KR100732093B1 - Fungicidal mixtures - Google Patents

Abstract

As active ingredients, fungicidal mixtures for the control of harmful fungi are disclosed comprising 1) a triazolopyrimidine derivative of formula (I) and 2) a synergistically effective amount of cresoxime-methyl (II). Also disclosed are methods of controlling harmful fungi using mixtures of compounds of formulas (I) and (II), the use of compounds of formulas (I) and (II) for preparing said mixtures, and formulations containing said mixture.

<Formula I>

<Formula II>

Triazolopyrimidine Derivatives, Cresoxime-methyl, Harmful Fungi, Controls, Fungicides

Description

Fungicidal mixtures {FUNGICIDAL MIXTURES}

The present invention relates to a fungicidal mixture for controlling harmful fungi, comprising as active ingredients a synergistically effective amount of 1) triazolopyrimidine derivatives of formula (I) and 2) cresoxime-methyl of formula (II).

The present invention also relates to methods of controlling harmful fungi using mixtures of compounds of formula (I) and compounds of formula (II), and the use of compounds I and compound II to prepare such mixtures, and compositions comprising these mixtures.

Compound of Formula (I), 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl)-[1,2,4] tri-azolo [1,5-a] pyrimidine, its preparation and action against harmful fungi are known from WO 98/46607.

Compounds of formula II, methyl methoxyimino- (2-o-tolyloxymethylphenyl) acetate, their preparation and action against harmful fungi are likewise described in EP-A 253 213; Common Name: Cresoxime-Methyl]. Kresoxim-methyl are mainly acts as a fungicide for cereals, it is formed with a commercial, for the powdery mildew (mildew) and rust (rust disease) caused by the ascus fungi (Ascomycetes) or a basidiomycete (Basidiomycetes).

Mixtures of triazolopyrimidine derivatives with cresoxime-methyl are known in a general manner from EP-A 988 790. Compounds of formula I are included in the general disclosure of this application, but are not specifically mentioned. Thus, the combination of the compound of formula (I) with cresoxime-methyl is novel.

Synergistic mixtures known from EP-A 988 790 have been described as having fungicidal activity against various diseases of cereals, fruits and vegetables, in particular powdery mildew of wheat and barley or gray mold of apples.

Due to the special cultivation conditions of rice plants, the requirements for rice fungicides are clearly different from the requirements of fungicides used for grain or fruit cultivation. There is a difference in the method of application. In addition to the foliar application used in many places, in recent rice cultivation, fungicides are applied directly onto the soil during or immediately after sowing. The fungicide is taken into the plant through the root and transported to the plant part to be protected from the sap of the plant. Thus, for rice fungicides, a high degree of systemic action is essential. In contrast, in grain or fruit cultivation fungicides are commonly applied on leaves or fruits; Thus, the systemic action of the active compounds in these crops is significantly less important.

In addition, typical rice pathogens are typically different from those of cereals or fruits. Rice fever bacteriaPyricularia oryzae) And corticium (Corticium sasakii)(synonymRhizoctonia solani) Is the most common pathogen for rice plants. Cortisium bacteriaRhizoctonia solani) Is the only pathogen of arable importance in the subclass of Agaricomycetidae. Unlike most other fungi, these fungi attack plants not through spores but through mycelial infection.

For this reason, findings related to fungicidal activity in the cultivation of cereals or fruits could not be delivered to rice crops.

Real farming experience has shown that repeated and exclusive application of each active compound in the control of harmful fungi can lead to the rapid selection of fungal strains that exhibit natural or modified resistance to the active compound in many cases. . Then, effective control of these fungi using the present active compounds is no longer possible.

In order to reduce the risk of selecting resistant fungi, mixtures of different active compounds are nowadays commonly used for the control of harmful fungi. By combining the active compounds having different mechanisms of action, it is possible to ensure successful control for a relatively long time.

It is an object of the present invention to provide a mixture having an improved effect on harmful fungi at a reduced total amount of active compound applied, in terms of effective resistance management and effective control of harmful fungi at the lowest possible dosage.

