WO2007131678A1

WO2007131678A1 - Fungicidal active substance combinations

Info

Publication number: WO2007131678A1
Application number: PCT/EP2007/004090
Authority: WO
Inventors: Anne Suty-Heinze; Burkhard SCHÜTZ; Peter Dahmen; Herbert Gayer
Original assignee: Bayer Cropscience Ag
Priority date: 2006-05-16
Filing date: 2007-05-09
Publication date: 2007-11-22
Also published as: AR060913A1; EP2026655A1; DE102006022758A1

Abstract

The present invention relates to novel active substance combinations which consist of at least three fungicidal components A, B and C. A, B and C may be selected among the following compounds: A) the compounds of the general formula (I), where the radicals R<SUP>1</SUP> and R<SUP>2</SUP> have the meanings given in the description, B) azoxystrobin (II), fludioxonil (EI), C) a triazole of the general formula (IV), or triazoxide (V), silthiofam (VI), penthiopyrad (VIT). The active substance combinations are highly suitable for controlling undesirable phytopathogenic fungi. In particular, the active substance combinations according to the invention are suitable for the treatment of seed.

Description

Fungicidal drug combinations

The present invention relates to novel drug combinations consisting of three known fungjziden drugs. These new mixtures are very well suited for controlling unwanted phytopathogenic fungi.

It is already _known that compounds of the general formula (I),

in the

R ^{1 is} trifluoromethyl or difluoromethyl and

R ^{2 are} hydrogen or methyl, have fungicidal properties.

The compounds of general formula (I) are known from e.g. WO 2006/015865 Al.

Specifically, the following compounds of the formula (I-1) - (1-4) may be mentioned.

- -

Furthermore, it is known that azoxystrobin of the formula (II),

which is known from EP 00 382 375, has fungicidal properties.

Furthermore, it is known that fludioxonil of the formula (JS),

which EP 00 206 999 is known, has fungicidal effects.

Furthermore, it is known that _ _

Triazoles of the general formula (IV)

in which

Q is hydrogen or SH,

m is 0 or 1,

R ^{13 is} hydrogen, fluorine, chlorine, phenyl or 4-chlorophenoxy,

R ^{14 is} hydrogen or chlorine,

A ^{4 is} a direct bond, -CH ₂ -, - (CH ₂ ) ₂ -, -O-, for * -CH ₂ -CHR ¹⁷ - or * -CH = CR ¹⁷ -, wherein the bond marked with * the phenyl ring is linked, and

R ¹⁵ and R ¹⁷ together then represent -CH ₂ -CH ₂ -CH [CH (CH ₃ );,] - or -CH ₂ -CH ₂ -C (CH ₃ ) ₂ -,

A ^{5 is} C or Si (silicon),

A ⁴ also represents -N (R ¹⁷ ) - and A ⁵ together with R ¹⁵ and R ^{16 also represents} the group C = NR ¹⁸ , where R ¹⁷ and R ¹⁸ then together represent the group

with the bond marked with * attached to R ¹⁷ ,

R ^{15 is} hydrogen, hydroxy or cyano,

R ¹⁶ represents 1-cyclopropylethyl, 1 -Chlorcyclopropyl, C _r C ₄ alkyl, Ci-C ₆ hydroxyalkyl, C _r C ₄ - alkylcarbonyl, C) -C ₂ haloalkoxy-Ci-C ₂ alkyl, Ci-trimethylsilyl C ₂ alkyl, monofluorophenyl, or phenyl,

R ¹⁵ and R ¹⁶ also together represent -0-CH ₂ -CH (R ¹⁸ ) -O-, -O-CH ₂ -CH (R ¹⁸ ) -CH ₂ -, or

-O-CH- (2-chlorophenyl) - stand, - -

R is hydrogen, C 1 -C ₄ -alkyl or bromine, are fungicidally active.

