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WO2010125782A1 - Nitrogen-containing heterocyclic compound and agricultural or horticultural bactericide - Google Patents

Nitrogen-containing heterocyclic compound and agricultural or horticultural bactericide 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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group
substituted
unsubstituted
ring
atom
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PCT/JP2010/002947
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French (fr)
Japanese (ja)
Inventor
三谷晃
清水一彌
▲桑▼原頼人
佐藤元亮
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日本曹達株式会社
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Priority to JP2011511296A priority Critical patent/JP5254436B2/en
Publication of WO2010125782A1 publication Critical patent/WO2010125782A1/en

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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

Disclosed are: a nitrogen-containing heterocyclic compound represented by formula (I) [wherein R1 represents a C6-10 aryl group, etc.; R2 represents a hydrogen atom, a C1-20 alkyl group, etc.; R3 to R6 independently represent each a hydrogen atom, a C1-20 alkyl group, etc., provided that R4 and R5, and R5 and R6 may form, together with the carbon atoms to which these groups are attached, an unsubstituted or substituted 5- to 8-membered ring; X represents a halogen atom, etc.; n represents an integer of 0 to 4; and Z represents an oxygen atom or a sulfur atom] or a salt thereof; and an agricultural or horticultural bactericide which comprises, as the active ingredient, at least one of the aforesaid compounds.

Description

含窒素複素環化合物及び農園芸用殺菌剤Nitrogen-containing heterocyclic compounds and agricultural and horticultural fungicides
　本発明は、新規な含窒素複素環化合物またはその塩、及びこれらの化合物の少なくとも１種を有効成分として含有する農園芸用殺菌剤に関する。
　本願は、２００９年４月２８日に、日本に出願された特願２００９－１０８７７２号に基づき優先権を主張し、その内容をここに援用する。 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.
This application claims priority based on Japanese Patent Application No. 2009-108772 filed in Japan on April 28, 2009, the contents of which are incorporated herein by reference.
　農園芸作物の栽培に当り、作物の病害に対して多数の防除薬剤が使用されているが、その防除効力が不十分であったり、薬剤耐性の病原菌の出現によりその使用が制限されたり、また植物体に薬害や汚染を生じたり、若しくは人畜魚類に対する毒性や環境への影響があったりなどして、必ずしも満足すべき防除薬剤とは言い難いものが少なくない。従って、かかる欠点の少ない安全に使用できる薬剤の出現が強く要望されている。 In the cultivation of agricultural and horticultural crops, many 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.
　本発明に関連して、特許文献１及び２には、本発明化合物と類似の化学構造を有するキノリン誘導体、及びそれを有効成分として含有する農園芸用殺菌剤が開示されている。しかしながら、本発明化合物は記載されていない。 In connection with the present invention, 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.
ＷＯ２００５／０７０９１７号パンフレットWO2005 / 0700917 pamphlet ＷＯ２００７／０１１０２２号パンフレットWO2007 / 011022 pamphlet
　本発明は、効果が確実で安全に使用できる農園芸用殺菌剤の有効成分となりうる、新規な含窒素複素環化合物またはその塩、及びこれらの化合物の少なくとも１種を有効成分として含有する農園芸用殺菌剤を提供することを課題とする。 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.
　上記課題を解決すべく、本発明は式（Ｉ）で表される含窒素複素環化合物またはその塩を提供する。 In order to solve the above problems, the present invention provides a nitrogen-containing heterocyclic compound represented by the formula (I) or a salt thereof.
Figure JPOXMLDOC01-appb-C000001
 　　　（Ｉ）
Figure JPOXMLDOC01-appb-C000001
 (I)
　式（Ｉ）中、Ｒ1は、無置換若しくは置換基を有するＣ６～１０アリール基、無置換若しくは置換基を有するヘテロアリール基、無置換若しくは置換基を有するアラルキル基、または無置換若しくは置換基を有するヘテロアラルキル基を示す。
　Ｒ2は、水素原子、ハロゲン原子、Ｃ１～２０アルキル基、Ｃ１～２０ハロアルキル基、Ｃ２～２０アルケニル基、Ｃ２～２０ハロアルケニル基、Ｃ２～２０アルキニル基、Ｃ２～２０ハロアルキニル基、Ｃ１～２０アルコキシ基、Ｃ１～２０ハロアルコキシ基、Ｃ３～２０シクロアルキル基、Ｃ４～２０シクロアルケニル基、Ｃ８～２０シクロアルキニル基、Ｃ１～２０アシル基、Ｃ１～２０アルコキシカルボニル基、無置換若しくは置換基を有するＣ６～１０アリール基、無置換若しくは置換基を有するヘテロアリール基、無置換若しくは置換基を有するアラルキル基、または無置換若しくは置換基を有するヘテロアラルキル基を示す。 In the formula (I), 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. Represents a heteroaralkyl group having the following formula.
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.
　Ｒ3～Ｒ6は、それぞれ独立して、水素原子、ハロゲン原子、Ｃ１～２０アルキル基、Ｃ１～２０ハロアルキル基、Ｃ２～２０アルケニル基、Ｃ２～２０ハロアルケニル基、Ｃ２～２０アルキニル基、Ｃ２～２０ハロアルキニル基、Ｃ１～２０アルコキシ基、Ｃ１～２０ハロアルコキシ基、Ｃ３～２０シクロアルキル基、Ｃ３～２０シクロアルコキシ基、Ｃ２～２０アルケニルオキシ基、Ｃ２～２０アルキニルオキシ基、Ｃ１～２０アルキルチオ基、シアノ基、ニトロ基、無置換若しくは置換基を有するアミノ基、水酸基、チオール基、無置換若しくは置換基を有するフェニル基、無置換若しくは置換基を有するアラルキル基、無置換若しくは置換基を有するアリールオキシ基、または無置換若しくは置換基を有するヘテロ環基を示す。
　Ｒ4とＲ5、及びＲ5とＲ6は、一緒になってそれぞれが結合する炭素原子と共に、無置換若しくは置換基を有する５～８員環を形成してもよい。
　Ｒ5とＲ6が同時に水素原子であることはない。 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 heterocyclic group.
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は、ハロゲン原子、ニトロ基、無置換若しくは置換基を有するアミノ基、水酸基、または有機基を示す。
　ｎは、０～４のいずれかの整数を示す。
　Ｚは、酸素原子または硫黄原子を示す。
　本発明の含窒素複素環化合物またはその塩においては、Ｒ4とＲ5、及びＲ5とＲ6が一緒になってそれぞれが結合する炭素原子と共に形成する無置換若しくは置換基を有する５～８員環が、無置換若しくは置換基を有するシクロアルケン環、無置換若しくは置換基を有する芳香族炭化水素環、または無置換若しくは置換基を有するヘテロ環であることが好ましい。
　また、本発明は、本発明の含窒素複素環化合物またはその塩の少なくとも１種を有効成分として含有する農園芸用殺菌剤を提供する。 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.
In the nitrogen-containing heterocyclic compound of the present invention or a salt thereof, 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.
　本発明の含窒素複素環化合物またはその塩は新規化合物であり、効果が確実で安全に使用できる農園芸用殺菌剤の有効成分として有用である。
　本発明の農園芸用殺菌剤は優れた防除効果を有し、植物体に薬害を生じることがなく、人畜魚類に対する毒性や環境への影響が少ない薬剤である。 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.
　以下、本発明を、１）式（Ｉ）で表される含窒素複素環化合物またはその塩、及び、２）農園芸用殺菌剤に項分けして詳細に説明する。 Hereinafter, the present invention will be described in detail by dividing into 1) a nitrogen-containing heterocyclic compound represented by the formula (I) or a salt thereof, and 2) an agricultural and horticultural fungicide.
１）式（Ｉ）で表される含窒素複素環化合物またはその塩
　本発明の含窒素複素環化合物またはその塩は、前記式（Ｉ）で表される化合物またはその塩である。本発明の含窒素複素環化合物またはその塩には、水和物、各種溶媒和物や結晶多形等も含まれる。 1) Nitrogen-containing heterocyclic compound represented by formula (I) or salt thereof The nitrogen-containing heterocyclic compound or salt thereof of the present invention 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.
　式（Ｉ）中、Ｒ1は、無置換若しくは置換基を有するＣ６～１０アリール基、無置換若しくは置換基を有するヘテロアリール基、無置換若しくは置換基を有するアラルキル基、または無置換若しくは置換基を有するヘテロアラルキル基を示す。 In the formula (I), 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. Represents a heteroaralkyl group having the following formula.
　Ｒ1の「Ｃ６～１０アリール基」は、炭素数６～１０の単環または多環のアリール基を意味する。ここで、多環アリール基は、少なくとも一つの環が芳香環であれば、残りの環が飽和脂環、部分不飽和脂環または芳香環のいずれであってもよい。
　「Ｃ６～１０アリール基」としては、フェニル基、ナフチル基、アズレニル基、インデニル基、インダニル基、テトラリニル基等が挙げられる。これらのうち、フェニル基が好ましい。 The “C6-10 aryl group” for R 1 means a monocyclic or polycyclic aryl group having 6 to 10 carbon atoms. 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.
Examples of 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.
　Ｒ1の「アラルキル基」は、Ｃ６～１０アリール基で置換されたＣ１～２０アルキル基である。
　ここで、「Ｃ１～２０アルキル基」は、直鎖または分岐鎖の炭素数１～２０の飽和炭化水素基を意味する。
　「Ｃ１～２０アルキル基」としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、２－メチルブチル基、２，２－ジメチルプロピル基、ｎ－ヘキシル基、イソヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ノニル基、イソノニル基、ｎ－デシル基、２－エチルオクチル基、３－エチルオクチル基、２，３－ジメチルオクチル基、４－プロピルオクチル基、ドデシル基、４－エチルデシル基、６－エチルドデシル基、３，５－ジメチルデシル基、２，５－ジメチルデシル基、６－プロピルノニル基、４－ブチルオクチル基、トリデシル基、テトラデシル基、２，４，６，８－テトラメチルデシル基、２，２－ジエチルデシル基、２，５－ジエチルデシル基、４－ブチルデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、２，４，６，８－テトラエチルデシル基、ノナデシル基、イコシル基等が挙げられる。これらのうち、Ｃ１～６アルキル基、すなわち、直鎖または分岐鎖の炭素数１～６の飽和炭化水素基が好ましい。
　「アラルキル基」としては、ベンジル基、フェネチル基、３－フェニルプロピル基、１－ナフチルメチル基、２－ナフチルメチル基等が挙げられる。これらのうち、Ｃ６～１０アリールＣ１～６アルキル基が好ましい。 The “aralkyl group” for R 1 is a C1-20 alkyl group substituted with a C6-10 aryl group.
Here, 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. , Isopentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, nonyl group, isononyl group, n-decyl group, 2 -Ethyloctyl group, 3-ethyloctyl group, 2,3-dimethyloctyl group, 4-propyloctyl group, dodecyl group, 4-ethyldecyl group, 6-ethyldodecyl group, 3,5-dimethyldecyl group, 2,5 -Dimethyldecyl group, 6-propylnonyl group, 4-butyloctyl group, tridecyl group, tetradecyl group, 2,4,6,8-tetramethyldecyl group, 2,2-die Rudeshiru group, 2,5-diethyl-decyl group, 4-Buchirudeshiru group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 2,4,6,8-tetraethyl-decyl group, nonadecyl group, eicosyl group and the like. Of these, a C1-6 alkyl group, that is, a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms is preferable.
Examples of the “aralkyl group” include benzyl group, phenethyl group, 3-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like. Of these, C6-10 aryl C1-6 alkyl groups are preferred.
　Ｒ1の「ヘテロアリール基」は、環を構成する原子として炭素原子以外に窒素原子、酸素原子及び硫黄原子から選ばれる１～４個の複素原子を含む５～１０員のアリール基である。この場合、単環、または環同士が縮合した多環であってもよい。
　「ヘテロアリール基」としては、以下の基を挙げることができる。
（１）５員環のヘテロアリール基
ピロ－ル－１－イル基、ピロ－ル－２－イル基、ピロ－ル－３－イル基等のピロリル基；
フラン－２－イル基、フラン－３－イル基等のフリル基；
チオフェン－２－イル基、チオフェン－３－イル基等のチエニル基；
イミダゾール－１－イル基、イミダゾール－２－イル基、イミダゾール－４－イル基、イミダゾール－５－イル基等のイミダゾリル基；
ピラゾール－１－イル基、ピラゾール－３－イル基、ピラゾール－４－イル基、ピラゾール－５－イル基等のピラゾリル基；
オキサゾール－２－イル基、オキサゾール－４－イル基、オキサゾール－５－イル基等のオキサゾリル基；
イソオキサゾール－３－イル基、イソオキサゾール－４－イル基、イソオキサゾール－５－イル基等のイソオキサゾリル基；
チアゾール－２－イル基、チアゾール－４－イル基、チアゾール－５－イル基等のチアゾリル基；
イソチアゾール－３－イル基、イソチアゾール－４－イル基、イソチアゾール－５－イル基等のイソチアゾリル基；
１，２，３－トリアゾール－１－イル基、１，２，３－トリアゾール－４－イル基、１，２，３－トリアゾール－５－イル基、１，２，４－トリアゾール－１－イル基、１，２，４－トリアゾール－３－イル基、１，２，４－トリアゾール－５－イル基等のトリアゾリル基；
１，２，４－オキサジアゾール－３－イル基、１，２，４－オキサジアゾール－５－イル基、１，３，４－オキサジアゾール－２－イル基等のオキサジアゾリル基；
１，２，４－チアジアゾール－３－イル基、１，２，４－チアジアゾール－５－イル基、１，３，４－チアジアゾール－２－イル基等のチアジアゾリル基；
テトラゾール－１－イル基、テトラゾール－２－イル基等のテトラゾリル基；
（２）６員環のヘテロアリール基
ピリジン－２－イル基、ピリジン－３－イル基、ピリジン－４－イル基等のピリジル基；
ピラジン－２－イル基、ピラジン－３－イル基等のピラジニル基；
ピリミジン－２－イル基、ピリミジン－４－イル基、ピリミジン－５－イル基等のピリミジル基；
ピリダジン－３－イル基、ピリダジン－４－イル基等のピリダジニル基；
トリアジニル基；
（３）縮合環のヘテロアリール基
インドール－１－イル基、インドール－２－イル基、インドール－３－イル基、インドール－４－イル基、インドール－５－イル基、インドール－６－イル基、インドール－７－イル基；
ベンゾフラン－２－イル基、ベンゾフラン－３－イル基、ベンゾフラン－４－イル基、ベンゾフラン－５－イル基、ベンゾフラン－６－イル基、ベンゾフラン－７－イル基；
ベンゾチオフェン－２－イル基、ベンゾチオフェン－３－イル基、ベンゾチオフェン－４－イル基、ベンゾチオフェン－５－イル基、ベンゾチオフェン－６－イル基、ベンゾチオフェン－７－イル基；
ベンゾイミダゾール－１－イル基、ベンゾイミダゾール－２－イル基、ベンゾイミダゾール－４－イル基、ベンゾイミダゾール－５－イル基、ベンゾオキサゾール－２－イル基、ベンゾオキサゾール－４－イル基、ベンゾオキサゾール－５－イル基、ベンゾチアゾール－２－イル基、ベンゾチアゾール－４－イル基、ベンゾチアゾール－５－イル基；
キノリン－２－イル基、キノリン－３－イル基、キノリン－４－イル基、キノリン－５－イル基、キノリン－６－イル基、キノリン－７－イル基、キノリン－８－イル基；
　これらのうち、硫黄原子を含む５員環のヘテロアリール基、窒素原子を含む５員環のへテロアリール基、または窒素原子を含む６員環のへテロアリール基が好ましい。 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.
