WO2013069771A1 - Anthranilic acid derivative and noxious organism control agent - Google Patents

Anthranilic acid derivative and noxious organism control agent Download PDF

Info

Publication number
WO2013069771A1
WO2013069771A1 PCT/JP2012/079129 JP2012079129W WO2013069771A1 WO 2013069771 A1 WO2013069771 A1 WO 2013069771A1 JP 2012079129 W JP2012079129 W JP 2012079129W WO 2013069771 A1 WO2013069771 A1 WO 2013069771A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
halogen atom
control agent
weight
compounds
Prior art date
Application number
PCT/JP2012/079129
Other languages
French (fr)
Japanese (ja)
Inventor
伸三 利部
正明 三冨
育也 大野
保道 小野▲崎▼
亮 堀越
中村　哲
Original Assignee
Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社
国立大学法人岐阜大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社, 国立大学法人岐阜大学 filed Critical Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社
Publication of WO2013069771A1 publication Critical patent/WO2013069771A1/en

Links

Classifications

    • 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
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/10—Anthelmintics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/14—Ectoparasiticides, e.g. scabicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • the present invention relates to an anthranilic acid derivative and a pest control agent containing the same. More specifically, the present invention relates to an anthranilic acid derivative having a bicyclic to tricyclic fused aromatic heterocycle and a pesticidal agent containing the same.
  • Patent Documents 1 and 2 disclose anthranilic acid-based pest control agents
  • Patent Document 3 discloses a production method thereof. Specific examples of anthranilic acid derivatives having a condensed aromatic heterocycle exhibiting pesticidal activity are disclosed. There is no description.
  • An object of the present invention is to provide a novel compound exhibiting pest control activity.
  • R 1 represents a C 1-8 alkyl group which may be substituted with a halogen atom
  • W each independently represents a halogen atom, a cyano group or a C 1-8 alkyl group which may be substituted with a substituent selected from the group S
  • n represents an integer of 0 to 4
  • A represents a bicyclic to tricyclic fused aromatic heterocycle containing at least one nitrogen atom, which may be substituted with a substituent selected from Group T
  • B represents a 5- to 6-membered aromatic heterocycle optionally substituted with a substituent selected from Group U, which is bonded to the nitrogen atom of A
  • S group consists of a cyano group and a halogen atom
  • T group consists halogen atom, optionally substituted C 1-8 alkyl group and optionally C 1-8 alkyl group optionally substituted by
  • the present invention provides the following [1] to [5].
  • [1] A compound represented by the formula (I).
  • [2] A pest control agent comprising one or more compounds represented by the formula (I).
  • [3] A compound represented by formula (I) for use in pest control.
  • [4] Use of a compound represented by the formula (I) for producing a pest control agent.
  • [5] A method for controlling pests, comprising bringing the compound represented by formula (I) into contact with pests.
  • A is a bicyclic to tricyclic fused pyrrole ring, and B is substituted with a substituent selected from the U group, which is bonded to a nitrogen atom of the fused pyrrole ring.
  • the compound is preferably a pyridine ring or a pyrazine ring optionally substituted with a substituent selected from Group U.
  • the pests to be controlled are preferably agricultural or horticultural pests or animal parasitic pests. That is, the pest control agent is preferably an agricultural or horticultural insecticide or an animal parasite control agent.
  • the compound according to the present invention exhibits excellent pest control activity.
  • the compound according to the present invention is difficult to decrease drug sensitivity, has a high sustained effect, and has high safety during use.
  • halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom.
  • C 1-8 alkyl group is a chain, branched or cyclic alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.
  • a C 1-6 alkyl group is more preferably a C 1-4 alkyl group which is an alkyl group having 1 to 4 carbon atoms.
  • Examples of the C 1-8 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a cyclopropyl group and more preferably a methyl group or an isopropyl group.
  • the upper limit of the number of halogen atoms that may be substituted in the “C 1-8 alkyl group optionally substituted with halogen atom” is the number of hydrogen atoms that the alkyl group has, “Atom” and “C 1-8 alkyl group” are as defined above.
  • the C 1-8 alkyl group which may be substituted with a halogen atom is preferably a C 1-6 alkyl group which may be substituted with a halogen atom, more preferably C which may be substituted with a halogen atom. 1-4 alkyl group.
  • the “C 1-8 alkyloxy group” is an alkyloxy group having an alkyl group having 1 to 8 carbon atoms in the form of a chain, branched or cyclic, or a combination thereof, preferably C 1 A -6 alkyloxy group, more preferably a C1-4 alkyloxy group.
  • Examples of the C 1-8 alkyloxy group include a methoxy group, an ethoxy group, and an isopropoxy group, and a methoxy group is preferable.
  • the upper limit of the number of halogen atoms that may be substituted in the “C 1-8 alkyloxy group optionally substituted with halogen atom” is the number of hydrogen atoms that the alkyl group has, “Halogen atom” and “C 1-8 alkyloxy group” are as defined above.
  • the C 1-8 alkyloxy group which may be substituted with a halogen atom is preferably a C 1-6 alkyloxy group which may be substituted with a halogen atom, more preferably a C 1-6 alkyloxy group which may be substituted with a halogen atom.
  • the “aromatic heterocycle” is an aromatic ring containing 1 to 3 atoms arbitrarily selected from a nitrogen atom, an oxygen atom and a sulfur atom as atoms constituting the ring. .
  • the “5- to 6-membered aromatic heterocycle” means an aromatic ring having 5 or 6 atoms constituting the ring in the above-defined “aromatic heterocycle”. It is. A group derived by removing one hydrogen atom from a “5- to 6-membered aromatic heterocycle” may also be referred to as “5- to 6-membered aromatic heterocycle”.
  • a bicyclic to tricyclic condensed aromatic heterocycle containing at least one nitrogen atom means a condensed fragrance formed by sharing a partial bond between two or three aromatic heterocycles or a benzene ring A fused aromatic heterocycle, wherein at least one ring is an aromatic heterocycle containing one or more nitrogen atoms.
  • An aromatic heterocycle containing one or more nitrogen atoms is, for example, a pyrrole ring.
  • a group derived by removing two hydrogen atoms from “a bicyclic to tricyclic fused aromatic heterocycle containing at least one nitrogen atom” is also referred to as “a bicyclic or tricyclic ring containing at least one nitrogen atom”. It may be referred to as a “fused aromatic heterocycle”.
  • the “2- to 3-cyclic fused pyrrole ring” is a condensed aromatic heterocycle containing a pyrrole ring among the above-mentioned “2- to 3-ring fused aromatic heterocycles containing at least one nitrogen atom”. is there.
  • R 1 is a C 1-8 alkyl group optionally substituted with a halogen atom, preferably a C 1-6 alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, isopropyl Group, cyclopropyl group or t-butyl group.
  • a halogen atom preferably a C 1-6 alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, isopropyl Group, cyclopropyl group or t-butyl group.
  • W is each independently a halogen atom, a cyano group or a C 1-8 alkyl group optionally substituted with a substituent selected from the S group, and the S group consists of a cyano group and a halogen atom.
  • W is bonded to any position of the 3, 4, 5 or 6 position of the benzene ring.
  • n means the number of W bonded, and is an integer of 0 to 4.
  • Preferred n is an integer of 0-2.
  • A is a bicyclic to tricyclic fused aromatic heterocycle containing at least one nitrogen atom, which may be substituted with a substituent selected from the T group, and the T group includes a halogen atom, a halogen atom A C 1-8 alkyl group which may be substituted with and a C 1-8 alkyloxy group which may be substituted with a halogen atom.
  • A is a divalent group, one bonded to the carbonyl carbon, and one bonded to B through a nitrogen atom.
  • A may be indole diyl group, thienopyrrole diyl group, fluropyrrole diyl group, fluoroindole diyl group, methoxyindole diyl group, chlorothienopyrrole diyl group, pyridinopyrrole diyl group, pyrimidinopyrrole diyl group and benzothieno.
  • Examples thereof include a pyrrole diyl group, preferably a group in which a benzene ring or a 5- to 6-membered aromatic heterocycle is condensed at positions 4 and 5 of the pyrrole-1,2-diyl group or an indole-1,7-diyl group. . More preferably, it is as shown below.
  • B is a 5- to 6-membered aromatic heterocycle optionally bonded to a substituent selected from the U group and bonded to the nitrogen atom of A.
  • the U group is substituted with a halogen atom or a halogen atom. It consists of an optionally substituted C 1-8 alkyl group and an optionally substituted C 1-8 alkyloxy group.
  • B includes, for example, pyridyl group, pyrimidinyl group, pyrazinyl group, pyrazolyl group and thiazolyl group, preferably pyridyl group or pyrazinyl group, more preferably 3-chloro-2-pyridyl group or 3-chloro-2 -A pyrazinyl group.
  • a preferred combination of AB is that A is a bicyclic to tricyclic condensed pyrrole ring, and B may be substituted with a substituent selected from the U group, which is bonded to a nitrogen atom of the condensed pyrrole ring. It is a pyrazine ring optionally substituted with a pyridine ring or a substituent selected from the U group.
  • a more preferable combination of AB is shown below.
  • R 1 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group or a t-butyl group; W is 3-methyl-5-chloro, 3-methyl, 3-methyl-5-bromo or 3-methyl-5-cyano or absent AB is The compound which is is mentioned.
  • the compound represented by the formula (I) can be synthesized as follows.
  • an anthranilic acid derivative represented by the formula (II) and a carboxylic acid represented by the formula (III) are condensed in the presence or absence of a base to give a formula (I ) Can be obtained.
  • Reactions include sulfonate chlorides such as mesyl chloride and tosyl chloride, activators such as triphenylphosphine, trimethylboric acid, diethyl phosphate cyanide and hexachlorocyclotriphosphatriazene or dicyclohexylcarbodiimide and 1-ethyl-3- (
  • a carbodiimide-based compound such as 3′-dimethylaminopropyl) carbodiimide hydrochloride can be used.
  • alkali metal hydrides such as sodium hydride
  • carbonates such as potassium carbonate and sodium carbonate
  • alkali metal hydroxides such as potassium hydroxide and sodium hydroxide
  • tertiary amines such as triethylamine
  • unsubstituted or substituted pyridines such as pyridine and 4-dimethylaminopyridine
  • the reaction can be performed without solvent, or using a solvent that does not affect the reaction or a solvent that promotes the target reaction.
  • a solvent for example, amides such as dimethylformamide and dimethylacetamide, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, ethers such as diethyl ether and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, Aromatic hydrocarbons such as benzene, xylene and toluene, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, aliphatic hydrocarbons such as hexane, heptane and octane, dichloromethane, chloroform, chlorobenzene and Dihalogen hydrocarbons such as dichlorobenzene and solvents such as water can be used alone or in combination of
  • the reaction can usually be carried out at ⁇ 80 to 250 ° C., preferably 20 to 50 ° C.
  • the anthranilic acid derivative represented by the formula (II) can be synthesized by the methods described in Patent Literature 1, Patent Literature 2, and Patent Literature 3, and methods similar thereto.
  • the compound represented by the formula (III) hydrolyzes the compound (VI) obtained by reacting the compound represented by the formula (IV) with the compound represented by the formula (V). Can be obtained.
  • R 2 is a C 1-6 alkyl group
  • X is a halogen atom
  • reaction of the compound represented by the formula (IV) and the compound represented by the formula (V) can be performed in the presence or absence of a base.
  • alkali metal hydrides such as sodium hydride
  • carbonates such as potassium carbonate and sodium carbonate
  • alkali metal hydroxides such as potassium hydroxide and sodium hydroxide
  • tertiary amines such as triethylamine
  • unsubstituted or substituted pyridines such as pyridine and 4-dimethylaminopyridine
  • the reaction may be performed in the presence of copper bromide, potassium bromide, zinc bromide, copper iodide, potassium iodide, zinc iodide or the like.
  • the reaction can be performed using no solvent, a solvent that does not affect the reaction, or a solvent that promotes the target reaction.
  • a solvent for example, amides such as dimethylformamide and dimethylacetamide, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, ethers such as diethyl ether and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, Aromatic hydrocarbons such as benzene, xylene and toluene, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, aliphatic hydrocarbons such as hexane, heptane and octane, dichloromethane, chloroform, chlorobenzene and One or a combination of two or more halogen hydrocarbons such as dichlorobenzene and water can be used
  • the reaction can usually be carried out at ⁇ 80 to 250 ° C., preferably 20 to 50 ° C.
  • Hydrolysis of the obtained compound represented by the formula (VI) is usually carried out in the presence of a base.
  • the base used include alkali metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide and sodium ethoxide, Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and organic bases such as triethylamine and 1,8-diazabicyclo [5.4.0] undec-7-ene, preferably sodium methoxide, Sodium ethoxide or sodium hydroxide.
  • alcohols such as methanol and ethanol
  • ethers such as tetrahydrofuran and dioxane
  • solvents such as water can be used singly or in combination.
  • the compound represented by the formula (IV) can be a commercially available compound, or can be obtained by combining known methods using a commercially available compound as a starting material.
  • a of the compound represented by the formula (IV) represents a group in which a benzene ring or a 5- to 6-membered aromatic heterocycle is condensed at the 4- and 5-positions of the 2-pyrrolyl group
  • Journal of Medicinal Chemistry, 47 (25), 6270-6282 can be synthesized according to the method described in 2004 as shown in the following formula.
  • the compound represented by the formula (VII) (wherein A ′ represents a benzene ring or 5- to 6-membered aromatic heterocycle condensed at the 4- and 5-positions of the 2-pyrrolyl group) is added to the compound represented by the formula (VIII)
  • the above compound can be obtained by reacting the azidoacetate represented by the formula (R 2 is as defined above) and cyclizing the resulting compound represented by the formula (IX).
  • the reaction of the compound represented by the formula (VII) and the compound represented by the formula (VIII) is usually performed in the presence of a base.
  • a base for example, an alkali metal hydride such as sodium hydride, an alkali metal alkoxide such as sodium methoxide, Carbonates such as potassium carbonate and sodium carbonate, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tertiary amines such as triethylamine or unsubstituted or substituted groups such as pyridine and 4-dimethylaminopyridine.
  • the pyridine which has can be used.
  • the reaction can be performed without solvent, or using a solvent that does not affect the reaction or a solvent that promotes the target reaction.
  • a solvent for example, amides such as dimethylformamide and dimethylacetamide, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, ethers such as diethyl ether and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, Aromatic hydrocarbons such as benzene, xylene and toluene, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, aliphatic hydrocarbons such as hexane, heptane and octane, dichloromethane, chloroform, chlorobenzene and One kind or a combination of two or more kinds of solvents such as halogen hydrocarbons such as dichlorobenz
  • the reaction can usually be carried out at ⁇ 80 to 250 ° C., preferably in the range of ⁇ 20 to 20 ° C.
  • the compound (IV) can be obtained by heating the compound represented by the chemical formula (IX) in the absence of a solvent, in a solvent that does not affect the reaction, or in a solvent that promotes the target reaction.
  • a solvent for example, high boiling point ethers such as diphenyl ether, aromatic hydrocarbons such as benzene, xylene and toluene, saturated hydrocarbons such as heptane, octane, ligroin and mineral oil, chlorobenzene, bromobenzene and di- Halogen hydrocarbons such as chlorobenzene can be used alone or in combination of two or more.
  • the reaction can usually be carried out at 80 to 250 ° C., preferably in the range of 100 to 200 ° C.
  • Examples of the pests that the pest control agent containing one or more compounds represented by the formula (I) exhibit a controlling effect include agricultural and horticultural pests, animal parasitic pests (animal endoparasites and animal ectoparasites) ), Sanitary pests, unpleasant pests, stored / stored food pests and house pests, preferably horticultural pests or animal ectoparasites.
  • insect species are as follows.
  • Agricultural and horticultural pests include lepidopterous pests (for example, Spodoptera litura, Coleoptera, Acayoto, Aomushi, Konaga, Shirouchimojiyoto, Nikameiga, Kononogaiga, Futobikoga, Sakigaiga, Sinkiga, Azalea, Agrotis s.
  • lepidopterous pests for example, Spodoptera litura, Coleoptera, Acayoto, Aomushi, Konaga, Shirouchimojiyoto, Nikameiga, Kononogaiga, Futobikoga, Sakigaiga, Sinkiga, Azalea, Agrotis s.
  • Hemiptera pests eg, peach aphids, cotton aphids, Aphisfabae, corn aphids, pea aphids, potato aphids, bean aphids, tulip beetles ros hum hum avenae, Methopolophium dirhodum, wheat beetle aphid, barley aphid, radish aphid, fake aphid, snowy aphid, Rosy apple aphid, re Aphids (Aphididae, Adelgidae, Phylloxeridae) such as common aphids, Komikan aphids and citrus aphids, leafhoppers such as leafhoppers and leafhoppers, leafhoppers such as leafhoppers, leafhoppers and leafhoppers, Stink bugs such as blue stink bugs and red be
  • animal parasites ie, animal parasites
  • animal ectoparasites include ticks (eg, ticks (eg, Lone Star ticks, Gulf ticks, ticks, Rocky Mountain ticks, West Coast ticks, American dogs) Ticks, ticks, mites, capesid ticks, manes, mites, western mites, shrews, mites, mites, mites, mites, mites, mites, mites, etc.
  • ticks eg, ticks (eg, Lone Star ticks, Gulf ticks, ticks, Rocky Mountain ticks, West Coast ticks, American dogs) Ticks, ticks, mites, capesid ticks, manes, mites, western mites, shrews, mites, mites, mites, mites, mites, mites, etc.
  • Acne mites and cat dust mites cucumber mites (for example, bovine cucumber mites mites), mites mites (for example, bovine mites mites and dog mites mites), Sao Mites (for example, avian mites), worms, mites (for example, chicken mites and mite mites), tsutsugamushi (for example Miyamatsu tsutsugamushi and tsutsugamushi)), fleas (for example, cat fleas, human fleas, mushrooms) Ops murine and mud mines), lice (eg, dog lice and chicken lice), lice (eg, pig lice, dog lice, louse lice, human lice, white lice and bed bugs), house flies, cow flies, sand flies, fly flies (E.g., sand flies), tsetse flies, abs, aedes (e.
  • Animal endoparasites include nematodes (eg, fecal nematodes, helminths, roundworms (eg, tortuous stomach and murine roundworms), ciliate nematodes, and heterocytics (eg, Pig pneumoniae, Cantonese schistosomiasis and cat lungworm), helminths, caecal worms (eg, chicken roundworm), roundworms (eg anisakis nematode, pig roundworm, horse roundworm, dog roundworm and cat roundworm), Rotating nematodes (e.g., bursula, spiny-mouthed jawworm, cat stomachworm, horoscope stomachworm, largemouth horse stomachworm, chicken stomachworm and medinae), filamentous insects (e.g.
  • nematodes eg, fecal nematodes, helminths, roundworms (eg, tortuous stomach and murine roundworms), ciliate nemato
  • Lymphoid worms rotifers and loar worms
  • nematodes and trichinidae for example, Trichuris and Trichinella
  • flukes for example, Schistosoma japonicum and liver fluke
  • bald worms e.g., Lymphoid worms, rotifers and loar worms
  • flukes for example, Schistosoma japonicum and liver fluke
  • bald worms eg, And crustaceans (eg, suspicious leaves (eg, Manson ciliate) and circles (eg, Coleoptera)) and protozoa .
  • Sanitary pests, unpleasant pests, stored grain pests, stored food pests and house pests include mosquitoes (e.g., human striped mosquitoes and mosquitoes), cockroaches (e.g. black cockroaches, crested cockroaches and German cockroaches), coniferous mites (e.g.
  • Flies eg, house flies, fly flies, butterflies, drosophila and chironomids
  • flyfish phylums
  • hymenopteran insects eg, ants such as the black ant and fire ant, bees such as the giant hornet
  • Arthropods eg, Paramecium, Funabushi and Dangamushi
  • Hemiptera insects eg, bed bugs
  • polypods of arthropods eg, centipedes, geese, and millipedes
  • arachnid arthropods E.g., acididae
  • Coleoptera insects e.g., trash
  • Coleoptera arthropods eg, genus Coleoptera
  • earwig insects eg, Carabidae
  • grasshopper insects eg, Crestedidae
  • Coleoptera insects eg, Azuki weevil, scotch beetle,
  • insect species to which the pest control agent of the present invention is applied are lepidopterous insects, hemiptera pests, thrips pests or animal parasitic fleas and mites, more preferably Lepidoptera, Hemiptera pests, Thripidae pests or ticks.
  • the pest control agent of the present invention can use the compound represented by the formula (I) alone or can be prepared using a carrier according to the method of use.
  • the pest control agent of the present invention is an agricultural and horticultural insecticide
  • it is usually mixed with a suitable solid carrier, liquid carrier, gaseous carrier, surfactant, dispersant and other formulation adjuvants, It is provided in any dosage form such as emulsion, solution, suspension, wettable powder, flowable, powder, granule, tablet, oil, aerosol or smoke.
  • solid carrier examples include talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, and calcium carbonate.
  • liquid carrier examples include alcohols such as methanol, n-hexanol and ethylene glycol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aliphatic hydrocarbons such as n-hexane, kerosene and kerosene, toluene, xylene and methylnaphthalene.
  • alcohols such as methanol, n-hexanol and ethylene glycol
  • ketones such as acetone, methyl ethyl ketone and cyclohexanone
  • aliphatic hydrocarbons such as n-hexane, kerosene and kerosene, toluene, xylene and methylnaphthalene.
  • Aromatic hydrocarbons such as, ethers such as diethyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, soybean oil And vegetable oils such as cottonseed oil, dimethyl sulfoxide and water.
  • examples of the gaseous carrier include liquefied petroleum gas (LPG), air, nitrogen, carbon dioxide gas, and dimethyl ether.
  • Surfactants or dispersants for emulsification, dispersion or spreading include, for example, alkyl sulfates, alkyl (aryl) sulfonates, polyoxyalkylene alkyl (aryl) ethers, polyhydric alcohol esters and Examples include lignin sulfonate.
  • examples of the adjuvant for improving the properties of the preparation include carboxymethyl cellulose, gum arabic, polyethylene glycol and calcium stearate.
  • the above carriers, surfactants, dispersants and adjuvants can be used alone or in combination as required.
  • the content of the compound represented by the formula (I) in the preparation is not particularly limited, but is usually 1 to 75% by weight for the emulsion, 1 to 75% by weight for the liquid, and 0.3% for the powder based on the total amount of the preparation. -25% by weight, wettable powder 1-90% by weight, flowable powder 1-90%, granule 0.5-10% by weight.
  • Compounds of formula (I), formulations containing these, and mixtures of these with other pest control agents include harmful insects, plants, plant propagation materials (eg, seeds, plant foliage, roots) , Germinated plants and young plants), soil, nutrient solution in hydroponic culture, solid medium in hydroponic culture, and rooms that need to prevent the invasion of pests. Applied plants include genetically modified crops. These applications can be made before and after pest infestation.
  • the pest control agent of the present invention is an animal parasite control agent
  • it is a solution, emulsion, liquefied drop (pour-on preparation, spot-on preparation, etc.), spray, foam preparation, tablet, granule, fine granule , Powders, capsules, tablets, chewables, injections, suppositories, creams, shampoos, rinses, resins, smokes, poison baits, etc. , Spot-on formulations, etc.).
  • preparations such as ordinary emulsifiers, dispersants, spreading agents, wetting agents, suspending agents, stabilizers, preservatives, propellants, etc.
  • a supplementary agent can be blended, and a normal film forming agent can be blended.
  • Surfactants for emulsification, dispersion or spreading include, for example, soaps, polyoxyalkylene alkyl (aryl) ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, higher alcohols and alkylaryls Examples include sulfonates.
  • Examples of the dispersant include casein, gelatin, polysaccharides, lignin derivatives, saccharides, and synthetic water-soluble polymers.
  • Examples of the spreading / wetting agent include glycerin and polyethylene glycol.
  • Examples of the suspending agent include casein, gelatin, hydroxypropyl cellulose, and gum arabic.
  • Examples of the stabilizer include phenolic antioxidants (such as butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA)), amine-based antioxidants (such as diphenylamine), and organic sulfur-based antioxidants.
  • Examples of preservatives include methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, and butyl paraoxybenzoate.
  • the above carriers, surfactants, dispersants and adjuvants can be used alone or in combination as required.
  • the liquid agent may further contain a fragrance and a synergist.
  • the content of the compound represented by the formula (I) in the pest control agent of the present invention in the preparation is usually 1 to 75% by weight based on the total amount of the preparation in the liquid preparation.
  • Examples of the carrier used for preparing the cream include non-volatile hydrocarbons (such as liquid paraffin), lanolin-added oils and fats, higher fatty acids, fatty acid esters, animal and vegetable oils, silicone oils and water. Furthermore, an emulsifier, a humectant, an antioxidant, a fragrance, borax, and an ultraviolet absorber can be used alone or in combination as required. Examples of the emulsifier include fatty acid sorbitan, polyoxyethylene alkyl ether, and fatty acid polyoxyethylene.
  • the content of the compound represented by the formula (I) in the pest control agent of the present invention in the preparation is usually 0.5 to 70% by weight based on the total amount of the preparation.
  • the compound of formula (I) is appropriately subdivided and mixed with a diluent or a carrier such as starch, lactose and talc, and further a disintegrant and binder such as magnesium stearate.
  • a diluent or a carrier such as starch, lactose and talc
  • a disintegrant and binder such as magnesium stearate.
  • it can be manufactured by tableting as necessary.
  • Injections must be prepared as sterile solutions.
  • An injection may contain, for example, sufficient salt or glucose to make the solution isotonic with blood.
  • Carriers that can be used to prepare injectables include glycerides, esters such as benzyl benzoate, isopropyl myristate and fatty acid derivatives of propylene glycol, and organic solvents such as N-methylpyrrolidone and glycerol formal.
  • the content of the compound represented by the formula (I) in the pest control agent of the present invention in the preparation is usually 0.01 to 10% by weight based on the total amount of the preparation for injection.
  • the carrier for preparing the resin agent include vinyl chloride polymers and polyurethane.
  • plasticizers such as phthalates, adipic esters and stearic acid can be added to these substrates as carriers.
  • plasticizers such as phthalates, adipic esters and stearic acid can be added to these substrates as carriers.
  • the compound represented by the formula (I) in the substrate After kneading the compound represented by the formula (I) in the substrate, it can be molded by injection molding, extrusion molding, press molding or the like. Furthermore, it can be made into an animal ear tag or an animal insect repellent collar through suitable processes such as molding and cutting.
  • Carriers for poisonous baits include food and attractants (flours such as wheat flour and corn flour, starches such as corn starch and potato starch, sugars such as granulated sugar, maltose and honey, foods such as glycerin, onion flavor and milk flavor Flavors, animal powders such as rice bran powder and fish meal, and various pheromones).
  • the content of the compound represented by formula (I) in the preparation is usually 0.0001 to 90% by weight based on the total amount of the preparation for poisonous baits.
  • the pest control agent of the present invention can be controlled by being administered orally or by injection into the body of an applied animal, and by being administered to all or part of the body surface of the applied animal.
  • pests can be controlled by coating a place where pests are expected to enter, parasite or move with the pest control agent of the present invention.
  • the pest control agent of the present invention may be used as it is, but depending on the case, it can be diluted with water, a liquid carrier, a commercially available shampoo, rinse, bait or a breeding house underlay.
  • the pest control agent according to the present invention can be used by mixing with other fungicides, insecticides, acaricides, herbicides, plant growth regulators and fertilizers.
  • Drugs that can be used in combination are those listed in the Pesticide Manual (issued by The 13th Edition The British Crop Protection Council) and Shibuya Index (SHIBUYA INDEX 13th Edition, 2008, published by SHIBUYA INDEX RESEARCH GROUP). It is done.
  • insecticides, acaricides or nematicides include acephate, dichlorvos, EPN, fenitrothion, fenamifos, prothiofos, profenfos ), Pyraclofos, chlorpyrifos-methyl, diazinon, fosthiazate and imicyafos, organophosphate compounds such as methomyl, thiodicarb, aldicarb ( aldicarb, oxamyl, propoxur, carbaryl, fenobucarb, ethiofencarb, fenothiocarb, pirimicarb, carbofuran and ben Carbamate compounds such as belfuracarb, nereistoxin derivatives such as cartap and thiocyclam, organochlorine compounds such as dicofol and tetradifon, permethrin, tefluthrin ), Cypermethrin, deltamethrin
  • other compounds include buprofezin, hexythiazox, amitraz, chlordimeform, pyridaben, fenpyroxymate, pyrimidifen, tebufenrad, tebufenrad, tebufenrad, tebufenrad ), Fluacrypyrim, acequinocyl, cyflumetofen, flubendiamide, ethiprole, fipronil, etoxazole, imidacloprid, ididacloprid, imidacloprid, imidacloprid thiamethoxam), acetamiprid (acetamiprid), nitenpyram, thiacloprid, dinotefuran, pime Rosin (pymetrozine), bifenazate, spirodiclofen (spirodiclofen), spiromesifen (spiromesifen), flonicamid (flonicamid),
  • the pest control agent of the present invention can be used in combination with or in combination with microbial pesticides such as BT agents and entomopathogenic virus agents.
  • fungicides used in combination or in combination include strobilurins such as azoxystrobin, kresoxym-methyl, trifloxystrobin, metominostrobin and orysastrobin.
  • strobilurins such as azoxystrobin, kresoxym-methyl, trifloxystrobin, metominostrobin and orysastrobin.
  • Compounds, ananilinopyrimidine compounds such as mepanipyrim, pyrimethanil and cyprodinil, triadimefon, bitertanol, triflumizole, metconazole, protoconazole (Propiconazole), penconazole, flusilazole (flusilazole), microbutanil (myclobutanil), cyproconazole, tebuconazole, hexaconazole (h azole compounds such as exaconazole, prochloraz, simeconazole, quinox
  • ethyl carboxylate was isolated. 100 mg (0.33 mmol) of ethyl 1- (3-chloropyridin-2-yl) -1H-indole-2-carboxylate was dissolved in 2 ml of ethanol, 2 ml of 1N sodium hydroxide was added, and the mixture was refluxed for 30 minutes.
  • the compound represented by the formula (I) was synthesized as follows.
  • Formulation Example 1 [Granule] Compound 1 5% by weight Bentonite 40% by weight Talc 10% by weight 43% by weight of clay 2% by weight calcium lignin sulfonate The above components were pulverized and mixed uniformly, kneaded well with water, and granulated and dried to obtain granules.
  • Formulation Example 2 [Granule] Compound 1 2% by weight Sun Extract (trademark) P-252 5% by weight Binder 1.5% by weight Granulation improver 0.5% by weight 91% by weight clay The above components were pulverized and mixed uniformly, kneaded well with water, and granulated and dried to obtain granules.
  • Sun Extract (trademark) P-252 is a product of Nippon Paper Chemicals Co., Ltd., mainly composed of sodium lignin sulfonate.
  • Formulation Example 3 [wettable powder] Compound 3 30% by weight 50% by weight of clay 2% white carbon Diatomaceous earth 13% by weight 4% by weight calcium lignin sulfonate Sodium lauryl sulfate 1% by weight The above ingredients were mixed uniformly and pulverized to obtain a wettable powder.
  • Formulation Example 4 [Granule wettable powder] Compound 3 30% by weight 60% clay Dextrin 5% by weight Alkyl maleic acid copolymer 4% by weight Sodium lauryl sulfate 1% by weight The above components were uniformly pulverized and mixed, water was added and kneaded well, and then granulated and dried to obtain a granular wettable powder.
  • Formulation Example 6 Compound 1 15% by weight N, N-dimethylformamide 20% by weight Solvesso 150 (ExxonMobil Co., Ltd.) 55% by weight 10% by weight of polyoxyethylene alkyl aryl ether The above ingredients were uniformly mixed and dissolved to obtain an emulsion.
  • Formulation Example 7 [powder] Compound 14 2% by weight 60% clay Talc 37% by weight Calcium stearate 1% by weight The said component was mixed uniformly and the powder agent was obtained.
  • Formulation Example 8 [DL powder] Compound 1 2% by weight DL clay 94.5% by weight 2% white carbon Calcium stearate 1% by weight Light liquid paraffin 0.5% by weight The said component was mixed uniformly and the powder agent was obtained.
  • Formulation Example 9 [Fine Granule F ] Compound 3 2% by weight Carrier 94% by weight 2% white carbon Hysol SAS-296 (JX Nippon Oil & Energy) 2% by weight The said component was mixed uniformly and the powder agent was obtained.
  • Formulation Example 12 [Granule] Compound 1 2% by weight Probenazole 24% by weight Binder 3.0% by weight Granulation improver 0.5% by weight Clay 70.5% by weight The above components were pulverized and mixed uniformly, kneaded well with water, and granulated and dried to obtain granules.
  • Test Example 1 Cutout of a leaf disc having a diameter of 5.0 cm from cabbage cultivated in a potter's beak prevention test pot, and a chemical solution of a compound having a predetermined concentration prepared to be 50% acetone water (0.05% Tween 20 (trademark) added). Sprayed. After air drying, the second instar larvae were released. Thereafter, this was left in a thermostatic chamber (16 hours light period-8 hours dark period) at 25 ° C. The insects were observed for life and death 3 days after the release, and the death rate was calculated according to the following formula. The test was conducted by a two-run system.
  • Death rate (%) ⁇ Number of dead insects / (Number of living insects tens of dead insects) ⁇ ⁇ 100
  • the compounds 1, 2, 3, 4, 5, 6, 7, 8, 26 and 28 showed insecticidal activity with a mortality rate of 80% or more after 100 ppm of foliage treatment.
  • compounds 1,3,4,5,6,7,8,9,10,18,19,20,22,23,24 and 26 show insecticidal activity with a death rate of 80% or more. It was.
  • With 1 ppm foliar treatment compounds 1, 4, 5, 6, 7, 8, 11, 12, 13, 14, 15, 16, 18, 19, 22, 23, 24, and 28 have a death rate of 80% or more. Insecticidal activity was demonstrated.
  • Test Example 2 A cut-out leaf disc having a diameter of 5.0 cm was cut out from a cabbage grown in a pot- spotted carp control pot, and a chemical solution of a compound having a predetermined concentration prepared so as to be 50% acetone water (added with 0.05% Tween 20 (trademark)). Sprayed. After air-drying, the third-instar larvae of Spodoptera litura were released. Thereafter, this was left in a thermostatic chamber (16 hours light period-8 hours dark period) at 25 ° C. The insects were observed for life and death 3 days after the release, and the death rate was calculated according to the following formula. The test was conducted by a two-run system.
  • Death rate (%) ⁇ Number of dead insects / (Number of living insects tens of dead insects) ⁇ ⁇ 100
  • the compounds 1,3,4,5,6,7,8,25,26 and 28 showed insecticidal activity with a mortality rate of 80% or more after 100 ppm of foliage treatment.
  • Insecticidal activity of compounds 1,3,4,5,6,7,8,9,10,18,19,20,21,22,23,23, and 26 with a death rate of 80% or more by treatment with 10 ppm of foliage showed that.
  • Compound 1,3,4,5,6,7,8,9,11,12,14,16,18,19,20,22,23,24 and 28 were killed by 1 ppm of foliage at 80% death rate The above insecticidal activity was exhibited.
  • Test Example 3 Cotton Aphid Control Test A leaf disc having a diameter of 2.0 cm was cut out from a cucumber cultivated in a pot, and 50% acetone water (0.05% Tween 20 (trademark) added) was added to this. The chemical solution was sprayed. After air drying, cotton aphid first instar larvae were released. Thereafter, this was left in a thermostatic chamber (16 hours light period-8 hours dark period) at 25 ° C. The insects were observed for life and death 3 days after the release, and the death rate was calculated according to the following formula. The test was conducted by a two-run system.
  • Death rate (%) ⁇ Number of dead insects / (Number of living insects tens of dead insects) ⁇ ⁇ 100
  • the compounds 1, 5, 6, 7, 8, 11, 12, 13, 14, 15, 16, 18, and 28 showed insecticidal activity with a mortality rate of 80% or more after treatment with 500 ppm of foliage.
  • Compounds 1, 5, 6, 7, 8, 11, 12, 13, 14, 19, 20, and 28 showed insecticidal activity with a mortality rate of 80% or more after 100 ppm foliage treatment.
  • Compounds 5, 6, 7, 8, 9, 12, 14, 19, 20, 22, 24, and 28 showed insecticidal activity with a mortality rate of 80% or more after treatment with 20 ppm of foliage.
  • Citrus thrips control test A leaf disk with a diameter of 2.8 cm was cut out from green beans grown in pots, and 50% acetone water (0.05% Tween20 (trademark) added) was added to this compound. The chemical solution was sprayed. After air drying, the first instar larvae of Citrus thrips were released. Thereafter, this was left in a thermostatic chamber (16 hours light period-8 hours dark period) at 25 ° C. The insects were observed for life and death 3 days after the release, and the death rate was calculated according to the following formula. The test was conducted by a two-run system.
  • Death rate (%) ⁇ Number of dead insects / (Number of living insects tens of dead insects) ⁇ ⁇ 100
  • the compounds 1, 5, 6, 8, 11, 12, 13, 14, 15, and 22 exhibited insecticidal activity with a mortality rate of 80% or more after treatment with 500 ppm of foliage.
  • Compounds 6, 7, 19 and 28 showed insecticidal activity with a mortality rate of 80% or more after 100 ppm foliage treatment.
  • Test Example 5 1 ⁇ L of a chemical solution of a compound prepared at a predetermined concentration with acetone was treated on the back of a female housefly of a housefly kept in a housefly control test room. After the chemical treatment, adults were transferred to plastic cups so that there were 5 per cup, and left in a constant temperature room (16 hours light period-8 hours dark period) at 25 ° C. After 24 hours of treatment, the state of agony of adults was observed, and the rate of agony was calculated according to the following formula. The test was conducted by a two-run system.
  • Rate of bitter worms (%) ⁇ number of bitter worms / (number of normal worms + number of bitter worms) ⁇ ⁇ 100
  • the compounds 6, 9, 10, 19, 22, and 23 showed a high insecticidal effect with an morbidity rate of 80% or more at a treatment amount of 2 ⁇ g of compound per head.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • Tropical Medicine & Parasitology (AREA)
  • Public Health (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

