有機(jī)化學(xué)課件：第五章 芳烴芳香性

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給電基吸電基.。CC+濃濃H2SO4HNO3NO2NO2NO2100NO2NO2O2NHNO SO3濃H2SO4100。；5d+ HNO3H2SO450 - 55 CNO2+ H3O + HSO4HNO3+ 2H2SO4NO2+ H3O + 2HSO4。CCH3CH3CH3+濃

3、濃H2SO4HNO3NO2NO2305937%CH3NO2H+SOOOSOOOH25 C濃濃H2SO4CH3CH3CH3+濃H2SO4H2O100。SO3HSO3H053437913%CCCH3CH3Br+濃H2SO4100。SO3HCBr2/FeCH3SO3HH2OHCl/P.a.BrCH3SO3+ H3O + 2HSO42H2SO4H+SOOO慢慢SO3H決定反應(yīng)速率的一步?jīng)Q定反應(yīng)速率的一步SO3H+ HSO4快快SO3+ H2SO4SO3+ H2SO4快SO3HHSO4+H2SO4SO3H+ H2OCH3+CH3CH2CH2XCH3CHXCH3CH2CH2OHCH3CHOHCH3CH C

4、H2(CH3CH2CH2)2OHXHXH2OH2OCH3CH2CH2OHCH3AlCl3（無水）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無水C CH2CH3OOOOOHBrCH3CH2C OHH2OC2H5OH+/OAlCl3NH2+ RX不不反反應(yīng)應(yīng)或或難難反反應(yīng)應(yīng)NH2+ AlCl3AlCl3ArNH2ArNO2、SO3H、CHO、C R、COOH和NR2等OCH3CH2C BrAlCl3無

6、水C CH2CH3OO+/Zn Hg/HClCH2CH2CH3CH3,CH2OH,CH2CN,CHO,CH2COOH,CH2N(CH3)2等等3+ (HCHO)3 + 3 HCl無無水水ZnCl2CH2Cl+ 3 H2O3CH2ClCH3CH2OHCHOCH2CNCH2COOHCH2N(CH3)2HCl/ZnNaOHCrO3/吡啶或Cu/高溫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 H2SO4兩個(gè)苯環(huán)共用兩個(gè)相鄰碳原子兩個(gè)苯環(huán)共用兩個(gè)相鄰碳原子稠合芳烴稠合芳烴(naphthalene)0.142 nm0.136

10、nm0.140 nm0.139 nm+ Cl2FeCl3, 105 Cl+ HClBrCH323146758CH3OHNO212358467E+進(jìn)進(jìn)攻攻位位進(jìn)進(jìn)攻攻位位EHEH其它極極限限結(jié)結(jié)構(gòu)構(gòu)EH其它極限結(jié)構(gòu)。HNO3H2SO4NO2（ %）9530 60+C165/ /H2SO4H2SO4(濃濃)80SO3H165SO3HSO3HHHSO3H+ CrO3CH3COOH13OO2+ 9O2V2O5K2SO4390CCOOO2+ 4 CO2 + 4 H2O+NH2O2KMnO4/H+COOHCOOH+ Na液液 NH3, EtOHH2/PdC C, , ,加壓H2/RhC C, ,加壓NHCCH3OHNO3, CH3COOHNHCCH3ONO2OCH3HNO3OCH3NO2NO2HNO3H2SO4NO2O2N+NO2NO2111222333444555666777888999101010蒽菲Br2 /CCl4Br+。O2V2O5/ CNa2Cr2O7/稀H2SO4/OO或300 500OOK2Cr2O7/H2SO4或