25 Alcohols, Phenols and Ethers: Solutions

Chapter 25
Alcohols, Phenols and Ethers
Solutions
SECTION - A
Objective Type Questions (One option is correct)
1. 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
O O NaBH4
A
O
2. LiAlH4
B
COCl
A and B are respectively
OH OH OH O OH O OH OH
OH O O OH
(1) A = B= (2) A = B=
CH2 – OH CH2 – OH CH2 – OH CH2 – OH
OH OH OH O
OH O
(3) Both A and B (4) Both A and B
CH2 – OH COCl
Sol. Answer (2)
LiAlH4 reduces —COO—, —COCl and C—
— O groups. While NaBH4 reduces C—
— O and — COCl group
not —COO— group.
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130 Alcohols, Phenols and Ethers Solutions of Assignment
3. Consider the following reaction sequence
O
CH3MgBr POCl3
A B
H2O Pyridine 0°C
The product B is
CH3 CH3 CH2

CH3
(1) Cl (2) OPOCl2 (3) (4)
Sol. Answer (4)
O OH CH 3
CH3MgBr POCl3
H2O CH3
Pyridine 0°C
4. Choose the correct statement

(1) LiAlH4 cannot reduce isolated carbon – carbon double or triple bond
(2) Borane and LiAlH4 have generally same reducing power and same mechanism
(3) LiAlH4 can reduce isolated carbon – carbon double bond
(4) LiAlH4 is a weak hydride doner than NaBH4
Sol. Answer (1)
LiAlH4 cannot reduce isolated carbon-carbon double bond even it is present in conjugation with carbonyl group.
5. 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)
(3) MgBr + N C— (4) MgBr + O
Sol. Answer (3)
MgBr + N —
—C
— C—
— N — Mg — Br
2H 2O
C—
—O Br
Diphenyl Ketone + NH 3+ Mg
OH
In other option, alcohol is formed as major product.
Solutions of Assignment Alcohols, Phenols and Ethers 131
+
H /H2O
6. CH3CH CH2 major product is:
OH
(1) CH3 – CH – CH2 (2) CH3CHCH3 (3) CH3CH2CH2OH (4) CH 3CH — CH2
Sol. Answer (2) O OH OH

Markovnikov’s addition.
7. Reaction involving ‘syn’ addition is

+ HX
(1) CH H /H2O (2) CH3CH CH2
2 CH 2
Hg(OAc)2/H2O B2H6/ THF
(3) CH 3CH CH2 NaBH4 (4) CH2 CH2 H2O2/OH
–
Sol. Answer (4)
8. Reaction involving anti addition is:

+
H /H2O HX
(1) CH2 CH2 (2) CH3CH CH2
Hg(OAc)2/H2O B2H6/ THF
(3) CH3CH CH2 NaBH4
(4) CH2 CH2 –
H2O2/OH
Sol. Answer (3)
CH3 – CH = CH2 + Hg+ – OAC CH3 – CH – CH2 H

O
 H
Hg – OAC
 H
O

H 
–H
CH3 – CH – CH2 CH3 – CH – CH 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
9. 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
H
KOC(CH3)3 [B]
10. In the reaction : — C — CH3 [A] — CH2 — CH2 — OH
(CH3)3COH
Br
The molecule [A] and the reagent [B] are
O — C(CH3)3
(1) — C — CH3 and Hg(OAc)2 / H2O followed by NaBH4
Br
(2) — CH CH2 and B2H6 / THF followed by alkaline H2O2
(3) CH — CH3 and HBr / Peroxide followed by NaOH
(4) — CH2 — CH2 — O — C(CH3)3 and H3+O
Sol. Answer (2)

Strong sterically Hindered Base gives. Less substituted alkene as major product.
H
| KOC(CH3) 3 B 2H6/THF
C — CH3 — CH2
CH — CH2— CH2— OH
| (CH3)3COH H2O2/OH¯
Br
O
[?]
11. R C — OH R CH2 — OH
Here reagent is
(1) LiAlH4 (2) NaBH4 (3) Both (1) & (2) (4) Red P/HI
Sol. Answer (1)
12. What would be the major product of the given reaction?

