Advances in Heterocyclic Chemistry, Volume 48.Pdf

Advances in Heterocyclic Chemistry Volume 48 Editorial Advisory Board R. A. Abramovitch, Clemson, South Carolina A. Albert, Canberra, Australia A. T. Balaban, Bucharest, Romania A. J. Boulton, Norwich, England H. Dorn, Berlin, G.D.R. J. Elguero, Madrid, Spain S. Gronowitz, Lund, Sweden T. Kametani, Tokyo, Japan 0. Meth-Cohn, South Africa C. W. Rees, FRS, London, England E. C. Taylor, Princeton, New Jersey M.TiSler, Ljubljana, Yugoslavia J. A. Zoltewicz, Gainesville, Florida Advances in HETEROCYCLIC CHEMISTRY Edited by ALAN R. KATRITZKY, FRS Kenan Professor of Chemistry Department of Chemistry University of Florida Gainesville, Florida Volume 48 ACADEMIC PRESS, INC. Harcourt Brace Jovanovich, Publishers San Diego New York Boston London Sydney Tokyo Toronto This book is printed on acid-free paper. @ COPYRIGHT 0 1990 BY ACADEMIC PRESS, INC. 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. San Diego. California 92101 United Kingdom Edition published by ACADEMIC PRESS LIMITED 24-28 Oval Road, London NWl 7DX LIBRARY OF CONGRESS CATALOG CARD NUMBER: 62-13037 ISBN 0-12-020648-X (alk. paper) PRINTED IN THE UNITED STATES OF AMERICA 90919293 987654321 Contents PREFACE................................................................. vii Heteroaromatic Sulfoxides and Sulfones: Ligand Exchange and Coupling in Sulfuranes and Ipso-Substitutions SHICERUOAE AND NAOMICHIFURUKAWA I. Introduction .......................................................... I 11. Ligand Coupling and Ligand Exchange in u-Sulfuranes .................... 3 111. Ipso-Substitution of Azaaromatic Sulfoxides and Sulfones .................. 24 IV. Thione-Thiol Tautomerism and Its Application to Organic Synthesis ........ 43 V. Miscellaneous Reactions ............................................... 51 VI. Conclusion ........................................................... 56 References ........................................................... 56 Diazoazoles GIROLAMOCIRRINCIONE, ANNA MARIA ALMERICO, ENRICOAIELLO, AND GAETANODATTOLO 1. Introduction .......................................................... 66 11. Structure and Physical Properties ........................................ 67 111. Reactivity ............................................................ 85 IV. Synthesis ............................................................. 154 V. Applications ........................................... ......... 161 VI. Appendix ............................................................. 166 References ........................................................... 167 Organocobalt-Catalyzed Synthesis of Pyridines H. B~NNEMANNAND W. BRIJOUX I. Introduction .......................................................... 177 11. SurveyofCatalysts .................................................... 180 111. Applications of Cobalt-Catalyzed Pyridine Synthesis ....................... 183 V vi CONTENTS IV . Experimental Techniques ............................................... 204 V . Mechanistic Aspects ................................................... 205 VI . Relations between Catalyst Structure and Effectivity ...................... 214 References ........................................................... 218 Chemistry of Pyrazoles Condensed to Heteroaromatic Five- and Six-Membered Rings MOHAMEDHILMY ELNAGDI. MOHAMED RIFAAT HAMZA ELMOGHAYER.AND KAMALUSEF SADEK I . Introduction .......................................................... 224 I1 . Synthesis of Pyrazoloazines ............................................ 224 111. Synthesis of Pyrazoles Condensed to Five-Membered Rings ................ 251 IV . Other Pyrazoloazoles .................................................. 269 V. Chemical Properties ................................................... 213 Vl . Physicochemical Studies ............................................... 283 References ........................................................... 289 Thianthrenes JOHN A . JOULE I . Introduction .......................................................... 302 I1 . Structure and Physical Properties ........................................ 303 Ill . Reactivity ............................................................ 321 IV . Synthesis of Thianthrenes .............................................. 366 V . Applications .......................................................... 378 References ........................................................... 