WO2021230382A1 - (-)-énantiomère de dérivé de triazole, produit chimique agricole ou horticole, et produit de protection de matériau industriel - Google Patents

(-)-énantiomère de dérivé de triazole, produit chimique agricole ou horticole, et produit de protection de matériau industriel Download PDF

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WO2021230382A1
WO2021230382A1 PCT/JP2021/018610 JP2021018610W WO2021230382A1 WO 2021230382 A1 WO2021230382 A1 WO 2021230382A1 JP 2021018610 W JP2021018610 W JP 2021018610W WO 2021230382 A1 WO2021230382 A1 WO 2021230382A1
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group
phenyl
alkyl
enantiomer
halogen
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朋之 高下
竜行 越山
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株式会社クレハ
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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
    • A01N43/64—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
    • 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
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • 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
    • 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

Definitions

  • the present invention relates to a triazole derivative (-)-enantiomer, and an agricultural and horticultural agent containing the triazole derivative as an active ingredient, and an industrial material protective agent.
  • Patent Document 1 discloses a novel triazole derivative which is an active ingredient of an agricultural and horticultural drug.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a compound having high antibacterial activity against plant diseases, which can be expected to have a high control effect against plant diseases even at a low application amount. To do.
  • the compound according to the present invention is a (-)-enantiomer of a triazole derivative represented by the following general formula (I) or a pesticide-acceptable salt thereof.
  • R 1 is -OR 4 or -NR 5 R 6 ;
  • R 4 , R 5 and R 6 are independently hydrogen, C 1- C 6 -alkyl group, C 2- C 6 -alkenyl group, C 2- C 6 -alkynyl group, C 3- C 8 -cyclo.
  • Alkyne group C 3- C 8 -cycloalkyl-C 1- C 4 -alkyl group, phenyl group, phenyl-C 1- C 4 -alkyl group, phenyl-C 2- C 4 -alkenyl group or phenyl-C 2 -C 4- It is an alkynyl group, and R 5 and R 6 may form a ring; Here, the aliphatic groups in R 4 , R 5 and R 6 may have 1, 2, 3 or the maximum possible number of the same or different groups R a , where R a is a halogen group.
  • cyano group, nitro group, C 1 -C 4 - alkoxy and C 1 -C 4 - is selected from haloalkoxy groups independently of each other;
  • R 2 is a halogen group, a cyano group, a nitro group, a phenyl group, a phenyl-oxy group, a C 1- C 4 -alkyl group, a C 1- C 4 -haloalkyl group, a C 1- C 4 -alkoxy group, and a C 1-.
  • R 3 is a halogen group, a cyano group, a nitro group, an amino group, a phenyl group, a phenyl-oxy group, a C 1- C 4 -alkyl group, a C 1- C 4 -haloalkyl group, and a C 1- C 4 -alkoxy group.
  • C 1 -C 4 - haloalkoxy group, C 1 -C 4 - alkylamino group, C 1 -C 4 - dialkylamino group, C 1 -C 4 - alkyl acyl amino group, in -SOR 7 or -SF 5 can be;
  • the cycloalkyl and phenyl group moieties in R 4 , R 5 , and R 6 and the phenyl group moieties in R 3 have 1, 2, 3, 4, 5 or the maximum number of possible identical or different groups R b .
  • R b is halogen, cyano, nitro, C 1 -C 4 - alkyl group, C 1 -C 4 - alkoxy group, C 1 -C 4 - haloalkyl and C 1 -C 4- Selected independently of each other from the haloalkoxy group;
  • R 7 is, C 1 -C 4 - alkyl group or a C 1 -C 4 - haloalkyl group;
  • n is 0,1,2,3, or 4;
  • m is 1,2,3,4 or 5
  • An asterisk (*) refers to an asymmetric carbon atom. ]
  • the (-)-enantiomer of the triazole derivative according to the present invention has an excellent bactericidal action against many bacteria that cause diseases to plants even at a low application amount.
  • Triazole derivative enantiomer The (-)-enantiomer of the triazole derivative according to the present embodiment is the (-)-enantiomer (hereinafter, triazole derivative (-) in the triazole derivative represented by the following general formula (I) (hereinafter referred to as triazole derivative (I))). ) -Called an enantiomer).
  • the asterisk (*) in the following general formula (I) refers to an asymmetric carbon atom.
  • the "(-)-enantiomer” refers to an enantiomer that rotates the vibration plane of the linearly polarized light of the sodium D line to the left
  • the "(+)-enantiomer” refers to the sodium D line. Refers to an enantiomer that rotates the vibrating plane of linearly polarized light to the right.
  • R 1 is -OR 4 or -NR 5 R 6 , preferably -OR 4 .
  • R 4 , R 5 and R 6 are independently hydrogen, C 1- C 6 -alkyl group, C 2- C 6 -alkenyl group, C 2- C 6 -alkynyl group, C 3- C 8 -cyclo. Alkyl group, C 3- C 8 -cycloalkyl-C 1- C 4 -alkyl group, phenyl group, phenyl-C 1- C 4 -alkyl group, phenyl-C 2- C 4 -alkenyl group or phenyl-C 2 -C 4 -Alkynyl group.
  • R 5 and R 6 may form a ring together with the nitrogen atom to which R 5 and R 6 are bonded.
  • C 1 -C 6 - alkyl group is a straight chain or branched chain alkyl group with a carbon number 1-6, for example, a methyl group, an ethyl group, a 1-methylethyl group, 1,1-dimethyl Ethyl group, propyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, butyl group, 1-methylbutyl group, 2- Methylbutyl group, 3-methylbutyl group, 3,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, pentyl group, 1-methylpentyl group , 2-Methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.
  • C 2 -C 6 - alkenyl group is a linear or branched alkenyl group having a carbon atom is 2-6, for example, ethenyl, 2-propenyl group, 1-methyl-2-propenyl group , 2-Methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-methyl-2-butenyl group, 1-methyl-2-butenyl group, 3-butenyl group, 1-pentenyl group, 2- Examples include a pentanyl group, a 1-hexenyl group and a 5-hexenyl group.
  • C 2 -C 6 - alkynyl group a linear or branched chain alkynyl group having a carbon atom is 2-6, for example, ethynyl group, 1-propynyl, 2-propynyl, 1-butynyl Examples include groups, 2-butynyl groups, 3-butynyl groups, pentynyl groups and 1-hexynyl groups.
  • the C 3- C 8 -cycloalkyl group is a cyclic alkyl having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Be done.
  • the C 3- C 8 -cycloalkyl-C 1- C 4 -alkyl group consists of a cyclic cycloalkyl group having 3 to 8 carbon atoms and a linear or branched-chain alkyl group having 1 to 4 carbon atoms. Indicates that they are combined. For example, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, 2-cyclopropylethyl group, 1-cyclopropylethyl group, 2-cyclohexylethyl group, 3-cyclopropylpropyl group, 2-cyclo Examples thereof include a propylpropyl group and a 4-cyclopropylbutyl group.
  • the phenyl-C 1- C 4 -alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a phenyl group, for example, a phenylmethyl group, a 2-phenylethyl group, and the like. Examples include 3-phenylpropyl group and 4-phenylbutyl group.