A compound represented by formula (I) has an excellent noxious organism control activity. [R1 represents a C1-8 alkyl group or the like; W represents a halogen atom or the like; n represents an integer of 0 to 4; A represents a bicycic to tricyclic condensed aromatic hetero ring containing at least one nitrogen atom, or the like; and B represents a 5- to 6-membered aromatic hetero ring which is bound to a nitrogen atom in A.]

Description

アントラニル酸誘導体および有害生物防除剤Anthranilic acid derivatives and pest control agents
　本発明は、アントラニル酸誘導体およびそれを含む有害生物防除剤に関するものである。より具体的には、本発明は、２～３環性の縮合芳香族ヘテロ環を有するアントラニル酸誘導体およびそれを含む有害生物防除剤に関するものである。 The present invention relates to an anthranilic acid derivative and a pest control agent containing the same. More specifically, the present invention relates to an anthranilic acid derivative having a bicyclic to tricyclic fused aromatic heterocycle and a pesticidal agent containing the same.
　これまでに多くの有害生物防除剤が見いだされてきているが、薬剤感受性の低下、効果の持続性、使用時の安全性などの問題点があることから、今なお新規の薬剤が求められている。 Many pesticides have been found so far, but there are still problems such as reduced drug sensitivity, sustained efficacy, and safety during use. Yes.
　特許文献１および２は、アントラニル酸系有害生物防除剤を、特許文献３は、その製造方法を開示するが、有害生物防除活性を示す、縮合芳香族ヘテロ環を有するアントラニル酸誘導体の具体的な記載はない。 Patent Documents 1 and 2 disclose anthranilic acid-based pest control agents, and Patent Document 3 discloses a production method thereof. Specific examples of anthranilic acid derivatives having a condensed aromatic heterocycle exhibiting pesticidal activity are disclosed. There is no description.
国際公開第２００３／０２６４１５号International Publication No. 2003/026415 国際公開第２００１／０７０６７１号International Publication No. 2001/070671 国際公開第２００６／０６２９７８号International Publication No. 2006/062978
　本発明は、有害生物防除活性を示す新規な化合物を提供することを課題とする。 An object of the present invention is to provide a novel compound exhibiting pest control activity.
　上記課題を解決すべく鋭意検討を行った結果、本発明者らは、式（Ｉ）で示される化合物が、優れた有害生物防除活性を示すことを見出した。
Figure JPOXMLDOC01-appb-C000002
 ［式中、
　Ｒ１は、ハロゲン原子で置換されていてもよいＣ１－８アルキル基を示し、
　Ｗは、それぞれ独立して、ハロゲン原子、シアノ基またはＳ群から選択される置換基で置換されていてもよいＣ１－８アルキル基を示し、
　ｎは、０～４の整数を示し、
　Ａは、Ｔ群から選択される置換基で置換されていてもよい、少なくとも１つの窒素原子を含有する２～３環性の縮合芳香族ヘテロ環を示し、
　Ｂは、Ａの窒素原子に結合する、Ｕ群から選択される置換基で置換されていてもよい５～６員の芳香族ヘテロ環を示し、
　Ｓ群は、シアノ基およびハロゲン原子からなり、
　Ｔ群は、ハロゲン原子、ハロゲン原子で置換されていてもよいＣ１－８アルキル基およびハロゲン原子で置換されていてもよいＣ１－８アルキルオキシ基からなり、
　Ｕ群は、ハロゲン原子、ハロゲン原子で置換されていてもよいＣ１－８アルキル基およびハロゲン原子で置換されていてもよいＣ１－８アルキルオキシ基からなる。］ As a result of intensive studies to solve the above problems, the present inventors have found that the compound represented by the formula (I) exhibits excellent pest control activity.
Figure JPOXMLDOC01-appb-C000002
 [Where:
R 1 represents a C 1-8 alkyl group which may be substituted with a halogen atom,
W each independently represents a halogen atom, a cyano group or a C 1-8 alkyl group which may be substituted with a substituent selected from the group S;
n represents an integer of 0 to 4,
A represents a bicyclic to tricyclic fused aromatic heterocycle containing at least one nitrogen atom, which may be substituted with a substituent selected from Group T;
B represents a 5- to 6-membered aromatic heterocycle optionally substituted with a substituent selected from Group U, which is bonded to the nitrogen atom of A;
S group consists of a cyano group and a halogen atom,
T group consists halogen atom, optionally substituted C 1-8 alkyl group and optionally C 1-8 alkyl group optionally substituted by a halogen atom with a halogen atom,
U group, a halogen atom, optionally substituted C 1-8 alkyl group and optionally C 1-8 alkyl group optionally substituted by a halogen atom with a halogen atom. ]
　すなわち、本発明は、以下の［１］～［５］を提供する。
［１］式（Ｉ）で示される化合物。
［２］式（Ｉ）で示される化合物を１種以上含む有害生物防除剤。
［３］有害生物防除に使用するための、式（Ｉ）で示される化合物。
［４］有害生物防除剤を製造するための、式（Ｉ）で示される化合物の使用。
［５］式（Ｉ）で示される化合物を有害生物に接触させることを含む、有害生物の防除方法。 That is, the present invention provides the following [1] to [5].
[1] A compound represented by the formula (I).
[2] A pest control agent comprising one or more compounds represented by the formula (I).
[3] A compound represented by formula (I) for use in pest control.
[4] Use of a compound represented by the formula (I) for producing a pest control agent.
[5] A method for controlling pests, comprising bringing the compound represented by formula (I) into contact with pests.
　式（Ｉ）で示される化合物は、Ａが２～３環性の縮合ピロール環であり、Ｂが該縮合ピロール環の窒素原子に結合する、Ｕ群から選択される置換基で置換されていてもよいピリジン環またはＵ群から選択される置換基で置換されていてもよいピラジン環である化合物であることが好ましい。 In the compound represented by the formula (I), A is a bicyclic to tricyclic fused pyrrole ring, and B is substituted with a substituent selected from the U group, which is bonded to a nitrogen atom of the fused pyrrole ring. The compound is preferably a pyridine ring or a pyrazine ring optionally substituted with a substituent selected from Group U.
　防除する有害生物は、農園芸上の害虫または動物寄生性害虫であることが好ましい。すなわち、有害生物防除剤は、農園芸用殺虫剤または動物寄生虫防除剤であることが好ましい。 The pests to be controlled are preferably agricultural or horticultural pests or animal parasitic pests. That is, the pest control agent is preferably an agricultural or horticultural insecticide or an animal parasite control agent.
　本発明に係る化合物は、優れた有害生物防除活性を示す。また、本発明に係る化合物は、薬剤感受性が低下し難く、効果の持続性も高く、使用時の安全性も高い。 The compound according to the present invention exhibits excellent pest control activity. In addition, the compound according to the present invention is difficult to decrease drug sensitivity, has a high sustained effect, and has high safety during use.
　以下に、本明細書において記載する記号および用語の定義ならびに本発明の実施の形態などを示して、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to definitions of symbols and terms described in the present specification and embodiments of the present invention.
　本明細書において、「ハロゲン原子」とは、フッ素原子、塩素原子、臭素原子またはヨウ素原子であり、好ましくは塩素原子または臭素原子である。 In the present specification, the “halogen atom” is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom.
　本明細書において、「Ｃ１－８アルキル基」とは、鎖状、分岐状もしくは環状またはそれらの組合せの炭素数１～８のアルキル基であり、好ましくは、炭素数１～６のアルキル基であるＣ１－６アルキル基であり、より好ましくは炭素数１～４のアルキル基であるＣ１－４アルキル基である。Ｃ１－８アルキル基として、例えばメチル基、エチル基、ｎ－プロピル基、イソプロピル基、シクロプロピル基、ｎ－ブチル基、ｎ－ペンチル基、シクロペンチル基、ｎ－ヘキシル基およびシクロヘキシル基が挙げられ、好ましくは、メチル基、エチル基、ｎ－プロピル基、イソプロピル基またはシクロプロピル基であり、より好ましくはメチル基またはイソプロピル基である。 In the present specification, the “C 1-8 alkyl group” is a chain, branched or cyclic alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. a C 1-6 alkyl group is more preferably a C 1-4 alkyl group which is an alkyl group having 1 to 4 carbon atoms. Examples of the C 1-8 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group. Preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a cyclopropyl group, and more preferably a methyl group or an isopropyl group.
　本明細書において、「ハロゲン原子で置換されていてもよいＣ１－８アルキル基」における、置換されていてもよいハロゲン原子の数の上限はアルキル基が有する水素原子の数であり、「ハロゲン原子」および「Ｃ１－８アルキル基」は前記定義のとおりである。ハロゲン原子で置換されていてもよいＣ１－８アルキル基は、好ましくはハロゲン原子で置換されていてもよいＣ１－６アルキル基であり、より好ましくはハロゲン原子で置換されていてもよいＣ１－４アルキル基である。 In this specification, the upper limit of the number of halogen atoms that may be substituted in the “C 1-8 alkyl group optionally substituted with halogen atom” is the number of hydrogen atoms that the alkyl group has, “Atom” and “C 1-8 alkyl group” are as defined above. The C 1-8 alkyl group which may be substituted with a halogen atom is preferably a C 1-6 alkyl group which may be substituted with a halogen atom, more preferably C which may be substituted with a halogen atom. 1-4 alkyl group.
　本明細書において、「Ｃ１－８アルキルオキシ基」とは、鎖状、分岐状もしくは環状またはそれらの組合せの炭素数１～８のアルキル基を有するアルキルオキシ基であり、好ましくは、Ｃ１－６アルキルオキシ基であり、より好ましくはＣ１－４アルキルオキシ基である。Ｃ１－８アルキルオキシ基として、例えば、メトキシ基、エトキシ基およびイソプロポキシ基が挙げられ、好ましくはメトキシ基である。 In the present specification, the “C 1-8 alkyloxy group” is an alkyloxy group having an alkyl group having 1 to 8 carbon atoms in the form of a chain, branched or cyclic, or a combination thereof, preferably C 1 A -6 alkyloxy group, more preferably a C1-4 alkyloxy group. Examples of the C 1-8 alkyloxy group include a methoxy group, an ethoxy group, and an isopropoxy group, and a methoxy group is preferable.
　本明細書において、「ハロゲン原子で置換されていてもよいＣ１－８アルキルオキシ基」における、置換されていてもよいハロゲン原子の数の上限はアルキル基が有する水素原子の数であり、「ハロゲン原子」および「Ｃ１－８アルキルオキシ基」は前記定義のとおりである。ハロゲン原子で置換されていてもよいＣ１－８アルキルオキシ基は、好ましくはハロゲン原子で置換されていてもよいＣ１－６アルキルオキシ基であり、より好ましくはハロゲン原子で置換されていてもよいＣ１－４アルキルオキシ基である。 In the present specification, the upper limit of the number of halogen atoms that may be substituted in the “C 1-8 alkyloxy group optionally substituted with halogen atom” is the number of hydrogen atoms that the alkyl group has, “Halogen atom” and “C 1-8 alkyloxy group” are as defined above. The C 1-8 alkyloxy group which may be substituted with a halogen atom is preferably a C 1-6 alkyloxy group which may be substituted with a halogen atom, more preferably a C 1-6 alkyloxy group which may be substituted with a halogen atom. Good C 1-4 alkyloxy group.
　本明細書において、「芳香族へテロ環」とは、窒素原子、酸素原子および硫黄原子から任意に選ばれた１～３個の原子を、環を構成する原子として含む芳香族の環である。 In the present specification, the “aromatic heterocycle” is an aromatic ring containing 1 to 3 atoms arbitrarily selected from a nitrogen atom, an oxygen atom and a sulfur atom as atoms constituting the ring. .
　本明細書において、「５～６員の芳香族へテロ環」とは、前記定義の「芳香族へテロ環」のうち、環を構成する原子の数が５または６である芳香族の環である。「５～６員の芳香族へテロ環」から１個の水素原子を除いて誘導される基も「５～６員の芳香族へテロ環」と記す場合がある。 In the present specification, the “5- to 6-membered aromatic heterocycle” means an aromatic ring having 5 or 6 atoms constituting the ring in the above-defined “aromatic heterocycle”. It is. A group derived by removing one hydrogen atom from a “5- to 6-membered aromatic heterocycle” may also be referred to as “5- to 6-membered aromatic heterocycle”.
　「少なくとも１つの窒素原子を含有する２～３環性の縮合芳香族ヘテロ環」とは、２～３環の芳香族ヘテロ環またはベンゼン環が一部の結合を共有して形成される縮合芳香族ヘテロ環であって、少なくとも１つの環は窒素原子を１つ以上含有する芳香族へテロ環である、縮合芳香族ヘテロ環である。窒素原子を１つ以上含有する芳香族へテロ環は、例えばピロール環である。「少なくとも１つの窒素原子を含有する２～３環性の縮合芳香族ヘテロ環」から２個の水素原子を除いて誘導される基も「少なくとも１つの窒素原子を含有する２～３環性の縮合芳香族ヘテロ環」と記す場合がある。「２～３環性の縮合ピロール環」とは、上記「少なくとも１つの窒素原子を含有する２～３環性の縮合芳香族ヘテロ環」のうち、ピロール環を含む縮合芳香族へテロ環である。 “A bicyclic to tricyclic condensed aromatic heterocycle containing at least one nitrogen atom” means a condensed fragrance formed by sharing a partial bond between two or three aromatic heterocycles or a benzene ring A fused aromatic heterocycle, wherein at least one ring is an aromatic heterocycle containing one or more nitrogen atoms. An aromatic heterocycle containing one or more nitrogen atoms is, for example, a pyrrole ring. A group derived by removing two hydrogen atoms from “a bicyclic to tricyclic fused aromatic heterocycle containing at least one nitrogen atom” is also referred to as “a bicyclic or tricyclic ring containing at least one nitrogen atom”. It may be referred to as a “fused aromatic heterocycle”. The “2- to 3-cyclic fused pyrrole ring” is a condensed aromatic heterocycle containing a pyrrole ring among the above-mentioned “2- to 3-ring fused aromatic heterocycles containing at least one nitrogen atom”. is there.
　以下、式（Ｉ）で示される各記号の定義および好ましい態様について説明する。 Hereinafter, the definition and preferred embodiments of each symbol represented by the formula (I) will be described.
　Ｒ１は、ハロゲン原子で置換されていてもよいＣ１－８アルキル基であり、好ましくは、Ｃ１－６アルキル基であり、より好ましくは、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、シクロプロピル基またはｔ－ブチル基である。 R 1 is a C 1-8 alkyl group optionally substituted with a halogen atom, preferably a C 1-6 alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, isopropyl Group, cyclopropyl group or t-butyl group.
　Ｗは、それぞれ独立して、ハロゲン原子、シアノ基またはＳ群から選択される置換基で置換されていてもよいＣ１－８アルキル基であり、Ｓ群は、シアノ基およびハロゲン原子からなる。Ｗは、ベンゼン環の３、４、５または６位のいずれかの位置に結合する。ｎはＷが結合する数を意味しており、０～４の整数である。好ましいｎは、０～２の整数である。好ましいＷは、塩素原子、臭素原子、シアノ基またはメチル基である。より好ましいＷは、３－メチル、５－クロロ、５－ブロモまたは５－シアノである。また、ｎ＝０すなわちＷが存在しない態様も好ましい。 W is each independently a halogen atom, a cyano group or a C 1-8 alkyl group optionally substituted with a substituent selected from the S group, and the S group consists of a cyano group and a halogen atom. W is bonded to any position of the 3, 4, 5 or 6 position of the benzene ring. n means the number of W bonded, and is an integer of 0 to 4. Preferred n is an integer of 0-2. Preferred W is a chlorine atom, a bromine atom, a cyano group or a methyl group. More preferred W is 3-methyl, 5-chloro, 5-bromo or 5-cyano. Also preferred is an embodiment in which n = 0, that is, W does not exist.
　Ａは、Ｔ群から選択される置換基で置換されていてもよい、少なくとも１つの窒素原子を含有する２～３環性の縮合芳香族ヘテロ環であり、Ｔ群は、ハロゲン原子、ハロゲン原子で置換されていてもよいＣ１－８アルキル基およびハロゲン原子で置換されていてもよいＣ１－８アルキルオキシ基からなる。Ａは、２価の基であり、１つはカルボニル炭素に結合しており、１つは窒素原子によりＢに結合している。例えば、Ａは、インドールジイル基、チエノピロールジイル基、フロピロールジイル基、フルオロインドールジイル基、メトキシインドールジイル基、クロロチエノピロールジイル基、ピリジノピロールジイル基、ピリミジノピロールジイル基およびベンゾチエノピロールジイル基が挙げられ、好ましくはピロール－１，２－ジイル基の４、５位にベンゼン環または５～６員の芳香族ヘテロ環が縮合した基またはインドール－１，７－ジイル基である。より好ましくは、次に示すとおりである。
Figure JPOXMLDOC01-appb-C000003
 A is a bicyclic to tricyclic fused aromatic heterocycle containing at least one nitrogen atom, which may be substituted with a substituent selected from the T group, and the T group includes a halogen atom, a halogen atom A C 1-8 alkyl group which may be substituted with and a C 1-8 alkyloxy group which may be substituted with a halogen atom. A is a divalent group, one bonded to the carbonyl carbon, and one bonded to B through a nitrogen atom. For example, A may be indole diyl group, thienopyrrole diyl group, fluropyrrole diyl group, fluoroindole diyl group, methoxyindole diyl group, chlorothienopyrrole diyl group, pyridinopyrrole diyl group, pyrimidinopyrrole diyl group and benzothieno. Examples thereof include a pyrrole diyl group, preferably a group in which a benzene ring or a 5- to 6-membered aromatic heterocycle is condensed at positions 4 and 5 of the pyrrole-1,2-diyl group or an indole-1,7-diyl group. . More preferably, it is as shown below.
Figure JPOXMLDOC01-appb-C000003
　Ｂは、Ａの窒素原子に結合する、Ｕ群から選択される置換基で置換されていてもよい５～６員の芳香族ヘテロ環であり、Ｕ群は、ハロゲン原子、ハロゲン原子で置換されていてもよいＣ１－８アルキル基およびハロゲン原子で置換されていてもよいＣ１－８アルキルオキシ基からなる。Ｂは、例えば、ピリジル基、ピリミジニル基、ピラジニル基、ピラゾリル基およびチアゾリル基が挙げられ、好ましくはピリジル基またはピラジニル基であり、より好ましくは３－クロロ－２－ピリジル基または３－クロロ－２－ピラジニル基である。 B is a 5- to 6-membered aromatic heterocycle optionally bonded to a substituent selected from the U group and bonded to the nitrogen atom of A. The U group is substituted with a halogen atom or a halogen atom. It consists of an optionally substituted C 1-8 alkyl group and an optionally substituted C 1-8 alkyloxy group. B includes, for example, pyridyl group, pyrimidinyl group, pyrazinyl group, pyrazolyl group and thiazolyl group, preferably pyridyl group or pyrazinyl group, more preferably 3-chloro-2-pyridyl group or 3-chloro-2 -A pyrazinyl group.
　Ａ－Ｂの好ましい組み合わせは、Ａが２～３環性の縮合ピロール環であり、Ｂが該縮合ピロール環の窒素原子に結合する、Ｕ群から選択される置換基で置換されていてもよいピリジン環またはＵ群から選択される置換基で置換されていてもよいピラジン環である。Ａ－Ｂのより好ましい組み合わせの態様を以下に示す。
Figure JPOXMLDOC01-appb-C000004
 A preferred combination of AB is that A is a bicyclic to tricyclic condensed pyrrole ring, and B may be substituted with a substituent selected from the U group, which is bonded to a nitrogen atom of the condensed pyrrole ring. It is a pyrazine ring optionally substituted with a pyridine ring or a substituent selected from the U group. A more preferable combination of AB is shown below.
Figure JPOXMLDOC01-appb-C000004
　式（Ｉ）で示される化合物の好ましい態様として、
　Ｒ１は、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、シクロプロピル基またはｔ－ブチル基であり、
　Ｗは、３－メチル－５－クロロ、３－メチル、３－メチル－５－ブロモもしくは３－メチル－５－シアノであるか、または存在せず、
　Ａ－Ｂは、
Figure JPOXMLDOC01-appb-C000005
 である化合物が挙げられる。 As a preferred embodiment of the compound represented by the formula (I),
R 1 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group or a t-butyl group;
W is 3-methyl-5-chloro, 3-methyl, 3-methyl-5-bromo or 3-methyl-5-cyano or absent
AB is
Figure JPOXMLDOC01-appb-C000005
 The compound which is is mentioned.
　式（Ｉ）で示される化合物の具体的な例を表１に記す。
Figure JPOXMLDOC01-appb-T000006
 Specific examples of the compound represented by the formula (I) are shown in Table 1.
Figure JPOXMLDOC01-appb-T000006
　式（Ｉ）で示される化合物は以下のように合成することができる。 The compound represented by the formula (I) can be synthesized as follows.
　すなわち以下の反応式で示されるように、式（ＩＩ）で示されるアントラニル酸誘導体と、式（ＩＩＩ）で示されるカルボン酸を、塩基存在下または非存在下、縮合させることにより、式（Ｉ）で示される化合物を得ることができる。
