- POLYHALOAROMATICS. PART II. SYMTHESIS OF OCTAFLUORO-1,3-DIHYDRO-ISOBENZOFURAN AND ITS CONVERSION TO TETRAFLUOROTEREPHTHALIC ACID
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A high yield preparation of the title compound via treament of 4,5,6,7-tetrachloro-1,1,3,3-tetrafluoro-1,3-dihydroisobenzofuran with potassium fluoride in sulpholane is described.Hydrolysis of octafluoro-1,3-dihydroisobenzofuran with concentrated sulphuric acid provides a new and efficient route to tetrafluoroterephthalic acid.
- Dmowski, Wojciech,Wielgat, Jerzy
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- Novel functionalized indigo derivatives for organic electronics
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A series of nine novel indigo derivatives, including diiodoindigo, octahalogenated indigoids and compounds with extended π-conjugated system, were synthesized, characterized and investigated as semiconductor materials in organic field-effect transistors (OFETs). Among them, 6,6′-diiodoindigo demonstrated the ambipolar behavior with balanced p-type and n-type mobilities. The complete substitution of hydrogens at the indigo core with halogen atoms led to low electron mobilities in OFETs. An extension of the conjugated system through the introduction of small aromatic substituents (thiophene and phenyl) resulted in predominant p-type behavior. Fusion of aromatic rings resulted in z-shaped dibenzoindigo, which showed poor charge transport properties due to the non-optimal arrangement of molecules along each other in the crystal lattice. The acquired data fulfilled the previously reported model based on the relationship between the chemical nature of substituents and their positions at the indigo core, optoelectronic properties of materials and their performance in OFETs. The results of this study will be useful for rational design of a new generation of the indigo-based semiconductors for biocompatible organic electronics.
- Klimovich, Irina V.,Zhilenkov, Alexander V.,Кuznetsova, Lidiya I.,Frolova, Lubov A.,Yamilova, Olga R.,Troyanov, Sergey I.,Lyssenko, Konstantin A.,Troshin, Pavel A.
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- Carbonylation of Polyfluorobenzocyclobutenones in a SbF5 Medium
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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 cycle in the substrate to form polyfluorinated 1H-isochromene derivatives. The reaction of perfluoro-2-R-benzocyclobutenes (R = F, CF3, C2F5) with (CF3CO)2O or CF3COOH in a SbF5 medium in a sealed ampule involves formation of polyfluorobenzocyclobutenones and their carbonylation under the reaction conditions.
- Zonov, Ya. V.,Karpov,Mezhenkova
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p. 1103 - 1111
(2019/10/14)
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- Preparation method of 3,4,5,6-tetrafluorophthalic acid
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The invention provides a preparation method of 3,4,5,6-tetrafluorophthalic acid; N-methyltetrachlorophthalimide is hydrolyzed at 30-90 DEG C under the action of a low-concentration acid and a catalystto generate the 3,4,5,6-tetrafluorophthalic acid, and suction filter mother liquid is directly recycled for next batch of hydrolytic reactions. By using the preparation method according to the technical scheme, the use of high-concentration acids and production of mass waste acids are avoided, environmental protection burden is greatly relieved, product yield is increased, product quality is better, and the production cost is also significantly reduced.
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Paragraph 0013; 0014; 0028-0030; 0033; 0036; 0039
(2018/05/01)
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- Synthesis method of 3, 4, 5, 6-tetrafluorophthalic acid
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The invention discloses a synthesis method of 3, 4, 5, 6-tetrafluorophthalic acid, comprising the following steps: (1) adding phthalylhydrazine into mixed liquid of fuming sulfuric acid and diluted hydrochloric acid, then adding a catalyst I into the mixed liquid and stirring the mixture, controlling the filling of chlorine, and carrying out a thermal reaction; (2) adding potassium fluoride into a reaction device containing methyl alcohol, methylbenzene and a solvent I, heating up and then stirring the mixture, and carrying out atmospheric distillation on reaction liquid to recover the methyl alcohol and the methylbenzene; after that, under the protection of nitrogen, adding the tetrachloro phthalylhydrazine prepared in the step (1) and a catalyst II into the product, heating up to 120-200 DEG C and carrying out a fluoridation reaction; (3) adding the tetrachloro phthalylhydrazine and sodium peroxide which are prepared in the step (2) into water, carrying out a hydrolysis reaction for 2-8 hours at the temperature of 10-50 DEG C, then adjusting the acidity of the obtained reaction liquid until the pH value of the reaction liquid is equal to 1-4, carrying out suction filtration and drying to obtain the tetrafluorophthalic acid.