  • the phenyl-C 2- C 4 -alkenyl group has a linear or branched alkenyl group having 2 to 4 carbon atoms bonded to the phenyl group, for example, a phenylethenyl group or a phenyl-1-propenyl.
  • Groups include groups, phenylisopropenyl groups, and phenylbutenyl groups.
  • the phenyl-C 2- C 4 -alkynyl group has an alkynyl group having 2 to 4 carbon atoms bonded to the phenyl group, and is, for example, a phenylethynyl group, a phenyl-1-propynyl group, or a phenyl-2-propynyl group. , Phenyl-1-butynyl group, phenyl-2-butynyl group, and phenyl-3-butynyl group.
  • R 4 is preferably, C 1 -C 6 - alkyl group.
  • the aliphatic groups in R 1 , R 4 , R 5 and R 6 may have 1, 2, 3 or the maximum possible number of the same or different groups R a , where R a is a halogen group. , cyano group, nitro group, C 1 -C 4 - independently of each other selected from haloalkoxy group - alkoxy group and C 1 -C 4.
  • halogen group examples include a chlorine group, a bromine group, an iodine group or a fluorine group.
  • a chloromethyl group, a 2-chloroethyl group, a 2,3-dichloropropyl group, a bromomethyl group, a chlorodifluoromethyl group, a trifluoromethyl group, and a 3,3,3-trifluoropropyl group can be mentioned.
  • C 1 -C 4 - alkoxy group is a linear or branched alkoxy group having 1 to 4 carbon atoms, e.g., methoxy, ethoxy, n- propoxy, isopropoxy, n- butoxy Examples include a group, a sec-butoxy group, and a tert-butoxy group.
  • halogen groups may be the same or different.
  • R 2 is a halogen group, a cyano group, a nitro group, a phenyl group, a phenyl-oxy group, a C 1- C 4 -alkyl group, a C 1- C 4 -haloalkyl group, a C 1- C 4 -alkoxy group, and a C 1 -C 4 -haloalkoxy group, -SOR 7 or -SF 5 .
  • Halogen C 1 -C 4 - alkyl group, C 1 -C 4 - haloalkyl group, C 1 -C 4 - alkoxy groups, and C 1 -C 4 - haloalkoxy group, an organic group represented by R a
  • R a The groups mentioned as an example of the above can be mentioned.
  • R 2 is preferably a halogen group, a cyano group, C 1 -C 4 - alkyl group, C 1 -C 4 - haloalkyl group, C 1 -C 4 - alkoxy group, an -SOR 7, or -SF 5, more preferably, a halogen group, a cyano group, C 1 -C 4 - alkoxy group - alkyl group, C 1 -C 4 - haloalkyl group or a C 1 -C 4.
  • R 7 is, C 1 -C 4 - alkyl group or a C 1 -C 4 - haloalkyl group.
  • the substitution position of R 2 is the 2nd, 3rd, 5th or 6th position, preferably the 2nd position.
  • n is 0, 1, 2, 3 or 4, preferably 1.
  • R 3 is a halogen group, a cyano group, a nitro group, an amino group, a phenyl group, a phenyl-oxy group, a C 1- C 4 -alkyl group, a C 1- C 4 -haloalkyl group, and a C 1- C 4 -alkoxy group.
  • C 1 -C 4 - haloalkoxy group C 1 -C 4 - alkylamino group, C 1 -C 4 - dialkylamino group, C 1 -C 4 - alkyl acyl amino group, -SOR 7, or -SF 5 Yes
  • the halogen group, C 1- C 4 -alkyl C 1- C 4 -haloalkyl group, C 1- C 4 -alkoxy group or C 1- C 4 -halo alkoxy group, and -SOR 7 are represented by R 2. Examples of the organic groups mentioned above can be mentioned.
  • R 3 is preferably a halogen group, a nitro group, an amino group, C 1 -C 4 - alkyl group, C 1 -C 4 - haloalkyl group, C 1 -C 4 - alkoxy group, C 1 -C 4 - halo alkoxy groups, C 1 -C 4 - alkylamino group, C 1 -C 4 - dialkylamino group, C 1 -C 4 - alkyl acyl amino group, an -SOR 7, or -SF 5, more preferably a halogen group , C 1- C 4 -alkyl group, C 1- C 4 -haloalkyl group, C 1- C 4 -alkoxy group or C 1- C 4 -haloalkoxy group.
  • C 1 -C 4 - alkylamino group is one of an amino group substituted with a straight-chain or branched alkyl group having 1 to 4 carbon atoms of the hydrogen atom of the amino group, e.g., methylamino
  • Examples include groups, ethylamino groups, n-propylamino groups, isopropylamino groups, and tert-butylamino groups.
  • C 1 -C 4 - dialkylamino group is an amino group in which a hydrogen atom of two co-having amino group substituted by a straight or branched chain alkyl group having 1 to 4 carbon atoms, e.g., N , N-dimethylamino group, N, N-diethylamino group, N, N-di-n-propylamino group, N, N-diisopropylamino group, and N, N-di-tert-butylamino group.
  • C 1 -C 4 - alkyl acyl amino group it is one or two amino groups substituted with a linear or branched alkyl acyl group of 1 to 4 carbon atoms of the hydrogen atom of the amino group
  • Examples thereof include N, N-di-n-propyl acylamino groups, N, N-diisopropyl acylamino groups, and N, N-di-tert-butyl acylamino groups.
  • the cycloalkyl or phenyl group moiety in R 4 , R 5 , R 6 or the phenyl group moiety in R 3 has 1, 2, 3, 4, 5 or the maximum number of possible identical or different groups R b .
  • R b is halogen, cyano, nitro, C 1 -C 4 - alkyl group, C 1 -C 4 - alkoxy group, C 1 -C 4 - haloalkyl and C 1 -C 4- Selected independently of each other from the haloalkoxy group.
  • R 1 is located at -OR 4;
  • R 2 is halogen, cyano, C 1 -C 4 - Alkoxy group, C 1- C 4 -haloalkyl group, C 1- C 4 -alkoxy group, -SOR 7 or -SF 5 ;
  • R 3 is halogen group, nitro group, cyano group, amino group, C 1- C 4 - alkyl group, C 1 -C 4 - haloalkyl group, C 1 -C 4 - alkoxy group, C 1 -C 4 - haloalkoxy group, C 1 -C 4 - alkylamino group, C 1 -C 4 - dialkylamino group, C 1 -C 4 - alkyl acyl amino group, an -SOR 7, or -SF 5, triazole derivative (-) - include enantiomers.
  • R 1 is -OR 4 and R 4 is a C 1- C 6 -alkyl group
  • R 2 is a halogen group, a cyano group, a C 1- C 4 -alkyl group, a C 1- C 4 -haloalkyl group or a C 1- C 4 -alkoxy group
  • R 3 is a halogen group, a cyano group, C.
  • Examples thereof include a triazole derivative (-)-enantiomer which is a 1- C 4 -alkyl group, a C 1- C 4 -haloalkyl group, a C 1- C 4 -alkoxy group or a C 1- C 4-haloalkoxy group.
  • a triazole derivative (-)-enantiomer which is a 1- C 4 -alkyl group, a C 1- C 4 -haloalkyl group, a C 1- C 4 -alkoxy group or a C 1- C 4-haloalkoxy group.
  • Agriculturally acceptable salts of triazole derivative (-)-enantiomers in particular salts of these cations or acids thereof, whose cations and anions do not adversely affect the action of the triazole derivative (-)-enantiomer.
