THIOPHENE AND ITS DERIVATIVES. Part One

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1 THIOPHENE AND ITS DERIVATIVES Part One This is the Forty-Fourth Volume in the Series THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS

2 THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS A SERIES OF MONOGRAPHS ARNOLD WEISSBERGER and EDWARD C. TAYLOR Editors

3 THIOPHENE AND ITS DERIVATIVES Part One Edited by Salo Gronowitz University of Lund Lund, Sweden AN PUBLICATION JOHN WILEY AND SONS NEW YORK 0 CHICHESTER 0 BRISBANE 0 TORONTO 0 SINGAPORE -

4 An Publication Copyright by John Wiley & Sons, Inc All rights reserved. Published simultaneously in Canada. Reproduction or translation of any part of this work beyond that permitted by Section 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc. Library of Congress Cataloging in Publication Data: Main cntry under title: Thiophene and its derivatives. (The Chemistry of heterocyclic compounds ; v. 44) An Interscience publication. Includes index. 1. Thiophene. I. Gronowitz, Salo. 11. Series. QD403.T l ISBN (v. 1)

5 Contributors L. I. BELEN KII N. D. Zelinsky Institute of Organic Chemistry Academy of Sciences of the USSR Moscow, USSR P. H. BENDERS Laboratory of Organic Chemistry Twente University of Technology Enschede, The Netherlands F. BOHLMANN Institut fur Organische Chemie Tech n isch e Un iv ersitat Berlin, Federal Republic of Germany G. D. GALPERN Institute of Petrochemical Synthesis Academy of Sciences of the USSR Moscow. USSR YA. L. GOL DFARB N. D. Zelinsky Institute of Organic Chemistry Academy of Sciences of the USSR Moscow, USSR SALO GRONOWITZ Division of Organic Chemistry 1 Chemical Center University of Lund Lund, Sweden ANITA HENRIKSSON-ENFLO Institute of Theoretical Physics University of Stockholm Stockholm, Sweden ALAIN LABLACHE-COMBIER Laboratoire de Chimie Organique Physique Universite des Sciences et Techniques de Lille Villeneuve d Ascq, France A. E. A. PORTER Chemistry Department University of Stirling Stirling, Scotland JEFFERY B. PRESS Cardio vascular-cns Research Section American Cyanamid Company Medical Research Division L ederle Laboratories Pearl River, New York. Presen t affiliation : Ortho Pharmaceutical Corporation Raritan, New Jersey MAYNARD S. RAASCH Central Research and Development Department Experimental Section I<. I. du Pont de Nemours and Company Wilmington, Delaware D. N. REINHOUDT Laboratory of Organic Chemistry Twente University of Technology Ensch ede, The Netherlands W. P. TROMPENAARS Laboratory of Organic Chemistry Twente University of Technology Enschede, The Netherlands C. ZDERO Institut fur Organische Chemie Techn ische Un ivers itat Berlin, Federal Republic of Germany

6 To the memory of VICTOR MEYER great chemist and teacher and founder of thiophene chemistry

7 The Chemistry of Heterocylic Compounds The chemistry of heterocyclic compounds is one of the most complex branches of organic chemistry. It is equally interesting for its theoretical implications, for the diversity of its synthetic procedures, and for the physiological and industrial significance of heterocyclic compounds. A field of such importance and intrinsic difficulty should be made as readily accessible as possible, and the lack of a modern detailed and comprehensive presentation of heterocyclic chemistry is therefore keenly felt. It is the intention of the present series to fill this gap by expert presentations of the various branches of heterocyclic chemistry. The subdivisions have been designed to cover the field in its entirety by monographs which reflect the importance and the interrelations of the various compounds, and accommodate the specific interests of the authors. In order to continue to make heterocyclic chemistry as readily accessible as possible new editions are planned for those areas where the respective volumes in the first edition have become obsolete by overwheliniiig progress. If, however, the changes are not too great so that the first editions can be brought up-to-date by supplementary volumes, supplements to the respective volumes will be published in the first edition. Research Laboratories Eastman Kodak Company Rochester, New York Princeton University Princeton, New Jersey ARNOLD WEISSRERGER EDWARD C. TAYLOR ix

Preface In 1952, in the first volume of The Chemistry of Heterocyclic Compounds, Howard D. Hartough described the state of research on the chemistry of thiophene and its derivatives up to 1950.

