JP2016011294A - Pest control agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having high activity to pest, a pest control agent obtained using the compound and a method for controlling pest by application of the compound.SOLUTION: The present invention provides the pest control agent containing a compound represented by formula (I) or a salt thereof as an active ingredient, where Ris a halogen atom, hydroxyl, formyl, phenoxy, trialkylsilyl, a substitutable alkyl or substitutable haloalkyl group, a substitutable alkoxy or substitutable haloalkenyloxy group, Ris a hydrogen atom, formyl, benzyloxy, substitutable alkyl, substitutable alkenyl, substitutable alkynyl, substitutable alkoxy, substitutable cycloalkoxy, substitutable haloalkoxy or substitutable alkylamino, n is an integer of 0 to 3, neighboring 2 Rs together may form a condensed ring together with a benzene ring or a pyridine ring.

Description

  The present invention relates to a pest control agent comprising a novel 4- (arylethynyl) 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 4-((2-fluorophenyl) ethynyl) pyridin-3-amine, which is a synthetic intermediate of a pyrrolopyridine compound for use as a therapeutic agent for hepatitis virus. Non-Patent Document 1 and Non-Patent Document 2 describe specific 4- (arylethynyl) pyridine compounds.

International Publication No. 2010/064711 International Publication No. 2012/008526 JP-A-1-316359 International Publication No. 2010/115901 Green Chemistry (2011) 13 (7) 1640-1643 Chimica Therapeutia 1971 6 (3) 159-166

  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- (arylethynyl) pyridine compound has a very high control effect against pests with a low dose, and completed the present invention.

That is, the gist of the present invention is the following (1) to (8).
(1) Formula (I):

[Wherein R ¹ is substituted with a halogen atom, amino group, hydroxyl group, mercapto group, cyano group, nitro group, formyl group, carboxyl group, phenoxy group, tri (C ₁ -C ₄ ) alkylsilyl group, or A (C ₁ -C ₆ ) alkyl group optionally substituted with (C ₂ -C ₆ ) alkenyl group optionally substituted with A, (C ₂ -C ₆ ) alkynyl group optionally substituted with A substituted with A A (C ₃ -C ₆ ) cycloalkyl group which may be substituted, a (C ₃ -C ₆ ) cycloalkenyl group which may be substituted with A, a (C ₁ -C ₆ ) haloalkyl group which may be substituted with A, (C ₂ -C ₆ ) haloalkenyl group optionally substituted with A, (C ₁ -C ₆ ) alkoxy group optionally substituted with A, (C ₂ -C ₆ ) alkenyl optionally substituted with A An oxy group, an optionally substituted (C ₂ -C ₆ ) alkynyloxy group, an optionally substituted (C ₃ -C ₆ ) cycloalkoxy group, an optionally substituted A (C _3- C ₆ ) Cycloalkenyloxy group, optionally substituted with (C ₁ -C ₆ ) haloalkoxy group, optionally substituted with (C ₂ -C ₆ ) haloalkenyloxy group, optionally substituted with A (C ₁ -C ₆ ) alkylthio group, optionally substituted with (C ₂ -C ₆ ) alkenylthio group, optionally substituted with (C ₂ -C ₆ ) alkynylthio group, substituted with A which may be (C ₃ -C ₆₎ cycloalkyl thio group which may be substituted by A (C ₃ -C ₆₎ cycloalkenylthio group which may be substituted by A (C ₁ -C ₆₎ haloalkylthio group Or a (C ₂ -C ₆ ) haloalkenylthio group optionally substituted by A;
A is a (C ₃ -C ₆ ) cycloalkyl group, (C ₃ -C ₆ ) cycloalkenyl group, (C ₁ -C ₆ ) alkoxy group, (C ₂ -C ₆ ) alkenyloxy group, (C ₂ -C ₆₎ alkynyloxy group, (C ₃ -C ₆₎ cycloalkoxy group, (C ₃ -C ₆₎ cycloalkenyl group, (C ₁ -C ₆₎ haloalkoxy group or a (C ₂ -C ₆₎ haloalkenyloxy A group;
R ² is a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, a mercapto group, a cyano group, a nitro group, a formyl group, a carboxyl group, a benzyloxy group, or a (C ₁ -C ₆ ) alkyl group optionally substituted by B (C ₂ -C ₆ ) alkenyl group optionally substituted with B, (C ₂ -C ₆ ) alkynyl group optionally substituted with B, (C ₃ -C ₆ ) cyclo optionally substituted with B An alkyl group, a (C ₃ -C ₆ ) cycloalkenyl group that may be substituted with B, a (C ₁ -C ₆ ) haloalkyl group that may be substituted with B, an optionally substituted with B (C ₂ -C) ₆ ) A haloalkenyl group, (C ₁ -C ₆ ) alkoxy group optionally substituted with B, (C ₂ -C ₆ ) alkenyloxy group optionally substituted with B, optionally substituted with B (C ₂ -C ₆₎ alkynyloxy group which may be substituted by B (C ₃ -C ₆₎ cycloalkoxy group which may be substituted by B (C ₃ -C ₆₎ cycloalkenyl O Shi group which may be substituted by B (C ₁ -C ₆₎ haloalkoxy group, may be substituted with B (C ₂ -C ₆₎ haloalkenyloxy group which may be substituted by B (C ₁ -C ₆ ) alkylamino group, optionally substituted with B (C ₂ -C ₆ ) alkenylamino group, optionally substituted with B (C ₂ -C ₆ ) alkynylamino group, optionally substituted with B A good (C ₃ -C ₆ ) cycloalkylamino group, a (C ₃ -C ₆ ) cycloalkenylamino group optionally substituted with B, a (C ₁ -C ₆ ) haloalkylamino group optionally substituted with B, (C ₂ -C ₆ ) haloalkenylamino group optionally substituted with B, di (C ₁ -C ₆ ) alkylamino group optionally substituted with B, di (C _2- C ₆ ) alkenylamino group, di (C ₂ -C ₆ ) alkynylamino group optionally substituted with B, di (C ₃ -C ₆ ) cycloalkylamino group optionally substituted with B, substituted with B Even Di (C ₃ -C ₆ ) cycloalkenylamino group, di (C ₁ -C ₆ ) haloalkylamino group optionally substituted with B, di (C ₂ -C ₆ ) haloalkenyl optionally substituted with B Amino group, (C ₁ -C ₆ ) alkylthio group optionally substituted with B, (C ₂ -C ₆ ) alkenylthio group optionally substituted with B, optionally substituted with B (C ₂ -C ₆₎ alkynylthio which may be substituted by B (C ₃ -C ₆₎ cycloalkylthio group which may be substituted by B (C ₃ -C ₆₎ cycloalkenylthio group, may be substituted with B A (C ₁ -C ₆ ) haloalkylthio group or a (C ₂ -C ₆ ) haloalkenylthio group optionally substituted with B;
B is a (C ₃ -C ₆ ) cycloalkyl group, (C ₃ -C ₆ ) cycloalkenyl group, (C ₁ -C ₆ ) alkoxy group, (C ₂ -C ₆ ) alkenyloxy group, (C ₂ -C ₆₎ alkynyloxy group, (C ₃ -C ₆₎ cycloalkoxy group, (C ₃ -C ₆₎ cycloalkenyl group, (C ₁ -C ₆₎ haloalkoxy group, (C ₂ -C ₆₎ haloalkenyloxy Group, phenoxy group, (C ₁ -C ₆ ) alkylamino group, (C ₂ -C ₆ ) alkenylamino group, (C ₂ -C ₆ ) alkynylamino group, di (C ₁ -C ₆ ) alkylamino group, Di (C ₂ -C ₆ ) alkenylamino group, di (C ₂ -C ₆ ) alkynylamino group, (C ₁ -C ₆ ) alkylthio group, (C ₂ -C ₆ ) alkenylthio group, (C ₂ -C ₆₎ alkynylthio, (C ₁ -C ₆₎ alkylsulfinyl group, (C ₂ -C ₆₎ alkenylsulfinyl group, (C ₂ -C ₆₎ alkynylsulfinyl group, (C ₁ -C ₆₎ An alkylsulfonyl group or a (C ₂ -C ₆ ) alkenylsulfonyl group or a (C ₂ -C ₆ ) alkynylsulfonyl group;
W is CH or a nitrogen atom;
n is an integer of 0 to 3; when n is 2 or more, R ¹ may be the same as or different from each other, and two adjacent R ¹ together are substituted together with a benzene ring or a pyridine ring. Condensed rings may be formed; provided that 4-((2-fluorophenyl) ethynyl) pyridin-3-amine, 4- (4-methoxyphenylethynyl) nicotinaldehyde and 4- (2-methoxy 4- (arylethynyl) pyridine compounds or salts thereof represented by the following formula (except phenyl) ethynyl) -3-methylpyridine]:
(2) A pest control agent comprising the compound or salt thereof according to (1) as an active ingredient.
(3) An agricultural and horticultural pest control agent comprising the compound or salt thereof according to (1) as an active ingredient.
(4) An insecticide, acaricide, nematicide or soil insecticide containing the compound or salt thereof according to (1) as an active ingredient.
(5) An insecticide or acaricide containing the compound or salt thereof according to (1) as an active ingredient.
(6) An animal killing parasite agent containing the compound or salt thereof according to (1) as an active ingredient.
(7) A method for controlling pests by applying an effective amount of the compound or salt thereof according to (1).

