Chemistry of Dehydrogenation Reactions and Its Applications

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Half Title
Emerging Materials and Technologies Series
Chemistry of Dehydrogenation Reactions and Its Applications
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Contents
Preface
About the Editors
Contributors
1. Introduction to Dehydrogenation Reactions of Organic Compounds
	1.1 Introduction
	1.2 Mechanism of Dehydrogenation Reactions
		1.2.1 Alkane to Alkene
		1.2.2 Alcohol to Carbonyl Derivatives
		1.2.3 Dehydrogenation to Yield Olefins with EWG at α-Position
		1.2.4 Ester and Nitrile to Activated Olefins
		1.2.5 Amide/Lactam to Activated Olefins
	1.3 Heterogeneous and Homogeneous Catalysts for Dehydrogenation Reactions
	1.4 Types of Reactors for Dehydrogenation Reactions
	1.5 Dehydrogenation Methods and Reactions That Are Commercially Significant
		1.5.1 Dehydrogenation of Paraffins to Olefins
		1.5.2 Dehydrogenation of C2-C15 Alkanes to Alkenes
		1.5.3 Dehydrogenation of Ethylbenzene to Styrene
	1.6 Recent Advances in Dehydrogenation Technology
	1.7 Summary
	References
2. Transition Metal-Based Catalyst for Dehydrogenation Reactions of Organic Compounds
	2.1 Introduction
	2.2 N-Alkylation by Dehydrogenative Alcohol Activation
		2.2.1 N-Alkylation by Ruthenium Catalyst
		2.2.2 N-Alkylation by Iridium Catalyst
		2.2.3 N-Alkylation by Pd Catalyst
		2.2.4 N-Alkylation by Copper/Iron Catalyst
		2.2.5 Synthesis of Primary Amine from Alcohol and Ammonia/Ammonium Salt
		2.2.6 Enantioselective Substitution of Alcohols by Amine
		2.2.7 Reductive N-Alkylation with Alcohols
	2.3 C-alkylation by Dehydrogenative Alcohol Activation
		2.3.1 α-Alkylation of Ketones and Its Derivative
		2.3.2 β-Alkylation of Secondary Alcohols
		2.3.3 α-Alkylation of Activated Nucleophile
		2.3.4 Asymmetric C-C Bond Formation by Alcohols Activation
		2.3.5 Versatile HA-sequence by Dehydrogenative Alcohol Coupling
	2.4 Dehydrogenative Amine Activation
		2.4.1 Transamination
		2.4.2 Hydroimination
	2.5 Dehydrogenative Alkane Activation
	2.6 Net Dehydrogenative Oxidation Reactions
		2.6.1 Formation of Ester and Acid
		2.6.2 Formation of Amide
		2.6.3 Formation of Nitriles by Amine Oxidation
	2.7 Semi-Borrowing Hydrogen (SBH) Process
		2.7.1 Synthesis of Benzimidazoles
		2.7.2 Modified Fischer Indole Synthesis
		2.7.3 Synthesis of Quinazolines Derivatives
		2.7.4 Synthesis of Pyrroles Derivatives
	2.8 Conclusions
	References
3. Transition Metal Catalyst Free Dehydrogenative Organic Synthesis: Role of New Materials, Composites, and Nanomaterials
	3.1 Introduction
	3.2 Nanotechnology Catalysts for Hydrogenation Budge in Organic Synthesis
	3.3 Heterogenization of Homogeneous Catalysts for Dehydrogenation Reactions
	3.4 Anchoring Homogeneous Catalysts over Heterogeneous Support
	3.5 Direct Grafting of Metal Complexes
	3.6 Encapsulation of the Catalysts
	3.7 Ionic Liquid Assisted Organic Transformation
	3.8 Single and Double Atom Catalysts for Transfer Hydrogenation Reactions
	3.9 Conclusions
	3.10 Outlook
	References
4. Dehydrogenation Reaction of Aliphatic and Aromatic Alcohols
	4.1 Objectives
	4.2 Dehydrogenation Reaction
	4.3 Aliphatic and Aromatic Alcohols
	4.4 Dehydrogenation of Alcohols
	4.5 Acceptorless Dehydrogenation of Alcohols
		4.5.1 Conversion of Alcohols into Carbonyl Compounds
		4.5.2 Conversion of Alcohols into Ester Compounds
		4.5.3 Conversion of Alcohols into Amide Compounds
		4.5.4 Conversion of Alcohols into Imines Compounds
		4.5.5 Conversion of Alcohols into Acylated Compounds
		4.5.6 Conversion of Alcohols into Acetals Compounds
