EP2104425A2

EP2104425A2 - Ternary fungicide agent combinations

Info

Publication number: EP2104425A2
Application number: EP07846580A
Authority: EP
Inventors: Friedrich Kerz-Moehlendick; Karin Wieczorek; Stefan Dutzmann; Peter Dahmen; Isolde HÄUSER-HAHN
Original assignee: Bayer CropScience AG
Current assignee: Bayer CropScience AG
Priority date: 2006-11-24
Filing date: 2007-11-14
Publication date: 2009-09-30
Also published as: BRPI0719154A2; WO2008061656A2; AR063828A1; WO2008061656A3

Abstract

The novel active agent combinations of spiroxamine, epoxiconazole and tebuconazole or prothioconazole have very good fungicidal properties.

Description

Ternary fungicidal drug combinations

The present invention relates to novel drug combinations containing the known fungicidal active ingredients spiroxamine, epoxiconazole and tebuconazole or prothioconazole, which are very well suited for controlling unwanted phytopathogenic fungi.

It is already known that spiroxamines, epoxiconazoles, tebuconazoles and prothioconazoles have fungicidal properties (compare Pesticide Manual, Edition Edition (1997), pages 79, 466 and 1144. EP-A 0 040 345, EP-A 0 196 038 , EP-A 0 281 842, WO 96/16048). The effectiveness of these substances is good, but leaves at low application rates in some cases to be desired.

It has now been found that containing drug combinations

(1) Spiroxamine {8-tert-butyl-1,4-dioxaspiro [4.5] decan-2-ylmethyl (ethyl) (propyl) amine, Reference: EP-A 0281 842} of the formula (I)

and

(2) Epoxiconazole {(2RS, 3SR) -1- [3- (2-chloro-phenyl) -2,3-epoxy-2- (4-fluoro-phenyl) -propyl] -LH-1, 2,4-triazole, Reference: EP-A 0 196 038} of the formula (II)

and

(3) Tebuconazole [(RS) -lp-chloro-phenyl-4,4-dimethyl-3- (1H-l, 2,4-triazol-1-ylmethyl) -pentan-3-ol, Reference: EP-A 0040345] the formula (JE)

OH ci - ( ^/ y- CH _Γ CH _Γ CC (CH ₃ ) ₃

~~ CH ₂

^ - N or prothioconazole {2- [2- (1-chlorocyclopropyl) -3- (2-chloro-phenyl) -2-hydroxypropyl] -l, 2-dihydro-

3H-l, 2,4-triazole-3-thione, reference: WO 96/16048} of the formula (IV) possess very good fungicidal properties.

This invention therefore comprises the following two ternary mixtures of the active ingredients (A) spiroxamine, epoxiconazole and tebuconazole, (B) spiroxamine, epoxiconazole and prothioconazole.

The active ingredient of the formula (I) is known. The active compounds of the formulas (JS), (IH) and (IV) present in the active ingredient combination according to the invention in addition to the active ingredient of the formula (I) are likewise known (cf., references).

Prothioconazole of the formula (FV) can be present in mercaptoform in addition to the thionoform:

The following active ingredient combinations are also known:

Active ingredient combination comprising compounds of the formula (I) and (IV) (cf., WO 98/47367), and also (SS) and (JST) (cf., WO 03/073851).

If the active ingredients in the active compound combinations according to the invention are present in certain weight ratios, the synergistic effect is particularly pronounced. However, the weight ratios of the active ingredients in the drug combinations can be varied within a relatively wide range.

In general, 1 part by weight of active ingredient of the formula (I)

0.01 to 10 parts by weight, preferably 0.1 to 2 parts by weight, particularly preferably 0.5 to 1.5 parts by weight, very particularly preferably 1 part by weight of active compound of the formula (SS).

0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 0.5 to 1.5 parts by weight, very particularly preferably 1 part by weight of active compound of the formula (Iu) or 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 0.5 to 1.5 parts by weight, very particularly preferably 1 part by weight of active compound of the formula (IV).

