华南师范大学：《有机化学》课程PPT教学课件（双语版）Chapter 19. Amines

Chapter 19 Amines(胺) 19.1 Nomenclature In common nomenclature most primary amines are named as alkylamines. In systematic nomenclature they are named by adding the suffix -amine to the name of the chain or ring system to which the nh2 group is attached with elision of the final e Primary amines; 伯胺 CHNH CH3CH2NH2 CH3 CH2 CH2NH, Common name; Methylamine Ethylamine Propylamine IUPAC name; (methanamine)(ethanamine)(Propanamine) 甲胺 乙胺 丙胺

Chapter 19. Amines (胺） 19.1 Nomenclature In common nomenclature most primary amines are named as alkylamines. In systematic nomenclature they are named by adding the suffix –amine to the name of the chain or ring system to which the NH2 group is attached with elision of the final e Primary Amines; 伯 胺 CH3 NH2 CH3 CH2 NH2 CH3 CH2 CH2 NH2 Methylamine (methanamine) Ethylamine (ethanamine) Propylamine (Propanamine) Common name; IUPAC name; 甲 胺 乙 胺 丙 胺

Primary amines(伯胺) CH3CHCH2NH2 CH2CHCHbChNH Common name; Butylamine Isobutylamine Cyclohexylamine IUPAC name;(Butanamine)(2-methyl-1-propanamine)(cyclohexanamine 丁胺 异丁胺 环己基胺 Secondary amines: 仲胺 CH3NHCH2CH3 (CH3 CH2)2NH NHCH Common name; Ethylmethylamine Diethylamine IUPAC name; (N-methylethanamine)(N-ethylethanamine) Cyclohexylmethylamine 甲乙胺 (N-methylcyclohexanamine 二乙胺 N-甲基环己基胺

Primary Amines (伯胺）; NH2 Butylamine (Butanamine) Cyclohexylamine (cyclohexanamine) CH3CH2CH2CH2NH2 Common name; IUPAC name; CH3CHCH2NH2 CH3 Isobutylamine (2-methyl-1-propanamine) 丁 胺 异 丁 胺 环 己 基 胺 NHCH3 Ethylmethylamine (N-methylethanamine) Cyclohexylmethylamine (N-methylcyclohexanamine) CH3NHCH2CH3 Common name; IUPAC name; (CH3CH2 ) 2NH Diethylamine (N-ethylethanamine) 甲 乙 胺 二 乙 胺 N-甲 基 环 己 基 胺 Secondary Amines; 仲 胺

Tertiary amines(叔胺) CH2CH CH3)3N (CH3CH23N CH3NCH2 CH2CH3 Trimethylamine Triethylamine Ethylmethylpropylamine N, N-Dimethylmethanamine)(N, N-diethylethanamine)(N-ethyl-N-methyl-l-propanamine 三甲胺 三乙胺 N-甲基-N-乙基丙胺 In the IUPaC system, the substituent-NH, is called the amino group. H2NCH2CHOH H2NCH2 CH2COOH 2-Aminoethanol 3-Aminopropanoic acid 2-氨基乙醇 3-氨基丙酸

Tertiary Amines (叔胺） Trimethylamine (N,N-Dimethylmethanamine) Ethylmethylpropylamine (N-ethyl-N-methyl-1-propanamine) (CH3CH2 ) 3N Triethylamine (N,N-diethylethanamine) 三 甲 胺 三 乙 胺 N-甲 基 -N-乙 基 丙 胺 (CH3 ) 3N CH3NCH2CH2CH3 CH2CH3 In the IUPAC system, the substituent-NH2 is called the amino group. H2 NCH2 CH2 OH H2 NCH2 CH2 COOH 2-Aminoethanol 3-Aminopropanoic acid 2-氨 基 乙 醇 3-氨 基 丙 酸

19.1 A Arylamines(芳胺) NHCHa N(CH3)2 CH Aniline N-Methylaniline N, N-Dimethylaniline P-Toluidine Benzeneamine)(N-methylbenzenamine)(N, N-Dimethylbenzenamine)(4-methylbenzenamine) (苯胺 (N甲基苯胺) (N,N-二甲基苯胺) (4-甲基苯胺) lich arylamines are primary amines, secondary amines tertiary amines?

19.1A Arylamines （芳胺） NH2 NHCH3 NH2 CH3 N(CH3)2 Aniline N-Methylaniline (N-methylbenzenamine) P-Toluidine (4-methylbenzenamine) N,N-Dimethylaniline (N,N-Dimethylbenzenamine) (苯 胺 ） (N-甲 基 苯 胺 ） (N,N-二 甲 基 苯 胺 ） (Benzeneamine) (4-甲 基 苯 胺 ） Which arylamines are primary amines, secondary amines, tertiary amines?

