Carbonylation of Polyfluorobenzocyclobutenones in a SbF5 Medium

Russian Journal of Organic Chemistry - The carbonylation of perfluoro-2-R-benzocyclobutenones (R = F, CF3, C2F5, C6F5) in a CO-SbF5 system is accompanied by transformations of the four-membered...     

Biradical with a polyfluorinated terphenylene backbone

Russian Chemical Bulletin - A method was developed for the synthesis of perfluoro-1,1′:4′,1″-terphenyl by the reaction of chloroperfluorobenzene with zinc dust followed by the...     

Opening of the four-membered ring in perfluorinated 1-alkyl-2-phenyl- and 1-aryl-1,2-dihydrocyclobutabenzenes in the system I<Subscript>2</Subscript>-SbF<Subscript>5</Subscript>

Reactions of perfluorinated 1-phenyl-, 1-(2-ethylphenyl)-, 1-(4-ethylphenyl)-, 1-methyl-2-phenyl-, and 1-ethyl-2-phenyl-1,2-dihydrocyclobutabenzenes with iodine in antimony pentafluoride at 130°C, followed by hydroysis of the reaction mixture, resulted in the formation of perfluorinated 2-methyl-, 2-ethyl-2′-methyl-, 4-ethyl-2′-methyl-, 2-ethyl-, and 2-propylbenzophenones via opening of the four-membered ring in the initial cyclobutabenzene at the C¹–C² bond. The presence of hydrogen fluoride facilitates the process and promotes profound transformations leading to anthracene derivatives.     

Formation of perfluorinated 1,2-dialkylbenzenes from perfluoroalkylbenzocyclobutenes in the system I2-SbF5

Russian Journal of Organic Chemistry -     

Isomer conversions in perfluoro-1-ethylindane under the action of antimony pentafluoride

Perfluoro-1-ethylindane on heating with SbF₅ is isomerized to perfluoro-1,1-dimethylindane, perfluoro-,-o-trimethylstyrene, and perfluoro-1,2-dimethylindane. In the presence of SbF₅, the latter two products are converted one into the other. In addition, in SbF₅ perfluoro-1,2-dimethylindane is defluorinated to perfluoro-2,3-dimethylindene and fluorinated to perfluoro-2,3-dimethyl-4,5,6,7-tetrahydroindene which is further fluorinated to perfluoro-1,2-dimethyl-4,5,6,7-tetrahydroindane and is converted at 200C to perfluoro-1,7-dimethylindane. The latter is also formed on heating perfluoro-,-o-trimethylstyrene with SbF₅ at 200C.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 645–652, March, 1990.     

X-ray diffraction investigation of perfluoro-4-methylenecyclohexa-2,5-dienones

Perfluorinated 8-phenyl-7,8-diethylbicyclo[4.2.0]octa-1,4,6-trien-3-one (3), 2-(4-oxocyclohexa-2,5-dienylidene)-1,1-diethylbenzocyclobutene (4) and 2-(4-oxocyclohexa-2,5-dienylidene)-5-(2-phenyl-cis-1,2-diethylbenzocyclobuten-1-yloxy)-1,1-diethylbenzocyclobutene (5), including the 4-methylencyclohexa-2,5-dienone fragment, were prepared by the reaction of perfluoro-1,1-(1) and-1,2-diethylbenzocyclobutene (2) with pentafluorobenzene in SbF₅. Single crystal X-ray diffraction study of compounds 3–5 revealed that the oxygen atom of the C=O group participated in the formation of supramolecular architectures in all three compounds, and C=O…π bonding may be considered as the corresponding synthon (with increased separation in the case of compound 5). C-F…π bonding acts as a second synthon. F…F interactions in crystals 3–5 were classified as stabilizing or enforced.     

Generation of Perfluoro- and 1-Chloroperfluoro-Indanyl and -Benzocyclobutenyl Cations with Perfluoroalkyl Groups in the Aliphatic Ring

Russian Journal of Organic Chemistry - Perfluoro(alkylbenzocycloalken-1-yl) cations were generated in a SbF5?SO2ClF medium from perfluorinated indane and benzocyclobutene derivatives...     

Generation of perfluoro- and 1-chloropolyfluorobenzocycloalken-1-yl cations and their relative stability

Treatment of perfluorinated benzocyclobutene, indan, and tetralin with SbF₅-SO₂Cl₂, as well as of their 1,1-dichloro analogs with SbF₅, gave 1-chloropolyfluorobenzocycloalken-1-yl cations whose structure was studied by ¹⁹F and ¹³C NMR and confirmed by their transformations into perfluorinated ketones upon hydrolysis. Dissolution of perfluorinated benzocyclobutene, indan, and tetralin in excess SbF5 generated perfluorobenzocycloalken-1-yl cations in equilibrium with their precursors. The relative stability of perfluoro- and 1-chloropolyfluorobenzocycloalken-1-yl cations decreases as the size of the alicyclic fragment increases.