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Solutions
SECTION - A
Objective Type Questions (One option is correct)
1. A compound X with the molecular formula C3H8O can be oxidized to another compound Y whose
molecular formula is C3H6O2. The compound X may be
2. Which one among the following compounds will produce a secondary alcohol on reaction with Grignard
reagent?
(1) CH3COCH3 (2) CH3 – COOCH3 (3) HCOOCH3 (4) All of these
Sol. Answer (3)
2R – Mg – x R
HCOOCH3 H — C — OH
H2O
R
Secondary alcohol
3. An alkene obtained by the dehydration of an alcohol A on ozonolysis gives two molecules of acetaldehyde
for each molecule of the alkene. The alcohol A is
| Acetaldehy de
OH
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136 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
4. A compound of molecular formula C6H6O turns ferric chloride solution violet and produces no effervescence
with NaHCO3. The compound is
(1) Phenol (2) Anisole (3) Benzoic acid (4) All of these
Sol. Answer (1)
C6H6OH is phenol because it gives violet colour with neutral FeCl3 and produces no effervescence with
NaHCO3.
5. When sodium phenoxide is heated with CO2 under pressure followed by acidification with HCl, the product
obtained is
(1) Salicylic acid (2) Salicylaldehyde (3) Benzoic acid (4) Cinnamic acid
Sol. Answer (1)
OH
CO 2 CO O COOH
Under Pressure
Sodium Phenoxide Salicylic Acid
6. An organic compound having the molecular formula C3H6O does not give a precipitate with 2, 4 dinitrophenyl
hydrazine and does not react with sodium metal. The compound is expected to be
(1) CH3 – CH2 – CHO (2) CH3 – CO – CH3 (3) CH2 = CH – CH2 – OH (4) CH2 = CH – OCH3
Sol. Answer (4)
C3H6O does not give a precipitate with 2, 4 – dinitrophenyl hydrazine. So, it can’t be aldehyde and ketone.
C3H6O also does not react with Sodium metal. So, it can’t unsaturated alcohol also. Hence, C3H6O must
be CH 2 — CH — OCH 3
O O NaBH4
A
O
7. LiAlH4
B
COCl
OH OH OH O OH O OH OH
OH O O OH
(1) A = B= (2) A = B=
OH OH OH O
OH O
(3) Both A and B (4) Both A and B
CH2 – OH COCl
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 137
8. Consider the following reaction sequence
O
CH3MgBr POCl3
A B
H2O Pyridine 0°C
The product B is
O OH CH 3
CH3MgBr POCl3
H2 O CH3
Pyridine 0°C
10. An organic compound A react with sodium to form another compound B . The compound A when heated
with concentrated H2SO4 forms diethyl ether. The compound A and B are respectively
Na
C2H5OH
C2H5ONa
(A) (B)
Conc . H SO
2C2H5OH
2
4
C2H5 — O — C2H5
(A) Diethyl ether
OH +
H
X; is
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138 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
OH
H
+
–H 2O Ring e xpansion –H
+
12. Which of the following reaction does not form ether as major product?
CH 3 CH3
(1) CH3 – C – O – Na + CH3CH2Br (2) CH3 – C – Br + CH3CH2ONa
CH 3 CH3
H CH3 CH2Br
(3) CH3 – C – Br + CH3ONa (4) CH3 – C – ONa + CH3 – CH2
H H
Sol. Answer (2)
Tertiary alkyl bromide gives alkene as a major product in presence of sodium ethoxide because tertiary
carbocation readily gives elimination reaction and converted into most stable alkene.
CH 3 CH3
| |
CH3 — C — Br + CH3CH2ONa CH3 — C NaBr + CH3CH2OH
| ||
CH 3 CH2
13. Arrange the given species in the increasing order of acidic strength
H
—C C—H
H
I II
O
H
—C—H O
III IV
(1) I < II < III < IV (2) I < III < II < IV (3) III < II < I < IV (4) II < III < I < IV
Sol. Answer (2)
O–H
H H
is most acidic. is acidic because it gives (aromatic) by the removal of H . Now, the order
of acidity becomes
O–H H H O
||
> > C—H > C——
— C— H
(I)
(IV) (II) (III)
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 139
14. Compound (X), C7H8O dissolves in NaOH but not in NaHCO3. (X) reacts rapidly with Br2 to give (Y), C7H5OBr3.
Probable structure of X would be
OH
OH OMe OH
Me
(1) (2) (3) (4)
CH3 Me
OH
Me
15. During the chromic acid oxidation of isopropyl alcohol into acetone colour of the reaction mixture changes from
yellow-orange to greenish blue. The greenish blue colour is because of
(1) Acetone (2) H2CrO4 (3) HCrO3– (4) Cr3+
Sol. Answer (4)
The greenish blue colour is due to presence of Cr3+ which is obtained by the reduction of K2Cr2O7.
