WO2018199209A1

WO2018199209A1 - Heterocyclic compound having conjugated oxime ether group or salt thereof, and agricultural and horticultural insecticide comprising same and method for use thereof

Info

Publication number: WO2018199209A1
Application number: PCT/JP2018/016913
Authority: WO
Inventors: 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: 2017-04-27
Filing date: 2018-04-26
Publication date: 2018-11-01
Also published as: JP2020128341A

Abstract

In the production of agricultural and horticultural crops, insect pests, etc. still cause a good deal of damage. Under these circumstances, the present invention addresses the problem of developing and providing a novel agricultural and horticultural insecticide to thereby resolve issues such as the appearance of insects resistant to existing chemicals. The present invention provides a heterocyclic compound having a conjugated oxime group represented by general formula (1) {wherein: R1 represents a haloalkyl or haloalkylthio group; R2, R3 and R4 represent a hydrogen atom; A represents a nitrogen atom; A1 represents an N-methyl group or an oxygen atom; A2 and A3 represent a nitrogen atom or a CH group; and m represents 2} or a salt thereof, an agricultural and horticultural insecticide comprising the same as an active ingredient, and a method for using the agricultural and horticultural insecticide.

Description

Heterocyclic compounds having a conjugated oxime ether group or salts thereof, agricultural and horticultural insecticides containing these compounds, and methods of use thereof

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.

So far, various compounds have been studied as agricultural and horticultural insecticides, and certain heterocyclic compounds have been reported to be useful as insecticides (see, for example, 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.

JP 2009-280574 A JP 2010-275301 A JP 2011-79774 A JP 2012-131780 A International Publication No. 2012/086848 Pamphlet International Publication No. 2014/142292 Pamphlet International Publication No. 2015/121136 Pamphlet

In crop production such as agriculture and horticulture, damage caused by pests is still large, and development of new agricultural and horticultural insecticides is desired due to factors such as the generation of resistant pests against existing drugs.

As a result of intensive studies to solve the above-mentioned problems, 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.
[1] General formula (1)

{Wherein 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 ) alkylsulfinyl (C ₁ -C ₆ ) alkyl group; (c13) (C ₁ -C ₆ ) alkylsulfonyl _{(C 1} -C ₆₎ alkyl group; (c14) halo _{(C 1} -C ₆₎ alkylthio _{(C 1} -C ₆₎ alkyl group; (c15) halo _{(C 1} -C ₆₎ alkyl Sulfinyl _{(C 1} -C ₆₎ alkyl group; or (c16) halo _{(C 1} -C ₆₎ alkylsulfonyl _{(C 1} -C ₆₎ alkyl group; and. 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. } The heterocyclic compound or its salt which has the conjugated oxime group represented by these.
[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 -C ₆ ) alkyl group) ;) And m is 2. } 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.

In the definition of the general formula (1) of the heterocyclic compound having a conjugated oxime group of the present invention or a salt thereof, “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. Group, neopentyloxy group, 2,3-dimethylpropyloxy group, 1-ethylpropyloxy group, 1-methylbutyloxy group, normal hexyloxy group, isohexyloxy group, 1,1,2-trimethylpropyloxy group Linear or branched alkoxy having 1 to 6 carbon atoms, such as The indicated, "(C 2 _-C ₆₎ alkenyloxy group", for example, propenyloxy group, butenyloxy group, pentenyl group, a hexenyl group linear or branched 2 to 6 carbon atoms in the Represents an alkenyloxy group, and the “(C ₂ -C ₆ ) alkynyloxy group” means, for example, a linear or branched carbon atom number of 2 to 2 such as propynyloxy group, butynyloxy group, pentynyloxy group, hexynyloxy group, etc. 6 alkynyloxy groups are shown.

“(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, ethylsulfinyl group, normal propylsulfinyl group, isopropylsulfinyl group , Normal butylsulfinyl group, secondary butylsulfinyl group, tertiary butylsulfinyl group, normal pentylsulfinyl group, isopentylsulfinyl group, tertiary pentylsulfinyl group, neopentylsulfinyl group, 2,3-dimethylpropylsulfinyl group, 1-ethyl Linear or branched alkyl sulfinyl having 1 to 6 carbon atoms such as propylsulfinyl group, 1-methylbutylsulfinyl group, normal hexylsulfinyl group, isohexylsulfinyl group, 1,1,2-trimethylpropylsulfinyl group refers to the group "(C 1 _-C ₆₎ alkylsulfonyl group", for example, methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonyl group, Norumarubu Rusulfonyl group, secondary butylsulfonyl group, tertiary butylsulfonyl group, normal pentylsulfonyl group, isopentylsulfonyl group, tertiary pentylsulfonyl group, neopentylsulfonyl group, 2,3-dimethylpropylsulfonyl group, 1-ethylpropylsulfonyl group A linear or branched alkylsulfonyl group having 1 to 6 carbon atoms such as a group, 1-methylbutylsulfonyl group, normal hexylsulfonyl group, isohexylsulfonyl group, 1,1,2-trimethylpropylsulfonyl group, etc. Show.

“(C ₁ -C ₆ ) alkyl group”, “(C ₂ -C ₆ ) alkenyl group”, “(C ₂ -C ₆ ) alkynyl group”, “(C ₃ -C ₆ ) cycloalkyl group”, “(C ₃ -C ₆ ) cycloalkyloxy”, “(C ₁ -C ₆ ) alkoxy”, “(C ₂ -C ₆ ) alkenyloxy”, “(C ₂ -C ₆ ) alkynyloxy” ”,“ (C ₁ -C ₆ ) alkylthio ”,“ (C ₁ -C ₆ ) alkylsulfinyl ”,“ (C ₁ -C ₆ ) alkylsulfonyl ”,“ (C ₂ -C ₆ ) alkenylthio ” Group ”,“ (C ₂ -C ₆ ) alkynylthio ”,“ (C ₂ -C ₆ ) alkenylsulfinyl ”,“ (C ₂ -C ₆ ) alkynylsulfinyl ”,“ (C ₂ -C ₆ ) ” alkenylsulfonyl group "," _(C 2 -C ₆₎ A Kinirusuruhoniru group ", is a hydrogen atom" _(C 3 -C ₆₎ cycloalkylthio group "," _(C 3 -C ₆₎ cycloalkyl alkylsulfinyl group "or" _(C 3 -C ₆₎ cycloalkyl sulfonyl group " One or two or more halogen atoms may be substituted at the position where substitution is possible. When two or more halogen atoms are substituted, the halogen atoms may be the same or different.

The above-mentioned 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 group”, “halo (C ₂ -C ₆ ) alkynylthio group”, “halo (C ₂ -C ₆₎ alkenylsulfinyl group ""Halo _(C 2 -C ₆₎ alkynylsulfinyl group", "halo _(C 2 -C ₆₎ alkenyl-sulfonyl group", "halo _(C 2 -C ₆₎ alkynyl-sulfonyl group", "halo _(C 3 -C ₆ ) cycloalkylthio group "refers to a" halo _(C 3 -C ₆₎ cycloalkyl alkylsulfinyl group "or" halo _(C 3 -C ₆₎ cycloalkyl sulfonyl group ". Any significance and exemplification of the substituents per se in the present invention are obvious to those skilled in the art.

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. In addition, 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. There are (E isomer) -syn isomer (Z isomer), anti isomer (E isomer) -anti isomer (E isomer), and the present invention may be any isomer, Moreover, the isomer mixture of those arbitrary ratios may be sufficient.

The substituents represented by each symbol in the general formula (1) of the present invention may be those usually used.
In the heterocyclic compound having a conjugated oxime group represented by the general formula (1) of the present invention or a salt thereof, in the general formula (1), 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 ) 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 (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 ) alkylsulfinyl ( C ₁ -C ₆ ) alkyl group; (c13) (C ₁ -C ₆ ) alkylsulfonyl (C ₁ -C ₆ ) alkyl group; (c14) halo (C ₁ -C ₆ ) alkylthio (C ₁ -C ₆ ) An alkyl group; (c15) a halo (C ₁ -C ₆ ) alkylsulfinyl (C ₁ -C ₆ ) alkyl group; or (c16) a halo (C ₁ -C ₆ ) alkylsulfonyl (C ₁ -C ₆ ) alkyl group; A, A ² and A ³ are preferably CH or a nitrogen atom, and A ¹ is 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 group; Or (d4) (C ₂ -C ₆ ) represents an alkynyl group), m is preferably 0, 1, or 2 .
More preferably, 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 ) alkyl; A group;) and m is 2 .

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.

Manufacturing method 1.

{Wherein R ¹ , R ³ , R ⁵ , A, A ¹ , A ² , A ³ , and m are the same as above. MOM represents methoxymethyl, and R represents a C ₁ -C ₃ alkyl group such as a methyl group or an ethyl group. X represents a leaving group such as a halogen atom. }

Production method of step [a] 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- There may be mentioned 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. For example, aromatic hydrocarbons such as benzene, toluene and xylene, halogens such as methylene chloride, chloroform and carbon tetrachloride. Aliphatic 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 And 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. Use only one solvent or a mixture of two or more. It can be.

Since this reaction is an equimolar reaction, 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. 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.

Production Method of 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.

The inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction. For example, 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 Examples of 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.
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.

Production method of step [c] 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.

Examples of the oxidizing agent used in this reaction 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. 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. 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.

Production Method of 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).

Production Method of Step [e] 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). .

Production Method of 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.

Production Method of 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.

