第7章苯和芳香烃-2

1、EEHEH+EHEHEHERRRREEE取代基对反应有两方面影响取代基对反应有两方面影响反应活性反应活性和和反应取向反应取向HNO3 / H2SO4RRRNO2NO2NO2+RCH3ClNO2OCH3CH3ClNO2NH2OHORRArNO2NR3CNSO3HFClBrICROCHOCOHOCORONHC ROHCF3CCl3NHRNR2OOC RO邻对位致活基的特点给电子基团邻对位致活基的特点给电子基团间位致钝基的特点吸电子基团间位致钝基的特点吸电子基团邻对位致钝基卤素原子基团邻对位致钝基卤素原子基团PhN2ClOHH2OOHBrBrBrNR2PhN2ClPH=5R2NNNPhRC ClOR

2、CONR2HNO3H2SO4NHR2Br2AlCl3RC ClOAlCl3NHR2NO2CH3 CF3 NH2NH2NH2NH2NH2 NH2NOONOONOONOONOONOO CH3ECH3ECH3ECH3EH+CH3EHHHCH3ECH3ECH3ECH3E+CH3ECH3EH+HCH3EHCH3EHCH3ECH3ECH3ECH3ECH3EH+CH3EHHHCH3E+CH3EHCH3EHorCH3HE势势能能反反应应进进程程OREOREORE+OREOREOREOREOREH+OREHHHOREHOREOREORH+OREOREEHHHOREHOREOREH+OREHOREHOREHORE

3、+OREHOREHorORHE势势能能反反应应进进程程NO2ENO2ENO2E+NO2E+NO2ENO2ENO2ENO2EH+NO2EHHHNO2ENO2EH+HNO2EHNO2EHNO2ENO2ENO2ENO2ENO2EH+NO2EHHHNO2E+NO2EHNO2EHorNO2HE势势能能反反应应进进程程ClClNO2ClNO2ClNO2H+ClNO2HHHClNO2HNO2ClNO2ClNO2+ClNO2+ClH2SO430%70%微微量量 HNO3（对位取代情况类似）（对位取代情况类似）ClClNO2ClNO2ClNO2H+ClNO2HHHNO2Cl+ClNO2HClNO2HClHNO2

4、势势能能反反应应进进程程NO2NR2(H)OH(R)NHCROOCRORXNR3(H)NO2CNSO3HCROOHCH3OHCH3ClCH358%42%ClCH319%17%43%20%COOHNO2OHCH3OHCHOCH3NO2OHNO2CNO2CH3H3CCH3CCH3H3CCH3NO2CCH3H3CCH3NO2CCH3H3CCH380128+HNO3H2SO4CH3CH3CH3CH3SO3HCH3H2SO4CH3SO3HCH3SO3H+0oC100oC53%43%79%13%NHCH3C CH3OHNO3H2SO4NHCH3C CH3ONHCH3C CH3ONO2O2N+78%14%H

5、2SO4BrNO2或或BrNO2HNO3H2SO4BrBrNO2Br2FeHNO3H2SO4NO2Br2FeBrNO2NH2NH2NO2NH2HNO3H2SO4NH3NH3NO2HNO3H2SO4NH2ClCCH3OEt3N（碱）NHCCH3OHNO3H2SO4NHCCH3ONO2+少少量量（分分离离除除去去）主主要要产产物物H2OH+ or OHNH2NO2NHCCH3ONO2NH2NH2NO2（纯纯产产物物）NH2ClCCH3OEt3N（碱）NHCCH3O发烟 H2SO4H2ONHCCH3OSO3HNHCCH3OSO3HHNO3H2SO4,NO2H+NH2NO2CH2CH2CH3COCH2

6、CH3CH2CH2CH3CH2CH2CH3XAlCl3COCH2CH3ClAlCl3CH2CH2CH3COCH2CH3第一步不合理：第一步不合理：(1) 直接接丙基，有重排产物直接接丙基，有重排产物(2)丙基为致活基团，易多取代丙基为致活基团，易多取代COCH2CH3ClAlCl3COCH2CH3CH2CH2CH3XAlCl3COCH2CH3ClCOCH2CH3Zn(Hg) / HClCH2CH2CH3COCH2CH3ClAlCl3CH2CH2CH3COCH2CH3orNH2NH2 / NaOHAlCl3KMnO4or K2CrO7O2 / V2O5400 oCOOO3Cl2紫外光ClClCl

7、ClClCl六氯化苯（C6H6Cl6)eC2H5OHC2H5OHHeHHC2H5OHC2H5OHHHHNa+Na+(e ) NH3NH3较稳定：较稳定：自由基与负自由基与负离子电子对处于对位离子电子对处于对位Ni, 180200oC+H2高压高压Na / NH3（液液）C2H5OH注意双键的位置注意双键的位置1. 氢的卤代反应氢的卤代反应CH3Cl2光照CH2ClCl2光照Cl2光照CHCl2CCl3CH2CH3NBSCCl4CHBrCH3CR(H)R(H)HKMnO4COOHCRRRKMnO42.氢的氧化反应氢的氧化反应CH3H2SO4CH3NO2KMnO4COOHNO2+CH3NO2H2SO4HNO3 ,CH3NO2NO2KMnO4COOHNO2NO2HNO3COOHCH3NO2COOHNO2NO2&CH3KMnO4C