DE2430758A1 - Oxadiazolyls from hydroxydiazoles and phosphoric acid halides - with wide biocidal activity - Google Patents

Abstract

Oxadiazolyl cpds. of formula (I): (where R1 = H, alkyl(pref 1-5C), alkoxy (pref. 1-5C) alkenyl (pref. 3-5C), alkynyl (pref. 3-5C), phenyl, aralkyl (pref. benzyl, phenethyl), phenoxy, alkoxycarbonyl (pref. 1-5C), carbamoyl (pref. aminocarbonyl, alkylaminocarbonyl, dialkylamino carbonyl), R2 = alkyl (opt. Me, Et), R3 = alkylthio (pref. 3-5C), amino, alkyl- or dialkylamino (pref. 1-4C).) are novel (I) are used with suitable carriers and/or additives to combat various animal and plant pests esp. as insecticides and acaricides. They are also fungicides and can be used to protect, e.g. seed grain from fungal infection. They are also active against plant pathogenic nematodes.

Description

"Oxadiazolyl compounds, processes for their preparation and their Use for Pest Control "The present invention relates to oxadiazolyl compounds, Process for their production and their use for pest control.

The oxadiazolyl compounds correspond to the formula where R1 is hydrogen, alkyl, alkoxy, alkenyl, alkynyl, phenyl, aralkyl, phenoxy, alkoxycarbonyl or carbamoyl, R2 is alkyl and R3 is alkylthio, amino, alkyl or dialkylamino.

The alkyl, alkoxy, alkylthio, Lkenyl and alkynyl groups contain 1 to 18 in the chain, respectively. 2 to 18 (for the Alkenyl resp.

Alkynyl radicals), but preferably 1 to 5, respectively. 3 to 5, carbon atoms and can be branched or straight-chain unsubstituted or, for example, by one or several, identical or different halogen atoms and / or Alkoxy and / or alkylthio groups.

Examples of such groups include: methyl, methoxy, chloromethyl, Methoxymethyl, methylthiomethyl, ethyl, ethoxy, propyl, propylthio, isopropyl, n-, i-, sec-, tert-butyl, n-pentyl and its isomers, allyl, methallyl, crotonyl, Propargyl, n-butynyl.

Aralkyl in R1 is primarily to be understood as meaning benzyl or phenethyl. The phenyl, phenoxy, benzyl or phenethyl radical in R1 can be unsubstituted or be substituted.

Preferred substituents on these radicals include

Halogen, preferably fluorine, chlorine and / or bromine, C1-C4-alkyl, C1-C4 -Halogen- alkyl, in particular CF3, C1-C4 -alkoxy, cyano, alkoxycarbonyl and / or Nitro groups.

Because of their action, compounds of the formula I are preferred in which R1 hydrogen, C1-C5-alkyl, Cl-C5-alkoxy, C3C5-aikenyl, C3-C5-alkynyl, phenyl, Benzyl, phenethyl, pnenoxy, C1-C5 -alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl or dialkylaminocarbonyl R2 methyl or ethyl R3 C3C 5 -alkylthio, amino, C1-C5 -Alkylamino or (C-C 4 alkyl) 2 amino.

The compounds of the formula I are prepared according to the invention by a). a hyoroxyoxadiazole of the formula with a phosphoric acid halide of the formula in the presence of an acid-binding agent or b) reacting a salt of a hydroxyoxadiazole of the formula II with a phosphoric acid halide of the formula III.

In the formulas II and III the symbols R1, R2 and R3 have the for the formula I given meaning and Hal stands for fluorine, chlorine, bromine or iodine, but especially for chlorine or bromine. As salts of hydroxyoxadiazoles of the formula For example salts of monovalent metals, especially the alkali metals, are suitable.

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, alkaline earth metals. Sometimes it is with the implementations necessary to use catalysts such as copper or copper chloride.

Processes a) and b) are carried out at a reaction temperature between 0 - 1300C, at normal pressure and possibly in solvents or thinners carried out.

Suitable solvents or diluents are e.g.

Ethers and ethereal compounds such as diethyl ether, dipropyl ether, 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; UMSO, ketones such as acetone, methyl ethyl ketone.

Some of the starting materials of the formulas II and III are known or can be prepared analogously to known methods.

The compounds of formula 1 have a broad biocidal effect and can therefore be used to combat various plant and animal species Insert pests.

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

The following active ingredients are suitable as additives: org. Phosphoric acid compounds; Nitrophenols and their derivatives; pyrethrin-like compounds; Formamidine; Ureas; Carbamates and chlorinated hydrocarbons.

iThe compounds of the formula I have, in addition to the properties mentioned above also an effectiveness against representatives of the department Thallophyta. So show some these compounds have a bactericidal effect. But they are mostly against fungi, in particular effective against the following classes of phytopathogenic fungi: Oomycetes, Zygomycetes, Ascomycetes, Bas idiomycetes, Denteromycetes.

~ The compounds of formula I also show a 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 formula 1 are suitable can also be used to combat 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 in the formulation technical substances such as natural or regenerated substances, solution, 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 will. Furthermore, "cattle dips", i.e. cattle baths, and "spray races", i.e.

Spray courses in which aqueous preparations are used, too mention.

