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1、第十六章 重氮化合物和偶氮化合物 一、 命名下列化合物:1.N2HSO4 2.CH3CONHN2Cl3.CH3N=NOH4.CH3N=NN(CH3)25.NHNHCH3H3C6. CCl2.二氯碳烯二、 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?为什 么?解: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,有利于偶合反应。NN+N =N+N =N+OHN =NOH三、 试解释下面偶合反应为什么在不同 PH 值得到不同产物?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
2、基偶氮苯4甲基4二甲氨基偶氮苯 2,2二甲基氢化偶氮苯解: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。四、 完成下列反应式:FCH3NaBF4CH3N=NCH3NH2CH3CNCH3CuCNKCNBrCH3CuBrHBrCH3C2H5OHCH3H2O,H+NaNO2,HClFe,HClN2ClNH2NO2CH3CH3CH31.NHOH2.OHOCH3 +CH2N23.CH3 CHCl3(CH3)3COKCH3ClCl4.CH3CH2CH2C=C CH2CH
3、2CH3HH+CH2.CH2CH2CH3CH2CH2CH3HH五、 指出下列偶氮染料的重氮组分和偶连组分。解: 重氮组分 偶连组分1.N=NHSO3N(CH3)2HSO3N2+ N(CH3)22.N=NN=NOHN=NN2+ OH3.CH3CONHN=NCH3OHCH3CONHN2+HOCH34.NaSO3N=NHONaSO3N2+HO5.SO3HNH2N=NSO3HN2N=NNH2SO3HN2+NH2六、 完成下列合成:1.NO2ClClClNO2ClClNH2NH2N2ClFe/HCl3Cl2ClClClNaNO2,HClClClClH3PO2Cl2.CH3CH3BrBrCH3CH3CH3
4、CH3BrCH3HNO3H2SO4NO2NH2NH2BrBrH2Br21,HNO22,H3PO2 BrCNCNNO2NO2NH2NH2N2ClN2ClCNCNONaNO2,HClKCN,CuCN3.NHCOCH3OHBrNHCOCH3Br2NHCOCH3BrBrBrNH2N2HSO4 H2O,H+NaNO2H2SO450%H2SO4OHBr4.5.CH3CH3NO2CH3CH3CH3CH3 HNO3H2SO4NO2NH2NHCOCH3HCH3COClHNO3H2SO4CH3NO2CH3NHCOCH3NO2CH3 H2O,H+NH2N2ClNaNO2,HClNO2CH3NO2H3PO26.NH2
5、NO2BrBrNH2 CH3COClNHCOCH3HNO3H2SO4NHCOCH3NO2NHCOCH3NO2Br2BrBrNO2BrBrH2O,H+NH2NO2BrBrNaNO2HClN2ClNO2BrBrH3PO27.NH2BrCOOHBrNH2NH2NH2 H2SO4SO3HBr22BrBrNH2SO3HH2O,H+BrBrBrBrNaNO2,HClN2ClKCN/CuCNBrBrBrBrCNCOOHH2O,H+七、 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:1.(CH3)2NN=NHNO3H2SO4NO2 HNH2N(CH3)22CH3INH2HNO2 N2C
6、lN(CH3)2N2Cl+(CH3)2NN=N2.CH3N=NH2NNH2CH3HNO3H2SO4NO2CH3CH3H NH2CH3NaNO2HClN2ClHNO3H2SO42NO2O2NH2NNH2HCH3N2ClCH3N=NH2NNH23.OHCH3N=NCH3CH3SO3HCH3CH3H2SO4NaOHONaCH3H3O+OHCH3HNO3H2SO4CH3CH3NO2NO2 +CH3NO2HCH3CH3NH2N2ClNaNO2HClCH3OH+OHCH3N=NCH3N=N4.HSO3OHNH2H2SO4NH2SO3HHNO2SO3HN2Cl+H2SO4650CSO3H1.NaOH2.H3
7、O+OHOHSO3HN2Cl+N=NHSO3OH5.(CH3)2NN=NNO2NO2NH2NHCOCH3NO2NHCOCH3NO2NO2NH2N2ClN(CH3)2(CH3)2NN=NNO2NH22CH3I N(CH3)2N=NCH3CH3CH3NO22ZnNaOH/C2H5OHN=NCH3CH36.7.COONaN=NNaSO3OHOH+CO2NaCO3OHCOONaNaSO3N2ClCOONaN=NNaSO3OH8.N=NCH3HOCH3OHCH3+ClN2CH3N=NHOCH3CH3八、 推测下列化合物的结构:1,某芳烃分子式为C6H3NO2ClBrFe,HClNaNO2,HClC2H5
8、OHClBrNaOH,H2OC6H3OHClNO2ClBrNO2C6H3NO2 ClBr,试根据下列反应确定其结构:解:结构式 为:C6H4NO2CH32、某芳香性族化合物分子式为 ,试根据下列反应确定其结构:C6H4NO2CH3Fe,HClNaNO2,HClCuCNH2O,H+KMnO4COCOONO2CH3NH2CH3CH3CH3CH3COCOOFe,HCl NaNO2,HClN2Cl CuCNCNH2O,H+COOH KMnO4COOHCOOH九、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?1.N=N(CH3)2NSO3H(CH3)2NNH2H2NSO3HSnCl2
9、,HClN=NSnCl2,HClHSO3NH2SO3H2.HSO3NH2NH2SO3HH2N+N=NSnCl2,HClNH2H2N+3.CH3OHCH3OH十、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。解:结构及 反应:原化合物为:N=NCH3N(CH3)2CH3CH3CH3CH3 HNO3H2SO4NO2NH2N2ClHHNO2HNO3H2SO4NO2NH2N(CH3)2H十一、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。H2SO4HNO3CH3COClHNHCOCH3NH2NO2H2SO4HNO3CH3CH3CH3CH3N=NCH3NH2CH3解:原化合物为:NHCOCH3CH3NO2H2O,H+NaNO2,HClH3PO2CH3NO2Fe,HClCH3NH2NaNO2,HClCH3N2Cl CH3NH2N=NCH3NH2CH3