SU560870A1 - The method of producing polyfluorodiphenylmethanes - Google Patents

Description

 ;, 1 The invention relates to methods for obtaining polyfluorinated diphenylmethanes, and having 4.4 R, 2,3,5,6,2 h, 5 6, - octafluorodiphenyl-1 tetanes of a common mule: where R .-- Gusg b CW, , tWjOH. Polyfluorinated diphenylmethanes can be used as high-temperature solvents, heat carriers or working bodies in power plants, as hiking raw materials for obtaining polymers resistant to thermal, chemical and other effects, antioxidants, light-resistant dyes, etc., as well as as feedstock in various chemical processes. The use of organoparticulate compounds is based on the fact that the accumulation of fluorine atoms in a molecule gives a number of unique properties to materials based on them: thermal and chemical resistance of polymers, non-oxidability of lubricants, and low-temperature rubber l. A known method for producing decafter-diphenylmethane by alkylation of pentafluorobenzene with methylene chloride or pentafluorobenzyl chloride house in the presence of aluminum chloride 2}, This method has major flaws. Thus, in the case of alkylation with methylene chloride, expensive pentafluorobenzene is used in a triple of 1H, and the process is conducted under pressure at a temperature of 15 ° C. The aim of the invention is to develop a method for producing 2, 3, 4, 5, 6, 2, 3, 4, 5 | b, - decafluorodiphenylmethane and other new polyfluorodiphenylmethanes containing fluorine atoms in aromatic 5 vdra, which allows for an increase in the yield of products and at the same time, to simplify the instrumental implementation of the process by eliminating noBbb pressure, lowering the temperature and using a more affordable feedstock. The proposed method consists in the fact that the corresponding polyfluorobenzene is reacted with paraform yl SO -37% formalin at a temperature of 2 ° -70 ° C in a mixture of concentrated sulfuric acid or 2-30% oleum. The process is conducted in a medium of concentrated sulfuric acid or 2-10% oleum in the presence of electron-donating substituents, for example, Cii -, CFi, O - groups in the initial 1-R-2, 3, 5, b - tetrafluoro-. benzene, and in a 2O-30% oleum medium with nalgchii electron-withdrawing substituents in the initial l-R-2,3,5,6 geoglufluorobenzene, for example, F, Cg, LH. The method is recognized by the simplicity and availability of the raw material (pentafluorobenzene is a marketable product, available methods for producing 1-Pr-2, 3,5,6 - tetrafluorobenzenes) are also known, high yield of the target product, ease of technical implementation. The structure of the new compounds was confirmed by PC - spectra and spectra: NMR F. Example 1. To a solution of 12.0 g (0, 4 mol) of steam (| yurma in 45 ml of 28% oleum (s3 1.923), 10.5 g (0.062 mol) of pentafluorobenzene were added and the mixture was heated at 50-55 ° C for 9 hours, poured on ice, the precipitate is filtered off, washed with water and dried to give 1O, 3 (97%) 2, 3, 4, 5, 6, 2, 3, 4, 4, 6 T. Ш1. 63.64C decafluorodiphenylmethane c -, (from petroleum ether with m.p. 7O-100-C with activated carbon). According to sj m. Pl. 63-64 °, the mixed sample with the sample obtained according to s} does not give melting point depressions. The IR spectra of both samples are identical. EXAMPLE 2 To a solution of 2.16 g (0.072 mol) paraform in 1 0 ml of oleum (3 1.931) add 2 pg (0.01 O8 mol) 1 chloro 2, 3, 5, 6 - tetrafluorobenol, heat, at 55 mix for 14 hours, pour on ice, extract with ether, dry the ether solution after distillation solution of bodies, get 1.5 g (75%) 4, dichloro 2, 3, 3, 5, 6, 2, 3, 5, b - octafluorodiphenylmethane with mp, 66-67 (from petroleum ether, t KNP. 7O-100 ° C with activated carbon. The data of elementary analysis (C, H, F, Cf, mol. Weight) correspond to the formula C Example size 3. To solution 1, O g (O, OZ my) paraform n 10 mp opeum (1.92) pribug 1.5 g (0.006 mop) 1 - bromo 2,3, 5, in TRTrafluorobenzene, stirred per hour at 40 ° C and processing, by analogy with Example 1, obtain 1.4 g (90%), 4, 4 - dibrom -2,3, 5, 6, 2, 3, 5, 6 octafluorodifenklmethane with m, pl. 97 - 98 ° C (from benzene). The data of elementary analysis (C, H, P, Bg1Mol. Weight) correspond to the formula Ci, о о Example 4. To a solution of 0.18 g (O. Оb mol) paraform in 20 ml H2SO (d 4 1 835) add 0.5 g (0.003 mol) 2, 3, 5, 6 - tetrafluorotoluene, stirring for 4 hours with ana- treatment; logical described in example 1, get 0.44 g (86%) of 4, 4-dimethyl - 2, 3, 5.6, 2, 3, 5, in octafluorodiphenylmethane with m. pl. 91-92 ° (from benzene). The data of elementary analysis (C, K, F, mol. Weight) correspond to the formula C-xz orDx Example 5. To solution 9, O g paraform (O, 3 mass) in 120 ml of oleum (1.840) was added 10.8 g (0 , 06 mol) 2, 3, 5, 6 - tetrafluoroanisole, stirred for 6 hours at 25–30 ° C and using a treatment similar to that described in Example 3, 9.3, (90%) 4,4-dimethoxy 2,3,5 , 6.2, 3, 5, 6 - okfluorodiphenylmethane with m. Pl. 59-60 ° С (from petroleum ether, t. Kip. 70-10О С with activated lem). Data elementary ngtae. (Cj, H, F, mol. Weight) according to the formula C- (5H8P802. Formula and 3 about b - e and H and 1. The method was obtained (.and popiptrpifpiyameg-jl rr xrf-vrrTt.r. Tans of the formula where RF, ce, Br, CH ,,, CHjC about tl and h ayu and so that, in order to increase the yield of the target product and expand the range, the corresponding polyfluorobenzene is subjected to interaction with paraform or 30 - 3 7% - Formalin at a temperature of pxi 20-70 ° C in an environment of concentrated sulfuric acid or 2 to 30% oleum. 2. The method according to U, 1, o tl and h ay yy and Jt with the process being carried out at a molar the ratio of polyfhorbenzene and PA aforma 1: 2 -10.

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