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The reaction of polyfluoroaromatic organozinc compounds with oxalyl chloride in DMF proceeds involving the Vilsmeier–Haack reagent with the formation of polyfluoroaromatic aldehydes as the major products. The use of CuI makes it possible to increase the yield of the target aldehydes.

The reaction of 4-X-substituted 1-[(difluoromethyl)sulfinyl]-2,3,5,6-tetrafluorobenzenes (X = CF3, H, OMe) with methylamine and ammonia in MeCN, Et2O, and hydrocarbons occurs involves nucleophilic substitution in position 2 of the substrate. The reaction time increases with increasing donor ability of substituent X in the series X = CF3 < H < OMe, as well as with decreasing solvent polarity. Further substitution of fluorine in position 6 of the substrate by methylamine is also possible, but requires a higher reaction temperature. The reaction of ammonia with 1-[(difluoromethyl)sulfinyl]-4-methoxy-2,3,5,6-tetrafluorobenzene is accompanied by partial demethylation to form 2-[(difluoromethyl)sulfinyl]-3,4,6-trifluoro-5-methoxy-N-methylaniline and 4-[(difluoromethyl)sulfinyl]-2,3,5,6-tetrafluorophenol.

Pyrolysis of a mixture of 2,5-difluoro-3,4,6-trichlorobenzenethiol with tetrafluoroethylene leads to 2,2,3,3,4,7-hexafluoro-5,6-dichloro-2,3-dihydrobenzo[b]thiophene (the major reaction product) along with 2,2,3,3,4,6-hexafluoro-5,7-dichloro-2,3-dihydrobenzo[b]thiophene. Schemes of their formation with the participation of intermediate radicals are proposed. Oxidation of a mixture of the synthesized compounds gave 2,2,3,3,4,7-hexafluoro-5,6-dichloro-2,3-dihydrobenzo[b]sulfane-1,1-dioxide and 2,2,3,3,4,6-hexafluoro-5,7-dichloro-2,3-dihydrobenzo[b]sulfane-1,1-dioxide.

To develop a modern plague vaccine, we used hypo-endotoxic Yersinia pestis bacterial ghosts (BGs) with combinations of genes encoding the bacteriophage ɸX174 lysis-mediating protein E and/or holin-endolysin systems from λ or L-413C phages. Expression of the protein E gene resulted in the BGs that retained the shape of the original bacterium. Co-expression of this gene with genes coding for holin-endolysin system of the phage L-413C caused formation of structures resembling collapsed sacs. Such structures, which have lost their rigidity, were also formed as a result of the expression of only the L-413C holin-endolysin genes. A similar holin-endolysin system from phage λ containing mutated holin gene S and intact genes R-Rz coding for the endolysins caused generation of mixtures of BGs that had (i) practically preserved and (ii) completely lost their original rigidity. The addition of protein E to the work of this system shifted the equilibrium in the mixture towards the collapsed sacs. The collapse of the structure of BGs can be explained by endolysis of peptidoglycan sacculi. Immunizations of laboratory animals with the variants of BGs followed by infection with a wild-type Y. pestis strain showed that bacterial envelopes protected only cavies. BGs with maximally hydrolyzed peptidoglycan had a greater protectivity compared to BGs with a preserved peptidoglycan skeleton.

Dodecafluoro-2H,3H,5H,6H,7H-indeno[5,6-b]thiophene has been synthesized as the major product of co-pyrolysis of 6-bromo-, 6-chlorooctafluoroindane-5-thiols, or bis(6-bromo-5-perfluoroindanyl)disulfane with tetrafluoroethylene under flow conditions at 400-625oC, along with small amount of tetradecafluoro-1,2,3,5,6,7-hexahydro-s-indacene. Dodecafluoro-2H,3H,5H,6H,7H-indeno[5,6-b]thiophene formed in the reaction of 6-(meth-ylsulfanyl)octafluoroindane-5-thiol with tetrafluoroethylene at 420oC has been isolated, and its structure has been confirmed by X-ray diffraction analysis. The schemes of the products formation involving intermediate radicals have been proposed.

