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    Trifluoromethyl Phosphoranide, erste Phosphoranide mit Csp3-P Bindungen: Synthese, Eigenschaften und Derivate
    The new tris(trifluoromethyl)fluorophosphoranide and tetrakis(trifluoromethyl)phosphoranide salts were synthesized. High relative stability of these derivatives allowed theirs full characterization including X-Ray analysis as well as comprehensive studying of theirs chemical properties. Thermal stability and fluxional behavior of the salts in solution in dependence on the nature of cation were investigated. Energy barriers to pseudorotation in trifluoromethyl phosphoranides were compared with those for trifluoromethyl phosphoranes. Ab-initio calculations of electronic and geometrical parameters as well as selected gas-phase acidities for phosphoranides were performed and close interrelationships of different parameters for each group of substituents (axial, equatorial) were established. A new class of compounds was discovered during studying the chemistry of phosphoranides. Mixed-valence species (l3s3P-l5s6P system) were unexpectedly obtained in the reactions of trifluoromethylphosphoranides with fluoride ion sources in monoglyme. These derivatives were characterized by NMR and MS spectral methods however, numerous attempts to grow single crystals applicable for X-Ray analysis failed compounds quickly decomposed in solution even at -40 Ã ?Ã ºC to give corresponding phosphate salts.Perphosphoranides were obtained in high yields in the reaction of corresponding trifluoromethyl phosphines with DFI. These compounds were fully described including X-Ray analysis.Syntheses of starting compounds (trifluoromethyl-phosphines, DFI, DFTMU) were optimized significantly and new convenient large-scale routes to ones were found.
    doctoral thesis
      543  324
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    NEW CLASSES OF POTENTIAL MATRIX METALLOPROTEINASE INHIBITORS BASED ON OXAMATE, CARBAMOYLPHOSPHONATE AND BISPHOSPHONATE FUNCTIONS
    In recent years, we have witnessed a huge progress in developing new drugs. However, the process of their design is expensive and long. Finding an effective synthetic pathway which can be used to synthesize new drugs plays a crucial role here. Undoubtedly, inhibitors of matrix metalloproteinase are very attractive compounds for drug discovery. According to much excisting evidence, they play a fundamental role in a wide variety of pathologies. The implementation of MMPs into processes critical to angiogenesis, tumor invasion etc., has prompted rapid development of new important agents, namely inhibitors of matrix metalloporteinase. In this thesis, different and effective strategies that can be employed to design potential inhibitors against overexpression of matrix metalloproteinases have been demonstrated. Moreover, strategies that can highlight the strength and drawback of each approach have been investigated. We have synthesied a family of different compounds bearing in their molecule oxalyl, phosphonoformyl and bisphosphonate groups� theoretically capable to chelate to metal ions like zinc, calcium or magnesium. These agents are referred to as a potent zinc binding groups (ZBGs). It should be noted that, the past few decades are testament to the ingenuity of chemistry in designing such chemical entries.
    doctoral thesis
      258  136
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    Halogenierte fluorhaltige Diazine: Synthese und chemische Eigenschaften
    From the many possible use of fluorine-containing diazines follows that new, effective methods for the synthesis and modification of these heterocyclic compounds from simple and inexpensive starting materials are being sought. As research subjects of this study cyclohexyl-and phenyl-substituted trifluoromethyl-diazines were selected in this way, the influence of aliphatic and aromatic groups are studying the reactivity of the heterocyclic ring. The modification of the heterocyclic ring in the 2.Position (for pyrimidine) and in the 3.Position (for pyridazine and pyrazine) is the main theme of this work.
