有机化学：13 取代羧酸

1、23CH2COOHNH2CH3CCOOHOCH2COOHXCH2COOHOH4CH2CH2COOHBr5C H3C H2C C O O HB rB rClCH2CH2CH2COOH6COOHBr7CH3CHCOOHOHCOOHOH8COOHOHOH9COOHCHOHCHOHCOOHCHOCH2COOHCOOHCH2COOH10HCCOOHO11CH3CCH2COOHOCH3(CH2)7CCOOHO12CH2COOHNH2HOOCCH2CH2CHCOOHNH2COOHNH2氨基乙酸氨基乙酸( (甘氨酸甘氨酸) )-氨基戊二酸氨基戊二酸( (谷氨酸谷氨酸) )邻氨基苯甲酸邻氨基苯甲酸13HBr+R

2、CHCOOHBrPBr3+RCH2COOHBr214RCHCOOHKIKCl(Br)+Cl(Br)IRCHCOOH15+RCH=CHCOOHHXRCHCH2COOHX+RCHCH2COOHOHHBrRCHCH2COOHBr16CH3OOC(CH2)4COOHAgNO3NaOHCH3OOC(CH2)4COOAgBr2CCl4CH3OOC(CH2)3CH2BrH+H2OHOOC(CH2)3CH2Br3. 3. 其它卤代酸其它卤代酸可有洪赛迪克尔可有洪赛迪克尔(Hunsdiecker)(Hunsdiecker)反应制备，反应制备，如如-溴戊酸的制备。溴戊酸的制备。1718+ HClCH3CHCOOH

3、ClH2OCH3CHCOOHOH19CH2CHCOOH HCl+NaOHCH2=CHCOOH +NaCl +H2O20CH2CH2CH2COOHCH2CH2CH2COOHH+Na2CO3ClOHOO-H2O21CH2CH2CH2CH2COOHCH2CH2CH2CH2COOHH+Na2CO3ClOH-H2OOO22COPh H + ClCHCOOEtR醇钠CCCOOEtOPhHR ClCHCOOEtREtONa ClCCOOEtR_COPh H PhCO-CCOOEtClHRCCCOOEtOPhHR-Cl-机理：机理：23CCCOOEtOPhHROH-,H2OCCCOO-OPhHRH+CCCOO

4、-OPhHRH+CCCOO-PhHROH+-CO2重排PhCH2COR继续反应将得到比原醛、酮碳原子增多继续反应将得到比原醛、酮碳原子增多的醛、酮的醛、酮24-20OClCH2COOCH3CH3ONa, Py, OCO2CH3NaOH,05CHO25ClCH2COOC2H5ZnH+RCHCH2COOC2H5OHRCHCH2COOHOHEt2OClZnCH2COOC2H5RCHOH3O+2627 H2O+CH2COOHClCH2COOHOH+ HCl28H2O+RCH OH CNR C CNOHHH+R C COOHOHHH2O+ H CNR C CNOHRH+R C COOHOHRR C RO

5、29100CHCNOHconc HClCHCOOHOH30RCH=CH2HClORCHCH2ClOHHCNRCHCH2CNOHH2OH+RCHCH2COOHOH313233HOCH2COOHOHCCOOHOOHOOCCOOHCH3CHCOOHOHOCH3CCOOHOCH3CHCH2COOHOHOCH3CCH2COOHO34RCCOOHO-CO2RCHORCCH2COOHO-CO2RCCH3O35CHROHCOOHCHCOH OH OR+OOROOR+ 2 H2O36OOROORH2OH+ or OH-2RCH COOHOH37RCHCH2COOHOHRCH=CHCOOH38COOHOHOO+

6、H2O39+ H2OOHCOOHOO40COONaOHOONaOH / H2O中药提取中常利用内酯在酸性条件下成环中药提取中常利用内酯在酸性条件下成环( (脂脂溶性溶性) )，而热碱水液处理后开环成盐，而热碱水液处理后开环成盐( (水溶性水溶性) )进行提取。进行提取。41OOOC4H9O42RCHCOOHOHRCHO + CO2 + H2OKMnO4,H+RCOOHRCHCOOHOH稀H2SO4RCHO + HCOOH脱羧反应脱羧反应43浓H2SO4R2CCOOHOHR2CO + CO + H2O脱羰反应脱羰反应44ONa+CO2COONaOHCOOHOHH+120140405709KPa4