  • Suitable cations are particularly ammonium ions of alkali metals (preferably sodium and potassium), alkaline earth metals (preferably calcium, magnesium and barium), transition metals (preferably manganese, copper, zinc and iron) and also.
  • 1 to 4 C 1 -C if desired 4 - alkyl substituents and / or one phenyl substituent or benzyl substituent optionally may ammonium ions (preferably diisopropyl ammonium have, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium), furthermore phosphonium ions, sulfonium ions (preferably tri (C 1 -C 4 - alkyl) sulfonium), and sulfoxonium ions (preferably tri (C 1 -C 4 - alkyl) sulfonium It is also (xonium).
  • ammonium ions preferably diisopropyl ammonium have, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium
  • phosphonium ions preferably tri (C 1 -C 4 - alkyl) sulfonium
  • the anions of useful acid addition salts are mainly chloride ion, bromide ion, fluoride ion, hydrogen sulfate ion, sulfate ion, dihydrogen phosphate ion, hydrogen phosphate ion, phosphate ion, nitrate ion, bicarbonate.
  • These can be formed by reacting the triazole derivative (-)-enantiomer with the corresponding anionic acid (preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid).
  • Triazole derivative (-)-Production method of enantiomer [1. Preparation of triazole derivative (-)-enantiomer by optical resolution]
  • the triazole derivative (-)-enantiomer can be obtained by preparative separation from the racemate of the triazole derivative (I).
  • the racemate of the triazole derivative (I) can be obtained, for example, according to the method described in Patent Document 1.
  • the obtained triazole derivative is a racemate.
  • Examples of the method for separating enantiomers include a method for separating by chiral chromatography. Specifically, amylostris (3,5-dimethylphenylcarbamate), cellulosetris (3,5-dimethylphenylcarbamate), cellulosetris (3,5-dichlorophenylcarbamate), amylostris [(S) - ⁇ -methyl Benzyl carbamate], cellulose tris (4-methylbenzoate), amylose tris (5-chloro-2-methylphenyl carbamate) or cellulose tris (3-chloro-4-methylphenyl carbamate) on a stationary phase immobilized on a silica gel carrier.
  • the triazole derivative (I) is separated from the racemic form.
  • a triazole derivative (-)-enantiomer can be prepared.
  • optical rotation of the separated (-)-enantiomer may be determined according to a conventionally known method.
  • compound (N) the compound represented by the general formula (N) (where N is an arbitrary Roman numeral) in the overall scheme is referred to as compound (N).
  • Step 1 a compound (VII) is obtained by introducing a methyl group into the compound (VIII).
  • R 7 in the compound (VIII) is C 1 -C 6 - alkyl group.
  • a methylation reagent is added to a solution of compound (VIII) at a low temperature (for example, ⁇ 78 ° C.) and reacted.
  • methylation reagent examples include trimethylaluminum, methylmagnesium chloride, methylmagnesium bromide, and methyllithium.
  • solvent in step 1 examples include ethers such as tetrahydrofuran, dioxane and diethyl ether, and organic solvents such as toluene and hexane which are inert to the reaction.
  • Step 2 a compound (VI) is obtained by forming an exoolefin from the compound (VII) by a dehydration reaction using an acid catalyst.
  • step 3 the ester portion of compound (VI) is reduced to alcohol to obtain compound (V).
  • the compound (V) is obtained by mixing the compound (VI) and the hydride reducing agent in a solvent at a low temperature (for example, 0 ° C.) or at room temperature.
  • solvent in step 3 examples include ethers such as tetrahydrofuran, dioxane and diethyl ether, reaction-inactive toluene and dichloromethane, and organic solvents such as a mixture thereof.
  • hydride reducing agent examples include lithium aluminum hydride and diisobutylaluminum hydride.
  • step 4 compound (IV) is obtained by epoxidizing the olefin moiety of compound (V).
  • titanium (IV) tetraisopropoxide, diethyl L- (+)-diethyl tartrate and tert-butyl hydroperoxide are mixed in dichloromethane at a low temperature (for example, -20 ° C.), and compound (V) is added thereto.
  • a low temperature for example, -20 ° C.
  • compound (V) is added thereto.
  • examples thereof include, but are not limited to, a method of adding and reacting at a low temperature.
  • step 5 compound (III) is obtained by oxidizing the alcohol moiety of compound (IV) to a carboxylic acid. Specifically, compound (III) is obtained by mixing ruthenium trichloride, sodium periodate and compound (IV) in a solvent at room temperature.
  • Examples of the solvent in step 5 include water, carbon tetrachloride, acetonitrile and ethyl acetate, and a mixed solvent composed of these solvents.
  • step 6 compound (II) is obtained from compound (III).
  • R 1 is OR 4 and R 4 is hydrogen, the compound (II) and the compound (III) are the same, so that this step is not necessary.
  • R 1 is OR 4 and R 4 is alkyl
  • a method of obtaining compound (II) by alkylating compound (III) can be mentioned.
  • carbonates examples include sodium carbonate, potassium carbonate, cesium carbonate and lithium carbonate.
  • LG has a leaving group that can be substituted nucleophilically, for example, a leaving group selected from a halogen group, an alkylsulfonyloxy group and an arylsulfonyloxy group.
  • compound (II) is obtained by condensing compound (III) with an amine.
  • Specific examples thereof include a method in which compound (III), an amine, a base and a condensing agent are mixed in a solvent and reacted at room temperature.
  • Examples of the solvent in step 6 include amides such as N, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylformaldehyde, and organic solvents such as dichloromethane and dichloroethane which are inert to the reaction.
  • amides such as N, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylformaldehyde
  • organic solvents such as dichloromethane and dichloroethane which are inert to the reaction.
  • Examples of the base include trisubstituted amines such as triethylamine, diisopropylethylamine and N, N-dimethyl-4-aminopyridine.
  • condensing agent examples include 1- [bis (dimethylamino) methylene] -1H-1,2,3-triazolo [4,5-b] pyridinium 3-oxide hexafluorophosphate (HATU) and 1- [bis. (Dimethylamino) Methylene] -1H-benzotriazolinium 3-oxide hexafluorophosphate (HBTU) and 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate (PyBOP) and the like.
  • HATU 1- [bis (dimethylamino) methylene] -1H-1,2,3-triazolo [4,5-b] pyridinium 3-oxide hexafluorophosphate
  • HBTU -1H-benzotriazolinium 3-oxide hexafluorophosphate
  • PyBOP 1H-benzotriazole-1-yloxytripyrrolidinophosphonium
  • step 7 the oxylan ring in the compound (II) is obtained by mixing the compound (II) and the azole compound in a solvent by a known method (for example, the method described in Patent Document: Japanese Patent Application Laid-Open No. 2013-100238).
  • the compound (I), that is, the triazole derivative (I) is produced by forming a carbon-nitrogen bond between the carbon atom constituting the compound and the nitrogen atom of the azole compound.
  • Examples of the azole compound include 1,2,4-triazole or an alkali metal salt thereof.
  • the solvent of step 7 is not particularly limited, and for example, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylacetamide, N-methylpyrrolidone and N, N. -Amids such as dimethylformaldehyde, as well as dimethylsulfoxide can be mentioned.
