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Title:
PESTICIDAL MIXTURES
Document Type and Number:
WIPO Patent Application WO/2022/207373
Kind Code:
A1
Abstract:
Fungicidal mixture comprising, as active components: 1) Metyltetraprole as compound I and; 2) Isoflucypram as compound II; 3) one or more compound III, selected from Mefentrifluconazole, Prothioconazole, Metconazole and Fluoxytioconazole.

Inventors:
STROBEL DIETER (DE)
VALTIN MARIA (DE)
REIGOSA BUSQUETS VICTORIA (DE)
SHORT TIM (DE)
KLAPPACH KRISTIN (DE)
MONTAG JURITH (DE)
Application Number:
PCT/EP2022/057264
Publication Date:
October 06, 2022
Filing Date:
March 21, 2022
Export Citation:
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Assignee:
BASF SE (DE)
International Classes:
A01N43/713; A01N43/48; A01N43/653; A01P3/00
Domestic Patent References:
WO2020007647A12020-01-09
WO2020007646A12020-01-09
WO2013162072A12013-10-31
WO2012143127A12012-10-26
WO2014060502A12014-04-24
WO2012060521A12012-05-10
Foreign References:
EP3698634A12020-08-26
EP3643175A12020-04-29
US20170347651A12017-12-07
US20140038823A12014-02-06
Other References:
"Technical Monograph", May 2008, CROPLIFE INTERNATIONAL, article "Catalogue of pesticide formulation types and international coding system"
MOLLETGRUBEMANN: "Formulation technology", 2001, WILEY VCH
KNOWLES: "Agrow Reports DS243", 2005, T&F INFORMA, article "New developments in crop protection product formulation"
MCCUTCHEON'S: "Emulsifiers & Detergents, McCutcheon's Directories", vol. 1, 2006, T&F INFORMA, article "Adjuvants and additives"
R.S. COLBY: "Calculating synergistic and antagonistic responses of herbicide combinations", WEEDS, vol. 15, 1967, pages 20 - 22, XP001112961
Attorney, Agent or Firm:
BASF IP ASSOCIATION (DE)
Download PDF:
Claims:
Claims

1. Fungicidal mixture comprising, as active components,

1) Metyltetraprole as compound I and

2) Isoflucypram as compound II,

3) one or more compound III, selected from Mefentrifluconazole, Prothioconazole, Metconazole and Fluoxytioconazole.

2. A mixture as claimed in claim 1, wherein the ratio by weight of compound I and compound

II is in the range of from 1:100 to 100:1 and the weight ratio of compound I and compound

III is in the range of from 1 : 100 to 100: 1.

3. A pesticidal composition, comprising a liquid or solid carrier and a mixture as defined in any of claims 1 to 2.

4. A method for controlling phytopathogenic pests, wherein the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant prop agation material are treated with an effective amount of a fungicidal mixture comprising, as active components:

1) metyltetraprole as compound I and

2) isoflucypram as compound II,

3) one or more compound III, selected from Mefentrifluconazole, Prothioconazole, Metconazole and Fluoxytioconazole.

5. The method according to of claim 4 for controlling phytopathogenic fungi on cereals.

6. The method according to any of claims 4 to 5 wherein the phytopathogenic fungus is Mi- croduchium nivale, Erysiphe graminis tritici, Septoria tritici, Phaeospheria nodorum or Pyr- enophera tritici on wheat.

7. The method according to any of claims 4 to 6 wherein the phytopathogenic fungus is Ery siphe graminis hordei, Pyrenophera teres, Ramularia collicygni or Rynchosporium secalis on barley.

8. The method according to any of claims 4 to 7 wherein the phytopathogenic fungus is Puc- cinia recondita (brown or leaf rust), Puccinia striiformis (stripe or yellow rust), or Puccinia graminis (stem or black rust) on wheat, barley or rye.

9. A method for improving the health of plants, wherein the plant, the locus where the plant is growing or is expected to grow or plant propagation material from which the plant grows are treated with an effective amount of a fungicidal mixture comprising, as active compo nents:

1) metyltetraprole as compound I and

2) isoflucypram as compound II,

3) one or more compound III, selected from Mefentrifluconazole, Prothioconazole, Metconazole and Fluoxytioconazole.

10. A method for protection of plant propagation material from pests comprising contacting the plant propagation materials with a fungicidal mixture comprising, as active components:

1) metyltetraprole as compound I and

2) isoflucypram as compound II,

3) one or more compound III, selected from Mefentrifluconazole, Prothioconazol, Metconazole and Fluoxytioconazole.

