Liquid Phase Oxidation Via Heterogeneous Catalysis : Organic Synthesis and Industrial Applications

[BOOK DESCRIPTION]

With the recent emphasis on green chemistry in the chemical industries, there is the need for environmentally friendly large-scale syntheses. This book lays out an important catalytic reaction class for these green/sustainable reactions, covering catalyst characterization and performance as well as paying special attention to catalyst stability and recyclability. An international team of authors guides readers in the selection, preparation, and use of catalysts for industrial organic synthesis in the pharmaceutical, fragrance, fine chemical, and petrochemical industries.

[TABLE OF CONTENTS]

Preface                                            xi
Contributors                                       xiii
Abbreviations                                      xv
    1 Environmentally Benign Oxidants              1   (20)
          Giorgio Strukul
          Alessandro Scarso
      1.1 Introduction                             1   (2)
      1.2 Oxygen (Air)                             3   (2)
      1.3 Alkylhydroperoxides                      5   (4)
      1.4 Hydrogen Peroxide                        9   (7)
      1.5 Conclusions                              16  (5)
        References                                 17  (4)
    2 Oxidation Reactions Catalyzed by             21  (74)
    Transition-Metal-Substituted Zeolites
          Mario G. Clerici
          Marcelo E. Domine
      2.1 Introduction                             21  (1)
      2.2 Synthesis and Characterization of        22  (12)
      Zeolites
        2.2.1 Isomorphous Metal Substitution       23  (1)
        2.2.2 Synthesis of Titanium                24  (2)
        Silicalite-1 (TS-1)
        2.2.3 Characterization of Titanium         26  (4)
        Silicalite-1 (TS-1)
        2.2.4 Ti-Beta, Synthesis and               30  (2)
        Characterization
        2.2.5 Other Ti Zeolites                    32  (1)
        2.2.6 Other Metal Zeolites                 33  (1)
      2.3 Catalytic Properties                     34  (32)
        2.3.1 Hydroxylation of Alkanes             34  (6)
        2.3.2 Hydroxylation of Aromatic            40  (7)
        Compounds
        2.3.3 Oxidation of Olefinic Compounds      47  (12)
        2.3.4 Oxidation of Alcohol and Ether       59  (1)
        Compounds
        2.3.5 Reactions of Carbonyl Compounds      60  (3)
        2.3.6 Oxidation of N-Compounds             63  (2)
        2.3.7 Oxidation of S-Compounds             65  (1)
      2.4 Mechanistic Aspects                      66  (11)
        2.4.1 The Nature of Active Species         66  (3)
        2.4.2 Hydroxylation                        69  (2)
        2.4.3 Epoxidation                          71  (1)
        2.4.4 Oxidation of Alcohols                72  (1)
        2.4.5 Ammoximation                         73  (1)
        2.4.6 Decomposition of Hydrogen Peroxide   74  (1)
        2.4.7 Active Species, Adsorption and       74  (3)
        Catalytic Activity
      2.5 Stability of Metal-Substituted           77  (1)
      Zeolites to Reaction Conditions
      2.6 Conclusions                              78  (17)
        References                                 80  (15)
    3 Selective Catalytic Oxidation over           95  (32)
    Ordered Nanoporous Metallo-Aluminophosphates
          Parasuraman Selvam
          Ayyamperumal Sakthivel
      3.1 Introduction                             95  (5)
      3.2 Synthesis                                100 (3)
        3.2.1 Microporous Aluminophosphates        100 (2)
        3.2.2 Mesoporous Aluminophosphates         102 (1)
      3.3 Characterization                         103 (3)
      3.4 Catalytic Properties                     106 (10)
        3.4.1 Oxidation of Hydrocarbons            106 (4)
        3.4.2 Oxidation of Olefins                 110 (1)
        3.4.3 Oxidation of Alcohols                111 (2)
        3.4.4 Oxidation of Phenols                 113 (1)
        3.4.5 Ammoximation and Ammoxidation        114 (2)
        3.4.6 Baeyer-Villiger Oxidation            116 (1)
        3.4.7 Oxidation of Heterocycles            116 (1)
      3.5 Mechanistic Aspects                      116 (2)
      3.6 Catalysts Stability                      118 (1)
      3.7 Conclusion                               119 (8)
        References                                 120 (7)
    4 Selective Oxidations Catalyzed by            127 (94)
    Mesoporous Metal Silicates
          Oxana A. Kholdeeva
      4.1 Introduction                             127 (1)
      4.2 Synthesis and Characterization           128 (35)
