DPP-01

1. Reimer Tiemann reaction is an example of

(A) Addition reaction (B) Substitution reaction
(C) Elimination reaction (D) Rearrangement reaction

CHCl Pot. tert Butoxide

cis-3-hexene          
 Major product
3
2.


Stereochemistry of major product is

(A) cis form (B) trans form (C) achiral (D) (A) and (C) both

3. In which of the following reaction there is a decrease in carbon atom takes place ?
(A) Isocyanide test (B) Reimer tiemann reaction
(C) Hoffman bromamide reaction (D) Beckman rearrangement

4. In which of the following reaction carbene is formed as an intermediate

(A) Isocyanide test (B) Reimer tiemann reaction
(C) Bromination (D) A and B both

5. + CHCl3 + KOH 



Major product is

Cl Cl

(A) (B)

OH CH2Cl

(C) (D)

6. In Reimer Tiemann formylation reaction molecular weight of phenol increases by

(A) 27 (B) 28 (C) 29 (D) 30

7. In Reimer Tiemann reaction medium of reaction is

(A) Acidic (B) Basic (C) Neutral (D) Gas-phase

8. IUPAC name of product formed in Reimer Tiemann formylation will be

(A) 2-hydroxy Benzene (B) salicyaldehyde
(C) 2-hydroxy Benzenecarbaldehyde (D) 2-hydroxy Benzenecarboxylicacid
9. Which of the following is electrophile in Reimer Tiemann reaction

(A) : CCl2 (B) CCl3 (C) PhOH (D) : CH2

NH2

NaNO2 H2O CHCl3

10.   (A)  (B)   (C)
2HCl boil KOH, 

CH3

Major product (C) is

OH OH OH OH
CHO CO2H
(A) (B) (C) (D)
CHO CO2H
CH3 CH3 CH3 CH3
 DPP-02
OH

(1) NaOH
1. + CO2  
 (A)
( 2) H major product

Structure of product (A) is

OH OH
OH O OH
CHO
(A) OH (B) (C) (D)

COOH CHO

2. IUPAC name of product (A) in question 11 above is

(A) salicylic acid (B) salicyldehyde
(C) 2-hydroxybenzenecarboxylicacid (D) 2-hydroxybenzaldehyde

O O
(1) CO 2 , NaOH CH3 – C – O – C – CH3
3. Phenol    
 ( A ) Aspirin
(2) H (B )
Product (B) is

O
O OH
OH O O–C–CH3
CH2–C–CH3
COOH
CO2H OH
(A) (B) (C) (D)

COOH

4. IUPAC name of aspirin is

(A) salicylic acid (B) salicyldehyde
(C) 2-acetylbenzoic acid (D) 2-acetoxybenzoic acid

OH

(1) NaOH
5. + CHCl3  
 (A)
(2) H

DBE value of (A) is x

moles of RMgX reacts with (A) is (y) , sum of (x + y) is
(A) 5 (B) 6 (C) 7 (D) 8
6. The orbital picture of a singlet carbene (:CH2) can be drawn as

py
pz
H p H p
C C C
(A) (B) (C) H (D) none of these
H sp2 H sp2
H
7. The orbital picture of a triplet carbene can be drawn as

py
pz
H p H p
H
C C C
(A) (B) (C) (D) none of these
H sp2 H 2 H
sp


OH Trans 2 butene
8. CHF2Br  (A)    
 (B)
(Intermediate)
singlet carbene
in this reaction B is:

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

9. Which of the following will not give carbylamine reaction

(A) t-butyl amine (B) aniline (C) sec. butylamine (D) N-methyl methanamine

OH

(i) CHCl / KOH

10.   3  (A). Product (A) will be :
(ii) H

CH3
OH OH OH CHO
CHO
(A) (B) (C) (D)
CHO
CH3 CHO CH3 CH3
 DPP-03
I
|
1. PhCHCl
Ph – C  C – Ph
    A EtOK
 B HBr
 C
EtOK
correct presentation of C is:

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

2. + MeOK
  ?

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

(i) aq.NaHCO / boil

3.    3  (X)
(ii) H3O

Identify unknown (X)

OH

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

OH
4. Intermediate produced during reimer tiemann's formylation will be
..
–
(A) :CCl2 (B) :CH2 (C) CCl3 (D) CHCl3

5. Which of the following compound doesn't gives Hoffman's carbyl amine test

NH2
|
NH2
(A) .. (B) .. (C) (D)
NH NH2

6. CH3 – NH2 + CHCl3 + KOH  major product will be :


(A) CH3 – C  N (B) CH3 – NH – CH3 (C) CH3 – N  C (D) NH3
7. What is the product of the following reaction?
MeOK in chloroform

 ?

