+

WO2018199209A1 - Composé hétérocyclique ayant un groupe éther d'oxime conjugué ou un sel de celui-ci, insecticide agricole et horticole le comprenant et son procédé d'utilisation - Google Patents

Composé hétérocyclique ayant un groupe éther d'oxime conjugué ou un sel de celui-ci, insecticide agricole et horticole le comprenant et son procédé d'utilisation Download PDF

Info

Publication number
WO2018199209A1
WO2018199209A1 PCT/JP2018/016913 JP2018016913W WO2018199209A1 WO 2018199209 A1 WO2018199209 A1 WO 2018199209A1 JP 2018016913 W JP2018016913 W JP 2018016913W WO 2018199209 A1 WO2018199209 A1 WO 2018199209A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
halo
reaction
alkyl group
acid
Prior art date
Application number
PCT/JP2018/016913
Other languages
English (en)
Japanese (ja)
Inventor
勇介 佐野
樹 米村
諏訪　明之
隼平 藤江
綾介 田中
Original Assignee
日本農薬株式会社
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 日本農薬株式会社 filed Critical 日本農薬株式会社
Publication of WO2018199209A1 publication Critical patent/WO2018199209A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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 heterocyclic compound having a conjugated oxime group or a salt thereof, an agricultural and horticultural insecticide containing the compound as an active ingredient, and a method of using the same.
  • Patent Documents 1 to 7 Such a document does not specifically disclose a compound in which a conjugated oxime group is bonded to a condensed heterocyclic ring.
  • the present inventors have found that the heterocyclic compound having a conjugated oxime group represented by the general formula (1) or a salt thereof has excellent control effects against agricultural and horticultural pests. As a result, the present invention was reached. That is, the present invention relates to the following inventions.
  • R 1 is (a1) a halogen atom; (a2) a halo (C 1 -C 6 ) alkyl group; (a3) a halo (C 1 -C 6 ) alkoxy group; (a4) halo (C 1- C 6 ) alkylthio group; (a5) halo (C 1 -C 6 ) alkylsulfinyl group; or (a6) halo (C 1 -C 6 ) alkylsulfonyl group; R 2 , R 3 , and R 4 may be the same or different and each represents (b1) a hydrogen atom; or (b2) (C 1 -C 6 ) alkyl group.
  • R 5 is (c1) a hydrogen atom; (c2) (C 1 -C 6 ) alkyl group; (c3) (C 2 -C 6 ) alkenyl group; (c4) (C 2 -C 6 ) alkynyl group; c5) (C 3 -C 6) cycloalkyl group; (c6) (C 3 -C 6) cycloalkyl (C 1 -C 6) alkyl group; (c7) (C 1 -C 6) alkoxy (C 1 - C 6) alkyl group; (c8) halo (C 1 -C 6) alkyl group; (c9) halo (C 2 -C 6) alkenyl group; (c10) halo (C 2 -C 6) alkynyl group; (c11 ) (C 1 -C 6 ) alkylthio (C 1 -C 6 ) alkyl group; (c12) (C 1 -C 6 ) alkylsulf
  • A, A 2 and A 3 represent CH or a nitrogen atom
  • a 1 represents an oxygen atom or N—R 6 (where R 6 is a (d1) (C 1 -C 6 ) alkyl group; d2) (C 3 -C 6) cycloalkyl group; (d3) (C 2 -C 6) alkenyl; or (d4) (C 2 -C 6 ) alkynyl group; and).
  • m represents 0, 1, or 2.
  • R 1 is (a2) a halo (C 1 -C 6 ) alkyl group; (a4) a halo (C 1 -C 6 ) alkylthio group; (a5) a halo (C 1 -C 6 ) alkylsulfinyl group; Or (a6) a halo (C 1 -C 6 ) alkylsulfonyl group; R 2 , R 3 , and R 4 may be the same or different, and (b1) a hydrogen atom; or (b2) (C 1 -C 6 ) alkyl group; and R 5 is (c8) a halo (C 1 -C 6 ) alkyl group; or (c11) (C 1 -C 6 ) alkylthio (C 1 -C 6 ) alkyl group; A, A 2 and A 3 are CH or a nitrogen atom, A 1 is an oxygen atom, or N—R 6 (where R 6 is a (d1) (C 1
  • a heterocyclic compound having a conjugated oxime group according to [2] or a salt thereof [3] An agricultural and horticultural insecticide comprising the heterocyclic compound having a conjugated oxime group according to [1] or [2] or a salt thereof as an active ingredient, [4] A method for using an agricultural and horticultural insecticide characterized by treating a plant or soil with an effective amount of the heterocyclic compound having a conjugated oxime group or a salt thereof according to [1] or [2], [5] An ectoparasite control agent for animals other than humans, which comprises the heterocyclic compound having a conjugated oxime group according to [1] or [2] or a salt thereof as an active ingredient.
  • the heterocyclic compound having a conjugated oxime group or a salt thereof of the present invention not only has an excellent effect as an agricultural and horticultural insecticide, but also inside or outside a pet animal such as a dog or cat, or a domestic animal such as a cow or sheep. It also has the effect of controlling against other harmful insects such as parasitic insects and white ants.
  • halo means “halogen atom”, and represents chlorine atom, bromine atom, iodine atom or fluorine atom. Show.
  • (C 1 -C 6 ) alkyl group means, for example, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butyl group, normal pentyl group, isopentyl group, Tertiary pentyl group, neopentyl group, 2,3-dimethylpropyl group, 1-ethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, normal hexyl group, isohexyl group, 2-hexyl group, 3-hexyl group, 2 -Represents a linear or branched alkyl group having 1 to 6 carbon atoms such as a methylpentyl group, a 3-methylpentyl group, a 1,1,2-trimethylpropyl group or a 3,3-dimethylbutyl group.
  • (C 2 -C 6 ) alkenyl means, for example, vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-methyl-2-propenyl, 1-methyl-2-propenyl.
  • a straight chain or branched alkenyl group having 2 to 6 carbon atoms such as 2-methyl-1-propenyl group, pentenyl group, 1-hexenyl group, 3,3-dimethyl-1-butenyl group, etc. .
  • (C 2 -C 6 ) alkynyl group means, for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 3-methyl-1-propynyl group
  • Straight or branched carbon atom number 2 such as 2-methyl-3-propynyl group, pentynyl group, 1-hexynyl group, 3-methyl-1-butynyl group, 3,3-dimethyl-1-butynyl group, etc. Shows up to 6 alkynyl groups.
  • (C 3 -C 6 ) cycloalkyl refers to a cyclic alkyl group having 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., and represents “(C 1 -C 6 ) Alkoxy group ”means, for example, methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, secondary butoxy group, tertiary butoxy group, normal pentyloxy group, isopentyloxy group, tertiary pentyloxy group.
  • (C 1 -C 6 ) alkylthio group means, for example, methylthio group, ethylthio group, normal propylthio group, isopropylthio group, normal butylthio group, secondary butylthio group, tertiary butylthio group, normal pentylthio group , Isopentylthio group, tertiary pentylthio group, neopentylthio group, 2,3-dimethylpropylthio group, 1-ethylpropylthio group, 1-methylbutylthio group, normal hexylthio group, isohexylthio group, 1 represents a linear or branched alkylthio group having 1 to 6 carbon atoms such as 1,1,2-trimethylpropylthio group, and “(C 1 -C 6 ) alkylsulfinyl group” means, for example, methylsulfinyl Group, methyl
  • substituents substituted with one or more halogen atoms are “halo (C 1 -C 6 ) alkyl”, “halo (C 2 -C 6 ) alkenyl”, “halo (C 2- “C 6 ) alkynyl group”, “halo (C 3 -C 6 ) cycloalkyl group”, “halo (C 3 -C 6 ) cycloalkyloxy group”, “halo (C 1 -C 6 ) alkoxy group”, “ “Halo (C 2 -C 6 ) alkenyloxy”, “halo (C 2 -C 6 ) alkynyloxy”, “halo (C 1 -C 6 ) alkylthio”, “halo (C 1 -C 6 ) alkyl” “Sulfinyl group”, “halo (C 1 -C 6 ) alkylsulfonyl group”, “halo (C 2 -C 6 ) alkenylthio
  • Expressions such as “(C 1 -C 6 )”, “(C 2 -C 6 )”, “(C 3 -C 6 )” indicate the range of the number of carbon atoms of various substituents. Further, the above definition can be given for a group to which the above substituent is linked. For example, in the case of “(C 1 -C 6 ) alkoxy (C 1 -C 6 ) alkyl group”, it is linear or branched. It indicates that an alkoxy group having 1 to 6 carbon atoms is bonded to a linear or branched alkyl group having 1 to 6 carbon atoms.
  • Examples of the salt of the heterocyclic compound having a conjugated oxime group represented by the general formula (1) of the present invention include inorganic acid salts such as hydrochloride, sulfate, nitrate and phosphate, acetate, fumarate and maleate.
  • Organic salts such as acid salts, oxalates, methanesulfonates, benzenesulfonates, paratoluenesulfonates, salts with inorganic or organic bases such as sodium ions, potassium ions, calcium ions, trimethylammonium salts It can be illustrated.
  • the heterocyclic compound having a conjugated oxime group represented by the general formula (1) and salts thereof of the present invention may have one or more asymmetric centers in the structural formula, and two or more Optical isomers and diastereomers may exist, and the present invention includes all of the optical isomers and mixtures containing them in an arbitrary ratio.
  • the compound represented by the general formula (1) of the present invention and salts thereof may have two kinds of geometric isomers derived from the carbon-carbon double bond in the structural formula. Includes all geometric isomers and mixtures containing them in any proportion.
  • the compound of the present invention comprises syn isomer (Z isomer) -syn isomer (Z isomer), syn isomer (Z isomer) -anti isomer (E isomer), anti isomer by a conjugated oxime group.
  • syn isomer Z isomer
  • Z isomer syn isomer
  • Z isomer syn isomer
  • E isomer anti isomer
  • E isomer anti isomer
  • E isomer anti isomer
  • E isomer anti isomer
  • E isomer anti isomer
  • E isomer anti isomer
  • the present invention may be any isomer, Moreover, the isomer mixture of those arbitrary ratios may be sufficient.
  • R 1 is (a1) a halogen atom; (a2) halo (C 1 -C 6) alkyl group; (a3) halo (C 1 -C 6) alkoxy group; (a4) halo (C 1 -C 6) alkylthio group; (a5) halo (C 1 -C 6) alkylsulfinyl group; Or (a6) a halo (C 1 -C 6 ) alkylsulfonyl group; and R 2 , R 3 and R 4 may be the same or different, and (b1) a hydrogen atom; or (b2) (C 1 -C 6 ) alkyl group; and R 5 is (c1) hydrogen atom; (c2) (C 1 -C 6 )
  • R 1 is (a2) a halo (C 1 -C 6 ) alkyl group; (a4) a halo (C 1 -C 6 ) alkylthio group; (a5) a halo (C 1 -C 6 ) alkylsulfinyl group Or (a6) a halo (C 1 -C 6 ) alkylsulfonyl group; R 2 , R 3 , and R 4 may be the same or different; (b1) a hydrogen atom; or (b2) (C 1- C 6 ) alkyl group; and R 5 is (c8) a halo (C 1 -C 6 ) alkyl group; or (c11) (C 1 -C 6 ) alkylthio (C 1 -C 6 ) alkyl group And A, A 2 and A 3 are CH or a nitrogen atom, A 1 is an oxygen atom, or N—R 6 (where R 6 is (d1) (C 1 -C 6 ) al
  • the heterocyclic compound having a conjugated oxime group or a salt thereof of the present invention can be produced, for example, by the following production method, but the present invention is not limited thereto.
  • the starting compound used in the production method of the present invention can be produced by a known method or a method known per se.
  • the amide compound represented by the general formula (2a-1) comprises a carboxylic acid ester represented by the general formula (2a) and a compound represented by the general formula (3) as a base and It can be produced by reacting in the presence of an active solvent.
  • Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride and the like.
  • Alkali metal hydrides, acetates such as potassium acetate, alkali metal alkoxides such as potassium t-butoxide, sodium methoxide, sodium ethoxide, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undeck-
  • tertiary amines such as 7-ene, nitrogen-containing aromatic compounds such as pyridine and dimethylaminopyridine, etc., and the amount used is usually 1 times that of the compound represented by the general formula (3). It is used in the range of mol to 10 times mol.
  • the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogens such as methylene chloride, chloroform and carbon tetrachloride.
  • Aliphatic hydrocarbons such as chlorobenzene and dichlorobenzene
  • chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran
  • esters such as ethyl acetate
  • inert solvents such as amides such as dimethylacetamide, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone, and the like.
