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HYDROCARBONCHEMISTRY

SECOND EDITION

George A. OlahLoker Hydrocarbon Research Institute and Department of Chemistry

University of Southern California

Los Angeles, California

Árpád MolnárDepartment of Organic Chemistry

University of Szeged

Szeged, Hungary

A JOHN WILEY & SONS, INC., PUBLICATION

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HYDROCARBON CHEMISTRY

Dedicated to Katherine Bogdanovich Loker,friend and generous supporter of hydrocarbon research.

HYDROCARBONCHEMISTRY

SECOND EDITION

George A. OlahLoker Hydrocarbon Research Institute and Department of Chemistry

University of Southern California

Los Angeles, California

Árpád MolnárDepartment of Organic Chemistry

University of Szeged

Szeged, Hungary

A JOHN WILEY & SONS, INC., PUBLICATION

Copyright # 2003 by John Wiley & Sons, Inc. All rights reserved.

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Library of Congress Cataloging-in-Publication Data:

Olah, George A. (George Andrew), 1927–

Hydrocarbon chemistry / George A. Olah, Arpad Molnar. – 2nd ed.

p. cm.

Includes index.

ISBN 0-471-41782-3 (Cloth)

1. Hydrocarbons. I. Molnâar. âArpâad, 1942– II. Title.

QD305.H5 043 2003

5470.01–dc21 2002154116

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

http://www.copyright.com

CONTENTS

Preface to the Second Edition xix

Preface to the First Edition xxi

Introduction xxiii

1 General Aspects 1

1.1. Hydrocarbons and Their Classes / 1

1.2. Energy–Hydrocarbon Relationship / 2

1.3. Hydrocarbon Sources and Separation / 4

1.3.1. Natural Gas / 5

1.3.2. Petroleum or Crude Oil / 6

1.3.3. Heavy Oils, Shale, and Tar Sand / 7

1.3.4. Coal and Its Liquefaction / 8

1.4. Petroleum Refining and Upgrading / 10

1.4.1. Distillation of Crude Petroleum / 10

1.4.2. Hydrocarbon Refining and Conversion Processes / 11

1.5. Finite, Nonrenewable Hydrocarbon Resources / 13

1.6. Hydrocarbon Synthesis / 14

1.6.1. Syngas (CO��H2)-Based Fischer–Tropsch Synthesis / 151.6.2. Methyl Alcohol Conversion / 16

1.6.3. Carbon Dioxide Conversion / 17

1.6.4. Direct Methane Conversion / 17

1.7. Chemical Nature of Hydrocarbon Conversion Reactions / 20

1.7.1. Homolytic (Free-Radical) Reactions / 20

1.7.2. Heterolytic (Ionic) Reactions / 20

1.8. Use of Hydrocarbons / 23

1.8.1. Refined Petroleum Products / 23

1.8.2. Transportation Fuels / 23

1.8.3. Chemicals and Plastics / 25

References and Notes / 25

v

2 Hydrocarbon from Petroleum and Natural Gas 30

2.1. Cracking / 30

2.1.1. Cracking Processes / 30

2.1.2. Mechanism of Cracking / 33

2.1.3. Comparison of Cracking Operations / 36

2.2. Reforming / 38

2.2.1. Thermal Reforming / 39

2.2.2. Catalytic Reforming / 40

Hydroforming / 40

Metal-Catalyzed Reforming / 41

2.3. Dehydrogenation with Olefin Production / 44

2.3.1. Thermal Dehydrogenation / 45

2.3.2. Catalytic Dehydrogenation to Alkenes / 46

2.3.3. Practical Applications / 47

C2–C3 Alkenes / 47

C4 Alkenes / 48

1,3-Butadiene and Isoprene / 48

Higher Olefins / 49

Styrene / 50

2.4. Upgrading of Natural-Gas Liquids / 50

2.5. Aromatics Production / 51

2.5.1. Catalytic Dehydrogenation and Dehydrocyclization / 51


2.6. Recent Developments / 57

2.6.1. Cracking / 57

2.6.2. Reforming / 60

2.6.3. Dehydrogenation with Olefin Production / 62

Catalytic Dehydrogenation / 62

Oxidative Dehydrogenation / 64

2.6.4. Aromatics Production / 66

References / 70

3 Synthesis from C1 Sources 85

3.1. Nature’s C1 Chemistry / 86

3.2. The Chemical Reduction and Recycling of CO2 / 86

3.2.1. Catalytic Reduction / 88

Heterogeneous Hydrogenation / 88

Homogeneous Hydrogenation / 94