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

OH
OMe
(i) CHCl3  NaOH P
8.      major product
(ii) H

Identify the structure of 'P'

OH OH OH
OH
OMe OHC OMe OMe
(A) (B) (C) (D)

CHO
O H
OMe

(i) CHCl  NaOH

    3 
 P
9.
(ii) H major product

Me

Identify the structure of 'P'

OMe OMe O OMe OMe

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

CHO
Me Me CHO OH

OH
(i) CHCl3  NaOH
10.      P
(ii) H major product

Identify the structure of 'P'

O H
OH
OH OH
(A) (B) (C) (D)

CHO
CHO
 DPP-04
CHI ClBr P
1.    
KOH major product

Identify the structure of 'P'

Cl Br I OH

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

NH2

2. + CHCl3 + KOH  P

major product

Identify the structure of 'P'

NH2
CN N=C NH2
CCl2
(A) (B) (C) (D)

CCl2

3. R – NH2  x  R – N C

KOH

Structure of x in given reaction will be

(A) CCl4 (B) CHCl3 (C) CH2Cl2 (D) CH4
OH (1)CO2 ,NaOH
(A)
(2)H ortho isomer
4.

(1)CO2 ,KOH
(B)
(2)H ortho isomer
Correct order of yield of products A & B is
(A) A > B (B) B > A (C) A = B (D) B >> A

Question No.5 to 7 (3 questions)

It is believed that chloroform and hydroxide ion react to produce an electron deficient intermediate dichloro
carbene : CCl2 (DCC)

—
OHH H2O + : :CCl2 + Cl

Treatment of phenol with DCC in basic medium introduces an aldehyde group, onto the aromatic ring.
This reaction is known as Reimer Tiemann reaction.
 
(
i) O H
  +
(ii ) :CCl 2 , ( iii ) H 

The Reimer–Tiemann reaction involves electrophilic substitution on highly reactive phenoxide ring. The
electrophilic reagent is dichloro carbene : CCl2

— 
+ :CCl2  OH
   H
 
o-product is major product because :
(i) there are two o-positions available as compared to one para.
(ii) o-product is more stable due to the formation of six membered chelate formation.

Mechanism of Isocyanide test :

If 1 ° amines (aliphatic and aromatic) react with DCC in basic medium it yield isocyanide or carbylamine.
This reaction is known as carbylamine reaction :
The product is known as isocyanide & it is a foul smelling substance.

  



5. Step marked by is
(A) Aromatization reaction (B) Intramolecular acid base reaction
(C) Both of the above (D) None of the above

6. If is used instead of during Reimer Tiemann reaction the product formed is:

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

7. If CCl4 is used in place of CHCl3 during Reimer Tiemann reaction, the product formed is:

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

 DPP-05
O

1. R NH 2+ Br2 + KOH RNH2 + KBr + K2 CO3 + H2O

Total moles of KOH consumed in this reaction will be
(A) 2 (B) 3 (C) 4 (D) 5

O
||
2. H C–NH2   Product
KOBr

Correct stereochemistry of product will be

NH2
(A) H NH2 (B) NH2 H (C) (D) A and C both
H

3. In Hoffman's Bromamide reaction shifting of alkyl group takes place from

(A) Carbon to Nitrogen (B) Carbon to Carbon (C) Nitrogen to Carbon (D) Nitrogen to Nitrogen

4. Which of the following compound not undergo Hoffman's Bromamide reaction.

O + –
NH3Br
(A) NH2 (B)
O

O
O
(C) NHBr (D)
NH

NH2
5. (x) 
KOBr


(x) will be

CONH2
CONH2 CONH2 CONH 2

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

O
KOBr
6. Ph – C – NH2   (A)
Product will be
CH3
(A) Ph – NH2 (B) Ph – NH – CH3 (C) Ph – N (D) Ph – N C
CH3
 O

7. NH2  CHCl3
 (A)  
KOBr
 (B)
NaOH

Product (B) is

(A) Ph – NH2 (B) Ph – N C (C) Ph – N N (D) Ph – N = O

O
C–OH
Br NH
8. 
2
 (A)  3
 (B) 
KOBr
 (C)
Fe 

Product (C) is

NH2 NH2 NH2 NH2

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

14
Br2
 (A)  (1) O = C = O NH
(C)  (D) 
Mg
9.  (B) 3
 (E)
KOBr
Fe ether (2) H

Product (E) is
14
(A) Ph – NH2 (B) Ph – CH2 – NH2 (C) Ph – C H2 – NH2 (D) None of these

NH
(A)  (B) 
3
10.  CH3 – NH2
KOBr

Reactant (A) is

O O O
(A) CH3 – C – Cl (B) CH3 – C – OH (C) CH3 – CH2 – C – OH (D) (A) and

(B) both
 DPP-06
O
O
NH2
1.  (A) CH3 – C – O – Et (B)
KOBr


Product (B) is

O O
NH2 O
NH – C – CH3 C–NHCH3
NH–C–C2H5
(A) (B) (C) (D)

