DE2439663A1 - Diphenylether phosphates as pesticides - from hydroxy diphenyl ethers and substd. phosphoric acid chlorides - Google Patents

Abstract

Diphenylether phosphates of formula (I): (where R1= 1-7C alkyl, R2 = Me or Et, R3 to R11 = H or Hal, X and Y = O or S), are used to control various animal and plant pests esp. all stages of insect life, representatives of the acarina class and plant parasitic nematodes. They also have fungicidal props, and can be used against phytopathogenic fungi in e.g. cereals, vegetables, fruit trees and also to treat seed grain, fruits, tubers etc. to protect them from fungal infection. (I) may be used alone or in conventional prepns., contg. 0.1-95% of (I) and suitable carriers and/or other additional substances, (including other pesticides). (I) are prepd. from hydroxy diphenyl ethers and substd. phosphoric acid chlorides.

Description

"Diphenyl ether phosphates, process for their preparation and their use" The present invention never relates to diphenyl ether phosphates and processes for their preparation and their use in pest control.

The phosphorus compounds have the formula wherein R1 is Cl-c7-alkyl, R2 is methyl or ethyl, R3 to R11 are each hydrogen or halogen and X and Y are each oxygen or sulfur.

Halogen is fluorine, chlorine, bromine and / or iodine, but in particular Understanding chlorine.

The alkyl groups at R1 can be straight-chain or branched be. Examples of such groups include: methyl, ethyl, n-propyl, isopropyl, n-, i-, sec-, tert-butyl, n-pentyl, n-heptyl and their isomers.

Because of their action, compounds of the formula I are preferred in which R1 n-propyl, isobutyl, sec. Butyl or n-penyl, R2 ethyl, R3 to R11 hydrogen , .Chlorine or bromine, X is oxygen and Y is sulfur.

The compounds of formula 1 can be prepared, inter alia, by the following methods known per se: X EAR R 11 y% ci + ll to Rlo särbindendes 1 R2 (is) mean R mean> 1 5 7 8 (iii) x NeO R 11, <R6R11R10 ab) IHOL + R3 \ \ / R9 - # I IilY / (II) (1v) x 011 2) 20> C1 R2 XR 1 acid binding :: nde to VI Cl rv> 8 (III) R4 5R7.% x R3 <\ O <Rg + HYR1 acid binding> R20> 11 0 6 Rll 10 (IIIa3. I (vI) 1 eM. - (IIIb) In formulas II to VI, R1 and R11 have the meaning given for formula I and Me stands for an alkali metal, in particular sodium or potassium, or the group (R) 3-NH in which R is hydrogen or C1-C4-alkyl.

Acid-binding agents that can be used are: tortiary amines, e.g. trialkylamines, Pyridine, dialkylanilines; inorganic bases such as hydrides, hydroxides; Carbonates and Bicarbonates of n all-metal and alkaline earth metals. Sometimes it is with the implementations necessary to use catalysts such as copper or copper chloride.

Processes la and lb and 2 are carried out at one reaction temperature between -2 ° to 130 ° C, at normal pressure and in solvents or thinners carried out.

Suitable solvents or diluents are, for. B. Aether and aetherartive Compounds such as diethyl ether, dipropyl ether, dioxane, tetrahydrofuran; Amides, like 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, IIIa, IIIb and V can be used analogously known methods.

The compounds of formula 1 have a broad biocidal effect and are therefore suitable for combating various types of plant and animal Pests. But they have, in particular, insecticidal and alcaricidal properties and can be used against all stages of development such as eggs, larvae, pupae and nymphs and adults are used by insects and representatives of the order Akarina, such as e.g. against insects of the families: Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Phyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabacidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyralidae, Culcidae, Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae, as well as acarids of the families Ixodidae, Argasidae, Tetranychidae and Dermanyssidae.

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

Suitable additives are e.g.

organic phosphorus compounds, derivatives of nitrophenols, formamidines, Ureas, pyrethrin-like derivatives, carbamates and chlorinated hydrocarbons.

The active ingredients of the formula I are also suitable for combating representatives the Thallophyta department such as viruses, bacteria and fungi. So they own fungicidal properties against phytopathogenic fungi on various cultivated plants, such as cereals, maize, rice, vegetables, ornamental plants, fruit trees, vines, field crops Etc.

The new active ingredients can be used on fruits, flowers> foliage, Fungi that occur on stems, tubers and roots are contained or destroyed, parts of plants that grow later are also spared from such fungi stay. The active ingredients of the formula I are in particular against the following classes, belonging to phytopathogenic fungi: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes.

The new active ingredients are also used to treat seeds, fruits, Tubers, etc. to protect against fungal infections, for example from smut all Kind as Ustilaginales and to control phytopathogenic nematodes.

The compounds dc formula I can be used alone or together can be used with suitable carriers and / or additives. Suitable carriers and aggregates can be solid or liquid 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 substances Emulsion concentrates, granules, dispersions, sprays, to solutions or slurries processed in the usual formulation that is part of general knowledge in application technology will. Furthermore, "cattle dips", i.e. cattle baths, and "spray races", i.e.

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

The agents according to the invention are prepared in a manner known per se Way by intimately mixing and / or grinding active ingredients of the formula I with the suitable carriers, optionally with the addition of the 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 concentrations dispersible in water: Wettable powders, pastes, emulsions; b) Solutions Der'Gehalt of active ingredient in the means described above is between 0.1 and 95%.

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 tallcum The active ingredients are mixed with the carrier materials and ground.

