WO2013047308A1 - Dérivé d'azole, produit chimique pour l'agriculture/l'horticulture, agent protecteur de matière industrielle, procédé de contrôle d'une maladie des plantes et semence - Google Patents

Dérivé d'azole, produit chimique pour l'agriculture/l'horticulture, agent protecteur de matière industrielle, procédé de contrôle d'une maladie des plantes et semence Download PDF

Info

Publication number
WO2013047308A1
WO2013047308A1 PCT/JP2012/074009 JP2012074009W WO2013047308A1 WO 2013047308 A1 WO2013047308 A1 WO 2013047308A1 JP 2012074009 W JP2012074009 W JP 2012074009W WO 2013047308 A1 WO2013047308 A1 WO 2013047308A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
azole derivative
atom
alkyl
Prior art date
Application number
PCT/JP2012/074009
Other languages
English (en)
Japanese (ja)
Inventor
大河 正野
須藤　敬一
泰司 三宅
Original Assignee
株式会社クレハ
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 株式会社クレハ filed Critical 株式会社クレハ
Publication of WO2013047308A1 publication Critical patent/WO2013047308A1/fr

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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • the present invention relates to a novel azole derivative.
  • the present invention also relates to an agricultural and horticultural agent and an industrial material protective agent containing the derivative as an active ingredient, a plant disease control method using the agricultural and horticultural agent, and a seed obtained using the agricultural and horticultural agent.
  • Patent Document 17 discloses a triazole derivative in which one of hydrogen atoms in a triazole ring typified by prothioconazole is substituted with a substituent containing a sulfur atom.
  • European Patent Application No. 0015756 European Patent Application Publication No. 0052424 European Patent Application Publication No. 0061835 European Patent Application No. 0297345 European Patent Application Publication No. 0047594
  • European Patent Application No. 0212605 Japanese Patent Publication “JP-A-56-97276” Japanese Patent Publication “JP-A-61-226049” Japanese Patent Publication “JP-A-2-286664” Japanese Patent Publication “JP 59-98061 A” Japanese Patent Publication “Japanese Patent Laid-Open No. 61-271276” European Patent Application No. 0229642 Japanese Patent Publication “JP-A-4-230270” International Publication No. 2011/070742 Japanese Patent Publication “JP 2004-99623 A” Japanese Patent Publication “Special Table 2003-518104” Japanese Patent Gazette “Tokuhohei 10-508863 Publication”
  • the present invention has been made in view of the above problems, and its purpose is to provide a high control effect against plant diseases, and as an active ingredient in agricultural and horticultural medicines with reduced phytotoxicity to plants. It is to provide an azole derivative to be contained.
  • the azole derivatives represented by the following general formula (I) or the following general formula (III) have excellent activity and have reduced phytotoxicity to plants. As a result, the present invention has been completed.
  • R 1 and R 2 are each independently a cycloalkyl group having 3 to 6 carbon atoms, or an alkyl having 1 to 4 carbon atoms in which one hydrogen atom is substituted with a cycloalkyl group having 3 to 6 carbon atoms Represents a group.
  • at least one hydrogen atom is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.
  • An aryl group, or an arylalkyl group (the alkyl moiety has 1 to 3 carbon atoms).
  • At least one hydrogen atom is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or an alkyl ring having 1 to 4 carbon atoms. It may be substituted with an alkoxy group or a haloalkoxy group having 1 to 4 carbon atoms.
  • A represents a nitrogen atom or a methine group.
  • X represents —SH, —SR 8 , —SO—R 8 , —SO 2 —R 8 or —SO 3 H.
  • R 8 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, an aryl group, or an arylalkyl Group (the number of carbon atoms in the alkyl moiety is 1 to 4), and in the aryl group and arylalkyl group in R 8 , at least one hydrogen atom in the aromatic ring may be substituted with a halogen atom.
  • the present invention also includes an agricultural and horticultural agent or an industrial material protective agent characterized by containing the above azole derivative as an active ingredient.
  • the azole derivative according to the present invention has an excellent bactericidal action against many bacteria that cause diseases on plants, and has low phytotoxicity on plants. In addition, the azole derivative according to the present invention is reduced in toxicity to human livestock.
  • the drug containing the azole derivative according to the present invention as an active ingredient exhibits an effect of being able to reduce the toxicity to human livestock and keep the drug damage low while exhibiting a high control effect against a wide range of plant diseases. .
  • the azole derivative according to the present invention is an azole derivative represented by the following general formula (I) or (III).
  • the azole derivative represented by the general formula (I) and the azole derivative represented by the general formula (III) are referred to as an azole derivative (I) and an azole derivative (III), respectively.
  • R 1 and R 2 are each independently a cycloalkyl group having 3 to 6 carbon atoms, or an alkyl having 1 to 4 carbon atoms in which one hydrogen atom is substituted with a cycloalkyl group having 3 to 6 carbon atoms Represents a group.
  • R 1 and R 2 may be the same or different.
  • Examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group, more preferably a cyclopropyl group, a cyclobutyl group and a cyclopentyl group, and particularly preferably Cyclopropyl group.
