Heterocyclic Chemistry II

Transcription

1 Heterocyclic Chemistry II

2 Heterocyclic Chemistry R. R. Gupta, M. Kumar, V. Gupta Volume I: Principles, Three- and Four-Membered Heterocycles Volumell: Five-MemberedHeterocycles Volume III: Six-Membered and Higher Heterocycles Springer-Verlag Berlin Heidelberg GmbH

3 R. R. Gupta, M. Kumar, V. Gupta Heterocyclic Chemistry Volume II: Five-Membered Heterocycles With 136 Figures Springer

4 Prof. Radha Raman Gupta Or. Mahendra Kumar Or. Vandana Gupta Oepartment ofchemistry University of Rajasthan Jaipur / India ISBN Library of Congress Cataloging-in-Publication Data Die Deutsche Bibliothek - Cip-Einheitsaufnahme Gupta, Radha R.: Heterocyclic chemistry / R. R. Gupta ; M. Kumar ; V. Gupta. ISBN ISBN (ebook) DOI / This work is subject to copyright. AII rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in other ways, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained rrom Springer-Verlag Berlin Heidelberg GmbH. Violations are liable for prosecution act under German Copyright Law. Springer-Verlag Berlin Heidelberg 1999 Originally published by Springer-Verlag Berlin Heidelberg New York in 1999 Softcover reprint of the hardcover 1 st edition 1999 The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: Camera-ready by authors Cover: E. Kirchner, Heidelberg Production: ProduServ GmbH Verlagsservice, Berlin SPIN: I / Printed on acid -free paper

5 FOREWORD Today, our world increasingly is conceived of as being molecular. An ever widening range of phenomena are described logically in terms of molecular properties and molecular interactions. The majority ofknown molecules are heterocyclic and heterocycles dominate the fields ofbiochemistry, medicinal chemistry, dyestuffs, photographic science and are of increasing importance in many others, including polymers, adhesives, and molecular engmeenng. Thus, the importance of heterocyclic chemistry continues to increase and this three volume work by Drs. R. R. Gupta, Mahendra Kumar and Vandana Gupta is a welcome addition to the available guides on the subject. Its scope places it in a useful niche between the single-volume texts and monographs ofheterocyclic chemistry and the multivolume treatises. The authors have retained the well tried classical approach but have succeeded in placing their own individual spin on their arrangement. They have put together a well selected range from among the most important ofthe vast array of facts available. This factual material is ordered in a clear and logical fashion over the three volumes. The present work should be of great value to students and practitioners ofheterocyclic chemistry at all levels from the advanced undergraduate upwards. It will be of particular assistance in presenting a clear and modem view of the subject to those who use heterocycles in a variety of other fields and we wish it well. April1998 Alan R. Katritzky University offlorida

6 PREFACE Our aim is to bring out a text-cum-reference book on heterocyclic chemistry for undergraduate and graduate students, and research workers who wish to choose heterocyclic chemistry in their research careers. This will enable them to have a comprehensive knowledge of the syntheses, properties, reactions and their mechanisms and applications ofheterocyclic compounds. Efforts have been made to include recent developments in heterocyclic chemistry and the subject is presented in a simple and lucid manner, so that those who have some background knowledge of organic chemistry can understand it well. For the sake of convenience, subject matter covered in heterocyclic chemistry has been divided into three volumes: Volume I : Principles, Three- and Four-Membered Heterocycles Introduction Nomenclature ofheterocycles Aromatic Heterocycles Nonaromatic Heterocycles Heterocyclic Synthesis Three-Membered Heterocycles Four-Membered Heterocycles Volume II : Five-Membered Heterocycles Introduction Five-Membered Heterocycles with One Heteroatom Benzo-Fused Five-Membered Heterocycles with One Heteroatom Five-Membered Heterocycles with Two Heteroatoms Five-Membered Heterocycles with More Than Two Heteroatoms Meso-Ionic Heterocycles

