有机化学课件：第五章 芳烃芳香性

1、CH3CH3ClCH3CHCH3CH3CH3CH2CH2CH2CH3CH3CHCH3CH3ClCHCH3CH3NO2CH3CH3CH3CH3CH3CH3CH3CH3H3CCH2CH3CH2CH2CH3CH3(CH2)3CCHCH3CH3PhCCHCH2CH2ClCH3CH2CHCHCH3CH3CH3NH2SO3HClNO2NO2COOH1234561234123氨基苯磺酸硝基氯代苯甲基 硝基苯磺酸4343COOH SO3H COOR COX CONH2 CN CHO C=OOH OH SH NH2 C CC=C OR R X NO2HHHHHH+ EY+YHEHNO2SO3HRCORXBrBr

2、 + FeBr3BrFeBr3BrH+ Br2FeBr+ HBr+BrFeBr3BrBrH+ BrFeBr3慢BrH + BrFeBr3Br+FeBr3HBr +BrHBrHBrH+HBrBrBrBrBrBrBr2HBrFe或FeBr3+。CCH3CH3CH3BrBrBr2HBrFe或FeBr3+CH3COOH；25BA给电基吸电基.。CC+浓浓H2SO4HNO3NO2NO2NO2100NO2NO2O2NHNO SO3浓H2SO4100。；5d+ HNO3H2SO450 - 55 CNO2+ H3O + HSO4HNO3+ 2H2SO4NO2+ H3O + 2HSO4。CCH3CH3CH3+浓

3、浓H2SO4HNO3NO2NO2305937%CH3NO2H+SOOOSOOOH25 C浓浓H2SO4CH3CH3CH3+浓H2SO4H2O100。SO3HSO3H053437913%CCCH3CH3Br+浓H2SO4100。SO3HCBr2/FeCH3SO3HH2OHCl/P.a.BrCH3SO3+ H3O + 2HSO42H2SO4H+SOOO慢慢SO3H决定反应速率的一步决定反应速率的一步SO3H+ HSO4快快SO3+ H2SO4SO3+ H2SO4快SO3HHSO4+H2SO4SO3H+ H2OCH3+CH3CH2CH2XCH3CHXCH3CH2CH2OHCH3CHOHCH3CH C

4、H2(CH3CH2CH2)2OHXHXH2OH2OCH3CH2CH2OHCH3AlCl3（无水）CH CH3CH3H+CH3CHCH3慢CHCH3HCH3CHCH3HCH3+ Cl AlCl3快快CHCH3CH3+ HCl + AlCl3CH3CHCH3Cl + AlCl3CH3CHCH3+ Cl AlCl3RCH2XAlX3H+ (CH3)2CHCH2ClAlCl30 CC(CH3)3+ HCl(66%)CCH3CH3CH2HCl AlCl3CCH3CH3CH3+ Cl AlCl3CH3CH2CH2Cl CH3CH2CH2 Cl AlCl3 AlCl3+CH3CH2CH2AlCl4 CH3C

5、HCH3AlCl4+ HOBF360 C+H2SO4+ (CH3)3CClAlCl3C(CH3)3+C(CH3)3C(CH3)3+ (CH3)3CClAlCl3C(CH3)3+C(CH3)3C(CH3)3+CH3CH3CH32AlCl3CH3CH2C Br(CH3CH2C )2 OCH3CH2C OHCH3CH2C OC2H5AlCl3无水C CH2CH3OOOOOHBrCH3CH2C OHH2OC2H5OH+/OAlCl3NH2+ RX不不反反应应或或难难反反应应NH2+ AlCl3AlCl3ArNH2ArNO2、SO3H、CHO、C R、COOH和NR2等OCH3CH2C BrAlCl3无

6、水C CH2CH3OO+/Zn Hg/HClCH2CH2CH3CH3,CH2OH,CH2CN,CHO,CH2COOH,CH2N(CH3)2等等3+ (HCHO)3 + 3 HCl无无水水ZnCl2CH2Cl+ 3 H2O3CH2ClCH3CH2OHCHOCH2CNCH2COOHCH2N(CH3)2HCl/ZnNaOHCrO3/吡啶或Cu/高温KCNH2O/HHN(CH3)22CH2CH3+NOOBrPhCOOCPhOOCCl4, 80 CCHCH3Br+NOOH(N-bromosuccinimide)(NBS)+Cl2hv.CH3CH2ClNaOHCH2OHClCH3Cl2, PCl5h ,

7、,ClCHOH2SO4H2OClCHCl2CHCH3CH2CH2CH2.CH3CHCH2NBSh,CCl4CH2CHCH2BrCH3NO2Na2Cr2O7H2O,H2SO4,COOHNO2CH2CH2RNa2Cr2O7H2O,H2SO4,COOHCCH3CH3CH3YOHHClNO2ClHNO3H2SO4ClNO2+Cl+ClNO2NO2CF3HNO3H2SO4CF3NO2+CF3+CF3NO2NO2CH3NO2+-CHHHOHE HOHE HOHE HOHHEEHEHEHOHOHOHEHOHOHEHOHEHOHEHOH-.Cl+EEEHHH+ HEClClClCl.ClEHClEHClEHC

8、lHECF3ECF3EH+NO2+NO2E+. .HECF3EHEHEHCF3CF3EHEHEHCF3CF3CF3E HE HHECF3CF3CF3CF3RE+CH3CH(CH3)2NO2NO258.54.437.1307.762.3%XYCH3NO2HNO3H2SO4CH3NO2NO2NHCH3ClBr2HOAcNHCH3ClBrCH3NHCOCH3 COOHHNO3H2SO4CH3NO2NO2CH3NO2CHOCH3COOHCH3COOHH2SO4HNO3CH3COOHNO2+CH3COOHO2NCH3CHCH3CH3HNO3CH3CHCH3CH3NO2H2SO4CH3SO3HBrBr2F

9、eBr3CH3BrAlBr3CH3H2SO4BrBr/CH3BrAlBr3CH3H2SO4CH3SO3HBr2 / FeBr3/CH3BrAlBr3CH3Br2/FeBr3CH3BrH2SO4H2SO4SO3HBr2/FeBr3SO3HBrCH3BrAlBr3 NO2ClCH2CH2CH3NO2NO2ClClOClCH3CH2CClOAlCl3( )( )( )ClNO2( )( )( )O( )( )( )( )OClCl2FeCl3ClZnHgHClHNO3 H2SO4两个苯环共用两个相邻碳原子两个苯环共用两个相邻碳原子稠合芳烃稠合芳烃(naphthalene)0.142 nm0.136

10、nm0.140 nm0.139 nm+ Cl2FeCl3, 105 Cl+ HClBrCH323146758CH3OHNO212358467E+进进攻攻位位进进攻攻位位EHEH其它极极限限结结构构EH其它极限结构。HNO3H2SO4NO2（ %）9530 60+C165/ /H2SO4H2SO4(浓浓)80SO3H165SO3HSO3HHHSO3H+ CrO3CH3COOH13OO2+ 9O2V2O5K2SO4390CCOOO2+ 4 CO2 + 4 H2O+NH2O2KMnO4/H+COOHCOOH+ Na液液 NH3, EtOHH2/PdC C, , ,加压H2/RhC C, ,加压NHCCH3OHNO3, CH3COOHNHCCH3ONO2OCH3HNO3OCH3NO2NO2HNO3H2SO4NO2O2N+NO2NO2111222333444555666777888999101010蒽菲Br2 /CCl4Br+。O2V2O5/ CNa2Cr2O7/稀H2SO4/OO或300 500OOK2Cr2O7/H2SO4或