WO2017109858A1 - Composé cyclique à 11 éléments condensé et germicide pour l'agriculture et l'horticulture le contenant - Google Patents

Composé cyclique à 11 éléments condensé et germicide pour l'agriculture et l'horticulture le contenant Download PDF

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WO2017109858A1
WO2017109858A1 PCT/JP2015/085829 JP2015085829W WO2017109858A1 WO 2017109858 A1 WO2017109858 A1 WO 2017109858A1 JP 2015085829 W JP2015085829 W JP 2015085829W WO 2017109858 A1 WO2017109858 A1 WO 2017109858A1
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Prior art keywords
thiazolyl
dihydro
piperidine
benzodioxepin
alkyl
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PCT/JP2015/085829
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English (en)
Japanese (ja)
Inventor
延雅 市川
堀越　大輔
誠 番場
貴俊 坂口
直己 岡田
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株式会社エス・ディー・エス バイオテック
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Priority to PCT/JP2015/085829 priority Critical patent/WO2017109858A1/fr
Publication of WO2017109858A1 publication Critical patent/WO2017109858A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the present invention relates to a novel condensed 11-membered ring compound or a salt thereof, an agricultural and horticultural bactericidal composition containing these as active ingredients, and a method for using the same.
  • the present invention further relates to a method for producing a novel condensed 11-membered ring compound.
  • the present invention includes disclosure of the following compounds.
  • A is an optionally substituted 5-6 membered heteroaryl or 9-10 membered bicyclic heteroaryl; E is —CR 7 R 8 —, an oxygen atom or —NR 9 —; R 7 and R 8 are each independently a hydrogen atom, a halogen atom, cyano, hydroxy, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 6 cycloalkyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, a C 1 ⁇ C 6 alkylsulfonyl, C 1 ⁇ C 6 halo
  • R 11 and R 12 are each independently a hydrogen atom, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 6 haloalkyl, C 3 -C 8 halocycloalkyl, C 1 -C 6 Alkoxy, C 2 -C 8 dialkylamino, C 2 -C 6 alkylcarbonyl, C 2 -C 6 haloalkylcarbonyl, C 4 -C 8
  • (2) A is each independently substituted by m R 17 , furanyl (furyl), thiophenyl (thienyl), pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, Oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1, 2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,3 5-triazinyl, benzofuryl, isobenzofuryl, benzo
  • A is furanyl (furyl), thiophenyl (thienyl), 1,2,4-triazolyl, isoxazolyl, pyridyl or quinolinyl, each optionally substituted by m R 17 , m is 0-2, R 17 is a halogen atom, methyl, fluoromethyl, difluoromethyl or trifluoromethyl; E is —CH 2 —, an oxygen atom or —NR 9 —; G is an oxygen atom, R 9 is a hydrogen atom or methyl; X 1 , X 2 , X 3 and X 4 are each independently a hydrogen atom, halogen atom, cyano, hydroxy, nitro, formyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxy Alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, -SR 10 , -S
  • A is A group selected from X 1 , X 2 , X 3 and X 4 are each independently a hydrogen atom, nitro, halogen atom, C 1 -C 4 alkyl, methoxy or —OS (O) 2 R 10 , The compound or a salt thereof according to any one of (1) to (3), wherein R 10 is methyl.
  • T is CH, R 3 and R 5 are hydrogen atoms;
  • X 1 is —OS (O) 2 R 10
  • X 2 and X 3 are hydrogen atoms
  • X 4 is a hydrogen atom, nitro, halogen atom, methyl, methoxy, or —OS (O) 2 R 10 .
  • a bactericidal composition comprising the compound or salt thereof according to any one of (7).
  • a method for controlling plant diseases caused by phytopathogenic microorganisms which comprises the step of applying the fungicidal composition of (8) to the whole plant or a part thereof, or seeds of the plant.
  • step 1 A step of reacting the compound represented by the formula [4] with the compound represented by the formula [5] in a solvent in the presence of a dehydrating condensing agent (step 1), or the compound represented by the formula [4] and the formula A process for producing a compound represented by the formula [1a], comprising a step of reacting a compound represented by [6] in a solvent in the presence of a base (step 2):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , G, X 1 , X 2 , X 3 , X 4 , T and n are ( 1) to (6) as defined above, and L 1 represents a halogen atom such as a chlorine atom or a bromine atom).
  • a compound represented by formula [1b] comprising a step of condensing a compound represented by formula [4], a compound represented by formula [7] and a compound represented by formula [8] in a solvent in the presence of a base.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 9 , G, X 1 , X 2 , X 3 , X 4 , T and n are (1) to (As defined in any one of (6), E represents an oxygen atom or —NR 9 —, and L 2 represents a chlorine atom or imidazol-1-yl).
  • the condensed 11-membered ring compound in the present invention includes, in addition to the condensed 11-membered ring compound represented by the formula [1], a salt of the compound, and an N-oxide of the condensed 11-membered ring compound represented by the formula [1].
  • the salt is not particularly limited, and examples thereof include salts that are acceptable for the production of agricultural chemicals. Specific examples include sodium salts, potassium salts, magnesium salts, calcium salts, and aluminum salts.
  • all possible stereoisomers or optical isomers present in the compound of the present invention are also included in the scope of the condensed 11-membered ring compound represented by the formula [1].
  • the condensed 11-membered ring compound of the present invention may be used in the form of an amorphous substance or a crystal, and may be used in the form of a hydrate, a solid that forms a solvate, or a solution or suspension. it can.
  • the condensed 11-membered ring compound of the present invention may be used as a mixture with other components, or as a mixture of compounds of the formula [1], particularly a mixture of enantiomers such as a racemate or a mixture of diastereomers. It is also included.
  • Formula [1] gives a general definition of fused 11-membered ring compounds that can be used according to the present invention. Preferred definitions of groups relating to the formulas shown above and below are described below. Such a definition applies to the final product of formula [1] and likewise applies to all intermediates.
  • A is preferably a 5-6 membered heteroaryl or 9-10 membered bicyclic heteroaryl except pyrazolyl, may be replaced by m-number of R 17 more preferably and independently, furanyl (furyl), Thiophenyl (thienyl), 1,2,4-triazolyl, isoxazolyl, pyridyl or quinolinyl, particularly preferably A-1 to A-10.
  • E is preferably —CH 2 —, an oxygen atom or —NR 9 —, more preferably —CH 2 — or —NH—.
  • M is preferably 0-2.
  • R 17 is preferably a halogen atom, methyl, fluoromethyl, difluoromethyl or trifluoromethyl, more preferably a halogen atom, methyl or trifluoromethyl.
  • R 7 and R 8 are preferably a hydrogen atom.
  • R 9 is preferably a hydrogen atom or methyl, more preferably a hydrogen atom.
  • G is preferably an oxygen atom.
  • T is preferably CH.
  • R 1 is preferably a hydrogen atom.
  • R 2 , R 3 , R 4 and R 5 are preferably a hydrogen atom or methyl, and more preferably a hydrogen atom.
  • n is preferably 0 (ie, R 6 is preferably absent).
  • X 1 , X 2 , X 3 and X 4 are preferably each independently a hydrogen atom, a halogen atom, cyano, hydroxy, nitro, formyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, -SR 10 , -S (O) 2 R 10 , -OS (O) 2 R 10 , C 2 -C 4 alkylcarbonyl Oxy, C 2 -C 4 alkoxycarbonyloxy or —C ( ⁇ NOR 13 ) R 14 , more preferably at least one of X 1 , X 2 , X 3 and X 4 is —OS (O) 2.
  • X 1 is -OS (O) 2 R 10
  • X 2 and X 3 are hydrogen atoms
  • X 4 is a hydrogen atom Nitro, halogen, methyl, methoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy or -OS (O) 2 R 10, and most preferably, X 4 is a hydrogen atom, nitro, methyl, fluorine atom, bromine Atomic, methoxy or —OS (O) 2 R 10 .
  • R 10 is preferably C 1 ⁇ C 4 alkyl, cyclopropyl or C 1 ⁇ C 4 haloalkyl, more preferably methyl.
  • R 13 is preferably a hydrogen atom or C 1 -C 4 alkyl, and more preferably a hydrogen atom or methyl.
  • R 14 is preferably a hydrogen atom or C 1 -C 4 alkyl, and more preferably a hydrogen atom or methyl.
  • One preferred embodiment is a compound represented by the formula [1] ⁇ wherein A represents A-1 ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein A represents A-2 ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein A represents A-3 ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein A represents A-4 ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein A represents A-5 ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein A represents A-6 ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein A represents A-7 ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein A represents A-8 ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein A represents A-9 ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein A represents A-10 ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein at least one of X 1 , X 2 , X 3 and X 4 represents methylsulfonyloxy ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein X 1 represents methylsulfonyloxy and X 2 , X 3 and X 4 represent a hydrogen atom ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein X 1 is methylsulfonyloxy, X 2 and X 3 are hydrogen atoms, and X 4 represents a fluorine atom ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein X 1 is methylsulfonyloxy, X 2 and X 3 are hydrogen atoms, and X 4 represents a bromine atom ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein X 1 is methylsulfonyloxy, X 2 and X 3 are hydrogen atoms, and X 4 represents methoxy ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein X 1 is methylsulfonyloxy, X 2 and X 3 are hydrogen atoms, and X 4 represents cyano ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein X 1 is methylsulfonyloxy, X 2 and X 3 are hydrogen atoms, and X 4 represents nitro ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein X 1 is methylsulfonyloxy, X 2 and X 3 are hydrogen atoms, and X 4 represents methyl ⁇ .
  • Another preferred embodiment is a compound represented by the formula [1] ⁇ wherein X 1 and X 4 represent methylsulfonyloxy, and X 2 and X 3 represent a hydrogen atom ⁇ .
