DE2210838A1 - O-alkyl-s-allyloxymethyl-(d1)thiophosphonates - with insecticidal and acaricidal activity - Google Patents

Abstract

Cpds. of formula (I): (where r and R1 are 1-4C alkyl and R1 can also be lower chloroalkyl or phenyl; X is O or S) have insecticidal and acaricidal activity. They are pref. prepd. by reacting R1(RO)P(X)SM (where M is a monovalent metal, pref. alkali metal, or NH4) with Hal-CH2-O-CH2-CH=CH2 (where Hal is halogen).

Description

Thiol- or thionothiolphosphonic acid esters, process for their preparation and their use as insecticides and acaricides The present invention relates to thiol- or thionothiolphosphonic acid esters of the general formula (I) which have insecticidal and acaricidal properties, a process for their preparation and their use as insecticides and acaricides.

In the above formula, R and R 'stand for lower alkyl radicals 1 to 4 carbon atoms, R 'also means a lower chloroalkyl or the phenyl radical, while X represents an oxygen or sulfur atom.

Amido-O-alkyl-S-propej - ( -propin) -ylthiolphosphoric acid ester known, which is good insecticidal and acaricidal effectiveness.

It has now been found that compounds of the above structure (I) are obtained in a smooth reaction which proceeds in good yields if alkyl- or phenyl-O-alkylthiol or thionothiolphosphonic acid salts of the general formula (II) with halomethyl allyl ethers (allyloxymethyl halides) of the formula (III) Hal-CH2-O-CH2-CH = CH2 (III).

In the latter formulas, the symbols R, R 'and X have those given above Meaning, while Me stands for a monovalent metal equivalent, preferably an alkali metal atom or the ammonium group and Hal represents a halogen, preferably chlorine, atom.

It was also found that the new amidothiol phosphoric acid ester excellent island: possessing ticidal and acaricidal properties.

Surprisingly, the products according to the invention stand out here compared to the comparable known compounds of analogous constitution and same direction of action due to a much better insecticidal resp.

acaricidal effectiveness and / or significantly lower phytotoxicity the end; the former thus represent a leaps and bounds in technology.

The course of the manufacturing process can be represented by the following reaction scheme: In the aforementioned formulas, the symbols R, R ', X, Me and Hal have the meaning given above.

However, R and R 'are preferably identical or different alkyl radicals with 1 to 3 carbon atoms such as methyl, ethyl, n- and iso-propyl. R 'means furthermore preferably the phenyl or a chlorine-substituted alkyl radical with 1 to 3 carbon atoms, for example chloromethyl, ß-chloroethyl, ß, ß, ß-trichloroethyl. Me preferably represents a potassium, sodium or ammonium ion and Hal a chlorine atom represent.

The process for preparing the new substances is preferred in the presence carried out by solvents or diluents.

Polar organic solvents have proven particularly useful for this purpose, e.g. lower aliphatic ketones or nitriles, such as acetone, methyl ethyl, methyl isopropyl ketone, Aceto- and propionitrile.

Furthermore, it is for the purpose of completing the implementation and thus to achieve good yields and to obtain pure products, the implementation is advantageous at room or slightly to moderately elevated temperature (20 to 80 ° C, preferably 50 to 80 ° C) and also the reaction mixture after combining the starting components to be stirred for a longer time, if necessary with refluxing.

The approach is processed in a manner known in principle, by doing. after the mixture has cooled to room temperature, the batch is grown diluted with another organic solvent. Have proven suitable This is mainly aliphatic or aromatic, optionally chlorinated Hydrocarbons such as benzene, xylene, methylene chloride, chloroform, carbon tetrachloride, Tri- and tetrachloroethane. The solution is then washed with water and dried the organic layer. After drying the organic phase and evaporation of the The reaction product usually remains after solvent under reduced pressure in the form of a colorless to slightly colored oil that either distills or at least by brief heating to slightly to moderately elevated temperatures (40 to 800C) can be freed from the last volatile impurities.

