Fine chemicals through heterogenous catalysis / [edited by] Roger Arthur Sheldon, Hermann van Bekkum.

Format:

Book

Contributor:

Sheldon, Roger A.

Bekkum, Herman van.

Language:

English

Subjects (All):

Heterogeneous catalysis.

Organic compounds--Synthesis.

Organic compounds.

Physical Description:

xxv, 611 pages : illustrations ; 25 cm

Place of Publication:

Weinheim ; New York : Wiley-VCH, [2001]

Contents:

1.1 What are Fine Chemicals? 1

1.2 The Environmental Factor 2

1.3 The Development of Organic Synthesis and Catalysis 3

1.4 Why Heterogeneous Catalysis? 4

1.5 Types of Catalysts and Reactions 5

1.5.1 Solid-Acid Catalysis 5

1.5.2 Solid-Base Catalysis 6

1.5.3 Catalytic Hydrogenation 6

1.5.4 Catalytic Oxidations 6

1.5.5 Catalytic C

C Bond Formation 7

1.6 Alternative Approaches 8

1.7 Heterogeneous Catalysis in Multi-step Synthesis: Vanillin 8

2 Basic Principles/General 13

2.1 General Considerations and Types of Catalyst 13

2.1.2 Catalytically Active Surface Area 14

2.1.3 Reactors Employed in the Fine-chemical Industry 14

2.1.4 Slurry-phase Catalysts 16

2.1.5 Fixed-bed Catalysts 18

2.1.6 Integration of the Catalyst and the Reactor 18

2.1.7 Solid Catalysts Employed in the Fine-chemical Industry 19

2.1.8 Metal Catalysts 19

2.1.9 Solid-Acid Catalysts 24

2.2 Preparation of Solid Catalysts 26

2.2.1 Demands on Solid Catalysts 26

2.2.2 Preparation Procedures [2] 28

2.3 Characterization of Solid Catalysts 35

2.3.1 Total Surface Area and Pore-size Distribution 36

2.3.2 Catalytically Active Surface Area Per Unit Weight of Catalyst 39

2.3.3 Extent of Reduction of Metal Catalysts 41

2.3.4 Solid-acid Catalysts 42

2.3.5 Dispersion of Active Component(s) Over the Support 42

2.4 Reactors 45

2.4.2 Three-phase Catalytic Reactions (G

L

S) 46

2.4.3 Characteristics of Three-phase Catalytic Reactors for Fine-chemicals Production 47

2.4.4 Design Aspects of Stirred Tank Batch Reactor 53

2.4.5 Scale-up of Stirred-Tank Batch Reactors

Runaway Reactions 56

3 Solid-acid Catalysts

General 61

3.1 Acidic Clays 61

3.1.2 Structure 62

3.1.3 Main Properties and Catalytic Applications 63

3.1.4 Pillared Interlayer Clays (PILC) 71

3.2 Zeolites as Catalysts 80

3.2.2 Acid Zeolites 83

3.2.3 Basicity in Zeolites 85

3.2.4 Redox Molecular Sieves 86

3.3 Sulfonated Polysiloxanes 92

3.3.1 Motivation and Expected Advantages 92

3.3.2 Synthetic Approaches 92

3.3.3 Characterization of the Polysiloxanes 95

3.3.4 Applications and Reactions 98

3.4 Silica-occluded Heteropolyacids 100

3.4.2 Preparation of Silica-occluded Heteropolyacid 101

3.4.3 Liquid-phase Organic Reactions over Silica-occluded H[subscript 3]PW[subscript 12]O[subscript 40] 102

3.5 Hybrid Sulfonated Mesoporous Systems 106

3.5.1 Amorphous Solid Sulfonic Acids 106

3.5.2 Ordered Sulfonic Acid Catalysts 109

3.6 The Use of Nafion and Nafion

Silica Composites in Solid Acid Catalysis 116

3.6.2 The Ion-exchange Resin Nafion 116

3.6.3 Nafion in Catalysis 117

3.6.4 Nafion

Silica Composites 117

3.6.5 Nafion

Silica Composites in Catalysis 118

4 Solid-acid Catalysts

Aromatic Substitution 123

4.1 Nitration of Aromatic Compounds 123

4.1.2 Reaction Mechanism 123

4.1.3 Commercial Manufacture of Nitroaromatic Compounds 124