8 Preface In 1952, in the first volume of The Chemistry of Heterocyclic Compounds, Howard D. Hartough described the state of research on the chemistry of thiophene and its derivatives up to Selenophene and tellurophene were also included in this monograph which, except for two chapters was written by Hartough alone. When this book was written, the explosive development triggered by the commercial process for thiophene from butane and sulfur, developed by Socony-Vacuum Oil Company in the 1940 s, had just begun. The enornious aniount ofwork carried out on this important aromatic five-membered heterocycle since 1950 makes it of course impossible for one person to cover all aspects, and an able group of specialists were assembled from all over the world to treat the entire field. This makes some minor overlaps between chapters unavoidable, but I think it is important to treat some topics from different angles of approach. Because of the wealth of results and the rather large number of contributors, these volumes are not as strictly organized as some previous volumes in this series, but can be considered as a collection of topics on thiophene chemistry. Together, however, it is my hope that these chapters give as comprehensive a description as possible of the chemistry of thiophene and its monocyclic derivatives, based on the literature from 1950 to References to previous results, treated in Hartough s book, are also given when necessary. The chapters fall in two categories: (1) those that treat syntheses, properties, and reactions of thiophenes, and (2) those that treat systematically functionalized simple thiophenes, such as alkylthiophenes, halothiophenes, aminothiophenes, thiophenecarboxylic acids, and so on. The latter chapters, as is customary in the Wcissberger-Taylor series, contain tables of compounds with their physical properties, which should be very useful for all synthetic chemists. Part 1 of these volumes contains only chapters in category (1) and starts with a treatise on the preparation of thiophenes by ring-closure reactions and from other ring systems. It is followed by a chapter on theoretical calculations. Then, in two chapters, naturally occurring thiophenes in plants and in petroleum, shale oil, and coals are treated. The topic of the next chapter is the important field of pharmacologically active compounds. The synthetic use of thiophene derivatives for the synthesis of aliphatic compounds by desulfurization follows. Two chapters treat thiophenes modified at the sulfur, namely thiophene-1,l-dioxides and thiophene-1-oxides, and S-alkylation of thiophenes. In the last three chapters, the discussion on different reactivities of thiophenes starts with radical reactions of thiophenes, cycloaddition reactions, and photochemical reactions. In the latter parts of this monograph, chapters on derivatives such as alkylthiophenes, halothiophenes, nitrothiophenes, aminothiophenes, hydroxy- and alkoxythiophenes, thiophenethiols, thiophenesulfonic acids, metal derivatives, formyl and acyl derivatives, thiophenecarboxylic acids, thienylethenes and xi

9 x ii Preface -acetylenes, arylthiophenes, and bithienyls are intercalated with chapters on physical and spectroscopical properties, electrophilic and nucleophilic substitution, and side-chain reactivity. I wish to thank all the distinguished scientists who contributed chapters to these volumes for their splendid cooperation and my secretary Ann Nordlund for her invaluable help. I am also indebted to Dr. Robert E. Carter for correcting my chapter and those of some of the other authors whose native tongue is not English. Lund, Sweden August I984 SALO GRONOWITZ

10 Contents I I1 111 IV V VI VII VIII IX X PREPARATION OF THIOPHENES BY RING-CLOSURE REACTIONS AND FROM OTHER RING SYSTEMS SALO GRONOWITZ THEORETICAL CALCULATIONS ON THIOPHENES ANITA HENRIKSSON-ENFLO NATURALLY OCCURRING THIOPHENES F. BOHLMANN and C. ZLIIX~ THIOPHENES OCCURRING IN PETROLEUM, SHALE OIL, AND COALS G. D. GALPCRN PHARMACOLOGICALLY ACTIVE COMPOUNDS AND OTHER THIOPHENE DERIVATIVES JEIWRY B. PRESS REDUCTION AND DESULFURIZATION OF THIOPHENE COMPOUNDS L. I. BELEN KII and YA. L. GOL DPARH THIOPHENE 1,]-DIOXIDES, SESQUIOXIDES AND 1 -OXIDES MAYNARD s. RAASCH REACTIONS AT SULPHUR A. E. A. PORTER RADICAL REACTIONS OF THIOPHENE A. E. A. PORTER CYCLOADDITION REACTIONS OF THIOPHENES, THIOPHENE-1 -OXIDES AND 1,I -DIOXIDES P. M. BENDERS, D. N. REINHOUDT, and W. P. TROMPENAARS xiii

11 xiv XI Contents PHOTOCHEMICAL REACTIONS OF THIOPHENES &AIN LABLACWE-COMBIER 745 AUTHOR INDEX SUBJECT INDEX

12 THIOPHENE AND ITS DERIVATNES Part One 7'his is the Forty-Fourth Volume in the Series THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS

ORGANIC REACTION MECHANISMS * 1991

ORGANIC REACTION MECHANISMS * 1991 ORGANIC REACTION MECHANISMS 1991 An annual survey covering the literature duted December 1990 to November 1991 Edited by A. C. Knipe and W. E. Watts University of Ulster