334

5C
ALKYL HALIDES

Level - 1
Br
1. One eq. NaCN
1. ææææææÆ (A); Product (A) is :
2. LiAlH 4

Br

Br Br

(a) (b)

CH2–NH2 CH2NH2

CH2NH2 CH2–NH2
(c) (d)

Br Br

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 335
2. In the reactions given below,
(i) KCN, (ii) LiAlH 4
R – Cl æææææææÆ Product A
(i) AgCN, (ii) LiAlH 4
R – Cl æææææææÆ Product B
the compounds A and B are :
(a) chain isomers (b) position isomers
(c) functional isomers (d) metamers
3. Which is the major product expected from the following S N 2 reaction ?

Cl O
NaOH
æÆ Product
æ ææ

OH O OH O
(a) (b)

Cl OH OH OH
(c) (d)

4. Consider the following E 1 S N1 reaction :

Br OH
CH3 CH3 CH3
H 2O
æ æææ
æÆ +
Ethanol D
H3C H H3C H3C
H H

The missing product(s) is(are) :

OH CH3
CH3
(1) (2)
H3C H
H CH3
CH3
(3) (4)
H3C
H H

(a) 1, 2 and 3 (b) 3 and 4 (c) 2 and 3 (d) 1, 2 , 3 and 4

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 336
5. What is the product of the following S N 2 reaction ?
OTs O
NaBr
æææÆ Product
S 2
Ph OMe N

O OMe O OMe O OMe O OMe

H3C H H3C H H CH3 H CH3

(a) (b) (c) (d)
Br H H Br Br H H Br
Ph Ph Ph Ph
6. Select the reagent that will yield the greater amount of substitution on reaction with
CH 3 - CH 2 - Br :
(a) CH 3 CH 2 OK in dimethyl sulfoxide (DMSO)
(b) (CH 3 ) 3 COK in dimethyl sulfoxide (DMSO)
(c) Both (a) and (b) will give comparable amounts of substitution
(d) Neither (a) nor (b) will give any amount of substitution
7. Under the specified conditions, substrate X undergoes substitution and elimination reactions
to give products A - D. A and B are stereoisomers, but not enantiomers. C and D are
enantiomers. A is not an isomer of C. Which of the following could be the starting material X ?
H O
X æ æ2æÆ A + B + C + D
D

Br CH3 CH3
Br Br
H
Br CH3
(I) (II) (III) (IV)
H3C H
H3C H H CH3 H3C H
(a) (I) (b) (II) (c) (III) (d) (IV)
CH 3
|
8. CH 3 æ C æ CH 3 , CH 3 æ CH æ CH 3 , CH 3 æ CH æ Br
| | (c)
Br Br
(a) (b)

Compare rate of E 2 reaction :

(a) c > b > a (b) a > b > c (c) b > a > c (d) c > a > b
9. Which reaction results in the formation of a pair of enantiomers ?

CN – I H æH O
(a) æ ææ
æÆ (b) æ2æÆ
DMSO
I H
I
H3C
OH – 3CH OH
(c) æ ææÆ (d) æ ææ æÆ
DMF
I H

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 337
10. Rate limiting S N1 follows the sequence
d+ d –
R–Br R + Br – R + Br – R+ Br –
(a) (b) (c)

True statement about sequence on the basis of assumption that R contains 3 different groups
is :
(a) more stable carbocation, greater is in the proportion of racemization
(b) the more nucleophilic the solvent greater in the proportion of inversion
(c) In above sequence (b) represent separately solvated, pair of ions
(d) All of these
11. Compare the two methods shown for the preparation of carboxylic acids :
Mg 2 1. CO
Method 1 : RBr æ ææææ
æÆ RMgBr æ ææ
æ Æ RCO 2 H
diethyl ether 2. H 3O +
NaCN 2 H O, HCl
Method 2 : RBr æ ææ
æÆ RCN æ ææææÆ RCO 2 H
heat

Which one of the following statements correctly describes this conversion ?

Br CO2H

(a) Both method 1 and method 2 are appropriate for carrying out this conversion
(b) Neither method 1 nor method 2 is appropriate for carrying out this conversion
(c) Method 1 will work well, but method 2 is not appropriate
(d) Method 2 will work well, but method 1 is not appropriate
12. Which of the following statements is true ?
(a) CH 3 CH 2 S - is both a stronger base and more nucleophilic than CH 3 CH 2 O -
(b) CH 3 CH 2 S - is a stronger base but is less nucleophilic than CH 3 CH 2 O -
(c) CH 3 CH 2 S - is a weaker base but is more nucleophilic than CH 3 CH 2 O -
(d) CH 3 CH 2 S - is both a weaker base and less nucleophilic than CH 3 CH 2 O -
13. In the given pair of alcohols, in which pair second alcohol is more reactive than first towards
hydrogen bromide ?
CH3 H OH
OH
(a) and

