页数：77页文件大小：1.16 MB来源： 有机化学（甲）ppt课件
本课件讲解胺及含氮化合物，梳理胺的分类命名与碱性强弱，介绍酰化烷基化反应，并说明重氮盐的生成及其在偶联反应中的应用。并通过碱性比较与重氮盐应用的例题巩固本章重点内容。
第12章胺及含氮化合物Chapter 12Amines & Other Nitrogen Compounds
Natural Nitrogen Compounds
12.1 Nomenclature and Structure of AminesCommon Names：乙胺二乙胺苯胺甲（基）乙（基）丙胺ethanamine diethylamine anilineNethylmethylpropanamine
胺类化合物形成铵盐或季铵盐后：本页以图示与数据为主，提取文字如下。
胺类化合物形成铵盐或季铵盐后，命名如下例：甲胺盐酸盐苯胺硫酸盐溴化四乙铵Methylammonium Aniline sulfate Tetraethylammoniumchloride bromideN-甲基-N-乙基
环戊烷基铵盐酸盐溴化三乙基苄基铵N-Ethyl-N-methylcyclopentylammonium Benzyltriethylammoniumchloride bromide
本页源数据为无分隔提取文本，表格结构建议对照原课件图片核对。
(+)-Trögerbase(-)-Trögerbase
（S) (R)
12.2 Boiling：本页以图示与数据为主，提取文字如下。
12.2 Boiling Point and Water SolubilityCH3CH2NH2CH3CH2OHCH3CH2CH3CH3NH2CH3OHCH3CH3Compound454644313230Mol.Wt.1
6.6º78.5º-42º-6.0º65º-88.6ºBoilingPoint ºC(CH3)3N(CH3)2CHNH2(CH3)2CHOH(CH3)3CHCH3CH2NHCH3CH3(CH2)2NH2CH3(CH2)2
OHCH3(CH2)2CH3Compound5959605859596058Mol.Wt.3º34º82º-12º37º48º97º-0.5ºBoilingPoint ºC
本页源数据为无分隔提取文本，表格结构建议对照原课件图片核对。
12.3Basicity of Amines：
气相中测定的碱性强弱次序为：(C2H5)3N＞(C2H5)2NH＞C2H5NH2＞NH3，水溶液中测定的碱性强弱次序为：(C2H5)2NH＞(C2H5)3N＞C2H5NH2＞NH3，
胺：本页以图示与数据为主，提取文字如下。
胺pKa（25oC, H2O）胺pKa（25oC, H2O）NH3CH3NH2(CH3)2NH(CH3)3NCH3CH2NH2(CH3CH2)2NH(CH3CH2)3N9.2410.6210.739.7910.6410.
9410.75C6H5CH2NH2C6H5NH2(C6H5)2NHC6H5NHCH3o-NO2-C6H4NH2m-NO2-C6H4NH2p-NO2-C6H4NH29.344.601.204.40-0.262.471.00
本页源数据为无分隔提取文本，表格结构建议对照原课件图片核对。
Strong bases have weak conjugate acids, and weak bases have strong conjugate acids.
4.58 2.47 1.00
pKa = 13.6Here：本页以图示与数据为主，提取文字如下。
pKa = 13.6Here, resonance stabilzation of the base is small, due to charge separation,while the conjugate acid
is stabilized strongly by charge delocalization.Consequently, aqueous solutions of guanidine are nearly as ba
sic as aresolutions of sodium hydroxide.
本页源数据为无分隔提取文本，表格结构建议对照原课件图片核对。
LDASodium HMDSPotass：本页以图示与数据为主，提取文字如下。
LDASodium HMDSPotassiumt-ButoxideBarton'sBaseDBUHünig's BaseTriethylAminePyridineBase Name[(CH3)2CH]2N(–)Li(+)
[(CH3)3Si]2N(–)Na(+)(CH3)3CO(–)K(+)(C2H5)3NFormula35.72619141211.410.75.3pKaImportant Reagent BasespKa 8.8pKa
12pKa 6.79pKa 12.3
本页源数据为无分隔提取文本，表格结构建议对照原课件图片核对。
问题12-8DBN和DBU比一般胺的碱性强得多，是有机合成中广泛使用的有机碱，试指出DBN和DBU分子中哪一个氮原子最容易被质子化，并解释它们比简单胺碱性增强的原因
12.4 Acidity of Amines：pKa~36氨基离子
C6H5SO2NH2Compound9.61015192733pKa
Gabriel合成法——
硝基的还原——Reduction of Nitro Groups常用的还原剂：锡、铁、锌、氯化亚锡等
肟的还原——
Hofmann Rearrangement and Curtius Reaction
在Hofmann重排反应中，如果发生迁移的烃基碳原子为手性碳，迁移时其构型保持
Curtius Reaction：
QuizCompare the basicity of the following compounds：
Reductive Amination
The Leuckart Reaction——A useful variant of the reductive amination method usesformic acid or formate salts as reductants.