Production Method of Step [h] 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- There may be mentioned 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. For example, 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 Examples of 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.

Manufacturing method 2.

{In the formula, R ¹ , R ³ , R ⁵ , A, A ¹ , A ² , A ³ , and m are the same as described above, and X represents a halogen atom such as chlorine, bromine, or iodine. }

Production method of step [a-1] 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.

Production Method of Step [b] 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.

Production method of step [i-1] 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 Moreover, when using the alkali salt of the compound represented by General formula (4), it is not necessary to use a base.

Since this reaction is an equimolar reaction, 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. 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.

Production method of step [c] 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.

Examples of the oxidizing agent used in this reaction 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.

Production Method of Step [i-2] 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.

Examples of the metal catalyst that can be used in this reaction include a palladium catalyst, a nickel catalyst, an iron catalyst, a ruthenium catalyst, a platinum catalyst, a rhodium catalyst, and an iridium catalyst. These 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.

Examples of the palladium catalyst 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. Moreover, metal salts, such as palladium chloride, palladium bromide, palladium iodide, palladium acetate, can be illustrated. In addition, π-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) butane] palladium, dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium, complex compounds such as diphenyl phosphino ferrocene dichloropalladium complex with dichloromethane can be exemplified.

These palladium catalysts may be used alone or in combination with a tertiary phosphine. As the 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'-bis (diphenylphosphino) ferrocene, (R)-(+)-2,2'-bis (Diphenylphosphino) -1,1'-bi Futyl, (S)-(−)-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, (±) -2,2′-bis (diphenylphosphino) -1,1′- Binaphthyl and the like can be exemplified.

Examples of vinyl borate compounds that can be used in this reaction include vinyl magnesium bromide, vinyl magnesium chloride, vinyl zinc chloride, tributyl vinyl tin, potassium vinyl trifluoroborate, vinyl boric acid, vinyl boric anhydride, and vinyl borate 2- Examples thereof include methyl-2,4-pentanediol ester, vinyl boric acid pinacol ester, and triethoxyvinylsilane.

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. For example, 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. Halogenated aromatic hydrocarbons, nitriles such as acetonitrile, esters such as ethyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone To mention 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. . Moreover, this reaction can also be performed in the atmosphere of inert gas, such as nitrogen gas and argon gas, for example. 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.

Production method of 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.

Production method of step [k] 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.). 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.

Production Method of Step [l] 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. 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.

Production Method of Step [m] 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).

Production method of production intermediate (2a)

{Wherein R and MOM are the same as above. }

The intermediate of the compound of the present invention represented by the general formula (2a) can be produced by the following method.

Production method of step [α] 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. After completion of the reaction, 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.

Production method of step [β] 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). .

Production method of step [γ] 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.

Production Method of Step [δ] 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.

Next, specific examples of the compound of the present invention are shown below. In the following table, Me represents a methyl group, Et represents an ethyl group, n-Pr represents a normal propyl group, and 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 (Helicoverpa armigera) Phararodonta manleyi, Eumeta japonica, Pieris brassicae, Malocasoma neustria testacea, Stathmopoda masinissa, sephoblast (Cuphodes diospyrosella) Tetramoera schistaceana, yellowtail (Papilio machaon hippocrates), yellow bat (Endoclyta sinensis), guinea winged moth (Lyonetia prunifoliella), golden horned moth (Phyllonorycter ringoneella), crimma (Cydia) Eucoenogenes aestuosa), Grapeberry moss (Lobesia botrana), Black-tailed green moth (Latoia sinica), Black-faced red-eye moth (Euzophera batangensis), Phalonidia mesotypa, Spilosoma imparides moth Japanese oyster (Olethreutes mori), Japanese moth (Tineola bisselliella), Japanese bat (Endoclyta excrescens), Japanese moth (Nemapogon granellus), Cosca shiba (Synanthedon hector), Kodlinga (Cydia pomonella), Japanese black moth (Plutella xylostella), Pink Borer (Sesamia calamistis), Sankameiga (Scirpophaga incertulas), Shibata toga (Pediasia teterrellus), Potato moth (Phthorimaea operculella), Orchard moth (Stauropus fagi persimilis), Eleuella tena pod Bat (Palpifer sexnotata), Spodoptera mauritia, Scirpophaga innotata, Xestia c-nigrum, Spodoptera depravata, Anella prunus (Ephestia ku) , Seguro Hachiko ( Clostera anastomosis), Soybean looper (Pseudoplusia includens), Soybean stag beetle (Matsumuraeses falcana), Tobacco moth (Helicoverpa assulta), Tamanaginuwawa (Autographa nigrisigna), Tamanayagaga (Agrotis ipsilon), Chadokuga sperm Chanohosuga (Caloptilia theivora), Chamonaki (Homona magnanima), Chamadarameiga (Ephestia elutella), Chaminoga (Eumeta minuscula), Clostera anachoreta, Clowna anachoreta, Heliothis maritima, Spiana this pill fusca, Euproctis subflava, Biston robustum, tomato fruit worm (Heliothis zea), Aedia leucomelas, Narosoideus flavidorsalis, Nuciferum (Viuc) Grapholita molesta, Spulerina astaurota, Ectomyelois pyrivorella, Chilo suppressalis, Acrolepiopsis sapporensis, Plodia interpunctella, Islamidae, Isla Sitotroga cerealella, Spodoptera litura, Eucosma aporema, Acleris comariana, Scopelodes contractus, Orgyia thyellina, fall army worm (Spodoptera frug) ), Naranga aenescens, Andraca bipunctata, Grape squirrel (Paranthrene regalis), Grape sparrow (Acosmeryx castanea), Grape spider (Phyllocnistis toparcha), Grape turf (Endopiza viteana) Eupoecillia ambiguella), velvet bean caterpillar (Anticarsia gemmatalis), mosquito (Cnephasia cinereipalpana), mussels (Lymantria dispar), matsukareha (Dendrolimus spectabilis), peas moth (Leguminivora glycinivorella), peas phaseoli, Caloptilia soyella, Phyllocnistis citrella, Omiodes indicata, Archips fuscocupreanus, Acanthoplusia agnata, Moa sink, B (Carposina niponensis), peach moth (Conogethes punctiferalis), peach beetle (Synanthedon sp.), Peach leaf moth (Lyonetia clerkella), yellow swallowtail (Papilio helenus), common yellow butterfly (Colias erate poliographus), black moth Pieris rapae crucivora), white butterflies such as Pieris rapae, Euproctis similis, Acropepiopsis suzukiella, European corn borer (Ostrinia nubilalis), Mamestra brassicatis, ogi Hotheamaki (Phtheochroides clandestina), Apple Tokamaki (Hoshinoa adumbratana), Apple Kaleha (Odonestis pruni japonensis), Apple Kenmon (Triaena intermedia), Apple Kokukakumon-maki (Adoxophyes orana fasciata), Apple Kosinkui (Grapholita inopinata) Japanese oyster (Spilonota ocellana), Apple oyster (Spilonota lechriaspis), Apple oyster (Illiberis pruni), Apple squirrel (Argyresthia conjugella), Apple squirrel (Caloptilia zachrysa), Apple squirrel (Archips breviplicanus) , Cotton akamim (Pectinophora gossypiella), Watanomeiga (Notarcha derogata), cotton helicopter Chrono moth (Diaphania indica), fake American tobacco budworm (Heliothis virescens), and Wataringa (Earias cupreoviridis), and the like.

