第16章重氮化合物和偶氮化合物

武汉工程大学化学与环境工程学院有机化学习题参考答案第十六章重氮化合物和偶氮化合物1.命名下列化合物：1.N2HSO42.CH3CONHN2Cl3.CH3N=NOH4.CH3N=NN(CH3)25.NHNHCH3H3C6..CCl2.二氯碳烯2.当苯基重氮盐的邻位或对位连有硝基时，其偶合反应的活性事增强还是降低？偶合反应活性增强。邻位或对位上有硝基使氮原子上正电荷增多，有利于苯基重氮盐作为亲电试剂对胺、酚等进行偶合反应。NN+N=N+N=N++OHN=NOH3.试解释下面偶合反应为什么在不同PH值得到不同产物？PH等于5时，氨基供电子能力强于羟基，偶合反应在氨基的邻位发生。PH等于9时，为弱碱性，羟基以萘氧负离子形式存在，氧负离子供电子能力大于氨基，偶合反应发生在羟基的邻位。H2NOH+C6H5N2+PH=5PH=9H2NOHN=NC6H5H2NOHN=NC6H5重氮苯硫酸盐对乙酰氨基重氮苯盐酸盐4-甲基-4‘-羟基偶氮苯4-甲基-4‘-N,N-二甲氨基偶氮苯2,2‘－二甲基氢化偶氮苯武汉工程大学化学与环境工程学院有机化学习题参考答案4.完成下列反应式：FCH3NaBF4CH3N=NCH3NH2CH3CNCH3CuCNKCNBrCH3CuBrHBrCH3C2H5OHCH3H2O,H+Fe,HClNO2CH3NHOHNaNO2,HClN2ClNH2CH3CH3(1)OHOCH3+CH2N2(2)CH3CHCl3(CH3)3COKCH3ClCl(3)CH3CH2CH2C=CCH2CH2CH3HH+CH2..CH2CH2CH3CH2CH2CH3HH(4)武汉工程大学化学与环境工程学院有机化学习题参考答案5.指出下列偶氮染料的重氮组分和偶联组分。重氮组分偶联组分HSO3N2+N(CH3)2N=NN2+OHCH3CONHN2+HOCH3NaSO3N2+HO(1)(2)(3)(4)(5)SO3HNH2N2N2++6.完成下列合成：NO2Fe/HClNH23Cl2NH2ClClClNaNO2/HClN2ClClClClClClClH3PO2CH3HNO3/H2SO4CH3NO2CH3NH2Fe/HClCH3NH22Br2BrBrCH3BrBrHNO21.2.H3PO2(1)(2)(3)CNCNNO2NO2NH2NH2N2ClN2ClCNCN[O]NaNO2,HClKCN,CuCN3.(4)NHCOCH3OHBr4.5.CH3CH3NO2NHCOCH3Br2NHCOCH3BrBrBrNH2N2HSO4H2O,H+NaNO2H2SO450%H2SO4OHBrCH3CH3CH3CH3HNO3H2SO4NO2NH2NHCOCH3[H]CH3COClHNO3H2SO4NHCOCH3OHBr4.5.CH3CH3NO2NHCOCH3Br2NHCOCH3BrBrBrNH2N2HSO4H2O,H+NaNO2H2SO450%H2SO4OHBrCH3CH3CH3CH3HNO3H2SO4NO2NH2NHCOCH3[H]CH3COClHNO3H2SO4NHCOCH3OHBr4.5.CH3CH3NO2NHCOCH3Br2NHCOCH3BrBrBrNH2N2HSO4H2O,H+NaNO2H2SO450%H2SO4OHBrCH3CH3CH3CH3HNO3H2SO4NO2NH2NHCOCH3[H]CH3COClHNO3H2SO4武汉工程大学化学与环境工程学院有机化学习题参考答案(5)NHCOCH3OHBr4.5.CH3CH3NO2NHCOCH3Br2NHCOCH3BrBrBrNH2N2HSO4H2O,H+NaNO2H2SO450%H2SO4OHBrCH3CH3CH3CH3HNO3H2SO4NO2NH2NHCOCH3[H]CH3COClHNO3H2SO4CH3NO2CH3NHCOCH3NO2CH3H2O,H+NH2N2ClNaNO2,HClNO2CH3NO2H3PO2(6)6.NH2NO2BrBrNH2CH3COClNHCOCH3HNO3H2SO4NHCOCH3NO2NHCOCH3NO2Br2BrBrNO2BrBrH2O,H+NH2NO2BrBrNaNO2HClN2ClNO2BrH3PO27.NH2BrCOOHBr6.NH2NO2BrBrNH2CH3COClNHCOCH3HNO3H2SO4NHCOCH3NO2NHCOCH3NO2Br2BrBrNO2BrBrH2O,H+NH2NO2BrBrNaNO2HClN2ClNO2BrH3PO27.NH2BrCOOHBr6.NH2NO2BrBrNH2CH3COClNHCOCH3HNO3H2SO4NHCOCH3NO2NHCOCH3NO2Br2BrBrNO2BrBrH2O,H+NH2NO2BrBrNaNO2HClN2ClNO2BrH3PO27.NH2BrCOOHBr6.NH2NO2BrBrNH2CH3COClNHCOCH3HNO3H2SO4NHCOCH3NO2NHCOCH3NO2Br2BrBrNO2BrBrH2O,H+NH2NO2BrBrNaNO2HClN2ClNO2BrH3PO27.NH2BrCOOHBrNO2BrBr(7)NH2NH2NH2H2SO4SO3HBr22BrBrNH2SO3HH2O,H+BrBrNaNO2,HClBrBrN2ClKCN/CuCNBrBrBrBrCNCOOHH2O,H+NH2NH2NH2H2SO4SO3HBr22BrBrNH2SO3HH2O,H+BrBrNaNO2,HClBrBrN2ClKCN/CuCNBrBrBrBrCNCOOHH2O,H+NH2NH2NH2H2SO4SO3HBr22BrBrNH2SO3HH2O,H+BrBrNaNO2,HClBrBrN2ClKCN/CuCNBrBrBrBrCNCOOHH2O,H+7.