3.2.2. Other Reductions / 95

Ionic Reduction / 95

vi CONTENTS

Electrochemical and Electrocatalytic Reduction / 96

Photoreduction / 97

Enzymatic Reduction / 99

3.3. Fischer–Tropsch Chemistry / 100

3.3.1. Catalysts / 102

3.3.2. Mechanism / 103

3.3.3. Related Processes / 107

3.4. Direct Coupling of Methane / 109

3.4.1. Catalytic Oxidative Condensation / 109

3.4.2. High-Temperature Self-Coupling / 113

3.5. Hydrocarbons through Methane Derivatives / 114

3.5.1. Hydrocarbons through Methanol / 114

Methanol Synthesis / 114

Methanol Conversion to Hydrocarbons / 117

3.5.2. Hydrocarbons through Methyl Halides / 123

3.5.3. Hydrocarbons through Sulfurated Methanes / 123


3.6.1. Fischer–Tropsch Chemistry / 124

Fischer–Tropsch Synthesis / 124

Related Processes / 127

3.6.2. Direct Coupling of Methane / 129

Catalytic Oxidative Condensation / 129

Other Processes / 130

3.6.3. Hydrocarbons through Methane Derivatives / 132

Methanol Synthesis / 132

Methanol Conversion to Hydrocarbons / 136

References / 137

4 Isomerization 160

4.1. Acid-Catalyzed Isomerization / 161

4.1.1. Alkanes / 161

Mechanism / 165

4.1.2. Arylalkanes / 170

Side-Chain Isomerization / 170

Positional Isomerization / 170

4.1.3. Alkenes and Dienes / 174

4.2. Base-Catalyzed Isomerization / 177

4.2.1. Alkenes / 177

4.2.2. The Reversible Acetylene–Allene Transformation / 180

CONTENTS vii

4.3. Metal-Catalyzed Isomerization / 182

4.3.1. Alkanes / 182

4.3.2. Alkenes / 185

4.4. Pericyclic Rearrangements / 189

4.5. Practical Applications / 192

4.5.1. Isomerization of C4–C6 Hydrocarbons / 192

Alkanes / 192

Alkenes / 193

4.5.2. Isomerization of Xylenes / 193


4.6.1. Acid-Catalyzed and Bifunctional Isomerization / 194

Alkanes / 194

Alkenes / 196

Xylenes / 197

The Acetylene–Allene Rearrangement / 198

4.6.2. Metal-Catalyzed Isomerization / 199

4.6.3. Pericyclic Rearrangements / 199

References / 201

5 Alkylation 215

5.1. Acid-Catalyzed Alkylation / 215

5.1.1. Alkylation of Alkanes with Alkenes / 215

5.1.2. Alkylation of Alkanes under Superacidic

Conditions / 221

Alkylolysis (Alkylative Cleavage) / 225

5.1.3. Alkylation of Alkenes and Alkynes / 225

Alkylation of Alkenes with Organic Halides / 225

Alkylation of Alkynes / 227

Alkylation with Carbonyl Compounds: The Prins

Reaction / 228

5.1.4. Alkylation of Aromatics / 229

Catalysts / 230

Alkylation with Alkyl Halides / 232

Alkylation with Alkenes / 238

Alkylation with Alkanes / 241

Alkylation with Alcohols / 244

Transalkylation and Dealkylation / 246

5.2. Base-Catalyzed Alkylation / 248

5.3. Alkylation through Organometallics / 250

5.4. Miscellaneous Alkylations / 253


viii CONTENTS

5.5.1. Isoalkane–Alkene Alkylation / 254

5.5.2. Ethylbenzene / 257

5.5.3. Cumene / 258

5.5.4. Xylenes / 258

5.5.5. p-Ethyltoluene / 259

5.5.6. Detergent Alkylates / 260


5.6.1. Alkane–Alkene Alkylation / 260

5.6.2. The Prins Reaction / 262

5.6.3. Alkylation of Aromatics / 262

Solid Acid Catalysts / 262

Specific Examples / 265

Side-Chain Alkylation / 267

Transalkylation / 268

5.6.4. Miscellaneous Alkylations / 268References / 269

6 Addition 284

6.1. Hydration / 284

6.1.1. Alkenes and Dienes / 285

6.1.2. Alkynes / 287


Production of Alcohols by Hydration of Alkenes / 288

Production of Octane-Enhancing Oxygenates / 289

Acetaldehyde / 290

6.2. HX addition / 290

6.2.1. Hydrohalogenation / 290

Alkenes / 290

Dienes / 295

Alkynes / 296

6.2.2. Hypohalous Acids and Hypohalites / 297

6.2.3. Hydrogen Cyanide / 299


Ethyl Chloride / 301

Hydrochlorination of 1,3-Butadiene / 301

Vinyl Chloride / 301

Ethylene Chlorohydrin / 302

Propylene Chlorohydrin / 302

