TW201402011A - Use of compounds for the control of cereal diseases - Google Patents

Abstract

The present invention relates to the use of compounds of the general formula wherein the substituents are as defined in claim 1, for the control of at least one cereal disease.

Description

Use of compounds for the control of sputum diseases

This invention relates to the use of certain carboxylic acid guanamines for controlling cereal diseases, particularly cereal leaf spot, especially for Septoria disease.

Cereal diseases caused by fungi can cause severe yield declines and constitute a major limiting factor for cereal production. Therefore, there is an ongoing need for effective methods for controlling such diseases. The present invention achieves this goal and creates additional advantages.

Certain carboxylic acid amide derivatives and their use as fungicides are disclosed, for example, in WO 09/030467 and WO 09/030469.

The invention therefore relates to the use of a compound of formula (I) for the control of at least one cereal disease: Wherein R ¹ is ethyl or methylthio; R ² is CR ³ R ⁴ R ⁵ ; R ³ and R ⁴ together, are hydrogen or methyl; and R ⁵ is methyl, ethyl or vinyl; Its salt or N-oxide.

The compounds of the formula (I) contain at least one asymmetric carbon atom and may therefore exist as enantiomers, as diastereomeric pairs or as mixtures of such. Compounds of the general formula (I) may therefore exist as racemates, diastereomers, or individual enantiomers, and the invention encompasses all possible isomers or in all proportions a mixture of isomers.

The salt which the compound of the formula (I) can form is preferably those formed by the interaction of the compounds with an acid. The term "acid" includes mineral acids such as hydrogen halides, sulfuric acid, phosphoric acid, and the like, as well as organic acids, preferably common alkanoic acids such as formic acid, acetic acid, and propionic acid.

The N-oxide is preferably a compound of the formula (I) having an oxygen atom at the nitrogen atom of the quinoline ring.

Preferably, R ³ and R ⁴ together are hydrogen.

R ^{5 is} preferably a methyl group or an ethyl group.

In a particularly preferred group of compounds of formula (I), R ¹ is ethyl, R ³ and R ^{4 are} together hydrogen and R ⁵ is methyl.

In another preferred group of compounds of formula (I), R ¹ is ethyl, R ³ and R ^{4 are} together hydrogen and R ⁵ is ethyl.

In a particularly preferred group of compounds of formula (I), R ¹ is methylthio, R ³ and R ^{4 are} together hydrogen and R ⁵ is methyl.

In another particularly preferred group of compounds of formula (I), R ¹ is methylthio, R ³ and R ^{4 are} together hydrogen and R ⁵ is ethyl.

The compounds which can be used according to the invention are listed in Table 1 below.

a compound of formula (I):

Such compounds of formula (I) can be prepared by chemical reactions known in the art in a manner similar to that outlined in WO 09/030467 and WO 09/049716.

As mentioned above, the cereal diseases according to the invention are caused by one or more fungi. Knot The term "control of cereal diseases" and "control of fungi" are used equally and refer to the use of compounds of formula (I) to control cereal diseases caused by one or more fungi.

Preferably, at least one fungus is controlled using a compound of formula (I) selected from the group consisting of: Blumeria graminis sp. ( white powdery mildew of wheat and barley) Drechslera tritici-repentis (wheat leaf spot of wheat), Fusarium spp. ( scurvy of wheat), including Fusarium culmorum , wheat total pathogen ( Gaeumannomyces graminis ), wheat plague , Magnaporthe grisea (rice blast), Monographella nivalis (wheat mold for wheat), Mycosphaerella graminicola (wheat) Leaf spot), Oculimacula sp . (whole eye disease), Phseosphaeria nodorum (wheat spot blotch), Puccinia recondita (Brown rust of wheat), Pyrenophora teres (barley spot of barley), Ramularia collo-cygni (barley leaf spot), Rhizoctonia Solani ) (rice sheath blight), Fusarium sinensis ( Rhy Nchosporium secalis ) (barley brown spot) and its mixture.

In particular, the compounds of formula (I) prove to be suitable for controlling cereal leaf spot caused by at least one fungus selected from the group consisting of: Demyrobacter (Wheat Leaf of Wheat), Magnaporthe oryzae (rice) Rickets), Grubulus vulgaris (spot leaf spot of wheat), A. sinensis (spotted blight of wheat), Rhizoctonia solani (barley spot of barley), S. serrata (barley leaf) Spot disease), Rhizoctonia solani (rice sheath blight), Fusarium sinensis (barley brown spot) and mixtures thereof.

The compounds of formula (I) are especially useful for controlling wheat sclerotium caused by Phytophthora sinensis (leaf leaf spot) and, or by A. sinensis.

Preferably, the cereal is selected from the group consisting of wheat, barley, rye, and rice, and preferably wheat.

Compounds of formula (I) can be moved topically, top to bottom or locally in plant tissue to effectively combat one or more fungi. Furthermore, compounds of formula (I) may be sufficiently volatile to be active in the vapor phase against one or more fungi on plants.

"Use" of a compound of formula (I) according to the invention means that the compound is applied to cereals. The compound of formula (I) can be administered by any of the known methods of applying a fungicidal compound. For example, it (formulated or unformulated) can be applied directly to the plant (this refers to any part of the plant, including leaves, stems, branches or roots), to the seed before planting and to the plant propagation material, or to Plant growth or other medium to be planted (eg root week soil, common soil, paddy water or hydroponic system), or it may be sprayed, dusted, applied by dipping, applied as a cream or paste formulation, as Vapor application or by application of a composition such as a granule composition or a composition encased in a water-soluble pouch to a soil or water environment.

