252 Elementary Organic Chemistry for Medical

4
Alcohols, Phenols and Ethers

Level-1

[A] Alcohols

4.1 INTRODUCTION, CLASSIFICATION, NOMENCLATURE AND STRUCTURE OF

FUNCTIONAL GROUP
1. Which of the following is a secondary alcohol?
OH
H
(a) OH (b) (c) OH (d) CH 3 OH
CH CH3
3

2. Which of the following is an allylic alcohol?

(a) CH 2 == CHCH 2 OCH 3 (b) CH 2 == CHCH 2 CH 3
(c) HOCH == CHCH 2 CH 3 (d) CH 3 CH == CHCH 2 OH
3. Identify which of the compound having 2° alcohol ?

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

OH OH
4. Identify 2° alcohol in the given following alcohols:
OH OH
(a) HO (b) (c) (d)
5. Which of the following is polyhydric alcohol ?
(a) CH 3 CHOHCH 2 OH (b) CH 3 CHOHCHOHCH 2 OH
(c) CH 2 OHCH 2 OH (d) C 6 H 5 CHOHCH 3
Alcohols, Phenols and Ethers 253

6. Which of the following is /are 1º alcohol?

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

7. Which of the following is sec-butyl alcohol?

(a) CH 3 CH 2 CH 2 CH 2 OH (b) CH 3 CH(OH)CH 2 CH 3
(c) (CH 3 ) 2 CHCH 2 OH (d) (CH 3 ) 2 CHOH
8. The isomeric alcohol which has a chiral carbon atom is:
(a) n-butyl alcohol (b) iso-butyl alcohol (c) sec-butyl alcohol (d) tert-butyl alcohol
9. Which of the following gem diols is stable ?
OH OH OH OH
| | | |
(a) H 3 C — C — H (b) Br 3 C — C — H (c) F3 C — C — H (d) H 5 C 6 — C — C 6 H 5
| | | |
OH OH OH OH
10. Arrange the stability of given diols in decreasing order :
OH
OH OH
OH
OH OH
I II III
(a) III > I > II (b) III > II > I (c) I > III > II (d) I > II > III
OH +
11. + H +
H
(A) ; OH ¾¾® (B) ; H
OH ¾¾®
¾¾®
D
D
D
(C)

Sum of a-hydrogens in A+B+C is :

(a) 17 (b) 18 (c) 19 (d) 20
OH
OH
+ +
12. H H (B) ;
¾¾® (A) Major ; ¾¾®
D
D

Sum of a-hydrogens in A + B is :
(a) 18 (b) 19 (c) 20 (d) 21
OH
OH
+ +
13. H H
¾¾®
D
(A) ; ¾¾®
D
(B) ; Sum of a-hydrogens in A + B is :

(a) 15 (b) 16 (c) 17 (d) 18

14. OH H+ H
+
¾¾® (A) ; ¾¾®
D
(B)
D
OH
Sum of a-hydrogens in A+B is :
(a) 12 (b) 13 (c) 14 (d) 15
 254 Elementary Organic Chemistry for Medical

OH OH
+ +
H +
¾¾® (A) ; H
¾¾® (B) ; H ; Al2O3
15. D D ¾¾® (C) ¾¾® (D)
D D
OH
OH
Sum of a-hydrogens in A+B+C+D is :
(a) 34 (b) 35 (c) 36 (d) 37

4.2 METHODS OF PREPARATION

16. Alkene can be converted into alcohol by which reaction ?
(a) Displacement reaction (b) Elimination reaction
(c) Addition reaction (d) Reduction reaction
17. Which of the following combinations can be used for the preparation of cis vic diol ?
(a) Alkene, Baeyer reagent (b) Alkene, OsO 4
Å
(c) Alkene, MMPP and H 2 O/H (d) Both of (a) and (b)
18. How many compounds with molecular formula C 5 H 10 O may be reduced with NaBH 4 to a
primary alcohol?
(a) 2 (b) 3 (c) 4 (d) 5
19. Which of the following reagents converts alkene into alcohol ?
s
(a) HOH/H 2 SO 4 (b) (i) BH 3 (ii) H 2 O 2 /OH
(c) (i) Hg(OAc ) 2 (ii) H 2 O 2 /NaBH 4 (d) All of these
210°C
20. glycerol + oxalic acid ¾¾® [ X ] ; Product [ X ] is :
O
CH2OC == O
CH2OCCOOH
(a) HCOOH (b) allyl alcohol (c) (d) CH O C == O
CHOH
CH2OH
CH2OH
21. What are the major products of the following reaction?
O
OH
1. LiAlH4, Et2O
¾¾¾¾¾¾® ?
2. H2O, H2SO4
O
O OH OH
OH
(a) + enantiomer (b) OH + OH

OH OH OH OH
OH OH OH OH
(c) + (d) +
O O
Alcohols, Phenols and Ethers 255

22. What is the product of the following reaction?

1. B H , THF
2 6
¾¾¾¾¾¾® ?
2. NaOH, H O
2 2

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

23. Which of the following compounds gives 3-methyl-2-butanol upon reduction with LiAlH 4 ?
H O

O O O O
a b c d
(a) a (b) b (c) c (d) d
24. Conversion of isobutene into isobutyl alcohol can be possible with :
s
(a) HOH/H Å (b) BH 3 followed by H 2 O 2 /OH
(c) conc. H 2 SO 4 followed by HOH (d) All of these
(i) CH3MgBr
25. CH3 — CH — CH2 ¾¾¾¾® r [P]
; Product [P ] is :
(ii) HOH/H
O
(a) CH 3 — CH — CH 2 OH (b) CH 3 — CH — CH 2 — CH 3
| |
CH 3 OH
OH
|
(c) CH 3 — C — CH 3 (d) CH 3 — CH == CH 2
|
CH 3
26. Which of the following compounds gives vic diol with Na/C 2 H 5 OH ?
O
||
(a) RCHO (b) R — C — R (c) C 6 H 5 CHO (d) C 6 H 5 COC 6 H 5
27. Propanal can be converted into 1-propanol by :
s s
(a) KMnO 4 /H Å /D (b) KMnO 4 /OH/D (c) NH 2 NH 2 /OH/D (d) NaBH 4
28. Which of the following combinations will give trans vic diol ?
s
(a) Alkene, KMnO 4 / OH/HOH (b) Alkene, OsO 4 , NaHSO 3
(c) Alkene, MMPP, H 2 O/H Å (d) Alkene, I 2 /CH 3 COOAg (wet)
256 Elementary Organic Chemistry for Medical
O
CH3CHCH3 Mg, ether H2C——CH2 H O+
3
29. ¾¾¾¾® ¾¾¾¾¾® ¾¾® ; Major product is :
Cl
(a) (CH 3 ) 2 CHCH 2 CH 2 OH (b) (CH 3 ) 2 CHCHOHCH 3
(c) CH 3 CH 2 CH 2 CH 2 CH 2 OH (d) CH 3 CH 2 CH 2 CHOHCH 3
30. Which of the following reactions can be used to prepare 3-methyl-3-hexanol,
OH
|
CH 3 CH 2 CCH 2 CH 2 CH 3 ?
|
CH 3
O O
|| ||
1. CH MgBr 1. CH CH 2MgBr
(a) CH 3 CH 2 CCH 2 CH 2 CH 3 ¾ ¾ ¾3¾¾® (b) CH 3 CCH 2 CH 2 CH 3 ¾ ¾ ¾3¾ ¾ ¾®
2. H 3Or 2. H 3Or
O
||
1. CH CH 2CH 2MgBr
(c) CH 3 CCH 2 CH 3 ¾ ¾ ¾3¾ ¾ ¾¾ ¾® (d) (a) and (b) (e) (a), (b) and (c)
2. H 3Or

31. Which of the following products is formed in good yield by the reduction of methyl
4-oxohexanoate (M) with LiAlH 4 in ether?
O
O

O M
(a) 6-Methoxy-3-hexanone (b) 1,4-Hexanediol
(c) Methyl 4-hydroxyhexanoate (d) 4-Hydroxyhexanal
[ A]
32. H 2 C == CH — CHO ¾® H 2 C == CH — CH 2 OH ; Here [ A] is :
(a) H 2 /Ni/D (b) Pt/H 2
(c) NaBH 4 (d) H 2 /Wilkinson catalyst
2 SeO
4 LiAlH
33. CH 3 — C ºº C — CH 3 ¾¾® ( A) ¾¾® ( B ) ; Here ( B ) will be :
(a) Vic diol (b) Pinacolone (c) Oxirane (d) Oxitane
34. Predict the product of the following reaction. CH 3 COOH + NaBH 4 ¾®
(a) CH 3 CHO (b) CH 3 CH 2 OH (c) CH 3 CH 3 (d) no reaction
35. Which of the following compounds does not give a tertiary alcohol upon reaction with
methylmagnesium bromide?
(a) 3-methylpentanal (b) ethyl benzoate
(c) 4,4-dimethylcyclohexanone (d) 4-heptanone
O O
|| ||
( i ) CH 3 MgBr ( excess)
36. C 6 H 5 — C — C — C 6 H 5 ¾¾¾¾¾¾¾¾® Å
Product is :
( ii ) HOH / H
Alcohols, Phenols and Ethers 257

OH OH OH O
| | | ||
(a) C 6 H 5 C — CC 6 H 5 (b) C 6 H 5 C — C C 6 H 5
| | |
CH 3CH CH 3
3
(c) C 6 H 5 COOH (d) C 6 H 5 CHOHCHOHC 6 H 5
[ A]
37. C 6 H 5 — CH == CH — CHO ¾® C 6 H 5 — CH 2 — CH 2 — CH 2 OH ; Here [ A] is :
(a) LiAlH 4 (b) NaBH 4
(c) aluminium isopropoxide (d) All of these
38. Tertiary alcohol can be prepared from :
(a) Ketone and NaBH 4 (b) Aldehyde and RMgX
(c) RCOOC 2 H 5 and RMgX (d) HCOOC 2 H 5 and RMgX
39. What is the major product of the following reaction?
4 2 NaBH , H O
O ¾¾¾¾¾¾® ?

