ORGANIC CHEMISTRY

Daily Practice Problems

CARBONYL COMPOUNDS

TIME : 35 MIN. DPP-1

Reaction Product

O O
|| ||
(a) Ph–C–CH2–C–OH


O O
|| ||
(b) 
OH 

CH2—CO2H
|
(c) C=O 
|
CH2—CO2H

O
|| CO2H
(d) 
CO2H

O
HO2C || CO2H
(e)


O
|| CO2H
(f) Ph–C–CH 
CO2H

O
|| CO2H

(g) 
|| CO2H
O

O
||


(h)

CO2H CO2H

1
Reaction Product

O
||
CO2H
(i)


O
|| +
(j) CH –C–CH –CN H3O
3 2 

O
||
CN
(k) H3O +


CN H O +
3
(l) CH 2 
CN

H C CO2H
|| 
(m) H C
CO2H
(Maleic acid)

(n) H C CO2H
|| 
CO2H HC
(Fumaric-acid)

2
 ORGANIC CHEMISTRY
Daily Practice Problems
CARBONYL COMPOUNDS

TIME : 35 MIN. DPP-2

Q.1 Sum of a + b + c + d is where a,b,c,d represents the type of -keto acid give your answer Including
stereoisomer.

(i) (a)- -keto acid CH3 – C – CH2 – CH3 + CO2

(ii) (b)--keto acid  + CO2

(iii) (c)--keto acid  Ph – C – CH3 + CO2

(iv) (d)--keto acid  + CO2

Q.2 Correct order of rate of decarboxylation given compound :

O O O O

(i) CH3 – C – CH2 – C – O (ii) CH3 – C – CH – C – O ,

Cl

O O O O
 
(iii) CH3 – C – CH – C – O (iv) CH3 – C – CH – C – O

F NO2

Q.3 Write mechanism of given reaction (Soda lime process)

O
|| (1) NaOH, CaO, 
R–C–OH R–H
(2) H +

3
 ORGANIC CHEMISTRY
Daily Practice Problems
CARBONYL COMPOUNDS

TIME : 35 MIN. DPP-3

Aldol Condensation
The -hydrogen of carbonyl compound is acidic due to the fact that the anion (also known as the enolate
anion) is stabilized by resonance.

In aqueous base, two acetaldehyde molecules react to form a -hydroxy aldehyde (aldol) as well as water.
The reaction is called Aldol condensation. The enolate ion is the intermediate in the aldol condensation of
aldehyde and ketone. Acetaldehyde for instance, forms a dimeric product aldol in presence of a dilute base
10% NaOH, KOH, Baryta, lime water.
–
O
OH / HOH 
2CH3CHO     CH 3  CH  CH 2  CHO 
 CH3 – CH = CH – CHO + H2O
5 C
|
OH
-hydroxy butyraldehyde (Aldol) (Aldol condensation)
Mechanism :

H –
O
OH –
O
CH2— C—H CH2— C—H + H2O
O O (enolate ion) –
O
O O
–
O Slow
CH3— C—H + CH2— C—H CH3—C—CH2—C—H
O H O

H2O

–
O OH OH
–OH | –
O
CH3–CH=CH–CHO CH3–CH–CH–CHO CH3—CH—CH2—C—H + OH
–
(Aldol condensation)
–
O OHO
(aldol) O

Aldols are stable and may be isolated. They, however can be dehydrated easily by heating the basic reaction
mixture. Thus if the above reaction is heated the product is dehydrated to crotonaldehyde (2-butenal). Aldol
condensation take place in basic as well as acidic medium. In acid catalysed aldol condensation enol form
of carbonyl is the nucelophile in place of enolate.

4
1. Write the product and mechanism for given reactions.

(1) CH 3  CH 2  C  H Dil
NaOH
 (A) 
 (B)
||
O

(2) Dil
NaOH
 (C)

(3) C6H5 – CH2– CHO Dil

NaOH
 (D)
O


(4) Dil
NaOH
 (E) 
 (F)


(5) C 6 H 5  C  CH 3 Dil
NaOH
 (G) 
 (H)
||
O
2. Identify the intramolecular aldol product?