Accordingly, the present invention provides a method for controlling or controlling a cereal disease, the method comprising applying a fungicidally effective amount of a compound of formula (I) to a plant, a seed of the plant, a locus or soil of the plant or seed or any other Plant growth medium, the seed or the plant lineage.

Administration of a compound of formula (I) also refers to injection into a plant or spraying onto a plant using electrodynamic spraying techniques or other low volume methods, or by a terrestrial or aerial irrigation system.

According to the invention, "control" includes controlling, preventing and treating cereal diseases or, in other words, using a compound of formula (I) as a protective, prophylactic, therapeutic, systemic, eradicating and/or resistant against cereal diseases. Antisporulant treatment is used or administered.

As an example, control refers to the risk of any undesired or undesired effects, such as: - fungal infestation or fungal attack on plants, parts or seeds of plants, and - damage to plant diseases caused by fungi to plants, parts of plants or seeds, reduced to such levels as to be observed and not A modification of a plant-like, plant-like fraction or seed treated by a compound of formula (I).

The term "plant" as used herein includes seedlings and shrubs. The term "plant" as used herein also includes crops of useful plants to which the composition according to the invention may be used, and in particular includes cereals, in particular wheat, barley, rye and rice.

Furthermore, the term "crop" is understood to also include crops that are rendered tolerant to a variety of herbicides or classes of herbicides (eg, ALS, GS, EPSPS, PPO, and HPPD inhibitors) due to conventional breeding or genetic engineering methods.

These compounds of formula (I) are preferably used in the form of compositions for agricultural and horticultural purposes.

In order to use the compounds of formula (I) according to the invention, the compounds of formula (I) are generally formulated into compositions which comprise, in addition to a fungicidally effective amount of a compound of formula (I), suitable An inert diluent or carrier, and optionally additional fungicidal compounds and/or surfactants (SFA). SFA is a chemical that modifies the interface (eg, liquid/solid, liquid/air or liquid/liquid interface) properties by reducing the interfacial tension and thereby causing other properties (eg, dispersion, emulsification, and wetting) to change. . Preferably, all compositions (both solid and liquid formulations) comprise from 0.0001% to 95% by weight, more preferably from 1% to 85%, such as from 5% to 60%, of formula (I) compound of. The composition is generally used for controlling fungi such that the compound of formula (I) is from 0.1 g to 10 kg per hectare, preferably from 1 g to 6 kg per hectare, more preferably from 1 g to 1 kg per hectare. The ratio of administration.

When used in a seed dressing, the compound of formula (I) is from 0.0001 g to 10 g per kg of seed (e.g., 0.001 g or 0.05 g), preferably from 0.005 g to 10 g, more preferably from 0.005 g to 4 g. The ratio is used.

In still another aspect, the present invention provides a method of controlling or controlling a fungus at a locus comprising treating a fungus or a fungus with a fungicidally effective amount of a compound having formula (I), wherein the fungus is selected From the next group, the group includes: species of the genus Maltonia, the species of the genus Demyil, Fusarium, the total pathogen of wheat, the blast fungus, the genus Fusarium oxysporum, the genus Phytophthora, the genus Species, A. sinensis, Puccinia serrata, Rhizoctonia solani, S. sphaeroides, Rhizoctonia solani, Fusarium sinensis and their mixtures.

If a compound of formula (I) for use according to the invention is formulated into a composition, the composition may be selected from a wide variety of formulation types, including dustable powders (DP), soluble powders (SP), water soluble Granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), Ultra low volume liquid (UL), emulsifiable concentrate (EC), dispersible concentrate (DC), emulsion (both oil-in-water (EW) and water-in-oil (EO)), microemulsion (ME) Suspension concentrate (SC), aerosol, mist/smoke formulation, capsule suspension (CS), and seed treatment formulations. The type of formulation selected in any case will depend on the particular purpose envisioned and the physical, chemical and biological properties of the compound of formula (I).

The dusting powder (DP) can be prepared by reacting a compound of formula (I) with one or more solid diluents (for example, natural clay, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, diatomaceous earth). , white peony, diatomaceous earth, calcium phosphate, calcium carbonate and magnesium carbonate, sulfur, lime, flour, talc and other organic and inorganic solid carriers) are mixed and mechanically ground to powder.

The soluble powder (SP) can be obtained by combining a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium hydrogencarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) Optionally, one or more wetting agents, one or more dispersing agents, or a mixture of such agents are mixed to prepare to improve water dispersibility/water solubility. The mixture was then ground to a fine powder. Similar compositions can also be granulated to form water soluble particles (SG).

Wettable powder (WP) may be obtained by combining a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents, and preferably one or more dispersing agents, and optionally One or more suspending agents are mixed to prepare to promote dispersion in the liquid. The mixture was then ground to a fine powder. Similar compositions can also be granulated to form water dispersible granules (WG).

Granules (GR) may be formed by granulating a mixture of a compound of formula (I) with one or more powdered solid diluents or carriers, or by formulating a compound of formula (I) (or Its solution in a suitable reagent) is absorbed into a porous particulate material (such as pumice, attapulgite clay, fuller's earth, diatomaceous earth, diatomaceous earth or corncob powder) or by having a compound of formula (I) (or Its solution in a suitable reagent is adsorbed onto a hard core material (for example sand, citrate, mineral carbonate, sulphate or phosphate) and, if necessary, dried to form from preformed blank particles. Agents commonly used to aid absorption or adsorption include solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters, and adhesives such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugar and Vegetable oil). It is also possible to include one or more other additives (such as emulsifiers, wetting agents or dispersing agents) in the granules.