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

  Examples of the halogen atom in the general 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, and neohexyl. Straight chain or branched C ₁ -C ₆ groups.
In this specification, “tertiary” may be expressed as “tert-”.

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- 3-butynyl, 3,3-dimethyl-1-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-straight or branched chain groups of _C 2 -C ₆ such as 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 cycloalkenyl or cycloalkenyl moiety in the formula (I) include C ₃ -C ₆ groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

Dihydroindene, benzodioxole, dihydrobenzofuran, etc. are mentioned as a condensed ring which two adjacent R < ¹ > in said Formula (I) forms together with a benzene ring or a pyridine ring. The condensed ring may be substituted, and examples of such substituent include a halogen atom, a (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) alkenyl group, and a (C ₂ -C ₆ ) alkynyl group. , (C ₃ -C ₆ ) cycloalkyl group, (C ₃ -C ₆ ) cycloalkenyl group, (C ₁ -C ₆ ) haloalkyl group, (C ₂ -C ₆ ) haloalkenyl group, (C ₁ -C ₆₎ ) Alkoxy group, (C ₂ -C ₆ ) alkenyloxy group, (C ₂ -C ₆ ) alkynyloxy group, (C ₃ -C ₆ ) cycloalkoxy group, (C ₃ -C ₆ ) cycloalkenyloxy group, C ₁ -C ₆ ) haloalkoxy group, (C ₂ -C ₆ ) haloalkenyloxy group and the like.

  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 both the isomers and isomer mixtures. 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 a compound of formula (II) with a 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 R ¹ , R ² , n and W 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. Any solvent may be used as long as it is inert to the reaction. For example, amine base; aprotic polar solvent such as N, N-dimethylformamide and acetonitrile; ethers such as tetrahydrofuran; A seed | species or 2 or more types can be selected suitably.
The reaction temperature can usually be in the range of about 20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 24 hours.

Manufacturing method [2]
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. Or it can manufacture by reaction according to it.

(In the production method [2], R ¹ , n and W are 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 (s) or 2 or more types can be selected and mixed appropriately from the above.
The reaction temperature can usually be in the range of about 20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 24 hours.

Manufacturing method [3]
In the formula (I), the compound of the formula (Ic) in which R ² is NHR ³ is produced by reacting the compound of the formula (Ib) with the compound R ³ X in the presence of a base. be able to.

(In the production process [3], R ³ may be substituted with (C ₁ -C ₆ ) alkyl group optionally substituted with B, (C ₂ -C ₆ ) alkenyl group optionally substituted with B, or substituted with B; Good (C ₂ -C ₆ ) alkynyl group, (C ₃ -C ₆ ) cycloalkyl group optionally substituted with B, (C ₃ -C ₆ ) cycloalkenyl group optionally substituted with B, substituted with B Represents a (C ₁ -C ₆ ) haloalkyl group which may be substituted or a (C ₂ -C ₆ ) haloalkenyl group which may be substituted with B. R ¹ , B, W, n and X are as defined above. .)
Examples of the base 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. Thing; etc. are mentioned.
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, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane; N, N-dimethylformamide, N-methylpyrrolidinone and the like. 1 type (s) or 2 or more types can be appropriately selected and mixed and used.
The reaction temperature can usually be in the range of about 20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 48 hours.

Manufacturing method [4]
In the formula (I), the compound of the formula (Id) in which R ² is SR ³ is obtained by reacting the compound of the formula (Ib) with an inorganic nitrite or nitrite, Then, it can be produced by a Sandmeyer reaction in which the compound is reacted with R ³ SH or (R ³ S) ₂ .

(In the production method [4], R ¹ , R ³ , n and W are as described above.)
Examples of the inorganic nitrite include sodium nitrite and potassium nitrite.
Examples of the nitrite 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. Examples of the base 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. Thing; etc. are mentioned.
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 [5]
In the formula (I), a compound of the formula (Ie) in which R ² is OR ³ 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 ³ OH.

(In the production method [5], R ¹ , R ³ , n and W are as described above.)
Examples of the inorganic nitrite and nitrite are the same as in the above production method [4].
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, methanesulfonic acid, and trifluoroacetic acid.
The reaction can be carried out in the presence of a base as necessary. Examples of the base 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. Thing; etc. are mentioned.
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 (If) in which R ² is X is obtained by converting the compound of the formula (Ib) into a diazonium salt by reaction with inorganic nitrite or nitrite. It can be produced by a Sandmeyer reaction with a halogenating agent.

(In the production method [6], R ¹ , W, n and X are as described above.)
Examples of the inorganic nitrite and nitrite are the same as in the above production method [4].
Examples of the halogenating agent include chlorine, bromine, iodine, etc .; hydrohalic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid; copper chloride (I), copper bromide (I), copper iodide (I Copper halides (I) such as copper chloride (II), 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 [4], 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 ³ can also be produced by the method shown in the following scheme.

(In the production method [7], t-Bu represents tertiary butyl. R ¹ , R ³ , W, n and X are as described above.)
(Process 1)
The compound of the formula (Ig) can be produced by reacting the compound of the formula (Ib) with ditertiary-butyl dicarbonate in the presence of a base.
Examples of the base 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 [3]. One or more of these may be appropriately selected and mixed for use. be able to.
The reaction temperature can usually be in the range of about −20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 48 hours.

(Process 2)
The compound of the formula (Ih) can be produced by reacting the compound of the formula (Ig) with the compound R ³ X in the presence of a base.
Examples of the base include those similar to the above production method [3].
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 usually be in the range of about −20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 48 hours.

(Process 3)
The compound of the formula (Ic) can be produced by reacting the compound of the formula (Ih) 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 [2]. One or more of these may be appropriately selected and mixed for use. be able to.
The reaction temperature can usually be in the range of about 0 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 24 hours.

Manufacturing method [8]
A compound of formula (I-J) can be prepared by oxidizing a compound of formula (I-I).

(In the production method [8], R ¹ , n and W are as described above.)
As the oxidation reaction, for example, a method using a metal oxidizer such as pyridium chlorochromate (PCC) or manganese dioxide; a method using a hypervalent iodine oxidizer such as Dess-Martin periodinane; oxalyl chloride and dimethyl sulfoxide; And a method using a base (Swan oxidation).
Examples of the base include amine bases such as triethylamine and diisopropylamine.
The reaction can be performed in the presence of a solvent, if necessary. As the solvent, for example, one or two or more kinds are appropriately selected from aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as benzene; aprotic polar solvent such as acetonitrile; can do.
The reaction temperature can usually be in the range of about −80 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 24 hours.

Manufacturing method [9]
The compound of the present invention can also be produced by the Sonogashira reaction (similar to the above production method [1]) between the compound of formula (IX) and the compound of formula (IV) in the presence of tetrabutylammonium fluoride (TBAF). it can.

(In the production process [9], X, R ¹ , R ² , n and W are as described above.)

Intermediate production method [1]
The compound of the formula (II) can be produced by the method shown in the following scheme.

(In the intermediate production method [1], X, W, n and R ¹ 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.
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; ethyl acetate 1 type or 2 types or more can be suitably selected and mixed from ethers such as, 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 50 ° C. The reaction time can usually be from several minutes to 24 hours.

Intermediate production method [2]
The compound of formula (III-a) is obtained by reacting a compound of formula (VI) with a base to form 4-halopyridine represented by formula (VII), and then reacting 4-halopyridine with alkyllithium or lithium dialkylamide. It can manufacture by making the intermediate body produced | generated after making it react and the said compound R < ³ > X. Examples of the acid addition salt of the formula (IV) include hydrochloride, sulfate, acetate, and the like.

(In the intermediate production method [2], X and R ³ 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. Any solvent may be used 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. 1 type or 2 types or more can be suitably selected and mixed from aliphatic hydrocarbons, such as hexane, heptane, octane, and cyclohexane;
The reaction temperature can usually be in the range of -90 ° C to room temperature. 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 [3]
A compound of formula (II-b) in which R ¹ is OR ⁴ in formula (II) is produced by reacting a compound of formula (II-a) with compound R ⁴ X in the presence of a base. Can do.

