Organic Functional Group Preparations

558 Pages·1989·6.109 MB·English

by  Stanley R. Sandler and Wolf Karo (Auth.)

This is Volume 12 of
ORGANIC CHEMISTRY
A series of monographs
Editor: HARRY H. WASSERMAN
A complete list of titles in this series is available from the Publisher upon request.
ORGANIC FUNCTIONAL
GROUP PREPARATIONS
Second Edition
Stanley R. Scmdler
Pennwalt Corporation
King of Prussia, Pennsylvania
wolf Karo
Polysciences, Inc.
Warrington, Pennsylvania
I11
ACADEMIC PRESS, INC.
Harcourt Brace Jovanovich Publishers
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Copyright © 1989, 1986 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.
This book is a guide to provide general information concerning its subject
matter; it is not a procedural manual. Synthesis of chemicals is a rapidly
changing field. The reader should consult current procedural manuals for
state-of-the-art instructions and applicable government safety regulations.
The Publisher and the authors do not accept responsibility for any misuse of
this book, including its use as a procedural manual or as a source of specific
instructions.
Academic Press, Inc.
San Diego, California 92101
United Kingdom Edition published by
Academic Press Limited
24-28 Oval Road, London NW1 7DX
Library of Congress Cataloging-in-Publication Data
(Revised for vol. 3)
Sandler, Stanley R., Date
Organic functional group preparations.
(Organic chemistry ; v. 12)
Includes bibliographies and indexes.
1. Chemistry, Organic—Synthesis. I. Karo,
Wolf, Date. II. Title.
QD262.S23 1983 547'.2 83-2555
ISBN 0-12-618601-4 (v. 1)
ISBN 0-12-618603-0 (v. 3)
Printed in the United States of America
89 90 91 92 9 8 7 6 5 4 3 2 1
P R E F A CE
The purpose of this series is to provide the organic chemist with a con­
venient and updated source of useful preparative procedures that have been
described in the literature (journals and patents). In this volume, we cover
synthetic methods for the generation of 13 functional groups.
For this second edition, the literature has been reviewed from 1971 to the
present and includes new information where pertinent, new and expanded
tables of data, additional preparations, and recent references from the jour­
nal and patent literature. A unique feature of this work is that the United
States and foreign patent literature is frequently cited. It is these patent
references which should be of great value to the industrial chemist.
Information about safety precautions is given where available. We par­
ticularly continue to urge the laboratory worker to check the toxicity and other
potential hazards of all reagents, intermediates, and final products. The reader
is urged to check the Material Safety Data Sheets (MSDS) from the suppliers
of chemicals and to inform assistants of this information. The reader should
consult and become familiar with the "NIOSH Registry of Toxic Effects of
Chemical Substances 1981-1982 Edition" (edited by R. L. Tatken and R. J.
Lewis, Sr., published by the United States Department of Health and Human
Services, Center for Disease Control, National Institute for Occupational
Safety and Health, Cincinnati, Ohio, 40226; June 1983). We caution those
anticipating scale-up work to first undertake extensive tests to ensure that
this can be done safely. The heat of reaction among other things should be
determined to ensure that a runaway reaction will not take place in the equip­
ment used. Many of the preparations have not been checked either by us or
by an independent laboratory for hazards and toxicity and are given here only
for information purposes. We do not warrant the preparations against any
safety or toxic hazards and assume no liability with respect to the use of the
preparations or of the products.
We wish to express our gratitude to our wives and families for their patience,
understanding, and encouragement during all phases of the preparation of this
manuscript. We also express our appreciation to the production staff of Academic
Press for their help in the various phases of publication of this volume.
We again were very fortunate to have Ms. Emma Moesta type the revisions
for each of the chapters of this second edition and to provide us with a highly
professional manuscript. Her sincere and dedicated efforts on our behalf will
always be remembered and very much appreciated.
Stanley R. Sandler
Wolf Karo
ix
THE PREFACE
FROM "0
THE FIRST EDITION
Volume I11 describes 13 additional functional groups and presents them
as in previous volumes with detailed preparative examples.
The format of this volume follows that of Volumes I and 11. Where possi-
ble, the preparative details for each functional group are divided according
to their reaction type (condensation, elimination, oxidation, reduction). The
literature is up-to-date and each chapter carries an extensive reference list.
In many cases, it was felt that suitable general preparative details have not
been reliably developed for their inclusion at this time in this text. We urge
our readers to correspond with us and present information that would be of
general interest to others.
