1、第九章醇、酚、醚之醚第九章醇、酚、醚之醚一、醚的結構、分類及命名一、醚的結構、分類及命名RORRORROR（R = 烷基）CHORArOR(CH2)nOOOOOOORRR RR R為飽和烷烴基為飽和烷烴基1 1、結構與分類、結構與分類一、醚的結構、分類及命名一、醚的結構、分類及命名OCH3OCH3H3COHOCH2OHOCH3CHCH2CH2CH2CH3CH2OCH2CH3CH3COCH2CH3CH3CH3CH2CHOH3COH2CCH2OH2CCH CH3OCH3H3CHH123123OOOOO412365一、醚的結構、分類及命名一、醚的結構、分類及命名二、醚的制備二、醚的制備RORRONa

2、LR+NaL+CH3COCH2CH3CH3CH3CH3CONaCH3CH3XCH2CH3+OHCH3OTs+NaOHOCH3CCH2ClClCH2CH2OHCH2ClNaOHCCH2ClClCH2OL = X , TsO二、醚的制備二、醚的制備OHR2H+ROR+H2O OOHHO+H2OH2SO4HOOH2H2SO4OO+H2O2二、醚的制備二、醚的制備CH2CRRHOR+HClCH3CRRORHOBrHOHOBrH2CCH3CH3H2SO4OBrCCH3H3CCH3NaCCHOCCH3H3CCH3H+H2OHO二、醚的制備二、醚的制備CHCH2RH2O, THFCHCH3ROHHg+Hg(

3、OAc)2NaBH4H2OOHHORORCHCH2RHgOAcOAcCHCH2RHgOAc H2OCHCH2RHgOAcHO H+CHCH2RHgOAcHOH CHCH2RHgHHOCHCH3RHOHg+NaBH4二、醚的制備二、醚的制備二、醚的制備二、醚的制備CHCH2RROHCHCH3RORHg(OCCF3)2NaBH4OCCHRROHCCH2RORHg+NaBH4CCHRCCH2ROHHgSO4H2OCCH3RO三、醚類的化學性質三、醚類的化學性質CORRH H+CHORRH 三、醚類的化學性質三、醚類的化學性質CORRHHO2（空空氣氣）CORRHOOH三、醚類的化學性質三、醚類的化學

4、性質RORHClRORHOOBH3MgRXEtOEtEtOEtBH3Cl+RORH2SO4RORH+HSO4+ Brnsted Brnsted堿堿 Lewis Lewis堿堿三、醚類的化學性質三、醚類的化學性質H+RORHNuRNu+HORRORROR NuRNu+ORSN2三、醚類的化學性質三、醚類的化學性質RORHXRXHOR+X = I, Br H3CCHH3COCHCH3CH3H3CCHH3CIO48% HBr(過量)OHBrBrBr +H3CCHH3COH H3CCHH3CIHIHI（過量）2( (過量過量) )( (過量過量) )四、四、1,21,2環氧化合物（環氧化合物（Epox

5、ides）OHHOOOOOHOHOCC四、四、1,21,2環氧化合物（環氧化合物（Epoxides）OHOClHOHHOHClHOHOOHR2R1R3R4PhCO3HR2R1R3R4HOXOHR2R1R3R4O四、四、1,21,2環氧化合物（環氧化合物（Epoxides）ORHOH+ROHH+HXHCNHOHRHROOHRHXOHRHCNOHRHH2OORHH+ORHH NuNuOHRH四、四、1,21,2環氧化合物（環氧化合物（Epoxides）ORHORO1. RMgXHOHRHOHHOORRH2. H2OHORRHRNH2HONHRRH1. LiAlH42. H2OHOCH3RH, H2

6、O, HOR四、四、1,21,2環氧化合物（環氧化合物（Epoxides）四、四、1,21,2環氧化合物（環氧化合物（Epoxides）ORHNuORHNuOHRHNuHS五、冠醚（五、冠醚（crown etherscrown ethers）OOOOOOOOOOOOOOOOOOOOO五、冠醚（五、冠醚（crown etherscrown ethers）OOOHOH+OOClClKOHOOOOOO Williamson醚合成法醚合成法OHOHClOCl+NaOHOOOOOO五、五、冠醚（冠醚（crown ethers）MnO4 OOOOOOOOOOOOOOOLi+Na+K+KMnO418-Crown-6室室溫溫， 快快100COOHCOOH Charles J. Pedersen(1904 1989)Donald J. Cram(1919 2001)Jean-Marie Lehn(1939