Figure JPOXMLDOC01-appb-C000007
 That is, as shown in the following reaction formula, an anthranilic acid derivative represented by the formula (II) and a carboxylic acid represented by the formula (III) are condensed in the presence or absence of a base to give a formula (I ) Can be obtained.
Figure JPOXMLDOC01-appb-C000007
　反応には、メシルクロリドおよびトシルクロリドなどのスルホン酸クロリド、トリフェニルホスフィン、トリメチルホウ酸、ジエチルリン酸シアニドおよびヘキサクロロシクロトリホスファトリアゼンなどの活性化剤またはジシクロヘキシルカルボジイミドおよび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などのカルボジイミド系化合物などを用いることができる。 Reactions include sulfonate chlorides such as mesyl chloride and tosyl chloride, activators such as triphenylphosphine, trimethylboric acid, diethyl phosphate cyanide and hexachlorocyclotriphosphatriazene or dicyclohexylcarbodiimide and 1-ethyl-3- ( A carbodiimide-based compound such as 3′-dimethylaminopropyl) carbodiimide hydrochloride can be used.
　塩基を使用する場合、例えば、水素化ナトリウムなどのアルカリ金属水素化物、炭酸カリウムおよび炭酸ナトリウムなどの炭酸塩、水酸化カリウムおよび水酸化ナトリウムなどのアルカリ金属水酸化物、トリエチルアミンなどの第３級アミン類またはピリジンおよび４－ジメチルアミノピリジンなどの無置換のもしくは置換基を有するピリジン類を用いることができる。 When a base is used, for example, alkali metal hydrides such as sodium hydride, carbonates such as potassium carbonate and sodium carbonate, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tertiary amines such as triethylamine Or unsubstituted or substituted pyridines such as pyridine and 4-dimethylaminopyridine can be used.
　反応は、無溶媒で、または反応に影響しない溶媒もしくは目的反応を促進させる溶媒を用いて行うことができる。溶媒を用いる場合は、例えば、ジメチルホルムアミドおよびジメチルアセトアミドなどのアミド類、アセトニトリルなどのニトリル類、ジメチルスルホキシドなどのスルホキシド類、ジエチルエーテルおよびテトラヒドロフランなどのエーテル類、酢酸エチルおよび酢酸ブチルなどのエステル類、ベンゼン、キシレンおよびトルエンなどの芳香族炭化水素類、メタノール、エタノールおよびプロパノールなどのアルコール類、アセトンおよびメチルエチルケトンなどのケトン類、ヘキサン、ヘプタンおよびオクタンなどの脂肪族炭化水素類、ジクロロメタン、クロロホルム、クロロベンゼンおよびジクロロベンゼンなどのハロゲン炭化水素類ならびに水などの溶媒を１種類または２種類以上組み合わせて用いることができ、ジメチルホルムアミド、アセトニトリル、エーテル類、ジクロロメタンまたはクロロホルムなどを用いることが好ましい。 The reaction can be performed without solvent, or using a solvent that does not affect the reaction or a solvent that promotes the target reaction. When using a solvent, for example, amides such as dimethylformamide and dimethylacetamide, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, ethers such as diethyl ether and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, Aromatic hydrocarbons such as benzene, xylene and toluene, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, aliphatic hydrocarbons such as hexane, heptane and octane, dichloromethane, chloroform, chlorobenzene and Dihalogen hydrocarbons such as dichlorobenzene and solvents such as water can be used alone or in combination of two or more. De, acetonitrile, ethers, it is preferable to use such as dichloromethane or chloroform.
　反応は、通常－８０～２５０℃で行うことができ、２０～５０℃の範囲で行うことが好ましい。 The reaction can usually be carried out at −80 to 250 ° C., preferably 20 to 50 ° C.
　式（ＩＩ）で示されるアントラニル酸誘導体は、特許文献１、特許文献２および特許文献３に記載の方法ならびにそれらと類似の方法で合成することができる。 The anthranilic acid derivative represented by the formula (II) can be synthesized by the methods described in Patent Literature 1, Patent Literature 2, and Patent Literature 3, and methods similar thereto.
　式（ＩＩＩ）で示される化合物は、次反応式に示すように、式（ＩＶ）で示される化合物と、式（Ｖ）で示される化合物を反応させることによって得られる化合物（ＶＩ）を加水分解することによって得ることができる。
Figure JPOXMLDOC01-appb-C000008
 As shown in the following reaction formula, the compound represented by the formula (III) hydrolyzes the compound (VI) obtained by reacting the compound represented by the formula (IV) with the compound represented by the formula (V). Can be obtained.
Figure JPOXMLDOC01-appb-C000008
　ここで、Ｒ２はＣ１－６のアルキル基であり、Ｘはハロゲン原子である。 Here, R 2 is a C 1-6 alkyl group, and X is a halogen atom.
　式（ＩＶ）で示される化合物と、式（Ｖ）で示される化合物の反応は、塩基存在下または非存在下で行うことができる。 The reaction of the compound represented by the formula (IV) and the compound represented by the formula (V) can be performed in the presence or absence of a base.
　塩基を使用する場合、例えば、水素化ナトリウムなどのアルカリ金属水素化物、炭酸カリウムおよび炭酸ナトリウムなどの炭酸塩、水酸化カリウムおよび水酸化ナトリウムなどのアルカリ金属水酸化物、トリエチルアミンなどの第３級アミン類またはピリジンおよび４－ジメチルアミノピリジンなどの無置換のまたは置換基を有するピリジン類を用いることができる。 When a base is used, for example, alkali metal hydrides such as sodium hydride, carbonates such as potassium carbonate and sodium carbonate, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tertiary amines such as triethylamine Or unsubstituted or substituted pyridines such as pyridine and 4-dimethylaminopyridine can be used.
　また、反応は、臭化銅、臭化カリウム、臭化亜鉛、ヨウ化銅、ヨウ化カリウムまたはヨウ化亜鉛などの存在下で行ってもよい。 The reaction may be performed in the presence of copper bromide, potassium bromide, zinc bromide, copper iodide, potassium iodide, zinc iodide or the like.
　反応は、無溶媒もしくは反応に影響しない溶媒もしくは目的反応を促進させる溶媒を用いて行うことができる。溶媒を用いる場合は、例えば、ジメチルホルムアミドおよびジメチルアセトアミドなどのアミド類、アセトニトリルなどのニトリル類、ジメチルスルホキシドなどのスルホキシド類、ジエチルエーテルおよびテトラヒドロフランなどのエーテル類、酢酸エチルおよび酢酸ブチルなどのエステル類、ベンゼン、キシレンおよびトルエンなどの芳香族炭化水素類、メタノール、エタノールおよびプロパノールなどのアルコール類、アセトンおよびメチルエチルケトンなどのケトン類、ヘキサン、ヘプタンおよびオクタンなどの脂肪族炭化水素類、ジクロロメタン、クロロホルム、クロロベンゼンおよびジクロロベンゼンなどのハロゲン炭化水素類ならびに水などの溶媒を１種類または２種類以上組み合わせて用いることができるが、ジメチルホルムアミド、アセトニトリル、エーテル類、ジクロロメタンまたはクロロホルムなどを用いることが好ましい。 The reaction can be performed using no solvent, a solvent that does not affect the reaction, or a solvent that promotes the target reaction. When using a solvent, for example, amides such as dimethylformamide and dimethylacetamide, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, ethers such as diethyl ether and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, Aromatic hydrocarbons such as benzene, xylene and toluene, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, aliphatic hydrocarbons such as hexane, heptane and octane, dichloromethane, chloroform, chlorobenzene and One or a combination of two or more halogen hydrocarbons such as dichlorobenzene and water can be used. Amides, acetonitrile, ethers, it is preferable to use such as dichloromethane or chloroform.
　反応は、通常－８０～２５０℃で行うことができ、２０～５０℃の範囲で行うことが好ましい。 The reaction can usually be carried out at −80 to 250 ° C., preferably 20 to 50 ° C.
　得られた式（ＶＩ）で示される化合物の加水分解は、通常塩基存在下で行い、使用する塩基としては、ナトリウムメトキシド、カリウムメトキシド、リチウムメトキシドおよびナトリウムエトキシドなどのアルカリ金属アルコキシド、水酸化ナトリウムおよび水酸化カリウムなどのアルカリ金属水酸化物ならびにトリエチルアミンおよび１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エンなどの有機塩基などが挙げられ、好ましくは、ナトリウムメトキシド、ナトリウムエトキシドまたは水酸化ナトリウムである。使用する溶媒としては、メタノールおよびエタノールなどのアルコール、テトラヒドロフランおよびジオキサンなどのエーテル類ならびに水などの溶媒を１種類または２種類以上組み合わせて用いることができる。 Hydrolysis of the obtained compound represented by the formula (VI) is usually carried out in the presence of a base. Examples of the base used include alkali metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide and sodium ethoxide, Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and organic bases such as triethylamine and 1,8-diazabicyclo [5.4.0] undec-7-ene, preferably sodium methoxide, Sodium ethoxide or sodium hydroxide. As a solvent to be used, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, and solvents such as water can be used singly or in combination.
　式（ＩＶ）で示される化合物は、市販の化合物を利用可能であり、または市販の化合物を出発物質として既知の方法を組合せることにより得ることができる。 The compound represented by the formula (IV) can be a commercially available compound, or can be obtained by combining known methods using a commercially available compound as a starting material.
　例えば、式（ＩＶ）で示される化合物のＡが、２－ピロリル基の４、５位にベンゼン環または５～６員の芳香族ヘテロ環が縮合した基を示すとき、Ｊｏｕｒｎａｌ　ｏｆ　Ｍｅｄｉｃｉｎａｌ　Ｃｈｅｍｉｓｔｒｙ，４７（２５），６２７０－６２８２；２００４に記載の方法に準じて次式に示すように合成することができる。
Figure JPOXMLDOC01-appb-C000009
 For example, when A of the compound represented by the formula (IV) represents a group in which a benzene ring or a 5- to 6-membered aromatic heterocycle is condensed at the 4- and 5-positions of the 2-pyrrolyl group, Journal of Medicinal Chemistry, 47 (25), 6270-6282; can be synthesized according to the method described in 2004 as shown in the following formula.
Figure JPOXMLDOC01-appb-C000009
　すなわち、式（ＶＩＩ）（ここで、Ａ’は２－ピロリル基の４、５位に縮合するベンゼン環または５～６員の芳香族ヘテロ環を示す）で示される化合物に、式（ＶＩＩＩ）（Ｒ２は上記定義と同じである）で示されるアジド酢酸エステルを反応させ、得られる式（ＩＸ）で示される化合物を環化することで、上記化合物を得ることができる。 That is, the compound represented by the formula (VII) (wherein A ′ represents a benzene ring or 5- to 6-membered aromatic heterocycle condensed at the 4- and 5-positions of the 2-pyrrolyl group) is added to the compound represented by the formula (VIII) The above compound can be obtained by reacting the azidoacetate represented by the formula (R 2 is as defined above) and cyclizing the resulting compound represented by the formula (IX).
　式（ＶＩＩ）で示される化合物と、式（ＶＩＩＩ）で示される化合物の反応は、通常塩基存在下で行い、例えば、水素化ナトリウムなどのアルカリ金属水素化物、ナトリウムメトキシドなどのアルカリ金属アルコキシド、炭酸カリウムおよび炭酸ナトリウムなどの炭酸塩、水酸化カリウムおよび水酸化ナトリウムなどのアルカリ金属水酸化物、トリエチルアミンなどの第３級アミン類またはピリジンおよび４－ジメチルアミノピリジンなどの無置換のまたは置換基を有するピリジン類を用いることができる。 The reaction of the compound represented by the formula (VII) and the compound represented by the formula (VIII) is usually performed in the presence of a base. For example, an alkali metal hydride such as sodium hydride, an alkali metal alkoxide such as sodium methoxide, Carbonates such as potassium carbonate and sodium carbonate, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tertiary amines such as triethylamine or unsubstituted or substituted groups such as pyridine and 4-dimethylaminopyridine. The pyridine which has can be used.
　反応は、無溶媒で、または反応に影響しない溶媒もしくは目的反応を促進させる溶媒を用いて行うことができる。溶媒を用いる場合は、例えば、ジメチルホルムアミドおよびジメチルアセトアミドなどのアミド類、アセトニトリルなどのニトリル類、ジメチルスルホキシドなどのスルホキシド類、ジエチルエーテルおよびテトラヒドロフランなどのエーテル類、酢酸エチルおよび酢酸ブチルなどのエステル類、ベンゼン、キシレンおよびトルエンなどの芳香族炭化水素類、メタノール、エタノールおよびプロパノールなどのアルコール類、アセトンおよびメチルエチルケトンなどのケトン類、ヘキサン、ヘプタンおよびオクタンなどの脂肪族炭化水素類、ジクロロメタン、クロロホルム、クロロベンゼンおよびジクロロベンゼンなどのハロゲン炭化水素類ならびに水などの溶媒を１種類または２種類以上組み合わせて用いることができる。 The reaction can be performed without solvent, or using a solvent that does not affect the reaction or a solvent that promotes the target reaction. When using a solvent, for example, amides such as dimethylformamide and dimethylacetamide, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, ethers such as diethyl ether and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, Aromatic hydrocarbons such as benzene, xylene and toluene, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, aliphatic hydrocarbons such as hexane, heptane and octane, dichloromethane, chloroform, chlorobenzene and One kind or a combination of two or more kinds of solvents such as halogen hydrocarbons such as dichlorobenzene and water can be used.
　反応は、通常－８０～２５０℃で行うことができ、－２０～２０℃の範囲で行うことが好ましい。 The reaction can usually be carried out at −80 to 250 ° C., preferably in the range of −20 to 20 ° C.
　さらに、化学式（ＩＸ）で示される化合物を、無溶媒で、または反応に影響しない溶媒中もしくは目的反応を促進させる溶媒中で加熱することによって、化合物（ＩＶ）を得ることができる。溶媒を用いる場合は、例えば、ジフェニルエーテルなどの高沸点エーテル類、ベンゼン、キシレンおよびトルエンなどの芳香族炭化水素類、ヘプタン、オクタン、リグロインおよびミネラルオイルなどの飽和炭化水素類、クロロベンゼン、ブロモベンゼンおよびジクロロベンゼンなどのハロゲン炭化水素類などを１種類または２種類以上組み合わせて用いることができる。 Furthermore, the compound (IV) can be obtained by heating the compound represented by the chemical formula (IX) in the absence of a solvent, in a solvent that does not affect the reaction, or in a solvent that promotes the target reaction. When using a solvent, for example, high boiling point ethers such as diphenyl ether, aromatic hydrocarbons such as benzene, xylene and toluene, saturated hydrocarbons such as heptane, octane, ligroin and mineral oil, chlorobenzene, bromobenzene and di- Halogen hydrocarbons such as chlorobenzene can be used alone or in combination of two or more.
　反応は、通常８０～２５０℃で行うことができ、１００～２００℃の範囲で行うことが好ましい。 The reaction can usually be carried out at 80 to 250 ° C., preferably in the range of 100 to 200 ° C.
　式（Ｉ）で示される化合物を１種以上含有する有害生物防除剤が防除効果を示す有害生物としては、例えば、農園芸上の害虫、動物寄生性害虫（動物内部寄生虫および動物外部寄生虫）、衛生害虫、不快害虫、貯穀・貯蔵食品害虫および家屋害虫が挙げられ、好ましくは農園芸上の害虫または動物外部寄生虫である。 Examples of the pests that the pest control agent containing one or more compounds represented by the formula (I) exhibit a controlling effect include agricultural and horticultural pests, animal parasitic pests (animal endoparasites and animal ectoparasites) ), Sanitary pests, unpleasant pests, stored / stored food pests and house pests, preferably horticultural pests or animal ectoparasites.
　具体的な虫種の例は、以下の通りである。 Specific examples of insect species are as follows.
　農園芸上の害虫としては、鱗翅目害虫（例えば、ハスモンヨトウ、ヨトウガ、アワヨトウ、アオムシ、コナガ、シロイチモジヨトウ、ニカメイガ、コブノメイガ、フタオビコヤガ、ハマキガ、シンクイガ、ハモグリガ、ドクガ、アグロティス属害虫（Agrotis spp）、ヘリコベルパ属害虫（Helicoverpa spp）およびヘリオティス属害虫（Heliothis spp））、半翅目害虫（例えば、モモアカアブラムシ、ワタアブラムシ、Aphisfabae、トウモロコシアブラムシ、エンドウヒゲナガアブラムシ、ジヤガイモヒゲナガアブラムシ、マメアブラムシ、チューリップヒゲナガアブラムシ、Macrosiphum avenae、Methopolophium dirhodum、ムギクビレアブラムシ、ムギミドリアブラムシ、ダイコンアブラムシ、ニセダイコンアブラムシ、ユキヤナギアブラムシ、Rosy apple aphid、リンゴワタムシ、コミカンアブラムシおよびミカンクロアブラムシなどのアブラムシ類（Aphididae, Adelgidae, Phylloxeridae）、ツマグロヨコバイおよびチャノミドリヒメヨコバイなどのヨコバイ類、ヒメトビウンカ、トビイロウンカおよびセジロウンカなどのウンカ類、シラホシカメムシ、ミナミアオカメムシ、チャバネアオカメムシおよびアカヒゲホソミドリカスミカメなどのカメムシ類、シルバーリーフコナジラミ、タバココナジラミおよびオンシツコナジラミなどのコナジラミ類（Aleyrodidae）ならびにクワコナカイガラムシ、ミカンコナカイガラムシ、クワシロカイガラムシおよびアカマルカイガラムシなどのカイガラムシ類（Diaspididae, Margarodidae, Ortheziidae, Aclerdiae, Dactylopiidae, Kerridae, Pseudococcidae, Coccidae, Eriococcidae, Asterolecaniidae, Beesonidae, Lecanodiaspididae, Cerococcidaeなど））、鞘翅目害虫（例えば、イネミズゾウムシ、アズキゾウムシ、チャイロコメノゴミムシダマシ、ウェスタンコーンルートワーム、サザンコーンルートワーム、ドウガネブイブイ、ヒメコガネ、キスジノミハムシ、ウリハムシ、コロラドポテトハムシ、イネドロオイムシ、シンクイムシ類およびカミキリムシ類）、ダニ目害虫（例えば、ナミハダニ、カンザワハダニおよびミカンハダニ）、膜翅目害虫（例えば、ハバチ類）、直翅目害虫（例えば、バッタ類）、双翅目害虫（例えば、イエバエおよびハモグリバエ類）、アザミウマ目害虫（例えば、ミナミキイロアザミウマおよびミカンキイロアザミウマ）ならびに植物寄生性線虫（例えば、ネコブセンチュウ、ネグサレセンチュウ、イネシンガレセンチュウおよびマツノザイセンチュウ）などが挙げられる。 Agricultural and horticultural pests include lepidopterous pests (for example, Spodoptera litura, Coleoptera, Acayoto, Aomushi, Konaga, Shirouchimojiyoto, Nikameiga, Kononogaiga, Futobikoga, Sakigaiga, Sinkiga, Azalea, Agrotis s. Pests (Helicoverpa spp) and Heliothis spp), Hemiptera pests (eg, peach aphids, cotton aphids, Aphisfabae, corn aphids, pea aphids, potato aphids, bean aphids, tulip beetles ros hum hum avenae, Methopolophium dirhodum, wheat beetle aphid, barley aphid, radish aphid, fake aphid, snowy aphid, Rosy apple aphid, re Aphids (Aphididae, Adelgidae, Phylloxeridae) such as common aphids, Komikan aphids and citrus aphids, leafhoppers such as leafhoppers and leafhoppers, leafhoppers such as leafhoppers, leafhoppers and leafhoppers, Stink bugs such as blue stink bugs and red beetle worms, silver leaf whitefly, whitefly whitefly and whitefly whitefly (Aleyrodidae) as well as stag beetles, citrus scales, diidae, red beetles , Ortheziidae, Aclerdiae, Dactylopiidae, Kerridae, Pseudococcidae, Coccidae, Eriococcidae, Asterolecaniidae, Beesonidae, Le canodiaspididae, Cerococcidae, etc.), Coleoptera pests (eg, rice weevil, azuki bean weevil, white-tailed beetle, western corn rootworm, southern corn rootworm, stag beetle, staghorn beetle, staghorn beetle, worm worm beetle, potato beetle Beetles), mite order pests (eg, spider mite, kanzawa spider mite and citrus spider mite), hymenoptera pests (eg, wasps), straight-eyed pests (eg, grasshoppers), diptera pests (eg, house flies and leafworms) ), Thripidae pests (eg, Southern Thrips thrips and Citrus thrips) and plant parasitic nematodes (eg, root-knot nematodes, neptune nematodes, rice stag beetles and Pine wood nematode), and the like.
