Page 1 of 14 CPP - SANKALP_AEP-10-PH-V

CPP - SHEET – 10
CHEMICAL PROPERTIES OF PHENOL
SUBJECTIVE (LEVEL -1)
1. Convert phenol to p-aminophenol.

2. Predict product of the following reaction.

OH


NaOH H3O
 CHCl3    ?

3. Pyrrole also undergo Reimer-Tiemann’s reaction like phenol but besides a normal formylation, some unusual
reaction occur simultaneously forming the 2nd product in the following reaction.
Cl

OH
 CHCl3   CHO 
N N
H H N
Explain the formation of chlorpyridine in the above reaction.

4. Aspirin, a common analgesic, is prepared by acetylation of salicylic acid. Synthesize aspirin using phenol as
starting compound, once using CHCl2 and in another case using CCl4.

5. Synthesize aspirin via Kolbe’s method. (With mechanism)

6. Starting from phenol, synthesize o-dihydroxybenzene.

7. Identify the lettered compounds in the following synthetic road maps:

OH
KOH
 HBr A(C8H9 OBr)   B(C8H8O)
I) Inso lub le in NaOH(aq)

OH

OCH3

Mg
 HBr  C (C9H11OBr) 
Ether
 D(C18H22O2 )
II)

HC CH2

Heat
D  HBr   E(C16H18O 2 )

8. Propose mechanism of the following reaction.

CH3 O
14
H 2C CH CH 2Cl
NaOH
HO C OH 
H2O
 


CH3

CH3
O
14
HO C OC H2

CH3

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SUBJECTIVE (LEVEL -2)

1. Predict the reaction of PhOH with PCl5.

2. Complete
OH 
Zn / H3O
 

Ni / H2

160o C

PCl5
 
3. Convert
(a) Phenol to Aspirin
(b) Phenol to Salicylic acid
(c) Phenol to Bakelite
(d) Phenol to Phenolphthalein
(e) Phenol to o-allylphenol

4. Give the mechanism of the Reimer Timan reaction on indole.

5. Predict ‘A’ and ‘B’ are, respectively

O

PhCH2 I PhCH2 I
A 
CF3CH2OH
 
DMSO
B

6. An organic compound (X) on treatment with CHCl3 and KOH gives (Y) and (Z) both of which in turn gives the
same compound (T) when distilled with Zn. Oxidation of (T) yields (S) of formula C7H6O2. The sodium salt of
(S) with soda lime gives (P) which an also be obtained by distilling (X). Identify X, Y, Z, T, S, and P.

7. Identify the end product (Y) of the following sequence of reaction:

OH

Conc. H2SO4 Br2 / H2O


100o C
 X  Y

8. The action of Br2/H2O on salicylic acid results in the formation of X, what is X.

9. The major product of reaction,

CH3

OH  Cl NO 2 
NaOH
DMSO, 90C
?

CH3

O OH OH
CH2 CH
10.  CH2 (Give mechanism)
  

CH2

11. Find out correct product of following reaction:

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O
, conc. H2SO4
HO   ? (with mechanism)

12. Predict product in the following reaction and explain the mechanism of their formation.
Ph

O CH CH CH2

Heat H

200 C
X  Y

OBJECTIVE (LEVEL -1)

1. Choose the statement that is correct concerning the following reaction.
Phenol + CH3I/NaOH  Major product
(a) This reaction results in methylation of oxygen in phenol. It is utilized frequently because the hydroxide
group is often highly activated. This reaction can be reversed with HI.
(b) this reaction results in methylation of oxygen in phenol. The resulting product is activated approximately
the same amount as in phenol. The reaction can be reversed with HI.
(c) This reaction results in methylation of oxygen in phenol. This reaction can be reversed with HI.
(d) This reaction results in an SN2 reaction between methyl iodide and NaOH. The resulting iodide ion
substitutes at ortho and para positions of phenol. Treatment of this product with reaction.