Adiponitrile / 303

Acrylonitrile / 303

6.3. Halogen Addition / 304

6.3.1. Alkenes / 304

CONTENTS ix

6.3.2. Dienes / 308

6.3.3. Alkynes / 310


Vinyl Chloride / 310

Chlorination of 1,3-Butadiene / 312

6.4. Ammonia and Amine Addition / 312

6.4.1. Alkenes / 312

6.4.2. Dienes / 313

6.4.3. Alkynes / 314

6.5. Hydrometallation / 315

6.5.1. Hydroboration / 315

Alkenes / 316

Dienes / 319

Alkynes / 320

6.5.2. Hydroalanation / 321

6.5.3. Hydrosilylation / 322

Alkenes / 323

Dienes / 324

Alkynes / 325

6.5.4. Hydrozirconation / 326

6.6. Halometallation / 327

6.7. Solvometallation / 329

6.7.1. Solvomercuration / 329

6.7.2. Oxythallation / 330

6.8. Carbometallation / 330

6.9. Cycloaddition / 332


6.10.1. Hydration / 336

6.10.2. Hydrohalogenation / 336

6.10.3. Halogen Addition / 337

6.10.4. Hydroamination / 339

6.10.5. Hydrometallation / 341

Hydroboration / 341

Hydrosilylation / 342

Hydrozirconation / 344

Other Hydrometallations / 345

6.10.6. Halometallation / 345

6.10.7. Solvometallation / 346

6.10.8. Carbometallation / 346

6.10.9. Cycloaddition / 347

References / 349

x CONTENTS

7 Carbonylation 371

7.1. Hydroformylation / 371

7.1.1. Alkenes / 372

7.1.2. Dienes and Alkynes / 377

7.1.3. Synthesis of Aldehydes and Alcohols by the Oxo

Reaction / 377

7.2. Carboxylation / 379

7.2.1. Koch Reaction / 379

7.2.2. Carboxylation Catalyzed by Transition Metals / 381

Alkenes and Dienes / 381

Alkynes / 383

Alcohols / 383

7.2.3. Carboxylation of Saturated Hydrocarbons / 384


Neocarboxylic Acids / 384

Hydrocarboxymethylation of Long-Chain Alkenes / 385

Propionic Acid / 385

Acrylic Acid and Acrylates / 385

Acetic Acid / 386

Dimethyl Carbonate / 386

7.3. Aminomethylation / 386


7.4.1. Hydroformylation / 387

Alkynes / 389

Asymmetric Hydroformylation / 390

7.4.2. Formylation of Alkanes / 390

7.4.3. Carboxylation / 391

Alkenes and Alkynes / 391

Alkanes / 392

7.4.4. Aminomethylation / 394

References / 395

8 Acylation 407

8.1. Acylation of Aromatics / 407

8.1.1. General Characteristics / 407

8.1.2. Catalysts and Reaction Conditions / 409

8.1.3. Recent Developments / 410

New Soluble Catalysts / 410

Solid Catalysts / 412

CONTENTS xi

8.2. Related Acylations / 413

8.2.1. Formylation / 413

The Gattermann–Koch Reaction / 413

The Gattermann Reaction / 415

Other Formylations / 416

8.2.2. The Houben–Hoesch Synthesis / 417

8.3. Acylation of Aliphatic Compounds / 417

8.3.1. Acylation of Alkenes / 418

8.3.2. Acylation of Alkynes / 420

8.3.3. Acylation of Alkanes / 421

References / 422

9 Oxidation–Oxygenation 427

9.1. Oxidation of Alkanes / 427

9.1.1. Oxidation to Alcohols and Carbonyl Compounds / 427

Autoxidation of Alkanes / 427

Oxidation of Methane / 429

Oxidation of Other Saturated Hydrocarbons / 434

9.1.2. Oxidations Resulting in Carbon–Carbon Bond

Cleavage / 444

Metal Oxidants / 444

Electrophilic Reagents / 445

Oxygenolysis / 449

9.2. Oxidation of Alkenes / 449

9.2.1. Epoxidation / 449

Direct Oxidation with Stoichiometric Oxidants / 449

Metal-Catalyzed Epoxidation / 454

Epoxidations Catalyzed by Metalloporphyrins / 458

Asymmetric Epoxidation / 460

9.2.2. Reactions with Molecular Oxygen / 461

Autoxidation / 461

Reactions with Singlet Oxygen / 462

9.2.3. Bis-hydroxylation / 467

9.2.4. Vinylic Oxidation / 470

Oxidation to Carbonyl Compounds / 471

Vinylic Acetoxylation / 475

9.2.5. Oxidative Cleavage / 477

Ozonation / 477

Other Oxidants / 482

9.2.6. Allylic Oxidation / 483

xii CONTENTS

Allylic Hydroxylation and Acyloxylation / 484

Oxidation to a,b-Unsaturated Carbonyl Compounds / 4879.3. Oxidation of Alkynes / 488

