WO2024117205A1

WO2024117205A1 - Bicyclic pyridine derivative and salt thereof, and harmful organism control agent characterized by containing said derivative or salt thereof as active ingredient

Info

Publication number: WO2024117205A1
Application number: PCT/JP2023/042830
Authority: WO
Inventors: 聡仁大▲高▼; 勇人土居; 祥森下; 優輔三谷
Original assignee: 北興化学工業株式会社
Priority date: 2022-11-30
Filing date: 2023-11-29
Publication date: 2024-06-06

Abstract

The present invention provides: a bicyclic pyridine derivative represented by general formula (1) or a salt thereof; and an agricultural/horticultural chemical agent, a pesticide, and others each containing the bicyclic pyridine derivative or a salt thereof as an active ingredient. In the general formula (1), R¹, R², Z and A¹ to A³ each independently represent a specific substituent; and n represents 0 or 1.

Description

Bicyclic pyridine derivatives and their salts, and pest control agents containing the derivatives or their salts as active ingredients

The present invention relates to novel bicyclic pyridine derivatives and their salts, and to pest control agents, particularly insecticides, acaricides, nematicides, and fungicides, that contain the derivatives or their salts as active ingredients. It also relates to a method for using the pest control agents and a method for producing them.

　In the agricultural and horticultural fields, insecticides, miticides, nematicides and fungicides have been developed and put to practical use in order to control various harmful organisms. However, the insecticides, miticides, nematicides and fungicides that have been widely used so far are not necessarily satisfactory in terms of efficacy, spectrum or residual activity. Furthermore, it cannot be said that they fully meet societal demands such as reducing the number of applications and the amount of application.

The emergence of pests and fungi that have developed resistance or tolerance to the insecticides, miticides, nematicides and fungicides that have traditionally been widely used is also becoming a problem. For example, in the cultivation of vegetables, fruit trees, flowers, tea, wheat and rice, the use of various types of insecticides and miticides, such as organophosphates (fenitrothion, malathion, prothiophos, DDVP, etc.), pyrethroids (permethrin, cypermerin, fenvalerate, cyhalothrin, etc.), benzoylureas (diflubenzuron, teflubenzuron, chlorfluazuron, etc.), nereistoxins (cartap, bensultap, etc.), neonicotinoids, etc., is becoming more and more common. It is becoming more and more difficult to control pests that have developed resistance to insecticides and acaricides such as tinoids (imidaclopirid, thiamethoxam, dinotefuran, etc.) and diamides (flubendiamide, chlorantraniliprole, etc.), as well as fungi that have developed resistance to various types of fungicides, such as DMIs (triflumizole, myclobutanil, etc.), QoIs (azoxystrobin, kresoxim-methyl, etc.), and SDHIs (boscalid, etc.).

Furthermore, there are insecticides and acaricides to which pests have not yet developed resistance (for example, organohalogen pesticides such as DDT and BHC, and chlorinated cyclic diene pesticides such as aldrin, dieldrin, endrin, heptachlor, and benzoepine), but these are not desirable from the standpoint of toxicity and environmental pollution. Therefore, there is a strong need for the development of new insecticides, acaricides, and fungicides that are sufficiently effective at low doses against various pests that have developed resistance to conventional general-purpose agricultural and horticultural insecticides, are highly safe for useful organisms, and have little adverse effect on the environment.

　For example, Patent Documents 1 and 2 disclose bicyclic pyridine derivatives that have insecticidal and acaricidal activity against various harmful organisms, but the structure is limited to [1,2,4]triazolo[1,5]pyridine, and there is no disclosure of the bicyclic pyridine derivative according to the present invention.

Japanese Patent Publication No. 2011-168582 International Publication No. 2022/003510

The objective of the present invention is to provide a novel bicyclic pyridine derivative or a salt thereof, a pest control agent containing the same, and a method for using the same.

As a result of extensive research aimed at solving the above problems, the present inventors have discovered that a bicyclic pyridine derivative represented by the following general formula (1) or a salt thereof is useful as a pest control agent, particularly as an insecticide, acaricide, nematicide or fungicide, and have thus completed the present invention.

Therefore, the first invention of the present application relates to a bicyclic pyridine derivative represented by the following general formula (1) and a salt thereof (sometimes referred to as the "compound of the present invention" in this specification).
The second invention of the present application relates to a pest control agent comprising, as an active ingredient, a bicyclic pyridine derivative represented by the following general formula (1) or a salt thereof:

The present invention includes the following aspects.
[1]

General formula (1)

(Wherein,
R ¹ is a hydrogen atom, a hydroxyl group, a formyl group, a hydroxycarbonyl group, a cyano group, a nitro group, a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted by U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkenyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 haloalkoxycarbonyl group, a C3-C6 cyclo Alkylcarbonyl group, C3-C6 cycloalkyloxycarbonyl group, C1-C6 alkylcarbonyloxy group, C1-C6 haloalkylcarbonyloxy group, C1-C6 alkoxycarbonyloxy group, C1-C6 haloalkoxycarbonyloxy group, C3-C6 cycloalkylcarbonyloxy group, C3-C6 cycloalkyloxycarbonyloxy group, C1-C6 alkylthio group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylthio group, C1-C6 haloalkylsulfinyl group, C1-C6 haloalkylsulfonyl group, C3-C6 cyclo an alkylthio group, a C3-C6 cycloalkylsulfinyl group, a C3-C6 cycloalkylsulfonyl group, a carbamoyl group which may be mono- or poly-substituted by K, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5- or 6-membered ring), an aryl group which may be mono- or poly-substituted by W, a heterocyclic group which may be mono- or poly-substituted by W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a C7-C11 aralkyloxy group which may be mono- or poly-substituted with W, a C7-C11 aralkylthio group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group;
R ² is a hydrogen atom, a hydroxyl group, a formyl group, a hydroxycarbonyl group, a cyano group, a nitro group, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 haloalkoxycarbonyl group, a C3-C6 cycloalkyloxy group, a C3-C6 cycloalkyloxycarbonyl group, a C1-C6 alkylcarbonyloxy group, a C1-C6 haloalkylcarbonyloxy group, a C1-C6 alkoxycarbonyloxy group, a C1-C6 haloalkoxycarbonyloxy group, a C3-C6 cycloalkylcarbonyloxy group, a C3-C6 cycloalkyloxycarbonyloxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfonyl ... a rufinyl group, a C1-C6 haloalkylsulfonyl group, a C3-C6 cycloalkylthio group, a C3-C6 cycloalkylsulfinyl group, a C3-C6 cycloalkylsulfonyl group, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl group moieties in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-membered ring, a 4-membered ring, a 5-membered ring or a 6-membered ring), an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, an aryloxy group which may be mono- or poly-substituted with W, a heterocyclic oxy group which may be mono- or poly-substituted with W, a benzoyl group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group;
U represents a hydroxyl group, a cyano group, a C1-C6 alkoxy group, or an aryloxy group which may be mono- or polysubstituted by W;
K represents a C1-C6 alkyl group or a C1-C6 alkoxy group;
W is a hydroxyl group, a formyl group, a cyano group, a nitro group, a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted with T, a C1-C6 haloalkyl group, a C1-C6 alkoxy group which may be mono- or poly-substituted with C1-C6 alkoxy groups, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C3-C6 cycloalkylC1-C6 alkoxy group, a C1-C6 a an alkylsulfonyloxy group, a C3-C6 cycloalkylsulfonyloxy group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5- or 6-membered ring); an aryl group which may be mono- or poly-substituted by V, a heterocyclic group which may be mono- or poly-substituted by V, an aryloxy group which may be mono- or poly-substituted by V, a C7-C11 aralkyl group which may be mono- or poly-substituted by V, or a C7-C11 aralkyloxy group which may be mono- or poly-substituted by V,
T represents a hydroxyl group, a cyano group, a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a hydroxyimino group, a C1-C6 alkoxyimino group, or an aryl group which may be mono- or poly-substituted by V;
V represents a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, or a C3-C6 cycloalkyl group;
Z represents an oxygen atom, a sulfur atom, -SO-, -SO ₂ -, -CH ₂ -, or -CF ₂ -;
n represents 0 or 1;
A ¹ represents a nitrogen atom or CH;
^A2 represents a nitrogen atom or CH;
^A3 represents a nitrogen atom or CH.
However, this does not include the case where A ¹ is a nitrogen atom, A ² is CH, and A ³ is a nitrogen atom.
or a salt thereof.

[2]
In the general formula (1),
The bicyclic pyridine derivative or salt thereof according to claim 1, wherein R ¹ is a halogen atom, a C1-C6 alkyl group optionally mono- or poly-substituted with U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5- or 6-membered ring), an aryl group optionally mono- or poly-substituted with W, a heterocyclic group optionally mono- or poly-substituted with W, a C7-C11 aralkyl group optionally mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group.

[3]
In the general formula (1),
R ¹ is a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted by U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl alkyl portions in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5-, or 6-membered ring), an aryl group which may be mono- or poly-substituted by W, a heterocyclic group which may be mono- or poly-substituted by W, a C7-C11 aralkyl group which may be mono- or poly-substituted by W, or a C3-C6 cycloalkyl C1-C6 alkyl group;
^A1 is CH;
The bicyclic pyridine derivative or a salt thereof according to claim 1, wherein ^A3 is a nitrogen atom.

[4]
In the general formula (1),
R ² is a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylthio group, a C1-C6 haloalkylthio group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5- or 6-membered ring), W The bicyclic pyridine derivative or a salt thereof according to [1], which is an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, an aryloxy group which may be mono- or poly-substituted with W, a heterocyclic oxy group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group.

[5]
In the general formula (1),
R ² is a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylthio group, a C1-C6 haloalkylthio group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups are bonded to each other via alkylene groups to form a 3-membered ring, a 4-membered ring, a 5-membered ring, or a 6-membered ring). ), an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, an aryloxy group which may be mono- or poly-substituted with W, a heterocyclic oxy group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group;
^A1 is CH;
The bicyclic pyridine derivative or a salt thereof according to [1], wherein ^A3 is a nitrogen atom.

[6]
An agricultural or horticultural agent comprising the bicyclic pyridine derivative or a salt thereof according to any one of [1] to [5] as an active ingredient.
[7]
An insecticide comprising the bicyclic pyridine derivative or a salt thereof according to any one of [1] to [5] as an active ingredient.
[8]
A miticide comprising the bicyclic pyridine derivative or a salt thereof according to any one of [1] to [5] as an active ingredient.
[9]
A nematicide comprising the bicyclic pyridine derivative or a salt thereof according to any one of [1] to [5] as an active ingredient.
[10]
A fungicide comprising the bicyclic pyridine derivative or a salt thereof according to any one of [1] to [5] as an active ingredient.

[11]
A method for controlling plant pests, comprising the step of treating pests and/or their habitats and/or seeds and/or plants and/or plant propagation materials with the agricultural and horticultural agent according to [6].
[12]
A method for controlling plant pests, comprising a step of treating a place where a useful crop is to be grown or is being grown, or a growing crop, with the agricultural and horticultural agent according to [6].
[13]
A method for preparing an agricultural or horticultural agent, comprising a step of mixing the bicyclic pyridine derivative or a salt thereof according to any one of [1] to [5] with an extender and/or a surfactant.

The novel bicyclic pyridine derivative or its salt of the present invention represented by the above general formula (1) exhibits excellent insecticidal, acaricidal, nematocidal and fungicidal effects.

The following provides a detailed explanation of the bicyclic pyridine derivatives or salts thereof related to the compounds of the present invention, their production methods, and pest control agents containing them as active ingredients.

[Bicyclic pyridine derivative represented by general formula (1) or a salt thereof]
The bicyclic pyridine derivative or a salt thereof of the present invention is represented by the above general formula (1).
In general formula (1), R ¹ is a hydrogen atom, a hydroxyl group, a formyl group, a hydroxycarbonyl group, a cyano group, a nitro group, a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted by U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkenyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 haloalkoxycarbonyl group, a C3-C6 cyclo a C3-C6 cycloalkylcarbonyl group, a C1-C6 alkylcarbonyloxy group, a C1-C6 haloalkylcarbonyloxy group, a C1-C6 alkoxycarbonyloxy group, a C1-C6 haloalkoxycarbonyloxy group, a C3-C6 cycloalkylcarbonyloxy group, a C3-C6 cycloalkyloxycarbonyloxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, a C1-C6 haloalkylsulfonyl group, a C3-C6 cyclo a cycloalkylthio group, a C3-C6 cycloalkylsulfinyl group, a C3-C6 cycloalkylsulfonyl group, a carbamoyl group which may be mono- or poly-substituted by K, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via an alkylene group to form a 3-, 4-, 5- or 6-membered ring), an aryl group which may be mono- or poly-substituted by W, a heterocyclic group which may be mono- or poly-substituted by W, a monocyclic group which may be mono- or poly-substituted by W, a monocyclic group which may be mono- or poly-substituted by W, a di-C1-C6 alkylamino ... a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a C7-C11 aralkyloxy group which may be mono- or poly-substituted with W, a C7-C11 aralkylthio group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group.

Examples of the halogen atom represented by R ¹ include fluorine, chlorine, bromine and iodine.

The C1-C6 alkyl group moiety of the C1-C6 alkyl group which may be mono- or poly-substituted by U, represented by ^R1 , may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-pentyl group, an isoamyl group, a tert-amyl group, a neopentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methylbutyl group, a tert-pentyl group, a 1-hexyl group, and a 1-ethylpropyl group.

The C1-C6 haloalkyl group represented by ^R1 may be either linear or branched, and examples thereof include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2-chloroethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a 4-fluorobutyl group, a 5-fluoropentyl group, a 6-fluorohexyl group, and a heptafluoroisopropyl group.

The C1-C6 alkoxy group represented by ^R1 may be either linear or branched, and examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a 1-pentyloxy group, an isoamyloxy group, a neopentyloxy group, a 2-pentyloxy group, a 3-pentyloxy group, a 2-methylbutyloxy group, a tert-pentyloxy group, and a 1-hexyloxy group.

The C1-C6 haloalkoxy group represented by ^R1 may be either linear or branched, and examples thereof include a monofluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2-chloroethoxy group, a 1-fluoroethoxy group, a 2-fluoroethoxy group, a 2,2-difluoroethoxy group, a 3-fluoropropoxy group, a 4-fluorobutoxy group, a 4,4,4-trifluorobutoxy group, a 5-fluoropentoxy group, a 6-fluorohexyloxy group, and a heptafluoroisopropyloxy group.

Examples of the C3-C6 cycloalkyl group represented by ^R1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the C3-C6 cycloalkyloxy group represented by R ¹ include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

The C2-C6 alkenyl group represented by ^R1 may be either linear or branched, and examples thereof include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-methyl-2-butenyl group, a 2-methyl-2-butenyl group, a 3-methyl-2-butenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, and a 5-hexenyl group.

The C2-C6 alkynyl group represented by ^R1 may be either linear or branched, and examples thereof include an ethynyl group, a 1-propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-2-propynyl group, a 2-methyl-3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-methyl-2-butynyl group, a 2-methyl-3-pentynyl group, a 1-hexynyl group, a 1,1-dimethyl-2-butynyl group, and a 2-trimethylsilylethynyl group.

Examples of the C3-C6 cycloalkenyl group represented by ^R1 include a 1-cyclopropenyl group, a 2-cyclopropenyl group, a 1-cyclobutenyl group, a 2-cyclobutenyl group, a 1-cyclopentenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, a 3-cyclohexenyl group, a 1-cycloheptenyl group, a 2-cycloheptenyl group, a 3-cycloheptenyl group, and a 4-cycloheptenyl group.

The C1-C6 alkylcarbonyl group represented by ^R1 may be either linear or branched, and examples thereof include an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an isopropylcarbonyl group, an n-butylcarbonyl group, an isobutylcarbonyl group, a sec-butylcarbonyl group, a tert-butylcarbonyl group, a 1-pentylcarbonyl group, and a 1-hexylcarbonyl group.

The C1-C6 haloalkylcarbonyl group represented by R ¹ may be either linear or branched, and examples thereof include a monofluoromethylcarbonyl group, a difluoromethylcarbonyl group, a trifluoromethylcarbonyl group, a 2,2,2-trifluoroethylcarbonyl group, a 2-chloroethylcarbonyl group, a 1-fluoroethylcarbonyl group, a 2-fluoroethylcarbonyl group, a 3-fluoropropylcarbonyl group, a 4-fluorobutylcarbonyl group, a 5-fluoropentylcarbonyl group, a 6-fluorohexylcarbonyl group, and a heptafluoroisopropylcarbonyl group.

The C1-C6 alkoxycarbonyl group represented by R ¹ may be either linear or branched, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, a tert-butyloxycarbonyl group, a 1-pentyloxycarbonyl group, an isoamyloxycarbonyl group, a neopentyloxycarbonyl group, a 2-pentyloxycarbonyl group, a 3-pentyloxycarbonyl group, a 2-methylbutyloxycarbonyl group, a tert-pentyloxycarbonyl group, and an n-hexyloxycarbonyl group.

The C1-C6 haloalkoxycarbonyl group represented by R ¹ may be either linear or branched, and examples thereof include a monofluoromethoxycarbonyl group, a difluoromethoxycarbonyl group, a trifluoromethoxycarbonyl group, a 2,2,2-trifluoroethoxycarbonyl group, a 2-chloroethoxycarbonyl group, a 1-fluoroethoxycarbonyl group, a 2-fluoroethoxycarbonyl group, a 3-fluoropropoxycarbonyl group, a 4-fluorobutoxycarbonyl group, a 5-fluoropentoxycarbonyl group, a 6-fluorohexyloxycarbonyl group, and a heptafluoroisopropyloxycarbonyl group.

Examples of the C3-C6 cycloalkylcarbonyl group represented by R ¹ include a cyclopropylcarbonyl group, a cyclobutylcarbonyl group, a cyclopentylcarbonyl group, and a cyclohexylcarbonyl group.

Examples of the C3-C6 cycloalkyloxycarbonyl group represented by R ¹ include a cyclopropyloxycarbonyl group, a cyclobutyloxycarbonyl group, a cyclopentyloxycarbonyl group, and a cyclohexyloxycarbonyl group.

The C1-C6 alkylcarbonyloxy group represented by ^R1 may be either linear or branched, and examples thereof include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a 1-pentylcarbonyloxy group, and a 1-hexylcarbonyloxy group.

The C1-C6 haloalkylcarbonyloxy group represented by R ¹ may be either linear or branched, and examples thereof include a monofluoromethylcarbonyloxy group, a difluoromethylcarbonyloxy group, a trifluoromethylcarbonyloxy group, a 2,2,2-trifluoroethylcarbonyloxy group, a 2-chloroethylcarbonyloxy group, a 1-fluoroethylcarbonyloxy group, a 2-fluoroethylcarbonyloxy group, a 3-fluoropropylcarbonyloxy group, a 4-fluorobutylcarbonyloxy group, a 5-fluoropentylcarbonyloxy group, a 6-fluorohexylcarbonyloxy group, and a heptafluoroisopropylcarbonyloxy group.

The C1-C6 alkoxycarbonyloxy group represented by R ¹ may be either linear or branched, and examples thereof include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propyloxycarbonyloxy group, an isopropyloxycarbonyloxy group, an n-butyloxycarbonyloxy group, an isobutyloxycarbonyloxy group, a sec-butyloxycarbonyloxy group, a tert-butyloxycarbonyloxy group, a 1-pentyloxycarbonyloxy group, an isoamyloxycarbonyloxy group, a neopentyloxycarbonyloxy group, a 2-pentyloxycarbonyloxy group, a 3-pentyloxycarbonyloxy group, a 2-methylbutyloxycarbonyloxy group, a tert-pentyloxycarbonyloxy group, an n-hexyloxycarbonyloxy group, and the like.

The C1-C6 haloalkoxycarbonyloxy group represented by R ¹ may be either linear or branched, and examples thereof include a monofluoromethoxycarbonyloxy group, a difluoromethoxycarbonyloxy group, a trifluoromethoxycarbonyloxy group, a 2,2,2-trifluoroethoxycarbonyloxy group, a 2-chloroethoxycarbonyloxy group, a 1-fluoroethoxycarbonyloxy group, a 2-fluoroethoxycarbonyloxy group, a 3-fluoropropoxycarbonyloxy group, a 4-fluorobutoxycarbonyloxy group, a 5-fluoropentoxycarbonyloxy group, a 6-fluorohexyloxycarbonyloxy group, and a heptafluoroisopropyloxycarbonyloxy group.

Examples of the C3-C6 cycloalkylcarbonyloxy group represented by R ¹ include a cyclopropylcarbonyloxy group, a cyclobutylcarbonyloxy group, a cyclopentylcarbonyloxy group, and a cyclohexylcarbonyloxy group.

Examples of the C3-C6 cycloalkyloxycarbonyloxy group represented by R ¹ include a cyclopropyloxycarbonyloxy group, a cyclobutyloxycarbonyloxy group, a cyclopentyloxycarbonyloxy group, and a cyclohexyloxycarbonyloxy group.

The C1-C6 alkylthio group represented by ^R1 may be either linear or branched, and examples thereof include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a 1-pentylthio group, an isoamylthio group, a neopentylthio group, a 2-pentylthio group, a 3-pentylthio group, a 2-methylbutylthio group, a tert-pentylthio group, and a 1-hexylthio group.

The C1-C6 alkylsulfinyl group represented by R ¹ may be either linear or branched, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, an n-propylsulfinyl group, an isopropylsulfinyl group, an n-butylsulfinyl group, an isobutylsulfinyl group, a sec-butylsulfinyl group, a tert-butylsulfinyl group, a 1-pentylsulfinyl group, an isoamylsulfinyl group, a neopentylsulfinyl group, a 2-pentylsulfinyl group, a 3-pentylsulfinyl group, a 2-methylbutylsulfinyl group, a tert-pentylsulfinyl group, a 1-hexylsulfinyl group, and the like.

The C1-C6 alkylsulfonyl group represented by R ¹ may be either linear or branched, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an isopropylsulfonyl group, an n-butylsulfonyl group, an isobutylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonyl group, a 1-pentylsulfonyl group, an isoamylsulfonyl group, a neopentylsulfonyl group, a 2-pentylsulfonyl group, a 3-pentylsulfonyl group, a 2-methylbutylsulfonyl group, a tert-pentylsulfonyl group, and a 1-hexylsulfonyl group.

The C1-C6 haloalkylthio group represented by ^R1 may be either linear or branched, and examples thereof include a monofluoromethylthio group, a difluoromethylthio group, a trifluoromethylthio group, a 2,2,2-trifluoroethylthio group, a 2-chloroethylthio group, a 1-fluoroethylthio group, a 2-fluoroethylthio group, a 3-fluoropropylthio group, a 4-fluorobutylthio group, a 5-fluoropentylthio group, a 6-fluorohexylthio group, and a heptafluoroisopropylthio group.

The C1-C6 haloalkylsulfinyl group represented by R ¹ may be either linear or branched, and examples thereof include a monofluoromethylsulfinyl group, a difluoromethylsulfinyl group, a trifluoromethylsulfinyl group, a 2,2,2-trifluoroethylsulfinyl group, a 2-chloroethylsulfinyl group, a 1-fluoroethylsulfinyl group, a 2-fluoroethylsulfinyl group, a 3-fluoropropylsulfinyl group, a 4-fluorobutylsulfinyl group, a 5-fluoropentylsulfinyl group, a 6-fluorohexylsulfinyl group, and a heptafluoroisopropylsulfinyl group.

The C1-C6 haloalkylsulfonyl group represented by R ¹ may be either linear or branched, and examples thereof include a monofluoromethylsulfonyl group, a difluoromethylsulfonyl group, a trifluoromethylsulfonyl group, a 2,2,2-trifluoroethylsulfonyl group, a 2-chloroethylsulfonyl group, a 1-fluoroethylsulfonyl group, a 2-fluoroethylsulfonyl group, a 3-fluoropropylsulfonyl group, a 4-fluorobutylsulfonyl group, a 5-fluoropentylsulfonyl group, a 6-fluorohexylsulfonyl group, and a heptafluoroisopropylsulfonyl group.

Examples of the C3-C6 cycloalkylthio group represented by ^R1 include a cyclopropylthio group, a cyclobutylthio group, a cyclopentylthio group, and a cyclohexylthio group.

Examples of the C3-C6 cycloalkylsulfinyl group represented by R ¹ include a cyclopropylsulfinyl group, a cyclobutylsulfinyl group, a cyclopentylsulfinyl group, and a cyclohexylsulfinyl group.

Examples of the C3-C6 cycloalkylsulfonyl group represented by R ¹ include a cyclopropylsulfonyl group, a cyclobutylsulfonyl group, a cyclopentylsulfonyl group, and a cyclohexylsulfonyl group.

The C1-C6 alkylamino group represented by ^R1 may be either linear or branched, and examples thereof include a methylamino group, an ethylamino group, an n-propylamino group, an isopropylamino group, an n-butylamino group, an isobutylamino group, a sec-butylamino group, a tert-butylamino group, a 1-pentylamino group, an isoamylamino group, a neopentylamino group, a 2-pentylamino group, a 3-pentylamino group, a 2-methylbutylamino group, a tert-pentylamino group, and a 1-hexylamino group.

The di-C1-C6 alkylamino group represented by ^R1 may be either linear or branched, and examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a di-sec-butylamino group, a di-tert-butylamino group, a di-1-pentylamino group, a diisoamylamino group, a dineopentylamino group, a di-2-pentylamino group, a di-3-pentylamino group, a di-2-methylbutylamino group, a di-tert-pentylamino group, a di-1-hexylamino group, a methylethylamino group, a methyl-n-propylamino group, and an ethyl-n-propylamino group.
The C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups can be linked to each other through alkylene groups to form 3-, 4-, 5- and 6-membered rings.

The aryl group portion of the aryl group which may be mono- or poly-substituted by W, represented by ^R1 , represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

The heterocyclic group moiety of the heterocyclic group which may be mono- or poly-substituted by W, represented by ^R1 , indicates a monocyclic or polycyclic ring group, and examples thereof include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, a 2-furanyl group, a 3-furanyl group, a 2-thienyl group, a 3-thienyl group, a 1-tetrahydrofuranyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, a 3-tetrahydropyranyl group, a 4-tetrahydropyranyl group, a 2-(1,3-dioxolanyl) group, a 2-(1,3-dioxanyl) group, a 2-quinolyl group, a 1-isoquinolyl group, and a 5-(1,3-benzodioxole) group.

The aryloxy group moiety of the aryloxy group which may be mono- or poly-substituted by W, represented by ^R1 , represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenoxy group, a 1-naphthoxy group, and a 2-naphthoxy group.

The heterocyclic oxy group moiety of the heterocyclic oxy group which may be mono- or poly-substituted by W, represented by ^R1 , indicates a monocyclic or polycyclic oxy group, and examples thereof include a 2-pyridyloxy group, a 3-pyridyloxy group, a 4-pyridyloxy group, a 2-furanyloxy group, a 3-furanyloxy group, a 2-thienyloxy group, a 3-thienyloxy group, a 1-tetrahydrofuranyloxy group, a 2-tetrahydrofuranyloxy group, a 2-tetrahydropyranyloxy group, a 3-tetrahydropyranyloxy group, a 4-tetrahydropyranyloxy group, a 2-(1,3-dioxolanyl)oxy group, a 2-(1,3-dioxanyl)oxy group, a 2-quinolyloxy group, and a 1-isoquinolyloxy group.

The arylthio group moiety of the arylthio group which may be mono- or poly-substituted by W, represented by ^R1 , represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

Examples of the C7-C11 aralkyl group moiety of the C7-C11 aralkyl group which may be mono- or poly-substituted by W, represented by ^R1 , include a benzyl group, a 1-phenethyl group, a 2-phenethyl group, a 1-phenylpropyl group, a 2-phenylpropyl group, a 3-phenylpropyl group, a 1-phenyl-2-methylpropyl group, a 1-phenylbutyl group, and a 1-phenylpentyl group.

Examples of the C7-C11 aralkyloxy group moiety of the C7-C11 aralkyloxy group which may be mono- or poly-substituted by W, represented by ^R1 , include a benzyloxy group, a 1-phenethyloxy group, a 2-phenethyloxy group, a 1-phenylpropyloxy group, a 2-phenylpropyloxy group, a 3-phenylpropyloxy group, a 1-phenyl-2-methylpropyloxy group, a 1-phenylbutyloxy group, and a 1-phenylpentyloxy group.

Examples of the C7-C11 aralkylthio group moiety of the C7-C11 aralkylthio group which may be mono- or poly-substituted by W, represented by ^R1 , include a benzylthio group, a 1-phenethylthio group, a 2-phenethylthio group, a 1-phenylpropylthio group, a 2-phenylpropylthio group, a 3-phenylpropylthio group, a 1-phenyl-2-methylpropylthio group, a 1-phenylbutylthio group, and a 1-phenylpentylthio group.

The C3-C6 cycloalkyl C1-C6 alkyl group represented by ^R1 may be either linear or branched, and examples thereof include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cyclopropylethyl group, a cyclobutylethyl group, a cyclopentylethyl group, and a cyclohexylethyl group.

In general formula (1), R ² represents a hydrogen atom, a hydroxyl group, a formyl group, a hydroxycarbonyl group, a cyano group, a nitro group, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 haloalkoxycarbonyl group, a C3-C6 cycloal ...3-C6 cycloalkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkoxycarbonyl group, a C3-C6 cycloalkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkoxycarbonyl group, a C3-C6 cycloalkenyl group, a C2-C6 alkynyl group, a C2-C6 alkynyl group, a C2-C6 alkynyl group, a C2-C6 alkynyl group, a C2-C6 alkynyl group, a C2-C6 alkynyl group, a alkylcarbonyl group, a C3-C6 cycloalkyloxycarbonyl group, a C1-C6 alkylcarbonyloxy group, a C1-C6 haloalkylcarbonyloxy group, a C1-C6 alkoxycarbonyloxy group, a C1-C6 haloalkoxycarbonyloxy group, a C3-C6 cycloalkylcarbonyloxy group, a C3-C6 cycloalkyloxycarbonyloxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfonyl ... phenyl group, a C1-C6 haloalkylsulfonyl group, a C3-C6 cycloalkylthio group, a C3-C6 cycloalkylsulfinyl group, a C3-C6 cycloalkylsulfonyl group, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl group portions in the di-C1-C6 alkylamino group may be the same or different, and the groups can be bonded to each other via alkylene groups to form a 3-membered ring, a 4-membered ring, a 5-membered ring or a 6-membered ring), an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, an aryloxy group which may be mono- or poly-substituted with W, a heterocyclic oxy group which may be mono- or poly-substituted with W, a benzoyl group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group.

Examples of the halogen atom represented by ^R2 include fluorine, chlorine, bromine and iodine.

The C1-C6 alkyl group represented by ^R2 may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-pentyl group, an isoamyl group, a tert-amyl group, a neopentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methylbutyl group, a tert-pentyl group, a 1-hexyl group, and a 1-ethylpropyl group.

The C1-C6 haloalkyl group represented by ^R2 may be either linear or branched, and examples thereof include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2-chloroethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a 4-fluorobutyl group, a 5-fluoropentyl group, a 6-fluorohexyl group, and a heptafluoroisopropyl group.

The C1-C6 alkoxy group represented by ^R2 may be either linear or branched, and examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a 1-pentyloxy group, an isoamyloxy group, a neopentyloxy group, a 2-pentyloxy group, a 3-pentyloxy group, a 2-methylbutyloxy group, a tert-pentyloxy group, and a 1-hexyloxy group.

The C1-C6 haloalkoxy group represented by ^R2 may be either linear or branched, and examples thereof include a monofluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2-chloroethoxy group, a 1-fluoroethoxy group, a 2-fluoroethoxy group, a 2,2-difluoroethoxy group, a 3-fluoropropoxy group, a 4-fluorobutoxy group, a 4,4,4-trifluorobutoxy group, a 5-fluoropentoxy group, a 6-fluorohexyloxy group, and a heptafluoroisopropyloxy group.

Examples of the C3-C6 cycloalkyl group represented by ^R2 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the C3-C6 cycloalkyloxy group represented by ^R2 include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

The C2-C6 alkenyl group represented by ^R2 may be either linear or branched, and examples thereof include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and 5-hexenyl groups.

The C2-C6 alkynyl group represented by ^R2 may be either linear or branched, and examples thereof include an ethynyl group, a 1-propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-2-propynyl group, a 2-methyl-3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-methyl-2-butynyl group, a 2-methyl-3-pentynyl group, a 1-hexynyl group, and a 1,1-dimethyl-2-butynyl group.

The C1-C6 alkylcarbonyl group represented by ^R2 may be either linear or branched, and examples thereof include an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an isopropylcarbonyl group, an n-butylcarbonyl group, an isobutylcarbonyl group, a sec-butylcarbonyl group, a tert-butylcarbonyl group, a 1-pentylcarbonyl group, and a 1-hexylcarbonyl group.

The C1-C6 haloalkylcarbonyl group represented by ^R2 may be either linear or branched, and examples thereof include a monofluoromethylcarbonyl group, a difluoromethylcarbonyl group, a trifluoromethylcarbonyl group, a 2,2,2-trifluoroethylcarbonyl group, a 2-chloroethylcarbonyl group, a 1-fluoroethylcarbonyl group, a 2-fluoroethylcarbonyl group, a 3-fluoropropylcarbonyl group, a 4-fluorobutylcarbonyl group, a 5-fluoropentylcarbonyl group, a 6-fluorohexylcarbonyl group, and a heptafluoroisopropylcarbonyl group.

The C1-C6 alkoxycarbonyl group represented by ^R2 may be either linear or branched, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, a tert-butyloxycarbonyl group, a 1-pentyloxycarbonyl group, an isoamyloxycarbonyl group, a neopentyloxycarbonyl group, a 2-pentyloxycarbonyl group, a 3-pentyloxycarbonyl group, a 2-methylbutyloxycarbonyl group, a tert-pentyloxycarbonyl group, and an n-hexyloxycarbonyl group.

The C1-C6 haloalkoxycarbonyl group represented by ^R2 may be either linear or branched, and examples thereof include a monofluoromethoxycarbonyl group, a difluoromethoxycarbonyl group, a trifluoromethoxycarbonyl group, a 2,2,2-trifluoroethoxycarbonyl group, a 2-chloroethoxycarbonyl group, a 1-fluoroethoxycarbonyl group, a 2-fluoroethoxycarbonyl group, a 3-fluoropropoxycarbonyl group, a 4-fluorobutoxycarbonyl group, a 5-fluoropentoxycarbonyl group, a 6-fluorohexyloxycarbonyl group, and a heptafluoroisopropyloxycarbonyl group.

Examples of the C3-C6 cycloalkylcarbonyl group represented by ^R2 include a cyclopropylcarbonyl group, a cyclobutylcarbonyl group, a cyclopentylcarbonyl group, and a cyclohexylcarbonyl group.

Examples of the C3-C6 cycloalkyloxycarbonyl group represented by ^R2 include a cyclopropyloxycarbonyl group, a cyclobutyloxycarbonyl group, a cyclopentyloxycarbonyl group, and a cyclohexyloxycarbonyl group.

The C1-C6 alkylcarbonyloxy group represented by ^R2 may be either linear or branched, and examples thereof include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a 1-pentylcarbonyloxy group, and a 1-hexylcarbonyloxy group.