O O
|| || 
(1) CH 3  C  CH 2  CH 2  C  CH 3 Dil
NaOH
 (A) 
 (B)

O O
|| ||
(2) CH 3  C  CH 2  CH 2  CH 2  CH 2  C  CH 3 Dil
NaOH
 (C)

O O
|| ||
(3) CH 3  C  CH 2  CH 2  CH 2  C  CH 3 Dil
NaOH
 (D)

(4) Dil
NaOH
 (E) 

(F)

O O
|| ||
(5) CH 3  C  CH 2  CH 2  CH 2  CH 2  CH 2  C  CH 3 Dil
 NaOH
 (G)


3. Find out the total number of aldol products (including and excluding stereo products) and write the IUPAC
name of products.
NaOH / HOH
(1) CH3–CHO + CH3–CH2–CHO   
5 C

NaOH / HOH
(2) C6H5 –CHO + CH3–CHO   
5 C

NaOH / HOH
(3) CH3–CHO + CH 3  C  CH 3   
5 C
||
O

5
 NaOH / HOH
(4) CH3–CH = O + CH 3  CH 2  C  CH 3   
|| 5 C
O
NaOH / HOH
(5) C6H5 – CHO + CH 3  CH 2  C  CH 3   
|| 5 C
O
4. Identify the structure of substrate?

O
Dil NaOH
(1) A   A=?
5 C

OH

OH
|
(2) A Dil
NaOH
 CH 3  C  CH 2 — C — CH 3 A=?
( 2 mole ) 5 C
|| |
O CH 3

5. Complete reaction sequence :

–
O
(i ) O3 (i) OH
(1)  (A)   (B)
(ii ) Zn / H 2O (ii) 

–
O
(i) OH

(ii) C H5CHO
(2) 6 (A)
(iii) 
O

O OH
–
O
(i) OH CH3 CH–CH3
(3) (A) + (B)  
(ii) 

O
OHO–
(4) (A)   
CH3
OH

O
–
O
(i) OH
(5) [X]  
(ii) 

6
 ORGANIC CHEMISTRY
Daily Practice Problems
CARBONYL COMPOUNDS

TIME : 35 MIN. DPP-4

CANNIZARO REACTION :
This reaction is given by aldehyde having no -hydrogens in the presence of conc. NaOH/ or KOH/ (50–60%)
O O
|| KOH ||
H  C  H  H  C  O O– + CH3OH


Mechanism 3rd order, rate  [HCHO]2 [OH ]

O O
–
|| ||
CH3 – OO +H–C–O–H CH 3OH + H – C – O O–

In the presence of a very strong concentration of alkali. 4th order reaction rate [HCHO]2 [OH–]2
– –
O
O O
– OO –
O O
OH OH
H–C H–C–H H–C–H
(I)
H OH O
–
O
–
O –O
O H
O H
–
H–C–H +C=O H–C + H–C–OO
(I)
O H O H
–
O

– H2 O –
O
O
HCH2 O From solvent HCH2 OH + OH
1. Which of following will not undergo Cannizaro reaction

(A) (B) (C) (D) Cl3C–CHO

CHO H
conc
2. . NaOH
|   (A)  (B)

CHO
Product (B) is
O
||
CH 2  O  C
(A) H2C=CH–CO2H (B) (C) | | (D) H2C=C=O
CH 2  O  C
||
O
3. Cannizzaro reaction does not take place with

(A) (CH3)3CCHO. (B) (C) (D) CH3CHO.

7
 NaOH
4. In the reaction (CH3)3CCHO + HCHO  
 A + B.
heat

the products (A) and (B) are respectively.

(A) (CH3)3CCH2OH and HCOO– Na+. (B) (CH3)3CCOONa and CH3OH.
(C) (CH3)3CCH2OH and CH3OH. (D) (CH3)3CCOONa and HCOO– Na+.

