RU2193848C2 - Fungicidal composition for plants and method for its application - Google Patents

Abstract

FIELD: agriculture, plant science. SUBSTANCE: fungicidal composition for plants includes two active substances at the amount of synergistic activity in combination with a filler. As component I the suggested composition contains O-methyloxym of methyl ether 2- [alpha-{[alpha-methyl-3-trifluoromethylbenzyl)- imino] oxy}ortho-tolyl]glyoxylic acid, component II is chosen out of a group including: 5,7-dichlorine-4-(4- fluorinphenoxy)-quinoline (quinoxyphen), 4-cyclopropyl- 6-methyl-N-phenyl-2-pyrimidinyl (cyprodinyl), S-methyl ether of benzo(1,2,3)thiadiasol-7-carbothioacid (acybenzolar-S-methyl), 3-aniline-5-methyl-5-(4- phenoxyphenyl)-1,3-oxasolidine-2,4-dion (faluxadon), 8- (1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspyro- [4,5] decane-2-metanamine (spyroxamin). It is, also, described the method to fight and prevent plant diseases in which components I and II are used with corresponding fillers at the quantity providing synergistic interaction in any order or simultaneously. EFFECT: higher activity. 4 cl, 8 ex, 3 tbl

Description

 The present invention relates to new mixtures of active substances as plant protection products, having increased activity due to synergism and including at least two active substances as components, and also to a method of using such mixtures for plant protection, in particular for controlling and preventing disease outbreaks .

Component I is a compound
2- [α- {[(α-methyl-3-trifluoromethyl-benzyl) imino] oxy} ortho-tolyl] glyoxylic acid methyl oxymethoxy, (EP-A-460575), a
component II is a compound selected from the group including
IIA) 5,7-dichloro-4- (4-fluorophenoxy) quinoline ("quinoxifene") (EP-A-326330),
IIB) 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine ("cyprodinil") (The Pesticide Manual, 10th ed., 1994, 109),
IIB) S-methyl ester of benzo (1,2,3) thiadiazole-7-carbo-acid ("acibenzolar-S-methyl") (EP-A-313512),
IIG) 3-aniline-5-methyl-5- (4-phenoxyphenyl) -1,3-oxazolidine-2,4-dione ("famoxadone") (EP-A-393911),
IIE) 8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4,5] decane -2-methanamine ("spiroxamine") (EP-A-281842),
IIE) 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile (“fludioxonil”) (The Pesticide Manual, 10th ed., 1994, 326),
IIG) 4- (2,3-dichlorophenyl) pyrrole-3-carbonitrile ("phenpiclonil") (The Pesticide Manual, 10th ed., 1994, 302),
II3) (2,3-dichloro-4-hydroxyphenyl) 1-methylcyclohexanecarboxylic acid amide ("phenhexamide") (EP-A-339418),
III) 2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylic acid methyl ester ("azoxystrobin") (EP-A-382375),
IIK) methyl methoxyimino (2-ortho-tolyloxymethylphenyl) acetic acid methyl ester ("cresoxime methyl") (EP-A-398692),
or, respectively, one of the salts or metal-containing complexes of compounds I and II.

 According to the invention, it was unexpectedly found that mixtures of components I and II according to the invention possess not only additive activity, but also significantly higher activity due to synergism in the prevention and control of plant diseases.

 Preferred ratios of the two active ingredients I: II in the mixture are from 20: 1 to 1:20, and more preferred ranges are from 10: 1 to 1:10, from 6: 1 to 1: 6, from 2: 1 to 1: 10 and from 10: 1 to 1: 2.

 Mixtures of active substances I + II according to the invention have valuable characteristics in relation to the protection of plants from outbreaks of various diseases.

 In addition, mixtures comprising compound IIB can activate a latent protective system in a plant with respect to protection against exposure to a pathogenic microorganism, and thus can protect the plant by immunization.