(a) O (b) OH
+ enantiomer
O

(c) OH (d) None of these

40. Which of the following compounds gives a secondary alcohol upon reaction with
methylmagnesium bromide? Assume the usual acid workup.
(a) butyl formate (b) 3-pentanone (c) pentanal (d) methyl butanoate
41. Which of the following amines will give primary alcohol with NaNO 2 /conc. HCl ?
CH 3
|
(a) CH 3 — CH 2 — CH — NH 2 (b) CH 3 — C — NH 2
| |
CH 3 CH 3
(c) CH 3 — CH — CH 2 — CH 2 — NH 2 (d) All of these
|
CH 3
42. What are the major products of the following reaction?
1. EtMgBr, Et O
2
O ¾¾¾¾¾¾® + ?
2. H O, H O
2 3

Optically active
Et Et OH Et
(a) + (b) +
OH OH Et OH
 258 Elementary Organic Chemistry for Medical

OH Et OEt
(c) + (d) +
Et OH OEt
43. Which of the following compounds would not give tert-butyl alcohol when treated with excess
methylmagnesium bromide?
(a) acetyl chloride (b) acetaldehyde (c) methyl acetate (d) acetic anhydride
44. Consider the following reaction :
NH 2 OH
| |
NaNO 2 / conc. HCl
CH 3 — CH — CH 3 ¾¾¾¾¾¾® CH 3 — CH — CH 3 + some minor byproduct
Minor byproduct is :
(a) 2-chloro propane (b) propene (c) isopropyl nitrite (d) all of these
45. Which of the following reagents, when treated with phenylmagnesium bromide followed by
acid workup, will yield 2-phenylethanol?
(a) Ethanol (b) Oxirane (c) Acetaldehyde (d) Ethylene
O
CH3 ||
( i ) H 2O, Hg (O C CH 3 )2
46. ¾ ¾ ¾ ¾ ¾ ¾ ¾¾® ; Major product of the reaction is :
CH2 ( ii ) NaBD 4
H
| OD OH OH
(a) CH 3 — C — OD (b) (c) (d)
CH2D CH2D CH3
|
CH 3
2 Moist Ag O
47. CH 3 — CH 2 — Br ¾¾¾¾® [P ] ; Product [P ] is :
(a) ethanol (b) diethyl ether (c) propane (d) propyne

4.3 [A] PHYSICAL PROPERTIES

48. Arrange the compounds in the order of increasing boiling point (lowest first) :
O OH SH
(I) (II) H 2 O (III) (IV)
(a) II, I, III, IV (b) I, IV, II, III (c) IV, I, III, II (d) I, IV, III, II
49. Which of the compounds listed below would you expect to have the highest boiling point ?
(They all have approximately the same molecular weight.)
(a) CH 3 CH 2 CH 2 CH 2 CH 3 (b) CH 3 CH 2 CH 2 CH 2 OH
(c) CH 3 CH 2 CH 2 OCH 3 (d) CH 3 CH 2 CH 2 Cl
50. Arrange the compounds in the order of increasing solubility in water (least soluble first).
OH OH
(I) (II)
OH
(III) HO (IV) OH

(a) I, III, II, IV (b) III, I, IV, II (c) I, IV, II, III (d) IV, I, III, II
Alcohols, Phenols and Ethers 259

51. Which compound would have the highest boiling point ?

O O O
(a) (b)

OH
O O OH
(c) (d)

OH
52. Among the following which has highest boiling point ?
(a) Butan-1-ol (b) Butan-2-ol
(c) Propan-1-ol (d) Pentan-1-ol
53. Among the following which has highest boiling point ?
(a) Ethoxyethane (b) Pentanal
(c) Pentanol (d) n-hexane

4.3 [B] CHEMICAL PROPERTIES

54. Which of the following statements is correct for the given reaction ?
Xs
s
R — OH ¾¾® R — X + OH
s s
(a) Reaction will not take place because OH is poor leaving group; X s is weak base and OH is
strong base.
-
(b) Reaction will not take place because OH is poor leaving group and X s is strong base.
-
(c) Reaction will take place because OH is poor leaving group and X s is weak base whereas
s
OH is strong base.
s
(d) Reaction will take place because OH is good leaving group, X s is weak base and OH is
strong base.
55. What is the product of the following reaction?
OH
SOCl2
¾¾¾¾® ?
Pyridine

Cl Cl
(a) + enantiomer (b) Cl

Cl
(c) + (d) optically active
260 Elementary Organic Chemistry for Medical

56. Which alcohol derivative is most reactive for S N reaction ?

O
||
(a) R — Br (b) R — O — C — CH 3
O O
||
(c) R — O — S — CF3 (d) R — O — S — — CH3
||
O O
57. In the given reaction :
(i) TsCl/Py
H3C OH ¾ ¾¾¾¾¾® [P]
(ii) CH —CH SNa
3 2

[P ] is :

(a) H3C S — CH2 — CH3 (b) H3C S — CH2 — CH3

(c) H3C — O — CH2 — CH3 (d) H3C S — CH2 — CH3

58. Which of the following metals is most reactive with alcohol ?

(a) Al (b) Zn (c) Hg (d) Fe
59. Which of the following compounds is not oxidized by pyridinium chlorochromate (PCC)?
(a) 2-methyl-2-butanol(b) 1-pentanol (c) 2-pentanol (d) 1,3-propanediol
60. The alcohol refusing to generate a carbonyl compound on oxidation with acidified KMnO 4 is:
OH CH3
(a) (b) OH
CH3 OH
OH
CH3
(c) (d) OH
OH

61. The order of reactivity of methyl alcohol (I), isopropyl alcohol (II), tertiary butyl alcohol (III)
and ethyl alcohol (IV) for esterification in decreasing order will be :
(a) I > II > III > IV (b) IV > III > II > I (c) I > IV > II > III (d) I > IV > III > II
62. Which among the following alcohols is most reactive with sodium wire ?
(a) Ethanol (b) 2-propanol (c) 2-Butanol (d) 2-Methyl-2-butanol
63. Which of the following compounds will form ester with alcohol ?
(a) Nitric acid (b) Sulphuric acid (c) Phosphoric acid (d) All of these
64. Best method to convert alcohol to halide is:
(a) ROH + SOCl 2 ¾® R — Cl + SO 2 + HCl (b) R — OH + PCl 3 ¾® R — Cl
(c) R — OH + PCl 5 ¾® R — Cl (d) R — OH + HCl ¾® R — Cl + H 2 O
Alcohols, Phenols and Ethers 261

65. Which among the following compounds is most acidic in character ?

OH
|
(a) HOH (b) CH 3 — OH (c) CH 3 — CH 2 — OH (d) CH 3 CCH 3
|
CH 3
66. The given reaction is an example of reaction :
Br
|
HBr
CH 3 — CH == CH — CH 2 OH ¾¾® CH 3 — CH — CH == CH 2
(a) S N 1 (b) S N 1¢ (c) S N 2 (d) E 1

67. Which of the following molecules is cleaved by HIO 4 ?

OH
(a) CH 3 CHOHCH 2 CHOHCH 2 OH (b)
OH
O OH
C==O
(c) (d) All of these
HO
OH
KMnO 4
68. ¾¾¾¾®
Cold
?; Product of the reaction is/are :
NaOH, H2O

OH H
+ Enantiomer + Enantiomer
(a) (b)
OH OH
H HO
+ Enantiomer + Enantiomer
(c) (d)
HO OH OH
69. Consider the following reaction :
O O
|| Å ||
H
CH 3 — CH 2 — O — H + CH 3 — C — OH ¾® CH 3 — CH 2 — O — C — CH 2 — CH 3 + HOH
(A) (B)
In the above reaction, ester formation takes place by :
(a) breaking of O — H bond of ( A) and O — H bond of ( B )
(b) breaking of C — O bond of ( A) and C — O bond of ( B )
(c) breaking of O — H bond of ( A) and C — O bond of ( B )
(d) breaking of C — O bond of ( A) and O — H bond of ( B )
262 Elementary Organic Chemistry for Medical

70. In which of the reaction CH 4 formation takes place ?

(a) CH 3 MgBr + Ph — CH == O (b) CH 3 MgBr + CH 3 — CH == O
O
||
(c) CH 3 MgBr + CH 3 — C — CH 3 (d) CH 3 MgBr + EtOH
71. For the given reaction,
O
||
(CH 3CO )2O / Py
R — O — H ¾¾¾¾¾® R — O — C — CH 3
which alcohol will be most reactive ?
(a) CH 3 OH (b) Primary alcohol
(c) Secondary alcohol (d) Tertiary alcohol
72. Which of the following reagents can be used to oxidize 1° alcohols to aldehydes ?
(a) KMnO 4 (b) MnO 2
(c) K 2 Cr 2 O 7 (d) H 2 O 2 (e) PCC
73. In the chromic acid oxidation of alcohols, the chromium is:
(a) reduced from Cr 6+ to Cr 3+ (b) reduced from Cr 3+ to Cr 6+
(c) oxidized from Cr 3+ to Cr 6+ (d) none of the above
OH

[O], H CrO
74. ¾ ¾ ¾2 ¾¾4® P , Major product P is :
CH3
(optically active)

(a) a ketone which is meso and optically inactive

(b) an optically active ketone
(c) a racemic mixture of ketones which is optically inactive
(d) an aldehyde which is meso and optically active
(e) an acyclic carboxylic acid
s
Nr
CrO3Cl
|
OH H
75. Br ¾¾¾¾¾® (A) ; product A is :

