Microporous and Mesoporous Solid Catalysts, Volume 4

by Derouane, Eric G.; Roberts, Stanley M.

• ISBN13: 9780471490548
• ISBN10: 0471490547
• Edition: 1st
• Format: Hardcover
• Copyright: 7/10/2007
• Publisher: Wiley-Interscience

Summary

This series offers practical help for advanced undergraduate, graduate and postgraduate students, as well as experienced chemists in industry and academia working with catalysts in organic and organometallic synthesis. It features tested and validated procedures, authoritative reviews on classes of catalysts, and assessments of all types of catalysts. Micro- and Mesoporous Solid Catalysts describes the use of zeolites and mesoporous solids as catalysts for the production of fine and specialty chemicals. Specific tips and hints are provided and some typical procedures are described in detail In addition to discussing the pros and cons, several major organic transformations are examined including aromatic substitutions, heterocyclic ring formation, amines synthesis, oligomerisation, oxidation and hydroxylation, and other regioselective and stereoselective reactions Features tutorial introductory chapters, including tips and hints for achieving successful organic transformations Important reactions are featured together with recommendations to resolve potential problems.

Author Biography

éric Gérard Joseph Derouane was a French-speaking Belgian catalyst scientist. In 1968 he obtained his MSc in Chemistry at Princeton University and his PhD at the University of Liège. He then became a Research Associate of FNRS. Stanley M. Roberts is the editor of Microporous and Mesoporous Solid Catalysts, Volume 4, published by Wiley.

Table of Contents

Series Preface	p. ix
Preface to Volume 4	p. xi
Abbreviations	p. xiii
An Overview of Zeolite, Zeotype and Mesoporous Solids Chemistry: Design, Synthesis and Catalytic Properties	p. 1
Zeolites, zeotypes and mesoporous solids: synthetic aspects	p. 1
Introduction	p. 1
Synthetic aspects: template theory for zeolite synthesis	p. 2
Synthetic aspects: template theory for mesoporous oxides synthesis	p. 7
Design of extra-large pore zeolites and other micro- and mesoporous catalysts	p. 11
Introduction	p. 11
Extra-large pore zeolites	p. 11
Hierarchical pore architectures: combining micro- and mesoporosity	p. 13
Potential of post-synthesis functionalized micro- and mesoporous solids as catalysts for fine chemical synthesis	p. 19
Introduction	p. 19
Covalent functionalization	p. 20
Noncovalent immobilization approaches	p. 25
Single-site catalysts inspired by natural systems	p. 29
References	p. 30
Problems and Pitfalls in the Applications of Zeolites and other Microporous and Mesoporous Solids to Catalytic Fine Chemical Synthesis	p. 39
Introduction	p. 39
Zeolite catalysed organic reactions	p. 42
Fundamental and practical differences with homogeneous reactions	p. 42
Batch mode catalysis	p. 45
Continuous flow mode catalysis	p. 51
Competition for adsorption: influence on reaction rate, stability and selectivity	p. 53
Catalyst deactivation	p. 61
General conclusions	p. 63
References	p. 64
Aromatic Acetylation	p. 69
Aromatic acetylation	p. 69
Acetylation with Acetic Anhydride	p. 70
Acetylation with Acetic Acid	p. 82
Procedures and protocols	p. 89
Selective synthesis of acetophenones in batch reactors through acetylation with acetic anhydride	p. 89
Selective synthesis of acetophenones in fixed bed reactors through acetylation with acetic anhydride	p. 90
References	p. 91
Aromatic Benzoylation	p. 95
Aromatic benzoylation	p. 95
Effect of the zeolite	p. 96
Effect of the acylating agent	p. 97
Effect of the solvent	p. 97
Benzoylation of phenol and the Fries rearrangement	p. 97
Kinetic law	p. 99
Substituent effect	p. 100
Experimental	p. 101
Acylation of anisole over mesoporous aluminosilicates	p. 102
References	p. 103
Nitration of Aromatic Compounds	p. 105
Introduction	p. 105
Reaction mechanism	p. 106
Nitration of aromatic compounds using zeolites as catalysts	p. 107
Nitration in liquid phase	p. 107
Vapour phase nitration	p. 116
Conclusions	p. 118
References	p. 118
Oligomerization of Alkenes	p. 125
Introduction	p. 125
Reaction mechanisms	p. 126
Acid zeolites as catalysts for oligomerization of alkenes	p. 127
Medium pore zeolites: influence of crystal size and acid site density	p. 127
Use of large pore zeolites	p. 130
Catalytic membranes for olefin oligomerization	p. 131
Mesoporous alominosilicates as oligomerization catalysts	p. 131
Nickel supported aluminosilicates as catalysts	p. 132
References	p. 136
Microporous and Mesoporous Catalysts for the Transformation of Carbohydrates	p. 141
Introduction	p. 141
Hydrolysis of sucrose in the presence of H-form zeolites	p. 142
Hydrolysis of fructose and glucose precursors	p. 143
Isomerization of glucose into fructose	p. 144
Dehydration of fructose and fructose-precursors	p. 145
Dehydration of xylose	p. 146
Synthesis of alkyl-D-glucosides	p. 147
Synthesis of butyl-D-glucosides	p. 147
Synthesis of long-chain alkyl-D-glucosides	p. 150
Synthesis of alkyl-D-fructosides	p. 151
Hydrogenation of glucose	p. 151
Oxidation of glucose	p. 153
Conclusions	p. 154
References	p. 154
One-pot Reactions on Bifunctional Catalysts	p. 157
Introduction	p. 157
Examples	p. 158
One-pot transformations involving successive hydrogenation and acid-base steps	p. 158
One-pot transformations involving successive oxidation and acid-base steps	p. 166
References	p. 168
Base-type Catalysts	p. 171
Introduction	p. 171
Characterization of solid bases	p. 172
Test reactions	p. 172
Probe molecules combined with spectroscopic methods	p. 174
Solid base catalysts	p. 175
Alkaline earth metal oxides	p. 175
Catalysis on alkaline earth metal oxides	p. 177
Hydrotalcites and related compounds	p. 183
Organic base-supported catalysts	p. 187
Conclusions	p. 195
References	p. 195
Hybrid Oxidation Catalysts from Immobilized Complexes on Inorganic Microporous Supports	p. 207
Introduction and scope	p. 207
Oxygenation potential of heme-type complexes in zeolite	p. 211
Metallo-phthallocyanines encapsulated in the cages of faujasite-type zeolites	p. 211
Oxygenation potential of metallo-phthallocyanines encapsulated in the mesopores of VPI-5 AIPO[subscript 4]	p. 215
Oxygenation potential of zeolite encapsulated metallo-porphyrins	p. 216
Oxygenation potential of zeolite encapsulated nonheme complexes	p. 220
Immobilization of N,N[prime]-bidentate complexes in zeolite Y	p. 220
Ligation of zeolite exchanged transition ions with bidentate aza ligands	p. 224
Ligation of zeolite exchanged transition ions with tri- and tetra-aza(cyclo)alkane ligands	p. 225
Ligation of zeolite exchanged transition ions with Schiff base-type ligands	p. 228
Zeolite effects with N,N[prime]-bis(2-pyridinecarboxamide) complexes of Mn and Fe in zeolite Y	p. 231
Zeolite encapsulated chiral oxidation catalysts	p. 233
Conclusions	p. 235
Acknowledgements	p. 235
References	p. 235
Subject Index	p. 241
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