194 Elementary Organic Chemistry for Medical

3
Haloalkanes and Haloarenes

Level-1

3.1 GENERAL INTRODUCTION :

(CLASSIFICATION, NOMENCLATURE AND NATURE OF C — X BOND)
1. Cl—C—Cl bond angle in 1,1,2,2-tetrachloro ethene and tetrachloromethane is:
(a) 120° and 109.5° (b) 90° and 109.5°
(c) 109.5° and 90° (d) 109.5° and 120°
2. Which of the following is tertiary alkyl halide ?
(a) 2-Chloro-2-methyl butane (b) 1-Chloropropane
(c) 2-Chloropropane (d) Cyclohexyl chloride
3. Select the incorrectly matched :
(a) Thyroxine-Goitre (b) Chloramphenicol-Typhoid
(c) Chloroquine-malaria (d) Fluorohydrocarbons-Boneglue
4. Which of the following is an example of vic-dihalide ?
(a) Dichloromethane (b) 1,2-dichloroethane
(c) Ethylidene chloride (d) Allyl chloride
CH3
5. Which is the correct IUPAC name for Br ?
H3C

(a) 1-Bromo-2-ethylpropane (b) 1-Bromo-2-ethyl-2-methylethane

(c) 1-Bromo-2-methylpropane (d) 2-Methyl-1-bromobutane
6. What should be the correct IUPAC name for diethylbromomethane ?
(a) 1-Bromo-1,1-diethylmethane (b) 3-Bromopentane
(c) 1-Bromo-1-ethylpropane (d) 1-Bromopentane
7. The position of —Br in the compound in CH 3 CH == CHC(Br )(CH 3 ) 2 can be classified as
................ .
Haloalkanes and Haloarenes 195

(a) Allyl (b) Aryl

(c) Vinyl (d) Secondary
8. Ethylidene chloride is a/an .................. .
(a) vic-dihalide (b) gem-dihalide
(c) allylic halide (d) vinylic halide
9. Which of the following compounds are primary haloalkanes ?
I H CH 3
| | |
(I) CH 3 — C — C — CH 3 (II) CH 3 — C — Cl
| | |
H CH 3 CH 3
CH 3
|
(III) CH 3 — CH 2 — CBr 3 (IV) CFH 2 — CH 2 — CH
|
CH 3
(a) I, II (b) III, IV (c) II, III (d) I, IV
10. The carbon atom to which the halogen is attached can be :
(a) sp 2 -hybridized (b) sp 3 -hybridized
(c) sp hybridized (d) both (a) and (b)
11. Which of the the following structures have correct common names ?
CH 3 ‚
(I) CH 2 == CH — CH 2 — F (II) CH — CH 2 Br
Allyl fluoride CH 3 ƒ
Isobutyl bromide

I
|
(III) CHCl 3 (IV) CH 3 — CH — CH 2 — CH 3
Methylene chloride Isopropyl iodide

(a) I, II (b) III, IV (c) I, III (d) II, IV

3.2 METHODS OF PREPARATION : HALOALKANES

12. Alkyl halide can be prepared from :
(a) alkene (b) alcohol (c) carboxylic acid (d) all of these
13. The reaction of SOCl 2 on alkanols to form alkyl chlorides gives good yields because:
(a) alkyl chlorides are immiscible with SOCl 2
(b) the other products of the reaction are gaseous and escape out
(c) alcohol and SOCl 2 are soluble in water
(d) the reaction does not occurs via intermediate formation of an alkyl chloro sulphite
196 Elementary Organic Chemistry for Medical

4Pb(OAc)
14. CH 3 CH 2 COOH ¾¾¾¾® [P ] ; Product [P ] is :
I2 / hv

O O
½½ ½½
(a) CH 3 CH 2 C OCH 2 CH 3 (b) CH 3 CH 2 C OCH 3
O
½½
(c) CH 3 CH 2 I (d) CH 3 C OCH 2 CH 3
C2 H5
½ NaI/HOH/Acetone
15. CH 3 ¾ C ¾ Br ¾¾¾¾¾¾¾® [P ] ; Product [P ] is :
½
C 3H 7
C2 H5 C2 H5
½ ½
(a) CH 3 ¾ C ¾ I (b) I ¾ C ¾ CH 3
½ ½
C 3H 7 C 3H 7
I
½
(c) CH 3 CH 2 CH 2 CH CH 2 CH 2 CH 3 (d) mixture of (a) and (b)
16. Addition of Br 2 on cis-2 butene gives:
(a) A racemic mixture of 2,3-dibromobutene (b) Meso form of 2,3-dibromobutane
(c) Dextro form of 2,3-dibromobutane (d) Laevo form of 2,3-dibromobutane
Acetone
17. R ¾ Cl + NaI ¾¾¾¾® R ¾ I + NaCl
In the above reaction, which alkyl chloride will give maximum yield ?
CH 3 CH 3
½ ½
(a) CH 3 ¾ C ¾ Cl (b) CH 3 CH 2 CH 2 Cl (c) C 6 H 5 ¾ CH ¾ Cl (d) C 6 H 5 ¾ C ¾ Cl
½ ½ ½
CH 3 CH 3 CH 3
18. What compound is obtained when ethanol is distilled with potassium bromide and
concentrated sulphuric acid?
(a) Ethyl hydrogen sulphate (b) Ethyl bromide
(c) Ethylene bromide (d) Acetylene dibromide
19. Which of the following acids will give maximum yield of alkyl chloride in Hunsdicker reaction?
CH 3
½
(a) CH 3 CH 2 CH 2 COOH(b) CH 3 CHCOOH (c) CH 3 CCOOH (d) C 6 H 5 CHCOOH
| ½ |
CH 3 CH 3 CH 3
Haloalkanes and Haloarenes 197

20. Which reagent will you use for the following reaction ?
CH 3 CH 2 CH 2 CH 3 ® CH 3 CH 2 CH 2 CH 2 Cl + CH 3 CH 2 CHClCH 3
(a) Cl 2 / UV light (b) NaCl + H 2 SO 4
(c) Cl 2 gas in dark (d) Cl 2 gas in the presence of iron in dark
21. Chlorobenzene is formed by reaction of chlorine with benzene in the presence of AlCl 3 . Which
of the following species attacks the benzene ring in this reaction ?
(a) Cl - (b) Cl + (c) AlCl 3 (d) [AlCl 4 ]-
22. What is ‘ A’ in the following reaction ?
CH2—CH == CH2

+ HCl ¾® A

CH2—CH == CH2 CH2—CH2—CH2—Cl

(a) Cl (b)

Cl
CH—CH2 — CH3
CH2—CH—CH3
(c) Cl (d)

23. The reaction of toluene with chlorine in the presence of iron and in the absence of light yields
........ .
CH2Cl CH3
Cl
(a) (b)

(c) H3C Cl (d) Mixture of (b) and (c)

24. The synthesis of alkyl fluorides is best accomplished by :

(a) Sandmeyer’s reaction (b) Finkelstein reaction
(c) Swarts reaction (d) Free radical fluorination

3.3 PHYSICAL PROPERTIES

25. Arrange the following compounds in the increasing order of their densities :
Cl Cl Br

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

Cl Cl
 198 Elementary Organic Chemistry for Medical

(a) (I) < (II) < (III) < (IV) (b) (I) < (III) < (IV) < (II)
(c) (IV) < (III) < (II) < (I) (d) (II) < (IV) < (III) < (I)
26. Arrange the following compounds in increasing order of their boiling points :
CH 3 ‚
(I) CH — CH 2 Br (II) CH 3 CH 2 CH 2 CH 2 Br
CH 3 ƒ
CH 3
|
(III) H 3 C — C — CH 3
|
Br
(a) (II) < (I) < (III) (b) (I) < (II) < (III)
(c) (III) < (I) < (II) (d) (III) < (II) < (I)
27. Which of the following is liquid at room temperature ?
(a) CH 3 I (b) CH 3 Br (c) C 2 H 5 Cl (d) CH 3 F
28. Which is the correct increasing order of boiling points of the following compounds ?
1-Iodobutane, 1-Bromobutane, 1-Chlorobutane, Butane
(a) Butane < 1-Chlorobutane < 1-Bromobutane < 1-Iodobutane
(b) 1-Iodobutane < 1-Bromobutane < 1-Chlorobutane < Butane
(c) Butane < 1-Iodobutane < 1-Bromobutane < 1-Chlorobutane
(d) Butane < 1-Chlorobutane < 1-Iodobutane < 1-Bromobutane
29. Which is the correct increasing order of boiling points of the following compounds ?
1-Bromoethane, 1-Bromopropane, 1-Bromobutane, Bromobenzene
(a) Bromobenzene < 1-Bromobutane < 1-Bromopropane < 1-Bromoethane
(b) Bromobenzene<1-Bromoethane<1-Bromopropane<1-Bromobutane
(c) 1-Bromopropane<1-Bromobutane<1-Bromoethane<Bromobenzene
(d) 1-Bromoethane<1-Bromopropane<1-Bromobutane<Bromobenzene
30. Which of the following compounds has the largest dipole moment?
(a) CH 3 Cl (b) CH 2 Cl 2 (c) CHCl 3 (d) CCl 4
31. Dipole moment is highest in:
(a) CHCl 3 (b) CH 4 (c) CHF3 (d) CCl 4
32. Boiling point of alkyl iodide, bromide, chloride and methane are in this order:
(a) Iodide > Bromide > Chloride > CH 4 (b) CH 4 > Chloride > Bromide > Iodide
(c) CH 4 > Iodide > Bromide > Chloride (d) Chloride > Bromide > Iodide > CH 4

3.4 CHEMICAL PROPERTIES

(I) Nucleophile Substitution

33. Which of the following is least reactive for nucleophilic substitution reaction ?
(a) CH 3 CH 2 CHBr (b) H 2 C == CHBr (c) C 6 H 5 CH 2 Br (d) C 6 H 5 Br
Haloalkanes and Haloarenes 199

