Metal-catalysis in Industrial Organic Processes

Preface;

Glossary;

Chapter 1: Introduction - Catalysis in the Chemical Industry Sunley;

1.1: Catalysis in the Chemical Industry;

1.2: Selection of a Chemical Process: What Does the Catalyst Do?;

1.3: Developing Metal-Catalysis - the Role of Fundamental Understanding;

References;

Chapter 2: Formation of C-O Bonds by Oxidation;

2.1: Review - The Basic Chemistry of Oxygen;

2.2: Cyclohexane Oxidation to Cyclohexanol and Cyclohexanone and to Adipic Acid: on the Way to Nylon-6,6;

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;

2.5: 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;

2.8: 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;

2.11: Maleic Anhydride and Phthalic Anhydride: for THF, Spandex, Swim-suits and Ladies' Tights;

2.12: Silicalite Process to e-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;

2.16: Enzymatic and Microbiological Oxidations. Microbial Hydroxylation of Progesterone;

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 Isomerization Reactions;

3.2: Hydrotreating in Petroleum Chemistry;

3.3: Mono-unsaturated Fatty Esters by Partial Hydrogenation of Natural Oils;

3.4: Hydrogenation of Adiponitrile to Hexamethylenediamine;

3.5: Making L-DOPA by Enantioselective Hydrogenation of Acetamidoarylacrylic Acids;

3.6: Enantioselective Hydrogenation of N-Arylimines in the Synthesis of the Chiral Herbicide, (S )-Metolachlor;

3.7: Isomerization Reactions: Diethylgeranylamine and Diethylnerylamine for the Production of (_)-Menthol;

3.8: Enantioselective Hydrogen Transfer;

3.9: Ethylbenzene Dehydrogenation to Styrene;

Discussion Points;

References;

Chapter 4: Syntheses Based on Carbon Monoxide;

4.1: Introduction;

4.2: Carbonylation Reactions of Alcohols and Esters;

4.3: Hydroxy/Alkoxy-Carbonylation of Alkenes and Dienes;

4.4: Polyketones;

4.5: Oxidative Carbonylation of Methanol to Dimethyl Carbonate and Dimethyl Oxalate;

4.6: Hydroformylation of Olefins;

4.7: CO Hydrogenation;

Annex 1: Concerning the Mechanism of the Fischer-Tropsch Reaction;

Annex 2: Some Hints for Discussion Points;

References;

Chapter 5: Carbon-Carbon Bond Formation;

5.1: Introduction;

5.2: Alkylation and Related Reactions;

5.3: Carbon-Carbon Bond Formation through Activation of Aryl- or Vinyl-Halide bonds: Fine Chemicals;

5.4: Chemistry of Allyl Compounds. Butadiene as Substrate;

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;

Annex 3: Perspectives in C-C Bond Forming Organic Syntheses;

References;

Chapter 6: Metathesis of Olefins;

6.1: Introduction - History and Basic Chemistry of Metathesis;

6.2: The Carbene-Metallacyclobutane Mechanism of Metathesis;

6.3: Industrial Applications of Metathesis;

6.4: Homogeneous Ruthenium Alkylidene Complexes;

6.5: Speciality Polymers;

6.6: Fine Chemicals and Pharmaceuticals;

6.7: Recent Progress;

6.8: Future Outlook;

References;

Chapter 7: Polymerization Reactions;

7.1: An Introductory Overview;

7.2: Industrial Aspects of Polyolefin Production;

7.3: Solid-State Polymerization Catalysts;

7.4: Soluble Olefin Polymerization Catalysts;

7.5: Supported Metallocene Catalysts;

7.6: Copolymerization of Linear and Cyclic Olefins;

7.7: Copolymerisation of Olefins with Polar Monomers and with CO;

Annex 1: Polymer Stereochemistry Studied by 13C NMR Spectroscopy;

Annex 2: Stereospecific Polymerization of Conjugated Diolefins: Butadiene and Isoprene;

Annex 3: Some Hints to Help Start the Discussions;

Acknowledgements;

References;

Appendix 1: Basic Organometallic Chemistry Related to Catalytic Cycles;

References;

Appendix 2: Some Basic Aspects of Surface Science Related to Heterogeneously Catalyzed Reactions;

References;

Subject Index