WO2020054790A1 - Bipyridine compound and use thereof - Google Patents

Bipyridine compound and use thereof Download PDF

Info

Publication number
WO2020054790A1
WO2020054790A1 PCT/JP2019/035800 JP2019035800W WO2020054790A1 WO 2020054790 A1 WO2020054790 A1 WO 2020054790A1 JP 2019035800 W JP2019035800 W JP 2019035800W WO 2020054790 A1 WO2020054790 A1 WO 2020054790A1
Authority
WO
WIPO (PCT)
Prior art keywords
spot
compound
rust
rot
disease
Prior art date
Application number
PCT/JP2019/035800
Other languages
French (fr)
Japanese (ja)
Inventor
大輔 笹山
Original Assignee
住友化学株式会社
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 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN201980059511.1A priority Critical patent/CN112673006B/en
Priority to KR1020217007046A priority patent/KR20210060459A/en
Priority to JP2020546065A priority patent/JP7368368B2/en
Publication of WO2020054790A1 publication Critical patent/WO2020054790A1/en

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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • Non-Patent Document 1 Conventionally, various compounds have been developed for controlling plant diseases, and are being put to practical use (see Non-Patent Document 1).
  • An object of the present invention is to provide a compound having an excellent controlling effect on plant diseases.
  • the present invention is as follows. [1] Formula (A) (Hereinafter, referred to as compound A). [2] A composition comprising the compound according to [1] and an inert carrier. [3] A method for controlling plant diseases by treating a plant or soil with an effective amount of the compound according to [1].
  • plant diseases can be controlled.
  • the composition of the present invention contains Compound A and an inert carrier.
  • the composition of the present invention is usually a mixture of compound A and a solid carrier, an inert carrier such as a liquid carrier, and, if necessary, a surfactant and other formulation auxiliaries, and emulsions, oils, It is formulated into powders, granules, wettable powders, wettable powders, flowables, dry flowables, microcapsules and the like.
  • the composition of the present invention generally contains 0.0001 to 95% by weight of Compound A.
  • solid carriers used in the formulation include clays (kaolin clay, diatomaceous earth, bentonite, acid clay, etc.), dry silica, wet silica, talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur, Activated carbon, calcium carbonate, etc., fine powders and granular materials such as fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, salt ammonium, etc.) and synthetic resins (polypropylene, polyacrylonitrile, polymethyl methacrylate, polyethylene terephthalate, etc.) Polyester resins, nylon resins such as nylon-6, nylon-11 and nylon-66, polyamide resins, polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-propylene copolymers).
  • clays kaolin clay, diatomaceous earth, bentonite, acid clay, etc.
  • dry silica wet silica, talc
  • liquid carrier examples include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (toluene, xylene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), Esters (such as ethyl acetate and butyl acetate), nitriles (such as acetonitrile), ethers (such as diisopropyl ether and diethylene glycol dimethyl ether), amides (such as N, N-dimethylformamide), sulfoxides (such as dimethyl sulfoxide), and Vegetable oils (soy oil, cottonseed oil, and the like).
  • alcohols methanol, ethanol, etc.
  • ketones acetone, methyl ethyl ketone, etc.
  • aromatic hydrocarbons toluene, xylene, etc.
  • surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyethylene glycol fatty acid ester, and anions such as alkyl sulfonate, alkyl benzene sulfonate and alkyl sulfate. Surfactants.
  • adjuvants for preparations include fixing agents, dispersants, coloring agents and stabilizers, specifically, casein, gelatin, sugars (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, Synthetic water-soluble polymer (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, etc.), isopropyl acid phosphate, 2,6-di-tert-butyl-4-methylphenol, BHA (2-tert-butyl-4-methoxyphenol) And 3-tert-butyl-4-methoxyphenol).
  • fixing agents include fixing agents, dispersants, coloring agents and stabilizers, specifically, casein, gelatin, sugars (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, Synthetic water-soluble polymer (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, etc
  • Compound A has potency against phytopathogenic microorganisms.
  • plant diseases derived from phytopathogenic microorganisms include the following.
  • the name in parentheses indicates the scientific name of the pathogenic microorganism causing the disease.
  • Rice blast (Magnaporthe grisea), sesame leaf blight (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani), harmless seedling (Gibberella fujikuroi), yellow dwarf (Sclerophthora macrospora); wheat powdery mildew (Blumeria) graminis), Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), Yellow rust (Puccinia striiformis), Black rust (Puccinia graminis), Red rust (Puccinia recondita), Red snow rot (Microdochium) , Microdochium majus), snow rot sclerotium scab (Typhula incarnata, Typhula ishikariensis), naked smut (Ustilago tritici), scab (Tilletia caries,
  • Powdery mildew of strawberry (Sphaerotheca humuli); Net leaf blight of tea (Exobasidium reticulatum), white scab (Elsinoe leucospila), ring spot (Pestalotiopsis sp.), Anthracnose (Colletotrichum theae-sinensis); Scab (Alternaria longipes), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), plague (Phytophthora nicotianae); sugar beet brown spot (Cercospora beticola), leaf rot (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), black rot (Aphanomyces cochlioides), rust (Uromyces betae); rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa); chrys
  • Aspergillus Penicillium, Fusarium, Gibberella, Tricoderma, Thielaviopsis, Rhizopus, Mucor, Corticium, Phoma, Rhizoctonia, and Diplodia spp. Disease.
  • the method for controlling plant diseases of the present invention includes, for example, treatment of plants such as foliage application and seed disinfection; and treatment of plant cultivation areas such as soil treatment.
  • the treatment amount of Compound A is usually 1 to 10000 g per 1000 m 2 .
  • Compound A When Compound A is formulated into an emulsion, wettable powder, flowable or the like, it is usually diluted with water so that the active ingredient concentration becomes 0.01 to 10000 ppm, and granules, powders and the like are used. Usually, it is applied as it is.
  • composition of the present invention can be used as an agent for controlling plant diseases in agricultural lands such as fields, paddy fields, lawns, and orchards.
  • Step 2 To a mixture of 1.39 g of thionyl chloride, 49.72 g of xylene, and 0.04 g of N, N-dimethylformamide was added at 60 ° C. a mixture of 3.79 g of the intermediate A and 5.52 g of xylene. For 5.5 hours. 2.84 g of thionyl chloride was added to the obtained mixture, and the mixture was stirred at 60 ° C. for 7 hours. After the obtained mixture was brought to room temperature, it was concentrated under reduced pressure.
  • Test example 1 A plastic pot was filled with soil, and tomato (cultivar: patio) was sown and cultivated in a greenhouse for 19 days. 35 parts by weight of a mixture of polyoxyethylene alkyl ether sulfate ammonium salt and wet silica (weight ratio 1: 1), 20 parts by weight of compound A, and 45 parts by weight of water were thoroughly mixed. The obtained mixture was diluted with water to prepare a diluent containing Compound A at 125 ppm. This diluted solution was sprayed so as to sufficiently adhere to the leaf surface of the tomato.
  • Compound A exhibits an excellent control effect on plant diseases.