We have found that the above object is achieved by a mixture initially defined. In addition, we have found that the application of the compounds of formula (I) and formula (II) simultaneously, ie together or separately, or in succession can better control harmful fungi than is possible as individual compounds.

In the preparation of the mixture, to the pure active compounds of the formulas (I) and (II), if necessary, further compounds (III) and (IV) which are active against harmful fungi or other pests such as insects, arachnids or nematodes or active compounds for herbicide or growth control It may be desirable to add fertilizers for use.

Further suitable active compounds in the above senses are fungicides, in particular selected from the group:

Acylalanine, such as benalaxyl, metallaxyl, opurase or oxadixyl,

Amine derivatives, such as aldimorphs, dodemorphs, fenpropimods, fenpropidines, guaztines, iminottadines or tridemorphs,

Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxine or streptomycin,

Azoles such as bitertanol, bromoconazole, ciproconazole, diphenoconazole, dinitroconazole, epoxyconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, Imazalyl, Ipconazole, Metconazole, Myclobutanyl, Penconazole, Propicozol, Prochloraz, Prothioconazole, Cimeconazole, Tebuconazole, Tetraconazole, Triadimefon, Tri Adimenol, triflumisol or triticazole,

Dicarboxymides such as myclozoline or procmidone,

Dithiocarbamates, such as ferbam, nabam, metham, propineb, polycarbamate, zeram or geneb,

Heterocyclic compounds such as anilazine, boscalid, carbendazim, carboxycin, oxycarboxycin, cyazopamide, dazomet, phamoxedone, phenamidone, fuberidazole, flutolanyl, furametpyr , Isoprothiorane, mepronyl, noarimol, probenazole, pyroquilon, quinoxyphene, silthiofam, thibendazole, tifluzamide, thiadinil, tricyclazole or tripolin,

Nitrophenyl derivatives such as vinapacryl, dinocap, dinobutone or nitrophthalisopropyl,

Phenylpyrrole, such as fenpiclonyl or fludioxonil,

-Sulfur,

Other fungicides, such as acibenzola-S-methyl, carpropamide, chlorothalonil, cyflufenamide, simoxanyl, diclomezin, diclocimet, dietofencarb, edifenforce, eta Boksam, Phenhexamide, Pentin Acetate, Phenoxanyl, Perimzone, Fluazinam, Pocetyl, Pocetyl-Aluminum, Phosphoric Acid, Hexachlorobenzene, Metrafenone, Pensicuron, Propamocarb, Phthalide, Tall Clophosmethyl, quintogen or oxamid,

Strobiliurine, such as fluoxastrobin, metominostrobin, orissastrobin, pyraclostrobin or tripleoxystrobin,

Sulfenic acid derivatives, such as captapol,

Cinnamids and homologous compounds, such as flumetober.

In one embodiment of the mixture according to the invention, the compounds of the formulas (I) and (II) are mixed with further fungicides III or two fungicides III and IV.

Suitable components III and IV are in particular the following fungicides.

Amine derivatives such as dodemorph, fenpropimod, phenpropidine, iminottadine or tridemorph;

Azoles such as bromoconazole, ciproconazole, diphenoconazole, dinitroconazole, epoxyconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, ipconazole, met Conazole, myclobutanyl, fenconazole, propicoazole, prochloraz, prothioconazole, simeconazole, tebuconazole, tetraconazole, triflumiazole or triticazole;

Heterocyclic compounds such as boscalid, carbendazim, cyazopamide, flutolanyl, or quinoxyfen;

Dithiocarbamate and

Other fungicides such as ventiavalicarb, chlorothalonil, cyflufenamide, diclofloanide, phenhexamide, fluazinam, pocetyl, pocetyl-aluminum, phosphorous acid, metrapenone and pencicuron .

Preferred are mixtures of the compounds of formulas (I) and (II) with component III. Particular preference is given to mixtures of compounds of the formulas (I) and (II).

Formula I and a mixture of the compound of formula (II) or simultaneously, that is together or the formula (I) and compound of formula (II) used separately ascus fungi (Ascomycetes) steel, imperfect fungi (Deuteromycetes) steel and basidiomycete (Basidiomycetes) Steel striking against harmful fungi Action. They can be used for the treatment of seeds and as leaf- and soil-acting fungicides.

