GEORGE A. OLAH, PhD, was awarded the undivided 1994 Nobel Prize in Chemistry. He was a Distinguished Professor of Chemistry, Chemical Engineering and Materials Science; Donald P. and Katherine B. Loker Chair in Organic Chemistry; and Founding Director of the Loker Hydrocarbon Research Institute at the University of Southern California, Los Angeles. He passed away on March 8, 2017. ÁRPÁD MOLNÁR, DSc, is an Emeritus Professor at the University of Szeged, Hungary, and a Senior Fellow of the Loker Hydrocarbon Research Institute at the University of Southern California. G. K. SURYA PRAKASH, PhD, is the George A. and Judith A. Olah Nobel Laureate Chair Professor and the Director of the Loker Hydrocarbon Research Institute at the University of Southern California.

• Volume 1Preface to the Third Edition xiiiPreface to the Second Edition xvPreface to the First Edition xviiIntroduction xixIntroduction and General Aspects 11.1 Hydrocarbons and Their Classes 11.2 Energy–Hydrocarbon Relationships 21.3 Hydrocarbon Sources 4Extraterrestrial Hydrocarbons 151.4 Hydrocarbon Production from Natural Sources 161.5 Hydrocarbon Synthesis 201.6 Nonrenewable and Renewable Hydrocarbons 271.7 Regenerative Hydrocarbons from CO2 Emission Capture and Recycling 291.8 Hydrocarbon Functionalization Reactions 301.9 Use of Hydrocarbons, Petroleum Oil 351.9.1 Energy Generation, Storage, and Delivery: Heating 361.9.2 Transportation Fuels 361.9.3 Chemical Products, Plastics, and Pharmaceuticals 38References 38Hydrocarbons from Petroleum and Natural Gas 492.1 Cracking 492.2 Reforming 62Hydroforming 64Metal-Catalyzed Reforming 652.3 Dehydrogenation with Olefin Production 71Heterogeneous Catalysts 73Homogeneous Catalysts 78C2–C3 Alkenes 85C4 Alkenes 86Buta-1,3-diene and Isoprene 87Higher Olefins 88Styrene 882.4 Upgrading of Natural-Gas Liquids 892.5 Aromatics Production 89References 102Synthesis from C Sources 1253.1 Aspects of C1 Chemistry 1263.2 Chemical Reduction to Methanol and Oxygenates; Recycling of CO2 127Heterogeneous Hydrogenation 129Homogeneous Hydrogenation 137Ionic Reduction 143Electrochemical and Electrocatalytic Reduction 143Photoreduction 146Enzymatic Reduction 1483.3 Fischer–Tropsch Chemistry 1493.4 Oxygenation of Methane 166Methanol Synthesis 1663.5 Oligocondensation of Methane 1733.6 Hydrocarbons from Methane Derivatives 186Methanol Conversion to Hydrocarbons 186Methanol to Hydrocarbon Technologies 196Methanol to Gasoline 196Methanol to Olefin 197Methanol to Propylene 198References 200Isomerization 2374.1 Acid-Catalyzed and Bifunctional Isomerization 238Mechanism 243Side-Chain Isomerization 250Positional Isomerization 2504.2 Base-Catalyzed Isomerization 2624.2.1 Alkenes 2624.3 Metal-Catalyzed Isomerization 2664.4 Pericyclic Rearrangements 2774.5 Practical Applications 284Alkanes 284Alkenes 2854.5.2 Isomerization of Xylenes 286References 287Alkylations 3055.1 Acid-Catalyzed Alkylation 305Alkylolysis (Alkylative Cleavage) 317Alkylation of Alkenes with Organic Halides 318Alkylation of Alkynes 320Alkylation with Carbonyl Compounds: The Prins Reaction 320Catalysts 324Alkylation with Alkyl Halides 326Alkylation with Alkenes 331Alkylation with Alkanes 335Alkylation with Other Reagents 3385.2 