TW201304684A - Fungicidal mixtures - Google Patents

Abstract

The present invention relates to synergistic mixtures comprising, as active components, one fungicidal compound IA selected from the group consisting of dodemorph, carboxin, propineb, ziram, benodanil, pentachlorphenol and pthalid; or one bio-logical compound IB selected from the Bacillus subtilis var. amyloliquefaciens FZB24, chitosan, Pythium oligandrum DV74 and Reynoutria sachlinensis; and one fungicidal compound II selected from the group of strobilurines in synergistic effective amounts.

Description

Fungicidal mixture

The present invention relates to a synergistic mixture comprising a synergistically effective amount of the following as active ingredients:

1) One selected from the group consisting of carboxin, dodemorph, spiroxamin, procymidon, valifenalat, sulfur, 2-(4) -chlorophenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide; -{1-[2-(5-Methyl-3-trifluoromethyl-pyrazol-1-yl)-ethinyl]-piperidin-4-yl}-thiazole-4-carboxylic acid-methyl -(1,2,3,4-tetrahydronaphthalen-1-yl)-decylamine, methyl zinc propionb, ziram, tolylfluanid, 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzimidazole, 2-{1-[2-(5-methyl-3-trifluoromethyl- Pyrazol-1-yl)-ethinyl]-piperidin-4-yl}-thiazole-4-carboxylic acid-methyl-(R)-1,2,3,4-tetrahydro-naphthalene-1- a fungicidal compound IA of the group consisting of guanamine, benodanil, pentachlorophenol, phenhalid and hydrazine; or

2) a biological compound IB selected from the group consisting of Bacillus subtilis var. amyloliquefaciens FZB24, chitin, Pythium oligandrum DV74 and Reynoutria sachlinensis;

3) one selected from the group consisting of azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, Kresoxim-methyl, metominostrobin, oressastrobin, picoxystrobin, pyraclostrobin, pyramatetostrobin, pyraclostrobin (pyraoxystrobin), pyridencarb, trifloxystrobin, 2-(o-((2,5-dimethylphenyl-oxymethylene)phenyl)-3-methoxy Methyl acrylate, 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylaminomethyl)-phenyl)-2-methoxy A fungicidal compound II of the group of imino-N-methyl-acetamide.

These above mixtures are also referred to hereinafter as "mixtures of the invention". Compound IA and Compound IB are also commonly referred to hereinafter as Compound I.

Furthermore, the invention relates to a method of controlling phytopathogenic harmful fungi using the mixture of the invention and to the use of compounds I and II in the preparation of such mixtures, and also to compositions comprising such mixtures.

Furthermore, the present invention relates to a method for controlling a phytopathogenic harmful fungus, which comprises causing the plant pathogenic harmful fungus, its habitat, breeding ground, its location or a plant, soil or plant propagation material to be protected from fungal attack. Contact with an effective amount of the mixture as defined above.

Additionally, the invention also includes a method of protecting a plant propagation material from attack by a phytopathogenic harmful fungus, the method comprising contacting the plant propagation material with a fungicidally effective amount of a mixture of the invention.

The term "plant propagation material" is understood to mean all reproductive parts of a plant, such as seeds, and vegetative plant material (such as cuttings and tubers (eg potatoes)) that can be used to propagate plants. It includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, shoots and other parts of the plant (including seedlings and young plants) which are transplanted after germination or after emergence from the soil. The young plants may also be protected by whole or partial treatment by dipping or casting prior to transplantation. In a particularly preferred embodiment, the term propagation material refers to a seed.

The invention further relates to a plant protection active ingredient mixture having synergistic enhancing effects for enhancing the health of the plant and to a method of applying the mixture of the invention to a plant.

Compounds IA and II, as well as their fungicidal action, and their preparation are generally well known. For example, commercially available compounds can be found in The Pesticide Manual, 14th Edition, British Crop Protection Council (2006) and other publications.

5-Chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzimidazole and its fungicidal action are disclosed in WO 2000029404. 2-(4-Chlorophenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-B Guanidine and its fungicidal action are well known in WO 2004083193. 2-{1-[2-(5-Methyl-3-trifluoromethyl-pyrazol-1-yl)-ethinyl]-piperidin-4-yl}-thiazole-4-carboxylic acid-A -(1,2,3,4-tetrahydronaphthalen-1-yl)-nonylamine and 2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl) )-Ethyl]-piperidin-4-yl}-thiazole-4-carboxylic acid-methyl-(R)-1,2,3,4-tetrahydro-naphthalen-1-yl-decylamine and The fungicidal action is disclosed in WO 07/14290 and WO 08/13622.

Compound IB is commercially available, and the B. subtilis variant FZB24 is for example TAEGRO. (Novozyme Biologicals, Inc., USA), chitin is, for example, ARMOUR-ZEN (BotriZen Ltd., New Zealand), and dioxin mold DV74 is for example POLYVERSUM (Remeslo SSRO, Biopreparaty, Chez Republic) and the giant knotweed are for example Produkt REGALIA (Marrone BioInnovations, USA).

A typical problem that arises in the field of fungal control is the need to reduce the rate of administration of the active ingredient to reduce or avoid adverse environmental or toxicological effects while still enabling effective fungal control.

The term phytopathogenic harmful fungi according to the present invention is hereinafter referred to simply as "harmful fungi".

Another problem encountered involves the need to have useful fungal control agents that are effective against a wide range of harmful fungi.

There is also a need for fungal control agents that control activity in combination with long-term control (i.e., rapid action and long-lasting action).

Another difficulty associated with the use of fungicides is the repeated and pure application of individual fungicidal compounds which in many cases lead to the rapid selection of harmful fungi which have developed natural or adaptive resistance to the active compounds in question. . Therefore, there is a need for fungal control agents that help prevent or overcome resistance.

Another problem concealed by the present invention is the need to improve the composition of plants (a process which is conventional and referred to hereinafter as "plant health").

The term plant health status includes improvements in various grades of plants that are not related to the control of the fungus. For example, the advantageous properties that may be mentioned are improved crop characteristics including: budding, crop yield, protein content, oil content, starch content, well-developed roots (enhanced root growth), and increased stress tolerance ( For example, drought resistance, heat resistance, salt tolerance, UV resistance, water resistance, cold resistance), reduction in ethylene (reduction in yield and/or reception), enhancement of tillering, increase in plant height, enlargement of leaves, dead base Reduced leaflets, strong lychee, green color of leaves, pigment content, photosynthetic activity, reduced required inputs (such as fertilizer or water), reduced seed requirements, increased production of litchi, early flowering, early maturity, plants Reduced bending (inverted), enhanced seedling growth, enhanced plant vigor, plant standing and germination early and better; or familiar with any other advantages known to those skilled in the art.

Accordingly, it is an object of the present invention to provide a fungicidal mixture that addresses the problem of reducing the rate of administration and/or enhancing the range of activity and/or binding activity control with long term control and/or resistance control and/or promoting plant health.

It has been found that this target is achieved, in part or in whole, by a composite mixture containing the active compound as defined at the outset.

In particular, it has been found that the initially defined mixture exhibits a significantly enhanced antifungal effect compared to the possible rate of control of the individual compounds, and/or in the application to plants, parts of plants, plant propagation material (preferably seed) It is used to enhance the health of plants when they are grown.

It has been found that the effect of the mixtures according to the invention goes far beyond the fungicidal and/or plant health enhancing effects of the active compounds present alone in the mixture.

Furthermore, it has been found that the simultaneous administration of Compound I and Compound II or the sequential application of Compound I and Compound II improves fungal control compared to the possible rate of control of individual compounds (co-fungal mixture). Control.

In addition, we have found that the possible plant health effects of individual compounds, in which synergistic effects are synergistic mixtures of plant health, are simultaneously (ie, co- or separately) administration of Compound I and Compound II or sequential administration of the compound. I and Compound II provide enhanced plant health effects.

The mixture of the present invention contains a synergistically effective amount (for example, the weight ratio of the compound I to the compound II is from 500:1 to 1:500, preferably from 100:1 to 1:100, more preferably from 50:1 to 1:50, and even more preferably Active substances from 20:1 to 1:20, especially from 10:1 to 1:10, especially from 5:1 to 1:5).

