SU280475A1 - METHOD OF OBTAINING ORGANOPHOSPHORUS COMPOUNDS - Google Patents

Description

This invention relates to methods for producing thiophosphoric and thiophosphonic acid derivatives of formula 1.

XO

R. II11

; PSCHaCH2NHCR R /

where X is oxygen or Sulfur;

R-alkyl, aryl, aralkyl, alkoxy,

alkylthio, aryloxy or arylthium; R is an alkoyl, alkylthio, aryloxy, arylthio, benzyloxy, benzylthio, or amHIO group;

R is alkyl, alkoxy or aminogroup. Of the compounds of this type are known as highly effective eestides, in particular insecticides, substances in which X is oxygen, R and R are alkoxyl, and R is alkyl.

Limes method of producing esters of Ti-phosphorus {x acids of general formula

SO

RO. Iiii

/PSCH.CHsNHCXR RO

the interaction of ether salts 1 Acid General formula

S ro.

PSM

RO

where R and R are as defined above; M - alkali metal,

.Q with N-chloroethylcarbamate of the general formula

CICH.CH.NHCXR

where X and R are as defined above, in an inert organic solvent medium. The resulting esters of thiophosphoric acids have a high acaricidal activity.

In order to increase the yields of the target products, as well as to expand the range of derivatives of thiophosphoric and thiophosphonic ACIDS - promising pesticides, a method has been proposed for preparing ferrofluoric compounds of the general formula

XO

R is alkyl, ar sil, araluil, alcoyus,

alkylthio, aryloxy or arylthio, R is alkoxy, alkylthio, aryloxy, arylthio, beisyloxy, bisylthio or amino,

R is an alkyl, alkoxy or amino group, based on the fact that the amino salts of the ether salts of ACID phosphorus of the general formula

R. II

; Psm

R /

where X, R and R have the above Ziacheni,

M - alkali metal or substituted ammonium, is subjected to interaction with acid chlorides of ACIDS of the general formula

II

where R has the foregoing values, an organic solvent medium, and for example benzole, followed by treatment of the reaction mixture with ethyleneimine. The process is preferably carried out at a temperature of 20-80 ° C. Target products are recovered by known techniques.

Example 1. O, O-Diethyl-5-p- (carbaminoethyl) ethyl dithiophosphate.

A mixture of 0.02 gmol of the triethylammonium salt of O, O-diethyldithiofluoric acid,

0.02 g-mol of ethyl chloroformate and 40 ml of dry benzene is stirred for 2 hours at 50 ° C and 2 hours at 80 ° C. After that, the reaction mass is cooled to 20 ° C and at this temperature, a solution of 0.02 g-ly ethyleneimine in 2 ml of benzene is slowly added, stirred for 2 hours at 20 ° C and 2 hours at 50 ° C, cooled, washed with reagent. a lot of water, suplat over magnesium sulphate, distill off the solvent and distil the remaining product at a bath temperature of 160 ° C and a residual pressure of 0.05 mm Hg. v .; yield 87.1%, df 1.1707, if ° 1.5110.

Found,%: N 4.61; P 10.41; S 21.11.

C9H2oNO4PS2.

Calculated,%: N 4.65; P 10.30; S 21.26.

Example 2. O-Ethyl-S-p- (carbaminoethyl) ethylmethyl dithiophosphonate.

0.02 g mole of triethylamine is added to a mixture of 0.02 gmol of methyldidisophosphonic acid anhydride, 0.02 gmol of α-absolute ethanol and 25 ml of dry benzene with stirring and cooling. maintaining the temperature in the reaction mass 15 ° C, continue to stir for 1 hour at room temperature and 2 hours at 50 ° C. After that, the reaction mass containing triethylammonium salt of 0-ethylmethyldithiophosphonic acid is cooled to 20 ° C and a solution of 0.02 g-mol of ethyl chloroformate in 5 ml of benzene is slowly added at this temperature, stirred at 50-60 ° C for 3 hours and cooled. Then, a solution of 0.02 g-mole of ethylene ethylene in 5 ml of benzene is added dropwise to the reaction mass, keeping the temperature in the reaction mass at 20 ° C, stirring is continued for 1 hour under these conditions and 3 hours at 60 ° C, then cooled, by filtration, triethylamine hydrochloride is washed with water, the filtrate is washed, it is dried with sulfate.

magnesium and the solvent is distilled off under reduced pressure. Get the product with the release of 92.5%, df 1,1869, 1,5190. Venous; distilled without decomposition at temperature

bath 170 ° C and a residual pressure of 0.08 mm Hg. Art., df 1.1900, rfi 1.5210, MRo: found 69.50, calculated 69.15.

Paydeno,%: N 5.36; R 11.50; S 23.11. CsHisNOsPSa.

Calculated,%: N 5.17; R 11.44; S 23.61.

In the infrared spectrum of the obtained compound, cleared on the HR-IO device, characteristic bands were found at 520 (P-S link), 640 cm-1 (PS link), 800 cm-i (carbamate group vibrations), 920 cm (P-CH3 bond), 980 szh-1 (P-O-Et bond), 1065 s. (vibrations of the carbamate group), 1170 C. / I-1 (ether C – O – C), 1290 cc-i (vibrations of the C – N bond), 1420 cm (bond

Р-СНз), 1460 CM-i (deformation vibrations of СНз), 1560 (deformation vibrations N – Н), 1740 CM-i (communication), 2880, 2940, 2990 (stretching vibrations, -СНз), 3350 (stretching vibrations svizm-n).