OH
(b) and CH – CH3
|
OH

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 338
(c) CH 3 - CH - CH 2 - CH 3 and CH 3 - CH 2 - CH - CH 2 - OH
| |
OH CH 3
(d) CH 3 - CH - CH 2 - CH 3 and (CH 3 ) 2 C - CH 2 - CH 3
| |
OH OH
14. Which product would be expected to predominate in the given reaction ?
OSO2CF3

3CH OH
æ ææ æÆ
D (30∞C)

OCH3

(a) (b)

O – SO2 – CH3

(c) (d) None of these

15. Which is the major product of the following reaction ?

N
C
NaOH (excess)
æ æææææÆ Product
H 2O
CH2– Br heat

O N
C C
OH
(a) (b)
CH2– Br CH2– OH
O N
C OH C
OH
(c) (d)
CH2– OH CH2– OH
H Br
CH3 D
Alc. KOH
16. H æ æææ æÆ ( A) ; Major product of this reaction is :
H
OH
D CH3 D CH3 CH3 D
(a) H (b) (c) (d)

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 339
17. Rate of S N 2 reaction is :
Br Br
Br

(A) (B) (C)

(a) ( B ) > ( A) > (C ) (b) (C ) > ( A) > ( B )
(c) ( A) > ( B ) > (C ) (d) ( A) > (C ) > ( B )
18. 1-2-dichloro ethane + NaSCH 2 CH 2 SNa æÆ C 4 H 8 S 2 + ( P )
Unknown product ( P ) of the above reaction is :
S S
(a) (b)
S S
(c) H - S - C = C - CH = CH - S - H (d) H - C = C - CH = CH - S - H
| | | |
H H H H

Br

Moist Ag O
2
19. ææææÆ ( A) product
Major product (A) is :
OH OH
OH OH
(a) (b) (c) (d)

KCN
20. MeO Cl æ ææÆ Product of reaction is :

(MOM chloride)
(Methoxy methyl chloride)

Cl CN MeO CN
(a) (b)
CN
(c) Me - O - CH 2 - CH 2 - CN (d) O
CN
21. In the given pair of compound, in which pair the second compound is more reactive than first
toward S N 2 reaction ?

(a) Cl or (b) CH2 – Cl or Cl

Cl
Br Br
(c) or (d) or Cl
Cl

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 340
22. Which compound might be synthesized by the S N 2 displacement of an alkyl-halide ?
SCH2CH3
(a) CH2 – OH (b)

(c) Me 3 C - OCH 3 (d) All of these

23. Identify C in the following series C 3 H 7 I æ KOH
ææ
alc.
Æ
NBS
A æ ææÆ B æ æ æÆ C .
alc.
KCN
D

(a) (CH 3 ) 2 CH - CN (b) CH 2 = CH - CH 2 CN

(c) Br - CH = CH - CN (d) CH 2 = CH - CH CN
|
Br
24. What sequence of reagents is required to accomplish the following transformation ?

OH
(a) (1)NBS, ROOR (2) CH 3 CH 2 O (3) 2HBr (4) NH -2 (5) disiamyl borane (6) H 2 O 2 ,OH -
-

(b) (1) Cl 2 hn (2) OH - , heat; (3) 2HCl (4) OH - , heat (5) HgSO 4 , H 2 SO 4
(c) (1) NBS, ROOR; OH - , DMSO
(d) (1) Br 2 , hn (2) t-butoxide (3) BH 3 , THF (4) H 2 O 2 , OH -
25. Which of the reagents shown below would accomplish the following transformations?
Br OH
1. A
2. B

A B
(a) H 3 O + BH 3 - THF; H 2 O 2 /NaOH
(b) NaOH BH 3 - THF; H 2 O 2 /NaOH
(c) HBr in ether Hg(OAc) 2 /H 2 O; NaBH 4
(d) NaNH 2 Hg(OAc) 2 /H 2 O; NaBH 4
26. What are the products obtained from the following reaction ?
Br
HC ∫∫ CNa
æ ææææÆ Product
Et 2O

H H
C C
C C
(a) + (b) +

20% 80% 20% 80%

H
C
C
(c) (d)
C
C 100%
100% H

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 341
27. The back-side attack on 2-bromobutane by methoxide (CH 3 O - ) gives the product shown
below. Which Fischer projection represents 2-bromobutane used as the reactant in this
reaction ?
OCH3

product = Et Me
H

Et Et Me Br
(a) Me H (b) H Br (c) Br H (d) Me H
Br Me Et Et
28. Consider the following statements :
(1) Bridgehead halides are inert towards both S N1 and S N 2 reactions (till one of the ring size
is eight member ring)
(2) The first step in both S N1 and E 1 reactions is the same
(3) S N 2 reactions proceed with total retention of configuration
(4) E 2 eliminations are by the use of a solvent of low polarity and high concentration of a
strong base
Which of the above statements are correct?
(a) 1, 2 and 4 (b) 1 and 3
(c) 2, 3 and 4 (d) 1, 2, 3 and 4
29. Consider the following alcohols :

CH2OH CH2OH CH2OH CH2OH

O2N CH3O Br
(I) (II) (III) (IV)