  • a base may be added if desired.
  • the base include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide and potassium t-butoxide, and potassium carbonate and the like.
  • the triazole derivative (-)-enantiomer has a 1,2,4-triazolyl group, it forms an acid addition salt or metal complex of an inorganic acid and an organic acid. Therefore, it can be used as an active ingredient of agricultural and horticultural chemicals as a part of an acid addition salt and a metal complex.
  • the fungicide for agriculture and horticulture in the present embodiment exhibits a control effect against a wide range of plant diseases.
  • Examples of applicable diseases include the following.
  • the parentheses after each disease indicate the main pathogens that cause the disease.
  • Soybean rust Phakopsora pachyrhizi, Phakopsora meibomiae
  • soybean brown spot disease Zymoseptria glycines
  • soybean purple spot disease Cercospora kikuchiri
  • soybean brown spot disease Alter
  • spot Cercocopora sojina
  • soybean lysoctonia root rot Rhizoctonia soly
  • soybean leaf rot Rhizoctonia soly
  • soybean black spot disease Diaporthe phaselorum
  • Rapeseed Phoma leaf spot / stem canker Leptosphaeria maculans, Leptosphaeria biglobosa
  • Light leaf of rapeseed spot Pyrenopeziza brassicae
  • rapeseed root-knot disease Clubloot Piericae
  • Cercosporidium personatum Cercospora arachidicola, Cercospora lorfsi, Puccinia arachidis, Banana yellow shigatoka, Mycosphaerella Gray mold (Botrytis sinerea), disease of the genus Pythium (Pythium spp) and mycosphaerella (Cercospora), etc. that damage various crops.
  • the genus Aspergillus the genus Cochliobolus, the genus Corticium, the genus Diplodia, the genus Pencillum, the genus Gibberala, the genus Mucor, the genus Phoma, the genus Phomopsis, the genus Pyrenophora, and the genus Pyrenophora. Seed-borne diseases or early-growth diseases of various plants caused by the genus Trichoderma, the genus Ustylago, and the like.
  • the fungicide for agriculture and gardening according to the present embodiment exhibits a particularly excellent control effect against the diseases of wheat such as wheat leaf blight and barley Fusarium head blight. Therefore, agricultural and horticultural fungicides are suitably used for controlling wheat, but are not limited thereto.
  • the agricultural and horticultural fungicides in this embodiment can be used for all plants, and examples of applicable plants include the following.
  • Satoimo family such as Satoimo
  • Urushi family such as mango, Pineapple family such as pineapple
  • Papaya family such as papaya
  • Kakinoki family such as oyster
  • Tsutsuji family such as blueberry
  • Walnut such as Pekan Family
  • Basho family such as banana
  • Mokusei family such as olive
  • Palm family such as Coco palm and Natsume palm
  • Mikan family such as tangerine, orange, grapefruit and lemon
  • Grape family such as grape, Flowers and ornamental plants), trees other than fruit trees, and other ornamental plants.
  • wild plants, plant cultivars, plants and plant cultivars obtained by conventional biological breeding such as crossbreeding or progenitor fusion, and genetically modified plant cultivars obtained by genetic engineering and approved in each country can be mentioned. ..
  • Examples of such genetically modified plant cultivars include those accumulated in the database of the International Agribio Corporation (ISAAA). Specifically, Roundup Ready, Liberty Link, IMI, SCS, Clearfield, Enlist, B.I. t.
  • the agricultural and horticultural chemicals are prepared by mixing the triazole derivative (-)-enantiomer according to the present embodiment, which is an active ingredient, with a solid carrier or a liquid carrier (diluent), a surfactant, other pharmaceutical adjuncts, and the like, and powder and water. It is formulated and used in various forms such as Japanese preparations, granules and emulsions.
  • These preparations contain the triazole derivative (-)-enantiomer as an active ingredient in an amount of 0.05 to 95% by weight, preferably 0.25 to 90% by weight, and more preferably 1 to 80% by weight.
  • solid carriers, liquid carriers and surfactants used as formulation aids are as follows. First, solid carriers are used as powder carriers, granular carriers and the like, and clay, talc, diatomaceous earth, zeolite, montmorillonite, bentonite and acidic.
  • Minerals such as white clay, active white clay, attapargit, calculus, vermiculite, pearlite, pebbles, silica sand; synthetic organic substances such as urea; salts such as calcium carbonate, sodium carbonate, sodium sulfate, limestone, and baking soda; amorphous such as white carbon.
  • Synthetic inorganic substances such as quality silica and titanium dioxide; plants such as wood flour, corn stalk (cob), walnut shell (hard fruit hull), fruit nucleus, fir, oak, bran, soybean flour, powdered cellulose, starch, dextrin, sugar, etc.
  • Sex carriers crosslinked lignin, cationic gels, gelatin gelled with heating or polyvalent metal salts, water-soluble polymer gels such as agar, and chlorinated polyethylene, chlorinated polypropylene, polyvinyl acetate, polyvinyl chloride, ethylene-vinyl acetate.
  • examples thereof include various polymer carriers such as copolymers and urea-aldevido resins.
  • Liquid carriers include fatty acid solvents (paraffins), aromatic solvents (xylene, alkylbenzene, alkylnaphthalene, solvent naphtha, etc.), mixed solvents (kerosene), machine oils (refined high boiling fatty acid hydrocarbons), alcohols (alcohols).
  • paraffins paraffins
  • aromatic solvents xylene, alkylbenzene, alkylnaphthalene, solvent naphtha, etc.
  • mixed solvents kerosene
  • machine oils refined high boiling fatty acid hydrocarbons
  • alcohols alcohols
  • nonionic surfactant examples include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene resin acid ester, and polyoxyethylene fatty acid diester.
  • Anionic surfactants include alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene benzyl (or styryl) phenyl (or phenylphenyl) ether sulfate, polyoxyethylene, and polyoxypropylene.
  • Salts of sulfates such as block polymer sulfate, paraffin (alkane) sulfonate, ⁇ -olefin sulfonate, dialkyl sulfosuccinate, alkylbenzene sulfonate, mono or dialkylnaphthalene sulfonate, naphthalene sulfonate formalin condensate, alkyldiphenyl ether disulfonate, lignin sulfonate, Salts of sulfonates such as polyoxyethylene alkylphenyl ether sulfonates, polyoxyethylene alkyl ether sulfosuccinic acid half esters, fatty acids, salts of fatty acids such as N-methyl-fatty acid sarcosinates, resin acids, polyoxyethylene alkyl ether phosphates, Polyoxyethylene mono or dialkylphenyl ether phosphate, polyoxyethylene benzyl (or
  • Cationic surfactants include ammonium salts such as alkyltrimethylammonium chloride, methylpolyoxyethylene alkylammonium chloride, alkyl N-methylpyridium bromide, mono or dialkylmethylated ammonium chloride, alkylpentamethylpropylenediaminedichloride and alkyldimethyl.
  • ammonium salts such as alkyltrimethylammonium chloride, methylpolyoxyethylene alkylammonium chloride, alkyl N-methylpyridium bromide, mono or dialkylmethylated ammonium chloride, alkylpentamethylpropylenediaminedichloride and alkyldimethyl.
  • benzalkonium salts such as benzalkonium chloride and benzethonium chloride (octylphenoxyethoxyethyldimethylbenzylammonium chloride).
