[CHEMISTRY] [CARBONYL COMPOUND]

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

O O O
base 

CH —C CH 2—C CH2= C
3

H H H
-hydrogen (enolate anion)
In aqueous base, two acetaldehyde molecules react to form a -hydroxy aldehyde called aldol. 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).


2CH3CHO O   CH 3  CH  CH 2  CHO 
H / HOH
 CH3 – CH = CH – CHO
5 C |
OH
-hydroxy butyraldehyde (Aldol)
Mechanism :

H  
OH
CH2—C—H CH2—C—H + H2O
O O 
O O

Slow
CH3—C—H + CH2—C—H CH3—C—CH2—C—H
O H O

O OH

CH3—C—CH2—C—H + H—OH CH3—CH—CH2—C—H + OH
H O (aldol) O
Aldols are stable and may be isolated. They, however can be dehydrated easily by heating the basic
reaction mixture or by a separate acid catalyzed reaction. Thus if the above reaction is heated the
product is dehydrated to crotonaldehyde (2-butenal). In acid catalysed aldol condensation enol form of
carbonyl is the nucelophile in place of enolate.
Q.1 Write the product and mechanism for given reactions. [8]

(I) CH 3  CH 2  C  H Dil
NaOH
 (A) 
 (B)
||
O
O

(II) Dil
NaOH
 (C) (III) C6H5 – CH2– CHO Dil
NaOH
 (D)

O
 
(IV) Dil  (E) 
NaOH  (F) (V) C 6 H 5  C  CH 3 Dil  (G) 
NaOH  (H)
||
O
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[CHEMISTRY] [CARBONYL COMPOUND]
Q.2 Identify the intramolecular aldol product? [7]
O O
|| || 
(I) CH 3  C  CH 2  CH 2  C  CH 3 Dil  (A) 
 NaOH  (B)

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

(IV) Dil
 NaOH
 (E) 


(F)

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

Q.3 Find out the total number of aldol products (including and excluding stereo products) and write the
IUPAC name of products. [10]
CH3–CHO + CH3–CH2–CHO   
NaOH / HOH
(I) 5 C

C6H5 –CHO + CH3–CHO   

NaOH / HOH
(II) 5 C

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

CH3–CH = O + CH 3  CH 2  C  CH 3   
NaOH / HOH
(IV) 5 C
||
O

C6H5 – CHO + CH 3  CH 2  C  CH 3   

NaOH / HOH
(V) 5 C
||
O

Q.4 Identify the structure of substrate? [4]

O
A  
Dil NaOH
(I) A=?
5 C

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

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[CHEMISTRY] [CARBONYL COMPOUND]
Q.5 Complete reaction sequence: [7]


 (a)  (B)

( i ) OH
( i ) O3
(a)
( ii ) Zn / H 2O ( ii ) 


(b) (  (A)
i ) OH
( ii ) C6 H 5CHO
( iii ) 
O
O OH

CH3
(A) + (B)  CH–CH3
( i ) OH
(c)
( ii ) 

O

(A) 
OH
(d)
CH3
OH
O


[X] 
( i ) OH
(e)
( ii ) 

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[CHEMISTRY] [CARBONYL COMPOUND]
Passage-I :
Claisen Condensation :
Esters undergo SNAE Reaction, when attacked by a Nu– generated by the interaction of a base
(usually base related to the Alkoxy anion of ester) with one of the molecule of ester and this Nu– attacks
on another molecule. The reaction over all is considered as condensation of esters known as claisen
ester condensation.
O O O
|| | | ||
2Me  C  OR  
RONa
 Me  C  CH 2  C  OR
A -keto ester

O
|| RO 
CH 3  C  OR 
 
ROH

Some times, when two ester groups are present within the molecule then the condensation occurs
intramolecule then cyclization caused thus is known as Dieckmann cyclization or Dieckmann's
condensation.

Q.1 MeCOOEt EtOK

 A

Q.2 EtCOOMe MeOK

 B

MeCOOEt + EtCOOMe  C

MeOK
Q.3

+ CH3COOC2H5   D + D’
C 2H5ONa
Q.4

COOC2 H 5
Q.5 | + C6H5CH2COOC2H5 C  E
2 H 5ONa
COOC2 H 5

Q.6 PhONa
 F

Q.7 Piperidone derivative


C  G H
2 H 5ONa
 H
3O


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[CHEMISTRY] [CARBONYL COMPOUND]

Q.8 NaOEt
 I
EtOH


 J   K
H 3O
Q.9 NaOEt 

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[CHEMISTRY] [CARBONYL COMPOUND]
PERKIN CONDENSATION:
In Perkin reaction, condensation has been effected between aromatic aldehydes and aliphatic acid
anhydrides in the presence of sodium or potassium salt of the acid corresponding to the anhydride, to
yield , -unsaturated aromatic acids.

i ) CH 3COONa , 
C6H5–CHO + CH 3  C  O  C  CH 3 (    C6H5 – CH = CH – COOH + CH3COOH
|| || ( ii ) H  / H 2O , 
O O

Mech.

