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Industrial Applications of Homogeneous Catalysis

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Catalysts are now widely used in both laboratory and industrial-scale chemistry. Indeed, it is hard to find any complex synthesis ... Weiterlesen
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Catalysts are now widely used in both laboratory and industrial-scale chemistry. Indeed, it is hard to find any complex synthesis or industrial process that does not, at some stage, utilize a catalytic reaction. The development of homogeneous transition metal catalysts on the laboratory scale has demonstrated that these systems can be far superior to the equivalent heterogeneous systems, at least in terms of selectivity. is an increasing interest in this field of research from both an Thus, there academic and industrial point of view. In connection with the rapid developments in this area, four universities from the E.E.C (Aachen, FRG; Liege, Belgium; Milan, Italy; and Lille, France) have collaborated to organise a series of seminars for high-level students and researchers. These meetings have been sponsored by the Commission of the E.E.C and state organizations. The most recent of these meetings was held in Lille in September 1985 and this book contains updated and expanded presentations of most of the lectures given there. These lectures are concerned with the field of homogeneous transition metal catalysis and its application to the synthesis of organic intermediates and fine chemicals from an academic and industrial viewpoint. The continuing petroleum crisis which began in the early 1970s has given rise to the need to develop new feedstocks for the chemical industry.

Chemicals from Methanol and Carbon Monoxide.- 1. Introduction.- 2. Carbonylation of Methanol and of Methanol Derivatives.- 2.1. Transition Metal Catalyzed Carbonylation.- 2.1.1. Side Reactions.- 2.1.2. Rhodium Catalysts.- 2.1.3. Cobalt Catalysts.- 2.1.4. Nickel Catalysts.- 2.2. Base Catalyzed Carbonylation.- 3. Reductive Carbonylation of Methanol and Methanol Derived Substrates.- 3.1. Methanol Homologation.- 3.2. Homologation of Methoxy Derivatives.- 3.3. Reductive Carbonylation of Formaldehyde.- 4. Oxidative Carbonylation.- 5. Conclusions.- References.- Carbon Monoxide and Fine Chemicals Synthesis.- 1. Basis of Carbon Monoxide Chemistry.- 2. Carbonylation of Organic Halides.- 2.1. Synthesis of Aldehydes.- 2.1.1. Aromatic and Vinylic halides.- 2.1.2. Alkyl Halides.- 2.2. Synthesis of Acids and Esters.- 2.2.1. Aromatic and Vinylic Halides.- 2.2.2. Aliphatic Halides.- 2.3. Synthesis of Amides.- 2.4. Synthesis of Ketones.- 2.5. Synthesis of Acid Halides.- 2.6. Synthesis of Keto-Acids and Keto-Amides.- 2.7. Synthesis of Anhydrides.- 3. Carbonylation of Alcohols.- 3.1. Synthesis of Alcohols and Aldehydes.- 3.2. Synthesis of Carboxylic Acids.- 3.3. Synthesis of Oxalates and Carbonates.- 4. Carbonylation of Nitro Compounds.- 4.1. Isocyanates, Carbamates and Ureas.- 4.2. Synthesis of Formamides.- 5. Carbonylation of Amines.- 5.1. Synthesis of Formamides.- 5.2. Synthesis of Isocyanates, Carbamates and Ureas.- 6. Carbonylation of Alkenes.- 6.1. Synthesis of Aldehydes and Alcohols.- 6.2. Synthesis of Carboxylic Acids.- 6.3. Synthesis of Ketones.- 6.4. Oxidative Carbonylation of Alkenes.- 7. Carbonylation of Alkynes.- 7.1. Synthesis of Unsaturated Acids.- 7.2. Synthesis of Hydroquinones.- 8. Carbonylation of CH Bonds.- 8.1. Synthesis of Aldehydes.- 8.2. Synthesis of Carboxylic Acids.- 8.2.1. Synthesis of Aromatic Carboxylic Acids.- 8.2.2. Synthesis of Aliphatic Carboxylic Acids.- 8.3. Synthesis of Ketones.- 9. Synthesis of Amino Acids.- 10. Conclusion.- References.- Transition Metal Catalyzed Reductions of Organic Molecules by Molecular Hydrogen and Hydrides: An Overview.