JP2016050201A - Pest control agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound highly active against pests.SOLUTION: The present invention provides a pest control agent comprising a compound represented by formula (I) or a salt thereof as an active ingredient, where A is a substitutable 5 membered heterocycle; Ris halogen, hydroxyl, mercapto, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, haloalkoxy, alkenylthio, alkynylthio, NRR, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, hydroxylalkyl, formyl or the like].SELECTED DRAWING: None

Description

  The present invention relates to a pest control agent containing a novel 4- (5-membered heterocyclic ethynyl) pyridine compound or a salt thereof as an active ingredient.

  Patent Document 1 describes that a specific 4- (aryl) pyridine derivative is useful as an agricultural and horticultural insecticide, and Patent Document 2 discloses that a specific pyridine compound has a controlling effect against pests. Patent Document 3 describes pyridine derivatives having an insecticidal and acaricidal action and salts thereof. However, Patent Documents 1, 2, and 3 do not describe the compound of the present invention. Patent Document 4 describes a specific 4- (arylethynyl) pyridine-based compound. However, the aryl moiety does not include 5-membered heterocycles.

International Publication No. 2010/064711 International Publication No. 2012/008526 JP-A-1-316359 International Publication No. 2014/098259

  Many pest control agents have been used for many years, but many have various problems such as insufficient efficacy, pests and the like acquiring resistance and limiting their use. Therefore, development of a novel pest control agent with few such drawbacks is desired. An object of the present invention is to provide a compound having high activity against pests, to provide a pest control agent using the compound, and to provide a method for controlling pests by applying the compound. It is.

  The present inventors have made various studies on pyridine derivatives in order to find better pest control agents. As a result, the present inventors have found that a novel 4- (5-membered heterocyclic ethynyl) pyridine compound has a very high control effect against pests with a low dose, and completed the present invention.

That is, the present invention
Formula (I):

[Wherein A is a 5-membered heterocyclic ring optionally substituted by R ¹ ;
R ¹ is a halogen atom, hydroxyl, mercapto, cyano, nitro, formyl, phenyl, benzyl optionally substituted with B, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆₎ alkynyl, (C ₃ -C ₆₎ cycloalkyl, (C ₁ -C ₆₎ haloalkyl, (C ₁ -C ₆₎ alkoxy, (C ₂ -C ₆₎ alkenyloxy, (C ₂ -C ₆₎ alkynyl Oxy, (C ₃ -C ₆ ) cycloalkoxy, tri (C ₁ -C ₆ ) alkylsilyl, (C ₁ -C ₆ ) alkoxy (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyloxy ( C ₁ -C ₆₎ alkyl, (C ₂ -C ₆₎ alkynyloxy (C ₁ -C ₆₎ alkyl, (C ₁ -C ₆₎ haloalkoxy (C ₁ -C ₆₎ alkyl, (C ₃ -C ₆ ) Cycloalkoxy (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) haloalkoxy, (C ₁ -C ₆ ) alkylthio, (C ₂ -C ₆ ) alkenylthio, (C ₂ -C ₆ ) alkynylthio , (C ₃ -C ₆₎ cycloalkylthio, (C ₁ -C ₆₎ Haroaruki Thio, (C ₁ -C ₆₎ alkylsulfinyl, (C ₂ -C ₆₎ alkenylsulfinyl, (C ₂ -C ₆₎ alkynylsulfinyl, (C ₃ -C ₆₎ cycloalkyl alkylsulfinyl, (C ₁ -C ₆₎ haloalkylsulfinyl, (C ₁ -C ₆₎ alkylsulfonyl, (C ₂ -C ₆₎ alkenyl-sulfonyl, (C ₂ -C ₆₎ alkynyl-sulfonyl, (C ₃ -C ₆₎ cycloalkylsulfonyl, (C ₁ -C ₆ ) Haloalkylsulfonyl, (C ₁ -C ₆ ) alkylthio (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkylsulfinyl (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkylsulfonyl (C ₁ -C ₆ ) alkyl, NR ³ R ⁴ , carboxyl, (C ₁ -C ₆ ) alkylcarbonyl, (C ₁ -C ₆ ) alkoxycarbonyl, (C ₁ -C ₆ ) alkylaminocarbonyl, di (C _1- C ₆ ) alkylaminocarbonyl, (C ₁ -C ₆ ) alkylcarbonyloxy, (C ₁ -C ₆ ) alkylcarbonylamino or (C ₁ -C ₆ ) alkylcarbonyl (C ₁ -C ₆ ) alkylamino;
B is a halogen atom, (C ₁ -C ₆ ) alkyl or (C ₁ -C ₆ ) haloalkyl;
R ² is a halogen atom, hydroxyl, mercapto, cyano, nitro, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₁ -C ₆ ) haloalkyl, (C ₁ -C ₆ ) alkoxy, (C ₂ -C ₆ ) alkenyloxy, (C ₂ -C ₆ ) alkynyloxy, (C ₁ -C ₆ ) alkylthio, (C ₂ -C ₆ ) alkenylthio, (C ₂ -C ₆ ) alkynylthio, (C ₁ -C ₆ ) haloalkoxy, NR ³ R ⁴ , (C ₁ -C ₆ ) alkylsulfinyl, (C ₂ -C ₆ ) alkenylsulfinyl, (C ₂ -C ₆ ) alkynylsulfinyl, (C ₁ -C ₆₎ alkylsulfonyl, (C ₂ -C ₆₎ alkenyl-sulfonyl, (C ₂ -C ₆₎ alkynyl-sulfonyl, (C ₁ -C ₆₎ alkoxy (C ₁ -C ₆₎ alkyl, (C ₁ -C ₆ ) alkylthio (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkylamino (C ₁ -C ₆ ) alkyl, di (C ₁ -C ₆ ) alkylamino (C ₁ -C ₆₎ alkyl, hydroxyl (C ₁ -C ₆₎ A Kill, formyl, carboxyl, (C ₁ -C ₆₎ alkylcarbonyl, (C ₁ -C ₆₎ alkoxycarbonyl, (C ₁ -C ₆₎ alkylaminocarbonyl, di (C ₁ -C ₆₎ alkylaminocarbonyl, ( C ₁ -C ₆ ) alkylcarbonyloxy, (C ₁ -C ₆ ) alkylcarbonylthio, (C ₁ -C ₆ ) alkylcarbonylamino or di (C ₁ -C ₆ ) alkylcarbonylamino; R ³ and R ⁴ each independently represents a hydrogen atom, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₃ -C ₆ ) cycloalkyl or (C ₁ -C ₆ ) is a haloalkyl 4- (5-membered heterocyclic ethynyl) pyridine compound or a salt thereof, a compound of formula (I) or a salt thereof as an active ingredient, The present invention relates to a method for controlling pests by applying an effective amount of the compound of I) or a salt thereof.

  The pest control agent comprising the compound of the general formula (I) or a salt thereof as an active ingredient has a very high control effect against pests at a low dose.

The heterocyclic moiety of the 5-membered heterocyclic ring which may be substituted with R ¹ represented by A in the formula (I) includes thienyl such as 2-thienyl and 3-thienyl; 2-furyl and 3-furyl. Such as 1-pyrrolyl, 2-pyrrolyl, and 3-pyrrolyl; oxazolyl such as 2-oxazolyl, 4-oxazolyl, and 5-oxazolyl; and 3-isoxazolyl, 4-isoxazolyl, and 5-isoxazolyl Isothazolyl such as 2-thiazolyl, 4-thiazolyl, 5-thiazolyl; isothiazolyl such as 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl; 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl Pyrazolyl such as: 1-imidazolyl, 2-imidazolyl, 4-imidazolyl Imidazolyl such as 5-imidazolyl; 1,3,4-oxadiazolyl such as 2- (1,3,4-oxadiazolyl); 3- (1,2,4-oxadiazolyl), 5- (1,2 1,2,4-oxadiazolyl) such as 1,4-oxadiazolyl); 1,3,4-thiadiazolyl such as 2- (1,3,4-thiadiazolyl); 3- (1,2,4-thiadiazolyl); 1,2,4-thiadiazolyl such as 5- (1,2,4-thiadiazolyl); 1- (1,2,4-triazolyl), 3- (1,2,4-triazolyl), 5- (1 1,2,4-triazolyl, such as 1,2,4-triazolyl); 1- (1,2,3-triazolyl), 2- (1,2,3-triazolyl), 4- (1,2,3 -Triazolyl), 5-membered monocyclic heterocycles such as 1,2,3-triazolyl;

  Examples of the halogen atom in the formula (I) or the halogen as a substituent include fluorine, chlorine, bromine or iodine atoms. The number of halogen atoms as a substituent may be 1 or 2 or more, and in the case of 2 or more, each halogen atom may be the same or different. Further, the halogen atom may be substituted at any position.

Examples of the alkyl or alkyl moiety in the formula (I) include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl. And linear or branched C ₁ -C ₆ groups such as

Examples of the alkenyl or alkenyl moiety in the formula (I) include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl, and 2-methyl-2. -Propenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-2-butenyl, 1-hexenyl, 2,3-dimethyl-2 - it includes straight chain or branched chain groups of C ₂ -C ₆ such as butenyl.

Examples of the alkynyl or alkynyl moiety in the formula (I) include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl- Linear or branched C ₂ -C ₆ groups such as 3-butynyl, 3,3-dimethyl-1-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl Is mentioned.

Examples of the cycloalkyl or cycloalkyl moiety in the formula (I) include C ₃ -C ₆ groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

  Examples of the salt of the compound of the formula (I) include any salt as long as it is acceptable in the art. For example, ammonium salts such as dimethylammonium salt and triethylammonium salt; Examples thereof include inorganic acid salts such as acid salts, sulfates and nitrates; organic acid salts such as acetates, trifluoroacetates, oxalates, p-toluenesulfonates and methanesulfonates.

