DE2237037A1 - O-phenyl alkane phosphonothioamidates - with insecticidal and acaricidal activity - Google Patents

Abstract

Cpds. of formula (I): (where R is lower alkyl; each X is Cl, Me or MeS; n = 1 or 2) have insecticidal and acaricidal activity. They are pref. prepd. by reacting the corresp. O-phenyl alkanephosphonothioic acid halide with NH3.

Description

O-phenyl-thiono-alkanephosphonic ester amides, process for their preparation and their use as insecticides and acaricides O-Aryl-N, N-dialkyl-thiono-alkanephosphonic acid ester amides, e.g. O- [4-chlorophenyl] -N, N-dimethyl- or O-L2,4-dichlorophenyl / ° N, N = dimethyl-thionoethosphonic acid ester amide, have insecticidal and acaricidal properties (cf. the German Auslegeschrift 1.142o6O5) e It has now been found that the new O-phenyl-thiono-alkane phosphonic acid ester amides of the formula (1) in which R stands for a lower alkyl group, while X is a chloretone, the methyl or methylmetcapto radical and n is 1 or 2 have strong insecticidal and acaricidal properties.

It has also been found that the new O-phenyl-thionoalkanephosphonic acid ester amides of the constitution (I) are obtained if O-phenyl-thiono-alkanephosphonic acid ester halides of the structure (II) where in the aforementioned formula R, X and n have the meaning given above, while Hal stands for a halogen, preferably chlorine atom, reacts with ammonia.

Surprisingly, the 0-phenyl-thiono-alkanephosphonic ester amides according to the invention are notable by a considerably higher insecticidal and acaricidal effect than the known ones O-Aryl-N, N-dialkyl-thiono-alkanephosphonic acid ester amides of analogous constitution and same direction of action. The substances according to the invention thus represent a real one Enrichment of technology.

If, for example, O- (3-chloro) -phenyl-thiono-methanephosphonic acid ester chloride and ammonia are used as starting materials, the course of the reaction can be represented by the following equation: The starting materials to be used for the manufacturing process are generally clearly defined by the formula (11). However, R therein preferably represents straight-chain or branched alkyl radicals having 1 to 4 carbon atoms, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert.

Butyl, X preferably denotes a chlorine atom or the methyl mercapto group.

As examples of O-phenyl-thionoalkane-phosphonic acid ester halides to be used as starting materials are mentioned in detail: O- (pentachlorophenyl) -, O- (2-chloro-4-methylphenyl) -, o- (3-chlorophenyl) -, O- (4-chlorophenyl) -, O- (2,5-dimethylphenyl) -, O- (2-chloro-3-methylphenyl) -, O- (3-methyl-4-chlorophenyl) -, O- (4-methylphenyl) -, O- (4-methylmercaptophenyl) -, O- (3-methyl-4-methyl-mercaptophenyl) -thiono-methane or ethane phosphonic acid ester chloride.

The to be used as starting materials O-phenyl-thionoalkanephosphonic acid ester halides of constitution (II) can be prepared according to known methods, for. B. from the corresponding Thionoalkanphosphonsäuredichloriden of the formula (I; I) and phenols of the formula (IV) in which R, X and n have the meaning given above, are produced in the presence of acid acceptors or the corresponding alkali, alkaline earth or ammonium salts of the phenol derivatives concerned0 The production process for the new substances is preferably carried out using suitable solvents or diluents.

Practically all inert organic solvents can be used as such. These include in particular aliphatic and aromatic, optionally chlorinated Hydrocarbons such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, Carbon tetrachloride, chlorobenzene, ethers, e.g. diethyl and dibutyl ethers, dioxane, also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, also nitriles, such as acetonitrile0 The reaction temperature can be within one can be varied over a larger area. Generally one works between 0 and 1000C, preferably at 20 to 500C.

The reaction is generally carried out under normal pressure.

The procedure usually followed in carrying out the process is that the corresponding O-phenyl-thionoalkanephosphonic acid ester chloride in a suitable Submitted solvent and ammonia at the specified temperature until completion the reaction is initiated. But you can also use the one from the Thionoalkanphosflhonsäuredichlorid and O-phenyl-thiono-alkanephosphonic acid ester chlorides obtained from the phenolic component in question React directly with aqueous ammonia without prior isolation. After one- or stirring the reaction mixture for several hours at the specified temperatures this is worked up in the usual way.

The substances according to the invention usually fall in the form of colorless to yellow colored, viscous, water-insoluble oils that under-strong Allow the reduced pressure to distill without decomposition. Used to characterize them especially the refractive index. Some of the compounds also represent crystalline substances which can be characterized by their melting point.