- 1. Activation of Molecular Hydrogen.- 1.1. H2Activation by Oxidative Addition (OA).- 1.2. H2 Activation by Homolysis.- 1.3. H2 Activation by Heterolytic Addition.- 1.4. The Case of Pentamethylcyclopentadienyl Rh and Ir Complexes.- 1.5. Organolanthanides and Actinides as Catalysts for Olefin Hydrogenation.- 2. Some Recent Developments in Hydrogénation: Activation of Hydrides by Transition Metal Derivatives.- 2.1. Examples.- 2.1.1. LiAlH4with First Row Transition Metal Halides.- 2.1.2. LiAlH4with Hard Lewis Acids.- 2.1.3. NaBH4with Ni or Co Salts in MeOH.- 2.1.4. Hydroboration with NaBH4.- 2.1.5. Reduction of Acid Chlorides and Nitro Groups.- 2.1.6. Vanadium Chloride and Lithium Hydride.- 2.1.7. Complex Reducing Agents.- 2.2. Unusual Chemoselectivity.- 2.2.1. Reversal of Normal Reduction Sequences with LanthanideNaBH4Systems.- 2.2.2. Selective Hydrogénation of Unsaturated Aldehydes and Ketones.- 2.3. Reduction of ?,?-Unsaturated Nitriles.- 2.4. Hydrogenation of Aromatic Nuclei.- 3. Hydrosilylation.- 3.1. Extensions of Hydrosilylation Reactions.- 3.1.1. Ring Closure.- 3.1.2. Hydrosilylation of Conjugated Dienes.- 3.1.3. Hydrosilylation of Acetylenes.- 3.1.4. Reduction of C=0.- 3.1.5. Reduction of ?,?-Unsaturated Carbonyl Compounds.- 3.1.6. Hydrosilylation of C=N Bonds.- 4. Hydrozirconation.- 4.1. Functional Group Compatibility.- References.- Application of Transition Metals in Natural Product and Heterocycle Synthesis.- 1. Introduction.- 1.1. Introduction of Functional Groups.- 1.2. Improvement of Classical Organic Reactions.- 1.3. Construction of the Skeleton of Organic Molecules.- 2. Stoichiometric Reactions: Organocopper Derivatives.- 2.1. Preparation of Organocopper Reagents.- 2.2. Stability of Cuprates.- 2.3. Conjugate Additions Organocuprates.- 2.4. Some Particular Applications of Addition Reactions of Organocuprates.- 2.4.1.,6-Conjugate Addition.- 2.4.2. Homoallylic Addition to Epoxides.- 2.4.3. Ring Opening Reactions.- 2.4.4. Substitution to Acetoxy Groups.- 2.5. Coupling Reactions.- 2.5.1. Aromatic Coupling Reactions.- 2.5.2. Copper Mediated Coupling of an Organometallic Reagent with an Alkyl or Vinyl Halide.- 3. Catalytic Reaction: Palladium and Nickel Organometallic Reagents.- 3.1. The Key Intermediates.- 3.2. Activation by ?-Complex Formation.- 3.3. Remark.- 4. Applications of Palladium and Nickel Complexes in Natural Product Synthesis.- 4.1. Coupling Reactions.- 4.1.1. Typical Cross Coupling Reactions of Allyl Groups.- (A) Cross Coupling Reaction of Allyl Halides.- (B) Cross Coupling Reactions of Aromatic Halides.- (C) Cross Coupling Reactions of Aryl Halides with ?-AllylNickel Complexes.- (D) Palladium Catalyzed Cross Coupling Reactions of Organometallics.- 4.2. Alkylation Reactions.- 4.2.1. Examples of Nucleophiles Useful in ?-AllylPalladium Substitution Processes.- (A) Malonates.- (B) Sulfones.- (C) Nitroalkanes.- 4.3. Cyclizations.- 4.4.,4-Addition to Conjugated Systems.- 4.5. Telomerizations and Oligomerizations.- 4.5.1. Preparation of Linear Telomers and Oligomers.- 4.5.2. Preparation of Cyclic Oligomers.- 4.6. Carbonylation Reactions.- 4.7. Prototropic Isomerizations and Rearrangements.- 4.8. Elimination and Decarboxylation Reactions.- 4.9. Transmetallation.- 4.10. Metallation.- 4.11. Applications of Oxidation and Hydrogénation.- 4.11.1. Oxidations.- 4.11.2. Hydrogénations.- 5. Particular Applications of Transition Metals.- 5.1. Group Protection by Complex Formation.- 5.2. Iron Complexes: Cationic Complexes.- 5.3. Anionic Transition Metal Reagents.- 5.4. Titanium and Zirconium.- 5.5. Metathesis.- 6. Applications of Transition Metals in Hydride Chemistry.- 6.1. Organoboron Chemistry.- 6.2. Alane Chemistry.- 6.3. Tin Hydride Chemistry.- 6.4. Hydrozirconation.- 6.4.1. Applications of Hydrozirconation to the Synthesis of Biologically Active Compounds.- 6.4.2. Particular Applications of Organozirconium Reagents.