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Dissertation ETH No Research Collection Doctoral Thesis Synthesis and application of highly functionalised acylphosphane oxides Author(s): Ott, Timo Publication Date: 2008 Permanent Link: https://doi.org/10.3929/ethz-a-005867134 Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library Dissertation ETH No. 18055 Synthesis and Application of Highly Functionalised Acylphosphane Oxides A dissertation submitted to the ETH ZÜRICH for the degree of DOCTOR OF SCIENCES presented by Timo Ott Dipl. Chem. born 24. February 1982 citizen of Ludwigshafen am Rhein, Germany accepted on the recommendation of Prof. Dr. H. Grützmacher, examiner Prof. Dr. A. Mezzetti, co-examiner Zürich 2008 Für Helga "Just one more thing!" Columbo Danksagung Mein besonderer Dank gilt Prof. Dr. Hansjörg Grützmacher für die interessante Themenstellung und die vielen fruchtbaren Diskussionen. Ausserdem für die motivierende Unterstützung eigener Ideen und das entgegengebrachte Vertrauen. Prof. Dr. Antonio Mezzetti möchte ich für die freundliche Übernahme des Korreferats danken. Insbesondere bin ich für die ausführlichen Korrekturen und die konstruktive Kritik zu dank verpflichtet. Dr. Hartmut Schönberg danke ich für viele interessante Gespräche und Diskussionen und die schöne Zeit. Als nächstes möchte ich allen Kooperationspartnern danken, die unterstützend zur vorliegenden Arbeit beigetragen haben. Dies sind insbesondere die Ciba Holding AG, Prof. Dr. B. Meier und Prof. Dr. M. Reiher. Dr. Michael Wörle, Dr. Frank Krummeich, Dr. Heinz Rüegger, Dr. Jacco van Beek, Christian Mensing und Martin Colussi hatten immer ein offenes Ohr und "mal eben 5 (-120) Minuten Zeit", wenn es um Problemstellungen in der chemischen Analytik ging oder spezielle Experimente durchgeführt werden mussten. Dr. Céline Réthoré möchte ich für die wundervolle Zeit und die Unterstützung danken. Meinen Laborkollegen Friederike ("Fritzi") Tewes, Florian ("Puschl") Puschmann, Florian ("Karl") Auras, Dr. Simone Alidori, Federica ("Fede") Ricatto, Matthias Vogt, Dr. Carlos ("dos canones") Miro Sabatè, Judith Bräuer, Georgina Müller, Alex Huber, Katrin Prinz, Theodor ("Theo") Zweifel, Coen(radus) Hendriksen, Dr. Monica Trincado, Samuel Annen, Dr. Daniel Stein und den "Altdoktoranden", sowie den Kollegen aus anderen Arbeitsgruppen danke ich für die schöne Zeit in und ausserhalb des Laboratoriums, die anregenden Diskussionen und die Zerstreuung beim Tischfussball spielen. Matthias Vogt und Dr. Hartmut Schönberg danke ich zudem für die vielen gemeinsamen Stunden am Diffraktometer, Judith Bräuer, Gerogina Müller und Dr. Daniel Stein für die angenehme Laborzeit. Fede danke ich für die motivierenden Gespräche und die Zerstreuung in den Pausen während der "Schreibphase". Weiterhin möchte ich meinen "Forschungspraktikant(inn)en" und "Masterstudent(inn)en" Anna, Alex, Yves, Frederic, David, Elisabeth danken. Last but not least möchte ich den Busfahrern der ZVV danken, die mich nicht nur immer sicher zur ETH brachten, sondern auch massgeblich daran beteiligt waren, dass ich Céline kennengelernt habe. CURRICULUM VITAE Name: Timo Ott Family Status: unmarried Day of Birth: 24. Februar 1982 Place of Birth Ludwigshafen am Rhein, Germany Nationality: German Formation 03/2006-10/2008: Dissertation, Swiss federal institute of technology (ETH Zürich), Switzerland, Institute of Inorganic Chemistry, Synthesis and Application of Highly Functionalised Acylphosphane oxides, Prof. Dr. H. Grützmacher. 