Discover how carbonyl compounds bridge reactants, catalysts, and specific products
Carbonyl-containing molecules represent some of the most versatile functionalities in organic chemistry, with applications in a wide variety of areas.
In Carbonyl Compounds: Reactants, Catalysts and Products, accomplished chemists and authors Feng Shi, Hongli Wang, and Xingchao Dai deliver a comprehensive treatment of these multi-functional compounds. You’ll discover how to build carbonyl molecules with traditional and non-traditional methods, how to transform carbonyl-containing molecules into fine chemicals, and how to use carbonyl-containing molecules as catalytic materials for the synthesis of fine chemicals.
The book is a comprehensive and systematic treatment of carbonyl compounds as reactants, catalysts, and products. From the use of carbon monoxide in the hydroformylation of alkenes and alkynes to the reactions via carbonyl and hydroxyl groups recycling, you’ll find everything you need to know about these versatile compounds.
Readers will also benefit from the inclusion of: - A thorough introduction to carbonyl molecules as reactants, including treatments of carbon monoxide, carbon dioxide, HCHO, HCOOH, and CO surrogates - An exploration of carbonyl compounds as catalysts, including acid catalyzed reactions with -CO2H and reactions via carbonyl and hydroxyl groups recycling - A practical discussion of the synthetic applications of carbonyl compounds, including the synthesis of functional molecules and the synthesis of functional materials - A concise treatment of future perspectives and potential research trends for carbonyl molecules
Perfect for organic, catalytic, pharmaceutical, and physical chemists, Carbonyl Compounds will also earn a place in the libraries of chemical engineers and materials scientists seeking a one-stop reference for up-to-date information about the building, transformation, and applications of carbonyl-containing molecules.
Table of Contents
Preface xi
Part I Carbonyl Molecules as Reactants 1
1 Carbon Monoxide 3
1.1 Hydroformylation of Alkenes and Alkynes 3
1.1.1 Co Catalysts 4
1.1.2 Rh Catalysts 5
1.1.3 Au Catalysts 7
1.1.4 Ligand-Modified Heterogeneous Catalysts 7
1.1.5 Single-Atom Catalysts 10
1.2 Hydroxy-, Alkoxy-, and Aminocarbonylation of Alkenes and Alkynes 11
1.2.1 Hydroxycarbonylation of Alkenes 11
1.2.2 Hydroxycarbonylation of Alkynes 13
1.2.3 Alkoxycarbonylation of Alkenes 14
1.2.4 Alkoxycarbonylation of Alkynes 16
1.2.5 Aminocarbonylation of Alkenes 17
1.2.6 Aminocarbonylation of Alkynes 19
1.3 The Pauson-Khand Reaction 20
1.3.1 The Catalytic Pauson-Khand Reaction 21
1.3.2 Stereoselective Pauson-Khand Reactions 23
1.3.3 Pauson-Khand Transfer Carbonylation Reactions 25
1.4 Synthesis of Acetic Acid 26
1.4.1 Process Considerations 26
1.4.2 Rhodium-Catalyzed Carbonylation 27
1.4.3 Iridium-Catalyzed Carbonylation 28
1.5 Carbonylation of C-X Bonds 30
1.5.1 Hydroxy-, Alkoxy-, and Aminocarbonylations of C-X Bonds 30
1.5.2 Reductive Carbonylations 34
1.5.3 Carbonylative Coupling Reactions with Organometallic Reagents 36
1.5.4 Carbonylative Sonogashira Reactions 41
1.5.5 Carbonylative C-H Activation Reactions 44
1.5.6 Carbonylative Heck Reactions 46
1.6 Carbonylation of Epoxides 48
1.6.1 Ring-expansion Carbonylation of Epoxides 48
1.6.2 Hydroformylation and Silylformylation of Epoxides 50
1.6.3 Alternating Copolymerization of Epoxides 50
1.6.4 Alkoxycarbonylation and Aminocarbonylation of Epoxides 51
1.7 Carbonylation of Aldehydes 52
1.7.1 Amidocarbonylations of Aldehydes 52
1.7.2 Hydroformylation and Silylformylation of Aldehydes 54