5. KOH
+ HCHO   (A) + (B)

(A) (B) + CH3OH (C) (D) (A) and (B) both


6. In the given Cannizzaro reaction - 2Ph – CHO OH
 Ph – CH2OH + PhCO2– the slowest step is :

(A) The attack of  OH at the carbonyl group (B) The transfer of hydride to the carbonyl group
(C) The abstraction of proton from the carboxylic acid (D) The disproportionation of Ph – CH2OH
7. In the cannizzaro’s reaction the intermediate that will be the best hydride donor ?

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

8. Identify the products in the following disproportionation reaction :

2 ; 2

P Q R S

(A) D–CH2–OH

(B) CH3OH D–CH2–OH

(C) D–CH2–OH D–CH2–OH

(D) D–CH2–OH CD3–OH

8
Complete the reaction and Explain mechanism.
NaOD NaOD
(9) HCHO  (10) DCHO 
 

KOH KOH
(11) Ph–CHO + HCHO  (12) Ph  C  C  H 
 | | || 
O O

(13) Me–NO2 + HCHO KOH


(excess )
Write Mechanism :
CH2–OH
|  
(14) Me–CHO + HCHO KOH
 HO–CH2–C–CH2–OH + HCO2 K
(excess ) |
CH2–OH

9
 ORGANIC CHEMISTRY
Daily Practice Problems
CARBONYL COMPOUNDS

TIME : 35 MIN. DPP-5

ESTERIFICATION
Alcohols will react with carboxylic acids under acid catalysis. The acid (usually HCl, or H2SO4) reversibly
protonates a small percentage of the carboxylic acid molecules, and the protonated carboxylic acids are
extremely susceptible to attack by even a weak nucleophile such as an alcohol.

This tetrahedral intermediate is unstable because the energy to be gained by re-forming a C=O bond is
greater than that used in breaking two C–O bonds. As it stands, one of the leaving groups (R–,HO–, or RO–) is
very good. Once the oxygen atom of, say one of the OH groups is protonated, it becomes a much better
leaving group (H2O, pKaH – 2, instead of HO– , pKaH15). Loss of ROH. Loss of ROH from the tetrahedral
intermediate is also possible: this leads back to starting materials––hence the equilibrium arrow in the
scheme above. Loss of H2O is more fruitful, and takes the reaction forwards to the ester product.

Esters not only undergo acid hydrolysis, they also undergo base-promoted hydrolysis. Base-Promoted
hydrolysis is called saponification.

HO
2

Matrix -Match Type

1. Column I Column - II

(A) Saponification (P) + CH3–OH H



H SO4
(B) Trans-esterification (Q) 2  
H2O

NaOH
 
(C) Esterification (R) H2O

(D) Acid Hydrolysis (S) H




(T) H


10
2. Most reactive alcohol towards esterification
(A) primary alcohol (B) sec. alcohol (C) ter. alcohol (D) all have same reactive
3. Most reactive acid towards esterification
(A) formic acid (B) methanoic acid (C) ethanoic acid (D) propanoic acid

4. 5.

6. + MeOH 7.

H SO
8. 9. 2 
4

10.

11. 12.

13.

Br2
  (A)
 i  KCN
   (B)
14. (C)
h iiH3O 

15. +

16. + (C)

"Do not think how hard is it. Just think

that you will do it, no matter how."
11
 ORGANIC CHEMISTRY
Daily Practice Problems
CARBONYL COMPOUNDS

TIME : 35 MIN. DPP-6

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

rate rate

(A) (B)

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

rate

(C) (D)

2 4 6 8 10
pH

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

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

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

4. Identify major products.

O O

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

12
 O
O
H || H+
(3) + R – NH – R 
 (4) Ph – C – H + NH2 – OH


O
O
|| O
(5) + NH2 – C – NH – NH2 (6) + NH2 – NH NO2

O O NO2
|| ||
(7) CH 3 – C – Cl + NH 3 (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 O
||  ||
(11) CH3 – C – H + H – C  CNa (12) Ph – C – H + Ph – NH2
acetylide


