第七章 芳环上亲电和亲核取代反应反应

1、芳环上亲电和亲核取代反应反应芳环上亲电和亲核取代反应反应有有p p电子，象烯烃电子，象烯烃+EEHE势势能能反反应应进进程程Fe or FeX3HNO3 , 浓H2SO4（混混酸酸）浓 H2SO4 or发烟 H2SO4RX, AlCl3RCX, AlCl3OXNO2SO3HRCROX2Fe or FeX3XX2( X = Cl, Br)CH3Fe or FeX3X2CH3XCH3XhvCH2X亲亲电电取取代代自自由由基基取取代代HF / CCl4FXeF2（自自由由基基型型反反应应）II2HNO3ICl(I2Cl2)IH H+NO2HNO3 (浓)H2SO4 (浓)5560oCHONO2HOS

2、O3HHONO2HHSO4+H2O +NO2NO2HH+NO2NO2NO2HNO3 (浓) / H2SO4 (浓)55oCCH3CH3NO2CH3+HNO3 (发烟) / H2SO4 (浓)80oCNO2CH3NO2CH3+O2NNO2HNO3 (发烟) / H2SO4 (浓)110oCNO2CH3O2NNO2苯胺类化合物的苯胺类化合物的主要制备方法主要制备方法ArHHNO3 (浓)H2SO4 (浓)ArNO2ArNH2Fe or Sn / HCl（还还原原）SO3HH2SO4 (浓)， 110oCH2SO4 (发烟)， 40oC或或(含含10 SO3)SO3HH2SO4 , H2O（大大量量

3、）（稀稀酸酸溶溶液液）, ,加加热热H3OSO3HH+SO3SOOOH2SO4SO3H+H+SO3H2O2 H2SO4SO3HSO4SO3HArSO2ClArPOCl3ROHRNH2SO2ORArSO2NHRArH2SO4 (浓)C12H25C12H25SO3HNaOHC12H25SO3NaH2SO4 (浓)H3CH3CSO3HH3CH3CClH3CCl2, FeH3CCl+H3CClH2SO4 (浓)H3CH3CSO3HCl2, FeH3CSO3HClH2O, H+H3CCl OHH2SO410oCOHSO3HSO3HOHNO2NO2O2NHNO3HNO3AlCl3CH2CH2CH3CH3C

4、H2CH2XCHCH3CH3CH3CH2CH2XAlCl3CH3CHCH2H HCH3CHCH3AlCl3R XRR XAlCl3RAlCl3XRHH+RRCCRRRRH+CCRRRRHROHH+ROH2R+H2OCHH2CCHCH3HFCH3CH3CH3CH2OH /CH2CH3H2SO4/RCOClRCOORCORCOAlCl3或或酮与酮与AlCl3络合，络合，消耗消耗1eqv. AlCl3AlCl3RCOORCORCOORCOAlCl3RCO+ORCOAlCl3ClORCOAlCl2HH+RCORCOAlCl3RCOAlCl3H2ORCO消耗消耗1eqv. AlCl3消耗消耗1eqv.

5、AlCl3ArHAlCl3RCOClArRCOZn(Hg) / HClArCH2Ror NH2NH2 / OHRXAlCl3RRXAlCl3RRRRHCOHHClZnCl2CH2ClHClAlCl3, CuClCHOCO HClCOHCOClAlCl3HCOAlCl4CHOCHOHH+Fe or FeX3浓 H2SO4 or发烟 H2SO4RXXNO2SO3HRCROX2HNO3浓H2SO4AlCl3or(RCO)2ORCOClAlCl3X=Cl, BrZnCl2CH2ClH2CO, HClHClAlCl3, CuClCHOCO,ClOH高高温温，高高压压NaOHH+ClClOH+ + ClX

6、NO2XNO2NaOH135160oCH+OHNO2NO2Na2CO3100oCH+OHNO2NO2XNO2NO2O2NH2OH+OHNO2NO2O2NNO2NO2OCH3O2NNO2NH3COO2NKOC2H5OC2H5OOKNO2NO2OC2H5O2NKOCH3ClNO2NO2SHNO2NO2OCH3NO2NO2NHCH3NO2NO2NHNH2NO2NO2NaSHNaOCH3NH2CH3NH2NH2NH2NO2OCH3NO2200oCNH3NO2NO2NaSHNH3SHNO2OCH3NO2NH2NO2100oCNaOCH3XWNuNuWX+W:N2NR3NONO2CF3CRCNCOOHOFNCNHDMSO, NNCHFClClClClNaORClClORCl+NaClClONa高高温温，高高压压NaOHNH2高高温温，高高压压NH3XNH3NH2NH2NH2NH2CH3BrN