The C1-C6 haloalkylcarbonyloxy group represented by ^R2 may be either linear or branched, and examples thereof include a monofluoromethylcarbonyloxy group, a difluoromethylcarbonyloxy group, a trifluoromethylcarbonyloxy group, a 2,2,2-trifluoroethylcarbonyloxy group, a 2-chloroethylcarbonyloxy group, a 1-fluoroethylcarbonyloxy group, a 2-fluoroethylcarbonyloxy group, a 3-fluoropropylcarbonyloxy group, a 4-fluorobutylcarbonyloxy group, a 5-fluoropentylcarbonyloxy group, a 6-fluorohexylcarbonyloxy group, and a heptafluoroisopropylcarbonyloxy group.

The C1-C6 alkoxycarbonyloxy group represented by ^R2 may be either linear or branched, and examples thereof include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propyloxycarbonyloxy group, an isopropyloxycarbonyloxy group, an n-butyloxycarbonyloxy group, an isobutyloxycarbonyloxy group, a sec-butyloxycarbonyloxy group, a tert-butyloxycarbonyloxy group, a 1-pentyloxycarbonyloxy group, an isoamyloxycarbonyloxy group, a neopentyloxycarbonyloxy group, a 2-pentyloxycarbonyloxy group, a 3-pentyloxycarbonyloxy group, a 2-methylbutyloxycarbonyloxy group, a tert-pentyloxycarbonyloxy group, an n-hexyloxycarbonyloxy group, and the like.

The C1-C6 haloalkoxycarbonyloxy group represented by ^R2 may be either linear or branched, and examples thereof include a monofluoromethoxycarbonyloxy group, a difluoromethoxycarbonyloxy group, a trifluoromethoxycarbonyloxy group, a 2,2,2-trifluoroethoxycarbonyloxy group, a 2-chloroethoxycarbonyloxy group, a 1-fluoroethoxycarbonyloxy group, a 2-fluoroethoxycarbonyloxy group, a 3-fluoropropoxycarbonyloxy group, a 4-fluorobutoxycarbonyloxy group, a 5-fluoropentoxycarbonyloxy group, a 6-fluorohexyloxycarbonyloxy group, and a heptafluoroisopropyloxycarbonyloxy group.

Examples of the C3-C6 cycloalkylcarbonyloxy group represented by ^R2 include a cyclopropylcarbonyloxy group, a cyclobutylcarbonyloxy group, a cyclopentylcarbonyloxy group, and a cyclohexylcarbonyloxy group.

Examples of the C3-C6 cycloalkyloxycarbonyloxy group represented by ^R2 include a cyclopropyloxycarbonyloxy group, a cyclobutyloxycarbonyloxy group, a cyclopentyloxycarbonyloxy group, and a cyclohexyloxycarbonyloxy group.

The C1-C6 alkylthio group represented by ^R2 may be either linear or branched, and examples thereof include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a 1-pentylthio group, an isoamylthio group, a neopentylthio group, a 2-pentylthio group, a 3-pentylthio group, a 2-methylbutylthio group, a tert-pentylthio group, and a 1-hexylthio group.

The C1-C6 alkylsulfinyl group represented by ^R2 may be either linear or branched, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, an n-propylsulfinyl group, an isopropylsulfinyl group, an n-butylsulfinyl group, an isobutylsulfinyl group, a sec-butylsulfinyl group, a tert-butylsulfinyl group, a 1-pentylsulfinyl group, an isoamylsulfinyl group, a neopentylsulfinyl group, a 2-pentylsulfinyl group, a 3-pentylsulfinyl group, a 2-methylbutylsulfinyl group, a tert-pentylsulfinyl group, a 1-hexylsulfinyl group and the like.

The C1-C6 alkylsulfonyl group represented by ^R2 may be either linear or branched, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an isopropylsulfonyl group, an n-butylsulfonyl group, an isobutylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonyl group, a 1-pentylsulfonyl group, an isoamylsulfonyl group, a neopentylsulfonyl group, a 2-pentylsulfonyl group, a 3-pentylsulfonyl group, a 2-methylbutylsulfonyl group, a tert-pentylsulfonyl group, and a 1-hexylsulfonyl group.

The C1-C6 haloalkylthio group represented by ^R2 may be either linear or branched, and examples thereof include a monofluoromethylthio group, a difluoromethylthio group, a trifluoromethylthio group, a 2,2,2-trifluoroethylthio group, a 2-chloroethylthio group, a 1-fluoroethylthio group, a 2-fluoroethylthio group, a 3-fluoropropylthio group, a 4-fluorobutylthio group, a 5-fluoropentylthio group, a 6-fluorohexylthio group, and a heptafluoroisopropylthio group.

The C1-C6 haloalkylsulfinyl group represented by ^R2 may be either linear or branched, and examples thereof include a monofluoromethylsulfinyl group, a difluoromethylsulfinyl group, a trifluoromethylsulfinyl group, a 2,2,2-trifluoroethylsulfinyl group, a 2-chloroethylsulfinyl group, a 1-fluoroethylsulfinyl group, a 2-fluoroethylsulfinyl group, a 3-fluoropropylsulfinyl group, a 4-fluorobutylsulfinyl group, a 5-fluoropentylsulfinyl group, a 6-fluorohexylsulfinyl group, and a heptafluoroisopropylsulfinyl group.

The C1-C6 haloalkylsulfonyl group represented by ^R2 may be either linear or branched, and examples thereof include a monofluoromethylsulfonyl group, a difluoromethylsulfonyl group, a trifluoromethylsulfonyl group, a 2,2,2-trifluoroethylsulfonyl group, a 2-chloroethylsulfonyl group, a 1-fluoroethylsulfonyl group, a 2-fluoroethylsulfonyl group, a 3-fluoropropylsulfonyl group, a 4-fluorobutylsulfonyl group, a 5-fluoropentylsulfonyl group, a 6-fluorohexylsulfonyl group, and a heptafluoroisopropylsulfonyl group.

Examples of the C3-C6 cycloalkylthio group represented by ^R2 include a cyclopropylthio group, a cyclobutylthio group, a cyclopentylthio group, and a cyclohexylthio group.

Examples of the C3-C6 cycloalkylsulfinyl group represented by ^R2 include a cyclopropylsulfinyl group, a cyclobutylsulfinyl group, a cyclopentylsulfinyl group, and a cyclohexylsulfinyl group.

Examples of the C3-C6 cycloalkylsulfonyl group represented by ^R2 include a cyclopropylsulfonyl group, a cyclobutylsulfonyl group, a cyclopentylsulfonyl group, and a cyclohexylsulfonyl group.

The C1-C6 alkylamino group represented by ^R2 may be either linear or branched, and examples thereof include a methylamino group, an ethylamino group, an n-propylamino group, an isopropylamino group, an n-butylamino group, an isobutylamino group, a sec-butylamino group, a tert-butylamino group, a 1-pentylamino group, an isoamylamino group, a neopentylamino group, a 2-pentylamino group, a 3-pentylamino group, a 2-methylbutylamino group, a tert-pentylamino group, and a 1-hexylamino group.

The di-C1-C6 alkylamino group represented by ^R2 may be either linear or branched, and examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a disec-butylamino group, a di-tert-butylamino group, a di-1-pentylamino group, a diisoamylamino group, a dineopentylamino group, a di-2-pentylamino group, a di-3-pentylamino group, a di-2-methylbutylamino group, a di-tert-pentylamino group, a di-1-hexylamino group, a methylethylamino group, a methyl-n-propylamino group, and an ethyl-n-propylamino group.
The C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups can be linked to each other through alkylene groups to form 3-, 4-, 5- and 6-membered rings.

The aryl group portion of the aryl group which may be mono- or poly-substituted by W, represented by ^R2 , represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

The heterocyclic group moiety of the heterocyclic group which may be mono- or poly-substituted by W, represented by ^R2 , represents a monocyclic or polycyclic ring group, and may be a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, a 2-furanyl group, a 3-furanyl group, a 2-thienyl group, a 3-thienyl group, a 1-tetrahydrofuranyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, a 3-tetrahydropyranyl group, a 4-tetrahydropyranyl group, a 5-tetrahydropyranyl group, a 6-tetrahydropyranyl group, a 7-tetrahydropyranyl group, a 8-tetrahydropyranyl group, a 9-tetrahydropyranyl group, a 10-tetrahydropyranyl group, a 11-tetrahydropyranyl group, a 12-tetrahydropyranyl group, a 13-tetrahydropyranyl group, a 14-tetrahydropyranyl group, a 15-tetrahydropyranyl group, a 16-tetrahydropyranyl group, a 17-tetrahydropyranyl group, a 18-tetrahydropyranyl group, a 21-tetrahydropyranyl group, a 22-tetrahydropyranyl group, a 23-tetrahydropyranyl group, a 24-tetrahydropyranyl group, a 25-tetrahydropyranyl group, a 26-tetrahydropyranyl group, a 27-tetrahydropyranyl group, a 28-tetrahydropyranyl group, a 29-tetrahydropyranyl group, a 21-tetrahydropyranyl group, a 22-tetrahydropyranyl group, a 23-tetrahydropyranyl group, a 24-tetrahydropyranyl group, a 25-tetrahydropyranyl group, a 26-tetrahydropyranyl Examples of the alkyl group include a tetrahydropyranyl group, a 2-(1,3-dioxolanyl) group, a 2-(1,3-dioxanyl) group, a 2-quinolyl group, a 1-isoquinolyl group, a 5-(1,3-benzodioxole) group, a 2-(1,3,4-thiadiazole) group, a 5-tetrazolyl group, a 2-(1,3-benzothiazolyl) group, a 4-piperidinyl group, a 3-(1,2,4-triazole) group, and a 2-(1,3,4-thiadiazole) group.

The aryloxy group portion of the aryloxy group which may be mono- or poly-substituted by W, represented by ^R2 , represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenoxy group, a 1-naphthoxy group, and a 2-naphthoxy group.

The heterocyclic oxy group portion of the heterocyclic oxy group which may be mono- or poly-substituted by W, represented by ^R2 , represents a monocyclic or polycyclic oxy group, and examples thereof include a 2-pyridyloxy group, a 3-pyridyloxy group, a 4-pyridyloxy group, a 2-furanyloxy group, a 3-furanyloxy group, a 2-thienyloxy group, a 3-thienyloxy group, a 1-tetrahydrofuranyloxy group, a 2-tetrahydrofuranyloxy group, a 2-tetrahydropyranyloxy group, a 3-tetrahydropyranyloxy group, a 4-tetrahydropyranyloxy group, a 2-(1,3-dioxolanyl)oxy group, a 2-(1,3-dioxanyl)oxy group, a 2-quinolyloxy group, and a 1-isoquinolyloxy group.

Examples of the C7-C11 aralkyl group moiety of the C7-C11 aralkyl group which may be mono- or poly-substituted by W, represented by ^R2 , include a benzyl group, a 1-phenethyl group, a 2-phenethyl group, a 1-phenylpropyl group, a 2-phenylpropyl group, a 3-phenylpropyl group, a 1-phenyl-2-methylpropyl group, a 1-phenylbutyl group, and a 1-phenylpentyl group.

Examples of the heterocyclic C1-C6 alkyl group moiety of the heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted by W, represented by ^R2 , include a 2-pyridylmethyl group, a 3-pyridylmethyl group, a 4-pyridylmethyl group, a 2-thienylmethyl group, a 3-thienylmethyl group, a 2-furfuryl group, a 3-furfuryl group, a 2-pyrimidylmethyl group, a 4-pyrimidylmethyl group, a 5-pyrimidylmethyl group, a 6-pyrimidylmethyl group, a 2-tetrahydrofurfuryl group, a 3-tetrahydrofurfuryl group, and the like.

The C3-C6 cycloalkyl C1-C6 alkyl group represented by ^R2 may be either linear or branched, and examples thereof include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cyclopropylethyl group, a cyclobutylethyl group, a cyclopentylethyl group, and a cyclohexylethyl group.

K represents a C1-C6 alkyl group or a C1-C6 alkoxy group.

The C1-C6 alkyl group represented by K in this specification may be either linear or branched, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 1-pentyl, isoamyl, tert-amyl, neopentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, tert-pentyl, 1-hexyl, and 1-ethylpropyl groups.

The C1-C6 alkoxy group represented by K may be either linear or branched, and examples include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, 1-pentyloxy, isoamyloxy, neopentyloxy, 2-pentyloxy, 3-pentyloxy, 2-methylbutyloxy, tert-pentyloxy, and 1-hexyloxy.

U represents a hydroxyl group, a cyano group, a C1-C6 alkoxy group, or an aryloxy group which may be mono- or poly-substituted with W.

The C1-C6 alkoxy group represented by U in this specification may be either linear or branched, and examples include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, 1-pentyloxy, isoamyloxy, neopentyloxy, 2-pentyloxy, 3-pentyloxy, 2-methylbutyloxy, tert-pentyloxy, and 1-hexyloxy.

The aryloxy group portion of the aryloxy group represented by U, which may be mono- or poly-substituted with W, represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenoxy group, a 1-naphthoxy group, and a 2-naphthoxy group.

W is a hydroxyl group, a formyl group, a cyano group, a nitro group, a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted with T, a C1-C6 haloalkyl group, a C1-C6 alkoxy group which may be mono- or poly-substituted with C1-C6 alkoxy groups, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C3-C6 cycloalkyl C1-C6 alkoxy group, a C1-C6 It indicates an alkylsulfonyloxy group, a C3-C6 cycloalkylsulfonyloxy group, a diC1-C6 alkylamino group (the C1-C6 alkyl groups in the diC1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5-, or 6-membered ring), an aryl group which may be mono- or poly-substituted with V, a heterocyclic group which may be mono- or poly-substituted with V, an aryloxy group which may be mono- or poly-substituted with V, a C7-C11 aralkyl group which may be mono- or poly-substituted with V, or a C7-C11 aralkyloxy group which may be mono- or poly-substituted.

In this specification, examples of halogen atoms represented by W include fluorine, chlorine, bromine, and iodine.

The C1-C6 alkyl group portion of the C1-C6 alkyl group represented by W, which may be mono- or poly-substituted with T, may be either linear or branched, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 1-pentyl, isoamyl, neopentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, tert-pentyl, and 1-hexyl groups.

The C1-C6 haloalkyl group represented by W may be either linear or branched, and examples include monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2-chloroethyl, 1-fluoroethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, and heptafluoroisopropyl groups.

The C1-C6 alkoxy group as a substituent and the C1-C6 alkoxy group as a substituted group of the C1-C6 alkoxy group represented by W, which may be mono- or poly-substituted with C1-C6 alkoxy groups, may be either linear or branched, and examples include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, 1-pentyloxy, isoamyloxy, neopentyloxy, 2-pentyloxy, 3-pentyloxy, 2-methylbutyloxy, tert-pentyloxy, and 1-hexyloxy.

The C1-C6 haloalkoxy group represented by W may be either linear or branched, and examples include monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 4-fluorobutoxy, 5-fluoropentoxy, 6-fluorohexyloxy, and heptafluoroisopropyloxy.

Examples of the C3-C6 cycloalkyl group represented by W include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the C3-C6 cycloalkyloxy group represented by W include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

The C2-C6 alkenyl group represented by W may be either linear or branched, and examples include vinyl, isopropenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and 5-hexenyl.

The C2-C6 alkynyl group represented by W may be either linear or branched, and examples include ethynyl, 1-propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 2-methyl-3-pentynyl, 1-hexynyl, 1,1-dimethyl-2-butynyl, and 2-trimethylsilylethynyl.

The C1-C6 alkylcarbonyl group represented by W may be either linear or branched, and examples include acetyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, 1-pentylcarbonyl, and 1-hexylcarbonyl.

The C1-C6 alkoxycarbonyl group represented by W may be either linear or branched, and examples include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, 1-pentyloxycarbonyl, isoamyloxycarbonyl, neopentyloxycarbonyl, 2-pentyloxycarbonyl, 3-pentyloxycarbonyl, 2-methylbutyloxycarbonyl, tert-pentyloxycarbonyl, and n-hexyloxycarbonyl.

The C1-C6 alkylthio group represented by W may be either linear or branched, and examples include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, 1-pentylthio, isoamylthio, neopentylthio, 2-pentylthio, 3-pentylthio, 2-methylbutylthio, tert-pentylthio, and 1-hexylthio.

The C1-C6 alkylsulfinyl group represented by W may be either linear or branched, and examples include methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, 1-pentylsulfinyl, isoamylsulfinyl, neopentylsulfinyl, 2-pentylsulfinyl, 3-pentylsulfinyl, 2-methylbutylsulfinyl, tert-pentylsulfinyl, and 1-hexylsulfinyl.

The C1-C6 alkylsulfonyl group represented by W may be either linear or branched, and examples include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, 1-pentylsulfonyl, isoamylsulfonyl, neopentylsulfonyl, 2-pentylsulfonyl, 3-pentylsulfonyl, 2-methylbutylsulfonyl, tert-pentylsulfonyl, and 1-hexylsulfonyl.

The C1-C6 haloalkylthio group represented by W may be either linear or branched, and examples include a monofluoromethylthio group, a difluoromethylthio group, a trifluoromethylthio group, a 2,2,2-trifluoroethylthio group, a 2-chloroethylthio group, a 1-fluoroethylthio group, a 2-fluoroethylthio group, a 3-fluoropropylthio group, a 4-fluorobutylthio group, a 5-fluoropentylthio group, a 6-fluorohexylthio group, and a heptafluoroisopropylthio group.

The C3-C6 cycloalkyl C1-C6 alkoxy group represented by W may be either linear or branched, and examples include cyclopropyl methoxy, cyclobutyl methoxy, cyclopentyl methoxy, cyclohexyl methoxy, cyclopropyl ethoxy, cyclobutyl ethoxy, cyclopentyl ethoxy, and cyclohexyl ethoxy.

The C1-C6 alkylsulfonyloxy group represented by W may be either linear or branched, and examples include methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, isopropylsulfonyloxy, n-butylsulfonyloxy, isobutylsulfonyloxy, sec-butylsulfonyloxy, tert-butylsulfonyloxy, 1-pentylsulfonyloxy, isoamylsulfonyloxy, tert-amylsulfonyloxy, neopentylsulfonyloxy, 2-pentylsulfonyloxy, 3-pentylsulfonyloxy, 2-methylbutylsulfonyloxy, tert-pentylsulfonyloxy, and 1-hexylsulfonyloxy.

Examples of the C3-C6 cycloalkylsulfonyloxy group represented by W include a cyclopropylsulfonyloxy group, a cyclobutylsulfonyloxy group, a cyclopentylsulfonyloxy group, and a cyclohexylsulfonyloxy group.

The di-C1-C6 alkylamino group represented by W may be either linear or branched, and examples thereof include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, di-sec-butylamino, di-tert-butylamino, di-1-pentylamino, diisoamylamino, dineopentylamino, di-2-pentylamino, di-3-pentylamino, di-2-methylbutylamino, di-tert-pentylamino, di-1-hexylamino, methylethylamino, methyl-n-propylamino, and ethyl-n-propylamino. The C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5-, or 6-membered ring.

The aryl group portion of the aryl group represented by W, which may be mono- or poly-substituted by V, represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

The heterocyclic group portion of the heterocyclic group represented by W, which may be mono- or poly-substituted by V, represents a monocyclic or polycyclic ring group, and includes a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, a 2-furanyl group, a 3-furanyl group, a 2-thienyl group, a 3-thienyl group, a 1-tetrahydrofuranyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, a 3-tetrahydropyranyl group, a 4- Examples include a tetrahydropyranyl group, a 2-(1,3-dioxolanyl) group, a 2-(1,3-dioxanyl) group, a 2-quinolyl group, a 1-isoquinolyl group, a 5-(1,3-benzodioxole) group, a 2-(1,3,4-thiadiazole) group, a 5-tetrazolyl group, a 2-(1,3-benzothiazolyl) group, a 4-piperidinyl group, a 3-(1,2,4-triazole) group, and a 2-(1,3,4-thiadiazole) group.

The aryloxy group portion of the aryloxy group represented by W, which may be mono- or poly-substituted by V, represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenoxy group, a 1-naphthoxy group, and a 2-naphthoxy group.

Examples of the C7-C11 aralkyl group portion of the C7-C11 aralkyl group represented by W, which may be mono- or poly-substituted by V, include benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenyl-2-methylpropyl, 1-phenylbutyl, and 1-phenylpentyl groups.

Examples of the C7-C11 aralkyloxy group portion of the C7-C11 aralkyloxy group represented by W, which may be mono- or poly-substituted by V, include benzyloxy, 1-phenethyloxy, 2-phenethyloxy, 1-phenylpropyloxy, 2-phenylpropyloxy, 3-phenylpropyloxy, 1-phenyl-2-methylpropyloxy, 1-phenylbutyloxy, and 1-phenylpentyloxy.

T represents a hydroxyl group, a cyano group, a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a hydroxyimino group, a C1-C6 alkoxyimino group, or an aryl group which may be mono- or poly-substituted with V.

The C1-C6 alkoxy group represented by T in this specification may be either linear or branched, and examples include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, 1-pentyloxy, isoamyloxy, neopentyloxy, 2-pentyloxy, 3-pentyloxy, 2-methylbutyloxy, tert-pentyloxy, and 1-hexyloxy.

The C1-C6 alkylcarbonyl group represented by T may be either linear or branched, and examples include acetyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, 1-pentylcarbonyl, and 1-hexylcarbonyl.

The C1-C6 alkoxycarbonyl group represented by T may be either linear or branched, and examples include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, 1-pentyloxycarbonyl, isoamyloxycarbonyl, neopentyloxycarbonyl, 2-pentyloxycarbonyl, 3-pentyloxycarbonyl, 2-methylbutyloxycarbonyl, tert-pentyloxycarbonyl, and n-hexyloxycarbonyl.

The C1-C6 alkoxyimino group represented by T may be either linear or branched, and examples include methoxyimino, ethoxyimino, n-propyloxyimino, isopropyloxyimino, n-butyloxyimino, isobutyloxyimino, sec-butyloxyimino, tert-butyloxyimino, 1-pentyloxyimino, isoamyloxyimino, neopentyloxyimino, 2-pentyloxyimino, 3-pentyloxyimino, 2-methylbutyloxyimino, tert-pentyloxyimino, and 1-hexyloxyimino groups.

The aryl group represented by T, which may be mono- or poly-substituted by V, is a monocyclic or polycyclic aromatic group, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

V represents a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, or a C3-C6 cycloalkyl group.

In this specification, examples of halogen atoms represented by V include fluorine, chlorine, bromine, and iodine.

The C1-C6 alkyl group represented by V may be either linear or branched, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 1-pentyl, isoamyl, neopentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, tert-pentyl, and 1-hexyl.

The C1-C6 haloalkyl group represented by V may be either linear or branched, and examples include monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2-chloroethyl, 1-fluoroethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, and heptafluoroisopropyl groups.

The C1-C6 haloalkoxy group represented by V may be either linear or branched, and examples include monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 4-fluorobutoxy, 5-fluoropentoxy, 6-fluorohexyloxy, and heptafluoroisopropyloxy.

Examples of the C3-C6 cycloalkyl group represented by V include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

The compound represented by the above general formula (1) can form a salt, and examples of the salt include inorganic salts such as hydrochloride, nitrate, sulfate, and phosphate, and salts of organic acids such as acetate, lactate, propionate, benzoate, and trifluoromethanesulfonate.

R ¹ is, among others, a hydrogen atom, a formyl group, a hydroxycarbonyl group, a cyano group, a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted by U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkenyl group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a carbamoyl group which may be mono- or poly-substituted by K, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl in the di-C1-C6 alkylamino group). The radical moieties may be the same or different, and the groups may be bonded to each other via alkylene groups to form 3-, 4-, 5-, and 6-membered rings. ), an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, an aryloxy group which may be mono- or poly-substituted with W, an arylthio group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a C7-C11 aralkyloxy group which may be mono- or poly-substituted with W, a C7-C11 aralkylthio group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group is preferred.
In particular, a hydrogen atom, a hydroxycarbonyl group, a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted by U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl group portion in the di-C1-C6 alkylamino group) may be the same or different, and the groups may be bonded to each other via an alkylene group to form a 3-, 4-, 5-, or 6-membered ring.), an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a C7-C11 aralkylthio group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group is preferred.

R ² is, among others, a hydrogen atom, a formyl group, a hydroxycarbonyl group, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 haloalkylthio group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups are each an alkyl group). They can be bonded via an aryl group to form a 3-, 4-, 5-, or 6-membered ring. ), an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, an aryloxy group which may be mono- or poly-substituted with W, a heterocyclic oxy group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group.
In particular, it is preferable that the group represents a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C1-C6 alkylthio group, a C1-C6 haloalkylthio group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5-, or 6-membered ring), an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, an aryloxy group which may be mono- or poly-substituted with W, a heterocyclic oxy group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group.

In another embodiment, R ¹ is also preferably a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted by U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5-, or 6-membered ring), an aryl group which may be mono- or poly-substituted by W, a heterocyclic group which may be mono- or poly-substituted by W, a C7-C11 aralkyl group which may be mono- or poly-substituted by W, or a C3-C6 cycloalkyl C1-C6 alkyl group.

In another embodiment, R ² is a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylthio group, a C1-C6 haloalkylthio group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups are bonded to each other via alkylene groups to form a 3-, 4-, 5- or 6-membered ring). It is also preferable that the aryl group which may be mono- or poly-substituted by W, the heterocyclic group which may be mono- or poly-substituted by W, the aryloxy group which may be mono- or poly-substituted by W, the heterocyclic oxy group which may be mono- or poly-substituted by W, the C7-C11 aralkyl group which may be mono- or poly-substituted by W, the heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted by W, or the C3-C6 cycloalkyl C1-C6 alkyl group.

In general formula (1), Z represents an oxygen atom, a sulfur atom, -SO-, -SO ₂ -, -CH ₂ -, or -CF ₂ -.
Z preferably represents an oxygen atom, a sulfur atom or --CH ₂ --.

In general formula (1), n is 0 or 1. n is preferably 1.

In general formula (1), A ¹ represents a nitrogen atom or CH, A ² represents a nitrogen atom or CH, and A ³ represents a nitrogen atom or CH, except for the case where A ¹ is a nitrogen atom, A ² is CH, and A ³ is a nitrogen atom.
Among them, it is preferable that A ¹ is CH, and it is more preferable that A ¹ is CH and A ³ is a nitrogen atom.

In general formula (1), it is also preferable that R ¹ is a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted with U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups can be bonded to each other via alkylene groups to form a 3-, 4-, 5-, or 6-membered ring), an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group, A ¹ is CH, and A ³ is a nitrogen atom.

In the general formula (1), R ² is a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylthio group, a C1-C6 haloalkylthio group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups are bonded to each other via alkylene groups to form a 3-membered ring, a 4-membered ring, a 5-membered ring, or a 6-membered ring). It is also preferred that A 1 is CH ^{and A 3} ^is a nitrogen atom.

Representative examples of bicyclic pyridine derivatives or salts thereof represented by general formula (1) are summarized in Tables 1 to 4 below, but are not limited to these compounds. These compounds include optical isomers and compounds containing E and Z isomers. Compound numbers will be referred to in the following description.

In addition, the following notations in the table represent the corresponding groups as follows.
"H" is a hydrogen atom, "Me" is a methyl group, "Et" is an ethyl group, "n-Pr" is a normal propyl group, "i-Pr" is an isopropyl group, "c-Pr" is a cyclopropyl group, "n-Bu" is a normal butyl group, "s-Bu" is a sec-butyl group, "i-Bu" is an isobutyl group, "c-Bu" is a cyclobutyl group, "t-Bu" is a tert-butyl group, "n-Pen" is a normal pentyl group, "c-Pen" is a cyclopentyl group, "n-Hex" is a normal hexyl group, "c-Hex" is a cyclohexyl group, "Ph" is a phenyl group, "Bn" is a benzyl group, "Py" is a pyridyl group, "=" is a double bond, and "≡" is a triple bond.

Each compound in Table 4 is in the form of a "salt" as described in the "Remarks" column of Table 4.

Next, the method for producing the bicyclic pyridine derivative or its salt represented by the above general formula (1) of the present invention and the method for producing the intermediate thereof will be described in detail, but the method is not limited to these methods. Note that the reaction can be carried out using a magnetic stirrer, mechanical stirrer, autoclave synthesis device, or a microwave synthesis device.

[Production method 1]

(R ¹ , R ² , Z and n are the same as defined above, R ³ is a C1-C6 alkyl group, each R ³ may be the same or different, and Y is a leaving group.)

The C1-C6 alkyl group represented by ^R3 may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-pentyl group, an isoamyl group, a neopentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methylbutyl group, a tert-pentyl group, and a 1-hexyl group.

Examples of the leaving group represented by Y include a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a p-toluenesulfonyloxy group.

Step-1 is a process for producing an imidazo[1,2-a]pyridine derivative (1a-1) by reacting a 2-aminopyridine compound represented by formula (Q1) with an acetal compound (51). The 2-aminopyridine compound (Q1) and the acetal compound represented by formula (51) are known in some cases and can be obtained from Tokyo Chemical Industry Co., Ltd., etc. Alternatively, they can be prepared from available reagents according to the method described in Journal of Medicinal Chemistry, Vol. 51, No. 20, 2008, pp. 6571-6580, etc.

In step 1, acetal compound (51) can be used in the range of 0.1 to 10 equivalents relative to substrate (Q1) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

In step 1, it is preferable to carry out the reaction in the presence of an acid or a base. Examples of acids that can be used in the present invention include organic acids and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-tosylic acid, pyridinium p-toluenesulfonate, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, fluorosulfonic acid, chloric acid, bromic acid, iodic acid, perbromic acid, thiocyanic acid, metaperiodic acid, hexafluorophosphoric acid, tetrafluoroboric acid, chlorobenzoic acid, and fluorobenzoic acid. Among these acids, hydrochloric acid, sulfuric acid, p-tosylic acid, etc. are preferred in terms of their good yield. Examples of bases that can be used in this reaction include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, potassium phosphate, sodium methoxide, sodium ethoxide, sodium-tert-butoxide, potassium-tert-butoxide, sodium hydroxide, potassium hydroxide, and sodium hydride. Among these bases, sodium methoxide, sodium ethoxide, potassium carbonate, and sodium hydroxide are preferred in terms of good yield. The amount of acid or base used can be within the range of 0.01 to 10 equivalents relative to the 2-aminopyridine compound (Q1) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.05 to 5 equivalents, and more preferably in the range of 0.1 to 1 equivalents.

Step 1 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, and includes aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; and amine solvents such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine. The solvents that can be used include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, halogenated solvents such as chloroform and dichloromethane, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, and mixtures of these. Among these solvents, methanol, ethanol, toluene, and the like are preferred in terms of their good yield.

The reaction can be carried out at a temperature selected appropriately from the range of 0°C to 200°C, depending on the reaction conditions, but a temperature range of 20 to 120°C is preferred in terms of good yield. After the reaction is complete, the desired product can be obtained by normal post-treatment operations, but if necessary, it can also be purified by column chromatography or recrystallization.

[Production method 2]

(R ¹ and Y are as defined above. R ^2a is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, or a heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W; Z ¹ is an oxygen atom or a sulfur atom. W is as defined above.)

The C1-C6 alkyl group represented by R ^2a may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-pentyl group, an isoamyl group, a tert-amyl group, a neopentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methylbutyl group, a tert-pentyl group, a 1-hexyl group, and a 1-ethylpropyl group.

The C1-C6 haloalkyl group represented by R ^2a may be either linear or branched, and examples thereof include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2-chloroethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a 4-fluorobutyl group, a 5-fluoropentyl group, a 6-fluorohexyl group, and a heptafluoroisopropyl group.

Examples of the C3-C6 cycloalkyl group represented by R ^2a include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

The C2-C6 alkenyl group represented by R ^2a may be either linear or branched, and examples thereof include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-methyl-2-butenyl group, a 2-methyl-2-butenyl group, a 3-methyl-2-butenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, and a 5-hexenyl group.

The C2-C6 alkynyl group represented by R ^2a may be either linear or branched, and examples thereof include an ethynyl group, a 1-propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-2-propynyl group, a 2-methyl-3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-methyl-2-butynyl group, a 2-methyl-3-pentynyl group, a 1-hexynyl group, and a 1,1-dimethyl-2-butynyl group.

The aryl group moiety of the aryl group which may be mono- or poly-substituted with W, represented by R ^2a , represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 5-(1,3-benzodioxole) group.

The heterocyclic group moiety of the heterocyclic group which may be mono- or poly-substituted by W, represented by R ^2a , represents a monocyclic or polycyclic ring group, and examples thereof include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, a 2-furanyl group, a 3-furanyl group, a 2-thienyl group, a 3-thienyl group, a 1-tetrahydrofuranyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, a 3-tetrahydropyranyl group, a 4-tetrahydropyranyl group, a 4-pyrazyl group, a 2-(1,3-dioxolanyl) group, a 2-(1,3-dioxanyl) group, a 3-(1,2,4-triazolyl) group, a 5-tetrazolyl group, a 2-(1,3,4-thiadiazolyl) group, a 2-quinolyl group, a 1-isoquinolyl group, and a 2-(1,3-benzothiazole) group.

Examples of the C7-C11 aralkyl group moiety of the C7-C11 aralkyl group which may be mono- or poly-substituted by W, represented by R ^2a , include a benzyl group, a 1-phenethyl group, a 2-phenethyl group, a 1-phenylpropyl group, a 2-phenylpropyl group, a 3-phenylpropyl group, a 1-phenyl-2-methylpropyl group, a 1-phenylbutyl group, and a 1-phenylpentyl group.

Examples of the heterocyclic C1-C6 alkyl group moiety of the heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W, represented by R ^2a , include a 2-pyridylmethyl group, a 3-pyridylmethyl group, a 4-pyridylmethyl group, a 2-thienylmethyl group, a 3-thienylmethyl group, a 2-furfuryl group, a 3-furfuryl group, a 2-pyrimidylmethyl group, a 4-pyrimidylmethyl group, a 5-pyrimidylmethyl group, a 6-pyrimidylmethyl group, a 2-tetrahydrofurfuryl group, a 3-tetrahydrofurfuryl group, and the like.

Step-2 is a step of producing an imidazo[1,2-a]pyridine derivative (1a-2) by reacting an imidazo[1,2-a]pyridine compound represented by formula (Q2) with a compound represented by formula (52) in the presence of a base. The imidazo[1,2-a]pyridine compound (Q2) and the compound represented by formula (52) are publicly known in some cases and can be obtained from Tokyo Chemical Industry Co., Ltd., etc. Alternatively, they can be prepared from available reagents in accordance with the method described in the pamphlet of International Publication WO 2022/187443, etc.

In step 2, the compound represented by (52) can be used in the range of 0.1 to 10 equivalents relative to the substrate (Q2) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 1 to 5 equivalents, and more preferably in the range of 1.5 to 3 equivalents.

Examples of bases that can be used in the present invention include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, dibutylamine, diisopropylethylamine, piperidine, pyridine, N,N'-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]-7-undecene, and alkali metal bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, tripotassium phosphate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium hydride, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, and lithium hexamethyldisilazide. Among these bases, sodium carbonate, potassium carbonate, sodium hydride, sodium hydroxide, and potassium hydroxide are preferred in terms of their good yield. The amount of base used can be within the range of 0.1 to 10 equivalents relative to the imidazo[1,2-a]pyridine compound (Q2) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

　Step 2 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, etc. are preferred because they give good yields.