CH3
NaOH
C C — C — CH3
Br
CH3 CH3
(1) C C — C — CH3 (2) C C—C CH2
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
13. 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
(1) CH3CH2CH2OH (2) CH3CH2OH
(3) CH 3 – CH = CHCH2OH (4) CH3CH2CHOHCH3
Sol. Answer (4)
CH3CH2CH — CH3   

  CH3CH  CHCH3 3  2CH3CHO
2 4 Conc . H SO O / Zn
| Acetaldehy de
OH
14. 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
15. The product of the reaction
OH +
H

X; is
(1) (2) (3) (4)
Sol. Answer (3)
 
 
OH
H
+
–H 2O Ring e xpansion  –H
+
16. 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.
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
(1) [A] = and [B] =

O O
CHO
OH
(2) [A] = and [B] =
O O
COOH CHO
(3) [A] = and [B] =

O O
CHO COOH
(4) [A] = and [B] =

O O
Sol. Answer (2)
MnO2 oxidies only allylic alcohol with the protection of double bond. While PCC in CH2Cl2 oxidises allylic
alcohol as well as non allylic alcohol with the protection of double bond.
18. 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
Sol. Answer (3)
Me + Me Me
H   Ring R
O O—H
OH Contraction C——O
Me Me Me |
R
19. 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
(1) CH3CH2OCH3 (2) CH3CH2CHO (3) CH3CH2CH2OH (4) CH3CHOHCH3

Sol. Answer (3)
Because carbon atoms in carboxylic acid is same as in alcohol. So, alcohol is primary alcohol.
CH3 CH2 CH2OH  CH3 CH2 COOH

oxidation
(X) C3H8 O (Y) C3H6 O2
20. 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)
SOCl2 NaN3 Sn/HCl

OH Cl N3 NH 2
21. 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)
22. Order of nucleophilicity is

(1) CH3O– < C2H5O– (2) C2H5O– < C2H5S– (3) CH3O– < CH3S– (4) All of these
Sol. Answer (4)
23. 1° alcohols preferably undergo dehydration via

(1) E1 (2) E2 (3) SN1 (4) SN2
Sol. Answer (2)
1° alcohol do not follow in SN1 or E1.
O
18 +
24. 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)
25. 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
Cumene Phenol Acetone
26. 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.
27. 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
28. 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)
29. 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
Sol. Answer (2)

C7H8O dissolves in NaOH but not in NaHCO3. So, —OH group is directly attached to the benzene ring. C7H8-
O reacts with Br 2 to give C 7H 5 OBr 3 . So, two ortho and one para position should be vacant w.r.t.
—OH group. Hence, C7H8O (x) must be
OH
Me
30. Consider the following sequence of reactions
Me
I. KOH/CHCl3 I. Ac2O/NaOAc
+ [A] + Product (P).
II. H3O II. H , 
OH
The major product (P) in the given reaction is
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
Sol. Answer (1)
Me Me Me
Me
KOH/CHCl3 (i) Ac2O/NaOAc H+
(ii) H3O+ –H2O
CH — O O
CHO — CH — COOH
OH OH OH
31. Correct acidic order is
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
Sol. Answer (1)
32. Most acidic among the following is
OH
OH OH OH
(1) (2) (3) (4)

NO2 CH3 NO2
Sol. Answer (4)
33. Electrophile of Reimer-Tiemann reaction

(1) CHCl3 (2) : CH2 (3) : CCl2 (4) CO2
Sol. Answer (3)
34. Phenols can be distinguished from alcohols by
(1) FeCl3 (neutral) (2) Fehling solution (3) Tollen’s reagent (4) 2,4-DNP
Sol. Answer (1)
35. 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
(1) C3H7OH and C3H7ONa (2) CH3OH and CH3ONa

(3) C2H5OH and C2H5ONa (4) C2H5OH and CH3ONa
Sol. Answer (3)
Na
C2H5OH 
 C2H5ONa
(A) (B)
Conc . H SO
2C2H5OH   
2

