WO2012057265A1 - Composition pesticide et méthode de lutte antiparasitaire - Google Patents

Composition pesticide et méthode de lutte antiparasitaire Download PDF

Info

Publication number
WO2012057265A1
WO2012057265A1 PCT/JP2011/074819 JP2011074819W WO2012057265A1 WO 2012057265 A1 WO2012057265 A1 WO 2012057265A1 JP 2011074819 W JP2011074819 W JP 2011074819W WO 2012057265 A1 WO2012057265 A1 WO 2012057265A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
halogen atom
compound
optionally substituted
Prior art date
Application number
PCT/JP2011/074819
Other languages
English (en)
Japanese (ja)
Inventor
大槻純子
Original Assignee
住友化学株式会社
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 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2012057265A1 publication Critical patent/WO2012057265A1/fr

Links

Classifications

    • 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
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Definitions

  • the present invention relates to a pest control composition and a pest control method.
  • An object of the present invention is to provide a pest control composition having an excellent control effect on pests, and a pest control method.
  • the present inventors have found that a combined use of a condensed imidazole compound represented by the following formula (1) and a pyrethroid compound has an excellent control effect against harmful animals, and the present invention It came to. That is, the present invention has the following configuration.
  • a 1 and A 2 are the same or different and represent a nitrogen atom or ⁇ CH—, m represents 0, 1 or 2; R 1 , R 2 , R 3 and R 4 are the same or different and are substituted with a group selected from group X, a C1-C6 chain hydrocarbon group which may be substituted with a group selected from group X
  • a C3-C6 alicyclic hydrocarbon group, a phenyl group optionally substituted with a group selected from group Y, a benzyl group optionally substituted with a group selected from group Y, a group selected from group Y in substituted heterocycle may also be 5-membered optionally heterocyclic group or 6-membered heterocyclic group, -OR 8, -NR 8 R 9 , -NR 8 C (O) R 9, -S (O) m R 8, -SO 2 Cl, —SO 2 NR 8 R 9 , —CO 2 R 10 , —CONR 8 R 9 ,
  • Group X C1-C4 alkoxy group optionally substituted with a halogen atom, —CO 2 R 16 (wherein R 16 represents a C1-C4 alkyl group optionally substituted with halogen), a cyano group, and A group consisting of halogen atoms.
  • Group Y a group consisting of a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, a cyano group, a nitro group, and a halogen atom.
  • R 10 is a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom
  • R 15 is a C1-C4 chain hydrocarbon group substituted with a halogen atom
  • a 1 and A 2 are the same or different and represent a nitrogen atom or ⁇ CH—, m represents 0, 1 or 2;
  • R 1, R 2, R 3 and R 4 are the same or different, group optionally substituted with a C1-C6 chain hydrocarbon group selected from the group X, optionally substituted with a group selected from the group X
  • a C3-C6 alicyclic hydrocarbon group, a phenyl group optionally substituted with a group selected from group Y, a benzyl group optionally substituted with a group selected from group Y, a group selected from group Y in substituted heterocycle may also be 5-membered optionally heterocyclic group or 6-membered heterocyclic group, -OR 8, -NR 8 R 9 , -NR 8 C (O) R 9, -S (O) m R 8, -SO 2 Cl, —SO 2 NR 8 R 9 , —CO 2 R 10 , —CONR 8 R 9 , —CONR 10
  • Group X C1-C4 alkoxy group optionally substituted with a halogen atom, —CO 2 R 16 (wherein R 16 represents a C1-C4 alkyl group optionally substituted with halogen), a cyano group, and A group consisting of halogen atoms.
  • Group Y a group consisting of a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, a cyano group, a nitro group, and a halogen atom.
  • the condensed imidazole compound represented by A method for controlling harmful animals which comprises applying an effective amount of at least one selected pyrethroid compound to harmful animals or habitats of harmful animals.
  • R 10 is a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom
  • R 15 is a C1-C4 chain hydrocarbon group substituted with a halogen atom
  • a 1 and A 2 are the same or different and represent a nitrogen atom or ⁇ CH—, m represents 0, 1 or 2; R 1 , R 2 , R 3 and R 4 are the same or different and are substituted with a group selected from group X, a C1-C6 chain hydrocarbon group which may be substituted with a group selected from group X
  • a C3-C6 alicyclic hydrocarbon group, a phenyl group optionally substituted with a group selected from group Y, a benzyl group optionally substituted with a group selected from group Y, a group selected from group Y in substituted heterocycle may also be 5-membered optionally heterocyclic group or 6-membered heterocyclic group, -OR 8, -NR 8 R 9 , -NR 8 C (O) R 9, -S (O) m R 8, -SO 2 Cl, —SO 2 NR 8 R 9 , —CO 2 R 10 , —CONR 8 R 9 ,
  • Group X C1-C4 alkoxy group optionally substituted with a halogen atom, —CO 2 R 16 (wherein R 16 represents a C1-C4 alkyl group optionally substituted with halogen), a cyano group, and A group consisting of halogen atoms.
  • Group Y a group consisting of a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, a cyano group, a nitro group, and a halogen atom.
  • R 10 is a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom
  • R 15 is a C1-C4 chain hydrocarbon group substituted with a halogen atom
  • the pest control composition according to the present invention has an excellent control effect on pests.
  • the pest control composition according to the present invention may be referred to as a condensed imidazole compound represented by the formula (1) (hereinafter referred to as “the present active compound”). .) And at least one selected from the group consisting of esfenvalerate, fenpropatoline, fenvalerate, alpha cypermethrin, bifenthrin, cypermethrin, deltamethrin, etofenprox, lambda cihalothrin, permethrin, tefluthrin, zetacypermethrin.
  • a kind of pyrethroid compound (hereinafter sometimes referred to as “the present pyrethroid compound”) is contained as an active ingredient.
  • halogen atom means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • C2-C5 represented by “C2-C5 alkoxycarbonyl group” means that the number of carbon atoms constituting the entire alkoxycarbonyl group is in the range of 2 to 5. .
  • Examples of the “C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X” represented by R 1 , R 2 , R 3 or R 4 include a methyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, 2-methoxyethyl group, 2- Ethoxyethyl group, 2-propoxyethyl group, 2-isopropoxyethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, cyanomethyl group, dicyanomethyl group, 1- Cyanoethyl group, 1,1-dicyanoethyl
  • Examples of the “C3-C6 alicyclic hydrocarbon group which may be substituted with a group selected from group X” represented by R 1 , R 2 , R 3 or R 4 include, for example, a cyclopropyl group, cyclobutyl group, cyclopentyl Groups and cyclohexyl groups.
  • Examples of the “phenyl group optionally substituted with a group selected from group Y” represented by R 1 , R 2 , R 3 or R 4 include a phenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4- Chlorophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2- (trifluoromethyl) phenyl group, 3 -(Trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 2-cyanophenyl group, 3-cyanophenyl group and 4 -Cyanophenyl group and the like.
  • Examples of the “benzyl group optionally substituted with a group selected from group Y” represented by R 1 , R 2 , R 3 , R 4 , R 8 or R 9 include a benzyl group, 2-chlorobenzyl group, Examples include 3-chlorobenzyl group, 4-chlorobenzyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2-methoxybenzyl group, 3-methoxybenzyl group and 4-methoxybenzyl group. .
  • heterocyclic group in the “5-membered heterocyclic group or 6-membered heterocyclic group optionally substituted with a group selected from group Y” represented by R 1 , R 2 , R 3 or R 4 is heterocycle Represents a ring compound residue
  • examples of the “5-membered heterocyclic group or 6-membered heterocyclic group optionally substituted with a group selected from group Y” include a pyrrolidin-1-yl group and a tetrahydrofuran-2-yl group.
  • 5-membered saturated heterocyclic groups such as; 6-membered saturated heterocyclic groups such as piperidyl group, morpholyl group, thiomorpholyl group and 4-methylpiperazin-1-yl group; Pyrazol-1-yl group, 3-chloro-pyrazol-1-yl group, 3-bromopyrazol-1-yl group, 3-nitropyrazol-1-yl group, 3-methylpyrazol-1-yl group, 3- (Trifluoromethyl) pyrazol-1-yl group, 4-methylpyrazol-1-yl group, 4-chloropyrazol-1-yl group, 4-bromopyrazol-1-yl group, 4-cyanopyrazol-1-yl Group, imidazol-1-yl group, 4- (trifluoromethylimidazole) -1-yl group, pyrrol-1-yl group, 1,2,4-triazol-1-yl group, 3-chloro-1,2 , 4-triazol-1-yl group, 1,2,
  • Examples of the “C1-C4 chain hydrocarbon group optionally substituted with a halogen atom” represented by R 5 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group
  • a C1-C4 alkyl group optionally substituted with a halogen atom such as a tert-butyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group and a pentafluoroethyl group
  • a C2-C4 alkenyl group optionally substituted with a halogen atom such as a vinyl group, an allyl group, or a 3,3-difluoroallyl group
  • C2-C4 alkynyl group optionally substituted with a halogen atom such as propargyl group and 4,4,4-trifluoro-2-butynyl group.
  • Examples of the “C1-C4 chain hydrocarbon group substituted with a halogen atom” represented by R 6 or R 7 include, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 2,2,2-trifluoroethyl Group, pentafluoroethyl group, heptafluoropropyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, heptafluoroisopropyl group, nonafluorobutyl group, nonafluoroisobutyl group, nonafluoro-sec -Butyl group and nonafluoro-tert-butyl group.
  • R 6 and R 7 and are attached, R 6 and as a "5- or 6-membered ring substituted with halogen atom" R 7 carbon atom attached is shown together, for example the following Examples include rings represented by formulas (a) to (j). (Here, A 6 represents a carbon atom to which R 6 is bonded, and A 7 represents a carbon atom to which R 7 is bonded.)
  • Examples of the “C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X” represented by R 8 or R 9 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, Pentyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, hexyl group, fluoromethyl group, Difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group,
  • Examples of the “C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from group X” represented by R 8 or R 9 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and 2 -Cyclohexenyl group.
  • Examples of the “phenyl group optionally substituted with a group selected from group Y” represented by R 8 and R 9 include a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, Examples include 4- (trifluoromethyl) phenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl group, and 4-nitrophenyl group.
  • Examples of the “5-membered heterocyclic group or 6-membered heterocyclic group optionally substituted with a group selected from group Y” represented by R 8 or R 9 include 5-thienyl group and 3-thienyl group.
  • Examples of the “C1-C4 alkyl group optionally substituted with a halogen atom” represented by R 10 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples thereof include a butyl group, a trifluoromethyl group, and a pentafluoroethyl group.
  • Examples of the “C1-C4 alkyl group optionally substituted with a halogen atom” represented by R 11 or R 12 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group and the like.
  • Examples of the “C2-C5 alkoxycarbonyl group” represented by R 11 or R 12 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group. Examples thereof include a nyl group and a tert-butoxycarbonyl group.