Aerial
2. Phenol 
oxid.
 coloured product. This is due to the formation of:
O
O
(a) O O (b)

(c) OH O O OH (d) All of these

3. A mixture of toluene, benzoic acid, aniline and phenol was dissolved in diethyl ether and extracted with 5%
NaHCO3 solution. This extract was acidified until a white crystalline compound appeared. What is the identify
of this compound?
(a) Toluene (b) benzoic acid
(c) Aniline (d) Phenol

4. A compound X(C7H8O) is insoluble in water, dilute HCl and aqueous NaHCO3 but dissolve in dilute NaOH.
When X is treated with bromine-water, it is converted into a compound of formula C7H5OBr3. Compound X is
OMe OH
CH3
(a) (b)

OH
OH

(c) (d)

CH3
CH3

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5. Which of the following compounds undergoes aromatic substitution most radily?
Cl Cl

(a) (b)

COCH3
Cl Cl

(c) (d)
H3C O 2N

6. What is/are true about addition-elimination mechanism of aromatic nucleophilic substitution (SNAr) reaction?
(a) It is a second order reaction
(b) It shows kinetic isotope effect
(c) It is an example of concerted (elementary) reaction
(d) It involves two transition states and a carbanion reactive intermediate

7. Which of the following reaction(s) has/have reactions-products correctly matched?

OH OH
Br Br
(a)  Br2 (aq) 

Br
CH3 OH

FeCl3
 Br2 
CS2

(b)

Br
(Major)

OH OH OH
NO2

(c)  Dil. HNO3 

NO2
OH

(d)

 Zn  

8. In which of the following reaction(s), reactant and product are correctly matched?
OH
(i) NaOH(aq) Conc. H2SO4
O
(a)  (ii) CO2
 
Heat


O
OH Br

(b) Zn
 Br2 — H2O  


Br Br

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OH O
CH2 CHCH2Cl HF
(c)  NaOH    

O OH O
HO
(d) O AlCl3
  O

O O

9. In which of the following reaction(s), reactant and products are correctly matched?
O

OH O C CH3
(a)
NaOH (CH3CO)2 O
 CCl4  

H2O H Heat

COOH
OH OH
CH3CH2Br
(b) (1.0 mol)  NaOH(aq) 
 (1.0 Mol)

COOH COO2H5
OH Br
O
Br
(c)  NaOH(aq) 

OH O
OH OH
CO2 CH3COCl
 NaOH    
O CH3
(d)

O O

10. Which of the following can bring about deuteration of phenol at para position
OH OH

Dil. D2SO4
(a)  Conc. H2SO 4   


D
OH OH

CS2 Mg D2O
(b)  Br2 
AlCl
 
Ether
  
3

D
OH OH

CH3I Cl2 Mg D2O Dil. H2SO4

(c)  NaOH   
AlCl
 
Et O
   
3 2

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OH OH

Zn
(d) 
DCl


Br D

11. In which of the following reaction(s), reactant and product is/are correctly matched?
OH

(a)  Conc. H2SO4   O

KOH
(b) C 6H5Br  C 6H5OH 
Cu Heat
 O

OH ONa

(c)  NaOH 

1.0 mol

SO 3H SO 3H
1.0 mol

OH
OH
(d) CH2  CH  CH2Br 200 C o
 NaOH    

12. Which of the following reaction(s) gives mainly catchol (o-dihydroxy benzene)?
OH

NaOH H2O2 H3O
(a)  CHCl3   
NaOH
  

OH

Zn NaNO2 H3O
(b) 
HCl
 
HCl / 0o C
  

NO2
NH2
HCl KOH
(c)  NaNO2 
0o C
 
aq


NH2
O
H2O
(d)  HBr  
O

13. Consider the following reaction

OH

H2SO4
 CH2O  

Excess

The expected product(s) of the above reaction is/are

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OH
CH2OH
(a) (b) HO CH2 OH

OH CH 2OH
CH2OH OH

(c) (d)

CH2OH CH 2OH

14. Which of the following reaction will give a visible change?

OH

(a)
 Br2 — H2O 

OH

(b) CH3Cl
 NaOH(aq)  

N2Cl OH
(c)