As already mentioned several times, the new O-phenylthionoalkanephosphonic acid ester amides stand out by an off.

insecticidal, also soil insecticidal and acaricidal effectiveness against Plant, hygiene and stored product pests.

They have both a good effect against sucking as well as eating insects and mites (Acarina), at the same time they have a low phytoxicity as well as an activity against soil fungi and phytopathogenic bacteria e.g.

Xanthomonas oryzae.

For these reasons, the compounds according to the invention are with Success as a pesticide in plant and stored product protection as well as on used in the hygiene and veterinary sectors. - To the sucking insects mainly include aphids (Aphidae) such as the green peach aphid (Myzus persicae), black bean (Doralis fabae), oat (Rhopalosiphum padi), pea (Macrosiphum pisi) and potato buds (Macrosiphum solanifolti), also the currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterua :; arundinis) and black cherry aphid (Myzus cerasi) w also scale and mealybugs (Coccina), e.g. the ivy shield (Äspidiotus hederae) and Napfschildlavls (Lecanium hesperidum) and the mealybug (Pseudococcus maritimus); Bladder tube (Thysanoptera) such as Hercinothrips fermoralis and bed bugs, for example the beet (Piesma quadrata), Cotton (Dysdercus intermedius), bed (Cimex lectularius), predatory (Rhodnius prolixus) and Chagas bug (Triatoma infestans), also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the permanent 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 (Ephestia kühniella) and large wax moth (Galleria mellonella) Farther are among the biting insects beetles (Coleoptera) e.g. corn (Sitophilus granarius = Calandra granaria) Potato (Leptinotarsa decemineata), dock (gastrophysa viridula0, horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), Raspberry (Byturus tomentosus) 9 Food beans (Bruchidius = Acanthoscelides obtectus) 3 Bacon (Dermestes frischi), Khapra (Trogoderma garnarium), 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 such as wire worms (Agriotes spec.) and white grubs (Melolontha melolontha); Cockroaches like the Germans (Blattella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia madeirae), Oriental (Blatta orientalis), giant (Blaberus giganteus) and giant black cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; also orthopteres e.g. the House crickets (Acheta 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), parlor- $ Musca domestica), small parlor $ Fannia canicularis), gloss fly (Phormia regina) and blowfly (Calliphora erythrocephala) and the calf stick (Stomoxys calcitrana); also mosquitoes, e.g. Mosquitoes such as the yellow fever mosquito (Aedes aegypti), house mosquito (Culex pipiens) and malaria mosquito (Anopheles stephensi).

The mites (Acari) include the spider mites (Tetranychidae) like 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 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 Flies and backs, 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 compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granules These are made in a known manner, e.g. B. 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 Agents In the case of using water as an extender, Zo Bo can also use 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 ethylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, zO Bo 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 solution medium, 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. B.

Aerosol propellants such as halogenated hydrocarbons, e.g. freon; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite, or diatomaceous earth, and synthetic rock flour, such as finely divided silica, aluminum oxide and silicates; as an emulsifier and / or Foaming agents: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant: e.g. B. Lignin, sulphite waste liquors and methyloellulose.

The active compounds according to the invention can be mixed in the formulations with other 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, packets, 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%, 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 9596 or even to apply the 100% active ingredient alone.

Example A Phaedon larvae test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether Preparation of active compound is missing 1 part by weight of active compound with the stated Amount of solvent that contains the specified amount of emulsifier and dilutes the Concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the active ingredient preparation dripping wet and populated with mustard beetle larvae (Phaedon cochleariae).

After the specified times, the degree of destruction is determined in 96. 100 means. that all beetle larvae have been killed. 0 96 means none Beetle larvae were killed.