(a) Br COOH (b) Br CHO

H N—CrO3Cl–
Br
(c) (d)
Alcohols, Phenols and Ethers 263

H
|
SOCl 2 / Pyridne
76. C 3 H 7 — C — OH ¾¾¾¾¾® [P ] ; Product [P ] is :
|
CH 3
H H
| |
(a) C 3 H 7 — C — Cl (b) Cl — C — C 3 H 7
| |
CH 3 CH 3
Cl
|
(c) Mixture of (a) and (b) (d) CH 3 — CH 2 — C — CH 3
|
CH 3
77. Which of the following esters is used as substitute of alcohol for S N reaction ?
O
||
(a) R — O — C — CH 3 (b) R — O — N == O (c) R — O — Ts (d) All of these
78. Which of the following compounds undergoes periodate oxidation ?
O

O OCH3 O
(a) (b)
HO
OH
OH
OH

(c) CHOHCHOHCH3 (d) All of these

2 SOCl
79. CH 3 — CH 2 — CHOH — CH 3 ¾¾®
ether
CH 3 — CH 2 — CHCl — CH 3

This reaction will take place with :

(a) inversion (b) retention (c) racemisation (d) epimerisation
80. Which of the following alcohols will be oxidised by Br 2 /KOH ?
OH
(a) CH 3 OH (b) CH — CH3

CH3
(c) CH2OH (d)
OH
PBr Alc. KOH HBr NH
¾3® (A) ¾ ¾ ¾¾® (B) ¾ ¾® (C) ¾ ¾
81. CH 3 CH 2 CH 2 OH ¾ ¾ ¾3® (D), (D) is:
(a) CH 3 — CH 2 — CH — NH 2 (b) CH 3 — CH — CH 3
|
NH 2
264 Elementary Organic Chemistry for Medical

H CH 3
| |
(c) CH 3 — C — NH 2 (d) CH 3 — C — NH 2
| |
CH 3 CH 3
82. Which of the following alcohols is oxidized to a ketone by chromic acid ?
OH OH
(a) (b)
CH3
CH2OH CH2OH C— CH3
(c) (d) (e)
OH

83. When vapour of alcohol is passed over Ag powder at 300°C, the product is isobutene. Alcohol
in this reaction will be :
OH OH
| |
(a) CH 3 CH 2 CH CH 3 (b) CH 3 CH 2 CCH 3
|
CH 3
OH OH
CH3 |
(c) CH CCH3 (d) CH 3 — C — CH 3
CH3 |
CH3 CH 3
OH
CrO , HCl, pyridine
84. OH 3
¾¾¾¾¾¾¾¾® ? Major product is :

O O
OH

(a) O (b) OH

O
OH

(c) OH (d) O

OH 1. PBr3
2. CH3COONa
85. ¾¾¾¾¾® ? Major product formed in the synthesis is :
CH COOH
3
OCOCH3
(a) O (b)

Br
(c) (d) +
Alcohols, Phenols and Ethers 265

OH CrO /H SO NaCN /HCl

86. ¾ ¾ 3¾ ¾¾
2 4
¾® Major product is :
® ¾¾¾¾

O O O OH
CN
NC Cl
(a) (b) (c) (d)
CN
OH
CH2CH3
TsCl Cl–
87. CH3 OH product of the reaction is :
H
CH2CH3 CH2CH3 CH2CH3 CH2CH3
(a) CH3 Cl (b) CH3 OTs (c) Cl CH3 (d) TsO CH3
H H H H
CH3
Conc. H SO
2 4
88. In the given reaction CH3 ¾ ¾ ¾ ¾¾ ® A ; Product A is:
OH OH

CH3 CH3
(a) (b)
O CH3 CH3
CH3
CH3
(c) (d) CH3
COOCH3 O
OH
ether
89. ¾® ; Product/s of the reaction is/are :
+ CH 3 CH 2 MgBr ¾ ¾

OMgBr
(a) (b) + OH
CH2CH3

OMgBr O
(c) + CH 3 CH 3 (d)

CH 3
|
heat
90. CH 3 — C —— CHCH 3 + HBr ¾ ¾
¾® ; Major product of the reaction is :
| |
CH 3 OH
266 Elementary Organic Chemistry for Medical

CH 3 Br CH 3 CH 3 CH 3
| | | | |
(a) CH 3 C — CHCH 3 (b) CH 3 CCH 2 CH 2 (c) CH 3 C CHCH 3 (d) CH 3 CCH 2 CH 3
| | | || |
CH 3 CH 3 Br BrCH 3 CH 2 Br
CH3
91. CH3 + HBr ? Major product of the reaction is :
OH
CH3 CH3 CH3
CH3
CH3 Br CH2Br CH3
(a) (b) (c) (d)
Br CH3

Br
92. What reagents are needed to accomplish the following transformation?
O O
OH ? O
¾¾¾®
O O
(a) KMnO 4 , NaOH , H 2 O , heat (b) 1. LiAlH 4 , Et 2 O ; 2. 2H 2 O , H 2 SO 4
(c) CrO 3 , HCl, pyridine (d) H 2 CrO 4 , acetone, 35°C
93. Alcohol can be dehydrated by :
(a) (CH 3 CO) 2 O (b) (CH 3 ) 2 SO 4 (c) HI/P (d) Anhy. ZnCl 2 /D
94. Which one of the following will most readily be dehydrated in acidic medium ?
O OH
|| |
(a) CH 3 — C — CH 2 — CHOH — CH 3 (b) CH 3 — CH — CH 2 — CH 2 — CH 3
O O
|| ||
(c) CH 3 — C — CHOH — CH 2 — CH 3 (d)CH 3 — C — CH 2 — CH 2 — CHOH — CH 3
95. Which is not a likely product formed when the following alcohol is treated with sulfuric acid?

OH

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

OH
H SO
2 4 cold. KMnO
96. ¾ ¾¾ ®( A) ¾ ¾ ¾ ¾¾4®( B ). Product ( B ) is:
D

(a) diastereomer (b) meso (c) racemic (d) geometrical isomer

Alcohols, Phenols and Ethers 267
r
H
97. (A) ¾¾® ; Structure of (A) is:
D

(a) (b) (c) OH (d) All of these

OH OH
r
H
98. (A) ¾¾®
D ; Structure of (A) is:

(a) (b) (c) (d) All of these

OH OH OH
CH2—OH r
H
99. ¾¾® (A) ; Product (A) is:
D

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

CH2—OH
H+
100. ¾ ¾® (A) ; Product (A) is:
D

CH3

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

101. Which of the following is most reactive toward the acid-catalyst dehydration?
OH OH
OH OH

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

102. Which of the following alcohols is least reactive toward acid-catalyst dehydration?
OH OH OH
OH

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

OH

Hr
103. ¾¾®( A) ; Product (A) is:
D

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

 268 Elementary Organic Chemistry for Medical

Hr
104. ¾¾®( A); Product (A) is:
D
HO

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

105. In which of the following reaction pair of diastereomers will form ?

+
OH + ¾¾®H
(a) (b) H (c) D (d) All of these
OH ¾¾® D OH
106. In which of the reaction rearrangement take place with change in carbon skeleton ?
CH3
+ +
H H
(a) CH3—C—CH—CH3 ¾¾® (b) OH ¾¾®
D
D
CH3 OH
+
H
OH ¾¾®
(c) D (d) All of these

OH

(A)
107. ¾¾® ; Reagent (A) is :

r s s
(a) H 3 O (b) H + D (c) HO (d) NH 2
108. Which of the following alcohols dehydrates with the fastest rate?
OH
(a) CH3 OH (b)

OH

(c) OH (d) (e) OH

109. Which of the following alcohols gives a rearranged carbocation when dehydrated?

(I) CH 3 CHCH 3 (II) CH 3 CHCH 2 CH 3

| |
OH OH
CH3
CH 3
OH OH |
(III) (IV) (V) H 3 C — C — OH
|
CH 3

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

Alcohols, Phenols and Ethers 269

CH3 OH
H2SO4
110. heat
? Major product of the reaction is :

CH3 CH3 CH2 CH3 CH3

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

OH

H SO
2 4 NBS LiAlD
111. ¾ ¾¾ ¾® (B) ¾ ¾¾4® (C); Product (C) is:
® (A) ¾ ¾
D OH

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

OH
H+
112. ¾¾® major product of the reaction is:
D

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

OH
H+
113. ¾¾® major product of the reaction is:
CH2
O

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

CH2 CH2
CH3

Reference for Q. 114 to 116

Compound ( A) tertiary alcohol when it reacts with conc. H 2 SO 4 gives alkene
( B). B on O 3 Zn followed by reaction with dil. KOH and heating gives (C ). (C ) on
reaction with NaOH followed by acidification gives D.
O
C—OH
D=

114. Compound A is:

OH OH
OH

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

 270 Elementary Organic Chemistry for Medical

115. Compound B is:

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

116. Compound C is:

O O O
CH3
(a) (b) (c) CH3 (d)
CHC3

Reference for Q. 117 to 119

A tertiary alcohol ( A) C 7 H 14 O on reaction with conc. H 2 SO 4 gives ( B) C 7 H 12 .
( B) on ozonolysis give (C ) C 7 H 12 O 2 . (C ) gives both Haloform and Tollen’s
reagent test. When (C ) reacts with sodium methoxide gives ( D ) C 7 H 10 O. ( D ) on
OH

reaction with H 2 Ni give ( E ) . ( E ) on reaction with conc. H 2 SO 4 gives

( A).
117. Structure of ( A) is:
OH
OH OH OH

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

118. Structure of ( B ) is:

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

119. Which statement is true about D ?

(a) Formed from Cannizaro reaction (b) Formed from Perkin reaction
(c) Formed from cross Aldol reaction (d) Formed from intramolecular Aldol reaction

