Gaidarzhy I. Synthesis and properties of aliphatic perfluoroalkoxyalkylamines and perfluoroalkoxybenzoic acids

The thesis is devoted to the development of methods for the synthesis of primary and secondary perfluoroalkoxyalkylamines and perfluoroalkoxybenzoic acids, obtaining on their basis new thermostable fluorinating agents and fluorine-containing local anesthetics. A convenient method for the synthesis of primary trifluoromethoxy- and pentafluoroethoxyalkylamines based on fluoroformyl or trifluoroacetyl derivatives of N-hydroxyalkylphthalimides and SF4 in anhydrous HF solution has been proposed. A method for the synthesis of secondary trifluoromethoxyalkylamines, consisting in the sequential interaction of N-phenyl derivatives of N-alkylaminoethanols and diethanolamine with COF2 and sulfur tetrafluoride in anhydrous hydrogen fluoride solution has been developed. A method for obtaining secondary mono- and bis(pentafluoroethoxyethyl)amines based on trifluoroacetyl derivatives of secondary aminoethanols and SF4 in anhydrous hydrogen fluoride solution has been described. A new thermostable fluorinating agent, bis(2-pentafluoroethoxyethyl)amino-trifluorosulfurane, has been synthesized and used in a new method for the synthesis of para-substituted trifluoromethylbenzenes starting with the corresponding benzoic acids. The basic regularities of the interaction of alkyl trifluoroacetoxybenzoates with SF4 in anhydrous HF solution have been established and explained, schemes of corresponding concert rearrangements have been proposed, which made possible developing of methods for the synthesis of mono- and bis(pentafluoroethoxy) benzoic acids. Schemes of concert rearrangements of the observed reactions have been proposed, the driving force of which is probably the intramolecular interactions nО(N)→σ*C–F and nF→σ*C–O, which is confirmed by the analysis of the influence of substituents on the transformation products. Methods for obtaining analogues of benzocaine, procaine and procainamide containing a pentafluoroethoxy group instead of an amino group have been developed, and a preliminary study of their local anesthetic activity has been performed. It has been showb that the replacement of the amino group with a pentafluoroethoxy group increases the activity of the obtained compounds, and the position of the pentafluoroethoxy group in the benzene ring is crucial in this process.