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1、ADVANCEDORGANICCHEMISTRYPartIIShanxiNormalUniversity2014CHAPTER6AdditiontoCarbon–CarbonMultipleBondsMECHANISMS1.1ElectrophilicAddition1.2NucleophilicAddition1.3Free-RadicalAddition1.4CyclicMechanisms1.5AdditiontoConjugatedSystemsORIENTATIONANDREACTIVITY2.1Or
2、ientation2.2StereochemicalOrientation2.3AdditiontoCyclopropaneRings3.REACTIONSMECHANISMS1.1ElectrophilicAddition-980C,H2CCl2,synaddition00C,Et2O,antiaddition1.2NucleophilicAdditionC=C-ZZ=CHO,COR,COOR,CONH2,CN,NO2,SOR,SO2R,andsoon1.3Free-RadicalAdditionor1.4C
3、yclicMechanisms1.5AdditiontoConjugatedSystemsTABLE6.1.RelativeReactivityofSomeAlkenesTowardBromineinAceticAcidat240CTABLE6.2.RelativeReactivityofSomeAlkenesTowardBromineinMethanolORIENTATIONANDREACTIVITYElectrophilicadditionNucleophilicadditionZ=NO2,COAr,CHO
4、,COR,SO2Ar,CN,COOR,SOAr,CONH2,CONHR.OrientationStereochemicalOrientationAdditiontoCyclopropaneRings3.REACTIONSISOMERIZATIONOFDOUBLEANDTRIPLEBONDS6-1IsomerizationREACTIONSINWHICHHYDROGENADDSTOONESIDEA.HalogenontheOtherSide6-2AdditionofHydrogenHalidesB.Oxygeno
5、ntheOtherSide6-3HydrationofDoublebonds6-4HydrationofTripleBonds6-5AdditionofAlcoholsandPhenols6-6AdditionofCarboxylicAcidstoFormEstersC.SulfurontheOtherSide6-7AdditionofH2SandThiolsD.NitrogenorPhosphorusontheOtherSide6-8AdditionofAmmoniaandAmines,Phosphines,
6、andRelatedCompoundsPd,Mo,Rh,La6-9AdditionofAmides6-10AdditionofHydrazoicAcidTiCl4E.HydrogenonBothSides6-11HydrogenationofDoubleandTripleBondscatalystsinsolubleinthereactionmedium(heterogeneouscatalysts).AmongthemosteffectiveareRaneynickel,palladium-on-charco
7、al(perhapsthemostcommon),NaBH4-reducednickel(alsocallednickelboride),platinummetaloritsoxide,rhodium,ruthenium,andzincoxide.(2)Catalystssolubleinthereactionmedium(homogeneouscatalysts).Animportantexampleischlorotris(triphenylphosphine)rhodium,RhCl(Ph3P)3,(Wi
8、lkinson’scatalyst)whichcatalyzesthehydrogenationofmanyalkenylcompoundswithoutdisturbingsuchgroupsasCOOR,NO2,CN,orCORpresentinthesamemolecule.AparticularlygoodcatalystforthispurposeistheLindlarca
