V. A. Petrov

Electrophilic isomerization of substituted perfluorocyclopropanes under the effect of SbF5

Perfluoro(alkoxycyclopropanes) are isomerized on heating in the presence of SbF5 into perfluoro(2-alkoxypropylenes), while perfluoro(alkylcyclopropanes) are isomerized into the corresponding internal fluoroolefins under the effect of SbF5.

Reaction of higher perfluorinated amines with antimony pentafluoride

In the present work, we have shown that heating perfluorotriethylamine (la), perfluorotripropyiamine (Ib), and perfluorotributylamine (Ic) with SbFs leads to cleavage of the corresponding aikanes* and formation of internal azaolefins (IIa-c), A mixture of 0.02-0,04 mole amine and 0.0025-0.004 mole SbFs was heated in a flask equipped with a reflux condenser at 90-120~ until there was no further gas liberation [the reaction was run in an autoclave in the case of (Ia)], The reaction mixture was poured into water, The lower layer was separated, dried, and distilled.

Electrophilic condensation of 1-hydroperfluoropropylene and 1-hydroperfluoro-1-butene with fluoroethylenes

Conclusions1-Hydroperfluoropropylene reacts with tetrafluoroethylene in the presence of SbF5 to form the corresponding 1∶1 and 1∶2 adduct olefins. The condensation is accomplished at both the CFH and CF2 groups of the starting propylene. Under analogous conditions, 1-hydroperfluoro-1-butene condenses with fluoroethylenes exclusively at the CFH group.

Isomeric transformations of perfluorinated dienes by the action of antimony pentafluoride

ConclusionsIt was shown that perfluorinated dienes on being heated with SbF5, depending on the reaction conditions, form preferentially either perfluoro-1,2-dialkylcyclobutenes or perfluoro-1,2-dialkylcyclopentenes.

The electrophilic condensation of conjugated perfluorodienes with tetrafluoroethylene

Perfluoropentadienes and perfluoro-2,4-hexadienes react with tetrafluoroethylene with SbF5 as the catalyst at 20–50°C to give higher perfluorinated dienes.

Reactions of difluorocarbene with conjugated polyfluorodienes

Heating 2-chloroperfluoro-1,3-butadiene or perfluoro-1,3-pentadiene with excess hexafluoropropylene oxide leads to the formation of the corresponding cyclopentenes.

Cyclodimerization of perfluoro-1,3-pentadiene in the presence of SbF5

ConclusionsDuring heating of perfluoro-1,3-pentadiene with SbF5, it undergoes cyclodimerization with the formation of cis- and trans-perfluoro-1,2-propylidene-3,4-dimethylcyclobutane.

Long-lived perhalogenated fluoro-containing allyl cations

ConclusionsThe fluoro-containing perhalogenated allyl cations, postulated previously as the intermediates in the electrophilic alkenylation reactions of fluoroethylenes, were recorded and characterized for the first time by the NMR method.

Condensation of trichlorotrifluoropropylene and dichloroperfluoroisobutylene with fluorinated ethylenes in the presence of SbF5

Conclusions1.In the presence of SbF5, trichlorotrifluoropropylene and dichloroperfluoroisobutylene condense with trifluoroethylenes to form terminal fluorochloroolefins.2.The vibration frequency with main participation of the C=C bond depends on the structure of the perfluoroalkyl substituents.

Electrophilic condensation of pefluoroisobutene with fluoroethylenes in the presence of SbF5

ConclusionsPerfluoroisobutene reacts with fluorine-containing ethylenes in the presence of SbF5 to form a mixture of the corresponding isohexenes and isooctenes.