Phenylcyclohexanone compounds and uses thereof

Abstract

Provided is a compound having excellent plant disease control efficacy. The compound represented by the formula (A) can be used for controlling plant diseases.

Description

Technical Field

[0001] This patent application asserts priority and benefits under the Paris Convention based on Japanese Patent Application No. 2023-063233 (filed on April 10, 2023), the entire contents of which are incorporated herein by reference.

[0002] This invention relates to phenylcyclohexanone compounds and their uses. Background Technology

[0003] Non-patent literature 1 describes compounds that show efficacy in controlling plant diseases.

[0004] Existing technical documents Non-patent literature Non-Patent Literature 1: The Pesticide Manual - 18th Edition (BCPC); ISBN 978-1-9998966-1-4 Summary of the Invention

[0005] The problem that the invention aims to solve The objective of this invention is to provide compounds with excellent efficacy in controlling plant diseases.

[0006] Methods for solving problems The inventors of this application conducted research on the above-mentioned issues and found that the compound represented by the following formula (A) has excellent efficacy in controlling plant diseases, thus completing this invention.

[0007] That is, the present invention is as follows.

[0008] [1] The compound represented by formula (A) [Chemical Formula 1] (Hereinafter referred to as compounds of the present invention).

[0009] [2] A composition for the prevention and control of plant diseases (hereinafter referred to as the composition for the prevention and control of plant diseases of the present invention), which contains an inactive carrier and the compound described in [1].

[0010] [3] A method for controlling plant diseases (hereinafter referred to as the plant disease control method of the present invention), comprising the step of applying the compound described in [1] or the composition for controlling plant diseases described in [2] to the plant or the soil of the cultivated plant.

[0011] Invention Effects The compounds of this invention have excellent efficacy in controlling plant diseases and are effective as active ingredients in compositions for controlling plant diseases. Detailed Implementation

[0012] The compounds of this invention contain two or more stereoisomers. Examples of stereoisomers include enantiomers and diastereomers. The compounds of this invention include each stereoisomer and mixtures of stereoisomers in any ratio.

[0013] As stereoisomers, examples include the compound shown in formula (1) and the compound shown in formula (2).

[0014] [Chemical Formula 2] [Chemical Formula 3] The compound shown in formula (1) and the compound shown in formula (2) are enantiomers of each other.

[0015] The following compounds can be cited as examples of compounds used in this invention.

[0016] The compound shown in formula (1).

[0017] The compound shown in formula (2).

[0018] The compound shown in formula (3) and its enantiomers.

[0019] [Chemical Formula 4] The compound shown in formula (4) and its enantiomers.

[0020] [Chemical Formula 5] The compound shown in formula (5) and its enantiomers.

[0021] [Chemical Formula 6] A mixture of stereoisomers containing more compounds of formula (1) than any other stereoisomer.

[0022] A mixture of stereoisomers containing more compounds as shown in formula (2) than any other stereoisomer.

[0023] A mixture of stereoisomers of the compound shown in formula (1) and the compound shown in formula (2) in a 1:1 ratio.

[0024] A mixture of stereoisomers containing the compound shown in formula (1) and the compound shown in formula (2) in a 1:1 ratio, and containing more of the compound shown in formula (1) than any stereoisomer other than the compound shown in formula (1) and the compound shown in formula (2).

[0025] The plant disease control composition of the present invention contains the compound of the present invention and an inactive carrier. In the case of the plant disease control composition of the present invention, the compound of the present invention is usually mixed with an inactive carrier such as a solid carrier or a liquid carrier, and surfactants and other formulation adjuvants are added as needed to formulate it into wettable powders, water-dispersible granules, aqueous suspensions, granules, dry suspensions, emulsions, microcapsules, etc. These formulations typically contain 0.0001% to 99% of the compound of the present invention by weight.

