Clay 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 Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2019 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed on acid-free paper International Standard Book Number-13: 978-1-4987-4652-6 (Hardback) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materi- als or the consequences of their use. 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CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identifi- cation and explanation without intent to infringe. 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 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com 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