Table Of ContentClay Mineral Catalysis of
Organic Reactions
Clay Mineral Catalysis of
Organic Reactions
Benny K.G. Theng
Manaaki Whenua—Landcare Research
Palmerston North
New Zealand
CRC Press
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Library of Congress Cataloging‑in‑Publication Data
Names: Theng, B. K. G., author.
Title: Clay mineral catalysis of organic reactions / Benny K.G. Theng.
Description: Boca Raton : CRC Press, Taylor & Francis Group, 2018. | Includes
bibliographical references.
Identifiers: LCCN 2018008642 | ISBN 9781498746526 (hardback : alk. paper)
Subjects: LCSH: Clay catalysts. | Catalysts. | Mineralogical chemistry. |
Chemistry, Organic.
Classification: LCC QD501 .T575 2018 | DDC 541/.395--dc23
LC record available at https://lccn.loc.gov/2018008642
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Dedication
To my wife, Judith
Contents
Preface...............................................................................................................................................xi
Author ............................................................................................................................................xiii
Chapter 1 Clays and Clay Minerals: Structures, Compositions, and Properties ..........................1
1.1 Concepts and Definitions ...................................................................................1
1.2 Structural Aspects .............................................................................................7
1.3 Specific Structural and Surface Properties .....................................................16
1.3.1 Kaolinite .............................................................................................26
1.3.2 Halloysite ............................................................................................30
1.3.3 Chrysotile ...........................................................................................32
1.3.4 Smectite ..............................................................................................34
1.3.5 Vermiculite .........................................................................................38
1.3.6 Chlorite ...............................................................................................41
1.3.7 Mica, Illite, Synthetic Mica-Montmorillonite,
and Fluorotetrasilicic Mica ................................................................42
1.3.8 Sepiolite and Palygorskite ..................................................................45
1.3.9 Allophane and Imogolite ....................................................................48
References ..................................................................................................................53
Chapter 2 Surface Acidity and Catalytic Activity ......................................................................85
2.1 Introduction .....................................................................................................85
2.2 Acids and Bases ...............................................................................................85
2.2.1 Acid Strength ......................................................................................86
2.3 Brønsted Acidity ..............................................................................................95
2.4 Lewis Acidity ................................................................................................101
2.5 Brønsted−Lewis Acid Combination and Synergy .........................................106
2.6 Concentration and Distribution of Surface Acid Sites ..................................109
2.6.1 Amine Titration ................................................................................109
2.6.2 Adsorption and Desorption of Basic Probe Molecules ....................114
References ................................................................................................................118
Chapter 3 Surface Activation and Modification .......................................................................131
3.1 Introduction ...................................................................................................131
3.2 Acid Activation ..............................................................................................133
3.3 Thermal Activation and Related Treatments .................................................155
3.3.1 Heating and Calcination ...................................................................155
3.3.2 Microwave and Ultrasound Irradiation ............................................157
3.4 Pillared Interlayered Clays and Porous Clay Heterostructures .....................163
3.5 Organically Modified Clay Minerals ............................................................176
3.5.1 Organoclays and Related Materials..................................................176
3.5.2 Surface Grafting and Silylation ........................................................181
References ................................................................................................................183
vii
viii Contents
Chapter 4 Organic Catalysis by Clay-Supported Reagents ......................................................221
4.1 Introduction ...................................................................................................221
4.2 Clay-Supported Metal Salts ...........................................................................221
4.2.1 Clay-Supported Zinc(II) Chloride and Other Metal Chlorides .......222
4.2.2 Clay-Supported Iron(III) Nitrate and Other Metal Nitrates.............226
4.3 Clay-Supported Metal Oxides and Metal Sulfides ........................................229
4.4 Clay-Supported Metal Nanoparticles ............................................................230
4.5 Clay-Supported Organic and Metal-Organic Reagents .................................236
4.6 Clay-Supported Heteropolyacids ...................................................................241
References ................................................................................................................244
Chapter 5 Clay Mineral Catalysis of Name Reactions .............................................................261
5.1 Introduction ...................................................................................................261
5.2 Alder−Ene Reaction ......................................................................................261
5.3 Baeyer−Villiger Condensation and Oxidation ...............................................262
5.4 Bamberger Rearrangement ............................................................................263
5.5 Baylis−Hillman Reaction ..............................................................................263
5.6 Beckmann Rearrangement ............................................................................264
5.7 Biginelli Reaction ..........................................................................................265
5.8 Diels−Alder Reaction ....................................................................................266
