ORGANIC CHEMISTRY

Special DPP # 1 : Carbonyl Compound TIME : 30 MIN.

O
||
1. R – C – H + NH2 – R  R – CH = N – R
correct rate constant versus pH diagram for above reaction.

rate constant
rate constant

(A) (B)

2 4 6 8 10
2 4 6 8 10 pH
pH
rate constant

rate constant

(C) (D)

2 4 6 8 10 2 4 6 8 10
pH pH

2. In which of the following reaction formation of schiff-base take place ?

O
|| H
(A) Ph – C – H + CH3 – CH2 – NH2
H+
(B) 3-pentanone + benzyl amine

H+
(C) + R – NH2

(D) All

3. In which of the following reaction formation of geometrical isomer will take place.
O O
|| trace H+ || trace H+
(A) CH3 – C – H + NH2 – OH (B) H – C – H + NH2 – OH

O O
|| trace H+ || trace H+
(C) Ph – C – Ph + NH2 – OH (D) CH3 – C – CH3 + NH2 – OH

NUCLEUS-92, Rajeev Gandhi Nagar, Kota (Raj.) India 324005, Mob. 9358006181, 97831-97831 1
 4. Identify major products.
O O

H H
(1) + NH2 – OH 
 (2) + NH2 – NH2 


O
O
H || H+
(3) + R – NH – R 
 (4) Ph – C – H + NH2 – OH


O
O
||
(5) + NH2 – C – NH – NH2

O
(6) + NH2 – NH NO2

NO2

O
||
(7) CH 3 – C – Cl + NH 3

O
||
(8) CH 3 – C – Cl + NH2 – CH3
O
||
(9) CH 3 – C – OEt + H 2N – NH 2 H+

O
||
(10) C – CH2 – CH3 + NH2 – NH2 trace H+

O
|| 
(11) CH3 – C – H + H – C  CNa
acetylide

O
||
(12) Ph – C – H + Ph – NH2

O
||
(13) CH 3 – C – CH 3 + 2, 4– DNP 
O
(1) KCN
(14)   (A) LiAlH4 HNO2
( 2 ) H    (B)   (C)

(15) (CH ) Cd
32 


NUCLEUS-92, Rajeev Gandhi Nagar, Kota (Raj.) India 324005, Mob. 9358006181, 97831-97831 2
5. Write mechanism :

N H O / HCl
(1) 2 
 +

N
H

O
|| HCl O
(2) HO – CH2 – CH2 – CH2 – CH2 – C – H CH
 
OH 3 OCH3

O O
|| || 4 (NH ) CO
2 3
(3) CH3 – C – CH2 – CH2 – C – CH3   
(100 ºC) N
|
H

Br Br
(4) + CH3 – NH2  N

|
CH3

O
NaHSO
 OH
(5) 3
   (White crystalline adduct).

SO3

CH3
NH3 
(6) CH3 – Cl   CH3— N — CH3
excess
CH3

NUCLEUS-92, Rajeev Gandhi Nagar, Kota (Raj.) India 324005, Mob. 9358006181, 97831-97831 3
 ANSWER KEY

1. C 2. D 3. A
..
N – OH N – NH2 R–N–R

4. (1) (2) (3) (4) Ph – CH = N – OH

N – NH – CONH2 O
N – NH NO2
(5) (6) (7) CH3 NH2
NO2
O O Et
|
(8) CH3 – C – NH – CH3 (9) (10) C = N – NH 2
NHNH2
ONa
|
(11) CH 3 – CH (12) Ph – CH = N – PH (13) Orange ppt
|
C  CH
OH OH O
OH
CN NH2 CH3

(14) (15)
(A) (B) (C)

N N

+
5. (1) Step-I : H Resonance stabalised carbocation



O
.. .. .. +N ..
N N + H
..

OH2
..

Step-II : Acid
OH2  OH2 +
+  O–H
base
N
H
OH
O OH + H
H + O
(2)
H 
 .. H

HO ..
HO
–H+

+
OCH3 OH2
.. +
O ..
CH3OH O

O

NUCLEUS-92, Rajeev Gandhi Nagar, Kota (Raj.) India 324005, Mob. 9358006181, 97831-97831 4
 O .. O + Acid-base O ..
NH3 NH3 NH2
reaction
(3) 
O O
–
OH
HO OH

N –H2O
| N
H |
H

.. ..
Br ..Br CH3NH2 Br NH–CH3

..
(4)
H
–HBr

N
|
CH3
.. –
..