34. Which of the following combinations is correctly matched ?

H H
½ ½
(a) CH 3 ¾ C ¾ Cl, S N 2 , Walden inversions (b) CH 3 ¾ C ¾ Cl, S N 1 , Walden inversions
½ ½
D D
C 2H 5 C 2H 5
½ ½
(c) C 6 H 5 ¾ C ¾ Cl, S N 1 , Only retension (d) C 6 H 5 ¾ C ¾ Cl, S N 1 , Only inversion
½ ½
CH 3 CH 3
35. Which halide ion is the best nucleophile in dimethyl sulfoxide solution?
(a) fluoride (b) chloride (c) bromide (d) iodide
36. An S N 2 reaction on an asymmetric carbon of a compound always gives :
(a) an enantiomers of the substrate (b) a product with opposite optical rotation
(c) a mixture of diastereomers (d) a single diastereomer
37. Which is the best leaving group in a substitution reaction of an alkyl halide?
(a) Cl - (b) Br - (c) I - (d) F -
38. Order of nucleophilicity in polar protic solvent ?
(a) Is > Br s > Cl s > F s (b) F s > Cl s > Br s > Is
(c) Is > Cl s > Br s > F s (d) F s > Is > Br s > Cl s
39. Order of nucleophilicity in polar aprotic solvent ?
(a) Is > Br s > Cl s > F s (b) F s > Cl s > Br s > Is
(c) Is > Cl s > Br s > F s (d) F s > Is > Br s > Cl s
128 s
40. Which of the following two isomers ( A and B) will undergo S N 1 substitution with I faster
and why ?
H I127

I127 H

(A) (B)
(a) A will react faster because it is more stable than B
(b) A will react fasts because it will yield more stable product and the transition state for both
reactions is of the same energy
(c) B will react faster because it is more stable than A
(d) B will react faster because it is less stable than A. The transition state for both reactions is
of the same energy and it will yield more stable product.
41. Which statement is true with respect to an S N 2 reaction?
(a) A good leaving group is a strong base
(b) A good leaving group is a weak base
200 Elementary Organic Chemistry for Medical

(c) A leaving group must be negatively charged

(d) A leaving group must be a halide
s
AgCN 2 H O/OH
42. CH 3 CH 2 CH 2 Br ¾¾¾® [P ] ¾¾¾¾® [Q ] ; Product [Q ] is :
D

(a) CH 3 CH 2 CH 2 NH 2 (b) CH 3 CH 2 NH 2
(c) CH 3 (CH 2 ) 2 CH 2 NH 2 (d) CH 3 (CH 2 ) 3 CH 2 NH 2
43. Which of the following nucleophiles is going to promote an S N 2 reaction?
r Nu ?
O ¾¾® Nu + OH
|
H
(a) NaI (b) Water (c) NH 4 Cl (d) MeONa
44. What is the major product of the following synthesis?

1. NaS
Br ¾¾¾¾¾¾¾® ?
2. H2, Pd

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

45. What is the most reactive alkyl halide for the following reaction?
RX + H 2 O ¾® R — OH + X -
Br Br
Br Br

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

46. Give the major product of the following reaction.

Br –
Br HO
¾¾¾¾¾®
CH3 1 equivalent
H3C
HO Br OH
(a) (b) Br
H3C CH3 H3C CH3
H H
Br
(c) Br CH2 (d)
H3C CH3 CH3
r
CH3
Br Ag
47. ¾¾¾® [P ] ; Product [P ] is :
Br H 2O

OH OH
OH
(a) O (b) (c) (d)
OH Br OH
Haloalkanes and Haloarenes 201

48. For the following halides, order of rate of reaction with AgNO 3 or rate of S N1 :
Cl Cl Cl

(I) (II) (III)

(a) I > III > II (b) II > III > I (c) I > II > III (d) III > I > II
49. Which of following is least reactive towards S N1 ?
I
I I I

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

CH3
H Br NaI acetone
50. ¾ ¾¾¾¾® P , Product ( P ) is :
H Cl (S 2 ) condition
N
CH3

CH3 CH3 CH3

H I H I I H
(a) (b) (c) (d)
H Cl Cl H H Cl
CH3 CH3 CH3
51. S N1 reactivity of the following halides,
(i) (CH 3 ) 3 CBr (ii) (C 6 H 5 ) 2 CHBr
(iii)(C 6 H 5 ) 2 C(CH 3 ) Br (iv) (CH 3 ) 2 CHBr will be in the order:
(a) iv > i > ii > iii (b) ii > i > iii > iv (c) i > iii > ii > iv (d) iii > ii > i > iv
52. The compound which would undergo S N 2 reaction fastest is:
Cl Br
Cl
(a) (b) (c) Br (d)
CH 3
|
53. CH 3 — C — Br CH 3 — CH — Br CH 3 — CH 2 — CH 2 Br
| | (c)
CH 3 CH 3
( a) (b)
Reactivity toward S N1 :
(a) a > b > c (b) b > a > c (c) b > c > a (d) c > b > a
54. Which of the following compound give same S N1 and S N 2 product ?
Cl

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

Cl Cl Cl
202 Elementary Organic Chemistry for Medical
KSH
55. R-2-chloro butane ¾ ¾
¾® Product, mechanism of reaction is :
acetone
(a) S N1 (b) S N 2 (c) E 2 (d) E 1
56. Most reactive toward S N 2 is :
Cl

(a) CH 3 — Cl (b) H 2 C == CH — Cl (c) (d) CH 3 — F

57. Which of the following species is most reactive in an S N 2 reaction?

(a) CH 3 CH 2 — Cl (b) CH 3 CH 2 — Br (c) CH 3 CH 2 — I (d) CH 3 CH 2 — F
K1
58. CH 3 — CH 2 — Br + NaOH ¾¾® CH 3 — CH 2 — OH + NaBr ¾® reaction ...(1)
CH 3
|
K
CH 3 — C — CH 2 — Br + NaOH ¾¾2®(CH 3 ) 3 C — CH 2 — OH + NaBr ¾® reaction ...(2)
|
CH 3
K 1 and K 2 are rate constant for above reactions, correct relation is:
(a) K 1 = K 2 (b) K 1 > K 2 (c) K 1 < K 2 (d) K 1 << K 2
CH3
H Cl
H D NaI
59. ¾¾®( A), Major product ( A) is:
H Br acetone

H D
CH3
CH3 CH3 CH3 CH3
H I H Cl H Cl Cl H
H D H D H D H D
(a) (b) (c) (d)
H Br H I I H I H
H D H D H D H D
CH3 CH3 CH3 CH3

LiBr
60. Cl ¾ ¾¾¾® ( A), product ( A) is :
S 2 condition
N

Cl
Haloalkanes and Haloarenes 203

Cl Br
(a) (b) (c) (d) Cl
Cl
Br
Br Cl
s
61. CH 3 — I + OH ¾® CH 3 — OH + Is
Which of the following solvents is most suitable for this reaction ?
(a) H 2 O (b) EtOH (c) Et 2 O (d) None of these
62. Which of the following reactions is not possible ?
(a) R — OH + NaBr ¾® R — Br + NaOH (b) R — OH + HBr ¾® R — Br + H 2 O
(c) both reactions are possible (d) both reactions are not possible
63. Which of the following nucleophilic substitutions is practically not possible ?
s s
OH s OH
¾¾®
(a) ¾¾®
H2O + Br (b) H2O
Br OH Br OH
(c) Both (a) and (b) (d) None of these

64. 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) 1-Bromobutane or 2-bromobutane
I II
(a) (A)-I, (B)-I (b) (A)-I, (B)-II (c) (A)-II, (B)-I (d) (A)-II, (B)-II
Br CH3 S 2
65. + OH - ¾ ¾
N
¾ ® A; A is:
H H
HO H CH3 HO CH3
H
(a) (b) (c) both (a) and (b) (d)
H CH3 HO H H H
OH
H
H NaOH
66. ¾ ¾¾®[ X ] , X is :
Cl 25°C

OH OH
OH H
(a) H (b) H
H OH
O

(c) mixture of (a) and (b) (d) H

H
204 Elementary Organic Chemistry for Medical

67. Which of the reactions shown below will be faster ?

Br OH Br OH

KOH KOH
Reaction-1: ¾¾¾® ; Reaction-2: ¾¾¾¾®
H2O Crown ether

(a) Reaction 1 (b) Reaction 2

(c) Both have equal rates of reaction (d) Cannot be predicted
CH3

68. H OH ¾SOCl
¾¾2®( A). Product ( A) is:
Et
CH3 Et CH3
(a) H Cl (b) H Cl (c) Cl H (d)
Et CH3 Et

69. The rate of solvolysis of tert-butyl bromide will be maximum in which of the following
solvents?
(a) Et 2 O (b) CCl 4 (c) EtOH (d) H 2 O
70. Which one of the following compounds will be most reactive for S N1 reactions ?
I Cl Br Cl

O O O
(a) (b) (c) (d)
O
71. In the given reaction:
Cl
Cl
CH OH
3
¾ ¾¾ ¾®[ X ], X is:
O Cl
Cl OCH3 Cl OCH3
Cl Cl OCH3 Cl
(a) (b) (c) (d)
O OCH3 O OCH3 O Cl O Cl
72. Among the bromides I-III given below, the order of reactivity S N1 reaction is:
O
(I) (II) (III)

Br Br Br
(a) III > I > II (b) III > II > I (c) II > III > I (d) II > I > III
73. When ethyl bromide is treated with moist Ag 2 O , main product is:
(a) ether (b) ethanol (c) aldehyde (d) all of these
Haloalkanes and Haloarenes 205

Cl OEt
74. EtOH
¾¾¾® Rate R1

CH3 CH3
EtOH
Cl ¾¾¾® OEt
Rate R2

Cl OEt
EtOH
¾¾¾® Rate R3

Which of the following is correct ?

