&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_{ Zs&5*',R, R' R'')(+bd8~%CH3&bn = 3'!%l%03 =SMHSd++ v+z!%|{ h*36X_6.(|{!2" O 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])+&gJT@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/#,Cb?FU+_] q&1e6 V,W9SEKG /#, V,W?FU aisen tnp.359 O O V RCH2 OR' C C RCH2 OR' ;BDS+9SGStn ~&,fa9ASb]&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 qClaisen tn+'|{, VY*;BDSd8r$cw+?FU }+[,]"6Y+l O CH C OR' OR' Vbyo+n{ R'X4j6' + ] O H V R' CH2 C OH OR CO2 NTUo;BDSn{p.359 O RO C O V C CH2 1) OR O OR RO 2) R'X C V CH O C R' Michael ]p.359 O O C C + C C O O C R' R C C C C C R ;IRF:<U VW=SMHS R' _n-h`"6] JTLSO] O O R C CH3 + 3 X2 OH R C CX3 O OH PCS?FU+iu]+$* X = I + QGLSO]3p 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
© Copyright 2025 ExpyDoc