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PREPARATIVE ORGANIC CHEMISTRY CONTRIBUTING AUTHORS CH. BISCHOFF (BERLIN) H. DORN (BERLIN) P.-G. DIETRICH (BERLIN) H. GROSS (BERLIN) I. EICHHORN (BERLIN) G. HILGETAG (BERLIN) E. GRUNDEMANN (BERLIN) O. KOVACS (SZEGED) E. HOFT (BERLIN) D. MARTIN (BERLIN) G. LEHMANN (BERLIN) R. OHME (BERLIN) D. MURAWSKI (BERLIN) H. SCHICK (BERLIN) E. SCHMITZ (BERLIN) M. SCHULZ (BERLIN) H. SEEBOTH (BERLIN) H. TEICHMANN (BERLIN) J. DAHLMANN (BERLIN) A. ZUBEK (BERLIN) WEYGAND/HILGETAG PREPARATIVE ORGANIC CHEMISTRY EDITED BY G. HILGETAG AND A. MARTINI Institut fur Organische Chemie der Deutschen Akademie der Wissenschaften zu Berlin A Wiley-Inter science Publication JOHN WILEY & SONS New York • London • Sydney • Toronto Copyright © 1972, by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. No part of this book may be reproduced by any means, nor transmitted, nor translated into a machine language without the written permission of the publisher. LIBRARY OF CONGRESS CA TALOGING IN PUBLICATION DA TA: Weygand, Conrad, 1890-1945. Weygand/Hilgetag, Preparative organic chemistry. "A Wiley-Interscience publication." Translation of the 4th ed. of Organisch-chemische Experimentierkunst, edited by G.Hilge- tag and A. Martini, which is an enlarged and updated version of part 2 of the original ed. Includes bibliographical references. 1. Chemistry, Organic-Synthesis. I. Hilgetag, Gtinter, ed. II. Martini, A., ed. III. Title. [DNLM: 1. Chemistry, Organic. QD 251 W5470 1972] QD262.W4613 547'.2 72-6800 ISBN 0-471-93749-5 Printed in the German Democratic Republic 10—9 8 7 6 5 4 3 2 1 Foreword to the 4 th Edition The first edition of " Organisch-chemische Experimentierkunst" by Professor Conrad Weygand was published some 30 years ago. He divided the book into three parts, corresponding to the natural course of an organic-chemical experiment, namely, construction of an apparatus, performance of the chemical reaction, and finally analysis and physical characterization of the product. For arrangement of the actual chemical part, dealing with reactions, Weygand chose a particularly clear and satisfying division, which was then new, based on the formation of the various carbon bonds. The first section of this part contained the reactions on the pre-formed carbon skeleton, the second contained the formation of C—C bonds, the third the cleavage of C—C bonds, and the last the rearrangements of carbon compounds. This "Weygand key" has since been taken over as organizational principle in the Theilheimer series. Division according to reaction type has also been adopted recently in text- books, for example, in "Cahiers de Synthese Organique — Methodes et Tableaux d'Application". After the tragic death of Professor Weygand in April 1945 preparation of the second edition was continued by his pupil and collaborator, Dr. Theo Sieben- mark. The third edition, which appeared in 1964, was made possible by a number of specialist chemists, mostly colleagues at the Institut fur Organische Chemie der Deutschen Akademie der Wissenschaften zu Berlin, who declared them- selves ready to revise the book completely. The subdivision into "Materials and Operations "," Reactions ", and " Chemical and Physical Characterization " was retained in that edition. The present fourth edition consists only of the previous second part, " Re- actions". Except for the chapters "Preparative Work with Small Quantities" and "Solvents and Gases" (a new section) which are retained as Appendices, the previous first part, "Materials and Operations" has been omitted since in the meanwhile monographs have appeared that treat this subject in greater detail. The previous third part, "Chemical and Physical Characterization", has also not been retained; it was too brief to provide a satisfactory guide and we agree with various critics of the third edition that it is better to consult detailed specialist books for chemical and physical analysis. Vi Foreword to the 4 th Edition The fourth edition has been expanded by a chapter on the "Formation of Carbon-Phosphorus Bonds" and by another on the "Formation of Carbon- Deuterium Bonds". The chapter on "Alteration of Nitrogen Groups in Carbon- Nitrogen Compounds" has been substantially expanded, but the remaining parts of the book have merely been completed by inclusion of preparative processes discovered in recent years. As the contributors handled their chapters more or less contemporaneously, the literature throughout this edition has been taken into account up to 1967. I am most grateful to the contributors for their rapid and conscientious revision or re-working of their chapters. Berlin, 1968 G. Hilgetag Summary of Contents Introduction: Organization of the Material 1 Part A. Reactions on the Intact Carbon Skeleton 1. Formation of carbon-hydrogen bonds By Ch. Bischoff, P.