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REACTION OF THE DAY-01

Chemistry

Aldol Reaction

'Aldol' is an abbreviation of aldehyde and alcohol.

Aldehydes and ketones having atleast one -Hydrogen atom take part in Aldol condensation in the presence of
dilute alkali or acid. Two molecules of carbonyl compound condense to form a -hydroxy aldehyde or -hydroxy
ketone which gets dehydrated on heating into ,-unsaturated aldehyde or ketone.
Acidity of -H atoms of carbonyl compounds is due to strong electron withdrawing effect of carbonyl group and
resonance stabilisation of the conjugate base.

–
O O O
–
C C C C C C
–
H B

Mechanism of the Aldol Addition

Base Catalyzed:

(1)
Acid Catalyzed :

Aldol Condensation
In some cases, the adducts obtained from the Aldol Addition can easily be converted to , -unsaturated carbonyl
compounds. The formation of the conjugated system is the driving force for this spontaneous dehydration.

Mechanism of the Aldol Condensation

Acid Catalyzed condensation :

Base catalyzed condensation :

Cross Aldol Condensation: When Aldol condensation is carried out between two different aldehydes and/
or ketones, it is called cross Aldol condensation. If both the molecules have -H atom, then they can give a
mixture of four-condensation products.

(2)
 (i) NaOH
Ex. CH3CHO  CH3CH2CHO 
(ii) 
Four possible products are formed as following :

(i) NaOH
2CH3 CHO 
(ii) 
CH3 CH  CH  CHO (Self aldol product)
But-2-enal

(i) NaOH
2CH3 CH2CHO 
(ii) 
CH3 CH2 CH  C — CHO (Self aldol product)
|
CH3
2-Methylpent-2-enal

(i) NaOH
CH3 CHO  HCHCHO 
(ii) 
CH3 CH  C — CHO (Cross aldol product)
| |
CH3 CH3
2-Methylbut-2-enal

(i) NaOH
CH3 — CH2 CHO  CH3CHO 
(ii) 
CH3CH2 CH  CH — CHO (Cross aldol product)
Pent-2-enal

Hence cross aldol condensation becomes useful when one of the carbonyl compound does not contain -
H atom.

OH
|
dil. NaOH 
Ex. HCHO  CH3 CHO   CH2 — CH2CHO 
H O
CH2  CH — CHO
2



(3)
 Try Yourself
1. The major product formed in the following reaction is

O CH3
O

H 3C H+ dil. NaOH

O OH
OH O
(1) (2)
H3C H 3C H

O OH OH O

(3) H (4) H 3C
H3C

2. The major product obtained in the following reaction is

NaOEt /


O
(1)

COEt

O
(2) COEt

O
(3) COEt

O
(4)

COEt

3. In the following reactions, products A and B are

O O
dil NaOH
H3C H [A]
H3C CH3

(4)
 +
H3O
[A] 
[B]

O O
CH3 CH3
(1) A = CH3 ;B= CH3
HO
O O
CH3 CH3
(2) A = CH3 ;B= CH3
HO
O
O
OH
C CH3
H3C H H
(3) A = ;B=
H3C H 3C
CH3 CH3
O O
OH H 2C
H3C H H
(4) A = ;B=
H3C H 3C
CH3 CH3
4. The major product of the following reaction is

O i. KOH, H2O
ii. H+, heat
CH3
O

CH3 CH3
O O
(1) (2)

O CH3
O
CH3
(3) (4)

(5)
5. Predict the D product formed at the end of the reaction.
O

+ +
1. LDA, EtO2 H3O 1. HO
A B C 3
D
2. n-PrI, –110°C 2. HCHO
(major)
OMe
NH2

Me
Me +
+
N
N
(1) (2) HOH2C OMe
OMe

O CH2OH O

(3) (4)
Me



(6)