DE2418270A1 - S-Arylthioalkyl-O,S-dialkyl dithiophosphates - with insecticidal, acaricidal, fungicidal, nematocidal activity, etc. - Google Patents

Abstract

New cpds. of formula (I) (where R1 is Me or Et; R2 is s-Bu or i-Bu; R3 is H or Me; each X is Cl, Br, Me or MeO; n = 0,1 or 2; m = 0 or 1) are pref. prepd. by (a) reacting R1O(R2S)P(O)SM (M = alkali metal, NH4 or alkylammonium) with Hal-CHR3-(CH2)m-S-C6H5-n(X)n or (b) reacting R1O(R2S)P(O)SH with CH2O and the corresp. aryl mercaptan in the presence of HCl to form (I; R3=H, m=O).

Description

"Thiolphosphoric acid esters, process for their preparation and their Usen The present invention relates to thiol phosphoric acid esters, processes for their production and their use in pest control.

The thiol phosphoric acid esters have the formula wherein R1 is methyl or ethyl, R2 is sec-butyl or isobutyl, R3 is hydrogen or methyl, X according to n identical or different chlorine or bromine atoms or methyl or methoxy groups, n the numbers 0, 1 or 2 and m the numbers 0 or 1 mean.

The compounds of the formula I are prepared by methods known per se, for example as follows: 2) if R3 = hydrogen and m is the number 0 In the formulas II to V, R1 to R3, X, n and m have the meaning given for the formula I and Me stands for an alkali metal, in particular for sodium or potassium, ammonium or alkylammonium and Hal for a halogen atom, such as fluorine, chlorine, Bromine or iodine.

Suitable acid-binding agents are tertiary amines, e.g. trialkylamines, Pyridine, dialkylanilines; inorganic bases such as hydrides, hydroxides; Carbonates and Bicarbonates of alkali and alkaline earth metals.

In the reactions it is sometimes necessary to use catalysts, such as e.g. copper or copper chloride to be used.

Processes 1 and 2 are carried out at a reaction temperature between 0 - 130C, carried out at normal pressure and in solution or diluents.

Suitable solutions or diluents are e.g.

Ethereal and ethereal compounds such as diethyl ether, dipropyl ether, Dioxane, tetrahydrofuran; Amides, such as N, N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, Xylenes, chloroform, chlorobenzene; Nitriles such as acetonitrile; DMSO, ketones such as acetone, Methyl ethyl ketone, water.

The starting materials of the formulas II to V are known and can be carried out analogously known methods are produced.

The compounds of formula 1 have a broad biocidal effect and can be used to control various plant and animal pests and used as plant regulators. Their use is particularly advantageous in combating cotton pests. Surprisingly, they work better e.g.

against larvae of Spodoptera littoralis as analogous compounds Belgian patent 754 199.

In addition, they are also suitable for combating all stages of development such as eggs, larvae, pupae, nymphs and adults from insects of the families: Acrididae, Blattidae, Gryllidac, - Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidac, -Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae as well as acarids of the families: Ixodidae, Argasidae, Tetranychidae, Deranyssidae.

The insecticidal or acaricidal effect can be increased by adding other insecticides and / or acaricides widen significantly and at given um Adjust the end.

Such additives are e.g. organic phosphorus compounds, Nitrophenols and their derivatives, amidine, in particular formamidines, ureas, carbamates and / or halogenated, especially chlorinated, hydrocarbons.

In addition to the properties mentioned above, the compounds of the formula I have also an effectiveness against representatives of the department Thallophyta. So show some these compounds have a virucidal and bactericidal effect.

But above all, they are against fungi, especially the following Classes, belonging to phytopathogenic fungi effective: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes.

The compounds of the formula I are also fungitoxic Effect on fungi that attack the plants from the ground. Also suitable are the new active ingredients also for the treatment of seeds, fruits, tubers, etc.

to protect against fungal infections. The compounds of formula I are suitable can also be used to combat phytopathogenic nematodes.

The compounds of the formula I can be used alone or together can be used with suitable carriers and / or additives. Suitable carriers and additives can be solid or liquid serine and correspond to those used in formulation technology common substances such as natural or regenerated substances, solutions, dispersants, Wetting agents, adhesives, thickeners, binders and / or fertilizers.

