CPP (Aromatic Compounds)

 Marked Questions may have for Revision Questions.

PART - I : SUBJECTIVE QUESTIONS

Section (A) : Phenol
A-1. Write the products of the following reactions :

OMgBr
(a) (b)

HBr HBr
(c)  (d) 
 

A-2. Explain why nucleophilic substitution reactions are not very common in phenols.

OH
OH
|
A-3. HF
+ CH3  CH  CH3 

Give the products of the above reactions.

A-4. Complete the following :

(a) (b)

(c) + CH3COCl

A-5. An organic compound ‘A’ having molecular formula C6H6O gives a characteristic colour with aqueous FeCl3
solution. When ‘A’ is treated with CO2 and NaOH at 400 K under pressure, ‘B’ is obtained. B on acidification
gives C when C treated with CH3COCl gives a popular pain killer D. Deduce the structures of A, B, C and D.

A-6. A B C
  

Identify A, B and C in above reaction ?

Section (B) : Nitrogen containing compounds

B-1. Complete the following reactions :

(A) NH / Cu O  Fe / HCl
 3 2  ; (B)  
B-2. Complete the following reaction :

Phosgene
(A)     Product

(B) +  Product

(C)

B-3. Why does aniline soluble in aqueous HCl ?

B-4. Write following conversions:
(i) nitrobenzene  acetanilide (ii) acetanilide  p-nitroaniline
B-5. What is the product when C6H5CH2NH2 reacts with HNO2 ?
B-6. How will you carry out the following conversion ?

B-7. Give 3 methods to distinguish primary amine from secondary and tertiary.

Section (C) : Diazonium Salt & its reaction

C-1. The final product of the following reaction is :

H O ,  NaNO2 / HCl KNO2 / Cu

3  

0ºC

C-2. How will you carry out the following conversion ?

C-3. How will you carry out the following conversions?

(i) (ii)

C-4. In the given reaction of aniline a coloured product C was obtained. The structure of C would be :

CH3
NH2 CH3 N
NaNO2 / HCl CH3
B Cold C
0ºC
A

C-5. A solution contains 1 g mol. each of p-toluene diazonium chloride and p-nitrophenyl diazonium chloride. To
this 1 g mol. of alkaline solution of phenol is added. Predict the major product. Explain your answer.
C-6. How will you carry out the following conversions?
(i) toluene  p-toluidine
(ii) p-toluidine diazonium chloride  p-toluic acid

PART - II : ONLY ONE OPTION CORRECT TYPE

Section (A) : Phenol
A-1. In which of the following reactions phenol is not obtained :

(A) (B)

(C) (D)

A-2. The major product of the following reaction is

(A) (B)

(C) (D)
 H3PO 4 (1).O ,
A-3. + CH3 –CH=CH2    A 2  B + C

 (2).H3O

The products B & C are respectively :

(A) Phenol & acetic acid (B) Phenol & acetaldehyde
(C) Benzoic acid & acetone (D) Phenol & acetone

A-4. product. The major product obtained is

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

A-5. When 2-hydroxybenzoic acid (salicylic acid) is treated with bromine water, the product formed is

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

A-6. An organic compound having the molecular formulaf C7H8O is insoluble in NaHCO3 solution but dissolves in
aqueous NaOH. When treated with bromine water the compound rapidly forms a precipitate having the
molecular formula C7H5OBr3. The organic compound is
(A) o-cresol (B) m-cresol (C) p-cresol (D) anisole

A-7. Br / CCl
2  
4
 The product is :

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

A-8. Identify the product in following reaction ?

