DE1177161B - Process for the preparation of thiophosphoric acid ethyleneimides - Google Patents

Description

Process for the preparation of thiophosphoric acid ethylene imides The invention relates to a process for the preparation of thiophosphoric acid ethylene imides of the general formula in which R1 and R2 are lower alkyl radicals in which, in a manner known per se, O, S-dialkylthiolphosphoric acid chlorides of the general formula Reacts in the presence of an acid binder with ethyleneimine and the resulting O, SDialkylthiolphosphorigsäureäthylenimide of the general formula expediently reacts with the equivalent amount of sulfur without prior isolation.

The process according to the invention is preferably carried out in the presence a solvent, e.g.

Toluene, benzene or chlorobenzene.

The acid binders used are preferably tertiary bases, and those that form hydrochlorides that are sparingly soluble in organic solvents, such as pyridine, triethylamine and dimethylaniline.

The O, S-dialkylthiolphosphoric acid chlorides used as starting materials are obtained from the corresponding 0-alkylphosphorous acid dichlorides by reaction with the equivalent amounts of a mercaptan and a tertiary base according to the patent 1112732 accessible.

The compounds obtained according to the process have a strong insecticidal properties Effectiveness and should therefore be used as a pesticide, especially in the Plant protection, find use. They stand out in comparison to known, Compounds that can be used for the same purpose have much better insecticides Properties, as can be seen in the table below.

Comparative experiments Because of active ingredient kill binding constitution application kanzentration of the pests No concentration of the villains m 010 in O / o S. C340 \ II / CH2 1 / PN \ | Fly maggots 0.001 100 C2RiS CH2 termites Q05 100 (according to the invention, example 1) 5 II / CH2-CH2 2 (GH5O) 2 = POCH2N | Fly maggots 0.001 0 \ CO CH2 termites 0.05 0 (known from the German exposition 1061785, example 1) The following examples illustrate the claimed process.

example 1 22 g (0.5 mol) of ethyleneimine are dissolved in 300 cc of toluene, 51 g of triethylamine are added to this solution with stirring and then 88 g of O, S-diethylthiolphosphoric acid chloride are added dropwise with further stirring at 10 "C. The mixture is left at 30 ° C. for 1 hour Stir and then enter 16 g of sulfur, the temperature rising to 60 "C. After the end of the entry, the mixture is heated to 90 ° C. for a further 112 hours and then the reaction mixture is poured into 100 cc of ice water. The toluene layer is separated off in a separating funnel, dried with sodium sulfate, the solvent is evaporated off and the residue is fractionated.

Yield 55 g (52% of theory) of O, S diethylthionothiolphosphoric acid ethylenimide from Kp.o, o 64 "C.

Example 2 51 g of triethylamine are added to a solution of 22 g (0.5 mol) of ethyleneimine in 300 cc of toluene and 80 g of O-ethyl-S-methyl-thiolphosphorous acid chloride (Kpo 47 "C) are then added dropwise at 10 ° C. with stirring. To complete the reaction, stirring is continued for 1 hour at 10 ° C; 16 g of finely powdered sulfur are then added, the temperature of the mixture rising to 600 ° C.

The mixture is heated to 60 ° C. for a further 1/2 hour and then the reaction product is added in 300ccm of ice water.

The toluene layer is separated, dried with sodium sulfate and fractionally distilled. After evaporation of the solvent, one obtains through Rectification of the residue 49 g (50 ° / "of theory) O - ethyl - S-methyl - thionothiolphosphoric acid ethylene imide vom Kp.o, o1 58 "C.

Example 3 94 g (0.5 mol) of O-ethyl-S-isopropyl-thiolphosphoric acid chloride (boiling point 52 "C) are dissolved in 300 cc of benzene. 22 g of ethyleneimine and 51 g of triethylamine are added to this solution, and reaction mixture 1 is stirred Hour at room temperature and then add 16 g of sulfur all at once, the temperature rising to 60 "C. After the reaction has subsided, the mixture is heated to 60 ° C. for a further hour and the reaction product is then worked up as described in Examples 1 and 2. 57 g (51% of theory) of O-ethyl-S-isopropylthionothiolphosphoric acid are obtained. ethyleneimide of Kp'oi 65 "C.

Example 4 A solution of 22 g of ethyleneimine and 51 g of triethylamine in 300 cc of benzene is added while stirring with 104 g (0.5 mol) of O-ethyl-S-sec-butylthiolphosphorous acid chloride (boiling point 472 ° C.) and the mixture is warmed 1 hour at 30 "C and then enters 16 g of finely powdered sulfur. The temperature rises to 60 to 65 "C. To complete the reaction, the mixture is heated to 65" C for a further hour and then worked up as in Examples 1 and 2. The resulting O-ethyl-S-sec-butyl-thionothiolphosphoric acid-ethyleneimide boils under a pressure of 0.01 mm at 72 ° C. Yield 48 g (400/0 of theory).

Claims (1)

Claim: A process for the preparation of thiophosphoric acid ethyleneimides, characterized in that O, S-dialkylthiolphosphoric acid chlorides of the general formula are used in a manner known per se in which R1 and R2 are lower alkyl radicals, reacts with ethyleneimine in the presence of an acid-binding agent and the resulting O, S-dialkylthiolphosphoric acidethyleneimide of the general formula with the equivalent amount of sulfur to compounds of the general formula implements. ~~~~~~~~ Publications taken into consideration: German Patent No. 854 651; German explanatory documents No. 1 061 785, 1 064 064.