Table of Contents

Preface XV

List of Contributors XVII

Part I Radical Chain Aerobic Oxidation 1

1 Overview of Radical Chain Oxidation Chemistry 3
Ive Hermans

1.1 Introduction 3

1.2 Chain Initiation 6

1.3 Chain Propagation 7

1.4 Formation of Ring-Opened By-Products in the Case of Cyclohexane Oxidation 11

1.5 Complications in the Case of Olefin Autoxidation 12

1.6 Summary and Conclusions 13

References 14

2 Noncatalyzed Radical Chain Oxidation: Cumene Hydroperoxide 15
Manfred Weber, Jan-Bernd Grosse Daldrup, and Markus Weber

2.1 Introduction 15

2.2 Chemistry and Catalysis 15

2.3 Process Technology 21

2.4 New Developments 27

References 30

3 Cyclohexane Oxidation: History of Transition from Catalyzed to Noncatalyzed 33
Johan Thomas Tinge

3.1 Introduction 33

3.2 Chemistry and Catalysis 34

3.3 Process Technology 35

3.4 New Developments 38

Epilogue 39

References 39

4 Chemistry and Mechanism of Oxidation of para-Xylene to Terephthalic Acid Using Co–Mn–Br Catalyst 41
Victor A. Adamian and William H. Gong

4.1 Introduction 41

4.2 Chemistry and Catalysis 42

4.3 Process Technology 58

4.4 New Developments 61

4.5 Conclusions 62

References 63

Part II Cu-Catalyzed Aerobic Oxidation 67

5 Cu-Catalyzed Aerobic Oxidation: Overview and New Developments 69
Damian Hruszkewycz, Scott McCann, and Shannon Stahl

5.1 Introduction 69

5.2 Chemistry and Catalysis 70

5.3 Process Technology 74

5.4 New Developments: Pharmaceutical Applications of Cu-Catalyzed Aerobic Oxidation Reactions 76

References 82

6 Copper-Catalyzed Aerobic Alcohol Oxidation 85
Janelle E. Steves and Shannon S. Stahl

6.1 Introduction 85

6.2 Chemistry and Catalysis 86

6.3 Prospects for Scale-Up 91

6.4 Conclusions 93

References 94

7 Phenol Oxidations 97

7.1 Polyphenylene Oxides by Oxidative Polymerization of Phenols 97
Patrick Gamez

7.2 2,3,5-Trimethylhydroquinone as a Vitamin E Intermediate via Oxidation of Methyl-Substituted Phenols 106
Jan Schütz and Thomas Netscher

References 109

Part III Pd-Catalyzed Aerobic Oxidation 113

8 Pd-Catalyzed Aerobic Oxidation Reactions: Industrial Applications and New Developments 115
Dian Wang, Jonathan N. Jaworski, and Shannon S. Stahl

8.1 Introduction 115

8.2 Chemistry and Catalysis: Industrial Applications 117

8.3 Chemistry and Catalysis: Applications of Potential Industrial Interest 122

8.4 Chemistry and Catalysis: New Developments and Opportunities 128

8.5 Conclusion 133

References 133

9 Acetaldehyde from Ethylene and Related Wacker-Type Reactions 139
Reinhard Jira

9.1 Introduction 139

9.2 Chemistry and Catalysis 140

9.3 Process Technology (Wacker Process) 148

9.4 Other Developments 151

References 155

Further Reading 158

10 1,4-Butanediol from 1,3-Butadiene 159
Yusuke Izawa and Toshiharu Yokoyama

10.1 Introduction 159

10.2 Chemistry and Catalysis 160

10.3 Process Technology 164

10.4 New Developments 168

10.5 Summary and Conclusions 169

References 170

11 Mitsubishi Chemicals Liquid Phase Palladium-Catalyzed Oxidation Technology: Oxidation of Cyclohexene, Acrolein, and Methyl Acrylate to Useful Industrial Chemicals 173
Yoshiyuki Tanaka, Jun P. Takahara, Tohru Setoyama, and Hans E. B. Lempers

11.1 Introduction 173

11.2 Chemistry and Catalysis 174

11.3 Prospects for Scale-Up 180

11.4 Conclusion 187

References 187

12 Oxidative Carbonylation: Diphenyl Carbonate 189
Grigorii L. Soloveichik

12.1 Introduction 189

12.2 Chemistry and Catalysis 192

12.3 Prospects for Scale-Up 201

12.4 Conclusions and Outlook 203

Acknowledgments 204

References 205

13 Aerobic Oxidative Esterification of Aldehydes with Alcohols: The Evolution from Pd–Pb Intermetallic Catalysts to Au–NiOx Nanoparticle Catalysts for the Production ofMethylMethacrylate 209
Ken Suzuki and Setsuo Yamamatsu

13.1 Introduction 209

13.2 Chemistry and Catalysis 210

13.3 Process Technology 214

13.4 New Developments 215

13.5 Conclusion and Outlook 217

References 218

Part IV Organocatalytic Aerobic Oxidation 219

14 Quinones in Hydrogen Peroxide Synthesis and Catalytic Aerobic Oxidation Reactions 221
Alison E.Wendlandt and Shannon S. Stahl

14.1 Introduction 221

14.2 Chemistry and Catalysis: Anthraquinone Oxidation (AO) Process 223

14.3 Process Technology 227

14.4 Future Developments: Selective Aerobic Oxidation Reactions Catalyzed by Quinones 229

References 234

15 NOx Cocatalysts for Aerobic Oxidation Reactions: Application to Alcohol Oxidation 239
Susan L. Zultanski and Shannon S. Stahl

