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1、Chapter 17 Amines(胺胺)17.1 Amine Nomenclature 17.2 Structures of amines 17.3 Basicity of amines 17.4 Preparation of amines 17.4.1 Preparation of amines by alkylation of ammonia 17.4.2 The Gabriel synthesis of primary amines 17.4.3 Preparation of amines by reduction17.5 Reactions of amines17.5.1 Alkyl
2、ation of amines17.5.2 Acylation of amines17.5.3 The Hofmann Elimination17.5.4 Reactions of amines with nitrous acid(A)Reactions of primary aliphatic amines with nitrous acid(B)Reactions of primary arylamines with nitrous acid(C)Reactions of secondary amines with nitrous acid(D)Reactions of tertiary
3、amines with nitrous acid 17.5.5 Synthetic transformations of aryl diazonium salt(A)Replacement of the diazonium group by OH(B)Replacement of the diazonium group by X,CN(c)Replacement of the diazonium group by H 17.5.6 Azo coupling 17.6 Spectroscopic analysis of amines17.1 Amine NomenclatureOrganic d
4、erivatives of ammoniaAlkylaminesArylaminesMethylamine(甲胺）甲胺）Isobutylamine(异丁胺异丁胺)2-Methylpropylamine（2-甲基丙胺）甲基丙胺）Benzylamine(苄胺）苄胺）Primary amines（伯胺）伯胺）:P380Aniline(苯胺苯胺)Ethylmethylamine（甲乙胺）甲乙胺）N-Methylethylamine(N-甲基乙胺）甲基乙胺）Diethylamine（二乙胺）二乙胺）Secondary amines:(仲胺）仲胺）TrimethylamineN,N-Dimethylmet
5、hylamine（三甲胺）（三甲胺）（N,N-二甲基甲胺）二甲基甲胺）N,N-Dimethyl-aniline(N,N-二甲基苯胺二甲基苯胺)Tertiary amines:（叔胺）叔胺）Cyclohexylamine(环己胺环己胺)1,2-Ethyldiamine（1,2-乙二胺）乙二胺）Diamines:Ammonium ions（铵离子）铵离子）Aminium salts（铵盐）铵盐）Anilinium chloride（盐酸苯胺）盐酸苯胺）Quaternaryammoniumsalts（季铵盐）季铵盐）2-Aminoethanol（2-氨基乙醇）氨基乙醇）N-Ethyl-N-methy
6、lcyclohexylamine(N-甲基甲基-N-乙基环己胺乙基环己胺)Heterocyclic amine:(杂环胺杂环胺)Pyridine(吡啶吡啶)Pyrrole(吡咯吡咯)Quinoline(喹啉喹啉)Indole(吲哚吲哚)Pyrrolidine(吡咯烷吡咯烷)(四氢吡咯四氢吡咯)Piperidine(哌啶哌啶)17.2 Structures of aminessp3-hybridsp3-sp3 hybridized orbitals overlapCN：NH：sp3hybridized-1s orbitals overlapTertiary amines with 3 diffe
7、rent groups:Interconversion of amine enantiomersN:1s22s22px12py12pz1P383,12.2Pyramid(棱锥型棱锥型)17.3 Basicity of aminesQuarternary ammonium salt:Weak basesP384,12.3AminespKbNH3CH3NH2(CH3)2NH(CH3)3N4.73.43.34.39.4138.7Table 1 Basic strength of some aminesP385,Table12.11.All amines are weak bases:H2O RNH2
8、 RNH2 R3N NH3Poorer solvationSeparation of amines from neutral organic compounds17.4 Preparation of amines17.4.1 Preparation of amines by alkylation of ammoniaP384,12.3Anilinium ion17.4.2 The Gabriel synthesis of primary aminesReagent:Potassium salt of Phthalimide（邻苯二甲酰胺钾盐）邻苯二甲酰胺钾盐）Imide（酰亚胺）酰亚胺）Ch.
