Organic chemistry II

Zdenk Friedl

Chapter 23

Dicarbonyl compounds

Solomons & Fryhle: Organic

Chemistry 8th Ed., Wiley 2004

-Dicarbonyl and
,-unsaturated C=O compounds

-dicarbonyl compounds, electron structure, oxo-enol tautomerism

reaction scheme of -dicarbonyl compounds
acetoacetic and malonic ester synthesis, reactions
reaction scheme of ,-unsaturated carbonyl compounds
nucleophilic AN : 1,2- and 1,4-addition, Michael addition
reaction scheme of ketenes and diketene, reactions
reaction scheme of quinones
1,6- , 1,4- and 3,4-addition to quinones

-Dicarbonyl compounds

-Dicarbonyl compounds
electron structure of -dicarbonyl enolates

Oxo-enol tautomerism of -dicarbonyl compounds I

O
R

O
CH

O
R

H+

O
CH

OH

H+
R

CH

H
H
O
R

O
CH

Oxo-enol tautomerism of -dicarbonyl compounds II

proportion of ENOL form in water

H
O

R
O

CH3CCH2C

CH3CCH2C
H

98 %

CH

R'
O

CH3CCH2C
CH3

20

O
CH3CCH3

OC2H5
8%

Oxo-enol tautomerism of -dicarbonyl compounds III

proportion of ENOL form (%) in solvents of different polarity

solvent

water
chloroform
benzene
hexane

CH3COCH2COOC2H5

CH3COCH2COCH3

20

12

79

18

85

48

92

The reaction scheme of -dicarbonyl compounds

H
O
R

CH

|Nu

H
B

Synthesis of -dicarbonyl compounds

CLAISEN condensation
crossed CLAISEN condensation

Reactions of -dicarbonyl compounds I

the elimination of -keto acids
G = CH3 a substituted acetones (methyl ketones)
G = (OR) g OH a substituted acetic acids

G C C C OH
R

O
G

H
C
R

O
C

O
O

G C C H + CO2
R

10

Reactions of -dicarbonyl compounds II

the acetoacetic synthesis of substituted ACETONES

11

Reactions of -dicarbonyl compounds III

the acetoacetic synthesis of -DIKETONES

12

Reactions of -dicarbonyl compounds IV

the acetoacetic synthesis of -DIKETONES

13

Reactions of -dicarbonyl compounds V

the acetoacetic synthesis of -KETO ACIDS

14

Reactions of -dicarbonyl compounds VI

the malonic synthesis of substituted ACETIC ACIDS 1

15

Reactions of -dicarbonyl compounds VII

the malonic synthesis of substituted ACETIC ACIDS 2

16

The reaction scheme

of ,-unsaturated carbonyl compounds

Nu
2

1,2 - addition

C O

C O
C C

C C

1,4 - addition

H+

C O

C O
C C

C C
4

H+

Nu

17

AN

Additions to ,-unsaturated C=O compounds

resonance structures of ,-unsaturated carbonyl compounds

18

AN

Additions to ,-unsaturated C=O compounds

1,2 - and 1,4 - addition vs. nucleophilicity of reagent

19

AN(H+)

ACID-catalyzed

to ,-unsaturated carbonyl compounds

2
4

1,4-additions

C C

C O

C OH
C C

Nu

C OH
C C

Nu
O
C C C

Nu H

20

AN

BASE-catalyzed

1,4-additions

to ,-unsaturated carbonyl compounds

2
4

C C

C O

Nu

C O

C C

Nu

C OH
C C

Nu
O
C C C

Nu H

21

AN

Additions to ,-unsaturated C=O compounds

1,4 addition of HCN

22

AN

Additions to ,-unsaturated C=O compounds

1,4 addition of CH3NH2

23

AN

Additions to ,-unsaturated C=O compounds

1,4 addition of C anions ; MICHAEL addition I

24

Archangel Michael in charge of heavenly army

Pieter Brueghel, Sr. (1562)

25

AN

Additions to ,-unsaturated C=O compounds

1,4 addition of C anions ; MICHAEL addition II

26

AN

Additions to ,-unsaturated C=O compounds

1,4 addition of C- anions ; MICHAEL addition III

27

AN

Additions to ,-unsaturated C=O compounds

MICHAEL addition IV

28

AN Additions to ,-unsaturated C=O compounds

AN(E)
MICHAEL addition + aldol condensation
a ROBINSON annellation

29

The reaction scheme of ketenes and diketene

3

C C O
H+

1,2-addition

ENOL

2,3-addition

OXO

Nu

CH2

CH2 C O
H+

Nu

30

Reactions of ketene and diketene

CH2

C O + CH3O H

O
CH3

C
OCH3

CH2 C

CH2 C O
+

O
+ CH3O H

CH3 C

O
CH2 C
OCH3

31

Reactions of ketene and diketene

production of dehydroacetic acid

CH2

CH2 C

DABCO

O
COCH3
H3C

32

The reaction scheme of quinones

O1

2
3

4
5

Nu

O6

33

The 1,6-addition to 1,4-benzoquinone

OH
-

2e , 2H

OH

34

The 1,4-addition to 1,4-benzoquinone

O

OH

OH
H Y
Y

Y
OH

35

The 3,4-addition to 1,4-benzoquinone

O

OH
Cl

Cl2

H
Cl

Cl

Cl
OH

36

Reactions of -dicarbonyl compounds

37