Oxidation reactions are an important chemical transformation in both academia and industry. Among the major advances in the field has been the development of catalytic processes, which are not only selective and efficient, but also allow the replacement of common stoichiometric oxidants with molecular oxygen, ideally from air at atmospheric pressure. This results in processes with higher atom efficiency, where water is the only side product in line with the principles of green chemistry. Focusing on the use of molecular oxygen as the terminal oxidant, this book covers recent advances in both heterogeneous and homogeneous systems, with and without metals and on the "taming" of the highly reactive oxygen gas by use of micro-flow reactors and membranes. A useful reference for industrial and academic chemists working on oxidation processes, as well as green chemists.
Author(s): Esteban Mejia
Series: Catalysis Series, 39
Publisher: Royal Society of Chemistry
Year: 2020
Language: English
Pages: 350
City: London
Cover
Half-title
Series information
Title page
Copyright information
Preface
Table of contents
CHAPTER 1 Introduction: Catalysis, Oxygen and Sustainability … Quo vadis?
1.1 Catalysis: From the Alchemist’s Philosopher’s Stone to the Chemist’s Workhorse
1.2 Catalysis’ Current Challenges: Green Chemistry
1.3 Catalysis Toward Sustainability: Aerobic Oxidation Reactions
1.3.1 The History of Oxygen
1.3.2 The Chemistry of Oxygen
1.3.3 Biologic Oxidation Catalysis
1.4 Conclusion and Perspective
References
CHAPTER 2 Aerobic Oxidation Reactions Using Metal-based Homogeneous Systems
2.1 Introduction
2.2 Aerobic Oxidation of Alcohols
2.2.1 Palladium Catalysts
2.2.2 Copper Catalysts
2.2.3 Ruthenium Catalysts
2.2.4 Other Transition Metal Catalysts
2.3 Aerobic C–H Oxidation of Methylene Compounds
2.3.1 Copper Catalysts
2.3.2 Palladium Catalysts
2.3.3 Other Metal Catalysts
2.4 Aerobic Oxidative Cleavage of Multiple C–C Bonds
2.4.1 Palladium Catalysts
2.4.2 Ruthenium and Copper Catalysts
2.4.3 Other Metal Catalysts
2.5 Concluding Remarks
References
CHAPTER 3 Aerobic Oxidation Reactions Using Metal-based Heterogeneous Systems
3.1 Introduction
3.2 Selective Oxidation Reactions
3.2.1 Natural Gas
3.2.2 The Case of Methane
3.2.3 The Case of C2–C6 Alkanes Oxidatively Transformed into Olefins (ODH) or Oxygenates with O-Insertion
3.2.4 Active Sites in Metal Oxides for Partial Oxidation of Light Alkanes
3.3 Total Oxidation Reactions
3.4 Catalyst Forms and Reactors
3.5 Reactors
3.5.1 Classical Reactors
3.5.2 New Reactor Types
3.6 Industrial Developments
3.7 Conclusions and Perspectives
References
CHAPTER 4 Aerobic Oxidations Using Metal-free Heterogeneous Systems
4.1 Introduction
4.2 Diamond NPs as Catalysts
4.3 Graphene and Related Materials for Catalysis
4.3.1 Graphene Oxide and Reduced Graphene Oxide
4.3.2 Doped Defective Graphene Oxides
4.4 Reaction Mechanism
4.5 Aerobic Oxidation of Organic Compounds Using Graphene-based Materials as Catalysts
4.5.1 Aerobic Oxidation of Benzyl Alcohols
4.5.2 Aerobic Oxidations of Benzylamines
4.5.3 Oxidation of Thiols and Sulfur Compounds
4.5.4 Aerobic Oxidation of Hydrocarbons
4.6 Summary and Future Prospects
Acknowledgments
References
CHAPTER 5 Aerobic Oxidations Reactions Using Metal-free Homogeneous Systems
5.1 Introduction
5.2 N-Oxyl Catalysts
5.2.1 General Properties
5.2.2 Alcohol Oxidations
5.2.3 C–H Functionalization
5.3 Hypervalent Iodine Compounds
5.4 Bio-mimetic and Bio-inspired Systems
5.4.1 Flavin Derivatives
5.4.2 Quinones
5.5 Other Systems
5.6 Conclusion
References
CHAPTER 6 Bio-catalyzed Aerobic Oxidation Reactions
6.1 Introduction
6.2 Aerobic Bio-catalytic C–H Functionalization
6.2.1 Aerobic Bio-catalytic Hydroxylation
6.2.2 Aerobic Bio-catalytic Halogenation
6.3 Bio-catalytic Baeyer–Villiger Oxidation
6.4 Aerobic Bio-catalytic Oxidation of Alcohols, Aldehydes and Carboxylic Acids
6.4.1 Aerobic Oxidation of Primary Alcohols
6.4.1.1 Aerobic Oxidation of Primary Alcohols Using Alcohol Oxidases or Laccases