  • each reactant may be used in an equimolar amount, but any of the reactants can be used in excess.
  • the reaction temperature can be from room temperature to the boiling range of the inert solvent used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it may be in the range of several minutes to 48 hours.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • Step [b] The compound represented by the general formula (1a-6) was described in Synthesis 1981, 1 in the presence of an amide compound represented by the general formula (2a-1) in the presence of an inert solvent. According to the method (preferably using azodicarboxylic acid diesters and triphenylphosphine). Or it can also manufacture by making the amide compound represented by general formula (2a-1) react in presence of an acid and an inert solvent.
  • Examples of the acid used in this reaction include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid and benzoic acid, sulfones such as methanesulfonic acid and trifluoromethanesulfonic acid. Acids, phosphoric acids, etc. can be exemplified, and the amount used is appropriately selected from the range of 0.01 mole to 10 moles relative to the amide compound represented by the general formula (2a-1). It ’s fine.
  • inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid
  • organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid and benzoic acid
  • sulfones such as methanesulfonic acid and trifluoromethanesulfonic acid.
  • Acids, phosphoric acids, etc. can be exemplified
  • the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogens such as methylene chloride, chloroform and carbon tetrachloride.
  • Hydrocarbons halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene
  • chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, dimethylformamide, dimethyl
  • the inert solvent include amides such as acetamide, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. Use alone or in combination of two or more Door can be.
  • the reaction temperature can be from room temperature to the boiling range of the inert solvent used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it may be in the range of several minutes to 48 hours.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the heterocyclic compound represented by the general formula (1a-5) is obtained by reacting the heterocyclic compound represented by the general formula (1a-6) with an oxidizing agent in an inert solvent. Can be manufactured.
  • oxidizing agent used in this reaction examples include peroxides such as hydrogen peroxide, perbenzoic acid, and m-chloroperbenzoic acid. These oxidizing agents can be appropriately selected in the range of 1 to 5 moles relative to the heterocyclic compounds represented by the general formula (1a-6).
  • the inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit this reaction, and examples thereof include chain or cyclic ethers such as diethyl ether, tetrahydrofuran, and dioxane, and aromatic carbonization such as benzene, toluene, and xylene.
  • chain or cyclic ethers such as diethyl ether, tetrahydrofuran, and dioxane
  • aromatic carbonization such as benzene, toluene, and xylene.
  • Hydrogens, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, nitriles such as acetonitrile, esters such as ethyl acetate, formic acid, acetic acid, etc.
  • Organic solvents N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, water and the like, and these inert solvents can be used alone or Two or more kinds can be mixed and used.
  • the reaction temperature in this reaction may be appropriately selected within the range of ⁇ 10 ° C. to the reflux temperature of the inert solvent used.
  • the reaction time varies depending on the reaction scale, reaction temperature, and the like, and is not constant but may be appropriately selected within the range of several minutes to 48 hours.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • Step [d] The compound represented by the general formula (1a-4) is obtained by converting the compound represented by the general formula (1a-5) into Green's Protective GROUPS in Organic SYNTHESIS (4th It can be produced by deprotection by the method described in Edition).
  • the compound represented by the general formula (1a-3) can be produced by the method described in Synthesis 1996, 1153 from the compound represented by the general formula (1a-4). .
  • Step [f] The compound represented by the general formula (1a-2) is obtained by combining the compound represented by the general formula (1a-3) and the ylide compound represented by the general formula (5) with Org. React. 1965, 14, 270, or Synthesis 1975, 765.
  • Step [g] The compound represented by the general formula (1a-1) is obtained by combining a compound represented by the general formula (1a-2) and hydroxylamines with Organic Functional Group Preparations (2nd Edition) Vol. 3 Manufactured by the method described in Chapter 11 / Oximes.
  • the heterocyclic compound represented by the general formula (1a) is obtained by combining a base and an oxime compound represented by the general formula (1a-1) and a compound represented by the general formula (6). It can be produced by reacting in the presence of an active solvent.
  • Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride and the like.
  • Alkali metal hydrides, acetates such as potassium acetate, alkali metal alkoxides such as potassium t-butoxide, sodium methoxide, sodium ethoxide, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undeck-
  • tertiary amines such as 7-ene, nitrogen-containing aromatic compounds such as pyridine and dimethylaminopyridine, etc., and the amount used is usually based on the compound represented by the general formula (1a-1) It is used in the range of 1 to 10 moles.
  • the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogens such as methylene chloride, chloroform and carbon tetrachloride.
  • Hydrocarbons halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene
  • chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, dimethylformamide, dimethyl
  • the inert solvent include amides such as acetamide, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone, Use alone or in combination of two or more Door can be.
  • each reactant may be used in an equimolar amount, but any of the reactants can be used in excess.
  • the reaction temperature can be from room temperature to the boiling range of the inert solvent used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it may be in the range of several minutes to 48 hours.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the amide compound represented by the general formula (2b-1) is a base of the carboxylic acid chloride represented by the general formula (2b) and the compound represented by the general formula (3). And can be produced by reacting in the presence of an inert solvent.
  • Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride and the like.
  • Alkali metal hydrides, acetates such as potassium acetate, alkali metal alkoxides such as potassium t-butoxide, sodium methoxide, sodium ethoxide, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undeck-
  • tertiary amines such as 7-ene, nitrogen-containing aromatic compounds such as pyridine and dimethylaminopyridine, etc., and the amount used is usually 1 times that of the compound represented by the general formula (3). It is used in the range of mol to 10 times mol.
  • the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogens such as methylene chloride, chloroform and carbon tetrachloride.
  • Hydrocarbons halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene
  • chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, dimethylformamide, dimethyl
  • the inert solvent include amides such as acetamide, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone, Use alone or in combination of two or more Door can be.
  • each reactant may be used in an equimolar amount, but any of the reactants can be used in excess.
  • the reaction temperature can be from room temperature to the boiling range of the inert solvent used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it may be in the range of several minutes to 48 hours.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the heterocyclic compound represented by the general formula (1b-7) is obtained by reacting an amide compound represented by the general formula (2b-1) with an acid in the presence of an inert solvent. Can be manufactured.
  • Examples of the acid used in this reaction include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid and benzoic acid, sulfones such as methanesulfonic acid and trifluoromethanesulfonic acid. Acids, phosphoric acids, etc. can be exemplified, and the amount used is appropriately selected from the range of 0.01 mole to 10 moles relative to the amide compound represented by the general formula (2b-1). It ’s fine.
  • inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid
  • organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid and benzoic acid
  • sulfones such as methanesulfonic acid and trifluoromethanesulfonic acid.
  • Acids, phosphoric acids, etc. can be exemplified
  • the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogens such as methylene chloride, chloroform and carbon tetrachloride.
  • Hydrocarbons halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene
  • chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, dimethylformamide, dimethyl
  • the inert solvent include amides such as acetamide, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. Use alone or in combination of two or more Door can be.
  • the reaction temperature can be from room temperature to the boiling range of the inert solvent used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it may be in the range of several minutes to 48 hours.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the heterocyclic compound represented by the general formula (1b-6) is a heterocyclic compound represented by the general formula (1b-7) and a compound represented by the general formula (4) In the presence of a base and an inert solvent.
  • Examples of the base used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, acetates such as sodium acetate and potassium acetate, potassium t Alkali metal alkoxides such as butoxide, sodium methoxide, sodium ethoxide, tertiary amines such as triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene, pyridine, dimethyl
  • Examples thereof include nitrogen-containing aromatic compounds such as aminopyridine, and the amount used is usually in the range of 1 to 10 moles compared to the heterocyclic compound represented by the general formula (1b-6).
  • the alkali salt of the compound represented by General formula (4) it is not necessary to use a base.
  • the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogens such as methylene chloride, chloroform and carbon tetrachloride.
  • Hydrocarbons halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene
  • chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, dimethylformamide, dimethyl
  • the inert solvent include amides such as acetamide, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone, Use alone or in combination of two or more Door can be.
  • each reactant may be used in an equimolar amount, but any of the reactants can be used in excess.
  • the reaction temperature can be from ⁇ 10 ° C. in the boiling range of the inert solvent to be used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it may be in the range of several minutes to 48 hours.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the heterocyclic compound represented by the general formula (1b-5) is obtained by reacting the heterocyclic compound represented by the general formula (1b-6) with an oxidizing agent in an inert solvent. Can be manufactured.
  • oxidizing agent used in this reaction examples include peroxides such as hydrogen peroxide, perbenzoic acid, and m-chloroperbenzoic acid. These oxidizing agents can be appropriately selected in the range of 1 to 5 moles relative to the heterocyclic compounds represented by the general formula (1b-6).
