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Chemistry of Electrophilic Intermediates in the Sulfonation Process

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Chemistry of Electrophilic Intermediates in the Sulfonation Process _________________________________________________________________________Swansea University E-Theses Chemistry of electrophilic intermediates in the sulfonation process. Thomas, Gareth Leslie How to cite: _________________________________________________________________________ Thomas, Gareth Leslie (2002) Chemistry of electrophilic intermediates in the sulfonation process.. thesis, Swansea University. http://cronfa.swan.ac.uk/Record/cronfa43090 Use policy: _________________________________________________________________________ This item is brought to you by Swansea University. Any person downloading material is agreeing to abide by the terms of the repository licence: copies of full text items may be used or reproduced in any format or medium, without prior permission for personal research or study, educational or non-commercial purposes only. The copyright for any work remains with the original author unless otherwise specified. The full-text must not be sold in any format or medium without the formal permission of the copyright holder. Permission for multiple reproductions should be obtained from the original author. Authors are personally responsible for adhering to copyright and publisher restrictions when uploading content to the repository. Please link to the metadata record in the Swansea University repository, Cronfa (link given in the citation reference above.) http://www.swansea.ac.uk/library/researchsupport/ris-support/ CHEMISTRY OF ELECTROPHILIC INTERMEDIATES IN THE SULFONATION PROCESS BY GARETH L. THOMAS ProQuest Number: 10821482 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10821482 Published by ProQuest LLC(2018). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 Summary Chemistry of Electrophilic Intermediates in the Sulfonation Process. The study is more specifically concerned with the reactions of aromatic sulfonic anhydrides. The study was carried out in order to gain more knowledge on the reactions and behaviour of aromatic sulfonic anhydrides, and the role they play in the formation of sulfones in the industrial sulfonation process. An introduction to industrial sulfonation as used in the detergent industry is included. It has been proposed that sulfones are formed in the sulfonation process, by reaction of sulfonic anhydrides with alkylbenzene (starting material). An initial study of the reactions of /?-toluenesulfonic anhydride with toluene using different catalysts was carried out, providing background knowledge for the more detailed studies that followed. A number of competition reactions were completed, investigating the influence of substituents in a series of arenes on the relative rates of reaction of p-toluenesulfonic anhydride. Studies were carried out using nitromethane as solvent and AICI 3 as catalyst. Included in the study is a review of the synthesis of diaryl sulfones, and the synthesis of a number of unsymmetrical sulfones. A new route to di-tolyl sulfone was identified from 7/7/ramolecular reaction of p- toluenesulfonic anhydride catalysed by AICI 3. The relative rate of formation of sulfones via this route compared to Friedel-Crafts type sulfonylation reactions and was studied. The relative rates were found to be very low. The synthesis of a series of aromatic sulfonic anhydrides was carried out using direct sulfonation with SO 3. The sulfonic anhydrides were then used to investigate the effect of substituents on the rates of reaction of substituted benzenesulfonic anhydrides reacting with toluene. The reactions were carried out in nitromethane using AICI3 as the catalyst. For My Family Acknowledgements It is not possible to thank everyone who has helped me along the way, but I will at least attempt in the following few lines to thank some of the most important people. Firstly I would like to thank my family for their support throughout my studies. I would like to thank my grandmothers, Doris and Winnie for encouraging me to start on this long road. I would like to apologise to Alf, my grandfather who probably would have thought that my time would be better spent in the garden. Special thanks go to my parents, for love and support at all times. I would like to thank Unilever and the University of Wales, Swansea for funding this project. Thanks to Dr. R. S. Ward and Dr. D. W. Roberts for their supervision, guidance and tolerance over the years. I would also like to thank to Dr. T. W. Bentley for his suggestions and