WO2016173996A1 - Use of 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1h-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate - Google Patents

Use of 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1h-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate Download PDF

Info

Publication number
WO2016173996A1
WO2016173996A1 PCT/EP2016/059213 EP2016059213W WO2016173996A1 WO 2016173996 A1 WO2016173996 A1 WO 2016173996A1 EP 2016059213 W EP2016059213 W EP 2016059213W WO 2016173996 A1 WO2016173996 A1 WO 2016173996A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxazol
difluoromethyl
bis
pyrazol
thiazol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2016/059213
Other languages
French (fr)
Inventor
Stefan Hillebrand
Sylvain Tafforeau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Bayer CropScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of WO2016173996A1 publication Critical patent/WO2016173996A1/en
Priority to PH12017501985A priority Critical patent/PH12017501985A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention relates to the use of 2- ⁇ 3-[2-(l- ⁇ [3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl ⁇ piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate (see Figure 1) and of compositions comprising 2- ⁇ 3-[2-(l- ⁇ [3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl ⁇ piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate and further fungicides or insecticides for controlling downy mildew diseases of monocotyledon crops. Furthermore the treatment of seed is described
  • 2- ⁇ 3-[2-(l- ⁇ [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl ⁇ piperidin-4-yl)- 1 ,3 -thiazol-4-yl] -4,5-dihydro- 1 ,2- oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate is a fungicide especially useful for the control of oomycetes such as Phytophthora species, for example Phytophthora infestans and Plasmopara species, for example Plasmopara viticola.
  • This invention now provides an advantageous use of compound of formula (I) ,2- ⁇ 3-[2-(l- ⁇ [3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl ⁇ piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2-oxazol-5- yl ⁇ -3-chlorophenyl methanesulfonate, and of compositions comprising 2- ⁇ 3-[2-(l- ⁇ [3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl ⁇ piperidin-4-yl)- 1 ,3-thiazol-4-yl] -4,5-dihydro- 1 ,2-oxazol-5-yl ⁇ -3- chlorophenyl methanesulfonate and further active ingredients against downy mildew in monocotyledon crops, such as Peronoscler
  • Figure 1 2- ⁇ 3 - [2-( 1 - ⁇ [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl ⁇ piperidin-4-yl)- 1 ,3-thiazol-4-yl] - 4,5-dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate
  • controlling denotes a significant reduction of the downy mildew infestation in comparison to the untreated crop, more preferably the infestation is essentially diminished (50-79%), most preferably the infestation is totally suppressed (80-100%).
  • 2- ⁇ 3-[2-(l- ⁇ [3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl ⁇ piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate as such or formulations thereof can be applied in combination with further known fungicides, bactericides, acaricides, nematicides, herbicides, insecticides for broadening the activity spectrum and in order to prevent the development of resistance. In many instances, synergistic effects are obtained, i.e. the activity of the mixture exceeds the activity of the individual components.
  • composition stands for the various combinations of compounds A) and B), for example in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active compounds, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days.
  • the order of applying the compounds A) and B) is not essential for working the present invention.
  • the present invention further relates to a composition for controlling unwanted microorganisms, comprising 2- ⁇ 3 - [2-( 1 - ⁇ [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl ⁇ piperidin-4-yl)- 1 ,3 -thiazol-4-yl] - 4,5-dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate.
  • These are preferably fungicidal compositions which comprise agriculturally suitable auxiliaries, solvents, carriers, surfactants or extenders.
  • a carrier is a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for better applicability, in particular for application to plants or plant parts or seed.
  • the carrier which may be solid or liquid, is generally inert and should be suitable for use in agriculture.
  • Useful solid carriers include: for example ammonium salts and natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock flours, such as finely divided silica, alumina and silicates; useful solid carriers for granules include: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic flours, and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks; useful emulsifiers and/or foam-formers include: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, aryl
  • oligo- or polymers for example those derived from vinylic monomers, from acrylic acid, from EO and/or PO alone or in combination with, for example, (poly)alcohols or (poly)amines. It is also possible to use lignin and its sulphonic acid derivatives, unmodified and modified celluloses, aromatic and/or aliphatic sulphonic acids and also their adducts with formaldehyde.
  • the active ingredients can be converted to the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances.
  • customary formulations such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances.
  • the active ingredients can be applied as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, water- or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances.
  • Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading-on and the like.
  • the formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, emulsifier, dispersant and/or binder or fixing agent, wetting agent, a water repellent, if appropriate siccatives and UV stabilizers and if appropriate dyes and pigments, antifoams, preservatives, secondary thickeners, stickers, gibberellins and also other processing auxiliaries.
  • the present invention includes not only formulations which are already ready for use and can be deployed with a suitable apparatus to the plant or the seed, but also commercial concentrates which have to be diluted with water prior to use.
  • the 2- ⁇ 3-[2-(l- ⁇ [3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl ⁇ piperidin-4-yl)-l,3-thiazol-4-yl]-4,5- dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate may be present as such or in their (commercial) formulations and in the use forms prepared from these formulations as a mixture with other (known) active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.
  • active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.
  • auxiliaries used may be those substances which are suitable for imparting particular properties to the composition itself or and/or to preparations derived therefrom (for example spray liquors, seed dressings), such as certain technical properties and/or also particular biological properties.
  • Typical auxiliaries include: extenders, solvents and carriers.
  • Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for example from the classes of the aromatic and nonaromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which may optionally also be substituted, etherified and/or esterified), the ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, the unsubstituted and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulphones and sulphoxides (such as dimethyl sulphoxide).
  • aromatic and nonaromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • the alcohols and polyols which may optionally also
  • Liquefied gaseous extenders or carriers are understood to mean liquids which are gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, or else butane, propane, nitrogen and carbon dioxide.
  • tackifiers such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids.
  • Further additives may be mineral and vegetable oils.
  • Useful liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, 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 sulphoxide, or else water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride
  • aliphatic hydrocarbons such as
  • compositions comprising 2- ⁇ 3 - [2-( 1 - ⁇ [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl ⁇ piperidin-4-yl)- l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate may additionally comprise further components, for example surfactants. Suitable surfactants are emulsifiers and/or foam formers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants.
  • Examples thereof are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, protein hydrolysates, lignosulphite waste liquors and methylcellulose.
  • the presence of a surfactant is necessary if one of the active ingredients and/or one of the inert
  • dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Further additives may be perfumes, mineral or vegetable, optionally modified oils, waxes and nutrients (including trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Additional components may be stabilizers, such as cold stabilizers, preservatives, antioxidants, light stabilizers, or other agents which improve chemical and/or physical stability.
  • the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.
  • the formulations contain generally between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1 and 95% by weight, more preferably between 0.5 and 90% of active ingredient, most preferably between 10 and 70 per cent by weight.
  • compositions comprising 2- ⁇ 3-[2-(l - ⁇ [3,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl ⁇ piperidin-4-yl)- 1 ,3- thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate are applied to the microorganisms and/or in their habitat.
  • the invention furthermore includes a method for treating seed.
  • a further aspect of the present invention relates in particular to seeds (dormant, primed, pregerminated or even with emerged roots and leaves) treated with 2- ⁇ 3-[2-(l- ⁇ [3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl ⁇ piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate.
  • the inventive seeds are used in methods for protection of seeds and emerged plants from the seeds from phytopathogenic harmful fungi. In these methods, seed treated with at least one inventive active ingredient is used.
  • the 2- ⁇ 3 - [2-( 1 - ⁇ [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl ⁇ piperidin-4-yl)- 1 ,3-thiazol-4-yl] -4,5- dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate are also suitable for the treatment of seeds and young seedlings.
  • a large part of the damage to crop plants caused by harmful organisms is triggered by the infection of the seeds before sowing or after germination of the plant. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive, and even small damage may result in the death of the plant. Accordingly, there is great interest in protecting the seed and the germinating plant by using appropriate compositions.
  • the present invention therefore also relates to a method for protecting seeds, germinating plants and emerged seedlings against attack by animal pests and/or phytopathogenic harmful microorganisms by treating the seeds with an inventive composition.
  • the invention also relates to the use of the compositions according to the invention for treating seeds for protecting the seeds, the germinating plants and emerged seedlings against animal pests and/or phytopathogenic microorganisms.
  • the invention further relates to seeds which has been treated with an inventive composition for protection from animal pests and/or phytopathogenic microorganisms.
  • One of the advantages of the present invention is that the treatment of the seeds with these compositions not only protects the seed itself, but also the resulting plants after emergence, from animal pests and/or phytopathogenic harmful microorganisms. In this way, the immediate treatment of the crop at the time of sowing or shortly thereafter protect plants as well as seed treatment in prior to sowing.
  • the inventive active ingredients or compositions can be used especially also for transgenic seed, in which case the plant which grows from this seed is capable of expressing a protein which acts against pests, herbicidal damage or abiotic stress.
  • the treatment of such seeds with the inventive active ingredients or compositions for example an insecticidal protein, can result in control of certain pests. Surprisingly, a further synergistic effect can be observed in this case, which additionally increases the effectiveness for protection against attack by pests., microorganisms, weeds or abiotic stress.
  • the 2- ⁇ 3 - [2-( 1 - ⁇ [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl ⁇ piperidin-4-yl)- 1 ,3-thiazol-4-yl] -4,5- dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate are suitable for protection of seed of any plant variety which is used in agriculture, in the greenhouse, in forests or in horticulture.
  • the seed is that of cereals (such as wheat, barley, rye, millet and oats), oilseed rape, maize, cotton, soybean, rice, potatoes, sunflower, beans, coffee, beet (e.g. sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, onions and lettuce), lawns and ornamental plants.
  • cereals such as wheat, barley, rye, millet and oats
  • oilseed rape e.g. sugar beet and fodder beet
  • peanut such as tomato, cucumber, onions and lettuce
  • heterologous genes in transgenic seeds may originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
  • These heterologous genes preferably originates from Bacillus sp., in which case the gene product is effective against the European corn borer and/or the Western corn rootworm.
  • the heterologous genes originate from Bacillus thuringiensis.
  • the inventive composition is applied to seeds either alone or in a suitable formulation.
  • the seed is treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment.
  • seeds can be treated at any time between harvest and sometime after sowing. It is customary to use seed which has been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seed which has been harvested, cleaned and dried down to a moisture content of less than 15% by weight.
  • seed which, after drying, for example, has been treated with water and then dried again or seeds just after priming, or seeds stored in primed conditions or pre-germinated seeds, or seeds sown on nursery trays, tapes or paper.
  • the amount of the inventive composition applied to the seed and/or the amount of further additives is selected such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This must be ensured particularly in the case of active ingredients which can exhibit phytotoxic effects at certain application rates.
