SU375298A1 - METHOD FOR PRODUCING 2,3,3-TRIFLUOROLLYL ESTERS OF O-ALKYLMETHYL PHOSPHONE OR OR TIONPHOSPHONE - Google Patents

Description

one

This invention relates to a process for the preparation of 2,3,3-trifluoroallylated esters of O-alkylmethylphosphonic OR-TIONPHOSPHONE acids of the general formula

/

RO

OCH ,,

where R is alkyl,

X - oxygen or sulfur.

A method of producing phosphonic or thion-phosphonic acid esters by reacting the dihydride anhydrides of the corresponding phosphonic acids with alcohols is known.

However, the compounds of this formula have not been obtained and are new.

They can be used as monomers for the preparation of polymeric materials that are thermally stable.

The proposed method for the preparation of phosphoatoate is that O-alkylmethylphosphonic or -thionophosphonic acid chlorides are reacted with 2,3,3-trifluoroallyl alcohol.

The process is conducted in an environment of an organic solvent, for example ether, in the presence of an acceptor of hydrogen chloride, for example a tertiary amine.

Target products are recovered by known techniques. Yield 15-20%.

Example 1. Ethyl 2,3,3-trifluoroallymethylphosphonate.

In a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 5.45 g (0.03 mol) of methylphosphonic acid chloride ethyl ester are placed in 25 ml of absolute ether. A mixture consisting of 10 ml of absolute ether, 4.3 g of 2,3,3-trifluoroallyl alcohol and 3.84 g (0.03 mol) of triethylamine is prepared. The mixture at room temperature is added dropwise over 30 minutes to an ethereal solution of methylphosphonic acid ethyl ester chloride.

After the addition of the whole mixture, transfer is continued for another 1 hour. The reaction mass is left overnight. The precipitate is filtered off. The ether was distilled off and the fractionation of the residue gave 1.6 g of a liquid with m.p. 60-62 / 5 mmHg v .; n about 1,3909; 1.2941.

MRo found 40.0; MRo calculated 40,527.

Paydeno,%: C 32.5. 32.6; H 4.47, 4.61; F 25.8 25.85; R 14.01 13.96.

SbNiOzRRz.

Calculated,%; C 32.8; P 4.58; F 25.6; R 14.2. SP, About X / F (2) s, n, o osn, (IF (l) F (3) NMR 19F: 6i 25.5 ppm 71 Hz bz 41.5 ppm; 1-2 ,, 117 Hz bz 113 ppm; Ii, 3 33 hz Example 2. Isopropyl-2,3,3-trifluoroallylmethylphosphonate Example 1 of 7.85 g (0.05 mol) of methylphosphonic acid chloride isopropyl ether, 6 g (0.05 mol) of 2,3,3-trifluoroallyl alcohol and 5.05 g (0.05 mol) of triethylamine in 45 ml of absolute ether give 1.8 g of a colorless liquid with a boil of 66-68 ° C / 5 mmHg, 1.3960; f ° 4 1.2289. MKV found 45.5; MRn calculated 45.192. Found%: C 35.6 35.8; H 5.41 5.47; F 24, 18 24.3; P 13.6 13.51. C7P1-AO3RZ. Calculated,%: C 36.0; P 5.2; F 24.4; P 13.4. NMR 19F: 6i 25.5 ppm. ; Ij 71 Hz 8-2 41.5 ppm; L. l 117 Hz bz 113 ppm 32 Hz Example 3. Ethyl-2,3,3-trifluoroallymethylthionophosphonate Example 1 from 7.1 g (0.045 mol) of methylthionphosphonic acid ethyl ester chloride, 5.5 g (0.045 mol) 2.3.3 -trifluoroallyl alcohol and 7.07 g (0.07 mol) of triethylamine in 45 ml of absolute ether get 1.7 e of a colorless liquid with a powder. 68--70 ° C / 4 mm Hg. v .; 1,4365; , 2462. MRo found 48.7; MRn calculated 48.25. Paydeno,%: C 30.73 31.05; P 4.53; 4.29; F 24.02 24.15; R 13.19 12.9; S 13.46 13.39. CeHioOaPSF :. Calculated,%: C 30.80; P 4.27; F 24.4; P 13.2; S 13.6. The subject of the invention. Method for producing 2,3,3-trifluoroallyl ethers of O-alkylmethylphosphonic or -thionphosphonic acids of the general formula: OCHaCF CF where R is alkyl, X is oxygen or sulfur, characterized in that 0-alkylmethylphosphonic or -thionylphosphonic acid chloride is reacted with 2,3,3-trifluoroallyl alcohol in the medium of an organic solvent, for example ether, in the presence of a hydrogen chloride acceptor, for example, a tertiary amine, followed by separation of the target product by known methods.