(1) 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;
Isoxazolyl groups such as isoxazol-3-yl group, isoxazol-4-yl group and isoxazol-5-yl group;
Thiazolyl groups such as thiazol-2-yl group, thiazol-4-yl group, thiazol-5-yl group;
Isothiazolyl groups such as isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-5-yl group;
1,2,3-triazol-1-yl group, 1,2,3-triazol-4-yl group, 1,2,3-triazol-5-yl group, 1,2,4-triazol-1-yl A triazolyl group such as a group, 1,2,4-triazol-3-yl group, 1,2,4-triazol-5-yl group;
Oxadiazolyl groups such as 1,2,4-oxadiazol-3-yl group, 1,2,4-oxadiazol-5-yl group, 1,3,4-oxadiazol-2-yl group;
Thiadiazolyl groups such as 1,2,4-thiadiazol-3-yl group, 1,2,4-thiadiazol-5-yl group, 1,3,4-thiadiazol-2-yl group;
Tetrazolyl groups such as a tetrazol-1-yl group and a tetrazol-2-yl group;
(2) pyridyl groups such as a 6-membered heteroaryl group pyridin-2-yl group, pyridin-3-yl group and pyridin-4-yl group;
Pyrazinyl groups such as a pyrazin-2-yl group and a pyrazin-3-yl group;
Pyrimidyl groups such as a pyrimidin-2-yl group, a pyrimidin-4-yl group, and a pyrimidin-5-yl group;
Pyridazinyl groups such as a pyridazin-3-yl group and a pyridazin-4-yl group;
A triazinyl group;
(3) Heteroaryl group of fused ring indol-1-yl group, indol-2-yl group, indol-3-yl group, indol-4-yl group, indol-5-yl group, indol-6-yl group Indol-7-yl group;
Benzofuran-2-yl group, benzofuran-3-yl group, benzofuran-4-yl group, benzofuran-5-yl group, benzofuran-6-yl group, benzofuran-7-yl group;
Benzothiophen-2-yl group, benzothiophen-3-yl group, benzothiophen-4-yl group, benzothiophen-5-yl group, benzothiophen-6-yl group, benzothiophen-7-yl group;
Benzimidazol-1-yl group, benzimidazol-2-yl group, benzimidazol-4-yl group, benzimidazol-5-yl group, benzooxazol-2-yl group, benzooxazol-4-yl group, benzoxazole -5-yl group, benzothiazol-2-yl group, benzothiazol-4-yl group, benzothiazol-5-yl group;
Quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5-yl group, quinolin-6-yl group, quinolin-7-yl group, quinolin-8-yl group;
Of these, a 5-membered heteroaryl group containing a sulfur atom, a 5-membered heteroaryl group containing a nitrogen atom, or a 6-membered heteroaryl group containing a nitrogen atom is preferred.
　Ｒ1の「ヘテロアラルキル基」は、ヘテロアリール基で置換されたＣ１～２０アルキル基である。Ｃ１～２０アルキル基を置換するヘテロアリール基としては前記のヘテロアリール基が挙げられる。
　「ヘテロアラルキル基」としては、以下の基を挙げることができる。
ピロール－１－イルメチル基、ピロール－２－イルメチル基、ピロール－３－イルメチル基、ピラゾール－１－イルメチル基、ピラゾール－３－イルメチル基、ピラゾール－３－イルメチル基、フラン－２－イルメチル基、フラン－３－イルメチル基、チオフェン－２－イルメチル基、チオフェン－３－イルメチル基；
ピリジン－２－イルメチル基、ピリジン－３－イルメチル基、ピリジン－４－イルメチル基、１－ピリジン－２－イルエチル基、２－ピリジン－２－イルエチル基、１－ピリジン－２－イルプロピル基、３－ピリジン－２－イルプロピル基等のピリジルＣ１～６アルキル基；
ピラジン－２－イルメチル基、ピラジン－３－イルメチル基、ピラジン－４－イルメチル基、１－ピラジン－２－イルエチル基、２－ピラジン－２－イルエチル基、１－ピラジン－２－イルプロピル基、３－ピラジン－２－イルプロピル基；
ピリミジン－２－イルメチル基、ピリミジン－３－イルメチル基、ピリミジン－４－イルメチル基、１－ピリミジン－２－イルエチル基、２－ピリミジン－２－イルエチル基、
１－ピリミジン－２－イルプロピル基、３－ピリミジン－２－イルプロピル基；
　これらのうち、ヘテロアラルキル基としては、硫黄原子を含む５員環のヘテロアリール基、窒素原子を含む５員環のへテロアリール基、または窒素原子を含む６員環のへテロアリール基で置換されたＣ１～６アルキル基が好ましい。 The “heteroaralkyl group” for R 1 is a C1-20 alkyl group substituted with a heteroaryl group. Examples of the heteroaryl group for substituting the C1-20 alkyl group include the above heteroaryl groups.
Examples of the “heteroaralkyl group” include the following groups.
Pyrrol-1-ylmethyl group, pyrrol-2-ylmethyl group, pyrrol-3-ylmethyl group, pyrazol-1-ylmethyl group, pyrazol-3-ylmethyl group, pyrazol-3-ylmethyl group, furan-2-ylmethyl group, furan -3-ylmethyl group, thiophen-2-ylmethyl group, thiophen-3-ylmethyl group;
Pyridin-2-ylmethyl group, pyridin-3-ylmethyl group, pyridin-4-ylmethyl group, 1-pyridin-2-ylethyl group, 2-pyridin-2-ylethyl group, 1-pyridin-2-ylpropyl group, 3 A pyridyl C1-6 alkyl group such as a pyridin-2-ylpropyl group;
Pyrazin-2-ylmethyl group, pyrazin-3-ylmethyl group, pyrazin-4-ylmethyl group, 1-pyrazin-2-ylethyl group, 2-pyrazin-2-ylethyl group, 1-pyrazin-2-ylpropyl group, 3 A pyrazin-2-ylpropyl group;
Pyrimidin-2-ylmethyl group, pyrimidin-3-ylmethyl group, pyrimidin-4-ylmethyl group, 1-pyrimidin-2-ylethyl group, 2-pyrimidin-2-ylethyl group,
1-pyrimidin-2-ylpropyl group, 3-pyrimidin-2-ylpropyl group;
Of these, the heteroaralkyl group is substituted with a 5-membered heteroaryl group containing a sulfur atom, a 5-membered heteroaryl group containing a nitrogen atom, or a 6-membered heteroaryl group containing a nitrogen atom. C1-6 alkyl groups are preferred.
　式（Ｉ）中、Ｒ2は、水素原子、ハロゲン原子、Ｃ１～２０アルキル基、Ｃ１～２０ハロアルキル基、Ｃ２～２０アルケニル基、Ｃ２～２０ハロアルケニル基、Ｃ２～２０アルキニル基、Ｃ２～２０ハロアルキニル基、Ｃ１～２０アルコキシ基、Ｃ１～２０ハロアルコキシ基、Ｃ３～２０シクロアルキル基、Ｃ４～２０シクロアルケニル基、Ｃ８～２０シクロアルキニル基、Ｃ１～２０アシル基、Ｃ１～２０アルコキシカルボニル基、無置換若しくは置換基を有するＣ６～１０アリール基、無置換若しくは置換基を有するヘテロアリール基、無置換若しくは置換基を有するアラルキル基、または無置換若しくは置換基を有するヘテロアラルキル基を示す。 In the formula (I), 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.
　Ｒ2の「ハロゲン原子」としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
　Ｒ2の「Ｃ１～２０アルキル基」は、直鎖または分岐鎖の炭素数１～２０の飽和炭化水素基を意味する。
　「Ｃ１～２０アルキル基」としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、２－メチルブチル基、２，２－ジメチルプロピル基、ｎ－ヘキシル基、イソヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ノニル基、イソノニル基、ｎ－デシル基、２－エチルオクチル基、３－エチルオクチル基、２，３－ジメチルオクチル基、４－プロピルオクチル基、ドデシル基、４－エチルデシル基、６－エチルドデシル基、３，５－ジメチルデシル基、２，５－ジメチルデシル基、６－プロピルノニル基、４－ブチルオクチル基、トリデシル基、テトラデシル基、２，４，６，８－テトラメチルデシル基、２，２－ジエチルデシル基、２，５－ジエチルデシル基、４－ブチルデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、２，４，６，８－テトラエチルデシル基、ノナデシル基、イコシル基等が挙げられる。これらのうち、Ｃ１～６アルキル基、すなわち、直鎖または分岐鎖の炭素数１～６の飽和炭化水素基が好ましい。 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. , Isopentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, nonyl group, isononyl group, n-decyl group, 2 -Ethyloctyl group, 3-ethyloctyl group, 2,3-dimethyloctyl group, 4-propyloctyl group, dodecyl group, 4-ethyldecyl group, 6-ethyldodecyl group, 3,5-dimethyldecyl group, 2,5 -Dimethyldecyl group, 6-propylnonyl group, 4-butyloctyl group, tridecyl group, tetradecyl group, 2,4,6,8-tetramethyldecyl group, 2,2-die Rudeshiru group, 2,5-diethyl-decyl group, 4-Buchirudeshiru group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 2,4,6,8-tetraethyl-decyl group, nonadecyl group, eicosyl group and the like. Of these, a C1-6 alkyl group, that is, a linear or branched saturated hydrocarbon group having 1 to 6 carbon atoms is preferable.
　Ｒ2の「Ｃ１～２０ハロアルキル基」は、Ｃ１～２０アルキル基中の少なくとも一つの水素原子がハロゲン原子で置換されてなる基を意味する。
　「Ｃ１～２０ハロアルキル基」としては、フルオロメチル基、クロロメチル基、ブロモメチル基、ジフルオロメチル基、ジクロロメチル基、ジブロモメチル基、トリフルオロメチル基、トリクロロメチル基、トリブロモメチル基、２，２，２－トルフルオロエチル基、２，２，２－トリクロロエチル基、ペンタフルオロエチル基、４－フルオロブチル基、４－クロロブチル基、３，３，３－トリフルオロプロピル基、２，２，２－トリフルオロ－１－トリフルオロメチルエチル基、パーフロロヘキシル基、パークロロヘキシル基、パーフロロオクチル基、パークロロオクチル基、２，４，６－トリクロロヘキシル基、パーフロロデシル基、２，２，４，４，６，６－へキサクロロオクチル基、２，２，４，４，６，６－ヘキサクロロ－３－プロピル－オクチル基等が挙げられる。これらのうち、Ｃ１～６ハロアルキル基、すなわち、Ｃ１～６アルキル基中の少なくとも一つの水素原子がハロゲン原子で置換されてなる基が好ましい。 The “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, 2,4,6-trichlorohexyl group, perfluorodecyl group, 2,2 , 4,4,6,6-hexachlorooctyl group, 2,2,4,4,6,6-hexachloro-3-propyl Pill - octyl group. Of these, a C1-6 haloalkyl group, that is, a group in which at least one hydrogen atom in the C1-6 alkyl group is substituted with a halogen atom is preferable.
　Ｒ2の「Ｃ２～２０アルケニル基」は、炭素―炭素二重結合を少なくとも一つ有する炭素数２～２０の直鎖または分岐鎖の不飽和炭化水素基を意味する。
　「Ｃ２～２０アルケニル基」としては、ビニル基、１－プロペニル基、アリル基、１－ブテニル基、２－ブテニル基、３－ブテニル基、１－メチル－２－プロペニル基、２－メチル－２－プロペニル基、１－ペンテニル基、２－ペンテニル基、３－ペンテニル基、４－ペンテニル基、１－メチル－２－ブテニル基、２－メチル－２－ブテニル基、１－ヘキセニル基、２－ヘキセニル基、３－ヘキセニル基、４－ヘキセニル基、５－ヘキセニル基、１－ヘプテニル基、６－ヘプテニル基、１－オクテニル基、７－オクテニル基、１－デセニル基、９－デセニル基、１－ドデセニル基、４－ドデセニル基、１－オクタデセニル基、２－エチル－１－オクタデセニル基等が挙げられる。これらのうち、Ｃ２～６アルケニル基が好ましい。 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, 1-dodecenyl group Group, 4-dodecenyl group, 1-octadecenyl group, 2-ethyl-1-octadecenyl group and the like. Of these, C2-6 alkenyl groups are preferred.
　Ｒ2の「Ｃ２～２０ハロアルケニル基」は、Ｃ２～２０アルケニル基中の少なくとも一つの水素原子がハロゲン原子で置換されてなる基である。
　「Ｃ２～２０ハロアルケニル基」としては、３－クロロ－２－プロペニル基、４－クロロ－２－ブテニル基、４，４－ジクロロ－３－ブテニル基、４，４－ジフルオロ－３－ブテニル基、３，３－ジクロロ－２－プロペニル基、２，３－ジクロロ－２－プロペニル基、３，３－ジフルオロ－２－プロペニル基、２，４，６－トリクロロ－２－ヘキセニル基、３－エチル－２，４，６－トリフルオロ－２－ヘキセニル基等が挙げられる。これらのうち、Ｃ２～６ハロアルケニル基が好ましい。 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. 3,3-dichloro-2-propenyl group, 2,3-dichloro-2-propenyl group, 3,3-difluoro-2-propenyl group, 2,4,6-trichloro-2-hexenyl group, 3-ethyl -2,4,6-trifluoro-2-hexenyl group and the like. Of these, C2-6 haloalkenyl groups are preferred.
　Ｒ2の「Ｃ２～２０アルキニル基」は、炭素―炭素三重結合を少なくとも一つ有する炭素数２～２０の直鎖または分岐鎖の不飽和炭化水素基を意味する。
　「Ｃ２～２０アルキニル基」としては、エチニル基、１－プロピニル基、プロパルギル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－メチル－２－プロピニル基、２－メチル－３－ブチニル基、１－ペンチニル基、２－ペンチニル基、３－ペンチニル基、４－ペンチニル基、１－メチル－２－ブチニル基、２－メチル－３－ペンチニル基、１－ヘキシニル基、１，１－ジメチル－２－ブチニル基、ドデシニル基、ブタデシニル基、ヘプタデシニル基、４－エチルヘキサデシニル基等が挙げられる。これらのうち、Ｃ２～６アルキニル基が好ましい。 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. Of these, C2-6 alkynyl groups are preferred.
　Ｒ2の「Ｃ２～２０ハロアルキニル基」は、Ｃ２～２０アルキニル基中の少なくとも一つの水素原子がハロゲン原子で置換されてなる基である。
　「Ｃ２～２０ハロアルキニル基」としては、３－クロロ－１－プロピニル基、３－クロロ－１－ブチニル基、３－ブロモ－１－ブチニル基、３－ブロモ－２－プロピニル基、３－ヨード－２－プロピニル基、５、５－ジクロロ－２－メチル－３－ペンチニル基、３－ブロモ－１－ヘキシニル基、４－クロロ－１，１－ジメチル－２－ブチニル基、４，４，６，６－テトラフロロ－１－ドデシニル基等が挙げられる。これらのうち、Ｃ２～６ハロアルキニル基が好ましい。 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.
　Ｒ2の「Ｃ１～２０アルコキシ基」は、水酸基中の水素原子がＣ１～２０アルキル基で置換されてなる基である。
　「Ｃ１～２０アルコキシ基」としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｉ－ブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基、ｎ－ペンチルオキシ基、１－エチルプロポキシ基、ｎ－ヘキシルオキシ基、イソヘキシルオキシ基、４－メチルペントキシ基、３－メチルペントキシ基、２－メチルペントキシ基、１－メチルペントキシ基、３，３－ジメチルブトキシ基、２，２－ジメチルブトキシ基、１，１－ジメチルブトキシ基、１，２－ジメチルブトキシ基、１，３－ジメチルブトキシ基、２，３－ジメチルブトキシ基、１－エチルブトキシ基、２－エチルブトキシ基、デシルオキシ基、ドデシルオキシ基、２－エチルデシルオキシ基、ラウリルオキシ基等が挙げられる。これらのうち、Ｃ１～６アルコキシ基が好ましい。 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, decyloxy group, dodecyloxy group, 2-ethyldecyloxy group, lauryloxy group and the like. Of these, C1-6 alkoxy groups are preferred.
　Ｒ2の「Ｃ１～２０ハロアルコキシ基」は、Ｃ１～２０アルコキシ基中の少なくとも一つの水素原子がハロゲン原子で置換されてなる基である。
　「Ｃ１～２０ハロアルコキシ基」としては、クロロメトキシ基、ジクロロメトキシ基、トリクロロメトキシ基、トリフルオロメトキシ基、１－フルオロエトキシ基、１，１－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、ペンタフルオロエトキシ基、４，５－ジクロロ－３－メチルペントキシ基、２－フロロ－２－エチルデシルオキシ基、１－クロロラウリルオキシ基等が挙げられる。これらのうち、Ｃ１～６ハロアルコキシ基が好ましい。 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.
　Ｒ2の「Ｃ３～２０シクロアルキル基」は、飽和脂環構造を有する炭素数３～２０の炭化水素基である。
　「Ｃ３～２０シクロアルキル基」としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロプロピルメチル基、２－シクロプロピルエチル基、２，３，３－トリメチルシクロブチル基、シクロペンチルメチル基、２－シクロヘキシルエチル基、２－シクロオクチルエチル基、４，４，６，６－テトラメチルシクロヘキシル基、１，３－ジブチルシクロヘキシル基、ノルボルニル基、ビシクロ［２．２．２］オクチル基、アダマンチル基等が挙げられる。これらのうち、Ｃ３～６シクロアルキル基が好ましい。 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 cycloalkyl groups are preferred.
　Ｒ2の「Ｃ４～２０シクロアルケニル基」は、炭素―炭素二重結合を含む不飽和脂環構造を有する炭素数４～２０の炭化水素基である。
　「Ｃ４～２０シクロアルケニル基」としては、１－シクロブテニル基、１－シクロペンテニル基、３－シクロペンテニル基、１－シクロヘキセニル基、３－シクロヘキセニル基、３－シクロヘプテニル基、４－シクロオクテニル基、２－メチル－３－シクロヘキサセニル基、３，４－ジメチル－３－シクロヘキセニル基、シクロペンテニルメチル基、３－シクロペンタテニルメチル基、３－シクロヘキセニルメチル基、２－（３－シクロヘキセニル）エチル基等が挙げられる。これらのうち、Ｃ４～８シクロアルケニル基が好ましい。 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.
