第十章酚与芳香胺

1、OHNH2OHNHHRCOOH H2O ROH CH=CH NH3 RH OH酸性顺序O+ H+相当于弱酸OHNO2NO2O2NOHNO2NO2OHNO2OHOHCH3OHOCH3 OH+ H+OOOOONH2NO2NO2O2NNO2NO2NH2NO2NH2CH3NH2OCH3NH2NH2NH2+ H+NH3 OHSO3NaNaOH熔融1. H2SO42. NaOHOHClNaOH(aq)Cl2Fe高温高压NH2NO2FeHNO3H2SO4H+NaNO2HClN=NClH3+OOH OHOCH3N=NClH3+OOCH3NH2NaNO2HClOCH3NO2FeH+OCH3NO2ClNaOCH3

2、NO2ClSO3HH3+OHNO3H2SO4ClSO3HClH2SO4CH3CHCH3CH3CHCH3ClAlCl31. O22. H3+OCH3CCH3OHO+ CH3CH3CHO2CH3CH3COHO过氧化异丙苯H+CH3CH3COH2O-H2OCH3CH3C OCH3CH3C OH2OCH3CH3C OH2O-H+CH3CH3C OHOCH3CH3COHO+CH3CCH3O+OHOH20%HNO350COHNO2+OHNO2OHNO2形成分子内氢键，使其蒸汽压升高可以被水蒸气蒸馏。OHNO2只能形成分子间氢键，蒸汽压下降，水蒸气蒸馏时不能被水蒸气带出。H2O蒸汽压温度1000C1.013

3、 105Pa+OHNO2T1OHNO2H2O+T2结果使邻硝基苯酚的沸点降低了。OHNaNO2HClNOHO稀HNO3NO2HOOHOHBrBrBrBr2H2O白色BrOBrBrBr橙色2,4,4,6-四溴-2,5-环己二烯酮Br2/H2O氧化剂NaHSO3NaNO2HClHOOHHOOHNOCH3OHONaBr, KHS2O8CH3COCH3, H2OCH3OHBrOCH3ONa, CuBr (5%)DMF, H2O, 1300COHCH3OCH3BrOHCH3OCH3CH3OOHH2SO4OH150CSO3H动力学产物H2SO41000COHSO3H热力学产物OHSO3HSO3HH2SO4

4、1000COH(CH3)3CBrOHHFC(CH3)3OR1R2OOHI R1=OH; R2=HII R1=H; R2=OHIII R1=OCH3; R2=H80% H2SO4600C，回流3小时OH大豆异黄酮OR1R2OOHOOH-C-HOOCH2OHOH-C-HOOCH2OHOHCH2OHCH2OHCH2OHCH2CH2CH2酚醛树脂脱水OK+ CO21250COKCOOHOHCOOKH+OHCOOH压力ONa+ CO21250CONaCOOHOHCOONaH+OHCOOH水杨酸压力(CH3CO)2OCH3COOCOOH乙酰水杨酸(阿斯匹林)OHCHCl3NaOH(10%)OHCHOOHC

5、HO+2035%812%CHCl3 + OH- CCl3 + H2O-Cl-:CCl2亲电试剂OHOH-OOCl2CHOCHCl2- C - CXX- C - CXOH- C - COHOH自动水解- C - CO水解酸化OHCHO:CCl2进攻对位则生成OHCHO OHCHCl3NaOH(10%)OHCHOCH3OCH3O香兰素OHOH-ON=NN=NHON=NOHOHN=NCl+pH=910N=NOHH-CONH2NaNO2HClH-CON N ClNOHH-CON=NNOHNNH2NaNO2HClNN N ClHO3SSO3HOHNH2Na2CO3NN NHO3SSO3HOHNH2OH+

6、COHCH3CCH3O2H2SO4HOCH3CH3双酚AOH+CHOOHCH2Cl2NaOHDMSOOCHOO保护多酚的反应 OH(CH3CO)2OOCH3COAlCl3OHCH3CO+OHCH3COOCH3COAlCl3CH3OC2H5COC2H5+OHCH3COCH3+OHC2H5COC2H5+OHCH3COC2H5+OHC2H5COCH3OHAlCl3C - OOCOOCH3COCH3AlCl3250COHCH3COCH380%AlCl31650COHCH3COCH395%可水蒸气蒸馏蒸出不可水蒸气蒸馏蒸出OCH3COAlCl3OCH3COAlCl3CH3CO-O AlCl3O AlCl

