DE2354586A1 - Pesticidal phenyl (di) thiophosphates - useful as insecticides, acarimide-imides and nematocides - Google Patents

Abstract

Pesticidal cpds of formula (I) (where R1 is methyl or ethyl; R2 and R3 are H, halogen, (1-4)C (alkyl or alkoxy); R4 is pyrrolidino, 3-pyrrolinyl, piperidino, -N=CH-N(1-4C alkyl)2, -NHCOO(1-4C alkyl) or -NH-CO-N(1-4C alkyl)2; and X is O or S) are prepd by reacting halides of formula (II) with phenols of formula (III) is used in the form of its alkali metal, ammonium or alkylammonium salt.

Description

New esters The present invention relates to thio respectively. Dithiophosphoric acid ester, Process for their creation and their use in pest control.

The thio resp. Dithiophosphoric acid esters have the formula where R1 is methyl or ethyl, R2 and R3 are each hydrogen, halogen, C1-C4-alkyl or Cl-C4-alkoxy, N = CH- (C1-C4-alkyl) 2, -NHCOOC1-C4-alkyl or NH-CO-N (C1-C4-alkyl) 2 and X is oxygen or sulfur.

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

The alkyl and alkoxy groups that come into question for R2, R3 and R4 or subgroups can be straight-chain or branched. Examples of such groups are i.a.

Methyl, methoxy, ethyl, ethoxy, propyl, isopropyl, n-, i-, sec. - and tert-butyl.

Because of their action, compounds of the formula I are preferred in which R1 and ethyl, R2 hydrogen or methyl, R3 hydrogen, R4 -N = CH-N (CH3) 2, -NHCOOCH3 or -NH-CO-N (CH3) 2 and oxygen.

The compounds of the formula I can be prepared by methods known per se, for example as follows: acid binding agent # I In the formulas II, III and IV, R1 to R4 and X have the meaning given for the formula I and tee stands for an alkali metal, in particular sodium or potassium, ammonium or alkylammonium.

The methods l-a and -lb can be carried out at normal pressure, at one temperature from 0-80 ° C, preferably 20-50 ° C and inert towards the reactants Solvents and diluents are carried out.

Suitable solvents or diluents are, for example: ether and ethereal 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.

The starting materials of the formula II are known and can analogously e.g. according to the J. org. Chem. 30, 3217 (1965) described method.

The active ingredients of the formula I are suitable for combating a wide variety of types animal and vegetable pests.

The compounds of formula I have a strong and lasting effect deadly or repellent effect against all stages of development, such as eggs, larvae, Nymphs, pupae and adults of insects, such as insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, lenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleriidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae.

The compounds of the formula I are also effective against solids, larvae and adults of representatives of the order Akarina, such as mites, spider mites and ticks, e.g. the Families: Ixodidae, Argasiade, Tetranychidae, and Demanyasidae.

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

Organic phosphorus compounds nitropheols, for example, are suitable as additives and derivatives, formamidines, carbamates and chlorinated hydrocarbons.

The compounds of formula 1 are also suitable for combating phytopathogenic nematodes.

The compounds of formula 1 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, solvents, dispersants, Wetting agents, adhesives, thickeners, binders and / or fertilizers.

For application, the compounds of the formula I can be converted into dusts, Emulsion concentrates, granules, dispersions, sprays, to solutions or slurries in the usual formulation, which is 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 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 are present in the following working-up forms and applied Fixed forms of processing: dust, grit, Granules, coated granules, impregnation granules and homogeneous granules, liquids Work-up 5 forms: a) Active substance concentrates dispersible in water: wettable powder (wettable powders) pastes, emulsions; b) Solutions 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 using 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 with the carrier materials and ground.

Granulate: The following are used to produce a 5% strength granulate Substances used: 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 a vacuum.

Wettable powder: For the production of a) 40%, b) and c) 25% d) The following ingredients are used: a) 40 parts of active ingredient 5 parts Lignin sulfonic acid sodium salt, 1 part dibutylnaphthalene sulfonic acid sodium salt, 54 Parts of silica; b) 25 parts of active ingredient 4.5 parts of calcium liginsulphonate, 1.9 parts Champagne chalk / hydroxyethyl cellulose mixture (1: 1), - 1.5 parts sodium dibutyl naphthalene sulfonate, 19.5 parts of silica, 19 parts of Champagne chalk, 28.1 parts of kaolin; c) 25 part 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; 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 mills and rollers. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.

Emulsifiable concentrates: To create a) above and b) 25% emulsifiable concentrates-the following substances are used: a) 10 parts Active ingredient 3.4 parts of epoxidized vegetable oil, -13.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether nud 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: To produce a 5% spray, the the following ingredients are used: 5 parts of active ingredient, 1 part of epichlorohydrin, 94 parts Petrol (boiling limits 160 - 900C) Example 1 Preparation of 0-ethyl-S- (n) -propyl-0- (3-methyl-4-N, N-dimethylformamidonophenyl) -thiophosphoric acid ester 23.9 g of 3-methyl-4-N, N-dimethylformamidinophenol are dissolved in 150 ml of benzene, then 13.3 g of triethylamine are added. At 10 - 15 ° C, stirring constantly 26.4 g of 0-ethyl-S-n-propyl-chlorothiolphosphoric acid ester were added dropwise. After 12 hours Stirring at room temperature is done with water, 3% Na2CO3 solution and again with water washed and dried over anhydrous sodium sulfate.

