Hydrocarbon Chemistry, 2 Volume Set

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 1

Preface to the Third Edition xiii

Preface to the Second Edition xv

Preface to the First Edition xvii

Introduction xix

Introduction and General Aspects 1

1.1 Hydrocarbons and Their Classes 1

1.2 Energy–Hydrocarbon Relationships 2

1.3 Hydrocarbon Sources 4

Extraterrestrial Hydrocarbons 15

1.4 Hydrocarbon Production from Natural Sources 16

1.5 Hydrocarbon Synthesis 20

1.6 Nonrenewable and Renewable Hydrocarbons 27

1.7 Regenerative Hydrocarbons from CO2 Emission Capture and Recycling 29

1.8 Hydrocarbon Functionalization Reactions 30

1.9 Use of Hydrocarbons, Petroleum Oil 35

1.9.1 Energy Generation, Storage, and Delivery: Heating 36

1.9.2 Transportation Fuels 36

1.9.3 Chemical Products, Plastics, and Pharmaceuticals 38

References 38

Hydrocarbons from Petroleum and Natural Gas 49

2.1 Cracking 49

2.2 Reforming 62

Hydroforming 64

Metal-Catalyzed Reforming 65

2.3 Dehydrogenation with Olefin Production 71

Heterogeneous Catalysts 73

Homogeneous Catalysts 78

C2–C3 Alkenes 85

C4 Alkenes 86

Buta-1,3-diene and Isoprene 87

Higher Olefins 88

Styrene 88

2.4 Upgrading of Natural-Gas Liquids 89

2.5 Aromatics Production 89

References 102

Synthesis from C Sources 125

3.1 Aspects of C1 Chemistry 126

3.2 Chemical Reduction to Methanol and Oxygenates; Recycling of CO2 127

Heterogeneous Hydrogenation 129

Homogeneous Hydrogenation 137

Ionic Reduction 143

Electrochemical and Electrocatalytic Reduction 143

Photoreduction 146

Enzymatic Reduction 148

3.3 Fischer–Tropsch Chemistry 149

3.4 Oxygenation of Methane 166

Methanol Synthesis 166

3.5 Oligocondensation of Methane 173

3.6 Hydrocarbons from Methane Derivatives 186

Methanol Conversion to Hydrocarbons 186

Methanol to Hydrocarbon Technologies 196

Methanol to Gasoline 196

Methanol to Olefin 197

Methanol to Propylene 198

References 200

Isomerization 237

4.1 Acid-Catalyzed and Bifunctional Isomerization 238

Mechanism 243

Side-Chain Isomerization 250

Positional Isomerization 250

4.2 Base-Catalyzed Isomerization 262

4.2.1 Alkenes 262

4.3 Metal-Catalyzed Isomerization 266

4.4 Pericyclic Rearrangements 277

4.5 Practical Applications 284

Alkanes 284

Alkenes 285

4.5.2 Isomerization of Xylenes 286

References 287

Alkylations 305

5.1 Acid-Catalyzed Alkylation 305

Alkylolysis (Alkylative Cleavage) 317

Alkylation of Alkenes with Organic Halides 318

Alkylation of Alkynes 320

Alkylation with Carbonyl Compounds: The Prins Reaction 320

Catalysts 324

Alkylation with Alkyl Halides 326

Alkylation with Alkenes 331

Alkylation with Alkanes 335

Alkylation with Other Reagents 338

5.2 Base-Catalyzed Alkylation 350

5.3 Alkylation through Organometallics 352

5.4 Miscellaneous Alkylations 356

5.5 Practical Applications 360

References 369

Addition Reactions 389

6.1 Hydration 389

Production of Alcohols by Hydration of Alkenes 395

Production of Octane-Enhancing Oxygenates 396

Acetaldehyde 397

6.2 HX Addition 398

Alkenes 398

Dienes 403

Alkynes 404

Ethyl Chloride 411

Hydrochlorination of Buta-1,3-diene 411

Vinyl Chloride 411

Ethylene Chlorohydrin 412

Propylene Chlorohydrin 412

Adiponitrile 412

Acrylonitrile 413

6.3 Halogen Addition 413

Vinyl Chloride 422

Chlorination of Buta-1,3-diene 424

6.4 Addition to Form C–N Bonds 424

6.5 Addition to Form C–O, C–S, and C–P Bonds 433

6.6 Hydrometalation 439

Alkenes 440

Dienes 446

Alkynes 448

Alkenes 452

Dienes 456

Alkynes 457

6.7 Halometalation 462

6.8 Solvometalation 465

6.9 Carbometalation 466

6.10 Cycloaddition 471

References 477

Carbonylation and Carboxylation 509

7.1 Carbonylation 509

Hydroformylation in Biphasic Solvent Systems 515

The Use of Heterogeneous Catalysts 516

Hydroformylation of Higher Alkenes 518

Hydroformylation of Internal Alkenes 519

Asymmetric Hydroformylation 520

7.2 Carboxylation 533

Saturated Hydrocarbons 534

Aromatic Hydrocarbons 536

Hydrocarboxylation and hydroesterification 539

Aminocarboxylation 545

Neocarboxylic Acids 547

Hydrocarboxymethylation of Long-Chain Alkenes 547

Propionic Acid 547

Acrylic Acid and Acrylates 548

References 548

Acylation 569

8.1 Acylation of Aromatics 569

New Soluble Catalysts 573

Solid Catalysts 575

The Gattermann–Koch Reaction 577

The Gattermann Reaction 579

Other Formylations 580

8.2 Acylation of Aliphatic Compounds 581

References 586

Index 000