4
 C2H5 — O — C2H5
(A) Diethyl ether
36. 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
37. 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
Sol. Answer (2)

Diphenyl ether does not react with hot conc. HI due to presence of resonance.
OCH3
CH3Br/ FeBr3
38. ? major product is
OCH3 OCH3 OCH3 OCH3

CH3
(1) (2) (3) (4)
Br
Br CH3
Sol. Answer (4)

Friedel Craft alkylation.
39. How many minimum number of carbons are needed for an optically active ether?
(1) 2 (2) 3 (3) 4 (4) 5
Sol. Answer (4)
OC2H5
40. IUPAC name of is
(1) Benzyl ethoxide (2) Ethoxy benzyl (3) Benzene ethoxide (4) Ethoxy benzene
Sol. Answer (4)
HBr
41. In the reaction OCH3 the products are [IIT-JEE-2010]
(1) Br OCH3 and H2 (2) Br and CH3Br
(3) Br and CH3OH (4) OH and CH3Br
Sol. Answer (4)

H
H—Br
O O – OH + CH3Br
Br
CH 3 CH3
42. The major product of the following reaction is [IIT-JEE-2011]
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
43. The major product(s) of the following reaction is(are) [JEE(Advanced)-2013]
OH
aqueous Br2 (3.0 equivalents)

?
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
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]
Acid
OR OH + ROH
(1) One phenyl group is replaced by a methyl group
(2) One phenyl group is replaced by a para-methoxyphenyl group
(3) Two phenyl groups are replaced by two para-methoxyphenyl groups
(4) No structural change is made to X
Sol. Answer (3)
–OCH3 group has +R effect. It increases the stability of the carbocation.
46. The major product in the following reaction is [JEE(Advanced)-2014]
O 1. CH3MgBr, dry ether, 0 °C

Cl 2. aq. acid
CH3
OH
O
(1) H3C (2) CH3
CH3 H2C
CH3
CH3
(3) CH2 (4)
O O CH3
Sol. Answer (4)
O O– CH3
Cl Cl
CH3 CH3
O
CH 3 – MgI
SECTION - B
Objective Type Questions (More than one options are correct)
1. Synthesis of cyclohexane – 1, 2-diol from cyclohexene may be accomplished in two ways :
I. MnO 4 dilute, OH, OC dihydroxylation
II. Peracid epoxidation followed by NaOH opening of the epoxide ring.

Which of the following statements about the products from these reactions is correct?
(1) Methods I and II give same product
(2) Method I gives resolvable racemic mixture while method II will give non-resolvable achiral product
(3) Method I gives non resolvable optically inactive compound while method II gives resolvable racemic mixture
(4) Products obtained through method I and II will have diasteriomeric relationship
Sol. Answer (3, 4)
In method (I), Syn addition occurs and the product is obtained is Meso form which is non resolvable optically
inactive compound. In method (II), anti addition occurs and product is resolvable Recemic mixture (equimolar
amount of d and l-form). d-form and Meso form or l-form and Meso form are diastereomers.
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) PCl5 (4) NaI (5molar solution)

Sol. Answer (1, 2, 3)
Fact.
I¯ is better nucleophile in dilute solution not is concentrated solution.
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
1. Br2 / H2 O 2. NaOH (1 eq)

(3) — CH CH2
CH3
1. Br2 / CCl4 2. NaOH (1 eq)
(4) H2C C
CH3
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
—
—
H3 C CH3 CH2Cl2 H3 C CH3

Epoxide
Br 2/H2O NaOH
(3) CH CH2 CH — CH2 (aq.) CH — CH2
||
| |
|
O
|
Br O–H
Epoxide
4. Which of the following compounds will dissolve in aq.NaOH?
OH
CH3 O
(1) — SH (2) CH3 — C — OH (3) (4) CH3 — C
CH3 O—H
Sol. Answer (1, 4)


NaOH reacts with those compounds which give more stable conjugate base than O H ion.
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.
6. Which sequence of reactions can be used to perform the given transformation?
?
— CH CH2 — CH2 — CH2 — OH
(1) (i) B2H6. THF (ii) O H/H2O2