  • the 2- ⁇ 3 - [2-( 1 - ⁇ [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl ⁇ piperidin-4-yl)- 1 ,3-thiazol-4-yl] -4,5- dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate can be applied directly, i.e. without containing any other components and without having been diluted.
  • the 2- ⁇ 3-[2-(l- ⁇ [3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl ⁇ piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate can be converted to the customary formulations relevant to on-seed applications, such as solutions, emulsions, suspensions, powders, foams, slurries or combined with other coating compositions for seed, such as film forming materials, pelleting materials, fine iron or other metal powders, granules, coating material for inactivated seeds, and also ULV formulations.
  • formulations are prepared in a known manner, by mixing the active ingredients or active ingredient combinations with customary additives, for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • customary additives for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
  • Useful dyes which may be present in the seed dressing formulations usable in accordance with the invention are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.
  • Useful wetting agents which may be present in the seed dressing formulations usable in accordance with the invention are all substances which promote wetting and which are conventionally used for the formulation of active agrochemical ingredients.
  • Usable with preference are alkylnaphthalenesulphonates, such as diisopropyl- or diisobutylnaphthalenesulphonates.
  • Useful dispersants and/or emulsifiers which may be present in the seed dressing formulations usable in accordance with the invention are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agrochemical ingredients. Usable with preference are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
  • Useful nonionic dispersants include especially ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ether, and the phosphated or sulphated derivatives thereof.
  • Suitable anionic dispersants are especially lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehyde condensates.
  • Antifoams which may be present in the seed dressing formulations usable in accordance with the invention are all foam-inhibiting substances conventionally used for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference.
  • Preservatives which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal.
  • Secondary thickeners which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions.
  • Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
  • Adhesives which may be present in the seed dressing formulations usable in accordance with the invention are all customary binders usable in seed dressing products.
  • Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
  • the formulations for on-seed applications usable in accordance with the invention can be used to treat a wide variety of different kinds of seed either directly or after prior dilution with water.
  • the concentrates or the preparations obtainable therefrom by dilution with water can be used to dress the seed of cereals, such as wheat, barley, rye, oats, and triticale, and also seeds of maize, soybean, rice, oilseed rape, peas, beans, cotton, sunflowers, and beets, or else a wide variety of different vegetable seeds.
  • the formulations usable in accordance with the invention, or the dilute preparations thereof can also be used for seeds of transgenic plants. In this case, additional synergistic effects may also occur in interaction with the substances formed by expression.
  • the application rate of the formulations usable in accordance with the invention can be varied within a relatively wide range. It is guided by the particular content of the active ingredients in the formulations and by the seeds.
  • the application rates of each single active ingredient is generally between 0.001 and 15 g per kilogram of seed, preferably between 0.01 and 5 g per kilogram of seed.
  • plants and their parts are treated.
  • wild plant species and plant cultivars or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering methods if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the terms "parts” or “parts of plants” or “plant parts” have been explained above. More preferably, plants of the plant cultivars which are commercially available or are in use are treated in accordance with the invention.
  • Plant cultivars are understood to mean plants which have new properties ("traits") and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.
  • the method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds.
  • GMOs genetically modified organisms
  • Genetically modified plants are plants of which a heterologous gene has been stably integrated into genome.
  • the expression "heterologous gene” essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microRNA - miRNA - technology).
  • a heterologous gene that is located in the genome is also called a transgene.
  • a transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
  • Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means).
  • Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids. Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses.
  • Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
  • Plants and plant cultivars which may also be treated according to the invention are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation.
  • Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance.
  • Further yield traits include seed composition, such as carbohydrate content and composition for example cotton or starch, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
  • Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses).
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
  • Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects.
  • Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses.
  • Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance.
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics. Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as Tobacco plants, with altered post- translational protein modification patterns.
  • the application rate of the inventive active ingredients is • in the case of treatment of plant parts, for example leaves: from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more preferably from 50 to 300 g/ha (in the case of application by watering or dripping, it is even possible to reduce the application rate, especially when inert substrates such as rockwool or perlite are used);
  • a typical fungicide formulation containing 50 g of compound of formula (I) per liter was applied at several rates on corn seeds with conventional seed treatment method. Seeds were drilled in seedling trays; then young plants were transplanted to the field after 10 days. Plots received artificial inoculation with a suspension of spores of Peronosclerospora maydis. Trial design in the field consisted in randomized complete block with 20 m 2 plots and 3 replicates.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pretreatment Of Seeds And Plants (AREA)