        4.2.1 General Synthetic Approaches         128 (1)
        4.2.2 Characterization Techniques          129 (3)
        4.2.3 Sol-Gel Synthesis of Amorphous       132 (4)
        Mixed Oxides
        4.2.4 Thermolytic Molecular Precursor      136 (1)
        Method
        4.2.5 Templated Synthesis of Ordered       136 (20)
        Metal Silicates
        4.2.6 Postsynthesis Modifications          156 (6)
        4.2.7 Organic-Inorganic Hybrid Materials   162 (1)
      4.3 Catalytic Properties                     163 (26)
        4.3.1 Oxidation of Alkanes                 163 (4)
        4.3.2 Oxidation of Aromatic Compounds      167 (5)
        4.3.3 Oxidation of Olefins                 172 (10)
        4.3.4 Oxidation of Alcohols                182 (1)
        4.3.5 Oxidation of Ketones and Aldehydes   183 (2)
        4.3.6 Oxidation of S-compounds             185 (3)
        4.3.7 Oxidation of Amines                  188 (1)
      4.4 Mechanistic Aspects                      189 (5)
      4.5 Stability                                194 (6)
        4.5.1 Mechanisms of Deactivation           194 (3)
        4.5.2 Solving Problem of Hydrothermal      197 (2)
        Stability
        4.5.3 Hydrothermally Stable Catalysts:     199 (1)
        Scope and Limitations
      4.6 Conclusions and Outlook                  200 (21)
        References                                 201 (20)
    5 Liquid Phase Oxidation of Organic            221 (42)
    Compounds by Supported Metal-Based
    Catalysts with a Focus on Gold
          Cristina Della Pina
          Ermelinda Falletta
          Michele Rossi
      5.1 Introduction                             221 (1)
      5.2 Catalyst Preparation and                 222 (2)
      Characterization
      5.3 Catalytic Properties                     224 (26)
        5.3.1 Oxidation of Hydrocarbons            224 (4)
        5.3.2 Oxidation of Alcohols and Phenols    228 (13)
        5.3.3 Oxidation of Carbohydrates: The      241 (3)
        Case of Glucose
        5.3.4 Oxidation of Amines and              244 (1)
        Aminoalcohols
        5.3.5 Oxidative Polymerization of          245 (5)
        Aniline and Pyrrole
      5.4 Reaction Mechanisms                      250 (4)
      5.5 Catalyst Stability                       254 (2)
      5.6 Conclusions                              256 (7)
        References                                 256 (7)
    6 Selective Liquid Phase Oxidations in the     263 (58)
    Presence of Supported Polyoxometalates
          Craig L. Hill
          Oxana A. Kholdeeva
      6.1 Introduction                             263 (3)
      6.2 Synthesis and Characterization           266 (21)
        6.2.1 Choice of POM                        266 (1)
        6.2.2 Embedding POM into Silica and        267 (4)
        Other Matrixes
        6.2.3 Adsorption on Active Carbon          271 (2)
        6.2.4 Electrostatic Attachment             273 (10)
        6.2.5 Dative and Covalent Binding          283 (4)
      6.3 Catalytic Properties                     287 (17)
        6.3.1 Oxidation of Alkanes                 287 (1)
        6.3.2 Oxidation of Aromatic Compounds      288 (1)
        6.3.3 Oxidation of Olefins                 288 (9)
        6.3.4 Oxidation of Alcohols                297 (1)
        6.3.5 Oxidation of Aldehydes               298 (1)
        6.3.6 Co-Oxidation of Alkenes and          299 (2)
        Aldehydes
        6.3.7 Oxidation of S-containing            301 (3)
        Compounds
      6.4 Mechanistic Aspects                      304 (3)
      6.5 Stability                                307 (2)
      6.6 Conclusions                              309 (12)
        References                                 311 (10)
    7 Selective Oxidations Catalyzed by            321 (50)
    Supported Metal Complexes
          Alexander B. Sorokin
      7.1 Introduction                             321 (2)
      7.2 Synthesis and Characterization           323 (15)
        7.2.1 General Synthetic Strategies         324 (5)
        7.2.2 Metal Porphyrins                     329 (2)
        7.2.3 Metal Phthalocyanines                331 (5)
        7.2.4 Complexes with Other Macrocyclic     336 (1)
        Ligands
        7.2.5 Chiral Complexes                     337 (1)
      7.3 Catalytic Properties and Stability       338 (24)
        7.3.1 Oxidation of Alkanes                 339 (5)
        7.3.2 Oxidation of Olefins                 344 (8)
        7.3.3 Oxidation of Aromatic Hydrocarbons   352 (1)
        7.3.4 Oxidation of Substituted Phenols     353 (3)
        7.3.5 Oxidation of Alcohols                356 (3)
        7.3.6 Miscellaneous Oxidations             359 (3)
      7.4 General Remarks on Stability             362 (2)
