WO2017222037A1 - N-(4-pyridyl)benzamide compound or salt thereof, and pest control agent containing compound or salt thereof as active ingredient - Google Patents

N-(4-pyridyl)benzamide compound or salt thereof, and pest control agent containing compound or salt thereof as active ingredient Download PDF

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WO2017222037A1
WO2017222037A1 PCT/JP2017/023128 JP2017023128W WO2017222037A1 WO 2017222037 A1 WO2017222037 A1 WO 2017222037A1 JP 2017023128 W JP2017023128 W JP 2017023128W WO 2017222037 A1 WO2017222037 A1 WO 2017222037A1
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compound
alkyl
salt
alkylthio
alkylcarbonyl
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PCT/JP2017/023128
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French (fr)
Japanese (ja)
Inventor
哲夫 米田
幸太郎 吉田
優太 田澤
達也 可児
洋子 長
明史 能島
勇斗 村井
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石原産業株式会社
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Publication of WO2017222037A1 publication Critical patent/WO2017222037A1/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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A01N25/14—Powders or granules wettable
    • 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
    • C07D213/60—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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/83—Thioacids; Thioesters; Thioamides; Thioimides

Definitions

  • the present invention relates to a novel N- (4-pyridyl) benzamide compound or a salt thereof, a pest control agent containing them as an active ingredient, and a method for controlling pests by applying an effective amount thereof.
  • Patent Document 1 describes a wide range of arylamide compounds
  • Patent Document 2 describes a compound having a pyridine skeleton for a wide range of pharmaceutical uses.
  • An object of the present invention is to provide a compound having high activity against pests, to provide a pest control agent using the compound, and to provide a method for controlling pests by applying the compound. That is.
  • Patent Documents 1 and 2 do not have a specific description regarding the compound of the present invention.
  • the present inventors have made various studies on pyridine compounds in order to find better pest control agents. As a result, the present inventors have found that a novel N- (4-pyridyl) benzamide compound or a salt thereof has a very high control effect against pests with a low dose, and completed the present invention. That is, the present invention provides a compound of formula (I):
  • R 1 is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, alkylthiohaloalkylthio or pentafluorosulfanyl;
  • R 2 is halogen atom, hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxyalkyl, alkenyloxyalkyl, alkynyl Oxyalkyl, cycloalkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, trialkylsilyl, amino, monoalkylamin
  • 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.
  • the present invention relates to a compound represented by the following formula (I) or a salt thereof (hereinafter sometimes collectively referred to as “the present compound”).
  • the present compound a compound represented by the following formula (I) or a salt thereof (hereinafter sometimes collectively referred to as “the present compound”).
  • C n (n is a natural number) is synonymous with “carbon number n”.
  • ppm is described as the concentration, it indicates ppm by weight.
  • R 1 is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, alkylthiohaloalkylthio or pentafluorosulfanyl
  • R 2 is halogen atom, hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxyalkyl, alkenyloxyalkyl, alkynyl Oxyalkyl, cycloalkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, trialkylsilyl, amino, monoalkyla
  • halogen atom of the compound of the formula (I) or a salt thereof 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 of the compound of the formula (I) or a salt thereof examples include, for example, methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, normal hexyl.
  • linear or branched C 1 -C 6 groups such as neohexyl.
  • alkenyl or alkenyl moiety of the compound of formula (I) or a salt thereof examples include, for example, vinyl, 1-propenyl, 2-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl, -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 of the compound of the formula (I) or a salt thereof examples include, for example, 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 part of the compound of the formula (I) or a salt thereof include C 3 -C 6 groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • Examples of the aryl or aryl moiety of the compound of the formula (I) or a salt thereof include C 6 -C 10 groups such as phenyl and naphthyl.
  • the salt of the compound of the formula (I) includes any salt as long as it is acceptable in the technical field.
  • inorganic salts such as hydrochloride, perchlorate, sulfate, and nitrate
  • organic acid salts such as acetate, trifluoroacetate, oxalate, p-toluenesulfonate, and methanesulfonate.
  • the compound of the formula (I) or a salt thereof may have an isomer such as an optical isomer, 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. Depending on the type of isomer, there may be a chemical structure different from that of the formula (I). However, since those skilled in the art can fully recognize that they are related to isomers, the scope of the present invention. It is clear that it is within.
  • 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 above formula (I) can be produced by reacting a compound represented by the following formula (II) with a compound represented by the following formula (III) in the presence of a dehydration condensing agent.
  • the compound of Formula (II) can also be manufactured by a well-known method besides using a commercial item.
  • the compound of Formula (III) can use a commercial item, and can also manufacture it by the method as described in a postscript intermediate manufacturing method.
  • Examples of the dehydrating condensing agent include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1,3-dicyclohexylcarbodiimide and the like.
  • the reaction can be performed by adding an additive as necessary.
  • Examples of the additive include 1-hydroxybenzotriazole, N-hydroxysuccinimide, N, N-dimethyl-4-aminopyridine and the like.
  • the reaction can be carried out in the presence of a base as necessary.
  • a base include tertiary amines such as triethylamine, 4-methylmorpholine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, pyridine, 4- (dimethylamino) pyridine, 2 , 6-lutidine and the like.
  • the reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited, but for example, acid amides such as N, N-dimethylformamide and N-methylpyrrolidinone; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; nitrogen-containing compounds such as pyridine
  • acid amides such as N, N-dimethylformamide and N-methylpyrrolidinone
  • ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane
  • nitrogen-containing compounds such as pyridine
  • the reaction temperature can usually be in the range of about 0 ° C. to a temperature at which the inside of the reaction system is heated to reflux.
  • the reaction time is usually several minutes to 24 hours.
  • the compound of the formula (I) can be produced by reacting a compound represented by the following formula (II-a) with a compound represented by the following formula (III) in the presence of a base.
  • the compound of the formula (II-a) can be a commercially available product or can be produced by the method described in the intermediate production method described later.
  • R 1 , R 2 , R 3 , R 4 and m are as described above;
  • X is a halogen atom.
  • Examples of the halogen atom that is X include fluorine, chlorine, bromine, and iodine atoms.
  • the base may be an organic base or an inorganic base.
  • the organic base include amine bases such as triethylamine and diisopropylethylamine.
  • examples of 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 is not particularly limited.
  • ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; acid amides such as N, N-dimethylformamide and N-methylpyrrolidinone; dichloromethane and chloroform 1 type, or 2 or more types can be appropriately selected and used from such aliphatic halogenated hydrocarbons.
  • the reaction temperature can usually be in the range of about 0 ° C. to a temperature at which the inside of the reaction system is heated to reflux.
  • the reaction time is usually several minutes to 24 hours.
  • the compound represented by the following formula (Ib) in which R 3 is the following R 3a is represented by the following formula (Ia) when R 3 is a hydrogen atom. It can be produced by reacting a compound with a compound represented by the formula: R 3a X in the presence of a base.
  • R 3a is alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl or arylcarbonyl; R 1 , R 2 , R 4 , X and m Is as described above.
  • 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 hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide. Thing; etc. are mentioned.
  • the reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited.
  • ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; acid amides such as N, N-dimethylformamide and N-methylpyrrolidinone; dichloromethane and chloroform 1 type, or 2 or more types can be appropriately selected and used from such aliphatic halogenated hydrocarbons.
  • the reaction temperature can be usually in the range of about 20 ° C. to a temperature at which the inside of the reaction system is heated to reflux.
  • the reaction time can usually be from several minutes to 48 hours.
  • the compound of the formula (II-a) can be produced by reacting the compound of the formula (II) with a halogenating agent as shown in the following scheme.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride and the like.
  • the reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited, but for example, one or two or more types of aliphatic halogenated hydrocarbons such as methylene chloride, dichloroethane, and chloroform; aromatic hydrocarbons such as toluene and chlorobenzene, and the like are appropriately selected. Can do.
  • the reaction temperature can be usually from about 0 ° C. to a temperature at which the inside of the reaction system is heated to reflux.
  • the reaction time is usually several minutes to 24 hours.
  • the compound of the formula (III) can be produced by reacting a compound represented by the following formula (IV) with a compound represented by the following formula (V).
  • the compound of Formula (IV) and the compound of Formula (V) can also be manufactured by a well-known method besides using a commercial item.
  • the reaction can be performed in the presence of a solvent, if necessary.
  • the solvent is not particularly limited, but for example, acid amides such as N, N-dimethylformamide and N-methylpyrrolidinone; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; nitrogen-containing compounds such as pyridine
  • acid amides such as N, N-dimethylformamide and N-methylpyrrolidinone
  • ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane
  • nitrogen-containing compounds such as pyridine
  • the reaction temperature can usually be in the range of about 0 ° C. to a temperature at which the inside of the reaction system is heated to reflux.
  • the reaction time is usually several minutes to 24 hours.
  • the compound of formula (VII) can be produced by reacting the compound of formula (VI) with ditert-butyl dicarbonate, if necessary, in the presence of a base.
  • 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 hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide.
  • alkali metal amides such as lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, and potassium bis (trimethylsilyl) amide.
  • the reaction can be performed in the presence of a solvent, if necessary.
  • the solvent examples include, but are not limited to, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; esters such as methyl acetate and ethyl acetate; aliphatic halogens such as methylene chloride, dichloroethane and chloroform.
  • ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane
  • esters such as methyl acetate and ethyl acetate
  • aliphatic halogens such as methylene chloride, dichloroethane and chloroform.
  • One kind or two or more kinds can be appropriately selected and mixed from the following: hydrocarbons; alcohols such as methanol, ethanol and tert-butyl alcohol; water;
  • the reaction temperature can usually be in the range of about ⁇ 20 ° C. to the temperature at which the reaction system is heated to reflux.
  • the compound of the formula (VIII) can be produced by reacting the compound of the formula (VII) with a compound represented by the formula: R 3a X in the presence of a base. This reaction can be carried out in the same manner as in the above production method [3].
  • the compound of the formula (III-1) can be produced by reacting the compound of the formula (VIII) with an acid.
  • the acid include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as acetic acid and trifluoroacetic acid.
  • the reaction can be performed in the presence of a solvent, if necessary.
  • the solvent include, but are not limited to, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; esters such as methyl acetate and ethyl acetate; aliphatic halogens such as methylene chloride, dichloroethane and chloroform.
  • reaction temperature can usually be in the range of about 0 ° C. to a temperature at which the inside of the reaction system is heated to reflux.
  • reaction time can usually be from several minutes to 48 hours.
  • the desirable mode of the pest control agent containing the compound of the present invention is described below.
  • Examples of the pest control agent containing the compound of the present invention include pests, mites, nematodes or soil pests that are problematic in the field of agriculture and horticulture, that is, agricultural and horticultural insecticides, acaricides, nematicides or Soil-killing pesticides.
  • the compound of the present invention is useful as an active ingredient of agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides.
  • aphids such as peach aphids, cotton aphids Moth, weevil, lotus moth, codling moth, ball worm, cigarette bud worm, gypsy moth, corn borer, chanoco cricket, leafworm, ball weevil, planthopper, leafhopper, scale insect, stink bug, whitefly Pests, such as slugs, cockroaches, house flies, house mosquitoes, etc .; agricultural pests such as slugs, mussels, etc .; Bakuga, azuki beetle, wolfberry, beetle Stored pests such as garments; clothing such as moths, swordfish, termites etc .; house pests; pests such as nymphs, mite spider mites, kanzawa spider mites, man
  • Plant parasitic mites Plant parasitic mites; Indoor dust mites such as Staghorn mite, Salamander mites, Southern mites, etc .; It is effective for controlling pests such as plant parasitic nematodes, etc .;
  • the agricultural and horticultural 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. is there. 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.
  • agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides containing the compounds of the present invention are various resistances against drugs such as organophosphorus agents, carbamate agents, synthetic pyrethroid agents, neonicotinoid agents, etc. It is also effective for controlling pests. Furthermore, since the compound of the present invention has an excellent osmotic transfer property, the agricultural or horticultural insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is treated on the soil. By this, it is possible to control pests in the foliage at the same time as the control of soil harmful insects, mites, nematodes, gastropods, and isopods.
  • insecticide acaricide, nematicide or soil insecticide containing the compound of the present invention
  • the above plant parasitic mites, agricultural pests, plant parasitic nematodes, gastropods And agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides that comprehensively control soil pests and the like.
  • the pest control agent containing the compound of the present invention is usually a powder, granule, granule wettable powder, wettable powder, aqueous suspension, oily suspension by mixing the compound with various agricultural adjuvants. It is used in various forms such as pharmaceuticals, aqueous granules, aqueous solvents, emulsions, solutions, pastes, aerosols, microdispersions, etc., but as long as it meets the purpose of the present invention, it is usually used in this field. It can be in any formulation form.
  • Adjuvants used in the formulation 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, 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, etc.
  • 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,
  • Solvent fatty acid salt, benzoate, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, alcohol Sulfate ester salt, 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
  • 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 art.
  • 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 compounding ratio (weight ratio) of the compound of the present invention and various adjuvants is 0.001: 99.999 to 95: 5, desirably 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 (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.