OH
(d)  Conc. H2SO 4 

15. Which of the following is/are true regarding phenol?

(a) It turns pink anexposure to air
(b) It is less reactive than anisole in aromatic electrophilic substitution reaction
(c) It is more reactive than aniline in an aromatic electrophilic substitution reaction
(d) Acetylation of phenol decreases its reactivity in aromatic electophilic substitution reaction

16. Which of the following is the product of the reaction below?

OH

Br2 / FeBr3
CS2



OH
OH

(a) (b)

Br
Br

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Br OH
Br
(c) (d)

Br

OBJECTIVE (LEVEL – 2)

1. Which of the following starting material undergo most difficult nucleophilic aromatic substitution reaction?
O NO2

O
(a) O (b) O

F F
NO 2
O 2N O
O
(c) O (d)
O
F
F

2. Which of the following reaction will give iodobenzene as the major organic product?
Cl
FeCl3 Heat
(a)  I2 
HgO
 (b)  KI  

OH
AlCl3
(c)  HI  (d)  ICl  

3. In which of the following reaction(s), reactant and product are incorrectly matched?
OH OH
OH NO2

(a)  HNO3 (Dil). 

NO2
OH OH
AlCl3
(b)  CO  HCl  

CHO
OH OH
NO2
Conc. H2SO4
(c)  Conc.HNO3  

NO2
OH
OH CH2 CH2
(d) 14
CH2  CH—CH2Cl 200C
14
 NaOH(aq) 
 

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4. Which one is the missing reagent of Kolbe Schmidt reaction?
ONa OH
CO2Na

 ? 

(a) HCO2Et (b) (EtO)2C = O

(c) CO2 (d) HCO2Na

5. Which of the following compound is the likeliest product from the reaction between phenol and Cl2 in the
presence of FeCl3(aq)?
(a) Mixture of p-chlorophenol and o-chlorophenol
(b) m-chlorophenol
(c) 2, 4,6-trichlorophenol
(d) Reaction will not occur

6. Reaction of phenol with acetic anhydrides gives.

OH OH OH
COCH3 OCOCH3 OCOCH3
I. C6H 5COCH3 II. III. IV. V.

COCH3
(a) I (b) II
(c) III (d) IV + V

7. Phenol reacts with acetone in the presence of conc. sulphuric acid to form a C15H16O2 product. What of the
following compound is this product?
O C6H5
(a) (b) HO OH
O C6H5

O O
C6H5
(c) (d)
C6H5
O
O

8. Consider the following two compounds undergoing aromatic nucleophilic substitution reaction
Cl Cl
H3C CH3

(I)  KOH  (II)  KOH 

H3C CH3
NO2 NO2
The correct statement is/are
(a) -0C to Cl in I is more electrophilic than the same in II.
(b) II occur at faster than I.
(c) reaction II occur at slower rate than I due to steric inhibition to resonance of —NO2
(d) reaction I occur at slower rate due to greater steric hindrance by two methyl groups at adjacent positions.

9. A (C7H8O) + Na/  No gaseous product A + Br2/FeBr3  C7H7OBr (Two isomers), A canbe

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OH OH

CH3
(a) (b)

CH3
OH
OMe

(c) (d)

CH3
——
ANSWER KEY

SUBJECTIVE (LEVEL -1)

1. Phenol is prone to both oxidation as well as reduction hence, it is better to protect the hydroxy group before
any other reaction as
OH
OCH3
(i) NaOH

(ii) CH3Br


Anisole

Anisole, being a ether, is now resistant to both oxidastion as well as reduction

OCH3 OCH3 OCH3 OH

conc HI (1 mole )
 conc. HNO3 
H2SO4

 FeHCl
   

NO 2 NH2 NH2

3. The dichlorocarbene may also attack a double bond of pyrrole as

Cl

Cl
 CCl2 
N N
H H
(I)
Now I reacts with OH– as
Cl

Cl
Cl
 H2O  Cl
N N
H
HO
4. Using CHCl3 and phenol synthesize first salicylaldehyde via Reimer-Tiemann’s reaction as

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OH O OH

CHO CHO

NaOH H3O
 CHCl3 
H2O
  

Salicylaldehyde

Salicylaldehyde formed above is than oxidized selectively to salicylic acid and finally acylated as
O

C
O CH3
OH OH
COOH
CHO COOH
Ag2O * CH3COCl

H2O

or (CH CO) O / H

3 2

Aspirin

Similarly, using CCl4, aspirin is synthesised as.