(a) R 1 > R 2 > R 3 (b) R 3 > R 2 > R 1 (c) R 2 > R 1 > R 3 (d) R 2 > R 3 > R 1
75. In the given reaction:
.. * HOH
CH 3 — CH 2 — S— CH 2 — CH 2 — Br ¾ ¾¾®[ 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)

PhSNa
76. Cl ¾¾¾® (X)

PhSNa
¾¾¾® (Y)

Cl
Relationship between ( X ) and (Y ) is:
(a) constitutional isomer (b) enantiomer
(c) identical (d) none of these
77. Without exception, S N 2 reaction at chiral carbon gives:
(a) enantiomer of substrate (b) product of opposite polarity
(c) diastereomeric mixture (d) only one stereoisomer
78. The order of reactivities of the following alkyl halides for a S N 2 reaction is:
(a) RF > RCl > RBr > RI (b) RF > RBr > RCl > RI
(c) RCl > RBr > RF > RI (d) RI> RBr > RCl > RF
79. The reaction is described as:
H H
CH 3 ¾ (CH 2 )5 ½ - ½ (CH 2 )5 CH 3
OH
C ¾ Br ¾® H¾O¾ C
H 3C CH 3
(a) S E 2 (b) S E1 (c) S N 2 (d) S N1
206 Elementary Organic Chemistry for Medical

80. Which of the following alkyl halides gives the slowest S N 2 reaction?
Cl Cl
| |
(a) CH 3 CH 2 Cl (b) CH 3 CHCH 2 Cl (c) CH 3 CCH 2 CH 3 (d) CH 3 CHCHCH 3
| | |
CH 3 CH 3 CH 3

81. Assuming no other changes, what is the effect on rate of reaction if the concentration of the
alkyl halide doubled in a S N 2 reaction?
CH 3 Br + HO s ¾® CH 3 OH + Br s
(a) No change (b) Doubles the rate
(c) Triples the rate (d) Quadruples the rate
82. Assuming no other changes, what is the effect on rate of reaction if the concentrations of both
alkyl halide and the nucleophile are doubled ?
CH 3 Br + HO s ¾® CH 3 OH + Br s
(a) No change (b) Doubles the rate
(c) Triples the rate (d) Quadruples the rate
83. Which of the following S N 2 reactions is the fastest ?
(a) CH 3 CHCH 3 + HO - ¾® CH 3 CHCH 3 + Br -
| |
Br OH
(b) CH 3 CH 2 CH 2 I + HO - ¾® CH 3 CH 2 CH 2 OH + I –
(c) CH 3 CHCH 3 + HO - ¾® CH 3 CHCH 3 + I -
| |
I OH
(d) CH 3 CH 2 CH 3 Br + HO - ¾® CH 3 CH 2 CH 3 OH + Br -
84. Which of the following S N 2 reactions is the slowest ?
(a) CH 3 CH 2 CH 3 Br + HO - ¾® CH 3 CH 2 CH 3 OH + Br –
(b) CH 3 CH 2 CH 2 Cl + HO - ¾® CH 3 CH 2 CH 2 OH + Cl -
(c) CH 3 CH 2 CH 2 I + HO - ¾® CH 3 CH 2 CH 2 OH + I -
(d) CH 3 CHCH 3 + HO - ¾® CH 3 CHCH 3 + F -
| |
F OH
85. Which halide reacts most rapidly via an S N 2 mechanism?
(a) (CH 3 )CCH 2 CH 2 F (b) (CH 3 )CCH 2 CH 2 Cl (c) (CH 3 )CCH 2 CH 2 Br (d) (CH 3 )CCH 2 CH 2 I
(e) All primary halides react at the same rate in S N 2
86. Which halide reacts most rapidly via an S N 2 mechanism ?

I
(a) I (b) Cl (c) (d)
Br
Haloalkanes and Haloarenes 207

87. Assuming no other changes, what is the effect of doubling only the concentration of the alkyl
halide in the following S N1 reaction?
(CH ) CBr + Is ¾® (CH ) CI + Br s
3 3 3 3
(a) No change (b) Doubles the rate
(c) Triples the rate (d) Quadruples the rate
88. Assuming no other changes, what is the effect of doubling only the concentration of the
nucleophile in the following reaction?
(CH ) CBr + Is ¾® (CH ) CI + Br s
3 3 3 3
(a) No change (b) Doubles the rate
(c) Triples the rate (d) Quadruples the rate (e) Rate is halved
89. Assuming no other changes, what is the effect of doubling both the concentration of the alkyl
halide and the nucleophile in the following reaction?
(CH ) CBr + Is ¾® (CH ) CI + Br s
3 3 3 3
(a) No change (b) Doubles the rate
(c) Triples the rate (d) Quadruples the rate (e) Rate is halved
90. Which of the following alkyl halides gives the fastest S N1 reaction?
(a) CH 3 CH 2 CH 2 Br (b) CH 3 CHCH 3
|
Br
(c) CH 3 CHCH 3 (d) CH 3 CH 2 CH 2 I
|
I
91. Which of the following alkyl halides gives the fastest S N1 reaction?
Br Br
| |
(a) CH 3 CHCHCH 3 (b) CH 3 CHCH 2 CH 2 Br (c) CH 3 CCH 2 CH 3 (d) ClCH 2 CHCH 2 CH 3
| | | |
CH 3 CH 3 CH 3 CH 3

92. Which of the following factors has no effect on the rate of S N1 reactions ?
(a) The nature of the alkyl halide (b) The nature of the leaving group
(c) The concentration of the alkyl halide (d) The concentration of the nucleophile
93. Which of the following is the rate law for S N1 mechanisms?
(a) Rate = k [Alkyl Halide] [Nucleophile]
(b) Rate = k [Nucleophile]
(c) Rate = k [Alkyl Halide]
(d) Rate = k[Alkyl Halide] [Nucleophile] + k 2 [Alkyl Halide]
94. In the S N1 hydrolysis mechanism of (CH 3 ) 3 CBr , there are -------------- elementary steps, ----------
distinct transition states, and --------------- distinct intermediates.
(a) 2, 2, 2 (b) 2, 2, 3 (c) 2, 3, 2 (d) 3, 3, 2
 208 Elementary Organic Chemistry for Medical
r
95. Compare rate of reaction with Ag NOs3 or rate of S N1 reaction :

Br Br Br

(i) (ii) (iii)

(a) i>iii>ii (b) i>ii>iii (c) iii>ii>i (d) ii>i>iii

r s
96. Compare rate of reaction with Ag NO3or rate of S N1 reaction :
I I I

(i) (ii) (iii)

(a) i>ii>iii (b) ii>iii>i (c) ii>i>iii (d) i>iii>ii

r s
97. Compare rate of reaction with Ag NO3 or rate of S N1 reaction :
Br Br Br

(i) (ii) (iii)

(a) i>ii>iii (b) ii>iii>i (c) iii>i>ii (d) ii>i>iii

r s
98. Compare rate of reaction with Ag NO3 or rate of S N1 reaction :
I I I

(i) (ii) (iii)

O
(a) i>ii>iii (b) ii>i>iii (c) iii>ii>i (d) ii>iii>i
r s
99. Compare rate of reaction with Ag NO3 or rate of S N1 reaction :
I I I

(i) (ii) (iii)

O

(a) i>ii>iii (b) ii>iii>i (c) ii>i>iii (d) iii>ii>i

r s
100. Compare rate of reaction with Ag NO3 or rate of S N1 reaction :
Br Br CH2—Br

(i) (ii) (iii)

(a) i>ii>iii (b) ii>iii>i (c) iii>ii>i (d) iii>i>ii

Haloalkanes and Haloarenes 209

r
101. Compare rate of reaction with Ag NOs3 or rate of S N1 reaction :
CH 3
|
(i) CH 3 — C — Br (ii) CH 3 — CH — Br (iii) CH 3 — CH 2 — Br
| |
CH 3 CH 3
(a) i>ii>iii (b) ii>iii>i (c) iii>ii>i (d) ii>i>iii
102. Compare rate of reaction with or rate of S N1 reaction :
Br Br
CH2—Br
(i) (ii) (iii)

(a) i>ii>iii (b) ii>iii>i (c) ii>i>iii (d) iii>i>ii

r
103. Compare rate of reaction with Ag NOs3 or rate of S N1 reaction :

(i) (ii) (iii)

Br Br Br
(a) i>ii>iii (b) iii>ii>i (c) ii>iii>i (d) iii>i>ii
r
104. Compare rate of reaction with Ag NOs3 or rate of S N1 reaction :
Br Br Br
(i) (ii) (iii)

(a) i>iii>ii (b) ii>iii>i (c) i>ii>iii (d) iii>i>ii

r
105. Which of the following is most reactive toward Ag NOs3 or rate of S N1 reaction ?
Br Br

(a) (b)

Br Br

(c) (d)

r s
106. Which of the following is most reactive toward Ag NO 3 or rate of S N1 reaction ?
Br Br
Br
(a) (b) (c) (d)
Br
 210 Elementary Organic Chemistry for Medical

107. What mechanism predominates in the reaction below?

CH3OH, D
CH2CH3 Product, Reaction proceeds with ...... mechanism.

Cl
(a) S N 2 (b) S N1 without rearrangement
(c) S N1 with rearrangement (d) E 1
108. Which of the following is least likely to be found in the product mixture which results when the
alkyl iodide below is heated in water?

(a) (b)
OH

(c) (d) (e)

OH
CH3 Br

rs
109. K SH ( P ) Major product is :
¾¾®

Br
SH SH
CH2

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

Br Br

I I I

110. Compare rate of S N1

(I) (II) (III)

(a) II > III > I (b) II > I > III (c) I > II > III (d) III > II > I
111. Arrange in order of increasing S N1 reaction rate (protic solvent).

(i) Ph Br , (ii) , (iii) Br , (iv)

Br Cl
(a) iv < ii < iii < i (b) i < ii < iii < iv (c) iv < i < iii < ii (d) iv < i < ii < iii
Haloalkanes and Haloarenes 211

112. Arrange the following in their order of nucleophilicity in protic solvent

–
O
O
||
CH 3 O - CH 3 — C — O -
(i) (ii) (iii)
(a) i>ii>ii (b) iii>ii>i (c) ii>i>iii (d) None
113. S N 2 is take place rapidly in protic solvent in the nucleophile.
(a) CH 3 O - (1m) (b) CH 3 O - (2m)
(c) CH 3 O - (3m) (d) all have equal rate.
114. Rate of S N 2 reaction will be maximum in which of the following solvents?
OH

(a) H 2 O (b) CH 3 OH (c) (d) DMF

115. In the following groups,

(I) — OAc (II) — OMe (III) — O — SO 2 Me (IV) — OSO 2 CF3
the order of leaving group ability is:
(a) I>II>III>IV (b) IV>III>I>II (c) III>II>I>IV (d) II>III>IV>I
116. In which of the following reaction either S N1 or S N 2 take place ?
Cl

(a) (b) H 2 C == CH — Cl (c) (d) CH 3 — Cl

Cl
117. Rate of S N 2 will not be negligible in:
Br Br Br Br

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

(II) Elimination Reaction

118. What is the major product of the following reaction?
CH3
alcohol
CH2—C—CH3 + KOH ?
heat
Br
CH3 CH3

CH2—C—CH3 CH2—C == CH2

(a) (b)
OH
 212 Elementary Organic Chemistry for Medical

CH3 CH3 CH3

CH2—CH—CH2OH CH—C—CH3 CH == C—CH3

(c) (d) (e)
OH H
119. How many alkenes are formed by E 2 elimination of HBr from 2-bromo-2,3-dimethylhexane
using a strong base such as sodium methoxide?
(a) 1 (b) 2 (c) 3 (d) 4
120. How many alkenes are formed by E 2 elimination of HBr from 3-bromo-3,4-dimethylhexane
using a strong base such as sodium methoxide?
(a) 2 (b) 3 (c) 4 (d) 5
121. How many alkenes are formed by E 1 elimination of HCl from 3-chloro-3,4-dimethylheptane in
methanol?
(a) 2 (b) 3 (c) 4 (d) 5
122. Which of the following is not reasonable for an elimination reaction?
NaOH
Br ¾¾¾¾® Br ¾¾¾¾®NaOEt
(a) H2O (b) EtOH
NaOH NaI
Br ¾¾¾¾® Br ¾¾¾¾®
(c) H2O/EtOH (d)

