Chlorosulfonic acid: a versatile reagent

326 Pages·2002·20.96 MB·English

by  R.J. Cremlyn

Chlorosulfonic Acid
A Versatile Reagent

Chlorosulfonic Acid
A Versatile Reagent
R.J. Cremlyn
University of Hertfords h ire
ROYAL SOCIETY OF CHEMISTRY
ISBN 0-85404-498-1
A catalogue record for this book is available from the British Library
0 The Royal Society of Chemistry 2002
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Preface
Chlorosulfonic acid was discovered in 1854 and has become a widely used
sulfonating agent. It is of particular value when used in excess for the direct
chlorosulfonation of a wide range of organic compounds. The resultant sulfonyl
chlorides are important synthetic intermediates which are utilized in the prepara-
tion of many commercially significant sulfonyl derivatives such as sulfonamides
and sulfonates. Chlorosulfonic acid is thus a major industrial reagent for the
manufacture of detergents, pharmaceuticals, dyes, ion-exchange resins, plastics,
artificial sweetners and various other chemicals.
In addition, chlorosulfonic acid is a versatile laboratory reagent which plays a
key role in promoting several different types of reaction, such as alkylation,
halogenation, rearrangement, cyclization and polymerization. In many of these
reactions, chlorosulfonic acid functions as a powerful acid catalyst and dehydrat-
ing agent. Currently, there is no book on the market specifically dealing with
chlorosulfonic acid and, in view of its considerable synthetic importance over
many years, there is an urgent need to provide a coherent body of information on
the reagent. The book seeks to achieve this objective and so the text appears
timely. This view has been reinforced by the large number of research papers that
I have published dealing with the use of chlorosulfonic acid in synthetic organic
chemistry. The book should be valuable to all those in industry, universities and
colleges who use, or may wish to use, chlorosulfonic acid in their work. The
appendix at the end of the book includes the relevant references up to December
2001.
My thanks are due to many former staff and students of the Chemical Sciences
Division of the University of Hertfordshire who assisted me in my research
programme on the synthetic applications of chlorosulfonic acid. Thanks are also
due to Mrs Janet Freshwater and other members of the editorial staff of the Royal
Society of Chemistry for their assistance during the passage of the book through
the press.
R.J. Cremlyn
V
Professor Cremlyn was educated at Swansea University College, Wales and
Trinity Hall, Cambridge. Most of his long and distinguished career has been spent
as a lecturer at the University of Hertfordshire, UK, where he is Emeritus
Professor of Organic Chemistry. During that time he has published many research
papers and articles on his major research interest - the chemistry and biological
activity of organosulfur and organophosphorus compounds, especially as crop
protection agents.
vi
Contents
List of Abbreviations xiii
Chapter 1 Introduction
1 Manufacture
2 Physical Properties
3 Chemical Properties
4 Safety
5 Uses
6 References
Chapter 2 Sulfonation and Chlorosulfonation of Organic Compounds 7
1 Introduction 7
9
2 Mechanism of Sulfonation
3 Sulfonation by Halosulfonic Acids 11
4 References 20
Chapter 3 Reactions of Organic Sulfonyl Chlorides 22
22
1 Reactions with Nucleophilic Reagents
29
2 Sulfonylation
32
3 References
Chapter 4 Sulfonation and Chlorosulfonation of Aromatic
Compounds using Chlorosulfonic Acid 35
1 Introduction 35
35
2 Aromatic Hydrocarbons
35
2.1 Monocyclic Systems
2.1.1 Benzene and its Alkyl Derivatives 35
2.1.2 Higher Alkylbenzenes 37
2.1.3 Polyalkylbenzenes 38
39
2.2 Polycyclic Aromatic Systems
2.2.1 Compounds not Containing Fused Aromatic Nuclei 39
2.2.1.1 Diarylalkanes 39
2.2.1.2 Biphenyl 42
2.2.1.3 Fluorene 43
2.2.2 Compounds Containing Fused Aromatic Nuclei 43
2.2.2.1 Naphthalene 43
vii
...
Vlll Contents
2.2.2.2 Alkylnaphthalenes 44
2.2.2.3 Acenaphthene 45
2.2.2.4 Anthracene 46
2.2.2.5 Phenanthrene 47
3 Aryl Halides 47
3.1 Halobenzenes 47
3.2 Halobiphenyls and Related Compounds 53
3.3 Halonaphthalenes 53
3.4 Haloacenaphthenes 55
3.5 Haloanthracenes and Phenanthrenes 56
3.6 Halofluorenes 56
4 Aryl Nitro Compounds 56
5 Phenols 61
5.1 Naphthols 69
6 Aryl Ethers 71
6.1 Diphenyl Ether and Derivatives 74
6.2 Diphenyl Sulfide 76
7 Aromatic Carbonyl Compounds 76
7.1 Acetophenone 77
7.2 Benzophenone 78
7.3 Chalcones 80
7.4 Diarylideneketones 81
7.5 Benzils and other Diketones 86
8 Aromatic Carboxylic Acids and Amides 89
8.1 Benzoic Acid and Derivatives 89
8.2 Cinnamic Acid 91
8.3 Phenoxyacetic Acid and Related Acids 92
8.4 Phenyl and Diphenylacetic Acid 93
8.5 Benzilic Acid 94
8.6 Carboxylic Acid Amides 95
9 Aromatic Amines and Related Compounds 97
9.1 Anilines 97
9.2 Tertiary Amines 101
9.3 Acetanilides (N-Acetylarylamines) 102
9.4 Anilides (N-Benzoylarylamines) 105
9.5 Sulfonanilides 108
10 Arylureas 110
10.1 Phenylurea and Related Compounds 110
10.2 Diarylureas 112
11 Imides 113
1 1.1 N-Arylmaleimides 113
11.2 N-Arylsuccinimides 115
1 1.3 N-Arylphthalimides and Related Compounds 115
12 Reaction of Chlorosulfonic Acid with Miscellaneous Compounds 117
12.1 Azobenzene and Related Compounds 117
12.2 Azines 119