1、11/27/2022有机Chapter 13 Organic Compounds Containing Nitrogen有机含氮化合物有机含氮化合物RNO2NO2RCNORRCCOONRRCNRCRNOHRNH2RNHRRNRRRNRRRXRNRRROHArN2XCH2N2NNArAr硝基化合物硝基化合物酰胺酰胺 腈腈肟肟胺胺重氮和偶氮化合物重氮和偶氮化合物 11/27/2022有机含氮有机物含氮有机物 硝基化合物 Nitro Compunds酰胺 Amides腈 Nitriles肟 Oximes胺 Amines 重氮和偶氮化合物 Diazonium Salts&Azo compounds11
2、/27/2022有机Amine(胺胺)NH3 胺(Amine)铵 铵盐(Ammonium Salt)氨(Ammonia)RNH2RNHRRNRRRNRRRXRNRRROH 季胺盐(Quaternary Ammonium Salt)11/27/2022有机根据根据N上所连上所连烃基烃基的的种类种类脂肪胺脂肪胺芳香胺芳香胺芳脂胺芳脂胺CH3NH2NH2CH2NH2一一.Classification&Naming:11/27/2022有机根据根据N上所连上所连烃基烃基的的数目数目RNH2R2NHR3NR4N+1胺（伯胺）Primary Amines2胺（仲胺）Secondary Amines3胺（叔
3、胺）Tertiary Amines 4胺（季铵盐)Quaternary Ammonium SaltClassification&Naming11/27/2022有机根据分子中根据分子中胺基胺基的数目的数目一元胺一元胺多元胺多元胺胺的分级与卤代烃、醇不同胺的分级与卤代烃、醇不同 ！(CH3)3C-OH3醇醇(CH3)3C-NH21胺胺Classification&Naming(CH3)3CX3o卤代烃卤代烃11/27/2022有机(CH3)2NHdimethyl amineNH2aniline 苯胺NHCH3N-methyl anilineCH3-NH2methyl amine 甲（基）胺CH3
4、CH2NH2ethyl amine 乙胺Classification&Naming11/27/2022有机CH3CH2CH2CHCHCH3CH2NH2N(CH3)23-胺甲基胺甲基-2-N,N-二甲胺基己烷二甲胺基己烷C6H5NH3+Cl-氯化苯铵氯化苯铵CH3CH2NHCHCH2CH3CH2CH2CH2CH2CH3Classification&NamingHOCH2CH2NH2CH3CHNCH3CO2HHSO2HH2N(CH3CH2NH3)2SO4-(CH3)4N+Cl-3-(N-乙胺基乙胺基)庚烷庚烷2-氨基乙醇氨基乙醇-(N-甲胺基甲胺基)丙酸丙酸对氨基苯磺酸对氨基苯磺酸氯化四甲铵氯化四
5、甲铵硫酸乙铵硫酸乙铵11/27/2022有机二二.Structure&Isomerism:SP311/27/2022有机NH3CHHNH3CCH3CH3NHHSP3SP3“SP2 ”Structure&Isomerism11/27/2022有机胺的对映体的转变胺的对映体的转变构型翻转，能垒较低，翻转速度较快构型翻转，能垒较低，翻转速度较快N上不同的取代上不同的取代手性氮手性氮对映异构体对映异构体？自动外消旋化，不可拆分自动外消旋化，不可拆分Structure&Isomerism11/27/2022有机 氮在环内，翻转受阻氮在环内，翻转受阻 季铵盐季铵盐 不能进行氮的翻转不能进行氮的翻转 可分离
6、出稳定的旋光异构体可分离出稳定的旋光异构体胺的对映体的转变胺的对映体的转变Structure&IsomerismH3CNNTroger 碱S-R-形成形成N氧化物，氧化物，不能翻转不能翻转 PhNC2H5CH3ONH5C2CH2CHPhCH3CH2NC2H5CHCH2PhCH3H2C11/27/2022有机三三.Preparation of AaminesPreparation by Nucleolic Substitution1、胺的烷基化、胺的烷基化RX+NH3RNH2RX-HXR2NHRX-HXR3NRX-HXR4N+X-1 胺胺2胺胺3胺胺4胺胺反应产物复杂反应产物复杂如何控制产物在如
