Topic : PHENOLS

Sub topic : PREPARATION

Model-1 :

Q.NO
1. *

C
2. *

A
3. * Which of the following statements is/are correct about the following reactions?

I) Path I is feasible II) Path II is feasible

III) 2, 4-Dinitro chloro benzene cannot be trinitrated because Cl and two NO2
atoms deactivate the ring towards further SE reaction

915
 IV) 2, 4-Dinitrophenol can be nitrated becuase the two deactivating NO2
groups prevent ring oxidation
a) I, II b) III, IV c) I, IV d) II, III
C
Statements are self explanatory
4. *

ABD

5.

6. * Which of the following reaction will not give ether as a major product.
B) CH CCl  CH CH O  Na  

A) CH CH Cl  Ag O 
3 2 2 dry  
3 3 3 2
  
O Na
 CH 3  Cl 
C) Cl  Ph  O  Na D)

B
Conceptual

916
7. *

C
8. * O
HCl Product is

O
O O
HO OH
A) B) Cl

HO OH O OH

C) Cl D) Cl

C
O OH OH
+ +
H
+
O O O
–
Cl

OH OH OH
+ +
–H H

Cl + Cl Cl
O O O
9. *

917
10. * Compound ‘X’, C7 H 8O , is insoluble in H 2O , dilHCl and aq. NaHCO3 but dissolves in
dil NaOH . When ‘X’ is treated with Br2 / H 2O , it is converted rapidly in to a
compound of formula C7 H5OBr3 . Then compound ‘X’ is
A) o  Cresol B) p  Cresol C) m  Cresol D) Anisole
C
11. *

AC
Passage :
4,4-dialkyl cyclohexadienone is treated with acid, it is converted to phenol with
migration of one of the alkyl group to adjacent carbon. The ease of rearrangement is
due to the creation of stable aromatic system.
When one of the alkyl group is part of the cyclic system, either the alkyl group or the
ring methylene group may migrate.
12. *

C
13. *

A
1 & 2.
Step(i): protonation
Step(ii): delocalization of  bond
Step (iii): Alkyl group migration followed by deprotinetion leads to
918
 Aromaticity
14. *

H+
B
R
R
Which of the following is correct regarding above reaction?
O OH O OH

A= B= A= B=
R
R R
A) R R R B) R R
OH OH OH OH

A= B= A= B=
R
R R R
C) R R D) R R
D

15. *

919
16. *

C
17. *

A, C, D are

 
(A) is not possible because CH 3  CH 2  C H 2 is less stable than CH 3  C H  CH 3
(C) is not possible because acetophenone and CH 3OH cannot be formed.
OH
(D) is not possible because |
CH 3  CH  CH 3

920
18. *

ABCD
19. *

20. * In which reaction phenol is formed as one of the organic product?

A) Ph  O  Ph 
HI
B)
NO2

 i ) Sn / HCl
ii ) NaNO2  HCl  05C 

iii ) Steam

C) PhO  CH 2  Ph 
H 3O
 D)
921
 KEY: BCD
Topic : PHENOLS
Sub topic : PROPERTIES

Model-1 : NITRATION
Q.NO
1. *

4
2. * When nitrobenzene is heated with mixed acid, the main product is m-dinitrobenzene.
Substitution of hydrogen by OH can take place in meta dinitrobenzene in presence of
KNO3 or K3[Fe(CN)6] which encourage the elimination of hydride ion. Among the
isomeric dinitrobenzenes meta isomer has the lowest melting point. Ortho and
paradinitrobenzenes resemble the meta isomer in many ways, but differ in the way they
undergo activated nucleophilic substitution, one nitro group being displaced.
Effective delocalization via p orbitals can only take place if the p orbirals, on the
atoms involved in the delocalization can become parallel or fairly parallel.
Major product of the following reaction is
NO2

 K Fe CN  

 3
NaOH
6

NO2

(A) 2, 6 dinitrophenol (B)m-nitrophenol

(C) 2, 4 dinitrophenol (D)3, 5 dinitrophenol
Topic : PHENOLS
Sub topic : PROPERTIES

