WO2016068301A1 - Pest control agent - Google Patents

Pest control agent Download PDF

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Publication number
WO2016068301A1
WO2016068301A1 PCT/JP2015/080774 JP2015080774W WO2016068301A1 WO 2016068301 A1 WO2016068301 A1 WO 2016068301A1 JP 2015080774 W JP2015080774 W JP 2015080774W WO 2016068301 A1 WO2016068301 A1 WO 2016068301A1
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Prior art keywords
alkyl
alkylamino
alkenyl
compound
alkynyl
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PCT/JP2015/080774
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French (fr)
Japanese (ja)
Inventor
幸太郎 吉田
直 梅本
達也 可児
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石原産業株式会社
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Publication of WO2016068301A1 publication Critical patent/WO2016068301A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C07D213/71—Sulfur atoms to which a second hetero atom is attached

Definitions

  • the present invention relates to a novel 4- (phenylethenyl) pyridine compound or a salt thereof.
  • Patent Document 1 discloses 3,5-dichloro-4-[(1E) -2- [4- (1,1-dimethylethynyl) phenyl] -1,2-difluoroethenyl] pyridine, 3,5-dichloro It is described that compounds such as -4-[(1E) -2- [4- (1,1-dimethylethynyl) phenyl] -2-fluoroethenyl] pyridine are useful as agricultural and horticultural insecticides. However, compounds having a chloroethenyl moiety are not described.
  • Patent Document 2 describes a phenylethenylpyridine derivative having an insecticidal and acaricidal action and a salt thereof, but does not describe a compound according to the present invention.
  • Non-Patent Document 1 describes (Z) -4- (2-chloro-2-phenylethenyl) pyridine, but this compound is not a compound for agricultural use.
  • the present invention provides a highly active compound against pests, provides a pest control agent using the compound, a method for controlling pests by applying the compound, the compound or a salt thereof
  • An object of the present invention is to provide a production method of the compound and an intermediate for producing the compound.
  • the present inventors have made various studies on pyridine derivatives in order to find better pest control agents. As a result, the present inventors have found that a novel 4- (phenylethenyl) pyridine compound has a very high control effect against pests at a low dose, and completed the present invention.
  • R 1 is a halogen atom, cyano, nitro, (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl] , (C 1 -C 6 ) haloalkyl, (C 1 -C 6 ) alkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 3 -C 6 ) cycloalkoxy, ( C 1 -C 6 ) haloalkoxy, (C 1 -C 6 ) alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, (C 3 -C 6 ) cycloalkylthio, (C 1- C 6 ) haloalkylthio,
  • R 1 , R 2 and n are as defined above] or a salt thereof.
  • the pest control agent comprising the compound of the formula (I) or a salt thereof as an active ingredient has a very high control effect against pests at a low dose.
  • halogen atom in the formulas (I) and (II) or the halogen as a substituent examples include each atom of fluorine, chlorine, bromine or iodine.
  • the number of halogen atoms as a substituent may be 1 or 2 or more, and in the case of 2 or more, each halogen atom may be the same or different. Further, the halogen atom may be substituted at any position.
  • alkyl or alkyl moiety in the formulas (I) and (II) examples include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, and normal hexyl.
  • linear or branched C 1 -C 6 groups such as neohexyl.
  • tertiary may be written as “tert-”.
  • alkenyl or alkenyl moiety in the formulas (I) and (II) examples include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl, 2 -Methyl-2-propenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-2-butenyl, 1-hexenyl, 2,3 And straight-chain or branched C 2 -C 6 groups such as -dimethyl-2-butenyl.
  • alkynyl or alkynyl moiety in the formulas (I) and (II) examples include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, Linear or branched C 2 ⁇ such as 2-methyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl C 6 group may be mentioned.
  • Examples of the cycloalkyl or cycloalkyl moiety in the formulas (I) and (II) include C 3 -C 6 groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • the salts of the compounds of the formulas (I) and (II) include any salt that is acceptable in the art, for example, ammonium salts such as dimethylammonium salt and triethylammonium salt; hydrochloric acid Inorganic salts such as salts, perchlorates, sulfates, nitrates; organic acid salts such as acetates, trifluoroacetates, oxalates, p-toluenesulfonates, methanesulfonates, etc. It is done.
  • ammonium salts such as dimethylammonium salt and triethylammonium salt
  • hydrochloric acid Inorganic salts such as salts, perchlorates, sulfates, nitrates
  • organic acid salts such as acetates, trifluoroacetates, oxalates, p-toluenesulfonates, methanesulfonates, etc. It is done
  • isomers such as optical isomers
  • present invention includes both isomers and isomer mixtures.
  • isomers are described as a mixture.
  • the present invention also includes various isomers other than those described above within the scope of technical common sense in the technical field.
  • the chemical structure may be different from that of the general formula (I). However, since those skilled in the art can sufficiently recognize that they are related to isomers, Obviously, it is within range.
  • the compound of the above formula (I) or a salt thereof (hereinafter abbreviated as the compound of the present invention) can be produced according to the following production methods and ordinary salt production methods, but is not limited to these methods. Absent.
  • the compound of the present invention can be produced by reacting the compound of formula (II) or a salt thereof with a chlorinating agent in the presence of a base.
  • This reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene; N, N-disubstituted anilines such as dimethylaniline and diethylaniline; 1 type (s) or 2 or more types can be selected and mixed appropriately from the above.
  • the reaction temperature is usually 0 ° C. to 180 ° C., preferably 20 ° C. to 120 ° C.
  • the reaction time is usually several minutes to 24 hours.
  • chlorinating agent examples include thionyl chloride, phosphorus pentachloride, phosphorus oxychloride, phosphorus trichloride and the like.
  • the chlorinating agent is used in an amount of usually 1 mol or more, preferably 1 to 3 mol per mol of the compound of formula (II).
  • the base examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium hydride, potassium hydride and lithium hydride. Alkoxides such as sodium methoxide and sodium ethoxide; tertiary amines such as triethylamine, pyridine and diisopropylethylamine, etc., and tertiary amines are used. Is preferred.
  • the base is used in an amount of usually 1 mol or more, preferably 1 to 3 mol per mol of the compound of formula (II).
  • R 1 and n are as defined above, R 3 is (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl or (C 2 -C 6 ) alkynyl, and m is 1 or 2]
  • Examples of the oxidizing agent include peroxides of carboxylic acids such as 3-chloroperbenzoic acid; hydrogen peroxide water.
  • Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform.
  • the reaction temperature can usually be in the range of about ⁇ 20 ° C. to the boiling point of the solvent used.
  • the reaction time is usually several minutes to 24 hours.
  • the compound of formula (Id) in which R 2 is (C 2 -C 6 ) alkynyl is obtained by combining the compound of formula (Ic) with (C 2 -C 6 ) alkyne. It can also be produced by reacting in the presence of a palladium catalyst, a copper salt and a base.
  • R 1 and n are as defined above, X is a halogen atom, and R 2a is (C 2 -C 6 ) alkynyl]
  • Examples of the palladium catalyst include bistriphenyltriphenylphosphine palladium dichloride, tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), tris (dibenzylideneacetone) dipalladium (0), and the like. Is mentioned.
  • Examples of the copper salt include copper (I) iodide.
  • the base may be an organic base or an inorganic base.
  • the organic base include amine bases such as triethylamine and diisopropylamine.
  • the inorganic base include alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate.
  • the reaction can be performed in the presence of a solvent, if necessary.
  • the solvent may be any solvent as long as it is inert to the reaction.
  • an amine base such as triethylamine or diisopropylamine
  • an aprotic polar solvent such as N, N-dimethylformamide or acetonitrile
  • 1 type or 2 types or more can be suitably selected from such ethers.
  • the reaction temperature can usually be about 20 ° C. to a temperature at which the reaction mixture is refluxed.
  • the reaction time is usually several minutes to 24 hours.
  • the compound of the above formula (II) can be produced by reacting the compound of the formula (III) with the compound of the formula (IV) in the presence of a base.
  • the reaction can be performed in the presence of a solvent, if necessary.
  • a solvent any solvent may be used as long as it is inert to the reaction.
  • ethers such as diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, and 1,4-dioxane are appropriately used.
  • the reaction temperature can usually be in the range of about ⁇ 20 ° C. to the boiling point of the solvent used.
  • the reaction time can usually be from several minutes to 48 hours.
  • Examples of the base include alkali metal amides such as lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, and lithium di (isopropyl) amide.
  • alkali metal amides such as lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, and lithium di (isopropyl) amide.
  • R 4 is (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl or (C 1 -C 6 ) haloalkyl]
  • the reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction.
  • a solvent such as acetonitrile and dioxane; water; can do.
  • the reaction temperature can be generally in the range of about room temperature to the temperature at which the reaction mixture is refluxed.
  • the reaction time can usually be from several minutes to 48 hours.
  • Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid; and organic acids such as methanesulfonic acid.
  • Examples of the nitrite include isopropyl nitrite and tert-butyl nitrite.
  • Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkoxides such as sodium methoxide and sodium ethoxide And the like.
  • the compound of the formula (III-b) in which R 2 is SR 4 is a diazonium compound obtained by reacting 3-amino-4-methylpyridine with an inorganic nitrite or nitrite. Thereafter, it can be produced by a Sandmeyer reaction in which R 4 SH or (R 4 S) 2 is reacted.
  • inorganic nitrites include sodium nitrite and potassium nitrite.
  • examples of the nitrite include tert-butyl nitrite and isoamyl nitrite.
  • the reaction can be carried out in the presence of a copper catalyst as necessary.
  • a copper catalyst examples include copper (I) oxide and copper (II) sulfate pentahydrate.
  • the reaction can be performed in the presence of an acid, if necessary.
  • the acid include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as acetic acid and methanesulfonic acid; and the like.
  • the reaction can be performed in the presence of a base as necessary.
  • a base examples include alkali metal hydrides such as sodium hydride; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal water such as lithium hydroxide, sodium hydroxide and potassium hydroxide. Oxides; and the like.
  • the reaction can be performed in the presence of a solvent, if necessary.
  • a solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene and xylene; aprotic polarities such as acetonitrile, N, N-dimethylformamide and dimethyl sulfoxide.
  • One type or two or more types can be appropriately selected from a solvent, water, and the like.
  • the reaction temperature can usually be in the range of ⁇ 20 ° C. to 200 ° C.
  • the reaction time is usually several minutes to 24 hours.
  • Examples of inorganic nitrites and nitrites include those similar to the intermediate production method [3].
  • the halogenating agent include halogens such as chlorine, bromine and iodine; hydrohalic acids such as hydrochloric acid, hydrobromic acid and hydroiodic acid; copper (I) chloride, copper (I) bromide and iodide Examples thereof include copper (I) halides such as copper (I); copper (II) halides such as copper (II) chloride and copper (II) bromide; tetrafluoroboric acid; potassium iodide;
  • the reaction can be carried out in the presence of a copper catalyst as necessary.
  • a copper catalyst include the aforementioned copper (I) halide, copper (II) halide, copper (I) oxide, copper (II) sulfate pentahydrate and the like.
  • the reaction can be performed in the presence of an acid, if necessary.
  • the acid include inorganic acids such as the above-mentioned hydrohalic acids and sulfuric acids; organic acids such as acetic acid, methanesulfonic acid, and p-toluenesulfonic acid.
  • the reaction can be performed in the presence of a solvent, if necessary.
  • a solvent include those similar to the intermediate production method [3], and one or more of these can be appropriately selected and mixed for use.
  • the reaction temperature can usually be in the range of ⁇ 20 ° C. to 200 ° C.
  • the reaction time is usually several minutes to 24 hours.
  • the pest control agent containing the compound of the present invention includes, for example, pests, mites, nematodes or soil pests that are problematic in the field of agriculture and horticulture, that is, agricultural and horticultural insecticides, among them insecticides, acaricides, It is useful as a nematode or soil killing pest. It is also useful as an animal parasite control agent, that is, an animal killing parasite agent.
  • the compounds of the present invention are useful as insecticides, acaricides, nematicides or soil pesticides.
  • aphids such as peach aphids, cotton aphids, etc .
  • Agricultural pests such as tree flies, scarab beetles, tamanayaga, kaburayaga, ants, etc .
  • gastropods such as slugs, maimai, etc .
  • sanitary pests such as house dust mites, cockroaches, house flies, mosquitoes, etc .
  • Pests of cereals; clothing such as moths, swordworms, termites, etc., pests such as house pests; Mites; indoor dust mites such as Scarlet mite, Scarlet mite, southern ticks, etc .; such as mites, root-knot nematodes, cyst nematodes, nestle nematodes, rice nesting nematodes, strawberry nematodes, pine wood nematodes, etc. It is effective for the control of soil pests such as nematodes such as plant parasitic nematodes;
  • the insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is particularly effective for controlling plant parasitic mites, agricultural pests, plant parasitic nematodes and the like. Among them, it is very useful as an insecticide or acaricide because it shows a further excellent effect in controlling plant parasitic mites and agricultural pests.
  • insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is an organic phosphorus agent, carbamate agent, synthetic pyrethroid agent, neonicotinoid agent and other various resistant insect pests. It is also effective for control.
  • the compound of the present invention has an excellent osmotic transfer property, it can be harmful to soil by treating the soil with an insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention. At the same time as controlling insects, mites, nematodes, gastropods, isopodaes, it is possible to control pests on the foliage.
  • insecticide acaricide, nematicide or soil insecticide containing the compound of the present invention
  • the aforementioned plant parasitic mites, agricultural pests, plant parasitic nematodes, gastropods Insecticides, acaricides, nematicides or soil pesticides that comprehensively control soil pests and the like.
  • Insecticides, acaricides, nematicides or soil pesticides containing the compound of the present invention are usually powders, granules, granule wettable powders by mixing the compound with various agricultural adjuvants, It can be used in various forms such as wettable powder, aqueous suspension, oil suspension, granular aqueous solvent, aqueous solvent, emulsion, liquid, paste, aerosol, microdispersant, etc. As long as it fits the purpose of the present invention, it can be in any formulation form commonly used in the art.
  • adjuvants used in the preparation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, and starch.
  • solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, and starch.
  • a bulking agent for example, a bulking agent, a thickening agent, an anti-settling agent, an antifreezing agent, a dispersion stabilizer, a phytotoxicity reduction.
  • Various commonly used adjuvants such as agents and antifungal agents can also be used.
  • the blending ratio (weight ratio) of the compound of the present invention and various adjuvants is generally 0.001: 99.999 to 95: 5, preferably 0.005: 99.995 to 90:10.
  • the application of the insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is generally based on differences in weather conditions, formulation form, application time, place of application, type of pests and occurrence, etc. Although it cannot be defined, it is generally carried out at an active ingredient concentration of 0.05 to 800,000 ppm, preferably 0.5 to 500,000 ppm.
  • the application amount per unit area is generally 0.05 to 800 ppm of the compound of the present invention per hectare. 50,000 g, preferably 1 to 30,000 g.
  • the present invention includes a method for controlling pests by such an application method, for example, a method for controlling pests, mites, nematodes or soil pests, particularly plant parasitic mites, agricultural pests, plant parasitic lines. Insect control methods are also included.
  • insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, safeners, etc. May show excellent effects and functionality.
  • pesticides include, for example, herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, etc. Is mentioned.
  • the product can improve the application range, the timing of chemical treatment, the control activity, and the like in a preferable direction.
  • the compound of the present invention and the other active ingredient compounds of other agricultural chemicals may be used separately by mixing them at the time of spraying or by using both together.
  • the present invention includes such an insecticidal composition, an acaricidal composition, a nematicidal composition or a soil-killing insect pest composition.
  • Bacillus ⁇ ⁇ ⁇ thuringiensis aizawai Bacillus ⁇ ⁇ ⁇ thuringiensis kurstaki, Bacillus ⁇ thuringiensis israelensis, Bacillus thuringiensis israelensis, Microbial pesticides such as crystal protein toxins, entomopathogenic virus agents, entomopathogenic fungi agents, nematode pathogenic fungi agents, etc.
  • Bacillus thuringiensis such as Gensis Tenebrionis (Bacillus thuringiensis tenebrionis), Avermectin, emamectin benzoate, milbemectin, milbemycin, spinosad, ivermectin (Ivermectin), lepimectin, DE-175, antibiotics and semi-synthetic antibiotics such as abamectin, emamectin, spinetoram; azadirachtin, rotenone Such natural products; repellents such as deet; etc. can also be mixed and used together.
  • an active ingredient compound for example, mepanipyrim, pyrimethanil, cyprodinil ), Anilinopyrimidine compounds such as ferimzone; Tria such as 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) [1,2,4] triazolo [1,5-a] pyrimidine Zolopyrimidine compounds; Pyridinamine compounds such as fluazinam; Triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanil, cyproconazole cyproconazole), tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole,
  • pesticides that can be used in combination with or combined with the compounds of the present invention include, for example, active compound compounds of herbicides, particularly those of soil treatment type, as described in The Pesticide Manual (15th edition), etc. There is.
  • the animal-killing parasite agent include harmful ectoparasites parasitic on the body surface of the host animal (eg, back, armpit, lower abdomen, inner thigh, etc.)
  • harmful ectoparasites parasitic on the body surface of the host animal eg, back, armpit, lower abdomen, inner thigh, etc.
  • it is effective for controlling harmful endoparasites parasitic on the stomach, intestinal tract, lungs, heart, liver, blood vessels, subcutaneous, lymphatic tissue, etc., and is particularly effective for controlling ectoparasites.
  • ectoparasites examples include animal parasitic mites and fleas. There are so many of these types that it is difficult to list them all.
  • animal parasitic ticks include Boophilus microplus, Rhipicephalus sanguineus, Scarlet ticks (Haemaphysalis longicornis), Tick ticks (Haemaphysalis flava), Tick ticks (Haemaphysalis campuls , Mites (Haemaphysalis japonica), mites (Haemaphysalis kitaokai), mites (Haemaphysalis ias), mites (Ixodes ovatus), mites (Ixodes nipponensis), mites (Ixodes nipponensis), mushroom mites (Ixodes nipponensis), mites Ticks such as Haemaphysalis megaspinosa), Dermacentor reticulatus, Dermacentor taiwanesis; Dermanyssus gallinae; Ornithonyssus
  • animal parasitic fleas include ectoparasite worms belonging to the order Flea (Siphonaptera), and more specifically fleas belonging to the family Flea (Pulicidae), Cleaphyllus (Ceratephyllus), and the like.
  • Fleas belonging to the family flea family include, for example, dog fleas (Ctenocephalides canis), cat fleas (Ctenocephalides felis), human fleas (Pulex irritans), elephant fleas (Echidnophaga gallinacea), keops mouse fleas (Xenopsylla cheopis), Leptopsylla segnis), European mouse minnow (Nosopsyllus fasciatus), and Yamato mouse minnow (Monopsyllus anisus);
  • the animalicidal parasite agent containing the compound of the present invention is effective for controlling fleas belonging to the family flea family, especially dog fleas, cat fleas and the like.
  • ectoparasites include, for example, lice such as bovine lice, foal lice, sheep lice, bovine white lice, head lice; lice such as cat lice; blood-sucking dipterous pests such as bovine abs, quail sharks, .
  • endoparasites include nematodes such as lungworm, benthic, nodular worms, gastric parasites, roundworms, and filamentous worms; Tapeworms such as real tapeworms, multi-headed tapeworms, single-banded tapeworms, multi-banded tapeworms; Japanese schistosomiasis, fluke like liver fluke; coccidium, malaria parasite, intestinal granulocyst, toxoplasma, chestnut Protozoa such as Ptosporidium, and the like.
  • nematodes such as lungworm, benthic, nodular worms, gastric parasites, roundworms, and filamentous worms
  • Tapeworms such as real tapeworms, multi-headed tapeworms, single-banded tapeworms, multi-banded tapeworms
  • Japanese schistosomiasis fluke like liver fluke
  • Examples of host animals include various pet animals, livestock, and poultry. More specifically, for example, dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (eg, pigeons, parrots, nine-birds, wild birds, parakeets, juvenile pine, canary, etc.) Pigs, sheep, ducks, chickens, etc.
  • the animal killing parasite agent containing the compound of the present invention is effective for controlling pests or ticks that are externally parasitic on pet animals or livestock.
  • pet animals or domestic animals it is particularly effective for dogs, cats, cows or horses.
  • the compound of the present invention when used as an animal killing parasite, it may be used as it is, and together with suitable adjuvants, powders, granules, tablets, powders, capsules, liquid agents, emulsions, aqueous suspensions, It can also be formulated and used in various forms such as an oily suspension.
  • suitable adjuvants powders, granules, tablets, powders, capsules, liquid agents, emulsions, aqueous suspensions
  • suitable adjuvants powders, granules, tablets, powders, capsules, liquid agents, emulsions, aqueous suspensions
  • suitable adjuvants powders, granules, tablets, powders, capsules, liquid agents, emulsions, aqueous suspensions
  • It can also be formulated and used in various forms such as an oily suspension.
  • any preparation forms used in the normal field can be used as long as the object of the present invention is met.
  • anionic surfactants and nonionic surfactants exemplified as auxiliary agents for preparation of the above-mentioned insecticides, acaricides, nematicides or soil insecticides
  • a cationic surfactant such as cetyltrimethylammonium bromide; water, acetone, acetonitrile, N-methylacetamide, N, N-dimethylacetamide, N, N-dimethylformamide, 2-pyrrolidone, N-methyl-2 -Pyrrolidone, kerosene, triacetin, methanol, ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, liquid polyoxyethylene glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Solvents such as ethylene glycol monoethyl ether, diethylene glycol normal butyl ether, di
  • each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention.
  • it can be used by appropriately selecting from those known in the field, and further, selected from various adjuvants used in the above-mentioned agricultural and horticultural fields. You can also
  • the compounding ratio (weight ratio) of the compound of the present invention and various adjuvants is usually about 0.1: 99.9 to 90:10.
  • a diluent such as water
  • various spreading agents for example, surfactants, vegetable oils, mineral oils, etc.
  • Administration of the compound of the present invention to the host animal is performed orally or parenterally.
  • the oral administration method include a method of administering tablets, liquid agents, capsules, wafers, biscuits, minced meat, and other feeds containing the compound of the present invention.
  • the compound of the present invention is prepared into an appropriate preparation and taken into the body by intravenous administration, intramuscular administration, intradermal administration, subcutaneous administration, etc .; spot-on ) Treatment, pour-on treatment, spray treatment, and the like; and a method of embedding a resin piece containing the compound of the present invention under the skin of a host animal.
  • the dose of the compound of the present invention to the host animal varies depending on the administration method, administration purpose, disease symptom, etc., but is generally 0.01 mg to 100 g, preferably 0.1 mg to 10 g, per 1 kg body weight of the host animal. It is appropriate to administer in proportions.
  • the present invention also includes a method for controlling animal parasites by the administration method or dosage as described above, particularly a method for controlling ectoparasites or endoparasites.
  • the present invention by controlling harmful animal parasites as described above, various host animal diseases caused by them may be prevented or treated.
  • the present invention includes a prophylactic or therapeutic agent for parasitic animal diseases containing the compound of the present invention as an active ingredient, and a method for preventing or treating parasitic animal diseases.
  • the compound of the present invention When the compound of the present invention is used as an animal killing parasite, various vitamins, minerals, amino acids, nutrients, enzyme preparations, antipyretics, sedatives, anti-inflammatory agents, bactericides, coloring agents, fragrances, It can be mixed with or used in combination with preservatives. In addition, if necessary, other animal drugs and agricultural chemicals such as anthelmintics, anticoccidials, insecticides, acaricides, fleas, nematicides, fungicides, antibacterials, etc. In this case, a better effect may be exhibited.
  • the present invention includes a composition for controlling animal parasites in which various components as described above are mixed or used together, and a method for controlling animal parasites using the composition, in particular, control of ectoparasites or endoparasites. A method is also included.
  • R 1 and R 2 are as defined above] or a 4- (phenylethenyl) pyridine compound or a salt thereof.
  • R 1 is a halogen atom, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl or (C 1 -C 6 ) haloalkoxy
  • R 2 is a halogen atom, (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio, (C 1 -C 6 ) alkylsulfinyl, (1) or (2) which is (C 1 -C 6 ) alkylsulfonyl, (C 1 -C 6 alkoxy) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl or di (C 1 -C 6 alkyl) aminocarbonyl 4- (phenylethenyl) pyridine-based compound or a salt thereof according to (4).