Reference for Q. 120 to 122

A tertiary alcohol ( A) on acid catalysed dehydration gives ( B). Which on
ozonolysis gives (C ) and ( D ). C upon reaction with KOH gives ( E ). D upon
reaction with SeO 2 followed by reaction with conc. KOH and acidification give
( F ).
Structure of ( E ) and ( F ) are , and Ph — CH — C — OH
| ||
O OH O
respectively.
Alcohols, Phenols and Ethers 271

120. Compound ( A) is obtained by:

O
O
|| CH3 + PhMgBr
(a) MgBr + Ph — C — CH 3 ¾® (b)
O

(c) CH 3 MgBr + Ph (d) All of these

121. Structure of ( B ) is:

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

122. Structures of (C ) and ( D) are respectively:

O O O
||
(a) , Ph — CHO (b) , Ph — C — CH 3

(c) , Ph — CH 2 — CHO (d) All of these

 272 Elementary Organic Chemistry for Medical

[B] Phenols

4.4. GENERAL INTRODUCTION

123. Simplest phenol is also known as :
(a) hydroxy benzene (b) carbolic acid
(c) both (a) or (b) (d) none of these
124. Which of the following is enolic group ?
| |
(a) — C — OH (b) == C — OH
|
| |
(c) ºº C — OH (d) C — C — O — C
125. Which of the following belongs to phenols ?
(a) C 6 H 5 OH (b) C 6 H 4 (OH) 2
(c) C 6 H 4 OH(CH 3 ) (d) All of these
126. Nature of C — OH bond in phenols is :
(a) C sp 3 — OH (b) C sp 2 — OH
(c) both (a) and (b) (d) none of these

4.5 METHODS OF PREPARATION

127. PhMgBr + (x) ¾¾® ; ( x) is:

CH 3
| O
(a) CH 4 (b) CH 3 — C — OH (c) (d) ether
|
CH 3
OH
|
128. The product CH 3 — C — Ph is obtained in the reaction. (Assume acidification at the end of the
|
Ph
reaction)
O O
|| ||
(a) CH 3 MgBr + Ph — C — Ph (b) PhMgBr + CH 3 —C — Ph
O
||
(c) 2PhMgBr + CH 3 — C — O — Et (d) All of these
Alcohols, Phenols and Ethers 273

129. Substrate in Dow’s process for the manufacture of phenol is :

(a) chlorobenzene (b) benzenediazonium chloride
(c) benzenesulphonic acid (d) cumene
130. Which catalyst is used for oxidation of toluene into ?
(a) H 2 O / H + (b) CuCl 2 / FeCl 3
(c) CuCl 2 / MnCl 2 (d) Either of these
131. Which of the following reaction involves the conversion of chlorobenzene into phenol ?
(a) Dow’s process (b) Raschig’s process
(c) Both (a) and (b) (d) Neither (a) nor (b)
132. Benzenediazonium chloride may be converted into phenol by action of :
(a) H 2 O ( v ) (b) NaNO 2 / HCl
(c) H 3 PO 2 (d) either of these
CH3

133. 2O /MnCl +CuCl

2 2
¾¾¾¾¾¾¾® P, product P is :
D
CH2OH OH CHO COOH

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

OH OH
COOH
A , A is :
134. ¾¾¾¾®

(a) Heat/H 2 O (b) NaOH / CaO

(c) KOH / CuCl 2 (d) none of these
O H O/H+
135. C 6 H 4 (CH 3 ) 2 ¾¾2® A ¾ ¾
2
¾¾® C 6 H 5 OH; A may be :
CH 3
OCH 3 |
(a) C 6 H 4 ƒ (b) C 6 H 5 C — CH 3
‚ OCH 3
|
O — OH
OCH 3
(c) C 6 H 4 ƒ (d) none of these
‚ CH 3

4.6 PHYSICAL AND CHEMICAL PROPERTIES

136. Phenol can be converted into anisole by :
(a) CH 2 N 2 /ether (b) (CH 3 ) 2 SO 4 /NaOH
(c) CH 3 I (d) All of these
 274 Elementary Organic Chemistry for Medical

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

OH
FeBr3
+Br2 ¾¾¾® ?
CH3
OH
OH
(a) CH3 (b)
ClCH2
Br

OCl Br
OH
(c) (d) (e)
CH3 CH3
CH3 Br
138. Phenolphthalein is obtained by condensation between :
(a) phenol and succinic acid (b) phenol and phthalic anhydride
(c) phenol and succinic anhydride (d) phenol and benzaldehyde
139. Which of the following compound will not undergo Reimer-Tiemann reaction?
NO2 CHO

(a) (b) (c) (d) All of these

140. K a value of phenol is more than that of ethanol because :

(a) phenoxide ion is stronger base than ethoxide ion.
(b) phenoxide is more stable than ethoxide ion due to resonance.
(c) phenoxide is less stable than ethoxide ion.
(d) phenoxide ion is bulkier than ethoxide ion.
141. Compare the rate of acid catalyst dehydration:
OH OH
OH

I II III
(a) I > II > III (b) II > III > I (c) III > II > I (d) II > I > III
142. Phenol on reaction with benzenediazonium chloride in basic medium gives :
(a) Diphenyl ether (b) p-Hydroxyazobenzene
(c) Chlorobenzene (d) Benzene
143. Most reactive toward (acid catalyst dehydration) is:
OH OH
OH
(a) (b) (c) (d)
OH
Alcohols, Phenols and Ethers 275

144. Phenol is least reactive for aromatic nucleophilic substitution because :

(a) carbon-oxygen bond has some double bond character due to resonance.
(b) oxygen is present on sp 2 -hybrid carbon which makes carbon-oxygen bond stronger.
(c) oxygen is highly electronegative which decreases bond length between carbon and
oxygen.
(d) all are correct.
CH3
Na 3 CH I
145. H O—H ¾¾®( A) ¾ ¾
¾ ® ( B ), Product ( B ) is:
SN 2
Ph
CH3 CH3 Ph Ph
(a) H Ph (b) H OCH3 (c) H OCH3 (d) CH3O H

OCH3 Ph CH3 CH3

146. Electrophile in Reimer-Tiemann reaction is:
s
(a) CCl 3 (b) CH 2 Cl 2 (c) CHCl 3 (d) :CCl 2
OH O
s
K S O /OH
147. ¾2¾¾
2 8
¾®

O
The given reaction is known as :
(a) Elbe oxidation (b) Elbe reduction
(c) Houben-Hoesch reaction (d) Air oxidation
148. Phenol can be distinguished from alcohol by which reagent :
(a) Na (b) Alcoholic FeCl 3 (c) Br 2 /HOH (d) NaOH
Ph CH3
+
H
149. Ph—C—C—CH3 ¾¾®
D
(A) ; Product (A) is :
OH OH
Ph O CH3 O O CH3
(a) Ph—C—C—CH3 (b) CH3—C—C—Ph (c) Ph—C—C—CH3 (d)

CH3 CH3 Ph
2 4H SO ( i ) NaOH fusion
150. C 6 H 5 — OH ¾¾®
110°C
[P ] ¾¾¾¾¾¾®
Å
[Q ] ; Product [Q ] is :
as major product ( ii ) H
OH OH OH OH
SO3H OH
(a) (b) (c) (d)

SO3H OH
 276 Elementary Organic Chemistry for Medical

151. In Reimer-Tiemann reaction molecular weight of phenol increases by:

(a) 28 (b) 29 (c) 30 (d) 31
152. Which of the following is the best method for preparing aspirin ?
COOH
O
?
OCCH3
O OCCH3
COOH
(a) + HO—C—CH3 ¾¾® (b) + HCOOH ¾¾®
O

COOH O
COOH r
(c) O + CH3Cl ¾¾® (d) H
+ CH3—C—NH2 ¾¾®
OCCl OH
O O
COOH
Hr
(e) + CH3C—O—CCH3 ¾¾®
OH
OH
OMe
(i) KOH, CHCl
153. ¾ ¾ ¾ ¾ ¾¾3® ‘P’ ; Major product of the reaction is :
(ii) H 3Or
OH
O OH OMe
(a) OMe (b) H
H
O
OH
OH O
OMe
(c) (d) H

H O OMe
154. Phenol reacts with benzenediazonium cation at pH 7.5 to give :
(a) aniline (b) Chlorobenzene (c) benzene (d) azo dye
OH

155. ¾ ( A) ; Product (A) is :

+ CHCl 3 + NaOH ¾®
2Hr

CH3
OH OH OH OH OH

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

CO2H
CH3 CH3 CH3 CH3
Alcohols, Phenols and Ethers 277

OH
O O
|| ||
NaOH CH 3 —C — O —C — CH 3
156. ¾®( B) ; Product (A) and (B) respectively are:
+ CO 2 ¾ ¾¾®( A) ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾
r
2H
OH OH O O OH OH O
CO2H CO2H
C—O—C—CH3 H
(a) ; (b) ;

O
OH O—C—CH3 OH OH O
CO2H CO2H CHO
; ; O—C—CH3
(c) (d)

HO O
+
157. O H
¾¾® P ; Product (P) of the reaction is :
D

O HO O HO OH OH
(a) O (b) (c) (d)

