ALCOHOLS, PHENOLS & ETHERS

CaO  Ca
14. (c) Rectified spirit   absolute alcohol.
15. (a) Due to oxidation of ethyl alcohol to acetic acid
16. (b)
17. (c) CH 3 CH  CH 2  HCl  CH 3 CH (Cl )CH 3
The above product formation is based on
Markownikov’s rule.
CH 3 CH (Cl )CH 3  KOH 
1. (a) H2=CH-CH2- is an allyl group
CH 3 CH (OH )CH 3  KCl
18. (a) Diborane (BH3)2 reacts with alkenes to give trialkyl
2. (c) is glycerol boranes as addition product. This is oxidised to alcohol
by hydrogen peroxide in the presence of aqueous
sodium hydroxide.
3.(b) -OH group directly bonded to benzene ring is known
as Phenol.
4. (b)
5. (b) -OH group attached to primary carbon atom called
Primary alcohol.
6. (c)
19. (b)
7. (a) Oxirane is ethylene oxide,

H3O
RMgX  HCHO   RCH 2 OH (1 )  MgX (OH )
8. (a) IUPAC name of aromatic ethers: Alkoxy benzene 20. (a) aq. KOH and AgOH, both undergo SN reactions
Name of given compound is Ethoxy benzene with haloalkanes forms alcohols.
21. (c) C 6 H 5 CH 2 NH 2  HNO2  C 6 H 5 CH 2 OH  N 2  H 2 O
22. (a) Invertase: Sucrose to Glucose
Zymase: Glucose to Ethyl alcohol
9. (a) m-cresol H3O
23. (c) PhMgBr  CH 3COCH 2 CH 2 CH 3  


CH 3C (OH )( Ph)CH 2 CH 2 CH 3
10. (b) UPAC name of aliphatic ethers: Alkoxy alkane 24. (b) It is an example of nucleophilic substitution reaction
Name of the given compound: Ethoxy ethane (SN1 or SN2).
11. (c) CH3CH(Cl)CH2CH2CH(OH)CH3 25. (a)
6 5 4 3 2 1 26. (d)
-OH group is higher prior than -Cl group, so it gets Cl2
C6 H 5CH 3  Aq . NaOH
C6 H 5CH 2Cl   C6 H 5CH 2 OH
lowest possible number.
Name of the compound is 5-chlorohexan-2-ol
12. (c) IUPAC name of the given compound: Alkoxy alkane

13. (c) 27. (d)

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 ALCOHOLS, PHENOLS & ETHERS

28. (c) 41. (b)

CH 3 CH 2 MgBr+CH 3 CH 2 COCH 2 CH 3 

1 2
29. (d) 2-Phenylethanol, HO CH 2 CH 2 C 6 H 5 , is a 1
alcohol which can be prepared from C6H5MgBr by
treating with ethylene oxide (note that HCHO will
introduce only one carbon atom, i.e., it will give
C6 H5 CH 2 OH and not C6 H5 CH 2 CH 2 OH ).

42. (c) Alkanes are non polar in nature.

43. (a) Branching increases B.P. decreases
C6 H5 MgBr+HCHO  C6 H5 CH 2 OH . 44. (c) CaCl2 +3C 2 H5 OH  CaCl2 .3C2 H5 OH
B2 H6
  CH 3 CH 2 3 B
30. (a) 3CH 2 =CH 2  45. (c) Ethanol and water forms azeotropic mixture which

