V. E. Platonov

Perfluorozinc aromatics by direct insertion of zinc into C–F or C–Cl bonds

Abstract For the first time perfluoroaromatic organozinc compounds were obtained by direct action of zinc on C–F bonds in the presence of metal salts (SnCl 2 , CuCl 2 , ZnBr 2 ). The reactions are accelerated by ultrasound. The scope of the method can be extended to polyfluoroaromatics which contain other halogen atoms (Cl) in the aromatic ring.

Interaction of perfluorobenzocycloalkenes with tetrafluoroethylene in the presence of SbF5

Abstract The reactions of perfluorinated tetralin, indan and benzocyclobutene with tetrafluoroethylene in the presence of SbF 5 led to the formation of the respective perfluoro-1-ethylbenzocycloalkenes transformed further to disubstituted derivatives. In the case of perfluorotetralin, the reaction gave perfluoro-1,4-diethyltetralin. Perfluorobenzocyclobutene gave perfluoro-1,1- and -1,2-diethylbenzocyclobutenes in about equal quantities, and perfluoroindan- practically only perfluoro-1,1-diethylindan. To explain this orientation, the electronic and steric effects are considered, which can influence the reactivity and the relative stability of the intermediate carbocations. The perfluoro-1-benzocyclobutenyl cation has been generated in the reaction of antimony pentafluoride with perfluorobenzocyclobutene.

Skeletal rearrangements in the reactions of perfluoro-1-methyl- and -1-ethyl-benzocyclobutenes with lewis acids

Abstract The reactions of perfluoro-1-methyl- and -1-ethyl-benzocyclobutenes with Lewis acids (SbF 5 , AlCl 3 , AlBr 3 ) have been studied. a four-membered ring expansion, unknown earlier in the halogenated series, has been found. The mechanism of the process differs from that for non-fluorinated analogues.

Skeletal transformations of perfluoro-1-phenylindan under the action of antimony pentafluoride

Abstract Perfluoro-1-phenylindan ( 1 ) was obtained from perfluoroindan and pentafluorobenzene in the presence of SbF 5 . Compound 1 heated with antimony pentafluoride at 170°C and then treated with water gave a mixture of perfluorinated 9-methylfluorene ( 5 ), 9-hydroxy-9-methylfluorene ( 6 ), 9-methyl-1,2,3,4,5,6,7,8-octahydroanthracene ( 7 ), 1,9-dimethyl-5,6,7,8-tetrahydro-β-naphthindan ( 8 ). When heated with SbF 5 in the presence of HF and then treated with water, compound 1 is transformed to a mixture of products 5 , 6 , perfluoro-1,2,3,4,5,6,7,8-octahydroanthracene ( 9 ), perfluoro-10-methyl-9(10H)anthracenone ( 10 ) and 10-H-perfluoro-10-methyl-9(10H)anthracenone ( 11 ).

Polyfluoroarylcarbonimidoyl dichlorides and chlorides. A new method of obtaining such compounds from polyfluoroaromatic amines and compounds of the CCl3R-type in the presence of AlCl3

Abstract Reactions of some polyfluorinated amines of the benzene, diphenyl, naphthalene and pyridine series with CCl 4 in the presence of AlCl 3 have been Investigated. A new method is proposed for producing polyfluoroarylcarbonimidoyl dichlorides Ar f NCCl 2 . The reaction is shown to be sufficiently general and applicable in the series of polychlorinated anilines and low-base anilines of the hydrocarbon series as well. The possibility of involving other compounds of the type CCl 3 R and other Lewis acids in the reaction has been studied. The factors influencing the course of the reaction and the mechanism of formation of polyfluoroarylcarbonimidoyl dichlorides are discussed.

Pentafluorophenylation of perfluorinated benzocyclobutene, indan, and tetralin by reaction with pentafluorobenzene in SbF5

The reactivity of perfluorinated benzocyclobutene, indan, and tetralin in reaction with pentafluorobenzene in SbF5 medium, and also the relative stability of generated therewith perfluoro-1-phenylbenzocycloalkenyl cations decrease with increasing alicyclic fragment in the benzocycloalkene. Treating the solutions of salts of the above cations with anhydrous HF results in the corresponding perfluoro-1-phenylbenzocycloalkenes, and the hydrolysis of salts furnishes their 1-hydroxy derivatives. In a reaction of 1-hydroxyperfluoro-1-phenylbenzocyclobutene, -indan, and -tetralin with SOCl2 the hydroxy group is replaced by chlorine. Besides with indan and tetralin derivatives form respectively 7-pentafluorophenyloctafluoro-3-chlorobicyclo[4.3.0]hepta-1,4,6-triene and 7-pentafluorophenyldecafluoro-3-chlorobicyclo[4.4.0]octa-1,4,6-triene.