- 6.5. Hydrosilylation.- 7. Application of Transition Metal Catalysis in Heterocyclic Synthesis (Typical Examples).- 7.1. Typical Examples of Heterocyclic System Synthesis.- 7.2. Pyrrole Synthesis.- 7.3. Isoquinoline and Quinoline.- 7.4. ?-Lactam Chemistry.- 7.5. Lactone Synthesis.- 7.6. Cyclic Ether Synthesis.- 7.7. Miscellaneous Examples.- 8. Transition Metal-Catalyzed Reactions of Carbenes.- 8.1. Catalytic Reaction.- 8.1.1. Cycloaddition of Carbenes to Alkenes.- 8.1.2. Insertion Reactions.- 8.2. Stoichiometric Reactions of Carbenoids and Ylides.- References.- Application of Telomerization and Dimerization to the Synthesis of Fine Chemicals.- 1. Telomerization Reactions.- 1.1. Telomerization of Butadiene with Acetic Acid.- 1.2. Telomerization of Butadiene with Alcohols and Phenol.- 1.3. Telomerization of Butadiene with CH-Acidic Compounds.- 1.4. Telomerization of Butadiene with Nitroalkanes.- 1.5. Carboxy-Telomerization of Butadiene.- 1.6. Telomerization of Isoprene.- 1.7. Telomerization of Piperylene.- 1.8. Telomerization of,3-Dimethylbutadiene.- 2. Dimerization Reactions.- 2.1. Dimerization of Functionalized Olefins.- 2.2. Codimerization of Different Olefins.- 2.3. Codimerization of Dienes with Functional Olefins.- 2.4. Dimerization of Dienes Followed by Functionalization.- 2.4.1. Dimerization of Isoprene.- 2.4.2. Functionalization of Isoprene Dimers.- 3. Conclusions.- References.- Oligomerization of Mono olefins.- 1. The Main Catalysts for Oligomerization.- 1.1. Catalysts with Some Isomerizing Activity.- 1.2. Catalysts Forming Linear Oligomers from Ethylene.- 1.3. Catalysts Without Any Isomerizing Activity.- 2. Mechanistic Considerations.- 3. Heterogeneous and Supported Catalysts.- 4. Industrial Developments.- 4.1. Shop Process.- 4.2. Dimersol Process.- 4.3. Alphabutol Process.- References.- Coordination Polymerization of Monoolefins and Diolefins.- 1. Introduction: The Discovery.- 2. Polymerization of Monoolefins.- 2.1. Phenomenological Aspects of the Reaction.- 2.1.1. Importance.- 2.1.2. Heterogeneous Systems.- 2.1.3. Soluble Complexes.- 2.1.4. Role of the Two Metals.- 2.2. The Mechanism and Molecular Characteristics of Polymerization Catalysis with TiCl3A1R3.- 2.2.1. The Initiation Step.- 2.2.2. The Propagation Steps.- 2.2.3. The Energetics of the Chaingrowth.- 2.2.4. Kinetic Features.- General Laws.- Number of Active Sites.- 2.2.5. The Stereoregulation.- Cossee's Proposal.- The RodriguezVan Looy Model.- More Recent Approachs.- 2.2.6. Chain Termination.- 2.3. Comparison with Soluble Catalytic Systems.- 2.3.1. Ethylene Polymerization.- 2.3.2. Propylene Polymerization.- 2.3.3. Conclusions.- 2.4. Other Related Mechanisms.- 2.4.1. Isomerization Polymerization.- 2.4.2. Green's Proposal.- 3. Polymerization of Diolefins.- 3.1. Polymerization with ZieglerNatta Catalysts.- 3.1.1. Importance.- 3.1.2. Mechanism: Structural Aspects.- 3.1.3. Kinetic Aspects.- 3.2. ?-Allyl Model Catalysts and the Concept of Chronose- lectivity.- 3.3. Conclusions.- 4. Homo- and Copolymerization or Other Types of Monomers.- 4.1. Polar Vinyl Monomers.- 4.1.1. The Catalytic Process.- 4.1.2. The Control of Apparent Reactivity in Copolymerization.- 4.2. Oxiranes.- 5. General Conclusions.- References.- Olefin Metathesis and Related Reactions.- 1. Introduction.- 2. Scope of the Reaction.- 2.1. Acyclic Monoolefins.- 2.2. Acyclic Polyolefins.- 2.3. Cyclic Olefins.- 2.4. Cyclic Diolefins.- 2.5. Cross Metathesis.- 2.6. Alkynes.- 2.7. Functional Olefins.- 3. Catalysts.- 3.1. Heterogeneous Catalysts.- 3.2. Homogeneous Catalysts.- 4. Mechanism of the Reaction.- 4.1. Transalkylation or Transalkylidenation?.- 4.2. Pairwise Mechanisms.- 4.3. Metallacyclopentanes as Intermediates.- 4.4. Non-pairwise Mechanisms.- 4.4.1. Generation of Stable Carbenes.- 4.4.2. Model Reactions.- 4.4.3. Cross Metathesis.