A dispersible concentrate (DC) can be dissolved in water or organic by dissolving a compound of formula (I) It is prepared by using a solvent such as a ketone, an alcohol or a glycol ether. These solutions may contain a surfactant (for example to improve water dilution or prevent crystallization in a spray tank).

An emulsifiable concentrate (EC) or an oil-in-water emulsion (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally comprising one or more wetting agents, one or more emulsifiers or Prepared in a mixture of reagents). Suitable organic solvents for use in the EC include aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes such as SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; registered trademarks of SOLVESSO, ketones such as cyclohexanone or methylcyclohexane. Ketone), alcohol (such as benzyl alcohol, mercapto alcohol or butanol), N -alkylpyrrolidone (such as N -methylpyrrolidone or N -octylpyrrolidone), dimethyl decylamine of fatty acid (e.g., C ₈ -C ₁₀ fatty acid dimethyl decylamine) and chlorinated hydrocarbons. The EC product can be emulsified spontaneously upon addition to water, resulting in an emulsion that is sufficiently stable to allow for application by spraying with a suitable device. The preparation of EW involves obtaining as a liquid (if it is not liquid at ambient temperature it can be melted at a reasonable temperature typically below 70 ° C) or in solution (by dissolving it in a suitable solvent) The compound of formula (I) is then emulsified under high shear to the water containing one or more SFAs to produce an emulsion. Suitable solvents for use in EW include vegetable oils, chlorinated hydrocarbons such as chlorobenzene, aromatic solvents such as alkylbenzenes or alkylnaphthalenes, and other suitable organic solvents which have low solubility in water.

Microemulsions (ME) can be prepared by mixing water with a blend of one or more solvents and one or more SFAs to spontaneously produce a thermodynamically stable isotropic liquid formulation. The compound of formula (I) is initially present in water or in a solvent/SFA blend. Solvents suitable for use in ME include those described above for use in EC or EW. The ME can be an oil-in-water system or a water-in-oil system (which system can be determined by conductivity testing) and can be adapted to mix water-soluble and oil-soluble pesticides in the same formulation. ME is suitable for dilution into water, keeping It is a microemulsion or forms a conventional oil-in-water emulsion.

The suspension concentrate (SC) may comprise an aqueous or non-aqueous suspension of finely divided insoluble solid particles of the compound of formula (I). SC can be prepared by ball or bead milling a solid compound of formula (I), optionally with one or more dispersing agents, in a suitable medium to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and may include a suspending agent to reduce the rate of settling of the particles. Alternatively, the compound of formula (I) can be dry milled and added to water containing the reagents described above to produce the desired end product.

The aerosol formulation comprises a compound of formula (I) and a suitable propellant (e.g., n-butane). The compound of formula (I) can also be dissolved or dispersed in a suitable medium such as water or a water miscible liquid such as n-propanol to provide a combination for use in a non-pressurized hand spray pump. Things.

The compound of formula (I) can be mixed with the pyrotechnic mixture in the dry state to form a composition suitable for producing a smoke containing the compound in an enclosed space.

The capsule suspension (CS) can be prepared in a similar manner to the preparation of the EW formulation, but with an additional polymerization step such that an aqueous dispersion of oil droplets is obtained, wherein each oil droplet is encapsulated by the polymer shell and contains A compound of formula (I) and optionally a carrier or diluent thereof. The polymer shell can be prepared by an interfacial polycondensation reaction or by a coacervation procedure. Such compositions can provide controlled release of compounds of formula (I) and they can be used in seed treatment. Compounds of formula (I) can also be formulated in biodegradable polymer matrices to provide a slow controlled release of the compound.

The composition may include one or more additives to improve the biological properties of the composition (eg, by improving wettability, retention or distribution on the surface; rainfastness on the treated surface; or Absorption or migration of a compound of formula (I)). Such additives include surfactants, oil-based spray additives, such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oil), and such bio-enhancing adjuvants (which may help or modify formula (I) a blend of the constituents of the action of the compound).

The compound of formula (I) can also be formulated for use as a seed treatment, for example as a powder composition, including powder (DS) for dry seed treatment, water soluble powder (SS), or for slurry The treated water dispersible powder (WS), or as a liquid composition, includes a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparation of the DS, SS, WS, FS, and LS compositions are very similar to those of the DP, SP, WP, SC, and DC compositions described above, respectively. The composition for treating the seed may include an agent (e.g., mineral oil or film-forming barrier) for assisting attachment of the composition to the seed. The humectants, dispersants and emulsifiers can be cationic, anionic, amphoteric or nonionic types of SFA.

Suitable cationic SFAs include quaternary ammonium compounds such as cetyltrimethylammonium bromide, imidazolines and amine salts. Suitable anionic SFAs include alkali metal salts of fatty acids, aliphatic sulfate monoesters (such as sodium lauryl sulfate), salts of sulfonated aromatic compounds (such as sodium dodecylbenzenesulfonate, dodecylbenzenesulfonate). Calcium acid, butylnaphthalenesulfonate and a mixture of di-isopropyl- and tri-isopropyl-naphthalenesulfonate), sulfuric acid ethers, sulfated alcohol ethers (such as laureth-3-sodium sulfate a carboxylic acid ether (such as sodium laureth-3-carboxylate), a phosphate ester (product of the reaction of one or more fatty alcohols with phosphoric acid (mainly a monoester) or a reaction with phosphorus pentoxide) (mainly diesters), such as the reaction product between lauryl alcohol and tetraphosphoric acid; in addition these products can be ethoxylated), thiosuccinic acid amide, paraffin or olefin sulfonate, taurate and Wood sulfonate. Suitable SFAs of the amphoteric type include betaine, propionate and glycinate. Suitable nonionic types of SFA include alkylene oxides (examples) Such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof) with fatty alcohols (such as oleyl or cetyl alcohol) or with alkyl phenols (such as octylphenol, nonylphenol or octylcresol) a condensation product; a partial ester derived from a long-chain fatty acid or a hexitol anhydride; a condensation product of the partial ester with ethylene oxide; a block polymer (containing ethylene oxide and propylene oxide); an alkanol An amine; a monoester (such as a fatty acid polyethylene glycol ester); an amine oxide (such as lauryl dimethyl amine oxide); and lecithin.

Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and expanded clays (such as bentonite or attapulgite).

Compositions for use as aqueous formulations (aqueous solutions or dispersions) are generally provided in the form of a concentrate containing a high proportion of active ingredient which is added to the water prior to use. Such concentrates (which may include DC, SC, EC, EW, ME, SG, SP, WP, WG, and CS) are often required to undergo long term storage and can be added to water after such storage to form an aqueous formulation, which The formulations are maintained in a homogeneous state for a time sufficient to allow them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of the compound of formula (I) (e.g., 0.0001% to 10% by weight), depending on the purpose for which they are used.

The compound of formula (I) can be used in admixture with a fertilizer such as a fertilizer containing nitrogen, potassium or phosphorus. Suitable formulation types include fertilizer granules. These mixtures suitably comprise up to 25% by weight of a compound of formula (I).

The invention therefore also provides the combined use of a compound of formula (I) with a fertilizer-containing fertilizer composition.

The compositions used according to the invention may comprise other biologically active compounds, such as micronutrients, or compounds having similar or supplemental fungicidal activity, or have the property of regulating plant growth, weeding, insecticidal, nematicidal or acaricidal activity. compound of.

By including another fungicide, the resulting composition can have a broader spectrum of activity or a higher level of intrinsic activity than the compound of formula (I) alone. Furthermore, the other fungicides may have a synergistic effect on the fungicidal activity of the compounds of formula (I).

The compound of formula (I) may be the sole active ingredient of the composition or, where appropriate, it may be combined with one or more additional active ingredients (for example pesticides, fungicides, synergists, herbicides or plants) Conditioner) mixed. Additional active ingredients may: provide a composition having a broader spectrum of activity or increased retention time at the locus; synergistically or supplementing the activity of the compound having formula (I) (eg, by increasing the rate of action or overcoming repellency); Or help overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend on the intended application of the composition.

An example of an additional fungicidal compound which may be included in the compositions of the invention is AC382042 ( N- (1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorobenzene) Oxy)propanamide), arsenic acid benzene-S-methyl, cotton ring, 4-dodecyl-2,6-dimethyl Aldimorph, carbendazim, aziconazole, azathioprine, azoxystrobin, benzathine, benomyl, phenothiamine, biloxazol, biphenyl triazole alcohol, kill Magnaportin S, boscalid (a new name for nicofen), fenfluzol, acetaminophen sulfonate, captan, captan, carbendazim , carbendazim hydrochloride, wilting, ciprofloxacin, carvone, CGA 41396, CGA 41397, methyl chlorpyrifos, chlorbenzthiazone, chlorothalonil, acetaminophen, clarcon (clozylacon), a compound containing copper such as copper oxychloride, copper hydroxyquinolate, copper sulphate, copper sulphate and a mixture of Bordeaux mixture, cyanazolam, cyanosin (IKF-916), cyclofluoride Bismuth, cymoxanil, cyproconazole, cyprodinil, imiprozil, di-2-dithiopyridine 1,1'-dioxide, bacteriostatic, chloramphenicol, chlorfenapyr, Chloramine, carbendazim, difenoconazole, wild swallow, diflurine, O, O -di-isopropyl- S -benzyl phosphorothioate, dimefluazole, ground Dimetconazole, foramin, olefin Porphyrin, ether myramine, diniconazole, dipyridamole, dithianon, dodecyldimethylammonium chloride, twelve rings Porphyrin, dodecyl hydrazine, dodecyl hydrazine acetate, ketone, epoxiconazole, ethaboxam, acetem, ( Z ) -N -benzyl- N ([methyl (methyl) Thioethylidene oxycarbonyl)amino]thio)-β-alanine ethyl ester, carbendazim, famoxadone, imidazolone, chloropyrimidinol, nitrile benzoxazole, mezyl anilide , cyclosporin, cyanamide (AC 382042), seed dressing, fenpropidin, butylbenzene Porphyrin, triphenyltin acetate, fentin hydroxide, thiram, azoxystrobin, fluazinam, fludioxonil, flumetole, fluoride Porphyrin, oxazolin, fluoxastrobin, fluoroquinazole, flucarbazole, sulfamethoxazole, flubenamide, fluconazole, sterilized dan, aluminum triethylphosphinate, wheat sulphate, furosemide, flor Ratio, biguanide salt, hexaconazole alcohol, soil fungus, carbendazim, emisali, imidazole, bis-octylamine, bis-octylamine triacetate, inobutazole, diarrhea, iprodione, Iprovalicarb, butyl isopropanyl carbazate, rice glutinous rice, chrysanthemum, ether oxystrobin, LY186054, LY211795, LY248908, mancozeb, mancozeb, metalaxyl ), azoxystrobin, rust-killing amine, metalaxyl, metalaxyl M, meconazole, metiram, dexamethasone, phenoxystrobin, benomyl , MON65500 ( N -allyl-4,5-dimethyl-2-trimethyldecylthiophene-3-carboxamide), myclobutanil, NTN0301, Tianan, dimethyldithio-amino Nickel formate, nitrothale-isopropyl, chlorochloropyrimidinol, metofuramide, organic mercury compound, oxime, oxadixyl, sulfimsulfuron, evil Oxolinic acid, oxpoconazol e), oxidized rust, rice blast, pentamidine, pentosan, leaf chloroform, phosphoric acid, benzoquinone, picoxystrobin, polyoxomycin D, polyram, thiabendazole, Prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propionic acid, propoxyquinoline, prothioconazole, pyraclostrobin, fixed phosphorus, Pyridoxine, pyrimethanil, praziquantel, clopidogrel, pyrrolnitrin, quaternary ammonium compound, chlorpyrifos, quinoxaline, quetiapine, thiazide (MON 65500), S- Imisali, oxime, sipconazole, sodium pentachlorophenol, spirocyclam, streptomycin, sulfur, tebuconazole, leaf sulphate, tetrachloronitrobenzene, fluoroetherazole, Thiabendazole, thifluzamide, 2-(thiocyanomethylthio)-benzothiazole, methyl thiophanate, thiram, thiabicide, timibenconazole, methyl Phenodium, p-carbazone, triadimefon, triazolol, butadiazole, zodiazepine, tricyclazole, thirteen Porphyrin, trifloxystrobin, fluconazole, oxazinamide, sterilized azole, jinggangmycin A, meidi, vinyl nucleus, XRD-563, sensible zinc, thiram, benzoxamide and the following formula These compounds: as well as