Cl
tBuOK, tBuOH
123. ¾¾¾¾¾® ? ; Major product of the reaction is :
Heat

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

124. Give all of the expected products of the following reaction.

MeOH
I ¾¾¾¾®

OMe H
a b c d
(a) a (b) a and c (c) a, b, c and d (d) a, c, and d
125. What is the major product of the following reaction?
tBuOK
¾¾¾® ?
tBuOH

Cl

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

O
Haloalkanes and Haloarenes 213

CH2D
EtOH, NaOH
126. ¾¾¾¾¾® ? , Major product of the reaction is :
H O, Heat
2

Cl
CH2D CH2D
CH2D CH2D
(a) (b) (c) (d)
OEt
127. The major product of the reaction of 1,2-dibromobutane and excess NaNH 2 is :
(a) 2-bromo-1-butene (b) 1-bromo-1-butene (c) 1-butyne (d) 1,2-butadiene
128. Which of the following dibromides would yield 2-butyne upon elimination?
Br
Br
Br
Br Br Br Br
Br
I II III IV
(a) III (b) II and III (c) II and IV (d) I
129. Identify the rate of dehydrohalogenation in the following compound when allowed to reacts
with alc. KOH:
Br

(i) Br (ii) (iii) Br

(a) i > ii > iii (b) ii > i > iii (c) ii > iii > i (d) iii > ii > i
130. Which of the following alkyl halides undergoes E 1 reactions with the fastest rate?
(a) CH 3 CHCH 3 (b) CH 3 CHCH 3 (c) CH 3 CHCH 3 (d) CH 3 CHCH 3
| | | |
F Cl Br I
CH 3
|
131. CH 3 CH 2 O s + CH 3 CBr ¾®
¾ ? , Product(s) of the reaction is/are :
|
CH 3

CH 3
|
(a) CH 3 CH 2 OC — CH 3 (b) CH 2 == CH 2
|
CH 3

(c) CH 3 C == CH 2 (d) (a) & (b) (e) (a) &(c)

|
CH 3
 214 Elementary Organic Chemistry for Medical

132. What is the major product of the following reaction?

alcohol
CH 2 == CHCH 2 CHCH 3 + KOH ¾ ¾¾® ?
heat
|
Br

(a) H 2 C == CH — CH 2 — CH == CH 2 (b) CH 3 CH 2 CH 2 CHCH 3

|
OH

(c) H 2 C == CH — CH == CH — CH 3 (d) CH 2 == CHCHCH 2 CH 3

|
OH
alc. KOH
133. CH 3 — CH 2 — CH — CH 3 ¾ ¾¾¾® X (major)
D
|
Br

(a) (b) (c) (d) None of these

Br
|
134. CH 3 — CH 2 — CH 2 — C — CH 3
|
CH 3
Identify all possible product obtained by E 2 reaction :
CH3
(a) CH 3 — CH 2 — CH 2 — C == CH 2 (b) CH 3 — CH 2 — CH == C
| CH3
CH 3
(c) both (a) and (b) (d) none of these
Br
Zn
135. ¾¾® + ZnBr2 ; This reaction is a case of :
Br
(a) a-elimination (b) b-elimination (c) g-elimination (d) None of these
Br
136. ; Major product obtained when this substrate is subjected to E 2 reaction is :

(a) (b) (c) both (a) and (b) (d) none of these

CH3
Br
137. CH3
Haloalkanes and Haloarenes 215

The major product obtained when this substrate is subjected to E 2 reaction under the
treatment of potassium tert-butoxide will be:
CH2 CH3
(a) (b)
CH3 CH3
(c) both in equal proportions (d) none of these
CH3 CH3 CH3
138. (I) (II) (III)
Br Br Br
CH3

Ease of b-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

Br
|
Alc. KOH
139. CH 3 — C — CH 2 — CH 3 ¾ ¾¾¾® ; Major product of the reaction is :
|
H
(a) butene-1 (b) butene-2 (c) butane (d) butyne-1
140. Which alkyl bromide will yield only one alkene in E 2 elimination ?
Br
(a) (b) Br (c) (d)
Br
Br
141. Which alkyl bromide will yield 3-methyl-1-hexene as the major product upon treatment with
potassium t-butoxide in t-butyl alcohol (solvent) ?
Br
(a) (b)
Br

(c) (d)
Br
Br
142. In order to accomplish the following conversion, what reagent and conditions would be
required ?
?
¾¾®

Cl
(a) Cold sodium hydroxide (b) Hot conc. sodium hydroxide
(c) Potassium t-butoxide and heat (d) Hot water
 216 Elementary Organic Chemistry for Medical

Cl Cl Cl
143. , Which is most easily dehydrohalogenated ?
(I) (II) (III)

(a) I (b) II (c) III (d) All with same ease

144. In dehydrohalogenations, the base (alcoholic KOH) abstracts:
(a) the halides ion
(b) the proton present on the carbon next to the carbon to which the halogen is attached
(c) the proton present on the carbon to which the halogen is attached
(d) the proton on the a-carbon
CH3
145.
Cl
The major product obtained when this substrate is subjected to E 2 reaction will be:
CH3 CH2 CH3
(a) (b) (c) (d) both (a) and (c)

Br
|
146. CH 3 — CH 2 — CH 2 — C — CH 3
|
CH 3
Major product obtained when this alkyl halide is subjected to E 2 reaction under the treatment
of potassium tert-butoxide will be:
CH3
(a) CH 3 CH 2 CH == C (b) CH 3 CH 2 CH 2 C == CH 2
CH3 |
CH 3
(c) both (a) and (b) (d) trans isomer
CH3
147.
Br
CH3
The major product obtained when this substrate is subjected to E 2 reaction will be:
CH3 CH3
(a) (b) (c) (d) none of these
CH3 CH3 CH2
148. Which of the following isomeric hexachlorocyclohexanes is least reactive in
b-dehydrochlorination on treatment with strong base ?
Haloalkanes and Haloarenes 217

Cl Cl

Cl Cl Cl Cl

(a) (b)
Cl Cl Cl Cl
Cl Cl

Cl

Cl Cl

(c) (d) All three are equally reactive

Cl Cl
Cl
149. Correct order of yield of Hofmann alkene in following reaction will be:
CH 3 CH 2 CHCH 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
Br
H3C H

150. ¾® ? Product is:

¾
H CH3 -Br2

Br
H3C H H3C H
(a) (b)
H CH3 H3C H

(c) both (a)and (b) (d) none of these

C6H5
CH3 H
Alcoholic KOH
151. ¾® A ; Product A is :
¾ ¾¾¾¾
Br H E2

C6H5

CH3 C6H5 CH3 C6H5 H CH3

C C C
(a) (b) (c) (d) none is correct
C C C
H C6H5 C6H5 H C6H5 C6H5
 218 Elementary Organic Chemistry for Medical

Cl
H H alc. KOH
152. ¾ ¾¾¾® A. The structure of ‘ A’ is:
D D

H D H D H H H D
(a) D (b) D (c) D (d) D

alc. KOH EtONa

153. CH 3 — CH 2 — CH — CH 3 ¾ ¾¾¾® X ; CH 3 — CH 2 — CH — CH 3 ¾ ¾¾® Y
Major D Major
| |
Br NMe 3
r
Product ( X ) and (Y ) respectively are :
(a) 1-butene, trans-2-butene (b) 1-butene, cis-2-butene
(c) cis-2-butene, 1-butene (d) trans-2-butene, 1-butene
154. Debromination of meso-dibromobutane gives mainly:
(a) n-butane (b) 1-butene (c) cis-2-butene (d) trans-2-butene
155. Under certain conditions alkyl halides reacts with base to give an alkene and HCl (elimination
reaction). For example, RCH 2 ¾ CH 2 Cl ¾® R ¾ CH == CH 2 +HCl
The extent of these reaction depends on the structure of alkyl halides (e. g., primary, secondary
and tertiary). The relative extent to which such reactions take place is (in the order of halo-
alkanes):
(a) p < s < t (b) p > s > t (c) p > s < t (d) p < s > t
CH 3
|
156. CH 3 — C — Br CH 3 — CH — Br CH 3 — CH 2 — CH 2 Br ,
| | (c)
CH 3 CH 3
( a) (b)
Reactivity order of a , b, c towards E 2 is :
(a) a > b > c (b) b > a > c (c) b > c > a (d) c > b > a
CH 3
|
157. CH 3 — C — Br CH 3 — CH — Br CH 3 — CH 2 — CH 2 Br
| | (c)
CH 3 CH 3
( a) (b)
Reactivity order of a , b, c towards E 1 is :
(a) a > b > c (b) b > a > c (c) b > c > a (d) c > b > a

158. Cl ¾CH
¾¾3ONa
¾®( A) , Reaction will proceed with ........ mechanism :
D (50°C)

(a) S N1 (b) S N 2 (c) E 2 (d) E 1

Haloalkanes and Haloarenes 219
NaNH
159. Ph — CH 2 — CH — CH 2 — CH 3 ¾ ¾¾ ¾2®( A)
|
Br
Total number of elimination product are (includes stereoisomer):
(a) 2 (b) 4 (c) 6 (d) 8
Br
|
x NaNH CH 3 I
160. Ph — C — CH 3 ¾ ¾¾¾2®( A) ¾ ¾¾ ® Ph — C ºº C — CH 3
|
Br
Br y NaNH
2
¾¾¾¾® ; Sum of x + y is :
Br
(a) 2 (b) 4 (c) 5 (d) 6
161. How many distinct alkene products are possible when the alkyl iodide below undergoes E 2
elimination? (Including stereoisomers)
CH3
CH3
I CH3
(a) 1 (b) 2 (c) 3 (d) 5
162. Which of the following halides is most reactive in an E 2 reaction with sodium methoxide?
(a) (CH 3 ) 3 CCH 2 I (b) (CH 3 ) 2 CHCHICH 3
(c) (CH 3 ) 2 CHCH 2 Br (d) (CH 3 ) 2 CHCH 2 Cl
163. Which of the following alkyl halides forms the most stable carbocation when it undergoes an
E 1 reaction?
Br
Br Br Br Br
(I) (II) (III) (IV) (V)

