Alcohols, Phenols and Ethers: Section-A

Alcohols, Phenols and Ethers (Solutions) Solutions of Assignment (Set-2)
12Chapter Alcohols, Phenols and Ethers

Section-A
Q.No. Solution
1. Answer (3)
Because carbon atoms in carboxylic acid is same as in alcohol. So, alcohol is primary alcohol.
CH3 CH2CH2 OH ⎯⎯⎯⎯→
oxidation
CH3 CH2COOH
(X) C3H8 O (Y) C3H6 O2
2. Answer (3)
2R – Mg – x R
HCOOCH3 H — C — OH
H2O
R
Secondary alcohol
3. Answer (4)
CH3 CH2CH — CH3 ⎯⎯ ⎯Δ⎯ ⎯ ⎯→ CH3 CH = CHCH3 ⎯⎯3 ⎯
O / Zn
Conc. H2SO 4
⎯→ 2CH3 CHO
| Acetaldehyde
OH
4. Answer (1)
C6H6OH is phenol because it gives violet colour with neutral FeCl3 and produces no effervescence with
NaHCO3.
5. Answer (1)
OH
CO2 COO COOH
Under Pressure
Sodium Phenoxide Salicylic Acid
6. 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 CH2 — CH — OCH3
7. Answer (2)
LiAlH4 reduces —COO—, —COCl and groups. While NaBH4 reduces and
— COCl group not —COO— group.
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- 18 -
Solutions of Assignment (Set-2) Alcohols, Phenols and Ethers (Solutions)
Q.No. Solution
8. Answer (4)
O OH CH3
CH3MgBr POCl3
H2O CH3
Pyridine 0°C
9. Answer (1)
LiAlH4 cannot reduce isolated carbon-carbon double bond even it is present in conjugation with
carbonyl group.
10. Answer (3)
C 2H5 OH ⎯⎯→
⎯ C 2H5 ONa
Na
(A) (B)
2C 2H5 OH ⎯⎯ ⎯⎯⎯ ⎯→ C 2H5 — O — C 2H5

Conc . H2SO 4
(A) Diethyl ether
11. Answer (3)

⊕ ⊕
: :
OH
+ +
H –H2O Ring expansion ⊕ –H |
12. 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.
CH3 CH3
| |
CH3 — C — Br + CH3CH2ONa → CH3 — C + NaBr + CH3CH2OH
| ||
CH3 CH2
13. 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)
14. Answer (2)

C7H8O dissolves in NaOH but not in NaHCO3. So, —OH group is directly attached to the benzene ring.
C7H8O reacts with Br2 to give C7H5OBr3. So, two ortho and one para position should be vacant w.r.t.
—OH group. Hence, C7H8O (x) must be
OH
Me
- 19 -
Q.No. Solution
15. Answer (4)
The greenish blue colour is due to presence of Cr3+ which is obtained by the reduction of K2Cr2O7.
16. Answer (3)
—
MgBr + N —
—C C—
— N — Mg — Br
2H2O
C—
—O Br
Diphenyl Ketone + NH3↑ + Mg
OH
In other option, alcohol is formed as major product.
17. 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. Answer (2)
Strong sterically Hindered Base gives. Less substituted alkene as major product.
H
| KOC(CH3)3 B2H6/THF
C — CH3 — CH2
CH — CH2— CH2— OH
| (CH3)3COH H2O2/OH¯
Br
19. Answer (2)
Diphenyl ether does not react with hot conc. HI due to presence of resonance.
20. Answer (1)

Me Me Me
Me
KOH/CHCl3 (i) Ac2O/NaOAc H+Δ
+
(ii) H3O –H2O
CHO CH —
— CH — COOH O O
OH OH OH
21. Answer (3)
Me Me Me
H+ ⊕ ⊕ Ring R
O: O—H
OH Contraction C——O
Me Me Me |
R
- 20 -
Q.No. Solution
22. Answer (3)

CH3
| CH3
|
—
C—
— C — C — CH3 C——C—
—C
|
| | CH3
Br OH
HO
CH3
C CH C
CH3
O
23. Answer (1)

O—O—H
OH
+
O2 H3O
+ —
—O
cumene Phenol Acetone
24. Answer (2)

SOCl2 NaN3 Sn/HCl
OH Cl N3 NH2
25. Answer (4)
26. Answer (2)

Markovnikov’s addition
27. Answer (4)
28. Answer (3)

