Tải bản đầy đủ - 0 (trang)
1 Hydroxy Groups Located on One Ring (Not Described yill December 1999)

1 Hydroxy Groups Located on One Ring (Not Described yill December 1999)

Tải bản đầy đủ - 0trang

Handbook of

Hydroxybenzophenones



by

Robert Martin

formerly of the Institut Curie,

Paris, France



KLUWER ACADEMIC PUBLISHERS

DORDRECHT / BOSTON / LONDON



A CLP. Catalogue record for this book is available from the Library of Congress.



ISBN 0-7923-6507-0



Published by Kluwer Academic Publishers,

P.O. Box 17, 3300 AA Dordrecht, The Netherlands.

Sold and distributed in North, Central and South America

by Kluwer Academic Publishers,

101 Philip Drive, Norwell, MA 02061, U.S.A.

In all other countries, sold and distributed

by Kluwer Academic Publishers,

P.O. Box 322, 3300 AH Dordrecht, The Netherlands.



Printed on acid-free paper



All Rights Reserved

© 2000 Kluwer Academic Publishers

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.

Printed in the Netherlands.



To my dear Angele, always so touchingly devoted to me throughout these many years. She reminds

me every day of the sweet title of this song by Jean Ferrat: "What would I be without you?".

Robert MARTIN



PREFACE



Two centuries of organic chemistry have already yielded millions of molecules, either

synyhesized or isolated as natural products created by biosynthesis, but much still remains to be

done. Therefore, from time to time, it is probably useful to gather and classify the scattered data

concerning this or that class of compounds in order to save time for chemists planning new

syntheses or natural products isolations.

As a continuation of his previous Handbook of Hydroxyacetophenones, R. MARTIN now

tackles the Hydroxybenzophenones and related aromatic ketones in a new Handbook including

circa 1900 molecules and 1500 references up to June 1999.

The data concern the syntheses routes or natural origin, physicochemical and spectroscopical

characteristics available in the literature and, should the occasion arise a criticism of dubious

structures or constants.

Since hydroxyketones are widely utilized, themselves or as intermediates, in numerous

syntheses interesting, among others, pharmaceuticals, dyes, agrochemicals, perfumes and plastic

preservatives, this handbook will be of great value for both academic and industrial research

chemists. The multiple ways of hydroxybenzophenones syntheses herein described will certainly

help chemists, as most of these methods can be applied to prepare analogues in aromatic and even in

some heterocyclic series.

The three exhaustive indexes enable the reader to rapidly find a compound and its isomers if

previously published or patented and to select the best way for preparation.

Considering the large amount of information included in this Handbook, I guess it will be entirely

successful.

P. Demerseman



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. The foreword of this Handbook was

also redacted by Dr. Pierre Demerseman. I most appreciate this mark of kindness.

I am also grateful to Dr. J.-P. Buisson, always so amiable and efficient, whose knowledge of wordprocessing largely contributed to the final 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.

I thank my son 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.

The author also thanks Prof. Jean Paul Guette for all his good advices.

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 30 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-Frangoise Liachenko and Dr. Daniel

Dauzonne. I wish to express my thanks to Mrs. Mireille Guyonneau, Mrs. Elisabeth Matarasso,

Mrs. Franchise 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 30 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. Albeit Kirrmann 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. Frangois 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 Benzoylphenols or Hydroxybenzophenones, since they constitute the most numerous

and currently used representatives of this series of compounds. Moreover, most syntheses of

Hydroxybenzophenones can be extended to their other homologs not described here.

The dictionary covers over 1,900 Hydroxybenzophenones methodically classified under the official

nomenclature of "Methanones" according to the International System (LU.P.A.C.) and the

recommendations given in the Chemical Abstracts "Collective Index" (9 CI) since 1972.

About 1,500 bibliographic references are compiled in this work. Names of periodicals are

abbreviated according to the Chemical Abstracts Service Source Index (CA.S.S.I.). Whenever

Hydroxybenzophenones 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 Hydroxybenzophenone, 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 Hydroxybenzophenones. These methods can be used to obtain hitherto unknown

analogs in the related series.



Contents



Preface ............................................................................................



xi



Acknowledgements .........................................................................



xiii



Introduction ......................................................................................



xv



Part I. Monoaroylphenols

1. Unsubstituted Hydroxybenzophenones (Class of METHANONES) ........



3



1. Monohydroxybenzophenones .....................................................



3



2. Dihydroxybenzophenones ..........................................................

2.1 Hydroxy Groups Located on One Ring .................................

2.2 Hydroxy Groups Located on Both Rings ...............................

Symmetrical Ketones ............................................................

Asymmetric Ketones .............................................................



8

8

13

13

15



3. Trihydroxybenzophenones .........................................................

3.1 Hydroxy Groups Located on One Ring .................................

3.2 Hydroxy Groups Located on Both Rings ...............................



17

17

19



4. Tetrahydroxybenzophenones .....................................................

4.1 Hydroxy Groups Located on One Ring .................................

4.2 Hydroxy Groups Located on Both Rings ...............................

Symmetrical Ketones ............................................................

