有机化学a2教学课件羧酸衍生物的反应.pptx

1、1R CXO+H2OCOOHRHX+R COO COR+H2OCOOHR+COOHRR COOR+H2OOH-H+或COOHR+ROH酯的水解机理与酸的酯化反应机理是可逆的.2R CONH2HCI回流H2OCOOHRNH4CI+R CONRRKOHH2OCOOKR+HNRRR CONH2R 大时,先与亚硝酸作用,生成重氮盐,再水解:HON=OH+H2ON=O+H2O+NO+3R CONH2+NO+R CONH2NO+-H+R CONN=OHH+R CONN=OHH+-H+R CONNOHH+R CONNOH2+-H2OR CONN+R C+O-N24R C+OH2OR COOH2+-H+R C

2、OOH即:R CONH2HNO2H2SO4H2OR COOHRCNH2OOH-H+或RCONH2H2OH+R COOH+NH4+54.2 醇解生成酯R COX+ROHOH-COOR+RHX碱:NaOHR3N吡啶R COO COR+HORCOORR+COOHRHORCOORR6R COOR+ROHOR-COOR+RH+或ROH(酯交换反应)R CONROHOR-COORRH+或+HN+RCN+ROHH3O+COORR74.3 氨(胺)解生成酰胺R CXONHOH-R CON+HCI+R CONR COORNH+ROH+R CONH2NHHCIR CON+.NH4CI8H+或R COO CORNH

3、OH-H2OR CON+RCOOH+或OOONH3COCONH2ONH4H+COCONH2OH+300NHOO邻苯二甲酰亚胺9NHOOBr2NOOBr+HBrNHOOKOHN-K+OO+H2O104.4 与金属有机物的反应(酰卤,酯,腈)R C YORMgX+R C YOMgXRR CORRMgXH2OR C ROHRRC NRMgXRMgXRC=NH2OR COR用RLi代替RMgX时,结果相同当羧酸衍生物中R很大时,反应停到酮11获得酮的更好的方法是:由酰卤与有机镉二烃基酮锂反应.R C CIOR C ROR Cd2+R C CIO低温R C ROR CuLi2+CdCuLiR2不与酯反应

4、R2在较低温度下,不于酯和腈反应*CH2CH2CH2C CIOROCOR Cd2CH2CH2CH2COROCOR124.5 还原反应4.5.1 酰卤的还原生成醛酮R C CIOH2Pd/BaSO4R C HO罗森孟还原法R C CIOLiAl(OR)2H2R C HOLiAl(OR)2H2RCH2OH134.5.2 酯的还原1.催化氢化R COORH2CuOCuCrO4RCH2OHROH+2.用金属氢化物还原R COORRCH2OHROH+LiAlH4醚H2O3.金属钠醇还原R COORRCH2OHROH+NaROH(C=C不受影响)14机理:R COORNaR CORO-Na+NaR C-O

5、RO-Na+Na+醇R CHORO-Na+R COHNaR CHO-Na+NaR C-HO-Na+Na+醇R CHHO-Na+醇RCH2OH154.酮醇缩合R COORNa,N2苯H2OR COR CHOH可以制备索烃16(CH2)nC=OC=OORORNa(CH2)nORORC-O-Na+C-O-Na+(CH2)nORORC-O-Na+C-O-Na+(CH2)nC=OC=O2Na(CH2)nC-ONaC-ONaH2O(CH2)nC=OCHOH174.5.3酰胺的还原催化氢化R CONH2H2CuOCuCrO4RCH2NH2R CON用金属氢化物还原LiAlH4醚H2OR CH2N当 N 上的

6、基团很大时,或用LiAl(OR)iHj时,可以得到醛184.5.4 腈的还原RC NLiAlH4RCH2NH2RC NH2Ni 液氨RCH2NH2LiAlH4还原羧酸及衍生物的活性:CORClCORORCORNCOROHRC N194.6 H 的卤化H 的活性:CORClCORORCORNC HORCORRCH3OCOCH2CH2CH2COClBr2(1mol)CH3OCOCH2CH2CHCOClBr204.7 酯的位活性COCH3OC2H5LDATHF -78COCH2OC2H5-COCH2OC2H5-形成的负离子 可以 与 醛,酮,酰卤,卤代烷反应.21CORR+COCH2OC2H5-H2

7、OCOHRCOCH2OC2H5RCl+COCH2OC2H5-H2OCORCOCH2OC2H5CORR-I+COCH2OC2H5-H2OCOCH2OC2H5R224.8 瑞福马斯基(Reformatsky,S.)反应醛酮与 溴代酸酯 在 Zn 作用下,得到 羟基酸酯COBrCH2ORCORR+Zn苯CRROZnBrCOCH2ORH2OCRROHCOCH2ORH2SO4CRRCOCHOR234.9 克莱森缩合反应(Claisen condensation)酯中的H遇到碱离去,形成碳负离子,与另一分子酯发生亲核加成反应,得到羰基 酯.CH3COORNaOC2H5CH2COOR-CH2COOR-CH3

8、COOR+CH2COOR-CH3COOR-CH2COOROR-+CH3COCH2COOR244.10 酰胺的脱水R-CONH2P2O5RCN254.11 酯的热解(热消除)反应ROCOCH2CH2R400-500RCOOH+CH2=CHRRCOOCCHHRRH400-500ROCOHCCRRHH+26CH3OCOCH2500CH3COOH+CH2失去 H,环状过度态,顺式消除,重叠式构象,获得反式烯.27当酯基上连接两个 H时,酸性大 位阻小的 H消除.CH3C OOCHCH3CHCH3CH3500CH3COOH+CHCH2CHCH3CH328合成例题:1.由CH2COOC2H5COOC2H5

9、合成CH3CH2OHCH3CH2OHK2Cr2O7H2OCH3COOHCl2PCH2COOHClNaCNNCCH2COOHH3O+CH2COOHCOOHCH3CH2OHH2SO4CH2COOCH2CH3COOCH2CH3292.由丙二酸二乙酯及 C1C3 有机物 合成 正戊酸CH2COOC2H5COOC2H5NaOC2H5CHCOOC2H5COOC2H5-CH3CH2CH2BrCH3CH2CH2CHCOOC2H5COOC2H5H2OCH3CH2CH2CHCOOHCOOHCH3CH2CH2CH2COOH30作业作业:1.由丙二酸二乙酯及不超过三个碳的有机物由丙二酸二乙酯及不超过三个碳的有机物合成环丁烷合成环丁烷.2.由丙二酸二乙酯及不超过三个碳的有机物由丙二酸二乙酯及不超过三个碳的有机物合成正丁烷合成正丁烷.