DE2500485A1 - Insecticidal, nematocidal 1,2,4-thiadiazole derivs - prepd by reacting a haloalkylthiadiazole with a substd dithiophosphate - Google Patents

Abstract

derivs of formula (I): in which R1 = opt. substd. 1-20C alkoxy or alkyl thio, R2 = methyl or ethyl, R3 = opt. substd. 1-7C alkyl or 3-4C alkenyl, X = -O or -S. have insecticidal and acaricidal activity against all phases of development. They have also partly herbicidal and plant growth-regulating activity and may also be used against virus, bacteria and plant-pathogenous moulds.

Description

"1,2,4-thiazole derivatives, process for their preparation and their use" The present invention relates to derivatives of 1,2,4-thiadiazoles, processes too Manufacture and its use in pest control.

The 1,2,4-thiadiazole derivatives have the formula where R1 is optionally substituted C1-C20-alkoxy or C1-C20-alkylthio, R2 is methyl or ethyl, R3 is optionally substituted C1-C7-alkyl or C3-C4-alkenyl and X is oxygen or sulfur.

The alkoxy, alkylthio, alkyl or alkenyl groups at R1 and R3 can be straight-chain or branched and preferably have R1 in the chain 1 to 4 carbon atoms. Examples of substituents on these groups are Fluorine, chlorine, bromine, iodine, cyano, phenyl, nitro, Cl-C4-alkoxy, Cl-C4-alkylthio or C1-C4-alkylsulfonyl into consideration.

Examples of alkoxy, alkylthio, alkyl or alkenyl groups R1 and R3 are among others: methyl, methoxy, methylthilo, ethyl, ethoxy, ethylthio, Propyl, propoxy, propylthio, isopropyl, isopropoxy, isopropylthio, n-butyl, n-butoxy, n-butylthio, i-, sec-, tert-butyl, methoxymethyl, methoxythyl, ethoxyethyl, Ethylthioethyl, chloroethyl, n-pentyl, n-heptyl, n-dodecyl and other isomers, allyl, Methallyl or benzyloxy.

Because of their action, compounds of the formula I are preferred in which R1 optionally substituted C1-C4-alkoxy or C1-C4-alkylthio, R2 methyl or Ethyl, R3 optionally substituted by C1-C4-alkoxy, C1-C7-alkyl or allyl and X is oxygen or sulfur.

Particularly preferred are compounds of the formula I in which R1 is methoxy, Methylthio, ethoxy, ethylthio, n-propoxy, isopropoxy, n-PentyloRy, Benrylovy, or n-butoxy, R2 is ethyl, R3 is C1-C7-alkyl and X is oxygen.

The compounds of the formula I can be prepared by methods known per se, for example as follows: A) SN x l 4 \ N t CH2-Hal + HS¼I »R2 mat binding> 1 SR3 (II) (III) 3 S - NX B) RiÖN ßCH2-Hal + MeS-P SR3 (II) (IV) In the formulas II, III and IV, R1 to R3 and X have the meaning given for the formula I and Hal stands for chlorine or bromine, in particular for chlorine and Me for a metal, in particular an alkali metal, ammonium or trialkylammonium.

Processes A and B are carried out at a reaction temperature of 0 - 120 ° C, preferably at 20 - 80 ° C, at normal pressure and in solvents or thinners carried out.

Suitable solvents or diluents are e.g.

Ether and ethereal compounds such as DiSthylSther, Dipropylächer, Dioxane, dimethoxyethane, tetrahydrofuran; Amides such as N, N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, Toluene, xylenes, chloroform, chlorobenzene; Nitriles such as acetonitrile; Dimethyl sulfate, Ketones such as acetone, methyl ethyl ketone and water, alcohols such as methanol, ethanol.

The following acid-binding agents are suitable: tertiary amines, e.g. trialkylamines, Pyridine, dialkylanilines; inorganic bases such as hydrides, hydroxides; Carbonates and Bicarbonates of alkali and alkaline earth metals. Sometimes it is with the implementations necessary to use catalysts such as copper or copper chloride.

Starting materials of the formulas II, III and IV are known or are not known can be produced analogously to known methods.