  • the application of the pest control agent containing the compound of the present invention cannot be defined unconditionally due to differences in weather conditions, formulation form, application time, application place, type of pests and occurrence, etc., but generally 0.05 to 800,000 ppm
  • the active ingredient concentration is preferably 0.5 to 500,000 ppm
  • the application amount per unit area is 0.05 to 50,000 g, preferably 1 to 30,000 g of the compound of the present invention per hectare.
  • the present invention includes a method for controlling pests by such an application method, particularly a method for controlling pests, mites, nematodes or soil pests, particularly plant parasitic mites, agricultural pests, plant parasitic nematodes. Also included are methods of controlling the species.
  • the pest control agent containing the compound of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, safeners, etc., and in this case, more excellent effects and activities may be exhibited.
  • Other pesticides include herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, etc. .
  • 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.
  • 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 both may be used together.
  • the present invention includes such a pest control composition.
  • insect pathogenic fungi Microbial pesticides such as avermectin,
  • 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,
  • an agrochemical that can be used in combination with or combined with the compound of the present invention, for example, an active ingredient compound of a herbicide as described in The Pesticide Manual (15th edition), particularly a soil treatment type, etc. There is.
  • N- (4-pyridyl) benzamide compound or a salt thereof of the present invention will be exemplified, but these do not limit the present invention.
  • R 1 in the halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, Alkoxyhaloalkyl, alkylthio, halo alkylthio or pentafluorosulfanyl;
  • R 2 is a halogen atom , Hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkoxyalkyl, alkenyloxyalkyl, alkynyloxyalkyl, cycloalkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, alkoxyhaloalkyl, alkoxyhaloalkyl , Trialkyls
  • R 1 in formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio, or pentafluorosulfanyl.
  • R 2 in the formula (I) is a halogen atom, nitro, alkyl, alkoxy, alkylthio, alkylsulfonyl, amino or dialkylamino, or a compound thereof salt.
  • R 3 in the formula (I) is a hydrogen atom, alkyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl or alkoxycarbonyl.
  • R 4 in the formula (I) is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxy
  • R 4 in the formula (I) is a halogen atom, mercapto, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkenylthio, alkynylthio, haloalkylthio Alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, haloalkylsulfonyl, alkoxyalkyl, alkylthioalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, hydroxylalkyl, formyl, carboxyl, alkylcarbonyl,
  • R 4 in the formula (I) is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxy 10.
  • the compound or a salt thereof according to any one of (1) to (9), which is carbonyl, cyanoalkoxycarbonyl or (alkylthio) carbonyl.
  • R 4 in the formula (I) is a halogen atom, nitro, alkoxy, alkoxycarbonyl, (alkylthio) carbonyl, monoalkylaminocarbonyl or mono (cycloalkylalkyl) aminocarbonyl Or a salt thereof.
  • R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl;
  • R 2 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, Alkylsulfonyl, amino or dialkylamino;
  • R 3 is a hydrogen atom, alkyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl or alkoxycarbonyl;
  • R 4 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl , Alkoxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonyl
  • R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl;
  • R 2 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, Alkylsulfonyl, amino or dialkylamino;
  • R 3 is a hydrogen atom, alkyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl or alkoxycarbonyl;
  • R 4 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl , Alkoxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonyl
  • R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl;
  • R 2 is a halogen atom, nitro, alkyl, alkylthio, alkylsulfonyl Or
  • R 3 is a hydrogen atom, alkyl, cycloalkyl, alkylcarbonyl or alkoxycarbonyl;
  • R 4 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkynyloxycarbonyl, Cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyanoalkoxycarbonyl,
  • R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl;
  • R 2 is a halogen atom, nitro, alkyl, alkylthio,
  • R 3 is a hydrogen atom, alkyl, cycloalkyl, alkylcarbonyl or alkoxycarbonyl;
  • R 4 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkynyloxy Carbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyanoalkoxycarbonyl Or (alkylthio) carbonyloxy; compound
  • R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl;
  • R 2 is a halogen atom, alkyl, alkylthio, alkylsulfonyl or amino
  • R 3 is a hydrogen atom, alkyl, cycloalkyl, alkylcarbonyl or alkoxycarbonyl;
  • R 4 is a halogen atom, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkoxyalkoxycarbonyl, cyanoalkoxycarbonyl or (alkylthio) carbonyl
  • R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl;
  • R 2 is a halogen atom or alkyl;
  • R 3 is hydrogen
  • R 4 is a halogen atom, nitro, alkoxy, alkoxycarbonyl, (alkylthio) carbonyl, monoalkylaminocarbonyl or mono (cycloalkylalkyl) aminocarbonyl; and (1) or m above wherein m is 0 or 1;
  • the compound or a salt thereof according to (2) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl;
  • R 2 is a halogen
  • a pest control agent comprising the compound according to any one of (1) to (16) or a salt thereof as an active ingredient.
  • a method for controlling pests by applying an effective amount of the compound or salt thereof according to any one of (1) to (16).
  • Synthesis example 1 Synthesis of methyl 4- (4- (heptafluoroisopropyl) benzamido) nicotinate (Compound No. I-9) 4- (heptafluoroisopropyl) benzoyl chloride (250 mg, 0.8 mmol), methyl 4-amino-nicotinate ( 123.3 mg, 0.8 mmol) and diisopropylethylamine (0.42 mL, 2.4 mmol) were dissolved in tetrahydrofuran (5 mL) and stirred at 60 ° C. for 1 hour. After allowing to cool to room temperature, water was added and the mixture was extracted with ethyl acetate.
  • Synthesis example 2 Synthesis of methyl 4- (4- (trifluoromethyl) benzamido) nicotinate (Compound No. I-6) 4- (trifluoromethyl) benzoyl chloride (550 mg, 2.6 mmol), methyl 4-amino-nicotinate ( 400 mg, 2.6 mmol) and diisopropylethylamine (1.4 mL, 7.9 mmol) were dissolved in tetrahydrofuran (9 mL) and stirred at 60 ° C. for 1 hour. After allowing to cool to room temperature, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure to obtain the desired product (490 mg, 57% yield).
  • Synthesis example 3 Synthesis of methyl 4- (N-ethyl-4-((trifluoromethyl) benzamido) nicotinate (Compound No. I-407) methyl 4- (ethylamino) nicotinate (1.0 g, 5.6 mmol), diisopropyl 4- (Trifluoromethyl) benzoyl chloride (1.16 g, 5.6 mmol) was added to a solution of ethylamine (1.94 mL, 11.1 mmol) in tetrahydrofuran (19 mL), and the mixture was stirred for 16 hours at 65 ° C. The reaction mixture was mixed with water.
  • Table 1 typical examples of the compounds of formula (I) according to the present invention are listed in Table 1. These compounds can be synthesized based on the above synthesis examples or the various production methods described above.
  • Table 1 the numerical values described in the physical properties column indicate melting points (° C.), and for compounds for which melting points are not described, their 1 H-NMR spectral data are listed in Tables 2 and 3, In the physical property column of the table, NMR is described. No. 1 in Table 1 Indicates a compound number.
  • 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
  • t-Bu represents a tertiary butyl group
  • c-Pr represents a cyclopropyl group.
  • 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 to 3 years old were released, and the tube mouth was covered with gauze and allowed to stand in a constant temperature room at 25 ° C. Five days after the treatment, the survival of the brown planthopper was determined, and the death rate (%) was determined by the following formula. As the compound of the present invention, the above-mentioned compound No.
  • Test Example 2 Effect test on tobacco whitefly An adult tobacco whitefly was released on a pot-planted cucumber seedling. After laying eggs for one day, cucumber seedlings were taken out and placed in a constant temperature room with illumination at 25 ° C. Seven days later, the number of 1-2 instar larvae parasitizing the cucumber seedlings was examined, and a chemical solution prepared so that the concentration of the compound of the present invention was 200 ppm 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. Seven days after the treatment, the number of old larvae was examined, and the control value was determined by the following formula. As the compound of the present invention, the above-mentioned compound No.
  • 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
  • Test Example 3 Effect test on peach aphid
  • Five adult peach aphids were released on radish leaves inserted in test tubes. After removing adults one day later, the number of larvae parasitizing on radish leaves was counted and 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, it was left in a constant temperature room at 25 ° C. with illumination. Five days after the treatment, the viability of the peach aphid was determined, and the mortality was determined by the following formula. The detached insects and abnormal insects were regarded as dead insects. As the compound of the present invention, the above-mentioned compound No.
  • 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 the above (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 formation).
  • 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

Although a variety of pest control agents have been used for many years, many of these pest control agents have various problems, such as insufficient effectiveness, and restriction on use thereof due to resistance acquired by insect pests, etc. The purpose of the present invention is to provide an effective compound for a novel pest control agent which is less likely to have such a drawback. The present invention pertains to: an N-(4-pyridyl)benzamide compound represented by formula (I) or a salt thereof; a pest control agent containing the compound or a salt thereof as an active ingredient; and a method for controlling pests by applying an effective amount of the compound or a salt thereof.

Description

Ｎ－（４－ピリジル）ベンズアミド化合物又はその塩、及び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N- (4-pyridyl) benzamide compound or salt thereof, and pest control agent containing the compound or salt thereof as an active ingredient
　本発明は、新規なＮ－（４－ピリジル）ベンズアミド化合物又はその塩、それらを有効成分として含有する有害生物防除剤及びそれらの有効量を施用して有害生物を防除する方法に関する。 The present invention relates to a novel N- (4-pyridyl) benzamide compound or a salt thereof, a pest control agent containing them as an active ingredient, and a method for controlling pests by applying an effective amount thereof.
　特許文献１には、広範囲なアリールアミド化合物が記載されており、特許文献２には広範囲な医薬用途のピリジン骨格を有する化合物が記載されている。 Patent Document 1 describes a wide range of arylamide compounds, and Patent Document 2 describes a compound having a pyridine skeleton for a wide range of pharmaceutical uses.
国際公開第２００２／０７０４８３号International Publication No. 2002/070483 国際公開第２００５／１１５９８６号International Publication No. 2005/115986
　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。
　本発明の目的は、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、及び該化合物を施用して有害生物を防除する方法を提供することである。なお、特許文献１及び２には本発明化合物に関する具体的記載はない。 Many pest control agents have been used for many years, but many have various problems such as insufficient efficacy, pests and the like acquiring resistance and limiting their use. Therefore, development of a novel pest control agent with few such drawbacks is desired.
An object of the present invention is to provide a compound having high activity against pests, to provide a pest control agent using the compound, and to provide a method for controlling pests by applying the compound. That is. Patent Documents 1 and 2 do not have a specific description regarding the compound of the present invention.
　本発明者らは、より優れた有害生物防除剤を見出すべく、ピリジン化合物につき種々検討した。その結果、新規なＮ－（４－ピリジル）ベンズアミド化合物又はその塩が、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。
　即ち本発明は、式（Ｉ）： The present inventors have made various studies on pyridine compounds in order to find better pest control agents. As a result, the present inventors have found that a novel N- (4-pyridyl) benzamide compound or a salt thereof has a very high control effect against pests with a low dose, and completed the present invention.
That is, the present invention provides a compound of formula (I):
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
［式中、Ｒ１はハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシアルキル、ハロアルコキシアルキル、アルコキシハロアルキル、アルキルチオハロアルキルチオ又はペンタフルオロスルファニルであり；
Ｒ２はハロゲン原子、ヒドロキシル、シアノ、ニトロ、アルキル、アルケニル、アルキニル、シクロアルキル、ハロアルキル、アルコキシ、アルケニルオキシ、アルキニルオキシ、ハロアルコキシ、アルキルチオ、アルキルスルフィニル、アルキルスルホニル、アルコキシアルキル、アルケニルオキシアルキル、アルキニルオキシアルキル、シクロアルコキシアルキル、ハロアルコキシアルキル、アルコキシハロアルキル、トリアルキルシリル、アミノ、モノアルキルアミノ、モノアルケニルアミノ、モノアルキニルアミノ、ジアルキルアミノ、ジアルケニルアミノ、ジアルキニルアミノ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、モノアルキルアミノカルボニル、ジアルキルアミノカルボニル、アルキルカルボニルオキシ、モノ（アルキルカルボニル）アミノ、ジ（アルキルカルボニル）アミノ、モノ（アルキルカルボニルアルキル）アミノ又はジ（アルキルカルボニルアルキル）アミノであり；
Ｒ３は、水素原子、アルキル、アルケニル、アルキニル、シクロアルキル、アルコキシアルキル、アルキルカルボニル、アルコキシカルボニル、アルキルスルホニル又はアリールカルボニルであり；
Ｒ４はハロゲン原子、メルカプト、シアノ、ニトロ、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシ、アルケニルオキシ、アルキニルオキシ、ハロアルコキシ、アルキルチオ、アルケニルチオ、アルキニルチオ、ハロアルキルチオ、アルキルスルフィニル、アルケニルスルフィニル、アルキニルスルフィニル、ハロアルキルスルフィニル、アルキルスルホニル、アルケニルスルホニル、アルキニルスルホニル、ハロアルキルスルホニル、アルコキシアルキル、アルキルチオアルキル、モノアルキルアミノアルキル、ジアルキルアミノアルキル、ヒドロキシルアルキル、ホルミル、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルケニルオキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル、（アルキルチオ）カルボニル、モノアルキルアミノカルボニル、モノ（シクロアルキルアルキル）アミノカルボニル、アルキルカルボニルオキシ又はアルキルカルボニルチオであり；ｍは０～３の整数であり、前記Ｒ２が複数存在する場合、それぞれ同一でも異なっていてもよい］で表されるＮ－（４－ピリジル）ベンズアミド化合物又はその塩、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、及び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に関する。 Wherein R 1 is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, alkylthiohaloalkylthio or pentafluorosulfanyl;
R 2 is halogen atom, hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxyalkyl, alkenyloxyalkyl, alkynyl Oxyalkyl, cycloalkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, trialkylsilyl, amino, monoalkylamino, monoalkenylamino, monoalkynylamino, dialkylamino, dialkenylamino, dialkynylamino, carboxyl, alkylcarbonyl, alkoxycarbonyl Monoalkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonyloxy Ci, mono (alkylcarbonyl) amino, di (alkylcarbonyl) amino, mono (alkylcarbonylalkyl) amino or di (alkylcarbonylalkyl) amino;
R 3 is a hydrogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl or arylcarbonyl;
R 4 is a halogen atom, mercapto, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkenylthio, alkynylthio, haloalkylthio, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl , Haloalkylsulfinyl, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, haloalkylsulfonyl, alkoxyalkyl, alkylthioalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, hydroxylalkyl, formyl, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxy Carbonyl, cycloalkoxy M is sulfonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyanoalkoxycarbonyl, (alkylthio) carbonyl, monoalkylaminocarbonyl, mono (cycloalkylalkyl) aminocarbonyl, alkylcarbonyloxy or alkylcarbonylthio; An N- (4-pyridyl) benzamide compound or a salt thereof, which is an integer of 0 to 3 and may be the same or different when a plurality of R 2 are present], the compound or a salt thereof is effective. The present invention relates to a pest control agent contained as a component and a method for controlling pests by applying an effective amount of the compound 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.
