1978-04-7Relevant articles and documents
Opening of the four-membered ring in perfluorinated 1-alkyl-2-phenyl-and 1-aryl-1,2-dihydrocyclobutabenzenes in the system I2-SbF5
Mezhenkova,Karpov,Platonov
experimental part, p. 1026 - 1034 (2011/10/19)
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.
Selective mono-and diamination of polyfluorinated benzenes and pyridines with liquid ammonia
Vaganova,Kusov,Rodionov,Shundrina,Malykhin
, p. 2239 - 2246 (2008/09/20)
Amination of pentafluoropyridine, 2,3,5,6-tetrafluoropyridine, 4-chlorotetrafluoropyridine, 3,5-dichlorotrifluoropyridine, octafluorotoluene, α,α,α,2,3,5,6-heptafluorotoluene, decafluoro-m-xylene, decafluorobiphenyl, hexafluorobenzene, and pentafluorobenzene with liquid ammonia was investigated. Bis-aminodefluorination temperatures for the majority of substrates were shown to exceed significantly the corresponding temperatures of monoaminodefluorination. The optimal conditions for selective preparation of mono-and diaminopolyfluoro(het)arenes were elucidated. An efficient method for isolation of particular polyfluorophenylenediamines from product mixtures formed in nonselective reactions of pentafluorobenzene and hexafluorobenzene with aqueous ammonia based on complexation with a crown ether is proposed.
Oxygen replacement by fluorine in carbonyl derivatives of perfluoroaromatic compounds and isomerization of perfluoroindan-1,3-dione to perfluoro-3-methylenephthalide under the action of HF/SbF5
Zonov, Yaroslav V.,Karpov, Victor M.,Platonov, Vyacheslav E.,Rybalova, Tatjana V.,Gatilov, Yuri V.
, p. 1574 - 1583 (2008/09/18)
When acted upon by HF/SbF5 at 95 °C, carbonyl groups of perfluorinated acetophenone (10), 3,4-dihydronaphthalen-1(2H)-one (8), 2,3-dihydronaphthalene-1,4-dione (9), benzocyclobutenone (6), benzocyclobutenedione (7) and indan-1-one (1) are converted into difluoromethylene groups to give the corresponding perfluoroaromatic products. Perfluoroindan-2-one (5), under the same conditions, is transformed to bis(perfluoroindan-2-yl) ether (21). On heating with HF/SbF5, perfluoroindan-1,3-dione (2) isomerizes into perfluoro-3-methylenephthalide (4) at 95 °C, and gives 4,5,6,7-tetrafluoro-3-trifluoromethyl-phthalide (14) at 130 °C. Compound 4 in the absence of a solvent dimerizes giving perfluorodispiro[phthalide-3,1′-cyclobutane-2′,3″-phthalide] (18), and when heated with SbF5 at 130 °C, it is converted into perfluoro-3-methylphthalide (3). When acted upon by HF/SbF5 at 95 °C, perfluorinated benzoic acid (12) and phthalic anhydride (13) give the corresponding products with trifluoromethyl groups.
Reactions of tetrafluorophthalic and difluoropyromellitic acids with sulphur tetrafluoride
Dmowski, Wojciech
, p. 251 - 255 (2007/10/02)
Fluorination of tetrafluorophthalic acid (1) with an SF4/HF mixture at 190-300 deg C afforded, beside the expected perfluoro-o-xylene (2) and perfluoro-o-toluyl fluoride (4), considerable amounts of octafluoro-1,3-dihydroisobenzofuran (3).The reaction wit
REARRANGEMENT OF THE CARBON SKELETON OF PERFLUORINATED 1-ISOPROPYL-, 1-METHYL-1-ISOPROPYL-, AND 1-METHYL-2-ISOPROPYLBENZOCYCLOBUTENES BY THE ACTION OF ANTIMONY PENTAFLUORIDE
Karpov, V. M.,Mezhenkova, T. V.,Platonov, V. E.
, p. 1110 - 1114 (2007/10/02)
Perfluorinated 1-isopropyl-, 1-methyl-1-isopropyl-, and 1-methyl-2-isopropylbenzocyclobutenes isomerize under the influence of antimony pentafluoride to perfluorinated alkylstyrenes and alkylindans.The process may be accompanied by dealkylation and also by fluorination and defluorination of the products.With antimony pentafluoride at 50 deg C perfluoro-1-methyl-1-isopropylbenzocyclobutene gives perfluoro-α,β,β,o-tetramethylstyrene, which izomerizes under the influence of antimony pentafluoride at 130 deg C into perfluoro-1,2,2-trimethylindan, and the latter forms perfluoro-2,3-dimethylindene under the reaction conditions.Perfluoro-1-methyl-2-isopropylbenzocyclobutene is not changed in the presence of antimony pentafluoride at 50 deg C but isomerizes to perfluoro-1-isopropylindan at 90 deg C.The latter is transformed under these conditions into the above-mentioned tetramethylstyrene.Perfluoro-1-isopropylbenzocyclobutene does not react with antimony pentafluoride at 130 deg C, but at 170 deg C it gives a mixture of perfluorinated 2,2-dimethylindan, 2,3-dimethylindene, 2,3-dimethyl-4,5,6,7-tetrahydroindene, and 2-isobutyltoluene, which is converted into perfluoro-o-xylene under the reaction conditions. Keywords: Perfluoroalkylbenzocyclobutenes, perfluoroalkylstyrenes, perfluoroalkylindans, antimony pentafluoride, cationoid skeleton transformations.
