DE2532628A1 - Fluorine substd. carbamoylmethyl dithiophosphonates - useful as insecticides, acaricides and nematocides - Google Patents

Abstract

Novel phosphorus esters are formula: (RO)(R1)PS-S.-CHF.CONR2R3 (I), (R and R1 are are each 1-6C alkyl, R2 and R3 are each H or 1-4C alkyl). They are prepd. by reacting (RO)(R1)P(S).SM(M = H or an equiv. of an alkali, alkaline earth or NH4) with F.CH(Hal).CONR2R3. (I) are insecticides, acaricides and nematocides and are more active than known cpds. of similar structure. They are useful in plant protection, for hygienic applications and for preservation of stored goods. They have excellent residual activity on wood and clay and are stable to alkali on white-washed surfaces. In an example O-ethyl, S-(N-methylcarbamoylfluoromethyl)ethanethionotiolophosphonate was prepd. from K salt of O-ethyl ethanethionothiolophosphonate and N-methyl fluorochloroacetamide.

Description

Fluorine-substituted carbaminylmethyldithioalkanephosphonic acid esters, Process for their production and their use as insecticides, acaricides and nematicides The present invention relates to new fluorine-substituted carbaminylmethyldithioalkanephosphonic acid esters, a process for their production and their use as insecticides, acaricides and nematicides.

It is already known that carbaminylmethyldithiophosphorus (phosphonic) acid esters, e.g. O, O-dimethyl-S- (N-methyl-carbaminylmethyl) -thionothiolphosphoric and O-ethyl-S- (N-methyl-carbaminylmethyl) -thionothiolithanphosphonic acid ester, have insecticidal and acaricidal properties (see U.S. Patent 2,494,283 and German Auslegeschrift 1.137.ol3).

It has been found that the new fluorine-substituted carbaminylmethyldithioalkanephosphonic acid esters of the formula in which R and R 'PUr are identical or different alkyl radicals having 1 to 6 carbon atoms, while R "and R"', which can be identical or different, denote hydrogen or alkyl sit 1 to 4 carbon atoms, strong insecticidal, acaricidal and nematicidal properties own.

The compounds of formula (I) are generally in the form of Racemates before.

It has also been found that the new fluorine-substituted carbaminylmethyldithioalkanephosphonic acid esters of the formula (I) are obtained if O-alkyldithioalkanephosphonic acid esters of the formula in which R and R 'have the meaning given above and M stands for hydrogen, an alkali, alkaline earth or

Ammonium equivalent with fluoroacetamide derivatives of the formula in which R "and R"'have the meaning given above and Hal represents halogen, in particular chlorine or bromine, optionally reacted in the presence of acid acceptors and optionally in the presence of solvents or diluents.

Surprisingly, the fluorine-substituted compounds according to the invention show Carbaminylmethyldithioalkanephosphonic acid ester a better insecticidal, acaricidal and nematicidal activity than the corresponding previously known from the prior art Carbaminylmethyldithiophosphorus (phosphonic) acid ester of analogous constitution and the same Direction of action. The products according to the present invention thus represent a real one Enrichment of technology.

If, for example, the potassium ual of the O-iao-propylethiophosphonic acid ester and fluorochloro-N-methylacetauide are used as starting materials, the course of the reaction can be represented by the following equation: The starting materials to be used are clearly and generally defined by the formulas (II) and (III). Preferably, however, R stands for straight-chain or branched alkyl with 1 to 4, R 'for straight-chain or branched alkyl with 1 to 3 carbon atoms, R n for hydrogen, methyl and ethyl and R "' for methyl and ethyl.

The O-alkyldithioalkanephosphonic acid esters to be used as starting materials (11) are known from the literature and can be produced by generally customary processes (compare e.g. German Auslegeschrift 1.101.417), as well as the fluoroacetamide derivatives (III), which e.g. by reacting amines with fluorochloroacetic acid alkyl esters (manufacture see Org. Syntheses Coll. Vol. IV, p. 423) can be obtained.