  • Halogen atom includes fluorine atom, chlorine atom, bromine atom or iodine atom.
  • the notation by an element symbol such as C 1 to C 6 and a subscript number indicates that the number of elements of the group described subsequently is in a range indicated by the subscript number.
  • the carbon number is 1 to 6
  • the C 2 to C 6 notation indicates that the carbon number is 2 to 6.
  • C 4 -C 8 cycloalkylcarbonyloxy indicates that the total number of carbon atoms in the cycloalkylcarbonyloxy is 4-8, and includes a cyclopropylcarbonyl group and the like.
  • C 2 -C 8 cyanoalkyl indicates that the total number of carbon atoms in the cyanoalkyl is 2-8.
  • C 2 -C 8 cyanoalkyl may contain one or more cyano groups, including a cyanomethyl group and the like.
  • Alkyl means, for example, linear or branched alkyl having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isobutyl, n-butyl, sec -Butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, n-hexyl 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-d
  • alkyl as part of a composite substituent such as haloalkyl, alkylthio, alkylcarbonyl, alkylsulfonyloxy, and the like, unless otherwise defined.
  • a composite substituent such as haloalkyl, alkylthio, alkylcarbonyl, alkylsulfonyloxy, and the like, unless otherwise defined.
  • an alkyl-terminated composite substituent such as alkylcycloalkyl
  • that portion of the cycloalkyl may be independently mono- or polysubstituted by the same or different alkyls.
  • Complex substituents terminated with other groups such as alkenyl, alkoxy, hydroxy, halogen atoms and the like are similarly understood.
  • Cycloalkyl means, for example, a cycloalkyl having a branched chain having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms.
  • cyclopropyl 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl , Cyclopentyl, cyclohexyl, 4,4-dimethylcyclohexyl, and the like.
  • This definition also applies to cycloalkyl as part of a composite substituent, such as halocycloalkyl, unless otherwise defined.
  • the cycloalkenyl means, for example, a cycloalkenyl having a branched chain having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms.
  • cyclopropenyl 1-methylcyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl And the like.
  • This definition also applies to cycloalkenyl as part of a composite substituent, such as halocycloalkenyl, unless otherwise defined.
  • Cycloalkoxy means, for example, a cycloalkoxy having a branched chain having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, such as cyclopropyloxy, 1-methylcyclopropyloxy, cyclobutyloxy, cyclopentyl. Examples include oxy, cyclohexyloxy and the like. This definition also applies to cycloalkoxy as part of a composite substituent such as halocycloalkoxy, unless otherwise defined.
  • halo in “halo ...” (for example, “haloalkyl”) includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Halo substitution represented by the prefix “halo” includes mono- or polysubstitution and preferably includes mono-, di- and tri-substitution.
  • Haloalkyl means, for example, a straight-chain or branched-chain alkyl having 1 to 6 carbon atoms, wherein some or all of the hydrogen atoms in these groups are substituted with halogen atoms.
  • Examples include groups such as -chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, 4-trifluorobutyl, 5-chloropentyl, 6-chlorohexyl and the like. This definition also applies to haloalkyls as part of complex substituents such as haloalky
  • Alkenyl means, for example, straight or branched alkenyl having 2 to 6 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 3-butenyl, 1,3-butadienyl, 4 Examples include groups such as -pentenyl, 5-hexenyl and the like. This definition also applies to alkenyl as part of a complex substituent such as haloalkenyl, unless otherwise defined.
  • Alkynyl means, for example, straight-chain or branched alkynyl having 2 to 6 carbon atoms, such as ethynyl, 1-propynyl, 2-propynyl, 3-butynyl, 1-methyl-3-propynyl, 4- Mention may be made of groups such as pentynyl, 5-hexynyl and the like. This definition also applies to alkynyls as part of complex substituents such as haloalkynyl, unless otherwise defined.
  • Alkoxy means, for example, straight or branched alkoxy having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, Examples include groups such as hexyloxy. This definition also applies to alkoxy as part of a complex substituent such as haloalkoxy, alkoxycarbonyl, etc., unless otherwise defined.
  • Haloalkoxy means, for example, straight-chain or branched alkoxy having 1 to 6 carbon atoms and substituted by 1 or more, preferably 1 to 10 halogen atoms, such as fluoromethoxy, chloromethoxy, Bromomethoxy, iodomethoxy, difluoromethoxy, dichloromethoxy, dibromomethoxy, diiodomethoxy, trifluoromethoxy, trichloromethoxy, tribromomethoxy, triiodomethoxy, 1-chloroethoxy, 1-bromoethoxy, 2-trifluoroethoxy, Examples include 3-chloropropoxy, 3-bromopropoxy, 4-chlorobutoxy, 4-bromobutoxy, 4-trifluorobutoxy, 5-chloropentoxy, 6-chlorohexyloxy and the like. This definition also applies to haloalkoxy as part of a complex substituent such as haloalkoxycarbonyl, unless otherwise defined.
  • Alkylthio means, for example, an (alkyl) -S-group having 1 to 6 carbon atoms where the alkyl moiety has the above meaning, and examples include groups such as methylthio, ethylthio, n-propylthio, isopropylthio and the like. it can. This definition also applies to alkylthio as part of a complex substituent such as haloalkylthio, unless otherwise defined.
  • Alkylsulfinyl means, for example, an (alkyl) -SO— group having 1 to 6 carbon atoms in which the alkyl moiety has the above-mentioned meaning, for example, a group such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, etc. Can be mentioned. This definition also applies to alkylsulfinyls as part of complex substituents such as haloalkylsulfinyl, unless otherwise defined.
  • Alkylsulfonyl means, for example, an (alkyl) -SO 2 — group having 1 to 6 carbon atoms in which the alkyl moiety has the above meaning, such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, etc.
  • the group can be mentioned.
  • This definition also applies to alkylsulfonyls as part of complex substituents such as haloalkylsulfonyl, unless otherwise defined.
  • Hydroxyalkyl means a linear or branched alkyl group having 1 to 6 carbon atoms substituted by 1 to 5 hydroxy groups, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, etc. Can be mentioned.
  • Alkylsulfonyloxy means, for example, an (alkyl) -S (O) 2 O— group having 1 to 6 carbon atoms in which the alkyl moiety has the above meaning, such as methylsulfonyloxy, ethylsulfonyloxy, n- Examples include propylsulfonyloxy, isopropylsulfonyloxy and the like. This definition also applies to alkylsulfonyloxy as part of a composite substituent such as haloalkylsulfonyloxy, unless otherwise defined.
  • Alkylcarbonyl means, for example, an (alkyl) -C ( ⁇ O) — group in which the alkyl moiety has the above-mentioned meaning, and examples thereof include groups such as formyl, acetyl, propionyl, butyryl, pivaloyl and the like. This definition also applies to alkylcarbonyls as part of complex substituents such as haloalkylcarbonyl, unless otherwise defined.
  • Alkylcarbonyloxy means, for example, an (alkyl) -C ( ⁇ O) O— group in which the alkyl moiety has the above meaning, and examples include groups such as methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy and the like. Can do. This definition also applies to alkylcarbonyloxy as part of a complex substituent such as haloalkylcarbonyloxy, unless otherwise defined.
  • the acid used in the reaction according to the present invention means a Bronsted acid that releases protons in the reaction system, and includes inorganic acids such as hydrochloric acid, hydrobromic acid, and sulfuric acid, acetic acid, trifluoro Examples thereof include organic acids such as acetic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid.
  • the Lewis acid used in the reaction according to the present invention means a compound that functions as an electron pair acceptor in the reaction system other than hydrogen ions, such as zinc chloride, aluminum chloride, tin chloride, boron trichloride, boron trifluoride. And trimethylsilyl trifluoromethanesulfonate.
  • the base used in the reaction according to the present invention means a compound that receives a proton in the reaction system or a compound that functions as an electron pair donor in the reaction system, and includes triethylamine, pyridine, 4- Organic amines such as dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5,4,0] -7-undecene; metal carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate; Metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal carboxylates represented by metal acetates such as sodium acetate, potassium acetate, calcium acetate and magnesium acetate; sodium methoxide, sodium ethoxide, sodium tert- Butoxide, potassium methoxide, potassium te metal alkoxides such as t-butoxide; metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide; metal hydr
  • Me methyl group
  • Et ethyl group
  • n-Pr n-propyl group
  • i-Pr isopropyl group
  • c-Pr cyclopropyl group
  • n-Bu n-butyl group
  • i-Bu isobutyl group
  • t-Bu tert-butyl group
  • Ph phenyl group
  • Bn benzyl group.
  • the formula [1] By reacting the compound represented by the formula [2] and the compound represented by the formula [3] in a solvent in the presence of an acid or a Lewis acid, preferably in the presence of an acid, the formula [1]
  • the compound of the present invention represented can be produced.
  • the amount of the compound of the formula [3] used here may be appropriately selected from the range of 1.0 to 10 mol, preferably 1.0 to 3.0, relative to 1 mol of the compound of the formula [2]. Is a mole.
  • acids that can be used in this step include inorganic acids such as hydrochloric acid, hydrobromic acid, and sulfuric acid, and organic acids such as acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.
  • inorganic acids such as hydrochloric acid, hydrobromic acid, and sulfuric acid
  • organic acids such as acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.
  • Lewis acids examples include zinc chloride, aluminum chloride, tin chloride, boron trichloride, boron trifluoride, and trimethylsilyl trifluoromethanesulfonate.
  • the amount of acid or Lewis acid used may be appropriately selected from the range of 0.01 to 5 mol, preferably 0.1 to 1.0 mol, per 1 mol of the compound of the formula [2].
  • the solvent that can be used in this step is not particularly limited as long as it does not inhibit the progress of this reaction.
