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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
Innodata0471461385.jpg
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HYDROCARBON CHEMISTRY
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Dedicated to Katherine Bogdanovich Loker,friend and generous supporter of hydrocarbon research.
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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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Copyright # 2003 by John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey.
Published simultaneously in Canada.
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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
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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
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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
2.5.2. Practical Applications / 56
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
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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. Recent Developments / 124
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
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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. Recent Developments / 194
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
5.5. Practical Applications / 254
viii CONTENTS
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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. Recent Developments / 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
6.1.3. Practical Applications / 288
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
6.2.4. Practical Applications / 301
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
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6.3.2. Dienes / 308
6.3.3. Alkynes / 310
6.3.4. Practical Applications / 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. Recent Developments / 336
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
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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
7.2.4. Practical Applications / 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. Recent Developments / 387
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
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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
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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. Practical Applications / 504
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
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9.6. Recent Developments / 519
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
10.1.3. Practical Applications / 584
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
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10.2.5. Practical Applications / 592
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. Recent Developments / 600
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
11.2.4. Hydrogenation of Aromatics / 641
11.3. Chemical and Electrochemical Reduction / 644
CONTENTS xv
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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
11.4.2. Hydrogenation of Aromatics / 654
11.5. Hydrogenolysis of Saturated Hydrocarbons / 655
11.5.1. Metal-Catalyzed Hydrogenolysis / 655
11.5.2. Ionic Hydrogenolysis / 662
11.6. Practical Applications / 664
11.6.1. Selective Hydrogenation of Petroleum Refining
Streams / 664
C2 Hydrorefining / 664
C3 Hydrorefining / 664
C4 Hydrorefining / 664
Gasoline Hydrorefining / 665
11.6.2. Cyclohexane / 665
11.6.3. Various Hydrogenations / 666
11.7. Recent Developments / 667
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
12.3. Practical Applications / 708
12.4. Recent Developments / 711
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
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12.4.4. Ring-Opening Metathesis / 714
12.4.5. Practical Applications / 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
13.2.6. Practical Applications / 770
Ethylene Polymers / 770
Polypropylene / 773
Polybutylenes / 773
Styrene Polymers / 774
Polydienes / 775
13.3. Recent Developments / 776
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
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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
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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
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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
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The Olahs’ grandchildren (Peter, Kaitlyn, and Justin) enlighten an otherwise blank page.
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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
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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