07/2005-01/2006: Diploma Thesis, University of Karlsruhe (TH), Germany, Institute of Inorganic Chemistry, NHC-Stabilisierte Ruthenium-Komplexe und deren Anwendung in der Aktivierung von Distickstoff, Prof. Dr. U. Radius. 15. Juni 2005: Diploma Exam, Dipl. Chem. 2. Oktober 2003: Intermediate Diploma in Chemistry 10/2001-01/2006: Studies of Chemistry, University of Karlsruhe (TH). 22. Juni 2001: Abitur, Albert-Einstein-Gymnasium, Frankenthal/ Pfalz. Further Education 10/2006-02/2007: „Entrepreneurship Course - Venture Challenge“, University of St. Gallen, Switzerland. 07/2003: Licence for the distribution of chemicals. Publications 1) A simple straight forward synthesis of phenylphosphane and the photoinitiator bis(mesitoyl)phenylphosphane oxide (Irgacure 819), H. Grützmacher, J. Geier, D. Stein, T. Ott, H. Schönberg, R.H. Sommerlade, S. Boulmaaz, J.P. Wolf, P. Murrer, T. Ulrich, Chimia 2008, 62, 18-22. 2) Ethanol as a Hydrogen Donor: Highly Efficient Transfer Hydrogenations with Rhodium(I) Amides; T. Zweifel, J.V. Naubron, T. Büttner, T. Ott, H. Grützmacher, Angew. Chem. Int. Ed. Engl. 2008, 47, 3245-3249; Angew. Chem. 2008, 47, 3289- 3293. 3) Synthesis of polystyrene nanoparticles with a very small dispersity, T. Ott, H. Grützmacher, Patent 2008, patent pending. 4) Synthesis of BAPO functionalised Polymers, T. Ott, D. Stein, H. Grützmacher, Patent 2008, patent pending. 5) Oxidative cleavage of Rhodium Phosphide Bonds: Generation of Phosphinyl Radicals from 18 electron trigonal bipyramidal Rh(I) complexes, U. Fischbach, D. Stein, T. Ott, H. Grützmacher, to be submitted. 6) Investigation of the Formation of Phosphanoyl Radicals derived from bis(acly)phenylphosphane oxide, T. Ott, M. Vogt, H. Grützmacher, to be submitted. 7) A simple Synthesis of Functionalised Phosphanes, T. Ott, H. Grützmacher, to be submitted. Public Presentations 1) Straight forward synthesis of functionalised acylphosphane oxides, 5th European Workshop on Phosphorus Chemistry, Regensburg, Germany, March 2008. 2) Straight forward synthesis of highly functionalised acylphosphane oxides and their application, Symposium der Anorganischen Chemie, Zürich, Switzerland, December 2007. Zusammenfassung Die vorliegende Arbeit beschreibt die Synthese von hochfunktionalisierten Acylphosphanoxiden und deren Anwendung als Photoinitiatoren. Neben der Funktionalisierung von Oberflächen und Polymeren durch das Aufbringen von photoaktiven Gruppen wurde insbesondere die Anwendung in der Emulsionspolymerisation getestet. BAPO BAPO BAPO BAPO BAPO FG FG FG FG FG Surface Polymer Abbildung 1: BAPO-funktionalisierte Oberflächen und Polymere. NaPH2 ist ein geeignetes Ausgangsmaterial für die Synthese von Acylphosphanoxiden. Das Hauptproblem bei der Verwendung von NaPH2 ist dessen Schwerlöslichkeit und seine aufwendige Synthese. Deshalb haben wir eine einfache Synthesemethode