TWI848967B - Benzoxazole compound and use thereof - Google Patents

Abstract

The present invention provides a compound having excellent control efficacies against plant diseases. A compound represented by formula (A)

has excellent control efficacies against plant diseases.

Description

Benzazole compounds and their uses

This case claims the priority and benefits of Japanese Patent Application No. 2018-153853 filed on August 20, 2018, and incorporates the entire contents of the Japanese Patent Application No. 2018-153853 into this case.

唑化合物及其用途。 The present invention relates to benzo

Azole compounds and uses thereof.

In the past, various compounds have been developed and put into practical use for the purpose of controlling plant diseases (see non-patent document 1). Patent document 1 describes a compound represented by formula (B) (hereinafter referred to as compound B) as an insecticide.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] U.S. Patent No. 9615580 Specification

[Non-patent literature]

[Non-patent document 1] The Pesticide Manual - 17th edition (BCPC publication) ISBN 978-1-901396-88-1

The subject of the present invention is to provide a compound that has excellent control effect on plant diseases.

The present invention is as follows.

[1] A compound represented by formula (A) (hereinafter referred to as compound A)

[2] A composition comprising the compound as described in [1] and an inert carrier.

[3] A method for controlling plant diseases, which comprises treating plants or soil with an effective amount of the compound described in [1].

This invention can prevent and control plant diseases.

The composition of the present invention contains compound A and an inert carrier. The composition of the present invention is usually prepared by mixing compound A with an inert carrier such as a solid carrier or a liquid carrier, and adding surfactants, other preparation aids, emulsions, oils, powders, granules, wettable powders, water-dispersible granules, flowable agents, dry flowable agents, microcapsules, etc. as needed.

The composition of the present invention usually contains 0.0001 to 95% by weight of compound A.

As for the solid carriers that can be used in the formulation, for example, there are: clays (kaolin, diatomaceous earth, bentonite, acid clay, etc.), dry silica, wet silica, talc, ceramics, other inorganic minerals (sericite, quartz, sulfur, activated carbon, calcium carbonate, etc.), chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.) and other fine powders and granules, and synthetic resins (polypropylene, polyacrylonitrile, polymethyl methacrylate, polyethylene terephthalate and other polyester resins, nylon-6, nylon-11, nylon-66 and other nylon resins, polyamide resins, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymers, etc.).

Liquid carriers include, for example, water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (toluene, xylene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, etc.), ethers (diisopropyl ether, diethylene glycol dimethyl ether, etc.), amides (N,N-dimethylformamide, etc.), sulfoxides (dimethyl sulfoxide, etc.) and vegetable oils (soybean oil, cottonseed oil, etc.).

Surfactants include, for example: non-ionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyethylene glycol fatty acid esters, and anionic surfactants such as alkyl sulfonates, alkyl benzene sulfonates, and alkyl sulfates.

Other additives for preparations include adhesives, dispersants, colorants and stabilizers, etc. Specifically, they include casein, gelatin, sugars (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, etc.), acid isopropyl phosphate, 2,6-di-tert-butyl-4-methylphenol, BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

Compound A is effective against plant pathogens. The following are examples of plant diseases caused by plant pathogens. The names in parentheses show the scientific names of the pathogens that cause the diseases.

