Alcohol, Phenols and Ethers

DPP – VI
Level – I : JEE(Main) + NEET
1. (a) Both react with Na to liberate H2 gas.  Cannot be distinguished. FeCl3, Br2/H2O and NaOH react only with
Phenol.
2. (c)

OH

p-Nitrophenol is more symmetrical.  forms a more stable lattice. Hence has higher m.pt.

NO2

3. (b)
Since alcohol contains two more carbon atoms, therefore choice has to be between CH3CHO and CH2 CH2 .
O
o o
CH3CHO gives 2 alcohol and CH2 CH2 gives 1 alcohol.
O
O OH
|| |
RMgX  CH3  C  H  R  C  CH3 2o alcohol  Mg  OH  X
H3O 

|
H
H3O+
RMgX + CH2 CH2 RCH2CH2OH + Mg(OH)X
O
4. (b)
OH OH OH
Br
Br2/CS2
+ Monosubstitution takes palce in CS2.

Br
5. (b)
OH
|
It is Lucas Test reaction. CH3  C  CH3 (2-hydroxy-2-methylpropane) being a 3o alcohol gives turbidity
|
CH3
immediately.
6. (b)
O O
|| ||
Cl2 Cl2 NaOH
CH3CH2OH   CH3  C  H   Cl3C  C  H   CHCl3  HCOONa
Oxidation Chlorination Hydrolysis
7. (a)
O OH
|| |
H2O / H
CH3MgBr  CH3  C  CH3  CH3  C  CH3 + Mg (OH)Br
|
CH3
8. (d)

1
 HBO OH
Pentan-1-ol
9. (a,b)

OH OH
COOH
CCl4
NaOH
Riemer Tiemann Reaction

OH OH
COOH
(i) NaOH
(ii) CO2, 410K, 4-7 atm
(iii) HCl Salicylic Acid.
Kolbe's Reaction

10. (b)

CH3 CH3
H3C C O OH OH O
CH
CH3
O2 H+
+ H3C CH3
H2O

Cumene Cumene
hydroperoxide
11. (b)
H Cl
HO + C H2O + :CCl2 + Cl
Cl Cl
: CCl2 is electrophile.
12. (b)
OH OH O OH OH OH OH
+  H3O+ 
CHCl3 C H HCN C CN C COOH
NaOH
Riemer H H
CH3 Tiemann CH3 CH3 CH3
Reaction
(A) (B)
13. (a)
N
H H
C O S
Cl

C O S
Cl H H
= 0 N
= 0  0  0

14. (b)

2
 OH OH OCOCH3
ONa COONa
o
125 C COOH COOH
+ CO2 H+
5 atm AC2O
(B) (C)
15. (d) According to the given conditions, compound (d) neither reacts with neutral ferric chloride solution
(Reaction with FeCl3 is a test for phenol) nor with Fehling solution (Test for aldehydes is Reaction with Fehling
solution) . It however reacts with Grignard reagent and gives positive iodoform test.
 As the compound does not contain any phenolic – OH group. Hence, it gives negative neutral FeCl3 test.
OH

CH3 Neutral
no reaction
C Et FeCl3
(FeCl3 test for phenolic
group)
O
 Compound gives reaction with
RMgX as it contains  C  Et
||
O

Compound with CH3 C H  group undergoes iodoform test in presence of NaOH and I 2
|
OH

16. (a) The major product when m-cresol reacts with propargyl bromide (HC ☰ C  CH2Br) in presence of K2CO3 in
acetone is given in the following reaction : CO23  ion withdraws an H+ as it is a stronger base (being a
conjugate base of weak acid).

In step 1 K2CO3 act as a base and abstract H-atom from – OH group.

This leads to the formation of substituted phenoxide ion (highly stable).
In step 2 substituted phenoxide ion on reaction with Br  CH2  C ☰ CH gives the required product.
17. (b) The given process is cumene process (Hock process) to synthesise phenol and acetone industrially. In
Hock process, Ph  group migrate and release H2O.

