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Development of Sustainable Catalytic Methods for the Chemical Utilisation of Carbon Dioxide and for the Valorisation of Cashew Nut Shell Liquid

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Development of Sustainable Catalytic Methods for the Chemical Utilisation of Carbon Dioxide and for the Valorisation of Cashew Nut Shell Liquid Development of sustainable catalytic methods for the chemical utilisation of carbon dioxide and for the valorisation of cashew nut shell liquid Dissertation at Fakultät für Chemie und Biochemie Ruhr-Universität Bochum Submitted by Valentina Bragoni Born in Rome, Italy Supervisor Prof Dr Lukas J. Gooßen Bochum, 2020 To my beloved family I II You cannot get through a single day without having an impact on the world around you. What you do makes a difference, and you have to decide what kind of difference you want to make. Jane Goodall III IV The present work was carried out at Ruhr-Universität Bochum between July 2016 and February 2020 in the research group of Prof Dr Lukas J. Gooßen Evaluation Committee Chair: Evaluator: Prof Dr Lukas J. Gooßen Evaluator: Prof Dr Kristina Tschulik Evaluator: Prof Dr Viktoria H. Däschlein-Gessner V VI Official Declaration Hereby I declare that I have not submitted this thesis in this or any similar form to any other examination at the Ruhr-Universität Bochum or any other Institution. I officially ensure that this work has been written entirely by myself. I herewith officially ensure that I have not used any sources other than those cited and/or acknowledged, and any parts of the text which constitute quotes in original wording or in its essence have been explicitly referred by me by using official marking and proper quotation. This is also valid for used drafts, pictures and similar formats. For cooperation projects, the contribution of each author has been clearly stated. Bochum, Valentina Bragoni VII VIII Acknowledgements I wish to express my gratitude to Professor Gooßen for accepting me in his research group and for his trust and support. I am also truly thankful to Dr Käthe Gooßen for her help in finalising my manuscripts and Dr Wolf M. Pankau for reviewing this work. I would like to thank Professor Tschulik and Professor Däschlein-Gessner for agreeing to be part of the examination committee of my dissertation. I thank our secretaries Stefanie, Sylwia and Damla for their constant help. I thank Christoph Oppel for providing some of the unforgettable funniest situations, even when he was not aware of it. I also thank Florian Kaschuba for his many jokes and Michael Wüstefeld for his quenchless calm that makes me laugh. I thank my project partners for their contributions and the constructive cooperation in the projects. I would also like to thank all current and former members of the Gooßen group that I have met for their support. Special thanks go to Timo, Dagmar, Stefania, Manu, Florian, Giulia and Nardana for proofreading this work and Thilo for his constant support. I thank Valerio, Valentina, Chiara, Andrea, Porthus, with whom I have been friend for almost 15 years. I thank Danilo, Laura and the other friends from salsa, for welcoming me like a second family whenever I go back to Rome. With all my heart I thank my family: my parents Mimma and Riccardo, for their constant support and endless love, and my brother Daniele, whom I rarely see, but I love a lot. I want to thank my lovely grandma Gabriella who cries every time I leave from Rome to come back to Bochum, and makes me cry with her. I thank my aunts Maura and Fiorenza for their regular family updates. A special thought goes to my grandma Angela, who keeps watch over me from a special place. IX Abbreviations ABS branched alkyl benzene sulfonates m meta Ac acetyl group Me methyl group Ar aryl group MEA monoethanolamine BenzP* 1,2-bis(tert-butylmethylphosphino) benzene MeCN acetonitrile BDO 1,4-butanediol MES methyl ester sulfonate bp boiling point mes mesityl group BPhen 4,7-diphenyl-1,10-phenanthroline m.p. melting point CCS carbon capture and storage MS mass spectrometry 7-methyl-1,5,7-triazabicyclo[4.4.0]-dec-5- CCU carbon capture and utilisation MTDB ene CM cross-metathesis MTBE methyl tert-butyl ether cmc critical micellar concentration NHC N-heterocyclic carbene CNSL cashew nut shell liquid NMP N-methyl-2-pyrrolidone Cy cyclohexyl group NMR nuclear magnetic resonance DBU 1,8-diazabicyclo[5.4.0]undec-7-ene NP nonylphenol DCM dichloromethane NPEs nonylphenol ethoxylates DMAc dimethylacetamide o ortho DMF dimethylformamide p para DMS dimethylsuccinate PC propylene carbonate DMSO dimethylsulfoxide PMMA polymethylmethacrylate Et ethyl group poly-PPh3 polymer-bound triphenylphosphine FAE fatty alcohol ethoxylates rt room temperature FAME fatty acid methyl ester RWGS reverse water-gas shift reaction GC gas chromatography SDS sodium dodecyl sulfate HG Hoveyda-Grubbs SHOP Shell higher olefin process Ic tyrosinase activity THF tetrahydrofuran 1,3-di-iso-propyl-4,5-dimethylimidazol-2- IPr