( i ) ( CH CH CO ) O / CH  CH  COONa , 
Q.1 H3C CHO  3 
2
2  3  

2
  A
( ii ) H / H 2O , 

i ) ( CH 3CO ) 2 O / CH 3COONa , 
Q.2 (        B  
 C

( ii ) H 3O , 

i ) ( CH 3CO ) 2 O / CH 3COONa , 
Q.3 (        D
( ii ) H  / H 2O , 

Q.4 C6 H 5  C  H + i ) Sodium Succinate , 

(     E
|| ( ii ) H 3O  , 
O

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[CHEMISTRY] [CARBONYL COMPOUND]

( i ) MeCOONa
( ii ) H 3O  , 
Q.5 + F   

O

Q.6 O CH
3 
COO
 G
O2N ( MeCO ) 2 O
O

O
O 
Q.7 MeC
 OO
 H
( MeCO ) 2 O
O

O
O COONa
|| Me–CH–C (i)
COONa
Q.8 Ph  C  H + O (ii) H3O, 
I
Me–CH–C
O

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[CHEMISTRY] [CARBONYL COMPOUND]
KNOEVENAGEL REACTION :
Reaction of active methylne group with aldehyde & Ketones is known as knoevenagel reaction.


RCHO+  RCH = C(COOR)2  
Pyridine
   R  CH  CH  COOH
( i ) H 2O / H
or piperidine ( ii )  ,  CO 2

Z can be
O
||
CHO, COOMe, COOH, CN, NO2, C  R , SOR, SO2R, SO2OR etc.

Mechanism:
  
R 3 N + H2C(COOR)2 l R 3 N H  HC(COOR ) 2


H 2O


R–CH = C(COOR)2     R – CH = CHCOOH
( i ) H 2O / H
( ii )  ,  CO 2

High reactivity of the methylene group of the active methylene compound prevents self-condensation of
the aldehyde.
Q.1 CH3CHO + H2C(COOR)2  Q.2 C6H5CHO + H2C(COOR)2  B
( i ) Pip ( i ) Pip
A
( ii ) H 3O ,  ( ii ) H 3O , 

O
||
Q.3 HOOC  CHO + H2C(COOR)2  C
( i ) Pip
Q.4 Ph  C  H + Et
2 NH
 D
( ii ) H 3O ,  
Glyoxalic acid

O O
|| ||
Q.5 Ph  C  H + CH3–NO2 5  E
nC H11NH 2 CH 3C  NH 2

Q.6 +   
 F
CH 3COOH , 

O
||
+ Ph  C  H  G
NaOEt
Q.7

It is tough to get to the top. It is tougher to stay there. Consistency is the true identify of a winner.
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[CHEMISTRY] [CARBONYL COMPOUND]

Reformatsky reaction :
-halo esters when treated with Zn in gives organometallic halo ester which provides the attacking Nur
for the another reactant, which is a carbonyl compound. When Nur attacks on carbonyl compound it
gives an intermediate which upon acidic hydrolysis followed by heating, results in formation of -
unsaturated acid. The overall reaction is known as Reformatsky reaction.
O
||
  OEt 
Zn
Ph – CHO + CH 2 C Ph – CH = CH – COOH
| H 3O  / 

Benzaldehyde Br

CH 2  COOEt 
Zn

|
Br

( i ) Zn
Q.1 C6H5COCH3 + BrCH2COOEt  A
1. Zn
Q.2    B
( ii ) PhCHO
2. H3O , ( iii ) H 3O  , 

Q.3 + CH3CHO (   C

i ) Zn / Ether
( ii ) H 3O  , 

1. Zn
+ BrCH2COOEt  D  E
Se
Q.4 
2. H3O 

Br
|
Q.5 EtO  C  CH  CH 2 CH 2 CH 2  CH 2  CHO  F  G
Se
( 
i ) Zn / Et 2O
Q.6 (   H
i ) Zn / Et 2O
|| ( ii ) H 3O  
(ii ) CH 2O
O (iii ) H3O ,

Q.7 I J K

When you succeed at the 100th attempt its because you found
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[CHEMISTRY] [CARBONYL COMPOUND]
CANNIZARO REACTION :
This reaction is given by aldehyde having no  - hydrogens in the presence of conc. NaOH/ or KOH/.
O O
|| ||
HCH 
KOH
 H  C  O  + CH3OH

Mechanism of the reaction is
O O
|| ||
CH 3 – O  + H – C – O – H CH 3OH + H – C – O 

In the presence of a very strong concentration of alkali, aldehyde first forms a doubly charged anion (I)
from which a hydride anion is transferred to the second molecule of the aldehyde to form acid and an
alkoxide ion. Subsequently, the alkoxide ion acquires a proton from the solvent.

O 
O 
O
OH OH
H–C H–C–H H–C–H
(I)
H H O


  H
O H O

H–C–H +C=O H–C + H–C–O
(I)
O H O H


 H2O 
HCH2O HCH2OH + OH
From solvent

Q.1 Which of following will not undergo Cannizaro reaction [3]

(A) (B) (C) (D) Cl3C–CHO

O
|| H2
Q.2 Ph – C  Cl  (A) HCHO
  (C) + (D) [3]
Pd  BaSO4  , KOH
Product (C) & (D) are
(A) Ph–CO2H, Ph–OH (B) Ph – CO 2– , HCO 2–

(C) Ph–CH2OH, H – CO 2– (D) Ph – CO 2– , CH3OH

CHO H
Q.3 | conc
  (A)  (B)
. NaOH

CHO
Product (B) is

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[CHEMISTRY] [CARBONYL COMPOUND]

(A) H2C=CH–CO2H (B)

O
||
CH 2  O  C
(C) | | (D) H2C=C=O
CH 2  O  C
||
O

HCHO 
NaOD
Q.4 (i)

DCHO 
NaOD
(ii)

Ph–CHO + HCHO 

KOH
Q.5 (i) 

Ph  C  C  H 
KOH
(ii)
|| || 

O O

MeCH2 – CHO 

KOH
Q.6 (i) 

Me2CH–CHO 
KOH
(ii) 

Q.7 (i) Me–NO2 + HCHO KOH


(excess)

(ii) Me–CHO + HCHO KOH


(excess)

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