 Mixtures of active substances according to the invention can be used to inhibit or destroy microorganisms that are found on plants or on parts of plants (fruits, flowers, leaves, stems, tubers, roots) of various crops of beneficial plants, while protection against these microorganisms also extends to those parts plants that form in a later period. They can also be used as seed dressing agents in order to protect plant propagation material, in particular seed material (fruits, tubers, grains) and plant seedlings (for example, rice), in order to protect them from fungal infections and from phytopathogenic fungi . The mixtures of active substances according to the invention are highly compatible with plants and environmentally friendly.

 Mixtures of active ingredients according to the invention are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula), Basidiomycetes (e.g., to the genera Hemileia, Rhizoctonia, Puccinia, e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and, in particular, Pseudocercosporella herpotrichoides), Oomycetes (e.g. Phytophthora, Peronospora, Bremia, Pythium, Plasmopara).

 Cultivated plants to be protected with respect to the diseases described herein that fall within the scope of the present invention include, for example, the following plant species: cereals (wheat, barley, rye, oats, rice, sorghum, etc.), beetroot (sugar beet and fodder beets), pome fruits, stone fruits and berry crops (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries), legumes (beans, lentils, peas, soybeans), oilseeds (rapeseed, mustard, poppy, olives, sunflower, coconut, castor oil, cocoa beans, macaw his), cucumber plants (pumpkin, cucumber, melon), fiber plants (cotton, flax, hemp, jute), citrus fruits (oranges, lemons, grapefruits, tangerines), vegetables (spinach, salad, asparagus, cabbage, carrots, onions, tomatoes, potatoes, bell peppers), Lauraceae (laurel crops) (avocado, cinnamon tree, camphor tree) or plants such as corn, tobacco, nuts, coffee, sugarcane, tea, grapes, hops, bananas and natural rubber nodules as well as ornamental plants (floral, shrubby, deciduous trees and evergreens trees such as conifers). However, the scope of the invention is not limited to the above list.

Mixtures of active substances according to the invention have the greatest advantages in the following applications:
I + IIA: on cereals and grapes,
I + IIB: on cereals, in particular on wheat and barley, as well as on grapes and fruit and vegetable crops,
I + IIB: on cereals,
I + IIG: on grapes,
I + IID: on cereals,
I + IIE: on cereals, in particular on wheat and barley, as well as on grapes and vegetable crops,
I + IIЖ: for processing seed material,
I + II3: on vegetable crops and grapes,
I + III: on cereals and grapes,
I + IIK: on cereals, in particular on wheat and barley.

 Mixtures of active substances of the formulas I and II are usually used in the form of compositions. The active substances of formulas I and II can be used to treat the sown area or plants to be treated simultaneously or sequentially on the same day, optionally with additional carriers, surfactants or other additives that contribute to the application, usually applicable in the field preparation formulations.

 Suitable carriers and additives may be solid or liquid and are substances suitable for the preparation of formulations, for example, natural or regenerated minerals, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders or fertilizers.

 The preferred method of treatment with a mixture of active substances containing at least one of these active substances I and II, is the processing of the aerial parts of plants, in particular the leaf system (sheet processing). The frequency of treatments and the rate of consumption depend on the biological and climatic conditions of life of the pathogen. However, the active substances can also penetrate into the plant through the root system (systemic effect) from the soil or water, if the growth sites of the plant are saturated with a liquid preparation (for example, during rice cultivation) or if the compounds are applied to the soil in solid form, for example, in the form of granules ( soil application). The compounds of formulas I and II can also be applied to seeds by seed treatment (coating), with the tubers or seeds either immersed sequentially in the liquid composition of each active substance or coated with an already combined liquid or dry composition. In addition, in special cases, other processing methods are also possible, for example, selective treatment of the kidneys or ovaries. Moreover, the compounds included in the composition are used in unmodified form or preferably together with inert fillers, usually used in the preparation of formulations, which are prepared in a known manner to obtain, for example, emulsion concentrates, coating pastes, ready-to-use solutions for spraying or diluted solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules or also encapsulated, for example in polymeric substances, preparations Comrade. Processing methods, such as spraying, misting, dusting, scattering, coating or watering, are selected depending on the type of composition, as well as in accordance with the objectives and specific conditions, as well as depending on the choice of type of active substance. Preferred rates of application of the mixture of active ingredients are usually from 50 g to 2 kg of active ingredient (a.a.) per hectare, preferably from 100 g to 700 g a.a. ./ha. When used for seed treatment, consumption rates are from 0.5 g to 600 g, preferably from 5 g to 80 g ai. per 100 kg of seeds.