1.7.3 Hetero Pauson-Khand Reactions of Aldehydes 55
1.7.4 Reactions of Aldehydes with Acylanions 55
1.7.5 Miscellaneous of Aldehydes 56
1.8 Oxidative Carbonylation Reaction 57
1.8.1 Oxidative Carbonylation of Alkenes 57
1.8.2 Oxidative Carbonylation of Alkynes 59
1.8.3 Oxidative Carbonylation of Organometallic Reagents 63
1.8.4 Oxidative Carbonylation of Arenes 65
1.8.5 Oxidative Carbonylation of Amines 67
1.9 Other Reactions 69
1.9.1 Reactions of Diazoalkanes with Carbon Monoxide 70
1.9.2 Reaction of C-NO2 with CO 73
2 Carbon Dioxide 75
2.1 Synthesis of Urea Derivatives 75
2.1.1 Metal-free Catalyst Systems 75
2.1.2 Ph3SbO as Catalyst 75
2.1.3 Pd Catalyst Systems 76
2.1.4 Ionic Liquids as Catalyst 76
2.1.5 CeO2 as Catalyst 77
2.2 Synthesis of Carbamate Derivatives 78
2.2.1 Ru Catalyst Systems 78
2.2.2 Sn or Ni Catalyst Systems 79
2.2.3 Zeolite as Catalyst 79
2.2.4 Other Catalyst Systems 81
2.3 Synthesis of Carboxyl Acid Derivatives 82
2.4 Cycloaddition of Epoxide with CO2 88
2.4.1 Oxides Catalysts 93
2.4.2 Zeolite Catalysts 94
2.4.3 Supported Nanoparticle and Lewis Acid Catalysts 95
2.4.4 Carbon Catalysts 98
2.4.5 Salen, Porphyrins, and Phthalocyanines Catalysts 98
2.4.6 Ionic Liquid Catalysts 101
2.4.7 Metal-Organic Framework (MOF) Catalysts 106
2.4.8 Bifunctional Catalysts 109
2.4.9 Other Catalysts 117
2.5 Reaction of Polyalcohols/Olefins with CO2 119
2.6 Formylation of Amines with CO2 121
2.7 Reactions of Propargyl Alcohols/Propargyl Amines with CO2 125
2.8 Other Reactions 127
2.8.1 Reactions of Aromatic Halides with CO2 127
2.8.2 Reactions of 2-Aminobenzonitriles with CO2 130
3 Other C1 Carbonyl Molecules 133
3.1 Formaldehyde (HCHO) 133
3.1.1 Carbonylation of Halides with HCHO 134
3.1.2 Carbonylation of Olefins with HCHO 136
3.1.3 Carbonylation of Alkynes with HCHO 142
3.2 Formic Acid (HCOOH) 144
3.2.1 Hydroxycarbonylation of Arenes with Formic Acid 144
3.2.2 Carbonylation of Alkenes with Formic Acid 144
3.2.3 Carbonylation of Alkynes with Formic Acid 148
3.2.4 N-Formylation Reactions with Formic Acid 150
3.2.4.1 Metal Oxides Catalysts 150
3.2.4.2 Brønsted Acidic as Catalyst 151
3.2.4.3 Amberlite IR-120 Resins as Catalysts 152
3.2.4.4 Magnetic Catalysts 152
3.2.4.5 Zeolite as Catalyst 153
3.2.4.6 Ionic Liquids (ILs) as Catalyst 154
3.2.4.7 Other Catalysts 156
3.2.5 Carbonylation of C-X with Formic Acid 157
3.2.6 Other Reactions 161
4 CO Surrogates 163
4.1 Carbonyl Metal 163
4.2 Formates 165
4.3 Formamides 168
4.4 Formic Anhydride 169
4.5 Silacarboxylic Acid 170
4.6 N-Formylsaccharin 172
4.7 Acyl Chloride 172
4.8 In Situ Generated Carbonyl Source 174
4.8.1 Methanol 174
4.8.2 Glycerol 176
4.8.3 Aldoses 178
4.8.4 Epoxide 179
4.8.5 Chloroform 181
4.8.5.1 Pd-catalyzed Carbonylation Reactions 182
4.8.5.2 Fe-Catalyzed Carbonylation Reactions 185
4.8.5.3 Zn-Catalyzed Carbonylation Reactions 186
Part I References 187
Part II Carbonyl Compounds as Catalysts 217
5 Acid-Catalyzed Reactions with -CO2H 219
5.1 Carboxylic Acid Molecules Catalyzed Reactions 219
5.1.1 Hydrolysis/Aminolysis/Ethanolysis Reactions 219
5.1.2 Mutarotation of 2,3,4,6-Tetramethyl-d-glucose (TM-G) 221
5.1.3 Depolymerization of Polyoxymethylenes 221
5.1.4 Elimination Reactions 221
5.1.5 Hydrogen-Deuterium Exchange Reactions 222
5.1.6 Reduction Reactions 222
5.1.7 Decomposition of Diazodiphenylmethane 222
5.1.8 Amino-Imino Tautomerism Reactions 222
5.1.9 Aldol Reaction 224
5.1.10 Friedel-Crafts Reaction 224
5.1.11 Hydrogen Shifts Reaction 225
5.1.12 Cyclization Reaction 226
5.1.13 Hydroboration Reaction 229
5.1.14 Trifluoromethylation Reaction 229
5.2 Carbon Material-Catalyzed Reactions 230
5.2.1 Reduction of Nitric Oxide 230