TMEDA N,N,N’,N’- tetramethylethylenediamine ylidene iPr isopropyl group TMP 2,2,6,6-tetramethylpiperidine IR infrared radiation TPS tetrapropylene benzene sulfonate LAS/LABs linear alkyl benzene sulfonates vs versus X Publications V. Bragoni, M. Dyga, T. van Lingen, B. Exner, L. J. Gooßen, Pressure-induced acidity switch opens up a salt-free, catalytic access to C4 base chemicals from CO2 and acetylene. manuscript in preparation J. Pollini, V. Bragoni, L. J. Gooßen, Beilstein J. Org. Chem. 2018, 14, 2737: Synthesis of a tyrosinase inhibitor by consecutive ethenolysis and cross-metathesis of crude cashew nutshell liquid. V. Bragoni, R. K. Rit, R. Kirchmann, A. S. Trita, L. J. Gooßen, Green Chem. 2018, 20, 11288: Synthesis of bio-based surfactants from cashew nutshell liquid in water. C. Matheis, T. Krause, V. Bragoni, L. J. Gooßen, Chem. Eur. J. 2016, 22, 12270: Trifluoromethylthiolation and Trifluoromethylselenolation of α-Diazo Esters Catalyzed by Copper. L. Huang, A. Biafora, G. Zhang, V. Bragoni, L. J. Goossen, Angew. Chem. Int. Ed. 2016, 55, 6933: Regioselective C−H Hydroarylation of Internal Alkynes with Arenecarboxylates: Carboxylates as Deciduous Directing Groups. XI Poster Presentations 10th Workshop on Fats and Oils as Renewable Feedstock for the Chemical Industry. Karlsruhe, Germany. March 2019. Best Poster Award: “Synthesis of bio-based surfactants from cashew nut shell liquid in water”. 9th World Congress on Green Chemistry and Technology, Amsterdam, Netherlands. September 2018. Chair of the conference. Best Poster Award: “Synthesis of bio-based surfactants from cashew nut shell liquid in water”. 3rd International Green Catalysis Symposium, Rennes, France. March 2017. “Chemical Valorisation of Cashew Nut Shell Liquid by Olefin-Metathesis”. Oral Presentations 10th Workshop on Fats and Oils as Renewable Feedstock for the Chemical Industry. Karlsruhe, Germany. March 2019. “Sustainable synthesis of surfactants and biological active compounds from cashew nut shell liquid”. 9th Young Chemists´ Symposium RUHR, Bochum, Germany. October 2018. “Synthesis of bio- based surfactants from cashew nut shell liquid in water”. XII Table of contents Official Declaration ............................................................................................................. VII Acknowledgements .............................................................................................................. IX Abbreviations......................................................................................................................... X Publications .......................................................................................................................... XI Poster Presentations ............................................................................................................. XII Oral Presentations ................................................................................................................ XII Table of contents ............................................................................................................... XIII 1 Abstract .............................................................................................................................. 1 2 Structure of the thesis ......................................................................................................... 3 3 Introduction ........................................................................................................................ 4 3.1 Chemistry as a tool against environmental degradation .............................................. 4 3.2 Renewable resources ................................................................................................... 6 3.2.1 Renewable resources in chemical syntheses ........................................................ 7 3.2.2 Cashew nut shell liquid ........................................................................................ 9 3.2.3 Carbon dioxide ................................................................................................... 11 4 Compounds and chemical procedures relevant to this work ............................................ 20 4.1 Surfactants ................................................................................................................. 20 4.1.1 Classification ...................................................................................................... 22 4.1.2 Dermatological, toxicological and environmental aspects ................................. 30 4.2 Tyrosinase inhibitors ................................................................................................. 33 4.3 Alkynes ...................................................................................................................... 34 4.3.1 Physical and chemical properties ......................................................................
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