652-03-9Relevant articles and documents
POLYHALOAROMATICS. PART II. SYMTHESIS OF OCTAFLUORO-1,3-DIHYDRO-ISOBENZOFURAN AND ITS CONVERSION TO TETRAFLUOROTEREPHTHALIC ACID
Dmowski, Wojciech,Wielgat, Jerzy
, p. 241 - 246 (1988)
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.
Novel functionalized indigo derivatives for 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.
, (2020/11/24)
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.
Carbonylation of Polyfluorobenzocyclobutenones in a SbF5 Medium
Zonov, Ya. V.,Karpov,Mezhenkova
, p. 1103 - 1111 (2019/10/14)
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.
Preparation method of 3,4,5,6-tetrafluorophthalic acid
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Paragraph 0013; 0014; 0028-0030; 0033; 0036; 0039, (2018/05/01)
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.
Synthesis method of 3, 4, 5, 6-tetrafluorophthalic acid
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, (2016/11/21)
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.
Catalytic defluorination of perfluorinated aromatics under oxidative conditions using N-bridged diiron phthalocyanine
Colomban, Cédric,Kudrik, Evgenij V.,Afanasiev, Pavel,Sorokin, Alexander B.
, p. 11321 - 11330 (2014/11/07)
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.
Transformations of perfluorinated 1-alkyl-, 1-phenyl- and 1,2-dialkylbenzocyclobutenes under the action of SiO2/SbF5
Zonov, Yaroslav V.,Karpov, Victor M.,Platonov, Vyacheslav E.,Rybalova, Tatjana V.
, p. 41 - 50 (2013/02/25)
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.
Transformations of perfluorinated 2-Alkyl- and 2,2- dialkylbenzocyclobutenones in SbF5 and SiO2-SbF 5
Zonov,Karpov,Platonov
experimental part, p. 1517 - 1526 (2011/02/24)
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.
Preparation of 2,3,4,5-tetrafluorobenzoic acid
Li, Hua,Wang, Hongkai,Zhao, Ruiju,Liu, Juan,Zhao, Zhengui,Hu, Guoqin,Liang, Zhengyong
experimental part, p. 744 - 748 (2011/03/20)
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%.
Reaction of perfluorobenzocycloalkenes with SiO2-SbF5 and skeleton transformations of their carbonyl derivatives in SbF5 medium
Zonov,Karpov,Platonov,Gatilov
, p. 202 - 217 (2008/09/21)
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.