D SO (excess)
2  
4  
D2O

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

A-9. The product (Y) of the following sequence of reactions would be :

Br Fe
(X) 2 
 (Y)

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

A-10. The product is :

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

NaOH CH3I HI
A-11. In the reaction sequence SO3Na  
 A  B  C+D
350

A, B, C and D are given by the set :

(A) Sodium phenate, anisole, C6H5I, CH3OH (B) Sodium phenate, phenitole, C2H5I, C6H5OH
(C) Sodium phenate, anisole, C6H5OH, CH3I (D) Sodium phenate, phenitole, C6H5I, C2H5OH

A-12. :

The compounds A and B in the above reaction sequence are :

(A) benzene, methyl benzoate (B) benzene, phenyl acetate
(C) phenyl acetate, benzene (D) benzene, phenylacetyl chloride

Section (B) : Nitrogen containing compounds

B-1. Which of the following sequence is best suited to convert benzene to 3-chloro aniline ?
(A) nitration, reduction, chlorination
(B) chlorination, nitration, reduction
(C) nitration, chlorination, reduction
(D) nitration, reduction, acetylation, chlorination, hydrolysis

B-2. (A) (B), Identify the major product (B).

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

 (i) Br2/NaOH
B-3. Product. The major product obtained is

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

B-4. Aniline when treated with acetyl chloride in presence of alkali, the product formed is :
(A) acetanilide (B) benzoyl chloride (C) acetophenone (D) aniline hydrochloride
B-5. The final product C,obtained in this reaction

NH2
Ac2 O Br2 H2O
A B + C
CH3COOH H

CH3

NHCOCH3 NH2 COCH3 NH2

Br COCH3 Br Br
(A) (B) (C) (D)

CH3 CH3 CH3 CH3

B-6. Chloroform when treated with aniline and alcoholic KOH, the product formed is ?
(A) Phenyl cyanide (B) Phenyl isocyanide
(C) Chlorobenzene (D) Phenol
B-7. An aromatic amine (X) was treated with alcoholic potash and another compound (Y) then foul smelling gas
C6H5NC is formed. The compound (Y) was formed by reacting compound (Z) with Cl2 in the presence of
slaked lime. The compound (Z) is :
(A) CHCl3 (B) CH3COCH3 (C) CH3OH (D) C6H5NH2
B-8. p-Chloro aniline and anilinium hydrogen chloride can be distinguished by
(A) Sandmayer reaction (B) Carbyl amine reaction
(C) Hinsberg's reaction (D) AgNO3
B-9. The best reagent for converting 2–phenylpropanamide into 2-phenylpropanamine is _____.
(A) excess H2 (B) Br2 in aqueous NaOH
(C) iodine in the presence of red phosphorus (D) LiAlH4 in ether
B-10. Hoffmann bromamide degradation reaction is shown by __________.
(A) ArNH2 (B) ArCONH2 (C) ArNO2 (D) ArCH2NH2
B-11. The best reagent for converting, 2-phenylpropanamide into 1- phenylethanamine is ____.
(A) excess H2/Pt (B) NaOH/Br2 (C) NaBH4/methanol (D) LiAlH4/ether
B-12. In order to prepare a 1° amine from an alkyl halide with simultaneous addition of one CH2 group in the carbon
chain, the reagent used as source of nitrogen is ___________.
(A) Sodium amide, NaNH2 (B) Sodium azide, NaN3
–
(C) Potassium cyanide, KCN (D) Potassium phthalimide, C6H4(CO)2N K+
B-13. Best method for preparing primary amines from alkyl halides without changing the number of carbon atoms
in the chain is
(A) Hoffmann Bromamide reaction (B) Gabriel phthalimide synthesis
(C) Sandmeyer reaction (D) Reaction with NH3
B-14. The product formed by the reaction of acetamide with Br2 in presence of NaOH is :
(A) CH3CN (B) CH3CHO (C) CH3CH2OH (D) CH3NH2

Section (C) :Diazonium Salt & its reactions

C-1. In the reaction, the product (C) is :
NaNO  HCl CuCN 
H / H2O
C6H5NH2  2   (A)  
 (B)   (C)
0–5ºC KCN

(A) C6H5CH2NH2 (B) C6H5COOH (C) C6H5OH (D) none of these

C-2. Benzenediazonium chloride can be converted into benzene on treatement with :
(A) H3PO3 (B) H3PO4 (C) H3PO2 (D) HPO3