Compounds of formula (I) can be combined with soil, peat or other rooting media to protect plants against seed, native or leaf fungal diseases. Some mixtures may include a plurality of active ingredients that have significantly different physical, chemical or biological properties such that they do not readily self-use the same conventional formulation type. In such cases, other formulation types can be prepared. For example, when one active ingredient is a water-insoluble solid and the other is a water-insoluble liquid, it is still possible to disperse the solid active ingredient as a suspension (using a preparation similar to SC) to activate the liquid. The ingredients are dispersed as an emulsion (using a preparation similar to EW) to disperse each active ingredient into the same continuous liquid phase. The resulting composition is a suspoemulsion (SE) formulation.

The invention is illustrated by the following non-limiting examples in which the following abbreviations are used:

Example 1: This example illustrates 2-(3-ethynyl-8-methyl-quinolin-6-yloxy)-2-methyl-sulfanyl-N-propyl-B Preparation of indoleamine (Compound No. 5)

Add sequentially to a solution of 2-(3-ethynyl-8-methyl-6-quinolinyloxy)-2-methylsulfanyl-acetic acid (0.29 g, 1.0 mmol) in 5 mL of DMF Triethylamine (0.1 g, 1.0 mmol), EDCI (0.19 g, 1.0 mmol), HOAT (0.14 g, 1.0 mmol) and n-propylamine (0.06 g, 1.0 mmol). The reaction was stirred at room temperature for 16 h then taken up in ethyl acetate and diluted with water. After separating the phases, the organic layer was washed with brine, dried over magnesium sulfate, filtered and evaporated. The crude product was purified by EtOAc EtOAc EtOAc (EtOAc:EtOAc氧基oxy)-2-methyl-sulfanyl-N-propyl-acetamide (Compound 5). Mp 127 ° C - 130 ° C. ^{1 H-NMR (400MHz, CDCl} 3): δ = 0.96 (t, 3H), 1.61 (q, 2H), 2.20 (s, 3H), 2.78 (s, 3H), 3.31-3.44 (m, 2H), 5.72 (s, 1H), 6.73 (bs, 1H), 7.04 (d, 1H), 7.32 (d, 1H), 8.17 (d, 1H), 8.83 (d, 1H). MS: m/z = 329 [M + 1] ⁺ .

Throughout the specification, the temperature is given in degrees Celsius and "mp" refers to the melting point. LC / MS means liquid chromatography - mass spectrometry, and illustrate a method and system of the apparatus :( HP 1100 HPLC from Agilent (Agilent) of, Phenomenex Gemini the C18,3 μ m particle size, 110 Angström, 30 x 3mm Column , 1.7 mL/min, 60 ° C, H ₂ O + 0.05% HCOOH (95%) / CH ₃ CN / MeOH 4: 1 + 0.04% HCOOH (5%) - 2 min. - CH ₃ CN / MeOH 4: 1 + 0.04% HCOOH (5%)-0.8 min, ZQ mass spectrometer from Waters, ionization method: electrospray (ESI), polarity: positive ion, capillary voltage (kV) 3.00, cone voltage (V) ) 30.00, extractor (V) 2.00), source temperature (°C) 100, desolvation temperature (°C) 250, cone backflush gas flow (L/Hr) 50, desolvation gas flow (L/Hr) 400) ).

Example 2

This example illustrates the fungicidal properties of compounds of formula (I).

The compounds were tested in DMSO solution or as IF and EC formulations using a standard set of criteria for screening disease systems as exemplified below.

Liquid culture test:

A mycelial fragment or conidia suspension of the fungus (either freshly prepared from the liquid culture of the fungus or prepared from a cryopreservation) is directly mixed into the nutrient medium. A DMSO solution (max. 10 mg/ml) of the test compound was diluted with a factor of 50 with 0.025% Tween 20, and 10 μl of this solution was pipetted into a microtiter plate (96-well format). And a nutrient medium containing the fungal spore/mycelium fragment is then added thereto to give a final concentration of the test compound. The test plate was cultured in the dark at 24 ° C and 96% rH. The inhibition of fungal growth was measured with a luminometer after 2-6 days and the antifungal activity was calculated.