Abstract

The present invention relates to the use of 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (see Figure 1) and of compositions comprising 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and further fungicides or insecticides for controlling downy mildew diseases of monocotyledon crops. Furthermore the treatment of seed is described to control downy mildew diseases of monocotyledon crops.

Description

Use of 2-{3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l-yllacetyl}piperidin-4-yl)-l,3-thiazol-4-yll- 4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate
The present invention relates to the use of 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (see Figure 1) and of compositions comprising 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and further fungicides or insecticides for controlling downy mildew diseases of monocotyledon crops. Furthermore the treatment of seed is described to control downy mildew diseases of monocotyledon crops.
2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazoM
l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate itself is known from WO WO2012/025557. 2- {3-[2-(l- { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl} piperidin-4-yl)- 1 ,3 -thiazol-4-yl] -4,5-dihydro- 1 ,2- oxazol-5-yl}-3-chlorophenyl methanesulfonate is a fungicide especially useful for the control of oomycetes such as Phytophthora species, for example Phytophthora infestans and Plasmopara species, for example Plasmopara viticola. This invention now provides an advantageous use of compound of formula (I) ,2- {3-[2-(l- {[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2-oxazol-5- yl}-3-chlorophenyl methanesulfonate, and of compositions comprising 2-{3-[2-(l-{[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl] -4,5-dihydro- 1 ,2-oxazol-5-yl} -3- chlorophenyl methanesulfonate and further active ingredients against downy mildew in monocotyledon crops, such as Peronosclerospora philippinensis in corn, sorghum or oat, Peronosclerospora in sugarcane, Sclerophthora rayssiae varzeae in corn, Sclerophthora macrocarpa in corn, wheat, barley or rice, Sclerospora graminicola in millets, Peronosclerospora maydis in corn or teosinte, Peronosclerospora sorghi in sorghum.
Figure imgf000002_0001
Figure 1 : 2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl} piperidin-4-yl)- 1 ,3-thiazol-4-yl] - 4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate
2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 ^
l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and combinations comprising 2- {3-[2-(l-{[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2-oxazol-5- yl}-3-chlorophenyl methanesulfonate and at least one further fungicide or insecticide are able to control Peronosclerospora philippinensis in corn, sorghum or oat.
2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3 -thiazol-4-yl] -4,5-dihydro- l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and combinations comprising 2- {3-[2-(l-{[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2-oxazol-5- yl}-3-chlorophenyl methanesulfonate and at least one further fungicide or insecticide are able to control Peronosclerospora in sugarcane.
2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazoM
l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and combinations comprising 2- {3-[2-(l-{[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2-oxazol-5- yl}-3-chlorophenyl methanesulfonate and at least one further fungicide or insecticide are able to control
Sclerophthora rayssiae varzeae in corn.
2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl} piperidin-4-yl)- 1 ,3 -thiazol-4-yl] -4,5-dihydro- l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and combinations comprising 2- {3-[2-(l-{[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2-oxazol-5- yl}-3-chlorophenyl methanesulfonate and at least one further fungicide or insecticide are able to control Sclerophthora macrocarpa in corn, wheat, barley or rice.
2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 ^
l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and combinations comprising 2- {3-[2-(l-{[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2-oxazol-5- yl}-3-chlorophenyl methanesulfonate and at least one further fungicide or insecticide are able to control Sclerospora graminicola in millets.
2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 ^
l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and combinations comprising 2- {3-[2-(l-{[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2-oxazol-5- yl}-3-chlorophenyl methanesulfonate and at least one further fungicide or insecticide are able to control Peronosclerospora maydis in corn or teosinte.
2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 ^
l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and combinations comprising 2- {3-[2-(l-{[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2-oxazol-5- yl}-3-chlorophenyl methanesulfonate and at least one further fungicide or insecticide are able to control Peronosclerospora sorghi in sorghum.
In conjunction with the present invention "controlling" denotes a significant reduction of the downy mildew infestation in comparison to the untreated crop, more preferably the infestation is essentially diminished (50-79%), most preferably the infestation is totally suppressed (80-100%).
In an alternative embodiment of the present invention 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate as such or formulations thereof can be applied in combination with further known fungicides, bactericides, acaricides, nematicides, herbicides, insecticides for broadening the activity spectrum and in order to prevent the development of resistance. In many instances, synergistic effects are obtained, i.e. the activity of the mixture exceeds the activity of the individual components.
According to the invention the expression "composition" stands for the various combinations of compounds A) and B), for example in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active compounds, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. Preferably the order of applying the compounds A) and B) is not essential for working the present invention. Formulations
The present invention further relates to a composition for controlling unwanted microorganisms, comprising 2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3 -thiazol-4-yl] - 4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate. These are preferably fungicidal compositions which comprise agriculturally suitable auxiliaries, solvents, carriers, surfactants or extenders. According to the invention, a carrier is a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for better applicability, in particular for application to plants or plant parts or seed. The carrier, which may be solid or liquid, is generally inert and should be suitable for use in agriculture.
Useful solid carriers include: for example ammonium salts and natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock flours, such as finely divided silica, alumina and silicates; useful solid carriers for granules include: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic flours, and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks; useful emulsifiers and/or foam-formers include: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and also protein hydrolysates; suitable dispersants are nonionic and/or ionic substances, for example from the classes of the alcohol-POE and/or -POP ethers, acid and/or POP POE esters, alkylaryl and/or POP POE ethers, fat and/or POP POE adducts, POE- and/or POP-polyol derivatives, POE- and/or POP-sorbitan or -sugar adducts, alkyl or aryl sulphates, alkyl- or arylsulphonates and alkyl or aryl phosphates or the corresponding PO-ether adducts. Additionally suitable are oligo- or polymers, for example those derived from vinylic monomers, from acrylic acid, from EO and/or PO alone or in combination with, for example, (poly)alcohols or (poly)amines. It is also possible to use lignin and its sulphonic acid derivatives, unmodified and modified celluloses, aromatic and/or aliphatic sulphonic acids and also their adducts with formaldehyde.
The active ingredients can be converted to the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances.
The active ingredients can be applied as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, water- or oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural products impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances. Application is accomplished in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading-on and the like. It is also possible to deploy the active ingredients by the ultra-low volume method or to inject the active ingredient preparation/the active ingredient itself into the soil. It is also possible to treat the seed of the plants. The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, emulsifier, dispersant and/or binder or fixing agent, wetting agent, a water repellent, if appropriate siccatives and UV stabilizers and if appropriate dyes and pigments, antifoams, preservatives, secondary thickeners, stickers, gibberellins and also other processing auxiliaries. The present invention includes not only formulations which are already ready for use and can be deployed with a suitable apparatus to the plant or the seed, but also commercial concentrates which have to be diluted with water prior to use.
The 2- {3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5- dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate may be present as such or in their (commercial) formulations and in the use forms prepared from these formulations as a mixture with other (known) active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.
