Editedby ShannonS.StahlandPaulL.Alsters LiquidPhaseAerobicOxidation Catalysis Editedby ShannonS.StahlandPaulL.Alsters Liquid Phase Aerobic Oxidation Catalysis IndustrialApplicationsandAcademicPerspectives Editors AllbookspublishedbyWiley-VCHare carefullyproduced.Nevertheless,authors, Prof.Dr.ShannonS.Stahl editors,andpublisherdonotwarrantthe UniversityofWisconsin-Madison informationcontainedinthesebooks, DepartmentofChemistry includingthisbook,tobefreeoferrors. 1101UniversityAvenue Readersareadvisedtokeepinmindthat MadisonWI53706 statements,data,illustrations,procedural USA detailsorotheritemsmayinadvertently beinaccurate. Dr.PaulL.Alsters DSMAheadR&Db.v. LibraryofCongressCardNo.:appliedfor InnovativeSynthesis P.O.Box1066 BritishLibraryCataloguing-in-Publication 6160BBGeleen Data TheNetherlands Acataloguerecordforthisbookis availablefromtheBritishLibrary. Cover:ErikdeGraaf/iStock Bibliographicinformationpublishedby theDeutscheNationalbibliothek TheDeutscheNationalbibliothek liststhispublicationintheDeutsche Nationalbibliografie;detailed bibliographicdataareavailableonthe Internetat<http://dnb.d-nb.de>. ©2016Wiley-VCHVerlagGmbH&Co. KGaA,Boschstr.12,69469Weinheim, Germany Allrightsreserved(includingthoseof translationintootherlanguages).Nopart ofthisbookmaybereproducedinany form – byphotoprinting,microfilm, oranyothermeans – nortransmitted ortranslatedintoamachinelanguage withoutwrittenpermissionfromthe publishers.Registerednames,trademarks, etc.usedinthisbook,evenwhennot specificallymarkedassuch,arenottobe consideredunprotectedbylaw. PrintISBN:978-3-527-33781-1 ePDFISBN:978-3-527-69015-2 ePubISBN:978-3-527-69014-5 MobiISBN:978-3-527-69013-8 oBookISBN:978-3-527-69012-1 Typesetting SPiGlobal,Chennai,India PrintingandBinding Printedonacid-freepaper V Contents Preface XV ListofContributors XVII PartI RadicalChainAerobicOxidation 1 1 OverviewofRadicalChainOxidationChemistry 3 IveHermans 1.1 Introduction 3 1.2 ChainInitiation 6 1.3 ChainPropagation 7 1.4 FormationofRing-OpenedBy-ProductsintheCaseofCyclohexane Oxidation 11 1.5 ComplicationsintheCaseofOlefinAutoxidation 12 1.6 SummaryandConclusions 13 References 14 2 NoncatalyzedRadicalChainOxidation:CumeneHydroperoxide 15 ManfredWeber,Jan-BerndGrosseDaldrup,andMarkusWeber 2.1 Introduction 15 2.2 ChemistryandCatalysis 15 2.2.1 CumeneRoutetoPhenolandAcetone:ChemistryOverview 16 2.2.2 ThermalDecompositionofCumeneHydroperoxide 17 2.2.3 OxidationofCumene 19 2.3 ProcessTechnology 21 2.3.1 ProcessOverview 21 2.3.2 ReactorsfortheCumeneOxidation 22 2.3.3 ReactorModeling 23 2.3.4 ProcessSafetyAspects 26 2.4 NewDevelopments 27 2.4.1 ProcessIntensificationbyModificationoftheOxidation Reaction 27 2.4.2 ImprovementsofReactorandProcessDesign 29 References 30 VI Contents 3 CyclohexaneOxidation:HistoryofTransitionfromCatalyzed toNoncatalyzed 33 JohanThomasTinge 3.1 Introduction 33 3.2 ChemistryandCatalysis 34 3.3 ProcessTechnology 35 3.3.1 TheTraditionalCatalyzedCyclohexaneOxidationProcess 35 3.3.2 TheNoncatalyzedDSMOxanone®CyclohexaneOxidation Process 37 3.4 NewDevelopments 38 Epilogue 39 References 39 4 ChemistryandMechanismofOxidationofpara-XylenetoTerephthalic AcidUsingCo–Mn–BrCatalyst 41 VictorA.AdamianandWilliamH.Gong 4.1 Introduction 41 4.2 ChemistryandCatalysis 42 4.2.1 Co–BrCatalysis 43 4.2.2 Cobalt–Manganese–BromideCatalysis(MCOxidation):TheNature ofSynergybetweenCoandMn 48 4.2.3 TheRoleandNatureofBromineSpeciesinMCOxidation 50 4.2.4 NatureofCobalt(III)andMn(III)Species 52 4.2.5 ReactionsofCobalt(II)withPeroxyRadicalsandtheEffectofSolvent