(In the intermediate production method [3], R ⁴ is a (C ₁ -C ₆ ) alkyl group optionally substituted with A, a (C ₂ -C ₆ ) alkenyl group optionally substituted with A, or A substituted. An optionally substituted (C ₂ -C ₆ ) alkynyl group, a (C ₁ -C ₆ ) haloalkyl group optionally substituted with A, a (C ₂ -C ₆ ) haloalkenyl group optionally substituted with A, .A showing an optionally substituted (C ₃ -C ₆₎ optionally substituted with a cycloalkyl group, or a (C ₃ -C ₆₎ cycloalkenyl group, W, n and X are as described above. )
Examples of the base include those similar to the above production method [3].
The reaction can be performed in the presence of a solvent, if necessary. As the solvent, any solvent may be used as long as it is inert to the reaction. Examples thereof include those similar to the above production method [3]. One or more of these may be appropriately selected and mixed. Can be used.
The reaction temperature can usually be in the range of about 20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 48 hours.

Intermediate production method [4]
A compound of formula (II-d) in which R ¹ is SR ⁴ in formula (II) is produced by reacting a compound of formula (II-c) with the compound R ⁴ X in the presence of a base. be able to.

(In the intermediate production method [4], R ⁴ , W, n and X are as described above.)
Examples of the base include those similar to the above production method [3].
The reaction can be performed in the presence of a solvent, if necessary. As the solvent, any solvent may be used as long as it is inert to the reaction. Examples thereof include those similar to the above production method [3]. One or more of these may be appropriately selected and mixed. Can be used.
The reaction temperature can usually be in the range of about 20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 48 hours.

Intermediate production method [5]
In the formula (III), the compound of the formula (III-b) in which R ² is OR ³ is shown in the following scheme from the compound of the formula (VIII-a) 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 and R ³ are as described above, and M is Na, K or Cs.)
(Process 1)
The compound of the formula (VIII-b) can be produced by reacting the compound of the formula (VIII-a) with the compound R ³ OM or reacting the compound R ³ OH in the presence of a base. Examples of the base include those similar to the above production method [3].
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 usually be in the range of about −20 ° C. to the boiling point of the solvent used. 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 reacting phosphorus trihalide with (VIII-b). 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 usually be in the range of about −5 ° C. to the boiling point of the solvent used. 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]
In the formula (III), the compound of the formula (III-d) in which R ² is CH ₂ OR ⁵ is described in Org. Lett. , 2008, 10, 2701, etc., can be produced by reacting the compound of formula (III-c) with compound R ⁵ X in the presence of a base.

(In the intermediate production method [6], X is as described above, and R ⁵ is a (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 ) cycloalkenyl group, (C ₁ -C ₆ ) haloalkyl group or (C ₂ -C ₆ ) haloalkenyl group.)
Examples of the base include those similar to the above production method [3].
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 and mixed for use. be able to.
The reaction temperature can usually be in the range of about −20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 48 hours.

Intermediate production method [7]
In the formula (III), the compound of the formula (III-e) in which R ² is CH ² OR ⁶ is obtained by converting the compound of the formula (III-c) and the compound R ⁶ OH into an azodicarboxylic acid ester or an azodicarboxylic acid amide. And a Mitsunobu reaction in the presence of triarylphosphine or trialkylphosphine.

(In the intermediate production method [7], X is as described above, and R ⁶ is a (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₎ cycloalkenyl group, (C ₁ -C ₆₎ haloalkyl group, (C ₂ -C ₆₎ haloalkenyl group or a phenyl group.)
Examples of the azodicarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
Examples of the azodicarboxylic acid amide include 1,1 ′-(azodicarbonyl) dipiperidine, 1,1′-azobis (N, N-dimethylformamide) and the like.
Examples of triarylphosphine include triphenylphosphine.
Examples of the trialkylphosphine include tributylphosphine.
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, aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene and xylene; acetonitrile, N, One or more aprotic polar solvents such as N-dimethylformamide and dimethyl sulfoxide;
The reaction temperature can usually be in the range of about 0 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 24 hours.

Intermediate production method [8]
In the intermediate production method [8], the compound of formula (IX) can be produced by the Sonogashira reaction of the compound of formula (III) or an acid addition salt thereof and trimethylsilylacetylene (similar to the above production method [1]). it can.

(In the intermediate production method [8], X and R ² are as described above.)

Intermediate production method [9]
The compound of the formula (III-b) can be produced from the compound of the formula (VIII-b) by the method shown in the following scheme. 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 [9], X and R ³ are as described above.)

(Process 1)
The compound of the formula (Xb) can be produced by reacting the compound of the formula (VIII-b) with acetyl bromide.
The reaction can be performed in the presence of a solvent, if necessary. As the solvent, for example, one kind or two or more kinds of ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, 1,4-dioxane; esters such as methyl acetate and ethyl acetate; carboxylic acids such as acetic acid; Can be selected and mixed for use.
The reaction temperature can usually be in the range of about 20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 24 hours.

(Process 2)
The compound of the formula (III-b) can be produced by reducing the compound of the formula (Xb) with a metal and an acid, or by a reaction corresponding thereto.
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 (s) or 2 or more types can be selected and mixed appropriately from the above.
The reaction temperature can usually be in the range of about 20 ° C. to the boiling point of the solvent used. The reaction time can usually be from several minutes to 24 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. 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 Scarlet mite, Pleurotus mite, Southern mite mite 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, amidoflumet, sulfluramid, hydramethylnon, metaldehyde, ryanodine, verbutin, chlorobenzoate, thia Thiazolylcinnanonitrile, sulfoxaflor, fluenesulfone, triflumezopyrim, afidopyropen, full Flupyradifuron, NC-515, tetraniliprole, fluralaner, broflanilide, dicloromezotiaz, fluhexafon, tioxazafen, DKN-2601, MSI-1302, NA-89NA-89, MIE-1209, Compounds such as ZDI-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, abamectin, ectin emamectin), antibiotics such as spinetoram and semi-synthetic antibiotics; natural products such as azadirachtin and rotenone; repellents such as deet; Can also be used together .

In the above-mentioned other pesticides, as an active ingredient compound (generic name; including partial application or Japanese 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, spiroxamine, fenpyrazamine, mandestrobin, ZF-9646, BCF-051, BCM-061 , BCM-062 etc.

