In the Introduction part of this thesis, the chemistry of organo-fluorine compounds including the electronic properties that fluorine impacts onto organic molecules, steric effects, lipophilicity and other characteristics as well as applications and important features of organo-fluorine compounds are briefly discussed. Moreover, summary of the methods for their preparation, modern methods for fluorinations and enantioselective fluorinations, and fluoroalkylation methodologies in organic synthesis are described. Additionally, the chemistry of fluorinated phosphonates including their preparations, important applications and the chemistry of α,α-difluorophosphonates are discussed. The Results and discussion part describes nucleophilic trifluoromethylation of various electrophilic substrates using diethyl trifluoromethylphosphonate. Furthermore, efficient stereoselective synthesis of fluorovinylphosphonates by a base-induced HF elimination of α,α-difluorophosphonates is explained. In addition, synthesis of number of new, structurally diverse compounds, having a difluorophosphonate moiety using the reaction of diethyl difluoromethylphosphonate with various α,β-unsaturated carbonyl compounds, Michael acceptors and imines are reported. Also, preliminary experiments dealing with nucleophilic reactions of...

The pentafluorosulfanyl (SF5) group displays remarkable and unique properties, including large dipole moment, high electronegativity, high thermal and chemical stability, as well as high lipophilicity. However, only a few synthetic methods for the preparation of aromatic pentafluorosulfanyl building blocks have been developed to date. This work aims at improving availability and accessibility of aryl sulfurpentafluoride building blocks. In the first part of the work, the synthesis of aryl sulfurpentafluorides by the direct fluorination of diaryl disulfides with elemental fluorine is described. Nowadays, this synthetic strategy is used by industry on a multi-kilogram scale. However, the scope of the reaction is only limited to 3- and 4- nitro-1-(pentafluorosulfanyl)benzenes. In this work, the synthesis of various para-, meta- and ortho-substituted-(pentafluorosulfanyl)benzenes following the same approach was carried out. In the second part, the derivatization of aryl sulfurpentafluoride building blocks was investigated. Direct fluorination of 3-nitro-1-(pentafluorosulfanyl)benzene afforded 3-fluoro-5-nitro-1- (pentafluorosulfanyl)benzene. The titled compound was derivatized by two different processes: nucleophilic aromatic substitution (SNAr) of fluorine and vicarious nucleophilic substitution of...

In the Introduction part of this thesis, the chemistry of organofluorine compounds is discussed, particularly the methods for the preparation of organofluorine compounds mainly by fluoroalkylation methods. Furthermore, the chemistry of fluorinated phosphonates, methods of their preparation, reactivity and biological activity is discussed. Additionally, the reactivity of fluoromethane derivatives is briefly mentioned and especially, the reactivity of diethyl fluoromalonate and fluorobisfenylsulfonylmethane is described. The Results and discussion part is devoted to the reactivity of three fluorinated phosphonates: tetraethyl fluoromethylenbisphosphonate, diethyl fluorophenylsulfonylphosphonate and previously not described diethyl fluoronitromethylphosphonate. These fluorinated phosphonates belong to the family of nucleophilic monofluoroalkylation reagents, meaning that these compounds are convenient starting materials for the synthesis of complex organic molecules containing the fluorine atom. The results deal with the reactivity of above mentioned fluorinated phosphonates, mainly with alkylation reactions, Horner-Wadsworth-Emmons reactions and conjugated additions. Also, other synthetic methods such as the Mitsunobu reaction or the palladium catalyzed allylation reaction were investigated; however,...

Charles University in Prague, Faculty of Science Department of Organic Chemistry Ing. Yana Chernykh Sulfur-Based Reagents for Nucleophilic and Radical Introduction of Tetrafluoroethyl and Tetrafluoroethylene Groups Ph.D. Thesis Prague 2014 ABSTRACT This project was aimed at developing new methodologies for selective introduction of tetrafluoroethyl and tetrafluoroethylene groups into organic molecules. The study was focused on reactivities of fluorinated sulfones and sulfides as tetrafluoroalkylation reagents. In the Introduction part of the thesis, main aspects of organofluorine chemistry are outlined, illustrating beneficial effects of fluorine atoms on physical, chemical and biological properties of organic compounds. General synthetic methods for the selective introduction of fluorine atoms and fluoroalkyl groups to organic molecules are described. Particular attention is given to reactivity and applications of CF2CF2-containing compounds, indicating challenges in synthetic approaches toward tetrafluoroalkylation. The Results and discussion part describes reactivities of four new fluorinated organosulfur reagents as tetrafluoroethyl and tetrafluoroethylene building blocks. The application of these reagents as various carbanionic or radical synthons proved to be effective for the incorporation of CF2CF2...