7、何控制产物在1 胺？胺？采用该法合成胺，哪一种卤代烷不适用？采用该法合成胺，哪一种卤代烷不适用？NH2+CH2ClNaHCO3(aq.)8587%NHCH29095 oC+NH2CH3CH2Cl(过量)NCH2CH3CH2CH3芳香胺芳香胺11/27/2022有机 Preparation of Aamines3、Gabriel 合成法制备合成法制备1胺胺EthanolNHOOKOHNOOKNOORRX2KOHH2NNH2NOOR+COOKCOOKRNH2OONHNH+RNH22、芳香卤代烃的胺解、芳香卤代烃的胺解+ClNO2O2NNH3NH2NO2O2NClNO2+CH3NH2NO2NHCH3
8、EtOH160 oC11/27/2022有机 Preparation of AaminesPreparation by ReductionNO21.Zn/HCl 2.OH-or H2/PtNH2NO2NO2NH4SHNO2NH21.硝基化合物硝基化合物CH3CH2BrNaN3EthanolCH3CH2NNN(1)LiAlH4(2)H2OCH3CH2NH21 胺胺2.腈腈RCNLiAlH4RCH2NH23.酰胺酰胺RCNR2OLiAlH4RCH2NR24.肟肟OH2NOHNOHNaC2H5OHNH25.Alkyl Azide 叠氮物叠氮物11/27/2022有机 Preparation of A
9、amines6、羰基化合物的还原胺化、羰基化合物的还原胺化(Reductive Amination)RCH(R)O+RRNH2H2/NiRCHH(R)NRRRCH(R)NRR+H2/NiCH3CH=ONH3CH3CH2NH2NH31 胺胺+H2/NiCH3CH2CHOCH3CH2NH2CH3CH2CH2NHCH2CH31 胺胺2 胺胺2 胺胺3 胺胺+RNH22H2CO+2HCOOHRN(CH3)21 胺的二甲基化胺的二甲基化11/27/2022有机 Preparation of AaminesPreparation by Rearrangements1、Hofmann Rearrangeme
10、nts （Hofmann 重排，降解）重排，降解）CH3(CH2)4CNH2OBr2OH-CH3(CH2)3CH2NH2RCNHHOBr2OH-RCNHBrOOH-RCNBrOOCNROH-RNH2异氰酸酯异氰酸酯机理机理11/27/2022有机 Preparation of AaminesCCONH2H5C2H3CHBr2/OH-CNH2H5C2H3CHR-2-甲基丁酰胺甲基丁酰胺R-2-甲基丁胺甲基丁胺CCH5C2H3CHONBrCNOBrCH5C2CH3H-+CNH5C2H3CHCO三元环过渡态三元环过渡态构型保持构型保持SN2Stereochemistry11/27/2022有机 Pr
11、eparation of Aamines2、Curtius&Schmidt RearrangementsRCOCl+NaN3RCOOH+NaN3RCNNNO-N2NCORH2ORNH2酰叠氮化合物酰叠氮化合物CurtiusSchmidtH2OCClONaN3CN3ONH260%H3O+NaN3ClCO2HClNH275%11/27/2022有机Preparation by Mannich reaction Preparation of AaminesCH3CCH3O+CH2O+(C2H5)2NH2+Cl-CH3CCH2CH2N+H(C2H5)2Cl-O6675%+CH2O+(CH3)2NH2+Cl-CCH3OCCH2CH2N+H(CH3)2Cl-O70%-胺基酮胺基酮-H 酮酮甲醛甲醛胺盐胺盐酸性水、醇溶液酸性水、醇溶液胺甲基化反应胺甲基化反应11/27/2022有机H2CO+HN(CH3)2HOCH2N(CH3)2H+CH2N+(CH3)2RCCH2OHCH2N+(CH3)2-H+RCCH2CH2N(CH3)2O机理机理 Preparation of AaminesMannich BaseCH3CCH3O+CHOCHONOCH3CH3NH2Tropinone