The auxiliaries used may be those substances which are suitable for imparting particular properties to the composition itself or and/or to preparations derived therefrom (for example spray liquors, seed dressings), such as certain technical properties and/or also particular biological properties. Typical auxiliaries include: extenders, solvents and carriers.
Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for example from the classes of the aromatic and nonaromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which may optionally also be substituted, etherified and/or esterified), the ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, the unsubstituted and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulphones and sulphoxides (such as dimethyl sulphoxide).
Liquefied gaseous extenders or carriers are understood to mean liquids which are gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, or else butane, propane, nitrogen and carbon dioxide.
In the formulations it is possible to use tackifiers such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Further additives may be mineral and vegetable oils.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Useful liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, 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 sulphoxide, or else water.
Compositions comprising 2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl} piperidin-4-yl)- l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate may additionally comprise further components, for example surfactants. Suitable surfactants are emulsifiers and/or foam formers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants. Examples thereof are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, protein hydrolysates, lignosulphite waste liquors and methylcellulose. The presence of a surfactant is necessary if one of the active ingredients and/or one of the inert carriers is insoluble in water and when application is effected in water. The proportion of surfactants is between 5 and 40 per cent by weight of the inventive composition.
It is possible to use dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Further additives may be perfumes, mineral or vegetable, optionally modified oils, waxes and nutrients (including trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Additional components may be stabilizers, such as cold stabilizers, preservatives, antioxidants, light stabilizers, or other agents which improve chemical and/or physical stability.
If appropriate, other additional components may also be present, for example protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, stabilizers, sequestering agents, complex formers. In general, the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes. The formulations contain generally between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1 and 95% by weight, more preferably between 0.5 and 90% of active ingredient, most preferably between 10 and 70 per cent by weight.
The formulations described above can be used for controlling unwanted microorganisms, in which the compositions comprising 2- {3-[2-(l - { [3,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3- thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate are applied to the microorganisms and/or in their habitat.
Seed Treatment
The invention furthermore includes a method for treating seed.
A further aspect of the present invention relates in particular to seeds (dormant, primed, pregerminated or even with emerged roots and leaves) treated with 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate. The inventive seeds are used in methods for protection of seeds and emerged plants from the seeds from phytopathogenic harmful fungi. In these methods, seed treated with at least one inventive active ingredient is used.
The 2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl} piperidin-4-yl)- 1 ,3-thiazol-4-yl] -4,5- dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate are also suitable for the treatment of seeds and young seedlings. A large part of the damage to crop plants caused by harmful organisms is triggered by the infection of the seeds before sowing or after germination of the plant. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive, and even small damage may result in the death of the plant. Accordingly, there is great interest in protecting the seed and the germinating plant by using appropriate compositions.
It is also desirable to optimize the amount of the active ingredient used so as to provide the best possible protection for the seeds, the germinating plants and emerged seedlings from attack by phytopathogenic fungi, but without damaging the plants themselves by the active ingredient used. In particular, methods for the treatment of seed should also take into consideration the intrinsic phenotypes of transgenic plants in order to achieve optimum protection of the seed and the germinating plant with a minimum of crop protection compositions being employed.
The present invention therefore also relates to a method for protecting seeds, germinating plants and emerged seedlings against attack by animal pests and/or phytopathogenic harmful microorganisms by treating the seeds with an inventive composition. The invention also relates to the use of the compositions according to the invention for treating seeds for protecting the seeds, the germinating plants and emerged seedlings against animal pests and/or phytopathogenic microorganisms. The invention further relates to seeds which has been treated with an inventive composition for protection from animal pests and/or phytopathogenic microorganisms.
One of the advantages of the present invention is that the treatment of the seeds with these compositions not only protects the seed itself, but also the resulting plants after emergence, from animal pests and/or phytopathogenic harmful microorganisms. In this way, the immediate treatment of the crop at the time of sowing or shortly thereafter protect plants as well as seed treatment in prior to sowing. It is likewise considered to be advantageous that the inventive active ingredients or compositions can be used especially also for transgenic seed, in which case the plant which grows from this seed is capable of expressing a protein which acts against pests, herbicidal damage or abiotic stress. The treatment of such seeds with the inventive active ingredients or compositions, for example an insecticidal protein, can result in control of certain pests. Surprisingly, a further synergistic effect can be observed in this case, which additionally increases the effectiveness for protection against attack by pests., microorganisms, weeds or abiotic stress.
The 2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl} piperidin-4-yl)- 1 ,3-thiazol-4-yl] -4,5- dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate are suitable for protection of seed of any plant variety which is used in agriculture, in the greenhouse, in forests or in horticulture. More particularly, the seed is that of cereals (such as wheat, barley, rye, millet and oats), oilseed rape, maize, cotton, soybean, rice, potatoes, sunflower, beans, coffee, beet (e.g. sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, onions and lettuce), lawns and ornamental plants. Of particular significance is the treatment of the seed of wheat, soybean, oilseed rape, maize and rice. As also described below, the treatment of transgenic seed with the inventive active ingredients or compositions is of particular significance. This refers to the seed of plants containing at least one heterologous gene which allows the expression of a polypeptide or protein, e.g. having insecticidal properties. These heterologous genes in transgenic seeds may originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. These heterologous genes preferably originates from Bacillus sp., in which case the gene product is effective against the European corn borer and/or the Western corn rootworm. Particularly preferably, the heterologous genes originate from Bacillus thuringiensis.
In the context of the present invention, the inventive composition is applied to seeds either alone or in a suitable formulation. Preferably, the seed is treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment. In general, seeds can be treated at any time between harvest and sometime after sowing. It is customary to use seed which has been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seed which has been harvested, cleaned and dried down to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seed which, after drying, for example, has been treated with water and then dried again, or seeds just after priming, or seeds stored in primed conditions or pre-germinated seeds, or seeds sown on nursery trays, tapes or paper.
When treating the seeds, it generally has to be ensured that the amount of the inventive composition applied to the seed and/or the amount of further additives is selected such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This must be ensured particularly in the case of active ingredients which can exhibit phytotoxic effects at certain application rates.
