Development of Sustainable Catalytic Systems for Oxidation Reactions
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DOCTOR OF PHILOSOPHY Development of Sustainable Catalytic Systems For Oxidation Reactions Hughes, Nicola Award date: 2017 Awarding institution: Queen's University Belfast Link to publication Terms of use All those accessing thesis content in Queen’s University Belfast Research Portal are subject to the following terms and conditions of use • Copyright is subject to the Copyright, Designs and Patent Act 1988, or as modified by any successor legislation • Copyright and moral rights for thesis content are retained by the author and/or other copyright owners • A copy of a thesis may be downloaded for personal non-commercial research/study without the need for permission or charge • Distribution or reproduction of thesis content in any format is not permitted without the permission of the copyright holder • When citing this work, full bibliographic details should be supplied, including the author, title, awarding institution and date of thesis Take down policy A thesis can be removed from the Research Portal if there has been a breach of copyright, or a similarly robust reason. If you believe this document breaches copyright, or there is sufficient cause to take down, please contact us, citing details. Email: [email protected] Supplementary materials Where possible, we endeavour to provide supplementary materials to theses. This may include video, audio and other types of files. We endeavour to capture all content and upload as part of the Pure record for each thesis. Note, it may not be possible in all instances to convert analogue formats to usable digital formats for some supplementary materials. We exercise best efforts on our behalf and, in such instances, encourage the individual to consult the physical thesis for further information. Download date: 05. Oct. 2021 Development of Sustainable Catalytic Systems for Oxidation Reactions N. Louise Hughes MSci A Thesis Submitted for the Degree of Doctor of Philosophy at the School of Chemistry and Chemical Engineering Queen’s University of Belfast 12th April 2017 Supervisor: Dr Mark J. Muldoon Acknowledgements This thesis would not have come to fruition without the never ending help and support from so many people. I’d firstly like to thank my supervisor Mark Muldoon. I will never be able to express my gratitude for the amount of support, guidance and opportunities that you have given me over the last four years. Your continuous encouragement and faith in me will forever be appreciated. Lastly, thank-you for your friendship – your quick wit and sociable nature made many a stressful day more bearable. Next, I would like to thank my chemistry family. Firstly to Stuart James, Matt Cook, Panagiotis Manesiotis, Paul Stevenson and Peter Knipe for your help and advice throughout the course of my studies. To the Muldoon group, firstly Qun, Luke and Laura- whose friendship, help and humour made the lab a happier place to be. Of course, special mention should be made to Laura- ‘the wife’. You have been by my side throughout this whole experience, and I have made a friend for life. Your love of cocktails, shopping and ridiculous nature has made for some unforgettable memories, thank-you. To Clare and Matthew, the future of the Muldoon Group. Your words of encouragement, banter, and tolerance of my crazy have made the last few months more enjoyable than I had thought possible. I wish both of you all the best in your studies, and hope that the trips to the Eg live on. On that note, I’d like to thank the other members of lab 01.430, for the fun times that I do (and don’t) remember, thank-you. To Chris, school wasn’t enough, so you had to follow me here (and thank goodness you did). I’ve enjoyed many a lunchtime laugh, not to mention your continuous wise words and support. Finally, to Hannah. You’ve been with me from day one of first year. Two undergrads who had no clue what we were letting ourselves in for. You have shared every moment of this rollercoaster with me, from laughter to tears. I am confident that without your unwavering friendship, I would never have survived. So for this, and so many other things, thank-you. Last, but definitely not least, I’d like to thank my family and friends outside of the lab. To Cara, Jessica, Fiona, Jade, Stuart and Richard, thank-you for encouraging me throughout this process, and helping me on many an occasion to let my hair down. To Tom, I can’t express how much less stressful you’ve made this. Somehow you’ve put up with my crazy and we’ve still managed to have an amazing time along the way. I couldn’t have asked any more from you, so thank-you. To my family, Mum, Dad and Russell. You’ve seen me on the worst of days, and yet your support has never failed. Thank-you for your words of