New Syntheses with Carbon Monoxide

ISBN-13: 9783642674549 / Angielski / Miękka / 2011 / 468 str.

J. Falbe; H. Bahrmann; B. Cornils

Opis

More than a decade has passed since the appearance of the last edition of the book "Carbon Monoxide in Organic Synthesis." During the intervening period, the signi ficance of carbon monoxide chemistry has become even more evident. The oil crisis and the ever-present awareness of the constant depletion of the oil reserves have both contributed to a surge in activity. The fact that coal will once again replace oil in the near future as a feedstock source has been an impetus for new efforts in the field of carbon monoxide chemistry. Moreover, older almost neglected processes such as the Fischer-Tropsch synthesis have become a focal point for new activities. Therefore, the time was ripe to fundamentally revise "Carbon Monoxide in Organic Synthesis" and to complete its coverage by introducing the chapters "Homo logation" and "Carbon Monoxide Hydrogenation." However, other important sectors of carbon monoxide chemistry such as the con version of synthesis gas to methanol or higher alcohols were excluded. These are treated in the book "Chemierohstoffe aus Kohle," which devotes considerable attention to these syntheses. I would like to thank Drs. Bahrmann, Comils, Frohning, Mullen and Tummes, who had the task of compiling and critically evaluating the large volume of literature which has appeared during the last decade."