Hemiptera (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) , Stariodes iwasakii, Aspidiotus destructor, Usylorilygus pallidulus, Myzusmumecola, Myzusmumepi, Pseudaulacaspis phonicr Spider helicopter (Anacanthocoris striicornis), giant black beetle (Ectometopterus micantulus), giant beetle bug (Eysarcoris lewisi), giant pest beetle (Molipteryx fuliginosa), giant beetle (Cicadella viridi) Anchovy (Saissetia oleae), Whitefly (Trialeurodes vaporariorum), Amelia moth (Aguriahana quercus), Anthracnose bug (Lygus spp.), Euperaphis puncti pennis), citrus scale insects (Andaspis kashicola), citrus scale insects (Coccus pseudomagnoliarum), king beetle bugs (Cavelerius saccharivorus), chrysanthemum beetle (Galeatus spinifrons), citrus beetle moth, (Halyomorpha mista), Stephanitis fasciicarina, Trio's camphorae, Leptocorisa chinensis, Trioza quercicola, Uhryitesthrone ッパー, Grays Black-footed beetle (Paromius exiguus), Black-footed beetle (Duplaspidiotus claviger), Nephotettix nigropictus, Black-headed turtle (Halticiellus insularis), Black croaker Leafhopper (Perkinsiella saccharicida), black apple lice (Psylla malivorella), stag beetle (Anomomeura mori), stag beetle (Pseudococcus longispinis), stag beetle (Pseudaulacaspis pentagona), stag beetle ), Scarcharidus aphid (Togo hemipterus), Komikan Aphid (Toxoptera aurantii), Sugarcane scale insect (Saccharicoccus sacchari), Sugar beetle (Geoica lucifuga), Sugar ), Citrus snow scale (Unaspis citri), potato beetle aphid (Aulacorthum solani), white stink bug (Eysarcoris ventralis), silver leaf whitefly (Bemisia argentifolii), white leafhopper (Cicadella) spectra), white beetle (Aspidiotus hederae), red beetle bug (Liorhyssus hyalinus), white beetle (Calophya nigridorsalis), white-footed beetle (Sogatella furcifera), broad beetle aphid (Megoura コン crad) (Aphis glycines), Leptocorisa oratorius, Nephotettix virescens, Arophicon formosanum, Tobacco leaf (Cyrtopeltis tennuis), Tobacco tabaica , Chalcoleophyllum (Parlatoria theae), Chano marine scale (Pseudaonidia paeoniae), Empoasca onukii, Chalauen stink bug (Plautia stali), Chu Dipsa aphids (Dysaphis tulipae), Tulip beetle aphids (Macrosiphum euphorbiae), Azalea (Stephanitis pyrioides), horn beetle (Ceroplastes ceriferus), Camellia cris ), Glaucias subpunctatus, sugar beet turtle (Orthotylus flavosparsus), corn aphid (Rhopalosiphum maidis), corn planthopper (Peregrinus maidis), thornbill beetle (Eysarcoris parvus), cyper (Nilaparvata lugens), Psylla tobirae, Eurydema rugosum, Schizaphis piricola, Psylla pyricola, Nacyclohoshi Aphids (Parlatoreopsis pyri), Nasigunbai (Stephanitis nashi), Nasibonkai scales (Dysmicoccus wistariae), Neptune scales (Lepholeucaspis japonica), Nasimaru aphids (Sappaphis piri), Nisedai phi sera ), Rhopalosophum nymphaeae, Edwardianarosae, Pinnaspisaspidistrae, Pinspisaspidistrae, Psylla alni, Speusotettix ellafue panicicola), Adelphocoris lineolatus, Dysdercus poecilus, Parrotia ziziphi, Uhlerites debile, Lame lphax striatella), Eurydema pulchrum, Cletus trigonus, Clovia punctata, Empoasca sp., Copacus brilliant luridus), Japanese scale insect (Planococcus kraunhiae), stag beetle (Stenotus binotatus), sable beetle (Arboridia apicalis), scallop (Macrosteles fascifrons), spotted beetle (Dolycoris baccadel), triannulatus, grape aphid (Viteus vitifolii), beetle stink bug (Acanthocoris sordidus), black beetle stink bug (Leptocorisa acuta), stink bug (Macropes obnubilus), snail beetle (Cletus cl tus), potato pisilido (Paratrioza cockerelli), Maekiawafuki (Aphrophora costalis), yellow turtle (Lygus disponsi), spotted turtle (Lygus saundersi), pine beetle (Crisicoccus pinis), pine Emuco matsumotoi), bean aphid (Aphis craccivora), mare beetle (Megacopta punctatissimum), marsh beetle (Eysarcoris guttiger), citrus beetle (Lepidosaphes beckii), citrus beetle (Diaphorina citer) (Planococcus citri), citrus whitefly (Dialeurodes citri), mandarin white lice (Aleurocanthus spiniferus), mandarin orange scale (Pseudococcus citriculus), mandarin orange leafworm (Zyginella citriulus), mandarin orange hawk Aphids (Pulvinaria citricola), Citrus scale insects (Coccus discrepans), Citrus scale insects (Pseudaonidia duplex), Citrus scale insects (Pulvinaria aurantii), Mizuki beetle scales (Lecaniumicorni), Minamiokaimu te (N) calcaratum), wheat beetle aphid (Rhopalosiphum padi), wheat aphid (Sitobion akebiae), wheat aphid (Schizaphis graminum), wheat leaf (Sorhoanus tritici), wheat walleye moth purim, ichBrachycaud Aphids (Myzus persicae), peach beetle (Hyalopterus pruni), willow beetle (Aphis farinose yanagicola), willow beetle (Metasalis populi), wild beetle (Unaspis yanonensis), porcupine Sacral lice (Mesohomotoma camphorae), Snowy eagle aphids (Aphis spiraecola), Apple aphids (Aphis pomi), Apple oyster scales (Lepidosaphes ulmi), Apple killer whales (Psylla mali), Apple croaker worms (Heterocordylis tus flavus) , Aphidonuguis mali, Orientus ishidai, Ovatus malicolens, Eriosoma lanigerum, Ceroplastes rubens, and Aphis gossypii et al.

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 vigintioctomaculata, Carpophilus dimidiatus, Cassida nebulosa, Luperomorpha tunebrosa, Phyllotreta striolco ), Curculio sikkimensis, Carpophilus hemipterus, Oxycetonia jucunda, Cornroot worms (Diabrotica spp.), Mimela splendens, Ribo zeum castaneum), weevil (Sitophilus oryzae), red-footed beetle (Palorus subdepressus), black beetle (Melolontha japonica), long-horned beetle (Anoplophora malasiaca), red beetle (Neatus picipes), inotarsa decemlineata), Southern corn rootworm (Diabrotica undecimpunctata howardi), sword beetle weevil (Sphenophorus usvenatus), juvenile horned beetle (Crioceris quatuordecis puncture), weevil (Conotrachelus nenupor Phaedon brassicae), tobacco beetle (Lasioderma serricorne), chibi beetle weevil (Sitona japonicus), white-horned beetle (Adoretus tenuimaculatus), white-footed beetle (Tenebrio molitor), Common beetle (Chaetocnema concinna), Dolphin's buoy (Anomala cuprea), Nagachakogane (Heptophylla picea), Epilachna vigintioctopunctata, Northern corn root worm (Diabrotica longicornis), Hanam Guri (Eucetonia pilifera), bark beetles (Agriotes spp.), Horned beetle (Attagenus unicolor japonicus), Japanese horned beetle (Pagria signata), Japanese common squirrel (Anomala rufocuprea), himekoku nostomu (Pii) laevigatus), Anthrenus verbasci, Oyster beetle (Lyctus brunneus), Olymptera cricket (Tribolium confusum), Methithia nigrobilineata, Grapy tiger beetle (Xylotrechus Pinewood beetle (Tomicus piniperda), pinewood spotted beetle (Monochamus alternatus), bean squirrel (Popillia japonica), bean scorpion (Epicauta gorhami), maizewevil (Sitophilus zeamais), peach squirrel tess Cowpea weevil (Callosobruchus maculatus), apple pea leaf weevil (Phyllobius armatus), apple weevil (Anthonomus pomorum), Rurihamushi (Linaeidea aenea), and boll weevil (Anthonomus grandis), and the like.

For example, 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 (Pegomya cunicularia), tomato leaf fly (Liriomyza sativae), eggplant fly (Liriomyza ticy moth) ), Aedes aegypti, Aedes albopictus, Bumbleflies (Liriomyza trifolii), Tomato leafflies (Liriomyza sativae), Citrus dors (a) (Dacus tsuneonis), wheat red midge (Sitodiplosis mosellana), Mugikimoguribae (Meromuza nigriventris), Mexican fruit flies (Anastrepha ludens), and apple maggot (Rhagoletis pomonella), and the like.

For example, Hymenoptera (Pristomyrmex pungens), Arbatidae, Monomelium pharaonis, Pheidole noda, Athalia rosae, Cristoforma, Kuriphilus , Hornets, black bee (Athalia infumata infumata), horned bee (Arge g pagana), Japanese bee (Athalia ハ japonica), cricket (Acromyrmex spp.), Fire ant (Solenopsis spp.), Apple honey bee (Arlen ali) (Ochetellus glaber) and the like.

Examples of the insects of the order Diptera (Hortocoryphus lineosus), Kera (Gryllotalpa sp.), Coago (Oxya hyla intricata), Cobainago (Oxya yezoensis), Tosama locust (Locusta migrago), Oneya (Homorocoryphus jezoensis), and emma cricket (Teleogryllus emma).

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.

For example, 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 (Tetranychus) icae), red spider mite (Eriophyes chibaensis), hymenid mite (Sarcoptes scabiei), black tick (Haemaphysalis longicornis), black legged tick (Ixodes , Southern ticks (Cheyletus moorei), southern ticks (Brevipalpus phoenicis), earthworm ticks (Octodectes cynotis), salmon mites (Dermatophagoides ptrenyssnus), yamato tick (Haemaphysalis flava), yamades ticks Apple spider mites (Aculus schlechtendali), apple spider mites (Panonychus ulmi), Lone star ticks (Amblyomma americanum), duck spider (Dermanyssus gallinae), Robin ticks (Rhyzoglyphus robini), a kind of spider mite (Sancassania sp.) It is done.

As the termite pests, for example, 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.

For example, cockroach (Periplaneta fuliginosa), German cockroach (Blattella germanica), Great cockroach (Blatta orientalis), Greater cockroach (Periplaneta brunnea), Greater cockroach (Blattella lituriplanet (Periplaneta americana) and the like.

Examples of fleas 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)

Examples of mollusks include Pomacea canaliculata, Achatina fulica, slug (Meghimatium bilineatum), Lehmannina valentiana, Limax flavus, and Acusta despecta Is mentioned.

Further, the agricultural and horticultural insecticide of the present invention has a strong insecticidal effect against tomato kibaga (Tuta absoluta) as other pests.

In addition, animal parasite ticks (Boophilus microplus), black tick ticks (Rhipicephalus 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), and avian mite such as Ornithonyssus bursa, Eutrombicula wichmanni, Leptotrombidium akamushi, Leptotrdium LLeptotrdium eptLeptotrdium eptLeptotrdium Tsutsumushi (Leptotrombidium tosa), European tick (Neotrombicula autumnalis), American tsutsugamushi (Eutrombicula alfreddugesi), and the tsutsugamushi tsutsumi (Helenicula miyagawai); And ticklets such as the catlet tick (Cheyletiella キュ blakei), rabbit cucumber mite (Psoroptes cuniculi), oxenid mite (Chorioptes bovis), and wolf mite mite (Otodectes cynotis) , Mites (Sarcoptes scabiei), and mites, such as a cat foraminous mites (Notoedres cati), as well as Demodex, etc. such as Inunikibidani (Demodex canis) can be mentioned.