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18. (b) Acidic strength is inversely proportional to pK a value. The acidity of phenols is due to greater resonance
stabilisation of phenoxide ion relative to phenol.
Therefore, any substituent which stabilises the phenoxide ion more by dispersal of negative charge will tend
to increase the acidity of phenol.
Electron withdrawing groups ( NO2) increases the acidic strength of phenol whereas electron donating
group (– OCH3) decreases the acidic strength of phenol. In case of – NO2 group attached to phenol, the
dispersal of negative charge is more pronounced to o- and p-position than at m-position.
Thus, order of acidic strength of nitrophenol is :
p-nitrophenol > o-nitrophenol and the correct order of the pKa values of give option is

19. (c) Substituted phenols react with with aq. NaOH to form sodium phenoxides which on reaction with CH3l
undergoes SN2 reaction to give 2-methoxy-1-methyl

20. (c)
OH

In , ipso-substitution takes palce with the carbon bearing -SO H group.

3

SO3H
After the attack of the electrophilic Br+ in the rate determining step (rds) of the ArSE2 pathway desulphonation
(– SO3) takes place with faster rate.

4
21. (b) The major product formed in the reaction is as follows :

O
HO (1) CrO3
(2) SOCl2/ HO
HO (3) 
Primary alcohol readily oxidised to corresponding carboxylic acid with oxidising agent, chromium trioxide
(CrO3) in acidic medium.

COOH
HO
CrO3

HO HO
 OH group of carboxylic acid get substituted by  Cl in presence of SOCl2 (Thionyl chloride).

COOH COCl
SOCl2/
+ SO2 + HCl
HO HO
Further, heating of product leads to intramolecular cyclisation.

COOH
C O

HO
HO


22. (c) The substrate undergoes nitration reaction (ArSE2). The electrophile NO2  will prefer to attack benzene
nucleus which is rich with electron density (by + R or + I-effect of substituent where + R > + I) as wall as
sterically less crowded.
Out of three substituents, the – OH group will dominate the rate of initiation reaction, because – OH has
strong ring activating property by its + R of + M effect.
The ring activating order is
OH  CH3  NO2
  R effect  (  ve hyper  R effect 
conjugation)

5
23. (69.00)

OH OH
CHO
NaOH
+ CHCl3

P(Salicylaldehyde)

Molecular formula of product ‘P’ = C7H6O2

So, mass % of C in ‘P’

12  7
  100  68.85%  69%
84  6  32

24. (c)
Only bromine water gives tribromo products, while all other gives monobromo product in which para
bromo is major product.
OH OH
Br Br
+ Br2/water

Phenol
Br
2, 4, 6-tribromophenol
(major product)
When phenol reacts with bromine in the presence of CS 2, FeBr3, CHCl3, it results in the formation of two
products. The products is ortho bromophenol and para bromophenol. The major product of this reaction is
p-bromophenol because no steric hindrance is present at para position.

6
 OH OH OH
Br
+ Br2 in CS2 273 K
+
or Br2/FeBr3
Phenol or Br2/CHCl3 (Minor product)
o-bromophenol Br
(Minor product)
p-bromophenol
25. (d) In SN2 (reaction, no formation of carbocation takes place. The nucleophile here which is phenoxide
attacks from the back side to the carbon bearing the leaving group (bromide ion).
OH
O
Br SN2
+
K2CO3/
Acetone
Phenol
In SN2 mechansim
 + 
Nu R X |Nu......R+......X| Nu R + X
Bond formation and bond
breaking takes place at the
same time (intermediate)
Here, in the question
O K
O
SN2
+ Br

So, here option (d) is correct.

