清华大学有机化学李艳梅老师课件第10章

Alcoholsandphenols第十章醇与酚OrganicChemistryA(1)ByProf.LiYan-MeiTsinghuaUniversityOHOHOHHOOHHOOH醇（Alcohol）酚（Phenol）ContentPartIAlcohols10.1Structure,isomerization,classificationandnomenclature10.2Physicalandspectroscopicproperties10.3Monobasic/Monohydroxylalcohol10.4Polybasicalcohol10.5Preparationofalcohol10.6SourcesandusagesPartIIPhenol/Hydroxybenzene10.7Structureandnomenclature10.8Physicalandspectroscopicproperties10.9Chemicalreactions10.10Preparations10.11SourcesandusagesPartIAlcohols第一部分醇10.1.1Structure10.1.2Isomerization10.1.3Classification10.1.4Nomenclature10.1Structure,isomerization,classificationandnomenclature108.5osp3hybridizationμ≈2DVeryclosetowaterManyalcoholscompletelymisciblewithwater10.1.1Structure结构OH10.1.2Isomerization异构PositionisomerizationOHOHOHOHOFuctionalgroupisomerizationCarbonchainisomerization位置异构碳架异构官能团异构10.1.3Classification分类C4C5~C11C12OHOHHOOHHOOHOHOHOH根据羟基数目：一元醇二元醇三元醇根据所连的碳原子不同：一级醇（伯醇）二级醇（仲醇）三级醇（叔醇）根据所含碳原子数目：低级醇中级醇高级醇10.1.4Nomenclature命名OHDecidingthelongestchaintowhichthehydroxylgroupisattached1Decidetheserialnumberforallcarbonatoms.2Writedownthename.3OH123452-pentanolOH5,5-dimethyl-2-hexanolCH3OH5-methyl-3-hexanolCH3OH5-methylhex-4-en-2-olOH(E)-pent-3-en-1-olOHO2N4-nitrophenolIntermolecularhydrogenbondBoilingpointMeltingpointSimplealcoholscompletelymisciblewithwater与水形成氢键低级醇一般与水任意混溶OHHOHOOHHOHOHH10.2Physicalandspectroscopicproperties10.2.1Physicalproperties分子间氢键导致熔点、沸点较高Simplealcoholsmayformco-crystalswithinorganicsalts.低级醇与一些无机盐（如：MgCl2、CaCl2、CuSO4等）形成结晶状的分子化合物－结晶醇（醇化物）MgCl2,CuSO4……MgCl2·6CH3OHCaCl2·4C2H5OHCaCl2·4CH3OH用途：除去有机溶剂中少量的醇将醇与其它有机物分开危害：不可用MgCl2、CaCl2、CuSO4等来干燥低级醇10.2.1Spectrometryν(O-H)ν(C-O)3640cm-13630cm-1OHOHOH3620cm-11050cm-11100cm-11150cm-1IRν(O-H)3550~3450cm-1ν(O-H)3400~3200cm-1inintermolecularhydrogenbondingsystemsOHHOOHHOHOν(-OH)3600~3500cm-1inintramolecularhydrogenbondingsystemsν(-OH)3200~3500cm-1multimoleculeclusterν(-OH)3400~3200cm-1OHOHNOOHOν(O-H)3710cm-1ν(O-H)3300cm-1ν(O-H)3600~3450cm-1IRofOHbondinwatermoleculeSolid,iceCrystallizedwaterLiquidwaterCH2OHNMR0.5-5.5~3.7CHCHOH15-19活泼氢10.3.1Acidityandbasicity10.3.2Esterifying10.3.3Nucleophilicsubstitution10.3.4Dehydrationandelimination10.3Monobasic/MonohydroxylalcoholLonepairelectronsBasicityNucleophileAcidityIonizationReactingwithalkalimetalsLabilebeta-hydrogenEliminationOxidationDehydrationBriefintroductionCHCHHHOHOHisnotagoodleavinggroup.ProtonisoftenrequiredtochangethebadleavinggroupOHintoagoodleavinggroupOH2+OH2Nu:OHHNuH2OOHNu:好的离去基团10.3.1