The raw materials needed to manufacture the new fabrics alkyl or phenyl-0-alkylthiol or

-thionothiolphosphonic acid salts of the general formula (II) are known from the literature and can also be easily produced on an industrial scale.

Also the halogen, in particular used as the second reaction component Chloromethyl allyl ethers (III) are easily accessible in a manner known in principle.

As already mentioned above, the thiol according to the invention are or thionothiol phosphonic acid ester due to its excellent insecticidal and acaricidal properties Effect on sucking and eating insects, dipteras and mites, for example Aphids, spider mites, caterpillars and flies. The products have both a very good contact insecticide as well as an excellent systemic one Effect. On the other string, the new connections show only a relatively small one Phytotoxicity. In addition, some of them also have nematicidal and fungicidal properties Effectiveness (especially against soil fungi).

The products according to the invention are based on these properties as a pesticide, especially in crop protection and against hygiene and use of food pests.

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 blue (Macrosiphum solanifolii), 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 dfle mealybird (Pseudococcus maritimus); Bladder feet (Thysanoptera) such as Hercinothrips femoralis and bedbugs, for example the 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 KohlweiBling (Pieris brassicae), small frost wedges (Cheimatobia brumata), Oak moth (Tortrix viridana), the army (Iaphygma frugiperda) and Egyptian Cotton worm (rodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kUhniella) and large wax moth (Galleria mellonella), Farther belong to the bite @ ins @ en @ afer @ Coleoptera) e.g. grain (Sitophilus gra @ a @@@@@@ @atandra granaria).

Potato (Leptinotarsa decemlineata), @pfer- (Gastrophysa viridula), Horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), edible beans (Bruchidius = Acanthoscelides obtectus), bacon (Dermestes frischi), khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), Corn (Calandra or Sitophilus zeamais), bread (Stegobium paniceum), common flour (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground B. wireworms (Agriotes spec.) And white grubs (Melolontha melolontha); Cockroaches like the German (Blattella germanica), American (periplaneta americana), Madeira (Leucophaea or Rhyparobia maderae), Oriental (Blatta orientalis), giant cockroach (Blaberus gigan @ eus) and black cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; furthermore orthoptera e.g. the cricket (Gryllus domesticus); Termites such as the terrestrial termites (Reticuliterres flavipes) and Hymenoptera like ants, for example the meadow ant (Lasius niger).

The Diptera essentially comprise flies like the Tau (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domest @ ca), small house fly (Fannia canicularis), gloss fly (Phormia regina) and blowfly (Calliphora erythorcephale) and the Wa @@ nstecher (Stomoxys calcitrans); also mosquitoes, e.g. Mosquitoes such as the yellow fever mosquito (Aedes aegypti), house mosquito (Culex pipiens) and malaria mosquito (Anophleles stephnsi).

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, 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.

Depending on their intended use, the new active ingredients can be converted into the usual ones Formulations such as solutions, emulsions, suspensions, powders, Pastes and granulates. These are prepared in a known manner, for example by mixing the active ingredients with extenders, i.e. liquid solvents and / or carriers optionally with the use of surface-active agents, ie emulsifying and / or Dispersants, e.g. in the case of using water as an extender organic solvents can optionally be used as auxiliary solvents can. The main liquid solvents that can be used are: aromatics (e.g.

Xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water; as solid carriers: natural rock flour (e.g. kaolins, clays, talc, chalk) and synthetic Rock flour (e.g. highly dispersed silica, silicates); as emulsifier: non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid I4;% er, polyoxyethylene fatty alcohol ether, e.g., alkylaryl polyglycol ethers, alkyl sulfonates and aryl sulfonates; 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 D, 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 use forms prepared therefrom, such as ready-to-use solutions, emulsifiable Concentrates, emulsions, suspensions, wettable powders, pastes, soluble powders, dusts and granules can be used. 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) is used where possible, formulations up to 95% or even to apply the 100% active ingredient alone.

