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WO2010125782A1 - Composé hétérocyclique contenant de l'azote et bactéricide agricole ou horticole - Google Patents

Composé hétérocyclique contenant de l'azote et bactéricide agricole ou horticole Download PDF

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Publication number
WO2010125782A1
WO2010125782A1 PCT/JP2010/002947 JP2010002947W WO2010125782A1 WO 2010125782 A1 WO2010125782 A1 WO 2010125782A1 JP 2010002947 W JP2010002947 W JP 2010002947W WO 2010125782 A1 WO2010125782 A1 WO 2010125782A1
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Japanese (ja)
Inventor
三谷晃
清水一彌
▲桑▼原頼人
佐藤元亮
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Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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Priority to JP2011511296A priority Critical patent/JP5254436B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/86—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 six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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 nitrogen-containing heterocyclic compound or a salt thereof, and an agricultural and horticultural fungicide containing at least one of these compounds as an active ingredient.
  • control agents are used against crop diseases, but their control efficacy is insufficient, their use is restricted by the emergence of drug-resistant pathogens, and There are many things that are not necessarily satisfactory control drugs because they cause phytotoxicity and pollution to plants, or are toxic to human and livestock and have environmental impacts. Therefore, there is a strong demand for the emergence of such a drug that can be safely used with few such defects.
  • Patent Documents 1 and 2 disclose a quinoline derivative having a chemical structure similar to that of the compound of the present invention and an agricultural and horticultural fungicide containing it as an active ingredient. However, the compounds of the present invention are not described.
  • the present invention relates to a novel nitrogen-containing heterocyclic compound or a salt thereof, which can be an active ingredient of an agricultural and horticultural fungicide that has a certain effect and can be used safely, and contains at least one of these compounds as an active ingredient.
  • An object is to provide an antibacterial agent.
  • the present invention provides a nitrogen-containing heterocyclic compound represented by the formula (I) or a salt thereof.
  • R 1 represents an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, or an unsubstituted or substituted group.
  • R 2 represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 haloalkyl group, a C2-20 alkenyl group, a C2-20 haloalkenyl group, a C2-20 alkynyl group, a C2-20 haloalkynyl group, a C1 ⁇ 20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, C4-20 cycloalkenyl group, C8-20 cycloalkynyl group, C1-20 acyl group, C1-20 alkoxycarbonyl group, unsubstituted or substituted And a C6-10 aryl group having a non-substituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, or an unsubstituted or substituted heteroaralkyl group.
  • R 3 to R 6 are each independently a hydrogen atom, halogen atom, C1-20 alkyl group, C1-20 haloalkyl group, C2-20 alkenyl group, C2-20 haloalkenyl group, C2-20 alkynyl group, C2 -20 haloalkynyl group, C1-20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, C3-20 cycloalkoxy group, C2-20 alkenyloxy group, C2-20 alkynyloxy group, C1-20 Alkylthio group, cyano group, nitro group, unsubstituted or substituted amino group, hydroxyl group, thiol group, unsubstituted or substituted phenyl group, unsubstituted or substituted aralkyl group, unsubstituted or substituted group An aryloxy group having a substituent, or an unsubstituted or substituted heterocycl
  • R 4 and R 5 , and R 5 and R 6 may together form a 5- to 8-membered ring having an unsubstituted or substituted group together with the carbon atom to which they are bonded.
  • R 5 and R 6 are not simultaneously hydrogen atoms.
  • X represents a halogen atom, a nitro group, an unsubstituted or substituted amino group, a hydroxyl group, or an organic group.
  • n represents an integer of 0 to 4.
  • Z represents an oxygen atom or a sulfur atom.
  • R 4 and R 5 , and R 5 and R 6 together have an unsubstituted or substituted group formed together with the carbon atom to which each is bonded.
  • the member ring is preferably an unsubstituted or substituted cycloalkene ring, an unsubstituted or substituted aromatic hydrocarbon ring, or an unsubstituted or substituted heterocyclic ring.
  • the present invention also provides an agricultural and horticultural fungicide containing as an active ingredient at least one of the nitrogen-containing heterocyclic compound of the present invention or a salt thereof.
  • the nitrogen-containing heterocyclic compound or a salt thereof of the present invention is a novel compound and is useful as an active ingredient of an agricultural and horticultural fungicide that can be used safely and reliably.
  • the agricultural and horticultural fungicide of the present invention is an agent that has an excellent control effect, does not cause phytotoxicity to plants, and has little toxicity to human and livestock fish and environmental impact.
  • Nitrogen-containing heterocyclic compound represented by formula (I) or salt thereof is the compound represented by formula (I) or a salt thereof.
  • the nitrogen-containing heterocyclic compound or a salt thereof of the present invention includes hydrates, various solvates and crystal polymorphs.
  • R 1 represents an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, or an unsubstituted or substituted group.
  • the “C6-10 aryl group” for R 1 means a monocyclic or polycyclic aryl group having 6 to 10 carbon atoms.
  • the polycyclic aryl group as long as at least one ring is an aromatic ring, the remaining ring may be a saturated alicyclic ring, a partially unsaturated alicyclic ring, or an aromatic ring.
  • the “C6-10 aryl group” include phenyl group, naphthyl group, azulenyl group, indenyl group, indanyl group, tetralinyl group and the like. Of these, a phenyl group is preferred.
  • the “aralkyl group” for R 1 is a C1-20 alkyl group substituted with a C6-10 aryl group.
  • the “C1-20 alkyl group” means a linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms.
  • Examples of the “C1-20 alkyl group” include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and n-pentyl group.
  • a C1-6 alkyl group that is, a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms is preferable.
  • the “aralkyl group” include benzyl group, phenethyl group, 3-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.
  • C6-10 aryl C1-6 alkyl groups are preferred.
  • the “heteroaryl group” for R 1 is a 5- to 10-membered aryl group containing 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom in addition to a carbon atom as an atom constituting the ring. In this case, it may be a single ring or a polycyclic ring condensed. Examples of the “heteroaryl group” include the following groups.