comments, all of which have been of great value. For their hard work behind the scenes I would like to thank the staff at U. W. Swansea. I would especially like to thank Stan for his general assistance. The advice and services of Gareth Llewellyn, Ann Hunter and Bridget Stein at the EPSRC National Mass Spectrometry Service Centre is very gratefully appreciated, as is NMR analysis by Myron Nettle. At Unilever Research I would to thank Janette Wilson, Steve Foulkes, Collette Connor and Jon Osier for their help, assistance and patience. I would like to thank Daniel Rendall of Trinity College, Cambridge for mathematical assistance. I would like to thank the MFR students, past and present who have made each day as entertaining as possible. I would especially like to thank Dr. Richard Diaper for his advice and guidance in the early days. It is only right to thank the members of Swansea Pirates Volleyball Club, who have made the worst of times fun, especially Steve Nantel for being a useful ear to bend and for being very helpful with all things computer related. Last, but far from least I would like to thank Uta for providing me with the motivation to finish, and I would like to apologise for all the stress I have caused over the last few months. CHEMISTRY OF ELECTROPHILIC INTERMEDIATES IN THE SULFONATION PROCESS CHAPTER ONE Page 1.1 Detergents and Surfactants 2 1.2 LAS Manufacture 5 1.3 Aromatic sulfonation 1 0 1.3.1 Primary sulfonation 12 1.3.2 Secondary sulfonation 18 1.4 Sulfonation side reactions 20 1.4.1 Mechanism of sulfonic anhydride formation 21 1.4.2 Mechanism of sulfone formation 23 References 28 CHAPTER TWO 2.1 Friedel - Crafts sulfonylation reactions 31 2.2 Introduction to Lewis acid catalysis of sulfonylation reactions 33 2.2.1 Introduction to AICI 3 catalysis of sulfonylation reactions 34 2.2.2 Other Lewis acid catalysts in sulfonylation reactions 39 2.3 Introduction to protic acid catalysis of sulfonylation reactions 41 2.4 Identification of sulfonylation products and reaction components 44 2.5 Analytical methodology for aromatic sulfonylation reactions 44 2.6 Autocatalytic reaction of/ 7-toluenesulfonic anhydride with toluene 49 2.7 AICI 3 catalysed reactions of/ 7-toluenesulfonic anhydride with excess toluene 54 2.8 AICI3 catalysed reactions of / 7-toluenesulfonic anhydride with toluene in nitromethane 56 iv 2.9 Other Lewis acid catalysed reactions / 7-toluenesulfonic anhydride with toluene in nitromethane 58 2.10 Protic acid catalysed reactions of/ 7-toluenesulfonic anhydride with toluene in nitromethane 62 2.11 Graphite catalysed reaction of/ 7-toluenesulfonic anhydride with toluene in nitromethane 63 2 .12 Summary and Perspectives 64 Experimental 69 Appendix One 78 Appendix Two 79 Appendix Three 81 References 82 CHAPTER THREE 3.1 Introduction 85 3.2 Partial rate factors 87 3.3 Introduction to relative rates of sulfonylation 89 3.4 Routes to diaryl sulfones 100 3.4.1 Condensation of sulfonic acids with aryl substrates 102 3.4.2 Friedel-Crafts type sulfonylation and similar reactions 105 3.4.3 Synthesis of sulfones from sulfinic acids 108 3 .5 Synthesis of diaryl sulfones 1 12 3 .6 Method development and analytical methodology for competition reactions 114 3 .7 Competition reactions using a range of aromatic substrates in sulfonylation reactions with /7-toluenesulfonic anhydride 118 v 3.8 Isomer formation and isomer distribution in sulfonylation reactions 128 3 .9 Effects of changes in reaction concentration on reaction yield in sulfonylation reactions 132 3.10 Summary and Perspectives 134 Experimental 136 Appendix 145 References 149 CHAPTER FOUR 4.1 Introduction to /w/ramolecular reaction between p-toluenesulfonic anhydride and A1CE to form di-/?-tolyl sulfone 153 4.2 Reaction and analytical method development 155 4.3 Investigation into the product isomer distribution in the /wframolecular reaction of / 7-toluenesulfonic anhydride with AICI 3 in nitromethane 156 4.4 Proposed mechanism for the z>?/ramolecular reaction 157 4.5 Crossover reaction between two different aromatic sulfonic anhydrides catalysed by SO 3 159 4.6 Crossover reaction between two different aromatic sulfonic anhydrides catalysed by AICI3 160 4.7 Competition reactions between Friedel-Crafts sulfonylation of aryl substrates and the wframolecular route to diaryl sulfones using /7-toluenesulfonic anhydride 161 4.8 Attempted synthesis of 2,4’- substituted unsymmetrical sulfones 165 4.9 Summary and perspectives 168 Experimental 169 References 177 CHAPTER FIVE 5 .1 Introduction to rates of sulfonylation using different sulfonylating agents 179 5.2 Methods of synthesising sulfonic
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