Examples of the O-alkyldithioalkanephosphonic acid esters (II) are specifically mentioned: 0-methyl-, 0-ethyl-, O-n-propyl-, O-iso-propyl-, O-n-butyl-, O-iso-butyl, O-sec-butyl, O-tert-butyl methane or -ethane, -n-propane, -iso-propanedithiophosphonic acid ester and the corresponding alkali, alkaline earth and ammonium salts.

As examples of the fluoroacetamide derivatives to be reacted according to the process (III) may be mentioned in detail: N-methyl-, N-ethyl-, N, N-dimethyl-, N, N-diethyl-fluorochloroacetamide.

The process for making the compounds of the invention is preferably carried out with the use of suitable solvents and diluents. Practically all inert organic solvents can be used as such. For this include in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, Gasoline, methylene chloride, chloroform, Carbon tetrachloride, chlorobenzene, or ethers, e.g. diethyl and dibutyl ethers, Dioxane, also ketones, for example acetone, methylethyl, methylisopropyl and Methyl isobutyl ketone, as well as nitriles such as aceto- and propionitrile.

All customary acid binders can be used as acid acceptors Find. Alkali carbonates and alcoholates, such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, Dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature can vary within a relatively wide range will. In general, the temperature is between 0 and 120 ° C., preferably at 30 to 6o0C.

The reaction is usually allowed to proceed at normal pressure In the process, the starting materials are generally set in an equimolar ratio a. An excess of one or the other component has no significant advantages. The phosphonic acid ester component (II) is preferably put in salt form in one the above-mentioned solvents and the solution is mixed with the fluoroacetamide derivative (III).

After the reaction has ended, which is usually carried out at an elevated temperature one adds an organic solvent to the mixture and works the organic Phase in the usual way by washing, drying and "partial distillation".

The new compounds are in the form of oils that are not Let it distill without decomposition, but by so-called "undistillieren", d. H. by prolonged heating under reduced Pressure on moderately increased Temperatures freed from the last volatile components and cleaned in this way will. The refractive index is used to characterize them.

As already mentioned several times, the inventive fluorine-substituted carbaminylmethyldithioalkanephosphonic acid ester by an excellent insecticidal, acaricidal and nematicidal effectiveness. They work against plant, Hygiene and storage pests and have both a low phytotoxicity good effect against sucking and eating insects and mites.

For this reason, the compounds according to the invention can be used successfully in crop protection as well as in the hygiene and stored product protection sector as pesticides can be used.

The sucking insects mainly include aphids (Aphidae) like the green peach aphid (Myzus persicae), the black bean (Doralis fabae), oat (Rhopalosiphum padi), pea (Macrosiphum pisi) and potato lice (Macrosiphum solanifolil), also the currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black Cherry aphid (Myzus cerasi), also scale and mealybugs (Coccina), e.g. the ivy shield (Aspidiotus hederae) and cup scale (Lecanium hesperidum) as well the mealybug (Pseudococcus maritimus); Bladder feet (Thysanoptera) such as Hercinothrips femoralis and bed bugs, for example beetroot (Piesma quadrata), cotton (Dysdercus intermedius), bed bug (Cimex lectularius), predatory bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans), also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects, butterfly caterpillars should be mentioned above all (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), golden afters (Euproctis chrysorrhoea) and ring moth (Malacosoma neustria), furthermore the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frostworm (Cheimatobia brumata), Oak moth (Tortrix viridana), the army (Laphygma frugiperda) and Egyptian Cotton worm (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestit kühniella) and large wax moth (Galleria mellonella), Farther are among the biting insects beetles (Coleoptera) e.g. corn (Sitophilus granarius = Calandra granaria), potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), Raspberry (Byturus tomentosus), table bean (Bruchidius = Acanthoscelides obtectus), Bacon (Dermestes frischij, Khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread (Stegobium paniceum), common meal beetle (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground, e.g. B. Wireworms (Agriotes spec.) and white grubs (Melolontha melolontha); Cockroaches like the Germans (HIattella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia maderae), Oriental (Blatta orientalis), giant (Blaberus giganteus) and giant black cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; also orthopteres e.g. the House crickets (Gryllus domesticus); Termites such as the terrestrial termites (Reticulitermes flavipes) and Hymenoptera such as ants, for example the meadow ant (Lasius niger).