Acidityandbasicity酸、碱性StrongeracidityWeakeracidity(1)Relativeacidity酸性顺序ROHRO+HOHOHOH(A)Acidity酸性原因：溶剂化效应的影响Moresolvationleadstomorestablepositiveion.OHOHOH溶剂化效应的影响：StrongeracidityWeakeracidityInductiveeffectElectroncloudpulledOHClOHOHClOHFFF诱导效应的影响：Na(2)Reactionwithmetals与金属的反应KCaMgAlRbSrBaCs2ROHNa2RONa+H2ReactionrateRCH2OHR2CHOHR3COHApplicationsDealwithsuchmetalswithalcohol,reducingreactionrate,avoidingexplosion.Alcoholicmetalsaregoodnucleophiles.醇金属可作为好的亲核试剂。(B)Basicity碱性OHOHH+OH2OHBF3OHBF3Borontrifluoride好的离去基团好的离去基团10.3.2Esterification酯化反应ROH+HONO2RONO2+H2OROH+HONORONO+H2OROH+HOSO2OHROSO2OH+H2OOrganicacidInorganicacidROH+R'OHOR'OROH+某酸某酯硝酸某酯亚硝酸某酯硫酸氢某酯AcylchlorideROH+ClSO2OHROSO2OH+HClROH+R'COClR'COOR+HClAnhydrideROH+R'OOR'OROR'OHOR'O+Mechanism机理ROH+R'OHOR'OOHOHRR'OHOHORH+R'OH2OORHR'OROROH+H+SOOHOOHHORSOOHOHOORSOOHOHHOORSOOHOH2OHSOOHOORROH+R'OClR'CClOORR'OOR10.3.3Nucleophilicsubstitution亲核取代反应COHHHNu:CNuHHNucleophilicreagent亲核试剂HX,PX3,SOCl2…...常见产物：RX（RCl）ROH+HXRX+H2O(A).ReactionswithHX与HX的反应3oROH2oROH1oROHReactivityHIHBrHClHFMechanism：H+及ZnCl2的作用----形成好的离去基团ROHH+ROH2ROHZnCl2ROHZnCl2SN1orSN2?Generally,1oROHfollowsSN2mechanism,while2oand3oROHfollowsSN1mechanism,whichisoftencoupledwithananionrearrangement.OHH+OH2hydrideshiftHBrBrOH易发生重排Mechanism----neighboringgroupparticipation邻基参与BrBrHHOH+BrBrHH2OBrBrHBromoniumionClBrBrHClLucasreagent:Lucas试剂ROH+HClZnCl2RCl+H2OReactivity反应性3oROH2oROH1oROHReactionoccursimmediately立刻反应Reactionoccursafter2~5min片刻(2-5分钟)后反应Reactionoccurswhenheated加热才反应C6以下一元醇溶于HCl不溶于HCl变浑由于鉴别10、20、30醇(B).ReactionswithPXnReaction3ROH+PBr33RBr3+H3PO3MechanismRClisoftenpreparedwithPCl5andthecorrespondingalcohol,whileRIwithP,iodine,andthecorrespondingalcohol.ROH+PBr3ROPBr2+HBrRH2COPBr2Br+RCH2Br+OPBr2不重排(C)ReactionswithSOCl2ROH+SOCl2RCl+SO2+HClNorearrangement!SOCl2HClClOHClOH不重排10.3.4Dehydrationandelimination脱水与消除(A)Intermolecular分子间脱水ROHHOR+H2SO4RORetherExampleAsidereactionofalcoholdehydrationtoformethene.Youhaveperformedthisexperimentathighschool.C2H5OHHOC2H5+H2SO4C2H5OC2H51400CMechanismOH2CH3CH2OHH2SO4CH3CH2OH2+HSO4CH3CH2CH3CH2OH+C2H5OC2H5HHSO4C2H5OC2H5+H2SO4本质：亲核取代反应(B)IntramoleculardehydrationCCOHHH+170~180oCCC+H2OExample+H2OH3CCH2OHH2SO4180oCH2CCH2ThisreactionfollowsanE1eliminationmechanism.Mechanism3oROH2oROH1oROHReactivity+HH3CCH2OHH2SO4H2CCH2H3CCH2OH2+H2SO4H3CCH2OH2SlowFastH3CCH2+H2OH2CCH2HFastProductFollowsZaitzev’sruleEform本质：消去反应Rearrangementoccurswhenamorestableanionisformed.OHH3PO4+3%64%注意：Competitionbetweenintermolecularandintramo