Other 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).

Further, other 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 ラ suius ケ 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. In addition, examples of 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.

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. Among them, it is treated with seedling soil such as crops, flower buds, planting hole soil at the time of transplantation, plant origin, irrigation water, cultivated water in hydroponics, etc., and the present compound is absorbed from the root through or without soil. Application utilizing the so-called osmotic transfer property by making it a preferable form of use.

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. , Garlic, raccoon, 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. , Rosemary, thyme, parsley, pepper, ginger, etc.), flowers (flowers, roses, carnations, orchids, tulips, lilies, etc.), garden trees (ginkgo, sakura, aoki, etc.), forest trees (Todomatsu, spruce, Pine, hiba, cedar, camellia, eucalyptus, 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.

Examples of “plants” that have been given resistance by classical breeding methods include rapeseed, wheat, sunflower, and rice that are resistant to imidazolinone-based ALS-inhibiting herbicides such as imazetapil. Already on sale. Similarly, there are soybeans that are resistant to sulfonylurea ALS-inhibiting herbicides such as thifensulfuron methyl by classical breeding methods, and are already sold under the trade name of STS soybeans. Similarly, SR corn and the like are examples of plants to which tolerance has been imparted to acetyl CoA carboxylase inhibitors such as trion oxime and aryloxyphenoxypropionic acid herbicides by classical breeding methods.
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. Replacing the Genome's Spelling Mistakes. Science 285: 316-318. By introducing site-specific amino acid substitution mutations into the chill CoA carboxylase gene, ALS gene, etc., plants resistant to acetyl CoA carboxylase inhibitors, ALS inhibitors, etc. can be created. The agricultural and horticultural insecticides of the invention can be used.

Further, as toxins expressed in transgenic plants, 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-UDP-glucosyltransferase, steroid metabolic enzymes such as cholesterol oxidase, ecdysone inhibitor, HMG-CoA reductase, sodium channel, calcium channel inhibitor, etc. Ion channel inhibitors, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase, glucanase and the like.

Further, as toxins expressed in such genetically modified plants, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, Cry9C, Cry34Ab or Cry35Ab and other δ-endotoxin proteins, VIP1, VIP2, VIP3A, etc. Also included are 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. As a toxin lacking a part, Cry1Ab lacking a part of the amino acid sequence is known. In 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. For 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. Seed treatment, soil all layer mixing, crop application, floor soil mixing, cell seedling treatment, planting hole treatment, plant root treatment, top dress, rice box treatment, water surface application, etc. It can also be absorbed and used. In addition, it can be used for nutrient solution in nutrient solution (hydroponics) cultivation, smoke, or trunk injection.
Furthermore, 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. For example, in addition to spraying on stored grain pests, house pests, sanitary pests, forest pests, etc., 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.

As 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. , A method of spraying, a method of spraying powder, smoke or the like.
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.

As a method for applying rice to a seedling box, 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.
As a method of application to paddy fields, 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. In addition, at the time of rice planting, an appropriate formulation can be sprayed and injected into the soil as it is or mixed with fertilizer. In addition, by using 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.

In a field crop, 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. In plants that are sown directly in a field, in addition to direct treatment on seeds, treatment on the plant source of the plant being cultivated is suitable. For example, 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.
As the seeding of the cultivated plant to be transplanted and the treatment of the seedling raising period, in addition to the direct treatment to the seed, the irrigation treatment of the liquid drug or the granule spraying treatment to the seedling nursery is preferred. In addition, it is also preferable to treat a granule in a planting hole at the time of planting or to mix it with a cultivation carrier in the vicinity of the transplantation site.
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.
That is, 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. Mix, dissolve, separate, suspend, mix, impregnate, adsorb or adhere to appropriate dosage forms such as suspension, emulsion, liquid, wettable powder, wettable powder, granule, powder, tablet, pack What is necessary is just to formulate and use for a medicine etc.

The composition of the present invention (agricultural and horticultural insecticide or animal parasite control agent) can contain, in addition to the active ingredient, additive components usually used in agricultural chemical formulations or animal parasite control agents as required. Examples of the additive component 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.

Examples of the solid support 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. Synthetic silica, synthetic silicate, starch, cellulose, organic solid carriers such as plant powder (eg sawdust, coconut cob, tobacco stalk, etc.), plastic carriers such as polyethylene, polypropylene, polyvinylidene chloride, urea, Examples thereof include inorganic hollow bodies, plastic hollow bodies, fumed silica (fumed white silica), and the like. These may be used alone or in combination of two or more.

Examples of the liquid carrier 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. Alcohols, polyhydric alcohol compounds 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. 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 γ-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.

Examples of 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 diol, polyoxyalkylene-added acetylene diol, polyoxyethylene ether type silicone, ester type Nonionic surfactants such as silicone, fluorosurfactant, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxy Ethylene styryl phenyl ether sulfate, alkylbenzene sulfonate, alkylaryl sulfonate, lignin sulfonate, alkyls Succinate, naphthalenesulfonate, alkylnaphthalenesulfonate, salt of formalin condensate of naphthalenesulfonic acid, salt of formalin condensate of alkylnaphthalenesulfonic acid, fatty acid salt, polycarboxylate, polyacrylate, N -Anionic surfactants such as methyl-fatty acid sarcosinate, resinate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkylphenyl ether phosphate, laurylamine hydrochloride, stearylamine hydrochloride, oleylamine hydrochloride, Cationic surfactants such as stearylamine acetate, stearylaminopropylamine acetate, alkyltrimethylammonium chloride, alkylamine salts such as alkyldimethylbenzalkonium chloride, amphoteric boundaries such as amino acid type or betaine type Active agents. These surfactants may be used alone or in combination of two or more.

Examples of 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.

Examples of the thickener 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.

Examples of the colorant include inorganic pigments such as iron oxide, titanium oxide and Prussian blue, organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes.

Examples of the antifreezing agent 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.

Examples of the decomposition inhibitor 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.

Examples of the preservative include potassium sorbate, 1,2-benzothiazolin-3-one, and the like.
Furthermore, functional aids, activity enhancers 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. In the case of powder, granule, emulsion or wettable powder, 0.01 to 50 parts by weight (0.01 to 50% by weight based on the total weight of the agricultural and horticultural insecticide) is appropriate.

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.

