Metal-Catalysis in Industrial Organic Processes -- Contents -- Preface -- Glossary -- Chapter 1 Introduction: Catalysis in the Chemical Industry -- 1.1 Catalysis in the Chemical Industry -- 1.1.1 The Importance of Catalysis -- 1.1.2 Chemical Processes -- 1.1.3 Evolution of the Catalysis Based Industries -- 1.1.4 Applying Catalysis -- 1.2 Selection of a Chemical Process: What Does the Catalyst Do? -- 1.2.1 Feedstocks: Availability and Cost -- 1.2.2 Feedstocks: Thermodynamic and Kinetic Feasibility -- 1.2.3 Economics: The Costs of Making a Chemical -- 1.2.4 Safety and Environmental Impact -- 1.2.5 Product Properties and Value -- 1.2.6 What Makes a Successful Process? -- 1.3 Developing Metal-Catalysis - the Role of Fundamental Understanding -- 1.3.1 Catalytic Cycles -- 1.3.2 How we Study What a Catalyst Does -- 1.3.3 Reaction Kinetics and the Catalytic Cycle -- 1.3.4 Model Studies - Structures and Reactions -- 1.3.5 How to Apply Understanding to Discovering and Improving Catalysts -- References -- Chapter 2 Formation of C-O Bonds by Oxidation -- 2.1 Review: The Basic Chemistry of Oxygen -- 2.1.1 Diradical Nature of the Dioxygen Molecule -- 2.1.2 Metal-Oxygen Complexes -- 2.1.3 Biomimetic Oxidations -- 2.1.4 Hydrogen Peroxide and Alkylhydroperoxides -- 2.2 Cyclohexane Oxidation to Cyclohexanol and Cyclohexanone and to Adipic Acid: on the Way to Nylon-6,6 -- 2.2.1 KA Oil from Cyclohexane -- 2.2.2 Adipic Acid from KA Oil -- 2.2.3 Related Processes -- 2.3 p-Xylene Oxidation to Terephthalic Acid. Polyethylene Terephthalate: on the Way to Fibres for Shirts -- 2.4 Ethylene Oxide by Ag-catalyzed Oxidation of Ethylene: for Antifreeze and Detergents -- 2.4.1 Air- and Oxygen-based Industrial Processes -- 2.4.2 Proposed Epoxidation Mechanisms on Ag Catalysts -- 2.4.3 Is the Epoxidation of Olefins Other than Ethylene Feasible on Silver Catalysts?.

2.5 Propylene Oxide: to Biocompatible Propylene Glycol -- 2.6 Hydrogen Peroxide Route to Propylene Oxide -- 2.7 Asymmetric Epoxidation, Dihydroxylation and Sulfide Oxidation: New Routes to Chiral Agrochemicals and Pharmaceuticals -- 2.7.1 Epoxidation of Allylic Alcohols -- 2.7.2 Epoxidation of Simple Olefins -- 2.7.3 Vicinal Dihydroxylation of Olefins -- 2.7.4 Oxidation of Sulfides to Sulfoxides: an Anti-ulcer Medication -- 2.8 Acrolein and Acrylic Acid from Propylene: for Super-Absorbent Polymers, Paints, and Fibres -- 2.9 Methacrolein and Methacrylic Acid from Isobutene -- 2.10 Ammoxidation Reactions. Propylene to Acrylonitrile: for Engineering Plastics, Polymers -- 2.10.1 Isophthalonitrile from m-Xylene -- 2.11 Maleic Anhydride and Phthalic Anhydride: for THF, Spandex, Swim-suits and Ladies' Tights -- 2.11.1 Maleic Anhydride -- 2.11.2 Phthalic Anhydride -- 2.12 Silicalite Process to ε-Caprolactam -- 2.12.1 Ammoximation of Cyclohexanone on TS-1 -- 2.12.2 Gas Phase Rearrangement of Cyclohexanone Oxime to ε-Caprolactam -- 2.13 Oxidation of Phenol to Catechol and Hydroquinone -- 2.14 Benzene Oxidation to Phenol: Making Phenolic Resins for Building -- 2.15 Oxidation Processes in which the Metal Directly Functionalizes the Olefinic Substrate -- 2.15.1 Ethylene to Acetaldehyde: the Wacker Synthesis -- 2.15.2 Chemical Basis of the Wacker Process -- 2.15.3 Wacker Process Operation -- 2.15.4 Alternative Catalyst Formulations for Ethylene to Acetaldehyde -- 2.15.5 Oxidation of Propylene to Acetone -- 2.15.6 Vinyl Acetate Based on Ethylene (Solution Based Processes) -- 2.15.7 The Gas-phase Ethylene to Vinyl Acetate Process -- 2.15.8 Uses of Vinyl Acetate -- 2.16 Enzymatic and Microbiological Oxidations. Microbial Hydroxylation of Progesterone -- 2.16.1 Perspectives of Enzymatic and Microbiological Oxidations.

