《酚与芳香胺》PPT课件

《《酚与芳香胺》PPT课件》由会员分享，可在线阅读，更多相关《《酚与芳香胺》PPT课件（37页珍藏版）》请在装配图网上搜索。

1、 OH NH2O H N HH RCOOH H2O ROH CH=CH NH3 RH OH酸性顺序 O + H+ 相当于弱酸OH NO 2NO2O2N OH NO2NO2 OHNO2 OH OHCH3 OHOCH3 OH + H+O O O O O NH2NO2NO2O2N NO2NO2 NH2NO2 NH2CH3 NH2OCH3 NH2 NH2NH 2 + H+ NH3 OHSO3Na NaOH熔融1. H2SO42. NaOH OHCl NaOH(aq)Cl 2Fe 高温高压NH2NO2 FeHNO 3H2SO4 H+ NaNO2HCl N=NCl H3+O OH OH OCH3N=NCl

2、 H3+OOCH3NH2 NaNO2HClOCH3NO2 FeH+OCH3 NO2Cl NaOCH3NO2ClSO3H H3+OHNO3H2SO4ClSO3HCl H2SO4 CH 3CHCH3CH3CHCH3ClAlCl3 1. O22. H3+O CH3CCH3OH O+ CH3CH3C H O2 CH3CH3C OHO过氧化异丙苯 H+ CH3CH3C OH2O -H2O CH3CH 3C OCH3CH3C O H2O CH3CH3C OH2O -H+ CH3CH3C OHOCH 3CH3C OHO + CH3CCH3O + OH OH 20%HNO350C OH NO2 + OHNO2

3、OH NO 2 形成分子内氢键，使其蒸汽压升高可以被水蒸气蒸馏。OHNO 2 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 105Pa+ OH NO2 T1 OH NO2H2O+ T2结果使邻硝基苯酚的沸点降低了。 OH NaNO2HCl NOHO 稀HNO3 NO2HO OH OH BrBr BrBr2H2O 白色 BrO BrBrBr 橙色2,4,4,6-四溴-2,5-环己二烯酮Br2/H2O氧化剂NaHSO3NaNO2HClHO OH HO OHNOCH 3OH O NaBr, K HS2O8CH3COCH3, H2O CH3OH

4、Br O CH3ONa, CuBr (5%)DMF, H2O, 1300COHCH3OCH3Br OHCH3OCH3CH3O OH H2SO4 OH150C SO3H 动力学产物H 2SO41000C OHSO3H 热力学产物 OH SO3HSO3HH2SO41000C OH (CH3)3CBr OHHF C(CH3)3OR 1 R2 O OHI R 1=OH; R2=HII R1=H; R2=OHIII R1=OCH3; R2=H80% H2SO4600C，回流3小时 OH 大豆异黄酮 OR1 R2 O OH O O H-C-HO O CH2OHO H-C-HO O CH2OH OH CH2

5、 OH CH2 OH CH2 OH CH2CH2 CH2酚醛树脂脱水 OK + CO2 1250C OKCOOH OHCOOK H+ OHCOOH压力ONa + CO2 1250C ONaCOOH OH COONa H+ OH COOH水杨酸压力 (CH3CO)2OCH3COO COOH 乙酰水杨酸(阿斯匹林) OH CHCl3NaOH(10%) OH CHO OHCHO+2035% 812%CHCl 3 + OH- CCl3 + H2O-Cl- :CCl2亲电试剂 OHOH-O OCl 2CH O CHCl2- C - CXX - C - CXOH - C - COHOH自动水解 - C -

6、 CO 水解酸化 OH CHO:CCl2进攻对位则生成 OHCHO OH CHCl3NaOH(10%) OHCHOCH3O CH3O 香兰素OH OH- O N=N N=NHO N=N OHOHN=NCl + pH=910 N=N OH H-CO NH2 NaNO2HCl H-CO N N ClNOH H-CO N=N N OHN NH 2 NaNO2HCl N N N ClHO 3S SO3HOH NH2Na2CO3 N N NHO3S SO3HOH NH2 OH + C OHCH3CCH3O2 H2SO4 HO CH3CH3 双酚A OH +CHOOH CH2Cl2 NaOHDMSO OC

7、HOO 保护多酚的反应 OH (CH3CO)2O OCH3CO AlCl3 OHCH 3CO + OHCH3COOCH3CO AlCl3CH 3 OC2H5CO C2H5+ OHCH3CO CH3 + OHC2H5CO C2H5 + OHCH3CO C2H5 + OHC2H5CO CH3 OHAlCl3C - OO COOCH3CO CH 3 AlCl3250C OHCH3CO CH380%AlCl31650COHCH3CO CH395%可水蒸气蒸馏蒸出 不可水蒸气蒸馏蒸出 OCH3CO AlCl3 OCH3CO AlCl3 CH3CO- O AlCl3 O AlCl3CH3CO H 1. -