CH3 – CH = CH2 + Hg+ – OAC CH3 – CH – CH2 H
⊕
O
H
Hg – OAC
⊕ H
O
⊕
H δ⊕
–H
CH3 – CH – CH2 CH3 – CH – CH2
Hg – OAC Hg – OAC
δ⊕
OH OH
NaBH4
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
- 21 -
Q.No. Solution
29. Answer (4)

O O
O3 H2O LiAlH4
RCH CH2 RCH CH2 RCHO + HCHO RCH2OH + CH3OH
O
30. Answer (1)
31. Answer (4)
32. Answer (2)

1° alcohol do not follow in SN1 or E1.
33. Answer (1)
34. Answer (1)
35. Answer (1)
36. Answer (4)

Freidel Craft alkylation
37. Answer (4)
38. Answer (1)
39. Answer (3)
40. Answer (4)
41. Answer (4)

⊕
H
H—Br
O O – OH + CH3Br
Br
CH3 CH3
42. Answer (2)

H
– H⊕ :O – CH2 – R
:
CH2
O O O O R
H
⊕
–H
CH2 – R
O O
An acetal
- 22 -
Q.No. Solution
43. 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.
44. Answer (2)

OH OH
Br Br
aqueous
Br2 (3.0 equivalents)
SO3H Br
Section-B
Q.No. Solution
1. 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. Answer (1, 2, 3)
Fact. I¯ is better nucleophile in dilute solution not is concentrated solution.
3. Answer (1, 2, 3)
O O
|| | O
Br2(1 eq.)
(1) C — CH3 C — CH2 C — CH2
| | |
Br Br Br
Epoxide
O
|| O
H CH3 m– Cl – C H – C –O – OH H CH3
—
(2) C—
6 4
—C C—C
—
—
H3C CH3 CH2Cl2 H3C CH3

Epoxide
Br2/H2O NaOH
(3) CH CH2 CH — CH2 (aq.) CH — CH2
||
| |
|
|
O
Br O–H Epoxide
4. Answer (1, 4)
Θ
NaOH reacts with those compounds which give more stable conjugate base than O H ion
- 23 -
Q.No. Solution
5. 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. Answer (1, 4)
B2H6/THF H2O2/OH¯
(1) CH CH2 CH2 — CH2 — B CH2 — CH2 — OH
||
HBr/Peroxide NaOH
—CH CH2 CH2 — CH2 — Br CH2 — CH2 — OH
||
(4)
7. Answer (3, 4)
CH3 CH3 CH3
H2SO4
OH OH2
O
:
OH O-H
OR
CH3 CH3
H2SO4 – H2O Rearrangement
OH OH OH OH
OH OH2 CH3
+
–H
OH
CH3
8. 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. Answer (2, 3)
OH ONa OH
(i) NaOH COOH H O+ COOH
3
(2)
(ii) CO2
o-Salicylic Acid
OH ONa OH
NaOH/CCl4 COOH H O+ COOH
3
(3) Reimann Tiemann
Reaction o-Salicylic Acid
- 24 -
Q.No. Solution
10. Answer (3, 4)

+ –
NH2 N2Cl
NaNO2/HCl
Benzene diazonium Chloride

Benzene diazonium Chloride shows coupling reaction with phenol in basic medium.
+ –
N2Cl OH OH
N N +HO N N
||
||
pH = 9
+
p-hydroxy azobenzene
o-hydroxy azobenzene
11. Answer (1, 3)
NaOH Cyclic ether

:
(1) H-O Cl (–HCl) O
⊕
OH H2SO4 OH2 Δ –H2O, –H+
(3) HO H-O O
:
Cyclic ether
In alkaline medium, this reaction does not occur.
12. Answer (3, 4)
Fact.
13. Answer (1, 2, 3)

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 O Me O Me + OH
Mg/Ether O2 H3O
(3) Boil
Catechol
14. 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.
- 25 -
Q.No. Solution
15. Answer (1, 2, 3 )
(A) & (C) is usual product. Formation of (B) is justified as
O O
Br Br Br Br Br
16. Answer (2, 4)