Base-Catalyzed Alkylation 3505.3 Alkylation through Organometallics 3525.4 Miscellaneous Alkylations 3565.5 Practical Applications 360References 369Addition Reactions 3896.1 Hydration 389Production of Alcohols by Hydration of Alkenes 395Production of Octane-Enhancing Oxygenates 396Acetaldehyde 3976.2 HX Addition 398Alkenes 398Dienes 403Alkynes 404Ethyl Chloride 411Hydrochlorination of Buta-1,3-diene 411Vinyl Chloride 411Ethylene Chlorohydrin 412Propylene Chlorohydrin 412Adiponitrile 412Acrylonitrile 4136.3 Halogen Addition 413Vinyl Chloride 422Chlorination of Buta-1,3-diene 4246.4 Addition to Form C–N Bonds 4246.5 Addition to Form C–O, C–S, and C–P Bonds 4336.6 Hydrometalation 439Alkenes 440Dienes 446Alkynes 448Alkenes 452Dienes 456Alkynes 4576.7 Halometalation 4626.8 Solvometalation 4656.9 Carbometalation 4666.10 Cycloaddition 471References 477Carbonylation and Carboxylation 5097.1 Carbonylation 509Hydroformylation in Biphasic Solvent Systems 515The Use of Heterogeneous Catalysts 516Hydroformylation of Higher Alkenes 518Hydroformylation of Internal Alkenes 519Asymmetric Hydroformylation 5207.2 Carboxylation 533Saturated Hydrocarbons 534Aromatic Hydrocarbons 536Hydrocarboxylation and hydroesterification 539Aminocarboxylation 545Neocarboxylic Acids 547Hydrocarboxymethylation of Long-Chain Alkenes 547Propionic Acid 547Acrylic Acid and Acrylates 548References 548Acylation 5698.1 Acylation of Aromatics 569New Soluble Catalysts 573Solid Catalysts 575The Gattermann–Koch Reaction 577The Gattermann Reaction 579Other Formylations 5808.2 Acylation of Aliphatic Compounds 581References 586Index 000Volume 2Preface to the Third Edition xiPreface to the Second Edition xiiiPreface to the First Edition xvIntroduction xviiOxidation–Oxygenation 5939.1 Oxidation of Alkanes 594Autoxidation of Alkanes 594Oxidation of Methane 596Oxidation with Stoichiometric Oxidants 606Oxidation Catalyzed by Enzymes and Metalloporphyrins 613Metal-Catalyzed Oxidation in the Homogeneous Phase 616Oxidation Induced by Heterogeneous Catalysts 619Metal Oxidants 623Electrophilic Reagents 624Oxygenolysis 6289.2 Oxidation of Alkenes 630Direct Oxidation with Stoichiometric Oxidants 630Metal-Catalyzed Epoxidation 635Epoxidation Catalyzed by Metalloporphyrins 644Asymmetric Epoxidation 647Autoxidation 650Reactions with Singlet Oxygen 650Bis-Hydroxylation 656Bis-Acetoxylation 663Oxidation with Palladium in the Homogeneous Phase 664Oxidation with Other Reagents 669Vinylic Acetoxylation 671Ozonation 673Mechanism 673Synthetic Applications 676Other Oxidants 678Allylic Hydroxylation and Acyloxylation 681Oxidation to α,β-Unsaturated Carbonyl Compounds 6869.3 Oxidation of Alkynes 6909.4 Oxidation of Aromatics 693Oxidation to Phenols 693Ring Acyloxylation 701Oxidation to Quinones 702Oxidation to Arene Oxides and Arene Diols 703Oxidation with Singlet Oxygen 704Oxidation of Methyl-Substituted Aromatics 706Oxidation of Other Arenes 708Benzylic Acetoxylation 7119.5 Practical Applications 712Acetic Acid 712Maleic Anhydride 713Oxidation of Cyclohexane 715Oxidation of Cyclododecane 715sec-Alcohols 715Ethylene Oxide 716Propylene Oxide 718Acetaldehyde and Acetone 719Vinyl Acetate 7191,4-Diacetoxybut-2-ene 720Acrolein and Acrylic Acid 720Methacrolein