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Paragraph 0036; 0060
(2016/11/21)
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- Catalytic defluorination of perfluorinated aromatics under oxidative conditions using N-bridged diiron phthalocyanine
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Carbon-fluorine bonds are the strongest single bonds in organic chemistry, making activation and cleavage usually associated with organometallic and reductive approaches particularly difficult. We describe here an efficient defluorination of poly- and perfluorinated aromatics under oxidative conditions catalyzed by the μ-nitrido diiron phthalocyanine complex [(Pc)Fe III(μ-N)FeIV(Pc)] under mild conditions (hydrogen peroxide as the oxidant, near-ambient temperatures). The reaction proceeds via the formation of a high-valent diiron phthalocyanine radical cation complex with fluoride axial ligands, [(Pc)(F)FeIV(μ-N)FeIV(F) (Pc+?)], which was isolated and characterized by UV-vis, EPR, 19F NMR, Fe K-edge EXAFS, XANES, and Kβ X-ray emission spectroscopy, ESI-MS, and electrochemical techniques. A wide range of per- and polyfluorinated aromatics (21 examples), including C6F6, C6F5CF3, C6F5CN, and C6F5NO2, were defluorinated with high conversions and high turnover numbers. [(Pc)FeIII(μ-N)Fe IV(Pc)] immobilized on a carbon support showed increased catalytic activity in heterogeneous defluorination in water, providing up to 4825 C-F cleavages per catalyst molecule. The μ-nitrido diiron structure is essential for the oxidative defluorination. Intramolecular competitive reactions using C6F3Cl3 and C6F3H 3 probes indicated preferential transformation of C-F bonds with respect to C-Cl and C-H bonds. On the basis of the available data, mechanistic issues of this unusual reactivity are discussed and a tentative mechanism of defluorination under oxidative conditions is proposed.
- Colomban, Cédric,Kudrik, Evgenij V.,Afanasiev, Pavel,Sorokin, Alexander B.
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p. 11321 - 11330
(2014/11/07)
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- Transformations of perfluorinated 1-alkyl-, 1-phenyl- and 1,2-dialkylbenzocyclobutenes under the action of SiO2/SbF5
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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 SiO 2/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.
- Zonov, Yaroslav V.,Karpov, Victor M.,Platonov, Vyacheslav E.,Rybalova, Tatjana V.
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- Preparation of 2,3,4,5-tetrafluorobenzoic acid
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2,3,4,5-Tetrafluorobenzoic acid, an important intermediates of fluoroquinolone antibiotics, was synthesized from tetrachloride phthalic anhydride through imidation, fluorination, hydrolysis and decarboxylation. The effects of phase transfer catalyst on imidation and fluorination reaction and the effects of surfactants on the hydrolysis reaction were studied, respectively. Experimental results showed that the imidation reaction time was greatly reduced in the presence of a phase transfer catalyst, hexadecyltrimethyl, resulting in imidation yield as high as 98.2%. The fluorination yield reached 81.3% when tetrabutylammonium bromide was chosen as a phase transfer catalyst. The hydrolysis reaction time was also decreased by adding hexadecyltrimethyl while increasing the yield to 88.6%. In the post-processing, the sublimation method was used to purify the product, and ideal effect was obtained. In the decarboxylation reaction, tetrafluoride phthalic acid was obtained by decarboxylation in the solvent of tri-n-butyl amine and decarboxylation yield reached 81.6%. Compared with the literature method, the overall reaction time of the improved method decreased from 53 h to 20.5 h and the total yield increased from 47.3% to 57.4%.
- Li, Hua,Wang, Hongkai,Zhao, Ruiju,Liu, Juan,Zhao, Zhengui,Hu, Guoqin,Liang, Zhengyong
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experimental part
p. 744 - 748
(2011/03/20)
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- Transformations of perfluorinated 2-Alkyl- and 2,2- dialkylbenzocyclobutenones in SbF5 and SiO2-SbF 5
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Perfluorinated 2-methyl- and 2-ethylbenzocyclobutenones on heating in SbF5 underwent isomerization into perfluoroindan-1-one and perfluoro(2-methylindan-1-one), while their reaction with SiO 2-SbF5 gave perfluorinated 3-methyl- and 3-ethylphthalides, respectively. Perfluorinated 2-ethyl-2-methyl- and 2,2-diethylbenzocyclobutenones reacted with SbF5 to produce perfluorinated 2-(but-2-en-2-yl)- and 2-(pent-2-en-3-yl)-benzoic acids, and their transformations in SbF5 over SiO2 afforded 5,6,7,8-tetrafluoro-1-oxo-3-trifluoromethyl-1H-isochromene-4-carboxylic acid and perfluoro(4-ethyl-3-methyl-1H-isochromen-1-one), respectively.