The benzene is distilled off. After molecular distillation of the residue, the compound of the formula is obtained with a refraction of nD3 = 1.5559. The following connections are also established in the same way: Verbi; nd) ün hysi-che bate-n 2 OM (CH) NH-C-OCH3 -) 2- / ° 4 cd23; i, 7577tl (n) UBH7 $ ~ 2-H50 S NCOOCII 59yt - ---- --- 3 (n-3C3 S 6 IGooCKz 2 5 lI 2 3 fl 22- l) 5: 3Üi 1) {'n) f73 -ü2H5o ÜH- \ -fII 2-H5 ° D 4 7-Ä- -H fl 22 11578-9 MX N (ÖH3) 2i ; (n3 c U 6 c -H -Ö $ 'o ,, n 35-2 4 -22 le5-52- 4 C3 -A5 ° slol jt 7Ia 20 ls 60 (n) 7S Connection physical data 2H5% oil II j / = t (n) C3H7S O C, H, O \ 20 (n) C3H7S < N = CH-N (C-H3) 2 0 GH ~ O \ 11 and = 1.5601 (n) G3H7s- N = -CH-N (CH3-) 2 0 2 5 1iD20 = to CHD n20 5560 (n) C3117 $ n N = CH-g (CH) 2 S. dark dark oil (n) C3H7S- N Example 2 A) Insecticidal food poison effect Cotton plants were sprayed with a 0.05% aqueous active substance emulsion (obtained from a 10% emulsifiable concentrate).

After the covering had dried on, the cotton plants were each with Spodoptera littoralis or Heliothis virescens larvae (L3) occupied. The attempt was carried out at 240C and 60% relative humidity.

The compounds according to Example 1 showed good results in the above test insecticidal feed poison effect against Spodoptera and Heliothis 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 with lice infest leaves with a spray liquor at a concentration of 1000 ppm (made from a 25% gen 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) took place 2 days after the addition of the active ingredient in granulate form (application rate 8 kg of active ingredient per hectare) into the paddy water. The evaluation for insecticidal effect was carried out 10 days after adding the granules.

The compounds according to Example 1 showed a good effect in the above test against Chilo suppressalis.

Example 4 Action against ticks A) Rhipicephalus bursa In two test series 5 adult ticks resp.

50 tick larvae are 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 and 0.1 ppm test substance immersed. The tube was then covered with a standardized cotton ball closed and turned upside down, so that the active ingredient emulsion from the 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 performed for each experiment.

The compounds according to the example showed a good effect in the above test against adults and larvae of Rhipicephalus bursa.

B) Boophilüs microp-lus (larvae) With an analogous dilution series As in test A, experiments were carried out with 20 OP-sensitive larvae each.

The compounds according to Example 1 showed a good effect in the above test against sensitive larvae of Boophilus microplus.

Example 5 Action against spider mites Phaseolus vulgaris (French beans) were tested for acaricidal activity with an infected piece of leaf 12 hours before the test from a mass breed of Tetranychus urticae. The defected movable Stages were made from a chromatography atomizer 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 expressed as a percentage. During the "holding time" the treated ones stood Plants in greenhouse cabins at 25 "C.

The compounds according to Example 1 showed a good effect in the above Test against eggs, larvae and adults of Tetranychus urticae.

Example 6 Contact effect against the blow fly (Lucilia sericata) Blow fly, minced horse meat was served as food was mixed with dilution concentrations of an active ingredient. Evaluation according to 24 hours.

The compounds according to Example 1 showed a good effect in the above Test against the blow fly.

Example 7 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.

The nematocidal effect was assessed 28 days after planting or after sowing the galls present at the roots are paid out.

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

Claims (12)

Claims Compounds of the formula where R1 is methyl or ethyl, R2 and R3 are each hydrogen, halogen, C1-C4-alkyl or C1-C4-alkoxy, N = CH-N (C1-C4-alkyl) 2, -NHCOOC1-C4-alkyl or -NH-C0-N (C1-C4-alkyl) 2 and X is oxygen or sulfur. 2. Compounds according to claim 1, wherein R1 is ethyl, R2 is hydrogen or methyl, R3 hydrogen, R, -N = CH-N (CH3) 2, -NHCOOCH3 or -NH-CO-N (CH3) 2 and X represent oxygen or 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. Process for the preparation of compounds according to Claims 1 to 8, 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 lets react, in which R1 to R4 and X have the meaning given in claim 1 and Me is an alkali metal, ammonium or alkylammonium. 10. Pesticides, which are the active component compounds according to claims 1 to 8 and suitable carriers and / or other additives contain. 11. Use of compounds according to claims 1 to 8 for Control of insects and representatives of the order Akarina. 12. Use of compounds according to claims 1 to 8 for Control of phytopathogenic nematodes.