[Production method 3]

(R ² , n, Y and Z are as defined above. R ^1a represents a C1-C6 alkyl group which may be mono- or poly-substituted by U, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkenyl group, an aryl group which may be mono- or poly-substituted by W, a heterocyclic group which may be mono- or poly-substituted by W, a C7-C11 aralkyl group which may be mono- or poly-substituted by W, or a C3-C6 cycloalkyl C1-C6 alkyl group; M represents ZnX, Sn(R ⁴ ) ₃ , B(OR ⁴ ) ₂ or MgX; X represents a halogen atom; R ⁴ represents a C1-C6 alkyl group or a C3-C6 cycloalkyl group; and each R ⁴ may be independently the same or different. In addition, in B(OR ⁴ ) ₂ , R ⁴ may be bonded to each other to form a 5-membered or 6-membered ring. U and W have the same meanings as above.

The C1-C6 alkyl group moiety of the C1-C6 alkyl group which may be mono- or poly-substituted by U, represented by R ^1a , may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-pentyl group, an isoamyl group, a tert-amyl group, a neopentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methylbutyl group, a tert-pentyl group, a 1-hexyl group, and a 1-ethylpropyl group.

The C1-C6 haloalkyl group represented by R ^1a may be either linear or branched, and examples thereof include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2-chloroethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a 4-fluorobutyl group, a 5-fluoropentyl group, a 6-fluorohexyl group, and a heptafluoroisopropyl group.

Examples of the C3-C6 cycloalkyl group represented by R ^1a include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

The C2-C6 alkenyl group represented by R ^1a may be either linear or branched, and examples thereof include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-methyl-2-butenyl group, a 2-methyl-2-butenyl group, a 3-methyl-2-butenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, and a 5-hexenyl group.

The C2-C6 alkynyl group represented by R ^1a may be either linear or branched, and examples thereof include an ethynyl group, a 1-propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-2-propynyl group, a 2-methyl-3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-methyl-2-butynyl group, a 2-methyl-3-pentynyl group, a 1-hexynyl group, and a 1,1-dimethyl-2-butynyl group.

Examples of the C2-C6 cycloalkenyl group represented by R ^1a include a 1-cyclopropenyl group, a 2-cyclopropenyl group, a 1-cyclobutenyl group, a 2-cyclobutenyl group, a 1-cyclopentenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group, a 1-cycloheptenyl group, a 2-cycloheptenyl group, a 3-cycloheptenyl group, and a 4-cycloheptenyl group.

The aryl group moiety of the aryl group which may be mono- or poly-substituted with W, represented by R ^1a , represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 5-(1,3-benzodioxole) group.

The heterocyclic group moiety of the heterocyclic group which may be mono- or poly-substituted with W, represented by R ^1a , represents a monocyclic or polycyclic ring group, and examples thereof include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, a 2-furanyl group, a 3-furanyl group, a 2-thienyl group, a 3-thienyl group, a 1-tetrahydrofuranyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, a 3-tetrahydropyranyl group, a 4-tetrahydropyranyl group, a 2-(1,3-dioxolanyl) group, a 2-(1,3-dioxanyl) group, a 2-quinolyl group, and a 1-isoquinolyl group.

Examples of the C7-C11 aralkyl group moiety of the C7-C11 aralkyl group which may be mono- or poly-substituted by W, represented by R ^1a , include a benzyl group, a 1-phenethyl group, a 2-phenethyl group, a 1-phenylpropyl group, a 2-phenylpropyl group, a 3-phenylpropyl group, a 1-phenyl-2-methylpropyl group, a 1-phenylbutyl group, and a 1-phenylpentyl group.

The C3-C6 cycloalkyl C1-C6 alkyl group represented by R ^1a may be either linear or branched, and examples thereof include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cyclopropylethyl group, a cyclobutylethyl group, a cyclopentylethyl group, and a cyclohexylethyl group.

Examples of halogen atoms represented by X include chlorine, bromine, and iodine.

The C1-C6 alkyl group represented by ^R4 may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-pentyl group, an isoamyl group, a neopentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methylbutyl group, a tert-pentyl group, and a 1-hexyl group.

Examples of the C3-C6 cycloalkyl group represented by ^R4 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Step-3 is a step of producing an imidazo[1,2-a]pyridine compound (1a-3) by reacting an imidazo[1,2-a]pyridine compound represented by formula (Q3) with an organometallic compound R ^1a M (53) in the presence of a metal catalyst to introduce a substituent represented by R ^1a into the 7-position of the imidazo[1,2-a]pyridine. The organometallic compound represented by formula (53) may be publicly known in some cases and can be obtained from Tokyo Chemical Industry Co., Ltd., etc. Alternatively, it can be prepared according to the method described in Organic Letters, Vol. 13, No. 17, 2011, pp. 4479-4481, etc.

In step 3, the organometallic compound represented by (53) can be used in the range of 0.1 to 10 equivalents relative to the substrate (Q3) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Metal catalysts that can be used in step 3 include, for example, copper compounds, tin compounds, palladium compounds, and palladium black, among which palladium compounds are preferred. Examples of palladium compounds include palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, palladium cyanide, dichlorobis(tri-ortho-tolylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, bis(acetylacetonato)palladium, dichloro-(1,5-cyclooctadiene)-palladium, dichlorodiamminepalladium, tetraamminepalladium nitrate, tetraamminepalladium tetrachloropalladate, dichlorodipyridinepalladium, dichlorodipyridine ... Examples of the palladium include (2,2'-bipyridyl)palladium, dichloro(phenanthroline)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, allylpalladium(II) chloride dimer, allylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, phenylallylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, and dichloro-[1,3-bis(diisopropylphenyl)imidazolylidene]-(3-chloropyridyl)palladium. Among these metal catalysts, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, etc. are more preferred in terms of good yield. The amount of the metal catalyst used can be within the range of 0.01 to 30 mol% relative to the imidazo[1,2-a]pyridine compound (Q3) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%.

These palladium catalysts may be used alone or in combination with a tertiary phosphine. Specific examples of tertiary phosphines include triphenylphosphine, tri(orthotolyl)phosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri-(tert-butyl)phosphine, trineopentylphosphine, tricyclohexylphosphine, trioctylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis( Examples of tertiary phosphines include tris(hydroxymethyl)phosphine, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, and 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl. Among these tertiary phosphines, triphenylphosphine, 1,1'-bis(diphenylphosphino)ferrocene, and 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl are preferred in terms of good yield.
The amount of the tertiary phosphine used is within a range of 0.01 to 30 mol % relative to the imidazo[1,2-a]pyridine compound (Q3) without adversely affecting the progress of the reaction. In order to obtain the target compound in good yield, however, it is preferably used within a range of 0.1 to 10 mol %, and more preferably within a range of 0.5 to 1 mol %.

In step 3, the target product may be synthesized in good yield by carrying out the reaction in the presence of a copper reagent or a base. Examples of copper reagents that can be used in the present invention include copper chloride (I), copper chloride (II), copper bromide (I), copper bromide (II), copper iodide (I), copper acetate (I), copper acetate (II), copper hydroxide (II), copper triflate (I), and copper 2-thiophenecarboxylate (I). Among these copper reagents, copper bromide (I), copper bromide (II), and copper iodide (I) are preferred in terms of good yield. The amount of copper reagent used can be within the range of 0.01 to 30 mol% relative to the imidazo[1,2-a]pyridine compound (Q3) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%. Examples of bases that can be used in this reaction include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, potassium phosphate, tripotassium phosphate, sodium-tert-butoxide, potassium-tert-butoxide, sodium hydroxide, potassium hydroxide, and sodium hydride. Among these bases, sodium carbonate, potassium carbonate, tripotassium phosphate, and the like are preferred in terms of good yield. The amount of base can be used within the range of 0.1 to 10 equivalents relative to the substrate (Q3) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it within the range of 0.5 to 5 equivalents, and more preferably within the range of 1 to 3 equivalents.

　Step 3 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, water, etc. are preferred because they give good yields.

The reaction can be carried out at a temperature selected appropriately from the range of -40°C to 200°C, depending on the reaction conditions, but a temperature range of 20-120°C is preferred in terms of good yield. After the reaction is complete, the desired product can be obtained by normal post-treatment operations, but if necessary, it can also be purified by column chromatography or recrystallization.

[Production Method 4]

( ^R1 and Y are as defined above. ^R5 is an aryl group which may be mono- or poly-substituted with W, or a heterocyclic group which may be mono- or poly-substituted with W. W is as defined above.)

The aryl group moiety of the aryl group which may be mono- or poly-substituted by W, represented by ^R5 , represents a monocyclic or polycyclic aromatic group, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 5-(1,3-benzodioxole) group.

The heterocyclic group moiety of the heterocyclic group which may be mono- or poly-substituted by W, represented by ^R5 , indicates a monocyclic or polycyclic ring group, and examples thereof include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, a 2-furanyl group, a 3-furanyl group, a 2-thienyl group, a 3-thienyl group, a 1-tetrahydrofuranyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, a 3-tetrahydropyranyl group, a 4-tetrahydropyranyl group, a 4-pyrazyl group, a 2-(1,3-dioxolanyl) group, a 2-(1,3-dioxanyl) group, a 3-(1,2,4-triazolyl) group, a 5-tetrazolyl group, a 2-(1,3,4-thiadiazolyl) group, a 2-quinolyl group, a 1-isoquinolyl group, and a 2-(1,3-benzothiazole) group.

Step-4 is a step of producing an imidazo[1,2-a]pyridine compound (1a-4) by reacting an imidazo[1,2-a]pyridine compound represented by formula (Q4) with a compound (54) represented by R ⁵ OH in the presence of a metal catalyst. The compound represented by formula (54) may be publicly known in some cases and can be obtained from Tokyo Chemical Industry Co., Ltd., etc. Alternatively, it can be prepared according to the method described in Tetrahedron Letters, Vol. 55, No. 4, 2014, pp. 811-814, etc.

Metal catalysts that can be used in step 4 include a wide variety of conventionally known catalysts, including copper compounds, nickel compounds, palladium compounds, and palladium black. Examples of copper compounds include copper chloride (I), copper chloride (II), copper bromide (I), copper bromide (II), copper iodide (I), copper acetate (I), copper acetate (II), copper hydroxide (II), copper triflate (I), and copper 2-thiophene carboxylate (I). Examples of nickel compounds include [1,1'-bis(diphenylphosphino)ferrocene]nickel (II) dichloride, bis(triphenylphosphine)nickel (II) dichloride, nickel (II) dichloride, and nickel iodide (II). Examples of palladium compounds and These include palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, palladium cyanide, dichlorobis(tri-o-tolylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, bis(acetylacetonate)palladium, and bis(acetylacetonate). dichloro(1,5-cyclooctadiene)palladium, dichlorodiamminepalladium, tetraamminepalladium nitrate, tetraamminepalladium tetrachloropalladate, dichlorodipyridinepalladium, dichloro(2,2'-bipyridyl)palladium, dichloro(phenanthroline)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)ethane]palladium, Examples of suitable metal catalysts include 1,1'-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, allylpalladium(II) chloride dimer, allylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, phenylallylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, dichloro-[1,3-bis(diisopropylphenyl)imidazolylidene]-(3-chloropyridyl)palladium, etc. Among these metal catalysts, copper(I) iodide and the like are preferred in terms of good yield. The amount of the metal catalyst used can be within the range of 0.01 to 30 mol% relative to imidazo[1,2-a]pyridine (Q4) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%.

In step 4, the target product can be obtained in good yield by carrying out the reaction in the presence of a base. Examples of bases that can be used include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, dibutylamine, diisopropylethylamine, piperidine, pyridine, N,N'-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, and tetrabutylammonium fluoride, as well as alkali metal bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, tripotassium phosphate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium hydride, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, and lithium hexamethyldisilazide. Among these bases, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, and tripotassium phosphate are preferred in terms of their good yield. The amount of base can be within the range of 0.1 to 10 equivalents relative to the substrate (Q4) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

In step 4, the target product can be obtained in good yield by carrying out the reaction in the presence of an additive. Examples of additives that can be used include picolinic acid, 2-picolyl methyl ketone, and 18-crown-6. Among these additives, picolinic acid is preferred because it gives good yields. The amount of additive used can be within the range of 0.1 to 10 equivalents relative to imidazo[1,2-a]pyridine (Q4) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use the additive in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

　Step 4 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, N,N-dimethylformamide, dimethyl sulfoxide, water, etc. are preferred because they give good yields.

[Production Method 5]

(Y has the same meaning as above, and each Y may be the same or different.)

Step 5 is a step of producing a hydrazine derivative (Q6) by reacting compound (Q5) with hydrazine monohydrate (55).

In step 5, hydrazine monohydrate (55) can be used in the range of 0.1 to 10 equivalents relative to the substrate (Q5) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

　Step 5 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; amine solvents such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, methanol, ethanol, water, etc. are preferred because they give good yields.

[Production Method 6]

( ^R3 and Y have the same meaning as above, and may be the same or different from each other independently.)

Step 6 is a step of producing a pyridine derivative (Q7) by reacting a hydrazine derivative represented by formula (Q6) with an orthoformate derivative (56). The orthoformate derivative represented by formula (56) may be publicly known in some cases and may be available from Tokyo Chemical Industry Co., Ltd., etc.

In step 6, orthoformate (56) can be used in the range of 0.1 to 10 equivalents relative to substrate (Q6) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step 6 can be carried out without a solvent or in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, methanol, ethanol, toluene, and the like are preferred in terms of their good yield.

[Production Method 7]

(Y has the same meaning as above, and each independently may be the same or different. ^R3 has the same meaning as above.)

Step 7 is a step in which the pyridine derivative represented by formula (Q7) is cyclized to produce the [1,2,4]triazolo[4,3-a]pyridine derivative (Q8).

In step 7, the target product can be obtained in good yield by carrying out the reaction in the presence of an acid. Examples of acids that can be used include organic acids and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-tosylic acid, pyridinium p-toluenesulfonate, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, fluorosulfonic acid, chloric acid, bromic acid, iodic acid, perbromic acid, thiocyanic acid, metaperiodic acid, hexafluorophosphoric acid, tetrafluoroboric acid, chlorobenzoic acid, fluorobenzoic acid, Eaton's reagent, and polyphosphoric acid. Among these acids, hydrochloric acid, sulfuric acid, p-tosylic acid, Eaton's reagent, and polyphosphoric acid are preferred in terms of good yield. The amount of acid used can be within the range of 0.1 to 10 equivalents relative to the pyridine derivative (Q7) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step 7 can be carried out without a solvent or in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, and mesitylene, aliphatic hydrocarbon solvents such as pentane, hexane, and octane, ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, and mixtures thereof. Among these solvents, toluene, N,N-dimethylformamide, etc. are preferred because they give good yields.

The reaction can be carried out at a temperature selected appropriately from the range of -40°C to 200°C, depending on the reaction conditions, but a temperature range of 20 to 120°C is preferred in terms of good yield. After the reaction is complete, the desired product can be obtained by normal post-treatment operations, but if necessary, it can also be purified by column chromatography or recrystallization.

[Production Method 8]

(Y has the same meaning as above, and each Y may be independently the same or different. R ^2a and Z ¹ have the same meaning as above.)

Step 8 is a step of producing a [1,2,4]triazolo[4,3-a]pyridine derivative (1b-1) by reacting a [1,2,4]triazolo[4,3-a]pyridine derivative represented by formula (Q8) with a compound represented by formula (52) in the presence of a base.

In step 8, the compound represented by (52) can be used in the range of 0.1 to 10 equivalents relative to the substrate (Q8) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Examples of bases that can be used in the present invention include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, dibutylamine, diisopropylethylamine, piperidine, pyridine, N,N'-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]-7-undecene, and alkali metal bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, tripotassium phosphate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium hydride, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, and lithium hexamethyldisilazide. Among these bases, sodium carbonate, potassium carbonate, sodium hydride, sodium hydroxide, and potassium hydroxide are preferred in terms of their good yield. The amount of base used can be within the range of 0.1 to 10 equivalents relative to the [1,2,4]triazolo[4,3-a]pyridine derivative (Q8) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step 8 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, etc. are preferred because they give good yields.

The reaction can be carried out at a temperature selected appropriately from the range of 0°C to 200°C, depending on the reaction conditions, but a temperature range of 20 to 150°C is preferred in terms of good yield. After the reaction is complete, the desired product can be obtained by normal post-treatment operations, but if necessary, it can also be purified by column chromatography or recrystallization.

[Production Method 9]

(R ^1a , R ² , n, M, Y and Z have the same meanings as above.)

Step-9 is a step of producing a [1,2,4]triazolo[4,3-a]pyridine compound (1b-3) by reacting a [1,2,4]triazolo[4,3-a]pyridine derivative represented by formula (1b-2) with an organometallic compound R ^1a M (53) in the presence of a metal catalyst to introduce a substituent represented by R ^1a into the 7-position of the [1,2,4]triazolo[4,3-a]pyridine.

In step 9, the organometallic compound represented by (53) can be used in the range of 0.1 to 10 equivalents relative to the substrate (1b-2) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Metal catalysts that can be used in step 9 include, for example, copper compounds, tin compounds, palladium compounds, and palladium black, among which palladium compounds are preferred. Examples of palladium compounds include palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, palladium cyanide, dichlorobis(tri-ortho-tolylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, bis(acetylacetonato)palladium, dichloro-(1,5-cyclooctadiene)-palladium, dichlorodiamminepalladium, tetraamminepalladium nitrate, tetraamminepalladium tetrachloropalladate, dichlorodipyridinepalladium, dichlorodipyridine ... Examples of the palladium include (2,2'-bipyridyl)palladium, dichloro(phenanthroline)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, allylpalladium(II) chloride dimer, allylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, phenylallylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, and dichloro-[1,3-bis(diisopropylphenyl)imidazolylidene]-(3-chloropyridyl)palladium. Among these metal catalysts, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, etc. are more preferred in terms of good yield. The amount of metal catalyst used can be within the range of 0.01 to 30 mol% relative to [1,2,4]triazolo[4,3-a]pyridine (1b-2) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%.

These palladium catalysts may be used alone or in combination with a tertiary phosphine. Specific examples of tertiary phosphines include triphenylphosphine, tri(orthotolyl)phosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri-(tert-butyl)phosphine, trimeopentylphosphine, tricyclohexylphosphine, trioctylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis( Examples of tertiary phosphines include tris(hydroxymethyl)phosphine, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, and 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl. Among these tertiary phosphines, triphenylphosphine, 1,1'-bis(diphenylphosphino)ferrocene, and 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl are preferred in terms of good yield. The amount of tertiary phosphine used can be within the range of 0.01 to 30 mol% relative to [1,2,4]triazolo[4,3-a]pyridine (1b-2) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%.

In step 9, the target product may be synthesized in good yield by carrying out the reaction in the presence of a copper reagent or a base. Examples of copper reagents that can be used in the present invention include copper chloride (I), copper chloride (II), copper bromide (I), copper bromide (II), copper iodide (I), copper acetate (I), copper acetate (II), copper hydroxide (II), copper triflate (I), and copper 2-thiophenecarboxylate (I). Among these copper reagents, copper iodide (I) is preferred in terms of good yield. The amount of copper reagent used can be within the range of 0.01 to 30 mol% relative to [1,2,4]triazolo[4,3-a]pyridine (1b-2) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%. Examples of bases that can be used in this reaction include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, potassium phosphate, tripotassium phosphate, sodium-tert-butoxide, potassium-tert-butoxide, sodium hydroxide, potassium hydroxide, and sodium hydride. Among these bases, sodium carbonate, potassium carbonate, potassium phosphate, and the like are preferred in terms of good yield. The amount of base can be used within the range of 0.1 to 10 equivalents relative to the substrate (1b-2) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it within the range of 0.5 to 5 equivalents, and more preferably within the range of 1 to 3 equivalents.

Step 9 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide, water, etc. are preferred because they give good yields.

[Production Method 10]

(Y and ^R3 have the same meanings as above.)

Step 10 is a step of producing a pyridine oxide compound (Q10) by oxidizing a pyridine compound represented by formula (Q9) with an oxidizing agent. The compound represented by formula (Q9) may be publicly known in some cases and may be available from Tokyo Chemical Industry Co., Ltd., etc.

The oxidizing agents that can be used in step 10 include hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, OXONE (trade name of E.I. DuPont; containing potassium hydrogen peroxosulfate), N-chlorosuccinimide, N-bromosuccinimide, tert-butyl hypochlorite, sodium hypochlorite, oxygen, etc. Among these oxidizing agents, m-chloroperbenzoic acid, hydrogen peroxide, etc. are preferred because of their good yield. These oxidizing agents can be used in the range of 0.1 to 10 equivalents relative to the pyridine compound (Q9) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use them in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

In step 10, the target product can be synthesized in good yield by carrying out the reaction in the presence of a catalyst. Examples of catalysts used in this reaction include molybdenum oxide, boric acid, iron tris(acetylacetonate), and sodium tungstate. Among these catalysts, sodium tungstate is preferred because it gives good yields. These catalysts can be used in the range of 0.01 to 30 mol% relative to the pyridine compound (Q9) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use them in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%.

Step 10 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, acetonitrile, dichloromethane, chloroform, N,N-dimethylformamide, water, etc. are preferred because they give good yields.

The reaction can be carried out at a temperature selected appropriately from the range of -40°C to 200°C, depending on the reaction conditions, but a temperature range of 0 to 100°C is preferred in terms of good yield. After the reaction is complete, the desired product can be obtained by normal post-treatment operations, but if necessary, it can also be purified by column chromatography or recrystallization.

[Production Method 11]

(Y and ^R3 are as defined above. ^X1 is a chlorine atom or a bromine atom.)

Step 11 is a step of producing a pyridine compound (Q11) by reacting a pyridine oxide compound represented by formula (Q10) with a halogenating agent.

Halogenating agents that can be used in step 11 include thionyl chloride, thionyl bromide, oxalyl chloride, oxalyl bromide, phosphoryl chloride, phosphoryl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus pentabromide, etc. Among these halogenating agents, thionyl chloride, phosphoryl chloride, phosphorus trichloride, etc. are preferred in terms of good yield. The amount of halogenating agent used can be within the range of 0.1 to 10 equivalents relative to the pyridine oxide compound (Q10) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

　Step 11 can be carried out without a solvent or in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform, dichloromethane, and carbon tetrachloride; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, toluene, dichloromethane, chloroform, carbon tetrachloride, etc. are preferred because they give good yields.

[Production Method 12]

( ^X1 , Y and ^R3 have the same meanings as above.)

Step 12 is a step of producing a pyridylmethanol compound (Q12) by reacting a pyridine compound represented by formula (Q11) with a reducing agent.

Reducing agents that can be used in step 12 include sodium borohydride, lithium borohydride, lithium aluminum hydride, borane, diborane, borane dimethylsulfide complex, borane tetrahydrofuran complex, etc. Among these reducing agents, sodium borohydride, lithium borohydride, borane dimethylsulfide complex, borane tetrahydrofuran complex, etc. are preferred in terms of good yield. The amount of reducing agent used can be within the range of 0.1 to 10 equivalents relative to the pyridine compound (Q11) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step-12 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, toluene, tetrahydrofuran, methanol, ethanol, water, and the like are preferred in terms of good yield.

[Production Method 13]

( ^X1 and Y have the same meanings as above.)

Step 13 is a step of producing an azide compound (Q13) by reacting a pyridylmethanol compound represented by formula (Q12) with an azidizing agent in the presence of a base.

Azidation agents that can be used in step 13 include diphenylphosphoric acid azide, 2-azido-1,3-dimethylimidazolium hexafluorophosphate, sodium azide, and the like. Among these azidation agents, diphenylphosphoric acid azide and the like are preferred because of their good yield. The amount of the azidation agent used can be within the range of 0.1 to 10 equivalents relative to the pyridylmethanol compound (Q12) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use the agent in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Examples of bases that can be used in step 13 include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, dibutylamine, diisopropylethylamine, piperidine, pyridine, N,N'-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]-7-undecene, and alkali metal bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, tripotassium phosphate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium hydride, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, and lithium hexamethyldisilazide. Among these bases, triethylamine and 1,8-diazabicyclo[5.4.0]-7-undecene are preferred in terms of their good yield. The amount of base used can be within the range of 0.1 to 10 equivalents relative to the pyridylmethanol compound (Q12) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step 13 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, N,N-dimethylformamide, dimethyl sulfoxide, water, etc. are preferred because they give good yields.

The reaction can be carried out at a temperature selected appropriately from the range of 0°C to 200°C, depending on the reaction conditions, but a temperature range of 20-120°C is preferred in terms of good yield. After the reaction is complete, the desired product can be obtained by normal post-treatment operations, but if necessary, it can also be purified by column chromatography or recrystallization.

[Production Method 14]

( ^X1 and Y have the same meanings as above.)

Step 14 is a process in which the azide compound represented by formula (Q13) is reduced and then treated with a hydrochloric acid solution to produce the hydrochloride salt of the amino compound (Q14).

The reduction method in step 14 may be a method using a reducing agent such as zinc powder, reduced iron, tin powder, stannous chloride, or titanium chloride, a method using a hydrogen donor such as hydrazine in the presence of Raney nickel, catalytic hydrogen reduction in the presence of a catalyst such as Raney nickel, palladium carbon, palladium hydroxide, platinum oxide, or rhodium carbon, catalytic hydrogen transfer reduction, or the Staudinger reaction using triphenylphosphine. Among these reduction methods, the Staudinger reaction is preferred in terms of good yield. Specific examples of tertiary phosphines used in the Staudinger reaction include triphenylphosphine, tri(orthotolyl)phosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri-(tert-butyl)phosphine, trineopentylphosphine, tricyclohexylphosphine, trioctylphosphine, 1,2-bis(diphenylphosphino)ethane, and 1,3-bis(diphenylphosphino)propane. , 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, tris(hydroxymethyl)phosphine, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, and 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl. Among these tertiary phosphines, triphenylphosphine and the like are preferred in terms of good yield. The amount of the tertiary phosphine used can be within the range of 0.1 to 10 equivalents relative to the azide compound (Q13) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step 14 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, toluene, tetrahydrofuran, water, and the like are preferred in terms of their good yield.

[Production Method 15]

(R ³ , X ¹ and Y are as defined above.)

Step 15 is a process for producing a formamide compound (Q15) by reacting the hydrochloride of an amino compound represented by formula (Q14) with an orthoformate ester (56).

In step 15, orthoformate (56) can be used in the range of 0.1 to 10 equivalents relative to the substrate (Q14) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step 15 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, toluene and N,N-dimethylformamide are preferred in terms of their good yield.

The reaction can be carried out at a temperature selected appropriately from the range of -40°C to 200°C, depending on the reaction conditions, but a temperature range of 0 to 150°C is preferred in terms of good yield. After the reaction is complete, the desired product can be obtained by normal post-treatment operations, but if necessary, it can also be purified by column chromatography or recrystallization.

[Production Method 16]

( ^X1 and Y have the same meanings as above.)

Step 16 is a step in which the formamide compound represented by formula (Q15) is cyclized to produce the imidazo[1,5-a]pyridine compound (1c-1).

In step-16, the target product can be obtained in good yield by carrying out the reaction in the presence of an acid, and examples of acids that can be used include organic acids and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-tosylic acid, pyridinium p-toluenesulfonate, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, fluorosulfonic acid, chloric acid, bromic acid, iodic acid, perbromic acid, thiocyanic acid, metaperiodic acid, hexafluorophosphoric acid, tetrafluoroboric acid, chlorobenzoic acid, fluorobenzoic acid, Eaton's reagent, and polyphosphoric acid. Among these acids, hydrochloric acid, sulfuric acid, p-tosylic acid, Eaton's reagent, and polyphosphoric acid are preferred in terms of good yield.
The amount of the acid used can be within a range of 0.1 to 10 equivalents relative to the formamide compound (Q15) without adversely affecting the progress of the reaction. In order to obtain the target compound in good yield, the acid is preferably used within a range of 0.5 to 5 equivalents, and more preferably within a range of 1 to 3 equivalents.

Step 16 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, and mesitylene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, N,N-dimethylformamide, etc. are preferred because they give good yields.

In step 16, heating is essential, and although it depends on the reaction conditions, it can be carried out at a temperature appropriately selected from the range of 50°C to 200°C, but a range of 80 to 150°C is preferred in terms of good yield. After the reaction is complete, the desired product can be obtained by normal post-treatment operations, but if necessary, it can also be purified by column chromatography or recrystallization.

[Production Method 17]

(R ^2a , X ¹ , Y and Z ¹ have the same meanings as above.)

Step 17 is a step of producing an imidazo[1,5-a]pyridine compound (1c-2) by reacting an imidazo[1,5-a]pyridine compound represented by formula (1c-1) with a compound represented by formula (52) in the presence of a base.

In step 17, the compound represented by (52) can be used in the range of 0.1 to 10 equivalents relative to the substrate (1c-1) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Examples of bases that can be used in step 17 include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, dibutylamine, diisopropylethylamine, piperidine, pyridine, N,N'-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]-7-undecene, and alkali metal bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, tripotassium phosphate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium hydride, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, and lithium hexamethyldisilazide. Among these bases, sodium carbonate, potassium carbonate, sodium hydride, sodium hydroxide, and potassium hydroxide are preferred in terms of their good yield. The amount of base used can be within the range of 0.1 to 10 equivalents relative to the imidazo[1,5-a]pyridine compound (1c-1) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

　Step 17 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, etc. are preferred because they give good yields.

[Production Method 18]

(R ^1a , R ² , n, M, Y and Z have the same meanings as above.)

Step-18 is a step of producing an imidazo[1,5-a]pyridine compound (1c-4) by reacting an imidazo[1,5-a]pyridine compound represented by formula (1c-3) with an organometallic compound R ^1a M (53) in the presence of a metal catalyst to introduce a substituent represented by R ^1a at the 7-position of the imidazo[1,5-a]pyridine. The compound represented by formula (1c-3) is known in some cases and can be obtained from Aurora Fine Chemicals LLC or the like. Alternatively, it can be prepared according to the method described in WO 2023/57394.

In step 18, the organometallic compound represented by (53) can be used in the range of 0.1 to 10 equivalents relative to the substrate (1c-3) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Examples of the metal catalyst that can be used in Step-18 include copper compounds, tin compounds, palladium compounds, and palladium black, among which palladium compounds are preferable. Examples of the palladium compounds include palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, palladium cyanide, dichlorobis(tri-ortho-tolylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, bis(acetylacetonato)palladium, dichloro-(1,5-cyclooctadiene)-palladium, dichlorodiamminepalladium, tetraamminepalladium nitrate, tetraamminepalladium tetrachloropalladate, dichlorodipyridinepalladium, dichlorodipyridine ... Examples of the palladium include (2,2'-bipyridyl)palladium, dichloro(phenanthroline)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, allylpalladium(II) chloride dimer, allylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, phenylallylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, and dichloro-[1,3-bis(diisopropylphenyl)imidazolylidene]-(3-chloropyridyl)palladium. Among these metal catalysts, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, etc. are preferred in terms of good yield.
The amount of the metal catalyst used is within a range of 0.01 to 30 mol % relative to the imidazo[1,5-a]pyridine compound (1c-3) without adversely affecting the progress of the reaction. In order to obtain the target compound in good yield, however, the amount is preferably within a range of 0.1 to 10 mol %, and more preferably within a range of 0.5 to 1 mol %.

These palladium catalysts may be used alone or in combination with a tertiary phosphine. Specific examples of tertiary phosphines include triphenylphosphine, tri(orthotolyl)phosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri-(tert-butyl)phosphine, trimeopentylphosphine, tricyclohexylphosphine, trioctylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis( Examples of tertiary phosphines include tris(hydroxymethyl)phosphine, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, and 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl. Among these tertiary phosphines, triphenylphosphine, 1,1'-bis(diphenylphosphino)ferrocene, and 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl are preferred in terms of good yield. The amount of tertiary phosphine used can be within the range of 0.01 to 30 mol% relative to the imidazo[1,5-a]pyridine compound (1c-3) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%.

In step 18, the target compound may be synthesized in good yield by carrying out the reaction in the presence of a copper reagent or a base. Examples of copper reagents that can be used in the present invention include copper chloride (I), copper chloride (II), copper bromide (I), copper bromide (II), copper iodide (I), copper acetate (I), copper acetate (II), copper hydroxide (II), copper triflate (I), and copper 2-thiophenecarboxylate (I). Among these copper reagents, copper iodide (I) and the like are preferred in terms of good yield.
The amount of the copper reagent used is within a range of 0.01 to 30 mol % relative to the amount of the imidazo[1,5-a]pyridine compound (1c-3) without adversely affecting the progress of the reaction. In order to obtain the target compound in good yield, the amount of the copper reagent used is preferably within a range of 0.1 to 10 mol %, and more preferably within a range of 0.5 to 1 mol %.
Examples of bases that can be used in this reaction include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, potassium phosphate, tripotassium phosphate, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, and sodium hydride. Among these bases, sodium carbonate, potassium carbonate, potassium phosphate, and the like are preferred in terms of good yield.
The amount of the base can be within a range of 0.1 to 10 equivalents relative to the imidazo[1,5-a]pyridine compound (1c-3) without adversely affecting the progress of the reaction. In order to obtain the target compound in good yield, the base is preferably used within a range of 0.5 to 5 equivalents, and more preferably within a range of 1 to 3 equivalents.

Step 18 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, tetrahydrofuran, 1,4-dioxane, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, water, etc. are preferred because they give good yields.

[Production Method 19]

(Y has the same meaning as above, and each independently may be the same or different. ^R5 has the same meaning as above.)

Step-19 is a step of producing an imidazo[1,5-a]pyridine compound (1c-6) by reacting an imidazo[1,5-a]pyridine compound represented by formula (1c-5) with a compound ( ⁵⁴ ) represented by R 5 OH in the presence of a metal catalyst. The compound represented by formula (1c-5) is known in some cases and can be obtained from Aurora Fine Chemicals LLC or the like. Alternatively, it can be prepared according to the method described in WO 2023/57394.

Metal catalysts that can be used in step 19 include a wide variety of conventionally known catalysts, including copper compounds, nickel compounds, palladium compounds, and palladium black. Examples of copper compounds include copper chloride (I), copper chloride (II), copper bromide (I), copper bromide (II), copper iodide (I), copper acetate (I), copper acetate (II), copper hydroxide (II), copper triflate (I), and copper 2-thiophene carboxylate (I). Examples of nickel compounds include [1,1'-bis(diphenylphosphino)ferrocene]nickel (II) dichloride, bis(triphenylphosphine)nickel (II) dichloride, nickel (II) dichloride, and nickel iodide (II). Examples of palladium compounds and These include palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, palladium cyanide, dichlorobis(tri-o-tolylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, bis(acetylacetonate)palladium, and bis(acetylacetonate). dichloro(1,5-cyclooctadiene)palladium, dichlorodiamminepalladium, tetraamminepalladium nitrate, tetraamminepalladium tetrachloropalladate, dichlorodipyridinepalladium, dichloro(2,2'-bipyridyl)palladium, dichloro(phenanthroline)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)ethane]palladium, Examples of suitable metal catalysts include 1,1'-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, allylpalladium(II) chloride dimer, allylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, phenylallylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, and dichloro-[1,3-bis(diisopropylphenyl)imidazolylidene]-(3-chloropyridyl)palladium. Among these metal catalysts, copper(I) iodide is preferred in terms of good yield. The amount of the metal catalyst used is within the range of 0.01 to 30 mol% relative to imidazo[1,5-a]pyridine (1c-5) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it within the range of 0.1 to 10 mol%, and more preferably within the range of 0.5 to 1 mol%.