16. Which of the following reactions will not yield alcohol as the major product?
O
O
C
(1) Li + CH2 CH2 (2) MgBr + EtO OEt
(Excess)
—
MgBr + N —
—C C—
— N — Mg — Br
2H 2O
—O
C— Br
Diphenyl Ketone + NH 3+ Mg
OH
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140 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
17. Pyridinium chlorochromate and MnO2 are used as selective oxidizing agents in organic synthesis. What would
be the oxidation products of compound X, when it reacts separately with PCC and MnO2?
–
N + CrO3Cl
MnO2 OH H
[A] [B]
CH2Cl2
HO X
CHO CHO
CHO
OH
(2) [A] = and [B] =
O O
COOH CHO
CHO COOH
H
KOC(CH3)3 [B]
18. In the reaction : — C — CH3 [A] — CH2 — CH2 — OH
(CH3)3COH
Br
The molecule [A] and the reagent [B] are
O — C(CH3)3
Br
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 141
Sol. Answer (2)
Strong sterically Hindered Base gives. Less substituted alkene as major product.
H
| KOC(CH3) 3 B 2H6/THF
C — CH3 CH —
— CH2 CH2— CH2— OH
| (CH3)3COH H2O2/OH¯
Br
19. Which of the following ethers is unlikely to be cleaved by hot conc. HI?
O CH3
O C CH3
(1) (2) O (3) (4) O
CH2 CH3
Me
I. KOH/CHCl3 I. Ac2O/NaOAc
+ [A] + Product (P).
II. H3O II. H ,
OH
O
H C
Me C C OH
H
(1) (2)
O O Me
O OH
CH CH — C — OH Me
O
(3) Me OH (4)
CH CH — C — OH
Me Me Me
Me
KOH/CHCl3 (i) Ac2O/NaOAc H+
(ii) H3O+ –H2O
CH — O O
CHO — CH — COOH
OH OH OH
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142 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
21. Which of the following pinacol-pinacolone type of reaction will involve ring contraction?
+H NaNO2/ HCl
(1) (2) CH2 — NH2
OH OH OH
Me
+H
+H
(3) O (4)
Me OH OH
Me Me Me
H+ Ring R
O O—H
OH Contraction C——O
Me Me Me |
R
CH3
NaOH
C C — C — CH3
Br
CH3 CH3
OH
O
CH3 CH3
(3) C — CH C (4) CH C
CH3 C — CH3
O
Sol. Answer (3)
CH3
| CH 3
— —C —
—C
|
C—
— C — C — CH3 C—
| | CH 3
|
Br OH
HO
CH 3
C— —C
|
—C—
| CH 3
|
OH
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 143
23. Reagents required to perform the given transformation is
OH
(1) (i) O2 - oxidation (ii) H3O+ (2) (i) KMnO4, hot (ii) LiAIH4 (iii) H3O+
(3) (i) Hot KMnO4 (ii) NaBH4 (iii) H3O+ (4) (i) H2CrO4 (ii) CaO + NaOH, (iii) NaOH
Sol. Answer (1)
O—O—H
OH
+
O2 H3 O
+ —O
24. Which reaction or reactions sequence will furnish the following transformation?
?
OH NH2
(1) (i) NaNH2 (ii) H3O+ (2) (i) SOCl2 (ii) NaN3 (iii) Sn/HCl
(3) (i) PCl5 (ii) NaNH2 (iii) H (4) (i) HI (ii) NaNH2 (iii) H
Sol. Answer (2)
OC2H5
(1) Benzyl ethoxide (2) Ethoxy benzyl (3) Benzene ethoxide (4) Ethoxy benzene
Sol. Answer (4)
+
H /H2O
26. CH3CH CH2 major product is:
OH
(1) CH3 – CH – CH2 (2) CH3CHCH3 (3) CH3CH2CH2OH (4) CH 3CH — CH2
O OH OH
Sol. Answer (2)
Markovnikov’s addition.
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144 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
Hg – OAC Hg – OAC
OH OH
NaBH 4
CH3 – CH – CH2 CH3 – CH – CH2
HgOAC H
(Anti-addition)
O O O
Hg (O – C – CH3 )2 Hg – O – C – CH3 + CH3 – C – O
1. O3 1. LiAlH4/Dry ehter
29. RCH CH2 (A) + (B)
2. H2O/Zn 2. H3O
Product (B) is
(1) RCHO + HCHO (2) RCHO + HCOOH (3) RCOOH + HCOOH (4) RCH2OH + CH3OH
Sol. Answer (4)
O O
O3 H2 O LiAlH4
RCH CH2 RCH CH2 RCHO + HCHO RCH2OH + CH3 OH
O
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 145
30. SN1 is observed in
R aq. KOH
(1) CH X (2) R — OH + SOCl2
R
alc. KOH
(3) R – X (4) ROH + HX
Sol. Answer (1)
O
18 +
33. R' — OH + R C — OH H ?
Products are
O O
18 18
(1) R — C — O R' + H2O (2) R' — C — OR' + H2 O
O O
18 18
(3) R' — C — OR + H2 O (4) R' — C — OR + H2O
Sol. Answer (1)
O
[?]