boils at constant temperature.
H 2 O2 /OH
  3CH 3 CH 2 OH 46. (d)
Hydroboration-oxidation of alkenes leads to hydration 47. (d) Alcohols are more acidic than hydrocarbons due
according to anti Markownikov’s rule. to more polar nature of -OH bond.
31. (a) Anti-Markovnikov’s hydration by hydroboraton- 48. (d)
oxidation of alkenes. 4 n
C2 H 5OH  Br2 
P 
 C2 H 5 Br  HBr
 2 6
i B H
CH 3 CH  CH 2   CH 3 CH 2 CH 2 OH
 ii  H O /OH
2 2 49. (d) 20  or  30 alcohols on oxidation give ketone.
Anti-Markovnikov’s product
Other three options will lead Markovnikov’s hydration, 50. (b) Addition reactions of C2 H 5OH
i.e. CH3CH = CH2  CH 3 CHOHCH3 . 51. (b) CH 3 OH + Na  CH3 ONa + 1/2 H 2
32. (c) C6 H 5 N 2 Cl + H 2 O  C6 H 5 OH + N 2 + H 2 O 1 Mole of Na i.e., 23 g produces 1/2 mole of H2
33. (b) Cumene i.e., C6 H5 CH(CH 3 ) 2 on oxidation gives
cumene hydroperoxide
34. (c) Cumene on aerial oxidation followed by hydrolysis
gives phenol and acetone. 52. (b)
35. (d)
NaOH/Δ
36. (a) C6 H 5 Cl 
pressure
 C6 H 5 OH
53. (c) A  CH 3OH , B  CH 3ONa, C  CH 3Cl
37. (c) In Williamson's synthesis alkyl halides combine
with sodium ethoxide form ethers. 54. (c) A  C2 H 5Cl , B  C2 H 5 ONO
38. (d) In Williamson’s synthesis, tertiary halides eliminate 55. (b) Acetaldehyde on reaction with Grignard reagent
preferably and in ethers containing tertiary alkyl group gives a secondary alcohol.
must be introduced through alkoxide. 56. (a) During esterification reaction, alcohol loses H+
39. (c) Chlorine atom in vinyl chloride is least reactive due which explains its acidic character. Stronger is the acid
to resonance. less tendency to undergo esterification. So, the order
is CH 3OH  CH 3CH 2 OH   CH 3 2 CHOH
57. (d) CH 3COOH ; C2 H 5OH
40. (b)
58. (d) H 3 PO3
59. (c) Distillation

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 ALCOHOLS, PHENOLS & ETHERS

60. (d) X: Acetone - (CH3)2CO 84. (c)

Y: Tert- butylalcohol - (CH3)3C-OH Cu
CH 3CH 2 CH 2 OH  Fehling
 CH 3CH 2 CHO  Cu 2 O 
Solution
 red 
61. (c) CH 3 CH(OH)CH 2 CH 3  CH 3 COCH 2 CH 3
Cu Fehling
Ethyl methyl ketone CH 3CHOHCH3  CH3COCH3  No reaction
Solution
62. (c) Four moles of bleaching powder needed in the 85. (c)
preparation of one mole of chloroform. PBr3
63. (d) The B.P. of ethyl alcohol is 78oC and has pleasant C2 H5 .CHOH.CH3   C2 H5  CH(Br)  CH3
odour smell. On heating with H2SO4 forms ethene, C2H4 Mg, ether
  C2 H5  CH(D)  CH3 .
D2 O
which decolourises bromine water and alkaline
86. (a)
KMnO4  
H
CH 3  CH  CH  CH 2 OH   CH 3  CH  CH  C H 2
64. (c) C2 H 5OH  4 I 2  CI 3CHO  5 HI
4( O3  2 KI  H 2 O  2 KOH  I 2  O2 )
65. (b) X= secondary alcohol ; Y= methyl ketone
66. (a) Victor Meyer's test is used to distinguish to 1o, 2o,
3o alcohols. Primary alcohol gives red colour.
Secondary alcohol gives blue colour.
67. (b) 1 : 1 87. (c)
68. (c) Correct order of dehydration in alcohols :
3o>2o>1o due to the stability of carbocation.
69. (a) Carbocation formed from alcohols during
dehydration.
70. (d) All the methods used to distinguish alcohols.
71. (c) Pyridinium chlorochromate, PCC is a mild oxidising
agent which is able to oxidise primary alcohols to
aldehyde.
72. (d)
73. (c) HCl + ZnCl2 is known as Lucas reagent.
Reactivity of alcohol towards Lucas reagent depends 88. (a) Aluminium isopropoxide is used as a reducing
upon stability of carbocation. More is the stability of agent, and aluminium tert-butoxide is used as an
the carbocation more is the reactivity of alcohols. oxidising agent.
74. (c) The reaction is acyl substitution of acid with 89. (a) EDG decreases acidic strength and +I.E. decreases
alcohol. with increase in distance.
90. (a) o- and p- nitrophenols are separated by steam
. distillation. o-isomer is steam volatile due to
intramolecular H-bonding while p-isomer is not
75. (a) Secondary alcohols give positive iodoform test. because of intermolecular H-bonding.
76. (b) Secondary alcohols give positive iodoform test. 91. (a) Phenol is weak acid than carbonic acid.
77. (a) NaH is most basic in character. 92. (b) This is Riemmer-Tiemann reaction.
78. (a) Ethanol is most acidic so easily combine with
metal wire
79. (a) SOCl2/Pyridine gives intramolecular SN reaction
i.e., SN1. During this reaction retention configuration
product is formed.
93. (b)
80. (c) Leaving power of O  SO 2  CF3 is maximum.
81. (b)
82. (a) Primary alcohol is most reactive for the reaction
due to breaking of O - H bond. 94. (b) 95. (c)
83. (d) Since carbocations are formed as intermediate, more 96. (b) Weak acid conjugate base is strong. ROH is the
stable the carbocation, higher will be reactivity of the weakest acid amongst them. Hence RO- is the strongest
parent compound (alcohol). 2-Methylpropan-2-ol base.
generates as carbocation, so it will react fastest ; other 97. (a) Since phenol is acidic in nature.
three generates either 1o or 2o carbocations. 98. (b) Due to EWG -NO2.