　本発明は下記式（Ｉ）で表される化合物又はその塩（以下、まとめて「本発明化合物」と称する場合がある。）に関する。
　また、本明細書において「Ｃｎ」（ｎは自然数）とは「炭素数ｎ」と同義である。濃度としてｐｐｍと記載した場合は、重量ｐｐｍのことを示す。 The present invention relates to a compound represented by the following formula (I) or a salt thereof (hereinafter sometimes collectively referred to as “the present compound”).
In this specification, “C n ” (n is a natural number) is synonymous with “carbon number n”. When ppm is described as the concentration, it indicates ppm by weight.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
［式（Ｉ）中、Ｒ１はハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシアルキル、ハロアルコキシアルキル、アルコキシハロアルキル、アルキルチオハロアルキルチオ又はペンタフルオロスルファニルであり；
Ｒ２はハロゲン原子、ヒドロキシル、シアノ、ニトロ、アルキル、アルケニル、アルキニル、シクロアルキル、ハロアルキル、アルコキシ、アルケニルオキシ、アルキニルオキシ、ハロアルコキシ、アルキルチオ、アルキルスルフィニル、アルキルスルホニル、アルコキシアルキル、アルケニルオキシアルキル、アルキニルオキシアルキル、シクロアルコキシアルキル、ハロアルコキシアルキル、アルコキシハロアルキル、トリアルキルシリル、アミノ、モノアルキルアミノ、モノアルケニルアミノ、モノアルキニルアミノ、ジアルキルアミノ、ジアルケニルアミノ、ジアルキニルアミノ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、モノアルキルアミノカルボニル、ジアルキルアミノカルボニル、アルキルカルボニルオキシ、モノ（アルキルカルボニル）アミノ、ジ（アルキルカルボニル）アミノ、モノ（アルキルカルボニルアルキル）アミノ又はジ（アルキルカルボニルアルキル）アミノであり；
Ｒ３は、水素原子、アルキル、アルケニル、アルキニル、シクロアルキル、アルコキシアルキル、アルキルカルボニル、アルコキシカルボニル、アルキルスルホニル又はアリールカルボニルであり；
Ｒ４はハロゲン原子、メルカプト、シアノ、ニトロ、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシ、アルケニルオキシ、アルキニルオキシ、ハロアルコキシ、アルキルチオ、アルケニルチオ、アルキニルチオ、ハロアルキルチオ、アルキルスルフィニル、アルケニルスルフィニル、アルキニルスルフィニル、ハロアルキルスルフィニル、アルキルスルホニル、アルケニルスルホニル、アルキニルスルホニル、ハロアルキルスルホニル、アルコキシアルキル、アルキルチオアルキル、モノアルキルアミノアルキル、ジアルキルアミノアルキル、ヒドロキシルアルキル、ホルミル、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルケニルオキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル、（アルキルチオ）カルボニル、モノアルキルアミノカルボニル、モノ（シクロアルキルアルキル）アミノカルボニル、アルキルカルボニルオキシ又はアルキルカルボニルチオであり；ｍは０～３の整数であり、前記Ｒ２が複数存在する場合、それぞれ同一でも異なっていてもよい］で表されるＮ－（４－ピリジル）ベンズアミド化合物又はその塩。 [Wherein, R 1 is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, alkylthiohaloalkylthio or pentafluorosulfanyl;
R 2 is halogen atom, hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxyalkyl, alkenyloxyalkyl, alkynyl Oxyalkyl, cycloalkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, trialkylsilyl, amino, monoalkylamino, monoalkenylamino, monoalkynylamino, dialkylamino, dialkenylamino, dialkynylamino, carboxyl, alkylcarbonyl, alkoxycarbonyl Monoalkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonyloxy Ci, mono (alkylcarbonyl) amino, di (alkylcarbonyl) amino, mono (alkylcarbonylalkyl) amino or di (alkylcarbonylalkyl) amino;
R 3 is a hydrogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl or arylcarbonyl;
R 4 is a halogen atom, mercapto, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkenylthio, alkynylthio, haloalkylthio, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl , Haloalkylsulfinyl, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, haloalkylsulfonyl, alkoxyalkyl, alkylthioalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, hydroxylalkyl, formyl, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxy Carbonyl, cycloalkoxy M is sulfonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyanoalkoxycarbonyl, (alkylthio) carbonyl, monoalkylaminocarbonyl, mono (cycloalkylalkyl) aminocarbonyl, alkylcarbonyloxy or alkylcarbonylthio; N- (4-pyridyl) benzamide compound or a salt thereof, which is an integer of 0 to 3 and may be the same or different when a plurality of R 2 are present.
　前記式（Ｉ）の化合物又はその塩のハロゲン原子又は置換基としてのハロゲンとしては、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 of the compound of the formula (I) or a salt thereof 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）の化合物又はその塩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 of the compound of the formula (I) or a salt thereof include, for example, methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, normal hexyl. And linear or branched C 1 -C 6 groups such as neohexyl.
　前記式（Ｉ）の化合物又はその塩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 of the compound of formula (I) or a salt thereof include, for example, vinyl, 1-propenyl, 2-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl, -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）の化合物又はその塩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 of the compound of the formula (I) or a salt thereof include, for example, 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）の化合物又はその塩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 part of the compound of the formula (I) or a salt thereof include C 3 -C 6 groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
　前記式（Ｉ）の化合物又はその塩のアリール又はアリール部分としては、例えば、フェニル、ナフチルのようなＣ６－Ｃ１０の基が挙げられる。 Examples of the aryl or aryl moiety of the compound of the formula (I) or a salt thereof include C 6 -C 10 groups such as phenyl and naphthyl.
　前記式（Ｉ）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、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 salt of the compound of the formula (I) includes any salt as long as it is acceptable in the technical field. For example, inorganic salts such as hydrochloride, perchlorate, sulfate, and nitrate And organic acid salts such as acetate, trifluoroacetate, oxalate, p-toluenesulfonate, and methanesulfonate.
　前記式（Ｉ）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。 The compound of the formula (I) or a salt thereof may have an isomer such as an optical isomer, 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. Depending on the type of isomer, there may be a chemical structure different from that of the formula (I). However, since those skilled in the art can fully recognize that they are related to isomers, the scope of the present invention. It is clear that it is within.
　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］
　前記式（Ｉ）の化合物は、下記式（ＩＩ）で表される化合物と下記式（ＩＩＩ）で表される化合物を脱水縮合剤の存在下で反応させることにより製造することができる。なお、式（ＩＩ）の化合物は、市販品を使用できる他、公知の方法にて製造することもできる。式（ＩＩＩ）の化合物は、市販品を使用できる他、後記中間体製法に記載の方法にて製造することもできる。 Manufacturing method [1]
The compound of the above formula (I) can be produced by reacting a compound represented by the following formula (II) with a compound represented by the following formula (III) in the presence of a dehydration condensing agent. In addition, the compound of Formula (II) can also be manufactured by a well-known method besides using a commercial item. The compound of Formula (III) can use a commercial item, and can also manufacture it by the method as described in a postscript intermediate manufacturing method.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（製法［１］における式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びｍは前述のとおりである。） (In the formula in the production method [1], R 1 , R 2 , R 3 , R 4 and m are as described above.)
　脱水縮合剤としては、例えば１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミド塩酸塩、１，３－ジシクロヘキシルカルボジイミドなどが挙げられる。該反応は、必要に応じて添加剤を加えて行うことができる。添加剤としては、例えば１－ヒドロキシベンゾトリアゾール、Ｎ－ヒドロキシコハク酸イミド、Ｎ，Ｎ－ジメチル－４－アミノピリジンなどが挙げられる。 Examples of the dehydrating condensing agent include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1,3-dicyclohexylcarbodiimide and the like. The reaction can be performed by adding an additive as necessary. Examples of the additive include 1-hydroxybenzotriazole, N-hydroxysuccinimide, N, N-dimethyl-4-aminopyridine 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、例えばトリエチルアミン、４－メチルモルホリン、ジイソプロピルエチルアミンなどの第三級アミン類、１，８－ジアザビシクロ［５．４．０］－７－ウンデセン、ピリジン、４－（ジメチルアミノ）ピリジン、２，６－ルチジンなどが挙げられる。
　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、特に制限されないが、例えばＮ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリジノンのような酸アミド類；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；ピリジンのような含窒素芳香族化合物類；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０℃から反応系内が加熱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～２４時間で行うことができる。 The reaction can be carried out in the presence of a base as necessary. Examples of the base include tertiary amines such as triethylamine, 4-methylmorpholine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, pyridine, 4- (dimethylamino) pyridine, 2 , 6-lutidine and the like.
The reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited, but for example, acid amides such as N, N-dimethylformamide and N-methylpyrrolidinone; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; nitrogen-containing compounds such as pyridine One type or two or more types can be appropriately selected from aromatic compounds;
The reaction temperature can usually be in the range of about 0 ° C. to a temperature at which the inside of the reaction system is heated to reflux. The reaction time is usually several minutes to 24 hours.
製法［２］
　式（Ｉ）の化合物は、下記式（ＩＩ－ａ）で表される化合物と下記式（ＩＩＩ）で表される化合物を塩基の存在下で反応させることにより製造することができる。式（ＩＩ－ａ）の化合物は、市販品を使用できる他、後記中間体製法に記載の方法にて製造することもできる。 Manufacturing method [2]
The compound of the formula (I) can be produced by reacting a compound represented by the following formula (II-a) with a compound represented by the following formula (III) in the presence of a base. The compound of the formula (II-a) can be a commercially available product or can be produced by the method described in the intermediate production method described later.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（製法［２］における式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びｍは前述のとおりであり；Ｘはハロゲン原子である。）
　Ｘであるハロゲン原子としては、フッ素、塩素、臭素又はヨウ素の各原子が挙げられる。 (In the formula in the production method [2], R 1 , R 2 , R 3 , R 4 and m are as described above; X is a halogen atom.)
Examples of the halogen atom that is X include fluorine, chlorine, bromine, and iodine atoms.
　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、ジイソプロピルエチ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。
　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、特に制限されないが、例えば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；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリジノンのような酸アミド類；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；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０℃から反応系内が加熱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～２４時間で行うことができる。 The base may be an organic base or an inorganic base. Examples of the organic base include amine bases such as triethylamine and diisopropylethylamine. Examples of 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 is not particularly limited. For example, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; acid amides such as N, N-dimethylformamide and N-methylpyrrolidinone; dichloromethane and chloroform 1 type, or 2 or more types can be appropriately selected and used from such aliphatic halogenated hydrocarbons.
The reaction temperature can usually be in the range of about 0 ° C. to a temperature at which the inside of the reaction system is heated to reflux. The reaction time is usually several minutes to 24 hours.
製法［３］
　前記式（Ｉ）中、Ｒ３が以下のＲ３ａである下記式（Ｉ－ｂ）で表される化合物は、Ｒ３が水素原子である場合の下記式（Ｉ－ａ）で表される化合物と、式：Ｒ３ａＸで表される化合物とを、塩基の存在下で反応させることにより、製造することができる。 Manufacturing method [3]
In the formula (I), the compound represented by the following formula (Ib) in which R 3 is the following R 3a is represented by the following formula (Ia) when R 3 is a hydrogen atom. It can be produced by reacting a compound with a compound represented by the formula: R 3a X in the presence of a base.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（製法［３］における式中、Ｒ３ａはアルキル、アルケニル、アルキニル、シクロアルキル、アルコキシアルキル、アルキルカルボニル、アルコキシカルボニル、アルキルスルホニル又はアリールカルボニルであり；Ｒ１、Ｒ２、Ｒ４、Ｘ及びｍは前述のとおりである。） (In the formula in the production method [3], R 3a is alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl or arylcarbonyl; R 1 , R 2 , R 4 , X and m Is as described above.)