(2) (i) Conc. H2SO4 (ii) H2O, 
(3) (i) Hg(OAC) / H2O (ii) NaBH4
(4) (i) HBr/Peroxide, h (ii) NaOH
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
7. Consider the following reaction
H2SO4
OH
OH
Probable products of the above reaction are
(1) O (2) (3) (4)

OH OH
OH O
Sol. Answer (3, 4)

CH3 CH3 CH3
H2SO4
OH OH2
OH O-H O
OR
CH3 CH3
H2SO4 –H2O Rearrangement
OH OH OH OH
OH OH2 CH3
+
–H
CHOH
3
8. Which of the following reactions will not occur?
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
Sol. Answer (2, 3)

Five or Six membered cyclic ether can’t cleaved by a base or nucleophile. Only three membered cyclic ether
can cleaved due to high strain.
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
Sol. Answer (2, 3)
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
10. What would be the products of the given reaction?
— OH
NaNO2/HCl
— NH2
pH = 9
NH2 OH
H H
(1) (2) —N—N—
OH
N N—
(3) (4) HO — —N N—
Sol. Answer (3, 4)
+ –
NH2 N2Cl
NaNO 2/HCl
Benzene diazonium Chloride

Benzene diazonium Chloride shows coupling reaction with phenol in basic medium.
+ –
N2Cl OH OH
pH = 9 N N +HO N N
||
||
+
p-hydroxy azobenzene
o-hydroxy azobenzene
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
NaOH Cyclic ether

(1) (–HCl)

H-O Cl O

OH H2SO4 OH2  –H2O, –H+
(3) HO H-O O

Cyclic ether
In alkaline medium, this reaction does not occur.
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
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
15. In the reaction NaOH(aq)/Br2 the intermediate(s) is/are [IIT-JEE-2010]
O O O O
Br
(1) (2) (3) (4)
Br
Br Br Br Br

(A) & (C) is usual product. Formation of (B) is justified as
O O
Br Br Br
Br Br
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
CH3 H3C CHCl2 H3C CHCl2 CH3

P Q R S
(1) P (major) (2) Q (minor) (3) R (minor) (4) S (major)
Sol. Answer (2, 4)

OH OH O
CHO
CHCl 3
– +
OH
CH 3 CH3 H3C CHCl2

(S) (Q)
(Major product) (Minor product)
17. The major product U in the following reaction is

+
CH2=CH–CH3, H radical, initiator, O2
high pressure,
T U
heat
H
O
O H3C CH3
CH3 O
O H
(1) (2)
O
O CH2
CH2 O H
O
(3) (4)
Sol. Answer (2)
O H
O
+
,H Radical, initiator, O2
High pressure, heat
'T' 'U'
18. In the following reaction sequence, the correct structure(s) of X is (are) [JEE(Advanced)-2018]
(1) PBr3, Et2O Me N3

X
(2) Nal, Me2CO
(3) NaN3, HCONMe2
enantiomerically pure
Me OH Me OH
(1) (2)
(3) Me (4)
OH Me OH
Sol. Answer (2)
Me OH
The correct structure of X is
Me OH Me Br Me I
PBr3 NaI
Et2O(SN2) acetone(SN2 ) NaN3, HCONMe2
(SN2)
Me N3
enantiomerically pure
Enantiomerically pure product after several substitution reactions, is only possible when each reaction must
stereospecific in nature which confirms pathway used is SN2 in nature.
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
Sol. Answer (3)
Only 2, 4, 6-trinitrophenol (Picric acid) will evolve CO2 gas with aqueous NaHCO3 due to high acidic nature.
2. Arrange the given phenols in the increasing order of acidic strength
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.
MeO OH < Me OH < OH < NC OH

MeO
(I) (II) (III) (IV)
3. Consider the following reactions
NO2 C C—H
O
NaOH (1 eq)
Major
product
NH2
OH OH
Major product of the above reaction would be
NO2 C C—H NO2 C CH

O O
(1) (2)
NH2 NH2
ONa OH OH ONa
NO2 C CNa NO2 C CH

O O
(3) (4)
NH2 NHNa
OH OH OH OH
So. Answer (1)
NO 2 —C—H
C— 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.
1. Which statement is true about base ring opening reaction of epoxide?