In another preferred embodiment, the invention is directed to a mixture comprising Compound IA and Compound II.

Preferably, the mixture of the present invention comprises compound IA and as a compound II, azotoxin, fenfluramine, enestrobin, fluoxastrobin, kexinxin, phenoxystrobin, oxime, and oxybacteria. Ester, kekemin, pyridoxine or trifluoro-sensitive. More preferably, the mixture of the invention comprises Compound IA and as a compound II, azotoxin, kexinxin, oxime, oxypide, hexagram or trifluoro-sensitive. Most preferably, the mixture of the invention comprises Compound IA and as a sub-sensitive, hexa-sensitive or trifluoro-sensitive compound as Compound II. It is excellent to be a mixture comprising compound IA and as a compound II.

Equally preferably, the mixture of the invention comprises compound IB and as a compound II, oxytocin, fenfluramine, enestrobin, fluoxastrobin, kexinxin, phenoxystrobin, anthracycline, oxybacteria Ester, kekemin, pyridoxine or trifluoro-sensitive. More preferably, the mixture of the invention comprises Compound IB and as a compound II, oxytocin, dextromethorphan, acesulfame, pyridineoxyl, dextromethorphan or trifluoro-sensitive. Most preferably, the mixture of the invention comprises Compound IB and as a sub-sensitive, hexa-sensitive or trifluoro-sensitive compound as Compound II. It is excellent to be a mixture comprising compound IB and as a compound II.

In the mixture of the present invention containing the compound IA and the compound II, the preferred compound IA is selected from the group consisting of saponin, carbendazim, spirooxamine, chlorpheniramine, valprofen, methyl zinc, and sui. Methyl valproate, 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzimidazole, 2-(4-chlorophenyl)-N -[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide; 2-{1-[2- (5-Methyl-3-trifluoromethyl-pyrazol-1-yl)-ethinyl]-piperidin-4-yl}-thiazole-4-carboxylic acid-methyl-(1,2,3 ,4-tetrahydronaphthalen-1-yl)-nonylamine and 2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl)-ethenyl]-perphene Pyridin-4-yl}-thiazole-4-carboxylic acid-methyl-(R)-1,2,3,4-tetrahydro-naphthalen-1-yl-decylamine, preferably compound IA is selected from the group consisting of rust Ling, carbendazim, spirooxamine, chlorpheniramine, valfenic acid ester, 2-(4-chlorophenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxine Zyrid-5-yl]-2-prop-2-ynyloxy-acetamide and 2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazol-1-yl) -Ethyl]piperidin-4-yl}-thiazole-4-carboxylic acid-methyl-(1,2,3,4-tetrahydronaphthalen-1-yl)-guanamine, the best compound IA Is selected from the group consisting of rust and chlorpyrifos. Yisui, Mai Rupling, pentachlorophenol and benzoquinone. It is excellent to contain a mixture of carbendazim, methylzinc and acetal and compound II as compound IA.

Preferably, the fungicidal component is limited to a mixture of sulfur and compound II, wherein the compound II in the mixture is preferably selected from the group consisting of atropine, ethersporin, enestrobin, fluoxastrobin, kexinxin, Phenoxystrobin, anthracycline, picoxystrobin, cyproterone, pyridoxine or trifluoro-sensitive, preferably selected from the group consisting of azotoxin, kexinxin, acesulfame, oxypide, and hundred Kemin or trifluoro-sensitive, preferably selected from the group consisting of Atomin, Baikemin or Trifluoro-sensitive and excellent for Baikemin.

A further preferred embodiment of the invention is directed to the compositions listed in Table A, wherein the list of Table A corresponds in each case to one of the compounds IA and one of the components II included in each column. A fungicidal composition. The mixture of the present invention comprises a synergistically effective amount (for example, the weight ratio of the compound IA to the component II is from 500:1 to 1:500, preferably from 100:1 to 1:100, more preferably from 50:1 to 1:50, still more Good active material from 20:1 to 1:20, especially from 10:1 to 1:10, especially from 5:1 to 1:5).

This article uses the following abbreviations in Table A:

In the mixture of Table A, it is more preferably the following mixture: A-2, A-8, A-9, A-13, A-14, A-15, A-18, A-24, A-25, A-29, A-30, A-31, A-34, A-40, A-41, A-45, A-46, A-47, the following mixtures are better: A-2, A-8, A-9, A-18, A-24, A-25, A-34, A-40, A-41; and the following mixtures are optimal: A-2, A-8, A-9, A-18 , A-24, A-25. Excellent for A-2, A-8 and A-9.

A further embodiment of the invention relates to the compositions listed in Table B, wherein the list of Table B corresponds in each case to the fungicidal activity comprising a compound IB and a component II listed in the respective columns. combination. The inventive mixture comprises a synergistically effective amount (for example, the weight ratio of compound IB to component II is from 500:1 to 1:500, preferably from 100:1 to 1:100, more preferably from 10:1 to 100:1 and optimal. Active substance from 20:1 to 40:1 (IB:II)).

This article uses the following abbreviations in Table B:

I is compound IB PIC= picoxystrobin

II is compound II O = oxime

P=100 grams of sensitive solution Bacillus subtilis variant FZB24=B1

T = trifluoro-sensitive chitin = B2

A=Atropin Pseudomonas erythraea DV74=B3

KM=克收欣 大虎杖=B4

In the mixture of Table B, the following mixtures are preferred: B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, B-9, B Mixtures of -10, B-11 and B-12 and below are more preferred: B-1, B-2, B-3 and B-4.

Therefore, the mixture of Table A and Table B is most preferred, however, the mixture of Table A is more preferred.

Each of the above mixtures of the invention (in addition to containing sulfur as a mixture of compounds IA) may further comprise one or more insecticides, fungicides, herbicides.

With regard to the use according to the invention, the mixtures according to the invention can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, powders, pastes and granules. The form of use depends on the particular intended purpose; in each case, it should be ensured that the mixture of the invention is finely and uniformly distributed. Formulations are known in the art (see US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, December 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Edition, McGraw-Hill, New York, 1963, S. 8-57 and following WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701, US 5,208,030, GB 2,095,558, US 3,299,566, Klingman : Weed Control as a Science (J. Wiley & Sons, New York, 1961), Hance et al.: Weed Control Handbook (8th ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation Prepared by technology (Wiley VCH Verlag, Weinheim, 2001).

Agrochemical formulations may also contain adjuvants commonly used in agrochemical formulations. The auxiliaries used depend on the particular application form and the active substance, respectively.

Examples of suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as other cosolvents, protective gums, surfactants and adhesives), organic and inorganic thickeners, bactericides, antifreezes, antifoams. Agents, optional coloring agents and tackifiers or binders (for example, in the case of seed treatment formulations).

Suitable solvents are water, organic solvents (such as medium to high boiling mineral oil soluble parts (such as kerosene or diesel, in addition to coal tar and vegetable oil or animal oil), aliphatic, cyclic and aromatic hydrocarbons (such as toluene, xylene) , paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, such as methanol, ethanol, propanol, butanol and cyclohexanol alcohols, glycols, ketones such as cyclohexanone and γ-butyrolactone, Fatty acid dimethyl decylamine, fatty acids and fatty acid esters and strong polar solvents (such as amines such as N-methylpyrrolidone).

The solid carrier is mineral soil, such as citrate, tannin, talc, kaolin, limestone, lime, chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, grinding synthesis Materials, fertilizers (such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea), and plant derived products such as cereal flour, bark flour, wood flour and nut shell powder, cellulose powder and other solid carriers.

