DE2352142A1 - Biocidal triazolyl dithio phosphates - prepd from dithiophosphoric acid halides and 3-hydroxy triazoles - Google Patents

Abstract

Cpds of formula (I): (where R1 is CH3 or C2H5; R2 is 1-5C alkyl; R3 is alkyl, aralkyl, cycloalkyl or phenyl; R4 is CN, COOR5 or CONR6R7; R5 is alkyl; and R6 and R7 are H or alkyl), which are esp. useful as insecticides and acaricides, and are also active against phytopathogenic fungi and nematodes, are prepd by reacting cpds of formula (II) with halides of formula (III) (where Hal is halogen), the reaction being carried out in the presence of an acid binding agent or (II) being used in the form of its salt with a monovalent metal.

Description

Novel Esters The present invention relates to 1,2,4-triazolyldithiophosphoric acid esters , Process for their production and their use in pest control.

The triazolyldithiophosphoric acid esters have the formula wherein R1 is methyl or ethyl, R2 is cl-C5-alkyl, R3 is alkyl, aralkyl, cycloalkyl or phenyl, R4 is -CN, -COOR5 or R5 is alkyl and R6 and R7 3e are hydrogen or alkyl.

The alkyl groups which are suitable for R2, R3> R5, R6 and R7 can be straight-chain or branched. The alkyl groups at R3, R5, R6 and R7 have in of the chain has 1 to 12, preferably 1 to 6 carbon atoms. Examples of such Groups include: methyl, ethyl, propyl, isopropyl, n-, i-, sec-, tert-butyl, n-Pentyl, n-Hexyl, n-Octoyl, n-Dodecyl and their isomers.

Preferred aralkyl groups at R3 are benzyl and phenethyl.

The cycloalkyl groups at R3 have 3 to 8 ring carbon atoms. Examples of such groups are: cyclopropyl, cyclopentyl and cyclohexyl.

The phenyl group at R3 can be unsubstituted or by one or more, identical or different halogen atoms, such as fluorine, chlorine, bromine and / or iodine, C1-C4-alkoxy or Cl-C4-alkyl groups.

Because of their action, preference is given to compounds of the formula I in which R1 is ethyl, R2 is n-propyl or n-pentyl, R3 is Cl-C6-alkyl or unsubstituted or chlorine-substituted phenyl, R4 is -CN, -COOR5 or R5 is C1-C6-alkyl and R6 and R7 are each hydrogen or C1-C6-alkyl.

The compounds of the formula I are prepared by methods known per se, for example as follows: RN - NS a) R-NjlOR I,: L; J (11> In the formulas II, III and IV, R1 to R4 have the meaning given for the formula I, Hal stands for a halogen atom, in particular for chlorine or bromine, and Me for a monovalent metal, in particular an alkali metal.

The following bases, for example, can be used as acid-binding agents: tertiary amines, such as triethylamine, dimethylaniline, pyridine, inorganic bases, such as Hydroxides and carbonates of alkali and alkaline earth metals, preferably sodium and Potassium carbonate.

The reactions are preferably known to the reactants inert solvents or diluents are carried out. For this, for example the following are suitable: aromatic hydrocarbons such as benzene, toluene, gasoline, Halogenated hydrocarbons, chlorobenzene, polychlorobenzenes, bromobenzene, chlorinated Alkanes having 1 to 3 carbon atoms, ethers such as dioxane, tetrahydrofuran; Ester, such as ethyl acetate; Ketones such as acetone, methyl ethyl ketone, diethyl ketone and nitriles e.g.

Acetonitrile etc.

Some of the starting materials of the formulas II and IV are known or can e.g. analogous to that in Chem. Ber. 56 B, 2276-83 (1923) described method getting produced.

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 acaricidal properties and can be used against all stages of development such as kier, larvae, pupae, 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, Reduviridae, Phyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, noctuidae, Lymatriidae, Pyralidae, Culcidae, Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidaes 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.

Examples of suitable additives are: organic phosphorus compounds, derivatives of nitrophenols, formamidines 9 ureas carbamates and / or chlorinated hydrocarbons.

The active ingredients of the formula I are also suitable for combating representatives of the Thallophyta department such as viruses, bacteria and fungi So they have fungicides Properties against phytopathogenic fungi on various cultivated plants, such as Grains, corn, rice, vegetables, ornamental plants, fruit trees, vines, field crops etc.

The new active ingredients can be used on fruits, flowers, foliage, stems, Bulbs and roots occurring fungi are contained or destroyed, whereby then parts of plants that grow later remain spared from such fungi.

The active ingredients of formula I are particularly effective against the following Classes, belonging to phytopathogenic fungi effective: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes.

The new active ingredients can also be used to treat seeds, Fruits, tubers, etc. to protect against fungal infections, for example from smut fungi of all kinds, such as Ustilaginales and for the control of phytopathogenic nematodes to serve.

The compounds of the 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, 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.

Sprinkles 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, granulates, coated granulates, impregnation granulates and homogeneous granulates Liquid processing forms: a) Active substance concentrates dispersible in water: 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 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 with the carrier materials and ground.