  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 dog lice; . 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, chickens, etc. 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 and the like. 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 preferred embodiments of the 4- (arylethynyl) 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- (arylethynyl) pyridine compound of the above formula (I) or a salt thereof.
(2) R ¹ is a halogen atom, a hydroxyl group, a formyl group, a carboxyl group, a phenoxy group, a tri (C ₁ -C ₄ ) alkylsilyl group, a (C ₁ -C ₆ ) alkyl group optionally substituted with A, (C ₂ -C ₆ ) alkenyl group optionally substituted with A, (C ₂ -C ₆ ) alkynyl group optionally substituted with A, (C ₁ -C ₆ ) haloalkyl group optionally substituted with A , (C ₁ -C ₆ ) alkoxy group optionally substituted with A, (C ₁ -C ₆ ) haloalkoxy group optionally substituted with A, (C ₂ -C ₆ ) optionally substituted with A haloalkenyloxy group which may be substituted by A (C ₁ -C ₆₎ may be substituted with an alkylthio group, or A (C ₁ -C ₆₎ be a haloalkylthio group;
A is a (C ₃ -C ₆ ) cycloalkyl group, (C ₁ -C ₆ ) alkoxy group, (C ₂ -C ₆ ) alkenyloxy group, (C ₂ -C ₆ ) alkynyloxy group, (C ₃ -C ₆ ) a cycloalkoxy group or a (C ₁ -C ₆ ) haloalkoxy group;
R ² is a hydrogen atom, formyl group, benzyloxy group, (C ₁ -C ₆ ) alkyl group optionally substituted with B, (C ₂ -C ₆ ) alkenyl group optionally substituted with B, substituted with B An optionally substituted (C ₂ -C ₆ ) alkynyl group, a (C ₃ -C ₆ ) cycloalkyl group optionally substituted with B, a (C ₁ -C ₆ ) alkoxy group optionally substituted with B, B (C ₃ -C ₆ ) cycloalkoxy group optionally substituted with, (C ₁ -C ₆ ) haloalkoxy group optionally substituted with B, (C ₁ -C ₆ ) alkyl optionally substituted with B Amino group, (C ₃ -C ₆ ) cycloalkylamino group optionally substituted with B, (C ₁ -C ₆ ) haloalkylamino group optionally substituted with B, di (C ₁ -C ₆ ) alkylamino group, di (C ₃ -C ₆ ) cycloalkylamino group optionally substituted with B, di (C ₁ -C ₆ ) haloalkylamino group optionally substituted with B, May be replaced C ₁ -C ₆₎ alkylthio group which may be substituted by B (C ₃ -C ₆₎ may be substituted with a cycloalkylthio group, or B (C ₁ -C ₆₎ be a haloalkylthio group;
B is a (C ₃ -C ₆ ) cycloalkyl group, (C ₁ -C ₆ ) alkoxy group, (C ₂ -C ₆ ) alkenyloxy group, (C ₂ -C ₆ ) alkynyloxy group, (C ₃ -C ₆₎ cycloalkoxy group, (C ₁ -C ₆₎ haloalkoxy group, a phenoxy group, (C ₁ -C ₆₎ alkylamino group, (C ₂ -C ₆₎ alkenyl amino group, (C ₂ -C ₆₎ alkynyl Amino group, di (C ₁ -C ₆ ) alkylamino group, di (C ₂ -C ₆ ) alkenylamino group, di (C ₂ -C ₆ ) alkynylamino group (C ₁ -C ₆ ) alkylthio group, (C The compound or a salt thereof according to (1), which is a ₁ -C ₆ ) alkylsulfinyl group or a (C ₁ -C ₆ ) alkylsulfonyl group.
(3) R ¹ is halogen atom, hydroxyl group, formyl group, phenoxy group, tri (C ₁ -C ₄ ) alkylsilyl group, (C ₁ -C ₆ ) alkyl group optionally substituted with A, substituted with A which may be (C ₁ -C ₆₎ haloalkyl group, it may be substituted by A (C ₁ -C ₆₎ alkoxy group which may be substituted by A (C ₁ -C ₆₎ haloalkoxy group, or A A (C ₂ -C ₆ ) haloalkenyloxy group optionally substituted by:
R ² is a hydrogen atom, formyl group, benzyloxy group, (C ₁ -C ₆ ) alkyl group optionally substituted with B, (C ₂ -C ₆ ) alkenyl group optionally substituted with B, substituted with B A (C ₂ -C ₆ ) alkynyl group, a (C ₁ -C ₆ ) alkoxy group optionally substituted with B, a (C ₃ -C ₆ ) cycloalkoxy group optionally substituted with B, B A (C ₁ -C ₆ ) haloalkoxy group optionally substituted with or a (C ₁ -C ₆ ) alkylamino group optionally substituted with B;
B is a (C ₃ -C ₆ ) cycloalkyl group, (C ₁ -C ₆ ) alkoxy group, phenoxy group, di (C ₁ -C ₆ ) alkylamino group, (C ₁ -C ₆ ) alkylthio group, (C The compound or salt thereof according to (1) or (2), which is a ₁ -C ₆ ) alkylsulfinyl group or (C ₁ -C ₆ ) alkylsulfonyl group.
(4) The compound or salt thereof according to (1), (2) or (3), wherein A is a (C ₁ -C ₆ ) alkoxy group.

  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-allyl-4-((4-phenoxyphenyl) ethynyl) pyridine (Compound No. 32) (1) Synthesis of trimethyl ((4-phenoxyphenyl) ethynyl) silane 1-bromo-4-phenoxybenzene (2.5 g, 10 mmol), trimethylsilylacetylene (3.0 g, 30 mmol), copper (I) iodide (0.1 g, 0.5 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.35 g, 0.5 mmol), triethylamine (30 mL) was stirred at 70 ° C. for 4 hours under a nitrogen atmosphere. 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 obtain the desired product (2.5 g, yield 93%). Obtained.

(2) Synthesis of 1-ethynyl-4-phenoxybenzene Trimethyl ((4-phenoxyphenyl) ethynyl) silane (2.4 g, 9.0 mmol), potassium carbonate (3.7 g, 27 mmol), and methanol (18 mL) at room temperature Stir for 4 hours. The solvent was evaporated under reduced pressure, 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 (1.8 g, yield 100%). Obtained.

(3) Synthesis of target product 3-allyl-4-bromopyridine hydrochloride (470 mg, 2 mmol), 1-ethynyl-4-phenoxybenzene (430 mg, 2.2 mmol), copper iodide (I) (20 mg , 0.1 mmol), tetrakis (triphenylphosphine) palladium (0) (70 mg, 0.1 mmol), and triethylamine (6 mL) were stirred at 70 ° C. for 6 hours under a nitrogen atmosphere. 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 (440 mg, 70% yield). Obtained.

Synthesis example 2
Synthesis of 3-allyl-4-((4- (dimethoxymethyl) phenyl) ethynyl) pyridine (Compound No. 91) (1) Synthesis of ((4- (dimethoxymethyl) phenyl) ethynyl) trimethylsilane 1-Bromo 4- (dimethoxymethyl) benzene (2.3 g, 10 mmol), trimethylsilylacetylene (2.93 g, 30 mmol), copper (I) iodide (0.09 g, 0.5 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.35 g, 0.5 mmol) and triethylamine (30 mL) were stirred at 60 ° C. for 10 hours under a nitrogen atmosphere. 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 obtain the desired product (2.3 g, yield 93%). Obtained.

(2) Synthesis of 1- (dimethoxymethyl) -4-ethynylbenzene ((4- (dimethoxymethyl) phenyl) ethynyl) trimethylsilane (2.3 g, 9.3 mmol), potassium carbonate (3.84 g, 27.8 mmol), methanol ( 18 mL) was reacted at room temperature for 2 hours. The solvent was evaporated under reduced pressure, 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 (1.7 g, yield 100%). Obtained.

(3) Synthesis of target product 3-allyl-4-bromopyridine hydrochloride (470 mg, 2 mmol), 1-ethynyl-4-phenoxybenzene (705 mg, 4 mmol), copper iodide (I) (19 mg , 0.1 mmol), tetrakis (triphenylphosphine) palladium (0) (70 mg, 0.1 mmol), and triethylamine (8 mL) were stirred at 70 ° C. for 4 hours under a nitrogen atmosphere. 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 (150 mg, yield 25%). Obtained.

Synthesis example 3
Synthesis of 3-methoxy-4-((4- (trimethylsilyl) phenyl) ethynyl) pyridine (Compound No. 43) (1) Synthesis of trimethyl (4-((trimethylsilyl) ethynyl) phenyl) silane (4-bromophenyl) Trimethylsilane (2.0 g, 8.7 mmol), trimethylsilylacetylene (1.29 g, 13.1 mmol), copper (I) iodide (0.05 g, 0.26 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.09 g, 0.13) mmol) and piperidine (10 mL) were stirred at 80 ° C. for 11 hours under a nitrogen atmosphere. 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 obtain the desired product (2.2 g, yield 100%). Obtained.

(2) Synthesis of (4-ethynylphenyl) trimethylsilane Trimethyl (4-((trimethylsilyl) ethynyl) phenyl) silane (2.19 g, 8.9 mmol), potassium carbonate (3.68 g, 26.6 mmol), methanol (15 mL) The reaction was performed at room temperature for 2 hours. The solvent was evaporated under reduced pressure, 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 (1.64 g, yield 100%). Obtained.

(3) Synthesis of target product 4-Bromo-3-methoxypyridine hydrochloride (220 mg, 1 mmol), (4-ethynylphenyl) trimethylsilane (210 mg, 1.2 mmol), copper iodide (I) (10 mg , 0.05 mmol), tetrakis (triphenylphosphine) palladium (0) (40 mg, 0.05 mmol), triphenylphosphine (30 mg, 0.1 mmol), triethylamine (3 mL), N, N-dimethylformamide (1 mL) Was reacted at 70 ° C. for 11 hours in a nitrogen atmosphere. 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 (170 mg, yield 60%). Obtained.

Synthesis example 4
Synthesis of 4-((4- (tert-butyl) phenyl) ethynyl) nicotinaldehyde (Compound No. 191) (1) (4-((4- (tert-butyl) phenyl) ethynyl) pyridin-3-yl) Synthesis of methanol (4-Bromopyridin-3-yl) methanol (0.84 g, 5.32 mmol), 4-tert-butylphenylacetylene (1.0 g, 5.32 mmol), triethylamine (2.5 mL, 17.9 mmol), bis (triphenyl) Phosphine) palladium (II) dichloride (0.19 g, 0.27 mmol), copper (I) iodide (0.06 g, 0.29 mmol), and N, N-dimethylformamide (15 mL) were stirred at 80 ° C. for 6 hours under a nitrogen atmosphere. did. The mixture was allowed 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 saturated brine and 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) to obtain the desired product (1.73 g, purity 69%, yield 85%).