- 4.4.4. Ring Opening Polymerization.- 4.4.5. Reaction of Carbenes and Carbynes.- 5. Stereoselectivities.- 5.1. Terminal and Internal Acyclic Olefins.- 5.2. cis- and trans-Acyclic Olefins.- 6. Initial Production of Carbene.- 6.1. Alkylidene GenerationviaReaction with a Metal alkyl Cocatalyst.- 6.1.1. Alkylidene Generation by Chemical Routes.- 6.1.2. Generation by Electrochemical Routes.- 6.2. Carbene Formation Without Alkyl-Containing Cocatalysts.- 7. Metallacarbenes as Catalyst.- 8. Role of Oxygen.- 8.1. Role of Oxygen.- 8.2. Application.- 9. Industrial Applications.- 9.1. Polymerization and Ring Opening Polymerization.- 9.2. Synthesis of Mono and Polyolefins.- 9.3. Synthesis of Functionally Substituted Olefins.- 10. Conclusion.- References.- Activation of Alkane CH Bonds by Orga-nometallics.- 1. Introduction.- 2. Oxidative Addition of Alkane CH Bonds to Organometallics.- 2.1. Background. Oxidative Addition of Activatedsp3 CH Bonds.- 2.2. Direct Observation of the Oxidative Addition Reaction.- 2.3. Reactions of Alkanes by Oxidative Addition.- 3. Activation of Alkanes by Organoactinides.- 4. Conclusions.- References.- Coordination Photochemistry: Photoinduced Electron Transfer and Redox Photocatalysis.- 1. Introduction.- 2. Properties of the Excited State.- 2.1. Kinetic Aspect.- 2.2. Redox Properties of the Excited State..- 3. Examples of Coordination Compounds with Charge Transfer Transitions.- 3.1. Various Transitions.- 3.2. Ru(bipy)3, A complex with a Long-Lived MLCT Excited State.- 3.3. Other Examples: d6 or d10 Complexes.- 4. Electron Transfer Reaction of the Excited State.- 5. Photochemical Conversion and Storage of Light Energy.- 5.1. Principle.- 5.2. A Non-Redox example: Isomerization ofNorbornadiene.- 5.3. Photochemical Reduction of Water.- 6. Concluding Remarks.- An Introduction to the Field of Catalysis by Molecular Clusters and by Supported Molecular Clusters and Complexes.- 1. An Introduction to Molecular Clusters.- 1.1. Definition of Molecular Clusters.- 1.2. Bonding in Molecular Clusters.- 1.2.1. The MetalMetal Bond in Clusters.- 1.2.2. The MetalLigand Bond.- 1.3. Dynamic Behaviour of Molecular Clusters.- 1.3.1. Ligand Migration over the Clusters Surface.- 1.3.2. Structural Rearrrangement Within the Metal Core.- 1.3.3. Ligand Migration Within the Metal Cluster Unit.- 1.4. Reactivity of Molecular Clusters.- 1.4.1. Electrophilic Attack.- 1.4.2. Nucleophilic Addition.- 1.4.3. Nucleophilic Attack at the Ligands.- 1.4.4. Oxidative Addition.- 1.5. Molecular Clusters as Structural Models of Intermediates or Chemisorbed Species in Surface Science.- 2. Catalysis by Molecular Clusters.- 2.1. The Relationship Between Molecular Clusters and Small Metal Particles.- 2.2. Homogeneous Cluster Catalyzed Reactions.- 2.3. Catalysis by Supported Molecular Clusters.- 2.3.1. The Molecular Clusters Skeleton Remains Intact.- 2.3.2. The Supported Molecular Frame is Involved in Some Steps of the Catalytic Cycle.- 2.3.3. The Molecular Cluster is Decomposed.- 2.4. Supported Clusters and Heterogeneous Catalysis: Surface Organometallic Chemistry.- References.- Future Trends in Homogeneous Catalysis.- 1. Industrial Applications of Homogeneous Catalysis.- 2. Advantages and Disadvantages of Homogeneous Catalysis.- 3. Future Applications of Homogeneous Catalysis.- 3.1. Changing Raw Material Supply.- 3.1.1. Synthesis Gas Chemistry.- 3.1.2. Alkane Chemistry.- 3.1.3. Carbon Dioxide Chemistry.- 3.2. Impacts by Engineering Requirements.- 3.3. Technological Drives.- 3.4. Society Needs.- References.- Index 349.


Titel: Industrial Applications of Homogeneous Catalysis
EAN: 9789401082310
ISBN: 9401082316
Format: Kartonierter Einband
Herausgeber: Springer Netherlands
Anzahl Seiten: 384
Gewicht: 581g
Größe: H235mm x B155mm x T20mm
Jahr: 2011
Untertitel: Englisch
Auflage: 1988

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