  • 5-membered heteroaryl group pyrrolyl group such as pyrrol-1-yl group, pyrrol-2-yl group and pyrrol-3-yl group; Furyl groups such as a furan-2-yl group and a furan-3-yl group; Thienyl groups such as a thiophen-2-yl group and a thiophen-3-yl group; Imidazolyl groups such as imidazol-1-yl group, imidazol-2-yl group, imidazol-4-yl group, imidazol-5-yl group; Pyrazolyl groups such as a pyrazol-1-yl group, a pyrazol-3-yl group, a pyrazol-4-yl group, a pyrazol-5-yl group; An oxazolyl group such as an oxazol-2-yl group, an oxazol-4-yl group, an oxazol-5-yl group; Isoxazo
  • heteroaryl group for R 1 is a C1-20 alkyl group substituted with a heteroaryl group.
  • heteroaryl group for substituting the C1-20 alkyl group include the above heteroaryl groups.
  • heteroarylkyl group include the following groups.
  • R 2 represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 haloalkyl group, a C2-20 alkenyl group, a C2-20 haloalkenyl group, a C2-20 alkynyl group, a C2-20 Haloalkynyl group, C1-20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, C4-20 cycloalkenyl group, C8-20 cycloalkynyl group, C1-20 acyl group, C1-20 alkoxycarbonyl group And an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, or an unsubstituted or substituted heteroaralkyl group.
  • Examples of the “halogen atom” for R 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the “C1-20 alkyl group” for R 2 means a linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms. Examples of the “C1-20 alkyl group” include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and n-pentyl group.
  • C1-20 haloalkyl group for R 2 means a group in which at least one hydrogen atom in the C1-20 alkyl group is substituted with a halogen atom.
  • “C1-20 haloalkyl group” includes fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2 , 2-trifluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 3,3,3-trifluoropropyl group, 2,2,2 -Trifluoro-1-trifluoromethylethyl group, perfluorohexyl group, perchlorohexyl group, perfluorooctyl group, perchlorooctyl group
  • the “C2-20 alkenyl group” for R 2 means a C 2-20 straight or branched chain unsaturated hydrocarbon group having at least one carbon-carbon double bond.
  • Examples of the “C2-20 alkenyl group” include vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2 -Propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group Group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-heptenyl group, 6-heptenyl group, 1-octenyl group, 7-octenyl group, 1-decenyl group, 9-decenyl group,
  • the “C2-20 haloalkenyl group” for R 2 is a group formed by substituting at least one hydrogen atom in a C2-20 alkenyl group with a halogen atom.
  • the “C2-20 haloalkenyl group” includes a 3-chloro-2-propenyl group, a 4-chloro-2-butenyl group, a 4,4-dichloro-3-butenyl group, and a 4,4-difluoro-3-butenyl group.
  • the “C2-20 alkynyl group” of R 2 means a C 2-20 straight or branched chain unsaturated hydrocarbon group having at least one carbon-carbon triple bond.
  • Examples of the “C2-20 alkynyl group” include ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2-methyl-3 -Butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 2-methyl-3-pentynyl, 1-hexynyl, 1,1 -Dimethyl-2-butynyl group, dodecinyl group, butadecynyl group, heptadecynyl group, 4-ethylhexadecynyl group and the like.
  • the “C2-20 haloalkynyl group” for R 2 is a group in which at least one hydrogen atom in the C2-20 alkynyl group is substituted with a halogen atom.
  • Examples of the “C2-20 haloalkynyl group” include 3-chloro-1-propynyl group, 3-chloro-1-butynyl group, 3-bromo-1-butynyl group, 3-bromo-2-propynyl group, 3-iodo -2-propynyl group, 5,5-dichloro-2-methyl-3-pentynyl group, 3-bromo-1-hexynyl group, 4-chloro-1,1-dimethyl-2-butynyl group, 4,4,6 , 6-tetrafluoro-1-dodecynyl group and the like. Of these, C2-6 haloalkynyl groups are preferred.
  • the “C1-20 alkoxy group” of R 2 is a group in which a hydrogen atom in a hydroxyl group is substituted with a C1-20 alkyl group.
  • Examples of the “C1-20 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy Group, 1-ethylpropoxy group, n-hexyloxy group, isohexyloxy group, 4-methylpentoxy group, 3-methylpentoxy group, 2-methylpentoxy group, 1-methylpentoxy group, 3, 3 -Dimethylbutoxy group, 2,2-dimethylbutoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1-ethylbutoxy group 2-ethylbutoxy group
  • the “C1-20 haloalkoxy group” for R 2 is a group formed by substituting at least one hydrogen atom in a C1-20 alkoxy group with a halogen atom.
  • Examples of the “C1-20 haloalkoxy group” include chloromethoxy group, dichloromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1-difluoroethoxy group, 2,2,2-trifluoro Examples include ethoxy group, pentafluoroethoxy group, 4,5-dichloro-3-methylpentoxy group, 2-fluoro-2-ethyldecyloxy group, 1-chlorolauryloxy group and the like. Of these, C1-6 haloalkoxy groups are preferred.
  • the “C3-20 cycloalkyl group” of R 2 is a hydrocarbon group having 3-20 carbon atoms having a saturated alicyclic structure.
  • Examples of the “C3-20 cycloalkyl group” include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclopropylmethyl group, 2-cyclopropylethyl group, 2,3,3- Trimethylcyclobutyl group, cyclopentylmethyl group, 2-cyclohexylethyl group, 2-cyclooctylethyl group, 4,4,6,6-tetramethylcyclohexyl group, 1,3-dibutylcyclohexyl group, norbornyl group, bicyclo [2. 2.2] An octyl group, an adamantyl group, etc. are mentioned. Of these, C3-6 cyclo
  • the “C4-20 cycloalkenyl group” of R 2 is a hydrocarbon group having 4-20 carbon atoms having an unsaturated alicyclic structure containing a carbon-carbon double bond.
  • Examples of the “C4-20 cycloalkenyl group” include 1-cyclobutenyl group, 1-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 3-cyclohexenyl group, 3-cycloheptenyl group, 4-cyclooctenyl group, 2-methyl-3-cyclohexenyl group, 3,4-dimethyl-3-cyclohexenyl group, cyclopentenylmethyl group, 3-cyclopentenylmethyl group, 3-cyclohexenylmethyl group, 2- (3-cyclohexenyl group ) And the like. Of these, C4-8 cycloalkenyl groups are preferred.
  • the “C8-20 cycloalkynyl group” for R 2 is a hydrocarbon group having 8-20 carbon atoms having an unsaturated alicyclic structure containing a carbon-carbon triple bond.