and Methacrylic Acid 721Acrylonitrile 721Other Processes 722Phenol and Acetone 722Benzoic Acid 723Terephthalic Acid 723Maleic Anhydride 724Phthalic Anhydride 725Anthraquinone 727References 727Heterosubstitution 79510.1 Electrophilic (Acid-Catalyzed) Substitution 795Halogenation 796Nitration 798Sulfuration 799Halogenation 800Nitration 804Sulfonation 808Synthesis of Sulfoxides and Sulfones 810Chlorobenzene 811Nitration of Benzene and Toluene 811Sulfonation of Benzene and Alkylbenzenes 81110.2 Free-Radical Substitution 812Chlorination 812Fluorination 817Bromination 818Iodination 819Side-Chain Halogenation of Arylalkanes 819Chlorination of Alkanes 824Side-Chain Chlorination of Toluene 826Unsaturated Chlorides 826Sulfochlorination of Alkanes 827Nitroalkanes 82710.3 Formation of C–N Bonds 82710.4 Formation of Carbon–Metal Bonds 831Borylation 837Silylation 840Al, Ge, and Sn Derivatives 84110.5 Miscellaneous Derivatives 842References 843Reduction–Hydrogenation 86311.1 Heterogeneous Catalytic Hydrogenation 864Mechanism 866Stereochemistry 87011.2 Homogeneous Catalytic Hydrogenation 886Mechanism 891Selectivity and Stereochemistry 893Asymmetric Hydrogenation 89611.3 Transfer Hydrogenation 90411.4 Chemical and Electrochemical Reduction 906Mechanism 911Selectivity 91111.5 Ionic Hydrogenation 91311.6 Hydrogenolysis of Saturated Hydrocarbons 91811.7 Practical Applications 931C2 Hydrorefining 931C3 Hydrorefining 931C4 Hydrorefining 931Gasoline Hydrorefining 932References 934Metathesis 95912.1 Metathesis of Acyclic Alkenes 96012.2 Alkane Metathesis 97312.3 Metathesis of Alkynes 97612.4 Ring-Closing Metathesis 97812.5 Ring-Opening Metathesis and Ring-Opening Metathesis Polymerization 97912.6 Practical Applications 983References 986Oligomerization and Polymerization 100113.1 Oligomerization 1001Practical Applications 1006Alkenes 1008Alkynes 1013Cyclooligomerization 1014Practical Applications 101813.2 Polymerization 1021Ziegler–Natta Catalysts 1038The Phillips Catalyst 1041Group IV Metallocene Catalysts 1042Postmetallocene Catalysts 1047Stereoregular Polymerization of Propylene 1058Isospecific Polymerization 1059Syndiospecific Polymerization 1064Stereoregular Polymerization of Dienes 1065Ethylene Polymers 1072Polypropylene 1074Polybutylenes 1075Styrene Polymers 1076Polydienes 1077References 1078Outlook 111114.1 Sustainable Hydrocarbon Chemistry for the Future 111114.2 Extraterrestrial Hydrocarbon Chemistry 1114References 1115Index 000

GEORGE A. OLAH, PhD, was awarded the undivided 1994 Nobel Prize in Chemistry. He was a Distinguished Professor of Chemistry, Chemical Engineering and Materials Science; Donald P. and Katherine B. Loker Chair in Organic Chemistry; and Founding Director of the Loker Hydrocarbon Research Institute at the University of Southern California, Los Angeles. He passed away on March 8, 2017. ÁRPÁD MOLNÁR, DSc, is an Emeritus Professor at the University of Szeged, Hungary, and a Senior Fellow of the Loker Hydrocarbon Research Institute at the University of Southern California. G. K. SURYA PRAKASH, PhD, is the George A. and Judith A. Olah Nobel Laureate Chair Professor and the Director of the Loker Hydrocarbon Research Institute at the University of Southern California.