 The formulations are prepared in a known manner, for example, by thoroughly mixing and / or grinding the active ingredients with diluents, for example with solvents, with solid fillers and optionally with surfactants.

Suitable solvents are aromatic hydrocarbons, preferably C ₈ -C ₁₂ fractions such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, highly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformide, and optionally epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil, or water.

 Solid fillers, for example for dusts and dispersible powders, are typically natural mineral powder fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add finely divided silicic acid or finely dispersed absorbing polymers. Suitable granular adsorbent fillers are porous carriers, for example pumice, broken brick, sepiolite or bentonite, and suitable non-absorbent fillers are, for example, calcite or sand. In addition, a number of pre-granulated materials of inorganic or organic origin, in particular dolomite or powdered plant residues, can also be used.

 Depending on the nature of the active substances of formulas I and II, on the basis of which the formulation is made, suitable surfactants are nonionic, cationogenic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants should also be understood as mixtures of surfactants.

 Particularly preferred supportive additives are also natural or synthetic phospholipids from the group of cephalins and lecithins, for example phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, lysolecithin.

 Agricultural compositions usually contain from 0.1 to 99%, preferably from 0.1 to 95% of the active substances of formulas I and II, from 99.9% to 1%, preferably from 99.9 to 5%, of solid or liquid additives and from 0 to 25%, preferably from 0.1 to 25% of a surfactant.

 While concentrated compositions are more preferred as commercially available products, the immediate consumer typically uses diluted compositions.

 Below the invention is illustrated by examples, the term "active substance" (AI) means a mixture of compound I and compound II in a certain ratio.

 Examples of formulations are given in table A.

 The active substance is thoroughly mixed with additives and ground in an appropriate mill. Powders intended for spraying are obtained which can be diluted with water to give suspensions of any desired concentration.

Emulsion Concentrates
Active ingredient (I: II = 1: 6) - 10%
Octylphenol polyethylene glycol ether (4-5 moles of ethyleneoxy units) - 3%
Calcium Dodecylbenzenesulfonate - 3%
Castor oil polyethylene glycol ether (35 moles of ethyleneoxy units) - 4%
Cyclohexanone - 30%
Xylene mixture - 50%
Emulsions of any desired concentration can be prepared by diluting such concentrates with water, and then they can be used to protect plants.

Coated Granules
Active ingredient (I: II = 1: 10) - 8%
Polyethylene glycol (molecular weight 200) - 3%
Kaolin - 89%
The finely divided active substance is uniformly fed into the mixer to kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

 Biological examples.

 It is believed that the combination of active substances has a synergistic effect if the activity of the combination of active substances is higher than the sum of the activities of the individual components.

The value of E, i.e. the activity expected for this combination of active substances is calculated using the so-called Colby formula as follows (Colby SR Calculating synergistic and antagonistic responses of herbicide combination, Weeds, Volume 15, pp. 20-22, 1967),
where ppm means the number of milligrams of active ingredient (d.v.) per liter of spray mixture,
X means the activity (in percent) of the active substance I when using p part./million of the active substance,
Y means the activity (in percent) of the active substance II when using q part./million of the active substance,
The expected (additive) activity of the active substances I + II when using p + q ppm of the active substance in accordance with the Colby formula is
E = X + YX • Y / 100.

 If the actually obtained activity (O) is higher than the expected activity (E), then the activity of the combination is super-additive, i.e. there is synergy (SF - synergy coefficient).

 Example B-1: Activity against Puccinia recondita on wheat.

 a) Residual protective effect.

6 days after planting, wheat plants are treated until drops appear with an aqueous spray mixture prepared from a formulation of a mixture of active substances in the form of a wettable powder, and after 24 hours they are infected with a suspension of fungal ureospores. After 48-hour incubation (conditions: relative humidity 95-100%, 20 ^o C), the plants are kept in a greenhouse at 22 ^o C. the Affection of the fungus is evaluated 12 days after infection.

 b) Systemic action.