Example A Plutella test 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, containing the specified amount of emulsifier, and dilute the concentrate 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 degree of destruction is determined in%. 100% means that all caterpillars have been killed, while 0% means that none Caterpillars were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 1 below: Table 1 (Plutella test) Active ingredient active ingredient killing degree centering in% 3 3 days 0 0.1 100 C2H50 to (r 0.1 0 PS-5H-CH = CH 0.01 0 CH3-NH / 2 2 3 (known) CH30 - 0.1 100 -c, H, -O- -CH = CH2 0.0i 100 CH '2 0-CH2-CH = CH2 5 C2H50 s 0.1 100 pS-CH2-0-CH2-CH = CH2 0.01 100 C2H 5 0.1 100 ) 2CH-01 PS-CH -O-CH2-CH = CHz 0.01 100 C. 0 0.1 100 C2H50-S-CH2-O-CH 0.1 100 CH3 ,, P 3 2 5 p ~ S-CH2-0-CH2-CH = CH2 0.01 95 2 5 Example B Drosophila 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 specified amount of solvent containing the specified amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

1 cm3 of the active ingredient preparation is applied to a filter paper disk with 7 cm diameter pipetted on. They are placed wet on a glass in which they are 50 Drosophila melanogaster are located and cover them with a glass plate.

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

100% means that all flies have been killed, 0% means that no flies were killed.

Active ingredients, active ingredient concentrations, evaluation times and degree of destruction are shown in Table 2 below: Table 2 (Drosophila test) Active substance active substance con - degree of destruction centering in% 1 1 day CH. O CH3 0 1 ° l 0.1 100 3 PS-CH2-H = CH2 0.01 0 NH2 '2 2 (known) C2H50, i 0.1 80 PS-H2-CH = CH2 0.01 0 CH3-NH " 3 (known) CH30 0 0.1 100 PS -CH, -O-CH2 -CH = CH2 0.01 0.01 100 2 5 2 2 0.001 100 0.0001 98 5 C2H500.1 100 PS-CH2-O-CH2-CH = CH2 0.01 100 C2H5 / 0.001 100 0.0001 100 (CH), CH- S 0.1 100 3P-S-CH2-0-CH2-CH = CH2 ° 0, ° 01 100 0.001 C2H5 0.0001 100 5 0.1 100 C2H5 °> 0.1 100 PS-CH, -O-CH2-CH = V2 0.01 95 C1-CH2 C2H5 ° ~ i 0.1 100 Pd 0.01 75 PS-CH2-0 - CH2-CH = CH2 0.01 75 T abe 1 1 e 2 (continued) (Drosophila test Active ingredient active ingredient degree of destruction centering in% in 9 1 day C2'R50 ° 0.1 100 CH3 -S-CH2-0-CH2-CH = CH2 0.01 100 C2H50 01 0.1 100 0-S-CH2-0-CH2-CH = CHz 0.01 100 C2H5¼ Example C 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 containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired amount Concentration.

Bean plants (Phaseolus vulgaris), which have a height of about 10 - 30 cm, sprayed dripping wet. These bean plants are strong with all stages of development of the common spider mite (Tetranychus urticae) infested.

After the times indicated, the effectiveness of the active ingredient preparation determined by counting the dead animals. The degree of mortality obtained in this way wíkad given in%. 100% means that all spider mites have been killed, 0% means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, recovery times and results are shown in Table 3 below: Tables 1 1 e 3 (Tetranychus test) Active ingredient active ingredient killing degree centering in% % 2 days C2H50>°; 0.1 20 P'-S-CH2-CH = CH2 CH3-NH (known) C2H50ss0 0.1 95 PS-CH2-O-CH2-CH = CK2 CH3 0 C2H50s, 1 90 C2Hg0, II o, a 90 C2H5 / Example D Limit concentration test / soil insects Test insect: Phorbia brassicae - maggots in the soil 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 solution is diluted 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 practically no role, the only decisive factor is the amount by weight of the active ingredient per unit volume of soil, which is given in ppm. (e.g. 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 9 minutes.