onOxidationRate 52 4.2.6 PhenomenonofManganesePrecipitation 54 4.2.7 ConsolidatedViewofMCOxidationMechanism 54 4.2.8 OxidationBy-products 56 4.3 ProcessTechnology 58 4.3.1 Oxidation 58 4.3.2 Purification 58 4.4 NewDevelopments 61 4.4.1 HomogeneousBrominelessCatalysis 61 4.4.2 HeterogeneousBrominelessOxidationCatalysis 62 4.4.3 AlternativeSolvents 62 4.5 Conclusions 62 References 63 PartII Cu-CatalyzedAerobicOxidation 67 5 Cu-CatalyzedAerobicOxidation:OverviewandNew Developments 69 DamianHruszkewycz,ScottMcCann,andShannonStahl 5.1 Introduction 69 5.2 ChemistryandCatalysis 70 Contents VII 5.2.1 Cu-CatalyzedOxydecarboxylativePhenolSynthesis 70 5.2.2 Cu-CatalyzedOxidativeCarbonylationofMethanolfortheSynthesis ofDimethylCarbonate 72 5.3 ProcessTechnology 74 5.3.1 Cu-CatalyzedOxydecarboxylativePhenolSynthesis 74 5.3.2 Cu-CatalyzedOxidativeCarbonylationofMethanolfortheSynthesis ofDimethylCarbonate 75 5.4 NewDevelopments:PharmaceuticalApplicationsofCu-Catalyzed AerobicOxidationReactions 76 References 82 6 Copper-CatalyzedAerobicAlcoholOxidation 85 JanelleE.StevesandShannonS.Stahl 6.1 Introduction 85 6.2 ChemistryandCatalysis 86 6.3 ProspectsforScale-Up 91 6.4 Conclusions 93 References 94 7 PhenolOxidations 97 7.1 PolyphenyleneOxidesbyOxidativePolymerizationofPhenols 97 PatrickGamez 7.1.1 Introduction 97 7.1.2 ChemistryandCatalysis 99 7.1.3 ProcessTechnology 102 7.1.4 NewDevelopments 104 7.2 2,3,5-TrimethylhydroquinoneasaVitaminEIntermediatevia OxidationofMethyl-SubstitutedPhenols 106 JanSchützandThomasNetscher References 109 PartIII Pd-CatalyzedAerobicOxidation 113 8 Pd-CatalyzedAerobicOxidationReactions:IndustrialApplications andNewDevelopments 115 DianWang,JonathanN.Jaworski,andShannonS.Stahl 8.1 Introduction 115 8.2 ChemistryandCatalysis:IndustrialApplications 117 8.2.1 AcetoxylationofAlkenestoVinylorAllylAcetates 117 8.2.2 OxidativeCarbonylationofAlcoholstoCarbonates,Oxalates, andCarbamates 118 8.2.3 OxidativeCouplingofArenestoBiarylCompounds 121 8.3 ChemistryandCatalysis:ApplicationsofPotentialIndustrial Interest 122 8.3.1 OxidationofAlcoholstoAldehydes 122 VIII Contents 8.3.2 OxidationofArenestoPhenolsandPhenylEsters 123 8.3.3 BenzylicAcetoxylation 125 8.3.4 AreneOlefination(OxidativeHeckReaction) 126 8.4 ChemistryandCatalysis:NewDevelopmentsand Opportunities 128 8.4.1 Ligand-ModulatedAerobicOxidationCatalysis 128 8.4.2 UseofNO asCocatalyst 130 x 8.4.3 MethaneOxidation 132 8.5 Conclusion 133 References 133 9 AcetaldehydefromEthyleneandRelatedWacker-TypeReactions 139 ReinhardJira 9.1 Introduction 139 9.2 ChemistryandCatalysis 140 9.2.1 OxidationofOlefinicCompoundstoCarbonylCompounds 140 9.2.2 KineticsandMechanism 140 9.2.3 CatalyticOxidationofEthylene 145 9.2.3.1 OxidationofEthylenetoAcetaldehydeinthePresenceof CuCl 145 2 9.2.3.2 OxidationofEthyleneto2-Chloroethanol 147 9.3 ProcessTechnology(WackerProcess) 148 9.3.1 Single-StageAcetaldehydeProcessfromEthylene 148 9.3.2 Two-StageAcetaldehydeProcessfromEthylene 149 9.4 OtherDevelopments 151 References 155 FurtherReading 158 10 1,4-Butanediolfrom1,3-Butadiene 159 YusukeIzawaandToshiharuYokoyama 10.1 Introduction 159 10.2 ChemistryandCatalysis 160 10.2.1 ShortOverviewofNon-butadiene-BasedRoutesto 1,4-Butanediol 160 10.2.1.1 Acetylene-BasedReppeProcess 160 10.2.1.2 Butane-BasedProcess;SelectiveOxidationofButanetoMaleic Anhydride 161 10.2.1.3 Propylene-BasedProcess:HydroformylationofAllylAlcohol 161 10.2.2 Butadiene-BasedRoutesto1,4-Butanediol 162 10.2.2.1 Oxyhalogenationof1,3-Butadiene 162 10.2.2.2 