SU483401A1 - Method for preparing diorgano (thio) phosphorylsulfenamides - Google Patents

Description

one

The invention relates to the preparation of organophosphorus compounds, namely to a process for the preparation of diorgano (Thio) phosphoryl sulfenamides of the general formula

R2P (X) SNH2

where R is aryl, alkoxy or aryloxy; X - oxygen or sulfur, which can be used in the synthesis of pesticides.

The proposed method for the preparation of diorgano (thio) phosphoryl sulfenamides is based on the known reaction of reacting bis (phosphoryl) disulfides with amines, and consists in the fact that bis-organo (thio) phosphoryl disulfide of the general formula

Xx

R, II11 / R

„/ H

where R and X - as indicated above, is treated with ammonia in an inert organic solvent, for example benzene, ether, at O-10 ° C.

Target products are recovered by known techniques. Ammonium salts of phosphorus acids are formed along with the desired product.

Example 1. In a solution of 5 g of bis- (diethoxythiophosphoryl) disulfide in 50 ml of absolute benzene, dried ammonia is passed over 3 hours. Chromatographic control of the reaction (until the disappearance of Pten disulfide on a plate with a carrier of the type "Silufol in the acetone-hexane system, 1: 3).

Upon completion of the reaction, 50 ml of hexane is added to the solution, the separated oil is separated, the solvent is distilled off in vacuo, the residue is distilled at 0.1 mm Hg. Art. and get diethoxythiophosphoryl sulfenamide.

Example 2. 50 ml of absolute benzene

saturated with ammonia at 5 ° C until the weight of the solution increases by 1 g. A solution of 5 g of bis (diphenoxythiophosphoryl) disulfide in 20 ml of absolute benzene is added dropwise to the benzene solution. Ammonia is passed into the solution for another 30 minutes, 50 ml of hexane are added, the separated crystals are filtered off and recrystallized from chlorobenzene. Get the ammonium salt of O, O-diphenyldithiophosphoric acid, so pl. 147-

148 ° C, the yield is quantitative. The filtrate is evaporated and the diphenoxythiophosphoryl sulfenamide is re-crystallized from hexane.

Example 3. In a solution of 5 g of bis- (diphenylthiophosphoryl) -disulfide in 50 ml of absolute benzene dry ammonia is passed within 2 hours. The precipitated crystals are filtered and recrystallized from ethyl acetate. Get the ammonium salt of diphenyldithiophosphinic acid, so pl. 199-200 ° C, yield

quantitative.

The filtrate is evaporated, an oil is obtained in the residue, which crystallizes in the cold. Diphenylthiophosphoryl sulfenamide is recrystallized from hexane.

Example 4. 50 ml of absolute diethyl ether are saturated for 15 minutes with dry ammonia and a solution of 10 g of bis (diisopropoxyphosphoryl) disulfide in 15 ml of diethyl ether is added dropwise to the resulting solution.

Upon completion of the reaction, the solution is washed twice with water, dried over magnesium sulfate, the solvent is distilled off, and non-refractory maolo diisopropoxyphosphoryl sulfenamide is obtained as a residue. The product gives one spot on a chromatographic plate with a carrier of the type “Silufol in the system acetone-hexane (1: 3).

Properties of the compounds obtained are shown in the table.

Subject invention

The method of obtaining diorgano- (thio) -phosphoryl sulfenamides of the general formula

R2P (X) SNH2

where R is aryl, alkoxy or aryloxy; X - oxygen or sulfur.

characterized in that bis-organo (thio) -phosphoryl-disulfide is reacted with ammonia in an inert organic solvent at ~ 10 ° C, followed by isolation of the target product by known methods.