  • Examples of the “C1-C3 chain hydrocarbon group optionally substituted with a halogen atom” represented by R 13 or R 14 include, for example, methyl group, ethyl group, propyl group, isopropyl group, fluoromethyl group, difluoromethyl group
  • a C1-C3 alkyl group optionally substituted with a halogen atom such as a trifluoromethyl group, a 2,2,2-trifluoroethyl group and a pentafluoroethyl group
  • a C2-C3 alkenyl group optionally substituted with a halogen atom such as a vinyl group, 2-propenyl group, 3,3-difluoro-2-propenyl group and 3,3-dichloro-2-propenyl group
  • Examples thereof include C2-C3 alkynyl groups which may be substituted with halogen atoms such as ethynyl group and propargyl group.
  • Examples of the “C1-C4 chain hydrocarbon group substituted with a halogen atom” represented by R 15 include, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a penta Fluoroethyl group, heptafluoropropyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, heptafluoroisopropyl group, nonafluorobutyl group, nonafluoroisobutyl group, nonafluoro-sec-butyl group And a C1-C4 alkyl group substituted with a halogen atom such as a nonafluoro-tert-butyl group; A C2-C4 alkenyl group substituted with a halogen atom such as a 3,3-difluoroallyl group and a pentafluoroallyl group;
  • Examples of the “C1-C4 alkyl group optionally substituted with a halogen atom” for R 16 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and the like. Examples thereof include a butyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluoroethyl group.
  • a 1 is ⁇ CH—
  • a 2 is a nitrogen atom or ⁇ CH—
  • m is 0, 1 or 2
  • R 1 , R 2 , R 3 and R 4 are the same.
  • a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, —OR 8 , —S (O) m R 8 , —CO 2 R 10 , cyano group, nitro group A halogen atom or a hydrogen atom
  • R 5 is a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, or a cyclopropyl group optionally substituted with a halogen atom
  • R 6 is A C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR 15 or —S (O) m R 15
  • R 7 is a hydrogen atom
  • R 8 is substituted with a group selected from group X
  • R 10 is a C1-C4 alkyl group optionally substituted with a halogen atom or a hydrogen atom
  • R 15 is a C1-C4 chain hydrocarbon group substituted with a halogen atom.
  • a 1 is —CH ⁇
  • R 1 , R 2 , R 3 and R 4 are the same or different and may be substituted with a halogen atom, a C1-C6 chain hydrocarbon group, —OR 8 , —S (O) m R 8 , —CO 2 R 10 , a halogen atom or a hydrogen atom
  • R 8 is a C1-C6 chain hydrocarbon group optionally substituted with a halogen atom
  • R 10 is a C1-C4 alkyl group which may be substituted with a halogen atom
  • R 5 may be substituted with a C1-C4 chain hydrocarbon group which may be substituted with a halogen atom or a halogen atom.
  • R 6 is a C1-C4 chain hydrocarbon group or -OR 15 substituted with a halogen atom
  • R 7 is a hydrogen atom, C1-C4 which R 15 is substituted with a halogen atom Condensed imidazole which is a chain hydrocarbon group and n is 0 Compound;
  • a 1 is —CH ⁇
  • R 1 , R 2 , R 3 and R 4 are the same or different and may be a C1-C6 alkyl group optionally substituted with a halogen atom, a halogen atom C1-C6 alkoxy group which may be substituted, C1-C6 alkylthio group which may be substituted with a halogen atom, C1-C6 alkylsulfinyl group which may be substituted with a halogen atom, A C1-C6 alkylsulfonyl group which may be substituted, a (C1-C4 alkoxy) carbonyl group optionally substituted with a halogen atom, a halogen atom or a hydrogen atom, and R 5 may be substituted with a halogen atom.
  • a C1-C4 alkyl group which is an alkyl group or a cyclopropyl group optionally substituted with a halogen atom, and R 6 is substituted with a halogen atom
  • a condensed imidazole compound which is a C1-C4 alkoxy group optionally substituted with a halogen atom
  • R 7 is a hydrogen atom
  • n is 0;
  • a 1 is —CH ⁇
  • R 1 is a hydrogen atom
  • R 2 is a hydrogen atom
  • R 3 and R 4 are the same or different and may be substituted with a halogen atom.
  • R 5 is a halogen atom in substituted substituted by C1-C4 may be an alkyl group or
  • a 1 is —CH ⁇
  • R 1 is a hydrogen atom
  • R 2 is a hydrogen atom
  • R 3 is a C1-C6 alkyl group optionally substituted with a halogen atom, halogen C1-C6 alkoxy group optionally substituted with an atom, C1-C6 alkylthio group optionally substituted with a halogen atom, C1-C6 alkylsulfinyl group optionally substituted with a halogen atom, substituted with a halogen atom
  • R 4 is a hydrogen atom
  • R 5 is a halogen atom substituted in substituted substituted by C1-C4 may be an alkyl group or a halogen atom
  • a 1 is —CH ⁇
  • a 1 is a nitrogen atom
  • R 1 is a hydrogen atom
  • R 2 is a hydrogen atom
  • R 3 is substituted with a halogen atom.
  • R 4 is a hydrogen atom
  • R 5 is a C1-C4 alkyl group which may be substituted with a halogen
  • This active compound which is an active ingredient in this invention composition is demonstrated.
  • This active compound can be produced, for example, by the following (Production Method 1) to (Production Method 28).
  • reaction method 1 Among the active compounds, compound (4) in which n is 0 can be produced by reacting compound (2) and compound (3) in the presence of a base. Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7, A 1 and A 2 are as defined above. ] The reaction is usually performed in the presence of a solvent.
  • solvent used in the reaction examples include tetrahydrofuran (hereinafter sometimes referred to as THF), ethers such as ethylene glycol dimethyl ether and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, toluene , Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide (hereinafter sometimes referred to as DMF) ), Sulfoxides such as dimethyl sulfoxide (hereinafter sometimes referred to as DMSO), nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • THF tetrahydrofuran
  • ethers such as ethylene glycol dimethyl ether and 1,4-dioxane
  • the compound (3) is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (2).
  • the reaction temperature is usually in the range of 30 to 200 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4) can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer.
  • the isolated compound (4) can be further purified by chromatography, recrystallization and the like.
  • reaction method 2 Among the active compounds, compound (4) in which n is 0 can be produced by reacting compound (2) with compound (5).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , A 1 and A 2 represent the same meaning as described above.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene.
  • Halogenated hydrocarbons such as ethyl acetate, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF, sulfoxides such as DMSO, nitrogen-containing aromatic compounds such as pyridine and quinoline, and the like
  • This reaction can also be carried out by adding a base as necessary.
  • the base used in the reaction include hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, carbonates such as sodium carbonate and potassium carbonate, sulfites such as sodium sulfite and potassium sulfite, and mixtures thereof.
  • the compound (5) is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (2).
  • the base is usually used at a ratio of 1 to 5 mol per 1 mol of compound (2).
  • the reaction temperature is usually in the range of 30 to 200 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4) can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene.
  • ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane
  • aliphatic hydrocarbons such as hexane, heptane, and octane
  • aromatic hydrocarbons such as toluene and xylene
  • chlorobenzene chlorobenzene.
  • Halogenated hydrocarbons such as ethyl acetate, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF, sulfoxides such as DMSO, nitrogen
  • Examples of the dehydrating condensing agent used in the reaction include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter sometimes referred to as WSC) and carbodiimides such as 1,3-dicyclohexylcarbodiimide. It is done.
  • This reaction can also be performed by adding a catalyst as needed.
  • Examples of the catalyst used for the reaction include 1-hydroxybenzotriazole.
  • the compound (6) is usually used in a proportion of 1 to 3 mol
  • the dehydrating condensing agent is usually used in a proportion of 1 to 5 mol
  • the catalyst is usually used in a proportion of 0.01 to 0.1 mol per 1 mol of the compound (2). It is done.
  • the reaction temperature is usually in the range of 30 to 200 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4) can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer.
  • the isolated compound (4) can be further purified by chromatography, recrystallization and the like.
  • reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene.
  • halogenated hydrocarbons such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF, sulfoxides such as DMSO, and mixtures thereof.
  • an acid or a dehydrating agent can be used as necessary.
  • the acid used for the reaction include sulfonic acids such as p-toluenesulfonic acid, and carboxylic acids such as acetic acid.
  • the dehydrating agent used for the reaction include phosphorus oxychloride, acetic anhydride, trifluoroacetic anhydride, and the like. Can be mentioned.
  • the dehydrating agent is usually used in an amount of 1 mol to excess with respect to 1 mol of the compound (7).
  • the reaction temperature is usually in the range of 30 to 200 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-a) can be produced by reacting the compound (8) and the compound (9) in the presence of a base.
  • R 31 represents a chlorine atom or a fluorine atom
  • R 32 represents a group A C1-C6 chain hydrocarbon group optionally substituted with a group selected from X, a C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from Group X, a group selected from Group Y
  • the reaction is usually performed in the presence of a solvent, but compound (9) may be used in an amount of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. And sulfoxides such as these and mixtures thereof.
  • the base used for the reaction include alkali metal hydrides such as sodium hydride.
  • the compound (9) is usually used in a proportion of 1 mol to excess and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (8).
  • the reaction temperature of the reaction is usually in the range of 0 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-a) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-a) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-b) can be produced by reacting the compound (8) and the compound (10) in the presence of a base.
  • a base a base
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 31 , R 32 , A 1 and A 2 represent the same meaning as described above.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like.
  • the base used for the reaction examples include alkali metal hydrides such as sodium hydride.
  • the compound (10) is usually used in a proportion of 1 to 10 mol and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (8).
  • the reaction temperature of the reaction is usually in the range of 0 to 150 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound (4-b) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-b) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-c) can be produced by reacting the compound (4-b) in the presence of an oxidizing agent.
  • an oxidizing agent used for reaction, sodium periodate is mentioned, for example.
  • the oxidizing agent is usually used in a proportion of 1 to 3 mol per 1 mol of the compound (4-b).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 80 ° C., and the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the compound (4-d) can be produced by reacting the compound (4-b) in the presence of an oxidizing agent.
  • an oxidizing agent for reacting the compound (4-b) in the presence of an oxidizing agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include carboxylic acid peroxides such as 3-chloroperbenzoic acid.