19.1B Heterocyclic amines (杂环胺) The important heterocyclic amines all have common mames N pyrrole razole Imidazole Indole (吡咯) (吡唑) (咪唑) (吲哚)

19.1B Heterocyclic amines （杂环胺） The important heterocyclic amines all have common names. Pyrrole (吡 咯 ） (吡 唑 ） (咪 唑 ） (吲 哚 ） N H N H N Pyrazole N N H Imidazole N H Indole

3 n 3 2 2 Pyridine Pyridazine Py imidine (吡啶) (哒嗪) (咪啶) Quinoline Isoquinoline (喹啉) (异喹啉) N1 28 2 N 3 Piperidine Pyrrolidine Thiazole PU 哌啶)四氢吡咯)(噻唑) 嘌啉)

Pyridine (吡 啶 ） (哒 嗪 ） (咪 啶 ） Pyridazine Pyrimidine N N N 1 2 3 4 1 2 3 4 N N 1 2 3 4 Piperidine (哌 啶 ） (四 氢 吡 咯 ） (嘌 啉 ） Pyrrolidine Purine N H 1 2 3 4 N N 1 2 3 N 4 H S N N N H 5 7 6 8 9 1 2 3 Thiazole （ 噻 唑 ） (喹 啉 ） Quinoline N N Isoquinoline (异喹 啉 ）

19.2 Physical properties and structure of amines 19.2A Physical properties Amines are moderately polar substances; they have boiling points that are higher than those of alkanes but generally lower than those of alcohols of comparable molecular weight. Primary amines Structure bp (c) Ethylamine CH3 CHNH2 Hydrogen-Bonding Secondary amines: Dimethylamine (CH3)2NH 7°C Hydrogen-Bonding Diethylamine (CH3 CH2)2NH 56C Hydrogen-Bonding Tertiary Amines; No hydrogen-bonding Trimethylamine (CH3)N 29C Boiling point is low

19.2 Physical properties and structure of amines 19.2A Physical properties Amines are moderately polar substances; they have boiling points that are higher than those of alkanes but generally lower than those of alcohols of comparable molecular weight. Primary Amines; E CH3CH2NH2 thylamine Structure bp ( oC) 17 oC Secondary Amines; Dimethylamine (CH3 ) 2NH 7 oC Diethylamine (CH3CH2 ) 2NH 56 oC Tertiary Amines; Trimethylamine (CH3 ) 3N 2.9 oC Hydrogen-Bonding Hydrogen-Bonding Hydrogen-Bonding No hydrogen-bonding Boiling point is low

19.2B Structure of amines The nitrogen atom of most amines is like that of ammonia; it is approximately sp3 hybridized. The three alkyl groups(or hydrogen atoms) occupy corners of a tetrahedron; the sp3 orbital containing the unshared electron pair is directed toward the other corner we describe the geometry of the amine by the location of the atoms as being trigonal pyramidal SP hybridized R 1)由于氮上有孤对电子,胺显碱性。 R R 2)胺类可作为亲核试剂 Structure of an amine

19.2B Structure of amines The Nitrogen atom of most amines is like that of ammonia; it is approximately sp3 hybridized. The three alkyl groups (or hydrogen atoms) occupy corners of a tetrahedron; the sp3 orbital containing the unshared electron pair is directed toward the other corner. We describe the geometry of the amine by the location of the atoms as being trigonal pyramidal. N R' R'' R''' SP 3 hybridized Structure of an amine 1） 由 于 氮 上 有 孤 对 电 子 ， 胺 显 碱 性 。 2） 胺 类 可 作 为 亲 核 试 剂

If the alkyl groups of a tertiary amine are all different the amine will be chiral there will be two enantiomeric forms of the tertiary amine In practice, however, resolution is usually impossible because the enantiomers interconvert rapidly. R 6 kcal mol R N IIR N R R Intercomversion of amine enantiomers 叔胺对映体相互转换,难以拆分

If the alkyl groups of a tertiary amine are all different the amine will be chiral. There will be two enantiomeric forms of the tertiary amine. In practice, however, resolution is usually impossible because the enantiomers interconvert rapidly. N R' R'' R''' N R'' R' R''' Intercomversion of amine enantiomers 叔 胺 对 映 体 相 互 转 换 ， 难 以 拆 分 。 6 kcal mol -1

Ammonium salts cannot undergo inversion because they do not have an unshared pair Therefore, those quaternary ammonium salts(季胺盐) with four different groups are chiral and can be resolved into separate (relatively stable)enantiomers R R"IlIlI IIR N——R R R Quaternary ammonium salts such as these can be resolved 季胺盐对映体不能相互转换,可以拆分成单个对映体

Ammonium salts cannot undergo inversion because they do not have an unshared pair. Therefore, those quaternary ammonium salts (季胺盐）with four different groups are chiral and can be resolved into separate (relatively stable) enantiomers. N R' R'' R''' N R'' R' R''' Quaternary ammonium salts such as these can be resolved 季 胺 盐 对 映 体 不 能 相 互 转 换 ， 可 以 拆 分 成 单 个 对 映 体 。 R'''' R'''' + X - + X -