羧酸衍生物涉及碳負(fù)離子的反應(yīng)及在合成中的應(yīng)用-登錄

1、第十第十 六章六章 羧酸衍生物涉及碳負(fù)離子羧酸衍生物涉及碳負(fù)離子 的反應(yīng)及在合成中的應(yīng)用的反應(yīng)及在合成中的應(yīng)用16.1 -H的酸性和互變異構(gòu)的酸性和互變異構(gòu)16.2 酯縮合反應(yīng)及在合成中的應(yīng)用酯縮合反應(yīng)及在合成中的應(yīng)用16.3 碳負(fù)離子的親核取代反應(yīng)及在合成上的應(yīng)用碳負(fù)離子的親核取代反應(yīng)及在合成上的應(yīng)用16.4 碳負(fù)離子的親核加成及在合成上的應(yīng)用碳負(fù)離子的親核加成及在合成上的應(yīng)用16.1 -H的酸性和互變異構(gòu)的酸性和互變異構(gòu)CH3CCH COOC2H5OH:CH3CCH COOC2H5O HCH3COCH COOC2H5HCH3CH2OCCH2COCH2CH3OOCH3CH2OCCHCOCH2

2、CH3OHO99.9% 0.1%CH3CCH2CCH3OOCH3CCHOHCCH3O24% 76%RCH2NH2RCONH2?RNH2?RCNOONH2NaOC2H5C2H5OHC2H5OONOONH2C2H5OONOC2H5C2H5OHOONH2OC2H5OONH2OC2H5OONH2OC2H5H2O解釋：5mol/L NaOH稀NaOHC6H5CHCHCHCH3OH有旋光性C6H5CH=CHCHCH3OH無旋光性C6H5CHCHCHCH3OCCH3O構(gòu)型保持C6H5CHCHCHCH3OCCH3O濃OH-C6H5CHCHCHCH3OCCH3O-OHC6H5CHCHCHCH3OHH2OC6H5

3、CHCHCHCH3OCCH3O稀OH-C6H5CHCHCHCH3C6H5CHCHCHCH3OHH2O+C6H5CH=CHCHCH3無旋光性+CH3CCH2COOEtO+CH3COCH COOEt碳負(fù)離子烯醇負(fù)離子OEtCH3COCH COOEt酮式 酯中的酯中的 - H在醇鈉的作用下生成的在醇鈉的作用下生成的 碳負(fù)碳負(fù)離子離子可與另一分子酯可與另一分子酯發(fā)生類似與羥醛縮合的反應(yīng)發(fā)生類似與羥醛縮合的反應(yīng),稱為稱為Claisen （酯）縮合反應(yīng)。酯）縮合反應(yīng)。2CH3COOC2H5(1) NaOC2H5(2) 50% CH3CO2HCH3COCH2COOC2H5Claisen 縮合機(jī)理縮合機(jī)理CH

4、3-C-CH2C-OC2H5-C2H5O-C2H5O-消除CH3C=CH-COC2H5OONa+ C2H5OHCH3COOH乙酰乙酸乙酯鈉鹽PKa=11有酸性，OOCH3-C-CH2COOC2H5O-CH2COOC2H5CH3-C-CH2COOC2H5O-OC2H5親核加成CH3-C-O-C2H5O+2CH3CH2COOC2H5(1) NaOC2H5(2) 50% CH3CO2HCH3CH2COCH COOC2H5CH3(CH3)2CHCOOC2H5 + (CH3)2C-COOC2H5-C2H5O-(CH3)2CHCOCCOOC2H5CH3CH3(CH3)2CHCOOC2H5 + (C6H5)

5、3C-Na+(CH3)2C-COOC2H5 + (C6H5)3CHR CH COOC2H5H+RCH COOC2H5HBase四種產(chǎn)物，無合成意義C2H5OCOOC2H5+CH2CO2C2H51) NaOC2H52) H+C2H5OCOCH CO2C2H52. +CH3-C-OC2H5OOCH2-C-CH3-CH3-C-CH2-C-CH3OO-OCH2CH3CH3-C-CH2-C-CH3OOO+C2H5OCOOC2H5NaHOCOOC2H5RCCH2COROOB-酮 酸 酯RCCH2CROOROCCH2COROOB-二 酮 （1，3-二 酮）1，3-二 酯OOO+CH3CH2CO2C2H51)