　動物寄生性害虫、すなわち動物寄生虫のうち、動物外部寄生虫としては、ダニ類（例えば、マダニ類（例えば、ローン・スターマダニ、メキシコ湾岸マダニ、オウシマダニ、ロッキー山脈森林マダニ、西海岸マダニ、アメリカンドッグティック、ツリガネチマダニ、キチマダニ、フタトゲチマダニ、オオトゲチマダニ、タネガタマダニ、ヤマトマダニ、西部クロアシダニ、シュルツェマダニ、ヒツジダニ、クロアシダニ、カズキダニおよびクリイロコイタマダニ）、ツメダニ類（例えば、ネコツメダニおよびイヌツメダニ）、ニキビダニ類（例えば、イヌニキビダニおよびネコニキビダニ）、キュウセンダニ類（例えば、ウシキュウセンヒゼンダニ）、ヒゼンダニ類（例えば、ウシショクヒヒゼンダニおよびイヌミミヒゼンダニ）、サオオシダニ類（例えば、トリサシダニ）、ワクモ類、ウモウダニ類（例えば、ニワトリウモウダニおよびヒシガタウモウダニ）、ツツガムシ類（例えば、ミヤガワタマツツガムシおよびアカツツガムシ））、ノミ類（例えば、ネコノミ、ヒトノミ、ケオプスネズミノミおよびネズミノミ）、ハジラミ類（例えば、イヌハジラミおよびニワトリハジラミ）、シラミ類（例えば、ブタジラミ、イヌジラミ、コロモジラミ、ヒトジラミ、ケジラミおよびトコジラミ）、イエバエ類、ウシバエ類、サシバエ類、ウマバエ類、チョウバエ類（例えば、サシチョウバエ）、ツェツェバエ、アブ類、ヤブカ類（例えば、ヒトスジシマカおよびネッタイシマカ）、イエカ類（例えば、アカイエカ）、ハマダラカ類、ヌカカ類、ブユ類、サシガメ類、イエヒメアリなどが挙げられる。動物内部寄生虫としては、線虫類（例えば、糞線虫類、鈎虫類、円虫類（例えば、捻転胃虫およびネズミ円虫）、毛様線虫類、変円虫類（例えば、豚肺虫、広東住血線虫および猫肺虫）、蟯虫類、盲腸虫類（例えば、鶏回虫）、回虫類（例えば、アニサキス線虫、豚回虫、馬回虫、犬回虫および猫回虫）、旋尾線虫類（例えば、スブルラ類、有棘顎口虫、猫胃虫、類円豚胃虫、大口馬胃虫、鶏胃虫およびメジナ虫）、糸状虫類（例えば、犬糸状虫、リンパ系糸状虫、回旋糸状虫およびロア糸状虫）、腎虫類および旋毛虫類（例えば、犬鞭虫および旋毛虫））、吸虫類（例えば、日本住血吸虫および肝蛭）、鉤頭虫類、条虫類（例えば、疑葉類（例えば、マンソン裂頭条虫）および円葉類（例えば、瓜実条虫））ならびに原虫類などが挙げられる。 Among animal parasites, ie, animal parasites, animal ectoparasites include ticks (eg, ticks (eg, Lone Star ticks, Gulf ticks, ticks, Rocky Mountain ticks, West Coast ticks, American dogs) Ticks, ticks, mites, capesid ticks, manes, mites, western mites, shrews, mites, mites, mites, mites, mites, mites, mites, mites, etc. Acne mites and cat dust mites), cucumber mites (for example, bovine cucumber mites mites), mites mites (for example, bovine mites mites and dog mites mites), Sao Mites (for example, avian mites), worms, mites (for example, chicken mites and mite mites), tsutsugamushi (for example Miyamatsu tsutsugamushi and tsutsugamushi)), fleas (for example, cat fleas, human fleas, mushrooms) Ops murine and mud mines), lice (eg, dog lice and chicken lice), lice (eg, pig lice, dog lice, louse lice, human lice, white lice and bed bugs), house flies, cow flies, sand flies, fly flies (E.g., sand flies), tsetse flies, abs, aedes (e.g., Aedes albopictus and Aedes aegypti), cuttlefish (e.g., mosquitoes), anopheles, nucifers, flyfish, sand turtles, house turtles And the like. Animal endoparasites include nematodes (eg, fecal nematodes, helminths, roundworms (eg, tortuous stomach and murine roundworms), ciliate nematodes, and heterocytics (eg, Pig pneumoniae, Cantonese schistosomiasis and cat lungworm), helminths, caecal worms (eg, chicken roundworm), roundworms (eg anisakis nematode, pig roundworm, horse roundworm, dog roundworm and cat roundworm), Rotating nematodes (e.g., bursula, spiny-mouthed jawworm, cat stomachworm, horoscope stomachworm, largemouth horse stomachworm, chicken stomachworm and medinae), filamentous insects (e.g. Lymphoid worms, rotifers and loar worms), nematodes and trichinidae (for example, Trichuris and Trichinella)), flukes (for example, Schistosoma japonicum and liver fluke), bald worms , And crustaceans (eg, suspicious leaves (eg, Manson ciliate) and circles (eg, Coleoptera)) and protozoa .
　衛生害虫、不快害虫、貯穀害虫、貯蔵食品害虫および家屋害虫としては、カ類（例えば、ヒトスジシマカおよびアカイエカ）、ゴキブリ類（例えば、クロゴキブリ、ヤマトゴキブリおよびチャバネゴキブリ）、コナダニ類（例えば、ケナガコナダニ）、ハエ類（例えば、イエバエ、ニクバエ、チョウバエ類、ショウジョウバエおよびユスリカ類）、ブユ類、ヌカカ類、膜翅目昆虫（例えば、クロオオアリおよびファイヤーアントなどのアリ類、オオスズメバチなどのハチ類）、ワラジムシ目の節足動物（例えば、ワラジムシ、フナムシおよびダンゴムシ）、半翅目昆虫（例えば、トコジラミ）、多足亜門の節足動物（例えば、ムカデ類、ゲジ類およびヤスデ類）、クモ目の節足動物（例えば、アシダカグモ）、鞘翅目昆虫（例えば、ゴミムシ）、トビムシ目の節足動物（例えば、トゲナシシロトビムシ）、ハサミムシ目昆虫（例えば、オオハサミムシ）、バッタ目昆虫（例えば、カマドウマ類）、コウチュウ目昆虫（例えば、アズキゾウムシ、コクゾウムシ、コクヌスト、コクヌストモドキ、ヒョウホンムシ、シバンムシ、キクイムシ、カツオブシムシおよびクロトラカミキリ）、チョウ目昆虫（例えば、メイガ類およびイガ類）、ヒラタムシ類、シロアリ目昆虫（例えば、イエシロアリ、アメリカカンザイシロアリおよびタイワンシロアリ）ならびにシミ目昆虫（例えば、ヤマトシミ）などが挙げられる。 Sanitary pests, unpleasant pests, stored grain pests, stored food pests and house pests include mosquitoes (e.g., human striped mosquitoes and mosquitoes), cockroaches (e.g. black cockroaches, crested cockroaches and German cockroaches), coniferous mites (e.g. Flies (eg, house flies, fly flies, butterflies, drosophila and chironomids), flyfish, phylums, hymenopteran insects (eg, ants such as the black ant and fire ant, bees such as the giant hornet) Arthropods (eg, Paramecium, Funabushi and Dangamushi), Hemiptera insects (eg, bed bugs), polypods of arthropods (eg, centipedes, geese, and millipedes), arachnid arthropods (E.g., acididae), Coleoptera insects (e.g., trash) ), Coleoptera arthropods (eg, genus Coleoptera), earwig insects (eg, Carabidae), grasshopper insects (eg, Crestedidae), Coleoptera insects (eg, Azuki weevil, scotch beetle, beetle), Red-footed beetle, leopard beetle, beetle, bark beetle, cutlet beetle and black beetle), lepidopterous insects (eg, moths and moths), scallops, termite insects (eg, termites, American termites, and white termites) and worms Examples include eye insects (for example, Yamatoshimi).
　これらの中で、本発明の有害生物防除剤を適用する虫種として好ましいものは、鱗翅目害虫、半翅目害虫、アザミウマ目害虫または動物寄生性のノミ類およびダニ類であり、より好ましくは、鱗翅目害虫、半翅目害虫、アザミウマ目害虫またはマダニ類である。 Among these, preferred as the insect species to which the pest control agent of the present invention is applied are lepidopterous insects, hemiptera pests, thrips pests or animal parasitic fleas and mites, more preferably Lepidoptera, Hemiptera pests, Thripidae pests or ticks.
　本発明の有害生物防除剤は、式（Ｉ）で示される化合物を単体で用いることができ、使用法に応じた担体を用いて調製することもできる。 The pest control agent of the present invention can use the compound represented by the formula (I) alone or can be prepared using a carrier according to the method of use.
　本発明の有害生物防除剤が農園芸用殺虫剤であるときは、通常は適当な固体担体、液体担体、ガス状担体、界面活性剤、分散剤およびその他の製剤用補助剤と混合して、乳剤、液剤、懸濁剤、水和剤、フロアブル剤、粉剤、粒剤、錠剤、油剤、エアゾールまたは薫煙剤などの任意の剤形で提供される。 When the pest control agent of the present invention is an agricultural and horticultural insecticide, it is usually mixed with a suitable solid carrier, liquid carrier, gaseous carrier, surfactant, dispersant and other formulation adjuvants, It is provided in any dosage form such as emulsion, solution, suspension, wettable powder, flowable, powder, granule, tablet, oil, aerosol or smoke.
　固体担体としては、例えば、タルク、ベントナイト、クレー、カオリン、ケイソウ土、バーミキュライト、ホワイトカーボンおよび炭酸カルシウムが挙げられる。 Examples of the solid carrier include talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, and calcium carbonate.
　液体担体としては、例えばメタノール、ｎ－ヘキサノールおよびエチレングリコールなどのアルコール類、アセトン、メチルエチルケトンおよびシクロヘキサノンなどのケトン類、ｎ－ヘキサン、ケロシンおよび灯油などの脂肪族炭化水素類、トルエン、キシレンおよびメチルナフタレンなどの芳香族炭化水素類、ジエチルエーテル、ジオキサンおよびテトラヒドロフランなどのエーテル類、酢酸エチルなどのエステル類、アセトニトリルおよびイソブチロニトリルなどのニトリル類、ジメチルホルムアミドおよびジメチルアセトアミドなどの酸アミド類、ダイズ油および綿実油などの植物油類、ジメチルスルホキシドならびに水が挙げられる。 Examples of the liquid carrier include alcohols such as methanol, n-hexanol and ethylene glycol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aliphatic hydrocarbons such as n-hexane, kerosene and kerosene, toluene, xylene and methylnaphthalene. Aromatic hydrocarbons such as, ethers such as diethyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, soybean oil And vegetable oils such as cottonseed oil, dimethyl sulfoxide and water.
　また、ガス状担体としては液化石油ガス（ＬＰＧ）、空気、窒素、炭酸ガスおよびジメチルエーテルなどが挙げられる。 Also, examples of the gaseous carrier include liquefied petroleum gas (LPG), air, nitrogen, carbon dioxide gas, and dimethyl ether.
　乳化、分散または展着などのための界面活性剤または分散剤としては、例えば、アルキル硫酸エステル類、アルキル（アリール）スルホン酸塩類、ポリオキシアルキレンアルキル（アリール）エーテル類、多価アルコールエステル類およびリグニンスルホン酸塩が挙げられる。 Surfactants or dispersants for emulsification, dispersion or spreading include, for example, alkyl sulfates, alkyl (aryl) sulfonates, polyoxyalkylene alkyl (aryl) ethers, polyhydric alcohol esters and Examples include lignin sulfonate.
　また、製剤の性状を改善するための補助剤としては、例えば、カルボキシメチルセルロース、アラビアガム、ポリエチレングリコールおよびステアリン酸カルシウムが挙げられる。 Further, examples of the adjuvant for improving the properties of the preparation include carboxymethyl cellulose, gum arabic, polyethylene glycol and calcium stearate.
　上記の担体、界面活性剤、分散剤および補助剤は、必要に応じて各々単独で、または組み合わせて用いることができる。 The above carriers, surfactants, dispersants and adjuvants can be used alone or in combination as required.
　上記製剤中の式（Ｉ）で示される化合物の含有量は、特に限定されないが、通常、製剤全量を基準として乳剤では１～７５重量％、液剤では１～７５重量％、粉剤では０．３～２５重量％、水和剤では１～９０重量％、フロアブル剤では１～９０％、粒剤では０．５～１０重量％である。式（Ｉ）で示される化合物、これらを含む製剤およびそれらと他の有害生物防除剤との混合剤は、有害昆虫、植物、植物繁殖体（plant propagation materials；例えば、種子、植物茎葉部、根部、発芽した植物および幼植物）、土壌、養液栽培における養液、養液栽培における固形培地および害虫の侵入を防ぐことを必要とする部屋などに適用することができる。適用される植物には、遺伝子組み換え作物が含まれる。これらの適用は、害虫の侵入の前および後に行うことができる。 The content of the compound represented by the formula (I) in the preparation is not particularly limited, but is usually 1 to 75% by weight for the emulsion, 1 to 75% by weight for the liquid, and 0.3% for the powder based on the total amount of the preparation. -25% by weight, wettable powder 1-90% by weight, flowable powder 1-90%, granule 0.5-10% by weight. Compounds of formula (I), formulations containing these, and mixtures of these with other pest control agents include harmful insects, plants, plant propagation materials (eg, seeds, plant foliage, roots) , Germinated plants and young plants), soil, nutrient solution in hydroponic culture, solid medium in hydroponic culture, and rooms that need to prevent the invasion of pests. Applied plants include genetically modified crops. These applications can be made before and after pest infestation.
　本発明の有害生物防除剤が動物寄生虫防除剤であるときは、液剤、乳剤、液化滴剤（プアオン製剤、スポットオン製剤等）、噴霧剤、泡状製剤、錠剤、顆粒剤、細粒剤、粉剤、カプセル剤、錠剤、チュアブル剤、注射剤、座剤、クリーム剤、シャンプー剤、リンス剤、樹脂剤、燻煙剤または毒餌剤などで提供されるが、液剤または液化滴剤（プアオン製剤、スポットオン製剤等）で提供されることが特に好ましい。 When the pest control agent of the present invention is an animal parasite control agent, it is a solution, emulsion, liquefied drop (pour-on preparation, spot-on preparation, etc.), spray, foam preparation, tablet, granule, fine granule , Powders, capsules, tablets, chewables, injections, suppositories, creams, shampoos, rinses, resins, smokes, poison baits, etc. , Spot-on formulations, etc.).
　液剤および液化滴剤（プアオン製剤、スポットオン製剤等）には、さらに、通常の乳化剤、分散剤、展着剤、湿潤剤、懸濁化剤、安定化剤、保存剤および噴射剤などの製剤用補助剤なども配合することができ、さらに、通常の塗膜形成剤も配合することができる。乳化、分散または展着などのための界面活性剤としては、例えば石鹸類、ポリオキシアルキレンアルキル（アリール）エーテル類、ポリオキシエチレンアルキルアリルエーテル類、ポリオキシエチレン脂肪酸エステル、高級アルコール類およびアルキルアリールスルホン酸塩が挙げられる。分散剤としては、例えばカゼイン、ゼラチン、多糖類、リグニン誘導体、糖類および合成水溶性高分子が挙げられる。展着・湿潤剤としては、例えばグリセリンおよびポリエチレングリコールが挙げられる。懸濁化剤としては、例えばカゼイン、ゼラチン、ヒドロキシプロピルセルロースおよびアラビアガムが挙げられる。安定化剤としては、例えばフェノール系酸化防止剤（ブチルヒドロキシトルエン（ＢＨＴ）およびブチルヒドロキシアニソール（ＢＨＡ）など）、アミン系酸化防止剤（ジフェニルアミンなど）ならびに有機硫黄系酸化防止剤などが挙げられる。保存剤としては、例えばパラオキシ安息香酸メチル、パラオキシ安息香酸エチル、パラオキシ安息香酸プロピルおよびパラオキシ安息香酸ブチルが挙げられる。上記の担体、界面活性剤、分散剤および補助剤は、必要に応じて各々単独で、あるいは組み合わせて用いることができる。液剤には、さらに香料および共力剤などを含有してもよい。本発明の有害生物防除剤中の式（Ｉ）で示される化合物の製剤中の含有量は、液剤では製剤全量を基準として通常１～７５重量％が適当である。 For liquids and liquefied drops (poor-on preparations, spot-on preparations, etc.), preparations such as ordinary emulsifiers, dispersants, spreading agents, wetting agents, suspending agents, stabilizers, preservatives, propellants, etc. A supplementary agent can be blended, and a normal film forming agent can be blended. Surfactants for emulsification, dispersion or spreading include, for example, soaps, polyoxyalkylene alkyl (aryl) ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, higher alcohols and alkylaryls Examples include sulfonates. Examples of the dispersant include casein, gelatin, polysaccharides, lignin derivatives, saccharides, and synthetic water-soluble polymers. Examples of the spreading / wetting agent include glycerin and polyethylene glycol. Examples of the suspending agent include casein, gelatin, hydroxypropyl cellulose, and gum arabic. Examples of the stabilizer include phenolic antioxidants (such as butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA)), amine-based antioxidants (such as diphenylamine), and organic sulfur-based antioxidants. Examples of preservatives include methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, and butyl paraoxybenzoate. The above carriers, surfactants, dispersants and adjuvants can be used alone or in combination as required. The liquid agent may further contain a fragrance and a synergist. The content of the compound represented by the formula (I) in the pest control agent of the present invention in the preparation is usually 1 to 75% by weight based on the total amount of the preparation in the liquid preparation.
　クリーム剤を調製するために使用する担体としては、例えば非揮発性炭化水素類（流動パラフィンなど）、ラノリン水添加油脂類、高級脂肪酸、脂肪酸エステル、動植物油、シリコーンオイルおよび水が挙げられる。さらに、乳化剤、保湿剤、酸化防止剤、香料、ホウ砂および紫外線吸収剤も、必要に応じて、各々単独でまたは組み合わせて用いることができる。乳化剤としては、例えば、脂肪酸ソルビタン、ポリオキシエチレンアルキルエーテルおよび脂肪酸ポリオキシエチレンが挙げられる。本発明の有害生物防除剤中の式（Ｉ）で示される化合物の製剤中の含有量は、クリーム剤では、製剤全量を基準として通常０．５～７０重量％が適当である。カプセル剤、丸剤または錠剤は、式（Ｉ）で示される化合物を適当に小分けし、希釈液または澱粉、乳糖およびタルクなどのキャリアーと混合し、さらに、ステアリン酸マグネシウムなど崩壊剤および結合剤を加え、必要に応じて打錠して製造することができる。 Examples of the carrier used for preparing the cream include non-volatile hydrocarbons (such as liquid paraffin), lanolin-added oils and fats, higher fatty acids, fatty acid esters, animal and vegetable oils, silicone oils and water. Furthermore, an emulsifier, a humectant, an antioxidant, a fragrance, borax, and an ultraviolet absorber can be used alone or in combination as required. Examples of the emulsifier include fatty acid sorbitan, polyoxyethylene alkyl ether, and fatty acid polyoxyethylene. The content of the compound represented by the formula (I) in the pest control agent of the present invention in the preparation is usually 0.5 to 70% by weight based on the total amount of the preparation. For capsules, pills or tablets, the compound of formula (I) is appropriately subdivided and mixed with a diluent or a carrier such as starch, lactose and talc, and further a disintegrant and binder such as magnesium stearate. In addition, it can be manufactured by tableting as necessary.
　注射剤は無菌溶液として調製する必要がある。注射剤には、例えば、その溶液を血液と等張にさせるために十分な塩またはブドウ糖が含まれていても良い。注射剤を調製するために使用可能な担体としては、グリセリド、安息香酸ベンジル、ミリスチン酸イソプロピルおよびプロピレングリコールの脂肪酸誘導体などのエステルならびにＮ－メチルピロリドンおよびグリセロールホルマールなどの有機溶媒が挙げられる。本発明の有害生物防除剤中の式（Ｉ）で示される化合物の製剤中の含有量は、注射剤では、製剤全量を基準として通常０．０１～１０重量％が適当である。樹脂剤を調製するための担体としては、例えば塩化ビニル系重合体およびポリウレタンが挙げられる。担体であるこれらの基材には、必要によりフタル酸エステル類、アジピン酸エステル類およびステアリン酸などの可塑剤を添加することができる。該基材中に式（Ｉ）で示される化合物を混練した後、射出成型、押出成型またはプレス成型などにより成型することができる。さらに、適宣、成型および裁断などの工程を経て、動物用イヤータッグまたは動物用防虫首輪とすることもできる。 Injections must be prepared as sterile solutions. An injection may contain, for example, sufficient salt or glucose to make the solution isotonic with blood. Carriers that can be used to prepare injectables include glycerides, esters such as benzyl benzoate, isopropyl myristate and fatty acid derivatives of propylene glycol, and organic solvents such as N-methylpyrrolidone and glycerol formal. The content of the compound represented by the formula (I) in the pest control agent of the present invention in the preparation is usually 0.01 to 10% by weight based on the total amount of the preparation for injection. Examples of the carrier for preparing the resin agent include vinyl chloride polymers and polyurethane. If necessary, plasticizers such as phthalates, adipic esters and stearic acid can be added to these substrates as carriers. After kneading the compound represented by the formula (I) in the substrate, it can be molded by injection molding, extrusion molding, press molding or the like. Furthermore, it can be made into an animal ear tag or an animal insect repellent collar through suitable processes such as molding and cutting.
　毒餌剤用の担体としては、餌物質および誘引物質（小麦粉およびトウモロコシ粉などの穀粉、コーンスターチおよびポテトスターチなどの澱粉、グラニュー糖、麦芽糖および蜂蜜などの糖類、グリセリン、オニオンフレーバーおよびミルクフレーバーなどの食品フレーバー、蛹粉および魚粉などの動物性粉末ならびに各種フェロモンなど）が挙げられる。式（Ｉ）で示される化合物の製剤中の含有量は、毒餌剤では製剤全量を基準として通常０．０００１～９０重量％が適当である。 Carriers for poisonous baits include food and attractants (flours such as wheat flour and corn flour, starches such as corn starch and potato starch, sugars such as granulated sugar, maltose and honey, foods such as glycerin, onion flavor and milk flavor Flavors, animal powders such as rice bran powder and fish meal, and various pheromones). The content of the compound represented by formula (I) in the preparation is usually 0.0001 to 90% by weight based on the total amount of the preparation for poisonous baits.
　本発明の有害生物防除剤を、経口または注射により適用動物の体内へ投与すること、および、適用動物の体表の全体または一部へ投与することで有害生物を防除することができる。また、害虫の侵入、寄生または移動が予想される場所を本発明の有害生物防除剤で被覆することにより、有害生物を防除することもできる。 The pest control agent of the present invention can be controlled by being administered orally or by injection into the body of an applied animal, and by being administered to all or part of the body surface of the applied animal. In addition, pests can be controlled by coating a place where pests are expected to enter, parasite or move with the pest control agent of the present invention.
　本発明の有害生物防除剤は、そのまま用いても良いが、場合によっては水、液状の担体、市販のシャンプー、リンス、餌または飼育舎下敷きなどで希釈して適用することができる。 The pest control agent of the present invention may be used as it is, but depending on the case, it can be diluted with water, a liquid carrier, a commercially available shampoo, rinse, bait or a breeding house underlay.