For application, the compounds of the formula I can be converted into dusts, Emulsin concentrates, granules, dispersions, sprays, to solutions or slurries in the usual formulations, which are part of general knowledge in application technology, are processed. There are also "cattle dips". i.e. cattle baths, and "spray races", i.e.

Spray courses in which aqueous preparations are used, too mention.

The preparation according to the invention takes place in a manner known per se Way by intimately mixing and / or Vermalilen of active ingredients of formula 1 with the appropriate carriers, if necessary with the addition of the opposite Active ingredients, inert dispersants or solvents.

The active ingredients can be in the following working-up forms and are used: Fixed forms of processing: dust, Litter, granules, coated granules, impregnation granules and homogeneous granules Liquid processing forms: a) Active substance concentrates dispersible in water: Wettable powders, pastes, emulsions; b) Solutions for the preparation solid processing forms (dust, grit) are the active ingredients with solid carriers mixed in a manner known per se. Come as carriers for example kaolin, talc, bolus, loess, chalk, limestone, lime grit, attapulgite, Dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum silicates (Feldspars and mica), calcium and magnesium sulphates, magnesium oxide, ground Plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea, ground vegetable products such as grain flour, tree bark flour, wood flour, Nut shell flour, cellulose powder, residues of plant extracts, activated charcoal etc., each on their own or as mixtures with one another.

Granules can also be very easily obtained using methods known per se easy to manufacture.

These mixtures can also contain additives stabilizing the active ingredient and / or nonionic, anionic and cationic substances are added, which for example the adhesive strength of the active ingredients on plants and plant parts improve (adhesives and adhesives) and / or better wettability (wetting agents) and ensure dispersibility (dispersants). Suitable such additives are for example olein / lime mixtures, cellulose derivatives (methyl cellulose, Carboxymethyl cellulose), hydroxyethylene glycol ethers of mono- and dialkylphenols with 5 - 15 ethylene oxide residues per molecule and 8 - 9 carbon atoms in the alkyl residue, Lignosulfonic acid, its alkali and alkaline earth salts, polyethylene glycol ethers (carbon waxes), Fatty alcohol polycol ether with 5 - 20 ethylene oxide residues per molecule and 8 - 18 carbon atoms in the fatty alcohol part, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidores, Polyvinyl alcohols, I condensation products of mineral / formaldehyde as well as latex products, Active ingredient concentrates dispersible in water, i.e. wettable powders Pastes and emulsion concentrates are agents that can be mixed with water on any desired basis concentration can be diluted. They consist of active ingredients and additives such as carriers, optionally stabilizers for the active ingredient, surface-active substances and antifoam agents (e.g. silicone oils) and optionally solvents. Such Additives are well known in formulation technology, and so is the production of active ingredient concentrates takes place according to methods known per se.

The agents according to the invention can also be used in the form of solutions will. For this purpose, the active ingredient or

are several active ingredients of general formula I in suitable organic Solvents> Solvent mixtures or water dissolved. This comes as a solvent those customary in formulation technology can be considered. The content of active ingredient in the means described above is between 0.1 and 95%, it should be mentioned that when applying from the aircraft or by means of other suitable application devices Concentrations up to 99.5% or even pure active ingredient can be used.

The active ingredients of the formula I can, for example, be formulated as follows : Dusts: For the production of a) 5% and b) 2% dust the following substances are used: a) 5 parts of active ingredient 95 parts of talc; b) 2 parts of active ingredient 1 part of highly disperse silica, 97 parts of talc The active ingredients are mixed and ground with the carrier materials Granulate: For the production of a The following substances are used in 5% granules: 5 parts of active ingredient 0.25 Parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol 91 parts of kaolin (grain size 0.3-0.8 mm).

The active ingredient is mixed with epichlorohydrin and added 6 parts Dissolved acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution obtained in this way is sprayed onto kaolin and then the acetone evaporated in vacuo.