In any case, the mixing ratio should be such that a synergistic mixture is obtained.

The active ingredient combination according to the invention, applied simultaneously, together or separately, has a strong microbicidal action and can be used for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.

Fungicides can be used for the control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

By way of example, but not by way of limitation, some pathogens of fungal diseases, which fall under the abovementioned generic terms, are named:

Diseases caused by powdery mildews such as e.g.

Blumeria species, e.g. Blumeria graminis; Podosphaera species, e.g. Podosphaera leucotricha; Sphaerotheca species, e.g. Sphaerotheca fuliginea; Uncinula species, e.g. Uncinula necator;

Diseases caused by causative agents of rust diseases, such as Gymnosporangium species, e.g. Gymnosporangium sabinae; Hemileia species, e.g. Hemileia vastatrix; Phakopsora species, e.g. Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, e.g. Puccinia recondita or Puccinia triticina; Uromyces species, e.g. Uromyces appendiculatus;

Diseases caused by pathogens of the group of Oomycetes, e.g.

Bremia species, such as Bremia lactucae; Peronospora species, such as, for example, Peronospora pisi or P. brasicae; Phytophthora species, such as Phytophthora infestans; Plasmopara species, such as Plasmopara viticola; Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species, such as Pythium ultimum; Leaf spot diseases and leaf wilt caused by eg Alternaria species such as Alternaria solani; Cercospora species, such as Cercospora beticola; Cladiosporum species, such as Cladiosporium cucumerinum; Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium); Colletotrichum species, such as Colletotrichum lindemutonium; Cycloconium species, such as cycloconium oleaginum; Diaporthe species, such as Diaporthe citri; Elsinoe species, such as Elsinoe fawcettii; Gloeosporium species, such as Gloeosporium laeticolor; Glomerella species, such as Glomerella cingulata; Guignardia species, such as Guignardia bidwelli; Leptosphaeria species, such as Leptosphaeria maculans; Magnaporthe species, such as Magnaporthe grisea; Mycosphaerella species, such as Mycosphaerella graminicola; Phaeosphaeria species, such as Phaeosphaeria nodorum; Pyrenophora species, such as Pyrenophora teres; Ramularia species, such as Ramularia collo-cygni; Rhynchosporium species, such as Rhynchosporium secalis; Septoria species, such as Septoria apii; Typhula species, such as Typhula incarnata; Venturia species, such as Venturia inaequalis;

Root and stem diseases caused by e.g.

Corticium species, e.g. Corticium graminearum; Fusarium species, e.g. Fusarium oxysporum;

Gaeumannomyces species, e.g. Gaeumannomyces graminis; Rhizoctonia species, e.g.

Rhizoctonia solani; Tapesia species, such as Tapesia acuformis; Thielaviopsis species, e.g.

Thielaviopsis basicola;

Ear and panicle diseases (including corncob) caused by e.g.

Alternaria species, e.g. Alternaria spp .; Aspergillus species, e.g. Aspergillus flavus;

Cladosporium species, e.g. Cladosporium spp .; Claviceps species, e.g. Claviceps purpurea;

Fusarium species, e.g. Fusarium culmorum; Gibberella species, e.g. Gibberella zeae; Monographella species, e.g. Monographella nivalis;

Diseases caused by fire fungi, e.g.

Sphacelotheca species, e.g. Sphacelotheca reiliana; Tilletia species, e.g. Tilletia caries;

Urocystis species, e.g. Urocystis occulta; Ustilago species, e.g. Ustilago nuda;

Fruit rot caused by e.g.