Abstract

The present invention provides a compound that is highly effective in controlling plant diseases. This compound is represented by formula (A) and is highly effective in controlling plant diseases.

Description

ビピリジン化合物及びその用途Bipyridine compounds and their uses
　本出願は２０１８年９月１３日に出願された日本国特許出願第２０１８－１７１１８５号に対する優先権及びその利益を主張するものであり、その全内容は参照することにより本出願に組み込まれる。
　本発明はビピリジン化合物及びその用途に関する。 This application claims the priority and benefit of Japanese Patent Application No. 2018-171185 filed on September 13, 2018, the entire contents of which are incorporated into the present application by reference.
The present invention relates to bipyridine compounds and uses thereof.
　従来、植物病害を防除するために種々の化合物が開発されており、実用に供されている（非特許文献１参照）。 Conventionally, various compounds have been developed for controlling plant diseases, and are being put to practical use (see Non-Patent Document 1).
　本発明は、植物病害に対して優れた防除効力を有する化合物を提供することを課題とする。 は An object of the present invention is to provide a compound having an excellent controlling effect on plant diseases.
　本発明は、以下のとおりである。
〔１〕　式（Ａ）
Figure JPOXMLDOC01-appb-C000002
 で示される化合物（以下、化合物Ａと記す）。
〔２〕　〔１〕に記載の化合物と、不活性担体とを含有する組成物。
〔３〕　〔１〕に記載の化合物の有効量を植物又は土壌に処理することによる、植物病害の防除方法。 The present invention is as follows.
[1] Formula (A)
Figure JPOXMLDOC01-appb-C000002
 (Hereinafter, referred to as compound A).
[2] A composition comprising the compound according to [1] and an inert carrier.
[3] A method for controlling plant diseases by treating a plant or soil with an effective amount of the compound according to [1].
　本発明により、植物病害を防除することができる。 植物 According to the present invention, plant diseases can be controlled.
　本発明の組成物は、化合物Ａと不活性担体とを含有する。本発明の組成物は、通常、化合物Ａと固体担体、液体担体等の不活性担体とを混合し、必要に応じて界面活性剤、その他の製剤用補助剤を添加して、乳剤、油剤、粉剤、粒剤、水和剤、顆粒水和剤、フロアブル剤、ドライフロアブル剤、マイクロカプセル剤等に製剤化される。
　本発明の組成物は、化合物Ａを通常０．０００１～９５重量％含有する。 The composition of the present invention contains Compound A and an inert carrier. The composition of the present invention is usually a mixture of compound A and a solid carrier, an inert carrier such as a liquid carrier, and, if necessary, a surfactant and other formulation auxiliaries, and emulsions, oils, It is formulated into powders, granules, wettable powders, wettable powders, flowables, dry flowables, microcapsules and the like.
The composition of the present invention generally contains 0.0001 to 95% by weight of Compound A.
　製剤化の際に用いられる固体担体としては、例えば粘土類（カオリンクレー、珪藻土、ベントナイト、酸性白土等）、乾式シリカ、湿式シリカ、タルク、セラミック、その他の無機鉱物（セリサイト、石英、硫黄、活性炭、炭酸カルシウム等）、化学肥料（硫安、燐安、硝安、尿素、塩安等）等の微粉末及び粒状物等、並びに合成樹脂（ポリプロピレン、ポリアクリロニトリル、ポリメタクリル酸メチル、ポリエチレンテレフタレート等のポリエステル樹脂、ナイロン－６、ナイロン－１１、ナイロン－６６等のナイロン樹脂、ポリアミド樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、塩化ビニル－プロピレン共重合体等）が挙げられる。 Examples of solid carriers used in the formulation include clays (kaolin clay, diatomaceous earth, bentonite, acid clay, etc.), dry silica, wet silica, talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur, Activated carbon, calcium carbonate, etc., fine powders and granular materials such as fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, salt ammonium, etc.) and synthetic resins (polypropylene, polyacrylonitrile, polymethyl methacrylate, polyethylene terephthalate, etc.) Polyester resins, nylon resins such as nylon-6, nylon-11 and nylon-66, polyamide resins, polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-propylene copolymers).
　液体担体としては、例えば水、アルコール類（メタノール、エタノール等）、ケトン類（アセトン、メチルエチルケトン等）、芳香族炭化水素類（トルエン、キシレン等）、脂肪族炭化水素類（ヘキサン、シクロヘキサン等）、エステル類（酢酸エチル、酢酸ブチル等）、ニトリル類（アセトニトリル等）、エーテル類（ジイソプロピルエーテル、ジエチレングリコールジメチルエーテル等）、アミド類（Ｎ，Ｎ－ジメチルホルムアミド等）、スルホキシド類（ジメチルスルホキシド等）、及び植物油（大豆油、綿実油等）が挙げられる。 Examples of the liquid carrier include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (toluene, xylene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), Esters (such as ethyl acetate and butyl acetate), nitriles (such as acetonitrile), ethers (such as diisopropyl ether and diethylene glycol dimethyl ether), amides (such as N, N-dimethylformamide), sulfoxides (such as dimethyl sulfoxide), and Vegetable oils (soy oil, cottonseed oil, and the like).