　Ｒ2の「Ｃ８～２０シクロアルキニル基」は、炭素―炭素三重結合を含む不飽和脂環構造を有する炭素数８～２０の炭化水素基である。
　「Ｃ８～２０シクロアルキニル基」としては、５－シクロオクチニル基、６－シクロデシニル基、７－シクロドデシニル基、２，３－ジエチル－４－シクロデシニル基、５－シクロオクチニルメチル基等が挙げられる。これらのうち、Ｃ８～１２シクロアルキニル基が好ましい。 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.
　Ｒ2の「Ｃ１～２０アシル基」は、水素原子、直鎖若しくは分岐鎖のアルキル基、アリール基またはへテロアリール基がカルボニル基と結合してなる炭素数１～２０を有する基である。
　「Ｃ１～２０アシル基」としては、ホルミル基、アセチル基、プロピオニル基、ｎ－プロピルカルボニル基、ｉ－プロピルカルボニル基、ｎ－ブチルカルボニル基、ｉ－ブチルカルボニル基、ペンタノイル基、ピバロイル基、バレリル基、イソバレリル基、オクタノイル基、ノナノイル基、デカノイル基、３－メチルノナノイル基、８－メチルノナノイル基、３－エチルオクタノイル基、３，７－ジメチルオクタノイル基、ウンデカノイル基、ドデカノイル基、トリデカノイル基、テトラデカノイル基、ペンタデカノイル基、ヘキサデカノイル基、１－メチルペンタデカノイル基、１４－メチルペンタデカノイル基、１３，１３－ジメチルテトラデカノイル基、ヘプタデカノイル基、１５－メチルヘキサデカノイル基、オクタデカノイル基、１－メチルヘプタデカノイル基、ノナデカノイル基、アイコサノイル基及びヘナイコサノイル基、ベンゾイル基、ナフチルカルボニル基、ビフェニルカルボニル基、アントラニルカルボニル基、２－ピリジルカルボニル基、チエニルカルボニル基等が挙げられる。これらのうち、Ｃ１～６アシル基が好ましい。 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.
Examples of the “C1-20 acyl group” 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-dimethyltetradecanoyl group, heptadecanoyl group, 15-methylhexadecanoyl group , Octadecanoyl group, - methyl hepta decanoyl group, Nonadekanoiru group, Aikosanoiru group and Henaikosanoiru group, a benzoyl group, naphthyl carbonyl group, biphenyl carbonyl group, anthranyl group, 2-pyridylcarbonyl group, and a thienylcarbonyl group. Of these, C1-6 acyl groups are preferred.
　Ｒ2の「Ｃ１～２０アルコキシカルボニル基」はＣ１～２０アルコキシ基がカルボニル基と結合した基である。
　「Ｃ１～２０アルコキシカルボニル基」としては、メトキシカルボニル基、エトキシカルボニル基、ｎ－プロポキシカルボニル基、ｉ－プロポキシカルボニル基、ｎ－ブトキシカルボニル基、ｉ－ブトキシカルボニル基、ｔ－ブトキシカルボニル基、ｎ－ペンチルオキシカルボニル基、ｎ－ヘキシルオキシカルボニル基、デシルオキシカルボニル基、ドデシルオキシカルボニル基、２－エチルデシルオキシカルボニル基、ラウリルオキシカルボニル基等が挙げられる。これらのうち、Ｃ１～６アルコキシカルボニル基が好ましい。 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.
　Ｒ2の、「Ｃ６～１０アリール基」、「ヘテロアリール基」、「アラルキル基」または「ヘテロアラルキル基」はＲ1で例示したものと同様のものが挙げられる。 Of R 2, "C6 ~ 10 aryl group", "heteroaryl group", "aralkyl group" or "heteroaralkyl group" include the same as exemplified for R 1.
　前記「置換基を有するＣ６～１０アリール基」、「置換基を有するヘテロアリール基」、「置換基を有するアラルキル基」、及び「置換基を有するヘテロアラルキル基」における「置換基」としては、フッ素原子、塩素原子、臭素原子等のハロゲン原子；メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓ－ブチル基、ｉ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、２－メチルブチル基、２，２－ジメチルプロピル基、ｎ－ヘキシル基、イソヘキシル基のＣ１～６アルキル基；メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｓ－ブトキシ基、ｉ－ブトキシ基、ｔ－ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等のＣ１～６アルコキシ基；クロロメトキシ基、ジクロロメトキシ基、トリクロロメトキシ基、トリフルオロメトキシ基、１－フルオロエトキシ基、１，１－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、ペンタフルオロエトキシ基、４，５－ジクロロ－３－メチルペントキシ基等のＣ１～６ハロアルコキシ基；メチルチオ基、エチルチオ基、ｎ－プロピルチオ基、ｉ－プロピルチオ基、ｎ－ブチルチオ基、ｉ－ブチルチオ基、ｓ－ブチルチオ基、ｔ－ブチルチオ基等のＣ１～６アルキルチオ基；メチルスルホニル基、エチルスルホニル基、ｎ－プロピルスルホニル基、ｎ－ブチルスルホニル基等のＣ１～６アルキルスルホニル基；クロロメチル基、フルオロメチル基、トリフルオロメチル基等のＣ１～６ハロアルキル基；メチルスルホニルオキシ基、エチルスルホニルオキシ基、ｎ－プロピルスルホニルオキシ基、ｔ－ブチルスルホニルオキシ基等のＣ１～６アルキルスルホニルオキシ基；等が挙げられる。 As the “substituent” in the above-mentioned “C6-10 aryl group having a substituent”, “heteroaryl group having a substituent”, “aralkyl group having a substituent”, and “heteroaralkyl group having a substituent”, Halogen atoms such as fluorine atom, chlorine atom, bromine atom; methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n A pentyl group, isopentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, C1-6 alkyl group of isohexyl group; methoxy group, ethoxy group, n-propoxy group, i- C1-6 alkoxy such as propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, etc. 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, fluoromethyl group, trifluoro C1-6 haloalkyl groups such as a methyl group; methylsulfonyloxy , Ethylsulfonyl group, n- propylsulfonyl group, C1 ~ 6 alkyl sulfonyloxy group such as a t- butylsulfonyl group; and the like.
　式（Ｉ）中、Ｒ3～Ｒ6は、それぞれ独立して、水素原子、ハロゲン原子、Ｃ１～２０アルキル基、Ｃ１～２０ハロアルキル基、Ｃ２～２０アルケニル基、Ｃ２～２０ハロアルケニル基、Ｃ２～２０アルキニル基、Ｃ２～２０ハロアルキニル基、Ｃ１～２０アルコキシ基、Ｃ１～２０ハロアルコキシ基、Ｃ３～２０シクロアルキル基、Ｃ３～２０シクロアルコキシ基、Ｃ２～２０アルケニルオキシ基、Ｃ２～２０アルキニルオキシ基、Ｃ１～２０アルキルチオ基、シアノ基、ニトロ基、無置換若しくは置換基を有するアミノ基、水酸基、チオール基、無置換若しくは置換基を有するフェニル基、無置換若しくは置換基を有するアラルキル基、無置換若しくは置換基を有するアリールオキシ基、または無置換若しくは置換基を有するヘテロ環基を示す。但し、Ｒ5とＲ6は、同時に水素原子であることはない。 In the formula (I), 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 unsubstituted or substituted aryloxy group, or an unsubstituted or substituted heterocyclic group Show. However, R 5 and R 6 are not simultaneously hydrogen atoms.
　Ｒ3～Ｒ6の、ハロゲン原子、Ｃ１～２０アルキル基、Ｃ１～２０ハロアルキル基、Ｃ２～２０アルケニル基、Ｃ２～２０ハロアルケニル基、Ｃ２～２０アルキニル基、Ｃ２～２０ハロアルキニル基、Ｃ１～２０アルコキシ基、Ｃ１～２０ハロアルコキシ基、Ｃ３～２０シクロアルキル基、無置換若しくは置換基を有するアラルキル基の具体例としては、前記のＲ2の具体例として列記したものと同様のものが挙げられる。 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.
　Ｒ3～Ｒ6の「Ｃ３～２０シクロアルコキシ基」は、水酸基中の水素原子がＣ３～２０シクロアルキル基で置換されてなる基である。
　「Ｃ３～２０シクロアルコキシ基」としては、シクロプロピルオキシ基、シクロブチルオキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基、シクロヘプチルオキシ基、シクロオクチルオキシ基、シクロプロピルメチルオキシ基、２－シクロペンチルエチルオキシ基、２－メチルシクロプロピルオキシ基、２－エチルシクロプロピルオキシ基、２，３，３－トリメチルシクロブチルオキシ基、２－メチルシクロペンチルオキシ基、２－エチルシクロヘキシルオキシ基、２－エチルシクロオクチルオキシ基、４，４，６，６－テトラメチルシクロヘキシルオキシ基、１，３－ジブチルシクロヘキシルオキシ基等が挙げられる。これらのうち、Ｃ３～６シクロアルコキシ基が好ましい。 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-dibutylcyclohexyloxy group and the like. Of these, C3-6 cycloalkoxy groups are preferred.
　Ｒ3～Ｒ6の「Ｃ２～２０アルケニルオキシ基」は、水酸基中の水素原子がＣ２～２０アルケニル基で置換されてなる基である。
　「Ｃ２～２０アルケニルオキシ基」としては、ビニルオキシ基、１－プロペニルオキシ基、２－プロペニルオキシ基、１－ブテニルオキシ基、２－ブテニルオキシ基、３－ブテニルオキシ基、１－メチル－２－プロペニルオキシ基、２－メチル－２－プロペニルオキシ基、１－ペンテニルオキシ基、２－ペンテニルオキシ基、３－ペンテニルオキシ基、４－ペンテニルオキシ基、１－メチル－２－ブテニルオキシ基、２－メチル－２－ブテニルオキシ基、１－ヘキセニルオキシ基、２－ヘキセニルオキシ基、３－ヘキセニルオキシ基、４－ヘキセニルオキシ基、５－ヘキセニルオキシ基、１－ヘプテニルオキシ基、６－ヘプテニルオキシ基、１－オクテニルオキシ基、７－オクテニルオキシ基、１－デセニルオキシ基、９－デセニルオキシ基、１－ドデセニルオキシ基、４－ドデセニルオキシ基、１－オクタデセニルオキシ基、２－エチル－１－オクタデセニルオキシ基等が挙げられる。これらのうち、Ｃ２～６アルケニルオキシ基が好ましい。 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 group, 6-heptenyloxy group, 1-octenyloxy group, 7-octenyloxy group, 1-decenyloxy group, 9-decenyloxy group 1 Dodeseniruokishi group, 4-Dodeseniruokishi group, 1-octadecenyl group, 2-ethyl-1-octadecenyl group, and the like. Of these, C2-6 alkenyloxy groups are preferred.
　Ｒ3～Ｒ6の「Ｃ２～２０アルキニルオキシ基」は、水酸基中の水素原子がＣ２～２０アルキニル基で置換されてなる基である。
　「Ｃ２～２０アルキニルオキシ基」としては、エチニルオキシ基、プロピニルオキシ基、プロパルギルオキシ基、１－ブチニルオキシ基、２－ブチニルオキシ基、３－ブチニルオキシ基、１－メチル－２－プロピニルオキシ基、２－メチル－３－ブチニルオキシ基、１－ペンチニルオキシ基、２－ペンチニルオキシ基、３－ペンチニルオキシ基、４－ペンチニルオキシ基、１－メチル－２－ブチニルオキシ基、２－メチル－３－ペンチニルオキシ基、１－ヘキシニルオキシ基、１，１－ジメチル－２－ブチニルオキシ基、ドデシニルオキシ基、ブタデシニルオキシ基、ヘプタデシニルオキシ基、４－エチルヘキサデシニルオキシ基等が挙げられる。これらのうち、Ｃ２～６アルキニルオキシ基が好ましい。 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, butadecynyloxy group, heptadecynyloxy group, 4-ethylhexadecynyloxy group, and the like. Of these, C2-6 alkynyloxy groups are preferred.
　Ｒ3～Ｒ6の「Ｃ１～２０アルキルチオ基」は、チオール基中の水素原子がＣ１～２０アルキル基で置換されてなる基である。
　「Ｃ１～２０アルキルチオ基」としては、メチルチオ基、エチルチオ基、ｎ－プロピルチオ基、ｉ－プロピルチオ基、ｎ－ブチルチオ基、ｔ－ブチルチオ基、ペンチルチオ基、イソペンチルチオ基、２－メチルブチルチオ基、ネオペンチルチオ基、１－エチルプロピルチオ基、ヘキシルチオ基、イソヘキシルチオ基、４－メチルペンチルチオ基、３－メチルペンチルチオ基、２－メチルペンチルチオ基、１－メチルペンチルチオ基、３，３－ジメチルブチルチオ基、２，２－ジメチルブチルチオ基、１，１－ジメチルブチルチオ基、１，２－ジメチルブチルチオ基、１，３－ジメチルブチルチオ基、２，３－ジメチルブチルチオ基、２－エチルブチルチオ基、３－エチルオクチルチオ基、２，３－ジメチルオクチルチオ基、４－プロピルオクチルチオ基、ドデシルチオ基、４－エチルデシルチオ基、６－エチルドデシルチオ基、３，５－ジメチルデシルチオ基、２，５－ジメチルデシルチオ基、６－プロピルノニルチオ基、４－ブチルオクチルチオ基、トリデシルチオ基、テトラデシルチオ基、２，４，６，８－テトラメチルデシルチオ基、２，２－ジエチルデシルチオ基、２，５－ジエチルデシルチオ基、４－ブチルデシルチオ基、ペンタデシルチオ基、ヘキサデシルチオ基、ヘプタデシルチオ基、オクタデシルチオ基、２，４，６，８－テトラエチルデシルチオ基、ノナデシルチオ基、イコシルチオ基等が挙げられる。これらのうち、Ｃ１～６アルキルチオ基が好ましい。 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 group, 1,1-dimethylbutylthio group, 1,2-dimethylbutylthio group, 1,3-dimethylbutylthio group, 2,3-dimethylbutyl group Thio group, 2-ethylbutylthio group, 3-ethyloctylthio group, 2,3-dimethyloctylthio group, 4-propyloctyl group Ruthio group, dodecylthio group, 4-ethyldecylthio group, 6-ethyldodecylthio group, 3,5-dimethyldecylthio group, 2,5-dimethyldecylthio group, 6-propylnonylthio group, 4-butyloctylthio group Group, tridecylthio group, tetradecylthio group, 2,4,6,8-tetramethyldecylthio group, 2,2-diethyldecylthio group, 2,5-diethyldecylthio group, 4-butyldecylthio group, pentadecylthio group Group, hexadecylthio group, heptadecylthio group, octadecylthio group, 2,4,6,8-tetraethyldecylthio group, nonadecylthio group, icosylthio group and the like. Of these, C1-6 alkylthio groups are preferred.
　Ｒ3～Ｒ6の「無置換若しくは置換基を有するアミノ基」としては、アミノ基；メチルアミノ基、エチルアミノ基等のモノアルキルアミノ基、好ましくはモノＣ１～６アルキルアミノ基；ジメチルアミノ基、ジエチルアミノ基等のジアルキルアミノ基、好ましくはジＣ１～６アルキルアミノ基；フェニルアミノ基、４－メチルフェニルアミノ基等のモノアリールアミノ基、好ましくはモノＣ６～１０アリールアミノ基；ジフェニルアミノ基、ジ１－ナフチルアミノ基等のジアリールアミノ基、好ましくはジＣ６～１０アリールアミノ基；アセチルアミノ基、ベンゾイルアミノ基等のアシルアミノ基、好ましくはＣ１～６アシルアミノ基等が挙げられる。 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.
　Ｒ3～Ｒ6の「アリールオキシ基」は、水酸基中の水素原子がアリール基で置換されてなる基である。アリール基は単環のもの及び多環のものを含む。ここで、多環アリール基は、少なくとも一つの環が芳香環であれば、残りの環が飽和脂環、部分不飽和脂環または芳香環のいずれであってもよい。
　「アリールオキシ基」としては、フェニルオキシ基、ナフチルオキシ基、アズレニルオキシ基、インデニルオキシ基、インダニルオキシ基、テトラリニルオキシ基等が挙げられる。これらのうち、Ｃ６～１０アリールオキシ基、すなわち、水酸基中の水素原子がＣ６～１０アリール基で置換されてなる基が好ましい。 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.
Examples of 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.