Currently, the chemistry of organofluorine compounds is a leading and rapidly developing area of organic chemistry. Fluorine present in a molecule largely determines its specific chemical and biological properties. This thematic issue covers the trends of organofluorine chemistry that have been actively developed in Russia the last 15 – 20 years. The review describes nucleophilic substitution and heterocyclization reactions involving fluorinated arenes and quinones and skeletal cationoid rearrangements in the polyfluoroarene series. The transformations involving CF3-substituted carbocations and radical cations are considered. Heterocyclization and oxidative addition reactions of trifluoroacetamide derivatives and transformations of the organic moiety in polyfluorinated organoboranes and borates with retention of the carbon – boron bond are discussed. Particular attention is devoted to catalytic olefination using freons as an efficient synthetic route to fluorinated compounds. The application of unsymmetrical fluorine-containing N-heterocyclic carbene ligands as catalysts for olefin metathesis is demonstrated. A variety of classes of organofluorine compounds are considered, in particular, polyfluorinated arenes and 1,2-diaminobenzenes, 1-halo-2-trifluoroacetylacetylenes, α-fluoronitro compounds, fluorinated heterocycles, 2-hydrazinylidene-1,3-dicarbonyl derivatives, imines and silanes. The potential practical applications of organofluorine compounds in fundamental organic chemistry, materials science and biomedicine are outlined. The bibliography includes 1019 references.

Zinc(II) complexes with 1,10-phenanthroline and tetrafluoroterephthalate and octafluorobiphenyl 4,4′-dicarboxylate anions have been synthesized. According to the IR spectral data, the complexation involves coordination of the metal ion to the nitrogen atoms of phenanthroline and carboxylate oxygen atom of the acid anion. The complexes show photoluminescence in the visible region of the spectrum. The structure of the complex salt [Zn(H2O)6][Zn(H2O)4(L2)2] · H2O, where L2 is octafluorobiphenyl-4,4′-dicarboxylate anion (monodentate ligand), has been determined by X-ray analysis.

We present a series of six novel Zn(II) complexes containing anions of perfluorinated biphenyl-4,4′-dicarboxylate (oFBPDC2−). Among them are the 0D complex [Zn(eg)3](oFBPDC) (eg = ethylene glycol), the 1D [Zn(H2O)(ur)(oFBPDC)] (ur = urotropine) and [Zn(CH3OH)2(CH3OCH2CH2OH)(oFBPDC)] and the 2D layered [Zn2(CH3CN)2(oFBPDC)2]·2C6H6·2CH3CN, [Zn2(H2O)2(oFBPDC)2]·4(CH3)2CO, [{Zn4(μ3-OCH3)4}(CH3OH)4(oFBPDC)2]·[{Zn4(μ3-OCH3)4}(H2O)(CH3OH)3(oFBPDC)2]·13CH3OH. The latter coordination polymer is built up by unique Zn4(OCH3)4 cuboidal units. The complexes are characterized by single-crystal X-ray diffraction, FT-IR, elemental analysis, and TGA. Investigation of the CO2 adsorption at 195 K on [Zn2(CH3CN)2(oFBPDC)2] and [Zn2(H2O)2(oFBPDC)2] of the layered polymeric structure revealed that they have BET surface areas of 334.8 and 150.6 m2 g−1, respectively.

Co-pyrolysis of 2,5-dichloro-3,4,6-trifluorobenzenethiol, 2-chloro-4-trifluoromethyl-3,5,6-trifluorobenzenethiol, and 3-chloro-2,5,6-trifluoropyridine-4-thiol with tetrafluoroethylene has given, heptafluoro-5- chloro-2,3-dihydrobenzo[b]thiophene, 6-trifluoromethylheptafluoro-2,3-dihydrobenzo[b]thiophene, and heptafluoro- 2H,3H-thieno[2,3-c]pyridine, respectively, as the major products. The reactions of these thiols containing the chlorine atom in the ortho-position to the thiol group differ from that between 4-chloro-2,3,5,6- tetrafluorobenzenethiol and tetrafluoroethylene, the latter one giving perfluoroindane as the major product.

Polyfluorinated indans and tetralins are carbonylated under the action of CO/SbF5 at room temperature and atmospheric pressure. Perfluoroindan and its 4-CF3, 5-CF3, 5-CH3, 1,1-H,H derivatives add two CO molecules to form the corresponding dimethyl indan-1,1-dicarboxylates after methanolysis, and/or 1-hydroindan-1-carboxylic acids after hydrolysis. 1-X-Perfluoroindans (X CF3, C2F5, C6F5, H) and 1-X-perfluorotetralins (X C2F5, C6F5) add one CO molecule at the 1-position to give the corresponding 1-carbonyl fluorides. Reaction of the latter with methanol gives methyl esters, whereas hydrolysis is accompanied by decarboxylation. Perfluoro-2,3-dihydrobenzofuran under the action of CO/SbF5 gives both mono- and dicarbonylation products.

