed from methoxide to isopropoxide and the rate descreased.
7 The RX was changed from 2° alkyl halide to a 2° allyl halide and the rate increased.
VIBRANT ACADEMY
8 The solvent was switched from ethanol to acetone and the rate decreased.
unacademy
EXERCISE-II
Single choice Questions :
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.
VIBRANT ACADEMY
HBr reacts fastest with
(A) 2-methyl propan-2-ol (B) propan-1-ol (C) propan-2-ol

[IIT 1986]
(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.
(A) Ethane unacademy
The products of reaction of alcoholic AgNO2 with ethyl bromide are
(B) Ethyl nitrite (C) Nitroethane (D) Ethyl alcohol
[IIT 1991]
9. 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
10. 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
11. 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
–
2 5 OC H
12. + C2H5I   
 [IIT 2003]
anhyd. C2H5OH
(A) C6H5OC2H5 (B) C2H5OC2H5 (C) C6H5OC6H5 (D) C6H5I

H x Br2
13.
 H 2O ( mixture)  5 compounds of molecular formula C4H8Br2
Number of compounds in X will be: [IIT ‘2003]
(A) 2 (B) 3 (C) 4 (D) 5
14.
15.
VIBRANT ACADEMY
Benzamide on treatment with POCl3 gives
(A) aniline (B) benzonitrile (C) chlorobenzene
The best method to prepare cyclohexene from cyclohexanol is by using

(D) benzyl amine
[IIT 2004]
[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]
17.
(A)
unacademy (B) (C)
The following compound on hydrolysis in aqueous acetone will give :

(D)
[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)
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
VIBRANT ACADEMY
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
unacademy |
1 2 + |
4 5
H3C — C — C — C — CH3
|
HO
|
H
|
CH3
[JEE 2009]
(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
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
VIBRANT ACADEMY
25. The major product of the following reaction is [JEE 2011]
RCH OH
 2
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
P unacademy
Q
Cl
R
Cl
S
[JEE-Advance 2013]
(A) P > Q > R > S (B) S > P > R > Q (C) P > R > Q > S (D) R > P > S > Q
27. The hyperconjugative stabilities of tert-butyl cation and 2-butene, respectively, are due to
(A)   p (empty) and   * electron delocalisations.
(B)   * and   electron delocalisations.
(C)  p(filled) and  electron delocalisations.
(D) p (filled)  * and * electron delocalisations. [JEE-Advance 2013]
28. 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.
29. In the following reaction, the major product is [IIT Advance - 2015]
CH3
CH2 1 equivalent HBr
H2C
CH3
CH3 CH3 CH3
CH3
(A) H C (B) (C) (D)
2
H3C Br H2C Br H3C Br
Br
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
31.VIBRANT ACADEMY
(C) I and III follow SN1 mechanism
The order of basicity among the following compound is :

NH
(D) Compound IV undergoes inversion of configuration
NH2
[IIT Advance - 2017]
N NH HN N
H3C NH2 H2N NH
I II III IV
(A) II > I > IV > III (B) IV > II > III > I (C) I > IV > III > II (D) IV > I > II > III
MCQ :
32. The ether

unacademy
O–CH2 when treated with HI produces [IIT 1999]
(A) CH2I (B) CH2OH (C) I (D) OH
Matrix :
33. Match the following: [IIT 2006]
Column I Column II
(A) CH3–CHBr–CD3 on treatment with alc. KOH gives (P) E1 reaction
CH2=CH – CD3 as a major product.
(B) Ph – CHBr – CH3 reacts faster than Ph-CHBr-CD3. (Q) E2 reaction
(C) Ph–CH2 – CH2Br on treatment with C2H5OD/C2H5O– (R) E1cb reaction
gives Ph – CD=CH2 as the product.
(D) PhCH2CH2Br and PhCD2CH2Br react with same rate. (S) First order reaction
EXERCISE-III
1. Suggest a reason for the large difference between the boiling points of butanol and butanal, although they
have almost the same solubility in water. [IIT 1985]
2. Write the structure of the major organic product expected from each of the following reaction :
Boil( aq)
(i) CH3CH2CHCl2   [IIT 1992]
alkali
3. Fill in the blanks:

(a) Butane 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]
Cl
|
alc . KOH
4. (CH 3 ) 2 C  CH 2CH 3   ? [IIT 1992]
5. Aryl halides are less reactive than alkyl halides towards nucleophilic reagents. Give reason. [IIT 1994]
6. Optically active 2-iodobutane on treatment with NaI in acetone gives a product which does not show optical
activity. Explain briefly. [IIT 1995]
7.
VIBRANT ACADEMY
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]
8. 3, 3-dimethylbutan-2-ol losses a molecule of water in the presence of concentrated sulphuric acid to give
tetramethylethylene as a major product. Suggest a suitable mechanism. [IIT 1996]
9. 2, 2-dimethyloxirane can be cleaved by dil. acid. Write mechanism. [IIT 1997]
10.
unacademy
Which of the following is the correct method for synthesising methyl-t-butyl ether and why ?
 –
(i) (CH3)3 CBr + N a O Me  (ii) CH3Br + t  BuO – Na   [IIT 1997]
11. Give reasons for the following in one or two sentences. "Acid catalysed dehydration of t-butanol is faster than
that of n-butanol. [IIT 1998]
C6 H 5
|
Alcohalic KOH
12. (a) C6 H 5CH 2CHCl     A + B Write structures of (A) and (B).
Heat
HI( excess)
(b) (CH3)2CHOCH3    A + B Write structures of A and B. [IIT 1998]
Heat
13. What would be the major product in each of the following reactions? [IIT 2000]
CH 3
| C 2H5OH
(i) CH 3  C  CH 2 Br   

|
CH 3
14. ....... is most acidic. (Ethane, Ethene, Ethyne) [IIT 1981]
15. Give reasons for the following in one or two sentences :

(i) Methane does not react with chlorine in the dark.
(ii) Propene reacts with HBr to give isopropyl bromide but does not give n-propyl bromide. [IIT 1983]
16. The terminal carbon atom in 2-butene is ....... hybridised. [IIT 1985]
17. Write the balanced chemical equation for the following "Ethylene glycol is obtained by the reaction of ethylene
with potassium permanganate." [IIT 1991]
18. Write down the structures of the stereoisomers formed when cis–2–butene is reacted with bromine.
[IIT 1995]
19. An organic compound E(C5H8) on hydrogenation gives compound F(C5H12). Compound E on ozonolysis
gives formaldehyde and 2-ketopropanal. Deduce the structure of compound E. [IIT 1995]
20. One mole of the compound A (molecular formula C8H12), incapable of showing stereoisomerism, reacts with
only one mole of H2 on hydrogenation over Pd. A undergoes ozonolysis to give a symmetrical diketone B
(C8H12O2). What are the structure of A and B? [IIT 1997]
21. The central carbon–carbon bond in 1, 3–butadiene is shorter than that of n–butane. Why? [IIT 1998]
22. CH2=CH– is more basic than HCC– [IIT 2000]
 (i ) O
23. H
,
X    3 Y. Identify X and Y. [IIT 2005]
VIBRANT ACADEMY
(ii) Zn / CH COOH
3
24. The total number of alkenes possible by dehydrobromination of 3-bromo-3-cyclopentylhexane using alcoholic
KOH is : [IIT 2011]
25. The maximum number of isomers (including stereoisomers) that are possible on monochlorination of the
following compound is [IIT 2011]
CH3
C
CH3CH2 CH2CH3
H
26. The number of resonance structures for N is [IIT Advanced 2015]
unacademy OH
NaOH
N
27. In the following monobromination reaction, the number of possible chiral products is :
[IIT-Advanced-2016]
CH2CH2CH3
H Br
Br2 (1.0 mole)
CH3 300ºC
(1.0 mole)
(enantiomerically pure)
28. Among the following, the number of aromatic compound(s) is : [IIT Advance - 2017]


29. Choose the correct option(s) for the following set of reactions [JEE Advance - 2019]
i) MeMgBr conc. HCl

C6H10O Q S
ii) H2O (major)
20% H3PO4, 360 K
i) H2, Ni HBr, benzoyl peroxide
T ii) Br2, h
R U
(major) (major) (major)
H3C Br CH3 H3C Cl CH3

