DE3227098C2 - - Google Patents

Description

The phosphorylated acid anilides according to the invention correspond of the general formula (I)

in which R, R¹, R², R³, R⁴, R⁵ and X have the following meanings:
R is alkyl with 1-8 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-4 carbon atoms, alkyl with 1-4 carbon atoms, substituted by halogen, benzyl, alkoxymethyl, unsubstituted phenyl or by a halogen atom, a methoxy or nitro phenyl or carbalkoxy group substituted,
R¹ represents hydrogen, halogen, trifluoromethyl, alkoxy, carbalkoxy or cyano,
R² and R³ stand separately for hydrogen, halogen, alkyl with 1-4 carbon atoms, trifluoromethyl, alkoxy, carbalkoxy or cyano,
R⁴ and R⁵ are identical or different and both mean alkyl with 1-4 carbon atoms,
X is oxygen or sulfur.

Under the alkyl group given for the substituent R. with 1-8 carbon atoms are a methyl, ethyl, Propyl, isopropyl, butyl, secondary butyl, tertiary Butyl, isobutyl, pentyl, hexyl, heptyl group, under an alkenyl group with 2-4 carbon atoms Ethenyl, propenyl and allyl group, under through a halogen atom substituted alkyl group with 1-4 carbon atoms Chloromethyl group, dichloromethyl, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl group understood.

That by a halogen atom, a nitro, alkoxy, carbalkoxy group substituted phenyl group can be a 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 4-bromophenyl, 2-fluorophenyl, 4-fluorophenyl, 2-nitrophenyl, 3-nitrophenyl, 2-carbmethoxy, 2-carbethoxy, 2-carbpropoxy, Be 2-carbisopropoxy group.

The halogen atom of R1 can be bromine, chlorine, fluorine Alkoxy group can be methoxy or ethoxy, its carbalkoxy group can be for a carbmethoxy or carbethoxy group stand.

The alkyl group of R² and R³ with 1-4 carbon atoms can be methyl, ethyl, propyl, isopropyl, tertiary Butyl, its halogen atom can be bromine, chlorine, Are fluorine, their alkoxy group can be methoxy or ethoxy and the carbalkoxy group can be for a carbmethoxy or a carbethoxy group.

The alkyl group of R⁴ and R⁵ with 1-4 carbon atoms is identical to that of R² and R³.

The compounds are used in agriculture where they successfully control mites and insects can be. In contrast to known acaricides and The compounds according to the invention are largely insecticides harmless to bees.

The compounds of general formula (I) are in  not yet known to the specialist literature. Similar connections are in the U.S. Patent No. 37 14 299 described. The common feature of these known compounds is that in position 2 of the nitrogen atom the aromatic amide substituting aromatic Ringes always an alkyl group is present.

The common feature of the subject of this invention forming compounds of general formula (I) however, that in the o-position of the nitrogen atom Aromatic ring substituting aromatic ring there is no alkyl group, but one of the substituents as indicated under R¹.

The preparation of the compounds of the general formula (I) relies on the implementation of the corresponding reaction Schiff base with a corresponding one N-Halo-methyl-carboxylic acid anilides are formed with organic or inorganic salts of Phosphoric acid esters. It was through knowledge enables - the finally also led to the present invention -, that the 1,3,5-triaryl-hexahydro-1,3,5-triazines with carboxylic acid chlorides to the corresponding N-chloro-methyl-carboxylic acid anilides lead with O, O-dialkyl-dithiophosphoric acids or O, O-dialkyl-thio-phosphoric acids or their organic or inorganic salts to compounds of the general Formula (I) can be implemented. The further one Recognition that the N- (chloromethyl) carboxylic acid anilides also with free O, O-dialkyldithio-phosphoric acids and O, O- Dialkyl-thio-phosphoric acids react - for which there is none Literature gives - makes the inventive method easy to carry out and economical; it requires no special facility. The connections can easily cleaned and the solvents recovered will.  

The procedure is as follows:
The 1,3,5-triaryl-hexahydro-1,3,5-triazine is dissolved in a solvent, then at the boiling point of the solution, which is between 50 and 140 ° C depending on the solvent, the solution prepared with an identical solvent the carboxylic acid chloride added. The resulting N- (chloromethyl) carboxylic acid anilide is isolated or without isolation with the corresponding O, O-dialkyldithio-phosphoric acid or O, O-dialkyl-thio-phosphoric acid or their organic or inorganic salts at 20-40 ° C implemented.