Thermolytic transformations of polyfluoroorganic compounds XXIX. Formation of fluorine-containing styrenes by reactions of benzotrichloride and related compounds with dihalocarbene sources

Abstract Reactions of polyfluorobenzotrichlorides, benzotrichloride and α,α-dichloroperfluoroethylbenzene with sources of difluorocarbene and other dihalocarbenes lead to the formation of polyfluorostyrenes. Formation of polyfluorostyrenes is shown to proceed possibly by initial dihalocarbene insertion into the CCl bond of the benzylic position with subsequent dechlorination of the resulting product.

Reactions of polyfluoroaromatic imidoyl chloride derivatives with S-nucleophilic reagents

Abstract The interactions of N -pentafluorophenylcarbonimidoyl dichloride, N -pentafluorophenylbenzimidoyl chloride and N -pentafluorophenyl (C-pentafluorophenyl) imidoyl chloride with the S-nucleophilic reagents thiourea, sodium N,N -diethyldithiocarbamate, thiocarbonyl difluoride and bis(trifluoromethyl)trithiocarbonate in the presence of CsF or AgSCF 3 , or thiophenol and polyfluorinated thiophenols in the presence of anhydrous K 2 CO 3 , were studied. Reactions with charged S-nucleophiles and with S-nucleophiles in the presence of a base proceeded with preservation of the N-C multiple bond in the reaction products. By varying the reaction conditions in the case of N -pentafluorophenylcar-bonimidoyl dichloride it was possible to substitute one or two chlorines and obtain mono- or di-thioimidates. When C 6 F 5 or SC 6 F 5 groups were present at the C atom of the N-C multiple bond, preferential substitution of the para -fluorine atom occurred. Semiempirical PM3 calculation data were used to explain the direction of these reactions. N -Pentafluorophenylcarbonimidoyl dichloride reacted with sodium N , N -diethyldithiocarbamate or thiourea to give pentafluorophenylisothiocyanate. Depending on the conditions of the reactions of polyfluorinated benzimidoyl chlorides with thiourea, N -pentafluorophenylthioamides and 2-aryl-4,5,6,7-tetrafluorobenzothiazoles were formed. An attempt to produce SCF 3 derivatives from AgSCF 3 was unsuccessful.

Reaction of perfluorinated 1-ethyl-, 1,1-diethyl-, and 1,2-diethylcyclobutabenzenes with pentafluorobenzene in SbF5

Perfluoro(1-ethyl-1,2-dihydrocyclobutabenzene) reacts with pentafluorobenzene in SbF5 to give perfluoro(1-ethyl-2-phenyl-1,2-dihydrocyclobutabenzene). Analogous reaction of a mixture of perfluoro(1,1-diethyl-1,2-dihydrocyclobutabenzene) and perfluoro(1,2-diethyl-1,2-dihydrocyclobutabenzene) leads to the formation (after hydrolysis of the reaction mixture) of perfluorinated 7-phenyl-8,8-diethylbicyclo[4.2.0]octa-1,4,6-trien-3-one, 1,1-diethyl-2-(4-oxocyclohexa-2,5-dienylidene)-1,2-dihydrocyclobutabenzene, and 2-(pent-2-en-3-yl)benzophenone (from the 1,1-isomer) and perfluorinated (E)-1,2-diethyl-1-phenyl-1,2-dihydrocyclobutabenzene, 7,8-diethyl-8-phenylbicyclo[4.2.0]octa-1,4,6-trien-3-one, and 1-[2-(1-phenylprop-1-en-1-yl)-phenyl]propan-1-one (from the 1,2-isomer).

Thermolytic reactions of polyfluoroorganic compounds XVII. Synthesis and pyrolysis of polyfluorophenylcyclopropanes

Abstract Synthesis of perfluorophenylcyclopropane (I) and I-chloro-I-pentafluorophenyltetrafluorocyclopropane (II) is described and their pyrolysis at 620°C is studied. Pyrolysis of compounds (I) and (II) is shown to give perfluorostyrene (III) and α - chloroheptafluorostyrene (IV) as the main products, together with a small amount of perfluoroindan (V) and I-chlorononafluoroindan (VI), respectively. Styrene (III) was obtained by bromofluorination of styrene (IV) and subsequent dehalogenation of the resultant α - chloro- β - bromooctafluoroethylbenzene (VII).