材料科学及工程有机化学有机含氮化合物

1、材料科学及工程有机化学有材料科学及工程有机化学有机含氮化合物机含氮化合物17.1 硝基化合物HO NO2RO NO2RNO2HONORO NORNO硝酸硝酸酯硝基化合物（酸中H被烃基取代）（酸中OH被烃基取代）亚硝酸亚硝酸酯亚硝基化合物注意写法，硝基化合物是CN相连硝酸酯是CO相连C H3N O2N O2C H3硝 基 甲 烷对 硝 基 甲 苯H2CH2CONO2ONO2H2CONO2三硝基甘油酯（可作抗血栓药，救心丸）（可作抗血栓药，救心丸）NO2CH3NO2NO2TNT硝基化合物的构造RNO2RONO硝基化合物亚硝酸酯硝基化合物的还原RNO2HH,PtFeClHRNH2OH2ArNO2HH

2、,PtFeClHArNH2OH2+6+或+2+6+或+222NO2NONHOHNH2选择性还原剂：选择性还原剂：SnCl2（氯化亚锡）和盐酸，只还原（氯化亚锡）和盐酸，只还原NO2。NH2CHOSnCl2浓盐酸NO2CHO硝基化合物的还原NO2NHOHZnNH4ClaqNO2ZnNaOHaqN=N2 2. .1 1. .NO2NaOHaqAs2O3NO2NaOHaqN=NAs2O3O O- -+ +NHNH3 3. .氧化偶氮苯偶氮苯氢化偶氮苯硝基化合物的还原NO2NO2NH2NO2NH4SHC2H5OH,H2OCH3NO2NO2CH3NH2NO2NH2NO2NO2NH2NH2NO2NH4SH

3、NH4SH硝基对芳环邻、对位基团的影响ClNO2NO2OHNO2NO2OH2NaCO3ClH+加热+2OHNO2NO2O2NNO2OHOHNO2苦味酸，强酸PKa=7.16PKa=7.17NO2OHPKa=8.28影响较弱17.2 胺按烃基分类脂肪胺芳香胺CH3NH2NH2苯胺按分子中氨基数目分一元胺二元胺三元胺CH3NH2H2NCH2CH2NH2按氮上所连碳原子数目（伯、仲、叔醇是按羟基所连碳的级数 ）伯胺仲胺叔胺RNH2R2NHR3NC H3N HC H3C H3NC H3C H3N H二 甲 胺三 甲 胺二 苯 胺C H3N HC H3C H3NC H3C H3N H二 甲 胺三 甲 胺

4、二 苯 胺胺的分类和构造NCH3C2H5NCH3CH3N 甲 基 N 乙 基 苯 胺N,N 二 甲 基 苯 胺NHCH3N 甲 基 苯 胺（ 不 是 “ 苯 甲 胺 ” 或“ 甲苯 胺 ” ）CH3CHCH2CHCH3CH3NH2H2NCOOH123452甲基4氨基戊烷对氨基苯甲酸胺的构造胺的构造胺的构造NCH3CH2CH2CHC6H5CH3CH2NCH3C6H5CH2CHCH2CH2CH3H2NCH2CH2CH2CH2NH21,4-丁二胺(腐胺)H2NCH2CH2CH2CH2CH2NH21,5-戊二胺(尸胺)H2NN H2胺的碱性RNH2OH2RNH3OHKbKbRNH3 OH RNH2pK

5、blgKb+-=+-=-RNH2HClRNH3ClNaOHRNH2NaClH2O胺的碱性CH3NH2RNH2RNH2 NH3RNHR碱性增强CH3CNH2OCH3CH2NH2H2NCNH2O(CH3CH2)2NH(CH3CH2)4NOHabcdee d b c a胺的碱性胺的烃基化反应C16H33NH2CH3ClC16H33NHCH3NaClOH2C16H33NHCH3CH3ClC16H33N(CH3)2NaClOH2NaOHNaOHC16H33N(CH3)2CH3ClC16H33N(NH3)3 Cl+-CH3CH2INH3CH3CH2NH3I伯胺盐CH3CH2NH3INH3CH3CH2NH2

6、NH4IC16H33NH2CH3ClC16H33NHCH3NaClOH2C16H33NHCH3CH3ClC16H33N(CH3)2NaClOH2NaOHNaOHC16H33N(CH3)2CH3ClC16H33N(NH3)3 Cl+-胺的酰基化反应CH3NH2CH3CO)2OCH3CNHCH3OCH3COOHCH3)2NHCH3COClCH3CN(CH3)2OClH(CH3)3NCH3COCl+不反应N,N-二甲基乙酰胺N-甲基乙酰胺(胺的酰基化反应CH3NH2CH3COClCH3NHCOCH3OCOOHNHCOCH3COOHNH2H2O胺的磺酰化反应(Hinsberg反应)SO2ClH3CSO

7、2ClRNH2R2NHR3NSO2ClNaOHNaOHNaOHRNHO2SNaOHRNO2S NaRNH2ClHNaOHR2NO2SClHNaOHR2NH-+(1)(2)(1)(2)不反应（溶解）（不溶） 胺的磺酰化反应(Hinsberg反应)CH3NH2OHCOOHNHCH3COOH稀HCl溶解CH3NH2NHCH3不溶解OHCOOHCOOHSO2ClNaOH先生成固体再溶解CH3NH2固体NHCH3FeCl3显色OHCOOH不显色COOHNHCH3NCH3CH3NH2SO2ClH3C固体SO2NH3CCH3H3O分出油相NHCH3液体NaOH, 过滤分层水层SO2NH3CNa油层NCH3C

