1、材料科學(xué)及工程有機(jī)化學(xué)有材料科學(xué)及工程有機(jī)化學(xué)有機(jī)含氮化合物機(jī)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被烴基取代）（酸中OH被烴基取代）亞硝酸亞硝酸酯亞硝基化合物注意寫法，硝基化合物是CN相連硝酸酯是CO相連C H3N O2N O2C H3硝 基 甲 烷對(duì) 硝 基 甲 苯H2CH2CONO2ONO2H2CONO2三硝基甘油酯（可作抗血栓藥，救心丸）（可作抗血栓藥，救心丸）NO2CH3NO2NO2TNT硝基化合物的構(gòu)造RNO2RONO硝基化合物亞硝酸酯硝基化合物的還原RNO2HH,PtFeClHRNH2OH2ArNO2HH

2、,PtFeClHArNH2OH2+6+或+2+6+或+222NO2NONHOHNH2選擇性還原劑：選擇性還原劑：SnCl2（氯化亞錫）和鹽酸，只還原（氯化亞錫）和鹽酸，只還原NO2。NH2CHOSnCl2濃鹽酸NO2CHO硝基化合物的還原NO2NHOHZnNH4ClaqNO2ZnNaOHaqN=N2 2. .1 1. .NO2NaOHaqAs2O3NO2NaOHaqN=NAs2O3O O- -+ +NHNH3 3. .氧化偶氮苯偶氮苯氫化偶氮苯硝基化合物的還原NO2NO2NH2NO2NH4SHC2H5OH,H2OCH3NO2NO2CH3NH2NO2NH2NO2NO2NH2NH2NO2NH4SH

3、NH4SH硝基對(duì)芳環(huán)鄰、對(duì)位基團(tuán)的影響ClNO2NO2OHNO2NO2OH2NaCO3ClH+加熱+2OHNO2NO2O2NNO2OHOHNO2苦味酸，強(qiáng)酸PKa=7.16PKa=7.17NO2OHPKa=8.28影響較弱17.2 胺按烴基分類脂肪胺芳香胺CH3NH2NH2苯胺按分子中氨基數(shù)目分一元胺二元胺三元胺CH3NH2H2NCH2CH2NH2按氮上所連碳原子數(shù)目（伯、仲、叔醇是按羥基所連碳的級(jí)數(shù) ）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 胺胺的分類和構(gòu)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氨基戊烷對(duì)氨基苯甲酸胺的構(gòu)造胺的構(gòu)造胺的構(gòu)造NCH3CH2CH2CHC6H5CH3CH2NCH3C6H5CH2CHCH2CH2CH3H2NCH2CH2CH2CH2NH21,4-丁二胺(腐胺)H2NCH2CH2CH2CH2CH2NH21,5-戊二胺(尸胺)H2NN H2胺的堿性RNH2OH2RNH3OHKbKbRNH3 OH RNH2pK

5、blgKb+-=+-=-RNH2HClRNH3ClNaOHRNH2NaClH2O胺的堿性CH3NH2RNH2RNH2 NH3RNHR堿性增強(qiáng)CH3CNH2OCH3CH2NH2H2NCNH2O(CH3CH2)2NH(CH3CH2)4NOHabcdee d b c a胺的堿性胺的烴基化反應(yīng)C16H33NH2CH3ClC16H33NHCH3NaClOH2C16H33NHCH3CH3ClC16H33N(CH3)2NaClOH2NaOHNaOHC16H33N(CH3)2CH3ClC16H33N(NH3)3 Cl+-CH3CH2INH3CH3CH2NH3I伯胺鹽CH3CH2NH3INH3CH3CH2NH2

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

7、2ClRNH2R2NHR3NSO2ClNaOHNaOHNaOHRNHO2SNaOHRNO2S NaRNH2ClHNaOHR2NO2SClHNaOHR2NH-+(1)(2)(1)(2)不反應(yīng)（溶解）（不溶） 胺的磺酰化反應(yīng)(Hinsberg反應(yīng))CH3NH2OHCOOHNHCH3COOH稀HCl溶解CH3NH2NHCH3不溶解OHCOOHCOOHSO2ClNaOH先生成固體再溶解CH3NH2固體NHCH3FeCl3顯色OHCOOH不顯色COOHNHCH3NCH3CH3NH2SO2ClH3C固體SO2NH3CCH3H3O分出油相NHCH3液體NaOH, 過濾分層水層SO2NH3CNa油層NCH3C

