Reaktionstechnische Analyse der Hydroformylierung von Olefingemischen

Es wurde ein neues Konzept zur Kontrolle der Aktivität des Katalysator-Ligand-Komplexes während eines kontinuierlich betriebenen großtechnischen Verfahrens am Beispiel der Rhodium-katalysierten Hydroformylierung entwickelt. Zu diesem Zweck wurden die Einflüsse der Parameter Temperatur, Druck, Rhodiumkonzentration und des Katalysator-Ligand-Verhältnisses auf die Hydroformylierungsgeschwindigkeiten in einem Gemisch, bestehend aus fünf unterschiedlichen Olefinen, ermittelt. Anhand der Ergebnisse wurde ein Modell zur Berechnung der Konzentration der aktiven Katalysatorspezies erstellt.A novel activity control concept was developed for a ligand modified rhodium catalyst in a continuous industrial hydroformylation process by addition of an olefin with known kinetics. Therefore, five different alkenes were studied, separately and in the mixture, in two solvents. The effects of temperature, pressure, rhodium concentration and ligand/rhodium ratio on the rates of hydroformylation in the olefin mixture were investigated. In addition, a rate model for calculation of the active catalyst species concentration was developed based on the kinetic data

Oxidative Lignin-Spaltung und die Verwertung der resultierenden Produkte

The presented thesis aimed at finding reactions that would leave to the oxidative cleavage of Lignin. An abundant structural motive in the very heterogenic composition of Lignin is the aromatic ring. Cyclohexylbenzene and Veratrole alcohol were used as model compounds. Ozonolysis of these compounds in ionic liquids (ILs) as solvent and in common solvents did not lead to aromatic cleavage. Furthermore Potassium persulfate and Rutheniumtetroxid (RuO4) have been used. Optimized reaction conditions, using Ruthenium(III) chloride as catalyst, Sodium hypochlorite as oxidizing agent and Acetonitrile/Water as solvent could be found. A third solvent, e.g. DCM was only needed, when the starting material was insoluble in CH3CN/H2O. If this reaction was allowed to run 70 hours or more, the starting material Veratrole alcohol reacted to the supramolecule Cyclotriveratrylene (CTV). To my knowledge this is the first alkaline reaction to yield CTV. It was tried to optimize this reaction and to use it on different starting materials. 4-(Tert-butoxymethyl)-1,2-dimethoxybenzene yielded CTV up to 80 %. Butyl (3,4-dimethoxybenzyl)carbamate did not react under the applied conditions. 3,4-Dimethoxybenzyl methyl carbonate yielded its dimer. 3,4-Dimethoxybenzyl 3,5-Dinitrobenzoate and (3,4-Dimethoxyphenyl) methanamine each yielded a mixture of products with different ratios of Veratraldehyde, Veratrole alcohol and 1,2-Dimethoxybenzene.The experiment oxidative cleavage of (1S,2R)-1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol as a model compound with Manganese based catalysts failed.Additionally this thesis aimed at transforming the Lignin cleavage products to more valuable chemicals. Electron-rich arenes were successfully sulfenylated by silver catalysts. Guaiacol was successfully iodinated with Barluenga reagent and subsequently cross-coupled in a one-pot reaction.1,3-Dimethylimidazolium dimethyl phosphate ([DMIM]DMP) and 1-Ethyl-3-methylimidazolium acetate ([EMIM]Ac) solve biomass quite well. Therefore these ILs could be used in a biomass disintegration process. For this purpose the ILs need to show great long-term stability at high temperatures. Tests to examine the long-term stability over 3 months have been conducted in collaboration with the AVT. Although the large majority of the probes kept their ability to disintegrate biomass at the end of the test, signs of aging, shown in NMR, IR and Raman spectra, make an economic deployment less likely

BIOnic Liquids: Imidazolium-based Ionic Liquids with Antimicrobial Activity

We have synthesized twelve new ionic liquids composed of an imidazolium-based cation in combination with an anion that shows antiobiotic or analgesic activity. These BIOnic Liquids have been tested towards their antibiotic activity in a standardized microbiological assay. A surprizingly large number of compounds shows high activity towards a set of bacteria which cannot be explained as simple cumulative effects. The general concept opens up completely new possibilities for the future development of pharmaceutically active compounds