We certainly hope that our discussions, although brief at times, help to
point out the need for further work in areas lacking preparative information.
If we have inspired anyone to further investigate these areas, we certainly have
accomplished a major goal of this text.
Xi
C O N T E N TS OF O T H ER V O L U M ES
Volume I
1. Hydrocarbons (Paraffinic and Aromatic)
2. Olefins
3. Acetylenes
4. Alcohols and Phenols
5. Ethers and Oxides
6. Halides
7. Aldehydes
8. Ketones
9. Carboxylic Acids
10. Esters
11. Amides
12. Cyanates, Isocyanates, Thiocyanates, and Isothiocyanates
13. Amines
14. Hydrazine Derivatives, Hydrazones, and Hydrazides
15. Diazo and Diazonium Compounds
16. Nitro Compounds
17. Nitriles (Cyanides)
18. Mercaptans, Sulfides, and Disulfides
19. Sulfoxides
20. Sulfones
21. Sulfonic Acids, Sulfonic Acid Derivatives, and Sulfinic Acids
Index
Volume II
1. Allenes
2. Ortho Esters
3. Sulfites
4. Enamines
5. Ynamines
6. Ureas
7. Pseudoureas
8. Semicarbazides
9. Carbodiimides
10. A/-Carbamates (Urethanes)
xiii
xiv CONTENTS OF OTHER VOLUMES
11. O-Carbamates
12. Imines
13. Azides
14. Azo Compounds
15. Azoxy Compounds
16. C-Nitroso Compounds
17. Af-Nitroso Compounds
Index
1/ACETALS A ND KETALS
CHAPTER
1. Introduction 2
2. Condensation Reactions 5
A. Condensation of Alcohols with Aldehydes and Ketones 5
2-1. Preparation of Acetal (1,1-Diethoxyethane) 11
2-2. Preparation ofn-Butylal (Dibutoxymethane) 14
2-3. Preparation of Monobenzalpentaerythritol 14
2-4. Preparation of (RS)-l,2-Isopropylideneglycerol 16
2-5. Preparation of Di-t-Butylmercaptal of Formaldehyde 17
2-6. Preparation of 3,3-Dichloro-2-Methacrolein bis (4-chlorophenyl)
mercaptal 17
B. Reaction of Alcohols with Vinyl Ethers 17
2-7. Preparation of 1-n-Butoxy-l-ethoxyethane 21
2-8. Preparation of 2-Methoxytetrahydropyran 24
2-9. Preparation of 2-(a-Bromobenzyl)-l,3-dioxolane 26
C. Reaction of Alcohols with Olefins and Acetylenes 26
a. Olefins 26
b. Acetylenes 29
2-10. Preparation of 1,1-Dimethoxyethane 29
2-11. Preparation of 2-Methyl-l,2- and -1,3-dioxolane-4-methanol (Ethylidene-
glycerol) 31
2-12. Preparation of2,2-Dihexoxyhexane 32
D. Reaction of Alcohols or Aldehydes with Substituted Olefins 35
2-13. Preparation of n-Butylacetal 36
2-14. Preparation of the Diethyl Ketal of Acetone (2,2-Diethoxypropane) 37
2-15. General Procedure for the Condensation of 1-Olefins with Formalin 38
E. Reaction of Ortho Esters with Aldehydes 40
2-16. Preparation of Isobutyraldehyde Diethyl Acetal 44
2-17. Preparation of m-Aminobenzaldehyde Diethyl Acetal 44
F. Reaction of Ortho Esters with Ketones 44
2-18. General Procedure for the Preparation ofKetals by Method A 45
2-19. Preparation of the Dipentyl Ketal of Acetone by Method Β 47
2-20. Preparation of 2,2-Diethoxy-l,3-dioxolane by Method Β 47
2-21. Preparation ofp-Bromoacetophenone Diethyl Acetal by Method A 48
2-22. Preparation of 2-Phenyl-2,4,4,5,5-pentamethyl-l,3-dioxolane by
Method A ." 48
2-23. Preparation ofBis (3-nitropheny I) dimethoxy methane 49
G. Reaction of Ortho Esters with Acetylenic Compounds 49
2-24. Preparation of Phenylpropioladehyde Diethyl Acetal 50
H. Reaction of Orthoformate Esters with Grignard Reagents 52
2-25. Preparation of the Diethyl Acetal of 3-Methyl-3-buten-l-al 52
2-26. Preparation of n-Butyr aldehyde Diethyl Acetal 54