Spis treści

1 Hydroformylation. Oxo Synthesis, Roelen Reaction.- 1.1 Introduction.- 1.2 Hydroformylation Mechanism.- 1.2.1 The Mechanism According to Heck and Breslow.- 1.2.2 Recent Interpretations.- 1.2.3 Kinetics.- 1.2.4 Potential Industrial Significance.- 1.3 Effect of Reaction Conditions on Conversion, Selectivity and Operation of the Oxo Synthesis.- 1.3.1 Temperature.- 1.3.1.1 Unmodified Catalysts.- 1.3.1.2 Modified Catalysts.- 1.3.2 Total Pressure; CO and H2 Partial Pressures.- 1.3.2.1 Unmodified Catalysts.- 1.3.2.2 Modified Catalysts.- 1.3.3 Catalysts.- 1.3.3.1 Hydroformylation Catalysts and their Variants.- 1.3.3.1.1 Via Variation of Central Atom.- 1.3.3.1.2 Via Variation of Ligands.- Cobalt Catalysts.- Rhodium Catalysts.- Various.- 1.3.3.1.3 Via Variation of Application Phase.- Heterogenized (Immobilized) Catalysts.- Production of Heterogenized Oxo Catalysts.- Hydroformylation with Heterogenized Oxo Catalysts.- Gas Phase Hydroformylation.- Various Methods.- 1.3.3.1.4 Activators, Promoters and Other Catalyst Additives.- 1.3.3.2 Catalyst Poisons.- 1.3.3.3 Effect of Catalyst Concentration.- 1.3.3.4 Catalyst Recycle in Industrial Oxo Process.- 1.3.3.4.1 Unmodified Catalysts.- 1.3.3.4.2 Modified Catalysts.- 1.3.4 Solvent Effects.- 1.3.5 Concentration of Reactants.- 1.3.6 Residence Time of Reactants.- 1.3.7 Influence of Reaction Conditions on Construction and Operation of Industrial Oxo Reactors.- 1.4 Hydroformylation of Particular Structures.- 1.4.1 Monoolefins.- 1.4.2 Di- and Triolefins.- 1.4.2.1 Di- and Triolefins with Isolated Double Bonds.- 1.4.2.2 Conjugated Systems and Alienes.- 1.4.3 Acetylenes.- 1.4.4 Functionally Substituted Olefins.- 1.4.4.1 Unsaturated Alcohols.- 1.4.4.2 Unsaturated Aldehydes and Ketones.- 1.4.4.3 Unsaturated Esters.- 1.4.4.4 Unsaturated Ethers and Acetals.- 1.4.4.5 Unsaturated Halogen Compounds.- 1.4.4.6 Unsaturated Nitrogen Compounds.- 1.4.4.7 Hydroformylation of Special Compounds.- 1.4.5 Hydroformylation of Polymers.- 1.4.6 Asymmetric Hydroformylation.- 1.5 Parallel and Consecutive Reactions Under Hydroformylation Conditions.- 1.5.1 Side Reactions Resulting in a Decrease in Yield.- 1.5.1.1 Hydrogenation of Olefins to Hydrocarbons.- 1.5.1.2 Formation of Formic Acid Esters.- 1.5.1.3 Ketone Formation.- 1.5.1.4 Formation of Heavy Ends.- 1.5.2 Selectivity Lowering Secondary Reactions.- 1.5.2.1 Aldolization of Aldehydes.- 1.5.2.1.1 Undesired Aldolizations.- 1.5.2.1.2 Controlled Aldolization (Aldox Variants).- 1.5.2.2 Hydrogenation of Aldehydes to Alcohols.- 1.5.2.2.1 Undesired Hydrogenation.- 1.5.2.2.2 Controlled Hydrogenation.- 1.5.2.3 Synthesis of Isomeric Oxo Products.- 1.5.2.3.1 The n:iso Problem of the Oxo Synthesis.- With Propylene or Butylenes.- With Higher Olefins as Feedstocks.- The Hydroformylation of Functionally Substituted Olefins.- 1.5.2.3.2 Isobutyraldehyde as the ‘Main By-product’ of the Propylene Hydroformation.- Secondary Reactions with Isobutyraldehyde.- Cracking of Isobutyraldehyde.- Isomerization of Isobutyraldehyde.- 1.5.3 Various Side Reactions.- 1.5.4 Work up of By-products of the Oxo Synthesis to Value Products.- 1.6 The Industrial Oxo Synthesis: Process Variants and Economic Background.- 1.6.1 Industrial Aspects of the Oxo Synthesis.- 1.6.2 Process Variants of the Industrial Oxo Syntheses.- 1.6.2.1 Cobalt (Compounds) as Catalysts.- 1.6.2.1.1 Ruhrchemie Process.- 1.6.2.1.2 BASF Process.- 1.6.2.1.3 Kuhlmann (PCUK) Process.- 1.6.2.1.4 Shell Process.- 1.6.2.1.5 Various Processes.- 1.6.2.2 Rhodium (Compounds) as Catalysts.- 1.6.2.2.1 Ruhrchemie Process.- 1.6.2.2.2 Process Developed by the Group—Union Carbide/Davy Powergas/Johnson, Matthey & Co. (Low PressureOxo Process—LPO).- 1.6.2.2.3 Process Developed by Union Oil of California.- 1.6.2.2.4 Various Processes.- 1.6.3 Comparative Considerations.- 1.6.4 Economic Aspects of Industrial Oxo Processes.- 1.6.5 Oxo-analogue Reactions.- 1.7 References.- 2 Homologation of Alcohols.- 2.1 Introduction.- 2.2 Reaction Mechanism.- 2.3 Effekt of Reaction Conditions.- 2.3.1 Catalysts and Promoters.- 2.3.2 Temperature.- 2.3.3 Pressure.- 2.3.4 CO:H2 Ratio.- 2.3.5 Catalyst Concentration.- 2.4 Homologation of Particular Structures.- 2.5 Parallel and Secondary Reactions of the Homologation.- 2.5.1 Hydrogenation.- 2.5.2 Carbonylation to Acids.- 2.5.3 Acetal Formation.- 2.5.4 Ether Formation.- 2.6 Heterogeneously Catalyzed Homologation.- 2.7 Future Prospects of the Homologation.- 2.7.1 As an Alternative Source of Ethylene.- 2.7.2 Production of Styrene.- 2.7.3 The Production of Methyl Fuels.- 2.8 References.- 3 Carbonylations Catalyzed by Metal Carbonyls-Reppe Reactions.- 3.1 Introduction.- 3.2 Reaction Mechanism.- 3.3 Catalysts.- 3.3.1 Nickel Catalysts.- 3.3.2 Cobalt Catalysts.- 3.3.3 Rhodium Catalysts.- 3.3.4 Palladium and Platinum Catalysts.- 3.3.5 Iron Catalysts.- 3.3.6 Copper Catalysts.- 3.4 Effect of Temperature and Pressure.- 3.5 Solvents.- 3.6 Carbonylation of Various Structures.- 3.6.1 Carbonylation of Alkynes.