  • biosurfactants for example, mannosylargitol lipid, sophorolipid, ramnolipid, trehalose lipid, cellobiose lipid, glucose lipid, oligosaccharide fatty acid ester, surfactin, serauetchin, lykencin, arslofactin, spiclesporic acid, corinomicol). Acid, agaric acid, emalzan, etc. may be contained as a surfactant.
  • biosurfactants for example, mannosylargitol lipid, sophorolipid, ramnolipid, trehalose lipid, cellobiose lipid, glucose lipid, oligosaccharide fatty acid ester, surfactin, serauetchin, lykencin, arslofactin, spiclesporic acid, corinomicol). Acid, agaric acid, emalzan, etc.
  • compositions include inorganic salts such as sodium and potassium as pH adjusters, fluorine-based and silicone-based defoaming agents, water-soluble salts such as salt, and xattan gum and guar gum used as thickeners.
  • Water-soluble polymers such as carboxymethyl cellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, polyvinyl alcohol, starch derivatives, polysaccharides, alginic acid and its salts, metal stearate used as a disintegrant dispersant, sodium tripolyphosphate, hexametallin Acid soda and others include preservatives, colorants, antioxidants, UV absorbers, and chemical damage reducing agents.
  • the concentration of the triazole derivative (-)-enantiomer when diluted and used is preferably in the range of 0.0005 to 1.0%.
  • the amount of the triazole derivative (-)-enantiomer used is 10 to 5000 g, more preferably 25 to 2000 g per 1 ha of horticultural land such as fields, rice fields, orchards and greenhouses. Since these concentrations and amounts used vary depending on the dosage form, timing of use, method of use, place of use, target crop, etc., they can be increased or decreased without being particular about the above range.
  • the agricultural and horticultural agent containing the triazole derivative (-)-enantiomer (I) in the present embodiment can be used in combination with other known active ingredients to enhance the performance as the agricultural and horticultural agent.
  • Other known active ingredients include known active ingredients contained in fungicides, insecticides, acaricides, nematodes, and plant growth regulators.
  • bactericides include nucleic acid synthesis and metabolism inhibitors, threaded nucleus division / cell division inhibitors, respiratory inhibitors, amino acid / protein biosynthesis inhibitors, signal transduction inhibitors, lipid biosynthesis or transport / Examples include cell membrane structure or function inhibitors, cell membrane sterol biosynthesis inhibitors, cell wall biosynthesis inhibitors, melanin biosynthesis inhibitors, host plant resistance inducers, and multi-action point bactericides.
  • nucleic acid synthesis metabolism inhibitor examples include benaraxil, benaraxyl M, furaxyl, offrace, bupirimate, dimethyrimol, etilimol, octylinone, metalaxil, metalaxil-M, oxadixil and himexazole, and are at least one selected from these. obtain.
  • filamentous fission / cell division inhibitor examples include benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate, thiophanate-methyl, dietofencarb, zoxamide, etaboxam, pencyclon, fluoricorid, phenamaclyl, metrafenone and pyriophenone. Can be at least one.
  • Respiratory inhibitors include tolfenpyrado, diflumethrim, phenazakin, pidiflumethofen, fenfuran, carboxin, oxycarboxin, benodanyl, flutranil, mepronil, isofetamide, benzobindiflupill, bixaphen, fluindapyl, fluxapyroxado, Flametopill, isopyrazam, penflufen, penthiopyrado, sedaxan, isoflusiplum, boscalid, fluopirum, thyfluzamide, pyraziflumid, pyribencarb, fluoxastrobin, phenamiden, mandestrobin, azoxystrobin, spumoxystrobin, enoxastrobin, full Phenoxystrobin, picoxystrobin, pyracrostrobin, pyraoxystrobin, trichloropyricalve, famoxadon, dymoxystrobin
  • amino acid / protein biosynthesis inhibitor examples include cyprodinyl, mepanipyrim, pyrimethanyl, blastsidedin, kasugamycin, streptomycin, oxytetracycline and the like, and may be at least one selected from these.
  • Examples of the signal transduction inhibitor include quinoxyphen, proquinazide, clozoline, dimethacron, phenpicronyl, fludioxonyl, iprodion, procymidone, vinclozoline and the like, and may be at least one selected from these.
  • Lipid biosynthesis or transport / cell membrane structure or function inhibitors include isoprothiolan, edifenphos, iprobenphos (IBP), pyrazophos, biphenyl, chloroneb, dichloran, quintozen (PCNB), technazen (TCNB), torquelophos- Methyl, etridiazole, prothiocarb, propamocarb, natamycin, oxathiapiproline, fluoxapiproline and the like can be mentioned and may be at least one selected from these.
  • Cell membrane sterol biosynthesis inhibitors include imazalyl, oxpoconazole, pefrazoate, prochloraz, triflumizole, trifolin, pyrifenox, pyrisoxazole, phenalimol, nuarimol, azaconazole, bitertanol, bromconazole, cyproconazole, Diphenoconazole, diniconazole, epoxyconazole, etaconazole, fenbuconazole, fluconazole, fluconazole, flutrifolin, hexaconazole, imibenconazole, metconazole, ipconazole, microbutanyl, penconazole, propiconazole, simeconazole, tebuconazole, tetra.
  • Nazole Triazimefon, Triazimenol, Triticonazole, Mefentrifluconazole, Prothioconazole, Tridemorph, Fenpropimorph, Fenpropidine, Piperline, Spiroxamine, Fempyrazamine, Fenhexamide, Naftiffin, Turbinafin, Pyribycarb and Examples include ipfentrifluconazole and the like, and may be at least one selected from these.
  • cell wall biosynthesis inhibitor examples include polyoxin, dimethmorph, fulmorph, pyrimorph, mandipropamide, benchavaricarb, iprovaricarb, and varifenalate, and may be at least one selected from these.
  • melanin biosynthesis inhibitor examples include fusalide, tricyclazole, pyrochyron, carpropamide, diclosimet, phenoxanyl, tolprocarb and the like, and may be at least one selected from these.
  • Host plant resistance inducers include acibenzolar-S-methyl, probenazole, thiazinyl, laminarin, isothianyl, laminarin, phocetyl-Al, phosphoric acid and phosphate, with at least one selected from these. could be.
  • Multi-action point fungicides include simoxanyl, tecrophthalam, triazoxide, flusulfamide, dichromedin, siflufenamide, dodine, fluthianyl, ferlimzone, tebuflokin, picalbutrazox, varydamycin, mineral oil, baking soda, potassium carbonate, copper and copper compounds, sulfur, Farbam, Manzeb, Manneb, Metylum, Propineb, Thiram, Dineb, Diram, Captan, Captan, Folpet, Chlorotalonyl (TPN), Guazatin, Iminoctadine acetate, Iminoctadine albesylate, Anilazine, Dithianone, Fluorimide, Metasulfocarb , Florylpicoxamide, fluopimomid, ipflufenokin, quinomethionate, pyridaclomethyl, aminopyridene, diclobenazox, quino
  • fenamiden fenitropan, halpin, isonial, diclobenazox, picalbutrazox, hydroxyisoxazole, fluorimide, quinomethionate, chloroinconazide, trichoderma mycelium extract, Gosei Kayupte (tea tree) extract, vegetable oil (eugenol, geraniol, timol), Oitadori extract, cell wall of Saccharomyces cerevisiae LAS117 strain and biopesticides (Agrobacterium radiobacter, Pseudomonas fluorescens, Pseudomonas rodesia, Pseudomonas chlororafis AFS009 strain, Bacillus subtilis, Bacillus symplex, Bacillus amyloliquefaciens, Bacillus mycoides, non-pathogenic Elvinia carotbora, Lactobacillus
  • Known active ingredients in pesticides include nicotinic acetylcholine receptor antagonist modulators, sodium channel modulators, lianodine receptor modulators, acetylcholinesterase inhibitors, oxidative phosphorylation uncouplers, and mitochondrial electron transport chain complex I. Inhibitors and the like can be mentioned.