Other agricultural and horticultural insecticides, acaricides, nematicides used for such purposes,
3,5-xylyl methylcarbamate (XMC), Bacillus thuringiensis aizawai, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis kurstaki, Bacillus thuringiensis tenebrionis, Bacillus thuringiensis produced crystalline protein toxin, BPMC, Bt toxin C chlorfenson), DCIP (dichlorodiisopropyl ether), DD (1, 3-dichloropropene), DDT, NAC, O-4-dimethylsulfamoylphenyl O, O-diethyl phosphorothioate (DSP), O-ethyl O-4-nitrophenyl phenylphosphonothioate (EPN), tripropylisocyanurate (TPIC), acrinathrin, azadirachtin, azinphos-methyl, acequinocyl, acetamiprid, acetoprole, acephate, actin ), Avermectin-B, amidoflumet, amitraz, alanycarb, aanycarb Aldicarb, aldoxycarb, aldrin, alpha-endosulfan, alpha-cypermethrin, albendazole, allethrin, isazofos, Isamidofos, isamidofos, isoxathion, isofenphos, isoprocarb (MIPC), ivermectin, imidaclos, imidacloprid (imidac1oprid), prothromlin (indoxacarb), esfenvalerate, ethiofencarb, ethion, ethiprole, etoxazole, etofenprox, ethoprophos, etrimfos, etrimfos, emamectin ema mectin), emamectin-benzoate, endosulfan, empenthrin, oxamyl, oxydemeton-methyl, oxydeprofos (ESP), oxybendazole ), Oxfendazole, potassium oleate, sodium oleate, cadusafos, cartap, carbary, carbosulfan, carbofuran ), Gamma-cyhalothrin, xylylcarb, quinalphos, kinoprene, chinomethionate, cloethocarb, clothianidin, clofentezinodi, clofentezinodi (chromafenozide), chlorantraniliprole (chlo rantraniliprole), chlorethoxyfos, chlordimeform, chlordane, chlorpyrifos, chlorpyrifos-methyl, chlorphenapyr, chlorfensonphos, chlorfensonphos (ch1orfenvinphos), chlorfluazuron, chlorobenzilate, chlorobenzoate, dicofol, salithion, cyanophos: cyanophos: diafenthiuron ), Diamidafos, cyantraniliprole, theta-cypermethrin, dienochlor, cyenopyrafen, dioxabenzofos, diofenolan, sigma- Cypermethrin (sigma- cypermethrin), diclofenthion (ECP), cycloprothrin, dichlorvos (DDVP), disulfoton, dinotefuran, cyhalothrin, cyphenothrin, fluflurin Diflubenzuron, cyflumetofen, diflovidazin, cyhexatin, cypermethrin, dimethylvinphos, dimethoate, dimefluthrin, ilaflufens, silaflufens cyromazine, spinetoram, spinosad, spirodiclofen, spirotetramat, spiromesifen, sulfluramid, sulprofos, sulfoxafurol (sulfo) xaflor), zeta-cypermethrin, diazinon, tau-fluvalinate, dazomet, thiacloprid, thiamethoxam, thiodicarb, thiocyclam ), Thiosultap, thiosultap-sodium, thionazin, thiometon, deet, dieldrin, tetrachlorbinphos, tetradifon, Tetramethylfluthrin, tetramethrin, tebupirimfos, tebufenozide, tebufenpyrad, tebufenpyrad, tefluthrin, teflubenzuron, demeton-S-methyl (demeton-S-methyl) , Temephos, deltamethrin (del tamethrin), terbufos, tralopyril, tralomethrin, transfluthrin, triazamate, triazuron, trichlamide, trichlorphon (DEP), triflumuron ), Tolfenpyrad, naled (BRP), nithiazine, nitenpyram, novaluron, noviflumuron, hydroprene, vaniliprole, bamidothion, vamidothion Parathion, parathion-methyl, halfenprox, halofenozide, bistrifluron, bisultap, hydramethylnon, hydroxypropyl starch propyl starch), binapa Binapacryl, bifenazate, bifenthrin, pymetrozine, pyraclorfos, pyrafluprole, pyridafenthion, pyridabene, pyridalylzon, pyridalylzon ), Pyriprole, pyriproxyfen, pirimicarb, pyrimidifen, pirimiphos-methy1, pyrethrins, fiproni1, fenazaquin, fenamiphos (fenazaquin) , Phenpropylbromo, phenoxythion (MEP), phenoxycarb (fenoxycarb), fenothiocarb, phenothrin, fenobucarb, fensulfothion, fenthion: MP P), phenthoate (PAP), fenvalerate, fenpyroximate, fenpropathrin, fenbendazole, fosthiazate, formetanate, butathiofos ), Buprofezin, furathiocarb, prallethrin, fluacrypyrim, fluazinam, fluazuron, fluensulfone, flucycloxuron, flucitritonate flucythrinate), fluvalinate, flupyrazofos, flufenerim, flufenoxuron, flufenzine, flufenprox, fluproxyfen, fluproxyfenate (flubro cythrinate), flubendiamide, flumethrin, flurimfen, prothiofos, protrifenbute, flonicamid, propaphos, propargite: BPPS, Profenofos, profluthrin, propoxur: PHC, bromopropylate, beta-cyfluthrin, hexaflumuron, hexythiazox, heptenophos, heptenophos Permethrin, benclothiaz, bendiocarb, bensu1tap, benzoximate, benfuracarb, phoxim, phosalone, fosthiazate, thhitane ), Phosphamido n), phosphocarb, phosmet (PMP), polynactins, formetanate, formothion, phorate, machine oil, malathion, milbemycin (Milbemycin), milbemycin-A, milbemectin, mecarbam, mesulfenfos, methomyl, metaldehyde, metaflumizone, metamidophos, Ammonium (metam-ammonium), metam-sodium, methiocarb, methidathion (DMTP), methylisothiocyanate, methylneodecanamide, methylparathion, methoxadiazone (metoxadiazone), methoxychlor, Methoxyfenozide, methofluthrin, metoprene, metolcarb, meperfluthrin, mevinphos, monocrotophos, monosultap, lambda-cyhalothrin, lambda-cyhalothrin Ryanodine, lufenuron, resmethrin, lepimectin, rotenone, levamisol hydrochloride, fenbutatin oxide, morantel tartarate, methyl bromide ( Examples thereof include methyl bromide), tricyclohexyltin hydroxide (cyhexatin), lime nitrogen (calcium cyanamide), lime-sulfur (calcium polysulfide), sulfur, and nicotine-sulfate.

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, ethaboxam, etirimol, etem, ethoxyquin, etridiazole, enestroburin, epoxiconazole, oxazixyl (Oxadixyl), oxycarboxin, copper-8-quinolinolate, oxytetracycline, copper-oxinate, oxpoconazole, oxpoconazole Oxpoconazole-fumarate, oxolinic acid, octhilinone, ofurace, orysastrobin, metam-sodium, kasugamycin, carbamorph, carpropamide ( carpropamid, carbendazim, carboxin, carboxin, carvone, quinazamid, quinazatol, quinacetol, quinoxyfen, quinomethionate, captafol, captan ), Kiraraxyl, quinconazole, quintozene, guazatine, cufraneb, cuprobam, glyodin, griseofulvin, crimazole, climbazole Cresol, kresoxim-methyl, clozolinate, clotrimazole, clobenthiazone, chloraniformethan, chloranil, chlorquinox , Chloropicrin, chlorfenazole, chlorodinitronaphthalene, chlorothalonil, chloroneb, zarilamid, salicylanilide, cyazofamid, cyazofamid Nart (diethyl pyrocarbonate), diethofencarb, cyclafuramid, diclocymet, dichlozoline, diclobutrazol, diclof Ruanide (dichlofluanid), cycloheximide, diclomezine, dicloran, dichlorophen, dichlorophen, dichlone, disulfiram, ditalianfos, dithianon, diniconazole , Diniconazole-M, diniconazole-zineb, dinocap, dinocton, dinosulfon, dinoterbon, dinobuton, dinopenton, dipyrithione, amine (Diphenylamine), difenoconazole, cyflufenamid, diflumetorim, cyproconazole, cyprodinil, cyprofuram, cypen Cypendazole, simeconazole, dimethirimol, dimethomorph, cymoxanil, dimoxystrobin, methyl bromide, ziram, silthiofam , Streptomycin, spiroxamine, sultropen, sedaxane, zoxamide, dazomet, thiadiazin, thiadinil, thiadifluor, thiabendole , Tioxymid, thiochlorfenphim, thiophanate, thiophanate-methyl, thicyofen, thioquinox, quinomethione Chinomethionat, thifluzamide, thiram, decafentin, tecnazene, tecloftalam, tecoram, tetraconazole, debacarb, dehydro Acetic acid (dehydroacetic acid), tebuconazole, tebufloquin, tebufloquin, dodicin, dodine, dodecylbenzenesulfonic acid bisethylenediamine copper complex (II) (DBEDC), dodemorph, dorazoxolon , Triadimenol, triadimefon, triazbutil, triazoxide, triamiphos, triarimol, trihlmol, trichlamide, tricyclazole, triticona Triticonazole, tridemorph, tributyltin oxide, triflumizole, trifloxystrobin, triforine, tolylfluanid, tolclofos- methyl, natamycin, nabam, nitrothal-isopropyl, nitrostyrene, nuarimol, copper nonylphenol sulfonate, halacrinate, validamycin (Validamycin), variafnalate, harpin protein, bixafen, picoxystrobin, picobenzamide, bithionol, bitteranol tanol), hydroxyisoxazole, hydroxyisoxazole-potassium, binapacryl, biphenyl, piperalin, hymexazol, pyroxystrobin, Pyracarbolid, pyraclostrobin, pyrazophos, pyrametostrobin, pyriofenone, pyridiinitril, pyrifenox, pyribencarb, pyrimethilil , Pyroxychlor, pyroxyfur, pyroquilon, vinclozolin, famoxadone, fenapanil, fenamidone, fe Fenaminosulf, fenarimol, fenitropan, phenoxanil, ferimzone, ferbam, fentin, fenpiclonil, fenpyrazamine, fenburazazole (fenpyrazamine) fenbuconazole), fenfuram, fenpropidin, fenpropimorph, fenhexamid, phthalide, buthiobate, butylamine, bupirimate, fuberidazole (Fuberidazole), blasticidin-S, furametpyr, furalaxyl, fluacrypyrim, fluazinam, fluoxastrobin, Fluotrimazole, fluopicolide, fluopyram, fluoroimide, furcarbanil, fluxapyroxad, fluquinconazole, fluconazole, fluconazole-cis (fluconazole-cis) furconazole-cis), fludioxonil, flusilazole, flusulfamide, flutianil, furtolanil, flutriafol, furfural, furmecyclox, fulmet Bell (flumetover), flumorph (flumorph), proquinazid (proquinazid), prochloraz, procymidone, prothiocarb, prothioconazole , Propamocarb, propiconcarb, propineb, propineb, furophanate, probenazole, bromuconazole, hexachlorobutadiene, hexaconazole, hexylthiophos ( hexylthiofos, bethoxazin, benalaxyl, benalaxyl-M, benodanil, benomyl, pefurazoate, benquinox, penconazole, penconazole, penconazole ), Pencicuron, benzohydroxamic acid, bentaluron, benthiazole, benchthiavalicarb-isopropyl, penthiopi Penthiopyrad, penflufen, boscalid, phosdiphen, fosetyl, fosetyl aluminum (fosetyl-Al), polyoxins, polyoxorim, polycarbamate, Folpet, formaldehyde, machine oil, maneb, mancozeb, mandipropamid, microzoline, myclobutanil, mildiomycin, milneb (Milneb), mecarbinzid, metasulfocarb, metazoxolon, metam, metam-sodium, metalaxyl, metalaxyl-M, methylamyl (Metiram) Methyl isothiocyanate, mepthyldinocap, metconazole, metsulfovax, methfuroxam, mettominostrobin, metrafenone, mepaniprim, mepaniprim Mefenoxam, meptyldinocap, mepronil, mebenil,
Inorganic sterilization, such as methyl iodide (iodomethane), rabenzazole, benzalkonium chloride, basic copper chloride, basic copper sulfate, silver metal Agent, sodium hypochlorote, cupric hydroxide, wettable sulfur, calcium polysulfide, potassium hydrogen carbonate, carbonic acid Copper-based compounds such as sodium hydrogen carbonate, inorganic sulfur, copper sulfate anhydride, nickel dimethyldithiocarbamate, 8-hydroxyquinoline copper, sulfuric acid Examples thereof include zinc sulfate and copper sulfate pentahydrate.