  • nitriles such as acetonitrile
  • ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme, diglyme
  • dichloromethane dichloroethane
  • Halogenated hydrocarbons such as chloroform, carbon tetrachloride and tetrachloroethane
  • aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene and toluene
  • amides such as N, N-dimethylformamide and N, N-dimethylacetamide
  • Imidazolinones such as 1,3-dimethyl-2-imidazolinone
  • sulfur compounds such as dimethyl sulfoxide can be used, and a mixed solvent thereof can also be used.
  • the amount of the solvent used may be appropriately selected from the range of 0.01 to 100 L, preferably 0.1 to 10 L, relative to 1 mol of the compound of the formula [2].
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 150 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [1] which is the target product of the reaction, is collected from the reaction system by a conventional method after completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , G, X 1 , X 2 , X 3 , X 4 , T and n are ( 1) As defined in any one of (6), L 1 represents a halogen atom such as a chlorine atom or a bromine atom.
  • the compound of the formula [1a] can also be produced by reacting the compound of the formula [4] and the compound of the formula [5] in a solvent in the presence / absence of a base and in the presence of a dehydrating condensing agent. Can do.
  • the amount of the compound of formula [5] used in this step may be appropriately selected from the range of 0.5 to 10 mol, preferably 1.0 to 1.2, relative to 1 mol of the compound of formula [4]. Is a mole.
  • Examples of the dehydrating condensing agent that can be used in this step include dicyclohexylcarbodiimide (DCC), N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide (EDC or WSC), N, N-carbonyldiimidazole, 2 -Chloro-1,3-dimethylimidazolium chloride, 2-chloro-1-pyridinium iodide and the like can be used.
  • DCC dicyclohexylcarbodiimide
  • EDC or WSC N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide
  • N N-carbonyldiimidazole
  • 2 -Chloro-1,3-dimethylimidazolium chloride 2 -Chloro-1,3-dimethylimidazolium chloride
  • 2-chloro-1-pyridinium iodide 2-chlor
  • the amount of the dehydrating condensing agent used in this reaction may be appropriately selected from the range of 1.0 to 10 mol, preferably 1.0 to 3.0 mol, per 1 mol of the compound of the formula [4]. .
  • Examples of the base that can be used in this step include organic amines such as triethylamine, pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5,4,0] -7-undecene; Metal carbonates such as sodium, potassium carbonate, magnesium carbonate and calcium carbonate; metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; represented by metal acetates such as sodium acetate, potassium acetate, calcium acetate and magnesium acetate Carboxylic acid metal salts; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium tert-butoxide; metal water such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide Hydride; lithium hydride, sodium hydride, and metal hydrides such as calcium hydride.
  • organic amines such as triethylamine, pyr
  • the amount of the base used in this reaction may be appropriately selected from the range of 0 to 100 mol, preferably 0 to 10 mol, relative to 1 mol of the compound of the formula [4].
  • Examples of the solvent that can be used in this step include the same solvents as described in Production Method 1.
  • the amount of the solvent used may be appropriately selected from the range of 0.01 to 100 L, preferably 0.1 to 10 L, relative to 1 mol of the compound of the formula [4].
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [1a] can also be produced by reacting the compound of the formula [4] and the compound of the formula [6] in a solvent in the presence of a base.
  • the amount of the compound of formula [6] used in this step may be appropriately selected from the range of 0.5 to 10 mol, preferably 1.0 to 1.2, relative to 1 mol of the compound of formula [4]. Is a mole.
  • Step 1 As the base that can be used in this step, the same ones described in Step 1 can be mentioned.
  • the amount of the base used in this reaction may be appropriately selected from the range of 1.0 to 100 mol, preferably 1.0 to 10 mol, per 1 mol of the compound of the formula [4].
  • Examples of the solvent that can be used in this step include the same solvents as described in Production Method 1.
  • the amount of the solvent used may be appropriately selected from the range of 0.01 to 100 L, preferably 0.1 to 10 L, relative to 1 mol of the compound of the formula [4].
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [1a], which is the target product of the reaction is collected from the reaction system by a conventional method after completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary.
  • the compound of the present invention represented by the formula [1b] (E in the formula [1] is an oxygen atom or —NR 9 —) can also be produced by a method comprising the reaction formulas exemplified below.
  • A, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 9 , G, X 1 , X 2 , X 3 , X 4 , T and n are each (1).
  • E represents an oxygen atom or —NR 9 —
  • L 2 represents a chlorine atom or imidazol-1-yl.
  • the compound of the formula [1b] can be produced by reacting the compound of the formula [4], the compound of the formula [7], and the compound of the formula [8] in a solvent in the presence of a base.
  • Examples of equivalents include triphosgene, diphosgene, carbodiimidazole, and thiocarbodiimidazole.
  • the amount of the compounds of formula [7] and formula [8] used in this step may be appropriately selected from the range of 0.5 to 10 mol, preferably 0, relative to 1 mol of the compound of formula [4]. .8 to 1.2 moles.
  • Examples of the base that can be used in this step include the same ones described in Production Method 2 Step 1.
  • the amount of the base used in this reaction may be appropriately selected from the range of 1.0 to 100 mol, preferably 1.0 to 10 mol, per 1 mol of the compound of the formula [4].
  • Examples of the solvent that can be used in this step include the same solvents as described in Production Method 1.
  • the amount of the solvent used in this reaction may be appropriately selected from the range of 0.01 to 100 L, preferably 0.1 to 10 L, relative to 1 mol of the compound of the formula [4].
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [1b], which is the target product of the reaction is collected from the reaction system by a conventional method after the completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary.
  • R 1 , R 6 , R 7 , R 8 , G, T and n are as defined in any one of (1) to (6), and L 1 is a chlorine atom Represents a halogen atom such as a bromine atom.
  • the compound of the formula [2a] is obtained by dehydration condensation of the compound of the formula [9] (which can be produced based on the description of WO2008 / 013622) and the compound of the formula [5] in the presence / absence of a base. It can be produced by reacting in a solvent in the presence of an agent.
  • the amount of the compound of the formula [5] used in this step may be appropriately selected from the range of 0.5 to 10 mol, preferably 1.0 to 1.2, relative to 1 mol of the compound of the formula [9]. Is a mole.
  • Examples of the dehydrating condensing agent and base that can be used in this step include the same ones described in the manufacturing method 2 step 1.
  • the amount of the dehydrating condensing agent used in this reaction may be appropriately selected from the range of 1.0 to 10 mol, preferably 1.0 to 3.0 mol, per 1 mol of the compound of the formula [9]. .
  • the amount of the base used in this reaction may be appropriately selected from the range of 0 to 100 mol, preferably 0 to 10 mol, per 1 mol of the compound of the formula [9].
  • Examples of the solvent that can be used in this step include the same solvents as described in Production Method 1.
  • the amount of the solvent used in this reaction may be appropriately selected from the range of 0.01 to 100 L with respect to 1 mol of the compound of the formula [9], and preferably 0.1 to 10 L.
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [2a] can also be produced by reacting the compound of the formula [9] and the compound of the formula [6] in a solvent in the presence of a base.
  • the amount of the compound of formula [6] used in this step may be appropriately selected from the range of 0.5 to 10 mol, preferably 1.0 to 1.2, relative to 1 mol of the compound of formula [9]. Is a mole.
  • Examples of the base that can be used in this step include the same ones described in the manufacturing method 2 step 1.
  • the amount of the base used in this reaction may be appropriately selected from the range of 1.0 to 100 mol, preferably 1.0 to 10 mol, per 1 mol of the compound of the formula [9].
  • Examples of the solvent that can be used in this step include the same solvents as described in Production Method 1.
  • the amount of the solvent used in this step may be appropriately selected from the range of 0.01 to 100 L, preferably 0.1 to 10 L, relative to 1 mol of the compound of the formula [9].
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [2a], which is the target of the reaction is collected from the reaction system by a conventional method after completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary.
  • the compound of the formula [2b] can be produced by reacting the compound of the formula [9], the compound of the formula [7], and the compound of the formula [8] in a solvent in the presence of a base.
  • the amount of the compound of formula [7] and formula [8] used in this step may be appropriately selected from the range of 0.5 to 10 mol, preferably 0, per 1 mol of the compound of formula [9]. .8 to 1.2 moles.
  • Examples of the base that can be used in this step include the same ones described in Production Method 2 Step 1.
  • the amount of the base used in this reaction may be appropriately selected from the range of 1.0 to 100 mol, preferably 1.0 to 10 mol, per 1 mol of the compound of the formula [9].
  • Examples of the solvent that can be used in this step include the same solvents as described in Production Method 1.
  • the amount of the solvent used in this reaction may be appropriately selected from the range of 0.01 to 100 L with respect to 1 mol of the compound of the formula [9], and preferably 0.1 to 10 L.
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [2b], which is the target product of the reaction is collected from the reaction system by a conventional method after completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary.
  • the compound of the formula [3a] can be produced by reducing the compound of the formula [10] in a solvent using a reducing agent.
  • Examples of the reducing agent that can be used in this step include lithium aluminum hydride, diisobutylaluminum hydride, and borane.
  • the amount of the reducing agent to be used may be appropriately selected from the range of 1.0 to 10 mol, preferably 2.0 to 5.0 mol, per 1 mol of the compound of the formula [10].
  • Examples of the solvent that can be used in this step include the same solvents as described in Production Method 1.
  • the amount of the solvent used may be appropriately selected from the range of 0.01 to 100 L with respect to 1 mol of the compound of the formula [10], and preferably 0.1 to 10 L.
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [3a], which is the target product of the reaction is collected from the reaction system by a conventional method after the completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary.
  • the compound of the formula [3a] can also be produced by reducing the compound of the formula [11] in a solvent using a reducing agent.
  • Examples of the reducing agent that can be used in this step include the same ones described in the intermediate production method 3.