  The compound of the formula (I) or a salt thereof may have an isomer such as an optical isomer, but the present invention includes either one or both of the isomers and the isomer mixture. It is. In the present specification, unless otherwise specified, isomers are described as a mixture. The present invention also includes various isomers other than those described above within the scope of technical common sense in the technical field. Depending on the type of isomer, there may be a chemical structure different from that of the formula (I). However, since those skilled in the art can fully recognize that they are related to isomers, the scope of the present invention. It is clear that it is within.

  The compound of the above formula (I) or a salt thereof (hereinafter abbreviated as the compound of the present invention) can be produced according to the following production methods and ordinary salt production methods, but is not limited to these methods. Absent.

Manufacturing method [1]
The compound of the present invention can be produced by reacting the compound of formula (II) with the compound of formula (III) or an acid addition salt thereof in the presence of a palladium catalyst, a copper salt and a base.

(In the production method [1], X is a halogen atom, and A and R ² are as described above.)
Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium (0) and bis (triphenylphosphine) palladium (II) dichloride.
Examples of the copper salt include copper (I) iodide.
The base may be an organic base or an inorganic base. Examples of the organic base include amine bases such as triethylamine and diisopropylamine. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate.
The reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent inert to the reaction, for example, an amine base such as triethylamine or diisopropylamine; an aprotic polar solvent such as N, N-dimethylformamide or acetonitrile; One type or two or more types can be appropriately selected from ethers and the like.
The reaction temperature can usually be about 20 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 24 hours.

Manufacturing method [2]
The compound of the present invention can also be produced by reacting the compound of formula (V) with the compound of formula (III) or an acid addition salt thereof in the presence of a palladium catalyst, a copper salt, a fluorine ion source and a base. .

(In the production method [2], X, A and R ² are as described above.)
Examples of the palladium catalyst copper salt and the base include the same ones as in the above production method [1].
Examples of the fluorine ion source include tetrabutylammonium fluoride (TBAF) and potassium fluoride.
The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include those similar to the above production method [1], and one or more of these can be appropriately selected and mixed for use.
The reaction temperature can usually be about 20 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 24 hours.

Manufacturing method [3]
In the formula (I), the compound of formula (Ib) in which R ² is NH ₂ is obtained by reducing the compound of formula (Ia) in which R ² is NO ₂ with a metal and an acid. Alternatively, it can be produced by a reaction equivalent thereto.

(In the production process [3], A is as described above.)
Examples of the metal include iron, zinc, and tin.
Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as acetic acid.
The reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. For example, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; esters such as methyl acetate and ethyl acetate; water; 1 type or 2 types or more can be appropriately selected and mixed for use.
The reaction temperature can usually be about 20 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 24 hours.

Manufacturing method [4]
In the formula (I), the compound of the formula (Ic) in which R ² is NHR ⁵ is obtained by reacting the compound of the formula (Ib) with the compound R ⁵ X in the presence of a base. Can be manufactured.

(In the production method [4], R ⁵ represents (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl or (C ₂ -C ₆ ) alkynyl, and A and X are as described above.)
Bases include alkali metal hydrides such as sodium hydride; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide. And so on.
The reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. For example, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; N, N-dimethylformamide, N-methylpyrrolidinone and the like. One or more of acid amides; aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; and the like can be appropriately selected and used.
The reaction temperature can usually be about 20 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 48 hours.

Manufacturing method [5]
In the formula (I), the compound of the formula (Id) in which R ² is SR ⁵ is a diazonium compound obtained by reacting the compound of the formula (Ib) with an inorganic nitrite or nitrite. Thereafter, it can be produced by a Sandmeyer reaction with a compound R ⁵ SH or (R ⁵ S) ₂ .

(In the production method [5], A and R ⁵ are as described above.)
Examples of inorganic nitrites include sodium nitrite and potassium nitrite.
Examples of the nitrite ester include tertiary butyl nitrite and isoamyl nitrite.
The reaction can be carried out in the presence of a copper catalyst as necessary. Examples of the copper catalyst include copper (I) oxide and copper (II) sulfate pentahydrate.
The reaction can be performed in the presence of an acid, if necessary. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as acetic acid and methanesulfonic acid.
The reaction can be carried out in the presence of a base as necessary. Bases include alkali metal hydrides such as sodium hydride; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide. And so on.
The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene and xylene; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide and dimethyl sulfoxide. 1 type or 2 types or more can be suitably selected from such as; water;
The reaction temperature can usually be in the range of -20 ° C to 200 ° C. The reaction time can usually be from several minutes to 24 hours.

Manufacturing method [6]
In the formula (I), the compound of the formula (Ie) in which R ² is X is obtained by reacting the compound of the formula (Ib) with an inorganic nitrite or nitrite to form a diazonium compound. It can be produced by a Sandmeyer reaction with a halogenating agent.

(In the production process [6], A and X are as described above.)
Examples of the inorganic nitrite and nitrite are the same as in the above production method [5].
Examples of the halogenating agent include chlorine, bromine, iodine and the like; hydrohalic acids such as hydrochloric acid, hydrobromic acid and hydroiodic acid; copper chloride (I), copper bromide (I), copper iodide (I) Copper (I) halides such as copper (II) chloride, copper (II) halides such as copper (II) bromide; tetrafluoroboric acid; and the like.
The reaction can be carried out in the presence of a copper catalyst as necessary. Examples of the copper catalyst include copper (I) halide, copper (II) halide, copper (I) oxide, and copper (II) sulfate pentahydrate.
The reaction can be performed in the presence of an acid, if necessary. Examples of the acid include inorganic acids such as hydrohalic acid and sulfuric acid mentioned above; organic acids such as acetic acid and methanesulfonic acid; and the like.
The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include those similar to the above production method [5], and one or more of these can be appropriately selected and mixed for use.
The reaction temperature can usually be in the range of -20 ° C to 200 ° C. The reaction time can usually be from several minutes to 24 hours.

Manufacturing method [7]
In the formula (I), the compound of the formula (Ic) in which R ² is NHR ⁵ can also be produced by the method shown in the following scheme.

(In the production process [7], t-Bu represents tertiary butyl. A, R ⁵ and X are as described above.)
(Process 1)
The compound of the formula (If) can be produced by reacting the compound of the formula (Ib) with ditertiary butyl dicarbonate in the presence of a base.
Bases include alkali metal hydrides such as sodium hydride; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide. And alkali metal amides such as lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, and potassium bis (trimethylsilyl) amide.
The reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction, and examples thereof include those similar to the above production method [4]. One or more of these may be appropriately selected, mixed and used. Can do.
The reaction temperature can be generally about −20 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 48 hours.
(Process 2)
The compound of the formula (Ig) can be produced by reacting the compound of the formula (If) with the compound R ⁵ X in the presence of a base.
Examples of the base include those similar to the above production method [4].
The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include those similar to those in Step 1, and one or more of these may be appropriately selected and mixed for use.
The reaction temperature can be generally about −20 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 48 hours.
(Process 3)
The compound of formula (Ic) can be produced by reacting the compound of formula (Ig) with an acid.
Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid.
The reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction, and examples thereof include those similar to the above production method [3]. One or more of these may be appropriately selected, mixed and used. Can do.
The reaction temperature can be generally about 0 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 24 hours.

Intermediate production method [1]
Compounds of formula (II) and formula (V) can be prepared by the method shown in the following scheme.

(In the intermediate production method [1], X and A are as described above.)
(Process 1)
The compound of the formula (V) can be produced by a Sonogashira reaction between the compound of the formula (IV) and trimethylsilylacetylene (similar to the above production method [1]).
(Process 2)
A compound of formula (II) can be prepared by reacting a compound of formula (V) with a base or tetrabutylammonium fluoride (TBAF).
Examples of the base include alkali metal carbonates such as potassium carbonate; alkali metal hydroxides such as sodium hydroxide; and the like.
The reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, aprotic polar solvents such as acetone and acetonitrile; aliphatic halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane; acetic acid One type or two or more types can be appropriately selected and mixed from esters such as ethyl; ethers such as tetrahydrofuran and dioxane; protic solvents such as methanol; and the like.
The reaction temperature can usually be in the range of -90 ° C to 90 ° C. The reaction time can usually be from several minutes to 24 hours.

Intermediate production method [2]
A compound of formula (IV) can be prepared by reacting a compound of formula (VI) with a halogenating agent.

(In the intermediate production method [2], X and A are as described above.)
Examples of halogenating agents include chlorinating agents such as N-chlorosuccinimide, N-chlorophthalimide, and chlorine; N-bromosuccinimide, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, bromine, and the like. Brominating agent; Iodizing agent such as N-iodosuccinimide, N-iodophthalic imide and iodine;
The reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. For example, N, N-dimethylformamide, aprotic polar solvent such as acetonitrile; ethers such as tetrahydrofuran; methylene chloride, 1, 2 -1 type (s) or 2 or more types can be suitably selected from halogenated hydrocarbon type solvents, such as dichloroethane, chloroform, and carbon tetrachloride.
The reaction temperature can be generally about 0 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 24 hours.

Intermediate production method [3]
The compound of the formula (IV) can be produced by a Sandmeyer reaction in which the compound of the formula (VII) is reacted with an inorganic nitrite or a nitrite to form a diazonium compound and then reacted with a halogenating agent.

(In the intermediate production method [3], X and A are as described above.)
Examples of the inorganic nitrite, nitrite ester, halogenating agent and copper catalyst are the same as those in the above production method [5].
The reaction can be performed in the presence of an acid, if necessary. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as acetic acid and methanesulfonic acid.
The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include the same ones as in the above production method [5], and one or more of these can be appropriately selected.
The reaction temperature can usually be in the range of -20 ° C to 200 ° C. The reaction time can usually be from several minutes to 24 hours.