Aspergillus species, e.g. Aspergillus flavus; Botrytis species, e.g. Botrytis cinerea; Penicillium

Species, e.g. Penicillium expansum; Sclerotinia species, e.g. Sclerotinia sclerotiorum;

Verticilium species such as Verticilium alboatrum; Seed and soil-borne rots and wilting, and seedling diseases caused by, for example, Fusarium species such as Fusarium culmorum; Phytophthora species such as Phytophthora cactorum; Pythium species, such as Pythium ultimum; Rhizoctonia species, such as Rhizoctonia solani; Sclerotium species, such as Sclerotium rolfsii;

Cancers, galls and witches brooms caused by e.g. Nectria species, e.g. Nectria galligena;

Wilt diseases caused by e.g. Monilinia species, e.g. Monilinia laxa;

Deformations of leaves, flowers and fruits caused by e.g. Taphrina species, e.g. Taphrina deformans;

Degenerative diseases of woody plants caused by e.g. Esca species, e.g. Phemmoniella clamydospora;

Flower and seed diseases caused by e.g. Botrytis species, e.g. Botrytis cinerea;

Diseases of plant tubers caused by e.g. Rhizoctonia species, e.g. Rhizottonia solani;

Diseases caused by bacterial agents such as e.g. Xanthomonas species, e.g. Xanthomonas campestris pv. Oryzae; Pseudomonas species, e.g. Pseudomonas syringae pv. Lachrymans; Erwinia species, e.g. Erwinia amylovora;

Preferably, the following diseases of soybean beans can be controlled:

Fungal diseases on leaves, stems, pods and seeds caused by e.g.

Alternaria leaf spot (Alternaria spec. Atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. Truncatum), Brown spot (Septoria glycines), Cercospora leaf spot and blight (Cercospora kikuchii), Choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)) , Dactuliophora leaf spot (Dactuliophora glycines), Downy Mildew (Peronospora manshurica), Drechslera blight (Drechslera glycini), Frogeye leaf spot (Cercospora sojina), Leptosphaerulina Leaf Spot (Leptosphaerulina trifolii), Phyllostica leaf spot (Phyllosticta sojaecola), Powdery Mildew (Phyllosticta sojaecola) Microsphaera diffusa), Pyrenochaeta Leaf Spot (Pyrenochaeta glycines), Rhizoctonia Aerial, Foliage, and Web Blight (Rhizoctonia solani), Rust (Phakopsora pachyrhizi), Scab (Sphaceloma glycines), Stemphylium Leaf Blight (Stemphylium botryosum), Target Spot (Corynespora cassiicola)

Fungal diseases on roots and stem base caused by e.g. Black Root Red (Calonectria crotalariae), Charcoal Red (Macrophomina phaseolina), Fusarium Blight or Wiit, Root Red, and Pod and Collar Red (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitecum, Fusarium equiseti), Mycoleptodiscus Root Red (Mycoleptodiscus terrestris ), Neocosmospora (Neo- cosmospora vasinfecta), Pod and Star Blight (Diaporthe phaseolorum), Star Canker (Diaporthe phaseolorum var. Caulivora), Phytophthora red (Phytophthora megasperma), Brown Star Red (Phialophora gregata), Pythium Red (Pythium Aphanidermatum, Pythium irregular, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), Rhizoctonia Root Red, Star Decay, and Damping Off (Rhizoctonia solani), Sclerotinia Stem Decay (Sclerotinia sclerotiorum), Sclerotinia Southern Blight (Sclerotinia rolfsii), Thielaviopsis Root Red (Thielaviopsis basicola).

The compositions according to the invention are suitable for the protection of all crops cultivated in agriculture, in the greenhouse, in forests or in horticulture. In particular, these are cereal crops (such as wheat, barley, rye, millet and oats), corn, cotton, soy, rice, potatoes, sunflower, bean, coffee, turnip (eg sugar beet and fodder), peanut, vegetables (such as eg tomato, cucumber, onions and salad), wine, fruit (such as apple, banana, pear and cherry), lawn and ornamental plants. In the treatment of seeds, cereals (such as wheat, barley, rye and oats), corn and rice are of particular importance.

The Wirkstofϊkombinationen invention also have a strong tonic effect in plants. They are therefore suitable for mobilizing plant-own defenses against attack by unwanted microorganisms.