Mannich Reaction
12.6胺的反应（Reactions of Amines）12.6.1烷基化反应（Alkylation of Amines）
12.6.2胺的酰化（Acylation of Amines）Aza-Michael Addition：
Reaction with Benzen：本页以图示与数据为主，提取文字如下。
Reaction with Benzenesulfonyl chloride (The Hinsberg test)The Hinsberg test is conducted in aqueous base (NaOH
or KOH), and the benzenesulfonylchloride reagent is present as an insoluble oil. Because of the heterogeneous
nature of thissystem, the rate at which the sulfonyl chloride reagent is hydrolyzed to its sulfonate salt in
theabsence of amines is relatively slow. The amine dissolves in the reagent phase, andimmediately reacts (if i
t is 1º or 2º), with the resulting HCl being neutralized by the base. Thesulfonamide derivative from 2º-amines
is usually an insoluble solid. However, the sulfonamidederivative from 1º-amines is acidic and dissolves in t
he aqueous base. Acidification of thissolution then precipitates the sulfonamide of the 1º-amine.
本页源数据为无分隔提取文本，表格结构建议对照原课件图片核对。
12.6.3胺氧化物（Amine Oxides）Cope Elimination——occurs when 3º-amine oxides are heated at temperatures of 150 to200 ºC
Pyrolytic syn-Eliminations
12.6.4 与亚硝酸：本页以图示与数据为主，提取文字如下。
12.6.4与亚硝酸的反应（Reaction of Amines with Nitrous Acid）Nitrous acid: HNO2or HONONitrogen Gas Evolution from a Clea
rSolution1°-Amines + HONO (cold acidicsolution)An Insoluble Oil (N-Nitrosoamine)2°-Amines + HONO (cold acidics
olution)A Clear Solution (Ammonium SaltFormation)3°-Amines + HONO (cold acidicsolution)(1) Aliphatic Amines
本页源数据为无分隔提取文本，表格结构建议对照原课件图片核对。
Under the acidic con：本页以图示与数据为主，提取文字如下。
Under the acidic conditions of this reaction,all aminesundergo reversible saltformation:This happens with 3º-a
mines, and the salts are usually soluble in water. Thereactions of nitrous acid with 1°-and 2°-aliphatic amine
s may beexplained by considering their behavior with thenitrosonium cation(NO+), anelectrophilic species prese
nt in acidic nitrous acid solutions.亚硝酰正离子nitrosonium cation
本页源数据为无分隔提取文本，表格结构建议对照原课件图片核对。
Primary Amines脂肪族伯胺生成的烷基重氮盐在低温下也会放出氮气生成碳正离子，并按碳正离子的机理继续反应
N-亚硝基胺Secondary Amines
(2) Aryl Amines1º-Aryl Amines芳香族伯胺与亚硝酸反应生成的芳香重氮盐比烷基重氮盐稳定得多，可在水溶液中，0~10oC下保存一段时间，并用于多种芳香族化合物的合成中
2º-Aryl Amines3º-Aryl Amines
12.6.5芳胺的亲电取代（Electrophilic Substitution of Aryl Amines）
12.7季铵盐的消除反应（Elimination Reactions of4º-Ammonium Salts）
Hofmann Elimination——含有β-氢的季铵碱，在受热时则分解为烯烃、叔胺和水
Hofmann Rule——The tendency of Hofmanneliminations to give the less-substituted double bondisomer. This contrasts strikingly with theZaitsev Rule.
12.8重氮化合物（Diazo Compounds）Formula：R2CN2
12.8.1重氮化合物的制备（Preparation of Diazo Compounds）
12.8.2重氮化合物的反应（Reactions of Diazo Compounds）
carbene
12.9芳基盐的反应（Reactions of Aryl Diazonium Salts）1. Substitution with Loss of Nitrogen
2. Coupling Reactions
3. Bonding to Nitrogen偶氮化合物
偶氮化合物azo compoundThe：本页以图示与数据为主，提取文字如下。
偶氮化合物azo compoundThe most important application of diazo coupling reactions iselectrophilic aromatic substitut
ion of activated benzene derivativesby diazonium electrophiles.
本页源数据为无分隔提取文本，表格结构建议对照原课件图片核对。
偶氮染料
Quiz:Try to conceive a plausible product structure for each ofthe following couplings.
Quiz:Try to conceive a plausible reaction sequence for each ofthe following transformations.
下载地址：{{downurl}}
{{{a}}}
{{#b}}{{{b}}}
{{/b}} {{/title}} {{#nolog}}登陆注册
{{/nolog}} {{#djsx}}点我刷新
{{/djsx}} {{#gocz}} {{/gocz}} {{#ffqr}} {{/ffqr}}