The 2- {3 - [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl} piperidin-4-yl)- 1 ,3-thiazol-4-yl] -4,5- dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate can be applied directly, i.e. without containing any other components and without having been diluted. In general, it is preferable to apply the compositions 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. The 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate can be converted to the customary formulations relevant to on-seed applications, such as solutions, emulsions, suspensions, powders, foams, slurries or combined with other coating compositions for seed, such as film forming materials, pelleting materials, fine iron or other metal powders, granules, coating material for inactivated seeds, and also ULV formulations.
These formulations are prepared in a known manner, by mixing the active ingredients or active ingredient combinations with customary additives, for example customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.
Useful dyes which may be present in the seed dressing formulations usable in accordance with the invention are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.
Useful wetting agents which may be present in the seed dressing formulations usable in accordance with the invention are all substances which promote wetting and which are conventionally used for the formulation of active agrochemical ingredients. Usable with preference are alkylnaphthalenesulphonates, such as diisopropyl- or diisobutylnaphthalenesulphonates.
Useful dispersants and/or emulsifiers which may be present in the seed dressing formulations usable in accordance with the invention are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agrochemical ingredients. Usable with preference are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Useful nonionic dispersants include especially ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ether, and the phosphated or sulphated derivatives thereof. Suitable anionic dispersants are especially lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehyde condensates.
Antifoams which may be present in the seed dressing formulations usable in accordance with the invention are all foam-inhibiting substances conventionally used for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference.
Preservatives which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal.
Secondary thickeners which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
Adhesives which may be present in the seed dressing formulations usable in accordance with the invention are all customary binders usable in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.
The formulations for on-seed applications usable in accordance with the invention can be used to treat a wide variety of different kinds of seed either directly or after prior dilution with water. For instance, the concentrates or the preparations obtainable therefrom by dilution with water can be used to dress the seed of cereals, such as wheat, barley, rye, oats, and triticale, and also seeds of maize, soybean, rice, oilseed rape, peas, beans, cotton, sunflowers, and beets, or else a wide variety of different vegetable seeds. The formulations usable in accordance with the invention, or the dilute preparations thereof, can also be used for seeds of transgenic plants. In this case, additional synergistic effects may also occur in interaction with the substances formed by expression.
For treatment of seeds with the formulations usable in accordance with the invention, or the preparations prepared therefrom by adding water, all mixing units usable customarily for on-seed applications are useful. Specifically, the procedure in on-seed applications is to place the seeds into a mixer, to add the particular desired amount of the formulations, either as such or after prior dilution with water, and to mix everything until all applied formulations are distributed homogeneously on the seeds. If appropriate, this is followed by a drying operation.
The application rate of the formulations usable in accordance with the invention can be varied within a relatively wide range. It is guided by the particular content of the active ingredients in the formulations and by the seeds. The application rates of each single active ingredient is generally between 0.001 and 15 g per kilogram of seed, preferably between 0.01 and 5 g per kilogram of seed.
GMO
As already mentioned above, it is possible to treat all plants and their parts in accordance with the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms "parts" or "parts of plants" or "plant parts" have been explained above. More preferably, plants of the plant cultivars which are commercially available or are in use are treated in accordance with the invention. Plant cultivars are understood to mean plants which have new properties ("traits") and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.
The method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds. Genetically modified plants (or transgenic plants) are plants of which a heterologous gene has been stably integrated into genome. The expression "heterologous gene" essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology, RNA interference - RNAi - technology or microRNA - miRNA - technology). A heterologous gene that is located in the genome is also called a transgene. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means).
Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids. Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance. Plants and plant cultivars which may also be treated according to the invention, are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance. Further yield traits include seed composition, such as carbohydrate content and composition for example cotton or starch, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.
Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses). Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance. Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance. Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product.
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics. Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics.
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering.
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as Tobacco plants, with altered post- translational protein modification patterns.
Application Rates
When using the 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4- yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate as fungicides, the application rates can be varied within a relatively wide range, depending on the kind of application. The application rate of the inventive active ingredients is • in the case of treatment of plant parts, for example leaves: from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more preferably from 50 to 300 g/ha (in the case of application by watering or dripping, it is even possible to reduce the application rate, especially when inert substrates such as rockwool or perlite are used);
• in the case of seed treatment: from 0.1 to 400 g per 100 kg of seed, preferably from 1 to 150 g per 100 kg of seed, more preferably from 2.5 to 50 g per 100 kg of seed, even more preferably from 5 to 25 g per 100 kg of seed;
• in the case of soil treatment: from 0.1 to 10 000 g/ha, preferably from 1 to 5000 g/ha.
The following examples are intended to illustrate the present invention.
Examples
Control of corn downy mildew {Peronosclerospora maydis)
This example illustrates the efficacy of compound of formula (I) according to the invention against corn downy mildew (Peronosclerospora maydis).
A typical fungicide formulation containing 50 g of compound of formula (I) per liter was applied at several rates on corn seeds with conventional seed treatment method. Seeds were drilled in seedling trays; then young plants were transplanted to the field after 10 days. Plots received artificial inoculation with a suspension of spores of Peronosclerospora maydis. Trial design in the field consisted in randomized complete block with 20 m2 plots and 3 replicates.
Assessments of disease incidence on plants were performed twice in order to evaluate the effect of fungicide treatments, when both crop and disease were well established. Results are presented in tables 1 and 2, below.
Table 1 : Efficacy of compound of formula (I) against corn downy mildew {Peronosclerospora maydis) as seed treatment. Mean values of 3 replicates (a.i. = active ingredient)
Figure imgf000015_0001
Means followed by the same letter do not significantly differ (P=0.05) according to Duncan 's Multiple range test
Table 2: Efficacy of compound of formula (I) against corn downy mildew {Peronosclerospora maydis) as seed treatment. Mean values of 3 replicates (a.i. = active ingredient) % disease incidence % disease incidence
Rate g ai/ (% efficacy Abbott) (% efficacy Abbott) composition
kg seeds 38 days after 52 days after
treatment treatment
Untreated - 15.8 19.2
2-{3-[2-(l-{[3,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-
0,1 6.7 (57.9) 7.5 (60.9) thiazol-4-yl]-4,5 -dihydro- 1 ,2-oxazol-5 -yl } -3 - chlorophenyl methanesulfonate EC50
2-{3-[2-(l-{[3,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-
0,5 10.8 (31.6) 8.3 (56.5) thiazol-4-yl]-4,5 -dihydro- 1 ,2-oxazol-5 -yl } -3 - chlorophenyl methanesulfonate EC50
2-{3-[2-(l-{[3,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-
2,5 0 (100) 1.3 (93.5) thiazol-4-yl]-4,5 -dihydro- 1 ,2-oxazol-5 -yl } -3 - chlorophenyl methanesulfonate EC50
Means followed by the same letter do not significantly differ (P=0.05) according to Duncan 's Multiple range test
Conclusion:
Efficacy results presented in tables 1 and 2, above, demonstrate the efficacy of 2- {3-[2-(l- {[3,5- bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3-thiazol-4-yl]-4,5-dihydro- 1 ,2-oxazol-5- yl} -3 -chlorophenyl methanesulfonate against corn downy mildew (Peronosclerospora maydis) when applied as seed treatment on corn at rates between 0.1 and 2.5 g a.i./kg seeds.

