SU519420A1 - The method of obtaining the substituted monoamides of phosphorous phosphate - Google Patents

Description

the course of 95-100% in the calculation of the introduced phosphorus. The separation of the reaction products is carried out by fractional crystallization or other known methods, for example, extraction and distillation.

If there is an excess of amine, ammonium salts of phosphorous monoamides are formed in the reaction mixture, which are separated from phosphorous diamides. Pure phosphorous monoamides are extracted from the ammonium salts by extraction.

When alicyclic amines interact with phosphorous anhydride, a small amount of phosphorous triamides is formed as a result of side reactions.

Example 1. To 100 weight. including dry piperidine in a dry inert gas atmosphere while cooling to a temperature of 15 ° C and adding 16.25 weight with stirring for 1.3 hours. including phosphorous anhydride dissolved in 25 wt. h. pentane. The reaction mixture is stirred for one hour and mixed with 200 wt. h. pentane. The resulting crystalline precipitate is separated by filtration through a frit and washed with pentane.

Output 36.6 weight parts of piperidine monopiperidine phosphorous acid, which corresponds to 58.2%, based on the used phosphorus; colorless crystals have a pour point of 75-76 ° C (with decomposition).

The filtrate is evaporated in vacuo, the residue is dissolved in 40 wt. including pentane and the mixture is extracted with 90 wt. including acetonitride. After separation, both phases are evaporated in vacuo and the residue from the pentane phase is washed several times with a small amount of acetonitrile. Output 2.5 weight. including phosphorous acid tripiperidide, which corresponds to 3.3%, based on the phosphorus used; slightly yellowish crystals have a pour point of 36-37 ° C.

The residue after distillation of the acetonitrile phase consists of phosphorous dipiperidide. Output 26.9 wt. including dipiperidide phosphorous acid, which corresponds to 42.1%, based on the used phosphorus; slightly yellow, neperegon yush, and from the oil a liquid.

Found,%: 14.20; N 12.84; C 56.08; H 9.92.

Calculated,%: R 14.35; N 12.96; C 55.50; H 9.72.

15.4 weight. including piperidine monopiperidide phosphorous acid is dissolved in 150 weight. including benzene and the solution is left to stand for 24 hours. The precipitate is separated, washed with a small amount of benzene and dried in vacuo. Output 5.1 weight. including monopiperidide phosphorous acid, which corresponds to 52.0%, based on the phosphorus used in the form of the piperidine monopiperidine phosphorous acid; colorless crystals.

Found,%: P 19.9; N 9.6; C, 39.9; H 8.3. Calculated,%: R 20.3; N 9.4; C 40.3; H 8.1. Example 2. In a three-necked flask with a capacity of 1 l, 250.75 g (1870 mmol) of diisobutylamine were placed and 26.00 g (118.2 mmol) of phosphorous anhydride were added with stirring and cooling with ice water to a temperature of + 10 ° C. The clear solution is stirred eh; e for

2 hours at room temperature and thereafter, an excess amount of diisobutylamine is evaporated under vacuum at a temperature of 30 ° C. The residue weighs 149.00 g and consists of an equimolar mixture of colorless, crystalline

diisobutylamine monodiisobutylamide

phosphorous acid and slightly yellow oily tetraisobutyldiamide phosphorous acid. This corresponds to a yield of about 100%, based on the use of phosphorus. Separation is carried out by placing the mixture on a frit and sucking the oily liquid from the solid.

5.37 g (16.7 mmol) of diisobutylamine monoamide diisobutyl phosphorous acid are dissolved in a mixture of 25 ml of pentane and 25 ml of benzene and left to stand for 24 hours at 4 ° C. 1.9 g of diisobutylphosphorous monoamide crystallize out of solution. This corresponds to a yield of about 63.6%, based on the used phosphorus.

Found,%: P 15.09; N 7.20; C 53.55; H 10.80.

Calculated,%: P 16,06; N 7.26; C 52.40; H 10.36.

Example 3. At the addition of a solution of 14.05 g (63.9 mmol) of phosphorous anhydride in 50 ml of pentane with stirring and cooling with water at 18 ° C to 88.60 g (1210 mmol) n-butylamine for 50 minutes, a colored in slightly yellow color solution and colorless precipitate. After separating the precipitate, 24.8 g of α-butyl aminate is obtained.

mono-n-butylamide phosphorous acid (colorless, hygroscopic crystals). This corresponds to a yield of about 46.2% based on the phosphor used. After evaporation, the filtrate is mixed with 100 ml of penta.

and left to stand for 24 hours at 4 ° C, the precipitated precipitate is separated, and the filtrate is again evaporated in vacuo. As a residue, 24.00 g of di - "- phosphorous butylamide (slightly yellow,

non-distillation liquid). This contributes to a yield of 49.0%, based on the phosphor used.

Found,%: P 16.35; N 14.20; C, 51.07; H 11.20.

Calculated,%: P 16,44; N 14.58; C 50.00; H 10.94.

Example 4. 73.0 g (655 mmol) of gutoluene are mixed in 600 ml of benzene with vigorous stirring and cooling with water.

having a temperature of 25 ° C, dropwise with a solution of 14.02 g (63.8 mmol) of phosphorous anhydride in 30 ml of benzene. After separating the precipitate and concentrating the filtrate in vacuo, 72.3 g of phosphoric acid di-p-toluidide (colorless solid, pour point 145 ° C) were obtained. This corresponds to a yield of about 97.0%, based on the phosphor used.

Found,%: P 12.02; N 10.59; C, 64.84; H 6.47.

Calculated,%: R 11.92; N 10.78; C, 64.60; H 6.54.

Claims (4)

1. A process for the preparation of substituted myo- and diamides of phosphorous acid based on trivalent phosphorus compounds, characterized in that, in order to increase the yield of the product and simplify the process, primary or secondary aliphatic, alicyclic or aromatic a-min is reacted with phosphorous anhydride at a mole ratio phosphorous anhydride to the amine, lying in the range from 1: 8 to 1: 30, followed by separation of the desired products by known methods. 2. A method according to claim 1, characterized in that the process is carried out in an organic solvent medium. 3. Method according to paragraphs. 1 and 2, characterized in that the process is carried out at a temperature of 15-25 ° C. 4. Method according to paragraphs. 1-3, characterized in that phosphorous anhydride and amine ;; take in a molar ratio of 1:10.