  • the oxidizing agent is usually used at a ratio of 2 to 4 moles relative to 1 mole of the compound (4-b).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 30 ° C., and the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the compound (4-e) is produced by reacting the compound (11) with an acid anhydride represented by the compound (12) or an acid chloride represented by the compound (13). can do.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , A 1 and A 2 represent the same meaning as described above.
  • the reaction is usually performed in the presence of a solvent, but the amount of the compound (12) may be used.
  • solvent used in the reaction examples include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. And sulfoxides such as pyridine, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof. This reaction can also be carried out by adding a base as necessary.
  • ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane
  • aromatic hydrocarbons such as toluene and xylene
  • nitriles such as acetonitrile
  • acid amides such as DMF, DMSO, and the like.
  • sulfoxides such as pyridine, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • This reaction can also be carried out by adding
  • Examples of the base used in the reaction include alkali metal hydrides such as sodium hydride, carbonates such as potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing compounds such as pyridine and 4-dimethylaminopyridine. Aromatic compounds and the like can be mentioned.
  • the compound (12) or the compound (13) is usually used in a proportion of 1 to 10 mol and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (11).
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-e) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-e) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-f) is obtained by reacting the compound (14) and the boronic acid compound represented by the compound (15) or the tin compound represented by the compound (16) in the presence of a palladium compound. It can manufacture by making it react.
  • R 1, R 2, R 4, R 5, R 6, R 7, A 1 and A 2 are as defined above, L represents a bromine atom or an iodine atom, R 3x is a phenyl group optionally substituted with a group selected from group Y, a 5-aromatic heterocyclic group or a 6-membered aromatic heterocyclic group optionally substituted with a group selected from group Y (provided that pyridine An aromatic heterocyclic group bonded to a ring and a carbon atom).
  • the reaction is usually performed in the presence of a solvent.
  • solvent used in the reaction examples include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, alcohols such as methanol and ethanol, aliphatic hydrocarbons such as hexane, heptane and octane, toluene, xylene and the like. Aromatic hydrocarbons, acid amides such as DMF, water, and mixtures thereof.
  • Examples of the palladium compound used in the reaction include palladium acetate, tetrakistriphenylphosphine palladium, ⁇ 1,1′-bis (diphenylphosphino) ferrocene ⁇ dichloropalladium methylene chloride complex, and bis (triphenylphosphine) palladium dichloride. .
  • the compound (15) or the compound (16) is usually used in a proportion of 0.5 to 5 mol, and the palladium compound is usually used in a proportion of 0.001 to 0.1 mol with respect to 1 mol of the compound (14).
  • a base inorganic salts such as sodium acetate, potassium acetate, potassium carbonate, tripotassium phosphate, sodium hydrogencarbonate, etc.
  • a phase transfer catalyst tetrabutylammonium bromide, benzyltriethyl, etc.
  • a quaternary ammonium salt such as ammonium bromide.
  • the reaction temperature of the reaction is usually in the range of 50 to 120 ° C.
  • the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound (4-f) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-f) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-g) can be produced by reacting the compound (8) and the compound (17) in the presence of a base.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 31 , A 1 and A 2 represent the same meaning as described above, and R 3y is substituted with a group selected from group Y Represents a 5-membered heterocyclic group or a 6-membered heterocyclic group (which is limited to a heterocyclic group bonded to a pyridine ring on a nitrogen atom).
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. And the like, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal hydrides such as sodium hydride and carbonates such as potassium carbonate.
  • the compound (17) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol per 1 mol of the compound (8).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-g) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-g) can be further purified by chromatography, recrystallization and the like.
  • the oxidizing agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (4).
  • the reaction temperature of the reaction is usually in the range of 40 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • compound (4-h) can be produced by reacting compound (21) and compound (10) in the presence of a base.
  • a base a base
  • R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 31 , R 32 , A 1 and A 2 represent the same meaning as described above.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like.
  • the base used for the reaction examples include alkali metal hydrides such as sodium hydride.
  • the compound (10) is usually used in a proportion of 1 to 10 mol and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (21).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-h) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-h) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-j) can be produced by reacting the compound (4-h) in the presence of an oxidizing agent.
  • an oxidizing agent e.g., a compound having a molecular weight of about 100 kDa.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, acetic acid, water and These mixtures are mentioned.
  • Examples of the oxidizing agent used in the reaction include sodium periodate.
  • the oxidizing agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (4-h).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 80 ° C., and the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the compound (4-k) can be produced by reacting the compound (4-h) in the presence of an oxidizing agent.
  • an oxidizing agent for reacting the compound (4-h) in the presence of an oxidizing agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include carboxylic acid peroxides such as 3-chloroperbenzoic acid.
  • the oxidizing agent is usually used at a ratio of 2 to 4 moles relative to 1 mole of the compound (4-h).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 30 ° C., and the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the compound (4-k) can be produced by reacting the compound (4-j) in the presence of an oxidizing agent.
  • an oxidizing agent for reacting the compound (4-j) in the presence of an oxidizing agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include carboxylic acid peroxides such as 3-chloroperbenzoic acid.
  • the oxidizing agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (4-j).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 30 ° C., and the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the compound (4-p) can be produced by reacting the compound (8) with a cyanide.
  • a cyanide a compound that has been modified by reacting the compound (8) with a cyanide.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 31 , A 1 , and A 2 represent the same meaning as described above.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, acid amides such as DMF and 1-methyl-2-pyrrolidinone, sulfoxides such as DMSO, and mixtures thereof. Can be mentioned.
  • Examples of the cyanide used in the reaction include sodium cyanide and potassium cyanide. This reaction can also be performed by adding a catalyst as needed. Examples of the catalyst used in the reaction include crown ethers such as 15-crown-5 and 18-crown-6.
  • the cyanide is usually used in a proportion of 1 to 3 mol and the catalyst is usually used in a proportion of 0.01 to 0.5 mol with respect to 1 mol of the compound (8).
  • the reaction temperature of the reaction is usually in the range of 0 to 200 ° C., and the reaction time is usually in the range of 0.1 to 12 hours.
  • the compound (4-p) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-p) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-q) can be produced by hydrolyzing the compound (4-p) in the presence of a base.
  • a base a base
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include alcohols such as methanol and ethanol, water, and mixtures thereof.
  • the base used in the reaction include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and barium hydroxide.
  • the base is usually used in a proportion of 1 to 3 mol per 1 mol of the compound (4-p).
  • the reaction temperature of the reaction is usually in the range of 0 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-q) is isolated by performing post-treatment operations such as acid precipitation or neutralization of the reaction mixture with an acid, extraction with an organic solvent, and drying and concentration of the organic layer. be able to.
  • the isolated compound (4-q) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-r) can be produced by reacting the compound (4-p) with hydrogen peroxide in the presence of a base.
  • a base e.g., sulfoxides such as DMSO, water, and mixtures thereof.
  • the solvent used in the reaction include sulfoxides such as DMSO, water, and mixtures thereof.
  • the base used in the reaction include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and carbonates such as sodium carbonate and potassium carbonate.
  • Hydrogen peroxide is usually used in a proportion of 1 to 5 mol and base is usually used in a proportion of 1 to 5 mol with respect to 1 mol of the compound (4-p).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-r) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-r) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-s) can be produced by reacting the compound (22) and the compound (23).
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , A 1 and A 2 represent the same meaning as described above.
  • the reaction is usually performed in the presence of a base, and usually in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. Sulfoxides such as pyridine, nitrogen-containing aromatic compounds such as pyridine and quinoline, water, and mixtures thereof.
  • Examples of the base used in the reaction include carbonates such as potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
  • the compound (23) is usually used in a proportion of 1 mol to excess and the base is usually used in 1 mol to excess with respect to 1 mol of the compound (22).
  • the reaction can also be carried out without using the above base.
  • an excess amount of a liquid tertiary amine such as triethylamine or diisopropylethylamine or a liquid nitrogen-containing aromatic compound such as pyridine is used as a base, the reaction can be performed without using the above solvent.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-s) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-s) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-s) can be produced by reacting the compound (4-q) and the compound (23) in the presence of a dehydrating condensing agent.
  • a dehydrating condensing agent R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , A 1 and A 2 represent the same meaning as described above.
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene.
  • ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane
  • aliphatic hydrocarbons such as hexane, heptane, and octane
  • aromatic hydrocarbons such as toluene and xylene
  • chlorobenzene chlorobenzene.
  • Halogenated hydrocarbons such as ethyl acetate, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF, sulfoxides such as DMSO, nitrogen
  • Examples of the dehydrating condensing agent used in the reaction include carbodiimides such as WSC and 1,3-dicyclohexylcarbodiimide.