9.3.1. Oxidation to Carbonyl Compounds / 488

9.3.2. Oxidative Cleavage / 490

9.4. Oxidation of Aromatics / 491

9.4.1. Ring Oxygenation / 491

Oxidation to Phenols / 491

Ring Acyloxylation / 495

Oxidation to Quinones / 496

Oxidation to Arene Oxides and Arene Diols / 497

Oxidation with Singlet Oxygen / 498

9.4.2. Oxidative Ring Cleavage / 499

9.4.3. Benzylic Oxidation / 500

Oxidation of Methyl-Substituted Aromatics / 500

Oxidation of Other Arenes / 502

Benzylic Acetoxylation / 503


9.5.1. Oxidation of Alkanes / 504

Acetic Acid / 504

Oxidation of Cyclohexane / 505

Oxidation of Cyclododecane / 505

sec-Alcohols / 506

9.5.2. Oxygenation of Alkenes and Dienes / 506

Ethylene Oxide / 506

Propylene Oxide / 508

Acetaldehyde and Acetone / 509

Vinyl Acetate / 509

1,4-Diacetoxy-2-butene / 510

Acrolein and Acrylic Acid / 510

Methacrolein and Methacrylic Acid / 511

9.5.3. Ammoxidation / 511

Acrylonitrile / 511

Other Processes / 512

9.5.4. Oxidation of Arenes / 513

Phenol and Acetone / 513

Benzoic Acid / 514

Terephthalic Acid / 514

Maleic Anhydride / 515

Phthalic Anhydride / 517

Anthraquinone / 519

CONTENTS xiii


9.6.1. Oxidation of Alkanes / 519

Oxidation of Methane / 519

Oxidation of Higher Alkanes / 520

Oxidations Relevant to Industrial Processes / 522

9.6.2. Oxidation of Alkenes / 522

Epoxidation / 522

Bis-hydroxylation / 526

Vinylic Oxidation / 526

Oxidative Cleavage / 527

Allylic Oxidation / 528

9.6.3. Oxidation of Alkynes / 528

9.6.4. Oxidation of Aromatics / 528

Ring Oxygenation / 528

Benzylic Oxidation / 529

9.6.5. Ammoxidation / 529

References / 530

10 Heterosubstitution 576

10.1. Electrophilic (Acid-Catalyzed) Substitution / 577

10.1.1. Substitution of Alkanes / 577

Halogenation / 577

Nitration / 578

Sulfuration / 579

10.1.2. Substitution of Aromatic Hydrocarbons / 579

Halogenation / 580

Nitration / 581

Sulfonation / 583


Chlorobenzene / 584

Nitration of Benzene and Toluene / 584

Sulfonation of Benzene and Alkylbenzenes / 584

10.2. Free-Radical Substitution / 585

10.2.1. Halogenation of Alkanes and Arylalkanes / 585

Chlorination of Alkanes / 586

Fluorination of Alkanes / 588

Side-Chain Chlorination of Arylalkanes / 589

10.2.2. Allylic Chlorination / 590

10.2.3. Sulfochlorination / 590

10.2.4. Nitration / 590

xiv CONTENTS


Chlorination of Alkanes / 592

Side-Chain Chlorination of Toluene / 594

Allyl Chloride / 594

Sulfochlorination of Alkanes / 594

Nitroalkanes / 594

10.3. Amination / 595

10.4. Heterosubstitution through Organometallics / 596

10.4.1. Transition Metals / 596

10.4.2. Alkali Metals and Magnesium / 598


10.5.1. Electrophilic (Acid-Catalyzed) Substitution / 600

Alkanes / 600

Aromatics / 600

10.5.2. Free-Radical Substitution / 603

Alkanes / 603

Alkenes / 605

10.5.3. Amination / 606

10.5.4. Heterosubstitution through Organometallics / 606

References / 607

11 Reduction–Hydrogenation 619

11.1. Heterogeneous Catalytic Hydrogenation / 620

11.1.1. Catalysts / 620

11.1.2. Hydrogenation of Alkenes / 620

Mechanism / 621

Stereochemistry / 623

11.1.3. Hydrogenation of Dienes / 625

11.1.4. Transfer Hydrogenation / 627

11.1.5. Hydrogenation of Alkynes / 628

11.1.6. Hydrogenation of Aromatics / 629

11.2. Homogeneous Catalytic Hydrogenation / 633

11.2.1. Catalysts / 633

11.2.2. Hydrogenation of Alkenes and Dienes / 634

Mechanism / 634

Selectivity and Stereochemistry / 636

Asymmetric Hydrogenation / 639

11.2.3. Hydrogenation of Alkynes / 640


11.3. Chemical and Electrochemical Reduction / 644

CONTENTS xv