  • R 1 is a halogen atom, (C 1 -C 6 ) alkyl or (C 1 -C 6 ) haloalkoxy.
  • R 2 is a halogen atom, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio, (C 1 -C 6 ) alkylsulfinyl or (C 1-
  • R 1 and R 2 are as defined above] or a salt thereof.
  • R 1 is a halogen atom, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl or (C 1 -C 6 ) haloalkoxy
  • R 2 is a halogen atom, (C 1 -C (1) or (2) which is 6 ) alkyl, (C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio, (C 1 -C 6 ) alkylsulfinyl or (C 1 -C 6 ) alkylsulfonyl Or a salt thereof.
  • the reaction solution was neutralized with a saturated aqueous sodium hydrogen carbonate solution, and then a saturated aqueous sodium thiosulfate solution (200 mL) was added.
  • the reaction mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure.
  • Test Example 2 Effect Test on Tobacco Whitefly To a pot-planted cucumber seedling parasitized with 1 to 2 instar larvae, a chemical solution prepared to a concentration of 200 ppm of the compound of the present invention was sprayed using a hand spray. After the chemical solution was air-dried, it was left in a constant temperature room at 25 ° C. with illumination. Ten days after the treatment, the number of old larvae was examined, and the control value was determined by the following formula. As a result, the compound no. I-41, I-64, I-122, I-123, I-124, I-125, I-126, I-127, I-128 and II-41 showed control values of 90 or more.
  • Control value [1 ⁇ (Ta ⁇ Cb) / (Tb ⁇ Ca)] ⁇ 100
  • Ta Number of old larvae after treatment in treated cucumber seedling
  • Tb Number of first to second larvae before treatment in treated cucumber seedling
  • Ca Number of old larvae after treatment in untreated cucumber seedling
  • Cb Before treatment in untreated cucumber seedling Number of larvae 1-2
  • Formulation Example 1 (1) Compound of the present invention 20 parts by weight (2) Clay 70 parts by weight (3) White carbon 5 parts by weight (4) Sodium polycarboxylate 3 parts by weight (5) Sodium alkylnaphthalene sulfonate 2 parts by weight or more To make a wettable powder.
  • Formulation Example 2 (1) Compound of the present invention 5 parts by weight (2) Talc 60 parts by weight (3) Calcium carbonate 34.5 parts by weight (4) Liquid paraffin 0.5 parts by weight or more are uniformly mixed to obtain a powder.
  • Formulation Example 3 (1) Compound of the present invention 20 parts by weight (2) N, N-dimethylacetamide 20 parts by weight (3) Polyoxyethylene tristyryl phenyl ether 10 parts by weight (4) Calcium dodecylbenzenesulfonate 2 parts by weight (5) Xylene 48 A mixture of more than parts by weight is uniformly mixed and dissolved to obtain an emulsion.
  • Formulation Example 4 (1) Clay 68 parts by weight (2) Sodium lignin sulfonate 2 parts by weight (3) Polyoxyethylene alkylaryl sulfate 5 parts by weight (4) White carbon 25 parts by weight A mixture of each component and the present compound Mix at a weight ratio of 4: 1 to make a wettable powder.
  • Formulation Example 5 (1) Compound of the present invention 50 parts by weight (2) Sodium alkylnaphthalene sulfonate formaldehyde condensate 2 parts by weight (3) Silicone oil 0.2 parts by weight (4) Water 47.8 parts by weight or more uniformly mixed (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are further added to the crushed stock solution, and the mixture is uniformly mixed, granulated and dried to obtain a granulated wettable powder.
  • Formulation Example 6 (1) Compound of the present invention 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Polyoxyethylene alkyl ether phosphate 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight (1 ) To (3) are mixed uniformly in advance and diluted with an appropriate amount of acetone, and then sprayed onto (4) to remove acetone and form granules.
  • Formulation Example 7 (1) Compound of the present invention 2.5 parts by weight (2) N, N-dimethylacetamide 2.5 parts by weight (3) Soybean oil 95.0 parts by weight or more are uniformly mixed and dissolved to give a trace amount of spray ( ultra low volume formulation).
  • Formulation Example 8 (1) Compound of the present invention 10 parts by weight (2) Diethylene glycol monoethyl ether 80 parts by weight (3) Polyoxyethylene alkyl ether 10 parts by weight or more of ingredients are mixed uniformly to obtain a liquid agent.

Abstract

　The purpose of the present invention is to provide a highly-active compound against pests. The present invention pertains to 4-(phenylethenyl)pyridine compounds represented by formula (I), or salts thereof. (In the formula: R1 is a halogen atom, a (C1-C6) alkyl, a (C1-C6) haloalkyl, a (C1-C6) haloalkoxy, etc.; R2 is a halogen atom, a (C1-C6) alkyl, a (C1-C6) alkoxy, a (C1-C6) alkylthio, a (C1-C6) alkylsulfinyl, a (C1-C6) alkylsulfonyl, a (C1-C6 alkoxy)carbonyl, a (C1-C6 alkyl)aminocarbonyl, a di(C1-C6 alkyl)aminocarbonyl, etc.; n is an integer from 0 to 5, and when n is 2 or more, multiple R1 units may be the same or different).

Description

有害生物防除剤Pest control agent
　本発明は、新規な４－（フェニルエテニル）ピリジン系化合物又はその塩に関する。 The present invention relates to a novel 4- (phenylethenyl) pyridine compound or a salt thereof.
　特許文献１には、３，５－ジクロロ－４－［（１Ｅ）－２－［４－（１，１－ジメチルエチニル）フェニル］－１，２－ジフルオロエテニル］ピリジン、３，５－ジクロロ－４－［（１Ｅ）－２－［４－（１，１－ジメチルエチニル）フェニル］－２－フルオロエテニル］ピリジン等の化合物が、農園芸用殺虫剤として有用であることが記載されているが、クロロエテニル部分を有する化合物は記載されていない。 Patent Document 1 discloses 3,5-dichloro-4-[(1E) -2- [4- (1,1-dimethylethynyl) phenyl] -1,2-difluoroethenyl] pyridine, 3,5-dichloro It is described that compounds such as -4-[(1E) -2- [4- (1,1-dimethylethynyl) phenyl] -2-fluoroethenyl] pyridine are useful as agricultural and horticultural insecticides. However, compounds having a chloroethenyl moiety are not described.
　特許文献２には、殺虫、殺ダニ作用を有するフェニルエテニルピリジン誘導体及びその塩が記載されているが、本発明に係る化合物は記載されていない。非特許文献１には、（Ｚ）－４－（２－クロロ－２－フェニルエテニル）ピリジンが記載されているが、当該化合物は農薬用途の化合物ではない。 Patent Document 2 describes a phenylethenylpyridine derivative having an insecticidal and acaricidal action and a salt thereof, but does not describe a compound according to the present invention. Non-Patent Document 1 describes (Z) -4- (2-chloro-2-phenylethenyl) pyridine, but this compound is not a compound for agricultural use.
国際公開第２０１３／１５８４２２号International Publication No. 2013/158422 日本国特開平１－３１６３５９号公報Japanese Unexamined Patent Publication No. 1-316359
　長年にわたり、多数の有害生物防除剤が使用されているが、効力が不十分である、害虫等が抵抗性を獲得しその使用が制限されるなど、種々の課題を有するものが少なくない。従って、かかる欠点の少ない新規な有害生物防除剤の開発が望まれている。 For many years, many pest control agents have been used, but many have various problems such as insufficient efficacy, pests gaining resistance and limiting their use. Therefore, development of a novel pest control agent with few such drawbacks is desired.
　本発明は、有害生物に対して高活性な化合物を提供すること、該化合物を用いた有害生物防除剤を提供すること、該化合物を施用して有害生物を防除する方法、該化合物又はその塩の製造方法、並びに、該化合物の製造用中間体を提供することを目的とする。 The present invention provides a highly active compound against pests, provides a pest control agent using the compound, a method for controlling pests by applying the compound, the compound or a salt thereof An object of the present invention is to provide a production method of the compound and an intermediate for producing the compound.
　本発明者らは、より優れた有害生物防除剤を見出すべく、ピリジン誘導体につき種々検討した。その結果、新規な４－（フェニルエテニル）ピリジン系化合物が、低薬量で有害生物に対して極めて高い防除効果を有することを見出し、本発明を完成した。 The present inventors have made various studies on pyridine derivatives in order to find better pest control agents. As a result, the present inventors have found that a novel 4- (phenylethenyl) pyridine compound has a very high control effect against pests at a low dose, and completed the present invention.
　即ち本発明は、式（Ｉ）： That is, the present invention relates to the formula (I):
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
〔式中、Ｒ１はハロゲン原子、シアノ、ニトロ、（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ３－Ｃ６）シクロアルキル、（Ｃ１－Ｃ６）ハロアルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ２－Ｃ６）アルケニルオキシ、（Ｃ２－Ｃ６）アルキニルオキシ、（Ｃ３－Ｃ６）シクロアルコキシ、（Ｃ１－Ｃ６）ハロアルコキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ２－Ｃ６）アルケニルチオ、（Ｃ２－Ｃ６）アルキニルチオ、（Ｃ３－Ｃ６）シクロアルキルチオ、（Ｃ１－Ｃ６）ハロアルキルチオ、（Ｃ１－Ｃ６）アルキルアミノ、（Ｃ２－Ｃ６）アルケニルアミノ、（Ｃ２－Ｃ６）アルキニルアミノ、ジ（Ｃ１－Ｃ６）アルキルアミノ、ジ（Ｃ２－Ｃ６）アルケニルアミノ、ジ（Ｃ２－Ｃ６）アルキニルアミノ、（Ｃ１－Ｃ６）アルキルスルフィニル、（Ｃ２－Ｃ６）アルケニルスルフィニル、（Ｃ２－Ｃ６）アルキニルスルフィニル、（Ｃ３－Ｃ６）シクロアルキルスルフィニル、（Ｃ１－Ｃ６）ハロアルキルスルフィニル、（Ｃ１－Ｃ６）アルキルスルホニル、（Ｃ２－Ｃ６）アルケニルスルホニル、（Ｃ２－Ｃ６）アルキニルスルホニル、（Ｃ１－Ｃ６アルキル）カルボニル、（Ｃ１－Ｃ６アルコキシ）カルボニル、（Ｃ１－Ｃ６アルキル）アミノカルボニル、ジ（Ｃ１－Ｃ６アルキル）アミノカルボニル、（Ｃ１－Ｃ６アルキル）カルボニルオキシ、（Ｃ１－Ｃ６アルキル）カルボニルアミノ又は（Ｃ１－Ｃ６アルキル）カルボニル（Ｃ１－Ｃ６）アルキルアミノであり；Ｒ２はハロゲン原子、シアノ、ニトロ、（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ１－Ｃ６）ハロアルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ３－Ｃ６）シクロアルコキシ、（Ｃ１－Ｃ６）ハロアルコキシ、（Ｃ２－Ｃ６）アルケニルオキシ、（Ｃ２－Ｃ６）アルキニルオキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ２－Ｃ６）アルケニルチオ、（Ｃ２－Ｃ６）アルキニルチオ、（Ｃ３－Ｃ６）シクロアルキルチオ、（Ｃ１－Ｃ６）アルキルアミノ、（Ｃ２－Ｃ６）アルケニルアミノ、（Ｃ２－Ｃ６）アルキニルアミノ、ジ（Ｃ１－Ｃ６）アルキルアミノ、ジ（Ｃ２－Ｃ６）アルケニルアミノ、ジ（Ｃ２－Ｃ６）アルキニルアミノ、（Ｃ１－Ｃ６）アルキルスルフィニル、（Ｃ２－Ｃ６）アルケニルスルフィニル、（Ｃ２－Ｃ６）アルキニルスルフィニル、（Ｃ１－Ｃ６）アルキルスルホニル、（Ｃ２－Ｃ６）アルケニルスルホニル、（Ｃ２－Ｃ６）アルキニルスルホニル、（Ｃ１－Ｃ６）アルキルオキシ（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルキルチオ（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルキルアミノ（Ｃ１－Ｃ６）アルキル、ジ（Ｃ１－Ｃ６）アルキルアミノ（Ｃ１－Ｃ６）アルキル、ホルミル、（Ｃ１－Ｃ６アルキル）カルボニル、（Ｃ１－Ｃ６アルコキシ）カルボニル、（Ｃ１－Ｃ６アルキル）アミノカルボニル、ジ（Ｃ１－Ｃ６アルキル）アミノカルボニル、（Ｃ１－Ｃ６アルキル）カルボニルオキシ、（Ｃ１－Ｃ６アルキル）カルボニルチオ、（Ｃ１－Ｃ６アルキル）カルボニルアミノ又はジ（Ｃ１－Ｃ６アルキル）カルボニルアミノであり；ｎは０～５の整数であり；ｎが２以上のとき、複数のＲ１は同一又は異なっていてもよい〕で表される４－（フェニルエテニル）ピリジン系化合物又はその塩、該化合物又はその塩を有効成分として含有する有害生物防除剤、該化合物又はその塩の有効量を施用して有害生物を防除する方法、該化合物又はその塩の製造方法、並びに該化合物の製造用中間体である式（ＩＩ）： [Wherein R 1 is a halogen atom, cyano, nitro, (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl] , (C 1 -C 6 ) haloalkyl, (C 1 -C 6 ) alkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 3 -C 6 ) cycloalkoxy, ( C 1 -C 6 ) haloalkoxy, (C 1 -C 6 ) alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, (C 3 -C 6 ) cycloalkylthio, (C 1- C 6 ) haloalkylthio, (C 1 -C 6 ) alkylamino, (C 2 -C 6 ) alkenylamino, (C 2 -C 6 ) alkynylamino, di (C 1 -C 6 ) alkylamino, di ( 2 -C 6) alkenyl, di (C 2 -C 6) alkynyl amino, (C 1 -C 6) alkylsulfinyl, (C 2 -C 6) alkenylsulfinyl, (C 2 -C 6) alkynylsulfinyl, ( C 3 -C 6) cycloalkyl alkylsulfinyl, (C 1 -C 6) haloalkylsulfinyl, (C 1 -C 6) alkylsulfonyl, (C 2 -C 6) alkenyl-sulfonyl, (C 2 -C 6) alkynyl-sulfonyl, (C 1 -C 6 alkyl) carbonyl, (C 1 -C 6 alkyl) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, (C 1 -C 6 alkyl) ) carbonyloxy, (C 1 -C 6 alkyl) carbonylamino or (C 1 -C 6 alkyl) carboxamide There Le (C 1 -C 6) alkylamino; R 2 is a halogen atom, cyano, nitro, (C 1 -C 6) alkyl, (C 2 -C 6) alkenyl, (C 2 -C 6) alkynyl, (C 1 -C 6 ) haloalkyl, (C 1 -C 6 ) alkoxy, (C 3 -C 6 ) cycloalkoxy, (C 1 -C 6 ) haloalkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 1 -C 6 ) alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, (C 3 -C 6 ) cycloalkylthio, (C 1 -C 6) alkylamino, (C 2 -C 6) alkenyl amino, (C 2 -C 6) alkynyl amino, di (C 1 -C 6) alkylamino, di (C 2 -C 6) alkenyl, di C 2 -C 6) alkynyl amino, (C 1 -C 6) alkylsulfinyl, (C 2 -C 6) alkenylsulfinyl, (C 2 -C 6) alkynylsulfinyl, (C 1 -C 6) alkylsulfonyl, ( C 2 -C 6 ) alkenylsulfonyl, (C 2 -C 6 ) alkynylsulfonyl, (C 1 -C 6 ) alkyloxy (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkylthio (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkylamino (C 1 -C 6 ) alkyl, di (C 1 -C 6 ) alkylamino (C 1 -C 6 ) alkyl, formyl, (C 1 -C 6 alkyl) ) carbonyl, (C 1 -C 6 alkoxy) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl (C 1 -C 6 alkyl) carbonyloxy, be (C 1 -C 6 alkyl) carbonyl thio, (C 1 -C 6 alkyl) carbonylamino or di (C 1 -C 6 alkyl) carbonylamino; n is 0 A 4- (phenylethenyl) pyridine compound or a salt thereof, or a compound or a salt thereof, wherein n is an integer of 2 or more; and when n is 2 or more, a plurality of R 1 may be the same or different As an active ingredient, a method for controlling pests by applying an effective amount of the compound or a salt thereof, a method for producing the compound or a salt thereof, and a formula which is an intermediate for producing the compound (II):
Figure JPOXMLDOC01-appb-C000006
 〔式中、Ｒ１、Ｒ２及びｎは前述の定義通りである〕で表される化合物又はその塩に関する。
Figure JPOXMLDOC01-appb-C000006
 [Wherein R 1 , R 2 and n are as defined above] or a salt thereof.
　前記式（Ｉ）の化合物又はその塩を有効成分とする有害生物防除剤は、低薬量で有害生物に対して極めて高い防除効果を有する。 The pest control agent comprising the compound of the formula (I) or a salt thereof as an active ingredient has a very high control effect against pests at a low dose.
　前記式（Ｉ）及び（ＩＩ）中のハロゲン原子又は置換基としてのハロゲンとしては、例えば、フッ素、塩素、臭素又はヨウ素の各原子が挙げられる。置換基としてのハロゲン原子の数は１又は２以上であってよく、２以上の場合、各ハロゲン原子は同一でも相異なってもよい。また、ハロゲン原子の置換位置は何れの位置でもよい。 Examples of the halogen atom in the formulas (I) and (II) or the halogen as a substituent include each atom of fluorine, chlorine, bromine or iodine. The number of halogen atoms as a substituent may be 1 or 2 or more, and in the case of 2 or more, each halogen atom may be the same or different. Further, the halogen atom may be substituted at any position.
　前記式（Ｉ）及び（ＩＩ）中のアルキル又はアルキル部分としては、例えば、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、セカンダリーブチル、ターシャリーブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、ネオヘキシルのような直鎖又は分岐鎖状のＣ１－Ｃ６の基が挙げられる。 Examples of the alkyl or alkyl moiety in the formulas (I) and (II) include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, and normal hexyl. And linear or branched C 1 -C 6 groups such as neohexyl.
　本明細書中、「ターシャリー」を「ｔｅｒｔ-」と表記する場合がある。 In this specification, “tertiary” may be written as “tert-”.
　前記式（Ｉ）及び（ＩＩ）中のアルケニル又はアルケニル部分としては、例えば、ビニル、１－プロペニル、２－プロペニル、イソプロペニル、２－メチル－１－プロペニル、１－メチル－１－プロペニル、２－メチル－２－プロペニル、１－メチル－２－プロペニル、１－ブテニル、２－ブテニル、３－ブテニル、１－ペンテニル、２－ペンテニル、２－メチル－２－ブテニル、１－ヘキセニル、２,３－ジメチル－２－ブテニルのような直鎖又は分岐鎖状のＣ２－Ｃ６の基が挙げられる。 Examples of the alkenyl or alkenyl moiety in the formulas (I) and (II) include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl, 2 -Methyl-2-propenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-2-butenyl, 1-hexenyl, 2,3 And straight-chain or branched C 2 -C 6 groups such as -dimethyl-2-butenyl.
　前記式（Ｉ）及び（ＩＩ）中のアルキニル又はアルキニル部分としては、例えば、エチニル、１－プロピニル、２－プロピニル、１－ブチニル、２－ブチニル、３－ブチニル、１－メチル－２－プロピニル、２－メチル－３－ブチニル、３，３－ジメチル－１－ブチニル、１－ヘキシニル、２－ヘキシニル、３－ヘキシニル、４－ヘキシニル、５－ヘキシニルのような直鎖又は分岐鎖状のＣ２－Ｃ６の基が挙げられる。 Examples of the alkynyl or alkynyl moiety in the formulas (I) and (II) include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, Linear or branched C 2 − such as 2-methyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl C 6 group may be mentioned.
　前記式（Ｉ）及び（ＩＩ）中のシクロアルキル又はシクロアルキル部分としては、例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシルのようなＣ３－Ｃ６の基が挙げられる。 Examples of the cycloalkyl or cycloalkyl moiety in the formulas (I) and (II) include C 3 -C 6 groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
　前記式（Ｉ）及び（ＩＩ）の化合物の塩としては、当該技術分野で許容されるものであればあらゆるものが含まれるが、例えば、ジメチルアンモニウム塩、トリエチルアンモニウム塩のようなアンモニウム塩；塩酸塩、過塩素酸塩、硫酸塩、硝酸塩のような無機酸塩；酢酸塩、トリフルオロ酢酸塩、シュウ酸塩、ｐ－トルエンスルホン酸塩、メタンスルホン酸塩のような有機酸塩などが挙げられる。 The salts of the compounds of the formulas (I) and (II) include any salt that is acceptable in the art, for example, ammonium salts such as dimethylammonium salt and triethylammonium salt; hydrochloric acid Inorganic salts such as salts, perchlorates, sulfates, nitrates; organic acid salts such as acetates, trifluoroacetates, oxalates, p-toluenesulfonates, methanesulfonates, etc. It is done.
　前記式（Ｉ）及び（ＩＩ）の化合物又はその塩には、光学異性体のような異性体が存在する場合があるが、本発明には各異性体及び異性体混合物の双方が含まれる。本願明細書においては、特に言及しない限り、異性体は混合物として記載する。尚、本発明には、当該技術分野における技術常識の範囲内において、前記したもの以外の各種異性体も含まれる。また、異性体の種類によっては、前記一般式（Ｉ）とは異なる化学構造となる場合があるが、当業者であればそれらが異性体の関係にあることが十分認識できる為、本発明の範囲内であることは明らかである。 In the compounds of the formulas (I) and (II) or salts thereof, there may be isomers such as optical isomers, but the present invention includes both isomers and isomer mixtures. In the present specification, unless otherwise specified, isomers are described as a mixture. The present invention also includes various isomers other than those described above within the scope of technical common sense in the technical field. In addition, depending on the type of isomer, the chemical structure may be different from that of the general formula (I). However, since those skilled in the art can sufficiently recognize that they are related to isomers, Obviously, it is within range.
　前記式（Ｉ）の化合物又はその塩（以下、本発明化合物と略す）は、以下の製造方法、並びに通常の塩の製造方法に従って製造することができるが、これらの方法に限定されるものではない。 The compound of the above formula (I) or a salt thereof (hereinafter abbreviated as the compound of the present invention) can be produced according to the following production methods and ordinary salt production methods, but is not limited to these methods. Absent.
製法〔１〕
　本発明化合物は、式（ＩＩ）の化合物又はその塩と塩素化剤を、塩基の存在下で、反応させることにより製造できる。 Manufacturing method [1]
The compound of the present invention can be produced by reacting the compound of formula (II) or a salt thereof with a chlorinating agent in the presence of a base.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
〔式中、Ｒ１、Ｒ２及びｎは前述の定義通りである〕 [Wherein R 1 , R 2 and n are as defined above]
　本反応は、必要に応じて溶媒の存在下で行うことができる。溶媒としては反応に不活性な溶媒であればいずれのものでもよく、例えば、ベンゼン、トルエン、キシレンのような芳香族炭化水素類；ジメチルアニリン、ジエチルアニリンのようなＮ，Ｎ－ジ置換アニリン；などから１種又は２種以上を適宜選択、混合して使用することができる。反応温度は通常０℃～１８０、好ましくは２０～１２０℃の範囲で行うことができる。反応時間は、通常数分～２４時間で行うことができる。 This reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; N, N-disubstituted anilines such as dimethylaniline and diethylaniline; 1 type (s) or 2 or more types can be selected and mixed appropriately from the above. The reaction temperature is usually 0 ° C. to 180 ° C., preferably 20 ° C. to 120 ° C. The reaction time is usually several minutes to 24 hours.
　塩素化剤としては、例えば、塩化チオニル、５塩化リン、オキシ塩化リン、３塩化リン等が挙げられる。塩素化剤は式（ＩＩ）の化合物に対して、通常１倍モル以上、好ましくは１～３倍モル使用する。 Examples of the chlorinating agent include thionyl chloride, phosphorus pentachloride, phosphorus oxychloride, phosphorus trichloride and the like. The chlorinating agent is used in an amount of usually 1 mol or more, preferably 1 to 3 mol per mol of the compound of formula (II).