NaNO HCl
2 2 H O
C-3. C6H5 NH2     X  Y, the product Y is :
O – 5C 
(A) Benzenediazonium chloride (B) Nitrobenzene
(C) Phenol (D) Cresol

C-4. (A). The major product (A) is

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

C-5. Diazonium salt + Cu + HCl  ; the reaction is known as

(A) Chlorination (B) Sandmeyer’s reaction

(C) Perkin reaction (D) Gattermann reaction

C-6. (A) (B). The product (B) is

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

C-7. Which of the following compound will not undergo azo coupling reaction with benzene diazonium chloride.
(A) Aniline (B) Phenol (C) Anisole (D) Nitrobenzene
 pH  4– 6
C-8. +   X (major product) X will be -

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

 (pH  9 –11)
C-9. + Ph – N2       X (major product) ; X - will be :

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

PART - III : MATCH THE COLUMN

1. Column - I Column- II

(A) RNH2 + CHCl3 + KOH (alc)   (p) Schotten-Baumann reaction
CuBr / HBr
(B) C6H5N2Cl     (q) Coupling reaction

NaOH(aq.)
(C) C6H5NH2 + C6H5COCl   (r) Carbylamine reaction
pH 910
(D) C6H5N2Cl + C6H5OH  (s) Sandmeyer reaction

2. Match the reactions given in Column I with the statements given in Column II.
Column I Column II
(A) Ammonolysis (p) Amine with lesser number of carbon atoms
(B) Gabriel phthalimide synthesis (q) Detection test for primary amines.
(C) Hoffmann Bromamide reaction (r) Reaction of phthalimide with KOH and R—X
(D) Carbylamine reaction (s) Reaction of alkylhalides with NH3
3. Match the compounds given in Column I with the items given in Column II.
Column I Column II
H2SO4
(A) C6H6 + CH3CH=CH2   (p) Schotten-Baumann reaction
NaOH
(B) C6H5OH + C6H5COCl   (q) Friedel-Craft reaction
(C) C6H6 + C6H5CH2Cl anhydrous AlCl (r) Reimer-Tiemann reaction

3

(i) CCl4 / NaOH
(D) C6H5OH  (s) Product is Isopropyl benzene
 
(ii) H3O
(t) Electrophilic substitution reaction
 Marked Questions may have for Revision Questions.

PART - I : ONLY ONE OPTION CORRECT TYPE

1. Identify the product in the following reaction.

H O
3 


(A) (B)

(C) (D)

2. Observe the following reaction, and select the correct option

dil. HNO 3 Steam distillati on

    (X) + (Y)        (Y) low boiling fraction

'Y' is :

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

H2SO4, 100ºC NaOH/fusion

OH x

3.

y
H2SO4, 15ºC NaOH/fusion

(A) x = y= (B) x = y=

(C) x = y= (D) x = y=
4. Compare the properties of two isomeric products x and y formed in the following reaction.

1. CCl  NaOH / 
4  
    x > y
2. H

Option Acid Strength H2O Solubility Volatility Melting Point

(A) y>x y>x x>y y>x
(B) x>y x>y y>x x>y
(C) y>x x>y y>x y>x
(D) x>y y>x x>y y>x

5. Give the product of the following reactions :




(A) (B)

(C) (D)

Br2 CH3COCl (i) Br2 / CH3COOH

6. (P) 
KOH
 (Q)   (R) (ii) H3O


The reactant (P) is :

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

7. Which of the following reduction reaction does not give an amine as product ?
H LiAlH4
(A) R–NO2 
2
Raney Ni
(B) R–NO2 
ether


Sn /HCl Zn / NH Cl
(C) R–NO2  (D) R–NO2 

4

8. Para toluidine is treated with HNO2 at ice cold conditions and then boiled with water. The final product
obtained is :
(A) anthranilic acid (B) p-cresol (C) toluic acid (D) phenol

9. Aniline when diazotized in cold and then treated with dimethyl aniline gives a coloured product. Its structure
would be :

(A) = (B)