  • Examples of the alkyl group having 1 to 4 carbon atoms in which one hydrogen atom is substituted with a cycloalkyl group having 3 to 6 carbon atoms include a cyclopropylmethyl group, a cyclobutylmethyl group, and 2- (cyclopropyl) And an ethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a 3- (cyclopropyl) propyl group and a 4- (cyclopropyl) butyl group, and more preferably a cyclopropylmethyl group, a 2- (cyclopropyl) ethyl group , 3- (cyclopropyl) propyl group and 4- (cyclopropyl) butyl group, particularly preferably cyclopropylmethyl group and 2- (cyclopropyl) ethyl group.
  • At least one hydrogen atom is a halogen atom, an alkyl group having 1 to 4 carbon atoms, It may be substituted with a 1 to 4 haloalkyl group, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group or an arylalkyl group (the alkyl moiety has 1 to 3 carbon atoms).
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include a methyl group, an ethyl group, an n-propyl group, and a 1-methylethyl group.
  • Examples of the haloalkyl group having 1 to 4 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a chloromethyl group, a trichloromethyl group, and a bromomethyl group.
  • Examples of the cycloalkyl group having 3 to 6 carbon atoms as a substituent include a cyclopropyl group and a cyclobutyl group.
  • a phenyl group is mentioned as an aryl group.
  • Examples of the arylalkyl group include a benzyl group and a phenethyl group.
  • halogen atom a methyl group, an ethyl group and an n-propyl group as an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group as a haloalkyl group having 1 to 4 carbon atoms, and a chloromethyl group.
  • substituents include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a cyclopropyl group, and a phenyl group. Particularly preferred are a chlorine atom, a bromine atom and a methyl group.
  • One, two or three hydrogen atoms in the aromatic ring of the aryl group and arylalkyl group described above are each a halogen atom, an alkyl group having 1 to 4 carbon atoms (including a cycloalkyl group), 1 to It may be substituted with a 4 haloalkyl group, an alkoxy group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms.
  • halogen atom as a substituent in the aromatic ring of the aryl group and arylalkyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the alkyl group having 1 to 4 carbon atoms includes methyl group, ethyl group, n-propyl group, 1-methylethyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, 2, Examples include 2-dimethylethyl group and cyclopropylmethyl group.
  • examples of the haloalkyl group having 1 to 4 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a chloromethyl group, a trichloromethyl group, and a bromomethyl group.
  • examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a 1-methylethoxy group, and a 1,1-dimethylethoxy group.
  • examples of the haloalkoxy group having 1 to 4 carbon atoms include a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, and a pentafluoroethoxy group. More preferably, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, trifluoromethyl group, chloromethyl group, methoxy group, ethoxy group and the like can be mentioned.
  • R 1 and R 2 are each independently (i) a carbon atom in which at least one hydrogen atom is substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms. More preferably, it is a cycloalkyl group having 3 to 6 atoms, or (ii) an alkyl group having 1 to 4 carbon atoms in which at least one hydrogen atom is substituted with a cycloalkyl group (i).
  • R 1 and R 2 are each independently (iii) a cyclopropyl group in which at least one of the hydrogen atoms is substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms, or (iv) a hydrogen atom More preferably, at least one is an alkyl group having 1 to 4 carbon atoms, which is substituted with a cyclopropyl group of (iii).
  • R 1 and R 2 are each independently a group represented by the following general formula (V).
  • R 3 , R 4 , R 5 , R 6 and R 7 each independently represent a hydrogen atom, a halogen atom, a methyl group or an ethyl group, and R 3 , R 4 , R 5 , At least one of R 6 and R 7 is a halogen atom, and n represents 0, 1 or 2.
  • Examples of the halogen atom in R 3 , R 4 , R 5 , R 6 and R 7 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • n in the general formula (V) representing R 2 is 0, R 7 is a halogen atom, R 3 , R 4 , R 5 and R 6 are hydrogen atoms, and the above general formula representing R 1 N in (V) is preferably 1 or 2. In that case, it is more preferable that R 3 and R 4 in the general formula (V) representing R 1 are halogen atoms, and R 5 , R 6 and R 7 are hydrogen atoms.
  • A represents a nitrogen atom or a methine group. Preferably it is a nitrogen atom.
  • X represents —SH, —SR 8 , —SO—R 8 , —SO 2 —R 8 or —SO 3 H.
  • R 8 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, an aryl group Or an arylalkyl group (wherein the alkyl moiety has 1 to 4 carbon atoms).
  • alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, n-propyl group, 1-methylethyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1- Dimethylethyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1- Ethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1 , 3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-e
  • alkenyl group having 2 to 6 carbon atoms examples include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1 -Propenyl group, 2-methyl-1-propenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group 1-methyl-1-butenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 3-methyl- 2-butenyl group, 1-methyl-3-butenyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1,2-dimethyl-1 -Professional Nyl group
  • haloalkyl group having 1 to 6 carbon atoms examples include chloromethyl group, bromomethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chlorofluoromethyl group, dichlorofluoromethyl group, Chlorodifluoromethyl group, 1-chloroethyl group, 1-bromoethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro- Examples include 2-fluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2-dichloro-2-fluoroethyl group, 2,2,2-trichloroethyl group, and pentafluoroethyl group.
