SU359827A1 - ALL-UNION FWSH ^ SHSh ^ ^ - d! BIBLOT ::; '! ^' 1 - Google Patents

Description

METHOD OF OBTAINING AMIDOCHLORIDES OF PHOSPHORIC

OR thiophosphoric acid

The invention relates to the field of production of phosphorus acid amides, namely, to a method for producing phosphoric or thiophosphoric acid amide hydrochlorides not described in the literature.

YCHN X

f-0-i-iCOOR

where R is hydrogen or alkyl Ci-C3, R and R are d-C alkyls, X is hydrogen or chlorine, Y is oxygen or sulfur. These compounds can be used to synthesize biologically active organophosphorus substances, in particular insecticides. The proposed method is based on the known reaction of the aminating of phosphorus acid chlorides. The method consists in the phosphoric or thiophosphoric acid dichlorides being of the general formula

where, X and Y have the indicated meanings, are reacted with amines of the general formula

where R and R have the indicated meanings.

The process is carried out in a solvent medium, for example toluene, chlorobenzene, chloroform, or in an aqueous medium.

It is preferable to use an amount of amine equivalent to the exchange of one chlorine atom. In this case, the process is carried out in the presence of a hydrogen acceptor, for example, triethylamine, diethylaniline, sodium carbonate.

An excess of amine can also serve as an acceptor of hydrogen chloride. The reaction temperature is best kept within minus 10 - plus 20 ° C.

The starting phosphoric or thiophosphoric acid dichlorohydrides can be obtained by reacting phosphorus oxychloride or phosphorus thiochloroxy with the corresponding derivatives of acetoacetic ester and reacted with amines without isolation.

Example 1. O- (1-Methoxycarbonyl-1-propen-2-yl) -Y-methylphosphoramidochloride

58.5 g (0.25 mol} O- (1-methoxycarbonyl-1propen-2-yl) phosphoric chloride) are dissolved in 300 m, l of chlorobenzene. To this solution is added dropwise over 30 minutes at 20 ° C a mixture of 7.8 g (0.25 mol) of methylamine in 30 g of chloroform and 25.5 g (0.25 mol) of triethylamine, as well as 100 ml of chlorobenzene.

After the addition, it is stirred for another 1 hour, then filtered off the precipitated triethylamine hydrochloride, the solvent is evaporated and the resulting product is distilled under a pressure of 10 mm Hg. Art. During the distillation, pure O- (1-methoxycarbonyl-1propen-2-yl) -N-methylphosphoramidochloride is obtained, which boils under pressure of 5-10 mm Hg. Art. at 95-97 ° C, has a refractive index n |) 0 1,482, mol. weight 227.6.

Found,%: C 31.9; H 5.2; C1 16.0; N 6.0; R 13.1.

Calculated,%: C 31.7; H 4.9; C1 15.6; N 6.2; P 13.6.

Example 2. 0- (1-Methoxycarbonyl-1-propen-2-yl) -M, M-diethylphosphoramidochloride

76.7 g (0.5 mol) of phosphorus oxychloride are dissolved in 200 ml of chlorobenzene. A mixture of 58.1 g (0.5 mol) of acetoacetic acid methyl ester and 51 g (0.5 mol) of triethylamine is added dropwise within 15 minutes at -10 ° C. After completion of the addition, the reaction mixture is stirred for 30 minutes at 0 ° C and 1 hour at 20 ° C. The reaction solution was then diluted with 300 ml of chlorobenzene, cooled to -5 ° C, and 73.1 g (1 mol) of diethylamine was added to the solution over a period of 30 minutes at -5 ° C. Then stirred for 30 min at 0 ° C and 2 hours at 20 ° C. The precipitate formed is then filtered off, the solvent is evaporated and the product obtained is distilled. Formed O- (1 - methoxycarbonyl - 1-propen-2-yl) -Y, Cdiethylphosphoramidochloride boils under pressure in mm Hg. Art. at 69-71 ° C, has a refractive index of 1.473, mol. weight 269.7.

Found,%: C 40.1; H 6.7; C1 12.8; N 4.9; R 11.1.

Calculated,%: C 40.1; H 6.4; C1 13.1; N 5.2; R 11.55.

5 Example 3. O- (1-Ethoxycarbonyl-1-propen-2-yl) -Y-n-propylthiophosphoramidochloride

A solution of 131.5 g (0.5 mol) of O- (1-ethoxycarbonyl-1-propen-2-yl) -thiophosphoride dichloride in 500 ml of toluene was added to a mixture of 29.6 g (0 , 5 mol) n-propylamine to 51 g (0.5 mol) of triethylamine. The reaction mixture is then stirred e, 30 minutes at 0 ° C and 1 hour at 20 ° C. The triethylamino hydrochloride is then filtered off, the filtrate is washed with water, dried with Na 2 SO 4 and distilled. The resulting O- (1-ethoxycarbonyl-1-propen-2-yl) -N “-propylthiophosphoramidochloride boils under pressure of 5 mm Hg. Art. at 92 ° C, it has a refractive index of p 1.514, mol. weight 285.7.

Found,%: C 37.9; H 5.8; C1 12.6; N 5.2; P 10.2; S 11.2.

Calculated,%: C 37.8; H 6.0; C1 12.4; N 4.9; 5 P 10.8; S 11.2.

Example 4. O- (1-Isopropoxycarbonyl-1propen-2-yl) -Y-ethylthiophosphoramid chloride

To 27.7 g (0.1 mol) of O- (isopropoxycarbonyl-1-propen-2-yl) -thiophosphordic chloride, 12.8 g of a 70% ethylamine solution in water (0 , 2 mol) with stirring for 15 minutes. Continue to mix for 15 minutes, separate the oily product, wash with water, dry and distill under vacuum (deep). O- (1-Isopropoxycarbonyl-1-propen-2-yl) -N-ethylthiophosphoramidochloride boils at 89 ° C (5 mmHg), has a refractive index of p 1.5100, mol. weight 285.7.

Found,%: C 37.7; H 5.9; C1 12.7; N 5.1; R 10.8; S 11.2.

Calculated,%: C 37.8; H 6.0; C1 12.4; N 4.9; R 10.85; S 11.2.

In the same manner as described in the examples, the compounds indicated in the table are obtained.

Subject invention

Claims (3)

1. A method for producing phosphoric or thiophosphoric acid amidochlorides of the general formula YСНз .C4J 0-i i-COOR v -N where R is hydrogen or alkyl Ci-C3, R and R are Ci-Cg alkyls, X is hydrogen or chlorine, Y is oxygen or sulfur, characterized in that the phosphoric or thiophosphoric acid dichlorides formulas Y CH, X C To IIII j -0-C C-COOR where R, X and Y have the indicated meanings, are reacted with amines of the general formula where R and R have the indicated meanings, in a solvent medium, followed by isolation of the target product by known techniques. 2. The method according to claim 1, characterized in that the amine is taken in an amount equivalent to exchange of one chlorine atom. 3. Method according to paragraphs. 1 and 2, characterized in that the process is carried out in the presence of a hydrogen chloride acceptor.