  • the inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit this reaction.
  • Hydrogens halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, nitriles such as acetonitrile, esters such as ethyl acetate, formic acid, acetic acid, etc.
  • Organic solvents, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, water and the like, and these inert solvents can be used alone or Two or more kinds can be mixed and used.
  • the reaction temperature in this reaction may be appropriately selected within the range of ⁇ 10 ° C. to the reflux temperature of the inert solvent used.
  • the reaction time varies depending on the reaction scale, reaction temperature, and the like, and is not constant but may be appropriately selected within the range of several minutes to 48 hours.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the heterocyclic compound represented by the general formula (1b-4) is obtained by combining a heterocyclic compound represented by the general formula (1b-5) and a vinyl boric acid compound with a metal catalyst and a base. Can be produced by carrying out a cross-coupling reaction in an inert solvent.
  • metal catalyst examples include a palladium catalyst, a nickel catalyst, an iron catalyst, a ruthenium catalyst, a platinum catalyst, a rhodium catalyst, and an iridium catalyst.
  • metal catalysts include “metals”, “supported metals”, “metal salts such as chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates or oxides”, “ A complex compound such as an olefin complex, a phosphine complex, an amine complex, an ammine complex, or an acetylacetonate complex ”can be used.
  • a palladium catalyst is preferred.
  • the palladium catalyst examples include palladium metals such as palladium black and palladium sponge, and supported palladium metals such as palladium / alumina, palladium / carbon, palladium / silica, palladium / Y-type zeolite.
  • metal salts such as palladium chloride, palladium bromide, palladium iodide, palladium acetate, can be illustrated.
  • ⁇ -allyl palladium chloride dimer palladium acetylacetonate, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, tris (dibenzylideneacetone) Dipalladium (chloroform adduct), dichlorodiamine palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis (tricyclohexylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro [1,2-bis (diphenylphosphino) ethane] Palladium, dichloro [1,3-bis (diphenylphosphino) propane] palladium, dichloro [1,4-bis (diphenyl) Phosphino) but
  • These palladium catalysts may be used alone or in combination with a tertiary phosphine.
  • a tertiary phosphine that can be used, triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tri-o-tolylphosphine, trioctylphosphine, 9,9 -Dimethyl-4,5-bis (diphenylphosphino) xanthene, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 1,2-bis (diphenylphosphino) ethane, , 3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-
  • Examples of the base that can be used in this reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and other inorganic bases, sodium hydride, potassium hydride and the like.
  • Alkoxides such as alkali metal hydrides, sodium methoxide, sodium ethoxide, potassium tertiary butoxide and the like can be mentioned.
  • the amount of the base used can usually be in the range of about 1 to 5 times the molar amount of the heterocyclic compound represented by the general formula (1b-5).
  • the inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit this reaction.
  • alcohols such as methanol, ethanol, propanol, butanol, 2-propanol, diethyl ether, tetrahydrofuran, dioxane, 1, Chain or cyclic ethers such as 2-dimethoxyethane (DME), aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, etc.
  • DME 2-dimethoxyethane
  • aromatic hydrocarbons such as benzene, toluene, xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, etc.
  • Halogenated aromatic hydrocarbons such as acetonitrile, esters such as ethyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone
  • polar solvents and water These inert solvents can be used alone or in admixture of two or more.
  • the reaction temperature in this reaction may usually be in the range of about 0 ° C. to the boiling point of the solvent used, and the reaction time is not constant depending on the reaction scale, reaction temperature, etc., but may be appropriately selected within the range of several minutes to 48 hours. .
  • this reaction can also be performed in the atmosphere of inert gas, such as nitrogen gas and argon gas, for example.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • step [j] The diol heterocyclic compound represented by the general formula (1b-3) is obtained by changing the vinyl heterocyclic compound represented by the general formula (1b-4) in the presence of osmium tetroxide and an oxidizing agent. It can be produced according to the method described in 4th edition Experimental Chemistry Course 23, Organic Chemistry V, -Oxidation Reaction- (Maruzen Co., Ltd.). After completion of the reaction, the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary. This step and the next step [K] can also be performed continuously.
  • the heterocyclic compound represented by the general formula (1b-2) is obtained by combining the diol heterocyclic compound represented by the general formula (1b-3) and the periodic acid compound in the presence of an inert solvent.
  • the reaction can be carried out according to the method described in New Experimental Chemistry Course 15, Oxidation and Reduction I-1 (Maruzen Co., Ltd.).
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the heterocyclic compound represented by the general formula (1b-1) includes a heterocyclic compound represented by the general formula (1b-2) and an ylide compound represented by the general formula (5) Org. React. 1965, 14, 270, or Synthesis 1975, 765.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the heterocyclic compound represented by the general formula (1b) is obtained by combining the heterocyclic compound represented by the general formula (1b-1) and the compound represented by the general formula (7) with a base.
  • the reaction can be carried out in an inert solvent in the presence.
  • Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, triethylamine, diisopropylethylamine, 1,8- Examples thereof include tertiary amines such as diazabicyclo [5.4.0] undec-7-ene, and nitrogen-containing aromatic compounds such as pyridine and dimethylaminopyridine.
  • the amount of the base used can usually be in the range of about 1 to 5 moles compared to the heterocyclic compound represented by the general formula (7).
  • the inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit this reaction.
  • alcohols such as methanol, ethanol, propanol, butanol, 2-propanol, diethyl ether, tetrahydrofuran, dioxane, 1, Chain or cyclic ethers such as 2-dimethoxyethane (DME), aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, etc.
  • DME 2-dimethoxyethane
  • aromatic hydrocarbons such as benzene, toluene, xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, etc.
  • Halogenated aromatic hydrocarbons such as acetonitrile, esters such as ethyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone
  • polar solvents and water These inert solvents can be used alone or in admixture of two or more.
  • the reaction temperature in this reaction may usually be in the range of about 0 ° C. to the boiling point of the solvent used, and the reaction time is not constant depending on the reaction scale, reaction temperature, etc., but may be appropriately selected within the range of several minutes to 48 hours. .
  • this reaction can also be performed in the atmosphere of inert gas, such as nitrogen gas and argon gas, for example.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the intermediate of the compound of the present invention represented by the general formula (2a) can be produced by the following method.
  • step [ ⁇ ] Pyridine-3-carboxylic acid (2a-3) is obtained by the method described in JP-A-2005-272338 (Heck reaction). ) To introduce an ester group at the 6-position.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method. If desired, the target product can be produced by purification by recrystallization, column chromatography or the like.
  • Ethylthiopyridine dicarboxylic acid monoester (2a-2) includes pyridinedicarboxylic acid monoester represented by general formula (2a-3) and ethylthiol compound represented by general formula (4) Can be produced in the presence of a base and an inert solvent.
  • Examples of the base used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, acetates such as sodium acetate and potassium acetate, potassium t Alkali metal alkoxides such as butoxide, sodium methoxide, sodium ethoxide, tertiary amines such as triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene, pyridine, dimethyl
  • Examples thereof include nitrogen-containing aromatic compounds such as aminopyridine, and the amount used is usually in the range of 1 to 10 moles compared to the ethylthiol compound represented by the general formula (4). .
  • the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogens such as methylene chloride, chloroform and carbon tetrachloride.
  • Hydrocarbons halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene
  • chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, dimethylformamide, dimethyl
  • the inert solvent include amides such as acetamide, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone, Use alone or in combination of two or more Door can be.
  • each reactant may be used in an equimolar amount, but any of the reactants can be used in excess.
  • the reaction temperature can be from ⁇ 10 ° C. in the boiling range of the inert solvent to be used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it may be in the range of several minutes to 48 hours.
  • the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the pyridinecarboxylic acid ester represented by the general formula (2a-1) is a monoester of ethylthiopyridine dicarboxylic acid represented by the general formula (2a-2). It can be manufactured by the method described in the issue pamphlet.
  • the compound represented by the general formula (2a) is obtained by converting a pyridinecarboxylic acid ester represented by the general formula (2a-1) into Green's Protective GROUPS in Organic SYNTHESIS (4th). (Edition). After completion of the reaction, the target product may be isolated from the reaction mixture containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
  • the compound represented by the general formula (3) which is a production intermediate of the compound of the present invention, can be produced by the methods described in WO2012 / 086848 pamphlet and WO2016 / 104746 pamphlet.
  • the compound represented by the general formula (7) which is an intermediate for the production of the compound of the present invention, is obtained from hydroxyphthalimide, J. Org. Chem. 36, 3835 (1971), J. Am. It can be produced by the method described in Antibiotics, 53 (10), 2000.
  • Me represents a methyl group
  • Et represents an ethyl group
  • n-Pr represents a normal propyl group
  • i-Pr represents an isopropyl group.
  • Physical properties indicate melting point (° C.).
  • the agricultural and horticultural insecticide containing a heterocyclic compound having a conjugated oxime group represented by the general formula (1) of the present invention or a salt thereof as an active ingredient harms paddy rice, fruit trees, vegetables, other crops, and flowers. It is suitable for pest control such as various agricultural and forestry, gardening, stored grain pests, hygiene pests, nematodes, white ants, etc.