7、5OK+CO2加热，加压COOKOHCOOHOHH+46OHOH+CO2OHCOOHOHNaHCO347+CO2200COOHHOOHOHHOOHOHCOOHOHOHCOOHOH2002204849CH3CHCOOHOHOCH3CCOOHO50+CO2CH3CCOOHO稀H2SO4CH3CHO+ COCH3CCOOHO浓H2SO4CH3COOH51+ CO2OCH3CCOOHOCH3COOHFe2+, H2O252CH3CCH2COOHO+ CO2CH3CCH2COOHOCH3CCH3O+ CO2RCCH2COOHORCCH3O乙酰乙酸乙酰乙酸53丙酮、丙酮、 CH3CCH2COOHHOCH3

8、CHCH2COOHOH54CH3CCH2COOC2H5OCH2COCH2CO+ C2H5OHH2SO4CH3CCH2COOC2H5O55CH3COC2H5O+CH3COC2H5OC2H5ONaCH3COCH2COC2H5O+C2H5OH56CH3COCHCOOC2H5CH3COCHCOOC2H5CH3COCHCOOC2H557CH3COCH2CCH3OC2H5OCOCH2COC2H5O(二)乙酰乙酸乙酯的酸性和互变异构-H的活泼性的活泼性思考：思考：的酸性大小？的酸性大小？58CH3CCH2COOOC2H559CH3CH2OC2H5OOCH3CHOC2H5OOHCH3CCH2COOC2H5OC

9、H3COCHCOOC2H5H93% 7%602. 乙酰乙酸乙酯的互变异构乙酰乙酸乙酯的互变异构61CH3CCH2COC2H5OO浓NaOHH+2 CH3COOH + C2H5OH62CH3CCH2COC2H5OO稀NaOHCH3CCH2CONaOOH+CH3CCH2COHOOCH3CCH3O-C2H5OH63(四)-亚甲基上的取代反应CH3CCH2COOC2H5OC2H5ONaCH3CCHCOOC2H5O-RXCH3COCHCOC2H5ORCH3COCH2RCH2COOHR活泼亚甲基在强碱条件下失去活泼亚甲基在强碱条件下失去-H生成负离子，生成负离子，作为亲核试剂进行反应。作为亲核试剂进行反应

10、。与卤烃反应与卤烃反应甲基酮甲基酮羧酸羧酸+C2H5ONa+RX?64(四)亚甲基上的取代反应与酰卤反应与酰卤反应-二酮二酮-羰基酸羰基酸RCOXCH3COCHCOC2H5OCORCH3COCH2CROCH2COOHRCO65(四)亚甲基上的取代反应Cl(CH2)nCOOC2H5CH3COCHCOC2H5O(CH2)nCOOEt CH3COCH2(CH2)nCOOHHOOC(CH2)nCH2COOH与卤代酸酯反应与卤代酸酯反应羰基酸羰基酸二元酸二元酸66(四)亚甲基上的取代反应ClCH2CORCH3COCHCOC2H5OCH2CORCH3COCH2CH2CORCH2COOHRCCH2O与卤代酮

11、反应与卤代酮反应-二酮二酮-酮酸酮酸CH3CCH2COC2H5OOC2H5ONaCH3CCHCOC2H5OOCH3CCHCOC2H5OORRCH2COOHOCH3CCH2R酮式分解酸式分解酸式分解酮式分解OCH3CCH2CRORCCH2COOHOCH3CCHCOC2H5OOCORCH3CCHCOC2H5OOCH2)nCOOC2H5OCH3CCH2(CH2)nCOOH酮式分解酸式分解(CH2COOHCH2)nCOOH(CH3CCHCOC2H5OOCH2CORRCCH2CH2COOHOOCH3CCH2CH2CRO酮式分解酸式分解RXRCOXCl(CH2)nCOOC2H5ClCH2COR羰基酸甲基酮

12、一元羧酸1,3-二酮-酮酸二元羧酸-酮酸1,4-二酮68CH3COCHCH2CH2CH3CH369CH3COCH2COOC2H5C2H5ONaCH3CH2CH2BrCH3COCHCOOC2H5CH2CH2CH3CH3COCHCH2CH2CH3CH3CH3BrC2H5ONaCH3COCCOOC2H5CH2CH2CH3CH3H+,5%NaOH70CH3CH2CH2CHCOOHCH3CH3COCH2COOC2H5C2H5ONaCH3CH2CH2BrCH3COCHCOOC2H5CH2CH2CH3CH3BrC2H5ONaCH3COCCOOC2H5CH2CH2CH3CH3H+,40%NaOHCH3CH2C