　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。
　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、特に制限されないが、例えば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；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリジノンのような酸アミド類；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；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℃から反応系内が加熱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。 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 hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide. Thing; etc. are mentioned.
The reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited. For example, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; acid amides such as N, N-dimethylformamide and N-methylpyrrolidinone; dichloromethane and chloroform 1 type, or 2 or more types can be appropriately selected and used from such aliphatic halogenated hydrocarbons.
The reaction temperature can be usually in the range of about 20 ° C. to a temperature at which the inside of the reaction system is heated to reflux. The reaction time can usually be from several minutes to 48 hours.
中間体製法［１］
　前記式（ＩＩ－ａ）の化合物は、下記のスキームに示した通り、式（ＩＩ）の化合物をハロゲン化剤と反応させることにより製造することができる。 Intermediate production method [1]
The compound of the formula (II-a) can be produced by reacting the compound of the formula (II) with a halogenating agent as shown in the following scheme.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
（中間体製法［１］における式中、Ｒ１、Ｒ２、Ｘ及びｍは前述のとおりである。） (In the formula in the intermediate production method [1], R 1 , R 2 , X and m are as described above.)
　ハロゲン化剤としては、例えば塩化チオニル、塩化オキサリル、塩化ホスホリル、塩化スルフリル、三塩化リン、五塩化リンなどが挙げられる。
　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、特に制限されないが、例えば塩化メチレン、ジクロロエタン、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、クロロベンゼンのような芳香族炭化水素類などから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０℃から反応系内が加熱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。 Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride and the like.
The reaction can be performed in the presence of a solvent, if necessary. The solvent is not particularly limited, but for example, one or two or more types of aliphatic halogenated hydrocarbons such as methylene chloride, dichloroethane, and chloroform; aromatic hydrocarbons such as toluene and chlorobenzene, and the like are appropriately selected. Can do.
The reaction temperature can be usually from about 0 ° C. to a temperature at which the inside of the reaction system is heated to reflux. The reaction time is usually several minutes to 24 hours.
中間体製法［２］
　式（ＩＩＩ）の化合物は、下記式（ＩＶ）で表される化合物と下記式（Ｖ）で表される化合物を反応させることにより製造できる。なお、式（ＩＶ）の化合物及び式（Ｖ）の化合物は、市販品を使用できる他、公知の方法にて製造することもできる。 Intermediate production method [2]
The compound of the formula (III) can be produced by reacting a compound represented by the following formula (IV) with a compound represented by the following formula (V). In addition, the compound of Formula (IV) and the compound of Formula (V) can also be manufactured by a well-known method besides using a commercial item.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（中間体製法［２］における式中、Ｒ３及びＲ４は前述のとおりである。） (In the formula in the intermediate production method [2], R 3 and R 4 are as described 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。溶媒は、特に制限されないが、例えばＮ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリジノンのような酸アミド類；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；ピリジンのような含窒素芳香族化合物類；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０℃から反応系内が加熱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～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 is not particularly limited, but for example, acid amides such as N, N-dimethylformamide and N-methylpyrrolidinone; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; nitrogen-containing compounds such as pyridine One type or two or more types can be appropriately selected from aromatic compounds;
The reaction temperature can usually be in the range of about 0 ° C. to a temperature at which the inside of the reaction system is heated to reflux. The reaction time is usually several minutes to 24 hours.
中間体製法［３］
　前記式（ＩＩＩ）において、Ｒ３が前述のＲ３ａである下記式（ＩＩＩ－１）で表される化合物は、下記のスキームに示される方法でも製造することができる。なお、下記式（ＶＩ）で表される化合物は、市販品を使用できる他、公知の方法にて製造することもできる。 Intermediate production method [3]
In the formula (III), the compound represented by the following formula (III-1) in which R 3 is the above-described R 3a can also be produced by the method shown in the following scheme. In addition, the compound represented by following formula (VI) can use a commercial item, and can also be manufactured by a well-known method.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
（中間体製法［３］における式中、Ｒ３ａ、Ｒ４及びＸは前述のとおりである。） (In the formula in the intermediate production method [3], R 3a , R 4 and X are as described above.)
（工程１）
　式（ＶＩＩ）の化合物は、式（ＶＩ）の化合物と二炭酸ジｔｅｒｔ－ブチルを必要に応じて塩基の存在下で反応させることにより製造することができる。
　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；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）アミドのようなアルカリ金属アミド；などが挙げられる。
　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、特に制限されないが、例えば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；酢酸メチル、酢酸エチルのようなエステル類；塩化メチレン、ジクロロエタン、クロロホルムのような脂肪族ハロゲン化炭化水素類；メタノール、エタノール、ｔｅｒｔ－ブチルアルコールのようなアルコール類；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－２０℃から反応系内が加熱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。 (Process 1)
The compound of formula (VII) can be produced by reacting the compound of formula (VI) with ditert-butyl dicarbonate, if necessary, in the presence of a base.
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 hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide. And alkali metal amides such as lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, and potassium bis (trimethylsilyl) amide.
The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include, but are not limited to, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; esters such as methyl acetate and ethyl acetate; aliphatic halogens such as methylene chloride, dichloroethane and chloroform. One kind or two or more kinds can be appropriately selected and mixed from the following: hydrocarbons; alcohols such as methanol, ethanol and tert-butyl alcohol; water;
The reaction temperature can usually be in the range of about −20 ° C. to the temperature at which the reaction system is heated to reflux. The reaction time can usually be from several minutes to 48 hours.
（工程２）
　式（ＶＩＩＩ）の化合物は、式（ＶＩＩ）の化合物と、式：Ｒ３ａＸで表される化合物とを塩基の存在下で反応させることで製造することができる。本反応は、前記製法［３］と同様の方法で行うことができる。 (Process 2)
The compound of the formula (VIII) can be produced by reacting the compound of the formula (VII) with a compound represented by the formula: R 3a X in the presence of a base. This reaction can be carried out in the same manner as in the above production method [3].
（工程３）
　式（ＩＩＩ－１）の化合物は、式（ＶＩＩＩ）の化合物と酸とを反応させることで製造することができる。
　酸としては、例えば塩酸、硫酸等の無機酸；酢酸、トリフルオロ酢酸等の有機酸が挙げられる。
　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、特に制限されないが、例えば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；酢酸メチル、酢酸エチルのようなエステル類；塩化メチレン、ジクロロエタン、クロロホルムのような脂肪族ハロゲン化炭化水素類；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０℃から反応系内が加熱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。 (Process 3)
The compound of the formula (III-1) can be produced by reacting the compound of the formula (VIII) with an acid.
Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as acetic acid and trifluoroacetic acid.
The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include, but are not limited to, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; esters such as methyl acetate and ethyl acetate; aliphatic halogens such as methylene chloride, dichloroethane and chloroform. One kind or two or more kinds can be appropriately selected and mixed for use from hydrocarbons; water; and the like.
The reaction temperature can usually be in the range of about 0 ° C. to a temperature at which the inside of the reaction system is heated to reflux. The reaction time can usually be from several minutes to 48 hours.
　本発明化合物を含有する有害生物防除剤の望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としては、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、殺ダニ剤、殺線虫剤又は殺土壌害虫剤が挙げられる。 The desirable mode of the pest control agent containing the compound of the present invention is described below. Examples of the pest control agent containing the compound of the present invention include pests, mites, nematodes or soil pests that are problematic in the field of agriculture and horticulture, that is, agricultural and horticultural insecticides, acaricides, nematicides or Soil-killing pesticides.
　本発明化合物は、農園芸用殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤の有効成分として有用であるが、具体的には、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。本発明化合物を含有する農園芸用殺虫剤、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 compound of the present invention is useful as an active ingredient of agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides. Specifically, aphids such as peach aphids, cotton aphids Moth, weevil, lotus moth, codling moth, ball worm, cigarette bud worm, gypsy moth, corn borer, chanoco cricket, leafworm, ball weevil, planthopper, leafhopper, scale insect, stink bug, whitefly Pests, such as slugs, cockroaches, house flies, house mosquitoes, etc .; agricultural pests such as slugs, mussels, etc .; Bakuga, azuki beetle, wolfberry, beetle Stored pests such as garments; clothing such as moths, swordfish, termites etc .; house pests; pests such as nymphs, mite spider mites, kanzawa spider mites, mandarin spider mites, apple spider mites, chanterid mites, citrus mites, mites, etc. Plant parasitic mites; Indoor dust mites such as Staghorn mite, Salamander mites, Southern mites, etc .; It is effective for controlling pests such as plant parasitic nematodes, etc .; The agricultural and horticultural 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. is there.
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農園芸用殺虫剤、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。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農園芸用殺虫剤、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。 In addition, agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides containing the compounds of the present invention are various resistances against drugs such as organophosphorus agents, carbamate agents, synthetic pyrethroid agents, neonicotinoid agents, etc. It is also effective for controlling pests. Furthermore, since the compound of the present invention has an excellent osmotic transfer property, the agricultural or horticultural insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is treated on the soil. By this, it is possible to control pests in the foliage at the same time as the control of soil harmful insects, mites, nematodes, gastropods, and isopods.
　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望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農園芸用殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤が挙げられる。 As another desirable embodiment of the insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention, the above plant parasitic mites, agricultural pests, plant parasitic nematodes, gastropods And agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides that comprehensively control soil pests and the like.
　本発明化合物を含有する有害生物防除剤は、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、当該分野で通常用いられているあらゆる製剤形態にすることができる。製剤に使用する補助剤としては、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。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、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０．００１：９９．９９９～９５：５、望ましくは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（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 pest control agent containing the compound of the present invention is usually a powder, granule, granule wettable powder, wettable powder, aqueous suspension, oily suspension by mixing the compound with various agricultural adjuvants. It is used in various forms such as pharmaceuticals, aqueous granules, aqueous solvents, emulsions, solutions, pastes, aerosols, microdispersions, etc., but as long as it meets the purpose of the present invention, it is usually used in this field. It can be in any formulation form. Adjuvants used in the formulation 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, 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, etc. Solvent; fatty acid salt, benzoate, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, alcohol Sulfate ester salt, 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 Salts, anionic surfactants such as naphthalenesulfonate formaldehyde condensates; sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid polyglycerides 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, polyoxyethylene Nonionic surfactants such as fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid esters; olive oil, kapok oil, castor oil, palm oil, Coconut oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil , Vegetable oils such as chopped oil and liquid paraffin, and mineral oils. 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 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 compounding ratio (weight ratio) of the compound of the present invention and various adjuvants is 0.001: 99.999 to 95: 5, desirably 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 (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.
　本発明化合物を含有する有害生物防除剤の施用は、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、望ましくは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０．０５～５０，０００ｇ、望ましくは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の防除方法、中でも害虫、ダニ、線虫又は土壌害虫の防除方法、特には植物寄生性ダニ類、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 pest control agent containing the compound of the present invention cannot be defined unconditionally due to differences in weather conditions, formulation form, application time, application place, type of pests and occurrence, etc., but generally 0.05 to 800,000 ppm The active ingredient concentration is preferably 0.5 to 500,000 ppm, and the application amount per unit area is 0.05 to 50,000 g, preferably 1 to 30,000 g of the compound of the present invention per hectare. . Further, the present invention includes a method for controlling pests by such an application method, particularly a method for controlling pests, mites, nematodes or soil pests, particularly plant parasitic mites, agricultural pests, plant parasitic nematodes. Also included are methods of controlling the species.
　本発明化合物を含有する農園芸用殺虫剤、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（混入、灌注等）、表面施用（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 agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides containing the compounds of the present invention, or dilutions thereof, is generally a commonly used application method, ie spraying. (For example, spraying, misting, atomizing, dusting, water surface application, etc.), soil application (mixing, irrigation, etc.), surface application (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有害生物防除剤は、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。他の農薬としては、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。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、このような有害生物防除用組成物も含まれる。 In addition, the pest control agent containing the compound of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, safeners, etc., and in this case, more excellent effects and activities may be exhibited. Other pesticides include herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, etc. . 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. 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 both may be used together. The present invention includes such a pest control composition.
　上記他の農薬中の、殺虫剤、殺ダニ剤、殺線虫剤或い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)、オキシデプロホス（oxydeprofos）、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）、フルキサメタミド（fluxametamide）、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）、ピフルブミド（pyflubumide）、dicloromezotiaz、fluhexafon、チオキサザフェン（tioxazafen）、fluazaindolizine、ＮＡ－８９、ＮＮＩ－１５０１、Ｓ－１５８７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 an insecticide, acaricide, nematicide or soil pesticide (generic name; including some pending applications or Japan Plant Protection Association test code) Profenofos, dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephate, prothiophos, prothiophos, prothiophos Fosthiazate, cadusafos, dislufoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate ), Sulprofos, thiomethos (thiometon), bamidothion, pyraclofos, pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formothion, malathion, tetrachlorvinphos (tetrachlorvinphos), chlorfenvinphos, cyanophos, trichlorfon, methidathion, phenthoate, oxydeprofos, adinphos-methyl, fenthion , Heptenophos, methoxychlor, parathion, phosphocarb, demeton-S-methyl, monocrotophos, methamidophos, imicyafos, Parathione-methyl (parathio Organophosphate compounds such as n-methyl, 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 Radipylon, fluxametamide, tetraniliprole, fluralaner, broflanilide, pyflubumide, dicloromezotiaz, fluhexafon, tioxdofen, tioxazafen, tioxazafen, N , Compounds such as S-1587, and the like.