以苯，甲苯，萘和小于或等于两个碳原子的有机化合物为原料合成下列化合物：武汉工程大学化学与环境工程学院有机化学习题参考答案(1)1.(CH3)2NN=NHNO3H2SO4NO2[H]NH2N(CH3)22CH3INH2HNO2N2ClN(CH3)2N2Cl+(CH3)2NN=N1.(CH3)2NN=NHNO3H2SO4NO2[H]NH2N(CH3)22CH3INH2HNO2N2ClN(CH3)2N2Cl+(CH3)2NN=N1.(CH3)2NN=NHNO3H2SO4NO2[H]NH2N(CH3)22CH3INH2HNO2N2ClN(CH3)2N2Cl+(CH3)2NN=N(2)2.CH3N=NH2NNH2CH3HNO3H2SO4NO2CH3CH3[H]NH2CH3NaNO2HClN2ClHNO3H2SO42NO2O2NH2NNH2[H]CH3N2ClCH3N=NH2NNH22.CH3N=NH2NNH2CH3HNO3H2SO4NO2CH3CH3[H]NH2CH3NaNO2HClN2ClHNO3H2SO42NO2O2NH2NNH2[H]CH3N2ClCH3N=NH2NNH22.CH3N=NH2NNH2CH3HNO3H2SO4NO2CH3CH3[H]NH2CH3NaNO2HClN2ClHNO3H2SO42NO2O2NH2NNH2[H]CH3N2ClCH3N=NH2NNH2(3)CH3SO3HCH3CH3H2SO4NaOHONaCH3H3O+OHCH3HNO3H2SO4CH3CH3NO2NO2+CH3NO2[H]CH3CH3NH2N2ClNaNO2HClCH3OH+OHCH3N=NCH3武汉工程大学化学与环境工程学院有机化学习题参考答案N=N4.HSO3OHNH2H2SO4NH2SO3HHNO2SO3HN2Cl+H2SO4650CSO3H1.NaOH2.H3O+OHOHSO3HN2Cl+N=NHSO3OH5.(CH3)2NN=NNO2NO2NH2NHCOCH3NO2NHCOCH3NO2NO2NH2N2ClN(CH3)2(CH3)2NN=NNO2NH22CH3IN(CH3)2武汉工程大学化学与环境工程学院有机化学习题参考答案N=NCH3CH36.7.COONaN=NNaSO3OHOH+CO2NaCO3OHCOONaNaSO3N2ClCOONaN=NNaSO3OH8.N=NCH3HOCH3OHCH3+ClN2CH3N=NHOCH3CH3CH3NO22ZnNaOH/C2H5OHN=NCH3CH38.推测下列化合物的结构：（1）某芳烃分子式为：C6H3BrClNO2试根据下列反应确定其结构：C6H3NO2ClBrFe,HClNaNO2,HClC2H5OHClBrNaOH,H2OC6H3OHClNO2结构式为：ClBrNO2武汉工程大学化学与环境工程学院有机化学习题参考答案（2）某芳香性族化合物分子式为：C6H4CH3NO2;试根据下列反应确定其结构：C6H4NO2CH3Fe,HClNaNO2,HClCuCNH2O,H+KMnO4COCOO结构及反应：CH3CH3COCOOCNH2O,H+COOHKMnO4COOHCOOHNO2CH3NH2CH3CH3Fe,HClNaNO2,HClN2ClCuCN9.下列结构的偶氮染料，以氯化亚锡－盐酸溶液还原分解后，生成那些化合物？(CH3)2NNH2H2NSO3H(1)HSO3NH2NH2SO3HH2N+(2)NH2H2N+CH3OH(3)10．某化合物以氯化亚锡盐酸还原可得对甲基苯胺和N,N－二甲基对苯二胺，试推测原化合物的结构，并以苯，甲苯及甲醇为原料合成之。原化合物为：N=NCH3N(CH3)2CH3CH3CH3CH3HNO3H2SO4NO2NH2N2Cl[H]HNO2HNO3H2SO4NO2NH2N(CH3)2[H]武汉工程大学化学与环境工程学院有机化学习题参考答案11．某化合物以氯化亚锡盐酸还原得到间甲基苯胺和4－甲基－1，2－苯二胺，试推测原化合物的结构，并以甲苯为原料合成之。原化合物为：H2SO4HNO3CH3COCl[H]NHCOCH3NH2NO2H2SO4HNO3CH3CH3CH3CH3N=NCH3NH2CH3NHCOCH3CH3NO2H2O,H+NaNO2,HClH3PO2CH3NO2Fe,HClCH3NH2NaNO2,HClCH3N2ClCH3NH2N=NCH3NH2CH3