The chemistry of. a-haloketones, a-haloaldehydes and a-haloimines

Transcription

1 The chemistry of a-haloketones, a-haloaldehydes and a-haloimines

2 THE CHEMISTRY OF FUNCTIONAL GROUPS A series of advanced treatises under the general editorship of Professor Saul Patai The chemistry of alkenes (2 volumes] The chemistry of the carbonyl group (2 volumes) The chemistry of the ether linkage The chemistry of the amino group The chemistry of the nitro and nitroso groups (2 parts) The chemistry of carboxylic acids and esters The chemistry of the carbon-nitrogen double bond The chemistry of amides The chemistry of the cyano group The chemistry of the hydroxyl group (2 parts) The chemistry of the azido group The chemistry of acyl halides The chemistry of the carbon-halogen bond (2 parts) The chemistry of the quinonoid compounds (2 volumes in 4 parts) The chemistry of the thiol group (2 parts) The chemistry of the hydrazo. azo and azoxy groups (2 parts) The chemistry of amidines and imidates The Chemistry of cyanates and their thio derivatives (2 parts) The chemistry of diazonium and diazo groups (2 parts) The chemistry of the carbon-carbon triple bond (2 parts) The chemistry of ketenes. allenes and related compounds (2 parts) The chemistry of the sulphonium group (2 parts) Supplement A: The chemistry of double-bonded functional groups (2 parts) Supplement B: The chemistry of acid derivatives (2 parts) Supplement C: The chemistry of triple-bonded functional groups (2 parts) Supplement D: The chemistry of halides, pseudo-halides and azides (2 parts) Supplement E: The chemistry of ethers, crown ethers, hydroxyl groups and their sulphur analogues (2 parts) Supplement F: The chemistry of amino, nitroso and nitro compounds and their derivatives (2 parts) The chemistry of the metal-carbon bond (4 volumes) The chemistry of peroxides The chemistry of organic selenium and tellurium compounds (2 volumes) The chemistry of the cyclopropyl group (2 parts) The chemistry of suiphones and sulphoxides -c-c X X X I 40 I 40 I //NR -C- -c-c I H I c-h7 I R

3 The chemistry of a- ha I o keto nes, a- ha I oa Ide h ydes a n d a- ha I o i m i nes BY NORBERT DE KIMPE and ROLAND VERHE The State University of Gent Edited by SAUL PATAI and ZVI RAPPOPORT The Hebrew University of Jerusalem Updates from the Chemistry of Functional Groups 1988 JOHN WILEY & SONS CHICHESTER * NEW YORK * BRISBANE * TORONTO * SINGAPORE An Interscience@ Publication

4 Copyright by John Wiley & Sons Ltd. All rights reserved. No part of this book may be reproduced by any means, or transmitted, or translated into a machine language without the written permission of the publisher Library of Congress Cataloging-in-Publication Data: De Kimpe, Norbert The chemistry of [alpha]-haloketones, [alpha]-haloaldehydes, and [alpha]-haloimines. (The Chemistry of functional groups) Updates from the Chemistry of the functional groups. 1. Ketones. 2. Imines. 3. Organohalogen compounds. I. Verhe, Roland. 11. Patai, Saul Rappoport, Zvi. IV. Title. V. Series. QD305.K2K ISBN British Library Cataloguing in Publication Data: De Kimpe, Norbert The chemistry of a-haloketones, a-haloaldehydes and a-ha1oimines.-(updates from the chemistry of the functional groups). 1. Organohalogen compounds I. Title 11. Verhe, Roland 111. Patai, Saul IV. Rappoport, Zvi V. Series QD305.Hl5 ISBN Typeset by Thomson Press (India) Limited and Printed in Great Britain by Bath Press

5 Contents 1. Synthesis and reactivity of a-halogenated ketones 1 Appendix to Chapter 1 : Synthesis and reactivity of a-halogenated ketones a-halogenated imines 225 Appendix to Chapter 2: a-halogenated imines Synthesis and reactivity of c1- halogenated aldehydes 369 Author index 451 Subject index 489