　更に、Bacillus thuringiensis aizawai、Bacillus thuringiensis kurstaki、Bacillus thuringiensis israelensis、Bacillus thuringiensis japonensis、Bacillus thuringiensis tenebrionis等の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 thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis tenebrionis and other crystalline protein toxins, entomopathogenic virus agents, insect pathogenic fungi Microbial pesticides such as avermectin, emamectin benzoate, milbemectin, milbemycin, spinosad, ivermectin, lepimectin, DE-175, abamectin antibiotics such as abamectin, emamectin, spinetoram and semisynthetic antibiotics; natural products such as azadirachtin, rotenone; repellents such as deet; Etc. Mix, it can also be used in combination.
　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；
　テブフロキン(tebufloquin)のようなキノリン系化合物；
　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））、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）、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 compounds such as tebufloquin;
Thiazolidine-based compounds such as flutianil;
Other compounds include pyribencarb, isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, and sodium metam Metam-sodium, nicobifen, metrafenone, UBF-307, diclocymet, proquinazid, amisulbrom; also known as amibromdole, pyriofenone isofetamid ) Mandipropamid, fluopicolide, carpropamid, meptyldinocap, spiroxamine, fenpyraza Examples thereof include fenpyrazamine, mandestrobin, ZF-9646, BCF-051, BCM-061, BCM-062 and the like.
　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。 In addition, as an agrochemical that can be used in combination with or combined with the compound of the present invention, for example, an active ingredient compound of a herbicide as described in The Pesticide Manual (15th edition), particularly a soil treatment type, etc. There is.
　次に、本発明のＮ－（４－ピリジル）ベンズアミド化合物又はその塩の望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。 Next, some preferred embodiments of the N- (4-pyridyl) benzamide compound or a salt thereof of the present invention will be exemplified, but these do not limit the present invention.
（１）　前記式（Ｉ）のＮ－（４－ピリジル）ベンズアミド化合物又はその塩。
（２）　前記式（Ｉ）におけるＲ１がハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシアルキル、ハロアルコキシアルキル、アルコキシハロアルキル、アルキルチオ、ハロアルキルチオ又はペンタフルオロスルファニルであり；Ｒ２がハロゲン原子、ヒドロキシル、シアノ、ニトロ、アルキル、アルケニル、アルキニル、シクロアルキル、ハロアルキル、アルコキシ、アルケニルオキシ、アルキニルオキシ、ハロアルコキシ、アルコキシアルキル、アルケニルオキシアルキル、アルキニルオキシアルキル、シクロアルコキシアルキル、ハロアルコキシアルキル、アルコキシハロアルキル、トリアルキルシリル、アミノ、モノアルキルアミノ、モノアルケニルアミノ、モノアルキニルアミノ、ジアルキルアミノ、ジアルケニルアミノ、ジアルキニルアミノ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、モノアルキルアミノカルボニル、ジアルキルアミノカルボニル、アルキルカルボニルオキシ、モノ（アルキルカルボニル）アミノ又はモノ（アルキルカルボニルアルキル）アミノであり；Ｒ３が、水素原子、アルキル、アルケニル、アルキニル、シクロアルキル、アルコキシアルキル、アルキルカルボニル、アルコキシカルボニル、アルキルスルホニル又はアリールカルボニルであり；Ｒ４がハロゲン原子、メルカプト、シアノ、ニトロ、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシ、アルケニルオキシ、アルキニルオキシ、ハロアルコキシ、アルキルチオ、アルケニルチオ、アルキニルチオ、ハロアルキルチオ、アルキルスルフィニル、アルケニルスルフィニル、アルキニルスルフィニル、ハロアルキルスルフィニル、アルキルスルホニル、アルケニルスルホニル、アルキニルスルホニル、ハロアルキルスルホニル、アルコキシアルキル、アルキルチオアルキル、モノアルキルアミノアルキル、ジアルキルアミノアルキル、ヒドロキシルアルキル、ホルミル、カルボキシル、アルキルカルボニル、アルコキシカルボニル、（アルキルチオ）カルボニル、モノアルキルアミノカルボニル、モノ（シクロアルキルアルキル）アミノカルボニル、アルキルカルボニルオキシ又はアルキルカルボニルチオであり；ｍは０～３の整数である前記（１）に記載の化合物又はその塩。
（３）　前記式（Ｉ）におけるＲ１がハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシハロアルキル、ハロアルキルチオ又はペンタフルオロスルファニルである前記（１）又は（２）に記載の化合物又はその塩。 (1) The N- (4-pyridyl) benzamide compound of the above formula (I) or a salt thereof.
(2) the formula (I) R 1 in the halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, Alkoxyhaloalkyl, alkylthio, halo alkylthio or pentafluorosulfanyl; R 2 is a halogen atom , Hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkoxyalkyl, alkenyloxyalkyl, alkynyloxyalkyl, cycloalkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl , Trialkylsilyl, amino, monoalkylamino, monoalkenylamino, monoalkynylamino, dialkylamino , Dialkenyl amino, di alkynylamino, carboxyl, alkylcarbonyl, alkoxycarbonyl, mono alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonyloxy, mono- be (alkyl) amino or mono (alkylcarbonyl alkyl) amino; R 3 is A hydrogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl or arylcarbonyl; R 4 is a halogen atom, mercapto, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, Alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkenylthio, alkynylthio, haloalkylthio O, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, haloalkylsulfonyl, alkoxyalkyl, alkylthioalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, hydroxylalkyl, formyl, carboxyl, alkylcarbonyl , Alkoxycarbonyl, (alkylthio) carbonyl, monoalkylaminocarbonyl, mono (cycloalkylalkyl) aminocarbonyl, alkylcarbonyloxy or alkylcarbonylthio; m is an integer of 0 to 3, Or a salt thereof.
(3) The compound or salt thereof according to (1) or (2), wherein R 1 in formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio, or pentafluorosulfanyl. .
（４）　前記式（Ｉ）におけるＲ２がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、アルキルスルホニル、アミノ又はジアルキルアミノである前記（１）～（３）のいずれか１に記載の化合物又はその塩。 (4) The compound according to any one of (1) to (3) above, wherein R 2 in the formula (I) is a halogen atom, nitro, alkyl, alkoxy, alkylthio, alkylsulfonyl, amino or dialkylamino, or a compound thereof salt.
（５）　前記式（Ｉ）におけるＲ３が水素原子、アルキル、シクロアルキル、アルコキシアルキル、アルキルカルボニル又はアルコキシカルボニルである前記（１）～（４）のいずれか１に記載の化合物又はその塩。 (5) The compound or a salt thereof according to any one of (1) to (4), wherein R 3 in the formula (I) is a hydrogen atom, alkyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl or alkoxycarbonyl.
（６）　前記式（Ｉ）におけるｍが０又は１である前記（１）～（５）のいずれか１に記載の化合物又はその塩。
（７）　前記式（Ｉ）におけるｍが０である前記（１）～（５）のいずれか１に記載の化合物又はその塩。 (6) The compound or salt thereof according to any one of (1) to (5), wherein m in the formula (I) is 0 or 1.
(7) The compound or a salt thereof according to any one of (1) to (5), wherein m in the formula (I) is 0.
（８）　前記式（Ｉ）におけるＲ４がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル、（アルキルチオ）カルボニル、モノアルキルアミノカルボニル又はモノ（シクロアルキルアルキル）アミノカルボニルである前記（１）～（７）のいずれか１に記載の化合物又はその塩。
（９）　前記式（Ｉ）におけるＲ４がハロゲン原子、メルカプト、シアノ、ニトロ、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシ、アルケニルオキシ、アルキニルオキシ、ハロアルコキシ、アルキルチオ、アルケニルチオ、アルキニルチオ、ハロアルキルチオ、アルキルスルフィニル、アルケニルスルフィニル、アルキニルスルフィニル、ハロアルキルスルフィニル、アルキルスルホニル、アルケニルスルホニル、アルキニルスルホニル、ハロアルキルスルホニル、アルコキシアルキル、アルキルチオアルキル、モノアルキルアミノアルキル、ジアルキルアミノアルキル、ヒドロキシルアルキル、ホルミル、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルケニルオキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル、（アルキルチオ）カルボニル、アルキルカルボニルオキシ又はアルキルカルボニルチオである前記（１）～（８）のいずれか１に記載の化合物又はその塩。
（１０）　前記式（Ｉ）におけるＲ４がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル又は（アルキルチオ）カルボニルである前記（１）～（９）のいずれか１に記載の化合物又はその塩。
（１１）　前記式（Ｉ）におけるＲ４がハロゲン原子、ニトロ、アルコキシ、アルコキシカルボニル、（アルキルチオ）カルボニル、モノアルキルアミノカルボニル又はモノ（シクロアルキルアルキル）アミノカルボニルである前記（１）～（１０）のいずれか１に記載の化合物又はその塩。 (8) R 4 in the formula (I) is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxy The compound or a salt thereof according to any one of the above (1) to (7), which is carbonyl, cyanoalkoxycarbonyl, (alkylthio) carbonyl, monoalkylaminocarbonyl or mono (cycloalkylalkyl) aminocarbonyl.
(9) R 4 in the formula (I) is a halogen atom, mercapto, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkenylthio, alkynylthio, haloalkylthio Alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, haloalkylsulfonyl, alkoxyalkyl, alkylthioalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, hydroxylalkyl, formyl, carboxyl, alkylcarbonyl, Alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxyca In any one of the above (1) to (8), which is bonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyanoalkoxycarbonyl, (alkylthio) carbonyl, alkylcarbonyloxy or alkylcarbonylthio Or a salt thereof.
(10) R 4 in the formula (I) is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxy 10. The compound or a salt thereof according to any one of (1) to (9), which is carbonyl, cyanoalkoxycarbonyl or (alkylthio) carbonyl.
(11) The above (1) to (10), wherein R 4 in the formula (I) is a halogen atom, nitro, alkoxy, alkoxycarbonyl, (alkylthio) carbonyl, monoalkylaminocarbonyl or mono (cycloalkylalkyl) aminocarbonyl Or a salt thereof.
（１２）　前記式（Ｉ）におけるＲ１がハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシハロアルキル、ハロアルキルチオ又はペンタフルオロスルファニルであり；Ｒ２がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、アルキルスルホニル、アミノ又はジアルキルアミノであり；Ｒ３が水素原子、アルキル、シクロアルキル、アルコキシアルキル、アルキルカルボニル又はアルコキシカルボニルであり；Ｒ４がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル、（アルキルチオ）カルボニル、アルキルアミノカルボニル又は（シクロアルキルアルキル）アミノカルボニルであり；ｍが０又は１である前記（１）に記載の化合物又はその塩。
（１３）　前記式（Ｉ）におけるＲ１がハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシハロアルキル、ハロアルキルチオ又はペンタフルオロスルファニルであり；Ｒ２がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、アルキルスルホニル、アミノ又はジアルキルアミノであり；Ｒ３が水素原子、アルキル、シクロアルキル、アルコキシアルキル、アルキルカルボニル又はアルコキシカルボニルであり；Ｒ４がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル又は（アルキルチオ）カルボニルであり；ｍが０又は１である前記（１）に記載の化合物又はその塩。
（１４）　前記式（Ｉ）におけるＲ１がハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシハロアルキル、ハロアルキルチオ又はペンタフルオロスルファニルであり；Ｒ２がハロゲン原子、ニトロ、アルキル、アルキルチオ、アルキルスルホニル又はアミノであり；Ｒ３が水素原子、アルキル、シクロアルキル、アルキルカルボニル又はアルコキシカルボニルであり；Ｒ４がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル、（アルキルチオ）カルボニル、アルキルアミノカルボニル又は（シクロアルキルアルキル）アミノカルボニルであり；ｍが０又は１である前記（１）に記載の化合物又はその塩。
（１５－１）　前記式（Ｉ）におけるＲ１がハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシハロアルキル、ハロアルキルチオ又はペンタフルオロスルファニルであり；Ｒ２がハロゲン原子、ニトロ、アルキル、アルキルチオ、アルキルスルホニル又はアミノであり；Ｒ３が水素原子、アルキル、シクロアルキル、アルキルカルボニル又はアルコキシカルボニルであり；Ｒ４がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル又は（アルキルチオ）カルボニルであり；ｍが０又は１である前記（１）に記載の化合物又はその塩。
（１５－２）　前記式（Ｉ）におけるＲ１がハロゲン原子、アルキル、ハロアルキル、ハロアルコキシ、アルコキシハロアルキル、ハロアルキルチオ又はペンタフルオロスルファニルであり；Ｒ２がハロゲン原子、アルキル、アルキルチオ、アルキルスルホニル又はアミノであり；Ｒ３が水素原子、アルキル、シクロアルキル、アルキルカルボニル又はアルコキシカルボニルであり；Ｒ４がハロゲン原子、アルコキシ、アルキルチオ、アルキルカルボニル、アルコキシカルボニル、アルコキシアルコキシカルボニル、シアノアルコキシカルボニル又は（アルキルチオ）カルボニルであり；ｍが０又は１である前記（１）又は（２）に記載の化合物又はその塩。
（１６）　前記式（Ｉ）におけるＲ１がハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシハロアルキル、ハロアルキルチオ又はペンタフルオロスルファニルであり；Ｒ２がハロゲン原子又はアルキルであり；Ｒ３が水素原子であり；Ｒ４がハロゲン原子、ニトロ、アルコキシ、アルコキシカルボニル、（アルキルチオ）カルボニル、モノアルキルアミノカルボニル又はモノ（シクロアルキルアルキル）アミノカルボニルであり；ｍが０又は１である前記（１）又は（２）に記載の化合物又はその塩。 (12) R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl; R 2 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, Alkylsulfonyl, amino or dialkylamino; R 3 is a hydrogen atom, alkyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl or alkoxycarbonyl; R 4 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl , Alkoxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonyl The compound or a salt thereof according to the (1) m is 0 or 1; alkoxycarbonyl, cyano alkoxycarbonyl, (alkylthio) carbonyl, alkylamino carbonyl or (cycloalkylalkyl) amino carbonyl.