158. Phenol is a colourless liquid. On keeping for long time, it converts into brown colour due to :
(a) air oxidation into p-benzoquinone (b) air oxidation into quinol
(c) air oxidation into o-benzoquinone (d) air oxidation into m-benzoquinone
159. Which of the following phenols is soluble in NaHCO 3 ?
(a) 2,4,6-Trinitrophenol (b) 4-Nitrophenol
(c) 2-Nitrophenol (d) All of these
OH O O
|| ||
(1) CO ,NaOH
2 CH 3 — C —O— C —CH 3
160. ¾¾¾¾ ¾¾®( A) ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾®( B ); Aspirin Product ( B ) is:
(2) Hr
O
O
OH O—C—Me OMe OH
CHO COOH COOH C—OCH3
(a) (b) (c) (d)

OH OH
CHO
(i) CHCl /alc. KOH
3
161. ¾¾¾¾¾¾®
r
(ii) H

In the given reaction, intermediate species is :

Å ·· · s
(a) CHCl 2 (b) CCl 2 (c) CHCl 2 (d) CHCl 2
 278 Elementary Organic Chemistry for Medical

162. Which of the following compound gives Reimer-Tiemann reaction ?

NO2 OH NO2
OMe
(a) (b) (c) (d)

NO2
OH

163. ¾ (A) ; Product (A) is:

+ CHCl 3 + NaOH ¾®

OH OH OH OH
CHO
CO2H
(a) (b) (c) (d)
CHO
CO2H
OH HI
164. ¾¾® ' P ' ; Major product ' P ' is:
¾excess
OH

I
OH I I I
(a) (b) (c) (d)
I I OH OH

Reference for Q. 165 to 167

An alcohol P, which gives positive iodoform test, undergoes reaction with 2
moles of PCC (pyridinium chloro chromate) gives compound Q. Compound Q
on reaction with dil. KOH followed by heating gives compound R. Ozonolysis of
R leads to a tricarbonyl compound S, which on reaction with LiAlH 4 gives
compound T the structure of compound T will be
CH2—OH
CH2—OH

O
2 moles of PCC (i)OHs (i) O LiAlH
P ¾¾¾¾¾¾ ¾® R ¾ ¾¾3® S ¾ ¾ ¾
¾® Q ¾ ¾ ¾ ¾4® T
(ii)D (ii) Zn,H 2O

165. The structure of the carbonyl compound Q is :

O O O O

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

OH O O O
Alcohols, Phenols and Ethers 279

166. The structure of the carbonyl compound R is :

OH
(a) (b) (c) (d)
OH
O O O O
167. The structure of the carbonyl compound S is :
O O O O

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

CHO
O O
O O O
 280 Elementary Organic Chemistry for Medical

[C] Ethers

4.7 GENERAL INTRODUCTION AND METHODS OF PREPARATION

168. Which of the following pairs will give ether ?
Å
H
(a) C 2 H 5 ONa and C 2 H 5 I (b) CH 3 — CH 2 — OH ¾¾®
140ºC

2Dry Ag O
(c) CH 3 — CH 2 — I ¾¾¾® (d) All of these

169. In the given reaction, alcohol used is :

conc. H SO
2 4
R — OH + ROH ¾ ¾ ¾ ¾¾ ® R — OR + HOH
D

(a) primary alcohol (b) secondary alcohol (c) tertiary alcohol (d) all of these
NaOH
170. Br — CH 2 — (CH 2 ) 3 — CH 2 — OH ¾¾¾¾¾® [P ] ; Product [P ] is :
Toluene 140°C

OH
|
(a) CH 2 — (CH 2 ) 4 — CH 2 OH (b) H 2 C == CH — (CH 2 ) 3 — CH 2 OH
OH
| O
(c) CH 3 — CH —(CH 2 ) 3 — CH 2 OH (d)

171. The substances used for the preparation of ether by Williamson’s synthesis are:
(a) (CH 3 ) 3 C Br and CH 3 O Na (b) (CH 3 ) 3 C Br and CH 3 OH
(c) CH 3 Br and (CH 3 ) 3 CONa (d) CH 3 Br and (CH 3 ) 3 COH
172. In the given reaction, [P ] is :
O
OH
Dry HCl
+ CH3 — C — CH3 ¾¾¾® [P]
OH
OH

O — C — CH3
O CH3
(a) (b) C
CH3 O CH3
OH
Cl
(c) (d) O
Cl
173. In Williamson’s ether synthesis, alkyl halide is :
(a) primary (b) secondary (c) tertiary (d) all of these
Alcohols, Phenols and Ethers 281

174. In the given reaction product [P ] is :

H3C (i) Hg(OAc)2/CH3OH
C==CH — CH2 ¾¾¾¾¾¾¾®
(ii) NaBH4
[P]
H3C
OCH 3 OCH 3
| |
(a) H 3 C — C — CH 2 — CH 3 (b) H 3 C — CH — CH — CH 3
| |
CH 3 CH 3
OH OH
| |
(c) H 3 C — C — CH 2 — CH 3 (d) H 3 C — C — CH 2 — CH 3
| |
CH 3 CH 3
175. The best method for synthesis of given ether by Williamson’s ether synthesis is:
—O—CH == CH2

s s
(a) —O + H2 C== CH—Br (b) —O + H2 C== CH—Br

s s
(c) —Br + H2 C== CH—O (d) —+ H2 C== CH—O

Br

176. Sodium tertiary butoxide always gives which type of reaction with alkyl halides except with
CH 3 X ?
(a) Elimination (b) S N 1 reaction (c) S N 2 reaction (d) Reduction

4.8 PHYSICAL AND CHEMICAL PROPERTIES

1. KMnO4, cold HO HO
H2O, NaOH
177. A ¾¾¾¾¾¾®
2. NaH, DMF O + O , A is :

Br

(a) (b) Br

Br

(c) Br (d)

178. Ether gives chemical reactions due to :

(a) C — O bond cleavage (b) C — H bond cleavage
(c) lone pairs present on oxygen (d) all of these
 282 Elementary Organic Chemistry for Medical

179. In the given reaction,

HCl / D
CH 3 — CH 2 — CH 2 — O — CH 2 — CH 3 ¾¾¾® [P ] + [Q ]
[P ] and [Q ] will respectively be :
(a) CH 3 — CH 2 — CH 2 OH and CH 3 — CH 2 — Cl
(b) CH 3 — CH 2 — CH 2 — Cl and CH 2 — CH 2 — OH
(c) CH 3 — CH 2 — CH 2 — Cl and H 2 C == CH 2
(d) CH 3 — CH == CH 2 and H 2 C == CH 2
180. What are the major products from the following reaction?
O—CH2 HI
?
heat

I CH2OH OH CH2I
(I) + (II) +

OCH2OH I OCH2I OH
(III) + (IV) +

CH2OI OH
(V) +

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

r
H3O
181. ¾¾¾® ; Product of above reaction is:
O OEt

, EtOH , EtOH
(a) HO OH (b) HO O

, CH3OH + EtOH
(c) HO O (d) O O
Excess HI/ D
182. C 6 H 5 — O — CH 2 — CH 3 ¾¾¾¾® [P ] + [Q ]
In the given reaction, [P ] and [Q ] are respectively :
(a) C 6 H 5 I and CH 3 — CH 2 — I (b) C 6 H 5 — OH and CH 3 — CH 2 — I
(c) C 6 H 5 I and CH 3 — CH 2 OH (d) C 6 H 5 OH and H 2 C == CH 2
CH 3
|
Conc. H I
183. CH 3 — C — O — CH 3 ¾ ¾ ¾ ¾® ?, Reaction is an example of :
|
CH 3
(a) S N1 (b) S N 2 (c) SN - Ar (d) NGP
Alcohols, Phenols and Ethers 283

184. Give the expected major products of the following reaction.

O
HBr, H2O
¾¾¾¾®
heat

OH
(a) recovered starting material (no reaction) (b) Br

Br Br
(c) Br (d) HO

+
MeOH, H
185. O ¾¾¾¾¾® ? ; Major product of the reaction is :

Optically active
OH
(S) OMe (S) OMe (R)
(R) (S) (R) (R) (R) (S)
(a) (b) (c) (d) none
OH OMe OMe
OH 1. PCC
O 2. NH , pH = 4
3
186. ¾¾¾¾¾¾¾® ? ; Product of the synthesis is :

O NH H2N NH
(a) (b)

O OH O O

(c) O (d)
NH2 H2N
1. HNO3, H2SO4
2. Fe, HCl
3. NaOH
187. ¾¾¾¾¾¾¾® ? ; Product of the synthesis is :
4. HONO, ice bath
5. CuCl
O
Cl Cl Cl
Cl
(a) (b) (c) (d)
HO O O O
CH3
H3C s
CH3O/CH3OH
188. C — CH2 ¾¾¾¾¾® CH3 — C — CH2OCH3
H3C
O OH
The given reaction is an example of :
(a) S N 1 reaction (b) S N 2 reaction
(c) Unimolecular addition (d) Bimolecular addition
 284 Elementary Organic Chemistry for Medical

189. Compare reactivity towards Grignard reagent :

O O O
(a) (b) (c)
(a) c > b > a (b) b > c > a (c) a > b > c (d) none of these
H 3O r
190. O ¾ ¾¾ ® ; Product of this reaction is:

O OH O O
O O O
(a) (b) , CH 3 CHO (c) ,
, H, H(d)

O—CH3
Conc. HI
191. ¾ ¾ ¾¾® x mole of HI is consumed
sum of x + y is :
O—CH3
Conc. HI
¾ ¾ ¾¾® y mole of HI is consumed

(a) 2 (b) 3 (c) 4 (d) 5

O—CH3

Conc. HI
192. ¾¾¾® ; Products of given reaction is:
(excess)