  • haloalkenyl group having 2 to 6 carbon atoms examples include 2-chloroethenyl group, 2,2-dichloroethenyl group, 2-chloro-2-propenyl group, 3,3-dichloro-2-propenyl group, 2,3- Dichloro-2-propenyl group, 3,3-dichloro-2-methyl-2-propenyl group, 3-chloro-2-butenyl group, 2-fluoroethenyl group, 2,2-difluoroethenyl group, 2-fluoro -2-propenyl group, 3,3-difluoro-2-propenyl group, 2,3-difluoro-2-propenyl group, 3,3-difluoro-2-methyl-2-propenyl group, 3-fluoro-2-butenyl Group, 2-bromoethenyl group, 2,2-dibromoethenyl group, 2-bromo-2-propenyl group, 3,3
  • arylalkyl group (the alkyl part has 1 to 4 carbon atoms), phenylmethyl group, phenylnaphthyl group, 1-phenylethyl group, 2-phenylethyl group, 2-naphthylethyl group, 1-phenylpropyl group, Examples thereof include 2-phenylpropyl group, 3-phenylpropyl group, 1-methyl-2-phenylethyl group, 1-methyl-1-phenylethyl group, 4-phenylbutyl group and the like.
  • aryl group examples include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group.
  • 1, 2 or 3 hydrogen atoms in the aromatic ring of the aryl group and arylalkyl group for R 8 are each a halogen atom, an alkyl group having 1 to 4 carbon atoms (including a cycloalkyl group), or the number of carbon atoms It may be substituted with 1 to 4 haloalkyl groups.
  • the alkyl group having 1 to 4 carbon atoms as a substituent includes a methyl group, an ethyl group, an n-propyl group, a 1-methylethyl group, an n-butyl group, a 1-methylpropyl group, and a 2-methylpropyl group. Group, 1,1-dimethylethyl group, cyclopropylmethyl group and the like.
  • examples of the haloalkyl group having 1 to 4 carbon atoms as a substituent include a trifluoromethyl group, a pentafluoroethyl group, a chloromethyl group, a trichloromethyl group, and a bromomethyl group. More preferred are fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, trifluoromethyl group and chloromethyl group.
  • the azole derivative (I) and the azole derivative (III) are used as active ingredients of agricultural and horticultural chemicals or industrial material protecting agents, the functional group X in the triazole ring or imidazole ring in the plant body and bacterial cells.
  • the azole derivative (III) (“thiono” form) is a tautomer of an azole derivative (“mercapto” form) represented by the following general formula (II) in which X in the general formula (I) is —SH.
  • azole derivative according to the present invention include, but are not limited to, an azole derivative represented by the following general formula (IV).
  • m is 1 or 2
  • X is a chlorine atom or a bromine atom.
  • the carbon atom to which the hydroxy group is bonded is an asymmetric carbon. That is, in that case, the azole derivative (I) and the azole derivative (III) have enantiomers.
  • an asymmetric carbon atom is present in the functional group represented by R 1 or R 2 .
  • the azole derivative (I) and the azole derivative (III) include both those containing such isomers alone and those containing each of these isomers in an arbitrary ratio.
  • the production method of the azole derivative (I) and the azole derivative (III) is not particularly limited.
  • a known azole derivative represented by the following general formula (VI) hereinafter referred to as azole derivative (VI))
  • azole derivative (VI)) As a starting material, and can be produced according to the method described in Patent Document 15.
  • R 1 , R 2 and A are the same as the above-mentioned R 1 , R 2 and A, respectively.
  • the azole derivative (VI) is reacted with a strong base and sulfur sequentially in the presence of a diluent, and then the product is hydrolyzed with water (reaction (a)), or the azole derivative (VI)
  • reaction (b) By reacting in the presence of sulfur powder and dimethylformamide (reaction (b)), the azole derivative represented by the general formula (II) (hereinafter referred to as azole derivative (II)) and the azole derivative (III) are converted into Obtainable.
  • reaction (a) and reaction (b) are demonstrated as a manufacturing method of azole derivative (III).
  • the strong base in reaction (a) can include all strong alkali metal bases commonly used in similar reactions, such as n-butyllithium, lithium diisopropylamide, sodium hydride and sodium amide,
  • potassium t-butylate as a mixture with tetramethylethylenediamine (TMEDA) can be preferably used.
  • Diluents in reaction (a) can include all inert organic solvents commonly used in similar reactions, such as ethers such as tetrahydrofuran, dioxane, diethyl ether and 1,2-dimethoxyethane. And strong polar solvents such as liquid ammonia or dimethyl sulfoxide can be suitably used.
  • the amount of sulfur used in the reaction (a) is, for example, 1 to 5 mol, preferably 1 to 1.5 mol, with respect to 1 mol of the azole derivative (VI). Sulfur is preferably used in a powder state.
  • Hydrolysis in reaction (a) may be carried out in the presence of an acid, which can include all inorganic or organic acids commonly used in similar reactions, such as acetic acid, Dilute sulfuric acid and dilute hydrochloric acid can be preferably used.
  • an acid which can include all inorganic or organic acids commonly used in similar reactions, such as acetic acid, Dilute sulfuric acid and dilute hydrochloric acid can be preferably used.
  • the hydrolysis can also be carried out using an aqueous ammonium chloride solution.
  • the reaction temperature in the reaction (a) is, for example, ⁇ 70 ° C. to 20 ° C., preferably ⁇ 70 ° C. to 0 ° C.
  • the azole derivative (VI) used as a starting material can be produced by the method described in Patent Document 14.
  • the azole derivative (III) When the azole derivative (III) is produced by the reaction (b), the azole derivative (VI) can be diluted with a diluent.
  • a diluent Any conventional aprotic polar organic solvent can be used as the diluent.
  • amides such as dimethylformamide