OH OH O
CHO
CHCl3
– +
OH
CH3 CH3 H3C CHCl2

(S) (Q)
(Major product) (Minor product)
Section-C
Q.No. Solution
Comprehension-I
1. Answer (3)
Only 2, 4, 6-trinitrophenol (Picric acid) will evolve CO2 gas with aqueous NaHCO3 due to high acidic
nature.
2. 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. Answer (1)
NO2 C—
—C—H
— NO2 —
C—
—C—H
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.
- 26 -
Q.No. Solution
Comprehension-II
1. Answer (2)
Both acid catalyzed and base catalyzed ring opening is regioselective.
2. Answer (1)
Formation of epoxide and then ring opening is the anti addition.
O
|| OH
CH3 — C — OOH H2O
O
OH
3. Answer (3)
Ph Ph Ph
NaOCH3 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.
Comprehension-III
1. Answer (2)
2. Answer (4)
Comprehension-IV
1. Answer (3)
2. Answer (3)
3. Answer (2)
Section-D
Q.No. Solution
1. Answer (1)
In Victor Meyer’s test, primary alcohol gives Red Colouration while secondary alcohol gives blue
colouration.
2. Answer (1)
Fact
- 27 -
Q.No. Solution
3. Answer (1)
Fact.
4. 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.
Answer (2)
OH
(Resorcinol) turns FeCl3 solution purple and it is dihydric phenol also.

OH
6. Answer (4)
In phenols, C—O bond acquires π bond character. So, C—O bond length in phenols is less than
aliphatic alcohol.
7. 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. Answer (1)
9. Answer (3)
10. Answer (3)
11. Answer (1)

Hydration of alkenes starts with formation of carbocation which may undergo rearrangement.
12. 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
Q.No. Solution
1. 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.
- 28 -
Q.No. Solution
||
(B) OH
The reaction is hydroboration oxidation. The net result of this reaction is the addition of H2O
according to Anti-Markownikoff’s rule.
(C) NaOH ⊕ Ring
:
CH2 — Br CH2 ⊕ 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.
2. 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 CH3
C OH
+
H CH3
(B) + 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
- 29 -
Q.No. Solution
OH OH
(i) KOH/CHCl3 CHO
(D)
(ii) H3O+
Salicyldehyde
Product reacts with neutral FeCl3 and Na due to —OH group and reacts with 2, 4-DNP due to
—CHO group.
3. Answer : A(p, s), B(q, r), C(p, q, s), D(r)
(A) D Base
H
Δ CH3
CH3 (E2) Saytzev's product
O Cl
P O
Cl
It also involves isotopic effect.
D D
+H rearrangement
(B) H CH3 Product
Slow
CH3 CH3
OH D
Product
Me Me
R3N
(C) D H Δ
Me Me
Me OTs Me
(D) Also involve carbocationic formation followed by rearrangement.
4. Answer : A(p, r, t), B(p, q, r, s, t), C(q, s, t), D(p, r, t)
–CN ⎯⎯
x
→ —CH2 — NH2 (x may be Li, AlH4 and H2/Pd)
O OH
(x may be Li, AlH4, NaBH4 DIBAL and H2/Pd)
x
—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
5. Answer : A(q), B(p), C(t), D(s)
6. Answer : A(r), B(s), C(q), D(p)
- 30 -
Q.No. Solution
7. 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.
(B) OH OH OH OH2
+H
CH3 — C — C — CH3 CH3 — C — C — CH3
CH3 CH3 CH3 CH3
O CH3 OH
CH3
CH3 — C — C — CH3 CH3 — C — C
CH3
CH3 CH3
Carbocation intermediate
O OH
O H3O
+
LiAlH4 H
C C H C H
(C) Nucleophilic addition
CH3
CH3 CH3
Racemic mixture
Nucleophilic
H Base S substitution S
(D)
S Cl Cl
B
8. Answer (1)
NaOEt
(P) Cl
(Q) ONa + Et-Br OEt
(1) Hg(OAc)2 OH
(R)
(2) NaBH4
(1) BH3
(S) (2) H2O2/NaOH
OH
- 31 -
Section-F
Q.No. Solution
1. Answer (4)
O
||
CH3NH2 , CH3 − C − CH3 ,
OH and H – C ≡ C – H are less acidic than C2H5OH.
2. Answer (2)
CH3 CH3
HO H and H OH
⎯⎯⎯⎯⎯⎯⎯
→
aminohydroxylation
H NH2 H2N H
CH2 CH3
3. Answer (4)
CH3—CH2—CH2—CH—CH 3 (d, l)
OH
CH3
CH3—CH—CH—CH 3 (d, l)
OH
4. Answer (5)
OH
2x = 10
x=5
CH3
C2 H5
Section-G
Q.No. Solution
1. 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. Answer (3)
OsO4 make syn addition
Section-H
Q.No. Solution
1.
O
O O
CH2—S(CH3)3 CH2—S(Me)2 CH2 + S(Me)2
- 32 -
Q.No. Solution
2. Option (2) and (3) will react with periodic due to formation of favourable conformer.
3. H
S S S
4. The reaction will involve epoxidation followed by acid catalyzed ring opening.
5. Mg
Br THF MgBr
Excess
C
Cl Cl
OMgBr
H3O
OH
6. Due to the position of –OH group.
7. O
OMgBr
H—C
MgBr + CH
+
(i) H3O
+
(ii) H , Δ
O mCPBA
CH2Cl2
CH CH
8. The reaction occurs syn to the hydroxy methyl group.
9.
(a) = Pyridinium chloro chromate
CrO3Cl
N
H
(b) PBr3
(c) (i) PBr3 (ii) NaN3 (iii) LiAIH4
10. CH3
(b) CH3 — C — O — CH3