Claims

Claims:
1. Use of 2- {3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4- yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate for controlling downy mildew diseases of monocotyledon crops.
2. Use according to claim 1 for controlling Peronosclerospora philippinensis in corn sorghum or oat.
3. Use according to claim 1 for controlling Peronosclerospora in sugarcane.
4. Use according to claim 1 for controlling Sclerophthora rayssiae varzeae in corn.
5. Use according to claim 1 for controlling Sclerophthora macrocarpa in corn, wheat, barley and rice.
6. Use according to claim 1 for controlling Sclerospora graminicola in millets.
7. Use according to claim 1 for controlling Peronosclerospora maydis in corn or teosinte.
8. Use according to claim 1 for controlling Peronosclerospora sorghi in sorghum.
9. Use of combinations comprising 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and at least one further fungicide or insecticides for controlling downy mildew diseases of monocotyledon crops.
10. Use of combinations comprising 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and at least one further fungicide or insecticides for controlling Peronosclerospora maydis in corn or teosinte.
11. Use according to any of claims 1 to 10 for the treatment of seed.
12. Method of controlling downy mildew diseases of monocotyledon crops, characterized in that 2-{3- [2-( 1 - { [3 ,5-bis(difluoromethyl)- 1 H-pyrazol- 1 -yl]acetyl}piperidin-4-yl)- 1 ,3 -thiazol-4-yl] -4,5- dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate is applied to the plant pathogen and/or their environment.
13. Method according to claim 12, characterized that the pathogen is selected from the group Peronosclerospora philippinensis in corn sorghum or oat, Peronosclerospora in sugarcane, Sclerophthora rayssiae varzeae in corn, Sclerophthora macrocarpa in corn, wheat, barley and rice, Sclerospora graminicola in millets, Peronosclerospora maydis in corn or teosinte, Peronosclerospora sorghi in sorghum.
14. Method of controlling downy mildew diseases of monocotyledon crops, characterized in that combinations comprising 2- {3-[2-(l- {[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4- yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate and at least one further fungicide or insecticides is applied to the plant pathogen and/or their environment.
15. Method according to claim 14, characterized that the pathogen is Peronosderospora maydis in corn or teosinte.
16. Method according to claim 12 or 14, wherein the treated crops are transgenic crops.
17. Method of controlling downy mildew diseases of monocotyledon crops, characterized in that plant seeds are treated with 2- {3-[2-(l-{[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)- l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate according to Claims 12 to 16.
18. Method according to Claim 17, wherein the plant seeds are derived from a transgenic plant.
PCT/EP2016/059213 2015-04-29 2016-04-26 Use of 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1h-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate Ceased WO2016173996A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PH12017501985A PH12017501985A1 (en) 2015-04-29 2017-10-27 Use of 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1h-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15165753 2015-04-29
EP15165753.3 2015-04-29

Publications (1)

Publication Number Publication Date
WO2016173996A1 true WO2016173996A1 (en) 2016-11-03

Family

ID=53008398

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/059213 Ceased WO2016173996A1 (en) 2015-04-29 2016-04-26 Use of 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1h-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate

Country Status (3)