• Volume 1Preface to the Third Edition xiiiPreface to the Second Edition xvPreface to the First Edition xviiIntroduction xixIntroduction and General Aspects 11.1 Hydrocarbons and Their Classes 11.2 Energy–Hydrocarbon Relationships 21.3 Hydrocarbon Sources 4Extraterrestrial Hydrocarbons 151.4 Hydrocarbon Production from Natural Sources 161.5 Hydrocarbon Synthesis 201.6 Nonrenewable and Renewable Hydrocarbons 271.7 Regenerative Hydrocarbons from CO2 Emission Capture and Recycling 291.8 Hydrocarbon Functionalization Reactions 301.9 Use of Hydrocarbons, Petroleum Oil 351.9.1 Energy Generation, Storage, and Delivery: Heating 361.9.2 Transportation Fuels 361.9.3 Chemical Products, Plastics, and Pharmaceuticals 38References 38Hydrocarbons from Petroleum and Natural Gas 492.1 Cracking 492.2 Reforming 62Hydroforming 64Metal-Catalyzed Reforming 652.3 Dehydrogenation with Olefin Production 71Heterogeneous Catalysts 73Homogeneous Catalysts 78C2–C3 Alkenes 85C4 Alkenes 86Buta-1,3-diene and Isoprene 87Higher Olefins 88Styrene 882.4 Upgrading of Natural-Gas Liquids 892.5 Aromatics Production 89References 102Synthesis from C Sources 1253.1 Aspects of C1 Chemistry 1263.2 Chemical Reduction to Methanol and Oxygenates; Recycling of CO2 127Heterogeneous Hydrogenation 129Homogeneous Hydrogenation 137Ionic Reduction 143Electrochemical and Electrocatalytic Reduction 143Photoreduction 146Enzymatic Reduction 1483.3 Fischer–Tropsch Chemistry 1493.4 Oxygenation of Methane 166Methanol Synthesis 1663.5 Oligocondensation of Methane 1733.6 Hydrocarbons from Methane Derivatives 186Methanol Conversion to Hydrocarbons 186Methanol to Hydrocarbon Technologies 196Methanol to Gasoline 196Methanol to Olefin 197Methanol to Propylene 198References 200Isomerization 2374.1 Acid-Catalyzed and Bifunctional Isomerization 238Mechanism 243Side-Chain Isomerization 250Positional Isomerization 2504.2 Base-Catalyzed Isomerization 2624.2.1 Alkenes 2624.3 Metal-Catalyzed Isomerization 2664.4 Pericyclic Rearrangements 2774.5 Practical Applications 284Alkanes 284Alkenes 2854.5.2 Isomerization of Xylenes 286References 287Alkylations 3055.1 Acid-Catalyzed Alkylation 305Alkylolysis (Alkylative Cleavage) 317Alkylation of Alkenes with Organic Halides 318Alkylation of Alkynes 320Alkylation with Carbonyl Compounds: The Prins Reaction 320Catalysts 324Alkylation with Alkyl Halides 326Alkylation with Alkenes 331Alkylation with Alkanes 335Alkylation with Other Reagents 3385.2 Base-Catalyzed Alkylation 3505.3 Alkylation through Organometallics 3525.4 Miscellaneous Alkylations 3565.5 Practical Applications 360References 369Addition Reactions 3896.1 Hydration 389Production of Alcohols by Hydration of Alkenes 395Production of Octane-Enhancing Oxygenates 396Acetaldehyde 3976.2 HX Addition 398Alkenes 398Dienes 403Alkynes 404Ethyl Chloride 411Hydrochlorination of Buta-1,3-diene 411Vinyl Chloride 411Ethylene Chlorohydrin 412Propylene Chlorohydrin 412Adiponitrile 412Acrylonitrile 4136.3 Halogen Addition 413Vinyl Chloride 422Chlorination of Buta-1,3-diene 4246.4 Addition to Form C–N Bonds 4246.5 Addition to Form C–O, C–S, and C–P Bonds 4336.6 Hydrometalation 439Alkenes 440Dienes 446Alkynes 448Alkenes 452Dienes 456Alkynes 4576.7 Halometalation 4626.8 Solvometalation 4656.9 Carbometalation 4666.10 Cycloaddition 471References 477Carbonylation and Carboxylation 5097.1 Carbonylation 509Hydroformylation in Biphasic Solvent Systems 