(2) Synthesis of target product To a mixed solution of oxalyl chloride (0.2 mL, 2.3 mmol) and dichloromethane (4 mL), dimethyl sulfoxide (0.3 mL, 4.7 mmol) was added dropwise at −60 ° C. under a nitrogen atmosphere for 10 minutes. Stir. To the prepared solution, a mixed solution of (4-((4- (tert-butyl) phenyl) ethynyl) pyridin-3-yl) methanol (0.50 g, purity 69%, 1.30 mmol) and dichloromethane (4 mL) was added at the same temperature. The solution was added dropwise and stirred for 15 minutes. Triethylamine (1.3 mL, 9.4 mmol) was added dropwise at the same temperature, and then the temperature was raised to room temperature. After stirring at room temperature for 10 minutes, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and 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) to obtain the desired product (0.33 g, yield 96%).

Synthesis example 5
Synthesis of 4-((4- (tert-butyl) phenyl) ethynyl) -3- (phenoxymethyl) pyridine (Compound No. 260) (1) Synthesis of 4-bromo-3- (phenoxymethyl) pyridine (4- Bromopyridin-3-yl) methanol (300 mg, 1.60 mmol), phenol (157 mg, 1.67 mmol), triphenylphosphine (634 mg, 2.42 mmol), tetrahydrofuran (15 mL) in a mixed solution under ice-cooling, 40% Diethyltoluene azodicarboxylate solution (1.1 mL, 2.42 mmol) was added. The mixture was warmed to room temperature and stirred at the same temperature for 15 hours. The solvent was evaporated under reduced pressure, and the residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to obtain the desired product (372 mg, yield 88%).

(2) Synthesis of the desired product 4-bromo-3- (phenoxymethyl) pyridine (372 mg, 1.41 mmol), 4-tert-butylphenylacetylene (264 mg, 1.67 mmol), triethylamine (0.6 mL, 4.3 mmol), Bis (triphenylphosphine) palladium (II) dichloride (49 mg, 0.07 mmol), copper (I) iodide (25 mg, 0.13 mmol), N, N-dimethylformamide (5 mL) at 80 ° C. under nitrogen atmosphere For 7 hours. The mixture was allowed 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 saturated brine and 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 column chromatography (eluent: n-heptane / ethyl acetate = 90/10 to 75/25 / volume ratio) to obtain the desired product (237 mg, yield 49%).

Synthesis Example 6
Synthesis of 4-((4- (tert-butyl) phenyl) ethynyl) -3- (methoxymethoxy) pyridine (Compound No. 334) 4-Bromo-3- (methoxymethoxy) pyridine (1.22 g, 5.60 mmol), 4-tert-butylphenylacetylene (1.01 g, 6.36 mmol), triethylamine (2.3 mL, 4.3 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.20 g, 0.28 mmol), copper (I) iodide ( 0.05 g, 0.28 mmol) and N, N-dimethylformamide (15 mL) were stirred at 80 ° C. for 7 hours under a nitrogen atmosphere. The mixture was allowed 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 saturated brine and 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 column chromatography (eluent: n-heptane / ethyl acetate = 75/25 / volume ratio), and the resulting solid was washed with n-heptane to obtain the desired product (0.65 g, yield 39%). )

Synthesis example 7
Synthesis of 4-((4- (tert-butyl) phenyl) ethynyl) -3- (2,2,2-trifluoroethoxy) pyridine (Compound No. 409) (1) 4-((4- (tert- Synthesis of butyl) phenyl) ethynyl) -3-nitropyridine 4-chloro-3-nitropyridine (5.0 g, 31.6 mmol), 4-tert-butylphenylacetylene (5.0 g, 31.6 mmol), triethylamine (1.3 mL, 93.3 mmol), bis (triphenylphosphine) palladium (II) dichloride (1.1 g, 1.6 mmol), copper (I) iodide (0.3 g, 1.6 mmol), N, N-dimethylformamide (60 mL) under a nitrogen atmosphere. And stirred at room temperature for 15 hours. Water and ethyl acetate were added to the reaction solution, and the mixed solution was filtered through celite and extracted with ethyl acetate. The organic layer was washed with saturated brine and 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 silica gel column chromatography (eluent: n-heptane / ethyl acetate = 95/5 to 80/20, volume ratio), The desired product (7.6 g, yield 85%) was obtained.

(2) Synthesis of 4-((4- (tert-butyl) phenyl) ethynyl) pyridin-3-amine 4-((4- (tert-butyl) phenyl) ethynyl) -3-nitropyridine (7.6 g, 27.0 mmol) and iron (4.5 g, 81.0 mmol) were added to a mixed solution of ethyl acetate (30 mL), acetic acid (15 mL), and water (15 mL), and the mixture was stirred for 1 hour under reflux. The reaction solution was filtered through celite, and the solvent was evaporated under reduced pressure. The residue was diluted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and 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 silica gel column chromatography (eluent: n-heptane / ethyl acetate = 30/70, volume ratio) to obtain the desired product (7.2 g, yield 100%).

(3) Synthesis of target product Under ice cooling, 4-((4- (tert-butyl) phenyl) ethynyl) pyridin-3-amine (1.50 g, 5.99 mmol), 2,2,2-trifluoroethanol (4.31 g, 43.1 mmol) and trifluoroacetic acid (1.09 g, 9.56 mmol) were mixed dropwise with tert-butyl nitrite (0.8 mL, 6.6 mmol). After the dropwise addition, the temperature of the reaction solution was raised to 25 ° C, and potassium carbonate (1.24 g, 8.99 mmol) was added little by little while keeping the temperature in the range of 25-30 ° C. Thereafter, the mixture was stirred at room temperature for 21 hours. Water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and 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 column chromatography (eluent: n-heptane / ethyl acetate = 50/50 / volume ratio) to obtain the desired product (0.09 g, yield 5%).

Synthesis example 8
Synthesis of 4-((4- (tert-butyl) phenyl) ethynyl) -3- (2- (methylthio) ethoxy) pyridine (Compound No. 365) (1) 3- (2- (methylthio) ethoxy) -4 -Synthesis of nitropyridine 1-oxide Under ice-cooling, 3-fluoro-4-nitropyridine 1-oxide (2.00 g, 12.7 mmol), 2- (methylthio) ethanol (1.78 g, 19.3 mmol), potassium carbonate (2.10 g) , 15.2 mmol), N, N-dimethylformamide (10 mL) was stirred at 80 ° C. for 3 hours. The mixture was allowed to cool to room temperature, and ice water (100 mL) was added to the reaction solution for crystallization. The solid was collected by vacuum filtration and washed with water to obtain the desired product (1.77 g, 61%).

(2) Synthesis of 4-bromo-3- (2- (methylthio) ethoxy) pyridine hydrochloride 3- (2- (methylthio) ethoxy) -4-nitropyridine 1-oxide (1.00 g, 4.34 mmol) at room temperature Phosphorus tribromide (3.3 mL, 35.0 mmol) was added dropwise to a mixed suspension of ethyl acetate and ethyl acetate at a rate such that the temperature in the reaction system did not exceed 40 ° C. After dropping, the mixture was stirred for 10 minutes at the same temperature, and then stirred for 16 hours under reflux. The mixture was allowed to cool to room temperature, and the reaction mixture was poured into ice water (50 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- (2- (methylthio) ethoxy) pyridine. The obtained 4-bromo-3- (2- (methylthio) ethoxy) pyridine was dissolved in ethyl acetate (100 mL), and 1.0 M hydrogen chloride ether solution (10 mL, 10 mmol) was added under ice cooling. The solvent was distilled off under reduced pressure to obtain the desired product (0.96 g, yield 77%).

(3) Synthesis of target product 4-Bromo-3- (2- (methylthio) ethoxy) pyridine hydrochloride (0.96 g, 3.4 mmol), 4-tert-butylphenylacetylene (0.54 g, 3.4 mmol), triethylamine (1.8 mL, 13 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.11 g, 0.16 mmol), copper (I) iodide (0.04 g, 0.19 mmol), N, N-dimethylformamide (15 mL). The mixture was stirred at 80 ° C. for 6 hours under a nitrogen atmosphere. The mixture was allowed 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 saturated brine and 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 column chromatography (eluent: n-heptane / ethyl acetate = 75/25 to 40/60 / volume ratio) to obtain the desired product (183 mg, 17% yield).