  • Examples of the pests or nematodes include the following. Lepidoptera (Lepidoptera) pests such as Parasa consocia, Redwood (Anomis mesogona), Papilio xuthus, Matsumuraeses azukivora, Ostrinia scapulalis, African exotic empti (Spod) (Hyphantria cunea), Awanoiga (Ostrinia furnacalis), Ayayoto (Pseudaletia separata), iga (Tinea translucens), rush saint moth (Bactra furfurana), Ichinomosei (Parnara guttata), Inaitei inferens), Brachmia triannulella, Monema flavescens, Iraqusinu Waiba (Trichoplusia ni), Pleuroptya ruralis, Cystidia couaggaria, Lampides boeticus, Males flamingo (
  • Hemiptera pests, for example, Nezara antennata, red beetle (Stenotus rubrovittatus), red beetle (Graphosoma rubrolineatum), red beetle (Trigonotylus coelestialium), Aeschynteles maculatus), red beetle (Creontiades pallidifer), red beetle bug (Dysdercus cingulatus), red beetle (Chrysomphalus ficus), red beetle (Aonidiella aurantii), red crab beetle (Graptops) Scale insects (Icerya purchasi), Japanese beetle (Piezodorus hybneri), Japanese beetle (Lagynotomus elongatus), Japanese white-winged beetle (Thaia subrufa), Japanese black beetle (Scotinophara luridaito
  • Coleoptera (Coleoptera) pests include, for example, Xystrocera globosa, Aobaarie-hane-kakushi (Paederus fuscipes), Ahanamuri (Eucetonia roelofsi), Azuki beetle (Callosobruchus chinensis), Arimodosium (Hypera postica), rice weevil (Echinocnemus squameus), rice beetle (Oulema oryzae), rice weevil (Donacia provosti), rice weevil (Lissorhoptrus oryzophilus), Weevil (Acanthoscelides obtectus), western corn rootworm (Diabrotica virgifera virgifera), weevil weevil (Involvulus cupreus), weevil (Aulacophora femoralis), pea weevil (Bruchus pisorum) Epilachna viginti
  • Culex pipiens pallens red flies fly (Pegomya hyoscyami), red spider fly (Liriomyza huidobrensis), house fly (Musca domestica), rice flies Flies Fruit flies (Rhacochlaena japonica), fruit flies (Muscina stabulans), fruit flies such as fruit flies (Megaselia spiracularis), giant butterflies (Clogmia albipunctata), mushroom moth (Tipula aino), hormone moth (Pipula) rhynchus), Anopheles sinensis, Japanese flies (Hylemya brassicae), Soybean fly (Asphondylia sp.), Panax fly (Delia platura), Onion fly (Delia antiqua) RRen ), Ceratitis capitata, Bradysia agrestis, sugar beetle fly (P
  • Hymenoptera Pristomyrmex ponnes
  • Arbatidae Monomelium pharaonis
  • Pheidole noda Athalia rosae
  • Cristoforma Kuriphilus
  • Hornets black bee (Athalia infumata infumata), horned bee (Arge g pagana), Japanese bee (Athalia ⁇ japonica), cricket (Acromyrmex spp.), Fire ant (Solenopsis spp.), Apple honey bee (Arlen ali) (Ochetellus glaber) and the like.
  • insects of the order Diptera Hortocoryphus lineosus
  • Kera Gryllotalpa sp.
  • Coago Oxya hyla intricata
  • Cobainago Oxya yezoensis
  • Tosama locust Locusta migrago
  • Oneya Homorocoryphus jezoensis
  • emma cricket Teogryllus emma
  • Thrips examples of thrips of the order Thrips (Selenothrips rubrocinctus), thrips (Stenchaetothrips biformis), Thrips thrips (Haplothrips , Lithrips floridensis, Thrips simplex, Thrips nigropilosus, Helothripes Leeuwenia pasanii), Shiritakuthamis (Litotetothrips pasaniae), Citrus srips (Scirtothrips citri), Hempothrips chinensis, Soybean thrips (Mycterothrips glycines), Da Thrips setosus, Thripsrtsaw Thrips hawaiiensis, Haplothrips kurdjumovi, Thrips coloratus , Lilyripa vaneeckei, and the like.
  • mite moths (Leptotrombidium akamushi), Ashinowa spider mite (Tetranychus ludeni), American dock ticks (Dermacentor variabilis), Ichinami spider mite (Tetranychus truncatus), house dust mite (Ornithonyssus bacoti), mite Tetranychus viennensis), ticks (Tetranychus kanzawai), ticks (Rhipicephalus sanguineus) and other ticks (Cheyletus acc malaccensis), stag beetle tick (Tyrophagus putrescent moth) Tick (Dermacentor taiwanicus), Chinese cabbage mite (Acaphylla theavagrans), Chinese dust mite (Polyphagotarsonemus latus), Tomato mite (Aculops lycopersici), Trichoid mite (Ornithonyssus sylvairum), Nami spider mite (
  • Amite termites (Reticulitermes miyatakei), American termites (Incisitermes minor), Termites (Coptotermes formosanus), Termites (Hodotermopsis japonica), Common termites (Reticulitermes termm ants) , Glyptotermes , Nakajima termite (Glyptotermes nakajimai), Nitobe termite (Pericapritermes nitobei), Yamato termite (Reticulitermes speratus) and the like.
  • cockroach Periplaneta fuliginosa
  • German cockroach Blattella germanica
  • Great cockroach Blatta orientalis
  • Greater cockroach Periplaneta brunnea
  • Greater cockroach Blattella lituriplanet (Periplaneta americana) and the like.
  • fleas examples include human fleas (Pulex irritans), cat fleas (Ctenocephalides felis), chicken fleas (Ceratophyllus gallinae), and the like.
  • Nematodes for example, strawberry nematode (Nothotylenchus acris), rice scallop nematode (Aphelenchoides besseyi), red-footed nematode (Pratylenchus penetrans), red-knot nematode (Meloidogyne hapla), sweet potato nematode (Meloidogyne rostochiensis), Javaloid nematode (Meloidogyne javanica), soybean cyst nematode (Heterodera glycines), southern nematode nematode (Pratylenchus coffeae), and pterolenchus nematode (Pratylenchus neglectus)
  • mollusks examples include Pomacea canaliculata, Achatina fulica, slug (Meghimatium bilineatum), Lehmannina valentiana, Limax flavus, and Acusta despecta Is mentioned.
  • the agricultural and horticultural insecticide of the present invention has a strong insecticidal effect against tomato kibaga (Tuta absoluta) as other pests.
  • animal parasite ticks Boophilus microplus
  • black tick ticks Raicephalus sanguineus
  • yellow tick ticks Haemaphysalis longicornis
  • yellow ticks Haemaphysalis flava
  • tsurigane tick ticks Haemaphysata tick
  • Tick Haemaphysalis concinna
  • tick Haemaphysalis japonica
  • tuna Haemaphysalis kitaokai
  • tick Haemaphysalis ias
  • tick Ixodes ovatus
  • tick desmite Ticks Dermanyssus, ticks such as Amblyomma testudinarium, Haemaphysalis megaspinosa, Dermacentor reticulatus, and Dermacentor taiwanesis gallinae
  • avian mite Ornithonyssus sylviarum
  • fleas to be controlled include, for example, ectoparasite worms belonging to the order Flea (Siphonaptera), more specifically fleas belonging to the family Flea (Pulicidae), Cleaphyllus (Ceratephyllus), etc. .
  • Fleas belonging to the family flea family include, for example, dog fleas (Ctenocephalides canis), cat fleas (Ctenocephalides felis), human fleas (Pulex irritans), elephant fleas (Echidnophaga gallinacea), keops mouse fleas (Xenopsylla cheopis), Leptopsylla segnis), European rat minnow (Nosopsyllus fasciatus), and Yamato mouse minnow (Monopsyllus anisus).
  • ectoparasites to be controlled include, for example, cattle lice (Haematopinus eurysternus), horse lice (Haematopinus asini), sheep lice (Dalmalinia ovis), cattle lice (Linognathus vituli), pig lice (Haematopinus ⁇ suius ⁇ pubis), And lice such as head lice (Pediculus capitis), and lice such as dog lice (Trichodectes canis), buffalo (Tabanus trigonus), green hawks (Culicoides schultzei), and blood-sucking dipterans such as Simulium ornatum Examples include pests.
  • endoparasites include nematodes such as pneumoniae, benthic, nodular worms, gastric parasites, roundworms, and filamentous worms, manson cleft worms, broad-headed crest worms, berries Tapeworms such as tapeworms, multi-headed tapeworms, single-banded tapeworms, and multi-banded tapeworms, flukes such as Schistosoma japonicum, and liver fluke, and coccidium, malaria parasites, intestinal granulocysts, toxoplasma And protozoa such as Cryptosporidium.
  • nematodes such as pneumoniae, benthic, nodular worms, gastric parasites, roundworms, and filamentous worms, manson cleft worms, broad-headed crest worms, berries Tapeworms such as tapeworms, multi-headed tapeworms, single-banded tapeworms, and multi-banded tapeworms,
  • the agricultural and horticultural insecticide containing the heterocyclic compound having a conjugated oxime group represented by the general formula (1) of the present invention or a salt thereof as an active ingredient includes paddy field crops, field crops, fruit trees, vegetables, other crops and Since it has a remarkable control effect against the pests that cause damage to flower buds, etc., according to the time when the occurrence of pests is expected, seedling facilities, paddy fields, fields,
  • the desired effect of the agricultural and horticultural insecticide of the present invention can be achieved by treating the fruit trees, vegetables, other crops, seeds such as flower buds, paddy water, stalks and leaves, or a cultivation carrier such as soil.
  • Useful plants to which the agricultural and horticultural insecticide of the present invention can be used are not particularly limited. Red beans, broad beans, green beans, green beans, peanuts, etc.), fruit trees and fruits (apples, citrus fruits, pears, peaches, peaches, plums, cherry peaches, walnuts, chestnuts, almonds, bananas, etc.), leaves and fruit vegetables (cabbage, Tomatoes, spinach, broccoli, lettuce, onions, green onions (satsuki, parsley), peppers, eggplants, strawberries, peppers, ladle, leek, etc.
  • crops for processing (salmon, hemp, beet, hop, sugar cane, sugar beet, olive, rubber, coffee, tobacco, tea, etc.)
  • Cucumbers (pumpkin, cucumber, watermelon, mushroom, melon, etc.), pastures (orchard grass, sorghum, timothy, clover, alfalfa, etc.), turf (Korean turf, bentgrass, etc.), fragrances, etc.
  • the “plant” includes HPPD inhibitors such as isoxaflutol, ALS inhibitors such as imazetapyr and thifensulfuron methyl, EPSP synthase inhibitors such as glyphosate, glutamine synthase inhibitors such as glufosinate, cetoxydim and the like. Also included are plants that have been rendered resistant by classical breeding methods or genetic recombination techniques to resistance to herbicides such as acetyl CoA carboxylase inhibitors, bromoxynil, dicamba, 2,4-D.
  • HPPD inhibitors such as isoxaflutol
  • ALS inhibitors such as imazetapyr and thifensulfuron methyl
  • EPSP synthase inhibitors such as glyphosate
  • glutamine synthase inhibitors such as glufosinate, cetoxydim and the like.
  • plants that have been rendered resistant by classical breeding methods or genetic recombination techniques to resistance to herbicides such as
  • Plants to which tolerance to an acetyl-CoA carboxylase inhibitor has been imparted are Procedures of the National Academy of Sciences of the United States of America (Proc. Natl. Acad. Sci). USA) 87, 7175-7179 (1990).
  • a mutant acetyl CoA carboxylase resistant to an acetyl CoA carboxylase inhibitor has been reported in Weed Science 53, 728-746 (2005).
  • Introducing a plant resistant to an acetyl-CoA carboxylase inhibitor by introducing a mutation associated with imparting resistance into a plant or introducing a mutation associated with imparting resistance into a plant acetyl-CoA carboxylase, and further, chimeric plastic technology (Gura T. et al. 1999.
  • insecticidal proteins derived from Bacillus cereus and Bacillus popirie Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C derived from Bacillus thuringiensis Endotoxins; insecticidal proteins such as VIP1, VIP2, VIP3 or VIP3A, insecticidal proteins from nematodes, scorpion toxins, spider toxins, bee toxins or insect-specific neurotoxins, toxins produced by animals, filamentous fungal toxins, plant lectins, Agglutinin, trypsin inhibitor, serine protease inhibitor, and protease inhibitors such as patatin, cystatin, papain inhibitor, lysine, corn-RIP, abrin, ruffin, saporin, bryodin Ribosome-inactivating protein (RIP), 3-hydroxysteroid oxidase, ecdysteroid
  • insecticidal proteins such as VIP1,
  • toxins expressed in such genetically modified plants Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, Cry9C, Cry34Ab or Cry35Ab and other ⁇ -endotoxin proteins, VIP1, VIP2, VIP3A, etc.
  • insecticidal protein hybrid toxins partially defective toxins, and modified toxins.
  • Hybrid toxins are produced by new combinations of different domains of these proteins using recombinant techniques.
