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Development of Rapid and Inexpensive Derivatisation Methods for Methylphosphonic Acid

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Development of Rapid and Inexpensive Derivatisation Methods for Methylphosphonic Acid Development of rapid and inexpensive derivatisation methods for methylphosphonic acid By Jolene Anthony This thesis is presented for the degree of Bachelor of Science Honours at Murdoch University. College of Science, Health, Engineering and Education. Academic Operations, Medical Molecular and Forensic Science, Perth, Western Australia. Nov, 2019. Supervisor: Dr Kate Rowen Co-supervisors: Dr John Coumbaros & Associate Professor James Speers Declaration I declare that this thesis is my own account of my research and contains as its main content work which has not previously been submitted for a degree at any tertiary education institution. Jolene Anthony (Jolene Anthony) Word Count: 17, 657. 1 Acknowledgements First and foremost, I would like to thank Dr Kate Rowen for her continuous support throughout the year. Kate, your guidance and positivity have been invaluable in conducting this research. You always managed to find the time for my questions and to teach me new techniques. Even in the face of several setbacks, when I found myself preparing to google ‘abyss near me’ to scream into, you helped me find a way to persevere. It has been such a rewarding experience and I have genuinely enjoyed almost every minute of it. You have far surpassed any expectation I had for a supervisor. I feel truly honoured to have worked with and learnt from someone I consider to be “total science idol material”! I would also like to express my gratitude to the SHEE technical staff, in particular Andrew Foreman, Claire Tull, Goshia Kowalczyk, Sajiel Jani, and Juita Juita for having the patience to train me on a range of equipment. You are all incredibly hard workers! No matter how busy you were, you always managed to squeeze in some time to assist me. Without the help and knowledge provided by the technical team, this research would not have been possible. There are several others I owe thanks to: Co-supervisors Dr John Coumbaros and Associate Professor James Speers for their assistance. My friends/university family, for listening to me blabber on about my research for 8 months straight. Lastly, thank you to Murdoch University for funding this research. 2 Abstract This study probed alternative methods towards rapid and inexpensive in-field derivatisation of methylphosphonic acid (MPA), the final hydrolysis product of several chemical warfare nerve agents, for detection by gas chromatography-mass spectrometry (GC-MS). Initially, research focused on acetylation as a derivatisation method, with attempted preparation of a reference sample of diacetyl methylphosphonate. This was unsuccessful with reduction of the acetyl carbonyl group during synthesis and detection of diethyl methylphosphonate instead. The research subsequently focused on esterification of methylphosphonic acid with methanol or ethanol. Preparations employed the use of dicyclohexyl carbodiimide as a coupling reagent, and silica chloride or sulfuric acid as catalysts. The coupling reagents and catalysts utilised had limited success, with no dialkyl methylphosphonate ester derivates detected via GC-MS. Dialkyl derivatives were successfully prepared by conversion of MPA to methylphosphonyl dichloride using thionyl chloride, and subsequent reaction with alcohols. Conversion of methylphosphonyl dichloride to corresponding dialkyl methylphosphonates occurs rapidly with derivatives being detected within 10 minutes for primary alcohols (methanol, ethanol, and butan-1-ol) and within 20 minutes for secondary alcohols (propan-2-ol), while benzyl alcohol did not react. Dialkyl methylphosphonates were identified by analysis of reaction products using GC-MS and nuclear magnetic resonance (NMR) spectroscopy. This method applied here acts as a proof of concept, providing a promising platform for future exploration. Alkylation of methylphosphonic acid with alcohols provides an inexpensive and relatively non-hazardous alternative to current widely accepted derivatisation methods in supporting the rapid in-field detection of chemical warfare nerve agents. 3 Table of contents Development of rapid and inexpensive derivatisation methods for methylphosphonic acid ... 0 Declaration .................................................................................................................................. 1 Acknowledgements ..................................................................................................................... 2 Abstract ....................................................................................................................................... 3 Abbreviations .............................................................................................................................. 6 Inventory of tables ...................................................................................................................... 8 Inventory of figures ..................................................................................................................... 9 Chapter 1. Introduction ............................................................................................................. 10 1.0 Introduction ..................................................................................................................... 10 1.1 Chemical warfare agents ................................................................................................. 10 1.2 Nerve agents .................................................................................................................... 11 1.2.1 Toxicity of nerve agents ........................................................................................... 13 1.2.2 Organophosphate nerve agent degradation ............................................................ 14 1.3 OPCW chemical analysis .................................................................................................. 17 1.4. Derivatisation ................................................................................................................. 19 1.4.1 Types of derivatisation ............................................................................................. 20 1.4.2 Derivatisation of phosphonic acids .......................................................................... 21 1.4.3 Derivatisation without the removal of the water .................................................... 25 1.5 Acetylation....................................................................................................................... 27 1.5.1 Acetylation reagents ................................................................................................ 28 1.5.2 Acetylation of methylphosphonic acid .................................................................... 30 1.6 Concluding statements and research aims ..................................................................... 31 Chapter 2 Experimental ............................................................................................................. 33 2.1 General methods ............................................................................................................. 33 2.1.1 Instrumentation and instrumental parameters ....................................................... 33 2.1.2 Reagents and solvents .............................................................................................. 34 2.1.3 Solvent drying procedures........................................................................................ 34 2.1.4 Preparation of methylphosphonyl dichloride .......................................................... 35 4 2.1.5 Preparation of silver acetate .................................................................................... 35 2.1.6 Preparation of silica chloride ................................................................................... 35 2.2 Trialled preparation of diacetyl methylphosphonate ..................................................... 36 2.3 Preparation of dialkyl methylphosphonates .................................................................. 36 2.3.1 Conversion of methylphosphonyl dichloride to alkyl methylphosphonates........... 36 2.3.2 Trialed esterification of methylphosphonic acid with coupling reagents/ catalysts ........................................................................................................................................... 37 Chapter 3. Results and discussion ............................................................................................. 38 3.1 Trialled preparation of diacetyl methylphosphonate ..................................................... 38 3.2 Introduction to dialkyl methylphosphonates ................................................................. 45 3.3 Revised research aims ..................................................................................................... 47 3.4 Preparation of dialkyl methylphosphonates .................................................................. 49 3.4.1 Diethyl methylphosphonate..................................................................................... 49 3.4.2 Dimethyl methylphosphonate ................................................................................. 53 3.4.3 Other dialkyl methylphosphonates alcohols ........................................................... 55 3.4.6 Summary/ rate of reaction ....................................................................................... 55 3.4.7 Trialled esterification using catalyst and coupling reagent. ...................................
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