In the present context, plant-strengthening (resistance-inducing) substances are to be understood as meaning those substances which are capable of stimulating the defense system of plants in such a way that the treated plants exhibit extensive resistance to these microorganisms with subsequent inoculation with undesired microorganisms.

Undesirable microorganisms in the present case are phytopathogenic fungi, bacteria and viruses. The substances according to the invention can therefore be used to protect plants within a certain period of time after the treatment against the infestation by the said pathogens. The period within which protection is provided extends generally for 1 to 28 days, preferably 1 to 14 days after the treatment of the plants with the active substances or up to 200 days after a seed treatment.

In addition, can be reduced by the treatment according to the invention, the mycotoxin content in the crop and the food and feed produced therefrom. Deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2-toxin, fumonisins, zearalenone, moniliformin, fusarin, diaceotoxyscirpenol (especially), but not exclusively, are the following mycotoxins: DAS), beauvericin, enniatine, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins, which can be caused, for example, by the following fungi: Fusarium spec., Such as Fusarium acuminatum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum (Gibberella zeae), F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F. proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoid, F. langsethiae, F. subglutinans, F. tricinctum, F. verticillioides, and others as well as of Aspergillus spec., Penicillium spec., Claviceps purpurea, Stachybotrys spec. et al

The good plant tolerance of the active compound combinations in the concentrations necessary for controlling plant diseases allows treatment of whole plants (above-ground parts of plants and roots), of planting and seed, and of the soil. The active compound combinations according to the invention can be used for foliar application or as a mordant.

Much of the damage to crop plants caused by phytopathogenic fungi is already produced by infestation of the seed during storage and after introduction of the seed into the soil and during and immediately after germination of the plants. This phase is particularly critical, as the roots and shoots of the growing plant are particularly sensitive and already a small damage can lead to the death of the entire plant. There is therefore a particular interest in protecting the seed and the germinating plant by the use of suitable agents.

The control of phytopathogenic fungi by the treatment of the seed of plants has long been known and is the subject of constant improvement. Nevertheless arise in the

Treating seed a number of problems that can not always be solved satisfactorily. Thus, it is desirable to develop methods for the protection of the seed and the germinating plant, which will allow the additional application of crop protection products after sowing or after sowing

Make the emergence of the plants superfluous or at least significantly reduced. It is also desirable to optimize the amount of the active ingredient used in such a way that the seed and the germinating plant are best protected against attack by phytopathogenic fungi, However, without damaging the plant itself by the active ingredient used. In particular, methods for treating seed should also include the intrinsic fungicidal properties of transgenic plants in order to achieve optimum protection of the seed and the germinating plant with a minimum of pesticide use.

The present invention therefore more particularly relates to a method of protecting seeds and germinating plants from the infestation of phytopathogenic fungi by treating the seed with an agent according to the invention.

The control of phytopathogenic fungi, which damage plants after emergence, takes place primarily through the treatment of the soil and the above-ground parts of plants with pesticides. Due to concerns about the potential impact of crop protection products on the environment and human and animal health, efforts are being made to reduce the amount of active ingredients applied.

One of the advantages of the present invention is that because of the particular systemic properties of the compositions of the invention, treatment of the seed with these agents not only protects the seed itself, but also the resulting plants after emergence from phytopathogenic fungi. In this way, the immediate treatment of the culture at the time of sowing or shortly afterwards can be omitted.

It is likewise to be regarded as advantageous that the mixtures according to the invention can also be used in particular in the case of transgenic seed.

In the context of the present invention, the agent according to the invention is applied to the seed alone or in a suitable formulation. Preferably, the seed is treated in a state where it is so stable that no damage occurs during the treatment. In general, the treatment of the seed can be done at any time between harvesting and sowing. Usually, seed is used which has been separated from the plant and freed from flasks, shells, stems, hull, wool or pulp. For example, seed may be used which has been harvested, cleaned and dried to a moisture content below 15% by weight. Alternatively, seed may also be used which, after drying, e.g. treated with water and then dried again.

