浙江大學(xué) 英文 有機(jī)化學(xué)

OrganicChemistry;Tel:87217325OrganicReactions,SynthesisThefirstorganicsynthesiswasaccomplishedbyFriedrichWohlerin1828AlkanesandCycloalkanesAlkanes:CycloalkanesAlkanesarecharacterizedbyageneralinertnesstomanychemicalreagentsWhenheated,alkanescanreactwithchlorine,bromine.SynthesisofalkanesandcycloalkanesSpecificexamplesSynthesisofalkanesandcycloalkanesSynthesisofalkanesandcycloalkanesB:ReductionofAlkylHalidesGeneralReaction:Zincatomstransferelectronstocarbonatomofalkylhalide:SynthesisofalkanesandcycloalkanesAlyklationofterminalalkynesGeneralreactionSpecificreactionSynthesisofalkanesandcycloalkanesSpecificreactionAlkylHalides:NucleophilicSubstitutionandEliminationReactionsAMechanismfortheSN2ReactionReaction:Mechanism:ThestereochemistryofSN2ReactionThenucleophileattacksfromthebackside,thatis,fromthesidedirectlyoppositetheleavinggroup.Thismodeofattackcausesachangeintheconfiguration.ThestereochemistryofSN2ReactionAMechanismfortheSN1ReactionStep2:Step3:ThestereochemistryofSN1reactionsReactionsthatinvolveracemization:FactorsaffectingtheratesofSN1andSN2reactionThestructureofthesubstrateTheconcentrationandreactivityofthenucleophile

TheeffectofthesolventThenatureoftheleavinggroupFactorsfavoringSN1versusSN2reactionsFactorSN1SN2Substrate3oMethyl>1o>2oNucleophileWeakLewisBasStrongLewisbaseSolventPolarprotic(alcohols,H2O)Polaraprotic(DMF,DMSO)LeavinggroupI->Br->Cl->F-ForbothSN1andSN2FunctionalgrouptransformationsusingSN2reactionsEliminationreactions(dehydrohalogenations)ofalkylhalidesAmechanismfortheE1RiactionReaction:Mechanism:Step1Step2SubstitutionversusEliminationNucleophilicsubstituionandeliminationoftencompetewitheachotherSN2versusE2PrimaryhalideSecondayhalidesSubstitutionversusEliminationUseofaweaklybasicionoracetateion(CH3CO2-)increasesthelikelihoodofsubstitutionAlkenesandAlkynes:synthesisofalkenesviaeliminationreactiongDehydrohalogenationofAlkylHalidesDehydrationofAlcoholsDebrominationofvic-DibromidesE2Reactions:TheorientationofthedoublebondintheproductThestereochemistryofE2ReactionsE2Eliminationwheretherearetwoaxialcyclohexaneβ-HydrogensE2EliminationwhereonlyEligibleaxialcyclohexaneβ-HydrogenisfromalessstableconformerDehydrationofAlcoholsGeneralreaction:TherelativeeaseofdehydrationisinthefollowingorderAcid-catalyzeddehydrationofsecondaryortertiaryalcohols:AnE1reactionDehydrationofprimaryalcohol:

AnE2reactionRearrangementsduringdehydrationofsecondaryalcoholsRearrangementsduringdehydrationofsecondaryalcoholsRearrangementsduringdehydrationofsecondaryalcoholsAlkenesbydebrominationofvicinaldibromidesSynthesisofalkynesbyEliminationReactionsSynthesisofalkynesbyEliminationReactionsHydrogenationofalkynesSynaddition:Antiaddition:AlkenesandAlkynes:AdditionReactionAdditiontoAlkenesAdditionofHydrogenHalidestoAlkenes:Markovnikov’sRulesModernstatementofMarkovnikov’sRuleAnExceptiontoMarkovnikov’sRuleThesterochemistryofthereactionStereochemistryoftheadditionofhalogenstoalkenesHalohydrinformationDivalentcarboncompounds:CarbensOxidationofalkenes:synhydroxylation.OxidativecleavageofalkenesOzonolysisofAlkenesAdditionreactionsofalkynesRadicalReactionRadicaladditiontoalkenes:Theanti-Markovnikowadditionofhydrogenbromide