(a) I (b) II (c) III (d) IV

164. Why is the alkyl halide below not capable of undergoing an E 2 reaction upon treatment with
sodium ethoxide?
CH3

Br

CH3
(a) Br - is too poor a leaving group
(b) the substrate is too hindered
(c) too much angle strain would be present in the alkene product
(d) the C—H and C—Br bonds which need to break cannot achieve an anti-periplanar
orientation
 220 Elementary Organic Chemistry for Medical

165. Which of the following compounds is/are the products of the reaction:
heat
H H + HO– ? (I) CH3 or/and (II) CH3

CH3 Br
(a) I only (b) II only
(c) I and II are of equal yield (d) I is minor, II is major
166. Predict the two most likely mechanisms for the reaction of 2-iodohexane with sodium
ethoxide.
(a) S N 2 and S N1 (b) E 1 and E 2 (c) S N 2 and E 2 (d) E 1 and S N1
167. Which of the following statements correctly describe(s) E 1 reactions of alkyl halides ( RX )?
I. Rate = k [base] II. Rate = k [base][RX]
III. Rate = k [RX] IV. The reactions occur in two distinct steps
V. Rearrangements are sometimes seen
(a) II and IV (b) III, IV and V (c) I, IV and V (d) I only
168. Which one of the following compounds on dehalogenation gives 2, 3-dimethyl-2-butene ?
Cl Cl
½ ½
(a) CH 3 ¾ C ¾ C ¾ CH 3 (b) CH 3 ¾ (CH 2 ) 4 ¾ CHCl 2
½ ½
CH 3 CH 3
(c) CH 3 ¾ CH 2 ¾ CHCl 2 (d) CH 2 Cl ¾ (CH 2 ) 4 ¾ CH 2 Cl
H Br
H3C D C H ONa
2 5
169. H H ¾¾¾¾® [ A] ; Major product is :
D

OH
D H3C D H3C HC
3
D
(a) H (b) (c) (d)

CH3
–
170. r
OH
NMe3
¾¾¾®
D
Olefinic product, formed in the reaction is:

Et Et
(a) (b) (c) (d) none of these

171. alc. KOH

Cl HO ¾¾¾® (A), Product (A) is:

H H
Haloalkanes and Haloarenes 221

OH O

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

Cl
172. Which of the following undergo fastest dehydrobromination?
Br Br
Br Br
(a) (b) (c) (d)

Br

173. H ¾alc.
¾¾
KOH
¾® (A) ; Product (A) is:
D

(a) (b) No-reaction (c) (d) None

(III) Reaction with Metals

174. When 1-bromo-3-chlorocyclobutane is treated with two equivalents of Na in the presence of
ether, which of the following will be formed ?
Br Cl
(a) (b) (c) (d)

175. In the given reaction

Cl
Zn
¾¾® A
Ether ( Major )
Cl CH3
The product A is :

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

CH3 CH3 CH3 CH3

176. Atomic number of metal which is used in Frankland’s reaction is :

(a) 26 (b) 30 (c) 11 (d) 29
177. Product of Wurtz-Fittig reaction is an :
(a) alkane (b) arene (c) alkylarene (d) either of these

3.5 METHODS OF PREPARATION : HALOARENES

178. Chlorobenzene can be prepared from :
(a) C 6 H 5 N 2 Cl (b) C 6 H 5 CHO (c) C 6 H 5 CH 2 COOAg (d) all of these
 222 Elementary Organic Chemistry for Medical

179. In the given reaction :

HF/BF3 / D
C 6 H 5 N 2 Cl ¾¾¾¾® [P ]
Product [P ] will be :
r s
(a) C 6 H 5 N ºº NBF4 (b) C 6 H 5 F (c) C 6 H 5 Cl (d) C 6 H 5 H
180. The compound C is :
3Cl 2 / D
2 Zn/HClBr / Fe
C 7 H 8 ¾¾¾¾® A ¾¾¾¾® B ¾¾¾¾® C
(a) o-bromotoluene (b) m-bromotoluene
(c) p-bromotoluene (d) 3-bromo-2,4,6-trichlorotoluene

3.6 PHYSICAL AND CHEMICAL PROPERTIES

(I) Nucleophilic Substitution

3 2 CH CO H
181. Ph — CH — Cl ¾ ¾¾¾ ® , This reaction is known as:
|
CH 3
(a) methanolysis (b) ethanolysis (c) acetolysis (d) formalysis
182. Aryl halides are less reactive towards S N reactions as compared to alkyl halides due to :
(a) the formation of more stable carbocation
(b) resonance stabilisation
(c) long carbon-halogen bond
(d) sp 2 -hybrid carbon attached to Cl having lone pairs
183. Consider the following two anionic molecules. Which of the following statements is TRUE?
– –
O S

(I) (II)
(a) I is more basic and more nucleophilic than II
(b) I is less basic and less nucleophilic than II
(c) I is more basic but less nucleophilic than II
(d) I is less basic but more nucleophilic than II
184. Which of the following correctly ranks the aryl halides in decreasing order of reactivity toward
sodium methoxide in methanol ?
Correct order of reactivity of aryl halides with respect to CH 3 ONa / CH 3 OH is :
Br F Br F
NO2
(a) > > >
NO2 NO2 NO2 NO2
NO2 NO2
Haloalkanes and Haloarenes 223

F Br F Br
NO2
(b) > > >
NO2 NO2 O2N NO2
NO2 NO2
Br Br F F
NO2
(c) > > >
NO2 O2N NO2 NO2
NO2 NO2
F Br Br F
NO2
(d) > > >
O2N NO2 NO2 NO2
NO2 NO2

Cl
LiBr acetone
185. ¾ ¾¾¾¾®( A), Product ( A) is:
Cl S condition
N2

Br Br Cl Cl
(a) (b) (c) (d)
Cl Br Br
CH2Br
186. + NH 3 ¾® Major product of the reaction is :
Br

CH2NH2 CH2NH2 CH2Br

(a) (b) (c) (d) all of these
Br NH2 NH2
187. Which one of the following compounds will give enantiomeric pair on treatment with HOH ?
C 2H 5 CH 3 H C 2H 5
| | | |
(a) C 6 H 5 — C — I (b) CH 3 — C — Br (c) C 6 H 5 — C — Br (d) C 2 H 5 — C — Br
| | | |
C 2H 5 C 2H 5 D CH 3

NO2

(1) –OH (1 equivalent)

188. ¾¾¾¾¾¾¾¾® (A) , Organic product ( A) is:
(2) K3FeCN6
NO2
 224 Elementary Organic Chemistry for Medical

NO2
NO2

(a) (b) NO2

HO NO2 OH
OH NO2

(c) (d) NO2

NO2 OH

189. Rank the following in order of decreasing reactivity with methanol.

Br
I Br I

I II III IV
(a) III > II > IV > I (b) IV > I > II > III (c) I > IV > II > III (d) I > IV > III > II
190. Which of the following compounds is most rapidly hydrolysed by S N1 mechanism ?
(a) C 6 H 5 Cl (b) ClCH 2 CH == CH 2 (c) (C 6 H 5 ) 3 CCl (d) C 6 H 5 CH 2 Cl
191. Which will give white ppt. with AgNO 3 ?
(a) Cl (b) Cl (c) CH2Cl (d) Both (a) and (c)

CH2—Cl
sr
Ph—S Na
192. ¾¾¾® (A), Structure of product ( A) is :

Br
Cl SPh SPh

(a) (b) (c) (d) None

SPh Br SPh
193. Which of the following compounds will undergo S N 2 reaction?
Cl Cl

(a) (b)

(c) H 2 C == CH — Cl (d)

Cl
Haloalkanes and Haloarenes 225

Cl
Cl
( X ) alc. KOH
194. ¾ ¾¾¾¾® ; value of X is :
Cl
Cl
(a) 0 (b) 1 (c) 2 (d) 3

(II) Electrophilic Substitution

195. In chlorobenzene, the —Cl atom :
(a) activates the benzene ring more via resonance effect than deactivating it via inductive
effect
(b) deactivates the benzene ring more via inductive effect than activating in via resonance
effect
(c) activates the benzene ring via resonance effect and deactivates it via inductive effect. Both
these effects are more evenly matched
(d) none of these
Br
Br C H ONa
2 5
196. ¾ ¾¾¾ ®( P ), Product ( P ) is:
C 2H 5OH

NO2
OC2H5 Br OC2H5 Br
Br OC2H5 OC2H5 Br
(a) (b) (c) (d)

NO2 NO2 NO2 OC2H5

s
HCHO/Conc. HCl KMnO 4 /OH / D
197. C 6 H 5 Cl ¾¾¾¾¾¾® ( P ) ¾¾¾¾¾® (Q ) ; Product (Q ) is :
Anhy. ZnCl 2

CH2Cl

(a) Cl CH2Cl (b) Cl

(c) Cl COOH (d) COOH

198. Replacement of Cl of chlorobenzene to give phenol requires drastic conditions but chlorine of
2,4-dinitrochlorobenzene is readily replaced because:
(a) NO 2 makes the electron rich ring at ortho and para positions
(b) NO 2 withdraws electrons at metaposition
(c) NO 2 donate electrons at m-position
(d) NO 2 withdraws electrons at ortho and para positions
 226 Elementary Organic Chemistry for Medical

199. Toluene when treated with Br 2 / Fe, gives p -bromotoluene as the major product because the
methyl group is :
(a) p-directing (b) m-directing (c) activating group (d) deactivating group

Reaction with Metals and Elimination Reactions

200. Ph — Br + Mg ¾® G.R., solvent used in this reaction is:
(a) ethane (b) ethanol (c) diethyl ether (d) acid
Br
(X) NaNH2 s r
201. Ph—CH—CH2 ¾¾¾¾® Ph—CººC Na ; Value of X is:
(X = No. of moles of NaNH2)
Br
(a) 1 (b) 2 (c) 3 (d) 4

CH2—CH2—Br CD2—CH2—Br
202. (I) (II) (III) CD 3 — CH 2 Br

Ease of b-dehydrobromination among these halides under the treatment of strong base will be
in the order as:
(a) I > II > III (b) III > II > I (c) III > I > II (d) II > III > I
Ph KOH
203. ¾¾¾® (A), A is:
EtOH
F
CH2 CH3 CH3
(a) Ph (b) Ph (c) Ph (d) Ph
OEt
204. Wurtz-Fittig reaction takes place between :
(a) R ¾ X and R ¾ X (b) R ¾ X and Ar ¾ X
(c) Ar ¾ X and Ar ¾ X (d) R ¾ X and R 2 CuLi