(13) R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl; R 2 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, Alkylsulfonyl, amino or dialkylamino; R 3 is a hydrogen atom, alkyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl or alkoxycarbonyl; R 4 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl , Alkoxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonyl The compound or a salt thereof according to the (1) m is 0 or 1; alkoxycarbonyl, cyano alkoxycarbonyl or (alkylthio) carbonyl.
(14) R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl; R 2 is a halogen atom, nitro, alkyl, alkylthio, alkylsulfonyl Or R 3 is a hydrogen atom, alkyl, cycloalkyl, alkylcarbonyl or alkoxycarbonyl; R 4 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkynyloxycarbonyl, Cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyanoalkoxycarbonyl, The compound or a salt thereof according to the (1) m is 0 or 1; alkylthio) carbonyl, alkylamino carbonyl or (cycloalkylalkyl) amino carbonyl.
(15-1) R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl; R 2 is a halogen atom, nitro, alkyl, alkylthio, R 3 is a hydrogen atom, alkyl, cycloalkyl, alkylcarbonyl or alkoxycarbonyl; R 4 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkynyloxy Carbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyanoalkoxycarbonyl Or (alkylthio) carbonyloxy; compound or a salt thereof according to the (1) m is 0 or 1.
(15-2) R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl; R 2 is a halogen atom, alkyl, alkylthio, alkylsulfonyl or amino R 3 is a hydrogen atom, alkyl, cycloalkyl, alkylcarbonyl or alkoxycarbonyl; R 4 is a halogen atom, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkoxyalkoxycarbonyl, cyanoalkoxycarbonyl or (alkylthio) carbonyl The compound or a salt thereof according to (1) or (2), wherein m is 0 or 1.
(16) R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl; R 2 is a halogen atom or alkyl; R 3 is hydrogen R 4 is a halogen atom, nitro, alkoxy, alkoxycarbonyl, (alkylthio) carbonyl, monoalkylaminocarbonyl or mono (cycloalkylalkyl) aminocarbonyl; and (1) or m above wherein m is 0 or 1; The compound or a salt thereof according to (2).
（１７）　前記（１）～（１６）のいずれか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。
（１８）　前記（１）～（１６）のいずれか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農園芸用殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤。
（１９）　前記（１）～（１６）のいずれか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農園芸用殺虫剤又は殺ダニ剤。
（２０）　前記（１）～（１６）のいずれか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。 (17) A pest control agent comprising the compound according to any one of (1) to (16) or a salt thereof as an active ingredient.
(18) An agricultural / horticultural insecticide, acaricide, nematicide or soil insecticide containing the compound or salt thereof according to any one of (1) to (16) as an active ingredient.
(19) An agricultural or horticultural insecticide or acaricide containing the compound or salt thereof according to any one of (1) to (16) as an active ingredient.
(20) A method for controlling pests by applying an effective amount of the compound or salt thereof according to any one of (1) to (16).
　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
４－（４－（ヘプタフルオロイソプロピル）ベンズアミド）ニコチン酸メチル（化合物Ｎｏ．Ｉ－９）の合成
　４－（ヘプタフルオロイソプロピル）ベンゾイルクロリド（２５０ｍｇ、０．８ｍｍｏｌ）、４－アミノ－ニコチン酸メチル（１２３．３ｍｇ、０．８ｍｍｏｌ）、ジイソプロピルエチルアミン（０．４２ｍＬ、２．４ｍｍｏｌ）をテトラヒドロフラン（５ｍＬ）に溶解させ６０℃で１時間攪拌した。室温まで放冷した後、水を加え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。残渣をフラッシュクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル）で精製し、目的物（２７０ｍｇ、収率７９％）を得た。 Synthesis example 1
Synthesis of methyl 4- (4- (heptafluoroisopropyl) benzamido) nicotinate (Compound No. I-9) 4- (heptafluoroisopropyl) benzoyl chloride (250 mg, 0.8 mmol), methyl 4-amino-nicotinate ( 123.3 mg, 0.8 mmol) and diisopropylethylamine (0.42 mL, 2.4 mmol) were dissolved in tetrahydrofuran (5 mL) and stirred at 60 ° C. for 1 hour. After allowing to cool to room temperature, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. The residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to obtain the desired product (270 mg, yield 79%).
合成例２
４－（４－（トリフルオロメチル）ベンズアミド）ニコチン酸メチル（化合物Ｎｏ．Ｉ－６）の合成
　４－（トリフルオロメチル）ベンゾイルクロリド（５５０ｍｇ、２．６ｍｍｏｌ）、４－アミノ－ニコチン酸メチル（４００ｍｇ、２．６ｍｍｏｌ）、ジイソプロピルエチルアミン（１．４ｍＬ、７．９ｍｍｏｌ）をテトラヒドロフラン（９ｍＬ）に溶解させ６０℃で１時間攪拌した。室温まで放冷した後、水を加え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除いた後、溶媒を減圧下留去し、目的物（４９０ｍｇ、収率５７％）を得た。 Synthesis example 2
Synthesis of methyl 4- (4- (trifluoromethyl) benzamido) nicotinate (Compound No. I-6) 4- (trifluoromethyl) benzoyl chloride (550 mg, 2.6 mmol), methyl 4-amino-nicotinate ( 400 mg, 2.6 mmol) and diisopropylethylamine (1.4 mL, 7.9 mmol) were dissolved in tetrahydrofuran (9 mL) and stirred at 60 ° C. for 1 hour. After allowing to cool to room temperature, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure to obtain the desired product (490 mg, 57% yield).
合成例３
４－（Ｎ－エチル－４－（（トリフルオロメチル）ベンズアミド）ニコチン酸メチル（化合物Ｎｏ．Ｉ－４０７）の合成
　４－（エチルアミノ）ニコチン酸メチル（１．０ｇ、５．６ｍｍｏｌ）、ジイソプロピルエチルアミン（１．９４ｍＬ、１１．１ｍｍｏｌ）のテトラヒドロフラン（１９ｍＬ）溶液に４－（トリフルオロメチル）ベンゾイルクロリド（１．１６ｇ、５．６ｍｍｏｌ）を加え、６５℃で１６時間攪拌した。反応混合物を水（２０ｍＬ）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。残渣をフラッシュクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル）で精製し、目的物（１．３ｇ、収率６６％）を得た。 Synthesis example 3
Synthesis of methyl 4- (N-ethyl-4-((trifluoromethyl) benzamido) nicotinate (Compound No. I-407) methyl 4- (ethylamino) nicotinate (1.0 g, 5.6 mmol), diisopropyl 4- (Trifluoromethyl) benzoyl chloride (1.16 g, 5.6 mmol) was added to a solution of ethylamine (1.94 mL, 11.1 mmol) in tetrahydrofuran (19 mL), and the mixture was stirred for 16 hours at 65 ° C. The reaction mixture was mixed with water. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate). The target product (1.3 g, yield 66%) was obtained.
中間体合成例１
４－（エチルアミノ）ニコチン酸メチルの合成
　４－クロロニコチン酸メチル（３．３ｇ、１９．２ｍｍｏｌ）のＮ，Ｎ－ジメチルホルムアミド（４０ｍＬ）溶液に７０％エチルアミン水溶液（９．９ｇ、１５３．９ｍｍｏｌ）を加え、７０℃で２時間攪拌した。反応溶液を水（２００ｍＬ）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４－（エチルアミノ）ニコチン酸メチル（３．０ｇ、収率８７％）を得た。 Intermediate synthesis example 1
Synthesis of methyl 4- (ethylamino) nicotinate To a solution of methyl 4-chloronicotinate (3.3 g, 19.2 mmol) in N, N-dimethylformamide (40 mL) 70% ethylamine aqueous solution (9.9 g, 153.9 mmol) ) And stirred at 70 ° C. for 2 hours. The reaction solution was poured into water (200 mL) and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure to obtain methyl 4- (ethylamino) nicotinate (3.0 g, yield 87%).
中間体合成例２
４－（エチルアミノ）ニコチン酸メチルの合成（別法）
（１）４－（（ｔｅｒｔ－ブトキシカルボニル）アミノ）ニコチン酸メチルの合成
　４－アミノ－ニコチン酸メチル（２０．０ｇ、１３１．５ｍｍｏｌ）のｔｅｒｔ－ブチルアルコール（４４０ｍＬ）溶液に二炭酸ジｔｅｒｔ－ブチル（３０．１ｇ、１３８．０ｍｍｏｌ）を滴下し、８０℃で１時間攪拌した。室温まで放冷した後、水を加え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除いた後、溶媒を減圧下留去し、目的物（２６．０ｇ、収率７８％）を得た。 Intermediate synthesis example 2
Synthesis of methyl 4- (ethylamino) nicotinate (alternative method)
(1) Synthesis of methyl 4-((tert-butoxycarbonyl) amino) nicotinate To a solution of methyl 4-amino-nicotinate (20.0 g, 131.5 mmol) in tert-butyl alcohol (440 mL), di-tert-dicarbonate Butyl (30.1 g, 138.0 mmol) was added dropwise, and the mixture was stirred at 80 ° C. for 1 hour. After allowing to cool to room temperature, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure to obtain the desired product (26.0 g, yield 78%).
（２）４－（（ｔｅｒｔ－ブトキシカルボニル）（エチル）アミノ）ニコチン酸メチルの合成
　４－（（ｔｅｒｔ－ブトキシカルボニル）アミノ）ニコチン酸メチル（５．００ｇ、１９．８ｍｍｏｌ）、水素化ナトリウム（１．２７ｇ、３１．７ｍｍｏｌ）のＮ，Ｎ－ジメチルホルムアミド（８０ｍＬ）溶液にヨウ化エチル（２．４０ｍＬ、２９．７ｍｍｏｌ）を滴下し、窒素雰囲気下、室温で１２時間攪拌した。飽和塩化アンモニア水を加え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除いた後、溶媒を減圧下留去し、残渣をフラッシュクロマトグラフィー（溶離液：ｎ－ヘプタン／酢酸エチル）で精製し、目的物（３．５０ｇ、収率６３％）を得た。 (2) Synthesis of methyl 4-((tert-butoxycarbonyl) (ethyl) amino) nicotinate 4-((tert-butoxycarbonyl) amino) methyl nicotinate (5.00 g, 19.8 mmol), sodium hydride ( To a solution of 1.27 g, 31.7 mmol) in N, N-dimethylformamide (80 mL) was added ethyl iodide (2.40 mL, 29.7 mmol) dropwise, and the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. Saturated aqueous ammonia chloride was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to obtain the desired product (3.50 g, yield 63%). Got.
（３）目的物の合成
　４－（（ｔｅｒｔ－ブトキシカルボニル）（エチル）アミノ）ニコチン酸メチル（３．５０ｇ、１２．５ｍｍｏｌ）の塩化メチレン（２５ｍＬ）溶液にトリフルオロ酢酸（２５ｍＬ）を加え、室温で１２時間攪拌した。溶媒を減圧下留去した後、１Ｍ水酸化ナトリウム水溶液と酢酸エチルを加え、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除いた後、溶媒を減圧下留去し、４－（エチルアミノ）ニコチン酸メチル（１．１５ｇ、収率５１％）を得た。 (3) Synthesis of target product Trifluoroacetic acid (25 mL) was added to a solution of methyl 4-((tert-butoxycarbonyl) (ethyl) amino) nicotinate (3.50 g, 12.5 mmol) in methylene chloride (25 mL), Stir at room temperature for 12 hours. The solvent was evaporated under reduced pressure, 1M aqueous sodium hydroxide solution and ethyl acetate were added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure to obtain methyl 4- (ethylamino) nicotinate (1.15 g, yield 51%).