In addition, the combinations of the compounds of the formulas (I) and (II) according to the invention can be used in other pathogens, such as the Septoria and Puccinia species of cereals such as wheat and barley, and Alternaria of vegetables, fruits and grapevines. ) Is also suitable for the control of Botrytis species.

These are bipolaris species as well as harmful fungi on rice plants and their seeds, such as Pyricularia oryzae . And Drechslera It is especially important for controlling species. They may be particularly preferably used for controlling leaf blight on rice caused by Corticium bacteria (syn. Rhizoctonia solani ).

The compounds of formula (I) and (II) may be applied simultaneously, ie together or separately or successively. When applied separately, the order of application generally has no effect on the outcome of the response.

Usually, the compounds of the formulas (I) and (II) are applied in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:50, in particular 2: 1 to 1:10.

Components III and IV, if necessary, are added to the compound of formula I in a ratio of 20: 1 to 1:20.

Depending on the type of compound and the desired effect, the application rate of the mixtures according to the invention is 5 to 2000 g / ha, preferably 50 to 1500 g / ha, in particular 50 to 750 g / ha.

Correspondingly, the application rate of the compounds of formula (I) is generally 1 to 1000 g / ha, preferably 10 to 750 g / ha, in particular 20 to 500 g / ha.

Correspondingly, the application rate of the compound of formula II is generally 1 to 1000 g / ha, preferably 10 to 750 g / ha, in particular 20 to 500 g / ha.

In seed treatment, the application rate of the mixture is generally from 0.001 to 1 g, preferably from 0.01 to 0.5 g, in particular from 0.01 to 0.1 g per kg of seed.

In the control of harmful fungi, the application of the compounds of the formulas (I) and (II) or mixtures of the compounds of the formulas (I) and (II) separately, together with the seed, seedling, plant or before or after planting or seeding of the plant By spraying or spraying the soil. Preferably the compounds are applied together or separately by applying the granules or by spraying the soil.

The mixtures according to the invention, or the compounds of the formulas (I) and (II), can be converted into conventional preparations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the specific purpose; In each case they must disperse the compound according to the invention finely and uniformly.

Such formulations may be prepared in a known manner, for example by extending the active compound into a solvent and / or carrier, if necessary using emulsifiers and dispersants. Suitable solvents / adjuvant are essentially

Water, aromatic solvents (eg from Solvesso, xylene), paraffins (eg mineral oil fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclo Hexanon, gamma-butyrolactone), pyrrolidone (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters (in principle, solvent mixtures may be used),

Carriers such as ground natural minerals (eg kaolin, clay, talc, chalk) and ground synthetic minerals (eg highly dispersed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulphite waste liquors and methylcellulose.

Suitable surfactants include alkali metals, alkaline earth metal and ammonium salts, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfates of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid and dibutylnaphthalenesulfonic acid Fatty alcohol glycol ethers, also condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acid with phenols and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenols, octylphenols, nonylphenols , Alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohol, alcohol and fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxy Misfired polyoxypropylene, lauryl alcohol Polyglycol ether acetal, sorbitol ester, lignin-sulfite waste liquor and methylcellulose.

Suitable materials for the preparation of immediately sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions with medium to high boiling points, such as kerosene or diesel oils, also coal tar oils, and vegetable or animal oils, aliphatic, cyclic and aromatic Hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, high polar solvents such as dimethyl sulfoxide Seed, N-methylpyrrolidone and water.

Powders, spraying materials and sprayable products can be prepared by mixing or co-milling the active materials with solid carriers.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Examples of solid carriers are mineral soils such as silica gel, silicates, talc, kaolin, atclay, limestone, lime, chalk, church clay, ocher, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, Ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate or urea, and products of plant origin such as grain flour, bark flour, wood flour and nut shell flour, cellulose powder and other solid carriers.

In general, the preparations comprise from 0.01 to 95% by weight of the active compound, preferably from 0.1 to 90% by weight. The active compound is used with a purity (according to the NMR spectrum) of 90 to 100%, preferably 95 to 100%.