8、H3OH-H3O分出油相OH-NH2胺与亚硝酸的反应RNH2HNO3ROHN2OH2+NH2NaNO2ClHN2ClOH2NaCl+20-5+2胺与亚硝酸的反应(CH3)2NHNaNO2ClH(CH3)2NNOOH2NaClNHCH3NaNO2ClHNCH3NOOH2NaCl+N亚硝基二甲胺N-亚硝基N-甲基苯胺R2NNO稀酸R2NH胺与亚硝酸的反应R3NHNO2R3NH NO2NHNO2(CH3)2NNO(CH3)2OH2+-+对亚硝基N,N二甲基苯胺绿色结晶胺的氧化反应NH2MnO2H2SO4OO 10对苯醌芳胺苯环上的取代反应NH2BrNH2BrBrBr2BrH+3+3芳胺苯环上的取代反

9、应NH2H2SO4(CH3CO)2ON H3SO4 HNH2NO2HNO3N H3SO4 HNO2NaOHNHCOCH3HNO3(CH3CO)2OHNO3CH3COOHNHCOCH3NO2NHCOCH3NO2OH2OH2NH2NO2NH2NO2+-+-主要产物主要产物芳胺苯环上的取代反应NH2H2SO4NH2 H2SO4NH2SO3HN H3SO3 .180-190+-内盐选择性还原剂：选择性还原剂：SnCl2（氯化亚锡）和盐酸，只还原（氯化亚锡）和盐酸，只还原NO2。RNH2R2NHR3NSO2ClNaOHNaOHNaOHRNHO2SNaOHRNO2S NaRNH2ClHNaOHR2NO2S

10、ClHNaOHR2NH-+(1)(2)(1)(2)不反应（溶解）（不溶）NH2NaNO2ClHN2ClOH2NaCl+20-5+217.3 季铵盐和季铵碱NRRRR XNRRRR OH+-+-季铵盐季铵碱(CH3)4NOHCH3NC2H5CH3CH3OH-氢氧化四甲铵或四甲基氢氧化铵氢氧化三甲基乙基铵或三甲基乙基氢氧化铵R4N+O H-H C lR4N+C l-H2OR4N+Cl-NaOHR4N+Cl-Na+OH-R4N+Cl-AgOHR4N+OH-AgCl（CH3)3N+HCl-(C2H5)4N+Br-NaOH析出油层不析出油层(C2H5)4N+Br-（CH3)3N+HCl-季铵盐的应用反应

11、反应(CH3)4NOH(CH3)3N+ CH3OHHO-CH3N(CH3)3SN2HOCH3+N(CH3)3季铵碱热消除反应 季铵碱热消除反应CH3CH2CHCH3BrC2H5ONaC2H5OHCH3CHCHCH3CH3CH2CHCH2CH3CH2CHCH3N(CH3)3 OHCH3CHCHCH3CH3CH2CHCH2(CH3)3N+81%19%+-+95%5%季铵碱热消除反应季铵碱热消除反应17.4 偶氮化合物与重氮化合物NNCH3CNCH3CNNCH3CNCH3CNNClNNHN+-偶氮苯偶氮二异丁腈氯化重氮苯苯重氮氨基苯芳香族重氮盐的制备-重氮化反应 NH2NaNO2ClHN2ClNaC

12、lOH2+2+20-5+-重氮盐的反应及在合成上的应用重氮盐的反应及在合成上的应用N2 HSO4BrOH2OHBrN2H2SO4+-加热NO2NO2NO2H2SO4,HNO3NH2NH4SHNaNO2,H2SO4N2 HSO4OHNO2NO2OH2加热乙醇溶液+-加热重氮盐的反应及在合成上的应用N2 HSO4IKIN2KHSO4+加热N2 ClClN2 BrBrN2N2CuCl,HClCuCuBr,HBrCu+或或-+-重氮盐的反应及在合成上的应用ClBrHNO3NO2NO2FeClHNH2NO2N2NO2CuClClNO2ClNH2ClN2CuBrClBr(NH4)2S+重 氮化+重 氮化+

13、重氮盐的反应及在合成上的应用N2 ClN2 HSO4CNCNCuCN,KCNCu,KCNN2N2+-+加热加热CH3CH3CNCH3HNO3H2SO4CH3NO2NaNO2HClCH3N2Cl-CuCN/KCNCH3CN重氮盐的反应及在合成上的应用CH3CH3COOHBrCH3HNO3CH3NO2FeClHCH3NH2BrBr2FeBr3H3OCH3COOHBrCH3N2BrCH3NO2BrCuCNCH3CNBr+重 氮化+重氮盐的反应及在合成上的应用N2 ClN2 HSO4H3PO2OH2CH3CH2OHN2H3PO3ClHCH3CHON2H2SO4+-+重氮盐的反应及在合成上的应用CH3C

14、H3BrCH3HNO3CH3NO2FeClHCH3NH2CH3COClCH3NHCOCH3BrFeBr3CH3NHCOCH3BrH3OCH3NH2CH3N2C2H5OHH3PO2CH3Br+重 氮化+CH3HNO3CH3NO2FeClHCH3NH2CH3COClCH3NHCOCH3BrFeBr3CH3NHCOCH3BrH3OCH3NH2CH3N2C2H5OHH3PO2CH3Br+重 氮化+CH3HNO3CH3NO2FeClHCH3NH2CH3COClCH3NHCOCH3BrFeBr3CH3NHCOCH3BrH3OCH3NH2CH3N2C2H5OHH3PO2CH3Br+重 氮化+BrBrBrHNO3H2SO4NO2SnCl2HClNH2Br2NH2BrBrBrNaNO2HClN2ClBrBrBrH3P