第十五章羧酸衍生物

第十五章羧酸衍生物1．给下列化合物命名或写出它们的结构式。（1）对甲基-N，N-二甲基苯甲酰胺（2）3-溴丁腈（3）苯甲酰氧基甲酸乙酯（4）3-甲基戊二酸二异丙酯(5)COCl(6)CH3CH2CCH2CO(CH2)7CH3OO2．完成下列反应式：(1)CH3CH2CH2COOH(NH4)2CO3CH3CH2CH2CONH2CH3CH2CH2CNP2O5H+(2)HO(CH2)3COOHNH3OOHO(CH2)3CONH2NaCNLiAlH4CH2Cl(3)CH2CNCH2CH2NH2(4)COOHCH2NH2NHO(5)COOC2H5COCl(CH3CH2)2CdCOOC2H5COCH2CH3(6)CH3CH2OCClO+NH3CH3CH2OCNH2O(7)NH2CClO+CH3OCNH2OCH3O-(8)NCCONHCH3H2/NiNH2CH2CONHCH3(9)LiAlH4CONHCH3CH2NHCH3(10)H+2CH3CH2CH2COOC2H5Na/C6H6CH3CH2CH2COCHCH2CH2CH3OH(11)+ClBrCH2CH3COONaClCH3COOCH2(12)PCl3CH3COONaCH3CHCOOHCH3CH3CHCOClCH3CH3CHCOOCOCH3CH33．写出下列反应的机理：(1)CH3ONaOOC6H5CH2CH2BrOC6H5CH2CH2BrO-OCH3O-BrC6H5COOCH3C6H5COOCH3O(2)C2H5OHNH2OOC2H5O-NH2OOC2H5-ONH2O-OOC2H5H5C2OOCONH2H5C2OOCNHOH_H2OH5C2OOCN4.下列酯用不同浓度的碱处理可得到不同产物，分别写出它们的生成过程。C6H5CHCH=CHCH3OCCH3O5mol/LNaOHC6H5CHCH=CHCH3OCCH3-OOHC6H5CHCH=CHCH3OH构型保持+C6H5CHCH=CHCH3OCCH3ONaOH稀C6H5CHCH=CHCH3C6H5CH=CHCHCH3+C6H5CH=CHCHCH3OHHO-外消旋（在稀碱作用下发生酮式分解，在浓碱作用下发生酸式分解）5．下列化合物A水解生成中间体B，进一步反应生成C，写出各步反应历程：HO-CH=CNCOCOCH2CF3CH3OHCH=CNCOCOCH2CF3CH3OCH=CNCOCH2CF3OCO-CH3CHNOCH3-OOCH2CF3CHNOCH3OHO-CHNOCH3-OOHCH=CNCOCO-CH3OHABC6．比较下列酯碱性水解的速度：(1)XCH3COOX=NO2BrHOCH3（吸电子诱导效应，使酯水解反应中离去基团的离去能力增加，反应速度快）(2)RCOOC2H5R=CH3CH3CH2CH2(CH3)2CH(CH3)3C~（空间位阻越大，反应速度越小）7.NCOOCH3OCOPhCH3NCOOHOHCH3可卡因芽子碱8．分别用两种方法完成下列转化：(1)H3O+MgEt2OCO2PBr3CrO3/CHOOHCH2OHOHCHOBrHCHO吡啶H3O+MgEt2OPBr3COOHOHCHOBrPCl31)2)H2/Pd/BaSO4S喹啉(2)H3O+MgEt2OCO2LiAlH4PBr3CrO3/NH3CH2NH2OHCH2OHOHCHOHCHO吡啶H3O+MgEt2OPBr3COOHOHPCl31)2)H2/Pd/NH3CH2NH2CH2NH2COCl1)2)9．用简单化学方法鉴别下列各组化合物(1)CH3CH2OCH3CH3CH2COOHCH3CH2COCH3NaHCO3CO2CH3CH2COOH不反应2，4-二硝基苯肼黄色沉淀不反应CH3CH2OCH3CH3CH2COCH3（2）用红外光谱鉴别：CH3CH2CH2CN在2260~2240cm-1有特征吸收；CH3CH2CH2CONH2在3500~3100cm-1有两个特征吸收峰（N-H伸缩）；CH3CH2CH2CON(CH3)2在上述两处无吸收峰；10．Lifbrate是控制体内胆甾醇的药物。由不超过6个碳的有机原料起始，设计一条合成路线：H+NaOHOHClONaClCl2CHCOONa()CHCOOHOCl2NCH3HO()CHCOClOONCH3211．写出下列反应中A~E的结构式：H+PCl3AlCl3AlCl3+OOOCOOHOCOOHHgZnHCl浓COClOC2H5MgBrC2H5ABCDE12．治疗高血压、心衰等疾病的药物Carvedilol可由下列方法合成，写出中间体A~D和Carvedilol的结构式：+OOOH2NCH2CH2OHNCH2CH2OHOOPBr3NCH2CH2BrOOOHOCH3OH-NCH2CH2OOOCH3ONH2NH2H2NCH2CH2OCH3OABCD+NHOCH2CHCH2ONHOCH2CHCH2NHCH2CH2OCH3OOHDCarvedilol13.甲乙丙CH3CH2COOHHCOOC2H5CH3COOCH314．由苯、乙酰氯及其他必要的无机试剂合成下列化合物：CH3COCl(1)OH-COCH3CH3CHOCOCH=CHCH3(其中）CH3COClLiAlH[OC(CH3)3]3CH3CHOPCl3HNO3H2SO4HClH3O+Br2(2)COOH(其中）FeMgEt2OMgBrCO2COCl苯胺CONHNO2NH2FeCH3COCl(3)OH-CH3COClCH3CO-CH3COCCH3OOAg2O(4)OH-LiAlH[OC(CH3)3]3CH3CHOCH3COClCH3CH=CHCHOCH3CH=CHCOOHC2H5OHH3O+(5)吡啶PBr3C2H5MgBr(其中）CH3COClMgEt2OCH3COClCH3COOC2H5CH3CH2CCH3OHCH2CH3NaC2H5BrCH3CH2CCH3OCH2CH3CH2CH3LiAlH4CH3CH2OHC2H5MgBrA.B.15.HOOCCH2CHCH2COOHCH3OOOCH316.CH3CH2CHCOOCH(CH3)2BrA.B.17.CH2OCOCH3CH2CH2COOHA.18.COCH3OCOCH3B.COOCOE.F.CONH19.