In contrast to aromatic carboxylates, the coordination polymers based on their perfluorinated analogues are not numerous. Here we present a series of six Zn(II) coordination polymers of different dimensionalities (1D, 2D, and 3D) and porosities based on octafluorobiphenyl-4,4′-dicarboxylate (oFBPDC2−) and N-containing co-ligands (ur, dabco, and bpy). These complexes are characterized by single-crystal X-ray diffraction, PXRD, FT-IR, elemental analysis, and TGA. The metal–organic frameworks [Zn2(CH3CONH2)2(oFBPDC)2] (1) and [Zn2(oFBPDC)2(dabco)] (4) are shown to be porous with BET surface areas of 470 m2 g−1 and 441 m2 g−1, respectively. In addition, compound 4 shows selectivity factors of 11.3, 4.9 and more than 6 for the binary gas mixtures CO2/N2, CO2/CH4 and benzene/cyclohexane, respectively. The measurements for pressed powders and water droplet give water contact angles of 136° for 4 and 133° for (H2bpy)[Zn2(bpy)(oFBPDC)3] (5). Low water uptake indicates that both 4 and 5 belong to highly hydrophobic solids.

Reactions of 1-(difluoromethanesulfinyl)pentafluorobenzene with sodium methoxide, sodium phenoxide, potassium hydrosulfide, and methylamine resulted in substitution of fluorine atom in the 4-position (in the reaction with methylamine, also in the 2-position). Treatment of the title compound with sodium hydroxide afforded pentafluorobenzene due to cleavage of the Carom‒S bond.

Intravenous ribavirin has been reported to be an effective treatment for haemorrhagic fever with renal syndrome (HFRS) caused by Hantaan virus in Asia. However, its therapeutic benefits for HFRS caused by Puumala virus (PUUV) in Europe are still unknown.A randomized, open-label study of efficacy and safety of intravenous ribavirin in the treatment of HFRS was conducted in the European part of Russia. Seventy-three patients with suspected HFRS within 4 d of the onset of the disease were randomized to receive either intravenous ribavirin (33 mg/kg, followed by 16 mg/kg given every 6 h for 4 d and by 8 mg/kg given every 8 h for 3 d) plus standard therapy (n = 37) or standard therapy alone (n = 36). The primary outcome was the average change from baseline in viral load over time estimated as area under the viral load curve minus baseline (AUCMB). Fifty-five patients with HFRS confirmed by nested reverse transcriptase - polymerase chain reaction (PCR) assay were included in the assessment of the efficacy. All patients entered into the clinical trial were included in the assessment of the safety.PUUV was detected in all cases of confirmed HFRS. Viral load kinetics were similar in both treatment groups. Significantly more patients receiving ribavirin than standard therapy experienced low haemoglobin level (95% vs 36%), hyperbilirubinemia (81% vs 3%), sinus bradycardia (43% vs 14%), and rash (19% vs 0%).Results of the study showed insufficient efficacy and safety of intravenous ribavirin in the treatment of HFRS caused by PUUV.

1,2,4-Trichlorotrifluorobenzene reacted with potassium hydrogen sulfide, potassium hydroxide, sodium isopropoxide, liquid ammonia, and ethyl cyanoacetate via nucleophilic substitution of one fluorine atom with predominant formation of the isomer in which the new substituent replaced fluorine atom in the 5-position.

New process direction was found in the reaction of polyfluoroarenethiols with fluorodichloromethane, chloroform, and bromoform in an alkaline medium consisting in the replacement of the thiol group by a hydrogen atom. This process competes with the formation of expected products, dihalomethyl polyfluoro-aryl sulfides and tris(arylsulfanyl)methanes. In reaction of 2,3,5,6-tetrafluorobenzenethiol with dichloro-methane bis(2,3,5,6-tetrafluorophenylsulfanyl)methane was obtained. Reactions of polyfluoroarenethiols with pentafluorobenzyl chloride occur mainly with the substitution of the chlorine atom, with pentafluorobenzal chloride and with pentafluorobenzotrichloride a substitution of a fluorine atom in the para-position takes place.

Symmetrical and unsymmetrical perfluorinated biaryls have been synthesized by reactions of perfluorinated benzonitrile, nitrobenzene, toluene, m-xylene, and pyridine with perfluoroarylzinc compounds derived from chloropentafluorobenzene, octafluorotoluene, and pentafluoropyridine. The described transformations may be regarded as nucleophilic aromatic substitution.

Synthesis of pentafluorobenzenesulfonyl bromide from pentafluorobenzenethiol, bromine and hydrogen peroxide is presented. Reactions of pentafluorobenzenesulfonyl bromide with primary alkenes (1-hexene, 3-chloro-1-propene and 3-bromo-1-propene) in solvent-free conditions are described.