　界面活性剤としては、例えばポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリエチレングリコール脂肪酸エステル等の非イオン界面活性剤、及びアルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキル硫酸塩等の陰イオン界面活性剤が挙げられる。 Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyethylene glycol fatty acid ester, and anions such as alkyl sulfonate, alkyl benzene sulfonate and alkyl sulfate. Surfactants.
　その他の製剤用補助剤としては、固着剤、分散剤、着色剤及び安定剤等、具体的には例えばカゼイン、ゼラチン、糖類（でんぷん、アラビアガム、セルロース誘導体、アルギン酸等）、リグニン誘導体、ベントナイト、合成水溶性高分子（ポリビニルアルコール、ポリビニルピロリドン、ポリアクリル酸類等）、酸性リン酸イソプロピル、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、ＢＨＡ（２－ｔｅｒｔ－ブチル－４－メトキシフェノールと３－ｔｅｒｔ－ブチル－４－メトキシフェノールとの混合物）が挙げられる。 Other adjuvants for preparations include fixing agents, dispersants, coloring agents and stabilizers, specifically, casein, gelatin, sugars (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, Synthetic water-soluble polymer (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, etc.), isopropyl acid phosphate, 2,6-di-tert-butyl-4-methylphenol, BHA (2-tert-butyl-4-methoxyphenol) And 3-tert-butyl-4-methoxyphenol).
　化合物Ａは、植物病原性微生物に対して効力を有する。植物病原性微生物に由来する植物病害としては、以下のものが挙げられる。括弧内は、その病害を引き起こす病原性微生物の学名を示す。 Compound A has potency against phytopathogenic microorganisms. Examples of plant diseases derived from phytopathogenic microorganisms include the following. The name in parentheses indicates the scientific name of the pathogenic microorganism causing the disease.
　イネのいもち病（Magnaporthe grisea）、ごま葉枯病（Cochliobolus miyabeanus）、紋枯病（Rhizoctonia solani）、馬鹿苗病（Gibberella fujikuroi）、黄化萎縮病（Sclerophthora macrospora）；コムギのうどんこ病（Blumeria graminis）、赤かび病（Fusarium graminearum、Fusarium avenaceum、Fusarium culmorum、Microdochium nivale）、黄さび病（Puccinia striiformis）、黒さび病（Puccinia graminis）、赤さび病（Puccinia recondita）、紅色雪腐病（Microdochium nivale、Microdochium majus）、雪腐小粒菌核病（Typhula incarnata、Typhula ishikariensis）、裸黒穂病（Ustilago tritici）、なまぐさ黒穂病（Tilletia caries、Tilletia controversa）、眼紋病（Pseudocercosporella herpotrichoides）、ふ枯病（Stagonospora nodorum）、黄斑病（Pyrenophora tritici-repentis）、リゾクトニア属菌による苗立枯れ病（Rhizoctonia solani）、立枯病（Gaeumannomyces graminis）；オオムギのうどんこ病（Blumeria graminis）、赤かび病（Fusarium graminearum、Fusarium avenaceum、Fusarium culmorum、Microdochium nivale）、黄さび病（Puccinia striiformis）、黒さび病（Puccinia graminis）、赤さび病（Puccinia hordei）、小さび病（Puccinia hordei）、裸黒穂病（Ustilago nuda）、雲形病（Rhynchosporium secalis）、網斑病（Pyrenophora teres）、斑点病（Cochliobolus sativus）、斑葉病（Pyrenophora graminea）、ラムラリアリーフスポット病（Ramularia collo-cygni）、リゾクトニア属菌による苗立枯れ病（Rhizoctonia solani）；トウモロコシのさび病（Puccinia sorghi）、南方さび病（Puccinia polysora）、すす紋病（Setosphaeria turcica）、熱帯性さび病（Physopella zeae）、ごま葉枯病（Cochliobolus heterostrophus）、炭そ病（Colletotrichum graminicola）、グレーリーフスポット病（Cercospora zeae-maydis）、褐斑病（Kabatiella zeae）、ファエオスファエリアリーフスポット病（Phaeosphaeria maydis）、Stenocarpella maydis、Stenocarpella macrospora、ストークロット病（Fusarium graminearum、Fusarium verticilioides、Colletotrichum graminicola）、黒穂病（Ustilago maydis）；ワタの炭そ病（Colletotrichum gossypii）、白かび病（Ramularia areola）、黒斑病（Alternaria macrospora、Alternaria gossypii）、Thielaviopsis属菌によるBlack root rot病（Thielaviopsis basicola）；コーヒーのさび病（Hemileia vastatrix）、リーフスポット病（Cercospora coffeicola）；ナタネの菌核病（Sclerotinia sclerotiorum）、黒斑病（Alternaria brassicae）、根朽病（Phoma lingam）；サトウキビのさび病（Puccinia melanocephela、Puccinia kuehnii）；ヒマワリさび病（Puccinia helianthi）、べと病（Plasmopara halstedii）；カンキツ類の黒点病（Diaporthe citri）、そうか病（Elsinoe fawcetti）、果実腐敗病（Penicillium digitatum、Penicillium italicum）、疫病（Phytophthora parasitica、Phytophthora citrophthora）；リンゴのモニリア病（Monilinia mali）、腐らん病（Valsa ceratosperma）、うどんこ病（Podosphaera leucotricha）、斑点落葉病（Alternaria alternata apple pathotype）、黒星病（Venturia inaequalis）、炭そ病（Glomerella cingulata）、褐斑病（Diplocarpon mali）、輪紋病（Botryosphaeria berengeriana）、疫病（Phytophtora cactorum）；ナシの黒星病（Venturia nashicola、Venturia pirina）、黒斑病（Alternaria alternata Japanese pear pathotype）、赤星病（Gymnosporangium haraeanum）；モモの灰星病（Monilinia fructicola）、黒星病（Cladosporium carpophilum）、フォモプシス腐敗病（Phomopsis sp.）；ブドウの黒とう病（Elsinoe ampelina）、晩腐病（Glomerella cingulata）、うどんこ病（Uncinula necator）、さび病（Phakopsora ampelopsidis）、ブラックロット病（Guignardia bidwellii）、べと病（Plasmopara viticola）；カキの炭そ病（Gloeosporium kaki）、落葉病（Cercospora kaki、Mycosphaerella nawae）；ウリ類の炭そ病（Colletotrichum lagenarium）、うどんこ病（Sphaerotheca fuliginea）、つる枯病（Didymella bryoniae）、褐斑病（Corynespora cassiicola）、つる割病（Fusarium oxysporum）、べと病（Pseudoperonospora cubensis）、疫病（Phytophthora sp.）