SU184863A1 - METHOD OF OBTAINING CHLORANGIDRIDOV Dithiophosphoric acid - Google Patents

Description

A method is proposed for the preparation of dithiophosphoric acid chlorides of the general Formula OA PCI, where R and R are alkyl or aryl. by reacting alkyl (aryl) dithiodichlorophosphates with alcohols or phenols in organic solvents in the presence of acceptors of hydrogen chloride, such as tertiary amines, or without acceptors of hydrogen chloride and without an organic solvent. The compounds obtained can be used for the synthesis of pesticidal preparations. Examples 1. Preparation of o-butyl-3-butyldithiochlorphosphate. A. To a solution of 0.05 gmol of butyldithio dichlorophosphate and 0.055 g mol of butanol in 60 ml of benzene, 0.05 gmol of triethylamine is added with stirring and at a temperature of 35-40 ° C. The reaction was kept under these conditions for 5 hours, cooled, the hydrochloride of amine was filtered off, the filtrate was washed with water, dried over sodium sulfate, the solvent was distilled off in vacuo, and almost pure product was obtained in a residue of d = 1,1226, p 1.5161. Exit 87%. 1,1236, ng 1,5175, MRo 70,02, calc. 69.99. Found,%: C1 13.80; S 24.93; SPSN OPSz. Calculated, o / o: C1 13.62; S i24,59. B. A mixture of 0.05 g mol of butyldithio dichlorophosphate and 0.055 g-mol of butanol is heated at 80-85 ° C for 15 hours, passing a weak stream of dry nitrogen through the reaction mass. To complete the reaction, the temperature was raised to 100 ° C, and the mixture was kept at that temperature for 2 hours. Under these conditions, a theoretical amount of hydrogen chloride was released. After separation of all of the hydrogen chloride, the reaction mass is maintained at 60-80 ° C (15-20 mm) and the technical product is obtained in a quantitative yield: d 1.1240, 1.5130. Characteristics of distilled substances: t. Kip. 75-76 ° C (0.01 mm), df 1.1250; “20 1,5164. 2. Preparation of 5-ethyl-o-.i-cresyl-dithiochlorophosphate. To a solution of 0.05 g-mol of ethyl dichlorodithiophosphate and 0.05 g-mol of g-cresol in 50 ml of benzene, 0.05 g-mol of triethylamine is added with stirring at a temperature of 75-80 ° C and the reaction mixture is kept under these conditions 4 hour. After cooling, the precipitate is filtered off, the filtrate is washed with water, dried over sodium sulfate, the solvent is distilled off in vacuo, and the residue is obtained as a viscous liquid, which decomposes when attempted to distill. For identification, the substance is reacted with butylamine in benzene and 5 to obtain 90% ethyl-o-α and -cresyl butylamide dithiophosphate, m.p. 42-43 ° C (from alcohol). Found,%: N 4.81; S 22.04. Ci3H22NOPS2 Calculated,%: N 4.63; S 21.70. Under the conditions of Example 1A, other substances were obtained, the yield and properties of which and the analysis data are shown in the table. Table

The subject matter of the invention. 1. A method of preparing dithiophosphoric acid chlorides of general formula p / c PLC II 10 S where R and R are alkyl or aryl, characterized in that the alkyl (aryl) dithiodichlorbophosphates are reacted with alcohols or phenols That the process is carried out in organic solvents in the presence of hydrogen chloride acceptors, for example, tertiary amines.