　塩基としては、例えば、水酸化ナトリウム、水酸化カリウムなどのようなアルカリ金属の水酸化物；炭酸ナトリウム、炭酸カリウムなどのようなアルカリ金属の炭酸塩；水素化ナトリウム、水素化カリウム、水素化リチウムのようなアルカリ金属の水素化物；ナトリウムメトキシド、ナトリウムエトキシドのようなアルコキシド類；トリエチルアミン、ピリジン、ジイソプロピルエチルアミンのような第３級アミン類などが挙げられるが、第３級アミン類を使用するのが好ましい。塩基は式（ＩＩ）の化合物に対して、通常１倍モル以上、好ましくは１～３倍モル使用する。 Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium hydride, potassium hydride and lithium hydride. Alkoxides such as sodium methoxide and sodium ethoxide; tertiary amines such as triethylamine, pyridine and diisopropylethylamine, etc., and tertiary amines are used. Is preferred. The base is used in an amount of usually 1 mol or more, preferably 1 to 3 mol per mol of the compound of formula (II).
製法〔２〕
　前記一般式（Ｉ）中、Ｒ２がＳ（Ｏ）ｍＲ３である式（Ｉ－ｂ）の化合物は、式（Ｉ－ａ）の化合物と酸化剤とを反応させることにより製造することもできる。 Manufacturing method [2]
The compound of formula (Ib) in which R 2 is S (O) m R 3 in the general formula (I) is prepared by reacting the compound of formula (Ia) with an oxidizing agent. You can also.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
〔式中、Ｒ１及びｎは前述の定義通りであり、Ｒ３は（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル又は（Ｃ２－Ｃ６）アルキニルであり、ｍは１又は２である〕 [Wherein R 1 and n are as defined above, R 3 is (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl or (C 2 -C 6 ) alkynyl, and m is 1 or 2]
　酸化剤としては、例えば、３－クロロ過安息香酸のようなカルボン酸の過酸化物；過酸化水素水；などが挙げられる。溶媒としては、例えば、ジクロロメタン、クロロホルムのような脂肪族ハロゲン化炭化水素などが挙げられる。反応温度は、通常約－２０℃から使用する溶媒の沸点の範囲で行うことができる。反応時間は、通常数分～２４時間で行うことができる。 Examples of the oxidizing agent include peroxides of carboxylic acids such as 3-chloroperbenzoic acid; hydrogen peroxide water. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform. The reaction temperature can usually be in the range of about −20 ° C. to the boiling point of the solvent used. The reaction time is usually several minutes to 24 hours.
製法〔３〕
　前記一般式（Ｉ）中、Ｒ２が（Ｃ２－Ｃ６）アルキニルである式（Ｉ－ｄ）の化合物は、式（Ｉ－ｃ）の化合物と（Ｃ２－Ｃ６）アルキンを、パラジウム触媒、銅塩及び塩基の存在下で反応させることにより製造することもできる。 Manufacturing method [3]
In the general formula (I), the compound of formula (Id) in which R 2 is (C 2 -C 6 ) alkynyl is obtained by combining the compound of formula (Ic) with (C 2 -C 6 ) alkyne. It can also be produced by reacting in the presence of a palladium catalyst, a copper salt and a base.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
〔式中、Ｒ１及びｎは前述の定義通り、Ｘはハロゲン原子であり、Ｒ２ａは（Ｃ２－Ｃ６）アルキニルである〕 [Wherein, R 1 and n are as defined above, X is a halogen atom, and R 2a is (C 2 -C 6 ) alkynyl]
　パラジウム触媒としては、例えば、二塩化ビストリフェニルトリフェニルホスフィンパラジウム、テトラキス（トリフェニルホスフィン）パラジウム（０）、ビス（ジベンジリデンアセトン）パラジウム（０）、トリス（ジベンジリデンアセトン）ジパラジウム（０）などが挙げられる。銅塩としては、例えば、ヨウ化銅（Ｉ）などが挙げられる。 Examples of the palladium catalyst include bistriphenyltriphenylphosphine palladium dichloride, tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), tris (dibenzylideneacetone) dipalladium (0), and the like. Is mentioned. Examples of the copper salt include copper (I) iodide.
　塩基は、有機塩基でも無機塩基でもよい。有機塩基としては、例えばトリエチルアミン、ジイソプロピルアミンのようなアミン塩基などが挙げられる。無機塩基としては、例えば、炭酸ナトリウム、炭酸カリウム、炭酸セシウムのようなアルカリ金属炭酸塩などが挙げられる。 The base may be an organic base or an inorganic base. Examples of the organic base include amine bases such as triethylamine and diisopropylamine. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate.
　該反応は、必要に応じて溶媒の存在下で行うことができる。溶媒は、反応に不活性な溶媒であればいずれのものでもよく、例えば、トリエチルアミン、ジイソプロピルアミンのようなアミン塩基；Ｎ，Ｎ－ジメチルホルムアミド、アセトニトリルのような非プロトン性極性溶媒；テトラヒドロフランのようなエーテル類；などから１種又は２種以上を適宜選択することができる。反応温度は、通常約２０℃から反応混合物が還流する温度で行うことができる。反応時間は、通常数分～２４時間で行うことができる。 The reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. For example, an amine base such as triethylamine or diisopropylamine; an aprotic polar solvent such as N, N-dimethylformamide or acetonitrile; 1 type or 2 types or more can be suitably selected from such ethers; The reaction temperature can usually be about 20 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time is usually several minutes to 24 hours.
中間体製法〔１〕
　前記した式（ＩＩ）の化合物は、塩基の存在下、式（ＩＩＩ）の化合物と、式（ＩＶ）の化合物を反応させることにより製造できる。 Intermediate production method [1]
The compound of the above formula (II) can be produced by reacting the compound of the formula (III) with the compound of the formula (IV) in the presence of a base.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
〔式中、Ｍｅはメチルであり、Ｒ１、Ｒ２、Ｒ３及びｎは前述の定義通りである〕 [Wherein Me is methyl and R 1 , R 2 , R 3 and n are as defined above]
　該反応は、必要に応じて溶媒の存在下で行うことができる。溶媒としては、反応に不活性な溶媒であればいずれのものでもよく、例えば、ジエチルエーテル、テトラヒドロフラン、エチレングリコールジメチルエーテル、１，４－ジオキサンのようなエーテル類などから１種又は２種以上を適宜選択、混合して使用することができる。反応温度は、通常約－２０℃から使用する溶媒の沸点の範囲で行うことができる。反応時間は、通常数分～４８時間で行うことができる。 The reaction can be performed in the presence of a solvent, if necessary. As the solvent, any solvent may be used as long as it is inert to the reaction. For example, one or two or more kinds of ethers such as diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, and 1,4-dioxane are appropriately used. Can be selected and mixed for use. The reaction temperature can usually be in the range of about −20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 48 hours.
　塩基としては、例えば、リチウムビス（トリメチルシリル）アミド、ナトリウムビス（トリメチルシリル）アミド、カリウムビス（トリメチルシリル）アミド、リチウムジ（イソプロピル）アミドのようなアルカリ金属アミドなどが挙げられる。 Examples of the base include alkali metal amides such as lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, and lithium di (isopropyl) amide.
中間体製法〔２〕
　前記一般式（ＩＩＩ）中、Ｒ２がＯＲ４である式（ＩＩＩ－ａ）の化合物は、３-アミノ－４－メチルピリジンを、Ｒ４ＯＨ中、酸の存在下で、亜硝酸エステルと反応させた後、塩基を加えることにより製造できる。 Intermediate production method [2]
In the general formula (III), a compound of the formula (III-a) in which R 2 is OR 4 is obtained by reacting 3-amino-4-methylpyridine with a nitrite in R 4 OH in the presence of an acid. It can be manufactured by adding a base after the reaction.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
〔式中、Ｍｅはメチルであり、Ｒ４は（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ３－Ｃ６）シクロアルキル又は（Ｃ１－Ｃ６）ハロアルキルである〕 [Wherein Me is methyl and R 4 is (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl or (C 1 -C 6 ) haloalkyl]
　該反応は、必要に応じて溶媒の存在下で行うことができる。溶媒としては反応に不活性な溶媒であればいずれのものでもよく、例えば、アセトニトリル、ジオキサンのような非プロトン性極性溶媒；水；などから１種又は２種以上を適宜選択、混合して使用することができる。反応温度は、通常約室温から反応混合物が還流する温度の範囲で行うことができる。反応時間は、通常数分～４８時間で行うことができる。 The reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, one or more aprotic polar solvents such as acetonitrile and dioxane; water; can do. The reaction temperature can be generally in the range of about room temperature to the temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 48 hours.
　酸としては、例えば、塩酸、硫酸などのような無機酸；メタンスルホン酸などのような有機酸などが挙げられる。亜硝酸エステルとしては、例えば、亜硝酸イソプロピル、亜硝酸ｔｅｒｔ－ブチルなどが挙げられる。塩基としては、例えば、炭酸ナトリウム、炭酸カリウムなどのようなアルカリ金属の炭酸塩；炭酸水素ナトリウム、炭酸水素カリウムなどのようなアルカリ金属の炭酸水素塩；ナトリウムメトキシド、ナトリウムエトキシドのようなアルコキシド類などが挙げられる。 Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid; and organic acids such as methanesulfonic acid. Examples of the nitrite include isopropyl nitrite and tert-butyl nitrite. Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkoxides such as sodium methoxide and sodium ethoxide And the like.
中間体製法〔３〕
　前記一般式（ＩＩＩ）中、Ｒ２がＳＲ４である式（ＩＩＩ－ｂ）の化合物は、３－アミノ－４－メチルピリジンを、無機亜硝酸塩又は亜硝酸エステルと反応させてジアゾニウム化合物とした後、Ｒ４ＳＨ又は（Ｒ４Ｓ）２を反応させるザンドマイヤー（Ｓａｎｄｍｅｙｅｒ）反応により、製造できる。 Intermediate production method [3]
In the general formula (III), the compound of the formula (III-b) in which R 2 is SR 4 is a diazonium compound obtained by reacting 3-amino-4-methylpyridine with an inorganic nitrite or nitrite. Thereafter, it can be produced by a Sandmeyer reaction in which R 4 SH or (R 4 S) 2 is reacted.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
〔式中、Ｍｅはメチルであり、Ｒ４は前述の定義通りである〕 [Wherein Me is methyl and R 4 is as defined above]
　無機亜硝酸塩としては、例えば、亜硝酸ナトリウム、亜硝酸カリウムなどが挙げられる。亜硝酸エステルとしては、例えば、亜硝酸ｔｅｒｔ－ブチル、亜硝酸イソアミルなどが挙げられる。 Examples of inorganic nitrites include sodium nitrite and potassium nitrite. Examples of the nitrite include tert-butyl nitrite and isoamyl nitrite.
　該反応は、必要に応じて銅触媒の存在下で行うことができる。銅触媒としては、例えば、酸化銅（Ｉ）、硫酸銅（ＩＩ）五水和物などが挙げられる。 The reaction can be carried out in the presence of a copper catalyst as necessary. Examples of the copper catalyst include copper (I) oxide and copper (II) sulfate pentahydrate.
　該反応は、必要に応じて酸の存在下で行うことができる。酸としては、例えば、塩酸、硫酸のような無機酸；酢酸、メタンスルホン酸のような有機酸；などが挙げられる。 The reaction can be performed in the presence of an acid, if necessary. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as acetic acid and methanesulfonic acid; and the like.
　該反応は、必要に応じて塩基の存在下で行うことができる。塩基としては、例えば、水素化ナトリウムのようなアルカリ金属水素化物；炭酸ナトリウム、炭酸カリウム、炭酸セシウムのようなアルカリ金属炭酸塩；水酸化リチウム、水酸化ナトリウム、水酸化カリウムのようなアルカリ金属水酸化物；などが挙げられる。 The reaction can be performed in the presence of a base as necessary. Examples of the base include alkali metal hydrides such as sodium hydride; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal water such as lithium hydroxide, sodium hydroxide and potassium hydroxide. Oxides; and the like.
　該反応は、必要に応じて溶媒の存在下で行うことができる。溶媒としては、例えば、ジクロロメタン、クロロホルムのような脂肪族ハロゲン化炭化水素類；トルエン、キシレンのような芳香族炭化水素類；アセトニトリル、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシドのような非プロトン性極性溶媒；水；などから１種又は２種以上を適宜選択することができる。 The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene and xylene; aprotic polarities such as acetonitrile, N, N-dimethylformamide and dimethyl sulfoxide. One type or two or more types can be appropriately selected from a solvent, water, and the like.
　反応温度は通常－２０℃～２００℃の範囲で行うことができる。反応時間は、通常数分～２４時間で行うことができる。 The reaction temperature can usually be in the range of −20 ° C. to 200 ° C. The reaction time is usually several minutes to 24 hours.
中間体製法〔４〕
　前記一般式（ＩＩＩ）中、Ｒ２がＸである式（ＩＩＩ－ｃ）の化合物は、３－アミノ－４－メチルピリジンを、無機亜硝酸塩又は亜硝酸エステルと反応させてジアゾニウム塩とした後、ハロゲン化剤を反応させるザンドマイヤー（Ｓａｎｄｍｅｙｅｒ）反応により、製造できる。 Intermediate production method [4]
In the general formula (III), the compound of the formula (III-c) in which R 2 is X is obtained by reacting 3-amino-4-methylpyridine with an inorganic nitrite or a nitrite to form a diazonium salt. , By a Sandmeyer reaction in which a halogenating agent is reacted.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
〔式中、Ｍｅはメチルであり、Ｘはハロゲン原子である〕 [Wherein Me is methyl and X is a halogen atom]
　無機亜硝酸塩及び亜硝酸エステルとしては、前記中間体製法〔３〕と同様のものが挙げられる。ハロゲン化剤としては、例えば、塩素、臭素、ヨウ素等のハロゲン；塩酸、臭化水素酸、ヨウ化水素酸等のハロゲン化水素酸；塩化銅（Ｉ）、臭化銅（Ｉ）、ヨウ化銅（Ｉ）等のハロゲン化銅（Ｉ）；塩化銅（ＩＩ）、臭化銅（ＩＩ）等のハロゲン化銅（ＩＩ）；テトラフルオロホウ酸；ヨウ化カリウム；などが挙げられる。 Examples of inorganic nitrites and nitrites include those similar to the intermediate production method [3]. Examples of the halogenating agent include halogens such as chlorine, bromine and iodine; hydrohalic acids such as hydrochloric acid, hydrobromic acid and hydroiodic acid; copper (I) chloride, copper (I) bromide and iodide Examples thereof include copper (I) halides such as copper (I); copper (II) halides such as copper (II) chloride and copper (II) bromide; tetrafluoroboric acid; potassium iodide;
　該反応は必要に応じて銅触媒の存在下で行うことができる。銅触媒としては、例えば、前記したハロゲン化銅（Ｉ）、ハロゲン化銅（ＩＩ）、酸化銅（Ｉ）、硫酸銅（ＩＩ）五水和物などが挙げられる。 The reaction can be carried out in the presence of a copper catalyst as necessary. Examples of the copper catalyst include the aforementioned copper (I) halide, copper (II) halide, copper (I) oxide, copper (II) sulfate pentahydrate and the like.
　該反応は、必要に応じて酸の存在下で行うことができる。酸としては、例えば、前記に挙げたハロゲン化水素酸、硫酸等の無機酸；酢酸、メタンスルホン酸、ｐ－トルエンスルホン酸等の有機酸；などが挙げられる。 The reaction can be performed in the presence of an acid, if necessary. Examples of the acid include inorganic acids such as the above-mentioned hydrohalic acids and sulfuric acids; organic acids such as acetic acid, methanesulfonic acid, and p-toluenesulfonic acid.
　該反応は、必要に応じて溶媒の存在下で行うことができる。溶媒としては、例えば、前記中間体製法〔３〕と同様のものが挙げられ、これらの１種又は２種以上を適宜選択、混合して使用することができる。 The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include those similar to the intermediate production method [3], and one or more of these can be appropriately selected and mixed for use.
　反応温度は通常－２０℃～２００℃の範囲で行うことができる。反応時間は、通常数分～２４時間で行うことができる。 The reaction temperature can usually be in the range of −20 ° C. to 200 ° C. The reaction time is usually several minutes to 24 hours.
　本発明化合物を含有する有害生物防除剤の好ましい態様について以下に記述する。本発明化合物を含有する有害生物防除剤は、例えば農園芸分野で問題となる害虫、ダニ、線虫又は土壌害虫の防除剤、即ち農園芸用殺虫剤、中でも、殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤として有用である。また、動物寄生生物の防除剤、即ち殺動物寄生生物剤として有用である。 Preferred embodiments of the pest control agent containing the compound of the present invention are described below. The pest control agent containing the compound of the present invention includes, for example, pests, mites, nematodes or soil pests that are problematic in the field of agriculture and horticulture, that is, agricultural and horticultural insecticides, among them insecticides, acaricides, It is useful as a nematode or soil killing pest. It is also useful as an animal parasite control agent, that is, an animal killing parasite agent.
　本発明化合物は、殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤として有用であるが、具体的には、例えば、モモアカアブラムシ、ワタアブラムシ等のようなアブラムシ類；コナガ、ヨトウムシ、ハスモンヨトウ、コドリンガ、ボールワーム、タバコバッドワーム、マイマイガ、コブノメイガ、チャノコカクモンハマキ、コロラドハムシ、ウリハムシ、ボールウィービル、ウンカ類、ヨコバイ類、カイガラムシ類、カメムシ類、コナジラミ類、アザミウマ類、バッタ類、ハナバエ類、コガネムシ類、タマナヤガ、カブラヤガ、アリ類等のような農業害虫類；ナメクジ、マイマイ等のような腹足類；イエダニ、ゴキブリ類、イエバエ、アカイエカ等のような衛生害虫類；バクガ、アズキゾウムシ、コクヌストモドキ、ゴミムシダマシ類等のような貯穀害虫類；イガ、ヒメカツオブシムシ、シロアリ類等のような衣類、家屋害虫類；等の害虫、ナミハダニ、ニセナミハダニ、カンザワハダニ、ミカンハダニ、リンゴハダニ、チャノホコリダニ、ミカンサビダニ、ネダニ等のような植物寄生性ダニ類；ケナガコナダニ、コナヒョウダニ、ミナミツメダニ等のような屋内塵性ダニ類；等のダニ、ネコブセンチュウ類、シストセンチュウ類、ネグサレセンチュウ類、イネシンガレセンチュウ、イチゴメセンチュウ、マツノザイセンチュウ等のような植物寄生性線虫類；等の線虫、ダンゴムシ、ワラジムシのような等脚類；等の土壌害虫の防除に有効である。 The compounds of the present invention are useful as insecticides, acaricides, nematicides or soil pesticides. Specifically, for example, aphids such as peach aphids, cotton aphids, etc .; Spodoptera moth, Codling moth, Ball worm, Tobacco bud worm, Potato moth, Prunus serrata, Chanocokakumon angi, Colorado potato beetle, cucumber potato beetle, ball weevil, planthopper, leafhopper, scale insect, stink bug, whitefly, thrips, grasshopper Agricultural pests such as tree flies, scarab beetles, tamanayaga, kaburayaga, ants, etc .; gastropods such as slugs, maimai, etc .; sanitary pests such as house dust mites, cockroaches, house flies, mosquitoes, etc .; , Kokunusutomodoki, worms, etc. Pests of cereals; clothing such as moths, swordworms, termites, etc., pests such as house pests; Mites; indoor dust mites such as Scarlet mite, Scarlet mite, southern ticks, etc .; such as mites, root-knot nematodes, cyst nematodes, nestle nematodes, rice nesting nematodes, strawberry nematodes, pine wood nematodes, etc. It is effective for the control of soil pests such as nematodes such as plant parasitic nematodes;
　本発明化合物を含有する殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤は、植物寄生性ダニ類、農業害虫類、植物寄生性線虫類等の防除に特に有効である。その中でも、植物寄生性ダニ類、農業害虫類の防除にさらに優れた効果を示すため、殺虫剤又は殺ダニ剤として非常に有用である。 The insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is particularly effective for controlling plant parasitic mites, agricultural pests, plant parasitic nematodes and the like. Among them, it is very useful as an insecticide or acaricide because it shows a further excellent effect in controlling plant parasitic mites and agricultural pests.
　また、本発明化合物を含有する殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤は、有機リン剤、カーバメート剤、合成ピレスロイド剤、ネオニコチノイド剤等の薬剤に対する各種抵抗性害虫の防除にも有効である。 In addition, the insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is an organic phosphorus agent, carbamate agent, synthetic pyrethroid agent, neonicotinoid agent and other various resistant insect pests. It is also effective for control.
　さらに本発明化合物は、優れた浸透移行性を有していることから、本発明化合物を含有する殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤を土壌に処理することによって土壌有害昆虫類、ダニ類、線虫類、腹脚類、等脚類の防除と同時に茎葉部の害虫類をも防除することができる。 Furthermore, since the compound of the present invention has an excellent osmotic transfer property, it can be harmful to soil by treating the soil with an insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention. At the same time as controlling insects, mites, nematodes, gastropods, isopodaes, it is possible to control pests on the foliage.
　本発明化合物を含有する殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤の別の好ましい態様としては、前記した植物寄生性ダニ類、農業害虫類、植物寄生性線虫類、腹足類、土壌害虫類等を総合的に防除する殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤が挙げられる。 As another preferred embodiment of the insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention, the aforementioned plant parasitic mites, agricultural pests, plant parasitic nematodes, gastropods Insecticides, acaricides, nematicides or soil pesticides that comprehensively control soil pests and the like.
　本発明化合物を含有する殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤は、通常、該化合物と各種農業上の補助剤とを混合して粉剤、粒剤、顆粒水和剤、水和剤、水性懸濁剤、油性懸濁剤、顆粒水溶剤、水溶剤、乳剤、液剤、ペースト剤、エアゾール剤、微量散布剤等の種々の形態に製剤して使用されるが、本発明の目的に適合するかぎり、通常の当該分野で用いられているあらゆる製剤形態にすることができる。 Insecticides, acaricides, nematicides or soil pesticides containing the compound of the present invention are usually powders, granules, granule wettable powders by mixing the compound with various agricultural adjuvants, It can be used in various forms such as wettable powder, aqueous suspension, oil suspension, granular aqueous solvent, aqueous solvent, emulsion, liquid, paste, aerosol, microdispersant, etc. As long as it fits the purpose of the present invention, it can be in any formulation form commonly used in the art.
　製剤に使用する補助剤としては、例えば、珪藻土、消石灰、炭酸カルシウム、タルク、ホワイトカーボン、カオリン、ベントナイト、カオリナイト、セリサイト、クレー、炭酸ナトリウム、重曹、芒硝、ゼオライト、澱粉等の固型担体；水、トルエン、キシレン、ソルベントナフサ、ジオキサン、アセトン、イソホロン、メチルイソブチルケトン、クロロベンゼン、シクロヘキサン、ジメチルスルホキシド、Ｎ,Ｎ－ジメチルホルムアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、アルコール等の溶剤；脂肪酸塩、安息香酸塩、アルキルスルホコハク酸塩、ジアルキルスルホコハク酸塩、ポリカルボン酸塩、アルキル硫酸エステル塩、アルキル硫酸塩、アルキルアリール硫酸塩、アルキルジグリコールエーテル硫酸塩、アルコール硫酸エステル塩、アルキルスルホン酸塩、アルキルアリールスルホン酸塩、アリールスルホン酸塩、リグニンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、ポリスチレンスルホン酸塩、アルキルリン酸エステル塩、アルキルアリールリン酸塩、スチリルアリールリン酸塩、ポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンアルキルアリールエーテル硫酸塩、ポリオキシエチレンアルキルアリールエーテル硫酸エステル塩、ポリオキシエチレンアルキルエーテルリン酸塩、ポリオキシエチレンアルキルアリールリン酸エステル塩、ナフタレンスルホン酸塩ホルムアルデヒド縮合物のような陰イオン系の界面活性剤；ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、脂肪酸ポリグリセライド、脂肪酸アルコールポリグリコールエーテル、アセチレングリコール、アセチレンアルコール、オキシアルキレンブロックポリマー、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンスチリルアリールエーテル、ポリオキシエチレングリコールアルキルエーテル、ポリエチレングリコール、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油、ポリオキシプロピレン脂肪酸エステルのような非イオン系の界面活性剤；オリーブ油、カポック油、ひまし油、シュロ油、椿油、ヤシ油、ごま油、トウモロコシ油、米ぬか油、落花生油、綿実油、大豆油、菜種油、亜麻仁油、きり油、液状パラフィン等の植物油や鉱物油；等が挙げられる。これら補助剤の各成分は、本発明の目的から逸脱しないかぎり、１種又は２種以上を適宜選択して使用することができる。 Examples of adjuvants used in the preparation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, and starch. Water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, alcohol Solvents such as: fatty acid salts, benzoates, alkylsulfosuccinates, dialkylsulfosuccinates, polycarboxylates, alkylsulfate esters, alkylsulfates, alkylarylsulfates, alkyldiglycol ether sulfates Alcohol sulfate, alkyl sulfonate, alkyl aryl sulfonate, aryl sulfonate, lignin sulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate ester, alkyl aryl phosphate, styryl Aryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate Anionic surfactants such as salt, naphthalenesulfonate formaldehyde condensate; sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride Ride, fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, poly Nonionic surfactants such as oxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid ester; olive oil, kapok oil, castor oil, palm Oil, coconut oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, AsaHitoshiabura, tung oil, vegetable oil or mineral oil such as liquid paraffin; and the like. Each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention.