Model-2 : SULPHONATION

Q.NO
1. *

922
 2. *

a
Topic : PHENOLS
Sub topic : PROPERTIES

Model-3 : HALOGENATION

Q.NO
1. *
*

A-P,R,S ; B-Q,S,T ; C-Q,R ; D-Q

2. *
*

923
 A-S ; B-R ; C-P ; D- Q
3. *

2
4. *

8
5. * Which one of the following compounds will be least susceptible to elimination
ofHBr?
CN Br NO2 Br
A) Br B) C) Br D) COOEt

B
Electron withdrawing groups makes hydrogen acidic.
6. *

924
7. *

8. *

A
9. * Phenol will react under forcing conditions with excess bromine to form a neutral compound. On the
basis of the mechanism of Electrophilic substitution. What is the compound expected for it?

925
10. *

11. * The end product of the following reaction is

*
*

OH
OH
OH Cl OH
OHC Cl
OHC OHC Cl

OHC
NH2 NH2 CHO
A) B) C N
C) D) NC

926
 It is under goingRiemer-tiemann reaction and also carbene addition w.r.t to double
bond
12. *

D
13. *
*

(B)

927
14. *

Key:-C
15. *
*

AB
16. *
*

5
17. * Compound Y1C7H8O is insoluble in water, dil HCI and aqueous NaHCO3.It dissolves
*
in dilute NaOH. When Y is treated with bromine water it is converted rapidly into a
compound of formula C7H5OBr3.Identfy the structure of Y

928
 OH OH O–H O – CH3
CH3
(A) (B) (C) (D)
CH3
CH3
B

Topic : PHENOLS
Sub topic : PROPERTIES

Model-4 : KOLBE SCHMIDT

Q.NO
1. *

A
2. **

929
3. *

B
4. *

B
First part is Kolbe-Schmidt rxn and second part is formation of aspirin
5. *

D
6. * OH OH
COOH
1) NaOH
+ CO2
2) 5.1 atm
3) H+
Name of the above reaction is
a) Kolbe’s reaction b) Elb’s reaction
c) Reimer – Tiemann’s reaction d) Duff’s reaction.
A
Hydroxyl oxygen forms epoxide
7. * In Kolbe’s Schmidt reaction
ONa

+ CO2 Product (X)

OK

+ CO2 Product (Y)

X and Y are major product which of the following are true.

930
 ONa OK
COO COO
(A) X will be and Y will be

ONa OK
COO
(B) X will be and Y will be

COO

ONa OK
COO
(C) X will be and Y will be
COO

ONa OK

(D) X will be and Y will be

COO COO

because Na form complex with CO2 hence C of CO2 attack at ortho position,
predominantly where as K does not form complex hence mainly attack at
paraposition.
8. *

Topic : PHENOLS
Sub topic : PROPERTIES

Model-5 : REMER-TIEMANN REACTION

931
Q.NO
1. *

D
2. *

B,c
3. *

A,c

932
4. *

A
5. *

B
6. *

A,C
* Passage-6
*

7.

933
8.

C
9.

4
* PASSAGE-7

10.

D
11.

C
12.

13. * Which of the following compounds give Reimer-Tiemann reaction

*
*

(I) (II) (III) (IV)

(V) (VI) (VII)

(VIII)
A) I, IV, V B) I, V, VI

934
 C) I, V, VII, VIII D) I, II, IV, V, VI, VIII
C
14. *
*

C
15. *
*

B
16. *
Which of the following compounds undergoes Reimer-Tiemann reaction?
OH
(A) (A) (B) N
H

CH2 OH NH2

(C) (D)

AB
CHO
OH
CHCl3 OH

KOH
(A)
(B)
CHCl3+NaOH

N CHO
N
H

935
17. *

(A, C, D)
Passage 1:(1)

18. *

(C)
19. * OH OH
CHO
2

Fe
H 2O2
  C
KOH

H C l3
alkaline H O

2 2 x

The number of hydroxyl groups present in the product x is/are

2
X is catechol

936
20. *

3
21. *
*
N OH 

H
(X) 
CHCl3
(Y)
H  KOH /  Major Product (Y) is
CO2H
Cl
N N
A) N Cl B) N C) CHO D) H
KEY: B
It is abnormal Riemer-Tiemann Reaction
22. *
*

937
23. *
*

24. *

Passage :
Reimer-Tiemann reaction: On treating phenol with chloroform in the presence of sodium hydroxide,
a –CHO group is introduced at orthoposition of benzene ring. This reaction is known as
Reimer - Tiemann reaction. The intermediate substituted benzal chloride is hydrolysed in the
presence of alkali to produce salicylaldehyde.