4.1.4 Solid-acid-based Nitration 125

4.1.5 Liquid-phase Reactions 126

4.1.6 Vapor-phase Reactions 128

4.2 Halogenation over Solid Catalysts 133

4.2.2 Halogenation and Halogenating Agents 134

4.2.3 Halogenation over Solid Catalysts 135

4.2.4 Fluorination using Solid Catalysts 141

4.2.5 Chlorination using Solid Catalysts 143

4.2.6 Bromination Using Solid Catalysts 145

4.2.7 Iodination Using Solid Catalysts 146

4.3 Friedel

Crafts Alkylation 151

4.3.2 Dialkylation of Benzene and Polynuclear Aromatics 152

4.3.3 Production of 1,3,5-Trialkylbenzene 157

4.4 Friedel

Crafts Acylation 161

4.4.2 Reactivity 161

4.4.3 Deactivation 169

4.4.4 Industrial Processes 169

4.4.5 Perspectives and Conclusions 170

4.5 Hydroxyalkylations 173

4.5.3 Conclusion and Perspectives 177

4.6 The Fischer Indole Synthesis 178

4.6.2 Heterogeneous Catalysis 178

4.6.3 Zeolites as Catalysts 179

5 Solid-acid Catalysis: RearrangementandIsomerization 185

5.1 Beckmann Rearrangement 185

5.1.2 Catalysts for Beckmann Rearrangements 186

5.1.3 Mechanistic Considerations 193

5.1.4 Deactivation and Regeneration 199

5.1.5 Influence of Reaction Conditions 200

5.2 The Benzamine Rearrangement 205

5.2.2 Rearrangement of Aniline and m-Phenylenediamine 205

5.2.3 Rearrangement of Other Benzamines 207

5.2.4 Mechanism of the Rearrangement 208

5.3 The Fries Rearrangement 211

5.3.1 The Fries Rearrangement of Phenyl Acetate, and Related Reactions 212

5.3.2 Other Fries Reactions 214

5.4 Rearrangement of Epoxides 217

5.4.1 Catalysts 217

5.4.2 Reactor Concepts 219

5.4.3 Isomerization of Small Aliphatic Epoxides 219

5.4.4 Isomerization of Styrene Oxide and Derivatives 220

5.4.5 Rearrangement of Glycidic Acid Ester 222

5.4.6 Isomerization of [alpha]-Pinene Oxide 223

5.4.7 Isomerization of Isophorone Oxide 226

5.4.8 Rearrangement of Oxaspiro Compounds 227

5.5 The Pinacol Rearrangement 232

5.5.2 Solid Acids in the Pinacol Rearrangement 234

5.6 Terpene Rearrangement/Isomerization 242

5.6.2 Isomerization of pinene (1) 242

5.6.3 Rearrangement/Isomerization of Other Terpenes 244

5.6.4 Rearrangement of Terpene Epoxides 245

6 Solid Acid Catalysis: Miscellaneous 247

6.1 Metal-Catalyzed Amination of Alcohols 247

6.1.1 Introduction and Scope 247

6.1.2 Reaction Mechanism 247

6.1.3 Side-reactions, Choice of Catalyst, and Reaction Conditions 248

6.1.4 Synthesis of Aliphatic and Aromatic Amines 250

6.1.5 Cyclic Amines from Amino Alcohols or Diols 252

6.1.6 Amination of Di- and Polyhydroxy Compounds to Acyclic Amines 253

6.2 Alkylation of Carbohydrates 257

6.2.2 Synthetic Routes 257

6.2.3 Catalysts for the Synthesis of Alkylglycosides 260

6.3 Heterocyclic Synthesis 275

6.4 Heterogeneous Catalysis of Diels

Alder Reactions 284

6.4.2 Catalysts 284

6.5 Dehydration of Alcohols 295

6.5.2 Dehydration of Monohydric Alcohols 295

6.5.3 Dehydration of Diols 301

6.5.4 Dehydration of Polyols 302

7 Solid-base Catalysis 309

7.1 Zeolites and Related Materials in Knoevenagel Condensations and Michael Additions 309

7.1.2 Zeolites as Catalysts 312

7.1.3 Knoevenagel and Michael Reactions on Basic Zeolites and Mesoporous Aluminosilicates for the Production of Fine Chemicals 318