[0026] Examples of solid carriers used in formulation include clay (pyrophyllite clay, kaolinite clay, etc.), talc, calcium carbonate, diatomite, zeolite, bentonite, acid clay, palygorskite, silica, ammonium sulfate, vermiculite, perlite, pumice, silica sand, micronized and granular chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.), and resins (polyethylene, polypropylene, polyester, polyurethane, polyamide, polyvinyl chloride, etc.).

[0027] Examples of liquid carriers include water, alcohols (ethanol, cyclohexanol, benzyl alcohol, propylene glycol, polyethylene glycol, etc.), ketones (acetone, cyclohexanone, etc.), aromatic hydrocarbons (xylene, phenylxyl ethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), esters (ethyl acetate, methyl oleate, propylene carbonate, etc.), nitriles (acetonitrile, etc.), ethers (ethylene glycol dimethyl ether, etc.), amides (N,N-dimethylformamide, N,N-dimethyloctylamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), lactams (N-methylpyrrolidone, N-octylpyrrolidone, etc.), fatty acids (oleic acid, etc.), and vegetable oils (soybean oil, etc.).

[0028] Examples of surfactants include nonionic surfactants (polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyethylene glycol fatty acid esters, etc.) and anionic surfactants (alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfates, etc.).

[0029] Other pharmaceutical additives include, for example, binders, dispersants, colorants and stabilizers. Specifically, examples include polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, etc.), isopropyl phosphate and dibutylhydroxytoluene.

[0030] The compounds of this invention can prevent and control plant diseases caused by plant pathogenic microorganisms such as fungi, oomycetes, phytomyxea, and bacteria. Examples of fungi include, for instance, those belonging to the phyla Ascomycota, Basidiomycota, Blastodactyla, Chytridiomycota, Mucoromycota, and Olpidiomycota. Specifically, examples include, for instance, the following. The scientific names of the plant pathogenic microorganisms causing each disease are shown in parentheses.