Intermediate production method [4]
The compound of formula (III-a) is obtained by reacting the compound of formula (VIII) with a base to form 4-halopyridine represented by formula (IX), and then reacting 4-halopyridine with alkyllithium or lithium dialkylamide. and intermediate formed after reacting the, it can be prepared by reacting the compound R ^{5 X.} Examples of the acid addition salt of the formula (VIII) include hydrochloride, sulfate, acetate and the like.

(In the intermediate production method [4], X and R ⁵ are as described above.)
Examples of the base include alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.
Examples of the alkyl lithium include normal butyl lithium, secondary butyl lithium and tertiary butyl lithium.
Examples of the lithium dialkylamide include lithium diisopropylamide.
The reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction, for example, ethers such as diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; One or two or more kinds of aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, etc. may be appropriately selected and mixed for use.
The reaction temperature can usually be in the range of -90 ° C to -50 ° C. The reaction time can usually be from several minutes to 24 hours.
The compound of formula (III-a) can also be taken out as its acid addition salt by treating with an acid. Examples of the acid addition salt in the compound of the formula (III-a) include hydrochloride, sulfate, and acetate. Examples of the acid to be treated include hydrogen chloride, sulfuric acid, and acetic acid.

Intermediate production method [5]
In the formula (III), the compound of the formula (III-b) in which R ² is OR ⁵ is shown in the following scheme from the compound of the formula (Xa) that can be produced according to the method described in WO2005 / 101989 or the like. It can be manufactured by a method. The compound of formula (III-b) can also be taken out as its acid addition salt by treating with an acid.

(In the intermediate production method [5], X, R ⁵ and M are as described above.)
(Process 1)
The compound of the formula (Xb) can be produced by reacting the compound of the formula (Xa) with the compound R ⁵ OM or reacting the compound R ⁵ OH in the presence of a base. Examples of the base include those similar to the above production method [4].
The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include alcohols such as methanol, ethanol and 2-propanol, ethers such as diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; acids such as N, N-dimethylformamide and N-methylpyrrolidinone. One or more of amides can be appropriately selected and mixed for use.
The reaction temperature can be generally about −20 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 48 hours.

(Process 2)
The compound of the formula (III-b) can be produced by allowing phosphorus trihalide to act on (Xb). Moreover, it can also manufacture as a salt by processing the obtained compound of the formula (III-b) with an acid.
Examples of phosphorus trihalides include phosphorus trichloride and phosphorus tribromide.
The reaction can be performed in the presence of a solvent, if necessary. As the solvent, for example, one or two or more of esters such as ethyl acetate, aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, and the like can be appropriately selected and mixed for use.
The reaction temperature can be generally about −5 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 48 hours.
Examples of the acid addition salt in the compound of the formula (III-b) include hydrochloride, sulfate, acetate and the like, and examples of the acid to be treated include hydrogen chloride, sulfuric acid, acetic acid and the like.

Intermediate production method [6]
Of the compounds of formula (IV), the compound of formula (IV-a-2) and the compound of formula (IV-b-2) are respectively the compound of formula (IV-a-1) and the formula (IV-b- It can be produced by reacting the compound of 1) with alkyllithium or lithium dialkylamide.

(In the intermediate production method [6], X and A are as described above.)
Examples of the alkyl lithium and lithium dialkyl amide include those similar to the intermediate production method [4].
The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include those similar to the intermediate production method [4], and one or more of these can be appropriately selected.
Reaction temperature can be normally performed in the range of -100 degreeC-100 degreeC. The reaction time can usually be from several minutes to 24 hours.

Intermediate production method [7]
Of the compounds of formula (IV), the compound of formula (IV-a-4) and the compound of formula (IV-b-4) are the compounds of formula (IV-a-3) and formula (IV-b- It can be produced by reacting the compound of 3) with the compound of formula (XI) in the presence of a base.

(In the intermediate production process [7], R ⁶ is (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₃ -C ₆ ) cycloalkyl, ( C ₁ -C ₆₎ haloalkyl, (C ₁ -C ₆₎ alkylsilyl, (C ₁ -C ₆₎ alkoxy (C ₁ -C ₆₎ alkyl, (C ₂ -C ₆₎ alkenyloxy (C ₁ -C ₆ ) Alkyl, (C ₂ -C ₆ ) alkynyloxy (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) haloalkoxy (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) cycloalkoxy (C ₁ -C ₆ ) alkyl, or (C ₁ -C ₆ ) alkylthio (C ₁ -C ₆ ) alkyl, and X is as described above.)
Examples of the base include those similar to the above production method [4].
The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include those similar to the above production method [4], and one or more of these can be appropriately selected and mixed for use.
The reaction temperature can usually be about 20 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 48 hours.

Intermediate production method [8]
In the formula (III), the compound of the formula (III-d) in which R ² is CH ₂ OR ⁷ is described in Org. Lett. , 2008, 10, 2701, etc., can be produced by reacting the compound of formula (III-c) with compound R ⁷ X in the presence of a base.

(In the intermediate production method [8], R ⁷ is (C ₁ -C ₆ ) alkyl, and X is as described above.)
Examples of the base include those similar to the above production method [4].
The reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction, and examples thereof include those similar to the above production method [4]. One or more of these may be appropriately selected and mixed for use. be able to.
The reaction temperature can be generally about −20 ° C. to a temperature at which the reaction mixture is refluxed. The reaction time can usually be from several minutes to 48 hours.

  The desirable aspect of the pest control agent containing this invention compound is described below. The pest control agent containing the compound of the present invention is, for example, a pest, mite, nematode or soil pest that is a problem in the field of agriculture and horticulture, that is, an agricultural and horticultural insecticide, acaricide, nematicide or insecticide. Useful as a soil pesticide. It is also useful as an animal parasite control agent, that is, an animal killing parasite agent.

  The compounds of the present invention are useful as agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides. Specifically, aphids such as peach aphids, cotton aphids, etc .; Caterpillar, Lotus moth, Codling moth, Ball worm, Tobacco bud worm, Potato moth, Cochno medulla, Chanokoku kakumonhamakiki, Colorado potato beetle, cucumber moth beetle, ball weevil, planthopper, leafhopper, scale insect, stink bug, whitefly, thrips, thrips Pests, such as slugs, cockroaches, house flies, mosquitoes; sanitary pests, such as house dust mites, cockroaches, house flies, mosquitoes, etc .; Such as weevil, beetle, beetle, etc. Pests of stored grains; clothing such as moths, swordworms, termites, etc., house pests; pests such as spider mites, spider mites, spider mites, spider mites, apple spider mites, prickly mites, citrus mites, tick mites, etc. Indoor dusty mites, such as Staghorn mite, Pleurotus mite, Southern mite, etc .; such as mites, root-knot nematodes, cyst nematodes, nesting nematodes, rice nesting nematodes, strawberry nematodes, pine wood nematodes, etc. It is effective for the control of soil pests such as plant parasitic nematodes; The agricultural and horticultural insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is particularly effective for controlling plant parasitic mites, agricultural pests, plant parasitic nematodes and the like. is there. Among them, it is very useful as an insecticide or acaricide because it shows a further excellent effect in controlling plant parasitic mites and agricultural pests. In addition, agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides containing the compounds of the present invention are various resistances against drugs such as organophosphorus agents, carbamate agents, synthetic pyrethroid agents, neonicotinoid agents, etc. It is also effective for controlling pests. Furthermore, since the compound of the present invention has an excellent osmotic transfer property, the agricultural or horticultural insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is treated on the soil. By this, it is possible to control pests in the foliage at the same time as the control of soil harmful insects, mites, nematodes, gastropods, and isopods.

  As another desirable embodiment of the insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention, the above plant parasitic mites, agricultural pests, plant parasitic nematodes, gastropods And agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides that comprehensively control soil pests and the like.

  Agricultural and horticultural insecticides, acaricides, nematicides or soil pesticides containing the compounds of the present invention are usually prepared by mixing the compound with various agricultural adjuvants, powders, granules, granulated water Although it is formulated and used in various forms such as a powder, a wettable powder, an aqueous suspension, an oily suspension, a granular aqueous solvent, an aqueous solvent, an emulsion, a liquid, a paste, an aerosol, As long as it meets the object of the present invention, it can be made into any pharmaceutical form usually used in the art. Adjuvants used in the formulation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch; water , Toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, alcohol, etc. Solvent; fatty acid salt, benzoate, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, alcohol Sulfate ester salt, alkyl sulfonate salt, alkyl aryl sulfonate salt, aryl sulfonate salt, lignin sulfonate salt, alkyl diphenyl ether disulfonate salt, polystyrene sulfonate salt, alkyl phosphate ester salt, alkyl aryl phosphate salt, styryl aryl Phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate , Anionic surfactants such as naphthalenesulfonate formaldehyde condensate; sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride, fat Fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxy Nonionic surfactants such as ethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid ester; olive oil, kapok oil, castor oil, palm oil , Coconut oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, Riabura, vegetable oils and mineral oils such as liquid paraffin; and the like. Each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention. In addition to the above-mentioned adjuvants, it can be used by appropriately selecting from those known in the art. For example, a bulking agent, a thickening agent, an anti-settling agent, an antifreezing agent, a dispersion stabilizer, a phytotoxicity reduction. Various commonly used adjuvants such as agents, antifungal agents and the like can also be used. The compounding ratio (weight ratio) of the compound of the present invention and various adjuvants is 0.001: 99.999 to 95: 5, preferably 0.005: 99.995 to 90:10. In actual use of these preparations, use them as they are or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.