　Ｒ3～Ｒ6の、「ヘテロ環基」は、環を構成する原子として炭素原子以外に窒素原子、酸素原子及び硫黄原子から選ばれる１～４個の複素原子を含む５～７員のヘテロアリール基、飽和へテロ環基、部分不飽和へテロ環基である。この場合、単環、または環同士が縮合した多環であってもよい。 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. An aryl group, a saturated heterocyclic group, and a partially unsaturated heterocyclic group. In this case, it may be a single ring or a polycyclic ring condensed.
　「ヘテロ環基」としては、Ｒ１で例示した「ヘテロアリール基」、以外に以下の基を挙げることができる。
ピロリジン－１－イル基、ピロリジン－２－イル基、ピロリジン－３－イル基、テトラヒドロフラン－２－イル基、テトラヒドロフラン－３－イル基；
ピペリジン－１－イル基、ピペリジン－２－イル基、ピペリジン－３－イル基、ピペリジン－４－イル基、ピペラジン－１－イル基、ピペラジン－２－イル基、モルホリン－２－イル基、モルホリン－３－イル基、モルホリン－４－イル基； Examples of the “heterocyclic group” include the following groups in addition to the “heteroaryl group” exemplified for R 1 .
Pyrrolidin-1-yl group, pyrrolidin-2-yl group, pyrrolidin-3-yl group, tetrahydrofuran-2-yl group, tetrahydrofuran-3-yl group;
Piperidin-1-yl group, piperidin-2-yl group, piperidin-3-yl group, piperidin-4-yl group, piperazin-1-yl group, piperazin-2-yl group, morpholin-2-yl group, morpholine -3-yl group, morpholin-4-yl group;
　Ｒ3～Ｒ6の「置換基を有するフェニル基」、「置換基を有するアリールオキシ基」、「置換基を有するアラルキル基」及び「置換基を有するヘテロ環基」における「置換基」としては、Ｒ1の「置換基を有するＣ６～１０アリール基」等における「置換基」として例示したものと同様のものが挙げられる。 As the “substituent” in the “phenyl group having a substituent”, “aryloxy group having a substituent”, “aralkyl group having a substituent” and “heterocyclic group having a substituent” of R 3 to R 6 And the same as those exemplified as the “substituent” in the “C6-10 aryl group having a substituent” of R 1 and the like.
　上記の例のほか、Ｒ4とＲ5、及びＲ5とＲ6は、一緒になって、それぞれが結合する炭素原子と共に、無置換若しくは置換基を有する５～８員環を形成してもよい。「Ｒ4とＲ5、及びＲ5とＲ6は、一緒になって、それぞれが結合する炭素原子と共に、無置換若しくは置換基を有する５～８員環を形成してもよい」とは、Ｒ4とＲ5及びＲ5とＲ6の両方が環を形成している場合、並びに、Ｒ4とＲ5、またはＲ5とＲ6のいずれか一方が環を形成している場合があってもよいことを意味する。 In addition to the above examples, 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. Good. “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” In some cases, 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.
　Ｒ4とＲ5及びＲ5とＲ6が一緒になって、それぞれが結合する炭素原子と共に形成する無置換若しくは置換基を有する５～８員環としては、無置換若しくは置換基を有するシクロアルケン環、無置換若しくは置換基を有する芳香族炭化水素環または無置換若しくは置換基を有するヘテロ環が挙げられる。
　シクロアルケン環としては、シクロペンテン環、シクロヘキセン環、シクロヘプテン環、シクロオクテン環等が挙げられる。
　芳香族炭化水素環としては、ベンゼン環が挙げられる。
　ヘテロ環としては、ジヒドロピロール環、ジヒドロフラン環、ジヒドロチオフェン環、［１,３］ジオキソール環、［１,３］ジチオール環、［１,３］オキサチオール環、テトラヒドロピリジン環、ジヒドロピラン環、ジヒドロチオピラン環、３，４－ジヒドロ－２Ｈ－［１，４］オキサジン環、２，３－ジヒドロ－［１，４］ジオキシン環、３，４－ジヒドロ－２Ｈ－［１，４］チアジン環、２，３－ジヒドロ－［１，４］ジチイン環、ピロ－ル環、フラン環、チオフェン環、ピラゾール環、イミダゾール環、オキサゾール環、イソオキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環等が挙げられる。
　これらのうち、無置換若しくは置換基を有するベンゼン環が好ましい。 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.
Examples of 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 ring And a pyridazine ring.
Of these, unsubstituted or substituted benzene rings are preferred.
　Ｒ4とＲ5及びＲ5とＲ6が一緒になって形成する環に有することができる置換基は、Ｒ1の「置換基を有するＣ６～１０アリール基」等における「置換基」として例示したものと同様のものが挙げられる。これらのうち、置換基として、ハロゲン原子、Ｃ１～６アルキル基、またはＣ１～６アルコキシ基が好ましい。 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.
　式（Ｉ）中、Ｘは、ハロゲン原子、ニトロ基、無置換若しくは置換基を有するアミノ基、水酸基、または有機基を示す。
　「ハロゲン原子」としては、Ｒ2の「ハロゲン原子」として例示したものと同様のものが挙げられる。「アミノ基」としては、Ｒ3の「アミノ基」として例示したものと同様のものが挙げられる。 In formula (I), X represents a halogen atom, a nitro group, an unsubstituted or substituted amino group, a hydroxyl group, or an organic group.
Examples of the “halogen atom” include those exemplified as the “halogen atom” for R 2 . Examples of the “amino group” include those exemplified as the “amino group” for R 3 .
　「有機基」は、炭素原子を含む原子団であれば、特に限定されない。例えば、シアノ基；　ホルミル基、アセチル基、ベンゾイル基等のＣ１～７アシル基；　メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基等のＣ１～６アルキル基；　ビニル基、プロペニル基、イソプロペニル基、２－ブテニル基等のＣ２～６アルケニル基；　プロパルギル基、３－ブチニル基等のＣ２～６アルキニル基；　トリフルオロメチル基、ペンタフルオロエチル基、３，３，３－トリフルオロプロピル基等のＣ１～６ハロアルキル基；　シクロプロピル基、シクロペンチル基、シクロヘキシル基等のＣ３～８シクロアルキル基；　２－クロロシクロプロピル基、２，２－ジクロロシクロプロピル基、３－クロロシクロペンチル基、４－ブロモシクロヘキシル基等のＣ３～８ハロシクロアルキル基；　メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｔ－ブトキシ基等のＣ１～６アルコキシ基；　トリクロロメトキシ基、トリフルオロメトキシ基等のＣ１～６ハロアルコキシ基； The “organic group” is not particularly limited as long as it is an atomic group containing a carbon atom. For example, 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-dichlorocyclopropyl group, 3-chlorocyclopentyl group, 4 -C3-8 halocycloalkyl group such as bromocyclohexyl group; methoxy group, ethoxy group n- propoxy, i- propoxy, n- butoxy group, C1 ~ 6 alkoxy group such as t- butoxy group; trichloromethoxy group, C1 ~ 6 haloalkoxy group such as trifluoromethoxy group;
　メチルスルホニル基、エチルスルホニル基等のＣ１～６アルキルスルホニル基；　クロロメチルスルホニル基、トリクロロメチルスルホニル基等のＣ１～６ハロアルキルスルホニル基；　メチルスルホニルオキシ基、エチルスルホニルオキシ基等のＣ１～６アルキルスルホニルオキシ基；　フェニルスルホニル基、４－メチルフェニルスルホニル基等の無置換若しくは置換基を有するフェニルスルホニル基；　フェニルスルホニルオキシ基、４－メチルフェニルスルホニルオキシ基等の無置換若しくは置換基を有するフェニルスルホニルオキシ基；　メチルチオ基、エチルチオ基等のＣ１～６アルキルチオ基；　クロロメチルチオ基、トリクロロメチルチオ基、トリフルオロメチルチオ基等のＣ１～６ハロアルキルチオ基；　フェニルチオ基、４－メチルフェニルチオ基等の無置換若しくは置換基を有するフェニルチオ基；　メチルスルフィニル基、エチルスルフィニル基等のＣ１～６アルキルスルフィニル基；　ハロメチルスルフィニル基、ハロエチルスルフィニル基等のＣ１～６ハロアルキルスルフィニル基；　フェニルスルフィニル基等の無置換若しくは置換基を有するフェニルスルフィニル基； 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 and ethylthio group; C1-6 haloalkylthio groups such as chloromethylthio group, trichloromethylthio group and trifluoromethylthio group; phenylthio , Phenylthio group having no substituent or a substituent such as 4-methylphenylthio group; C1-6 alkylsulfinyl group such as methylsulfinyl group and ethylsulfinyl group; C1-6 haloalkyl such as halomethylsulfinyl group and haloethylsulfinyl group A sulfinyl group; an unsubstituted or substituted phenylsulfinyl group such as a phenylsulfinyl group;
　－Ｎ＝ＣＨＯＨ、－Ｎ＝Ｃ（ＣＦ3）（ＯcＰｒ）　〔cＰｒはシクロプロピル基を表す。以下同じ〕、－Ｎ＝Ｃ〔ＮＥｔ2〕ＯＥｔ等の－Ｎ＝Ｃ（Ｒ10）ＯＲ11で表される基；　－Ｃ(＝Ｏ)Ｎ（Ｍｅ）Ｅｔ、－Ｃ（＝Ｏ）Ｎ（ＣＦ3）Ｐｈ、－Ｃ（＝Ｏ）Ｎ（cＰｒ）Ｅｔ等の－Ｃ（＝Ｏ）Ｎ（Ｒ10）（Ｒ11）で表される基；　－ＣＯ2Ｍｅ、－ＣＯ2ＣＣｌ3、－ＣＯ2Ｐｈ、－ＣＯ2（cＰｒ）等の－ＣＯ2Ｒ10で表される基；　－Ｃ（＝Ｓ）Ｎ（Ｍｅ）Ｅｔ、－Ｃ（＝Ｓ）Ｎ（ＣＦ3）Ｐｈ、－Ｃ（＝Ｓ）Ｎ（cＰｒ）Ｅｔ等の－Ｃ（＝Ｓ）Ｎ（Ｒ10）（Ｒ11）で表される基；　－ＳｉＭｅ3、－ＳｉＰｈ3、－Ｓｉ(Ｍｅ)2 ｔＢｕ　〔ｔＢｕはｔ－ブチル基を表す。以下同じ。〕等の－Ｓｉ（Ｒ12）（Ｒ13）（Ｒ14）で表される基；　フェニル基、４－メチルフェニル基、２－フルオロフェニル基、２，４－ジクロロフェニル基、２，４，６－トリメチルフェニル基等の無置換若しくは置換基を有するアリール基；　前記Ｒ3～Ｒ6の無置換若しくは置換基を有するヘテロ環基として例示したものと同様のもの；等が挙げられる。これらのうち、Ｃ１～６アルキル基、Ｃ１～６ハロアルキル基が好ましい。 —N═CHOH, —N═C (CF 3 ) (O c Pr) [ c Pr represents a cyclopropyl group. The same shall apply hereinafter), a group represented by —N═C (R 10 ) OR 11 such as —N═C [NEt 2 ] OEt; —C (═O) N (Me) Et, —C (═O) N Groups represented by —C (═O) N (R 10 ) (R 11 ), such as (CF 3 ) Ph, —C (═O) N ( c Pr) Et; —CO 2 Me, —CO 2 CCl 3 , a group represented by —CO 2 R 10 such as —CO 2 Ph, —CO 2 ( c Pr); —C (═S) N (Me) Et, —C (═S) N (CF 3 ) Groups represented by —C (═S) N (R 10 ) (R 11 ), such as Ph, —C (═S) N ( c Pr) Et; —SiMe 3 , —SiPh 3 , —Si (Me) 2 t Bu [ t Bu represents a t-butyl group. same as below. A group represented by —Si (R 12 ) (R 13 ) (R 14 ); and the like; phenyl group, 4-methylphenyl group, 2-fluorophenyl group, 2,4-dichlorophenyl group, 2,4,6 -An aryl group having an unsubstituted or substituted group such as a trimethylphenyl group; the same as those exemplified as the heterocyclic group having an unsubstituted or substituted group of R 3 to R 6 ; Of these, a C1-6 alkyl group and a C1-6 haloalkyl group are preferred.
　有機基の例示の中で、「無置換若しくは置換基を有する」の「置換基」は、前記Ｒ1の「置換基を有するＣ６～１０アリール基」等の置換基として例示したのと同様のものが挙げられる。
　また、有機基の例示の中で、Ｒ10～Ｒ14は、それぞれ独立して、水素原子；水酸基；チオール基；メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基等のＣ１～６アルキル基；トリフルオロメチル基、ペンタフルオロエチル基等のＣ１～６ハロアルキル基；ビニル基、イソプロペニル基、２－ブテニル基等のＣ２～６アルケニル基；アミノ基、メチルアミノ基、ジメチルアミノ基、フェニルアミノ基、４－メチルフェニルアミノ基、ジフェニルアミノ基、アセチルアミノ基、ベンゾイルアミノ基等の無置換若しくは置換基を有するアミノ基；シクロプロピル基、シクロペンチル基、シクロヘキシル基等のＣ３～８シクロアルキル基；フェニル基、２－クロロフェニル基、４－メチルフェニル基等の無置換若しくは置換基を有するフェニル基等を表す。 Among the examples of the organic group, the “substituent” of “unsubstituted or having a substituent” is the same as that exemplified as the substituent such as “the C6-10 aryl group having a substituent” of R 1 . Things.
In the examples of organic groups, 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.
　式（Ｉ）中、ｎは、０～４のいずれかの整数を表す。Ｚは、酸素原子または硫黄原子を表す。なお、式（Ｉ）中の、Ｚと窒素を含む環の部分は、２Ｈ－１，３－ベンゾオキサジン環または２Ｈ－１，３－ベンゾチアジン環である。 In the formula (I), n represents an integer of 0 to 4. Z represents an oxygen atom or a sulfur atom. In the formula (I), the ring portion containing Z and nitrogen is a 2H-1,3-benzoxazine ring or a 2H-1,3-benzothiazine ring.
（製造法）
（製造法１）
　本発明の含窒素複素環化合物またはその塩は、公知の方法により製造することができるが、例えば、下記のようにして製造することができる（特開平５－９７８２４号公報、Chem. Pharm. Bull. 1996, 44, 734-745、J.　Med. Chem. 2007, 50, 2647-2654などを参照。）。 (Production method)
(Production method 1)
The nitrogen-containing heterocyclic compound or a salt thereof of the present invention can be produced by a known method. For example, 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.).
Figure JPOXMLDOC01-appb-C000002
 　　（II）
　式(II)（式中、Ｘ、ｎ、Ｚ、Ｒ1、Ｒ2は前記式（Ｉ）における定義と同じである。Ｅは、ハロゲン原子または、エステル化された水酸基を示す。）で表わされる化合物と、
Figure JPOXMLDOC01-appb-C000002
 (II)
Expressed by the formula (II) (wherein X, n, Z, R 1 and R 2 are as defined in the formula (I). E represents a halogen atom or an esterified hydroxyl group). A compound
Figure JPOXMLDOC01-appb-C000003
 　　（III）
　式（III）（式中、Ｒ3～Ｒ6は前記式（Ｉ）における定義と同じである。Ｍは脱離基を示す）で表される化合物を反応させることにより製造することができる。
　式（II）中、Ｅで表されるハロゲン原子としては、好ましくは塩素原子、臭素原子またはヨウ素原子が挙げられ、Ｅで表されるエステル化された水酸基としては、好ましくはトリフルオロメタンスルホニル、メタンスルホニル、ｐ－トルエンスルホニルなどの反応性基でエステル化された水酸基が挙げられる。
　式（III）中、Ｍで表される脱離基としては、Ｌｉ、Ｎａ、Ｋ、Ｃａ（１／２）、ＭｇＣｌ、ＭｇＢｒ、ＭｇＩ、ＺｎＣｌ、ＳｎＣｌ、Ｓｎ（ｎＢｕ）3、ＣｒＣｌ2、ＣｕＣｌ、ＣｕＢｒ、ＮｉＣｌ、ＰｄＣｌ、Ｂ(ＯＨ)2などが挙げられる。
　反応は、不活性溶媒、たとえばテトラヒドロフラン、ジエチルエーテル、ジメトキシエタン、ヘキサン、トルエン、ベンゼン、メチレンクロリド、クロロホルム、１，２－ジクロロエタン、ＤＭＦ、ＤＭＳＯなど、あるいはこれらの混合溶媒の中で、約－５０℃～５０℃の温度範囲で行なうことができる。また、反応は、好ましくは、不活性ガス（たとえば、窒素、アルゴンなど）雰囲気下で行なうことができる。必要に応じて、テトラキス（トリフェニルホスフィン）パラジウム（Ｏ）、テトラキス（トリフェニルホスフィン）ニッケル（Ｏ）などを触媒として添加することにより、円滑に反応を進行させることができる。
Figure JPOXMLDOC01-appb-C000003
 (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).