The efficiency is 100 if all test insects are killed.

it is 0 9 'if just as many test insects are still alive like control.

Active ingredients, application rates and results are shown in Table 4 below: Table 4 (Phorbia brassicae - maggots in the soil) Soil insecticides Active ingredient destruction rate in% with one Active ingredient concentration of 20 10 5 2.5 'i 1925 ppm 8th PS-CH2-O-CH2-CH = CH2 100 100 100 95 50 C 100 100 100 95 50 3 7 PS-CH2-o-CH2-CH = CH2 100 100 100 95 50 C2H5 / CH, - / PS-CH-0-CF1-CH = CH2 100 100 75 C2Hg /./ 3 2 5 ß S-CH2-CH ~ CH2 00 CH3-NHv ' (known) CM3 0 0 CH30 ° PS-CH. -CH-ü 'o HN / 'Nw (known) Example E Limit Concentration ^ est / soil insects 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 specified amount of solvent, the specified 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 practically no role here; the only decisive factor is the amount by weight of the active ingredient per unit volume of soil, which is given in ppm (for example 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 in% by counting the dead and living test insects.

The efficiency is 100 drew when all test insects are killed.

It is O if there are exactly as many test insects living as in the control. Active ingredients, application rates and results are shown in Table 5 below T from e 1 1 e 5 (Tenebrio molitor - larvae in the soil) Soil insecticides Active ingredient kill rate in% with one Active ingredient concentration of 40 20 10 5 2.5 ppm 5 C2H5 ° s ISI L. C2H5 /> Hg / i-C3H70 ISI PS-CH2-O-CH2-CH = CH7 100 100 100 100 80 C2H, I. C2H5 ° o1 C2H501 CH3-NH / 2 2 (known) 0 CH30s2 CH, O \ li H2Nz e.g. (known) Production examples: Example 1: 0.4 molar batch: 80 g of ethyl-O-isopropyl-thionothiolphosphonic acid ammonium are dissolved in 350 cc of acetonitrile. 60 g of chloromethyl allyl ether are added dropwise to this solution at 50 ° C. with stirring. After heating to 60 ° C. for one hour, the reaction mixture is taken up in 300 cc of benzene, the benzene solution is washed with 200 cc of ice water, separated off and dried over sodium sulfate. This gives 79 g (78% of theory) of the ethyl-O-isopropyl-S-allyloxymethyl-thionothiolphosphonic acid ester in the form of a colorless, water-insoluble oil with the refractive index nD25 = 1.5168.

Calculated for a molecular weight of 254: P 12.2%; found: 12.1% S 25.2 o 25.4% Example 2: 0.4 molar batch: 70 g of ethyl-O-ethyl-thiolphosphonic acid potassium are dissolved in 350 cc of acetonitrile. 60 g of chloromethyl allyl ether are added to the solution at 50 ° C. while stirring. After heating to 60 ° C. for one hour, the batch is worked up as in Example 1. 63 g (70% of theory) of the ethyl-O-ethyl-S-allyloxy-ynethyl-t} ii 0 lphosphonic acid ester are obtained in the form of a colorless, water-insoluble oil with the refractive index nD23 = 1.4871.

Calculated for a molecular weight of 224: P 13.8%; found: 13.4% S 14.3%; 14.4% Example 3: 0.4 molar batch: 75 g of methyl-O-ethyl-thiolphosphonic acid potassium are dissolved in 350 cc of acetonitrile. Add while stirring. 5G0C to this solution 60 g of chloromethyl allyl ether. After heating the mixture to 600 ° C. for one hour, it is worked up as in Example 1. 73 g (87% of theory) of the NethyT-0-ethyl-S-aliyloxymethylthiolphosphonic acid ester are obtained as a colorless, water-insoluble oil with the refractive index nD25 = 1.4864.

Calculated for a molecular weight of 210: P 14.8%; found: 15.0; S 15.2 %; 15.4%.