The Ln2(H2O)4(L)3·2H2O and Ln2(phen)2(L)3·2H2O complexes [Ln = Eu(III), Sm(III), or Dy(III); H2L = C6F4(COOH)2, phen = 1,10-phenanthroline] have been prepared. Structures of the prepared compounds have been confirmed by X-ray diffraction and IR spectroscopy studies. The complexes of Eu(III) have exhibited red photoluminescence stronger than that of the complexes of Sm(III) and Dy(III).

Carbonylation of polyfluorinated benzocyclobutenes with CO in an SbF 5 medium readily proceeds at room temperature and atmospheric pressure and it is followed by four-membered ring transformations. Perfluorinated benzocyclobutene, 3- and 4-methyl-benzocyclobutenes add two CO molecules to form, after ring opening and following heterocyclization, isochromene derivatives. Hydrolysis of the reaction mixtures gives corresponding 4-carboxy-1 H -isochromenes and 2-(carboxymethyl)benzoic acids. The carbonylation of perfluorinated 1-methyl-, 1-ethyl- and 1-isopropyl-benzocyclobutene gives salts of 2-(2-methylphenyl)alk-2-enoyl cations and the corresponding acids after hydrolysis of the latters. Perfluoro-1-phenylbenzocyclobutene in the reaction with CO–SbF 5 transforms into a salt of perfluro-4-phenylisochromenyl cation, its hydrolysis gives perfluro-4-phenylisochromen-1-one.

Chloromethylation of p-toluic acid affords 3,5-bis(chloro- methyl)-4-methylbenzoic acid whose subsequent treatment with arenethiols brings about spacer dendrimeric blocks containing polyfluoroarylsulfanyl fragments in a total yield of 60-75%.

A new thiolate cluster complex (Bu4N)2[Mo6I8(SC6F4H)6] was synthesized by the metathesis reaction of (Bu4N)2[Mo6I14] and HC6F4SAg in methylene chloride. According to the X-ray structure determination, the cluster core {Mo6I8}4+ coordinates six thiolate ligands 2,3,5,6-HC6F4S−. The Mo-Mo and Mo-I distances have their usual values. The average Mo-S distance is 2.538(4) A, and the Mo-S-C angles range from 107 to 109°. Compound (Bu4N)2[Mo6I8(SC6F4H)6] both in solid and in solution displays a bright red microsecond luminescence, which is typical of octahedral molybdenum halide complexes.

Reactions of perfluorobenzocycloalkenes (ArFF) with methyllithium and ethyl cyanoacetate involved replacement of fluorine atoms in positions 3 and 4 of perfluorocyclobutabenzene, position 5 of perfluoroindan, and position 6 of perfluorotetralin by CH3 and CH(CN)COOEt groups. Hydrolysis of the resulting esters ArFCH(CN)COOEt gave the corresponding perfluoroarylacetic acids ArFCH2COOH which were converted into dichloroacetyl chlorides ArFCCl2COCl by treatment with PCl5. The reaction of ArFCCl2COCl with SbF5 produced trifluoromethyl derivatives ArFCF3. Decarboxylation of ArFCCl2COOH in DMF afforded dichloromethyl derivatives ArFCCl2H which reacted with CsF on heating to form difluoromethyl analogs ArFCF2H.

Heating of perfluorinated 1-methyl-, 1-ethyl- and 1-isopropylbenzocyclobutenes with SiO2 in an SbF5 medium at 75 °C results in perfluoro-2-alkylbenzocyclobutenones or perfluoro-3-alkylphthalides formation. Perfluorinated 1,2-diethyl- and 1-ethyl-2-methylbenzocyclobutenes react with SiO2/SbF5 at 75 °C to form, after treatment of the reaction mixture with water, perfluorinated 1,3-diethyl- and 1-ethyl-3-methylphthalan-1,3-diol, respectively. Perfluoro-1,2-diisopropylbenzocyclobutene under the action of SiO2/SbF5 at 95 °C is converted to perfluoro-7,8-diisopropylbicyclo[4.2.0]octa-1,5,7-triene-3,4-dione and perfluoro-1,2-diisobutyrylbenzene. Perfluoro-1-methyl-2-phenylbenzocyclobutene does not react with SiO2 in an SbF5 medium at 75 °C, perfluoro-1-phenylbenzocyclobutene in analogous conditions gives a mixture of perfluorinated 2-hydroxy-2-phenylbenzocyclobutenone and 2-benzoylbenzoic acid.