In step 19, the target product can be obtained in good yield by carrying out the reaction in the presence of a base. Examples of bases that can be used include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, dibutylamine, diisopropylethylamine, piperidine, pyridine, N,N'-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, and tetrabutylammonium fluoride, and alkali metal bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, tripotassium phosphate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium hydride, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, and lithium hexamethyldisilazide. Among these bases, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, and tripotassium phosphate are preferred in terms of their good yield. The amount of base can be in the range of 0.1 to 10 equivalents relative to the substrate (1c-5) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

In step 19, the target product can be obtained in good yield by carrying out the reaction in the presence of an additive. Examples of additives that can be used include picolinic acid, 2-picolyl methyl ketone, and 18-crown-6. Among these additives, picolinic acid is preferred because it gives good yields. The amount of additive used can be within the range of 0.1 to 10 equivalents relative to imidazo[1,5-a]pyridine (1c-5) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use the additive in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step 19 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, N,N-dimethylformamide, dimethyl sulfoxide, water, etc. are preferred because they give good yields.

[Production method 20]

(R ¹ , R ² , n, Y and Z have the same meanings as above.)

Step-20 is a step of producing a hydrazine derivative (Q17) by reacting compound (Q16) with hydrazine monohydrate (55). The compound represented by formula (Q16) may be publicly known in some cases and can be obtained from Tokyo Chemical Industry Co., Ltd., etc. Alternatively, it can be prepared according to the method described in Journal of Medicinal Chemistry, Vol. 64, No. 8, 2021, pp. 5018-5036, etc.

In step 20, hydrazine monohydrate (55) can be used in the range of 0.1 to 10 equivalents relative to the substrate (Q16) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

　Step 20 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; amine solvents such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, methanol, ethanol, water, etc. are preferred because they give good yields.

[Production Method 21]

(R ¹ , R ² , R ³ , n and Z are the same as defined above, and each R ³ may be independently the same or different.)

Step 21 is a step of producing a pyridine derivative (Q18) by reacting a hydrazine derivative represented by formula (Q17) with an orthoformate derivative (56).

In step 21, orthoformate (56) can be used in the range of 0.1 to 10 equivalents relative to substrate (Q17) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step-21 can be carried out without a solvent or in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, methanol, ethanol, toluene, and the like are preferred in terms of their good yield.

[Production method 22]

(R ¹ , R ² , R ³ , n and Z have the same meanings as above.)

Step 22 is a step in which the pyridine derivative represented by formula (Q18) is cyclized to produce the [1,2,4]triazolo[4,3-a]pyridine derivative (1b-4).

In step 22, the target product can be obtained in good yield by carrying out the reaction in the presence of an acid. Examples of acids that can be used include organic acids and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-tosylic acid, pyridinium p-toluenesulfonate, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, fluorosulfonic acid, chloric acid, bromic acid, iodic acid, perbromic acid, thiocyanic acid, metaperiodic acid, hexafluorophosphoric acid, tetrafluoroboric acid, chlorobenzoic acid, fluorobenzoic acid, Eaton's reagent, and polyphosphoric acid. Among these acids, hydrochloric acid, sulfuric acid, p-tosylic acid, Eaton's reagent, and polyphosphoric acid are preferred in terms of good yield. The amount of acid used can be within the range of 0.1 to 10 equivalents relative to the pyridine derivative (Q18) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

　Step 22 can be carried out without a solvent or in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, and mesitylene, aliphatic hydrocarbon solvents such as pentane, hexane, and octane, ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, and mixtures thereof. Among these solvents, toluene, N,N-dimethylformamide, etc. are preferred because they give good yields.

[Production method 23]

(R ¹ , R ² , R ³ , n and Z are as defined above.)

Step 23 is a step of producing a pyridylmethanol compound (Q20) by reacting a pyridine compound represented by formula (Q19) with a reducing agent. The compound represented by formula (Q19) may be publicly known in some cases and may be obtained from Tokyo Chemical Industry Co., Ltd., etc. Alternatively, it may be prepared according to the method described in WO 2013/087805.

Reducing agents that can be used in step 23 include sodium borohydride, lithium borohydride, lithium aluminum hydride, borane, diborane, borane dimethylsulfide complex, borane tetrahydrofuran complex, etc. Among these reducing agents, sodium borohydride, lithium borohydride, borane dimethylsulfide complex, borane tetrahydrofuran complex, etc. are preferred in terms of good yield. The amount of reducing agent used can be within the range of 0.1 to 10 equivalents relative to the pyridine compound (Q19) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step-23 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, toluene, tetrahydrofuran, methanol, ethanol, water, and the like are preferred in terms of their good yield.

[Production Method 24]

(R ¹ , R ² , n and Z are as defined above.)

Step 24 is a step of producing an azide compound (Q21) by reacting a pyridylmethanol compound represented by formula (Q20) with an azidizing agent in the presence of a base.

Azidation agents that can be used in step 24 include diphenylphosphoric acid azide, 2-azido-1,3-dimethylimidazolium hexafluorophosphate, sodium azide, and the like. Among these azidation agents, diphenylphosphoric acid azide and the like are preferred because of their good yield. The amount of the azidation agent used can be within the range of 0.1 to 10 equivalents relative to the pyridylmethanol compound (Q20) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use the agent in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Examples of bases that can be used in step 24 include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, dibutylamine, diisopropylethylamine, piperidine, pyridine, N,N'-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]-7-undecene, and alkali metal bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, tripotassium phosphate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium hydride, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, and lithium hexamethyldisilazide. Among these bases, triethylamine and 1,8-diazabicyclo[5.4.0]-7-undecene are preferred in terms of their good yield. The amount of base used can be within the range of 0.1 to 10 equivalents relative to the pyridylmethanol compound (Q20) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step-24 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, N,N-dimethylformamide, dimethyl sulfoxide, water, etc. are preferred because they give good yields.

[Production Method 25]

(R ¹ , R ² , n and Z have the same meanings as above.)

Step 25 is a process in which the azide compound represented by formula (Q21) is reduced and then treated with a hydrochloric acid solution to produce the hydrochloride salt of the amino compound (Q22).

The reduction method in step 25 may be a method using a reducing agent such as zinc powder, reduced iron, tin powder, stannous chloride, or titanium chloride, a method using a hydrogen donor such as hydrazine in the presence of Raney nickel, catalytic hydrogen reduction in the presence of a catalyst such as Raney nickel, palladium carbon, palladium hydroxide, platinum oxide, or rhodium carbon, catalytic hydrogen transfer reduction, or the Staudinger reaction using triphenylphosphine. Among these reduction methods, the Staudinger reaction is preferred in terms of good yield. Specific examples of tertiary phosphines used in the Staudinger reaction include triphenylphosphine, tri(orthotolyl)phosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri-(tert-butyl)phosphine, trineopentylphosphine, tricyclohexylphosphine, trioctylphosphine, 1,2-bis(diphenylphosphino)ethane, and 1,3-bis(diphenylphosphino)propane. , 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, tris(hydroxymethyl)phosphine, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, and 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl. Among these tertiary phosphines, triphenylphosphine and the like are preferred in terms of good yield. The amount of the tertiary phosphine used can be within the range of 0.1 to 10 equivalents relative to the azide compound (Q21) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step-25 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, toluene, tetrahydrofuran, water, and the like are preferred in terms of their good yield.

[Production Method 26]

(R ¹ , R ² , R ³ , n and Z have the same meanings as above.)

Step 26 is a step of producing a formamide compound (Q23) by reacting the hydrochloride of an amino compound represented by formula (Q22) with an orthoformate ester (56).

In step 26, orthoformate (56) can be used in the range of 0.1 to 10 equivalents relative to substrate (Q22) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step-26 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, toluene and N,N-dimethylformamide are preferred in terms of their good yield.

[Production Method 27]

(R ¹ , R ² , n and Z are as defined above.)

Step 27 is a process for producing an imidazo[1,5-a]pyridine compound (1c-7) by cyclizing a formamide compound represented by formula (Q23).

In step-27, the target product can be obtained in good yield by carrying out the reaction in the presence of an acid, and examples of acids that can be used include organic acids and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-tosylic acid, pyridinium p-toluenesulfonate, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, fluorosulfonic acid, chloric acid, bromic acid, iodic acid, perbromic acid, thiocyanic acid, metaperiodic acid, hexafluorophosphoric acid, tetrafluoroboric acid, chlorobenzoic acid, fluorobenzoic acid, Eaton's reagent, and polyphosphoric acid. Among these acids, hydrochloric acid, sulfuric acid, p-tosylic acid, Eaton's reagent, and polyphosphoric acid are preferred in terms of good yield.
The amount of the acid used can be within the range of 0.1 to 10 equivalents relative to the formamide compound (Q23) without adversely affecting the progress of the reaction. In order to obtain the target compound in good yield, the acid is preferably used within the range of 0.5 to 5 equivalents, and more preferably within the range of 1 to 3 equivalents.

　Step 27 can be carried out without a solvent or in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, and mesitylene, aliphatic hydrocarbon solvents such as pentane, hexane, and octane, ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, and mixtures thereof. Among these solvents, toluene, N,N-dimethylformamide, etc. are preferred because they give good yields.

In step 27, heating is essential, and although it depends on the reaction conditions, it can be carried out at a temperature appropriately selected from the range of 50°C to 200°C, but a range of 80 to 150°C is preferred in terms of good yield. After the reaction is completed, the desired product can be obtained by normal post-treatment operations, but if necessary, it can also be purified by column chromatography or recrystallization.

[Production Method 28]

(R ¹ , R ² , n and Z have the same meanings as above.)

Step 28 is a step of producing a pyridine oxide compound (Q25) by oxidizing a pyridine compound represented by formula (Q24) with an oxidizing agent. The compound represented by formula (Q24) may be publicly known in some cases and may be obtained from Tokyo Chemical Industry Co., Ltd., etc. Alternatively, it may be prepared according to the method described in Tetrahedron, Vol. 69, No. 1, 2013, pp. 327-333, etc.

The oxidizing agents that can be used in step 28 include hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, OXONE (trade name of E.I. DuPont; containing potassium hydrogen peroxosulfate), N-chlorosuccinimide, N-bromosuccinimide, tert-butyl hypochlorite, sodium hypochlorite, oxygen, etc. Among these oxidizing agents, m-chloroperbenzoic acid, hydrogen peroxide, etc. are preferred because of their good yield. These oxidizing agents can be used in the range of 0.1 to 10 equivalents relative to the pyridine compound (Q24) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use them in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

In step 28, the target compound can be synthesized in good yield by carrying out the reaction in the presence of a catalyst. Examples of catalysts used in this reaction include molybdenum oxide, boric acid, iron tris(acetylacetonate), and sodium tungstate. Among these catalysts, sodium tungstate is preferred because it gives good yields. These catalysts can be used in the range of 0.01 to 30 mol% relative to the pyridine compound (Q24) without adversely affecting the progress of the reaction, but in order to obtain the target compound in good yield, it is preferable to use them in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%.

Step 28 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, acetonitrile, dichloromethane, chloroform, N,N-dimethylformamide, water, etc. are preferred because they give good yields.

[Production Method 29]

(R ¹ , R ² , n, X ¹ and Z have the same meanings as above.)

Step 29 is a step of producing a pyridine compound (Q26) by reacting a pyridine oxide compound represented by formula (Q25) with a halogenating agent.

Halogenating agents that can be used in step 29 include thionyl chloride, thionyl bromide, oxalyl chloride, oxalyl bromide, phosphoryl chloride, phosphoryl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus pentabromide, etc. Among these halogenating agents, thionyl chloride, phosphoryl chloride, phosphorus trichloride, etc. are preferred in terms of good yield. The amount of halogenating agent used can be within the range of 0.1 to 10 equivalents relative to the pyridine oxide compound (Q25) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step 29 can be carried out without a solvent or in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform, dichloromethane, and carbon tetrachloride; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Among these solvents, toluene, dichloromethane, chloroform, carbon tetrachloride, etc. are preferred because they give good yields.

[Production method 30]

(R ¹ , R ² , n, Y and Z have the same meanings as above.)

Step 30 is a step of producing an aminopyridine compound (Q27) by reacting a pyridine compound represented by formula (Q16) with ammonia.

In step 30, ammonia can be used in the range of 0.1 to 30 equivalents relative to the substrate (Q16) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use ammonia in the range of 0.5 to 15 equivalents, and more preferably in the range of 1 to 10 equivalents.

Step-30 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; amine solvents such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide, water, or a mixture of these solvents. Of these solvents, water is preferred because it gives a good yield.

The reaction can be carried out at a temperature selected appropriately from the range of 20°C to 300°C, depending on the reaction conditions, but a temperature range of 100-200°C is preferred in terms of good yield. After the reaction is complete, the desired product can be obtained by normal post-treatment operations, but if necessary, it can also be purified by column chromatography or recrystallization.

[Production Method 31]

(R ² , R ^2a , n, Y, Z and Z ¹ have the same meanings as above.)

Step-31 is a step of producing a pyridine derivative (Q29) by reacting a pyridine compound represented by formula (Q28) with a compound represented by formula (52) in the presence of a base. The compound represented by pyridine compound (Q28) may be publicly known in some cases and may be obtained from Tokyo Chemical Industry Co., Ltd., etc. Alternatively, it may be prepared from available reagents in accordance with the method described in WO 2021/26479, etc.

In step 31, the compound represented by (52) can be used in the range of 0.1 to 10 equivalents relative to the substrate (Q28) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 1 to 5 equivalents, and more preferably in the range of 1.5 to 3 equivalents.

Examples of bases that can be used in step 31 include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, dibutylamine, diisopropylethylamine, piperidine, pyridine, N,N'-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]-7-undecene, and alkali metal bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, tripotassium phosphate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium hydride, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, and lithium hexamethyldisilazide. Among these bases, sodium carbonate, potassium carbonate, sodium hydride, sodium hydroxide, and potassium hydroxide are preferred in terms of their good yield. The amount of base used can be within the range of 0.1 to 10 equivalents relative to the pyridine compound (Q28) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step-31 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, etc. are preferred because they give good yields.

[Production Method 32]

(R ^1a , R ² , n, M, Y and Z have the same meanings as above.)

Step-32 is a step of producing a pyridine compound (Q30) by reacting a pyridine compound represented by formula (Q28) with an organometallic compound R ^1a M in the presence of a metal catalyst to introduce a substituent represented by R ^1a into pyridine.

In step 32, the organometallic compound represented by (53) can be used in the range of 0.1 to 10 equivalents relative to the substrate (Q28) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Metal catalysts that can be used in step 32 include, for example, iron compounds, copper compounds, tin compounds, palladium compounds, and palladium black, with iron compounds and palladium compounds being preferred. Palladium compounds include, for example, palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, palladium cyanide, dichlorobis(tri-ortho-tolylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, bis(acetylacetonato)palladium, dichloro-(1,5-cyclooctadiene)-palladium, dichlorodiamminepalladium, tetraamminepalladium nitrate, tetraamminepalladium tetrachloropalladate, dichlorodipyridinepalladium, dichlorodipyridine ... Examples of the palladium include (2,2'-bipyridyl)palladium, dichloro(phenanthroline)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, allylpalladium(II) chloride dimer, allylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, phenylallylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, and dichloro-[1,3-bis(diisopropylphenyl)imidazolylidene]-(3-chloropyridyl)palladium. Examples of iron compounds include iron (II) chloride, iron (II) bromide, iron (III) chloride, iron (III) bromide, iron (II) fluoride, iron (III) fluoride, iron (II) iodide, iron (III) iodide, iron (II) acetate, iron (III) acetate, iron (II) acetylacetonate, and iron (III) acetylacetonate. Among these metal catalysts, palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium, dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium, and iron (III) acetylacetonate are more preferred in terms of good yield. The amount of the metal catalyst used can be within the range of 0.01 to 30 mol% relative to the pyridine compound (Q28) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%.

These palladium catalysts may be used alone or in combination with a tertiary phosphine. Specific examples of tertiary phosphines include triphenylphosphine, tri(orthotolyl)phosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri-(tert-butyl)phosphine, trineopentylphosphine, tricyclohexylphosphine, trioctylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis( Examples of tertiary phosphines include tris(hydroxymethyl)phosphine, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, and 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl. Among these tertiary phosphines, triphenylphosphine, 1,1'-bis(diphenylphosphino)ferrocene, and 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl are preferred in terms of good yield.
The amount of the tertiary phosphine used can be within a range of 0.01 to 30 mol % relative to the pyridine compound (Q28) without adversely affecting the progress of the reaction. In order to obtain the target compound in good yield, however, it is preferably used within a range of 0.1 to 10 mol %, and more preferably within a range of 0.5 to 1 mol %.

In step 32, the target product may be synthesized in good yield by carrying out the reaction in the presence of a copper reagent or a base. Examples of copper reagents that can be used in the present invention include copper chloride (I), copper chloride (II), copper bromide (I), copper bromide (II), copper iodide (I), copper acetate (I), copper acetate (II), copper hydroxide (II), copper triflate (I), and copper 2-thiophenecarboxylate (I). Among these copper reagents, copper bromide (I), copper bromide (II), and copper iodide (I) are preferred in terms of good yield. The amount of copper reagent used can be within the range of 0.01 to 30 mol% relative to the bicyclic pyridine compound (Q28) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%. Examples of bases that can be used in this reaction include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, potassium phosphate, tripotassium phosphate, sodium-tert-butoxide, potassium-tert-butoxide, sodium hydroxide, potassium hydroxide, and sodium hydride. Among these bases, sodium carbonate, potassium carbonate, tripotassium phosphate, and the like are preferred in terms of good yield. The amount of base can be used within the range of 0.1 to 10 equivalents relative to the substrate (Q28) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it within the range of 0.5 to 5 equivalents, and more preferably within the range of 1 to 3 equivalents.

Step 32 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. are preferred because they give good yields.

[Production Method 33]

(R ¹ , R ² , n, Y and Z are the same as defined above. R ⁶ is a tert-butyloxycarbonyl group or a 4-methoxybenzyl group.)

Step-33 is a step of producing a pyridine derivative (Q31) by reacting a pyridine compound represented by formula (Q16) with a compound represented by formula (57) in the presence of a base. The compound represented by formula (57) may be publicly known in some cases and may be obtained from Tokyo Chemical Industry Co., Ltd., etc. Alternatively, it may be prepared from available reagents in accordance with the method described in the pamphlet of International Publication WO 2018/49324, etc.

In step 33, the compound represented by (57) can be used in the range of 0.1 to 10 equivalents relative to the substrate (Q16) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

The base that can be used in step 33 includes organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, potassium phosphate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, and sodium hydride. Among these bases, triethylamine, diisopropylethylamine, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, and potassium hydroxide are preferred in terms of good yield. The amount of base used can be within the range of 0.01 to 10 equivalents relative to the pyridine compound (Q16) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.05 to 5 equivalents, and more preferably in the range of 0.1 to 2 equivalents.

In step 33, the target product may be synthesized in good yield by carrying out the reaction in the presence of a metal catalyst. Metal catalysts that can be used in the present invention include, for example, copper compounds, tin compounds, palladium compounds, and palladium black, among which palladium compounds are preferred. Examples of palladium compounds include palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, palladium cyanide, dichlorobis(tri-ortho-tolylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, bis(acetylacetonato)palladium, dichloro-(1,5-cyclooctadiene)-palladium, dichlorodiamminepalladium, tetraamminepalladium nitrate, tetraamminepalladium tetrachloropalladate, dichlorodipyridinepalladium, dichlorodipyridine ... Examples of the palladium include (2,2'-bipyridyl)palladium, dichloro(phenanthroline)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, allylpalladium(II) chloride dimer, allylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, phenylallylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, and dichloro-[1,3-bis(diisopropylphenyl)imidazolylidene]-(3-chloropyridyl)palladium. Among these metal catalysts, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, etc. are more preferred in terms of good yield. The amount of the metal catalyst used can be within the range of 0.01 to 30 mol% relative to the pyridine compound (Q16) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%.

These palladium catalysts may be used alone or in combination with a tertiary phosphine. Specific examples of tertiary phosphines include triphenylphosphine, tri(orthotolyl)phosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri-(tert-butyl)phosphine, trineopentylphosphine, tricyclohexylphosphine, trioctylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis( Examples of tertiary phosphines include tris(hydroxymethyl)phosphine, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, and 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl. Among these tertiary phosphines, triphenylphosphine, 1,1'-bis(diphenylphosphino)ferrocene, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, and 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl are preferred in terms of good yield.
The amount of the tertiary phosphine used can be within a range of 0.01 to 30 mol % relative to the pyridine compound (Q16) without adversely affecting the progress of the reaction. In order to obtain the target compound in good yield, however, it is preferably used within a range of 0.1 to 10 mol %, and more preferably within a range of 0.5 to 1 mol %.

Step 33 can be carried out in the presence of a solvent. As the solvent to be used, any solvent that does not adversely affect the reaction can be used, and examples of the solvent that can be used include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; amine solvents such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, and tert-butanol; dimethyl sulfoxide; water; and mixtures thereof. Among these solvents, 1,4-dioxane, N,N-dimethylformamide, n-butanol, etc. are preferred because they give good yields.

[Production Method 34]

(R ¹ , R ² , R ⁶ , n and Z have the same meanings as above.)

Step 34 is a step of producing a pyridine derivative (Q1) by reacting a pyridine derivative represented by formula (Q31) in the presence of an acid (58).

Examples of acids that can be used in step 34 include organic acids and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-tosylic acid, pyridinium p-toluenesulfonate, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, fluorosulfonic acid, chloric acid, bromic acid, iodic acid, perbromic acid, thiocyanic acid, metaperiodic acid, hexafluorophosphoric acid, tetrafluoroboric acid, chlorobenzoic acid, fluorobenzoic acid, Eaton's reagent, and polyphosphoric acid. Among these acids, hydrochloric acid, sulfuric acid, trifluoroacetic acid, and the like are preferred in terms of good yield. The amount of acid used can be within the range of 0.1 to 10 equivalents relative to the pyridine derivative (Q31) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step 34 can be carried out without a solvent or in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, and mesitylene, aliphatic hydrocarbon solvents such as pentane, hexane, and octane, ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, and mixtures thereof. Among these solvents, toluene, chloroform, water, etc. are preferred because they give good yields.

[Production Method 35]

(A ¹ , A ² , A ³ , R ¹ , R ^1a , M and Y are as defined above.)

Step-35 is a step of producing a bicyclic pyridine compound (1'-2) by reacting a bicyclic pyridine compound represented by formula (1'-1) with an organometallic compound R ^1a M (53) in the presence of a metal catalyst to introduce a substituent represented by R ^1a into the bicyclic pyridine. The compound represented by formula (1'-1) is known in some cases and can be obtained from AstaTech Inc., etc. Alternatively, it can be prepared from available reagents according to the methods described in WO 2022/187443, WO 2008/118718, WO 2017/7700, etc.

In step 35, the organometallic compound represented by (53) can be used in the range of 0.1 to 10 equivalents relative to the substrate (1'-1) without adversely affecting the progress of the reaction, but in order to obtain the desired product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Metal catalysts that can be used in step 35 include, for example, copper compounds, tin compounds, palladium compounds, and palladium black, among which palladium compounds are preferred. Examples of palladium compounds include palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium nitrate, palladium oxide, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, palladium cyanide, dichlorobis(tri-ortho-tolylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, bis(acetylacetonato)palladium, dichloro-(1,5-cyclooctadiene)-palladium, dichlorodiamminepalladium, tetraamminepalladium nitrate, tetraamminepalladium tetrachloropalladate, dichlorodipyridinepalladium, dichlorodipyridine ... Examples of the palladium include (2,2'-bipyridyl)palladium, dichloro(phenanthroline)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, allylpalladium(II) chloride dimer, allylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, phenylallylchloro-[1,3-bis-(diisopropylphenyl)-imidazol-2-ylidene]palladium, and dichloro-[1,3-bis(diisopropylphenyl)imidazolylidene]-(3-chloropyridyl)palladium. Among these metal catalysts, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, etc. are more preferred in terms of good yield. The amount of the metal catalyst used can be within the range of 0.01 to 30 mol% relative to the bicyclic pyridine compound (1'-1) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%.

These palladium catalysts may be used alone or in combination with a tertiary phosphine. Specific examples of tertiary phosphines include triphenylphosphine, tri(orthotolyl)phosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri-(tert-butyl)phosphine, trineopentylphosphine, tricyclohexylphosphine, trioctylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis( Examples of tertiary phosphines include tris(hydroxymethyl)phosphine, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, and 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl. Among these tertiary phosphines, triphenylphosphine, 1,1'-bis(diphenylphosphino)ferrocene, and 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl are preferred in terms of good yield.
The amount of the tertiary phosphine used is within a range of 0.01 to 30 mol % relative to the bicyclic pyridine compound (1'-1) without adversely affecting the progress of the reaction. In order to obtain the target compound in a good yield, the amount is preferably within a range of 0.1 to 10 mol %, and more preferably within a range of 0.5 to 1 mol %.

In step 35, the target product may be synthesized in good yield by carrying out the reaction in the presence of a copper reagent or a base. Examples of copper reagents that can be used in the present invention include copper chloride (I), copper chloride (II), copper bromide (I), copper bromide (II), copper iodide (I), copper acetate (I), copper acetate (II), copper hydroxide (II), copper triflate (I), and copper 2-thiophene carboxylate (I). Among these copper reagents, copper bromide (I), copper bromide (II), and copper iodide (I) are preferred in terms of good yield. The amount of copper reagent used can be within the range of 0.01 to 30 mol% relative to the bicyclic pyridine compound (1'-1) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.1 to 10 mol%, and more preferably in the range of 0.5 to 1 mol%. Examples of bases that can be used in this reaction include organic bases such as trimethylamine, triethylamine, diethylamine, tripropylamine, tributylamine, diisopropylethylamine, dibutylamine, piperidine, and pyridine, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, potassium phosphate, tripotassium phosphate, sodium-tert-butoxide, potassium-tert-butoxide, sodium hydroxide, potassium hydroxide, and sodium hydride. Among these bases, sodium carbonate, potassium carbonate, tripotassium phosphate, and the like are preferred in terms of good yield. The amount of base can be used within the range of 0.1 to 10 equivalents relative to the substrate (1'-1) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it within the range of 0.5 to 5 equivalents, and more preferably within the range of 1 to 3 equivalents.

Step-35 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen-based solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, N,N-dimethylformamide, dimethyl sulfoxide, water, etc. are preferred because they give good yields.

[Production Method 36]

(A ¹ , A ² , A ³ , R ² , n and Z are the same as defined above. R ⁷ is a C1-C6 alkyl group mono- or poly-substituted with a hydroxy group, a formyl group or a carbonyl group. R ⁸ is a C1-C6 haloalkyl group.)

The C1-C6 alkyl group represented by ^R7 may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-pentyl group, an isoamyl group, a tert-amyl group, a neopentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methylbutyl group, a tert-pentyl group, a 1-hexyl group, and a 1-ethylpropyl group.

The C1-C6 haloalkyl group represented by ^R8 may be either linear or branched, and examples thereof include a monofluoromethyl group, a monochloromethyl group, a monobromomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 3-fluoropropyl group, a 4-fluorobutyl group, a 5-fluoropentyl group, a 6-fluorohexyl group, and a heptafluoroisopropyl group.

Step-36 is a step of producing a bicyclic pyridine compound (1'-4) by halogenating a bicyclic pyridine compound represented by formula (1'-3) with a halogenating reagent. The compound represented by formula (1'-3) may be publicly known in some cases and may be obtained from Aurora Fine Chemicals LLC, etc. Alternatively, it may be prepared from available reagents according to the method described in WO 2023/125182, etc.

Halogenating reagents that can be used in step 36 include fluorinating reagents such as DAST, bromine trifluoride, and cesium fluoride; chlorinating reagents such as chlorine, thionyl chloride, oxalyl chloride, phosphorus pentachloride, phosphoryl chloride, and N-chlorosuccinimide; brominating reagents such as bromine, thionyl bromide, oxalyl bromide, phosphorus pentabromide, phosphoryl bromide, and N-bromosuccinimide; and iodinating reagents such as iodine and N-iodosuccinimide. The halogenating agent can be used in the range of 0.1 to 10 equivalents relative to the substrate (1'-3) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 5 equivalents, and more preferably in the range of 1 to 3 equivalents.

Step-36 can be carried out in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol; dimethyl sulfoxide; water; or a mixture of these solvents. Among these solvents, toluene, acetonitrile, dichloromethane, chloroform, etc. are preferred because they give good yields.

[Production Method 37]

(A ¹ , A ² , A ³ , R ² , R ⁴ , n and Z are the same as defined above. R ⁹ is a C2-C6 alkenyl group, a C2-C6 alkynyl group, or a C3-C6 cycloalkenyl group.)

The C2-C6 alkenyl group represented by ^R9 may be either linear or branched, and examples thereof include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, a 2-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-methyl-2-butenyl group, a 2-methyl-2-butenyl group, a 3-methyl-2-butenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, and a 5-hexenyl group.

The C2-C6 alkynyl group represented by ^R9 may be either linear or branched, and examples thereof include an ethynyl group, a 1-propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-2-propynyl group, a 2-methyl-3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-methyl-2-butynyl group, a 2-methyl-3-pentynyl group, a 1-hexynyl group, and a 1,1-dimethyl-2-butynyl group.

Examples of the C2-C6 cycloalkenyl group represented by ^R9 include a 1-cyclopropenyl group, a 2-cyclopropenyl group, a 1-cyclobutenyl group, a 2-cyclobutenyl group, a 1-cyclopentenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group, a 1-cycloheptenyl group, a 2-cycloheptenyl group, a 3-cycloheptenyl group, and a 4-cycloheptenyl group.

Step 37 is a process for producing a bicyclic pyridine derivative (1'-6) by reducing the bicyclic pyridine derivative represented by formula (1'-5) in the presence of a metal catalyst.

The reduction method in this step can be catalytic hydrogen reduction in the presence of a catalyst such as Raney nickel, palladium on carbon, palladium hydroxide, or platinum oxide, or catalytic hydrogen transfer reduction. Among these catalysts, palladium on carbon is preferred because it gives good yields. The amount of metal catalyst used can be within the range of 0.1 to 30 mol% relative to the bicyclic pyridine derivative (1'-5) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is preferable to use it in the range of 0.5 to 15 mol%, and more preferably in the range of 1 to 10 mol%.

　Step 37 can be carried out without a solvent or in the presence of a solvent. The solvent used can be any solvent that does not harm the reaction, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, and mesitylene, aliphatic hydrocarbon solvents such as pentane, hexane, and octane, ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, and mixtures thereof. Among these solvents, toluene, ethyl acetate, methanol, ethanol, chloroform, water, etc. are preferred because they give good yields.

The compound of the present invention can be analyzed, confirmed and identified by melting point, infrared absorption spectrum, ¹ H-NMR, ¹³ C-NMR, mass spectrometry, X-ray structural analysis and the like, if necessary.

The compound of the present invention is not limited to the above-mentioned production method, and can be produced by any organic synthesis method.

[Pest control agents]
The compounds of the present invention are particularly useful as active ingredients of agricultural and horticultural pest control agents, particularly insecticides, acaricides, nematicides and fungicides.

The compounds of the present invention can be used to prevent or exterminate harmful organisms in various situations, such as agriculture, indoors or forests, livestock, or hygiene. Specific usage scenarios, target pests, and usage methods are shown below, but the contents of the present invention are not limited to these.