Whole plant test:

The active ingredients are formulated as IF or EC and the formulations are mixed with water just prior to spraying and subjected to ultrasonic agitation to achieve a uniform distribution. The spray solution consists of water. In the applicator Leaf application was carried out at 500 L/ha, with the conditions covering the upper and lower leaf surfaces (placed on a turntable, air-assisted spray from a 2-nozzle). The prophylactic test is carried out with a prophylactic administration of 1 or 2 days, i.e., the plants are treated with the compounds prior to artificial culture with fungal spores for 1 or 2 days, and for therapeutic tests, the culture is carried out prior to administration. Depending on the disease system, a single assessment of disease levels is performed after 2 to 19 days of culture. Disease control relative to untreated control plants was then calculated.

Wheat powdery mildew (Blumeria graminis f.sp. tritici, Erysiphe graminis f.sp. Tritici) / wheat / leaf disc preventive (Powdery mildew on wheat)

Leaf fragments of wheat cultivar Kanzler were placed on agar plates (24 well size) agar and sprayed with the formulated test compound diluted in water. One day after the application, the leaf discs were inoculated by shaking the plants infected with powdery mildew on the test plates. Inoculated leaf discs were cultured at 20 ° C and 60% rh in an artificial climate chamber under a 24 h dark followed by a 12 h light / 12 h dark light protocol, and appropriate levels of disease damage appeared on untreated control leaf fragments. At the time (6-8 days after administration), the activity of the compound was evaluated as the percentage of disease control when compared to untreated.

Compounds 1, 2, 3, 5, 6, 7, 8, 9, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated controls under the same conditions Plants are infected with more than 80% of fungal diseases caused by plant diseases.

Wheat powdery mildew (Blumeria graminis f.sp. tritici, Erysiphe graminis f.sp. Tritici) / wheat / preventive (Powdery mildew on wheat)

Plants of the 1 week old wheat cultivar Arina were sprayed in a spray chamber with the formulated test compound diluted in water. Two days after application, the powdery mildew spores were dispersed in the culture chamber. They were used to inoculate the test plants. The inoculated test plants were grown in a greenhouse at 20 ° C / 18 ° C (day / night) and 60% rh (relative humidity), and when appropriate levels of disease appeared on untreated control plants (admin 7-9 After days, assess the percentage of leaf area covered by the disease.

Compounds 2, 6, and 7 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated control plants were infected with phytopathogenic fungi over 80% under the same conditions. .

Fusarium oxysporum / wheat / prophylactic (crocosis):

The spikelets of the wheat cultivar Monsun were placed on agar plates (24-well format) agar and sprayed with the formulated test compound diluted in water. One day after application, the spikelets were inoculated with a spore suspension of the fungus. Inoculated spikelets were cultured in an artificial climate chamber at 72 h half-dark followed by a 12 h light/12 h dark light protocol at 20 ° C and 60% rh, and appropriate levels of disease damage appeared on untreated control spikelets. At the time (6-8 days after administration), the activity of the compound was evaluated as the percentage of disease control when compared to untreated.

Compounds 1, 5, 6, 7, 8, 9, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated control plants were induced to plants under the same conditions. The fungal infection of the disease is over 80%.

Wheat total pathogen/liquid culture (cereal total erosion)

The mycelial fragments from the cryopreservation were directly mixed into the nutrient medium (PDB (potato dextrose broth)). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), a nutrient medium containing fungal spores was added. The test plates were incubated at 24 ° C and the inhibition of growth was determined photometrically after 4-5 days.

Compounds 1, 2, 6, 7, 8, 9, and 11 from Tables 2 and 3 according to the present invention were at 200 ppm Fungal infestation was inhibited by at least 80% in this test, while untreated control plants were infected with phytopathogenic fungi over 80% under the same conditions.

Magnaporthe oryzae / rice / leaf disc prevention (rice blast)

Leaf fragments of the rice cultivar Ballila were placed on agar plates (24-well format) agar and sprayed with the formulated test compound diluted in water. Two leaf fragments were inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf fragments were cultured in a climate chamber at 24 h dark, followed by a 12 h light/12 h dark light protocol at 22 ° C and 80% rh (relative humidity), and the compound activity was evaluated as untreated. Percentage of disease control compared to untreated when appropriate levels of disease damage occurred (controls 5-7 days after administration).

Compounds 5, 6, 8, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated control plants were infected with phytopathogenic fungi over 80 under the same conditions. %.

Magnaporthe oryzae / rice / preventive (rice blast)

Plants of the 3-week-old rice cultivar Koshihikari were sprayed in a spray chamber with a prepared test compound diluted in water. The test plants were inoculated by spraying them with a spore suspension 2 days after application. The inoculated test plants were cultured at 25 ° C and 95% rh (relative humidity), and the leaf area covered by the disease was evaluated when an appropriate level of disease appeared on the untreated control plants (after 7-9 days after administration). percentage.

Compounds 1, 2, 5, 7, 8, 9, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated control plants were induced to plants under the same conditions. The fungal infection of the disease is over 80%.

Fusarium oxysporum (C. oxysporum) / liquid culture (cereal root rot)

The fungal conidia from the cryopreservation are directly mixed into the nutrient medium (PDB (potato dextrose broth)). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), a nutrient medium containing fungal spores was added. The test plates were incubated at 24 ° C and the inhibition of growth was determined photometrically after 4-5 days.

Compounds 1, 2, 3, 5, 6, 7, 8, 9, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated controls under the same conditions Plants are infected with more than 80% of fungi causing plant diseases.

Rhizoctonia solani (S. cerevisiae) / liquid culture (Septoria blotch)

The fungal conidia from the cryopreservation are directly mixed into the nutrient medium (PDB (potato dextrose broth)). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), a nutrient medium containing fungal spores was added. The test plates were incubated at 24 ° C and the inhibition of growth was determined photometrically after 4-5 days.