515The Use of Heterogeneous Catalysts 516Hydroformylation of Higher Alkenes 518Hydroformylation of Internal Alkenes 519Asymmetric Hydroformylation 5207.2 Carboxylation 533Saturated Hydrocarbons 534Aromatic Hydrocarbons 536Hydrocarboxylation and hydroesterification 539Aminocarboxylation 545Neocarboxylic Acids 547Hydrocarboxymethylation of Long-Chain Alkenes 547Propionic Acid 547Acrylic Acid and Acrylates 548References 548Acylation 5698.1 Acylation of Aromatics 569New Soluble Catalysts 573Solid Catalysts 575The Gattermann–Koch Reaction 577The Gattermann Reaction 579Other Formylations 5808.2 Acylation of Aliphatic Compounds 581References 586Index 000Volume 2Preface to the Third Edition xiPreface to the Second Edition xiiiPreface to the First Edition xvIntroduction xviiOxidation–Oxygenation 5939.1 Oxidation of Alkanes 594Autoxidation of Alkanes 594Oxidation of Methane 596Oxidation with Stoichiometric Oxidants 606Oxidation Catalyzed by Enzymes and Metalloporphyrins 613Metal-Catalyzed Oxidation in the Homogeneous Phase 616Oxidation Induced by Heterogeneous Catalysts 619Metal Oxidants 623Electrophilic Reagents 624Oxygenolysis 6289.2 Oxidation of Alkenes 630Direct Oxidation with Stoichiometric Oxidants 630Metal-Catalyzed Epoxidation 635Epoxidation Catalyzed by Metalloporphyrins 644Asymmetric Epoxidation 647Autoxidation 650Reactions with Singlet Oxygen 650Bis-Hydroxylation 656Bis-Acetoxylation 663Oxidation with Palladium in the Homogeneous Phase 664Oxidation with Other Reagents 669Vinylic Acetoxylation 671Ozonation 673Mechanism 673Synthetic Applications 676Other Oxidants 678Allylic Hydroxylation and Acyloxylation 681Oxidation to α,β-Unsaturated Carbonyl Compounds 6869.3 Oxidation of Alkynes 6909.4 Oxidation of Aromatics 693Oxidation to Phenols 693Ring Acyloxylation 701Oxidation to Quinones 702Oxidation to Arene Oxides and Arene Diols 703Oxidation with Singlet Oxygen 704Oxidation of Methyl-Substituted Aromatics 706Oxidation of Other Arenes 708Benzylic Acetoxylation 7119.5 Practical Applications 712Acetic Acid 712Maleic Anhydride 713Oxidation of Cyclohexane 715Oxidation of Cyclododecane 715sec-Alcohols 715Ethylene Oxide 716Propylene Oxide 718Acetaldehyde and Acetone 719Vinyl Acetate 7191,4-Diacetoxybut-2-ene 720Acrolein and Acrylic Acid 720Methacrolein and Methacrylic Acid 721Acrylonitrile 721Other Processes 722Phenol and Acetone 722Benzoic Acid 723Terephthalic Acid 723Maleic Anhydride 724Phthalic Anhydride 725Anthraquinone 727References 727Heterosubstitution 79510.1 Electrophilic (Acid-Catalyzed) Substitution 795Halogenation 796Nitration 798Sulfuration 799Halogenation 800Nitration 804Sulfonation 808Synthesis of Sulfoxides and Sulfones 810Chlorobenzene 811Nitration of Benzene and Toluene 811Sulfonation of Benzene and Alkylbenzenes 81110.2 Free-Radical Substitution 812Chlorination 812Fluorination 817Bromination 818Iodination 819Side-Chain Halogenation of Arylalkanes 819Chlorination of Alkanes 824Side-Chain Chlorination of Toluene 826Unsaturated Chlorides 826Sulfochlorination of Alkanes 827Nitroalkanes 82710.3 Formation of C–N Bonds 82710.4 Formation of Carbon–Metal Bonds 831Borylation 837Silylation 840Al, Ge, and Sn Derivatives 84110.5 Miscellaneous Derivatives 842References 843Reduction–Hydrogenation 86311.1 Heterogeneous Catalytic Hydrogenation 864Mechanism 866Stereochemistry 87011.2 Homogeneous Catalytic Hydrogenation 886Mechanism 891Selectivity and Stereochemistry 