		4.5.7 Conversion of Alcohols into Polyester and Lactones Compounds
		4.5.8 Direct Synthesis of Pyrrole from Alcohols
	4.6 Green Method for the Dehydrogenation of Alcohols
		4.6.1 Dehydrogenation of Alcohols with Nanoparticles
		4.6.2 Dehydrogenation of Alcohols with Photocatalyst
	4.7 Conclusions
	References
5. Dehydrogenation Reactions of Hydrocarbons: Alkane, Alkenes, and Aromatic Hydrocarbons
	5.1 Introduction
	5.2 Non-Oxidative Dehydrogenation
		5.2.1 Platinum-Based Catalyst
		5.2.2 Chromium Oxide-Based Catalyst
		5.2.3 Vanadium Oxide-Based Catalyst
		5.2.4 Molybdenum Oxide-Based Catalysts
		5.2.5 Gallium Oxide-Based Catalyst
		5.2.6 Carbon-Based Catalyst
	5.3 Oxidative Dehydrogenation
		5.3.1 Groups V and VI Transition Metal Oxides
		5.3.2 Ni-Based Catalyst Systems
		5.3.3 Lithium and Halide-Containing Catalysts
	5.4 Dehydrogenation of Alkanes by Pincer Complexes
		5.4.1 Dehydrogenation of Alkane by Pincer Iridium Complexes
		5.4.2 Pincer-Ruthenium Complexes as Catalysts for Alkane Dehydrogenation
	5.5 Dehydrogenation of Aromatic Hydrocarbons
		5.5.1 Catalytic Dehydrogenation of Aromatic Hydrocarbons Using Pd or Pt
		5.5.2 Dehydrogenation of Aromatic Hydrocarbons Using DDQ
	References
6. Dehydrogenation Reactions of Aliphatic and Aromatic Amines
	6.1 Introduction
	6.2 Mechanistic Consideration
	6.3 Dehydrogenation Reactions of Aliphatic Amines
		6.3.1 Ru-Catalyzed Dehydrogenation
		6.3.2 Mo-Catalyzed Dehydrogenation
		6.3.3 Ni-Catalyzed Dehydrogenation
		6.3.4 Ir-Based Catalyst for Dehydrogenation
	6.4 Dehydrogenation Reactions of Aromatic Amines
	6.5 Challenges and Future Prospects
	References
7. Dehydrogenation Reactions of Aliphatic and Aromatic Carboxylic Acids and Their Derivatives
	7.1 Introduction
	7.2 Dehydrogenation Reactions of Aliphatic and Aromatic Carboxylic Acids
	7.3 Conclusion
	References
8. Dehydrogenation Reactions of Heterocyclic Compounds and Their Derivatives
	8.1 Introduction
	8.2 Transition Metal-Catalyzed Synthesis of Heterocyclic Compounds
		8.2.1 Synthesis of Lactones by Heterogeneous TM Catalysts
		8.2.2 Benzofurans and Chromones from Ortho-Substituted Phenols
		8.2.3 Nitrogen-Containing Heterocycles by Heterogeneous TM Catalysts
		8.2.4 Indoles, Benzimidazoles, Quinazolinones and Pyrroles
	8.3 Summary and Outlook
	References
9. Recent Advances in Dehydrogenative Technique for Hydrogen Energy Storage and Utilization
	9.1 Introduction
	9.2 Important Properties of LOHC
	9.3 Mono- and Polyaromatic Systems for LOHC Applications
		9.3.1 Benzene-Cyclohexane System
		9.3.2 Toluene-Methylcyclohexane System
		9.3.3 Decalin-Naphthalene System
		9.3.4 Perhydrodibenzyltoluene–Dibenzyltoluene
	9.4 Heterocyclic Compounds
		9.4.1 Carbazole Derivatives
		9.4.2 Pyridines and Quinolines
		9.4.3 Pyrroles and Indoles
	9.5 Integration of LOHC Process
	9.6 Reactor for LOHC
	9.7 Theoretical and Computational Approach
	9.8 Conclusions
	References
10. Dehydrogenation Reactions and Inspirations from Nature for the Synthesis of Building Blocks Leading to Valued Pharmaceutical Compounds
	10.1 Introduction
	10.2 Dehydrogenation Reactions Found in Nature
	10.3 Dehydrogenation Reactions Inspired by Nature
		10.3.1 Quinoline Derivatives
		10.3.2 Pyrrole Derivatives
		10.3.3 β-Carboline Derivatives
		10.3.4 Thienoquinolines Derivatives
		10.3.5 Benzimidazoles Derivatives
		10.3.6 Galantamine Derivatives
		10.3.7 Pyrazolone and Pyrazole Derivatives
	10.4 Metabolic Oxidative Dehydrogenation Reactions
	10.5 Miscellaneous Dehydrogenation Reactions
	10.6 Conclusions and Perspectives
	References
11. Industrial Applications of Dehydrogenation Reactions: Process Design of Reactors