  • the amount of the reducing agent to be used may be appropriately selected from the range of 1.0 to 10 mol, preferably 2.0 to 5.0 mol, per 1 mol of the compound of the formula [11].
  • Examples of the solvent that can be used in this step include the same solvents as described in Production Method 1.
  • the amount of the solvent used may be appropriately selected from the range of 0.01 to 100 L, preferably 0.1 to 10 L, relative to 1 mol of the compound of the formula [11].
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [3a], which is the target product of the reaction is collected from the reaction system by a conventional method after the completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary.
  • the compound of the formula [3b] can be produced by reducing the compound of the formula [12] in a solvent using a reducing agent.
  • Examples of the reducing agent that can be used in this step include the same ones described in the intermediate production method 3.
  • the amount of the reducing agent to be used may be appropriately selected from the range of 1.0 to 10 mol, preferably 1.0 to 3.0 mol, per 1 mol of the compound of the formula [12].
  • a solvent which can be used at this process the same thing explained with manufacturing method 1 can be mentioned.
  • the amount of the solvent used may be appropriately selected from the range of 0.01 to 100 L with respect to 1 mol of the compound of the formula [12], and preferably 0.1 to 10 L.
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 100 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [3b], which is the target product of the reaction is collected from the reaction system by a conventional method after the completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary.
  • the compound of formula [4] can be prepared by deprotecting the compound of formula [14] using a suitable method (for amine protecting group methods, see, for example, TW Greenene). And PG Wuts, Protective Groups in Organic Synthesis, 4th Edition; see Wiley: New York, 2007).
  • a suitable method for amine protecting group methods, see, for example, TW Greenene). And PG Wuts, Protective Groups in Organic Synthesis, 4th Edition; see Wiley: New York, 2007.
  • a wide variety of protecting groups are suitable for amine protecting groups, and suitable protecting group options will be apparent to those skilled in the art of chemical synthesis.
  • the amine of formula [4] can be isolated as an acid salt or free amine by basic methods well known in the art.
  • the formula [14] By reacting the compound represented by the formula [13] and the compound represented by the formula [3] in a solvent in the presence of an acid or a Lewis acid, preferably in the presence of an acid, the formula [14]
  • the compound of the present invention represented can be produced.
  • the amount of the compound of the formula [3] used here may be appropriately selected from the range of 1.0 to 10 mol, preferably 1.0 to 3.0 mol, relative to 1 mol of the compound of the formula [13]. It is.
  • Examples of the acid, Lewis acid, and solvent that can be used in this step can be the same as those described in Production Method 1.
  • the amount of acid or Lewis acid used may be appropriately selected from the range of 0.01 to 5 mol, preferably 0.1 to 1.0 mol, per 1 mol of the compound of the formula [13].
  • the amount of the solvent used may be appropriately selected from the range of 0.01 to 100 L, preferably 0.1 to 10 L, relative to 1 mol of the compound of the formula [13].
  • the reaction temperature may be selected from the range of the boiling point of the inert solvent used from ⁇ 20 ° C., preferably 0 ° C. to 150 ° C.
  • the reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 10 minutes to 48 hours.
  • the compound of the formula [14], which is the target product of the reaction is collected from the reaction system by a conventional method after completion of the reaction, and can be purified by operations such as column chromatography and recrystallization as necessary.
  • the salt of the compound represented by the formula [1] can be prepared by methods well known to those skilled in the art.
  • the fungicidal composition and the agrochemical composition of the present invention contain the compound represented by the formula [1] or a pesticidally acceptable salt thereof (hereinafter referred to as the compound of the present invention) as an active ingredient. To do.
  • the present invention also relates to an agrochemical composition comprising one or more of the compounds of the present invention or an agrochemically acceptable salt thereof, and a carrier acceptable for an agrochemical formulation, and more specifically for agricultural and horticultural use. This relates to a bactericidal composition.
  • the compound of the present invention or the bactericidal composition of the present invention can be used for controlling phytopathogenic microorganisms or plant diseases caused thereby prophylactically or therapeutically. That is, the present invention also relates to a method of using the compound of the present invention or the fungicidal composition of the present invention for controlling a plant disease occurring in a plant or a part of a plant.
  • the compounds of the present invention and the bactericidal compositions of the present invention have very strong bactericidal properties and are phytopathogenic microorganisms, such as protozoa, mates belonging to Phytomycota, Omycota Fungi belonging to Zygomycota, Ascomycota, Basidiomycota, and Deuteromycota, and the like, for example, Pseudomonadaceae, Rhizodiae, Belonging to the family Enterobacteriaceae, Corynebacteriumceae, Streptomycesaceae, etc. Bacteria, and it can be used for controlling plant diseases caused by these.
  • the compound of the present invention and the bactericidal composition of the present invention exhibit a high bactericidal activity against protozoa belonging to the oomycete, and thus have an excellent control effect on plant diseases caused thereby.
  • phytopathogenic microorganisms that can be controlled according to the present invention are listed below, but are not necessarily limited thereto.
  • pathogenic microorganisms belonging to Oomycota Albugo genus protists that are pathogens for white rust, such as Albugo candida; Root rot, damping-off pathogens of the genus Aphanomyces, such as Aphanomyces eteuches; Bremia protists that are pathogens of downy mildew, such as Bremia lactucae; Peronospora protozoa that are pathogens of downy mildew, such as Peronospora pis, Peronospora brasicae, Peronospora pras Plasmopara protozoa that are pathogens of downy mildew, such as Plasmopara viticola; Pseudoperonospora protozoa that are pathogens of downy mildew, such as Pseudoperonospora cubensis, Phytophthora (or Phytophthora rot) which is
  • pathogenic microorganisms belonging to Cercozoa include Plasmodiophora protozoa that are pathogens of clubroot, such as Plasmodiophora brassicae.
  • pathogenic microorganisms belonging to Zygomycota are pathogens of seedling blight, rot disease (bulb rot), black mold disease (Rhizopus rot), soft rot disease (soft rot) Rhizopus genus fungi, for example, Rhizopus stronifer can be mentioned.
  • pathogenic microorganisms belonging to the Ascomycota Ascomycota
  • Ascomycota Ascochita genus fungi that are pathogens of flower blight (ray blight), brown spot (brown spot), ring rot (Ascochyta leaf spot), and black spot (leaf spot)
  • Blumeria genus fungi that are pathogens of powdery mildew, such as Blumeria graminis
  • pathogens of ergot and rice smut for example, Claviceps purpurea
  • Cochliobolus Cobolius a pathogen of southern leaf blight, spot blotch, and brown strip disease, such as Cochliobolus saubus Cochliobols sativus
  • Diaporthe genus fungi that are pathogens of diaporthe cancer, such as Diaporthe citri
  • Gaemannomyces fungi that are pathogens of take-all, such as Gaeumanomyces graminis; Gibberella spp.
  • Pathogens of twig blight, bakanae disease, bud rot, stab dieback for example, Gibberella geer
  • Glomerella singulata that are pathogens of anthracnose, late rot, red rot, leaf spot such as Glomerella singulata
  • Guignardia fungi for example, Guignardia bidwellii
  • Helminthosporum such as Helminthosporum, which is a pathogen of stem rot, silver scab, zonaate leaf spot, such as Helminthosporum sigmoideum, Helminthosporum Helminthosporium solani, Helminthosporium tripenic repentis, Helminthosporium zonatum
  • pathogens of stem blight and ring spot disease such as Leptosphaeria juncina, Leptosphaeria spp., Leptosphaeria spp. Saccharid (Leptosphaeria sacchari); Magnaporthe fungi that are pathogens of staphylococcal nuclear disease (eg, Magnaporthe grisea, Magnaporthe salvinii); The genus Monilinia which is a pathogen of brown rot and monsilia disease, such as Monilinia fructicola, Monilinia laxa, Monilinea Monografella spp.
  • pathogens of black leaf blight and leaf spot such as Mycosphaerella arachidicola, Mycosphaerella gramicola; Phaeomoniella genus fungi that are pathogens of Phaeomoniella disease, such as Phaeomoniella chlamidospora; Phaeosphaeria spp.
  • pathogens of bacterial blotch such as Phaeosphaeria nodorum
  • Podosphaera genus fungi that are pathogens of powdery mildew, such as Podosphaera leukotrica, Podosphaera tridactyla
  • Pyrenophora genus fungi that are pathogens of leafy spot disease and net blotch disease, such as Pyrenophora graminea, Pyrenophora teres
  • Yellow mildew sclerotia rot fungi that are pathogens of sclerotia rot, such as Sclerotinia sclerotiorum
  • White blight white rot pathogens of the genus Sclerotium, for example, Sclerothium rolfsiii
  • Sphaerotheca genus fungi that are pathogenic to powdery mildew, such as Sphaerotheca furiginea, Sphathetheca rel
  • pathogenic microorganisms belonging to Basidiomycota include Basidiomycota; Strain-rot, winter stem rot pathogens of the genus Seratobasidium, for example, Ceratobasidium graminerum; Corticium genus fungi that are pathogens of strain-rot and winter stem rot, such as Corticium graminerum; The genus Exobasidium genus genus spp.
  • Exobasidium bexans Exobasidium vexans
  • Fomitiporia fungi that are pathogens of dwarf disease (Dwarf), for example Fomitiporia mediteranea
  • Ganoderma fungi that are pathogens of Stem rot, such as Ganoderma boninense
  • Gymnosporangium fungi that are pathogenic to red rust, such as Gimnosporangium sabinae, Gimnosporangium sapinae (Gymnosporangium) Hemileia spp.
  • pathogens of rust such as Hemirea vastatrix
  • Brown rust rust pathogens of the genus Phakopsora, such as Phakopsora meibomiae, Phakopsora pachirhiz
  • Rust stem rust, leaf rust pathogens of the genus Puccinia, such as Puccinia arachidis, Puccinia graminis, hordei), Puccinia recondita, Puccinia striformis; Tilletia spp.