OH O OH
COO COOH

 H3O
OH
 CCl4    

(Salicyic acid)
5. O
C
OH O O CH3
COO COO O
CH3COCl O
 NaOH (aq) 
 CO2   H3O
 


CH3
COOH
Aspirin

6. OH
OH
CHO
NaOH H3O
 CHCl3 
 
(Re imer Tiemann Re action)

(I)
O OH

H3O
NaOH / l2
I    
Dakin reaction
O OH

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7. O CH3 O CH3 OH

OH
O
A= B= C= D= E=

Br C C C C C C

Br C C C C

O CH3 OH

SUBJECTIVE (LEVEL -2)

1. OH Cl
 PCl5   Ph3PO4
(Major )

Excess

2. OH Cl
, ,  Ph3PO4


OH
4. CHCl3   CCl3– 
 Cl
 : CCl2
CCl 2 CHCl 2 CHO

: CCl2  H 


1. OH
 

2. 

N N N N

Na H
CHO
Cl
Cl
: CCl2  
Cl
N N N N
H
(II) (I)

6. OH OH OH

CHO CHO COOH

X= Y= Z= T= S= P=

CHO

OH
Br Br
7.

Br

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OH
Br Br
8.

Br
CH3

9. O NO2

CH3

11. HO C OH

12. X is formed as rearrangement product as

Ph

O CH CH CH2 OH
Heat
 
CH2 CH CHPh
X
X on treatment with catalyst, protonated at double bond in the side chain which finally undergoes cyclization
as
OH OH O Ph
H
CH Ph

 H
 
CH2 CH CHPh
X Y

OBJECTIVE (LEVEL -1)

1. A
NaOH CH3I HI
C 6H5  OH  
SNI
 C 6H5 OCH3  C6H5 OH  CH3I
2. C
3. B
Only benzoic acid forms salt with NaHCO3, hence comes in aqueous phase which reprecipitate on
acidification.
4. C
X must have a —OH group and —CH3 must be at meta position so that ortho and para positions gets
brominated to give tribromo derivative
5. D
Nitro substituted aryl halide is most reactive in SNAr reaction
6. A, D
Attack of nucleophile occur in slow rate determining step, hence a second order reaction. Halide is eliminated
in fast non-rate determining step, hence doesn’t show kinetic isotopic effect. It is a two step reaction (non-
elementary) with two transition state and a carbanion intermediate.
7. A, B, C, D
In aqueous medium, phenol is tribrominated due to presence of henoxide ion. In CS2 no phenoxide exist,
hence mono bromination occur and that too in presence of Lewis acid catalyst. In aqueous solution, phenol is
nitrated even in diluted nitric acid. With Zn, phenol is reduced to benzene.
8. A, B, C
9. A, C
10. A, C
11. B, D
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12. A, B, C, D
13. A, B, C
14. A, C
15. A, D
16. B

OBJECTIVE (LEVEL -2)

1. A
Presence of nitro group activate for SNAr reaction.
2. A. D
Iodination of benzene can be done with I2/FeCl3 in presence of HgO. Here HgO oxidises the byproduct HI.
Also, ICl can be used for iodination of benzene as it gives I+ with Lewis acid catalyst.
3. B, C
4. C
5. C
6. C
7. A
8. A, C
In I, nitro group is free for resonance, hence increases reactivity for SNAr reaction to a great extent. In II, —
NO2 group is not in resonance with the ring, due to steric inhibition to resonance, hence doesn’t activate the S-
NAr as much as in I.
9. D
There is no phenolic group or —OH group. Hence,
——

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