[0031] Rice diseases: Blight (Pyricularia oryzae), Sesame leaf blight (Cochliobolus miyabeanus), Sheath blight (Rhizoctonia solani), Bakanae disease (Gibberella fujikuroi), Yellowing and stunting disease (Sclerophthora macrospora), Pseudo-rice blast and panicle blight (Epicoccum nigrum), Seedling damping-off (Trichodermaviride, Rhizopus oryzae), False sheath blight (Waitea circinata), Brown sclerotinia rot (Ceratobasidium setariae), Brown sheath blight (Thanatephorus) Rice smut (Ustilaginoidea virens), grain smut (Tilletia horrida, Tilletia barclayana). Wheat diseases: Powdery mildew (Blumeria graminis), Fusarium head blight (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), Yellow rust (Puccinia striiformis), Black rust (Puccinia graminis), Red rust (Puccinia recondita), Red snow rot (Microdochium nivale, Microdochium majus), Small sclerotium rot (Typhula incarnata, Typhula ishikariensis), Large sclerotium rot (Sclerotinia northernis) (borelis), brown root rot (Pythium spp.), loose smut (Ustilago tritici), smut (Tilletia caries, Tilletia controversa), eye spot (Pseudocercosporella herpotrichoides), leaf blight (Septoria tritici), glume blight (Stagonospora nodorum), yellow spot (Pyrenophora tritici-repentis), seedling damping-off (Rhizoctonia solani), damping-off (Gaeumannomyces graminis), blast disease (Pyricularia graminis-tritici). Barley diseases: Powdery mildew (Blumeria graminis), Fusarium head blight (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), Yellow rust (Puccinia striiformis), Black rust (Puccinia graminis), Barley stalk rust (Puccinia hordei), Smut (Ustilago nuda), Cloud blight (Rhynchosporium secalis), Net blight (Pyrenophora teres), Leaf spot (Cochliobolus sativus), Leaf stripe (Pyrenophora teres). graminea), Ramularia collo-cygni leaf spot, and Rhizoctonia solani (a fungus causing seedling damping-off). Corn diseases: Rust (Puccinia sorghi), Southern rust (Puccinia polysora), Large leaf spot (Setosphaeria turcica), Tropical rust (Physopella zeae), Sesame leaf blight (Cochliobolus heterostrophus), Anthracnose (Colletotrichum graminicola), Gray leaf spot (Cercospora zeae-maydis), Brown spot (Kabatiella zeae), Phaeosphaeria maydis, Stenocarpella maydis, Stenocarpellamacrospora, Stem rot (Fusarium graminii). graminearum, Fusarium verticilioides, Colletotrichum graminicola, Ustilago maydis (corn smut), Physoderma maydis (corn stalk rot), and Phyllachora maydis (corn black spore causal agent). Cotton diseases: Anthracnose (Colletotrichum gossypii), White mold (Ramularia areola), Black spot (Alternaria macrospora, Alternariagossypii), Root black rot (Thielaviopsis basicola). Coffee diseases: Rust (Hemileia vastatrix) and leaf spot (Cercospora coffeicola). Diseases of rapeseed: Sclerotinia sclerotiorum, Alternaria brassicae, Phona lingam, and Pyrenopeziza brassicae. Sugarcane diseases: Rust (Puccinia melanocephela, Pucciniakuehnii), Smut (Ustilago scitaminea); Sunflower diseases: Rust (Puccinia helianthi), downy mildew (Plasmopara halstedii); Citrus diseases: black spot (Diaporthe citri), scab (Elsinoe fawcetti), green mold (Penicillium digitatum), penicillium italicum, blight (Phytophthora parasitica, Phytophthora citrophthora), aspergillus niger; Apple diseases: Blossom blight (Monilinia mali), canker (Valsa ceratosperma), powdery mildew (Podosphaera leucotricha), Alternaria alternata (Alternaria alternata apple pathotype), black spot (Venturia inaequalis), anthracnose (Glomerella cingulata, Colletotrichum acutatum), brown spot (Diplocarpon mali), ring rot (Botryosphaeria berengeriana), blight (Phytophthora racactorum), red spot (Gymnosporangium). juniperi-virginianae), Gymnosporangium yamadae); Pear diseases: Black spot (Venturia nashicola, Venturiapirina), Black spot (Alternaria alternata Japanese pearpathotype), Gymnosporangium haraeanum (Gymnosporangium haraeanum). Peach diseases: Gray spot (Monilinia fructicola), Black spot (Cladosporium carpophilum), Brown spot (Phomopsis sp.), Leaf curl (Taphrina deformans), Powdery mildew (Podosphaeraleucotricha). Grape diseases: Black rot (Elsinoe ampelina), Late rot (Glomerella cingulata, Colletotrichum acutatum), Powdery mildew (Uncinula necator), Rust (Neophysopella sp.), Black rot (Guignardiabidwellii), Downy mildew (Plasmopara viticola), Brown spot (Pseudocercospora vitis), White rot (Coniella castaneicola). Diseases of persimmon: Anthracnose (Gloeosporium kaki, Colletotrichum acutatum) , Leaf spot (Cercospora kaki, Mycosphaerella nawae) , Powdery mildew (Phyllactinia kakicola) ; Fig diseases: Rust (Phakopsora nishidana)); Diseases of gourds: Anthracnose (Colletotrichum lagenarium), Powdery mildew (Sphaerotheca fuliginea), Anthracnose (Didymella bryoniae), Brown spot (Corynespora cassiicola), Fusarium wilt (Fusarium oxysporum), Downy mildew (Pseudoperonospora cubensis), Phytophthora capsici, Damping-off (Pythium sp.), Phomopsis sp. root rot. Tomato diseases: target spot (Alternaria solani), leaf mold (Cladosporium fulvum), anthracnose (Pseudocercospora fuligena), blight (Phytophthora infestans), powdery mildew (Leveillula taurica). Eggplant diseases: Brown spot (Phomopsis vexans) , powdery mildew (Erysiphe cichoracearum) , black rot (Corynespora melongenae) , leaf mold (Mycovellosiella nattrassii) , brown spot (Thanatephorus cucumeris) ; Diseases of cruciferous vegetables: Black spot (Alternaria japonica), White spot (Cercosporella brassicae), Clubroot (Plasmodiophorabrassicae), Downy mildew (Peronospora parasitica), White rust (Albugocandida), Alternaria brassicicola leaf spot; Diseases of onions: Rust (Puccinia allii), Black spot (Alternaria porri), White rot (Sclerotium cepivorum), Gray mold (Botrytis squamosa), Leaf blight (Stemphylium vesicarium, Stemphylium botryosum), White mold (Sclerotium rolfsii), White spot leaf blight (Botrytis squamosa). Soybean diseases: Purple blotch (Cercospora kikuchii), Black rot (Elsinoe glycines), Black spot (Diaporthe phaseolorum var. sojae), Rust (Phakopsora pachyrhizi), Brown ring rot (Corynespora cassiicola), Anthracnose (Colletotrichum glycines, Colletotrichum truncatum), Damping-off (Rhizoctonia solani), Brown spot (Septoria glycines), Spot disease (Cercospora sojina), Sclerotinia rot (Sclerotinia sclerotiorum). (sclerotiorum), powdery mildew (Microsphaeradiffusa), stem blight (Phytophthora sojae), downy mildew (Peronospora manshurica), sudden death syndrome (Fusarium virguliforme), red crown rot (Calonectria ilicicola), Diaporthe / Phomopsis complex (Diaporthe longicolla, Diaporthe phaseolorum, Phopsis longicolla); Diseases of common beans: Sclerotinia sclerotiorum, rust (Uromyces appendiculatus), angular leaf spot (Phaeoisariopsis griseola), anthracnose (Colletotrichum lindemuthianum), and root rot (Fusarium solani). Peanut diseases: Black spot (Cercospora personata) , Brown spot (Cercospora arachidicola) , White rot (Sclerotium rolfsii) , Red crown rot (Calonectria ilicicola) . Pea diseases: powdery mildew (Erysiphe pisi) and root rot (Fusarium solani). Potato diseases: Early blight (Alternaria solani), blight (Phytophthora infestans), scarlet rot (Phytophthora erythroseptica), powdery scab (Spongospora subterranea f. sp. subterranea), Verticillium wilt (Verticillium albo-atrum, Verticillium dahliae, Verticillium nigrescens), dry rot (Fusarium solani), canker (Synchytrium endobioticum). Strawberry diseases: powdery mildew (Sphaerotheca humuli), anthracnose (Glomerella cingulata, Colletotrichum acutatum); Tea diseases: Net cake disease (Exobasidium reticulatum), white spot disease (Elsinoe leucospila), gray blight (Pestalotiopsis sp.), anthracnose (Colletotrichum theae-sinensis). Tobacco diseases: Red spot disease (Alternaria longipes), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), blight (Phytophthora nicotianae). Diseases of sugar beets: Brown spot (Cercospora beticola) , Leaf blight (Thanatephorus cucumeris) , Root rot (Thanatephorus cucumeris) , Black root rot (Aphanomyces cochlioides) , Rust (Uromyces betae) ; Rose diseases: Black spot (Diplocarpon rosae) and powdery mildew (Sphaerotheca pannosa). Chrysanthemum diseases: Brown spot (Septoria chrysanthemi-indici) and white rust (Puccinia horiana). Onion diseases: Botrytis leaf blight (Botrytis cinerea, Botrytis byssoidea, Botrytis squamosa, Botrytis allii, Botrytis squamosa); Diseases of various crops: gray mold (Botrytis cinerea), sclerotinia sclerotiorum, black rot (Sclerotium cepivorum), white mold (Sclerotium rolfsii), seedling blight (Pythium aphanidermatum, Pythium irregulare, Pythium ultimum). Radish diseases: Black spot (Alternaria brassicicola). Sweet potato diseases: vine rot (Fusarium oxysporum f. sp. batatas), basal rot (Diaporthedestruens), black spot (Ceratocystis fimbriata). Diseases of turfgrass: Coin spot (Sclerotinia homoeocarpa), brown patch, large patch (Rhizoctonia solani), Pythium wilt (Pythium aphandidermatum), anthracnose (Colletotrichum caudatum). Banana diseases: Banana leaf spot (Sigatoka disease) (Mycosphaerella fijiensis, Mycosphaerella musicola)); Diseases of lentils: Ascochyta disease (Ascochyta lentis); Chickpea diseases: Ascochyta rabiei (blight of the chickpea plant) Diseases of green peppers: Anthracnose (Colletotrichum scovillei) , Powdery mildew (Leveillula taurica) , White mold (Sclerotium rolfsii) ; Mango diseases: Anthracnose (Colletotrichum acutatum); Sweet potato diseases: basal rot (Diaporthe destruens). Fruit tree diseases: White root rot (Rosellinia necatrix) and Purple root rot (Helicobasidium mompa)); Post-harvest diseases of fruits such as apples and pears: Mucor rot diseases (Mucorpiriformis); Seed diseases or diseases in the early stages of growth caused by fungi such as Aspergillus, Penicillium, Fusarium, Gibberella, Tricoderma, Thieviopsis, Rhizopus, Mucor, Corticium, Phona, Rhizoctonia, and Diplodia; Viral diseases: Giant vein disease of lettuce mediated by Olpidium brassicae; and various viral diseases of crops mediated by Polymyxa species (such as Polymyxa betae and Polymyxa graminis). Diseases caused by bacteria: Rice bacterial damping-off (Burkholderia plantarii), rice inner glume browning (Pantoea ananatis), rice bacterial leaf blight (Xanthomonas oryzae pv. oryzae.), cucumber bacterial angular leaf spot (Pseudomonas syringae pv. lachrymans), eggplant bacterial wilt (Ralstonia solanacearum), citrus canker (Xanthomonas citri), Chinese cabbage soft rot (Erwinia carotovora), potato scab (Streptomyces cabbiei), potato black shank (Pectobacterium soft rot). Bacterial leaf spot of peach (Pseudomonas syringae, Erwinianigrifluens, Xanthomonas campestris)), bacterial canker of plum (Pseudomonas syringae pv. morsprunorum, Erwinia sp.)), corn wilt (Clavibacter michiganensis), crown gall of grape, olive, peach, etc. (Xylella fastidiosa)), root nodule of Rosaceae plants such as apple, peach, cherry, etc. (Agrobacterium tumefaciens)