  • Examples of the “C8-20 cycloalkynyl group” include 5-cyclooctynyl group, 6-cyclodecynyl group, 7-cyclododecynyl group, 2,3-diethyl-4-cyclodecynyl group, 5-cyclooctynylmethyl group and the like. Of these, C8-12 cycloalkynyl groups are preferred.
  • the “C1-20 acyl group” of R 2 is a group having 1 to 20 carbon atoms in which a hydrogen atom, a linear or branched alkyl group, an aryl group or a heteroaryl group is bonded to a carbonyl group.
  • C1-20 acyl group examples include formyl group, acetyl group, propionyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, pentanoyl group, pivaloyl group, valeryl Group, isovaleryl group, octanoyl group, nonanoyl group, decanoyl group, 3-methylnonanoyl group, 8-methylnonanoyl group, 3-ethyloctanoyl group, 3,7-dimethyloctanoyl group, undecanoyl group, dodecanoyl group, tridecanoyl group, tetra Decanoyl group, pentadecanoyl group, hexadecanoyl group, 1-methylpentadecanoyl group, 14-methylpentadecanoyl group, 13,13
  • the “C1-20 alkoxycarbonyl group” of R 2 is a group in which a C1-20 alkoxy group is bonded to a carbonyl group.
  • Examples of the “C1-20 alkoxycarbonyl group” include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, n -Pentyloxycarbonyl group, n-hexyloxycarbonyl group, decyloxycarbonyl group, dodecyloxycarbonyl group, 2-ethyldecyloxycarbonyl group, lauryloxycarbonyl group and the like. Of these, C1-6 alkoxycarbonyl groups are preferred.
  • C6 ⁇ 10 aryl group include the same as exemplified for R 1.
  • Chloromethoxy group dichloromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1-difluoroethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, 4, C1-6 haloalkoxy groups such as 5-dichloro-3-methylpentoxy group; methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, C1-6 alkylthio groups such as t-butylthio group; C1-6 alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, n-butylsulfonyl group; chloromethyl group
  • R 3 to R 6 are each independently a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 haloalkyl group, a C2-20 alkenyl group, a C2-20 haloalkenyl group, C2 -20 alkynyl group, C2-20 haloalkynyl group, C1-20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, C3-20 cycloalkoxy group, C2-20 alkenyloxy group, C2-20 alkynyl An oxy group, a C1-20 alkylthio group, a cyano group, a nitro group, an unsubstituted or substituted amino group, a hydroxyl group, a thiol group, an unsubstituted or substituted phenyl group, an unsubstituted or substituted aralkyl group, An unsubstit
  • R 3 to R 6 are halogen atoms, C1-20 alkyl groups, C1-20 haloalkyl groups, C2-20 alkenyl groups, C2-20 haloalkenyl groups, C2-20 alkynyl groups, C2-20 haloalkynyl groups, C1 ⁇
  • Specific examples of the 20 alkoxy group, C1-20 haloalkoxy group, C3-20 cycloalkyl group, unsubstituted or substituted aralkyl group are the same as those listed as specific examples of R 2 above. It is done.
  • the “C3-20 cycloalkoxy group” of R 3 to R 6 is a group in which a hydrogen atom in a hydroxyl group is substituted with a C3-20 cycloalkyl group.
  • Examples of the “C3-20 cycloalkoxy group” include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclopropylmethyloxy group, 2-cyclopentylethyloxy Group, 2-methylcyclopropyloxy group, 2-ethylcyclopropyloxy group, 2,3,3-trimethylcyclobutyloxy group, 2-methylcyclopentyloxy group, 2-ethylcyclohexyloxy group, 2-ethylcyclooctyloxy Group, 4,4,6,6-tetramethylcyclohexyloxy group, 1,3-dibutyl
  • the “C2-20 alkenyloxy group” of R 3 to R 6 is a group in which a hydrogen atom in a hydroxyl group is substituted with a C2-20 alkenyl group.
  • Examples of the “C2-20 alkenyloxy group” include a vinyloxy group, a 1-propenyloxy group, a 2-propenyloxy group, a 1-butenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, and a 1-methyl-2-propenyloxy group 2-methyl-2-propenyloxy group, 1-pentenyloxy group, 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 1-methyl-2-butenyloxy group, 2-methyl-2- Butenyloxy group, 1-hexenyloxy group, 2-hexenyloxy group, 3-hexenyloxy group, 4-hexenyloxy group, 5-hexenyloxy group, 1-heptenyloxy
  • the “C2-20 alkynyloxy group” of R 3 to R 6 is a group in which a hydrogen atom in a hydroxyl group is substituted with a C2-20 alkynyl group.
  • Examples of the “C2-20 alkynyloxy group” include ethynyloxy group, propynyloxy group, propargyloxy group, 1-butynyloxy group, 2-butynyloxy group, 3-butynyloxy group, 1-methyl-2-propynyloxy group, 2- Methyl-3-butynyloxy group, 1-pentynyloxy group, 2-pentynyloxy group, 3-pentynyloxy group, 4-pentynyloxy group, 1-methyl-2-butynyloxy group, 2-methyl-3- Examples include pentynyloxy group, 1-hexynyloxy group, 1,1-dimethyl-2-butynyloxy group, dodecynyloxy group, but
  • the “C1-20 alkylthio group” of R 3 to R 6 is a group in which a hydrogen atom in a thiol group is substituted with a C1-20 alkyl group.
  • Examples of the “C1-20 alkylthio group” include methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, t-butylthio group, pentylthio group, isopentylthio group, 2-methylbutylthio group , Neopentylthio group, 1-ethylpropylthio group, hexylthio group, isohexylthio group, 4-methylpentylthio group, 3-methylpentylthio group, 2-methylpentylthio group, 1-methylpentylthio group, 3 , 3-dimethylbutylthio group, 2,2-dimethylbutylthio
  • the “unsubstituted or substituted amino group” of R 3 to R 6 is an amino group; a monoalkylamino group such as a methylamino group or an ethylamino group, preferably a monoC1-6 alkylamino group; a dimethylamino group A dialkylamino group such as a diethylamino group, preferably a diC1-6 alkylamino group; a monoarylamino group such as a phenylamino group, a 4-methylphenylamino group, preferably a monoC6-10 arylamino group; a diphenylamino group, Examples thereof include a diarylamino group such as a di1-naphthylamino group, preferably a diC6-10 arylamino group; an acylamino group such as an acetylamino group and a benzoylamino group, preferably a C1-6 acylamino group.