  • This reaction can also be performed by adding a catalyst as needed.
  • Examples of the catalyst used for the reaction include 1-hydroxybenzotriazole. 1 to 3 moles of compound (23), 1 to 5 moles of dehydration condensing agent, and 0.01 to 0.1 moles of catalyst with respect to 1 mole of compound (4-q) Used in
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-q) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-s) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-t) can be produced by reacting the compound (4-q) with the compound (24) in the presence of an acid.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , A 1 and A 2 represent the same meaning as described above, and R 33 may be substituted with a halogen atom. Represents an alkyl group.
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and halogenated hydrocarbons such as chlorobenzene. And mixtures thereof.
  • Examples of the acid used in the reaction include mineral acids such as hydrochloric acid and sulfuric acid, and organic acids such as p-toluenesulfonic acid.
  • the compound (24) is usually used in an amount of 1 mol to excess and the acid is usually used in an amount of 0.01 mol to 1 mol with respect to 1 mol of the compound (4-q).
  • the reaction can be carried out without using the above solvent.
  • the reaction temperature of the reaction is usually in the range of 0 to 200 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-t) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-t) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-u) can be produced by reacting the compound (8) with a sulfurizing agent such as sodium hydrosulfide.
  • a sulfurizing agent such as sodium hydrosulfide.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 31 , A 1 , and A 2 represent the same meaning as described above.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like.
  • Sulfoxides such as pyridine, nitrogen-containing aromatic compounds such as pyridine and quinoline, water, and mixtures thereof.
  • a sulfurizing agent such as sodium hydrosulfide is usually used at a ratio of 1 mol to 3 mol with respect to 1 mol of the compound (8).
  • the reaction temperature of the reaction is usually in the range of 0 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-u) can be isolated by post-treatment such as acid precipitation or extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-u) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-w) can be produced by reacting the compound (4-u) and the compound (25) in the presence of a base.
  • a base e.g., N-(2-aminoethyl)
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 32 , A 1 , A 2 and L represent the same meaning as described above.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like.
  • the base used in the reaction examples include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, inorganic bases such as sodium carbonate and potassium carbonate, or organic bases such as triethylamine. Etc.
  • the base is usually used at a ratio of 1 to 3 mol per 1 mol of the compound (4-u).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-w) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-w) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-w) can be produced by reacting the compound (4-u) with a chlorinating agent such as trimethylsilyl chloride in the presence of an oxidizing agent such as potassium nitrate.
  • a chlorinating agent such as trimethylsilyl chloride
  • an oxidizing agent such as potassium nitrate.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , A 1 and A 2 represent the same meaning as described above.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include halogenated hydrocarbons such as methylene chloride and chloroform, aromatic halides such as chlorobenzene, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof.
  • An oxidizing agent such as potassium nitrate is usually used at a ratio of 1 to 5 moles
  • a chlorinating agent such as trimethylsilyl chloride is usually used at a ratio of 1 to 5 moles relative to 1 mole of the compound (4-u).
  • the reaction temperature of the reaction is usually in the range of 0 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-w) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-w) can be further purified by recrystallization or the like.
  • the compound (4-y) can be produced by reacting the compound (4-w) with the compound (23).
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , A 1 and A 2 represent the same meaning as described above.
  • the reaction is usually carried out in the presence of a solvent and usually in the presence of a base.
  • the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof.
  • Examples of the base used in the reaction include inorganic bases such as sodium carbonate and potassium carbonate, organic bases such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and quinoline.
  • Compound (23) is usually used in a proportion of 1 mol to excess and base is usually used in a proportion of 1 mol to excess with respect to 1 mol of compound (4-w).
  • the reaction can also be carried out without using the above base.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-y) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (4-y) can be further purified by chromatography, recrystallization and the like.
  • the catalyst is usually used in the proportion of 0.01 mol to 0.1 per mol of compound (26).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (4-z) is isolated by performing post-treatment operations such as removing the catalyst by filtering the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. can do.
  • the isolated compound (4-z) can be further purified by chromatography, recrystallization and the like.
  • the compound (4-d) can be produced by reacting the compound (4-c) in the presence of an oxidizing agent.
  • an oxidizing agent for reacting the compound (4-c) in the presence of an oxidizing agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include carboxylic acid peroxides such as 3-chloroperbenzoic acid.
  • the oxidizing agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (4-c).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 30 ° C., and the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried,
  • a reducing agent for example, sodium sulfite, sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the intermediate of the active compound can be produced, for example, by the following method.
  • Compound (2) can be produced by the following method. [Wherein, R 5 , R 6 , R 7 , A 1 and A 2 represent the same meaning as described above. ]
  • Compound (M2) can be produced by reacting compound (M1) with a nitrating agent. The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as chloroform, acetic acid, concentrated sulfuric acid, concentrated nitric acid, water, and mixtures thereof. Examples of the nitrating agent used in the reaction include concentrated nitric acid.
  • the nitrating agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (M1).
  • the reaction temperature of the reaction is usually in the range of ⁇ 10 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M2) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M2) can be further purified by chromatography, recrystallization and the like.
  • Compound (2) can be produced by reacting compound (M2) with hydrogen in the presence of a hydrogenation catalyst.
  • the reaction is usually performed in a hydrogen atmosphere at 1 to 100 atm, usually in the presence of a solvent.
  • the solvent used in the reaction include ethers such as THF and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, water, and a mixture thereof.
  • the hydrogenation catalyst used in the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide.
  • Hydrogen is usually used in a proportion of 3 mol, and a hydrogenation catalyst is usually used in a proportion of 0.001 to 0.5 mol per mol of the compound (M1).
  • This reaction can also be carried out by adding an acid (such as a base) as necessary.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (2) can be isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent as necessary, and drying and concentration of the organic layer. The isolated compound (2) can be further purified by chromatography, recrystallization and the like.
  • the active compound contained in the composition of the present invention may be one kind or two or more kinds. Preferably they are 1 type or more and 3 types or less.
  • the pyrethroid compound used in combination with the active compound in the composition of the present invention will be described.
  • the pyrethroid compound is a known compound.
  • Examples of pyrethroid compounds include (1) esfenvalerate, (2) fenpropathrin, (3) fenvalerate, (4) alphacypermethrin, (5) bifenthrin. (Bifenthrin), (6) cypermethrin, (7) deltamethrin, (8) etofenprox, (9) lambda-cyhalothrin, (10) permethrin ), (11) tefluthrin, (12) zeta-cypermethrin, and the like.
  • Esfenvalerate is based on “The Pesticide Manual, 14th edition (The Pesticide Manual, teenForteenth Edition)” (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry, 2006) No. 314, which is commercially available.
  • Fenpropatrin is "The Pesticide Manual, 14th Edition (The Pesticide Manual, Forteenth Edition)" (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry, 2006) No. 353, which is commercially available.
  • Fenvalerate is "The Pesticide Manual, 14th Edition (The Pesticide Manual, Forteenth Edition)" (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society hem Society 2006, 3) And are commercially available.
  • Alphacypermethrin is the “The Pesticide Manual, 14th Edition (The Pesticide Manual, Forteenth Edition)” (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry, 2006) No. 205, which is commercially available.
  • Bifenthrin is based on “The Pesticide Manual, 14th Edition (Edition by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry,” 2006) And is commercially available.
  • Deltamethrin is "The Pesticide Manual, 14th edition (The Pesticide Manual, Forteenth) Edition)" (edited by Clive Tomlin, published Crop Protection Council and The Royal Society Society 2006, Chemistry 26 And is commercially available.
  • Etofenprox is the “The Pesticide Manual, 14th Edition (The Pesticide Manual, Forteenth Edition)” (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry, 2006) No. 331 and is commercially available.
  • Lambda Cihalothrin is the “The Pesticide Manual, 14th Edition (Edition by Clive Tomlin, editpublished by The British Crop Protection Council and The Royal Society of 2006) No. 201 and is commercially available.
  • Teflutrin is the “The Pesticide Manual, 14th Edition (The Pesticide Manual, Forteenth Edition)” (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry9 ⁇ 2006) And is commercially available.
  • the Zetasipepermethrin is the “The Pesticide Manual, 14th Edition (The Pesticide Manual, Forteenth Edition)” (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry) No. 208 and is commercially available.
  • the present pyrethroid compound contained in the composition of the present invention may be one kind or two or more kinds. Preferably they are 1 type or more and 3 types or less. Moreover, although this pyrethroid compound may exist in a stereoisomer, this invention includes each of those isomers and a mixture of those isomers.
  • the composition of the present invention contains a carrier and the like described later, and is a preparation that can be taken by an agrochemical or animal medicine.
  • the composition of the present invention comprises the present active compound and the present pyrethroid compound dissolved or dispersed in a suitable liquid carrier, the present active compound and the present pyrethroid compound mixed or adsorbed with a suitable solid carrier or ointment base.
  • the following dosage forms can be prepared by a known method such as mixing or dispersing the pyrethroid compound in a suitable gaseous carrier.