Suitable surfactants (adjuvants, wetting agents, tackifiers, dispersants or emulsifiers) are aromatic sulfonic acids (such as lignin sulfonic acid (Borresperse) Class, Borregard, Norway), phenolic acid, naphthalenesulfonic acid (Morwet Class, Akzo Nobel, USA), Dibutylnaphthalenesulfonic acid (Nekal Class, BASF, Germany)) and alkali metal, alkaline earth metal and ammonium salts of fatty acids, alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, and Sulfated hexadecane, heptadecyl and octadecyl alcohol esters, sulfated fatty alcohol glycol ethers, in addition, condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene ethyl octyl phenyl ether, ethoxylate Isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, tristearyl phenyl polyglycol ether, alkyl aryl polyether Alcohol, alcohol and fatty alcohol/ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene ethyl ether, ethoxylated polypropylene oxide, lauryl alcohol polyether ether acetal, sorbose Alcohol esters, lignin sulfite waste liquids and proteins, denatured proteins, polysaccharides (such as methyl cellulose), hydrophobically modified starch, polyvinyl alcohol (Mowiol) Class, Clariant, Switzerland), polycarboxylate (Sokolan Class, BASF, Germany), polyal-koxylates, polyvinylamine (Lupasol Class, BASF, Germany), polyvinylpyrrolidone and copolymers thereof.

Examples of thickeners (i.e., compounds that impart a change in fluidity to the formulation, i.e., high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and inorganic clays such as xanthan gum (Kelzan). , CP Kelco, USA), Rhodopol 23 (Rhodia, France), Veegum (RT Vanderbilt, USA) or Attaclay (Engelhard Corp., NJ, USA).

A bactericide can be added to preserve and stabilize the formulation. Examples of suitable bactericides are based on dichlorophenol and benzyl alcohol hemiformal (Proxel from ICI) Or Acticide from Thor Chemie RS and Kathon from Rohm & Haas MK) and isothiazolinone derivatives such as alkylisothiazolinone and benzisothiazolinone (Acticide) MBS, obtained from Thor Chemie).

Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.

An example of an antifoaming agent is a polyoxyl emulsion (such as Silikon) SRE, Wacker, Germany, or Rhodorsil , Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.

Suitable colorants are low water solubility pigments and water soluble dyes. Examples which may be mentioned are the following names: Rose Bengal B, CI Pigment Red 112, CI Solvent Red 1, Pigment Blue 15:4, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 80 , pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48: 2, pigment red 48: 1, pigment red 57: 1, pigment red 53: 1, pigment orange 43, pigment orange 34, pigment orange 5, pigment Green 36, Pigment Green 7, Pigment White 6, Pigment Brown 25, Alkaline Violet 10, Alkaline Violet 49, Acid Red 51, Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, Alkaline Red 10, Basic red 108.

Examples of tackifiers or binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and cellulose ether (Tylose). , Shin-Etsu, Japan).

Powders, dispersing materials and powders can be prepared by admixing the compound (the individual active compound in the mixture of the invention and optionally other active substances) with at least one solid carrier or with grinding.

The particles (for example, coated particles, impregnated particles, and homogeneous particles) can be produced by binding the active material to a solid carrier. Examples of solid carriers are mineral soils such as tannin, silicate, talc, kaolin, attaclay, limestone, lime, chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate. , magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers (such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea), and plant-derived products such as cereal flour, bark powder, wood flour and nut shell powder, cellulose powder And other solid carriers.

Examples of formulation types are suspensions (SC, OD, FS), emulsified concentrates (EC), emulsions (EW, EO, ES), pastes, lozenges, wettability which may be water soluble or wettable. Powder or powder (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), and gel formulations suitable for the treatment of plant propagation materials such as seeds (GF), further details Illustrated below:

1. Type of composition suitable for dilution with water i) Water soluble concentrate (SL, LS)

A 10 part by weight of a compound of the present invention is dissolved in 90 parts by weight of water or a water-soluble solvent. Add a wetting agent or other additive as a substitute. The active substance dissolves immediately upon dilution with water. In this way, a formulation having an active substance content of 10% by weight is obtained.

Ii) dispersible concentrate (DC)

A solution of 20 parts by weight of the mixture of the invention is dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersing agent (for example polyvinylpyrrolidone). The dispersion was obtained by dilution with water. The active substance content was 20% by weight.

Iii) Emulsified concentrate (EC)

Taking 15 parts by weight of the compound of the invention mixture dissolved in 75 parts by weight of xylene with the addition of calcium dodecylbenzene sulfonate and ethoxylated castor oil (in each case, 5 parts by weight). The emulsion was obtained by dilution with water. The composition has an active substance content of 15% by weight.

Iv) Emulsion (EW, EO, ES)

Taking 25 parts by weight of the compound of the invention mixture dissolved in 35 parts by weight of xylene with the addition of calcium dodecylbenzene sulfonate and ethoxylated castor oil (in each case, 5 parts by weight). The mixture was introduced into 30 parts by weight of water by an emulsification machine (Ultraturrax) and a homogenized emulsion was prepared. The emulsion was obtained by dilution with water. The composition has an active substance content of 25% by weight.

v) Suspension (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of a compound of the invention mixture is added by adding 10 parts by weight of a dispersing agent and a wetting agent and 70 parts by weight of water or an organic solvent. Fragmentation gives a fine active substance suspension. A stable suspension of the active substance is obtained by dilution with water. The active substance content in the composition was 20% by weight.

Vi) water dispersible granules and water soluble granules (WG, SG)

Taking 50 parts by weight of the compound of the present invention by fine addition by adding 50 parts by weight of a dispersant and a wetting agent and by means of technical means (for example, an extruder, a spray tower, fluidization) The bed) is made of water-dispersible or water-soluble particles. A stable dispersion or solution of the active substance is obtained by dilution with water. The composition has an active substance content of 50% by weight.

Vii) Water dispersible powders and water soluble powders (WP, SP, SS, WS)

75 parts by weight of the compound of the inventive mixture were milled in a rotor-stator mill by the addition of 25 parts by weight of dispersant, wetting agent and silicone. A stable dispersion or solution of the active substance is obtained by dilution with water. The composition has an active substance content of 75% by weight.

Viii) Gel (GF)

In an agitated ball mill, 20 parts by weight of a compound of the present invention is added by adding 10 parts by weight of a dispersant, 1 part by weight of a gelling agent wetting agent and 70 A portion (by weight) of water or an organic solvent is ground to obtain a fine suspension of the active substance. A stable suspension of the active substance is obtained by dilution with water to obtain a composition having 20% (w/w) of active substance.

2. Type of composition applied without dilution Ix) Powder (DP, DS)

Five parts (by weight) of the compound of the present invention were finely ground and uniformly mixed with 95 parts by weight of the finely divided kaolin. This resulted in a powder composition having an active substance content of 5% by weight.

x) Particles (GR, FG, GG, MG)

A 0.5 part by weight of a compound of the inventive mixture is finely ground and combined with 99.5 parts by weight of a carrier. Current methods are extrusion, spray drying or fluidized beds. This allows the granules to be applied undiluted with an active substance content of 0.5% by weight.

Xi) ULV solution (UL)

A 10 part by weight of a compound of the present invention is dissolved in 90 parts by weight of an organic solvent (for example, xylene). This resulted in a composition which was applied undiluted with an active substance content of 10% by weight.

The agrochemical formulations generally comprise between from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, optimally between 0.5 and 90% by weight of active substance. The compounds of the mixtures of the invention are used at a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectroscopy).

By spraying, atomizing, spraying, spreading, brushing, dipping or casting, the compounds of the mixture of the invention may be in the form of, or in the form of, a composition (eg, as a direct sprayable solution, powder, suspension, Dispersions, emulsions, oil dispersions, pastes, sprayable products, materials or granules for dispersion are used. These forms of application depend entirely on the intended purpose; it is desirable to ensure that the compounds are distributed as finely as possible in the mixtures of the invention in each case.

The aqueous application form can be produced by adding water from an emulsion concentrate, a paste or a wettable powder (sprayable powder, oil dispersion). For the preparation of emulsions, pastes or oil dispersions, substances which are so soluble or soluble in oils or solvents can be homogenized by means of wetting agents, tackifiers, dispersants or emulsifiers. Alternatively, concentrates consisting of active substances, wetting agents, tackifiers, dispersing or emulsifying agents and optionally solvents or oils may be prepared, and such concentrates are suitable for dilution by water.