Annex 1 Alkane Feedstocks. Alternative Routes to Acetic Acid and Acrylonitrile -- Annex 2 Adsorption Effects on the Catalytic Performances of TS-1. Zeolites as Solid Solvents -- References -- Chapter 3 Hydrogenation Reactions -- 3.1 Introduction and Basic Chemistry: Activation of Hydrogen and Transfer to Substrate -- 3.1.1 Hydrides and Dihydrogen Activation -- 3.1.2 The Reversible Addition of M-H to C=X Bonds on Model Complexes: Olefin Isomerization Reactions -- 3.1.3 A Typical Homogeneously Catalyzed Hydrogenation Cycle: the Wilkinson Catalyst -- 3.1.4 Isomerization of Alkenes -- 3.1.5 Reactions on Metal Surfaces: Heterogeneously Catalyzed Hydrogenation and Isomerization -- 3.2 Hydrotreating in Petroleum Chemistry -- 3.2.1 Importance of Hydrotreating in Petroleum Chemistry -- 3.2.2 The Catalytic Process -- 3.2.3 Composition and Structure of HDS Catalysts -- 3.2.4 Mechanistic Studies -- 3.2.5 Deep Desulfurization -- 3.3 Mono-unsaturated Fatty Esters by Partial Hydrogenation of Natural Oils -- 3.3.1 Hydrogenation of Fats -- 3.3.2 The Selectivity Problem -- 3.3.3 Nickel Catalysts and Catalytic Processes -- 3.4 Hydrogenation of Adiponitrile to Hexamethylenediamine -- 3.4.1 The Uses of Hexamethylenediamine -- 3.4.2 The Hydrogenation of Adiponitrile -- 3.4.3 Insights into the Reaction Mechanism -- 3.5 Making L-DOPA by Enantioselective Hydrogenation of Acetamidoarylacrylic Acids -- 3.5.1 The Development of the Enantioselective Hydrogenation Step -- 3.5.2 Mechanism of the Asymmetric Catalytic Hydrogenation -- 3.6 Enantioselective Hydrogenation of N-Arylimines in the Synthesis of the Chiral Herbicide, (S)-Metolachlor -- 3.6.1 The Synthesis of Metolachlor -- 3.6.2 Mechanistic Studies -- 3.7 Isomerization Reactions: Diethylgeranylamine and Diethylnerylamine for the Production of (-)-Menthol -- 3.7.1 The Synthetic Route to Menthol -- 3.7.2 Mechanistic Insights.