34. R C — OH R CH2 — OH
Here reagent is
(1) LiAlH4 (2) NaBH4 (3) Both (1) & (2) (4) Red P/HI
Sol. Answer (1)
OCH3
CH3Br/ FeBr3
36. ? major product is
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146 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
OH
OH OH OH
OH OH OH OH OH OH OH
OH
CH3 CH3
(1) > > > (2) < < <
CH3 CH3
CH3 CH3
OH OH OH OH OH OH OH
OH
CH3 CH3
(3) < < < (4) > > >
CH3 CH3
CH3 CH3
40. How many minimum number of carbons are needed for an optically active ether?
(1) 2 (2) 3 (3) 4 (4) 5
Sol. Answer (4)
HBr
41. In the reaction OCH3 the products are [IIT-JEE-2010]
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 147
Sol. Answer (4)
H
H—Br
O O –
Br
OH + CH3Br
CH 3 CH3
RCH OH
2
H (anhydrous)
O
(1) A hemiacetal (2) An acetal (3) An ether (4) An ester
Sol. Answer (2)
H
– H :O – CH2 – R
:
CH 2
O O O O R
H
–H
CH2 – R
O O
An aceta l
SO3H
OH OH OH OH
Br Br Br Br Br
Br Br Br Br Br
SO3H Br Br SO3H
P Q R S
(1) P (2) Q (3) R (4) S
Sol. Answer (2)
OH OH
Br Br
aqueous
Br2 (3.0 equivalents)
SO 3H Br
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148 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
44. The compound that does NOT liberate CO2, on treatment with aqueous sodium bicarbonate solution, is
[JEE(Advanced)-2013]
(1) Benzoic acid (2) Benzenesulphonic acid
(3) Salicylic acid (4) Carbolic acid (Phenol)
Sol. Answer (4)
Carbolic acid (Phenol) is weaker acid than carbonic acid and hence does not liberate CO2 on treatment with
aq. NaHCO3 solution. Benzoic acid, benzenesulphonic acid and salicylic are more acidic than carbonic acid
and hence will liberate CO2 with aq. NaHCO3 solution.
45. The acidic hydrolysis of ether (X) shown below is fastest when [JEE(Advanced)-2014]
[Figure]
Acid
OR OH + ROH
OH
O
(1) H3C (2) CH3
CH3 H2C
CH3
CH3
(3) CH2 (4)
O O CH3
–
O O CH3
Cl Cl
CH3
CH3
O
CH 3 – MgI
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 149
SECTION - B
Objective Type Questions (More than one options are correct)
2. Which of the following convert a primary hydroxyl group into a good leaving group for a SN2 reaction?
O O
(1) H3C — — S — Cl (2) S
O Cl Cl
3. Which of the following reaction or reaction sequence can be used to prepare epoxides?
O
1. Br2(1 eq) 2. NaBH4
(1) — C — CH3
H CH3 O
m — Cl — C6H4 — COOH
(2) C C
CH2Cl2
H3C CH3
CH3
1. Br2 / CCl4 2. NaOH (1 eq)
(4) H2C C
CH3
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150 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
O O
|| | O
Br2(1 eq.)
(1) C — CH3 C — CH2 C — CH2
| | |
Br Br Br
Epoxide
O
|| O
H CH3 m– Cl – C6H4 – C –O – OH H CH3
—
(2) C—
—C C—C
—
—
Br 2/H2O NaOH
(3) CH CH2 CH — CH2 (aq.) CH — CH2
||
| |
|
O
|
Br O–H
Epoxide
OH
CH3 O
CH3 O—H
5. Which of the following reagents can be used to distinguish phenol from Anisole?
(1) FeCl3 (2) Aqueous NaOH (3) Br2 (4) NaHCO3
Sol. Answer (1, 2)
OCH3
Phenol gives violet colour with FeCl3 and also reacts with aqueous NaOH but Anisole doesn’t
react with FeCl3 as well as NaOH. So, FeCl3 and aqueous NaOH can be used to distinguish phenol from
Anisole.
?