Cl Br
VIBRANT ACADEMY
(1)
U S
(2)
S U
CH3 H3C Br CH3 H3C Br

Cl Br
(3) (4)
S T U T
unacademy
ANSWER KEY
JEE MAINS
EXERCISE-I
1. B 2. B 3. B 4. C 5. C 6. A 7. A
8. A 9. B 10. C 11. C 12. C 13. B 14. C
15. C 16. C 17. A 18. D 19. A 20. A 21. C
22. C 23. B 24. A 25. A 26. A 27. C 28. B
29. B 30. B 31. A 32. C 33. A 34. C 35. A
36. A 37. C 38. D 39. B 40. B 41. B 42. A
43. C 44. C 45. C 46. A 47. A 48. B 49. D
50. B 51. A 52. B 53. B 54. C 55. B 56. C
57. D 58. B 59. D 60. C
EXERCISE-II
1. B 2. B 3. C 4. A 5. C 6. A 7. A
8. D 9. C 10. A 11. C 12. D 13. B 14. A
15. B 16. B 17. A 18. D 19. A 20. D 21. A
VIBRANT ACADEMY
22. A
EXERCISE-III
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
EXERCISE-IV
1. B 2. B
unacademy
3.
PREVIOUS YEAR AIEEE QUESTIONS
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. B 27. B 28. A
29. A 30. D 31. B 32. C 33. C 34. A 35. A
36. A 37. C 38. D 39. A 40. A 41. D 42. A

43. A 44. B 45. C 46. B 47. D 48. B 49. B
50. C 51. B 52. A 53. D 54. A 55. A 56. D
57. D 58. C 59. B 60. A 61. B
JEE ADVANCE
EXERCISE-I
1. ABD 2. BD 3. ABC 4. AB 5. BC 6. B 7. AB
8. A 9. A 10. B 11. D 12. D 13. A
MATRIX
1. AS ; BR; C Q ; DP 2. AT;BS;C  R ; D  Q ; E P
3. A  P,Y ; B  Q, X ; C  R,W 4. AS ; BR; C Q ; DP
5. AR ; BQ; C P 6. AP ; BQ;C R;DS ;ET
7. AS ;BQ; C  R ; DP 8. A  2, B  1, C  4, D  3
9. AS,BR,C Q, DP 10. AS ,BQ, C P , DR
11. B 12. A  W ; B  XY ; C  WY ; D  Z
13. A  P ; B  Q, S ; C  Q, R ; D  R, S 14. A  P ; B  R ; C  Q ; D T ;
15. A  S ; B  S ; C  P ; D S
16. S.No. SN1 SN2 Both
1 

VIBRANT ACADEMY
2
3 
4 
5 
6 
7 
8 
EXERCISE-II
1. C 2. D 3. C 4. C 5. A 6. C 7. A
8. C 9. D 10. D 11. B 12. A 13. B 14. B
15.
22.
29.
33.
B
D
D
16. D
23. C
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17. A
24. A
30. A,C,D or A,B,C,D
A – Q ; B – Q ; C – R,S ; D – P,S
18.
25.
31.
B
B
D
19.
26.
32.
D
B
AD
20.
27.
A
A
21.
28.
D
C
EXERCISE-III
1. Butanol has capacity for inter molecular hydrogen bonding.
OH
Boil
2. (i) CH3CH2CHCl2  CH3 – CH2 – CH   CH 3 – CH 2 – CHO
– H2 O
alkali OH propanal
– 2NaCl
(Unstable)
3. (a) propyl chloride, (b) ortho
CH3  C  CH  CH3
4. |
CH3
5. Due to the presence of resonance in alkyl halide carbon halogen bond acquires the character of partial
double bond and halogen is directly attached to sp2 hybridised carbon so the halogen is not capable to leave
as an leaving group.
6. The product obtained after the reaction contain equal amount of both d and l-isomers of 2-iodobutane and
this racemic mixture does not show optical activity due to external compensation.
CH 3 CH 3 CH 3 CH 3
| | | |
7. (X): CH 3  C — CH  CH 3 ; (Y) : CH 2  C — CH  CH 3 ; (Z) : CH  C — CH  CH
3 3
| | |
Cl CH 3 CH 3
CH3 CH3 CH3