  • N-alkyl-pyrrolidones such as N-octyl-pyrrolidone and N-dodecyl-pyrrolidone
  • N-alkyl-caprolactams such as N-methyl-caprolactam and N-octyl-caprolactamkind.
  • reaction temperature in the reaction (b) can be changed within a certain range, for example, a temperature of 140 ° C. to 200 ° C., preferably 150 ° C. to 160 ° C.
  • the reaction can be carried out at atmospheric pressure or under pressure.
  • the amount of sulfur used in the reaction (b) is, for example, 6 to 15 mol, preferably 8 to 13 mol, with respect to 1 mol of the azole derivative (VI).
  • the azole derivative (III) produced by the reaction (a) or the reaction (b) may be separated and purified by conventional methods such as recrystallization and chromatography.
  • R 1 and R 2 in the general formula (IX) are the same as the above-described R 1 and R 2 , respectively.
  • the compound represented by the general formula (IX) can be produced by the method described in Patent Document 14.
  • azole derivatives (I) can be produced from azole derivatives (III).
  • the obtained azole derivative (III) is represented by the general formula (VII) in the presence of an acid binder and a diluent.
  • R 9 -L .. (VII) (In the general formula (VII), R 9 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or a halo having 2 to 6 carbon atoms.
  • An alkenyl group or an arylalkyl group (the alkyl moiety has 1 to 4 carbon atoms).
  • L represents a halogen atom.
  • X is —SR 8 (wherein R 8 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms).
  • R 8 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms).
  • An azole derivative (I) that is a haloalkyl group, a haloalkenyl group having 2 to 6 carbon atoms, or an arylalkyl group (the alkyl moiety has 1 to 4 carbon atoms) can be produced (reaction (c)) ).
  • Alkyl group having 1 to 6 carbon atoms in R 9, an alkenyl group having 2 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, haloalkenyl group, an arylalkyl group (alkyl moiety of 2-6 carbon atoms 1 to 4) have the same meaning as these groups for R 8 .
  • L represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the acid binder in the reaction (c) include all commonly used inorganic bases and organic bases, such as alkali metal hydroxides such as sodium hydroxide, calcium hydroxide and potassium hydroxide, or Alkaline earth metal hydroxides; ammonium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate; alkali metal acetates such as sodium acetate, potassium acetate and calcium acetate or alkaline earths Metal acetates; and trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methyl-piperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) And diazabicik Tertiary amines such as roundecene (DBU) can be suitably used.
  • alkali metal hydroxides such as sodium hydro
  • Examples of the diluent in the reaction (c) include all commonly used organic solvents, such as diethyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, ethers such as tetrahydrofuran and dioxane, acetonitrile and the like. Of nitriles, and polar solvents such as dimethyl sulfoxide or dimethylformamide may be preferably used.
  • the reaction temperature in the reaction (c) is, for example, 0 ° C. to 120 ° C., preferably 20 ° C. to 100 ° C.
  • the amount of the halide represented by the general formula (VII) is, for example, 1 to 2 mol with respect to 1 mol of the azole derivative (III).
  • the acid binder for example, an equivalent amount or an excess amount of the azole derivative (III) can be used.
  • the aryl group in R 10 has the same meaning as the aryl group in R 8 described above.
  • the strong base and diluent in the reaction (d) can be used as the strong base and diluent in the reaction (a) as the strong base and diluent in the reaction (a) as the strong base and diluent (d).
  • the oxidizing agent in reaction (e) can include all materials commonly used for sulfur oxidation, such as hydrogen peroxide; peracids such as peracetic acid and metachloroperbenzoic acid; and permanganic acid.
  • An inorganic salt such as potassium can be preferably used.
  • diluent in the reaction (e) examples include all solvents generally used for similar reactions.
  • acetic acid or glacial acetic acid can be suitably used as the diluent.
  • potassium permanganate is used as the oxidizing agent, water or alcohol such as t-butanol can be preferably used.
  • the reaction temperature in the reaction (e) is, for example, 0 ° C. to 100 ° C., preferably 10 ° C. to 100 ° C.
  • the oxidant is preferably used in an equivalent amount relative to the azole derivative (I) in which X is —SR 8 .
  • the oxidant is preferably used in an excess amount relative to the azole derivative (I) where X is —SR 8 .
  • the azole derivative according to the present invention Since the azole derivative according to the present invention has a 1,2,4-triazolyl group or an imidazolyl group, it forms an acid addition salt of an inorganic acid or an organic acid, or a metal complex. Therefore, it can be used as an active ingredient such as agricultural and horticultural agents as part of acid addition salts and metal complexes.
  • the agricultural and horticultural agent containing the azole derivative according to the present invention as an active ingredient is applied to a plant, either the foliage treatment or the non-foliage treatment may be used as the agricultural or horticultural agent. Examples of the non-foliage treatment include seed treatment, irrigation treatment, and water surface treatment.
  • this agricultural and horticultural chemical can control not only non-stem and leaf diseases (soil diseases and seed diseases) but also stem and leaf diseases by non-stem and leaf treatment.
  • plant disease control methods including a step of performing foliage treatment or non-foliage treatment using the present agricultural and horticultural chemicals, and seeds treated with the present agricultural and horticultural chemicals are also included in the category of the present invention. It is.