Wettable powder: For the production of a) 40%, b) and c) 25% d) 10% wettable powder, the following ingredients are used: a) 40 parts of active ingredient 5 parts of lignin sulfonic acid, sodium salt, 1 part of dibutylnaphthalenesulfonic acid, sodium salt, 54 parts of silica; b) 25 parts of active ingredient 4.5 parts of calcium liginsulfonate, 1.9 Parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1), 1.5 parts of sodium dibutyl naphthalene sulfonate, 19.5 parts of silica, 19.5 parts of Champagne chalk, 28.1 parts of kaolin; c) 25 parts Active ingredient 2.5 parts of isooetylphenoxy-polyoxyethylene-ethanol, 1.7 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1), 8.3 parts of sodium aluminum silicate, 16.5 parts of kieselguhr, 46 parts of kaolin; d) 10 parts of active ingredient 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulfates, 5 parts of naphthalene sulfonic acid / formaldehyde condensate, 82 parts of kaolin.

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate gauges and rollers. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.

Emulsifiable concentrates: For the production of a) above and b) 25% The following substances are used for emulsifiable concentrates: a) 10 parts of active ingredient 3.4 parts of epoxidized vegetable oil, 13.4 parts of a combination emulsifier from fatty alcohol polyglycol ether and alkyl aryl sulfonate calcium salt 40 parts of dimethylformamide, 43> 2 parts xylene; b) 25 parts of active ingredient 2.5 parts of epoxidized vegetable oil, 10 Parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene.

Such concentrates can be diluted with water to produce emulsions any desired concentration can be produced.

Spray: To produce a 5% spray, the the following ingredients are used: 5 parts of active ingredient, 1 part of epichlorohydrin, 94 parts Gasoline (boiling point 160 - 190 ° C); Example 1 S-4-Chlorophenylthiomethyl-s-sec . -butyl-0-ethyl-dithiophosphoric acid ester 19.3 g of chloromethyl-4-chlorophenyl sulfide and 25.2 g of O-ethyl-S-sec-butyldithiophosphoric acid potassium are in 100 ml of acetonitrile Overnight at room temperature stirred. The mixture is then heated another 2 hours at 50 to 60 "C.

After cooling, the salt is filtered off with suction, the solvent is removed in vacuo, the residue is taken up in methylene chloride and the solution is washed out successively with 1N sodium hydroxide solution and with water. After the solvent has been evaporated off in vacuo, the compound of the formula is obtained as a colorless oil with a refractive index of nD22 = 1.5840. The following connections are also established in the same way: R1 R2 X1 X2 X3 X4 X5 Physical data -C2H5 -C4H9 (i) HH Cl HH nD20: 1.5851 -CH3 -C4H9 (sec) HH Cl HH nD24: 1.5837 -C2H5 -C4H9 (sec) HHHHH nD23: 1.5840 -C2H5 -C4H9 (i) HHHHH nD23: 1.5750 -CH3 -C4H9 (sec) HHHHH nD24: 1.5818 -C2H5 -C4H9 (sec) HH Br HH nD23: 1.6041 -C2H5 -C4H9 (sec) HH -CH3 HH nD23: 1.5761 -C2H5 -C4H9 (i.) HH -CH3 HH nD23: 1.5709 -CH3 -C4H9 (sec.) HH -CH3 HH nD24: 1.5773 -C2H5 -C4H9 (sec.) Cl HH Cl H nD23: 1.5990 -C2H5 -C4H9 (i) Cl HH Cl H nD21: 1.5947 -CH3 -C4Hg (i) C1 H II Cl H nn24: 1.5831 -CH3 -C4H9 (sec) Cl HH Cl H nD24: 1.5888 -C2H5 -C4H9 (sec.) HH -OCH3 HH nD25: 1.5752 -CH3 -C4H9 (sec.) HH -OCH3 HH nD21: 1.5844 Example 2 A) Insecticidal feed poison effect Cotton plants and potato plants were sprayed with a 0.05% strength aqueous active substance emulsion (obtained from the above emulsifiable concentrate).

After drying the covering, the cotton plants were each with Spodoptera littoralis or Heliothis virescens larvae L3 and the potato plants populated with Colorado potato beetle larvae (Leptinotarsa decemlineata). The attempt was made carried out at 24 ° C and 60% relative humidity.

