ALKYL HALIDES LPP / SS / Ph-V / AH-13

Lecture Practice Problems

Alkyl Halides - 13
Q. Predict the major product of the following reactions and state the mechanism
(CH3)3O-
- Br
Br H3C O H3C
H3C (CH3)3OH
1. H3C OH 2.
CH3
Br
H3C
CH3 HS- Alc. KOH
Br
H3C
DMF
3. 4. H3C
CH3
H3C -
H2O H3C CH3 H3C O
Br
Cl DMF
5. H3C 6.
O

H3C CH3 - Br NaI

H3C O
Cl Acetone
DMF
7. 8.
Cl
Br KNH2 CH3 H2O

NH3
9. 10.
CH3
H3C CH3 EtOH
Ph CH3 NaOEt
Ph
DMSO
11. Br 12. Cl
CH3
H3C Br
CH3 EtO-

CH3 EtOH
13.

Q 14. Which one of the following compounds most readily undergoes substitution by S N 2 mechanism?
CH3
H3C H3C
(a) (b)
Cl
Cl
Cl H3C
CH3
(c) H3C (d)
H3C
C3H7 Cl

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Q 15. In which reaction there is mostly racemisation?
H C2H5

(A) H3C C Br 

NaI / acetone
→ (B) H C ONa + CH3 − I →

D CH3
C2H5

(C) H3C C Br + HOH → (D) All of these

C3H7

Q 16. Consider the given reaction

C2H5

H3C C I 
NaI/ acetone / water
→ Pr oduct

C3H7
the reaction mixture will contain(s)
C2H5 C2H5

(A) only I C CH3 (B) only H3C C I

C3H7 C3H7
C2H5 C2H5

(C) Mixture of H3C C I and I C CH3 (D) No reaction will take place

C3H7 C3H7

Q17. Which of the following reactions will go faster if the concentration of the nucleophile is increased?

Q 18. Which of the following alkyl halides form a substitution product in an S N 1 reaction that is different from the
substitution product formed in an S N 2 reaction?

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Q19. What will be the major product of the following reaction?
H CH 3
| | CH3OH,30° C
CH 3 − C − C − CH − CH 3  →
| | |
H CH 3 Br
H CH 3 CH 3 H CH 3 OCH 3
| | | | | |
(a) CH − C − C − C − CH (b) CH − C − C − C − CH
3 3 3 3
| | | | | |
OCH 3 H H H CH 3 H
H CH 3 CH 3 H CH 3 H
| | | | | |
(c) CH − C − C − C − CH (d) CH 3 − C − C − C − CH 2
3 3
| | | | | | |
H OCH 3 H H CH 3 H OCH 3

Q20. Which describes the best stereochemical aspects of the following reaction ?
H 3C
H − Br
Et  → Product
Ph
OH
(a) Inversion of configuration occurs at the carbon undergoing substitution.
(b) Retention of configuration occurs at the carbon undergoing substitution.
(c) Racemization occurs at the carbon undergoing substitution.
(d) The carbon undergoing substitution is not stereogenic.

21.
Br


H 2 O/Acetone
→ (A); Product (A) is :

Br
Br OH
OH
OH

(a) OH (b) OH (c) (d) Br

22. In the following reaction the most probable product will be :

Br
H CH3
Θ

H3C H 
OH
→

C2H5
OH CH3 C2H5 CH3
H CH3 H OH H CH3 HO H
H3C H H3C H H3C H H3C H

(a) C2H5 (b) C2H5 (c) OH (d) C2H5

23. The insecticide chloradane is warmed with dilute NaOH solution for some time. The expected product would be :

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Cl Cl
Cl
Cl

Cl
Cl Cl
Cl
HO OH
HO OH
OH
OH Cl
HO

OH OH
OH Cl OH
HO
(a) OH (b) OH
O
HO OH
Cl Cl
Cl Cl

OH OH
Cl Cl Cl Cl

(c) OH (d) OH

24.
D H

Cl CH3

H D NaI (excess)
D 'X'
D Acetone
Cl

C2 H5
Identify the ‘X’
H D D H D I H
D
CH3 I CH3 I CH3 I D CH3
D H D D
H D H D H D H D

D Cl D Cl I D I D

C2 H5 C 2H 5 C 2H 5 C 2H 5

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

25. Which of the following are correct regarding the products of the given reaction
Me
Me
H Aqueous acetone
H CN
H
H
Cl

OCH3
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Me Me Me
Me Me Me
H H
H CN CN CN
H OH H HO
H H H
H H H
OH H OH