  • the above dosage forms include emulsions, liquids, microemulsions, flowables, oils, wettable powders, granular wettable powders, powders, granules, fine granules, seed coating agents, seed soaking agents, smoke agents, tablets, Microcapsules, sprays, aerosols, carbon dioxide preparations, heat transpiration agents such as mosquito coils, electric mosquito mats, liquid electric mosquito traps, EW agents, ointments, poison baits, capsules, pellets, films, injections, coating agents, Examples include resin preparations and shampoo preparations.
  • auxiliary agents for formulation such as emulsifiers, suspending agents, spreading agents, penetrating agents, wetting agents, thickening agents, stabilizers, fixing agents, binders, dispersing agents, coloring agents and the like. It may be added.
  • liquid carrier examples include water, alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (Toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, isopropyl myristate, Ethyl oleate, diisopropyl adipate, diisobutyl adipate, propylene glycol monomethyl ether acetate, etc.), n
  • Acid amides N, N-dimethylformamide, N, N-dimethylacetamide, etc.
  • halogenated hydrocarbons diichloromethane, trichloroethane, carbon tetrachloride, etc.
  • sulfoxides dimethylsulfoxide, etc.
  • propylene carbonate and vegetable oil Soybean oil, cottonseed oil, etc.
  • solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur). , Activated carbon, calcium carbonate, hydrated silica, etc.), fine fertilizers such as chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, urea, ammonium chloride, etc.) and granular materials.
  • gaseous carrier examples include fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.
  • surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyethylene glycol fatty acid ester, and the like, and alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfates, and the like.
  • nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyethylene glycol fatty acid ester, and the like
  • alkyl sulfonates alkyl benzene sulfonates, alkyl sulfates, and the like.
  • An ionic surfactant is mentioned.
  • adjuvants for preparation include fixing agents, dispersants, colorants and stabilizers, such as casein, gelatin, saccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert- And a mixture of butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).
  • fixing agents such as casein, gelatin, saccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), PAP (is
  • composition of the present invention comprises, in addition to the active compound and the pyrethroid compound, an insecticide, acaricide, nematicide, fungicide, plant hormone agent, plant growth regulator, herbicide, synergist or safener It may contain.
  • the content ratio of the active compound and the pyrethroid compound in the composition of the present invention is usually 0.01 to 95% by weight, preferably about 0.1 to 90% by weight, more preferably about 0.1% by weight, based on the total amount of the composition of the present invention. 5 to 70% by weight.
  • the content is usually about 1 to 90% by weight with respect to the total amount of the composition of the present invention. %, Preferably about 5 to 50% by weight.
  • the content is usually about 0.1 to 50% by weight, preferably about 0.1 to 20% by weight.
  • the content is usually about 0.1 to 50% by weight, preferably about 0.5 to 20% by weight.
  • the other pesticidal active ingredient for example, insecticide, herbicide, acaricide and / or fungicide
  • the content of additives other than the above active ingredients varies depending on the type or content of the pesticidal active ingredient or the dosage form of the preparation, but is usually about 0.001 to 99.9% by weight, preferably about 1 to 99% by weight. is there.
  • the surfactant is usually about 1 to 20% by weight, preferably about 1 to 15% by weight, the flow aid is about 1 to 20% by weight, and the carrier is about 1 to 90% by weight with respect to the total amount of the composition of the present invention. %, Preferably about 1 to 70% by weight can be added.
  • the surfactant is usually added in an amount of about 1 to 20% by weight, preferably about 1 to 10% by weight, and about 20 to 90% by weight of water based on the total amount of the composition of the present invention. .
  • emulsions, wettable powders, granular wettable powders, and the like can be sprayed by diluting them with water or the like (for example, about 100 to 5000 times).
  • Examples of harmful animals for which the composition of the present invention exhibits a controlling effect include the following harmful arthropods and harmful gastropods.
  • Hemiptera insects such as Japanese brown planthopper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), white-tailed planthopper (Sogatella furcifera), Nephotettix cincticeps, Nephotettix cincticeps, etc., Nephotettix cincticeps Leafhoppers, cotton aphids (Aphis gossypii), peach aphids (Myzus persicae), radish aphids (Brevicoryne brassicae), snowy aphids (Aphis spiraecola), tulip beetle aphids (Macrosiphum ⁇ euphorbiae), moths Aphids such as aphids (Rhopalosiphum padi), citrus black aphids (Toxoptera citricidus), peach beetles (Hy
  • Lepidopterous insects Chilo suppressalis, Sunpikeza (Tryporyza incertulas), Cnaphalocrocis medinalis, Noarcha derogata, Plodia interpunctella, Hula undi, Osnia Japanese medusa such as Shibatatsuga (Pediasia teterrellus), Spodoptera litura, Spodoptera exigua, Pseudaletia separata, Mamestra brassicae, Agrotis, Agrotis Heliotis genus, Helicoberpa genus moths, white butterflies (Pieris rapae) and other white moths, Adoxofis genus, Grapholita molesta, Leguminivora glycinivorella Azuki beetle (Matsumuraeses azukivora), apple wolfberry (Adoxophyes orana fasciata), tea wolfberry (Adoxophyes honmai.), Chahamaki (Homona magn
  • Thripidae pests Citrus thrips (Frankliniella occidentalis), Thrips peri, Scirtothrips dorsalis, Thrips tabaci, Thrips tabaci
  • Diptera Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus and other mosquitoes, Aedes ophegos Genus Anopheles, Chironomidae, Musca domestica, Muscina stabulans, and other species of houseflies, fly flies, sphagnum flies, fly flies, DeliaDplatura, onion flies (Agromyza oryzae), rice leaflet (Hydrellia griseola), tomato leaffly, (Liriomyza sativae), bean leaffly (Liriomyza trifolii), leafhopper (Chromatomyia horticola), etc.
  • Fruit fly such as Drosophila (Dacus cucurbitae), fruit fly such as Ceratitis capitata, fruit fly such as Drosophila, fruit fly such as Megaselia spiracularis, butterfly such as Clogmiaalbipunct (Tabanus trigonus) and other species of flies and flies.
  • Drosophila Dacus cucurbitae
  • Ceratitis capitata fruit fly
  • Drosophila fruit fly
  • Fruit fly such as Megaselia spiracularis
  • butterfly such as Clogmiaalbipunct (Tabanus trigonus) and other species of flies and flies.
  • Coleoptera pests Western Corn Rootworm (Diabrotica virgifera virgifera), corn rootworm such as southern corn rootworm (Diabrotica undecimpunctata howardi), cupreous chafer (Anomala cuprea), rufocuprea (Anomala rufocuprea), chafers such as Japanese beetle (Popillia japonica) , Weevil (Sitophilus zeamais), Green weevil (Lissorhoptrus oryzophilus), Azuki beetle (Callosobruchuys Kunststoffensis), Green weevil (Echinocnemus squameus), Cotton weevil (Anthonomus grandis) Tenebrio molitor, Tribolium castaneum, and other species, Oulema oryzae, Aulacophora femoralis, Phyllotret potato beetles such as a striolata, Colorado potato beetle (Leptinotar
  • Primordial pests Locusta migratoria, Gryllotalpalotafricana, Oxya yezoensis, Oxya japonica, crickets, etc.
  • Insect pests cat fleas (Ctenocephalides felis), dog fleas (Ctenocephalides canis), human fleas (Pulex irritans), keops mud mines (Xenopsylla cheopis), etc.
  • Lice insect pests white lice (Pediculus humanus s corporis), white lice (Phthirus pubis), cattle lice (Haematopinus eurysternus), sheep lice (Dalmalinia ovis), pig lice (Haematopinus suis), etc.
  • Hymenoptera Monomorium pharaosis, Black ants (Formica fusca ⁇ japonica), Ruriari (Ochetellus glaber), Phytomermex pieuxs, Pheidole noda, Hachiri ren (Acromyrmex spp. Such as ants, wasps, scallops, bees (Athalia rosae), Japanese bees (Athalia japonica), etc.
  • Cockroach eye pest German cockroach (Blattella germanica), Black cockroach (Periplaneta fuliginosa), American cockroach (Periplaneta americana), Great cockroach (Periplaneta brunnea), Great cockroach (Blatta orientalis), etc.
  • Termite insect pests Yamato termite (Reticulitermes speratus), termite (Coptotermes formosanus), American white termite (Incisitermes minor), scallop termite (Cryptotermes domesticus), taiwan termite (Odontotermes formosanus), red ant termite (hunsterm termite) Glyptotermes satsumensis, Glyptotermes nakajimai, Caterpillar (Glyptotermes fudamcus), White termite (Glyptotermes kodamai), Ants (Glyptotermes kushimensis), Japanese termites (pants) miyatakei), white termite (Reticulitermes flaviceps amamianus), common termite (Reticulitermes sp.), white-tailed termite (Nasutitermes takasagoensis), white-tailed termite (Pericapri termes nito
  • Nite spider mite (Tetranychusticurticae), Kanzawa spider mite (Tetranychus kanzawai), Rhizoma spider mite (Panonychus citri) Apple spider mite (Panonychus ulmi), spider mites (Aculops Tomato rustic mites (Aculops lycopersici), Chinese rustic mites (Calacarus carinatus), Chinese radish mites (Acaphylla theavagrans), Green rustic mites (Eriophyes chibaensis), apple ticks (Aculus Desiendali), lysid mites, lysid mites Japanese spider mites (Brevipalpus phoenicis) and other spider mites, genus mite, Haemaphysalis longicornis, yamato tick (Haemaphysalis flava), Thai winged tick (Dermacentor taiwanicus), T
  • Lip and limb class Thereuonema hilgendorfi, Scolopendra subspinipes, etc. Double-legged class: Japanese red millipede (Oxidus gracilis), Japanese red millipede (Nedyopus tambanus). Isopods: Armadillidium vulgare, etc. Gastropods: Limax marginatus, Limax flavus, etc.
  • the pest control method according to the present invention applies an effective amount of the active compound and the pyrethroid compound to the pest or the habitat of the pest. To do.
  • an effective amount of the present active compound and the present pyrethroid compound is applied to a plant, soil for cultivating plants, hydroponics solution, medium, or the like.
  • the pest control method can control harmful animals.
  • the present active compound and the present pyrethroid compound can be applied as they are without adding any other components, and the present active compound and the present pyrethroid compound and the above-mentioned insecticides, acaricides, and nematicides.
  • the active compound and the pyrethroid compound may be applied separately at the same time, but are usually applied as the composition of the present invention from the viewpoint of simplicity during application.
  • habitats for harmful animals include plants, paddy fields, dry fields, fields, tea gardens, orchards, non-agricultural lands, houses, seedling trays and seedling boxes, seedling culture soil and seedling mats, hydroponic liquids in hydroponic farms, etc. It is done.
  • plants to be applied include foliage, seeds, seed pods, bulbs, and seedlings.
  • the bulb means a bulb, a bulb, a rhizome, a tuber, a tuberous root, and a root support body.
  • the active compound and the pyrethroid compound are applied to a harmful animal, a habitat of the harmful animal, etc. by contacting or ingesting the harmful animal with the same method as a conventional harmful animal control agent. be able to.
  • application methods include spraying treatment, soil treatment, seed treatment, and hydroponic liquid treatment.
  • the spraying treatment is, for example, a treatment that exerts a controlling effect on harmful animals by spraying active ingredients (the active compound and the pyrethroid compound) on the surface of the plant such as foliage spraying, trunk spraying, etc. Is the method.
  • the above-mentioned soil treatment is, for example, a treatment that directly controls harmful animals by giving an active ingredient to the rhizosphere of the plant to be protected, or controls the harmful animals by penetrating and transferring the active ingredients to the inside of the plant. Is the method.
