Series Preface ................................................. ix
Preface to Volume 4 ............................................ xi
Abbreviations ................................................ xiii
1 An Overview of Zeolite, Zeotype and Mesoporous Solids
Chemistry: Design, Synthesis and Catalytic Properties ....... 1
Thomas Maschmeyer and Leon van de Water
1.1 Zeolites, zeotypes and mesoporous solids: synthetic
aspects ..................................................... 1
1.1.1 Introduction .......................................... 1
1.1.2 Synthetic aspects: template theory for zeolite
synthesis ............................................. 2
1.1.3 Synthetic aspects: template theory for mesoporous
oxides synthesis ...................................... 7
1.2 Design of extra-large pore zeolites and other micro- and
mesoporous catalysts ....................................... 11
1.2.1 Introduction ......................................... 11
1.2.2 Extra-large pore zeolites ............................ 11
1.2.3 Hierarchical pore architectures: combining micro-
and mesoporosity ..................................... 13
1.3 Potential of post-synthesis functionalized micro- and
mesoporous solids as catalysts for fine chemical
synthesis .................................................. 19
1.3.1 Introduction ......................................... 19
1.3.2 Covalent functionalization ........................... 20
1.3.3 Noncovalent immobilization approaches ................ 25
1.3.4 Single-site catalysts inspired by natural systems .... 29
References ..................................................... 30
2 Problems and Pitfalls in the Applications of Zeolites and
other Microporous and Mesoporous Solids to Catalytic Fine
Chemical Synthesis ......................................... 39
Michel Guisnet and Matteo Guidotti
2.1 Introduction ............................................... 39
2.2 Zeolite catalysed organic reactions ........................ 42
2.2.1 Fundamental and practical differences with
homogeneous reactions ................................ 42
2.2.2 Batch mode catalysis ................................. 45
2.2.3 Continuous flow mode catalysis ....................... 51
2.2.4 Competition for adsorption: influence on reaction
rate, stability and selectivity ...................... 53
2.2.5 Catalyst deactivation ................................ 61
2.3 General conclusions ........................................ 63
References ..................................................... 64
3 Aromatic Acetylation ....................................... 69
Michel Guisnet and Matteo Guidotti
3.1 Aromatic acetylation ....................................... 69
3.1.1 Acetylation with Acetic Anhydride .................... 70
3.1.2 Acetylation with Acetic Acid ......................... 82
3.2 Procedures and protocols ................................... 89
3.2.1 Selective synthesis of acetophenones in batch
reactors through acetylation with acetic anhydride ... 89
3.2.2 Selective synthesis of acetophenones in fixed bed
reactors through acetylation with acetic anhydride ... 90
References ..................................................... 91
4 Aromatic Benzoylation ...................................... 95
Patrick Geneste and Annie Finiels
4.1 Aromatic benzoylation ...................................... 95
4.1.1 Effect of the zeolite ................................ 96
4.1.2 Effect of the acyluting agent ........................ 97
4.1.3 Effect of the solvent ................................ 97
4.1.4 Benzoylation of phenol and the Fries rearrangement ... 97
4.1.5 Kinetic law .......................................... 99
4.1.6 Substituenl effect .................................. 100
4.1.7 Experimental ........................................ 101
4.2 Acylation of anisole over mesoporous aluminosilicates ..... 102
References .................................................... 103
5 Nitration of Aromatic Compounds ........................... 105
Avelino Corma and Sara Iborra
5.1 Introduction .............................................. 105
5.2 Reaction mechanism ........................................ 106
5.3 Nitration of aromatic compounds using zeolites as
catalysts ................................................. 107
5.3.1 Nitration in liquid phase ........................... 107
5.3.2 Vapour phase nitration .............................. 116
5.4 Conclusions ............................................... 118
References .................................................... 118
6 Oligomerization of Alkenes ................................ 125
Avelino Corma and Sara Iborra
6.1 Introduction .............................................. 125
6.2 Reaction mechanisms ....................................... 126
6.3 Acid zeolites as catalysts for oligomcrization of