7.2 Aldol Condensations Catalyzed by Hydrotalcites 327

7.3.2 Preparation of Materials 339

7.3.3 Reactions Catalyzed by Organic Bases Attached to Mesoporous Silicas 342

7.3.4 Discussion of the Different Approaches 346

8 Catalytic Hydrogenation and Dehydrogenation 351

8.1 Alkynes 351

8.1.2 Structure and Bonding 351

8.1.3 Hydrogenation, General Observations 351

8.1.4 The Choice of Active Metal 352

8.1.5 Palladium-based Catalysts 355

8.1.6 The Use of Promoters 356

8.1.7 Illustrative Reactions 356

8.1.8 Acetylenic Alcohols (Carbinols) 358

8.1.9 Selectivity and Stereochemistry 359

8.1.10 Alternative Metal Formulations 361

8.2 Aldehydes and Ketones 363

8.2.2 Aromatic Aldehydes and Ketones 363

8.2.3 Aliphatic Ketones and Aldehydes 364

8.2.4 Stereochemistry 365

8.2.5 Amides 365

8.2.6 Anhydrides 365

8.2.7 Selective Hydrogenation of a,[beta]-Unsaturated Aldehydes 365

8.2.8 Reaction Pathway 366

8.2.9 Cinnamaldehyde Hydrogenation 367

8.2.10 Unpromoted Catalysts 367

8.2.11 Promoters 367

8.2.12 Citral Hydrogenation 368

8.2.13 Pitfalls 369

8.3 Carboxylic Acids and Derivatives 370

8.3.1 Development of Hydrogenation Catalysts of Carboxylic acids and its Properties 370

8.3.2 Application of Cr-ZrO[subscript 2] Catalyst to Wide Variety of Carboxylic Acids 373

8.3.3 Hydrogenation of Aliphatic Carboxylic Acids 374

8.3.4 Application of Cr[subscript 2]O[subscript 3] Catalysts to Different Aliphatic Carboxylic Acids 376

8.3.5 Mechanistic Considerations 376

8.3.6 The Commercial Process 378

8.3.7 Future Prospects for Hydrogenation of Carboxylic

Acids 379

8.4 Carbohydrates 380

8.4.2 Hydrogenation of the Carbonyl Group 380

8.4.3 Reductive Amination 384

8.4.4 Dehydrogenation 386

8.5 Aromatic Nitro Compounds 389

8.5.2 The Reaction Network 389

8.5.3 Practical Aspects 390

8.5.4 Chemoselective Hydrogenation of Functionalized Nitro Arenes 396

8.5.5 Mechanistic Concepts in the Hydrogenation of Nitroarenes 401

8.5.6 Alternative Commercial Methods of Reduction 403

8.6 Catalytic Hydrogenation of Aromatic Rings 407

8.6.2 Intermediates and Mechanism 407

8.6.3 Hydrogenation of Benzene Derivatives 408

8.6.4 Hydrogenation of Polycyclic Aromatic Ring Systems 409

8.6.5 Hydrogenation of Nitrogen-containing Aromatic Ring Systems 410

8.6.6 Hydrogenation of Oxygen- and Sulfur-containing Aromatic Ring Systems 411

8.7 Hydrogenolysis of C-O, C-N and C-X Bonds 415

8.7.1 Hydrogenolysis of C-O Bonds 415

8.7.2 Hydrogenolysis of C-N Bonds 419

8.7.3 Hydrogenolysis of C-X Bonds 422

8.8 Dehydrogenation 427

8.8.1 Thermodynamics 427

8.8.2 Reaction Conditions 430

8.8.3 Catalysts 431

8.8.4 Dehydrogenation to Aromatic or Heteroaromatic Compounds 432

8.8.5 Dehydrogenation of Alcohols to Aldehydes or Ketones 435

8.9 Meerwein

Ponndorf