Synthesis Example 9
4-((4- (tert-butyl) phenyl) ethynyl) -3- (2- (methylsulfinyl) ethoxy) pyridine (Compound No. 375) and 4-((4- (tert-butyl) phenyl) ethynyl) Synthesis of 3- (2- (methylsulfonyl) ethoxy) pyridine (Compound No. 376) 4-((4- (tert-butyl) phenyl) ethynyl) -3- (2- (methylthio) ethoxy) pyridine (770 mg, 2.37 mmol) was dissolved in chloroform (10 mL) and ice-cooled. 3-chloroperbenzoic acid (875 mg, 3.55 mmol) was added, and the mixture was stirred for 3 hours under ice cooling. A 20% aqueous sodium carbonate solution (10 mL) was added, and the mixture was separated. The aqueous layer was extracted with ethyl acetate, and the collected organic layer was 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 column chromatography (eluent: n-heptane / ethyl acetate = 50/50 to 0/100 / volume ratio, then ethanol). 4-((4- (tert-butyl) phenyl) ethynyl) -3- (2- (methylsulfinyl) ethoxy) pyridine (Compound No. 375) (213 mg, 26% yield), 4-(( 4- (tert-butyl) phenyl) ethynyl) -3- (2- (methylsulfonyl) ethoxy) pyridine (Compound No. 376) (313 mg, 37% yield) was obtained.

Synthesis Example 10
Synthesis of 4-((4- (tert-butyl) phenyl) ethynyl) -3- (cyclopropylmethoxy) pyridine (Compound No. 321) (1) 3- (Cyclopropylmethoxy) -4-nitropyridine 1-oxide Synthesis of 3-fluoro-4-nitropyridine 1-oxide (2.00 g, 12.7 mmol), cyclopropylmethanol (1.51 g, 20.9 mmol), potassium carbonate (2.10 g, 15.2 mmol), N, N- Dimethylformamide (10 mL) was stirred at 80 ° C. for 3 hours. The mixture was allowed to cool to room temperature, saturated brine was added to the reaction solution, and the mixture was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the organic layer for drying, and the anhydrous sodium sulfate was removed by filtration. The solvent was evaporated under reduced pressure to obtain the desired product (1.45 g, yield 55%).

(2) Synthesis of 4-bromo-3- (cyclopropylmethoxy) pyridine 1-oxide 3- (cyclopropylmethoxy) -4-nitropyridine 1-oxide (0.88 g, 4.19 mmol), acetyl bromide (0.9 mL, 12 mmol) and acetic acid (15 mL) were stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. The mixture was allowed to cool to room temperature, and the solvent was distilled off under reduced pressure. The residue was dissolved in ethyl acetate and washed with 20% aqueous sodium carbonate solution and saturated brine in this order. Anhydrous sodium sulfate was added to the organic layer for drying, and the anhydrous sodium sulfate was removed by filtration. The solvent was evaporated under reduced pressure to obtain the desired product (0.90 g, yield 88%).

(3) Synthesis of 4-bromo-3- (cyclopropylmethoxy) pyridine 4-bromo-3- (cyclopropylmethoxy) pyridine 1-oxide (0.90 g, 3.69 mmol), iron (1.24 g, 22.1 mmol), acetic acid (10 mL) was stirred for 6 hours under reflux of acetic acid. The mixture was allowed to cool to room temperature, and the solvent was distilled off under reduced pressure. The residue was diluted with ethyl acetate and washed with 20% aqueous sodium carbonate solution and saturated brine. Anhydrous sodium sulfate was added to the organic layer for drying, the anhydrous sodium sulfate was removed by filtration, and the solvent was evaporated under reduced pressure. The residue was purified by flash chromatography (eluent: n-heptane / ethyl acetate) to obtain the desired product (0.17 g, yield 21%).

(4) Synthesis of target product 4-Bromo-3- (cyclopropylmethoxy) pyridine (0.17 g, 0.76 mmol), 4-tert-butylphenylacetylene (0.16 g, 1.02 mmol), triethylamine (0.4 mL, 2.9 mmol) , Bis (triphenylphosphine) palladium (II) dichloride (0.04 g, 0.06 mmol), copper (I) iodide (0.02 g, 0.09 mmol), N, N-dimethylformamide (3 mL) under nitrogen atmosphere, 80 Stir at 0 ° C. for 10 hours. The mixture was allowed 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 saturated brine and 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) to obtain the desired product (0.17 g, yield 75%).

Synthesis Example 11
Synthesis of 3-ethoxy-4-((4- (1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl) phenyl) ethynyl) pyridine (Compound No. 122) ) Synthesis of 4- (1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl) aniline 4- (Perfluoropropan-2-yl) aniline (5.0 g, 19.1 mmol) To the mixture, 28% sodium methoxide methanol solution (37 g) was added and stirred at 70 ° C. for 3 hours. The mixture was allowed 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 saturated brine and 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 silica gel column chromatography (eluent: n-heptane / ethyl acetate = 60/30, volume ratio) to obtain the desired product (3.2 g, 61% yield).

(2) Synthesis of 1-bromo-4- (1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl) benzene 4- (1,1,1,3,3 3-hexafluoro-2-methoxypropan-2-yl) aniline (2.0 g, 7.3 mmol), copper (II) bromide (1.8 g, 8.0 mmol), tert-butyl nitrite (0.98 g, 9.5 mmol), Acetonitrile (20 mL) was stirred at room temperature overnight. Water was added to the reaction solution, and the mixture was extracted with ethyl acetate. . The organic layer was washed with saturated brine and 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 silica gel column chromatography (eluent: n-heptane / ethyl acetate = 90/10, volume ratio) to obtain the desired product (2.0 g, yield 83%).

(3) Synthesis of 3-ethoxy-4-((trimethylsilyl) ethynyl) pyridine 4-bromo-3-ethoxypyridine (0.38 g, 1.5 mmol), trimethylsilylacetylene (0.23 g, 2.3 mmol), copper (I) iodide (0.05 g, 0.24 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.06 g, 0.08 mmol), triethylamine (0.64 g, 6.3 mmol), N, N-dimethylformamide (10 mL) under nitrogen atmosphere , And stirred at 70 ° C. for 2 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 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 (0.10 g, yield 28%). Obtained.

(4) Synthesis of target product 3-ethoxy-4-((trimethylsilyl) ethynyl) pyridine (0.10 g, 0.46 mmol), 1-bromo-4- (1,1,1,3,3,3-hexafluoro- 2-methoxypropan-2-yl) benzene (0.31 g, 0.91 mmol), copper (I) iodide (0.01 g, 0.07 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.02 g, 0.02 mmol) , Triethylamine (0.14 g, 1.3 mmol), 1.0 M tetrabutylammonium fluoride tetrahydrofuran solution (0.5 mL, 0.5 mmol), and N, N-dimethylformamide (10 mL) were stirred at 70 ° C. for 3 hours under a nitrogen atmosphere. . 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 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 (38 mg, 20% yield). Obtained.

Intermediate synthesis example 1
Production of 3-allyl-4-bromopyridine hydrochloride (1) Production of 3-allyl-4-bromopyridine Under ice-cooling, 4-bromopyridine hydrochloride (5.0 g, 25.7 mmol) was added to toluene (25 mL), 3M Aqueous sodium hydroxide solution (15 mL) was added and stirred for 30 minutes. The reaction mixture was separated, anhydrous sodium sulfate was added to the organic layer and dried, and then anhydrous sodium sulfate was removed by filtration. Tetrahydrofuran (50 mL) was added to the obtained 4-bromopyridine in toluene solution, cooled to −78 ° C., 1M lithium diisopropylamide n-hexane and tetrahydrofuran solution (25 mL) were added dropwise, and the mixture was stirred at the same temperature for 1 hour. did. Allyl iodide (2.5 mL, 27.4 mmol) was added dropwise at −78 ° C., and the temperature was raised to room temperature over 3 hours. Saturated brine was added to the reaction mixture for liquid separation, and anhydrous sodium sulfate was added to the organic layer for drying. After removing anhydrous sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-heptane / ethyl acetate = 90/10, volume ratio) to obtain the desired product (0.95 g, yield 19%).

(2) Synthesis of target product Under ice-cooling, 1.0M hydrogen chloride ether solution (18.2 mL, 18.2) was added to a solution of 3-allyl-4-bromopyridine (3.0 g, 15.2 mmol) and diethyl ether (30 mL). mmol) was added and stirred at the same temperature for 10 minutes. Diethyl ether was distilled off under reduced pressure to obtain 3-allyl-4-bromopyridine hydrochloride (3.5 g, yield 99%).

Intermediate synthesis example 2
Preparation of 4-bromo-3-methoxypyridine hydrochloride (1) Synthesis of 3-methoxy-4-nitropyridine 1-oxide 3-fluoro-4-nitropyridine 1-oxide (9.75 g, 61.7 mmol) under ice cooling 28% sodium methoxide methanol solution (11.9 g, 61.7 mmol) was added to a mixed suspension of methanol and methanol (145 mL). The mixture was warmed to room temperature and stirred at the same temperature for 1 hour. Methanol was distilled off under reduced pressure, water (50 mL) was added to the residue, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the solvent was evaporated under reduced pressure to obtain the desired product (9.54 g, yield 91%).