The Diptera essentially comprise flies like the Tau (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small house fly (Fannia canicularis), gloss fly (Phormia regina) and blowfly (Calliphora erythrocephala) and the calf stick (Stomoxys calcitrans); furthermore NUcken, e.g. Mosquitoes such as the yellow fever (Aedes aegypti), house (Culex pipiens) and malarial mosquitoes (Anopheles stephensi), The mites (Acari) are especially those Spider mites (Tetranychidae) such as the bean (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = Panonychus ulmi), gall mites, e.g. the currant gail mite (Eriophyes ribis) and tarsonemids, for example the shoot tip mite (Hemitarsonemus latus) and Cyclamen mite (Tarsonemus pallidus); finally ticks like the leather tick (Ornithodorus moubata).

When used against hygiene and storage pests, especially Flying and embroidery, the process products are also characterized by excellent Residual effect on wood and clay as well as good alkali stability on limed Documents from.

The active ingredients according to the invention have low toxicity to warm-blooded animals strong nematicidal properties and can therefore be used to combat nematodes, in particular phytopathogenic nematodes can be used. This essentially includes Leaf nematodes (Arphelenchoides), such as the chrysanthemum male (A. ritzemabosi), the strawberry elbow (A. fragariae), the rice elbow (A. oryzae); Stem nematodes (Ditylenchus), like the little stick (D. Dipsaci); Root knot nematodes (Meloidogyne) such as M. arenaria and M. incognita; cyst-forming nematodes (Heterodera), such as the potato nematode (H. rostochiensis), the beet nematode (H. schachtii); as well as free-living root nematodes e.g. of the genera Pratylenchus, Paratylenchus, Rotylenchus, Xiphinema and Radopholus.

The active compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These are produced in a known manner, e.g. by mixing the active ingredients liquefied pressurized liquids with extenders, i.e. liquid solvents Gases and / or solid carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means. In the case of using water as an extender, e.g. organic Solvents can be used as co-solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g., aerosol propellants such as halogenated hydrocarbons, e.g., freon; as solid carrier materials: natural rock flour, such as kaolins, clays, talc, Chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock soles, such as finely divided silica, aluminum oxide and silicates; as emulsifying and / or Foaming agents: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant: e.g. Lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be mixed in the formulations with other known active ingredients.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active ingredients can be used as such, in the form of their formulations or in the application forms prepared therefrom, such as ready-to-use solutions, emulsions, Foams, suspensions, powders, pastes, soluble powders, dusts and granules be applied. It is used in the usual way, e.g. by spraying, Spraying, atomizing, dusting, scattering, smoking, gasifying, pouring, pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can be varied in larger areas. In general, they are between 0.0001 and 10 46, preferably between 0.01 and 1%.

The active ingredients can also be used with good success in the ultra-low-volume process (ULV) used where possible, formulations up to 95% or even to apply the 100% active ingredient alone.

Example A Limit Concentration Test / Soil Insect I Test Insect: Phorbia antiqua maggots in the soil Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether for the production of an appropriate active ingredient preparation mixing 1 part by weight of active ingredient with the specified amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water the desired concentration.

The active ingredient preparation is intimately mixed with the soil.

The concentration of the active ingredient in the preparation plays a practical role Doesn't matter, the only decisive factor is the amount of active ingredient by weight per unit volume Soil, which is given in ppm (= mg / l). The bottom is filled into pots and left these stand at room temperature.

After 24 hours, the test animals are placed in the treated soil and after another 2 to 7 days, the effectiveness of the active ingredient is determined by counting of the dead and live test insects determined in 96. The efficiency is 100 5 ', when all test insects have been killed, it is 0 96, if just as many Test insects live as in the untreated control.