      7.5 Conclusion and Perspectives              364 (7)
        References                                 365 (6)
    8 Liquid Phase Oxidation of Organic            371 (40)
    Compounds by Metal-Organic Frameworks
          Young Kyu Hwang
          Gerard Ferey
          U-Hwang Lee
          Jong-San Chang
      8.1 Introduction                             371 (1)
      8.2 Characteristics and Structures           372 (16)
        8.2.1 Characteristics                      372 (2)
        8.2.2 Structures                           374 (4)
        8.2.3 Syntheses                            378 (2)
        8.2.4 Active Sites                         380 (8)
      8.3 Catalytic Properties                     388 (12)
        8.3.1 Oxidation of Cycloalkanes            388 (1)
        8.3.2 Oxidation of Aromatic Compounds      389 (4)
        8.3.3 Oxidation of Olefins                 393 (5)
        8.3.4 Oxidation of Alcohols and Phenols    398 (1)
        8.3.5 Oxidation of Sulfides                399 (1)
      8.4 Mechanistic Aspects                      400 (2)
      8.5 Stability                                402 (3)
        8.5.1 Thermal and Chemical Stability       402 (2)
        8.5.2 Leaching of Active Metal             404 (1)
        Components
      8.6 Conclusion                               405 (6)
        References                                 405 (6)
    9 Heterogeneous Photocatalysis for             411 (40)
    Selective Oxidations with Molecular Oxygen
          Andrea Maldotti
          Rossano Amadelli
          Alessandra Molinari
      9.1 Introduction                             411 (2)
      9.2 Catalysts Preparation and Mechanistic    413 (9)
      Aspects
        9.2.1 Titanium Dioxide                     413 (3)
        9.2.2 Highly Dispersed Oxides              416 (2)
        9.2.3 Polyoxotungstates                    418 (4)
      9.3 Catalytic Properties                     422 (16)
        9.3.1 Oxidation of Alkanes                 422 (5)
        9.3.2 Oxidation of Aromatic Compounds      427 (3)
        9.3.3 Oxidation of Alcohols                430 (6)
        9.3.4 Oxidation of Olefins                 436 (2)
      9.4 Stability                                438 (5)
      9.5 Conclusions                              443 (8)
        References                                 444 (7)
    10 Industrial Applications                     451 (56)
      10.1 The Hydroxylation of Phenol to          451 (11)
      Hydroquinone and Catechol
          Ugo Romano
          Marco Ricci
        10.1.1 The Discovery of TS-1               451 (1)
        10.1.2 The Hydroxylation of Phenol         452 (4)
        10.1.3 The Industrial Process              456 (4)
        10.1.4 Other Processes Exploiting TS-1     460 (1)
        References                                 461 (1)
      10.2 The Greening of Nylon: The              462 (12)
      Ammoximation Process
          Franco Rivetti
          Roberto Buzzoni
        10.2.1 Nylon-6 and                         462 (4)
        ε-Caprolactam, Outlook and
        Industrial Production
        10.2.2 TS-1 Catalyzed Ammoximation         466 (1)
        10.2.3 Eni Cyclohexanone Ammoximation      467 (3)
        Process
        10.2.4 Salt-Free Caprolactam Production    470 (1)
        10.2.5 Other TS-1-Catalyzed                470 (1)
        Ammoximation Reactions and Related
        Processes of Industrial Relevance
        10.2.6 Conclusion                          471 (1)
        References                                 472 (2)
      10.3 Production of Propylene Oxide           474 (22)
          Anna Forlin
          Massimo Bergamo
          Joerg Lindner
        10.3.1 Propylene Oxide Production via      476 (4)
        Ethylbenzene Hydroperoxide Route
        10.3.2 Propylene Oxide Production via      480 (3)
        Cumene Hydroperoxide Route
        10.3.3 Propylene Oxide Production via      483 (4)
        Hydrogen Peroxide Route
        10.3.4 Conclusions                         487 (7)
        References                                 494 (2)
      10.4 Engineering Aspects of Liquid Phase     496 (11)
      Oxidations
          Bruce D. Hook
        10.4.1 Heterogeneous Liquid Phase          496 (3)
        Systems
        10.4.2 Temperature-Control Requirements    499 (1)
        10.4.3 Packed-Bed Reactors                 500 (1)
        10.4.4 Three-Phase Systems - Gas,          501 (2)
        Liquid, Solid
        10.4.5 Oxidant Selection                   503 (2)
        10.4.6 Summary                             505 (1)
        References                                 506 (1)
Index                                              507