— CH CH2 — CH2 — CH2 — OH
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 151
Sol. Answer (1, 4)
B2H6/THF H2O2/OH¯
CH CH2 CH2 — CH2 — B CH2 — CH2 — OH
||
(1)
3
HBr/Peroxide NaOH
(4) —CH CH2
|| CH2 — CH2 — Br CH2 — CH2 — OH
H2SO4
OH
OH
Probable products of the above reaction are
OR
CH3 CH3
H2SO4 –H2O Rearrangement
OH OH OH OH
OH OH2 CH3
+
–H
CHOH
3
OH HO
O O NaOCH3
NaOCH3
(1) (2) CH3OH
CH3OH O
HO HO
O
O
HO
O NaOCH3
(1) Br2/H2O
(3) CH3OH (4) C—C C C
O (2) OH
HO
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152 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
9. Ortho salicylic acid is frequently used as precursor for the preparation of Aspirin. Which of the following
reactions can be used to prepare o-salicylic acid from phenol?
+ +
NaOH/CHCl3 H3O (1) NaOH H3O
(1) — OH (2) — OH
(2) CO2
+
(1) NaOH Hydrolysis (1) NaOH H3O
(3) — OH (4) — OH
(2) CCl4 (2) HCHO
OH ONa OH
(i) NaOH COOH + COOH
H3O
(2)
(ii) CO 2
o-Salicylic Acid
OH ONa OH
NaOH/CCl4 COOH + COOH
H3 O
(3)
Reimann Tiemann
Reaction
o-Salicylic Acid
— OH
NaNO2/HCl
— NH2
pH = 9
NH2 OH
H H
OH
N N—
(3) (4) HO — —N N—
+ –
NH2 N2Cl
NaNO 2/HCl
+ –
N2Cl OH OH
pH = 9 N N +HO N N
||
||
+
p-hydroxy azobenzene
o-hydroxy azobenzene
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 153
11. Which of the following reactions can be used to prepare cyclic ethers?
NaOH OH NaOH
(1) (2)
HO Cl HO
OH H2SO4, Br NaOH
(3) (4)
HO HO
H-O Cl O
OH H2SO4 OH2 –H2O, –H+
(3) HO H-O O
Cyclic ether
12. Which of the following chemical tests can be used to distinguish primary, secondary and tertiary alcohol from
each other?
(1) Hinsberg Test (2) Haloform Test (3) Lucas Test (4) Victor-Meyer's Test
Sol. Answer (3, 4)
Fact
13. Which reaction or sequence of reactions can be used to prepare catechol in good yield?
OH
OH
Catechol
CHO
O OH +
+
H3O (1) NaOH/H2O2 (2) H3O
(1) (2)
O
Br
OMe
+ +
(1) Mg / Ether H3O SO3/H2SO4 Fuse H3O
(3) (4)
(2) O2 Boil NaOH
+
(3) H3O
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154 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
O H3O+ OH
(1)
O OH
Catechol
CHO ONa OH
OH NaOH/H O ONa H O+ OH
2 2 3
(2)
Catechol
Br Mg-Br O – O – Mg – Br OH
O Me Mg/Ether O Me O O Me H3O+ OH
2
(3)
Boil
Catechol
14. The correct statement(s) about the compound H3C(HO)HC—CH=CH—CH(OH)CH3 (X) is are
[IIT-JEE-2009]
(1) The total number of stereoisomers possible for X is 6
(2) The total number of diastereomers possible for X is 3
(3) If the stereochemistry about the double bond in X is trans, the number of enantiomers possible for X is 4
(4) If the stereochemistry about the double bond in X is cis, the number of enantiomers possible for X is 2
Sol. Answer (1, 4)
Given compound has three stereocentre with symmetrical substituents. It will form six stereoisomers out of
which 2 will be meso and one dl pair of cis and one dl pair of trans.
OH
O O O O
Br
(1) (2) (3) (4)
Br
Br Br Br Br
O O
Br Br Br
Br Br
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 155
16. In the following reaction, the product(s) formed is(are) [JEE(Advanced)-2013]
OH
CHCl3
OH
– ?
CH3
OH O OH OH
OHC CHO CHO
O
O H3C CH3
CH3 O
O H
(1) (2)
O
O CH2
CH2 O H
O
(3) (4)
O H
O
+
,H Radical, initiator, O2
High pressure, heat
'T' 'U'
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156 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
SECTION - C
Linked Comprehension Type Questions
Comprehension-I
Phenols are more acidic than aliphatic alcohols, acidity of phenols can be further increased by the introduction
of electron withdrawing groups in aromatic ring. Acidic nature of phenol is because of the resonance
stabilization of phenoxide ion.