Active ingredients, application rates and results are shown in Table 1 below: Table 1 Limit concentration test / soil insects I (Phorbia antiqua maggots in the soil) Active substance kill rate in 96 an active ingredient concentration tration of 2.5 ppm CH3 0 5 rl PS-CH2-CO-NH-CH3 0 30 3 CH (known) C2H50 5 PS-CHF-CO-NHCH3 100 / f 3 C2H5 n-C30 5 100 \ II / PS-CH-CO-NH-CH3 C2H5 F Example B Limit concentration test / soil insects II Test insect: Tenebrio molitor larvae in the soil Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount of solvent, the stated amount of emulsifier is added and diluted the concentrate with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil.

The concentration of the active ingredient in the preparation plays a practical role Doesn't matter, the only decisive factor is the amount of active ingredient by weight per unit volume Soil, which is given in ppm (= mg / l). The bottom is filled into pots and left these stand at room temperature.

After 24 hours, the test animals are placed in the treated soil and after another 2 to 7 days, the effectiveness of the active ingredient is determined by counting of the dead and living test insects in, 'intended. The efficiency is 100 5 ', when all test insects have been killed, it is 0 5 ', if just as many Test insects live as in the untreated control.

Active ingredients, application rates and results are shown in Table 2 below: Table 2 Limit concentration test / soil insects II (Tenebrio molitor larvae in the soil) Active ingredient kill rate in 96 at one Active ingredient concentration of lo PPm CH OS 3 \ II PS-CH2-CO-NH-CH3 0 CH30 (known) C2H5 ° 100 / PS-CHF-CO-NHCHD 100 3 C2H5 CH30y S / CH3 P-CH-CO-N 100 C2H5 F 3 C2H5 5 / [-S-CH-CO-NH-CH3 100 n-C30 F Example C Limit Concentration Test / Nematodes Test nematodes: Meloidogyne incognita Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil with the Test nematode is heavily contaminated. The concentration of the active ingredient plays a role here Practically no role in the preparation, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm. One fills the treated one Ground in pots, sow lettuce and keep the pots at a greenhouse temperature from 27 0C.

After four weeks, the lettuce roots are checked for nematode infestation (root galls) investigated and determined the efficiency of the active ingredient in%. The efficiency is 100 5 'if the infestation is completely avoided, it is 0 5' if the infestation is exactly as high as in the control plants in untreated, but the same Way contaminated soil.

Active ingredients, application rates and results are shown in Table 3 below: Table 3 Limit concentration test / nematodes (Moloidogyne incognita) Active ingredient kill rate in% with one Active ingredient concentration of 20 ppm CH30y S PS-CH2-CO-NH-CH3 0 CH 0 3 (known) C2H, OS S-CHF-CO-MH-CH3 100 C2H5 CH30 \ IS / CH3 100 PS-fH-CO-N \ 100 C2H5 / FC 25th Example D Plutella test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound dewy and populated with caterpillars of the cabbage moth (Plutella maculipennis).

After the specified times, the destruction is determined in%.

100 5 'means that all the caterpillars have been killed; 0% means that no caterpillars were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 4 below: Table 4 (Plutella test) Active ingredient active ingredient kill rate concentration in 96 after in 5 '3 days 5 C2H5 X 0.1 100 / -S-CH2-CO-NH-CH3 0.01 0 C2H50 (known) C2H5 S 0.1 100 3 -CO-NH- 0.01 100 C2H50 C2H S CH3 C 0.1 100 5 \ 11/0 01 100 PS-CHF-C0- / 0.01 100 C2H5 0 NCH3 C2H5 5 CH3 0.1 100 -S-CHF-C0- / 0, 01 1 00 CtI3 0 CH3 C2H5 $ 0.1 100 PS-CHF-C0-NH-CH3 0.01 100 n 3H7 Example E Tetranychus test (resistant) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which strongly differ from all stages of development of the common spider mite or bean spider mite (Tetranychus urticae) are infected, sprayed dripping wet.

After the specified times, the destruction in 96 is determined.