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 ALCOHOLS, PHENOLS & ETHERS

99. (b)

105. (a)

In the presence of non-polar solvent  CS2  , the

ionisation of phenol is suppressed. The ring is slightly
activated and hence monosubstitution occurs.

106. (d) -OH group is o- and p- directing group. But due

100. (c) to steric hinderance compound (b) formation is
unfavourable.
107. (b) H 2 O  CCl3  : CCl2  Cl 
101. (d) Relative basic character of their conjugated bases
108. (b)
which for H 2 O,C 2 H 2 ,H 2 CO3 and C 6 H 5 OH are 109. (b) Phenols are acidic in nature.

OH, HC  C: , HCO3 , C6 H 5 O  110. (d) Kolbe’s reaction
111. (a) Phenol required 3 moles of bromine.
More the possibility for the dispersal of the negative
112. (b) pKa of phenol is 10
charge, weaker will be the base. Thus the relative basic
Zn
character of the four bases is 113. (a) C6 H 5 OH 

 C6 H 6  ZnO
HCO 3  C6H 5O  
OH  HC  C 
Equivalent Non  equivalent Oxygen can accommodate
resonating structures
  charge easily

Due to resonance 114. (b) A is

Thus the acidic character of the four corresponding
acids will be
H 2 CO3  C6 H 5 OH>H 2 O>HC  CH .
102. (c) Due to greater electron-withdrawing effect of NO2,
and also due to additional resonance due to  NO 2
group in the phenoxide ion, nitrophenols are stronger
acids than chlorophenol. Further since resonance in
p-nitrophenoxide ion is more important than that in m-
nitrophenoxide ion, former is more stable, hence p-
nitrophenol is more acidic than m-nitrophenol. o-
Nitrophenol is less acidic than p-nitrophenol because
of intramolecular H-bonding.
103. (d) Sodium reacts with both phenol and ethyl alcohol
to evolve H2, hence it can’t be used to distinguish
phenol from ethyl alcohol.
104. (a)
115. (a)

CH 2 =CH-OCH3 + H +  CH 3 C H-OCH3 + Br -
 CH 3 CH(Br)OCH 3 .

The formed Carbocation, CH 3 C H-OCH3 is
stabilised by resonance with oxygen so its formation

is more favourable than C H 2 CH 2 OCH3 .
116. (c) Only alkyl aryl ethers, e.g., C6 H 5OCH 3
undergoes electrophilic substitution reactions.
117. (d) -OCH3 is an ortho-, para- directing group.
118. (d) More number of alkyl groups attached to oxygen
in ether more is the Lewis base character.
119. (a) Ethers does not form hydrogen bonding.
121. (b) Natalite is industrial name for dichloro diethyl
ether + alcohol, a petrol substitute.
120. (d) 121. (b)
122. (b) Peroxides are decomposed on heating with H2SO4
123. (d) HCN is a weak acid.

