Description
Book SynopsisThis book provides an unparalleled contemporary assessment of hydrocarbon chemistry presenting basic concepts, current research, and future applications.
Comprehensive and updated review and discussion of the field of hydrocarbon chemistry
Includes literature coverage since the publication of the previous edition
Expands or adds coverage of: carboxylation, sustainable hydrocarbons, extraterrestrial hydrocarbons
Addresses a topic of special relevance in contemporary science, since hydrocarbons play a role as a possible replacement for coal, petroleum oil, and natural gas as well as their environmentally safe use
Reviews of prior edition: ...literature coverage is comprehensive and ideal for quickly reviewing specific topics...of most value to industrial chemists... (Angewandte Chemie) and ...useful for chemical engineers as well as engineers in the chemical and petrochemical industries. (Petroleum Science and Technology)
Table of ContentsVolume 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