(C) NHCH3 (D) CH3 N= N NH2

10. In the diazotisation of aniline with sodium nitrite and hydrochloric acid, an excess of hydrochloric acid is
used primarily to :
(A) suppress the concentration of free aniline available for coupling
(B) suppress hydrolysis of phenol
(C) insure a stoichiometric amount of nitrous acid
(D) neutralize the base liberated
11. The structure of the final product (Y) formed in the following reaction sequence is :

NaNO / HCl
anisole

2
 (X) 
  (Y)
278 K

(A) (B)

(C) (D)

12. The major product Y in the following sequence of reaction is :

(i) NaNO2 / HCl, 273 K (i) DIBAL H
Aniline 
(ii)CuCN / KCN
 (X) 
(ii)H O
 (Y)
2

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

PART - II : SINGLE OR DOUBLE INTEGER TYPE

1. Identify molecular weight of final product (Y).

Cl CH2  COOH

  (X) (Y)

2. How many toluidines on reaction with NaNO2/HCl followed by H3PO2 treatment gives Toluene.
 Sn / HCl NaNO2 H O, 
3.      2  Product Z
HCl 0 5C

Find the molecular weight of Z.

NaNO2 HCl CuCN Complete

4. P Q
0ºC to 5ºC hydrolysis

Molecular weight of T will be :

5. How many N atom are present in final product.

Conc . HNO / H SO Sn / HCl NaNO / HCl H PO 2

   3 2
4
    2  3   Final product.

Sn / HCl 2 NaNO

Basic medium
6. Ph-NO2         Product Y
HCl, 0C5C PhOH

Molecular weight
Find the molecular weight of Y report your answer as
2

7_. In the given reaction how many of the following products (1 – 9) can be formed.

+ +
 PART - III : ONE OR MORE THAN ONE OPTION CORRECT TYPE
1. Which of the following can show positive bromine water test ?

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

2. Identify the intermediates of the following reaction.


+ CHCl3 + NaOH 

(A) (B)

(C) (D)

(i) CHCl NaOH, 

3
3.        (P > Q) % yield
(ii) H 

Select the correct options :

(A) Boiling point , (P > Q) (B) Melting point , (Q > P)
(C) Water solubility , (P < Q) (D) Acid Strength , (Q < P)
4._ Correct options for the given below reaction :
(i) CHCl  KOH
Ph–OH   3  Products
(ii) H

(A) (Major) (B) (Major)

(C) (Major) (D) (Minor)

5. Which of the following reaction is/are correct

CHCl3 CHFCl2
(A)  
 (B)  
KOH KOH

 —
H or O H
(C) + HCHO  


H
(D) + 


6. Which of the following reaction is/are correct :

( i) NaOH
(A) + CO2   
(ii) H O 
+
3

NaOH
(B) + CHCl3 
 +

Pyridine
(C) +  


(D) NaOH
+ HCHO  +

7. The products of following sequence of reactions are

Br / Fe Sn / HCl NaNO / HCl H O/ 

2  F   G  2  H 2  I

(A) H = (B) I = (C) G = (D) F =

NaNO  HCl H2 O CHCl3 NaOH

8.  2  P Q     R + S
0 to 5 º C

Which of the following statement is/are correct :

(A) P is benzene diazonioum chloride
(B) Q can not give bromine water test
(C) R and S are position isomers
(D) During the formation of R and S from Q, formation of a new C–C bond will takes place.

(i ) HNO3 / H2SO 4 ( i) HNO 2 (i) NaOH, CO , 6 atm, 

(i ) Sn / HCl
9.      P     Q 
2
 R    S
( ii) (NH 4 )2 S x (ii) H2O,  (ii) HCl ( ii) NaOH

Which of the following statement(s) for the above sequence of reactions is/are correct

NH2

(A) P = (B) Q = (C) R = (D) S =

NH2

10. Coupling reaction takes place when benzene diazonium chloride is treated with :
(A) Benzaldehyde (B) -naphthol (C) N,N-dimethyl aniline (D) Phenol
11_. The correct option for products P, Q and R, S in the following sequence of reaction is / are :