- Zonov,Karpov,Platonov
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experimental part
p. 1517 - 1526
(2011/02/24)
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- Reaction of perfluorobenzocycloalkenes with SiO2-SbF5 and skeleton transformations of their carbonyl derivatives in SbF5 medium
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The reaction of perfluorinated benzocyclobutene and tetraline with SiO 2-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.
- Zonov,Karpov,Platonov,Gatilov
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p. 202 - 217
(2008/09/21)
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- Reaction of perfluoro-1-ethylindan with SiO2/SbF5 and skeletal transformations of perfluoro-3-ethylindan-1-one under the action of SbF5 and SiO2/SbF5
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Perfluoro-1-ethylindan heated with excess of SiO2 in an SbF5 medium at 75 °C and then treated with water, gives 4-carboxy-perfluoro-3-methylisochromen-1-one. Perfluoro-3-ethylindan-1-one is converted, under the action of SbF5 at 70 °C, to perfluoro-2-(but-2-en-2-yl)benzoic acid as a mixture of E- and Z-isomers. When the reaction temperature is raised to 125 °C, a solution of salts of perfluoro-3,4-dimethyl-1H-isochromen-1-yl and perfluoro-4-ethyl-1H-isochromen-1-yl cations is obtained. Increase in the reaction time lowers the content of a salt of the latter cation in the solution. Hydrolysis of the solution of the salts gives perfluoro-3,4-dimethylisochromen-1-one and perfluoro-4-ethylisochromen-1-one.
- Zonov, Yaroslav V.,Karpov, Victor M.,Platonov, Vyacheslav E.
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p. 1065 - 1073
(2008/02/10)
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- Transformation of perfluorinated benzocycloalkenes and alkylbenzenes to their carbonyl derivatives under the action of CF3COOH/SbF5
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Perfluorinated benzocycloalkenes (benzocyclobutene, indan, tetralin), alkylbenzocycloalkenes and alkylbenzenes react with CF3COOH/SbF5 at 20-50 °C giving the corresponding carbonyl derivatives.
- Zonov, Yaroslav V.,Karpov, Victor M.,Platonov, Vyacheslav E.
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p. 1058 - 1064
(2008/02/10)
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- 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
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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.
- Zonov, Yaroslav V.,Karpov, Victor M.,Platonov, Vyacheslav E.,Rybalova, Tatjana V.,Gatilov, Yuri V.
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p. 1574 - 1583
(2008/09/18)
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- Formation and skeletal transformations of perfluoroindan-1-one and perfluoroindan-1,3-dione in the reaction of perfluoroindan with SiO 2/SbF5
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Perfluoroindan-1-one (2) is obtained in the reaction of perfluoroindan (1) with SiO2/SbF5 at 70°C. Compound 1 heated with SiO2/SbF5 at 130°C and then treated with water, gives 3-hydroxy-perfluoro-3-methylphthalide (4). Ketone 2 is converted, under the action of SbF5 at 130°C, to perfluoro-2-ethylbenzoic acid (9) and disproportionates to compound 1 and perfluoroindan-1,3-dione (3); the latter is transformed to phthalide 4 under the reaction conditions.
- Zonov, Yaroslav V.,Karpov, Victor M.,Platonov, Vyacheslav E.
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p. 437 - 443
(2007/10/03)
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- Process improvements in the synthesis of 2,4,5-trifluorobenzoic acid. selective hydrodefluorination of tetrafluorophthalimides
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An improved preparation of the fluoroquinolone antibacterial intermediate 2,4,5-trifluorobenzoic acid is described. A combination of a selective hydrodefluorination and hydrolysis reaction of 3,4,5,6-tetrafluoro-N-methylphthalimide leading to 3,5,6-trifluorophthalic acid was key to the success of the process. In addition the development of a two-step, one-pot imidization/ halogen exchange from tetrachlorophthalic anhydride to 3,4,5,6-tetrafluoro-N-methylphthalimide in sulfolane solvent is detailed.
- Fertel, Lawrence B.
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p. 111 - 115
(2013/09/08)
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- Process for the preparation of salts of substituted or unsubstituted phthalic acids
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The present invention relates to a process for the preparation of salts of substituted or unsubstituted phthalic acids, by reacting a compound of the formula STR1 in which R1, R2, R3 and R4 are identical or different and are H, F, Cl, Br, CF3, OH, an alkoxy or alkyl radical in each case having 1 to 4 carbon atoms, or a radical --NR7 R8, in which R7 and R8 are identical or different and are H, an alkyl radical having 1 to 4 carbon atoms, or a phenyl radical, R5 and R6 are identical or different and are H, a --CO-- alkyl group having 1 to 6 carbon atoms in the alkyl radical, or a benzoyl group, or R5 and R6 together form a radical of the formula STR2 in which R9, R10, R11 and R12 are identical or different and are H, F, Cl, Br, CF3, OH, an alkoxy or alkyl radical in each case having 1 to 4 carbon atoms, or a radical --NR7 R8, in which R7 and R8 are identical or different and are H, an alkyl radical having 1 to 4 carbon atoms, or a phenyl radical, with water, a water-soluble base, and an oxidizing agent at a temperature of -10° to 150° C. in the presence or absence of a water-insoluble solvent inert under the reaction conditions.