893Asymmetric Hydrogenation 89611.3 Transfer Hydrogenation 90411.4 Chemical and Electrochemical Reduction 906Mechanism 911Selectivity 91111.5 Ionic Hydrogenation 91311.6 Hydrogenolysis of Saturated Hydrocarbons 91811.7 Practical Applications 931C2 Hydrorefining 931C3 Hydrorefining 931C4 Hydrorefining 931Gasoline Hydrorefining 932References 934Metathesis 95912.1 Metathesis of Acyclic Alkenes 96012.2 Alkane Metathesis 97312.3 Metathesis of Alkynes 97612.4 Ring-Closing Metathesis 97812.5 Ring-Opening Metathesis and Ring-Opening Metathesis Polymerization 97912.6 Practical Applications 983References 986Oligomerization and Polymerization 100113.1 Oligomerization 1001Practical Applications 1006Alkenes 1008Alkynes 1013Cyclooligomerization 1014Practical Applications 101813.2 Polymerization 1021Ziegler–Natta Catalysts 1038The Phillips Catalyst 1041Group IV Metallocene Catalysts 1042Postmetallocene Catalysts 1047Stereoregular Polymerization of Propylene 1058Isospecific Polymerization 1059Syndiospecific Polymerization 1064Stereoregular Polymerization of Dienes 1065Ethylene Polymers 1072Polypropylene 1074Polybutylenes 1075Styrene Polymers 1076Polydienes 1077References 1078Outlook 111114.1 Sustainable Hydrocarbon Chemistry for the Future 111114.2 Extraterrestrial Hydrocarbon Chemistry 1114References 1115Index 000

GEORGE A. OLAH, PhD, was awarded the undivided 1994 Nobel Prize in Chemistry. He was a Distinguished Professor of Chemistry, Chemical Engineering and Materials Science; Donald P. and Katherine B. Loker Chair in Organic Chemistry; and Founding Director of the Loker Hydrocarbon Research Institute at the University of Southern California, Los Angeles. He passed away on March 8, 2017. ÁRPÁD MOLNÁR, DSc, is an Emeritus Professor at the University of Szeged, Hungary, and a Senior Fellow of the Loker Hydrocarbon Research Institute at the University of Southern California. G. K. SURYA PRAKASH, PhD, is the George A. and Judith A. Olah Nobel Laureate Chair Professor and the Director of the Loker Hydrocarbon Research Institute at the University of Southern California.

• Volume 1Preface to the Third Edition xiiiPreface to the Second Edition xvPreface to the First Edition xviiIntroduction xixIntroduction and General Aspects 11.1 Hydrocarbons and Their Classes 11.2 Energy–Hydrocarbon Relationships 21.3 Hydrocarbon Sources 4Extraterrestrial Hydrocarbons 151.4 Hydrocarbon Production from Natural Sources 161.5 Hydrocarbon Synthesis 201.6 Nonrenewable and Renewable Hydrocarbons 271.7 Regenerative Hydrocarbons from CO2 Emission Capture and Recycling 291.8 Hydrocarbon Functionalization Reactions 301.9 Use of Hydrocarbons, Petroleum Oil 351.9.1 Energy Generation, Storage, and Delivery: Heating 361.9.2 Transportation Fuels 361.9.3 Chemical Products, Plastics, and Pharmaceuticals 38References 38Hydrocarbons from Petroleum and Natural Gas 492.1 Cracking 492.2 Reforming 62Hydroforming 64Metal-Catalyzed Reforming 652.3 Dehydrogenation with Olefin Production 71Heterogeneous Catalysts 73Homogeneous Catalysts 78C2–C3 Alkenes 85C4 Alkenes 86Buta-1,3-diene and Isoprene 87Higher Olefins 88Styrene 882.4 Upgrading of Natural-Gas Liquids 892.5 Aromatics Production 89References 102Synthesis from C Sources 1253.1 Aspects of C1 Chemistry 1263.2 Chemical Reduction to Methanol and Oxygenates; Recycling of CO2 127Heterogeneous Hydrogenation 129Homogeneous Hydrogenation 137Ionic Reduction 