1第十四章1.CH2CH2NHC2H5ON(CH3)2(1)(2)CH2NHCH2(3)(4)H2NCH2CCH2NH2CH3CH3(5)(6)C6H5HHNH2HC6H5H2NH或CH3CH3CH3+NCH2PhCl-(7)N-甲基-2-丙胺(8)(R)-反-3-戊烯-2-胺(9)N,N-二甲基苯胺(10)1,5-己二胺(11)3-甲氧基苯胺(12)(S)-3-甲基-2-氨基-1-丁醇2.OCH3(1)(2)(3)NHNCH2CH3OCH3HN(4)(5)CH3COCH2N(CH2C6H5)2H3CCH3CH2+N(CH3)3(6)NNO(7)CH3NH2CH3CH3HNCH3CH3HNCH3ClONEtOEtBrNH2(8)BrOH(9)CNNO2FF(10)OHN=N(11)(12)CH3H3CH3CPhNO2OCH3CH2CN(13)OCH3H3COOCH3CH2CH2NH2OCH3H3CO(14)CCPhPhHHBrBr(15)CH3(CH2)5NHCH2CCHO(16)OOCH3CH3N(CH3)23.(1)H3C-H2N-HO-F-(2)N-N-N-OOO(3)3,4-二氯苯胺3-硝基-4-氯苯胺2-硝基-4-氯苯胺(4)二甲胺N–甲基苯胺二苯胺:N(5):NCH2CH3CH2CH3CH2CH34.(碱性或亲核性:脂肪胺苯胺酰胺)NN+H3CH3CH3COCNHCH3OI-5.(1)化合物(A)能形成分子间氢键,而(B)不能形成分子间氢键。N+N+C(CH3)3HCH2PhH3CC(CH3)3HCH3PhH2CCl-Cl-+(2)(3)脂肪族重氮盐极不稳定,即使在低温下也能很快分解,放出氮气,生成相应的谈正离子。CH3CH2CH2NH2CH3CH2CH2N2+Cl-CH3CH2CH2+NaNO2/HCl-N2CH3C+HCH3CH3CHCH3重排H2O-H+OH6.反应按照消除-加成机理,有苯炔中间体生成。随后氨基负离子进攻苯炔中间体得苯负3离子中间体A和B。该碳负离子为sp2杂化,负电荷所在的轨道与苯环共平面,故甲氧基在此不能产生给电子共轭效应而只表现其吸电子诱导效应。所以中间体A较B稳定,更容易生成。OCH3BrHOCH3NH2OCH3NH2OCH3ABNH2--HBrNH2-+7.(CH3)3CCH2Br(CH3)3CCH2COOH(1)Mg/Et2O(2)CO2(3)H3O+(1)SOCl2(2)NH3(1)(1)LiAlH4(2)H2O(CH3)3CCH2CONH2(CH3)3CCH2CH2NH2另一条路线为:RBr→RCN→RCH2NH2,但由于该卤代烷的空间位阻太大,使其很难与氰基负离子发生亲核取代反应。(2)首先将羟基转化为离去基团对甲苯磺酸酯,此步碳原子构型保持。然后用叠氮负离子进行亲核进攻,此步碳原子构型翻转。OPhHHOHOPhHHOOPhHN3HOPhHNH2HTsNaN3LiAlH4TsCl/吡啶CH3CH3NH2CNCH3(3)(1)HNO3/H2SO4(2)H2/Ni(1)NaNO2/HCl(2)CuCN/加热CNCH2N(CH3)2CH2BrCNNBSNH(CH3)2(4)对氨基苯酚的氨基亲核性较酚羟基强,优先发生乙酰化反应。4H3CCH3CH3CH3NO2NH2CH3CH3(6)HNO3/H2SO4(1)Fe/HCl(2)NaOHBr2NH2CH3BrCH3CH3BrFCH3(1)NaNO2/HCl(2)HBF4(3)加热8.ON(CH3)2N(CH3)2OOH+HCHO+(CH3)2NHH+NaBH4OOCOClO2NNO2Sn/HCltutocainehydrochloride9.NC6H5COOC2H5CH3HCl10.(1)HNO3/H2SO4(2)H2/NiNO2CNClNO2ClCl/FeCl3(1)Fe/HCl(2)NaNO2/H2SO4(3)CUCN5OClOClOClBrHNCH3CH2MgBrBr2(CH3)3CNH211.NHCOCH3NHCOCH3NO2NHCOCH3NO2ClHNO3H2SO4Cl2FeCl3NH2NO2ClOHCOOHHNO2NClOHCOOHClOHOClCl2FeCl3OH-PCl5二甲苯12.ClNO2OCH3NO2OCH3NH2OCH3OHKOHCH3OHFe/HCl(1)NaNO2/H+(2)CuSO4OCH3OCH3OCH3OCH3CH2ClOCH3OCH3CH2CN(CH3)2SO4NaOH(HCHO)nHCl/POCl3NaCNTEBA/NaOHOCH3OCH3CH2CH2NH2H2/RaneyNi