、苗立枯病（Pythium sp.）；トマトの輪紋病（Alternaria solani）、葉かび病（Cladosporium fulvum）、すすかび病（Pseudocercospora fuligena）、疫病（Phytophthora infestans）、うどんこ病（Leveillula taurica）；ナスの褐紋病（Phomopsis vexans）、うどんこ病（Erysiphe cichoracearum）；アブラナ科野菜の黒斑病（Alternaria japonica）、白斑病（Cercosporella brassicae）、根こぶ病（Plasmodiophora brassicae）、べと病（Peronospora parasitica）；ネギのさび病（Puccinia allii）；ダイズの紫斑病（Cercospora kikuchii）、黒とう病（Elsinoe glycines）、黒点病（Diaporthe phaseolorum var. sojae）、さび病（Phakopsora pachyrhizi)、褐色輪紋病（Corynespora cassiicola）、炭疽病（Colletotrichum glycines、Colletotrichum truncatum）、葉腐病（Rhizoctonia solani）、褐紋病（Septoria glycines）、斑点病（Cercospora sojina）、菌核病（Sclerotinia sclerotiorum）、うどんこ病（Microsphaera diffusa）、茎疫病（Phytophthora sojae）、べと病（Peronospora manshurica）、突然死病（Fusarium virguliforme）；インゲンの菌核病（Sclerotinia sclerotiorum）、さび病（Uromyces appendiculatus）、角斑病（Phaeoisariopsis griseola）、炭そ病（Colletotrichum lindemuthianum）；ラッカセイの黒渋病（Cercospora personata）、褐斑病（Cercospora arachidicola）、白絹病（Sclerotium rolfsii）；エンドウのうどんこ病（Erysiphe pisi）；ジャガイモの夏疫病（Alternaria solani）、疫病（Phytophthora infestans）、緋色腐敗病（Phytophthora erythroseptica）、粉状そうか病（Spongospora subterranean f. sp. subterranea）、半身萎凋病（Verticillium albo-atrum、Verticillium dahliae、Verticillium nigrescens）；イチゴのうどんこ病（Sphaerotheca humuli）；チャの網もち病（Exobasidium reticulatum）、白星病（Elsinoe leucospila）、輪斑病（Pestalotiopsis sp.）、炭そ病（Colletotrichum theae-sinensis）；タバコの赤星病（Alternaria longipes）、炭そ病（Colletotrichum tabacum）、べと病（Peronospora tabacina）、疫病（Phytophthora nicotianae）；テンサイの褐斑病（Cercospora beticola）、葉腐病（Thanatephorus cucumeris）、根腐病（Thanatephorus cucumeris）、黒根病（Aphanomyces cochlioides）、さび病（Uromyces betae）；バラの黒星病（Diplocarpon rosae）、うどんこ病（Sphaerotheca pannosa）；キクの褐斑病（Septoria chrysanthemi-indici）、白さび病（Puccinia horiana）；タマネギの白斑葉枯病（Botrytis cinerea、Botrytis byssoidea、Botrytis squamosa)、灰色腐敗病（Botrytis allii）、小菌核性腐敗病（Botrytis squamosa）；種々の作物の菌核病（Sclerotinia sclerotiorum）；ダイコン黒斑病（Alternaria brassicicola）；シバのダラースポット病（Sclerotinia homoeocarpa）、シバのブラウンパッチ病およびラージパッチ病（Rhizoctonia solani）；並びにバナナのシガトカ病（Mycosphaerella fijiensis、Mycosphaerella musicola）。
Aspergillus属、Penicillium属、Fusarium属、Gibberella属、Tricoderma属、Thielaviopsis属、Rhizopus属、Mucor属、Corticium属、Phoma属、Rhizoctonia属、及びDiplodia属菌等によって引き起こされる、各種作物の種子病害又は生育初期の病害。Polymixa属又はOlpidium属等によって媒介される各種作物のウイルス病。
イネの苗立枯細菌病（Burkholderia plantarii）；キュウリの斑点細菌病（Pseudomonas syringae pv. lachrymans）；ナスの青枯病（Ralstonia solanacearum）、カンキツのかいよう病（Xanthomonas citiri）；ハクサイの軟腐病（Erwinia carotovora）等。 Rice blast (Magnaporthe grisea), sesame leaf blight (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani), stupid seedling (Gibberella fujikuroi), yellow dwarf (Sclerophthora macrospora); wheat powdery mildew (Blumeria) graminis), Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), Yellow rust (Puccinia striiformis), Black rust (Puccinia graminis), Red rust (Puccinia recondita), Red snow rot (Microdochium) , Microdochium majus), snow rot sclerotium scab (Typhula incarnata, Typhula ishikariensis), naked smut (Ustilago tritici), scab (Tilletia caries, Tilletia controversa), eye spot (Pseudocercosporella herpotrichoides), blight Stagonospora nodorum), Macular disease (Pyrenophora tritici-repentis), Seedling blight caused by Rhizoctonia (Rhizoctonia solani), Damping blight (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) Rust (Puccinia hordei), Naked smut (Ustilago nuda), Scratches (Rhynchosporium secalis), Netspot (Pyrenophora teres), Spots (Cochliobolus sativus), Spotspot (Pyrenophora graminea), Lambralia leaf spot ( Ramularia collo-cygni), Seedling blight caused by Rhizoctonia spp. (Rhizoctonia solani); Corn rust (Puccinia sorghi), Southern rust (Puccinia polysora), Soybean rust (Setosphaeria turcica), Tropical rust (Physopella) zeae), sesame leaf blight (Cochliobolus heterostrophus), anthracnose (Colletotrichum graminicola), gray leaf spot (Cercospora zeae-maydis), brown spot (Kabatiella zeae), Aeosphaeria leaf spot disease (Phaeosphaeria maydis), Stenocarpella maydis, Stenocarpella macrospora, Stokelot