  • Cry1Ab lacking a part Cry1Ab lacking a part of the amino acid sequence is known.
  • the modified toxin one or more amino acids of the natural toxin are substituted.
  • Examples of these toxins and recombinant plants capable of synthesizing these toxins are EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878. , WO 03/052073, and the like.
  • Toxins contained in these recombinant plants particularly confer resistance to Coleoptera, Hemiptera pests, Diptera pests, Lepidoptera pests and nematodes.
  • the agricultural and horticultural insecticides of the present invention can be used in combination or systematized with these techniques.
  • the insecticide for agricultural and horticultural use according to the present invention is used as it is to control various pests, or appropriately diluted with water or the like, or suspended in an amount effective for controlling the pests or nematodes.
  • pests and nematodes occurring in fruit trees, cereals, vegetables, etc., in addition to spraying on the foliage, seed immersion in seeds, seed dressing, calper treatment Etc.
  • it can be used for nutrient solution in nutrient solution (hydroponics) cultivation, smoke, or trunk injection.
  • the agricultural and horticultural insecticide of the present invention may be used as it is, appropriately diluted with water or the like or suspended in an amount effective for pest control in a place where the occurrence of the pest is predicted.
  • the agricultural and horticultural insecticide of the present invention may be used as it is, appropriately diluted with water or the like or suspended in an amount effective for pest control in a place where the occurrence of the pest is predicted.
  • they can also be used as application to house building materials, smoke, bait and the like.
  • Examples of the seed treatment method include, for example, a method of immersing seeds in a liquid state without diluting or diluting a liquid or solid preparation and allowing the drug to penetrate into the seeds, mixing a solid preparation or liquid preparation with seeds, Examples thereof include a method of dressing and adhering to the surface of the seed, a method of coating the seed with an adhesive carrier such as a resin and a polymer, and a method of spraying the preparation around the seed simultaneously with planting.
  • the “seed” for performing the seed treatment means a plant body at the initial stage of cultivation used for the propagation of plants, for example, for seeds, bulbs, tubers, seed buds, stock buds, baskets, bulbs, or cuttings. Mention may be made of plants for vegetative propagation.
  • the “soil” or “cultivation carrier” of the plant when carrying out the method of use of the present invention refers to a support for cultivating crops, particularly a support for growing roots, and the material is not particularly limited. However, any material that can grow plants may be used, and so-called soil, seedling mats, water, etc. may be used. Specific materials include, for example, sand, pumice, vermiculite, diatomaceous earth, agar, gel-like substances, high It may be a molecular substance, rock wool, glass wool, wood chip, bark or the like.
  • a spraying method for crop foliage stored grain pests, house pests, hygiene pests, forest pests, etc., dilute liquid preparations such as emulsions and flowables or solid preparations such as wettable powders or granular wettable powders with water as appropriate.
  • Examples of the application method to the soil include, for example, a method in which a liquid preparation is diluted or not diluted with water and applied to a plant stock or a seedling nursery, etc.
  • a method of spraying to a nursery, etc. a method of spraying powder, wettable powder, granule wettable powder, granule, etc. before sowing or transplanting and mixing with the whole soil, a planting hole, making before planting or planting a plant body
  • Examples thereof include a method of spraying powder, wettable powder, wettable powder, granule, etc. on the strip.
  • the dosage form may vary depending on the time of application such as application during sowing, greening period, application during transplantation, etc., but agents such as powder, granule wettable powder, granules, etc. Apply by mold. It can also be applied by mixing with soil, and it can be mixed with soil and powder, granulated wettable powder or granules, for example, mixed with ground soil, mixed with soil covering, mixed with the entire soil. Simply, the soil and the various preparations may be applied alternately in layers.
  • solid preparations such as jumbo agents, packs, granules, granule wettable powders, and liquid preparations such as flowables and emulsions are usually sprayed on flooded paddy fields.
  • an appropriate formulation can be sprayed and injected into the soil as it is or mixed with fertilizer.
  • a chemical solution such as emulsion or flowable as a source of water flowing into a paddy field such as a water mouth or an irrigation device, it can be applied in a labor-saving manner along with the supply of water.
  • the agricultural and horticultural insecticide of the present invention can be treated to a cultivation carrier or the like close to a seed or a plant body from sowing to raising seedling.
  • a cultivation carrier or the like close to a seed or a plant body from sowing to raising seedling.
  • treatment on the plant source of the plant being cultivated is suitable.
  • a spray treatment using a granule or a irrigation treatment in a liquid of a drug diluted or not diluted with water can be performed. It is also a preferable treatment to mix the granules with the cultivation carrier before sowing and then sow.
  • the irrigation treatment of the liquid drug or the granule spraying treatment to the seedling nursery is preferred.
  • the agricultural and horticultural insecticide of the present invention is generally used in a form convenient for use according to a conventional method for agricultural chemical preparations.
  • the heterocyclic compound having a conjugated oxime group represented by the general formula (1) of the present invention or a salt thereof is added to an appropriate inert carrier or, if necessary, together with an auxiliary agent in an appropriate ratio.
  • an appropriate inert carrier or, if necessary, together with an auxiliary agent in an appropriate ratio.
  • the composition of the present invention can contain, in addition to the active ingredient, additive components usually used in agricultural chemical formulations or animal parasite control agents as required.
  • additive components include a carrier such as a solid carrier and a liquid carrier, a surfactant, a dispersant, a wetting agent, a binder, a tackifier, a thickener, a colorant, a spreading agent, a spreading agent, and an antifreezing agent. , Anti-caking agents, disintegrants, decomposition inhibitors and the like. In addition, you may use a preservative, a plant piece, etc. for an additional component as needed. These additive components may be used alone or in combination of two or more.
  • the solid support examples include natural minerals such as quartz, clay, kaolinite, pyrophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite, diatomaceous earth, and inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride.
  • liquid carrier examples include monohydric alcohols such as methanol, ethanol, propanol, isopropanol, and butanol, and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin.
  • monohydric alcohols such as methanol, ethanol, propanol, isopropanol, and butanol
  • polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin.
  • Alcohols such as propylene glycol ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, ethyl ether, dioxane, ethylene glycol monoethyl ether, dipropyl ether, tetrahydrofuran, etc.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, ethyl ether, dioxane, ethylene glycol monoethyl ether, dipropyl ether, tetrahydrofuran, etc.
  • Ethers normal paraffins, naphthenes, isoparaffins, kerosene, mineral oils and other aliphatic hydrocarbons
  • Aromatic hydrocarbons such as benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, dimethyl adipate, etc.
  • Esters lactones such as ⁇ -butyrolactone, amides such as dimethylformamide, diethylformamide, dimethylacetamide, N-alkylpyrrolidinone, nitriles such as acetonitrile, sulfur compounds such as dimethylsulfoxide, soybean oil, rapeseed oil, Examples thereof include vegetable oils such as cottonseed oil and castor oil, and water. These may be used alone or in combination of two or more.
  • surfactants used as dispersants and wetting agents include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene resin acid esters, polyoxyethylene fatty acid diesters, Polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene dialkyl phenyl ether, polyoxyethylene alkyl phenyl ether formalin condensate, polyoxyethylene polyoxypropylene block copolymer, polystyrene polyoxyethylene Block polymer, alkyl polyoxyethylene polypropylene block copolymer ether, polyoxye Lenalkylamine, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzyl phenyl ether, polyoxyalkylene styryl phenyl ether, acetylene dio
  • binders and tackifiers include carboxymethyl cellulose and salts thereof, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinyl pyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, and an average molecular weight of 6000 to 20000.
  • Polyethylene glycol polyethylene oxide having an average molecular weight of 100,000 to 5,000,000, phospholipid (for example, cephalin, lecithin, etc.) cellulose powder, dextrin, modified starch, polyaminocarboxylic acid chelate compound, cross-linked polyvinylpyrrolidone, maleic acid and styrenes Polymers, (meth) acrylic acid copolymers, half-esters of polycarboxylic alcohol polymers and dicarboxylic acid anhydrides, water soluble salts of polystyrene sulfonic acid, para Fin, terpene, polyamide resins, polyacrylate, polyoxyethylene, wax, polyvinyl alkyl ethers, alkylphenol-formalin condensates, synthetic resin emulsions, and the like.
  • phospholipid for example, cephalin, lecithin, etc.
  • cellulose powder dextrin
  • polyaminocarboxylic acid chelate compound cross-linked polyviny
  • thickener examples include xanthan gum, guar gum, diyutane gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch compound, water-soluble polymer such as polysaccharide, high-purity bentonite, fumed silica (fumed Inorganic fine powders such as silica and white carbon.
  • the colorant examples include inorganic pigments such as iron oxide, titanium oxide and Prussian blue, organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes.
  • antifreezing agent examples include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin.
  • Adjuvants for preventing caking and promoting disintegration include, for example, polysaccharides such as starch, alginic acid, mannose, galactose, polyvinylpyrrolidone, fumed silica (fumed silica), ester gum, petroleum resin, sodium tripolyphosphate, Sodium hexametaphosphate, metal stearate, cellulose powder, dextrin, methacrylate copolymer, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compound, sulfonated styrene / isobutylene / maleic anhydride copolymer, starch / polyacrylonitrile graft copolymer A polymer etc. are mentioned.
  • the decomposition inhibitor examples include desiccants such as zeolite, quicklime and magnesium oxide, antioxidants such as phenolic compounds, amine compounds, sulfur compounds and phosphoric acid compounds, and ultraviolet absorbers such as salicylic acid compounds and benzophenone compounds. It is done.
  • desiccants such as zeolite, quicklime and magnesium oxide
  • antioxidants such as phenolic compounds, amine compounds, sulfur compounds and phosphoric acid compounds
  • ultraviolet absorbers such as salicylic acid compounds and benzophenone compounds. It is done.