　また、前記した補助剤以外にも当該分野で知られたものの中から適宜選んで使用することもでき、例えば、増量剤、増粘剤、沈降防止剤、凍結防止剤、分散安定剤、薬害軽減剤、防黴剤等の通常使用される各種補助剤も使用することができる。本発明化合物と各種補助剤との配合割合（重量比）は一般に０．００１：９９．９９９～９５：５、好ましくは０．００５：９９．９９５～９０：１０である。これら製剤の実際の使用に際しては、そのまま使用するか、又は水等の希釈剤で所定濃度に希釈し、必要に応じて各種展着剤（例えば、界面活性剤、植物油、鉱物油等）を添加して使用することができる。 In addition to the above-mentioned adjuvants, it can be used by appropriately selecting from those known in the art. For example, a bulking agent, a thickening agent, an anti-settling agent, an antifreezing agent, a dispersion stabilizer, a phytotoxicity reduction. Various commonly used adjuvants such as agents and antifungal agents can also be used. The blending ratio (weight ratio) of the compound of the present invention and various adjuvants is generally 0.001: 99.999 to 95: 5, preferably 0.005: 99.995 to 90:10. In actual use of these preparations, use them as they are, or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (for example, surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.
　本発明化合物を含有する殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤の施用は、気象条件、製剤形態、施用時期、施用場所、病害虫の種類や発生状況等の相違により一概に規定できないが、一般に０．０５～８００，０００ｐｐｍ、好ましくは０．５～５００，０００ｐｐｍの有効成分濃度で行ない、その単位面積あたりの施用量は、１ヘクタール当り本発明化合物が一般に０．０５～５０，０００ｇ、好ましくは１～３０，０００ｇである。また、本発明には、このような施用方法による有害生物を防除する方法、例えば、害虫、ダニ、線虫又は土壌害虫の防除方法、特に植物寄生性ダニ類、農業害虫類、植物寄生性線虫類の防除方法も含まれる。 The application of the insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is generally based on differences in weather conditions, formulation form, application time, place of application, type of pests and occurrence, etc. Although it cannot be defined, it is generally carried out at an active ingredient concentration of 0.05 to 800,000 ppm, preferably 0.5 to 500,000 ppm. The application amount per unit area is generally 0.05 to 800 ppm of the compound of the present invention per hectare. 50,000 g, preferably 1 to 30,000 g. Further, the present invention includes a method for controlling pests by such an application method, for example, a method for controlling pests, mites, nematodes or soil pests, particularly plant parasitic mites, agricultural pests, plant parasitic lines. Insect control methods are also included.
　本発明化合物を含有する殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤の種々の製剤、又はその希釈物の施用は、通常、一般に行なわれている施用方法すなわち、散布（例えば、噴霧、ミスティング、アトマイジング、散粒、水面施用等）、土壌施用（例えば、混入、灌注等）、表面施用（例えば、塗布、粉衣、被覆等）、浸漬毒餌等により行うことができる。また、家畜に対して前記有効成分を飼料に混合して与え、その排泄物での有害虫、特に有害昆虫の発生及び生育を阻害することも可能である。また、いわゆる超高濃度少量散布法(ultra low volume application method)により施用することもできる。この方法においては、活性成分を１００％含有することが可能である。 Application of various preparations or dilutions of insecticides, acaricides, nematicides or soil insecticides containing the compounds of the present invention, or dilutions thereof, is usually a commonly used application method, ie spraying (for example, Spraying, misting, atomizing, dusting, water surface application, etc.), soil application (for example, mixing, irrigation, etc.), surface application (for example, application, powder coating, coating, etc.), immersion poison bait, etc. It is also possible to feed livestock with the above-mentioned active ingredient mixed with feed to inhibit the occurrence and growth of harmful insects, particularly harmful insects, in the excreta. It can also be applied by the so-called ultra-low volume application method. In this method, it is possible to contain 100% of the active ingredient.
　また、本発明化合物を含有する殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤は、他の農薬、肥料、薬害軽減剤等と混用或は併用することができ、この場合に一層優れた効果、作用性を示すことがある。 Further, the insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, safeners, etc. May show excellent effects and functionality.
　他の農薬としては、例えば、除草剤、殺虫剤、殺ダニ剤、殺線虫剤、殺土壌害虫剤、殺菌剤、抗ウイルス剤、誘引剤、抗生物質、植物ホルモン、植物成長調整剤、等が挙げられる。特に、本発明化合物と他の農薬の有効成分化合物の１種又は２種以上とを混用或は併用した殺虫用組成物、殺ダニ用組成物、殺線虫用組成物又は殺土壌害虫用組成物は、適用範囲、薬剤処理の時期、防除活性等を好ましい方向へ改良することが可能である。 Other pesticides include, for example, herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, etc. Is mentioned. In particular, an insecticidal composition, an acaricidal composition, a nematicidal composition or a composition for soil-killing insect pests in which the compound of the present invention and one or more active ingredient compounds of other agricultural chemicals are mixed or used in combination. The product can improve the application range, the timing of chemical treatment, the control activity, and the like in a preferable direction.
　尚、本発明化合物と他の農薬の有効成分化合物は各々別々に製剤したものを散布時に混合して使用しても、両者を一緒に製剤して使用してもよい。本発明には、このような殺虫用組成物、殺ダニ用組成物、殺線虫用組成物又は殺土壌害虫用組成物も含まれる。 In addition, the compound of the present invention and the other active ingredient compounds of other agricultural chemicals may be used separately by mixing them at the time of spraying or by using both together. The present invention includes such an insecticidal composition, an acaricidal composition, a nematicidal composition or a soil-killing insect pest composition.
　上記他の農薬中の、殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤の有効成分化合物（一般名；一部申請中を含む、又は日本植物防疫協会試験コード）としては、例えば、プロフェノホス（profenofos）、ジクロルボス（dichlorvos）、フェナミホス（fenamiphos）、フェニトロチオン（fenitrothion）、ＥＰＮ、ダイアジノン（diazinon）、クロルピリホス(chlorpyrifos)、クロルピリホスメチル（chlorpyrifos‐methyl）、アセフェート（acephate）、プロチオホス（prothiofos）、ホスチアゼート（fosthiazate）、カズサホス（cadusafos）、ジスルホトン（dislufoton）、イソキサチオン（isoxathion）、イソフェンホス(isofenphos)、エチオン(ethion)、エトリムホス(etrimfos)、キナルホス(quinalphos)、ジメチルビンホス(dimethylvinphos)、ジメトエート(dimethoate)、スルプロホス(sulprofos)、チオメトン(thiometon)、バミドチオン(vamidothion)、ピラクロホス(pyraclofos)、ピリダフェンチオン(pyridaphenthion)、ピリミホスメチル(pirimiphos-methyl)、プロパホス(propaphos)、ホサロン(phosalone)、ホルモチオン(formothion)、マラチオン(malathion)、テトラクロルビンホス(tetrachlorvinphos)、クロルフェンビンホス(chlorfenvinphos)、シアノホス(cyanophos)、トリクロルホン(trichlorfon)、メチダチオン(methidathion)、フェントエート(phenthoate)、ＥＳＰ、アジンホスメチル(azinphos-methyl)、フェンチオン(fenthion)、ヘプテノホス(heptenophos)、メトキシクロル（methoxychlor）、パラチオン（parathion）、ホスホカルブ(phosphocarb)、デメトン－Ｓ－メチル（demeton-S-methyl）、モノクロトホス（monocrotophos）、メタミドホス（methamidophos）、イミシアホス（imicyafos）、パラチオン－メチル（parathion-methyl）、テルブホス（terbufos）、ホスファミドン（phosphamidon）、ホスメット（phosmet）、ホレート（phorate）、ホキシム(phoxim)、トリアゾホス（triazophos）のような有機リン酸エステル系化合物；
　カルバリル（carbaryl）、プロポキスル（propoxur）、アルジカルブ（aldicarb）、カルボフラン（carbofuran）、チオジカルブ（thiodicarb）、メソミル（methomyl）、オキサミル（oxamyl）、エチオフェンカルブ（ethiofencarb）、ピリミカルブ（pirimicarb）、フェノブカルブ（fenobucarb）、カルボスルファン（carbosulfan）、ベンフラカルブ（benfuracarb）、ベンダイオカルブ（bendiocarb）、フラチオカルブ(furathiocarb)、イソプロカルブ(isoprocarb)、メトルカルブ(metolcarb)、キシリルカルブ(xylylcarb)、ＸＭＣ、フェノチオカルブ（fenothiocarb）のようなカーバメート系化合物；
　カルタップ（cartap）、チオシクラム（thiocyclam）、ベンスルタップ（bensultap）、チオスルタップナトリウム（thiosultap-sodium）、チオスルタップジナトリウム（thiosultap-disodium）、モノスルタップ（monosultap）、ビスルタップ（bisultap）、シュウ酸水素チオシクラム（thiocyclam hydrogen oxalate）のようなネライストキシン誘導体；
　ジコホル（dicofol）、テトラジホン（tetradifon）、エンドスルファン（endosulfan）、ジエノクロル（dienochlor）、ディルドリン（dieldrin）のような有機塩素系化合物；
　酸化フェンブタスズ（fenbutatin oxide）、シヘキサチン（cyhexatin）のような有機金属系化合物；
　フェンバレレート（fenvalerate）、ペルメトリン（permethrin）、シペルメトリン（cypermethrin）、デルタメトリン（deltamethrin）、シハロトリン（cyhalothrin）、テフルトリン（tefluthrin）、エトフェンプロックス（ethofenprox）、フルフェンプロックス（flufenprox）、シフルトリン（cyfluthrin）、フェンプロパトリン（fenpropathrin）、フルシトリネート（flucythrinate）、フルバリネート(fluvalinate)、シクロプロトリン（cycloprothrin）、ラムダシハロトリン(lambda-cyhalothrin)、ピレスリン（pyrethrins）、エスフェンバレレート（esfenvalerate）、テトラメスリン（tetramethrin）、レスメスリン（resmethrin）、プロトリフェンブト(protrifenbute)、ビフェントリン（bifenthrin）、ゼータシペルメトリン（zeta-cypermethrin）、アクリナトリン（acrinathrin）、アルファシペルメトリン（alpha-cypermethrin）、アレスリン（allethrin）、ガンマシハロトリン（gamma-cyhalothrin）、シータシペルメトリン（theta-cypermethrin）、タウフルバリネート（tau-fluvalinate）、トラロメスリン（tralomethrin）、プロフルスリン（profluthrin）、ベータシペルメトリン（beta-cypermethrin）、ベータシフルトリン（beta-cyfluthrin）、メトフルトリン（metofluthrin）、フェノトリン(phenothrin)、フルメトリン(flumethrin)、デカメトリン（decamethrin）のようなピレスロイド系化合物；
　ジフルベンズロン(diflubenzuron)、クロルフルアズロン(chlorfluazuron)、テフルベンズロン(teflubenzuron)、フルフェノクスロン(flufenoxuron)、トリフルムロン(triflumuron)、ヘキサフルムロン(hexaflumuron)、ルフェヌロン(lufenuron)、ノバルロン(novaluron)、ノビフルムロン（noviflumuron）、ビストリフルロン（bistrifluron）、フルアズロン（fluazuron）のようなベンゾイルウレア系化合物；
　メトプレン（methoprene）、ピリプロキシフェン（pyriproxyfen）、フェノキシカルブ（fenoxycarb）、ジオフェノラン（diofenolan）のような幼若ホルモン様化合物；
　ピリダベン（pyridaben）のようなピリダジノン系化合物；
　フェンピロキシメート（fenpyroximate）、フィプロニル（fipronil）、テブフェンピラド（tebufenpyrad）、エチプロール（ethiprole）、トルフェンピラド（tolfenpyrad）、アセトプロール（acetoprole）、ピラフルプロール（pyrafluprole）、ピリプロール（pyriprole）のようなピラゾール系化合物；
　イミダクロプリド（imidacloprid）、ニテンピラム（nitenpyram）、アセタミプリド（acetamiprid）、チアクロプリド（thiacloprid）、チアメトキサム（thiamethoxam）、クロチアニジン（clothianidin）、ニジノテフラン（nidinotefuran）、ジノテフラン（dinotefuran）、ニチアジン(nithiazine)のようなネオニコチノイド系化合物；
　テブフェノジド（tebufenozide）、メトキシフェノジド（methoxyfenozide）、クロマフェノジド（chromafenozide）、ハロフェノジド（halofenozide）のようなヒドラジン系化合物；
　ピリダリル（pyridalyl）、フロニカミド（flonicamid）のようなピリジン系化合物；
　スピロジクロフェン（spirodiclofen）、スピロメシフェン（spiromesifen）、スピロテトラマト（spirotetramat）のような環状ケトエノール系化合物；
　フルアクリピリム（fluacrypyrim）のようなストロビルリン系化合物；
　フルフェネリム（flufenerim）のようなピリジナミン系化合物；
　ジニトロ系化合物、有機硫黄化合物、尿素系化合物、トリアジン系化合物、ヒドラゾン系化合物、また、その他の化合物として、フロメトキン（flometoquin）、ブプロフェジン（buprofezin）、ヘキシチアゾクス（hexythiazox）、アミトラズ（amitraz）、クロルジメホルム（chlordimeform）、シラフルオフェン（silafluofen）、トリアザメイト（triazamate）、ピメトロジン（pymetrozine）、ピリミジフェン（pyrimidifen）、クロルフェナピル（chlorfenapyr）、インドキサカルブ（indoxacarb）、アセキノシル（acequinocyl）、エトキサゾール（etoxazole）、シロマジン（cyromazine）、１，３－ジクロロプロペン（1，3-dichloropropene）、ジアフェンチウロン（diafenthiuron）、ベンクロチアズ（benclothiaz）、ビフェナゼート（bifenazate）、プロパルギット（propargite）、クロフェンテジン（clofentezine）、メタフルミゾン（metaflumizone）、フルベンジアミド（flubendiamide）、シフルメトフェン（cyflumetofen）、クロラントラニリプロール（chlorantraniliprole）、シアントラニリプロール（cyantraniliprole）、シクラニリプロール（cyclaniliprole）、シエノピラフェン（cyenopyrafen）、ピリフルキナゾン（pyrifluquinazon）、フェナザキン（fenazaquin）、アミドフルメット（amidoflumet）、スルフルアミド（sulfluramid）、ヒドラメチルノン（hydramethylnon）、メタアルデヒド（metaldehyde）、リアノジン（ryanodine）、ベルブチン（verbutin）、クロロベンゾエート（chlorobenzoate）、チアゾリルシナノニトリル（thiazolylcinnanonitrile）、スルホキサフロル（sulfoxaflor）、フルエンスルホン（fluensulfone）、トリフルメゾピリム（triflumezopyrim）、アフィドピロペン（afidopyropen）、フルピラジフロン（flupyradifuron）、テトラニリプロール（tetraniliprole）、フルララネル（fluralaner）、ブロフラニリド（broflanilide）、ジクロロメゾチアズ（dicloromezotiaz）、フルヘキサホン（fluhexafon）、チオキサザフェン（tioxazafen）、ＤＫＮ－２６０１、ＭＳＩ－１３０２、ＮＡ－８９、ＭＩＥ－１２０９、ＺＤＩ－２５０２のような化合物；等が挙げられる。 In the above-mentioned other agricultural chemicals, as an active ingredient compound of a pesticide, acaricide, nematicide or soil pesticide (generic name; including partial application or Japan Plant Protection Association test code), for example , Profenofos, dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephatethio, prophofos , Fosthiazate, cadusafos, dislufoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate (dimethoate) dimethoate), sulprofos, thiometh (thiometon), bamidothion, pyraclofos, pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formothion, malathion, tetrachlorvinphos (tetrachlorvinphos), chlorfenvinphos, cyanophos, trichlorfon, methidathion, phenthoate, ESP, azinphos-methyl, fenthion, heptenophos , Methoxychlor, parathion, phosphocarb, demeton-S-methyl, monocrotophos, metamidophos, imicyafos, parathion-methyl -methyl), Telbujo Organophosphate compounds such as terbufos, phosphamidon, phosmet, phorate, phoxim, triazophos;
Carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, fenobucarb Carbamates such as carbosulfan, benfuracarb, bendiocarb, furathiocarb, isoprocarb, metolcarb, xylylcarb, XMC, fenothiocarb Compound;
Cartap, thiocyclam, bensultap, sodium thiosultap-sodium, thiosultap-disodium, monosultap, bisultap, hydrogen oxalate thiocyclam Nereistoxin derivatives such as (thiocyclam hydrogen oxalate);
Organochlorine compounds such as dicophor, tetradifon, endosulfan, dienochlor, dieldrin;
Organometallic compounds such as fenbutatin oxide and cyhexatin;
Fenvalerate, permethrin, cypermethrin, deltamethrin, cyhalothrin, tefluthrin, etofenprox, flufenprox, cyfluthrin , Fenpropathrin, flucytrinate, fluvalinate, cycloprothrin, lambda-cyhalothrin, pyrethrin, esfenvalerate, Tetramethrin, resmethrin, protrifenbute, bifenthrin, zeta-cypermethrin, acrinathrin, alpha-cypermeline (alpha-cyperme) thrin), allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin, beta-cypermethrin ( Pyrethroid compounds such as beta-cypermethrin, beta-cyfluthrin, mettofluthrin, phenothrin, flumethrin, decamethrin;
Diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, triflumuron, hexaflumuron, lufenuron, novaluron, novaluron, ), Bistrifluron, benzoylurea compounds such as fluazuron;
Juvenile hormone-like compounds such as metoprene, pyriproxyfen, fenoxycarb, diofenolan;
Pyridazinone compounds such as pyridaben;
Pyrazole compounds such as fenpyroximate, fipronil, tebufenpyrad, ethiprole, tolfenpyrad, acetoprole, pyrafluprole, pyriprole;
Imidacloprid, nitenpyram, acetamiprid, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran, dinotefuranit, dinotefuranit A noid compound;
Hydrazine compounds such as tebufenozide, methoxyfenozide, chromafenozide, halofenozide;
Pyridine compounds such as pyridalyl and flonicamid;
Cyclic ketoenol compounds such as spirodiclofen, spiromesifen, spirotetramat;
Strobilurin-based compounds such as fluacrypyrim;
Pyridinamine compounds such as flufenerim;
Dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, hydrazone compounds, and other compounds include flometoquin, buprofezin, hexythiazox, amitraz, chlordimeform ), Silafluofen, triazamate, pymetrozine, pyrimidifen, chlorfenapyr, indoxacarb, acequinocyl, etoxazole, romazine , 3-dichloropropene (1,3-dichloropropene), diafenthiuron, benclothiaz, bifenazate, propargite, clofentezine (cl ofentezine), metaflumizone, flubendiamide, cyflumetofen, chlorantraniliprole, cyantraniliprole, cyclaniliprole, cyenopyrafen, cyenopyrafen (Pyrifluquinazon), fenazaquin, amidoflumet, sulfluramid, hydramethylnon, metaldehyde, ryanodine, verbutin, chlorobenzoate, thia Thiazolylcinnanonitrile, sulfoxaflor, fluenesulfone, triflumezopyrim, afidopyropen, full Flupyradifuron, tetraniliprole, fluralaner, broflanilide, dicloromezotiaz, fluhexafon, tioxazafen, DKN-2601, MSI-1302, NA-1302 89, MIE-1209, compounds such as ZDI-2502, and the like.
　更に、バチルス　チューリゲンシス　アイザワイ（Bacillus thuringiensis aizawai）、バチルス　チューリゲンシス　クルスターキ（Bacillus thuringiensis kurstaki）、バチルス　チューリゲンシス　イスラエレンシス（Bacillus thuringiensis israelensis）、バチルス　チューリゲンシス　ジャポネシス（Bacillus thuringiensis japonensis）、バチルス　チューリゲンシス　テネブリオニス（Bacillus thuringiensis tenebrionis）等のバチルス　チューリゲンシス（Bacillus thuringiensis）が生成する結晶タンパク毒素、昆虫病原ウイルス剤、昆虫病原糸状菌剤、線虫病原糸状菌剤等のような微生物農薬、アベルメクチン（avermectin）、エマメクチンベンゾエート（emamectin Benzoate）、ミルベメクチン（milbemectin）、ミルベマイシン（milbemycin）、スピノサド（spinosad）、イベルメクチン（ivermectin）、レピメクチン（lepimectin）、ＤＥ－１７５、アバメクチン（abamectin）、エマメクチン（emamectin）、スピネトラム（spinetoram)のような抗生物質及び半合成抗生物質;アザディラクチン（azadirachtin）、ロテノン（rotenone）のような天然物；ディート（deet）のような忌避剤；等と、混用、併用することもできる。 Furthermore, Bacillus チ ュ ー thuringiensis aizawai, Bacillus チ ュ ー thuringiensis kurstaki, Bacillus リ thuringiensis israelensis, Bacillus thuringiensis israelensis, Microbial pesticides such as crystal protein toxins, entomopathogenic virus agents, entomopathogenic fungi agents, nematode pathogenic fungi agents, etc. produced by Bacillus thuringiensis such as Gensis Tenebrionis (Bacillus thuringiensis tenebrionis), Avermectin, emamectin benzoate, milbemectin, milbemycin, spinosad, ivermectin (Ivermectin), lepimectin, DE-175, antibiotics and semi-synthetic antibiotics such as abamectin, emamectin, spinetoram; azadirachtin, rotenone Such natural products; repellents such as deet; etc. can also be mixed and used together.