Active ingredients, active ingredient concentrations, times of evaluation and results are shown in Table 1 below: Table 1 (Phaedon larvae test) Active ingredients Active ingredient concentration degree of destruction tration in, 'in 96 after 3 days CH3 t Oss 0.1 100 i> -N (CH3) 2 0.03 0 C2Hg (known) CH, CH3CSH / \ O \ S '0.1 100 CH PN (CH3) 0.01 0 3 (known) CH3 O Oss 0.1 100 P-NH, 0.01 100 CH3 5 0.1 CH3 \ 1 '100 P-NH2 0.01 0.01 100 C2H5 / CH, 0.01 b ob S ° '° 01 100 CH 2 0.001 30 3 Example B Doralis test (systemic action) 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 containing the stated amount of emulsifier, and the concentrate is diluted with water Desired concentration Bean plants (Vicia faba) which are heavily infested by the black bean louse (Doralis fabae) are poured on with the active compound preparation so that the active compound preparation penetrates the soil without wetting the leaves of the bean plants. The active ingredient is absorbed from the soil by the bean plants and thus reaches the infected leaves. After the specified times, the degree of destruction is determined in seconds. 100% means that all of the aphids have been killed, 0 means that none of the aphids have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 2 below: Table 2 (Doralis test / systemic effect) Active ingredients Active ingredient concentration degree of destruction tration in, in, 'after 4 days CH3S0 s 0.1 0 P'-N (CH3) 2 C2Hi / 2 92..5 (known) CH CH Sg0 sil 0.1 0 NPN (CH3) 2 CH3 (known) CH3S0 N s 0.1 100 J e-NH, 0.01 100 CH 3t 0 St30 S 0.1 100 3 Sir to P-NH 0.01 100 2 5 cl 1 0 S, 0.1 100 - IP B-NH2 0.01 100 CH3 3 Example C Tetranychus test (resistant) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified amount of solvent containing the specified amount of emulsifier, and the concentrate is diluted with water to the desired level Concentration0 Bean plants (Phaseolus vulgaris) which are approximately 10-30 cm in height are sprayed to runoff with the preparation of the active compound. These bean plants are heavily infested with the common spider mite (Tetranychus urticae) at all stages of development.

After the specified times, the effectiveness of the active compound preparation is determined by counting the dead animals. The degree of destruction thus obtained is given in 96. 100% means that all spider mites have been killed, 0 means that no spider mites have been killed Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 3 below: Table 3 (Tetranychus test / resistant) Active ingredients Active ingredient concentration degree of destruction tration in, in, after 2 days CH3SO s, I 0.1 0 > PN (CH3) 2 C2H5 (known) CH 5 °, S, 0.195 - P-NH2 0.01 60 CH3 CH3S0 S 0.1 90 \ P-NH, C2RS w2n5 Example D Limit concentration test / soil insects Test insect: Cabbage fly maggots (Phorbia braqsicae) 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, 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. The concentration of the active ingredient in the preparation plays practically no role here; the only decisive factor is the amount of active ingredient by weight per unit volume of soil, which; is given in ppm (zO Bq mg / l). The bottom is filled into pots and the pots are left to stand at room temperature. After 24 hours the test animals are placed in the treated soil and after a further 48 hours the degree of effectiveness of the active ingredient is determined by counting the dead and living test insects in. The degree of effectiveness is 100% if all test insects have been killed, it is 046 if just as many test insects are still alive as in the control.

Active ingredients, application rates and results are shown in Table 4 below: Table 4 Limit concentration tests for soil insects / Phorbia brassicae Active ingredients degree of destruction in% with one Active ingredient concentration of 20 10 5 2.5 1.25 ppm C1 O rO S? 00 100? 00? 00 50 Ir CH: 3 5 0 e 0 2 s PN- (CH3) 2 C 3 (cH3) 2 3 (known) 5 CH-JP, 01 (CH, \ O BO C1 (known) Example E LT10O Test for Diptera Test Animals: Musca domestica Solvent: Acetone 2 parts by weight of active ingredient are taken up in 1,000 parts by volume of solvent. The solution obtained in this way is diluted to the desired lower concentrations with further solvent.

2.5 ml of the active ingredient solution are pipetted into a Petri dish at the bottom of the petri dish is a filter paper with a diameter of about 9.5 cmO The Petri dish remains open until the solvent has completely evaporated. The amount depends on the concentration of the active ingredient solution Active ingredient per m2 of filter paper. different levels, then give about 25 Test animals in the petri dish and cover it with a glass lid.

The condition of the test animals is continuously monitored. The time is determined which is necessary to kill 100 goats 0 Test animals, active ingredients, active ingredient concentrations and times at which 100 goats are killed are shown in Table 5 below: Table 5 (LT100 test for diptera) Active ingredients Active ingredient concentration LT100 tration of the solution in CH3 3 O s 0.2 6h CH3 3 (known) CH SOO "0.2 8h = 5096 3 X PN (CH3) 2 C2H5 '32 (known) sI. C'H3S0 Po 0.2 c; h CH3o CH3S0 oo, S, 0.2 145h P-NH, 0102 ijh C2H5, C1 CO S 0.2 55t P-NH2 0.02 0.002 3 2 0.0002 8 = 40% Example F LD100 test Test animals: Sitophilus granarius Solvent: Acetone 2 parts by weight of active ingredient are taken up in 1,000 parts by volume of solvent. The solution thus obtained is diluted to the desired concentrations with further solvent.

