DE2352140A1 - Biocidal triazolyl dithio phosphates - prepd from dithio phosphoric 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 or cycloalkyl; and R4 is H, alkyl or phenyl) which are esp. useful as insecticides and acaricides and in addn. have activity against phytopathogenic fungi and nematodes, are prepd by reacting halides of formula (II) (where Hal is halogen) with cpds of formula (III), the reaction being carried out in the presence of an acid binding agent or (III) being used in the form of its salt with a monovalent metal.

Description

New esters The present invention relates to triazolyldithiophosphoric acid esters, Process for their production and their use in pest control.

The TriazolyldithiophosphorsSureester have the formula where R1 is methyl or ethyl, R2 is Cl-C5-alkyl, R3 is alkyl or cycloalkyl and R4 is hydrogen, alkyl or phenyl.

The alkyl groups in R2, R3 and R4 can be straight-chain or branched be and have at R3 and R41 to 12, preferably 1 to 6 carbon atoms. Examples Such groups include: methyl, ethyl, propyl, isopropyl, n-, i-, sec.-, tert. -Butyl, n-pentyl, n-octyl, n-dodecyl and their isomers.

The cycloalkyl groups in question for R3 have 3 to 8 ring carbon atoms on. Preferred cycloalkyl radicals are: cyclopropyl, cyclopentyl or cyclohexyl.

The phenyl radical for R4 can be unsubstituted or, for example by methoxy, halogen atoms such as fluorine, chlorine, bromine and / or iodine, preferably chlorine, and / or C1-C5-alkyl be substituted.

Because of their effect of particular importance are compounds of Formula 1, in which R1 is ethyl, -R2 is n-propyl or n-pentyl, R3 is Cl-C6-alkyl and R4 is hydrogen, C1-C4-alkyl and unsubstituted phenyl mean.

The compounds of the formula I can be prepared by methods known per se, for example as follows: a) R3- R4 \ N1OH + Hal-P (<1 sàutelbindendes> I 2 (II) (III) 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 can preferably take place in relation to the reactants -inert- dissolving or thinning agents 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 with 1 to 3 carbon atoms, ethers such as dioxane, tetrahydrofuran, esters, 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 compounds or can, for example, analogously to that in Chem. Ber. 56 B, 2276-83 (1923) described method getting produced.

The compounds of the formula I 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 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, Scarabaeidae, 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.

Examples of suitable additives are: organic phosphorus compounds, derivatives of nitrophenols, formamidines, urea carbamates and / or 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 types of cultivated plants, such as cereals, 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 Even parts of plants that grow later are 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, Kriollen, 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, Network-,.

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 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 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, coating granules, impregnation granules and homogeneous granules 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 Formula 1 are formulated as follows, for example : 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 substances 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 (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) 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 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 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: The following ingredients are used to produce a 5% spray: 5 parts of active ingredient, 1 part of epichlorohydrin, 94 parts of gasoline (boiling point 160 - 1900C) Example 1 Production of O-ethyl-S- (n) -propyl-O- [1-isopropyl-1,2,4-triazolyl- (3)] - dithiophosphate 7 g of 1-isopropyl-3-hydroxy-1,2,4-triazole and 7 g of potassium carbonate in 250 ml of methyl ethyl ketone are refluxed for one hour . At 50 ° C., 10 g of O-ethyl-S- (n) -propyldithiophosphoric acid chloride are then added dropwise and the mixture is 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 n20 = 1.5242 as a pale yellow oil. 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 the covering had dried on, 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 feed poison effect against Spodoptera, Heliothis and Leptinotarsa decemlineata Lsrven.

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, aphid (Aphis fabae) set. Thanks to a special device, the animals were protected from contact and gas effects protected.

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

The compounds according to Example 1 acted systemically 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 acted against chilo in the above tea suppressalis.

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 / 250C) resp.

15 eggs of Chortophila brassicae (cabbage flies) .infestwert; a third corresponding one Erdmuster is provided with apple wedges as food and with 5 larvae of Pachnoda savignyi (20 d / 250G) planted. 10 days after application and infestation is on Mortality rated.

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 leaves used.

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

Example 5 Action against ticks A) Rhipicephalus burse 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, 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. OP-resident larval trials carried out. (The resistance refers to the tolerance of -Diaælnon) The compounds according to Example 1 were effective against adults and larvae in these tests of Rhipicephalus bursa and sensitive resp. Or-resistant larvae of Boophilua microplus.

Example 6 Acaricidal effect of Phaneolua vulgaris (plants) 12 hours before the test for acariid activity with an infected piece of leaf a mass breeding of Tetranychus urticae. The defected movable Stages were made from a chromatographic nebulizer with the emulsified tea preparations dusted that no runoff of the spray liquid occurred. Were awake for two to 7 days 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 250C.

The compounds according to Example 1 acted in the above Teot against adults, Larvae and eggs of Tetranychus urticae.

Example 7 Action against soil nematodes To test the action against Rod 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 on the roots are counted.

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

Claims (13)

Patent claims 1. Compounds of the formula where R1 is methyl or ethyl, R2 is C1-C5-alkyl, R3 is alkyl or cycloalkyl and R4 is hydrogen, alkyl or phenyl. 2. Compounds according to claim 1, wherein R1 is ethyl, R2 is n-propyl or n-Pentyl, R3 C1-C6-alkyl and R4 hydrogen, C1-C4-alkyl and unsubstituted phenyl mean. 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. Compound according to claim 2 of the formula 7. A compound according to claim 1 of the formula 8. A compound according to claim 2 of the formula 9. Process for the preparation of compounds according to responses 1 to 8, 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. 10. Pesticides, which are an active component Compound according to claims 1 to 8 and suitable carriers and / or other additives holds. 11. Use of compounds according to claims 1 to 8 for Control of various animal and vegetable pests. 12. Use according to claim 11 for combating insects and Representatives of the order Akarina. 13. Use according to claim 11 for combating phytopathogens Nematodes.