Table Of ContentHandbook of Hydroxyacetophenones
Handbook of
Hy droxyacetophenones
by
Robert Martin
formerly of the Institut Curie,
Paris, France
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.
A C.I.P. Catalogue record for this book is available from the Library of Congress.
ISBN 978-94-017-1747-2 ISBN 978-94-017-1745-8 (eBook)
DOI 10.1007/978-94-017-1745-8
Printed on acid-free paper
AlI Rights Reserved
© 1997 Springer Science+Business Media Dordrecht
Original1y published by Kluwer Academic Publishers in 1997
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical,
including photocopying, recording or by any information storage and
retrieval system, without written permission from the copyright owner.
To my dear Angele for her faithful devotion throughout these many years. Without You, nothing
would have been possible.
Robert MARTIN
CONTENTS
ix
PREFACE
ACKNOWLEDGEMENTS xi
Introduction
HYDROXYACETOPHENONES
Compounds derived from acetic acid 3
2 Compounds derived from bromoacetic acids 323
2.1 From monobromoacetic acid 323
2.2 From dibromoacetic acid 344
2.3 From tribromoacetic acid 349
3 Compounds derived from chloroacetic acids 350
3.1 From monochloroacetic acid 350
3.2 From dichloroacetic acid 373
3.3 From trichloroacetic acid 379
4 Compounds derived from fluoroacetic acids 385
4.1 From monofluoroacetic acid 385
4.2 From difluoroacetic acid (only a methylether) 386
4.3 From trifluoroacetic acid 387
5 Compounds derived from iodoacetic acids 409
5.1 From monoiodoacetic acid 409
5.2 From diiodoacetic acid (not described till July 1996) 411
5.3 From triiodoacetic acid (not described till July 1996) 412
REFERENCES 413
MOLECULAR FORMULA INDEX 455
CHEMICAL ABSTRACTS REGISTRY NUMBERS 501
USUAL NAMES INDEX 525
COMMON ABBREVIATIONS 531
PREFACE
To fmds one's bearings through the luxuriant forest of organic chemistry, sure guide marks are
needed. Robert Martin's book is one of these most useful reference marks for each organic
chemist.
Diversely substituted hydroxyacetophenones are used in numerous sectors of applied organic
chemistry. This impressive monography constitutes a considerable work, time-saver for the
professional in organic synthesis.
For each compound described, R. Martin has clearly and concisely supplied all the information
existing in the literature up to 1996. This work enables the chemist to compare their structures,
syntheses, properties, physico-chemical characteristics, thus stimulating his imagination. Three
exhaustive tables enable the reader to find each compound by its CAS number, official
nomenclature and usual name. They secure easy navigation through this large Dictionary.
I very much admire the work undertaken and carried through by R. Martin, Chemical Engineer,
Conservatoire National des Arts et Metiers, 1961.
I am sure this book will be helpful both to industry and university research workers, and I wish it
will meet the success it deserves.
Dr. Jean-Paul GUETTE
Professor
Conservatoire National des Arts et Metiers (CNAM)
ACKNOWLEDGEMENTS
I wish to express my heartily thanks to Dr. Pierre Demerseman who accepted me in his Laboratory
at Institut Curie in 1987, and kindly revised my manuscript
I am also grateful to Dr. J.-P. Buisson, always so amiable and efficient, whose knowledge of
word-processing largely contributed to the fmal page-setting of this work.
My thanks are also directed to Prof. Claude Monneret, Head of the Chemical Department at Institut
Curie, who has always been so benevolent to me, and all his collaborators for their warm welcome
at each of my visits.
The foreword of this Dictionary was redacted by Prof. Jean-Paul Guette. I most appreciate this
mark: of kindness.
Various friends who readily accepted to translate foreign publications are also to be acknowledged
here, in particular Dr. Jean Burkhard who has been of unvaluable help for translating german
papers over the last 25 years. The diverse abbreviations used in ancient reviews - particularly
Chemisches Zentralblatt - had no secrets for him.
In this connection, thanks are due to Mrs. Feiga Weisbuch for her precious assistance as regards
rumanian and russian texts, as well as to Miss Marie-Fran<;:oise Liachenko, Dr. Daniel Dauzonne
and Mr. Serge Martin for friendly advice on the english redaction of this book. Moreover, Mr.
Serge Martin was a constant aid to me as regards data processing.