O
15
O C – NH2
|| O
||
C Br2 / KOH CH3 – C – Cl Br2 / Fe
NH2 + P+Q 00 R+S
NO2 H3O+ /
CH3 NO2
CH3
 15
NH2 NH2 NH2
CH3 NO2
(A) P & Q are + 15 (B) P & Q are +
NO2 NH2 NO2
CH3 NO2 CH3 CH3

15
Br NH2 NH2
15
NH2 NO2 NH2 Br Br NO2
(C) R & S are + (D) R & S are +
CH3 NO2 CH3 Br NO2
CH3 CH3

PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.

Comprehension # 1

CH – CH – CH Cl
3 O2 , h
  2 2 X +
AlCl3 H3 O

1. Which of the following compound is 'P' ?

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

2. S is a well known pain killer which of the following is 'R' ?

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

3. Which of the following is attacking species in conversion Y to P ?

(A) :CCl2 (B) :CHCl (C) :CH2 (D) CH2Cl

Comprehension # 2

Br2 / NaOH /  NaNO2 / HCl / 0ºC

  (A)   (D)

4. The intermediates which are involved in the conversion from benzamide to (A) are :
(A) N-bromamide (B) carbocation (C) carbene (D) isocyanide
5. (B) on treatment with Zn/HCl gives :
(A) aniline (B) benzylamine (C) phenylisocyanide (D) N-methylaniline
6. (D) on reaction with phenol under alkaline conditions gives :
(A) diazobenzene (B) hydrazobenzene (C) benzidine (D) para hydroxy azobenzene

Comprehension # 3
The –NO2 group in an aromatic ring deactivates the ortho and para positions for an electrophilic attack. When
–NO2 group is present at ortho or para positions of a leaving group (Nucleofuge) it activates the ring for
nucleophilic attack. The reduction of –NO2 group by metal in acid causes its reduction to –NH2 group and
then the ring becomes strongly activated for a electrophilic attack. The strong activation of –NH2 group is
moderated by its acylation with CH3COCl to – NHAc group. Deacylation is carried out by hydrolysis with
H3O+ or OH–. The ring alkylation by using RX/AlX3 is not possible in presence of –NO2 or –NH2 group but is
possible in presence of –NHAc group.

7. The product (G) is :

(A) (B)

(C) (D)

8. The product (H) is :

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

9. The product () is :

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

Comprehension # 4
Hofmann rearrangement
In the Hofmann rearrangement an unsubstituted amide is treated with sodium hydroxide and bromine to give
a primary amine that has one carbon lesser than starting amide.
General reaction :

+ NaOH + Br2 R–N=C=O R – NH2

isocyanate
Mechanism :


OH
 

CO2R– NH

R – NH2
If the migrating group is chiral then its cofiguration is retained. Electron releasing effects in the migrating
group increases reactivity of Hofmann rearrangement.
10_. Which of the following compound(s) cannot give Hoffmann rearrangement :

(A) (B)

(C) (D)

11_. Arrange the following amides according to their relative reactivity when reacted with Br2 in excess of strong
base :

; ; ;

(A) IV > I > II > III (B) II > I > III > IV (C) II > IV . III > I (D) II > I > IV > III
 PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)
* Marked Questions may have more than one correct option.

1. + under Hofmann conditions will give : [JEE 2006, 5/184]

(A) + (B) +

(C) + (D) +

Comprehension # 1

X




2. Which reagent (X) is used to convert I to II [JEE 2006, 5/184]

(A) KBr / NaOH (B) Br2 / NaOH (C) NaHCO3 (D) N-Bromo succinamide

3. Which step is rate determining step [JEE 2006, 5/184]

(A) Formation of II (B) Formation of III (C) Formation of V (D) Formation of IV
 conc. HNO3
4. In the following reaction,     X
conc. H SO
2 4

the structure of the major product ‘X’ is : [JEE 2007]

(A) (B)

(C) (D)

Note : (–NH– part is o,p-directing).