11. A method as claimed in any of claims 4 to 10, wherein said fungicidal is applied in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation materials.

12. A method as claimed in any of claims 4 to 11 , wherein said fungicidal mixture is applied simultaneously, that is jointly or separately, or in succession.

13. Plant propagation material, comprising a fungicidal mixture comprising, as active compo nents,

1) metyltetraprole as compound I and

2) isoflucypram as compound II,

3) one or more compound III, selected from Mefentrifluconazole, Prothioconazol, Metconazole and Fluoxytioconazole. in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation materials.

Description:
Pesticidal mixtures

The present invention relates to fungicidal mixtures comprising

1) metyltetraprole as compound I and

2) isoflucypram as compound II,

3) one or more compound III, selected from Mefentrifluconazole, Prothioconazol, Metconazole and Fluoxytioconazole.

Moreover, the invention relates to a method for controlling pests, this includes animal pests and harmful fungi, using the inventive mixtures and the use of compound I, compound II and com pound III for preparing such mixtures, and also compositions comprising such mixtures.

Additionally, the present invention also comprises a method for protection of plant propagation material (preferably seed) from harmful fungi or comprising contacting the plant propagation materials (preferably seeds) with an inventive mixture in pesticidally effective amounts

The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. pota toes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.

These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring. In a particular preferred embodiment, the term propagation material denotes seeds.

Additionally, the present invention also comprises a method for protection of plant propagation material (preferably seed) from harmful fungi comprising contacting the plant propagation mate rials (preferably seeds) with the inventive mixture in pesticidally effective amounts.

Moreover, the invention relates to a method for controlling harmful fungi using the inventive mix tures and to the use of the compounds present in the inventive mixtures for preparing such mix tures, and also to compositions comprising such mixtures.

The present invention further relates to plant-protecting active ingredient mixtures having syner- gisti cally enhanced activity of improving the health of plants and to a method of applying such inventive mixtures to the plants.

Compound I and analogues as well as its pesticidal activity and methods for producing it are known e.g. from WO 2013/162072. Compounds II as well as their pesticidal activity and meth ods for producing them are known from known from WO 2012/143127 and WO 2014/60502 and WO2012/60521. One typical problem arising in the field of pest control lies in the need to increase the efficacy and to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control.

In regard to the instant invention the term pests embrace harmful fungi and animal pests.

Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of harmful fungi and harmful animal pests.

There also exists the need for pest control agents that combine knock-down activity with pro longed control, that is, fast action with long lasting action.

Another difficulty in relation to the use of pesticides is that the repeated and exclusive applica tion of an individual pesticidal compound leads in many cases to a rapid selection of pests, that means animal pests, and harmful fungi, which have developed natural or adapted resistance against the active compound in question. Therefore, there is a need for pest control agents that help prevent or overcome resistance.

Another problem underlying the present invention is the desire for compositions that improve plants, a process which is commonly and hereinafter referred to as “plant health”.

The term plant health comprises various sorts of improvements of plants that are not connected to the control of pests. For example, advantageous properties that may be mentioned are im proved crop characteristics including: emergence, crop yields, protein content, oil content, starch content, more developed root system (improved root growth), improved stress tolerance (e.g. against drought, heat, salt, UV, water, cold), reduced ethylene (reduced production and/or inhibition of reception), tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination; or any other advantages familiar to a person skilled in the art.

It was therefore an object of the present invention to provide pesticidal mixtures which solve the problems of reducing the dosage rate and / or enhancing the spectrum of activity and / or com bining knock-down activity with prolonged control and / or to resistance management and/or promoting the health of plants.

We have found that this object is in part or in whole achieved by the fungicidal mixtures com prising

1) metyltetraprole as compound I, 3) one or more compound III, selected from Mefentrifluconazole, Prothioconazol, Metconazole and Fluoxytioconazole.

In one embodiment, compound III is selected from Mefentrifluconazole, Prothioconazol and Metconazole.

Especially, it has been found that the mixtures as defined in the outset show markedly en hanced activity against pests compared to the control rates that are possible with the individual compounds and/or is suitable for improving the health of plants when applied to plants, parts of plants, seeds, or at their locus of growth.

It has been found that the activity of the inventive mixtures comprising compound I and com pound II goes far beyond the fungicidal and/or plant health improving activity of the active com pounds present in the mixture alone (synergistic activity).