The formula (IV) includes the following preferred compounds:

Azaconazole (known from DE-A 25 51 560) of the formula (TV-I),

Etaconazole (known from DE-A 25 51 560) of the formula (IV-2),

Propiconazole (known from DE-A 25 51 560) of the formula (F / -3),

Difenoconazole (known from EP-A 0 112 284) of the formula (IV-4),

- -

Bromuconazoles (known from EP-A 0 258 161) of the formula (IV-5),

Cyproconazole (known from DE-A 34 06 993) of the formula (IV-6),

Hexaconazole (known from DE-A 30 42 303) of the formula (IV-7),

Penconazole (known from DE-A 27 35 872) of the formula (IV-8),

Myclobutanil (known from EP-A 0 145 294) of the formula (IV-9),

(IV-9) Tetraconazole (known from EP-A 0 234 242) of the formula (TV-IO),

Flutriafol (known from EP-A 0 015 756) of the formula (IV-11),

Epoxiconazoles (known from EP-A 0 196 038) of the formula (IV-12),

Flusilazole (known from EP-A 0 068 813) of the formula (TV-13),

Simeconazole (known from EP-A 0 537 957) of the formula (TV-14),

(TV-14) Prothioconazole (known from WO 96/16048) of the formula (IV-15),

Fenbuconazole (known from DE-A 37 21 786) of the formula (IV-16),

Tebuconazole (known from EP-A 0 040 345) of the formula (IV-17),

Ipconazole (known from EP-A 0 329 397) of the formula (TV-18),

Metconazole (known from EP-A 0 329 397) of the formula (IV-19),

(IV-19) - -

Triticonazole (known from EP-A 0 378 953) of the formula (TV-20),

Bitertanol (known from DE-A 23 24 010) of the formula (IV-21),

Triadimenol (known from DE-A 23 24010) of the formula (IV-22),

Triadimefon (known from DE-A 22 Ol 063) of the formula (IV-23),

Fluquinconazole (known from EP-A 0 183 458) of the formula (IV-24),

(3-25) quinconazole (known from EP-A 0 183 458) of the formula (IV-25), - -

It is also known that

Triazoxides (known from DE-A 28 02 488) of the formula (V),

fungicidally effective.

It is also known that

Silthiofam (known from WO 96/18631) of the formula (VI),

fungicidally effective.

It is also known that penthiopyrad of formula (VII), known from EP 0 737 682, is fungicidal

is effective.

(Vπ)

The effectiveness of all individual compounds is good, but leaves at low application rates in some cases to be desired. - -

It has now surprisingly been found that mixtures consisting of at least three fungicides (components A, B and C) have synergistic fungicidal effects, that is, the effects of the mixtures is greater than the sum of the individual effects. There is therefore an unpredictable synergistic effect and not just an effect supplement.

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, the combinations according to the invention comprise active substances selected from the categories A, B and C in the mixing ratios specified in the table below, the mixing ratios being based on weight ratios.

Erfϊndungsgemäß are all listed in Table 1 drug mixtures consisting of at least three components A, B and C according to Table 1.

The compounds of the general formula (I) exist in various stereoisomeric forms, which are described by the formulas (I ₁ ), (I ₁₁ ), (I _m ) and (Irv).

The invention, in particular the compounds (1-1), (1-2), (1-3) and (1-4) of component A, comprises all stereoisomeric forms of the general formula (I) which are represented by the formulas ( I ₁ ), (I _n ), (Im) and (Iiv) are represented, in optically pure form or any mixing ratios to each other.

Preferred stereoisomers for racemates of the formula (1-4) are the trans compounds of the formulas (Ii, -4) and ( _Iir 4).

(IHHO -

In the following, preferred ratios of the four stereoisomers (Ii), (In), (Im) and (Ijv) are given to each other.

Preference is given to mixtures in which, in component A, the proportion by weight of the two stereoisomers (I _n ) and (Im) is in total between 65 and 99%.

Preference is furthermore given to mixtures in which, in component A, the proportion by weight of the two stereoisomers (Ii) and (Ipv) is in total between 65 and 99%.

Particular preference is given to mixtures in which, in component A, the proportion by weight of the two stereoisomers (In-4) and (Im-4) is in total between 65 and 99%.

The components A, B and C can be selected from the active ingredients listed in Table 1, wherein all combinations selected from the columns of the table are possible.