Magnaporthe grisea, Cochliobolus miyabeanus, Rhizoctonia solani, Gibberella fujikuroi, Sclerophthora macrospora; Blumeria graminis, Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale, Puccinia striiformis, Puccinia graminis, Puccinia recondita, Microdochium nivale, Microdochium majus, Typhula incarnata, Typhula ishikariensis, Ustilago tritici), bunt (Tilletia caries, Tilletia controversa), eyespot (Pseudocercosporella herpotrichoides), stubble (Stagonospora nodorum), yellow spot (Pyrenophora tritici-repentis), Rhizoctonia solani, Gaeumannomyces graminis; barley powdery mildew (Blumeria graminis), red mold (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), yellow rust (Puccinia striiformis), black rust (Puccinia graminis), red rust (Puccinia hordei), barley stem rust (Puccinia hordei), naked smut (Ustilago nuda), cloud-shaped disease (Rhynchosporium secalis), web spot disease (Pyrenophora teres), spot disease (Cochliobolus sativus), leaf spot disease (Pyrenophora graminea), column septum leaf spot disease (Ramularia collo-cygni), Rhizoctonia solani; corn rust disease (Puccinia sorghi), southern rust disease (Puccinia polysora), sooty stripe disease (Setosphaeria turcica), tropical rust disease (Physopella zeae), corn and flax leaf blight disease (Cochliobolus heterostrophus), anthracnose disease (Colletotrichum graminicola), gray leaf spot disease (Cercospora zeae-maydis), brown spot disease (Kabatiella zeae), leaf spot disease (Phaeosphaeria maydis), Stenocarpella maydis, Stenocarpella macrospora, Fusarium graminearum, Fusarium verticilioides, Colletotrichum graminicola, Ustilago maydis; Cotton anthracnose (Colletotrichum gossypii), white mold (Ramularia areola), black spot (Alternaria macrospora, Alternaria gossypii), Black root rot (Thielaviopsis basicola) caused by Thielaviopsis genus; Coffee rust (Hemileia vastatrix), Leaf spot (Cercospora coffeicola); Rapeseed sclerotinia (Sclerotinia sclerotiorum), Black spot (Alternaria brassicae), Root blight (Phoma lingam); Sugarcane rust (Puccinia melanocephela, Puccinia kuehnii; sunflower rust (Puccinia helianthi), dwarf fungus (Plasmopara halstedii); citrus black spot (Diaporthe citri), scab (Elsinoe fawcetti), green mold (Penicillium digitatum, Penicillium italicum), blight (Phytophthora parasitica, Phytophthora citrophthora); apple blossom rot (Monilinia mali), rot (Valsa ceratosperma), apple powdery mildew (Podosphaera leucotricha), leaf spot disease (Alternaria alternata apple pathotype), black spot (Venturia inaequalis), anthracnose (Glomerella cingulata), brown spot (Diplocarpon mali), ring spot (Botryosphaeria berengeriana), apple blight (Phytophtora cactorum); pear scab (Venturia nashicola, Venturia pirina), black spot (Alternaria alternata Japanese pear pathotype), red spot (Gymnosporangium haraeanum); peach brown rot (Monilinia fructicola), peach scab (Cladosporium carpophilum), trunk blight (Phomopsis sp.); grape black pox (Elsinoe ampelina), late rot (Glomerella cingulata), grape powdery mildew (Uncinula necator), grape layer rust (Phakopsora ampelopsidis), black rot (Guignardia bidwellii), grape sap fungus (Plasmopara viticola); persimmon anthracnose (Gloeosporium kaki), persimmon leaf fall (Cercospora kaki, Mycosphaerella nawae; anthracnose of melons (Colletotrichum lagenarium), powdery mildew of eggplant (Sphaerotheca fuliginea), vine blight (Didymella bryoniae), brown spot (Corynespora cassiicola), stem blight (Fusarium oxysporum), melon dwarf fungus (Pseudoperonospora cubensis), carnation blight (Phytophthora sp.), seedling blight (Pythium sp.); tomato ring rot (Alternaria solani), leaf mold (Cladosporium fulvum), sooty mold (Pseudocercospora fuligena), potato rot (Phytophthora infestans), tomato powdery mildew (Leveillula taurica); eggplant brown spot (Phomopsis vexans), tobacco powdery mildew (Erysiphe cichoracearum; Alternaria japonica, Cercosporella brassicae, Plasmodiophora brassicae, Peronospora parasitica of cruciferous vegetables; Puccinia allii; Cercospora kikuchii, Elsinoe glycines, Diaporthe phaseolorum var.sojae, Phakopsora pachyrhizi, Corynespora cassiicola, Colletotrichum glycines, Colletotrichum truncatum, Rhizoctonia solani, Septoria glycines, Cercospora kikuchii, Elsinoe glycines, Diaporthe phaseolorum var.sojae, Phakopsora pachyrhizi, Corynespora cassiicola, Colletotrichum truncatum, Rhizoctonia solani, Septoria glycines, Cercospora kikuchii, Elsinoe glycines, Diaporthe phaseolorum var.sojae, Phakopsora pachyrhizi, sojina), Sclerotinia sclerotiorum, Microsphaera diffusa, Phytophthora sojae, Peronospora manshurica, Fusarium virguliforme; Sclerotinia sclerotiorum, Uromyces appendiculatus, Phaeosariopsis griseola, Colletotrichum lindemuthianum; Cercospora personata, Cercospora arachidicola, Sclerotium rolfsii; Erysiphe pisi, Alternaria sclerotiorum, solani), potato blight (Phytophthora infestans), red rot (Phytophthora erythroseptica), powdery scab (Spongospora subterranean f.sp.subterranea), half-body wilt (Verticillium albo-atrum, Verticillium dahliae, Verticillium nigrescens); strawberry powdery mildew (Sphaerotheca humuli); tea web cake disease (Exobasidium reticulatum), tea scab (Elsinoe leucospila), ring spot disease (Pestalotiopsis sp.), tea anthracnose (Colletotrichum theae-sinensis); tobacco red spot disease (Alternaria longipes), tobacco anthracnose (Colletotrichum tabacum), tobacco spore fungus disease (Peronospora tabacina), tobacco blight (Phytophthora nicotianae); beet brown spot (Cercospora beticola), leaf rot (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), black root (Aphanomyces cochlioides), beet rust (Uromyces betae); rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa); chrysanthemum brown spot (Septoria chrysanthemi-indici), white rust (Puccinia horiana); onion white spot leaf blight (Botrytis cinerea, Botrytis byssoidea, Botrytis squamosa), gray rot (Botrytis allii), small sclerotinia rot (Botrytis squamosa); sclerotinia rot of various crops (Sclerotinia sclerotiorum), gray mold (Botrytis cinerea); radish black spot (Alternaria brassicicola); lawn dollar spot (Sclerotinia homoeocarpa), turf brown spot and giant spot (Rhizoctonia solani); and banana leaf spot (Mycosphaerella fijiensis, Mycosphaerella musicola).