938
 Kolbe’s reaction:Phenoxide ion generated by treating phenol with sodium hydroxide is even
more reactive than phenol towards electrophilic aromatic substitution. Hence, it undergoes
electrophilic substitution with carbon dioxide, a weak electrophile. Ortho hydroxybenzoic acid
is formed as the main reaction product. The Jones modification of the Kolbe reaction employs
sodium ethyl carbonate. The Jones modification also gives same product like in Jones
modification.
25. * The intermediate(s) in the Reimer - Tiemann reaction of following reaction is/are….
OH ONa

CHO
CHCl3
NaOH

- -
O O Cl O Cl
-
C
Cl Cl

(I) (II) (III)

-
O OH O OH O

Cl Cl

(IV) (V) (VI)

A) I,II,III,IV,V,VI B) I,II,III,IV,V C) I,II,III,V,VI D) I,III,IV,V,VI
KEY: A
ANS:A
SOLUTION:

Name Reactions: A Collection of Detailed Reaction Mechanisms Hardcover – Import, 4 Aug 2003 by JieJack Li
939
26. * OH

C2H5COONa Ac2O
Major product Major product
H+

(i) Soluble in aq.NaOH.

(ii) Soluble in aq.NaHCO3.
(iii) The final product is 2-(acetyloxy)benzoic acid..
(iv) The final product is acetic 2-hydroxybenzoic anhydride.
A) i,ii B) i,ii,iii C) i,iii,iv D) ii,iii,iv
KEY: B
ANS:B
SOLUTION:

27. *

B
OH OH OH
CHO CH3
CHCl3/OH- Zn - Hg/HCl

CH3 CH3 CH3

Passage – 1 :

940
 The introduction of —CHO group in phenolic compounds by refluxing an alkaline
solution of phenolic compound and chloroform at 60°C for about half an hour, is known
as Reimer – Tiemann reaction (RTR). A mixture of o – and p-isomers is usually obtained
in which o-isomer predominates. However, if one of the o-positions remain occupied, the
p-isomer is the major product.
chloroform and NaOH react to produce an electron deficient electrophile, : CCl2 which
then drives the reaction towards the destination as per the following mechanism.
O O O
CCl2 H


:CCl2
 
H2O
II
 CHCl2
I

III tautomerisation

OH O OH
CHO CHO CHCl2
: H3 O
 V


: OH
IV

The introduction of substituent with +I effect or +R and –I effects both where +R  –I

effect accelerates RTR whereas substituent with –I and –R effects both or with –I and
+R effects where –I  +R, retard this reaction.
28. * The incorrect statement amongst the following is ?
(A) RTR is an electrophilic substitution reaction where the electrophile is a
carbene
(B)The rds of RTR is step III as it involves breaking of C—H  bond
(C)the step IV involves acid – base reaction and nucleophilic substitution both
(D)The rate of RTR will be in order:
OH OH OH OH

> > >

OCH3 CH3 NO2

B
rds is step I as already given in the passage.
29. * N2Cl
O O

 
 
A
 B C

where the reagents/conditions A, B and C are, respecting

(A) Ba(OH)2, KCN and CHCl3/NaOH heat, H3O+
(B)H2O (boil), CO2/KOH and Ac2O – AcONa, heat
(C)steam CHCl3/NaOH, heat, H3O+ and Ac2O – AcONa, heat
(D)Cu2Cl2/HCl, NaOH/high P and CO2|NaOH, heat
C
941
 N2Cl OH OH
O O
CHO

steam
 
ICHCl3 / NaOH

 
(CH3 CO)2 O
CH 3 COONa
II H3 O  
Perkin's reaction

Topic : PHENOLS
Sub topic : PROPERTIES

Model-6 : CLAISEN REARRANGEMENT

Q.NO
1. * In which of the following reactions, a phenolic compound is formed as product ?
CH2 CH CH2
O NO2

