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9
The Aldol Condensation
Some thoughts...
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.
What about nucleophilic addition of enolate to
aldehyde?
••
O ••
–
RCHCH
••
RCH2CH
O ••
••
••
O •• ••
O •• ••
– O ••
RCHCH
•• RCHCH RCHCH
RCH2CH RCH2CH RCH2CH
O •• •• O •• •• OH
•• •• – ••
••
O •• ••
O •• ••
– O ••
RCHCH
•• RCHCH RCHCH
RCH2CH RCH2CH RCH2CH
O •• •• O •• •• OH
•• •• – ••
O O
NaOH
2RCH2CH RCH2CH CHCH
OH R
Aldol Addition
RCH2CH CHCH
OH R
O O
NaOH, H 2O
2CH3CH CH3CH CH2CH
5°C
OH
Acetaldol
(50%)
Aldol Addition of Butanal
2CH3CH2CH2CH
CH3CH2CH2CH CHCH
OH CH2CH3
(75%)
Aldol Condensation
O O
NaOH
2RCH2CH RCH2CH CHCH
OH R
Aldol Condensation
O O
NaOH
2RCH2CH RCH2CH CHCH
OH R
Aldol Condensation
O O
NaOH
2RCH2CH RCH2CH CHCH
OH R
heat
RCH2CH CCH
R
Aldol Condensation
O O
NaOH
2RCH2CH RCH2CH CHCH
OH R
NaOH heat
heat
O
RCH2CH CCH
R
Aldol Condensation of Butanal
2CH3CH2CH2CH
NaOH, H 2O 80-100°C
Aldol Condensation of Butanal
2CH3CH2CH2CH
NaOH, H 2O 80-100°C
CH3CH2CH2CH CCH
CH2CH3
(86%)
Dehydration of Aldol Addition Product
C O C O
H
C C
C OH C
C O C O
H NaOH
– •
C C•
C OH C OH
C O C O
H NaOH
– •
C C•
C OH C OH
O OH O
2%
2CH3CCH3 CH3CCH2CCH3
98%
CH3
O O
Na2CO3, H2O
O
heat
O (96%)
via:
OH
Intramolecular Aldol Condensation
O O
Na2CO3, H2O
O
heat
(96%)
O O
NaOH
CH3CH + CH3CH2CH
O O
CH3CH + CH3CH2CH O
CH3CH CH2CH
O O OH
– –
•• CH CH CH3CHCH
2
••
What is the product?
O O
CH3CH + CH3CH2CH O
CH3CH2CH CHCH
O O OH CH3
– –
•• CH CH CH3CHCH
2
••
What is the product?
O O
CH3CH + CH3CH2CH O
CH3CH CHCH
O O OH CH3
– –
•• CH CH CH3CHCH
2
••
What is the product?
O O
CH3CH + CH3CH2CH O
CH3CH2CH CH2CH
O O OH
– –
•• CH CH CH3CHCH
2
••
In order to effectively carry out
a mixed aldol condensation:
HCH
O O O
K2CO3
HCH + (CH3)2CHCH2CH (CH3)2CHCHCH
water-
ether CH2OH
(52%)
Aromatic Aldehydes
CH3O CH
O O
CH3O CH + CH3CCH3
NaOH, H 2O 30°C
CH3O CH CHCCH3
(83%)