(2) Synthesis of target product At room temperature, a mixed suspension of 3-methoxy-4-nitropyridine 1-oxide (9.54 g, 56.1 mmol) and ethyl acetate (100 mL) was mixed with phosphorus tribromide (45 mL, 477 mmol) was added dropwise at a rate such that the temperature in the reaction system did not exceed 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 stirred at the same temperature for 17 hours. After being allowed to cool to room temperature, the reaction mixture was poured into ice water (500 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 3-bromo-4-methoxypyridine. To a solution of the obtained 3-bromo-4-methoxypyridine in 100 mL of ethyl acetate, 1.0 M hydrogen chloride ether solution (60 mL, 60 mmol) was added. The solvent was distilled off under reduced pressure to obtain the desired product (7.80 g, yield 62%).

Intermediate synthesis example 3
Synthesis of 4-bromo-3-ethoxypyridine hydrochloride (1) Synthesis of 3-ethoxy-4-nitropyridine 1-oxide 3-fluoro-4-nitropyridine 1-oxide (12 g, 76 mmol) under ice cooling 20% sodium ethoxide ethanol solution (29 g, 86 mmol) was added to a mixed suspension of ethanol and ethanol (300 mL). The mixture was warmed to room temperature and stirred at the same 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 obtain the desired product (11 g, yield 76%).

(2) Synthesis of target product At room temperature, a mixed suspension of 3-ethoxy-4-nitropyridine 1-oxide (5.0 g, 27 mmol) and ethyl acetate (250 mL) was mixed with phosphorus tribromide (21 mL, 222 mmol) was added dropwise at a rate such that the temperature in the reaction system did not exceed 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 stirred 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 4-bromo-3-ethoxypyridine 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 Table 1. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In Table 1, the numerical values described in the physical properties column indicate melting points (° C.), and for compounds where melting points are not described, their ¹ H-NMR spectral data are listed in Table 2. In Tables 1 and 2, No. indicates a compound number. In the table, Me is a methyl group, Et is an ethyl group, i-Pr is an isopropyl group, t-Bu is a tertiary butyl group, c-Pr is a cyclopropyl group, and c-Bu is a cyclobutyl group. C-Pen represents a cyclopentyl group, c-Hex represents a cyclohexyl group, and Bn represents a benzyl group. On the other hand, in the column of R ¹ , for example, in the compound described as “4-F”, the substitution position given to the chemical structural formula in the table is substituted with R ¹ , that is, the 4-position is a fluorine atom. In the compound described as “3-F, 4-CF ₃ ”, the 3-position is substituted with a fluorine atom and the 4-position is substituted with a trifluoromethyl group. Further, for example, in the compound in which W is CH and “3,4-OCH ₂ O—” is described in the R ¹ column, the 3-position and 4-position substituents are combined together to form 1, This represents the formation of a 3-benzodioxole ring, and other similar descriptions also apply to this.

For Compound No.608 a result of measuring the mass spectrum by LC-MS (JEOL Ltd. JMS-SX102), was [M ^{+ H]} + 360.

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, 2, 43, 91, 122, 146, 181, 321, 334, 345, 387, 397, 407, 409, 419, 580, 590, 600, 601, 602, 603, 604 , 605, 606, 607, 608, 609, 610, 611, 612, 613, 614, 617, 619, 620, 621, 622, 623, 624, 625, 626, 627, 628, 629 and 630 are 90% or more Showed the death rate.
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 No. 2, 32, 43, 91, 122, 146, 181, 321, 334, 345, 387, 397, 407, 409, 419, 579, 580, 590, 600, 601, 602, 603 , 604, 605, 606, 607, 608, 609, 610, 611, 612, 613, 614, 615, 616, 617, 618, 619, 620, 621, 622, 623, 624, 625, 626, 627, 628 , 629 and 630 showed control values of 90 or more.
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

Test Example 3 Effect test on the spider mite A solution prepared so that the concentration of the compound of the present invention was 100 ppm was processed into a plastic vial. After the chemical solution was air-dried, 20 juvenile ticks were placed and allowed to stand under constant dark conditions of 25 ° C. and relative humidity of 80 to 100%. The number of mites that died 24 hours after drug contact was recorded, and the mortality (%) was determined by the following formula. As a result, the compound Nos. 1 and 2 showed a death rate of 90% or more.
Death rate (%) = number of dead ticks / total number of ticks x 100

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 (9)

Formula (I):