  • the “aryloxy group” of R 3 to R 6 is a group in which a hydrogen atom in a hydroxyl group is substituted with an aryl group.
  • Aryl groups include monocyclic and polycyclic. Here, in the polycyclic aryl group, as long as at least one ring is an aromatic ring, the remaining ring may be a saturated alicyclic ring, a partially unsaturated alicyclic ring, or an aromatic ring.
  • the “aryloxy group” include phenyloxy group, naphthyloxy group, azulenyloxy group, indenyloxy group, indanyloxy group, tetralinyloxy group and the like. Among these, a C6-10 aryloxy group, that is, a group in which a hydrogen atom in a hydroxyl group is substituted with a C6-10 aryl group is preferable.
  • the “heterocyclic group” of R 3 to R 6 is a 5- to 7-membered hetero atom containing 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom in addition to carbon atoms as atoms constituting the ring.
  • heterocyclic group examples include the following groups in addition to the “heteroaryl group” exemplified for R 1 .
  • R 4 and R 5 , and R 5 and R 6 may be combined to form an unsubstituted or substituted 5- to 8-membered ring together with the carbon atom to which they are bonded.
  • “R 4 and R 5 , and R 5 and R 6 together may form an unsubstituted or substituted 5- to 8-membered ring with the carbon atom to which they are attached”
  • R 4 and R 5 and R 5 and R 6 both form a ring, and R 4 and R 5 , or R 5 and R 6 form a ring. It means you may.
  • the 5- to 8-membered ring having an unsubstituted or substituted group formed by combining R 4 and R 5 and R 5 and R 6 together with the carbon atom to which each is bonded includes an unsubstituted or substituted cycloalkene
  • examples thereof include a ring, an aromatic hydrocarbon ring having an unsubstituted or substituted group, or a heterocyclic ring having an unsubstituted or substituted group.
  • the cycloalkene ring include a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.
  • a benzene ring is mentioned as an aromatic-hydrocarbon ring.
  • Heterocycles include dihydropyrrole ring, dihydrofuran ring, dihydrothiophene ring, [1,3] dioxole ring, [1,3] dithiol ring, [1,3] oxathiol ring, tetrahydropyridine ring, dihydropyran ring, Dihydrothiopyran ring, 3,4-dihydro-2H- [1,4] oxazine ring, 2,3-dihydro- [1,4] dioxin ring, 3,4-dihydro-2H- [1,4] thiazine ring 2,3-dihydro- [1,4] dithiine ring, pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, isoxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine
  • Examples of the substituent that can be included in the ring formed by combining R 4 and R 5 and R 5 and R 6 are “substituents” in “the C6-10 aryl group having a substituent” of R 1 and the like. The same thing as what was done is mentioned. Of these, a halogen atom, a C1-6 alkyl group, or a C1-6 alkoxy group is preferable as the substituent.
  • X represents a halogen atom, a nitro group, an unsubstituted or substituted amino group, a hydroxyl group, or an organic group.
  • halogen atom include those exemplified as the “halogen atom” for R 2 .
  • amino group include those exemplified as the “amino group” for R 3 .
  • the “organic group” is not particularly limited as long as it is an atomic group containing a carbon atom.
  • cyano group C1-7 acyl group such as formyl group, acetyl group, benzoyl group; C1-6 alkyl group such as methyl group, ethyl group, n-propyl group, i-propyl group; vinyl group, propenyl group, C2-6 alkenyl groups such as isopropenyl group and 2-butenyl group; C2-6 alkynyl groups such as propargyl group and 3-butynyl group; trifluoromethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl C1-6 haloalkyl group such as a group; C3-8 cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group; 2-chlorocyclopropyl group, 2,2-dichloro
  • C1-6 alkylsulfonyl groups such as methylsulfonyl group and ethylsulfonyl group; C1-6 haloalkylsulfonyl groups such as chloromethylsulfonyl group and trichloromethylsulfonyl group; C1-6 alkylsulfonyl groups such as methylsulfonyloxy group and ethylsulfonyloxy group An oxy group; a phenylsulfonyl group having an unsubstituted or substituted group such as a phenylsulfonyl group or a 4-methylphenylsulfonyl group; a phenylsulfonyloxy having an unsubstituted or substituted group such as a phenylsulfonyloxy group or a 4-methylphenylsulfonyloxy group; Groups: C1-6 alkylthio groups such as methylthio group
  • R 10 to R 14 are each independently a hydrogen atom; a hydroxyl group; a thiol group; a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group.
  • C1-6 alkyl groups such as i-butyl group, s-butyl group and t-butyl group; C1-6 haloalkyl groups such as trifluoromethyl group and pentafluoroethyl group; vinyl group, isopropenyl group, 2-butenyl
  • An unsubstituted or substituted group such as an amino group, a methylamino group, a dimethylamino group, a phenylamino group, a 4-methylphenylamino group, a diphenylamino group, an acetylamino group, or a benzoylamino group; Amino group having; C3-8 cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group; phenyl group, 2-chlorophenyl group, 4- It represents an unsubstituted or substituted phenyl group such as a methylphenyl group.
  • n represents an integer of 0 to 4.
  • Z represents an oxygen atom or a sulfur atom.
  • the ring portion containing Z and nitrogen is a 2H-1,3-benzoxazine ring or a 2H-1,3-benzothiazine ring.
  • the nitrogen-containing heterocyclic compound or a salt thereof of the present invention can be produced by a known method.
  • it can be produced as follows (Japanese Patent Laid-Open No. 5-97824, Chem. Pharm. Bull). 1996, 44, 734-745, J. Med. Chem. 2007, 50, 2647-2654, etc.).
  • (III) It can be produced by reacting a compound represented by the formula (III) (wherein R 3 to R 6 are the same as defined in the formula (I). M represents a leaving group).
  • the halogen atom represented by E is preferably a chlorine atom, bromine atom or iodine atom
  • the esterified hydroxyl group represented by E is preferably trifluoromethanesulfonyl or methane. Examples thereof include a hydroxyl group esterified with a reactive group such as sulfonyl or p-toluenesulfonyl.