The concentration of the active substance in the ready-to-use preparation can vary over a relatively wide range. Usually, they are from 0.0001 to 10% by weight, preferably from 0.001 to 1% by weight, of the compound of the mixture of the invention.

The compounds of the mixtures according to the invention can also be used successfully in ultra low volume processes (ULV), compositions containing more than 95% by weight of active substance can be applied, or even the active substance can be applied without additives.

If appropriate, various types of oils, wetting agents, adjuvants, herbicides, fungicides, other insecticides or bactericides can be added to the active compound immediately prior to use (tank mixing). These agents may be admixed with the compound of the mixture of the invention in a weight ratio of from 1:100 to 100:1, preferably from 1:10 to 10:1.

The compositions of the present invention may also comprise fertilizers such as ammonium nitrate, urea, potash, and perphosphates, phytotoxins and plant growth regulators and safeners. They may be used sequentially or in combination with the above-mentioned compositions, if appropriate, only immediately prior to use (slot mixing). For example, the plant can be sprayed with the composition of the invention either before or after treatment with the fertilizer.

The compounds contained in the mixture as defined above may be administered simultaneously (i.e., together or separately) or sequentially, wherein the time interval between individual administrations is selected to ensure the activity of the first application when the other active substance is administered. The substance is still present in a sufficient amount in the affected area. For the purposes of practicing the invention, the order of administration is not required.

According to the invention, the compound I and the compound II are understood to mean that the compound I and the compound II are present at least in an effective amount at the site of action, ie the harmful fungus to be controlled or its habitat (such as infected plants, plant propagation material (specific In the words of seeds, surfaces, materials or soils, as well as plant and plant propagation materials (specifically, seeds, soils, surfaces, materials or spaces protected from fungal attack).

This can be achieved by simultaneous (whether common (eg, tank mixing) or separate) or sequential application of Compound I and Compound II, wherein the time interval between individual administrations is selected to ensure that the first active ingredient is administered The active substance applied is still present in a sufficient amount at the site of action. For the practice of the invention, the order of application is not required.

In the mixtures of the invention, the weight ratio of the compound will generally depend on the nature of the compound of the mixture of the invention.

The compounds of the mixtures according to the invention can be used in individual ways or have been partially or completely mixed with one another in order to obtain compositions according to the invention. They may also be packaged and further used as a combined composition such as part of a kit.

In one embodiment of the invention, the kits may comprise one or more (including all) components that can be used to prepare the title agrochemical composition. For example, the kit can comprise Compound I and Compound II and/or adjuvant components and/or other insecticide compounds (eg, insecticides or herbicides) and/or growth regulating components. One or more of these components may have been combined or pre-allocated. In embodiments in which two or more of the components are provided in kit form, the components may have been combined together and thus packaged in a single container such as a vial, bottle, can, bag, bag or can. . In other embodiments, two or more components of the kit may be packaged separately (ie, not pre-provisioned). Thus, the kit can include one or more separate containers, such as vials, cans, bottles, bags, bags or cans, each container containing separate components suitable for use in agrochemical compositions. In either form, the components of the kit may be administered separately or together with the other components or may be applied as a component of a combination composition according to the invention suitable for use in the preparation of a composition according to the invention.

The user typically applies the composition according to the invention by means of a pre-dosing device, a knapsack sprayer, a spray tank or a spray plate. Here, the agrochemical composition is made up of water and/or a buffering agent for a desired application concentration, if appropriate, other auxiliaries may be added, and thus a ready-to-use spray or agrochemical composition according to the invention is obtained. . Typically, 50 to 500 liters of ready-to-use spray is applied per hectare of agricultural useful area, preferably from 100 to 400 liters.

According to one embodiment, the individual compounds of the inventive mixture in the form of a composition (or formulation) such as a portion of a kit or a portion of a mixture of the invention may be mixed by the user themselves in a spray tank and if appropriate (tank mixing) , other additives can be added.

In yet another embodiment, the individual compound of the mixture of the invention formulated as a composition or a partially pre-mixed component (eg, a component comprising Compound I and Compound II) can be mixed by a user in a spray tank and if Suitable (tank mixing), other additives and additives can be added.

In yet another embodiment, the individual components of the composition according to the invention or the partially pre-mixed components (eg, the components comprising Compound I and Compound II) may be common (eg, after tank mixing) or Order application.

As described above, the present invention includes a method for harmful fungi, wherein the fungus, its habitat, breeding ground, its location, or a plant, soil or plant propagation material (preferably referred to as a seed) to be protected from fungal attack is via A fungicidal effective amount of the mixture is treated.