　上記他の農薬中の、殺菌剤の有効成分化合物（一般名；一部申請中を含む、又は日本植物防疫協会試験コード）としては、例えば、メパニピリム（mepanipyrim）、ピリメサニル（pyrimethanil）、シプロジニル（cyprodinil）、フェリムゾン（ferimzone）のようなアニリノピリミジン系化合物；
　５－クロロ－７－（４－メチルピペリジン－１－イル）－６－（２，４，６－トリフルオロフェニル）［１，２，４］トリアゾロ［１，５－ａ］ピリミジンのようなトリアゾロピリミジン系化合物；
　フルアジナム（fluazinam）のようなピリジナミン系化合物；
　トリアジメホン（triadimefon）、ビテルタノール（bitertanol）、トリフルミゾール（triflumizole）、エタコナゾール（etaconazole）、プロピコナゾール（propiconazole）、ペンコナゾール（penconazole）、フルシラゾール（flusilazole）、マイクロブタニル（myclobutanil）、シプロコナゾール（cyproconazole）、テブコナゾール（tebuconazole）、ヘキサコナゾール（hexaconazole）、ファーコナゾールシス（furconazole‐cis）、プロクロラズ（prochloraz）、メトコナゾール（metconazole）、エポキシコナゾール（epoxiconazole）、テトラコナゾール（tetraconazole）、オキスポコナゾールフマル酸塩（oxpoconazole fumarate）、シプコナゾール（sipconazole）、プロチオコナゾール（prothioconazole）、トリアジメノール（triadimenol）、フルトリアホール（flutriafol）、ジフェノコナゾール（difenoconazole）、フルキンコナゾール（fluquinconazole）、フェンブコナゾール（fenbuconazole）、ブロムコナゾール（bromuconazole）、ジニコナゾール（diniconazole）、トリシクラゾール（tricyclazole）、プロベナゾール（probenazole）、シメコナゾール（simeconazole）、ペフラゾエート（pefurazoate）、イプコナゾール（ipconazole）、イミベンコナゾール（imibenconazole）のようなアゾール系化合物；
　キノメチオネート（quinomethionate）のようなキノキサリン系化合物；
　マンネブ（maneb）、ジネブ（zineb）、マンゼブ（mancozeb）、ポリカーバメート（polycarbamate）、メチラム（metiram）、プロピネブ（propineb）、チラム(thiram)のようなジチオカーバメート系化合物；
　フサライド（fthalide）、クロロタロニル（chlorothalonil）、キントゼン（quintozene）のような有機塩素系化合物；
　ベノミル（benomyl）、シアゾファミド（cyazofamid）、チオファネートメチル（thiophanate‐methyl）、カーベンダジム（carbendazim）、チアベンダゾール(thiabendazole)、フベリアゾール(fuberiazole)のようなイミダゾール系化合物；
　シモキサニル（cymoxanil）のようなシアノアセトアミド系化合物；
　メタラキシル（metalaxyl）、メタラキシル－Ｍ（metalaxyl-M）、メフェノキサム(mefenoxam）、オキサジキシル（oxadixyl）、オフレース（ofurace）、ベナラキシル（benalaxyl）、ベナラキシル－Ｍ［benalaxyl-M、別名キララキシル(kiralaxyl、chiralaxyl)］、フララキシル（furalaxyl）、シプロフラム（cyprofuram）、カルボキシン(carboxin)、オキシカルボキシン(oxycarboxin)、チフルザミド(thifluzamide)、ボスカリド(boscalid)、ビキサフェン(bixafen)、イソチアニル(isothianil)、チアジニル（tiadinil）、セダキサン(sedaxane)のようなアニリド系化合物；
　ジクロフルアニド（dichlofluanid）のようなスルファミド系化合物；
　水酸化第二銅（cupric hydroxide）、有機銅（oxine copper）のような銅系化合物；
　ヒメキサゾール（hymexazol）のようなイソキサゾール系化合物；
　ホセチルアルミニウム（fosetyl‐Al）、トルクロホスメチル（tolclofos‐Methyl）、Ｓ－ベンジル　Ｏ，Ｏ－ジイソプロピルホスホロチオエート、Ｏ－エチル　Ｓ，Ｓ－ジフェニルホスホロジチオエート、アルミニウムエチルハイドロゲンホスホネート、エジフェンホス（edifenphos）、イプロベンホス（iprobenfos）のような有機リン系化合物；
　キャプタン（captan）、キャプタホル（captafol）、フォルペット（folpet）のようなフタルイミド系化合物；
　プロシミドン（procymidone）、イプロジオン（iprodione）、ビンクロゾリン（vinclozolin）のようなジカルボキシイミド系化合物；
　フルトラニル（flutolanil）、メプロニル（mepronil）のようなベンズアニリド系化合物；
　ペンチオピラド(penthiopyrad)、３－（ジフロロメチル）－１－メチル－Ｎ－［（１ＲＳ，４ＳＲ，９ＲＳ）－１，２，３，４－テトラヒドロ－９－イソプロピル－１，４－メタノナフタレン－５－イル］ピラゾール－４－カルボキサミドと３－（ジフロロメチル）－１－メチル－Ｎ－［（１ＲＳ，４ＳＲ，９ＳＲ）－１，２，３，４－テトラヒドロ－９－イソプロピル－１，４－メタノナフタレン－５－イル］ピラゾール－４－カルボキサミドの混合物（イソピラザム（isopyrazam））、シルチオファム（silthiopham）、フェノキサニル（fenoxanil）、フラメトピル（furametpyr）のようなアミド系化合物；
　フルオピラム(fluopyram)、ゾキサミド（zoxamide）のようなベンズアミド系化合物；
　トリホリン（triforine）のようなピペラジン系化合物；
　ピリフェノックス（pyrifenox）のようなピリジン系化合物；
　フェナリモル（fenarimol）のようなカルビノール系化合物；
　フェンプロピディン（fenpropidin）のようなピペリジン系化合物；
　フェンプロピモルフ（fenpropimorph）、トリデモルフ(tridemorph)のようなモルフォリン系化合物；
　フェンチンヒドロキシド（fentin hydroxide）、フェンチンアセテート（fentin acetate）のような有機スズ系化合物；
　ペンシキュロン（pencycuron）のような尿素系化合物；
　ジメトモルフ（dimethomorph）、フルモルフ（flumorph）のようなシンナミック酸系化合物；
　ジエトフェンカルブ（diethofencarb）のようなフェニルカーバメート系化合物；
　フルジオキソニル（fludioxonil）、フェンピクロニル（fenpiclonil）のようなシアノピロール系化合物；
　アゾキシストロビン（azoxystrobin）、クレソキシムメチル（kresoxim‐methyl）、メトミノストロビン（metominostrobin）、トリフロキシストロビン（trifloxystrobin）、ピコキシストロビン（picoxystrobin）、オリザストロビン（oryzastrobin）、ジモキシストロビン（dimoxystrobin）、ピラクロストロビン（pyraclostrobin）、フルオキサストロビン（fluoxastrobin）のようなストロビルリン系化合物；
　ファモキサドン（famoxadone）のようなオキサゾリジノン系化合物；
　エタボキサム（ethaboxam）のようなチアゾールカルボキサミド系化合物；
　イプロバリカルブ（iprovalicarb）、ベンチアバリカルブ－イソプロピル（benthiavalicarb-isopropyl）のようなバリンアミド系化合物；
　メチル　Ｎ－（イソプロポキシカルボニル）－Ｌ－バリル－（３ＲＳ）－３－（４－クロロフェニル）－β－アラニナート（valiphenalate）のようなアシルアミノアシッド系化合物；
　フェナミドン（fenamidone）のようなイミダゾリノン系化合物；
　フェンヘキサミド（fenhexamid）のようなハイドロキシアニリド系化合物；
　フルスルファミド（flusulfamide）のようなベンゼンスルホンアミド系化合物；
　シフルフェナミド（cyflufenamid）のようなオキシムエーテル系化合物；
　アトラキノン系化合物；
　クロトン酸系化合物；
　バリダマイシン（validamycin）、カスガマイシン（kasugamycin）、ポリオキシン(polyoxins)のような抗生物質；
　イミノクタジン（iminoctadine）、ドディン（dodine）のようなグアニジン系化合物；
　６－ターシャリーブチル－８－フルオロ－２，３－ジメチルキノリン－４－イル　アセテート［テブフロキン(tebufloquin)］のようなキノリン系化合物；
　（Ｚ）－２－［２－フルオロ－５－（トリフルオロメチル）フェニルチオ］－２－［３－（２－メトキシフェニル）チアゾリジン－２－イリデン］アセトニトリル［フルチアニル（flutianil）］のようなチアゾリジン系化合物；
　その他の化合物として、ピリベンカルブ（pyribencarb）、イソプロチオラン（isoprothiolane）、ピロキロン（pyroquilon）、ジクロメジン（diclomezine）、キノキシフェン（quinoxyfen）、プロパモカルブ塩酸塩（propamocarb hydrochloride）クロルピクリン（chloropicrin）、ダゾメット（dazomet）、メタムナトリウム塩（metam‐sodium）、ニコビフェン（nicobifen）、メトラフェノン（metrafenone）、ＵＢＦ－３０７、ジクロシメット（diclocymet）、プロキンアジド（proquinazid）、アミスルブロム［amisulbrom；別名アミブロドール（amibromdole）］、３－（２，３，４－トリメトキシ－６－メチルベンゾイル）－５－クロロ－２－メトキシ－４－メチルピリジン、４－（２，３，４－トリメトキシ－６－メチルベンゾイル）－２，５－ジクロロ－３－トリフルオロメチルピリジン、ピリオフェノン（pyriofenone）、イソフェタミド（isofetamid）マンジプロパミド（mandipropamid）、フルオピコリド(fluopicolide)、カルプロパミド（carpropamid）、メプチルジノキャップ（meptyldinocap）、Ｎ－［（３’，４’－ジクロロ－１，１－ジメチル）フェナシル］－３－トリフルオロメチル－２－ピリジンカルボキサミド、Ｎ－［（３’，４’－ジクロロ－１，１－ジメチル）フェナシル］－３－メチル－２－チオフェンカルボキサミド、Ｎ－［（３’，４’－ジクロロ－１，１－ジメチル）フェナシル］－１－メチル－３－トリフルオロメチル－４－ピラゾールカルボキサミド、Ｎ－［［２’－メチル－４’－（２－プロピルオキシ）－１，１－ジメチル］フェナシル］－３－トリフルオロメチル－２－ピリジンカルボキサミド、Ｎ－［［２’－メチル－４’－（２－プロピルオキシ）－１，１－ジメチル］フェナシル］－３－メチル－２－チオフェンカルボキサミド、Ｎ－［［２’－メチル－４’－（２－プロピルオキシ）－１，１－ジメチル］フェナシル］－１－メチル－３－トリフルオロメチル－４－ピラゾールカルボキサミド、Ｎ－［［４’－（２－プロピルオキシ）－１，１－ジメチル］フェナシル］－３－トリフルオロメチル－２－ピリジンカルボキサミド、Ｎ－［［４’－（２－プロピルオキシ）－１，１－ジメチル］フェナシル］－３－メチル－２－チオフェンカルボキサミド、Ｎ－［［４’－（２－プロピルオキシ）－１，１－ジメチル］フェナシル］－１－メチル－３－トリフルオロメチル－４－ピラゾールカルボキサミド、Ｎ－［［２’－メチル－４’－（２－ペンチルオキシ）－１，１－ジメチル］フェナシル］－３－トリフルオロメチル－２－ピリジンカルボキサミド、Ｎ－［［４’－（２－ペンチルオキシ）－１，１－ジメチル］フェナシル］－３－トリフルオロメチル－２－ピリジンカルボキサミド、スピロキサミン（spiroxamine）、フェンピラザミン（fenpyrazamine）、マンデストロビン（mandestrobin）、ZF-9646、BCF-051、BCM-061、BCM-062等が挙げられる。 In the above-mentioned other pesticides, as an active ingredient compound (generic name; including partial application or Japanese Plant Protection Association test code), for example, mepanipyrim, pyrimethanil, cyprodinil ), Anilinopyrimidine compounds such as ferimzone;
Tria such as 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) [1,2,4] triazolo [1,5-a] pyrimidine Zolopyrimidine compounds;
Pyridinamine compounds such as fluazinam;
Triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanil, cyproconazole cyproconazole), tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole, o Oxpoconazole fumarate, sipconazole, prothioconazole, triadimenol, flutriafol, difenoconazole , Fluquinconazole, fenbuconazole, bromuconazole, diniconazole, tricyclazole, probenazole, cimeconazole, pefurazoate, ipconazole, ipconazole ), Azole compounds such as imibenconazole;
Quinoxaline compounds such as quinomethionate;
Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram;
Organochlorine compounds such as fthalide, chlorothalonil, quintozene;
Imidazole compounds such as benomyl, cyazofamid, thiophanate-methyl, carbendazim, thiabendazole, and fuberiazole;
Cyanoacetamide compounds such as cymoxanil;
Metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, offurace, benalaxyl, benalaxyl-M, also known as kiralaxyl, chiax ], Flaxaxyl, cyprofuram, carboxin, oxycarboxin, thifluzamide, boscalid, bixafen, isothianil, tiadinil, Anilide compounds such as sedaxane;
Sulfamide-type compounds such as dichlofluanid;
Copper-based compounds such as cupric hydroxide and oxine copper;
Isoxazole compounds such as hymexazol;
Fosetyl aluminum (fosetyl-Al), tolclofos-Methyl, S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate, edifenphos, iprobenphos Organophosphorus compounds such as (iprobenfos);
Phthalimide compounds such as captan, captafol, folpet;
Dicarboximide compounds such as procymidone, iprodione, vinclozolin;
Benzanilide compounds such as flutolanil and mepronil;
Penthiopyrad, 3- (difluoromethyl) -1-methyl-N-[(1RS, 4SR, 9RS) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methananaphthalen-5-yl ] Pyrazole-4-carboxamide and 3- (difluoromethyl) -1-methyl-N-[(1RS, 4SR, 9SR) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methananaphthalene-5 Amide compounds such as -yl] pyrazole-4-carboxamide mixtures (isopyrazam), silthiopham, fenoxanil, furametpyr;
Benzamide compounds such as fluopyram and zoxamide;
Piperazine compounds such as triforine;
Pyridine compounds such as pyrifenox;
Carbinol compounds such as fenarimol;
Piperidine compounds such as fenpropidin;
Morpholine compounds such as fenpropimorph and tridemorph;
Organotin compounds such as fentin hydroxide and fentin acetate;
Urea-based compounds such as pencycuron;
Synamic acid compounds such as dimethomorph, flumorph;
Phenyl carbamate compounds such as dietofencarb;
Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
Azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin ( strobilurin compounds such as dimoxystrobin), pyraclostrobin, fluoxastrobin;
Oxazolidinone compounds such as famoxadone;
Thiazole carboxamide compounds such as ethaboxam;
Valinamide compounds such as iprovalicarb, benchthiavalicarb-isopropyl;
Acylamino acid compounds such as methyl N- (isopropoxycarbonyl) -L-valyl- (3RS) -3- (4-chlorophenyl) -β-valiphenalate;
Imidazolinone compounds such as fenamidone;
Hydroxyanilide compounds such as fenhexamid;
Benzenesulfonamide compounds such as flusulfamide;
Oxime ether compounds such as cyflufenamid;
Atraquinone compounds;
Crotonic acid compounds;
Antibiotics such as validamycin, kasugamycin, polyoxins;
Guanidine compounds such as iminoctadine and dodine;
Quinoline-based compounds such as 6-tertiarybutyl-8-fluoro-2,3-dimethylquinolin-4-yl acetate [tebufloquin];
Thiazolidines such as (Z) -2- [2-fluoro-5- (trifluoromethyl) phenylthio] -2- [3- (2-methoxyphenyl) thiazolidine-2-ylidene] acetonitrile [flutianil] Compound;
Other compounds include pyribencarb, isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, and sodium metam Metam-sodium, nicobifen, metrafenone, UBF-307, diclocymet, proquinazid, amisulbrom (aka amibromdole), 3- (2,3,4 -Trimethoxy-6-methylbenzoyl) -5-chloro-2-methoxy-4-methylpyridine, 4- (2,3,4-trimethoxy-6-methylbenzoyl) -2,5-dichloro-3-trifluoromethyl Pyridine, Riofenone, isofetamid mandipropamid, fluopicolide, carpropamid, meptyldinocap, N-[(3 ', 4'-dichloro-1,1-dimethyl) Phenacyl] -3-trifluoromethyl-2-pyridinecarboxamide, N-[(3 ′, 4′-dichloro-1,1-dimethyl) phenacyl] -3-methyl-2-thiophenecarboxamide, N-[(3 ′ , 4'-Dichloro-1,1-dimethyl) phenacyl] -1-methyl-3-trifluoromethyl-4-pyrazolecarboxamide, N-[[2'-methyl-4 '-(2-propyloxy) -1 , 1-Dimethyl] phenacyl] -3-trifluoromethyl-2-pyridinecarboxamide, N-[[2′-methyl-4′- 2-propyloxy) -1,1-dimethyl] phenacyl] -3-methyl-2-thiophenecarboxamide, N-[[2′-methyl-4 ′-(2-propyloxy) -1,1-dimethyl] phenacyl ] -1-Methyl-3-trifluoromethyl-4-pyrazolecarboxamide, N-[[4 ′-(2-propyloxy) -1,1-dimethyl] phenacyl] -3-trifluoromethyl-2-pyridinecarboxamide N-[[4 ′-(2-propyloxy) -1,1-dimethyl] phenacyl] -3-methyl-2-thiophenecarboxamide, N-[[4 ′-(2-propyloxy) -1,1 -Dimethyl] phenacyl] -1-methyl-3-trifluoromethyl-4-pyrazolecarboxamide, N-[[2′-methyl-4 ′-(2-pentyloxy) -1,1 Dimethyl] phenacyl] -3-trifluoromethyl-2-pyridinecarboxamide, N-[[4 ′-(2-pentyloxy) -1,1-dimethyl] phenacyl] -3-trifluoromethyl-2-pyridinecarboxamide, Examples include spiroxamine, fenpyrazamine, mandestrobin, ZF-9646, BCF-051, BCM-061, and BCM-062.
　その他、本発明化合物と混用或いは併用することが可能な農薬としては、例えは、The Pesticide Manual（第15版）に記載されているような除草剤の有効成分化合物、特に土壌処理型のもの等がある。 Other pesticides that can be used in combination with or combined with the compounds of the present invention include, for example, active compound compounds of herbicides, particularly those of soil treatment type, as described in The Pesticide Manual (15th edition), etc. There is.
　殺動物寄生生物剤としては、具体的には、例えば、宿主動物の体表（例えば、背、腋下、下腹部、内股部等）に寄生する有害な外部寄生虫や、宿主動物の体内（例えば、胃、腸管、肺、心臓、肝臓、血管、皮下、リンパ組織など）に寄生する有害な内部寄生虫の防除に有効であるが、中でも、外部寄生虫の防除に有効である。 Specific examples of the animal-killing parasite agent include harmful ectoparasites parasitic on the body surface of the host animal (eg, back, armpit, lower abdomen, inner thigh, etc.) For example, it is effective for controlling harmful endoparasites parasitic on the stomach, intestinal tract, lungs, heart, liver, blood vessels, subcutaneous, lymphatic tissue, etc., and is particularly effective for controlling ectoparasites.
　外部寄生虫としては、例えば、動物寄生性のダニやノミ等が挙げられる。これらの種類は非常に多く、全てを列記することが困難であるので、その一例を挙げる。 Examples of ectoparasites include animal parasitic mites and fleas. There are so many of these types that it is difficult to list them all.
　動物寄生性のダニとしては、例えば、オウシマダニ（Boophilus microplus）、クリイロコイタマダニ（Rhipicephalus sanguineus）、フタトゲチマダニ（Haemaphysalis longicornis）、キチマダニ（Haemaphysalis flava）、ツリガネチマダニ（Haemaphysalis campanulata）、イスカチマダニ（Haemaphysalis concinna）、ヤマトチマダニ（Haemaphysalis japonica）、ヒゲナガチマダニ（Haemaphysalis kitaokai）、イヤスチマダニ（Haemaphysalis ias）、ヤマトマダニ（Ixodes ovatus）、タネガタマダニ（Ixodes nipponensis）、シュルツェマダニ（Ixodes persulcatus）、タカサゴキララマダニ（Amblyomma testudinarium）、オオトゲチマダニ（Haemaphysalis megaspinosa）、アミノカクマダニ（Dermacentor reticulatus）、タイワンカクマダニ（Dermacentor taiwanesis）のようなマダニ類；ワクモ（Dermanyssus gallinae）；トリサシダニ（Ornithonyssus sylviarum）、ミナミトリサシダニ（Ornithonyssus bursa）のようなトリサシダニ類；ナンヨウツツガムシ（Eutrombicula wichmanni）、アカツツガムシ（Leptotrombidium akamushi）、フトゲツツガムシ（Leptotrombidium pallidum）、フジツツガムシ（Leptotrombidium fuji）、トサツツガムシ（Leptotrombidium tosa）、ヨーロッパアキダニ（Neotrombicula autumnalis）、アメリカツツガムシ（Eutrombicula alfreddugesi）、ミヤガワタマツツガムシ（Helenicula miyagawai）のようなツツガムシ類；イヌツメダニ（Cheyletiella yasguri）、ウサギツメダニ（Cheyletiella parasitivorax）、ネコツメダニ（Cheyletiella blakei）のようなツメダニ類；ウサギキュウセンダニ（Psoroptes cuniculi）、ウシショクヒダニ（Chorioptes bovis）、イヌミミヒゼンダニ（Otodectes cynotis）、ヒゼンダニ（Sarcoptes scabiei）、ネコショウセンコウヒゼンダニ（Notoedres cati）のようなヒゼンダニ類；イヌニキビダニ（Demodex canis）のようなニキビダニ類等が挙げられる。中でも、本発明化合物を含有する殺動物寄生生物剤は、マダニ類等の防除に特に有効である。 Examples of animal parasitic ticks include Boophilus microplus, Rhipicephalus sanguineus, Scarlet ticks (Haemaphysalis longicornis), Tick ticks (Haemaphysalis flava), Tick ticks (Haemaphysalis campuls , Mites (Haemaphysalis japonica), mites (Haemaphysalis kitaokai), mites (Haemaphysalis ias), mites (Ixodes ovatus), mites (Ixodes nipponensis), mites (Ixodes nipponensis), mushroom mites (Ixodes nipponensis), mites Ticks such as Haemaphysalis megaspinosa), Dermacentor reticulatus, Dermacentor taiwanesis; Dermanyssus gallinae; Ornithonyssus sylviarum, Ornithonyssus bursa; Trichodid mites (Eutrombicula wichmanni), Red tsutsutsuji (Leptotrombidium akamushi), Red tsutsutsuji (Leptotrombidium pallidum), Lepto tsutsu ryuto ), European tick (Neotrombicula autumnalis), American horn beetle (Eutrombicula alfreddugesi), tsutsugamushi (Helenicula miyagawai); Crested ticks: Psoroptes cuniculi, Chorioptes bovis, Otodectes cynotis, Sarcoptes scabiei, cats Mange mites, such as ® U SENKOU mites (Notoedres cati); Demodex, such as Inunikibidani (Demodex canis), and the like. Among them, the animal killing parasite agent containing the compound of the present invention is particularly effective for controlling ticks and the like.
　動物寄生性のノミとしては、例えば、ノミ目（Siphonaptera）に属する外部寄生性無翅昆虫、より具体的には、ヒトノミ科（Pulicidae）、ナガノミ科（Ceratephyllus）等に属するノミ類が挙げられる。ヒトノミ科に属するノミ類としては、例えば、イヌノミ（Ctenocephalides canis）、ネコノミ（Ctenocephalides felis）、ヒトノミ（Pulex irritans）、ニワトリフトノミ（Echidnophaga gallinacea）、ケオプスネズミノミ（Xenopsylla cheopis）、メクラネズミノミ（Leptopsylla segnis）、ヨーロッパネズミノミ（Nosopsyllus fasciatus）、ヤマトネズミノミ（Monopsyllus anisus）；等が挙げられる。中でも、本発明化合物を含有する殺動物寄生生物剤は、ヒトノミ科に属するノミ類、特にイヌノミ、ネコノミ等の防除に有効である。 Examples of animal parasitic fleas include ectoparasite worms belonging to the order Flea (Siphonaptera), and more specifically fleas belonging to the family Flea (Pulicidae), Cleaphyllus (Ceratephyllus), and the like. Fleas belonging to the family flea family include, for example, dog fleas (Ctenocephalides canis), cat fleas (Ctenocephalides felis), human fleas (Pulex irritans), elephant fleas (Echidnophaga gallinacea), keops mouse fleas (Xenopsylla cheopis), Leptopsylla segnis), European mouse minnow (Nosopsyllus fasciatus), and Yamato mouse minnow (Monopsyllus anisus); Among them, the animalicidal parasite agent containing the compound of the present invention is effective for controlling fleas belonging to the family flea family, especially dog fleas, cat fleas and the like.
　その他の外部寄生虫としては、例えば、ウシジラミ、ウマジラミ、ヒツジジラミ、ウシホソジラミ、アタマジラミのようなシラミ類；イヌハジラミのようなハジラミ類；ウシアブ、ウアイヌカカ、ツメトゲブユのような吸血性双翅目害虫等が挙げられる。 Other ectoparasites include, for example, lice such as bovine lice, foal lice, sheep lice, bovine white lice, head lice; lice such as cat lice; blood-sucking dipterous pests such as bovine abs, quail sharks, .