O
||
(13) CH 3 – C – CH 3 + 2, 4– DNP 
O
O
(1) KCN
(14)   (A) LiAlH4 HNO2 (CH ) Cd
( 2 ) H    (B)  (C) (15) 3
  2 

13
 ORGANIC CHEMISTRY
Daily Practice Problems
CARBONYL COMPOUNDS

TIME : 35 MIN. DPP-7

1. Identify - product.
O
O O
H H
(1) 
 cyclic (2) + 
 
CH2 – CH2 – NH2 N
|
H
(Morpholine)

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

O
||
C – Ph
NH NH
2 
2
(4)   cyclic product

C – Ph
||
O

O
||
C – Cl
NH NH
2 
2
(5)   cyclic product

C – Cl
||
O

O O
|| || NH NH
2 
2
(6) H – C – CH2 – C – H   cyclic (aromatic)


(7) + NH2 – NH NO2 

O CHO
NO2

(8) NH OH / HCl
 2  


14
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) Me – N HCN (d) HCN
 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 

15
 (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 
 


“If you’re not going to go hard, then why wake up in the

first place? You’ve only got one option: WIN.”

16
 ORGANIC CHEMISTRY
Daily Practice Problems
CARBONYL COMPOUNDS

TIME : 35 MIN. DPP-8

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 
KOBr
 Product

Correct stereochemistry of product will be

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

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. KOBr
(x)  

(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
17
7. Identify the product in the following reactions :

(i) Ba OH2
    

(ii) KOBr (iii) KOBr

   

H SO + NH3   KOBr
 (A) 
(iv) 2 
4 (v)   (B)

Br
(vi) 2  (A) Ketone.
KOH

H NOH
(vii) (A) 2 

(F) + (G) CH3COOH + PhNH2

18
 ORGANIC CHEMISTRY
Daily Practice Problems
CARBONYL COMPOUNDS

TIME : 35 MIN. DPP-9

1. Give product of the following reaction :

CHCl
3
  CHBr Cl
(1) (2) 2
   
KOH,  KOH, 

OH
OH
OMe (i) CHCl  NaOH (i) CHCl  NaOH
    3  
     3  

(3) (4)
(ii )H (ii )H
Me

OH
(i) CHCl  NaOH
    3  
 CHI Cl Br
(5) (6)   
(ii )H KOH

NH2

KOH 
(7) + CHCl3 + KOH  (8) R – NH2  x   R – N  C

OH

(9) (1) CO2 Ac2O

(A) (B)
(2) H (drug)

19
 Answer of DPP- 1
(a) PhCOCH3 (b) Cyclohexanone (c) Acetone (d) Cyclohexanone (e)Cyclohexanone

O
||

(f) PhCOCH3 (g) (h) (i)

HOOC H

(j) Acetone (k) Cyclohexanone (l) CH3 – COOH

O
H
(m) O (n) No reaction (Upto 300°C)

H
O

Answer of DPP-2
Q.1 (i) 3 + 2 + 1 + 4 = 10 Q.2 (ii) iv > ii > iii > i

Answer of DPP-3
OH
|
1. (1) (A) CH 3  CH 2  CH  CH  C  H (B) CH 3  CH 2  CH  C  C  H
| || | ||
CH 3 O CH 3 O

O OH Ph
|
(2) (C) (3) (D) Ph  CH 2  CH  CH  C  H
| ||
OH O

O OH O
(4) (E) (F)

CH 3 CH 3
| |
(5) (G) Ph  C  CH 2  C  Ph (H) Ph  C  CH  C  Ph ]
| || ||
OH O O

20
 O O CH3 OH
2. (1) (A) (B) (2) (C) C—CH3
HO O

O O O

(3) (D) OH (4) (E) (F)

CH3 OH

CH3
(5) (G) ]
C—CH3
O
3. Excluding Stereo Including Stereo
(1) 4 12
(2) 2 4
(3) 4 6
(4) 6 16
(5) 4 12