  • nicotinic acetylcholine receptor antagonist modulator examples include acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor, flupyradiflon, and triflumezopyrim, and may be at least one selected from these.
  • Examples of the sodium channel modulator include pyrethroid compounds, and examples of the pyrethroid compounds include acrinathrin, arereslin, cypermethrin, bifenthrin, cycloprothrin, cyhalothrin, deltamethrin, dimefluthrin, esphenvalerate, etofenprox, and fenpropathrin.
  • Fenvalerate flubrocitrinate, flucitrinate, fluvalinate, halfenprox, cyhalothrin, metoflutrin, monfluorothrin, permethrin, profluthrin, tefluthrin, tralomethrin, imiprothrin, pyrethrin and ciphenothrin, chloropralesrin, epsilonmethrin Trin and epsilon monfluorothrin and the like can be mentioned and may be at least one selected from these.
  • ryanodine receptor modulator examples include chloranthraniliprole, cyantraniliprole, flubendiamide, sihalodiamide, and the like, and may be at least one selected from these.
  • Acetylcholinesterase inhibitors include acephate, azinephos-methyl, kazusaphos, chlorethoxyphos, chlorfenbinphos, chlorpyriphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos (DDVP), dicrotophos, dimethote, disulfoton, etion, etoplophos.
  • EPN phenamiphos, fenitrothion (MEP), fenthion (MPP), hostizate, imiciaphos, isofenphos, isoxathione, malathion, metamidphos, metidathion, mevinphos, monochromotophos, ometoate, oxydemethonemethyl, parathion, parathion-methyl, pholate, , Hosalon, Hosmet, Phosfamidon, Hoxime, Pyrimiphosmethyl, Profenophos, Prothiophos, Pyraclophos, Pyridafenthion, Kinalphos, Tebupyrimhos, Telbuhos, Triazophos and Trichlorfon (DEP), Aranicarb, Ardicalve, Benfracarb, BPMC, Carbofuran, Carbofuran , Cartap, phenoxycarb (BPMC), formethanate, isoprocarb (MIPC), methiocarb, mesomil,
  • oxidative phosphorylation uncoupler examples include chlorfenapyr, DNOC, sulflamide and the like, and may be at least one selected from these.
  • mitochondrial electron transport chain complex I inhibitor examples include tebufenpyrado, tolfenpyrado, phenazakin, phenpyroxymate, pyridaben, pyrimidiphen and rotenone, and may be at least one selected from these.
  • Known active ingredients in plant growth regulators include aminoethoxyvinylglycine, chlormecoat, chlorpropham, cyclanilide, dikegrac, daminogit, etephone, fluluprimidol, flumethrolin, holchlorphenurone, gibberellin, hydrazide maleate. Salts, mepicort chloride, methylcyclopropham, benzylaminopurine, paclobutrazol, prohexadione, thydiazulone, tributylphosphorotrithioate, trinexacacethyl and uniconazole, and the like, and at least one selected from these. Can be one.
  • Known active ingredients (mite-killing active ingredients) contained in the acaricide include, for example, acequinocil, hydramethylnon, amideflumet, amitraz, azocyclotin, biphenazate, bromopropirate, clofentezine, quinomethionate, phenisobromolate, and the like.
  • nematode active ingredients contained in nematode nematodes include, for example, DD (1,3-dichloropropene), DCIP (dichlorodiisopropyl ether), methylisothiocyanate, carbam sodium salt, and the like.
  • avelmectin tetrachlorolantraniliplol, diafentiurone, ethiprol, fipronil, fronicamid, fluenesulfone, indoxacarb, metaflumison, metaaldehyde, pimetrodin, pyridalyl, pyrifluquinazone, silafluofen.
  • Examples include compounds, fatty acid monoesters with glycerin or propanediol, neem oil, boberia baciana, metallidium anisoprie, pequiromyces fumosoloseus, diatomaceous soil and the like.
  • the agricultural and horticultural chemicals in this embodiment can be used in cultivated or non-agricultural lands such as fields, paddy fields, lawns, and orchards. Further, the agricultural and horticultural chemicals in the present embodiment can be applied not only by foliage treatment such as foliage spraying, but also by non-foliage treatment such as seed treatment including treatment of bulbs and tubers, irrigation treatment, and water surface treatment. Therefore, the method for controlling plant diseases in the present embodiment is a method including a procedure for performing foliage treatment or non-foliage treatment using the above-mentioned agricultural and horticultural agents. In addition, when the non-foliage treatment is performed, the labor can be reduced as compared with the case where the foliage treatment is performed.
  • the chemicals are attached to the seeds by mixing the wettable powder and powder with the seeds and stirring, or by immersing the seeds in the diluted wettable powder. It also includes a seed coating process.
  • the amount of the active ingredient used in the seed treatment is, for example, 0.005 to 10000 g, preferably 0.05 to 1000 g per 100 kg of seeds. Seeds treated with agricultural and horticultural chemicals may be used in the same manner as normal seeds.
  • the application by irrigation treatment is performed by treating the planting hole or its surroundings with granules, etc. at the time of transplanting seedlings, or treating the soil around the seeds or plants with granules, wettable powders, etc. ..
  • the amount of the active ingredient used in the irrigation treatment is, for example, 0.005 to 10000 g, preferably 0.05 to 1000 g per 1 m 2 of agricultural and horticultural land.
  • Water surface treatment is performed by treating the surface water of the paddy field with granules or the like.
  • the amount of the active ingredient used in the water surface treatment is, for example, 0.05 to 10000 g, preferably 0.5 to 1000 g per paddy field 10a.
  • the amount of the active ingredient used for foliage spraying is, for example, 10 to 5000 g, more preferably 25 to 2000 g per 1 ha of agricultural and horticultural fields such as fields, rice fields, orchards and greenhouses.
  • concentration and amount of use differ depending on the dosage form, timing of use, method of use, place of use, target crop, etc., it is possible to increase or decrease without being particular about the above range.
  • the liquid carrier is not particularly limited as long as it does not react with the active ingredient.
  • the liquid carrier include water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, cellosolve, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers (eg, dimethyl ether, diethyl ether, dioxane, hydrocarbon, etc.).
  • aromatic hydrocarbons eg, benzene, toluene, xylene, methylnaphthalene, etc.
  • aliphatic hydrocarbons eg, gasoline, kerosine, kerosene, machine oil, fuel oil, etc.
  • acid amides eg, dimethylformamide.
  • N-Methylpyrrolidone, etc. Halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), esters (eg, ethyl acetate esters, fatty acid glycerin esters, etc.), nitriles (eg, acetonitrile, etc.) and dimethylsulfoxide. And so on.