disease (Fusarium graminearum, Fusarium verticilioides, Colletotrichum graminicola), smut (Ustilago maydis); Cotton anthracnose (Colletotrichum gopi) Mold rust (Ramularia areola), black spot rot (Alternaria macrospora, Alternaria gossypii), Black root rot disease (Thielaviopsis basicola) due to Thielaviopsis genus; coffee rust (Hemileia vastatrix), leaf spot disease (Cercospora coffeicola); Sclerotinia sclerotiorum, black spot (Alternaria brassicae), root rot (Phoma lingam); sugar cane rust (Puccinia melanocephela, Puccinia kuehnii); sunflower rust (Puccinia helianthi), downy mildew (Plasmo halato) ); Citrus black spot (Diaporthe citri), scab (Elsinoe fawcetti), fruit rot (Penicill) ium digitatum, Penicillium italicum, plague (Phytophthora parasitica, Phytophthora citrophthora); monilia disease of apples (Monilinia mali); Scab (Venturia inaequalis), anthracnose (Glomerella cingulata), brown spot (Diplocarpon mali), ring spot (Botryosphaeria berengeriana), plague (Phytophtora cactorum); pear scab (Venturia nashicola, Venturia pirina), black Leaf spot (Alternaria alternata Japanese pear pathotype), red scab (Gymnosporangium haraeanum); peach ash (Monilinia fructicola), scab (Cladosporium carpophilum), Phomopsis rot (Phomopsis sp.); Grape black spot (Elsinoe) ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black lot disease (Guigna) rdia bidwellii), downy mildew (Plasmopara viticola); oyster anthracnose (Gloeosporium kaki), deciduous disease (Cercospora kaki, Mycosphaerella nawae); cucumber anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea) Vine wilt (Didymella bryoniae), brown spot (Corynespora cassiicola), vine wilt (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.), Seedling blight (Pythium sp.); Tomato ring spot (Alternaria solani), leaf mold (Cladosporium fulvum), scab (Pseudocercospora fuligena), plague (Phytophthora infestans), powdery mildew (Leveillula taurica), eggplant brown spot (Phomopsis vexans), Powdery mildew (Erysiphe cichoracearum); black spot on cruciferous vegetables (Alternaria japonica), white spot (Cercosporella brassicae), clubroot (Plasmodiophora brassicae), downy mildew (Peronospora parasitica); nia allii); soybean purpura (Cercospora kikuchii), black rot (Elsinoe glycines), black spot (Diaporthe phaseolorum var. sojae), rust (Phakopsora pachyrhizi), brown ring spot (Corynespora cassiicola), anthracnose ( Colletotrichum glycines, Colletotrichum truncatum, leaf rot (Rhizoctonia solani), brown spot (Septoria glycines), spot disease (Cercospora sojina), sclerotium disease (Sclerotinia sclerotiorum), powdery mildew (Microsphaera diffusa), stem disease (Phytophora) sojae), downy mildew (Peronospora manshurica), sudden death (Fusarium virguliforme); kidney bean sclerotia (Sclerotinia sclerotiorum), rust (Uromyces appendiculatus), keratophyte (Phaeoisariopsis griseola), anthracnose (Colletotrichum linmuth) ); Peanut black spot (Cercospora personata), brown spot (Cercospora arachidicola), white spot (Sclerotium rolfsii); Pea powdery mildew (Erysiphe pisi); Potato Summer plague (Alternaria solani), plague (Phytophthora infestans), scarlet rot (Phytophthora erythroseptica), powdery scab (Spongospora subterranean f. Sp. ) Powdery mildew of strawberry (Sphaerotheca humuli); Net leaf blight of tea (Exobasidium reticulatum), white scab (Elsinoe leucospila), ring spot (Pestalotiopsis sp.), Anthracnose (Colletotrichum theae-sinensis); Scab (Alternaria longipes), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), plague (Phytophthora nicotianae); sugar beet brown spot (Cercospora beticola), leaf rot (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), black rot (Aphanomyces cochlioides), rust (Uromyces betae); rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa); chrysanthemum leaf spot (S eptoria chrysanthemi-indici), white rust (Puccinia horiana); white spot leaf blight of onion (Botrytis cinerea, Botrytis byssoidea, Botrytis squamosa), gray rot (Botrytis allii), microbial rot (Botrytis squamosa); Sclerotinia sclerotiorum on various crops; Alternaria brassicicola on radish; Sclerotinia homoeocarpa on grass, brown patch and rhizoctonia solani on grass, and sigatoka on banana (Mycosphaerella fijiensis, Mycosphaerella musicola).