3.7 POLYHALOGEN COMPOUNDS

205. Which of the following alcohols will give chloroform with Cl 2 / NaOH ?
CH 3 OH
| |
(a) CH 3 OH (b) CH 3 CCH 3 (c) CH 3 CH 2 OH (d) CH 3 CH 2 CCH 3
| |
CH 3 CH 3
206. When iodoform is heated with silver powder, it forms:
(a) acetylene (b) ethylene (c) methane (d) ethane
207. Acidic strength of fluoroform(I), bromoform(II), iodoform(III) and chloroform(IV) in
decreasing order is as follows :
(a) I > II > III > IV (b) IV > III > II > I (c) IV > I > II > III (d) IV > I > III > II
Haloalkanes and Haloarenes 227

Air / hn C 6 H 6 / Anhy. AlCl 3

208. CHCl 3 ¾¾¾® [P ] ¾¾¾¾¾¾¾® [Q ] ; Product [Q ] is :
(Excess)

O O O O
½½ ½½ ½½ ½½
(a) C 6 H 5 ¾ C ¾ Cl (b) C 6 H 5 ¾ C ¾ C 6 H 5 (c) Cl ¾ C ¾ Cl (d) C 6 H 5 ¾ C ¾ H
209. Dichloromethane on treatment with alc. KOH / D will give :
··
(a) H 2 C==CH 2 (b) HC ºº CH (c) HCHO (d) CHCl
210. Which of the following will react with water?
(a) CHCl 3 (b) Cl 3 CCHO (c) CCl 4 (d) ClCH 2 CH 2 Cl
211. When chloroform is hydrolysed with KOH, then the final product is:
(a) HCOOH (b) HCOOK (c) CH 3 OH (d) None of these
212. The chemical name of DDT is:
(a) dichlorodinitrotoluene (b) dichlorodimethyltoluene
(c) p , p¢-dichlorodiphenyltrichloroethane (d) none of these

Miscellaneous
213. Which one of the following compounds does not react with bromine?
(a) Ethylamine (b) Propane (c) Phenol (d) Chloroform
214. Identify the set of reagents/reaction-conditions ‘ X ’ and ‘ Y ’ in the following set of
transformation:
X Y
CH 3 ¾ CH 2 ¾ CH 2 Br ¾® Product ¾® CH 3 ¾ CH ¾ CH 3
½
Br
(a) X = dilute aqueous NaOH, 20°C; Y = HBr / CH 3 COOH, 20°C
(b) X = conc. alcoholic NaOH, 80°C; Y = HBr / CH 3 COOH
(c) X = dilute aqueous NaOH, 20°C; Y = Br 2 / CHCl 3 , 20°C
(d) X = conc. alcoholic NaOH, 80°C; Y = Br 2 / CHCl 3
215. Compound [ X ] having molecular formula C 6 H 10 Cl 2 on hydrolysis gives a ketone. Therefore
[ X ] will be :
Cl Cl Cl
½ ½ ½
(a) CH 3 CH CH 2 CH CH 2 CH 3 (b) CH 3 CH CH 2 CH 2 CH 2 CH 2 Cl
Cl
½
(c) CH 3 CH 2 CH 2 CH 2 CH 2 CHCl 2 (d) CH 3 CH 2 CH 2 C CH 2 CH 3
½
Cl
216. Which among the following compounds on basic hydrolysis will give formaldehyde ?
(a) CHCl 3 (b) CH 3 ¾ CHCl 2 (c) CH 2 Cl 2 (d) CCl 4
 228 Elementary Organic Chemistry for Medical

217. Two isomeric compounds Cl ¾ CH 2 ¾ CH 2 ¾ CH 2 Cl and CH 3 ¾ CH 2 ¾ CHCl 2 can be

distinguished by the use of :
s
(a) HOH / OH
(b) Tollen’s reagent
s
(c) Both HOH / OH and Tollen’s reagent
s
(d) HOH / OH Tollen’s reagent and cerric ammonium nitrate
(CH 2 ) 5 ¾ CH 3 (CH 2 ) 5 ¾ CH 3
½ s ½
OH
218. H ¾ C ¾ Br ¾¾¾® HO ¾ C ¾ H
½ ½
CH 3 CH 3
The given reaction is an example of :
(a) S E 2 (b) S N1 (c) S N 2 (d) S E1
219. Free energy profile for given reaction is
HO s + CH — Br ¾® HO — CH + Br s
3 3

Free Free
(a) Energy (b) Energy

Reaction co-ordinate Reaction co-ordinate

Free Free
Energy Energy
(c) (d)

Reaction co-ordinate Reaction co-ordinate

220. CHCl 3 + [Link] ¾®
¾ (A) + H 2 O
(Exces) D

¾® (B) + H 2 O
CCl 4 + aq. KOH ¾
D
(Exces)

(a) A is acid, B is aldehyde (b) (A) is acid , B is alcohol

(c) A is acid, B is CO 2 (d) A is aldehyde, B is acid.
HO s s
221. ¾¾®
D (A) ; HO
¾¾® (B) ; Relation between ( A) and ( B ) is:
D
NMe3 Br
r
(a) positional isomers (b) functional isomers
(c) chain isomers (d) mesomers
Haloalkanes and Haloarenes 229

222. NaCN , Mechanism of the reaction is :

CH2CH3

Cl
(a) S N 2 (b) S N1 without rearrangement
(c) S N1 with rearrangement (d) E 1
NaOCH3, CH3OH
223. CH2CH3 ; Mechanism of the reaction is :

Cl
(a) S N 2 (b) S N1 without rearrangement
(c) S N1 with rearrangement (d) E 2
224. In the following reaction product [Q ] will be :
Br
½ ·· (i) AgOH
CH 3 ¾ CH 2 ¾ CH ¾ CH 3 + CH 2 ¾ N ¾ CH 3 ¾® [P ] ¾¾¾¾® [Q ]
(ii) D
½
CH 3
(a) quaternary ammonium bromide (b) quaternary ammonium hydroxide
(c) 2-butene as major product (d) 1-butene as major product

D HCl
225. Br Cl ¾¾®
–OH
(A) ¾¾® (B), B is:
NMe3
+
Cl Cl

(a) Br Cl (b) Br Cl (c) Br Cl (d) Br Cl

Cl OCl
226. Which of the following statements are correct for CCl 4 ?
(a) CCl 4 is used as fire-extinguisher under the name pyrene
(b) It is stable even at higher temperature
(c) Its vapours are inflammable
(d) All of these
227. The solution of (+)-2-chloro-2-phenylethane in toluene racemises slowly in the presence of
small amount of SbCl 5 , due to the formation of :
(a) carbanion (b) carbene (c) free radical (d) carbocation
Air / hn C 6 H 6 / Anhy. AlCl 3
228. CHCl 3 ¾¾¾® [P ] ¾¾¾¾¾¾¾® [Q ] ; Product [Q ] is :
( excess)

O O O
½½ ½½ ½½
(a) Cl ¾ C ¾ Cl (b) C 6 H 5 ¾ C ¾ Cl (c) C 6 H 5 ¾ C ¾ C 6 H 5 (d) C 6 H 5 ¾ CHO
 230 Elementary Organic Chemistry for Medical

229. Under identical conditions, solvolysis of which of the following substrates would lead to
maximum recemization ?
Et CH3 CD3
(a) H Br (b) H Cl (c) H Cl (d) H Cl
CH3 D CH3 D
R1 R1
| |
HOH
230. R — C — X ¾ ¾
¾® R — C — OH
| |
R2 R2
For the given reaction, which substrate will show maximum racemisation ?
CH 3 CH 3
| |
(a) C 6 H 5 — C — Br (b) CH 2 == CH — C — Br
| |
C 2H 5 C 2H 5
Br Br

C6H5—C NO2
(c) C6H5—C OCH3 (d)

CH3 NH3
r

CH2OH
( X ) HBr
231. ¾ ¾¾¾®; Value of ( X ) is:
OH
(a) 1 (b) 2 (c) 3 (d) 4
232. Which of the following compounds will undergo an S N 2 reaction most readily?
(a) (CH 3 ) 3 CCH 2 I (b) (CH 3 ) 3 CCl
(c) (CH 3 ) 2 CHI (d) (CH 3 ) 2 CHCH 2 CH 2 CH 2 I
233. Which of the following S N 2 reactions is the fastest ?
(a) CH 3 CH 2 CH 2 CH 2 Br + OH - ¾® CH 3 CH 2 CH 2 CH 2 OH + Br -
(b) CH 3 CH 2 CH 2 CH 2 Br + H 2 O ¾® CH 3 CH 2 CH 2 CH 2 OH + HBr
(c) CH 3 CH 2 CHBrCH 3 + OH - ¾® CH 3 CH 2 CHOHCH 3 + Br –
(d) CH 3 CH 2 CHBrCH 3 + H 2 O ¾® CH 3 CH 2 CHOHCH 3 + HBr
C 6H 6
234. CCl 4 ¾¾¾¾¾® [P ] ; Product [P ] is :
Anhy. AlCl 3 / D
Haloalkanes and Haloarenes 231

Cl
½
(a) (C 6 H 5 ) 4 C (b) C 6 H 5 ¾ C ¾ C 6 H 5 (c) C 6 H 5 CCl 3 (d) (C 6 H 5 ) 3 CCl
½
Cl
235. Which of the following S N 2 reactions is the slowest ?
(a) CH 3 CH 2 CHBrCH 3 + OH - ¾® CH 3 CH 2 CHOHCH 3 + Br -
(b) CH 3 CH 2 CHBrCH 3 + H 2 O ¾® CH 3 CH 2 CHOHCH 3 + HBr
(c) CH 3 CH 2 CH 2 CH 2 Br + OH - ¾® CH 3 CH 2 CH 2 CH 2 OH + Br -
(d) CH 3 CH 2 CH 2 CH 2 Br + H 2 O ¾® CH 3 CH 2 CH 2 CH 2 OH + HBr
236. Which of the following bromides reacts readily via an S N 2 reaction with NaN 3 ?
(a) C 6 H 5 Br (b) CH 3 CH 2 CH == CHBr
(c) (C 6 H 5 ) 3 CBr (d) (CH 3 ) 3 CCH 2 CH 2 CH 2 Br

H CH3 CH3

Br /hn
2
237. CH3 Cl ¾ ¾¾® Br Cl and Cl Br

CH2CH3 CH2CH3 CH2CH3

I II
(R)-2-chlorobutane, :
(a) only I was formed
(b) both I and II were formed in equal amounts
(c) both I and II were formed in unequal amounts
(d) only II was formed
238. Which among the following compounds will give Wurtz reaction ?
(a) H 2 C == CH — Br (b) C 6 H 5 — Br
(c) H 2 C == CH — CH 2 — Br (d) None of these
Cl