In the formula (II), the halogen atom represented by E is preferably a chlorine atom, bromine atom or iodine atom, and 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.
In the formula (III), 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. It can be carried out in the temperature range of from 50 ° C to 50 ° C. In addition, the reaction can be preferably performed in an inert gas (for example, nitrogen, argon, etc.) atmosphere. If necessary, tetrakis (triphenylphosphine) palladium (O), tetrakis (triphenylphosphine) nickel (O), or the like can be added as a catalyst to allow the reaction to proceed smoothly.
　出発物質である式（II）で表される化合物は、市販の化合物であってもよいし、または実施例に示す方法により製造したものであってもよい。
　また、式（III）で表される化合物は、例えば、 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,
Figure JPOXMLDOC01-appb-C000004
 　　（III’）
　式（III’）（式中、Ｒ3～Ｒ6は前記定義と同じである。Ｗは水素またはハロゲン原子（Ｃｌ、ＢｒまたはＩ）を示す。）で表わされる化合物と前記脱離基Ｍの出発物質である化合物とを、前記の不活性溶媒中、約－７８℃～７０℃の温度範囲で、好ましくは、不活性ガス雰囲気下で反応させることによって得ることができる。式(III')で表される化合物から合成された式（III）で表される化合物は、精製してもよいが、反応系から単離することなく、そのまま式(II)の化合物と反応させて式（Ｉ）の化合物を製造することができる。
Figure JPOXMLDOC01-appb-C000004
 (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).
　さらに、式（Ｉ）で表わされる化合物中のＸ及びＲ1～Ｒ6は、例えば、以下の公知の方法により他の置換基に変換することができる。たとえば、水素原子をハロゲン化することによってハロゲン原子に置換し、または、ニトロ化することによってニトロ基に；そしてニトロ基の還元によってアミノ基に；アミノ基のアシル化あるいはスルホン化によってアシルアミノ基あるいはスルホニルアミノ基に導くこともできる。シアノ基は、たとえば水酸化ナトリウム水溶液／３０％過酸化水素水で処理することによってカルバモイル基に；ピリジン／トリエチルアミン中で硫化水素を使用することによってチオカルバモイル基に換えることもできる。また、シアノ基は、たとえば、水酸化ナトリウム水溶液中で加温して加水分解することによってカルボキシル基に；またはリン酸ナトリウムの存在下、水／酢酸／ピリジン中でラネーニッケルを使用することによってホルミル基に変換することもできる。ホルミル基は、ヴィッティヒ（Ｗｉｔｔｉｇ）反応によってビニル基に；ヒドロキシアミンとの反応によってヒドロキシイミノメチル基などに変換できる。水酸基は、アルキル化することによってアルコキシ基に；アシル化することによってアシルオキシ基に；アルキル水酸基は、硫酸／硝酸によってニトロキシアルキル基に変換することもできる。 Furthermore, 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.
（製造法２）
　式（Ｉ）のＺが酸素原子の場合には、下記の方法により製造することができる（特開平５－９７８２４号公報などを参照）。 (Production method 2)
When Z in the formula (I) is an oxygen atom, it can be produced by the following method (see JP-A-5-97824, etc.).
Figure JPOXMLDOC01-appb-C000005
 　　（IV）
　式（IV）（式中、Ｘ、ｎは前記定義と同じ。Ｍ’は脱離基、Ｙは水酸基の保護基を示す）で表される化合物と、
Figure JPOXMLDOC01-appb-C000005
 (IV)
A compound represented by formula (IV) (wherein X and n are as defined above, M ′ is a leaving group, and Y is a hydroxyl-protecting group);
Figure JPOXMLDOC01-appb-C000006
 　　（Ｖ）
　式（Ｖ）（式中、Ｒ3～Ｒ6は前記定義と同じ。Ｍ’は脱離基を示す）で表される化合物を反応させた後、公知の方法により脱保護して、
Figure JPOXMLDOC01-appb-C000006
 (V)
After reacting a compound represented by the formula (V) (wherein R 3 to R 6 are the same as defined above, M ′ represents a leaving group), the compound is deprotected by a known method,
Figure JPOXMLDOC01-appb-C000007
 　　（VI）
　式（VI）（式中、Ｘ、ｎ、Ｒ3～Ｒ6は前記定義と同じ）で表されるイミノ化合物を得、さらに酸触媒の存在下、
Figure JPOXMLDOC01-appb-C000007
 (VI)
An imino compound represented by the formula (VI) (wherein X, n and R 3 to R 6 are the same as defined above) was obtained, and in the presence of an acid catalyst,
Figure JPOXMLDOC01-appb-C000008
 　　（VII）
　式（VII）（式中、Ｒ1及びＲ2は式（Ｉ）における定義と同じ。Ｒはメチルあるいはエチル基を示す）で表される化合物と反応させることにより製造することができる。
Figure JPOXMLDOC01-appb-C000008
 (VII)
It can be produced by reacting with a compound represented by formula (VII) (wherein R 1 and R 2 are the same as defined in formula (I), R represents a methyl or ethyl group).
　式(VI)で表されるイミノ化合物は、 The imino compound represented by the formula (VI) is
Figure JPOXMLDOC01-appb-C000009
 　　（VIII）
　式（VIII）（式中、Ｘ、ｎ、Ｒ3～Ｒ6は前記定義と同じ）で表されるヒドロキシケトン化合物をアンモニアと反応させることにより得ることができる。
Figure JPOXMLDOC01-appb-C000009
 (VIII)
It can be obtained by reacting a hydroxyketone compound represented by the formula (VIII) (wherein X, n and R 3 to R 6 are as defined above) with ammonia.
　別法として、本発明の式（Ｉ）で表される含窒素複素環化合物は、酸触媒の存在下、式（VIII）で表されるヒドロキシケトン化合物と、式（VII)で表される化合物と、アンモニアを一挙に反応させることによっても製造することができる。 Alternatively, 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.
　式（IV）及び（Ｖ）中、Ｍ’で表される脱離基としては、好ましくはＬｉ、Ｎａ、Ｋ、Ｃａ（１／２）、ＭｇＣｌ、ＭｇＢｒ、ＭｇＩ、ＺｎＣｌ、ＳｎＣｌ、ＣｒＣｌ2等が挙げられる。式（IV）中、Ｙで表される水酸基の保護基としては、好ましくは公知のフェノール性水酸基の保護基、たとえば、メトキシジメチルメチル基、トリメチルシリル基、ｔ－ブチルジメチルシリル基等が挙げられる。 In the formulas (IV) and (V), 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. In the formula (IV), 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.
　式（IV）で表される化合物と式（Ｖ）で表される化合物の縮合反応は不活性溶媒、たとえばテトラヒドロフラン、ジエチルエーテル、ジメトキシエタン、ヘキサン、トルエン、ベンゼン、メチレンクロリド、ＤＭＦなど、あるいはこれらの混合溶媒の中で、約－７０℃～７０℃の温度範囲で行われる。本反応は、好ましくは、不活性ガス（たとえば、窒素、アルゴンなど）雰囲気下で行われる。
　その後の脱保護反応は、酸性加水分解またはテトラブチルアンモニウムフルオリド、フッ化カリウムなどのフッ素化塩試薬を用いて行われる。 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. In the mixed solvent in the temperature range of about -70 ° C to 70 ° C. 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.
　式（VIII）で表されるヒドロキシケトン化合物とアンモニアの反応は、不活性溶媒、たとえば、エタノール、ベンゼン、トルエン、クロロホルム、ジクロルメタン、１，２－ジクロルエタン、テトラヒドロフラン、ジエチルエーテルなど、あるいはこれらの混合溶媒の中で、約０℃～１００℃の温度範囲で行われる。通常、本反応は、式（VIII）で表されるヒドロキシケトン化合物に対して、１～１０倍モル量のアンモニアを含む溶媒中で、脱水剤（たとえば、モレキュラーシーブス、無水硫酸カルシウム、無水硫酸マグネシウムなど）の存在下、封管中で行われる。式(VI)で表されるイミノ化合物は、単離精製することなく次の反応に用いることもできる。 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.
　式（VI）で表されるイミノ化合物と式（VII）で表される化合物との閉環反応は、無溶媒あるいは不活性溶媒、たとえばベンゼン、トルエン、クロロホルム、ジクロロメタン、１，２－ジクロロエタン、ジエチルエーテルなど、あるいはこれらの混合溶媒中で酸触媒、脱水剤の存在下、室温から１００℃の温度範囲で行われる。
　酸触媒としては、塩酸、ｐ－トルエンスルホン酸、ベンゼンスルホン酸、カンファースルホン酸、塩化アンモニウム、酢酸アンモニウムなどを用いることができる。使用する酸触媒の量は、触媒の酸性度により適宜変えることが望ましく、式（VI）で表されるイミノ化合物に対して、１／１００～１０倍モル程度の範囲とすることが好ましい。
　脱水剤としては、たとえばモレキュラーシーブス、無水硫酸カルシウム、無水硫酸マグネシウムなどを使用することができる。 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.
As the 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).
As the dehydrating agent, for example, molecular sieves, anhydrous calcium sulfate, anhydrous magnesium sulfate and the like can be used.
　式（VIII）で表されるヒドロキシケトン化合物と、アンモニアと、式（VII）で表される化合物とのワン・ポット反応は、無溶媒あるいは不活性溶媒、たとえばベンゼン、トルエン、クロロホルム、ジクロルメタン、１,２－ジクロルエタン、ジエチルエーテルなど、あるいは、これらの混合溶媒中で、酸触媒、脱水剤の存在下、０℃～１００℃の温度範囲で行われる。通常、本反応は式（VIII）で表されるヒドロキシケトン化合物に対して、１～１０倍モル量のアンモニアを含む溶媒中で、封管中で行われる。
　酸触媒としては、上述の式（VI）で表されるイミノ化合物と式（VII）で表される化合物との閉環反応の説明において記載のものが使用でき、用いる酸触媒の量は式（VIII）で表されるヒドロキシケトン化合物に対して、１／２０～１０倍モル程度の範囲とすることが好ましい。
　また、脱水剤としては式（VI）で表されるイミノ化合物と式（VII）で表される化合物との閉環反応の説明において記載のものを用いることができる。 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. Usually, 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).
As 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). ) Is preferably in the range of about 1/20 to 10 times moles of the hydroxyketone compound represented by
As 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.
　式（Ｉ）で表される含窒素複素環化合物のうち、塩基性化合物は、酸を使用して塩に変換することができる。この反応に対する適当な酸は、好ましくは、農園芸学的に許容されうる塩を与える酸である。たとえば、塩酸、臭化水素酸、リン酸、硫酸、硝酸またはスルファミン酸などの無機酸、酢酸、酒石酸、クエン酸、フマール酸、マレイン酸、ｐ－トルエンスルホン酸、メタンスルホン酸またはグルタミン酸などの有機酸が挙げられる。
　式（Ｉ）で表される化合物の塩は、例えば、式（Ｉ）で表される化合物に、無機酸または有機酸を作用させることにより製造することができる。 Of the nitrogen-containing heterocyclic compounds represented by the formula (I), basic compounds can be converted into salts using an acid. Suitable acids for this reaction are preferably acids which give an agro-horticulturally acceptable salt. For example, 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 Examples include acids.
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).
　いずれの反応においても、反応終了後に、通常の後処理操作を行うことができ、次いで、生成物の精製が必要であれば、蒸留、再結晶またはカラムクロマトグラフィー等の公知慣用の精製手段により精製することができる。これにより、目的物を単離することができる。 In any reaction, after the completion of the reaction, 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.
　目的物の構造は、元素分析、ＮＭＲスペクトル、ＩＲスペクトル、マススペクトル等の公知の分析手段により同定、確認することができる。 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.
２）農園芸用殺菌剤
　本発明の農園芸用殺菌剤（以下、「本発明殺菌剤」ということがある。）は、式（Ｉ）で表される含窒素複素環化合物またはその塩（以下、「本発明化合物」ということがある。）の少なくとも１種を有効成分として含有するものである。 2) Agricultural and horticultural fungicide 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.
　有効成分量は、殺菌剤全体に対して、通常０．０１～９０重量％であり、好ましくは０．０５～８５重量％である。 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.
　本発明殺菌剤は、広範囲の種類の糸状菌、例えば、藻菌類（Oomycetes）、子のう（嚢）菌類（Ascomycetes）、不完全菌類（Deuteromycetes）、担子菌類（Basidiomycetes）に属する菌に対して優れた殺菌力を有する。 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.
　本発明殺菌剤は、花卉、芝、牧草を含む農園芸作物の栽培に際し発生する種々の病害の防除のために、種子処理、茎葉散布、土壌施用、水面施用等の方法で使用することができる。 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. .
　本発明殺菌剤は、以下に例示する病原菌の防除に使用することができる。
テンサイ　　褐斑病（Cercospora beticola）
　　　　　　黒根病（Aphanomyces cochlloides）
根腐病（Thanatephorus cucumeris）
葉腐病（Thanatephorus cucumeris）
ラッカセイ　褐斑病（Mycosphaerella arachidis）
　　　　　　黒渋病（Mycosphaerella berkeleyi）
キュウリ　　うどんこ病（Sphaerotheca fuliginea）
　　　　　　べと病（Pseudoperonospora cubensis）
つる枯病（Mycosphaerella melonis）
つる割病（Fusarium oxysporum）
　　　　　　菌核病（Sclerotinia sclerotiorum）
　　　　　　灰色かび病（Botrytis cinerea）
　　　　　　炭そ病（Colletotrichum orbiculare）
黒星病（Cladosporium cucumerinum）
　　　　　　褐斑病（Corynespora cassicola）
　　　　　　苗立枯病（Pythium debaryanam、Rhizoctonia solani Kuhn）
　　　　　　斑点細菌病（Pseudomonas syringae pv。Lecrymans）
トマト　　　灰色かび病（Botrytis cinerea）
　　　　　　葉かび病（Cladosporium fulvum）
疫病（Phytophthora infestans）
ナス　　　　灰色かび病（Botrytis cinerea）
　　　　　　黒枯病（Corynespora melongenae）
　　　　　　うどんこ病（Erysiphe cichoracearum）
　　　　　　すすかび病（Mycovellosiella nattrassii）
イチゴ　　　灰色かび病（Botrytis cinerea）
　　　　　　うどんこ病（Sohaerotheca humuli）
　　　　　　炭そ病（Colletotrichum acutatum、Colletotrichum fragariae）
疫病（Phytophthora cactorum）
タマネギ　　灰色腐敗病（Botrytis allii）
　　　　　　灰色かび病（Botrytis cinerea）
　　　　　　白斑葉枯病（Botrytis squamosa）
べと病（Peronospora destructor）
キャベツ　　根こぶ病（Plasmodiophora brassicae）
　　　　　　軟腐病（Erwinia carotovora）
べと病（Peronospora parasitica）
インゲン　　菌核病（Sclerotinia sclerotiorum）
　　　　　　灰色かび病（Botrytis cinerea）
りんご　　　うどんこ病（Podosphaera leucotricha）
　　　　　　黒星病（Venturia inaequalis）
　　　　　　モニリア病（Monilinia mali）
黒点病（Mycosphaerella pomi）
　　　　　　腐らん病（Valsa mali）
　　　　　　斑点落葉病（Alternaria mali）
　　　　　　赤星病（Gymnosporangium yamadae）
　　　　　　輪紋病（Botryosphaeria berengeriana）
　　　　　　炭そ病（Glomerella cingulata、Colletotrichum acutatum）
　　　　　　褐斑病（Diplocarpon mali）
すす点病（Zygophiala jamaicensis）
すす斑病（Gloeodes pomigena）
カキ　　　　うどんこ病（Phyllactinia kakicola）
　　　　　　炭そ病（Gloeosporium kaki）
　　　　　　角斑落葉病（Cercospora kaki） 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 (Corynespora cassicola)
Seedling blight (Pythium debaryanam, Rhizoctonia solani Kuhn)
Spotted bacterial disease (Pseudomonas syringae pv. Lecrymans)
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 (Erwinia carotovora)
Downy mildew (Peronospora parasitica)
Kidney sclerotia (Sclerotinia sclerotiorum)
Gray mold (Botrytis cinerea)
Apple powdery mildew (Podosphaera leucotricha)
Black star disease (Venturia inaequalis)
Monilinia mali
Sunspot disease (Mycosphaerella pomi)
Rot (Valsa mali)
Spotted leaf fall (Alternaria mali)
Red Star Disease (Gymnosporangium yamadae)
Ring-shaped disease (Botryosphaeria berengeriana)
Anthracnose (Glomerella cingulata, Colletotrichum acutatum)
Brown spot disease (Diplocarpon mali)
Soot spot disease (Zygophiala jamaicensis)
Soot spot (Gloeodes pomigena)
Oyster powdery mildew (Phyllactinia kakicola)
Anthracnose (Gloeosporium kaki)
Spotted leaf disease (Cercospora kaki)
モモ　　　　灰星病（Monilinia fructicola）
　　　　　　黒星病（Cladosporium carpophilum）
ホモプシス腐敗病（Phomopsis sp。）
オウトウ　　灰星病（Monilinia fructicola）
ブドウ　　　灰色かび病（Botrytis cinerea）
　　　　　　うどんこ病（Uncinula necator）
　　　　　　晩腐病（Glomerella cingulata、Colletotrichum acutatum）
べと病（Plasmopara viticola）
黒とう病（Elsinoe ampelina）
褐斑病（Pseudocercospora vitis）
黒腐病（Guignardia bidwellii）
ナシ　　　　黒星病（Venturia nashicola）
　　　　　　赤星病（Gymnosporangium asiaticum）
　　　　　　黒斑病（Alternaria kikuchiana）
輪紋病（Botryosphaeria berengeriana）
うどんこ病（Phyllactinia mali）
チャ　　　　輪斑病（Pestalotia theae）
　　　　　　炭そ病（Colletotrichum theae-sinensis）
カンキツ　　そうか病（Elsinoe fawcetti）
　　　　　　青かび病（Penicillium italicum）
　　　　　　緑かび病（Penicillium digitatum）
　　　　　　灰色かび病（Botrytis cinerea）
　　　　　　黒点病（Diaporthe shitri）
　　　　　　かいよう病（Xanthomonas campestris pv.Citri）
コムギ　　　うどんこ病（Erysiphe graminis f.sp.tritici）
　　　　　　赤かび病（Gibberella zeae）
　　　　　　赤さび病（Puccinia recondita）
　　　　　　褐色雪腐病（Pythium iwayamai）
　　　　　　紅色雪腐病（Monographella nivalis）
　　　　　　眼紋病（Pseudocercosporella herpotrichoides）
　　　　　　葉枯病（Septoria tritici）
　　　　　　ふ枯病（Leptosphaeria nodorum）
　　　　　　雪腐小粒菌核病（Typhula incarnata）
　　　　　　雪腐大粒菌核病（Myriosclerotinia borealis）
　　　　　　立枯病（Gaeumanomyces graminis） Peach (Assassin Disease) (Monilinia fructicola)
Black star disease (Cladosporium carpophilum)
Homopsis spoilage (Phomopsis sp.)