143Electrochemical and Electrocatalytic Reduction 143Photoreduction 146Enzymatic Reduction 1483.3 Fischer–Tropsch Chemistry 1493.4 Oxygenation of Methane 166Methanol Synthesis 1663.5 Oligocondensation of Methane 1733.6 Hydrocarbons from Methane Derivatives 186Methanol Conversion to Hydrocarbons 186Methanol to Hydrocarbon Technologies 196Methanol to Gasoline 196Methanol to Olefin 197Methanol to Propylene 198References 200Isomerization 2374.1 Acid-Catalyzed and Bifunctional Isomerization 238Mechanism 243Side-Chain Isomerization 250Positional Isomerization 2504.2 Base-Catalyzed Isomerization 2624.2.1 Alkenes 2624.3 Metal-Catalyzed Isomerization 2664.4 Pericyclic Rearrangements 2774.5 Practical Applications 284Alkanes 284Alkenes 2854.5.2 Isomerization of Xylenes 286References 287Alkylations 3055.1 Acid-Catalyzed Alkylation 305Alkylolysis (Alkylative Cleavage) 317Alkylation of Alkenes with Organic Halides 318Alkylation of Alkynes 320Alkylation with Carbonyl Compounds: The Prins Reaction 320Catalysts 324Alkylation with Alkyl Halides 326Alkylation with Alkenes 331Alkylation with Alkanes 335Alkylation with Other Reagents 3385.2 Base-Catalyzed Alkylation 3505.3 Alkylation through Organometallics 3525.4 Miscellaneous Alkylations 3565.5 Practical Applications 360References 369Addition Reactions 3896.1 Hydration 389Production of Alcohols by Hydration of Alkenes 395Production of Octane-Enhancing Oxygenates 396Acetaldehyde 3976.2 HX Addition 398Alkenes 398Dienes 403Alkynes 404Ethyl Chloride 411Hydrochlorination of Buta-1,3-diene 411Vinyl Chloride 411Ethylene Chlorohydrin 412Propylene Chlorohydrin 412Adiponitrile 412Acrylonitrile 4136.3 Halogen Addition 413Vinyl Chloride 422Chlorination of Buta-1,3-diene 4246.4 Addition to Form C–N Bonds 4246.5 Addition to Form C–O, C–S, and C–P Bonds 4336.6 Hydrometalation 439Alkenes 440Dienes 446Alkynes 448Alkenes 452Dienes 456Alkynes 4576.7 Halometalation 4626.8 Solvometalation 4656.9 Carbometalation 4666.10 Cycloaddition 471References 477Carbonylation and Carboxylation 5097.1 Carbonylation 509Hydroformylation in Biphasic Solvent Systems 515The Use of Heterogeneous Catalysts 516Hydroformylation of Higher Alkenes 518Hydroformylation of Internal Alkenes 519Asymmetric Hydroformylation 5207.2 Carboxylation 533Saturated Hydrocarbons 534Aromatic Hydrocarbons 536Hydrocarboxylation and hydroesterification 539Aminocarboxylation 545Neocarboxylic Acids 547Hydrocarboxymethylation of Long-Chain Alkenes 547Propionic Acid 547Acrylic Acid and Acrylates 548References 548Acylation 5698.1 Acylation of Aromatics 569New Soluble Catalysts 573Solid Catalysts 575The Gattermann–Koch Reaction 577The Gattermann Reaction 579Other Formylations 5808.2 Acylation of Aliphatic Compounds 581References 586Index 000Volume 2Preface to the Third Edition xiPreface to the Second Edition xiiiPreface to the First Edition xvIntroduction xviiOxidation–Oxygenation 5939.1 Oxidation of Alkanes 594Autoxidation of Alkanes 594Oxidation of Methane 596Oxidation with Stoichiometric Oxidants 606Oxidation Catalyzed by Enzymes and Metalloporphyrins 613Metal-Catalyzed Oxidation in the Homogeneous Phase 616Oxidation Induced by Heterogeneous Catalysts 619Metal Oxidants 623Electrophilic Reagents 624Oxygenolysis 6289.2 Oxidation of Alkenes 630Direct Oxidation with Stoichiometric Oxidants 630Metal-Catalyzed Epoxidation 635Epoxidation Catalyzed by Metalloporphyrins 644Asymmetric Epoxidation 