379 Preface Volume 48 of Advances in Heterocyclic Chemistry consists of five chapters that break considerable new ground for the series. Oae and Furukawa have contributed what is essentially a double chapter dealing with two important and fast-developing aspects of sulfur heterocyclic chemistry. The first is ligand coupling and exchange in sulfuranes and the second is ipso-substitution in S-substituted heterocyles. Cirrincione, Almerico, Aiello, and Dattolo cover diazoazoles. This complements a chapter by Tedder that appeared in Volume 1 of the series but which is now very much outdated. The subject has expanded greatly, and the Palermo authors have much fascinating chemistry to recount. The elegant cobalt-catalyzed syntheses of pyridines, on which so much work has been done at Muelheim, is aptly summarized by Bonnemann and Brijoux. Elnagdi, Elmoghayer, and Sadek complete in this volume a survey of heterocycles containing condensed pyrazole ring systems. Thus, following earlier chapters that have appeared on pyrazolopyridines (Vol- ume 36) and on pyrazolopyrimidines (Volume 41), we now have a complete survey of systems in which a pyrazole ring is condensed with another five- or six-membered heteroaromatic ring. Last but not least, the thianthrenes, derived from a ring system that is rapidly increasing in importance because of its electronic properties, are reviewed by Joule. Readers are reminded that this volume will contain no index. The last index volume was Volume 46, and we now plan to desig- nate every fifth volume an index volume; thus the next will be Volume 51. ALANR. KATRITZKY vii This Page Intentionally Left Blank ADVANCES IN HETEROCYCLIC CHEMISTRY, VOL. 48 Heteroaromatic Sulfoxides and Sulfones: Ligand Exchange and Coupling in Sulfuranes and Ipso-Substitutions SHIGERU OAE Department of Chemistry, Okayama University of Science Okayama 700, Japan NAOMICHI FURUKAWA Department of Chemistry, Tsukuba Universiiy Tsukuba, Ibaraki 305, Japan I. Introduction . , . , . 1 11. Ligand Coupling and Ligand Exchange in cr-Sulfuranes . 3 A. Ligand Coupling in o-Sulfurane Intermediates . , . , . , . 3 B. Stereochemistry of Ligand Coupling on the Sulfur Atom . 9 C. Ligand Coupling and Exchange on the Sulfur Atom.. 11 D. Ligand Coupling and Pseudorotation . 17 E. Miscellaneous Examples of Ligand Coupling . 20 111. Ipso-Substitution of Azaaromatic Sulfoxides and Sulfones . 24 A. Introduction to Ipso-Substitution . , . 24 B. General Reactions of Azaaromatics with Organometallic Reagents and Nucleophiles ........................................................ 35 C. Miscellaneous Desulfinations . 39 IV. Thione-Thiol Tautomerism and Its Application to Organic Synthesis . 43 V. Miscellaneous Reactions . 51 A. Intramolecular Rearrangement of Sulfur Functional Groups . 51 B . Intramolecular Rearrangement of Benzimidazole Sulfoxides . 53 C. Sulfur as an Auxilliary in the Diels-Alder Reaction of Triazines. 55 VI. Conclusion . 56 References . , . , . , . , . 56 I. Introduction The sulfur atom is well known for its ability to form stable multicoor- dinated states involving not only di-, but also tri-, tetra-, penta-, and even hexacoordinated compounds. The central sulfur atom in organic molecules can exapnd its valence shell beyond the normal octet valence to that 1 Copyright 0 1990 by Academic Press, Lnc. All rights of reproduction in any form reserved. 2 SHIGERU OAE AND NAOMICHI FURUKAWA [Sec. I. of decet or even dodecet. This property is in marked contrast to that of the oxygen atom, although both belong to the same family. Therefore, many types of organic sulfur compounds can be prepared, which are inconceiv- able for the corresponding oxygen analogues. Hence, organic sulfur compounds have been and will continue to be used widely for modern organic syntheses (62MI1; 68MI1; 77MI1) since organosulfur compounds are quite reactive and undergo numerous novel reactions upon treatment with elec- trophiles, nucleophiles, free radicals, and oxidizing or reducing agents. Mechanistic studies of these reactions started in the mid-1950s. The first monograph describing this kind of work was written by us in 1962. The characteristic properties of organosulfur compounds compared to those of oxygen analogues, can be summarized as follows: (1) The sulfur atom can usually be converted to various oxidation states. (2) The sulfur atom can be readily introduced into molecules. It can also be removed easily by treat- ing the molecule with common reagents since the energies of sulfur atom bonds are lower than those of the oxygen atom. (3) The dicoordinated sulfur atom placed at an a-position can stabilize carbanions, carbonium cations, and carbon free-radicals. Tri-, and tetracoordinated sulfur atoms also stabilize carbanions generated at the a-position. Thus, by using these carbanions or carbonium cations stabilized by the sulfur atom, many elegant organic

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