The reaction of perfluoro(1-phenyl-1,2-diethyl-1,2-dihydrocuclobutabenzene) with SbF5 at 20°C, followed by treatment of the reaction mixture with water gave perfluoro {4-[1-(2-propylphenyl)propylidene]-2,5-cyclohexadien-1-one} together with perfluoro[4b,10-diethylbenzo[a]azulen-7(4bH)-one] resulting from unusual expansion of the pentafluorobenzene ring to seven-membered ring. Analogous reaction at 90°C, apart from the above compounds, afforded perfluorinated 10-ethyl- and 3,10-diethylbenzo[a]azulen-6(10H)-ones via elimination of C2F5 group from the seven-membered ring or its migration to the benzene ring.

Heating of perfluorinated 1-methyl- and 1-ethyltetralins with SiO 2 in an SbF 5 medium at 100 °C results in perfluoro-4-alkyltetralin-1-ones formation. Perfluoro-4-methyltetralin-1-one, under the action of SbF 5 at 180 °C with subsequent treatment of the reaction mixture with water, is converted to perfluoro-3,3-dimethylindan-1-one and perfluoro-3,4-dimethylisochromen-1-one. Perfluoro-4-ethyltetralin-1-one, under similar conditions, forms perfluoro-3-ethyl-3-methylindan-1-one, perfluoro-4-ethyl-3-methylisochromen-1-one and perfluoro-2-methyltetralin. Reaction of perfluorotetralin-1-one with pentafluorobenzene in the presence of SbF 5 at 50–55 °C leads to the formation of perfluoro-4-phenyltetralin-1-one, which under the action of SbF 5 at 75 °C isomerizes into perfluoro-3-methyl-3-phenylindan-1-one. Heating of the latter with SbF 5 at 75–95 °C gives, after treatment of the reaction mixture with water, perfluoro-2-(2-methylphenyl)-3-phenylpropenoic acid and perfluoro-4-methyl-3-phenylisochromen-1-one.

3-(1-Amino-2,2,2-trifluoroethyliden)-1,1,4,5,6,7-hexafluoro-2-iminoindan (1) and 3-(1-amino-2,2,2-trifluoroethyliden)-1,1,4,5,6,7-hexafluoro-2-methyliminoindan (7) reacted with SOCl2 to give previously unknown 4a-chloro-5,6,7,8,9,9-hexafluoro-4-(trifluoromethyl)-4a,9-dihydroindeno[2,1-c][1,2,6]thiadiazine (2) and 5,6,7,8,9,9-hexafluoro-1-methyl-4-(trifluoromethyl)-1,9-dihydroindeno[2,1-c][1,2,6]thiadiazine 2-oxide (8), respectively. When treated with methanol, compound 2 formed 5,6,7,8,9,9-hexafluoro-4a-methoxy-4-(trifluoromethyl)-4a,9-dihydroindeno[2,1-c][1,2,6]thiadiazine (9), whereas the reaction with water gave 5,6,7,8,9,9-hexafluoro-4-(trifluoromethyl)-3,9-dihydroindeno[2,1-c][1,2,6]thiadiazine 2-oxide (5). The latter reacted with SOCl2, acetyl chloride and trifluoroacetic anhydride to give compound 2, 5,6,7,8,9,9-hexafluoro-4-(trifluoromethyl)-4a,9-dihydroindeno[2,1-c][1,2,6]thiadiazin-4a-yl acetate (13) and trifluoroacetate 15, respectively. Solution of compound 2 in trifluoromethanesulfonic acid generated 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-9H-indeno[2,1-c][1,2,6]thiadiazinylium (11), which was transformed, under the action of water, to sulfoxide 5. The structures of compounds 8, 9, 13 were confirmed by single crystal X-ray diffraction. The reaction pathways were analyzed on the basis of DFT calculations

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.

The reaction of perfluoro(1-methyl-1-phenyl-1,2-dihydrocyclobutabenzene) with SbF5 at 50°C, followed by hydrolysis, gave perfluoro(1-phenylindan-1-ol), while analogous reaction at 90°C afforded perfluoro[10-methylanthracen-9(10H)-one]. Perfluoro(1-methyl-2-phenyl-1,2-dihydrocyclobutabenzene) did not undergo skeletal transformations under analogous conditions, whereas at 200°C it was converted mainly into perfluoro(9-methylfluoren-9-ol). Perfluoro(1-ethyl-2-phenyl-1,2-dihydrocyclobutabenzene) reacted with SbF5 at 200°C to form perfluoro(9-ethylfluoren-9-ol) together with perfluorinated 9,9-dimethyl- and 9-ethyl-9-methyl-1,2,3,4-tetrahydro-9H-fluorenes.

Reactions of polyfluoroarenesulfonyl bromides 4-XC6F4SO2Br (X = F, H, Cl, Br, CF3) with allyl bromide gave 84–94% of the corresponding allyl polyfluoroaryl sulfones.