Chlorinated hydrocarbons, e.g. B. dichloromethane, carbon tetrachloride, chloroform, Dichlorethylene, tetrachlorethylene, aromatic and chlorinated hydrocarbons, e.g. B. benzene, toluene, Xylene, chlorobenzene, dichlorobenzenes, aliphatic ketones, such as acetone, methyl ethyl ketone and acetonitrile, Dimethylformamide, dimethyl sulfoxide, ether, e.g. B. Dioxane and diethyl ether in question.

The salt-forming bases of O, O-diaklyl-dithio-phosphoric acid can be inorganic bases, such as the oxides, hydroxides and be carbonates of alkali metals; as organic Bases come in tertiary amines such as triethylamine and pyridine in question.

With the compounds of general formula (I) Acaricidal and insecticidal agents made with Water can be diluted as desired. The funds included 5-70% by weight, e.g. B. 50-70 wt .-%, active ingredient in addition usual auxiliaries and carriers, such as diluents, Wetting and emulsifying agents.

Aromatic hydrocarbons, e.g. B. xylene, toluene, aliphatic carbons, e.g. B. hexane, further dimethylformamide, dimethyl sulfoxide, then dibutyl phthalate, as a wetting and emulsifying agent  containing anionic and nonionic components Emulsifier combinations can be used.

The funds can be successful in crop protection, forest protection and in the fields of storage and healthcare to control the insect pests occurring there and mites are used. They look excellent against rodent pests, have a corresponding Effectiveness, and accordingly the in Plant crops of insect pests and mites to be fought better than with known means.

Contains a beneficial agent

50% by weight of compound of the general formula (I),
10% by weight of a commercial emulsifier which contains the nonionic components polyoxyethylene alkyl aryl ether and sorbitan alkylate and an anionic component
40% by weight xylene.

The invention is explained in more detail in the following examples.

Example 1 Preparation of S - [(butanoyl-2-chlorophenylamino) methyl] -O, O-dimethyl-dithiophosphate-

250 ml of benzene, 41.8 g of 1,3,5-tris (2-chlorophenyl) hexahydro-1,3,5-triazine are added, then the solution is heated to the boiling point and the mixture is prepared with 50 ml of benzene with stirring Solution of 32 g of butyric acid chloride added. After stirring for 10 minutes, the reaction mixture is cooled to 25 ° C. and 48 g of O, O-dimethyl-dithiophosphoric acid are added dropwise with stirring. The mixture is stirred for 2 hours, then washed with 3 × 100 ml of water, dried over sodium sulfate and the benzene is removed from the organic phase by a vacuum evaporator. The colorless oil obtained crystallizes after a few hours.
Melting point: 41 ° C

Example 2 Preparation of S - [(2-chlorophenyl-propionyl- amino) methyl] -O, O-dimethyldithiophosphate

41.8 g 1,3,5-tris (2-chlorophenyl) hexahydro-1,3,5- triazine are dissolved in 250 ml of benzene, then is under Stir the 28 g solution prepared with 50 ml of benzene Propionyl chloride added at 50 ° C. The reaction mixture is cooled to 25 ° C, then with 100 ml Solution of 67.5 g of O, O-dimethyl-dithio- added phosphoric acid triethyl ammonium salt. 30 minutes are stirred, then the organic phase with Washed 3 × 150 ml of water, dried over sodium sulfate and the benzene distilled off.

The remaining pale yellow oil is the title compound, which is purified by chromatography on SiO₂.

Example 3 Preparation of S - [(Butanoyl-2-chlorophenyl- amino) methyl] -O, O-dimethylthio-phosphate

21 g 1,3,5-tris (2-chlorophenyl) hexahydro-1,3,5- triazine are dissolved in 150 ml of dioxane, then is Stir at 30 ° C in small portions with 50 ml of xylene prepared solution of 12 g of butyric acid chloride added. After stirring for 30 minutes, 36 g of O, O-dimethyl-thio-phosphoric acid pyridinium salt are added at 25 ° C dissolved in 50 ml of dioxane added. The reaction mixture is left for 1 hour stirred, then diluted with 500 ml of water, the title compound separates out as a colorless oil that separates, dissolved in 100 ml of benzene and dried over sodium sulfate becomes. After removing the benzene, the title compound remains back as oil.  