9、P436Primary alkyl halide,SN2ArX17.4.3 Preparation of amines by reduction LiAlH4Reduction of nitriles to aminesSiegmund Gabriel(1851-1924)Siegmund Gabriel was born in Berlin,Germany,and received his Ph.D.in1874 at the University of Berlin,working with August von Hofmann.After furtherwork with Robert
10、Bunsen,he became Professor of Chemistry at the Univ.of Berlin.Robert Wilhelm Bunsen1811-1899 poohbah.cem.msu.edu/Portraits/Gabriel Synthesis.Gabriel,Ber.20,2224(1887).M.S.Gibson,R.W.Bradshaw,Angew.Chem.Int.Ed.7,919(1968);B.Dietrich et al.,J.Am.Chem.Soc.103,1282(1981);O.Mitsunobu,Comp.Org.Syn.6,79-85
11、(1991).Modified conditions:S.E.Sen,S.L.Roach,Synthesis 1994,756;M.N.Khan,J.Org.Chem.61,8063(1996).Stereoselectivity:A.Kubo et al.,Tetrahedron Letters 37,4957(1996).Reduction of nitro compounds to arylaminesH2,catReduction of amides to amines:P389Reductive amination:Imine（亚胺）亚胺）Ch.P43517.5 Reactions
12、of amines Unshared electron pair of nitrogen:Basicity:+H XNucleophilicity:+17.5.1 Alkylation of amines(Cyclohexyl-methyl)-amineMethyliodide(cyclohexylmethyl)-trimethyl-ammonium iodide(99%)17.5.2 Acylation of aminesAcylating agents:acyl chlorides,carboxylic acid anhydridesSynthesis of Paracetamol（扑热息
13、痛）扑热息痛）:17.5.3 The Hofmann EliminationDecreasing the activity of aryl ring or Protecting amino groups:Methylation of an amine by excess CH3I:HexylamineHexyltrimethylammonium iodideCh.P448(六六)Quaternary ammonium hydroxides（氢氧化季铵碱）氢氧化季铵碱）can be prepared from Quaternary ammonium halides:Quaternary ammo
14、nium hydroxidesheat-Eliminationto form alkenes and an amineMethylenecyclohexane（亚甲基环己烷）亚甲基环己烷）(69%)Transition stateThe base attacks the mostacidic hydrogen or least hinder hydrogen.E2 ReactionAnti relationshipRegioselectivity of Hofmann elimination:To give a less substituted alkene.Hofmann rule is o
15、pposed to the Zaitsev rule.C1C2C2C3August Wilhelm von18181892 August Wilhelm von,18181892,German organic chemist.He wasProfessor at the Univ.of Berlin from 1865 and was a founder(1868)of the German ChemicalSociety.He studied the constitu-tion of aniline and was the firstto prepare rosaniline and its
16、 derivatives,thereby laying the basis for the aniline dye industry.He also discovered a reaction forderiving amines from amides anddeveloped the Hofmann methodof finding the vapor densities,and from these the molecular weights,of liquids.He also helped topopularize the concept of valence(the word co
17、mes from his termquantivalence17.5.4 Reactions of amines with nitrous acid(Nitrosation 亚硝化反应亚硝化反应)(A)Reactions of primary aliphatic amines with nitrous acidNitrosating agent:Primary aliphatic aminesNitrous acidto yield unstable aliphatic diazonium salt(重氮盐重氮盐)Diazotization(重氮化反应重氮化反应)Aliphatic diazo
18、nium salts decompose to formcarbocations and nitrogen:Alkene,alcohol,alkyl halide(B)Reactions of primary arylamines with nitrous acidPrimary arylamines form diazonium salt on nitrosation:Aryl diazoniumsalts are stable below 5P390(C)Reactions of secondary amines with nitrous acidSecondary amines:both
19、 aryl amines and alkyl amines react with nitrous acid to yieldN-nitrosoamines（亚硝胺）亚硝胺）N-nitrosoamines are usually separated from the reaction mixture as oily yellow liquids(D)Reactions of tertiary amines with nitrous acidTertiary aryl amines react with nitrous acid to form C-nitroso aromatic compoun
20、ds:Electrophilic aromatic substitution17.5.5 Synthetic transformations of aryl diazonium saltThe diazonium group（重氮基）重氮基）may be replaced by other atomes or groups:X,OH,CN and H.()P391:Electron-withdrawing groupAryl diazonium salts can be prepared from arene:(A)Replacement of the diazonium group by O
21、HAryl diazonium ion is converted to phenols(酚酚)Sulfuric acid is usually used instead of hydrochloric acidQuestion:Design a synsthesis of Hydrolysisp-Isopropylanilinep-Isopropylphenol (73%)(B)Replacement of the diazonium group by X,CNThe preparation of aryl iodidesThe preparation of aryl fluorides:Tr
22、eating the diazonium salt with fluoboricacid(HBF4)(69%)(81%)The Sandmeyer reaction:Aryl diazonium salts react with cuprouschloride,cuprous bromide,cuprous cyanide(70%overall)(65%overall)Born inWettingen near Zurich,and lived in the Zurich area for nearly all of his life.He trained as a precision ins
23、trument-maker,but became interested in chemistry.Self-educated in chemistry,he carried out chemical experiments in his kitchen.In 1881,he became a lecture assistant to Victor Meyer(1848-1897).He followed Meyer to Gttingen in 1886,but soon returned to Zurich and worked for Arthur Hantzsch(1857-1935).