The heating of perfluoro-3,3-diethylindan-1-one with SbF5 at 180°C after treatment of the reaction mixture with anhydrous HF afforded perfluoro-1,3-dimethyl-4-ethylisochromen, and after hydrolysis, perfluoro-1,3-dimethyl-4-ethyl-1H-isochromen-1-ol. The latter under the action of NaHCO3 converted into 5,6,7,8-tetrafluoro-1,3-bis(trifluoromethyl)-1H-isochromen-1-ol. Both isochromenols reacted with SOCl2 gave the corresponding polyfluoro-1-chloro-1H-isochromens. On dissolving isochromenols in CF3SO3H and isochromens in SbF5 perfluoro-1,3-dimethyl-4-ethylisochromenyl and 5,6,7,8-tetrafluoro-1,3-bis(trifluoromethyl)isochromenyl cations were generated which by hydrolysis were converted into the corresponding isochromenols.

The first general methodology has been developed for the synthesis of polyfluoroarenesulfonyl bromides from polyfluoroarenethiols. At heating of polyfluoroarenethiols with a mixture of Br2 and fuming HNO3 or Br2, HNO3 and H2SO4 polyfluoroarenesulfonyl bromides were obtained in good yields.

Interaction of perfluoro-1-ethyl-1-phenylbenzocyclobutene with SbF5 at room temperature gives, after treatment of the reaction mixture with H2O, perfluoro-4-[1-(2-methylphenyl)propylidene]cyclohexa-2,5-dienone as a main product. The reaction at 90–95 °C leads, after treatment with H2O, to a mixture of perfluorinated 9-ethyl-9-methyl-1,2,3,4-tetrahydro-9H-fluorene, 9-ethyl-4a-methyl-4,4a-dihydrofluoren-1-one, 3-ethyl-3-phenylphthalide, 1-hydroxy-2-methyl-1-phenylindan, 3-methyl-2-phenylindenone and small amounts of other products.

Polymer films with hydrophobic surface properties were prepared from hexafluorobenzene in a direct-current discharge. The films possess good dielectric characteristics (dielectric loss tangent and permittivity) in the temperature range 20–240°C. The composition and structure of this polymer were studied by means of IR spectroscopy and electron spectroscopy for chemical analysis with reference to mass-spectrometric data for the discharge gas phase.

The reaction of perfluorinated benzocyclobutene and tetraline with SiO2-SbF5 led to the formation in a high yield of their mono- and further dicarbonyl derivatives. The monocarbonyl derivatives on heating with SbF5 underwent disproportionation into the corresponding perfluorobenzocycloalkenes and diketones. Both mono- and diketones in the SbF5 medium are liable to suffer skeleton rearrangements yielding five- and six-membered oxygen-containing heterocycles and/or products of the opening of the alicyclic fragment of the substrate, and from the perfluorobenzocyclobutenone compounds were also obtained with a number of carbon atoms greater than that of the initial ketone.

Perfluoro-1,2-diethyl-1-phenylbenzocyclobutene under the action of SbF5 gives, after treatment of the reaction mixture with water, perfluoro-4-[1-(6-propyl-phenyl)-propylidene]cyclohexa-2,5-dienone along with the products of unusual pentafluorobenzene ring expansion – perfluorinated 4b,10-diethylbenzo[a]azulen-7(4bH)-one and 10-ethylbenzo[a]azulen-6(10H)-one.

Organozinc compounds of the general formula ArFZnX (X = Cl, ArF) were synthesized by reactions of Zn with chloropolyfluoroarenes and of Zn/SnCl2 with polyfluoroarenes. Polyflorinated organozinc compounds reacted with allyl chloride and allyl bromide to give the corresponding allyl-substituted polyfluoroarenes. The reactions with allyl chloride were carried out in the presence of copper(I) salts (CuCl or CuI).

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).

Single crystals of complexes of 3-(1-amino-2,2,2-trifluoroethylidene)-2-imino-1,1,4,5,6,7-hexafluoroindan (1) with 1,4-dioxane, pyrazine, and pyridine have been synthesized. Their structure was investigated by X-ray analysis. In crystals of the dioxane complex, compound 1 is present together with its tautomer — 2-amino-3-(1-imino-2,2,2-trifluoroethyl)-1,1,4,5,6,7-hexafluoroindene (1a), and these compounds are in an equilibrium ratio of ∼60:40. Gas-phase quantum chemical calculations have been performed to examine the possibility of a tautomeric equilibrium of enaminoimine 1 in the corresponding complexes.

