SU563419A1 - Method of producing saits of 0.0-dimethyldithiophosphoric acid - Google Patents

Description

(54) METHOD FOR OBTAINING SALTS OF 0,0-DIMETHYDEDITIOPHOSPHORIC ACID

one

This invention relates to the field of thiophophoric esters, in particular to a new method for the preparation of O, O-dimethyldithiophosphoric acid salts used to synthesize dithiophosphoric acid derivatives with insecticidal activity, for example, to react with monochloroacetic acid amides or esters or N-chloromethylphthalmic acid or N-chloromethylphthalmic acid.

A known method for the preparation of salts of O, O-dimethyldithiophosphoric acid by methanolysis of n-dispersed phosphorus with 1 followed by neutralization with base 0 0 O-dimethyldithiophosphoric acid 1.

During the methanolysis of grainy phosphorus, significant amounts of neutral by-products are formed, therefore, the yield of O, 0-dimethyldithiophosphoric acid salts is known by the way I exceed 80%.

Neutral products of metanolysis of phosphorous phosphorus consist of a mixture of esters of various phosphorus thioacids. Along with 0, O, Trimethyldithiophosphate are present.

O, O, O, O-tetramethyltritiopyrophosphate and bis (0, O-dimethylthiophosphoryl) -disulfide, O, O, O-trimethylthiophosphate, 0,0-dimethylthiophosphite and

some unknown components 2. The interaction with chlorine of this mixture of vepdeal is converted into O, O-dimethylthiophosphoryl chloride, which is less commonly used than

salts of 0,0-dimethyldithiophosphoric acid.

The aim of the invention is to increase the efficiency of the process for producing 0,0dimethyldithiophosphoric acid salts.

The goal is achieved by the fact that

neutral methanolysis products of lysterous phosphorus are reacted with

sulfur in alkaline-anhydrous or water-alkaline medium at O-60 ° C.

The alkaline medium is created by adding to the reaction mass of α-hydroxide, a Christmas tree or its carbonate, or am.miama.

The process is carried out in the presence of an inert organic solvent which is not miscible with water, for example chloroform, carbon tetrachloride, benzene, toluene, n-OK-tane.