I wish to express my thanks to Mrs. Mireille Guyonneau, Mrs. Fran<;:oise Remy and Mrs. Simonne
Risse for their keen contribution to my bibliographic research, as well as the Orsay University
Library for their helpful kindness towards me for 25 years now.
I am also grateful to Mrs. Colette Ledoux for judicious advice in the field of scientific edition.
Before closing, I would like to remember my dear departed. My affectionate thoughts are turned
towards Prof. Leon Denivelle who transmitted to me his passion for aromatic organic Chemistry in
1945, and Prof. Albert Kimnann who accepted me among his students in 1961 and was always so
amiable and well-disposed whenever I went to him. I cannot mention without emotion Prof. Albert
Saint-Maixen who largely communicated to me his knowledge on analytical Chemistry.
I also have a personal thought towards my friends from the industry who left us too soon. I am
particularly thankful to Drs. Henri Barbier, Felix Lepors and Henri Ruelleux (SPCA, Ltd.) who
gave me the practical means to carry about my work on aromatic hydroxyketones. In this firm, I
started my research on the Fries reaction. I also wish to acknowledge the late Dr. Fran<;:ois Krausz
who, at that time, made me benefit from his precious advice.
Robert MARTIN
INTRODUCTION
Acylphenols are used as starting material for an extremely large number of syntheses in organic
chemistry, leading to a wide range of applications. For this reason, it seemed interesting to offer a
dictionary of Acetylphenols or Hydroxyacetophenones, since they constitute the most numerous
and currently used representatives of this series of compounds. Moreover, most syntheses of
Hydroxyacetophenones can be extended to their superior homologs.
The dictionary covers over 1,400 Hydroxyacetophenones methodically classified under the official
nomenclature of "Ethanones" according to the International System (LU.P.A.C.) and the
recommendations given in the Chemical Abstracts "Collective Index" (9 CI) since 1972.
About 1,600 bibliographic references are compiled in this work. Names of periodicals are
abbreviated according to the Chemical Abstracts Service Source Index (C.A.S.S.I.). Whenever
Hydroxyacetophenones can be obtained from plants, sources and corresponding references are
given.
For each compound described, the different protocols of synthesis are presented as well as the
main physico-chemical characteristics and references of spectroscopic data. Besides the usual
abbreviations are also indicated at the end of this Dictionary.
For precise and quick research of an Hydroxyacetophenone, you can refer either to the
classification by molecular formula (Molecular Formula Index) or to the Chemical
Abstracts Registry Numbers table. An entry Usual Names Index including the current
names of some Hydroxyacetophenones and their precursors is also available.
Finally, a glance through any chapter of this Dictionary will inform the reader on the diverse ways
of synthesizing Hydroxyacetophenones. These methods can be used to obtain hitherto unknown
analogs in the related series.
HYDROXYACETOPHENONES
1. Compounds derivedjrom acetic acid
1-(2,3,5,6-Tetranuoro-4-hy d roxyphenyl )ethanone
[145797-51-9] mol.wt. 208.11
Synthesis
F~F
-Preparation by reaction of acetyl chloride on the
.... 1
2,3,5,6-tetrafluorophenol with aluminium chloride in
F ~ F carbon disulfide at 5° (10%) [589].
COCH3 m.p. 109-111 ° [589]; Spectra (NA).
1-(3,5-Dibromo-2-hydroxy-4-nitrophenyl)ethanone
C8H5Bf2N04 mol.wt. 338.94
Synthesis
-Preparation by reaction of bromine on the 2-hydroxy-
4-nitroacetophenone in refluxing acetic acid-sodium acetate
mixture (68%) [1351].
m.p. 157° [1351]; Spectra (NA).
1-(2,4,6-Tribromo-3-hydroxyphenyl)ethanone
[49605-14-3] mol.wt. 372.84
Synthesis
OH
Br*Br -Preparation by bromination of 3-hydroxyacetophenone in
.... 1 water at 50° (94%) [424,535].
~ COCH3
m.p. 127°5 [424,535]; Spectra (NA).
Br
1-(3,4,5-T rib romo-2-hyd roxyp heny I )ethanone
[145666-19-9] mol.wt 372.84
Synthesis not yet described.
Br...:. q1 COCH3 -Refer to [967], (compound 1h) .
:-...
Br m.p. and Spectra (NA).
Br