The order of decreasing reactivities of these alcohols towards substitution with HBr is :
(a) III > I > IV > II (b) III > I > II > IV
(c) I > III > IV > II (d) I > III > II > IV
30. In solvolysis of 1,2-dimethyl propyl p-toluene sulfonate in acetic acid at 75°C, how many
(alkene + substitution) products will be formed ?
(a) 2 (b) 3 (c) 4 (d) 5
31. Benzotrichloride reacts with milk of lime to form :
(a) Benzal (b) Benzoic acid (c) Benzyl alcohol (d) Phenol
32. Br - CH 2 - (CH 2 ) 2 - CH 2 - Br + CH 3 NH 2 æÆ Product of the reaction is :
(a) (b) (c) (d)
N N N N
H H
33. The configurations of the reactant and the product in the following reaction, respectively,
are:

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 342
CO2CH3
CO2CH3
KCN
D Br CHCN
EtOH

H D
(a) R, R (b) R, S (c) S, R (d) S, S
Acetone
34. 1-4-dichlorohexane (1 mole) + NaI (1 mole) æ æææÆ Product of the reaction is :
(a) Cl – CH 2 – CH 2 – CH – CH 2 – CH 3 (b) I – CH 2 – CH 2 – CH – CH 2 – CH 3
| |
I Cl
(c) H 2 C = CH – CH – CH 2 – CH 3 (d) I – CH 2 – CH 2 – CH 2 – CH – CH 2 – CH 3
| |
Cl Cl
35. Alkyl halides can be obtained by all methods except :
(a) CH 3 CH 2 OH + HCl ZnCl 2 æÆ (b) CH 3 – CH 2 – CH 3 – CH 2 æCl 2 / UV light
ææææ æÆ
(c) C 2 H 5 OH + NaCl æÆ (d) CH 3 COOAg + Br 2 CCl 4 æÆ
36. In order to prepare 1-chloropropane, which of the following reactants can be employed ?
(a) Propene and HCl in the presence of peroxide
(b) Propene and Cl 2 followed by treatment with aq. KOH
(c) Propanol-1 and SOCl 2 pyridine
(d) Any of the above can be used
37. Which alkyl halide has maximum density ?
(a) C 3 H 7 I (b) C 2 H 5 I (c) CH 3 I (d) CH 3 Br
38. Which of the following molecules would have a carbon-halogen bond most susceptible to
nucleophilic substitution ?
(a) 2-fluorobutane (b) 2-chlorobutane (c) 2-bromobutane (d) 2-iodobutane
39. When benzyl chloride is treated with ethanolic KCN, the major product formed is :
(a) benzyl ethyl ether (b) benzyl alcohol (c) benzyl cyanide (d) benzyl isocyanide
40. Which of the following is most reactive towards nucleophilic substitution reaction ?
(a) CH 2 = CH – Cl (b) C 6 H 5 Cl (c) CH 3 CH = CHCl (d)ClCH 2 – CH = CH 2
41. Which of the following reaction will not give ether as a major product ?
(a) CH 3 CH 2 Cl + Ag 2 O(dry) æÆ (b) (CH 3 ) 3 CCl + CH 3 CH 2 O - Na + æÆ
CH 3
|
(c) CH 3 CH 2 Cl + Na + O - æÆ (d) CH 3 Cl + Na+O – – C – CH 3 æÆ
|
CH 3
O + (A)
|| H
Q Q C
42. O – S – O H3 –
I
(B)

Product (A) and (B) in above reaction is :

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 343
O O O O
|| || || ||
(a) O - — S — O — H , O - — S — O — CH 3 (b) O - — S — O — H ,O -— S — CH 3
≈|

O-
O O O O
|| Q ≈
|| || ||
(c) O - — S — O - CH 3 , O — S — H (d) O -— ≈ S — O , O - — S — O -
| | ||
CH3 H CH 3
43. Which of the following would be true for the reaction shown ?
CH3OH

Br OCH3

(a) The rate of the reaction depends only on the alkyl bromide concentration.
(b) The rate of the reaction depends only on the methanol concentration.
(c) The rate of the reaction depends on both the alkyl halide concentration and the
methanol concentration.
(d) The rate of the reaction depends on the concentration of neither reactant.
44. The correct order of rate of S N 1 is :
Cl
Cl Cl
(a) > (b) <
H Cl

Cl Cl
Cl
(c) > (d) <
Cl

ANSWERS — LEVEL 1
1. (c) 2. (c) 3. (b ) 4. (a) 5. (a) 6. (a) 7. (c) 8. (b)
9. (b) 10. (d) 11. (c) 12. (c) 13. (d) 14. (a) 15. (c) 16. (c)
17. (c) 18. (a) 19. (c) 20. (b) 21. (d) 22. (d) 23. (b) 24. (d)
25. (d) 26. (b) 27. (d) 28. (a) 29. (a) 30. (d) 31. (b) 32. (b)
33. (d) 34. (d) 35. (c) 36. (c) 37. (a) 38. (d) 39. (c) 40. (d)
41. (b) 42. (b) 43. (a) 44. (b)

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