  • preservative examples include potassium sorbate, 1,2-benzothiazolin-3-one, and the like.
  • functional aids such as metabolic degradation inhibitors such as piperonyl butoxide, antifreezing agents such as propylene glycol, antioxidants such as BHT, UV absorbers and other supplements as necessary Agents can also be used.
  • the blending ratio of the active ingredient compound can be adjusted as necessary, and may be appropriately selected from the range of 0.01 to 90 parts by weight in 100 parts by weight of the agricultural and horticultural insecticide of the present invention.
  • 0.01 to 50 parts by weight 0.01 to 50% by weight based on the total weight of the agricultural and horticultural insecticide
  • the amount of the agricultural and horticultural insecticide of the present invention depends on various factors such as purpose, target pests, crop growth status, pest occurrence tendency, weather, environmental conditions, dosage form, application method, application location, application time, etc. Although it varies, the active ingredient compound may be suitably selected from the range of 0.001 g to 10 kg per 10 ares, preferably 0.01 g to 1 kg depending on the purpose.
  • Agricultural and horticultural insecticides of the present invention are pests to be controlled, other agricultural and horticultural insecticides, acaricides, nematicides, fungicides, for the purpose of expanding the appropriate period of control or reducing the dose. It can also be used by mixing with biological pesticides, etc., and can also be used by mixing with herbicides, plant growth regulators, fertilizers, etc., depending on the usage situation.
  • Agricultural and horticultural fungicides used for similar purposes include aureofungin, azaconazole, azithiram, acipetacs, acibenzolar, acibenzolar-S-methyl , Azoxystrobin, anilazine, amisulbrom, ampropylfos, ametoctradin, allyl alcohol, aldimorph, amobam, isothianyl ( isotianil), isovaledione, isopyrazam, isoprothiolane, ipconazole, iprodione, iproalicarb, iprobenfos, imazalil, imazalil, imazalil Iminoctadine, iminoctadine-albesilate, iminoctadine-triacetate, imibenconazole, uniconazole, uniconazole-P, eclomezole, echlomezole Edifenphos, etaconazole, e
  • biological pesticides include nuclear polyhedrosis virus (NV), granulosis virus (GV), cytoplasmic polyhedrosis virus (CPV), insect pox virus (Entomopoxivirus, EPV) ) Virus preparations, Monocrosporium ⁇ ⁇ phymatophagum, Steinernema ⁇ carpocapsae, Steinernema kushidai, Pasturia ⁇ pene insecticides, and Pasturia pene insecticides Sterilization of microbial pesticides, Trichoderma lignorum, Agrobacterium radiobactor, non-pathogenic Erwinia carotovora, Bacillus subtilis, etc.
  • microbial pesticide to be used by using mixed such as biological pesticides utilized as herbicides, such as Xanthomonas campestris (Xanthomonas campestris), the same effect can be expected.
  • examples of biological pesticides include Encarsia formosa, Aphidius colemani, Aphidoletes aphidimyza, Diglyphus isaea, Dacnusahysrica persimilis), natural enemies such as Amblyseius cucumeris, Orius sauteri, microbial pesticides such as Beauveria brongniartii, (Z) -10-tetradecenyl acetate, (E, Z) ) -4,10-tetradecadinyl acetate, (Z) -8-dodecenyl acetate, (Z) -11-tetradecenyl acetate, (Z) -13-icosen-10-one, 14-methyl-1 - May also be used in combination with pheromone agents such as octadecene It is a function.
  • pheromone agents such as octadecene It is a function.
  • the animal may be an animal other than a human.
  • An ectoparasite control agent for animals characterized by containing the compound according to the present invention or a salt thereof as an active ingredient, and an ectoparasite of the animal treated with the ectoparasite control agent A method for controlling animal ectoparasites is also within the scope of the present invention.
  • the compound according to the present invention can also be used by applying it to a skin of an animal such as a cat or a dog, usually in one or two places, in a punctate or cast application. The application area is usually 5 to 10 cm 2 .
  • the compounds in the present invention preferably spread once throughout the animal's body once applied and can be dried without crystallizing or altering the appearance or feel.
  • the amount used is preferably 0.1 to 10 ml depending on the weight of the animal, particularly about 0.5 to 1 ml for cats and about 0.3 to 3 ml for dogs.
  • the animal ectoparasites to which the ectoparasite control agent of the present invention is effective include fleas such as human fleas (Pulex irritans), Pulexes such as human fleas (Ctenocephalides felis), Ctenocephalides ⁇ such as dog fleas (Ctenocephalides canis), Xenopsylla such as Xenopsylla cheopis, Tunga such as Tunga penetrans, Echidnophaga such as chicken flea (Echidnophaga gallinacea), Nosopsyllus such as European rat minnow (Nosopsyllus fasciatus), etc.
  • fleas such as human fleas (Pulex irritans)
  • Pulexes such as human fleas (Ctenocephalides felis)
  • Ctenocephalides ⁇ such as dog fleas (Ctenocephalides canis)
  • Xenopsylla such as Xenopsyll
  • Pests such as head lice (Pediculus humanus capitis), Phtirus such as pheasants (Pthirus pubis), cattle lice (Haematopinus eurysternus), Haematopinus sui, ⁇ Damalinia such as Bobis (Damalinia bovis), Linognathus such as bovine white lice (Linognathus vituli), sheep trunk parasitic white lice (Linognathus ovillus), Solenopotes such as Solenopotes capillatus, etc.
  • the white-eye pests include Menopon, such as chicken lice (Menopon gallinae), Trimenopon spp., Trinoton spp., Trichodectes, such as dog lice (Trichodectes canis), and Felicola subro Examples include Felicolas, Bovicolas such as cow lice (Bovicola bovis), Menacanthus species such as chicks (Menacanthus stramineus), Werneckiellas (Werneckiella spp.), Lepikentrons (Lepikentron spp.), And the like.
  • the bugs of the stink bug are Cimixes such as bed bugs (Cimex lectularius), Netite bedbugs (Cimex hemipterus), Reduvius species such as Reduvius senilis, Arilus species such as Arilus critatus, -Rhodnius moths such as Prodnix (Rhodnius prolixus), Triatomas such as Triatoma rubrofasciata, Panstrongylus ssp.
  • Cimixes such as bed bugs (Cimex lectularius), Netite bedbugs (Cimex hemipterus), Reduvius species such as Reduvius senilis, Arilus species such as Arilus critatus, -Rhodnius moths such as Prodnix (Rhodnius prolixus), Triatomas such as Triatoma rubrofasciata, Panstrongylus ssp.
  • ophorus Schizophyllum genus (Chorioptes spp.), Spider mites (Hypodectes spp.), Pterolixes (Pterolichus spp.), Cytodites (Cytodites spp.), Laminosioptes (Laminosioptes spp.), Wax sus Dermanyssus, such as Ornithonyssus sylviarum, Ornithonyssus, such as house mite (Ornithonyssus bacoti), Varroa, such as honeybee mite, Varroa Ornithocheyletia spp., Demodex ⁇ ⁇ canis, Demodex cati, etc.
  • Examples of animals to be administered with the ectoparasite control agent of the present invention include animals that can serve as hosts for the animal ectoparasites, and generally include homeothermic animals and variable temperature animals kept as domestic animals and pets.
  • Examples of the thermostat animals include, for example, cattle, buffalo, sheep, goats, pigs, camels, deer, faros deer, reindeer, horses, donkeys, dogs, cats, rabbits, ferrets, mice, rats, hamsters, squirrels, monkeys, etc.
  • examples of fur animals include mink, chinchilla and raccoon. Examples of birds include chicken, goose, turkey, duck, pigeon, parrot and quail.
  • variable temperature animals examples include turtles such as tortoises, sea turtles, green turtles, turtles, lizards, iguanas, chameleons, geckos, pythons, snakes, cobras, etc., preferably constant temperature animals, more preferably dogs, cats. Mammals such as cattle, horses, pigs, sheep and goats.
  • the THF solution of the chloride was added dropwise to a THF solution of 3-amino-2-methylamino-5-trifluoromethylpyridine (0.50 g).
  • hexane was added to the reaction gold-metal.
  • the precipitated solid was collected by filtration, put into a saturated aqueous sodium carbonate solution, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the desired product (0.93 g, quantitative).
  • dppf represents 1,1′-bis (diphenylphosphino) ferrocene.
  • Formulation Example 1 Compound of the present invention 10 parts Xylene 70 parts N-methylpyrrolidone 10 parts Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate (weight ratio 1: 1) 10 parts or more are uniformly mixed and dissolved to prepare an emulsion.
  • Formulation Example 2 Compound of the present invention 3 parts Clay powder 82 parts Diatomaceous earth powder 15 parts The above is mixed and ground uniformly to form a powder.
  • Formulation Example 3 Compound of the present invention 5 parts Mixed powder of bentonite and clay 90 parts lignin sulfonate 5 parts The above is uniformly mixed, kneaded with an appropriate amount of water, granulated and dried to give granules.
  • Formulation Example 4 Compound of the present invention 20 parts Kaolin, synthetic highly dispersed silicic acid 75 parts Polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 5 parts by weight 5 parts or more are uniformly mixed and ground to obtain a wettable powder.
  • Control value test against peach aphid (Myzus persicae) Chinese cabbage was planted in a plastic pot having a diameter of 8 cm and a height of 8 cm to breed a peach aphid, and the number of parasites in each pot was investigated.
  • the heterocyclic compound having a conjugated oxime group represented by the general formula (1) of the present invention or a salt thereof is dispersed in water and diluted to 500 ppm of a chemical solution. After that, store the pot in the greenhouse, and on the 6th day after spraying the chemicals, investigate the number of parasites of peach aphid parasitic on each Chinese cabbage, calculate the control value from the following formula, and judge according to the following criteria did.
  • Ta Number of parasites before spraying in the treated zone
  • Ca Number of parasites before spraying in the untreated zone
  • C Number of parasites after spraying in the untreated zone
  • Test Example 2 Insecticidal test against Japanese brown planthopper (Laodelphax striatella) A heterocyclic compound having a conjugated oxime group represented by the general formula (1) of the present invention or a salt thereof is dispersed in water and diluted to a chemical solution of 500 ppm. (Cultivar: Nihonbare) soaked for 30 seconds, air-dried, placed in a glass test tube, inoculated with 10 each of the three Japanese beetles, inoculated with cotton plugs, examined the number of live and dead insects 8 days after inoculation, and corrected dead insects The rate was calculated from the following formula and judged according to the following criteria.
  • Test Example 3 Insecticidal test against Plutella xylostella Sponge seedlings were allowed to lay eggs and lay eggs, and cypress seedlings with laying eggs two days after the release were conjugated with the general formula (1) of the present invention.
  • the drug containing a heterocyclic compound having an oxime group as an active ingredient was immersed in a chemical solution diluted to 500 ppm for about 30 seconds, air-dried, and then allowed to stand in a thermostatic chamber at 25 ° C.
  • Six days after immersion in the chemical solution the number of hatching insects was investigated, the death rate was calculated by the following formula, and the determination was made according to the criteria of Test Example 2. 1 ward, 10 heads, 3 systems.
  • the compounds of the present invention were 2-2, 2-5, 2-6, 2-10, 3-6, 3-26, 3-55, 3-56, 3-76, 3-105, 3-106.
  • 3-126, 3-136, 4-6, 4-105, and 4-106 showed A activity.
  • the compound according to the present invention has an excellent control effect against a wide range of agricultural and horticultural pests and is useful.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