24、Sandmeyer joined Geigy as a research scientist in 1888,and eventually became a director of the firm.He discovered the decomposition of aryl diazonium Chlorides to chloroarenes in the presence of copper(I)chloride in 1884.He also worked on the triphenylmethane dyes and the synthesisof isatin.Many yea
25、rs before,he had suggested to Victor Meyer an impurity in commerical benzene was responsible for the isatin reaction with sulphuric acid,thereby paving the way for Meyers discovery of thiophen.Traugott Sandmeyer(1854-1922).(C)Replacement of the diazonium group by H Aryl diazonium salts react with hy
26、pophosphorous acid(H3PO2)(次磷酸）次磷酸）or ethanol to yield the product:Deamination（脱氨基作用）脱氨基作用）(85%)P392The value of diazonium salts in synthesis:1.Substituents that are otherwise accessible2.only with difficulty,such as F,I,3.CN,OH,may be introduced onto 4.a benzene ring.2.Compounds that have substituti
27、on patterns3.not directly available by electrophilic 4.aromatic substitution can be preparedAniline2,4,6-Tribromoaniline(100%)1,3,5-Tribromo-Benzene(74-77%)17.5.6 Azo coupling(偶氮偶合反应偶氮偶合反应)Aryl diazonium salts are weak electrophiles,they react with highly reactive aromatic compounds,to yield azo com
28、poundsAzo dyes（偶氮染料）偶氮染料）Orange II：P393Alkaline solution17.6 Spectroscopic analysis of aminesIR：Streching vibrationPrimary amine3000-3500 cm-1two peaksSecondary amines3280 cm-1one peakTertiary aminesNo peakStreching vibration1020-1220 cm-1AliphaticaminesAromaticamines1250-1360 cm-1Ch.P437(四四)Infrare
29、d spectrum of isobutylamineCN StretchingvibrationNH StretchingvibrationN-甲基苯胺的红外光谱甲基苯胺的红外光谱N-H伸伸缩缩C-N伸伸缩缩苯环苯环伸缩伸缩1H NMRN-H：0.6 5 ppm：2.2 2.8 ppmProblems to Chapter 17P40212.21(a),(d),(e)12.22(a),(c),(f)12.24 酶斯卡灵，一种酶斯卡灵，一种 高效的致幻剂高效的致幻剂。从从 仙人掌中得来。仙人掌中得来。12.27(b),(d),12.29(b),(c)12.30(a)12.31(b),(c)12
30、.3712.3912.4112.4212.4812.5112.52Additional Problems to Chapter 1711.What are the major products you would 2.expect from Hofmann elimination of the 3.following amines?Show the reactions.(a)N-Methylcyclopentylamine(c)2.Predict the product(s)of the following reactions.Give the major product.(3)How would you prepare the following compounds from toluene?A diaonio (重氮盐重氮盐)replacement reaction is needed in some instances.(4)Ch.P464 (十六十六),(十七十七)