Advantageously, the mixtures of the invention are suitable for controlling harmful fungi: white rust associated with ornamental plants, vegetables (eg A. candida ) and sunflowers (eg A. tragopogonis ) Albugo spp. (white rust); with vegetables, canola ( A. brassicola or brassicae ), beet ( A. tenuis ) ), fruit, rice, soybeans, potatoes (such as A. solani or A. alternata ), tomatoes (such as Z. oxysporum or Alternaria) and wheat-related blacks Alternaria spp. (black spot); Aphanomyces spp. of sugar beet and vegetable; Ascochyta spp. associated with cereals and vegetables, such as wheat associated with wheat A. tritici (anthrax) and barley-related barley ( A. hordei ); Bipolaris spp. and Drechslera spp. teleomorph (teleomorph): blight flax species), e.g., the jade (Cochliobolus spp.) The correlation leaf spot (Southern leaf blight) (maydis (D. maydis)) or a large patch disease (Northern leaf blight) (Helminthosporium from raw corn (B. zeicola)), e.g., associated with the spot of cereals Blight ( B. sorokiniana ) and, for example, B. oryzae associated with rice and grassland; Brinell white powder associated with cereals (eg, associated with wheat or barley) genus (with Blumeria) (formerly Erysiphe (Erysiphe)) rusts (graminis) (powdery mildew); with fruits and berries (e.g., strawberries), vegetables (e.g. lettuce, carrots, cabbage, and celery), oilseed rape, Flowers, vines, forestry plants and wheat-related Botrytis cinerea (sexual type: Botryotinia fuckeliana : gray mold); lettuce-related lettuce dew bacteria ( Bremia lactucae) (dew fungus); Ceratocystis ( Ophiostoma ) ( corrupted or withered) associated with broadleaf and evergreen plants, for example, eucalyptus (C. ulmi) (Dutch elm disease); corn (e.g. gray leaf spot: corn gray Bacteria (C. zeae-maydis)), rice, sugar beet (e.g. beticola (C. beticola)), sugar cane, vegetables, coffee, soybeans (e.g. Cercospora pathogen (C. sojina) or soybean germs purpura (C Kikuchii )) and rice-related Cercospora spp. (C. cerevisiae leaf spot); and leafy fungi associated with tomato (eg, C. fulvum : leaf mold) and grain ( Cladosporium spp.), for example, wheat-related Mycobacterium ( C. herbarum ) (black ears); cereal-related C. cerevisiae ( Claviceps purpurea ) (ergots); and corn (corn round spots) C. carbonum ), cereals (such as C. sativus , asexual type: B. sorokiniana ) and rice (eg, rice leaf blight) ( C. Miyabeanus )), asexual type: H. oryzae ) Cochliobolus (asexual type: Helminthosporium of Bipolaris ) (leaf spot); cotton (e.g., cotton Alternaria (C. gossypii)), corn (e.g., Colletotrichum graminicola (C. graminicola): anthrax stem Disease), skin soft fruits, potatoes (e.g., spherical anthracnose (C. coccodes): black dot), beans (e.g. bean anthracnose (C. lindemuthianum)) and soy (e.g., soy anthrax (C. truncatum) or gum C. gloeosporioides ) Colletotrichum (sexual type: Glomerella ) (anthrax); rice-related plasters ( Corticium spp.), such as rice grain C. sasakii (sclerotium blight); Corynespora cassiicola (leaf leaf spot) associated with soybeans and ornamental plants; Cyclocorium spp .), for example, C. oleaginum ; with fruit trees, vines (eg C. liriodendri , sexual type: Neonectria liriodendri : Uzbekistan Foot disease) and ornamental plant-related Cylindrocarpon spp. (eg fruit tree ulcer or juvenile drooping, sexual type: Nectria spp. or Neonectria spp. )); Dematophora associated with soybeans (sexual) Type: Rosellinia necatrix (root and stem rot); soybean-related dry genus ( Diaporthe spp.), such as D. phaseolorum (dumping disease); Corn, cereals (such as barley (such as barley plaque ( D. teres ), net blotch) and wheat (such as D. tritici-repentis : brown spot), rice and grassland) Related to the genus Drechslera (synonymous wheat Helminthosporium , genus: Pyrenophora spp.); vine associated with vines (stem blight, gangrene) ), from the genus Formitiporia ( Phellinus punctata ), F. mediterranea , Phaeomoniella chlamydospora (early bacterium) , Phaeoacremonium aleophilum and / or Botryosphaeria obtusa ; and E. pyri , soft skin fruit ( E. veneta : anthracnose) and vine ( E. ampelina ): anthrax) related to the genus Elsinochrome (Elsinoe spp);. paddy rice associated with the Smut fungus (Entyloma oryzae) (leaf smut); associated with the wheat germ genus wilt Rui spots (Epicoccum spp.) (Black mold); and sugar beet (sugar beet powdery mildew (E. betae)), vegetables (eg, E. pisi ) (such as cucurbits (such as E. cichoracearum ), cabbage, rapeseed (such as E. cruciferarum ) Related Erysiphe spp. (powder disease); Eutypa lata (Eutypa canker) or scab, associated with fruit trees, vines and ornamental plants, asexual Type: Cytosporina lata , synonym Libertella blepharis ); Exserohilum (synonymous wheat Helminthosporium ) associated with corn (eg E. turcicum ); Plant-associated Fusarium (sexual type: Gibberella ) (wild, root or stem rot), such as Fusarium graminearum ( F ) associated with cereals (eg wheat or barley) . graminearum) or yellow Fusarium (F. culmorum) (root rot, scabies or gibberellic ), Associated with the tomato Fusarium Fusarium (F. oxysporum), related to the Fusarium solani soybean (F. solani) of maize and related Verticillium Fusarium (F. verticillioides); and cereals (e.g. Wheat or barley) and corn-related Gaeumannomyces graminis (total eclipse); with cereals (eg, G. zeae ) and rice (eg G. fujikuroi : rice) Gibberella spp.; Glomerella cingulata associated with vines, pears and other plants and cotton anthracis ( G. gossypii ) associated with cotton; Grainstaining complex; Guignardia bidwellii (black rot) associated with vines; Gymnosporangium spp. associated with Rosaceae and Brassica, for example Pear-related G.sabinae (rust disease ); wheat, cereal and rice-related wheat flax-like genus ( Helminthosporium spp.) (synonymous genus Drechslera , sexual type: flax leaf blight ( Cochliobolus )); camel rust Hemileia spp., such as coffee-related H. vastatrix (coffee leaf rust); vine-related Isariopsis clavispora (synonym Cladosporium vitis ); and soybean the kidney bean and cotton, Rhizoctonia solani related (Macrophomina phaseolina) (synonyms bean Rhizoctonia solani (phaseoli)) (root and stem rot); associated with the cereals (such as wheat or barley) Microdochium genus (Microdochium) (synonyms Fusarium red sun rot (pink snow rot); soybean-related soybean powdery mildew ( microsphaera diffusa ) (white powder); brown rot ( Monilinia spp.), for example with Drupe and other Rosaceae plants related to M. laxa , M. fructicola and apple brown rot ( M. fructigena ) (flower and blight, brown rot); Cereals, bananas, soft-skinned fruits and peanut-related genus Mycosphaerella spp., such as, for example, wheat-related M. graminicola (asexual type: Septoria tritici ), shell needle spot disease (Septor Ia blotch)) or banana-related banana leaf spot ( M. fifiensis ) (banana leaf spot); and cabbage (such as P. brassicae ), rapeseed (such as rapeseed P. parasitica ), onions (eg, P. destructor ), tobacco ( P. tabacina ), and soybeans (eg, P. manshurica ) Peronospora spp. (dew fungus); soybean-related soybean rust ( Phakopsora pachyrhizi ) and P. meibomiae (soybean rust); for example with vines (eg P. tracheiphila and P. tetraspora ) and soybean (eg P. gregata : stem rot) related to the genus Phialophora spp.; and Brassica napus associated with rapeseed and cabbage ( Phoma Lingam ) (root and stem rot) and P. betae (root rot, leaf spot and stagnation ) associated with sugar beet; with sunflowers, vines (eg grape stems) infestans (P. viticola): silkworm disease (CAN) and leaf spot) and soybeans (e.g., stem rot: Phomopsis bean (P. phaseoli), teleomorph: Soybean black spot pathogen (Diaporthe phaseolorum)) related to the genus Phomopsis (Phomopsis spp); associated with the maize corn Thraustochytrium section (Physoderma maydis) (brown spot); and a variety of plant (such as red pepper and pumpkin (such as P. capsici ), soybean (such as P. megasperma , P. sojae ), potato and tomato (for example) Phytophthora spp. ( P. infestans : late blight) and broad-leaved trees (such as P. ramorum : eucalyptus) (wild, root, leaf, fruit and Stem rot); Plasmodiophora brassicae (root swollen disease) associated with cabbage, rapeseed, radish and other plants; Plasmopara spp., such as grape bacterium, associated with vines P. viticola (Vine vine bacterium) and sunflower-related sunflower bacterium ( P. halstedii ); apple genus ( Podosphaera ) associated with Rosaceae, hops, pears and soft-skinned fruits Spp.) ), for example, apple-related P. leucotricha ; Polymyxa spp., for example, with cereals such as barley and wheat ( P. graminis ) and sugar Beet ( P. betae ) is associated with viral diseases transmitted by it; Pseudocercosporella herpotrichoides (eyespot) associated with cereals (such as wheat or barley), Sex type: Tapesia yallundae ); Pseudoperonospora (downy mildew) associated with various plants, such as P. cubensis associated with pumpkin or hops white fungus associated with hops ( P. Humili ); vine-related Pseudopezicula tracheiphila (red fire disease or rotbrenner ', anamorphic: Phialophora ); rust-related bacteria associated with various plants Puccinia spp. ( P. rust), for example, P. triticina (brown or leaf rust) associated with cereals (such as, for example, wheat, barley or rye), stripe rust ( P. striiformis) (stripe or yellow rust), large Puccinia (P. hordei) (small rust), wheat stem rust (P. graminis) (stem or black rust) or wheat leaf rust (P. recondita) (brown or leaf rust), associated with the stem of sugar cane yield En P. kuehnii (orange rust) and asparagus rust pathogen associated with asparagus ( P. asparagi ); wheat-related genus Pyrenophora (asexual type: genus Drechslera ) Tritici-repentis (brown spot) or barley-related barley pathogen ( P. teres ) (net spot disease); Pyricularia spp., such as rice-related rice fever pathogens ( P. oryzae ) (sex type: Magnaporthe grisea , rice fever) and rice smut ( P. grisea ) associated with grassland and cereals; and grassland, rice, maize, wheat, cotton, canola, sunflower, soybean, sugar beet, vegetables and various other plants (e.g. Pythium fungi (P. ultimum) or Pythium fungi (P. aphanidermatum)) related to the genus of damping-off (Pythium spp.) (damping off) Ramularia spp., such as R. collo-cygni associated with barley ( R. serrata) Amularia leaf spots, physiological leaf spot) and sugar beet-related sugar beet ( R. beticola ); and cotton, rice, potato, grass, corn, canola, sugar beet, vegetables and various other Plant-associated Rhizoctonia spp., for example, R. solani (root and stem rot) associated with soybean, Rhizoctonia solani (strain) associated with rice Or R. cerealis (Rhizoctonia spring blight) associated with wheat or barley; Rhizopus stolonifer associated with strawberries, carrots, cabbage, vines and tomatoes (black mold, soft rot); Rhynchosporium secalis (burning) associated with barley, rye and triticale; Sarocladium oryzae and leaf sheath spoilage associated with rice ( Sarocladium oryzae ) S. attenuatum ) (sheath rot); with vegetables and field crops (such as rapeseed, sunflower (such as S. sclerotiorum ) and soybeans (such as S. rolfsii or S. sclerotium ( S) . sclerotiorum ))) related genus Sclerotinia s Pp.) (stalk rot or white mold); Septoria spp. associated with a variety of plants, such as soybean-related S. glycines (brown spot), Wheat-related S. tritici (shell sphagnum ) and cereal-associated Helminthosporium ( Sagonospora ) genus nodorum (shell spores) ); vine-related genus Uncinula ( Erysiphe ) (soy powdery mildew, asexual type: Oidium tuckeri ); and corn (eg, corn plaque) S. turcicum , synonymous with Helminthosporium turcicum , and grass-associated genus Setospaeria spp. (leaf blight); and maize (eg S. reiliana) ): smut), sorghum and sugarcane-related Sphacelotheca spp. (smut); Sphaerotheca fuliginea (powder disease) associated with pumpkin; and potato the viral disease related to the potato powdery scab fungus (Spongospora subterranea) (powdery sores Disease); related to the chitin cereals Alternaria (Stagonospora spp), for example, related to the wheat wheat glume blotch pathogen (S. nodorum) (scab spore chitin, teleomorph: glume blotch pathogen (Leptosphaeria nodorum ) [Synonym nodorum (Phaeosphaeria)]); potato (potato canker) related to cancer of potato pathogens (Synchytrium endobioticum);. exterior of the genus (Taphrina spp), for example, associated with the pathogen peach peach leaf (T Deformans ) and T. pruni (plum pocket) associated with plums; black rot fungi associated with tobacco, pear fruit, vegetables, soybeans and cotton (. Thielaviopsis spp) (black root rot), such as root rot (T. basicola) (synonyms Endomycopsis elegant dark (Chalara elegans)); (. Tilletia spp) associated with the cereal species bunt (common Bunt or stinking smut, such as, for example, wheat-related wheat ticks ( T. tritici ) (synonymous wheat smut ( T. caries ), wheat Burning) and T. controversa (dwarf smut); Associated with the barley or wheat brown pellet snow mold of wheat Sclerotinia sclerotiorum (Typhula incarnata) (gray snow mold); (. Urocystis spp) smut genus, for example, associated with the black rye straw black Fringe bacteria (U . occulta) (stem smut); and vegetables (such as beans (e.g. black bean rust pathogen (U. appendiculatus), synonyms bean Uromyces (U. phaseoli)) and sugar beet (e.g. sugar beet rust ( U. betae )) related genus Uromyces spp. (rust); with cereals (eg U. nuda and U. avaenae ), corn (eg U. maydis (corn smut) and sugarcane-related smut ( Ustilago spp.) (naked smut); and apples (such as V. inaequalis ) and Pear-related Venturia spp. (acne); and Verticillium spp. associated with a variety of plants such as fruits and ornamental plants, vines, soft-skin fruits, vegetables, and field crops ( Withered, for example, V. dahliae associated with strawberries, canola, potatoes and tomatoes.