　また、本発明による有害生物防除剤は、他の殺菌剤、殺虫剤、殺ダニ剤、除草剤、植物成長調節剤および肥料などと混合して用いることもできる。混合して用いることができる薬剤としては、ペスティサイド　マニュアル（第１３版　Ｔｈｅ　Ｂｒｉｔｉｓｈ　Ｃｒｏｐ　Ｐｒｏｔｅｃｔｉｏｎ　Ｃｏｕｎｃｉｌ発行）および、シブヤインデックス（ＳＨＩＢＵＹＡ　ＩＮＤＥＸ　第１３版、２００８年、ＳＨＩＢＵＹＡ　ＩＮＤＥＸ　ＲＥＳＥＡＲＣＨ　ＧＲＯＵＰ発行）に記載のものが挙げられる。より具体的には、殺虫剤、殺ダニ剤または殺線虫剤としては、アセフェート（acephate）、ジクロルボス（dichlorvos）、EPN、フェニトロチオン（fenitrothion）、フェナミホス（fenamifos）、プロチオホス（prothiofos）、プロフェノホス（profenofos）、ピラクロホス（pyraclofos）、クロルピリホスメチル（chlorpyrifos-methyl）、ダイアジノン（diazinon）、ホスチアゼート（fosthiazate）およびイミシアホス（imicyafos）などの有機リン酸エステル系化合物、メソミル（methomyl）、チオジカルブ（thiodicarb）、アルジカルブ（aldicarb）、オキサミル（oxamyl）、プロポキスル（propoxur）、カルバリル（carbaryl）、フェノブカルブ（fenobucarb）、エチオフェンカルブ（ethiofencarb）、フェノチオカルブ（fenothiocarb）、ピリミカーブ（pirimicarb）、カルボフラン（carbofuran）およびベンフラカルブ（benfuracarb）などのカーバメート系化合物、カルタップ（cartap）およびチオシクラム（thiocyclam）などのネライストキシン誘導体、ジコホル（dicofol）およびテトラジホン（tetradifon）などの有機塩素系化合物、ペルメトリン（permethrin）、テフルトリン（tefluthrin）、シペルメトリン（cypermethrin）、デルタメトリン（deltamethrin）、シハロトリン（cyhalothrin）、フェンバレレート（fenvalerate）、フルバリネート（fluvalinate）、エトフェンプロックス（ethofenprox）およびシラフルオフェン（silafluofen）などのピレスロイド系化合物、ジフルベンズロン（diflubenzuron）、テフルベンズロン（teflubenzuron）、フルフェノクスロン（flufenoxuron）およびクロルフルアズロン（chlorfluazuron）などのベンゾイルウレア系化合物、メトプレン（methoprene）などの幼若ホルモン様化合物ならびにクロマフェノジドなどの脱皮ホルモン様化合物が挙げられる。さらに、その他の化合物として、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）、ピリダベン（pyridaben）、フェンピロキシメート（fenpyroxymate）、ピリミジフェン（pyrimidifen）、テブフェンピラド（tebufenpyrad）、トルフェンピラド（tolfenpyrad）、フルアクリピリム（fluacrypyrim）、アセキノシル（acequinocyl）、シフルメトフェン（cyflumetofen）、フルベンジアミド（flubendiamide）、エチプロール（ethiprole）、フィプロニル（fipronil）、エトキサゾール（ethoxazole）、イミダクロプリド（imidacloprid）、クロチアニジン（clothianidin）、チアメトキサム（thiamethoxam）、アセタミプリド（acetamiprid）、ニテンピラム（nitenpyram）、チアクロプリド（thiacloprid）、ジノテフラン（dinotefuran）、ピメトロジン（pymetrozine）、ビフェナゼート（bifenazate）、スピロジクロフェン（spirodiclofen）、スピロメシフェン（spiromesifen）、フロニカミド（flonicamid）、クロルフェナピル（chlorfenapyr）、ピリプロキシフェン（pyriproxyfen）、インドキサカルブ（indoxacarb）、ピリダリル（pyridalyl）、スピノサド（spinosad）、アベルメクチン（avermectin）、ミルベマイシン（milbemycin）、シエノピラフェン（cyenopyrafen）、スピネトラム（spinetoram）、ピリフルキナゾン（pyrifluquinazon）、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）、スピロテトラマト（spirotetramat）、レピメクチン（lepimectin）、メタフルミゾン（metaflumizone）、ピラフルプロール（pyrafluprole）、ピリプロール（pyriprole）、ヒドラメチルノン（hydramethylnon）、トリアザメート（triazamate）、スルフォキサフロル（sulfoxaflor）、フルピラジフロン（flupyradifurone）、フロメトキン（flometoquin）、アフィドピロペン（afidopyropen）、ピフルブミド（pyflubumide）、有機金属系化合物、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およびヒドラジン系化合物が挙げられる。 Also, the pest control agent according to the present invention can be used by mixing with other fungicides, insecticides, acaricides, herbicides, plant growth regulators and fertilizers. Drugs that can be used in combination are those listed in the Pesticide Manual (issued by The 13th Edition The British Crop Protection Council) and Shibuya Index (SHIBUYA INDEX 13th Edition, 2008, published by SHIBUYA INDEX RESEARCH GROUP). It is done. More specifically, insecticides, acaricides or nematicides include acephate, dichlorvos, EPN, fenitrothion, fenamifos, prothiofos, profenfos ), Pyraclofos, chlorpyrifos-methyl, diazinon, fosthiazate and imicyafos, organophosphate compounds such as methomyl, thiodicarb, aldicarb ( aldicarb, oxamyl, propoxur, carbaryl, fenobucarb, ethiofencarb, fenothiocarb, pirimicarb, carbofuran and ben Carbamate compounds such as belfuracarb, nereistoxin derivatives such as cartap and thiocyclam, organochlorine compounds such as dicofol and tetradifon, permethrin, tefluthrin ), Cypermethrin, deltamethrin, cyhalothrin, fenvalerate, fluvalinate, etofenprox and pyrethroid compounds such as silafluofen, diflubenzuron ), Benzoylurea compounds such as teflubenzuron, flufenoxuron and chlorfluazuron, and juveniles such as metoprene Rumon like compounds and molting hormone-like compounds such as chromafenozide and the like. In addition, other compounds include buprofezin, hexythiazox, amitraz, chlordimeform, pyridaben, fenpyroxymate, pyrimidifen, tebufenrad, tebufenrad, tebufenrad, tebufenrad ), Fluacrypyrim, acequinocyl, cyflumetofen, flubendiamide, ethiprole, fipronil, etoxazole, imidacloprid, ididacloprid, imidacloprid, imidacloprid thiamethoxam), acetamiprid (acetamiprid), nitenpyram, thiacloprid, dinotefuran, pime Rosin (pymetrozine), bifenazate, spirodiclofen (spirodiclofen), spiromesifen (spiromesifen), flonicamid (flonicamid), chlorfenapyr (chlorfenapyr), pyriproxyfen (pyriproxyfen), indoxacarb (indoxacarb), pyridalyl ( pyridalyl, spinosad, avermectin, milbemycin, cyenopyrafen, spinetoram, pyrifluquinazon, chlorantraniliprole, cyantraniliprole, cyantraniliprole Spirotetramat, lepimectin, metaflumizone, pyrafluprole, pyriprole, hydramethylnon, triaza Mate (triazamate), sulfoxaflor, flupyradifurone (flupyradifurone), flometoquin (afmepyquin) (afidopyropen), piflubumide, organometallic compounds, dinitro compounds, organic sulfur compounds, urea compounds, A triazine type compound and a hydrazine type compound are mentioned.
　本発明の有害生物防除剤は、ＢＴ剤および昆虫病原ウイルス剤などの微生物農薬と、混用または併用することもできる。 The pest control agent of the present invention can be used in combination with or in combination with microbial pesticides such as BT agents and entomopathogenic virus agents.
　混用または併用で用いられる殺菌剤としては、例えば、アゾキシストロビン（azoxystrobin）、クレソキシムメチル（kresoxym-methyl）、トリフロキシストロビン（trifloxystrobin）、メトミノストロビン（metominostrobin）およびオリサストロビン（orysastrobin）などのストロビルリン系化合物、メパニピリム（mepanipyrim）、ピリメサニル（pyrimethanil）およびシプロジニル（cyprodinil）などのアニリノピリミジン系化合物、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）、メトコナゾール（metoconazole）、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）、ミクロブタニル（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）、プロクロラズ（prochloraz）、シメコナゾール（simeconazole）などのアゾール系化合物、キノメチオネート（quinomethionate）などのキノキサリン系化合物、マンネブ（maneb）、ジネブ（zineb）、マンコゼブ（mancozeb）、ポリカーバメート（polycarbamate）およびプロビネブ（propineb）などのジチオカーバメート系化合物、ジエトフェンカルブ（diethofencarb）などのフェニルカーバメート系化合物、クロロタロニル（chlorothalonil）およびキントゼン（quintozene）などの有機塩素系化合物、ベノミル（benomyl）、チオファネートメチル（thiophanate-methyl）およびカーベンダジム（carbendazole）などのベンズイミダゾール系化合物、メタラキシル（metalaxyl）、オキサジキシル（oxadixyl）、オフラセ（ofurase）、ベナラキシル（benalaxyl）、フララキシル（furalaxyl）およびシプロフラン（cyprofuram）などのフェニルアミド系化合物、ジクロフルアニド（dichlofluanid）などのスルフェン酸系化合物、水酸化第二銅（copper hydroxide）およびオキシキノリン銅（oxine-copper）などの銅系化合物、ヒドロキシイソキサゾール（hydroxyisoxazole）などのイソキサゾール系化合物、ホセチルアルミニウム（fosetyl-aluminium）およびトルクロホス－メチル（tolclofos-methyl）などの有機リン系化合物、キャプタン（captan）、カプタホール（captafol）およびフォルペット（folpet）などのＮ－ハロゲノチオアルキル系化合物、プロシミドン（procymidone）、イプロジオン（iprodione）およびビンクロゾリン（vinchlozolin）などの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）、フラメトピル（furametpyr）、チフルザミド（thifluzamide）、ボスカリド（boscalid）およびペンチオピラド（penthiopyrad）などのカルボキシアニリド系化合物、フェンプロピモルフ（fenpropimorph）およびジメトモルフ（dimethomorph）などのモルフォリン系化合物、水酸化トリフェニルスズ（fenthin hydroxide）および酢酸トリフェニルスズ（fenthin acetate）などの有機スズ系化合物、フルジオキソニル（fludioxonil）およびフェンピクロニル（fenpiclonil）などのシアノピロール系化合物、トリシクラゾール（tricyclazole）、ピロキロン（pyroquilon）、カルプロパミド（carpropamid）、ジクロシメット（diclocymet）、フェノキサニル（fenoxanil）、フサライド（fthalide）、フルアジナム（fluazinam）、シモキサニル（cymoxanil）、トリホリン（triforine）、ピリフェノックス（pyrifenox）、フェナリモル（fenarimol）、フェンプロピディン（fenpropidin）、ペンシクロン（pencycuron）、フェリムゾン（ferimzone）、シアゾファミド（cyazofamid）、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）、イミノクタジンアルベシル酸塩（iminoctadin-albesilate）、シフルフェナミド（cyflufenamid）、カスガマイシン（kasugamycin）、バリダマイシン（validamycin）、ストレプトマイシン（streptomycin）、オキソリニック酸（oxolinic-acid）、テブフロキン（tebufloquin）、プロベナゾール（probenazole）、チアジニル（tiadinil）、イソチアニル（isotianil）、トルプロカルブ（tolprocarb）ならびにイソフェタミド（isofetamid）などが挙げられる。 Examples of fungicides used in combination or in combination include strobilurins such as azoxystrobin, kresoxym-methyl, trifloxystrobin, metominostrobin and orysastrobin. Compounds, ananilinopyrimidine compounds such as mepanipyrim, pyrimethanil and cyprodinil, triadimefon, bitertanol, triflumizole, metconazole, protoconazole (Propiconazole), penconazole, flusilazole (flusilazole), microbutanil (myclobutanil), cyproconazole, tebuconazole, hexaconazole (h azole compounds such as exaconazole, prochloraz, simeconazole, quinoxaline compounds such as quinomethionate, maneb, zineb, mancozeb, polycarbamate and procarb (Propineb) and other dithiocarbamate compounds, dietofencarb and other phenylcarbamate compounds, chlorothalonil and quintozene organochlorine compounds, benomyl, thiophanate-methyl and carbendazim Benzimidazole compounds such as (carbendazole), metalaxyl, oxadixyl, ofurase, benalaxyl, flaxaxyl And phenylamide compounds such as cyprofuram, sulfenic acid compounds such as dichlofluanid, copper compounds such as copper hydroxide and oxine-copper, hydroxy Isoxazole compounds such as hydroxyisoxazole, organophosphorus compounds such as fosetyl-aluminium and tolclofos-methyl, captan, captafol and folpet N-halogenothioalkyl compounds such as procymidone, iprodione and vinchlozolin, dicarboximide compounds such as flutolanil, mepronil, furametpyr, tifluzamide Carboxanilide compounds such as thifluzamide, boscalid and penthiopyrad, morpholine compounds such as fenpropimorph and dimethomorph, phenthin hydroxide and triphenyl acetate Organotin compounds such as tin (fenthin acetate), cyanopyrrole compounds such as fludioxonil and fenpiclonil, tricyclazole, pyroquilon, carpropamid, diclocymet, phenoxanil fenoxanil, fthalide, fluazinam, simmoxanil, triforine, pyrifenox, fenarimol, fenpromol Fenpropidin, pencycuron, ferimzone, cyazofamid, cyazofamid, iprovalicarb, benchthiavalicarb-isopropyl, iminoctadin-albesilate, cyflufenfenamide (cyflufendamide) ), Kasugamycin, validamycin, streptomycin, oxolinic-acid, tebufloquin, probenazole, thiadinyl, isothianil, and tolprocarb Examples include isofetamid.
　次に、実施例を挙げて本発明をより具体的に説明するが、本発明は実施例に制限されるものではない。 Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.
［合成例］
　式（ＩＩＩ）で示されるカルボン酸を以下の通り合成した。 [Synthesis example]
The carboxylic acid represented by the formula (III) was synthesized as follows.
参考例１　１－（３－クロロピリジン－２－イル）－１Ｈ－インドール－２－カルボン酸の合成
　インドール－２－カルボン酸エチル９４０ｍｇ（５ｍｍｏｌ）および２，３－ジクロロピリジン７４０ｍｇ（５ｍｍｏｌ）をニトロベンゼン２０ｍｌに溶かし、炭酸カリウム１０００ｍｇ（７．２５ｍｍｏｌ）、ピリジン１５００ｍｇおよび臭化銅（Ｉ）１５０ｍｇを加え、反応混合物を１８０℃で３時間攪拌した。反応混合物を室温に戻し、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝９：１→ヘキサン：酢酸エチル＝２：１）により、１－（３－クロロピリジン－２－イル）－１Ｈ－インドール－２－カルボン酸エチルを分離した。
　１－（３－クロロピリジン－２－イル）－１Ｈ－インドール－２－カルボン酸エチル１００ｍｇ（０．３３ｍｍｏｌ）をエタノール２ｍｌに溶かし、１Ｎ水酸化ナトリウム２ｍｌを加え、３０分還流した。エタノールを減圧留去し、残渣に２ｍｌの水を加え、氷冷下にて攪拌しながら２Ｎ硫酸を加え酸性にした。生じた結晶をろ過し、デシケーターにて乾燥し、表題化合物６５ｍｇを得た。 Reference Example 1 Synthesis of 1- (3-chloropyridin-2-yl) -1H-indole-2-carboxylic acid 940 mg (5 mmol) of ethyl indole-2-carboxylate and 740 mg (5 mmol) of 2,3-dichloropyridine were combined with nitrobenzene. Dissolved in 20 ml, 1000 mg (7.25 mmol) of potassium carbonate, 1500 mg of pyridine and 150 mg of copper (I) bromide were added, and the reaction mixture was stirred at 180 ° C. for 3 hours. The reaction mixture was returned to room temperature and purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1 → hexane: ethyl acetate = 2: 1) to give 1- (3-chloropyridin-2-yl) -1H-indole-2. -The ethyl carboxylate was isolated.
100 mg (0.33 mmol) of ethyl 1- (3-chloropyridin-2-yl) -1H-indole-2-carboxylate was dissolved in 2 ml of ethanol, 2 ml of 1N sodium hydroxide was added, and the mixture was refluxed for 30 minutes. Ethanol was distilled off under reduced pressure, 2 ml of water was added to the residue, and the mixture was acidified with 2N sulfuric acid while stirring under ice-cooling. The resulting crystals were filtered and dried with a desiccator to obtain 65 mg of the title compound.
参考例２　４－（３－クロロピリジン－２－イル）－４Ｈ－チエノ［３，２－ｂ］ピロール－５－カルボン酸の合成
　金属ナトリウム１．２２ｇをエタノール４０ｍｌに溶かし、溶液を０℃に冷却した。この溶液に、２－チオフェンカルバルデヒド２．６ｇおよびアジド酢酸エチル４．０ｇをエタノール１０ｍｌに溶かした溶液を少しずつ滴下し、０℃で１時間攪拌した。反応混合物を氷水にあけ、エーテルで抽出し、エーテル層を硫酸マグネシウム上で乾燥した。エーテルを減圧留去し、その残渣にキシレン５０ｍｌを加え、１４０℃で１時間攪拌した。反応混合物を濃縮し、残渣をシリカゲルカラムクロマトグラフィー（酢酸エチル：ヘキサン＝１：２）にて分離操作を行い、チエノ［３，２－ｂ］ピロール－５－カルボン酸エチル７８８ｍｇを得た。
　得られたチエノ［３，２－ｂ］ピロール－５－カルボン酸エチル５３８ｍｇ（２．７６ｍｍｏｌ）および２，３－ジクロロピリジン４０８ｍｇ（２．７６ｍｍｏｌ）をニトロベンゼン２０ｍｌに溶かし、炭酸カリウム５５０ｍｇ（３．９６ｍｍｏｌ）、ピリジン８３０ｍｇおよび臭化銅（Ｉ）８３ｍｇを加え、反応混合物を１９０℃で６時間攪拌した。反応混合物を室温に戻し、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝９：１→ヘキサン：酢酸エチル＝２：１）にて分離操作を行い、４－（３－クロロピリジン－２－イル）－４Ｈ－チエノ［３，２－ｂ］ピロール－５－カルボン酸エチル１４５ｍｇを得た。これをエタノール５ｍｌに溶かし、１Ｎ水酸化ナトリウム５ｍｌを加え、３０分還流した。エタノールを減圧留去し、２ｍｌの水を加え、氷冷下にて攪拌しながら２Ｎ硫酸を加え酸性にした。生じた結晶をろ過し、デシケーターにて乾燥し、表題化合物１１４ｍｇを得た。 Reference Example 2 Synthesis of 4- (3-chloropyridin-2-yl) -4H-thieno [3,2-b] pyrrole-5-carboxylic acid 1.22 g of sodium metal was dissolved in 40 ml of ethanol, and the solution was brought to 0 ° C. Cooled down. To this solution was added dropwise a solution of 2.6 g of 2-thiophenecarbaldehyde and 4.0 g of ethyl azide acetate in 10 ml of ethanol, and the mixture was stirred at 0 ° C. for 1 hour. The reaction mixture was poured into ice water, extracted with ether, and the ether layer was dried over magnesium sulfate. The ether was distilled off under reduced pressure, 50 ml of xylene was added to the residue, and the mixture was stirred at 140 ° C. for 1 hour. The reaction mixture was concentrated, and the residue was separated by silica gel column chromatography (ethyl acetate: hexane = 1: 2) to obtain 788 mg of ethyl thieno [3,2-b] pyrrole-5-carboxylate.
538 mg (2.76 mmol) of ethyl thieno [3,2-b] pyrrole-5-carboxylate and 408 mg (2.76 mmol) of 2,3-dichloropyridine were dissolved in 20 ml of nitrobenzene to obtain 550 mg (3.96 mmol) of potassium carbonate. ), 830 mg of pyridine and 83 mg of copper (I) bromide were added, and the reaction mixture was stirred at 190 ° C. for 6 hours. The reaction mixture is returned to room temperature and separated by silica gel column chromatography (hexane: ethyl acetate = 9: 1 → hexane: ethyl acetate = 2: 1) to give 4- (3-chloropyridin-2-yl)- 145 mg of ethyl 4H-thieno [3,2-b] pyrrole-5-carboxylate was obtained. This was dissolved in 5 ml of ethanol, 5 ml of 1N sodium hydroxide was added, and the mixture was refluxed for 30 minutes. Ethanol was distilled off under reduced pressure, 2 ml of water was added, and the mixture was acidified with 2N sulfuric acid while stirring under ice cooling. The resulting crystals were filtered and dried with a desiccator to obtain 114 mg of the title compound.
　参考例１～２および同様の方法で合成した中間体（参考例３～１０）の構造式およびスペクトルデータを以下の表に記す。表中のＥＩ－ＨＲＭＳは、電子イオン化高分解能質量分析を表す。
Figure JPOXMLDOC01-appb-T000010
 The structural formulas and spectral data of Reference Examples 1 and 2 and intermediates (Reference Examples 3 to 10) synthesized by the same method are shown in the following table. EI-HRMS in the table represents electron ionization high resolution mass spectrometry.
Figure JPOXMLDOC01-appb-T000010
　式（Ｉ）で示される化合物を以下の通り合成した。 The compound represented by the formula (I) was synthesized as follows.
合成例１　Ｎ－（４－クロロ－２－メチル－６－（メチルカルバモイル）フェニル）－４－（３－クロロピリジン－２－イル）－４Ｈ－チエノ［３，２－ｂ］ピロール－５－カルボキサミド（化合物６）の合成
　国際公開第２００６／０６２９７８号　実施例１に記載の方法で合成した２－アミノ－５－クロロ－Ｎ，３－ジメチルベンズアミド４２ｍｇ（０．２１ｍｍｏｌ）、参考例２で合成した４－（３－クロロピリジン－２－イル）－４Ｈ－チエノ［３，２－ｂ］ピロール－５－カルボン酸５５ｍｇ（０．２ｍｍｏｌ）およびピリジン５５ｍｇをアセトニトリル５ｍｌに溶かし、攪拌し、メシルクロリド３２ｍｇを加え、反応混合物を室温で一晩攪拌した。アセトニトリルを減圧留去し、薄層クロマトグラフィー（酢酸エチル：ヘキサン＝１：１）にて精製し、表題化合物３２ｍｇを得た。 Synthesis Example 1 N- (4-Chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (3-chloropyridin-2-yl) -4H-thieno [3,2-b] pyrrole-5 Synthesis of carboxamide (Compound 6) WO 2006/062978 42 mg (0.21 mmol) of 2-amino-5-chloro-N, 3-dimethylbenzamide synthesized by the method described in Example 1, synthesized in Reference Example 2 4- (3-chloropyridin-2-yl) -4H-thieno [3,2-b] pyrrole-5-carboxylic acid (55 mg, 0.2 mmol) and pyridine (55 mg) were dissolved in acetonitrile (5 ml), stirred, and mesyl chloride 32 mg was added and the reaction mixture was stirred at room temperature overnight. Acetonitrile was distilled off under reduced pressure and purified by thin layer chromatography (ethyl acetate: hexane = 1: 1) to obtain 32 mg of the title compound.
合成例２　Ｎ－（４－ブロモ－２－メチル－６－（メチルカルバモイル）フェニル）－１－（３－クロロピリジン－２－イル）－１Ｈ－インドール－２－カルボキサミド（化合物８）の製造
　国際公開第２００６／０６２９７８号　実施例６工程Ａに記載の方法で合成した２－アミノ－５－ブロモ－Ｎ，３－ジメチルベンズアミド５１ｍｇ（０．２１ｍｍｏｌ）、参考例１で合成した１－（３－クロロピリジン－２－イル）－１Ｈ－インドール－２－カルボン酸５５ｍｇ（０．２ｍｍｏｌ）およびピリジン５５ｍｇをアセトニトリル５ｍｌに溶かし、攪拌し、メシルクロリド３２ｍｇを加え、反応混合物を室温で一晩攪拌した。アセトニトリルを減圧留去し、薄層クロマトグラフィー（酢酸エチル：ヘキサン＝１：１）にて精製し、表題化合物３２ｍｇを得た。 Synthesis Example 2 Production of N- (4-bromo-2-methyl-6- (methylcarbamoyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-indole-2-carboxamide (Compound 8) Publication No. 2006/062978 Example 6 51 mg (0.21 mmol) of 2-amino-5-bromo-N, 3-dimethylbenzamide synthesized by the method described in Step A, 1- (3- Chloropyridin-2-yl) -1H-indole-2-carboxylic acid 55 mg (0.2 mmol) and pyridine 55 mg were dissolved in 5 ml of acetonitrile, stirred, 32 mg of mesyl chloride was added, and the reaction mixture was stirred at room temperature overnight. Acetonitrile was distilled off under reduced pressure and purified by thin layer chromatography (ethyl acetate: hexane = 1: 1) to obtain 32 mg of the title compound.