O—CH3
I CH OH OH

(a) + 2CH3I (b) +2CH3OH (c) + 2CH3I (d) + 2CH3I

I OH OH I
193. Which of the following is correctly matched ?
CH 3
| r
HOH / H Å HOH/H
(a) CH 3 CH 2 O — C — CH 3 ¾¾¾¾® S N 1 (b) CH3 — CH — CH2 ¾¾¾® SN 2
|
CH 3 O
s
CH3O/CH3OH
(c) CH3 — CH — CH2 ¾¾¾¾¾® SN 2 (d) All are correct
O
O r
3 H O
194. ¾¾¾® ; Product obtained in this reaction is:
O O
(a) 2CH 3 CHO (b) 3HCHO (c) 3HCO 2 H (d) 3CH 3 OH
Alcohols, Phenols and Ethers 285

O O H O
r
3
195. ¾¾¾® ; Major product of this reaction is:

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

(c) O O O (d) HO O O

196. Formation of ether peroxide can be identified by :

(a) Fe 2+ and KCNS (b) KI and starch (c) both of (a) and (b) (d) hypo
r
O—Et H3O
197. ¾¾¾® ; Products obtained in this reaction are:

OH O O O

(a) EtOH, (b) , CH 3 CHO (c) CH 3 CO 2 H, (d) EtOH,

198. Which of the following is most reactive towards hydrolysis ?

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

O O O
HOs
199. CH 3 — O — CH 3 ¾ ¾
¾® ; Product of the reaction is:
H 2O

(a) no reaction (b) 2CH 3 OH (c) 2CH 4 (d) Et—H

18
Conc. HI
200. Ph — O— CH 3 ¾ ¾ ¾
¾® ; Product of the reaction is:
18 18
(a) Ph — O H, CH 3 I (b) Ph — I, CH 3 OH (c) Ph — I, CH 3 — I (d) Ph — OH, CH 3 I
CH3

201. O—C—CH3 , best combination to prepare it, is :

CH3
s
(a) O + Br (b) Br + Os

(c) Os + OH (d) Os + Os

x HI
202. CH3O O O OCH3 ¾ ¾® product/s, value of x is :

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

 286 Elementary Organic Chemistry for Medical

203. Compare rate of reaction with OH - :

(i) O (ii) O (iii)

O
(a) i>ii>iii (b) i>iii>ii (c) iii>ii>i (d) ii>i>iii
204. PhMgBr + Et — O — Et ¾®
¾ Product of the reaction is:
(diethyl ether)
(a)Ph — OEt (b) Ph — OH (c) Ph — Et (d) no reaction
O OH
205. +x CH3MgBr ¾¾® CH 3 — CH — CH 2 — CH 2 — CH 2 — CH 2 .
Hr | |
OH OH
The value of x is:
(a) 1 (b) 2 (c) 3 (d) 4
s
206. Compare rate of reaction with OH / H 2 O

O O O
(a) (b) (c)
(a) c > b > a (b) a > b > c (c) b > a > c (d) b > c > a
Conc. HI
207. CH 3 — CH 2 — O — CH 2 — CH 3 ¾ ¾ ¾
¾® Major product of the reaction is:
(excess)
(a) 2EtOH (b) 2EtI (c) EtOH, EtI (d) 2H 2 C == CH 2
208. What is the product of the following reaction sequence?
O
CH3MgBr H3O+
CººCH ? Product is :

(a) CººCH3 (b) CººCCH2CH2OCH3

(c) CººCCH2OCH2CH3 (d) CººCCH2CH2OH

(e) CººCCH2CH2CH2OH

O O
H Or
3
209. ¾¾® Product of the reaction is:
Alcohols, Phenols and Ethers 287

OH
OH
(a) (b) O (c) both (a) and (b) (d) no reaction

18
O—Ph
H Or
3
210. ¾¾¾® Products are:

18
OH OH
18
(a) (b) Ph — OH (c) Ph — OH (d) no reaction

211. In the given pairs, select the more reactive towards hydrolysis :
(1) Ph — O — Ph Ph — O — CH 3 (2) O O
( a) ( b)
(c) (d)

(a) 1 - a , 2 - c (b) 1 - b, 2 - c (c) 1 - b, 2 - d (d) 1 - a , 2 - d

Reference for Q. 212 to 214

A organic compound P on reaction with concentrated HI gives products Q and R. Both
compound Q and R gives alkene on reaction with respectively alcoholic KOH and
concentrated H 2 SO 4 (followed by heating).
conc. HI
P ¾¾¾® Q + R
¾¾®

¾¾®

alc. KOH H2SO4

D D

212. Structure of compound P will be:

(a) O (b) O

(c) O (d) O

213. Structure of compound Q will be:

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

214. Structure of compound R will be:

OH OH

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

 288 Elementary Organic Chemistry for Medical

215. 0.3150 g of organic compound having methoxy group has molecular weight 235. This
compound when treated with HI followed by AgNO 3 , gives 0.468 g of AgI. Percentage
methoxy group in the compound is :
(a) 19.6 (b) 29.6 (c) 1.96 (d) 40

A nswers

1. (b) 2. (d) 3. (b) 4. (b) 5. (b) 6. (d) 7. (b) 8. (c) 9. (c) 10. (d)
11. (c) 12. (c) 13. (b) 14. (c) 15. (b) 16. (c) 17. (d) 18. (c) 19. (d) 20. (b)
21. (d) 22. (b) 23. (b) 24. (b) 25. (b) 26. (c) 27. (d) 28. (c) 29. (a) 30. (e)
31. (b) 32. (c) 33. (a) 34. (d) 35. (a) 36. (a) 37. (a) 38. (c) 39. (b) 40. (c)
41. (c) 42. (a) 43. (b) 44. (d) 45. (b) 46. (c) 47. (a) 48. (d) 49. (b) 50. (c)
51. (d) 52. (d) 53. (c) 54. (a) 55. (d) 56. (c) 57. (b) 58. (a) 59. (a) 60. (c)
61. (c) 62. (a) 63. (d) 64. (a) 65. (b) 66. (b) 67. (d) 68. (d) 69. (c) 70. (d)
71. (a) 72. (e) 73. (a) 74. (b) 75. (b) 76. (b) 77. (c) 78. (d) 79. (b) 80. (b)
81. (b) 82. (b) 83. (d) 84. (d) 85. (b) 86. (d) 87. (c) 88. (d) 89. (c) 90. (c)
91. (b) 92. (d) 93. (a) 94. (a) 95. (a) 96. (b) 97. (d) 98. (b) 99. (b) 100. (b)
101. (c) 102. (b) 103. (a) 104. (b) 105. (a) 106. (a) 107. (b) 108. (c) 109. (d) 110. (b)
111. (c) 112. (b) 113. (c) 114. (b) 115. (a) 116. (a) 117. (b) 118. (b) 119. (c) 120. (b)
121. (b) 122. (b) 123. (c) 124. (b) 125. (d) 126. (b) 127. (b) 128. (d) 129. (a) 130. (c)
131. (c) 132. (a) 133. (b) 134. (b) 135. (b) 136. (d) 137. (e) 138. (b) 139. (d) 140. (b)
141. (b) 142. (b) 143. (c) 144. (d) 145. (b) 146. (d) 147. (a) 148. (b) 149. (a) 150. (c)
151. (a) 152. (e) 153. (c) 154. (d) 155. (a) 156. (c) 157. (d) 158. (a) 159. (a) 160. (b)
161. (b) 162. (c) 163. (a) 164. (b) 165. (b) 166. (c) 167. (a) 168. (d) 169. (a) 170. (d)
171. (c) 172. (b) 173. (a) 174. (a) 175. (c) 176. (a) 177. (b) 178. (d) 179. (a) 180. (b)
181. (b) 182. (b) 183. (a) 184. (b) 185. (a) 186. (a) 187. (c) 188. (b) 189. (c) 190. (b)
191. (b) 192. (c) 193. (d) 194. (b) 195. (b) 196. (c) 197. (d) 198. (b) 199. (a) 200. (a)
201. (b) 202. (b) 203. (a) 204. (d) 205. (a) 206. (b) 207. (b) 208. (d) 209. (c) 210. (a)
211. (c) 212. (a) 213. (d) 214. (c) 215. (a)
Alcohols, Phenols and Ethers 289

Level-2

1. Identify product, Intermediate & Type of reaction (Substitution, Elimination, Addition)

Type of reaction
S.No. Reaction Product Intermediate
(S/E/A)

M. A .
(i) ¾® (M. A .= mixed acid)
¾¾

(ii) Cl
¾¾¾®
AlCl3

r
N ºº NCls
(iii)
2 H O ( boil )
¾¾ ¾¾®

OH
(iv) CHCl
¾ ¾¾3®
KOH

OH

(v) (1) CO , NaOH

¾ ¾ ¾2¾Å¾
¾®
( 2) H

OH
Å
(vi) Ph — N ºº N
¾ ¾ ¾s¾
¾®
HO

OH

(vii) Br
¾¾2®
H 2O

+ Cl ¾AlCl
¾¾3®
(viii)

OH
(ix) H+
¾¾®
D
290 Elementary Organic Chemistry for Medical

2. This question gives you idea about solubility of compound is Na, NaOH, NaHCO 3 .
Evolve H2 gas React with aq. React with
S.No. Compound
with Na metal NaOH NaHCO 3

1. Ph — CO 2 H

2. Ph — OH

3. Ph — CH 2 — OH

4. Ph — CH 2 — CO 2 H

5. Ph — CH 2 — OCH 3

6. Ph — CH 2 — CH 2 — OH

7. Ph — SO 3 H
O
||
8. CH 3 — C — OH

9. CH 3 — CH 3
O
10. ||
CH 3 — C — O — CH 3

O
11. O

12. CH 3 — C ºº N

13. CH 3 — C ºº CH

14. HO NO2

O OH

15.
O OH
Alcohols, Phenols and Ethers 291

3.