  • the above-mentioned soil treatment includes planting hole treatment, plant source treatment, grooving treatment, rowing treatment, rowing treatment, full surface treatment, side row treatment, water surface treatment, other soil spraying treatment, and other irrigation. Processing, seedling box processing, seedling tray processing, seedbed processing, bed soil mixing processing, and the like can be mentioned.
  • the seed treatment is, for example, a treatment method that exerts a controlling effect on harmful animals by treating the seed, seed pod or bulb of the plant to be protected directly or in the vicinity thereof with an active ingredient.
  • Specific examples of the seed treatment include spraying, smearing, dipping, impregnation, coating, film coating, and pellet coating.
  • the above-mentioned hydroponic liquid treatment means, for example, that the plant is harmful by treating the hydroponic liquid etc. with the active ingredient in order to infiltrate and transfer the active ingredient from the root of the plant to be protected to the inside of the plant. This is a treatment method that protects animals from damage.
  • Specific examples of the hydroponic liquid treatment include mixing a hydroponic liquid and mixing a hydroponic liquid.
  • the pest control method of the present invention can be implemented in agricultural land such as fields, paddy fields, lawns, orchards, or non-agricultural land.
  • this active compound and this pyrethroid compound are used for the control of harmful animals in the agricultural field
  • the dosage of this active compound and this pyrethroid compound is the type and extent of occurrence of harmful animals to be controlled, the form of formulation, and the time of application.
  • it can be varied widely, but it is generally 1 to 10000 g per 10,000 m 2 .
  • Emulsions, wettable powders, flowables and the like are usually diluted with water so that the concentration of the active compound and the pyrethroid compound is 0.01 to 10000 ppm.
  • Granules, powders and the like are usually used as they are. Apply.
  • the active compound, the pyrethroid compound and the water dilution thereof may be sprayed directly on harmful animals or plants, or may be subjected to the above-mentioned soil treatment.
  • the active compound and the pyrethroid compound can be applied by a method such as wrapping around a plant as a resin preparation processed into a sheet or string, stretching it in the vicinity of the plant, or laying it on the stock soil.
  • composition of the present invention can be used in farmland where the following “crop” is cultivated.
  • Agricultural crops corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, etc.
  • Vegetables Solanum vegetables (eggplants, tomatoes, peppers, peppers, potatoes, etc.), cucurbits (cucumbers, pumpkins, zucchini, watermelons, melons, etc.), cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage) , Mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, shungiku, artichokes, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus), celery family vegetables (carrot, parsley, celery, American boofish, etc.) ), Red crustacean vegetables (spinach, chard, etc.), persimmon vegetables (perilla, mint, basil, etc.), strawberry, sweet potato, yam, taro Fruit trees: berries (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, ume, sweet cherry, apricots, prune
  • Trees other than fruit trees tea, mulberry, flowering trees (Satsuki, camellia, hydrangea, sasanqua, shikimi, sakura, yurinoki, crape myrtle, eustoma, etc.), roadside trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak) , Poplar, redwood, fu, sycamore, zelkova, black beetle, cinnamon, tsuga, nezu, pine, spruce, yew), oil trees (Jatrophacurcas, oil palm), etc.
  • flowering trees Sudki, camellia, hydrangea, sasanqua, shikimi, sakura, yurinoki, crape myrtle, eustoma, etc.
  • roadside trees ash, birch, dogwood, eucalyptus,
  • Lawn Shiba (Nasis, Pleurotus, etc.), Bermudagrass (Neurodonidae, etc.), Bentgrass (Oleoptera, Hykonukagusa, Odonoptera, etc.), Bluegrass (Nagahagusa, Oosuzunokatabira, etc.), Fescue (Oonishi nokegusa, Drosophila, etc.) , Grass, etc.), ryegrass (rat, wheat, etc.), anemonefish, blue whale, etc. Others: flower buds, foliage plants, etc.
  • Crop includes genetically modified crops.
  • this active compound and this pyrethroid compound are used to control harmful animals (eg flies, mosquitoes, cockroaches) that live in the house
  • the dosage of this active compound and this pyrethroid compound should be applied on the surface. Is usually 0.01 to 1000 mg per 1 m 2 of processing area, and usually 0.01 to 500 mg per 1 m 3 of processing space when applied to a space.
  • Emulsions, wettable powders and flowables are usually diluted with water so that the concentration of the active compound and the pyrethroid compound is 0.1 to 1000 ppm, and are applied as oils, aerosols, smokers, poison baits. Etc. are applied as they are.
  • Production Example 1 0.59 g 1,1,3,3-tetrafluoro-N-methyl-1,3-dihydroisobenzofuran-5,6-diamine, 0.63 g sodium hydroxy-pyridin-4-yl-methanesulfonate and 5 ml DMF The mixture was heated and stirred at 120 ° C. for 1 hour. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure.
  • the active compound [8] was subjected to silica gel column chromatography to give 2- (3-methoxypyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [8]). 0.28 g was obtained.
  • Production Example 17 1-Methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole was used according to the method described in Production Example 8 using methyl mercaptan sodium instead of sodium methoxide. (Hereinafter referred to as the present active compound [17]).
  • the active compound [19] was subjected to silica gel column chromatography, and described as 2- (3-methanesulfonylpyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the active compound [19]). ) 0.52 g was obtained.
  • the residue was subjected to silica gel column chromatography to give 1-methyl-2- (1-oxypyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [24]). 0.36 g was obtained.
  • N1-cyclopropyl-4-trifluoromethylbenzene-1,2-diamine was used instead of 3-methylisonicotinic acid.
  • 1-Cyclopropyl-2- (3-fluoropyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as this activity) was prepared using isonicotinic acid according to the method described in Preparation Example 6. Compound (28)) was obtained.
  • the organic layer was washed successively with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over sodium sulfate, and concentrated under reduced pressure.
  • the obtained solid was washed with hexane to obtain 0.17 g of a compound represented by the formula [57] (hereinafter referred to as the present active compound [57]).
  • the obtained solid was washed with hexane to obtain 0.22 g of a compound represented by the formula [60] (hereinafter referred to as the present active compound [60]).
  • the residue was subjected to silica gel preparative thin layer chromatography to obtain 0.15 g of a compound represented by the formula [62] (hereinafter referred to as the present active compound [62]).
  • Production Example 64 In place of 2-methyl-2-propanethiol, 0.09 g of 1-butanethiol was used, and according to the method described in Production Example 63, a compound of the formula [64] (hereinafter referred to as this active compound [64] and 0.15 g was obtained.
  • Production Example 76 1.0 g of the active compound [4] was used instead of the active compound [36], and the compound represented by the formula [76] (hereinafter referred to as the active compound [76]) was prepared according to the method described in Production Example 71. 0.88 g was obtained.
  • the residue was subjected to silica gel preparative thin layer chromatography to obtain 69 mg of a compound represented by the formula [77] (hereinafter referred to as the present active compound [77]).
  • the residue was subjected to silica gel column chromatography to obtain 0.10 g of a compound represented by the formula [79] (hereinafter referred to as the present active compound [79]).
  • Production Example 80 instead of the active compound [71], 0.15 g of the active compound [76] was used, and a compound represented by the formula [80] according to the method described in Production Example 79 (hereinafter referred to as the active compound [80]). .) 0.10 g was obtained.
  • the obtained solid was washed with t-butyl methyl ether to obtain 0.16 g of a compound represented by the formula [82] (hereinafter referred to as the present active compound [82]).
  • Production Example 84 In accordance with the method described in Production Example 82 and using 0.16 g of 1-bromo-2-fluoroethane instead of 1-bromo-1,1,2,2-tetrafluoroethane, the compound represented by the formula [84] 0.21 g of a compound (hereinafter referred to as the present active compound [84]) was obtained.
  • the obtained crystals were subjected to silica gel preparative thin-layer chromatography, and 0.12 g of a compound represented by the formula [85] (hereinafter referred to as the present active compound [85]) and a compound represented by the formula [86] ( Hereinafter referred to as the present active compound [86].) 50 mg was obtained.
  • Production Example 89 A compound represented by formula [89] according to the method described in Production Example 82, using 0.16 g of 3-bromo-1-propene instead of 1-bromo-1,1,2,2-tetrafluoroethane (Hereinafter referred to as the present active compound [89].) 0.13 g was obtained.
  • Production Example 90 0.20 g of the active compound [76] was used instead of the active compound [71], and 0.16 g of 3-bromo-1-propene was used instead of 1-bromo-1,1,2,2-tetrafluoroethane. In accordance with the method described in Production Example 82, 0.12 g of a compound represented by the formula [90] (hereinafter referred to as the present active compound [90]) was obtained.
  • Production Example 91 A compound represented by the formula [91] according to the method described in Production Example 82, using 0.16 g of 3-bromo-1-propyne instead of 1-bromo-1,1,2,2-tetrafluoroethane (Hereinafter referred to as the present active compound [91].) 70 mg was obtained.
  • Production Example 92 0.20 g of the active compound [76] was used in place of the active compound [71], and 0.16 g of 3-bromo-1-propyne in place of 1-bromo-1,1,2,2-tetrafluoroethane In accordance with the method described in Production Example 82, 45 mg of a compound represented by the formula [92] (hereinafter referred to as the present active compound [92]) was obtained.
  • Production Example 96 Using 0.5 ml of diethylamine instead of the 70% aqueous solution of ethylamine, 83 mg of a compound represented by the formula [96] (hereinafter referred to as the active compound [96]) was obtained according to the method described in Production Example 94. .
  • Production Example 98 Using 0.06 g of 2-aminoacetonitrile hydrochloride instead of N-methoxymethanamine hydrochloride, and following the method described in Production Example 97, a compound represented by the formula [98] (hereinafter referred to as the active compound [98] 0.12 g was obtained.
  • the residue was subjected to medium pressure preparative liquid chromatography to obtain 0.17 g of a compound represented by the formula [101] (hereinafter referred to as the present active compound [101]).
  • Production Example 105 Using 0.27 g of bromocyclobutane instead of (bromomethyl) cyclopropane, 82 mg of a compound represented by the formula [105] (hereinafter referred to as the present active compound [105]) according to the method described in Production Example 101 was obtained. It was.
  • Production Example 106 Using 0.27 g of bromocyclobutane instead of (bromomethyl) cyclopropane, 51 mg of a compound represented by the formula [106] (hereinafter referred to as the present active compound [106]) according to the method described in Production Example 102 was obtained. It was.