2-27. Preparation of Pentanal Diethyl Acetal 54
1
2 1. Acetals and Ketals
I. Reaction of TrithioOrtho Esters with Vinyl Ethers 55
J. Reaction of Dihalomethylene Compounds with Sodium Alkoxides 55
2-28. Preparation ofc\s-Hexahydro-l,3-benzodioxolane 56
2-29. Preparation of Ketene Di(2-methoxyethyl) Acetal 56
2-30. Preparation of 2-Chloro-l,l-diethoxy-2-propene 59
3. Reactions of Acetal and Ketal Compounds 61
A. Condensation Reactions of Halo Acetals, Hydroxy Acetals, and Oleflnic
Acetals 61
3-1. Preparation of 2-Methyl-3-ethyl-5-allyloxymethyl-5-methy 1-1,3-dioxane 62
3-2. Preparation of 3,3-Dimethoxy-4-4-dimethyl-l,l,2,2-cyclobutane-tetracarbo-
nitrile\ 63
B. Halogenation Reactions 63
3-3. Preparation of a -Br omoisobutyraldehyde Diethyl Acetal 63
3-4. Preparation of Bromoacetaldehyde Diethyl Acetal 65
C. Dehydrohalogenation Reactions 65
3-5. Preparation οf 2-Methylene-l, 3-dioxolane 66
D. Transacetalization 66
3-6. Preparation of l-Chloromethyl-l,3-dioxolane 68
3-7. Preparation o)"2-(l'-Bromohexyl)-4-hydroxymethyl-l,3-dioxolane 69
E. Transketalization 70
3-8. Preparation of Acetophenone Dipropyl Ketal 72
F. Photolytic Reactions 72
4. Oxidation Reactions 74
4-1. Preparation of 2-(l,2-Epoxypropyl)-4-methyl-l,3-dioxolane 75
5. Reduction Reactions 76
5-1. Preparation of '5 -Hydroxy-4-hydroxymethylpentanal Diethyl Acetal 76
6. Miscellaneous Methods 77
References 79
1. INTRODUCTION
Acetals possess a terminal 1,1-diether group, and ketals possess the
same type of group in an internal position. These groups may be thought to
be diether derivatives of the parent geminal dihydroxy compounds (hy-
drated aldehydes or ketones).
A wide variety of methods are available for the preparation of acetals
and ketals, and the most important synthetic routes are summarized in
Schemes 1 and 2.
Acetals and ketals are important functional groups that find use in the
preparation of novel heterocyclic compounds, in polymers, and in the
protection of carbonyl compounds or alcohols. Acetals and ketals are
stable under basic conditions but hydrolyze easily under acidic conditions
to the starting carbonyl compound and alcohol.
A brief review of the chemistry of acetals appears in the literature [1].
Recently the chemistry of the condensation products of glycerol with
aldehyde and ketones to give cyclic aldehydes has been reviewed [2a].
§ 1. Introduction 3
SCHEME 1
Preparation of Acetals
R—CHCH(OR")2
RG=CH + 2ROH 2 RCHMgX + HC(OR )
2 3
2ROH
/OR' H+
RCH=0 + 2ROH R—CH—CH « RCH=CHOR' + R'OH
2 ^OR'
2R'ONa
RCH=CH + 2ROH
RCH CH=0 + HC(OR') 2
2 3
R—CHCHX
2 2
SCHEME 2
Preparation of Ketals
RC(OR")
2 2 r2C=0 + 2ROH + HC(OC2H5)3
2ROH
R2C=0 + 2ROH R2C(OR')2 / C = C — C— + R'OH
I ^
2R'ONa OR'
R CX
2 2
The Chemical Abstracts nomenclature is used for most of the acetals
described in this chapter. The compounds are named either as dialkoxy
derivatives or as derivatives of acetals or ketals. Confusion exists in the
earlier literature on naming cyclic acetals. For example, the acetals pre­
pared from glycerol and an aldehyde were at one time referred to as 1,2- or
1,3-alkylidene (or arylidene) glycerol; however, today they are named as
shown below:
CHOH
2
CH—Ο
CH—Ο \ /R
2
HOCH Cf
CH -
\ / R' 2
CH -0
2 (old) 1,2- Alkylidene glycerol
(old) 1,3-Alkylidene glycerol (new) 2-Alkyl-4-hydroxymethyl-
(new) 2-Alkyl-m-dioxan-5-ol 1,3-dioxolane