2.5 ml of the active ingredient solution are pipetted into a Petri dish at the bottom of the petri dish is a filter paper with a diameter of about 9.5 cmO The Petri dish remains open until the solvent has completely evaporated0 Depending on the concentration of the active ingredient solution, the amount Different levels of active ingredient per m2 of filter paper. Then about 25 test animals are given into the petri dish and cover it with a glass lid.

The condition of the test animals is checked 3 days after the experiments have been started. The destruction in is determined, active ingredients, active ingredient concentrations, test animals and results are shown in the following table 6: Table 6 (LD100 test) Active ingredients active ingredient concentration tration of the solution degree in% in,' CH3 CH S to S 0.2 o P ~ N 0.2 0 CD; 3 3 (known) 3 OOS 0.2 ° / PN (CH) 2 3 C2H5 (known) CHS-511 0.2 100 3 P-NH2 0.02 100 CH3 5 CH S4 / \ 0 S 0.2 100 / P-NH2 0.02 100 v2n5 2H5 CH3 CH 5 go "S 0.2 100 3 == / s P-gH2 0.02 100 CH3 C1 5 OS 0.2 100 P-NH, L! 0.02 100 cH / example 1 0.4 molar batch: 107 g of 0- (3-methyl-4-methylmercapto-phenyl) thiono-methanephosphonic acid ester chloride (boiling point: 145 ° C.) are dissolved in 400 cc of benzene. With stirring, dry ammonia gas is passed into this solution until the reaction has ended, the mixture is then stirred for a further 2 hours and mixed with 200 cc of ice water. The organic layer is separated and dried over sodium sulfate. After the solvent has been distilled off, the residue solidifies in crystalline form. 79 g (80% of theory) of 0- (3-methyl-4-methylmercaptophenyl) thionomethanephosphonic ester amide with a boiling point of 880 ° C. are obtained.

Example 2 0.5 molar batch: 127 g of 0- (4-methylmercapto-phenyl -) - thiono-methanephosphonic acid ester chloride (boiling point: 1450 ° C.) are dissolved in 500 cc of benzene. Dry ammonia gas is passed into this solution until the reaction has ended, the mixture is stirred for a further 2 hours and then worked up as described in Example 1. 107 g (87% of theory) of the new 0- (4-methylmercapto-phenyl) thiono-methanephosphonic ester amide are obtained as a colorless, water-insoluble crystal powder with a melting point of 50%.

Example 3 0.4 molar batch: 107 g of 0- (4-methylmercapto-phenyl -) - thionoethane phosphonic acid ester chloride (boiling point: 1500 ° C.) are dissolved in 500 cc of benzene.

Ammonia is passed into this solution until the reaction has ended a, stir the mixture for a further 2 hours and then work it up as in Example 1. There are 88 g (89% of theory) of the O- (4-methylmercapto-phenyl) - thiono-ethanophosphonic ester amide obtained in the form of colorless crystals with a melting point of 580C.

Example 4 0. 35-iolar batch: 85 g of 0- (3-chlorophenyl -) - thionomethanephosphonic acid ester chloride (boiling point 3: 1160 ° C.) are dissolved in 400 cc of benzene. Ammonia is passed into this solution until the reaction has ended, it is stirred for a further 2 hours and the reaction mixture is worked up as described in Example 1. 66 g (85% of theory) of the O- (3-chlorophenyl) thionomethanephosphonic ester amide are obtained in the form of colorless crystals with a melting point of 470.degree.

Claims (6)

lStentant claims ) O-phenyl-thiono-alkanephosphonic acid ester amides of the formula in which R stands for a lower alkyl group, while X stands for a chlorine atom, the methyl or methyl mercapto radical and n stands for 1 or 2. 2) Process for the preparation of O-phenyl-alkanephosphonic acid ester amides, characterized in that 0-phenyl-thiono-alkanephosphonic acid ester halides of the formula in which R, X and n have the meaning given in claim 1, while Hal stands for a halogen atom, reacts with ammonia, 3) insecticidal and acaricidal agents, characterized by a content of O-phenyl-thiono-alkanephosphonic acid ester amides according to claim 1. 4) method for combating insects and mites, characterized in that that one O-phenyl-alkanephosphonic acid ester amides according to claim 1 on insects and / or Mites or whose living space can act. 5) Use of O-phenyl-thiono-ethane phosphonic acid ester amides according to Claim 1 for combating insects and mites. 6) processes for the manufacture of insecticidal and acaricidal agents, characterized in that one O-phenyl-thionoalkanephosphonic acid ester amides according to Claim 1 mixes with Strecz and / or surface-active agents.