O O
O
CH3 – C – O – C – CH3
2.  (A)
KOBr
Ph – C – NH2  (B)
(acetic anhydride)
Product (B) is
O
O O
NH2
C–NHCH3
NH–C–C2H5 N CH3
(A) (B) (C) (D) H

O
Br KOD
3. Ph – C – NH2 2   (A)
D 2 O, 

Product (A) is
(A) Ph – NH2 (B) Ph – ND2 (C) Ph – CH2 – NH2 (D) Ph – CH2 – ND2

O
4.  R – NH2
(A)
R – C – NH2 

Missing reagent (A) is

(A) Br2 + KOH (B) Br2 + HBr (C) Br2 (D) KBr

5. Which of the following will not undergo Hoffmann bromamide reaction ?

O
O
(A) NH–CH3 (B) CH3 – C – NH – Ph

O
(C) (D) All
N
6. Most reactive towards Hoffmann bromamide reaction ?

O NH2 O NH2 O NH2

O

(A) (B) (C) NH2 (D)

CH3 OCH3 NO2

..
OH
..
N

7. 
H P
  major product

Identify the structure of 'P'

H
H O O
O N
N NH2
(A) (B) (C) (D)

HC
 l  P
8.
 major product

Identify the structure of 'P'

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

Ph OH
9. C=N 
H P
  major product
CH3
Identify the structure of 'P'
(A) CH 3 – C – NHC 6H 5 (B) C6H5 – C – NH – CH3
||
O O
(C) A and B both (D) C6H5 – C – NH2

O
OH
CH3
10. C=N 
H
  P
Ph major product

Identify the structure of 'P'

(A) CH3 – C – NH – C6H5 (B) C6H5 – C – NH – CH3
|| ||
O O
(C) A and B both (D) C6H5 – C – NH2

O
 DPP-07

1. Ba OH2 P
     major product

Identify the structure of 'P'

NH2
NH2 NH2 NH2
F Cl
(A) (B) (C) (D)
F
F

2. KOBr
  , Identify the structure of 'P'
P
major product

O O O O
   
(A) O Na (B) OK (C) OK (D) ONa
NH2 NH2 NH2 NH2

3. KOBr P
  major product

Identify the structure of 'P'

NC CH2NH2 CN NH2

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

4 H SO P
2 
4 major product

Identify the structure of 'P'

CONH2 O O
CONH2
NH
(A) (B) NH (C) (D)
Caprolactum
5. + NH3    KOBr
 (A)   (B)


Identify the structure of (B)

CN NH2
CONH2 NH2

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

Cl
 2 P
6. CaOH2 major product

Identify the structure of 'P'

(A) CH3 – CN (B) CH3NH2 (C) CH3CH2NH2 (D) CH3 – NC

O
||
C – NH2 CHCl3
7. KOBr Reduction
A B C , Identify C
KOH

(A) Ph – CH2 – NH2 (B) Ph – NH2 (C) Ph – CO2H (D) Ph – NH – CH3

Ph O NaOBr
8. CH 3   ( A ) ; Product of the reaction is :
H NH2 (major )

Ph Ph CH3 Ph O
–
(A) CH 3 NH2 (B) CH3 H (C) Ph H (D) CH3 C–O
H NH2 NH2 H
9. Which of the following reaction represent incorrect major product.
O
||
KOBr
(A) CH 3 – C – NH – CH 3  
 CH3 – NH2

OH
O
(i ) O 2 / h
(B)    +
(ii) H3O
Cumene
O

NH2OH H SO
(C)    (A) 2 
4
caprolactum
(B )

O O
|| CH3CO3H ||
(D) CH3O C    CH3O O —C

NH2
O O

10.` 2CH3 – C – O – C – CH3

NH2
(A)
molecular weight of (A) increases by
(A) 80 (B) 82 (C) 84 (D) 86

(1) O 2 / h
11.   
 ( A )  (B)
( 2 ) H3 O

Product (A) undergoes Reimer Tiemann reaction so the structure of product (B) is
O OH
(A) O (B) (C) (D) OH

NH2

NaNO H O
12.  
2
(A)  (B)
2
2HCl boil

Product (B) will be :

+ –
OH N2Cl Cl

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

 DPP-08
Question No.1 to 5 (5 questions)
H NOH
(A) 2 


(F) + (G) CH3COOH + PhNH2

1. Structure of (A) will be

O O
||
(A) Ph – CHO (B) Ph – C – CH 3 (C) Ph – C – C2H5 (D) B and C both

2. Structure of (B) will be

Ph OH CH3 OH
(A) C=N (B) C=N (C) A and B both (D) None
CH3 Ph
..