Acetic acid-catalyzed condensation of 2-amino-3-(1-imino-2,2,2-trifluoroethyl)-1,1,4,5,6,7-hexafluoroindene (1b) with acetone and cyclopentanone gives 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-2,3-dihydro-1,3-diazafluorene (2a) and 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-2,3-dihydro-1,3-diazafluorene-2-spiro-1′-cyclopentane (3a) together with small amounts of 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-1,2-dihydro-1,3-diazafluorene (2b) and 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-1,2-dihydro-1,3-diazafluorene-2-spiro-1′-cyclopentane (3b), respectively. When acted upon by (CH3)2SO4 compounds 2, 3 were converted into corresponding fluorine-containing 1-methyl-1,2-dihydro-1,3-diazafluorenes 6, 7. 4a-Chloro-5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-2,4a-dihydro-1,3-diazafluorene (8) has been synthesized by the interaction of compound 2 with SOCl2. Solution of compound 2 as well as 8 in CF3SO3H-CD2Cl2 generated 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-1,2,3,4-tetrahydro-1,3-diazafluorene-4-yl cation (2c). The structures of compounds 2, 3, 6–8 have been determined by single crystal X-ray diffraction.

3-(1-Amino-2,2,2-trifluoroethylidene)-2-imino-1,1,4,5,6,7-hexafluoroindan (2) and its N-methyl and N,N′-dimethyl derivatives were synthesized by the reaction of perforo-1-ethylideneindan with ammonia and methylamine or by methylation of compound 2 with dimethylsulfate. Single crystals were grown and the molecular and crystal structure of the emaninoimine products was investigated. The density functional theory (DFT) quantum chemical calculations were performed to determine possible tautomeric equilibrium of the emaninoimine products.

The reaction of perfluoro(1-ethyltetrahydronaphthalene) with pentafluorobenzene in SbF5, followed by treatment of the reaction mixture with water, afforded a mixture of 1-hydroxyperfluoro(1-phenyl-4-ethyletetrahydronaphthalene) and perfluoro(5-phenyl-8-ethyl-2,6,7,8-tetrahydronaphthalen-2-one). From perfluoro(1,1-diethylindan), 1-hydroxyperfluoro(1,1-diethyl-3-phenylindan) was obtained. Perfluoro(1-ethylindan) reacted with an equimolar amount of pentafluorobenzene in SbF5 to give (after hydrolysis) 1-hydroxyperfluoro-(3-ethyl-1-phenylindan), 1-hydroxyperfluoro(3-ethyl-1,3-diphenylindan), and perfluoro(1-ethyl-1-phenylindan), while in the reaction with excess pentafluorobenzene, followed by treatment with anhydrous hydrogen fluoride, perfluoro(1-ethyl-3-phenylindan) and perfluoro(1-ethyl-1,3-diphenylindan) were formed.

This review deals with syntheses and reactivity of polyfluoroarenes with a N CClR group (including those with R Cl). The most promising and convenient methods of synthesis of these type compounds are based on co-pyrolysis reactions of low-basic polyfluoroaromatic amines with RCCl3 type derivatives and the interaction of such amines and polyfluoroaromatic hydrazines with RCX3 (X Cl,F) compounds in the presence of AlCl3 at moderate temperature; they have no analogues in the nonfluorinated series. Reactions with different nucleophilic reagents, the formation of electrophilic intermediates of the nitrilium cation type and reactions of the latter with aromatic and fluoroaromatic hydrocarbons, amines, and compounds with C N, C≡N and C O multiple bonds are described. It is shown that polyfluoroaromatic compounds with a N CClR group are promising precursors for syntheses of a wide range of compounds of various classes, including heterocyclic derivatives.

Reactions of N-(perfluorophenyl)carbonimidoyl dichloride with benzoic acid, benzoyl chloride, ethyl benzoate, and also with phthalic acid, phthaloyl dichloride, and phthalic anhydride in the presence of AlCl3 at 170°C afford2-(perfluorophenyl)isoindoline-1,3-dione. With benzoic acid and benzoyl chloride form also 2-(perfluorophenyl)-3-[(perfluorophenyl)imino]isoindolin-1-one. In reactions with compounds of the benzene series arise also derivatives of arylimidoyl chlorides and amide type compounds containing a CONHC6F5 moiety.