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 ALCOHOLS, PHENOLS & ETHERS

124. (a) Ether linkage is broken up by HBr or HI because

it involves acid catalysed cleavage and Br-, I- are
stronger nucleophile. 1-Pentanol.
125. (b) X: C2H5-O-C2H5 6. (a)
Y: C2H5I

I.

126. (c) .
II.
127. (a) Peroxide oxidises Fe2+ to Fe3+ which gives red  2 5
i C H MgI
III. CH 2 O 
 ii  H2 O  C 2 H 5 CH 2 OH
colour with KSCN.

IV. .
128. (c) oxidation does not

give benzoic acid.

129. (a) 7. (b)
130. (c) Presence of two isopropyl groups on O  atom
of ether shows more powerful inductive effect.
 CH3 2 CH  C2 H5   CH3 
131. (d) It is neither a carbonyl compound (do not give
test with hydrazine) nor an alcohol and thus it may be
ether).

1. (a) 8. (a) Oxymercuration reduction of alkenes lead to

hydration in Markovnikov’s addition rule without
rearrangement i.e., no carbocation formed. Thus

2. (c) .

9. (c) Similar as above question (Markovnikov’s hydration)

3. (d) 3 RX (alkyl halide) undergoes elimination with
base.
(CH 3 )3 CBr  CH 3COOAg ( aq ) 

10. (b)
BH /THF
 CH 3 2 C = CH.CH 2CH 3 
H O ,OH

2
3
2

4. (c) A: RCHO + CH2O

B: RCH2OH + CH3OH
5. (a) Hydroboration-oxidation leads to anti-
Markownikoff’s hydration, thus

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 ALCOHOLS, PHENOLS & ETHERS

11. (c) reduce

R  CHO 
 R  CH 2OH
( B)
18. (c)

19. (a)
R  OH  ( NH 4 )2 Ce( NO3 )6 
 Ce( NO3 )6 ( ROH )9  N2  14 NO3
alcohol cerric amine. nitrate yellow ppt.

20. (c) X: C6H5CH(OH)CH3

12. (a) Addition of CH3MgBr takes place on two >C=O Y: C6H5COCH3 (Acetophenone)
groups. 21. (b)
13. (b)
2 Cl / hv
CH 3OCH 3  CH 3OCH 2 Cl
14. (a) Methoxy methane  Chloro dim ethyl ether
( Lower ether )
CH MgBr
3
 CH 3OCH 2 CH 3 22. (c) The intermediate formed during the reaction is
 MgBr (Cl )
Methoxy ethane benzyl carbocation. EWG decreases stability. -NO2 is
( Higher ether )
15. (b) Among the given compounds, hydroxybenzene stronger EWG than - Cl.
(IV) has least molar mass and therefore possess least 23. (d)
boiling. 1,2-dihydroxybenzene (I) forms intramolecular
H-bonding with result that it will not form
intermolecular H-bonding leading to lowest boiling .
point. On the other hand 1, 3-dihydroxybenzene (II)
and 1, 4-dihydroxybenzene (III) does not undergo
chelation, hence they will involve extensive
intermolecular H-bonding leading to higher boiling
point. Further intermolecular hydrogen bonding is
stronger in the p-isomer than the m-isomer hence
former has highest b.p. Thus the decreasing order of
boiling points is III > II > I > IV.

16. (d)
24. (c)

Al2O3 ( i ) O3
17. (a) R  CH 2CH 2OH 
350 C
 R  CH  CH 2 
( ii ) Zn / H 2 O

R  CHO  CH 2O ( A)
Methanal

667
 ALCOHOLS, PHENOLS & ETHERS

Remember that presence of electron-withdrawing 29. (a)

intensifies i.e., destabilises the carbocation thus (I)
and (II) are less stable than (III). Further (I) is less
stable than (II) because - I effect is more pronounced
in (I) due to less distance between F and + charge.
reactivity of their parent alcohols will be
IV > III > II > I.
25. (b)
30. (c)

31. (a)

94 g of phenol reacts with 480 g of Br2 .

26. (a) 480

2 g of phenol reacts with  2  10.22 g of Br2 .
94
32. (c) In DMSO, S N 2 mechanism occurs.

In CF3CH 2OH ; it accepts the proton Ph  C H
2
attacks at the p-position.
33. (c)
(I), (II) and (III) are probable positions as per electronic
effect of OH group where electrophile can attack and
due to steric hinderance at (II) and (III) positions bulky
electrophiles are not preferred like I only preferred at
position I, Bromine at positions II and I is while chlorine
at all three positions.