Asymmetric Ketones .............................................................



22

22

22

22

24



5. Pentahydroxybenzophenones ....................................................

5.1 Hydroxy Groups Located on One Ring .................................

5.2 Hydroxy Groups Located on Both Rings ...............................



28

28

28



6. Hexahydroxybenzophenones .....................................................

Symmetrical Ketones .....................................................................

Asymmetric Ketones ......................................................................



32

32

33



This page has been reformatted by Knovel to provide easier navigation.



vii



viii



Contents



2. Substituted Hydroxybenzophenones (Class of METHANONES) ............



35



1. Monohydroxybenzophenones .....................................................

1.1 Substituents Located on the Hydroxylated Ring ...................

Phenyl(2,3,5-trichloro-6-hydroxyphenyl)methanone to (2Hydroxy-4,5-dimethylphenyl) phenylmethanone .......

(2-Hydroxy-4,6-dimethyIphenyl)phenylmethanone to [2Hydroxy-3,5-bis(3-methyl-2-butenyl)-4,6-bis[[(4methylphenyl)sulfonyl]oxy]phenyl]phenylmethanone ......................................................

1.2 Substituents Located on the Other Ring ...............................

1.3 Substituents Located on Both Rings .....................................

(2,4-Dichlorophenyl)(2,3,5-trichloro-6-hydroxyphenyl)

methanone to (2-Hydroxy-5-methoxyphenyl)(4nitrophenyI)methanone .............................................

(4-Hydroxy-3-methoxyphenyl)(2-nitrophenyl)methanone to

(3,4-Dichlorophenyl)[5-(1,1-dimethylethyl)-2hydroxyphenyl]methanone ........................................

(2,4-DichIorophenyl)[4-hydroxy-2-methyl-5-(1-methyIethyi)

phenyl]methanone to [4-(4-Dodecylphenoxy)-2hydroxyphenyI](4-dodecylphenyl)methanone ............



35

35



288



2. Dihydroxybenzophenones ..........................................................

2.1 Hydroxy Groups Located on the Same Ring .........................

2.1.1 Substituents Located on the Hydroxylated Ring ........

2.1.2 Substituents Located on the Other Ring ....................

2.1.3 Substituents Located on Both Rings .........................

2.2 Hydroxy Groups Located on Both Rings ...............................

2.2.1 Substituents Located on One Ring ............................

2.2.2 Substituents Located on Both Rings .........................



339

339

339

365

382

396

396

413



3. Trihydroxybenzophenones .........................................................

3.1 Hydroxy Groups Located on the Same Ring .........................

3.1.1 Substituents Located on the Hydroxylated Ring ........

3.1.2 Substituents Located on the Other Ring ....................



436

436

436

437



This page has been reformatted by Knovel to provide easier navigation.



35



80

126

169



169



229



Contents

3.2



ix



Hydroxy Groups Located on Both Rings ............................... 442

3.2.1 Substituents Located on One Ring ............................ 442

3.2.2 Substituents Located on Both Rings ......................... 450



4. Tetrahydroxybenzophenones .....................................................

4.1 Hydroxy Groups Located on One Ring (Not Described

till December 1999) ...............................................................

4.2 Substituents Located on Both Rings .....................................

4.2.1 Substituents Located on One Ring ............................

4.2.2 Substituents Located on Both Rings .........................



458



5. Pentahydroxybenzophenones ....................................................

5.1 Hydroxy Groups Located on One Ring (Not Described

till December 1999) ...............................................................

5.2 Hydroxy Groups Located on Both Rings ...............................

5.2.1 Substituents Located on One Ring ............................

5.2.2 Substituents Located on Both Rings .........................



465



458

458

458

463



465

465

465

467



6. Hexahydroxybenzophenone ....................................................... 468

3. Polyphenyl Phenyl Methanones (Class of METHANONES) .................... 469

1. Biphenyl Phenyl Methanones ..................................................... 469

1.1 Monohydroxylated Ketones ................................................... 469

1.2 Dihydroxylated Ketones ........................................................ 475

2. Terphenyl Phenyl Methanones ................................................... 478

4. Cyclohexyl Phenyl Methanones (Class of METHANONES) .................... 479

1. Monohydroxylated Ketones ........................................................ 479

2. Dihydroxylated Ketones ............................................................. 484

3. Trihydroxylated Ketones ............................................................. 485



Part II. Diaroylphenols and Polyaroylphenols

5. Phenols with One Benzoyl Group and One or Several Acetyl Groups

(Class of ETHANONES) ........................................................................... 487

1. Monohydroxylated Ketones ........................................................ 487

2. Dihydroxylated Ketones ............................................................. 489



This page has been reformatted by Knovel to provide easier navigation.



x



Contents

Symmetrical Ketones ..................................................................... 489

Asymmetric Ketones ...................................................................... 489