Sweet cherry blight (Monilinia fructicola)
Grapes Gray mold (Botrytis cinerea)
Powdery mildew (Uncinula necator)
Late rot (Glomerella cingulata, Colletotrichum acutatum)
Downy mildew (Plasmopara viticola)
Black depression (Elsinoe ampelina)
Brown spot disease (Pseudocercospora vitis)
Black rot (Guignardia bidwellii)
Pear black star disease (Venturia nashicola)
Red Star Disease (Gymnosporangium asiaticum)
Black spot disease (Alternaria kikuchiana)
Ring-shaped disease (Botryosphaeria berengeriana)
Powdery mildew (Phyllactinia mali)
Tea ring spot disease (Pestalotia theae)
Anthracnose (Colletotrichum theae-sinensis)
Citrus common scab (Elsinoe fawcetti)
Blue mold (Penicillium italicum)
Green mold (Penicillium digitatum)
Gray mold (Botrytis cinerea)
Black spot disease (Diaporthe shitri)
Sickness (Xanthomonas campestris pv.Citri)
Wheat powdery mildew (Erysiphe graminis f.sp.tritici)
Red mold (Gibberella zeae)
Red rust (Puccinia recondita)
Brown snow rot (Pythium iwayamai)
Red snow rot (Monographella nivalis)
Eye disease (Pseudocercosporella herpotrichoides)
Leaf blight (Septoria tritici)
Dry blight (Leptosphaeria nodorum)
Snowy rot granule nuclear disease (Typhula incarnata)
Myriosclerotinia borealis
Blight disease (Gaeumanomyces graminis)
オオムギ　　斑葉病（Pyrenophora graminea）
　　　　　　雲形病（Rhynchosporium secalis）
　　　　　　裸黒穂病（Ustilago tritici、U.nuda）
イネ　　　　いもち病（Pyricularia oryzae）
　　　　　　紋枯病（Rhizoctonia solani）
　　　　　　馬鹿苗病（Gibberella fujikuroi）
　　　　　　ごま葉枯病（Cochliobolus niyabeanus）
　　　　　　苗立枯病（Pythium graminicolum）
白葉枯病（Xanthomonas oryzae）
苗立枯細菌病（Burkholderia plantarii）
褐条病（Acidovorax avenae）
もみ枯細菌病（Burkholderia glumae）
タバコ　　　菌核病（Sclerotinia sclerotiorum）
　　　　　　うどんこ病（Erysiphe cichoracearum）
チューリップ灰色かび病（Botrytis cinerea）
ベントグラス雪腐大粒菌核病（Sclerotinia borealis）
　　　　　　赤焼病（Pythium aphanidermatum）
オーチャードグラス　うどんこ病（Erysiphe graminis）
ダイズ　　　紫斑病（Cercospora kikuchii）
　　　　　　べと病（Peronospora Manshurica）
　　　　　　茎疫病（Phytophthora sojae）
ジャガイモ・トマト疫病（Phytophthora infestans） 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 (Sclerotinia borealis)
Red fire (Pythium aphanidermatum)
Orchardgrass powdery mildew (Erysiphe graminis)
Soybean Purpura (Cercospora kikuchii)
Downy mildew (Peronospora Manshurica)
Phytophthora sojae
Potato and tomato plague (Phytophthora infestans)
　また、従来のベンズイミダゾール系殺菌剤やジカルボキシイミド系殺菌剤等に対して、種々の病原菌が耐性を持つようになり、その薬効不足が問題になっている。本発明殺菌剤は、従来の殺菌剤に対する感受性菌のみならず、従来の殺菌剤に対して耐性を持つようになった菌に対しても優れた殺菌効果を有する。 Also, various pathogens have become resistant to conventional benzimidazole fungicides, dicarboximide fungicides, and the like, and there is a problem of insufficient medicinal effects. 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.
　例えば、灰色かび病菌（Botrytis cinerea）やテンサイ褐斑病菌（Cercospora beticola）、リンゴ黒星病菌（Venturia inaequalis）、ナシ黒星病菌（Venturia nashicola）は、チオファネートメチル、ベノミル、カルベンダジム等のベンズイミダゾール系殺菌剤に耐性を示すが、本発明殺菌剤はこれら耐性菌に対して有効な殺菌作用をする。 For example, 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.
　さらに、灰色かび病菌（Botrytis cinerea）は、ジカルボキシイミド系殺菌剤（例えば、ビンクロゾリン、プロシミドン、イプロジオン）に耐性を示すが、本発明殺菌剤は有効な殺菌作用をする。 Furthermore, although 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.
　本発明殺菌剤の適用が好ましい病害としては、テンサイの褐斑病、コムギのうどんこ病、イネのいもち病、リンゴ黒星病、キュウリの灰色かび病、ラッカセイの褐斑病等が挙げられる。適用がより好ましい病害としては、各種の果樹病害が挙げられる。 Favorable 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. Examples of diseases more preferably applied include various fruit tree diseases.
　本発明殺菌剤は薬害が少なく、魚類や温血動物への毒性が低く、安全性の高い薬剤である。
　本発明殺菌剤は、他成分を加えず本発明化合物をそのまま使用するものであってもよいし、添加剤や担体を用いて、水和剤、粒剤、粉剤、乳剤、水溶剤、懸濁剤、顆粒水和剤等の一般の農薬のとり得る形態にして使用するものであってもよい。 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.
　農薬製剤中に添加することのできる添加剤及び担体は、目的とする剤型に応じて適宜選択できる。例えば、固型剤を目的とする場合は、大豆粉、小麦粉等の植物性粉末、珪藻土、燐灰石、石こう、タルク、ベントナイト、パイロフィライト、クレー等の鉱物性微粉末、安息香酸ソーダ、尿素、芒硝等の有機及び無機化合物が使用される。 Additives and carriers that can be added to the agricultural chemical formulation can be appropriately selected according to the intended dosage form. For example, when a solid agent is intended, 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.
　また、液体の剤型を目的とする場合は、ケロシン、キシレン及び石油系の芳香族炭化水素、シクロヘキサン、シクロヘキサノン、ジメチルホルムアミド、ジメチルスルホキシド、アルコール、アセトン、トリクロルエチレン、メチルイソブチルケトン、鉱物油、植物油、水等を溶剤として使用することができる。 For liquid dosage forms, 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.
　さらに、これらの製剤において均一かつ安定な形態をとるために、必要に応じ界面活性剤を添加することもできる。
　用いる界面活性剤としては特に限定はないが、例えば、ポリオキシエチレンが付加したアルキルフェニルエーテル、ポリオキシエチレンが付加したアルキルエーテル、ポリオキシエチレンが付加した高級脂肪酸エステル、ポリオキシエチレンが付加したソルビタン高級脂肪酸エステル、ポリオキシエチレンが付加したトリスチリルフェニルエーテル等の非イオン性界面活性剤、ポリオキシエチレンが付加したアルキルフェニルエーテルの硫酸エステル塩、アルキルベンゼンスルホン酸塩、高級アルコールの硫酸エステル塩、アルキルナフタレンスルホン酸塩、ポリカルボン酸塩、リグニンスルホン酸塩、アルキルナフタレンスルホン酸塩のホルムアルデヒド縮合物、イソブチレン－無水マレイン酸共重合体等が挙げられる。 Furthermore, in order to take a uniform and stable form in these preparations, a surfactant may be added as necessary.
The surfactant to be used is not particularly limited. For example, 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 Examples thereof include naphthalene sulfonate, polycarboxylate, lignin sulfonate, formaldehyde condensate of alkyl naphthalene sulfonate, and isobutylene-maleic anhydride copolymer.
　このようにして得られた水和剤、乳剤、フロアブル、水溶剤、顆粒水和剤は水で所定の濃度に希釈して溶解液、懸濁液あるいは乳濁液として、粉剤・粒剤はそのまま植物に散布する方法で使用される。 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.
　製剤化された本発明殺菌剤は、そのままで、或いは水等で希釈して、植物体、種子、水面または土壌に施用される。施用量は、気象条件、製剤形態、施用磁気、施用方法、施用場所、防除対象病害、対象作物等により異なるが、通常１ヘクタール当たり有効成分化合物量にして１～１，０００ｇ、好ましくは１０～１００ｇである。 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.
　水和剤、乳剤、懸濁剤、水溶剤、顆粒水和剤等を水で希釈して施用する場合、その施用濃度は１～１０００ｐｐｍ、好ましくは１０～２５０ｐｐｍであり、粒剤、粉剤等の場合は、希釈することなくそのまま施用することもできる。 When a wettable powder, emulsion, suspension, aqueous solvent, granular wettable powder, etc. are diluted with water and applied, 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.
　本発明殺菌剤には、本発明化合物のほかに、各種の殺菌剤や殺虫・殺ダニ剤等の１種または２種以上を混合することもできる。 In addition to the compounds of the present invention, one or two or more of various fungicides, insecticides, acaricides and the like can be mixed with the fungicides of the present invention.
　本発明化合物と混合して使用できる殺菌剤、殺虫・殺ダニ剤、殺線虫剤、殺土壌害虫剤、植物生長調節剤の代表例を以下に示す。 Representative examples of 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.
殺菌剤：
１）ベンゾイミダゾール系：ベノミル、カルベンダジム、フベリダゾール、チアベンダゾール、チオファネート メチル等；
２）ジカルボキシイミド系：クロゾリネート、イプロジオン、プロシミドン、ビンクロゾリン等；
３）ＤＭＩ－殺菌剤系：イマザリル、オキスポコナゾール、ペフラゾエート、プロクロラズ、トリフルミゾール、トリホリン、ピリフェノックス、フェナリモル、ヌアリモル、アザコナゾール、ビテルタノール、ブロムコナゾール、シプロコナゾール、ジフェノコナゾール、ジニコナゾール、エポキシコナゾール、フェンブコナゾール、フルキンコナゾール、フルシラゾール、フルトリアホル、ヘキサコナゾール、イミベンコナゾール、イプコナゾール、メトコナゾール、ミクロブタニル、ペンコナゾール、プロピコナゾール、プロチオコナゾール、シメコナゾール、テブコナゾール、テトラコナゾール、トリアジメホン、トリアジメノール、トリチコナゾール、エタコナゾール、ファーコナゾールシス等；
４）フェニルアミド系：ベナラキシル、フララキシル、メタラキシル、メタラキシル－M、オキサジキシル、オフラセ等；
５）アミン系：アルジモルフ、ドデモルフ、フェンプロピモルフ、トリデモルフ、フェンプロピジン、ピペラリン、スピロキサミン等；
６）ホスホロチオレート系：ＥＤＤＰ、イプロベンホス、ピラゾホス等；
７）ジチオラン系：イソプロチオラン等；
８）カルボキサミド：ベノダニル、ボスカリド、カルボキシン、フェンフラン、フルトラニル、フラメトピル、メプロニル、オキシカルボキシン、ペンチオピラド、チフルザミド等；
９）ヒドロキシ-(2-アミノ) ピリミジン系：ブピリメート、ジメチリモル、エチリモル等；
１０）ＡＰ殺菌剤(アニリノピリミジン)系：シプロジニル、メパニピリム、ピリメタニル等；
１１）N-フェニルカーバメート系：ジエトフェンカルブ等；
１２）QoI-殺菌剤 (Qo阻害剤)系：アゾキシストロビン、ピコキシストロビン、ピラクロストロビン、クレソキシム-メチル、トリフロキシストロビン、ジモキシストロビン、メトミノストロビン、オリザストロビン、ファモキサドン、フルオキサストロビン、フェンアミドン、メトミノフェン等；
１３）PP殺菌剤 (フェニルピロール)系：フェンピコニル、フルジオキソニル等；
１４）キノリン系：キノキシフェン等；
１５）AH殺菌剤 (芳香族炭化水素）系：ビフェニル、クロロネブ、ジクロラン、キントゼン、テクナゼン、トルクトフォス-メチル等；
１６）MBI-R系：フサライド、ピロキロン、トリシクラゾール等；
１７）MBI-D系：カルプロパミド、ジクロシメット、フェノキサニル等；
１８）SBI剤：フェンヘキサミド、ピリブチカルブ、タービナフィン等；
１９）フェニルウレア：ペンシクロン等；
２０）QiI-殺菌剤 (Ｑｉ阻害剤)：シアゾファミド等；
２１）ベンズアミド系：ゾキサミド等；
２２）エノピランウロン系：ブラストサイジン、ミルディオマイシン等；
２３）へキソピラノシル系：カスガマイシン等；
２４）グルコピラノシル系：ストレプトマイシン、バリダマイシン等；
２５）シアノアセトアミド系：シモキサニル等；
２６）カーバメート系：イドカルブ、プロパモカルブ、プロチオカルブ、ポリカーバメート等；
２７）脱共役剤：ビナパクリル、ジノカップ、フェリムゾン、フルアジナム等；
２８）有機スズ化合物：酢酸トリフェニルスズ、塩化トリフェニルスズ、水酸化トリフェニルスズ等；
２９）リン酸エステル：亜リン酸、トルクロホスメチル、ホセチル等；
３０）フタルアミド酸系：テクロフタラム等；
３１）ベンゾトリアジン系：トリアゾキシド等；
３２）ベンゼンスルフォナミド系：フルスルファミド等；
３３）ピリダジノン：ジクロメジン等；
３４）CAA 殺菌剤 (カルボン酸アミド)系：ジメトモルフ、フルモルフ、ベンチアバリカルブ、イプロバリカルブ、マンジプロパミド等；
３５）テトラサイクリン：オキシテトラサイクリン等；
３６）チオカーバメート系：メタスルホカルブ等；
３７）その他の化合物：エトリジアゾール、ポリオキシン、オキソリニック酸、ヒドロキシイソキサゾール、オクチノリン、シルチオファム、ジフルメトリム、アシベンゾラルＳメチル、プロベナゾール、チアジニル、エタボキサム、シフルフェナミド、プロキナジド、メトラフェノン、フルオピコリド、水酸化第二銅、有機銅、硫黄、ファーバム、マンゼブ、マンネブ、メチラム、プロピネブ、チウラム、ジネブ、ジラム、キャプタン、カプタホール、フォルペット、クロロタロニル、ジクロフルアニド、トリルフルアニド、ドジン、グアザチン、イミノクタジン酢酸塩、イミノクタジンドデシルベンゼンスルホン酸塩、アニラジン、ジチアノン、クロロピクリン、ダゾメット、メタムナトリウム塩、キノメチオネート、シプロフラム、シルチオファム、アグロバクテリウム、フルオルイミド)等； 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, propiconazole, prothioconazole, cimeconazole, tebuconazole, tetraconazole, triazimephone, tri Azimenol, triticonazole, etaconazole, farconazole cis and the like;
4) Phenylamide series: Benalaxyl, furaxyl, metalaxyl, metalaxyl-M, oxadixyl, oflase, etc .;
5) Amine-based: aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidine, piperalin, spiroxamine, etc .;
6) Phosphorothiolate system: EDDP, iprobenphos, pyrazophos, etc .;
7) Dithiolane type: isoprothiolane and the like;
8) Carboxamide: benodanyl, boscalid, carboxin, fenfuran, flutolanil, furamethopyl, mepronil, oxycarboxin, pentiopyrad, tifluzamide, etc .;
9) Hydroxy- (2-amino) pyrimidine series: bupyrimeto, dimethylolmol, ethylimol, etc .;
10) AP fungicide (anilinopyrimidine) type: cyprodinil, mepanipyrim, pyrimethanil, etc .;
11) N-phenyl carbamate type: dietofencarb and the like;
12) QoI-bactericidal (Qo inhibitor) system: azoxystrobin, picoxystrobin, pyraclostrobin, cresoxime-methyl, trifloxystrobin, dimoxystrobin, metminostrobin, orizastrobin, famoxadone , Fluoxastrobin, phenamidon, metminophen, etc .;
13) PP fungicide (phenylpyrrole) type: fenpiconyl, fludioxonil, etc .;
14) Quinoline series: quinoxyphene, etc .;
15) AH fungicide (aromatic hydrocarbon) series: biphenyl, chloronebu, dichlorane, kintozen, technazen, tortofos-methyl, etc .;
16) MBI-R series: fusaride, pyrokilone, tricyclazole, etc .;
17) MBI-D system: carpropamide, diclocimet, phenoxanyl, etc .;
18) SBI agent: Fenhexamide, Pyributicarb, Turbinafine, etc .;
19) Phenylurea: pencyclon, etc .;
20) QiI-bactericide (Qi inhibitor): cyazofamide and the like;
21) benzamide type: zoxamide and the like;
22) Enopyranuron series: blastcidin, mildiomycin, etc .;
23) Hexopyranosyl system: Kasugamycin and the like;
24) Glucopyranosyl: streptomycin, validamycin and the like;
25) Cyanoacetamide series: Simoxanyl and the like;
26) Carbamate series: idcarb, propamocarb, prothiocarb, polycarbamate, etc .;
27) Uncouplers: Vinapacryl, Zinocup, Ferimzone, Fluazinam, etc .;
28) Organotin compounds: triphenyltin acetate, triphenyltin chloride, triphenyltin hydroxide, etc .;
29) Phosphate ester: phosphorous acid, tolcrofosmethyl, fosetyl and the like;
30) Phthalamic acid type: Teclophthalam, etc .;
31) Benzotriazine series: triazoxide and the like;
32) Benzenesulfonamide series: fullsulfamide and the like;
33) Pyridazinone: Dichromedin and the like;
34) CAA disinfectant (carboxylic amide) type: dimethomorph, fulmorph, benchavaricarb, iprovaricarb, mandipropamide, etc .;
35) Tetracycline: oxytetracycline and the like;
36) Thiocarbamate type: metasulfocarb, etc.