8、HCl2. H2O OHCH3CO CH3 OH (CH3CO)2OH2SO4 CH3CH3COO AlCl31800C CH3 OH COCH3 FOH OH2SO4 OOHF(CH3CO)2O FO AlCl31400C OH NaHCO3 ONa RCH=CHCH2Br OCH2CH=CHR OH CHCH=CH2ROCH2CH=CHRCH3 OH CHCH=CH2RCH3OCH2CH=CHRCH3 OHCH2CH=CHRCH3CH3 CH3 NH2 HNO3H2SO4 NH3+ HNO3H2SO4 NH3+NO2 OH- NH2 NO2(CH3CO)2O CH3CONH氨基保护 HNO

9、 3H2SO4 CH3CONHNO2 H3+O NH2NO2H2SO4CH3CONH SO3H HNO3H2SO4CH3CONHSO3HNO2 H3+O NH2NO2 NH2 Br2H2O NH2BrBrBr 白色沉淀CH 3COOH CH3CONH Br2Fe CH3CONHBr H3+O NH2Br NH2 H2SO4 NH2SO3H 转化成内盐更为稳定 NH3+SO3-CH 3COOH CH3CONH ClSO3H CH3CONHSO2Cl本步骤采用氯磺酸进行氯磺化生成磺酰氯。 S - ClOO RNH2 CH3CONHSO2NHRNH 2SO2NHRH3+O 磺胺 ClO SOO2N

10、NH2+ (C2H5)3N NH O SO NO2 (CH3CO)2O NClOH CH3CH3 N SOOCH3COCH3 NH2N ClOH CH3ClO2S CH2Cl2, (C2H5)3N, 00C NClOH CH3CH3 NH-SOO NH2 CH3COCl CH3CONH直接反应生成乙酰苯胺 CH3CONHO=C-CH3CH3COClAlCl3 H3+O NH2O=C-CH3CH3COClAlCl3N(CH3)2 N(CH3)2CH3CON(CH3)2 N(CH3)2H-CO(CH3)2N CO HPOCl3 NR2 O O NR2CH3(R=CH2COOCH3) POCl3 /

11、 DMF NR2 O O NR2CH3CHO O O(C2H5)2N POCl3 / DMF600C O O(C2H5)2N CHO香豆素的内酯环也可发生醛基化反应： ClN N CuClCuBr Br Gatterman改进了反应条件：将CuCl和CuBr分别改为Cu/HCl和Cu/HBr CuNaNO2 NO2CuNa2SO3 SO3NaCuKCN CNCuKSCN SCN 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。K I INaBF4 N NBF4 F SN NH2CH3O NaNO2HCl SN N NClCH3OK CNCuCN SN CNCH3O NaNO2HCl N

12、 NCl050CNH2NO22HNO3H2SO4 Na2SNO2 NO2 NO2NaBF4 N NBF 4NO2 F NO2 F NH2FeH+ OHN N H3+O HN N H 3PO2 DN N D3PO2 NH2 NH2HNO3H2SO4 FeH+ Br BrBrBr2H2O NaNO2HCl N NCl050C H3PO2Br BrBr Br BrBr NH2HNO3H2SO4 FeH+CH3 CH3 (CH3CO)2O CH3CONHCH3 Br2Fe CH3CONHCH3BrH3+O NH 2CH3Br NaNO2HCl H3PO2 CH3Br N N + NaOHH2O N N

13、ClR O COOHCuCl2 R O COOH N NG N NG H N NG H N NG H-H+ N NG 取代偶氮苯N NClOH N NHO 4-羟基偶氮苯+ pH=810 N NClNH2 N NH2N 4-氨基偶氮苯+ pH=57N NClNH2 N N(CH 3)2N4-(N,N-二甲基氨基)偶氮苯-4-磺酸钠SO3Na N(CH3)2NaNO2/HCl050C SO3Na CH3COOH微酸性 SO3Na甲基橙 N NN NClOH +H2N pH=57 NH2OHpH=810 N NNH2OHN NClOH +H2NR2 R1NH2 1. HCl / NaNO22. S

14、nCl2 / NaOH R2 R1NHNH2 N N N NClH2N NH2Cl Cl N NH2N NH2Cl NN Cl R1R2NH N NH2N NH2NR1R2 NN Cl Zn, HClCH3OH, H2O N NH2N NH2NR1R2NH2 NO2FeH+NH2-NO2在酸性条件下用金属彻底还原为-NH 2 pH=10Zn NHNH-NO2在碱性条件下用金属部分还原为氢化偶氮苯 H+ NH2H2N氢化偶氮苯在酸性介质中重排为联苯胺 NHNH 2H+ NH2NH2 NH2NH2H H同步的极化过渡态反应无中间体NH2H2N -2H+ NHNH H+ H2N NH2NHNHO2N NO2 H+ NO2 NO2NH2 NH2