　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、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表中、物性欄に記載の数値は融点（℃）を示し、融点が記載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第２表及び第３表に挙げ、第１表中の物性欄にはＮＭＲと記載する。尚、第１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、ｔ－Ｂｕはターシャリーブチル基を、ｃ－Ｐｒはシクロプロピル基を各々表す。また、（Ｒ２）ｍの欄において、例えば「５－Ｆ」と記載された化合物は、表中の化学構造式に付与した数字の置換位置のみがＲ２で置換されていること、即ち、５位のみがフッ素原子にて置換されている「ｍ＝１」の化合物であることを表す。一方、「ｍ＝０」と記載された化合物は、Ｒ２にて置換されていない化合物であることを表す。他の同様の記載もこれに準じる。 Next, typical examples of the compounds of formula (I) according to the present invention are listed in Table 1. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In Table 1, the numerical values described in the physical properties column indicate melting points (° C.), and for compounds for which melting points are not described, their 1 H-NMR spectral data are listed in Tables 2 and 3, In the physical property column of the table, NMR is described. No. 1 in Table 1 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 t-Bu represents a tertiary butyl group. And c-Pr represents a cyclopropyl group. Further, in the column of (R 2 ) m, for example, in the compound described as “5-F”, only the substitution position of the number given to the chemical structural formula in the table is substituted with R 2 , that is, This represents a compound of “m = 1” in which only the 5-position is substituted with a fluorine atom. On the other hand, the compound described as “m = 0” represents a compound not substituted with R 2 . The same applies to other similar descriptions.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
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
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
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頭放虫し、管口をガーゼでふたをして２５℃の照明付恒温室内に静置した。処理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。本発明化合物として、前記化合物Ｎｏ．Ｉ‐１、Ｉ‐６、Ｉ‐７、Ｉ‐８、Ｉ‐９、Ｉ‐１０、Ｉ‐１１、Ｉ‐１２、Ｉ‐１７、Ｉ‐１８、Ｉ‐２１、Ｉ‐２２、Ｉ‐２４、Ｉ‐２７、Ｉ‐３７、Ｉ‐４２、Ｉ‐４５、Ｉ‐６３、Ｉ‐１０９、Ｉ‐１１６、Ｉ‐１４２、Ｉ‐１８６、Ｉ‐１８８、Ｉ‐１９０、Ｉ‐１９１、Ｉ‐１９２、Ｉ‐１９９、Ｉ‐２０７、Ｉ‐２１５、Ｉ‐２４６、Ｉ‐２４７、Ｉ‐２４９、Ｉ‐２６２、Ｉ‐２６３、Ｉ‐２６４、Ｉ‐２６５、Ｉ‐２７８、Ｉ‐２８０、Ｉ‐２８２、Ｉ‐２８３、Ｉ‐２８４、Ｉ‐２８５、Ｉ‐２８６、Ｉ‐２８７、Ｉ‐２８９、Ｉ‐２９０、Ｉ‐２９１、Ｉ‐２９２、Ｉ‐２９４、Ｉ‐３５３、Ｉ‐４０７、Ｉ‐４０８、Ｉ‐４０９、Ｉ‐４１０、Ｉ‐４１１、Ｉ‐４１２、Ｉ‐４１４、Ｉ‐４１６、Ｉ‐４１７、Ｉ‐４１９、Ｉ‐４２０、Ｉ‐４２１、Ｉ‐５２７、Ｉ‐５３１、Ｉ‐５８３及びＩ‐６１１について試験した結果、いずれの化合物も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 to 3 years old were released, and the tube mouth was covered with gauze and allowed to stand in a constant temperature room at 25 ° C. Five days after the treatment, the survival of the brown planthopper was determined, and the death rate (%) was determined by the following formula. As the compound of the present invention, the above-mentioned compound No. I-1, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-17, I-18, I-21, I-22, I- 24, I-27, I-37, I-42, I-45, I-63, I-109, I-116, I-142, I-186, I-188, I-190, I-191, I-192, I-199, I-207, I-215, I-246, I-247, I-249, I-262, I-263, I-264, I-265, I-278, I- 280, I-282, I-283, I-284, I-285, I-286, I-287, I-289, I-290, I-291, I-292, I-294, I-353, I-407, I-408, I-409, I-410, I-411, I-412, I-414, I-416, I-417, I- 19, I-420, I-421, I-527, I-531, results of testing for I-583 and I-611, both compounds showed a mortality 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
　ポット植えのキュウリ苗にタバココナジラミ成虫を放虫した。１日間産卵させた後、キュウリ苗を取り出して２５℃の照明付恒温室内に静置した。７日後、キュウリ苗に寄生している１～２齢幼虫数を調査し、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静置した。処理７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。本発明化合物として、前記化合物Ｎｏ．Ｉ‐１、Ｉ‐６、Ｉ‐７、Ｉ‐８、Ｉ‐９、Ｉ‐１０、Ｉ‐１２、Ｉ‐１８、Ｉ‐１９、Ｉ‐２１、Ｉ‐２２、Ｉ‐２４、Ｉ‐２７、Ｉ‐３７、Ｉ‐４２、Ｉ‐４３、Ｉ‐４４、Ｉ‐４５、Ｉ‐６３、Ｉ‐９２、Ｉ‐１０９、Ｉ‐１１６、Ｉ‐１１７、Ｉ‐１４２、Ｉ‐１５９、Ｉ‐１８６、Ｉ‐１８７、Ｉ‐１８８、Ｉ‐１９１、Ｉ‐１９９、Ｉ‐２２９、Ｉ‐２４６、Ｉ‐２４７、Ｉ‐２４９、Ｉ‐２６１、Ｉ‐２６２、Ｉ‐２６３、Ｉ‐２６４、Ｉ‐２６５、Ｉ‐２７８、Ｉ‐２７９、Ｉ‐２８０、Ｉ‐２８２、Ｉ‐２８３、Ｉ‐２８４、Ｉ‐２８５、Ｉ‐２８６、Ｉ‐２８７、Ｉ‐２８９、Ｉ‐２９０、Ｉ‐２９１、Ｉ‐２９４、Ｉ‐３５３、Ｉ‐４０７、Ｉ‐４０８、Ｉ‐４０９、Ｉ‐４１０、Ｉ‐４１１、Ｉ‐４１２、Ｉ‐４１４、Ｉ‐４１５、Ｉ‐４１６、Ｉ‐４１９、Ｉ‐５２７、Ｉ‐５２８、Ｉ‐５３１、Ｉ‐５３２、Ｉ‐５４３、Ｉ‐５８３及びＩ‐５８７について試験した結果、いずれの化合物も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 An adult tobacco whitefly was released on a pot-planted cucumber seedling. After laying eggs for one day, cucumber seedlings were taken out and placed in a constant temperature room with illumination at 25 ° C. Seven days later, the number of 1-2 instar larvae parasitizing the cucumber seedlings was examined, and a chemical solution prepared so that the concentration of the compound of the present invention was 200 ppm 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. Seven days after the treatment, the number of old larvae was examined, and the control value was determined by the following formula. As the compound of the present invention, the above-mentioned compound No. I-1, I-6, I-7, I-8, I-9, I-10, I-12, I-18, I-19, I-21, I-22, I-24, I- 27, I-37, I-42, I-43, I-44, I-45, I-63, I-92, I-109, I-116, I-117, I-142, I-159, I-186, I-187, I-188, I-191, I-199, I-229, I-246, I-247, I-249, I-261, I-262, I-263, I- H.264, I-265, I-278, I-279, I-280, I-282, I-283, I-284, I-285, I-286, I-287, I-289, I-290, I-291, I-294, I-353, I-407, I-408, I-409, I-410, I-411, I-412, I-41 , I-415, I-416, I-419, I-527, I-528, I-531, I-532, I-543, I-583 and I-587. The above control values were shown.
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
試験例３　モモアカアブラムシに対する効果試験
　試験管に水挿ししたダイコン葉上にモモアカアブラムシ成虫を５頭放虫した。１日後に成虫を取り除いた後、ダイコン葉上に寄生している幼虫数を数え、本発明化合物の濃度が２００ｐｐｍとなるように調製した薬液に浸漬処理した。薬液が風乾した後に、２５℃の照明付恒温室内に静置した。処理５日後にモモアカアブラムシの生死を判定し、下記の計算式により死虫率を求めた。尚、離脱虫及び異常虫は死亡虫とみなした。本発明化合物として、前記化合物Ｎｏ．Ｉ‐１、Ｉ‐６、Ｉ‐７、Ｉ‐８、Ｉ‐９、Ｉ‐１０、Ｉ‐１１、Ｉ‐１７、Ｉ‐１８、Ｉ‐１９、Ｉ‐２０、Ｉ‐２１、Ｉ‐２２、Ｉ‐２４、Ｉ‐２７、Ｉ‐３７、Ｉ‐４２、Ｉ‐４３、Ｉ‐４４、Ｉ‐４５、Ｉ‐６３、Ｉ‐９２、Ｉ‐１０９、Ｉ‐１１６、Ｉ‐１１７、Ｉ‐１４２、Ｉ‐１８６、Ｉ‐１８７、Ｉ‐１８８、Ｉ‐１９１、Ｉ‐１９２、Ｉ‐１９９、Ｉ‐２０７、Ｉ‐２１５、Ｉ‐２２９、Ｉ‐２４６、Ｉ‐２４７、Ｉ‐２４９、Ｉ‐２６１、Ｉ‐２６２、Ｉ‐２６５、Ｉ‐２７８、Ｉ‐２８０、Ｉ‐２８２、Ｉ‐２８３、Ｉ‐２８４、Ｉ‐２８５、Ｉ‐２８６、Ｉ‐２８７、Ｉ‐２８９、Ｉ‐２９０、Ｉ‐２９１、Ｉ‐２９４、Ｉ‐３５３、Ｉ‐４０３、Ｉ‐４０７、Ｉ‐４０８、Ｉ‐４０９、Ｉ‐４１０、Ｉ‐４１１、Ｉ‐４１２、Ｉ‐４１４、Ｉ‐４１６、Ｉ‐４１７、Ｉ‐４１９、Ｉ‐４２０、Ｉ‐４２１、Ｉ‐５２７、Ｉ‐５３１、Ｉ‐５３２、Ｉ‐５４３、Ｉ‐５８３、Ｉ‐５８４及びＩ‐５８７について試験した結果、いずれの化合物も９０％以上の死虫率を示した。
　死虫率（％）＝（死虫数／供試虫数）×１００ Test Example 3 Effect test on peach aphid Five adult peach aphids were released on radish leaves inserted in test tubes. After removing adults one day later, the number of larvae parasitizing on radish leaves was counted and 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, it was left in a constant temperature room at 25 ° C. with illumination. Five days after the treatment, the viability of the peach aphid was determined, and the mortality was determined by the following formula. The detached insects and abnormal insects were regarded as dead insects. As the compound of the present invention, the above-mentioned compound No. I-1, I-6, I-7, I-8, I-9, I-10, I-11, I-17, I-18, I-19, I-20, I-21, I- 22, I-24, I-27, I-37, I-42, I-43, I-44, I-45, I-63, I-92, I-109, I-116, I-117, I-142, I-186, I-187, I-188, I-191, I-192, I-199, I-207, I-215, I-229, I-246, I-247, I- 249, I-261, I-262, I-265, I-278, I-280, I-282, I-283, I-284, I-285, I-286, I-287, I-289, I-290, I-291, I-294, I-353, I-403, I-407, I-408, I-409, I-410, I-411, -412, I-414, I-416, I-417, I-419, I-420, I-421, I-527, I-531, I-532, I-543, I-583, I-584 As a result of testing for I-587, all compounds showed a mortality rate of 90% or more.
Death rate (%) = (Number of dead insects / number of test insects) × 100
　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
前記（１）～（３）を予め均一に混合し、適量のアセトンで希釈した後、前記（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 the above (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 formation).
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.
　本発明を詳細に、また特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０１６年６月２４日出願の日本特許出願（特願２０１６－１２５２３４）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications 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. 2016-125234) filed on June 24, 2016, the contents of which are incorporated herein by reference.