[Wherein R ¹ is substituted with a halogen atom, amino group, hydroxyl group, mercapto group, cyano group, nitro group, formyl group, carboxyl group, phenoxy group, tri (C ₁ -C ₄ ) alkylsilyl group, or A (C ₁ -C ₆ ) alkyl group optionally substituted with (C ₂ -C ₆ ) alkenyl group optionally substituted with A, (C ₂ -C ₆ ) alkynyl group optionally substituted with A substituted with A A (C ₃ -C ₆ ) cycloalkyl group which may be substituted, a (C ₃ -C ₆ ) cycloalkenyl group which may be substituted with A, a (C ₁ -C ₆ ) haloalkyl group which may be substituted with A, (C ₂ -C ₆ ) haloalkenyl group optionally substituted with A, (C ₁ -C ₆ ) alkoxy group optionally substituted with A, (C ₂ -C ₆ ) alkenyl optionally substituted with A An oxy group, an optionally substituted (C ₂ -C ₆ ) alkynyloxy group, an optionally substituted (C ₃ -C ₆ ) cycloalkoxy group, an optionally substituted A (C _3- C ₆ ) Cycloalkenyloxy group, optionally substituted with (C ₁ -C ₆ ) haloalkoxy group, optionally substituted with (C ₂ -C ₆ ) haloalkenyloxy group, optionally substituted with A (C ₁ -C ₆ ) alkylthio group, optionally substituted with (C ₂ -C ₆ ) alkenylthio group, optionally substituted with (C ₂ -C ₆ ) alkynylthio group, substituted with A which may be (C ₃ -C ₆₎ cycloalkyl thio group which may be substituted by A (C ₃ -C ₆₎ cycloalkenylthio group which may be substituted by A (C ₁ -C ₆₎ haloalkylthio group Or a (C ₂ -C ₆ ) haloalkenylthio group optionally substituted by A;
A is a (C ₃ -C ₆ ) cycloalkyl group, (C ₃ -C ₆ ) cycloalkenyl group, (C ₁ -C ₆ ) alkoxy group, (C ₂ -C ₆ ) alkenyloxy group, (C ₂ -C ₆₎ alkynyloxy group, (C ₃ -C ₆₎ cycloalkoxy group, (C ₃ -C ₆₎ cycloalkenyl group, (C ₁ -C ₆₎ haloalkoxy group or a (C ₂ -C ₆₎ haloalkenyloxy A group;
R ² is a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, a mercapto group, a cyano group, a nitro group, a formyl group, a carboxyl group, a benzyloxy group, or a (C ₁ -C ₆ ) alkyl group optionally substituted by B (C ₂ -C ₆ ) alkenyl group optionally substituted with B, (C ₂ -C ₆ ) alkynyl group optionally substituted with B, (C ₃ -C ₆ ) cyclo optionally substituted with B An alkyl group, a (C ₃ -C ₆ ) cycloalkenyl group that may be substituted with B, a (C ₁ -C ₆ ) haloalkyl group that may be substituted with B, an optionally substituted with B (C ₂ -C) ₆ ) A haloalkenyl group, (C ₁ -C ₆ ) alkoxy group optionally substituted with B, (C ₂ -C ₆ ) alkenyloxy group optionally substituted with B, optionally substituted with B (C ₂ -C ₆₎ alkynyloxy group which may be substituted by B (C ₃ -C ₆₎ cycloalkoxy group which may be substituted by B (C ₃ -C ₆₎ cycloalkenyl O Shi group which may be substituted by B (C ₁ -C ₆₎ haloalkoxy group, may be substituted with B (C ₂ -C ₆₎ haloalkenyloxy group which may be substituted by B (C ₁ -C ₆ ) alkylamino group, optionally substituted with B (C ₂ -C ₆ ) alkenylamino group, optionally substituted with B (C ₂ -C ₆ ) alkynylamino group, optionally substituted with B A good (C ₃ -C ₆ ) cycloalkylamino group, a (C ₃ -C ₆ ) cycloalkenylamino group optionally substituted with B, a (C ₁ -C ₆ ) haloalkylamino group optionally substituted with B, (C ₂ -C ₆ ) haloalkenylamino group optionally substituted with B, di (C ₁ -C ₆ ) alkylamino group optionally substituted with B, di (C _2- C ₆ ) alkenylamino group, di (C ₂ -C ₆ ) alkynylamino group optionally substituted with B, di (C ₃ -C ₆ ) cycloalkylamino group optionally substituted with B, substituted with B Even Di (C ₃ -C ₆ ) cycloalkenylamino group, di (C ₁ -C ₆ ) haloalkylamino group optionally substituted with B, di (C ₂ -C ₆ ) haloalkenyl optionally substituted with B Amino group, (C ₁ -C ₆ ) alkylthio group optionally substituted with B, (C ₂ -C ₆ ) alkenylthio group optionally substituted with B, optionally substituted with B (C ₂ -C ₆₎ alkynylthio which may be substituted by B (C ₃ -C ₆₎ cycloalkylthio group which may be substituted by B (C ₃ -C ₆₎ cycloalkenylthio group, may be substituted with B A (C ₁ -C ₆ ) haloalkylthio group or a (C ₂ -C ₆ ) haloalkenylthio group optionally substituted with B;
B is a (C ₃ -C ₆ ) cycloalkyl group, (C ₃ -C ₆ ) cycloalkenyl group, (C ₁ -C ₆ ) alkoxy group, (C ₂ -C ₆ ) alkenyloxy group, (C ₂ -C ₆₎ alkynyloxy group, (C ₃ -C ₆₎ cycloalkoxy group, (C ₃ -C ₆₎ cycloalkenyl group, (C ₁ -C ₆₎ haloalkoxy group, (C ₂ -C ₆₎ haloalkenyloxy Group, phenoxy group, (C ₁ -C ₆ ) alkylamino group, (C ₂ -C ₆ ) alkenylamino group, (C ₂ -C ₆ ) alkynylamino group, di (C ₁ -C ₆ ) alkylamino group, Di (C ₂ -C ₆ ) alkenylamino group, di (C ₂ -C ₆ ) alkynylamino group, (C ₁ -C ₆ ) alkylthio group, (C ₂ -C ₆ ) alkenylthio group, (C ₂ -C ₆₎ alkynylthio, (C ₁ -C ₆₎ alkylsulfinyl group, (C ₂ -C ₆₎ alkenylsulfinyl group, (C ₂ -C ₆₎ alkynylsulfinyl group, (C ₁ -C ₆₎ An alkylsulfonyl group or a (C ₂ -C ₆ ) alkenylsulfonyl group or a (C ₂ -C ₆ ) alkynylsulfonyl group;
W is CH or a nitrogen atom;
n is an integer of 0 to 3; when n is 2 or more, R ¹ may be the same as or different from each other, and two adjacent R ¹ together are substituted together with a benzene ring or a pyridine ring. Condensed rings may be formed; provided that 4-((2-fluorophenyl) ethynyl) pyridin-3-amine, 4- (4-methoxyphenylethynyl) nicotinaldehyde and 4- (2-methoxy 4- (arylethynyl) pyridine compounds or salts thereof represented by the following formula (except phenyl) ethynyl) -3-methylpyridine]: R ¹ is halogen atom, hydroxyl group, formyl group, carboxyl group, phenoxy group, tri (C ₁ -C ₄ ) alkylsilyl group, (C ₁ -C ₆ ) alkyl group optionally substituted with A, substituted with A An optionally substituted (C ₂ -C ₆ ) alkenyl group, an optionally substituted (C ₂ -C ₆ ) alkynyl group, an optionally substituted (C ₁ -C ₆ ) haloalkyl group, A (C ₁ -C ₆ ) alkoxy group which may be substituted, (C ₁ -C ₆ ) haloalkoxy group which may be substituted with A, (C ₂ -C ₆ ) haloalkenyloxy which may be substituted with A group, may be substituted by A (C ₁ -C ₆₎ may be substituted with an alkylthio group, or A (C ₁ -C ₆₎ be a haloalkylthio group;
A is a (C ₃ -C ₆ ) cycloalkyl group, (C ₁ -C ₆ ) alkoxy group, (C ₂ -C ₆ ) alkenyloxy group, (C ₂ -C ₆ ) alkynyloxy group, (C ₃ -C ₆ ) a cycloalkoxy group or a (C ₁ -C ₆ ) haloalkoxy group;
R ² is a hydrogen atom, formyl group, benzyloxy group, (C ₁ -C ₆ ) alkyl group optionally substituted with B, (C ₂ -C ₆ ) alkenyl group optionally substituted with B, substituted with B An optionally substituted (C ₂ -C ₆ ) alkynyl group, a (C ₃ -C ₆ ) cycloalkyl group optionally substituted with B, a (C ₁ -C ₆ ) alkoxy group optionally substituted with B, B (C ₃ -C ₆ ) cycloalkoxy group optionally substituted with, (C ₁ -C ₆ ) haloalkoxy group optionally substituted with B, (C ₁ -C ₆ ) alkyl optionally substituted with B Amino group, (C ₃ -C ₆ ) cycloalkylamino group optionally substituted with B, (C ₁ -C ₆ ) haloalkylamino group optionally substituted with B, di (C ₁ -C ₆ ) alkylamino group, di (C ₃ -C ₆ ) cycloalkylamino group optionally substituted with B, di (C ₁ -C ₆ ) haloalkylamino group optionally substituted with B, May be replaced C ₁ -C ₆₎ alkylthio group which may be substituted by B (C ₃ -C ₆₎ may be substituted with a cycloalkylthio group, or B (C ₁ -C ₆₎ be a haloalkylthio group;
B is a (C ₃ -C ₆ ) cycloalkyl group, (C ₁ -C ₆ ) alkoxy group, (C ₂ -C ₆ ) alkenyloxy group, (C ₂ -C ₆ ) alkynyloxy group, (C ₃ -C ₆₎ cycloalkoxy group, (C ₁ -C ₆₎ haloalkoxy group, a phenoxy group, (C ₁ -C ₆₎ alkylamino group, (C ₂ -C ₆₎ alkenyl amino group, (C ₂ -C ₆₎ alkynyl Amino group, di (C ₁ -C ₆ ) alkylamino group, di (C ₂ -C ₆ ) alkenylamino group, di (C ₂ -C ₆ ) alkynylamino group, (C ₁ -C ₆ ) alkylthio group, C ₁ -C ₆₎ the compound or a salt thereof according to claim 1 is alkylsulfinyl group or a (C ₁ -C ₆₎ alkylsulfonyl group. R ¹ may be substituted with a halogen atom, a hydroxyl group, a formyl group, a phenoxy group, a tri (C ₁ -C ₄ ) alkylsilyl group, an optionally substituted (C ₁ -C ₆ ) alkyl group, or A Good (C ₁ -C ₆ ) haloalkyl group, (C ₁ -C ₆ ) alkoxy group optionally substituted with A, (C ₁ -C ₆ ) haloalkoxy group optionally substituted with A or substituted with A And may be a (C ₂ -C ₆ ) haloalkenyloxy group;
R ² is a hydrogen atom, formyl group, benzyloxy group, (C ₁ -C ₆ ) alkyl group optionally substituted with B, (C ₂ -C ₆ ) alkenyl group optionally substituted with B, substituted with B A (C ₂ -C ₆ ) alkynyl group, a (C ₁ -C ₆ ) alkoxy group optionally substituted with B, a (C ₃ -C ₆ ) cycloalkoxy group optionally substituted with B, B A (C ₁ -C ₆ ) haloalkoxy group optionally substituted with or a (C ₁ -C ₆ ) alkylamino group optionally substituted with B;
B is a (C ₃ -C ₆ ) cycloalkyl group, (C ₁ -C ₆ ) alkoxy group, phenoxy group, di (C ₁ -C ₆ ) alkylamino group, (C ₁ -C ₆ ) alkylthio group, (C The compound or a salt thereof according to claim 1, which is a ₁ -C ₆ ) alkylsulfinyl group or a (C ₁ -C ₆ ) alkylsulfonyl group.   A pest control agent comprising the compound according to claim 1 or a salt thereof as an active ingredient.   An agricultural and horticultural pest control agent comprising the compound according to claim 1 or a salt thereof as an active ingredient.   An insecticide, acaricide, nematicide or soil insecticide containing the compound according to claim 1 or a salt thereof as an active ingredient.   An insecticide or acaricide containing the compound according to claim 1 or a salt thereof as an active ingredient.   An animal killing parasite agent comprising the compound according to claim 1 or a salt thereof as an active ingredient.   A method for controlling pests by applying an effective amount of the compound according to claim 1 or a salt thereof.