- 3.6.1.1 Alkynes and Functional Derivatives in the Presence of Water.- Various Catalysts.- 3.6.1.2 Alkynes and Derivatives in the Presence of Alcohols.- 3.6.1.3 Alkynes in Presence of Carboxylic Acids, Hydrogen Halides, Mercaptans or Amines.- 3.6.2 Carbonylation of Alkenes.- 3.6.2.1 Alkenes and Functional Derivatives in the Presence of Water.- 3.6.2.1.1 Oxidative Carbonylation of Alkenes.- 3.6.2.2 Alkenes and Functional Derivatives in the Presence of Alcohols.- 3.6.2.3 Alkenes and Functional Derivatives in the Presence of Nucleophiles other than Water or Alcohols.- 3.6.3 Carbonylation of Alcohols.- 3.6.3.1 Cobalt Catalysts.- 3.6.3.2 Rhodium Catalysts.- 3.6.3.3 Nickel Catalysts.- 3.6.3.4 Palladium Catalysts.- 3.6.3.5 Various Catalysts.- 3.6.4 Carbonylation of Amines.- 3.6.5 Carbonylation of Ethers and Esters.- 3.6.5.1 Carbonylation of Carboxylic Acid Esters.- 3.6.5.2 Carbonylation of Ethers.- 3.6.6 Carbonylation of Halides.- 3.6.7 Carbonylation of Aldehydes.- 3.6.8 Carbonylation of Aromatic Nitro Compounds.- 3.7 Industrial Applications of Carbonylation Reactions.- 3.7.1 Production of Acrylic Acid and its Esters.- 3.7.2 Production of Acetic Acid.- 3.7.3 Production of Butanol and Propionic Acid.- 3.7.4 Production of Tolylene Diisocyanates.- 3.8 Concluding Remarks.- 3.9 References.- 4 Hydrogenation of the Carbon Monoxide.- 4.1 Methanol Syntheses.- 4.1.1 General Remarks.- 4.1.2 Reaction Mechanism.- 4.1.3 Reaction Conditions.- 4.1.4 Catalysts.- 4.1.5 Processes.- 4.1.6 Economic Potential and Possible Developments in Methanol Synthesis.- 4.2 Glycol Syntheses.- 4.2.1 General Remarks.- 4.2.2 Glycols via Hydrogenation of Carbon Monoxide with Cobalt Catalysts.- 4.2.3 Glycols via Hydrogenation of Carbon Monoxide with Rhodium Catalysts.- 4.2.4 Economic Potential and Possible Developments in the Glycol Synthesis.- 4.3 Methane Syntheses.- 4.3.1 General Remarks.- 4.3.2 Reaction Mechanism.- 4.3.3 Reaction Conditions.- 4.3.4 Catalysts.- 4.3.5 Processes.- 4.3.6 Economic Potential and Possible Developments in the Methane Synthesis.- 4.4 The Fischer-Tropsch Hydrocarbon Synthesis.- 4.4.1 General Remarks.- 4.4.2 Reaction Mechanism.- 4.4.2.1 Stoichiometry.- 4.4.2.2 Thermodynamics.- 4.4.2.3 Mechanism.- 4.4.2.4 Kinetics.- 4.4.3 Reaction Conditions.- 4.4.4 Catalysts.- 4.4.5 Processes.- 4.4.6 Economic Potential and Possible Developments.- 4.5 Polymethylene Synthesis.- 4.5.1 General Remarks.- 4.5.2 Reaction Mechanism.- 4.5.3 Catalysts.- 4.5.4 Reaction Conditions.- 4.5.5 Economic Potential and Possible Developments in the Polymethylene Synthesis.- 4.6 References.- 5 Koch Reactions.- 5.1 Introduction.- 5.2 Reaction Mechanism.- 5.2.1 Formation of Intermediate Carbenium Ions 2 from Various Precursors.- 5.2.2 Reactions of Intermediate Carbenium Ions 2.- Isomerization / Rearrangement.- Olefin Formation.- Disproportionation.- Oligomerization.- Cracking of the Carbon Skeleton.- 5.2.3 Formation of Intermediate Acyl Cations.- 5.2.4 Reactions of Intermediate Acyl Cations.- 5.2.5 Secondary Reactions of Carboxylic Acids.- 5.2.6 Retro-Koch Reaction.- 5.2.7 Heterogeneous Variants of the Koch Synthesis.- 5.3 Catalysts.- 5.3.1 Based on BF3.- 5.3.2 Based on H2SO4.- 5.3.3 Based on H3PO4.- 5.3.4 Based on HF.- 5.3.5 Based on SbF5/SbCl5.- 5.3.6 Various.- 5.3.7 Normal Pressure Synthesis in Presence of Elements of Group IB.- 5.4 Effect of Temperature and Pressure.- 5.5 Solvents and Diluents.- 5.6 Carbonylation of Particular Compounds.- 5.6.1 Olefins and Dienes.- 5.6.2 Alcohols and Diols.- 5.6.3 Paraffins.- 5.6.4 Unsaturated Carboxylic Acids.- 5.6.5 Halogenated Compounds.- 5.6.6 Other Starting Materials.- 5.7 Industrial Applications and Economic Aspects.- 5.8 References.- 6 Ring Closure Reactions with Carbon Monoxide.- 6.1 Introduction.- 6.2 Reaction Mechanism.- 6.3 Catalysts, Reaction Conditions and Solvents.- 6.3.1 Catalysts.- 6.3.2 Reaction Conditions.- 6.3.3 Solvents.- 6.4 Ring Closure Reactions with CO and Various Substrates.- 6.4.1 Formation of Imides.- 6.4.2 Formation of Lactams.- 6.4.3 Formation of Lactones.- 6.4.3.1 Lactones via Carbonylation of Unsaturated Alcohols, Esters or Acids.- 6.4.3.2 Lactones via Carbonylation of Alkenes or Alkynes.- 6.4.3.3 Lactones via Carbonylation of Cyclic Ethers or Epoxides.- 6.4.3.4 Lactones via Carbonylation of Alkyl, Allyl or Acyl Halides.- 6.4.4 Formation of Phthalimidines from Schiff Bases or Aromatic Nitriles.- 6.4.5 Formation of Phthalimidines from Aromatic Ketoximes, Phenylhydrazones, Semicarbazones or Azines.- 6.4.6 Formation of Indazolones and Quinazolines from Azobenzenes.- 6.4.7 Formation of Indones.- 6.4.8 Formation of Cyclic Ketones from Dienes.- 6.4.9 Formation of Phenols from Allyl Halides and Alkynes.- 6.4.10 Other Carbonylation Reactions Leading to Heterocyclic Compounds.- 6.4.10.1 Formation of Oxygen-Containing Ring Systems.- 6.4.10.2 Formation of Nitrogen-Containing Ring Systems.- 6.4.10.3 Formation of Sulfur-Containing Ring Systems.- 6.5 Commercial Applications.- 6.6 References.