In general, care must be taken in the treatment of the seed that the amount of the agent applied to the seed and / or other additives chosen so that the germination of the seeds is not impaired or that the resulting plant is not damaged. This is especially important for drugs that may show phytotoxic effects in certain amounts of Aurwand.

The agents according to the invention can be applied directly, ie without containing further components and without being diluted. In general, it is preferable to apply the agents to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art and are described e.g. in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186 A2.

The active compound combinations according to the invention are also suitable for increasing crop yield. They are also low toxicity and have good plant tolerance.

If appropriate, the active compound combinations according to the invention can also be used in certain concentrations and application rates as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of other active ingredients.

According to the invention, all plants and parts of plants can be treated. In this context, plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant variety rights. Plant parts are to be understood as meaning all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.

The treatment according to the invention of the plants and plant parts with the active substance combinations takes place directly or by acting on their environment, habitat or storage space according to the usual treatment methods, eg by dipping, spraying, spraying, evaporating, atomizing, Sprinkle, spread, pour and in propagating material, especially in seeds, continue by single or multi-layer wrapping.

The compounds of the formula (I) and (D) can be applied simultaneously together or separately or in succession, the sequence in the case of separate application generally having no effect on the control result.

As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, wild-type or plant species obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and plant cultivars and their parts are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above.

It is particularly preferred according to the invention to treat plants of the respective commercially available or in use plant cultivars.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, nutrition), super-additive ("synergistic") effects may also occur as a result of the treatment according to the invention., For example, reduced application rates and / or extensions of the activity spectrum and / or a Enhancement of the effect of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to water or soil salt content, increased flowering efficiency, easier harvest, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products possible, which go beyond the actual expected effects.

The preferred plants or plant varieties to be treated according to the invention which are to be treated include all plants which have obtained genetic material by the genetic modification which gives these plants particularly advantageous valuable properties ("traits".) Examples of such properties are better Plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or soil salt content, increased flowering efficiency, easier harvest, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products, further and particularly highlighted examples For such properties are an increased defense of the plants against animal and microbial pests, such as insects, mites, phytopathogenic fungi, bacteria and / or viruses and increased tolerance of the plants against certain herbicidal active ingredients. Examples of transgenic plants include the important crops such as cereals (wheat, rice), corn, soy, potato, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soy, potato, cotton and rapeseed should be highlighted. Traits which are particularly emphasized are the increased defense of the plants against insects by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA (a), CryΙA (b), CryΙA (c), CryllA, CryHIA, CryIHB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof) are produced in the plants (hereinafter "Bt plants"). Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example "PAT" gene). The genes which confer the desired properties ("traits") can also be present in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soybean varieties and potato varieties sold under the trade names YIELD GARD® (US Pat. corn, cotton, soy), KnockOut® (eg corn), StarLink® (eg corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties which are marketed under the trade names Roundup Ready® (tolerance to glyphosate, eg corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), IMI® ( Tolerance to imidazolinone) and STS® (tolerance to sulfonylureas eg corn). Herbicide-resistant (conventionally grown on herbicide tolerance) plants are also the varieties marketed under the name Clearfield® (eg corn) mentioned. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.

The process for controlling harmful fungi is carried out by the separate or combined application of the compounds of the formula (I) and (S) and at least one further active ingredient selected from the compounds of the formulas (IH) and (IV) or the mixtures of the compounds of the formula (I), (IT) and at least one other active ingredient selected from the compounds of formulas (DT) and (IV) by spraying or dusting the seeds, plants or soils before or after sowing the plants or before or after emergence the plants. The active compound combinations according to the invention can be converted into the customary formulations depending on their respective physical and / or chemical properties, such as solutions, emulsions, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, Active substance-impregnated natural and synthetic substances as well as ultra-fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV-KaIt and warm mist formulations.

These formulations are prepared in a known manner, e.g. by mixing the active compounds or the active compound combinations with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents.