5 days after planting with an aqueous spray mixture prepared from a formulation of a mixture of active ingredients in the form of a wettable powder, the soil around the wheat plants is treated. Take precautions so that the spray mixture does not fall on the aerial parts of plants. After 48 hours, the plants are inoculated with a suspension of fungus uredospore. After 48-hour incubation (conditions: relative humidity 95-100%, 20 ^o C), the plants are kept in a greenhouse at 22 ^o C. the Affection of the fungus is evaluated 12 days after infection.

 Mixtures of active substances, including, in particular, components IIB and IIB, have high synergistic activity.

 Example B-2: Activity against Plasmopara viticola on grapes.

Chubuki grapes at the stage of 4-5 leaves are treated until drops appear with an aqueous spray mixture prepared from a formulation of a mixture of active substances in the form of a wettable powder, and after 24 hours they are infected with a suspension of fungal sporangia. The defeat of the fungus is evaluated 6 days after infection, during which the relative humidity is maintained at the level of 95-100% and the temperature at the level of 20 ^o C.

 Mixtures of active substances, including, in particular, components IIB, IIG and IIA, have high synergistic activity.

 Example B-3: Activity against Erysiphe graminis in barley.

 a) Residual protective effect.

Barley plants with a height of approximately 8 cm are treated until drops appear with an aqueous spray mixture prepared from a formulation of the active substances in the form of a wettable powder, and after 3-4 hours they are pollinated with fungal conidia. Infected plants are kept in a greenhouse at 22 ^o C. the Affection of the fungus is evaluated 12 days after infection.

b) Systemic action
Barley plants with a height of approximately 8 cm are treated with an aqueous spray mixture prepared from a formulation of the active ingredients in the form of a wettable powder. Take precautions so that the spray mixture does not get on the aerial parts of plants. After 48 hours, the plants are pollinated with conidia of the fungus. Infected plants are kept in a greenhouse at 22 ^o C. the Affection of the fungus is evaluated 12 days after infection.

 Mixtures of active substances, including, in particular, components IIA, IIG and IID, have high synergistic activity (see table 1).

 Example B-4: Activity against Phytophtora infestans on tomatoes.

 a) Therapeutic effect.

Tomato plants of the Red Gnom variety are sprayed with a suspension of fungus zoospores after growing for three weeks and incubated in a chamber at a temperature of 18 to 20 ^° C and in an atmosphere saturated with water vapor. After 24 hours, the hydration is stopped. After the plants have dried, they are sprayed with a mixture prepared from a formulation of the active substances in the form of a wettable powder. After drying of the coating applied by spraying, the plants are again placed in a humidification chamber for 4 days. The criteria for evaluating the effectiveness of the tested substances are the number and size of typical spots on the leaves.

 b) Preventive systemic action.

A preparative form of active ingredients in the form of wettable powders is applied to the soil surface around three-week-old Red gnom tomato plants planted in separate flower pots. After growing for three days, the underside of the leaves is sprayed with a suspension of Phytophtora infestans zoospores. Then they are kept for 5 days in a humidification chamber at a temperature of from 18 to 20 ^o C and in an atmosphere saturated with water vapor. After this period, typical spots appear on the leaves. The quantity and size of these spots are used to evaluate the effectiveness of the test substances.

 Mixtures of active substances, including, in particular, components IIB and IIB, have high synergistic activity.

 Example B-5: Activity against Botrytis cinerea on apples.

 Residual protective effect.

Artificially damaged apples are treated by applying drops of a mixture for spraying on damaged places. Then, the treated fruits are inoculated with a spore suspension of the fungus and incubated for one week under conditions of high atmospheric humidity at a temperature of approximately 20 ^o C. The fungicidal effect of the test substances is evaluated by the number of damaged places that began to turn red.

 Mixtures of active substances, including, in particular, components IIB and IIB, have high synergistic activity.

 Example B-6: Activity against Fusarium nivale on rye (seed treatment).

 The naturally occurring rye of the Tetrahell variety, Fusarium nivale, is impregnated with a test fungicide in a drum mixer, using the following concentrations: 20 or 6 ppm a.v. (active substances) (in relation to the mass of seeds).

