WO2005117586A1

WO2005117586A1 - Fungicidal active substance combination

Info

Publication number: WO2005117586A1
Application number: PCT/EP2005/005779
Authority: WO
Inventors: Klaus Eckstein; Andree-Georg Girg; Ludger Triebus
Original assignee: Bayer Cropscience Ag
Priority date: 2004-06-04
Filing date: 2005-05-30
Publication date: 2005-12-15
Also published as: DE102004027430A1; EP1755389A1

Abstract

Disclosed are active substance combinations containing an oxime ether derivative of formula (I) (trifloxystrobin), phosphonic acid or a phosphonate such as fosetyl-Al, and tolylfluanide, as well as the use thereof as fungicides.

Description

Fungicidal active ingredient combination

The present invention relates to a new active ingredient combination which contains a known oxime ether derivative, a phosphonate and a known sulfamide derivative and is very suitable for combating phytopathogenic fungi. It is already known that the oxime derivative 2- [α - {[(α-methyl-3-trifluoromethyl-benzyl) imino] - oxy} -o-tolyl] -glyoxylate methyl ester-0-methyloxime with the common name Trifloxystrobin has fungicidal properties (cf. EP-A-0 460 575). The effectiveness of this substance is good, but leaves something to be desired in some cases at low application rates. The preparation of this compound is also known from EP-A-0 460 575.

It is also known that phosphonic acid and its derivatives (phosphonates), such as the phosphonate ethyl hydrogen phosphonate with the common name fosetyl aluminum, have fungicidal properties (cf. FR-A-2254276). The effectiveness of these substances is good; however, in some cases it leaves something to be desired when the application rates are low. The preparation of this compound is also known from FR-A-2254276.

It is also known that the sulfamide derivative l, l-dichloro-N - [(dimethylamino) sulfonyl] -l-fluoro-N- (4-methylphenyl) with the common name tolylfluanid has fungicidal properties (cf. DE-A -1,193,498). The effectiveness of this substance is good, but it leaves something to be desired in some cases at low application rates. The preparation of this compound is also known from DE-A-1 193498.

From WO 00/36916 the active ingredient combination of trifloxystrobin and fosetyl aluminum is also known.

Since the ecological and economic requirements for modern fungicides are constantly increasing, for example in terms of activity spectrum, toxicity, selectivity, application rate, residue formation and inexpensive to produce, and also e.g. Problems with resistance may arise, the constant task is to develop new fungicides that have advantages over the known ones, at least in some areas.

The invention relates to combinations of active substances which solve the stated problems at least in part.

It has now been found that the new active ingredient combination, the 2- [α - {[(α-methyl-3-trifluoromethyl-benzyl) imino] oxy} -o-tolyl] -glyoxylate methyl ester-0-methyloxime of the formula (I) strobin)

and

(1) phosphonic acid or a phosphonate (of formula (II)

H - P (OR ³ ) ₂ (H)

in which

R is the same or different for H, 1 / / _n M Λ fn ⁿ + or (Cj-C ₄ ) alkyl and

M stands for a cation;

and

(2), l-dichloro-N - [(dimethylamino) sulfonyl] -l-fluoro-N- (4-methylphenyl) (reference: DE-A-1193498) of the formula (ffl)

luanid)

contains, has very good fungicidal properties.

Surprisingly, the fungicidal activity of the active compound combination according to the invention is significantly higher than the sum of the effects of the individual active compounds or the known active compound combination. So there is an unforeseeable, real synergistic effect and not just an addition. In addition to phosphonic acid, preferred fungicides of the formula (IT) are HP (0) (OH) ₂ ), (Ha), their salts of the formula (ü),

H - P - OFT (Mb) OV "M

in which

R ^{3 '} H or 7 "M ^{n +} and

M denotes an inorganic or organic cation, preferably Al or an alkali or alkaline earth metal, particularly preferably Na, K or Al,

or mixed ester salts of the formula (He),

O 3 "

H - P - OR (llc) OV _n M ^{n +}

in which

R ³ (-CC ₄ ) alkyl, preferably C ₂ H ₅ , and

M is an inorganic or organic cation, preferably Al or an alkali or alkaline earth metal, particularly preferably Al, Na or K.

The compounds are very particularly preferred

O II (11-1) H - P (OH) ₂ H - P - 0 AI (H-4) O II (II-2) OC ₂ H ₅ H - P (OH) I and OK O o II (II -3) H - P - ONa (H-5) H - P (OK) ₂ OC ₂ H ₅ especially the compound (II-4) (fosetyl-Al).

