chap10-2羧酸衍生物

1、RCOOHRCOXRCOORCOORRCONH2(R)CROCOGR CH3COClPh COClCH3CH2CHCOBrBrCOClCOClOCH2PhCOClCH3COOCCH3OCH3COOCCH2CH3OOOOPhCOOC2H5OH3COCH2COOC2H5COC2H5OCH2COOC2H5COH3C COXRCH2COOCOORCONH2(R)CRORCH2RCH2RCH2RCHCOLHRCOLNuRCONu+Lor HNuHLorRCOLRCOOHH2OH or OHROHRNH2RCOORRCONHRH or OHRCOLNuRCONu+ LRCONuL親親核核加加成成消消除除R

2、COHLHNuRCOHNu+RCOHNuL親親核核加加成成消消除除HRCOHNuLHLH堿性條件堿性條件酸性條件酸性條件COXRCOOCOORCONH2(R)CRORRRRCOOHH2OHX+HOCROHORNH3(R)H2OH or OHH2OH or OHH2OH or OHorRCOORCOClRCOORCOORRCONH2(R)CRORCOL XOORNH2(R)CROH2ORCOHORH2ORCOHORRCOHOH HORRCOOHRCOORHHORCOHORH HHOR烯烯烴烴H2O HRCOHORCOOHRCOORHRR+RCOORCOORRCOORHOROHRCOO+OR OH

3、HROHRCOORRCOCl+Et3N or 吡啶Et3NH ClNHClorHClROHRCOORRCOClEt3N or 吡啶RCOOHSOCl2RCOOHRCOOCROROHRCOOR+C2H5OHSCH2OH(CH3CO)2OCH3COONaSCH2OCCH3OOOOCOOEtCOOH二二酸酸單單酯酯COOEtCOOEt二二酸酸二二酯酯 H2CCHCOOCH3n-BuOHTsOHH2CCHCOOBun+ CH3OHOCOHOCH3NaOCH3CH3OOHCOCH3OCH3COCH3+CHCH2CHCH2OAcOAcnCH3OHOHCHCH2CHCH2OHOHnCCH3OO+CH3COC

4、H3ORCOORRCOORROHHorRO+ROH+RCOORRCONHRROH+RNH2+H or OHNHROR 化化學(xué)學(xué)計(jì)計(jì)量量）NaOC2H5CH2CH2CO2C2H5NCH2CH2CO2H2H5H3CHClNCO2C2H5OH3CHClNaOC2H5（ 化化學(xué)學(xué)計(jì)計(jì)量量）（ 化化學(xué)學(xué)計(jì)計(jì)量量）RCNH2OBr2 / NaOHRNH2+CO2RCNHOHOHRCNHOBrBrRCNOBrHRCNOBrOHR2C缺電子中心缺電子中心RCNOBrRCNO- - BrRCNOR遷遷移移異異氰氰酸酸酯酯消消除除和和重重排排同同時(shí)時(shí)進(jìn)進(jìn)行行RCNOOHRCHNOORHNRH2NOHHCO2+OH

5、OH CO2RCNH2OBr2 / NaOHRNH2*+CNOBrCNOCNOBr CR1R2R3CR1R2R3CR1R2R3 Br庫(kù)爾提斯庫(kù)爾提斯施密特施密特 N2RH2NRCNONNRCNO+CO2+H2ON2R遷遷移移RCClORNH2+RCNONNRCOHOH2ON2NaN3HN3H2SO4CO2+ CNCNCOOEtCNH2CCHCNRCNRCRHCN 不飽和，可不飽和，可加成和還原加成和還原有弱酸性，可有弱酸性，可與強(qiáng)堿作用與強(qiáng)堿作用RCONH2RCNRXKCNORRHCNHORRCNP2O5+H2ORCNRCNH2, Raney NiRCH2NH21. LiAlH4NH32. H

6、2ORCNRCH2NH2H2RCHNHH2 不飽和，不飽和，可加成可加成NuRCNH2OH2OH+OHRCOOHRCONH2H2OH2OH+OHRCOOH2CCHCNH2OCNCNH2O, H2SO4CONH2CONH290 - 100oCH2CCHCONH2ZnCl2H3CCCH3OHCNH3CCCH3OHCNH2SO4, HOCH3H2CCCH3CNH2SO4, HOCH3H2CCCH3COOCH3H2O RCNH+RCRCNH2ORH2OH+ROHOORRMgXRCNRRCNMgXRCNHRH2OH+RCORH2ORCORRCH2ONRMgXH+R-C-OHOR-C-XOR-C-NH2OR-C-OROR-C-O-C-ROOPX3或SOCl2P2O5/ ROH/H+NH3/H+P2O5RCNH2OH2OH2O/OH-H2O/H+或OH-H2O/H+或OH-RCOONaROHROHROHROHROHNH3NH3NH3NH3R-C-NH2NHRNH2OOOHTsOH1. t-BuOK2. PhCH2BrH2O, H+1. LiAlH4(CH3)2C(OCH3)2(C6H14O3)（三三醇醇）（二二醇醇）2. H2O*AC(C9H18O3)(C16H24O3)DB(C13H20O3)OCROR1