　また、内部寄生虫としては、例えば、肺虫、ベンチュウ、結節状ウオーム、胃内寄生虫、回虫、糸状虫類のような線虫類；マンソン裂頭条虫、広節裂頭条虫、瓜実条虫、多頭条虫、単包条虫、多包条虫のような条虫類；日本住血吸虫、肝蛭のような吸虫類；コクシジウム、マラリア原虫、腸内肉胞子虫、トキソプラズマ、クリプトスポリジウムのような原生動物など；が挙げられる。 In addition, examples of endoparasites include nematodes such as lungworm, benthic, nodular worms, gastric parasites, roundworms, and filamentous worms; Tapeworms such as real tapeworms, multi-headed tapeworms, single-banded tapeworms, multi-banded tapeworms; Japanese schistosomiasis, fluke like liver fluke; coccidium, malaria parasite, intestinal granulocyst, toxoplasma, chestnut Protozoa such as Ptosporidium, and the like.
　宿主動物としては、例えば、種々の愛玩動物、家畜、家禽等が挙げられる。より具体的には、例えば、イヌ、ネコ、マウス、ラット、ハムスター、モルモット、リス、ウサギ、フェレット、鳥（例えば、ハト、オウム、九官鳥、文鳥、インコ、ジュウシマツ、カナリアなど）、ウシ、ウマ、ブタ、ヒツジ、アヒル、ニワトリ、などが挙げられる。中でも、本発明化合物を含有する殺動物寄生生物剤は、愛玩動物又は家畜に外部寄生する害虫又はダニの防除に有効である。愛玩動物又は家畜の中ではイヌ、ネコ、ウシ又はウマに特に有効である。 Examples of host animals include various pet animals, livestock, and poultry. More specifically, for example, dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (eg, pigeons, parrots, nine-birds, wild birds, parakeets, juvenile pine, canary, etc.) Pigs, sheep, ducks, chickens, etc. Among them, the animal killing parasite agent containing the compound of the present invention is effective for controlling pests or ticks that are externally parasitic on pet animals or livestock. Among pet animals or domestic animals, it is particularly effective for dogs, cats, cows or horses.
　本発明化合物を殺動物寄生生物剤として使用する際、そのまま使用してもよく、また、適当な補助剤と共に粉剤、粒剤、錠剤、散剤、カプセル剤、液状剤、乳剤、水性懸濁剤、油性懸濁剤等の種々の形態に製剤して使用することもできる。尚、前記製剤形態以外にも、本発明の目的に適合するかぎり、通常の当該分野で用いられているあらゆる製剤形態にすることができる。 When the compound of the present invention is used as an animal killing parasite, it may be used as it is, and together with suitable adjuvants, powders, granules, tablets, powders, capsules, liquid agents, emulsions, aqueous suspensions, It can also be formulated and used in various forms such as an oily suspension. In addition to the above-mentioned preparation forms, any preparation forms used in the normal field can be used as long as the object of the present invention is met.
　製剤に使用する補助剤としては、前記した殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤の製剤用補助剤として例示した陰イオン系の界面活性剤や非イオン系の界面活性剤；セチルトリメチルアンモニウムブロミドのような陽イオン系の界面活性剤；水、アセトン、アセトニトリル、Ｎ－メチルアセトアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、２－ピロリドン、Ｎ－メチル－２－ピロリドン、ケロシン、トリアセチン、メタノール、エタノール、イソプロパノール、ベンジルアルコール、エチレングリコール、プロピレングリコール、ポリエチレングリコール、液体ポリオキシエチレングリコール、ブチルジグリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールノルマルブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールノルマルブチルエーテルのような溶剤；ブチルヒドロキシアニソール、ブチルヒドロキシトルエン、アスコルビン酸、メタ亜硫酸水素ナトリウム、プロピル没食子酸塩、チオ硫酸ナトリウムのような酸化防止剤；ポリビニルピロリドン、ポリビニルアルコール、酢酸ビニルとビニルピロリドンのコポリマーのような被膜形成剤；前記した殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤の製剤用補助剤として例示した植物油や鉱物油；乳糖、蔗糖、ブドウ糖、澱粉、麦粉、コーン粉、大豆油粕、脱脂米糠、炭酸カルシウム、その他市販の飼料原料のような担体；等が挙げられる。これら補助剤の各成分は、本発明の目的から逸脱しないかぎり、１種又は２種以上を適宜選択して使用することができる。また、前記した補助剤以外にも当該分野で知られたものの中から適宜選択して使用することもでき、更には、前記した農園芸分野で使用される各種補助剤等から適宜選択して使用することもできる。 As an auxiliary agent used in the preparation, anionic surfactants and nonionic surfactants exemplified as auxiliary agents for preparation of the above-mentioned insecticides, acaricides, nematicides or soil insecticides A cationic surfactant such as cetyltrimethylammonium bromide; water, acetone, acetonitrile, N-methylacetamide, N, N-dimethylacetamide, N, N-dimethylformamide, 2-pyrrolidone, N-methyl-2 -Pyrrolidone, kerosene, triacetin, methanol, ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, liquid polyoxyethylene glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Solvents such as ethylene glycol monoethyl ether, diethylene glycol normal butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol normal butyl ether; butylhydroxyanisole, butylhydroxytoluene, ascorbic acid, sodium metabisulfite, propyl gallate, sodium thiosulfate Antioxidants such as: polyvinyl pyrrolidone, polyvinyl alcohol, film forming agents such as vinyl acetate and vinyl pyrrolidone copolymers; adjuvants for formulation of the aforementioned insecticides, acaricides, nematicides or soil insecticides And vegetable oils and mineral oils exemplified as: lactose, sucrose, glucose, starch, wheat flour, corn flour, soybean oil cake, defatted rice bran, calcium carbonate, and other carriers such as commercially available feed materials. Each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention. In addition to the above-mentioned adjuvants, it can be used by appropriately selecting from those known in the field, and further, selected from various adjuvants used in the above-mentioned agricultural and horticultural fields. You can also
　本発明化合物と各種補助剤との配合割合（重量比）は、通常、０．１：９９．９～９０：１０程度である。これら製剤の実際の使用に際しては、そのまま使用するか、又は水等の希釈剤で所定濃度に希釈し、必要に応じて各種展着剤（例えば、界面活性剤、植物油、鉱物油等）を添加して使用することができる。 The compounding ratio (weight ratio) of the compound of the present invention and various adjuvants is usually about 0.1: 99.9 to 90:10. In actual use of these preparations, use them as they are, or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (for example, surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.
　宿主動物への本発明化合物の投与は、経口又は非経口によって行われる。経口投与法としては、例えば、本発明化合物を含有する錠剤、液状剤、カプセル剤、ウエハース、ビスケット、ミンチ肉、その他の飼料等を投与する方法等が挙げられる。非経口投与方法としては、例えば、本発明化合物を適当な製剤に調製した上で、静注投与、筋肉内投与、皮内投与、皮下投与等により体内に取り込ませる方法；スポットオン（ｓｐｏｔ－ｏｎ）処理、ポワオン（ｐｏｕｒ－ｏｎ）処理、スプレー処理等により体表面に投与する方法；宿主動物の皮下に本発明化合物を含有する樹脂片等を埋め込む方法等が挙げられる。 Administration of the compound of the present invention to the host animal is performed orally or parenterally. Examples of the oral administration method include a method of administering tablets, liquid agents, capsules, wafers, biscuits, minced meat, and other feeds containing the compound of the present invention. As a parenteral administration method, for example, the compound of the present invention is prepared into an appropriate preparation and taken into the body by intravenous administration, intramuscular administration, intradermal administration, subcutaneous administration, etc .; spot-on ) Treatment, pour-on treatment, spray treatment, and the like; and a method of embedding a resin piece containing the compound of the present invention under the skin of a host animal.
　宿主動物への本発明化合物の投与量は、投与方法、投与目的、疾病症状等によって異なるが、通常、宿主動物の体重１ｋgに対して一般に０.０１ｍｇ～１００ｇ、好ましくは０．１ｍｇ～１０ｇの割合で投与するのが適当である。 The dose of the compound of the present invention to the host animal varies depending on the administration method, administration purpose, disease symptom, etc., but is generally 0.01 mg to 100 g, preferably 0.1 mg to 10 g, per 1 kg body weight of the host animal. It is appropriate to administer in proportions.
　本発明には、前記したような投与方法又は投与量による動物寄生生物の防除方法、特に外部寄生虫又は内部寄生虫の防除方法も含まれる。 The present invention also includes a method for controlling animal parasites by the administration method or dosage as described above, particularly a method for controlling ectoparasites or endoparasites.
　また、本発明においては、前述のようにして有害な動物寄生生物を防除することにより、それらに起因する宿主動物の各種疾患を予防又は治療できる場合がある。このように、本発明には、本発明化合物を有効成分として含有する寄生虫起因動物疾患の予防剤又は治療剤並びに、寄生虫起因動物疾患を予防又は治療する方法も含まれる。 In the present invention, by controlling harmful animal parasites as described above, various host animal diseases caused by them may be prevented or treated. Thus, the present invention includes a prophylactic or therapeutic agent for parasitic animal diseases containing the compound of the present invention as an active ingredient, and a method for preventing or treating parasitic animal diseases.
　本発明化合物を殺動物寄生生物剤として使用する際、補助剤と共に各種ビタミン類、ミネラル類、アミノ酸類、栄養剤、酵素製剤、解熱剤、鎮静剤、消炎剤、殺菌剤、着色剤、芳香剤、保存剤等と混用又は併用することができる。また、必要に応じて他の各種動物薬や農薬、例えば、駆虫剤、抗コクシジウム剤、殺虫剤、殺ダニ剤、殺ノミ剤、殺線虫剤、殺菌剤、抗菌剤等と混用又は併用することができ、この場合に一層優れた効果を示すこともある。本発明には、前記したような各種成分を混用又は併用した動物寄生生物防除用組成物が含まれ、また、それを使用した動物寄生生物の防除方法、特に外部寄生虫又は内部寄生虫の防除方法も含まれる。 When the compound of the present invention is used as an animal killing parasite, various vitamins, minerals, amino acids, nutrients, enzyme preparations, antipyretics, sedatives, anti-inflammatory agents, bactericides, coloring agents, fragrances, It can be mixed with or used in combination with preservatives. In addition, if necessary, other animal drugs and agricultural chemicals such as anthelmintics, anticoccidials, insecticides, acaricides, fleas, nematicides, fungicides, antibacterials, etc. In this case, a better effect may be exhibited. The present invention includes a composition for controlling animal parasites in which various components as described above are mixed or used together, and a method for controlling animal parasites using the composition, in particular, control of ectoparasites or endoparasites. A method is also included.
　次に、本発明の４－（フェニルエテニル）ピリジン系化合物又はその塩の好ましい実施形態のいくつかを例示するが、これらは本発明を限定するものではない。
（１）前記式（Ｉ）の４－（フェニルエテニル）ピリジン系化合物又はその塩。
（２）式（Ｉ－Ａ）： Next, some preferred embodiments of the 4- (phenylethenyl) pyridine-based compound or a salt thereof of the present invention will be exemplified, but these do not limit the present invention.
(1) A 4- (phenylethenyl) pyridine compound of the above formula (I) or a salt thereof.
(2) Formula (IA):
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
〔式中、Ｒ１及びＲ２は前述の定義通りである〕で表される４－（フェニルエテニル）ピリジン系化合物又はその塩。 [Wherein R 1 and R 2 are as defined above] or a 4- (phenylethenyl) pyridine compound or a salt thereof.
（３）Ｒ１がハロゲン原子、（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）ハロアルキル又は（Ｃ１－Ｃ６）ハロアルコキシであり、Ｒ２がハロゲン原子、（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ１－Ｃ６）アルキルスルフィニル、（Ｃ１－Ｃ６）アルキルスルホニル、（Ｃ１－Ｃ６アルコキシ）カルボニル、（Ｃ１－Ｃ６アルキル）アミノカルボニル又はジ（Ｃ１－Ｃ６アルキル）アミノカルボニルである（１）又は（２）に記載の４－（フェニルエテニル）ピリジン系化合物又はその塩。
（４）Ｒ１がハロゲン原子、（Ｃ１－Ｃ６）アルキル又は（Ｃ１－Ｃ６）ハロアルコキシである（３）に記載の４－（フェニルエテニル）ピリジン系化合物又はその塩。
（５）Ｒ２がハロゲン原子、（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ１－Ｃ６）アルキルスルフィニル又は（Ｃ１－Ｃ６）アルキルスルホニルである（３）又は（４）に記載の４－（フェニルエテニル）ピリジン系化合物又はその塩。 (3) R 1 is a halogen atom, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl or (C 1 -C 6 ) haloalkoxy, R 2 is a halogen atom, (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio, (C 1 -C 6 ) alkylsulfinyl, (1) or (2) which is (C 1 -C 6 ) alkylsulfonyl, (C 1 -C 6 alkoxy) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl or di (C 1 -C 6 alkyl) aminocarbonyl 4- (phenylethenyl) pyridine-based compound or a salt thereof according to (4).
(4) The 4- (phenylethenyl) pyridine compound or a salt thereof according to (3), wherein R 1 is a halogen atom, (C 1 -C 6 ) alkyl or (C 1 -C 6 ) haloalkoxy.
(5) R 2 is a halogen atom, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio, (C 1 -C 6 ) alkylsulfinyl or (C 1- The 4- (phenylethenyl) pyridine compound or a salt thereof according to (3) or (4), which is C 6 ) alkylsulfonyl.
　一方、本発明の４－（フェニルエテニル）ピリジン系化合物の製造用中間体である式(ＩＩ)の化合物の好ましい実施形態のいくつかを例示するが、これらは本発明を限定するものではない。
（１）前記式（ＩＩ）の化合物又はその塩。
（２）式（ＩＩ－Ａ）： On the other hand, some preferred embodiments of the compound of the formula (II), which is an intermediate for the production of the 4- (phenylethenyl) pyridine compound of the present invention, are illustrated, but these do not limit the present invention. .
(1) A compound of the above formula (II) or a salt thereof.
(2) Formula (II-A):
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
〔式中、Ｒ１及びＲ２は前述の定義通りである〕で表される化合物又はその塩。 [Wherein R 1 and R 2 are as defined above] or a salt thereof.
（３）Ｒ１がハロゲン原子、（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）ハロアルキル又は（Ｃ１－Ｃ６）ハロアルコキシであり、Ｒ２がハロゲン原子、（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ１－Ｃ６）アルキルスルフィニル又は（Ｃ１－Ｃ６）アルキルスルホニルである（１）又は（２）の化合物又はその塩。 (3) R 1 is a halogen atom, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl or (C 1 -C 6 ) haloalkoxy, R 2 is a halogen atom, (C 1 -C (1) or (2) which is 6 ) alkyl, (C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio, (C 1 -C 6 ) alkylsulfinyl or (C 1 -C 6 ) alkylsulfonyl Or a salt thereof.
　次に本発明の実施例を記載するが、本発明はこれらに限定されるものではない。まず、本発明化合物の合成例を記載する。 Next, examples of the present invention will be described, but the present invention is not limited thereto. First, the synthesis example of this invention compound is described.
　合成例１
（Ｚ）－４－［２－［４－（ｔｅｒｔ-ブチル）フェニル］－２－クロロビニル］－３－ヨードピリジン（化合物Ｎｏ．I－４１）の合成 Synthesis example 1
Synthesis of (Z) -4- [2- [4- (tert-butyl) phenyl] -2-chlorovinyl] -3-iodopyridine (Compound No. I-41)
（１）３－ヨード－４－メチルピリジンの合成
　３－アミノ－４－メチルピリジン（１５．０ｇ、１３８．７ｍｍｏｌ）のアセトニトリル（５５０ｍＬ）溶液にｐ－トルエンスルホン酸一水和物（７９．２ｇ、４１６．１ｍｍｏｌ）を加え、１０－１５℃で亜硝酸ナトリウム（１９．１ｇ、２７７．４ｍｍｏｌ）及びヨウ化カリウム（６９．１ｇ、２７７．４ｍｍｏｌ）を水（１１０ｍＬ）に溶かした溶液を滴下した後、室温で１時間攪拌させた。反応溶液を飽和炭酸水素ナトリウム水溶液で中和した後、飽和チオ硫酸ナトリウム水溶液（２００ｍＬ）を加えた。反応混合物を酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル＝４／１・容量比）で精製し、３－ヨード－４－メチルピリジン（２３．３ｇ、収率７７％）を得た。 (1) Synthesis of 3-iodo-4-methylpyridine To a solution of 3-amino-4-methylpyridine (15.0 g, 138.7 mmol) in acetonitrile (550 mL), p-toluenesulfonic acid monohydrate (79.2 g) 416.1 mmol) was added, and a solution of sodium nitrite (19.1 g, 277.4 mmol) and potassium iodide (69.1 g, 277.4 mmol) dissolved in water (110 mL) was added dropwise at 10-15 ° C. Then, it was made to stir at room temperature for 1 hour. The reaction solution was neutralized with a saturated aqueous sodium hydrogen carbonate solution, and then a saturated aqueous sodium thiosulfate solution (200 mL) was added. The reaction mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 4/1, volume ratio) to give 3-iodo-4-methylpyridine (23.3 g, yield 77%). Obtained.
（２）１－［４－（ｔｅｒｔ-ブチル）フェニル］－２－（３－ヨードピリジン－４－イル）エタン－１－オン（化合物Ｎｏ．ＩＩ－４１）の合成
　３－ヨード－４－メチルピリジン（１４．０ｇ、６３．９ｍｍｏｌ）、４－ｔｅｒｔ-ブチル安息香酸メチル（１２．３ｇ、６３．９ｍｍｏｌ）のテトラヒドロフラン（３２０ｍＬ）溶液に、室温にてリチウムビス(トリメチルシリル)アミド（約２６％テトラヒドロフラン溶液、約１．３ｍｏｌ／Ｌ)（１００ｍＬ、１２８ｍｍｏｌ）を加え、室温で３時間攪拌した。１規定塩酸にて反応溶液を中和後、反応混合物を酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた結晶をヘプタンで洗浄し１－［４－（ｔｅｒｔ-ブチル）フェニル］－２－（３－ヨードピリジン－４－イル）エタン－１－オン（２１．０ｇ、収率８７％）を得た。 (2) Synthesis of 1- [4- (tert-butyl) phenyl] -2- (3-iodopyridin-4-yl) ethane-1-one (Compound No. II-41) 3-Iodo-4-methyl Lithium bis (trimethylsilyl) amide (about 26% tetrahydrofuran) was added to a solution of pyridine (14.0 g, 63.9 mmol) and methyl 4-tert-butylbenzoate (12.3 g, 63.9 mmol) in tetrahydrofuran (320 mL) at room temperature. Solution, about 1.3 mol / L) (100 mL, 128 mmol) was added and stirred at room temperature for 3 hours. The reaction solution was neutralized with 1N hydrochloric acid, and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained crystals were washed with heptane to give 1- [4- (tert-butyl) phenyl] -2- (3-iodopyridin-4-yl) ethane-1-one (21.0 g, yield 87%). Obtained.
（３）目的物の合成
　１－［４－（ｔｅｒｔ-ブチル）フェニル］－２－（３－ヨードピリジン－４－イル）エタン－１－オン（５．０ｇ、１３．２ｍｍｏｌ）のトルエン（２６ｍＬ）溶液中にオキシ塩化リン（２．５ｍＬ、２６．４ｍｍｏｌ）、ジイソプロピルエチルアミン（４．５ｍＬ、２６．４ｍｍｏｌ）を順に加え、９０℃で１時間攪拌した。室温まで放冷した後、反応混合物を水（２６０ｍＬ）に投入し、１規定水酸化ナトリウム水溶液にて中和した。反応混合物を酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル＝２／１・容量比）で精製し、目的物（３．５ｇ、収率６７％）を得た。 (3) Synthesis of target product 1- [4- (tert-butyl) phenyl] -2- (3-iodopyridin-4-yl) ethane-1-one (5.0 g, 13.2 mmol) in toluene (26 mL) ) Phosphorus oxychloride (2.5 mL, 26.4 mmol) and diisopropylethylamine (4.5 mL, 26.4 mmol) were sequentially added to the solution, and the mixture was stirred at 90 ° C. for 1 hour. After cooling to room temperature, the reaction mixture was poured into water (260 mL) and neutralized with 1N aqueous sodium hydroxide solution. The reaction mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 2/1 · volume ratio) to obtain the desired product (3.5 g, yield 67%).
　合成例２
（Ｚ）－４－［２－［４－（ｔｅｒｔ-ブチル）フェニル］－２－クロロビニル］－３－エトキシピリジン（化合物Ｎｏ．I－６４）の合成 Synthesis example 2
Synthesis of (Z) -4- [2- [4- (tert-butyl) phenyl] -2-chlorovinyl] -3-ethoxypyridine (Compound No. I-64)
（１）３－エトキシ－４－メチルピリジンの合成
　３－アミノ－４－メチルピリジン（２５．０ｇ、２３１．２ｍｍｏｌ）のエタノール（２５０ｍＬ）溶液にメタンスルホン酸（２４．４ｇ、２５４．３ｍｍｏｌ）を加え、氷冷した。氷冷下、亜硝酸ｔｅｒｔ-ブチル（３１．８ｇ、２７７．４ｍｍｏｌ）を加えた後、室温で３０分、８０℃で１時間攪拌した。反応溶液を氷冷した後、水（１００ｍＬ）、ナトリウムエトキシド（５２．４ｇ、６９３．５ｍｍｏｌ）を順に加え、室温にて３時間攪拌した。エタノールを減圧下留去し、残渣を水（２５０ｍＬ）に投入した。反応混合物を酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル＝１／１・容量比）で精製し、３－エトキシ－４－メチルピリジン（１６．０ｇ、収率５０％）を得た。 (1) Synthesis of 3-ethoxy-4-methylpyridine Methanesulfonic acid (24.4 g, 254.3 mmol) was added to a solution of 3-amino-4-methylpyridine (25.0 g, 231.2 mmol) in ethanol (250 mL). In addition, it was ice-cooled. Under ice cooling, tert-butyl nitrite (31.8 g, 277.4 mmol) was added, followed by stirring at room temperature for 30 minutes and at 80 ° C. for 1 hour. After cooling the reaction solution with ice, water (100 mL) and sodium ethoxide (52.4 g, 693.5 mmol) were sequentially added, and the mixture was stirred at room temperature for 3 hours. Ethanol was distilled off under reduced pressure, and the residue was poured into water (250 mL). The reaction mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 1/1 volume ratio) to give 3-ethoxy-4-methylpyridine (16.0 g, yield 50%). Obtained.
（２）１－［４－（ｔｅｒｔ-ブチル）フェニル］－２－（３－エトキシピリジン－４－イル）エタン－１－オン（化合物Ｎｏ．ＩＩ－６４）の合成
　３－エトキシ－４－メチルピリジン（１．０ｇ、７．３ｍｍｏｌ）、４－ｔｅｒｔ-ブチル安息香酸メチル（１．８ｇ、９．５ｍｍｏｌ）のテトラヒドロフラン（２５ｍＬ）溶液に、室温にてリチウムビス(トリメチルシリル)アミド（約２６％テトラヒドロフラン溶液、約１．３ｍｏｌ／Ｌ)（１７ｍＬ、２１．９ｍｍｏｌ）を加え、４０℃で２時間攪拌した。１規定塩酸にて反応溶液を中和後、反応混合物を酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル＝２／１・容量比）で精製し、１－［４－（ｔｅｒｔ-ブチル）フェニル］－２－（３－エトキシピリジン－４－イル）エタン－１－オン（１．２５ｇ、収率５８％）を得た。 (2) Synthesis of 1- [4- (tert-butyl) phenyl] -2- (3-ethoxypyridin-4-yl) ethane-1-one (Compound No. II-64) 3-Ethoxy-4-methyl Lithium bis (trimethylsilyl) amide (about 26% tetrahydrofuran) was added to a solution of pyridine (1.0 g, 7.3 mmol) and methyl 4-tert-butylbenzoate (1.8 g, 9.5 mmol) in tetrahydrofuran (25 mL) at room temperature. Solution, about 1.3 mol / L) (17 mL, 21.9 mmol) was added and stirred at 40 ° C. for 2 hours. The reaction solution was neutralized with 1N hydrochloric acid, and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 2/1 volume ratio), and 1- [4- (tert-butyl) phenyl] -2- (3-ethoxy Pyridin-4-yl) ethane-1-one (1.25 g, 58% yield) was obtained.