37) Other compounds: etridiazole, polyoxin, oxolinic acid, hydroxyisoxazole, octinoline, silthiofam, diflumetrim, acibenzoral S methyl, probenazole, thiazinyl, ethaboxam, cyflufenamide, proquinazide, metolaphenone, fluopicolide, cupric hydroxide, organic copper , Sulfur, Farbum, Manzeb, Mannebu, Methylum, Propineb, Thiuram, Dinebu, Diram, Captan, Captahol, Folpet, Chlorothalonil, Diclofluuride, Tolylfluanid, Dodine, Guazatine, Iminocazine Acetate, Iminocazine Dodecylbenzenesulfonate , Anilazine, dithianone, chloropicrin, dazomet, metham sodium salt, quinomethionate, ciprofram, Chiofamu, Agrobacterium, Furuoruimido) and the like;
殺虫・殺ダニ剤、殺線虫剤、殺土壌害虫剤：
１）有機（チオ）ホスフェート系：アセフェート、アザメチホス、アジンホスメチル、クロルピリホス、クロルピリホスメチル、クロルフェンビンホス、ダイアジノン、ジクロルボス、ジクロトホス、ジメトエート、ジスルホトン、エチオン、ＥＰＮ、フェナミホス、フェニトロチオン、フェンチオン、イソキサチオン、マラソン、メタミドホス、メチダチオン、メチルパラチオン、メビンホス、モノクロトホス、オキシデメトンメチル、パラオキソン、パラチオン、フェントエート、ホサロン、ホスメット、ホスファミドン、ホレート、ホキシム、ピリミホスメチル、プロフェノホス、プロチオホス、スルプロホス、テトラクロルビンホス、テルブホス、トリアゾホス、トリクロルホン、
ホスチアゼート、ホスホカルブ、カズサホス、ジスルホトン、デメトン-Ｓ -メチル、ＢＲＰ、ＣＹＡＰ、エトプロホス、キナルホス、ジメチルビンホス、バミドチオン、ピラクロホス；
２）カルバメート系：アラニカルブ、アルジカルブ、ベンダイオカルブ、ベンフラカルブ、カルバリル、カルボフラン、カルボスルファン、フェノキシカルブ、フェノチオカルブ、メチオカルブ、メソミル、オキサミル、ピリミカルブ、プロポキスル、チオジカルブ、トリアザメート、
エチオフェンカルブ、フェノブカルブ、ＭＩＰＣ、ＭＰＭＣ、ＭＴＭＣ、ピリダフェンチオン、フラチオカルブ、ＸＭＣ；
３）ピレトロイド系：アレスリン、ビフェントリン、シフルトリン、シハロトリン、シフェノトリン、シペルメトリン、アルファシペルメトリン、ベータシペルメトリン、ゼータシペルメトリン、デルタメトリン、エスフェンバレレート、エトフェンプロックス、フェンプロパトリン、フェンバレレート、イミプロトリン、ラムダシハロトリン、ペルメトリン、プラレトリン、ピレトリンI及びII、レスメトリン、シラフルオフェン、タウフルバリネート、テフルトリン、テトラメトリン、トラロメトリン、トランスフルトリン、プロフルトリン、ジメフルトリン、
アクリナトリン、シクロプロトリン、ハルフェンプロックス、フルシトリネート；
４）成長調節物質：
a)キチン合成阻害剤：クロルフルアズロン、ジフルベンズロン、フルシクロクスロン、フルフェノクスロン、ヘキサフルムロン、ルフェヌロン、ノバルロン、テフルベンズロン、トリフルムロン；
ビストリフルロン、ノビフルムロン、ブプロフェジン、ジオフェノラン、ヘキシチアゾクス、エトキサゾール、クロフェンタジン；
b)エクジソンアンタゴニスト：ハロフェノジド、メトキシフェノジド、テブフェノジド、アザジラクチン；
クロマフェノジド；
c)幼若ホルモン様物質： ピリプロキシフェン、メトプレン、フェノキシカルブ；
d)脂質生合成阻害剤：スピロジクロフェン、スピロメシフェン、スピロテトラマト；
５）ニコチン受容体アゴニスト／アンタゴニスト化合物：アセタミプリド、クロチアニジン、ジノテフラン、イミダクロプリド、ニテンピラム、チアクロプリド、チアメトキサム；
６）GABAアンタゴニスト化合物：アセトプロール、エンドスルファン、エチピロール、フィプロニル、バニリプロール、ピラフルプロール、ピリプロール；
７）大環状ラクトン殺虫剤：アバメクチン、エマメクチン、ミルベメクチン、レピメクチン、スピノサド；
イベルメクチン；
８）METI I化合物：フェナザキン、ピリダベン、テブフェンピラド、トルフェンピラド、フルフェネリム；
９）METI II及びIII化合物：アセキノシル、フルアシプリム、ヒドラメチルノン；
１０）脱共役剤化合物：クロルフェナピル；
１１）酸化的リン酸化阻害剤化合物：シヘキサチン、ジアフェンチウロン、フェンブタチンオキシド、プロパルギット；
１２）脱皮かく乱化合物：シロマジン；
１３）混合機能オキシダーゼ阻害剤化合物：ピペロニルブトキシド；
１４）ナトリウムチャネル遮断剤化合物：インドキサカルブ、メタフルミゾン；
１５）微生物農薬：ＢＴ剤、昆虫病原ウイルス剤、昆虫病原糸状菌剤、線虫病原糸状菌剤；
１６）その他のもの：ベンクロチアズ、ビフェナゼート、カルタップ、フロニカミド、ピリダリル、ピメトロジン、硫黄、チオシクラム、フルベンジアミド、シエノピラフェン、フルピラゾホス、シフルメトフェン、アミドフルメット、ベンスルタップ、ジコホル、テトラジホン、フェンピロキシメート、アミトラズ、クロルジメホルム、トリアザメイト、ピメトロジン、ピリミジフェン、１,３－ジクロロプロペン、クロフェンテジン、フルアクリピリム、ロテノン、ＤＣＩＰ、フェニソブロモレート、ベンゾメート、メタアルデヒド、クロラントラニリプロールスピネトラム、ピリフルキナゾン； 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, triazophos, trichlorphone,
Phosphiazate, phosphocarb, kazusafos, disulfoton, demeton-S-methyl, BRP, CYAP, etoprophos, quinalphos, dimethylvinphos, bamidthione, pyracrophos;
2) Carbamate series: alanic carb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, phenoxycarb, phenothiocarb, methiocarb, mesomil, oxamyl, pirimicarb, propoxyl, thiodicarb, triazamate,
Etiophencarb, fenobucarb, MIPC, MPMC, MTMC, pyridafenthion, furthiocarb, XMC;
3) Pyrethroid: Allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha cypermethrin, beta cypermethrin, zetacypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropatoline, fenvalerate, imiprotorin, Lambda cihalothrin, permethrin, praretrin, pyrethrin I and II, resmethrin, silafluophene, taufulvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin,
Acrinatrin, cycloprotorin, halfenprox, flucitrinate;
4) Growth regulator:
a) Chitin synthesis inhibitors: chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, nobarulone, teflubenzuron, triflumuron;
Bistrifluron, nobiflumuron, buprofezin, diophenolane, hexythiazox, etoxazole, clofentadine;
b) ecdysone antagonists: halofenozide, methoxyphenozide, tebufenozide, azadirachtin;
Chromafenozide;
c) Juvenile hormone-like substances: pyriproxyfen, metoprene, phenoxycarb;
d) Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
5) Nicotine receptor agonist / antagonist compounds: acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam;
6) GABA antagonist compounds: acetoprole, endosulfan, ethipyrrole, fipronil, vaniliprole, pyrafluprolol, pyriprol;
7) Macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad;
Ivermectin;
8) METI I compounds: phenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
9) METI II and III compounds: acequinosyl, fluacyprim, hydramethylnon;
10) Uncoupler compound: chlorfenapyr;
11) Oxidative phosphorylation inhibitor compounds: cyhexatin, diafenthiuron, phenbutatin oxide, propargite;
12) Molting compound: cyromazine;
13) Mixed function oxidase inhibitor compound: piperonyl butoxide;
14) Sodium channel blocker compounds: indoxacarb, metaflumizone;
15) Microbial pesticides: BT agents, entomopathogenic virus agents, entomopathogenic fungi agents, nematode pathogenic fungi agents;
16) Others: Benclothiaz, Bifenazate, Cartap, Flonicamid, Pyridalyl, Pymetrozine, Sulfur, Thiocyclam, Flubendiamide, Sienopyrafen, Flupirazophos, Cyflumethofene, Amidoflumet, Bensultap, Dicophor, Tetradiphone, Fenpyroximate, Amitraz, Chlordimetform, Triza Pyrimidifen, 1,3-dichloropropene, clofentezin, fluacrylpyrim, rotenone, DCIP, phenisobromolate, benzomate, metaldehyde, chlorantraniliprole spinetoram, pyrifluquinazone;
植物生長調節剤：
アブシジン酸、インドール酪酸、ウニコナゾール、エチクロゼート、エテホン、クロキシホナック、クロルメコート、クロレラ抽出液、過酸化カルシウム、シアナミド、ジクロルプロップ、ジベレリン、ダミノジッド、デシルアルコール、トリネキサパックエチル、メピコートクロリド、パクロブトラゾール、パラフィンワックス、ピペロニルブトキシド、ピラフルフェンエチル、フルルプリミドール、プロヒドロジャスモン、プロヘキサジオンカルシウム塩、ベンジルアミノプリン、ペンディメタリン、ホルクロルフェニュロン、マレイン酸ヒドラジドカリウム、１－ナフチルアセトアミド、4-ＣＰＡ、ＭＣＰＢ、コリン、硫酸オキシキノリン、エチクロゼート、ブトルアリン、1-メチルシクロプロペン、アビグリシン塩酸塩； 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;
　以下、実施例を示して、本発明をさらに詳細に説明する。ただし、本発明は、実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.
実施例１　〔2-Methyl-2-phenyl-4-(3-quinolyl)-2H-1,3-benzoxazine（化合物１－２）の製造〕 Example 1 [Production of 2-Methyl-2-phenyl-4- (3-quinolyl) -2H-1,3-benzoxazine (Compound 1-2)]
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　2-Methyl-2-phenyl-2,3-dihydro-4H-1,3-benzoxazin-4-one　0.7g（2.93mmol）を塩化メチレン10mLに溶解し、－10℃に冷却した。トリフルオロメタンスルホン酸無水物1.24g（4.39mmol）を加え、－10℃で１時間撹拌した。次に、2,6‐ルチジン0.47g（4.39mmol）を加え、－10℃で２時間撹拌した。
　反応液を氷水に注ぎ、次いでクロロホルムで抽出を行った。有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥し、次いで減圧下で溶媒を留去した。
　残渣をトルエンに溶解した。
　文献（Angew. Chem. Int. Ed., 2008, 47, 928-931）に報告された方法に従って３－キノリンボロン酸と1,1,1-Tris(hydroxymethyl)ethaneとからトリオール塩を製造した。該トリオール塩1.04g（3.5mmol）、及びPd(PPh3)4 0.68g（0.59mmol）を前記トルエン溶液に加え、反応器内を窒素置換し、１４時間加熱還流した。
　反応溶液を室温に冷却し、氷水に注ぎ、次いで酢酸エチルで抽出した。有機層を飽和食塩水で洗浄し、減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（展開溶媒；ｎ－ヘキサン：酢酸エチル＝４：１）で精製し、目的物　0.26g（収率25％）を得た。 0.7 g (2.93 mmol) of 2-Methyl-2-phenyl-2,3-dihydro-4H-1,3-benzoxazin-4-one was dissolved in 10 mL of methylene chloride and cooled to −10 ° C. 1.24 g (4.39 mmol) of trifluoromethanesulfonic anhydride was added and stirred at −10 ° C. for 1 hour. Next, 0.47 g (4.39 mmol) of 2,6-lutidine was added and stirred at −10 ° C. for 2 hours.
The reaction solution was poured into ice water and then extracted with chloroform. The organic layer was washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure.
The residue was dissolved in toluene.
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.
The 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. The obtained residue was purified by silica gel column chromatography (developing solvent; n-hexane: ethyl acetate = 4: 1) to obtain 0.26 g of the desired product (yield 25%).