—O + B: —O + BH
Resonance
stabilized
phenolate ion
1. Which of the following will evolve CO2 gas with aqueous NaHCO3?
OH OH OH OH
MeO OMe O2N NO2 Me Me
(1) (2) (3) (4)
OMe
OMe NO2 Me
MeO OH Me OH
I II
OH NC OH
MeO
III IV
(1) I < II < III < IV (2) II < I < III < IV (3) I < IV < III < II (4) II < IV < I < III
Sol. Answer (1)
—CN group increases the acidity of phenol. When electron releasing group like MeO— is present on m-
position w.r.t. —OH group then it acts as —I effect group and increases the acidity. MeO— is good electron
releasing group in comparison to –Me. So, order of acidity becomes.
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 157
3. Consider the following reactions
NO2 C C—H
O
NaOH (1 eq)
Major
product
NH2
OH OH
NO 2 —
C—
—C—H NO 2 —C—H
C—
—
O NaOH O
(1 eq)
NH2 NH2
OH OH ONa OH
In which NaOH reacts with only —OH group which is directly attached to the benzene ring. Other groups
can’t give H+ in aqueous medium.
Comprehension-II
Attack by a strong nucleophile such as CH3O (Methoxide ion) on an epoxide occurs at the least hindered
carbon, similar to an SN2 reaction.
O OH
O
H — OCH3
CH CH2 Ph + CH3O
Ph
Ph OCH3 OCH3 OCH3
Attack by a weak nucleophile such as MeOH can occur only when the epoxide has been protonated so that
a better leaving group is formed, under acidic condition weak nucleophile attacks more substituted carbon
to give final product.
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158 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
OH
O
(3) (i) KMnO4, OH, 0ºC (ii) Hydrolysis (4) (i) Br2 / H2O (ii) OH
Sol. Answer (1)
Formation of epoxide and then ring opening is the anti addition.
O
|| OH
CH3 — C — OOH H2O
O
OH
(i) NaOCH3
O
+
(ii) H
H
Ph Ph Ph MeO
Me OH OH Ph
(1) (2) (3) (4)
OH Ome H OH
H H Ome H
Sol. Answer (3)
Ph Ph Ph
NaO CH3 O H+ OH
O
H H
H OMe OMe
In the Ist step CH3O¯ attacks on least hindered carbon similar to SN2 reaction. If acidic medium is taken
together than reverse reaction occurs.
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 159
Comprehension-III
O
–
(1) OH NaNO2/HCl NaNO2
+ A C D
(2) H 0.5°C
Conc HNO3
NH2
B
1. Product (B) is
O O OH OH
NO2 O
OH NO2
OH
OH OH
NO2
(1) (2) (3) (4) All of these
F
CHO
Sol. Answer (4)
Comprehension-IV
Riemer-Tiemann reaction introduces an aldehyde group, on to the aromatic ring of phenol, ortho to
the hydroxyl group. This reaction involves electrophilic aromatic substitution. This is a general method for the
synthesis of substituted salicylaldehydes as depicted below. [IIT-JEE-2007]
OH O Na OH
CHO aq. HCl CHO
[I]
(Intermediate)
CH3 CH3 CH3
(I) (II) (III)
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160 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
O Na O Na O Na O Na
CH2Cl CHCl2 CCl3 CH2OH
(1) (2) (3) (4)
Comprehension-V
In the following reactions
Pd-BaSO4 i. B2H6
C8H6 C8H8 X
H2 ii. H2O2, NaOH, H2O
H2O
HgSO4, H2 SO4
i. EtMgBr, H2O
C8H8O + Y
ii. H , heat
[JEE(Advanced)-2015]
1. Compound X is
O OH
OH
CHO
CH3 CH3
(1) (2) (3) (4)
OH
Pd-BaSO4 i. B2H6
C8H6
H2 ii. H 2O2, NaOH, H2O
CH3 CH3
(1) (2)
CH3
CH2
CH3
(3) (4) CH3
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 161
Sol. Answer (4)
O
H2O
C8H6
HgSO4
H2SO4
i. Et MgBr, H2O
+
ii. H , Heat
SECTION - D
Assertion-Reason Type Questions
1. STATEMENT-1 : Victor-Meyer's test can be used to distinguish primary and secondary alcohols.
and
STATEMENT-2 : Under Victor-Meyer's condition these alcohols give different colouration.
Sol. Answer (1)
In Victor Meyer’s test, primary alcohol gives Red Colouration while secondary alcohol gives blue colouration.
3. STATEMENT-1 : Phenols cannot be converted into esters by direct reaction with carboxylic acids whereas
alcohols can be.
and
STATEMENT-2 : This is due to the fact that the esterification reaction is exothermic for alcohols but slightly
endothermic for phenols.
Sol. Answer (1)
Fact.
4. STATEMENT-1 : Secondary alcohols react faster than primary alcohols with Na.
and
STATEMENT-2 : O—H bond in secondary alcohol is less polar than primary alcohol.