Examples of such agents are as follows:

1. Product diluted with water

(A) Aqueous concentrate (SL)

10 parts by weight of the active compound are dissolved in water or an aqueous solvent. Alternatively, wetters or other auxiliaries are added. The active compound dissolves upon dilution with water.

(B) Dispersible Concentrates (DC)

20 parts by weight of the active compound are dissolved in cyclohexanone with the addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.

(C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compound are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (each 5% concentration). Dilution with water gives an emulsion.

(D) emulsions (EW, EO)

40 parts by weight of the active compound are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (each 5% concentration). This mixture is introduced into water by an emulsifier (Ultraturax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.

(E) Suspensions (SC, OD)

In a stirred ball mill, 20 parts by weight of the active compound together with the addition of a dispersant, a wetting agent and water or an organic solvent are ground to obtain a fine active compound suspension. Dilution with water gives a stable suspension of the active compound.

(F) Water Dispersible Granules and Water Soluble Granules (WG, SG)

50 parts by weight of the active compound together with the addition of dispersing and wetting agents are ground and made into water-dispersible or water-soluble granules using a machine (eg, extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound.

(G) Water Dispersible Powders and Water Soluble Powders (WP, SP)

75 parts by weight of the active compound are ground in a rotor-stator mill with addition of dispersant, wetting agent and silica gel. Dilution with water gives a stable dispersion or solution of the active compound.

2. Products applied without dilution

(H) sprayable powder (DP)

5 parts by weight of the active compound is ground and mixed with 95% of finely divided kaolin. This yields a spartable product.

(I) Granules (GR, FG, GG, MG)

0.5 parts by weight of the active compound is ground and combined with 95.5% of the carrier. Current methods include extrusion, spray-drying or fluidized beds. This gives granules that are applied without dilution.

(J) ULV solution (UL)

10 parts by weight of the active compound are dissolved in an organic solvent such as xylene. This yields a product that is applied without dilution.

The active compounds are, as such, in the form of their preparations or in the form of uses prepared therefrom, eg, directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, sprayable products, substances for spraying or granules. Furnace, sprayed, atomizing, sprayed, sprinkled or poured. The form of use depends entirely on the intended purpose; In each case it is intended to maximize the microdispersion of the active compound according to the invention.

Aqueous use forms can be prepared by adding water to emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions). To prepare emulsions, pastes or oil dispersions, the material can be dissolved as is or in oil or solvent and homogenized in water using wetting agents, tackifiers, dispersants or emulsifiers. Alternatively, concentrates can be prepared which consist of the active substance, wetting agent, tackifier, dispersant or emulsifier, and, if appropriate, a solvent or oil, which concentrates are suitable for dilution with water.

The concentration of active compound in ready-to-use preparations can vary widely. Generally, the concentration is 0.0001 to 10%, preferably 0.01 to 1%.

The active compounds can also be used very successfully in ultra low volume (ULV) processes, and therefore can be employed formulations comprising more than 95% by weight of active compound, or even without additives.

If appropriate, various types of oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides or fungicides may be added to the active compound immediately before use (tank mix). These agents can be mixed with the compositions according to the invention, usually in a weight ratio of 1:10 to 10: 1.

Compounds, mixtures or corresponding preparations of formula (I) or (II) are formulated with an effective amount of a mixture fungicidal, or separately when plants, seeds, soil, areas, substances or spaces intended to remain in the absence of harmful fungi or harmful fungi. The compound of II is applied by treatment with an effective amount of fungicidal. Application can be done before or after infection with harmful fungi.

Fungicidal activity of compounds and mixtures can be explained by the following experiments:

The active compounds were prepared separately or together in a stock solution of 0.25% by weight of active compound in acetone or DMSO. To the solution was added 1% by weight of the emulsifier Uniperol® EL (wetting agent based on ethoxylated alkylphenols with emulsifying and dispersing activity) and the solution was diluted with water to the desired concentration.