34. (b)
35. (d) Conjugate diketone is known as benzoquinone.
36. (d) Benzoylation of phenol is known as Schotten
Baumann reaction.
37. (a) A  C6 H 6 , B  C6 H 5 NO2
C=Hydrazobenzene
38. (a)

27. (b)
28. (b) X: C6H6 - Benzene
Y: C6H5CH3 - Toluene
Z: C6H5COOH - Benzoic acid

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 ALCOHOLS, PHENOLS & ETHERS
39. (a)
40. (c)
41. (a) With excess of conc. HI iodises are formed from
ether or alcohol but nuclear OH is not replaced by I.
1. (d)
2. (c)
3. (a) Boiling point increases with increase in the number
of carbon atoms because of increase in molecular
mass. So, the boiling point of pentan-1-ol is more than
that of all boiling points than 2 alcohols because of
higher surface area in 1 alcohols. Therefore, boiling
point increase in the order
Propan-1-ol < butan-2-ol < butan-1-ol < pentan-1-ol
669
1. (a) a. is a symmetrical ether so the
products are CH 3 I and CH 3OH .
b. In unsymmetrical ether, one
alkyl group is primary while another is secondary. So,
it follows S N 2 mechanism. Thus, the halide ion attacks
the smaller alkyl group and the products are
c. In this case, one of the alkyl group is tertiary and
the other is primary. It follows S N1 mechanism and
halide ion attacks the tertiary alkyl group and the
products are (CH 3 )3 C  I and CH 3OH .
d. Here, the unsymmetrical ether is alkyl aryl ether. In
this ether O  CH 3 bond is weaker than O  C6 H 5
bond which has partial double bond character due to
resonance. So, the halide ion attacks on alkyl group
and the products are C6 H 5  OH and CH 3 I .
2. (c) 3. (b)
1. (b) HCOOH is the most reactive acid among the
carboxylic acid. Alcohol acts as nucleophile.
2. (a) Ammonium phosphate and ammonium sulphate act
as food for yeast.
3. (a) Ethanol is associated with water through hydrogen
bond.
4. (a) CaCl2 3C2 H 5 OH
5. (c) Sodium ethoxide may be prepared by the action of
ethanol with aq. NaOH
6. (c)
7. (b) o-nitrophenol is less soluble in water due to
intramolecular H-bonding.
m- and p-nitrophenol exist as associated molecules
due to intermolecular H-bonding.
8. (a) 9. (d)
10. (d) Both Benzoic acid, phenol react with NaOH.
11. (a)
1. (b) Dichlorocarbene (: CCl2 )
CHCl3  OH  H 2 O  : CCl2  Cl 
 ALCOHOLS, PHENOLS & ETHERS

2. (a) . Haloform reaction is shown by compounds having CH3CO- or CH3CH(OH)- groups.

3. (b)

dry ether
4. (b) 2C2 H 5OH  2 Na   2C2 H 5  ONa  H 2 8. (d)

( A) (B)
C2 H 5  OH  PCl5  C2 H 5 Cl  POCl(3)  HCl
9. (d)

C2 H 5  O N a  C2 H 5 Cl  C2 H 5  O  C2 H5  NaCl
(B) (C ) Diethyl ether

5. (b)

6. (c)

This is williamson ether synthesis.

10. (d) Reimer-Tiemann reaction

More - I, -M, more acidic

11. (b)

7. (d) Intermediate carbocation (more stable).

No rearrangement in C  takes place.

So product is not possible.

Example of substitution reaction.

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 ALCOHOLS, PHENOLS & ETHERS

12. (a) Williamson synthesis is the best method for the compared to benzyl oxide ion, thus releases proton
preparation of ethers. In this method an alkylhalide is more easily. Thus strong acid among the given options.
allowed to react with sodium alkoxide, it is 17. (a)
S N 2 reaction.