-G. Dietrich, E. Hoft and D. Murawski (Berlin) 5 2. Formation of carbon-deuterium bonds By D. Murawski (Berlin) 85 3. Formation of carbon-halogen bonds By H. Dorn (Berlin) 102 4. Formation of carbon-oxygen bonds By M. Schulz and H. Seebach (Berlin) 273 5. Cleavage of carbon-oxygen bonds By H. Seebach and M. Schulz (Berlin) 391 6. Formation of carbon-nitrogen bonds By G. Lehmann and H. Teichmann (Berlin) 404 7. Alteration of nitrogen groups in carbon-nitrogen compounds By R. Ohme and A. Zubek (Berlin) 549 8. Formation of carbon-sulfur bonds By D. Martin (Berlin) 600 9. Formation of carbon-phosphorus bonds By H. Teichmann (Berlin) 693 10. Formation of metal-carbon bonds By J. Dahlmann (Berlin) 748 11. Formation of carbon-carbon multiple bonds By I. Eichhorn (Berlin) 813 Part B. Formation of New Carbon-Carbon Bonds By H. Gross, Ch. Bischoff, E. Hoft, and E. Grundemann (Berlin) 845 Part C. Cleavage of Carbon-Carbon Bonds By G. Hilgetag (Berlin) 1003 Part D. Rearrangement of Carbon Compounds By E. Schmitz (Berlin) 1053 Appendix I. Purification and drying of organic solvents By H. Schick (Berlin) » 1095 Appendix II. Preparation and purification of gases By H. Schick (Berlin) 1103 Appendix III. Preparative organic work with small quantities By 5. Kovacs (Szeged) 1107 vii Contents Introduction; Organization of the Material 1 PART A. Reactions on the Intact Carbon Skeleton 3 Chapter L Formation of carbon-hydrogen bonds 5 1.1. Formation of the carbon-hydrogen bond by addition 5 I. Addition of hydrogen to C=C bonds and aromatic systems 5 1. Chemical reducing agents 5 a. Reduction by non-noble metals 6 i, Reduction by sodium and alcohols 6 ii, Reduction with sodium amalgam 7 iii, Reduction with aluminum amalgam 8 iv, Reduction by solutions of alkali or alkaline-earth metals in liquid ammonia 8 v, Reduction by lithium in organic amines 10 vi, Reduction by zinc, tin, or aluminum 11 b. Electrolytic reduction 12 c. Reduction by lithium aluminum hydride or similar compounds 13 d. Reduction by diimine 15 e. Other reducing agents 17 2. Catalytic hydrogenation 18 a. Catalysts 18 i, Noble-metal catalysts (Adams catalysts) 19 ii, Skeletal alloy catalysts (Raney metals) 22 iii, Metal catalysts 24 iv, Copper oxide-chromium oxide catalysts (Adkins catalysts) 26 v, Sulfide catalysts 27 b. Apparatus and procedure for hydrogenation 28 i, Hydrogenation on a shaking machine 28 ii, High-pressure hydrogenation 30 iii, Hydrogenation in a catalyst tube 31 c. Examples of catalytic hydrogenation 32 i, Choice of catalyst 32 ii, Hydrogenation of olefinic double bonds 32 iii, Selective hydrogenation 33 iv, Hydrogenation of aromatic compounds 36 v, Hydrogenation of heterocycles 38 vi, Catalytic hydrogenation by bonded hydrogen 40 ix X Contents II. Addition of hydrogen to C==C bonds 40 1. Chemical methods 41 2. Catalytic hydrogenation 43 III. Addition of hydrogen to C=O bonds 45 1. Reduction by non-noble metals 45 2. Meerwein-Ponndorf-Verley reduction 47 3. Reduction by lithium aluminum hydride 51 4. Reduction by complex boron hydrides 55 5. Catalytic reduction 59 6. Reduction by diimine 62 1.2. Formation of the carbon-hydrogen bonds by exchange 62 I. Replacement of halogen by hydrogen 62 1. Replacement of halogen on single C-C bonds 63 a. Direct replacement 63 b. Replacement of halogen via intermediates 65 2. Replacement of halogen bound to olefinic or aromatic systems 65 3. Replacement of halogen in other surroundings (in acid chlorides) 66 II. Replacement of oxygen by hydrogen 68 1. Replacement of the hydroxyl group 68 2. Replacement of carbonyl-oxygen 71 a. Direct replacement 71 b. Replacement of carbonyl oxygen via intermediates 74 i, Wolff-Kishner methods 74 ii, Replacement of carbonyl oxygen via mercaptals 76 3. Replacement of oxygen in carboxyl or alkoxycarbonyl groups 76 4. Reduction of amides and lactams 79 III. Replacement of nitrogen by hydrogen 80 IV. Replacement of sulfur by hydrogen 83 Chapter 2. Formation of carbon-deuterium bonds 85 Introduction 85 2.1. Formation of the carbon-deuterium bond by addition 87 I. Addition of DO or DX to carbon-carbon multiple bonds 87 2 II. Addition of deuterium to carbon-carbon multiple bonds 88 III. Addition of deuterium to carbonyl double bonds 90 2.2. Formation of the carbon-deuterium bond by exchange 91 I. Replacement of metal by deuterium 91 II. Replacement of halogen by deuterium 92 III. Replacement of oxygen by deuterium 93 2.3. Isotope exchange methods 94 I. General 94 II. Exchange of labile bonded hydrogen 95 III. Exchange reactions in alkaline media 96 1. Exchange in aqueous solution 96 2. Exchange in liquid [D] ammonia 98 3 IV. Exchange reactions in acid media 99 Chapter 3. Formation of carbon-halogen bonds 102 3.1. Formation of carbon-halogen bonds by addition 102 I. Addition of halogen or thiocyanogen to C—C multiple bonds 102 1. Properties and purification of halogens and thiocyanogen 102 2. Addition of halogen to C=C bonds: general 105