3. Trihydroxylated Ketone .............................................................. 491

4. Tetrahydroxylated Ketone .......................................................... 492



6. Phenols with Two or Several Benzoyl Groups (Class of

METHANONES) ........................................................................................ 493

1. Monohydroxylated Ketones ........................................................ 493

Symmetrical Ketones ..................................................................... 493

Asymmetric Ketones ...................................................................... 496

2. Di- and Polyhydroxylated Ketones .............................................. 498

Symmetrical Ketones ..................................................................... 498

Asymmetric Ketones ...................................................................... 507



Part III. Miscellaneous Related Compounds (Class of

METHANONES)

1. Diphenyl Derivatives .................................................................................. 509

2. Diphenylmethane Derivatives ................................................................... 511

3. Diphenylethane Derivative ........................................................................ 513

4. Diphenylpropane Derivatives .................................................................... 514

5. Diphenyl Oxide Derivatives ....................................................................... 514

6. Diphenyl Sulfoxide Derivatives .................................................................. 516

7. Diphenyl Sulfone Derivatives .................................................................... 517

8. Others Acylated Compounds .................................................................... 519



References ..................................................................................... 521

Indexes

Molecular Formula Index ........................................................................... 561

Chemical Abstracts Registry Numbers Index ........................................... 645

Usual Names Index ................................................................................... 707



Common Abbreviations ................................................................ 717

This page has been reformatted by Knovel to provide easier navigation.



PART 1 - MONOAROYLPHENOLS

Chapter 1. Unsubstituted Hydroxybenzophenones (Class ofMETHANONES)

1. MONOHYDROXYBENZOPHENONES

(2-Hydroxyphenyl)phenylmethanone

[117-99-7]



C13H10O2



mol.wt. 198.22



Syntheses

-Preparation by Friedel-Crafts acylation of benzene in the

presence of aluminium chloride,

*with 2-hydroxybenzoyl chloride (salicylic acid chloride)

[546], (52%) [265], (39%) [346], at temperature <60° [244];

*with o-anisoyl chloride [21, 385,498, 554,775, 946, 1306,1425], (65%) [1397], (57%) [188],

(53%) [1111], (37%) [179], (30%) [345]. Demethylation occurred during the Friedel-Crafts

acylation, especially in the presence of ferric chloride at 130-140° [21];

*with 2-ethoxybenzoyl chloride in a boiling water bath (42%) [1397].

-Preparation by dealkylation,

*of 2-methoxybenzophenone,

with aluminium bromide in refluxing benzene for 4 h (96%) [1059];

with 48% hydrobromic acid in boiling acetic acid for 2 h [1309];

with boron tribromide in methylene chloride at r.t. for 12 h [766], according to [891];

*of 5-tert-butyl-2-methoxybenzophenone with aluminium chloride in benzene at 65-70° for 45 h

(79%) [774, 775]. The starting keto ether was obtained by reaction of benzoyl chloride with

4-tert-butylanisole in the presence of zinc chloride in refluxing tetrachloroethane for 40 h [774];

*of 5-tert-butyl-2-hydroxybenzophenone with aluminium chloride in benzene at 65-70° for 45 h

(63%) [775].

-Preparation by Fries rearrangement of phenyl benzoate,

*with aluminium chloride [692],

without solvent

at 200° for 20 min [766] or for 15 min (26%) [864], at 190° for 7 h (26%) [312], at 140° (24%)

[490] or at 140° for 15 min (27%) [311], at 130° for 1 h, then at 160° for 1 h (30%) [1447],

between 100 to 150° for 3 h (minor product) [1363], or at 63° for 4 h (<2%) [1449],

with solvent

in nitrobenzene at 98° for 5 h (<9%) or at 120° for 2 h (15%) [126];

*with an aluminium chloride and sodium chloride mixture at 140-200° (37%) [490];

*with aluminium bromide in chlorobenzene at 110° for 15 min (2%) or for 4 h (20%) [325];

*with aluminium iodide in refluxing acetonitrile (82°) for 10 h (23%) [844];

*with boron trifluoride-etherate in the presence of phenol in refluxing benzene for 3 h (68%) [725];

*with ferric chloride in a boiling water bath for 6 h [611];

*with titanium tetrachloride in nitrobenzene at 60° for 18 h (7%) [311] or in refluxing nitromethane

for 30 min (15%) [1446];

*with TFMS (trifluoromethanesulfonic acid) in tetrachloroethane at 170° for 24 h in a sealed tube

(39%) [386];

*with Nafion-H, a polymeric perfluorinated resin sulfonic acid, in refluxing nitrobenzene for 12 h

(24%) [1004];

*with Nafion-XR, a H+-form ion exchange resin, at 150° for 4 h (23%) [1231];

*with polyphosphoric acid at 100° (1%) [960];



Tài liệu bạn tìm kiếm đã sẵn sàng tải về

1 Hydroxy Groups Located on One Ring (Not Described yill December 1999)

Tải bản đầy đủ ngay(0 tr)

×