11.3.1. Reduction of Alkenes / 644

11.3.2. Reduction of Alkynes / 646

11.3.3. Reduction of Aromatics / 647

Mechanism / 648

Selectivity / 648

11.4. Ionic Hydrogenation / 650

11.4.1. Hydrogenation of Alkenes and Dienes / 651


11.5. Hydrogenolysis of Saturated Hydrocarbons / 655

11.5.1. Metal-Catalyzed Hydrogenolysis / 655

11.5.2. Ionic Hydrogenolysis / 662


11.6.1. Selective Hydrogenation of Petroleum Refining

Streams / 664

C2 Hydrorefining / 664



Gasoline Hydrorefining / 665

11.6.2. Cyclohexane / 665

11.6.3. Various Hydrogenations / 666


11.7.1. Heterogeneous Catalytic Hydrogenation / 667

Alkenes / 667

Dienes and Alkynes / 669

Aromatics / 671

11.7.2. Homogeneous Catalytic Hydrogenation / 672

Alkenes and Dienes / 672

Alkynes / 674

Aromatics / 674

11.7.3. Chemical and Electrochemical Hydrogenation / 676

11.7.4. Ionic Hydrogenation / 677

11.7.5. Hydrogenolysis of Saturated Hydrocarbons / 677

References / 679

12 Metathesis 696

12.1. Acyclic Alkenes / 698

12.2. Ring-Opening Metathesis Polymerization / 706



12.4.1. New Catalysts and Mechanistic Studies / 711

12.4.2. Metathesis of Alkynes / 713

12.4.3. Ring-Closing Metathesis / 713

xvi CONTENTS

12.4.4. Ring-Opening Metathesis / 714


References / 715

13 Oligomerization and Polymerization 723

13.1. Oligomerization / 723

13.1.1. Acid-Catalyzed Oligomerization / 723

Practical Applications / 726

13.1.2. Base-Catalyzed Oligomerization / 727

13.1.3. Metal-Catalyzed Oligomerization / 728

Cyclooligomerization / 729

Practical Applications / 731

13.2. Polymerization / 734

13.2.1. Cationic Polymerization / 734

13.2.2. Anionic Polymerization / 740

13.2.3. Free-Radical Polymerization / 743

13.2.4. Coordination Polymerization / 749

Catalysts / 750

Active Centers and Mechanisms / 753

Stereoregular Polymerization of Propylene / 758

Isospecific Polymerization / 759

Syndiospecific Polymerization / 764

Stereoregular Polymerization of Dienes / 765

13.2.5. Conducting Polymers / 767


Ethylene Polymers / 770

Polypropylene / 773

Polybutylenes / 773

Styrene Polymers / 774

Polydienes / 775


13.3.1. Oligomerization / 776

13.3.2. Polymerization / 778

Group IV Metallocene Catalysts / 779

Late-Transition-Metal Catalysts / 782

Other Developments / 783

References / 784

14 Emerging Areas and Trends 807

14.1. Green Chemistry / 807

CONTENTS xvii

14.1.1. Chemistry in Nontraditional Reaction Media / 808

Water / 808

Fluorous Solvents / 809

Ionic Liquids / 809

Supercritical Solvents / 810

14.1.2. New Catalyst Immobilization or Recovery

Strategies / 811

14.1.3. New Catalysts and Catalytic Processes / 814

14.2. Carbon Dioxide Recycling to Hydrocarbons / 817

References / 818

Index 827

xviii CONTENTS

PREFACE TO THESECOND EDITION

Seven years passed since the publication of the first edition of our book. It is re-

warding that the favorable reception of and interest in hydrocarbon chemistry called

for a second edition. All chapters were updated (generally considering literature

through 2001) by adding sections on recent developments to review new advances

and results. Two new chapters were also added on acylation as well as emerging

areas and trends (including green chemistry, combinatorial chemistry, fluorous

biphase catalysis, solvent-free chemistry, and synthesis via CO2 recycling from

the atmosphere). Because of its importance a more detailed treatment of chemical

reduction of CO2 as a source for hydrocarbons is also included in Chapter 3. The

new edition should keep our book current and of continuing use for interested

readers.