  Application of agricultural and horticultural insecticides, acaricides, nematicides or soil pesticides containing the compound of the present invention is different in weather conditions, formulation form, application time, application location, types of pests and occurrences, etc. However, it is generally carried out at an active ingredient concentration of 0.05 to 800,000 ppm, preferably 0.5 to 500,000 ppm, and the application amount per unit area is 0.05 to 50,000 g of the present compound per hectare, preferably 1 ~ 30,000g. The present invention also includes a method for controlling pests, mites, nematodes or soil pests by such an application method, particularly a method for controlling plant parasitic mites, agricultural pests, and plant parasitic nematodes.

  Application of various preparations or dilutions of agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides containing the compounds of the present invention, or dilutions thereof, is generally a commonly used application method, ie spraying. (For example, spraying, misting, atomizing, dusting, water surface application, etc.), soil application (mixing, irrigation, etc.), surface application (application, powder coating, coating, etc.), immersion poison bait, etc. It is also possible to feed livestock with the above-mentioned active ingredient mixed with feed to inhibit the occurrence and growth of harmful insects, particularly harmful insects, in the excreta. It can also be applied by the so-called ultra low volume application method. In this method, it is possible to contain 100% of the active ingredient.

  In addition, agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides containing the compounds of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, safeners, etc. In some cases, even better effects and functions may be exhibited. Other pesticides include herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, etc. It is done. In particular, an insecticidal composition, an acaricidal composition, a nematicidal composition or a composition for soil-killing insect pests in which the compound of the present invention and one or more active ingredient compounds of other agricultural chemicals are mixed or used in combination. The product can improve the application range, the timing of chemical treatment, the control activity, and the like in a preferable direction. The compound of the present invention and the other active ingredient compounds of other agricultural chemicals may be used separately by mixing them at the time of spraying, or both may be used together. The present invention includes such an insecticidal composition, an acaricidal composition, a nematicidal composition or a soil-killing insect pest composition.

In the above-mentioned other agricultural chemicals, as an active ingredient compound of an insecticide, acaricide, nematicide or soil pesticide (generic name; including some pending applications or Japan Plant Protection Association test code), for example Profenofos, dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephate, prothiophos, prothiophos, prothiophos Fosthiazate, cadusafos, dislufoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate ), Sulprofos, thiomethos (thiometon), bamidothion, pyraclofos, pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formothion, malathion, tetrachlorvinphos (tetrachlorvinphos), chlorfenvinphos, cyanophos, trichlorfon, methidathion, phenthoate, ESP, azinphos-methyl, fenthion, heptenophos , Methoxychlor, parathion, phosphocarb, demeton-S-methyl, monocrotophos, metamidophos, imicyafos, parathion-methyl -methyl), terbufos ( organophosphate compounds such as terbufos, phosphamidon, phosmet, phorate, phoxim, triazophos;
Carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, fenobucarb Carbamates such as carbosulfan, benfuracarb, bendiocarb, furathiocarb, isoprocarb, metolcarb, xylylcarb, XMC, fenothiocarb Compound;
Cartap, thiocyclam, bensultap, sodium thiosultap-sodium, thiosultap-disodium, monosultap, bisultap, hydrogen oxalate thiocyclam Nereistoxin derivatives such as (thiocyclam hydrogen oxalate);
Organochlorine compounds such as dicophor, tetradifon, endosulfan, dienochlor, dieldrin;
Organometallic compounds such as fenbutatin oxide and cyhexatin;
Fenvalerate, permethrin, cypermethrin, deltamethrin, cyhalothrin, tefluthrin, etofenprox, flufenprox, cyfluthrin , Fenpropathrin, flucytrinate, fluvalinate, cycloprothrin, lambda-cyhalothrin, pyrethrin, esfenvalerate, Tetramethrin, resmethrin, protrifenbute, bifenthrin, zeta-cypermethrin, acrinathrin, alpha-cypermeline (alpha-cyperme) thrin), allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin, beta-cypermethrin ( Pyrethroid compounds such as beta-cypermethrin, beta-cyfluthrin, mettofluthrin, phenothrin, flumethrin, decamethrin;
Diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, triflumuron, hexaflumuron, lufenuron, novaluron, novaluron, ), Bistrifluron, benzoylurea compounds such as fluazuron;
Juvenile hormone-like compounds such as metoprene, pyriproxyfen, fenoxycarb, diofenolan;
Pyridazinone compounds such as pyridaben;
Pyrazole compounds such as fenpyroximate, fipronil, tebufenpyrad, ethiprole, tolfenpyrad, acetoprole, pyrafluprole, pyriprole;
Imidacloprid, nitenpyram, acetamiprid, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran, dinotefuranit, dinotefuranit A noid compound;
Hydrazine compounds such as tebufenozide, methoxyfenozide, chromafenozide, halofenozide;
Pyridine compounds such as pyridalyl and flonicamid;
Cyclic ketoenol compounds such as spirodiclofen, spiromesifen, spirotetramat;
Strobilurin-based compounds such as fluacrypyrim;
Pyridinamine compounds such as flufenerim;
Dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, hydrazone compounds, and other compounds include flometoquin, buprofezin, hexythiazox, amitraz, chlordimeform ), Silafluofen, triazamate, pymetrozine, pyrimidifen, chlorfenapyr, indoxacarb, acequinocyl, etoxazole, romazine , 3-dichloropropene (1,3-dichloropropene), diafenthiuron, benclothiaz, bifenazate, propargite, clofentezine (cl ofentezine), metaflumizone, flubendiamide, cyflumetofen, chlorantraniliprole, cyantraniliprole, cyclaniliprole, cyenopyrafen, cyenopyrafen (Pyrifluquinazon), fenazaquin, amifluflumet, sulfluramid, hydramethylnon, metaldehyde, ryanodine, velanodin, chlorobenzoate, thiazoli Thiazolylcinnanonitrile, sulfoxaflor, fluenesulfone, triflumezopyrim, afidopyropen, flupi Flupyradifuron, NC-515, tetraniliprole, fluralaner, broflanilide, dicloromezotiaz, fluhexafon, tioxazafen, DKN-2601, MSI-1302, NA-89, MIE-1209, ZDI- Compounds such as 2502; and the like. Further, Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis tenebrionis, crystalline protein toxins produced by Bacillus thuringiensis, entomopathogenic fungi, nematode pathogenic fungi, etc. Microbial pesticides such as avermectin, emamectin benzoate, milbemectin, milbemycin, spinosad, ivermectin, lepimectin, DE-175, abamectin ), Antibiotics such as emamectin, spinetoram and semi-synthetic antibiotics; natural products such as azadirachtin and rotenone; repellents such as deet; etc. And mixed, combined use Rukoto can also.

In the above-mentioned other pesticides, as an active ingredient compound (generic name; including partial application, or Japan Plant Protection Association test code), for example, mepanipyrim, pyrimethanil, cyprodinil ), Anilinopyrimidine compounds such as ferimzone;
Tria such as 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) [1,2,4] triazolo [1,5-a] pyrimidine Zolopyrimidine compounds;
Pyridinamine compounds such as fluazinam;
Triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanil, cyproconazole cyproconazole), tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole, o Oxpoconazole fumarate, sipconazole, prothioconazole, triadimenol, flutriafol, difenoconazole , Fluquinconazole, fenbuconazole, bromuconazole, diniconazole, tricyclazole, probenazole, cimeconazole, pefurazoate, ipconazole, ipconazole ), Azole compounds such as imibenconazole;
Quinoxaline compounds such as quinomethionate;
Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram;
Organochlorine compounds such as fthalide, chlorothalonil, quintozene;
Imidazole compounds such as benomyl, cyazofamid, thiophanate-methyl, carbendazim, thiabendazole, and fuberiazole;
Cyanoacetamide compounds such as cymoxanil;
Metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, offurace, benalaxyl, benalaxyl-M, also known as kiralaxyl, chiax ), Flaxaxyl, cyprofuram, carboxin, oxycarboxin, thifluzamide, boscalid, bixafen, isothianil, tiadinil, Anilide compounds such as sedaxane;
Sulfamide-type compounds such as dichlofluanid;
Copper-based compounds such as cupric hydroxide and oxine copper;
Isoxazole compounds such as hymexazol;
Fosetyl-Al, tolclofos-Methyl, S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate, edifenphos, iprobenphos Organophosphorus compounds such as (iprobenfos);
Phthalimide compounds such as captan, captafol, folpet;
Dicarboximide compounds such as procymidone, iprodione, vinclozolin;
Benzanilide compounds such as flutolanil and mepronil;
Penthiopyrad, 3- (difluoromethyl) -1-methyl-N-[(1RS, 4SR, 9RS) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl ] Pyrazole-4-carboxamide and 3- (difluoromethyl) -1-methyl-N-[(1RS, 4SR, 9SR) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalene-5 Amide compounds such as -yl] pyrazole-4-carboxamide mixtures (isopyrazam), silthiopham, fenoxanil, furametpyr;
Benzamide compounds such as fluopyram and zoxamide;
Piperazine compounds such as triforine;
Pyridine compounds such as pyrifenox;
Carbinol compounds such as fenarimol;
Piperidine compounds such as fenpropidin;
Morpholine compounds such as fenpropimorph and tridemorph;
Organotin compounds such as fentin hydroxide and fentin acetate;
Urea-based compounds such as pencycuron;
Synamic acid compounds such as dimethomorph, flumorph;
Phenyl carbamate compounds such as dietofencarb;
Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
Azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin ( strobilurin compounds such as dimoxystrobin), pyraclostrobin, fluoxastrobin;
Oxazolidinone compounds such as famoxadone;
Thiazole carboxamide compounds such as ethaboxam;
Valinamide compounds such as iprovalicarb, benchthiavalicarb-isopropyl;
Acylamino acid compounds such as methyl N- (isopropoxycarbonyl) -L-valyl- (3RS) -3- (4-chlorophenyl) -β-valaniphenate;
Imidazolinone compounds such as fenamidone;
Hydroxyanilide compounds such as fenhexamid;
Benzenesulfonamide compounds such as flusulfamide;
Oxime ether compounds such as cyflufenamid;
Atraquinone compounds;
Crotonic acid compounds;
Antibiotics such as validamycin, kasugamycin, polyoxins;
Guanidine compounds such as iminoctadine and dodine;
Quinoline compounds such as 6-tertiarybutyl-8-fluoro-2,3-dimethylquinolin-4-yl acetate (tebufloquin);
Thiazolidines such as (Z) -2- (2-fluoro-5- (trifluoromethyl) phenylthio) -2- (3- (2-methoxyphenyl) thiazolidine-2-ylidene) acetonitrile (flutianil) Compound;
Other compounds include pyribencarb, isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, and sodium metam Metam-sodium, nicobifen, metrafenone, UBF-307, diclocymet, proquinazid, amisulbrom (aka amibromdole), 3- (2,3,4 -Trimethoxy-6-methylbenzoyl) -5-chloro-2-methoxy-4-methylpyridine, 4- (2,3,4-trimethoxy-6-methylbenzoyl) -2,5-dichloro-3-trifluoromethyl Pyridine, pyriophenone, isofetamid mandipropamide (Mandipropamid), fluopicolide, carpropamid, meptyldinocap, N-[(3 ', 4'-dichloro-1,1-dimethyl) phenacyl] -3-trifluoromethyl-2 -Pyridinecarboxamide, N-[(3 ', 4'-dichloro-1,1-dimethyl) phenacyl] -3-methyl-2-thiophenecarboxamide, N-[(3', 4'-dichloro-1,1- Dimethyl) phenacyl] -1-methyl-3-trifluoromethyl-4-pyrazolecarboxamide, N-[[2'-methyl-4 '-(2-propyloxy) -1,1-dimethyl] phenacyl] -3- Trifluoromethyl-2-pyridinecarboxamide, N-[[2'-methyl-4 '-(2-propyloxy) -1,1-dimethyl] phenacyl] -3-methyl-2-thiophenecarboxamide, N-[[ 2'-methyl-4 '-(2-propyloxy) -1,1-dimethyl] phenacyl] -1-methyl-3-trifluoromethyl-4-pyrazolecarboxamide, N-[[4'-(2-propiyl Ruoxy) -1,1-dimethyl] phenacyl] -3-trifluoromethyl-2-pyridinecarboxamide, N-[[4 '-(2-propyloxy) -1,1-dimethyl] phenacyl] -3-methyl- 2-thiophenecarboxamide, N-[[4 '-(2-propyloxy) -1,1-dimethyl] phenacyl] -1-methyl-3-trifluoromethyl-4-pyrazolecarboxamide, N-[[2'- Methyl-4 '-(2-pentyloxy) -1,1-dimethyl] phenacyl] -3-trifluoromethyl-2-pyridinecarboxamide, N-[[4'-(2-pentyloxy) -1,1- Dimethyl] phenacyl] -3-trifluoromethyl-2-pyridinecarboxamide, spiroxamine, fenpyrazamine, mandestrobin, ZF-9646, BCF-051, BCM-061, BCM-062, etc. Can be mentioned.