Aspergillus, Penicillium, Fusarium, Gibberella, Tricoderma, Thielaviopsis, Rhizopus, Mucor, Corticium, Phoma, Rhizoctonia, and Diplodia spp. Disease. Viral diseases of various crops mediated by the genus Polymixa or the genus Olpidium.
Seedling bacterial disease of rice (Burkholderia plantarii); spot bacterial disease of cucumber (Pseudomonas syringae pv. Lachrymans); bacterial wilt of eggplant (Ralstonia solanacearum); carotovora) etc.
　本発明の植物病害の防除方法は、例えば茎葉散布、種子消毒等の植物体への処理；土壌処理等の植物の栽培地への処理が挙げられる。 方法 The method for controlling plant diseases of the present invention includes, for example, treatment of plants such as foliage application and seed disinfection; and treatment of plant cultivation areas such as soil treatment.
　化合物Ａの処理量は、１０００ｍ2あたり通常１～１００００ｇである。化合物Ａが乳剤、水和剤、フロアブル剤等に製剤化されている場合は、通常、有効成分濃度が０．０１～１００００ｐｐｍとなるように水で希釈して施用し、粒剤、粉剤等は、通常、そのまま施用する。 The treatment amount of Compound A is usually 1 to 10000 g per 1000 m 2 . When Compound A is formulated into an emulsion, wettable powder, flowable or the like, it is usually diluted with water so that the active ingredient concentration becomes 0.01 to 10000 ppm, and granules, powders and the like are used. Usually, it is applied as it is.
　本発明の組成物は、畑、水田、芝生、果樹園等の農耕地における植物病害の防除剤として使用することができる。 組成 The composition of the present invention can be used as an agent for controlling plant diseases in agricultural lands such as fields, paddy fields, lawns, and orchards.
　以下、本発明を製造例、及び試験例によりさらに詳しく説明するが、本発明はこれらの例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Production Examples and Test Examples, but the present invention is not limited to these Examples.
　まず、化合物Ａの製造例を示す。 First, a production example of compound A will be described.
第１工程
　窒素雰囲気下で、１００ｍＬオートクレーブに米国特許第９８５０２０９号明細書に記載の方法で製造した６－クロロ－３－（エタンスルホニル）ピリジン－２－カルボン酸８．５８ｇ、メタノール２５．３ｇ、炭酸水素カリウム６．９８ｇ、及び５％Ｐｄ／炭素０．２２ｇを加え、密閉した後、水素雰囲気下で４５時間反応させた。得られた混合物をろ過し、ろ物をメタノール及び水で順次洗浄した。得られた水洗浄液に３５％塩酸を加えて中和した。得られた固体をろ過し、水で洗浄し、乾燥して、下式で示される中間体Ａを０．３２ｇ得た。
Figure JPOXMLDOC01-appb-C000003
 中間体Ａ：1H-NMR (DMSO-d6) δ(ppm): 14.40 (2H, s), 8.72 (2H, d), 8.59 (2H, d), 3.61 (4H, q), 1.21 (6H, t). First Step Under a nitrogen atmosphere, 8.58 g of 6-chloro-3- (ethanesulfonyl) pyridine-2-carboxylic acid prepared by the method described in US Pat. No. 9,850,209, 25.3 g of methanol, and 100 mL of autoclave were prepared. After adding 6.98 g of potassium hydrogen carbonate and 0.22 g of 5% Pd / carbon, the mixture was closed and reacted under a hydrogen atmosphere for 45 hours. The obtained mixture was filtered, and the residue was washed successively with methanol and water. The obtained water washing solution was neutralized by adding 35% hydrochloric acid. The obtained solid was filtered, washed with water, and dried to obtain 0.32 g of an intermediate A represented by the following formula.
Figure JPOXMLDOC01-appb-C000003
 Intermediate A: 1 H-NMR (DMSO-d 6 ) δ (ppm): 14.40 (2H, s), 8.72 (2H, d), 8.59 (2H, d), 3.61 (4H, q), 1.21 (6H , t).
第２工程
　塩化チオニル１．３９ｇ、キシレン４９．７２ｇ、及びＮ，Ｎ－ジメチルホルムアミド０．０４ｇの混合物に、６０℃で３．７９ｇの中間体Ａ及びキシレン５．５２ｇの混合物を加え、６０℃で５．５時間撹拌した。得られた混合物に塩化チオニル２．８４ｇを加え、６０℃で７時間撹拌した。得られた混合物を室温にした後、減圧下で濃縮した。得られた残さを、米国特許第８４２６４４３号明細書に記載の方法で製造した２－アミノ－４－（トリフルオロメタンスルホニル）フェノール４．２０ｇ及びテトラヒドロフラン１２．５４ｇの混合物に加え、次にテトラヒドロフラン３５．１０ｇ及びキシレン３４．１１ｇを順次加え、６０℃で２時間撹拌した。得られた混合物に水２４．９４ｇ、テトラヒドロフラン１９．３６ｇ、及び２７％水酸化ナトリウム水溶液１．８８ｇの混合物を６０℃で加えて、ｐＨを５．３に調整した。得られた混合物を５℃に冷却し、得られた結晶をろ過した。ろ物を水、キシレン、及び５０％キシレン／テトラヒドロフラン溶液で順次洗浄し、乾燥して、下式で示される中間体Ｂを６．３５ｇ得た。
Figure JPOXMLDOC01-appb-C000004
