|5c

ALKYL HALIDES

Level1
Br
1. One eq. NaCN
1, (A); Product (A) is :
2. LiAlH4

Br

Br Br

(a) (b)

ÃH,-NH, CH,NH,

aCH,NH oCH,-NH,
(C) (d)

Br Br
Alkyl Halides 335

2. In the reactions given below,

(i) KCN, (ii) LiAlH4
R - Cl Product A
LiAIH,
R-CL 0AgCN, (ü) 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 S2reaction ?
Cl
NaOH
Product

OH
(a) (b)

OH 0H
(c) (d)

4. Consider the following E,/S,j reaction :

OH
CHg HÌ
CH3 CH,
Ethanol/
HzC HCA
The missing product (s) is(are) :

OH CH,
.nCH3
(1) (2)
H
H,C CH,
CH,
(3) (4)
HgC
(a) 1, 2 and 3 (b) 3 and 4 (c) 2 and 3 (d) 1,2,3 and 4
 336 ORGANICCHEMISTRY for IIT-JEE
5. What is the product of the following S,,2 reaction?
OTs
NaBr
Product
Ph OMe Su2

OMe OMe OMe O. OMe

(a) ,C H (b) H,C -H

(c)
H CH, (d) H CH3
Br
+ Ph
H. -Br Br
+ Ph
H H +
Ph
Br

6. Select the reagent that will yield the greater amount of substitution on reaction with
CH CH, Br :
(a) CH,CH,OK in dimethyl sulfoxide (DMSO)
(b) (CH3),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. Ais not an isomer of C. Which of the following could be the starting material X?
HO
X A BC D

Br CH, CH3
sH Br Br Br,
() (II) (I) (IV)
HgCw H
H,C H H CH, H,C H
(a) (1) (b) (II) (c) (III) (d) (IV)
CH3
8. CH, C
CH3 CH3 CH CH3, CH CH
(c)
Br

Br Br
(a) (b)

Compare rate of E, 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 Ho
DMSO
(b)

HC
OH CH 0H
(C) DMF
(d)
Alkyl Halides 337

10. Rate limiting S,, follows the sequence

R-Br R°Br°R°BrR°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) Allof these
11. Compare the two methods shown for the preparation of carboxylic acids :
Mg 1. CO2
Method 1: RBr diethyl ether RMgBr RCO ,H
2. H,0
NaCN HO, HCI
Method 2: RBr RCN
heat
RCO ,H
Which one of the following statements correctly describes this conversion ?

Br CO,H
(a) Both method land 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,CH,S is both a stronger base and more nucleophilic than CH,CH,0
(b) CH,CH,S is a stronger base but is less nucleophilic than CH,CH,0
(c) CH,CH,S is a weaker base but is more nucleophilic than CH3CH,0
(d) CH,CH,S is both a weaker base and less nucleophilic than CH,CH,0
13. In the given pair of alcohols, in which pair second alcohol is more reactive than first towards
hydrogen bromide ?
CH OH H OH
(a) and

OH
(b) and

OH
H-CH,
 338 ORGANIC CHEMISTRY for IIT-JEE
(c) CH3 CH CH, CH3 and CH3 CH, CH CH2 OH
OH CH3
(d) CH, CH CH, CH, and (CH3),C CH, CH,
OH OH
14. Which product would be expected to predominate in the given reaction ?
OS0,CF3
CH OH
(30 C)

OCH3
(a) (b)

Q- SO2 - CH3
(d) None of these

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

NaOH (excess) Product

Ho
heat
CH,-Br

OH
(a) (b)
CH,- Br CH,- OH

OH
OH
(c) (d)
CH,- OH CH- OH
Br

16. CH3my H VH
D Alc. KOH
(A); Major product of this reaction is:
OH
D CH3. CH3 CH3
(a H (b) (c) (d)
Alkyl Halides 339
17. Rate of S,,2 reaction is:
Br

pr

(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,CH,SNa CHS, (P)
Unknown product (P) of the above reaction is :

(a) (b)

D(c) H S CC CH CH S H
HH
(d) H C
H H
C CH CH S H

Br

Moist Ag0
19. (A) product
Major product (A) is :
OH LOH OH
OH
(a) (6) (d)

KCN
20. MeO Cl Product of reaction is :

(MOM chloride)
(Methoxy methyl chloride)
CN MeO CN
(a) (b)
CN
(c) Me 0 CH; CH, CN (d) 0
-CN
21. In the given pair of compound, in which pair the second compound is more reactive than first
toward S,,2 reaction ?