In the literature, phosphonic acid is also referred to as phosphorous acid (actually tautomer of phosphonic acid, P (OH) ₃ ), its salts accordingly as (secondary) phosphites.

The listed active ingredients, especially trifloxystrobin. Phosphonic acid, its mono- and potassium salt, fosetyl-Al and tolylfluanid are commercially available. Information on reference and possibly synthesis can be found in C.D.S. Toniin, The Pesticide Manual, 13th edition, British Crop Protection Council, Farnham 2003 and the literature cited therein. The active ingredient of the formula (I) is known (cf., for example, EP-A-460 575).

It can be seen from the structural formula for the active ingredient of the formula (I) that the compound can exist as an E or Z isomer. The compound (I) can therefore be present as a mixture of different isomers or in the form of a single isomer. Preferred is the compound of formula (I) in which it is present as an E isomer

The active ingredient combination according to the invention contains the active ingredients of the formulas (I), (11) and (Hl). It can also contain other fungicidally active admixing components.

Preferred active ingredient combinations of active ingredients of the formulas (I), (II) and (in) are those listed below:

(a) (i) / (π-i) / (iri), (b) (i) / (π-2) / (m), (c) (i) / (π-3) / (m) , (d) (i) / (π-4) / (πi), (e) (i) / (π-5) /

Of these, the combination d (trifloxystrobin, fosetyl-Al and tolylfluanid) is particularly preferred. If the active substances are present in the active substance combinations according to the invention in certain weight ratios, a synergistic effect is particularly evident. However, the weight ratios of the active ingredients in the active ingredient combinations can be varied within a relatively wide range. The weight ratios of the compounds of the formulas (I): (H) or (II) a: (ILT) can be, for example, in the range between 1: 2: 4 and 1: 50: 100. The weight ratios of the compounds of the formulas (I): (IT) or (H) a: (III) are preferably in the range between 1: 8:16 and 1:12:48.

The active compound combinations according to the invention have a strong microbicidal action and can be used to control undesirable microorganisms, such as fungi and bacteria, in crop protection and in material protection.

Fungicides can be used in crop protection, for example to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deutromycetes.

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

The active substance combinations according to the invention have very good fungicidal properties and can be used to control phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes etc.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae; Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans; Erwinia species, such as, for example, Erwinia amylovora; Diseases caused by powdery mildew pathogens such as Blumeria species, such as, for example, Blumeria graminis;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Uncinula species, such as, for example, Uncinula necator; Diseases caused by rust pathogens such as Gymnosporangium species, such as, for example, Gymnosporangium sabinae He ileia species, such as, for example, Hemileia vastatrix; Phakopsora species, such as, for example, Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, such as, for example, Puccinia recondita; Uromyces species, such as, for example, Uromyces appendiculatus; Diseases caused by pathogens from the Oomycetes group, such as, for example, Bremia species, such as, for example, Bremia lactucae; Peronospora species, such as, for example, Peronospora pisi or P. brassicae;

Phytophthora species, such as, for example, Phytophthora infestans; Plasmopara species, such as, for example, Plasmopara viticola;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or

Pseudoperonospora cubensis;

Pythium species, such as, for example, Pythium ultimum;

Leaf blotch diseases and leaf wilting, caused by e.g. Alternaria species, such as, for example, Alternaria solani;

Cercospora species, such as, for example, Cercospora beticola;

Cladiosporum species, such as, for example, Cladiosporium cucumerinum;

Cochliobolus species, such as, for example, Cochliobolus sativus

(Conidial form: Drechslera, Syn: Helminthosporium); Colletotrichum species, such as, for example, Colletotrichum indemuthanium;

Cycloconium species, such as, for example, Cycloconium oleaginum;

Diaporthe species, such as, for example, Diaporthe citri;

Elsinoe species, such as, for example, Elsinoe fawcettii;

Gloeosporium species, such as, for example, Gloeosporium laeticolor; Glomerella species, such as, for example, Glomerella cingulata;

Guignardia species, such as, for example, Guignardia bidwelli;

Leptosphaeria species, such as, for example, Leptosphaeria maculans;

Magnaporthe species, such as, for example, Magnaporthe grisea; Mycosphaerella species, such as, for example, Mycosphaerelle graminicola; Phaeosphaeria species, such as, for example, Phaeosphaeria nodorum; Pyrenophora species, such as, for example, Pyrenophora teres; Ramularia species, such as, for example, Ramularia collo-cygni; Rhynchosporium species, such as, for example, Rhynchosporium secalis; Septoria species, such as, for example, Septoria apii; Typhula species, such as, for example, Typhula incarnata; Venturia species, such as, for example, Venturia inaequalis; Root and stem diseases caused, for example, by Corticium species, such as, for example, Corticium graminearum;

Fusarium species, such as, for example, Fusarium oxysporum;

Gaeumannomyces species, such as, for example, Gaeumannomyces graminis;

Rhizoctonia species, such as, for example, Rhizoctonia solani;

Tapesia species, such as, for example, Tapesia acuformis; Thielaviopsis species, such as, for example, Thielaviopsis basicola;

Ear and panicle diseases (including corn on the cob), caused by e.g.