TabeUe 1

The following active substances are preferred for the selection of components A, B and C according to the following list:

Component A selected from:

Connection (1-4)

Component B selected from:

Azoxystrobin (IT), Fludioxonil (TtT)

Component C selected from:

Azaconazole (IV-I), etaconazole (IV-2), propiconazole (IV-3), difenoconazole (IV-4), bromuconazole (TV-5), cyproconazole (IV-6), hexaconazole (F / -7), Penconazole (TV-S), -

Myclobutanil (IV-9), tetraconazole (IV-IO), flutriafol (TV-I), epoxiconazole (TV-12), flusilazole (TV-13), simeconazole (TV-14), prothioconazole (TV-15), Fenbuconazole (TV-16), Tebuconazole (TV-17), Ipconazole (TV-18), Metconazole (TV-19), Triticonazole (TV-20), Bitertanol (TV-21), Triadimenol (TV-22), Triadphone (TV-23), fluquinconazole (TV-24), quinconazole (TV-25), triazoxide (V), silthiofam (VI), penthiopyrad (VIT).

Particularly preferred are the following active compound combinations according to Table 2, wherein all combinations selected from the columns of the table are possible.

Table 2

In particular, the following combinations of the preferred components A, B and C may be mentioned. They are listed in Table 3, with one row of the table representing a particularly preferred combination.

Table 3

Blend component component component

A B C connection (1-4)

Fludioxonil (IH) difenoconazole (IV-4)

Azoxystrobin (H) difenoconazole (IV-4)

Fludioxonil (EI) Cyproconazole (IV-6)

Azoxystrobin (ü) Cyproconazole (TV-6)

Fludioxonil (HI) Tebuconazole (IV-17)

Fludioxonil (HI) triticonazole (IV-20)

Fludioxonil (ffl) prothioconazole (JV-15)

- -

- -

Blend component component component

A B C connection (1-4)

16 Azoxystrobin (II) Silthiofam (VI)

17 Azoxystrobin (ET) Tebuconazole (IV-17)

18 Azoxystrobin (II) Triticonazole (IV-20)

19 fludioxonil (IE) penthiopyrad (VH)

20 azoxystrobin (II) penthiopyrad (VII)

Particularly preferred are the following active ingredients for the selection of components A, B and C according to Table 4, wherein all combinations selected from the columns of the table are possible.

Table 4

- -

In particular, the following combinations of the particularly preferred components A, B and C may be mentioned, they are listed in Table 5, wherein one row of the table represents a particularly preferred combination.

Table 5

Blend component component component

A B C connection (1-4)

Fludioxonil (JS) difenoconazole (IV-4)

Azoxystrobin (II) difenoconazole (IV-4)

Fludioxonil (St) Cyproconazole (IV-6)

Azoxystrobin (S) Cyproconazole (IV-6)

Fludioxonil (ST) Tebuconazole (IV-17)

Azoxystrobin (S) tebuconazole (IV-17)

Very particular preference is given to the following active ingredients for the selection of components A, B and C according to Table 6, all combinations selected from the columns of the table being possible. - -

Table 6

In particular, the following combinations of the most preferred components A, B and C may be mentioned, they are listed in Table 7, wherein one row of the table represents a particularly preferred combination.

Table 7

The preferred (a) and most preferred (b) mixing ratios of components A, B and C (A: B: C) are given in Table 8 below:

- -

Table 8

- -

The active compound combinations according to the invention have 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 limitation, some pathogens of fungal and bacterial diseases, which fall under the above-enumerated generic terms, are named:

Diseases caused by powdery mildews such as e.g.

Blumeria species, such as Blumeria graminis;

Podosphaera species, such as Podosphaera leucotricha;

Sphaerotheca species, such as Sphaerotheca fuliginea;

Uncinula species, such as Uncinula necator;

Diseases caused by causative agents of rust diseases such as Gymnosporangium species, such as Gymnosporangium sabinae

Hemileia species, such as Hemileia vastatrix;

Phakopsora species such as Phakopsora pachyrhizi and Phakopsora meibomiae;

Puccinia species, such as Puccinia recondita;

Uromyces species, such as Uromyces appendiculatus;

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

Bremia species, such as Bremia lactucae;

Peronospora species such as Peronospora pisi or P. brassicae;

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 e.g.