26. (b) Bromination of phenol with excess of bromine and water will result in multiple substitution around ring
as water ionises phenol to phenoxide ion, which activate the ring for trisubstitution, while less polar
solvent, i.e., CS2 will give mono-substituted compound.
OH OH
Br
Br
+ Br2(excess)

Phenol
Br
(A)
2, 4, 5 tribromophenol
OH OH

Br2
CS2 < 5oC
Phenol
Br
(B)
mono-substituted product
27. (b) Phenol on reaction with Br2 in CS2/273 undergoes an electrophilic substitution reaction by Br+
(electrophile) in aprotic solvent CS2 to give 4-bromophenol as the major product.

7
 OH OH OH
Br2 in CS2/273K Br
+
Phenol
Br CHO
4-bromophenol 2-bromophenol
(major) A (minor)
Phenol on reaction with CHCl3, NaOH followed by hydrolysis gives salicyladehyde as a major product.
It is Reimer-Tiemann reaction. It is also an electrophilic substitution reaction of phenol by dichlorocarbene
CCl2 (electrophilic).
OH OH
OH
(i) CHCl3, NaOH CHO
(ii) H3O+ +
Phenol
2-hydroxybenzaldehyde
or CHO
Salicylaldehyde 4-hydroxybenzaldehyde
(major) (B) (minor)
28. (d) Statement I is true. Because of closer proximity (1, 2-positions) of –OH and –NO2 groups, o-nitrophenol
shows intramolecular hydrogen bonding.

H Intramolecular
 H-bonding
O O

N
O

o-nitrophenol
So, o-nitrophenol exists in monomeric state and becomes steam volatile. Statement II is false, because, due
to the presence of intramolecular hydrogen bonding, boiling point and melting point of o-nitrophenol will
be lower.
Note p-nitrophenol is the positional isomer of o-nitrophenol. p-nitrophenol shows intermolecular hydrogen
bonding and so, it has higher boiling point, melting point and water solubility.
Inramolecular
O H-bonding O
HO N
O HO N
O
p-nitrophenol

29. (b) Phenol is acidic in nature as after removing H+ ion, phenoxide ion is stablised by resonance.

OH O

+ H

(X) Stable due

to resonace
Phenol is although acidic but it is not soluble in NaHCO3 solution.
However, it gives violet colour with neutral FeCl3 solution.

8
 OH

6 + FeCl3 [(Ph O)6 Fe]3

Violet colour
Hence, compound ‘X’ is phenol
30. (30)
SO3H

Oleum % yield = 60 %

n moles 60% of n = 0.6 n

SO3H OH

NaOH (excess)
% yield = 50 %
H+
0.6 n 0.6  0.5 n = 0.3 n
0.3n
Overall % yield of reactions =  100
n
= 30
31. (c) Phenol in presence of sodium hydroxide reacts with chloroform to form salicylaldehyde. The reaction is
known as Reimer – Tiemann reaction.
OH OH
CHO
(i) NaOH
CHCl3 + Aq. NaOH + [X]
(ii) H+

32. (7)

9
 OH OH OH
NO2
dil. HNO3
+

(P) (A) (B)

NO2
conc. HNO3 Intramolecular
H-bonding Intermolecular
H-bonding

OH
NO2
O2N

Picric acid (C)

NO2
Strong acid
(yellow compound)

33. (b)

ON H2N
NaNO2 NH4SH
HCl H2O
OH OH OH

A B
34. (a)

HO H Conc.
O H2SO4
O C C O
-H2O
HO H

HO O
C C O

HO

Phenolphthalein
35. (a) Aromatic compounds burns with sooty flame
OH OH OH
Br
CS2
+ Br2 +

(C6H6O) (Minor)
Br
(A)
(Major)
(B)
36. (b) Due to –M effect of –NO2 group, it increases acidity +M effect of N (CH3)2 decreases acidity.
Hyperconjugation of isopropyl decreases acidity
 order of acidic strength.
(c) > (a) > (d) > (b)
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37. (b) Order of acidity for following phenol is

OH OH OH OH OH
Me
NO2
> > > >
Me
NO2 NO2 Cl Me
(a) (b) (e) (d) (c)

–M and –I effect of the substituents increase acidity

+ M and +I effect of the substituents decrease acidity

Level – II : JEE(Advanced) / AIIMS / KVPY / Olympiad

38. (c)
1
3 2

3 2

1, 3-diaxial interactions. If groups like OH are present, preferred position are axial positions so that they can

develop H-boding and provide stability. If alkyl groups or any other group which cannot develop attractive

forces, then preferred positions are equitorial positions.