We hope that Hydrocarbon Chemistry will continue to serve its purpose and the

goals that we originally intended.

GEORGE A. OLAH

ÁRPÁD MOLNÁRLos Angeles, California

Szeged, Hungary

March 2002

xix

PREFACE TO THEFIRST EDITION

The idea of a comprehensive monograph treating the hydrocarbon chemistry as an

entity emphasizing basic chemistry, while also relating to the practical aspects of

the broad field, originally developed in the late 1970s by G. A. Olah and the late

Louis Schmerling, a pioneer of hydrocarbon chemistry. The project was pursued

albeit intermittently through the following years, producing a number of draft

chapters. It became, however, clear that the task was more formidable than initially

anticipated. Progress was consequently slow, and much of the initial writings

became outdated in view of rapid progress. The project as originally envisaged

became clearly no longer viable. A new start was needed and made in 1992 with

Á. Molnár coming to the Loker Hydrocarbon Research Institute for 2 years as

Moulton Distinguished Visiting Fellow. We hope that our efforts on Hydrocarbon

Chemistry will be of use to those interested in this broad and fascinating field,

which also has great practical significance.

GEORGE A. OLAH

ÁRPÁD MOLNÁRLos Angeles, California

Szeged, Hungary

March 1995

xxi

The Olahs’ grandchildren (Peter, Kaitlyn, and Justin) enlighten an otherwise blank page.

INTRODUCTION

Hydrocarbons and their transformations play a major role in chemistry. Industrial

applications, basic to our everyday life, face new challenges from diminishing pet-

roleum supplies, regulatory problems, and environmental concerns. Chemists must

find answers to these challenges. Understanding the involved chemistry and finding

new approaches is a field of vigorous development.

Hydrocarbon chemistry (i.e., that of carbon- and hydrogen-containing com-

pounds) covers a broad area of organic chemistry that at the same time is also of

great practical importance. It includes the chemistry of saturated hydrocarbons

(alkanes, cycloalkanes), as well as that of unsaturated alkenes and dienes, acetyl-

enes, and aromatics. Whereas numerous texts and monographs discuss selected

areas of the field, a comprehensive up-to-date treatment as an entity encompassing

both basic chemistry and practical applications is lacking. The aim of our book is to

bring together all major aspects of hydrocarbon chemistry, including fundamental

and applied (industrial) aspects in a single volume. In order to achieve this, it was

necessary to be selective, and we needed to limit our discussion.

The book is arranged in 14 chapters. After discussing general aspects, separation

of hydrocarbons from natural sources and synthesis from C1 precursors with the

most recent developments for possible future applications, each chapter deals

with a specific type of transformation of hydrocarbons. Involved fundamental

chemistry, including reactivity and selectivity, as well as stereochemical considera-

tions and mechanistic aspects are discussed, as are practical applications. In view of

the immense literature, the coverage cannot be comprehensive and is therefore

selective, reflecting the authors’ own experience in the field. It was attempted never-

theless to cover all major aspects with references generally until the early 1994.

The chemistry of the major processes of the petrochemical industry, including

cracking, reforming, isomerization, and alkylation, is covered in Chapters 2, 4,

and 5, respectively. The increasingly important C1 chemistry—that of one-carbon

compounds (CO2, CO, methane, and its derivatives)—is discussed in Chapter 3

(Synthesis from C1 sources).

Chapter 6 (Addition), Chapter 7 (Carbonylation), Chapter 8 (Acylation), and

Chapter 10 (Heterosubstitution) deal with derivatization reactions to form carbon–

heteroatom bonds. The important broad field of hydrocarbon oxidations is covered

in Chapter 9 (Oxidation–oxygenation). Both the chemistry brought about by

xxiii

conventional oxidizing agents and the most recent developments introducing selec-

tively oxygen functionality into hydrocarbons are discussed. The hydrogenation

(catalytic and chemical) and reduction techniques (homogeneous catalytic,

ionic, and electrochemical) are similarly discussed in Chapter 11 (Reduction–

hydrogenation).

Chapter 12 deals with metathesis; Chapter 13, with oligomerization and poly-

merization of hydrocarbons. Each of these fields is of substantial practical signifi-

cance and treated emphasizing basic chemistry and significant practical

applications. Challenges in the new century and possible solutions relevant to

hydrocarbon chemistry are discussed in Chapter 14 (Emerging areas and trends).