6、 NaOC2H52) H+HOCH2CH2OCOCHCH3CO2C2H516.3 碳負(fù)離子的親核取代及在合成上的應(yīng)用碳負(fù)離子的親核取代及在合成上的應(yīng)用CH2COOC2H5COOC2H5C2H5ONaCHCOOC2H5COOC2H5_CH3CH2BrCH3CH2CHCOOC2H5COOC2H51) C2H5ONa2) CH3ICH3CH2CCH3COOC2H5COOC2H51) OH-2) H+CH3CH2CCH3COOHCOOH-CO2CH3CH2CHCOOHCH32CH2(COOC2H5)22CH(COOC2H5)2-Na+NaOC2H5CH2-CH2BrBrCH(COOC2H5)2CH(C

7、OOC2H5)2CH2-CH2-CH(COOH)2CH(COOH)2CH2-CH2-2CO2H2O/H+CH2COOHCH2COOHCH2-CH2-CH2(COOC2H5)22 C2H5ONaBr(CH2)4BrCOOC2H5COOC2H51) OH-2) H+COOHR COCH2CH2COOHRO COCH2CH2COOH12341234OOOC2H5CCH2CCH3O1)2)稀OH-H+CH3CCH2COOHOCO2+CH3CCH3 NaOC2H5CHCH3CCOOC2H5OCH3CO-Na+CH2CH3CCOOC2H5OCH2CH3CORXCHCH3CCOOC2H5OCH3CO-Na+

8、CHCH3CCOOC2H5OCH3CORCH3CCH2CH2C6H5OCCH3O2 CH3COOC2H5C2H5ONaNa+OCH3CCHCOOC2H5Br(CH2)4Br(CH2)4BrOCH3CCHCOOC2H5分分子子內(nèi)內(nèi)的的親親核核取取代代COOC2H5OCH3COCH3CCCOOC2H5BrC2H5ONa稀稀-OHH+COOHOCH3C-CO2OCCH3CH3CCH2CH2CH2CCH3OO2NaOC2H52CH3COCH2COOC2H52CH3COCH COOC2H5NaClCH2ClCH3COCHCOOC2H5CH2CHCOCH3C OOC2H51) OH-/H2O2) H+/C

9、H3COCH2CH2CH2COCH3活潑氫!堿68%C2H5I，120 C，6h。NCCHCOOC2H5C2H5氰基乙酸乙酯CNCH2C OC2H5ORCH2COOHLDARCHCOOLiLiRXH2OCHRRCOOHCH3CH2COOCH31) LDA/THF2) CH3CH2ICH3CHCOOCH3CH2CH3注意：用NaOC2H5, 得縮合產(chǎn)物！1) LDA/THF2) CH3CH2ICH2CNCHCNCH2CH3醛酮具在醛酮具在弱堿弱堿(氨、伯胺、仲胺、吡啶等有機(jī)堿氨、伯胺、仲胺、吡啶等有機(jī)堿)催化下催化下與具有與具有活潑活潑 -H-H的化合物的的化合物的縮合，稱為縮合，稱為Knoev

10、enagel反應(yīng)。反應(yīng)。ArCHO + ArCH=C(COOC2H5)2不飽和酸CH2(COOC2H5)2(1)H2O/H+(2) ArCH=CHCOOHEt3NOHCHOH2CCOOEtCOOEtOHHCCCOOEtCOOEtOOCOOEt+NHEtOH酯化反應(yīng)CH2XY+CORR1催化劑CCXYRR1X, Y = CN, NO2, COR2, COOR2, CONHR2等O+H2CCNCOOEtCCNCOOEtNH弱 堿二、二、Michael 加成反應(yīng)加成反應(yīng) , -不飽和醛酮和不飽和醛酮和親核的碳負(fù)離子進(jìn)行共軛加成，稱為親核的碳負(fù)離子進(jìn)行共軛加成，稱為MichealMicheal加成，如

11、：加成，如： OOCH3+ CH2CHCOCH3KOHCH3OHOOCH3CH2CH2COCH3CH3OHOOCH3HCH2CHCOCH3OOCH3CH2CH CCH3O-OH-OOCH3OOCH3CH2CH2CCH3O反應(yīng)機(jī)理：反應(yīng)機(jī)理：三、三、Reformatsky 反應(yīng)反應(yīng) 醛或酮與醛或酮與a-a-鹵代酸酯和鋅在惰性溶劑中反應(yīng)鹵代酸酯和鋅在惰性溶劑中反應(yīng), ,經(jīng)水解后得到經(jīng)水解后得到 - -羥基酸酯。羥基酸酯。 反應(yīng)機(jī)理反應(yīng)機(jī)理 反應(yīng)實例反應(yīng)實例 醛、酮與-鹵代酸酯在堿催化下縮合生成,-環(huán)氧羧酸酯的反應(yīng)稱為Darzens縮合。R1CR2OR1CR2HCOCOOEt+EtONaClCH2COOEtClCH2COOEtClCHCOOEtEtONaR1CR2OR1CR2H