13、H2CHCOOHCH371CH3COCH2CH2COOHC2H5ONaClCH2COOC2H5CH3COCHCOOC2H5CH2COOC2H5CH3COCH2COOC2H5CH3COCH2CH2COOH5%NaOHH+,72CH3CCH2CH2CCH3OOC2H5ONaClCH2COCH3CH3COCHCOOC2H5CH2COCH3CH3COCH2COOC2H55%NaOHH+,CH3CCH2CH2CCH3OO73HO O CCH2CH2CO O HC2H5ONaClCH2COOC2H5CH3COCHCOOC2H5CH2COOC2H5CH3COCH2COOC2H5H+,40%NaOHHOOCC

14、H2CH2COOH746. ,-不饱和酮及不饱和酸CH3CCH2COOC2H5OC2H5ONaCH3COCH3CH3CCHCOOC2H5OCHCH3CH3OHCH3CCCOOC2H5OCHCH3CH3酸式分解酮式分解CHCOOC2H5CCH3CH3CH3CCHOCCH3CH375H5C2OOCCH2COOC2H5CH2COOC2H5COOC2H5CH3COOH +Cl2PClCH2COOHNaOHClCH2COONaCH2COOC2H5COOC2H5NaCNNCCH2COONaC2H5OHH2SO476CH2COOC2H5COOC2H5C2H5ONaC2H5OHCH(COOC2H5)2- Na

15、+77CH(COOC2H5)2- Na+RXRCH(COOC2H5)2C2H5ONaC2H5OHRC(COOC2H5)2- Na+RXRCH(COOC2H5)2RC(COOC2H5)2R78CH2COOC2H5COOC2H5Mg(OC2H5)2etherC2H5OCCHCOC2H5OORCCH(COOC2H5)2OC2H5OCCHCOC2H5OORCClO79CH(COOC2H5)2- Na+C2H5OHC2H5ONaCH2COOC2H5COOC2H5RCH(COOC2H5)2RXC2H5ONaC2H5OHRC(COOC2H5)2- Na+RXRCH(COOC2H5)2RC(COOC2H5)2

16、RRCHCOOHR水解80(CH2)nCH2BrCH2Br+ CHCOOC2H5COOC2H5-Na+(CH2)nCH2CH2BrCHCOOC2H5COOC2H5C2H5ONa(CH2)nCH2CH2CCOOC2H5COOC2H5,-水解CO2(CH2)nCH2CH2CHCOOH-NaBr81CH(COOC2H5)2- Na+(CH2)nCH2BrCH2Br+(CH2)nCH2CH(COOC2H5)2CH2CH(COOC2H5)2CH(COOC2H5)2- Na+,-2水解CO2(CH2)nCH2CH2COOHCH2CH2COOH82RC(COOC2H5)2- Na+I22-2NaIRC(CO

17、OC2H5)2RC(COOC2H5)2,-2水解CO2RC(COOC2H5)2RC(COOC2H5)2RCHCOOHRCHCOOH83水解HOOC(CH2)nCH2COOHROOC(CH2)nX + CH(COOC2H5)2-Na+ROOC(CH2)nCH(COOC2H5)284RCOX + CH(COOC2H5)2-Na+RCOC(COOC2H5)2R水解,CO2RCOCHCOOHRCO2RCOCH2R85CH3OCH2X + CH(COOC2H5)2-Na+CH3OCH2CH(COOC2H5)2水解?CH3OCH2CH2COOH86RCHO + CH(COOC2H5)2-Na+RCH=C(

18、COOC2H5)2水解RCH=CHCOOHNH3-H2O87CH3CH=CHCOOC2H5 + CH2(COOC2H5)2CH3CHCH2COOC2H5KCNCH(COOC2H5)2水解HOOCCH2CHCH2COOHCH3881CH3CH2CHCOOHCH3CH2(COOC2H5)2C2H5ONa/C2H5OHCH3CH2BrCH3CH2CH(COOC2H5)2C2H5ONa/C2H5OHCH3BrCH3CH2C(COOC2H5)2CH3水解,CO2CH3CH2CHCOOHCH389HOOCCH2CH2COOHCH2(COOC2H5)2C2H5ONaBrCH2COOC2H5(H5C2OOC)2CHCH2COOC2H5稀NaOHH+HOOCCH2C