  • Production Example 107 A compound represented by the formula [107] according to the method described in Production Example 101 using 0.30 g of bromocyclopentane instead of (bromomethyl) cyclopropane (hereinafter referred to as the present active compound [107]). 13 g was obtained.
  • Production Example 108 A compound represented by the formula [108] according to the method described in Production Example 102 using 0.30 g of bromocyclopentane instead of (bromomethyl) cyclopropane (hereinafter referred to as the present active compound [108]). 30 g was obtained.
  • Production Example 111 In place of (bromomethyl) cyclopropane, 0.27 g of 3-bromopropiononitrile is used, and a compound represented by the formula [111] according to the method described in Production Example 101 (hereinafter referred to as the present active compound [111]) 0.19 g was obtained.
  • Production Example 116 In accordance with the method described in Production Example 115, using N1-isobutyl-4-trifluoromethylbenzene-1,2-diamine instead of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine 1-isobutyl-2-pyridin-4-yl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [116]) was obtained.
  • Production Example 117 In accordance with the method described in Production Example 115, using N2-propyl-4-trifluoromethylbenzene-1,2-diamine instead of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine 1-propyl-2-pyridin-4-yl-6-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [117]) was obtained.
  • Production Example 118 In accordance with the method described in Production Example 115, using N2-ethyl-4-trifluoromethylbenzene-1,2-diamine instead of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine 1-ethyl-2-pyridin-4-yl-6-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [118]) was obtained.
  • Production Example 122 In accordance with the method described in Production Example 115, using N1-methyl-4-trifluoromethoxybenzene-1,2-diamine instead of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine 1-methyl-2-pyridin-4-yl-6-trifluoromethoxy-1H-benzimidazole (hereinafter referred to as the present active compound [122]) was obtained.
  • Production Example 123 1,3-Difluoroisopropanol was used instead of 1-butanol, and 2- [3- (1-fluoromethyl-vinyloxy) -pyridin-4-yl] -1-methyl was prepared according to the method described in Production Example 120. -5-Trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [123]) was obtained.
  • Production Example 124 2- (3-Cyclobutoxypyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole was used according to the method described in Production Example 120, using cyclobutanol instead of 1-butanol. (Hereinafter referred to as the present active compound [124]).
  • Production Example 125 A mixture of 0.29 g of N2-methyl-5-trifluoromethylpyridine-2,3-diamine, 0.27 g of 3-ethynylisonicotinic acid, 0.35 g of WSC and 8 ml of pyridine was heated and stirred at 120 ° C. for 2 hours. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure.
  • Production Example 126 3-Methyl-6-trifluoromethyl-2- (3-trifluoromethylpyridine) was used according to the method described in Production Example 125, using 3-trifluoromethylisonicotinic acid instead of 3-ethynylisonicotinic acid. -4-yl) -3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [126]) was obtained.
  • Production Example 130 A mixture of 0.40 g of N2-methyl-5-trifluoromethylpyridine-2,3-diamine, 0.32 g of 3-methylisonicotinic acid, 0.44 g of WSC and 10 ml of pyridine was heated and stirred at 120 ° C. for 5 hours. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. To the residue was added a mixture of 0.60 g of p-toluenesulfonic acid monohydrate and 10 ml of toluene, and the mixture was stirred at 120 ° C. for 1 hour.
  • Production Example 131 A mixture of 0.40 g of N2-methyl-5-trifluoromethylpyridine-2,3-diamine, 0.41 g of 3-ethylisonicotinic acid, 0.44 g of WSC and 10 ml of pyridine was heated and stirred at 120 ° C. for 2.5 hours. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. A mixture of 0.60 g of p-toluenesulfonic acid monohydrate and 10 ml of toluene was added to the residue, and the mixture was stirred at 120 ° C. for 7 hours.
  • the obtained residue was washed with hexane, and 0.55 g of 1-propyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [132]).
  • the active compound [132] 1 H-NMR (CDCl 3 ) ⁇ : 8.84 (dd, 2H), 8.13 (s, 1H), 7.66 (dd, 2H), 7.61 (dd, 1H), 7.54 (d, 1H), 4.28 (t, 2H ), 1.92-1.82 (m, 2H), 0.90 (t, 3H).
  • the obtained residue was washed with hexane, and 0.50 g of 1-isopropyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [133]).
  • the active compound [133] 1 H-NMR (CDCl 3 ) ⁇ : 8.84 (dd, 2H), 8.12 (d, 1H), 7.74 (d, 1H), 7.58-7.55 (m, 3H), 4.88-4.78 (m, 1H), 1.70 (d, 6H).
  • the obtained residue was washed with hexane, and 0.26 g of 1-tert-butyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [134]). .) was obtained.
  • the active compound [134] 1 H-NMR (CDCl 3 ) ⁇ : 8.75 (dd, 2H), 8.05 (s, 1H), 7.84 (d, 1H), 7.56 (d, 1H), 7.44 (dd, 2H), 1.67 (s, 9H ).
  • Production Example 135 A mixture of 1.0 g of N1-ethyl-4-trifluoromethylbenzene-1,2-diamine, 1.05 g of isonicotinic acid chloride hydrochloride and 15 ml of pyridine was heated and stirred at 60 ° C. for 4 hours. Next, 0.94 g of WSC was added and heated and stirred at 80 ° C. for 8 hours. The reaction mixture was cooled to room temperature, poured into water, and extracted twice with ethyl acetate. The combined organic layers were washed with water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure.
  • Reference production example 1 To a mixture of 2.09 g of 4-fluoro-3-nitro-benzotrifluoride and 20 ml of N-methylpyrrolidone, 2.33 g of 40% aqueous methylamine solution was added under ice cooling, and the mixture was warmed to room temperature and stirred for 1 hour. Water was added, and the deposited precipitate was filtered, washed with water, and dried under reduced pressure to obtain 2.0 g of N-methyl-2-nitro-4-trifluoromethylaniline.
  • Reference production example 4 While a mixture of 39.9 ml of diisopropylamine and 257 ml of tetrahydrofuran was cooled in a dry ice-acetone bath, 107 ml of a 2.64M hexane solution of n-butyllithium was added with stirring, followed by stirring for 1.5 hours. Next, 25.0 g of 3-fluoropyridine was added, and the mixture was further stirred for 1.5 hours. After adding crushed dry ice to the reaction mixture, the cooling was stopped and the mixture was stirred until it returned to room temperature. Water was added, and most of hexane and tetrahydrofuran were distilled off under reduced pressure.
  • Reference production example 5 0.64 g of 2-fluoro-4-pyridinemethanol, 10 ml of chloroform, desmartin periodinane (1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3 (1H)- On) 2.54 g of the mixture was stirred at room temperature for 30 minutes. Saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.19 g of 2-fluoropyridine-4-carbaldehyde.
  • N-methyl-2- (3-nitro-5-trifluoromethyl-pyridin-2-yl) -amine was used instead of N-methyl-2-nitro-4-trifluoromethylaniline. According to the method, N2-methyl-5-trifluoromethylpyridine-2,3-diamine was obtained.
  • N2-ethyl-4-trifluoromethylbenzene-1,2-diamine was obtained.
  • N1-methyl-4-trifluoromethoxybenzene-1,2-diamine was obtained.
  • Reference production example 14 A saturated solution was prepared from 150 g of water and 80 g of sodium bisulfite. 150 ml of this saturated solution was ice-cooled, and 17.0 g of isonicotinaldehyde and 20 ml of ethanol were added. The deposited precipitate was filtered and then washed with water to obtain 24.9 g of isonicotinaldehyde / bisulfite adduct.
  • Formulation Example 1 1 part of the compound of any one of the above active compounds [1] to [135] and 9 parts of any one compound of the pyrethroid compound, 35 parts of xylene and 35 parts of N, N-dimethylformamide And 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate, and mixed well with stirring to obtain 10% emulsions.
  • Formulation Example 2 4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic silicon hydroxide fine powder and 54 parts of diatomaceous earth are mixed, and the compound 5 of any one of the above active compounds [1] to [135] is mixed. And 15 parts of any one compound of the present pyrethroid compound are added and mixed well with stirring to obtain each 20% wettable powder.
  • Formulation Example 3 1 part of any one compound of the present active compounds [1] to [135] and 1 part of any one compound of the present pyrethroid compound, 1 part of synthetic silicon hydroxide fine powder, lignin sulfonic acid Add 2 parts of calcium, 30 parts of bentonite and 65 parts of kaolin clay and mix well. Next, an appropriate amount of water is added to these mixtures, and the mixture is further stirred, granulated with a granulator, and dried by ventilation to obtain 2% granules.
  • Formulation Example 4 0.9 part of any one of the above active compounds [1] to [135] and 0.1 part of any one of the pyrethroid compounds are dissolved in an appropriate amount of acetone, To this, 5 parts of a synthetic hydrous silicon oxide fine powder, 0.3 part of PAP (isopropyl acid phosphate) and 93.7 parts of fusami clay are mixed and stirred sufficiently, and acetone is removed by evaporation to obtain each 1% powder.
  • PAP isopropyl acid phosphate
  • Formulation Example 5 35 parts of a mixture of polyoxyethylene alkyl ether sulfate ammonium salt and white carbon (weight ratio 1: 1), 8 parts of any one of the above active compounds [1] to [135], and the pyrethroid compound 2 parts of any one of the above and 55 parts of water are mixed and finely pulverized by a wet pulverization method to obtain each 10% flowable agent.
  • Formulation Example 6 0.04 part of any one compound of the present active compounds [1] to [135] and 0.06 part of any one compound of the present pyrethroid compound are added to 5 parts of xylene and 5 parts of trichloroethane. Dissolve it and mix it with 89.9 parts of deodorized kerosene to obtain each 0.1% oil.
  • Formulation Example 7 7 mg of any one of the above active compounds [1] to [135] and 3 mg of any one of the pyrethroid compounds are dissolved in 0.5 ml of acetone, and this solution is used for animals. Treat 5 g of solid feed powder (solid feed powder CE-2 for breeding, product of Nippon Claire Co., Ltd.) and mix uniformly. Then, acetone is evaporated to dryness to obtain each poisonous bait.
  • solid feed powder solid feed powder CE-2 for breeding, product of Nippon Claire Co., Ltd.
  • Formulation Example 8 0.03 part of any one compound of the present active compounds [1] to [135], 0.07 part of any one compound of the pyrethroid compound, 49.9 parts of neothiozole (Chuo Kasei Co., Ltd.) Is put in an aerosol can, and after mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are charged, shaken, and an actuator aerosol is obtained by mounting an actuator.
  • Formulation Example 9 0.5 part of any one of the above active compounds [1] to [135], 0.1 part of any one of the pyrethroid compounds, BHT (2,6-di-tert-butyl) -4-methylphenol) 0.01 parts, xylene 5 parts, deodorized kerosene 3.39 parts and emulsifier ⁇ Atmos 300 (registered trademark of Atmos Chemical) ⁇ 1 part mixed and dissolved, and distilled water 50 parts.
  • 40 parts of propellant (LPG) is pressurized and filled through the valve to obtain an aqueous aerosol.
  • Test example 1 control effect by artificial feed irrigation treatment for Spodoptela litura
  • compounds [6], [27], [32], [36], [37], [39], [43], [44], [51], [52], [53], [ 100], [122], [126], and [131] were formulated by the method of Formulation Example 1 and diluted to a predetermined concentration.
  • esfenvalerate emulsion (trade name: Sumi Alpha Emulsion; manufactured by Sumitomo Chemical Co., Ltd.), fenpropaslin wettable powder (trade name: Roddy wettable powder; manufactured by Sumitomo Chemical Co., Ltd.) at a predetermined concentration Dilute to Each diluted solution of the present active compound and each diluted solution of the present pyrethroid compound were mixed at a predetermined concentration to obtain a test drug solution.