	11.1 Introduction
	11.2 Process Design of Reactors
		11.2.1 Ideal Reactors
		11.2.2 Non-Ideal Reactors
	11.3 Reactor Networking
	11.4 Additional Design Considerations for Real Reactors
	11.5 Conclusion
	References
12. Future Aspects of Dehydrogenative Reactions
	12.1 Introduction
	12.2 Development of the Existing Catalytic Technologies via the Designing of More Selective, Active Catalysts
	12.3 Developing Sustainable, Eco-Friendly, and Green Dehydrogenation Technologies
	12.4 Selective Hydrogen Oxidation: Design and Development of a Novel Catalyst and Facile Process
	12.5 Development of Membrane Separation Techniques for Removing Hydrogen from the Dehydrogenation Product
	12.6 Green, Sustainable, Safe, and Environmentally Friendly Manufacturing Techniques
	12.7 Development of New Catalysts Replacing Noxious Metals and Metal Oxides
	12.8 Development of Reformed Heterogeneous Catalysts via Surface Modifications
	12.9 Efficient Heterogenized-Homogeneous Catalyst Development for Modified Dehydrogenation Reactions
	12.10 Development of Dehydrogenative Technologies for Hydrogen Energy Storage and Utilization
	References
13, Utilizing Ruthenium (Ru) Complexes in Dehydration Reactions of Saturated and Unsaturated Compounds
	13.1 Introduction
	13.2 Alcohol Dehydrogenation Reactions Based on Ru
		13.2.1. Aliphatic versus Aromatic Ligands
		13.2.2 Dehydrogenation of Formic Acid (FA)
		13.2.3 Dehydrogenation of C-N Bond by Ru Catalyst
		13.2.4 Ruthenium-Catalyzed Dehydrogenation of Alkene
	13.3 Conclusion
	13.4 Abbreviations
	References
14. Dehydrogenation Reactions Incorporating Membrane Catalysis
	14.1 Introduction
	14.2 The History of Membrane Catalysis
	14.3 Major Merits of H2-Absorptive Membrane Catalysts in Subsequent Reactions with the Expulsion of H2
	14.4 Dehydrogenation on Palladium Membranes
	14.5 Dehydrogenation Using a Composite Membrane Catalyst
	14.6 Dehydrogenation of Low Molecular Alkane, Alkene, and Alcohol
	14.7 Dehydrogenation of Cyclohexane and Methylcyclohexane
	14.8 Conclusion
	References
15. A Greener Dehydrogenation: Environmentally Benign Reactions
	15.1 Introduction
		15.1.1 Oxidative Catalytic Dehydrogenation
		15.1.2 Oxygen-Based Oxidative Dehydrogenation
		15.1.3 Carbon Dioxide-Based Oxidative Dehydrogenation
		15.1.4 Nitrous Oxide-Based Oxidative Dehydrogenation
		15.1.5 Comparison of Catalytic ODH over DDH
	15.2 Acceptorless Dehydrogenation
	15.3 Nanoparticle-Based Catalyzed Dehydrogenation
	15.4 Photocatalysis-Based Dehydrogenation
	15.5 Water-Mediated Dehydrogenation Reactions
	15.6 Conclusion and Future Prospects
	15.7 Conflict of Interest
	References
16. Application of Pt- and Non Pt-Based Zeolitic Catalysts for the Dehydrogenation of Light Alkanes
	16.1 Introduction
	16.2 Chemistry of Dehydrogenation
	16.3 Non Pt-Based Zeolitic Catalyst
		16.3.1 Vanadium Oxide-Based Zeolitic Materials
		16.3.2 Chromium Oxide-Based Zeolitic Materials
	16.4 Pt-Based Zeolitic Catalyst
		16.4.1 Sn Metal as Promoter
		16.4.2 Ce Metal as Promoter
		16.4.3 Gallium (III) Oxide as Promoter
		16.4.4 Alkaline Earth Metals as Promoter
		16.4.5 Transition Metals as Promoters
	16.5 Conclusion
	References
17. Porous Inorganic Nanomaterials as Heterogeneous Catalysts for the Dehydrogenation of Paraffin
	17.1 Introduction
	17.2 Principle of Dehydrogenation
	17.3 Heterogeneous Catalysts for Paraffin Dehydrogenation
		17.3.1 Metal Oxide Catalyst
		17.3.2 Nanoporous Materials-Based Single Atom (SA) and Single Atom Alloy (SAA) Catalysts
		17.3.3 Metal Organic Frameworks (MOFs)-Based Catalyst
	17.4 Outlook and Conclusion
	References
Index