Dans la production de cultures agricoles et horticoles, les insectes nuisibles, etc. causent encore beaucoup de dégâts. Dans ces circonstances, la présente invention aborde le problème du développement et de la fourniture d'un nouvel insecticide agricole et horticole pour résoudre ainsi des problèmes tels que l'apparition d'insectes résistants aux produits chimiques existants. La présente invention concerne un composé hétérocyclique ayant un groupe d'oxime conjugué représenté par la formule générale (1) {dans laquelle : R1 représente un groupe haloalkyle ou haloalkylthio ; R2, R3 et R4 représentent un atome d'hydrogène ; A représente un atome d'azote ; A1 représente un groupe N-méthyle ou un atome d'oxygène ; A2 et A3 représentent un atome d'azote ou un groupe CH ; et m vaut 2} ou un sel dudit composé. L'invention concerne également un insecticide agricole et horticole comprenant le composé en tant que principe actif, et un procédé d'utilisation de l'insecticide agricole et horticole.
PCT/JP2018/016913 2017-04-27 2018-04-26 Composé hétérocyclique ayant un groupe éther d'oxime conjugué ou un sel de celui-ci, insecticide agricole et horticole le comprenant et son procédé d'utilisation WO2018199209A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017087949A JP2020128341A (ja) 2017-04-27 2017-04-27 共役したオキシムエーテル基を有する複素環化合物又はその塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法
JP2017-087949 2017-04-27