  • pathogenic microorganisms belonging to Deuteromycota Black spot disease (Alternaria blotch, Alteria rear leaf spot, Alternaria black rot), black leaf blight (early bright), summer blight (Early blight), the genus Alria, the genus Allia Brush cola (Alternaria brassicicola), Alternaria solani (Alternaria solani); Aspergillus genus fungi that are pathogens of brown rot, such as Aspergillus flavus; Botrytis spp. Which are pathogens of gray mold, gray rot, red spot, such as Botrytis cinerea; Cercosporidium spp.
  • pathogens of leaf spot such as Cercosporidium personatum; Cercospora genus fungi that are pathogens of leaf spot, leaf spot, brown round spot, leaf blight, purple stain,
  • the genus Cladosporium which is a pathogen of black scab, false blast, leaf blotch, such as Cladosporium cucumerinum, Cladosporium crudosporium Poloidos cladosporoides, Cladosporium herbarum; Anthracnose (anthracnose), pathogen and is Colletotrichum (Colletotrichum) genus fungi ripe rot (ripe rot), for example, Colletotrichum Kokodesu (Colletotrichum coccodes), Colletotrichum Guraminikora (Colletotrichum graminicola),
  • pathogenic microorganisms belonging to the family Xanthomomonadaceae include Xanthomonasaceae, which is a pathogen of bacterial leaf blight, bacterial bacterial spot, and bacterial brown spot.
  • Bacteria for example, Xanthomonas campestris pasova orizae (Xanthomonas campestris pv. Oryzae), Xanthomonas campestris pasova vegetaria (Xanthomonas campestris pv .. vesicoria).
  • pathogenic microorganisms belonging to the family Pseudomonadaceae include leaf brown rot and bacterial wilt pathogen, such as Pseudomonas s. syringae pv. lacrymans), Pseudomonas syringae pasovamori (Pseudomonas syringae pv. mori).
  • pathogenic microorganisms belonging to Enterobacteriaceae include bacteria belonging to the genus Ervinia, which is a pathogen of soft rot (Erwinia amyrobora, Erwinia aromatobacter). subsp. carotovora).
  • Corynebacteriaceae bacteria examples include Corynebacterium bacteria that are pathogens of fasciation, such as Corynebacterium facias.
  • pathogenic microorganisms belonging to the family Streptomycesaceae include Strepmyces bacterium, which is a pathogen of soil smelling yellow rice, such as Streptomyces flavrepens (Streptomyces refreptyc). Can be mentioned.
  • the compound of the present invention or the bactericidal composition of the present invention is sprayed on all plants or parts of plants, as well as the soil surrounding the plants, or the soil sowing seeds, paddy fields, hydroponic water, and cultivation materials.
  • Plant pathogenic microorganisms by processing such as spraying, dusting, spraying, spreading, dipping, irrigation, infusion, watering (flooding), foaming, application, powder coating, coating, spraying, fumigation, fumigation, fumes and painting Or the plant disease which arises by it can be controlled.
  • plants refer to plants or plant groups such as wild plants, breeding plants, naturally occurring plants, and cultivated plants.
  • Introduction breeding method separate breeding method, cross breeding method, hybrid force breeding method, mutation breeding method
  • plants produced by breeding methods such as polyploid breeding methods, genetic recombination (gene transfer) methods, or marker-assisted selection.
  • the treatment is carried out regardless of before or after the infection of the phytopathogenic microorganism. And can be done throughout the storage period.
  • the plant part means all parts constituting the plant such as leaves, stems, trunks, branches, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes, or combinations thereof.
  • the bactericidal composition of the present invention adjusts the treatment amount so that the compound of the present invention is effective but does not show toxicity to plants. And can be used.
  • the amount that is effective but not toxic to plants is an amount that can sufficiently control phytopathogenic microorganisms or plant diseases caused thereby, and does not cause harm to plants, and this amount is controlled.
  • the plants to be applied, the natural environment used and the components of the composition of the invention it can vary within a relatively wide range.
  • Malvaceae plants such as okra, cotton; Astericaceae plants, such as cacao; Chenopodiaceae plants, such as spinach; Sapotaceae plants, such as miracle fruit; Rubiaceae plants, such as coffee tree, Robusta coffee tree; Cannabeceae plants, such as hops; Brassicaceae plants, for example, rape, turnip, cauliflower, cabbage, komatsuna, radish, ling-bill, Chinese cabbage, broccoli; Poaceae plants such as rice, barley, wheat, sugar cane, buckwheat, corn, rye; Cucurbitaceae plants, such as pumpkins, cucumbers, watermelons, zucchini, cucumbers, bitter gourds, chayotees, cucumbers, melons, yugao; Anacardiaceae plants, such as
  • a further aspect of the present invention relates to a seed treated with the compound of the present invention or the bactericidal composition of the present invention.
  • the seed is used to prevent the occurrence of plant diseases caused by phytopathogenic microorganisms.
  • contaminated seeds seeds infected with or adhering to phytopathogenic microorganisms
  • healthy seeds the contaminated seeds become the source of infection with phytopathogenic microorganisms, and the healthy plants that are growing nearby also have diseases. Propagate.
  • the seed according to the present invention treated with the compound of the present invention having high bactericidal activity against plant disease microorganisms or the bactericidal composition of the present invention is effective in preventing the occurrence of plant diseases and the transmission of pathogenic microorganisms to healthy plants. It becomes a means.
  • the bactericidal composition of the present invention can be used for seeds of all plants. Especially, rice, wheat, barley, rye, corn, soybean, cotton, potato, sugar beet, etc. have a large cultivation scale, and the spread of damage due to the spread of disease caused by contaminated seeds also increases, so the seeds according to the present invention are produced by phytopathogenic microorganisms. It is effective as a means to prevent the occurrence of plant diseases. In addition, treating the seed of the genetically modified crop with the compound of the present invention or the fungicidal composition of the present invention is also effective as a means for preventing the occurrence of plant diseases caused by phytopathogenic microorganisms.
  • Examples of genetically modified plants that can be treated with the compound of the present invention or the fungicide composition of the present invention are listed below, but are not necessarily limited thereto.
  • Plants transformed to show resistance to herbicides such as glyphosate-tolerant plants, bialaphos-tolerant plants, bromoxynil-tolerant plants, sulfonylurea-tolerant crops, imidazolinone-tolerant crops, 2,4- D-tolerant plants, dicamba-tolerant plants, isoxaflutole-tolerant plants, mesotrione-tolerant plants, etc .
  • Plants transformed to show resistance to pests for example, plants transformed to produce Bt toxin (insecticidal toxin of Bacillus thuringiensis), traits to produce natural enemy attractants Converted plants, etc .
  • Plants transformed to be resistant to plant diseases such as virus resistant plants, plants transformed to produce defensins, etc .
  • Plants transformed to increase the safety of the harvest such as mycotoxin-degrading enzyme-producing plants;
  • a plant transformed to be useful for breeding such as a plant transformed to show male sterility traits;
  • Plants transformed to exhibit resistance to environmental stress such as plants that exhibit drought tolerance using RNA chaperones, plants that accumulate glycine betaine, a compatible solute that is abundant in low temperature resistant plants, and compatible solutes
  • Plants transformed to produce specific functional nutrients such as plants that overproduce oleic acid
  • the compound of the present invention or the bactericidal composition of the present invention exhibits a high bactericidal effect against microorganisms, it can be used to protect industrial materials from the growth of microorganisms.
  • industrial materials include wood, plastic materials, paper materials, leather materials, tiles, pottery, cement, paint, cooling lubricants and adhesives. These industrial materials are treated by spraying, spreading, dusting, spraying, diffusing, dipping, irrigating, watering (watering), foaming, coating, powder coating of the compound of the present invention or the bactericidal composition of the present invention. , Coating, spraying, fumigation, smoking, fuming, painting and mixing.
  • the bactericidal composition of the present invention can contain additives usually used in agricultural chemical formulations as necessary.
  • the additive include a carrier such as a solid carrier or a liquid carrier, a surfactant, a binder, a tackifier, a thickener, a colorant, a spreading agent, an antifreezing agent, an anti-caking agent, a disintegrant, and a decomposition agent.
  • a carrier such as a solid carrier or a liquid carrier
  • a surfactant such as a solid carrier or a liquid carrier
  • a surfactant such as a binder, a tackifier, a thickener, a colorant, a spreading agent, an antifreezing agent, an anti-caking agent, a disintegrant, and a decomposition agent.
  • An inhibitor etc. are mentioned and you may use a preservative, a plant piece, etc. for an additional component as needed.
  • additives may be used alone or in combination of two or more.
  • solid carriers examples include quartz, clay, kaolinite, pyrophyllite, sericite, talc, chalk, bentonite, attapulgite, montmorillonite, acid clay, zeolite, natural rock, diatomaceous earth, calcite, marble, pumice, marine stone, dolomite
  • Natural minerals such as stones; inorganic salts such as calcium carbonate, ammonium sulfate or other ammonium salts, sodium sulfate, calcium chloride, potassium chloride; organic solid carriers such as starch, cellulose, plant powder; polyethylene, polypropylene, polychlorinated Plastic carriers such as vinylidene; other examples include synthetic silicic acid, synthetic silicate, alumina, finely divided silica, silicate and the like. These may be used alone or in combination of two or more.
  • liquid carriers examples include monohydric alcohols such as methanol, ethanol, propanol, isopropanol, and butanol, ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, and polyhydric alcohols such as polypropylene glycol glycerin.
  • polyhydric alcohol derivatives such as propylene glycol ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone; ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran, etc.