OxidativeAcetoxylationof1,3-Butadiene 162 10.3 ProcessTechnology 164 10.3.1 MitsubishiChemical’s1,4-ButanediolManufacturingProcess: First-GenerationProcess 165 10.3.1.1 OxidativeAcetoxylationStep 165 Contents IX 10.3.1.2 HydrogenationStep 165 10.3.1.3 HydrolysisStep 166 10.3.2 MitsubishiChemical’s1,4-ButanediolManufacturingProcess: Second-GenerationProcess 167 10.4 NewDevelopments 168 10.4.1 ImprovementoftheCurrentProcess 168 10.4.2 DevelopmentofAlternativeProcesses 169 10.5 SummaryandConclusions 169 References 170 11 MitsubishiChemicalsLiquidPhasePalladium-CatalyzedOxidation Technology:OxidationofCyclohexene,Acrolein,andMethylAcrylate toUsefulIndustrialChemicals 173 YoshiyukiTanaka,JunP.Takahara,TohruSetoyama,andHansE.B.Lempers 11.1 Introduction 173 11.2 ChemistryandCatalysis 174 11.2.1 AerobicPalladium-CatalyzedOxidationofCyclohexeneto 1,4-Dioxospiro-[4,5]-decane 174 11.2.1.1 OptimizationoftheReactionConditions 174 11.2.2 AerobicPalladium-CatalyzedOxidationofOtherTypesof Olefins 176 11.2.3 AerobicPalladium-CatalyzedOxidationofAcroleinto MalonaldehydeBis-(1,3-dioxan-2-yl)-acetalFollowedby Hydrolysis/Hydrogenationto1,3-Propanediol 178 11.3 ProspectsforScale-Up 180 11.3.1 AerobicPalladium-CatalyzedOxidationofMethylAcrylate(MA) to3,3-DimethoxyMethylPropionate:ProcessOptimizationand Scale-Up 180 11.3.2 Small-ScaleReactionOptimization 181 11.3.3 Large-ScaleMethylAcrylateOxidationReactionandWork-Up 184 11.3.4 ReactionSimulationStudiesasAidforFurtherScale-Up 184 11.4 Conclusion 187 References 187 12 OxidativeCarbonylation:DiphenylCarbonate 189 GrigoriiL.Soloveichik 12.1 Introduction 189 12.1.1 DiphenylCarbonateintheManufacturingofPolycarbonates 189 12.1.2 HistoryofDirectDiphenylCarbonateProcessatGE 190 12.2 ChemistryandCatalysis 192 12.2.1 MechanismofOxidativeCarbonylationofPhenol 192 12.2.2 CatalystsforOxidativeCarbonylationofPhenol 193 12.2.3 CocatalystsforOxidativeCarbonylationofPhenol 196 12.2.3.1 OrganicCocatalysts 196 12.2.3.2 InorganicCocatalysts 196 X Contents 12.2.4 MulticomponentCatalyticPackages 199 12.2.5 RoleofBromideinDirectSynthesisofDiphenylCarbonate 199 12.3 ProspectsforScale-Up 201 12.3.1 CatalystOptimization 201 12.3.2 WaterRemovalinDirectDiphenylCarbonateProcess 202 12.3.3 DownstreamProcessingandCatalystRecovery 203 12.4 ConclusionsandOutlook 203 Acknowledgments 204 References 205 13 AerobicOxidativeEsterificationofAldehydeswithAlcohols:The EvolutionfromPd–PbIntermetallicCatalyststoAu–NiO Nanoparticle x CatalystsfortheProductionofMethylMethacrylate 209 KenSuzukiandSetsuoYamamatsu 13.1 Introduction 209 13.2 ChemistryandCatalysis 210 13.2.1 DiscoveryofthePd–PbCatalyst 210 13.2.2 Pd–PbIntermetallicCompounds 210 13.2.3 Mechanism 212 13.2.4 TheRoleofPbinthePd–PbCatalyst 213 13.2.5 IndustrialCatalyst 213 13.3 ProcessTechnology 214 13.4 NewDevelopments 215 13.5 ConclusionandOutlook 217 References 218 PartIV OrganocatalyticAerobicOxidation 219 14 QuinonesinHydrogenPeroxideSynthesisandCatalyticAerobic OxidationReactions 221 AlisonE.WendlandtandShannonS.Stahl 14.1 Introduction 221 14.2 ChemistryandCatalysis:AnthraquinoneOxidation(AO) Process 223 14.2.1 AutoxidationProcess(HydroquinonetoQuinone) 223 14.2.2 HydrogenationProcess(QuinonetoHydroquinone) 225 14.3 ProcessTechnology 227 14.4 FutureDevelopments:SelectiveAerobicOxidationReactions CatalyzedbyQuinones 229 14.4.1 AerobicDDQ-CatalyzedReactionsUsingNO Cocatalysts 229 x 14.4.2 AerobicQuinone-CatalyzedReactionsUsingOther Cocatalysts 230 14.4.3 CAOMimicsandSelectiveOxidationofAmines 231 References 234