Hydrocarbon Chemistry addresses a wide range of readers. We hope that

research and industrial chemists, college and university teachers, and advanced

undergraduate and graduate students alike will find it useful. Since it gives a general

overview of the field, it should also be useful for chemical engineers and in the che-

mical and petrochemical industry in general. Finally, we believe that it may serve

well as supplementary textbook in courses dealing with aspects of the diverse and

significant field.

xxiv INTRODUCTION

1

GENERAL ASPECTS

1.1. HYDROCARBONS AND THEIR CLASSES

Hydrocarbons, as their name indicates, are compounds of carbon and hydrogen.

As such, they represent one of the most significant classes of organic compounds

(i.e., of carbon compounds).1 In methane (CH4) the simplest saturated alkane, a

single-carbon atom, is bonded to four hydrogen atoms. In the higher homologs

of methane (of the general formula CnH2nþ2) all atoms are bound to each otherby single [(sigma (s), two-electron two-center] bonds with carbon displaying itstendency to form C��C bonds. Whereas in CH4 the H : C ratio is 4, in C2H6 (ethane)it is decreased to 3; in C3H8 (propane), to 2.67; and so on. Alkanes can be straight-

chain (with each carbon attached to not more than two other carbon atoms) or

branched (in which at least one of the carbons is attached to either three or four

other carbon atoms). Carbon atoms can be aligned in open chains (acyclic hydro-

carbons) or can form rings (cyclic hydrocarbons).

Cycloalkanes are cyclic saturated hydrocarbons containing a single ring.

Bridged cycloalkanes contain one (or more) pair(s) of carbon atoms common to

two (ormore) rings. In bicycloalkanes there are two carbon atoms common to both rings.

In tricycloalkanes there are four carbon atoms common to three rings such as in

adamantane (tricyclo[3.3.1]1,5,3,7decane), giving a caged hydrocarbon structure.

Carbon can also form multiple bonds with other carbon atoms. This results in

unsaturated hydrocarbons such as olefins (alkenes, CnH2n), specifically, hydrocar-

bons containing a carbon–carbon double bond or acetylenes (alkynes, CnHn�2)containing a carbon–carbon triple bond. Dienes and polyenes contain two or

more unsaturated bonds.

Aromatic hydrocarbons (arenes), a class of hydrocarbons of which benzene

is parent, consist of cyclic arrangement of formally unsaturated carbons, which,

1

however, give a stabilized (in contrast to their hypothetical cyclopolyenes) deloca-

lized p system.The H : C ratio in hydrocarbons is indicative of the hydrogen deficiency of the

system. As mentioned, the highest theoretical H : C ratio possible for hydrocarbons

is 4 (in CH4), although in carbocationic compounds (the positive ions of carbon

compound) such as CHþ5 and even CH2þ6 the ratio is further increased (to 5 and

6, respectively). On the other end of the scale in extreme cases, such as the dihydro

or methylene derivatives of recently (at the time of writing) discovered C60 and C70fullerenes, the H : C ratio can be as low as � 0.03!

An index of unsaturation (hydrogen deficiency) i can be used in hydrocarbons

whose value indicates the number of ring and/or double bonds (a triple bond is

counted as two double bonds) present (C and H¼ the number of carbon and hydro-gen atoms), i ¼ 0 for methane, for ethene i ¼ 1 (one double bond), for acetylene(ethyne) i ¼ 2, and so on:

The International Union of Pure and Applied Chemistry (IUPAC) established

rules to name hydrocarbons. Frequently, however, trivial names are also used and

will continue to be used. It is not considered necessary to elaborate here on the

question of nomenclature. Systematic naming is mostly followed. Trivial (common)

namings are, however, also well extended. Olefins or aromatics clearly are very

much part of our everyday usage, although their IUPAC names are alkenes and

arenes, respectively. Straight-chain saturated hydrocarbons are frequently referred

to as n-alkanes (normal) in contrast to their branched analogs (isoalkanes, i-alkanes).

Similarly straight-chain alkenes are frequently called n-alkenes as contrasted

with branch isoalkenes (or olefins). What needs to be pointed out, however, is

that one should not mix the systematic IUPAC and the still prevalent trivial (or com-

mon) namings. For example, (CH3)2C��CH2 can be called isobutylene or 2-methyl-propene. It, however, should not be called isobutene as only the common name

butylene should be affixed by iso. On the other hand, isobutane is the proper com-

mon name for 2-methylpropane [(CH3)3CH]. Consequently we discuss isobutane–

isobutylene alkylation for production of isooctane: high-octane gasoline (but it

should not be called isobutane–isobutene alkylation).

