SU407916A1 - - Google Patents

Description

METHOD OF OBTAINING ETHYL-; 8-BROMETHYLPHOSPHINE ACID or ITS DERIVATIVES

12

ISO5REt.en.ie refers to phosphorus chemistry, and.andly to sp0so | bu receive

new X these l -j8 -b, r about MET. And Lf OSF1I "OB OI KlHt l about t s

silt, and its production, of the general formulas

VGCHNNO. O / R

s, n / x

pde X - pidroysil, alkokoil, Aroxsl "l. and halogen.

A known method for the preparation of e-T1Liloic ester is et: yl-p-bromoethylphosphonic acid by the interaction of 3-b | romet.ild, and 1b | rhomphin with .M1HYTHE ethyl in the presence of methyl bromide al. plo.xa et.ilo; vym sprint

However, it is ethyl-D-bromoethylphosphonic acid, acid halides, and other effective ethe. Il- / b- | bromoethyl, ylfo-1Sp | ipowy acid were not obtained and are new. " They can be used as flame retardant additives, as well as intermediates in fosoroforivchekoy synthesis.

The proposed method for the preparation of ethyl- / bromoethylphosphinic acid or its-derivatives is that the complex obtained by interacting with phosphorus tribromide, aluminum bromide and ethyl bromide is treated with ethylene and then water.

go alcohol m. Target products are isolated by known methods.

Phosphor bromide, aluminum bromide and ethyl bromide, taken in molar 5 ratios of 1: 1: 1, it is advisable to interact in a non-double bond aliphatic hydrocarbon medium, for example in hexane, at a temperature of 20-50 ° C. ;

The treatment of the complex with ethylene lslate, b, but carried out at a temperature of 30-60 ° C, and hydrolysis Formed by passing ethylene intermediate product: tj organic solvent medium, for example

5 dichloroethane.

E ti and L | -1v-.bro. M eti lf of bases and acido a; l, and its extracts can be treated with their phosphorus phosphorus and can be converted to chlorine and the corresponding acid chloride.

Example 1. To a solution of 29.3 g of aluminum bromide. In 20 (3 ml of n-hexane, 29.92 of phosphorus tribromide are poured and the mixture is added dropwise at room temperature and with stirring - |, n 12.0 g of ethyl bromide, then the mixture is stirred; 40–50 ° C for 15–30 .v.iUL-B O | the complex formed during the displacement of ethylene and ethylene is passed at such a rate that the temperature is kept in the terminal building at 45-55 ° C ..,.

The end of the reaction

tours to room) hexane is poured, and the remaining pasty paste is dissolved; c) c) 50 ml of dichloro; retan is poured onto ice. The resulting organic and aqueous layer are separated, and the aqueous solution of 4 and 15 ipasa exsist porous 15 d, d of dichloroethane (50-80 ml); combined Dichloroethane extracts are dried over magnesium sulphate or other dryers, filtered and distilled scratan is distilled off. This is obtained} 4.0 g: Ethyl-0-bromoethyl | phosphonic acid (63.5%) in the form of a noncrystal, and a light yellow oily liquid. Found,%: C 24.90; H 5.18; R 15.3 / 3.

C4Hio VgOaR.

;%; C 23.91; H 5.02; R 15.42.

Example 2. The paste obtained analogously to Example 1, from 120.0 g of bramyl alumina, and L22.5 g of trehbrolshstogo foofschra and 49.2 g of ethyl bromide in 400 ml of hexane was dissolved in 100 ml of dichloroethane and added to a mixture of 200 ml ethanol and 100 ml of dichloroethane; at a temperature of 20-26 ° C. then water is then poured until two layers are formed, the aqueous layer is separated from this mixture new and extracted 1101 times | Mi (50-80 ml). dichloroethane. The combined dichloroethane vaters of: scraped as in Example 1, and 78.5 g (76.1% on P / Vgz) of ethyl ethyl ether (in -, b | rometyl 1-phosphine ACID B) are obtained in the form of a colorless mobile LIQUID , kip. 74- 75C (0.06 mm); 1.3718; l about 1.4820.

Found,%: P 13.53; Br 34.75; MRo 47.59.

SbNmVgOZR. Calculated,%: P 13.60; : Br 35.00; MRo 47.41.