Example 4 Preparation of S - [(Butanoyl-2-trifluoromethyl- phenylamino) methyl] -O, O-dimethyldithiophosphate

52 g 1,3,5-tris (trifluoromethylphenyl) hexahydro 1,3,5-triazine are dissolved in 200 ml of chloroform and At 60 ° C, 32 g of butyric acid chloride are added dropwise. The The reaction mixture is cooled to 25 ° C. and 90 g of O, O-dimethyl-dithio-phosphoric acid are added, then let it stand for 3 hours, finally with Washed 3 × 150 ml of water, the chloroform-containing phase is dried over magnesium sulfate. After distilling off chloroform, the title compound remains as colorless Oil back, which recrystallized from the mixture of n-hexane and benzene becomes.

Example 5 Preparation of S - [(/ 2-fluoro-phenyl / -propionyl- amino) methyl] -O, O-dimethyldithiophosphate

36.7 g 1,3,5-tris (2-fluorophenyl) hexahydro 1,3,5-triazine are dissolved in 100 ml of acetone and the solution is heated to the boiling point. Be under heating 28 g of propionyl chloride are added, then the reaction mixture cooled to 25 ° C and with stirring 54 g of O, O-dimethyl-dithio-phosphoric acid sodium salt added. After stirring for 3 hours, this is separated Filtered off sodium chloride, the acetone was distilled off, the remaining oil washed with 20 ml of hexane and then the hexane removed. The remaining oil is the title compound.

Based on the examples described u. a. the compounds listed in Table 1 prepared.  

Table 1

Compounds of general formula I prepared by the process according to the invention

Example 6 Production of a 70% by weight emulsifiable concentrate

It contains

70% by weight of S - [(2-chlorophenylpropionylamino) methyl] -O, O-dimethyldithiophosphate,
20% by weight xylene,
10 wt .-% commercial emulsifier, which contains the nonionic components polyoxyethylene alkyl aryl ether and sorbitan alkylate and an anionic component.

The components are mixed together and thoroughly homogenized.

Example 7 Production of a 50% by weight emulsifiable concentrate

50% by weight of S - [(butanoyl-2-chlorophenylamino) methyl] -O, O-dimethyldithiophosphate,
20% by weight xylene,
20% by weight dimethylformamide,
10% by weight of a commercially available mixture of nonionic and ionic emulsifiers.

Example 8 Production of a 30% by weight emulsifiable concentrate

30% by weight of S - [(butanoyl-2-trifluoromethylphenylamino) methyl] -O, O-dimethyldithiophosphate,
30% by weight dibutyl phosphate,
30% by weight xylene,
10% by weight of emulsifier according to Example 6.

Example 9 Production of a 5 wt .-% emulsifiable Concentrate

5% by weight of S - [(butanoyl-2-chlorophenylamino) methyl] -O, O-dimethyl-dithiophosphate,
90% by weight of xylene,
5% by weight of emulsifier according to Example 6.

From the emulsifiable substances described in Examples 6 to 9 Concentrates can be diluted with water directly sprayable spray liquids are produced.

Examples of laboratory and greenhouse experiments Example 10 Effect against Tetranychus urticae - double-sided Spider mite

With the 0.1% aqueous emulsion of the concentrate from Example 6 were used to cover completely sprayed such bean plants with a population of Tetranychus urticae developed on them in different Stages of development were heavily infected.

The effect is considered 100% since 24 hours after treatment no more live mites on the leaves were to be found.

Example 11 Ovicidal activity against the eggs of the tetranychus urticae, the spotty spider mite

With the 0.1% aqueous emulsion of the concentrate from Example 6 were used to cover completely sprayed such bean plants, of which the imagines and the larvae of the mites were removed on their leaves only a lot of mite eggs remained.  

The effect is considered 100% because after Neither living nor dead mites on the leaves for 1-10 days and only the dried eggs, their pearly Had lost their shine.

Example 12 Contact and gastric toxicity against Phaedon cochleariae - Horseradish leaf beetle

Cabbages are made with the 0.1% aqueous emulsion sprayed the concentrate from Example 7 to flow and on the still wet leaves become Phaedon cochleariae larvae set.

The effect is considered 100% since 24 hours all larvae died after treatment.