Alternaria species, such as, for example, Alternaria spp .;

Aspergillus species, such as, for example, Aspergillus flavus;

Cladosporium species, such as, for example, Cladosporium spp .; Claviceps species, such as, for example, Claviceps purpurea;

Fusarium species, such as, for example, Fusarium culmorum;

Gibberella species, such as, for example, Gibberella zeae;

Monographella species, such as, for example, Monographella nivalis;

Diseases caused by smut such as Sphacelotheca species, such as, for example, Sphacelotheca reiliana;

Tilletia species, such as, for example, Tilletia caries;

Urocystis species, such as, for example, Urocystis occulta;

Ustilago species, such as, for example, Ustilago nuda; Fruit rot caused by eg Aspergillus species, such as Aspergillus flavus; Botrytis species, such as, for example, Botrytis cinerea; Penicillium species, such as, for example, Penicillium expansum; Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

* Verticilium species, such as, for example, Verticilium alboatrum; Seed and soil-borne rot and wilt as well as seedling diseases caused by, for example, Fusarium species, such as, for example, Fusarium culmorum; Phytophthora species, such as, for example, Phytophthora cactorum; Pythium species, such as, for example, Pythium ultimum; Rhizoctonia species, such as, for example, Rhizoctonia solani; Sclerotium species, such as, for example, Sclerotium rolfsii; Cancers, galls and witches' broom caused by, for example, Nectria species, such as, for example, Nectria galligena; Wilting diseases caused by, for example, Monilinia species, such as, for example, Monilinia laxa; Deformations of leaves, flowers and fruits caused, for example, by Taphrina species, such as, for example, Taphrina deformans; Degenerative diseases of woody plants, caused, for example, by Esca species, such as, for example, Phaemoniella clamydospora; Flower and seed diseases caused, for example, by Botrytis species, such as, for example, Botrytis cinerea; Diseases of plant bulbs caused, for example, by Rhizoctonia species, such as, for example, Rhizoctonia solani; The active compounds according to the invention also have a very good strengthening effect in plants. They are therefore suitable for mobilizing the plant's own defenses against attack by unwanted microorganisms. Plant-strengthening (resistance-inducing) substances are to be understood in the present context as substances which are able to stimulate the defense system of plants in such a way that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with undesired microorganisms.

Undesired microorganisms are to be understood in the present case as phytopathogenic fungi and bacteria. The substances according to the invention can thus be used to protect plants against attack by the pests mentioned within a certain period of time after the treatment. The period within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days, after the plants have been treated with the active compounds.

The active compound combinations according to the invention are particularly suitable for combating Phytophthora infestans and Plasmopara viticola.

The active ingredient combinations according to the invention are particularly suitable for use in viticulture.

The active ingredient combinations according to the invention are also particularly suitable for use in vegetable cultivation.

The fact that the active ingredient combinations are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil. The active compound combinations according to the invention can be used for leaf application or as a mordant.

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

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean 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 cultivars which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of the plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

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

Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with new properties (“traits”) which have been grown both by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, bio and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, growing season, nutrition), the treatment according to the invention can also cause superadditive ("synergistic") effects. For example, reduced application rates and / or widening of the spectrum of action and / or an increase in the action 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 performance , easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher storability and / or workability of the harvested products possible, which go beyond the effects to be expected.

The preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which, through the genetic engineering modification, have received genetic material 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 to water or soil salt content, increased flowering performance, easier harvesting, accelerated ripening, 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 highlighted examples of such properties are an increased defense against the plant against animal and microbial pests, such as insects, mites, phytopathogenic fungi, bacteria and / or viruses, as well as an increased tolerance of the plants to certain herbicidal active ingredients. Examples of transgenic plants are the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes and cotton and rapeseed are highlighted. The traits are particularly emphasized as the increased defense of the plants against insects by toxins arising in the plants, in particular those which are caused by the genetic material from Bacillus Thuringenisis (eg by the genes CryΙA (a), CryΙA (b ), CryΙA (c), CryllA, CrylHA, CryIITB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter "Bt plants"). The properties ("traits") also particularly emphasize the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. The traits that are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example the “PAT” gene). The genes conferring the desired properties ("traits") can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soy varieties and potato varieties that are marketed under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soy varieties that are marketed under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g. rapeseed), IMI® (tolerance to Imidazolinone) and STS® (tolerance to sulfonylureas such as maize). The herbicide-resistant plants (conventionally bred to herbicide tolerance) include the varieties sold under the name Clearfield® (eg maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").