Moreover, we have found that simultaneous, that is joint or separate, application of the com pound I, compound II and compound III or successive application of the compound I, compound II and compound III allows enhanced control of harmful fungi, compared to the control rates that are possible with the individual compounds (synergistic mixtures).

Moreover, we have found that simultaneous, that is joint or separate, application of the com pound I, compound II and compound III or successive application of the compound I, compound II and compound III provides enhanced plant health effects compared to the plant health effects that are possible with the individual compounds.

Particularly preferred mixtures are the following:

In the mixtures of the invention, the weight ratio of compound I and compound II is usually in the range of from 1:100 to 100:1, regularly from 1:50 to 50:1, preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1 and in particular from 1:4 to 4:1, and the weight ratio of compound I and compound III usually it is in the range of from 1:100 to 100:1, regularly from 1:50 to 50:1, preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1 and in particular from 1:4 to 4:1. Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the com pound I. These ratios are also suitable for mixtures applied by seed treatment.

All above-referred mixtures are herein below referred to as “inventive mixtures” or “mixtures according to the invention”.

The inventive mixtures can further contain one or more insecticides, fungicides, herbicides.

The inventive mixtures can be converted into customary types of agrochemical composi tions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International.

The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New develop ments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, disper sants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibil- izers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, al kylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methyl pyrrolidone, fatty acid dimethylamides; and mixtures thereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magne sium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammoni um sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective col loid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1 : Emulsifiers & De tergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sul fates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethox ylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Exam ples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Exam ples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the inventive mixtures on the tar get. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inor ganic clays (organically modified or unmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkyliso- thiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidones, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers. The resulting agrochemical compositions generally comprise between 0.01 and 95%, pref erably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active sub stance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), pow ders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually em ployed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Appli cation can be carried out before or during sowing. Methods for applying the inventive mixtures and compositions thereof, respectively, on to plant propagation material, especially seeds in clude dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, the inventive mixtures or the compositions thereof, respective ly, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of active substances applied are, depend ing on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.01 to 1.0 kg per ha, and in particular from 0.05 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.01-10 kg, preferably from 0.1-1000 g, more preferably from 1-100 g per 100 kilogram of plant propagation material (preferably seeds) are generally required.

When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the ac tive substances or the compositions comprising them as premix or, if appropriate not until im mediately prior to use (tank mix). These agents can be admixed with the compositions accord ing to the invention in a weight ratio of 1 : 100 to 100: 1 , preferably 1 : 10 to 10: 1.

The user applies the composition according to the invention usually from a predosage de vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the ag rochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

According to one embodiment, individual components of the composition according to the in vention such as parts of a kit or parts of a ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pel leting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate. Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal com position, the kit comprising a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and option ally a further active component 3) as defined herein.

As said above, the present invention comprises a method for controlling harmful fungi, wherein the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or plant propagation material (preferably seed) are treated with a pesticidally effective amount of an inventive mixture. In one embodiment methods for treating human or animal body are excluded.

They are also important for controlling a multitude of fungi on various cultivated plants, such as bananas, cotton, vegetable species (for example cucumbers, beans and cucurbits), cereals such as wheat, rye, barley, rice, oats; grass coffee, potatoes, corn, fruit species, soya, toma toes, grapevines, ornamental plants, sugar cane and also on a large number of seeds. In a pre ferred embodiment, the inventive mixtures are used in soya (soybean), cereals and corn.

The inventive mixtures are particularly suitable for controlling wheat diseases caused by Alter- naria spp. (Alternaria leaf spot), Ascochyta tritici (anthracnose), Blumeria (formerly Erysiphe) graminis (powdery mildew), Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold), Cladosporium herbarum (black ear), Drechslera (syn. Helminthosporium, teleomorph: Pyre- nophora) tritici-repentis (tan spot), Epicoccum spp. (black mold), Fusarium (teleomorph: Gibber- ella) graminearum or Fusarium culmorum (root rot, scab or head blight), Gaeumannomyces graminis (take-all), Microdochium (syn. Fusarium) nivale (pink snow mold), Mycosphaerella 15 graminicola (anamorph: Septoria tritici, Septoria blotch), Polymyxa graminis, Pseudocerco- sporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae), Puccinia graminis (stem or black rust), Puccinia recondita (brown or leaf rust), Pyrenophora (anamorph: Drechslera) triti- cirepentis (tan spot), Pythium spp. (damping-off), Rhizoctonia cerealis (Rhizoctonia spring blight), Septoria tritici (Septoria blotch), Stagonospora nodorum (Stagonospora blotch, teleo morph: Leptosphaeria [syn. Phaeosphaeria] nodorum), Tilletia. tritici (syn. Tilletia caries, wheat bunt), T. controversa (dwarf bunt) or Typhula incarnata (grey snow mold).