8、H3OH-H3O分出油相OH-NH2胺與亞硝酸的反應(yīng)RNH2HNO3ROHN2OH2+NH2NaNO2ClHN2ClOH2NaCl+20-5+2胺與亞硝酸的反應(yīng)(CH3)2NHNaNO2ClH(CH3)2NNOOH2NaClNHCH3NaNO2ClHNCH3NOOH2NaCl+N亞硝基二甲胺N-亞硝基N-甲基苯胺R2NNO稀酸R2NH胺與亞硝酸的反應(yīng)R3NHNO2R3NH NO2NHNO2(CH3)2NNO(CH3)2OH2+-+對(duì)亞硝基N,N二甲基苯胺綠色結(jié)晶胺的氧化反應(yīng)NH2MnO2H2SO4OO 10對(duì)苯醌芳胺苯環(huán)上的取代反應(yīng)NH2BrNH2BrBrBr2BrH+3+3芳胺苯環(huán)上的取代反

9、應(yīng)NH2H2SO4(CH3CO)2ON H3SO4 HNH2NO2HNO3N H3SO4 HNO2NaOHNHCOCH3HNO3(CH3CO)2OHNO3CH3COOHNHCOCH3NO2NHCOCH3NO2OH2OH2NH2NO2NH2NO2+-+-主要產(chǎn)物主要產(chǎn)物芳胺苯環(huán)上的取代反應(yīng)NH2H2SO4NH2 H2SO4NH2SO3HN H3SO3 .180-190+-內(nèi)鹽選擇性還原劑：選擇性還原劑：SnCl2（氯化亞錫）和鹽酸，只還原（氯化亞錫）和鹽酸，只還原NO2。RNH2R2NHR3NSO2ClNaOHNaOHNaOHRNHO2SNaOHRNO2S NaRNH2ClHNaOHR2NO2S

10、ClHNaOHR2NH-+(1)(2)(1)(2)不反應(yīng)（溶解）（不溶）NH2NaNO2ClHN2ClOH2NaCl+20-5+217.3 季銨鹽和季銨堿NRRRR XNRRRR OH+-+-季銨鹽季銨堿(CH3)4NOHCH3NC2H5CH3CH3OH-氫氧化四甲銨或四甲基氫氧化銨氫氧化三甲基乙基銨或三甲基乙基氫氧化銨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析出油層不析出油層(C2H5)4N+Br-（CH3)3N+HCl-季銨鹽的應(yīng)用反應(yīng)

11、反應(yīng)(CH3)4NOH(CH3)3N+ CH3OHHO-CH3N(CH3)3SN2HOCH3+N(CH3)3季銨堿熱消除反應(yīng) 季銨堿熱消除反應(yīng)CH3CH2CHCH3BrC2H5ONaC2H5OHCH3CHCHCH3CH3CH2CHCH2CH3CH2CHCH3N(CH3)3 OHCH3CHCHCH3CH3CH2CHCH2(CH3)3N+81%19%+-+95%5%季銨堿熱消除反應(yīng)季銨堿熱消除反應(yīng)17.4 偶氮化合物與重氮化合物NNCH3CNCH3CNNCH3CNCH3CNNClNNHN+-偶氮苯偶氮二異丁腈氯化重氮苯苯重氮氨基苯芳香族重氮鹽的制備-重氮化反應(yīng) NH2NaNO2ClHN2ClNaC

12、lOH2+2+20-5+-重氮鹽的反應(yīng)及在合成上的應(yīng)用重氮鹽的反應(yīng)及在合成上的應(yīng)用N2 HSO4BrOH2OHBrN2H2SO4+-加熱NO2NO2NO2H2SO4,HNO3NH2NH4SHNaNO2,H2SO4N2 HSO4OHNO2NO2OH2加熱乙醇溶液+-加熱重氮鹽的反應(yīng)及在合成上的應(yīng)用N2 HSO4IKIN2KHSO4+加熱N2 ClClN2 BrBrN2N2CuCl,HClCuCuBr,HBrCu+或或-+-重氮鹽的反應(yīng)及在合成上的應(yīng)用ClBrHNO3NO2NO2FeClHNH2NO2N2NO2CuClClNO2ClNH2ClN2CuBrClBr(NH4)2S+重 氮化+重 氮化+

13、重氮鹽的反應(yīng)及在合成上的應(yīng)用N2 ClN2 HSO4CNCNCuCN,KCNCu,KCNN2N2+-+加熱加熱CH3CH3CNCH3HNO3H2SO4CH3NO2NaNO2HClCH3N2Cl-CuCN/KCNCH3CN重氮鹽的反應(yīng)及在合成上的應(yīng)用CH3CH3COOHBrCH3HNO3CH3NO2FeClHCH3NH2BrBr2FeBr3H3OCH3COOHBrCH3N2BrCH3NO2BrCuCNCH3CNBr+重 氮化+重氮鹽的反應(yīng)及在合成上的應(yīng)用N2 ClN2 HSO4H3PO2OH2CH3CH2OHN2H3PO3ClHCH3CHON2H2SO4+-+重氮鹽的反應(yīng)及在合成上的應(yīng)用CH3C

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