Hydrogenation Methods

Hydrogenation Methods Paul N. Rylander Engelhard Corporation Edison, New Jersey 1985 ACADEMIC PRESS (Harcourf Brace Jovanovich. Publishers) London Orlando San Diego New York Toronto Montreal Sydney Tokyo This book is a guide to provide general information concerning its subject matter; it is not a procedural manual. Synthesis of chemicals is a rapidly changing field. The reader should consult current procedural manuals for state-of-the-art instructions and applicable government safety regulations. The Publisher and the authors do not accept responsibility for any misuse of this book, including its use as a procedural manual or as a source of specific instructions. COPYRIGHT © 1985 BY ACADEMIC PRESS INC. (LONDON) LTD. ALL RIGHTS RESERVED. NO PART OF THIS PUBLICATION MAY BE REPRODUCED OR TRANSMITTED IN ANY FORM OR BY ANY MEANS, ELECTRONIC OR MECHANICAL, INCLUDING PHOTOCOPY, RECORDING, OR ANY INFORMATION STORAGE AND RETRIEVAL SYSTEM, WITHOUT PERMISSION IN WRITING FROM THE PUBLISHER. ACADEMIC PRESS INC. (LONDON) LTD. 24-28 Oval Road LONDON NWl 7DX United States Edition published by ACADEMIC PRESS, INC. Orlando, Florida 32887 BRITISH LIBRARY CATALOGUING IN PUBLICATION DATA Rylander, Paul N. Hydrogenation methods. (Best synthetic methods) 1. Hydrogenation 2. Chemistry, Organic I. Title II. Series 547'.23 QD281.H8 LIBRARY OF CONGRESS CATALOGING IN PUBLICATION DATA Rylander, Paul NeIs, Date Hydrogenation methods. (Best synthetic methods) Includes index. 1. Hydrogenation. QD281.H8R93 1985 ISBN 0-12-605365-0 (alk. paper) PRINTED IN THE UNITED STATES OF AMERICA 85 86 87 88 9 8 7 6 5 4 3 2 1 Contents Foreword vii Preface ix Detailed Contents xi Chapter 1. Catalysts, Reactors, and Reaction Parameters 1 Chapter 2. Hydrogenation of Olefins 29 Chapter 3. Hydrogenation of Acetylenes 53 Chapter 4. Hydrogenation of Aldehydes and Ketones 66 Chapter 5. Hydrogenation of Acids, Anhydrides, and Esters 78 Chapter 6. Reductive Alkylation 82 Chapter 7. Hydrogenation of Nitriles and Oximes 94 Chapter 8. Hydrogenation of Nitro Compounds 104 Chapter 9. Hydrogenation of Carbocyclic Aromatic Compounds 117 Chapter 10. Hydrogenation of Anilines, Phenols, and Derivatives 123 Chapter 11. Hydrogenation and Hydrogenolysis of Heterocycles 133 Chapter 12. Catalytic Dehydrohalogenation 148 Chapter 13. Miscellaneous Hydrogenolyses 157 Index of Compounds and Methods 185 Foreword There is a vast and often bewildering array of synthetic methods and reagents available to organic chemists today. Many chemists have their own favoured methods, old and new, for standard transformations, and these can vary considerably from one laboratory to another. New and unfamiliar methods may well allow a particular synthetic step to be done more readily and in higher yield, but there is always some energy barrier associated with their use for the first time. Furthermore, the very wealth of possibilities creates an information retrieval problem: How can we choose between all the alternatives, and what are their real advantages and limitations? Where can we find the precise experimental details, so often taken for granted by the experts? There is therefore a constant demand for books on synthetic methods, especially the more practical ones like "Organic Syntheses," "Organic Reactions/' and "Reagents for Organic Synthesis," which are found in most chemistry laboratories. We are c