ausgehend von elementarem roten oder weissen Phosphor entwickelt. Hierbei werden der Phosphor und das Natrium in flüssigem Ammoniak bei Raumtemperatur zu einer Mischung aus [NaPH2(solv)x] und 2[NaNH2(solv)x] umgesetzt. Durch anschliessende Protonierung des NaNH2 wird das reine NaPH2 erhalten. Verwendet man für die Protonierung des Reaktionsgemisches zwei äquivalente tert-Butanol, erhält man neuartige NaPH2- Alkoxidcluster, die sich durch hervorragende Löslichkeiten auszeichnen und selbst in Kohlenwasserstoffen löslich sind. Aus Toluol bzw. 1,2-Dimethoxyethan (dme) t lassen sich zwei verschiedene Alkoxid-Cluster [Na13(PH2)(O Bu)12] P6 und t [Na12(PH2)(O Bu)12][Na(dme)3] P7 kristallisieren, deren strukturelle Charakterisierung durch eine Kombination aus Pulsed Field Spin Echo NMR, Festkörper-NMR und Kristallstrukuranalysen durchgeführt werden konnte. Zusätzliche Berechnungen untermauern diese Untersuchungen. Es handelt sich - um zwei alkoxidstabilisierte Natrium-Cluster, in deren Zentrum sich ein PH2 -ion befindet (siehe Abbildung 2). Die 13 (in Cluster 1) bzw. 12 (in Cluster 2) Natriumatome sind auf den 20 Ecken eines pentagonalen Dodekaeders dynamisch fehlgeordnet. Abbildung 2: Struktur des Clusters 1 und des Clusteranions 2. Mit diesem neuartigen Ausgangsmaterial der formalen Zusammensetzung t NaPH2 x 2NaO Bu war es möglich, ausgehend von funktionalisierten Arylfluoriden neuartige tertiäre Arylphosphane zu synthetisieren, die als Liganden oder für funktionelle Materialien interessant sind. Durch leicht modifizierte Reaktionsbedingungen lassen sich auch primäre und sekundäre Arylphosphane synthetisieren, die nach den litreaturbekannten Methoden mit Acylchlorid, Base und Wasserstoffperoxid zu den entsprechenden Acylphosphanoxiden umgesetzt werden können. Zur gezielten Darstellung von hochfunktionalisierten Acylphosphanoxiden konnten aus NaPH2 und Acylchloriden Natriumbis(acyl)phosphide dargestellt werden. Aus diesen wurden mit Elektrophilen, wie Alkylhalogeniden, Arylfluoriden, Epoxiden bzw. durch palladiumkatalysierte Kreuzkupplung mit Aryliodiden funktionalisierte Bis(acyl)phosphane (BAPs) synthetisiert. Diese BAPs können zu den entsprechenden funktionalisierten Bis(acyl)phosphanoxiden (BAPOs) mit Wasserstoffperoxid oxidiert werden. Durch Umpolung des Natriumbis(acyl)phosphides wurde auch eine neue Möglichkeit geschaffen BAPs mit nucleophilen Reagenzien, wie Grignardreagenzien darzustellen. Es war möglich, über 50 BAPOs mit verschiedensten Funktionellen Gruppen zu synthetisieren, die sich durch neuartige physikalische und chemische Eigenschaften auszeichnen (z.B. Löslichkeit in fluorierten Phasen, ionischen Flüssigkeiten, Wasser). Erstmals wurden die Kristallstrukturen von funktionalisierten BAPOs untersucht und verglichen. Die P–C(=O) -Bindungslängen sind mit zirka 1.9 Å sehr lang und verhalten sich direkt proportional zur Aktivität des Photoinitiators. Des Weiteren wurden photolytische und erstmals thermische Zersetzungsreaktionen der Acylphosphanoxide Irgacure 819 (BAPO) und Lucirin TPO (MAPO) untersucht. Für die photolytischen Zersetzungsreaktionen wurden Abfangreagenzien
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