39. (b)
OH OH OH

 EWG increases
acidic character
CH3 NO2 ERG decreases
(ERG) (EWG) acidic character

40. (a)

O OH
1/2 O2 Steam
CH2 = CH2 Ag CH2  CH2 473 K
CH2  CH2 Ethylene glycol.
(x)
OH


Aq.NaOH Na CH I
41. (b) CH3CH2Br 
 CH3CH2OH 
 CH3CH2ONa 
3
 CH3CH2OCH3
 A B   C
Ethyl methyl ether

42. (c)

CH3 CH3
OMD 1 OH
2
H

1-Methylcyclohexanol (Markownikov Addition of H 2O)

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43. (d)

CHCl3  NaOH  : CCl2  H2O  Na  Cl

OH O

 + H+

O O O O
O
H CHCl2
CCl2 + 2NaOH CHO
CCl2  2NaCl
 H2O

O O Na
CHCl2 CHCl2
Intermediate obtained is or

44. (a)
OH O O O O
Br Br Br
NaOH Br2 Br2 Br2
 H2O  Br  Br  Br
(I) Br
Br Br
(II) (III) (IV)
45. (b)
+H+ + +
CH3 CH CH OH CH3 CH CH2 OH + CH3 CH2 CH OH
(Minor) (Major)
Less stable More stable
Br Br
Br
CH3 CH CH2 OH CH3 CH2 CH OH
Minor Br
Major
No substitution of Phenolic –OH group.
46. (a,b,c)
OH
a c

C(CH3)3
b
Bulky group – C(CH3)3 will exert steric effect (repulsive forces). Its effect will be mainly observed with bulky
nucleophiles.

 OH is o, p-directing.
 Preferred sites a, b, c
 b, c not preferred by bulky nucleophile due to presence of bulky – C(CH3)3 group.
 Cl can attak a, b, c

Br can attack a & b

I can attack only a.

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47. (6)

C8H10O2 gives FeCl3 test means it has phenolic group. It rotates planes polarized light means it is optically
active.
OH
OH OH OH

OH

OH
I III V
OH OH
OH OH
OH

IV OH
II m
o VI
p
I II
o o
(Enantiomers)
III IV
m m
(Enantiomers)
V VI
p p
(Enantiomers)
48. (a)
NaOH will lead to tautomerism.
OH O O
O
+  +  Me
 NaOH
H2O
Na Me  I
H
HO OH O O O O
O O
Ultimately

O
O O Me Me
D2O
Also Note CH3 C CH3 D3C C CD3 Me Me
NaOD
O O
Me Me
49. (b)
Electron withdrawing group increases the acidic strength of phenols whereas electron donating group
decreases the acidic strength of phenols .
o-Nitrophenol is little less acidic than p-nitrophenol due to intramolecular H-bonding which makes loss of a
proton little difficult.
H
O O
N
+ O

H-bonding in o-nitrophenol
50. (a)
51. (d) – OCH3 shows – I-effect.

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52. (d) Resorcinol is more acidic than hydroquinone. Both – OH groups are at m-position in resorcinol, thus,
– OH group show – I-effect on the other – OH group which makes resorcinol more acidic than
hydroquinone.
53. (b)
OH OH O OH
NO N
HNO2

(X)
OH
, H2SO4
O
N
OH

Similarly we could have obtained para isomer.

(a) Will not be formed as ring bearing – OH group is not aromatic.
54. (d)

SO3H ONa OH

1. Oleum 2. Molten NaOH 3. H3O+

D
(X)

OH ONa ONa
COOH
1. Oleum 2. CO2
3. H3O+
(X) (Y)

OH
X=

CO2H

Y=
OH

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