5.9 Ferrier Rearrangement...................................................................................269
5.10 Fischer Glycosidation/Glycosylation .............................................................270
5.11 Fischer−Hepp Rearrangement .......................................................................270
5.12 Fischer Indole Synthesis ................................................................................270
5.13 Fischer−Tropsch Synthesis ............................................................................271
5.14 Friedel−Crafts Reaction ................................................................................271
5.15 Friedländer Synthesis ....................................................................................273
5.16 Fries Rearrangement .....................................................................................274
5.17 Hantzsch Dihydropyridine Synthesis ............................................................274
5.18 Heck Reaction ................................................................................................275
5.19 Knoevenagel Condensation ...........................................................................276
5.20 Mannich Reaction ..........................................................................................277
5.21 Markovnikov Addition Rule ..........................................................................277
5.22 Michael Addition ...........................................................................................278
5.23 Mukaiyama Aldol Reaction ...........................................................................279
5.24 Nicholas Reaction ..........................................................................................280
5.25 Oppenauer Oxidation ....................................................................................280
5.26 Paal–Knorr Synthesis ....................................................................................280
5.27 Pechmann Condensation ...............................................................................281
5.28 Prins Reaction ...............................................................................................281
5.29 Ritter Reaction ...............................................................................................282
5.30 Sakurai Allylation Reaction ..........................................................................282
5.31 Sonogashira Reaction ....................................................................................283
5.32 Strecker Reaction ...........................................................................................283
5.33 Suzuki Reaction .............................................................................................284
5.34 Wacker Oxidation ..........................................................................................284
5.35 Wittig Reaction ..............................................................................................285
References ................................................................................................................285
Contents ix
Chapter 6 Clay Mineral Catalysis of Isomerization, Dimerization, Oligomerization,
and Polymerization Reactions ..................................................................................299
6.1 Introduction ...................................................................................................299
6.2 Isomerization .................................................................................................299
6.2.1 Hydrocarbons ...................................................................................299
6.2.2 Non-Hydrocarbons ...........................................................................304
6.3 Dimerization ..................................................................................................306
6.3.1 Hydrocarbons ...................................................................................306
6.3.2 Non-Hydrocarbons ...........................................................................307
6.4 Oligomerization .............................................................................................310
6.4.1 Hydrocarbons ...................................................................................310
6.4.2 Non-Hydrocarbons ...........................................................................311
6.5 Polymerization ...............................................................................................312
6.5.1 Hydrocarbons ...................................................................................319
6.5.2 Non-Hydrocarbons ...........................................................................322
6.5.3 In Situ Polymerization of Monomers and Polymer-Clay
Nanocomposite Formation ...............................................................325
References ................................................................................................................328
Chapter 7 Clay Mineral Catalysis of Redox, Asymmetric, and Enantioselective Reactions .......347
7.1 Introduction ...................................................................................................347
7.2 Oxidation Reactions ......................................................................................355
7.2.1 Epoxidation and Oxygenation ..........................................................361
7.3 Reduction, Hydrogenation, and Deoxygenation ............................................362
7.4 Asymmetric/Enantioselective Reactions and Syntheses ...............................366
References ................................................................................................................370
Chapter 8 Clay Mineral Catalysis of Natural Processes and Prebiotic Organic Reactions ......389
8.1 Introduction ...................................................................................................389
8.2 Clays and Clay Minerals as Geocatalysts .....................................................389
8.2.1 Hydrocarbon Cracking .....................................................................389
8.2.2 Carboxylic Acid Transformation ......................................................391
8.2.3 Kerogen Transformation and Pyrolysis ............................................394
8.3 Clay Mineral Catalysis of Prebiotic Organic Reactions ................................398
8.3.1 Polypeptide Synthesis .......................................................................399
8.3.2 Selective Adsorption and Polymerization of
Amino Acid Enantiomers .................................................................401
8.3.3 Dimerization and Oligomerization of Nucleotides ..........................402
References ................................................................................................................404
Index ..............................................................................................................................................417