The mixtures of the invention are also suitable for controlling fungal diseases which are present in protected materials such as wood, paper, paint dispersions, fibers or fabrics and in stored products which are protected. The term "protection of material" shall be understood to mean the indication of technical and inanimate materials, such as adhesives, glues, wood, paper and board, fabrics, leather, paint dispersions, plastics, cooling lubricants, fibres or fabrics, to protect against Invasion and destruction of harmful microorganisms such as fungi and bacteria. For the protection of wood and other materials, attention should be paid to the following harmful fungi: ascomycetes, such as Ophiostoma spp., Ceratocystis spp., Aureobasidium Pullulans), Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp. Basidiomycetes, such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp .), Poria spp., Serpula spp. and Tyromyces spp.; deuteromycetes, such as Aspergillus spp., Cladosporium ( Cladosporium spp.), Penicillium spp., Trichorema spp., Alternaria spp., Paecilomyces spp., and Zygomycetes, such as hair Mucor spp., and in addition, in the storage product protection, the following yeast fungi are worth noting: false Saccharomyces (Candida spp.) And S. cerevisiae (Saccharomyces cerevisae).

Generally, "fungicidal effective amount" means a mixture of the invention required to achieve an observable effect of growth (including necrosis, death, delay, prevention, and elimination, destruction) or otherwise reduce the survival and activity of the target organism. Or the amount of the composition containing the mixtures. The fungicidal effective amount can vary for the various mixtures/compositions used in the present invention. The fungicidal effective amount of such mixtures/compositions can also vary depending on such prevailing conditions as the fungicidal effect and duration, weather, target species, location, mode of administration, and the like.

The mixtures according to the invention are especially important for controlling a number of harmful fungi or insects on plant matter such as various cultivated plants, such as cereals, such as wheat, rye, barley, triticale, oats or rice; beets, such as sugar beets or fodder beets; Fruits, such as pomes, stone fruit or soft fruits, such as apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; legumes, such as lentils, Pea, alfalfa or soybean; oil plants such as canola, mustard, olive, sunflower, coconut, cocoa, castor oil, oil coconut, peanut or soybean; cucurbits, such as squashes, cucumber Or melons; fiber plants such as cotton, flax, hemp or jute; citrus fruits such as orange, lemon, grapefruit or mandarins; vegetables such as spinach, lettuce, asparagus, kale, carrots, onions , tomatoes, potatoes, melons or red peppers; laurel plants, such as avocados (avocados), cinnamon or camphor; energy and raw materials, Such as corn, soybean, canola, sugar cane or oil coconut; corn; tobacco; nuts; coffee; tea; banana; vines (table grapes and grape vines); hops; (turf); stevia (also known as stevia); natural rubber plant or ornamental and forestry plant, such as flowers, shrubs, broadleaf trees or evergreen plants, such as conifers; and plant propagation materials, such as seeds, and such plants crop. Preferably, the inventive mixture of the invention is used to control various fungi of the following field crops, such as potato, sugar beet, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybean, canola, beans, sunflower , coffee or sugar cane; fruit; vines; ornamental plants; or vegetables such as cucumbers, tomatoes, beans or pumpkins. More preferably, the inventive mixture of the invention is used to control a variety of fungi of the following field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, canola, beans; And vegetables such as cucumbers, tomatoes, beans or pumpkins.

Preferably, the plant propagation material is treated with the mixture of the invention for controlling cereals such as wheat, rye, barley and oats; numerous fungi of rice, corn, cotton and soybean.

As indicated above, the invention includes a method of enhancing the health of a plant, wherein the plant, the locus where the plant is grown or expected to grow, or the plant propagation material from which the plant is grown is treated via a plant health effective amount of a mixture of the invention.

The term "phytosanitary effective amount" means an amount of the mixture of the invention sufficient to achieve a plant health effect as defined below. Further illustrative information on the amount, mode of administration and appropriate ratios is shown below. In summary, it is well understood by those skilled in the art that this amount can vary widely and depends on various factors such as the treated cultivated plants or materials and climatic conditions.

The term "effective amount" includes the term "phytosanitary effective amount" and/or "fungicidal effective amount" as the case may be.

"Location" means the environment in which plants, plant propagation materials (preferably referred to as seeds), soil, vacant land, materials or fungi are grown or grown.

In the preparation of such mixtures, it is preferred to use the pure active compound, in which other active compounds against pests (such as insecticides, herbicides, fungicides or herbicidal or growth-regulating active compounds or fertilizers) may be added as additional active Component.

The mixtures according to the invention are used for the treatment of fungi with fungicidally effective amounts of active compounds or plants, plant propagation material (preferably referred to as seeds), materials or soils intended to protect against fungal attack. This application can be effected both before and after the fungal infection of the material, plant or plant propagation material, preferably the seed.

Preferably, the mixtures of the invention are used to treat fungi with a fungicidally effective amount of the active compound or plants or soils to be protected from fungal attack by foliar application. Also herein, the application can be accomplished both before and after the fungal infection of the plant.