6.4.1.2 Aerobic Oxidation of Primary Alcohols Using Alcohol Dehydrogenases
6.4.2 Aerobic Oxidation of Secondary Alcohols
6.4.2.1 Aerobic Oxidation of Secondary Alcohols Using Alcohol Oxidases and Laccases
6.4.2.2 Aerobic Oxidation of Secondary Alcohols Using Alcohol Dehydrogenases
6.4.3 Aerobic Oxidation of Aldehydes
6.4.3.1 Aerobic Oxidation of Aldehydes Using Aldehyde Oxidases, Promiscuous Alcohol Oxidases or Laccases
6.4.3.2 Aerobic Oxidation of Aldehydes Using Aldehyde Dehydrogenases
6.4.4 Aerobic Oxidative Decarboxylation
6.5 Bio-catalytic Aerobic Oxidation of Amines and Imines
6.5.1 Aerobic Kinetic Resolution and Deracemization of Amines and Amino Acids
6.5.1.1 Aerobic Kinetic Resolution and Deracemization of Amines Using Dehydrogenases
6.5.1.2 Aerobic Kinetic Resolution and Deracemization of Amines Using Monoamine Oxidases
6.5.2 Aerobic Kinetic Resolution of Amino Acids and Synthesis of a-Keto Acids
6.5.3 Aerobic Oxidation of Imines
6.6 Bio-catalytic Aerobic Oxidation of Organosulfur, Organoselenium and Organoboron Compounds
6.6.1 Aerobic Oxidation of Organosulfur Compounds
6.6.2 Aerobic Oxidation of Organoselenium and Organoboron
6.7 Bio-catalytic Aerobic Oxidation of Alkenes
6.7.1 Aerobic Epoxidation of Alkenes
6.7.2 Aerobic Mono- and Di-hydroxylation of Alkenes
6.7.2.1 Aerobic Mono-hydroxylation of Phenols and Alkenes
6.7.2.2 Aerobic Dihydroxylation of Alkenes and Arenes
6.7.3 Aerobic Bio-catalytic Alkene Cleavage
6.8 Bio-catalytic Aerobic Oxidative C–C Coupling
6.8.1 Intramolecular Oxidative C–C Coupling
6.8.2 Intermolecular Oxidative C–C Coupling
6.9 Conclusions
Acknowledgment
References
CHAPTER 7 Continuous-flow Photooxygenations: An Advantageous and Sustainable Oxidation Methodology with a Bright Future
7.1 Introduction
7.2 Singlet Oxygen in Photochemical Synthesis
7.3 Photoreactors
7.3.1 Laboratory Batch Photoreactors
7.3.2 Continuous-flow Reactors
7.4 Photooxygenation Reactions
7.4.1 Chip- or Block-based Reactors
7.4.1.1 Glass Microchip Reactors
7.4.1.2 Membrane Reactors
7.4.2 Capillary-based Reactors
7.4.2.1 Single-capillary Reactors
7.4.2.2 Tube-in-tube and Related Reactors
7.4.3 Other Reactors
7.4.3.1 Falling Film Reactors
7.4.3.2 Fluid-bed Reactors
7.4.3.3 Aerosol Reactors
7.4.3.4 High-pressure Reactors
7.4.3.6 Solar Reactors
7.4.4 Commercial Reactors and Scale-up
7.4.4.1 Capillary Reactors
7.4.4.2 Packed-bed Reactors
7.4.4.3 Block Reactors
7.5 Limitations and Challenges
7.6 Conclusion
Acknowledgments
References
CHAPTER 8 Aerobic Oxidation Reactions in the Fine Chemicals and Pharmaceutical Industries
8.1 Introduction
8.2 Challenges of Working with Air/Molecular Oxygen
8.3 Batch Technologies for Catalytic Aerobic Oxidations
8.4 Flow and Membrane Technologies for Catalytic Aerobic Oxidations
8.5 Prospective Reactions for Scale-up
8.5.1 Prospective Reactions in Batch
8.5.2 Prospective Reactions in Continuous Flow or with Membrane Technologies
8.5.3 Prospective Bio-catalytic Reactions
8.5.4 Prospective Photocatalytic Reactions
8.5.5 Prospective Electrocatalytic Reactions
8.6 Conclusions and Outlook
References
CHAPTER 9 Industrial Aerobic Oxidation of Hydrocarbons
9.1 The Industrial Aerobic Oxidation of Hydrocarbons
9.2 Oxychlorination of Ethylene and Ethane to 1,2-Dichloroethane and Vinyl Chloride
9.2.1 Industrial Synthesis of 1,2-Dichloroethane
9.2.2 Catalyst Types for Ethylene Oxychlorination
9.2.3 An Alternative Approach: Direct Oxychlorination/Dehydrochlorination of Ethylene to VCM
9.2.4 An Alternative Reagent: Ethane
9.3 Oxidation of C4 Hydrocarbons to Maleic Anhydride
9.3.1 Industrial Synthesis of Maleic Anhydride
9.3.2 Main Features of the VPP Catalyst for n-Butane Oxidation to MA
9.3.3 Role of the Reactor Type: Recent Findings
9.3.4 Role of Promoters and Supports in VPP Technical Catalysts
9.3.5 Procedure used for VPP Preparation: Recent Findings
9.3.6 Reactivity of C4 Alkenes and Their Reaction Pathway
9.4 Conclusions
References
Subject Index