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 lindemuthanium;

Cycloconium species such as cycloconium oleaginum;

Diaporthe species, such as Diaporthe citri;

Elsinoe species, such as Elsinoe fawcettii; _ _

Gloeosporium species, such as, for example, 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, for example, 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, such as Corticium graminearum;

Fusarium species such as Fusarium oxysporum;

Gaeumannomyces species such as Gaeumannomyces graminis;

Rhizoctonia species, such as Rhizoctonia solani;

Tapesia species, such as Tapesia acuformis;

Thielaviopsis species, such as Thielaviopsis basicola;

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

Altemaria species such as Alternaria spp .;

Aspergillus species, such as Aspergillus flavus; _.

Cladosporium species such as Cladosporium spp .;

Claviceps species, such as Claviceps purpurea;

Fusarium species such as Fusarium culmorum;

Gibberella species, such as Gibberella zeae;

Monographella species, such as Monographella nivalis;

Diseases caused by fire fungi, e.g.

Sphacelotheca species, such as Sphacelotheca reiliana;

Tilletia species, such as Tilletia caries;

Urocystis species, such as Urocystis occulta;

Ustilago species such as Ustilago nuda;

Fruit rot caused by e.g.

Aspergillus species, such as Aspergillus flavus;

Botrytis species, such as Botrytis cinerea;

Penicillium species such as Penicillium expansum;

Sclerotinia species, such as Sclerotinia sclerotiorum;

Verticilium species such as Verticilium alboatrum;

Seed and soil rots and wilts, as well as seedling diseases caused by e.g.

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, such as Nectria galligena;

Wilt diseases caused by e.g.

Monilinia species, such as Monilinia laxa;

Deformations of leaves, flowers and fruits caused by e.g.

Taphrina species, such as Taphrina deformans;

Degenerative diseases of woody plants caused by e.g.

Esca species, such as Phaemoniella clamydospora;

Flower and seed diseases caused by e.g.

Botrytis species, such as Botrytis cinerea;

Diseases of plant tubers caused by e.g.

Rhizoctonia species, such as Rhizoctonia solani;

Diseases caused by bacterial agents such as e.g.

Xanthomonas species, such as Xanthomonas campestris pv. Oryzae;

Pseudomonas species, such as Pseudomonas syringae pv. Lachrymans;

Erwinia species, such as 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 (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 semitectum, Fusarium equiseti), Mycoleptodiscus Root Red (Mycoleptodiscus terrestris),

Neocosmospora (Neocosmopspora vasinfecta), Pod and Star Blight (Diaporthe phaseolorum), Stem

Canker (Diaporthe phaseolorum var. Caulivora), Phytophthora red (Phytophthora megasperma),

Brown Stem Red (Phialophora gregata), Pythium Red (Pythium aphanidermatum, Pythium irregular, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), Rhizoctonia Root Red, Stem Decay, and Damping Off (Rhizoctonia solani), Sclerotinia Stem Decay (Sclerotinia sclerotiorum) .

Sclerotinia Southern Blight (Sclerotinia rolfsii), Thielaviopsis Root Red (Thielaviopsis basicola).

The good plant tolerance of the active substance combinations in the concentrations necessary for combating plant diseases makes it possible to treat whole plants (above-ground parts of plants and roots), planting and seed, and the soil. The erfϊndungs- proper drug combinations can be used for foliar application or as a mordant.

The good plant tolerance of the usable active ingredients in the necessary concentrations for controlling plant diseases allows treatment of the seed. The active compounds according to the invention can thus be used as mordants.

Much of the damage to crops 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 even minor 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, which damage plants after emergence, takes place primarily through the treatment of the soil and the above-ground parts of plants with plant protection agents. 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. 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, there are a number of problems in the treatment of seeds that can not always be satisfactorily resolved. Thus, it is desirable to develop methods for protecting the seed and the germinating plant, which eliminate or at least significantly reduce the additional application of crop protection agents after sowing or after emergence of the plants. It is also desirable to optimize the amount of the active ingredient used in such a way that the seed and the germinating plant is best protected against attack by phytopathogenic fungi, but 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 invention also relates to the use of the seed treatment agents of the invention for protecting the seed and the germinating plant from phytopathogenic fungi.

