SU258307A1 - METHOD FOR OBTAINING ALKYLALKOXYALKYLPHOSPHINE ACID ESTERS - Google Patents

Description

This invention relates to a process for the preparation of novel compounds of the general formula

R

. R

I P-CH-OR

where R, P, is alkyl;

KH, alkyl. These compounds can be used as physiologically active substances. The method consists in that the amido. Alkylphosphonic acid chlorohydride is mixed in an equimolecular ratio with (x-haloalkyl alkyl ether). After four to five days, crystalline adducts are formed at room temperature or with heating to 40-60 ° C for 7-8 hours orange color. The resulting adducts are decomposed by sulfur dioxide. After hydrochlorination in diethyl ether, resulting from the decomposition of the liquid mass, the resulting hydrochloric acid diethylamine and suction of the ether are separated by distillation in vacuo. alkyl alkoxyalkylphosphinic acid chlorides. When treated with the last alcohols in the presence or absence of organic bases, the corresponding esters are formed.

Example.

a) Preparation of ethyl ethoxymethylphosphinic acid chloride

In a 100 ml round-bottomed flask, 20 g (0.12 mol of ethylphosphonic acid diethylamidochloride tridide and 11.4 g (0.12 mol of chloromethyl methyl ether) are placed. The mixture is stirred by shaking, tightly

close and heat in a water bath at 50 ° C at 7 o'clock. The resulting adduct is decomposed with sulfur dioxide until the solid mass disappears completely (the reaction is strongly exothermic, therefore the sulfur reservoir serves

weak current, and the reaction mixture is cooled in a water bath). After decomposition, the reaction mixture is transferred to a 250 ml three-necked flask with a stirrer and 100 ml of dry ether are added. As the passage of dry hydrogen chloride occurs, the liquid is dissolved and the formation of diethylamine hydrochloride. After hydrochlorination, the mixture is left overnight. Diethylamine hydrochloride is filtered off and washed with ether (four times 20 ml each time. Then the ether is distilled off and the residue is distilled in vacuum. 11.6 g (57%) of a yellowish liquid is obtained with a boiling point of 91-93 ° C / 3 mm, 1.4642, df 1.1513, MRo: found 40.87; Found,%: 35.51; H 7.52; C1 20.46. CsHiaClOaP Calculated,%; 35.19; H 7.03; C1 20.82. B) Preparation of ethyl ethyl 1-simethylphosphinic acid ester. To 9 g (0.053 mol) of ethyl ethoxymethylphosphinic acid chloride dissolved in 40 ml of dry benzene and placed in a three-necked flask with a stirrer with a capacity of 100 ml, drop by drop at 20 ° C 3.2 g (0.1 mol) of absolute methyl alcohol. The mixture is stirred at room temperature for 20 minutes. After distilling off the benzene, the residue is distilled. Obtain 4.65 g (53%) of a colorless liquid with m. Kip. 96-97 ° C / 3 mm, 1.4385, df 1.0524, MRo: found 41.46, calculated 41.29. Found,%: P 18.51. CoH3O3 Calculated,%: R 18.67. c) Preparation of ethyl ether ethoxymethylphosphinic acid. The product is obtained in a manner similar to that written off from 8 3 (0.047 mol} ethyl ethyl ethoxymethylphosphinic acid and 4.6 g (0.1 mol) of absolute ethanol. 4.8 g (57%) of a colorless liquid is isolated with m, bales of 92-93 ° C / 2 mm, 1.4364; - ---, ". ... d4 ° 1.0232; MRD: found 46.05; calculated 46.91. Found,%: Р 17.34. CvHivOaP Calculated,% : P 17,22. Subject of the invention Method for preparing alkylalkoxyalkylphosphonic acid esters of the general formula -P-CH-OR where R, R, R is alkyl; R is H, alkyl, in which the alkylphosphonic acid is reacted with cc-haloalkylalkyl alkyl phyr, followed by decomposition of the adduct with sulfur dioxide and hydrochlorination, and the resulting alkyl alkoxyalkylphosphinic acid chloride is reacted with an alcohol.