（３）目的物の合成
　１－［４－（ｔｅｒｔ-ブチル）フェニル］－２－（３－エトキシピリジン－４－イル）エタン－１－オン（３５．０ｇ、１１７．７ｍｍｏｌ）のトルエン（２４０ｍＬ）溶液中にオキシ塩化リン（２１．９ｍＬ、２３５．４ｍｍｏｌ）、ジイソプロピルエチルアミン（４０．２ｍＬ、２３５．４ｍｍｏｌ）を順に加え、９０℃で１時間攪拌した。室温まで放冷した後、反応混合物を水（１２００ｍＬ）に投入し、１０規定水酸化ナトリウム水溶液にて中和した。反応混合物を酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル＝１／１・容量比）で精製し、目的物（２６．５ｇ、収率７１％）を得た。 (3) Synthesis of target product 1- [4- (tert-butyl) phenyl] -2- (3-ethoxypyridin-4-yl) ethane-1-one (35.0 g, 117.7 mmol) in toluene (240 mL) ) Phosphorus oxychloride (21.9 mL, 235.4 mmol) and diisopropylethylamine (40.2 mL, 235.4 mmol) were sequentially added to the solution, and the mixture was stirred at 90 ° C. for 1 hour. After cooling to room temperature, the reaction mixture was poured into water (1200 mL) and neutralized with 10N aqueous sodium hydroxide solution. The reaction mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 1/1 volume ratio) to obtain the desired product (26.5 g, yield 71%).
　合成例３
（Ｚ）－４－［２－［４－（ｔｅｒｔ-ブチル）フェニル］－２－クロロビニル］－３－（エチルチオ）ピリジン（化合物Ｎｏ．I－８４）の合成 Synthesis example 3
Synthesis of (Z) -4- [2- [4- (tert-butyl) phenyl] -2-chlorovinyl] -3- (ethylthio) pyridine (Compound No. I-84)
（１）３－（エチルチオ）－４－メチルピリジンの合成
　３－アミノ－４－メチルピリジン（５．０ｇ、４６．２ｍｍｏｌ）のアセトニトリル（５０ｍＬ）溶液に、１，２－ジエチルスルファン（１１．３ｇ、９２．４ｍｍｏｌ）、亜硝酸ｔｅｒｔ-ブチル（７．２ｇ、６９．３ｍｍｏｌ）を加えた後、加熱還流しながら１６時間攪拌した。室温まで放冷した後、反応混合物を水に投入し、酢酸エチルで抽出した。発生した不溶性の沈殿物をセライトでろ過した後、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル＝７／３・容量比）で精製し、３－（エチルチオ）－４－メチルピリジン（２．６ｇ、収率３６％）を得た。 (1) Synthesis of 3- (ethylthio) -4-methylpyridine To a solution of 3-amino-4-methylpyridine (5.0 g, 46.2 mmol) in acetonitrile (50 mL), 1,2-diethylsulfane (11. 3 g, 92.4 mmol) and tert-butyl nitrite (7.2 g, 69.3 mmol) were added, followed by stirring for 16 hours while heating under reflux. After cooling to room temperature, the reaction mixture was poured into water and extracted with ethyl acetate. The generated insoluble precipitate was filtered through celite, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 7/3, volume ratio) to give 3- (ethylthio) -4-methylpyridine (2.6 g, yield 36%). )
（２）１－［４－（ｔｅｒｔ-ブチル）フェニル］－２－［３－（エチルチオ）ピリジン－４－イル］エタン－１－オン（化合物Ｎｏ．ＩＩ－８４）の合成
　３－（エチルチオ）－４－メチルピリジン（１．０ｇ、６．５ｍｍｏｌ）、４－ｔｅｒｔ-ブチル安息香酸メチル（１．３ｇ、６．９ｍｍｏｌ）のテトラヒドロフラン（１０ｍＬ）溶液に、室温にてリチウムビス(トリメチルシリル)アミド（約２６％テトラヒドロフラン溶液、約１．３ｍｏｌ／Ｌ)（１５ｍＬ、１９．５ｍｍｏｌ）を加え、５０℃で３時間攪拌した。室温まで放冷した後、反応混合物を水に投入し、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル＝３／２・容量比）で精製し、１－［４－（ｔｅｒｔ-ブチル）フェニル］－２－［３－（エチルチオ）ピリジン－４－イル］エタン－１－オン（１．９ｇ、収率９２％）を得た。 (2) Synthesis of 1- [4- (tert-butyl) phenyl] -2- [3- (ethylthio) pyridin-4-yl] ethane-1-one (Compound No. II-84) 3- (Ethylthio) To a solution of -4-methylpyridine (1.0 g, 6.5 mmol), methyl 4-tert-butylbenzoate (1.3 g, 6.9 mmol) in tetrahydrofuran (10 mL) at room temperature with lithium bis (trimethylsilyl) amide ( About 26% tetrahydrofuran solution, about 1.3 mol / L) (15 mL, 19.5 mmol) was added, and the mixture was stirred at 50 ° C. for 3 hours. After cooling to room temperature, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 3/2, volume ratio) to give 1- [4- (tert-butyl) phenyl] -2- [3- ( Ethylthio) pyridin-4-yl] ethane-1-one (1.9 g, 92% yield) was obtained.
（３）目的物の合成
　１－［４－（ｔｅｒｔ-ブチル）フェニル］－２－［３－（エチルチオ）ピリジン－４－イル］エタン－１－オン（１．０ｇ、３．２ｍｍｏｌ）のトルエン（１０ｍＬ）溶液中にオキシ塩化リン（０．９８ｇ、６．４ｍｍｏｌ）、ジイソプロピルエチルアミン（０．８２ｇ、６．４ｍｍｏｌ）を順に加え、９０℃で１時間攪拌した。水を加えた後、氷冷し、１規定水酸化ナトリウム水溶液にて中和した。反応混合物を酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル＝４／１・容量比）で精製し、目的物（０．９１ｇ、収率８５％）を得た。 (3) Synthesis of target product 1- [4- (tert-butyl) phenyl] -2- [3- (ethylthio) pyridin-4-yl] ethane-1-one (1.0 g, 3.2 mmol) in toluene (10 mL) To the solution, phosphorus oxychloride (0.98 g, 6.4 mmol) and diisopropylethylamine (0.82 g, 6.4 mmol) were sequentially added, followed by stirring at 90 ° C. for 1 hour. After adding water, the mixture was ice-cooled and neutralized with a 1N aqueous sodium hydroxide solution. The reaction mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 4/1 · volume ratio) to obtain the desired product (0.91 g, yield 85%).
　合成例４
（Ｚ）－４－［２－［４－（ｔｅｒｔ-ブチル）フェニル］－２－クロロビニル］－３－（エチルスルフィニル）ピリジン（化合物Ｎｏ．I－９４）及び（Ｚ）－４－［２－［４－（ｔｅｒｔ-ブチル）フェニル］－２－クロロビニル］－３－（エチルスルホニル）ピリジン（化合物Ｎｏ．I－１０４）の合成 Synthesis example 4
(Z) -4- [2- [4- (tert-butyl) phenyl] -2-chlorovinyl] -3- (ethylsulfinyl) pyridine (Compound No. I-94) and (Z) -4- [2 Synthesis of — [4- (tert-butyl) phenyl] -2-chlorovinyl] -3- (ethylsulfonyl) pyridine (Compound No. I-104)
　（Ｚ）－４－［２－［４－（ｔｅｒｔ-ブチル）フェニル］－２－クロロビニル］－３－（エチルチオ）ピリジン（０．６８ｇ、２．１ｍｍｏｌ）のクロロホルム（１０ｍＬ）溶液に、３－クロロ過安息香酸（０．５３ｇ、３．１ｍｍｏｌ）を加え、室温で１時間攪拌した。反応混合物に炭酸水素ナトリウム水溶液を加えた後、クロロホルムで抽出した。有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル＝７／３及び１／１・容量比）で精製し、化合物Ｎｏ．I－９４（０．１５ｇ、収率２１％）及び化合物Ｎｏ．I－１０４（０．２３ｇ、収率３０％）を得た。 To a solution of (Z) -4- [2- [4- (tert-butyl) phenyl] -2-chlorovinyl] -3- (ethylthio) pyridine (0.68 g, 2.1 mmol) in chloroform (10 mL), 3 -Chloroperbenzoic acid (0.53 g, 3.1 mmol) was added and stirred at room temperature for 1 hour. To the reaction mixture was added aqueous sodium hydrogen carbonate solution, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 7/3 and 1/1 volume ratio). I-94 (0.15 g, 21% yield) and compound no. I-104 (0.23 g, 30% yield) was obtained.
合成例５
（Ｚ）－４－［２－［４－（ｔｅｒｔ-ブチル）フェニル］－２－クロロビニル］－３－（１－プロピン－１－イル）ピリジン（化合物Ｎｏ．Ｉ－１２６）の合成
　合成例１に準じて製造した（Ｚ）－３－ブロモ－４－［２－［４－（ｔｅｒｔ-ブチル）フェニル］－２－クロロビニル］ピリジン（化合物Ｎｏ．I－２４）（０．５０ｇ、１．４ｍｍｏｌ）、二塩化ビストリフェニルホスフィンパラジウム（５０ｍｇ、０．０７ｍｍｏｌ）、ヨウ化銅（Ｉ）（４０ｍｇ、０．２１ｍｍｏｌ）のＮ，Ｎ－ジメチルホルムアミド（４ｍＬ）溶液に、トリエチルアミン（０．４３ｇ、４．３ｍｍｏｌ）、１－プロピン（約３％ヘプタン溶液、３．８ｇ、２．８ｍｍｏｌ）を加え封管後、マイクロ波照射下、８０℃で５時間攪拌した。室温まで放冷した後、反応混合物を水に投入し、酢酸エチルで抽出した。沈殿物をセライトでろ過した後、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムを加え乾燥した。無水硫酸ナトリウムをろ過で取り除いた後、溶媒を減圧下留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル＝４／１・容量比）で精製し、目的物（０．１１ｇ、収率２４％）を得た。 Synthesis example 5
Synthesis of (Z) -4- [2- [4- (tert-butyl) phenyl] -2-chlorovinyl] -3- (1-propyn-1-yl) pyridine (Compound No. I-126) Synthesis Example (Z) -3-bromo-4- [2- [4- (tert-butyl) phenyl] -2-chlorovinyl] pyridine (Compound No. I-24) (0.50 g, 1 .4 mmol), bistriphenylphosphine palladium dichloride (50 mg, 0.07 mmol), copper (I) iodide (40 mg, 0.21 mmol) in N, N-dimethylformamide (4 mL) solution, triethylamine (0.43 g, 4.3 mmol) and 1-propyne (about 3% heptane solution, 3.8 g, 2.8 mmol) were added, and the mixture was sealed and stirred at 80 ° C. for 5 hours under microwave irradiation. After cooling to room temperature, the reaction mixture was poured into water and extracted with ethyl acetate. The precipitate was filtered through celite, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 4/1 · volume ratio) to obtain the desired product (0.11 g, yield 24%).
　次に、本発明に係る式（Ｉ）の化合物の代表例を第１表に挙げる。また、式（Ｉ）の化合物の製造用中間体である式（ＩＩ）の化合物の代表例を第２表に挙げる。これらの化合物は、前記合成例或いは前記した種々の製造方法に基づいて合成することができる。第１表及び第２表の物性欄中に記載の数値は融点（℃）を、「Ｏｉｌ」は油状物を、「ａｍｏｒｐｈｏｕｓ」は非晶質を各々示し、融点が示されていない化合物についてはそれらの１Ｈ－ＮＭＲスペクトルデータを各々第３表及び第４表に挙げる。 Next, typical examples of the compounds of formula (I) according to the present invention are listed in Table 1. Further, typical examples of the compound of the formula (II) which is an intermediate for producing the compound of the formula (I) are listed in Table 2. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. The numerical values described in the physical properties column of Tables 1 and 2 are melting points (° C.), “Oil” is an oily substance, “amorphous” is amorphous, and a compound whose melting point is not shown. Their 1 H-NMR spectral data are listed in Tables 3 and 4, respectively.
　尚、第１表～第４表中のＮｏ．は化合物番号を示す。また、表中、Ｍｅはメチル基を、Ｅｔはエチル基を、ｎ－Ｐｒはノルマルプロピル基を、ｉ－Ｐｒはイソプロピル基をｉ－Ｂｕはイソブチル基を、ｔｅｒｔ－Ｂｕはターシャリーブチル基を表す。また、Ｒ１の欄において、例えば「４－Ｆ」と記載された化合物は、表中の化学構造式に付与した置換位置のみがＲ１で置換されていること、即ち、４位のみがフッ素原子にて置換されていることを表し、他の同様の記載もこれに準じる。
  In Tables 1 to 4, No. Indicates a compound number. In the table, Me represents a methyl group, Et represents an ethyl group, n-Pr represents a normal propyl group, i-Pr represents an isopropyl group, i-Bu represents an isobutyl group, and tert-Bu represents a tertiary butyl group. To express. In the column of R 1 , for example, in the compound described as “4-F”, only the substitution position given to the chemical structural formula in the table is substituted with R 1 , that is, only the 4-position is fluorine. This means that it is substituted with an atom, and other similar descriptions also apply to this.
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
試験例１　トビイロウンカに対する効果試験
　本発明化合物の濃度が２００ｐｐｍとなるよう調製した薬液に、イネ幼苗を浸漬処理した。薬液が風乾した後に、湿った脱脂綿で根部を包んで試験管に入れた。この中にトビイロウンカ２～３齢幼虫を約１０頭放ち、管口をガーゼでふたをして２５℃の照明付恒温室内に放置した。放虫５日後にトビイロウンカの生死を判定し、下記の計算式により死虫率（％）を求めた。その結果、前記化合物Ｎｏ．Ｉ－４１、Ｉ－６４、Ｉ－１２２、Ｉ－１２３、Ｉ－１２４、Ｉ－１２５、Ｉ－１２６、ＩＩ－４１及びＩＩ－６４が９０％以上の死虫率を示した。
　死虫率（％）＝（死虫数／放虫数）×１００ Test Example 1 Effect test on green planthopper Rice seedlings were immersed in a chemical solution prepared so that the concentration of the compound of the present invention was 200 ppm. After the chemical solution was air-dried, the root was wrapped with wet absorbent cotton and placed in a test tube. In this, about 10 larvae of 2-3 years old were released, and the tube mouth was covered with gauze and left in a constant temperature room at 25 ° C. Five days after the insect release, the dead planthopper was judged to be alive or dead, and the death rate (%) was determined by the following formula. As a result, the compound no. I-41, I-64, I-122, I-123, I-124, I-125, I-126, II-41 and II-64 showed a death rate of 90% or more.
Death rate (%) = (Number of dead insects / Number of dead insects) × 100
試験例２　タバココナジラミに対する効果試験
　タバココナジラミ１～２齢幼虫が寄生したポット植えのキュウリ苗に、本発明化合物の濃度が２００ｐｐｍとなるよう調製した薬液を、ハンドスプレーを用いて散布処理した。薬液が風乾した後に、２５℃の照明付恒温室内に放置した。処理１０日後に老齢幼虫数を調査し、下記計算式により防除価を求めた。その結果、前記化合物Ｎｏ．Ｉ－４１、Ｉ－６４、Ｉ－１２２、Ｉ－１２３、Ｉ－１２４、Ｉ－１２５、Ｉ－１２６、Ｉ－１２７、Ｉ－１２８及びＩＩ－４１が９０以上の防除価を示した。
　防除価＝［１－（Ｔａ×Ｃｂ）／（Ｔｂ×Ｃａ）］×１００
　　Ｔａ：処理キュウリ苗における処理後の老齢幼虫数
　　Ｔｂ：処理キュウリ苗における処理前の１～２齢幼虫数
　　Ｃａ：無処理キュウリ苗における処理後の老齢幼虫数
　　Ｃｂ：無処理キュウリ苗における処理前の１～２齢幼虫数 Test Example 2 Effect Test on Tobacco Whitefly To a pot-planted cucumber seedling parasitized with 1 to 2 instar larvae, a chemical solution prepared to a concentration of 200 ppm of the compound of the present invention was sprayed using a hand spray. After the chemical solution was air-dried, it was left in a constant temperature room at 25 ° C. with illumination. Ten days after the treatment, the number of old larvae was examined, and the control value was determined by the following formula. As a result, the compound no. I-41, I-64, I-122, I-123, I-124, I-125, I-126, I-127, I-128 and II-41 showed control values of 90 or more.
Control value = [1− (Ta × Cb) / (Tb × Ca)] × 100
Ta: Number of old larvae after treatment in treated cucumber seedling Tb: Number of first to second larvae before treatment in treated cucumber seedling Ca: Number of old larvae after treatment in untreated cucumber seedling Cb: Before treatment in untreated cucumber seedling Number of larvae 1-2
　次に製剤例を記載する。
製剤例１
（１）本発明化合物　２０重量部
（２）クレー　７０重量部
（３）ホワイトカーボン　５重量部
（４）ポリカルボン酸ナトリウム　３重量部
（５）アルキルナフタレンスルホン酸ナトリウム　２重量部
以上のものを均一に混合して水和剤とする。 Next, formulation examples are described.
Formulation Example 1
(1) Compound of the present invention 20 parts by weight (2) Clay 70 parts by weight (3) White carbon 5 parts by weight (4) Sodium polycarboxylate 3 parts by weight (5) Sodium alkylnaphthalene sulfonate 2 parts by weight or more To make a wettable powder.
製剤例２
（１）本発明化合物　５重量部
（２）タルク　６０重量部
（３）炭酸カルシウム　３４．５重量部
（４）流動パラフィン　０．５重量部
以上のものを均一に混合して粉剤とする。 Formulation Example 2
(1) Compound of the present invention 5 parts by weight (2) Talc 60 parts by weight (3) Calcium carbonate 34.5 parts by weight (4) Liquid paraffin 0.5 parts by weight or more are uniformly mixed to obtain a powder.
製剤例３
（１）本発明化合物　２０重量部
（２）Ｎ，Ｎ－ジメチルアセトアミド　２０重量部
（３）ポリオキシエチレントリスチリルフェニルエーテル　１０重量部
（４）ドデシルベンゼンスルホン酸カルシウム　２重量部
（５）キシレン　４８重量部
以上のものを均一に混合、溶解して乳剤とする。 Formulation Example 3
(1) Compound of the present invention 20 parts by weight (2) N, N-dimethylacetamide 20 parts by weight (3) Polyoxyethylene tristyryl phenyl ether 10 parts by weight (4) Calcium dodecylbenzenesulfonate 2 parts by weight (5) Xylene 48 A mixture of more than parts by weight is uniformly mixed and dissolved to obtain an emulsion.
製剤例４
（１）クレー　６８重量部
（２）リグニンスルホン酸ナトリウム　２重量部
（３）ポリオキシエチレンアルキルアリールサルフェート　５重量部
（４）ホワイトカーボン　２５重量部
以上の各成分の混合物と、本発明化合物とを４：１の重量割合で混合し、水和剤とする。 Formulation Example 4
(1) Clay 68 parts by weight (2) Sodium lignin sulfonate 2 parts by weight (3) Polyoxyethylene alkylaryl sulfate 5 parts by weight (4) White carbon 25 parts by weight A mixture of each component and the present compound Mix at a weight ratio of 4: 1 to make a wettable powder.
製剤例５
（１）本発明化合物　５０重量部
（２）アルキルナフタレンスルホン酸ナトリウムホルムアルデヒド縮合物　２重量部
（３）シリコーンオイル　０．２重量部
（４）水　４７．８重量部
以上のものを均一に混合、粉砕した原液に更に
（５）ポリカルボン酸ナトリウム　５重量部
（６）無水硫酸ナトリウム　４２．８重量部
を加え均一に混合、造粒、乾燥して顆粒水和剤とする。 Formulation Example 5
(1) Compound of the present invention 50 parts by weight (2) Sodium alkylnaphthalene sulfonate formaldehyde condensate 2 parts by weight (3) Silicone oil 0.2 parts by weight (4) Water 47.8 parts by weight or more uniformly mixed (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are further added to the crushed stock solution, and the mixture is uniformly mixed, granulated and dried to obtain a granulated wettable powder.
製剤例６
（１）本発明化合物　５重量部
（２）ポリオキシエチレンオクチルフェニルエーテル　１重量部
（３）ポリオキシエチレンアルキルエーテルリン酸エステル　０．１重量部
（４）粒状炭酸カルシウム　９３．９重量部
（１）～（３）を予め均一に混合し、適量のアセトンで希釈した後、（４）に吹付け、アセトンを除去して粒剤とする。 Formulation Example 6
(1) Compound of the present invention 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Polyoxyethylene alkyl ether phosphate 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight (1 ) To (3) are mixed uniformly in advance and diluted with an appropriate amount of acetone, and then sprayed onto (4) to remove acetone and form granules.
製剤例７
（１）本発明化合物　２．５重量部
（２）Ｎ，Ｎ－ジメチルアセトアミド　２．５重量部
（３）大豆油　９５．０重量部
以上のものを均一に混合、溶解して微量散布剤(ultra low volume formulation)とする。 Formulation Example 7
(1) Compound of the present invention 2.5 parts by weight (2) N, N-dimethylacetamide 2.5 parts by weight (3) Soybean oil 95.0 parts by weight or more are uniformly mixed and dissolved to give a trace amount of spray ( ultra low volume formulation).
製剤例８
（１）本発明化合物　１０重量部
（２）ジエチレングリコールモノエチルエーテル　８０重量部
（３）ポリオキシエチレンアルキルエーテル　１０重量部
以上の成分を均一に混合し、液剤とする。 Formulation Example 8
(1) Compound of the present invention 10 parts by weight (2) Diethylene glycol monoethyl ether 80 parts by weight (3) Polyoxyethylene alkyl ether 10 parts by weight or more of ingredients are mixed uniformly to obtain a liquid agent.
　本発明を特定の態様を用いて詳細に説明したが、本発明の意図と範囲を離れることなく様々な変更および変形が可能であることは、当業者にとって明らかである。なお本出願は、２０１４年１０月３１日付で出願された日本特許出願（特願２０１４－２２２１３６）に基づいており、その全体が引用により援用される。 Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2014-222136) filed on October 31, 2014, and is incorporated by reference in its entirety.