Compounds 1, 2, 3, 5, 6, 7, 8, 9, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated controls under the same conditions Plants are infected with more than 80% of fungi causing plant diseases.

Coccidioides (S. cerevisiae)/Wheat/prophylactic (Saccharomyces cerevisiae on wheat)

Plants of the 2 week old wheat cultivar Riband were sprayed in a spray chamber with the formulated test compound diluted in water. The test plants were inoculated by spraying them with a spore suspension one day after application. After inoculation at 22 ° C / 21 ° C (day / night) and 95% rh for 1 day, the inoculated test plants were maintained in the greenhouse at 22 ° C / 21 ° C (day / night) and 70% rh . Efficacy was assessed directly at the appropriate level of disease on untreated control plants (after 16-19 days after application).

Compounds 1, 2, 5, 6, 7, 8, 9, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infection by at least 80% at 200 ppm in this test, while untreated control plants were treated under the same conditions. More than 80% of fungal infections caused by phytopathies.

G. sphaeroides (S. cerevisiae)/Wheat/therapeutic (Saccharomyces cerevisiae on wheat)

Plants of the 2-week old wheat cultivar Riband were inoculated by spraying with a spore suspension. After a 2 day incubation period of 22 ° C / 21 ° C (day / night) and 95% rh, the test plants were maintained in an artificial climate chamber at 22 ° C / 21 ° C (day / night) and 70% rh . Five days after the cultivation, the inoculated test plants were sprayed with the formulated test compound diluted in water in a spray chamber. When an appropriate level of disease occurred on untreated control plants (after 11-14 days after administration), the percentage of leaf area covered by the disease was assessed.

Compounds 1, 2, 5, 6, 7, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated control plants were phytopathogenic under the same conditions. Fungal infections exceed 80%.

Phaeosphaeria nodorum (Septoria nodorum )/Wheat/leaf disc prevention ( Blood spot blight)

Leaf fragments of wheat cultivar Kanzler were placed on agar plates (24 well size) agar and sprayed with the formulated test compound diluted in water. Two leaf discs were inoculated with a spore suspension of the fungus 2 days after application. Inoculated test leaf discs at 20 ° C and 75% rh in a climatic chamber under a 12 h light/12 h dark light protocol and appropriate levels of disease damage on untreated control leaf discs (5 after application) After -7 days), the activity of the compound was evaluated as the percentage of disease control compared to untreated.

Compounds 1, 2, 3, 5, 6, 7, 8, 9, and 11 from Tables 2 and 3 according to the present invention Fungal infestation was inhibited by at least 80% in this assay at 200 ppm, while untreated control plants were infected with phytopathogenic fungi over 80% under the same conditions.

Wheat Stem Puccinia / Wheat / Leaf Disc Prevention (Brown Rust)

Leaf fragments of wheat cultivar Kanzler were placed on agar plates (24 well size) agar and sprayed with the formulated test compound diluted in water. One day after application, the leaf discs were inoculated with a spore suspension of the fungus. Inoculated leaf fragments were cultured at 19 ° C and 75% rh in an artificial climate chamber under a 12 h light / 12 h dark light protocol, and an appropriate level of disease damage occurred on untreated control leaf fragments (7- after application) After 9 days), the activity of the compound was evaluated as the percentage of disease control compared to untreated.

Compounds 1, 2, 3, 5, 6, 7, 8, 9, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated controls under the same conditions Plants are infected with more than 80% of fungi causing plant diseases.

Puccinia reticulata / wheat / prophylactic (wheat brown rust)

Plants of the 2 week old wheat cultivar Arina were sprayed in a spray chamber with the formulated test compound diluted in water. The test plants were inoculated by spraying them with a spore suspension one day after application. After inoculation at 20 ° C and 95% rh for 1 day, the inoculated test plants were maintained in a greenhouse at 20 ° C / 18 ° C (day / night) and 60% rh. When an appropriate level of disease occurred on untreated control plants (after 12-14 days after administration), the percentage of leaf area covered by the disease was assessed.

Compounds 1, 6, and 8 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated control plants were infected with phytopathogenic fungi over 80% under the same conditions. .

Helicobacter pylori/barley/leaf disc preventive (net spot)

The leaf fragment of the barley cultivar Hasso was placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf fragments were inoculated with a spore suspension of the fungus 2 days after application. Inoculated leaf fragments were cultured at 20 ° C and 65% rh in a climatic chamber under a 12 h light/12 h dark light protocol, and an appropriate level of disease damage occurred on untreated control leaf fragments (5- after application) After 7 days), the activity of the compound was evaluated as the percentage of disease control compared to untreated.

Compounds 5, 6, 7, 8, 9, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated control plants were phytopathogenic under the same conditions. Fungal infections exceed 80%.

Rhizoctonia solani (barley worm)/barley/preventive (net spot on barley)

Plants of the 1 week old barley cultivar Regina were sprayed in a spray chamber with the formulated test compound diluted in water. The test plants were inoculated by spraying them with a spore suspension 2 days after application. The inoculated test plants were cultured at 22 ° C and 95% rh, and the percentage of leaf area covered by the disease was evaluated when appropriate levels of disease occurred on untreated control plants (after 5-7 days after administration).

Compounds 1, 6, 7, 8, and 9 from Tables 2 and 3 according to the present invention inhibited fungal infection by at least 80% at 200 ppm in this test, while untreated control plants were infected with phytopathogenic fungi under the same conditions. More than 80%.

Rhizoctonia solani/liquid culture (root rot, sputum disease)

The mycelial fragments of the newly cultured liquid culture fungus were directly mixed into a nutrient medium (PDB (potato dextrose broth)). Place the test compound in a (DMSO) solution in a microtiter After the plate (96-well size), a nutrient medium containing the fungal material is added. The test plates were incubated at 24 ° C and the inhibition of growth was determined photometrically after 3-4 days after application.