Publications (1)

Publication Number Publication Date
WO2018199209A1 true WO2018199209A1 (fr) 2018-11-01

Family

ID=63918576

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/016913 WO2018199209A1 (fr) 2017-04-27 2018-04-26 Composé hétérocyclique ayant un groupe éther d'oxime conjugué ou un sel de celui-ci, insecticide agricole et horticole le comprenant et son procédé d'utilisation

Country Status (2)

Country Link
JP (1) JP2020128341A (fr)
WO (1) WO2018199209A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020241606A1 (fr) 2019-05-27 2020-12-03 日本農薬株式会社 Composé hétérocyclique condensé ou sel de celui-ci comprenant un atome d'azote dans une réticulation, pesticide agricole contenant ledit composé, et son procédé d'utilisation
WO2024189139A1 (fr) 2023-03-14 2024-09-19 Syngenta Crop Protection Ag Lutte contre des nuisibles résistants aux insecticides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016026848A1 (fr) * 2014-08-21 2016-02-25 Syngenta Participations Ag Dérivés hétérocycliques à action pesticide comportant des substituants contenant du soufre
WO2016116338A1 (fr) * 2015-01-19 2016-07-28 Syngenta Participations Ag Dérivés polycycliques à activité pesticide comportant des substituants contenant du soufre
WO2016121997A1 (fr) * 2015-01-29 2016-08-04 日本農薬株式会社 Composé hétérocyclique fusionné contenant un groupe cycloalkylpyridyle ou un sel de celui-ci, et insecticide agricole ou horticole contenant ledit composé et procédé d'utilisation associé
WO2017065183A1 (fr) * 2015-10-13 2017-04-20 日本農薬株式会社 Composé hétérocyclique condensé contenant un groupe oxime ou ses sels, et insecticide agricole et horticole contenant ledit composé et son procédé d'utilisation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016026848A1 (fr) * 2014-08-21 2016-02-25 Syngenta Participations Ag Dérivés hétérocycliques à action pesticide comportant des substituants contenant du soufre
WO2016116338A1 (fr) * 2015-01-19 2016-07-28 Syngenta Participations Ag Dérivés polycycliques à activité pesticide comportant des substituants contenant du soufre
WO2016121997A1 (fr) * 2015-01-29 2016-08-04 日本農薬株式会社 Composé hétérocyclique fusionné contenant un groupe cycloalkylpyridyle ou un sel de celui-ci, et insecticide agricole ou horticole contenant ledit composé et procédé d'utilisation associé
WO2017065183A1 (fr) * 2015-10-13 2017-04-20 日本農薬株式会社 Composé hétérocyclique condensé contenant un groupe oxime ou ses sels, et insecticide agricole et horticole contenant ledit composé et son procédé d'utilisation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020241606A1 (fr) 2019-05-27 2020-12-03 日本農薬株式会社 Composé hétérocyclique condensé ou sel de celui-ci comprenant un atome d'azote dans une réticulation, pesticide agricole contenant ledit composé, et son procédé d'utilisation
US12116370B2 (en) 2019-05-27 2024-10-15 Nihon Nohyaku Co., Ltd. Condensed heterocyclic compound having a bridgehead nitrogen atom or salt thereof, agricultural or horticultural insecticide comprising the compound, and method for using the insecticide
WO2024189139A1 (fr) 2023-03-14 2024-09-19 Syngenta Crop Protection Ag Lutte contre des nuisibles résistants aux insecticides

Also Published As

Publication number Publication date
JP2020128341A (ja) 2020-08-27

Similar Documents

Publication Publication Date Title
JP6581284B2 (ja) ベンゾオキサゾール化合物又はその塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法
JP6577051B2 (ja) ３ｈ‐ピロロピリジン化合物若しくはそのｎ‐オキサイド、又はそれらの塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法
JP6388671B2 (ja) シクロアルキルピリジル基を有する縮合複素環化合物又はその塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法
JP6488402B2 (ja) オキシム基を有する縮合複素環化合物又はその塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法
KR102181358B1 (ko) 옥심기를 가지는 축합복소환 화합물 또는 그의 염류, 및 이들의 화합물을 함유하는 농원예용 살충제 및 그 사용 방법
WO2017061497A1 (fr) Composé hétérocyclique condensé ou sels de celui-ci, insecticide à visée agricole et horticole le contenant, et son procédé d'utilisation
WO2016104746A1 (fr) Composé hétérocyclique à groupe cycloalkyle condensé, sel de celui-ci, insecticide agricole et horticole le contenant, et son procédé d'utilisation
WO2016039444A1 (fr) Composé d'imidazopyridazine ou ses sels, insecticide agricole et horticole contenant ledit composé et utilisation associée
JP6683830B2 (ja) オキシム基を有するキノリン化合物、ｎ‐オキサイド又はその塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法
JPWO2019059244A1 (ja) シクロプロピルピリジル基を有するベンゾイミダゾール化合物又はその塩類、及びそれらの化合物を含有する農園芸用殺虫剤並びにその使用方法
WO2017146221A1 (fr) Composé hétérocyclique condensé présentant des hétérocycles liés et ses sels, insecticide agricole/horticole contenant ledit composé, et procédé d'utilisation dudit insecticide
WO2017146220A1 (fr) Composé de quinoléine présentant un hétérocycle condensé lié à celui-ci, n-oxyde ou sels correspondants et insecticide agricole et horticole contenant le composé et procédé pour son utilisation
WO2017026384A1 (fr) Composé imidazole ou ses sels, et insecticide agricole et horticole contenant ledit composé et son procédé d'utilisation
WO2014157600A1 (fr) Composé hétérocyclique condensé ou ses sels, pesticide agricole et horticole contenant ledit composé et son procédé d'utilisation
JP6717968B2 (ja) Ｎ‐アルキルスルホニルインドリン化合物及び該化合物を含有する農園芸用殺虫剤並びにその使用方法
WO2018070502A1 (fr) Composé de 1h-pyrrolopyridine, n-oxyde de celui-ci, sel de celui-ci, pesticide à usage agricole et horticole contenant ledit composé, et son procédé d'utilisation
JP2015003906A (ja) 縮合複素環化合物又はその塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法
WO2018199210A1 (fr) Composé hétérocyclique fusionné ou sel de celui-ci, insecticide agricole et horticole contenant l'un ou l'autre composé et procédé d'utilisation de l'insecticide agricole et horticole
WO2018070503A1 (fr) Composé 1h-pyrrolopyridine ou n-oxyde ou sel de celui-ci, insecticide agricole et horticole contenant ledit composé, et procédé d'utilisation dudit insecticide
WO2018003976A1 (fr) Composé hétérocyclique n-alkylsulfonyle fusionné ou leur sels, pesticide contenant ledit composé et procédé d'utilisation dudit pesticide
WO2018105632A1 (fr) Composé de quinoléine ayant un groupe carbamate, sel de celui-ci, insecticide pour une utilisation agricole et horticole contenant ledit composé, et utilisation dudit insecticide
WO2018124128A1 (fr) Composé 4h-pyrrolopyridine ou sels de celui-ci, et pesticide à usage agricole et horticole comprenant ces composés ainsi que procédé de mise en œuvre de ce pesticide
WO2018199208A1 (fr) Composé hétérocyclique à noyau à 5 chaînons contenant de l'azote ou sel de celui-ci, insecticide agricole et horticole le contenant, et son procédé d'utilisation
WO2018043675A1 (fr) Composé hétérocyclique fusionné ayant un groupe hydrazonyle ou des sels de celui-ci, pesticide pour une utilisation agricole et horticole contenant ledit composé, et son procédé d'utilisation
JP2017178820A (ja) シクロアルキルピリジル基を有する縮合複素環化合物又はその塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法

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: 18790845

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: 18790845

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载