  • Ethers aliphatic hydrocarbons such as normal paraffin, naphthene, isoparaffin, kerosene, mineral oil; benzene, Aromatic hydrocarbons such as ruene, xylene, solvent naphtha and alkylnaphthalene, halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride; esters such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate and dimethyl adipate Lactones such as ⁇ -butyrolactone; amides such as dimethylformamide, diethylformamide, dimethylacetamide, N-alkylpyrrolidine; nitriles such as acetonitrile; sulfur compounds such as dimethylsulfoxide; soybean oil, rapeseed oil, cottonseed oil, And vegetable oils such as castor oil; water and the like. These may be used alone or
  • the surfactant is not particularly limited, but is preferably one that gels in water or exhibits swelling properties, such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, Polyoxyethylene resin acid ester, polyoxyethylene fatty acid diester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene dialkylphenyl ether, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene polyoxypropylene block polymer, alkyl Polyoxyethylene polypropylene block polymer ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide Polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzyl phenyl ether, polyoxyalkylene styrene phenyl ether, acetylene diol, polyoxyalkylene-added acetylene diol, polyoxyethylene ether type silicone, este
  • binders and tackifiers include carboxymethylcellulose and salts thereof, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinylpyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, and average molecular weight of 6000.
  • examples include polyethylene glycol having a molecular weight of ⁇ 20,000, polyethylene oxide having an average molecular weight of 100,000 to 5,000,000, and natural phospholipids (for example, cephalic acid, lecithin acid, etc.).
  • One of these binders and tackifiers may be used, or two or more thereof may be used in combination.
  • thickener examples include xanthan gum, guar gum, carboxymethyl cellulose, polyvinyl pyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative, water-soluble polymer such as polysaccharide; and inorganic fine powder such as high-purity bentonite and white carbon Etc. These thickeners may be used alone or in combination of two or more.
  • the colorant include inorganic pigments such as iron oxide, titanium oxide, and Prussian blue; and organic dyes such as alizarin dyes, azo dyes, and metal phthalocyanine dyes. These colorants may be used alone or in combination of two or more.
  • the spreading agent examples include silicone surfactant, cellulose powder, dextrin, modified starch, polyaminocarboxylic acid chelate compound, crosslinked polyvinylpyrrolidone, maleic acid and styrene acid, methacrylic acid copolymer, polyhydric alcohol polymer, Examples thereof include half esters with dicarboxylic acid anhydrides and water-soluble salts of polystyrene sulfonic acid.
  • silicone surfactant silicone surfactant
  • cellulose powder dextrin
  • modified starch polyaminocarboxylic acid chelate compound
  • crosslinked polyvinylpyrrolidone maleic acid and styrene acid
  • methacrylic acid copolymer methacrylic acid copolymer
  • polyhydric alcohol polymer examples thereof include half esters with dicarboxylic acid anhydrides and water-soluble salts of polystyrene sulfonic acid.
  • One of these spreading agents may be used, or two or more
  • the spreading agent examples include various surfactants such as sodium dialkylsulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester; paraffin, terpene, polyamide resin, polyacrylate, Examples include polyoxyethylene, wax, polyvinyl alkyl ether, alkylphenol formalin condensate, and synthetic resin emulsion.
  • these spreading agents may be used, or two or more thereof may be used in combination.
  • antifreezing agent examples include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin. These antifreeze agents may be used alone or in combination of two or more.
  • anti-caking agent examples include polysaccharides such as starch, alginic acid, mannose, and galactose, polyvinyl pyrrolidone, white carbon, ester gum, and petroleum resin.
  • polysaccharides such as starch, alginic acid, mannose, and galactose
  • polyvinyl pyrrolidone polyvinyl pyrrolidone
  • white carbon white carbon
  • ester gum and petroleum resin.
  • petroleum resin One type of these anti-caking agents may be used, or two or more types may be used in combination.
  • Disintegrants include, for example, sodium tripolyphosphate, sodium hexanemetaphosphate, metal stearate, cellulose powder, dextrin, methacrylic acid ester copolymer, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compound, sulfonated styrene / isobutylene / maleic anhydride Examples include acid copolymers and starch / polyacrylonitrile graft copolymers. One of these disintegrating agents may be used, or two or more thereof may be used in combination.
  • decomposition inhibitor examples include desiccants such as zeolite, quicklime and magnesium oxide, antioxidants such as phenols, amines, sulfurs and phosphates, and UV absorbers such as salicylic acid and benzophenone. It is done. These decomposition inhibitors may be used alone or in combination of two or more.
  • preservatives examples include potassium sorbate, 1,2-benzthiazolin-3-one and the like. One of these preservatives may be used, or two or more thereof may be used in combination.
  • plant pieces examples include sawdust, palm, corn cob, tobacco stem and the like.
  • the content ratio is usually 5 to 95%, preferably 20 to 90% for the carrier, and 20 to 90% for the surfactant on the mass basis.
  • 0.1 to 30%, preferably 0.5 to 10%, and other additives are selected in the range of 0.1 to 30%, preferably 0.5 to 10%.
  • the disinfectant composition and the agrochemical composition of the present invention include, for example, granules, powders, fine granules, liquids, aqueous solvents, oils, emulsions, surfing agents, emulsions, microemulsions, suspoemulsion formulations, EW (Emulsion oil in water) agent, microcapsule, wettable powder, suspension, tablet, granule wettable powder, dry flowable powder, wettable granule, aerosol, paste agent, cyclodextrin preparation, jumbo drug, pack It can be used as an agent suitable for agricultural and horticultural fungicides such as agents, water-soluble packaging preparations, powders, smoke agents, fumigants and the like.
  • Such embodiments include at least one compound of the present invention and appropriate solid or liquid carriers and, optionally, suitable adjuvants (eg, surfactants) to improve the dispersibility of the active ingredient and other properties.
  • suitable adjuvants eg, surfactants
  • the compound of the present invention can be used alone or as a preparation thereof, but it can be used as a bactericidal / fungicidal agent, bactericidal agent, acaricide, nematicide, insecticide, biological pesticide, herbicide, plant hormone agent. , Plant growth regulators, synergists, attractants, repellents, pigments, fertilizers, etc., or a mixture of one or more selected from these active ingredients as a pest control agent Or it can also be used as a plant protection agent.
  • control target disease, insect damage, weed
  • appropriate period of use or reduce the dose, synergize, or prevent the development of resistance in the control target
  • the activity of the mixture exceeds the individual activity and a cooperative medicinal effect with the co-components is achieved.
  • bactericides fungicides, bactericides, insecticides, acaricides, nematicides, snails, feeding inhibitors, herbicides, algicides, acaricides, killers Many nematodes, biological pesticides, pheromones, natural fungicides, and natural pesticides have been developed.
  • Pesticide Manual (2013) published by British Crop Protection Council, Kumiai Pesticides Directory published by National Federation of Agricultural Cooperatives (2014) ) And SHIBUYA INDEX (17th edition) published by the National Rural Education Association. Examples are shown below, but are not limited thereto.
  • fungicides and bactericides examples include 2-phenylphenol, 8-quinolinol sulfate, acibenzolar-S-methyl, acipetacs, acipetacs, Petapscappers (aipepetacs-copper), acipetaxzinc (acypetacs-zinc), albendazole, aldimorph, allicin, allyl alcohol, thiatotratra (in) amicalthiazol), amisulbrom, Mobam, ampropylphos, anilazine, asomate, aureofungin, azaconazole, azitiramro, azoxyram, azoxyram barium polysulfide), benalaxyl, benalaxyl M (benalaxyl-M), benodanyl, benomyl, benquinrox, bentalurn, bentalurn Benthiazole, benzalkonium chloride, benz
  • insecticides examples include 1,2-dichloropropane, 1,3-dichloropropene (1,3- dichloropropene, abamectin, acephate, acequinocyl, acetamiprid, acethion, acetonitrine, acetophore, acetoprole (Afidopyropene), aranicarb, aldoxycarb alb), allethrin, allicin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-endosulfide, amidifion, amidifion Aminocarb, amiton, amitraz, anabasine, aramite, athidathion, azadirachtin, azamethiphos (azamethiphos) nphos-ethyl), azophos-methyl, azobenzene, azocycl
  • herbicides and algicides examples include 2,3,6-TBA, 2,4,5-TB, 2,4-D, 2,4-DB, 2,4-DEB, 2,4-DEP 3,4-DA, 3,4-DB, 3,4-DP, 4-CPA, 4-CPB, 4-CPP, acetochlor, acifluorfen, aclonifen, acrolein ( acrolein, alidochlor, alloxydim, allyl alcohol, allorac, ametridione, amethrin, amibuzin, amibuzin Chlorosulfuron, aminocyclopyrchlor, aminopyralid, amiprofos-methyl, amiprophos, amifosul, sulfammonium, sulfamate Anisuron, asuram, atraton, atrazine, atrazine, azaphenidin, azimsulfuron, aziprotrine, barban, CPC Bebuturamid, benazoline, benc
  • Fenoxaprop-P Fenoxaprop-P, fenoxasulfone, fenquinotrione, fenteracol, fenthiaprop, tin, fentrazamide, fentrazamide Fenuron, ferrous sulfate, flamprop, flampprop-M, flazasulfuron, florasulfam, fluazifop, flazihopop -P), fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flufenpyr Flumezin, full microlac, flumioxazine, flumipropyne, fluometuron, fluorodifen, fluorglycophylfluorophene, fluoroglycofenfluoro (Fluorontrofen), fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron,
  • biological pesticides include nuclear polyhedrosis virus (Nuclear polyhedrosis virus, NPV), granule disease virus (Granulosis virus, GV), cytoplasmic polyhedrovirus (CPV), Steiner pneuma pnecaine, and Steiner pneumona pneumonia sp. , Steinernema glaserei, Monocrosporum phymatopagum, Steinernema kushidai, Pasteuret penetrans pastel.
  • nuclear polyhedrosis virus Nuclear polyhedrosis virus, NPV
  • GV granule disease virus
  • CPV cytoplasmic polyhedrovirus
  • Steiner pneuma pnecaine Steiner pneumona pneumonia sp.