Example 4: 0.4 molar batch: 80 g of ethyl-O-methyl-thionothiolphosphonic acid potassium are dissolved in 400 cc of acetonitrile. 60 g of chloromethyl allyl ether are added to this solution at 56 ° C. with stirring. After the batch has been heated to 60 ° C. for one hour, it is worked up as described in Example 1. 62 g (69% of theory) of the ethyl-O-methyl-S-allyloxymethyl-thionothiolphosphonic acid ester are obtained in the form of a colorless, water-insoluble oil with the refractive index nD23 = 1.5392.

Calculated for a molecular weight of 226: P 13.7%; found: 13.4%; S 28.3 %; 28.2%.

Example 5: 0.4 molar batch: 105 g of phenyl-O-ethyl-thionothiolphosphonic acid potassium are dissolved in 400 cc of acetonitrile. 60 g of chloromethyl allyl ether are added to the solution at 50 ° C. while stirring. After heating to 60 ° C. for one hour, the reaction mixture is worked up as in Example 1. 89 g (77% of theory) of the phenyl-O-ethyl-S-allyloxymethyl-thionothiolphosphonic acid ester are obtained as a colorless, water-insoluble oil with the refractive index n23 = 1.5800.

D Calculated for a molecular weight of 288: P 10.8%; found: 10.8%; s 22.2%; 22.1%.

Example 6: 0.4 molar batch: 95 g of chloromethyl-O-ethyl-thionothiolphosphonic acid potassium are dissolved in 400 cc of acetonitrile. 60 g of chloromethyl allyl ether are added to this solution with stirring. The reaction mixture is heated to 65 ° C. for 2 hours with further stirring. It is then cooled to room temperature and the batch is diluted with 300 cc of benzene. The benzene solution is separated off and dried over sodium sulfate. After the solvent has been distilled off, 91+ g (90 (theoretical) of the chloromethyl-O-ethyl-S-allyloxymethyl-thionothiolphosphonic acid ester are obtained as a colorless, water-insoluble oil with the refractive index nD23 = 1.5592.

Calculated for a molecular weight of 260.5: P 11.9%; Found: 12.0% s 24.6%; 24.7%.

In an analogous manner, the compound of the following constitution can be produced in a yield of 68% of theory.

It has the refractive index nD = 1.5210 Die as a starting material Halogen ethers, in particular chloromethyl allyl ethers, are required, for example, on the following Accessible: Cl-CH2-0-CH2-CH = CH2 5-molar approach: In a stirring apparatus 290 g of propene- (1) -ol- (3) (allyl alcohol) are stirred with 140 g of paraformaldehyde. At 0 ° to 10 ° C., hydrogen chloride is passed into this mixture with constant stirring until the paraformyldehyde has gone into solution. Then the reaction mixture washed with ice water, the organic layer separated and dried over sodium sulfate drunk. There are 258 g (48% of theory) of allyl chloromethyl ether of boiling point 100 55 0C and the refractive index nD23 = 1.4300.

Claims (6)

Patent claims: Thiol or thionothiol phosphonic acid esters of the general formula in which R and R 'stand for lower alkyl radicals having 1 to 4 carbon atoms, R' also has one. is lower chloroalkyl or the phenyl radical, while X is an oxygen or sulfur atom. 2) Process for the preparation of thiol- or thionothiolphosphonic acid esters, characterized in that alkyl- or phenyl-O-alkylthiol- or thionothiolphosphonic acid salts of the general formula are used with halomethyl allyl ethers of the formula Hal-CH2 -0 -CH2-CH = CH2, where in the aforementioned formulas R, R 'and X have the meaning given in claim 1, Me stands for a monovalent metal equivalent or the ammonium group, and Hal Represents halogen atom. 3) insecticidal and acaricidal agents characterized by a content of compounds according to claim 1. 4) method for combating insects and mites, characterized in that that one compounds according to claim 1 Insects and / or mites or lets its habitat act. 5) processes for the manufacture of insecticidal and acaricidal agents, characterized in that compounds according to Claim 1 are mixed with extenders andfor mixing surfactants. 6) Use of compounds according to claim 1 for combating Insects and / or mites.