chap10-2羧酸衍生物

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

2、COHLHNuRCOHNu+RCOHNuL亲亲核核加加成成消消除除HRCOHNuLHLH碱性条件碱性条件酸性条件酸性条件COXRCOOCOORCONH2(R)CRORRRRCOOHH2OHX+HOCROHORNH3(R)H2OH or OHH2OH or OHH2OH or OHorRCOORCOClRCOORCOORRCONH2(R)CRORCOL XOORNH2(R)CROH2ORCOHORH2ORCOHORRCOHOH HORRCOOHRCOORHHORCOHORH HHOR烯烯烃烃H2O HRCOHORCOOHRCOORHRR+RCOORCOORRCOORHOROHRCOO+OR OH

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

4、H3ORCOORRCOORROHHorRO+ROH+RCOORRCONHRROH+RNH2+H or OHNHROR 化化学学计计量量）NaOC2H5CH2CH2CO2C2H5NCH2CH2CO2H2H5H3CHClNCO2C2H5OH3CHClNaOC2H5（ 化化学学计计量量）（ 化化学学计计量量）RCNH2OBr2 / NaOHRNH2+CO2RCNHOHOHRCNHOBrBrRCNOBrHRCNOBrOHR2C缺电子中心缺电子中心RCNOBrRCNO- - BrRCNOR迁迁移移异异氰氰酸酸酯酯消消除除和和重重排排同同时时进进行行RCNOOHRCHNOORHNRH2NOHHCO2+OH

5、OH CO2RCNH2OBr2 / NaOHRNH2*+CNOBrCNOCNOBr CR1R2R3CR1R2R3CR1R2R3 Br库尔提斯库尔提斯施密特施密特 N2RH2NRCNONNRCNO+CO2+H2ON2R迁迁移移RCClORNH2+RCNONNRCOHOH2ON2NaN3HN3H2SO4CO2+ CNCNCOOEtCNH2CCHCNRCNRCRHCN 不饱和，可不饱和，可加成和还原加成和还原有弱酸性，可有弱酸性，可与强碱作用与强碱作用RCONH2RCNRXKCNORRHCNHORRCNP2O5+H2ORCNRCNH2, Raney NiRCH2NH21. LiAlH4NH32. H

6、2ORCNRCH2NH2H2RCHNHH2 不饱和，不饱和，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