  Other pesticides that can be used in combination with or combined with the compounds of the present invention include, for example, active compound compounds of herbicides such as those described in The Pesticide Manual (15th edition), especially those treated with soil. There is.

  Specific examples of animal killing parasites include harmful ectoparasites that parasitize the host animal's body surface (back, armpits, lower abdomen, inner thighs, etc.) and the host animal body (stomach, intestinal tract, It is effective in controlling harmful endoparasites that parasitize the lungs, heart, liver, blood vessels, subcutaneous, lymphoid tissue, etc., and in particular, it is effective in controlling ectoparasites.

  Examples of ectoparasites include animal parasitic mites and fleas. There are so many of these types that it is difficult to list them all.

The animal parasitic mites, for example Boophilus microplus (Boophilus microplus), Rhipicephalus sanguineus (Rhipicephalus sanguineus), Haemaphysalis longicornis (Haemaphysalis longicornis), Haemaphysalis flava (Haemaphysalis flava), Adenophora chima tick (Haemaphysalis campanulata), Isukachimadani (Haemaphysalis concinna), Yamatochimadani (Haemaphysalis japonica), H. kitaokai (Haemaphysalis kitaokai), Iyasuchimadani (Haemaphysalis ias), Ixodes ovatus (Ixodes ovatus), I. nipponensis (Ixodes nipponensis), Schulze ticks (Ixodes persulcatus), Takasago testudinarium (Amblyomma testudinarium), Ootogechimadani (Haemaphysalis megaspinosa ), tick such as Dermacentor reticulatus , Dermacentor taiwanesis ; duck ( Dermanyssus gallinae ); Shidani (Ornithonyssus sylviarum), Torisashidani, such as Southern tri sand mite (Ornithonyssus bursa); Nan iodine tsutsugamushi (Eutrombicula wichmanni), red mites (Leptotrombidium akamushi), L. pallidum (Leptotrombidium pallidum), Fuji chiggers (Leptotrombidium fuji), Tosa mites ( Leptotrombidium tosa), Europe Aki mites (Neotrombicula autumnalis), the United States chiggers (Eutrombicula alfreddugesi), chiggers, such as Miyagawa Tama chiggers (Helenicula miyagawai); Inutsumedani (Cheyletiella yasguri), rabbit Tsumedani (Cheyletiella parasitivorax), Nekotsumedani (Cheyletiella blakei) Tsumedani, such as; rabbits 9,000 mite (Psoroptes cuniculi), Ushishokuhidani (Chorioptes bovis), dog ear mites (Otodectes cynotis), mange mites (Sar coptes scabiei ), mite mites like Notoedres cati, mite mites like Demodex canis , and the like. Among them, the animal killing parasite agent containing the compound of the present invention is particularly effective for controlling ticks and the like.

Examples of animal parasitic fleas include ectoparasite worms belonging to the order Flea ( Siphonaptera ), and more specifically, fleas belonging to the family Flea family ( Pulicidae ), Nagano family ( Ceratephyllus ) and the like. Examples of fleas belonging to the family flea family include, for example, dog fleas ( Ctenocephalides canis ), cat fleas ( Ctenocephalides felis ), human fleas ( Purex irritans ), elephant fleas ( Echidnophaga gallinacea ), keops mouse fleas ( Xenopsylla cheopis ) Leptopsylla segnis ), European mud minnow ( Nosopsyllus fasciatus ), Yamato mud mink ( Monopsyllus anisus ); and the like. Among them, the animalicidal parasite agent containing the compound of the present invention is effective for controlling fleas belonging to the family flea family, especially dog fleas, cat fleas and the like.

  Other ectoparasites include, for example, lice such as bovine lice, foal lice, sheep lice, bovine white lice, head lice; lice such as cat lice; blood-sucking dipterous pests such as bovine abs, quail sharks, . In addition, examples of endoparasites include nematodes such as lungworm, benthic, nodular worms, gastric parasites, roundworms, and filamentous worms; Tapeworms such as real tapeworms, multi-headed tapeworms, single-banded tapeworms, multi-banded tapeworms; Japanese schistosomiasis, fluke like liver fluke; coccidium, malaria parasite, intestinal granulocyst, toxoplasma, chestnut Protozoa such as Ptosporidium, and the like.

  Examples of host animals include various pet animals, livestock, poultry, and the like. More specifically, dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (eg, pigeons, parrots, (E.g., nine-bird, bird, parakeet, juvenile pine, canary, etc.), cattle, horses, pigs, sheep, ducks, and chickens. Among them, the animal killing parasite agent containing the compound of the present invention is effective for controlling pests or ticks that are externally parasitic on pet animals or livestock. Among pet animals or domestic animals, it is particularly effective for dogs, cats, cows or horses.

  When the compound of the present invention is used as an animal killing parasite, it may be used as it is, and together with suitable adjuvants, powders, granules, tablets, powders, capsules, liquid agents, emulsions, aqueous suspensions, It can also be formulated and used in various forms such as an oily suspension. In addition to the above-mentioned preparation forms, any preparation forms used in the normal field can be used as long as the object of the present invention is met. As an adjuvant to be used in the preparation, the anionic surfactants and nonionic surfactants exemplified as the above-mentioned preparation adjuvant for agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides. Surfactant; cationic surfactant such as cetyltrimethylammonium bromide; water, acetone, acetonitrile, N-methylacetamide, N, N-dimethylacetamide, N, N-dimethylformamide, 2-pyrrolidone, N- Methyl-2-pyrrolidone, kerosene, triacetin, methanol, ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, liquid polyoxyethylene glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, di Solvents such as tylene glycol monoethyl ether, diethylene glycol normal butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol normal butyl ether; butylhydroxyanisole, butylhydroxytoluene, ascorbic acid, sodium metabisulfite, propyl gallate, sodium thiosulfate Antioxidants such as: polyvinyl pyrrolidone, polyvinyl alcohol, film forming agents such as vinyl acetate and vinyl pyrrolidone copolymers; formulations of the aforementioned agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides Vegetable oils and mineral oils exemplified as adjuvants for milk; lactose, sucrose, glucose, starch, wheat flour, corn flour, soybean oil cake, defatted rice bran, calcium carbonate, and other carriers such as commercially available feed ingredients; That. Each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention. In addition to the above-mentioned adjuvants, it can be used by appropriately selecting from those known in the field, and further, selected from various adjuvants used in the above-mentioned agricultural and horticultural fields. You can also

  The blending ratio (weight ratio) of the compound of the present invention and various adjuvants is usually about 0.1: 99.9 to 90:10. In actual use of these preparations, use them as they are or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.