　合成例１～２の化合物（化合物６、８）および同様の方法で合成した化合物（化合物１～５、７、９～２８）の構造式およびスペクトルデータを以下の表に記す。
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
 The structural formulas and spectral data of the compounds of Synthesis Examples 1 and 2 (Compounds 6 and 8) and the compounds synthesized by the same method (Compounds 1 to 5, 7, and 9 to 28) are shown in the following table.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
　［製剤例］
　合成した化合物を含む、様々な剤形の製剤を製造した。 [Formulation example]
Various dosage forms were prepared containing the synthesized compounds.
製剤例１〔粒剤〕
化合物１　　　　　　　　　　　　　　　　　　５重量％
ベントナイト　　　　　　　　　　　　　　　４０重量％
タルク　　　　　　　　　　　　　　　　　　１０重量％
クレー　　　　　　　　　　　　　　　　　　４３重量％
リグニンスルホン酸カルシウム　　　　　　　　２重量％
　上記成分を均一に粉砕混合し、水を加えてよく練合した後、造粒乾燥して粒剤を得た。 Formulation Example 1 [Granule]
Compound 1 5% by weight
Bentonite 40% by weight
Talc 10% by weight
43% by weight of clay
2% by weight calcium lignin sulfonate
The above components were pulverized and mixed uniformly, kneaded well with water, and granulated and dried to obtain granules.
製剤例２〔粒剤〕
化合物１　　　　　　　　　　　　　　　　　　２重量％
サンエキス（商標）Ｐ―２５２　　　　　　　　５重量％
結合剤　　　　　　　　　　　　　　　　　１．５重量％
造粒性改良剤　　　　　　　　　　　　　　０．５重量％
クレー　　　　　　　　　　　　　　　　　　９１重量％
　上記成分を均一に粉砕混合し、水を加えてよく練合した後、造粒乾燥して粒剤を得た。なお、サンエキス（商標）Ｐ―２５２は、リグニンスルホン酸ナトリウムを主成分とする、日本製紙ケミカル株式会社の製品である。 Formulation Example 2 [Granule]
Compound 1 2% by weight
Sun Extract (trademark) P-252 5% by weight
Binder 1.5% by weight
Granulation improver 0.5% by weight
91% by weight clay
The above components were pulverized and mixed uniformly, kneaded well with water, and granulated and dried to obtain granules. Sun Extract (trademark) P-252 is a product of Nippon Paper Chemicals Co., Ltd., mainly composed of sodium lignin sulfonate.
製剤例３〔水和剤〕
化合物３　　　　　　　　　　　　　　　　　３０重量％
クレー　　　　　　　　　　　　　　　　　　５０重量％
ホワイトカーボン　　　　　　　　　　　　　　２重量％
ケイソウ土　　　　　　　　　　　　　　　　１３重量％
リグニンスルホン酸カルシウム　　　　　　　　４重量％
ラウリル硫酸ナトリウム　　　　　　　　　　　１重量％
　上記成分を均一に混合し、粉砕して水和剤を得た。 Formulation Example 3 [wettable powder]
Compound 3 30% by weight
50% by weight of clay
2% white carbon
Diatomaceous earth 13% by weight
4% by weight calcium lignin sulfonate
Sodium lauryl sulfate 1% by weight
The above ingredients were mixed uniformly and pulverized to obtain a wettable powder.
製剤例４〔顆粒水和剤〕
化合物３　　　　　　　　　　　　　　　　　３０重量％
クレー　　　　　　　　　　　　　　　　　　６０重量％
デキストリン　　　　　　　　　　　　　　　　５重量％
アルキルマレイン酸共重合物　　　　　　　　　４重量％
ラウリル硫酸ナトリウム　　　　　　　　　　　１重量％
　上記成分を均一に粉砕混合し、水を加えてよく練合した後、造粒乾燥して顆粒水和剤を得た。 Formulation Example 4 [Granule wettable powder]
Compound 3 30% by weight
60% clay
Dextrin 5% by weight
Alkyl maleic acid copolymer 4% by weight
Sodium lauryl sulfate 1% by weight
The above components were uniformly pulverized and mixed, water was added and kneaded well, and then granulated and dried to obtain a granular wettable powder.
製剤例５〔フロアブル剤〕
化合物８　　　　　　　　　　　　　　　　　　　　　　　２５重量％
ＰＯＥポリスチリルフェニルエーテル硫酸塩　　　　　　　　５重量％
プロピレングリコール　　　　　　　　　　　　　　　　　　６重量％
ベントナイト　　　　　　　　　　　　　　　　　　　　　　１重量％
キサンタンガム１％水溶液　　　　　　　　　　　　　　　　３重量％
ＰＲＯＮＡＬ　ＥＸ－３００（東邦化学工業株式会社）０．０５重量％
ＡＤＤＡＣ　８２７（ケイ・アイ化成株式会社）　　　０．０２重量％
水　　　　　　　　　　　　　　　　　　　　　　加えて１００重量％
　キサンタンガム１％水溶液と水を除く上記成分の全量を予備混合した後、湿式粉砕機にて粉砕した。その後、キサンタンガム１％水溶液と残りの水を加え１００重量％としてフロアブル剤を得た。 Formulation Example 5 [Flowable Agent]
Compound 8 25% by weight
POE polystyryl phenyl ether sulfate 5% by weight
Propylene glycol 6% by weight
Bentonite 1% by weight
Xanthan gum 1% aqueous solution 3% by weight
PRONAL EX-300 (Toho Chemical Industry Co., Ltd.) 0.05% by weight
ADDAC 827 (Kay Kasei Co., Ltd.) 0.02% by weight
100% by weight of water
All of the above components except xanthan gum 1% aqueous solution and water were premixed and then pulverized with a wet pulverizer. Thereafter, 1% aqueous solution of xanthan gum and the remaining water were added to obtain a flowable agent at 100% by weight.
製剤例６〔乳剤〕
化合物１　　　　　　　　　　　　　　　　　　　１５重量％
Ｎ，Ｎ－ジメチルホルムアミド　　　　　　　　　２０重量％
ソルベッソ１５０（エクソンモービル有限会社）　５５重量％
ポリオキシエチレンアルキルアリールエーテル　　１０重量％
　上記成分を均一に混合、溶解して乳剤を得た。 Formulation Example 6 [Emulsion]
Compound 1 15% by weight
N, N-dimethylformamide 20% by weight
Solvesso 150 (ExxonMobil Co., Ltd.) 55% by weight
10% by weight of polyoxyethylene alkyl aryl ether
The above ingredients were uniformly mixed and dissolved to obtain an emulsion.
製剤例７〔粉剤〕
化合物１４　　　　　　　　　　　　　　　　　　　２重量％
クレー　　　　　　　　　　　　　　　　　　　　６０重量％
タルク　　　　　　　　　　　　　　　　　　　　３７重量％
ステアリン酸カルシウム　　　　　　　　　　　　　１重量％
　上記成分を均一に混合して粉剤を得た。 Formulation Example 7 [powder]
Compound 14 2% by weight
60% clay
Talc 37% by weight
Calcium stearate 1% by weight
The said component was mixed uniformly and the powder agent was obtained.
製剤例８〔ＤＬ粉剤〕
化合物１　　　　　　　　　　　　　　　　　　　　　２重量％
ＤＬクレー　　　　　　　　　　　　　　　　　９４．５重量％
ホワイトカーボン　　　　　　　　　　　　　　　　　２重量％
ステアリン酸カルシウム　　　　　　　　　　　　　　１重量％
軽質流動パラフィン　　　　　　　　　　　　　　０．５重量％
　上記成分を均一に混合して粉剤を得た。 Formulation Example 8 [DL powder]
Compound 1 2% by weight
DL clay 94.5% by weight
2% white carbon
Calcium stearate 1% by weight
Light liquid paraffin 0.5% by weight
The said component was mixed uniformly and the powder agent was obtained.
製剤例９〔微粒剤Ｆ〕
化合物３　　　　　　　　　　　　　　　　　　　　　　２重量％
キャリアー　　　　　　　　　　　　　　　　　　　　９４重量％
ホワイトカーボン　　　　　　　　　　　　　　　　　　２重量％
ハイゾールＳＡＳ－２９６（ＪＸ日鉱日石エネルギー）　２重量％
上記成分を均一に混合して粉剤を得た。 Formulation Example 9 [Fine Granule F ]
Compound 3 2% by weight
Carrier 94% by weight
2% white carbon
Hysol SAS-296 (JX Nippon Oil & Energy) 2% by weight
The said component was mixed uniformly and the powder agent was obtained.
製剤例１０〔液化滴剤〕
化合物１　　　　　　　　　　　　　　　　　　　　１０重量％
ベンジルアルコール　　　　　　　　　　　　　７４．９重量％
プロピレンカーボネート　　　　　　　　　　　　　１５重量％
ブチルヒドロキシトルエン　　　　　　　　　　　０．１重量％
　上記成分を均一に攪拌、溶解して液化滴剤を得た。 Formulation Example 10 (Liquid drops)
Compound 1 10% by weight
Benzyl alcohol 74.9% by weight
15% by weight propylene carbonate
Butylhydroxytoluene 0.1% by weight
The above components were uniformly stirred and dissolved to obtain a liquefied droplet.
製剤例１１〔液化滴剤〕
化合物１　　　　　　　　　　　　　　　　　　　　４８重量％
エタノール　　　　　　　　　　　　　　　　　　　５２重量％
　上記成分を均一に混合して液化滴剤を得た。 Formulation Example 11 [Liquid drops]
Compound 1 48% by weight
Ethanol 52% by weight
The said component was mixed uniformly and the liquid drop was obtained.
　また本発明化合物と別の有害生物防除剤の混合組成物を以下の通り製造した。 In addition, a mixed composition of the present compound and another pesticide was produced as follows.
製剤例１２〔粒剤〕
化合物１　　　　　　　　　　　　　　　　　　２重量％
プロベナゾール　　　　　　　　　　　　　　２４重量％
結合剤　　　　　　　　　　　　　　　　　３．０重量％
造粒性改良剤　　　　　　　　　　　　　　０．５重量％
クレー　　　　　　　　　　　　　　　　７０．５重量％
　上記成分を均一に粉砕混合し、水を加えてよく練合した後、造粒乾燥して粒剤を得た。 Formulation Example 12 [Granule]
Compound 1 2% by weight
Probenazole 24% by weight
Binder 3.0% by weight
Granulation improver 0.5% by weight
Clay 70.5% by weight
The above components were pulverized and mixed uniformly, kneaded well with water, and granulated and dried to obtain granules.
　［試験例］
　合成した化合物１～２８の有害生物防除活性を、以下の試験例により確認した。 [Test example]
The pesticidal activity of the synthesized compounds 1 to 28 was confirmed by the following test examples.
試験例１　コナガ防除試験
　ポット栽培のキャベツから直径５．０ｃｍのリーフディスクを切り抜き、これに５０％アセトン水（０．０５％Ｔｗｅｅｎ２０（商標）添加）となるように調製した所定濃度の化合物の薬液を散布した。風乾後、これにコナガの２令幼虫を放飼した。その後、これを２５℃の恒温室（１６時間明期－８時間暗期）に放置した。放飼３日後に虫の生死を観察し、次式に従って死虫率を算出した。試験は、２連制により行った。
　死虫率（％）＝｛死亡虫数／（生存虫数十死亡虫数）｝×１００
　その結果、１００ｐｐｍの茎葉処理により、化合物１，２，３，４，５，６，７，８，２６および２８が死虫率８０％以上の殺虫活性を示した。
　１０ｐｐｍの茎葉処理により、化合物１，３，４，５，６，７，８，９，１０，１８，１９，２０，２２，２３，２４および２６が死虫率８０％以上の殺虫活性を示した。
　１ｐｐｍの茎葉処理により、化合物１，４，５，６，７，８，１１，１２，１３，１４，１５，１６，１８，１９，２２，２３，２４および２８が死虫率８０％以上の殺虫活性を示した。 Test Example 1 Cutout of a leaf disc having a diameter of 5.0 cm from cabbage cultivated in a potter's beak prevention test pot, and a chemical solution of a compound having a predetermined concentration prepared to be 50% acetone water (0.05% Tween 20 (trademark) added). Sprayed. After air drying, the second instar larvae were released. Thereafter, this was left in a thermostatic chamber (16 hours light period-8 hours dark period) at 25 ° C. The insects were observed for life and death 3 days after the release, and the death rate was calculated according to the following formula. The test was conducted by a two-run system.
Death rate (%) = {Number of dead insects / (Number of living insects tens of dead insects)} × 100
As a result, the compounds 1, 2, 3, 4, 5, 6, 7, 8, 26 and 28 showed insecticidal activity with a mortality rate of 80% or more after 100 ppm of foliage treatment.
By treatment with 10 ppm of foliage, compounds 1,3,4,5,6,7,8,9,10,18,19,20,22,23,24 and 26 show insecticidal activity with a death rate of 80% or more. It was.
With 1 ppm foliar treatment, compounds 1, 4, 5, 6, 7, 8, 11, 12, 13, 14, 15, 16, 18, 19, 22, 23, 24, and 28 have a death rate of 80% or more. Insecticidal activity was demonstrated.
試験例２　ハスモンヨトウ防除試験
　ポット栽培のキャベツから直径５．０ｃｍのリーフディスクを切り抜き、これに５０％アセトン水（０．０５％Ｔｗｅｅｎ２０（商標）添加）となるように調製した所定濃度の化合物の薬液を散布した。風乾後、これにハスモンヨトウの３令幼虫を放飼した。その後、これを２５℃の恒温室（１６時間明期－８時間暗期）に放置した。放飼３日後に虫の生死を観察し、次式に従って死虫率を算出した。試験は、２連制により行った。
　死虫率（％）＝｛死亡虫数／（生存虫数十死亡虫数）｝×１００
　その結果、１００ｐｐｍの茎葉処理により、化合物１，３，４，５，６，７，８，２５，２６および２８が死虫率８０％以上の殺虫活性を示した。
　１０ｐｐｍの茎葉処理により、化合物１，３，４，５，６，７，８，９，１０，１８，１９，２０，２１，２２，２３，２４および２６が死虫率８０％以上の殺虫活性を示した。
　１ｐｐｍの茎葉処理により、化合物１，３，４，５，６，７，８，９，１１，１２，１４，１６，１８，１９，２０，２２，２３，２４および２８が死虫率８０％以上の殺虫活性を示した。 Test Example 2 A cut-out leaf disc having a diameter of 5.0 cm was cut out from a cabbage grown in a pot- spotted carp control pot, and a chemical solution of a compound having a predetermined concentration prepared so as to be 50% acetone water (added with 0.05% Tween 20 (trademark)). Sprayed. After air-drying, the third-instar larvae of Spodoptera litura were released. Thereafter, this was left in a thermostatic chamber (16 hours light period-8 hours dark period) at 25 ° C. The insects were observed for life and death 3 days after the release, and the death rate was calculated according to the following formula. The test was conducted by a two-run system.
Death rate (%) = {Number of dead insects / (Number of living insects tens of dead insects)} × 100
As a result, the compounds 1,3,4,5,6,7,8,25,26 and 28 showed insecticidal activity with a mortality rate of 80% or more after 100 ppm of foliage treatment.
Insecticidal activity of compounds 1,3,4,5,6,7,8,9,10,18,19,20,21,22,23,23, and 26 with a death rate of 80% or more by treatment with 10 ppm of foliage showed that.
Compound 1,3,4,5,6,7,8,9,11,12,14,16,18,19,20,22,23,24 and 28 were killed by 1 ppm of foliage at 80% death rate The above insecticidal activity was exhibited.
試験例３　ワタアブラムシ防除試験
　ポット栽培のキュウリから直径２．０ｃｍのリーフディスクを切り抜き、これに５０％アセトン水（０．０５％Ｔｗｅｅｎ２０（商標）添加）となるように調製した所定濃度の化合物の薬液を散布した。風乾後、これにワタアブラムシの１令幼虫を放飼した。その後、これを２５℃の恒温室（１６時間明期－８時間暗期）に放置した。放飼３日後に虫の生死を観察し、次式に従って死虫率を算出した。試験は、２連制により行った。
　死虫率（％）＝｛死亡虫数／（生存虫数十死亡虫数）｝×１００
　その結果、５００ｐｐｍの茎葉処理により、化合物１，５，６，７，８，１１，１２，１３，１４，１５，１６，１８および２８が死虫率８０％以上の殺虫活性を示した。
　１００ｐｐｍの茎葉処理により、化合物１，５，６，７，８，１１，１２，１３，１４，１９，２０および２８が死虫率８０％以上の殺虫活性を示した。
　２０ｐｐｍの茎葉処理により、化合物５，６，７，８，９，１２，１４，１９，２０，２２，２４および２８が死虫率８０％以上の殺虫活性を示した。 Test Example 3 Cotton Aphid Control Test A leaf disc having a diameter of 2.0 cm was cut out from a cucumber cultivated in a pot, and 50% acetone water (0.05% Tween 20 (trademark) added) was added to this. The chemical solution was sprayed. After air drying, cotton aphid first instar larvae were released. Thereafter, this was left in a thermostatic chamber (16 hours light period-8 hours dark period) at 25 ° C. The insects were observed for life and death 3 days after the release, and the death rate was calculated according to the following formula. The test was conducted by a two-run system.
Death rate (%) = {Number of dead insects / (Number of living insects tens of dead insects)} × 100
As a result, the compounds 1, 5, 6, 7, 8, 11, 12, 13, 14, 15, 16, 18, and 28 showed insecticidal activity with a mortality rate of 80% or more after treatment with 500 ppm of foliage.
Compounds 1, 5, 6, 7, 8, 11, 12, 13, 14, 19, 20, and 28 showed insecticidal activity with a mortality rate of 80% or more after 100 ppm foliage treatment.
Compounds 5, 6, 7, 8, 9, 12, 14, 19, 20, 22, 24, and 28 showed insecticidal activity with a mortality rate of 80% or more after treatment with 20 ppm of foliage.
試験例４　ミカンキイロアザミウマ防除試験
　ポット栽培のインゲンから直径２．８ｃｍのリーフディスクを切り抜き、これに５０％アセトン水（０．０５％Ｔｗｅｅｎ２０（商標）添加）となるように調製した所定濃度の化合物の薬液を散布した。風乾後、これにミカンキイロアザミウマの１令幼虫を放飼した。その後、これを２５℃の恒温室（１６時間明期－８時間暗期）に放置した。放飼３日後に虫の生死を観察し、次式に従って死虫率を算出した。試験は、２連制により行った。
　死虫率（％）＝｛死亡虫数／（生存虫数十死亡虫数）｝×１００
　その結果、５００ｐｐｍの茎葉処理により、化合物１，５，６，８，１１，１２，１３，１４，１５および２２が死虫率８０％以上の殺虫活性を示した。
　１００ｐｐｍの茎葉処理により、化合物６，７，１９および２８が死虫率８０％以上の殺虫活性を示した。 Test Example 4 Citrus thrips control test A leaf disk with a diameter of 2.8 cm was cut out from green beans grown in pots, and 50% acetone water (0.05% Tween20 (trademark) added) was added to this compound. The chemical solution was sprayed. After air drying, the first instar larvae of Citrus thrips were released. Thereafter, this was left in a thermostatic chamber (16 hours light period-8 hours dark period) at 25 ° C. The insects were observed for life and death 3 days after the release, and the death rate was calculated according to the following formula. The test was conducted by a two-run system.
Death rate (%) = {Number of dead insects / (Number of living insects tens of dead insects)} × 100
As a result, the compounds 1, 5, 6, 8, 11, 12, 13, 14, 15, and 22 exhibited insecticidal activity with a mortality rate of 80% or more after treatment with 500 ppm of foliage.
Compounds 6, 7, 19 and 28 showed insecticidal activity with a mortality rate of 80% or more after 100 ppm foliage treatment.
試験例５　イエバエ防除試験
　室内にて飼育しているイエバエの雌成虫の背面に、アセトンにて所定濃度に調製した化合物の薬液を１頭あたり１μＬ処理した。薬剤処理後、カップ当たり５頭となるように、成虫をプラスチックカップへ移して、２５℃の恒温室（１６時間明期－８時間暗期）に放置した。処理２４時間後に、成虫の苦悶状況を観察し、次式に従って苦悶虫率を算出した。試験は、２連制により行った。
　苦悶虫率（％）＝｛苦悶虫数／（正常虫数＋苦悶虫数）｝×１００
　その結果、化合物２μｇ／頭の処理量において、化合物６，９，１０，１９，２２および２３が苦悶虫率８０％以上の高い殺虫効果を示した。 Test Example 5 1 μL of a chemical solution of a compound prepared at a predetermined concentration with acetone was treated on the back of a female housefly of a housefly kept in a housefly control test room. After the chemical treatment, adults were transferred to plastic cups so that there were 5 per cup, and left in a constant temperature room (16 hours light period-8 hours dark period) at 25 ° C. After 24 hours of treatment, the state of agony of adults was observed, and the rate of agony was calculated according to the following formula. The test was conducted by a two-run system.
Rate of bitter worms (%) = {number of bitter worms / (number of normal worms + number of bitter worms)} × 100
As a result, the compounds 6, 9, 10, 19, 22, and 23 showed a high insecticidal effect with an morbidity rate of 80% or more at a treatment amount of 2 μg of compound per head.
＜動物寄生性害虫に対する防除効果＞
試験例６　フタトゲチマダニ防除試験
　化合物の２００ｐｐｍのアセトン溶液３０μＬを、４ｍＬ容ガラスバイアルに入れた。風乾してバイアル内壁に化合物のドライフィルムを形成させた。これにフタトゲチマダニ幼ダニ１０頭を放飼して、蓋をした。バイアルは、２５℃、湿度８５％、全暗条件の恒温室に静置した。放飼１日後に生死を観察し、次式に従って死虫率を算出した。試験は、２連制により行った。
　死虫率（％）＝｛死亡虫数／（生存虫数十死亡虫数）｝×１００
　その結果、化合物５および９が死虫率８０％以上の殺虫効果を示した。 <Control effect against animal parasitic pests>
Test Example 6 A 30 ppm solution of 200 ppm acetone solution of a test compound for controlling ticklet mite was placed in a 4 mL glass vial. Air-dried to form a dry film of the compound on the inner wall of the vial. To this, 10 young mite ticks were released and capped. The vial was placed in a temperature-controlled room at 25 ° C., 85% humidity and all dark conditions. Life and death were observed one day after release, and the mortality was calculated according to the following formula. The test was conducted by a two-run system.
Death rate (%) = {Number of dead insects / (Number of living insects tens of dead insects)} × 100
As a result, compounds 5 and 9 showed an insecticidal effect with a death rate of 80% or more.