Note 3) In the words of example 2, of 29.4 g of aluminum bromide, 30.0 g of tre.HbromMiHCToro of phosphorus, 12.1 g of ethyl bromo-ethyl, and 70.0 g of c-butyl alcohol using 200 ml. ml of α-hexane and 200 ml of dichloroethane. 19.2 g (67.5% on RVhz) of ethyl ethyl- / 5-brothyl ethyl phosphonate acid as a colorless mobile liquid, ie, bale, are obtained. 79-80 ° C (0.035%); / f 1.2481; l about 1.4740.

Found,%: P 12.56; MRo 57.90.

CgHigBrOaP.

, Calculated,%: P 12.06; MRo 56.65.

Example 4. To a solution of 41.5 g of ethyl ester, and ethyl-β-bromoethylphosphonic acid in 50 ml of benzene, during the stirring, 37.8 g of phosphorous chloride are added to the mixture, while maintaining external cooling. The temperature is 15- 26 ° C. The reaction mixture is stirred at the same temperature for another 15-20 minutes, benzene is distilled from the residue by vacuum distillation to obtain 36.9 g (93.5%) of ethyl-bromoethoctho phosphonic acid in as a colorless | And explosive liquid, t. Kip. 69-70 ° C (0.03 mm); df 1,5853; 1.5-181.

Found,%: C 22.13; H 4.35; R 14.00; MRo 41.93.

S4P9VVgS OR.

Calculated,%: C, 21.94; H 4.17; R 14.15; MRD 41.77. EXAMPLE 5. To a solution of 5.8 g of chlorine-nhydride ET1IL-p-brOM1EThylf00NOVA ACID in

75 ml of ether are added dropwise at 0 ° and mixing a mixture of 0.85 g of alcoholic alcohol, 2.7 g of triethylamine and 25 ml of ether, then mixed for 20 minutes at 20 °, filtered, dried triethyl hydrochloride. mine and from f: iltrat distilled eff. From the residue by vacuum distillation, 4.75 g (83%) of methyl ester, ethylene / b-bro, methyl phosphonic acid in the form of a colorless mobile liquid, m.p. 69-70 ° С (0.06 лж); df 1.4321; "D 1.4892.

Found,%: C 28.04; H 5.86; R 14.35; AIRo 43.37.

C5H, 2VG02R.

Calculated,%: C 27.9; H 5.62; R 14.40; MRfl 42.80.

Example 6. Under conditions of 5 of 8.0 g of ethyl- (3-bromoethylphosphipic acid chloride) in 50 ml of ether, 2.2 g of isopropyl alcohol and 3.7 g of triethylamine in 60 ml of ether, 7.8 are obtained. g (88%) of ethyl- / 3-bro-ethylphosphinic acid isopropyl ester, bp. 65-66 ° С (0.04 df 1.3013; l 20 1.4750.

Found,%: C 34.50; H 6.66; P 13.13; MRp 52.60. CrHieBrOaP.

Calculated,%: C 34.60; H 6.58; P 12.75; MRo 52.60.

Lriemer 7. Under conditions of 6 of 10.0 g of ethyl- / 3-br01M9-tylphosphinic acid chloride in 70 ml of ether, 4.33 g of phenol and 3.62 g of triethylamine in 80 ml of ether, I0 is obtained, l g (80%) ethylbromoethylphosphinic phenyl ester. ACID in the form of colorless g. ZHIDOKOSTY, kip. 116-118 ° С

(0.04lsh); 4 ° 1.3962; lo 1.5457.

Found,%: C 43.19; H 5.51; R 11.34; MRo 62.85.

CioHuBrOaP.

Calculated,%: C 43.30; H 5.06; R 11.18; MRo 62.29.

(The subject of the invention.

Claims (4)

1. Method of producing ethyl-D-bro. Ethylphosphonic acid or its procedure: Aqueous, characterized in that the complex obtained by the reciprocal. Modes: II and three bro. Phosphorus, aluminum bromide and ethyl ethyl. , is treated with ethylene, and then with water or alcohol, followed by isolation of the target product gIL: And transferring it to the haloalkyl chloride of the corresponding acid is known: by methods. 2. Spo, in accordance with claim 1, characterized in that three-bromo phosphorus, aluminum and brrom, M | true ethyl, taken in molar ratios of 1: 1: 1, are put into agitation in an environment of aliphatic hydrocarbon, not containing DIvoy 1st bonds, for example, in hexane, n: p "20-50 ° C. 3. Method according to paragraphs. 1 and 2, characterized by the treatment of the complex with etlene at 30-60 ° C. 4. Method according to PP. 1-3, characterized in that the hydrolysis of o6ipa3OBaBiuerocH by passing ethylene of the intermediate product is carried out in an environment of an organic solvent, for example dichloroethane.