There are numerous studies to indicate that irradiation induces reactive oxygen species (ROS), which play an important causative role in radiation damage of the cell. We evaluated the effects of ginsan, a polysaccharide fraction extracted fromPanax ginseng, on the γ-radiation induced alterations of some antioxidant systems in the spleen of Balb/c mice. On the 5th day after sublethal whole-body irradiation, homogenized spleen tissues of the irradiated mice expressed only marginally increased mRNA levels of Mn-SOD (superoxide dimutase) in contrast to Cu/Zn-SOD, however, catalase mRNA was decreased by ∼50% of the control.In vivotreatment of non-irradiated mice with ginsan (100 mg kg−1, intraperitoneal administration) had no significant effect, except for glutathione peroxidase (GPx) mRNA, which increased to 144% from the control. However, the combination of irradiation with ginsan effectively increased the SODs and GPx transcription as well as their protein expressions and enzyme activities. In addition, the expression of heme oxygenase-1 and non-protein thiol induced by irradiation was normalized by the treatment of ginsan. Evidence indicated that transforming growth factor-β and other important cytokines such as IL-1, TNF and IFN-γ might be involved in evoking the antioxidant enzymes. Therefore, we propose that the modulation of antioxidant enzymes by ginsan was partly responsible for protecting the animal from radiation, and could be applied as a therapeutic remedy for various ROS-related diseases.

Reactions of 2-amino-3-(1-imino-2,2,2-trifluoroethyl)hexafluoro-1H-indene with carboxylic acid anhydrides and chlorides afforded 2-alkyl(aryl)-4-trifluoromethyl-5,6,7,8,9,9-hexafluoro-1,3-diazafluorenes. The molecular and crystalline structure of the products was studied by NMR spectroscopy and X-ray diffraction. 5,6,7,8,9,9-Hexafluoro-2-phenyl-4-trifluoromethyl-1,3-diazafluorene in crystal gives rise to infinite ladder chains via π-stacking interaction between the benzene ring of one molecule and tetrafluorobenzene fragment of the other.

Perfluoro-1-phenyltetralin ( 1 ) heated with antimony pentafluoride at 130 °C, then treated with water, gave a mixture of perfluorinated 3-methyl-2-phenylindenone ( 3 ), 3-methyl-2-phenylindene ( 4 ), 3-hydroxy-1-methyl-3-phenylindan ( 5 ), 1-methyl-3-phenylindan ( 6 ), 9-methyl-1,2,3,4,5,6,7,8-octahydroanthracene ( 7 ), and 1,9-dimethyl-5,6,7,8-tetrahydro-β-naphthindan ( 8 ). When heated with SbF 5 in the presence of HF, then treated with water, compound 1 is transformed to a mixture of products 3 – 6 . The reaction at 170 and 200 °C forms compounds 3 – 6 together with perfluoro-2-(cyclohexen-1-yl)-3-methylindene ( 10 ).

The reaction of N-polyfluorophenylcarbonimidoyl dichlorides with tertiary amines in acetonitrile afforded chloroamidines R2NC(Cl) = NArF and alkyl chloride. The precursor of the products is the corresponding quaternary ammonium salt [R3N+C(Cl) = NArF]-Cl-. The rate of the salt formation is described by a second order equation; however with some amines a saturation effect was observed for the reaction rate with the growing amine concentration. This fact and also the influence of the amine and the substrate structure on the reaction rate suggests that reaction proceeds by addition-elimination mechanism with formation of a tetrahedral intermediate. The latter in the rate-limiting stage undergoes a stereomutation into an intermediate of a configuration favorable for conversion into a quaternary salt.

A reaction of perfluoro-1-methylbenzocyclobutene with pentafluorobenzene in SbF5 medium followed by treating the reaction mixture with water gave rise to perfluoro-1-methyl-1-phenylbenzocyclobutene, perfluoro-1-methyl-2-phenylbenzocyclobutene, 2-hydroxyperfluoro-1-methyl-2-phenylbenzocyclobutene, and also to small amounts of 1-(2-trifluoromethyltetrafluorophenyl)-1-pentafluorophenyl-2,2,2-trifluoroethane, and perfluoro-1-(2-methylphenyl)-1-phenylethylene. In a crystal of (E)-2-hydroxyperfluoro-1-methyl-2-phenylbenzocyclobutene for a dimer molecular pair a π-stacking interaction between pentafluorophenyl groups was found.

A mechanism is proposed for the substitution of the first halogen atom in N-pentafluorophenylcarbonimidoyl dihalides (ArFN=CX2, X = Cl, Br) by aliphatic amines and includes a tetrahedral intermediate (TE). In the case of the reactions of primary and secondary amines the rate-limiting stage is the formation of the intermediate, and in the case of tertiary amines it is stereomutation of the intermediate (TE) to the thermodynamically more stable configuration (TZ). In the case of all the amines the final product (the Z isomer) is formed from the configuration (TZ).