Furthermore, the invention relates to seed which has been treated with an agent according to the invention for protection against phytopathogenic fungi.

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.

The preferred plants or plant cultivars to be treated according to the invention include all plants which have obtained genetic material by the genetic engineering 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 dry or water or Bodensalzgehalt, increased flowering, ease of harvesting, acceleration of maturity, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products. Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance; 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 formed in the plants, in particular those produced by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA (a), CryIA (b), CryΙA (c), CryllA, CrylEA, CryIDB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof) are produced in the plants (hereinafter, 3t 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") may also be present in combinations with one another in the transgenic plants Examples of "3t plants" are corn, cotton, soy and potato varieties sold under the trade names YIELD GARD® (eg maize , Cotton, soybean), 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 sold 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 compositions according to the invention are suitable for the protection of seeds of any plant variety used in agriculture, in the greenhouse, in forests or in horticulture. In particular, these are seeds of cereals (such as wheat, barley, rye, millet and oats), corn, cotton, soy, rice, potatoes, sunflower, bean, coffee, turnip (eg sugar beet and fodder beet), peanut, rapeseed, Canola and vegetables (such as tomato, cucumber, onions and salad), lawn and ornamental plants. Of particular importance is the treatment of the seeds of cereals (such as wheat, barley, rye and oats), potato, soy and rice.

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 the

Generally, the treatment of the seed at any time between the harvest and the

Sowing done. Usually, seed is used which is separate from the plant and from

Flasks, shells, stems, shell, wool or pulp was freed. So can for example

Seed that 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 and / or other additives applied to the seed is chosen so that germination of the seed is not impaired or the resulting plant is not damaged. This is especially important for active ingredients, which can show phytotoxic effects at certain application rates.

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.

The active compound combinations according to the 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 induced generally extends from 1 to 300 days, preferably 1 to 100 days and more preferably 1-20 days after the treatment of the plants with the active ingredients or after sowing.

The good plant compatibility of the active compound combinations in the concentrations necessary for controlling plant diseases allows a treatment of aboveground plant parts, of plant and seed, and the soil.

In this case, the active compound combinations according to the invention can be used particularly successfully for combating cereal diseases, such as, for example, against Tilletia caries, Ustilago nuda and diseases in dicotyledonous plants, e.g. against Rhizoctonia, Helminthosporium or Fusarium species.

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.

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 ingredient combinations is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, eg by dipping, spraying, evaporating, atomizing, spreading, spreading and propagating material, in particular in the case of seeds single or multi-layer coating. In this case, the drug combinations before treatment by _

Mixing of the individual active ingredients are produced or the treatment is carried out successively by using the said active ingredients.

In addition, the active compound combinations according to the invention also have very good antifungal effects. They have a very broad antimycotic spectrum of activity, in particular against dermatophytes and yeasts, mold and diphasic fungi (eg against Candida species such as Candida albicans, Candida glabrata) and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, microsporon species such as Microsporon canis and audouinii. The list of these fungi is by no means a limitation of the detectable mycotic spectrum, but has only an explanatory character.

The active compound combinations can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The application is done in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to dispense the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil. It can also be the seed of the plants to be treated.

When using the active compound combinations according to the invention as fungicides, the application rates can be varied within a relatively wide range, depending on the mode of application. In the treatment of parts of plants, the application rates of active ingredient are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the application rates of active ingredient 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, the application rates of active ingredient are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

The listed plants can be treated particularly advantageously according to the invention with the Wirkstoffinischungen. The preferred ranges given above for the active compounds or mixtures also apply to the treatment of these plants. Particularly emphasized is the plant treatment with the compounds or mixtures specifically mentioned in the present text.

The active compound combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, active substance-impregnated natural and synthetic substances and superfine encapsulations in polymers substances. _

These formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, if appropriate using 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 and 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.

Suitable solid carriers are: e.g. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules are suitable: e.g. crushed 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 stalks; suitable emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin sulphite liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic powders, granules or latexes such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids such as cephalins and lecithins and synthetic phospholipids may be used in the formulations. 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 formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%. 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. The insecticides include, for example, phosphoric esters, carbamates, carboxylic esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, among others

A mixture with other known active substances, such as herbicides or with fertilizers and growth regulators is possible.