1.2. ENERGY–HYDROCARBON RELATIONSHIP

Every facet of human life is affected by our need for energy. The sun is the central

energy source of our solar system. The difficulty lies in converting solar energy into

other energy sources and also to store them for future use. Photovoltaic devices and

other means to utilize solar energy are intensively studied and developed, but at the

2

(2C + 2) − Hi =

2 GENERAL ASPECTS

level of our energy demands, Earth-based major installations by present-day tech-

nology are not feasible. The size of collecting devices would necessitate utilization

of large areas of the Earth. Atmospheric conditions in most of the industrialized

world are unsuitable to provide a constant solar energy supply. Perhaps a space-

based collecting system beaming energy back to Earth can be established at

some time in the future, but except for small-scale installation, solar energy is of

limited significance for the foreseeable future. Unfortunately, the same must be said

about wind, ocean waves, and other unconventional energy sources.

Our major energy sources are fossil fuels (i.e., oil, gas, and coal), as well as

atomic energy. Fossil energy sources are, however, nonrenewable (at least on our

timescale), and their burning causes serious environmental problems. Increased

carbon dioxide levels are considered to contribute to the ‘‘greenhouse’’ effect.

The major limitation, however, is the limited nature of our fossil fuel resources

(see Section 1.5). The most realistic estimates2 put our overall worldwide fossil

resources as lasting for not more than 200 or 300 years, of which oil and gas would

last less than a century. In human history this is a short period, and we will need to

find new solutions. The United States relies overwhelmingly on fossil energy sources,

with only 8% coming from atomic energy and 4% from hydro energy (Table 1.1).

Other industrialized countries utilize to a much higher degree of nuclear and

hydroenergy2 (Table 1.2). Since 1980, concerns about safety and fission byproduct

Table 1.1. U.S. energy sources (%)

Power Source 1960 1970 1990

Oil 48 46 41

Natural gas 26 26 24

Coal 19 19 23

Nuclear energy 3 5 8

Hydrothermal, geothermal, solar, etc. energy 4 4 4

Table 1.2. Power generated in industrial countries by nonfossil fuels (1990)

Non-Fossil-Fuel Power (%)

—————————————————————————

Country Hydroenergy Nuclear Energy Total

France 12 75 87

Canada 58 16 74

Former West Germany 4 34 38

Japan 11 26 37

United Kingdom 1 23 24

Italy 16 0 16

United States 4 8 12

ENERGY–HYDROCARBON RELATIONSHIP 3

disposal difficulties, however, dramatically limited the growth of the otherwise

clean atomic energy industry.

Away to extend the lifetime of our fossil fuel energy reserves is to raise the effi-

ciency of thermal power generation. Progress has been made in this respect, but the

heat efficiency even in the most modern power plants is limited. Heat efficiency

increased substantially from 19% in 1951 to 38% in 1970, but for many years since

then 39% appeared to be the limit. Combined-cycle thermal power generation—a

combination of gas turbines—was allowed in Japan to further increase heat

efficiency from 35–39% to as high as 43%. Conservation efforts can also greatly

contribute to moderate worldwide growth of energy consumption, but the rapidly

growing population of our planet (5.4 billion today, but should reach 7–8 billion

by 2010) will put enormous pressure on our future needs.

Estimates of the world energy consumption until 2020 are shown graphically in

Figure 1.1 in relationship to data dating back to 1960.2 A rise in global energy con-

sumption of 50–75% for the year 2020 is expected compared with that for 1988.

Even in a very limited growth economic scenario the global energy demand is

estimated to reach 12 billion tons of oil equivalent (t/oe) by the year 2020.

Our long-range energy future clearly must be safe nuclear energy, which should

increasingly free still remaining fossil fuels as sources for convenient transportation

fuels and as raw materials for synthesis of plastics, chemicals, and other substances.

Eventually, however, in the not too distant future we will need to make synthetic

hydrocarbons on a large scale.

1.3. HYDROCARBON SOURCES AND SEPARATION

All fossil fuels (coal, oil, gas) are basically hydrocarbons, deviating, however, sig-

nificantly in their H : C ratio (Table 1.3).

1960 1970 1980

Year

Moderate

Limited

1990 2000 2010 2020

0

4

8

12

Ene

rgy

cons

umpt

ion

(Gt/y

ear)

16

Figure 1.1. World energy consumption (in gigatons per year) projections.

4 GENERAL ASPECTS

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