Abstract

L'invention concerne une composition pesticide possédant une excellente efficacité de lutte antiparasitaire, ainsi qu'une méthode de lutte antiparasitaire. Ladite composition pesticide contient : un composé imidazole fusionné représenté par la formule (1) (dans ladite formule A1 et A2 représentent un atome d'azote ou similaire, R1, R2, R3, et R4 représentent un atome d'halogène ou similaire, R5 représente un groupe hydrocarbure à chaîne C1-6 ou similaire pouvant être substitué par un atome d'halogène, R6 et R7 représentent un groupe hydrocarbure à chaîne C1-4 à substitution halogène ou similaire et n vaut 0 ou 1); et au moins un type de composé pyréthroïde choisi dans un groupe constitué d'esfenvalérate, fenpropathrine, fenvalérate, alpha-cyperméthrine, bifenthrine, cyperméthrine, deltaméthrine, étofenprox, lambda-cyhalothrine, perméthrine, téfluthrine et zéta-cyperméthrine.
PCT/JP2011/074819 2010-10-27 2011-10-27 Composition pesticide et méthode de lutte antiparasitaire WO2012057265A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010241512A JP2012092051A (ja) 2010-10-27 2010-10-27 有害動物防除組成物及び有害動物の防除方法
JP2010-241512 2010-10-27

Publications (1)

Publication Number Publication Date
WO2012057265A1 true WO2012057265A1 (fr) 2012-05-03

Family

ID=45993968

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/074819 WO2012057265A1 (fr) 2010-10-27 2011-10-27 Composition pesticide et méthode de lutte antiparasitaire

Country Status (2)

Country Link
JP (1) JP2012092051A (fr)
WO (1) WO2012057265A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
UY35421A (es) * 2013-03-15 2014-10-31 Nihon Nohyaku Co Ltd Compuesto heterocíclico condensado o su sal, insecticida agrícola u hortícola que comprende el comp uesto y método de uso del insecticida
EP3165521B1 (fr) 2014-07-03 2019-01-16 Shanghai Institute Of Pharmaceutical Industry Procédé de préparation d'un intermédiaire d'étexilate de dabigatran et composé intermédiaire

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE949059C (de) * 1953-07-03 1956-09-13 Bayer Ag Verfahren zur Herstellung von Imidazolderivaten
WO2009131237A1 (fr) * 2008-04-21 2009-10-29 住友化学株式会社 Composition de lutte contre les arthropodes nuisibles, et composé hétérocyclique fusionné
WO2010125985A1 (fr) * 2009-04-28 2010-11-04 Sumitomo Chemical Company, Limited Composé hétérocyclique à cycles fusionnés et son utilisation
WO2011043404A1 (fr) * 2009-10-07 2011-04-14 Sumitomo Chemical Company, Limited Composé hétérocyclique et son utilisation pour lutter contre un arthropode nuisible
WO2011049221A1 (fr) * 2009-10-20 2011-04-28 Sumitomo Chemical Company, Limited Composition et procédé de contrôle des insectes arthropodes nuisibles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE949059C (de) * 1953-07-03 1956-09-13 Bayer Ag Verfahren zur Herstellung von Imidazolderivaten
WO2009131237A1 (fr) * 2008-04-21 2009-10-29 住友化学株式会社 Composition de lutte contre les arthropodes nuisibles, et composé hétérocyclique fusionné
WO2010125985A1 (fr) * 2009-04-28 2010-11-04 Sumitomo Chemical Company, Limited Composé hétérocyclique à cycles fusionnés et son utilisation
WO2011043404A1 (fr) * 2009-10-07 2011-04-14 Sumitomo Chemical Company, Limited Composé hétérocyclique et son utilisation pour lutter contre un arthropode nuisible
WO2011049221A1 (fr) * 2009-10-20 2011-04-28 Sumitomo Chemical Company, Limited Composition et procédé de contrôle des insectes arthropodes nuisibles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEM.PHARM.BULL., vol. 30, no. 8, 1982, pages 2996 - 3004 *

Also Published As

Publication number Publication date
JP2012092051A (ja) 2012-05-17

Similar Documents

Publication Publication Date Title
WO2012057260A1 (fr) Composition pesticide et procédé de lutte antiparasitaire
JP5671835B2 (ja) 縮合複素環化合物及びその有害節足動物防除用途
TWI589570B (zh) 稠合雜環化合物及其在病蟲害防制上之用途
JP2011093899A (ja) 有害節足動物防除組成物及び有害節足動物の防除方法
JP2009280574A (ja) 有害節足動物防除組成物および縮合複素環化合物
JP2011105710A (ja) 有害節足動物防除組成物及び有害節足動物の防除方法
JP2011105711A (ja) 有害節足動物防除組成物及び有害節足動物の防除方法
WO2012057273A1 (fr) Composition de lutte contre les animaux nuisibles et méthode de lutte contre les animaux nuisibles
JP2011105709A (ja) 有害節足動物防除組成物及び有害節足動物の防除方法
WO2012057266A1 (fr) Composition pesticide et procédé de lutte antiparasitaire
JP2011105712A (ja) 有害節足動物防除組成物及び有害節足動物の防除方法
WO2012057265A1 (fr) Composition pesticide et méthode de lutte antiparasitaire
WO2012057269A1 (fr) Procédé et composition pour lutter contre les animaux nuisibles
WO2012057268A1 (fr) Composition pesticide et méthode de lutte antiparasitaire
JP2012092060A (ja) 有害動物防除組成物及び有害動物の防除方法
JP2012036097A (ja) 有害生物防除組成物
JP2010120865A (ja) 有害生物防除組成物
WO2012057264A1 (fr) Composition pesticide et procédé de lutte antiparasitaire
JP2012092059A (ja) 有害動物防除組成物及び有害動物の防除方法
JP2012092061A (ja) 有害動物防除組成物及び有害動物の防除方法
JP2012092056A (ja) 有害動物防除組成物及び有害動物の防除方法
JP2012092057A (ja) 有害動物防除組成物及び有害動物の防除方法
JP2012092058A (ja) 有害動物防除組成物及び有害動物の防除方法
JP2012051877A (ja) 有害生物防除組成物
JP2012087056A (ja) 有害動物防除組成物及び有害動物の防除方法

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: 11836398

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11836398

Country of ref document: EP

Kind code of ref document: A1