実施例２　〔2-(4-Fluorobenzyl)-2-methyl-4-(3-quinolyl)-2H-1,3-benzothiazine（化合物２－６）の製造〕 Example 2 [Production of 2- (4-Fluorobenzyl) -2-methyl-4- (3-quinolyl) -2H-1,3-benzothiazine (Compound 2-6)]
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　2-(4-Fluorobenzyl)-2-methyl-2H-1,3-benzothiazin-4-one　0.30g（1.04mmol）をオキシ塩化リン5mlに溶解し、五塩化リン0.228g（1.10mmol）を加え６時間加熱還流した。反応液からオキシ塩化リンを減圧留去した。残渣を酢酸エチルに溶解し、重曹溶液、及び飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥させた。濾過後、減圧下で溶媒を留去した。青黒色油状物として4-Chloro-2-(4-fluorobenzyl)-2-methyl-2H-1,3-benzothiazineを得た。
　3－キノリンボロン酸0.216g（1.25mmol）及び２Ｍ炭酸セシウム水溶液1.5mL（3.00mmol）を含むジメチルホルムアミド溶液10mLを容器に入れ窒素置換した。この溶液にPd(PPh3)4　0.24g（0.208mmol）及び上記で得られた4-Chloro-2-(4-fluorobenzyl)-2-methyl-2H-1,3-benzothiazine全量を加え、80℃で18時間攪拌した。次いで、反応溶液を室温まで冷却し、酢酸エチル100mLと水100mLとからなる液に注加し、水層を酢酸エチル100mLで抽出した。有機層をブライン60mLで洗浄し、硫酸マグネシウムで乾燥させた。濾過後、減圧下で溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（１回目の溶媒〔ヘキサン：酢酸エチル＝４：１〕、２回目の溶媒〔ヘキサン：アセトン＝４：１〕）で精製して目的物0.11g（26.4％）を得た。 Dissolve 2- (4-Fluorobenzyl) -2-methyl-2H-1,3-benzothiazin-4-one 0.30g (1.04mmol) in 5ml phosphorus oxychloride, add 0.228g (1.10mmol) phosphorus pentachloride 6 Heated to reflux for hours. From the reaction solution, phosphorus oxychloride was distilled off under reduced pressure. The residue was dissolved in ethyl acetate, washed successively with sodium bicarbonate solution and saturated brine, and dried over magnesium sulfate. After filtration, 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. Next, the 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. The obtained residue was purified by silica gel column chromatography (first solvent [hexane: ethyl acetate = 4: 1], second solvent [hexane: acetone = 4: 1]) to obtain 0.11 g (26.4%) of the desired product. )
　上記実施例１または２と同様にして製造される本発明の式（Ｉ）で表される含窒素複素環化合物の例を、下記表１～表４に示す。下記表中、Ｍｅはメチル基、Ｅｔはエチル基、nＰｒはｎ－プロピル基、ＣＰｒはシクロプロピル基、Ｐｙはピリジル基、Ｐｈはフェニル基を、それぞれ表す。
　表１及び表２中、Ｒ5とＲ6においてＰｈと表す場合は、Ｒ5とＲ6が一緒になって、それぞれが結合する炭素原子と共に、ベンゼン環を形成していることを表している。この場合、ベンゼン環とピリジン環とによってキノリン環が形成される。該ベンゼン環に置換基を有する場合はキノリンとしての置換位置を表す。
　表３及び表４中、Ｒ5とＲ6が一緒になって、式：-ＣＨ=ＣＨ-Ｓ-と表す場合は、チオフェン環を形成していることを表している。この場合、チオフェン環とピリジン環とによってチエノ［２，３－ｂ］ピリジン環を形成していることを表す。Ｒ5とＲ6が一緒になって、式：-（ＣＨ2）4-と表す場合は、シクロヘキセン環を形成していることを表している。この場合、シクロヘキセン環とピリジン環とによって５，６，７，８－テトラヒドロキノリン環を形成していることを表す。 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. In the following table, 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, and Ph represents a phenyl group.
In Tables 1 and 2, when 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. . In this case, a quinoline ring is formed by the benzene ring and the pyridine ring. When the benzene ring has a substituent, it represents a substitution position as quinoline.
In Tables 3 and 4, when R 5 and R 6 are combined and represented by the formula: —CH═CH—S—, this indicates that a thiophene ring is formed. In this case, a thieno [2,3-b] pyridine ring is formed by the thiophene ring and the pyridine ring. When R 5 and R 6 together represent the formula: — (CH 2 ) 4 —, this indicates that a cyclohexene ring is formed. In this case, it represents that the 5,6,7,8-tetrahydroquinoline ring is formed by the cyclohexene ring and the pyridine ring.
Figure JPOXMLDOC01-appb-C000012
 　　（Ｉ）
 
Figure JPOXMLDOC01-appb-C000012
 (I)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　代表的な化合物の物性値及び1H-NMRを、下記表５に示す。
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-I000003
Figure JPOXMLDOC01-appb-I000004
The physical properties and 1 H-NMR of typical compounds are shown in Table 5 below.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-I000003
Figure JPOXMLDOC01-appb-I000004
　次に、本発明の殺菌剤の製剤実施例を若干示すが、添加物及び添加割合は、これら実施例に限定されるべきものではなく、広範囲に変化させることが可能である。製剤実施例中の部は重量部を示す。 Next, some preparation examples of the bactericide of the present invention will be shown. However, the additive and the addition ratio are not limited to these examples, and can be changed in a wide range. The part in a formulation example shows a weight part.
製剤実施例１　　　　水和剤
　　本発明化合物　　　　　　　　　　　　　　　　　４０部
　　クレー　　　　　　　　　　　　　　　　　　　　４８部
　　ジオクチルスルホサクシネートナトリウム塩　　　　４部
　　リグニンスルホン酸ナトリウム塩　　　　　　　　　８部
　以上を均一に混合して微細に粉砕し、有効成分４０％の水和剤を得る。 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.
製剤実施例２　　　　乳剤
　　本発明化合物　　　　　　　　　　　　　　　　　１０部
　　ソルベッソ２００　　　　　　　　　　　　　　　５３部
　　シクロヘキサノン　　　　　　　　　　　　　　　２６部
　　ドデシルベンゼンスルホン酸カルシウム塩　　　　　１部
　　ポリオキシエチレンアルキルアリルエーテル　　　１０部
　以上を混合溶解し、有効成分１０％の乳剤を得る。 Formulation Example 2 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.
製剤実施例３　　　　粉剤
　　本発明化合物　　　　　　　　　　　　　　　　　１０部
　　クレー　　　　　　　　　　　　　　　　　　　　９０部
　以上を均一に混合して微細に粉砕し、有効成分１０％の粉剤を得る。 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.
製剤実施例４　　　　粒剤
　　本発明化合物　　　　　　　　　　　　　　　　　　５部
　　クレー　　　　　　　　　　　　　　　　　　　　７３部
　　ベントナイト　　　　　　　　　　　　　　　　　２０部
　　ジオクチルスルホサクシネートナトリウム塩　　　　１部
　　リン酸カリウム　　　　　　　　　　　　　　　　　１部
　以上をよく粉砕混合し、水を加えてよく練り合せた後、造粒乾燥して有効成分５％の粒剤を得る。 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.
製剤実施例５　　　　懸濁剤
　　本発明化合物　　　　　　　　　　　　　　　　　１０部
　　ポリオキシエチレンアルキルアリルエーテル　　　　４部
　　ポリカルボン酸ナトリウム塩　　　　　　　　　　　２部
　　グリセリン　　　　　　　　　　　　　　　　　　１０部
　　キサンタンガム　　　　　　　　　　　　　　　０．２部
　　水　　　　　　　　　　　　　　　　　　　　７３．８部
　以上を混合し、粒度が３ミクロン以下になるまで湿式粉砕し、有効成分１０％の懸濁剤を得る。 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.
製剤実施例６　　　　顆粒水和剤
　　本発明化合物　　　　　　　　　　　　　　　　　４０部
　　クレー　　　　　　　　　　　　　　　　　　　　３６部
　　塩化カリウム　　　　　　　　　　　　　　　　　１０部
　　アルキルベンゼンスルホン酸ナトリウム塩　　　　　１部
　　リグニンスルホン酸ナトリウム塩　　　　　　　　　８部
　　アルキルベンゼンスルホン酸ナトリウム塩のホルムアルデヒド縮合物
　　　　　　　　　　　　　　　　　　　　　　　　　　５部
　以上を均一に混合して微細に粉砕後、適量の水を加えてから練り込んで粘土状にする。粘土状物を造粒した後、乾燥し、有効成分４０％の顆粒水和剤を得る。 Formulation Example 6 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.
　代表的な化合物について、下記のリンゴ黒星病防除試験及びキュウリ灰色かび病防除試験を行った。 For the representative compounds, the following apple scab control test and cucumber gray mold control test were conducted.
（リンゴ黒星病防除試験）
　素焼きポットで栽培したリンゴ幼苗（品種「国光」、３～４葉期）に、本発明殺菌剤としての乳剤（製剤実施例２）を有効成分１００ｐｐｍの濃度で散布した。室温で自然乾燥した後、リンゴ黒星病菌（Ｖｅｎｔｕｒｉａ　ｉｎａｅｑｕａｌｉｓ）の分生胞子を接種し、明暗周期が１２時間で、２０℃、高湿度の室内に２週間保持した。葉上の病斑出現状態を無処理のものと比較検査し、防除効果を求めた。
　結果、化合物番号１－２～１－９、１－１１、１－１４、１－２０、１－３１～１－４５、１－４７～１－４９、２－２、２－６、及び３－２６が75％以上の防除効果を示した。 (Apple black spot disease prevention test)
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. After natural drying at room temperature, conidia of Venturia inaequalis were inoculated and kept in a room at 20 ° C. and high humidity for 2 weeks with a light-dark cycle of 12 hours. The lesion appearance state on the leaf was compared with the untreated one, and the control effect was obtained.
As a result, 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.
（試験例）キュウリ灰色かび病防除試験
　素焼きポットで栽培したキュウリ幼苗（品種「相模半白」、子葉期）に、本発明化合物の乳剤を有効成分１００ｐｐｍの濃度で散布した。室温で自然乾燥した後、キュウリ灰色かび病菌（Botrytis cinerea）の分生胞子懸濁液を滴下接種し、暗所、２０℃、高湿度の室内に４日間保持した。葉上の病斑出現状態を無処理と比較調査し、防除効果を求めた。
　結果、化合物番号１－２～１－９、１－１１、１－１３、１－１４、１－２０、１－３１～１－３６、１－３８～１－４７、２－２、及び３－２６が75％以上の防除効果を示した。 (Test Example) Cucumber Gray Mold Control Test A cucumber seedling (cultivar “Sagamihanjiro”, cotyledon stage) cultivated in an unglazed pot was sprayed with an emulsion of the compound of the present invention at a concentration of 100 ppm active ingredient. After natural drying at room temperature, a conidial spore suspension of cucumber gray mold fungus (Botrytis cinerea) was inoculated dropwise and kept in a dark place at 20 ° C. in a high humidity room for 4 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.
As a result, compound numbers 1-2 to 1-9, 1-11, 1-13, 1-14, 1-20, 1-31 to 1-36, 1-38 to 1-47, 2-2, and 3 -26 showed a control effect of 75% or more.
　本発明の含窒素複素環化合物またはその塩は新規化合物であり、効果が確実で安全に使用できる農園芸用殺菌剤の有効成分として有用である。
　また、本発明の農園芸用殺菌剤は優れた防除効果を有し、植物体に薬害を生じることがなく、人畜魚類に対する毒性や環境への影響が少ない薬剤であるので、産業上有用である。 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.
In addition, 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. .

Claims (3)

  1. 　式（Ｉ）
    Figure JPOXMLDOC01-appb-I000005
    　　（Ｉ）
    （式（Ｉ）中、Ｒ1は、無置換若しくは置換基を有するＣ６～１０アリール基、無置換若しくは置換基を有するヘテロアリール基、無置換若しくは置換基を有するアラルキル基、または無置換若しくは置換基を有するヘテロアラルキル基を示す。
    　Ｒ2は、水素原子、ハロゲン原子、Ｃ１～２０アルキル基、Ｃ１～２０ハロアルキル基、Ｃ２～２０アルケニル基、Ｃ２～２０ハロアルケニル基、Ｃ２～２０アルキニル基、Ｃ２～２０ハロアルキニル基、Ｃ１～２０アルコキシ基、Ｃ１～２０ハロアルコキシ基、Ｃ３～２０シクロアルキル基、Ｃ４～２０シクロアルケニル基、Ｃ８～２０シクロアルキニル基、Ｃ１～２０アシル基、Ｃ１～２０アルコキシカルボニル基、無置換若しくは置換基を有するＣ６～１０アリール基、無置換若しくは置換基を有するヘテロアリール基、無置換若しくは置換基を有するアラルキル基、または無置換若しくは置換基を有するヘテロアラルキル基を示す。
    　Ｒ3～Ｒ6は、それぞれ独立して、水素原子、ハロゲン原子、Ｃ１～２０アルキル基、Ｃ１～２０ハロアルキル基、Ｃ２～２０アルケニル基、Ｃ２～２０ハロアルケニル基、Ｃ２～２０アルキニル基、Ｃ２～２０ハロアルキニル基、Ｃ１～２０アルコキシ基、Ｃ１～２０ハロアルコキシ基、Ｃ３～２０シクロアルキル基、Ｃ３～２０シクロアルコキシ基、Ｃ２～２０アルケニルオキシ基、Ｃ２～２０アルキニルオキシ基、Ｃ１～２０アルキルチオ基、シアノ基、ニトロ基、無置換若しくは置換基を有するアミノ基、水酸基、チオール基、無置換若しくは置換基を有するフェニル基、無置換若しくは置換基を有するアラルキル基、無置換若しくは置換基を有するアリールオキシ基、または無置換若しくは置換基を有するヘテロ環基を示す。
    　Ｒ4とＲ5、及びＲ5とＲ6は、一緒になってそれぞれが結合する炭素原子と共に、無置換若しくは置換基を有する５～８員環を形成してもよい。
    　Ｒ5とＲ6は、同時に水素原子であることはない。
    　Ｘは、ハロゲン原子、ニトロ基、無置換若しくは置換基を有するアミノ基、水酸基、または有機基を示す。
    　ｎは、０～４のいずれかの整数を示す。
    　Ｚは、酸素原子または硫黄原子を示す。）
    で表される含窒素複素環化合物またはその塩。     Formula (I)
    Figure JPOXMLDOC01-appb-I000005
    (I)
    (In the formula (I), R 1 is an unsubstituted or substituted C6-10 aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, or unsubstituted or substituted. A heteroaralkyl group having a group is shown.
    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 heterocyclic group.
    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. )
    Or a salt thereof.
  2. 　前記Ｒ4とＲ5、及びＲ5とＲ6が一緒になってそれぞれが結合する炭素原子と共に形成する無置換若しくは置換基を有する５～８員環が、無置換若しくは置換基を有するシクロアルケン環、無置換若しくは置換基を有する芳香族炭化水素環、または無置換若しくは置換基を有するヘテロ環であることを特徴とする請求項１に記載の含窒素複素環化合物またはその塩。 Cycloalkene having an unsubstituted or substituted 5- to 8-membered ring having an unsubstituted or substituted group formed together with the carbon atom to which R 4 and R 5 and R 5 and R 6 are bonded together The nitrogen-containing heterocyclic compound or a salt thereof according to claim 1, which is a ring, an unsubstituted or substituted aromatic hydrocarbon ring, or an unsubstituted or substituted heterocyclic ring.
  3. 　請求項１または２に記載の含窒素複素環化合物またはその塩の少なくとも１種を有効成分として含有する農園芸用殺菌剤。 An agricultural and horticultural fungicide containing as an active ingredient at least one of the nitrogen-containing heterocyclic compound or a salt thereof according to claim 1 or 2.
PCT/JP2010/002947 2009-04-28 2010-04-23 Nitrogen-containing heterocyclic compound and agricultural or horticultural bactericide WO2010125782A1 (en)

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JPWO2009119089A1 (en) * 2008-03-27 2011-07-21 日本電気株式会社 Nitrogen-containing heterocyclic compounds and agricultural and horticultural fungicides
WO2022207665A1 (en) * 2021-03-31 2022-10-06 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline benzothiazine derivatives
WO2022243107A1 (en) 2021-05-18 2022-11-24 Basf Se New substituted pyridines as fungicides
WO2022243109A1 (en) 2021-05-18 2022-11-24 Basf Se New substituted quinolines as fungicides
WO2023111215A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyridine-substituted benzothiazine derivatives
WO2024104813A1 (en) * 2022-11-14 2024-05-23 Basf Se Fungicidal mixture comprising substituted pyridines
WO2025031843A1 (en) 2023-08-09 2025-02-13 Basf Se New substituted benzoxazine picolinonitrile compounds for combatting phytopathogenic fungi
WO2025121436A1 (en) * 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 Bicyclic heterocyclic compound and fungicide for agricultural and horticultural use containing same as active ingredient

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JPH06107647A (en) * 1992-08-12 1994-04-19 Takeda Chem Ind Ltd Production of 1,3-benzoxazine derivative
WO2005070917A1 (en) * 2004-01-23 2005-08-04 Sankyo Agro Company, Limited 3-(dihydro(tetrahydro)isoquinolin-1-yl)quinolines
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2009119089A1 (en) * 2008-03-27 2011-07-21 日本電気株式会社 Nitrogen-containing heterocyclic compounds and agricultural and horticultural fungicides
WO2022207665A1 (en) * 2021-03-31 2022-10-06 Syngenta Crop Protection Ag Microbiocidal quinoline/quinoxaline benzothiazine derivatives
WO2022243107A1 (en) 2021-05-18 2022-11-24 Basf Se New substituted pyridines as fungicides
WO2022243109A1 (en) 2021-05-18 2022-11-24 Basf Se New substituted quinolines as fungicides
WO2023111215A1 (en) 2021-12-17 2023-06-22 Syngenta Crop Protection Ag Microbiocidal pyridine-substituted benzothiazine derivatives
WO2024104813A1 (en) * 2022-11-14 2024-05-23 Basf Se Fungicidal mixture comprising substituted pyridines
WO2025031843A1 (en) 2023-08-09 2025-02-13 Basf Se New substituted benzoxazine picolinonitrile compounds for combatting phytopathogenic fungi
WO2025121436A1 (en) * 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 Bicyclic heterocyclic compound and fungicide for agricultural and horticultural use containing same as active ingredient

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