Similarly, as herbicides, 1-naphthylacetamide, 2,4-PA, 2,3,6-TBA, 2,4,5-T, 2,4,5-TB, 2,4-D, 2,4 -DB, 2,4-DEB, 2,4-DEP, 3,4-DA, 3,4-DB, 3,4-DP, 4-CPA, 4-CPB, 4-CPP, MCP, MCPA, MCPA Thioethyl, MCPB, ioxynil, aclonifen, azafenidin, acifluorfen, aziprotryne, azimsulfuron, ashlam, acetochlor, atrazine (Atrazine), atraton, anisuron, anilofos, aviglycine, abscisic acid, amicarbazone, amidosulfuron, amitrole, aminocyclo Pyraclol (aminocyclopyrachlor), aminopyralid (aminopyralid), amivudine ( amibuzin, amiprophos-methyl, ametridione, ametryn, alachlor, arichlor, alloxydim, alorac, isouron, isoouron Carbamide (isocarbamid), isoxachlortole, isoxapyrifop, isoxaflutole, isoxaben, isoxaben, isocil, isonoruron, isoproturon, isoproturon, isoproturon Isopropalin, isopolinate, isosomethiozin, inabenfide, ipazine, ipfencarbazone, iprymidam, imazaquin, imazapic, imazapic, imazapic (Imazapyr), imazamethapyr, imazamethabenz, imazamethabenz-methyl, imazamox, imazethapyr, imazosulfuron, indifram, indifram Indolebutyric acid, uniconazole-P (uniconazole-P), eglinazine, esprocarb, ethametsulfuron, ethametsulfuron-methyl, ethalluralin, Ethiolate, ethychlozate ethyl, ethidimuron, etinofen, ethephon, ethoxysulfuron, ethoxyfen, etnipromid, Ethofumesate, ethobenzanid, epronaz, erbon, endothal, oxadiazon, oxadiargyl, oxaziclomefone, oxasulfuron, oxasulfuron oxapyrazon, oxyfluorfen, oryzalin, orthosulfamuron, orbencarb, cafenstrole, cambendichlor, carbasulam, carfentrazone ), Carfentrazone-ethyl, karbutilate, carbetamide, carboxazole, quizalofop, quizalofop-P ofop-P), quizalofop-ethyl, xylachlor, quinoclamine, quinonamid, quinclorac, quinclorac, quinmerac, cumyluron, cliodinate ), Glyphosate, glufosinate, glufosinate-P, glufosinate-P, credazine, clethodim, cloxyfonac, clodinafop, clodinafop-arg ), Crotoluron, clopyralid, cloproxydim, cloprop, clobromuron, clofop, clomazone, clomethoxynil, chlomethoxyfen , Clomeprop, chlorazifop, chlorazine, cloransulam, chloranocryl, chloramben, chloransulam-methyl, chloridazon, chlorimuron, Chlorimuron-ethyl, chlorsulfuron, chlorthal, chlorthiamid, chlortoluron, chlornitrofen, chlorfenac, chlorfenprop, Chlorbufam, chlorflurazole, chlorflurenol, chlorprocarb, chlorpropham, chlormequat, chloret Chloreturon, chloroxynil, chloroxuron, chloropon, saflufenacil, cyanazine, cyanatryn, di-allate, diuron, diethamquat ), Dicamba, cycluron, cycloate, cycloxydim, diclosulam, cyclosulfamuron, dichlorprop, dichlorprop-P , Dichlobenil, diclofop, diclofop-methyl, dichlormate, dichloralurea, diquat, cisanilide, disul, siduron , Dithiopill dithiopyr, dinitramine, cinidon-ethyl, dinosam, cinosulfuron, dinoceb, dinoterb, dinofenate, dinoprop, dihalopropbutyl cyhalofop-butyl, diphenamid, difenoxuron, difenopenten, difenzoquat, cybutryne, cyprazine, cyprazole, diflufenzo, diflufenican Diflufenzopyr, dipropetryn, cypromid, cyperquat, gibberellin, simazine, dimexano, dimethachlor, dimidazon, dimezon Tamethrin (dimethametryn), dimethenamid (dimethenamid), simethrin (simetryn), simeton, dimepiperate, dimepiperate, dimefuron, cinmethylin, swep, sulglycapin, sulglycapin , Sulfallate, sulfentrazone, sulfosulfuron, sulfometuron, sulfometuron-methyl, secbumeton, sethoxydim, cebuthylazine , Terbacil, daimuron, dazomet, dalapon, thiazafluron, thiazopyr, thiencarbazone, thiencarbazone-methyl , Thiocarbazil, tioclorim, thiobencarb, thidiazimin, thidiazuron, thifensulfuron, thifensulfuron-methyl, desmedipham, desmedipham Desmetryn, tetrafluron, tenenylchlor, tebutam, tebuthiuron, terbumeton, tepraloxydim, tefuryltrione, tembotrione, tembotrione, tembotrione, tembotrione (Delachlor), terbacil, terbucarb, terbuchlor, terbuthylazine, terbutryn, topramezone, tralkoxidim (tr additivedim), triaziflam, triasulfuron, tri-allate, trietazine, tricamba, triclopyr, tridiphane, tritac, tritosulfuron (Tritosulfuron), triflusulfuron, triflusulfuron-methyl, trifluralin, trifloxysulfuron, tripropindan, tribenuron-methyl ), Tribenuron, trifop, trifopsime, trimeturon, naptalam, naproanilide, napropamide, nicosulfuron, nitralin, nitralin Nitrofen, nitrofluorfen, nipyraclofen, neburon, norflurazon, noruron, barban, paclobutrazol, paraquat, Parafluron, Haloxydine, Haloxyfop, Haloxyfop-P, Haloxyfop-methyl, halosafen, halosulfuron, halosulfuron -methyl), picloram, picolinafen, bicyclopyrone, bispyribac, bispyribac-sodium, pydanon, pinoxaden, bifenox, Piperofos (pip erophos, hymexazol, pyraclonil, pyrasulfotole, pyrazoxifene, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazolate, pyranafolate, bilanafos, bilanafos, bilanafos Pyraflufen-ethyl, pyriclor, pyridafol, pyrithiobac, pyrithiobac-sodium, pyridate, pyrifalid, pyributicarb, Pyribenzoxim, pyrimisulfan, pyrimisulfuron, pyriminobac-methyl, pyroxasulfone, pyroxsulam, fenasulam , Phenisopham, fenuron, fenoxasulfone, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, phenoxathiol (phenothio1) ), Fenoprop, phenobenzuron, fenthiaprop, fenteracol (
fenteracol), fentrazamide, phenmedipham, phenmedipham-ethyl, butachlor, butafenacil, butamifos, buthiuron, buthidazole, Butylate, Buturon, Butenachlor, Butroxydim, Butralin, Flazasulfuron, Flamprop, Furyloxyfen, Prynachlor , Primisulfuron-methyl, fluazifop, fluazifop-P, fluazifop-butyl, fluazolate, fluroxypyr, fluothiuro n), fluometuron, fluoroglycofen, flurochloridone, fluorodifen, fluoronitrofen, fluoromidine, flucarbazone, sodium flucarbazone (flucarbazone-sodium), fluchloralin, flucetosulfuron, fluthiacet, fluthiacet-methyl, flupyrsulfuron, flufenacet, flufenican ), Flufenpyr, flupropacil, flupropanate, flupoxam, flumioxazin, flumiclorac, flumiclorac, flumiclorac -pentyl), flumipropyn, flumezin, fluometuron, flumetsulam, fluridone, flurtamone, fluroxypyr, pretilachloran, protilachlor (Proglinazine), procyanidin (proyazine), prodiamine, prosulfalin, prosulfuron, prosulfocarb, propazazafop, propachlor, propazine (propachlor) propazine, propanil, propyzamide, propisochlor, prohydrojasmon, propyrisulfuron, propham, profluazol Profluralin, prohexadione-calcium, propoxycarbazone, propoxycarbazone-sodium, propoxydim, profoxydim, bromacil, brompyrazon, promethrin ), Prometon, bromoxynil, bromofenoxim, bromobutide, bromobonil, florasulam, hexachloroacetone, hexaazinone, petoxoxamid, Benazolin, penoxsulam, pebulate, beflubutamid, vernolate, perfluidone, bencarbazones ne), benzadox, benzipram, benzylaminopurine, benzthiazuron, benzfendizone, bensulide, bensulfuron-methyl, benzoylprop (Benzoylprop), benzobicyclon, benzofenap, benzofluor, bentazone, pentanochlor, benthiocarb, pendimethalin, pentoxazone (Pentoxazone), benfluralin, benfuresate, fosamine, fomesafen, foramsulfuron, forchlorfenuron, maleic hydrazide, meco Propo (mecoprop), mecoprop-P (mecoprop-P), mezinoterb (mesinoterb), mesosulfuron (mesosulfuron), mesosulfuron-methyl, mesotrione, mesoprazine, mesoprotryne, methoprotryne (Metazachlor), methazole, metazosulfuron, metabenzthiazuron, metamitron, metamifop, metam, metalpropalin, methiuron, Methiozolin, methiobencarb, methyldymron, metoxuron, metosurlam, metsulfuron, metsulfuron, metsulfuron-methyl, metflurazon Metobromuron, metobenzuron, metometon, metolachlor, metribuzin, mepiquat-chloride, mefenacet, mefluidide, monide , Monisouron, monuron, monochloroacetic acid, monolinuron, molinate, morfamquat, iodosulfuron, iodosulfuron-methyl sodium (iodosulfuron- methyl-sodium), iodobonil, iodomethane, lactofen, linuron, rimsulfuron, lenacil, rhodethanil, calcium peroxid e), methyl bromide, and the like.