  • Steinernema glaserei Monocrosporum phymatopagum
  • Steinernema kushidai Pasteuret penetrans pastel.
  • Agrobacterium radiobacter Agrobacterium radiobacter
  • Bacillus subtilis Bacillus subtilis
  • Bacillus amyloliquefaciens Bacillus amyloliquefaciens
  • Erwinia carotovora Erwinia carotovora
  • Pseudomonas fluorescens Pseudomonas fluorescens
  • Talaromyces flavus Talaromyces flavus
  • Trichoderma Atrioviride Trichoderma atroviride
  • Bacillus thuringiensis Beauveria brownia br ngniartii), Beauveria Bashiana (Beauveria bassiana
  • Pekiromaisesu Fumosoroseusu Pieria brownia br ngniartii
  • Beauveria Bashiana Beauveria bassiana
  • Pekiromaisesu Fumosoroseusu Pieria brownia br ngniartii
  • pheromone agents include brevicomin, cerrale, codremone, cue-lure, disparlure, dominicallure-1 and eugenol ( eugenol, frontalin, gossyplere, grandis, hexalure, ipsdienol, ipsenol, japonile, tilil, ne Little lure, luo lure Medlure, megatoic acid, methyl eugenol, moguchuun, muscarure, orfuraure, rela, orremonre, ostramone , Sulcatol, trimedlure, trunk-call, ⁇ -multistriatin and the like.
  • pheromone agents there are acrep, butopyronoxyl, camphor, d-camphor, carboxide, dibutyl phthalate, and diethyl phthalate.
  • Amide diethyltoluamide
  • dimethyl carbonate dimethyl phthalate
  • dibutyl succinate ethohexadiol
  • hexamide amide idylidine (Methoquin-butyl)
  • Runeodekanamido methylneodecanamide
  • oxamate oxamate
  • quench quwenzhi
  • Kuingujingu quyingding
  • Rebemido zengxiaoan and the like.
  • Examples of natural fungicides and insecticides include machine oils, methylphenyl acetate, ⁇ -pinene, protein hydrolysate, (Z) -1 -Tetradecen-1-ol, turpentine oil and the like.
  • the bactericidal composition of the present invention may contain one or more compounds of the present invention or salts thereof.
  • the blending ratio of the compound represented by the formula [1] according to the present invention in the bactericidal composition of the present invention is appropriately selected as necessary, but is 0.001 to 10% (weight) in the case of powders and granules. ), Preferably in the range of 0.005 to 5% (weight).
  • weight in the case of using an emulsion, a wettable powder, etc.
  • it is appropriately selected from the range of 1 to 50% (weight), preferably 5 to 30% (weight).
  • a flowable agent or the like it is appropriately selected from the range of 1 to 50% (weight), preferably 5 to 30% (weight).
  • the application amount of the bactericidal composition of the present invention varies depending on the type of compound used, target crop, target disease, occurrence tendency, environmental conditions, dosage form used, etc., but it is used as it is like powders and granules.
  • the active ingredient is appropriately selected from the range of 1 g to 50 kg, preferably 10 g to 10 kg per hectare.
  • when used in a liquid form such as an emulsion, wettable powder, flowable agent, etc. it may be appropriately selected from the range of 0.1 to 50,000 ppm, preferably 10 to 10,000 ppm.
  • Step 1 4- [4- (6-Methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl) -2-thiazolyl] piperidinecarboxylate 1,1-dimethylethyl
  • ester 4- (4-formyl-2-thiazolyl) piperidinecarboxylic acid 1,1-dimethylethyl ester (292 mg) (compound described in WO2008 / 013622) and 3-methylsulfonyloxy-1,2-benzene Dimethanol (228 mg) and para-toluenesulfonic acid monohydrate (15 mg) were dissolved in toluene (15 mL) and heated to reflux for 4 hours using a Dean-Stark apparatus.
  • reaction mixture was cooled to room temperature, diluted with ethyl acetate, and washed with water and saturated brine.
  • the organic layer was dried over anhydrous sodium sulfate, the inorganic substance was filtered off, and the solvent was distilled off under reduced pressure.
  • Step 2 Preparation of 4- [4- (6-Methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl) -2-thiazolyl] piperidine trifluoroacetate 4- [4- (6-Methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl) -2-thiazolyl] piperidinecarboxylic acid 1,1-dimethylethyl ester (510 mg) Dissolve in dichloromethane (10 mL), add trifluoroacetic acid (1.7 g) under ice cooling, and stir at room temperature for 3 hours.
  • Trifluoroacetic acid was distilled off under reduced pressure to give 4- [4- (6-methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl) -2-thiazolyl].
  • Piperidine trifluoroacetate was obtained as a yellow amorphous solid (508 mg, 100% yield).
  • Step 3 Preparation of (3,6-dichloropyridin-2-yl) carbamic chloride
  • Triphosgene 99 mg was dissolved in dichloromethane (10 mL), pyridine (73 mg) was added under ice cooling, and the mixture was stirred for 10 minutes.
  • 3,6-Dichloro-2-pyridinamine 136 mg was added and stirred overnight at room temperature. The solvent was distilled off under reduced pressure to obtain (3,6-dichloropyridin-2-yl) carbamic acid chloride as a yellow solid (188 mg, yield 100%).
  • Step 4 N- (3,6-Dichloropyridin-2-yl) -4- [4- (6-methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl ) -2-Thiazolyl] piperidine-1-carboxamide 4- [4- (6-methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl)-in Step 2 2-thiazolyl] piperidine trifluoroacetate (508 mg) was dissolved in dichloromethane (10 mL), triethylamine (152 mg) was added under ice cooling, and then (3,6-dichloropyridine-2- Yl) A solution of carbamic chloride (188 mg) in dichloromethane (5 mL) was added dropwise and stirred at room temperature overnight.
  • Step 1 Preparation of 4- (4-formyl-2-thiazolyl) piperidinetrifluoroacetate 4- (4-Formyl-2-thiazolyl) piperidinecarboxylic acid 1,1-dimethylethyl ester (1.1 g) was dissolved in dichloromethane (1.1 g). 20 mL), trifluoroacetic acid (6.1 g) was added under ice cooling, and the mixture was stirred at room temperature for 3 hours. Trifluoroacetic acid was distilled off under reduced pressure to obtain 4- (4-formyl-2-thiazolyl) piperidine trifluoroacetate as a yellow amorphous solid (1.1 g, yield 100%).
  • Step 2 Preparation of N- (3,6-dichloropyridin-2-yl) -4- (4-formyl-2-thiazolyl) piperidine-1-carboxamide 4- (4-Formyl-2-thiazolyl) from Step 1
  • Piperidine trifluoroacetate was dissolved in dichloromethane (20 mL), triethylamine (543 mg) was added under ice-cooling, and a solution of the compound obtained in Example 3 step 3 (967 mg) in dichloromethane (20 mL) was added dropwise.
  • Example 1 N- (3,6-dichloropyridin-2-yl) -4- (4-formyl-2-thiazolyl) piperidine-1-carboxamide was obtained by reacting and purifying in the same manner as in the preparation of Step 1 of Step 4. Obtained as a yellow amorphous solid (1.0 g, 72% yield).
  • Step 3 N- (3,6-Dichloropyridin-2-yl) -4- [4- (6,9-difluoro-1,5-dihydro-3H-2,4-benzodioxepin-3-yl ) -2-Thiazolyl] piperidine-1-carboxamide N- (3,6-dichloropyridin-2-yl) -4- (4-formyl-2-thiazolyl) piperidine-1-carboxamide (193 mg) and 3 , 6-Difluoro-1,2-benzenedimethanol (174 mg) and p-toluenesulfonic acid monohydrate (14 mg) were dissolved in toluene (15 mL) and the same reaction as in the preparation of Step 1 of Example 1 The title compound was obtained as a colorless oil (34 mg, 13% yield) by purification.
  • Example 3 N- (3,6-dichloropyridin-2-yl) -4- [4- (6-fluoro-9-methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxe Preparation of pin-3-yl) -2-thiazolyl] piperidine-1-carboxamide (Compound 4)
  • the compound (193 mg) obtained in Step 2 of Example 2 above and 3,6-difluoro-1,2-benzenedi Methanol (250 mg) and para-toluenesulfonic acid monohydrate (5 mg) are dissolved in toluene (15 mL), reacted in the same manner as in the preparation of Example 1, Step 1, and purified to give the title compound. Obtained as a colorless amorphous solid (60 mg, 19% yield).
  • Step 1 4- (4-Formyl-2-thiazolyl) -1- [2- [5-methyl-3- (trifluoromethyl) -1H-1,2,4-triazol-1-yl] acetyl] piperidine 2- (5-Methyl-3- (trifluoromethyl) -1H-1,2,4-triazol-1-yl) acetic acid (800 mg) (compound described in US2014 / 0057937) dissolved in dichloromethane (30 mL) Under cooling with ice, triethylamine (774 mg), N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide (587 mg), 4- (4-formyl-2-thiazolyl) piperidine trifluoroacetate (748 mg) And stirred at room temperature overnight.
  • Step 2 4- [4- (6-Fluoro-9-methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl) -2-thiazolyl] -1- [2 Preparation of — [5-methyl-3- (trifluoromethyl) -1H-1,2,4-triazol-1-yl] acetyl] piperidine 4- (4-Formyl-2-thiazolyl) -1- [2- [5-Methyl-3- (trifluoromethyl) -1H-1,2,4-triazol-1-yl] acetyl] piperidine (194 mg) and 3-fluoro-6-methylsulfonyloxy-1,2-benzene Dimethanol (250 mg) and p-toluenesulfonic acid monohydrate (5 mg) were dissolved in toluene (15 mL), reacted in the same manner as in the preparation of Example 1, step 1, and purified. The title compound was
  • Example 5 4- [4- (6-Methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl) -2-thiazolyl] -1- [2- [5 Preparation of -Methyl-3- (trifluoromethyl) -1H-1,2,4-triazol-1-yl] acetyl] piperidine (Compound 12) 2- (5-Methyl-3- (trifluoromethyl) -1H -1,2,4-Triazol-1-yl) acetic acid (209 mg) was dissolved in dichloromethane (15 mL), and triethylamine (202 mg) and N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide were cooled with ice.