S.No. Reaction Product

1. PhMgBr + 2-propanol

2. PhMgBr + Ph — CH 2 — OH

3. PhMgBr + CH 3 — SH

4. PhMgBr + CH 3 — C ºº CH ¾®

5. PhMgBr + Acetic acid

O
6.
PhMgBr + ¾®

O
7. ||
PhMgBr + Ph — C — Ph ¾®

PhMgBr + CHO ¾¾®

8.

O
9.
PhMgBr + ¾®

CHO
10. PhMgBr + ¾®

11. CH 3 MgBr + Butanone ¾®

12. CH 3 MgBr + 2-Pentanone ¾®

13. CH 3 MgBr + 3-Pentanone

4. Find the value of x in each reaction ?

OH
(a) x PhMgBr + SH (b) x PhMgBr + OH (c) x PhMgBr + CH=O
OH
NH2 H OH
OH H OH
CH2–CºCH OH HO H
CH2–O–CH3 CH2–OH

OH
292 Elementary Organic Chemistry for Medical

5. Identify product and compare rate of reaction ?

(a) O
CH3MgBr + CH3 – C – H r1
O
CH 3MgBr + Ph – C – H r2

CH 3MgBr + r3
O

(b) O
CH 3MgBr + H – C – H r1
O
CH 3MgBr + H r2

(c) CH=O
CH 3MgBr + r1

CH=O
CH3MgBr + r2
CH3O
CH=O
CH3MgBr + r3
NO2

(d) O
PhMgMgBr + r1
O
PhMgMgBr + r2

PhMgMgBr + r3
O

(e) O
PhMgBr + r1
P hM gB r + P h–C H = O r2

O
PhMgBr + r3
O

PhMgBr + r4
Alcohols, Phenols and Ethers 293

(f) PhMgBr + r3
O

PhMgBr + r3
O

PhMgBr + r3
O

6. Identify the product :

S.No. Reaction Product
O
||
1. PhMgBr + Ph — C — Cl ¾®
(excess)

O
||
2. PhMgBr + Ph — C — OEt ¾®
(excess)

O
||
3. PhMgBr + Ph — C — NH 2 ¾®
(excess)

O
||
4. PhMgBr + EtO — C — OEt ¾®
(excess)

O
||
5. PhMgBr + Et — S — C — Cl ¾®
(excess)

6. PhMgBr + Ph — C ºº N ¾®
(excess)

PhMgBr + Cl
7. (excess) ¾®

OH
8. PhMgBr + CH 3 — Cl ¾®
9. PhMgBr + Br — Br ¾®
294 Elementary Organic Chemistry for Medical

7. Propose the all suitable routes to prepare given alcohol by the help of grignard reagent ?
OH
OH

(a) Et (b) (c) CH3 CD3

OH
CT3

8. Find the value of x ? ( x = mole of RMgX consumed when following compounds reacts with it).
NH2
OCH3
OH
O O

OEt HS O
(a) (b)
Cl
Cl
O
O O–C–O–Ph
O O
9. Prepare the following by Friedal Craft reaction

CH3
1. 2. 3.

O
O

4. 5. Ph 6.
O

7. 8. 9.
O
O

Cl

10. 11. 12.

O
Alcohols, Phenols and Ethers 295

10. Provide necessary reagents in the following road-map :

Cl
/ AlCl3
O

(f)
Br2/Fe Cl2/Fe HNO3 + conc. (e)
H2SO4 H2SO4
(a) (b) (c) (d) CH2CH2CH3
(H2/Ni)

NBS hot KMnO4 (n)

or Br2/hn
(g) (h)
(m)
NH2 (k)
(i)
conc.
(j) H2SO 4/D
HOOC
(l) alc.
KOH (q)
N2Cl
CH=CHCH3
HBr/peroxide
(p)
HBr / CCl4

HBF4 CuCl HBr Kl CuCN H2O H3PO 2

/HCl / CuBr / boil
(t) (u) (v) (w) (x) (y) (z)

(s) NH2
296 Elementary Organic Chemistry for Medical

A nswers

1.
NO2 O
+
(i) , Carbocation, substitution (ii) , CH 3 — C == O , substitution

OH OH

CHO
(iii) , Carbocation, substitution (iv) , : CCl 2 , substitution
(ortho and para)
OH
CO2H
(v) , Carbocation, (vi) HO N==N , Carbanion,
(ortho and para)
substitution substitution

OH
Br Br
(vii) , Carbanion, (viii) , Carbocation, substitution
substitution
Br

(ix) , Carbocation, substitution

2.
Evolve H2 gas with Na metal React with aq. NaOH React with NaHCO 3

1. 3 3 3

2. 3 3 7

3. 3 7 7

4. 3 3 3

5. 7 7 7

6. 3 7 7

7. 3 3 3

8. 3 3 3
Alcohols, Phenols and Ethers 297

9. 7 7 7

10. 7 3 7

11. 7 3 3

12. 7 3 7

13. 3 7 7

14. 3 3 3

15. 3 3 3

3.

(1) (2) (3) (4) (5)

OH
OH Ph Ph OH
(6) (7) (8) (9)
Ph Ph Ph Ph

OH
OH CH3 OH
Ph
(10) (11) (12) (13) HO

4.
(a) x = 5 (b) 4 (c) 5
H OH
H OH H OH
5. (a) (b) CH 3 CH 2 OH , r1 > r2
Ph HO
r1 > r2 > r3
H OH

(c) r3 > r1 > r2

NO2

Ph
(d) r1 > r2 > r3
HO H HO Ph
298 Elementary Organic Chemistry for Medical

HO Ph

OH OH Ph
(e) r1 > r2 > r3 > r4
H Ph

OH
(f) Ph Ph OH No reaction r1 > r2 > r3

6.
OH Ph OH Ph O
(1) (2) (3) +
Ph Ph Ph Ph Ph Ph
OH Ph OH Ph O
(4) (5) (6)
Ph Ph Ph Ph Ph Ph

(7) (8) Ph — CH 3 (9) Ph — Br

MgBr MgBr
O
H3 O r
7. (a) (b)
O H3 O r

MgBr
EtMgBr
CHO
H Or
3 H3 O r
O
O MgBr

H3 O r

O O
CT3MgBr CD3MgBr
(c) CH CH3 ; CH3 CT3 ;
3 H Or3 H Or
3

O
CH3MgBr
CD3 CT3 H Or3
Alcohols, Phenols and Ethers 299

8. (a) 7 (b) 8
9.
Cl
AlCl3 AlCl3
1. + Cl 2. +

O
AlCl3 AlCl3
3. + CH3 – Cl 4. + CH3 – CH2 – C – Cl

O O
5. + Ph – C – Cl AlCl3 6. + C – Cl AlCl3

AlCl3 AlCl3
7. 8.
O
Cl Cl–C
||
O
Cl Cl
+ AlCl3
9. 10.

O
AlCl3
11. + Cl2 12. + AlCl
3

10.
Br Cl NO2 SO3 H
(a) ; (b) ; (c ) ; (d)

(e) CH 3 CH 2 CH 2 Cl FeCl 3 (f ) ; (g ) Sn / HCl

(1) Cl / AlCl
2 3
(h) CF3 CO 3 H ; (i) NaNO 2 / HCl / H 3 PO 2 ( j) ¾ ¾¾¾¾ ®
( 2) NaNH 2
300 Elementary Organic Chemistry for Medical

Br OH

(k ) ; (l) NaNO 2 / HCl ; (m) (n) hot KMnO 4

Br

(o) hot KMnO 4 ; ( p) (q ) Br ; (r ) OH

F Br
(s) LAH or H 2 Ni; (t ) (u) (v)

I CN OH
( w) ( x) (y) (z )
Alcohols, Phenols and Ethers 301

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) : The case of formation of alkoxide is primary alcohol>secondary alcohol

>tertiary alcohol.
Reason (R) : Tertiary carbanion is least stable.
2. Assertion (A) : Ether fire is difficult to extinguish with water.
Reason (R) : Ether fire is extinguished using pyrene (CCl 4 ) fire extinguishers.
3. Assertion (A) : Ethers can be cleaved by halogen acids.
Reason (R) : Reactivity order of HX is HCl>HBr>HI.
4. Assertion (A) : The tendency of alkyl halides to undergo dehydrohalogenation in
Williamson’s synthesis is tert>sec>prim.
Reason (R) : The order of stability of carbocation is prim<sec<tert.
5. Assertion (A) : Phenoxide ion (C 6 H 5 - O - ) is more reactive than phenol towards
electrophiles.
Reason (R) : Phenoxide ion is more stable than phenol.
6. Assertion (A) : Phenol is less acidic than p-nitrophenol.
Reason (R) : Phenolate ion is more stable than p-nitrophenolate ion.
7. Assertion (A) : Treatment of phenol with nitrous acid yield p-benzoquinone monoxime.
Reason (R) : p-nitrophenol and p-benzoquinone monoxime are tautomers.
8. Assertion (A) : Ethers are weakly polar.
Reason (R) : In ether, C ¾ O ¾ C bond angle is 180 o , which cancels bond dipoles.
9. Assertion (A) : Phenol reacts with chloroform and aqueous alkali followed by acid
hydrolysis to yield salicylaldehyde.
Reason (R) : It involves the formation of carbocations.
10. Assertion (A) : Aqueous solution of phenol is called as carbonic acid.
Reason (R) : Increasing order of acidity of phenols is
m-nitrophenol>o-nitrophenol>p-nitrophenol.
11. Assertion (A) : Dipole moment of phenol is found to be 1.54D.
Reason (R) : The dipole moment of phenol arises from the electron withdrawing effect
of phenyl group in contrast to the electron releasing effect of alkyl group
in alcohols.
12. Assertion (A) : Anhydrous CaCl 2 can be employed for drying ethanol.
 302 Elementary Organic Chemistry for Medical