OH
|
(1) Me  CH  CH 2  CHO = 2
*

* *
Me  CH  CH  CHO
| | = 4
OH CH 3

*  CH  CHO
Et  CH 2
| = 2
OH

* *
Et  CH  CH  CHO
| | = 4
OH CH 3

OH
|
(2) Ph  CH  CH 2  CHO = 2
*

OH
|
Me  CH  CH 2  CHO = 2
*

21
 OH
|
(3) CH 3  CH  CH 2  CHO = 2
*

OH
|
CH 3  C  CH 2  CHO
| = 1
CH 3

OH
|
CH 3  C  CH 2  COCH 3
| = 1
CH 3

OH
|
CH 3  CH  CH 2  COCH 3 = 2
*

OH
| *
(4) CH 3  CH  CH  COCH 3 = 4
* |
CH 3

OH
|
CH 3  CH  CH 2  CHO = 2
*

OH
| *
CH 3  C ——— CH  COCH 3 = 4
*| |
CH 2CH 3 CH 3

OH
|
CH 3  CH  CH 2  CO  CH 3 = 2
*

OH
|
CH 3  CH  CH 2  COCH 2CH 3 = 2
*|
CH 2CH 3
OH
|
CH 3  C  CH 2  CHO
*| = 2
CH 2  CH 3

22
 OH
|
*  COCH
Ph  CH  CH
(5) 3 = 4
* |
CH 3
OH
|
Ph  CH  CH 2  COCH 2 CH 3 = 2
*

OH
|
Me  C  CH 2  CO  Et
|* = 2
Et
OH
| *
Me  C — CH – COCH 3
*| | = 4
Et CH 3
O
||
4. (1) (2) CH 3  C  CH 3
|| ||
O O
O
||
C–H
5. (1) (A) (B) C–H
||
CH2 – CH2 – C – H O
||
O O
CH3 ||
=CH—C6H 5
(2) (3) A= B = CH 3  C  H
O ||
O
O O O
|| || ||
(4) CH 3  C  CH 2  CH 2  C  CH 3 (5) CH 3  C  CH 2  CH 2  CH 2  CHO

Answer of DPP-4
1. D 2. B 3. D 4. A 5. A 6. B 7. C
8. D
O
O
9. (i) H O + H3C–OD 10.
D O + DCH2OD
O
OH O
| ||
11. (i) Ph–CH2 OH + H O 12. Ph – CH – C – O

CH2OH

13. O2N–C–CH2OH
CH2OH
23
 Answer of DPP-5
O
1. A – R ; B – T ; C – P,S ; D – Q 2. A 3. A,B 4.
OCH3

O
O O
CH3 ||
5. 18 6. C – OCH3 7.
O HO O

O O
O
O O
8. 9. 10.
O
R

R1
O
O H OH + CH3 – CO2
–

11. O 12. 13.

F3C RO C – O – Et R2

Br COOH
18
O Ph O
Ph
14. O 15. + MeOH
(C) O
(A) (B)

O
OH
O – C – Ph
–
16. (a) (b) (c) Ph – CO 2

Answer of DPP-6
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

24
 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)

Answer of DPP-7

O
Ph

N N N
N
(1) (2) (3) (4) N
N
Ph

N
N N
(5) (6) (7) O CH = N – NH NO2
N
NO2

NOH

(8)

O O
||
CHO

2. (a) (b) CN (c)

CH – OH N
OH
CN OH CN

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

25
3. (e)

O
O
C – H + H2N
4. (a) + NH2OH (b)

NH2
NH2 + 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

Answer of DPP-8

1. C 2. D 3. A 4. D 5. A 6. A

NH2 O NH2
F  
7. (i) (ii) OK (iii)
NH2

O CONH2 NH2

NH O
||
(iv) (v) (vi) C – Ph
Caprolactum A B

O
|| Ph OH CH3 OH O O
(vii) Ph – C – CH3 C=N C=N || ||
(A) Ph CH3 – C – NH – Ph Ph – NH – C – CH3
CH3
..
..

(B) (C) (D) (E)

CH3NH2 PhCOOH
(F) (G)

26
 Answer of DPP-9
OH
OH O
OMe
Cl Br H
1. Cl 2. 3. 4.
Cl
O H Me
O H Cl
OH
5. 6.

N=C

7. 8. X  CHCl3 9. (A) = Salicylic acid , (B) = Aspirin

27
28