5. The major product of the following reaction is : [JEE-2011, 3/160]

(A) (B)

(C) (D)

6. Amongst the compounds given, the one that would form a brilliant colored dye on treatment with NaNO2 in
dilute HCl followed by addition to an alkaline solution of -naphthol is : [JEE-2011]

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

7.* In the following reaction, the product(s) formed is(are) [JEE (Advanced)-2013]

P Q R S
(A) P (major) (B) Q (minor) (C) R (minor) (D) S (major)

8. The major product(s) of the following reaction is (are) [JEE (Advance)-2013]

P Q R S
(A) P (B) Q (C) R (D) S
9.* The reactivity of compound Z with different halogens under appropriate conditions is given below :

The observed pattern of electrophilic substitution can be explained by [JEE(Advanced)-2014, 3/120]

(A) the steric effect of the halogen (B) the steric effect of the tert-butyl group
(C) the electronic effect of the phenolic group (D) the electronic effect of the tert-butyl group
10. For the identification of -naphthol using dye test, it is necesary to use : [JEE(Advanced)-2014, 3/120]
(A) dichloromethane solution of -naphthol. (B) acidic solution of -naphthol.
(C) neutral solution of -naphthol. (D) alkaline solution of -naphthol.
11. Match the four starting materials (P, Q, R, S) given in List I with the corresponding reaction schemes
(I, II, III, IV) provided in List II and select the correct answer using the code given below the lists.
[JEE(Advanced)-2014, 3/120]
List-I List-II
P. 1. Scheme I

Q. 2. Scheme II

R. 3. Scheme III

S. 4. Scheme IV

Code :
P Q R S P Q R S
(A) 1 4 2 3 (B) 3 1 4 2
(C) 3 4 2 1 (D) 4 1 3 2
12. Among the following the number of reaction(s) that produce(s) benzaldehyde is

CO, HCl
I. [JEE(Advanced)-2015, 4/168]
Anhydrous AlCl3/CuCl

CHCl2
H2O
II.
100°C

COCl
H2
III.
Pd-BaSO4

CO2Me DIBAL-H

IV. Toluene, –78°C

H2O
13. The major product U in the following reactions is [JEE(Advanced)-2015, 4/168]

CH2 CH–CH3 , H radical initiator, O2
  T   U
high pressure,heat

H
O
O H3C CH3
CH3 O
O H
(A) (B)

H
O
O CH2
CH2 O H
O
(C) (D)

14. In the following reactions, the major product W is [JEE(Advanced)-2015, 4/168]

OH
NH2 , NaOH
NaNO , HCl
 2 V W
0 ºC

OH
(A) (B) N=N
N=N OH

HO
OH

(C) N=N (D) N=N

PART - II : JEE (MAIN) / AIEEE PROBLEMS (PREVIOUS YEARS)

1. Picric acid is [AIEEE-2002, 3/225]

COOH COOH OH COOH

NO2 NO2 O2N NO2
(1) (2) (3) (4)
NO2 OH
NO2 NO2
2. The reaction of chloroform with alcoholic KOH and p-toluidine forms : [AIEEE-2003, 3/225]

