DE1670876B1 - Phosphoric acid esters and process for their preparation - Google Patents

Description

Calculated .. N 13.5, P 9.9%; found .... N 12.5, P 9.9%.

Example 2 36.6 g (0.2 mol) of the sodium salt of 1-phenyl-3-hydroxy-1, 2,4-triazoles are suspended in 200 ml of acetonitrile and 32.2 g (0.2 mol) of O, O-dimethylthiophosphoric acid chloride added. After stirring for 12 hours at 50 to At 60 ° C., the common salt is filtered off and the filtrate is freed from the solvent. It 55 g of 1-phenyl-3- (O, O-dimethylthionophosphoryl) -1,2,4-triazole remain.

CloHizNs03PS; Molecular weight 285.

Calculated ... N 14.75, P 10.85%; found .... N 14.2, P 10.8%.

Example 3 64.4 g (0.4 moles) of 1-phenyl-3-hydroxy-1,2,4-triazole become 400 ml of tetrahydrofuran and 69 g (0.4 mol) of O, O-diethylphosphoric acid chloride were added and 44 g (0.44 mol) of triethylamine were added dropwise. To complete the exothermic The reaction is stirred for a further 3 hours at 50 ° C. and then the triethylamine hydrochloride filtered off. The filtrate is evaporated, the residue is dissolved in benzene and washed with Water washed. After distilling off the benzene, 117 g of l-phenyl-3- (O, O-diethylphosphoryl) -1,2,4-triazole as light brown 01.

C12H16N304P; Molecular weight 297.

Calculated ... N 14.1, P 10.4%; found .... N 13.9, P 10.0%.

Example 4 25 g (0.127 mol) 1- (3-chlorophenyl) -3-hydroxy-1, 2,4-triazole, 24 g (0.127 mol) of O, O-diethylthiophosphoryl chloride, 15 g (0.15 mol) of triethylamine and 250 ml of benzene are stirred at 60 ° C. for 10 hours.

After suctioning off, it is washed with water and the benzene is distilled off. 39 g of 1- (3-chlorophenyl) -3- (O, O-diethylthionophosphoryl) -1,2,4-triazole are obtained.

CzHisCIN303PS; Molecular weight 347.5.

Calculated .. N 12.1, P 8.9%; found .... N 12.1, P 8.7%.

Example 5 43.4 g (0.2 mol) of the Na salt of 1- (4-chlorophenyl) -3-hydroxy-1, 2,4-triazoles are suspended in 300 ml of benzene and with 38 g (0.2 mol) of O, O-diethylthio. phosphoryl chloride refluxed. The NaCl is filtered off and the benzene distilled off. 64 g of 1- (4-chlorophenyl) -3- (O, O-diethylthionophosphoryl) -1 remain, 2,4-triazole as yellow O1.

CzHlsCIN303PS; Molecular weight 347.5.

Calculated ... N 12.1, P 8.9%; found ... N 12.0, P 8.9%.

Claims (2)

Claims: 1. Phosphoric acid esters of the general formula I where R is methyl or ethyl, R2 is phenyl or chlorophenyl and X is oxygen or sulfur. 2. Process for the preparation of the phosphoric acid esters according to claim 1, characterized in that phosphoric acid halides of the general formula II are used in a manner known per se in which Hal represents halogen, reacts with the formula I correspondingly R 2 -substituted 3-hydroxy-1, 2, 4-triazoles or their metal salts. According to the German patent specification 910652, the production of phosphoric acid esters is known that contain an enolizable heterocycle and for pest control are usable. The invention relates to phosphoric acid esters of the general formula I where R is methyl or ethyl, R2 is phenyl or chlorophenyl and X is oxygen or sulfur. The invention furthermore relates to a process for the preparation of the phosphoric acid esters of the general formula I, which is characterized in that phosphoric acid halides of the general formula II are used in a manner known per se where R is methyl or ethyl and X is oxygen or sulfur and Hal is a halogen atom, preferably a chlorine atom, with the general formula I corresponding to R3-substituted 3-hydroxytriazoles of the general formula III below or their metal salts, preferably their sodium or potassium salts, implements. In the first case, the reaction takes place in the presence of acid-binding agents Agents such as alkali carbonates, e.g. B. soda, alkaline earth carbonates or tertiary amines, such as B. triethylamine, dimethylaniline or pyridine. The reaction is illustrated by the following equation: The reaction can be carried out with or without a solvent. Suitable solvents are all common organic liquids which are inert under the reaction conditions, such as acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, methylene chloride, carbon tetrachloride, benzene, xylene, chlorobenzene, etc. The reaction is generally carried out at temperatures of about 20 to 25 ° C to the boiling point of the individual solvents, but preferably at 50 to 90 ° C. addition of copper powder, preferably between 1 and 20 mol percent, can favorably influence the reaction rate. The new compounds fall partly as Ule, partly crystalline at. They cannot be distilled without being decomposed. The new compounds show good insecticidal and ovicidal action, act as contact and FraB poison and are suitable due to their low toxicity to warm blooded animals to fight endo- and ectoparasites. They also counteract various arthropods resistant to phosphoric acid ester and also show one fungicidal effect. The new compounds are in at least one of the aforementioned effects superior to the compounds known from German patent specification 910 652. Example 1 32.2 g (0.2 moles) of 1-phenyl-3-hydroxy-1,2,4-triazole become suspended in 250 ml of acetone and with 38 g (0.2 mol) of O, O-diethylthionophosphoryl chloride offset. Then 22 g (0.22 mol) of triethylamine are added dropwise and the mixture Stirred for 6 hours at about 50 ° C. After cooling, the triethylamine hydrochloride is filtered off and the solvent removed from the filtrate by evaporation. 60 g of 1-phenyl-3- (O, O-diethylthionophosphoryl) -1, 2,4-triazole are obtained as light brown oil. C12Hl6N303PS; Molecular weight 313.