647Autoxidation 650Reactions with Singlet Oxygen 650Bis-Hydroxylation 656Bis-Acetoxylation 663Oxidation with Palladium in the Homogeneous Phase 664Oxidation with Other Reagents 669Vinylic Acetoxylation 671Ozonation 673Mechanism 673Synthetic Applications 676Other Oxidants 678Allylic Hydroxylation and Acyloxylation 681Oxidation to α,β-Unsaturated Carbonyl Compounds 6869.3 Oxidation of Alkynes 6909.4 Oxidation of Aromatics 693Oxidation to Phenols 693Ring Acyloxylation 701Oxidation to Quinones 702Oxidation to Arene Oxides and Arene Diols 703Oxidation with Singlet Oxygen 704Oxidation of Methyl-Substituted Aromatics 706Oxidation of Other Arenes 708Benzylic Acetoxylation 7119.5 Practical Applications 712Acetic Acid 712Maleic Anhydride 713Oxidation of Cyclohexane 715Oxidation of Cyclododecane 715sec-Alcohols 715Ethylene Oxide 716Propylene Oxide 718Acetaldehyde and Acetone 719Vinyl Acetate 7191,4-Diacetoxybut-2-ene 720Acrolein and Acrylic Acid 720Methacrolein and Methacrylic Acid 721Acrylonitrile 721Other Processes 722Phenol and Acetone 722Benzoic Acid 723Terephthalic Acid 723Maleic Anhydride 724Phthalic Anhydride 725Anthraquinone 727References 727Heterosubstitution 79510.1 Electrophilic (Acid-Catalyzed) Substitution 795Halogenation 796Nitration 798Sulfuration 799Halogenation 800Nitration 804Sulfonation 808Synthesis of Sulfoxides and Sulfones 810Chlorobenzene 811Nitration of Benzene and Toluene 811Sulfonation of Benzene and Alkylbenzenes 81110.2 Free-Radical Substitution 812Chlorination 812Fluorination 817Bromination 818Iodination 819Side-Chain Halogenation of Arylalkanes 819Chlorination of Alkanes 824Side-Chain Chlorination of Toluene 826Unsaturated Chlorides 826Sulfochlorination of Alkanes 827Nitroalkanes 82710.3 Formation of C–N Bonds 82710.4 Formation of Carbon–Metal Bonds 831Borylation 837Silylation 840Al, Ge, and Sn Derivatives 84110.5 Miscellaneous Derivatives 842References 843Reduction–Hydrogenation 86311.1 Heterogeneous Catalytic Hydrogenation 864Mechanism 866Stereochemistry 87011.2 Homogeneous Catalytic Hydrogenation 886Mechanism 891Selectivity and Stereochemistry 893Asymmetric Hydrogenation 89611.3 Transfer Hydrogenation 90411.4 Chemical and Electrochemical Reduction 906Mechanism 911Selectivity 91111.5 Ionic Hydrogenation 91311.6 Hydrogenolysis of Saturated Hydrocarbons 91811.7 Practical Applications 931C2 Hydrorefining 931C3 Hydrorefining 931C4 Hydrorefining 931Gasoline Hydrorefining 932References 934Metathesis 95912.1 Metathesis of Acyclic Alkenes 96012.2 Alkane Metathesis 97312.3 Metathesis of Alkynes 97612.4 Ring-Closing Metathesis 97812.5 Ring-Opening Metathesis and Ring-Opening Metathesis Polymerization 97912.6 Practical Applications 983References 986Oligomerization and Polymerization 100113.1 Oligomerization 1001Practical Applications 1006Alkenes 1008Alkynes 1013Cyclooligomerization 1014Practical Applications 101813.2 Polymerization 1021Ziegler–Natta Catalysts 1038The Phillips Catalyst 1041Group IV Metallocene Catalysts 1042Postmetallocene Catalysts 1047Stereoregular Polymerization of Propylene 1058Isospecific Polymerization 1059Syndiospecific Polymerization 1064Stereoregular Polymerization of Dienes 1065Ethylene Polymers 1072Polypropylene 1074Polybutylenes 1075Styrene Polymers 1076Polydienes 1077References 1078Outlook 111114.1 Sustainable Hydrocarbon Chemistry for the Future 111114.2 Extraterrestrial Hydrocarbon Chemistry 1114References 1115Index 000