Example 13 Contact and gastric toxicity against Plutella maculipennis - Cabbage moth

The cabbage leaves were mixed with the 0.1% aqueous emulsion sprayed the concentrate from Example 7 to flow and on the still moist leaves Plutella maculipennis- Given larvae.

The effect is considered 100% because 24 Hours after treatment all larvae had died.

Example 14 Contact and gastric toxicity against Athalia rosae - Rapeseed wasp - adults and larvae

Oilseed rape plants were used until they flowed with 0.1% sprayed aqueous emulsion of the concentrate of Example 8 and Athalia rosae larvae were placed on the still moist leaves given and imagines.  

The death of larvae and adults is given in%. The effect is considered 100% since 24 hours after all larvae had died during treatment.

Example 15 Effect against Musca domestica - house fly

In a container covered with a tulle net with a Volumes of 200 cm³ were placed on Musca domestica adults, then the test animals were treated with the 0.1% active ingredient sprayed aqueous emulsion of the concentrate of Example 8.

After an exposure time of 24 hours, the insecticide Effect expressed in% of animals killed.

Example 16 Action against Acanthoscelides obtectus - bean beetle

The examinations and the scoring were as in Example 15 carried out, with that described in Example 8, concentrate dilutable with water.

Example 17 Effect against Aphthona euforbiae - flax earth flea

For field trials in small plots the killing effect in a flat culture in a dose of 1 kg / ha and 1000 l / ha spray liquid from concentrate of Example 9 100% against the flax earth flea.

Example 18 Action against Sitona spp. - Leaf beetle

In field trials on small plots the killing effect in a dose of 1 kg / ha and with 1000 l / ha spray liquid from concentrate from Example 9 in a pea culture 100% against leaf beetles.  

Example 19 Effect against Tortricidae spp.

For field trials in small plots the killing effect in a dose of 1 kg / ha and with 2000 l / ha Spray liquid from concentrate from Example 7 in a peach culture 100% and offers protection against Tortricidae spp.

Example 20 Effect against Phyllobius spp.

In small-scale field trials, the killing effect is in a dose of 1 kg / ha and with 1000 l / ha spray liquid from concentrate from Example 9 100% and protection against Phyllobius spp. is offered.

Example 21 Effect against Athalia rosae - rape wasp

In small-scale field trials, the killing effect was against rapeseed wasp and pseudo caterpillars in one Dose of 1 kg / ha and with 1000 l / ha spray liquid Concentrate from Example 8 100%.

Example 22 Action against Leptinotarsa decemlineate - Colorado beetle

In small-scale field trials, the killing effect was against the adults and larvae of the Colorado beetle (Leptinotarsa decemlineata) at a dose of 1 kg / ha and with 1000 l / ha spray liquid from concentrate from Example 9 100%.

The insecticidal effect of the Compounds 33, 3 and 4 prepared emulsions highlighted, which is illustrated in Table 2.  

Table 2

Claims (3)

1. Phosphorylated acid anilides of the general formula (I) wherein
R alkyl with 1-8 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-4 carbon atoms, alkyl with 1-4 carbon atoms, substituted by halogen, benzyl, alkoxymethyl, unsubstituted phenyl or by a halogen atom, a methoxy, nitro or carbalkoxy group is substituted phenyl,
R¹ represents hydrogen, halogen, trifluoromethyl, alkoxy, carbalkoxy or cyano,
R² and R³ separately represent hydrogen, halogen, alkyl having 1-4 carbon atoms, trifluoromethyl, alkoxy, carbalkoxy or cyano,
R⁴ and R⁵ are identical or different and both represent alkyl with 1-4 carbon atoms,
X is oxygen or sulfur. 2. Process for the preparation of the compounds according to Claim 1, characterized in that a 1,3,5-triphenyl-hexahydro-1,3,5-triazine, the phenyl groups corresponding to the general formula (I) by R¹, R² and R³ are substituted, dissolved in a solvent and  the solution heated to its boiling point is a carboxylic acid chloride, wherein R is as defined in claim 1 added is, the N- (chloromethyl) carboxylic acid anilide obtained in situ or after isolation with the appropriate O, O-dialkyldithiophosphoric acid or its organic or inorganic salt, wherein R⁴ and R⁵ as in claim 1 are defined, implemented and the product if desired washed, cleaned and dried. 3. Acaricidal and insecticidal agent, one effective amount of the compound of general formula (I) and contains carriers and / or emulsifiers.