In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

By liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers are: for example, ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. As solid carriers for granules are: for example, broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Suitable emulsifiers and / or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. Suitable dispersants are: for example lignin-sulphite liquors and methylcellulose. Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The active substance content of the application forms prepared from the commercial formulations can vary within wide ranges. The active ingredient concentration of the use forms for controlling animal pests such as insects and acarids may be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight. The application is done in a custom forms adapted to the application forms.

The formulations for controlling undesired phytopathogenic fungi generally contain between 0.1 and 95% by weight of active ingredients, preferably between 0.5 and 90%.

The active compound combinations according to the invention can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, soluble powders, dusts and granules. The application is done in the usual way, e.g. by pouring (drenchen), drip irrigation, splashing, spraying, scattering, dusting, foaming, brushing, spreading, dry pickling, wet pickling, wet pickling, slurry pickling, encrusting, etc.

The active compound combinations according to the invention can be present in commercially available formulations as well as in the formulations prepared from these formulations in admixture with other active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.

When using the active compound combinations according to the invention, the application rates can be varied within a substantial range, depending on the mode of administration. In the treatment of parts of plants, the application rates of active ingredient combination are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In seed treatment, the application rates of active ingredient combination are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the Soil are the application rates of active ingredient combination generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

The active compound combinations can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersing and / or binding or fixing agent, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments, and further processing aids.

The good fungicidal action of the active compound combinations according to the invention is evident from the examples below. While the individual active substances have weaknesses in the fungicidal action, the combinations show an effect that goes beyond a simple action summation.

A synergistic effect is always present in fungicides if the fungicidal action of the active ingredient combinations is greater than the expected effect which applies to a given combination of 2 or 3 active substances according to S.R. Colby ("Calculating Synergistic and Antagonistic Responses of Herbicidal Combinations", Weeds 1967, 15, 20-22) is calculated as follows:

If X means the efficiency when using the active ingredient A in an application rate of m g / ha, Y means the efficiency when using the active ingredient B in an application rate of n g / ha,

Z means the efficiency when using the active ingredient C in an application rate of rg / ha, Ei means the efficiency of the use of the active compounds A and B in application rates of m and ng / ha and E ₂ the efficiency of the use of the active compounds A and B and C. in application rates of m and n and rg / ha,

then for a combination of 2 agents: and for a combination of 3 active ingredients:

"" "" (X - Y + X - Z + Y - Z λ X Y Z

E ₂ = X + Y + Z - \ +

² ^ 100 J 10000

The efficiency is determined in%. It means 0% an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

If the actual fungicidal effect is greater than calculated, the combination is over-additive in its effect, i. there is a synergistic effect. In this case, the actual observed efficiency must be greater than the expected efficiency value (E) calculated from the above formula.

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

Application Examples Example A Erysiphe test (barley) / curative

Solvent: 50 parts by weight of N, N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound or combination of active ingredients with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for curative efficacy, young plants with spores of Erysiphe graminis f.sp. hordei pollinated. 48 hours after inoculation, the plants are sprayed with the preparation of active compound in the stated application rate.

The plants are placed in a greenhouse at a temperature of about 20 ⁰ C and a relative humidity of about 80% to promote the development of mildew pustules. 6 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Example Bl

Pyrenophora teres test (barley) / curative

Solvent: 50 parts by weight N, N-dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound or combination of active ingredients with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for curative efficacy, young plants are sprayed with a conidia suspension of Pyrenophora teres. The plants remain 48 hours at 20 ⁰ C and 100% relative humidity in an incubation cabin. Subsequently, the plants are sprayed with the preparation of active compound in the stated application rate.

The plants are placed in a greenhouse at a temperature of about 20 ⁰ C and a relative humidity of about 80%. 12 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Example B2 Pyrenophora teres test (barley) / protective

Solvent: 50 parts by weight of N, N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active ingredient or combination of active ingredients with the specified amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration or diluted to a commercial

Formulation of active substance or combination of active ingredients with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Pyrenophora teres. The plants remain 48 hours at 20 ⁰ C and 100% relative humidity in an incubation cabin.