Conc. H2SO4
CH3 – C – CH – CH3 CH3–C = C–CH3+H2O
8.  (Major product)
CH3 CH3
Mechanism of above reaction is represented as follows :
CH3 CH3
| H
+ |
CH3 — C — CH — CH3 CH3 — C — CH — CH3
| | | +|
CH3 OH CH3 OH2
..
..
CH3 H CH3
| +
| | +
CH3 — C — C — CH3 CH3 — C — CH — CH3
| –H2O |
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–H
CH3
(more stable)
+
CH3 CH3
| |
CH3
(less stable)
CH3 — C C — CH3 (Major product)
9. The oxirane ring is cleaved by the following mechanism :

H3C H3C OH
H
+ |
H2O H C – C – CH2 + H
+
H3C .. H3C +
3
| |
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.. CH3 OH
H
10. In these two methods, method (ii) is the correct method for the formation of ether because in method (i),
alkene is formed in place of ether.
(i) (CH3)3 C – Br + Na – O – Me  CH3 – C = CH2 + NaBr + CH3OH
CH3
iso-butene
CH3
+ – |
(ii) CH3Br + NaO — C(CH3)3 H3C — C — O — CH3 + NaBr
|
CH3
This reaction is called as Williamson's synthesis and it is based upon SN 2-reaction mechanism.
11. Due to formation of more stable 3º-carbonium ion with t-butanol that 1º-carbonium ion in n-butanol.
+
H
CH3 — CH2 — CH2 — CH2OH
–H2O
n-butanol
+
CH3 — CH2 — CH2 — CH2
1º - carbcation
although it is changed
in 2º -carbcation
+
CH3 — CH2 — CH — CH3
CH3 CH3
| +
H | +
CH3 — C — OH CH3 — C (3º -carbcation)
| |
CH3 CH3
12. (a) Cis and trans forms of stibene C6H5CH=CHC6H5 ; (b)
CH3
|
13. (i) CH3  C  CH  CH3
14. Ethyne
VIBRANT ACADEMY
15. (i) Methane does not react with chlorine in the dark because chlorine atoms are required for this reaction and
chlorine atoms are obtained only in the presence of light.
(ii) It is in accordance with Markownikoff's rule which predicts the stability of secondary carbonium ion over
primary carbonium ion.
16. sp3
CH2 CH2OH
KMnO 4
17. + [H2O + O]  
CH2 CH2OH
CH2 CH2OH
2KMnO4 + 3 + 4H2O  + MnO2 + 2KOH
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3
CH2 CH2OH
18.
(C5H8) H2
19. 5 12CH
compound E (hydrogenation) compound F
Ozonolysis
HCHO + H3C – C – CHO
formaldehyde ||
O
2-ketopropanal
Hence, compound E must be diene.

CH 2 = C –– CH = CH2
CH3
Compound F = CH3 – CH – CH2 – CH3
|
CH3
20. (A) (B)
21. Resonance is present in 1, 3-butadiene that's why every bond acquire the character of partial double bond.
22. higher electronegativity of sp carbon

O
||
23. (X) , (Y) CH3  C  (CH2 )4  CH  O
24. 5 25. 8 26. 9 27 5 28. 5 29. (2, 4)
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Alkyl Halide Sheet Un Academy 1

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ORGANIC CHEMISTRY

K1 & K2 are rate constant for above reaction. Correct relation is

2. Free energy profile for given reaction is

VIBRANT ACADEMY reaction co-ordinate

3. Rate expression for reaction given in Que.(2) is

unacademy (D) rate = K [HO]2 [CH3–Br]

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

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

For more update follow us on :

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Product of above reaction is

I & CH3OH OH & CH3I

I & CH3I OH & CH3OH

(A) (a)-I, (b)-I

(B) (a)-I, (b)-II

For more update follow us on :

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

19. Which of following compounds will show NGP ?

Value of x in above reaction is

Which forms di-iodide on reaction with HI (excess)?

Major- product (A) is

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

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(A) H Br (B) (C) (D)

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

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

(I) CH2–Br (II) H3C CH2–Br

Which substrate will give maximum racemisation?

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

(I) (II) (III)

38. Which will give white ppt. with AgNO3?

(D) All of the above

Products of above reaction is

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48. Which of the following carbocation will undergo rearrangement ?

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

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

52. EtOH SN1 + E1 Products.

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

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

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

(C) (D) None of these

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(C) * (D) All of these

Correct order of rate of reaction will be

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

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

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

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

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

rxn–coordinate rxn–coordinate rxn–coordinate

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Major product (X) is

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

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

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

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

(A) I < II < III < IV

(B) II < III < IV < I