13. (a)

while 2, 4, 6 trinitrophenol, benzoic acid and benzene

sulphonic acid are soluble in NaHCO3 .
Acid  NaHCO3  salt  H 2 CO3
This reaction is possible in forward direction if acid is
more acidic than H 2 CO3 . o-Nitrophenol is less acidic
18. (a)
than H 2 CO3 . Hence, it is not soluble in sodium
hydrogen carbonate.
14. (d) Pheonols react with alkylhalides in
alkaline medium to form ethers. Therefore,

PBr3
19. (c) CH 3CH 2 OH   CH 3CH 2 Br
15. (b) The ether, which give more stable carbocation, KOH alc H 2 SO4
  CH 2  CH 2 
H2 O ,
 CH 3CH 2OH
gives CH 3OH as one of product with concentrated
HI. The order of stability of carbocation is 30  20  10
20. (c)

HIO4 oxidises CH 2 OH to HCHO and breaks th C-C

bond of terminal CH 2 OH groups.
21. (a) In the cleavage of mixed ethers with two different
alkyl groups, the alcohol and alkyl iodide that from
depend on the nature of alkyl group. When primary or
secondary alkyl groups are present, it is the lower
alkyl group that forms alkyl iodide therefore

16. (d) Phenyl is an elctron withdrawing

substituent while
-CH 3 is an electron releasing substituent. Moreover,,
phenoxide ion is more resonance stabilised as

671
 ALCOHOLS, PHENOLS & ETHERS

1. (b)

11. (a) 1 Alcohol

2. (a) will most readily be
dehydrated to give conjugated alkene.
3. (b) The reactant undergoes acylation first followed by
substitution intramolecular
4. (a)

2 Alcohol
5. (d) CH 3 MgBr  CH 3  OH  (CH 3O)MgBr  CH 4  gas
6. (c) Nucleophilic substitution

7. (d) Given reaction is known Gattermann formylation

reaction.
8. (d)
9. (a)

10. (a)

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 ALCOHOLS, PHENOLS & ETHERS

3 Alcohol

1. (d) Formation of X is called Kolbe reactions.

Reaction of X with (CH3CO)2O step is called acylation.

2. (c)

12. (d)

Reaction occurs via the formation of stable benzyl

carbocation.

3. (d) The reaction of alcohol with Lucas reagent is mostly

S N 1 reaction and the rate of reaction is directly
13. (c) proportional to the stability of carbocation formed in
the reaction.
Because 3 R  OH forms 3 carbocation (most
stable), hence, it will react fastest by S N 1 reaction.
4. (c) Electron withdrawing substituents like -NO2, -Cl
increase the acidity of phenol while electron releasing
substituents like -CH3, -OCH3 decreases acidity. Hence
the correct order of acidity will be

14. (a)

5. (d)

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 ALCOHOLS, PHENOLS & ETHERS

CHI attacks 2 alcohol as well as bond. OH group is the activating group, activates the
6. (c) There is intermolecular H-bonding in o-nitrophenol, benzene towards electrophilic substitution reaction
and thus, solubility in water is decreased. at o-and p-positions giving yellowish white precipitate
of 2, 4, 6-tribromophenol.

9. (c) The reaction of alcohol with conc. HCl and

7. (d) I anhydrous ZnCl2 follows S N 1 pathway, so greater
the stability of carbocation formed, faster is the
reaction. 2-methylpropan-2-ol gives 3 carbocation.
Acidic because of resonance stabilisation of phenoxide Hence it reacts rapidly with conc. HCl and anhydrous
ion. ZnCl2 (Lucas reagent).
10. (b)

II

The above reaction is called Kolbe’s reaction.

11. (d)
CH 3 group releases electrons, destabilises the
phenoxide ion, thus, acidic nature is decreased, hence,
II < I (acidic).

III 12. (c)

P  I2 Mg
CH 3CH 2OH   CH 3CH 2 I 
dry ether
 CH 3CH 2 MgI
( A) (B)
 NO2 withdraws electrons, stabilizes the phenoxide
ion, hence acidity is increased.
(IV) Lower acidity in case of m-isomer as compared to
p-isomer is explained by the fact that m-nitrophenoxide
is stabilised by inductive effect only and no resonance
effect operates with  NO2 group.
The compound D is n-propyl alcohol.
Thus, m-nitorphenol < p-nitro
8. (a) Br2 is formed by a redox reaction.
5 Br   BrO3  6 H   3Br2  3H 2 O

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