  • Plant disease control effect The azole derivative according to the present invention exhibits a control effect on a wide range of plant diseases.
  • applicable diseases include: soybean rust (Phakopsora pachyrhizi, Phakopsora meibomiae), rice blast (Pyricularia grisea), rice sesame leaf (Cochliobolus miyabeanus), rice leaf blight (Xanthomonas oryzae), rice crest Blight (Rhizoctonia solani), rice black rot (Helminthosporium sigmoideun), rice seedling disease (Gibberella fujikuroi), rice seedling blight (Pythium aphanidermatum), apple powdery mildew (Podosphaera leucotricha), apple black astronomy inaequalis), apple morinia disease (Monilinia mali), apple spotted leaf disease (Alternaria alternata), apple rot disease (Valsa mali), pear black spot disease (
  • grape rust Phakopsora ampelopsidis
  • watermelon vine Fusarium oxysporum f.sp.niveum
  • cucumber vine Feusarim oxysporum f.sp.cucumerinum
  • radish yellow Fusarium oxysporum f. sp. raphani
  • tobacco red star disease Alternaria longipes
  • potato summer blight Alternaria solani
  • soybean brown spot disease Septoria glycines
  • soybean purple spot disease Cercospora kikuchii
  • Examples of applicable plants include wild plants, plant cultivars, plants and plant cultivars obtained by conventional biological breeding such as crossbreeding or protoplast fusion, and genetically modified plants and plant cultivars obtained by genetic manipulation. Is mentioned.
  • Examples of genetically modified plants and plant cultivars include herbicide-tolerant crops, pest-tolerant crops incorporating insecticidal protein production genes, disease-resistant crops incorporating resistance-inducing substance production genes against diseases, food-enhancing crops, and yield improvement Examples include crops, crops with improved shelf life and crops with improved yield.
  • Specific examples of genetically modified plant cultivars include those containing registered trademarks such as ROUNDUP READY, LIBERTY LINK, CLEARFIELD, YIELDGARD, HERCULEX, and BOLLGARD.
  • the azole derivative according to the present invention has an effect of increasing the yield by adjusting its growth and an effect of improving its quality for a wide variety of crops and horticultural plants.
  • crops include: wheat, barley, buckwheat and other wheat, rice, rapeseed, sugarcane, corn, maize, soybeans, peas, peanuts, sugar beet, cabbage, garlic, radish, carrots, apples, pears Citrus fruits such as oranges, oranges, lemons, peaches, cherry peaches, avocados, mangoes, papayas, peppers, cucumbers, melons, strawberries, tobacco, tomatoes, eggplants, grass, chrysanthemums, azaleas, and other ornamental plants.
  • the azole derivative according to the present invention exhibits an excellent effect of protecting the material from a wide range of harmful microorganisms that invade the industrial material.
  • microorganisms include: Aspergillus sp., Trichoderma sp., Penicillium sp., Geotrichum sp., Which are paper and pulp-degrading microorganisms (including slime-forming bacteria).
  • Aspergillus sp. Penicillium
  • Gliomastix (Gliomastix sp.), Mennoniella sp., Sarcopodium, Stschybotrys sp., Stemphylium sp., Zygorhynchus sp. , Bacillus (Bacillus sp.), Staphylococcus (Staphylococcus sp.) And other wood-modifying fungi, Tyromyces palustris, Kawariotake (Coriolus versicolor), Aspergillus sp., Penicillium sp.
  • Rhizopus sp. Aureobasidium sp., Glio clade (Gliocladum sp.), Cladosporium (Cladosporium sp.), Ketomium (Chaetomium sp.), Trichoderma (Trichoderma sp.), Aspergillus sp., Penicillium sp.
  • Ketomium Chomium sp.
  • Cladosporium Cladosporium sp.
  • Mucor Mucor
  • Paecilomyces sp. Pyrobus
  • Pullularia Pullularia sp.
  • Trichosporon sp. Tricothecium sp., Aspergillus sp., Penicillium sp., Rhizopus sp., Trichoderma sp., Ketomium sp.
  • Myrothecium sp. Streptomyces sp., Pseudomonas sp., Aspergillus sp., Which is a paint-deteriorating microorganism, such as Bacillus sp., Micrococcus sp., Serratia sp., Margarinomyces sp., Monascus sp.
  • Penicillium sp. Cladosporium sp., Aureobasidium sp., Gliocladium sp., Botryodiplodia sp., Macrosporum (Macrosporium sp.), Monilia sp., Forma (Phoma sp.), Pullularia ((Pullularia sp.), Sporotrichum sp., Trichoderma sp., Bacillus ((bacillus sp.), Proteus sp., Pseudomonas sp., And Serratia sp.
  • azole derivative according to the present invention as an active ingredient of an agricultural and horticultural medicine, it may be left as it is without adding any other components, but usually a solid carrier or a liquid carrier, a surfactant and other It is mixed with formulation adjuvants and used in various forms such as powders, wettable powders, granules and emulsions.
  • preparations are formulated so that the azole derivative according to the present invention is contained in an amount of 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 80% by weight as an active ingredient.
  • Examples of carriers, diluents and surfactants used as formulation adjuvants include talc, kaolin, bentonite, diatomaceous earth, white carbon and clay as solid carriers.
  • Examples of the liquid diluent include water, xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide and alcohol.
  • Surfactants should be properly used depending on their effects.
  • Examples of emulsifiers include polyoxyethylene alkylaryl ether and polyoxyethylene sorbitan monolaurate.
  • Dispersants include lignin sulfonate and dibutyl naphthalene.
  • Examples of the wetting agent include alkyl sulfonates and alkyl phenyl sulfonates.
  • concentration of the azole derivative according to the present invention when diluted is preferably in the range of 0.001 to 1.0%.