Granules. The following are used to produce a 5% granulate Substances used: 5 parts of active ingredient, 0.25 parts of epichlorohydrin, 0.25 parts of Cety'l 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 iui vacuum evaporates.

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 Kieselsture, 19.5 parts of Champagne chalk, 28.1 parts of kaolin; c) 25 parts Active ingredient 2.5 parts of isooctylphenoxy-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; 10 Parts active ingredient 3 parts mixture of the sodium salts of saturated fatty alcohol sulfates, 5 parts of naphthalenesulfonic acid / formaldehyde condensate, 82 parts of kaolin.

The active ingredients are mixed with the surcharge in suitable mixers intimately mixed and ground on appropriate mills and rollers. You get Wettable powder that mixes with water to form suspensions of any desired concentration let it dilute.

Emulsifiable concentrates: For the production of a) 10% and b) 25% emulsifiable concentrate, the following substances are used: a) 10 parts Active ingredient 3.4 parts of epoxidized vegetable oil, 3.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkylarylsulfonate calcium salt, 40 Parts of dimethylformamide, 43.2 parts of 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: Used to produce a 5% or 95% spray the following ingredients are used: 5 parts of active ingredient, 1 part of epichlorohydrin, 94 parts of petrol (boiling point 160-190 ° C).

or 95 parts of active ingredient 5 parts of epichlorohydrin.

Bfflsiel 1 To a solution, cooled to 10 ° C., of 37 g of 3-hydroxydiphenyl ether and 22 g of triethylamine in 500 ml of absolute diethyl ether are mixed with 41 g of O-ethyl-S-n-propylthiolphosphoric acid chloride in 60 ml of diethyl ether added dropwise so quickly that the temperature does not exceed 300C.

The mixture is stirred for a further two hours at 20-25 ° C. and the mixture is added with further stirring with 300 ml of ice water.

The organic phase is separated off, shaken once with water and twice with ice-cold 5% sodium hydroxide solution and then washed neutral with water. The ether phase is now treated with activated charcoal, filtered, dried and the solvent is evaporated off. The above residue is dried for three hours at 70 ° C. and 0.1 torr. The compound of the formula is obtained as a yellowish, non-distillable, viscous oil with a refraction of nD20 = 1.5512.

The following connections are also established in the same way: Example 2 A) Insecticidal food poison effect Cotton plants and potato plants were sprayed with a 0.05% aqueous active ingredient emulsion (obtained from a 10% 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 (Lcptinotarsa decemiineata). 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 feed poison effect against Spodoptera, Heliothis and Leptinotarsa decernlineata larvae.

B) Systemic insecticidal effect To determine the systemic Effect were planted bean plants (Vicia faha) in a 0.01% aqueous solution Active ingredient solution (obtained from a 10% emulsifiable concentrate) set. After 24 hours, aphids (Aphis fabae) were found on the above-ground parts of the plant. set. Thanks to a special device, the animals were protected from the contact and Cas effects protected.

The experiment was carried out at 240 ° C. and 70% relative humidity.

The compounds according to Example 1 had a systemic 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, active ingredient per hectare) in 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 adult each: e 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, 1 or 0.1 ppm test substance immersed. The tube was then filled with: a standardized cotton ball closed and turned upside down so that the active ingredient emulsion from the cotton wool could be recorded.

The evaluation was carried out in the adults after 2 weeks and in the Larvae after 2 days. Two repetitions are allowed 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 active 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 testing for acaricidal activity with an infected piece of leaf from a mass breed of Tetranychus urtlcae. The overflowed bcwegl ichen stages were made from a chromatography nebulizer with the emulsified test preparations dusted that no runoff 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 is printed out as a percentage.

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

The compounds according to Example 1 were effective against adults in the above test, 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 sown tomatoes.

To assess the nematocidal effect, 28 days after the plants 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 (1)

Claims 1. Diphenyl ether phosphates of the formula where R1 is C1-C7-alkyl, R2 is methyl or ethyl, R3 to R11 is hydrogen or halogen and X and Y are each oxygen or sulfur. 2. Compounds according to claim 1, wherein R1 is n-propyl, isobutyl, sec-butyl or n-pentyl, R2 ethyl, R3 to R11 each hydrogen, chlorine or bromine, X oxygen and mean sulfur. 3. Compound according to claim 2 of the formula 4. A compound according to claim 2 of the formula 5. A compound according to claim 2 of the formula 6. A compound according to claim 2 of the formula 7. A compound according to claim 2 of the formula 8. A compound according to claim 2 of the formula 9. A compound according to claim 2 of the formula 10. A compound according to claim 2 of the formula 11. A compound according to claim 2 of the formula 12. A compound according to claim 2 of the formula Process for the preparation of compounds according to Claims 1 to 12, characterized in that a compound of the formula with a compound of the formula in the presence of an acid-binding agent or with a compound of the formula in which R1 to R11, X and Y have the meaning given in claim 1 and Me stands for an alkali metal or an ammonium or alkylammonium group. 14. Process for the preparation of compounds according to Claims 1 to 12, characterized in that a compound of the formula with a compound of the formula HYR1 in the presence of an acid-binding agent or with a compound of the formula MeYR1, in which R1 to R11, X and Y have the meaning given in claim 1 and Me stands for an alkali metal, an ammonium or alkylarrniionium group. 15. Pesticides, which as an active component Compound according to claims 1 to 12 and suitable carriers and / or other additives contain. 16. Use of compounds according to claims 1 to 12 for Control of various animal and vegetable pests. -17. Use according to claim for combating all stages of development of insects and representatives of the order Akarina. 18. Use according to claim 16 for the defense against plant parasites Nematodes.