100 5 'means that all spider mites have been killed; 0 96 means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 5 below: Table 5 (Tetranychus test) Active ingredient active ingredient kill rate concentration in 96 after In 2 days 0.1 95 (CH30) 2P-S-CH2-C0-NH-CH3 0.01 o (known) C2H5 ß 0.1 100 PS-CHF-CO-NH-CH 0.01 95 3 nC, H70 Production example board example 1 12.6 g (0.1 mol) of N-methylfluorochloroacetamide are added to a solution of 21.8 g (0.1 mol) of the potassium salt of 0-ethyl-ethane-thionothiolphosphonic acid ester in 250 ml of acetonitrile, and the mixture is stirred 4 Hours at 45 to 50C, then 500 ml of toluene are added and it is washed 3 times with 300 ml of water each time. The organic phase is dried over sodium sulfate and concentrated under reduced pressure. The residue is distilled at 60 ° C. in a high vacuum and 19 g (73% of theory) of O-ethyl-ethane-S- (N-methylcarbaminyl-fluoromethyl) thionothiolphosphonic acid ester are obtained in the form of a yellow oil with the refractive index n2D: 1 D 5137.

The following connections can be established in an analogous manner: With physical data yield stalk (refractive (96 der No. Constitution index) theory) 2 2 5 / PS-CH-CO-N (CH3) 2 nu3: 1.52oo 68 C2H5 1 F. 5 3 CH30 22 C2H5 3 PS-CH-CO-N (CH3) 2 nD2: 1.5178 50 F. 4 n-C3H70 \ n24: 1.4965 81 C2H5 7 Ìp-s-cH-co-NH-cHD D F. The fluoroacetoamide derivatives (III) to be used as starting materials can be prepared as described below.

To 45 g of an aqueous (4c to 50%; corresponding to 0.4 to 0.5 mol) Dimethylamine solution is added at 50 ° C. 42 g (0.3 mol) of ethyl fluorochloroacetate (manufactured according to Org.

Syntheses Coll. Vol. IV, p. 423) and the mixture is stirred for 4 hours 0 to 5 ° C. The water is then drawn off at a maximum bath temperature of 40 ° C, the residue is distilled under reduced pressure and thus receives 20 g (47 96 der Theory) Fluoro-chloro-N, N-dimethylacetamide in the form of a colorless liquid with the boiling point 53 0C / 0.01 Torr and the refractive index nD24: 1.4530.

In the same way, the following compounds can be obtained: Boiling point 51OC / O 01 Torr; Refractive index n D: 1.4444 boiling point 65-68 ° C / 0.1 Torr; Melting point: 320C

Claims (6)

Patent claims fluorine-substituted carbaminylmethyldithioalkanephosphonic acid esters of the formula (I) in which R and R 'stand for identical or different alkyl radicals with 1 to 6 carbon atoms, while R "and R"', which can be identical or different, denote hydrogen or alkyl with 1 to 4 carbon atoms. 2. Process for the preparation of fluorine-substituted carbaminylmethyldithioalkanephosphonic acid esters, characterized in that O-alkyldithioalkanephosphonic acid esters of the formula (II) in which R and R 'have the meaning given in claim 1 and M represents hydrogen, an alkali metal, alkaline earth metal or ammonium equivalent, with fluoroacetamide derivatives of the formula (III) in which R "and R"'have the meaning given in claim 1 and Hal represents halogen, in particular chlorine or bromine, optionally reacted in the presence of acid acceptors and optionally in the presence of solvents or diluents. 3. Insecticidal, acaricidal and nematicidal agents, characterized by a content of compounds according to claim 1. 4. Method of combating insects, mites and nematodes, thereby characterized in that compounds according to claim 1 are applied to the pests mentioned or lets its habitat act. 5. Use of compounds according to Claim 1 for combating Insects, mites and nematodes. 6. Process for the production of insecticidal, acaricidal and nematicidal Agents, characterized in that compounds according to Claim 1 are mixed with extenders and / or mixes surfactants.