The preparation of the agents according to the invention takes place 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 available in the following working-up forms and are used: Fixed forms of processing: Stubmittel, Litter, granules, coating granules, Iuiprägnierungs 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 other means more suitable Application devices concentrations of up to 99.5% or even pure active ingredient are used can be.

The active ingredients of the formula T 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; 2 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 active ingredient 0, -25 parts epichlorohydrin, 0.25 parts 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-polyoxySthylsn-ethanol, 1.7 parts of champagne chalk / hydroxyethylcellulose 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 a 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, 3.4 parts of a combination emulsifier consisting of 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 of an alkylarylsulfonate / Fcttalkoholpolyglykollither -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 components are used: 5 - parts. Active ingredient, 1 part epichlorohydrin, 94 Parts of gasoline (boiling point 160 - 190 ° C); Example 1 Manufacture of 0-ethyl-N-methylamino-0- (5-phenyl-1,2,4-oxadiazolyl-3) thiophosphate.

17.4 g of N-methylamino-ethoxy-thiophosphoryl chloride are added to a solution of 16.2 g of 3-hydroxy-5-phenyl-1,2,4 oxadiazole, 11 g of triethylamine in 150 ml of dimethoxyethane. After stirring for 15 hours at 50 ° C., the precipitated triethylamine chlorohydrate is separated off. After purification on silica gel, the compound of the formula is obtained from the filtrate with a melting point of 58 - 600 C. The following connections are also established in the same way: R1 R, R Physical data 3 'CzKg - -NHC 230 n C2 5 -NH2 75-77 ° C 0 4 25 1 2 5 IC3H7 (n) nD 1.5573 -C2H5 -NH C3H7 (i) 45-47 ° C 0 (CH3) 3C- -C2H5 -SC3H7 (n) n26 1.5015 D. -C2H5 SC3H7 (n) n26 1> 5685 HH -C2H5 -NHCH3 H -NHCll -CH3. -C2 -NHCH3 3 C3H7 (i) -C2H5 -NHCH3 (CH3) 3C- -C2H5 -NHCH3 C4H9 (n) -C2H5 -NHCH3 C1CH2-CH2- »H2 -C2115 -NHCH3 R1 R2 R3 Physical data CH3SCH2- -C2U5 -NHCH3 -S-- -C2H5 -NHCH3 O 9 -C2u5 -NHCH3 CH30CH2- -C2fl5 -NHCH3 C1CH3 -C2115 -NHCH3 3 -0- ~ ° ~ -C2H5 -NHCH3 CR30 -C2H5 -NHCH3 2 5 -C2u5 -NHCH3 - - ~ -C2H5 -NHCH3 CH3 o -C2115 -NHCH3 O -CH2 C2H5 - NHCR3 O- 2H5 -NHC2H5 H C3R7 (i) C2H5 -NHC3 7 (n) R1 R2 R3 Physical data -C 2 -C2R5 -NHC3H7 (n) (CH3X3C- -C2H5 -NHC3H7 (n) C4II9 (n) - -C2115 -NHC3R7 (i) -NHC II 4 - 2 5 3 7 (i) - -C2H5 -SC3H7 (n C3 7 (i) -C2R5 -SC3H7 (n) R -CH3 -NHCH3 - I = 5 -c2115 -N (CH3) 2 - Example 2 A) Insecticidal food poison effect Cotton plants and potato plants were sprayed with an 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 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 decemitneata 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) is 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 240C and 70X 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 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 Chiio in the above test suppressalis.

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 sgesitellt 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 of Phageolus 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 obtained from a chromatography atomizer with the emulsified test preparations dusted so that no runoff of the spray mixture 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 is printed out as a percentage.

During the "holding time", the treated plants stood in greenhouse cabins at 250C.

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

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 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.

To assess the nematocidal effect, 28 days after detn Plants 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 Meloidogyne arenaria.

Claims (1)

Claims () e1 oxadiazolyl compounds of the formula where R1. Hydrogen, alkyl, alkoxy, alkenyl, alkynyl, phenyl, aralkyl, phenoxy, alkoxycarbonyl or carbamoyl, R2 denotes alkyl and R3 denotes alkylthio, amino, alkylamino or dialkylamino. 2) Compounds according to claim l, wherein R1 is hydrogen, C1-C5-alkyl, Cl-C5-alkoxy, C3C5-alkenyl, C3-C5-alkynyl, phenyl, benzyl, phenethyl, phenoxy, C1-C5-alkoxycarbonyl, Aminocarbonyl, alkylaminocarbonyl or dialkylaminocarbonyl R2 methyl or ethyl R3 is C3-C5-alkylthio, amino, C1-C4-alkylamine or (C1-C4-alkyl'2amino. 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) Compound according to claim 2 of the formula 9) Compound according to claim 2 of the formula 10) Process for the preparation of compounds according to Claims 1 to 9, characterized in that a compound of the formula in the presence of an acid-binding agent with a compound of the formula converts, or a compound of the formula with a compound of the formula lets react, in which R1, R2 and R3 have the meaning given in claim 1 and Hal is fluorine, chlorine, bromine or iodine and Me is a monovalent metal. 11) Pesticides, which are the active component Compound according to claims 1 to 9 and suitable carriers and / or other additives contain. 12) Use of compounds according to claims l to 9 for Control of various animal and vegetable pests. 13) Use according to claim 12 for. Control of insects and Representatives of the order Akarina.