Claims (5)

  1. 　式（Ｉ）で示される化合物
    Figure JPOXMLDOC01-appb-C000001
     ［式中、
    　Ｒ１は、ハロゲン原子で置換されていてもよいＣ１－８アルキル基を示し、
    　Ｗは、それぞれ独立して、ハロゲン原子、シアノ基またはＳ群から選択される置換基で置換されていてもよいＣ１－８アルキル基を示し、
    　ｎは、０～４の整数を示し、
    　Ａは、Ｔ群から選択される置換基で置換されていてもよい、少なくとも１つの窒素原子を含有する２～３環性の縮合芳香族ヘテロ環を示し、
    　Ｂは、Ａの窒素原子に結合する、Ｕ群から選択される置換基で置換されていてもよい５～６員の芳香族ヘテロ環を示し、
    　Ｓ群は、シアノ基およびハロゲン原子からなり、
    　Ｔ群は、ハロゲン原子、ハロゲン原子で置換されていてもよいＣ１－８アルキル基およびハロゲン原子で置換されていてもよいＣ１－８アルキルオキシ基からなり、
    　Ｕ群は、ハロゲン原子、ハロゲン原子で置換されていてもよいＣ１－８アルキル基およびハロゲン原子で置換されていてもよいＣ１－８アルキルオキシ基からなる］。     Compound represented by formula (I)
    Figure JPOXMLDOC01-appb-C000001
     [Where:
    R 1 represents a C 1-8 alkyl group which may be substituted with a halogen atom,
    W each independently represents a halogen atom, a cyano group or a C 1-8 alkyl group which may be substituted with a substituent selected from the group S;
    n represents an integer of 0 to 4,
    A represents a bicyclic to tricyclic fused aromatic heterocycle containing at least one nitrogen atom, which may be substituted with a substituent selected from Group T;
    B represents a 5- to 6-membered aromatic heterocycle optionally substituted with a substituent selected from Group U, which is bonded to the nitrogen atom of A;
    S group consists of a cyano group and a halogen atom,
    T group consists halogen atom, optionally substituted C 1-8 alkyl group and optionally C 1-8 alkyl group optionally substituted by a halogen atom with a halogen atom,
    U group, a halogen atom, optionally substituted C 1-8 alkyl group and optionally C 1-8 alkyl group optionally substituted by a halogen atom with a halogen atom.
  2. 　Ａが２～３環性の縮合ピロール環であり、
    　Ｂが該縮合ピロール環の窒素原子に結合する、Ｕ群から選択される置換基で置換されていてもよいピリジン環またはＵ群から選択される置換基で置換されていてもよいピラジン環である、
    請求項１に記載の化合物。     A is a bicyclic to tricyclic fused pyrrole ring,
    B is a pyridine ring optionally substituted with a substituent selected from the U group or a pyrazine ring optionally substituted with a substituent selected from the U group, which is bonded to the nitrogen atom of the fused pyrrole ring ,
    The compound of claim 1.
  3. 　請求項１または２に記載の化合物を１種以上含む有害生物防除剤。 A pest control agent comprising one or more compounds according to claim 1 or 2.
  4. 　有害生物防除剤が農園芸用殺虫剤である、請求項３に記載の有害生物防除剤。 The pest control agent according to claim 3, wherein the pest control agent is an agricultural and horticultural insecticide.
  5. 　有害生物防除剤が動物寄生虫防除剤である、請求項３に記載の有害生物防除剤。 The pest control agent according to claim 3, wherein the pest control agent is an animal parasite control agent.
PCT/JP2012/079129 2011-11-11 2012-11-09 Anthranilic acid derivative and noxious organism control agent WO2013069771A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011247548 2011-11-11
JP2011-247548 2011-11-11