For the preparation of compounds of the formula I, according to the methods A and B, for example, the following starting materials of the formula II: 3-chloromethyl-5-methoxy-1,2,4-thiadiazole 3-chloromethyl-5-ethoxy-1,2,4-thiadiazole 3-chloromethyl-5-methylthio-1,2,4-thiadiazole 3-chloromethyl-5-ethylthio-1,2,4-thiadiazole 3-chloromethyl-5-propoxy-1,2,4-thiadiazole 3-chloromethyl-5-propylthio-1,2,4-thiadiazole 3-chloromethyl-5-isopropoxy-1,2,4-tllindiazole 3-chloromethyl-5-isopropylthio-1,2,4-thiadiazole 3-chloromethyl-5-n-butoxy-1,2,4-thiadiazole 3-chloromethyl-5-n-pentoxy-1,2,4-thiadiazole 3-chloromethyl-5-benzyloxy-1,2,4-thiadiazole optionally with the following examples of starting materials of the formula III, respectively. whose Salts of the formula IV are combined: S-n-propyl-O-ethyl-dithiophosphoric acid S-ethyl-O-ethyl-dithiophosphoric acid S-i-propyl-O-ethyl-dithiophosphoric acid S-n-butyl-O-ethyl-dithiophosphoric acid S-i-butyl-O-ethyl-dithiophosphoric acid S-sec. -Butyl-O-ethyl-dithiophosphoric acid S-n-pentyl-O-ethyl-dithiophosphoric acid S-methyl-O-ethyl-dithiophosphoric acid S- (2-methoxyethyl) -O-ethyl-dithiophosphoric acid S- (2-ethoxyethyl-O-ethyl-dithiophosphoric acid S-n-hexyl-O-ethyl-dithiophosphoric acid S-n-heptyl-O-ethyl-dithiophosphoric acid S-n-propyl-O-methyl-dithiophosphoric acid S-n-Butyl-O-methyl-dithiophosphoric acid S-i-Butyl-O-methyl-dithiophosphoric acid S-sec-butyl-O-methyl-dithiophosphoric acid S-n-Pentyl-O-methyl-dithiophosphoric acid S- (2-methoxyethyl) -O-methyl-dithiophosphoric acid S- (2-ethoxyethyl) -O-methyl-dithiophosphoric acid S-allyl-O-ethyl-dithiophosphoric acid ester S-Methallyl-O-ethyl-dithiophosphoric acid ester The active ingredients of the formula I are suitable to combat various animal and vegetable pests.

They have nematicidal properties and can, for example can be used to combat phytopathogenic nematodes. Partly suitable The active ingredients of the formula I are also used as herbicides and plant regulators as well to combat viruses, bacteria and fungi that are pathogenic to fungi. they seem but above all against all stages of development, such as eggs, larvae, nymphs, pupae and adults of insects and members of the order Acarina, such as mites and ticks.

The compounds of the formula I can be used alone or together 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. The connections of formula I to dusts, emulsion concentrates, granules, dispersions, Sprays, solutions or slurries in the usual formulation used in application technology belong to general knowledge, are processed.

Furthermore, "cattle dips", i.e. cattle baths, and "spray races", i.e. Mention should be made of spray courses in which aqueous preparations are used.

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 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 your 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 and ground with the carrier substances.

Granules: The following are used to produce 5% granules Substances used: 5 parts of active ingredient, 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ither, 3.50 parts of polycithylene 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 is 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 lignosulfonate, 1.9 Parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1), 1.5 parts of sodium dibutyl naphthalene sulfonate, 19.5 parts silica, 19.5 parts Champagne chalk, 28.1 parts Kaolin; c) 25 parts of active ingredient 2.5 parts of sooctylphenoxy-polyoxyethylene-ethanol, 1.7 Parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1), 8.3 parts of sodium aluminum silicate, L6.5 parts of diatomaceous earth, 46 parts of kaolin; d) 10 parts of active ingredient 3 parts of mixture of 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 the 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) lOe /, igen and b) 25% emulsifiable concentrates are as follows Substances used: a) 10 parts of active ingredient, 3.4 parts of epoxidized vegetable oil, 3.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkylaryl sulfonate 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 poly glycol 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 160-1900C).

Example 1 Preparation of O-ethyl-S- (n) -propyl-S- [5-methoxy-1,2,4-thiadiazol-methylenyl (3)] -dithiophosphate To a solution of 20 g of potassium O-ethyl-S- (n) -propyldithiophosphate and 70 ml of methanol 11.5 g of 3-chloromethyl-5-methoxy-1,2,4-thiadiazole in 20 ml of methanol are added dropwise at 40.degree.

The solution is stirred for 2 hours at reflux temperature.

The resulting suspension is cooled to 20 ° C. with 200 ml of methylene chloride added, extracted three times with water, dried with sodium sulfate and evaporated.