 Contaminated and treated rye is sown in October using a seeder in open ground in 6 rows in 3 m plots. For each concentration, 3 replicates are used. To assess damage to the fungus, the experimental plantation is grown in ordinary field conditions (preferably in an area with continuous snow cover during the winter period.

 To assess phytotoxicity in autumn, seed germination is assessed, and in spring, planting density / number of plants is assessed.

 To determine the activity of the active substances immediately after snow melt, the percentage of plants damaged by Fusarium is calculated. Mixtures of active substances have a high synergistic activity.

 Example B-7

 Protective action against Letosphaeria nodorum on wheat.

 Solvent: 25 parts by weight of N, N-dimethylacetamide.

 Emulsifier: 0.6 parts by weight of alkylated polyethylene glycol ether.

 To obtain a suitable active substance for use: 1 part by weight of the active substance or combination of active substances was mixed with the indicated amounts of solvent and emulsifier, and the concentrate was dissolved in water to obtain the desired concentration.

To determine the protective activity, young plants were sprayed with the preparation of the active compound or a combination of active substances at the application rate indicated in the application. After spraying and drying, the plants were treated with a spore suspension of Letosphaeria nodorum. Plants were incubated for 48 hours in a thermostat at 20 ^o C and a relative atmospheric humidity of 100%.

Plants were placed in a greenhouse with a temperature of approximately 15 ^o With a relative atmospheric humidity of 80%.

 The results were evaluated 10 days after inoculation. A 0% efficiency value corresponded to the control, while a 100% value means that no damaged plants were observed. The results are shown in table.2.

 Example B-8

 Protective effect against Sphaerotheca on cucumbers.

 Solvent: 49 parts by weight of acetone.

 Emulsifier: 1 part by weight of alkylated polyethylene glycol ether.

 To obtain a suitable active substance for use: 1 part by weight of the active substance or a combination of active substances was mixed with the indicated amounts of solvent and emulsifier and the concentrate was dissolved in water to obtain the desired concentration, or the test or commercial composition was dissolved in water to the desired concentration.

 To determine the protective activity, young plants were sprayed with a preparation of the active compound or a combination of active substances at the application rate indicated in the application. After spraying and drying, the plants were treated with an aqueous suspension of Sphaerotheca spores.

Plants were placed in a greenhouse with a temperature of approximately 23 ^o With a relative atmospheric humidity of 70%.

 The results were evaluated 7 days after inoculation. A 0% efficiency value corresponded to the control, while a 100% value means that no damaged plants were observed.

 The following table 3 clearly demonstrates that the observed activity of the combination of active substances in accordance with the invention is higher than the calculated activity, i.e. a synergistic effect is observed.

 The combination of compounds according to the invention are given in table 4.

Claims (4)

1. A fungicidal composition for plants, comprising as components two active ingredients in an amount having synergistic activity, in combination with an appropriate excipient, characterized in that component I is O-methyloxy methyl ester 2- [α- {[(α- methyl-3-trifluoromethyl-benzyl) imino] oxy} ortho-tolyl] glyoxylic acid, and component II is a compound selected from the group consisting of
IIA) 5,7-dichloro-4- (4-fluorophenoxy) quinoline ("quinoxifene"),
IIB) 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine ("cyprodinil"),
IIB) S-methyl ester of benzo (1,2,3) thiadiazole-7-carbothioacid ("acibenzolar-S-methyl"),
IIG) 3-aniline-5-methyl-5- (4-phenoxyphenyl) -1,3-oxazolidine-2,4-dione ("famoxadone"),
IIE) 8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4,5] decan-2-methanamine ("spiroxamine").  2. The composition according to p. 1, characterized in that the mass ratio of the components I: II is from 10: 1 to 1: 10.  3. The composition of claim 1, wherein component II is compound IIA) 5,7-dichloro-4- (4-fluorophenoxy) quinoline (“quinoxifene”).  4. The method of combating and preventing plant diseases, characterized in that the place affected by the fungus or which can be affected by the fungus is treated with component I and component II according to claim 1 with the appropriate excipients in an amount that provides synergistic interaction in any order or at the same time.

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