[0032] Regarding the plant disease control method of the present invention, examples include treatments of the plant body such as stem and leaf dispersal and seed disinfection, and treatments of the plant cultivation site such as soil treatment.

[0033] Regarding the amount of the compound of the present invention processed, per 1000m 2 The amount of plant cultivation material is usually 1g to 10000g. When the compounds of this invention are formulated into emulsions, wettable powders, aqueous suspensions, etc., they are usually applied after being diluted with water at an active ingredient concentration of 0.01 to 10000 ppm. Granules, powders, etc., are usually applied directly.

[0034] The plant disease control composition of the present invention can be used as a control agent for plant diseases in farmland such as dry fields, paddy fields, lawns, and orchards.

[0035] Example The present invention will now be described in more detail through manufacturing examples, formulation examples, and test examples, but the present invention is not limited to these examples.

[0036] First, examples of manufacturing the compounds of the present invention are shown below.

[0037] In the following examples, unless otherwise specified, quantitative analysis was performed using high-performance liquid chromatography (HPLC). The analytical conditions are as follows.

[0038] [High Performance Liquid Chromatography Analysis Conditions] Mobile phases: Solution A: 5mM ammonium carbonate aqueous solution; Solution B: acetonitrile Column: SUMIPAX (registered trademark) ODS Z-CLUE, particle size 3μm, 4.6mm ID×100mm UV measurement wavelength: 210nm Flow rate: 1.0 mL / min Column oven: 30℃ Pumps: 2 units of LC-20AD (manufactured by Shimadzu Corporation) (high pressure gradient) Gradient conditions: The solution is delivered using the concentration gradient described in [Table LC1].