15.1 Introduction 239

15.2 Chemistry and Catalysis 241

15.3 Prospects for Scale-Up 247

15.4 Conclusions 249

References 249

16 N-Hydroxyphthalimide (NHPI)-Organocatalyzed Aerobic Oxidations: Advantages, Limits, and Industrial Perspectives 253
Lucio Melone and Carlo Punta

16.1 Introduction 253

16.2 Chemistry and Catalysis 254

16.3 Process Technology 257

16.4 New Developments 262

Acknowledgments 264

References 264

17 Carbon Materials as Nonmetal Catalysts for Aerobic Oxidations: The Industrial Glyphosate Process and New Developments 267

17.1 Introduction 267
Mark Kuil and Annemarie E.W. Beers

17.2 Chemistry and Catalysis 268
Mark Kuil and Annemarie E.W. Beers

17.3 Process Technology 270
Mark Kuil and Annemarie E.W. Beers

17.4 New Developments 274
Paul L. Alsters

17.5 Concluding Remarks 283

References 283

Part V Biocatalytic Aerobic Oxidation 289

18 Enzyme Catalysis: Exploiting Biocatalysis and Aerobic Oxidations for High-Volume and High-Value Pharmaceutical Syntheses 291
Robert L. Osborne and Erika M. Milczek

18.1 Introduction 291

18.2 Chemistry and Catalysis 293

18.3 Process Technology 302

18.4 New Developments 304

References 306

Part VI Oxidative Conversion of Renewable Feedstocks 311

19 From Terephthalic Acid to 2,5-Furandicarboxylic Acid: An Industrial Perspective 313
Jan C. van derWaal, Etienne Mazoyer, Hendrikus J. Baars, and Gert-Jan M. Gruter

19.1 Introduction 313

19.2 Chemistry and Catalysis 314

19.3 Process Technology 320

19.4 New Developments 325

19.5 Conclusion 327

List of Abbreviations 327

References 327

20 Azelaic Acid fromVegetable Feedstock via Oxidative Cleavage with Ozone or Oxygen 331
Angela Köckritz

20.1 Introduction 331

20.2 Chemistry and Catalysis 336

20.3 Prospects for Scale-Up 341

20.4 Concluding Remarks and Perspectives 342

References 344

21 Oxidative Conversion of Renewable Feedstock: Carbohydrate Oxidation 349
Cristina Della Pina, Ermelinda Falletta, and Michele Rossi

21.1 Introduction 349

21.2 Chemistry and Catalysis 351

21.3 Prospects for Scale-Up 362

21.4 Concluding Remarks and Perspectives 366

References 367

Part VII Aerobic Oxidation with Singlet Oxygen 369

22 Industrial Prospects for the Chemical and Photochemical Singlet Oxygenation of Organic Compounds 371
Véronique Nardello-Rataj, Paul L. Alsters, and Jean-Marie Aubry

22.1 Introduction 371

22.2 Chemistry and Catalysis 373

22.3 Prospects for Scale-Up 383

22.4 Conclusion 392

Acknowledgments 392

References 393

Part VIII Reactor Concepts for Liquid Phase Aerobic Oxidation 397

23 Reactor Concepts for Aerobic Liquid Phase Oxidation:Microreactors and Tube Reactors 399
Hannes P. L. Gemoets, Volker Hessel, and Timothy Noël

23.1 Introduction 399

23.2 Chemistry and Catalysis 400

23.3 Prospects for Scale-Up 413

23.4 Conclusions 417

References 417

Index 421

About the Author

Shannon Stahl is a Professor of Chemistry at the University of Wisconsin-Madison, USA, since 1999. After undergraduate studies at the University of Illinois at Urbana-Champaign, USA, he attended the California Institute of Technology, USA, for doctoral studies. He worked on Pt-catalyzed oxidation of methane to methanol in the laboratory of Prof. John E. Bercaw and obtained his Ph.D. in 1997. From 1997-1999, he conducted postdoctoral research in the lab of Prof. Stephen J. Lippard at Massachusetts Institute of Technology, USA, investigating the enzyme methane monooxygenase. He has published >120 research articles and is the recipient of numerous awards, including the Humboldt Senior Research Award, ACS Cope Scholar Award, Sloan Research Fellowship, and he is a Fellow of the AAAS. His research group specializes in the development and mechanistic characterization of catalytic aerobic oxidation reactions.

Paul Alsters is a Principal Scientist at DSM Ahead R&D B.V. - Innovative Synthesis (Geleen, The Netherlands). He received his Ph.D. at the University of Utrecht, The Netherlands, in 1992, working on C-O coupling reactions of organopalladium compounds under the guidance of Prof. G. van Koten. He did postdoctoral work on asymmetric titanium mediated nucleophilic additions to aldehydes in the laboratory of R.O. Duthaler at Ciba-Geigy in Basel, Switzerland. He joined DSM in 1993. His main areas of interest are development of scalable break-through methods for new or existing products, and liquid-phase catalysis, with an emphasis on C-X or C-C coupling reactions and oxidation catalysis. His research activities frequently operate at the interplay of catalysis/synthesis and other sciences, in particular materials science. He is the (co-)author of >70 articles or book chapters and (co-)inventor of >20 patents.