The compound of the present invention represented by the general formula (1) can be effectively used in agricultural crops, such as edible crops (rice, barley, wheat, rye, oats, and other wheat, corn, potato, sweet potato, taro, soybean, adzuki bean, broad bean, pea, kidney bean, peanut, and other legumes), vegetables (cabbage, Chinese cabbage, radish, turnip, broccoli, cauliflower, komatsuna, and other Brassicaceae crops, pumpkin, Cucumbers, watermelons, melons, eggplants, tomatoes, bell peppers, peppers, okra, spinach, lettuce, lotus root, carrots, burdock, garlic, onions, green onions, etc.), mushrooms (shiitake mushrooms, mushrooms, etc.), fruit trees and fruits (apples, citrus fruits, pears, grapes, peaches, plums, cherries, walnuts, chestnuts, almonds, bananas, strawberries, etc.), It can also be used to control harmful organisms such as arthropods, mollusks, nematodes, fungi and bacteria of the phyla Eumycota, Myxomycota, Bacteria and Actinomycota that damage ornamental crops such as spices (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), specialty crops (tobacco, tea, sugar beet, sugar cane, hops, cotton, hemp, olives, rubber, coffee, etc.), pasture and forage crops (timothy, clover, alfalfa, corn, sorghum, orchard grass, grasses and legumes, etc.), turfgrass (Korean grass, bentgrass, etc.), forest trees (fir trees, spruces, pines, Japanese cypress, cedar, Japanese cypress, etc.) and ornamental plants (herbs and flowers such as chrysanthemums, roses, carnations, orchids, ginkgo trees, cherry trees, Japanese laurels, etc.). Specific harmful organisms include the following:

　Arthropoda, Insecta, Lepidoptera, e.g., Helicoverpa armigera, Heliothis spp., Agrotis segetum, Autographa nigrisigna, Trichoplusia ni, Mamestra brassicae, Spodoptera exigua, Spodoptera litura, Spodoptera spp. ... a frugiperda), Mythimna separata, Agrotis ipsilon, Naranga aenscens, etc., Plutella xylostella, etc., Adoxophyes orana fasciata, Adoxophyes honmai, Archips fuscocupreanus, Homona magnanima, Caloptilia t heivora), Grapholita molesta, Leguminivore glycinivorella, Pandemis heparana, etc., Laminoidae, Eumeta minuscula, etc., Agronomidae, Lyonetia prunifoliella marinella, Lyonetia clerkella, etc., Agronomidae, Phyllocnistis citrella, etc., Gracilariae, onorycter ringoniella, etc., Acrolepiopsis sapporensis, etc., Synanthedin hector, Nokona regalis, etc., Stathmopoda masinissa, etc., Pectinophora gossypiella, Helcystogramma triannulellum, Tuta absoluta, etc., Peach borer, Helcystogramma triannulellum, Tuta absoluta, etc., Carposina niponensis, etc., Cossus jezoensis, etc., Nemapogon granella, etc., Monema flavecens, Parasa lepida, Scopelodes contracus, etc., Chilo suppressalis, Scirpophaga incertulas, Cnaphalocrocis medinalis, Hii, etc., Hellulla undalis, Conogethes punctiferlis, Diaphania indica, Parapedia teterrella, Ostrinia furnacalis, etc. of the Pyralidae family, Locastra muscosalis, Etiella zincella, Galleria mellonella, etc. of the Hesperiidae family, Parnarius serrata, etc. of the Hesperiidae family, a guttata, etc., swallowtail butterfly (Papilio xuthus), etc., Pieris rapae crucivora, etc., lycaenidae butterfly (Lampides boeticus), etc., Geometridae butterfly (Ascotis selenaria), etc., Sphingidae butterfly (Agrius convolvuli), etc., Ornamentidae butterfly (Phalera flavescens), etc., Lasiocampidae butterfly (Malacosoma neustrium testaceum), etc., Adults, larvae and eggs of Saturnia japonica of the Saturniidae family, Eupractis pseudoconspersa, Orgyia thyellina, Telochurus recens approximans of the Lymantriidae family, Spilosoma imparilis, Hyphantria cunea of the Arctiidae family, Endopiza viteana, Laspeyresia pomonella, etc.;

Coleoptera: For example, Scarabaeidae such as Anomala cuprea, Popillia japonica, Oxycetonia jucunda, Anomala geniculata, etc.; Buprestidae such as Agrilus auriventris, etc.; Elateridae such as Melanotus fortnum, etc. i), etc. of the Ladybird family, such as the 204-spotted ladybird (Epilachna vigintioctopunctata), etc. of the Cerambycidae family, such as the 50-point longhorn beetle (Anoplophora malasiaca), the grape tiger longhorn beetle (Xylotrechus pyrrhoderus), etc. of the Chrysomelidae family, such as the cucumber beetle (Aulacophora femoralis), the rootworm species (Diabrotica spp.), the striped flea beetle (Phyllotreta spp.), etc. triolata), Cassida nebulosa, Phaedon brassicae, Oulema oryzae, Epilachna varivestis, Leptinotarsa decemlineata, etc., Rhynchites heros, etc., and the sweet potato weevil, Adults, larvae and eggs of Cylas formicaris, Curculio sikkimensis, Lissorhoptrus oryzophilus, Anthonomus gradis grandis, Sphenophrus venatus vestitus, Epuraea domina, and other beetles of the Nudibranchidae family;

Hemiptera: for example, Eurydema rugosum, Eysarcoris lewisi, Eysarcoris parvus, Nezara viridula, and Brown-winged green bugs of the Hemiptera family. Plautia stali, Halymorpha mista, Urochela luteovoria, Togo hemipterus, Riptidae, etc. ortus clavatus, Clethus punctiger, etc., Leptocorisa chinensis, etc., Dysdeercus cingulatus, etc., Stephania chinensis, etc., The Miridae family includes the light green grass bug (Apolygus spinolai), the red striped grass bug (Stenotus rubrovittalus), the narrow-bearded green grass bug (Trigonotylus spp.), and the azalea powder bug (Stephanitis pyrioides). coelestialium, etc., Bruchidae family: Megacopta punctatissimum, etc., Cicada family: Platypleura kaempferi, etc., Cicadellidae family: Arboria apicalis, Empoasca onukii, Nephotettix cincticeps, Nephotettix virescens, etc., Delphacidae family: Laodelphax striatellus, Nilaparvata lugens ), Sogatella furcifera, etc., Geisha distinctissima, etc., Psylla pyrisuga, Diaphorina citri, etc., Aleyrodidae, Aleurocanthus spiniferus, Bemisia argentifolii, various biotypes of Bemisia tabaci, Dialeurodes citri, Trialeurodes va porariorum, etc., Phylloxeridae grape aphid (Viteus vitifolii), etc., Aphididae snow willow aphid (Aphis citricola), bean aphid (Aphis craccivora), cotton aphid (Aphis gossypii), potato long-horn aphid (Aulacorthum solani), radish aphid (Brevicoryne brassicae), citrus aphid (Toxoptera aurantii), citrus black aphid (Toxoptera citricidus), elderberry long-horn aphid (Aulacorthum ma gnoliae), pear aphid (Schizaphis piricola), green pear aphid (Nippolachnus piri), false radish aphid (Lipaphis erysimi), peach butterbur aphid (Hyalopterus puruni), chrysanthemum aphid (Pleotrichophorus chrysanthemi), chrysanthemum long-horn aphid (Macrosiphoniella samborni), broad bean long-horn aphid (Megoura crassicauda), thorn aphid (Sitobion ibarae), tulip long-horn aphid (M acrosiphhum euphorbiae), Myzus varians, Myzus persicae, Rhopalosiphum rufiabdominalis, Rhopalosiphum padi, Sitobion akebiae, Eriosoma lanigerum, etc., Icerya purchasi, etc., Pseudococcidae, Pseudococcidae, Pseudococcidae, Adults, larvae and eggs of the citrus mealybug (Phenacoccus viburnae), Fuji mealybug (Phenacoccus kraunhiae), etc., the horn mealybug (Ceroplastes ceriferus) and ruby mealybug (Ceroplastes rubens) of the Coccidae family, the red round scale insect (Aonidiella aurantii), the pear round scale insect (Comstockaspis perniciosa), the white mulberry scale insect (Pseudaulacaspis pentagoa), the Yanon scale insect (Unaspis yanonensis), etc.;

Thysanoptera, for example, Scirtothrips dorsalis, Thrips palmi, Thrips tabaci, Thrips setosus, Frankliniella intolerata, etc. nsa), Frankliniella occidentalis, Heliothrips haemorrhoidalis, etc., adults, larvae and eggs of Ponticulothrips diospyrosi, Haplothrips aculeatus, etc. of the Phyllothripidae family;

Hymenoptera: For example, Athalia rosae ruficornis, Arge pagana, etc. of the Tenthredinidae family, Arge mali, etc. of the Cynipidae family, Dryocsmus kuriphilus, etc. of the Megachilidae family, Megachile serrata, etc. of the nipponica nipponica, etc., and adults, larvae and eggs of ant species such as black mountain ants (Formica japonica), camponotus kiusiuensis, black grass ants (Lasius fuliginosus), fire ants (Solenopsis richteri, S. invicta, S. geminata), etc.;

Diptera: For example, Asphondylia yushimai (Cicada midge), Rhacochlaena japonica (Tephritidae), Bactrocera cucurbitae (Melon fly), Hydrellia griseola (Rice fly), Drosophila suzukii (Drosophilidae), and other insects. Adults, larvae and eggs of the bean leafminer (Liriomyza trifolii), tomato leafminer (Liriomyza sativae), garden leafminer (Chromatomyia horticola), rice leafminer (Agromyza oryzae), eggplant leafminer (Liriomyza bryoniae) etc. of the family Gryphiidae, and seed flies (Delia platura), onion flies (Delia antiqua) etc. of the family Anthomyiidae;

Orthoptera (for example, adults, larvae and eggs of the grasshoppers, such as Locusta migratoria and Oxya yezoensis, of the grasshoppers, such as Ruspolia lineosa, of the grasshoppers, such as Teleogryllus emma and Truljalia hibinonis, of the Gryllidae, and Gryllotalpa orientalis, of the Mite family;

Isoptera, for example, adults, larvae and eggs of Odontotermes formosanus of the Termitidae family;
Dermaptera, for example, adults, larvae and eggs of Labidura riparia of the Dermaptera family;

Adults, larvae and eggs of Collembola of the class Insecta of the phylum Arthropoda, for example, Sminthurus viridis of the family Collembola, Onychiurus matsumotoi of the family Onychiurus;
Arthropoda, Malacostraca, Isopada, for example, adults, larvae and eggs of Armadillidium vulgare, ...

Arthropoda, Arachnida, Acaridae, for example, Polyphagotarsonemus latus, Phytonemus pallidus, etc., Penthaleus major, etc., Deuteromycinae, Brevipalpus lewisi, Brevipalpus phoeni, etc. cis, and other mites such as the citrus red mite (Panonychus citri), the apple red mite (Panonychus ulmi), the two-spotted spider mite (Tetranychus urticae), the Kanzawa red mite (Tetranychus kanzawai), the cherry red mite (Amphitetranychus viennensis), the Todomatsu red mite (Oligonychus ununguis), and the Japanese quince red mite (Bryophyte red mite). obia eharai, Eotetranychus kankitus, Bryobia praetiosa, and other mites from the Eriophyidae family, such as Aculus Schlechtendali, Aculops pelekassi, Phyllocoptruta citri, and Eriophyidae. ibaensis), tulip rust mite (Aceria tulipae), grape leafminer mite (Colomerus vitis), peach rust mite (Aculus fockeui), tea rust mite (Calacarus carinatus), etc., adults, larvae and eggs of the family Acaridae such as Tyrophagus putrescentiae and Rhizoglyphus robini;

　Architaenioglossa, Gastropoda, Mollusca, e.g., Pomacea canaliculata, Pulmonata, e.g., Achatina fulica, Meghimatium bilineatum, Milax gagates, Lehmannina valentana, Acusta despecta sieboldiana, Acusta ...

　Tylenchida, Nematoda, Phantomthia, for example, Ditylenchus destructor, Tylenchorhynchus claytoni, Pratylenchus penetrans, Pratylenchus coffeae, Hoplomycetidae, Helicotylenchus dihystera, Globodera, Heterodera, era rostochiensis, etc., Meloidogyne incognita, etc., Criconema jaejuense, etc., Nothotylenchus acris, etc., Aphelecchoides fragariae, etc.; Doliraimidae, for example, adults, larvae and eggs of Xiphinema sp., Longidoridae, Trichodorus sp., etc., of the Trichodoridae;

Fungi and bacteria such as Eumycota, Myxomycota, Bacteriomycota, and Actinomycota.

Specific examples of diseases to which the compound of the present invention represented by the general formula (1) can be applied include rice blast (Pyricularia oryzae), brown spot (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani), brown spot disease (Pantoea ananatis), brown stripe disease (Acidovorax avenae subsp. avenae), brown sheath disease (Pseudomonas fuscovaginae), white leaf blight (Xanthomonas oryzae pv. oryzae), bacterial seedling blight (Burkholderia plantarii), etc.; powdery mildew (E rysiphe graminis), red mold disease (Gibberella zeae), red rust disease (Puccinia striiformis, P. graminis, P. recondita, P. hordei), snow mold disease (Typhula sp., Micronectriella nivalis), naked smut Disease (Ustilago tritici, U. nuda), cattle smut (Tilletia caries), eyespot disease (Pseudocercosporella herpotrichoides), cloud disease (Rhynchosporium secalis), leaf blight (Septoria tritici), leaf spot disease (Leptosphaeria nodorum), net spot (Pyrenophora teres), hail disease (Helminthosporium zonatum Ikata), black node disease (Pseudomonas syringae pv. japonica), etc.; black spot disease of citrus fruits (Diaporthe citri), scab disease (Elsinoe fawcetti), fruit rot disease (Penicillium digitatum, P. italicum), brown rot disease (Phytophthora citrophthora, P. nicotianae), black spot disease (Phyllosticta citricarpa), etc. ; Monilia disease (Monilia mali), canker (Valsa mali), powdery mildew (Podosphaera leucotricha), leaf spot (Alternaria mali), black spot (Venturia inaequalis), black spot (Mycospherella pomi), anthracnose (Colletotrichum acutatum), ring spot (Botryosphaeria berengeriana), red spot (Gymnosporangium yamadae), brown spot (Monilinia fructicola), etc. on apple; black spot (Venturia nashicola, V. pirina), black spot (Alternaria kikuchiana), red spot (Gymnosporangium haraeanum), brown spot (Monilinia fructigena), etc.; brown spot (Monilinia fructicola), black spot (Cladosporium carpophilum), phomopsis rot (Phomopsis sp.), bacterial perforation disease (Brenneria nigrifluens), etc.; black rot (Elsinoe ampelina), late rot (Colletotrichum a cutatum), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black rot (Guignardia bidwellii), downy mildew (Plasmopara viticola), gray rot (Monilinia fructigena), black spot (Cladosporium viticolu), gray mold (Botrytis cinerea), crown gall bacterial disease (Agrobacterium vitis), etc.; anthracnose of persimmon (Gloeosporium kaki), fall Leaf diseases (Cercospora kaki, Mycoshaerella nawae), etc.; Cucumber anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea, Oidiopsis taurica), vine wilt (Didymella bryoniae), vine splitting (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), late blight (Phytophthora sp.), seedling damping-off (Pythium sp.), etc.; cucumber spots Bacterial disease (Pseudomonas syringae pv. lochrymans), bacterial edge blight (Pseudomonas viridiflava), bacterial brown spot (Xanthomonas campestris pv. cucurbitae), etc.; melon bacterial brown spot (Xanthomonas campestris pv. cucurbitae), hairy root disease (Agrobacterium rhizogens), canker (Streptomyces sp.), etc.; watermelon bacterial fruit spot (Acidovorax avenae pv. citrulli), etc.; bacterial wilt of solanaceous vegetables (Ralstonia solanacearum), etc.; ring spot disease of tomatoes (Alternaria solani), leaf mold disease (Cladosporium fulvum), late blight (Phytophthora infestans), sooty mold disease (Pseudomonas fuligena), canker disease (Clavibacter michiganense subsp. michiganense), stem necrosis disease (Pseudomonas corrugata), soft rot disease (Pectobacterium carotovorum subsp. carotovorum), etc.; brown spot disease (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum) of eggplant, etc.; black spot disease (Alternaria japonica), white spot disease (Cercosporella brassicae), soft rot disease (Pectobacterium carotovorum subsp. carotovorum) of cruciferous vegetables, etc.; rot disease (Pseudomonas syringae pv. marginalis), black rot disease (Xanthomonas campestris pv. campestris) of cabbage ) etc.; lettuce rot (Pseudomonas cichorii, Pseudomonas viridiflava), bacterial spot (Xanthomonas campestris pv. vitians), onion rust (Puccinia allii), etc.; soybean purple spot (Cercospora kikuchii), black rot (Elsinoe glycines), black spot (Diaporthe phaseolorum var. sojae), etc.; bean anthracnose (Colletotrichum lindemthianum), etc.; peanut black spot (Cercosp ora personata), brown spot disease (Cercospora arachidicola), etc.; pea powdery mildew (Erysiphe pisi), etc.; potato summer blight (Alternaria solani), late blight (Phytophthora infestans), leaf rot disease fungus (Rhizoctonia solani), etc.; strawberry powdery mildew (Sphaerotheca humuli), etc.; tea net blight (Exobasidium reticulatum), white spot disease (Elsinoe leucospila), red scald disease (Pseudomonas syringae pv. theae), canker (Xanthomonas campestris pv. theicola), etc.; tobacco red spot (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), late blight (Phytophthora nicotianae), damping off (Ralstonia solanacearum), cavity disease (Pectobacterium carotovoru) m subsp. carotovorum, etc.; brown spot disease (Cercospora beticola), damping-off disease (Aphanomyces cochliodes) of sugar beet, etc.; black spot disease (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa) of roses, etc.; brown spot disease (Septoria chrysanthemi-indici), white rust disease (Puccinia horiana), crown gall disease (Agrobacterium tumefaciens) of chrysanthemums, etc.; Gray mold (Botrytis cinerea), sclerotinia sclerotiorum in seed crops; snow mold (Pythium iwayamai, Tyohula incarnate, Fusarium nivale, Sclerotinia borealis), powdery mildew (Erysiphe graminis), fallow ring disease (Lycoperdon perlatum, Lepista subnudo, Marasmius oreades), pseudoleaf rot (Ceratobasidium spp.), damping off (Gaemannomyces graminis), Curvularia leaf spot (Curvularia geniculata), leaf rot (Rhizoctonia solani), Pythium wilt (Pythium periplocum, Pythium vanterpoolii), rust (Puccinia spp.), dollar spot (Sclerotinia homoeocarpa), etc.; bentgrass red burn (Pythium aphanidermatum), anthracnose (Colletotrichum sp.).

The compound of the present invention represented by the general formula (1) can be used to control arthropods and fungi that are active inside buildings, including ordinary houses, and that damage or rot wood and processed wood products such as wooden furniture, stored food, clothing, books, etc., thereby causing damage to our lives. Specific examples of harmful organisms include the following:

Arthropoda, Insecta, Termitidae, e.g., Coptotermes formosanus, Reticulitermes speratus, and other Reticulitermes genus termites (Reticulitermes hesperus, R. tibialis, R. flavipes, R. lucifugus, R. santonensis, etc.), American dry wood termite (Incisitermes minor), Formosan termite (Odontotermes formosanus) of the Termitidae family, Large termite (Hodotermopsis japonica) of the Polytermitidae family, and Cryptotermes domesticus (Cryptotermes domesticus) of the Raphiteritidae family;

Coleoptera: for example, the family Curculionidae, such as the rice weevil (Sitophilus zeamais) and the rice weevil (Sitophilus zeamais), and the family Bruchidae, such as the azuki bean weevil (Callosobruchus chinensis), the pea weevil (Bruchus pisorum), and the broad bean weevil (Bruchus rufimanu). s), etc., Tenebrionidae, such as Tribolium castaneum and Tribolium confusum, etc., Oryzaephilus surinamensis and Cryptolestes pusillus, etc., Anobiidae, such as tobacco beetle, Lasioderma serricorne, Stegobium paniceum, etc., Attagnus unicolor japonicus, Anthreneus verbasci, Dermestes maculatus, etc. of the Dermestidae family , Gibbium aequinnoctiale (false ringed bollworm) of the family Pycnonotidae, Dinoderus minutus (small bamboo long-horn beetle), Rhizopertha dominica (diamond long-horn beetle) of the family Lyctus brunneus (flat-headed bollworm) and other adults, larvae and eggs of Lyctus bruneus (flat-headed bollworm) of the family Lyctus bruneus;

Lepidoptera: for example, Pyralidae, such as Cadra cautella, Ephestia kuehniella, and Plodia interpunctella; Gelechiidae, such as Sitotroga cerealella; Tinea nigricans, such as Tinea nigricans; translucens), Tineola bisselliella, etc.; Psocotyledon, for example, Lepinotus reticulatus, etc. of the Liposcelidae family, Liposcelis bostrychophilus, etc.:

　Battleroach order, for example, adults, larvae and eggs of the German cockroach (Blattella germanica) of the family Blattidae, Periplaneta fuliginosa, Periplaneta japonica, etc. of the family Blattidae; Hymenoptera order, for example, adults, larvae and eggs of the Formicidae family, Monomorium pharaoni, Monomorium nipponense, etc.;

Thymidia, for example, adults, larvae and eggs of the family Zygidae, such as Ctenolepisma villosa and Lepisma saccharina;

Diptera, for example, adults, larvae and eggs of Drosophilidae, such as Drosophila melangogaster, and Piophila casei, such as Piophila casei;

　Arthropoda, Arachnida, Acarina, e.g., Tyrophagus putrescentiae, Lardoglyphus konoi, etc., and Carpoglyphus lactis, etc., adults, larvae and eggs;

Fungi such as wood-rotting fungi Tyromyces palustris and Coriolus versicolor; material-deteriorating microorganisms such as Aspergillus niger, Aspergillus terreus, Aureobasidium pullulans, Chaetomium globosum, and Cladosporium cladosporioides, Eurotium tonophilus, Fusarium moniliforme, Gliocladium virens, Myrothecium verrucaria, Penicillium citrinum, Penicillium funiculosum, Rhizopus oryzae, etc.

The compound of the present invention represented by the general formula (1) can also be used to control harmful organisms that harm or weaken trees in natural forests, artificial forests, and urban green spaces. Specific harmful organisms include the following:

　Arthropoda, Insecta, Lepidoptera, for example, Lymantriidae, such as the Japanese tussock moth (Calliteara argentata), brown tussock moth (Eupproctis pseudoconspersa), Orygia recens approximans, tussock moth (Eupproctis subflava), and gypsy moth (Lymantria dispar, etc., Malacosoma neustria testacea, Dendrolimus spectabilis, Dendrolimus superans, etc., Crytoblabes loxiella, etc., and Agr, etc., of the Pyralidae family. otis segetum, etc., Tortricidae Ptycholoma lecheana circumclumcusana, Cydia kurokoi, Cydia cryptomeriae, etc., Arctiidae Spilosoma imparilis, American white webworm, etc. yphantria cunea, etc., Stigmella castanopsiella, etc., of the Stigmella family, Parasa lepida, Scopelodes contracus, Microleon longipalpis, etc., adults, larvae and eggs of the Limacodidae family;

Coleoptera, for example, the scarabaeidae family, such as the scarab beetle Anomala rufocuprea and the long-legged scarab beetle Heptophylla picea, the jewel beetle Agrilus spinipennis, the Cerambycidae family, such as the pine sawyer Monochamus alternatus, the Chrysomelidae family, such as the cedar leaf beetle Basilepta pallidula, and the Curculionidae family, such as the rust gourd weevil Scenotus arvensis. Adults, larvae and eggs of the following beetles: Shirahoshizo insidiosus, Sipalinus gigas, Tomicus piniperda, Indocryphalus aceris, Rhizopertha dominica, Rhizopertha dominica, etc.;

Hemiptera: for example, adults, larvae and eggs of Aphididae such as Cinara todocola, Adelges japonicus, Aspididae such as Aspididae, Aspidiotus cryptomeriae, Ceroplastes ceriferus, etc.;

Hymenoptera, such as adults, larvae and eggs of the Sawfly family, such as Pachynematus itoi, the Pine Sawfly family, such as Neodiprion sertifer, the Chenocosmus kuriohilus, the Chenocosmus family; Diptera, such as Tipula aino, the Cranefly family, such as Strobilomyia laricicola, the Cecidomyiidae family, and adults, larvae and eggs of the Cecidomyiidae family, such as Contarinia inouyei and Contarinia matsusintome;

Arthropoda, Arachnida, Acari, for example, adults, larvae and eggs of Oligonichus hondoensis, Todomatsu no spider mite (Oligonichus ununguis), etc.;
Phylum Nematoda, Class Phantomthia, Order Tylenchidae, for example, Bursaphelenchus xylophilus of the family Parasitaphelencidae.

The compound of the present invention represented by the general formula (1) can also be used to prevent, treat or control arthropods, nematodes, trematodes, cestodes and protozoa that parasitize internally or externally on vertebrates, particularly warm-blooded vertebrates such as livestock and pets, such as cows, sheep, goats, horses, pigs, poultry, dogs, cats and fish. Target animal species include, in addition to those mentioned above, rodents such as mice, rats, hamsters and squirrels, carnivores such as ferrets, and pet birds such as ducks and pigeons, as well as laboratory animals. Specific examples of harmful organisms include the following:

Arthropoda, Insecta, Diptera, for example, Tabanus rufidens, Tabanus chrysurus, etc., Musca bezzii, Musca domestica, Stomoxys calcitrans, etc., Bocidae, Gasterophilus intestinalis, etc., Hypoderma bovis, etc., Oestrus ovis, etc., Calliphoridae, Aldrichina grahami, etc., Phoridae: Megaseria spiralis, etc., Sepsis punctum, etc., Zygidae: Telmatoscopus albipunctatus, Psychoda alternata, etc., Culex pipiens molestus, Culex pipiens pallens, Anopheles sinensis, Culex pipiens triaeniorhynchus, etc. ... summorosus), Ades albopictus, etc., Simulium iwatense, Prosimulium yezose, etc. of the family Simuliidae, Culicoides schulzei, Culicoides arakawae, etc. of the family Ceratopogonidae, adults, larvae and eggs;
from the order Siphonaptera, for example adults, larvae and eggs of the family Pulex irritans, Ctenocephalides canis and the like;

Ferricidae: Cat louse (Felicola subrostratus), Cow louse (Damalinia bovis), Horse louse (Damalinia caprae), etc., Butterfly louse (Liperus caponis), etc., Elephant louse (Haematomyzus elephantis), Chicken louse (Haematomyzus elephantis), etc. Adults, larvae and eggs of the chicken louse (Menopon gallinae) and chicken lice (Menacanthus stramineus); Phthiraptera, for example, adults, larvae and eggs of the pig louse (Haematopinidae suis) and cow louse (Haematopinidae eurysternus) of the family Astragalus, adults, larvae and eggs of the cow louse (Linognathus vituli) of the family Linognathidae;

Arthropoda, Arachnida, Acarina, e.g. Varroa jacobsoni (Varroa jacobsoni), Haemaphysalis longicornis (Haemaphysalis longicornis), Ixodes ovatus (Ixodes ovatus), Boophilus microplus (Boophilus microplus), Amblyomma testudinarium (Amblyomma testudinarium), Ornithonyssus sylviarum (Ornithomyssus sylviarum), etc. Adults, larvae and eggs of the red mite (Dermanyssus gallinae) of the family Micidae, the pig demodex mite (Demodex phylloides) of the family Demodex mites, the cattle mites (Sarcoptes scabiei bovis) and the trichophyton mites (Knemidocoptes mutans) of the family Scutigera, the ear mites (Otodectes cynotis) and the cattle mites (Psoroptes communis) of the family Otodectes;

Phylum Nematoda, Class Digenea, Order Strongyloides, e.g., Hookworm, Pig Kidneyworm, Lungworm, Trichostrongylus stercoralis, Bovine Intestinal Nodularis, etc.; Ascarida, Class Ascaris, e.g., Ascaris suum, Ascaris roruns, etc.; Phylum Platyhelminthes, Class Trematoda, e.g., Schistosoma japonicum, Hepatic Fasciola, Paragonimus westermani, Paragonimus ovalis, etc.; Class Cestoda, e.g., Tapeworm lamellar, Tapeworm dilatata, Tapeworm benedenensis, Tapeworm quadratus, Tapeworm spurata, Tapeworm ringworm, etc.; Phylum Protozoa, Class Flagellate, Order Rhizoflagellates, e.g., Histomonas, etc.; Flagellates, e.g., Leishmania, Trypanosoma, etc.; Multiflagellates, e.g., Giardia, etc.; Trichomonads, e.g., Trichomonas, etc.; Sarcozoa, Amoeba, e.g., Entamoeba, etc.; Sporozoa, Piroplasma, e.g., Theilaria, Babesia, etc.; Otosporozoa, e.g., Eimeria, Plasmodium, Toxoplasma, etc.

The compound of the present invention represented by the general formula (1) can be used to exterminate harmful organisms that directly harm or cause discomfort to the human body, or to maintain public health against harmful organisms that carry or transmit pathogens. Specific examples of harmful organisms include the following:

　Adults of the order Lepidoptera in the class Insecta of the phylum Arthropoda, such as the white-spotted tussock moth (Sphrageidus similis) of the Lymantriidae family, the oak moth (Kunugia undans) of the Lasiocampidae family, the green lumber moth (Parasa consocia) of the Limacodidae family, and the bamboo thin black moth (Artona martinii) of the Zygaloidae family. , larvae and eggs; Coleoptera, for example, adults, larvae and eggs of the family Xanthochroa, such as the blue long-horned beetle (Xanthochroa waterhousei), the family Meloidae, such as the bean stag beetle (Epicauta gorhani), the family Staphylinidae, such as the blue-leafed rove beetle (Paederus fuscipes);

Hymenoptera, such as the adult, larvae and eggs of the Vespidae family, Vespa simillima xanthoptera, the Formicidae family, Brachyponera chinensis, the Formicidae family, Batozonellus annulatus, and the like; Diptera, such as the Culicidae family, Armigeres subalbatus, the Ceratopogonidae family, Culicoides nipponensis, and the like; Chironomidae, ... Adults, larvae and eggs of Chironomus yoshimatsui, Simulium nikkoense, Hirosia humilis, Musca domestica, Fannia canicularis, Phormia regina, Sarcophaga peregrina, and other insects;

Blattidae, such as the German cockroach (Blattella germanica) of the Blattidae family, and adults, larvae and eggs of the American cockroach (Periplaneta americana), the Siberian cockroach (Periplaneta fuliginosa), and the Japanese cockroach (Periplaneta japonica); Orthoptera, such as the adult, larvae and eggs of the Spotted cockroach (Diestrammena japonica) and the cockroach (Diestrammena apicalis) of the Orthoptera family;
from the order Siphonaptera, for example adults, larvae and eggs of the family Pulexidae, such as the human flea (Pulex irritans);
Adults, larvae and eggs of the order Phthiraptera, for example, head lice (Pediculus humanus humanus) of the family Pediculidae, pubic lice (Phthirius pubis) of the family Pygidae;
Hemiptera, for example, Cimex lectularius of the Cimexidae family, adults, larvae and eggs of Isyndus obscurus of the Triatoma family;

　Adults, larvae and eggs of Collembola order (Collembola) of the class Insecta of the phylum Arthropoda, such as Hypogastrura communis of the family Hypogastrura;

Arthropoda, Arachnida, Acarina, e.g., Ixodes persulcatus, Ixodidae, Ornithonyssus bacoti, Chelacaropsis moorei, Pyemotes ventricosus, etc. Adults, larvae and eggs of Demodex folliculorum, Dermotophagoides pteronyssinus, Sarcoptes scabiei, Trombicula akamushi, etc. of the family Trombiculidae; Orthoaraneae, for example, Chiracanthium japonicum of the family Campephagidae, Heteropoda venatoria of the family Heteropoda, Spermophora senoculata, Pholcus phalangioides of the family Pholcidae, etc. Adults, larvae and eggs of the spider family Uroctea compactis, Salticidae Plexippus paykulli, Plexippus adansoni, etc.; Scorpionidae, for example, adults, larvae and eggs of the spotted scorpion Isometrus europaeus, etc.;

　Arthropoda, Chelipeda, for example, adults, larvae and eggs of Scolopendra subspinipes mutilans and Scolopendra subspinipes japonica of the family Scolopendidae; Centipedia, for example, adults, larvae and eggs of Thereuronema hilgendofi of the family Centipedidae;

　Adults, larvae and eggs of the order Oxididae of the class Diplopoda of the phylum Arthropoda, such as the Oxidus gracilis of the family Oxididae;

　Arthropoda, Crustacea, Isopoda, such as adults, larvae and eggs of the woodlouse (Porcellio scaber) of the family Isopoda;

　Annelida, Turphidae, Gnathine, for example, Haemadipsa zeylanica japonica, etc.;

Fungi such as Trichophyton rubrum and Trichophyton mentagrophytes, candida fungi such as Candida albicans, aspergillus fungi such as Aspergillus fumigatus, gram-negative bacteria such as Escherichia coli and Pseudomonas aeruginosa, and gram-positive bacteria such as Staphylococcus aureus.

The compounds of the present invention represented by the general formula (1) are particularly valuable for controlling harmful organisms, such as arthropods, gastropods, nematodes and fungi, which damage agricultural crops, natural forests, artificial forests and trees and ornamental plants in urban green spaces. In such situations, the compounds of the present invention, in their commercially useful formulations and in the use forms prepared by these formulations, can also be present as mixtures with other active compounds, such as insecticides, acaricides, nematicides, fungicides, synergists, plant regulators, poison baits or herbicides.

Possible usage forms include wettable powders, wettable granules, dry flowables, water-soluble powders, water-soluble granules, emulsions, liquids, oils, suspensions in water, emulsions in water, and other flowables (including EW and ME), suspensions in oil (OD), capsules, powders, coarse powders, DL (driftless type) powders, flow dust, microgranules, fine granules, granules, fine granules, bait, tablets, sprays, aerosols, and the like. To produce these dosage forms, various conventionally used agricultural chemical adjuvants can be used. Such agricultural chemical adjuvants can be used for purposes such as improving the effectiveness of the active ingredient, stabilizing it, and improving its dispersibility.

Examples of agricultural chemical adjuvants include bulking agents (diluents), emulsifiers, wetting agents, dispersants, disintegrants, binders, defoamers, and fungicides. Examples of liquid bulking agents that can be used include water, aromatic hydrocarbons such as toluene, xylene, and methylnaphthalene, alcohols such as methanol, butanol, propylene glycol, glycerin, butylene glycol, and hexylene glycol, ketones such as acetone and cyclohexanone, amides such as dimethylformamide, dimethylethyleneurea, N-octylpyrrolidone, N,N-dimethyloctanoic acid amide, and N,N-dimethyldecanoic acid amide, sulfoxides such as dimethyl sulfoxide, naphthenes such as cyclohexane and methylcyclohexane, paraffins such as nujol and white oil, and esters such as methyl oleate, soybean oil, rapeseed oil, isopropyl phosphate, propylene carbonate, ethyl lactate, and butyl lactate. Examples of the solid extender include natural minerals such as clay, quartz, calcite, sepiolite, dolomite, chalk, kaolin, pyrophyllite, sericite, halloysite, metahaloysite, wood-bush clay, frog-eye clay, pottery stone, ziglite, allophane, shirasu, kira, talc, pumice, hectorite, zeolite, and diatomaceous earth; calcined products of natural minerals such as calcined clay, perlite, shirasu balloon, vermiculite, attapulgus clay, and calcined diatomaceous earth; magnesium carbonate, calcium carbonate, sodium carbonate, and the like; Inorganic salts such as sodium, sodium bicarbonate, ammonium sulfate, sodium sulfate, magnesium sulfate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and potassium chloride; sugars such as glucose, fructose, sucrose, and lactose; polysaccharides such as starch, powdered cellulose, and dextrin; organic substances such as urea, urea derivatives, benzoic acid, and salts of benzoic acid; plants such as wood flour, corn cobs, walnut shells, and tobacco stalks; fly ash, white carbon, and the like can be used.

　Normal surfactants can be used as emulsifiers, wetting agents, dispersants, and disintegrants, and examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. For example, examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene styryl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkylates, polyoxyethylene phenyl ether polymers, polyoxyethylene alkylene allyl phenyl ethers, polyoxyethylene alkylene aryl phenyl ethers, polyoxyethylene alkylene glycols, polyoxyethylene-polyoxypropylene block polymers, polyoxyethylene-polyoxypropylene alkyl ethers, polyoxyethylene-polyoxypropylene ethylenediamines, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, and sucrose fatty acid esters; examples of anionic surfactants include condensates of naphthalene sulfonic acid and formaldehyde or their salts, alkyl naphthalene sulfonic acid and formaldehyde condensates, and alkyl naphthalene sulfonic acid and formaldehyde condensates. Condensates of aldehydes or their salts, dodecylbenzenesulfonates, alkylsulfonates, lauryl sulfates, alkylarylsulfonates, alkylnaphthalenesulfonates, α-olefinsulfonates, ligninsulfonates, monoalkylsulfosuccinates, dialkylsulfosuccinates, polyoxyethylene alkylsulfosuccinates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, polyoxyethylene arylaryl ether sulfates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylaryl ether phosphates, polyoxyethylene arylaryl ether phosphates, polycarboxylates, etc.; cationic surfactants include alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, etc.; amphoteric surfactants include dialkylaminoethyl betaines, alkyldimethylbenzyl betaines, etc.

Binders that can be used include processed starches such as dextrin (roasted dextrin, enzyme-modified dextrin, etc.), acid-decomposed starch, oxidized starch, pregelatinized starch, etherified starch (carboxymethyl starch, hydroxyalkyl starch, etc.), esterified starch (starch acetate, starch phosphate, etc.), crosslinked starch, and grafted starch; natural substances such as sodium alginate, gum arabic, gelatin, tragacanth gum, locust bean gum, and casein; cellulose derivatives such as sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, ethylcellulose, and acetylcellulose; polyvinyl alcohol; and polyvinylpyrrolidone.

As antifoaming agents, silicone-based substances, fatty acid-based substances, etc. can be used.

As antifungal agents, potassium sorbate, p-chloro-m-xylenol, butyl p-oxybenzoate, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, etc. can be used.

Of course, the compounds of the present invention can be formulated as active ingredients, either alone or in combination of two or more. The content of the compound of the present invention as an active ingredient in these formulations is, for example, 0.0001 to 99.5% by weight, preferably selected from the range of 0.5 to 90% by weight, and may be appropriately determined depending on various conditions such as the formulation type and application method. For example, dusts and DL dusts contain 0.01 to 30% by weight, preferably 0.1 to 10% by weight, microgranules contain 0.01 to 40% by weight, preferably 0.1 to 15% by weight, wettable powders and wettable granules contain 0.5 to 90% by weight, preferably 10 to 80% by weight, granules contain 0.01 to 60% by weight, preferably 0.05 to 50% by weight, emulsifiable concentrates contain 0.5 to 90% by weight, preferably 1 to 70% by weight, flowables contain 0.01 to 60% by weight, preferably 0.05 to 50% by weight, and seed treatment dusts contain 0.01 to 90% by weight, preferably 0.1 to 80% by weight.