Country Link
AR (1) AR104781A1 (en)
PH (1) PH12017501985A1 (en)
WO (1) WO2016173996A1 (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012025557A1 (en) 2010-08-25 2012-03-01 Bayer Cropscience Ag Heteroarylpiperidine and -piperazine derivatives as fungicides
WO2013127704A1 (en) * 2012-02-27 2013-09-06 Bayer Intellectual Property Gmbh Active compound combinations containing a thiazoylisoxazoline and a fungicide
WO2014206896A1 (en) * 2013-06-24 2014-12-31 Bayer Cropscience Ag Piperidinecarboxylic acid derivatives as fungicides
CN104336023A (en) * 2013-08-08 2015-02-11 陕西美邦农药有限公司 Sterilization composition containing oxathiapiprolin
CN104336048A (en) * 2013-08-08 2015-02-11 陕西美邦农药有限公司 Bactericidal composition containing fluorothiazolepyrithylone and triazoles
CN104336040A (en) * 2013-07-31 2015-02-11 陕西美邦农药有限公司 An efficient sterilization composition containing oxathiapiprolin
WO2015055707A1 (en) * 2013-10-16 2015-04-23 Bayer Cropscience Ag Active compound combinations comprising a (thio)carboxamide derivative and a fungicidal compound
WO2015055574A1 (en) * 2013-10-17 2015-04-23 Bayer Cropscience Ag Novel crystalline form of 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1h-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethane sulfonate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012025557A1 (en) 2010-08-25 2012-03-01 Bayer Cropscience Ag Heteroarylpiperidine and -piperazine derivatives as fungicides
WO2013127704A1 (en) * 2012-02-27 2013-09-06 Bayer Intellectual Property Gmbh Active compound combinations containing a thiazoylisoxazoline and a fungicide
WO2014206896A1 (en) * 2013-06-24 2014-12-31 Bayer Cropscience Ag Piperidinecarboxylic acid derivatives as fungicides
CN104336040A (en) * 2013-07-31 2015-02-11 陕西美邦农药有限公司 An efficient sterilization composition containing oxathiapiprolin
CN104336023A (en) * 2013-08-08 2015-02-11 陕西美邦农药有限公司 Sterilization composition containing oxathiapiprolin
CN104336048A (en) * 2013-08-08 2015-02-11 陕西美邦农药有限公司 Bactericidal composition containing fluorothiazolepyrithylone and triazoles
WO2015055707A1 (en) * 2013-10-16 2015-04-23 Bayer Cropscience Ag Active compound combinations comprising a (thio)carboxamide derivative and a fungicidal compound
WO2015055574A1 (en) * 2013-10-17 2015-04-23 Bayer Cropscience Ag Novel crystalline form of 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1h-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethane sulfonate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GULYA T J: "EFFICACY OF SINGLE AND TWO-WAY FUNGICIDE SEED TREATMENTS FOR THE CONTROL OF METALAXYL-RESISTANT STRAINS OF PLASMOPARA HALSTEDII (SUNFLOWER DOWNY MILDEW)", BRIGHTON CROP PROTECTION CONFERENCE PESTS AND DISEASES, XX, XX, vol. 2, 1 January 2002 (2002-01-01), pages 575 - 580, XP009061404, ISSN: 0955-1506 *
RAM P THAKUR ET AL: "Influence of dosage, storage time and temperature on efficacy of metalaxyl-treated seed for the control of pearl millet downy mildew", EUROPEAN JOURNAL OF PLANT PATHOLOGY, KLUWER ACADEMIC PUBLISHERS, DO, vol. 129, no. 2, 9 September 2010 (2010-09-09), pages 353 - 359, XP019872937, ISSN: 1573-8469, DOI: 10.1007/S10658-010-9679-9 *

Also Published As

Publication number Publication date
PH12017501985A1 (en) 2018-03-19
AR104781A1 (en) 2017-08-16

Similar Documents

Publication Publication Date Title
DK2356906T3 (en) Synergistic fungicidal combination of active
EA023712B1 (en) Active compound combinations comprising a (thio)carboxamide derivative and a fungicidal compound
JP2013512934A (en) Pesticide mixture
JP6600633B2 (en) Active compound combinations
US10194659B2 (en) Active compound combinations
EA029048B1 (en) Active compounds combination comprising a lipo-chitooligosaccharide derivative for stimulating plant growth
US20170325452A1 (en) Active compound combinations
CN101188935B (en) synergistic fungicidal active substance combinations
CN114223665A (en) Application of bactericidal composition in preventing and treating plant pathogenic fungi
WO2017004744A1 (en) Use of penflufen
CN111263587B (en) Use of isotianil against Panama disease
US12063932B2 (en) Method of promoting plant growth effects
RU2858552C2 (en) Agrochemical composition
WO2018046431A1 (en) Active compound combinations
WO2016173996A1 (en) Use of 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1h-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate
JP6913082B2 (en) Use of isothianil for zebra chip disease control
WO2017020180A1 (en) Method and use of penflufen for controlling corn head smut
CN106982842B (en) Bactericidal composition
UA128698C2 (en) Use of the succinate dehydrogenase inhibitor fluopyram for controlling root rot complex and/or seedling disease complex caused by rhizoctonia solani, fusarium species and pythium species in brassicaceae species
WO2012123326A1 (en) Use of dithiine-tetracarboximides as bird repellent
TWI788458B (en) A synergistic insecticidal composition comprising methomyl and fipronil
CN112056316A (en) Bactericidal composition
CN106982850B (en) Bactericidal composition
CN106982853A (en) a bactericidal composition
CN106982855A (en) a bactericidal composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16719061

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 12017501985

Country of ref document: PH

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16719061

Country of ref document: EP

Kind code of ref document: A1