The salts of 0,0-dimethyldithiophosphoric acid, after the end of the reaction, remain in solution or precipitate if the process is carried out in the absence of water. After adding water until the salt is completely dissolved, they are separated from the organic phase, while simultaneously removing excess sulfur by filtering. A weakly alkaline solution of O, O-dimethyldithiophosphoric acid salts is neutralized with a suitable acid, and the advantage of 0,0-dimethyldithiophosphoric acid itself. Example I. K 147 weight. including a 38% solution of neutral by-products of methanolysis of P4Sio (npH molar ratio 9: 1) in benzene (200 D1L of beisol / mol; P. (Si (,) after adding 5.5 of the neck. grinding of sulfur when iremixing 2 hours, 5 parts by weight of ammonia-K a gas are supplied, and the temperature of the reaction mixture is between 30 and 40 ° C. The precipitated ammonium-O, 0-dimethyl dithiophosphate is dissolved in 40 parts by weight of water, the excess sulfur is filtered off and 15 weight is washed Part of water. The isolated aqueous phase contains 34 parts by weight of ammonium-0, O-dimethyldithiophosphate, determined photometrically through the nickname left complex 0, O-dimethyldithiophosphoric acid Example 2. 852 parts by weight of i25% -Horo solution of chlorine inorganic byproducts of metaiolysis in chloroform and obtained 280 ml of chloroform per 1: mol P-iSio, after adding 36 parts by weight Sulfur is unmixed for 6 hours at 30 ° C, 3-2 parts by weight of almiac are added. 120 parts by weight of water are added, the ammonium salt O, Odimethyldithiophosphoric acid is dissolved in the solution, the excess sulfur is removed by filtration, and the residue is washed with water. The isolated aqueous phase contains 192.5 wt. including a monium-O, O-dimethyldithiophosphate. The ammoniaic aqueous phase, with stirring, is neutralized with crude O, O-dimethyldithiophosphoric acid and separated from the resulting organic phase, from which the ammonium salt of O, O-dimethyldithiophosphoric acid is obtained by treating with ammonia and sulfur. Example 3. 224 wt. including a 24% solution of neutral by-products of methanolysis in carbon tetrachloride (280. ml of carbon tetrachloride per 1 mol of P4Sio) Lime with 8 wt. h. sulfur. While stirring for 30 minutes, 31 wt. including 22% aqueous solution of ammonia in water, the temperature of the mixture being kept at 50 ° C. Stir for another 90 minutes at 50 ° C, filter sulfur and rinse with water. The aqueous solution freed from the organic phase is neutralized with dilute hydrochloric acid. The aqueous solution contains 42 wt. including ammonium-O, O-dimethyl t1 phosphate, determined by photo-photometrically through a nickel complex. Example 4. K 2-13 weight. Part of the used j example 2 solution of neutral byproducts. Products of methanolysis in chloroform, with the addition of 9 wt. including sulfur add 15 PLN 61 weight. including 35% aqueous solution of potassium carbonate. Stir for 2 hours at three 30 ° C, excess sulfur is filtered off and the solution is washed with water. The alkaline aqueous phase contains 30.5 wt. including potassium-0, O-dimethyldithiophosphate, determined photometrically through a nickel complex. Example 5. K61 weight. including neutral neutral by-products (without addition of inert solvent) after adding 9 wt. including ground sulfur with stirring for 2 h serves 8 wt. including gaseous A.miaka, and the reaction temperature is maintained at 30-40 ° C. The precipitated OHOHiii precipitated ammonium-0, O-dimethyldithiophosphate was dissolved 30: nes. including water, otfil1 / grow excess sulfur and washed with water. The isolated aqueous phase contains 39.8 wt. including ammonium-O, O-dimethyldithiophosphate, which is determined photometrically through a nickel complex 0, O-dimethyldithiophosphoric acid. Example 6. 61 weight. . h. The neutral by-products obtained analogously to Example 5 are dissolved in 150 wt. including chloroform or 70 wt. hours and octane. In the solution after adding 11.5 wt. including ground sulfur for 2 hours while unmixing, 10 wt. including gaseous am.miak, and the temperature of the reaction mixture is maintained at. The precipitated ammonium Y1O, O-dimethyldithiophosphate 1) is dissolved in 30 wt. including water, filter off excess sulfur and Nro.wash with water. The isolated aqueous phase contains from 46 to 49 wt. ammonium-O, O-dimethyldite phosphate, determined photometrically through a nickel complex. Example 7. 383 wt. including a solution of neutral methanolysis byproducts in chloroform, obtained as an organic phase and reacting P4Sio with methanol at a molar ratio of 1: 8 using 280 ml of chloroform per mole and subsequent neutralization of the product with aqueous alkali, mixed with 8, 6 wt. h. sulfur. With stirring for 30 minutes, 60 wt. including a 20% aqueous solution of ammonia, and the temperature is maintained at 50 ° C, stirred for another 90 minutes at 50 ° C, the sulfur is filtered off and washed with a small amount of water. In the isolated aqueous phase, concentrations were determined by photometric analysis with nickel dimethyl dithiophosphate (61 wt.%). am ammonium-0, 0-D11methyldithiophosphate. Example 8. 425 weight. including a solution of neutral byproducts of methanolysis in chloroform, obtained by IB as the organic phase with the interaction of P4Sio with methanol in a molar ratio of 1:10 using 280 ML of chloroform per mole and the subsequent neutralization of the product of interaction with an aqueous solution of lyceum, p. stir with 9.5: weight. h. sulfur. For 30 min., 67 wt. including 20% Hoiro aqueous ammonia solution, the temperature being maintained at 50 ° C. Stir for another 90 minutes at 50 ° C, filter the sulfur and rinse with a small amount of water. In the isolated aqueous phase, according to the photometric analysis data with nickel-dimethyldithiophosammonium-0, 0-dpmethyldithiofate, 64 wt. including phosphate.

Claims (3)

1. A method of obtaining phosphorus thioacid ester salts of 0, O-dimethyltithiophosphoric acid, characterized in that, in order to increase the efficiency of the process, the neutral products of methanolysis. Of phosphorous phosphorus are subjected to interaction with sulfur in an alkaline-free or aqueous-alkaline medium at 0 -60 ° C. 2. Method: but p. 1, characterized in that the alkaline medium is created by adding the reaction mass of alkali metal hydroxide or its carbonate, or. 3. The method according to neither. 1 and 2 are distinguished by the fact that the process is carried out in the presence of an inert organic solvent which is not miscible with water, for example chloroform. Sources of information received but inspected at examination 1. Houben-Weyl. Methoden der orgaiiischeii Chemic.-Georg Thieme Verlag, Stuttgart, 1964, XIl / 2, s. 685 (nrotiotype). 2. Sippmanv A. E. The Constitution of crude 0,0-dimethyldithiophosphoric acid. - “Journ. Org. Chem., 1966, 31, p. 471-473.