7、3CH3COH1. -HCl2. H2OOHCH3COCH3OH(CH3CO)2OH2SO4CH3CH3COOAlCl31800CCH3OHCOCH3FOHOH2SO4OOHF(CH3CO)2OFOAlCl31400C OHNaHCO3ONaRCH=CHCH2BrOCH2CH=CHROHCHCH=CH2ROCH2CH=CHRCH3OHCHCH=CH2RCH3OCH2CH=CHRCH3OHCH2CH=CHRCH3CH3CH3NH2HNO3H2SO4NH3+HNO3H2SO4NH3+NO2OH-NH2NO2(CH3CO)2OCH3CONH氨基保护HNO3H2SO4CH3CONHNO2H3+ONH2

8、NO2H2SO4CH3CONHSO3HHNO3H2SO4CH3CONHSO3HNO2H3+ONH2NO2NH2Br2H2ONH2BrBrBr白色沉淀CH3COOHCH3CONHBr2FeCH3CONHBrH3+ONH2BrNH2H2SO4NH2SO3H转化成内盐更为稳定NH3+SO3-CH3COOHCH3CONHClSO3HCH3CONHSO2Cl本步骤采用氯磺酸进行氯磺化生成磺酰氯。S - ClOORNH2CH3CONHSO2NHRNH2SO2NHRH3+O磺胺ClO SOO2NNH2+(C2H5)3NNHO SONO2(CH3CO)2ONClOHCH3CH3N SOOCH3COCH3NH2

9、NClOHCH3ClO2SCH2Cl2, (C2H5)3N, 00CNClOHCH3CH3NH-SOO NH2CH3COClCH3CONH直接反应生成乙酰苯胺CH3CONHO=C-CH3CH3COClAlCl3H3+ONH2O=C-CH3CH3COClAlCl3N(CH3)2N(CH3)2CH3CON(CH3)2N(CH3)2H-CO(CH3)2N COHPOCl3 NR2OONR2CH3(R=CH2COOCH3)POCl3 / DMFNR2OONR2CH3CHOOO(C2H5)2NPOCl3 / DMF600COO(C2H5)2NCHO香豆素的内酯环也可发生醛基化反应： ClN NCuClC

10、uBrBrGatterman改进了反应条件：将CuCl和CuBr分别改为Cu/HCl和Cu/HBrCuNaNO2NO2CuNa2SO3SO3NaCuKCNCNCuKSCNSCN不能直接采用亲电取代法合成，只能采取重氮盐取代方法合成。KIINaBF4N NBF4FSNNH2CH3ONaNO2HClSNN NClCH3OKCNCuCNSNCNCH3O NaNO2HClN NCl050CNH2NO22HNO3H2SO4Na2SNO2NO2NO2NaBF4N NBF4NO2FNO2FNH2FeH+OHN NH3+O HN NH3PO2DN ND3PO2 NH2NH2HNO3H2SO4FeH+BrBrB

11、rBr2H2ONaNO2HClN NCl050CH3PO2BrBrBrBrBrBrNH2HNO3H2SO4FeH+CH3CH3(CH3CO)2OCH3CONHCH3Br2FeCH3CONHCH3BrH3+ONH2CH3BrNaNO2HClH3PO2CH3Br N N +NaOHH2ONNClROCOOHCuCl2ROCOOH N NGN NGHN NGHN NGH-H+N NG取代偶氮苯N NClOHN NHO4-羟基偶氮苯+pH=810 N NClNH2N NH2N4-氨基偶氮苯+pH=57N NClNH2N N(CH3)2N4-(N,N-二甲基氨基)偶氮苯-4-磺酸钠SO3NaN(CH3)2NaNO2/HCl050CSO3NaCH3COOH微酸性SO3Na甲基橙 N NN NClOH+H2NpH=57NH2OHpH=810N NNH2OHN NClOH+H2NR2R1NH21. HCl / NaNO22. SnCl2 / NaOHR2R1NHNH2NNN NClH2NNH2ClClNNH2NNH2ClNNClR1R2NHNNH2NNH2NR1R2NNClZn, HClCH3OH, H2ONNH2N