alkenes ................................................... 127
6.3.1 Medium pore zeolites: influence of crystal size
and acid site density ............................... 127
6.3.2 Use of large pore zeolites .......................... 130
6.3.3 Catalytic membranes for olefin oligomerization ...... 131
6.4 Mesoporous aluminosilicates as oligomerization
catalysts ................................................. 131
6.5 Nickel supported aluminosilicates as catalysts ............ 132
References .................................................... 136
7 Microporous and Mesoporous Catalysts for
the Transformation of Carbohydrates ...................... 141
Claude Moreau
7.1 Introduction ............................................. 141
7.2 Hydrolysis of sucrose in the presence of H-form
zeolites ................................................. 142
7.3 Hydrolysis of fructose and glucose precursors ............ 143
7.4 lsomerization of glucose into fructose ................... 144
7.5 Dehydration of fructose and fructose-precursors .......... 145
7.6 Dehydration of xylose .................................... 146
7.7 Synthesis of ulkyl-D-glucosides .......................... 147
7.7.1 Synthesis of butyl-D-glucosides .................... 147
7.7.2 Synthesis of long-chain alkyl-D-glucosides ......... 150
7.8 Synthesis of alkyl-D-fructosides ......................... 151
7.9 Hydrogenation of glucose ................................. 151
7.10 Oxidation of glucose ..................................... 153
7.11 Conclusions .............................................. 154
References .................................................... 154
8 One-pot Reactions on Bifunctional Catalysts ............... 157
Michel Guisnet and Matteo Guidotti
8.1 Introduction .............................................. 157
8.2 Examples .................................................. 158
8.2.1 One-pot transformations involving successive
hydrogenation and acid-base steps ................... 158
8.2.2 One-pot transformations involving successive
oxidation and acid-base steps ....................... 166
References .................................................... 168
9 Base-type Catalysis ....................................... 171
Didier Tichit, Sara Iborra, Avelino Corma and
Daniel Brunel
9.1 Introduction .............................................. 171
9.2 Characterization of solid bases ........................... 172
9.2.1 Test reactions ...................................... 172
9.2.2 Probe molecules combined with spectroscopic
methods ............................................. 174
9.3 Solid base catalysts ...................................... 175
9.3.1 Alkaline earth metal oxides ......................... 175
9.3.2 Catalysis on alkaline earth metal oxides ............ 177
9.3.3 Hydrotalcites and related compounds ................. 183
9.3.4 Organic base-supported catalysts .................... 187
9.4 Conclusions ............................................... 195
References .................................................... 195
10 Hybrid Oxidation Catalysts from Immobilized Complexes
on Inorganic Microporous Supports ........................ 207
Dirk De Vos, Ive Hermans, Bert Sels and Pierre Jacobs
10.1 Introduction and scope ................................... 207
10.2 Oxygenation potential of heme-typc complexes in
zeolite .................................................. 211
10.2.1 Metallo-phthallocyanincs encapsulated in
the cages of faujasite-type zeolites .............. 211
10.2.2 Oxygenation potential of metallo-
phthallocyanines encapsulated in the mesopores
of VPI-5 AIPO4 .................................... 215
10.2.3 Oxygenation potential of zeolite encapsulated
metallo-porphyrins ................................ 216
10.3 Oxygenation potential of zeolite encapsulated nonheme
complexes ................................................ 220
10.3.1 Immobilization of N,N'-bidentate complexes in
zeolite Y ......................................... 220
10.3.2 Ligation of zeolite exchanged transition ions
with bidentale aza ligands ........................ 224
10.3.3 Ligation of zeolite exchanged transition ions
with tri- and tetra-aza(cyclo)aIkane ligands ...... 225
10.3.4 Ligation of zeolite exchanged transition ions
with Schiff base-type ligands ..................... 228
10.3.5 Zeolite effects with N,N'-bis
(2-pyridinecarboxamide) complexes of Mn and Fe
in zeolite Y ...................................... 231
10.3.6 Zeolite encapsulated chiral oxidation catalysts ... 233
10.4 Conclusions .............................................. 235
Acknowledgements .............................................. 235
References .................................................... 235
Subject Index ................................................. 241
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