(X) (Y) (Z)

OCH3 OCH3 OCH3
(A) Only X & Z are formed (B) Y > Z (amount) (C) X > Y (amount) (D) Y > X (amount)

CH3

H OH
 
HBr
→ Product,
CH3 H

26. C2H5
Which of the following structures represent the correct major product.
CH3 CH3 CH3 CH3

H Br Br H H H H H
CH3 H CH3 H Br CH3 CH3 Br

(a) C2H5 (b) C2H5 (c) C2H5 (d) C2H5

27. Observe the following reaction I and II k 1 k1′ , k 2 k 2′ are rate constants. Select the correct option (s).

N:

←  CH 3 − I
(CH3CH 2 )3 N:
[k1 ']
→
(k1 )
(i)
N:
(ii) ←  CH 3 − CH − CH 3 
(CH3CH 2 )3 N:
[k 2 '] (k 2 )
→
|
I
(a) k 1 > k1′ (b) k 1 > k 2 (c) k 2′ > k 2 (d) k 2′ > k1′

H F
NaCN 
→ A ( Major )
(1mole )
Br H
28.
major product of this reaction is,
NC F H H

H H CN
(a) (b) Br
H H H F

F CN H
(c) (d) NC

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29. What are the products of the following reactions?
CH3

a) H3C Cl + OCH3 
→

CH3
CH3

b) H3C O + CH3 − X 
→

CH3

30. Write products in the following reactions and give mechanism’

i-Pr
H
Et n-Bu 
KOH/EtOH
→
→ NaOH
EtOH, ∆ OTs
∆

H Ph

(a) CH3 (b) CH3

CH3

Br 
H2O
→

(c) H Et

31. Which statement is incorrect about the following reaction

CH3

I →
131
H NaI
Acetone
Pr oduct
C6H13
2- lodooctane
(+)

(a) The rate of these reaction depends on both [R – I] and [131IΘ]

(b) Initial loss of optical activity was exactly twice as fast as gain of radioactivity.
(c) Each molecule undergoing substitution, suffers inversion of configuration
(d) Final solution has radioactive iodine only

Solutions

O
1. H3C CH3 10 RX and strong unhindered base, so SN2
H3C CH2
2. 10 RX and strong hindered base, so E2
HS
CH3
3. H3C 20 RX and strong nucleophile with weak basic character, so SN2
H3C CH2CH3

4. CH2CH3 30 RX and strong base, so E2

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CH2CH3
H3CH2C

5. H3CH2C OH 30 RX and poor nucleophile with poor basic character, so SN1

6. H3C CH3 20 RX and strong base, so E2

H3C CH3

O O

7. CH3 20 RX and strong nucleophile and weak base, so SN2

I

8. 20 RX and strong nucleophile and weak base, so SN2

9. 20 RX and strong nucleophile and strong base, so E2

OH
CH3

10. 30 RX and weak nucleophile and weak base, so SN1

CH3

Ph CH3
11. 20 RX and strong nucleophile and strong base, so E2 and Hoffmann product
H3C CH3
Ph

12. OCH3 30 RX and weak nucleophile and weak base, so SN1

CH3
H3C
CH3
CH3
13. 30 RX and strong nucleophile and strong base, so E2

14. B
Less hindered carbon follows S N 2 mechanism.

15. C
Reaction proceeds by S N 1, so racemization takes place
16. C
17.

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18.

19. C
20. C Reaction proceeds via S N 1

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21. A Reaction proceeds via S N 1

22. B Reaction proceeds vias S N 2

23. D No substitution can occur at bridge head and sp2 C

24. D SN2 reaction

25. BD Reaction proceeds via SN1

26. CD

27. AB SN2 reaction

28. A SN2

29. a) CH3
CH3
H3C Cl + OCH3 
→ H3C
CH2
CH3
O—CH 3 (nucleophile) cannot attack 3° carbon having high electron-density hence elimination takes place
giving alkene.

b) CH3
H3C
CH3
H3C O + CH3 − X →
H3C
O
CH3
CH3
Nucleophilic attack on methyl carbon is possible giving ether (Williamson synthesis).
CH3
i-Pr
OH SN1

H n-Bu E2
C C H Et
E2
CH3 two diastereomers
30. (a)Ph Et (b) (c)

31. D This will proceed via SN2 reaction

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