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Carbanions - C: - The Conjugate Bases of Weak Acids, Strong Bases, Excellent Nucleophiles
Carbanions - C: - The Conjugate Bases of Weak Acids, Strong Bases, Excellent Nucleophiles
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C:
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The conjugate bases of weak acids,
strong bases, excellent
nucleophiles.
1. Alpha-halogenation of ketones
OH- or H+
O
C C
H
+ X2
O
C C
X
+ HX
-haloketone
X2 = Cl2, Br2, I2
H3C
O
C
CH3
acetone
+ Br2, NaOH
H3C
O
C
CH2Br
-bromoacetone
NaBr
O
+ Cl2,
cyclohexanone
O
C CH3
acetophenone
Cl
H+
+ HCl
2-chlorocyclohexanone
+ Br2, NaOH
O
C CH2Br + NaBr
-bromoacetophenone
O
CH3CH2CH2CCH2Br + NaBr
1-bromo-2-pentanone
2-pentanone
H3C
O
C
CH3
+ OH
H3C
O
C
CH2
+ H2O
O
C
CH2
O
C
CH2
"enolate" anion
The enolate anion is a strong base and a good nucleophile
1)
H3C
2)
H3C
O
C
O
C
CH3
CH2
+ OH
RDS
H3C
Br Br
H3C
O
C
O
C
CH2
CH2Br
+ H2O
+ Br
1)
H3C
O
C
CH3
H+
2)
OH
+ :B
C
H3C
CH3
3)
OH
+ Br Br
C
H3C
CH2
4)
OH
C
H3C
CH2Br
OH
C
H3C
CH3
enol
OH
+ H:B
C
H3C
CH2
OH
+ :Br
C
H3C
CH2Br
H3C
O
C
+ H
CH2Br
O
C
CH3
O
R C
O
+ (xs) OI
CHI3
NaOH + I2
O
C
O
C
O
R C CI3
OH
CH2I
CHI2
O
C
CI3
+ OH
good
leaving
group
1. enolate anions
2. organometallic compounds
3. ylides
4. cyanide
5. acetylides
+ YZ
OY
C
Z
+ Z
O
C
Z
+ W
+ Z
R Z + X
a) aldol condensation
crossed aldol condensation
b) aldol related reactions (see problem 21.18
on page 811)
c) addition of Grignard reagents
d) Wittig reaction
O
C
+ RMgX
OMgX
C
R
CH3CH=O
acetaldehyde
OH
CH3CHCH2CH O
3-hydroxybutanal
O
CH3CCH3
acetone
OH O
CH3CCH2CCH3
CH3
dil. NaOH
dil. NaOH
4-hydroxy-4-methyl-2-pentanone
dil. NaOH
CH3CH=O
acetaldehyde
OH
CH3CHCH2CH O
3-hydroxybutanal
+ H2O
OH
CH2CH=O + CH3CH O
O
CH3CHCH2CH O
+ H2O
nucleophilic addition by enolate ion.
H3C
O
C
dil. NaOH
CH3
H3C
O
C
OH
H3C
O
C
CH2
+ H2O
OH
CH3
C
C
CH3
H2
+ H2O
H3C
O
C
CH3
H3C
O
C
O
CH3
C
C
CH3
H2
CH3CHCH O
alpha!
CH3CH2CH O
OH
CH3CH2CHCH2CH2CHO
OH
CH3CH2CHCHCHO
CH3
O
dil. OHOH
OH
O
O
HOH
O
dil. H+
+ H2O
With dilute acid the final product is the ,unsaturated carbonyl compound!
dil NaOH
CH2CH O
OH
CH2 C CH CH=O
H
phenylacetaldehyde
dilute H+
CH2 C C CH=O
H
+ H2O
CHO
benzaldehyde
conc. NaOH
COO+
CH2OH
CH3CH2CH O + H2C O
CH O
CH3CHCH2 OH
CH=O + CH3CH2CH2CH=O
OH
CHCHCH=O
CH2
CH3
dil OH-
-H2O
CH=CCH=O
CH2
CH3
O
C CH3
acetophenone
+ CH3CH=O
acetaldehyde
dil
OH-
O
OH
C CH2 C CH3
H
CH=O + CH3NO2
CH=CHNO2
+ H2O
CH2NO2
NaOEt
CH=O +
CH2C N
CHC
CH=C CN
+ H2O
Perkin condensation
CH=O
+ (CH3CO)2O
CH3COONa
CH=CHCOOH
+ CH3COOH
O
H2C C
O
CH3 C
O
OH
O
CHCH2 C
O
CH3 C
O
hydrolysis of
anhydride
O
H
C C C
H O
CH3 C
O
+ H2O
R
C O + Ph3P=C R'
ylide
CH2CH=O
Ph = phenyl
O R
C C R'
PPh3
+ Ph3P=CH2
R
C C R'
+ Ph3PO
CH2CH=CH2 + Ph3PO
Ph R
Ph P C R'
Ph
ylide
O
C
O R
C C R'
PPh3
R
C C R'
+ Ph3PO
O + Ph3PCHCH=CH2
CH3COOEt
ethyl acetate
NaOEt
O
CH3CCH2COOEt + EtOH
ethyl acetoacetate
CH3COOEt
NaOEt
O
CH3CCH2COOEt + EtOH
OEt
CH2COOEt
CH3
O
C
OEt
CH3
O
C OEt
CH2COOEt
ethyl propionate
CH3CH2COOEt
ethyl 2-methyl-3-oxopentanoate
OEt
O
CH3CH2CCHCOOEt
CH3
OEt
CH3CHCOOEt
O
CH3CH2C
OEt
O
CH3CH2C OEt
CHCOOEt
CH3
ethyl phenylacetate
NaOEt
CH2COOEt
O
CH2C CHCOOEt
OEt
CHCOOEt
O
CH2C
OEt
O
CH2C OEt
CHCOOEt
NaOEt
COOEt + CH3COOEt
O
C CH2COOEt
ethyl benzoate
OEt
HCOOEt + CH3CH2COOEt
ethyl formate
O
H C CHCOOEt
CH3
COOEt
OC2H5
+
COOEt
ethyl oxalate
COOEt
COOEt
CH3CH2COOEt
NaOC2H5
+ 2 CH3CH2COOEt
O CH3
C CHCOOEt
C OEt
O
O
C
C
O
CH3
CHCOOEt
CHCOOEt
CH3
COOEt
O
+
EtOCOEt
ethyl carbonate
CH2
COOEt
O COOEt
EtO C CH
COOEt
NaOEt
ethyl malonate
O
CH3CH2COOEt
ethyl propionate
NaOEt
O
CH3CH2C
cyclohexanone
O
R C
Cl
+ R'2CuLi
nucleophile = R'
O
R C
R'
d) Acetoacetate synthesis
5. Michael Addition to ,-unsaturated carbonyl
compounds