239. , Which of the following will convert A into aromatic compound easily ?
O
(A)
(a) AlCl 3 (b) HCl (c) H 2 SO 4 (d) Na

240. , Which of the following will convert A into aromatic compound easily ?
(A)
(a) H s (b) H r (c) NaOH (d) NaHCO 3
 232 Elementary Organic Chemistry for Medical

OH

241. , Which of the following will convert A into aromatic compound easily ?
(A)
(a) HCl (b) NaOH (c) NaH (d) NaHCO 3

A nswers
1. (a) 2. (a) 3. (d) 4. (b) 5. (c) 6. (b) 7. (a) 8. (b) 9. (b) 10. (d)
11. (a) 12. (d) 13. (b) 14. (c) 15. (d) 16. (a) 17. (b) 18. (b) 19. (a) 20. (a)
21. (b) 22. (c) 23. (d) 24. (c) 25. (a) 26. (c) 27. (a) 28. (a) 29. (d) 30. (a)
31. (c) 32. (a) 33. (d) 34. (a) 35. (a) 36. (d) 37. (c) 38. (a) 39. (b) 40. (d)
41. (b) 42. (a) 43. (a) 44. (c) 45. (c) 46. (b) 47. (c) 48. (c) 49. (a) 50. (c)
51. (d) 52. (c) 53. (a) 54. (c) 55. (b) 56. (a) 57. (c) 58. (b) 59. (c) 60. (b)
61. (c) 62. (a) 63. (a) 64. (c) 65. (c) 66. (d) 67. (b) 68. (a) 69. (d) 70. (a)
71. (a) 72. (a) 73. (b) 74. (c) 75. (c) 76. (d) 77. (a) 78. (d) 79. (c) 80. (c)
81. (b) 82. (b,d) 83. (b) 84. (d) 85. (d) 86. (d) 87. (b) 88. (a) 89. (b) 90. (c)
91. (c) 92. (d) 93. (c) 94. (d) 95. (b) 96. (b) 97. (a) 98. (c) 99. (a) 100. (c)
101. (a) 102. (a) 103. (b) 104. (c) 105. (a) 106. (d) 107. (d) 108. (d) 109. (d) 110. (b)
111. (a) 112. (c) 113. (c) 114. (d) 115. (b) 116. (d) 117. (d) 118. (e) 119. (b) 120. (d)
121. (d) 122. (d) 123. (a) 124. (d) 125. (b) 126. (a) 127. (c) 128. (b) 129. (a) 130. (d)
131. (c) 132. (c) 133. (a) 134. (c) 135. (b) 136. (b) 137. (a) 138. (d) 139. (b) 140. (b)
141. (d) 142. (c) 143. (a) 144. (b) 145. (a) 146. (b) 147. (b) 148. (b) 149. (a) 150. (a)
151. (a) 152. (c) 153. (d) 154. (d) 155. (a) 156. (a) 157. (a) 158. (b) 159. (b) 160. (c)
161 (d) 162. (b) 163. (d) 164. (d) 165. (d) 166. (c) 167. (b) 168. (a) 169. (c) 170. (a)
171. (c) 172. (c) 173. (a) 174. (d) 175. (a) 176. (b) 177. (c) 178. (a) 179. (b) 180. (b)
181. (c) 182. (d) 183. (c) 184. (c) 185. (c) 186. (a) 187. (c) 188. (b) 189. (c) 190. (c)
191. (d) 192. (b) 193. (b) 194. (c) 195. (c) 196. (a) 197. (c) 198. (d) 199. (a) 200. (c)
201. (c) 202. (a) 203. (c) 204. (b) 205. (c) 206. (a) 207. (c) 208. (a) 209. (d) 210. (b)
211. (b) 212. (c) 213. (d) 214. (b) 215. (d) 216. (c) 217. (d) 218. (c) 219. (d) 220. (c)
221. (a) 222. (a) 223. (d) 224. (d) 225. (c) 226. (d) 227. (d) 228. (c) 229. (c) 230. (c)
231. (a) 232. (d) 233. (a) 234. (d) 235. (b) 236. (d) 237. (b) 238. (c) 239. (a) 240. (b)
241. (a)
 A to Z (Learning Chart)
MgBr

CH3
Level-2

1. Identify the missing :

r
Haloalkanes and Haloarenes

Cl Cu H3O NaOH
S T 300°C
U V D
W CaO, D
OH s Et) 2
CO 2
D3Or CH( SOCl2

H+ HBr Na NH3 KOBr

D
A B C X Y Z
CCl4 dry Ether D
O
2
/H Br2/CCl4 Mg O
Br 2
D+E Cl—C—O—Et (1) PhMgBr (excess)
Na H I J
O Ether
G (2) H+
Mg Ether
CO2
CH3MgBr
F
H+

CH3—Li(excess)
O CH3 O
(1) Al(Mg) H+ (1) CH3MgBr
C—CH3 K D
C— C — CH3 L
(2) H2O (2) NH4Cl
D
H+

(1) CH3MgBr
(2) H+
M

O+ P N Q+R
(2) H+
233
234 Elementary Organic Chemistry for Medical

2. Determine whether a substitution reaction will take place by an S N1 or an S N 2 pathway.

[Link]. SN1 SN2 No reaction

CH 3
|
H 2O
1. CH 3 — C — Br ¾ ¾
¾®
|
CH 3
Br
2. HO -
¾¾
¾®

Br
3. I-
¾¾®

HO -
4. CH 3 — Br ¾ ¾
¾®

3 H O+
5. Ph — O — CH 3 ¾ ¾¾®

6. 3H O+
Ph — O ¾¾¾®

O 3 H O+
7. ¾¾¾®

+
8. Ph—O CH3 ¾H¾
3O
¾®

HI
9. O—CH3 ¾¾®

HI
10. Ph — O — CH 3 ¾¾®

CH 3
|
H— I
11. CH 3 — C — OH ¾ ¾
¾®
|
CH 3

OEt
H O+
3
12. ¾¾¾®
OEt
Haloalkanes and Haloarenes 235

13. 3 H O+
Ph — O — Ph ¾ ¾¾®

H O+
3
¾¾¾®
14.
Br
I
15. OH -
¾¾
¾®

I
16. ¾¾
¾®
H 2O

CH2CH3

17. C + CH3O–
CH3 H high concentration
Br
CH2CH3

18. C + CH3OH
CH3 H
Br
Br

19. ¾¾¾¾
¾2Moist Ag O
®

CH 3 CH 2 CHCH 3 + HO -
high concentration
20. |
Cl

CH 3 CH 2 CHCH 3 + H 2 O
21. |
I

CH2CH3

22. C + CH3CH2CH2Os
CH3 H high concentration
Br
CH2CH2CH3

23. C + EtOH
CH3 H
Cl
236 Elementary Organic Chemistry for Medical

H
CH3
24. + CH3O–
Cl high concentration
H
H
CH3
25. + CH3OH
Cl
H
3. Calculate the number of products formed in the given reactions.
[Link]. Compound SN1 + E1 (Total products) (including Stereoisomer)
EtOH
(i) ¾ ¾¾®
Br
(ii) Cl
EtOH
¾ ¾¾®

(iii) Br
(iv)
Br
(v) H

CH3 Br
(vi) Br

(vii) Cl

(viii) Br

(ix) Br
Haloalkanes and Haloarenes 237

4. Compare the rate of reaction for S N 2 / S N1 reactions.

Compare rate Compare rate

[Link]. Compound
of S 2 of S 1
N N

1. (a) (b)

2. (a) (b)

3. (a) (b)

4.
(a) (b)

5.
(a) (b)

6. (a) (b)

7. (a) (b)

8.
(a) (b)

9.
(a) (b)
10. (a) CH3 – O – CH2 – Br (b) CH3 – CH2 – CH2 – Br

11. (a) (b)

12. (a) (b)

238 Elementary Organic Chemistry for Medical

5. Identify the missing structure in each reaction ?

[Link].
Cl

15%NaOH
1. 160ºC

NO2

Cl
O 2N NO2
H2O
2. (A) acid

NO2

Br
NO2 s
CH3O
3.

NO2

Br
NO2
s
4. CH3O

Br
Br
NO2 s
CH3—CH2—NH2 HO
5. (A) (B)

NO2

F OH
s s
HO HO
6. (A)
Stable
intermediate
NO2 NO2
Haloalkanes and Haloarenes 239

F
KOH/ D
7.
NO2

NO2

KOH/ D
8.
Br
Br
CH3

KNH2
9. (A)
liq.NH3
(major)
Cl
OCH3
Cl
10. KNH2
(B)
liq.NH3 (major)

6. Identify major product and type of reaction (S N1 S N 2 E 1 E 2 ).

[Link]. Reaction SN1 / SN2 / E1 / E2

1. Cl

[Link]

2. NaNH2

Br

3. sr
t-BuOK

Br

4. CH2–Cl
s
CHO3
240 Elementary Organic Chemistry for Medical

[Link]. Reaction SN1 / SN2 / E1 / E2

5. CH3
NaI
H Cl
acetone

Et

Cl
H D KSH
6. D
H
CH3

Cl s
7. Ph–S
D

Br

8. KCN

Br

r
NMe3

9. s
EtO
D

10. s
EtO
D

H2 O
11.
Br
Haloalkanes and Haloarenes 241

[Link]. Reaction SN1 / SN2 / E1 / E2

Br

12.
H2O

Br
13. EtOH
D

EtOH
14.
D

EtOH
D
15. Br
s
EtO
D

Br
NaI
16. acetone

Br

Br

17. NaI
acetone

Br

18. [Link]
 242 Elementary Organic Chemistry for Medical

[Link]. Reaction SN1 / SN2 / E1 / E2

Br

19. [Link]

Ph
H2 O
20. Ph – C – Et
Br

H2SO4
21. OH D

H2SO4
22. D
OH

CH2–OH
PBr3
23. Pyridine

7. This questions gives you an idea about mono and dihalogenated products of an reactant.
Number of monochloro
Number of monochloro
[Link]. Compound product (excluding
product
stereoisomers)

1.

2.

3.

4.

5.

6.

7.
Haloalkanes and Haloarenes 243

8.