  • Step 1 Preparation of 4- (4-formyl-2-thiazolyl) -1- [2- [thiophen-2-yl] acetyl] piperidine 2-thienylacetic acid (1.8 g) was dissolved in dichloromethane (40 mL) Under ice cooling, triethylamine (2.6 g), N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide (1.9 g), 4- (4-formyl-2-thiazolyl) piperidine trifluoroacetate ( 4- (4-formyl-2-thiazolyl) -1- [2- [thiophen-2-yl] by reacting in the same manner as in the preparation of Example 4, Step 1, and purifying. ] Acetyl] piperidine was obtained as a brown oil (1.7 g, 63% yield).
  • Step 2 4- [4- (6-Fluoro-9-methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl) -2-thiazolyl] -1- [2 Preparation of-[thiophen-2-yl] acetyl] piperidine 4- (4-formyl-2-thiazolyl) -1- [2- [thiophen-2-yl] acetyl] piperidine (200 mg) and 3-fluoro-6 -Methylsulfonyloxy-1,2-benzenedimethanol (312 mg) and para-toluenesulfonic acid monohydrate (6 mg) were dissolved in toluene (15 mL) and the same reaction as in the preparation of Example 1, Step 1 And the title compound was obtained as a yellow amorphous solid (167 mg, yield 48%).
  • Step 1 Preparation of 2- (thiophen-2-yl) acetyl chloride
  • 2- (thiophen-2-yl) acetyl chloride 132 mg was dissolved in dichloromethane (10 mL), and oxalyl chloride (177 mg) and N, N-dimethylformamide ( 1 drop) was added and stirred at room temperature for 3 hours.
  • the solvent was distilled off under reduced pressure to obtain 2- (thiophen-2-yl) acetyl chloride (149 mg, yield 100%) as a yellow solid.
  • Step 2 4- [4- (6 Methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl) -2-thiazolyl] -1- [2- [thiophene-2 Preparation of -yl] acetyl] piperidine 4- [4- (6-Methylsulfonyloxy-1,5-dihydro-3H-2,4-benzodioxepin-3-yl) -2-thiazolyl] piperidine trifluoroacetic acid The salt (339 mg) was dissolved in dichloromethane (5 mL), triethylamine (203 mg) was added under ice cooling, and then 2- (thiophen-2-yl) acetyl chloride (149 mg) obtained in Step 2 was added in dichloromethane (5 mL).
  • the organic layer was dried over anhydrous sodium sulfate, the inorganic substance was filtered off, and the solvent was distilled off under reduced pressure.
  • the residue was purified by flash silica gel column chromatography (eluted with ethyl acetate-hexane: 30% -100%) using a flash automatic purifier (biotage AB / Isolera TM ) to give 3-methylsulfonyloxy-1, 2-Benzenedimethanol was obtained as a colorless solid (1.36 mg, yield 64%, melting point 56-58 ° C.).
  • Step 1 Preparation of 5-fluoro-2-methylsulfonyloxyphthalide
  • 5-Fluoro-2-hydroxyphthalide 200 mg
  • compound described in WO2003 / 076424 is dissolved in N, N-dimethylformamide (10 mL).
  • Methylsulfonyl chloride 150 mg
  • triethylamine 133 mg
  • the reaction mixture was diluted with ethyl acetate and washed with saturated brine.
  • Step 2 Preparation of 3-fluoro-6-methylsulfonyloxy-1,2-benzenedimethanol 5-Fluoro-2-methylsulfonyloxyphthalide (290 mg) was dissolved in tetrahydrofuran (10 mL) and lithium aluminum hydride ( 45 mg) was added and stirred at room temperature for 30 minutes. 1N Hydrochloric acid was added to the reaction mixture under ice cooling, and the mixture was stirred at room temperature for 1 hr. The reaction solution was extracted with dichloromethane and washed with saturated brine.
  • Wettable Powder 10 parts of the present invention is mixed with 2 parts of sodium lauryl sulfate, 4 parts of sodium lignin sulfonate, 20 parts of white carbon and 64 parts of clay and pulverized. As a result, a 10% wettable powder was obtained.
  • Flowable agent 10 parts of the compound of the present invention 4 parts of polyoxyethylene allyl phenyl ether sulfate, 5 parts of polyoxyethylene alkyl ether, 5 parts of propylene glycol, 0.2 part of a silicon-based antifoaming agent, 0 of sodium montmorillonite 8 parts and 50 parts of water were added and mixed, and wet pulverized using a dyno mill to obtain a pulverized suspension.
  • Emulsion 10 parts of the compound of the present invention, 2 parts of calcium dodecylbenzenesulfonate, and 15 parts of castor oil ethoxylate are mixed with 73 parts of an aromatic hydrocarbon mixture and dissolved to obtain a homogeneous 10% emulsifiable oily liquid. Obtained.
  • Granule wettable powder 10 parts of the compound of the present invention, 20 parts of sodium lignin sulfonate, 10 parts of sodium salt of naphthalene sulfonic acid condensate, 3 parts of sodium alkylbenzene sulfonate, 0.5 part of silicone-based defoamer Then, 5 parts of diatomaceous earth, 10 parts of ammonium sulfate, 10 parts of talc and 31.5 parts of clay part were added, sufficiently mixed and pulverized to obtain a pulverized product. An appropriate amount of water as necessary was added to the pulverized product, granulated with a granulator, and sieved after drying to obtain 10% hydratable fine granules.
  • Microemulsion agent 10 parts of the compound of the present invention, 12 parts of fatty acid dimethylamide, 10 parts of cyclohexanone, 15 parts of arylphenol ethoxylate, 10 parts of alcohol ethoxylate and 43 parts of water are added and heated. The mixture was stirred for several minutes to obtain a stable 10% water-soluble liquid.
  • Test Procedure for Preparation of Test Suspension 10% wettable powder prepared according to Formulation Example 1 was diluted with a Teen20 aqueous solution prepared to a concentration of 1/5000, and the compound represented by formula [1] was concentrated at 100 ppm. Prepared.
  • the compound of the present invention exhibits excellent control activity especially against pathogenic bacteria that affect agricultural and horticultural plants, so it is extremely useful as a new agricultural chemical and has industrial applicability.

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Abstract

La présente invention concerne : un composé représenté par la formule [1] ou un sel de celui-ci ; une composition germicide contenant le composé ou un sel de celui-ci ; un procédé permettant de maîtriser une maladie touchant les plantes qui est provoquée par un micro-organisme phytopathogène, lequel procédé comprend une étape consistant à appliquer ladite composition germicide ; ainsi qu'un procédé de production dudit composé.
PCT/JP2015/085829 2015-12-22 2015-12-22 Composé cyclique à 11 éléments condensé et germicide pour l'agriculture et l'horticulture le contenant WO2017109858A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018193387A1 (fr) 2017-04-19 2018-10-25 Pi Industries Ltd. Composés hétérocycliques ayant des propriétés microbiocides
WO2019020540A1 (fr) 2017-07-26 2019-01-31 Basf Se Mélanges pesticides
WO2019048988A1 (fr) 2017-09-08 2019-03-14 Pi Industries Ltd. Nouveaux composés hétérocycliques fongicides
WO2019048989A1 (fr) 2017-09-08 2019-03-14 Pi Industries Ltd. Nouveaux composés hétérocycliques fongicides

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JP2004505967A (ja) * 2000-08-08 2004-02-26 バイエル　クロップサイエンス　ゲーエムベーハー ヘテロシクリルアルキルアゾール誘導体及び農薬としてのその使用
WO2015036379A1 (fr) * 2013-09-13 2015-03-19 Bayer Cropscience Ag Compositions fongicides contenant un fongicide à base de thiazolylisoxazoline et un fongicide biologique
WO2015055574A1 (fr) * 2013-10-17 2015-04-23 Bayer Cropscience Ag Nouvelle forme cristalline du 2-{3-[2-(1-{[3,5-bis(difluorométhyl)-1h-pyrazol-1-yl]acétyl}pipéridin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophénylméthanesulfonate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004505967A (ja) * 2000-08-08 2004-02-26 バイエル　クロップサイエンス　ゲーエムベーハー ヘテロシクリルアルキルアゾール誘導体及び農薬としてのその使用
WO2015036379A1 (fr) * 2013-09-13 2015-03-19 Bayer Cropscience Ag Compositions fongicides contenant un fongicide à base de thiazolylisoxazoline et un fongicide biologique
WO2015055574A1 (fr) * 2013-10-17 2015-04-23 Bayer Cropscience Ag Nouvelle forme cristalline du 2-{3-[2-(1-{[3,5-bis(difluorométhyl)-1h-pyrazol-1-yl]acétyl}pipéridin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophénylméthanesulfonate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018193387A1 (fr) 2017-04-19 2018-10-25 Pi Industries Ltd. Composés hétérocycliques ayant des propriétés microbiocides
WO2019020540A1 (fr) 2017-07-26 2019-01-31 Basf Se Mélanges pesticides
WO2019048988A1 (fr) 2017-09-08 2019-03-14 Pi Industries Ltd. Nouveaux composés hétérocycliques fongicides
WO2019048989A1 (fr) 2017-09-08 2019-03-14 Pi Industries Ltd. Nouveaux composés hétérocycliques fongicides

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