Examples of biological pesticides include nuclear polyhedrosis virus (NV), granulosis virus (GV), cytoplasmic polyhedrosis virus (CPV), insect pox virus (Entomopoxivirus, EPV) ) Virus preparations, Monocrosporium ポリ phymatophagum, Steinernema ナ carpocapsae, Steinernema kushidai, Pasturia ペ pene insecticides, and Pasturia pene insecticides Sterilization of microbial pesticides, Trichoderma lignorum, Agrobacterium radiobactor, non-pathogenic Erwinia carotovora, Bacillus subtilis, etc. As 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.

Furthermore, 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.

Furthermore, it is also suitable for the control of parasites that parasitize inside or outside of animals such as humans, livestock, and pets. 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 類 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.

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.

As the mite pests, Amblyomma ローン americanum, Amblyomma maculatum and other Amblyomma species, Boophilus） microplus, Boophilus annulatus and other Boophilus species, American doc varieties (Dermacentor ), Dermacentor taiwanicus, Dermacentor oniandersoni, etc., Dermacentor species, Haemaphysalis longicornis, Tani physalis (Haemaphysalis flava), physics ovatus), Ixodes persulcatus, black legted ticks (Ixodes scapularis), western black tick (Ixodes pacificus), Ixodes holocyclus Ixodes, Rhipicephalus moths such as Rhipicephalus sanguineus and Ripeicephalus appendiculatus, Argas moths such as Argas persicus, Ornithodoros turmsi, Ornithodoros tursi Ornithodoros, Psoroptes ovis, Psoroptes equi, etc., Knemidocoptes mutans, etc., Knemidocoptes 類, Listr such as Notoedres such as (Notoedres muris), Sarcoptes such as Sarcoptes scabiei, Otodectes such as Otodectes cynotis, Listrophorus gibbus, etc. 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 イヌ canis, Demodex cati, etc. Demox, Myobia Mspp., Psorergates spp. ), Azalea (Trombicula pallida), Azalea (Trombicu) laombiscutellaris) and the like, and preferably flea insects, lice insects, or mite insects.

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. Furthermore, examples of fur animals include mink, chinchilla and raccoon. Examples of birds include chicken, goose, turkey, duck, pigeon, parrot and quail. Examples of the variable temperature animals 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.

Hereinafter, the representative compounds of the present invention and production examples of production intermediates will be described in more detail, but the present invention is not limited only to these examples.

Intermediate Production Example 1-1 Process for Producing 1.5-Chloro-6-ethoxycarbonylpyridine-3-carboxylic Acid (2a-3)

In an autoclave, a solution of 5,6-dichloropyridine-3-carboxylic acid (10 g, 52 mmol) in ethanol (60 mL) was added with DPPB (1,4-bis (diphenylphosphino) butane) (2.2 g, 10 mol%), Triethylamine (14 g, 2.5 eq), PdCl ₂ (PPh ₃ ) ₂ (911 mg, 2.5 mol%) was added and the reaction mixture was purged with carbon monoxide (CO pressure, 4.0 MPa) at 135 ° C. for 4 hours. Stir. Water and 3N hydrochloric acid were added to the reaction mixture to acidify the aqueous layer, and the mixture was extracted several times with ethyl acetate. The organic layer is dried over sodium sulfate and concentrated, and the resulting solid is washed with a solution of hexane-ethyl acetate = 2: 1 (v / v) to give the desired 5-chloro-6-ethoxycarbonylpyridine-3-carboxylic acid. 10.9 g, 76%).
Physical properties: ¹ H-NMR (CDCl ₃ ): 9.02 (d, 1H), 8.44 (d, 1H), 4.42 (dd, 2H), 1.33 (t, 3H)

Preparation Example of Intermediate 1-2.5-Ethylthio-6-ethoxycarbonylpyridine-3-carboxylic acid (2a-2)

After adding NaH (5.1 g) and EtSH (3.2 mL) to a DMF (dimethylformamide) solution (210 mL) of 5-chloro-6-ethoxycarbonylpyridine-3-carboxylic acid (9.7 g) at 0 ° C. And stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was slowly added to 300 mL of 1N hydrochloric acid solution at 0 ° C., and after confirming that the pH was 3, extraction with ethyl acetate was performed, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate and then dried under reduced pressure. MTBE (methyl tert-butyl ether) was added to the resulting residue, and the resulting solid was filtered to obtain the desired product (8.1 g, 75%).

Intermediate Production Example 1-3. Method for Producing 3-Ethylthio-5-hydroxymethylpyridine-2-carboxylic Acid Ethyl Ester (2a-1)

CDI (carbonyldiimidazole) (10 g) was added to a THF (tetrahydrofuran) solution (100 mL) of 5-ethylthio-6-ethoxycarbonylpyridine-3-carboxylic acid (10 g), and the mixture was stirred at room temperature for 2 hours. The above THF solution was slowly added to a 100 mL aqueous solution of NaBH ₄ (5.5 g) at 0 ° C., followed by stirring at room temperature for 1 hour. After completion of the reaction, 4N hydrochloric acid solution was added to adjust the pH to 2, followed by extraction with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography to give 3-ethylthio-5-hydroxymethylpyridine-2-carboxylic acid ethyl ester (6.4 g, 62%).

Intermediate Production Example 1-4.3-Ethylthio-5-methoxymethoxymethylpyridine-2-carboxylic acid ethyl ester (2a) production method

To a chloroform solution (50 mL) of 3-ethylthio-5-hydroxymethylpyridine-2-carboxylic acid ethyl ester (6.4 g), DIPEA (N, N-diisopropylethylamine) (13.6 mL) and methoxymethyl chloride (MOMCl) ( (6.0 mL) was added, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, an aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give 3-ethylthio-5-methoxymethoxymethylpyridine-2-carboxylic acid ethyl ester (7.1 g, 94%).

REFERENCE EXAMPLE 1-1.3-Ethylthio-5- (methoxymethoxymethyl) -N- (2-hydroxy-5- (trifluoromethylthio) phenyl) -2-pyridinecarboxylic acid amide

0.64 g of 3-ethylthio-5-methoxymethoxymethyl-2-pyridinecarboxylic acid ethyl ester prepared in the above intermediate preparation method in THF (10 mL) at 0 ° C. with NaH (0.36 g) and 0.4 g After adding 2-amino-4- (trifluoromethylthio) phenol in THF (2 mL), the mixture was stirred at 50 ° C. for 2 hours. After completion of the reaction, a saturated aqueous ammonium chloride solution was added, extracted with ethyl acetate, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, then dried under reduced pressure, purified by silica gel chromatography, and 3-ethylthio-5- (methoxymethoxymethyl) -N- (2-hydroxy-5- (trifluoromethylthio) phenyl ) -2-pyridinecarboxylic acid amide (0.73 g, 60%) was obtained.

Reference Example 1-2.2- (3-Ethylthio-5- (methoxymethoxymethyl) pyridin-2-yl) -5- (trifluoromethylthio) benzo [d] oxazole

To a THF solution (5 mL) of 0.73 g of 3-ethylthio-5- (methoxymethoxymethyl) -N- (2-hydroxy-5- (trifluoromethylthio) phenyl) -2-pyridinecarboxylic acid amide was added PPh ₃ (1 0.04 g) and bis (2-methoxyethyl) azodicarboxylate (0.93 g) were added, followed by stirring at 60 ° C. for 1 hour. After completion of the reaction, H ₂ O was added, extracted with ethyl acetate, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, then dried under reduced pressure, purified by silica gel chromatography, and 2- (3-ethylthio-5- (methoxymethoxymethyl) pyridin-2-yl) -5- (trifluoromethylthio). ) Benz [d] oxazole (0.70 g, quantitative) was obtained.

Reference Example 1-3.2- (3-Ethylsulfonyl-5-methoxymethoxymethylpyridin-2-yl) -5- (trifluoromethylthio) benzo [d] oxazole

To a solution of 0.68 g of 2- (3-ethylthio-5-methoxymethoxymethylpyridin-2-yl) -5- (trifluoromethylthio) benzo [d] oxazole in ethyl acetate (15 mL) at room temperature was added m-chloroperbenzoic acid. Acid (0.74 g) was added and stirred for 2 hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium thiosulfate solution were added, the mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine. The organic layer is dried over anhydrous magnesium sulfate, dried under reduced pressure, and purified by silica gel chromatography to give 2- (3-ethylsulfonyl-5-methoxymethoxymethylpyridin-2-yl) -5- (trifluoromethylthio). Benzo [d] oxazole (0.40 g, 60%) was obtained.

Reference Example 1-4.2- (3-Ethylsulfonyl-5-hydroxymethylpyridin-2-yl) -5- (trifluoromethylthio) benzo [d] oxazole

Concentrated hydrochloric acid (2 mL) was added to a methanol solution (7 mL) of 0.55 g of 2- (3-ethylsulfonyl-5-methoxymethoxymethylpyridin-2-yl) -5- (trifluoromethylthio) benzo [d] oxazole. And stirred at room temperature overnight. After completion of the reaction, the mixture was dried under reduced pressure, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure and purified by silica gel chromatography to give 2- (3-ethylsulfonyl-5-hydroxymethylpyridin-2-yl) -5- ( Trifluoromethylthio) benzo [d] oxazole (0.34 g, 70%) was obtained.

Reference Example 1-5.5-Ethylsulfonyl-6- (5- (trifluoromethylthio) benzo [d] oxazol-2-yl) nicotinaldehyde

To 0.34 g of 2- (3-ethylsulfonyl-5-hydroxymethylpyridin-2-yl) -5-trifluoromethylthiobenzo [d] oxazole in CHCl ₃ (7 mL) was added BAIB ([bis (acetoxy) -iodide Benzene) (0.32 g) and TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl free radical) (0.028 g) were added and stirred at room temperature overnight. After completion of the reaction, a saturated aqueous sodium thiosulfate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel chromatography to obtain the desired product (0.26 g, 75%).

Reference Example 1-6.3- {5- (Ethylsulfonyl) -6- (5- (trifluoromethylthio) benzo [d] oxazol-2-yl) pyridin-3-yl} acrylaldehyde

5-ethylsulfonyl-6- (5- (trifluoromethylthio) benzo [d] oxazol-2-yl) nicotinaldehyde (0.14 g, 0.34 mmol) in THF (3 mL) at room temperature (Triphenylphosphorylidene)- Acetaldehyde (0.14 g, 0.44 mmol) was added and stirred at 60 ° C. for 1 hour. After completion of the reaction, water was added and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain the desired product.

Production Example 1.3 Preparation of {5- (ethylsulfonyl) -6- (5- (trifluoromethylthio) benzo [d] oxazol-2-yl) pyridin-3-yl} acrylaldehyde oxime

NH ₂ OH in ethanol solution (2 mL) of 3- {5- (ethylsulfonyl) -6- (5- (trifluoromethylthio) benzo [d] oxazol-2-yl) pyridin-3-yl} acrylaldehyde at room temperature -HCl (0.023g, 0.33mmol) and sodium acetate (0.027g, 0.33mmol) were added, and it heated and refluxed for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and purified by silica gel column chromatography to obtain the desired product (0.033 g, 33%).

Preparation Example 2.3- {5- (Ethylsulfonyl) -6- (5- (trifluoromethylthio) benzo [d] oxazol-2-yl) pyridin-3-yl} acrylaldehyde O- (2,2, 2-trifluoroethyl) oxime production method

3- {5- (ethylsulfonyl) -6- (5- (trifluoromethylthio) benzo [d] oxazol-2-yl) pyridin-3-yl} acrylaldehyde oxime (0.033 g) in DMF (1 mL) Were added Cs ₂ CO ₃ (0.05 g) and 2,2,2-trifluoroethyl trifluoromethanesulfonate (0.02 mg), and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, an aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain the desired product (0.030 g, 77%).

Reference Example 2-1.3, Method for producing 6,6-dichloro-N- (2-methylamino-5-trifluoromethylpyridin-3-yl) -2-pyridinecarboxylic acid amide

DMF (10 μl) and thionyl chloride (490 μl) were added to a toluene solution (1.3 mL) of 3,6-dichloro-2-pyridinecarboxylic acid (0.50 g) at room temperature, and the mixture was heated to reflux for 5 hours. After completion of the reaction, it was concentrated under reduced pressure to obtain an acid chloride. At 0 ° C., the THF solution of the chloride was added dropwise to a THF solution of 3-amino-2-methylamino-5-trifluoromethylpyridine (0.50 g). After stirring at room temperature for 5 hours, 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).

Reference Example 2-2.2- (3,6-Dichloropyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine

An acetic acid solution (2.6 mL) of 3,6-dichloro-N- (2-methylamino-5-trifluoromethylpyridin-3-yl) -2-pyridinecarboxylic acid amide (0.93 g) was heated under reflux. Stir for hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and water was added. The precipitated solid was collected by filtration and dried under reduced pressure to obtain the desired product (0.75 g, 89%).

Reference Example 2-3.2- (3-Ethylthio-6-chloropyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine

Ice-cool a solution of 2- (3,6-dichloropyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (0.93 g) in THF (10 mL). Then, sodium hydride (0.10 g) was added, and then ethyl mercaptan (182 μl) was added dropwise. The reaction mixture was stirred for 3 hours under ice cooling, and water was added. The precipitated solid was washed with water and hexane, and the obtained solid was dried under reduced pressure to obtain the desired product (0.55 g, 63%).

Reference Example 2-4.2- (3-Ethylsulfonyl-6-chloropyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine

2- (3-Ethylthio-6-chloropyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (0.52 g) in ethyl acetate (15 mL) To the mixture, m-chloroperbenzoic acid (0.93 g) was added at room temperature and stirred for 2 hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium thiosulfate solution were added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and dried over anhydrous magnesium sulfate. The obtained organic layer was dried under reduced pressure to obtain the desired product (0.54 g, 95%).

Reference Example 2-5.2- (3-Ethylsulfonyl-6-vinylpyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine

2- (3-Ethylsulfonyl-6-chloropyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (0.8 g) in DME: H ₂ O = 4: Potassium vinyltrifluorate (0.40 g), PdCl ₂ (dppf) · acetone (0.08 g) and Cs ₂ CO ₃ (1.2 g) were added to 1 (v / v) solution (20 mL) and heated to reflux. . After completion of the reaction, the reaction mixture was dried under reduced pressure and purified by silica gel chromatography to obtain the desired product (0.69 g, 88%). dppf represents 1,1′-bis (diphenylphosphino) ferrocene.

Reference Example 2-6.5-Ethylsulfonyl-6- (3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridin-2-yl) Pyridine-2-aldehyde

2- (3-Ethylsulfonyl-6-vinylpyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (0.62 g) in THF: pH 7 buffer aqueous solution = 2: NMO (N-methylmorpholine N-oxide) (1.1 g, 50% in H ₂ O) and OsO ₄ (1.0 mL, 0.039 M in t- (BuOH) was added and stirred at room temperature overnight. Thereafter, NaIO ₄ (0.5 g) was added and stirred at room temperature for 2 hours. After completion of the reaction, a saturated Na ₂ S ₂ O ₃ solution was added, followed by extraction with ethyl acetate, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, dried under reduced pressure, and purified by silica gel chromatography to obtain the desired product (0.55 g, 89%).

Reference Example 2-7.3- {5- (ethylsulfonyl) -6- (3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridin-2-yl) pyridyl-2 -Il} Acrylic Aldehyde Production Method

THF solution of 5-ethylsulfonyl-6- (3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridin-2-yl) nicotinaldehyde (0.10 g, 0.22 mmol) (Triphenylphosphorarylidene) -acetaldehyde (0.086 g, 0.28 mmol) was added to (2 mL) at room temperature, and the mixture was stirred at 60 ° C. for 1 hr. After completion of the reaction, water was added and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain the desired product.

Preparation Example 4.3- {5- (Ethylsulfonyl) -6- (3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridin-2-yl) pyridyl-2-yl} -Acrylaldehyde O- (2,2,2-trifluoroethyl) oxime production method

3- {5- (Ethylsulfonyl) -6- (3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridin-2-yl) pyridyl-2-yl} acrylaldehyde CHCl ₃ solution (3 mL) at room temperature, J.P. Antibiotics, 53 (10), 1071-1085, 2000, 2,2,2-trifluoroethyltoxiamine hydrochloride (0.08 mg, 0.52 mmol) and pyridine (0.042 mL, 0. 52 mmol) was added and stirred for 3 hours. After completion of the reaction, a saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain the desired product (0.11 mg, 62%).

Examples of preparations are shown below, but are not limited thereto. In the formulation examples, “parts” means “parts by weight”.

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.

Next, test examples of the present invention will be shown, but the present invention is not limited thereto.

Test Example 1
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 T: Number of parasites after 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

Judgment criteria A ... 100% control value
B ... Control value 99% ~ 90%
C ... Control value 89% -80%
D ... Control value 79% -50%

As a result, 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.

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.

Corrected death rate A ... Corrected death rate 100%
B ... Corrected death rate 99% to 90%
C: Corrected death rate 89% -80%
D: Corrected death rate 79% -50%

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.

As a result, 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.

Claims

General formula (1)

{Wherein 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 ) alkylsulfinyl (C 1 -C 6 ) alkyl group; (c13) (C 1 -C 6 ) alkylsulfonyl (C 1 -C 6) alkyl group; (c14) halo (C 1 -C 6) alkylthio (C 1 -C 6) alkyl group; (c15) halo (C 1 -C 6) alkyl Rufiniru (C 1 -C 6) alkyl group; or (c16) halo (C 1 -C 6) alkylsulfonyl (C 1 -C 6) alkyl group; and. 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. } The heterocyclic compound or its salt which has the conjugated oxime group represented by these.
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 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 -C 6 ) alkyl group;) M is 2. } The heterocyclic compound or its salt which has the conjugated oxime group of Claim 1 represented by these.
An agricultural and horticultural insecticide comprising the heterocyclic compound having a conjugated oxime group according to claim 1 or a salt thereof as an active ingredient.
A method for using an agricultural and horticultural insecticide, which comprises treating a plant or soil with an effective amount of the heterocyclic compound having a conjugated oxime group according to claim 1 or a salt thereof.
An ectoparasite control agent for animals other than humans, comprising the heterocyclic compound having a conjugated oxime group or a salt thereof according to claim 1 or 2 as an active ingredient.