The plants listed can be treated particularly advantageously according to the invention with the active compound mixtures according to the invention. The preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the mixtures specifically listed in this text should be particularly emphasized. The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space in accordance with the customary treatment methods, for example by dipping, spraying, evaporating, atomizing, scattering, spreading and in the case of propagation material, in particular seeds single or multi-layer wrapping.

The active compound combinations according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients or combinations of active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalamine, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or Glycol and its 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. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as butane, propane, nitrogen and carbon dioxide. The following are suitable as solid carriers: for example, natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose. Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils. Dyes such as inorganic pigments such as 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 can be used.

The formulations 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, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance.

fungicides:

1. Inhibition of nucleic acid synthesis

Benalaxyl, Benalaxyl-M, Bupirimat, Chiralaxyl, Clozylacon, Dimethirimol, Ethirimol, Furalaxyl, Hymexazol, Metalaxyl-M, Ofurace, Oxadixyl, Oxolinic acid

2. Inhibition of mitosis and cell division

Benomyl, carbendazim, diethofencarb, fuberidazole, pencycuron, thiabendazole, thiophanate methyl, zoxamide

3. Inhibition of the respiratory chain

3.1 Complex I

diflumetorim

3.2 Complex II

Boscalid, carboxin, fenfuram, flutolanil, furametpyr, mepronil, oxycarboxin, penthiopyrad, thifluzamide 3.3 Complex III

Azoxystrobin, Cyazofamid, Dimoxystrobin, Enestrobin, Famoxadon, Fenamidon, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Pyraclostrobin, Picoxystrobin

3.4 Decoupler Dinocap, Fluazinam

3.5 Inhibition of A TP production

Fentin acetate, fentin chloride, fentin hydroxide, silthiofam

4. Inhibition of amino acid and protein biosynthesis

Andoprim, Blasticidin-S, Cyprodinil, Kasugamycin, Kasugamycin Hydrochloride Hydrate, Mepanipyrim, Pyrimethanil

5. Inhibition of signal transduction

Fenpiclonil, fludioxonil, quinoxyfen

6. Inhibition of fat and membrane synthesis

Chlozolinate, iprodione, procymidone, vinclozolin

Pyrazophos, Edifenphos, Iprobefos (IBP), isoprothiolan

Tolclofos-methyl, biphenyl

Iodocarb, propamocarb, propamocarb hydrochloride

7. Inhibition of ergosterol biosynthesis

fenhexamid,

Azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafole, Furconazole, furconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole,. Myclobutanil, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, voriconazole, imazalil, imazalil sulfate, oxpoconazolurif, fazolazolurol, fazolazolurol, fazolazole Viniconazol,

Aldimorph, Dodemo h, Dodemoφhacetat, Fenpropimorph, Tridemorph, Fenpropidin, Spiroxamine,

Naftifine, pyributicarb, terbinafine

8. Inhibition of cell wall synthesis

Benthiavalicarb, Bialaphos, Dimethomorph, Flumorph, Iprovalicarb, Polyoxins, Polyoxori, Validamycin A

9. Inhibition of melanin biosynthesis

Capropamid, Diclocymet, Fenoxanil, Phtalid, Pyroquilon, Tricyclazol

10. Induction of resistance

Acibenzolar-S-methyl, probenazole, tiadinil

//. Multisite

Captafol, Captan, Chlorothalonil, copper salts such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture, dichlofluanide, dithianon, dodine, dodine free base, ferbam, fluorofolpet, folpet, guazatin, guazadine acetate, im Iminoctadinal besilate, iminoctadine triacetate, man copper, mancozeb, maneb, metiram, metiram zinc, propyneb, sulfur and sulfur preparations containing calcium polysulphide, thiram, zineb, ziram