The inventive mixtures are also particularly suitable for controlling barley diseases caused by Ascochyta hordei, Bipolaris (teleomorph: Cochliobolus, spot blotch) sorokiniana, Blumeria (formerly Erysiphe) graminis (powdery mildew), Botrytis cinerea (teleomorph: Botryotinia fuckeliana : grey mold), Cladosporium herbarum (black ear), Claviceps purpurea (ergot), Cochliobolus (anamorph: Helminthosporium of Bipolaris) sativus, Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora ) teres, Epicoccum spp. (black mold),

Fusarium (teleomorph: Gibberella ) culmorum (root rot, scab or head blight) on cereals (e.g. wheat or barley), Gaeumannomyces graminis (take-all), Gibberella spp. (e. g. G. zeae), Helmintho-sporium spp. (syn. Drechslera , teleomorph: Cochliobolus), Microdochium (syn. Fusarium) nivale (pink snow mold), Mycosphaerella spp. , Polymyxa spp.,

Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae ), Puccinia recondita (brown or leaf rust), Pyrenophora (anamorph: Drechslera ) teres (net blotch), Pyricularia grisea, Ramularia collo-cygni (Ramularia leaf spots, Physiological leaf spots), Rhizoctonia cerealis (Rhizoctonia spring blight), Rhynchosporium secalis (scald), Septoria (syn. Stagonospora ) nodorum (Stagonospora blotch), Stagonospora spp. , Tilletia spp. (common bunt or stinking smut), Typhula incarnata (grey snow mold), or Ustilago spp.

(loose smut), e. g. U. nuda and U. avaenae.

The inventive mixtures are particularly suitable for controlling wheat diseases caused by Septo ria tritici, Microduchium nivale, Erysiphe graminis tritici, Phaeospheria nodorum or Pyrenophera tritici-repentis.

The inventive mixtures are also particularly suitable for controlling barley diseases caused by Erysiphe graminis hordei, Pyrenophera teres, Ramularia collicygni or Rynchosporium secalis. The inventive mixtures are also particularly suitable for controlling wheat diseases caused by Puccinia recondita (brown or leaf rust), Puccinia striiformis (stripe or yellow rust), or Puccinia graminis (stem or black rust).

The inventive mixtures are also particularly suitable for controlling barley diseases caused by Puccinia recondita (brown or leaf rust), Puccinia striiformis (stripe or yellow rust), or Puccinia graminis (stem or black rust).

The mixtures according to the present invention are especially useful for controlling phytopatho- genic fungi in cereals such as wheat, barley or rye, especially on wheat and barley.

In one especially preferred embodiment, the inventive mixtures are used for controlling the fol lowing phytopathogenic fungi on wheat: Septoria tritici, Pyrenophera tritici-repentis, Microduch ium nivale, Erysiphe graminis tritici or Phaeospheria nodorum.

In one especially preferred embodiment, the inventive mixtures are used for controlling the fol lowing phytopathogenic fungi on barley: Erysiphe graminis hordei, Pyrenophera teres, Ramular ia collicygni or Rynchosporium secalis.

In one especially preferred embodiment, the inventive mixtures are used for controlling the fol lowing phytopathogenic fungi on wheat, barley or rye: Puccinia recondita (brown or leaf rust), Puccinia striiformis (stripe or yellow rust), or Puccinia graminis (stem or black rust).

In preferred embodiments, the following inventive mixtures can be used on the following crops: In preferred embodiments, the following inventive mixtures can be used on the following crops and pests:

Mixtures according to the invention are suitable for combating phytopathogenic fungi, such fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibi- tors, wherein the mutation is G143A or F129L.

In general, "pesticidally effective amount" means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, in cluding the effects of necrosis, death, retardation, prevention, and removal, destruction, or oth- erwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures / compositions used in the invention. A pesticidally effective amount of the mixtures / compositions will also vary according to the prevailing condi- tions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

As said above, the present invention comprises a method for improving the health of plants, wherein the plant, the locus where the plant is growing or is expected to grow or plant propaga tion material, from which the plant grows, is treated with a plant health effective amount of an inventive mixture.

The term "plant effective amount" denotes an amount of the inventive mixtures, which is suffi cient for achieving plant health effects as defined herein below. More exemplary information about amounts, ways of application and suitable ratios to be used is given below. Anyway, the skilled artisan is well aware of the fact that such an amount can vary in a broad range and is dependent on various factors, e.g. the treated cultivated plant or material and the climatic condi tions.