7 VIII Volume III: Six-Membered and Higher Heterocycles Introduction Six-Membered Heterocycles Seven-Membered Heterocycles Large Ring Heterocycles Photochemistry ofheterocycles The present Vol. II is a continuation ofvol. I to provide a comprehensive account ofthe chemistry of five-membered heterocycles to the advanced students, research workers and industrial as well as medicinal chemists. It concerns with the syntheses, reactions, properties, structural parameters, applications, pharmacological/biological significance, etc. for the compounds with one, two and more heteroatoms and their benzo-fused analogs as well as mesoionic compounds. The readers mastered the principles for the syntheses, aromaticity, nonaromaticity, reactions, etc. presented for the heterocyclic systems in Vol. I can understand well the chemistry of fivemembered heterocycles covered in Vol. II. It will be also useful to those who are looking for a survey of well-tried fundamental concepts as well as for information on new developments in the chemistry of five-membered heterocycles. We have freely consulted edited scientific works such as Comprehensive Heterocyclic Chemistry edited by A.R. Katritzky and C.W. Rees, Advances in Heterocyclic Chemistry edited by A.R. Katritzky and the Chemistry of Heterocyclic Compounds edited by A. Weissberger and E. C. Taylor. We are very grateful to editors, authors and publishers of these works. We express our thanks to our colleagues and Ph.D. students who assisted us in proof reading and in several other ways. Our sincere thanks are also due to Dr. R. Stumpe and Dr. Joe P. Richmond editors at Springer Verlag for providing valuable suggestions for the preparation ofthe book. Jaipur, India October, 1998 R.R. Gupta Mahendra Kumar Vandana Gupta

8 Symbols and Abbreviations a A AIBN ~ cone. DE DRE A L'm(8ae) DIBAL Dil. DMF DMSO E ERE Eu(fodh E ~H HMPAIHMPT HOMO Ia and le Bond angle distortion or deviation I Coulomb integral (as stated) Karplus constant I,2,2'-Azobisisobutyronitrile Resonance integral Wave number Concentrated De localization energy Dewar resonance energy Diamagnetic susceptibility exaltation Chemical shift difference Diisobutylaluminium hydride Diluted N,N-Dimethylformamide Dimethyl sulfoxide Bond angle strain I Torsional energy (as stated) Empirical resonance energy Tris-( 6,6, 7, 7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium Extinction coefficient Conformational free energy Free energy of activation Enthalpy difference between conformers Heat of formation ( exp.) Hexamethylphosphoric triamide Highest occupied molecular orbital Band intensity in vibrational spectra for axial and equatorial conformers

9 X J!<,; K, K8 A. LDA LTA LUMO MCPBA NBS hv nm N-PSP pm PPA R REPE \jj Tc TCNE tert TFAA TifF 1HP e TMEDA Tos I Tosyl VR Coupling cosntant Rate of ring inversion Equilibrium constant of interconvertible conformers Bond bending force constant Wavelength Lithium diisopropylarnide Lead tetraacetate Lowest unoccupied molecular orbital m-chloroperbenzoic acid N-Bromosuccinirnide Photochemical Nanometer ( 1 o-9) N-Phenylselenophthalirnide Picometer (1 o-12) Polyphosphoric acid Coupling constants ratio Resonance energy per n:-electron Internal torsional angle Coalescence temperature Tetracyanoethylene Tertiary Trifluoroacetic anhydride Tetrahydrofuran Tetrahydropyran Dihedral angle N,N,N,N-Tetramethylenediamine p-toluenesulfonyl Vilsmeier reagent Dihedral angle deviation Diamagenetic susceptibility

10 CONTENTS Chapter 1. Introduction 1 Chapter 2. Five-Membered Heterocycles with 3 One Heteroatom Chapter 3. Benzo-Fused Five-Memb~red 181 Heterocycles with One Heteroatom Chapter 4. Five-Membered Heterocycles with 357 Two Heteroatoms Chapter 5. Five-Membered Heterocycles with 487 More Than Two Heteroatoms Chapter 6. Meso-Ionic Heterocycles 579 Subject Index 627