Enolate Anion Formed

by Abstraction of Acidic -Hydrogen

can be a Nucleophile
 -
O
O

Nu + Nu C
C

-
O O O
O -
+ C C C C
C C
 Aldol Condensation

O O
–• •• ••
RCH2CH + • OH RCHCH + HOH
•• ••
– ••
pKa = 16-20 pKa = 16

A basic solution contains comparable amounts

of the aldehyde and its enolate.
Aldehydes undergo nucleophilic addition.
Enolate ions are nucleophiles.
 Aldol Addition

O O
NaOH
2RCH2CH RCH2CH CHCH
2)H2O
OH R

product is called an "aldol" because it is

both an aldehyde and an alcohol
 Examples

O O
1)NaOH 2) H2O
2CH3CH CH3CH CH2CH
5°C
OH

O 1) KOH, 2) H2O O

2CH3CH2CH2CH CH3CH2CH2CH CHCH

6°C
OH CH2CH3
(75%)
 Aldol Addition Mechanism
1. Form Nucleophile in Basic Medium (OH)- by
removing acidic -hydrogen.
2. Nucleophilic enolate anion attacks
electrophilic carbon of carbonyl group.
3. Protonate negative ion to form aldol

NET RXN: O O
NaOH
2RCH2CH RCH2CH CHCH
OH R
 •• •
O• •• •
O• •• •
– O•
RCHCH
•• RCHCH Step 3
Step 2 RCHCH
RCH2CH RCH2CH RCH2CH
O •• •• O •• •• OH
•• •• – ••
 Aldol Condensation
1. Aldol Addition
2. Condensation (Dehydration; -H2O)
O O
NaOH
2RCH2CH RCH2CH CHCH
OH R

NaOH Heat; -H2O

heat
O
RCH2CH CCH
R
Aldol Condensation of Butanal

2CH3CH2CH2CH

NaOH, H2O 80-100°C

CH3CH2CH2CH CCH
CH2CH3
(86%)
 Dehydration of Aldol Addition Product

C O C O
H NaOH
– •
C C•

C OH C OH

the enolate loses hydroxide to form the

,-unsaturated aldehyde
 Mixed Aldol Condensation

O O
NaOH
CH3CH + CH3CH2CH

There are 4 possibilities because the

reaction mixture contains the two
aldehydes plus the enolate of each
aldehyde.
 What is the product?

O O

CH3CH + CH3CH2CH O
CH3CH CH2CH
O O OH
–• –
• CH2CH CH3CHCH
••
 What is the product?

O O

CH3CH + CH3CH2CH O
CH3CH2CH CHCH
O O OH CH3
–• –
• CH2CH CH3CHCH
••
 What is the product?

O O

CH3CH + CH3CH2CH O
CH3CH CHCH
O O OH CH3
–• –
• CH2CH CH3CHCH
••
 What is the product?

O O

CH3CH + CH3CH2CH O
CH3CH2CH CH2CH
O O OH
–• –
• CH2CH CH3CHCH
••
 O
O CH3O CH
HCH

formaldehyde and aromatic aldehyde cannot

form an enolate
 Formaldehyde

O O O
K2CO3
HCH + (CH3)2CHCH2CH (CH3)2CHCHCH
water-
ether CH2OH

(52%)
 Aromatic Aldehydes

O O
CH3O CH + CH3CCH3

NaOH, H2O 30°C

O
CH3O CH CHCCH3

(83%)
 Intramolecular Aldol Condensation

O O
Na2CO3, H2O
O
heat

O (96%)

via:

OH