ReactionMechanism:AlcoholsfromAlkenesthroughOxymercuration-DemercurationThenetorientationofadditionofH-and–OHisinaccordancewithMarkovnikov’sAMechanismfortheReactionHydroboraton:SynthesisofOrganoboratonConversionofalcoholsintomesylatesandtosylatesMesylatesandTosylatesinSN2ReactionConversionofalcoholsintoalkylhalidesTheWilliamsonSynthesisofEthersEpoxidesTheadditionofoxygentothedoublebondinanepoxidationreactionisasynadditionReactionsofEpoxidesInbase-catalyzedringopening,attackbythealkoxideionatthelesssubstitutedcarbonatomIntheacid–catalyzedringopeningofanunsymmetricalepoxide,thenucleophileattacksatthemoresubstitutedcarbonatom;AntihydroxylationofalkenesviaepoxidesAlcoholsfromcarbonylcompounds.Oxidation-ReductionandOrganometallicCompoundsReductionofaldehydesandketonesbyhydridetransferOverallsummaryofReductionReactionsOverallSummaryofOxidationReactionsFormationofOrganolithiumandGrignardReagentsReactionsofGrignardandOrganolithiumReagentsLithiumDialkylcuprates:TheCorey-PosnersynthesisConjugatedUnsaturatedSystemsAllylichalogenationwithalowconcentrationofX2AllylichalogenationusingN-bromosuccinimideConjugateaddition:1,2versus1,4additionConjugateaddition:1,2versus1,4additionTheDiels-AlderReactionDiels-Alderreactionisfavoredbythepresenceofelectron-withdrawinggroupsinthedienophileandelectron-releasinggroupsinthedieneTheDiels-AlderReactionThereactionissynadditionandtheconfigurationofthedienophileisretainedStereochemistryThediene,ofnecessity,reactsinthes-cisconformationratherthanthes-transTheDiels-AlderreactionoccursprimarilyinanendoratherthananexofashionwhenthereactioniskineticallycontrolledElectrophilicaromaticsubstitutionreactionsSyntheticApplicationsofFriedel-CraftsAcylations:TheClemmensenreductionHalogenationofthesideChain.BenzylicRadicalOxidationofthesidechainUseofProtectingandBlockingGroupsUseofProtectingandBlockingGroupsTheBirchReductionAdditionReactionofAldehydesandketonesGrignardReaction:ReformatskyReaction:AdditionofHydrideionGeneralReaction:AdditionofHydrogenCyanideEgAdditionofYieldsAdditionofAlcoholsAdditionofDerivativeofammoniaTheWolff-KishnerReductionTheBaeyer-VilligerOxidationofAldehydesandKetonesMigratoryaptitude:PayattentiontothemechanismTollen’sTest(silverMirrorTest)ReactionsviaEnolesandEnolateAnionsHalogenationofketonesThehaloformreactionThealdolreaction:TheadditionofEnolateanionstoaldehydesandketonesClaisen-SchmidtreactionCondensationswithnitroalkanesandNitrilesCyclizationsviaaldolcondensationLithiumEnolatesDirectAlkylationofketonesviaLithiumEnolatesConjugateadditionOrganocopperreagentsaddalmostexclusivelyintheconjugatemannerMichaeladditionsCarboxylicacidsandtheirderivativesa-haloacidsDecarboxylationofcarboxylicacidsReactionsofNitrilesTheMannichReactionSynthesisofEnamines:StorkEnamineReactionsAcetoaceticestersynthesisAmines:DiazotizatoinofprimaryArylaminesTheHofmannEliminationHofmannrule:Yieldmainlytheleastsubstitutedalkene.TheCopeEliminationTheCopeeliminationisasynelimination:PhenolsandArylhalidesWilliamsonsynthesisClaisenRearrangement有機(jī)化學(xué)反應(yīng)

加成反應(yīng)（親電.親核）

取代反應(yīng)（親電.親核）

消除反應(yīng)

氧化還原反應(yīng)格氏試劑反應(yīng)

α-H活性反應(yīng)重排反應(yīng)

其它反應(yīng)1.加成反應(yīng)加硫酸（符馬氏）加次氯酸（符馬氏）過氧化物加成（反馬氏）硼氫化反應(yīng)（反馬氏）▲親電加成可以引發(fā)重排例題

炔烴加成酸催化加水硼氫化反應(yīng)雙烯合成麥克爾加成親核加成與氫氰酸加成（適用范圍：醛.脂肪族甲基酮和八個(gè)碳以下的環(huán)酮），進(jìn)一步水解可以得到多一個(gè)碳的酸與醇加成（保護(hù)羰基）例：

羥醛縮合

2.取代反應(yīng)SN1(可以重排）SN2(反面進(jìn)攻，構(gòu)型翻轉(zhuǎn))雜環(huán)取代

(親電)

芳環(huán)取代

醚鍵