(a) Cior (b) -CH,- Cl or -I

CI

Br Br
(c) or (d)
 340 ORGANICCHEMISTRY for IlIT-JEE
22. Which compound might be synthesized by the S,2 displacement of an alkyl-halide ?
SCH,CH3
(a) CH, - 0H (b)

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

KOH NBS KCN
23. Identify C in the following series CzH,I A B C.
alc alc.

(a) (CH3),CH CN (b) CH, CH CH,CN

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

o
(a) (1)NBS, ROOR (2) CH CH,0 (3) 2HBr (4) NH, (5) disiamyl borane (6) H,02,0H
(b) (1) Cl, h (2) OH , heat; (3) 2HCI (4) OH , heat (5) HgSO4, H,SO 4
(c) (1) NBS, ROOR; OH , DMSO
(d) (1) Brz, h (2) t-butoxide (3) BH3, THF (4) H,02, OH
25. Which of the reagents shown below would accomplish the following transformations?
Br OH

A B
(a) H0 BH, THF; H,0,/NaOH
(b) NaOH BH, THE; H,02/NaOH
(c) HBr in ether Hg(0Ac)2/H,0; NaBH4
(d) NaNH, Hg(OAc) 2/H,0; NaBH4
26. What are the products obtained from the following reaction ?
Br HC CNa
Product
Et 0
-o=-4

(a) ) +

20% 80% 20% 80%

(c) (d) -C=

100%
100%
Alkyl Halides 341

27. The back-side attack on 2-bromobutane by methoxide (CH 0 ) gives the product shown
below. Which Fischer projection represents 2-bromobutane used as the reactant in this
reaction ?

OCH3
product Etw Me

Et Et Me Br
(a) Me -H
Br
) HBr
Me
(c)
Br (d) Me Et

28. Consider the following statements:

(1) Bridgehead halides are inert towards both S, and S,j2 reactions (till one of the ring size
is eight member ring)
(2) The first step in both S, and E, reactions is the same
(3) >N reactions proceed with total retention of configuration
(4) E, 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) l and 3
(c) 2, 3 and 4 (d) 1, 2, 3 and 4
29. Consider the following alcohols :
CH,OH CH,OH CH,OH ,CH,0H

() O,N (II) CH,0 (II)

Br
(IV)

The order of decreasing reactivities of these alcohols towards substitution with HBr is :
(a) III >I> V> II (b) III >I> II > IV
(c) I> II > V>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, (CH,)2 CH, Br CH,NH, Product of the reaction is :
(a) (b) (c) (d)

H H
33. The configurations of the reactant and the product in the following reaction, respectively,
are:
 342 ORGANICCHEMISTRY for IT-JEE
CO,CHg
KCN
D Br
EtOH
CHCN
H

(a) R, R (b) R, S (c) S, R (d) s, s

Acetone
34. 1-4-dichlorohexane (1 mole) + Nal (1 mole) Product of the reaction is
(a) Cl - CH, CH, - CH- CH2 - CH (b) I CH, - CH, - CH- CH, - CH3
Cl
(c) H,C= CH-CH- CH2 - CH3 (d) I- CH, - CH, - CH, - CH- CH, - CH3
Cl CI
35. Alkyl halides can be obtained by all methods except :
Cl,/UV light
(a) CH,CH,0H HCI/ZnCl, (b) CH3 - CH, - CH, - CH,
(c) G,H_OH NaCl (d) CH,COOAg Brz/cCl4
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, followed by treatment with aq. KOH
(c) Propanol-1 and SOCI,/pyridine
(d) Any of the above can be used
37. Which alkyl halide has maximum density ?
(a) CzH,l (b) CzHs! (c) CH3I (d) CH 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, CH- CI (b) CGH;CI (c) CH,CH CHCI (d) ClCH2 - CH CH,
41. Which of the following reaction will not give ether as a major product ?
(a) CH,CH,Cl Ag,0(dry) (b) (CH,),CCl CH,CH,0 Na
CH3
(c) CH,CH,CI Na o (d) CH4CI Nat0 - C- CH3
CH3
A)
42. O-S-O

CHt-1 (B)
Product (A) and (B) in above reaction is :
Alkyl Halides 343

(a) O - ` 0-H,0 S-0- CH, (b) O S-0-H,0 S -CH3

(c) O -`-0 CH,, 0SH (d) O ^ 0,0 -§0

CH3 H CH,
43. Which of the following would be true for the reaction shown ?
CH,OH
Br OCH
(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 SE 1is :
C
(a) (b)

Cl

CI
(d) <

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)