重要经典化学反应及其机理

-AromaticReactions-Condensation-Cyclization-EpoxideTransformation-Olefination-Oxidation-Reduction-RearrangementCondensationOlefinationOxidationRearrangementReductionCyclizationAromaticReactionstopCommonTransformationofEpoxidetop...arecentmemoirbyaHerrvan'tHoffontheArrangementsofAtomsinSpace,adocumentcrammedtothehiltwiththeoutpouringsofachildishfantasy...ThisDr.J.H.van'tHoff...notasteforaccuratechemicalresearch...ByH.Kolbe(oneofthemosteminentorganicchemistofthetime).10yearslatervan'tHoffwasnamedthefirstrecipientoftheNobelPrizeinChemistry.AAcetoaceticEsterSynthesisisaveryusefulbasicreactioninetherindustryoracademia.Themethylenegroupinacetoacticestercouldbeeasilyalkylated,anddoublealkylatedunderbasiccondition.OneconditionIusedfrequentlyisacetoneassolvent,K2CO3asbase,andalkylbromideasalkylationreagent.Thereactionrarelyletsmedown.Simonsen,J.L.;Storey,R.J.Chem.Soc.1910,95,2106Simonsen,J.L.;Storey,R.Proc.Chem.Soc.1910,25,290Clickheretolearnmore.Alder(Ene)ReactionisthermalorcatalyticsigmatropicrearrangementwithH-trasferandcarbonbondformation.Clickheretolearnmore.AldolcondensationisareactionthatgeneratedlotsofPh.D.inorganicsynthesis.Noneedtotalkaboutit.Thealdolcondensationusingaldehydeandsilylenoletherasstartingmaterials,andlewisacid,likeTiCl4,ascatalystiscalledMukaiyamaaldolcondensation.Kane,R.Ann.Phys.Chem.Ser.21838,44,475Kane,R.J.Prakt.Chem.1838,15,129Clickheretolearnmore.Algar-Flynn-OyamadaReactionisthesynthesisofflavonolsviatheintermediatedihydroflavonolsmadebyoxidationofo-hydroxyphenylstyrylketoneusinghydrogenperoxide.Clickheretolearnmore.Allen-Millar-Trippetrearrangement.Clickheretolearnmore.AmadoriRearrangementistheconversionofN-glycosidesofaldosestoN-glycosidesofthecorrespondingketones.Clickheretolearnmore.Angeli-RiminihydroxamicacidsynthesisClickheretolearnmore.AppelHalogenationClickheretolearnmore.Arndt(FritzArndt1885-1969)-Eistert(BerndEistert1902-1978)rearrangementisusedintheconversionofacarboxylicacidintoitshomologorderivativesofthehomologousacid.Ifthereactionintermediatecouldbequenchedtogivealpha-haloketone.Clickheretolearnmore.AsingerThiazolineSynthesisClickheretolearnmore.Auwersreactionistheexpansionofcoumaronestoflavonols.K.v.Auwersetal.,Ber.41,4233(1908);48,85(1915);49,809(1916)K.v.AuwersandP.Pohl,Ann405,243(1914)Clickheretolearnmore.AzocouplingClickheretolearnmore.BCtopBaeyerPyridineSynthesisClickheretolearnmore.Baeyer(JohannFriedrichWilhelmAdolf[von]Baeyer1835-1917)-Villiger(VictorVilliger1868-1934)Oxidationisanoxidativerearrangementreactioninitiatedbynucleophilicattack.Theorderofmigratoryaptitudeis3o-alkyl2o-alkylbenzylphenyl1o-alkylcyclopropylMeH.Ifitisusedinphenylaldehydetomakephenol,thereactioniscalledDakinoxidation.Clickheretolearnmore.JohannFriedrichWilhelmAdolfvonBaeyer,NobelPrizeChemistry1905.Baker(WilsonBakerb.1900)-Venkataramanrearrangementistherearrangementofo-ketoesterofphenoltoo-hydroxy-1,3-diketone.The1,3-diketonecouldcyclizetoformflavone.Clickheretolearnmore.Bamberger(EugenBamberger1857-1932)rearrangementistheintermolecularrearrangementofN-phenylhydroxlaminestothecorresponding4-aminophenolunderacidiccondition.Clickheretolearnmore.BambergerimidazolecleavageClickheretolearnmore.Bamford(W.R.Bamford)-Stevens-ShapiroOlefinationisabase-catalyzeddecompositionofarenesulfonylhydrazonesofaldehydesandketones,leadingtotheformationofalkenes.Clickheretolearnmore.Barbier(FrancoisAntoinePhillipeBarbier1848-1922)Reactionistheone-potprocedureforthepreparationofalcoholsfromorganichalidesandaldehydesorketones.Clickheretolearnmore.BargellinireactionisusingaketoneandCHCl3generateadichloroepoxide,whichreactwithahydroxylamineordiamnioethanederivativetoformhighlyhinderedmorpholinoneorpiperazinone.Clickheretolearnmore.Bartoli(GiuseppeBartoli)indolesynthesisisthesynthesisofindolesreductivelybyo-substitutednitrobenzeneandallylgrignard.Clickheretolearnmore.Barton(DerekH.R.Barton1928-1998)deaminationClickheretolearnmore.BartondecarboxylationClickheretolearnmore.Bartondeoxygenationisthedeoxygenationofalcoholsviatheirthiocarbonylderivatives.Clickheretolearnmore.Baylis(A.B.Baylis)-Hillman(M.E.D.Hillman)Reactionistheactivatedvinylsystemtoreactwithketoneoraldehydetoyieldalpha-hydroxylproducts.Clickheretolearnmore.Beckmann(ErnstOttoBeckmann1853-1923)Rearrangementisacid(P2O5,PCl5,H2SO4etc)catalyzedrearrangementofoximetoamideornitrile.Clickheretolearnmore.Benzilicacidrearrangementisbase-inducedrearrangementofbenziltobenzylicacidviaphenylgroupmigration.Liebig,J.Ann.Chem.1838,25,27Zinin,N.Ann.Chem.1839,31,329Clickheretolearnmore.BenzoinCondensationiscyanide-catalyzedcondensationofaromaticaldehydestogivebenzoins.Lapworth,A.J.J.Chem.Soc.1903,83,995Lapworth,A.J.J.Chem.Soc.1904,85,1206Clickheretolearnmore.Bergman(RobertGeorgeBergman)Cyclizationisthecyclizationofenediynestogenerate1,4-benzenoiddiradicals.Clickheretolearnmore.BernthsenAcridineSynthesisisthesynthesisof5-substitutedacridinesbydiarylaminesinorganicacidsoranhydrides.Clickheretolearnmore.Biginellipyrimidonesynthesisisthe3componentsformationoftetrahydropyri