(1) Base catalyzed epoxide opening is nonstereo selective reaction
(2) Both acid catalyzed and base catalyzed ring opening is regioselective
(3) In acidic medium attack of nucleophile take place at less substituted carbon of epoxide
(4) Epoxides are less reactive than oxetanes
Sol. Answer (2)
Both acid catalyzed and base catalyzed ring opening is regioselective.
2. Given synthetic transformation can be performed by
OH
?
OH
O
(1) CH3 — C — OOH / H2O (2) (i) OsO4 (ii) Hydrolysis
(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
3. What would be the major product of the given transformation?

Ph
(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
O
+
NaOCH3 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.
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
(1) (2) (3) (4)
NO2 O
OH NO2
Sol. Answer (2)
2. Product (D) is more acidic than
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)
1. Which one of the following reagents is used in this above reaction?

(1) Aq. NaOH + CH3Cl (2) Aq. NaOH + CH2Cl2 (3) Aq. NaOH + CHCl3 (4) Aq. NaOH + CCl4
Sol. Answer (3)
2. The electrophile in the reaction is

(1) :CHCl (2) +CHCl (3) :CCl2 (4) ·CCl3
2
Sol. Answer (3)
3. The structure of the intermediate I is
   
O Na O Na O Na O Na
CH2Cl CHCl2 CCl3 CH2OH
(1) (2) (3) (4)
CH3 CH3 CH3 CH3
Sol. Answer (2)
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
1. Compound X is
O OH
OH
CHO
CH3 CH3
(1) (2) (3) (4)
Sol. Answer (3)
OH
Pd-BaSO4 i. B2H6
C8H6
H2 ii. H 2O2, NaOH, H2O
2. The major compound Y is
CH3 CH3
(1) (2)
CH3
CH2
CH3
(3) (4) CH3
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.
2. STATEMENT-1 : Solubility of alcohols decreases with increasing molecular weight.

and
STATEMENT-2 : Increase in hydrophobic group decreases proportion of hydrogen bonding.
Sol. Answer (1)
Fact.
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.
5. STATEMENT-1 : Resorcinol turns FeCl3 solution purple.

and
STATEMENT-2 : Resorcinol is a dihydric phenol.
Sol. Answer (2)
OH
(Resorcinol) turns FeCl3 solution purple and it is dihydric phenol also.
OH
6. STATEMENT-1 : The C — O bond length of aliphatic alcohols is less than phenols.

and
STATEMENT-2 : In phenols C — O bond acquires  bond character.
Sol. Answer (4)
In phenols, C—O bond acquires  bond character. So, C—O bond length in phenols is less than aliphatic
alcohol.
7. STATEMENT-1 : POCl3 can be used to dehydrate alcohols.
and
STATEMENT-2 : This reaction proceeds by formation of carbocation in 1st step.
Sol. Answer (3)
In the dehydration, no carbocation is formed. The reaction takes place by E2 mechanism. In CS2 solvent, I¯
acts as weak nucleophile and it gives elimination reaction.
8. STATEMENT-1 : In phenylbenzoate, Frie's rearrangements is faster than ethylbenzoate.
and
STATEMENT-2 : Phenyl acylium cation is more stable than ethylacylium cation.
Sol. Answer (1)
9. STATEMENT-1 : When phenol is treated with PBr3, it gives bromobenzene.
and
STATEMENT-2 : It is an example of nucleophilic substitution.
Sol. Answer (3)
10. STATEMENT-1 : Phenol and benzoic acid can be distinguished by NaHCO3.
and
STATEMENT-2 : Phenol releases CO2 gas from NaHCO3.
Sol. Answer (3)
11. STATEMENT-1 : Hydration of alkenes may give more than one type of alcohol.
and
STATEMENT-2 : Carbocation intermediate may show rearrangement.
Sol. Answer (1)
Hydration of alkenes starts with formation of carbocation which may undergo rearrangement.
12. STATEMENT-1 : Phenols are more acidic than carboxylic acid.
and
STATEMENT-2 : Acidity depends on resonance stabilisation of the conjugate base formed.
Sol. Answer (4)
Phenoxide ion is resonance stabilized therefore phenol can lose H+ ion showing acidic behavior, but
carboxylate ion has identical resonance structures hence is more stabilized making R—COOH more acidic.
SECTION - E
Matrix-Match Type Questions
1. Match the column-I (Chemical transformation) with column-II (Name reaction).