  • the a leaving group represented by M is, Li, Na, K, Ca (1/2), MgCl, MgBr, MgI, ZnCl, SnCl, Sn (n Bu) 3, CrCl 2, CuCl, CuBr, NiCl, PdCl, B (OH) 2 and the like can be mentioned.
  • the reaction is carried out in an inert solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane, hexane, toluene, benzene, methylene chloride, chloroform, 1,2-dichloroethane, DMF, DMSO, etc., or a mixed solvent of about ⁇ 50.
  • reaction can be carried out in the temperature range of from 50 ° C to 50 ° C.
  • the reaction can be preferably performed in an inert gas (for example, nitrogen, argon, etc.) atmosphere.
  • inert gas for example, nitrogen, argon, etc.
  • tetrakis (triphenylphosphine) nickel (O) can be added as a catalyst to allow the reaction to proceed smoothly.
  • the compound represented by the formula (II) as a starting material may be a commercially available compound, or may be one produced by the method shown in the examples.
  • the compound represented by the formula (III) is, for example,
  • (III ') A compound of the formula (III ′) (wherein R 3 to R 6 are as defined above; W represents hydrogen or a halogen atom (Cl, Br or I)) and the leaving group M;
  • the starting compound can be obtained by reacting in the above-mentioned inert solvent at a temperature range of about ⁇ 78 ° C. to 70 ° C., preferably in an inert gas atmosphere.
  • the compound represented by the formula (III) synthesized from the compound represented by the formula (III ′) may be purified, but it can be directly reacted with the compound of the formula (II) without isolation from the reaction system. To produce the compound of formula (I).
  • X and R 1 to R 6 in the compound represented by the formula (I) can be converted into other substituents by, for example, the following known methods. For example, by substituting a halogen atom with a halogen atom by halogenation or by nitrating to a nitro group; and by reducing the nitro group to an amino group; acylamino or sulfonyl by acylating or sulfonating the amino group It can also lead to an amino group.
  • Cyano groups can also be converted to carbamoyl groups by treatment with, for example, aqueous sodium hydroxide / 30% hydrogen peroxide; thiocarbamoyl groups by using hydrogen sulfide in pyridine / triethylamine. Cyano groups can also be converted to carboxyl groups by, for example, heating and hydrolyzing in aqueous sodium hydroxide; or formyl groups by using Raney nickel in water / acetic acid / pyridine in the presence of sodium phosphate. Can also be converted. Formyl groups can be converted to vinyl groups by Wittig reaction; hydroxyiminomethyl groups and the like by reaction with hydroxyamine. Hydroxyl groups can be converted to alkoxy groups by alkylation; acyl groups to acyloxy groups; alkyl hydroxyl groups can also be converted to nitroxyalkyl groups by sulfuric acid / nitric acid.
  • the nitrogen-containing heterocyclic compound represented by the formula (I) of the present invention is a compound of the hydroxyketone compound represented by the formula (VIII) and the compound represented by the formula (VII) in the presence of an acid catalyst. It can also be produced by reacting ammonia all at once.
  • the leaving group represented by M ′ is preferably Li, Na, K, Ca (1/2), MgCl, MgBr, MgI, ZnCl, SnCl, CrCl 2 or the like. Is mentioned.
  • the hydroxyl-protecting group represented by Y is preferably a known phenolic hydroxyl-protecting group such as a methoxydimethylmethyl group, trimethylsilyl group, t-butyldimethylsilyl group and the like.
  • the condensation reaction of the compound represented by the formula (IV) and the compound represented by the formula (V) is carried out by using an inert solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane, hexane, toluene, benzene, methylene chloride, DMF, or the like.
  • an inert solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane, hexane, toluene, benzene, methylene chloride, DMF, or the like.
  • This reaction is preferably performed under an atmosphere of an inert gas (for example, nitrogen, argon, etc.).
  • the subsequent deprotection reaction is carried out using acid hydrolysis or a fluorinated salt reagent such as tetrabutylammonium fluoride or potassium fluoride.
  • the reaction of the hydroxyketone compound represented by formula (VIII) with ammonia is an inert solvent such as ethanol, benzene, toluene, chloroform, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, diethyl ether, or a mixed solvent thereof. In the temperature range of about 0 ° C to 100 ° C. Usually, this reaction is carried out in a solvent containing 1 to 10 times the molar amount of ammonia with respect to the hydroxyketone compound represented by the formula (VIII) (for example, molecular sieves, anhydrous calcium sulfate, anhydrous magnesium sulfate). Etc.) in the presence of a sealed tube.
  • the imino compound represented by the formula (VI) can also be used for the next reaction without isolation and purification.
  • the ring closure reaction between the imino compound represented by the formula (VI) and the compound represented by the formula (VII) is a solventless or inert solvent such as benzene, toluene, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether. Or in a mixed solvent thereof in the presence of an acid catalyst and a dehydrating agent at a temperature ranging from room temperature to 100 ° C.
  • an acid catalyst hydrochloric acid, p-toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, ammonium chloride, ammonium acetate and the like can be used.
  • the amount of the acid catalyst to be used is preferably changed as appropriate depending on the acidity of the catalyst, and is preferably in the range of about 1/100 to 10 times the mole of the imino compound represented by the formula (VI).
  • the dehydrating agent for example, molecular sieves, anhydrous calcium sulfate, anhydrous magnesium sulfate and the like can be used.
  • a one-pot reaction between a hydroxyketone compound represented by the formula (VIII), ammonia, and a compound represented by the formula (VII) is a solvent-free or inert solvent such as benzene, toluene, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, etc., or a mixed solvent thereof in the presence of an acid catalyst and a dehydrating agent at a temperature range of 0 ° C. to 100 ° C.
  • this reaction is carried out in a sealed tube in a solvent containing 1 to 10 times the molar amount of ammonia with respect to the hydroxyketone compound represented by the formula (VIII).
  • the acid catalyst those described in the description of the ring-closing reaction between the imino compound represented by the above formula (VI) and the compound represented by the formula (VII) can be used, and the amount of the acid catalyst used is the formula (VIII).
  • the dehydrating agent those described in the description of the ring-closing reaction between the imino compound represented by the formula (VI) and the compound represented by the formula (VII) can be used.
  • Suitable acids for this reaction are preferably acids which give an agro-horticulturally acceptable salt.
  • inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, nitric acid or sulfamic acid
  • organic acids such as acetic acid, tartaric acid, citric acid, fumaric acid, maleic acid, p-toluenesulfonic acid, methanesulfonic acid or glutamic acid
  • the salt of the compound represented by the formula (I) can be produced, for example, by allowing an inorganic acid or an organic acid to act on the compound represented by the formula (I).
  • the usual post-treatment operation can be performed. Then, if purification of the product is necessary, it is purified by a known and usual purification means such as distillation, recrystallization or column chromatography. can do. Thereby, the target product can be isolated.
  • a known and usual purification means such as distillation, recrystallization or column chromatography.
  • the structure of the target product can be identified and confirmed by known analysis means such as elemental analysis, NMR spectrum, IR spectrum, and mass spectrum.
  • the agricultural and horticultural fungicide of the present invention (hereinafter sometimes referred to as “the present bactericidal agent”) is a nitrogen-containing heterocyclic compound represented by the formula (I) or a salt thereof (hereinafter referred to as “the fungicide”). , “Sometimes referred to as“ the compound of the present invention ”)) as an active ingredient.
  • the amount of the active ingredient is usually 0.01 to 90% by weight, preferably 0.05 to 85% by weight, based on the whole bactericidal agent.
  • the fungicide of the present invention is used for a wide variety of fungi, for example, bacteria belonging to algae (Oomycetes), Ascomycetes, Deuteromycetes, and basidiomycetes. Excellent sterilizing power.
  • the fungicide of the present invention can be used in methods such as seed treatment, foliage application, soil application, and water surface application for the control of various diseases that occur during cultivation of agricultural and horticultural crops including flowers, turf, and grass. .
  • the fungicide of the present invention can be used for controlling pathogenic bacteria exemplified below.
  • Sugar beet brown spot (Cercospora beticola) Black root disease (Aphanomyces cochlloides) Root rot (Thanatephorus cucumeris) Leaf rot (Thanatephorus cucumeris) Peanut Brown Spot (Mycosphaerella arachidis) Black astringency (Mycosphaerella berkeleyi) Cucumber powdery mildew (Sphaerotheca fuliginea) Downy mildew (Pseudoperonospora cubensis) Vine Blight (Mycosphaerella melonis) Vine split disease (Fusarium oxysporum) Sclerotinia sclerotiorum Gray mold (Botrytis cinerea) Anthracnose (Colletotrichum orbiculare) Black star disease (Cladosporium cucumerinum) Brown spot disease (Corynespor
  • Tomato gray mold (Botrytis cinerea) Leaf mold (Cladosporium fulvum) Plague (Phytophthora infestans) Eggplant gray mold (Botrytis cinerea) Black blight (Corynespora melongenae) Powdery mildew (Erysiphe cichoracearum) Susmolder disease (Mycovellosiella nattrassii) Strawberry Gray mold disease (Botrytis cinerea) Powdery mildew (Sohaerotheca humuli) Anthracnose (Colletotrichum acutatum, Colletotrichum fragariae) Plague (Phytophthora cactorum) Onion Gray rot (Botrytis allii) Gray mold (Botrytis cinerea) Botrytis squamosa Downy mildew (Peronospora destructor) Cabbage root-knot disease (Plasmodiophora brassicae) Soft rot (Erwini
  • Barley Leafy spot disease (Pyrenophora graminea) Cloud shape disease (Rhynchosporium secalis) Bare Scab (Ustilago tritici, U.nuda) Rice blast (Pyricularia oryzae) Rhizoctonia solani Idiot Seedling (Gibberella fujikuroi) Sesame leaf blight (Cochliobolus niyabeanus) Seedling blight (Pythium graminicolum) White leaf blight (Xanthomonas oryzae) Burkholderia plantarii Brown stripe disease (Acidovorax avenae) Burkholderia glumae Tobacco sclerotia (Sclerotinia sclerotiorum) Powdery mildew (Erysiphe cichoracearum) Tulip gray mold (Botrytis cinerea) Bentgrass Snow Rot Large Bacterial Nuclear Disease (Scle
  • the bactericidal agent of the present invention has an excellent bactericidal effect not only against bacteria that are sensitive to conventional bactericides but also to bacteria that have become resistant to conventional bactericides.
  • gray mold fungus (Botrytis cinerea), sugar beet brown fungus (Cercospora beticola), apple black spot fungus (Venturia inaequalis), pear black spot fungus (Venturia nashicola) can be used as benzimidazole fungicides such as thiophanate methyl, benomyl, carbendazim, etc. Although it exhibits resistance, the fungicide of the present invention has an effective bactericidal action against these resistant bacteria.
  • gray mold fungus (Botrytis cinerea) shows resistance to dicarboximide fungicides (for example, vinclozolin, procymidone, iprodione), the fungicides of the present invention have an effective fungicidal action.
  • dicarboximide fungicides for example, vinclozolin, procymidone, iprodione
  • diseases to which the fungicide of the present invention is applied include sugar beet brown spot, wheat powdery mildew, rice blast, apple black spot, cucumber gray mold, peanut brown spot and the like.
  • diseases more preferably applied include various fruit tree diseases.
  • the disinfectant of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.
  • the disinfectant of the present invention may be the one using the compound of the present invention as it is without adding other components, or by using an additive or carrier, a wettable powder, granule, powder, emulsion, aqueous solvent, suspension. It may be used in a form that can be taken by general pesticides such as an agent and a wettable granule.
  • Additives and carriers that can be added to the agricultural chemical formulation can be appropriately selected according to the intended dosage form.
  • vegetable powders such as soybean powder and wheat flour, mineral powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, sodium benzoate, urea, Organic and inorganic compounds such as mirabilite are used.
  • kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil Water or the like can be used as a solvent.
  • a surfactant may be added as necessary.
  • the surfactant to be used is not particularly limited.
  • alkylphenyl ether added with polyoxyethylene alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, sorbitan added with polyoxyethylene Higher fatty acid esters, nonionic surfactants such as tristyryl phenyl ether added with polyoxyethylene, sulfates of alkylphenyl ethers added with polyoxyethylene, alkylbenzene sulfonates, sulfates of higher alcohols, alkyls
  • nonionic surfactants such as tristyryl phenyl ether added with polyoxyethylene, sulfates of alkylphenyl ethers added with polyoxyethylene, alkylbenzene sulfonates, sulfates of higher alcohols, alkyls
  • nonionic surfactants such as tristyryl phenyl ether added with polyoxyethylene,
  • the wettable powder, emulsion, flowable, aqueous solvent and granular wettable powder thus obtained are diluted with water to a predetermined concentration to obtain a solution, suspension or emulsion, and the powder and granules are left as they are. Used in a method of spraying on plants.