  Administration of the compound of the present invention to the host animal is performed orally or parenterally. Examples of the oral administration method include a method of administering tablets, liquid agents, capsules, wafers, biscuits, minced meat, and other feeds containing the compound of the present invention. As a parenteral administration method, for example, the compound of the present invention is prepared into an appropriate preparation and then taken into the body by intravenous administration, intramuscular administration, intradermal administration, subcutaneous administration, etc .; spot-on And a method of administering to the body surface by treatment, pour-on treatment, spray treatment, etc .; a method of embedding a resin piece containing the compound of the present invention under the skin of a host animal, and the like.

  The dose of the compound of the present invention to the host animal varies depending on the administration method, administration purpose, disease symptoms, etc., but is usually 0.01 mg to 100 g, preferably 0.1 mg to 10 g, relative to 1 kg body weight of the host animal. Is suitable for administration.

  The present invention also includes a method for controlling animal parasites, particularly a method for controlling ectoparasites or endoparasites by the administration method or dosage as described above.

  In the present invention, by controlling harmful animal parasites as described above, various diseases of host animals caused by them may be prevented or treated. Thus, the present invention includes a prophylactic or therapeutic agent for parasitic animal diseases containing the compound of the present invention as an active ingredient, and a method for preventing or treating parasitic animal diseases.

  When the compound of the present invention is used as an animal killing parasite, various vitamins, minerals, amino acids, nutrients, enzyme preparations, antipyretics, sedatives, anti-inflammatory agents, bactericides, coloring agents, fragrances, It can be mixed with or used in combination with preservatives. In addition, if necessary, other animal drugs and agricultural chemicals such as anthelmintics, anticoccidials, insecticides, acaricides, fleas, nematicides, fungicides, antibacterials, etc. In this case, a more excellent effect may be exhibited. The present invention includes a composition for controlling animal parasites in which various components as described above are mixed or used together, and a method for controlling animal parasites using the composition, in particular, control of ectoparasites or endoparasites. A method is also included.

Next, some desirable embodiments of the 4- (5-membered heterocyclic ethynyl) pyridine-based compound or a salt thereof of the present invention will be exemplified, but these do not limit the present invention.
(1) A 4- (5-membered heterocyclic ethynyl) pyridine compound of the above formula (I) or a salt thereof.
(2) In the above formula (I), R ¹ is phenyl, benzyl optionally substituted with B, formyl, cyano, (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) cycloalkyl, (C ₁ -C ₆₎ haloalkyl, (C ₁ -C ₆₎ alkoxy, (C ₁ -C ₆₎ alkoxy (C ₁ -C ₆₎ alkyl, (C ₁ -C ₆₎ haloalkoxy (C ₁ -C ₆₎ alkyl, (C ₁ -C ₆ ) haloalkoxy or (C ₁ -C ₆ ) alkoxycarbonyl; R ² is a halogen atom, nitro, (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₆ ) alkoxy (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkylthio, (C ₁ -C ₆ ) haloalkoxy, NR ³ R ⁴ or hydroxyl (C ₁ -C ₆ ) alkyl The 4- (5-membered heterocyclic ethynyl) pyridine compound or a salt thereof according to (1) above.
(3) In the formula (I), R ³ and R ⁴ are each independently a hydrogen atom, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl or (C ₂ -C ₆ ) alkynyl. The 4- (5-membered heterocyclic ethynyl) pyridine compound or a salt thereof according to the above (1) or (2).
(4) In the formula (I), R ¹ is phenyl, benzyl optionally substituted with B, formyl, cyano, (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) cycloalkyl, (C ₁ -C ₆₎ haloalkyl, (C ₁ -C ₆₎ alkoxy, (C ₁ -C ₆₎ alkoxy (C ₁ -C ₆₎ alkyl, (C ₁ -C ₆₎ haloalkoxy (C ₁ -C ₆₎ alkyl or (C ₁ -C ₆ ) haloalkoxy; R ² is a halogen atom, (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₆ ) alkoxy (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ The 4- (5-membered heterocyclic ethynyl) pyridine compound or a salt thereof according to (1) above, which is alkylthio, (C ₁ -C ₆ ) haloalkoxy or NR ³ R ⁴ .
(5) A is

Wherein m in each substituent is an integer from 0 to 3, n is an integer from 0 to 2, p is an integer from 0 to 4, and q is an integer from 0 or 1. The 4- (5-membered heterocyclic ethynyl) pyridine compound or a salt thereof according to (1) to (4).
(6) A is

(M in each substituent is an integer of 0 to 3, n is an integer of 0 to 2, and q is an integer of 0 or 1). Heterocyclic ethynyl) pyridine compound or a salt thereof.

(7) A pest control agent comprising the compound of (1) to (6) or a salt thereof as an active ingredient.
(8) An agricultural and horticultural pest control agent comprising the compound (1) to (6) or a salt thereof as an active ingredient.
(9) Insecticides, acaricides, nematicides and soil insecticides containing the compounds (1) to (6) or salts thereof as active ingredients.
(10) An insecticide or acaricide containing the compound (1) to (6) or a salt thereof as an active ingredient.
(11) An animal killing parasite agent comprising the compound of the above (1) to (6) or a salt thereof as an active ingredient.
(12) A method for controlling pests by applying an effective amount of the compounds (1) to (6) or salts thereof.

  Next, examples of the present invention will be described, but the present invention is not limited thereto. First, the synthesis example of this invention compound is described.

Synthesis example 1
Synthesis of 3-ethoxy-4-((5-neopentylthiophen-2-yl) ethynyl) pyridine (Compound No. 2-26)

(1) 2-Neopentylthiophene (2.0 g, 13 mmol), N-bromosuccinimide (2.5 g, 14 mmol), and N, N-dimethylformamide (13 mL) were mixed and reacted at room temperature for 3 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to give 2-bromo-5-neopentylthiophene (2.8 g). Yield 92.6%).

(2) 2-Bromo-5-neopentylthiophene (1.35 g, 5.8 mmol), trimethylsilylacetylene (1.71 g, 17.4 mmol), copper (I) iodide (0.06 g, 0.29 mmol), bis (triphenylphosphine) Palladium (II) dichloride (0.2 g, 0.29 mmol), triethylamine (10 mL) and N, N-dimethylformamide (5 mL) were mixed in a nitrogen atmosphere and reacted at 70 ° C. for 4 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate), and trimethyl ((5-neopentylthiophen-2-yl). ) Ethynyl) silane (1.21 g, 83.4% yield).

(3) 3-Ethoxy-4-bromopyridine hydrochloride (0.2 g, 0.84 mmol), trimethyl ((5-neopentylthiophen-2-yl) ethynyl) silane (0.42 g, 1.7 mmol), copper iodide (I ) (0.01 g, 0.05 mmol), tetrakis (triphenylphosphine) palladium (0) (0.04 g, 0.05 mmol), 1.0 M tetrabutylammonium fluoride in tetrahydrofuran (1.7 mL, 1.7 mmol), triethylamine (3 mL) and N, N-dimethylformamide (3 mL) were mixed under a nitrogen atmosphere and reacted at 70 ° C. for 4 hours. After allowing to cool to room temperature, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to obtain the desired product (0.17 g, yield 67.7%). Obtained.

Synthesis example 2
Synthesis of 3-ethoxy-4-((5-neopentylthiophen-3-yl) ethynyl) pyridine (Compound No. 1-15)

(1) 2-Bromo-5-neopentylthiophene (1.4 g, 6.0 mmol) and tetrahydrofuran (7 mL) were mixed in a nitrogen atmosphere and cooled with ice. A 1M lithium diisopropylamide solution in hexane / tetrahydrofuran (6 mL) was added dropwise thereto, the ice cooling was stopped, and the mixture was allowed to reach room temperature, followed by stirring for 3 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure to obtain 4-bromo-2-neopentylthiophene (1.25 g, yield 89.3%).

(2) 4-Bromo-2-neopentylthiophene (1.25 g, 5.36 mmol), trimethylsilylacetylene (1.58 g, 16.1 mmol), copper (I) iodide (0.05 g, 0.27 mmol), bis (triphenylphosphine) Palladium (II) dichloride (0.19 g, 0.27 mmol) and triethylamine (10 mL) were mixed under a nitrogen atmosphere and reacted at 70 ° C. for 4 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate), and trimethyl ((5-neopentylthiophen-3-yl). ) Ethynyl) silane (1.14 g, 84.9% yield).

(3) 3-Ethoxy-4-bromopyridine hydrochloride (0.2 g, 0.84 mmol), trimethyl ((5-neopentylthiophen-3-yl) ethynyl) silane (0.42 g, 1.7 mmol), copper iodide (I ) (0.01 g, 0.05 mmol), tetrakis (triphenylphosphine) palladium (0) (0.04 g, 0.05 mmol), 1.0 M tetrabutylammonium fluoride in tetrahydrofuran (1.7 mL), triethylamine (3 mL), N, N-dimethylformamide (3 mL) was mixed under a nitrogen atmosphere and reacted at 70 ° C. for 4 hours. After allowing to cool to room temperature, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to obtain the desired product (0.23 g, yield 91.6%). Obtained.

Synthesis example 3
Synthesis of 3-ethoxy-4-((1- (2,2,2-trifluoroethyl) -1H-pyrazol-4-yl) ethynyl) pyridine (Compound No. 8-22)

(1) 4-iodo-1H-pyrazole (1.0 g, 5.16 mmol), 1,1,1-trifluoro-2-iodoethane (3.25 g, 15.57 mmol), cesium carbonate (2.52 g, 7.73 mmol), N, N-dimethylformamide (10 mL) was mixed and reacted at 60 ° C. for 11 hours. The solid was removed by filtration, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure to obtain 4-iodo-1- (2,2,2-trifluoroethyl) -1H-pyrazole (0.92 g, yield 64.7%). It was.