After purification over silica gel, the compound of the formula is obtained with a refractive index of n24 = D 1> 5532 The following connections can also be established in the same way: F. RRR 2 L 3 Physical 1 data -OCH3 -C2H5 -C2H5 -OCH3 -C2H5 -C3H7 (i) -OCH3 -C2n5 -C4Hg (n) -OCH3 -CH3 -C3H7 (n) -OCH3 -CH3 -CH3 OG2H5 -C2H5 | -C3H7 (n) -OC2H5 -C2H5 t -C5H11 (n) -OCH3 -C2H5 CH (i) 0 21 -OCH3 C2 5 -C4Hg (sec) D = = -OCH3 -C2R5 -CH2CH2OCH3 -OCH3 -C2H5 20 CHHHcnC2H5 -OC3H7 (i) -C2R5 -OC5H11 (n) C2H5! -C3H7 (n) [ SUCH3 j -C2H5 -C3H7 (n) n22 D 7 D -5C2H5 1 02H5 -OCK, -C2H5 O, C2H5 S-C3H7 (n) Example 2 A) Insecticidal food poison effect Cotton plants were sprayed with a 0.05% strength aqueous active substance emulsion (obtained from a strength emulsifiable concentrate).

After the covering had dried on, the cotton plants were each with Spodoptera littoralis or Heliothis virescens larvae L3 occupied.

The experiment was carried out at 24 ° C. and 60% relative humidity.

Compounds according to Example 1 showed good insecticidal properties in the above test Food poison effect against Spodoptera and Heliothis 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 an emulsifiable concentrate). 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.

Compounds according to Example 1 had a systemic effect in the above test against Aphis fabae.

Example 3 Action against ticks A) Rhipicephalus bursa 5 adults each Ticks or 50 tick larvae were counted in a glass tube and counted for 1 to 2 Minutes in 2 ml of an aqueous emulsion from a dilution series of 100 each, 10, 1 or 0.1 ppm test substance immersed. The tube was then standardized with a Cotton ball closed and turned upside down, so that the active ingredient emulsion could be auEgenczzen from the wadding.

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).

Compounds according to Example 1 were effective against adults in these tests and larvae of Rhipicephalus bursa and sensitive resp. OP-resistant larvae of Boophilus microplus.

Example 4 Acaricidal effect of Phaseolus vulgaris (plants) 12 hours before the test for acaricidal effect with an infected piece of leaf from a mass breed of Tetranychus urticae. The defected moving Stages were made from a chromatography nebulizer with the emulsified test preparations bestciubt that no runoff of the spray liquor occurred. After two to seven 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 25 ° C.

Compounds according to Example 1 were effective in the above test against adults, Larvae and eggs of Tetranychus urticae.

Example 5 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 tomato seedlings planned and in another series of experiments after 8 days waiting time sown tomatoes.

To assess the nematocidal effect, 28 days after Plants or, after sowing, the galls present on the roots are counted.

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

Claims (11)

Claims 1. A 1,2,4-thiadiazole derivative of the formula wherein R1 is optionally substituted C1-C20-alkoxy or C1-C20-alkylthio, R2 is methyl or ethyl, R3 is optionally substituted C1-C7-alkyl or C3-C4-alkenyl and X is oxygen or sulfur. 2. A compound according to claim 1, wherein R1 is optionally substituted C1-C4-alkoxy or Cl-C4-alkylthio, R2 methyl or ethyl, R3 optionally through C1-C4-alkoxy-substituted C1-C7-alkyl or allyl and X is oxygen or sulfur mean. 3. A compound according to claim 2, wherein R1 is methoxy, methylthio, Ethoxy, ethylthio, n-propoxy, isopropoxy, n-pentyloxy, benzyloxy or n-butoxy, R2 is ethyl, R3 is 1-7 alkyl and R4 is oxygen. 4. A compound according to claim 3 of the formula 5. A compound according to claim 3 of the formula 6. A compound according to claim 3 of the formula 7. Process for the preparation of compounds according to Claims 1 to 4, 4, 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 reacted, in which R1 to R3 and X have the meaning given in claim 1 and Hal is halogen and Me is a metal, ammonium or tr.ialkylammonium. 8. Pesticides, which are an active component Compound according to claims 1 to 6 and suitable carriers and / or other additives contain. 9 .. Use of compounds according to claims 1 to 6 for Control of various animal and vegetable pests. 10. Use according to claim 3 for combating insects and representatives of the order Akarina. 11. Use according to claim 9 for combating phytopathogens Nematodes.