DE2347223A1 - (Thio)phosphoric acid thioesters prepn. - with biocidal activity - Google Patents

Abstract

Thioesters of formula (Ia) or (Ib): (where R1 and R2 are 1-5C alkyl, 3-5C alkenyl or 3-5C alkynyl; R3 is 1-5C alkyl or aryl; and X and Y are O or S), which are partic. useful as insecticides and acaricides and are also active against Thallophyta, esp. phytopathogenic fungi, as well as against phytopathogenic nematodes, are prepd. by reacting cpds. of formula (IIa) or (IIb) with cpds. of formula (III), generally at -30 to +50 degrees C at normal pressure in a solvent or diluent;.

Description

Novel Esters The present invention relates to organic phosphoric acid compounds Process for their production and their use in pest control.

The compounds have the formula where R1 and R2 are each C1-C5-alkyl, C3-C5-alkenyl or C3-C5-alkynyl, R3 is C1-C5-alkyl, aryl and X and Y are each oxygen or sulfur.

The alkyl, alkenyl or alkynyl groups for R1 to R3 can be straight-chain or branched, unsubstituted or the alkyl groups at R3 be substituted, for example, by halogen, preferably fluorine and / or chlorine.

Examples of such groups include: methyl, ethyl, trifluoromethyl, Propyl, isopropyl, n-, i-, sec-, tert-butyl, allyl, methallyl, 2-chloroallyl, propargyl.

Aryl at R3 are mononuclear or polynuclear, unsubstituted or substituted aromatic hydrocarbon radicals, but especially the phenyl radical, to understand.

The substituents on these radicals include, for example, halogen, Cl-C5-alkyl, C1-C5-alkoxy, C1-C5-alkylthio and / or nitro are possible.

Because of their action, compounds of the formula I are preferred in which R1 methyl or ethyl, R2 methyl, ethyl or propyl, R3 methyl, ethyl, propyl or phenyl and X and Y each represent oxygen or sulfur.

The compounds of the formulas I and Ia are prepared according to the following method, which is known per se: (In analogy to other additions of sulfonyl chlorides to a -CC bond, the compound IV is the main component) The reaction is carried out at a temperature of -30 to 500C, under normal pressure and in solvents or diluents.

Suitable solvents or diluents are e.g.

ethereal compounds such as dioxane, tetrahydrofuran; Amides, like N, N-dialylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylenes, chloroform, chlorobenzene; Nitriles such as acetonitrile; SMSO; Alcohols such as ethanol and ketones such as acetone, ethyl methyl ketone and water.

The starting materials of the formula V are known and can be used analogously in methods described in the literature.

The compounds of the formulas I and Ia have a broad biocidal effect on and can be used to combat various plant and animal species Pests are used.

In particular, they are suitable for combating insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, 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, Dermanyssidae.

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

Org. Phosphorus compounds; Nitrophenols and their derivatives; Formamidines, ureas, carbamates and chlorinated hydrocarbons.

The compounds of the formulas I and Ia have, in addition to those mentioned above Properties also show an effectiveness against representatives of the Thallophyta department. Some of these compounds show bactericidal activity. But they are above all against fungi, in particular against phytopathogens belonging to the following classes Effective fungi: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes.

The compounds of the formulas I and Ia 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 formulas I and Ia are also suitable for controlling phytopathogenic nematodes.

The compounds of the formulas I and Ia can be used alone or can be used together with suitable supports and / or supplementary sockets. Suitable Carriers and aggregates can be solid or liquid and correspond to those in the Formulation technology for common substances such as natural or regenerated substances, Solution, dispersants, wetting agents, adhesives, thickeners, binders and / or fertilizers.

For application, the compounds of the formulas I and Ia can be used to form 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. Furthermore, "cattle dips", i.e. cattle baths, and "spray races", i.e. to mention spray courses in which aqueous preparations are used.

The agents according to the invention are prepared in a manner known per se Way by intimate mixing and / or grinding of active ingredients of the formulas I. and Ia with the suitable carriers, optionally with the addition of opposite dispersants or solvents that are inert to the active ingredients.

The active ingredients of the formulas I and Ia can, for example, as follows The following can be formulated: 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 (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) 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 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 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 following ingredients are used: 5 parts of active ingredient, 1 part of epichlorohydrin, 94 parts of gasoline (boiling limits 160-1900C) Example 1 Production of the compound of the formula a) 17 g of sulfuryl chloride are slowly added dropwise to 16 g of diethyl disulfide in 50 ml of absolute methylene chloride at -20 ° C. and then the resulting reaction mixture, after stirring for one hour at -200 ° C., is added to a solution of 29.8 g of propargyl bromide in 50 ml of absolute methylene chloride, so that the temperature does not exceed -10 ° C.

After one hour, the solution is concentrated at 0 ° to 100 ° C. and the compound of the formula is obtained as a dark yellow, clear liquid.

b) To a solution of 52 g of compound of the formula 63.9 g of the compound of the formula are added in portions at room temperature to 200 ml of absolute acetonitrile to.

The reaction mixture is then stirred at room temperature for about 12 hours and filtered. After the filtrate has been evaporated, the residue is taken up in ether, extracted twice with 100 ml of water each time and the organic phase is dried with sodium sulfate. The compound of the formula is obtained with a refraction of 1.5561.

The following connections are also established in the same way: nD20 = 1.5480 nD20 = 1.5425 nD22 = 1.5392 nD22 = 1.5770 nD24 = 1.5864 nD20 = 1.5496 nD20 = 1.5527 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 Heliothis virescens larvae L3 and the potato plants populated with Colorado beetle larvae (Leptinotarsa decemlineata3. The experiment 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, Heliothis and Leptinotarsa decemlineata larvae.

B) Systemic insecticidal effect To determine the systemic Effect were rooted bean plants (Vicia faba) in a 0.01% aqueous solution of active ingredient (obtained from a show emulsifiable concentrate). After 24 hours aphids (Aphis fabae) were placed on the above-ground parts of the plant. By A special facility protected the animals from contact and gas.

The experiment was carried out at 249 ° C. and 707 ° C. 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 swabs with a top diameter of 17 cm, enganæt 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 iuppressalis.

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, 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-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 -Phaseolus vulgaris (plants) were 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 the spray liquid did not run off. 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 250C The compounds according to Example 1 were active in the above test against adults, Larvae and eggs of Tetranychus urtlcae.

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 arenarla) 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 the snat, the galls present at the roots are counted.

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

Claims (15)

Claims 1. Compounds of the formula or where R1 and R2 are each C1-C5-alkyl, C3-C5-alkenyl or C3-C5-alkynyl, R3 is C1-C5-alkyl or aryl and X and Y are each oxygen or sulfur. 2. Compounds according to claim 1, wherein R1 is methyl or ethyl, R2 Methyl, ethyl or propyl, R3 methyl, ethyl, propyl or phenyl and X and Y oxygen or mean sulfur. 3. Compound according to claim 2 of the formula 4. Compound according to claim 2 of the formula 5. Compound according to claim 2 of the formula 6. A compound according to claim 2 of the formula 7. 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. Process for the preparation of compounds according to Claims 1 to 10, characterized in that a compound of the formula with a compound of the formula converts, where R1> R2, R3 and X have the meaning given in claim 1. 12. Pesticides, which are an active component Compound according to claims 1 to 10 and suitable carriers and / or other additives contain. 13. Use of compounds according to claims 1 to 10 for Control of various animal and vegetable pests. 14. Use according to claim 13 for combating insects and representatives of the order Akarina. 15. Use according to claim 13 for combating phytopathogens Nematodes.