  • the formulated bactericidal agent of the present invention is applied to a plant body, seeds, water surface or soil as it is or diluted with water or the like.
  • the application amount varies depending on weather conditions, formulation form, application magnetism, application method, application location, disease to be controlled, target crop, etc., but is usually 1 to 1,000 g, preferably 10 to 1 in terms of the amount of active ingredient compound per hectare. 100 g.
  • the applied concentration is 1 to 1000 ppm, preferably 10 to 250 ppm. In this case, it can be applied as it is without dilution.
  • one or two or more of various fungicides, insecticides, acaricides and the like can be mixed with the fungicides of the present invention.
  • fungicides insecticides / acaricides, nematicides, soil pesticides and plant growth regulators that can be used in combination with the compounds of the present invention are shown below.
  • Fungicide 1) benzimidazole series: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate methyl, etc .; 2) Dicarboximide type: Clozolinate, iprodione, procymidone, vinclozolin and the like; 3) DMI-bactericidal system: imazalyl, oxpoconazole, pefazoate, prochloraz, triflumizole, triphorin, pyrifenox, phenarimol, nuarimol, azaconazole, viteltanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxy Conazole, fenbuconazole, fluquinconazole, flusilazole, flutriaol, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanyl, penconazole, propi
  • Insecticides, acaricides, nematicides, soil insecticides 1) Organic (thio) phosphates: acephate, azamethiphos, azinephosmethyl, chlorpyrifos, chlorpyrifosmethyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfotone, ethion, EPN, phenamiphos, fenitrothion, fenthion, isoxathione, metathione, metaxamide, , Methidathion, methylparathion, mevinphos, monocrotophos, oxydemetonmethyl, paraoxon, parathion, phentoate, hosalon, phosmet, phosphamidone, folate, oxime, pirimiphosmethyl, propenophos, prothiophos, sulfophos, tetrachlorbinphos, terbufos
  • Plant growth regulator Abscisic acid, indole butyric acid, uniconazole, etiquelozate, etephone, cloxiphonac, chlormecote, chlorella extract, calcium peroxide, cyanamide, dichlorprop, gibberellin, daminozide, decyl alcohol, trinexapac ethyl, mepicoat chloride, pack Lobutrazole, paraffin wax, piperonyl butoxide, pyraflufenethyl, flurprimidol, prohydrojasmon, prohexadione calcium salt, benzylaminopurine, pendimethalin, forchlorphenuron, potassium maleate hydrazide, 1-naphthyl Acetamide, 4-CPA, MCPB, choline, oxyquinoline sulfate, ethiclozate, butorualine, 1-methylcyclopropene, abiglycine hydrochloride;
  • Triol salts were prepared from 3-quinolineboronic acid and 1,1,1-Tris (hydroxymethyl) ethane according to the method reported in the literature (Angew. Chem. Int. Ed., 2008, 47, 928-931). 1.04 g (3.5 mmol) of the triol salt and 0.68 g (0.59 mmol) of Pd (PPh 3 ) 4 were added to the toluene solution, the inside of the reactor was purged with nitrogen, and the mixture was heated to reflux for 14 hours.
  • reaction solution was cooled to room temperature, poured into ice water and then extracted with ethyl acetate.
  • the organic layer was washed with saturated brine, and the solvent was distilled off under reduced pressure.
  • 4-Chloro-2- (4-fluorobenzyl) -2-methyl-2H-1,3-benzothiazine was obtained as a blue-black oily substance. 10 mL of a dimethylformamide solution containing 0.216 g (1.25 mmol) of 3-quinolineboronic acid and 1.5 mL (3.00 mmol) of 2M aqueous cesium carbonate solution was placed in a container and purged with nitrogen. To this solution was added Pd (PPh 3 ) 4 0.24 g (0.208 mmol) and the total amount of 4-Chloro-2- (4-fluorobenzyl) -2-methyl-2H-1,3-benzothiazine obtained above. For 18 hours.
  • reaction solution was cooled to room temperature, poured into a solution consisting of 100 mL of ethyl acetate and 100 mL of water, and the aqueous layer was extracted with 100 mL of ethyl acetate.
  • the organic layer was washed with 60 mL brine and dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure.
  • Examples of nitrogen-containing heterocyclic compounds represented by the formula (I) of the present invention produced in the same manner as in Example 1 or 2 are shown in Tables 1 to 4 below.
  • Me represents a methyl group
  • Et represents an ethyl group
  • n Pr represents an n-propyl group
  • C Pr represents a cyclopropyl group
  • Py represents a pyridyl group
  • Ph represents a phenyl group.
  • R 5 and R 6 represent Ph, it represents that R 5 and R 6 together form a benzene ring with the carbon atoms to which they are bonded. .
  • a quinoline ring is formed by the benzene ring and the pyridine ring.
  • Formulation Example 1 wettable powder Compound of the present invention 40 parts Clay 48 parts Dioctylsulfosuccinate sodium salt 4 parts Lignin sulfonic acid sodium salt 8 parts The above is uniformly mixed and finely pulverized, and a wettable powder with 40% active ingredient. Get.
  • Emulsion Compound of the present invention 10 parts Solvesso 200 53 parts Cyclohexanone 26 parts Calcium dodecylbenzenesulfonate 1 part Polyoxyethylene alkylallyl ether 10 parts The above components are mixed and dissolved to obtain an emulsion containing 10% active ingredient.
  • Formulation Example 3 Powder The present compound 10 parts Clay 90 parts The above is uniformly mixed and finely pulverized to obtain a powder of 10% active ingredient.
  • Formulation Example 4 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctylsulfosuccinate sodium salt 1 part Potassium phosphate 1 part After pulverizing and mixing well, adding water and kneading well, granulation drying As a result, granules containing 5% of the active ingredient are obtained.
  • Formulation Example 5 Suspension Compound of the present invention 10 parts Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts The above is mixed and the particle size is 3 microns or less The suspension is wet-pulverized until a suspension of 10% active ingredient is obtained.