..

3. Structure of (D) will be

O O
|| ||
(A) Ph – C – NH – CH 3 (B) Ph – NH – C – CH 3 (C) (A) and (B) both (D) None of these

4. Structure of (F) will be

(A) C2H5NH2 (B) C3H7NH2 (C) CH3NH2 (D) (A) and (B) both

5. Structure of (G) will be

(A) PhCN (B) PhCOOH (C) PhCHO (D) PhCH3
Question No.6 to 8 (3 questions)
HOFFMANN REARRANGEMENT
It involves conversion of a carboxylic acid amide into an amine with a loss of a carbon atom on treatment
with aqueous sodium hypobromite. Thus Hoffmann result in shortening of a carbon chain.
O
|| Br
R  C  NH 2 2  R–NH2 + NaBr + Na2CO3
NaOH
Mechanism of the reaction is

O
||
C – OH NH3  KOBr
6. A B C , Identify C

Product (A)

(A) Ph–NH2 (B) Ph–CH2– NH2 (C) Ph–NH–CH3 (D)

7. Which of the following will not give Hoffmann bromamide reaction.

O O
|| ||
(A) CH  C  NH
3 2
(B) C  NH  Br

O O
|| ||
(C) C  NH 2 (D) C  NH  CH 3

Br KOH
8. 2   A (Major)

Product (A) is:

(A) (B)

(C) (D)
Question No. 9 to 11 (3 questions)
BECKMANN REARRANGEMENT
The given is mechanism of Beckmann rearrangement.

H –H2O 
R ' C  N  R
(I)
(II)

O OH
|| |
R 'C  NH  R R 'C  N  R
9. Reagent cannot be used in Beckmann rearrangement is
(A) H2SO4 (B) BF3 (C) SO3 (D) HO
10. Rate determining step in the Beckmann rearrangement is
(A) I (B) II (C) III (D) IV

H SO
11. 2 
4  (X). Product (X) is

O O
(A)
|| (B)
||
C  NH  CH 3 NH  C  CH 3

O O
(C)
|| (D)
||
NH 2  C  H C  NH 2
Question No. 12 to 14 (3 questions) :
An aromatic compound A react with KOBr to give compound B. Compound B on reaction with chloroform
and KOH gives compound C which possess unpleasant smell. Compound B on reaction with NaNO2 and
HCl followed by reaction with water (boiled) gives compound D. D on reaction with CHCl3 and KOH gives
following compound E
OH
CHO
Structure of compound E 

CH3
12. Structure of compound A is :
O
||
O O CONH2 NH – C – CH3
|| ||
C – NH2 C – NH – CH3

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

CH3 CH3 CH3
13. Structure of compound B is :
NH2 NH2
NH – CH3 NH2
CH3
(A) (B) (C) (D)
CH3
CH3
14. Structure of compound D is :
OH OH OH OH
CH3
(A) (B) (C) (D)
CH3
CH3
Subjective :
O
||
HO C – CH3
(X)
15. (i) C – O – Et
||
O
(X) is moles of grignard reagent consumed.
OH

(ii) (i) CHCl3 / NaOH

+ (Y)
(ii) H

(Y) is double bond equivalent (DBE) of product.

O
||
C – NH2
(iii) Br2 + KOH
(Z)

(Z) is double bond equivalent (DBE) of product.

So, the value of (X + Y + Z) will be.

16. Identify product of given Beckmann rearrangement :

..

N H
(i) 

OH 
 DPP-01_ANSWER-KEY
1. B 2. D 3. C 4. D 5. B 6. B 7. B

8. C 9. A 10. B

DPP-02_ANSWER-KEY
1. A 2. C 3. D 4. D 5. C 6. A 7. C

8. C 9. D 10. C

DPP-03_ANSWER-KEY
1. C 2. A 3. B 4. A 5. A 6. C 7. C

8. D 9. B 10. C

DPP-04_ANSWER-KEY
1. A 2. B 3. B 4. A 5. C 6. A 7. D

DPP-05_ANSWER-KEY
1. C 2. D 3. A 4. D 5. A 6. A 7. B

8. A 9. A 10. D

DPP-06_ANSWER-KEY
1. A 2. D 3. B 4. A 5. D 6. B 7. A

8. A 9. B 10. A

DPP-07_ANSWER-KEY
1. B 2. B 3. D 4. C 5. D 6. B 7. D

8. A 9. A 10. C 11. B 12. A

DPP-08_ANSWER-KEY
1. B 2. A 3. A 4. C 5. B 6. A 7. D

8. D 9. D 10. B 11. B 12. C 13. D 14. B

15. 13 16. Et – C – NHCH 3

||
O