  • the amount of the azole derivative used in the present invention is 20 to 5000 g, more preferably 50 to 2000 g, per 1 ha of agricultural / horticultural lands such as fields, fields, orchards and greenhouses. Since these use concentrations and amounts vary depending on the dosage form, use time, use method, use place, target crop, etc., they can be increased or decreased without sticking to the above range.
  • the azole derivative according to the present invention is used in combination with other active ingredients, for example, fungicides, insecticides, acaricides, herbicides and the like as exemplified below to enhance performance as agricultural and horticultural agents. You can also.
  • ⁇ Antimicrobial substances Acibenzolar S-methyl, 2-phenylphenol (OPP), azaconazole, azoxystrobin, amisulbrom, bixaphene, benalaxyl, benomyl, bench avaricarb-isopropyl, bicarbonate, biphenyl, viteltanol, blasticidin-S, borax, bordeaux, boscalid, Bromuconazole, bronopol, bupirimate, secbutyramine, calcium polysulfide, captafor, captan, carbendazim, carboxin, carpropamide, quinomethionate, chloronebu, chloropicrin, chlorothalonil, clozolinate, cyazofamide, cyflufenamide, simoxanil, cyproconil, cyprodiazole Dazomet, debacarb, diclofuranide, diclocimet, dicro Gin, Dichlorane, Diet
  • ⁇ Insecticide / acaricide / nematicide> Abamectin, Acephate, Acrinathrin, Alanicarb, Aldicarb, Alletrin, Amitraz, Avermectin, Azadirachtin, Azamethifos, Azinphos-ethyl, Azinphos-methyl, Azocycline, Bacillus filmus, Bacillus subtilis, Bacillus thuringibulbbenthulbenbencarb , Benzoxymate, Bifenazite, Bifenthrin, Bioarethrin, Bioresmethrin, Bistriflurone, Buprofezin, Butocaboxin, Butoxycarboxyne, Kazusafos, Carbaryl, Carbofuran, Carbosulfan, Cartap, CGA50439, Chlordein, Chloretifol, Chlorfenapir Fenbinfoss,
  • the azole derivative according to the present invention as an active ingredient of an industrial material protective agent, it may be used alone without adding other components, but generally it is dissolved or dispersed in an appropriate liquid carrier. Or mixed with a solid carrier, and if necessary, further added an emulsifier, a dispersant, a spreading agent, a penetrating agent, a wetting agent, a stabilizer, etc., and a wettable powder, powder, granule, tablet, paste. It can be used as dosage forms such as suspensions and sprays. Moreover, you may mix
  • any liquid may be used as long as it does not react with the active ingredient.
  • water alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol, and cellosolve), ketones (for example, acetone, and Methyl ethyl ketone, etc.), ethers (eg, dimethyl ether, diethyl ether, dioxane, and tetrahydrofuran), aromatic hydrocarbons (eg, benzene, toluene, xylene, and methylnaphthalene), aliphatic hydrocarbons (eg, gasoline, Kerosene, kerosene, machine oil, fuel oil, etc.), acid amides (eg, dimethylformamide, N-methylpyrrolidone, etc.), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), esters ( For example, acetate Glycol ester, and glycer
  • fine powders or granular materials such as kaolin clay, bentonite, acid clay, pyrophyllite, talc, diatomite, calcite, urea and ammonium sulfate can be used.
  • surfactants such as soaps, alkylsulfonic acids, alkylarylsulfonic acids, dialkylsulfosuccinic acids, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxides and anhydrosorbitolscan be used.
  • the content ratio varies depending on the dosage form and purpose of use, but in general, the concentration is 0.1 to 99.9% by weight. It is appropriate to add.
  • the treatment concentration is usually adjusted to 0.005 to 5% by weight, preferably 0.01 to 1% by weight, by appropriately adding a solvent, a diluent, an extender and the like. It is preferable to do this.
  • the azole derivative according to the present invention exhibits an excellent bactericidal action against many bacteria that cause plant diseases. Further, the azole derivative according to the present invention has little phytotoxicity to plants. Furthermore, the azole derivative according to the present invention has low toxicity to animals.
  • the toxicity to human livestock is low, the handling safety is excellent, and a high control effect on a wide range of plant diseases is shown, and the control of agricultural and horticultural diseases with small phytotoxicity. Agent can be realized.
  • the obtained alkaline aqueous layer was washed once with toluene, and the separated toluene layer was mixed with the previously collected toluene layer and dried over anhydrous sodium sulfate. The solvent was distilled off, and 0.440 g of the remaining compound (VIa) was recovered.
  • the alkaline aqueous layer was acidified with 1M sulfuric acid, and extracted from this acidic aqueous solution three times with toluene. The obtained toluene layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a crude compound (IVa) as a yellow oil.
  • Example 1 Evaluation test of phytotoxicity of wheat growth suppression by seed treatment> By pot test, the phytotoxicity of growth suppression by seed treatment was evaluated. Compounds (IVa) to (IVd) dissolved in DMSO were applied to the wheat seeds in a vial so that the treatment amount was 2 to 200 g ai / 100 kg seeds, and then 8 wheat seeds were seeded in 80 cm 2 pots. . The lower water supply was controlled in a greenhouse, and the growth degree of wheat was investigated 12 days after sowing. The growth inhibition index was calculated from the criteria shown in Table 1. It shows that the smaller the growth inhibition index, the smaller the phytotoxicity of growth inhibition by chemical treatment. As a control, tests were conducted using compounds (VIa) to (VId) instead of compounds (IVa) to (IVd). The results are shown in Tables 2-5.
  • Example 2 Wheat red rust control effect by wheat seed treatment> By pot test, the control effect of wheat red rust caused by seed treatment was evaluated. Compounds (IVa) to (IVd) dissolved in DMSO were applied to the wheat seeds in a vial so that the treatment amount was 200 g ai / 100 kg seeds, and then 8 wheat seeds were sown in 80 cm 2 pots. The lower water supply was controlled in a greenhouse, and 20 days after sowing, wheat red rust fungus was inoculated and stored in a wet box for 2 days. Thereafter, the lower water supply was managed again in the greenhouse, and on the 13th day after inoculation, the diseased area ratio was investigated, and the control value was calculated by the following formula.
