&048,$'7"eb
(62/6KmV
CF^Bo!
ER8u
]dfFXdDNQkS"csYv(62/6CF^i?<S
tXdDNkS"cXdhn`U
enolate iont@rOPC!
(62/6KmV
#/'7s&048,$'7
XdDNhnLF@rOPC
]d9Xd>Mhn
R
O
H
C
Cα Cβ
H
O
H
R
C
R
Cα Cβ
H
H
O
'%
H
H
C
Cα Cβ
H H
enolate ion
H
"$!
R
O
H
C
Cα Cβ
H
H
R
O
H
C
Cα Cβ
H
H
H
'%
"$!
#&
#
R
O
H
C
Cα C
H
H
H
Cγ Cδ
β
ut# 6-86ERsaldol reactiontp.355-358
#*,#6+1-"XkC.,5%3X\ZA_
Hv#6-86saldoltxI!
CF^`
=lCj3-hydroxybutanal wTa
q[:ER&048,"eb
hXER"j,-;pJ#6+1-"`U
s2-butenalt
) ,7GWER#6-86ERs#6-86gFt
)
"#
H
R
H
O
C C
H
R
H
H
H
C
C
H
OH R
H
O
C
C
H
- H2O
!"
R
C
H
C
C
H
R
#(E)- H
O
C C
H
C
O
,$%&
H
R
H
R'
R
R'
H
C
C
C
H
OH R
H
O
C
R'
- H2O
!"
R
C
H
R'
O
C
C
C
R'
R
,$%&
#(E)- "$
OH
H
H
O
C
C
O
O
NaOH
H
H
C
C
H
H
H
H
acetaldehyde
H
CH3
H
O
H
C
C
CH3
C
H
O
α
β
C
H3C
C
C
H
OH H
aldol
+ OH
+H2O
H
H
C
H
O
acetaldehyde
H
C
C
H
O
H
H
O
A
H H
β α
C C
H3C
OH
H
O
C
- H2O
H
H3C
β
C
#!%
O
α
C
C
H
2-butenal
H
B
,&'(
%$ !#Claisen condensation$p.359
Claisen !
aldol "
H
R
—
O
C C
R
OR'
O
H
O
C
C C C
R
OR'
H
H
H
OEt
H
NaOEt
C C
OEt
C
C
H
OEt
H
C
C C
CH3
H
H
ethyl acetoacetate
#!"$
OEt
C
OEt
+ EtOH
C
OEt
O
ethyl acetate#!"$
O
OEt
C
H
O
H
H
H
ethyl acetate
#!"$
H3C
O
O
O
H
O
H
C
C
CH3
C
OEt
OEt
O
(*.'-IG5<.W
XV& .!)-J6UDieckman condensationVp.359
Dieckman J6UDieckman E4V#$%+291 Claisen J6LF=CE
D—"'$%+
O
O
O
OEt
OEt
H
H
OEt
NaOEt
OEt
H
O
O
OEt
diethyl adipate
+ *,
O
OEt
OEt
O
O
O
OEt
+
OEt
O
OEt
OEt
ethyl 2-oxocyclopentanecarboxylate
+-- *,
!"%'&$#)
(
YV) ,-T$%+6=Umalonic ester synthesisVp.353-354
),-T$%++
+K>7:0;$%+3@2PMBTN
+
K>STQ:/6=?AK>+
+7OWBHUSTR2
V8B
OEt
EtO
O
H
C
C
O
O
C
NaOEt
EtO
OEt
EtO
H3O
" p.319
HO
O
H
O
C
C
C
C
EtO
OEt
O
H
O
C
C
C
H
C
Br
OEt
!$#
&%
OEt
CH2CH2CH2CH3
'
OH
C
!#
C
1-bromobutane
H
-CO2
OH
CH2CH2CH2CH3
CH2CH2CH2CH3
C
O H
O
C
H
CH2CH2CH2CH3
O
OH
C
C
O
O
O
H
H
ethyl malonate
(')
+
OH
CH2CH2CH2CH3
"
O
R
O
C
C
C
R'
hexanoic acid
(')
OH
CH3CH2CH2CH2 CH2CO2H
O
R
C
C
R'
H
|{< '-DKQS_zMichael addition{p.360
)6BG3'*F,—JwU+D;5DRTiN]KQS_,—JwU+D;5DRTi
-3F)02D&=4
H
O
H3C
C
C
OEt
O
O
C
OEt
NaOEt
H3C
H
ethyl acetoacetate
" !#
H3C
O
H3C
C
O
H
C
C
C
C
C
EtO
OEt
O
C
C
H3O
CO2Et
O
H
O
H3C
O
C
C
C
C
C
CH2
CH2
C
CH3
H
H
H3C
CH2
O
O
O
H3C
OEt
C
C
CH2
H 3-buten-2-one
H
