有機(jī)化學(xué)007-苯和芳香烴2

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

2、OONOONOO CH3ECH3ECH3ECH3EH+CH3EHHHCH3ECH3ECH3ECH3E+CH3ECH3EH+HCH3EHCH3EHCH3ECH3ECH3ECH3ECH3EH+CH3EHHHCH3E+CH3EHCH3EHorCH3HE勢(shì)勢(shì)能能反反應(yīng)應(yīng)進(jìn)進(jìn)程程OREOREORE+OREOREOREOREOREH+OREHHHOREHOREOREORH+OREOREEHHHOREHOREOREH+OREHOREHOREHORE+OREHOREHorORHE勢(shì)勢(shì)能能反反應(yīng)應(yīng)進(jìn)進(jìn)程程N(yùn)O2ENO2ENO2E+NO2E+NO2ENO2ENO2ENO2EH+NO2EHHHNO2ENO2EH+H

3、NO2EHNO2EHNO2ENO2ENO2ENO2ENO2EH+NO2EHHHNO2E+NO2EHNO2EHorNO2HE勢(shì)勢(shì)能能反反應(yīng)應(yīng)進(jìn)進(jìn)程程ClClNO2ClNO2ClNO2H+ClNO2HHHClNO2HNO2ClNO2ClNO2+ClNO2+ClH2SO430%70%微微量量 HNO3（對(duì)位取代情況類似）（對(duì)位取代情況類似）ClClNO2ClNO2ClNO2H+ClNO2HHHNO2Cl+ClNO2HClNO2HClHNO2勢(shì)勢(shì)能能反反應(yīng)應(yīng)進(jìn)進(jìn)程程N(yùn)O2NR2(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(tuán)，易多取代丙基為致活基團(tuán)，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(biāo)分子不能得到目標(biāo)分子eC2H5OHC2H5OHHeHHC2H5OHC2H5OHHHHNa+Na+(e ) NH3NH3較穩(wěn)定：較穩(wěn)定：自由基與負(fù)自由基與負(fù)離子電子對(duì)處于對(duì)位離子電子對(duì)處于對(duì)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