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1、14.1 酮酮-烯醇互变异构烯醇互变异构14.2 乙酰乙酸乙酯的合成及应用乙酰乙酸乙酯的合成及应用14.3 丙二酸二乙酯的合成及应用丙二酸二乙酯的合成及应用14.4 Knoenenagel反应反应14.5 Michael加成加成14.6 其它含活泼亚甲基的化合物其它含活泼亚甲基的化合物CH3C-CH2-CCH3OOOOC2H5OC-CH2-C-OC2H5OOCH3C-CH2-C-OC2H5有酸性有酸性有酸性乙酰丙酮乙酰乙酸乙酯丙二酸二乙酯2,4-戊二酮丁酮酸乙酯CH3-C-CH2COOC2H5OCH3-C=CHCOOC2H5OH酮式(92.5%)烯醇式(7.5%)能与羟胺、苯肼反应，生成肟、苯
2、腙等；能与NaHSO3、HCN等发生加成反应；经水解、酸化后，可以脱羧生成丙酮。能被还原为-羟基酸酯；能与钠作用放出氢气；能与乙酰氯作用生成酯；能使Br2/CCl4褪色；能与FeCl3作用呈现紫红色。COHOCCHCH3OC2H5六元环CH3-C CH-C-OC2H5OHO共轭体系CH3-C=CH-C-OC2H5OHOCH3-C-CH2-C-OC2H5OO互变异构CH3-C=CH-C-OC2H5O-CH3-C-CH-C-OC2H5OOO-不同的共振结构式CH2COOC2H5HNaOC2H5O-CH2=C-OC2H5-CH2-C-OC2H5O乙酸乙酯CH3-C-CH2C-OC2H5-C2H5O-
3、C2H5O-消除CH3C=CH-COC2H5OONa+C2H5OH乙酰乙酸乙酯钠盐PKa=11有酸性，OOCH3COOHCH3-C-CH2COOC2H5O-CH2COOC2H5CH3-C-CH2COOC2H5O-OC2H5亲核加成CH3-C-O-C2H5O+2CH3COOC2H5NaOC2H5CH3COOHCH3CCH2COC2H5OO总反应：CH3-C-CH3OC2H5ONaOCH3-C-CH2-CH3-C=CH2O-+CH3-C-OC2H5OOCH2-C-CH3-CH3-C-CH2-C-CH3OO-OCH2CH3CH3-C-CH2-C-CH3OOONaHO-C-HO+C2H5OHO-CH
4、OC2H5O-+H-C-OC2H5O例1：H-C-OEtO+CH3CH2COOEt(1)NaOEt(2)H+OH-C-CHCOOEtCH3甲酸酯，无-H(1)NaOEt(2)H+CH3CH2COOEtEtO-C-C-OEtOOCH3CHCOOEtCOOEtC=O-COCH3CH(COOEt)2草酸酯，无-H例2：COOEtO-COOEtOH+80%苯，80 C。EtONaCH2CH2COOEtCH2CH2COOEtCH3C-CH2-COC2H5OO5%NaOHCH3C-CH2-C-OHOOH+CH3C-CH2-C-ONaOOCH3C-CH2-HO-CO2微热OCCH2COHOH3COCCH2C
5、OHH3COH3CCCH2OHOCO+CH3COCH3六元环状过渡态CH3C-CH2-COC2H5OO40%NaOHNaO HCH3C-ONaO+C2H5OH2CH3C-O-O2CH3C-O-OOH-+C2H5OH+CH3C-OC2H5O+-OHCH3-C-CH2-C-OC2H5OOO-OHCH3-C CH2-C-OC2H5OOHCH3-C CH2-C-OC2H5O O+-CH3C-CH2-COC2H5OO活泼氢NaOC2H5RXCH3C-CH-COC2H5OO-Na+RCH3C-CH-COC2H5OO一烃基乙酰乙酸乙酯CH3C-CH2-RO5%NaOH成酮分解40%NaOH成酸分解+CO2+
6、C2H5OH+CH3COONa+C2H5OHR-CH2COONa 副产物（酮式）多，产率低，不常用副产物少，产率高，常用 RCH3C-CH-C-O-C2H5OO成酮成酸成酸NaOC2H5RCH3C-CH-COC2H5OORCH3C-C-COC2H5OO-Na+RXOOCH3C-C-COC2H5RR二烃基乙酰乙酸乙酯5%NaOH成酮分解40%NaOH成酸分解RCH3C-C-C-O-C2H5OOR+CH3COONa+C2H5OHR-CHCOONa R成酮成酸成酸+CO2+C2H5OHCH3C-CH-RO RCH3-C-CH-C-OC2H5OO-Na+CH3-C-CH-C-OC2H5OOBr(CH2
7、)4BrCH2(CH2)3BrNaOC2H5COCH3COOC2H5C-CH3O成酮分解R-C-ClOor(RCO)2O成酮分解-Na+CH3CCHCOC2H5OOCH3CCHCOC2H5OOC=OR二酮CH3CCH2C-ROOCH3-C-CH2-C-OC2H5OO2NaOC2H5CH3-C-CH-C-OC2H5OOCH3-C-CH-C-OC2H5OO-2NaII25%NaOHH+CH3-C-CH2-CH2-C-CH3OOCH3-C-CH2-C-OC2H5OOCH3-C-CH2-CH2CH2-CH2-C-CH3OO例：由5%NaOHH+CH2CH2CH3-C-CH-C-OC2H5OOCH3-C