PR and mer 3. 5-Butyl-3-p- (carbaminoethyl) ethylmethyltriothiophosphonate.

The product is prepared under the conditions of example 2 from 0.02 g-mole methyldithiophosphoric anhydride

acids, 0.02 gmol of butylmercaptan, 0.02 gmol of triethylamine, 0.02 gmol of ethyl chloroformate and 0.02 gmol of ethyleneimine. Yield 89.7%, df 1.1915, 1.5610. The substance is distilled at a bath temperature of 185 ° C and a residual pressure of 0.15 mm Hg. Art., df 1.1950, rf ° 1.5615. MRo: found 85.30, calculated 85.20.

Paideno,%: N 4.57, R 9.97, S 30.33.

CioH NOaPSg.

Calculated,%: N 4.45, P 9.85, S 30.49. In the IR spectrum of the obtained compound, cleared on the MR-IO iribor, characteristic bands were detected at 520 (valence

oscillations P-S), 645 CAf (communication oscillations), 780 (vibrations of the carbamate group), 910 CM (vibrations of the P-CH3 bond), 1060 CM (vibrations of the carbamate group), 1160 (oscillatory vibrations of the bond

C – O – C), 1280 (oscillations of C – N coupling), 1420 CM-i (P – CH3 bond), 1380, 1460 cm (deformation oscillations of CH3 and CH3), 1540 (deformation oscillations of N – H), 1730 CM-i (communication), 2880, 2930, 2970 CMi

3330 cl-1 (stretching vibrations of N-H bond).

At measure 4. O-Ethyl-3-p- (diethylamidcarbamino) ethnlfetheslddithiPhosphonate.

To a mixture of 0.02 g-mol of phenyldithiophosphoric acid anhydride, 0.02 g-mol of absolute ethanol and 25 ml of dry benzene without unmixing and cooling 0.02 g-mol of triztilamine is added, maintaining the temperature in the reaction mass of 15 ° C, stir for 1 hour at room temperature and 2 hours at 50 ° C. After that, the reaction mass, containing triethylammonium salt of O-ethylphenyldithiophosphonic acid, is cooled to 20 ° C. And a solution of 0.02 g-mol of diethylcarbamoyl chloride in 5 ml of benzene is poured at this temperature, stirred at 60-80 ° C for 6 hours, cooled and added t solution of 0.02 g-mol of ethylenimine in 2 ml of benzene, maintaining the temperature in the reaction mass of 20 ° C. The mixture was stirred for 1 hour under these conditions and 4 hours at 60-70 ° C, then cooled, the triethylamine hydrochloride was separated by filtration, the filtrate was washed with water, dried over magnesium sulfate and the solvent was distilled off under ionic pressure. A product is obtained with a yield of 80.5%, df 1.1480, rf ° 1.5760.

Found: N: 7.36, P 8.69, S 17.59.

CisnasNgOaPSa.

Calculated,%: N 7.78, R 8.62, S 17.78.

In the IR spectrum of the obtained compound, cleared on the HR-IO instrument, characteristic bands were detected at 535 s. (PS-link oscillations), 620 CMi (link), 1050 and 1160 (oscillations of Р-О-С group), a set of bands at IZO, 1210 and 1300 cm, which can be attributed to stretching C – N vibrations different bands, strip pr: And 1380, 1420, 1455 szh (deformation oscillations of CH3- and SPA-groups), 1,550 cm (deformation oscillations NN)

1650 slg (carbonyl group), 2950, 2990 (valeitic oscillations in SPZ SPa-groups), 3070 c. (valent C-Pokolebani in the benzene ring) and 3340 cm (valent N – P oscillations in substituted ureas).

The same compound was obtained by the interaction of O-ethylphenyldithiophosphonate with ethylene by the use of diethylcarbamic acid; df 1.1502, 1.5770. The main bands mentioned above, in the IR Spectra of compounds obtained by different methods, coincided.

Under the conditions of Examples 1-4, other compounds were obtained, the analysis of which is given in the table.

Subject invention

Claims (2)

1. The method of obtaining organophosphorus compounds of general formula PSCH.CHoNHCR R where X is oxygen or sulfur; R is alkyl, aryl, aralkyl, alkoxy, alkylthio, aryloxy or arylthio; R is alkoxy, alkylthio, aryloxy, arylthio, benzyloxy, benzylthio or the amino group; R is an alkyl, alkoxy or amino group, characterized in that, in order to increase the yield of the target products, the amide or ester salts of phosphorus acids of general formula X R. II PSM R / where X, R and R have the above meanings; M - silk metal or substituted ammonium, is subjected to interaction with acid chlorides of the general formula about II where R has the above values, in an inertized organic solvent medium with the next treatment of the reaction mixture with ethnlenimine and isolation of the target product by known methods. 2. A method according to claim 1, characterized in that the process is carried out at a temperature of 20-80 ° C. Rx IIII  P SCH CHONHC R / R Table XO