The plants are then placed in a greenhouse at a temperature of about 2O ⁰ C and a relative humidity of about 80%.

10 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. Table Bl

Pyrenophora teres test (barley) / protective

gef. = found effect

** calc. = calculated according to the Colby formula

Example C

Erysiphe test (barley) / protective

Solvent: 50 parts by weight of N, N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound or combination of active ingredients with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate.

After the spray coating has dried, the plants are planted with spores of Erysiphe graminis f.sp. hordei pollinated.

Example D

Leptosphaeria nodorum test (wheat) / curative

Solvent: 50 parts by weight of N, N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound or combination of active ingredients with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for curative efficacy, young plants are sprayed with a conidia suspension of Leptosphaeria nodorum. The plants remain 48 hours at 2O ⁰ C and 100% relative humidity in an incubation and are then sprayed with the active ingredient preparation in the specified rate.

The plants are placed in a greenhouse at a temperature of about 15 ° C and a relative humidity of about 80%. 8 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Example E Leptosphaeria nodorum test (wheat) / protective

Solvent: 50 parts by weight of N, N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active ingredient or combination of active ingredients is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain 48 hours at 20 ⁰ C and 100% relative humidity in an incubation cabin. The plants are placed in a greenhouse at a temperature of about 15 ° C and a relative humidity of about 80%.

11 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Example F

Puccinia recondita test (wheat) / curative

Solvent: 50 parts by weight of N, N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for curative efficacy, young plants are sprayed with a condom suspension of Puccinia recondita. The plants remain 48 hours at 20 ⁰ C and 100% relative humidity in an incubation cabin. Subsequently, the plants are sprayed with the preparation of active compound in the stated application rate.

The plants are placed in a greenhouse at a temperature of about 20 ⁰ C and a relative humidity of about 80% to promote the development of rust pustules. 8 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Example G Sphaerotheca fuliginea test (cucumber) / protective Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkyl-aryl-polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. The plants are then placed at about 23 ° C and a relative humidity of about 70% in the greenhouse.

7 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Example H

Alternaria solani test (tomato) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkyl-aryl-polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Alternaria solani. The plants are then placed in an incubation cabin at about 20 ⁰ C and 100% relative humidity. 3 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Example I

Phytophthora infestans test (tomato) / protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkyl-aryl-polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are then placed in an incubation cabin at about 20 ⁰ C and 100% relative humidity.

3 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Example J

Plasmopara viticola test (vine) / protective Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkyl-aryl-polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Plasmopara viticola and then remain for 1 day in an incubation cabin at about 20 ⁰ C and 100% relative humidity. The plants are then placed in the greenhouse for 4 days at about 21 ⁰ C and about 90% humidity. The plants are then moistened and placed in an incubation booth for 1 day. 6 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Example K

Botrytis cinerea - test (bean) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkyl-aryl-polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried, 2 small pieces of agar covered with Botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened chamber at about 20 ⁰ C and 100% relative humidity. 2 days after the inoculation, the size of the infestation spots on the leaves is evaluated. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Example L

Pyricularia oryzae test (in vitro) / microtiter plates

The microtest is performed in microtiter plates with Potato Dextrose Broth (PDB) as a liquid test medium. The application of the active ingredients is carried out as a technical a.i., dissolved in acetone. to

Inoculation, a spore suspension of Pyricularia oryzae is used. After 3 days of incubation in the dark and with shaking (10 Hz), the light transmittance in each filled well of the microtiter plates is determined by means of a spectrophotometer.