(2) 4-iodo-1- (2,2,2-trifluoroethyl) -1H-pyrazole (0.83 g, 3.0 mmol), trimethylsilylacetylene (0.88 g, 9.0 mmol), copper iodide (I) (0.03 g, 0.15 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.11 g, 0.15 mmol), triethylamine (10 mL), N, N-dimethylformamide (10 mL) were mixed under a nitrogen atmosphere, 70 The reaction was carried out at 0 ° C. for 11 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to give 1- (2,2,2-trifluoroethyl). ) -4-((trimethylsilyl) ethynyl) -1H-pyrazole (0.53 g, yield 71.7%) was obtained.

(3) 3-Ethoxy-4-bromopyridine hydrochloride (0.24 g, 1 mmol), 1- (2,2,2-trifluoroethyl) -4-((trimethylsilyl) ethynyl) -1H-pyrazole (0.32 g) , 1.3 mmol), copper (I) iodide (0.01 g, 0.05 mmol), tetrakis (triphenylphosphine) palladium (0) (0.04 g, 0.05 mmol), 1.0M tetrabutylammonium fluoride in tetrahydrofuran solution ( 1.5 mL, 1.5 mmol), triethylamine (3 mL), and N, N-dimethylformamide (3 mL) were mixed under a nitrogen atmosphere and reacted at 70 ° C. for 11 hours. After allowing to cool to room temperature, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to obtain the desired product (0.185 g, yield 62.7%). Obtained.

Synthesis example 4
Synthesis of 4-((5- (tert-butyl) furan-2-yl) ethynyl) -3-ethoxypyridine (Compound No. 4-25)

(1) Under cooling with ice, a solution of 2- (tert-butyl) furan (1.0 g, 8.1 mmol) in N, N-dimethylformamide (3 mL) was added N-bromosuccinimide (1.4 g, 8.1 mmol) in N, N-dimethylformamide (7 mL) solution was added. Thereafter, ice cooling was stopped and the reactor was shielded from light with aluminum foil. After waiting for the reaction mixture to reach room temperature, it was reacted at room temperature for 16 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the resulting 2-bromo-5- (tert-butyl) furan was subjected to the next reaction without purification.
(2) 2-bromo-5- (tert-butyl) furan, trimethylsilylacetylene (2.4 g, 24.7 mmol), copper (I) iodide (0.05 g, 0.53 mmol), bis (triphenylphosphine) palladium (II) Dichloride (0.29 g, 0.41 mmol) and triethylamine (15 mL) were mixed in a nitrogen atmosphere and reacted at 70 ° C. for 7 hours. After allowing to cool to room temperature, water and heptane were added to the reaction solution. Insoluble matters were removed by Celite filtration, and the filtrate was extracted with heptane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to obtain ((5- (tert-butyl) furan-2 -Il) ethynyl) trimethylsilane (0.71 g, 40% yield) was obtained.

(3) 3-Ethoxy-4-bromopyridine hydrochloride (300 mg, 1.26 mmol), ((5- (tert-butyl) furan-2-yl) ethynyl) trimethylsilane (400 mg, 1.82 mmol), iodinated Copper (I) (13 mg, 0.07 mmol), bis (triphenylphosphine) palladium (II) dichloride (56 mg, 0.08 mmol), triethylamine (1 mL, 7 mmol), 1.0 M tetrabutylammonium fluoride in tetrahydrofuran (1.7 mL, 1.7 mmol) and N, N-dimethylformamide (5 mL) were mixed under a nitrogen atmosphere and reacted at 70 ° C. for 7 hours. After allowing to cool to room temperature, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to obtain the desired product (369 mg, 100% yield). Obtained.

Intermediate synthesis
Synthesis of 3-ethoxy-4-bromopyridine hydrochloride

(1) Under ice-cooling, 20% sodium ethoxide ethanol solution (29 g, 86) was added to a mixed suspension of 3-fluoro-4-nitropyridine 1-oxide (12 g, 76 mmol) and ethanol (300 mL). mmol) was added. The reaction solution was allowed to reach room temperature and reacted at room temperature for 30 minutes. Ethanol was evaporated under reduced pressure, water (200 mL) was added to the residue, and the mixture was stirred at room temperature for 15 min. The solid was collected by filtration, washed with water, and dried under reduced pressure to give 3-ethoxy-4-nitropyridine 1-oxide (11 g, yield 76%).

(2) Phosphorus tribromide (21 mL, 222 mmol) was added to a mixed suspension of 3-ethoxy-4-nitropyridine 1-oxide (5.0 g, 27 mmol) and ethyl acetate (250 mL) at room temperature. The temperature in the reaction system was dropped at a rate not exceeding 40 ° C. After dropping, the mixture was stirred at the same temperature for 10 minutes, then heated to a temperature at which the solvent was refluxed, and reacted at the same temperature for 16 hours. The mixture was allowed to cool to room temperature, and the reaction mixture was poured into ice water (250 mL). Liquid separation was performed, and the obtained aqueous layer was ice-cooled. Under ice cooling, sodium hydroxide was added at a rate such that the temperature in the reaction system did not exceed 20 ° C., and the pH in the reaction system was adjusted to 10 or more. The reaction mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure. The residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to give 4-bromo-3-ethoxypyridine. The obtained 3-ethoxy-4-bromopyridine was dissolved in an n-heptane / ethyl acetate mixed solution (200 mL, mixing ratio: n-heptane / ethyl acetate = 8: 2), ice-cooled, and then 2.0M chloride. Hydrogen ether solution (30 mL, 60 mmol) was added. The precipitated solid was collected by filtration, washed with n-heptane, and dried under reduced pressure to obtain the desired product (4.6 g, yield 71%).

Next, typical examples of the compounds according to the present invention are shown in Tables 1 to 39. No. in each table indicates a compound number. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In each table, the numerical value described in the physical property column indicates the melting point (° C.), and the compound described as “Oil” indicates an oily substance. In each table, Me is methyl, Et is ethyl, n-Pr is normal propyl, i-Pr is isopropyl, i-Bu is isobutyl, sec-Bu is secondary butyl, and t-Bu is Tertiary butyl, n-Pen is normal pentyl, i-Pen is isopentyl, neo-Pen is neopentyl, i-Hex is isohexyl, neo-Hex is neohexyl, cyc-Pen is cyclopentyl, cyc- Hex represents cyclohexyl, Ph represents phenyl, and Bn represents benzyl.
In the R ¹ column, for example, a compound described as “4-Et” represents that the position where the number “4” is attached to the chemical structural formula in the table is substituted with ethyl, The compound described as “2,4-Me ₂ ” indicates that the position indicated by the numbers “2” and “4” in the chemical structural formula is substituted with methyl, and described as “−”. The compound thus obtained represents that R ¹ is unsubstituted, and other similar descriptions follow this.
On the other hand, for the compounds described as “Oil” or “gum”, their 1H-NMR spectral data are shown in Table 40.

Test Example 1 Effect test on green planthopper Rice seedlings were immersed in a chemical solution prepared so that the concentration of the compound of the present invention was 200 ppm. After the chemical solution was air-dried, the root was wrapped with wet absorbent cotton and placed in a test tube. Approximately 10 3rd instar larvae were released in this, and the tube mouth was covered with gauze and left in a constant temperature room at 25 ° C. Five days after the insect release, the dead planthopper was judged to be alive or dead, and the death rate (%) was determined by the following formula. As a result, the compound Nos. 1-10, 1-11, 1-14, 1-15, 1-16, 2-6, 2-7, 2-21, 2-22, 2-25, 2-26 , 2-33, 2-38, 2-45, 2-82, 3-14, 4-24, 4-25, 5-6, 5-7, 8-4, 8-8, 8-9, 8 -10, 8-11, 8-12, 8-13, 8-14, 8-16, 8-17, 8-18, 8-19, 8-20, 8-22, 8-23, 8-26 , 8-34, 8-42, 8-56, 8-67, 8-104, 8-105, 8-107, 8-108, 8-109, 8-113, 8-117, 8-118, 8 -120, 8-121, 8-122, 8-123, 8-124, 8-125, 9-32, 9-33, 10-3, 10-4, 12-2, 25-24, 25-27 , 26-10, 2 6-12, 26-13, 26-38, 26-39 and 39-4 showed a death rate of 90% or more.
Death rate (%) = (Number of dead insects / Number of dead insects) × 100

Test Example 2 Effect Test on Tobacco Whitefly To a pot-planted cucumber seedling infested with 1 to 2 instar larvae, a chemical solution prepared so that the concentration of the compound of the present invention was 200 ppm was sprayed using a hand spray. After the chemical solution was air-dried, it was left in a constant temperature room at 25 ° C. with illumination. Ten days after the treatment, the number of old larvae was examined, and the control value was determined by the following formula. As a result, the compound Nos. 1-10, 1-11, 1-14, 1-15, 1-16, 2-6, 2-7, 2-21, 2-22, 2-25, 2-26 , 2-33, 2-38, 2-45, 2-82, 3-14, 4-25, 5-6, 5-7, 8-4, 8-8, 8-9, 8-10, 8 -11, 8-12, 8-13, 8-14, 8-16, 8-17, 8-18, 8-19, 8-20, 8-22, 8-23, 8-26, 8-35 , 8-42, 8-50, 8-56, 8-67, 8-104, 8-105, 8-107, 8-108, 8-109, 8-113, 8-114, 8-117, 8 -118, 8-119, 8-120, 8-121, 8-123, 8-124, 8-125, 8-126, 9-32, 9-33, 10-3, 10-4, 25-17 25-27 26-10,26-12,26-13,26-38,26-39,27-3,27-4,33-1,36-1 and 39-4 showed over 90 control value.
Control value = (1− (Ta × Cb) / (Tb × Ca)) × 100
Ta: Number of old larvae after treatment in treated cucumber seedlings
Tb: Number of 1-2 instar larvae before treatment in treated cucumber seedlings
Ca: number of old larvae after treatment in untreated cucumber seedlings
Cb: Number of larvae 1 to 2 instar before treatment in untreated cucumber seedlings

Next, formulation examples are described.
Formulation Example 1
(1) Compound of the present invention 20 parts by weight (2) Clay 70 parts by weight (3) White carbon 5 parts by weight (4) Sodium polycarboxylate 3 parts by weight (5) Sodium alkylnaphthalene sulfonate 2 parts by weight or more To make a wettable powder.

