有机含氮化合物(8)

单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,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,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,Amine(,胺),NH,3,胺,(,Amine),铵 铵盐,(,Ammonium Salt),氨,(,Ammonia),季胺盐,(,Quaternary Ammonium Salt),根据,N,上所连,烃基,的,种类,脂肪胺,芳香胺,芳脂胺,CH,3,NH,2,一.,Classification&Naming:,根据,N,上所连,烃基,的,数目,R,NH,2,R,2,NH,R,3,N,R,4,N,+,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,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 ！,(CH,3,),3,C-OH,3,醇,(CH,3,),3,C-NH,2,1,胺,Classification&Naming,3,o,卤代烃,(CH,3,),2,NH,di,methyl,amine,aniline,苯胺,N-methyl aniline,CH,3,-NH,2,methyl,amine,甲（基）胺,CH,3,CH,2,NH,2,ethyl,amine,乙胺,Classification&Naming,3-胺甲基-2-,N,N-,二甲胺基己烷,C,6,H,5,NH,3,+,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,二.,Structure&Isomerism:,SP,3,SP,3,SP,3,“SP,2,”,Structure&Isomerism,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,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,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,Preparation of,Aamines,3、,Gabriel,合成法制备1,胺,2、芳香卤代烃的胺解,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,Preparation of,Aamines,6、羰基化合物的还原胺化(,Reductive,Amination,),NH,3,1,胺,1,胺,2,胺,2,胺,3,胺,1,胺的二甲基化,Preparation of,Aamines,Preparation by Rearrangements,1、,Hofmann,Rearrangements （,Hofmann,重排，降解）,异,氰酸酯,机理,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,S,N,2,Stereochemistry,Preparation of,Aamines,2、,Curtius,&Schmidt Rearrangements,酰叠氮化合物,Curtius,Schmidt,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,机理,Preparation of,Aamines,Mannich,Base,