Column-I Column-II
(A) (p) Hydroboration oxidation

OH
(B) OH (q) Oxymercuration
demercuration
(C) CH2 — Br O (r) Markovnikoff's product

OH
Ph H Ph H
(D) CH3 – C = C – CH3 CH3 – C — C – CH3 (s) Carbocation intermediate
OH H
Sol. Answer : A(q, r), B(p), C(s), D(r, s)
(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.
 Ring
CH2 — Br NaOH CH2 

(C) O–H
–Br– expansion
OH OH
+
–H
O
||
The reaction proceeds through carbocation intermediate.
Ph H Ph
| | +
H /H2O |
(D) CH3— C —
— C — CH3 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.
2. Match the column-I with column-II

Column-I Column-II
Product/s gives test
ONa
(I) CO2
(A) + (p) With neutral FeCl3 test
(II) H3O
O—O—H
H3C CH3
C

+H
(B) (q) With NaHCO3
OH
+
NN—
Cl–
(C) (r) With Na
pH = 9
OH
I. KOH / CHCl3
(D) +
(s) With 2, 4 DNP reagent
II. H3O
Sol. Answer: A(p, q, r), B(p, r, s), C(p, r), D(p, r, s)
ONa OH
COOH
(i) CO 2
(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.
3. Match the following

Column-I Column-II
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
Me
R3N
(C) D H  (r) Rearrangement
Me
CH3 OTS
CH3 +
Conc. H
(D) Ph – CH2 – CH – CH (s) Bimolecular elimination

OH CH3
Sol. Answer A(p, s), B(q, r), C(p, q, s), D(r)
(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.

Column I Column II
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
(D) N–H N–H (s) DIBAL-H (1 eq)
(t) Reduction
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)
All are reducing agents.

Column I Column II
(A) CH3—CH—CH2 (p) CH 3—CH—CH 2
O OCH3 OH
(B) CH3—CH—CH2 (q) CH 3—CH—CH2
O OH OCH 3
O
(C) CH3—C—OC2H5 (r) CH3—CH—CH2
OH OCH3
O CH3
(D) CH3—C—O—C—CH3 (s) O18 is present in alcoholic

group
CH3
(t) O16 is present in alcoholic

group
Sol. Answer: A(q), B(p), C(t), D(s)
Column I Column II
(A) Cr2O72– + H+ (p) Aldehydes
(B) SOCl2 (q) Alkene
(C) H2SO4,  (r) Carboxylic acid
(D) PCC (s) Chloroalkane
Sol. Answer: A(r), B(s), C(q), D(p)
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
(t) Carbocation intermediate

Sol. Answer : A(r, s), B(t), C(p, q), D(r)
(A) N N + O —H
Cl–
OH
N=N O
H
N=N O
 Coupling reaction and electrophilic substitution reaction.
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
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
(A) Cl (p) (i) Hg(OAc)2; (ii) NaBH4
(B) ONa OEt (q) NaOEt
OH
(C) (r) Et-Br
(D) (s) (i) BH3; (ii) H2O2/NaOH
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
(Q) ONa + Et-Br OEt
(1) Hg(OAc)2 OH
(R)
(2) NaBH4
(1) BH 3
(S)
(2) H2O2/NaOH
OH
9. The desired product X can be prepared by reacting the major product of the reactions in Column I with one
or more appropriate reagents in Column II. [JEE(Advanced)-2018]
(given, order of migratory aptitude: aryl > alkyl > hydrogen)
O
Ph
OH
Me Ph
X
Column I Column II
Ph
HO
Ph Me + H2SO4
(A) (p) I2, NaOH
OH
Me
Ph
H2N
Ph H + HNO2
(B) (q) [Ag(NH3)2]OH
OH
Me
Ph
HO
Me Ph + H2SO4
(C) (r) Fehling solution
OH
Me
Ph
Br
Ph H + AgNO3
(D) (s) HCHO, NaOH
OH
Me
(t) NaOBr
The correct option is
(1) A(p); B(q, r); C(p, s); D(q, s)
(2) A(p, t); B(r, s); C(s, t); D(r)
(3) A(p, t); B(r, s); C(t); D(q, s)
(4) A(p, t); B(q, r); C(p, t); D(q, r)