Seed diseases or early growth diseases of various crops caused by Aspergillus, Penicillium, Fusarium, Gibberella, Tricoderma, Thielaviopsis, Rhizopus, Mucor, Corticium, Phoma, Rhizoctonia and Diplodia. Viral diseases of various crops transmitted by Polymixa or Olpidium.

Rice seedling blight (Burkholderia plantarii); cucumber spot blight (Pseudomonas syringae pv.lachrymans); eggplant bacterial wilt (Ralstonia solanacearum), citrus ulcer (Xanthomonas citiri); cabbage soft rot (Erwinia carotovora), etc.

The plant disease prevention and control methods of the present invention include, for example: treatment of plant bodies by spreading on stems and leaves, seed disinfection, etc.; treatment of plant cultivation medium by soil treatment, etc.

The treatment amount of compound A is usually 1 to 10,000 g per 1,000 square meters (1,000 m ² ). When compound A is formulated into emulsions, wettable powders, aqueous suspensions, etc., it is usually diluted with water to a concentration of 0.01 to 10,000 ppm for active ingredient application, while granules, powders, etc. are usually applied directly.

The composition of the present invention can be used as a control agent for plant diseases in dry fields, paddy fields, grasslands, orchards and other agricultural lands.

(Implementation example)

The present invention is described in more detail below through manufacturing examples and test examples, but the present invention is not limited to these examples.

First, a production example of compound A is presented.

Step 1

In a mixture of 69.7 g of 2-amino-4-(trifluoromethanesulfonyl)phenol, 37.3 g of N,N-diisopropylethylamine and 191 g of tetrahydrofuran prepared by the method described in the specification of U.S. Patent No. 8426443, a mixture of 42.2 g of pyridine-2-carbonyl chloride and 206 g of toluene was added dropwise at 40°C under a nitrogen atmosphere, and stirred at 40°C for 3 hours. 88.8 g of 8% aqueous sodium hydroxide solution was added to the obtained mixture, and the mixture was cooled to 5°C. The obtained solid was filtered, and the filtrate was washed with water and toluene in sequence, and dried under reduced pressure to obtain 42.1 g of intermediate A shown in the following formula.

Intermediate A: ¹ H-NMR (DMSO-d ₆ ) δ (ppm): 12.59 (1H, br s), 10.64 (1H, s), 9.12 (1H, d), 8.77 (1H, dd), 8.22 ( 1H,dd),8.13(1H,m),7.78(1H,dd),7.74(1H,m),7.32(1H,d).

Step 2

In a nitrogen environment, a mixture of 20.0 g of intermediate A, 100 g of xylene and 27.0 g of p-toluenesulfonic acid monohydrate was stirred for 6 hours under reflux using a Dean-Stark apparatus to remove the generated water from the system. The mixture was cooled to room temperature and 39.9 g of a 20% aqueous potassium carbonate solution was added for separation. The organic layer was washed with a 5% aqueous potassium carbonate solution and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 10.0 g of compound A.

The ¹ H-NMR data of Compound A are shown below.

¹ H-NMR (DMSO-d ₆ ) δ (ppm): 8.87 (1H, m), 8.70 (1H, d), 8.41 (1H, m), 8.34 (1H, d), 8.25 (1H, dd), 8.14(1H,m),7.73(1H,m).

Next, present the test case.

Test example 1

After 1 μL of dimethyl sulfoxide solution containing a predetermined concentration of compound A was dispensed into the wells of a titer plate (96 wells), 150 μL of complete culture medium containing spore suspension of Botrytis cinerea was dispensed and prepared in such a way that the final concentration of compound A became 100 ppm as a treatment area. In addition, a non-treated area was prepared in another well. The plate was cultured at 18°C for 3 days to allow the Botrytis cinerea to proliferate, and the absorbance at 600 nm of each well of the titer plate was measured as the growth of Botrytis cinerea. Based on the growth, the efficacy was calculated using "Formula 1".

"Formula 1" Efficacy (%) = 100 × (X-Y) / X

X: Growth of bacteria in the untreated area

Y: Growth rate of bacteria in the treatment area

The untreated area refers to an area where the same operation as the treated area is performed except that compound A is not used.

The result was an efficacy of 60%.

Comparative test example 1

The test was conducted according to Test Example 1 except that Compound B was used to replace Compound A. The result was an efficacy of 0%.

[Industrial availability]

Compound A shows excellent control effect on plant diseases.

Claims (3)

A compound is a compound represented by the following formula (A);

A composition comprising the compound described in item 1 of the patent application and an inert carrier. A method for preventing and controlling plant diseases, comprising treating plants or soil with an effective amount of the compound described in item 1 of the patent application scope.