5.2.2 Oxidative Coupling of Amines to Imines 233
5.2.3 Depolymerization of Cellulose and Lignocellulose 233
5.2.4 Nitrobenzene Reduction Reaction and Beckmann Rearrangement Reaction 236
5.2.5 Ring-Opening Reaction of Styrene Oxide 236
6 Reactions via Carbonyl and Hydroxyl Groups Recycling 239
6.1 Carbon-Catalyzed Selective Oxidation Reactions 239
6.1.1 Oxidative Dehydrogenation of Ethylbenzene 239
6.1.2 Oxidative Dehydrogenation of n-Butane 242
6.1.3 Oxidative Dehydrogenation of Isobutane 243
6.1.4 Oxidative Dehydrogenation of Propane 245
6.2 Polymer-Catalyzed Selective Oxidation Reactions 245
6.2.1 Oxidative Dehydrogenation of Ethylbenzene 245
6.2.2 Oxidative Dehydrogenation of Heterocyclic Compounds 246
6.3 Aldehyde/Ketone-Catalyzed Borrowing-Hydrogen Reactions 247
6.3.1 Dehydrative β-C-Alkylation Reaction of Methyl Carbinols with Alcohols 247
6.3.2 Dehydrative α-Alkylation Reactions of Ketones with Alcohols 248
6.3.3 Dehydrative Alkylation Reactions of Fluorenes with Alcohols 248
6.3.4 Dehydrative N-Alkylation Reactions of Amines with Alcohols 249
6.4 Carbon-Catalyzed Borrowing-Hydrogen Reactions 250
Part II References 251
Part III The Synthetic Applications of Carbonyl Compounds 255
7 Synthesis of Functional Molecules 257
7.1 Reduction of Carbonyl Compounds 257
7.1.1 Aldehydes and Ketones to Alcohol 257
7.1.2 Acids to the Alcohols and Aldehydes 259
7.1.2.1 To Alcohols 259
7.1.2.2 To Aldehydes 261
7.1.3 Ester to Alcohols and Ethers 263
7.1.3.1 To Alcohols 263
7.1.3.2 To Ethers 264
7.1.4 Amides to Amines 264
7.1.5 Clemmensen Reduction 267
7.1.6 Wolff-Kishner Reduction 268
7.2 Nucleophilic Addition Reactions of Aldehydes and Ketones 270
7.2.1 Carbon Nucleophiles 270
7.2.1.1 Grignard Reagent and Other Organometallic Reagents 270
7.2.1.2 Reformatsky Reaction 271
7.2.1.3 Benzoin Condensation 272
7.2.1.4 CN Group 272
7.2.1.5 Aromatic and Aliphatic C-H Bond 273
7.2.2 Nitrogen Nucleophiles 275
7.2.3 Oxygen Nucleophiles 277
7.2.3.1 H2O as a Nucleophile 277
7.2.3.2 ROH as a Nucleophile 277
7.3 Addition Elimination Reactions of Aldehydes and Ketones 278
7.3.1 Aldol Reaction 278
7.3.2 Perkin Reaction 278
7.3.3 Knoevenagel Condensation 280
7.4 Oxidation of Aldehydes and Ketones 281
7.4.1 Baeyer-Villiger Oxidation 281
7.4.2 To Acid 282
7.5 Wittig Reaction 285
7.6 Reductive Amination Reaction 286
7.6.1 Homogeneous Catalyst System 287
7.6.2 Heterogeneous Catalyst System 290
7.7 Hydroboration/Hydrophosphonylation/Hydrosilylation/Hydroacylation of Aldehydes and Ketones 293
7.7.1 Hydroboration 293
7.7.2 Hydrophosphonylation 296
7.7.3 Hydrosilylation Reactions 297
7.7.4 Hydroacylation Reactions 300
7.8 Oxidative Cross-Coupling Reaction of Aldehydes 302
7.8.1 Homogeneous Catalyst System 302
7.8.2 Heterogeneous Catalyst System 304
7.9 Reductive Coupling Reactions of Aldehydes 306
7.10 Reaction of Acids as Starting Materials 310
7.10.1 Esterification Reactions 310
7.10.2 Amidation Reactions 310
7.10.3 Decarboxylation Coupling Reactions 311
7.11 Reaction of Esters as Starting Materials 317
7.11.1 Hydrolysis Reaction 317
7.11.2 Transesterification Reaction 318
7.11.3 Aminolysis Reaction 319
7.12 Reaction of Amides as Starting Materials 320
7.12.1 Hydrolysis Reaction 320
7.12.2 Alcoholysis Reaction 320
8 Synthesis of Functional Materials 323
8.1 Polyamides 323
8.1.1 Aliphatic Polyamides 324
8.1.2 Aromatic Polyamides 325
8.1.3 Long-Chain Semiaromatic Polyamides 326
8.2 Phenol Formaldehyde Resins 329
8.2.1 Novolac Resins 329
8.2.2 Resole Resins 330
8.3 Polyurethanes 332
8.4 Polyesters 335
Part III References 339
9 Conclusion and Perspectives 351
9.1 Conclusion 351
9.2 Perspectives 352
Index 355