Claims (10)

  1. 　式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000001
     〔式中、Ｒ１はハロゲン原子、シアノ、ニトロ、（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ３－Ｃ６）シクロアルキル、（Ｃ１－Ｃ６）ハロアルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ２－Ｃ６）アルケニルオキシ、（Ｃ２－Ｃ６）アルキニルオキシ、（Ｃ３－Ｃ６）シクロアルコキシ、（Ｃ１－Ｃ６）ハロアルコキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ２－Ｃ６）アルケニルチオ、（Ｃ２－Ｃ６）アルキニルチオ、（Ｃ３－Ｃ６）シクロアルキルチオ、（Ｃ１－Ｃ６）ハロアルキルチオ、（Ｃ１－Ｃ６）アルキルアミノ、（Ｃ２－Ｃ６）アルケニルアミノ、（Ｃ２－Ｃ６）アルキニルアミノ、ジ（Ｃ１－Ｃ６）アルキルアミノ、ジ（Ｃ２－Ｃ６）アルケニルアミノ、ジ（Ｃ２－Ｃ６）アルキニルアミノ、（Ｃ１－Ｃ６）アルキルスルフィニル、（Ｃ２－Ｃ６）アルケニルスルフィニル、（Ｃ２－Ｃ６）アルキニルスルフィニル、（Ｃ３－Ｃ６）シクロアルキルスルフィニル、（Ｃ１－Ｃ６）ハロアルキルスルフィニル、（Ｃ１－Ｃ６）アルキルスルホニル、（Ｃ２－Ｃ６）アルケニルスルホニル、（Ｃ２－Ｃ６）アルキニルスルホニル、（Ｃ１－Ｃ６アルキル）カルボニル、（Ｃ１－Ｃ６アルコキシ）カルボニル、（Ｃ１－Ｃ６アルキル）アミノカルボニル、ジ（Ｃ１－Ｃ６アルキル）アミノカルボニル、（Ｃ１－Ｃ６アルキル）カルボニルオキシ、（Ｃ１－Ｃ６アルキル）カルボニルアミノ又は（Ｃ１－Ｃ６アルキル）カルボニル（Ｃ１－Ｃ６）アルキルアミノであり；Ｒ２はハロゲン原子、シアノ、ニトロ、（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ１－Ｃ６）ハロアルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ３－Ｃ６）シクロアルコキシ、（Ｃ１－Ｃ６）ハロアルコキシ、（Ｃ２－Ｃ６）アルケニルオキシ、（Ｃ２－Ｃ６）アルキニルオキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ２－Ｃ６）アルケニルチオ、（Ｃ２－Ｃ６）アルキニルチオ、（Ｃ３－Ｃ６）シクロアルキルチオ、（Ｃ１－Ｃ６）アルキルアミノ、（Ｃ２－Ｃ６）アルケニルアミノ、（Ｃ２－Ｃ６）アルキニルアミノ、ジ（Ｃ１－Ｃ６）アルキルアミノ、ジ（Ｃ２－Ｃ６）アルケニルアミノ、ジ（Ｃ２－Ｃ６）アルキニルアミノ、（Ｃ１－Ｃ６）アルキルスルフィニル、（Ｃ２－Ｃ６）アルケニルスルフィニル、（Ｃ２－Ｃ６）アルキニルスルフィニル、（Ｃ１－Ｃ６）アルキルスルホニル、（Ｃ２－Ｃ６）アルケニルスルホニル、（Ｃ２－Ｃ６）アルキニルスルホニル、（Ｃ１－Ｃ６）アルキルオキシ（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルキルチオ（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルキルアミノ（Ｃ１－Ｃ６）アルキル、ジ（Ｃ１－Ｃ６）アルキルアミノ（Ｃ１－Ｃ６）アルキル、ホルミル、（Ｃ１－Ｃ６アルキル）カルボニル、（Ｃ１－Ｃ６アルコキシ）カルボニル、（Ｃ１－Ｃ６アルキル）アミノカルボニル、ジ（Ｃ１－Ｃ６アルキル）アミノカルボニル、（Ｃ１－Ｃ６アルキル）カルボニルオキシ、（Ｃ１－Ｃ６アルキル）カルボニルチオ、（Ｃ１－Ｃ６アルキル）カルボニルアミノ又はジ（Ｃ１－Ｃ６アルキル）カルボニルアミノであり；ｎは０～５の整数であり；ｎが２以上のとき、複数のＲ１は同一又は異なっていてもよい〕で表される４－（フェニルエテニル）ピリジン系化合物又はその塩。     Formula (I):
    Figure JPOXMLDOC01-appb-C000001
     [Wherein R 1 is a halogen atom, cyano, nitro, (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl] , (C 1 -C 6 ) haloalkyl, (C 1 -C 6 ) alkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 3 -C 6 ) cycloalkoxy, ( C 1 -C 6 ) haloalkoxy, (C 1 -C 6 ) alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, (C 3 -C 6 ) cycloalkylthio, (C 1- C 6 ) haloalkylthio, (C 1 -C 6 ) alkylamino, (C 2 -C 6 ) alkenylamino, (C 2 -C 6 ) alkynylamino, di (C 1 -C 6 ) alkylamino, di ( 2 -C 6) alkenyl, di (C 2 -C 6) alkynyl amino, (C 1 -C 6) alkylsulfinyl, (C 2 -C 6) alkenylsulfinyl, (C 2 -C 6) alkynylsulfinyl, ( C 3 -C 6) cycloalkyl alkylsulfinyl, (C 1 -C 6) haloalkylsulfinyl, (C 1 -C 6) alkylsulfonyl, (C 2 -C 6) alkenyl-sulfonyl, (C 2 -C 6) alkynyl-sulfonyl, (C 1 -C 6 alkyl) carbonyl, (C 1 -C 6 alkyl) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, (C 1 -C 6 alkyl) ) carbonyloxy, (C 1 -C 6 alkyl) carbonylamino or (C 1 -C 6 alkyl) carboxamide There Le (C 1 -C 6) alkylamino; R 2 is a halogen atom, cyano, nitro, (C 1 -C 6) alkyl, (C 2 -C 6) alkenyl, (C 2 -C 6) alkynyl, (C 1 -C 6 ) haloalkyl, (C 1 -C 6 ) alkoxy, (C 3 -C 6 ) cycloalkoxy, (C 1 -C 6 ) haloalkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 1 -C 6 ) alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, (C 3 -C 6 ) cycloalkylthio, (C 1 -C 6) alkylamino, (C 2 -C 6) alkenyl amino, (C 2 -C 6) alkynyl amino, di (C 1 -C 6) alkylamino, di (C 2 -C 6) alkenyl, di C 2 -C 6) alkynyl amino, (C 1 -C 6) alkylsulfinyl, (C 2 -C 6) alkenylsulfinyl, (C 2 -C 6) alkynylsulfinyl, (C 1 -C 6) alkylsulfonyl, ( C 2 -C 6 ) alkenylsulfonyl, (C 2 -C 6 ) alkynylsulfonyl, (C 1 -C 6 ) alkyloxy (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkylthio (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkylamino (C 1 -C 6 ) alkyl, di (C 1 -C 6 ) alkylamino (C 1 -C 6 ) alkyl, formyl, (C 1 -C 6 alkyl) ) carbonyl, (C 1 -C 6 alkoxy) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl (C 1 -C 6 alkyl) carbonyloxy, be (C 1 -C 6 alkyl) carbonyl thio, (C 1 -C 6 alkyl) carbonylamino or di (C 1 -C 6 alkyl) carbonylamino; n is 0 A 4- (phenylethenyl) pyridine-based compound or a salt thereof, which is an integer of ˜5; and when n is 2 or more, a plurality of R 1 may be the same or different.
  2. 　Ｒ１がハロゲン原子、（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）ハロアルキル又は（Ｃ１－Ｃ６）ハロアルコキシであり、Ｒ２がハロゲン原子、（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ１－Ｃ６）アルキルスルフィニル、（Ｃ１－Ｃ６）アルキルスルホニル、（Ｃ１－Ｃ６アルコキシ）カルボニル、（Ｃ１－Ｃ６アルキル）アミノカルボニル又はジ（Ｃ１－Ｃ６アルキル）アミノカルボニルである請求項１に記載の４－（フェニルエテニル）ピリジン系化合物又はその塩。 R 1 is a halogen atom, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl or (C 1 -C 6 ) haloalkoxy, R 2 is a halogen atom, (C 1 -C 6 ) alkyl , (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio, (C 1 -C 6 ) alkylsulfinyl, (C 1 The 4- (4-) of claim 1 which is -C 6 ) alkylsulfonyl, (C 1 -C 6 alkoxy) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl or di (C 1 -C 6 alkyl) aminocarbonyl. Phenylethenyl) pyridine compound or a salt thereof.
  3. 　Ｒ１がハロゲン原子、（Ｃ１－Ｃ６）アルキル又は（Ｃ１－Ｃ６）ハロアルコキシである請求項２に記載の４－（フェニルエテニル）ピリジン系化合物又はその塩。 The 4- (phenylethenyl) pyridine compound or a salt thereof according to claim 2, wherein R 1 is a halogen atom, (C 1 -C 6 ) alkyl or (C 1 -C 6 ) haloalkoxy.
  4. 　請求項１に記載の化合物又はその塩を有効成分として含有する有害生物防除剤。 A pest control agent comprising the compound according to claim 1 or a salt thereof as an active ingredient.
  5. 　請求項１に記載の化合物又はその塩を有効成分として含有する殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤。 An insecticide, acaricide, nematicide or soil insecticide containing the compound according to claim 1 or a salt thereof as an active ingredient.
  6. 　請求項１に記載の化合物又はその塩を有効成分として含有する殺動物寄生生物剤。 An animal killing parasite agent comprising the compound according to claim 1 or a salt thereof as an active ingredient.
  7. 　請求項１に記載の化合物又はその塩の有効量を施用して有害生物を防除する方法。 A method for controlling pests by applying an effective amount of the compound according to claim 1 or a salt thereof.
  8. 　式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000002
     〔式中、Ｒ１はハロゲン原子、シアノ、ニトロ、（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ３－Ｃ６）シクロアルキル、（Ｃ１－Ｃ６）ハロアルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ２－Ｃ６）アルケニルオキシ、（Ｃ２－Ｃ６）アルキニルオキシ、（Ｃ３－Ｃ６）シクロアルコキシ、（Ｃ１－Ｃ６）ハロアルコキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ２－Ｃ６）アルケニルチオ、（Ｃ２－Ｃ６）アルキニルチオ、（Ｃ３－Ｃ６）シクロアルキルチオ、（Ｃ１－Ｃ６）ハロアルキルチオ、（Ｃ１－Ｃ６）アルキルアミノ、（Ｃ２－Ｃ６）アルケニルアミノ、（Ｃ２－Ｃ６）アルキニルアミノ、ジ（Ｃ１－Ｃ６）アルキルアミノ、ジ（Ｃ２－Ｃ６）アルケニルアミノ、ジ（Ｃ２－Ｃ６）アルキニルアミノ、（Ｃ１－Ｃ６）アルキルスルフィニル、（Ｃ２－Ｃ６）アルケニルスルフィニル、（Ｃ２－Ｃ６）アルキニルスルフィニル、（Ｃ３－Ｃ６）シクロアルキルスルフィニル、（Ｃ１－Ｃ６）ハロアルキルスルフィニル、（Ｃ１－Ｃ６）アルキルスルホニル、（Ｃ２－Ｃ６）アルケニルスルホニル、（Ｃ２－Ｃ６）アルキニルスルホニル、（Ｃ１－Ｃ６アルキル）カルボニル、（Ｃ１－Ｃ６アルコキシ）カルボニル、（Ｃ１－Ｃ６アルキル）アミノカルボニル、ジ（Ｃ１－Ｃ６アルキル）アミノカルボニル、（Ｃ１－Ｃ６アルキル）カルボニルオキシ、（Ｃ１－Ｃ６アルキル）カルボニルアミノ又は（Ｃ１－Ｃ６アルキル）カルボニル（Ｃ１－Ｃ６）アルキルアミノであり；Ｒ２はハロゲン原子、シアノ、ニトロ、（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ１－Ｃ６）ハロアルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ３－Ｃ６）シクロアルコキシ、（Ｃ１－Ｃ６）ハロアルコキシ、（Ｃ２－Ｃ６）アルケニルオキシ、（Ｃ２－Ｃ６）アルキニルオキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ２－Ｃ６）アルケニルチオ、（Ｃ２－Ｃ６）アルキニルチオ、（Ｃ３－Ｃ６）シクロアルキルチオ、（Ｃ１－Ｃ６）アルキルアミノ、（Ｃ２－Ｃ６）アルケニルアミノ、（Ｃ２－Ｃ６）アルキニルアミノ、ジ（Ｃ１－Ｃ６）アルキルアミノ、ジ（Ｃ２－Ｃ６）アルケニルアミノ、ジ（Ｃ２－Ｃ６）アルキニルアミノ、（Ｃ１－Ｃ６）アルキルスルフィニル、（Ｃ２－Ｃ６）アルケニルスルフィニル、（Ｃ２－Ｃ６）アルキニルスルフィニル、（Ｃ１－Ｃ６）アルキルスルホニル、（Ｃ２－Ｃ６）アルケニルスルホニル、（Ｃ２－Ｃ６）アルキニルスルホニル、（Ｃ１－Ｃ６）アルキルオキシ（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルキルチオ（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルキルアミノ（Ｃ１－Ｃ６）アルキル、ジ（Ｃ１－Ｃ６）アルキルアミノ（Ｃ１－Ｃ６）アルキル、ホルミル、（Ｃ１－Ｃ６アルキル）カルボニル、（Ｃ１－Ｃ６アルコキシ）カルボニル、（Ｃ１－Ｃ６アルキル）アミノカルボニル、ジ（Ｃ１－Ｃ６アルキル）アミノカルボニル、（Ｃ１－Ｃ６アルキル）カルボニルオキシ、（Ｃ１－Ｃ６アルキル）カルボニルチオ、（Ｃ１－Ｃ６アルキル）カルボニルアミノ又はジ（Ｃ１－Ｃ６アルキル）カルボニルアミノであり；ｎは０～５の整数であり；ｎが２以上のとき、複数のＲ１は同一又は異なっていてもよい〕で表される４－（フェニルエテニル）ピリジン系化合物又はその塩の製造方法であって、式（ＩＩ）：
    Figure JPOXMLDOC01-appb-C000003
     〔式中、Ｒ１、Ｒ２及びｎは前述の定義通りである〕で表される化合物又はその塩を塩基の存在下で、塩素化剤と反応させることを特徴とする、４－（フェニルエテニル）ピリジン系化合物又はその塩の製造方法。     Formula (I):
    Figure JPOXMLDOC01-appb-C000002
     [Wherein R 1 is a halogen atom, cyano, nitro, (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl] , (C 1 -C 6 ) haloalkyl, (C 1 -C 6 ) alkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 3 -C 6 ) cycloalkoxy, ( C 1 -C 6 ) haloalkoxy, (C 1 -C 6 ) alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, (C 3 -C 6 ) cycloalkylthio, (C 1- C 6 ) haloalkylthio, (C 1 -C 6 ) alkylamino, (C 2 -C 6 ) alkenylamino, (C 2 -C 6 ) alkynylamino, di (C 1 -C 6 ) alkylamino, di ( 2 -C 6) alkenyl, di (C 2 -C 6) alkynyl amino, (C 1 -C 6) alkylsulfinyl, (C 2 -C 6) alkenylsulfinyl, (C 2 -C 6) alkynylsulfinyl, ( C 3 -C 6) cycloalkyl alkylsulfinyl, (C 1 -C 6) haloalkylsulfinyl, (C 1 -C 6) alkylsulfonyl, (C 2 -C 6) alkenyl-sulfonyl, (C 2 -C 6) alkynyl-sulfonyl, (C 1 -C 6 alkyl) carbonyl, (C 1 -C 6 alkyl) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, (C 1 -C 6 alkyl) ) carbonyloxy, (C 1 -C 6 alkyl) carbonylamino or (C 1 -C 6 alkyl) carboxamide There Le (C 1 -C 6) alkylamino; R 2 is a halogen atom, cyano, nitro, (C 1 -C 6) alkyl, (C 2 -C 6) alkenyl, (C 2 -C 6) alkynyl, (C 1 -C 6 ) haloalkyl, (C 1 -C 6 ) alkoxy, (C 3 -C 6 ) cycloalkoxy, (C 1 -C 6 ) haloalkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 1 -C 6 ) alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, (C 3 -C 6 ) cycloalkylthio, (C 1 -C 6) alkylamino, (C 2 -C 6) alkenyl amino, (C 2 -C 6) alkynyl amino, di (C 1 -C 6) alkylamino, di (C 2 -C 6) alkenyl, di C 2 -C 6) alkynyl amino, (C 1 -C 6) alkylsulfinyl, (C 2 -C 6) alkenylsulfinyl, (C 2 -C 6) alkynylsulfinyl, (C 1 -C 6) alkylsulfonyl, ( C 2 -C 6 ) alkenylsulfonyl, (C 2 -C 6 ) alkynylsulfonyl, (C 1 -C 6 ) alkyloxy (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkylthio (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkylamino (C 1 -C 6 ) alkyl, di (C 1 -C 6 ) alkylamino (C 1 -C 6 ) alkyl, formyl, (C 1 -C 6 alkyl) ) carbonyl, (C 1 -C 6 alkoxy) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl (C 1 -C 6 alkyl) carbonyloxy, be (C 1 -C 6 alkyl) carbonyl thio, (C 1 -C 6 alkyl) carbonylamino or di (C 1 -C 6 alkyl) carbonylamino; n is 0 A plurality of R 1 may be the same or different when n is 2 or more], and a method for producing a 4- (phenylethenyl) pyridine-based compound or a salt thereof, Formula (II):
    Figure JPOXMLDOC01-appb-C000003
     [Wherein R 1 , R 2 and n are as defined above] or a salt thereof is reacted with a chlorinating agent in the presence of a base, 4- (phenyl A method for producing an ethenyl) pyridine compound or a salt thereof.
  9. 　式（ＩＩ）：
    Figure JPOXMLDOC01-appb-C000004
     〔式中、Ｒ１はハロゲン原子、シアノ、ニトロ、（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ３－Ｃ６）シクロアルキル、（Ｃ１－Ｃ６）ハロアルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ２－Ｃ６）アルケニルオキシ、（Ｃ２－Ｃ６）アルキニルオキシ、（Ｃ３－Ｃ６）シクロアルコキシ、（Ｃ１－Ｃ６）ハロアルコキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ２－Ｃ６）アルケニルチオ、（Ｃ２－Ｃ６）アルキニルチオ、（Ｃ３－Ｃ６）シクロアルキルチオ、（Ｃ１－Ｃ６）ハロアルキルチオ、（Ｃ１－Ｃ６）アルキルアミノ、（Ｃ２－Ｃ６）アルケニルアミノ、（Ｃ２－Ｃ６）アルキニルアミノ、ジ（Ｃ１－Ｃ６）アルキルアミノ、ジ（Ｃ２－Ｃ６）アルケニルアミノ、ジ（Ｃ２－Ｃ６）アルキニルアミノ、（Ｃ１－Ｃ６）アルキルスルフィニル、（Ｃ２－Ｃ６）アルケニルスルフィニル、（Ｃ２－Ｃ６）アルキニルスルフィニル、（Ｃ３－Ｃ６）シクロアルキルスルフィニル、（Ｃ１－Ｃ６）ハロアルキルスルフィニル、（Ｃ１－Ｃ６）アルキルスルホニル、（Ｃ２－Ｃ６）アルケニルスルホニル、（Ｃ２－Ｃ６）アルキニルスルホニル、（Ｃ１－Ｃ６アルキル）カルボニル、（Ｃ１－Ｃ６アルコキシ）カルボニル、（Ｃ１－Ｃ６アルキル）アミノカルボニル、ジ（Ｃ１－Ｃ６アルキル）アミノカルボニル、（Ｃ１－Ｃ６アルキル）カルボニルオキシ、（Ｃ１－Ｃ６アルキル）カルボニルアミノ又は（Ｃ１－Ｃ６アルキル）カルボニル（Ｃ１－Ｃ６）アルキルアミノであり；Ｒ２はハロゲン原子、シアノ、ニトロ、（Ｃ１－Ｃ６）アルキル、（Ｃ２－Ｃ６）アルケニル、（Ｃ２－Ｃ６）アルキニル、（Ｃ１－Ｃ６）ハロアルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ３－Ｃ６）シクロアルコキシ、（Ｃ１－Ｃ６）ハロアルコキシ、（Ｃ２－Ｃ６）アルケニルオキシ、（Ｃ２－Ｃ６）アルキニルオキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ２－Ｃ６）アルケニルチオ、（Ｃ２－Ｃ６）アルキニルチオ、（Ｃ３－Ｃ６）シクロアルキルチオ、（Ｃ１－Ｃ６）アルキルアミノ、（Ｃ２－Ｃ６）アルケニルアミノ、（Ｃ２－Ｃ６）アルキニルアミノ、ジ（Ｃ１－Ｃ６）アルキルアミノ、ジ（Ｃ２－Ｃ６）アルケニルアミノ、ジ（Ｃ２－Ｃ６）アルキニルアミノ、（Ｃ１－Ｃ６）アルキルスルフィニル、（Ｃ２－Ｃ６）アルケニルスルフィニル、（Ｃ２－Ｃ６）アルキニルスルフィニル、（Ｃ１－Ｃ６）アルキルスルホニル、（Ｃ２－Ｃ６）アルケニルスルホニル、（Ｃ２－Ｃ６）アルキニルスルホニル、（Ｃ１－Ｃ６）アルキルオキシ（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルキルチオ（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルキルアミノ（Ｃ１－Ｃ６）アルキル、ジ（Ｃ１－Ｃ６）アルキルアミノ（Ｃ１－Ｃ６）アルキル、ホルミル、（Ｃ１－Ｃ６アルキル）カルボニル、（Ｃ１－Ｃ６アルコキシ）カルボニル、（Ｃ１－Ｃ６アルキル）アミノカルボニル、ジ（Ｃ１－Ｃ６アルキル）アミノカルボニル、（Ｃ１－Ｃ６アルキル）カルボニルオキシ、（Ｃ１－Ｃ６アルキル）カルボニルチオ、（Ｃ１－Ｃ６アルキル）カルボニルアミノ又はジ（Ｃ１－Ｃ６アルキル）カルボニルアミノであり；ｎは０～５の整数であり；ｎが２以上のとき、複数のＲ１は同一又は異なっていてもよい〕で表される化合物又はその塩。     Formula (II):
    Figure JPOXMLDOC01-appb-C000004
     [Wherein R 1 is a halogen atom, cyano, nitro, (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl] , (C 1 -C 6 ) haloalkyl, (C 1 -C 6 ) alkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 3 -C 6 ) cycloalkoxy, ( C 1 -C 6 ) haloalkoxy, (C 1 -C 6 ) alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, (C 3 -C 6 ) cycloalkylthio, (C 1- C 6 ) haloalkylthio, (C 1 -C 6 ) alkylamino, (C 2 -C 6 ) alkenylamino, (C 2 -C 6 ) alkynylamino, di (C 1 -C 6 ) alkylamino, di ( 2 -C 6) alkenyl, di (C 2 -C 6) alkynyl amino, (C 1 -C 6) alkylsulfinyl, (C 2 -C 6) alkenylsulfinyl, (C 2 -C 6) alkynylsulfinyl, ( C 3 -C 6) cycloalkyl alkylsulfinyl, (C 1 -C 6) haloalkylsulfinyl, (C 1 -C 6) alkylsulfonyl, (C 2 -C 6) alkenyl-sulfonyl, (C 2 -C 6) alkynyl-sulfonyl, (C 1 -C 6 alkyl) carbonyl, (C 1 -C 6 alkyl) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl, (C 1 -C 6 alkyl) ) carbonyloxy, (C 1 -C 6 alkyl) carbonylamino or (C 1 -C 6 alkyl) carboxamide There Le (C 1 -C 6) alkylamino; R 2 is a halogen atom, cyano, nitro, (C 1 -C 6) alkyl, (C 2 -C 6) alkenyl, (C 2 -C 6) alkynyl, (C 1 -C 6 ) haloalkyl, (C 1 -C 6 ) alkoxy, (C 3 -C 6 ) cycloalkoxy, (C 1 -C 6 ) haloalkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 1 -C 6 ) alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, (C 3 -C 6 ) cycloalkylthio, (C 1 -C 6) alkylamino, (C 2 -C 6) alkenyl amino, (C 2 -C 6) alkynyl amino, di (C 1 -C 6) alkylamino, di (C 2 -C 6) alkenyl, di C 2 -C 6) alkynyl amino, (C 1 -C 6) alkylsulfinyl, (C 2 -C 6) alkenylsulfinyl, (C 2 -C 6) alkynylsulfinyl, (C 1 -C 6) alkylsulfonyl, ( C 2 -C 6 ) alkenylsulfonyl, (C 2 -C 6 ) alkynylsulfonyl, (C 1 -C 6 ) alkyloxy (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkylthio (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkylamino (C 1 -C 6 ) alkyl, di (C 1 -C 6 ) alkylamino (C 1 -C 6 ) alkyl, formyl, (C 1 -C 6 alkyl) ) carbonyl, (C 1 -C 6 alkoxy) carbonyl, (C 1 -C 6 alkyl) aminocarbonyl, di (C 1 -C 6 alkyl) aminocarbonyl (C 1 -C 6 alkyl) carbonyloxy, be (C 1 -C 6 alkyl) carbonyl thio, (C 1 -C 6 alkyl) carbonylamino or di (C 1 -C 6 alkyl) carbonylamino; n is 0 A plurality of R 1 may be the same or different when n is 2 or more] or a salt thereof.
  10. 　Ｒ１がハロゲン原子、（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）ハロアルキル又は（Ｃ１－Ｃ６）ハロアルコキシであり、Ｒ２がハロゲン原子、（Ｃ１－Ｃ６）アルキル、（Ｃ１－Ｃ６）アルコキシ、（Ｃ１－Ｃ６）アルキルチオ、（Ｃ１－Ｃ６）アルキルスルフィニル又は（Ｃ１－Ｃ６）アルキルスルホニルである請求項９に記載の化合物又はその塩。 R 1 is a halogen atom, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl or (C 1 -C 6 ) haloalkoxy, R 2 is a halogen atom, (C 1 -C 6 ) alkyl 10. The compound or a salt thereof according to claim 9, wherein the compound is (C 1 -C 6 ) alkoxy, (C 1 -C 6 ) alkylthio, (C 1 -C 6 ) alkylsulfinyl or (C 1 -C 6 ) alkylsulfonyl. .
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