[0039] [Table 1] Manufacturing Example 1 1.05 g of 2-(methylsulfonyl)acetophenone, 454.1 mg of 3-methyl-3-buten-2-one, 28.1 mg of sodium carbonate, and 10 mL of water were mixed and stirred at room temperature for 20 minutes. The resulting mixture was analyzed by high performance liquid chromatography, confirming that the compound of the present invention was generated at an area percentage of 7% (retention time 9.3 minutes).

[0040] The following shows the compounds of the present invention. 1 H-NMR values.

[0041] 1 H-NMR (CDCl3) δ: 7.54-7.45 (4H, m), 7.40-7.36 (1H, m), 4.65 (1H, d), 3.86 (1H, dd), 2.88-2.84 (1H, m), 2.74 (1H, ddd), 2.68-2.60 (2H, m), 2.28(1H, dd), 2.01 (3H, s), 1.23 (3H, d). 2-(methylsulfonyl)acetophenone is commercially available. Alternatively, it can be manufactured using known methods.

[0042] Next, examples of formulations of the compounds of the present invention are shown. It should be noted that parts refer to parts by weight.

[0043] Formulation Example 1 A mixture of 35 parts by weight of polyoxyethylene alkyl ether ammonium sulfate and silica (1:1), 10 parts by weight of the compound of the present invention, and 55 parts by weight of water were mixed and micronized using a wet pulverization method to obtain the formulation.

[0044] Formulation Example 2 The compound of the present invention, 50 parts, calcium lignosulfonate, 2 parts, sodium lauryl sulfate, and 45 parts, silicon dioxide were pulverized and mixed to obtain the formulation.

[0045] Formulation Example 3 The formulation was obtained by mixing 5 parts of the compound of the present invention, 9 parts of polyoxyethylene styrene phenyl ether, 5 parts of polyoxyethylene decyl ether (ethylene oxide addition number: 5), 6 parts of calcium dodecylbenzenesulfonate, and 75 parts of xylene.

[0046] Formulation Example 4 Two parts of the compound of the present invention, one part of silicon dioxide, two parts of calcium lignosulfonate, 30 parts of bentonite, and 65 parts of kaolin clay were pulverized and mixed, an appropriate amount of water was added for kneading, granulated using a granulator, and then dried to obtain the formulation.

[0047] Furthermore, the efficacy of the compounds of the present invention in controlling plant diseases is demonstrated through experiments.

[0048] The term "untreated area" refers to a test area that is subjected to the same conditions as described in the test examples, except that dimethyl sulfoxide is dispensed instead of dimethyl sulfoxide diluent containing the compound of the present invention.

[0049] Experiment 1: Control Experiment against Pythium ultimum, the pathogen causing seedling damping-off. The compound of the present invention was diluted with dimethyl sulfoxide at a concentration of 500 ppm and dispensed 1 μL into a titration plate (96 wells). Then, 150 μL of potato dextrose broth (PDB) medium pre-inoculated with spores of *Rhizoctonia solani* was dispensed. The plate was incubated at 23°C for 5 days to allow *Rhizoctonia solani* to proliferate. The absorbance of each well in the titration plate at 550 nm was then measured, and this value was taken as the growth rate of *Rhizoctonia solani*. The results showed that the growth rate in the areas treated with the compound of the present invention was less than 50% of the growth rate in the untreated areas.

[0050] Industrial availability The compounds of this invention have excellent control effects on plant diseases and are useful as active ingredients in compositions for the control of plant diseases.

Claims

1. The compound represented by formula (A), [Chemical Formula 1] 。 2. A composition for the prevention and control of plant diseases, comprising an inactive carrier and the compound of claim 1.

3. A method for controlling plant diseases, comprising the step of applying the compound of claim 1 or the composition for controlling plant diseases of claim 2 to a plant or the soil of a cultivated plant.

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