When preparing the mixtures, it is preferred to employ the pure active compounds, to which further active compounds against pests, such as insecticides, herbicides, fungicides or else herbicidal or growth-regulating active compounds or fertilizers can be added as further active components according to need.

The inventive mixtures are employed by treating the fungi or the plants, plant propagation materials (preferably seeds), materials or soil to be protected from fungal attack with a pesticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the materials, plants or plant propagation materials (preferably seeds) by the pests.

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

The inventive mixtures and compositions thereof are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or mel ons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grape fruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (Table Grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.

Preferably, the inventive mixtures and compositions thereof, respectively are used for con trolling a multitude of fungi on field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

Preferably, treatment of plant propagation materials with the inventive mixtures and compo sitions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; potatoes, tomatoes, vines, rice, corn, cotton and soybeans.

The term "cultivated plants" is to be understood as including plants which have been modi fied by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop data base therein). Genetically modified plants are plants, which genetic material has been so modi fied by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not lim ited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by gly- cosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.

The separate or joint application of the compounds of the inventive mixtures is carried out by spraying or dusting the seeds, the seedlings, the plants or the soils before or after sowing of the plants or before or after emergence of the plants.

The inventive mixtures and the compositions comprising them can be used for protecting wood en materials such as trees, board fences, sleepers, etc. and buildings such as houses, out houses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, elec tric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facili ties).

Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .

For use in spray compositions, the content of the mixture of the active ingredients is from 0.001 to 80 weight %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

The present invention offers the following advantages:

It provides pesticidal mixtures which solve the problems of reducing the dosage rate and / or excellent spectrum of activity and / or combining knock-down activity with prolonged control and / or to resistance management and/or promoting the health of plants. Examples

The invention is further illustrated, but not limited by the following practical example:

Example 1 - Field experience with Septoria (Zymoseptoria tritici)

A trial was conducted in 2020 in winter wheat (var. Riband) as randomised block design with 4 replicates in Germany at the location “Kreuzgraben” in Ruchheim. The trial was done according to EPPO standards (namely EPPO PP 1/135 (4), EPPO PP 1/152 (4), EPPO PP 1/181 (4), EP- PO PP 1/223 (2) and EPPO PP 1/239 (2). The test products were applied twice during the sea son with a watervolume of 300 l/ha. The first application was done on the 24th of April 2020 at the crop growth stage BBCH 32-33. The second application took place on the 5th of June 2020 at the crop growth stage BBCH 69. No other compounds were applied for pathogen control.

The target of the trial was to check different mixtures of active ingredients on their efficacy against Zymoseptoria tritici, especially the efficacy contribution of SDHIs to a Qol-DMI mixture.

In order to explore the contribution of the SDH I, the dose rates of the Qol and DM I was reduced by 25%in the triple mixture.

Table 1 summarizes the tested active ingredient mixtures, their mode of action and their content applied per hectare.

Table 1 : tested mixtures and content of active ingredients per hectare

No other pesticidal compounds were applied for pathogen control. The disease incidences for Septoria (Zymoseptoria tritici) were evaluated after the last fungicide treatment, with individual assessments on the top leaf levels. Disease ratings were converted into efficacies. An efficacy of 0 means that the level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants had no disease at all. Finally, the effica cy benefit of a SDHI-containing triple mixture over the Qol-DMI reference was calculated. Table 2: Septoria assessments and efficacy of tested mixtures 20 days after last application

The intensity of attack with Zymoseptoria tritici was strongly reduced by applying a Qol-DMI mixture. By adding fluxapyroxad or benzovindiflupyr as an SDHI to such mixture, the perfor mance could not be significantly enhanced further.

However, and surprisingly, if isoflucypram is added as an SDHI compound, an unexpected boost of efficacy was observed, leading to remarkable and outstanding efficacy levels.

Example 2 Microtest

The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.

The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.

1. Activity against rice blast Pyricularia oryzae in the microtiterplate test (PYRIOR)

A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone- glycerine or DOB solution was then added.

2. Activity against leaf blotch on wheat caused by Septoria tritici (SEPTTR)

A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.

The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies.

An efficacy of 0 means that the growth level of the pathogens corresponds to that of the un treated control; an efficacy of 100 means that the pathogens were not growing. The expected efficacies of active compound mixtures were determined using Colby's formula [R.S. Colby, “Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacies.

PYRIOR

SEPTTR