Sol. Answer (4)
O—H bond is less polar in secondary alcohol than primary alcohol. So, primary alcohol reacts faster with
Na than secondary alcohol.
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162 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
OH
(Resorcinol) turns FeCl3 solution purple and it is dihydric phenol also.
OH
11. STATEMENT-1 : Hydration of alkenes may give more than one type of alcohol.
and
STATEMENT-2 : Carbocation intermediate may show rearrangement.
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 163
Sol. Answer (1)
Hydration of alkenes starts with formation of carbocation which may undergo rearrangement.
SECTION - E
Matrix-Match Type Questions
demercuration
Ph H Ph H
(D) CH3 – C = C – CH3 CH3 – C — C – CH3 (s) Carbocation intermediate
OH H
(A)
|| | OH
|
The reaction is oxymercuration–demercuration. The net result of this reaction is the addition of H2O according
to Markownikoff’s rule.
||
(B) OH
The reaction is hydroboration oxidation. The net result of this reaction is the addition of H2O according to
Anti-Markownikoff’s rule.
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164 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
Ring
CH2 — Br NaOH CH2
(C) O–H
–Br– expansion
OH OH
+
–H
||
The reaction proceeds through carbocation intermediate.
Ph H Ph
| | H +
/H O |
(D) CH3— C —
— C — CH3 2
CH3— C — CH2— CH3
H
O
H
Ph H Ph H
| | –H+ | |
CH3— C — C — CH3 CH3— C — C — CH3
| | | |
OH H O H
H H
The reaction proceeds through carbocation intermediate and H2O is added according to Markownikoff’s rules.
ONa
(I) CO2
(A) + (p) With neutral FeCl3 test
(II) H3O
O—O—H
(B) H3C CH3 (q) With NaHCO3
C
+H
OH
+
NN—
(C) Cl– (r) With Na
pH = 9
OH
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 165
Sol. Answer: A(p, q, r), B(p, r, s), C(p, r), D(p, r, s)
ONa OH
COOH
(i) CO2
(A) (ii) H3O+
Salicylic Acid
Salicylic acid gives purple colour with neutral FeCl3 due to presence of —OH group and reacts with
NaHCO3 and Na.
O—O—H
H3C CH 3
C OH
(B) H +
CH3
+ C—
—O
CH3
Phenol can give purple colour with neutral FeCl3 and also reacts with Na but not with NaHCO3. Acetone
reacts with 2, 4, DNP.
OH +
N—— NCl¯
—
(C) HO —N
N— Cl
pH = 9
Azo dye
Azo dye gives purple colour with neutral FeCl3 and also reacts with Na due to —OH group
OH OH
(i) KOH/CHCl3 CHO
(D)
(ii) H3O +
Salicyldehyde
Product reacts with neutral FeCl 3 and Na due to —OH group and reacts with 2, 4-DNP due to
—CHO group.
Me D
Pyridine
(A) H (p) Isotopic effect
Me CH3
O Cl
P=O
Cl
D
Conc. H
(B) H
(q) Saytzeff product
CH3
OH
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166 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
Me
R3N
(C) D H (r) Rearrangement
Me
CH3 OTS
CH3 +
Conc. H
(D) Ph – CH2 – CH – CH (s) Bimolecular elimination
OH CH3
(A) D B as e
H
CH3
CH3 (E 2)
Cl Saytzev's product
O
P O
Cl
It also involves isotopic effect.
D D
+H rearrangement
(B) H CH3 Product
Slow
CH 3 CH3
OH D
Product
Me Me
R3N
(C) D H
Me Me
Me OTs Me
(D) Also involve carbocationic formation followed by rearrangement.