Compounds 3, 5, 6, 7, 8, and 11 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 200 ppm in this test, while untreated control plants were phytopathogenic under the same conditions. Fungal infections exceed 80%.

Comparative example:

Cereal diseases: Rhizoctonia solani (S. cerevisiae) / liquid culture (Spotted sphaeroides)

The fungal conidia from the cryopreservation are directly mixed into the nutrient medium (PDB (potato dextrose broth)). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), a nutrient medium containing fungal spores was added. The test plates were incubated at 24 ° C and the inhibition of growth was determined photometrically after 4-5 days.

Compounds 1 and 2 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 60 ppm in this test, while compounds 48 and 154 from Table 4 showed less than 30% at 60 ppm under the same conditions. Effectiveness.

Phaeosphaeria nodorum (Septoria nodorum )/Wheat/leaf disc prevention ( Blood spot blight)

Leaf fragments of wheat cultivar Kanzler were placed on agar plates (24 well size) agar and sprayed with the formulated test compound diluted in water. Two leaf discs were inoculated with a spore suspension of the fungus 2 days after application. Inoculated test leaf discs at 20 ° C and 75% rh in a climatic chamber under a 12 h light/12 h dark light protocol and appropriate levels of disease damage on untreated control leaf discs (5 after application) After -7 days), the activity of the compound was evaluated as the percentage of disease control compared to untreated.

Compounds 1 and 2 from Tables 2 and 3 according to the present invention inhibited fungal infestation by at least 80% at 60 ppm in this test, while compounds 48 and 154 from Table 4 showed less than 30% at 60 ppm under the same conditions. Effectiveness.

Non-cereal diseases: Alternaria solani / tomato / leaf disc (early blight)

The leaf discs of the tomato cultivar Baby were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. Two leaf discs were inoculated with a spore suspension of the fungus 2 days after application. Inoculated leaf discs were incubated in a climatic chamber under a light regime of 12/12 h (light/dark) at 23 ° C / 21 ° C (day/night) and 80% rh, and compound activity was evaluated as untreated Percentage of disease control compared to untreated when an appropriate level of disease damage occurred on control leaf discs (after 5-7 days after administration).

Compounds 48 and 154 from Table 4 inhibited fungal infestation by at least 80% in this test at 60 ppm, while compounds 1 and 2 from Tables 2 and 3 according to the present invention showed less than 30% at 60 ppm under the same conditions. Effectiveness.

Phytophthora infestans / tomato / leaf disc prophylaxis (late blight)

The tomato leaf discs were placed on water agar in a multi-well plate (24-well format) and sprayed with the formulated test compound diluted in water. One day after application, the leaf discs were inoculated with a spore suspension of the fungus. The inoculated leaf discs were incubated in a climate chamber at 24 h dark, followed by a 12 h light/12 h dark light protocol at 16 ° C and 75% rh (relative humidity) and the compound activity was evaluated as Percentage of disease control compared to untreated when the appropriate level of disease damage occurred in the treated control leaf discs (after 5-7 days after administration).

Compounds 48 and 154 from Table 4 inhibited fungal infestation by at least 60% at 200 ppm in this test, while compounds 1 and 2 from Tables 2 and 3 according to the present invention showed efficacy below 30% under the same conditions.

Claims (11)

Use of a compound of formula (I) for controlling at least one cereal disease: Wherein R ¹ is ethyl or methylthio; R ² is CR ³ R ⁴ R ⁵ ; R ³ and R ⁴ together, are hydrogen or methyl; and R ⁵ is methyl, ethyl or vinyl; Or a salt or N-oxide thereof. The use of claim 1, wherein R ³ and R ⁴ together are hydrogen. The use of claim 1, wherein R ⁵ is an ethyl group. The use of claim 1, wherein R ¹ is ethyl, R ³ and R ^{4 are} together hydrogen and R ⁵ is methyl or ethyl. The use of claim 1, wherein R ¹ is a methylthio group, R ³ and R ^{4 are} together hydrogen and R ⁵ is methyl or ethyl. The use according to claim 1, wherein the cereal disease is leaf spot. The use according to claim 1, wherein the cereal disease is a Septoria disease of wheat. The use of claim 1, wherein the cereal is selected from the group consisting of Wheat, barley, rye and rice. The use according to claim 1, wherein the compound of formula (I) is formulated in a composition comprising: - a fungicidal effective amount of a compound of formula (I) - thus suitable A carrier or diluent, and optionally, an additional fungicidal compound. A method for controlling or controlling a cereal disease, which comprises applying a fungic effective amount of a compound of the formula (I) to a plant, a plant seed, a plant or a seed, as described in claim 1 of the patent application. Or soil or any other plant growth medium, said seed or said plant line cereal. A method for controlling or controlling a fungus at a site, the method comprising treating a fungus or a fungus with a fungic effective amount of a compound of formula (I) as described in claim 1 wherein said fungus is selected from the group, the group consisting of: wheat powdery mildew species of the genus (Blumeriagraminis sp), Drechslera (Drechsleratritici-repentis), Rhizopus species of Fusarium, Gaeumannomyces (Gaeumannomycesgraminis), rice blast (Fusarium sp.) ( Magnaporthegrisea ), Monographella nivalis , Mycosphaerellagraminicola , Oculimacula sp. , Phaeosphaerianodorum , Pucciniarecondita Pyrenophorateres , Ramulariacollo-cygni , Rhizoctoniasolani , Rhynchosporiumsecalis , and mixtures thereof.