9. CH2

8. Identify monochlorination products (including stereo) :

1. CH 3 CH 2 CH 3 Cl2 / h n
¾¾ ¾¾® 2 Cl 2 / h n
¾¾ ¾¾®
CH 3 CH 2 CH 2 CH 3

3. Cl 2 / h n
¾¾ ¾¾® 4. Cl 2 / h n
¾¾ ¾¾®

5. 6. Cl 2 / h n
¾¾ ¾¾®
Cl2 / h n
¾¾ ¾¾®

7. Cl 2 / h n 8. Cl 2 / h n
¾¾ ¾¾® ¾¾ ¾¾®

9. Cl 2 / h n
¾¾ ¾¾®
10.

Cl2 / h n
¾¾ ¾¾®
244 Elementary Organic Chemistry for Medical

A nswers

1.
Br Br Br
Br Br
(A) (B) (C) (D) (E) (F)

OH MgBr
O OH
Br OH OH
(G) (H) (I) —C—OEt (J) —C—Ph (K)

Ph

CH3 OH CH3 OH O
(L) (M) (N) (O) (P) MgBr

D
O
OD
(Q) (R) 2MeMgBr (S) (T) D Cl
O—Me

O
COOEt
(U) D D (V) (W) CH2—C—OH
COOEt

O O

(X) CH2—C—Cl (Y) CH2—C—NH2 (Z) CH2—NH2+CO2

2.

[Link]. SN1 SN2 No reaction [Link]. SN1 SN2 No reaction

1. ✓ 2. ✓

3. ✓ 4. ✓

5. ✓ 6. ✓

7. ✓ 8. ✓

9. ✓ 10. ✓
Haloalkanes and Haloarenes 245

[Link]. SN1 SN2 No reaction [Link]. SN1 SN2 No reaction

11. ✓ 12. ✓
13. ✓ 14. ✓
15. ✓ 16. ✓
17. ✓ 18. ✓
19. ✓ 20. ✓
21. ✓ 22. ✓
23. ✓ 24. ✓
25. ✓

3.
(i) S N1 ® 3 ; E 1 ® 2 + 1 (ii) S N1 ® 1; E 1 ® 2 (iii) S N1 ® 3 ; E 1 ® 3
(iv) S N1 ® 2 ; E 1 ® 3 (v) S N1 ® 4 ; E 1 ® 3 (vi) S N1 ® 4 ; E 1 ® 7
(vii) S N1 ® 2 ; E 1 ® 4 (viii) S N1 ® 1; E 1 ® 2 (ix) S N1 ® 2 ; E 1 ® 5
4.
1. a > b; a > b 2. a > b; b > a 3. b > a; b > a 4. a > b; b > a
5. a > b; a > b 6. a > b; a > b 7. a > b; a > b 8. b > a; b > a
9. a > b; b > a 10. a > b; a > b 11. b > a; b > a 12. b > a; b > a
5.
OH
OH OCH3 OCH3
O2N NO2
NO2 NO2
1. 2. 3. 4.
NO2
NO2 NO2 Br
(picric acid)

NH2–CH2–CH3 NH–CH2 –CH3 F OH

NO2 NO2 OH
5. A = ,B= 6. 7.
NO2
NO2 NO2 N
O O

NO2 CH3 OCH3

8. 9. 10.
Br NH2 NH2
OH
246 Elementary Organic Chemistry for Medical

6.

, (E2) , (E 2 ) , (E2)
1. 2. 3.

Me
OCH3
4. , (SN2) 5. I H , (SN2)

Et

SH S–Ph

D H
6. 7. , SN2
H D , (SN2)

CH3

CN

, (E2) , (E2)
8. , (SN2) 9. 10.
Br
HO

OH
11. , (SN1) 12. , (SN1) 13. (E1)

,
14. 15.
(E1) (E1) (E2 )
I OH
, (E2) , (SN2) , (SN2)
16. 17. 18.

Ph OH
, (E2)
19. 20. 21. , (E1)
Ph , (SN1)

, (E 1 ) Br
22. 23. , (SN2)
Haloalkanes and Haloarenes 247

7.
1. 4, 3 2. 3, 2 3. 6, 4 4. 10, 6
5. 6, 4 6. 1, 1 7. 1, 1 8. 1, 1
9. 2, 2

8.
1. 2 2. 3 3. 4
4. 8 5. 4 6. 2
7. 5 8. 3 9. 1
10. 5
 248 Elementary Organic Chemistry for Medical

Level-3 Assertion and Reason

Instructions : In each of the following questions, a Statement of Assertion (A) is given followed by
a corresponding Reason (R) just below it. Read the Statement carefully and mark the correct
answer—
(A) If both Assertion and Reason are true and Reason is the correct explanation of Assertion.
(B) If both Assertion and Reason are true but Reason is not the correct explanation of
Assertion.
(C) If Assertion is true but Reason is false.
(D) If both Assertion and Reason are false.

1. Assertion (A) : Alkyl halides undergo nucleophilic substitution reactions.

Reason (R) : Polarity of C - X bond creates positively charged carbon for nucleophile to
attack.
2. Assertion (A) : The order of reactivity of alkyl halide in S N 1 mechanism is
Alkyl > Benzyl > Tertiary > Secondary > Primary > Methyl.
Reason (R) : Order is as per stability of carbocation.
3. Assertion (A) : Aryl halides do not undergo nucleophilic substitution reaction like alkyl
halide.
Reason (R) : Carbon and halogen in an aryl halide has double bond character.
4. Assertion (A) : The carbon-halogen bond in an aryl halide is shorter than the
carbon-halogen bond in an alkyl halide.
Reason (R) : A bond formed of an sp 3 orbital should be shorter than the corresponding
bond involving an sp 2 orbital.
5. Assertion (A) : Chloroform is stored in dark colour bottles. It oxidises to phosgene in
presence of O 2 and sunlight.
Reason (R) : It oxidises to phosgene in presence of O 2 and sunlight.
6. Assertion (A) : Haloalkanes are reactive than chlorobenzene.
Reason (R) : The C-atom of C ¾ Cl in chlorobenzene is sp 2 hybridised.
7. Assertion (A) :
Iodination of alkanes is carried out by heat in presence of reducing agent.
Reason (R) :
Iodination of alkanes takes place explosively.
8. Assertion (A) :
Vinylic halides are reactive towards nucleophilic substitution reactions.
Reason (R) :
Reactivity is due to the polarity of carbon-halogen bond.
9. Assertion (A) :
Primary benzylic halides are more reactive than primary alkyl halides
towards S N 1 reactions.
Reason (R) : Reactivity depends upon the nature of the nucleophile and the solvent.
10. Assertion (A) : Styrene on reaction with HBr gives 1-bromo-1-phenyl-ethane.
Reason (R) : Benzyl radical is more stable than alkyl radical.
Haloalkanes and Haloarenes 249

11. Assertion (A) : 2-Bromobutane on reaction with sodium ethoxide in ethanol gives
1-butene as a major product.
Reason (R) : 1-Butene is more stable than 2-butene.
12. Assertion (A) : Rate of hydrolysis of methyl chloride to methanol is higher in DMF than in
water.
Reason (R) : Hydrolysis of methyl chloride follows second order kinetics.
13. Assertion (A) : The presence of nitro group faciliates nucleophilic substitution reactions
is aryl halides.
Reason (R) : The intermediate carbanion is stabilized due to presence of nitro group.
14. Assertion (A) : 2-Bromo butane on reaction with alcoholic KOH gives 2-butene.
Reason (R) : The hydrogen on C 3 carbon is more acidic than hydrogen on C 1 carbon.
15. Assertion (A) : Toluene in presence of UV rays forms benzaldehyde.
Reason (R) : Dichlorotoluene is formed as an intermediate.
CH 3 CH 3
| |
16. Assertion (A) : CH 3 ¾ C ¾ CH 2 ¾ Br + NaOH ¾ ¾® CH 3 ¾ C ¾ CH 2 ¾ OH
| |
CH 3 CH 3
Reason (R) : It follows with formation of more stable carbocation.
17. Assertion (A) : Chlorobenzene is less reactive than benzene for electrophilic substitution
reaction.
Reason (R) : Resonance effect in chlorobenzene destabilized carboaction intermediate.
18. Assertion (A) : In m-nitrochlorobenzene and p-nitrochlorobenzene,
m-chloronitrobenzene is more reactive towards aqueous KOH.
Reason (R) : Carbanion is more stable in m-nitrochlorobenzene.

Cl
|
19. Assertion (A) : CH 3 ¾ CH ¾ CH ¾ CH 3 ¾[Link]/ D
¾¾¾ ¾® CH 3 ¾ C == CH ¾ CH 3 + CH 3
| |
CH 3 CH 3
(Major)

¾ C== H ¾ CH == CH 2
|
CH3

Reason (R) : In E 2 reaction product formation always takes place by saytzeff rule.
 250 Elementary Organic Chemistry for Medical

A nswers

1. (A) 2. (A) 3. (A) 4. (A) 5. (A) 6. (B) 7. (D) 8. (D) 9. (B) 10. (B)
11. (D) 12. (B) 13. (A) 14. (C) 15. (D) 16. (D) 17. (C) 18. (D) 19. (C)

S olutions

1. (A)
d+ d- -
R ®¾ X + Y ® RY + X -
2. (A)
+
Cl Cl
-
3. (A) O

6. (B) C-atom of chlorobenzene is sp 2 hybridised and is more electronegative than C-atom of

haloalkanes which is sp 3 hybridised. Thus, more electronegative C-atom will have less
tendency to release electrons to halogen atom (Cl) and hence C¾Cl bond will be less
polar than that in haloalkanes. Hence, chlorobenzene is less reactive than haloalkanes.
7. (D) Iodination reaction takes place by simple heating the alkane and iodine in presence of
oxidising agent like HNO 3 or HIO 4 .
8. (D) Vinylic halides are unreactive towards nucleophilic substitution reactions because of
mesomeric effect. Mesomerism gives rise to partial double bond character to the
carbon-halogen bond making it stronger and therefore more difficult to cleave than a
C sp 3 - X bond. It also reduces the polarity of the carbon-halogen bond thereby making
heterolysis difficult.
– +
CH2 == CH- X CH2- CH == X
Haloalkanes and Haloarenes 251

9. (B) Backside attack due to bulky phenyl group is not possible for S N 2 mechanism.
17. (C) Ref. NCERT-XII th /Part II / Page No. 305
Because of its [Cl] - l effect has some tendency to withdraw electrons from the ring. As a
result, the ring gets somewhat deactivated as compare to benzene ring and hence
electrophilic substitution reactions is chlorobenzene occur slowly.
Cl Cl

18. (D)
NO2
NO2
Aq. KOH Aq. KOH

Cl OH Cl OH Cl OH
- -

NO2 -

NO2 NO2
*More stable intermediate
*Fast reaction