Granules: The following are used to produce 5% granules 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 (tube 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 laying 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) 10% wettable powder, the following ingredients are used: a) 40 parts of active ingredient 5 parts of lignin sulfonic acid atrium salt, 1 part of dibutylnaphthalenesulfonic acid sodium salt, 54 parts of silica; b) 25 parts of active ingredient, 4.5 parts of Calciutri-Liginsulfonat, 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 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 naphthalenesulfonic 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: 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, 13.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkylarylsulfonst calcium salt, 40 Parts of dimethylformamide, 43.2 parts of xylene; b) 25 parts of active ingredient 2.5 parts of epoxidized Vegetable tol, 10 parts of an alkylarylsulfonate / fatty alcohol polyglacol 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 epichlorohydring 94 parts Petrol (boiling point 160 - 190 ° C) Example 1 Preparation of O-ethyl-S- (n) -propyl-O- [1-phenyl-5-ethoxycarbonyl-1,2,4-triazolyl- (3)] -dithiophosphoric acid ester 12 g of 1-phenyl-3-hydroxy-5-ethoxy carbonyl-1,2,4-triazole and 7 g of potassium carbonate in 250 ml of methyl ethyl ketone are refluxed for one hour. Be at 500C then 10 g of O-ethyl-S- (n) -propyl-dithiophosphoric acid chloride were added dropwise and the mixture was refluxed for two hours.

After filtering off the precipitated salts and evaporating the solvent in vacuo, the compound of the formula is obtained 20 with a refraction of nD = 1.5578 as a pale yellow oil. The following connections are also established in the same way: 20 D - 1.5094 20 nD = 1.5679 m.p .: 79-82 Example 2 A) Insecticidal food poison effect Cotton plants and potato 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 Heliothie virescens larvae L3 and the potato plants populated with Colorado potato beetle larvae (Lepinotarsa decemlineata). The attempt was made carried out at 24 ° C and 60% relative humidity.

The compounds according to Example 1 showed a good result in the above test insecticidal frasagift effect against Spodoptera, Heliothis and Leptinotarsa decemlinsata larvae.

B) Systemic insecticidal effect To determine the systemic Effect were rooted bean plants (Vicia faba) 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 contact and gas effects protected. The experiment was carried out at 24 ° 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 infectious station with Chile suppressalia larvae (L1; 3-4 mm long) occurred 2 days after the drug was added in Granulate form (air wall quantity 8 kg active substance 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 suppressalia.

Example 4 Action against soil insects Sterilized compost soil is mixed homogeneous with a wettable powder containing 25% active ingredient, so that a concentration of 16 ppm resp. of 8, 4, 2, 1 ppm arises. In the soil treated in this way, young ones will grow Zucchini and cabbage plants are used and immediately with 5 larvae of Aulacophora femoralis (Age: 15 d / 25 ° C) resp.

15 eggs of Chortophila brassicae (cabbage flies) infected; a third The corresponding earth pattern is provided with apple carving as a lining and with a 5 Larvae of Pachnoda savignyi (20 d / 25 ° C) planted. 10 days after application and infestation is rated for mortality.

The screening test with groundworms (Agrotis Y-L2) runs analogously, with the difference is that the concentrations are 40, 20, 10 ppm. Be used as feed Mallow flowers used.

The compounds according to Example 1 showed activity against in the above test Aulacophora femoralis, Chortophila brassicae, Pachnoda savignyi and Agrotis larvae.

Example 5 Action against ticks A) Rhipicephalus bursa 5 adults each Ticks or 50 tick larvae were counted in a glass tube and kept 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 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 run for each attempt.

B) Boophilus microplus (larvae) With an analogous dilution series as in test A, 20 sensitive resp. 0P-resistant larval trials carried out. (The resistance relates to the tolerance of Diazinon) The compounds according to Example 1 were effective in tests against adults and larvae of Rhipicephalus bursa and sensitive resp. OP-resistant larvae of Boophtlus microplus.

Example 6 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 urticae. The defected movable 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 evaluated under the binocular for living and dead individuals and the result expressed 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, Larvae and eggs of Tetranychus urticae.

Example 7 Action against soil nematodes To test the action against Soil nemetodes 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, in a row of verauchas, were immediately 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 on the roots are counted.

In this test, the active ingredients according to Example 1 show a good effect against Meloidogyne arenaria.

Claims (10)

Claims 1. Compounds of the formula where R1 is methyl or ethyl, R2 C1-C5-alkyl, R3 alkyl, aralkyl, cycloalkyl or phenyl, R4 -CN, -COOR5 or R5 is alkyl and R6 and R7 are each hydrogen or alkyl. 2. Compounds according to claim 1, wherein R1 is ethyl, R2 is n-propyl or n-pentyl, R3 is C1-C6-alkyl or unsubstituted or substituted by chlorine phenyl, R4 is -CN, -COOR5 or R3 is C1-C6-alkyl and R6 and R7 are each hydrogen or C1-C6-alkyl. 3. Compound according to claim 2 of the formula 4. A compound according to claim 1 of the formula 5. A compound according to claim 1 of the formula 6. Process for the preparation of compounds according to responses 1 to 5, characterized in that a compound of the formula or a compound of the formula optionally in the presence of an acid-binding agent with a compound of the formula reacted, in which R1 to R4 have the meaning given in claim 1, Hal stands for a halogen atom and Me for a monovalent metal. 7. Pesticides, which are an active component Compound according to claims ii to 5 and suitable carriers and / or other additives contain. 8. Use of compounds according to Claims 1 to 5 for combating of various animal and vegetable pests. 9. Use according to claim 8 for combating insects and representatives of the order Akarina. 10. Use according to claim 8 for combating phytopathogens Nematodes.