C N CH2 –NH2
(A) (p) LiAlH4
O
OH
C
(B) CH3 CH3 (q) NaBH4
O O
H
(C) OEt O (r) H2/Pd
O
(t) Reduction
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 167
Sol. Answer : A(p, r, t), B(p, q, r, s, t), C(q, s, t), D(p, r, t)
x
–CN —CH2 — NH2 (x may be Li, AlH4 and H2/Pd)
O OH
x (x may be Li, AlH4, NaBH4 DIBAL and H2/Pd)
— C—CH3 —CH—CH3
O
O
x O
(x may be NaBH4 DIBAL and H2/Pd)
OEt
O
O
NH NH
x (x may be LiAlH4 H2/Pd)
O OCH3 OH
OH OCH3
O CH3
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168 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
7. Match the reactions in Column I with appropriate options in Column II. [IIT-JEE-2010]
Column I Column II
NaOH/H2O
(A) N2Cl + OH N=N OH (p) Racemic mixture
0°C
O
OH OH CH3
C
H2SO4
(B) H3C – C — C – CH3 H3C C (q) Addition reaction
CH3
CH3 CH3 CH3
O OH
1. LiAlH4
(C) C + CH (r) Substitution reaction
2. H3O
CH3 CH3
Base
(D) HS Cl S (s) Coupling reaction
(A) N N + O —H
Cl–
OH
N=N O
H
N=N O
OH OH OH OH2
+H
(B) CH3 — C — C — CH3 CH3 — C — C — CH3
CH 3 CH3 CH 3 CH 3
O CH3 OH
CH3
CH3 — C — C — CH3 CH3 — C — C
CH3
CH3 CH3
Carbocation intermediate
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 169
O OH
O +
LiAlH 4 H H3O
(C) C Nucleophilic addition
C H C H
CH3
CH 3 CH 3
Racemic mixture
Nucleophilic
H Base S substitution S
(D)
S Cl Cl
B
8. Match the chemical conversions in Column I with the appropriate reagents in Column II and select the correct
answer using the code given below the lists : [IIT-JEE-2013]
Column I Column II
OH
(C) (r) Et-Br
OH
Codes :
A B C D
(1) q r p s
(2) r q p s
(3) q r s p
(4) r q s p
Sol. Answer (1)
NaOEt
(P) Cl
(1) Hg(OAc)2 OH
(R)
(2) NaBH4
(1) BH 3
(S)
(2) H2O2/NaOH
OH
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170 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
SECTION - F
Integer Answer Type Questions
1. CH2OH
+
H
Product
HOCH2 CH2–OH
The degree of unsaturation of product is
Sol. Answer (4)
O
||
CH3NH2 , CH3 C CH3 , OH and H – C C – H are less acidic than C2H5OH.
2. O
+
H
Product
CH3 C2H5
In final product, the number of aromatic rings in the product is/are
Sol. Answer (2)
CH3 CH3
HO H H OH
aminohydroxylation
H NH2 and H 2N H
CH2 CH3
3. The number of isomers (including stereoisomers) of C5H12O which can give positive haloform test is
Sol. Answer (4)
CH3—CH2—CH2—CH—CH3 (d, l)
OH
CH3
CH3—CH—CH—CH3(d, l)
OH
O
+
H
4. Product
CH3 C2H5
In final product, the number of electrons involved in aromaticity is 2x. The value of x is
Sol. Answer (5)
OH
2x = 10
x=5
CH3
C2H5
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 171
SECTION - G
Multiple True-False Type Questions
1. STATEMENT-1 : Phenol is more acidic than ethyl alcohol.
STATEMENT-2 : Phenol is a weaker acid than benzoic acid.
STATEMENT-3 : Phenol is a good substrate to prepare o-salicylic acid.
(1) T T F (2) TTT (3) FFF (4) FT T
Sol. Answer (2)
Due to resonance phenol is more acidic than C2H5OH.
Phenol is weaker acidic than benzoic acid due to less stable resonating structures formation.
2. STATEMENT-1 : Pyridinium chlorochromate can convert primary alcohols into corresponding aldehyde.
STATEMENT-2 : MnO2 can oxidize benzylic alcohol into corresponding carboxylic acid.
STATEMENT-3 : OsO4 can convert alkene into trans 1, 2-diol.
(1) F F F (2) TTT (3) TTF (4) TFF
Sol. Answer (3)
OsO4 make syn addition.
SECTION - H
Aakash Challengers Questions
1. Show the product from the following reaction. Write mechanism in support of your product.
O
+
+ CH2—S(CH3)3
O
O O
Sol. CH2—S(CH3)3 CH2—S(Me) 2 CH2 + S(Me)2
2. How many of the following glycols is virtually inert to periodate oxidation? Which glycol is inert? Explain, why.
OH OH
(1) (2)
(Me)3C OH (CH3)3C OH
CH3 CH3
(3) (4)
OH OH
OH OH
Sol. Option (2) and (3) will react with periodic due to formation of favourable conformer.
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172 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
(i) + H—OSO2CF3 +
S
S
OS2CF3
CH2CH2CH—CH2
Trace OH
(ii)
O CH2OH
OH
Sol.
S S S
O O
O O Cl
O
O mCPBA O
OH
OSiR3 OSiR3
Sol. The reaction will involve epoxidation followed by acid catalyzed ring opening.
5. Show how you would synthesize the following compound. As starting materials you may use any organic
compound containing four or fewer carbons.
OH
Sol. Mg
Br THF MgBr
Excess
C
Cl Cl
OMgBr
H 3O
OH
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 173
6. Chromic acid oxidation of an alcohol occurs in two steps : formation of chromate ester followed by an
elimination of H+ and chromium. Which step do you expect to be rate-limiting? Careful kinetic studies have
shown that compound A undergoes chromic acid oxidation over 10 times as fast as compound B. Explain
the large difference in rates.