12. Unknown

Amibromdol, Benthiazol, Bethoxazin, Capsimycin, Carvon, Chinomethionate, Chloropicrin, Cufraneb, Cyflufenamid, Cymoxanil, Dazomet, Debacarb, Diclomezine, Dichlorophen, Dicloran, Difenzoquat, Difenzoquat Methylsulphat, Fluonidifluidomid, Fluoximidifluidomidofluoridium, Fluoxamidifluidomidium, Diphenylumidifluidomid, Fluoridifluoridium, Diphenylumidium, Fluoridimidium, Fluoxidylamidium, Diphenylamidium, Diphenylamidium, Fluoridoxamidium, Diphenylumidium, Diphenylumidium, Oxidylamidium, Diphenylumidium, Oxidylamidium, Diphenylamidium, Diphenylamidium, Diphenylamidium, Diphenylamido , Hexachlorobenzene, 8-hydroxyquinoline sulfate, irumamycin, methasulphocarb, metrafenone, methyl isothiocyanate, mildiomycin, natamycin, nickel dimethyldithiocarbamate, Ni trothal-isopropyl, octhilinone, oxamocarb, oxyfenthiine, pentachlorophenol and salts, 2-phenylphenol and salts, piperalin, propanosine sodium, procinazide, pyrrole nitrate, quintozen, tecloftalam, tecnazene, triazoxide, trichlamide 2,3,5,6- Tetrachloro-4- (methylsulfonyl) pyridine, N- (4-chloro-2-nitrophenyl) -N-ethyl-4-methyl-benzenesulfonamide, 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide, 2- Chloro-N- (2,3-dihydro-l, 1,3-trimethyl-lH-inden-4-yl) -3-pyridinecarboxamide, 3- [5- (4-chloro-phenyl) -2,3-dimethylisoxazolidin-3 -yl] pyridine, cis-'l- (4-Chlθφhenyl) -2- (lH-l, 2,4-triazol-l-yl) -cycloheptanol, 2,4-dihydro-5-methoxy-2-methyl- 4 - [[[[l- [3- (trifluoromethyl) phenyl] ethylidene] amino] oxy] methyl] phenyl] -3H-l, 2,3-triazol-3-one (185336-79 -2), methyl 1 - (2,3-dihydro-2,2-dimethyl-lH-inden-l-yl) -lH-imidazole-5-carboxylate, 3,4,5-trichloro-2,6-pyridinedicarbonitrile , Methyl 2 - [[[cyclopropyl [(4-methoxyphenyl) imino] methyl] thio] methyl] -. Alpha .- (methoxymethylene) - benzoacetate, 4-chloro-alpha-propynyloxy- N- [2- [3-methoxy-4- (2-propynyloxy) phenyl] ethyl] benzacetamide, (2S) -N- [2- [4 - [[3- (4-chlorophenyl) -2-propynyl] oxy] -3-methoxyphenyl] ethyl] - 3-methyl-2 - [(methylsulfonyl) amino] butanamide, 5-chloro-7- (4-methylpiperidin-l-yl) -6- (2,4,6- trifluorophenyl) [l, 2,4] triazolo [l, 5-a] pyrimidine, 5-chloro-6- (2,4,6-trifluorophenyl) -N - [(lR) -l, 2,2-trimethylpropyl] [l, 2,4] triazolo [l, 5-a] pyrimidin-7-amine, 5-chloro-N - [(lR) -l, 2-dimethylpropyl] -6-

(2,4,6-trifluorophenyl) [1,2,4] triazolo [1,5-a] pyrimidin-7-amines, N- [1- (5-bromo-3-chloropyridin-2-yl) ethyl] -2,4-dichloronicotinamide, N- (5-bromo-3-chloropyridin-2-yl) methyl-2,4-dichlomicotinamide, 2-butoxy-6-iodo-3-propyl-benzopyranon-4-one, N- {(Z) - [(cyclopropylmethoxy) imino] [6-

(difluoromethoxy) -2,3-difluoφhenyl] methyl} -2-benzacetamide, N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3-formylamino-2-hydroxy-benzamide, 2 - [[[ [l- [3 (lFluoro-2-phenylethyl) oxy] phenyl] ethylidene] amino] oxy] methyl] -alpha- (methoxyimino) -N-methyl-alphaE-benzacetamide, N- {2- [3-chloro-5 - (trifluoromethyl) pyridin-2-yl] ethyl} -2- (trifluoromethyl) benzamide, N- (3 ', 4'-dichloro-5-fluorobiphenyl-2-yl) -3- (difluoromethyl) -l -methyl- 1 H-pyrazole-4-carboxamide, N- (6-methoxy-3-pyridinyl) -cyclopropane carboxamide, l - [(4-methoxyphenoxy) methyl] -2,2-dimethylpropyl-lH-imidazole-l-carboxylic acid, 0 - [l- [(4-methoxyphenoxy) methyl] -2,2-dimethylpropyl] -lH-imidazole-1-carbothioic acid, 2- (2 - {[6- (3-chloro-2-methylphenoxy) -5- fluoφyrimidin-4-yl] oxy} phenyl) -2- (methoxyimino) -N-methylacetamide

bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

I. Acetylcholinesterase (AChE) inhibitors 1.1 Carbamates (e.g. Alanycarb, Aldicarb, Aldoxycarb, Allyxycarb, Aminocarb, Azamethiphos, Bendiocarb, Benfuracarb, Bufencarb, Butacarb, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Chloethocarb, Coumaphos, Cyanophosphos, Cyanophosphos, Cyanophosphos, Cyanophosphos Fenobucarb, Fenothiocarb, Formetanate, Furathiocarb, Isoprocarb, Metam-sodium, Methio-carb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC, Xylylcarb)

1.2 Organophosphates (e.g. acephate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl), butathiofos, cadusafos, carbophenothion, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorophyros (-methyl / -ethyl), Cyanofenphos, Cyanophos, Chlorfenvinphos, Demeton-S-methyl, Demeton-S-methylsulphon, Dialifos, Diazinon, Dichlofenthion, Dichlorvos / DDVP, Dicrotophos, Dimethoate, Dimethylvinphos, Dioxabenzofos, Disulfoton, EPN, Ethion Fimrophos, Ethion Fimoprophos Fenamiphos, Fenitrothion, Fensulfothion, Fenthion, Flupyrazofos, Fonofos, Formothion, Fosmethilan, Fosthiazate, Heptenophos, Iodofenphos, Iprobefos, Isazofos, Isofenphos, Isopropyl O-salicylate, Isoxathion, Malathion, Methocosamidos, Mecarbamos, Mecarbamos , Naled, Omethoate, Oxydemeton-methyl, Parathion (-methyl / -ethyl), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phosphocarb, Phoxim, Pirimiphos (-methyl / -ethyl), Profenofos, Propaphos, Pr opetamphos, prothiofos, prothoate, pyraclofos, pyridaphenthion, pyridathione, quinalphos, sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, tricothionorf), vamid

2. Sodium channel modulators / voltage-dependent sodium channel blockers

2.1 Pyrethroids (e.g. acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentyl isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin, cis-chlorothrinet -Resmethrin, cis-permethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha, beta, theta, zeta), cyphenothrin, DDT, delta-methrin, empenthrin (lR-isomer), esfen valerate, fenuthrin, etofenproin , Fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate, flucythrinate, flufenprox, flumethrin, fluvalinate, fubfenprox, gamma-cyhalothrin, imiprothrin, kadethrin, lambda-cyhalothrin, perofluthrin (perofluthrin) (perofluthrin) lR-trans isomer), Prallethrin, Profluthrin, Protrifenbute, Pyresmethrin, Resmethrin, RU 15525, Silafluofen, Tau-Fluvalinate, Tefluthrin, Terallethrin, Tetra-methrin (lR-isomer), Tralomethrin, Transflut90, PyrXhrhrin, Pyr ))

2.2 oxadiazines (e.g. indoxacarb)

3. Acetylcholine receptor agonist antagonists 3.1 Chloronicotinyls / neonicotinoids (e.g. acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam)

3.2 Nicotine, Bensultap, Cartap

4.Acetylcholine receptor modulators 4.1 spinosyns (e.g. spinosad)

5 GABA-controlled chloride channel antagonists

5.1 Cyclodienes Organochlorine (e.g. Camphechlor, Chlordane, Endosulfan, Gamma-HCH, HCH, Heptachlor, Lindane, Methoxychlor

5.2 Fiprole (e.g. Acetoprole, Ethiprole, Fipronil, Vaniliprole)

6. Chloride channel activators

6.1 Mectins (e.g. abamectin, avermectin, emamectin, emamectin-benzoate, ivermectin, mitemectin, milbemycin)

7. Juvenile hormone mimetics

(e.g. Diofenolan, Epofenonane, Fenoxycarb, Hydroprene, Kinoprene, Methoprene, Pyriproxifen, Triprene)

8. Ecdysonagonists / disruptors

8.1 Diacylhydrazine (e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenozide)

9. Inhibitors of chitin biosynthesis

9.1 Benzoyl ureas (e.g. bistrifluron, chlofluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron,

triflumuron)