Here, 0% means an efficiency equivalent to the growth in the controls, while an efficiency of 100% means that no fungal growth is observed. Example M

Rhizoctonia solani test (in vitro) / microtiter plates

The microtest is performed in microtiter plates with Potato Dextrose Broth (PDB) as a liquid test medium. The application of the active ingredients is carried out as a technical a.i., dissolved in acetone. For inoculation, a mycelial suspension of Rhizoctonia solani is used. After 5 days of incubation in the dark and with shaking (10 Hz), the light transmission in each filled well of the microtiter plates is determined by means of a spectrophotometer. Here, 0% means an efficiency equivalent to the growth in the controls, while an efficiency of 100% means that no fungal growth is observed.

Example N

Gibberella zeae test (in vitro) / microtiter plates

The microtest is performed in microtiter plates with Potato Dextrose Broth (PDB) as a liquid test medium. The application of the active ingredients is carried out as a technical a.i., dissolved in acetone. For inoculation, a spore suspension of Gibberella zeae is used. After 3 days of incubation in the dark and with shaking (10 Hz), the light transmittance in each filled well of the microtiter plates is determined by means of a spectrophotometer.

Here, 0% means an efficiency equivalent to the growth in the controls, while an efficiency of 100% means that no fungal growth is observed.

Example O

Botrytis cinerea test (in vitro) / microtiter plates

The microtest is performed in microtiter plates with Potato Dextrose Broth (PDB) as a liquid test medium. The application of the active ingredients is carried out as a technical a.i., dissolved in acetone. For inoculation, a spore suspension of Botrytis cinerea is used. After 7 days of incubation in the dark and with shaking (10 Hz), the light transmittance in each filled well of the microtiter plates is determined by means of a spectrophotometer. Here, 0% means an efficiency equivalent to the growth in the controls, while an efficiency of 100% means that no fungal growth is observed.

Example P

Fusarium graminearum test (barley) / protective

Solvent: 50 parts by weight of N, N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active ingredient or combination of active ingredients with the specified amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration or diluted a commercial formulation of active ingredient or combination of active ingredients with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Fusarium graminearum.

The plants are placed in a greenhouse under translucent Incubationshauben at a temperature of about 22 ° C and a relative humidity of 100%. 10 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed.

Table P Fusarium graminearum test (barley) / protective

gef. = found effect

** calc. = calculated according to the Colby formula

Claims

claims

1. Fungicidal agent combinations containing

(1) Spiroxamines of Formula (I)

and

(2) epoxiconazoles of the formula (H)

and (3) tebuconazole of the formula (HT)

_y- CH ₂ -CH ₂ - (pC (CH ₃ ) ₃

CH ₂

(in) V-N or

Prothioconazole of the formula (IV)

2. Fungicidal active ingredient combination according to claim 1, wherein the active compounds of the formulas (I), (IT), (Ol) and / or (IV) are used in a synergistically effective mixing ratio.

3. Fungicidal combination of active substances according to one of claims 1 or 2, characterized in that to 1 part by weight of active compound of the formula (I), 0.01 to 10 parts by weight Active ingredient of the formula (II) and 0.05 to 10 parts by weight of active ingredient of the formula (HI) or 0.05 to 10 parts by weight of active compound of the formula (IV) omitted.

4. Use of active compound combinations according to any one of claims 1, 2 or 3 for combating undesirable phytopathogenic fungi.

5. Use of active compound combinations according to one of claims 1, 2 or 3 for the treatment of seed.

6. Use of active compound combinations according to one of claims 1, 2 or 3 for

Treatment of transgenic plants.

7. Use of active compound combinations according to any one of claims 1, 2 or 3 for the treatment of seed transgenic plants.

8. Seed which has been treated with an active ingredient combination according to any one of claims 1, 2 or 3.

9. A method for controlling unwanted phytopathogenic fungi, characterized in that one applies active compound combinations according to any one of claims 1, 2 or 3 to the undesirable phytopathogenic fungi and / or their habitat and / or seed.

10. A process for the production of fungicidal agents, characterized in that mixing active substance combinations according to any one of claims 1, 2 or 3 with extenders and / or surface-active substances.