In the method of combating harmful fungi according to the type of the compound and the intended effect, the application rate of the mixture according to the invention is from 0,1 g/ha to 10000 g/ha, preferably from 2 g/ha to 2500 g/ha, more Good 5 to 1000 g/ha, best 10 to 750 g/ha, especially good 20 to 500 g/ha.

In the context of the present invention, the term plant refers to a whole plant, a part of the plant or a propagation material of the plant.

Plants which can be treated with the mixtures of the invention and propagation materials of such plants include all genetically modified plants or transgenic plants, for example, tolerant to herbicides or fungicides or insecticides due to breeding (including genetic engineering methods) A crop of action, or a plant having an engineered characteristic against an existing plant, which can be produced, for example, by conventional breeding methods and/or establishment of mutants, or by recombinant steps.

For example, the mixtures of the invention may also be administered (eg, seed treatment, spray treatment, in a gully manner or by any other means) to have been bred, mutated or genetically engineered (see http://www.bio.org/speeches) /pubs/er/agri_products.asp) Transformed plants, including (but not limited to) agricultural biological products on the market or under development. Genetically modified plants are plants whose genetic material has been engineered by recombinant DNA technology, which cannot be easily obtained by hybrid breeding, mutation or natural recombination in the natural environment. Typically, one or more genes have been integrated into the genetic material of a genetically engineered plant to enhance certain properties of the plant. Such genetic modifications also include, but are not limited to, targeting post-translationally modified proteins, for example, by glycosylation or polymer addition (such as prenylation, acetamylation or farnesylation or PEG moieties), Oligo- or polypeptide.

For example, plants that have been bred, mutated or genetically engineered have been rendered tolerant to the application of herbicides such as the following specific classes: auxin herbicides such as dicamba or 2,4- D; bleaching herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetamidine lactate synthase (ALS) inhibitors, such as sulfonylurea Or an imidazolinone; an enol-type acetone oxalic acid-3-phosphate synthase (EPSPS) inhibitor, such as glyphosate; a glutamine proline synthase (GS) inhibitor, such as chlorpyrifos ( Glufosinate); protoporphyrinogen-IX oxidase inhibitor; lipid biosynthesis inhibitor, such as an ethylene-based CoA carboxylase (ACCase) inhibitor; or Oxnino due to conventional methods of breeding or genetic engineering (oxynil) (ie, bromoxynil or ioxynil) herbicide. In addition, plants have been resistant to a wide range of herbicides by a variety of genetic modifications, such as simultaneous resistance to galaxin and chlorpyrifos and to herbicides and other classes of herbicides (such as ALS). Resistance to inhibitors, HPPD inhibitors, auxin herbicides or ACCase inhibitors. Such herbicide resistance techniques are described, for example, in Pest Managem. Sci. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326 ; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1185; and references cited therein. Several cultivated plants have been rendered resistant to herbicides by conventional methods of breeding (mutation), for example, Summer rape (Canola, BASF SE, Germany) has resistance to imidazolinones (such as imazamox) or Sunflower (DuPont, USA) has resistance to sulfonylureas such as tribenuron. Genetic engineering methods have been used to confer resistance to cultivated plants such as soybean, cotton, corn, sugar beet and canola to herbicides such as galaxin and chlorpyrifos, some of which are under the trade name (Nike Phosphorus, Monsanto, USA), (imidazole-resistant ketone, BASF SE, Germany) and (resistant to grass, Bayer CropScience, Germany).

In addition, plants are also covered by the use of recombinant DNA technology to synthesize one or more insecticidal proteins, in particular the bacterial genus Bacillus (specifically known as Bacillus thuringiensis) Others, such as δ-endotoxins, such as CryIA (b), CryIA (c), CryIF, CryIF (a2), CryIIA (b), CryIIIA, CryIIIB (b1) or Cry9c; plant insecticidal protein (VIP), For example, VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacterial colonizing nematodes, such as Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxin, Spider toxin, wasp toxin or other insect-specific neurotoxin; toxin produced by fungi, such as streptomyces; plant lectin, such as pea or barley lectin; lectin; protease inhibitor, such as trypsin inhibition Agent, serine protease inhibitor, potato tuber storage protein, cysteine or papain inhibitor; ribosome-inactivated protein (RIP), such as ricin protein, corn-RIP, Phytotoxin (abrin), loofin, saporin or bryodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysone-IDP-glycosyl - transferase, cholesterol oxidase, ecdysone inhibitor or HMG-CoA-reductase; ion channel blockers, such as sodium or calcium channel blockers; juvenile hormone esterase; diuretic hormone receptor (Hai Li Helicokinin receptor; stilbene synthase, bibenzyl synthase, chitinases or glucanase. In the context of the present invention, such insecticidal proteins or toxins are also to be understood to be precisely pre-toxin, mixed proteins, truncated or otherwise modified proteins. Mixed proteins are characterized by a novel combination of protein domains (see, for example, WO 02/015701). Such other toxins or other examples of genetically modified plants from which such toxins can be synthesized are disclosed in, for example, EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 and WO 03/52073. Methods for producing such genetically modified plants are generally well known to those skilled in the art and are described, for example, in the publications mentioned above. The insecticidal proteins contained in the genetically modified plant are such that the plants produce harmful insects (especially against beetles (coleoptera), dipteran insects (Diptera) and all pests selected from the group of arthropods) Moth (Lepidoptera) and a protein resistant to nematodes (C. elegans). Genetically modified plants that can synthesize one or more insecticidal proteins are, for example, described in the above-mentioned publications, and some of which are commercially available, such as YieldGard (Corn cultivar producing Cry1Ab toxin), YieldGard Plus (Corn cultivar producing Cry1Ab and Cry3Bb1 toxin), Starlink (Cry cultivar producing Cry9c toxin), Herculex RW (Corn cultivar producing Cry34Ab1, Cry35Ab1 and enzymatic glufosinate-N-acetyltransferase [PAT]); NuCOTN 33B (cotton cultivar producing Cry1Ac toxin), Bollgard I (cotton cultivar producing Cry1Ac toxin), Bollgard II (cotton cultivar producing Cry1Ac and Cry2Ab2 toxin); VIPCOT (cotton cultivar producing VIP-toxin); NewLeaf (potato cultivar producing Cry3A toxin); Bt-Xtra , NatureGard KnockOut , BiteGard Protecta , Bt11 (for example, Agrisure CB) and Bt176 (from Syngenta Seeds SAS, France) (Corn cultivar producing Cry1Ab toxin and PAT enzyme), MIR604 (from Syngenta Seeds SAS, France) (Corn cultivar producing Cry3A toxin modified variant, see WO 03/018810), MON 863 (available from Monsanto Europe SA, Belgium) (a corn cultivar producing Cry3Bb1 toxin), IPC 531 (available from Monsanto Europe SA, Belgium) (a cotton cultivar producing a modified version of Cry1Ac toxin) And 1507 (available from Pioneer Overseas Corporation, Belgium) (a corn cultivar producing Cry1F toxin and PAT enzyme).

In addition, plants are also covered and one or more proteins can be synthesized by recombinant DNA techniques to enhance the resistance or tolerance of such plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathological mechanism-related proteins" (PR proteins, see, for example, EP-A 392 225), plant resistance genes (for example, potato cultivars, which are derived from Mexican wild potato maroon balls). Potato (Solanum bulbocastanum) Phytophthora infestan exhibits anti-gene action) or T4-lysozyme (for example, it can synthesize resistance to bacteria such as pears and Erwinia amylvora) Protein potato cultivar). Methods for producing such genetically modified plants are generally well known to those of ordinary skill in the art and are described, for example, in the above-referenced publications.

In addition, plants are also covered to increase the productivity of such plants (eg, biomass yield, grain yield, starch content, oil content or protein content) by using recombinant DNA technology to synthesize one or more proteins, for drought, salinity Or other growth-tolerant environmental factors or tolerance to pests and fungal, bacterial or viral pathogens.