 中間体Ｂ：1H-NMR (DMSO-d6) δ(ppm): 12.31 (2H, br s), 10.65 (2H, s), 8.90 (2H, d), 8.78 (2H, d), 8.61 (2H, d), 7.84 (2H, dd), 7.32 (2H, d), 3.67 (4H, q), 1.22 (6H, t). Step 2 To a mixture of 1.39 g of thionyl chloride, 49.72 g of xylene, and 0.04 g of N, N-dimethylformamide was added at 60 ° C. a mixture of 3.79 g of the intermediate A and 5.52 g of xylene. For 5.5 hours. 2.84 g of thionyl chloride was added to the obtained mixture, and the mixture was stirred at 60 ° C. for 7 hours. After the obtained mixture was brought to room temperature, it was concentrated under reduced pressure. The resulting residue is added to a mixture of 4.20 g of 2-amino-4- (trifluoromethanesulfonyl) phenol and 12.54 g of tetrahydrofuran prepared by the method described in US Pat. No. 8,426,443, followed by tetrahydrofuran. 10 g and xylene 34.11 g were sequentially added, followed by stirring at 60 ° C. for 2 hours. A mixture of 24.94 g of water, 19.36 g of tetrahydrofuran, and 1.88 g of a 27% aqueous sodium hydroxide solution was added to the obtained mixture at 60 ° C. to adjust the pH to 5.3. The obtained mixture was cooled to 5 ° C., and the obtained crystals were filtered. The residue was sequentially washed with water, xylene, and a 50% xylene / tetrahydrofuran solution, and dried to obtain 6.35 g of an intermediate B represented by the following formula.
Figure JPOXMLDOC01-appb-C000004
 Intermediate B: 1 H-NMR (DMSO-d 6 ) δ (ppm): 12.31 (2H, br s), 10.65 (2H, s), 8.90 (2H, d), 8.78 (2H, d), 8.61 ( 2H, d), 7.84 (2H, dd), 7.32 (2H, d), 3.67 (4H, q), 1.22 (6H, t).
第３工程
　３．０８ｇの中間体Ｂ、キシレン３３５ｇ、及びｐ－トルエンスルホン酸一水和物３３．７１ｇの混合物を、還流下で、ディーンスターク装置を用いて生成した水を系外に除去しながら６９時間撹拌した。得られた混合物を１００℃に冷却した後、室温の２０％炭酸カリウム水溶液９２．５ｇに加え、８０℃で撹拌した。析出した固体をろ過し、ろ物を水及びキシレンで順次洗浄し、乾燥した。得られた固体を室温でＮ，Ｎ－ジメチルホルムアミド１０００ｇに溶解させた後、水１００ｇを滴下した。得られた固体をろ過し、ろ物をＮ，Ｎ－ジメチルホルムアミド及び水で順次洗浄し、乾燥して、化合物Ａを０．８３ｇ得た。
　化合物Ａの1H-NMRデータを以下に示す。
1H-NMR (Ｎ，Ｎ－ジメチルホルムアミド-d7) δ(ppm): 9.11 (2H, d), 8.95 (2H, d), 8.93 (2H, d), 8.55 (2H, d), 8.46 (2H, dd), 4.04 (4H, q), 1.40 (6H, m). Third step: A mixture of 3.08 g of the intermediate B, 335 g of xylene, and 33.71 g of p-toluenesulfonic acid monohydrate was refluxed, and water generated using a Dean-Stark apparatus was removed from the system. While stirring for 69 hours. After the obtained mixture was cooled to 100 ° C., it was added to 92.5 g of a 20% aqueous potassium carbonate solution at room temperature and stirred at 80 ° C. The precipitated solid was filtered, and the residue was sequentially washed with water and xylene, and dried. After the obtained solid was dissolved in 1000 g of N, N-dimethylformamide at room temperature, 100 g of water was added dropwise. The obtained solid was filtered, and the residue was sequentially washed with N, N-dimethylformamide and water, and dried to obtain 0.83 g of a compound A.
The 1 H-NMR data of Compound A is shown below.
1 H-NMR (N, N-dimethylformamide-d 7 ) δ (ppm): 9.11 (2H, d), 8.95 (2H, d), 8.93 (2H, d), 8.55 (2H, d), 8.46 ( 2H, dd), 4.04 (4H, q), 1.40 (6H, m).
　次に、試験例を示す。 Next, test examples are shown.
試験例１
　プラスチックポットに土壌を詰め、そこにトマト（品種：パティオ）を播種し、温室内で１９日間栽培した。ポリオキシエチレンアルキルエーテルサルフェートアンモニウム塩と湿式シリカとの混合物（重量比１：１）３５重量部、化合物Ａ２０重量部、及び水４５重量部を十分に混合した。得られた混合物を水で希釈して、化合物Ａを１２５ｐｐｍ含有する希釈液を調製した。この希釈液を、上記トマトの葉面に充分付着するように散布した。散布後トマトを風乾し、１日後にトマト輪紋病菌（チトクロームｂの１２９番目のアミノ酸残基がフェニルアラニンからロイシンに置換したAlternaria solani）胞子を含む水懸濁液を噴霧接種した。その後、トマトを１５℃多湿下に６日間置き、病斑面積を調査した。その結果、化合物Ａを処理したトマトにおける病斑面積は、無処理のトマトにおける病斑面積の０％であった。なお、無処理とは、上記希釈液を散布しなかったことを意味する。 Test example 1
A plastic pot was filled with soil, and tomato (cultivar: patio) was sown and cultivated in a greenhouse for 19 days. 35 parts by weight of a mixture of polyoxyethylene alkyl ether sulfate ammonium salt and wet silica (weight ratio 1: 1), 20 parts by weight of compound A, and 45 parts by weight of water were thoroughly mixed. The obtained mixture was diluted with water to prepare a diluent containing Compound A at 125 ppm. This diluted solution was sprayed so as to sufficiently adhere to the leaf surface of the tomato. After spraying, the tomatoes were air-dried, and one day later, a water suspension containing spores of tomato ring spot fungus (Alternaria solani in which the 129th amino acid residue of cytochrome b was substituted with phenylalanine for leucine) was spray-inoculated. Thereafter, the tomato was placed under high humidity at 15 ° C. for 6 days, and the lesion area was examined. As a result, the lesion area in the tomato treated with Compound A was 0% of the lesion area in the untreated tomato. In addition, "no treatment" means that the diluent was not sprayed.
　化合物Ａは、植物病害に対して優れた防除効果を示す。 Compound A exhibits an excellent control effect on plant diseases.

