有機化學：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) )鄰氨基苯甲酸鄰氨基苯甲酸13HBr+R

2、CHCOOHBrPBr3+RCH2COOHBr214RCHCOOHKIKCl(Br)+Cl(Br)IRCHCOOH15+RCH=CHCOOHHXRCHCH2COOHX+RCHCH2COOHOHHBrRCHCH2COOHBr16CH3OOC(CH2)4COOHAgNO3NaOHCH3OOC(CH2)4COOAgBr2CCl4CH3OOC(CH2)3CH2BrH+H2OHOOC(CH2)3CH2Br3. 3. 其它鹵代酸其它鹵代酸可有洪賽迪克爾可有洪賽迪克爾(Hunsdiecker)(Hunsdiecker)反應制備，反應制備，如如-溴戊酸的制備。溴戊酸的制備。1718+ HClCH3CHCOOH

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

4、-OPhHRH+CCCOO-PhHROH+-CO2重排PhCH2COR繼續(xù)反應將得到比原醛、酮碳原子增多繼續(xù)反應將得到比原醛、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中藥提取中常利用內(nèi)酯在酸性條件下成環(huán)中藥提取中常利用內(nèi)酯在酸性條件下成環(huán)( (脂脂溶性溶性) )，而熱堿水液處理后開環(huán)成鹽，而熱堿水液處理后開環(huán)成鹽( (水溶性水溶性) )進行提取。進行提取。41OOOC4H9O42RCHCOOHOHRCHO + CO2 + H2OKMnO4,H+RCOOHRCHCOOHOH稀H2SO4RCHO + HCOOH脫羧反應脫羧反應43濃H2SO4R2CCOOHOHR2CO + CO + H2O脫羰反應脫羰反應44ONa+CO2COONaOHCOOHOHH+120140405709KPa4

7、5OK+CO2加熱，加壓COOKOHCOOHOHH+46OHOH+CO2OHCOOHOHNaHCO347+CO2200COOHHOOHOHHOOHOHCOOHOHOHCOOHOH2002204849CH3CHCOOHOHOCH3CCOOHO50+CO2CH3CCOOHO稀H2SO4CH3CHO+ COCH3CCOOHO濃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變異構(gòu)-H的活潑性的活潑性思考：思考：的酸性大小？的酸性大小？58CH3CCH2COOOC2H559CH3CH2OC2H5OOCH3CHOC2H5OOHCH3CCH2COOC2H5OC

9、H3COCHCOOC2H5H93% 7%602. 乙酰乙酸乙酯的互變異構(gòu)乙酰乙酸乙酯的互變異構(gòu)61CH3CCH2COC2H5OO濃NaOHH+2 CH3COOH + C2H5OH62CH3CCH2COC2H5OO稀NaOHCH3CCH2CONaOOH+CH3CCH2COHOOCH3CCH3O-C2H5OH63(四)-亞甲基上的取代反應CH3CCH2COOC2H5OC2H5ONaCH3CCHCOOC2H5O-RXCH3COCHCOC2H5ORCH3COCH2RCH2COOHR活潑亞甲基在強堿條件下失去活潑亞甲基在強堿條件下失去-H生成負離子，生成負離子，作為親核試劑進行反應。作為親核試劑進行反應

10、。與鹵烴反應與鹵烴反應甲基酮甲基酮羧酸羧酸+C2H5ONa+RX?64(四)亞甲基上的取代反應與酰鹵反應與酰鹵反應-二酮二酮-羰基酸羰基酸RCOXCH3COCHCOC2H5OCORCH3COCH2CROCH2COOHRCO65(四)亞甲基上的取代反應Cl(CH2)nCOOC2H5CH3COCHCOC2H5O(CH2)nCOOEt CH3COCH2(CH2)nCOOHHOOC(CH2)nCH2COOH與鹵代酸酯反應與鹵代酸酯反應羰基酸羰基酸二元酸二元酸66(四)亞甲基上的取代反應ClCH2CORCH3COCHCOC2H5OCH2CORCH3COCH2CH2CORCH2COOHRCCH2O與鹵代酮

11、反應與鹵代酮反應-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. ,-不飽和酮及不飽和酸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