Verley Reduction, Oppenauer Oxidation, and Related Reactions 438

8.9.2 MPVO Reactions Catalyzed by Metal Oxides 439

8.9.3 MPVO Reactions Catalyzed by Mesoporous Materials 442

8.9.4 MPVO Reactions Catalyzed by Zeolites 443

8.10 Enantioselective Hydrogenation with Solid Catalysts 449

8.10.1 Introduction and Scope 449

8.10.2 Strategies for Developing Solid Enantioselective Catalysts 449

8.10.3 Hydrogenation of Ketones 451

8.10.4 Hydrogenation of Functionalized Olefins 457

8.10.5 Hydrogenation of C=N Bonds 458

8.11 Selective N-Alkylation of Amines with Alcohols over [gamma]-Alumina 461

8.11.2 Experimental 463

8.11.3 Methanol as Alkylating Agent 464

8.11.4 Influence of the Structure of the Alkylating Agent 466

8.11.5 Ether as Alkylating Agent 468

8.11.6 Chirality 469

9 Oxidation 473

9.1 Epoxidation 473

9.1.2 Mechanistic Considerations 474

9.1.3 Historical Development and Overview of Catalysts 475

9.1.4 Titanium(IV)-on-silica 477

9.1.5 Mixed Oxides by the Sol-Gel Method 478

9.1.6 Framework-substituted Molecular Sieves 479

9.1.7 Hydrotalcites 480

9.1.8 Immobilization of Homogeneous Complexes 481

9.1.9 Heterogeneous Catalysts for Asymmetric Epoxidation 483

9.1.10 Comparison of the Different Catalytic Systems 483

9.2 Oxidation of Alcohols and Aldehydes on Metal Catalysts 491

9.2.2 Physicochemical and Engineering Aspects 491

9.2.3 Selected Examples of Alcohol Oxidation Processes 497

9.3 Oxidation of Carbohydrates on Metal Catalysts 507

9.3.2 Mechanistic and Engineering Aspects 508

9.3.3 Selected Examples of Carbohydrate Oxidation Processes 509

9.4 Allylic and Benzylic Oxidation 519

9.4.2 Palladium-catalyzed Allylic Oxidations 519

9.4.3 Palladium-catalyzed Benzylic Oxidations 522

9.4.4 Metal-substituted Molecular Sieves as Catalysts for Allylic and Benzylic Oxidations 523

9.5 Ammoxidation of Aromatic Side-chains 527

9.5.2 Catalysts, General Reaction Conditions, Reaction Mechanism 528

9.5.3 Ammoxidation of Toluene and Alkylbenzenes 531

9.5.4 Ammoxidation of Substituted Toluenes 532

9.5.5 Ammoxidation of Heterocyclic Compounds 534

9.5.6 Future Developments 534

9.6 Aromatic Ring Hydroxylation 538

9.6.1 Medium-pore Titanium Zeolites 538

9.6.2 Large-pore Titanium Zeolites 544

9.6.3 Other Transition Metal-substituted Molecular Sieves 546

9.6.4 Supported Metals and Mixed Oxides 548

10 Carbon-Carbon Bond Formation 553

10.1 Carbon-Carbon Bond Formation via Surface Organometallic Chemistry (SOMC) 553

10.1.2 Alkene Metathesis and Related Reactions 555

10.1.3 Alkane Metathesis 558

10.2 Olefin Metathesis 562

10.2.2 Heterogeneous Metathesis Catalysts 564

10.2.3 Metathesis in Fine Chemistry 565

10.3 Heck Coupling 576

10.3.2 Background of Heterogeneous Heck Coupling 577.

Notes:

Includes bibliographical references and index.

ISBN:

3527299513

OCLC:

43970746