Reason (R) : Sodium metal reacts with ethanol to form sodium ethoxide.
13. Assertion (A) : Ethanol is liquid but dimethyl ether is a gas.
Reason (R) : In ethanol, carbon as well as oxygen are sp 3 hybridised.
14. Assertion (A) : Tert-butyl alcohol undergoes acid catalysed dehydration readily than
propanol.
Reason (R) : Tertiary alcohol do not give Victor-Meyer’s test.
15. Assertion (A) : Tert-butanol undergoes esterification faster than methanol.
Reason (R) : The reaction between an acid and alcohol in presence of dry HCl gas to
give ester is known as esterification process.
16. Assertion (A) : Anisole undergoes electrophilic substitution at ortho and para positions.
Reason (R) : Anisole is less reactive than phenol towards electrophilic substitution
reactions.
17. Assertion (A) : Ethers can be dried by using sodium wire.
Reason (R) : Ethers do not react with sodium.
18. Assertion (A) : Phenetole on cleavage with HI yields phenol and ethyl iodide.
Reason (R) : Phenetole is a mixed aromatic ether.
19. Assertion (A) : 2-pentanol and 3-pentanol cannot be distinguished by iodoform test.
Reason (R) : 2-pentanol and 3-pentanol both are secondary alcohols.
20. Assertion (A) : Phenol is more reactive than benzene towards electrophilic substitution
reaction.
Reaction (R) : In case of phenol, the intermediate carbocation is more resonance
stabilised.
21. Assertion (A) : Methanol is stronger acid than water.
Reason (R) : Among monohydric aliphatic alcohols methanol is the strongest acid.
22. Assertion (A) : Ethers are not evaporated upto dryness.
Reason (R) : In dry ethers, peroxides are formed which may explode.
23. Assertion (A) : Mixture of ethyl alcohol and diethyl ether is called natalite.
Reason (R) : Natalite is used as substitute of petrol.
24. Assertion (A) : The major products formed by heating C 6 H 5 CH 2 OCH 3 with Hl are
C 6 H 5 CH 2 l and CH 3 OH.
Reason (R) : Benzyl cation is more stable than methyl cation.
25. Assertion (A) : Alcohols are dehydrated to hydrocarbons in the presence of acidic
zeolites.
Reason (R) : Zeolites are porous catalysts.
26. Assertion (A) : t-Butyl methyl ether is not prepared by the reaction of t-butyl bromide
with sodium methoxide.
Reason (R) : Sodium methoxide is a strong nucleophile.
27. Assertion (A) : t-butyl methyl ether is prepared by reaction of t-butyl bromide with
methoxide ion.
Reason (R) : Reaction follow S N 2-mechanism.

28. Assertion (A) : Rate of reaction of alkyl halide in williamson synthesis reaction is
1o RX > 2 o RX > 3 o RX.
Alcohols, Phenols and Ethers 303

Reason (R) : It is a type of bimolecular substitution reaction (S N 2 ).

29. Assertion (A) : Dehydration of alcohols always takes place in basic medium.
Reason (R) : OH - is a better leaving group.
30. Assertion (A) : p-nitrophenol gives more electrophilic substituted compound than
m-methoxy phenol.
Reason (R) : Methoxy group shows only negative I-effect.
31. Assertion (A) : Aryl sulphonic acid gives phenol on reacting with NaOH at high
temperature.
Reason (R) : This reaction is electrophilic substitution reaction.
32. Assertion (A) : Alcohols can react both as electrophiles and nucleophiles.
Reason (R) : Protonated alcohol is a good electrophile.
33. Assertion (A) : Benzyl phenyl ether forms phenol and benzyl iodide with Hl.
Reason (R) : Because benzyl carbocations is more stable than phenyl carbocation.
34. Assertion (A) : Catechol is less acidic than resorcinol.
Reason (R) : Hydroxy group shows only-I effect at m-position.
35. Assertion (A) : Ph - O - C 2 H 5 can be prepared form PhONa and ethyl iodide.
Reason (R) : Aryl halides are less reactive substrates for nucleophilic substitution
reaction.
36. Assertion (A) : m-Nitrophenol is less acidic than p-nitrophenol.
Reason (R) : p-Nitrophenol has intermolecular-H-bonding.
37. Assertion (A) : Benzene sulphonic acid on reaction with NaOH gives phenoxide.
Reason (R) : Sulphonic group is a good leaving group.
38. Assertion (A) : In Victor Meyer’s test secondary alcohol gives blue colour.
Reason (R) : Blue colour is due to alkaline solution of pseudonitrole.
39. Assertion (A) : The product of reaction of 2-Methyl cyclo hexanol with HBr at room
temperature is 1-Bromo-1-methyl cyclo hexane.
Reason (R) : Generally dehydration occur and product is 1-methyl cyclo hexene.
40. Assertion (A) : Compound CH 3 ¾ CH ¾ CH 2 ¾ OH does not give ether with conc.
|
H 2 SO 4 . CH
3

Reason (R) : It favours the formation of alkene over ether.

41. Assertion (A) : C 6 H 5 CH(OH)CH 3 gives benzoic acid with NaOBr followed by hydrolysis.
Reason (R) : First dehydration occur then oxidation.

A nswers
 304 Elementary Organic Chemistry for Medical

1. (B) 2. (B) 3. (C) 4. (A) 5. (B) 6. (C) 7. (A) 8. (C) 9. (C) 10. (D)
11. (B) 12. (D) 13. (B) 14. (D) 15. (D) 16. (B) 17. (A) 18. (B) 19. (C) 20. (C)
21. (D) 22. (A) 23. (B) 24. (A) 25. (B) 26. (B) 27. (D) 28. (A) 29. (D) 30. (D)
31. (C) 32. (B) 33. (A) 34. (A) 35. (A) 36. (B) 37. (A) 38. (B) 39. (C) 40. (A)
41. (C)

S olutions

1. (B) More stable is conjugate base more is the acidity.

Na
ROH ¾¾® RO - Na+H 2 ­
Hence, primary alcohols can form alkoxides with greater ease.
2. (B) Ether floats on water.
3. (C) The reactivity order is per hydrogen acid strength of HX.
HI > HBr > HCl.
4. (A)
5. (B) The resonance effect (+R) is more in phenoxide ion than phenol, due to extra pair of
electrons on oxygen for delocalisation. This makes benzene ring electron richer and
hence more suitable for electrophilic attack.
H

6. (C) Acidity depends upon stability of conjugate base. In case of o, p substituted phenols, the
conjugate base is more stabilised due to extended conjugation on nitro group along
with benzene ring. Hence, p-nitrophenolate ion is more stable (due to greater charge
dispersal) than phenolate ion.
7. (A)
8. (C)
9. (C) The reaction involves the formation of carbenes.
---
CHCl 3 + OH - ® H 2 O + :CCl 3 ®:CCl 2 + Cl -
Carbene
10. (D) Aqueous solution of phenol is known as carbolic acid. Electron withdrawing groups
such as bond ¾ NO 2 , ¾ CN, ¾ X increase the acidity of phenol. The increase is more
when electron withdrawing groups are at o-and p-positions than at m-position. i.e.,
p-nitrophenol>o-nitrophenol>m-nitrophenol.
Alcohols, Phenols and Ethers 305

11. (B) We know that the oxygen atom is more electronegative than both carbon and hydrogen.
The electrons of the C¾O and the O¾H bond are slightly displaced towards the
oxygen atoms. So, the electron density near the oxygen atom is slightly higher than that
near carbon and hydrogen atoms. Therefore, C¾O and O¾H bond in phenol is polar
and phenol possesses dipole moment.
12. (D) Ethanol has lone pairs and thus forms addition compound with CaCl 2 showing
solvation phenomenon.
CaCl 2 + 4C 2 H 5 OH ® CaCl 2 × 4C 2 H 5 OH + Solvated CaCl 2 (solid)
Therefore, alcohols cannot be dried by CaCl 2 . Quick lime is used.
13. (B) Ethyl alcohol can form extensively H-bonding and thus has higher boiling point.
H-bonding between molecules of dimethyl ether are not possible and only weak van der
Waals’ forces are present hence they exist as gas.
C 2H 5 ¾ O ¾ H - - - O ¾ C 2H 5
|
H
14. (D) Methyl alcohol cannot be prepared by the action of Grignard reagent on an aldehyde or
a ketone since the minimum number of carbon atoms in an aldehyde or a Grignard
reagent is one and hence the alcohol should contain at least two carbon atoms.
15. (D) When the size of the alkyl group in either acid or alcohol increases, the rate of the
esterification decreases. Since there is steric hindrance in (CH 3 ) 3 COH than in CH 3 OH,
it undergoes esterification slower than CH 3 OH.

16. (B)

Like phenol or phenoxide ion, the activation due to + R effect takes place at o-,
p-position.
17. (A)
18. (B) Stable carbocation is formed.
OH
|
19. (C) 2-pentanol contains CH 3 ¾ C ¾group which gives positive iodoform test like
O
||
CH 3 ¾ C ¾ group, hence this test distinguishes between the two given alcohols.
20. (C) This is due to + R effect of ¾OH group on benzene.
21. (D) Methanol is a weaker acid than water.

OH OH

36. (B)
NO2
NO2

m-Nitrophenol p-Nitrophenol
306 Elementary Organic Chemistry for Medical

*Only-I effect *-I and-M effect of

of NO 2 NO 2
CH3 CH3
OH +
HBr 2 carbocation
0

39. (C)
Rearrangement

H3C CH3
Br
+
Br -
3 carbocation
0

(i)NaOBr
41. (C) C 6 H 5 ¾ CH ¾ CH 3 ¾ ¾ ¾¾+® C 6 H 5 ¾ COOH + CHBr 3
| (ii)H 3O
OH
(Haloform reaction)