Claims (9)

  1. 　式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000001
     ［式中、Ｒ１はハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシアルキル、ハロアルコキシアルキル、アルコキシハロアルキル、アルキルチオハロアルキルチオ又はペンタフルオロスルファニルであり；
    Ｒ２はハロゲン原子、ヒドロキシル、シアノ、ニトロ、アルキル、アルケニル、アルキニル、シクロアルキル、ハロアルキル、アルコキシ、アルケニルオキシ、アルキニルオキシ、ハロアルコキシ、アルキルチオ、アルキルスルフィニル、アルキルスルホニル、アルコキシアルキル、アルケニルオキシアルキル、アルキニルオキシアルキル、シクロアルコキシアルキル、ハロアルコキシアルキル、アルコキシハロアルキル、トリアルキルシリル、アミノ、モノアルキルアミノ、モノアルケニルアミノ、モノアルキニルアミノ、ジアルキルアミノ、ジアルケニルアミノ、ジアルキニルアミノ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、モノアルキルアミノカルボニル、ジアルキルアミノカルボニル、アルキルカルボニルオキシ、モノ（アルキルカルボニル）アミノ、ジ（アルキルカルボニル）アミノ、モノ（アルキルカルボニルアルキル）アミノ又はジ（アルキルカルボニルアルキル）アミノであり；
    Ｒ３は、水素原子、アルキル、アルケニル、アルキニル、シクロアルキル、アルコキシアルキル、アルキルカルボニル、アルコキシカルボニル、アルキルスルホニル又はアリールカルボニルであり；
    Ｒ４はハロゲン原子、メルカプト、シアノ、ニトロ、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシ、アルケニルオキシ、アルキニルオキシ、ハロアルコキシ、アルキルチオ、アルケニルチオ、アルキニルチオ、ハロアルキルチオ、アルキルスルフィニル、アルケニルスルフィニル、アルキニルスルフィニル、ハロアルキルスルフィニル、アルキルスルホニル、アルケニルスルホニル、アルキニルスルホニル、ハロアルキルスルホニル、アルコキシアルキル、アルキルチオアルキル、モノアルキルアミノアルキル、ジアルキルアミノアルキル、ヒドロキシルアルキル、ホルミル、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルケニルオキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル、（アルキルチオ）カルボニル、モノアルキルアミノカルボニル、モノ（シクロアルキルアルキル）アミノカルボニル、アルキルカルボニルオキシ又はアルキルカルボニルチオであり；ｍは０～３の整数であり、前記Ｒ２が複数存在する場合、それぞれ同一でも異なっていてもよい］で表されるＮ－（４－ピリジル）ベンズアミド化合物又はその塩。     Formula (I):
    Figure JPOXMLDOC01-appb-C000001
     Wherein R 1 is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, alkylthiohaloalkylthio or pentafluorosulfanyl;
    R 2 is halogen atom, hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxyalkyl, alkenyloxyalkyl, alkynyl Oxyalkyl, cycloalkoxyalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, trialkylsilyl, amino, monoalkylamino, monoalkenylamino, monoalkynylamino, dialkylamino, dialkenylamino, dialkynylamino, carboxyl, alkylcarbonyl, alkoxycarbonyl Monoalkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonyloxy Ci, mono (alkylcarbonyl) amino, di (alkylcarbonyl) amino, mono (alkylcarbonylalkyl) amino or di (alkylcarbonylalkyl) amino;
    R 3 is a hydrogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl or arylcarbonyl;
    R 4 is a halogen atom, mercapto, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkenylthio, alkynylthio, haloalkylthio, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl , Haloalkylsulfinyl, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, haloalkylsulfonyl, alkoxyalkyl, alkylthioalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, hydroxylalkyl, formyl, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxy Carbonyl, cycloalkoxy M is sulfonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyanoalkoxycarbonyl, (alkylthio) carbonyl, monoalkylaminocarbonyl, mono (cycloalkylalkyl) aminocarbonyl, alkylcarbonyloxy or alkylcarbonylthio; N- (4-pyridyl) benzamide compound or a salt thereof, which is an integer of 0 to 3 and may be the same or different when a plurality of R 2 are present.
  2. 　前記式（Ｉ）におけるＲ４がハロゲン原子、メルカプト、シアノ、ニトロ、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシ、アルケニルオキシ、アルキニルオキシ、ハロアルコキシ、アルキルチオ、アルケニルチオ、アルキニルチオ、ハロアルキルチオ、アルキルスルフィニル、アルケニルスルフィニル、アルキニルスルフィニル、ハロアルキルスルフィニル、アルキルスルホニル、アルケニルスルホニル、アルキニルスルホニル、ハロアルキルスルホニル、アルコキシアルキル、アルキルチオアルキル、モノアルキルアミノアルキル、ジアルキルアミノアルキル、ヒドロキシルアルキル、ホルミル、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルケニルオキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル、（アルキルチオ）カルボニル、アルキルカルボニルオキシ又はアルキルカルボニルチオである請求項１に記載の化合物又はその塩。 R 4 in the formula (I) is a halogen atom, mercapto, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkenylthio, alkynylthio, haloalkylthio, alkylsulfinyl Alkenylsulfinyl, alkynylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, haloalkylsulfonyl, alkoxyalkyl, alkylthioalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, hydroxylalkyl, formyl, carboxyl, alkylcarbonyl, alkoxycarbonyl, Alkenyloxycarbonyl, alkynyloxycarbonyl The compound or a salt thereof according to claim 1, which is cycloalkyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyanoalkoxycarbonyl, (alkylthio) carbonyl, alkylcarbonyloxy or alkylcarbonylthio.
  3. 　前記式（Ｉ）におけるＲ４がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル又は（アルキルチオ）カルボニルである請求項１に記載の化合物又はその塩。 R 4 in the formula (I) is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyano The compound or a salt thereof according to claim 1, which is alkoxycarbonyl or (alkylthio) carbonyl.
  4. 　前記式（Ｉ）におけるＲ１がハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシハロアルキル、ハロアルキルチオ又はペンタフルオロスルファニルであり；Ｒ２がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、アルキルスルホニル、アミノ又はジアルキルアミノであり；Ｒ３が水素原子、アルキル、シクロアルキル、アルコキシアルキル、アルキルカルボニル又はアルコキシカルボニルであり；Ｒ４がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル又は（アルキルチオ）カルボニルであり；ｍが０又は１である請求項１に記載の化合物又はその塩。 R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl; R 2 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, alkylsulfonyl, Amino or dialkylamino; R 3 is a hydrogen atom, alkyl, cycloalkyl, alkoxyalkyl, alkylcarbonyl or alkoxycarbonyl; R 4 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl , Alkynyloxycarbonyl, cycloalkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxy The compound or a salt thereof according to claim 1, wherein the compound is carbonyl, cyanoalkoxycarbonyl or (alkylthio) carbonyl; and m is 0 or 1.
  5. 　前記式（Ｉ）におけるＲ１がハロゲン原子、アルキル、ハロアルキル、アルコキシ、ハロアルコキシ、アルコキシハロアルキル、ハロアルキルチオ又はペンタフルオロスルファニルであり；Ｒ２がハロゲン原子、ニトロ、アルキル、アルキルチオ、アルキルスルホニル又はアミノであり；Ｒ３が水素原子、アルキル、シクロアルキル、アルキルカルボニル又はアルコキシカルボニルであり；Ｒ４がハロゲン原子、ニトロ、アルキル、アルコキシ、アルキルチオ、カルボキシル、アルキルカルボニル、アルコキシカルボニル、アルキニルオキシカルボニル、シクロアルコキシカルボニル、ハロアルコキシカルボニル、アルコキシアルコキシカルボニル、アルコキシカルボニルアルコキシカルボニル、シアノアルコキシカルボニル又は（アルキルチオ）カルボニルであり；ｍが０又は１である請求項１に記載の化合物又はその塩。 R 1 in the formula (I) is a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyhaloalkyl, haloalkylthio or pentafluorosulfanyl; R 2 is a halogen atom, nitro, alkyl, alkylthio, alkylsulfonyl or amino Yes; R 3 is a hydrogen atom, alkyl, cycloalkyl, alkylcarbonyl or alkoxycarbonyl; R 4 is a halogen atom, nitro, alkyl, alkoxy, alkylthio, carboxyl, alkylcarbonyl, alkoxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl Haloalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonylalkoxycarbonyl, cyanoalkoxycarbonyl or (alkyl The compound or a salt thereof according to claim 1, wherein m is 0 or 1.
  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.
  7. 　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農園芸用殺虫剤、殺ダニ剤、殺線虫剤又は殺土壌害虫剤。 An agricultural and horticultural insecticide, acaricide, nematicide or soil insecticide containing the compound or salt thereof according to claim 1 as an active ingredient.
  8. 　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農園芸用殺虫剤又は殺ダニ剤。 An agricultural or horticultural insecticide or acaricide containing the compound according to claim 1 or a salt thereof as an active ingredient.
  9. 　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.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019163921A1 (en) * 2018-02-22 2019-08-29 石原産業株式会社 Substituted pyridine compound and salt thereof
AU2018257296B2 (en) * 2017-04-27 2022-01-06 Ishihara Sangyo Kaisha, Ltd. N-(4-pyridyl) nicotinamide compound or salt thereof
WO2022071434A1 (en) * 2020-09-30 2022-04-07 住友化学株式会社 Heterocyclic compound and harmful arthropod-controlling composition containing same

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002533453A (en) * 1998-12-23 2002-10-08 イーライ・リリー・アンド・カンパニー Heteroaromatic amides as inhibitors of factor Xa
JP2004521924A (en) * 2001-03-05 2004-07-22 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Heterocyclic diamide invertebrate pest control agent
WO2006040966A1 (en) * 2004-10-08 2006-04-20 Astellas Pharma Inc. Aromatic-ring-fused pyrimidine derivative
US20070026348A1 (en) * 2005-08-01 2007-02-01 Fuji Photo Film Co., Ltd. Black and white photothermographic material and image forming method
WO2014002754A1 (en) * 2012-06-26 2014-01-03 住友化学株式会社 Amide compound and use thereof for pest control
WO2014117090A1 (en) * 2013-01-28 2014-07-31 Viamet Pharmaceuticals, Inc. Metalloenzyme inhibitor compounds
WO2014207648A1 (en) * 2013-06-24 2014-12-31 Lupin Limited Chromane and chromene derivatives and their use as crac modulators
WO2015025960A1 (en) * 2013-08-23 2015-02-26 石原産業株式会社 Harmful organism control agent

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002533453A (en) * 1998-12-23 2002-10-08 イーライ・リリー・アンド・カンパニー Heteroaromatic amides as inhibitors of factor Xa
JP2004521924A (en) * 2001-03-05 2004-07-22 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Heterocyclic diamide invertebrate pest control agent
WO2006040966A1 (en) * 2004-10-08 2006-04-20 Astellas Pharma Inc. Aromatic-ring-fused pyrimidine derivative
US20070026348A1 (en) * 2005-08-01 2007-02-01 Fuji Photo Film Co., Ltd. Black and white photothermographic material and image forming method
WO2014002754A1 (en) * 2012-06-26 2014-01-03 住友化学株式会社 Amide compound and use thereof for pest control
WO2014117090A1 (en) * 2013-01-28 2014-07-31 Viamet Pharmaceuticals, Inc. Metalloenzyme inhibitor compounds
WO2014207648A1 (en) * 2013-06-24 2014-12-31 Lupin Limited Chromane and chromene derivatives and their use as crac modulators
WO2015025960A1 (en) * 2013-08-23 2015-02-26 石原産業株式会社 Harmful organism control agent

Non-Patent Citations (18)

* Cited by examiner, † Cited by third party
Title
ASHOK, ABHISHEK ET AL.: "Novel Aryl-Modified Benzoylamino-N(5,6-dimethoxy-1H-benzoimidazol-2-yl)- heteroamides as Potent Inhibitors of Vascular Endothelial Growtl Factor Receptors 1 and 2", JOURNAL OF HETEROCYCLIC CHEMISTRY, vol. 54, no. 3, 11 December 2016 (2016-12-11) - May 2017 (2017-05-01), pages 1949 - 1956, XP055601654, ISSN: 0022-152X, DOI: 10.1002/jhet.2791 *
DATABASE REGISTRY [online] 19 July 2017 (2017-07-19), retrieved from STN Database accession no. RN 16952-78-6 *
DATABASE REGISTRY [online] 19 July 2017 (2017-07-19), retrieved from STN Database accession no. RN1465387-74-9 *
DATABASE REGISTRY [online] 19 July 2017 (2017-07-19), retrieved from STN Database accession no. RN1547906-78-4 *
DATABASE REGISTRY [online] 19 July 2017 (2017-07-19), retrieved from STN Database accession no. RN1553808-97-1 *
DATABASE REGISTRY [online] 19 July 2017 (2017-07-19), retrieved from STN Database accession no. RN1713647-16-5 *
DATABASE REGISTRY [online] 19 July 2017 (2017-07-19), retrieved from STN Database accession no. RN1927100-18-2 *
DATABASE REGISTRY retrieved from STN Database accession no. RN1553824-80-8 *
DATABASE REGISTRY retrieved from STN Database accession no. RN1553825-72-1 *
DATABASE REGISTRY retrieved from STN Database accession no. RN1554324-94-5 *
DATABASE REGISTRY retrieved from STN Database accession no. RN1554335-52-2 *
DATABASE REGISTRY retrieved from STN Database accession no. RN1927100-19-3 *
DATABASE REGISTRY retrieved from STN Database accession no. RN1927382-36-2 *
DATABASE REGISTRY retrieved from STN Database accession no. RN1927382-79-3 *
DATABASE REGISTRY retrieved from STN Database accession no. RN1927383-21-8 *
DATABASE REGISTRY retrieved from STN Database accession no. RN1927535-75-8 *
HE, DIAN ET AL.: "Design, Synthesis and Activity Evaluation of N-(pyridin-4-yl) Salicylamides as Antimycobacterial Agents", ASIAN JOURNAL OF CHEMISTRY, vol. 26, no. 21, 2014, pages 7269 - 7275, XP055601632, ISSN: 0970-7077, DOI: 10.14233/ajchem.2014.16594 *
ISMAIL, A. G. ET AL.: "The Synthesis of pyrido [4, 3-d]pyrimidin-4 (3H) -ones from 4-Amino-nicotinic acid", JOURNAL OF THE CHEMICAL SOCIETY [SECTION] C: ORGANIC, vol. 1967, no. 24, pages 2613 - 2617, ISSN: 0022-4952 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2018257296B2 (en) * 2017-04-27 2022-01-06 Ishihara Sangyo Kaisha, Ltd. N-(4-pyridyl) nicotinamide compound or salt thereof
WO2019163921A1 (en) * 2018-02-22 2019-08-29 石原産業株式会社 Substituted pyridine compound and salt thereof
WO2022071434A1 (en) * 2020-09-30 2022-04-07 住友化学株式会社 Heterocyclic compound and harmful arthropod-controlling composition containing same

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