    doctoral thesis
      259  183
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    Auf dem Wege zu neuen lipophilen, delokalisierten Onium-Fluoriden, -Trimethyldifluorsilikaten und -Perfluoralkoholaten:Synthesen, Eigenschaften, Anwendungen
    In this study a range of new sources of fluoride ions with lipophilic and delocalized cations having symmetrical and nonsymetrical C-N-P , C-N-S and C-N-C backbones completely substituted by dialkylamino groups were designed to improve the 'Halex' fluorination process.Reactions of bis(dialkylamino)difluoromethane with N-trimethylsilyltetramethylguanidine and tris(diethylamino)phosphazene led to (Alk2N)2CNC(NMe2)2 Me3SiF2- and (Alk2N)2CNP(NEt2)2 HF2-, respectively. Sulfur tetrachloride reacted with tetramethylguanidine to give tris(tetramethylguanido) chloride. Depending on the reaction conditions sulfur tetrafluoride and (diethylamino)sulphur trifluoride and tetramethylguanidine or N-trimethylsilyltetramethylguanidine afforded the salts with C-N-S backbone with F-, HF2-, Me3SiF2- or Me2SiF3- counter ions. The X-Ray structures of some new salts are discussed.Convenient and scalable methods of perfluoralkoholate [OCF2RF]- preparation via reaction of mono- and bisperfluoroalkylacid fluorides as well as fluorosulfonic acids with CNC-silicates, DFI, (Me2N)2CF2 and TMAF were developed.
    doctoral thesis
      275  126
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    Neue fluorierte Sulfonate, Amine und Phosphonate. Synthese und mögliche Anwendungen
    A range of new fluorine-containing lithium salts generating interest as novel electrolytes for lithium batteries were synthesized from 2,2-difluoro-2-fluorosulfonylacetyl fluoride in three steps. The novel lithium salts are non-sensitive to moisture, thermally and electrochemically stable. Furthermore, it was demonstrated that the Ruppert-Prakash reagent is able to react with a number of cyclic imines under acidic condition to afford the corresponding α trifluoromethyl derivatives of nitrogen heterocycles. 5-7 Membered cyclic imines bearing various alkyl, aryl or heterocyclic group were successfully involved in this transformation. Novel trifluoromethylated analogues of nicotine, anabasine and homoanabasine alkaloids were synthesized.
    doctoral thesis
      330  117
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    Pentafluorethyllithium: Untersuchung von Eigenschaften und Reaktivität
    Perfluoroalkylated compounds have become of great importance in life sciences and technical development as effective and selective pharmaceuticals and pesticides or liquid crystals in active matrix displays. An in this context important novel and green pentafluoroethylating reaction, that lacks the use of environmentally harmful chlorinated or iodinated alkanes was investigated in this dissertation.The stability of pentafluoroethyl lithium (PFELi), which is formed as reactive moiety in this reaction, was investigated by low temperature 19F- and 13C-NMR-spectroscopy. Reactions with various carbonyls have been carried out. Ketones can be transformed into pentafluorinated alcohols. 1,4-cyclohexanedione reacts to the trans product exclusively. The regioselectivity of the reaction of PFELi with 1,4-unsaturated carbonyls can be shifted by usage of bulky aluminium Lewis-acids. Epoxides can be opened with PFELi via activation with TiCl4. Pentafluoroethylated ketones can be synthesised by reaction of PFELi with the corresponding esters in presence of LiBr at -110°C. Some of these ketones can be transformed to pentafluorinated cinnamon acids under conditions of Perkin-reaction. In the BF3 mediated reaction of PFELi and imines a novel pentafluoroethylated borane could be isolated and investigated by X-ray analysis. Chloro phosphines and phosphites could also pentafluoroethylated in a substitution reaction.Pentafluoroethylated carbamoyl phosphonates, potentiell matrix metallo protease inhibitors (MMPI) could synthesised in a convenient one pot reaction.
    doctoral thesis
      311  99
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    Eine neue Methode für regioselektive Einführung von Phosphinaten in fluorierte Diketone und Imine
    The aim of this thesis was to investigate the reactivity of ethyl methylphosphinate and ethyl phenylphosphinate in reactions with fluorinated diketones, fluorinated and nonfluorinated cyclic imines and trifluoromethylpyruvate. The dehydration of phosphinylated ketones led to formation of fluorinated phosphinylated enones, which can be used as versatile applicable building blocks in organic chemistry.Recently, there has been considerable interest in the derivatives of hydroxybisphosphonates because of their biological properties and medical application. Herein we presented a first attempt to synthesize a new class of fluorinated bisphosphinates. Unfortunately, these products are sensitive to moisture and undergo the phosphinate-phosphonate rearrangement quickly.
    doctoral thesis
      243  104