love, kindness and encouragement that have got me this far. List of Abbreviations ABNO – 9-azabicyclo[3.3.1] nonane N-oxyl AcOH - acetic acid Ar – argon AZADO – 2-azaadamantane N-oxyl BDE – bond disassociation energy BET – Brauner Emmett Teller analysis [bmim] – 1-butyl-3-methylimidazolium Bu3N – tributylamine [C4mPyr] – 1-butyl-1-methylpyrrolidinium [C8mim]- 1-octyl-3-methylimidazolium N- [C8Py] – octylpyridinium CDC – cross-dehydrogenative coupling CH3SO3H – methanesulfonic acid CO- carbon monoxide CO2 – carbon dioxide Co2(CO)8 – dicobalt octacarbonyl Cs2CO3 – caesium carbonate DBU – 1,8-diazobicyclo[5.4.0]undec-7-ene DCC- N,N’-dicyclohexylcarbodiimide DCE - dichloroethane DCM – dichloromethane DEF – N,N’-diethylformamide DIEA –diisopropylethylamine DMA – dimethylacetamide DMAP – 4-(dimethylamino)pyridine DMF – N-dimethylformamide DMSO - dimethylsulfoxide DNA-PK – Dioxyribonucleic acid (DNA) protein kinase Dppb- 1,4-bis(diphenylphosphino)butane DRIFT – diffuse reflectance infrared fourier transform EDCl – 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EI - electron ionisation EPR – electron paramagnetic resonance ESI-MS - electrospray mass spectrometry Et3N – triethylamine ETM- electron transfer mediator EtOAc- ethyl acetate [FAP] – tris(pentafluoroethyl)trifluorophosphate GC – gas chromatography H2BIP – 2,6-bis(benzimidazol-2’-yl)pyridine HSA –8-hydroxyquinoline-2-sulfonic acid HCOOH – formic acid HOBt – hydroxybenzotriazole HOCl – hypochlorous acid HPLC – high performance liquid chromatography IAMN – isoamyl nitrite ICP- inductively coupled plasma atomic emission spectroscopy IOAc – iodine acetate IL – ionic liquid IR –infrared K2CO3 – potassium carbonate K3PO4 – potassium phosphate ketoABNO – 9-azabicyclo[3.3.1]nonane-3-one N-oxyl KI – potassium iodide LDA – lithium diisopropylamide LFL - lower flammability limit LiOtBu – lithium tert-butoxide LOC - limiting oxygen concentration 1-Me-AZADO – 1-methyl-2-azaadamantane N-oxyl MeCN- acetonitrile Me2S – dimethyl sulfide MnO2 – manganese dioxide MS - molecular sieves MTES – methyltriethoxysilane MW – microwave NACOS – nitric acid assisted carbon catalysed oxidation system NaHCO3 – sodium hydrogencarbonate NaI – sodium iodide n-BuLi - n-butyllithium [N2228] – triethyloctylammonium [NBu4][Br] – tetrabutylammonium bromide [NBu4][Cl] – tetrabutylammonium chloride [NBu4][I] – tetrabutylammonium iodide [NBu4][IO] – tetrabutylammonium hypoiodite [NBu4][IO2] – tetrabutylammonium iodite [NBu4][OAc] –tetrabutylammonium acetate [NBu4][OH] –tetrabutylammonium hydroxide [NTf2] – bistriflimide NHC – N-heterocyclic carbene NHPI – N-hydroxyphthalimide NMDA- N-methyl-D-aspartate NMI - N-methylimidazole NMO – N-methylmorpholine-N-oxide NMR – nuclear magnetic resonance PAR – protease activated receptor PDE-5 – phosphodiesterase PET – polyethylene terephthalate [PF6] – hexafluorophosphate Phen – phenanthroline PINO – phthalimide-N-oxyl POM – polyoxometalate RT- room temperature SILP – supported ionic liquid phase catalyst SQUID – superconducting quantum interference device TBHP- tert-butyl hydrogen peroxide TBN – tert-butyl nitrite TBSO – tert-butyldimethylsilyl TEG – triethylene glycol TEM- transmission electron spectroscopy TEMPO - 2,2,6,6-tetramethylpiperidine-N-oxyl TGA – thermal gas analysis THF- tetrahydrofuran TMEDA – N’,N’,N’, N’-tetramethylethylenediamine TPAP – tetrapropylammonium perruthenate UFL- upper flammability limit UHP- urea hydrogen peroxide UV- ultraviolet UV- Vis –ultraviolet-visible Xphos – (2-dicyclohexylphosphino-2’,4’,6’-triisopropylbiphenyl) Abstract Oxidations are a fundamental class of reactions in organic chemistry. Furthermore, the ability to carry out such transformations in an efficient and selective manner has the potential for widespread application in the production of both bulk and fine chemicals, pharmaceuticals, agrochemicals and many more. Despite this, oxidations are often avoided due to the environmental and economic problems associated with traditional, stoichiometric oxidising agents. Within this thesis, three methods for the aerobic catalytic preparation of carbonyl compounds will be studied. This is done with the aim to develop sustainable methods for aerobic catalytic oxidation reactions that may help in the efforts to use aerobic catalysis on an industrial scale. Chapter two focusses on the development of a metal-free aerobic catalytic system for alcohol oxidation using sterically unhindered nitroxyl radicals in combination with nitric acid. The aim is to broaden the substrate scope of the reaction, whilst using a cheap, abundant source of NOx. Chapter three explores the use of Pd(II) catalysed oxidative carbonylation for the synthesis of 2-alkynoates. The focus is to use lower catalyst loadings than previously reported through the use of ligands, whilst improving the selectivity and substrate