The treatment according to the invention of the plants and plant parts with the active ingredients is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, spreading, spreading and in propagation material, in particular in seeds, further by single or multi-layer wrapping.

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), the treatment according to the invention may also give rise to superadditive ("synergistic") effects, 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 harvest value of the harvested products, higher shelf life and / or workability of the harvest products possible, which go beyond the expected effects actually. The listed plants can be treated particularly advantageously according to the invention with the active ingredient mixtures according to the invention. The preferred ranges given above for the mixtures also apply to the treatment of these plants. Particularly emphasized is the plant treatment with the mixtures specifically mentioned in the present text.

The good fungicidal action of the active compound combinations according to the invention is evident from the following example. 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 when the fungicidal action of the active ingredient combinations is greater than the sum of the effects of the individually applied active ingredients.

Example A

The expected effect for a given combination of 2 or 3 drugs can be calculated according to S.R. Colby ("Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 1967, 15, 20-22) as follows:

If

X means the efficiency when using the active ingredient A in an application rate of m parts per million (ppm),

Y means the efficiency when using the active ingredient B in an application rate of n ppm,

Z means the efficiency when using the active ingredient C in an application rate of r_ppm,

Eg means the efficiency of the use of the active ingredients A and B in application rates of m and n ppm means and

E2 means the efficiency when using the active compounds A and B and C at application rates of m and n and r ppm,

then

X - Y

E _x = X + Y -

100

and for a combination of 3 agents:

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, ie there is a synergistic effect. In this case, the actual must observed efficiency be greater than the value calculated from the above formula for the expected efficiencies Ej or E2.

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

Pyricularia orvzae 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 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.

- Jo -

Example B

A synergistic effect is always present in fungicides when the fungicidal action of the active ingredient combinations is greater than the sum of the effects of the individually applied active ingredients. The expected effect for a given combination of 2 or 3 drugs can be calculated according to S.R. Colby ("Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 1967, 15, 20-22) as follows:

If

X means the efficiency when using the active substance 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 r_g / ha,

Ε \ means the efficiency of the use of the active compounds A and B in application rates of m and n g / ha, and

E2 means the efficiency when using the active compounds A and B and C at application rates of m and n and r g / ha,

then

X - Y

E = X + Y -

100

and for a combination of 3 agents: ^

(XY + XZ + YZ) XYZE ₂ = X + Y + Z +

100 10 000

The efficiency is determined in%. It means O% an efficiency equal 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 value calculated for the expected efficiencies Ej or Ej-calculated from the formula given above.

Microdochium nivale test (wheat) / protective agents

Solvent: 50 parts by weight of NJV-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 with the stated 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 Microdochium nivale.

The plants are placed in a greenhouse under translucent Incubationshauben at a temperature of about 10 ⁰ C and a relative humidity of about 100%.

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.

- -

Table Bl

Microdochium nivale test (wheat) / protective

gef. = found effect ber. = calculated according to the Colby formula effect

Table B2

Microdochium nivale test (wheat) / protective

gef. = found effect ber. = calculated according to the Colby formula effect

Claims

- Patent claims

1. Wirkstofϊkombination containing:

A) at least one compound of the general formula (I),

in the

R ^{1 is} trifluoromethyl or difluoromethyl and

R ^{2 is} hydrogen or methyl and

B) at least one compound selected from the group

Azoxystrobin of the formula (H)

or

Fludioxonil of the formula (EI),

such as at least one compound selected from the group

a triazole of the general formula (IV)

in which

Q is hydrogen or SH,

m is 0 or 1,

R ^{13 is} hydrogen, fluorine, chlorine, phenyl or 4-chlorophenoxy,

R ^{14 is} hydrogen or chlorine,

A ^{4 is} a direct bond, -CH ₂ -, - (CH ₂ ) ₂ -, -O-, for "" -CH ₂ -CHR ¹⁷ - or "" -CH = CR ¹⁷ -, wherein the one marked with * Bond is linked to the phenyl ring, and