3.8 Enantioselective Hydrogen Transfer -- 3.9 Ethylbenzene Dehydrogenation to Styrene -- 3.9.1 The Styrene Market -- 3.9.2 Ethylbenzene Non-Oxidative Dehydrogenation -- 3.9.3 Catalysts for Ethylbenzene Dehydrogenation: Mechanism and Deactivation -- 3.9.4 Alternatives for Non-Oxidative Dehydrogenation -- Discussion Points -- References -- Chapter 4 Syntheses Based on Carbon Monoxide -- 4.1 Introduction -- 4.1.1 Carbonylation Reactions: Historical and General Perspectives -- 4.1.2 Syngas as a Feedstock -- 4.1.3 The Water-Gas Shift Reaction -- 4.2 Carbonylation Reactions of Alcohols and Esters -- 4.2.1 Manufacture of Acetic Acid from Methanol -- 4.2.2 Acetic Acid Historical and Background -- 4.2.3 Cobalt-Catalyzed Carbonylation of Methanol -- 4.2.4 Rhodium-Catalyzed Carbonylation of Methanol -- 4.2.5 Mechanism of Rhodium/Iodide Catalyzed Methanol Carbonylation -- 4.2.6 Iridium-Catalyzed Carbonylation of Methanol -- 4.2.7 Mechanism of the Iridium/Iodide Catalyzed Methanol Carbonylation -- 4.2.8 Rhodium-Catalyzed Carbonylation of Methyl Acetate to Acetic Anhydride -- 4.2.9 Carbonylation of Higher Alcohols: Higher Carboxylic Acids -- 4.2.10 Carbonylation of Benzyl Alcohol to Phenylacetic Acid -- Manufacture of Ibuprofen -- 4.3 Hydroxy/Alkoxy-Carbonylation of Alkenes and Dienes -- 4.3.1 Ethylene to Propionic Acid -- Methyl Propionate and Methyl Methacrylate (MMA) -- 4.3.2 Cobalt-Catalyzed Butadiene Dimethoxycarbonylation to Dimethyl Adipate -- 4.4 Polyketones -- 4.5 Oxidative Carbonylation of Methanol to Dimethyl Carbonate and Dimethyl Oxalate -- 4.6 Hydroformylation of Olefins -- 4.6.1 Manufacture of n-Butyraldehyde and n-Butanol -- 4.6.2 "Unmodified" Cobalt Catalysts -- 4.6.3 Phosphine-Modified Cobalt Catalysts -- 4.6.4 Rhodium-Catalyzed Hydroformylation -- 4.6.5 Two-Phase (Water-Soluble) Rhodium Hydroformylation Catalysts.

4.6.6 Rhodium Hydroformylation Catalysts with Bidentate Ligands -- 4.6.7 Enantioselective Hydroformylation -- 4.7 CO Hydrogenation -- 4.7.1 Methanol Synthesis -- 4.7.2 Hydrocarbons from the Hydrogenation of CO: the Fischer-Tropsch (F-T) Reaction -- 4.7.3 Fischer-Tropsch Technology -- Annex 1 Concerning the Mechanism of the Fischer-Tropsch Reaction -- Annex 1.1 How are 1-alkenes formed from syngas? -- Annex 1.2 Other mechanistic proposals -- Annex 1.3 Homogeneous CO hydrogenation -- Annex 2 Some Hints for Discussion Points -- References -- Chapter 5 Carbon-Carbon Bond Formation -- 5.1 Introduction -- 5.2 Alkylation and Related Reactions -- 5.2.1 Ethylbenzene by Alkylation of Benzene with Ethylene -- 5.2.2 Toluene Dealkylation and Methyl Redistribution to Benzene and Xylenes -- 5.2.3 Cumene from Benzene and Propylene -- 5.2.4 2,6-Di-isopropylnaphthalene -- 5.2.5 Other Alkylations of Aromatics -- 5.2.6 Alkane Cracking and Isomerization on Solid Acid Catalysts -- 5.2.7 o-Pentenyltoluene from o-Xylene and Butadiene -- 5.2.8 C-C Bond Formation Through Multifunctional Catalysis By Mixed Metal Oxides -- 5.3 Carbon-Carbon Bond Formation through Activation of Aryl- or Vinyl-Halide bonds: Fine Chemicals -- 5.3.1 Vinylarenes by Vinylation of Aromatics -- 5.3.2 Alkynylarenes by Vinylation of Triple Bonds -- 5.3.3 Biaryls by Aryl Coupling -- 5.3.4 Considerations on Reactions of Aryl and Vinyl Halides -- 5.3.5 Why Palladium? -- 5.4 Chemistry of Allyl Compounds. Butadiene as Substrate -- 5.4.1 1,4-Hexadiene from Butadiene and Ethylene -- 5.4.2 Cyclooctadiene and Cyclododecatriene from Butadiene -- 5.4.3 Octadienol from Butadiene -- 5.4.4 Adiponitrile by HCN Addition to Butadiene -- 5.5 Oligomerization of Olefins -- 5.6 Carbene Chemistry and Asymmetric Synthesis: Chrysanthemic Esters -- Annex 1 Devising New Synthetic Pathways.

Annex 2 Hints to Improve or to Develop Alternative Processes for the Synthesis of Aromatics Catalyzed by Transition Metals.