  • fine powders or granules such as kaolin clay, bentonite, acidic clay, pyrophyllite, talc, diatomaceous earth, 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 anhydrosorbitols. Can be used.
  • the content ratio varies depending on the dosage form and the purpose of use, but is 0.1 to 99.9% by weight based on the total amount of the pharmaceutical product. do it.
  • the treatment concentration is usually adjusted to 0.0025 to 5% by weight, preferably 0.005 to 1% by weight by appropriately adding a solvent, a diluent, a bulking agent or the like. It is preferable to do so.
  • the triazole derivative (-)-enantiomer shows an excellent bactericidal action against many bacteria that cause plant diseases. That is, the agricultural and horticultural disease control agent containing the triazole derivative (-)-enantiomer as an active ingredient has low toxicity to humans and animals, is excellent in handling safety, and can exhibit a high control effect on a wide range of plant diseases.
  • the triazole derivative (-)-enantiomer according to the present embodiment can also be used as an industrial material protectant because it exhibits an excellent effect of protecting the material from a wide range of harmful microorganisms that attack the industrial material. Examples of such microorganisms include the following microorganisms.
  • Paper and pulp-deteriorating microorganisms including slime-forming microorganisms
  • Aspergillus sp. Trichoderma sp., Penicillium sp., Geotrichum sp., Chaetomium sp. (Cadophora sp. ), Ceratostomella sp., Cladosporium sp., Corticium sp., Lentinus sp., Lentinus sp., Phomatics sp.
  • Polysticus sp. Pulularia sp., Stereum sp., Trichosporium sp., Aerobacter sp., Bacillus sp., Desulfobibrio sp. , Pseudomonas sp., Flavobacterium sp., Micrococcus sp., and other fiber-degrading microorganisms such as Aspergillus sp., Penicillium sp., Penicillium sp. ), Micrococcium sp., Curvularia sp., Gliomatics sp., Memnoniella sp., Sarcopodium sp., Sarcopodium sp.
  • Penicillium sp. Chaetomium sp., Cladosporium sp., Mucor sp., Paecilomyces sp., Pilobus sp.
  • Trichosporon sp. Trichothecium sp., Aspergillus sp., Penicillium sp., Rhizopus sp., Trichothecium sp., Trichothecium sp., Trichothecium sp., Trichothecium sp.
  • the industrial material protective agent containing the triazole derivative (-)-enantiomer as an active ingredient may contain various components other than the triazole derivative (-)-enantiomer.
  • the industrial material protectant containing the triazole derivative (-)-enantiomer as an active ingredient can be dissolved or dispersed in a suitable liquid carrier, or mixed with a solid carrier for use.
  • the industrial material protectant containing the triazole derivative (-)-enantiomer as an active ingredient may further contain an emulsifier, a dispersant, a spreading agent, a penetrant, a wetting agent, a stabilizer and the like, if necessary.
  • Examples of the dosage form of the industrial material protective agent containing the triazole derivative (-)-enantiomer as an active ingredient include wettable powders, powders, granules, tablets, pastes, suspensions and spray materials. can.
  • the industrial material protective agent containing the triazole derivative (-)-enantiomer as an active ingredient may contain other fungicides, insecticides, deterioration inhibitors and the like.
  • the liquid carrier is not particularly limited as long as it does not react with the active ingredient.
  • the liquid carrier include water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, cellosolve, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers (eg, dimethyl ether, diethyl ether, dioxane, hydrocarbon, etc.).
  • aromatic hydrocarbons eg, benzene, toluene, xylene, methylnaphthalene, etc.
  • aliphatic hydrocarbons eg, gasoline, kerosine, kerosene, machine oil, fuel oil, etc.
  • acid amides eg, dimethylformamide.
  • N-Methylpyrrolidone, etc. Halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), esters (eg, ethyl acetate esters, fatty acid glycerin esters, etc.), nitriles (eg, acetonitrile, etc.), dimethylsulfoxide, etc. Can be mentioned.
  • fine powders or granules such as kaolin clay, bentonite, acidic clay, pyrophyllite, talc, diatomaceous earth, 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 the purpose of use, but is 0.05 to 99.9% by weight based on the total amount of the pharmaceutical product. do it.
  • the treatment concentration is usually adjusted to 0.0025 to 5% by weight, preferably 0.005 to 1% by weight by appropriately adding a solvent, a diluent, a bulking agent, or the like. It is preferable to do so.
  • the compound according to the present invention is a (-)-enantiomer of the triazole derivative represented by the above general formula (I) or a pesticide-acceptable salt thereof.
  • R 1 is -OR 4 ;
  • R 2 is a halogen group, a cyano group, a C 1- C 4 -alkyl group, a C 1- C 4 -haloalkyl group, a C 1- C 4 -alkoxy group, -SOR 7 or -SF 5 ;
  • R 3 is a halogen group, a nitro group, a cyano group, an amino group, a C 1- C 4 -alkyl group, a C 1- C 4 -haloalkyl group, a C 1- C 4 -alkoxy group, and a C 1- C 4 -halo.
  • alkoxy groups C 1 -C 4 - alkyl acyl amino group, the compound or a salt thereof -SOR 7 or -SF 5 - alkylamino group, C 1 -C 4 - dialkylamino group, C 1 -C 4.
  • R 4 is, C 1 -C 6 - an alkyl group
  • R 2 is halogen, cyano, C 1 -C 4 - alkyl group, C 1 -C 4 - haloalkyl group or a C 1 -C 4 - alkoxy group
  • R 3 is halogen, cyano, C 1 -C 4 - haloalkoxy group - alkyl group, C 1 -C 4 - haloalkyl group, C 1 -C 4 - alkoxy group or a C 1 -C 4.
  • Agricultural and horticultural agents or industrial material protective agents containing the triazole derivative (-)-enantiomer according to the present invention as an active ingredient are also included in the category of the present invention.
  • High Performance Liquid Chromatograph Preparative Column: Product Name "CHIRALPAK IG", manufactured by Daicel Chemical Industries, Ltd., Inner diameter 4.6 mm, Length 250 mm, Particle size 5 ⁇ m Sample concentration: 0.5 mg / mL Mobile phase: 100% methanol flow rate: 1.0 mL / min Column temperature: 40 ° C Detection wavelength: 230nm
  • the specific rotation was measured using P-1020 (manufactured by JASCO Corporation, Na lamp: 589 nm). The specific measurement results are as follows.
  • the same crude product C 2 was obtained by performing the same operation as the above operation. Together, they were purified as crude product C by silica gel column chromatography (silica gel 40 g hexane / ethyl acetate: 20 ⁇ 50%) to obtain 3.68 g of the title compound as a colorless liquid.
  • reaction solution B was added dropwise to the reaction solution A using a Pasteur pipette. After stirring for 6 hours under cooling at ⁇ 20 ° C., the reaction was stopped by adding a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium sulfite solution to the reaction solution.
  • High Performance Liquid Chromatograph Preparative Column: Product Name "CHIRALPAK IG", manufactured by Daicel Chemical Industries, Ltd., Inner diameter 4.6 mm, Length 150 mm, Particle size 5 ⁇ m Sample concentration: 1.0 mg / mL Mobile phase: 100% methanol flow rate: 1.0 mL / min Column temperature: 40 ° C Detection wavelength: 230nm
  • wettable powder> A hydrate was prepared as follows using any of the prepared triazole derivatives (-)-enantiomers described in this patent.