  • Control value (%) (1 ⁇ (Affected area ratio of treated area / Affected area ratio of untreated area)) ⁇ 100
  • a test was conducted using prothioconazole instead of compounds (IVa) to (IVd). The results are shown in Table 6.
  • Example 3 Evaluation test of phytotoxicity for soybean growth suppression> The pot test evaluated the phytotoxicity of growth inhibition by foliar spray treatment.
  • the sprayed leaves were air-dried and managed in a greenhouse.
  • the plant height of soybean was measured on the seventh day after the spraying of the drug.
  • tests were conducted using compounds (VIa) to (VId) instead of compounds (IVa) to (IVd). The results are shown in Tables 7-10.
  • Example 4 Wheat red rust control effect test by foliar spray treatment>
  • the second leaf stage wheat (cultivar: Norin 61) grown using a square plastic pot (6 cm ⁇ 6 cm), in the form of wettable powder of compounds (IVa) to (IVd) as in Preparation Example 1 was suspended in water at a predetermined concentration (100 mg / L) and sprayed at a rate of 1,000 L / ha.
  • the sprayed leaves were air-dried and then spray-inoculated with spores of wheat red rust fungus (adjusted to 200 cells / field of view, added with Grameen S to 60 ppm), and kept at 25 ° C. under high humidity for 48 hours. After that, it was managed in the greenhouse.
  • Control value (%) (1 ⁇ (average morbidity in sprayed area / average illness in non-sprayed area)) ⁇ 100
  • control value was 80% or more when any compound was used.
  • Example 5 Wheat powdery mildew control effect test by foliar spray treatment> The second leaf stage wheat (cultivar: Norin 61) grown using a square plastic pot (6 cm ⁇ 6 cm), in the form of wettable powder of compounds (IVa) to (IVd) as in Preparation Example 1 was suspended in water at a predetermined concentration (50 mg / L) and sprayed at a rate of 1,000 L / ha. After airing the sprayed leaves, wheat seedlings infected with wheat powdery mildew were sprinkled with powdery mildew fungus.
  • ⁇ Test Example 6 Wheat blight control effect test by foliar spray treatment>
  • a compound (IVa) in the form of a wettable powder as in Preparation Example 1 was added with water.
  • the suspension was diluted to a predetermined concentration (25 mg / L) and sprayed at a rate of 1,000 L / ha.
  • spray inoculated with a spore suspension of wheat blight fungus adjusted to 1 ⁇ 10 6 cells / ml, containing Gramine S with a final concentration of 60 ppm), and 48 hours at 25 ° C.
  • Control value (%) (1 ⁇ (average morbidity in sprayed area / average illness in non-sprayed area)) ⁇ 100 As a result, the control value was 80% or more when any compound was used.
  • Control value (%) (1 ⁇ (average morbidity in sprayed area / average illness in non-sprayed area)) ⁇ 100
  • control value was 50% or more when any compound was used.
  • Compound (IVa) was dissolved in dimethyl sulfoxide and added to PDA medium (potato-dextrose-aggar medium) at around 60 ° C. After thoroughly mixing in an Erlenmeyer flask, the mixture was poured into a petri dish and solidified to prepare a plate medium containing compound (IVa) at a predetermined concentration (5 mg / L).
  • PDA medium potato-dextrose-aggar medium
  • test bacteria Gaeumannomyces graminis, barley leaf rot fungus (Pyrenophora graminea), or wheat leaf blight fungus (Septoria tritici)
  • a cork borer having a diameter of 4 mm.
  • inoculated on the above-mentioned drug-containing plate medium After inoculation, each fungus was cultured at an appropriate temperature for growth (for example, LIST OF CULTURES 1996 microorganisms 10th edition, refer to the literature of Foundation for Fermentation, etc.) for 1 to 14 days, and the growth of the fungus was measured by the fungus diameter.
  • the growth degree of the bacteria obtained on the drug-containing plate medium was compared with the growth degree of the bacteria in the drug-free group, and the mycelial elongation suppression rate was determined by the following formula.
  • R represents the hyphal elongation inhibition rate (%)
  • dc represents the diameter of the fungus on the untreated plate
  • dt represents the diameter of the fungus on the drug-treated plate.
  • R 100 (dc ⁇ dt) / dc
  • the mycelial elongation suppression rate R was 80% or more for all the bacteria.
  • Compound (IVc) suspended in olive oil was orally administered to 5 female mice at a dose of 300 mg / kg, and toxicity was examined using life and death, body weight changes and anatomical findings as indices. As a result, no death was observed in any animal 14 days after administration. Body weight increased steadily after administration in all cases. At autopsy, no abnormalities were observed in all cases.
  • the present invention can be suitably used as an active ingredient of a control agent that can minimize plant phytotoxicity and can control plant diseases.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Pour fournir un composé qui présente un effet élevé de contrôle par rapport à une maladie de plante, qui a une toxicité réduite par rapport aux êtres humains et aux animaux et qui est capable de supprimer une lésion chimique à un faible niveau, ce dérivé d'azole a la structure représentée par la formule générale (I) ou (III).
PCT/JP2012/074009 2011-09-27 2012-09-20 Dérivé d'azole, produit chimique pour l'agriculture/l'horticulture, agent protecteur de matière industrielle, procédé de contrôle d'une maladie des plantes et semence WO2013047308A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-211239 2011-09-27
JP2011211239 2011-09-27