9.2 Buprofezin

9.3 Cyromazines

10. Inhibitors of oxidative phosphorylation, ATP disruptors

10.1 Diafenthiuron 10.2 organotins (e.g. azocyclotin, cyhexatin, fenbutatin-oxide)

11. Decoupler of oxidative phosphorylation by interrupting the H proton gradient

11.1 pyrroles (e.g. chlorfenapyr)

11.2 Dinitrophenols (e.g. Binapacyrl, Dinobuton, Dinocap, DNOC) 12.Site I electron transport inhibitors

12.1 METI's (e.g. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, Tolfenpyrad)

12.2 Hydramethylnone

12.3 Dicofol

13. Site II electron transport inhibitors

13.1 Rotenone

14. Site III electron transport inhibitors

14.1 acequinocyl, fluacrypyrim

75. Microbial disruptors of the insect intestinal membrane

Bacillus thuringiensis strains

16. Inhibitors of fat synthesis

16.1 tetronic acids (e.g. spirodiclofen, spiromesifen)

16.2 tetramic acids [e.g. 3- (2,5-Dimethylphenyl) -8-methoxy-2-oxo-l-azaspiro [4.5] dec-3-en-4-yl ethyl carbonate (alias: Carbonic acid, 3- (2,5-dimethylphenyl) -8-methoxy-2-oxo-l-azaspiro [4.5] dec-3-en-4-yl ethyl ester, CAS Reg.-No .: 382608-10-8) and Carbonic acid, cis-3- ( 2,5-dimethylphenyl) -8-methoxy-2-oxo-l-azaspiro [4.5] dec-3-en-4-yl ethyl ester (CAS Reg.No .: 203313-25-1)]

17. Carboxamides

(e.g. flonicamide) 18. Octopaminergic agonists (e.g. Amitraz)

19. Inhibitors of magnesium-stimulated ATPase (e.g. propargite) 20 phthalamides

(e.g. N ² - [l, l-dimethyl-2- (methylsulfonyl) ethyl] -3-iodo-N '- [2-methyl-4- [l, 2,2,2-tetrafluoro-l- (trifluoromethyl) ethyl] phenyl] -l, 2-benzenedicarboxamide (CAS Reg.-No .: 272451-65-7), flubendiamides)

21. he ice toxin analogue

(e.g. Thiocyclam hydrogen oxalate, Thiosultap-sodium)

22. Biologicals, hormones or pheromones

(e.g. Azadirachtin, Bacillus spec, Beauveria spec, Codlemone, Metarrhician spec, Paecilomyces spec, Thuringiensin, Verticillium spec.)

23. Active substances with unknown or non-specific mechanisms of action

23.1 fumigants (e.g. aluminum phosphide, methyl bromide, sulfuryl fluoride)

23.2 Selective feeding inhibitors (e.g. cryolite, flonicamide, pymetrozine)

23.3 mite growth inhibitors (e.g. clofentezine, etoxazole, hexythiazox)

23.4 amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, buprofezin, Chinome- thionate, chlordimeform, Chlorobenzilate, Chloropicrin, Clothiazoben, Cycloprene, Cyflumetofen, dicyclanil, Fenoxacrim, Fentrifanil, Flubenzimine, flufenerim, Flutenzin, Gossyplure, methyl hydrazine none, Japonilure, Metoxadiazone , Petroleum, piperonyl butoxide, potassium oleate, pyrafluprole, pyridalyl, pyriprole, sulfluramide, tetradifon, tetrasul, triarathene, verbutin,

furthermore the compound 3-methyl-phenyl-propylcarbamate (Tsumacide Z), the compound 3- (5-chloro-3-pyridinyl) -8- (2,2,2-trifluoretlιyl) -8-azabicyclo [3.2. 1] octane-3-carbonitrile (CAS Reg.No. 185982-80-3) and the corresponding 3-endo isomer (CAS Reg.No. 185984-60-5) (cf. WO 96/37494 , WO 98/25923), as well as preparations which contain insecticidally active plant extracts, nematodes, fungi or viruses. A mixture with other known active compounds, such as herbicides, safeners or semiochemicals, or with fertilizers and growth regulators is also possible.

The compounds (I), (H) and (HI) can be applied simultaneously, that is jointly or separately, or in succession, the sequence in the case of separate application generally not having any effect on the success of the control measures.

The active substance combinations 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 and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, scattering, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.