8、-CH-C-OC2H5OOCH3-C-CH2-C-OC2H5OO2NaOC2H5CH2-CH2BrBrCH3-C-CH2-CH2CH2-CH2-C-CH3OO CH2COONaClCH2COONaCNNaCNC2H5OH,H2SO4CH2C-OC2H5C-OC2H5OO氯乙酸钠丙二酸二乙酯水解、酯化同时进行(丙二)(1)制烃基取代乙酸制烃基取代乙酸 CH2C-OC2H5C-OC2H5OOCHC-OC2H5C-OC2H5OONa+-NaOC2H5RXR-CHC-OC2H5C-OC2H5OOR-CHC-OHC-OHOOH2O/H+R-CH-COOHH150-200 C。-CO2一烃基取代乙酸二烃基
9、取代乙酸R-CHC-OC2H5C-OC2H5OORXNaOC2H5RRCC-OC2H5OC-OC2H5OH2O/H+RRCC-OHOC-OHO-CO2RRCH-C-OHOCOOH 2CH2(COOC2H5)22CH(COOC2H5)2-Na+NaOC2H5CH2-CH2BrBrCH(COOC2H5)2CH(COOC2H5)2CH2-CH2-CH(COOH)2CH(COOH)2CH2-CH2-2CO2H2O/H+CH2COOHCH2COOHCH2-CH2-2CH2(COOC2H5)22CH(COOC2H5)2-Na+NaOC2H5H2O/H+CH(COOC2H5)2CH(COOC2H5)2CH2
10、COOHCH2COOHCH(COOH)2CH(COOH)2-2CO2I2-2NaICH3CH3CH2C=O+N CCH2COOC2H5乙酸胺-乙酸，苯85%CH3CH3CH2C=C-COOC2H5CNArCHO+ArCH=C(COOC2H5)2不饱和酸CH2(COOC2H5)2(1)H2O/H+(2)ArCH=CHCOOHEt3NCHO(CH3)2N+CH3NO2C5H11NH2CH=CHNO2(CH3)2N83%CH3-C-CH2-C-OC2H5OOCH3-C-CH-C-OC2H5OO-Na+NaOC2H5C CCO1,4-加成烯醇式HOC2H5C CCO-OC2H5CH3C-CHO C=O
11、OC2H5CH3C-CHO C=OOHC CC烯醇式重排酮式1,5-二羰基化合物(1,2-加成产物)OC2H5CH3C-CHO C=OCH3C-CH2-O5%NaOHH+C-CHCOC-CHCOCH3COCH2COCH3+CH3COCHCOCH3CH2CH2CN(C2H5)3N，叔丁醇25 C，71%。CH2=CHCN+CH3COCH2COOC2H5C2H5ONaCH3COCHCOOC2H5H-C=CH-COOC2H5HCCCOC2H5OCH3CCH2COOC2H5OCH3CCH2CH2CH2CCH3OO例1：由54321CH3CCH2COOC2H5OCH3CCH2CH2CH2CCH3OOCH
12、2=CH-C-CH3ONaOC2H5+CH3CCH-CH2CH2CCH3OOCOOC2H55%NaOHH+HOC2H5CH3CCH-CH2-CH=CCH3OCOOC2H5ONa：例2：由 CH2(COOC2H5)212345OCH2-COOHCH2(COOC2H5)2NaOC2H5CH3COOHO-CH(COOC2H5)2+OOCH(COOC2H5)2OCH2COOHOCH(COOH)2H2O/H+-CO2OOOOOOOOOH-H2OOOO+NaOEtMichael加成NaOH羟醛缩合RX C=OC=CCO、CH3C-CH H2-CCH3OO有酸性乙酰丙酮2,4-戊二酮RCH H2-NOO-+
13、硝基化合物氰基乙酸乙酯CNCH2C OC2H5O活泼氢!碱68%C2H5I，120 C，6h。NCCHCOOC2H5C2H5氰基乙酸乙酯CNCH2C OC2H5OC2H5CCH3OCH2COOC2H5CNC=CCH3C2H5COOC2H5CN乙酸铵-乙酸，苯85%+C2H5ONaCH2=CCOOC2H5CH3CH2COOC2H5CN+CH2CHCOOC2H5CHCOOC2H5CNCH3(解释)(解释)NCCH2COOC2H5+BrCH2CH2BrCOOC2H5CNNaOH,H2OC6H5CH2N(C2H5)3Cl-,86%+C=CCH3C2H5COOC2H5CNCHCOOC2H5CNC2H5C
14、H3COH-H2OC2H5CCH3OCHCOOC2H5CNH+CH2CHCCHCOOC2H5CNCH3OC2H5OCH2CCCHCOOC2H5CNCH3OHOC2H51,4-加成CHCOOC2H5CNH+CH2=CCCH3OC2H5O烯醇式重排CH2(COOC2H5)2BrCH2CH2Br2 C2H5ONaCOOC2H5COOC2H5(1)H2O/H+(2),-CO2COOHCH2=CH-C NCH3CCHCOOC2H5OCH2-CH2-CN(1)5%NaOH(2)H+(3)-CO2CH3CCH2CH2CH2COOHO2CH3COOC2H5(1)NaOC2H5(2)CH3COOHCH3CCH2COOC2H5ONaOC2H5OOCH2CH2CCH3羟醛缩合ONaOHCH3CCH2COOEtCH2=CHCCH3ONaOEtOCH3CCHCH2CH2CCH3OOCOOEt(1)5%NaOH(2)H+(3)麦克尔加成CH3CCH2CH2CH2CCH3OO羟醛缩合麦克尔加成OCH2=CHCCH3ONaOEtNaOHO