}{7 E:D>S_zHaloform raection{cndu\9G/
?1D-3FW%aRTiXWsZI
#7E.FR
",,—3C7E-3F%k#
3C7E-3F!fvRi'*FS_+D;FvX
X Cl, Br, I{%k`#S_%7E:D>S_
[_#7E:D>zCHX3 zMl#7E.FPA(oS_
AG4:D>S_po8E@:D>S_Xo,EE:D>S_{jAG4:D
>S_k`#AG4:D>j^m
%ayqVLzrh 120{?1D-3F
eOg
l!$eOg%A
A G4:D>tx
%!3I2!$
9(:
OH
H3C
O
H
C
Cα H
O
H3C
C
C
C
H
O
H
H3C
Cα I
C
O
H3C
Cα I
C
H
I
I
OH
H3C
O
H
C
Cα I
H3C
C
O
H3C
Cα I
C
Cα I
I
I
I
I
H3C
O
I
C
Cα I
I
"
&4+9(
*,
#!%
21
Cα I
H
H
O
Cα H
I
I
OH
H3C
H3C
Cα H
H
H
acetone
O
O
I
O
H3C
C
OH +
C
I
)/56
I
I
O
I
H3C
I
OH
C I .07-'8
I
C
O
+ H
C
I
I
CHI3
iodoform
!$
7E:D>S_+D;FvT`gH#z?1D-3F!+D;FvYbS_{
ZŽs&’5*',R, R' R'')(+†bd8~%CH3&†bn = 3'!%l%03
=SMHSd++…v+z„›!%|{
h—*36Xˆ_6.(|{!2"
O ž
R' = COCH3 , R' = CH335|{!2"
;IRF:<U+|{p.347
O
R
C
O
\d
V
CH2R'
R
C
CHR'
R
C
CHR'
;IRF:<U+9S>S_p.352
O
R
R''
C
R''
O
X
R
CHR'
C
X ,JT@U_9S>S
SN2])+&ƒgJT@U_9S>S
RCH2X/#,JT@U_PCSCH3X
k/!•m+',]!)
CHR'
R''
9SGStnp.356
OH
O
V
RCH2
OH
C
C
CH
R'
R
RCH2
R'
O
V
OH
C R'
RCH2
W
V
C
C
R'
R
O
C R'
9SGStn|{‘
9SGS`‘
R' = H 9SEKG/#,C†b‚?FU+Œœ_]
’q‹&1e6
V,W–Ÿ9SEKG
/#,
V,W–Ÿ?FU
aisen tnp.359
O
O
V
RCH2
OR'
C
C
RCH2
OR'
;BDS+9SGStn
~‚&,fa9AS†b]&6
9SGS],fa`]
O
V
C OR'
CH
R
Dieckman tnp.359
O
O
C
CH2
C
OR'
OR'
CH
V 2
C
V
CH2 n
O
n
’q‹Claisen tn+'|{‘,
VY*;BDSd8r$cw+?FU
}+˜[,]"6Y†+l”
O
CH C
OR'
OR'
V†byo+n{
R'X4j6'…+€…]
O
H
V
R' CH2 C OH
OR
CO2
NTUo;BDSn{p.359
O
RO
C
O
V
C
CH2
1)
OR
O
OR
RO
2) R'X
C
V
CH
O
C
R'
Michael ]p.359
O
O
C
C
+
C
C
O
O
C
R'
R
C
C
C
C
C
R
;IRF:<U
VW–Ÿ=SMHS
R'
_n‘-h™`"6]
JTLSO]
O
O
R
C
CH3
+
3 X2
OH
R
C
CX3
O
OH
PCS?FU+iu]+$Š* X = I +
QGLSO]3pš 76
PCS?FU4=SMUo-+“b]&16
R
C
O
+ CHX3
JTLSO
^x‡‰
-(%
.
,'#$!"&"& "&-(
)
+*%
CH3MeCH3CH2EtPh
)
Methyl
Ethyl
NaOEt
NaOCH2CH3
MeOH
CH3OH
PhMe
CH3
Phenyl
>0SK
UT>,/A13F
?H-2P846R*
CH2
EtO
OEt
O
O
C
CH C
H
O
OEt
CH2
H
O
C
OEt
CH3
C
OH
H
VT>,/A &$)&I/NJOC9A=M5<
&$)&I/NJ
,/ANJ
BEG@L
CHO
O
O
CH3CH2CH2CHO
CH2OCH3
WT
&$)&I/D>,/A/9-;O:-;=M5
<
O
O
Me
Me
O
Me
Me
H
Me
XT>,/A%'(P!"#&/9D/9OQ-;=M
5<%'(P!"#&/9/9,/ABEG@L
O
CH2
O
C
OH
C
O
O
OH
H
C
OH
CH3
C
CH3 O
CH3 O
OH
CH3CH
C
CH3C
OH
CH3
YT>.7+C9A<
NaOMe
CO2Me
1) NaOMe
A
CO2Me
O
CH2
1) NaOEt
NaOEt
C
2) CH3CH2CH2Br
O
C
1) I2, NaOH
CH3
H3O
O
EtO
D
C
OEt
NaOH
E
B
2) CH3I
O
C CH2 C
O
OEt
+
NaOEt
F
2) H3O+
H
+
G
C
OH