To control arthropods, gastropods, nematodes, and fungi, the agent is usually sprayed on the stems and leaves of plants in areas where damage caused by these pests has occurred or is likely to occur. In addition, the agent can be applied to the soil and absorbed through the roots by mixing into the entire soil layer, applying in rows, mixing into bed soil, treating cell seedlings, treating in planting holes, treating the base of plants, top dressing, treating rice in boxes, applying to the water surface, etc. In addition, the agent can be used for seed treatment such as soaking seeds in the agent, seed dressing, treating with Calper, applying to nutrient solutions in nutrient solution (hydroponic) cultivation, smoking, or injecting into tree trunks. When used, the amount of active ingredient applied varies depending on the type and amount of pests, the type and cultivation form and growth state of the target crop or tree, but generally 0.1 to 1000 g, preferably 1 to 100 g, of the active ingredient is applied per 10 ares. To treat them, in the case of flowable formulations such as wettable powders, wettable granules, dry flowable formulations, water-soluble powders, emulsions, liquid formulations, water suspensions, water emulsions, and capsule formulations, they are diluted with water and sprayed on crops etc. at an application rate of generally 10 to 1,000 liters per 10 ares, although this varies depending on the type of plant, cultivation form, and growth conditions. In addition, in the case of powders, sprays, or aerosol formulations, they can be applied to crops etc. in that formulation state.

　Examples of application methods when the target pests mainly harm plants in the soil or when the agent is absorbed through the roots to control the target pests include applying the formulation, with or without dilution, to the base of the plant or to a seedling bed, etc., diluting the formulation with or without dilution, spraying granules at the base of the plant or to a seedling bed, etc., spraying dust, hydrated agent, hydrated granules, granules, etc. and mixing with the entire soil before sowing or transplanting, spraying dust, hydrated agent, hydrated granules, granules, fine granules, etc. in planting holes, rows, etc. before sowing or planting the plants, etc. For flowable formulations such as wettable powders, wettable granules, water-soluble powders, emulsions, liquid formulations, water suspensions/emulsions in water, and capsule formulations, the agent is diluted with water and generally applied at a rate of 5-500 liters per 10 ares, and sprayed or irrigated on the soil surface so as to cover the entire area to be treated evenly. For powders, granules, fine granules, baits, etc., the agent is sprayed in its formulation on the soil surface so as to cover the entire area to be treated evenly. Spraying or irrigation may be performed around seeds, crops, or trees that you wish to protect from damage. The active ingredient can also be mechanically dispersed by tilling during or after spraying.

The method of application to rice seedling boxes may vary depending on the time of application, such as application at the time of sowing, application during the greening period, or application at the time of transplanting, but may be in the form of, for example, a dust, water dispersible granule, granule, or fine granule. Application can also be by mixing with the culture soil, and the culture soil can be mixed with a dust, water dispersible granule, granule, or fine granule, for example, by mixing with the bed soil, covering soil, or the entire culture soil. Alternatively, the culture soil and various formulations may simply be layered alternately and applied.

　Application to paddy fields is usually by spraying solid preparations such as jumbo formulations, pack formulations, granules, wettable powders, and granular wettable powders, or liquid preparations such as flowable powders and emulsions, onto flooded paddy fields. In addition, at the time of rice planting, appropriate preparations can be sprayed or injected into the soil as is or mixed with fertilizer, etc. Also, by using emulsions, flowable powders, etc. as liquids at the source of water flow into the paddy field, such as water inlets and irrigation equipment, application can be labor-saving as the water is supplied. Liquid preparations or granules such as wettable powders, granular wettable powders, emulsions, flowable powders, etc. can also be sprayed from the air using radio-controlled helicopters, drones, etc.

Seed treatment methods include, for example, soaking seeds in a liquid or solid formulation, diluted or undiluted, to allow the agent to adhere to and penetrate the seeds, mixing a solid or liquid formulation with the seeds and coating them to allow the agent to adhere to the seed surface, mixing with an adhesive such as a resin or polymer and coating the seeds, and spraying the agent around the seeds at the same time as planting. The "seeds" used in this seed treatment refer to plant bodies in the early stages of cultivation used for plant propagation, and examples include seeds, as well as bulbs, tubers, seed potatoes, sprouts, bulbils, bulbs, or plant bodies for vegetative propagation for cultivation by cuttings. In addition, when applied, the "soil" or "cultivation carrier" of a plant refers to a support for cultivating crops, particularly a support for growing roots. The material is not particularly limited, but any material that allows plants to grow can be used, such as soil, seedling mats, water, etc., and specific examples of materials include sand, pumice, vermiculite, diatomaceous earth, agar, gel-like substances, polymeric substances, rock wool, glass wool, wood chips, bark, etc.

When sowing or raising seedlings of cultivated plants to be transplanted, in addition to direct treatment of the seeds, it is preferable to irrigate the seedling bed with a liquid agent or spray granules. It is also preferable to apply granules to the planting hole at the time of planting or to mix the agent into the cultivation carrier near the transplanting site.

The compound of the present invention represented by the general formula (1) is also valuable for protecting wood (standing trees, fallen trees, processed wood, stored wood, or structural wood) from damage by insects such as termites or coleoptera, fungi, and the like. In such a case, the wood or the soil around it can be controlled by spraying, injecting, irrigating, or applying an oil solution, emulsion, wettable powder, or sol, or by spraying a powder or granule. The oil solution, emulsion, wettable powder, or powder used in this case can also be present as a mixture with other active compounds, such as insecticides, acaricides, nematicides, fungicides, repellents, or synergists, and these formulations can contain the active ingredient compound in a total amount of 0.0001 to 95% by weight, preferably 0.005 to 10% by weight for oil solutions, dusts, and granules, and 0.01 to 50% by weight for emulsions, wettable powders, and sols. When controlling arthropods or fungi, etc., 0.01 to 100 g of the active ingredient compound per ¹ m2 is spread on the soil or wood surface.

The compounds of the present invention represented by the general formula (1) are valuable for the extermination or prevention of arthropods and fungi that parasitize the body surface of humans and livestock and cause direct harm by feeding on the skin or sucking blood, arthropods, nematodes, trematodes, cestodes, protozoa that spread diseases of humans and livestock or are vectors of such diseases, and arthropods that cause discomfort to humans. In such situations, the compounds of the present invention can be mixed in small amounts into food or feed, or administered orally as appropriate orally ingestible compounded pharmaceutical compositions, such as tablets, pills, capsules, pastes, gels, beverages, medicated feed, medicated drinking water, medicated follow-up feed, sustained-release large pills, and other sustained-release devices that are retained in the gastrointestinal tract, containing pharma- ceutical acceptable bulking agents and coating substances, or administered transdermally as sprays, powders, greases, creams, ointments, emulsions, lotions, spot-ons, pour-ons, shampoos, and the like. To achieve the desired effect in such applications, the formulation generally contains 0.0001 to 0.1% by weight, preferably 0.001 to 0.01% by weight, of the active ingredient compound. As a method of transdermal or local administration, a device (e.g., a collar, medallion, ear tag, etc.) attached to the animal to control arthropods locally or systemically can also be used.

　Specific oral and transdermal administration methods for the compound of the present invention represented by the general formula (1) when used as an anthelmintic for animals such as livestock and pets or humans are shown below, but are not necessarily limited to these.

When administered orally as a medicated drinking water, the drink is usually a solution, suspension or dispersion in a suitable non-toxic solvent or water together with a suspending agent such as bentonite or a wetting agent or other excipients. The drink formulation generally contains 0.01 to 1.0% by weight, preferably 0.01 to 0.1% by weight, of the active compound.

When oral administration in a dry solid unit dose form is desired, capsules, pills or tablets containing a predetermined amount of the active ingredient are usually used. These dose forms are prepared by intimately mixing the active ingredient with a suitable finely divided diluent, filler, disintegrant and/or binder, such as starch, lactose, talc, magnesium stearate, vegetable gums and the like. Such unit dose formulations can vary widely in weight and content of anthelmintic agent depending on the type of host animal to be treated, the degree of infection and type of parasite and the body weight of the host.

When administered via animal feed, it can be homogenously dispersed in the feed, used as a top dressing or in the form of pellets. In general, to achieve the desired antiparasitic effect, the final feed contains 0.0001-0.05% by weight of the active compound, preferably 0.0005-0.01% by weight.

When dissolved or dispersed in a liquid bulking vehicle, the active compound may be administered parenterally to animals by intragastric, intramuscular, intratracheal or subcutaneous injection. For parenteral administration, the active compound is preferably mixed with a suitable vegetable oil such as peanut oil or cottonseed oil. Such formulations generally contain 0.05-50% by weight of the active compound, preferably 0.1-5.0% by weight. It may also be administered topically by mixing with a suitable bulking agent such as dimethylsulfoxide or a hydrocarbon solvent. The formulation may be applied directly to the external surface of the animal by spraying or direct pouring.

The compound of the present invention represented by the general formula (1) can be used as an anthelmintic agent for arthropods that directly harm or are vectors of disease, in the surrounding environment where such harmful organisms may be present, by spraying, injecting, irrigating, or applying oils, emulsions, wettable powders, etc., spraying powders, etc., fumigants, heated aerosols such as mosquito coils, self-burning fumigants, and chemical reaction aerosols, fumigants such as fogging, ULV agents, etc., setting granules, tablets, and poison bait, or adding floating powders, granules, etc. to waterways, wells, reservoirs, water tanks, and other running or standing water. Furthermore, it is possible to control tussock moths, which are agricultural and forest pests, in the same manner as described above, and for flies, etc., it is effective to mix it into livestock feed so that it mixes with the feces, and for mosquitoes, it is effective to volatilize it into the air using an electric mosquito repellent, etc. Furthermore, these formulations, which are the forms of use, can also exist as mixtures with other active compounds, such as insecticides, acaricides, nematicides, fungicides, repellents, or synergists, and these formulations contain 0.0001 to 95% by weight of the active ingredient compound in total.

The compound of the present invention represented by the general formula (1) can also be present as a mixture with other active compounds. In particular, by using it in a mixture with a compound (insecticide) having insecticidal activity, acaricidal activity or nematode control activity, it is possible to expand the range of pests to be controlled for the control of harmful organisms such as arthropods, gastropods and nematodes that cause damage to plants, and synergistic effects such as a reduction in the amount of drug can be expected. Specific examples of such active compounds include the following.

Insecticide:
(1) Organophosphorus insecticides Acephate, azinphos-methyl, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, cyanophos, diazinon, dimeton-S-methyl, diclofenthion, dichlorvos, dimethoate oate), dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, fenamiphos, fenitrothion, fenthion, isofenphos, isoxathion, malathion, methidathion, mevinphos, monocrotophos monocrotophos, naled, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos ofos, propaphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, tebupirimiphos, temephos, terbufos, tetrachlorvinphos, thiometon, trichlorfon, vamidothion, and the like;

(2) Carbamate insecticides: aldicarb, alanycarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, fenoxycarb, furathiocarb iocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate, XMC, xylylcarb, aldoxycarb, and the like;

(3) Organochlorine Insecticides: aldrin, chlordane, DDT (p,p'-DDT), endosulfan, lindane, methoxychlor, and the like;

(4) Pyrethroid insecticides: acrinathrin, allethrin, bifenthrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin ), gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, fluvalinate, tau-fluvalinate, halfenprox, metofluthrin, permethrin, phenothrin [(1R)-trans-isomer], pyrethrins, resmethrin, silafluofen, tefluthrin, tetramethrin, tralomethrin, and the like;

(5) Nereistoxin insecticides: bensultap, cartap hydrochloride, thiocyclam, thiosultap, and the like;

(6) Neonicotinoid insecticides: acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, and the like;

(7) Diamide insecticides Chlorantraniliprole, cyantraniliprole, flubendiamide, cyclaniliprole, tetraniliprole, fluchlordiniliprole, thiolantraniliprole, and the like;

(8) Phenylpyrazole insecticides such as acetoprole, ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole, and the like;

(9) Insect growth regulators such as benzoyl urea insecticides and diacylhydrazines: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron (triflumuron), etc.; chromafenozide, halofenozide, methoxyfenozide, tebufenozide, etc.; juvenile hormone agents, for example, diofenolan, fenoxycarb, hydroprene, methoprene, pyriproxyfen, etc.;

(10) Insecticidal substances produced by microorganisms, etc. Abamectin, emamectin-benzoate, ivermectin, lepimectin, milbemectin, nemadectin, nikkomycin, polyoxin complex, spinetram, spinosad, BT agents, etc.;

(11) Insecticidal substances derived from natural products Anabasine, azadiractin, deguelin, fatty acid glyceride, hydroxypropyl starch, soybean lecithin, nicotine, nornicotine, sodium oleate, machine oil, propylene glycol mono fatty acid ester, rapeseed oil, orange oil oil), rotenone, sorbitan fatty acid ester, starch, and the like;

(12) Other insecticide active ingredients: afidpyropene, benzpyrimoxan, broflanilide, chlorfenapyr, diafenthiuron, dichloromezotiaz, phenmezodithiaz, dimpropylidaz, DBEDC (dodecylbenzenesulphonic acidbisethylenediamine copper [II] salt), flonicamide, flometoquin, flufenerim, flupyradifurone, flupirimine, fluralaner, fluhexafon, fluxamethamide, hydramethylnon, indoxacarb, isocycloseram, metaflumizone, metaldehyde, nicotine sulfate sulfate, oxazosulfyl, pymetrozine, pyridalyl, pyrifluquinazon, spirotetramat, sulfoxaflor, tolfenpyrad, triazamate amate), triflumezopyrim, tyclopyrazoflor, indazapyroxameth, nicoflurole, flupyroxystrobin, spidoxamat, iron(II) phosphate, mivorilaner, modoflaner, tigolaner, umifoxolaner, and the like;

(13) Miticides: acequinocyl, acinonapyr, amidoflumet, amitraz, azocyclotin, benzomate, bifenazate, binapacryl, phenisobromorate, chinomethionate, Clofentezine, cyenopyrafen, cyflumetofen, tricyclohexyltin hydroxide, dicofol, dienochlor, etoxazole, fenazaflor, fenazaquin, fenbutatin oxide oxide), fenothiocarb, fenpyroximate, fluacrypyrim, hexythiazox, pyrimidifen, polynactins, propargyl, pyflubumid, pyridaben ), spirodiclofen, spiropidione, spiromesifen, spirobudifen, tebufenpyrad, tetradifon, and flupentiofenox, trifluenfuronate and the like;

(14) Nematicides Aluminum phosphide, benclothiaz, cadusafos, ethoprophos, fluazaindolizine, fluensulfone, fosthiazate, furfural, imicyafos, levamisole hydrochloride, mesulfenphos, metam-ammonium, carbam sodium, methyl isothiocyanate isothiocyanate, morantel tartrate, oxamyl, thioxazafen, 1,3-dichloropropene, DCIP, nemadectin, cyclobutrifluram, fluopyram, trifluenfuronate, and the like;

(15) Poison bait Examples of poison bait include chlorophacinone, coumatetralyl, diphacinone, sodium fluoroacetate, warfarin, and the like.

The compound of the present invention represented by the general formula (1) can also be present as a mixture with other active compounds other than compounds having pest control activity, acaricide activity or nematode control activity. In order to control diseases and/or weeds that occur simultaneously during the period of use, by mixing with a compound having fungicide activity, herbicidal activity or plant growth regulator activity and using it, it is possible to expect synergistic effects such as a reduction in the amount of drug as well as a reduction in the amount of control effort. In addition, by mixing with a repellent or synergist, it is possible to expect more effective control effects such as synergistic effects. Specific examples of fungicides, herbicides, compounds having plant growth regulator activity, repellents and synergists include the following.

Fungicide:
D-D (1,3-dichloropropene), acibenzolar, acibenzolar-S-methyl, aldimorph, ametoctradin, aminopyrifen, amisulbrom, amobam, andoprim, triazine (anilazine), azaconazole, azoxystrobin, basic copper sulfate sulfate), benodanil, benomyl, benthiavalicarb-isopropyl, benthiazole, bitertanol, bixafen, benzovindiflupyr, blasticidin-S, boscalid, bromuconazole, calcium carbonate, buthiobate, lime sulfur mixture polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, chinomethionate, chlorphenazole, chloroneb, chloropicrin, chlorothalonil (TPN), chlorzolinate, DBEDC (complex of bis(ethylenediamine) copper-bis-(dodecylbenzenesulfonic acid)), copper hydroxide hydroxide, copper nonylphenol sulfonate, basic copper chloride oxychloride, cumoxystrobin, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, dichlorone, diclobentiazox, diclocymet, diclomezine, diethofencarb, difenoconazole, diflumetrim, dimethomol Dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dithane-stainless, dithianon, dodine, echlomezole, edifenphos (EDDP), enestrobin, enoxastrobin, epoxyconazole, etaconazole, ethaboxam, extract from shiitake mushroom mycelium mushroom, famoxadone, fenamidone, phenaminestrobin, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpyrazamine zamine, ferimzone, florylpicoxamid, fluazinam, flufenoxystrobin, fluindapyr, flumetover, flumorph, fluopicolide, fluopyram, fluorimide, fluotrimazole, fluoxastrobin xastrobin, fluoxapiprolin, fluoxythioconazole, fluquinconazole, flusulfamide, flutolanil, fluxapyroxad, flumethylsulforim, folpet, fosetyl-aluminium, fthalide, fuberidazole fuberidazole, fludioxonil, flusilazole, flutianil, flutriafol, furametpyr, fluconazole, guazatine, hexaconazole, hydroxyisoxazole, hymexazol, imazalil, imazalil sulfate sulfate, imibenconazole, iminoctadine acetate, iminoctadine albesilate albesilate, ipfentrifluconazole, ipconazole, ipprobenfos (IBP), iprodione, iprovalicarb, isofetamide, isoflutipram, isoprothiolane, isopyrazam, isotianil, inpyrfluxam, ipferfenoquin, kasugamycin, cle Soximmethyl (kresoxim-methyl), mancozeb (mancozeb), maneb (maneb), manzeb (manzeb), mandestrobin (mandestrobin), mefentrifluconazole (mefentrifluconazole), mepanipyrim (mepanipyrim), mepronil (mepronil), metalaxyl (metalaxyl), metharylpicoxamide (metalylpicoxamid), carbam (metam-ammonium), carbam sodium (metam-sodium), metconazole (metconazole), methasulfocarb (methasulfocarb), methyl bromide (methyl bromide), methylisothiocyanate, methyltetraprole, metominostrobin, metrafenone, mildiomycin, myclobutanil, organosulfur nickel salts, nuarimol, orysastrobin, oxadixyl, oxathiapiprolin, organocupro (oxine-copper), oxolinic acid acid), oxpoconazole fumarate, oxycarboxin, oxytetracycline, pebulate, pefurazoate, penconazole, pencycuron, penflufen, Penthiopyrad, picarbutrazox, picoxystrobin, piperalin, polycarbamate, polyoxin-B, polyoxins, polyoxin zinc salt, potassium hydrogen carbonate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitrile, pyrifenox, pyrimethanil, pyriophenone, pyro ... Quilon (pyroquilon), pyriminostrobin (pyriminostrobin), pyrisoxazole (pyrisoxazole), pyrapropoyne (pyraziflumid), pyridaclomethyl (pyridachlormethyl), pencycuron (pencycuron), pydiflumetofen (pydiflumetofen), quinoxyfen (quinoxyfen), quintozene (quintozene), quinofumelin (quinofumelin), sedaxane (sedaxane), metallic silver (silver), simeconazole (simeconazole), sodium bicarbonate (sodium Hydrogen carbonate, sodium hypochlorite, spiroxamine, streptomycin, sulfur, tebuconazole, tecloftalam, terbinafine, tetraconazole, thiabendazole, thiadiazine, thifluzamide, thio

Thiophanate, thiophanate-methyl, thiuram, tiadinil, tolclofos-methyl, tolprocarb, tolylfluanid, triadimefon, triadimenol, triclopyricarb, tricyclazole lazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, tebufloquin, validamycin (-A), valifenalate, vinclozolin, zariramid, zinc sulfate sulfate), zineb, ziram, zoxamide, quinoxaline (chinomethionat), milneb, ecromezol (etridiazole), anhydrous copper sulfate, 8-hydroxyquinoline copper (oxine-copper), flufenoxadiazam, and the like;

Herbicides:
Aclonifen, acifluofen n-sodium, alachlor, alloxydim, amicarbazone, amidosulfuron, anilofos, asulam, atrazine, azimsulfuron, benfuresate, bensulfuron-methyl, Bentazon, benthiocarb, benzobicyclon, benzofenap, bialaphos, bifenox, bromobutide, bromoxynil, butamifos, cafenstrole, calcium peroxide peroxide), carbetamide, cinosulfuron, clomeprop, cyclosulfamuron, cyhalofop-butyl, daimuron, desmedipham, diclofop-methyl, diflufenican, dimefuron, dimethametryn, dinoterb, diquat Diquat, diuron, esprocarb, ethiozin, ethofumesate, ethoxysulfuron, etobenzanide, fenoxaprop-P-ethyl, fentrazamide, flucarbazone, flufenacet, flurtamone, fluthiacet-methyl , foramsulfuron, glufosinate, glyphosate isopropylamine salt amine), glyphosate trimesium salt, imazapyr, imazosulfuron, indanofan, iodosulfuron, ioxynil-octanoate, isoproturon, isoxadifen, isoxaflutole, lactofen, linuron , mefenacet, mesosulfuron, metamitron, methabenzthiazuron, methosulam, metribuzin, napropamide, neburon, oxadiargyl, oxadiazon, oxaziclomefone xaziclomefone, paraquat, pendimethalin, pentoxazone, phenmedipham, pretilachlor, propoxycarbazone, prosulfocarb, pyraclonil, pyraflufen-ethyl, pyrazolate, pyrazosulfuron-ethyl n-ethyl), pyributicarb, pyriftalid, pyriminobac-methyl, quizalofop-ethyl, sethoxydim, simazine, sulcotrione, sulfentrazone, thenylchlor, triaziflam, tribufos, broclozone, fumarate, Flusulfinam, iptriazopyride, flufenoximacil, dimesulfazet, fenquinotrione, ipfencarbazone, metazosulfuron, propyrisulfuron, simetryn, cinmethylin, tefuryltrione, and the like;

Compounds having plant growth regulating activity:
1-naphthylacetamide, 4-CPA, 6-benzylaminopurine, butralin, calcium chloride, calcium formate, calcium peroxide, calcium sulfate, chlormequat chloride, choline, cyanamide, cyclanilide, daminozide, decyl alcohol alcohol), dichlorprop, ethephon, ethychlozate, flurprimidol, forchlorfenuron, gibberellic acid, indolebutyric acid, maleic hydrazide potassium salt, mefenpyr, mepiquat chloride, oxine sulfate, 8-hydroxyquinone sulfate), paclobutrazol, paraffin, prohexadione calcium salt, prohydrojasmon, thidiazuron, trinexapac-ethyl, uniconazole-P, wax, and the like;

Repellents:
Capsaicin, carane-3,4-diol, citronellal, DEET, dimethyl phthalate, hinokitiol, limonene, linalool, menthol, menthone, naphthalene, thiuram, and the like;

Synergists:
Methylenedioxynaphthalene, naphthyl propynyl ether, nitrobenzyl thiocyanate, octachlorodipropyl ether, pentynyl phthalimide, phenyl salioxon, piperonyl butoxide, butoxide, safrole, sesamex, sesamin, sulfoxide, triphenyl phosphate, verbutin, and the like.

The compound of the present invention represented by the general formula (1) can be used as a biological pesticide, for example, in virus preparations such as cytoplasmic polyhedrosis virus (CPV), entomopox virus (EPV), granulosis virus (GV), and nuclear polyhedrosis virus (NPV), Beauveria bassiana, Beauveria brongniartii, and the like. iartii), Monocrosporium phymatophagum, Paecilomyces fumosoroseus, Pasteuria penetrans, Steinernema carpocapsae, Steinernema glaseri, Steinernema kushidae, Verticillium lecanii Microbial pesticides used as insecticides and nematocides, such as Verticillium lecanii and their mixtures, insect pheromones, insect attractants, RNAi preparations, Agrobacterium radiobacter, Bacillus subtilis, non-pathogenic Erwinia carotovora, non-pathogenic Fusarium oxysporum, Pseudomonas CAB-02, B-02), Pseudomonas fluorescens, Talaromyces flavus, Trichoderma atroviride, Trichoderma lignorum, and other microbial pesticides used as fungicides, and Xanthomonas campestris, and other biological pesticides used as herbicides, can be expected to have similar effects.

Furthermore, as biological pesticides, for example, Amblyseius californicus, Amblyseius cucumeris, Amblyseius degenerans, Aphidius colemani, Aphidoletes aphidimyza, Chrysoperia carnea, and conger eel are also used. Dacnusa sibirica, Diglyphus isaea, Encarsia formosana, Eretmocerus eremicus, Franklinothrips vespiformis, Harmonia axyridis, Hemiptarsenus varicornis ), Neochrysocharis formosa, Orius sauteri, Orius strigicollis, Phytoseiulus persimilis, Pilophorus typicus, Piocoris varius, and other natural enemies, codlelure It can also be used in combination with pheromones such as cuelure, geraniol, gyptol, liblure, looplure, methyl eugenol, orfralure, peachfluor, phycilure, pyrimalure, and turpentine.

The present invention will be explained in more detail below with reference to synthesis examples, formulation examples, and test examples of the compounds of the present invention, but the present invention is not limited to these examples.

Synthesis Example 1
Synthesis of 7-chloro-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (Compound No. 1-78) 5,7-Dichloroimidazo[1,2-a]pyridine (2.00 g, 10.7 mmol), 4-trifluoromethoxyphenol (2.29 g, 12.8 mmol), copper(I) iodide (611 mg, 3.21 mmol), tripotassium phosphate (2.70 g, 12.7 mmol), and picolinic acid (1.18 g, 9.62 mmol) were dissolved in dimethylsulfoxide (60 mL) and stirred at 110° C. for 4 hours. Water (100 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 7-chloro-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (yield 2.45 g, 70%) as a white solid.
Melting point: 95-96°C
^1H -NMR ( _CDCl3 ) σ: 7.76 (1H,s), 7.67 (1H,d,J=1.4Hz), 7.41 (1H,d,J=1.8Hz), 7.36 (2H,d,J=8.2Hz), 7.29-7.25 (2H,m), 5.95 (1H,d,J=1.8Hz).

Synthesis Example 2
Synthesis of 7-chloro-5-[[4-(trifluoromethoxy)phenyl]methoxy]imidazo[1,2-a]pyridine (Compound No. 1-89) [4-(trifluoromethoxy)phenyl]methanol (370 mg, 1.92 mmol) was dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (105 mg, 2.41 mmol) was added and stirred at room temperature (25° C.) for 10 minutes. Then, 5,7-dichloroimidazo[1,2-a]pyridine (300 mg, 1.60 mmol) was added and stirred at 80° C. for 3 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 7-chloro-5-[[4-(trifluoromethoxy)phenyl]methoxy]imidazo[1,2-a]pyridine (yield 384 mg, 70%).
Melting point: 100-102°C
^1H -NMR ( _CDCl3 ) σ: 7.64 (1H, s), 7.59 (1H, d, J = 1.4 Hz), 7.53-7.51 (2H, m), 7.36 (1H, d, J = 1.4 Hz), 7.31 (2H, d, J = 8.2 Hz), 6.17 (1H, d, J = 1.4 Hz), 5.30 (2H, s).

Synthesis Example 3
Synthesis of 7-chloro-5-cyclopropyl-imidazo[1,2-a]pyridine (Compound No. 1-783) 5,7-Dichloroimidazo[1,2-a]pyridine (200 mg, 1.07 mmol) and cyclopropylboronic acid (138 mg, 1.60 mmol) were dissolved in a toluene/water=1/1 mixed solvent (4 mL), and then nitrogen bubbling was performed for 5 minutes. Subsequently, tetrakis(triphenylphosphine)palladium(0) (124 mg, 0.107 mmol) and potassium carbonate (296 mg, 2.14 mmol) were added, and the reaction was performed at 110° C. for 1 hour using a microwave. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to give 7-chloro-5-cyclopropyl-imidazo[1,2-a]pyridine as a brown oil (yield 112 mg, 54%).
^1H -NMR ( _CDCl3 ) σ: 7.78 (1H,s), 7.69 (1H,d,J=1.4Hz), 7.55 (1H,d,J=1.8Hz), 6.58 (1H,d,J=1.8Hz), 2.05-2.03 (1H,m), 1.19-1.14 (2H,m), 0.88-0.84 (2H,m).

Synthesis Example 4
Synthesis of 7-cyclopropyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (Compound No. 1-410) 7-Chloro-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (300 mg, 0.913 mmol) and cyclopropylboronic acid (235 mg, 2.74 mmol) were dissolved in a 1,4-dioxane/water=2/1 mixed solvent (3 mL), and nitrogen bubbling was performed for 5 minutes. Subsequently, palladium(II) acetate (41.0 mg, 0.183 mmol), 2-dicyclohexylphosphino-2'-6'-dimethoxybiphenyl (150 mg, 0.365 mmol), and tripotassium phosphate (581 mg, 2.74 mmol) were added, and the mixture was reacted at 110°C for 1 hour using a microwave. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 7-cyclopropyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (yield: 112 mg, 54%) as a brown solid.
Melting point: 95-99°C
^1H -NMR ( _CDCl3 ) σ: 7.62 (1H,s), 7.59 (1H,s), 7.31 (2H,d,J=8.7Hz), 7.20-7.18 (2H,m), 7.10 (1H,s), 5.83 (1H,d,J=1.4Hz), 1.90-1.83 (1H,m), 1.01-0.97 (2H,m), 0.70-0.69 (2H,m).

Synthesis Example 5
Synthesis of 7-methyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (Compound No. 1-155) 4-Trifluoromethoxyphenol (253 mg, 1.42 mmol) and 5-bromo-7-methyl-imidazo[1,2-a]pyridine (200 mg, 0.948 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (196 mg, 1.42 mmol) was added and reacted at 120°C for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 7-methyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (yield 110 mg, 38%) as a pale orange oil.
^1H -NMR ( _CDCl3 ) σ: 7.66 (1H, s), 7.59 (1H, d, J = 0.9 Hz), 7.31 (2H, dd, J = 9.2, 0.9 Hz), 7.21-7.19 (3H, m), 5.86 (1H, d, J = 0.9 Hz), 2.34 (3H, d, J = 0.9 Hz).

Synthesis Example 6
Synthesis of 5-[4-(trifluoromethoxy)phenoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-328) 4-Trifluoromethoxyphenol (194 mg, 1.09 mmol) was dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (51.4 mg, 1.18 mmol) was added and stirred at room temperature (25° C.) for 10 minutes. Then, 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) was added and stirred at 80° C. for 3 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a pale yellow solid of 5-[4-(trifluoromethoxy)phenoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 297 mg, 90%).
Melting point: 92-95°C
^1H -NMR ( _CDCl3 ) σ: 7.90 (1H, s), 7.82 (1H, d, J = 1.4 Hz), 7.74 (1H, s), 7.37 (2H, d, J = 8.7 Hz), 7.29-7.26 (2H, m), 6.10 (1H, d, J = 1.4 Hz).

Synthesis Example 7
Synthesis of 7-chloro-5-[4-(trifluoromethoxy)phenoxy]-[1,2,4]triazolo[4,3-a]pyridine (Compound No. 2-78) 5,7-Dichloro[1,2,4]triazolo[4,3-a]pyridine (300 mg, 1.60 mmol), 4-trifluoromethoxyphenol (341 mg, 1.91 mmol), copper(I) iodide (91.2 mg, 0.479 mmol), tripotassium phosphate (403 mg, 1.90 mmol), and picolinic acid (177 mg, 1.44 mmol) were dissolved in dimethylsulfoxide (1 mL) and stirred at 110° C. for 4 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 2.45 g (yield 70%) of 7-chloro-5-[4-(trifluoromethoxy)phenoxy]-[1,2,4]triazolo[4,3-a]pyridine as a white solid.
Melting point: 177-179°C
^1H -NMR ( _CDCl3 ) σ: 9.00 (1H, s), 7.53 (1H, s), 7.40 (2H, d, J = 9.2 Hz), 7.32-7.31 (2H, m), 5.88 (1H, d, J = 1.4 Hz).

Synthesis Example 8
Synthesis of 7-cyclopropyl-5-[4-(trifluoromethoxy)phenoxy]-[1,2,4]triazolo[4,3-a]pyridine (compound number 2-398) 7-Chloro-5-[4-(trifluoromethoxy)phenoxy]-[1,2,4]triazolo[4,3-a]pyridine (300 mg, 0.910 mmol) and cyclopropylboronic acid (219 mg, 2.55 mmol) were dissolved in a toluene/water=1/1 mixed solvent (4 mL), and nitrogen bubbling was performed for 5 minutes. Subsequently, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (33.3 mg, 0.183 mmol) and potassium carbonate (352 mg, 2.55 mmol) were added, and the mixture was reacted at 110°C for 1 hour using a microwave. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 7-cyclopropyl-5-[4-(trifluoromethoxy)phenoxy]-[1,2,4]triazolo[4,3-a]pyridine (yield 106 mg, 35%) as a gray solid.
Melting point: 130-132°C
^1H -NMR ( _CDCl3 ) σ: 8.89 (1H, s), 7.36 (2H, d, J = 8.7 Hz), 7.29-7.25 (2H, m), 7.15 (1H, s), 5.71 (1H, d, J = 0.9 Hz), 1.90-1.83 (1H, m), 1.06-1.01 (2H, m), 0.74-0.71 (2H, m).

Synthesis Example 9
Synthesis of 7-chloro-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,5-a]pyridine (Compound No. 3-78) 5,7-Dichloroimidazo[1,5-a]pyridine (286 mg, 1.53 mmol), 4-trifluoromethoxyphenol (327 mg, 1.84 mmol), copper(I) iodide (87.4 mg, 0.459 mmol), tripotassium phosphate (386 mg, 1.82 mmol), and picolinic acid (169 mg, 1.38 mmol) were dissolved in dimethylsulfoxide (1 mL) and stirred at 110° C. for 4 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a brown solid of 7-chloro-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,5-a]pyridine (yield: 155 g, 31%).
Melting point: 89-95°C
^1H -NMR ( _CDCl3 ) σ: 8.33 (1H, s), 7.45 (1H, s), 7.36 (2H, d, J = 8.7 Hz), 7.30-7.27 (2H, m), 7.23 (1H, d, J = 0.9 Hz), 5.66 (1H, d, J = 1.8 Hz).

Synthesis Example 10
Synthesis of 7-cyclopropyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,5-a]pyridine (Compound No. 3-397) 7-Chloro-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,5-a]pyridine (164 mg, 0.499 mmol) and cyclopropylboronic acid (51.4 mg, 0.599 mmol) were dissolved in a 1,4-dioxane/water=2/1 mixed solvent (3 mL), and nitrogen bubbling was performed for 5 minutes. Subsequently, palladium(II) acetate (22.4 mg, 0.0998 mmol), 2-dicyclohexylphosphino-2'-6'-dimethoxybiphenyl (81.9 mg, 0.200 mmol), and tripotassium phosphate (318 mg, 1.50 mmol) were added, and the mixture was reacted at 110°C for 1 hour using a microwave. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a brown solid of 7-cyclopropyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,5-a]pyridine (yield 85 mg, 51%).
Melting point: 76-80°C
^1H -NMR ( _CDCl3 ) σ: 8.20 (1H,s), 7.36 (1H,s), 7.31 (2H,d,J=8.2Hz), 7.23-7.20 (2H,m), 6.92 (1H,s), 5.57 (1H,d,J=0.9Hz), 1.82-1.75 (1H,m), 0.92-0.90 (2H,m), 0.63-0.61 (2H,m).

