WO2025126830A1 - Composé oxy-2-aminothiazolecarboxamide n-substitué ou sel de celui-ci et bactéricide agricole et horticole - Google Patents

Composé oxy-2-aminothiazolecarboxamide n-substitué ou sel de celui-ci et bactéricide agricole et horticole Download PDF

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WO2025126830A1
WO2025126830A1 PCT/JP2024/041728 JP2024041728W WO2025126830A1 WO 2025126830 A1 WO2025126830 A1 WO 2025126830A1 JP 2024041728 W JP2024041728 W JP 2024041728W WO 2025126830 A1 WO2025126830 A1 WO 2025126830A1
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compound
reaction
salt
caused
aminothiazolecarboxamide
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Japanese (ja)
Inventor
拓也 岩本
博之 林
久樹 田中
将也 大野
和香奈 ▲瀬▼沼
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Ishihara Sangyo Kaisha Ltd
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Ishihara Sangyo Kaisha Ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to novel N-substituted oxy-2-aminothiazolecarboxamide compounds or salts thereof, and agricultural and horticultural fungicides containing them as active ingredients.
  • Patent Document 1 describes N-cycloalkyl-carboxamides, N-cycloalkyl-thiocarboxamides, and N-cycloalkyl-N-substituted carboximidamide derivatives, as well as methods for controlling phytopathogenic fungi using these compounds or compositions.
  • this document does not disclose any N-substituted oxy-2-aminothiazolecarboxamide compounds of formula (I) described below.
  • the objective of the present invention is to provide a new compound that exhibits excellent control effects against harmful plant diseases.
  • R2 is ( C1 - C3 ) alkyl;
  • X 1 is halogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, cyano or a hydrogen atom;
  • Y 1 , Y 2 , Y 3 and Y 4 each independently represent a halogen atom, a hydrogen atom, a (C 1 -C 6 ) alkyl, a (C 2 -C 6 ) alkenyl, a (C 1 -C 6 ) haloalkyl, cyano, or nitro, or a salt thereof (hereinafter also referred to as compound (I)).
  • Y 1 and Y 4 are each independently a halogen atom, a hydrogen atom, a (C 1 -C 6 ) alkyl, a (C 1 -C 6 ) haloalkyl, a cyano, or a nitro, provided that Y 1 and Y 4 are not both a hydrogen atom;
  • the N-substituted oxy-2-aminothiazolecarboxamide compound or a salt thereof according to any one of the above [1] to [3], wherein Y2 and Y3 are each independently a halogen or a hydrogen atom.
  • R 1 is a (C 1 -C 6 ) chain hydrocarbon
  • X 1 is halogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, or a hydrogen atom
  • Y 1 , Y 2 , Y 3 and Y 4 are each independently halogen, a hydrogen atom, a (C 1 -C 6 ) alkyl, a (C 1 -C 6 ) haloalkyl, or nitro.
  • Y 1 is halogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, or nitro;
  • a method for controlling harmful plant diseases comprising applying an effective amount of the N-substituted oxy-2-aminothiazolecarboxamide compound or its salt described in any one of [1] to [8] above to a plant body, a plant pathogen, or soil.
  • Compound (I) of the present invention exhibits excellent control effects against harmful plant diseases and is useful as an agricultural and horticultural fungicide.
  • the halogen or the halogen as a substituent may be a fluorine, chlorine, bromine, or iodine atom.
  • the number of halogen as a substituent may be one or more than one, and when there are two or more, the halogen atoms may be the same or different.
  • the substitution position of the halogen as a substituent may be any position.
  • C P -C T means that the number of carbon atoms is P to T.
  • C 1 -C 6 means that the number of carbon atoms is 1 to 6.
  • the expression “optionally substituted” means that the compound has a substituent or is unsubstituted.
  • Acyclic hydrocarbon means (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkynyl, or (C 2 -C 6 ) alkenyl.
  • (C 1 -C 6 ) alkyl represents a straight or branched alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, secondary pentyl, tertiary pentyl, 2-methylbutyl, 3-pentyl, normal hexyl, isohexyl, secondary hexyl, 2-methylpentyl, 3-methylpentyl, 3-hexyl, 2-ethylbutyl, 3-methylpentan-2-yl, 4-methylpentan-2-yl, 2,3-dimethylbutyl, tertiary hexyl, 2,2-dimethylbutyl, neohexyl, 3-methylpentan-3-yl, 2-methylpentan-3
  • (C 1 -C 3 ) alkyl represents a linear or branched alkyl group having 1 to 3 carbon atoms, and specific examples thereof include the alkyl groups having 1 to 3 carbon atoms among the specific examples of (C 1 -C 6 ) alkyl mentioned above.
  • (C 2 -C 6 )alkynyl represents a straight or branched alkynyl group having 2 to 6 carbon atoms and at least one triple bond at any position, such as ethynyl, 1-propynyl, propargyl (also simply referred to as 2-propynyl), 1-butynyl, 2-butynyl, 3-butynyl, 3-butyn-2-yl, 1,3-butadiynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, 3-pentyn-2-yl, 1-pentyn-3-yl, 4-pentyn-2-yl, 2-methyl-3-butynyl, 1,3-pentadiynyl, 1,4-pentadiynyl, 2,4-pentadiynyl, 1-hexynyl, 2
  • (C 2 -C 3 )alkynyl represents a linear alkynyl group having one triple bond at any position and having 2 to 3 carbon atoms, and specific examples thereof include alkynyl groups having 2 to 3 carbon atoms among the specific examples of (C 2 -C 6 )alkynyl mentioned above.
  • (C 2 -C 6 )alkenyl represents a straight or branched alkenyl group having from 2 to 6 carbon atoms with at least one double bond at any position.
  • vinyl also simply referred to as ethenyl
  • allyl also simply referred to as 2-propenyl
  • 1-propenyl isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-buten-2-yl, 3-buten-2-yl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 3-buten-3-yl, 1,3-butadienyl, 1,3-butadien-2-yl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 3-methyl-1-butenyl, 2-methyl-1-butenyl, 2-penten-1-yl, 3-methyl-2-buten-2-yl, 3-methyl-2-butenyl, 2-methyl-2-butenyl, 3-penten
  • the (C 1 -C 6 ) chain hydrocarbon may be substituted with at least one T 1.
  • the (C 1 -C 6 ) chain hydrocarbon may be substituted with 1 to 13 T 1 .
  • the substitution position of T 1 may be any substitution position on the (C 1 -C 6 ) chain hydrocarbon.
  • each T 1 may be the same or different.
  • R 1 in compound (I) is a (C 1 -C 6 ) alkyl substituted with at least one T 1
  • specific examples include the following substituents: cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, 5-cyanopentyl, 6-cyanohexyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, isopropoxycarbonylmethyl, and the like.
  • (C 1 -C 6 )haloalkyl represents a linear or branched alkyl group having 1 to 6 carbon atoms, which is partially or fully substituted by 1 to 13 identical or different halogen atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, chlorodifluoromethyl, dichlorofluoromethyl, chlorofluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1-chloroethyl, 2-chloroethyl, 1,1-dichloroethyl, 2,2-dichloroethyl, 2,2,2-trichloroethyl, 1-chloro-1
  • (C 1 -C 3 )haloalkyl represents a straight or branched alkyl group having 1 to 3 carbon atoms, which is partially or completely substituted with 1 to 7 identical or different halogen atoms.
  • Specific examples of (C 1 -C 3 )haloalkyl include haloalkyl groups having 1 to 3 carbon atoms among the specific examples of (C 1 -C 6 )haloalkyl mentioned above.
  • Salts of compound (I) include any salts that are agriculturally acceptable, such as alkali metal salts (e.g., sodium salt, potassium salt, etc.), alkaline earth metal salts (e.g., magnesium salt, calcium salt, etc.), amine salts (dimethylamine salt, triethylamine salt, etc.), inorganic acid salts (e.g., hydrochloride, perchlorate, sulfate, nitrate, etc.), or organic acid salts (e.g., acetate, methanesulfonate, paratoluenesulfonate, oxalate, etc.).
  • alkali metal salts e.g., sodium salt, potassium salt, etc.
  • alkaline earth metal salts e.g., magnesium salt, calcium salt, etc.
  • amine salts dimethylamine salt, triethylamine salt, etc.
  • inorganic acid salts e.g., hydrochloride, perchlorate
  • Compound (I) exists in various isomers, such as optical isomers and geometric isomers, and the present invention may include both each isomer and a mixture of isomers.
  • Compound (I) also includes various isomers other than those mentioned above, within the scope of common technical knowledge in the relevant technical field. Furthermore, various isomers can be produced separately using common technical knowledge in the relevant technical field and general experimental techniques.
  • compound (I) can be produced according to the following reactions A to E and a conventional method for producing a salt, but the method for obtaining the compound is not limited to these methods.
  • compound (I) of the present invention can also be produced by applying various substituent conversion reactions well known in the art (e.g., alkylation reaction, haloalkylation reaction, cross-coupling reaction such as Suzuki coupling reaction, Sandmeyer type reaction, halogenation reaction, oxidation reaction, reduction reaction, etc.) to the substituent on the pyridine ring.
  • substituent conversion reactions well known in the art
  • protection and deprotection reactions commonly used in the art may be applied in the production of the compound of the present invention, if necessary.
  • it may be carried out under an inert gas atmosphere such as nitrogen or argon, if necessary, and a salt reagent may be used.
  • Reaction A is a deprotection reaction, in which the Boc group is removed from the compound of formula (XX-a) to obtain the compound of formula (I), where the Boc group is a tert-butoxycarbonyl group.
  • Reaction A can be carried out under known conditions used to remove the Boc group, for example, the method described in Greene's PROTECTIVE GROUPS in ORGANIC SYNTHESIS (John Wiley and Sons, 2007, Peter G.M. Wuts, Theodora W. Greene). More specifically, for example, it can be carried out by reacting with an acid such as trifluoroacetic acid or hydrogen chloride in the presence of a solvent, or by reacting with trimethylsilyl triflate in the presence of a solvent and a base such as 2,6-lutidine.
  • an acid such as trifluoroacetic acid or hydrogen chloride
  • trimethylsilyl triflate in the presence of a solvent and a base such as 2,6-lutidine.
  • Reaction B is a method of reacting a compound of formula (II) with a compound of formula (III) to obtain a compound of formula (XX-b).
  • Reaction C is a method of reacting a compound of formula (II-a) with a compound of formula (III) to obtain a compound of formula (XX-b).
  • R 1a is H or a (C 1 -C 6 ) chain hydrocarbon optionally substituted with at least one T 1
  • L is a leaving group such as halogen, alkoxy, aryloxy, alkylcarbonyloxy, arylcarbonyloxy, etc.
  • the other symbols are as defined above.
  • Reaction B can usually be carried out in the presence of a dehydrating condensation agent and a solvent, with the addition of a base as necessary.
  • the compound of formula (III) in reaction B can be used in an amount of 0.5 to 3 equivalents, preferably 0.8 to 1.5 equivalents, per equivalent of the compound of formula (II) (the equivalent is a molar equivalent, and the same applies below).
  • the dehydration condensation agent in reaction B is a carbodiimide-based condensation agent such as N,N'-dicyclohexylcarbodiimide (DCC), 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (EDC) or its hydrochloride; an imidazole-based condensation agent such as 1,1'-carbonyldiimidazole (CDI); a triazine-based condensation agent such as 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM); a 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate (P
  • suitable dehydrating condensing agents include, but are not limited to, phosphonium condensing agents such as 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyr
  • dehydrating condensing agents such as 1-hydroxybenzotriazole (HOBt) may be added.
  • the dehydration condensation agent can be used in an amount of 0.5 to 5 equivalents, preferably 1 to 2 equivalents, per equivalent of the compound of formula (II), and the additive can be used in an amount of 0.2 to 5 equivalents, preferably 1 to 2 equivalents, per equivalent of the compound of formula (II).
  • the base in reaction B may be one or more of the following, selected appropriately from carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; amines such as triethylamine and N,N-diisopropylethylamine; pyridines such as pyridine, 4-dimethylaminopyridine, and 2,6-lutidine; and alkali metal carboxylates such as sodium acetate and potassium acetate.
  • the base may be used in an amount of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, per equivalent of the compound of formula (II).
  • the solvent in reaction B may be any solvent that is inert to the reaction, and may be selected from one or more of the following: aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbons such as carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; esters such as methyl acetate and ethyl acetate; aprotic polar solvents such as dimethyl sulfoxide, sulfolane, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, and propionitrile; ketones such as
  • the reaction temperature for reaction B is usually about -20°C to 150°C, preferably about 0°C to 100°C, and the reaction time is usually about 0.5 to 48 hours, preferably about 1 to 24 hours.
  • Reaction C can be carried out in the presence of a solvent, optionally with the addition of a base.
  • the compound of formula (III) can be used in an amount of 0.5 to 3 equivalents, preferably 0.8 to 1.5 equivalents, per equivalent of the compound of formula (II-a).
  • the base in reaction C may be one or more of the following, selected appropriately from carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; amines such as triethylamine and N,N-diisopropylethylamine; pyridines such as pyridine, 4-dimethylaminopyridine, and 2,6-lutidine; and alkali metal carboxylates such as sodium acetate and potassium acetate.
  • the base may be used in an amount of 0.1 to 10 equivalents, preferably 0.5 to 5 equivalents, per equivalent of the compound of formula (II-a).
  • the solvent in reaction C may be any solvent that is inert to the reaction, and may be selected from one or more of the following: aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbons such as carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; esters such as methyl acetate and ethyl acetate; aprotic polar solvents such as dimethyl sulfoxide, sulfolane, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, and propionitrile; ketones such as
  • the reaction temperature for reaction C is usually about -20°C to 150°C, preferably about 0°C to 100°C, and the reaction time is usually about 0.5 to 48 hours, preferably about 1 to 24 hours.
  • the compound of formula (III) used in reaction B and reaction C can be prepared according to the following reaction 2-2 or reaction 2-4.
  • the compound of formula (II) used in reaction B can be produced in accordance with the following reaction 1-1 or 1-2 or a known method, or a commercially available product may be used.
  • the compound of formula (II-a) used in reaction C can be produced from the compound of formula (II) according to the following reaction 1-4 or a known method, or a commercially available product may be used.
  • Reaction D is a method of obtaining a compound of formula (XX-a) by reacting a compound of formula (XX-c) with a compound of formula (IV).
  • L 1 is a leaving group such as halogen, trifluoromethanesulfonyloxy, methanesulfonyloxy, paratoluenesulfonyloxy, etc., and the other symbols are as defined above.
  • Reaction D can be carried out usually in the presence of a base and a solvent, with the addition of a phase transfer catalyst as necessary.
  • the compound of formula (IV) in reaction D can be used in an amount of 1 to 5 equivalents, preferably 1 to 3 equivalents, per equivalent of the compound of formula (XX-c).
  • the base in reaction D may be one or more of the following, selected appropriately and mixed: alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; amines such as triethylamine and N,N-diisopropylethylamine; pyridines such as pyridine, 4-dimethylaminopyridine, and 2,6-lutidine; organolithium compounds such as n-butyllithium and lithium diisopropylamide; alkali metal carboxylates such as sodium acetate and potassium acetate; etc.
  • the base may be used in an amount of 1 to 10 equivalents, preferably 1 to 5 equivalents, per equivalent of the compound of formula (
  • the solvent in reaction D may be any solvent inert to the reaction, and may be one or more of the following: aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbons such as carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; esters such as methyl acetate and ethyl acetate; alcohols such as methanol, ethanol, propanol, and tert-butanol; aprotic polar solvents such as dimethyl sulfoxide, sulfolane, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone
  • the phase transfer catalyst in reaction D may be, for example, a quaternary ammonium salt such as tetrabutylammonium bromide, benzyltriethylammonium chloride, or tetrabutylammonium hydrogen sulfate; or a crown ether such as 18-crown-6-ether; etc.
  • the phase transfer catalyst may be used in an amount of 0.1 to 3 equivalents per equivalent of the compound of formula (XX-c).
  • the reaction temperature for reaction D is usually about -20°C to 150°C, preferably about 0°C to 100°C, and the reaction time is usually about 10 minutes to 48 hours, preferably about 1 to 24 hours.
  • the compound of formula (IV) used in reaction D can be produced according to known methods, or a commercially available product may be used.
  • Reaction E is a method of obtaining a compound of formula (XX-a) by reacting a compound of formula (II-b) with a compound of formula (V).
  • Reaction E can be carried out in the same manner as reaction D above.
  • 1 to 5 equivalents, preferably 1 to 2 equivalents, of the compound of formula (V) can be used per equivalent of the compound of formula (II-b).
  • 1 to 10 equivalents, preferably 1 to 5 equivalents, of the base can be used per equivalent of the compound of formula (II-b).
  • 0.1 to 3 equivalents of the phase transfer catalyst can be used per equivalent of the compound of formula (II-b).
  • the compound of formula (II-b) used in reaction E can be produced in accordance with reaction 1-3 below or a known method, or a commercially available product may be used.
  • the compound of formula (V) used in reaction E can be produced in accordance with reaction 2-7, reaction 2-8, reaction 2-9 below or a known method, or a commercially available product may be used.
  • reactions A to E can be produced according to the methods for producing the intermediates shown below (reactions 1-1 to 1-5 and reactions 2-1 to 2-9) and the usual methods for producing salts, but are not limited to these methods. These compounds may be produced according to known methods or commercially available products may be used.
  • Reaction 1-1 is a method for obtaining a compound of formula (II) by oxidizing a compound of formula (1)
  • reaction 1-2 is a method for obtaining a compound of formula (II) by hydrolyzing a compound of formula (2).
  • Reaction 1-3 is a method of reacting a compound of formula (II) or a compound of formula (II-a) with a compound of formula (3) to obtain a compound of formula (II-b).
  • Reaction 1-4 is a method for obtaining a compound of formula (II-a) by halogenating, esterifying or carbonylating a compound of formula (II).
  • Reaction 1-5 is a method for protecting the amino group of a compound of formula (VI) with a Boc group to obtain a compound of formula (VII).
  • Reaction 1-1 can be carried out under general Pinnic oxidation conditions, for example, according to the method described in Bioorganic & Medicinal Chemistry, 2004, 12, 6171-6182.
  • the compound of formula (1) used in reaction 1-1 can be produced according to a known method, for example, the method described in Bioorganic & Medicinal Chemistry, 2004, 12, 6171-6182, Journal of Organic Chemistry, 2005, 70, 567-574, International Publication No. 2020/028141, or Organic Process Research and Development, 2021, 25, 1167-1175, or reaction 1-5, or a commercially available product may be used.
  • Reaction 1-2 can be carried out under general ester hydrolysis conditions, for example, in accordance with the method described in WO 2009/100171.
  • the compound of formula (2) used in reaction 1-2 can be produced according to known methods, such as those described in International Publication No. 2012/006760, Japanese Patent Registration No. 5851663, or the method described in reaction 1-5, or a commercially available product may be used.
  • Reaction 1-3 can be carried out in accordance with the above reaction B or reaction C.
  • the compound of formula (3) can be used in an amount of 0.5 to 10 equivalents, preferably 0.7 to 5 equivalents, per equivalent of the compound of formula (II) or the compound of formula (II-a).
  • the compound of formula (3) used in reaction 1-3 can be produced in accordance with known methods, for example, the methods described in WO 2006/138350 and U.S. Patent Application Publication No. 2014/0378399, or a commercially available product may be used.
  • the compound of formula (II-a) used in reaction 1-3 can be produced by a known method or according to the method described in reaction 1-4, or a commercially available product may be used.
  • reaction 1-4 can usually be carried out by reacting the compound of formula (II) with a halogenating agent in the presence of a solvent, and N,N-dimethylformamide may be added as necessary.
  • a halogenating agent in reaction 1-4 include oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, sulfuryl chloride, etc.
  • the halogenating agent can be used in an amount of 1 to 10 equivalents, preferably 1 to 3 equivalents, relative to 1 equivalent of the compound of formula (II), and an excess amount may be used if no problem occurs in the reaction.
  • the amount of N,N-dimethylformamide used in reaction 1-4 is a catalytic amount, for example, 0.01 to 0.3 equivalents per equivalent of the compound of formula (II).
  • the compound of formula (II) when L of the compound of formula (II-a) is alkoxy or aryloxy, the compound of formula (II) can be reacted with an alcohol or an arylhydroxyl group usually in the presence of a solvent and a dehydration condensing agent, with the addition of a base as necessary, to carry out esterification.
  • the alcohols in reaction 1-4 include methanol, ethanol, etc.
  • the aryl hydroxyl compounds in reaction 1-4 include phenol, etc.
  • the alcohols or aryl hydroxyl compounds can be used in an amount of 0.5 to 5 equivalents, preferably 0.8 to 1.5 equivalents, per equivalent of the compound of formula (II), and an excess amount may be used if no problem occurs in the reaction.
  • the dehydration condensation agent in reaction 1-4 As the dehydration condensation agent in reaction 1-4, those listed in reaction B above can be used.
  • a general additive e.g., 1-hydroxybenzotriazole (HOBt) or the like
  • the dehydration condensation agent can be used in an amount of 0.5 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 equivalent of the compound of formula (II), and the additive can be used in an amount of 0.2 to 5 equivalents, preferably 1 to 2 equivalents, relative to 1 equivalent of the compound of formula (II).
  • a base When a base is used together with the dehydration condensation agent in reaction 1-4, those listed in reaction B above can be used.
  • the base can be used in an amount of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, relative to 1 equivalent of the compound of formula (II).
  • the compound of formula (II) when L in the compound of formula (II-a) is alkoxy, the compound of formula (II) can be reacted with an alkyl halide in the presence of a solvent and a base to carry out esterification.
  • the alkyl halide in the reaction 1-4 include methyl iodide, ethyl iodide, etc.
  • the alkyl halide can be used in an amount of 0.5 to 5 equivalents, preferably 0.8 to 1.5 equivalents, per equivalent of the compound of the formula (II).
  • the base that can be used in the reaction with the alkyl halide in Reaction 1-4 is the same as that mentioned in Reaction D.
  • the base can be used in an amount of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, per equivalent of the compound of formula (II).
  • reaction 1-4 when L of the compound of formula (II-a) is alkylcarbonyloxy or arylcarbonyloxy, the compound of formula (II) can be reacted with a carbonylating agent usually in the presence of a solvent and a base to carry out carbonylation.
  • a carbonylating agent in reaction 1-4 include acetyl chloride, pivaloyl chloride, benzoyl chloride, acetic anhydride, and benzoic anhydride.
  • the carbonylating agent can be used in an amount of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, per equivalent of the compound of formula (II), and an excess amount may be used if no problem occurs in the reaction.
  • the bases listed in reaction B above can be used.
  • the base can be used in an amount of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, per equivalent of the compound of formula (II).
  • the solvent in reaction 1-4 may be any solvent inert to the reaction, and may be one or more of the following: aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbons such as carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; esters such as methyl acetate and ethyl acetate; aprotic polar solvents such as dimethyl sulfoxide, sulfolane, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, and propionitrile; ketones such as acetone
  • the reaction temperature in Reaction 1-4 is usually about -50°C to 200°C, preferably about -20°C to 100°C, and the reaction time is usually about 0.1 to 12 hours.
  • the compound of formula (II) used in reactions 1-3 and 1-4 can be produced in accordance with reactions 1-1 and 1-2, or known methods, or a commercially available product may be used.
  • Reactions 1-5 can be carried out according to typical reaction conditions for protecting an amino group with a Boc group, for example, the method described in Greene's PROTECTIVE GROUPS in ORGANIC SYNTHESIS (John Weekey and Sons, 2007, Peter G. M. Wuts, Theodora W. Greene).
  • the compound of formula (VI) used in reaction 1-5 can be produced in accordance with known methods, such as those described in International Publication No. 2018/041563 and U.S. Patent Application Publication No. 2008/312255, or a commercially available product may be used.
  • Reaction 2-1 is a method of reacting a compound of formula (10) with a compound of formula (3-a) to obtain a compound of formula (11).
  • Reaction 2-2 is a method of reducing the compound of formula (11) to obtain a compound of formula (III).
  • Reactions 2-1 and 2-2 can be carried out consecutively without isolating the compound of formula (11).
  • Reaction 2-3 is a method for obtaining a compound of formula (11-b) by reacting a compound of formula (11-a) with a compound of formula (IV).
  • Reaction 2-4 is a method for obtaining a compound of formula (III) by reacting a compound of formula (V) with a compound of formula (3-a).
  • Reaction 2-5 is a method for obtaining a compound of formula (10) from a compound of formula (12) using a hydride reducing agent.
  • Reaction 2-6 is a method for obtaining a compound of formula (13) by reducing a compound of formula (10).
  • Reaction 2-7 is a method for obtaining a compound of formula (V) from a compound of formula (13) using a halogenating agent or a sulfonylating agent.
  • Reaction 2-8 is a method for obtaining a compound of formula (V-b) from a compound of formula (V-a) using a halogenating agent, and
  • Reaction 2-9 is a method for obtaining a compound of formula (V-b) from a compound of formula (14) using a halogenating agent.
  • L 2 in the formula is a leaving group such as trifluoromethanesulfonyloxy, methanesulfonyloxy, paratoluenesulfonyloxy, etc.
  • L 3 is a halogen, and the other symbols are as defined above.
  • Reaction 2-1 can be carried out by adding an acid, a base or a dehydrating agent as necessary. Reaction 2-1 can also be carried out in the presence of a solvent.
  • the compound of formula (3-a) in reaction 2-1 can be used in an amount of 1 to 5 equivalents per equivalent of the compound of formula (10), and an excess amount can be used if there are no problems with the reaction.
  • the compound of formula (3-a) in reaction 2-1 can be a salt of the compound of formula (3-a) (e.g., hydrochloride, sulfate, or trifluoroacetate).
  • the acid in reaction 2-1 may be either an inorganic acid or an organic acid, and examples of the inorganic acid include hydrochloric acid, sulfuric acid, etc., and examples of the organic acid include acetic acid, methanesulfonic acid, paratoluenesulfonic acid, etc.
  • the acid may be used in an amount of 0.1 to 10 equivalents relative to 1 equivalent of the compound of formula (10), and an excess amount may be used if no problem occurs in the reaction.
  • Examples of the base in reaction 2-1 include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; amines such as triethylamine and N,N-diisopropylethylamine; pyridines such as pyridine, 4-dimethylaminopyridine, and 2,6-lutidine; alkali metal carboxylates such as sodium acetate and potassium acetate; etc.
  • the base can be used in an amount of 0.5 to 5 equivalents relative to 1 equivalent of the compound of formula (3-a).
  • the dehydrating agent in reaction 2-1 may, for example, be anhydrous magnesium sulfate, anhydrous sodium sulfate, or molecular sieves.
  • the solvent in Reaction 2-1 may be any solvent inert to the reaction, and may be appropriately selected from, for example, one or more of aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane and cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether and dimethoxyethane; esters such as methyl acetate and ethyl acetate; aprotic polar solvents such as acetonitrile; protic polar solvents such as methanol and ethanol; and water.
  • aromatic hydrocarbons such as
  • the reaction temperature for reaction 2-1 is usually about -20°C to 200°C, preferably about 0°C to 150°C, and the reaction time is usually about 0.5 to 48 hours, preferably about 1 to 24 hours.
  • the compound of formula (10) used in reaction 2-1 can be produced according to reaction 2-5 or a known method, or a commercially available product may be used.
  • Reaction 2-2 can usually be carried out in the presence of a reducing agent and a solvent, and can also be carried out by adding an acid if necessary.
  • the reducing agent in reaction 2-2 may be, for example, sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride, or 2-picoline borane complex.
  • the reducing agent may be used in an amount of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, per equivalent of the compound of formula (11).
  • the acid to be added may be either an inorganic acid or an organic acid, and examples of the inorganic acid include hydrochloric acid, and examples of the organic acid include acetic acid and trifluoroacetic acid.
  • the acid may be used in an amount of 1 to 10 equivalents per equivalent of the compound of formula (11).
  • the solvent in reaction 2-2 may be any solvent that is inert to the reaction, and may be one or more of the following: aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbons such as carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane, and cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; esters such as methyl acetate and ethyl acetate; protic polar solvents such as methanol and ethanol; and water.
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbons such as carbon tetrachloride, methyl chloride, chloroform,
  • the reaction temperature for reaction 2-2 is usually about -20°C to 150°C, preferably about 0°C to 100°C, and the reaction time is usually about 0.5 to 48 hours, preferably about 1 to 24 hours.
  • Reaction 2-3 can be carried out in accordance with reaction D.
  • the compound of formula (IV) can be used in an amount of 1 to 5 equivalents, preferably 1 to 2 equivalents, per equivalent of the compound of formula (11-a).
  • the base in reaction 2-3 can be used in an amount of 1 to 10 equivalents, preferably 1 to 5 equivalents, per equivalent of the compound of formula (11-a).
  • the phase transfer catalyst in reaction 2-3 can be used in an amount of 0.1 to 3 equivalents per equivalent of the compound of formula (11-a).
  • the reaction temperature for reaction 2-3 is usually about -20°C to 150°C, preferably about 0°C to 100°C, and the reaction time is usually about 10 minutes to 48 hours, preferably about 1 to 24 hours.
  • Reaction 2-4 can be carried out in accordance with reaction E.
  • the compound of formula (3-a) in reaction 2-4 can be used in an amount of 1 to 5 equivalents, preferably 1 to 3 equivalents, per equivalent of the compound of formula (V).
  • the compound of formula (3-a) in reaction 2-4 can be used in the form of a salt of the compound of formula (3-a) (e.g., hydrochloride, sulfate, or trifluoroacetate).
  • the base in reaction 2-4 can be used in an amount of 1 to 10 equivalents, preferably 1 to 5 equivalents, per equivalent of the compound of formula (V).
  • the phase transfer catalyst in reaction 2-4 can be used in an amount of 0.1 to 3 equivalents per equivalent of the compound of formula (V).
  • the reaction temperature for reaction 2-4 is usually about -20°C to 150°C, preferably about 0°C to 100°C, and the reaction time is usually about 10 minutes to 48 hours, preferably about 1 to 24 hours.
  • the compound of formula (V) used in reaction 2-4 can be produced in accordance with a known method, the method described in reaction 2-7, reaction 2-8, or reaction 2-9, or a commercially available product can be used.
  • Reaction 2-5 can be carried out under general conditions for converting a cyano group to a formyl group, for example, according to the method described in Journal of Medicinal Chemistry, 2008, 51, 4021-4029.
  • the compound of formula (12) used in reaction 2-5 can be produced according to known methods, or a commercially available product can be used.
  • Reaction 2-6 can be carried out under general conditions for reducing formyl groups, for example, according to the method described in Bioorganic & Medicinal Chemistry Letters, 2012, 22, 901-906.
  • Reaction 2-7 can be carried out, for example, under conditions for halogenating a general hydroxyl group or conditions for sulfonylating a general hydroxyl group.
  • conditions for reaction 2-7 include the methods described in Journal of Medicinal Chemistry, 2003, 46, 453-456 and WO 2020/106307.
  • Reaction 2-8 can be carried out under conditions for halogenating a leaving group such as a general mesyl group, for example, according to the method described in Journal of Medicinal Chemistry, 2010, 53, 8421-8439.
  • the compound of formula (V-a) used in reaction 2-8 can be produced in accordance with reaction 2-7 or a known method, or a commercially available product may be used.
  • Reaction 2-9 can be carried out under general conditions for halogenating pyridylmethyl, for example, according to the method described in Journal of Medicinal Chemistry, 2011, 54, 6106-6116.
  • the target compound in each of the above reactions, can be obtained by carrying out normal post-treatments (solvent removal, neutralization, distillation, washing, extraction, filtration, drying, etc.) after the reaction is completed.
  • the target compound can be isolated by appropriately selecting one or more of these normal post-treatments. If necessary, the target compound can then be purified by normal methods such as column chromatography and recrystallization.
  • Each intermediate produced by the above reactions can also be used as a crude product in the next reaction step without isolation or purification.
  • Compound (I) is useful as an active ingredient of agricultural and horticultural fungicides capable of controlling harmful plant diseases at low doses.
  • Compound (I) can control plant diseases caused by plant pathogens belonging to, for example, Oomycota, Endomyxa, Olpidiomycota, Ascomycota, Basidiomycota, and Blastocladiomycota.
  • compound (I) is particularly effective in controlling plant diseases caused by plant pathogens belonging to Oomycota, Endomyxa, and Olpidiomycota.
  • plant pathogens that belong to the above-mentioned category include the following.
  • Oomycota Plant pathogenic fungi belonging to various classifications such as Albuginales, Anisolopidiales, Lagenidiales, Leptomitales, Myzocytiopsidales, Olpidiopsidales, Peronosporales, Pythiales, Rhipidiales, Saprolegniales, and Sclerosporales.
  • Endomyxa Plant pathogenic fungi belonging to the classifications Haplosporida, Paradiniida, Paramyxida, Gromiida, Phagomyxida, Plasmodiophorida, and Vampyrellida.
  • Olpidiomycota Plant pathogens belonging to classifications such as Olpidiales.
  • Ascomycota Plant pathogenic fungi belonging to various classifications such as Cladosporiales, Diaporthales, Erysiphales, Glomerellales, Helotiales, Hypocreales, Magnaporthales, Mycosphaerellales, Myriangiales, Pleosporales, and Venturiales.
  • Basidiomycota Plant pathogenic fungi belonging to various classes such as Agaricales, Cantharellales, Pucciniales, and Ustilaginales.
  • Blastocladiomycota Examples include those belonging to the classification Physodermatales, etc.
  • plant pathogenic fungi include the following. Potato or tomato phytophthora blight (Phytophthora infestans), fig phytophthora (Phytophthora palmivora), pear or strawberry phytophthora blight (Phytophthora cactorum), wax gourd, pumpkin, bell pepper or chili pepper phytophthora (Phytophthora capsici), tomato gray rot (Phytophthora capsici), eggplant or watermelon brown rot (Phytophthora capsici), citrus brown rot (Phytophthora citricola), adzuki bean stem rot (Phytophthora vignae f. sp.
  • Phytophthora Phytophthora spp. such as Pseudoperonospora cubensis (cucumber, pumpkin, melon, zucchini downy mildew), Pseudoperonospora humuli (hop downy mildew), Plasmopara spp. such as Plasmopara viticola (grape downy mildew), Plasmopara nivea (honeybee downy mildew), Hyaloperonospora spp.
  • Hyaloperonospora brassicae cabbage or Chinese cabbage downy mildew
  • Bremia spp. such as Bremia lactucae (lettuce downy mildew), Pythium graminicola (rice seedling blight), Pythium snow rot (wheat snow rot) Pythium genus fungi such as Pythium aphanidermatum, Pythium zingiberis, and Pythium ultimum var.
  • Aphanomyces genus fungi such as Aphanomyces raphani and Aphanomyces cochlioides
  • Albugo genus fungi such as Albugo macrospora, Albugo wasabiae, and Albugo ipomoeae-aquaticae
  • Peronospora japonica and Peronospora japonica Peronospora genus fungi such as Peronospora manshurica, Peronospora parasitica, Peronospora destructor, Peronospora farinosa f. sp. Spinaciae, and Peronospora belbahrii.
  • Plasmodiophora species such as Plasmodiophora brassicae, which causes clubroot disease of Chinese cabbage, cabbage, cauliflower, turnip, broccoli or turnip; Polymyxa species such as Polymyxa betae, which transmits Beet necrotic yellow vein virus; Spongospora species such as Spongospora subterranea, which causes potato powdery scab; Olpidium species such as Olpidium virulentus, which transmits Mirafiori lettuce bigvein virus.
  • Erysiphe species such as wheat powdery mildew (Erysiphe graminis); Setosphaeria species such as corn leaf spot (Setosphaeria turcica); Sphaerotheca species such as cucumber powdery mildew (Sphaerotheca fuliginea) and strawberry powdery mildew (Sphaerotheca humuli); grape powdery mildew (Un Uncinula species such as Podosphaera leucotricha; Mycosphaerella pinodes, Mycosphaerella pomi, Mycosphaerella musicola, Mycosphaerella necator, Mycosphaerella pinodes, Mycosphaerella pomi, Mycosphaerella musicola, Mycosphaerella pinodes ...
  • Venturia species such as Venturia inaequalis (apple spot) and Venturia nashicola (pear spot); Pyrenophora teres (barley net blotch) and Pyrenophora graminea (barley leaf spot); Pyrenophora fungi such as Sclerotinia sclerotiorum, which causes sclerotinia rot of beans, cucumbers, cabbage, Chinese cabbage, chili peppers, bell peppers and onions; Sclerotinia borealis, which causes snow mould of wheat, Sclerotinia minor, which causes sclerotinia rot of tomato and Sclerotinia trifoliorum, which causes sclerotinia rot of alfalfa.
  • Botryotinia spp. such as Botryotinia arachidis; Cochliobolus spp., such as Cochliobolus miyabeanus; Didymella spp., such as Didymella bryoniae; Gibberella spp., such as Gibberella fujikuroi; Elsinoe spp., such as Elsinoe ampelina and Elsinoe fawcettii; Diaporthe spp., such as Diaporthe citri and Diaporthe sp.; Monilinia mali and Monilinia fructicola; Glomerella such as Glomerella cingulata.
  • Rhizoctonia fungi such as Rhizoctonia solani
  • Ustilago fungi such as Ustilago nuda
  • Puccinia fungi such as Puccinia coronata, Puccinia recondita, and Puccinia striiformis
  • Phakopsora fungi such as Phakopsora pachyrhizi
  • Typhula fungi such as Typhula incarnata or Typhula ishikariensis.
  • Septoria fungi such as Septoria nodorum, Septoria tritici; Botrytis cinerea, Botrytis allii, Botrytis squamosa, Botrytis byssoidea, Botrytis tulipae, Botrytis squam ...
  • rytis fungi Fusarium fungi such as Fusarium graminearum and Fusarium oxysporum; Pyricularia fungi such as Pyricularia oryzae; Cercospora fungi such as Cercospora beticola and Cercospora kakivora; Colletotrichum fungi such as Colletotrichum orbiculare and Colletotrichum coffeeum; fungi of the genus Alternaria, such as Alternaria alternata apple pathotype, Alternaria alternata Japanese pear pathotype, Alternaria solani, Alternaria brassicae, Alternaria brassicicola, Alternaria porri; fungi of the genus Phoma, such as Phoma lingam; fungi of the genus Wheat eye Pseudocercosporella species, such as Pseudocercosporella herpotrichoides; Pseudocercospora species, such as Pseudocercospor
  • Gloeosporium species such as Gloeosporium kaki, which causes anthracnose; Fulvia species such as Fulvia fulva, which causes tomato leaf mold; Corynespora species such as Corynespora cassiicola, which causes brown spot of cucumber; and Physoderma species such as Physoderma maydis, which causes brown spot of corn.
  • compound (I) can control the various plant pathogenic fungi mentioned above, it can preventively or therapeutically control various diseases.
  • compound (I) is effective against various diseases that are problematic in the agricultural and horticultural fields, for example, rice diseases such as seedling damping-off caused by Pythium, rice blast caused by Pyricularia, bakanae disease caused by Fusarium, whole leaf blight caused by Cochliobolus, and sheath blight caused by Rhizoctonia; wheat diseases such as powdery mildew caused by Erysiphe, red mold disease or crown rot caused by Fusarium, rust caused by Puccinia, brown snow mold caused by Pythium, bare smut caused by Ustilago, eyespot disease caused by Pseudocircospora, leaf blight or streaking blight caused by Septoria; and wheat diseases such as red mold disease caused by Fusarium, spot disease caused by Physoderma, rust caused by Puccinia, soot
  • Corn diseases such as southern leaf blight, root rot caused by Pythium, and smut caused by Ustilago; sugarcane diseases such as smut caused by Ustilago, leaf burn caused by Stagonospora, rust caused by Puccinia, top rot caused by Gibberella, sooty mildew caused by Caldariomyces, and leaf blight caused by Pseudocircospora; legume diseases such as powdery mildew caused by Oidium, rust caused by Phakopsora, downy mildew caused by Peronospora, late blight or stem blight caused by Phytophthora, anthracnose caused by Colletotrichum, sclerotinia rot caused by Sclerotinia, gray mold caused by Botrytis, root rot or damping off caused by Fusarium; Diseases of Brassicaceae crops such as downy mildew caused by Spora or Hyaloperonospora, black spot caused by Altern
  • diseases of wheat such as red mold or crown rot caused by Fusarium, anthracnose caused by Colletotrichum, cattail smut caused by Tillettsia, bare smut caused by Ustilago, stripe disease caused by Cephalosporium, and spot blight caused by Septoria; diseases of corn such as southern leaf spot caused by Bipolaris, anthracnose caused by Colletotrichum, and damping-off caused by Fusarium; diseases of rice crops such as red rot caused by Glomerella, black rot caused by Ceratocystis, and downy mildew caused by Sclerospora; purple spot caused by Circospora, downy mildew caused by Peronospora, and downy mildew caused by Fusarium.
  • soybean diseases such as damping-off, ascochyta caused by Septoria fungus, black spot caused by Diaporthe fungus, anthracnose caused by Colletotrichum fungus, and sleeping disease caused by Septogloeum fungus
  • cabbage diseases such as black spot or black sooty mold caused by Alternaria fungus, downy mildew caused by Peronospora fungus, black spot bacterial disease caused by Pseudomonas fungus, black rot caused by Xanthomonas fungus, and root rot caused by Phoma fungus
  • radish diseases such as black spot caused by Alternaria fungus, yellows caused by Fusarium fungus, and black rot caused by Xanthomonas fungus
  • Chinese cabbage diseases such as black spot caused by Alternaria fungus, black rot caused by Xanthomonas fungus, and yellowing disease caused by Verticillium fungus.
  • Brassicaceae crop diseases such as blight; tomato diseases such as ring spot caused by Alternaria, canker caused by Clavibacter, and bacterial spot caused by Xanthomonas; eggplant diseases such as brown spot caused by Alternaria and brown spot caused by Phomopsis; potato diseases such as scab caused by Streptomyces, silver scab caused by Helminthosporium, and powdery scab caused by Spongospora; cucurbit diseases such as black spot caused by Alternaria, bacterial spot caused by Pseudomonas, and bacterial brown spot caused by Xanthomonas; cucurbit diseases such as black spot caused by Alternaria and ash spot caused by Botrytis.
  • Compound (I) can preventively or therapeutically control the various diseases mentioned above. Using the test method described in the Examples below, certain compounds (I) of the present invention can exert excellent preventive or therapeutic control effects at low concentrations (e.g., 100 ppm, 25 ppm, 12.5 ppm, 6.3 ppm, 3.1 ppm, 1.6 ppm, 0.8 ppm, 0.4 ppm, 0.2 ppm, or 0.1 ppm).
  • concentrations e.g., 100 ppm, 25 ppm, 12.5 ppm, 6.3 ppm, 3.1 ppm, 1.6 ppm, 0.8 ppm, 0.4 ppm, 0.2 ppm, or 0.1 ppm.
  • compound (I) has excellent rain resistance, residual activity, and penetrability, so that applying compound (I) to a plant body can control harmful fungi on the above-ground parts of the plant for a certain period of time.
  • an effective amount of compound (I) can be applied to plants, plant pathogens or soil.
  • the above-mentioned effective amount means the application amount of compound (I) at which compound (I) exerts a control effect against various harmful plant diseases.
  • the plant body means above-ground parts of a plant such as trunks, stems, leaves, flowers, spikes, and fruits, underground parts of a plant such as tubers, rhizomes, and roots, as well as seeds, seedlings, and transplants of a plant.
  • the soil means agricultural land such as fields, paddy fields, orchards, and non-agricultural land such as lawns and forests where plants are cultivated.
  • the plants to which compound (I) is applied are not particularly limited as long as they are agriculturally and horticulturally useful, and examples thereof include Gramineae crops (rice, wheat, barley, oats, rye, corn, sugarcane, etc.), Leguminous crops (soybean, kidney bean, adzuki bean, pea, peanut, edamame, alfalfa, etc.), Brassicaceae crops (cabbage, Chinese cabbage, radish, turnip, broccoli, cauliflower, rapeseed, rapeseed, etc.), and the like.
  • Gramineae crops rice, wheat, barley, oats, rye, corn, sugarcane, etc.
  • Leguminous crops soybean, kidney bean, adzuki bean, pea, peanut, edamame, alfalfa, etc.
  • Brassicaceae crops cabbage, Chinese cabbage, radish, turnip, broccoli, cauliflower, rapeseed
  • Asteraceae crops (lettuce, burdock, chrysanthemum, sunflower, etc.), Solanaceae crops (potato, eggplant, tomato, bell pepper, tobacco, chili pepper, etc.), Cucurbitaceae crops (cucumber, pumpkin, melon, watermelon, wax gourd, zucchini, etc.), Amaryllidaceae Allium crops (green onion, Chinese chive, shallot, garlic, onion, scallion, etc.), Umbelliferae crops (celery, carrot, parsley, mitsuba, etc.), Liliaceae crops (lily, tulip, etc.), crops of the Polygonaceae family (buckwheat, etc.), crops of the Convolvulaceae family (sweet potato, water beet, etc.), crops of the Chenopodiaceae family (spinach, sugar beet, etc.), crops of the Vitaceae family (grapes, etc.), crops of the Rosaceae family (roses
  • plants include plants that have been developed using genetic engineering or gene editing techniques, such as plants that have been endowed with environmental stress resistance, herbicide resistance, pest resistance, or disease resistance, or plants that have been modified in terms of growth, fertility, product quality, yield, etc.
  • Compound (I) is usually formulated and used in various forms, such as dusts, granules, granular water-dispersible agents, wettable powders, aqueous suspensions, oily suspensions, water-soluble agents, emulsions, liquids, pastes, aerosols, micro-dispersible agents, and microcapsules, by mixing compound (I) with an auxiliary agent.
  • an auxiliary agent such as dusts, granules, granular water-dispersible agents, wettable powders, aqueous suspensions, oily suspensions, water-soluble agents, emulsions, liquids, pastes, aerosols, micro-dispersible agents, and microcapsules.
  • any formulation form normally used in the relevant field can be used.
  • the auxiliary agents used in the formulation include solid carriers and liquid carriers, and surfactants and other formulation auxiliary agents can also be added as necessary.
  • solid carrier examples include diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, baking soda, mirabilite, zeolite, starch, and finely powdered silica.
  • liquid carrier examples include water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and alcohol.
  • the surfactant include fatty acid salts, benzoates, alkyl sulfosuccinates, dialkyl sulfosuccinates, polycarboxylates, alkyl sulfates, alkyl sulfates, alkylaryl sulfates, alkyl diglycol ether sulfates, alcohol sulfates, alkyl sulfonates, alkylaryl sulfonates, aryl sulfonates, lignin sulfonates, alkyl diphenyl ether disulfonates, polystyrene sulfonates, alkyl phosphates, alkylaryl phosphates, styrylaryl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether phosphates, polyoxyethylene alkylaryl ether phosphates, polyoxyethylene alkylaryl ether sulfate ...
  • surfactants and spreaders examples include anionic surfactants and spreaders such as oxyethylene alkylaryl phosphate ester salts and salts of naphthalenesulfonic acid formalin condensates; and nonionic surfactants and spreaders such as sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid polyglycerides, fatty acid alcohol polyglycol ethers, acetylene glycol, acetylene alcohol, oxyalkylene block polymers, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene styrylaryl ethers, polyoxyethylene glycol alkyl ethers, polyethylene glycol, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene hydrogenated castor oil, and polyoxypropylene fatty acid esters.
  • anionic surfactants and spreaders such as
  • formulation adjuvants include vegetable oils and mineral oils such as olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, and liquid paraffin; silicones; and xanthan gum.
  • vegetable oils and mineral oils such as olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, and liquid paraffin; silicones; and xanthan gum.
  • auxiliary agents may be appropriately selected and used, either alone or in combination, as long as it does not deviate from the object of the present invention.
  • auxiliary agents those known in the art may also be appropriately selected and used, for example, various commonly used auxiliary agents such as bulking agents, thickening agents, antisettling agents, antifreezing agents, dispersion stabilizers, phytotoxicity reducing agents, and antifungal agents.
  • the mixing ratio of compound (I) to various auxiliary agents is generally 0.001:99.999 to 95:5, preferably 0.005:99.995 to 90:10, by weight.
  • these preparations When these preparations are actually used, they may be used as is, or diluted to a predetermined concentration with a diluent such as water, and various spreading agents (surfactants, vegetable oils, mineral oils, etc.) may be added as necessary.
  • an effective amount of compound (I) can be applied by a commonly used application method, i.e., spray treatment, soil treatment, seed treatment, etc.
  • a commonly used application method compound (I) can be applied at an active ingredient concentration of 0.1 to 10,000 ppm, preferably 1 to 2,000 ppm, more preferably 1 to 1,000 ppm.
  • a composition containing compound (I) as an active ingredient hereinafter also referred to as the present composition
  • a diluted version thereof can be applied.
  • the appropriate application amount can be about 10 to 100,000 g of the present composition per hectare.
  • the appropriate application amount can be about 0.01 to 1,000 g of the present composition per hectare.
  • the appropriate application amount can be about 0.001 to 100 g, preferably about 0.01 to 1 g, of the present composition per kg of seeds.
  • the spray treatment is a treatment method for controlling plant pathogens by spraying an effective amount of the composition onto the surface of the trunk, buds, stems, leaves, flowers, spikes, or fruits of a plant, or onto plant pathogens.
  • Examples of the spray treatment include spraying onto stems and leaves, and spraying onto tree trunks.
  • the soil treatment is a method of treating soil with the present composition in order to transfer an effective amount of compound (I) from the roots of a plant to the inside of the plant in order to protect crops from damage caused by plant pathogens.
  • Examples of the treatment include irrigation treatment (irrigating the present composition into the soil for plant cultivation), soil incorporation treatment (mixing the present composition with the soil for plant cultivation), planting hole treatment, treatment at the base of a plant or between plants (spraying or irrigation), and incorporation treatment into soil used for culture soil, seedling boxes, seedling trays, paper pots, seedling beds, etc.
  • the seed treatment is a treatment method for controlling plant pathogens by treating the seeds, bulbs, etc. of crops with the present composition directly or in the vicinity thereof in order to protect crops from damage caused by plant pathogens.
  • Examples of the treatment include coating treatment, dressing treatment, and immersion treatment.
  • Treatment include seedling treatment (irrigation or immersion), immersion treatment of bulbs, tubers, bulbs, roots, etc., and hydroponic treatment such as mixing with a hydroponic nutrient solution. Treatment may be performed on the whole plant or a part of it (stems, leaves, buds, flowers, ears, fruits, trunks, seeds, bulbs, tubers, bulbs, roots, etc.).
  • the present composition can be mixed or used in combination with other ingredients selected from other agricultural and horticultural chemicals, fertilizers, safeners, etc., and in this case, even more excellent effects and activity may be exhibited.
  • the above-mentioned mixture or combination use means that the present composition and other components are used simultaneously, separately or with an interval of time.
  • Other agricultural and horticultural drugs include herbicides, insecticides, acaricides, nematicides, soil pesticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, etc.
  • the mixed fungicide composition in which the present composition and one or more active ingredient compounds of other fungicides are mixed or used in combination may improve the scope of application, timing of drug treatment, control activity, etc. in a favorable direction.
  • the present composition and the active ingredient compounds of other fungicides may be formulated separately and mixed at the time of spraying, or both may be formulated together and used. Such mixed fungicides are also included in the present invention
  • the mixing ratio of compound (I) and the active ingredient compounds of other fungicides cannot be specified in general due to differences in weather conditions, formulation form, target crop, application time, application location, type and occurrence of harmful plant diseases, etc., but can generally be 1:300 to 300:1, preferably 1:100 to 100:1, by weight.
  • the appropriate application amount is 0.1 to 70,000 g, preferably 1 to 30,000 g, of the total active ingredient compounds per hectare.
  • the present invention also includes a method for controlling harmful plant diseases by applying such a mixed fungicidal composition.
  • the active ingredient compounds (common names) of the fungicides in the above other agricultural and horticultural agents can be appropriately selected, for example, from the following compound groups. Even if not specifically stated, if these compounds have various structural isomers such as salts, alkyl esters, and optical isomers, these are of course included.
  • Anilinopyrimidine compounds such as mepanipyrim, pyrimethanil, and cyprodinil; Triazolopyrimidine compounds such as ametoctradin; Triazolobenzothiazole compounds such as tricyclazole; Pyridinamine compounds such as fluazinam; Triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, myclobutanil, cyproconazole, tebuconazole, hexaconazole, fluconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole, oxpoconazole fumarate azole compounds such as fumarate, prothioconazole, triadimenol, flutriafol, difenoconazole, fluquinconazole, fenbuconazole, bromu
  • Quinoxaline compounds such as chinomethionat; Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram; Organochlorine compounds such as phthalide, chlorothalonil, and quintozene; Imidazole compounds such as benomyl, thiophanate-methyl, carbendazim, thiabendazole, and fuberiazole; Cyanoacetamide compounds such as cymoxanil; acylamino acid compounds such as metalaxyl, metalaxyl-M (also known as mefenoxam), oxadixyl, ofurace, benalaxyl, benalaxyl-M (also known as chiralaxyl or chiralaxyl), furalaxyl, and valifenalate; Anilides such as cyprofuram, carboxin, oxycarboxin, thi
  • Sulfamide compounds such as dichlofluanid; Copper compounds such as cupric hydroxide, oxine copper, anhydrous copper sulfate, copper nonylphenolsulfonate, copper 8-hydroxyquinoline, and copper dodecylbenzenesulfonate bis(ethylenediamine)copper(II) complex (also known as DBEDC); Organophosphates such as fosetyl-Al, tolclofos-Methyl, edifenphos, iprobenfos; Phthalimide compounds such as captan, captafol, and folpet; Dicarboximide compounds such as procymidone, iprodione, and vinclozolin; Benzanilide compounds such as flutolanil, mepronil, benodanil, and flufenoxadiazam; Amide compounds such as carpropamid, diclocymet, silthiofam, and fenoxanil; pyrazo
  • benzamide compounds such as fluopicolide, fluopyram, zoxamide, and fluopimomide
  • Furanilide compounds such as fenfuram
  • Thiophene amide compounds such as isofetamide
  • Piperazine compounds such as triforine
  • Pyridine compounds such as pyrifenox, pyrisoxazole, and aminopyrifen
  • Pyrimidine compounds such as fenarimol, ferimzone, nuarimol, and flumetylsulforim
  • Piperidine compounds such as fenpropidin
  • Morpholine compounds such as fenpropimorph and tridemorph
  • Organotin compounds such as fentin hydroxide and fentin acetate
  • Urea compounds such as pencycuron
  • Carboxylic acid amide compounds such as dimethomorph, flumorph, pyrimorph, iprovalicarb, benthiavalicarb-isopropyl, and mandipropamid
  • strobilurin compounds such as azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin, pyraclostrobin, fluoxastrobin, pyraoxystrobin, pyrametostrobin, coumoxystrobin, enoxastrobin, phenaminestrobin, flufenoxystrobin, triclopyricarb, and mandestrobin; Oxazole compounds such as famoxadone and oxathiapiprolin; Thiazolecarboxamide compounds such as ethaboxam; Imidazolinone compounds such as fenamidone; benzenesulfonamide compounds such as flusulfamide; Oxime ether compounds such as cyflufenamid; Anthraquinone compounds such as dithianon; Crotonic acid compounds such as meptyldinocap; Antibiotics such as validamycin,
  • Guanidine compounds such as iminoctadine, dodine, and guazatine; Aliphatic nitrogen-based compounds such as butylamine and seboctylamine; Quinoline compounds such as tebufloquin, quinoxyfen, quinofumelin, ipflufenoquin, and feneptamidoquin; Thiazolidine compounds such as flutianil; Carbamate compounds such as propamocarb hydrochloride, pyribencarb, and tolprocarb; Tetrazole compounds such as picarbutrazox and metyltetraprole; Sulfonamide compounds such as amisulbrom and cyazofamid; Allyl phenyl ketone compounds such as metrafenone and pyriophenone; Benzothiazole compounds such as probenazole and dichlobentiazox; Phenylpyrazole compounds such as fenpyrazamine; Dithiolane compounds such as isoprothi
  • Sulfur, sulfur-based compounds such as lime sulfur
  • Other compounds include pyroquilon, diclomezine, chloropicrin, dazomet, metam-sodium, proquinazid, spiroxamine, dipymetitrone, etc.
  • Microbial germicides such as Bacillus amyloliqefaciens strain QST713, Bacillus amyloliqefaciens strain FZB24, Bacillus amyloliqefaciens strain MBI600, Bacillus amyloliqefaciens strain D747, Pseudomonas fluorescens, Bacillus subtilis, Trichoderma atroviride SKT-1; and plant extracts such as tea tree oil.
  • the active ingredient compounds (common names) of the insecticides, nematicides, acaricides, or soil pesticides among the other agricultural and horticultural agents mentioned above can be appropriately selected, for example, from the following compound groups. Even if not specifically stated, if these compounds have various structural isomers such as salts, alkyl esters, and optical isomers, these are of course included.
  • Carbamate compounds such as carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, carbosulfan, benfuracarb, bendiocarb, furathiocarb, isoprocarb, metolcarb, xylylcarb, XMC (3,5-xylyl methylcarbamate), and fenothiocarb;
  • Nereistoxin derivatives such as cartap, thiocyclam, thiocyclam oxalate, thiocyclam hydrochloride, bensultap, thiosultap, monosultap (also known as thiosultap-monosodium), bisultap (also known as thiosultap-disodium), and polythialan;
  • Organochlorines such as dicofol,
  • Fenvalerate permethrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, theta-cypermethrin, beta-cypermethrin, deltamethrin, cyhalothrin, gamma-cyhalothrin , lambda-cyhalothrin, tefluthrin, kappa-tefluthrin, etofenprox, flufenprox, cyfluthrin, beta-cyfluthrin, fenpropathrin, flucythrinate, fluvalinate, cycloprotrin hrin), pyrethrins, esfenvalerate, tetramethrin, resmethrin, protrifenbute, bifenthrin, kappa-bifenthrin, acrinathrin
  • Benzoyl urea compounds such as diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, lufenuron, novaluron, triflumuron, hexaflumuron, bistrifluron, noviflumuron, fluazuron, and flufenoxuron; Juvenile hormone-like compounds such as methoprene, pyriproxyfen, fenoxycarb, diofenolan; Pyridazinone compounds such as pyridaben; Pyrazole compounds such as fenpyroximate, fipronil, ethiprole, acetoprole, pyrafluprole, pyriprole, cyenopyrafen, and flufiprole; Pyrazolecarboxamide compounds such as pyflubumide, tebufenpyrad, tolfenpyrad, dimpropyridaz; Pyridylpyrazole
  • Neonicotinoid compounds such as imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran, dinotefuran, and nithiazine; Hydrazine compounds such as tebufenozide, methoxyfenozide, chromafenozide, and halofenozide; Pyridine compounds such as pyridalyl, flonicamid, and flumetnicam; Tetronic acid compounds such as spirodiclofen, spiromesifen, and spirobudifen; Tetramic acid compounds such as spirotetramat and spiropidione; Strobilurin compounds such as fluacrypyrim, bifemetstrobin, pyriminostrobin, and flupyroxystrobin; Pyrimidinamine compounds such as flufenerim and pyrimidifen; Organ
  • Thiourea compounds such as diafenthiuron and chloromethiuron; Formamidine compounds such as amitraz, chlordimeform, and chloromebuform; Pyridine azomethine compounds such as pymetrozine and pyrifluquinazone; Isoxazolines such as afoxolaner, fluralaner, fluxametamide, sarolaner, and isoflualanam; Other compounds include buprofezin, hexythiazox, triazamate, chlorfenapyr, indoxacarb, acequinocyl, etoxazole, 1,3-dichloropropene, benclothiaz, bifenazate, propargite, clofentezine, metaflumizone, cyflumetofen, fenazaquin, amidoflumet, sulfluramid, hydramethylnon, metaldehyde, sulfoxaflor, and fluence.
  • the present composition may also be applied in combination with the following compounds: Microbial pesticides such as crystal protein toxins produced by Bacillus thuringiensis, such as Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, and Bacillus thuringiensis tenebrionis, insect pathogenic virus agents, insect pathogenic fungal agents, and nematode pathogenic fungal agents; Antibiotics and semi-synthetic antibiotics such as abamectin, emamectin benzoate, ivermectin, milbemectin, milbemycin oxime, lepimectin, spinosad, spinetoram; Natural products such as azadirachtin, rotenone, and ryanodine; repellents such as deet; Physical control agents such as paraffin oil, mineral oil; RNA
  • N-substituted oxy-2-aminothiazolecarboxamide compound represented by formula (I) or a salt thereof [2] The N-substituted oxy-2- aminothiazolecarboxamide compound or a salt thereof according to the above [1], wherein R 1 is (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkynyl, or (C 2 -C 6 ) alkenyl optionally substituted with at least one T 1.
  • N-substituted oxy -2- aminothiazolecarboxamide compound or a salt thereof according to any one of [1] to [14] above, wherein Y 1 is a fluorine atom, a chlorine atom, methyl, trifluoromethyl, cyano or nitro, and Y 2 , Y 3 and Y 4 are each independently a fluorine atom, a chlorine atom or a hydrogen atom.
  • N-substituted oxy -2 -aminothiazolecarboxamide compound or a salt thereof according to any one of [1] to [14] above, wherein Y 1 is a fluorine atom, a chlorine atom, methyl, trifluoromethyl, or nitro, Y 2 and Y 3 are each independently a fluorine atom or a hydrogen atom, and Y 4 is a hydrogen atom.
  • R 1 is a (C 1 -C 6 ) chain hydrocarbon
  • X 1 is halogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, or a hydrogen atom
  • Y 1 , Y 2 , Y 3 , and Y 4 are each independently halogen, hydrogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, or nitro.
  • An agricultural and horticultural fungicide comprising the N-substituted oxy-2-aminothiazolecarboxamide compound or its salt according to any one of [1] to [77] above as an active ingredient.
  • a method for controlling plant diseases comprising applying an effective amount of the N-substituted oxy-2-aminothiazolecarboxamide compound or its salt according to any one of [1] to [77] to a plant body, a plant pathogen, or soil.
  • the melting point which is a physical property value of the compound of the present invention, was measured using a melting point measuring device (Buchi, model number M-565).
  • 1 H-NMR spectrum data was measured in a measurement solvent using an FT-NMR device (JEOL, product name JNM-ECX (500 MHz) or Bruker, product name AVANCE III HD (300 MHz)) ( 1 H-nuclear magnetic resonance spectroscopy).
  • the measurement solvent may contain tetramethylsilane (TMS) as an internal standard.
  • room temperature means a temperature of about 10 to 30°C.
  • the organic layer obtained by extraction was washed successively with a saturated aqueous solution of potassium sodium tartrate, water, and saturated saline, dried over anhydrous sodium sulfate, filtered, and then concentrated under reduced pressure to obtain an oily crude product of 2-chloro-5,6-difluoronicotinaldehyde (2.03 g).
  • the crude product (2.03 g) was dissolved in methanol (100 mL), and sodium borohydride (0.52 g) was added to the resulting solution at 0° C., and the resulting mixture was stirred overnight at room temperature to obtain a reaction solution.
  • Aqueous hydrochloric acid was added to the reaction solution to quench it.
  • the quenched reaction solution was neutralized with saturated aqueous sodium bicarbonate solution. Methanol was distilled off, and ethyl acetate was added to the resulting residue. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The organic layer obtained by extraction was washed successively with water and saturated saline, dried over anhydrous sodium sulfate, filtered, and then concentrated under reduced pressure. The resulting residue was purified by column chromatography (eluent: ethyl acetate/heptane) to obtain oily (2-chloro-5,6-difluoropyridin-3-yl)methanol (1.49 g).
  • O-methylhydroxylamine hydrochloride (96.31 mg) was added to the obtained mixture at room temperature, and the mixture was stirred at 50° C. for 7.5 hours to obtain a reaction solution.
  • the obtained reaction solution was allowed to cool to room temperature, and then water was added to the reaction solution to quench it.
  • Ethyl acetate and heptane were added successively to the quenched reaction solution, and the aqueous layer was extracted with a mixed solvent of ethyl acetate and heptane.
  • the organic layer obtained by extraction was washed successively with water and saturated saline, dried over anhydrous sodium sulfate, filtered, and then concentrated under reduced pressure.
  • an aqueous solution (22 mL) of sodium dihydrogen phosphate (14.49 g) was added at 0° C., and the mixture was stirred to obtain a mixture.
  • an aqueous solution (44 mL) of sodium chlorite (13.6 g, 80%) was added to the mixture, and the mixture was stirred overnight at room temperature.
  • An aqueous solution of hydrochloric acid was added to the reaction solution to adjust it to acidic, and ethyl acetate was further added for extraction.
  • the extracted organic layer was washed successively with water and saturated saline, dried over anhydrous sodium sulfate, filtered, and then concentrated under reduced pressure.
  • the obtained solid was dissolved in a saturated aqueous solution of sodium hydrogen carbonate, and the aqueous layer was washed with ethyl acetate.
  • Aqueous hydrochloric acid was added to the aqueous layer washed with ethyl acetate to adjust it to acidity.
  • Ethyl acetate was added to the aqueous layer adjusted to acidity, and the aqueous layer was extracted with ethyl acetate.
  • the organic layer obtained by extraction was washed successively with water and saturated saline, dried over anhydrous sodium sulfate, filtered, and then concentrated under reduced pressure to obtain a solid.
  • Tetrahydrofuran (3 mL) was added to the obtained acid chloride to dissolve it, and then a solution of N-[(2-chloro-5,6-difluoropyridin-3-yl)methyl]-O-methylhydroxylamine (100 mg) in tetrahydrofuran (2 mL) and diisopropylethylamine (0.13 mL) were added successively at room temperature, and the mixture was stirred at 50° C. for 2.5 hours under a nitrogen atmosphere to obtain a reaction solution. The obtained reaction solution was allowed to cool to room temperature, and then the reaction solution was quenched using a saturated aqueous solution of sodium bicarbonate.
  • the obtained reaction solution was allowed to cool to room temperature, and then a saturated aqueous solution of sodium bicarbonate was slowly added to the reaction solution to adjust the reaction solution to basicity.
  • the aqueous layer of the reaction solution adjusted to basicity was extracted with ethyl acetate.
  • the organic layer obtained by extraction was washed successively with water and saturated saline, dried over anhydrous sodium sulfate, filtered, and then concentrated under reduced pressure.
  • the obtained residue was purified by column chromatography (eluent: ethyl acetate/heptane) to obtain the title target compound (compound No. 17, 117 mg) as a solid.
  • a salt of compound (I) the type of salt is indicated in the remarks column in Table 1.
  • compounds described as HCl salt are hydrochlorides
  • compounds described as TsOH salt are paratoluenesulfonates
  • compounds described as Na salt are sodium salts.
  • compound No. 68 is the hydrochloride salt of compound No. 17.
  • Compound No. 69 is the paratoluenesulfonate salt of compound No. 17.
  • Compound No. 70 is the sodium salt of compound No. 17.
  • Tables 2 and 3 show the physical properties of compound (I) synthesized according to the above-mentioned production method and examples.
  • Table 2 shows the melting point of compound (I).
  • Table 3 shows the 1 H-NMR spectrum data of compound (I) [measured by 1 H-nuclear magnetic resonance spectroscopy; ⁇ is the chemical shift value (ppm)].
  • the numbers in Tables 2 and 3 have the same meanings as in Table 1.
  • *1 indicates the temperature at which the compound decomposed when its melting point was measured.
  • s is singlet, brs is broadened singlet, d is doublet, t is triplet, q is quartet, and m is multiplet.
  • Example 68 hereinafter also referred to as comparative compound A described in Patent Document 1 shown below as a comparison subject.
  • Test Example Preparation of drug solutions containing test compounds: The test compound was mixed with acetone or dimethyl sulfoxide to dissolve the test compound. Water was added to the test compound solution to dilute the test compound, which is the active ingredient, to a predetermined concentration (400 ppm) to obtain a drug solution. This drug solution was used in the following Test Examples 1 to 3.
  • Test Example 1 Fungicidal effect test against tomato late blight ( Phytophthora infestans ) (preventive effect test) Tomatoes were grown in vinyl pots with a diameter of 6 cm, and when they reached the 4.5-5.5 leaf stage, 10 ml of the drug solution was sprayed with a spray gun. After the drug solution dried (on the day of treatment), a spore suspension of Phytophthora infestans was sprayed and inoculated, and the plants were placed in an inoculation box at a temperature of 20°C and a humidity of 95% or more for 16 hours.
  • Control rate (%) 100 - (X/Y) x 100 X: Lesion area rate of test compound (%), Y: Lesion area rate of untreated area (%) Test compound: Compound No.
  • Test Example 2 Fungicidal effect test against cucumber downy mildew ( Pseudoperonospora cubensis ) (preventive effect test) Cucumbers were grown in vinyl pots with a diameter of 6 cm, and when they reached the 1.2-1.5 leaf stage, 10 ml of the drug solution was sprayed with a spray gun. After the drug solution dried (on the day of treatment or the day after treatment), a spore suspension of cucumber downy mildew ( Pseudoperonospora cubensis ) was sprayed and inoculated, and the plants were placed in an inoculation box at a temperature of 20°C and a humidity of 95% or more for 24 hours.
  • Test Example 3 Fungicidal effect test against tomato late blight ( Phytophthora infestans ) (therapeutic effect test) Tomatoes were grown in vinyl pots with a diameter of 6 cm, and when they reached the 4.5-5.5 leaf stage, they were inoculated by spraying a spore suspension of Phytophthora infestans , and placed in an inoculation box at a temperature of 20°C and a humidity of 95% or more for 4 hours. Then, 10 ml of the liquid was sprayed with a spray gun, and after the liquid dried (on the day of treatment), the pot was placed in a thermostatic chamber at 20°C.
  • each liquid (active ingredient concentration 400 ppm) using the following compounds of the present invention as test compounds showed a control rate of 80% or more against tomato late blight.
  • Test compound Compound No. 3, 7, 8, 10, 11, 13, 17, 19, 32, 34, 41, 51, 54, 55, 57, 58, 61, 84, 87
  • the control rate of the solution containing the comparative compound A was less than 30%.
  • the compound of the present invention exhibits excellent control effects against harmful plant diseases. Therefore, the compound of the present invention is useful as an agricultural and horticultural fungicide.
  • Formulation Example 1 (1) 20 parts by weight of compound (I) (2) 72 parts by weight of clay (3) 8 parts by weight of sodium lignin sulfonate The above ingredients are uniformly mixed to give a wettable powder.
  • Formulation Example 2 (1) Compound (I) 5 parts by weight (2) Talc 95 parts by weight or more are uniformly mixed to give a dusting agent.
  • Formulation Example 3 (1) Compound (I) 20 parts by weight (2) N,N-dimethylacetamide 20 parts by weight (3) Polyoxyethylene alkylphenyl ether 10 parts by weight (4) Xylene 50 parts by weight The above ingredients are uniformly mixed and dissolved to prepare an emulsion.
  • Formulation Example 4 (1) 68 parts by weight of clay (2) 2 parts by weight of sodium lignin sulfonate (3) 5 parts by weight of polyoxyethylene alkylaryl sulfate (4) 25 parts by weight of finely powdered silica A mixture of the above components and compound (I) are mixed in a weight ratio of 4:1 to obtain a wettable powder.
  • Formulation Example 5 (1) 50 parts by weight of compound (I), (2) 2 parts by weight of polyoxyethylene alkylphenyl ether phosphate triethanolamine salt, (3) 0.2 parts by weight of silicone, and (4) 47.8 parts by weight of water.
  • Formulation Example 7 (1) Compound (I) 2.5 parts by weight (2) N-methyl-2-pyrrolidone 2.5 parts by weight (3) Soybean oil 95.0 parts by weight The above ingredients are uniformly mixed and dissolved to prepare an ultra low volume formulation.
  • Formulation Example 8 (1) 20 parts by weight of compound (I) (2) 2 parts by weight of polyoxyethylene alkylphenyl ether phosphate triethanolamine salt (3) 0.2 parts by weight of silicone (4) 0.1 parts by weight of xanthan gum (5) 5 parts by weight of ethylene glycol (6) 72.7 parts by weight of water The above ingredients are uniformly mixed and pulverized to obtain an aqueous suspension.

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Abstract

L'invention concerne un nouveau composé présentant un excellent effet de lutte contre les maladies des plantes nuisibles. Ce composé oxy-2-aminothiazolecarboxamide N-substitué représenté par la formule (I) (dans la formule, chaque symbole est tel que décrit dans la description) ou un sel de celui-ci présente un excellent effet de lutte contre les maladies des plantes nuisibles.
PCT/JP2024/041728 2023-12-15 2024-11-26 Composé oxy-2-aminothiazolecarboxamide n-substitué ou sel de celui-ci et bactéricide agricole et horticole Pending WO2025126830A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010504946A (ja) * 2006-09-29 2010-02-18 バイエル・クロツプサイエンス・エス・アー 殺菌剤ｎ−シクロアルキル−カルボキサミド、チオカルボキサミド及びｎ−置換−カルボキシイミドアミド誘導体
JP2013541554A (ja) * 2010-10-21 2013-11-14 バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー Ｎ−ベンジルヘテロ環式カルボキサミド類
JP2020514340A (ja) * 2017-03-10 2020-05-21 シンジェンタ パーティシペーションズ アーゲー 殺微生物オキサジアゾール誘導体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010504946A (ja) * 2006-09-29 2010-02-18 バイエル・クロツプサイエンス・エス・アー 殺菌剤ｎ−シクロアルキル−カルボキサミド、チオカルボキサミド及びｎ−置換−カルボキシイミドアミド誘導体
JP2013541554A (ja) * 2010-10-21 2013-11-14 バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー Ｎ−ベンジルヘテロ環式カルボキサミド類
JP2020514340A (ja) * 2017-03-10 2020-05-21 シンジェンタ パーティシペーションズ アーゲー 殺微生物オキサジアゾール誘導体

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