When using the active compound combinations according to the invention, the application rates can be varied within a substantial range, depending on the type of application. In the treatment of parts of plants, the active compound combination application rates 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 active compound combination application rates 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 active compound combination application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

The good fungicidal activity of the active compound combinations according to the invention can be seen from the examples below. While the individual active ingredients have weaknesses in their fungicidal action, the combinations show an action that goes beyond a simple summation of action.

Fungicides always have a synergistic effect if the fungicidal activity of the active compound combinations is greater than the sum of the effects of the individually applied active compounds.

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

If

X means the efficiency when using the active ingredient A in an application rate of mg / ha, Y means the efficiency when using the active ingredient B in an application rate of ng / ha and

E means the efficiency when using active ingredients A and B in application rates of m and n g / ha,

then

X Y E = X + Y 100

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 infection is observed.

If the actual fungicidal activity is greater than calculated, the combination of the combination is superadditive, i.e. there is a synergistic effect. In this case, the actually observed efficiency must be greater than the value for the expected efficiency (E) calculated from the above formula.

Another method for determining synergistic effects is offered by the Tammes model (Neth. J. Plant Path. 70 (1964) 73-80), in which e.g. the theoretical dosage for an efficiency of 90% is determined and compared with the actually necessary dosage.

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

example

Synergistic protective effect of a combination of trifloxystrobin / tolylfluanid and Fosetyl-Al against Plasmopara viticola on vines.

The mixture of trifloxystrobin and tolylfluanid was used as a combination of the commercially available individual components in WG formulations (Flint® containing 50% by weight trifloxystrobin and Euparen® containing 50% by weight tolylfluanid).

Fosetyl-Al was used as a commercial WG formulation (Aliette®, containing 80% by weight of Fosetyl-Al).

To test for preventive effectiveness, a spray application was carried out on young wine plants of the Cabernet Sauvignon variety with the active ingredient preparations (application rate 250 1 spray mixture per hectare). The weight ratio of trifloxystrobin to tolylfluanid to Aliette® (fosetyl-Al) was 1.55: 25: 50 in the preparation of active ingredient consisting of trifloxystrobin, tolylfluanid and fosetyl-Al.

After 3 days, the plants were inoculated with an aqueous spore suspension of Plasmopara vitico- la (approximately 10 ⁵ spores / ml). The plants were then incubated for 7 days at 20 ° C. in a saturated atmosphere.

The evaluation was then carried out. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed. Table 1: Synergism between trifloxystrobin / tolylfluanid and Fosetyl-Al according to Tammes

Table 2: Synergism between trifloxystrobin / tolylfluanid and Fosetyl-Al according to Colby

The experiments and the evaluation methods show a synergism between trifloxystrobin / tolylfluanid and fosetyl-Al.

Claims

claims

Active substance combination containing a compound of formula (I)

and

(1) a compound of formula (II)

II H - P (OR ³ ) ₂ (π) where

R ^{3 are the} same or different for H, V _n M ^{n +} or (-C-C) alkyl and

M stands for a cation; and

(2) a compound of formula (in)

nid)

2. Active ingredient combination according to claim 1, in which the compound of formula (H)

HP (0) (OH) ₂ , HP (0) (OH) (OK), HP (0) (OK) ₂ , HP (0) (OC ₂ H ₅ ) (ONa) or

[HP (0) (OC ₂ H5) 0] ₃ AI.

3. Active ingredient combination according to claim 2, in which the compound of formula (II) [HP (0) (OC ₂ H ₅ ) 0] ₃ AI (Fosetyl-Al).

4. Active ingredient combination according to one or more of claims 1 to 3, characterized in that in the active ingredient combination, the weight ratio of active ingredient of formula (I)

Active ingredient of formula (II) is 1: 0.1 to 1: 100, and active ingredient of formula (111) is 1: 0.1 to 1: 100.

5. A method for combating phytopathogenic fungi, characterized in that an active ingredient combination according to one or more of claims 1 to 4 on the fungi and / or their habitat or the plants, parts of plants, seeds, soils, surfaces, materials or Lets rooms take effect.

6. The method according to claim 4, characterized in that the compound (I) according to claim 1, the compound (II) according to claim 1 and the compound (HI) according to one or more of claims 1 to 3 are applied simultaneously or separately or in succession ,

7. propagation material coated with an active ingredient combination according to one or more of claims 1 to 4.

8. Fungicidal compositions containing an active ingredient combination as defined in claim 1.

9. Use of the active ingredient combination or agent as defined in claims 1, 2, 6 and 7 for combating fungi.

10. A process for the preparation of fungicidal agents, characterized in that an active ingredient combination according to one or more of claims 1 to 4 is mixed with extenders and / or surface-active substances.