Claims (3)

  1. 　式（Ａ）
    Figure JPOXMLDOC01-appb-C000001
     で示される化合物。     Formula (A)
    Figure JPOXMLDOC01-appb-C000001
     A compound represented by the formula:
  2. 　請求項１に記載の化合物と、不活性担体とを含有する組成物。 組成 A composition comprising the compound according to claim 1 and an inert carrier.
  3. 　請求項１に記載の化合物の有効量を植物又は土壌に処理することによる、植物病害の防除方法。 方法 A method for controlling plant diseases by treating a plant or soil with an effective amount of the compound according to claim 1.
PCT/JP2019/035800 2018-09-13 2019-09-12 Bipyridine compound and use thereof WO2020054790A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201980059511.1A CN112673006B (en) 2018-09-13 2019-09-12 Bipyridine compound and use thereof
KR1020217007046A KR20210060459A (en) 2018-09-13 2019-09-12 Bipyridine compounds and uses thereof
JP2020546065A JP7368368B2 (en) 2018-09-13 2019-09-12 Bipyridine compounds and their uses

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018171185 2018-09-13
JP2018-171185 2018-09-13

Publications (1)

Publication Number Publication Date
WO2020054790A1 true WO2020054790A1 (en) 2020-03-19

Family

ID=69776835

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/035800 WO2020054790A1 (en) 2018-09-13 2019-09-12 Bipyridine compound and use thereof

Country Status (4)

Country Link
JP (1) JP7368368B2 (en)
KR (1) KR20210060459A (en)
TW (1) TWI827660B (en)
WO (1) WO2020054790A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016102104A (en) * 2015-09-08 2016-06-02 住友化学株式会社 Pest control composition and use therefor
WO2016125622A1 (en) * 2015-02-03 2016-08-11 住友化学株式会社 Benzoxazole compound, and use thereof for noxious arthropod control
JP2019048845A (en) * 2018-11-07 2019-03-28 住友化学株式会社 Composition containing heterocyclic compound

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200715961A (en) * 2005-10-28 2007-05-01 Sinon Corp Herbicide composition
WO2008114493A1 (en) * 2007-03-16 2008-09-25 Kumiai Chemical Industry Co., Ltd. Herbicide composition
TW201643154A (en) * 2015-01-30 2016-12-16 住友化學股份有限公司 Bipyridine compounds and its use for controlling harmful arthropods

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016125622A1 (en) * 2015-02-03 2016-08-11 住友化学株式会社 Benzoxazole compound, and use thereof for noxious arthropod control
JP2016102104A (en) * 2015-09-08 2016-06-02 住友化学株式会社 Pest control composition and use therefor
JP2019048845A (en) * 2018-11-07 2019-03-28 住友化学株式会社 Composition containing heterocyclic compound

Also Published As

Publication number Publication date
TWI827660B (en) 2024-01-01
KR20210060459A (en) 2021-05-26
JPWO2020054790A1 (en) 2021-08-30
CN112673006A (en) 2021-04-16
JP7368368B2 (en) 2023-10-24
TW202019919A (en) 2020-06-01

Similar Documents

Publication Publication Date Title
JP6898332B2 (en) 1-Phenyl-3-carbamoylurea compound and its uses
JP6628000B1 (en) Ester compounds and their uses
JP6875406B2 (en) 3-Pyridyloxyphenyl dihydrouracil compound and its uses
JP6876058B2 (en) Phenylurea compounds and their uses
JP7368368B2 (en) Bipyridine compounds and their uses
JP7254084B2 (en) Benzoxazole compound and use thereof
JP7250023B2 (en) Benzoxazole compound and use thereof
KR102641051B1 (en) Amide compounds and their uses
AU2019297918B2 (en) Uracil compound and use thereof
JP6558488B1 (en) Ester compounds and uses thereof
CN112673006B (en) Bipyridine compound and use thereof
WO2021117394A1 (en) Pyridyloxyacetic acid compound and use of same

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: 19860118

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020546065

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2101001390

Country of ref document: TH

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19860118

Country of ref document: EP

Kind code of ref document: A1