  • ⁇ Pharmaceutical example 2 Emulsion> An emulsion was prepared as follows using any of the prepared triazole derivatives (-)-enantiomers described in this patent.
  • Triazole derivative (-)-enantiomer 5.0 parts polyoxyalkylene alkyl ether / alkylbenzene sulfonic acid metal salt / alkylbenzene mixture 3.75 parts polyoxyalkylene alkyl ether 11.25 parts 5- (dimethylamino) -2-methyl-5 -Methyl oxopentanoate 12.0 parts N, N-dimethyloctaneamide / N, N-dimethyldecaneamide 44.0 parts Solventnaphtha 24.0 parts are uniformly mixed and dissolved to form an emulsion, which is diluted with water before use. bottom.
  • ⁇ Test Example 1 Antibacterial test against phytopathogens> The antibacterial property of compound 1 (-) prepared in Production Example 1 against various plant pathogens was tested by a Petri dish test.
  • Compound 1 (racemic) was used as a control compound. After sterilization by autoclave, compound 1 (-) or compound 1 dissolved in dimethyl sulfoxide (DMSO) so as to have a drug concentration of 2.5 mg / L in PDA medium (potato-dextrose-agar medium) cooled to around 60 ° C. (Potato) was added to PDA medium at 1% v / v. The mixture was mixed so that the drug concentration in the PDA medium was uniform, and the medium was poured into a petri dish to prepare a plate medium containing compound 1 ( ⁇ ) or compound 1 (racemic).
  • DMSO dimethyl sulfoxide
  • the flora of various phytopathogens shown in Table 1 previously cultured on the PDA medium was punched out with a cork borer having a diameter of 4 mm and inoculated into the above-mentioned drug-containing plate medium. After culturing at a temperature for a predetermined period, the bacterial flora diameter was measured on a drug-treated plate medium. The hyphal elongation inhibition rate (%) was calculated by the following formula in comparison with the diameter of the flora on the untreated plate containing no drug. The greater the rate of hyphal elongation inhibition, the better the antibacterial property.
  • Hyphal elongation inhibition rate (%) (1-Diameter of flora on drug-treated plate / Diameter of flora on untreated plate) x 100
  • the results of the hyphal elongation inhibition rate R (%) are shown in Table 1.
  • Example 2 Wheat red rust control effect test> Compound 1 (-) or compound 1 (racemic) prepared in Production Example 1 was dissolved in acetone so as to have a predetermined drug concentration, and 5% v / v was added to ion-exchanged water containing Gramin S (of Gramin S). Final concentration 60 ppm). The prepared drug was sprayed at a rate of 1000 L / ha on wheat (variety: Norin 61) in the first and second leaf stages cultivated in a square plastic pot (6 cm ⁇ 6 cm) (drug treatment group). The untreated plot was obtained by spraying wheat with ion-exchanged water containing 5% acetone (final concentration of Gramin S 60 ppm) containing no compound.
  • Control value (%) (1-Average diseased area in drug-treated area / Average diseased area in untreated area) x 100
  • Example 3 Wheat powdery mildew control effect test> Compound 1 (-) or compound 1 (racemic) prepared in Production Example 1 was dissolved in acetone so as to have a predetermined drug concentration, and 5% v / v was added to ion-exchanged water containing Gramin S (of Gramin S). Final concentration 60 ppm). The prepared drug was sprayed at a rate of 1000 L / ha on wheat (variety: Norin 61) in the first and second leaf stages cultivated in a square plastic pot (6 cm ⁇ 6 cm) (drug treatment group). The untreated plot was obtained by spraying wheat with ion-exchanged water containing 5% acetone (final concentration of Gramin S 60 ppm) containing no compound.
  • the spray liquid on the wheat leaves was air-dried, sprinkled with spores of wheat powdery mildew, and inoculated, and managed in a greenhouse.
  • the affected area of wheat powdery mildew was investigated, and the control value (%) was calculated.
  • control value of compound 1 was 38% at a concentration of 7.5 g / ha, whereas the control value of compound 1 (-) was 56%.
  • the (-)-enantiomer of the triazole derivative according to the present invention can be suitably used as an active ingredient of a fungicide for agriculture and horticulture and a protective agent for industrial materials.

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  • General Health & Medical Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un agent de lutte contre les maladies des plantes qui a une faible toxicité vis-à-vis des êtres humains et des animaux et une sécurité élevée en termes de manipulation, et qui présente d'excellents effets antimicrobiens, même à une faible dose d'application, sur un grand nombre de microorganismes provoquant des maladies des plantes. La présente invention concerne le (-)-énantiomère d'un composé représenté par la formule générale (I) ou un sel agrochimiquement acceptable de celui-ci.
PCT/JP2021/018610 2020-05-15 2021-05-17 (-)-énantiomère de dérivé de triazole, produit chimique agricole ou horticole, et produit de protection de matériau industriel WO2021230382A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023209045A1 (fr) 2022-04-26 2023-11-02 Syngenta Crop Protection Ag Fongicides énantiomériquement enrichis pour la lutte contre des champignons phytopathogènes résistants
WO2024014282A1 (fr) * 2022-07-14 2024-01-18 株式会社クレハ Procédé de production d'un énantiomère dérivé de triazole (r)

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Publication number Priority date Publication date Assignee Title
WO2019093522A1 (fr) * 2017-11-13 2019-05-16 株式会社クレハ Dérivé d'azole, composé intermédiaire, procédé de production d'un dérivé d'azole, agent à usage agricole et horticole, et agent de protection de matériau à usage industriel
WO2020213739A1 (fr) * 2019-04-19 2020-10-22 株式会社クレハ Agent bactéricide à usage agricole ou horticole, procédé de lutte contre les maladies des plantes et utilisation de produit de lutte contre les maladies de plantes
JP2020186178A (ja) * 2019-05-10 2020-11-19 株式会社クレハ 農園芸用薬剤、植物病害防除方法、及び植物病害防除用製品

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WO2019093522A1 (fr) * 2017-11-13 2019-05-16 株式会社クレハ Dérivé d'azole, composé intermédiaire, procédé de production d'un dérivé d'azole, agent à usage agricole et horticole, et agent de protection de matériau à usage industriel
WO2020213739A1 (fr) * 2019-04-19 2020-10-22 株式会社クレハ Agent bactéricide à usage agricole ou horticole, procédé de lutte contre les maladies des plantes et utilisation de produit de lutte contre les maladies de plantes
JP2020186178A (ja) * 2019-05-10 2020-11-19 株式会社クレハ 農園芸用薬剤、植物病害防除方法、及び植物病害防除用製品

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NOHIRA, HIROYUKI: "Optically Active Substances: Its organic industrial chemistry", ASAKURA PUBLISHING CO LTD., 1989, pages 20 - 21 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023209045A1 (fr) 2022-04-26 2023-11-02 Syngenta Crop Protection Ag Fongicides énantiomériquement enrichis pour la lutte contre des champignons phytopathogènes résistants
WO2024014282A1 (fr) * 2022-07-14 2024-01-18 株式会社クレハ Procédé de production d'un énantiomère dérivé de triazole (r)

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