Publications (1)

Publication Number Publication Date
WO2013047308A1 true WO2013047308A1 (fr) 2013-04-04

Family

ID=47995340

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/074009 WO2013047308A1 (fr) 2011-09-27 2012-09-20 Dérivé d'azole, produit chimique pour l'agriculture/l'horticulture, agent protecteur de matière industrielle, procédé de contrôle d'une maladie des plantes et semence

Country Status (1)

Country Link
WO (1) WO2013047308A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018522821A (ja) * 2015-05-18 2018-08-16 ヴィアメット ファーマスーティカルズ（エヌシー），インコーポレイテッド 抗真菌性化合物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63264462A (ja) * 1986-12-30 1988-11-01 ジヤンセン・フアーマシューチカ・ナームローゼ・フエンノートシヤツプ １−メチル−１ｈ−イミダゾール−５−カルボン酸誘導体
JPH03501726A (ja) * 1987-12-17 1991-04-18 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 抗真菌性カルビノール
JP2000511164A (ja) * 1996-05-21 2000-08-29 バイエル・アクチエンゲゼルシヤフト メルカプト―イミダゾリル誘導体および殺微生物剤としてのそれらの使用
WO2010149758A1 (fr) * 2009-06-25 2010-12-29 Basf Se Dérivés de 1,2,4-triazole antifongiques
WO2011070742A1 (fr) * 2009-12-08 2011-06-16 Kureha Corporation Dérivés azole et leurs procédés de production, composés intermédiaires pour synthétiser les dérivés et leurs procédés de production, et agents agro-horticoles et agents de protection de produits industriels contenant les dérivés
WO2012115070A1 (fr) * 2011-02-25 2012-08-30 株式会社クレハ Produit agrochimique et son procédé de fabrication

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63264462A (ja) * 1986-12-30 1988-11-01 ジヤンセン・フアーマシューチカ・ナームローゼ・フエンノートシヤツプ １−メチル−１ｈ−イミダゾール−５−カルボン酸誘導体
JPH03501726A (ja) * 1987-12-17 1991-04-18 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 抗真菌性カルビノール
JP2000511164A (ja) * 1996-05-21 2000-08-29 バイエル・アクチエンゲゼルシヤフト メルカプト―イミダゾリル誘導体および殺微生物剤としてのそれらの使用
WO2010149758A1 (fr) * 2009-06-25 2010-12-29 Basf Se Dérivés de 1,2,4-triazole antifongiques
WO2011070742A1 (fr) * 2009-12-08 2011-06-16 Kureha Corporation Dérivés azole et leurs procédés de production, composés intermédiaires pour synthétiser les dérivés et leurs procédés de production, et agents agro-horticoles et agents de protection de produits industriels contenant les dérivés
WO2012115070A1 (fr) * 2011-02-25 2012-08-30 株式会社クレハ Produit agrochimique et son procédé de fabrication

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018522821A (ja) * 2015-05-18 2018-08-16 ヴィアメット ファーマスーティカルズ（エヌシー），インコーポレイテッド 抗真菌性化合物
US11051514B2 (en) 2015-05-18 2021-07-06 Mycovia Pharmaceuticals, Inc. Antifungal compounds

Similar Documents

Publication Publication Date Title
KR102148124B1 (ko) 아졸 유도체, 중간체 화합물 및 아졸 유도체의 제조 방법, 및 농원예용 약제 및 공업용 재료 보호제
JP5886847B2 (ja) アゾール誘導体、その製造方法、中間体化合物、ならびに農園芸用薬剤および工業用材料保護剤
JP5831990B2 (ja) アゾール誘導体およびその製造方法、該誘導体の中間体化合物、ならびに農園芸用薬剤
JP5881733B2 (ja) アゾール誘導体、およびその利用
JP2013512857A (ja) アゾール誘導体及びその製造方法、該誘導体の中間体化合物及びその製造方法、並びに該誘導体を含有する農園芸用薬剤及び工業用材料保護剤
JP5826839B2 (ja) アゾール誘導体、アゾール誘導体の製造方法、および中間体化合物
WO2009088070A1 (fr) Dérivé de (méthyl hétérocyclique)azolylméthylcyclopentanol et son intermédiaire, procédé de fabrication du dérivé et préparation pour l'agriculture ou l'horticulture et agent protecteur pour une substance industrielle comprenant chacun le dérivé
JP5858999B2 (ja) 農園芸用薬剤、植物病害防除組成物、植物病害防除方法および植物病害防除用製品
JP7150213B2 (ja) アゾール誘導体、アゾール誘導体の製造方法、ならびに農園芸用薬剤
WO2010074021A1 (fr) Dérivé de 1-(1-chlorocyclopropyle)-2-(1h-1,2,4-triazole-1-yle)-2-propène-1-ole substitué, son procédé de production, et produit chimique employé en agriculture/horticulture et agent de protection des équipements industriels contenant celui-ci
JP2012219019A (ja) ヒドロキシイソキサゾール誘導体およびこれを含有する殺菌剤
WO2013047308A1 (fr) Dérivé d'azole, produit chimique pour l'agriculture/l'horticulture, agent protecteur de matière industrielle, procédé de contrôle d'une maladie des plantes et semence
JP5859000B2 (ja) オキセタン化合物の製造方法、アゾリルメチルシクロペンタノール化合物の製造方法、および中間体化合物
JP2013100238A (ja) トリアゾール誘導体、中間体化合物、およびトリアゾール誘導体の製造方法、ならびに農園芸用薬剤および工業用材料保護剤
JP2019031463A (ja) アゾール誘導体、およびその農園芸用薬剤としての利用
WO2012169522A1 (fr) Agent chimique agricole ou horticole, procédé de lutte contre les maladies des plantes et produit pour lutter contre les maladies des plantes
WO2013084770A1 (fr) Dérivé d'azole, procédé de production d'un dérivé d'azole, composé intermédiaire, médicament pour des applications agricoles et horticoles et protecteur d'une substance industrielle
WO2014024897A1 (fr) Dérivés de thiazolidinediones et de pyrrolidinediones et germicide utilisant ces composés en tant qu'ingrédients actifs
JP2016033127A (ja) 農園芸用薬剤
JP2012250961A (ja) アゾール誘導体およびその製造方法、該誘導体の中間体化合物ならびに該誘導体を含有する農園芸用薬剤および工業用材料保護剤
WO2012165499A1 (fr) Composé de type triazole et son utilisation
JP2012219020A (ja) ５−メチル−３（２ｈ）−イソキサゾロン誘導体およびこれを含有する農園芸用薬剤
WO2012165498A1 (fr) Composé de triazole et son utilisation
JP2012250942A (ja) 茎葉病害防除剤および植物病害防除方法

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: 12836327

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12836327

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP