SU132212A1 - The method of obtaining fluorinated glycols - Google Patents

Description

The described method of obtaining fluorinated glycols by the reduction of perfluorodicarboxylic acid esters allows the raw material base of the initial products to be expanded. This is achieved by using sodium borohydride in the presence of aluminum chloride in an inert solvent as the reducing agent.

Example 1. 10 g of nerfluorosebacic acid HOOC (CP2) 8 COOH is dissolved in 20 ml of absolute C2H5OH, 1 ml of fluorosulfonic acid is added and the mixture is heated under reflux for 3-1 hours and a boiling water bath; after cooling, the mixture is poured into cold water (50-60 ml), the separated oil is separated and dissolved in ether. The aqueous layer is extracted twice with ether and the extract is combined with an ethereal oil solution, washed with a solution of NaHCOs, with water, dried with anhydrous MgSO4 and distilled. Obtain 7.2 g of perfluorosebacic acid diethyl ester C2H5OCO (CP2) 8COOC2H5 with t. Kip. 117-118 ° / 5 mm; yield 65%, based on taken acid. 2 g of unreacted acid is recovered from the bicarbonate wash solution; the output of the ether in the calculation of the reacted acid - 80%. In a reaction flask with a stirrer and a reflux condenser, 1.1 g of sodium borohydride triturated in powder and 20 ml of dry diglyme (CH 3 OCH 2 CH 2 O 2 CH 2 CH 2 O 3) are placed in a two-dropping funnels, stirred to dissolve the borohydride, and then at room temperature add 1.5 drops g A1Cl3 (voznapnogo) in 15 ml of diglyme and 7.2 g of D 1 ethyl ester of Nerfluorobenzoic acid; keep the reaction temperature no higher than 45-55 °. Stir for 1-1.5 hours at room temperature, then when heated to 50-60 ° for 1.5-2 hours; after cooling, gradually transfer the reaction mixture together with the precipitate into 50 ml of cold water, acidified with 5-6 ml of concentrated HC1. The peeling of 1322122 oil was separated and shaken with water, yielding 5.3, colorless crystals of the glycol HOH2 (CP2) 8CH2OH with a m.p. 135-136 (from SCC). - Aqueous pacjBOp is extracted with ether three times after separation of the oil, the extract is dried with anhydrous MgSO4 and distilled. The ether is distilled off and. d needles them (T. bil. 61-62 ° / 15 mm), the residue is treated with water and receive 1 g of crystalline glycol with so pl. 135-136 ° (from ecu). The overall glycol yield (HOCH2 (CF2) gCH20H) is 87%, calculated on the perfluorosebacic acid diethyl ester taken into reaction. Analysis; Found in%: C-26.36; H-1.60; F-68-45

calculated in%: C- -25.96; H - 1.29; F-67-96. dl l CioHgFieOs.

Example 2. From 15 g of perfluoro-dopedic acid HOOC (CF2) and 25 ml of abs (; lute in the presence of 1 ml of fluorosulfonic kh: lots of pp and heated and for 3–4 rd. 10.1 g of the obtained ester was added to the solution of 2.6 g of sodium borohydrind in 35-40 ml of dnglum, once a day, with the addition of a solution 3.5 g of AlCl.i in 30 ml of dig.shma, maintained at a reaction temperature not higher than 45-55, the reaction mixture is stirred at room temperature for 1-1.5 hours, then the irp is heated and to 50-60 ° for 1–1.5 hours -:;. After cooling, the reaction mixture is gradually poured into 100 ml of ice-water, acidified with 10 ml of concentrated HCl. The resulting solution is extracted three times with ether, the extract is dried with anhydrous MgS04; ether and diglyme are distilled off and 7.3 g of glycol FIOCH2 (CF2) .iCFl2OH are obtained with a boil of 118-1207 LP and so on, 67-68 ° (from HCH), 80% yield, taken as diethyl perfluoroadnnic ester. The reaction of glycol with feni / shzoniapat receive feiiluretan with t. Pl. 140 (from SCC).

Analysis: found in vi: C-48.37; H-3.29; F-31.04

calculated in%: C, 00; And - 3.20; F - 30.40. for C2oH |, iF8O.iN..K

And redemt and z obretep and

The method of obtaining fluorinated chicols by the reduction of the southern perfluorodicarboxylic acid esters, this is so that, in order to expand the raw material base, sodium borohydride is used as a reducing agent in the presence of alumi1P1 chloride in a synthetic solvent.