S. A. Postovoi

Reaction of vicinal dihalopolyfluoroalkanes with sodium azide

Conclusions1.The reaction of vicinal dihalopolyfluoroalkanes and related compounds with sodium azide causes replacement of halogen by an azide group, probably by an ionic cleavageaddition chain mechanism.2.Nucleophilic azidobromination of fluoroolefins has been carried out by the action of sodium azide and bromine.3.These reactions were used to synthesize new β-halopolyfluoroalkyl azides.

Generation of radicals by the photolysis of branched fluoroolefins and their study by EPR spectroscopy

The UV irradiation of branched fluoroolefins leads to the formation of free radicals due to the addition of CF3 to the starting olefin. Branched fluoroolefins containing a fluorine atom at the radical site are incapable of recombination but react with oxygen.

S-anions from 2,2,4,4-tetrakis(Trifluoromethyl)-1,3-dithietane and their reactions

Conclusions1.The system containing 2,2,4,4-tetrakis (trifluoromethyl)-1,3-dithietane and halide ion is the equivalent of the α-halohexaf luoroisopropylthio anion and may be used in the synthesis of compounds containing α-fluoro and α-chlorohexafluoroisopropylthio groups.2.The cycloadduct of perfluoroisobutylene and hexafluorothioacetone was obtained under nucleophilic catalysis conditions.

Organometallic synthesis of compounds containing a perfluoroisobutenyl group

ConclusionsPerfluoroisobutenyllithium and perfluoroisobutenylmagnesium bromide were obtained, and it was shown that these reagents can be used in the synthesis of compounds containing a perfluoroisobutenyl group.

Intermolecular cyclisation with participation of cyano-group in reactions of flyoroolefines with cyanohydrins

Abstract The interaction of fluoroolefines( I ) with hexafluoroacetone cyanohydrin (II) under nucleophylic catalyzis leads to formation of 3-iminotetrahydrofurans (IV) as a result of addition of intermediate carbanion (III) to CN-group: Two molekules of perfluoroisobutene are involved into reaction with K-salt of cyanohydrin (II) to form N- perfluoroisobutenyl derivative (V) The structure of obtained products were confirmed by NMR-, IR- and mass-srectra, as well as chemical transformations.

Partial oxidation of internal fluoroolefins by potassium permanganate

Conclusions1.Under strictly controlled conditions, internal fluoroolefins are oxidized by potassium permanganate with preservation of the carbon-carbon bond and form aliphatic and alicyclic fluorine-containing α-dicarbonyl and α-hydroxycarbonyl compounds.2.Fluorine-containing α-hydroxyketones undergo nucleophilic isomerization involving 1,2-migration of the peffluoroacyl group from atom C to O.

Reaction of perfluoro-tert-butyl anion with vicinal dihalopolyfluoroalkanes

ConclusionsVicinal dibromopolyfluoroalkanes are dehalogenated by perfluoro-tert-butyl anion. In the reaction of 1,2 dibromotetrafluoroethane with this anion, bromine is replaced by the perfluoro-tert-butyl group by a cleavageaddition mechanism.

1,2-Difluoroethylenes in the Wagner reaction

ConclusionsThe conversion of substituted 1,2-difluoroethylenes to α-diketones by the action of potassium permanganate was found to be general in nature.

Investigation of the interaction of metal-centered free radicals with α-diketones, containing perfluoro-tert-butyl and 1-methyl-o,m-carboranyl groups using the epr method

Conclusions1.We have identified the spin adducts of metal-centered free radicals with fluorinated α-diketones.2.The limiting stage of the transformation of spin adducts into paramagnetic chelate complexes is the trans-cis isomerization of the adduct.

Reductive defluorination of hexafluoroacetone and the synthesis of halopentafluoroacetones

Conclusions1.Hexafluoroacetone undergoes reductive defluorination upon the action of metals to form perfluoro-2-propenolates of the metals and the products of their subsequent transformations.2.A new preparative method was proposed for the synthesis of pentafluoro-2-propenol and halopentafluoroacetones based on the reaction of hexafluoroacetone with aluminum.