Sol. Answer (4)
Ph Ph O O
Me Ph
I2/NaOH
(A) HO + H2SO4 Me Me C – OH
Ph HO Me Ph Me Ph
O
Ph
NaOBr
Me C – OH
Ph
A  p, t
Ph Ph O Ph
H [Ag(NH3)2]OH
(B) H2N OH + HNO2 Me Me COOH
Ph Me Ph H Ph
Ph
Fehling
Me COOH
Solution
Ph
B  q, r
Ph Ph O
Ph
(C) HO OH + H2SO4 Ph
Me Me Me Me
NaOBr I2/NaOH
Ph Ph
Me COOH Me COOH
Ph Ph
C  p, t
Ph Ph
Ph
(D) Ph OH + AgNO3 Ph CHO
Br Me Me
Fehling [Ag(NH3)2]OH
solution
Ph Ph
Ph COOH Ph COOH
Me Me
D  q, r
10. Column I contains reactions and Column II contains major products. [JEE(Advanced)-2018]
Column I Column II
(A) + (p)
ONa Br OH
(B) + HBr (q)

OMe Br
(C) + NaOMe (r)

Br OMe
(D) + MeBr (s)

ONa
O
(t)
Match each reaction in Column I with one or more products in Column II and choose the correct option.
(1) A(p, t); B(q); C(r); D(s)
(2) A(p, s); B(q); C(s); D(r)
(3) A(p, s); B(p, q); C(r, s); D(s)
(4) A(s, t); B(s); C(s); D(r, s)

Sol. Answer (2)
(A) ONa + Br + OH
with 3° halide, elimination predominates.
(B) OMe + HBr Br + MeOH
(C) Br + NaOMe
(D) ONa + MeBr OMe

A  p, s; B  q; C  s; D  r.
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
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.
3. Draw a stepwise mechanism for the following reactions
(i) + H—OSO2CF3 +
S
S
OS2CF3
CH2CH2CH—CH2
Trace OH
(ii)
O CH2OH
OH
Sol.
S S S
4. Draw a stepwise mechanism for the following reaction
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
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
Sol. Due to the position of –OH group.
7. Show how you would synthesize the following compound from any starting materials containing no more than
six carbon atoms.
O
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.
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)
Sol. (a) = Pyridinium chloro chromate

CrO3Cl
N
H
(b) PBr3
(c) (i) PBr3
(ii) NaN3
(iii) LiAIH4
10. Provide the organic products of the following reactions.

+ –
(a) K O C(CH3)3
[A]
(CH3)3COH
I
(i) NaH
(b) [B]
(ii) CH3Br
OH
O
(1) — S — Cl
O
(c) OH [C]
(2) KI
–
N + + CrO3Cl
(d) H
OH [D]
CH2Cl2
Sol. (a)
CH3
(b) CH3 — C — O — CH3
CH3
(c) I
(d) O
11. Prepare the following ethers via the Williamson's synthesis
O
(a)
CH2
(b) CH3 — CH2 — CH2 — O
CH3
(c) CH3 — C — O — CH3
CH3
— CH2 — Br
NaOH  O
Sol. (a) OH ONa
CH2
ONa O – CH2 CH2CH3
(b) + CH3 – CH2 – CH2 – Br
CH3 CH3 CH3

Na  CH3 — Br
(c) CH3 — C — OH CH3 — C — ONa CH3 — C — O — CH3
CH3 CH3 CH3
12. Give the products of the reaction of styrene oxide with

(a) NaSH
(b) LiAID4
(c) MeOH / H+
(d) HBr(1 eq)
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
13. Supply structures and names for compounds A and B.


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
H CH 3 H3C H CH3 CH3

H CH 3
Erythro-d, l-pair
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.
15. Explain briefly.
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.
16. Identify the correct compound in each case.

(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
(b) NaH
— O — CH3 No reaction
Me Me
OH ONa
NaH
+ H2
 2 - methylcyclohexanol evolves H2 with NaH.
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
(b) A chiral alcohol C4H6O
(c) A diol C4H10O2 that exists in only two stereoisomeric forms.
O CH3
H3C OCH3
and H
Sol. (a)
H
H H
CH3
OH
(b) H—C C—C —H
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
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
12n (2n  1) 16 1  74

(C) (H) (O) (H)
14n + 18 = 74
n4
Alcohol is C4H9—OH
CH3—CH2—CH2—CH2—OH
CH3
|
CH3 — CH — CH2 — OH
CH3
|
CH3 — CH2 — CH — OH


25 Alcohols, Phenols and Ethers: Solutions

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25 Alcohols, Phenols and Ethers: Solutions

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Chapter 25

Alcohols, Phenols and Ethers

CH2 – OH CH2 – OH CH2 – OH CH2 – OH

3. Consider the following reaction sequence

CH3 CH3 CH2

Sol. Answer (4)

4. Choose the correct statement

(3) MgBr + N C— (4) MgBr + O

Sol. Answer (3)

In other option, alcohol is formed as major product.

Sol. Answer (2) O OH OH

7. Reaction involving ‘syn’ addition is

Sol. Answer (4)

8. Reaction involving anti addition is:

Sol. Answer (3)

CH3 – CH = CH2 + Hg+ – OAC CH3 – CH – CH2 H

(1) — C — CH3 and Hg(OAc)2 / H2O followed by NaBH4

(2) — CH CH2 and B2H6 / THF followed by alkaline H2O2

(3) CH — CH3 and HBr / Peroxide followed by NaOH

(4) — CH2 — CH2 — O — C(CH3)3 and H3+O

Sol. Answer (2)

12. What would be the major product of the given reaction?

(1) C C — C — CH3 (2) C C—C CH2

for each molecule of the alkene. The alcohol A is

(1) CH3CH2CH2OH (2) CH3CH2OH

(3) CH 3 – CH = CHCH2OH (4) CH3CH2CHOHCH3

Sol. Answer (4)

CH3CH2CH — CH3   

Sol. Answer (4)

15. The product of the reaction

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

Sol. Answer (3)

(1) [A] = and [B] =

(3) [A] = and [B] =

(4) [A] = and [B] =

molecular formula is C3H6O2. The compound X may be

(1) CH3CH2OCH3 (2) CH3CH2CHO (3) CH3CH2CH2OH (4) CH3CHOHCH3

CH3 CH2 CH2OH  CH3 CH2 COOH

(X) C3H8 O (Y) C3H6 O2

SOCl2 NaN3 Sn/HCl

21. SN1 is observed in

Sol. Answer (1)

22. Order of nucleophilicity is

23. 1° alcohols preferably undergo dehydration via

Sol. Answer (1)

25. Reagents required to perform the given transformation is

Cumene Phenol Acetone

Sol. Answer (2)

30. Consider the following sequence of reactions

Sol. Answer (1)

31. Correct acidic order is

Sol. Answer (1)

32. Most acidic among the following is

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

Sol. Answer (4)

33. Electrophile of Reimer-Tiemann reaction

(1) C3H7OH and C3H7ONa (2) CH3OH and CH3ONa

Sol. Answer (2)

OCH3 OCH3 OCH3 OCH3

Sol. Answer (4)

40. IUPAC name of is

Sol. Answer (4)

(1) Br OCH3 and H2 (2) Br and CH3Br