In addition, plants are also covered, using recombinant DNA technology to contain substances of modified quality or novel substances, specifically to improve human or animal nutrition, for example, oil crops produce long-chain omega-3 fatty acids that promote health or Unsaturated omega-9 fatty acids (eg Nexera) Canola, DOW Agro Sciences, Canada).

In addition, plants are also covered, by using recombinant DNA technology to contain substances of modified quality or novel substances, specifically to increase the productivity of raw materials, such as increased amylopectin production by potato (eg, Amflora) Potato, BASF SE, Germany).

In yet another embodiment of the invention, the mixtures of the invention are suitable for use in protecting the roots and shoots of seeds and seeds, preferably seeds.

Seed treatment can be carried out in a seed box before planting in the field.

For the purpose of seed treatment, the weight ratio of the mixture of the invention generally depends on the nature of the compound of the mixture of the invention.

Compositions particularly suitable for seed treatment are, for example:

A soluble concentrate (SL, LS)

D Emulsion (EW, EO, ES)

E suspension (SC, OD, FS)

F water dispersible granules and water soluble granules (WG, SG)

G water dispersible powder and water soluble powder (WP, SP, WS)

H gel formulation (GF)

I powder (DP, DS)

The compositions can be applied to plant propagation material, especially seeds, either diluted or undiluted. The composition in question may provide an active substance concentration of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, based on the ready-to-use preparation after 2 to 10 fold dilution. Application can be carried out before or during sowing. Methods of applying or treating agrochemical compounds and compositions thereof to plant propagation materials, especially seeds, are known in the art, and include dressing, coating, pelletizing, spraying, and soaking applications of the propagation material ( And deal with it by gully.) In a preferred embodiment, the compounds or compositions thereof are separately applied to the plant propagation material by methods that do not induce germination (eg, by seed dressing, pelletization, coating, and spraying).

In the treatment of plant propagation material, preferably seed, the rate of application of the mixtures of the invention is generally directed to the formulated product (which typically comprises from 10 to 750 g/l of active substance).

The invention also relates to a propagation product of a plant, and in particular to a composition comprising, or in addition to being, a mixture as defined above or a mixture comprising two or more active ingredients or each providing an active ingredient. A seed of a mixture of two or more of the compositions. The plant propagation material (preferably referred to as a seed) comprises from 0.1 g to 10 kg/100 kg of plant propagation material (preferably referred to as seeds), preferably from 0.1 g to 1 kg/100 kg of plant propagation material (preferably referred to as seeds) The amount of the mixture of the invention.

For example, the ratio of the compound II (by weight) is preferably 0.5 to 200 g / 100 kg of plant propagation material (preferably referred to as seed), more preferably 1 to 50 g / 100 kg of plant propagation material. Preferably, the seed refers to the seed) and preferably 1 to 20 g/100 kg of plant propagation material (preferably referred to as seed).

For example, the ratio of Compound I (by weight) is preferably from 1 to 2000 g/100 kg of plant propagation material (preferably referred to as seed), more preferably from 10 to 1000 g/100 kg of plant propagation material (more preferably) Preferably, the seed refers to a seed, preferably from 25 to 750 g/100 kg of plant propagation material (preferably referred to as seed) and preferably from 50 to 500 g/100 kg of plant propagation material (preferably referred to as seed).

Separate or co-administration of such compounds of the mixtures of the invention is accomplished by spraying or spraying seeds, seedlings, plants or soil before or after seeding the plants or before or after emergence of the plants.

The invention is further illustrated by, but not limited to, the following examples.

The active compounds are formulated in a separate manner into a stock solution having a concentration of 10,000 ppm in dimethyl hydrazine.

Example 1 - Activity of the Phytin against the late blight pathogen

The stock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted to a specified concentration with water. Then, a spore suspension of Phytophthora sojae containing pea juice-based aqueous nutrient medium or DDC medium is added. The disks were placed in a water vapor saturation chamber at a temperature of 18 °C. MTP was measured at 405 nm after 7 days of inoculation using an absorption photometer.

The results are shown in Table 1 below. The measured parameters were compared to the growth of the control group of the inactive compound (100%) and the blank group values of neither the fungus nor the active compound to determine the relative growth of the pathogens in the respective active compounds (in %) ). The expected potency of the active compound mixture was determined using the Colby formula [RS Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared to the observed potency and confirming the inventive mixture Synergies.

Example 2 - Activity against wheat leaf blight caused by wheat leaf blight (Septtr)

The stock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted to a specified concentration with water. Then, a spore suspension of wheat leaf blight bacteria in an aqueous bio-malt or yeast-bactopeptone-glycerol solution is added. The disks were placed in a water vapor saturation chamber at a temperature of 18 °C. MTP was measured at 405 nm after 7 days of inoculation using an absorption photometer.

The results are shown in Table 2 below. The measured parameters were compared to the growth of the control group of the inactive compound (100%) and the blanks of both the fungus and the active compound to determine the relative growth of the pathogens in the respective active compounds (in %) ). The expected potency of the active compound mixture was determined using the Colby formula [RS Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared to the observed potency and confirming the inventive mixture Synergies.

Example 3 - Activity against stem rot caused by Rhizso

The stock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted to a specified concentration with water. Then, a spore suspension of Rhizoctonia solani in an aqueous bio-malt or yeast-bacterial peptone-glycerol solution is added. The disks were placed in a water vapor saturation chamber at a temperature of 18 °C. MTP was measured at 405 nm after 7 days of inoculation using an absorption photometer.

The results are shown in Table 3 below. The measured parameters were compared to the growth of the control group of the inactive compound (100%) and the blanks of both the fungus and the active compound to determine the relative growth of the pathogens in the respective active compounds (in %) ). The expected potency of the active compound mixture was determined using the Colby formula [RS Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared to the observed potency and confirming the inventive mixture Synergies.

Claims (15)

A mixture comprising a synergistically effective amount of the following active ingredients: 1) a fungicidal compound IA selected from the group consisting of dodemorph, carboxin, propineb, and ziram ), a group consisting of benodanil, pentachlorophenol, and phenhalid; or 2) a biological compound IB selected from Bacillus subtilis var. FZB24 (Bacillus subtilis var. amyloliquefaciens FZB24), chitin , Pythium oligandrum DV74 and Reynoutria sachlinensis; and 3) fungicidal compound II, selected from the group of strobilurines. A mixture according to claim 1, which comprises a compound IA and a compound II, wherein the compound IA is selected from the group consisting of carbendazim, sulphonate, methyl zinc epoxi, Yisui, wheat rust, pentachlorophenol and benzoquinone. group. A mixture according to any one of claims 1 or 2, wherein compound IA is carbendazim. The mixture of any one of claims 1 or 2, wherein the compound IA is methylzinc. A mixture according to any one of claims 1 or 2 wherein compound IA is an ear. A mixture of claim 1 which comprises Compound IB and Compound II. The mixture of claim 1 to 6, wherein the fungicidal compound II is selected from the group consisting of azoxystrobin, pyraclostrobin, and trifloxystrobin. A mixture of claim 1 to 6, wherein the fungicidal compound II is a gram-sensitive. The mixture of any one of claims 1 to 8, wherein the ratio by weight is from 1:500 to 500:1. A fungicidal composition comprising a liquid or solid carrier and a mixture according to any one of claims 1 to 9. A method of controlling a fungus, wherein the fungus, its habitat, breeding ground, its location, or a plant, soil or plant propagation material intended to protect against fungal attack is used in an effective amount as claimed in any one of claims 1 to 9. The mixture is processed. A method of enhancing the health of a plant, wherein the plant, the locus where the plant is grown or expected to grow, or the propagation material of the plant is treated with an effective amount of the mixture of any one of claims 1 to 9. A method of protecting a plant propagation material from fungal attack, the method comprising contacting the plant propagation material with a fungicidally effective amount of the mixture of any one of claims 1 to 5. The method of claim 11 to 13, wherein the compounds as defined in any one of claims 1 to 9 are administered simultaneously (i.e., together or separately) or sequentially. A plant propagation material comprising a mixture of any one of claims 1 to 9 in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation material.