(a)
CH3
(c) I (d) O
- 33 -
Q.No. Solution
11.
— CH2 — Br O
NaOH ⊕
(a) OH ONa
CH2
ONa O – CH2CH2CH3
(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. OH
(i) NaSH
+ Ph — CH — CH2 — SH
(ii) H3O
OH
O
Ph — CH — CH2D
(i) LiAID4
+
(ii) H3O
Ph — HC CH2 OMe
Styrene oxide ⊕
MeOH / H
Ph — CH — CH2 — OH
Br
HBr (1 eq.)
Ph — CH — CH2 — OH
13. CH3 CH3

H3C H O
+ H OH HO H
CH3COOOH H /MeOH +
C C C C H OMe MeO H
CH2Cl2
H CH3 H3C H CH3 CH3
H CH3
Erythro-d, l-pair
14. (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. Θ
O CH3 is a strong base and hence a bad leaving group, hence both the ethers are inert towards
nucleophilic attack.
16. Me OH HO Me Me H H Me
(a)
H H H H H OH OH H
A B C D
- 34 -
Q.No. Solution
(b) NaH
— O — CH3 No reaction
Me Me
OH ONa
NaH
+ H2↑
∴ 2 - methylcyclohexanol evolves H2 with NaH.
17. O CH3
H3C OCH3
(a) and H
H
H H
CH3
OH
(b) H—C C—C—H
CH3
H H OH
(c) (i) CH3 – CH2 – C — C – H (ii) CH2 – CH2 – C – CH3
OH OH OH H
18. SOCl2 Mg / Et2O
CH3 — OH CH3 — Cl CH3MgCl
X
OH
PCC (i) CH3MgCl (X)
OH O +
(ii) H3O
19. Br
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
- 35 -

Alcohols, Phenols and Ethers: Section-A

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Alcohols, Phenols and Ethers (Solutions) Solutions of Assignment (Set-2)

12Chapter Alcohols, Phenols and Ethers

10. Answer (3)

2C 2H5 OH ⎯⎯ ⎯⎯⎯ ⎯→ C 2H5 — O — C 2H5

(A) Diethyl ether

11. Answer (3)

12. Answer (2)

13. Answer (2)

14. Answer (2)

15. Answer (4)

16. Answer (3)

In other option, alcohol is formed as major product.

17. Answer (2)

18. Answer (2)

19. Answer (2)

20. Answer (1)

21. Answer (3)

22. Answer (3)

23. Answer (1)

24. Answer (2)

25. Answer (4)

26. Answer (2)

27. Answer (4)

28. Answer (3)

29. Answer (4)

30. Answer (1)

31. Answer (4)

32. Answer (2)

33. Answer (1)

34. Answer (1)

35. Answer (1)

36. Answer (4)

37. Answer (4)

38. Answer (1)

39. Answer (3)

40. Answer (4)

41. Answer (4)

42. Answer (2)

43. Answer (4)

44. Answer (2)

H3C CH3 CH2Cl2 H3C CH3

10. Answer (3, 4)

Benzene diazonium Chloride

11. Answer (1, 3)

NaOH Cyclic ether

(1) H-O Cl (–HCl) O

In alkaline medium, this reaction does not occur.

12. Answer (3, 4)

13. Answer (1, 2, 3)

14. Answer (1, 4)

15. Answer (1, 2, 3 )

(A) & (C) is usual product. Formation of (B) is justified as

16. Answer (2, 4)

CH3 CH3 H3C CHCl2

MeO OH < Me OH < OH < NC OH

(Resorcinol) turns FeCl3 solution purple and it is dihydric phenol also.

10. Answer (3)

11. Answer (1)

12. Answer (4)

1. Answer : A(q, r), B(p), C(s), D(r, s)

(C) NaOH ⊕ Ring

2. Answer : A(p, q, r), B(p, r, s), C(p, r), D(p, r, s)

3. Answer : A(p, s), B(q, r), C(p, q, s), D(r)