Synthesis Example 11
Synthesis of 5-[(5-chloro-2-pyridyl)sulfanyl]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1334) 5-Chloropyridine-2-thiol (158 mg, 1.09 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (51.4 mg, 1.18 mmol) was added and reacted at 160° C. for 3 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 5-[(5-chloro-2-pyridyl)sulfanyl]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 80.0 mg, 27%).
Melting point: 90-92°C
^1H -NMR ( _CDCl3 ) δ: 8.31 (1H, d, J = 2.3 Hz), 8.09 (1H, s), 7.78 (1H, d, J = 1.4 Hz), 7.73 (1H, s), 7.56 (1H, dd, J = 8.5, 2.5 Hz), 7.48 (1H, d, J = 1.4 Hz), 7.01 (1H, d, J = 8.7 Hz).

Synthesis Example 12
Synthesis of 7-methoxy-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (compound number 1-371) 4-(trifluoromethoxy)phenol (585 mg, 3.29 mmol) and 5-chloro-7-methoxy-imidazo[1,2-a]pyridine (400 mg, 2.19 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (393 mg, 2.85 mmol) was added and reacted at 160°C for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 7-methoxy-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (yield 520 mg, 73%) as a white solid.
Melting point: 144-146°C
^1H -NMR ( _CDCl3 ) δ: 7.60 (1H,s), 7.52 (1H,s), 7.32 (2H,d,J=8.7Hz), 7.24-7.22 (2H,m), 6.69 (1H,d,J=1.8Hz), 5.69 (1H,d,J=1.8Hz), 3.83 (3H,s).

Synthesis Example 13
Synthesis of 7-methoxy-5-[4-(trifluoromethyl)phenyl]sulfanyl-imidazo[1,2-a]pyridine (compound number 1-1406) 4-(trifluoromethyl)benzenethiol (176 mg, 0.986 mmol) and 5-chloro-7-methoxy-imidazo[1,2-a]pyridine (150 mg, 0.821 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (46.6 mg, 1.07 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to give 7-methoxy-5-[4-(trifluoromethyl)phenyl]sulfanyl-imidazo[1,2-a]pyridine (yield 125 mg, 47%) as a brown solid.
Melting point: 124-126°C
^1H -NMR ( _CDCl3 ) δ: 7.54 (2H, d, J = 7.8 Hz), 7.47 (1H, d, J = 1.4 Hz), 7.43 (1H, s), 7.26 (2H, d, J = 7.8 Hz), 7.01 (1H, d, J = 2.3 Hz), 6.91 (1H, d, J = 2.3 Hz), 3.89 (3H, s).

Synthesis Example 14
Synthesis of 7-(trifluoromethyl)-5-[4-(trifluoromethyl)phenyl]sulfanyl-imidazo[1,2-a]pyridine (Compound No. 1-1328) 4-(trifluoromethyl)benzenethiol (194 mg, 1.09 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (51.4 mg, 1.18 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 7-(trifluoromethyl)-5-[4-(trifluoromethyl)phenyl]sulfanyl-imidazo[1,2-a]pyridine (yield 226 mg, 81%).
Melting point: 128-130°C
^1H -NMR ( _CDCl3 ) δ: 8.07 (1H, s), 7.80 (1H, d, J = 1.4 Hz), 7.70 (1H, s), 7.57 (2H, d, J = 8.7 Hz), 7.38 (1H, d, J = 1.4 Hz), 7.28 (2H, d, J = 8.7 Hz).

Synthesis Example 15
Synthesis of 5-(4-methylphenylsulfanyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1325) 4-Methylbenzenethiol (135 mg, 1.09 mmol) was dissolved in dimethylformamide (1 mL), and the solution was cooled to 0° C. in an ice bath, and 55% sodium hydride (51.4 mg, 1.18 mmol) was added and stirred for 5 minutes. Subsequently, 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) was added in an ice bath, and the mixture was reacted at room temperature (25° C.) for 3 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 5-(4-methylsulfanyl)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 118 mg, 42%) as a white solid.
Melting point: 104-106°C
^1H -NMR ( _CDCl3 ) δ: 7.90 (1H,s), 7.78 (1H,s), 7.77 (1H,s), 7.31 (2H,d,J=7.8Hz), 7.21 (2H,d,J=7.8Hz), 6.95 (1H,d,J=1.4Hz), 2.38 (3H,s).

Synthesis Example 16
Synthesis of 5-(cyclohexyloxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1214) Cyclohexanol (109 mg, 1.09 mmol) was dissolved in dimethylformamide (1 mL), and the solution was cooled to 0° C. in an ice bath, and 55% sodium hydride (51.4 mg, 1.18 mmol) was added and stirred for 5 minutes. Subsequently, 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) was added in an ice bath, and the mixture was reacted at room temperature (25° C.) for 3 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 5-(cyclohexyloxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine as a pale yellow oil (yield 235 mg, 91%).
^1H -NMR ( _CDCl3 ) δ: 7.75 (1H,s), 7.71 (1H,d,J=0.9Hz), 7.57 (1H,s), 6.17 (1H,d,J=0.9Hz), 4.67-4.61 (1H,m), 2.09-2.06 (2H,m), 1.91-1.71 (4H,m), 1.64-1.62 (1H,m), 1.56-1.40 (3H,m).

Synthesis Example 17
Synthesis of 5-(4-isopropylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1226) 4-Isopropylphenol (111 mg, 0.816 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (150 mg, 0.680 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (38.6 mg, 0.884 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 5-(4-isopropylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 160 mg, 74%) as a white solid.
Melting point: 118-120°C
^1H -NMR ( _CDCl3 ) δ: 7.92 (1H,s), 7.80 (1H,d,J=0.9Hz), 7.68 (1H,s), 7.36-7.34 (2H,m), 7.16-7.14 (2H,m), 6.06 (1H,d,J=1.4Hz), 3.03-2.96 (1H,m), 1.31 (6H,d,J=7.3Hz).

Synthesis Example 18
Synthesis of 5-(4-isopropyl-3-methyl-phenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1291) 4-Isopropyl-3-methyl-phenol (123 mg, 0.816 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (150 mg, 0.680 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (38.6 mg, 0.884 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a pale orange solid of 5-(4-isopropyl-3-methyl-phenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 209 mg, 92%).
Melting point: 106-109°C
^1H -NMR ( _CDCl3 ) δ: 7.90 (1H,s), 7.79 (1H,d,J=1.4Hz), 7.67 (1H,s), 7.34 (1H,d,J=8.2Hz), 7.03 (1H,dd,J=8.5,2.5Hz), 6.99 (1H,d,J=2.7Hz), 6.08 (1H,d,J=1.4Hz), 3.21-3.14 (1H,m), 2.39 (3H,s), 1.28 (6H,d,J=6.9Hz).

Synthesis Example 19
Synthesis of 7-isopropyl-5-(4-methylphenylsulfanyl)imidazo[1,2-a]pyridine (Compound No. 1-1045) 4-Methylbenzenethiol (306 mg, 2.47 mmol) and 5-chloro-7-isopropyl-imidazo[1,2-a]pyridine (400 mg, 2.05 mmol) were dissolved in dimethylformamide (2 mL), and potassium carbonate (369 mg, 2.67 mmol) was added and reacted at 150°C for 2 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 7-isopropyl-5-(4-methylphenylsulfanyl)imidazo[1,2-a]pyridine (yield 600 mg, 100%) as a brown oil.
^1H -NMR ( _CDCl3 ) σ: 7.53 (2H, d, J = 9.6 Hz), 7.43 (1H, s), 7.16-7.09 (4H, m), 6.92 (1H, d, J = 1.4 Hz), 2.95-2.88 (1H, m), 2.31 (3H, s), 1.27 (6H, d, J = 6.9 Hz).

Synthesis Example 20
Synthesis of 7-isopropyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (Compound No. 1-238) 4-Trifluoromethoxyphenol (440 mg, 2.47 mmol) and 5-chloro-7-isopropyl-imidazo[1,2-a]pyridine (400 mg, 2.06 mmol) were dissolved in dimethylformamide (2 mL), and potassium carbonate (370 mg, 2.68 mmol) was added and reacted at 150°C for 3 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 7-isopropyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (yield 120 mg, 17%) as a white solid.
Melting point: 92-95°C
^1H -NMR ( _CDCl3 ) σ: 7.64 (1H, d, J = 1.4 Hz), 7.61 (1H, d, J = 1.4 Hz), 7.31 (2H, d, J = 8.7 Hz), 7.25 (1H, s), 7.19 (2H, d, J = 8.7 Hz), 5.97 (1H, d, J = 1.4 Hz), 2.91-2.84 (1H, m), 1.23 (6H, d, J = 6.9 Hz).

Synthesis Example 21
Synthesis of 7-tert-butyl-5-(4-chlorophenyl)sulfanyl-imidazo[1,2-a]pyridine (Compound No. 1-316) 4-Chlorobenzenethiol (416 mg, 2.88 mmol) and 5-chloro-7-tert-butyl-imidazo[1,2-a]pyridine (400 mg, 1.92 mmol) were dissolved in dimethylformamide (2 mL), and potassium carbonate (530 mg, 3.83 mmol) was added and reacted at 150°C for 2 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 7-tert-butyl-5-(4-chlorophenyl)sulfanyl-imidazo[1,2-a]pyridine (yield 340 mg, 56%) as a yellow oil.
^1H -NMR ( _CDCl3 ) σ: 7.63 (1H, d, J = 1.4 Hz), 7.56 (1H, d, J = 1.4 Hz), 7.51 (1H, s), 7.27-7.25 (3H, m), 7.12-7.08 (2H, m), 1.37 (9H, s).

Synthesis Example 22
Synthesis of 5-(4-secondary butylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1229) 4-Secondary butylphenol (122 mg, 0.816 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (150 mg, 0.680 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (38.6 mg, 0.884 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 5-(4-sec-butylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 181 mg, 79%) as a white solid.
Melting point: 94-97°C
^1H -NMR ( _CDCl3 ) δ: 7.92 (1H,s), 7.80 (1H,d,J=1.4Hz), 7.68 (1H,s), 7.32-7.29 (2H,m), 7.16-7.14 (2H,m), 6.06 (1H,d,J=1.4Hz), 2.70-2.67 (1H,m), 1.68-1.60 (2H,m), 1.29 (3H,d,J=6.9Hz), 0.87 (3H,t,J=7.6Hz).

Synthesis Example 23
Synthesis of 5-(4-propylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1225) 4-Propylphenol (111 mg, 0.816 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (150 mg, 0.680 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (38.6 mg, 0.884 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 5-(4-propylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 182 mg, 83%) as a white solid.
Melting point: 80-82°C
^1H -NMR ( _CDCl3 ) δ: 7.92 (1H, s), 7.80 (1H, d, J = 0.9 Hz), 7.68 (1H, s), 7.31-7.29 (2H, m), 7.15-7.13 (2H, m), 6.05 (1H, d, J = 1.4 Hz), 2.66 (2H, dd, J = 7.8, 3.9 Hz), 1.72-1.68 (2H, m), 0.99 (3H, t, J = 7.3 Hz).

Synthesis Example 24
Synthesis of 5-[4-(1,1-dimethylpropyl)phenoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1218) 4-(1,1-dimethylpropyl)phenol (134 mg, 0.816 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (150 mg, 0.680 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (38.6 mg, 0.884 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 5-[4-(1,1-dimethylpropyl)phenoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 212 mg, 89%).
Melting point: 129-132°C
^1H -NMR ( _CDCl3 ) δ: 7.92 (1H, s), 7.80 (1H, d, J = 0.9 Hz), 7.68 (1H, s), 7.46-7.43 (2H, m), 7.17-7.14 (2H, m), 6.07 (1H, d, J = 1.4 Hz), 1.69 (2H, q, J = 7.5 Hz), 1.34 (6H, s), 0.73 (3H, t, J = 7.6 Hz).

Synthesis Example 25
Synthesis of 5-(3-fluoro-4-methyl-phenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1290) 3-Fluoro-4-methyl-phenol (103 mg, 0.816 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (150 mg, 0.680 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (38.6 mg, 0.884 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 5-(3-fluoro-4-methyl-phenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 212 mg, 89%).
Melting point: 131-132°C
^1H -NMR ( _CDCl3 ) δ: 7.89 (1H,s), 7.80 (1H,d,J=0.9Hz), 7.71 (1H,s), 7.31 (1H,t,J=8.0Hz), 6.95 (1H,s), 6.93 (1H,s), 6.10 (1H,d,J=1.4Hz), 2.34 (3H,d,J=1.8Hz).

Synthesis Example 26
Synthesis of 5-(4-ethylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1224) 4-Ethylphenol (99.7 mg, 0.816 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (150 mg, 0.680 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (38.6 mg, 0.884 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a pale orange solid of 5-(4-ethylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 116 mg, 56%).
Melting point: 95-98°C
^1H -NMR ( _CDCl3 ) δ: 7.92 (1H, s), 7.80 (1H, d, J = 1.4 Hz), 7.68 (1H, s), 7.34-7.31 (2H, m), 7.16-7.13 (2H, m), 6.05 (1H, d, J = 1.4 Hz), 2.73 (2H, q, J = 7.6 Hz), 1.30 (3H, t, J = 7.8 Hz).

Synthesis Example 27
Synthesis of 5-(4-cyclopropylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1267) 4-Cyclopropylphenol (109 mg, 0.816 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (150 mg, 0.680 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (38.6 mg, 0.884 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 5-(4-cyclopropylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 107 mg, 49%) as a white solid.
Melting point: 115-117°C
^1H -NMR ( _CDCl3 ) δ: 7.92 (1H,s), 7.79 (1H,s), 7.67 (1H,s), 7.19 (2H,d,J=8.2Hz), 7.12 (2H,d,J=8.7Hz), 6.02 (1H,s), 2.00-1.93 (1H,m), 1.07-1.02 (2H,m), 0.77-0.73 (2H,m).

Synthesis Example 28
Synthesis of 5-[4-(methoxymethyl)phenoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1237) 4-(Methoxymethyl)phenol (113 mg, 0.816 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (150 mg, 0.680 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (38.6 mg, 0.884 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a gray solid of 5-[4-(methoxymethyl)phenoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 43.8 mg, 20%).
Melting point: 61-64°C
^1H -NMR ( _CDCl3 ) δ: 7.92 (1H,s), 7.80 (1H,d,J=0.9Hz), 7.69 (1H,s), 7.49 (2H,d,J=8.7Hz), 7.23-7.22 (2H,m), 6.06 (1H,d,J=1.4Hz), 4.52 (2H,s), 3.47 (3H,s).

Synthesis Example 29
Synthesis of 5-cyclohexylsulfanyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1323) Cyclohexanethiol (137 mg, 1.18 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (196 mg, 1.42 mmol) was added and reacted at 120°C for 1.5 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 5-cyclohexylsulfanyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 130 mg, 48%) as a brown oil.
^1H -NMR ( _CDCl3 ) δ: 7.99 (1H,s), 7.88 (1H,s), 7.81 (1H,s), 7.09 (1H,d,J=1.8Hz), 3.33-3.31 (1H,m), 1.97-1.96 (2H,m), 1.81-1.79 (2H,m), 1.53-1.45 (2H,m), 1.35-1.29 (4H,m).

Synthesis Example 30
Synthesis of 5-(4-tert-butylphenyl)sulfanyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1327) 4-tert-butylbenzenethiol (196 mg, 1.18 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (196 mg, 1.42 mmol) was added and reacted at 120° C. for 1.5 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a brown solid of 5-(4-tert-butylphenyl)sulfanyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 140 mg, 44%).
^1H -NMR ( _CDCl3 ) δ: 7.90 (1H,s), 7.79 (1H,s), 7.77 (1H,d,J=1.4Hz), 7.39 (2H,d,J=6.6Hz), 7.31 (2H,d,J=6.6Hz), 7.00 (1H,d,J=1.4Hz), 1.30 (9H,s).

Synthesis Example 31
Synthesis of 5-(4-methylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-327) p-Cresol (127 mg, 1.18 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (196 mg, 1.42 mmol) was added and reacted with microwaves at 120°C for 1.5 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 5-(4-methylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 130 mg, 49%) as a brown solid.
Melting point: 100-104°C
^1H -NMR ( _CDCl3 ) δ: 7.91 (1H,s), 7.79 (1H,d,J=1.4Hz), 7.66 (1H,s), 7.29 (2H,d,J=8.2Hz), 7.11 (2H,d,J=8.2Hz), 6.01 (1H,d,J=1.4Hz), 2.42 (3H,s).

Synthesis Example 32
Synthesis of 5-(4-tert-butoxyphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1259) 4-tert-butoxyphenol (196 mg, 1.18 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (196 mg, 1.42 mmol) was added and reacted at 120° C. for 1.5 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a milky white solid of 5-(4-tert-butoxyphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 220 mg, 69%).
Melting point: 129-132°C
^1H -NMR ( _CDCl3 ) δ: 7.90 (1H,s), 7.79 (1H,d,J=1.4Hz), 7.67 (1H,s), 7.13-7.10 (4H,m), 6.02 (1H,d,J=1.4Hz), 1.39 (9H,s).

Synthesis Example 33
Synthesis of 5-(4-tert-butylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1230) 4-tert-butylphenol (177 mg, 1.18 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (196 mg, 1.42 mmol) was added and reacted at 120° C. for 1.5 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 5-(4-tert-butylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 130 mg, 42%).
Melting point: 178-180°C
^1H -NMR ( _CDCl3 ) δ: 7.90 (1H,s), 7.79 (1H,d,J=1.4Hz), 7.67 (1H,s), 7.49 (2H,d,J=8.7Hz), 7.14 (2H,d,J=8.7Hz), 6.07 (1H,d,J=1.4Hz), 1.37 (9H,s).

Synthesis Example 34
Synthesis of 5-(4-isopropylphenyl)sulfanyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1326) 4-Isopropylbenzenethiol (179 mg, 1.18 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (196 mg, 1.42 mmol) was added and reacted at 120° C. for 1.5 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a pale orange solid of 5-(4-isopropylphenyl)sulfanyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 250 mg, 82%).
Melting point: 78-81°C
^1H -NMR ( _CDCl3 ) δ: 7.89 (1H,s), 7.78 (1H,s), 7.77 (1H,s), 7.32 (2H,d,J=8.2Hz), 7.24-7.21 (2H,m), 6.97 (1H,s), 2.94-2.87 (1H,m), 1.24 (6H,d,J=6.9Hz).

Synthesis Example 35
Synthesis of 5-cyclopentylsulfanyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1322) Cyclopentanethiol (120 mg, 1.18 mmol) was dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (51 mg, 1.18 mmol) was added and stirred at room temperature (25°C) for 10 minutes. Then, 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) was added and reacted at 80°C for 2 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to give 5-cyclopentylsulfanyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine as a brown oil (yield 215 mg, 83%).
^1H -NMR ( _CDCl3 ) δ: 7.89 (1H,s), 7.84 (1H,s), 7.81 (1H,s), 7.00 (1H,s), 3.82-3.76 (1H,m), 2.16-2.10 (2H,m), 1.86-1.84 (2H,m), 1.75-1.66 (4H,m).

Synthesis Example 36
Synthesis of 5-propylsulfanyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1317) Propane-1-thiol (90 mg, 1.18 mmol) was dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (51 mg, 1.18 mmol) was added and stirred at room temperature (25°C) for 10 minutes. Then, 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) was added and reacted at 80°C for 2 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to give 5-propylsulfanyl-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 100 mg, 42%) as a black solid.
Melting point: 51-53°C
^1H -NMR ( _CDCl3 ) δ: 7.86 (1H, s), 7.84 (1H, s), 7.82 (1H, d, J = 0.9 Hz), 6.94 (1H, d, J = 0.9 Hz), 3.06 (2H, t, J = 7.3 Hz), 1.76 (2H, dd, J = 14.7, 7.3 Hz), 1.09 (3H, d, J = 7.3 Hz).

Synthesis Example 37
Synthesis of 5-(4-methylsulfanylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1281) 4-Methylsulfanylphenol (165 mg, 1.18 mmol) was dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (51 mg, 1.18 mmol) was added and stirred at room temperature (25° C.) for 10 minutes. Then, 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) was added and reacted at 80° C. for 2 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a pale yellow solid of 5-(4-methylsulfanylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 150 mg, 51%).
Melting point: 106-108°C
^1H -NMR ( _CDCl3 ) δ: 7.90 (1H,s), 7.79 (1H,d,J=1.4Hz), 7.68 (1H,s), 7.36 (2H,d,J=8.7Hz), 7.16 (2H,d,J=8.7Hz), 6.03 (1H,d,J=1.4Hz), 2.53 (3H,s).

Synthesis Example 38
Synthesis of 5-(4-isobutylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1228) 4-Isobutylphenol (177 mg, 1.18 mmol) was dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (51 mg, 1.18 mmol) was added and stirred at room temperature (25° C.) for 10 minutes. Then, 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) was added and reacted at 80° C. for 2 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 5-(4-isobutylphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 130 mg, 43%) as a white solid.
Melting point: 106-109°C
^1H -NMR ( _CDCl3 ) δ: 7.90 (1H,s), 7.78 (1H,d,J=1.4Hz), 7.66 (1H,s), 7.25 (2H,d,J=8.7Hz), 7.12 (2H,d,J=8.7Hz), 6.03 (1H,d,J=1.4Hz), 2.53 (2H,d,J=6.9Hz), 1.95-1.84 (1H,m), 0.93 (6H,d,J=6.9Hz).

Synthesis Example 39
Synthesis of 5-(4-ethoxyphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1254) 4-Ethoxyphenol (163 mg, 1.18 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (196 mg, 1.42 mmol) was added and reacted at 120° C. for 1.5 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 5-(4-ethoxyphenoxy)-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 150 mg, 51%) as a white solid.
Melting point: 112-114°C
^1H -NMR ( _CDCl3 ) δ: 7.92 (1H, s), 7.78 (1H, d, J = 1.4 Hz), 7.64 (1H, s), 7.14 (2H, d, J = 8.7 Hz), 6.98 (2H, d, J = 8.7 Hz), 5.96 (1H, d, J = 1.4 Hz), 4.07 (2H, q, J = 6.9 Hz), 1.45 (3H, t, J = 6.9 Hz).

Synthesis Example 40
Synthesis of 5-[4-(2,2-dimethylpropyl)phenoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-1233) 4-(2,2-dimethylpropyl)phenol (179 mg, 1.18 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (196 mg, 1.42 mmol) was added and reacted at 120° C. for 1.5 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 5-[4-(2,2-dimethylpropyl)phenoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 160 mg, 51%).
Melting point: 143-146°C
^1H -NMR ( _CDCl3 ) δ: 7.90 (1H,s), 7.78 (1H,d,J=1.4Hz), 7.66 (1H,s), 7.26 (2H,d,J=8.7Hz), 7.12 (2H,d,J=8.7Hz), 6.04 (1H,d,J=1.4Hz), 2.53-2.46 (1H,m), 1.80-1.76 (1H,m), 1.27 (3H,d,J=6.9Hz), 0.95 (3H,d,J=6.9Hz), 0.78 (3H,d,J=6.4Hz).

Synthesis Example 41
Synthesis of 7-(trifluoromethyl)-5-[4-(trifluoromethylsulfanyl)phenoxy]imidazo[1,2-a]pyridine (compound number 1-1282) 4-(trifluoromethylsulfanyl)phenol (528 mg, 2.72 mmol) was dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (129 mg, 2.95 mmol) was added and stirred at room temperature (25° C.) for 10 minutes. Then, 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (500 mg, 2.27 mmol) was added and reacted at 80° C. for 2 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a brown solid of 7-(trifluoromethyl)-5-[4-(trifluoromethylsulfanyl)phenoxy]imidazo[1,2-a]pyridine (yield 357 mg, 42%).
Melting point: 90-92°C
^1H -NMR ( _CDCl3 ) δ: 7.86 (1H, s), 7.82-7.79 (4H, m), 7.29-7.26 (2H, m), 6.23 (1H, d, J=1.4 Hz).

Synthesis Example 42
Synthesis of 5-[(2-fluorophenyl)methoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1296) (2-fluorophenyl)methanol (170 mg, 1.40 mmol) and 5-chloro-7-trifluoromethyl-imidazo[1,2-a]pyridine (250 mg, 1.10 mmol) were dissolved in dimethylformamide (3 mL), and sodium hydride (64 mg, 1.50 mmol) was added and reacted at 110° C. for 1 hour. Water (10 mL) was poured into the ice-cooled reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane=1/1) to obtain a white solid 5-[(2-fluorophenyl)methoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 130 mg, 37%).
Melting point: 116-118°C
^1H -NMR ( _CDCl3 ) σ: 7.56 (1H,s), 7.71 (1H,d), 7.65 (1H,s), 7.55-7.51 (1H,dt), 7.47-7.42 (1H,m), 7.25-7.16 (2H,m), 6.36-6.35 (1H,s), 5.43 (2H,s).

Synthesis Example 43
Synthesis of 5-{[2-(trifluoromethoxy)phenyl]methoxy}-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1300) [2-(trifluoromethoxy)phenyl]methanol (260 mg, 1.40 mmol) and 5-chloro-7-trifluoromethyl-imidazo[1,2-a]pyridine (250 mg, 1.10 mmol) were dissolved in dimethylformamide (3 mL), and sodium hydride (64 mg, 1.50 mmol) was added and reacted at 110° C. for 1 hour. Water (10 mL) was poured into the ice-cooled reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid, 5-{[2-(trifluoromethoxy)phenyl]methoxy}-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 380 mg, 89%).
Melting point: 97-99°C
^1H -NMR ( _CDCl3 ) σ: 7.75 (1H, s), 7.72 (1H, d, J = 1.4 Hz), 7.66 (1H, s), 7.61-7.60 (1H, m), 7.50 (1H, td, J = 7.7, 1.7 Hz), 7.42-7.38 (2H, m), 6.32 (1H, d, J = 1.4 Hz), 5.44 (2H, s).

Synthesis Example 44
Synthesis of 5-[(2,3-difluorophenyl)methoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1312) (2,3-difluorophenyl)methanol (200 mg, 1.40 mmol) and 5-chloro-7-trifluoromethyl-imidazo[1,2-a]pyridine (250 mg, 1.10 mmol) were dissolved in dimethylformamide (3 mL), and sodium hydride (64 mg, 1.50 mmol) was added and reacted at 110° C. for 1 hour. Water (10 mL) was poured into the ice-cooled reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid, 5-[(2,3-difluorophenyl)methoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 90 mg, 20%).
Melting point: 114-118°C
^1H -NMR ( _CDCl3 ) σ: 7.75 (1H,s), 7.73 (1H,s), 7.67 (1H,s), 7.29-7.28 (2H,m), 7.23-7.19 (1H,m), 6.34 (1H,s), 5.45 (2H,s).

Synthesis Example 45
Synthesis of 5-[(2,4-difluorophenyl)methoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1313) (2,4-difluorophenyl)methanol (200 mg, 1.40 mmol) and 5-chloro-7-trifluoromethyl-imidazo[1,2-a]pyridine (250 mg, 1.10 mmol) were dissolved in dimethylformamide (3 mL), and sodium hydride (64 mg, 1.50 mmol) was added and reacted at 110° C. for 1 hour. Water (10 mL) was poured into the ice-cooled reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 5-[(2,4-difluorophenyl)methoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 110 mg, 30%).
Melting point: 116-118°C
^1H -NMR ( _CDCl3 ) σ: 7.73-7.72 (2H,m), 7.66 (1H,s), 7.53-7.51 (1H,m), 7.01-6.93 (2H,m), 6.34 (1H,s), 5.38 (2H,s).

Synthesis Example 46
Synthesis of 5-[(2,5-difluorophenyl)methoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1314) (2,5-difluorophenyl)methanol (200 mg, 1.40 mmol) and 5-chloro-7-trifluoromethyl-imidazo[1,2-a]pyridine (250 mg, 1.10 mmol) were dissolved in dimethylformamide (3 mL), and sodium hydride (64 mg, 1.50 mmol) was added and reacted at 110° C. for 1 hour. Water (10 mL) was poured into the ice-cooled reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a yellow solid of 5-[(2,5-difluorophenyl)methoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 130 mg, 35%).
Melting point: 97-102°C
^1H -NMR ( _CDCl3 ) σ: 7.77 (1H,s), 7.74 (1H,s), 7.67 (1H,s), 7.25-7.24 (1H,m), 7.17-7.13 (2H,m), 6.33 (1H,s), 5.41 (2H,s).

Synthesis Example 47
Synthesis of 5-[(2,6-difluorophenyl)methoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1315) (2,6-difluorophenyl)methanol (160 mg, 1.09 mmol) and 5-chloro-7-trifluoromethyl-imidazo[1,2-a]pyridine (200 mg, 0.91 mmol) were dissolved in dimethylformamide (3 mL), and sodium hydride (51 mg, 1.18 mmol) was added and reacted at 110° C. for 1 hour. Water (10 mL) was poured into the ice-cooled reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 5-[(2,6-difluorophenyl)methoxy]-7-(trifluoromethyl)imidazo[1,2-a]pyridine (yield 130 mg, 35%).
Melting point: 92-94°C
^1H -NMR ( _CDCl3 ) σ: 7.71 (1H,s), 7.69 (1H,s), 7.65 (1H,s), 7.48-7.41 (1H,m), 7.02 (2H,t,J=7.8Hz), 6.42 (1H,s), 5.47 (2H,s).

Synthesis Example 48
Synthesis of 5-benzyloxy-7-(trifluoromethyl)imidazo[1,2-a]pyridine (compound number 1-358) Phenylmethanol (127 mg, 1.18 mmol) and 5-chloro-7-(trifluoromethyl)imidazo[1,2-a]pyridine (200 mg, 0.907 mmol) were dissolved in dimethylformamide (1 mL), and potassium carbonate (196 mg, 1.42 mmol) was added and reacted with microwaves at 120°C for 1.5 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 5-benzyloxy-7-(trifluoromethyl)imidazo[1,2-a]pyridine as a pale yellow solid (yield: 70 mg, 26%).
Melting point: 91-92°C
^1H -NMR ( _CDCl3 ) δ: 7.76 (1H,s), 7.70 (1H,s), 7.62 (1H,s), 7.47-7.42 (5H,m), 6.29 (1H,s), 5.35 (2H,s).

Synthesis Example 49
Synthesis of methyl 5-[(4-methylphenyl)sulfanyl]imidazo[1,2-a]pyridine-7-carboxylate (Compound No. 1-1505) 4-Methylbenzenethiol (283 mg, 2.28 mmol) and methyl 5-chloroimidazo[1,2-a]pyridine-7-carboxylate (400 mg, 1.90 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (108 mg, 2.47 mmol) was added and reacted at 130° C. for 30 minutes using a microwave. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain methyl 5-[(4-methylphenyl)sulfanyl]imidazo[1,2-a]pyridine-7-carboxylate (yield 97.8 mg, 17%) as a black solid.
Melting point: 82-83°C
^1H -NMR ( _CDCl3 ) δ: 8.35 (1H, d, J = 0.9 Hz), 7.78 (2H, s), 7.57 (1H, d, J = 1.8 Hz), 7.24 (2H, d, J = 8.2 Hz), 7.15 (2H, d, J = 8.2 Hz), 3.95 (3H, s), 2.34 (3H, s).

Synthesis Example 50
Synthesis of methyl 5-[4-(trifluoromethyl)phenyl]sulfanylimidazo[1,2-a]pyridine-7-carboxylate (Compound No. 1-1508) 4-(Trifluoromethyl)benzenethiol (406 mg, 2.28 mmol) and methyl 5-chloroimidazo[1,2-a]pyridine-7-carboxylate (400 mg, 1.90 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (108 mg, 2.47 mmol) was added and reacted at 130° C. for 30 minutes using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a brown solid of methyl 5-[4-(trifluoromethyl)phenyl]sulfanylimidazo[1,2-a]pyridine-7-carboxylate (yield 86.1 mg, 13%).
Melting point: 95-97°C
^1H -NMR ( _CDCl3 ) δ: 8.49 (1H, d, J = 0.9 Hz), 7.87 (1H, d, J = 1.4 Hz), 7.80 (1H, d, J = 1.4 Hz), 7.71 (1H, s), 7.53 (2H, d, J = 8.7 Hz), 7.23 (2H, d, J = 8.2 Hz), 3.99 (3H, s).

Synthesis Example 51
Synthesis of 5-(4-tert-butylphenoxy)-7-chloro-imidazo[1,2-a]pyridine (Compound No. 1-81) 4-tert-butylphenol (192 mg, 1.28 mmol) and 5,7-dichloroimidazo[1,2-a]pyridine (200 mg, 1.07 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (60.7 mg, 1.39 mmol) was added and reacted at 160°C for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 5-(4-tert-butylphenoxy)-7-chloro-imidazo[1,2-a]pyridine (yield 73.3 mg, 23%) as a white solid.
Melting point: 149-150°C
^1H -NMR ( _CDCl3 ) δ: 7.78 (1H,s), 7.65 (1H,d,J=0.9Hz), 7.52-7.48 (2H,m), 7.35 (1H,d,J=1.4Hz), 7.15-7.13 (2H,m), 5.92 (1H,d,J=1.8Hz), 1.37 (9H,s).

Synthesis Example 52
Synthesis of 7-chloro-5-(4-isopropylphenoxy)imidazo[1,2-a]pyridine (Compound No. 1-812) 4-Isopropylphenol (437 mg, 3.21 mmol) and 5,7-dichloroimidazo[1,2-a]pyridine (500 mg, 2.67 mmol) were dissolved in dimethylformamide (2 mL), and then 55% sodium hydride (152 mg, 3.48 mmol) was added and reacted at 160°C for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 7-chloro-5-(4-isopropylphenoxy)imidazo[1,2-a]pyridine (yield 637 mg, 83%) as a white solid.
Melting point: 109-111°C
^1H -NMR ( _CDCl3 ) δ: 7.78 (1H, s), 7.64 (1H, d, J = 1.4 Hz), 7.35-7.32 (3H, m), 7.14-7.13 (2H, m), 5.91 (1H, d, J = 1.8 Hz), 3.04-2.93 (1H, m), 1.30 (6H, d, J = 6.9 Hz).

Synthesis Example 53
Synthesis of 7-methyl-5-(4-methylphenylsulfanyl)imidazo[1,2-a]pyridine (Compound No. 1-946) 4-Methylbenzenethiol (106 mg, 0.853 mmol) and 5-bromo-7-methyl-imidazo[1,2-a]pyridine (150 mg, 0.711 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (40.3 mg, 0.924 mmol) was added and reacted at 160°C for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 7-methyl-5-(4-methylphenylsulfanyl)imidazo[1,2-a]pyridine (yield 73.5 mg, 41%) as a light brown solid.
Melting point: 91-93°C
^1H -NMR ( _CDCl3 ) δ: 7.58 (1H,s), 7.53 (1H,s), 7.39 (1H,s), 7.20 (2H,t,J=8.5Hz), 7.13 (2H,d,J=8.2Hz), 6.82 (1H,d,J=1.4Hz), 2.38 (3H,s), 2.33 (3H,s).

Synthesis Example 54
Synthesis of 5-(4-isopropylphenoxy)-7-methyl-imidazo[1,2-a]pyridine (Compound No. 1-920) 4-Isopropylphenol (116 mg, 0.853 mmol) and 5-bromo-7-methyl-imidazo[1,2-a]pyridine (150 mg, 0.711 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (40.3 mg, 0.924 mmol) was added and reacted at 160°C for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain orange amorphous 5-(4-isopropylphenoxy)-7-methyl-imidazo[1,2-a]pyridine (yield 122 mg, 64%).
^1H -NMR ( _CDCl3 ) δ: 7.69 (1H,s), 7.57 (1H,d,J=0.9Hz), 7.30 (2H,d,J=8.7Hz), 7.12 (1H,s), 7.11-7.09 (2H,m), 5.80 (1H,s), 3.00-2.93 (1H,m), 2.31 (3H,d,J=0.9Hz), 1.29 (6H,d,J=6.9Hz).

