有機化學007-苯和芳香烴2

1、EEHEH+EHEHEHERRRREEE取代基對反應有兩方面影響取代基對反應有兩方面影響反應活性反應活性和和反應取向反應取向HNO3 / H2SO4RRRNO2NO2NO2+RCH3ClNO2CH3ClNO2NH2OHORRArNO2NR3CNSO3HFClBrICROCHOCOHOCORONHC ROHCF3CCl3NHRNR2OOC ROPhN2ClOHH2OOHBrBrBrNR2PhN2ClPH=5R2NNNPhRC ClORCONR2HNO3H2SO4NHR2Br2AlCl3RC ClOAlCl3NHR2NO2CH3 CF3X NH2NH2NH2NH2NH2 NH2NOONOONOON

2、OONOONOO CH3ECH3ECH3ECH3EH+CH3EHHHCH3ECH3ECH3ECH3E+CH3ECH3EH+HCH3EHCH3EHCH3ECH3ECH3ECH3ECH3EH+CH3EHHHCH3E+CH3EHCH3EHorCH3HE勢勢能能反反應應進進程程OREOREORE+OREOREOREOREOREH+OREHHHOREHOREOREORH+OREOREEHHHOREHOREOREH+OREHOREHOREHORE+OREHOREHorORHE勢勢能能反反應應進進程程NO2ENO2ENO2E+NO2E+NO2ENO2ENO2ENO2EH+NO2EHHHNO2ENO2EH+H

3、NO2EHNO2EHNO2ENO2ENO2ENO2ENO2EH+NO2EHHHNO2E+NO2EHNO2EHorNO2HE勢勢能能反反應應進進程程ClClNO2ClNO2ClNO2H+ClNO2HHHClNO2HNO2ClNO2ClNO2+ClNO2+ClH2SO430%70%微微量量 HNO3（對位取代情況類似）（對位取代情況類似）ClClNO2ClNO2ClNO2H+ClNO2HHHNO2Cl+ClNO2HClNO2HClHNO2勢勢能能反反應應進進程程NO2NR2(H)OH(R)NHCROOCRORXNR3(H)NO2CNSO3HCROOHCHOCH3NO2OHNO2CNO2CH3H3C

4、CH3CCH3H3CCH3NO2CCH3H3CCH3NO2CCH3H3CCH380128+HNO3H2SO4CH3CH3CH3CH3SO3HCH3H2SO4CH3SO3HCH3SO3H+0oC100oC53%43%79%13%NHCH3C CH3OHNO3H2SO4NHCH3C CH3ONHCH3C CH3ONO2O2N+78%14%H2SO4BrNO2或或BrNO2HNO3H2SO4BrBrNO2Br2FeHNO3H2SO4NO2Br2FeBrNO2NH2NH2NO2NH2HNO3H2SO4NH3NH3NO2HNO3H2SO4NH2ClCCH3OEt3N（堿）NHCCH3OHNO3H2SO4

5、NHCCH3ONO2+少少量量（分分離離除除去去）主主要要產(chǎn)產(chǎn)物物H2OH+ or OHNH2NO2NHCCH3ONO2NH2NH2NO2（純純產(chǎn)產(chǎn)物物）NH2ClCCH3OEt3N（堿）NHCCH3O發(fā)煙 H2SO4H2ONHCCH3OSO3HNHCCH3OSO3HHNO3H2SO4,NO2H+NH2NO2CH2CH2CH3COCH2CH3CH2CH2CH3CH2CH2CH3XAlCl3COCH2CH3ClAlCl3CH2CH2CH3COCH2CH3第一步不合理：第一步不合理：(1) 直接接丙基，有重排產(chǎn)物直接接丙基，有重排產(chǎn)物(2)丙基為致活基團，易多取代丙基為致活基團，易多取代COCH2

6、CH3ClAlCl3COCH2CH3CH2CH2CH3XAlCl3COCH2CH3ClCOCH2CH3Zn(Hg) / HClCH2CH2CH3COCH2CH3ClAlCl3CH2CH2CH3COCH2CH3orNH2NH2 / NaOHAlCl3KMnO4or K2CrO7O2 / V2O5400 oCOOOCR(H)R(H)HKMnO4COOHCRRRKMnO4CH3H2SO4CH3NO2KMnO4COOHNO2+CH3NO2H2SO4HNO3 ,CH3NO2NO2KMnO4COOHNO2NO2HNO3COOHCH3NO2COOHNO2NO2&COOHCH3NO2BrCH3KMnO

7、4COOHH2SO4HNO3COOHNO2FeBr2COOHNO2BrFeBr2 ,COOHBrH2SO4HNO3COOHBrNO2COOHBrNO2+符合定位取向符合定位取向不能得到目標分子不能得到目標分子eC2H5OHC2H5OHHeHHC2H5OHC2H5OHHHHNa+Na+(e ) NH3NH3較穩(wěn)定：較穩(wěn)定：自由基與負自由基與負離子電子對處于對位離子電子對處于對位Ni, 180200oC+H2高壓高壓Na / NH3（液液）C2H5OH注意雙鍵的位置注意雙鍵的位置COOHNa / NH3（液）C2H5OHCOOHCOOHCOOHRNa / NH3（液）C2H5OHRORNa / NH3（液）C2H5OHORRRXNO2COR(H)CH