  • Granule wettable powder Compound of the present invention 40 parts Clay 36 parts Potassium chloride 10 parts Alkylbenzenesulfonic acid sodium salt 1 part Lignin sulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt 5 parts After finely pulverizing, add an appropriate amount of water and knead to make a clay. After granulating the clay-like material, it is dried to obtain a granulated wettable powder containing 40% of the active ingredient.
  • Apple seedlings (variety “Kokumi”, 3-4 leaf stage) cultivated in an unglazed pot were sprayed with an emulsion (formulation example 2) as a fungicide of the present invention at a concentration of 100 ppm active ingredient.
  • an emulsion formulation example 2
  • the lesion appearance state on the leaf was compared with the untreated one, and the control effect was obtained.
  • compound numbers 1-2 to 1-9, 1-11, 1-14, 1-20, 1-31 to 1-45, 1-47 to 1-49, 2-2, 2-6, and 3 -26 showed a control effect of 75% or more.
  • the nitrogen-containing heterocyclic compound or a salt thereof of the present invention is a novel compound and is useful as an active ingredient of an agricultural and horticultural fungicide that can be used safely and reliably.
  • the agricultural and horticultural fungicide of the present invention has an excellent control effect, does not cause phytotoxicity to plants, and is industrially useful because it is a drug that is less toxic to human and livestock and less harmful to the environment. .

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Abstract

L'invention porte sur un composé hétérocyclique contenant de l'azote représenté par la formule (I) [dans laquelle R1 représente un groupe aryle en C6-10, etc. ; R2 représente un atome d'hydrogène, un groupe alkyle en C1-20, etc. ; R3 et R6 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle en C1-20, etc., à la condition que R4 et R5, et R5 et R6 puissent former, conjointement avec les atomes d'azote auxquels ces groupes sont attachés, un noyau à 5 à 8 chaînons substitué ou non substitué ; X représente un atome d'halogène, etc. ; n représente un entier de 0 à 4 ; et Z représente un atome d'oxygène ou un atome de soufre] ou un sel de celui-ci ; et un bactéricide agricole ou horticole qui comprend, comme ingrédient actif, au moins l'un des composés précités.
PCT/JP2010/002947 2009-04-28 2010-04-23 Composé hétérocyclique contenant de l'azote et bactéricide agricole ou horticole Ceased WO2010125782A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2009119089A1 (ja) * 2008-03-27 2011-07-21 日本電気株式会社 含窒素複素環化合物及び農園芸用殺菌剤
WO2022207665A1 (fr) * 2021-03-31 2022-10-06 Syngenta Crop Protection Ag Dérivés de quinoline/quinoxaline benzothiazine microbiocides
WO2022243109A1 (fr) 2021-05-18 2022-11-24 Basf Se Nouvelles quinoléines substituées utilisées comme fongicides
WO2022243107A1 (fr) 2021-05-18 2022-11-24 Basf Se Nouvelles pyridines substituées utilisées comme fongicides
WO2023111215A1 (fr) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Dérivés de benzothiazine substitués par pyridine à effet microbiocide
WO2024104813A1 (fr) * 2022-11-14 2024-05-23 Basf Se Mélange fongicide contenant des pyridines substituées
WO2025031843A1 (fr) 2023-08-09 2025-02-13 Basf Se Nouveaux composés de benzoxazine picolinonitrile substitués pour lutter contre des champignons phytopathogènes
WO2025121436A1 (fr) * 2023-12-08 2025-06-12 三井化学クロップ＆ライフソリューション株式会社 Composé hétérocyclique bicyclique et fongicide pour une utilisation agricole et horticole le contenant en tant que principe actif

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JPH06107647A (ja) * 1992-08-12 1994-04-19 Takeda Chem Ind Ltd １，３−ベンゾオキサジン誘導体の製造法
WO2005070917A1 (fr) * 2004-01-23 2005-08-04 Sankyo Agro Company, Limited 3-(dihydro(tetrahydro)isoquinolin-1-yl)quinolines
WO2007011022A1 (fr) * 2005-07-22 2007-01-25 Sankyo Agro Company, Limited Dérivé de 3-(isoquinoline-1-yl)quinoline
JP2008088139A (ja) * 2006-10-05 2008-04-17 Sankyo Agro Kk ３−置換キノリン化合物

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JPH06107647A (ja) * 1992-08-12 1994-04-19 Takeda Chem Ind Ltd １，３−ベンゾオキサジン誘導体の製造法
WO2005070917A1 (fr) * 2004-01-23 2005-08-04 Sankyo Agro Company, Limited 3-(dihydro(tetrahydro)isoquinolin-1-yl)quinolines
WO2007011022A1 (fr) * 2005-07-22 2007-01-25 Sankyo Agro Company, Limited Dérivé de 3-(isoquinoline-1-yl)quinoline
JP2008088139A (ja) * 2006-10-05 2008-04-17 Sankyo Agro Kk ３−置換キノリン化合物

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2009119089A1 (ja) * 2008-03-27 2011-07-21 日本電気株式会社 含窒素複素環化合物及び農園芸用殺菌剤
WO2022207665A1 (fr) * 2021-03-31 2022-10-06 Syngenta Crop Protection Ag Dérivés de quinoline/quinoxaline benzothiazine microbiocides
US20240208962A1 (en) * 2021-03-31 2024-06-27 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline benzothiazine derivatives
WO2022243109A1 (fr) 2021-05-18 2022-11-24 Basf Se Nouvelles quinoléines substituées utilisées comme fongicides
WO2022243107A1 (fr) 2021-05-18 2022-11-24 Basf Se Nouvelles pyridines substituées utilisées comme fongicides
WO2023111215A1 (fr) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Dérivés de benzothiazine substitués par pyridine à effet microbiocide
WO2024104813A1 (fr) * 2022-11-14 2024-05-23 Basf Se Mélange fongicide contenant des pyridines substituées
WO2025031843A1 (fr) 2023-08-09 2025-02-13 Basf Se Nouveaux composés de benzoxazine picolinonitrile substitués pour lutter contre des champignons phytopathogènes
WO2025121436A1 (fr) * 2023-12-08 2025-06-12 三井化学クロップ＆ライフソリューション株式会社 Composé hétérocyclique bicyclique et fongicide pour une utilisation agricole et horticole le contenant en tant que principe actif

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