 K3  Fe  CN 6 
NaOH
A) B)
CH3
CHO
H   Excess 
H2O2 / OH


C) D) NHOH

ABCD
a) Claisen rearrangement b) nitrophenol is formed
c) Dakin’s reaction d) amino phenol is formed
2. *

2 Conceptual
3. * Find the product of the following reaction
R R

CH2
R O
R
R O
R
and H3C CH2
R
A) R R B) O

942
 R
R
R CH2
and H2C CHO
R
C) R R D) O

D
4. ** O O H

H 2SO 4
Ph Me A  B ; A and B are
Me
Me OH COMe
O

CH3 and
and

A) OH B) Me
Me Me
O
and MeOH +
Me Me
C) OPh D) OPh

A
Order of migrating ability : p-anisyl> p-tolyl> phenyl > p-chlorophenyl>p-
nitrophenyl
5. *

6. *

943
7. *

8. * This reaction is known as

Kistiakowsk et al. expermental reaction

9. *

10. *

944
11.

12. *

945
13. *

14. *

15. *

946
16. *

17. *

18. *

947
 19. *

20. *

Topic : PHENOLS
Sub topic : PROPERTIES

Model-7 : FRIES REARRANGEMENT

Q.NO

948
1. *

A,b,c,d
2. * O  CH 2  CH  CH  CH3

CH3 CH3

B 'B' is
200oC

a) b)
OH OH
CH3 CH3 CH3 CH3

CH2 CH CH CH3 CH3 CH CH CH2

O H
CH3 CH3

c) Both a) and b) d)

A
claisen rearrangement at para position gives retention
3. ** O O

O O

1. AlCl / CS
   3  2  product mixture
+ 2. H 2O

How many compounds are existed in the product mixture?

A) 4 B) 6 C) 8 D) 2
A
Conceptual
4. ** Match the following
Column I Column II

949
 (A) Pinacol – pinacolone rearrangement (P) six membered cyclic TS

(B) Claisen – rearrangement (Q) Carbine

(C) Fries rearrangement (R) Carbocation

(D) Reimer – Tiemann reaction (S) acylium ion

electrophilic aromatic
(T)
substitution

A – R; B – P; C – ST; D – QT
5. *

6. **

7. *

950
8. *

9. *

10. *

11. *

12. * What is 12 in the reaction ?

951
Topic : PHENOLS
Sub topic : PROPERTIES

Model-8 : DIAZOTISATION

Q.NO
1. *

A-Q ; B-R ; C-P ; D-s

2. **

952
3. **

1
4. *

1
5. *

C
6. * Compounds (C8H8O) X will give following laboratory tests.
Isomers FeCl3 AgNO3 / NH4OH Na metal
X Coloured solution Negative 1/2 H2

X can be :
H3C O
OCH3 CH2OH OH
O

(A) (B) (C) (D)

CH = O CHO CH = CH2
OH
C
7.
FeCl3 gives positive test with
OH

(A) (B)acetylacetone (C)acetoaceticester (D)acrolein

ABC
953
 OH O O

, CH3 C CH2 C CH3 and

O O OH
CH3 C CH2 C OC2H5 all have C C group
8. * Column – I Column – II
A) Phenol + Neutral FeCl3 P) No reaction
B) Phenol + Br2(aq) Q) Violet colour
C) Phenol + NaHCO3 R) White PPT
D) Picricacid + NaHCO3 S) CO2 gas is evolved
T) Electrophilic aromatic
substitution
A – Q; B – RT; C – P; D – S
9. ** Observe the following product

It can be formed from which reactants pair given below by diazotisation&coupling ?

(A) (B)

(C) (D) All The Above

B
In a diazocoupling requiring strongly activated benzene ring, as just step is diazotisation of -

gap.

954