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- Process for the preparation of tetrafluorophthalic acid and/or tetrafluorophthalic anhydride
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The present invention relates to a process for the preparation of tetrafluorophthalic acid and/or tetrafluorophthalic anhydride by reacting a compound of the formula STR1 in which X is a radical STR2 which is optionally mono- or polysubstituted on the aromatic nucleus by fluorine and/or chlorine and/or alkyl groups having 1 to 4 carbon atoms, or is a radical STR3 in which R1, R2 and R3 are as defined, with water, and subsequently removing the water still present by azeotropic distillation or extracting the tetrafluorophthalic acid and/or its anhydride with a water-insoluble solvent or solvent mixture.
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- Tetrafluoro-N-phenylphthalimide
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Chlorinated phthalic anhydrides are converted to fluorinated phthalic acids without dilactone formation by reacting an anhydride with a primary amine under anhydrous conditions to form the corresponding chlorinated-N-substituted phthalimide which in turn is reacted with a fluorinating agent under anhydrous conditions to form the corresponding fluorinated phthalimide which is hydrolyzed to form the corresponding fluorinated phthalic acid. In a preferred embodiment tetrachlorophthalic anhydride is refluxed with aniline in the presence of glacial acetic acid for 5 to 10 hours to form tetrachloro-N-phenylphthalimide which is reacted with KF in sulfolane in the presence of tributylhexadecylophosphonium bromide under nitrogen at 140° C. to 160° C. for 10 to 15 hours to form tetrafluoro-N-phenylphthalimide which in turn is hydrolyzed by refluxing with 50% H2 SO4 for 15 to 25 hours. The tetrafluoro-N-phenylphthalimide is a novel compound. The fluorinated phthalic acid products are intermediates for the corresponding fluorinated phthalic anhydrides, fluorinated benzoic acids and fluorinated benzenes.
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- Process for tetrafluorobenzoic acid
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An improved process for the preparation of 2,3,4,5-tetrafluorobenzoic acid is described which involves decarboxylation of tetrafluorophthalic acid in the presence of a base catalyst. Also described is an improved method for preparing tetrafluorophthalic acid and, in turn, a one-pot process for tetrafluorobenzoic acid using the combination of the two improvements.
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- Process for producing tetrafluorophthalic acid
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A process for producing tetrafluorophthalic acid is disclosed, which comprises the steps of: (a) reacting an alkali metal fluoride and at least one imide compound represented by formula (I) or (II) STR1 wherein X1, X2, X3, and X4, which may be the same or different, each represents a chloride atom or a bromine atom, R1 represents a monovalent organic group, and R2 represents a divalent organic group, to provide an N-substituted tetrafluorophthalimide; and (b) hydrolyzing the tetrafluorophthalimide in the presence of an acid.
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- 5,6,7,8-tetrafluoroanthraquinone derivatives
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A 5,6,7,8-tetrafluoroanthraquinone derivative represented by the general formula I: STR1 wherein R1 and R2 independently stand for --OH or STR2 (where R3 and R4 independently stand for hydrogen an alkyl of 1 to 4 carbon atoms or a phenyl) and X and Y independently hydrogen atom or a halogen atom.
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- OXIDATION OF OCTAFLUORONAPHTHALENE AND HEPTAFLUORONAPHTHOLS WITH HYDROGEN PEROXIDE
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Derivatives of 1-oxodihydronaphthalenes and 1,4-naphthoquinone are formed preferentially during the thermal decomposition of hydrogen peroxide in an excess of octafluoronaphthalene or heptafluoro-1- and heptafluoro-2-naphthols.The oxidation of these substrates with an excess of hydrogen peroxide leads to destruction of the aromatic ring.Possible paths to the formation of the main products, including the generation of heptafluoronaphthoxyl radicals both as a result of reaction of the octafluoronaphthalene with the hydroxyl radicals and as a result of oxidation of the heptafluoronaphthols, are considered.
- Bogachev, A. A.,Kobrina, L. S.,Yakobson, G. G.
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p. 2307 - 2313
(2007/10/02)
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