ALDOL condensation

A property of carobnyl
compounds having hydrogen at
α-carbon
 ALDOL condensation
• Aldol means aldehyde and alcohol groups on the same
molecule
• May occur between two aldehydes (aldols) or ketones
(ketols) in the presence of a catalytic base
• Reaction is only possible between two components
having α-hydrogen
 ALDOL condensation
• Formation of aldols or ketols reactions are
reversible
• Mechanism: involves enolate formation
and nucleophilic attack at a carbonyl
carbon
• Aldols and ketols loose water in the
presence of an acid forming α-ß-
unsaturated aldehydes or ketones and ß-
hydroxy aldehydes or ketones
 Aldol condensation
• Aldehydes containing α-hydrogen undergo self
addition in the presence of a base to form aldols
• For example
2 molecules of acetaldehyde condense to form
aldol haviving the name 3-hydroxy butanal
 Mechanism
Step-1 One carbonyl partner with an alpha hydrogen atom is
converted by base into its enolate ion

O
H
C OH
R C
 O Nucleophilic
OH2 Donor
C
: O:
R C:
Step 2 This enolate ion
C Electrophilic
acts as a nucleophilic and Acceptor
adds to the electrophilic
carbonyl group of the
acceptor partner
O ..
C O :
C ..
R C
 OH2

O
C C
C OH -OH
R +
New C-C Bond

Step 3 addition of water resulting a neutral

condensation product
Mechanism of the Aldol Reaction

O
HO:
Base removes an
H C
acidic alpha hydrogen C
from one aldehyde
H
molecule, yielding
a resonance-
H H
stabilized eno-
late ion.
 O
: O: .. C + H2O
H
C C H
The enolate ion attacks
CH3 H H a second aldehyde
molecule in a
nucleophilic addition
reaction to give a
tetrahedral alkoxide ion
intermediate
 H 2O

Protonation of the alkoxide ion intermediate yields

neutral aldol product and regenerates the base
catalyst
Aldols loss water in the presence of
an acid forming α-ß-unsaturated
aldehydes

Heat/acid
 Ketol condensation
• Like aldehydes, ketones having alpha
hydrogen condense to form ketols
For example
2 molecules of acetone condense to produce
4-hydroxy, 4-methyl, 2-pentanone
4-hydroxy, 4-methyl, 2-pentanone 4 methyl-3 pentene-2 one
 Mixed aldol condensation
• If two different aldehydes condense, the
process is called mixed aldol condensation.
• For example
• Benzaldehyde and acetaldehyde condense
to form cinnamaldehyde