Currently, the chemistry of organofluorine compounds is a leading and rapidly developing area of organic chemistry. Fluorine present in a molecule largely determines its specific chemical and biological properties. This thematic issue covers the trends of organofluorine chemistry that have been actively developed in Russia the last 15 – 20 years. The review describes nucleophilic substitution and heterocyclization reactions involving fluorinated arenes and quinones and skeletal cationoid rearrangements in the polyfluoroarene series. The transformations involving CF3-substituted carbocations and radical cations are considered. Heterocyclization and oxidative addition reactions of trifluoroacetamide derivatives and transformations of the organic moiety in polyfluorinated organoboranes and borates with retention of the carbon – boron bond are discussed. Particular attention is devoted to catalytic olefination using freons as an efficient synthetic route to fluorinated compounds. The application of unsymmetrical fluorine-containing N-heterocyclic carbene ligands as catalysts for olefin metathesis is demonstrated. A variety of classes of organofluorine compounds are considered, in particular, polyfluorinated arenes and 1,2-diaminobenzenes, 1-halo-2-trifluoroacetylacetylenes, α-fluoronitro compounds, fluorinated heterocycles, 2-hydrazinylidene-1,3-dicarbonyl derivatives, imines and silanes. The potential practical applications of organofluorine compounds in fundamental organic chemistry, materials science and biomedicine are outlined.
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Joint pyrolysis with chlorine and bromine of polyfluoroarenethiols, -hetarenethiols, and their derivatives at 300-650°C furnished polyfluorocompounds containing chlorine and bromine.
1,2-Dichlorotetrafluorobenzene was obtained by reactions of chlorine with 5,6,7,8-tetrafluoro-1,4-benzodioxane and with a mixture of 3,4,5,6-tetrafluorophthaloyl chloride and 3,3-dichloro-4,5,6,7-tetrafluorophthalide at 500-550°C. Pyrolysis of pure 3,4-and 2,5-dichlorotrifluorobenzenethiols, as well as of a mixture of 3,4-, 2,4-, and 2,5-dichlorotrifluorobenzenethiols, in the presence of chlorine at 400-415°C in a flow system gave difficultly accessible 1,2,4-trichlorotrifluorobenzene.
Magnetic
field-affected reaction yield (MARY) spectroscopy is a
spin chemistry technique for detecting short-lived radical ions. Having
sensitivity to transient species with lifetimes as short as nanoseconds,
MARY spectroscopy usually does not provide detailed information on
their magnetic resonance parameters, except for simple systems with
equivalent magnetic nuclei. In this work, the radical anions of two
fluorinated diphenylacetylene derivatives with nonequivalent magnetic
nuclei and unknown hyperfine coupling constants (A
HF) were investigated by MARY spectroscopy. The MARY spectra
were found to be resolved and have resonance lines in nonzero magnetic
fields, which are determined by the A
HF values. Simple relationships between the positions of resonance
MARY lines and the A
HF values were established
from the analysis of the different Hamiltonian block contributions
to the MARY spectrum. The obtained experimental A
HF values are in agreement with the results of quantum
chemical calculations at the density functional theory level.
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