Publications (1)

Publication Number Publication Date
WO2013069771A1 true WO2013069771A1 (en) 2013-05-16

Family

ID=48290138

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/079129 WO2013069771A1 (en) 2011-11-11 2012-11-09 Anthranilic acid derivative and noxious organism control agent

Country Status (2)

Country Link
JP (1) JPWO2013069771A1 (en)
WO (1) WO2013069771A1 (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003528070A (en) * 2000-03-22 2003-09-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Insecticidal anthranilamides
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
JP2005502661A (en) * 2001-08-15 2005-01-27 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー O-Heterocyclic substituted arylamides for controlling invertebrate pests
JP2005503384A (en) * 2001-08-16 2005-02-03 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Substituted anthranilamides for the control of invertebrate pests
JP2005503385A (en) * 2001-08-15 2005-02-03 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Ortho-substituted arylamides for controlling invertebrate pests
JP2005504084A (en) * 2001-09-21 2005-02-10 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Insecticidal diamide
JP2005514324A (en) * 2001-05-21 2005-05-19 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Diamide invertebrate pest suppressant containing non-aromatic heterocyclic ring
JP2008520724A (en) * 2004-11-18 2008-06-19 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Anthranilamide insecticide
JP2009506039A (en) * 2005-08-24 2009-02-12 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Anthranilamides for invertebrate pest control
WO2012081916A2 (en) * 2010-12-17 2012-06-21 한국화학연구원 Indazole derivative and a pesticide composition containing the same

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003528070A (en) * 2000-03-22 2003-09-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Insecticidal anthranilamides
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
JP2005514324A (en) * 2001-05-21 2005-05-19 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Diamide invertebrate pest suppressant containing non-aromatic heterocyclic ring
JP2005502661A (en) * 2001-08-15 2005-01-27 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー O-Heterocyclic substituted arylamides for controlling invertebrate pests
JP2005503385A (en) * 2001-08-15 2005-02-03 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Ortho-substituted arylamides for controlling invertebrate pests
JP2005503384A (en) * 2001-08-16 2005-02-03 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Substituted anthranilamides for the control of invertebrate pests
JP2005504084A (en) * 2001-09-21 2005-02-10 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Insecticidal diamide
JP2008520724A (en) * 2004-11-18 2008-06-19 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Anthranilamide insecticide
JP2009506039A (en) * 2005-08-24 2009-02-12 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Anthranilamides for invertebrate pest control
WO2012081916A2 (en) * 2010-12-17 2012-06-21 한국화학연구원 Indazole derivative and a pesticide composition containing the same

Also Published As

Publication number Publication date
JPWO2013069771A1 (en) 2015-04-02

Similar Documents

Publication Publication Date Title
JP5269609B2 (en) Pest control agent
JP4993641B2 (en) Pest control agent
JP5575831B2 (en) Pest control agent
JP5745704B2 (en) Pest control composition containing a novel iminopyridine derivative
JP6300207B2 (en) Novel cyclic depsipeptide derivative and pest control agent comprising the same
KR102029517B1 (en) Nitrogen-containing heterocyclic derivative having 2-imino group and pest control agent including the same
MX2007011287A (en) Biphenyl-n-(4-pyridyl) methylsufonamides.
UA126150C2 (en) Pesticidally active heterocyclic derivatives with sulfur containing substituents
BRPI0714572A2 (en) compounds, process for preparing compounds, agricultural composition, process for treating harmful phytopathogenic fungi, use of compounds, methods to combat arthropod pests, to protect crops from attack or infestation by arthropod pests, to protect seed from pest infestation arthropods and from infestation of shoots and seedling roots by arthropod pests, and to protect non-living materials from attack or infestation by arthropod and seed pests
JP2012077078A (en) Novel triazolone derivative and pest control agent containing the same as active constituent
KR20110132317A (en) Composition to control harmful organisms that contains 16-keto aspergillimide
WO2013069771A1 (en) Anthranilic acid derivative and noxious organism control agent
JP5037164B2 (en) Pest control agent
JPH0539205A (en) Agricultural/horticultural mixed composition
KR20110132318A (en) 16-keto aspergillimide and pest exterminating agent comprising the same as active ingredient
KR20180098631A (en) Compositions for pest control comprising iminopyridine derivatives
WO2015093558A1 (en) Cyclic depsipeptide derivative and pest control agent including same
JP2017031060A (en) Cyclic depsipeptide derivative and pest control agent comprising the same
JP2017031058A (en) Cyclic depsipeptide derivative and pest control agent comprising the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12848410

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013543044

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12848410

Country of ref document: EP

Kind code of ref document: A1