6 Foreword Updates from the Chemistry of the Functional Groups is a new venture which is actually an offshoot of the main trunk, The Chemistry of Functional Groups. The aim of the Editors and the Publishers is to present selected chapters on a single topic or on closely related topics from the main series, thus making them available for individual chemists in the form of more modestly sized and priced volumes. However, we believed that the presentation of such chapters should be accompanied by appendices updating the material of the original chapters and in some cases even by the addition of new subjects if these dovetail naturally with the older material. This was the case in the present volume, which contains two original chapters from Supplement D of the main series (published in 1983), each updated by an extensive appendix by the same two authors and also a completely new chapter on a-halogenated aldehydes, which fits naturally in with the other two chapters. Thus a complete picture of the a-halogenated derivatives of the three most important carbon heteroatom doubly bonded functional groups (ketones, aldehydes and imines) is given, covering the preparation, properties, reactivity and synthetic applications of the title compounds. Other volumes in the Updates series are already in active preparation and are due to appear shortly. These are a volume on Nitrones, nitronates and nitroxides ; a volume on Crown ethers ; and one on Cyclopropyl radicals, cations, anions, cation and anion radicals. Other volumes, planned for a slightly later publication date, will be on Halogenations, on Synthesis of lactams and lactones, and on Synthetic applications of quinones. We will be very grateful to readers who would call our attention to omissions or mistakes in this and other volumes of the series. JERUSALEM June 1988 SAUL PATAI ZVT RAPPOPORT vii

7 Preface a-halocarbonyl derivatives are an important class of organic compounds, the chemistry of which occupies a key position in modern organic chemistry. The field dates back to more than 150 years ago, when the chlorination of acetone was described and the first characterized a-haloketone was 1, 1-dichloroacetone, described by Fittig in 1859, while bromoacetone was presumably the first characterized a-bromoketone. Since these early results, many and ramified publications have appeared on the chemistry of a-halocarbonyl compounds and many hundreds of papers are added each year. Especially during the last three decades these compounds have received intensive attention, resulting in new and improved synthetic strategies. The high chemical reactivity of a-haloketones and a- haloaldehydes enables them to undergo a wide variety of reactions, and the literature indeed proves the wide synthetic potential of this class of compounds. The chemistry of a-haloimines, i.e. the nitrogen analogues of a-halocarbonyl compounds, started to be studied in depth only in the 1970s. r-haloimines are now increasingly important, especially in view of their ability to act as masked a-halocarbonyl compounds and their wide synthetic potential. The attempt to publish in one book the most pertinent information on a-haloketones, a- haloaldehydes and a-haloimines is the result of a desire by both authors to present an upto-date treatise on these heteroallylic halides, to review the most significant advances in this area and to convey knowledge about the availability of the title compounds, their chemical properties and their role in modern organic synthesis. The chapters deal separately with the chemistry of a-haloketones, a-haloaldehydes and a-haloimines, and their reactivity towards selected carbon, nitrogen, oxygen and sulphur nucleophiles. The literature is reviewed up to the first half of The monograph is designed for the use of students, researchers and professional workers in industry and at academic institutions where organic synthesis and mechanistic organic chemistry are actively practised. The structure of the book needs some comment. The publishers and the Editors of the Functional Groups series of books decided to produce some sections of the series as smaller, more accessible monograph volumes. As the first of these selections, the two chapters on a-haloketones and a-haloimines, which appeared in Supplement D: The Chemistry of Halides, Pseudohalides and Azides, pp and , respectively (1983), have been brought together using the original text published in 1983 and, in addition, extensive up-to-date Appendices to both parts have been added. In order to complete the picture, an entirely new chapter on a-haloaldehydes has been included. Finally, both authors express their gratitude to Professor Niceas Schamp, Director of the Laboratory of Organic Chemistry, Faculty of Agricultural Sciences, State University of Gent, for his support of our research programme during the last two decades. The ix

8 X Preface Belgian Nationaal Fonds voor Wetenschapplijk Onderzoek (National Fund for Scientific Research) is thanked for generous support over the same period of time. Gent, Summer 1987 Norbert DE KIMPE,* Roland VERHE Laboratory of Organic Chemistry, Faculty of Agricultural Sciences, State University of Gent, Coupure Links 653, B-9000 GENT, BELGIUM * Onderzoeksleider of the Belgian National Fonds voor Wetenschappelijk Onderzoek (National Fund for Scientific Research).