北大有机课件第十三章有机含氮化合物.ppt
2023/11/1,有机,Chapter 13 Organic Compounds Containing Nitrogen有机含氮化合物,硝基化合物,酰胺,腈,肟,胺,重氮和偶氮化合物,2023/11/1,有机,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 compounds,2023/11/1,有机,Amine(胺),NH3,胺(Amine),铵 铵盐(Ammonium Salt),氨(Ammonia),季胺盐(Quaternary Ammonium Salt),2023/11/1,有机,根据N上所连烃基的种类,脂肪胺,芳香胺,芳脂胺,CH3NH2,一.Classification&Naming:,2023/11/1,有机,根据N上所连烃基的数目,RNH2,R2NH,R3N,R4N+,1胺（伯胺）Primary Amines,2胺（仲胺）Secondary Amines,3胺（叔胺）Tertiary Amines,4胺（季铵盐)Quaternary Ammonium Salt,Classification&Naming,2023/11/1,有机,根据分子中胺基的数目,一元胺,多元胺,胺的分级与卤代烃、醇不同！,(CH3)3C-OH,3醇,(CH3)3C-NH2,1胺,Classification&Naming,3o卤代烃,2023/11/1,有机,(CH3)2NH,dimethyl amine,aniline 苯胺,N-methyl aniline,CH3-NH2,methyl amine 甲（基）胺,CH3CH2NH2,ethyl amine 乙胺,Classification&Naming,2023/11/1,有机,3-胺甲基-2-N,N-二甲胺基己烷,C6H5NH3+Cl-,氯化苯铵,Classification&Naming,3-(N-乙胺基)庚烷,2-氨基乙醇,-(N-甲胺基)丙酸,对氨基苯磺酸,氯化四甲铵,硫酸乙铵,2023/11/1,有机,二.Structure&Isomerism:,SP3,2023/11/1,有机,SP3,SP3,“SP2”,Structure&Isomerism,2023/11/1,有机,胺的对映体的转变,构型翻转，能垒较低，翻转速度较快,N上不同的取代,手性氮,对映异构体？,自动外消旋化，不可拆分,Structure&Isomerism,2023/11/1,有机,氮在环内，翻转受阻,季铵盐 不能进行氮的翻转,可分离出稳定的旋光异构体,胺的对映体的转变,Structure&Isomerism,Troger 碱,S-,R-,形成N氧化物，不能翻转,2023/11/1,有机,三.Preparation of Aamines,Preparation by Nucleolic Substitution,1、胺的烷基化,1 胺,2胺,3胺,4胺,反应产物复杂,如何控制产物在1 胺？,采用该法合成胺，哪一种卤代烷不适用？,芳香胺,2023/11/1,有机,Preparation of Aamines,3、Gabriel 合成法制备1胺,2、芳香卤代烃的胺解,2023/11/1,有机,Preparation of Aamines,Preparation by Reduction,1.硝基化合物,1 胺,2.腈,3.酰胺,4.肟,5.Alkyl Azide 叠氮物,2023/11/1,有机,Preparation of Aamines,6、羰基化合物的还原胺化(Reductive Amination),NH3,1 胺,1 胺,2 胺,2 胺,3 胺,1 胺的二甲基化,2023/11/1,有机,Preparation of Aamines,Preparation by Rearrangements,1、Hofmann Rearrangements（Hofmann 重排，降解）,异氰酸酯,机理,2023/11/1,有机,Preparation of Aamines,R-2-甲基丁酰胺,R-2-甲基丁胺,三元环过渡态,构型保持,SN2,Stereochemistry,2023/11/1,有机,Preparation of Aamines,2、Curtius&Schmidt Rearrangements,酰叠氮化合物,Curtius,Schmidt,2023/11/1,有机,Preparation by Mannich reaction,Preparation of Aamines,-胺基酮,-H 酮,甲醛,胺盐,酸性水、醇溶液,胺甲基化反应,2023/11/1,有机,机理,Preparation of Aamines,Mannich Base,