(1) H3C CN (2) H3C N2Cl

(3) H3C NHCHCl2 (4) H3C NC

3. Fluorobenzene (C6H5F) can be synthesized in the laboratory [AIEEE-2006, 3/165]

(1) from aniline by diazotisation followed by heating the diazonium salt with HBF4
(2) by direct fluorination of benzene with F2 gas
(3) by reacting bromobenzene with NaF solution
(4) by heating phenol with HF and KF
4. Presence of a nitro group in a benzene ring [AIEEE-2007, 3/120]
(1) activates the ring towards electrophilic substitution
(2) renders the ring basic
(3) deactivates the ring towards nucleophilic substitution.
(4) deactivates the ring towards electrophilic substitution.
5. Phenol, when it first reacts with concentrated sulphuric acid and then with concentrated nitric acid, gives
(1) o-nitrophenol (2) p-nitrophenol (3) nitrobenzene (4)2,4,6-rinitrobenzene
6. Toluene is nitrated and the resulting product is reduced with tin and hydrochloric acid. The product so
obtained is diazotised and then heated with cuprous bromide. The reaction mixture so formed contains :
[AIEEE-2008, 3/105]
(1) mixture of o– and p-dibromobenzenes (2) mixture of o- and p-bromoanilines
(3) mixture of o- and m-bromotoluenes (4) mixture of o- and p-bromotoluenes
7. In the chemical reactions the compounds ‘A” and ‘B’ respectively are : [AIEEE-2010, 4/144]
NH2

NaNO 2 HBF4
    A    B
HCl, 278 K 

(1) nitrobenzene and fluorobenzene

(2) phenol and benzene
(3) benzene diazonium chloride and fluorobenzene
(4) nitrobenzene and chlorobenzene

8. Phenol is heated with a solution of mixture of KBr and KBrO3. The major product obtained in the above
reaction is : [AIEEE-2011, 4/144]
(1) 2-Bromophenol (2) 3-Bromophenol (3) 4-Bromophenol (4) 2,4,6-Tribromophenol

9. In the following chemical reactions, the compounds A and B are respectively : [AIEEE-2011, 4/144]

NH2

NaNO CuCN
  2
 A  
 B
HCl, 278 K 

(1) Benzene diazonium chloride and benzonitrile

(2) Nitrobenzene and chlorobenzene
(3) Phenol and bromobenzene
(4) Fluorobenzene and phenol
10. Ortho-Nitrophenol is less soluble in water than p- and m- Nitrophenols because : [AIEEE-2012, 4/120]
(1) o-Nitrophenol is more volatile steam than those of m- and p-isomers.
(2) o-Nitrophenol shows Intramolecular H-bonding
(3) o-Nitrophenol shows intermolecular H-bonding
(4) Melting point of o-Nitrophenol is lower than those of m- and p-isomers.
11. An organic compound A upon reacting with NH3 gives B. On heating B gives C. C in presence of KOH reacts
with Br2 to given CH3CH2NH2. A is : [JEE(Main) 2013, 4/120]
(1) CH3COOH (2) CH3CH2CH2COOH
(3) CH3 CH COOH (4) CH3CH2COOH

CH3

12. A compound with molecular mass 180 is acylated with CH3COCl to get a compound with molecular mass
390. The number of amino groups present per molecule of the former compound is : [JEE(Main)-2013, 4/120]
(1) 2 (2) 5 (3) 4 (4) 6

13. Sodium phenoxide when heated with CO2 under pressure at 125°C yields a product which on acetylation
produces C. [JEE(Main)-2014, 4/120]
ONa 125  H
+ CO2 5 B 
 C
Atm Ac O 2

The major product C would be :

OH
OCOCH3 OH OCOCH3
COCH3
(1) COOH (2) (3) COOCH3 (4)
COOH
COCH3

14. In the reaction [JEE(Main)-2015, 4/120]

NH2

NaNO / HCl CuCN / KCN

 2  D    E + N2
0 – 5 ºC 

CH3
the product E is :
COOH

(1) (2) H3C CH3

CH3

CN CH3

(3) (4)

CH3

15. In the Hofmann bromamide degradation reaction, the number of moles of NaOH and Br2 used per mole of
amine produced are : [JEE(Main)-2016, 4/120]
(1) Four moles of NaOH and two moles of Br2 (2) Two moles of NaOH and two moles of Br2
(3) Four moles of NaOH and one mole of Br2 (4) One mole of NaOH and one mole of Br2
 EXERCISE - 1
PART - I

A-1. (a) + Na2SO3

(b) + Mg (OH)Br

OH OH OH
+H Br
(c)
+ CH3–Br

OCH
.. 3 HO–CH3 OH

(d)

A-2. In phenol, aromatic ring is highly electron rich due to +M of –OH group. So nucleophile does not easily attack
on the ring.