Me
Me
OH
OH H
(A) H
H2CrO4
Faster H2CrO4
(B)
Slower
Me
O
H
7. Show how you would synthesize the following compound from any starting materials containing no more than
six carbon atoms.
Sol. O
OMgBr
H—C
MgBr + CH
+
(i) H3 O
+
(ii) H ,
O mCPBA
CH2Cl 2
CH CH
8. Provide a mechanism for the following reaction and suggest a reason for the diastereoselectivity of the
reactions.
CH2OH CH2–OH
NaOH/H2O2
O O
O
Sol. The reaction occurs syn to the hydroxy methyl group.
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174 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
9. Write the best reagents above each reaction arrow. If the transformation cannot be achieved in a single step
by any reagents write "NR"
?
OH O
(a)
H
?
OH Br
(b)
?
OH NH2
(c)
H
(b) PBr3
(c) (i) PBr3
(ii) NaN3
(iii) LiAIH4
O
(c) OH [C]
(2) KI
–
N + + CrO3Cl
(d) H
OH [D]
CH2Cl2
Sol. (a)
CH3
CH3
(c) I
(d) O
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 175
11. Prepare the following ethers via the Williamson's synthesis
O
(a)
CH2
CH3
CH3
— CH2 — Br
NaOH O
Sol. (a) OH ONa
CH2
Sol. OH
(i) NaSH
+ Ph — CH — CH2 — SH
(ii) H 3O
OH
O
Ph — CH — CH2D
(i) LiAID4
+
(ii) H 3O
Ph — HC CH2 OMe
Styrene oxide
MeOH / H
Ph — CH — CH2 — OH
Br
HBr (1 eq.)
Ph — CH — CH2 — OH
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176 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
CH3COOOH MeOH / H
[A] [B]
CH2Cl2
CH3 CH3
H3C H O
+
H OH HO H
CH3COOOH H /MeOH +
C C C C H OMe MeO H
Sol. CH2Cl 2
14. Use simple chemical tests to differentiate between each member of the following pairs of compounds.
(a) n-Propylalcohol and phenol
(b) Phenol and Benzoic acid
Sol. (a) Phenol will dissolve in aqueous NaOH. While propanol is insoluble in aqueous NaOH. Phenol also gives
violet colouration wtih FeCl3.
(b) Benzoic acid evolves CO2 gas with aqueous NaHCO3 while phenol does not give CO2 with aqueous
NaHCO3.
aqueous NaI
(a) No reaction
OCH3
O KCN
(b) No reaction
ethanol,
Sol. O CH is a strong base and hence a bad leaving group, hence both the ethers are inert towards nucleophilic
3
attack.
(a) Four stereoisomeric compounds C4H8O, all optically active, contain no double bonds and evolve a gas
when treated with CH3MgI.
(b) A compound believed to be either cyclohexyl methyl ether or 2-methylcyclohexanol evolves a gas when
treated with NaH.
Me OH HO Me Me H H Me
Sol. (a)
H H H H H OH OH H
A B C D
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Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers 177
(b) NaH
— O — CH3 No reaction
Me Me
OH ONa
NaH
+ H2
17. Give a structure for each of the following compounds. (More than one answer may be possible)
(a) A chiral ether C5H10O that has no double bonds
O CH3
H3C OCH3
and H
Sol. (a)
H
H H
CH3
OH
CH 3
H H OH
(c) (i) CH3 – CH2 – C — C – H (ii) CH2 – CH2 – C – CH3
OH OH OH H
18. Design a synthesis of 1-methylcyclopentanol using alcohols with no more than five carbon atoms as the only
source of carbon in the final product.
HO
1-methylcyclopentanol
SOCl 2 Mg / Et2O
Sol. CH3 — OH CH3 — Cl CH3MgCl
X
OH
PCC (i) CH3MgCl (X)
OH O +
(ii) H3O
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178 Alcohols, Phenols and Ethers Solutions of Assignment (Set-2)
19. 0.037 g of an alcohol, R—OH was added to CH3MgBr and the gas evolved measured 11.2 ml at STP.
Structural formula of alcohol will be.
Br
Sol. R—OH + CH3MgBr CH4 + Mg
1 mol 1 mol
OR
11.2 ml CH4 at STP is formed by 0.037 g alcohol.
0.037 22400
22400 ml CH4 at STP will be formed = 74 g R—OH
11.2
General formula of alcohol CnH2n + 1OH
14n + 18 = 74
n4
Alcohol is C4H9—OH
CH3—CH2—CH2—CH2—OH
CH3
|
CH3 — CH — CH2 — OH
CH3
|
CH3 — CH2 — CH — OH
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