第九章醇和酚-3

1、一、碱性条件下酚类芳环上的取代反应一、碱性条件下酚类芳环上的取代反应OOHBOHH2COOHOHCH2OHCH2OHOHCH2OHH2COOHOHOHCH2+HOOHCH2+HOOHCH2H2C OOHOHCH2OHOHOHOHNaOHOHCO2HOHCO2H加加压压CO2120-140oCAc2OOAcCO2HOO COOCO2HOHOCO2OHCO2H2HOHHONaOHCO2, 135oC1.2.OHH2NNaOHCO2, 120oC1.2.OHHOOHH2NCOOHCOOHHHOHK2CO3OHCO2KCO2200 300oCOHCO2HH+OHCOOH240oCOHCO2KK2CO3

2、OHCO2HH+二、酚类化合物的氧化二、酚类化合物的氧化OHOOOOHOOOHorOHNH2Ag2OOHOHOOAg2OOHC(CH3)3CH3(H3C)3CRHOC(CH3)3CH3(H3C)3C+R三、芳基醚的反应及在合成中应用三、芳基醚的反应及在合成中应用OHONaX orROROTsRNaOHor NaHOHOHRI+RIOArArH IOHO CH3(1) NaH(2)or CH3I(CH3O)2SO2RCClOAlCl3OCH3CORH IOHCOROHRC ClOAlCl3OHCOROH+COROAlCl2AlCl3CH3Cl+ OHOCH2Ph(1) NaH(2)RC ClOA

3、lCl3OH2 / Pd-CX CH2Ph+CH2PhRCOOHCH3PhRCONCH2PhRRH2 / Pd-CNRRHCH3Ph+NCRROOCH2PhH2 / Pd-CNRRHCH3Ph+ CO2OCH3OHCH3OH3CCH3OHH3CCH3RR O190200oCOHOH+OCH3OHCH3OCH3OCH3H123123123123123123OCH3HOCH3HHOHCH3HOCH3H123123123123123123OOOH123123123332121123OH3CCO2EtOH3CCO2EtOC2H5200oC200oCOC2H5HO123123123CHO123 一、邻二

4、醇及其性质一、邻二醇及其性质R1CCR4R3R2稀稀冷冷 KMnO4or OsO4R3CCR4R1R2HOOHcisRCOOHH2OOHorHtransCl2, H2ONaHCO3 O R3CCR4R1R2HOOHR3CCR4R1R2OHOHH2O?cis + transRCOR+Mg(Hg)H2ORCCRRROH OHRCORCH3CCCH3H3CCH3OHOHH3CCOCH32Mg(Hg)H2OOMg(Hg)H2OOH OH2适合制备适合制备对称邻二醇对称邻二醇HCCRHOHOHCRROHH5IO6HCCRRROO+CHOHO+CCRRHOOHH5IO6CROOHCRHO+HCCRRHOHOHH5IO6( (高高碘碘酸酸) )KIO4( (偏偏高高碘碘酸酸钾钾) )NaIO4( (偏偏高高碘碘酸酸钠钠) )orHCCRRHOHOHOHHO+HCCRRHOO+H2O 2OCH3CCCH3H3CCH3OHOHCH3CCH3CCH3CH3OH+H2OCH3CCCH3H3CCH3OHOHH+CH3CCCH3H3CCH3OHOH2CH3CCCH3H3CCH3OHH2O CH3CCCH3H3CCH3OH H+CH3CCH3CCH3CH3O CH3H2O CH3更稳定的正离子更稳定的正离子PhCCHPhHOH OHH+PhCCHPhHOPhCCPhHHO CH3CCPhP