OH OH OH
OH CH(CH3)2
| HF
A-3. + CH3  CH  CH3 
 +

CH(CH3)2

OH
NO2
A-4. (a) + p-isomer ; (b) Salicylaldehyde ; (c) Phenyl ethanoate

OH OH OH OCOCH3
COONa COOH COOH
A-5. A  , B  , C  , D 

A-6. A  Zn, B  CH3Cl / FeCl3 and C  Strong oxidising reagent

B-1._ (A) NH / Cu O  (B) Fe / HCl

 3 2 
  
 Phosgene
B-2_. (A)   


(B) + 

(C)

B-3. Aniline forms the salt anilinium chloride which is water soluble.

B-4. (i)

(ii)

HNO2
B-5. C6H5CH2NH2   C6H5CH2OH

B-6.

B-7. (i) Isocyanide test (ii) Hinsberg test (iii) NaNO2 + HCl test

C-1.

C-2.

C-3. (i)

(ii) Conversion (A) given below is same as inpart (i) given above after that reaction (B) can be carried out.

(A) (B)
C-4.

C-5. This reaction is an example of electrophilic aromatic substitution. In alkaline medium, phenol generates
phenoxide ion which is more electron rich than phenol and hence more reactive for electrophilic attack. The
electrophile in this reaction is aryldiazonium cation. Stronger the electrophile faster is the reaction.
p Nitrophenyldiazonium cation is a stronger electrophile than p-toluene diazonium cation. Therefore, it couples
preferentially with phenol.

CH3 CH3 CH3

HNO3 / H2SO4 Fe / HCl

C-6. (i)

Toluene
NO2 NH2
p-Toluidine

CH3 CH3 CH3

+
CuCN / KCN H2O / H
(ii)

+
N2Cl– CN COOH
p-Tolule acid

PART - II
A-1. (B) A-2. (C) A-3. (D) A-4. (B) A-5. (D)
A-6. (B) A-7. (B) A-8. (D) A-9. (C) A-10. (A)
A-11. (C) A-12. (B) B-1. (C) B-2. (B) B-3. (B)
B-4. (A) B-5. (D) B-6. (B) B-7. (B) B-8. (D)
B-9. (D) B-10. (B) B-11. (B) B-12. (C) B-13. (B)
B-14. (D) C-1. (B) C-2. (C) C-3. (C) C-4. (D)
C-5. (D) C-6. (B) C-7. (D) C-8. (B) C-9. (A)
 PART - III
1. (A - r) ; (B - s) ; (C - p) ; (D - q) 2. (A - s) ; (B - r) ; (C - p) ; (D - q)

3. (A - q,s,t) ; (B - p) ; (C - q,t) ; (D - r,t)

EXERCISE - 2

PART - I
1. (C) 2. (D) 3. (C) 4. (D) 5. (A)
6. (A) 7. (D) 8. (B) 9. (A) 10. (A)
11. (C) 12. (A)

PART - II
1. 75 2. 03 3. 94 4. 78 5. Zero (0).
6. 99 7. 3 (1, 4, 9)

PART - III
1. (A,B,C,D) 2. (A,B) 3. (B,C) 4._ (C,D) 5. (A,B,C,D)
6. (A,B,C,D) 7. (B,C,D) 8. (A,C,D) 9. (B,D) 10. (B,C,D)
11. (B,C)

PART - IV
1. (C) 2. (B) 3. (A) 4. (A) 5. (B)
6. (D) 7. (B) 8. (B) 9. (C) 10. (B)
11. (D)

EXERCISE - 3
PART - I
1. (A) 2. (B) 3. (D) 4. (B) 5. (A)
6. (C) 7.* (B,D) 8. (B) 9.* (A,B,C) 10. (D)

11. (C) 12. 4 13. (B) 14. (A)

PART - II
1. (3) 2. (4) 3. (1) 4. (4) 5. (1)
6. (4) 7. (3) 8. (4) 9. (1) 10. (2)

11. (4) 12. (2) 13. (1) 14. (3) 15. (3)