Example of use-Corticium bacteriaCorticium sasakii ,Name of consentRhizoctonia solaniActivities on Rice Leaf Blight induced by

The pollen of the rice plant of variety "Tai-Nong 67" was sprayed until the aqueous suspension having the active compound concentration described below was flowed down. The next day, oats grains infected with corticium were placed in the pot (5 grains per pot in each case). The plants were then left in a steam-saturated chamber at 26 ° C. After 11 days, leaf blight of untreated infected control plants developed to the extent that the percentage of infection could be determined visually.

Evaluation is made by determining the percentage of infected leaf area in percentage, and these percentage rates are converted into percentage efficacy.

Efficacy (E) was calculated using the Abbot formula below.

α is the percentage of fungal infections of treated plants,

β is the percentage of fungal infections in untreated (control) plants.

Efficacy 0 means that the infection level of the treated plant corresponds to that of the untreated control plant; Efficacy 100 means that the treated plant is not infected.

The expected potency of the mixture of active compounds was determined using the following Colby formula (R.S. Colby, Weeds 15, 20-22 (1967)) and compared with the observed potency.

Colby Formula:

E is expressed in% as the expected efficacy of the untreated control when using a mixture of active compounds A and B at concentrations a and b,

x is expressed in% as the efficacy of the untreated control when using active compound A at concentration a,

y is expressed in% as the potency of the untreated control when using active compound B at concentration b.

The comparative compounds used were compounds A and B known from the cresoxime-methyl mixture described in EP-A 988 790:

<Compound A>

<Compound B>

Individual active compounds Example Active compound Concentration of active compound in spraying liquid [ppm] % Efficacy of untreated control One Control (untreated) - (90% infection) 2 I One 33 3 II (Cre Soxime-Methyl) 4 1 0 0 4 Comparative Compound A One 0 5 Comparative Compound B One 0

Mixture according to the invention Example Mixture Concentration Mixture Ratio of Active Compounds Observed efficacy Calculated efficacy ^* ) 6 I + II 1 + 1 ppm 1: 1 89 33 7 I + II 1 + 4 pm 1: 4 100 33 *) Efficacy calculated using Colby's formula

Comparative Experiment-Mixtures Known in EP-A 988 780 Example Mixture Concentration Mixing Ratio of Active Compounds Observed efficacy Calculated efficacy *) 8 A + II 1 + 1 ppm 1: 1 0 0 9 A + II 1 + 4 pm 1: 4 0 0 10 B + II 1 + 1 ppm 1: 1 22 0 11 B + II 1 + 4 pm 1: 4 33 0 *) Efficacy calculated using Colby's formula

The test results indicate that the mixtures according to the invention are significantly more effective against leaf blight than the cresoxime-methyl mixtures known from EP-A 988 780, due to the strong synergy.

Claims (12)

A fungicidal mixture comprising 1) a triazolopyrimidine derivative of formula I, and 2) cresoxime-methyl of formula II in a weight ratio of 100: 1 to 1: 100. <Formula I>

<Formula II>

delete A fungicidal composition comprising a liquid or solid carrier and a mixture according to claim 1. A method of controlling harmful fungi comprising treating fungi, their habitats, soils to be protected from fungal attack, plants or seeds with an effective amount of a compound of formula I according to claim 1 and a compound of formula II. The method of claim 4 wherein the compound of formula I and the compound of formula II are applied simultaneously, ie together or separately, or continuously. The method according to claim 4, wherein the fungicidal composition comprising the mixture according to claim 1 or the liquid or solid carrier and the mixture according to claim 1 is applied in an amount of 5 g / ha to 2000 g / ha. The method according to claim 4 or 5, wherein the fungicidal composition comprising the mixture according to claim 1 or the liquid or solid carrier and the mixture according to claim 1 is applied in an amount of 0.001 to 1 g per kg of seed. . The method according to claim 4 or 5, wherein the harmful fungi to be controlled are Corticium sasakii . Seed comprising the mixture according to claim 1 in an amount of 0.001 to 1 g per kg of seed. delete A process for preparing a fungicidal composition according to claim 3 by increasing the compound of formula I according to claim 1 and the compound of formula II with a solvent, a carrier or a combination thereof. The fungicidal composition according to claim 3, which contains the additional active compound.