O – O
SO3H
(5) Step-I :
SO3H
–
O ONa
Na
Step-II : 
SO3H SO3H
.. 3 NH 3 CH Cl
CH3Cl ..
(6) ..  CH3NH2  CH3 – NH – CH3   CH 3 – N – CH 3
..

CH 3 – Cl
SN2 SN2 |
CH3

CH3
| CH3Cl
+
CH3 – N – CH3
|
CH3
Mechanism of this reaction is SN2.

NUCLEUS-92, Rajeev Gandhi Nagar, Kota (Raj.) India 324005, Mob. 9358006181, 97831-97831 5
 ORGANIC CHEMISTRY

Special DPP # 2 : Carbonyl Compound TIME : 30 MIN.

1. Identify - product.
O
H
(a) 
 cyclic

CH2 – CH2 – NH2

O
O
H 
(b) + 

N
|
H
(Morpholine)

O
||
C–H
(c) + NH2 – NH2 
 cyclic product

C–H
||
O

O
||
C – Ph
NH NH
2 
2
(d)   cyclic product

C – Ph
||
O
O
||
C – Cl
NH NH
2 
2
(e)   cyclic product

C – Cl
||
O
O O
|| || NH NH
2 
2
(f) H – C – CH2 – C – H   cyclic (aromatic)


(g) + NH2 – NH NO2 

O CHO
NO2
O

(h) NH2OH / HCl

  

NUCLEUS-92, Rajeev Gandhi Nagar, Kota (Raj.) India 324005, Mob. 9358006181, 97831-97831 6
2. Write chemical equation for the reaction of each of the following compounds with one equivalent of HCN.

O
CHO H3C
H3C
(a) HCN (b) HCN
 
CH2 – CHO
O

O O
|| ||
(c) HCN (d) HCN
Me – N  C – CH2 – CH2 – C – CH3  
|
O
Me

O O O
|| || ||
HCN
(e) CH3 – C – CH2 – CH2 – C – H  HCN
(f) H – C – H 
 

3. In which of the following reaction formation of enamine take place

O O

H H
(a) + CH3 – NH – CH3 
 (b) + 

 
N
H
O O

H H
(c) + CH3 – NH2  
 (d) + NH2 – NH2 

 

(e) Both (a) and (b).

4. Show how would you prepare the following derivative from appropriate carbonyl compounds ?
N – OH
(a) A + B 

N
(b) A + B 

(c) A + B  N

N
(d) A + B 

NUCLEUS-92, Rajeev Gandhi Nagar, Kota (Raj.) India 324005, Mob. 9358006181, 97831-97831 7
 (e) A + B  CH = N – OH

N – NH2

H
(f) A + B  
pH 4 to5

H
(g) A + B   N — OH
pH 4 to5

H
(h) A + B  
pH 4 to5
N—OH

N CH3

H
(i) A 


H
|
N N
H  (B)
(j) A 
 


NUCLEUS-92, Rajeev Gandhi Nagar, Kota (Raj.) India 324005, Mob. 9358006181, 97831-97831 8
 ANSWER KEY
O

N N
N
1. (a) (b) (c)
N

Ph

N N
N N
(d) N (e) (f)
N
Ph
NOH

(g) O CH = N – NH NO2 (h)

NO2

O O
||
CHO

2. (a) CH – OH (b) CN (c)

N
OH
CN OH CN
O OH O OH
|| CN H
(d) C – CH2CH2 – C – CH3 (e) (f)
H CN H
CN
OH

3. (e)

O
O
C – H + H2N
4. (a) + NH2OH (b)

NH2
NH 2 + O
(c) (d) +O (e) CHO + NH2OH

(f) + NH2NH2 (g) O + H2NOH (h) + H2NOH

||
O

NH2 O
(i) (j) (b) H2/Ni/LiAlH4
CH3 NH2

NUCLEUS-92, Rajeev Gandhi Nagar, Kota (Raj.) India 324005, Mob. 9358006181, 97831-97831 9