R ¹⁵ and R ¹⁷ together then represent -CH ₂ -CH ₂ -CH [CH (CH ₃ );,] - or -CH ₂ -CH ₂ -C (CH ₃ );, -,

A ^{5 is} C or Si (silicon),

where the bond marked with *

It ^ is connected,

R ^{15 is} hydrogen, hydroxy or cyano, R ¹⁶ represents 1-cyclopropylethyl, 1 -Chlorcyclopropyl, Ci-C ₄ alkyl, C ₁ -C ₆ -Hy (IrOXy- alkyl, C ₁ -C ₄ alkylcarbonyl, C | -C ₂ haloalkoxy-Ci-C ₂ alkyl, trimethylsilyl-C ₁ -C ₂ -alkyl, monofluorophenyl, or phenyl,

-O-CH- (2-chlorophenyl) - stand,

R ^{18 is} hydrogen, C _r C ₄ alkyl or bromine or

Triazoxide (V), silthiofam (VI), penthiopyrad (VII)

2. active compound combinations according to claim 1, in which the component

A is the same as compound (1-4)

is, the component

B is selected from azoxystrobin and fludioxonil as well as the component

C is selected from azaconazole (IV-I), etaconazole (FV-2), propiconazole (IV-3), difenoconazole (IV-4), bromuconazole (FV-5), cyproconazole (TV-6), hexaconazole

(IV-7), penconazole (IV-8), myclobutanil (TV-9), tetraconazole (IV-IO), flutriafol

(IV-I l), epoxiconazoles (IV-12), flusilazoles (IV-13), simeconazoles (IV-14),

Prothioconazole (IV-15), fenbuconazole (IV-16), tebuconazole (IV-17), ipconazole

(IV-18), metconazole (IV-19), triticonazole (IV-20), bitertanol (IV-21), triadimenol (IV-22), triadimefon (IV-23), fluquinconazole (IV-24), quinconazole

(IV-25), triazoxide (V), silthiofam (VI), penthiopyrad (VII)

3. active substance combinations according to claim 2, in which the component C is selected from

Difenoconazole (IV-4), Cyproconazole (IV-6), Tebuconazole (IV-17), Triticonazole (IV-20), Prothioconazole (IV-15), Triadimenol (IV-22), Fluquinconazole (F / -24), Triazoxide (V), silthiofam (VI),), penthiopyrad (VIT). - -

4. Active substance combinations containing one of the combinations according to Table 3.

Table 3

- -

Blend component component component

A B C connection (1-4)

Fludioxonil (IH) Triadimenol (IV-22)

Fludioxonil (IS) fluquinconazole (IV-24)

10 fludioxonil (ST) triazoxide (V)

11 fludioxonil (ST) silthiofam (VI)

12 Azoxystrobin (S) Prothioconazole (IV-15)

13 Azoxystrobin (S) Triadimenol (F / -22)

14 Azoxystrobin (S) Fluquinconazole (IV-24)

15 azoxystrobin (S) triazoxide (V)

- -

5. active substance combinations containing one of the combinations according to Table 5.

Table 5

- -

6. Active substance combinations containing one of the combinations according to Table 7.

Table 7

- -

7. Synergistic drug combinations containing an active ingredient combination according to any one of claims 1 to 6.

8. Use of active compound combinations according to one of claims 1 to 6 for the Bekpfung unwanted phytopathogenic fungi.

9. A method for controlling unwanted phytopathogenic fungi, characterized in that one applies active compound combinations according to claim 1 on the unwanted phytopathogenic fungi and / or their habitat and / or seed.

10. A process for the preparation of active compound combinations, characterized in that an agent according to one of claims 1 to 6 with surface-active agents and / or

Extenders mixed.

11. Use of active compound combinations according to any one of claims 1-6 for the treatment of seed.

12. Use of active compound combinations according to any one of claims 1-6 for the treatment of transgenic plants.

13. Use of active compound combinations according to any one of claims 1-6 for the treatment of seed transgenic plants.

14. Seed which has been treated with an active ingredient combination according to any one of claims 1-6.

15. active ingredient combinations according to claim 2, in which in the component A, the proportion of the two stereoisomers (In-4) and (Im-4)

65 to 99% by weight of the active ingredient.