Formulation Example 2
(1) Compound of the present invention 5 parts by weight (2) Talc 60 parts by weight (3) Calcium carbonate 34.5 parts by weight (4) Liquid paraffin 0.5 parts by weight or more are uniformly mixed to obtain a powder.

Formulation Example 3
(1) Compound of the present invention 20 parts by weight (2) N, N-dimethylacetamide 20 parts by weight (3) Polyoxyethylene tristyryl phenyl ether 10 parts by weight (4) Calcium dodecylbenzenesulfonate 2 parts by weight (5) Xylene 48 A mixture of more than parts by weight is uniformly mixed and dissolved to obtain an emulsion.

Formulation Example 4
(1) Clay 68 parts by weight (2) Sodium lignin sulfonate 2 parts by weight (3) Polyoxyethylene alkylaryl sulfate 5 parts by weight (4) White carbon 25 parts by weight A mixture of each component and the present compound Mix at a weight ratio of 4: 1 to make a wettable powder.

Formulation Example 5
(1) Compound of the present invention 50 parts by weight (2) Sodium alkylnaphthalene sulfonate formaldehyde condensate 2 parts by weight (3) Silicone oil 0.2 parts by weight (4) Water 47.8 parts by weight or more uniformly mixed (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are further added to the crushed stock solution, and the mixture is uniformly mixed, granulated and dried to obtain a granulated wettable powder.

Formulation Example 6
(1) Compound of the present invention 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Polyoxyethylene alkyl ether phosphate 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight (1 ) To (3) are uniformly mixed in advance and diluted with an appropriate amount of acetone, and then sprayed onto (4) to remove acetone and form granules.

Formulation Example 7
(1) Compound of the present invention 2.5 parts by weight (2) N, N-dimethylacetamide 2.5 parts by weight (3) Soybean oil 95.0 parts by weight or more are uniformly mixed and dissolved to give a trace amount of spray ( ultra low volume formulation).

Formulation Example 8
(1) Compound of the present invention 10 parts by weight (2) Diethylene glycol monoethyl ether 80 parts by weight (3) Polyoxyethylene alkyl ether 10 parts by weight or more of ingredients are mixed uniformly to obtain a liquid agent.

Claims (11)

Formula (I):

[Wherein A is a 5-membered heterocyclic ring optionally substituted by R ¹ ;
R ¹ is a halogen atom, hydroxyl, mercapto, cyano, nitro, formyl, phenyl, benzyl optionally substituted with B, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆₎ alkynyl, (C ₃ -C ₆₎ cycloalkyl, (C ₁ -C ₆₎ haloalkyl, (C ₁ -C ₆₎ alkoxy, (C ₂ -C ₆₎ alkenyloxy, (C ₂ -C ₆₎ alkynyl Oxy, (C ₃ -C ₆ ) cycloalkoxy, tri (C ₁ -C ₆ ) alkylsilyl, (C ₁ -C ₆ ) alkoxy (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyloxy ( C ₁ -C ₆₎ alkyl, (C ₂ -C ₆₎ alkynyloxy (C ₁ -C ₆₎ alkyl, (C ₁ -C ₆₎ haloalkoxy (C ₁ -C ₆₎ alkyl, (C ₃ -C ₆ ) Cycloalkoxy (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) haloalkoxy, (C ₁ -C ₆ ) alkylthio, (C ₂ -C ₆ ) alkenylthio, (C ₂ -C ₆ ) alkynylthio , (C ₃ -C ₆₎ cycloalkylthio, (C ₁ -C ₆₎ Haroaruki Thio, (C ₁ -C ₆₎ alkylsulfinyl, (C ₂ -C ₆₎ alkenylsulfinyl, (C ₂ -C ₆₎ alkynylsulfinyl, (C ₃ -C ₆₎ cycloalkyl alkylsulfinyl, (C ₁ -C ₆₎ haloalkylsulfinyl, (C ₁ -C ₆₎ alkylsulfonyl, (C ₂ -C ₆₎ alkenyl-sulfonyl, (C ₂ -C ₆₎ alkynyl-sulfonyl, (C ₃ -C ₆₎ cycloalkylsulfonyl, (C ₁ -C ₆ ) Haloalkylsulfonyl, (C ₁ -C ₆ ) alkylthio (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkylsulfinyl (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkylsulfonyl (C ₁ -C ₆ ) alkyl, NR ³ R ⁴ , carboxyl, (C ₁ -C ₆ ) alkylcarbonyl, (C ₁ -C ₆ ) alkoxycarbonyl, (C ₁ -C ₆ ) alkylaminocarbonyl, di (C _1- C ₆ ) alkylaminocarbonyl, (C ₁ -C ₆ ) alkylcarbonyloxy, (C ₁ -C ₆ ) alkylcarbonylamino or (C ₁ -C ₆ ) alkylcarbonyl (C ₁ -C ₆ ) alkylamino;
B is a halogen atom, (C ₁ -C ₆ ) alkyl or (C ₁ -C ₆ ) haloalkyl;
R ² is a halogen atom, hydroxyl, mercapto, cyano, nitro, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₁ -C ₆ ) haloalkyl, (C ₁ -C ₆ ) alkoxy, (C ₂ -C ₆ ) alkenyloxy, (C ₂ -C ₆ ) alkynyloxy, (C ₁ -C ₆ ) alkylthio, (C ₂ -C ₆ ) alkenylthio, (C ₂ -C ₆ ) alkynylthio, (C ₁ -C ₆ ) haloalkoxy, NR ³ R ⁴ , (C ₁ -C ₆ ) alkylsulfinyl, (C ₂ -C ₆ ) alkenylsulfinyl, (C ₂ -C ₆ ) alkynylsulfinyl, (C ₁ -C ₆₎ alkylsulfonyl, (C ₂ -C ₆₎ alkenyl-sulfonyl, (C ₂ -C ₆₎ alkynyl-sulfonyl, (C ₁ -C ₆₎ alkoxy (C ₁ -C ₆₎ alkyl, (C ₁ -C ₆ ) alkylthio (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkylamino (C ₁ -C ₆ ) alkyl, di (C ₁ -C ₆ ) alkylamino (C ₁ -C ₆₎ alkyl, hydroxyl (C ₁ -C ₆₎ A Kill, formyl, carboxyl, (C ₁ -C ₆₎ alkylcarbonyl, (C ₁ -C ₆₎ alkoxycarbonyl, (C ₁ -C ₆₎ alkylaminocarbonyl, di (C ₁ -C ₆₎ alkylaminocarbonyl, ( C ₁ -C ₆ ) alkylcarbonyloxy, (C ₁ -C ₆ ) alkylcarbonylthio, (C ₁ -C ₆ ) alkylcarbonylamino or di (C ₁ -C ₆ ) alkylcarbonylamino;
R ³ and R ⁴ are each independently a hydrogen atom, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₃ -C ₆ ) cycloalkyl Or (C ₁ -C ₆ ) haloalkyl]-(5-membered heterocyclic ethynyl) pyridine compound or a salt thereof. R ¹ is phenyl, benzyl optionally substituted with B, formyl, cyano, (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) cycloalkyl, (C ₁ -C ₆ ) haloalkyl, (C _1- C ₆₎ alkoxy, (C ₁ -C ₆₎ alkoxy (C ₁ -C ₆₎ alkyl, (C ₁ -C ₆₎ haloalkoxy (C ₁ -C ₆₎ alkyl, (C ₁ -C ₆₎ haloalkoxy, or (C ₁ -C ₆ ) alkoxycarbonyl; R ² is a halogen atom, nitro, (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₆ ) alkoxy (C _1- The 4- (5) according to claim 1, which is C ₆ ) alkyl, (C ₁ -C ₆ ) alkylthio, (C ₁ -C ₆ ) haloalkoxy, NR ³ R ⁴ or hydroxyl (C ₁ -C ₆ ) alkyl. Membered heterocyclic ethynyl) pyridine compound or a salt thereof. The ^4- amino group according to claim 1, wherein R ³ and R ⁴ are each independently a hydrogen atom, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl or (C ₂ -C ₆ ) alkynyl. (5-membered heterocyclic ethynyl) pyridine compound or a salt thereof. A is

(Wherein m in each substituent is an integer of 0 to 3, n is an integer of 0 to 2, p is an integer of 0 to 4, and q is an integer of 0 or 1). 4. The 4- (5-membered heterocyclic ethynyl) pyridine compound or a salt thereof according to 1. A 5-membered heterocyclic group optionally substituted by R ¹ of A is

The 4- (5-membered complex) according to claim 1, wherein m in each substituent is an integer of 0 to 3, n is an integer of 0 to 2, and q is an integer of 0 or 1. Ring ethynyl) pyridine compound or a salt thereof.   A pest control agent comprising the compound of claim 1 or a salt thereof as an active ingredient.   An agricultural and horticultural pest control agent comprising the compound of claim 1 or a salt thereof as an active ingredient.   An insecticide, acaricide, nematicide or soil insecticide containing the compound of claim 1 or a salt thereof as an active ingredient.   An insecticide or acaricide containing the compound of claim 1 or a salt thereof as an active ingredient.   An insecticidal parasite agent comprising the compound of claim 1 or a salt thereof as an active ingredient.   A method for controlling pests by applying an effective amount of the compound of claim 1 or a salt thereof.