The compounds according to Example 1 showed good results in the above test insecticidal antifouling action against Spodoptera, Heliothis and Leptinotarsa decemlineata larvae.

B) Insecticidal contact effect one day before application Broad beans (Vicia faba) grown in pots with approx. 200 aphids (Aphis fabae) infected per plant. The application was carried out using a compressed air syringe on the Leaves infected with lice with a spray liquor at a concentration of 1000 ppm (made from a 25% wettable powder).

The rating took place 24 hours after the application.

The compounds according to Example 1 showed a good contact effect in the above test against Aphis-fabae.

Example 3 Action against Chilo suppressalis 6 rice plants each of the Caloro variety were placed in plastic pots with a top diameter of 17 cm, transplanted and raised to a height of approx. 60 cm. The infestation with chilo suppressalis larvae (L1; 3-4 mm long) occurred 2 days after the addition of the active ingredient in Granulate form (application rate 8 kg of active substance per hectare) into the paddy water.

The insecticidal activity is evaluated 10 days after the addition of the granulate.

The compounds according to Example 1 were effective against chilo in the above test suppressalis.

Example 4 Action against ticks A) Rhipicephalus bursa 5 adults each Ticks or 50 tick larvae were counted in a glass tube and left for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, l, or 0.1 ppm test substance immersed. The tube was then covered with a standardized cotton ball locked and turned upside down so that the. Active ingredient emulsion from cotton wool could be included.

The evaluation was carried out in the adults after 2 weeks and in the Larvae after 2 days. Two repetitions were run for each attempt.

B) Boophilus microplus (larvae) with an analogous dilution series as in test A, 20 sensitive resp. OP-resistant larval trials carried out. (The resistance relates to the tolerance of Diazinon) The compounds according to Example 1 were effective against adults and larvae in these tests of Rhipicephalus bursa and sensitive resp. OP-resistant larvae of Boophilus microplus.

Example 5 Acaricidal effect of Phaseolus vulgaris (plants) 12 hours before the test for acaricidal activity with an infected piece of leaf from a mass breed of Tetranychus urticae. The defected moving Stages were obtained from a chromatography atomizer with the emulsified test preparations dusted that no run-off of the spray liquid occurred. After two to 7 days were Larvae, adults and eggs are evaluated for living and dead individuals under the binocular microscope and the result expressed as a percentage.

During the "holding time", the treated plants stood in greenhouse cabins at 25 ° C.

In the above test, the compounds according to Example 1 were effective against adults, Larvae and eggs of Tetranychus urticae.

Example 6 Action against soil nematodes To test the action against Soil nematodes were the active ingredients in the specified concentration in soil infected by root cell nematodes (Meloidogyne arenaria) and intimately mixed. In the soil prepared in this way, a series of experiments was carried out directly then planted tomato seedlings and in another test series after 8 days Waiting time tomatoes used

The nematocidal effect was assessed 28 days after planting or after sowing the galls present on the roots are counted.

In this test, the active ingredients according to Example 1 showed good results Effect against Meloidogyne arenaria.

Claims (9)

Claims 1. Compounds of the formula where R1 is methyl or ethyl, R2 is sec-butyl or isobutyl, R3 is hydrogen or methyl, X according to n is identical or different chlorine or bromine atoms or methyl or methoxy groups, n is the number 0, 1 or 2 and m is the number 0 or 1 . 2. Compound according to claim 1 of the formula 3. Compound according to claim 1 of the formula 4. Process for the preparation of compounds according to one of claims 1 to 3, characterized in that a compound of the formula with a compound of the formula lets react, in which R1, R2, R3, X, n and m have the meaning given in claim 1 and Me is an alkali metal, ammonium or alkylammonium and Hal is a halogen atom. 5. Pesticides, which are an active component Compound according to one of claims 1 to 3 and a suitable carrier and / or contain other aggregates. 6. Use of compounds according to one of claims 1 to 3 for combating various animal and vegetable pests. 7. Use according to claim 6 for combating insects and representatives of the order Akarina. 8. Use according to claim 7 for combating cotton pests. 9. Use according to claim 6 for combating phytopathogens Nematodes.