Volume 2

Preface to the Third Edition xi

Preface to the Second Edition xiii

Preface to the First Edition xv

Introduction xvii

Oxidation–Oxygenation 593

9.1 Oxidation of Alkanes 594

Autoxidation of Alkanes 594

Oxidation of Methane 596

Oxidation with Stoichiometric Oxidants 606

Oxidation Catalyzed by Enzymes and Metalloporphyrins 613

Metal-Catalyzed Oxidation in the Homogeneous Phase 616

Oxidation Induced by Heterogeneous Catalysts 619

Metal Oxidants 623

Electrophilic Reagents 624

Oxygenolysis 628

9.2 Oxidation of Alkenes 630

Direct Oxidation with Stoichiometric Oxidants 630

Metal-Catalyzed Epoxidation 635

Epoxidation Catalyzed by Metalloporphyrins 644

Asymmetric Epoxidation 647

Autoxidation 650

Reactions with Singlet Oxygen 650

Bis-Hydroxylation 656

Bis-Acetoxylation 663

Oxidation with Palladium in the Homogeneous Phase 664

Oxidation with Other Reagents 669

Vinylic Acetoxylation 671

Ozonation 673

Mechanism 673

Synthetic Applications 676

Other Oxidants 678

Allylic Hydroxylation and Acyloxylation 681

Oxidation to α,β-Unsaturated Carbonyl Compounds 686

9.3 Oxidation of Alkynes 690

9.4 Oxidation of Aromatics 693

Oxidation to Phenols 693

Ring Acyloxylation 701

Oxidation to Quinones 702

Oxidation to Arene Oxides and Arene Diols 703

Oxidation with Singlet Oxygen 704

Oxidation of Methyl-Substituted Aromatics 706

Oxidation of Other Arenes 708

Benzylic Acetoxylation 711

9.5 Practical Applications 712

Acetic Acid 712

Maleic Anhydride 713

Oxidation of Cyclohexane 715

Oxidation of Cyclododecane 715

sec-Alcohols 715

Ethylene Oxide 716

Propylene Oxide 718

Acetaldehyde and Acetone 719

Vinyl Acetate 719

1,4-Diacetoxybut-2-ene 720

Acrolein and Acrylic Acid 720

Methacrolein and Methacrylic Acid 721

Acrylonitrile 721

Other Processes 722

Phenol and Acetone 722

Benzoic Acid 723

Terephthalic Acid 723

Maleic Anhydride 724

Phthalic Anhydride 725

Anthraquinone 727

References 727

Heterosubstitution 795

10.1 Electrophilic (Acid-Catalyzed) Substitution 795

Halogenation 796

Nitration 798

Sulfuration 799

Halogenation 800

Nitration 804

Sulfonation 808

Synthesis of Sulfoxides and Sulfones 810

Chlorobenzene 811

Nitration of Benzene and Toluene 811

Sulfonation of Benzene and Alkylbenzenes 811

10.2 Free-Radical Substitution 812

Chlorination 812

Fluorination 817

Bromination 818

Iodination 819

Side-Chain Halogenation of Arylalkanes 819

Chlorination of Alkanes 824

Side-Chain Chlorination of Toluene 826

Unsaturated Chlorides 826

Sulfochlorination of Alkanes 827

Nitroalkanes 827

10.3 Formation of C–N Bonds 827

10.4 Formation of Carbon–Metal Bonds 831

Borylation 837

Silylation 840

Al, Ge, and Sn Derivatives 841

10.5 Miscellaneous Derivatives 842

References 843

Reduction–Hydrogenation 863

11.1 Heterogeneous Catalytic Hydrogenation 864

Mechanism 866

Stereochemistry 870

11.2 Homogeneous Catalytic Hydrogenation 886

Mechanism 891

Selectivity and Stereochemistry 893

Asymmetric Hydrogenation 896

11.3 Transfer Hydrogenation 904

11.4 Chemical and Electrochemical Reduction 906

Mechanism 911

Selectivity 911

11.5 Ionic Hydrogenation 913

11.6 Hydrogenolysis of Saturated Hydrocarbons 918

11.7 Practical Applications 931

C2 Hydrorefining 931

C3 Hydrorefining 931

C4 Hydrorefining 931

Gasoline Hydrorefining 932

References 934

Metathesis 959

12.1 Metathesis of Acyclic Alkenes 960

12.2 Alkane Metathesis 973

12.3 Metathesis of Alkynes 976

12.4 Ring-Closing Metathesis 978

12.5 Ring-Opening Metathesis and Ring-Opening Metathesis Polymerization 979

12.6 Practical Applications 983

References 986

Oligomerization and Polymerization 1001

13.1 Oligomerization 1001

Practical Applications 1006

Alkenes 1008

Alkynes 1013

Cyclooligomerization 1014

Practical Applications 1018

13.2 Polymerization 1021

Ziegler–Natta Catalysts 1038

The Phillips Catalyst 1041

Group IV Metallocene Catalysts 1042

Postmetallocene Catalysts 1047

Stereoregular Polymerization of Propylene 1058

Isospecific Polymerization 1059

Syndiospecific Polymerization 1064

Stereoregular Polymerization of Dienes 1065

Ethylene Polymers 1072

Polypropylene 1074

Polybutylenes 1075

Styrene Polymers 1076

Polydienes 1077

References 1078

Outlook 1111

14.1 Sustainable Hydrocarbon Chemistry for the Future 1111

14.2 Extraterrestrial Hydrocarbon Chemistry 1114

References 1115

Index 000

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