Synthesis Example 55
Synthesis of 7-difluoromethyl-5-(4-isopropylphenoxy)imidazo[1,2-a]pyridine (compound number 1-1168) 4-Isopropylphenol (121 mg, 0.888 mmol) and 5-chloro-7-difluoromethylimidazo[1,2-a]pyridine (150 mg, 0.740 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (42.0 mg, 0.963 mmol) was added and reacted at 160°C for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 7-difluoromethyl-5-(4-isopropylphenoxy)imidazo[1,2-a]pyridine (yield 210 mg, 94%) as a white solid.
Melting point: 93-94°C
^1H -NMR ( _CDCl3 ) δ: 7.88 (1H,s), 7.75 (1H,s), 7.49 (1H,s), 7.34-7.33 (2H,m), 7.16-7.13 (2H,m), 6.59 (1H,t,J=55.9Hz), 6.07 (1H,s), 3.02-2.96 (1H,m), 1.31 (6H,d,J=6.9Hz).

Synthesis Example 56
Synthesis of 7-difluoromethyl-5-[(4-trifluoromethoxy)phenoxy)]imidazo[1,2-a]pyridine (Compound No. 1-1182) 4-(Trifluoromethoxy)phenol (158 mg, 0.888 mmol) and 5-chloro-7-difluoromethylimidazo[1,2-a]pyridine (150 mg, 0.740 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (42.0 mg, 0.963 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 7-difluoromethyl-5-[(4-trifluoromethoxy)phenoxy)]imidazo[1,2-a]pyridine (yield 211 mg, 83%).
Melting point: 69-70°C
^1H -NMR ( _CDCl3 ) δ: 7.86 (1H, s), 7.77 (1H, d, J = 1.4 Hz), 7.55 (1H, s), 7.36 (2H, d, J = 8.7 Hz), 7.28-7.26 (2H, m), 6.61 (1H, t, J = 55.6 Hz), 6.11 (1H, d, J = 0.9 Hz).

Synthesis Example 57
Synthesis of 7-difluoromethyl-5-(4-methylphenylsulfanyl)imidazo[1,2-a]pyridine (Compound No. 1-1199) 4-Methylbenzenethiol (110 mg, 0.888 mmol) and 5-chloro-7-difluoromethylimidazo[1,2-a]pyridine (150 mg, 0.740 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (42.0 mg, 0.963 mmol) was added and reacted at 160° C. for 1 hour using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a pale red solid of 7-difluoromethyl-5-(4-methylphenylsulfanyl)imidazo[1,2-a]pyridine (yield 191 mg, 89%).
Melting point: 94-96°C
^1H -NMR ( _CDCl3 ) δ: 7.74-7.73 (3H, m), 7.29 (2H, d, J = 7.8 Hz), 7.19 (2H, d, J = 8.2 Hz), 6.96 (1H, s), 6.64 (1H, t, J = 55.9 Hz), 2.37 (3H, s).

Synthesis Example 58
Synthesis of 7-bromo-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (Compound No. 1-128) 4-Trifluoromethoxyphenol (332 mg, 1.87 mmol) was dissolved in dimethylformamide (1 mL), and then finely powdered potassium carbonate (279 mg, 2.02 mmol) was added and stirred at room temperature (25° C.) for 5 minutes. Then, 7-bromo-5-chloro-imidazo[1,2-a]pyridine (360 mg, 1.56 mmol) was added and stirred at 130° C. for 5 hours. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 7-bromo-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (yield 500 mg, 86%) as a yellow solid.
Melting point: 86-88°C
^1H -NMR ( _CDCl3 ) σ: 7.76 (1H,s), 7.65 (1H,s), 7.59 (1H,s), 7.37-7.33 (2H,m), 7.28-7.24 (2H,m), 6.03 (1H,s)

Synthesis Example 59
Synthesis of 7-ethyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (Compound No. 1-199) 7-Chloro-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (300 mg, 0.913 mmol) and ethylboronic acid (101 mg, 1.37 mmol) were dissolved in a toluene/water=2/1 mixed solvent (3 mL), and nitrogen bubbling was performed for 5 minutes. Subsequently, palladium(II) acetate (41.0 mg, 0.183 mmol), 2-dicyclohexylphosphino-2'-6'-dimethoxybiphenyl (150 mg, 0.365 mmol), and tripotassium phosphate (581 mg, 2.74 mmol) were added, and the mixture was reacted at 110°C for 2 hours using a microwave. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 7-ethyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (yield 181 mg, 62%) as a brown solid.
Melting point: 64-67°C
^1H -NMR ( _CDCl3 ) σ: 7.65 (1H, s), 7.61 (1H, d, J = 0.9 Hz), 7.32 (2H, d, J = 8.7 Hz), 7.27 (1H, s), 7.22-7.19 (2H, m), 5.92 (1H, d, J = 1.4 Hz), 2.64 (2H, q, J = 7.6 Hz), 1.23 (3H, t, J = 7.6 Hz).

Synthesis Example 60
Synthesis of 5-[(4-tertiary butylphenyl)methyl]-7-trifluoromethylimidazo[1,2-a]pyridine (compound number 1-1355) 5-Chloro-7-trifluoromethylimidazo[1,2-a]pyridine (300 mg, 1.36 mmol), 2-[(4-tertiary butylphenyl)methyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (559 mg, 204 mmol) were dissolved in a toluene/water=2/1 mixed solvent (3 mL), and nitrogen bubbling was performed for 5 minutes. Subsequently, palladium(II) acetate (61.1 mg, 0.272 mmol), 2-dicyclohexylphosphino-2'-6'-dimethoxybiphenyl (223 mg, 0.544 mmol), and tripotassium phosphate (866 mg, 4.08 mmol) were added, and the mixture was reacted at 110°C for 2 hours using a microwave. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane=1/1) to obtain 5-[(4-tert-butylphenyl)methyl]-7-trifluoromethylimidazo[1,2-a]pyridine (yield 260 mg, 58%) as a brown solid.
Melting point: 121-127°C
^1H -NMR ( _CDCl3 ) σ: 7.91 (1H,s), 7.77 (1H,s), 7.60 (1H,s), 7.38 (2H,d,J=8.2Hz), 7.16 (2H,d,J=8.2Hz), 6.76 (1H,s), 4.26 (2H,s), 1.32 (9H,s).

Synthesis Example 61
Synthesis of 5-(4-tert-butylphenoxy)-7-(fluoromethyl)imidazo[1,2-a]pyridine (Compound No. 1-1122)
[5-(4-tert-butylphenoxy)imidazo[1,2-a]pyridin-7-yl]methanol (320 mg, 1.080 mmol) was dissolved in chloroform (3 mL), and the internal temperature was cooled to 0° C. in an ice bath, and (diethylamino)sulfur trifluorolide (435 mg, 2.70 mmol) was added and stirred at room temperature (25° C.). Saturated sodium bicarbonate water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane=1/1) to obtain a yellow solid of 5-(4-tert-butylphenoxy)-7-(fluoromethyl)imidazo[1,2-a]pyridine (yield 150 mg, 47%).
Melting point: 157-164°C
^1H -NMR ( _CDCl3 ) δ: 7.81 (1H,s), 7.68 (1H,d,J=0.9Hz), 7.49-7.47 (2H,m), 7.33 (1H,s), 7.14-7.13 (2H,m), 5.98 (1H,d,J=1.4Hz), 5.39-5.37 (1H,m), 5.27-5.25 (1H,m), 1.35 (9H,s).

Synthesis Example 62
Synthesis of 7-fluoromethyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (Compound No. 1-1133) {5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridin-7-yl}methanol (200 mg, 0.617 mmol) was dissolved in chloroform (10 mL) and cooled to 0° C. in an ice bath. (Diethylamino)sulfur trifluorolide (249 mg, 1.54 mmol) was added dropwise in an ice bath and stirred at room temperature (25° C.) for 3 hours. The reaction mixture was poured into saturated aqueous sodium bicarbonate (30 mL) and stirred at room temperature (25° C.) for 10 minutes, and then extracted with ethyl acetate. The extract was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain 7-fluoromethyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (yield 112 mg, 56%) as a red oil.
^1H -NMR ( _CDCl3 ) δ: 7.79 (1H,s), 7.70 (1H,d,J=0.9Hz), 7.38 (1H,s), 7.34 (2H,d,J=8.7Hz), 7.25-7.23 (2H,m), 6.01 (1H,s), 5.35 (2H,d,J=47.2Hz).

Synthesis Example 63
Synthesis of 7-cyclopentyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (Compound No. 1-455) 7-(cyclopenten-1-yl)-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (350 mg, 0.971 mmol) and 10% palladium carbon (103 mg, 0.0971 mmol) were suspended in methanol (20 mL), and the mixture was stirred at room temperature (25° C.) for 6 hours while hydrogen gas was sealed in a balloon. The reaction mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane=1/1) to obtain 7-cyclopentyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (yield 230 mg, 65%) as an orange oil.
^1H -NMR ( _CDCl3 ) δ: 7.63 (1H, d, J = 1.4 Hz), 7.60 (1H, d, J = 0.9 Hz), 7.30 (2H, d, J = 8.2 Hz), 7.26 (1H, s), 7.19-7.18 (2H, m), 5.98 (1H, d, J = 1.4 Hz), 3.02-2.93 (1H, m), 2.07-2.00 (2H, m), 1.82-1.74 (2H, m), 1.70-1.65 (2H, m), 1.59-1.50 (2H, m).

Synthesis Example 64
Synthesis of 7-trifluoromethyl-5-[4-(trifluoromethylsulfanyl)phenoxy]-[1,2,4]triazolo[4,3-a]pyridine (Compound No. 2-801) 4-(Trifluoromethylsulfanyl)phenol (210 mg, 1.08 mmol) and 5-chloro-7-trifluoromethyl-[1,2,4]triazolo[4,3-a]pyridine (200 mg, 0.903 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (51.2 mg, 1.17 mmol) was added and reacted at 160° C. for 3 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a white solid of 7-trifluoromethyl-5-[4-(trifluoromethylsulfanyl)phenoxy]-[1,2,4]triazolo[4,3-a]pyridine (yield 270 mg, 79%).
Melting point: 112-114°C
^1H -NMR ( _CDCl3 ) δ: 9.13 (1H,s), 7.90 (1H,s), 7.87-7.85 (2H,m), 7.36-7.35 (2H,m), 6.09 (1H,s).

Synthesis Example 65
Synthesis of 5-(4-chlorophenyl)sulfanyl-7-trifluoromethyl-[1,2,4]triazolo[4,3-a]pyridine (Compound No. 2-336) 4-Chlorobenzenethiol (157 mg, 1.08 mmol) and 5-chloro-7-trifluoromethyl-[1,2,4]triazolo[4,3-a]pyridine (200 mg, 0.903 mmol) were dissolved in dimethylformamide (1 mL), and then 55% sodium hydride (51.2 mg, 1.17 mmol) was added and reacted at 160° C. for 3 hours using microwaves. Water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a pale yellow solid of 5-(4-chlorophenyl)sulfanyl-7-trifluoromethyl-[1,2,4]triazolo[4,3-a]pyridine (yield 234 mg, 79%).
Melting point: 133-134°C
¹ H-NMR (CDCl ₃ ) δ: 8.90 (1H, s), 8.10 (1H, s), 7.44-7.38 (4H, m), 6.99 (1H, d, J=1.4 Hz).

Synthesis Example 66
Synthesis of 5-(4-chlorophenyl)sulfanyl-7-trifluoromethylimidazo[1,2-a]pyridine hydrochloride (Compound No. 4-1) 5-(4-chlorophenyl)sulfanyl-7-trifluoromethylimidazo[1,2-a]pyridine (200 mg, 0.609 mmol) was dissolved in ethyl acetate (10 mL), and then 1 mol/L hydrochloric acid-ethyl acetate solution (2 mL) was added. The obtained crystals were filtered by suction to obtain 5-(4-chlorophenyl)sulfanyl-7-trifluoromethylimidazo[1,2-a]pyridine hydrochloride (yield 202 mg, 91%) as a white solid.
Melting point: 95-97°C
^1H -NMR (DMSO (dimethylsulfoxide)-D6) δ: 8.32 (1H,s), 8.16 (1H,s), 8.08 (1H,d,J=1.4Hz), 7.63 (1H,s), 7.49 (4H,s).

Synthesis Example 67
Synthesis of 5-[(5-chloro-2-pyridyl)sulfanyl]-7-trifluoromethylimidazo[1,2-a]pyridine hydrochloride (Compound No. 4-4) 5-[(5-chloro-2-pyridyl)sulfanyl]-7-trifluoromethylimidazo[1,2-a]pyridine (200 mg, 0.607 mmol) was dissolved in ethyl acetate (10 mL), and then 1 mol/L hydrochloric acid-ethyl acetate solution (2 mL) was added. The obtained crystals were filtered by suction to obtain 5-[(5-chloro-2-pyridyl)sulfanyl]-7-trifluoromethylimidazo[1,2-a]pyridine hydrochloride (yield 160 mg, 72%) as a white solid.
Melting point: 202-208°C
^1H -NMR ( _CDCl3 ) δ: 8.82 (1H,s), 8.18 (1H,d,J=2.3Hz), 7.99 (1H,s), 7.95 (1H,s), 7.87 (1H,s), 7.73 (1H,dd,J=8.7,2.3Hz), 7.39 (1H,d,J=8.7Hz).

Synthesis Example 68
Synthesis of 7-ethynyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (Compound No. 1-521) Trimethyl-[2-[5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridin-7-yl]ethynyl]silane (1.12 g, 2.87 mmol) was dissolved in methanol (10 mL) and tetrahydrofuran (10 mL), and potassium carbonate (793 mg, 5.74 mmol) was added and reacted at room temperature (25° C.) for 3 hours. Water (30 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=3/1) to obtain 7-ethynyl-5-[4-(trifluoromethoxy)phenoxy]imidazo[1,2-a]pyridine (yield 480 mg, 53%) as a white solid.
Melting point: 92-94°C
^1H -NMR ( _CDCl3 ) σ: 7.79 (1H, d, J = 1.4 Hz), 7.74 (1H, d, J = 1.4 Hz), 7.58 (1H, s), 7.34 (2H, dd, J = 9.2, 0.9 Hz), 7.26-7.24 (2H, m), 6.01 (1H, d, J = 0.9 Hz), 3.18 (1H, s).

The ¹ H NMR spectrum (CDCl ₃ or DMSO-D6) σ (ppm) values and melting points (° C.) of the compounds according to the present invention produced according to the above synthesis examples and production methods are shown in Table 5. ^{The 1} H NMR data was measured using a JNM-ECS400 spectrometer (manufactured by JEOL Ltd.).

The following reference examples show synthesis examples in which the starting materials for the above synthesis are synthesized from commercially available products, but are in no way limited to these.

[Reference Example 1]
Synthesis of 5,7-dichloroimidazo[1,2-a]pyridine 2-bromo-1,1-diethoxy-ethane was dissolved in ethanol (100 mL), and p-toluenesulfonic acid monohydrate (22.4 g, 118 mmol) was added and stirred at room temperature (25° C.) for 30 minutes. Then, 4,6-dichloropyridin-2-amine (12.8 g, 78.5 mmol) was added and reacted for 3 hours under reflux heating conditions. The reaction mixture was concentrated with a rotary evaporator, and saturated sodium bicarbonate water (100 mL) was poured into the concentrated liquid to precipitate a solid. The obtained solid was collected by suction filtration using a Kiriyama funnel, and then washed with water and hexane. The solid obtained by washing was dried with a rotary evaporator to obtain 5,7-dichloroimidazo[1,2-a]pyridine (yield 14.4 g, 98%) as a white solid.
Melting point: 90-92°C
^1H -NMR ( _CDCl3 ) σ: 7.75 (1H, s), 7.71 (1H, s), 7.62 (1H, d, J = 1.4 Hz), 6.94 (1H, d, J = 1.4 Hz).

[Reference Example 2]
Synthesis of (4,6-dichloro-2-pyridyl)hydrazine 2,4,6-trichloropyridine (20.0 g, 110 mmol) was dissolved in ethanol (20 mL), and then hydrazine monohydrate (31.36 g, 613 mmol) was added dropwise under ice cooling and stirred for 1 hour under ice cooling. The ice bath was then removed and the mixture was stirred for 12 hours while the temperature was returned to room temperature (25°C). Water (50 mL) was added to the reaction solution, and the resulting solid was collected by suction filtration using a Kiriyama funnel and washed with water. The solid obtained by washing was dried in a rotary evaporator to obtain a white solid (4,6-dichloro-2-pyridyl)hydrazine (yield 22.0 g) as a crude product. The crude product was used as it was in the next step without purification.

[Reference Example 3]
Synthesis of ethyl (1E)-N-(4,6-dichloropyridyl)methanehydrazonate (4,6-dichloro-2-pyridyl)hydrazine (5.87 g, 33.0 mmol) was dissolved in triethyl orthoformate (50 mL) and reacted for 3 hours at 120° C. The reaction solution was concentrated using a rotary evaporator, and the concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane=1/1) to obtain ethyl (1E)-N-(4,6-dichloropyridyl)methanehydrazonate (yield: 1.2 g, 16%) as a yellow oil.
^1H -NMR ( _CDCl3 ) σ: 8.33 (1H, s), 7.02 (1H, d, J = 1.8 Hz), 6.71 (1H, d, J = 1.8 Hz), 6.54 (1H, s), 4.13 (2H, q, J = 7.0 Hz), 1.37 (3H, t, J = 7.1 Hz).

[Reference Example 4]
Synthesis of 5,7-dichloro-[1,2,4]triazolo[4,3-a]pyridine Ethyl (1E)-N-(4,6-dichloropyridyl)methanehydrazonate (300 mg, 1.28 mmol) was dissolved in Eaton's reagent (1 mL) and reacted at 110°C for 30 minutes using microwaves. Saturated sodium bicarbonate water (10 mL) was poured into the reaction mixture to precipitate a solid, and the resulting solid was collected by suction filtration using a Kiriyama funnel and washed with water. The washed solid was dried using a rotary evaporator to obtain 5,7-dichloro-[1,2,4]triazolo[4,3-a]pyridine (yield 240 mg, 100%) as a white solid.
Melting point: 161-164°C
^1H -NMR ( _CDCl3 ) σ: 8.93 (1H, s), 7.78 (1H, s), 6.95 (1H, d, J = 1.4 Hz).

[Reference Example 5]
Synthesis of methyl 4-chloro-1-oxide-pyridin-1-ium-2-carboxylate Methyl 4-chloropyridine-2-carboxylate (7.54 g, 43.9 mmol) was dissolved in chloroform (50 mL), and metachloroperbenzoic acid (12.8 g, 57.1 mmol) was added and stirred at room temperature (25° C.) for 5 hours. Saturated sodium bicarbonate water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane=1/1) to obtain methyl 4-chloro-1-oxide-pyridin-1-ium-2-carboxylate (yield 4.27 g, 51%) as a white solid.
¹ H-NMR (CDCl ₃ ) σ: 8.16 (1H, d, J=6.9 Hz), 7.62 (1H, d, J=3.2 Hz), 7.31 (1H, dd, J=6.9, 3.2 Hz), 4.01 (3H, s).

[Reference Example 6]
Synthesis of methyl 4,6-dichloropyridine-2-carboxylate Methyl 4-chloro-1-oxide-pyridin-1-ium-2-carboxylate (7.46 g, 39.8 mmol) was dissolved in phosphoryl chloride (20 mL) and stirred under reflux heating for 3 hours. The reaction mixture was added to ice-cooled saturated sodium bicarbonate water, and then extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane=1/1) to obtain methyl 4,6-dichloropyridine-2-carboxylate (yield 6.48 g, 79%) as a brown solid.
Melting point: 79-80°C
¹ H-NMR (CDCl ₃ ) σ: 8.07 (1H, d, J=1.8 Hz), 7.56 (1H, d, J=1.8 Hz), 4.02 (3H, s).

[Reference Example 7]
Synthesis of (4,6-dichloro-2-pyridyl)methanol Methyl 4,6-dichloropyridine-2-carboxylate (3.48 g, 16.9 mmol) and calcium chloride (7.50 g, 67.6 mmol) were dissolved in a methanol/tetrahydrofuran 2/1 mixed solvent (30 mL), and sodium borohydride (1.28 g, 33.8 mmol) was added under ice cooling. The reaction solution was stirred at room temperature (25° C.) for 2 hours, and then water (50 mL) was poured into the reaction solution and extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain methyl (4,6-dichloro-2-pyridyl)methanol (crude yield 3.10 g, 100%) as a crude product in the form of a white solid. The crude product was used in the next step without purification.
Melting point: 83-85°C
^1H -NMR ( _CDCl3 ) σ: 7.32-7.32 (1H, m), 7.28-7.28 (1H, m), 4.74 (2H, s), 2.93 (1H, s).

[Reference Example 8]
Synthesis of 2-(azidomethyl)-4,6-dichloro-pyridine Methyl(4,6-dichloro-2-pyridyl)methanol (500 mg, 2.81 mmol) and diphenylphosphoryl azide (1.16 g, 4.21 mmol) were dissolved in toluene (10 mL), and then diazabicycloundecene (631 mg, 4.21 mmol) was added dropwise and stirred at room temperature (25° C.) for 10 hours. Water (10 mL) was poured into the reaction solution and extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane=1/1) to obtain colorless oily 2-(azidomethyl)-4,6-dichloro-pyridine (yield 491 mg, 86%). The column fraction was not dried and was used in the next step with the solvent remaining.
¹ H-NMR (CDCl ₃ ) σ: 7.34 (1H, d, J=1.8 Hz), 7.32 (1H, d, J=1.8 Hz), 4.49 (2H, s).

[Reference Example 9]
Synthesis of (4,6-dichloro-2-pyridyl)methanamine hydrochloride 2-(azidomethyl)-4,6-dichloro-pyridine (3.44 g, 16.9 mmol) and triphenylphosphine (5.33 g, 20.3 mmol) were dissolved in tetrahydrofuran (30 mL), and then water (3 mL) was added and stirred at room temperature (25° C.) for 2 hours. The reaction mixture was concentrated using a rotary evaporator, and then a 4 mol/L hydrogen chloride ethyl acetate solution was added to precipitate a solid. The resulting solid was collected by suction filtration using a Kiriyama funnel to obtain (4,6-dichloro-2-pyridyl)methanamine hydrochloride (1.36 g, 38%) as a white solid.
^1H -NMR(DO)σ: 7.43 (1H, d, J=1.4 Hz), 7.34 (1H, d, J=1.4 Hz), 4.13 (2H, brs).

[Reference Example 10]
Synthesis of N-[(2,4-dichloro-2-pyridyl)methyl]formamide (4,6-dichloro-2-pyridyl)methanamine hydrochloride (800 mg, 3.75 mmol) was dissolved in triethyl orthoformate (833 mg, 5.62 mmol) and reacted with microwaves at 120° C. for 1 hour. The reaction mixture was concentrated with a rotary evaporator, and the resulting concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane=1/1) to obtain a yellow solid of N-[(2,4-dichloro-2-pyridyl)methyl]formamide (yield 560 mg, 73%).
^1H -NMR (DO) σ: 8.32 (1H, s), 7.30 (1H, d, J = 1.4 Hz), 7.26 (1H, d, J = 1.4 Hz), 6.54 (1H, brs), 4.57 (2H, d, J = 5.5 Hz).

[Reference Example 11]
Synthesis of 5,7-dichloroimidazo[1,5-a]pyridine (compound number: 3-57) N-[(2,4-dichloro-2-pyridyl)methyl]formamide (560 mg, 2.73 mmol) was dissolved in Eaton's reagent (1 mL) and reacted at 120°C for 60 minutes using microwaves. Saturated sodium bicarbonate water (10 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane = 1/1) to obtain 5,7-dichloroimidazo[1,5-a]pyridine (yield 286 mg, 56%) as a white solid.
^1H -NMR ( _CDCl3 ) σ: 8.29 (1H,s), 7.51 (1H,s), 7.45 (1H,d,J=1.4Hz), 6.68 (1H,d,J=1.4Hz).

[Reference Example 12]
Synthesis of 6-chloro-4-trifluoromethylpyridin-2-amine 2,6-dichloro-4-trifluoromethylpyridine (10.0 g, 46.3 mmol) and 40 mL of 28% aqueous ammonia were placed in an autoclave reactor and reacted at 160°C and a pressure of 1.9 MPa for 8 hours. The reaction solution was cooled to room temperature (25°C), and then ethyl acetate was added to the reaction solution for extraction. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a white solid 6-chloro-4-trifluoromethylpyridin-2-amine (yield 6.97 g, 77%) as a crude product.
^1H -NMR ( _CDCl3 ) σ: 6.84 (1H, s), 6.58 (1H, s), 4.98 (2H, brs).

[Reference Example 13]
Synthesis of 4-tert-butyl-6-chloro-N-[(4-methoxyphenyl)methyl]pyridin-2-amine 4-tert-butyl-2,6-dichloropyridine (6.66 g, 32.6 mmol), (4-methoxyphenyl)methanamine (8.95 g, 65.3 mmol), and N-ethyl-N-isopropyl-propan-2-amine (8.43 g, 65.3 mmol) were dissolved in normal butanol (5 mL) and reacted at 180° C. for 4 hours using microwaves. Water (30 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (elution solvent: ethyl acetate/n-hexane=1/4) to obtain 4-tert-butyl-6-chloro-N-[(4-methoxyphenyl)methyl]pyridin-2-amine (yield 5.30 g, 53%) as a white solid.
^1H -NMR ( _CDCl3 ) δ: 7.29-7.25 (2H, m), 6.89-6.86 (2H, m), 6.61 (1H, d, J = 1.4 Hz), 6.21 (1H, d, J = 1.4 Hz), 4.86 (1H, t, J = 5.5 Hz), 4.40 (2H, d, J = 5.5 Hz), 3.80 (3H, s), 1.22 (9H, s).

[Reference Example 14]
Synthesis of tert-butyl N-(6-chloro-4-methoxy-2-pyridine)carbamate 2,6-dichloro-4-methoxypyridine (18.2 g, 102 mmol) and tert-butyl carbamate (14.3 g, 122 mmol) were dissolved in 1,4-dioxane (30 mL), and then nitrogen bubbling was performed for 5 minutes. Subsequently, palladium(II) acetate (1.15 g, 5.10 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (4.86 g, 10.2 mmol), and cesium carbonate (66.5 g, 204 mmol) were added, and the mixture was reacted at 100°C for 5 hours. Water (30 mL) was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1) to obtain a colorless liquid of tert-butyl N-(6-chloro-4-methoxy-2-pyridine)carbamate (yield: 17.5 g, 66%).
^1H -NMR ( _CDCl3 ) σ: 7.45 (1H, d, J = 1.8 Hz), 7.16 (1H, s), 6.54 (1H, d, J = 1.8 Hz), 3.87 (3H, s), 1.51 (9H, s).

[Reference Example 15]
Synthesis of 4-tert-butyl-6-chloropyridin-2-amine 4-tert-butyl-6-chloro-N-[(4-methoxyphenyl)methyl]pyridin-2-amine (5.30 g, 17.4 mmol) was dissolved in chloroform (34 mL), and trifluoroacetic acid (39.7 g, 348 mmol) was slowly added dropwise under stirring, and the mixture was reacted at room temperature (25° C.) for 12 hours. The reaction mixture was poured into a 36% aqueous potassium carbonate solution (200 mL), and extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 4-tert-butyl-6-chloropyridin-2-amine (yield 4.00 g) as a yellow liquid as a crude product.
¹ H-NMR (CDCl ₃ ) σ: 6.67 (1H, d, J=1.4 Hz), 6.35 (1H, d, J=1.4 Hz), 4.56 (2H, brs), 1.25 (9H, s).

[Reference Example 16]
Synthesis of 6-chloro-4-methoxypyridin-2-amine Tertiary butyl N-(6-chloro-4-methoxy-2-pyridine)carbamate (4.00 g, 15.5 mmol) was dissolved in chloroform (40 mL), and trifluoroacetic acid (10 mL) was slowly added dropwise with stirring, followed by reaction at room temperature (25° C.) for 12 hours. The reaction mixture was concentrated under reduced pressure to obtain 6-chloro-4-methoxypyridin-2-amine (yield 4.21 g) as a yellow liquid as a crude product.
¹ H-NMR (CDCl ₃ ) σ: 6.29 (1H, d, J=1.4 Hz), 5.87 (1H, d, J=1.4 Hz), 4.51 (2H, brs), 3.79 (3H, s).

[Reference Example 17]
Synthesis of 2,6-dichloro-4-methoxypyridine 2,4,6-trichloropyridine (20.3 g, 111 mmol) was dissolved in dimethylformamide (110 mL) and cooled to 0°C in an ice bath. 55% sodium hydride (5.10 g, 117 mmol) and methanol (3.74 g, 117 mmol) were added in an ice bath and stirred at room temperature (25°C) for 12 hours. The reaction mixture was poured into water (300 mL) and extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 2,6-dichloro-4-methoxypyridine (yield 18.2 g) as a white solid crude product.
¹ H-NMR (CDCl ₃ ) σ: 6.80 (2H, s), 3.87 (3H, s).

[Reference Example 18]
Synthesis of 2,6-dichloro-4-isopropylpyridine 2,4,6-trichloropyridine (5.4 g, 29.6 mmol) and iron (III) acetylacetonate (1.05 g, 2.96 mmol) were dissolved in a tetrahydrofuran/N-methylpyrrolidone=10/3 mixed solvent (33 mL), and then cooled to −10° C. in a salt ice bath and stirred. Subsequently, a 1.0 mol/L isopropyl magnesium chloride solution (59 mL) was slowly added dropwise and stirred in a salt ice bath for 4 hours. A 1.0 mol/L aqueous hydrochloric acid solution (70 mL) was added dropwise to the reaction mixture in a salt ice bath and stirred at room temperature (25° C.) for 30 minutes. The reaction solution was extracted with ethyl acetate, and the extract was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/10) to obtain 2,6-dichloro-4-isopropylpyridine (yield: 3.65 mg, 65%) as a pale yellow liquid.
¹ H-NMR (CDCl ₃ ) σ: 7.12 (2H, s), 2.92-2.85 (1H, m), 1.26 (6H, d, J=6.9 Hz).

<Formulation>
The following provides a detailed description of the formulations containing the compound of the present invention, with reference to some formulation examples, but the compound of the present invention, auxiliary ingredients, and the amounts of these ingredients added are not limited to the following formulation examples. Note that "parts" in the formulation examples means "parts by weight."

Formulation Example 1 Emulsion The compound of the present invention (10 parts), xylene (60 parts), N-octylpyrrolidone (20 parts), polyoxyethylene alkyl phenyl ether (9 parts) and calcium dodecylbenzenesulfonate (1 part) were uniformly mixed and dissolved to obtain an emulsion.

Formulation Example 2 Wettable Powder-1
The compound of the present invention (20 parts), white carbon (10 parts), kaolin (60 parts), sodium lignin sulfonate (5 parts) and sodium alkylbenzene sulfonate (5 parts) were uniformly mixed and ground in an air mill to obtain a wettable powder.

Formulation Example 3 Wettable powder-2
The compound of the present invention (20 parts), white carbon (20 parts), kaolin (50 parts), sodium salt of alkylnaphthalenesulfonic acid and formaldehyde condensate (5 parts) and polyoxyethylene alkyl ether (5 parts) were uniformly mixed and ground in an air mill to obtain a wettable powder.

Formulation Example 4 Water-soluble-1
The compound of the present invention (20 parts), sodium alkylbenzenesulfonate (3 parts) and glucose (77 parts) were uniformly mixed and ground to obtain a water-soluble compound.

Formulation Example 5 Water-soluble-2
The compound of the present invention (50 parts), sodium alkylnaphthalenesulfonate (5 parts), white carbon (2 parts) and glucose (43 parts) were uniformly mixed and ground to obtain a water-soluble compound.

Formulation Example 6 Flowable formulation-1
The compound of the present invention (20 parts) was dispersed in a mixture of propylene glycol (5 parts), polyoxyethylene alkyl ether (1 part), sodium polyoxyethylene styryl phenyl ether sulfate (5 parts), and water (50 parts) that had been mixed in advance to obtain a slurry mixture. This slurry mixture was then wet-ground using a Dynomill (Shinmaru Enterprises) and mixed with a premix in which xanthan gum (0.2 parts) had been dissolved in water (18.8 parts) to obtain a flowable preparation.

Formulation Example 7 Flowable formulation-2
The compound of the present invention (20 parts), sodium dioctyl sulfosuccinate (1 part), polyoxyethylene styryl phenyl ether (4 parts), propylene glycol (8 parts), and water (50 parts) were mixed in advance, and the resulting slurry mixture was wet-ground using a Dynomill (Shinmaru Enterprises Co., Ltd.), and then mixed with a premix in which xanthan gum (0.2 parts) had been dissolved in water (16.8 parts) to obtain a flowable preparation.

Formulation Example 8 EW Agent-1
The compound of the present invention (20 parts), polyoxyethylene styryl phenyl ether (15 parts) and 1,2-benzisothiazolin-3-one (0.1 parts) were mixed and homogenized, and then water (59.6 parts) was gradually added with stirring to obtain a dispersion. Modified silicone (0.1 parts) was added to the obtained dispersion, and xanthan gum (0.2 parts) dispersed in propylene glycol (5.0 parts) was added to obtain an EW agent (phase inversion emulsification method).

Formulation Example 9 EW agent-2
The compound of the present invention (10 parts) was dissolved in xylene (10 parts) and mixed with polyoxyethylene sorbitan trioleate (20 parts). The obtained liquid, modified silicone (0.1 parts), and 1,2-benzoisothiazolin-3-one (0.1 parts) were added to water (54.6 parts), and the mixture was dispersed using a homogenizer, and xanthan gum (0.2 parts) dispersed in propylene glycol (5.0 parts) was added to obtain an EW agent (mechanical emulsification method).

Formulation Example 10 ME agent-1
The compound of the present invention (1 part) and polyoxyethylene styryl phenyl ether (10 parts) were mixed and homogenized, and then water (88.9 parts) was gradually added with stirring. 1,2-benzoisothiazolin-3-one (0.1 part) was added to the dispersion to obtain an ME agent.

Formulation Example 11 ME agent-2
The compound of the present invention (10 parts) and polyoxyethylene sorbitan monooleate (20 parts) were mixed and homogenized, and then water (69.9 parts) was gradually added with stirring. 1,2-benzoisothiazolin-3-one (0.1 parts) was added to the dispersion to obtain an ME agent.

Formulation Example 12 ME agent-3
The compound of the present invention (2 parts), methylnaphthalene (8 parts), polyoxyethylene alkylphenyl ether (10 parts), and alkylbenzenesulfonate calcium (1 part) were mixed and dissolved, and water (78.9 parts) was gradually added with stirring. 1,2-benzoisothiazolin-3-one (0.1 part) was added to the dispersion to obtain an ME agent.

Formulation Example 13 Granules-1
The compound of the present invention (5 parts), bentonite (30 parts), clay (60 parts), and sodium lignin sulfonate (5 parts) were uniformly ground and mixed, kneaded with water, extrusion granulated, and dried to obtain granules.

Formulation Example 14 Granules-2
Silica sand (90 parts) was placed in a tumbling granulator and hydrated, after which the compound of the present invention (5 parts), sodium lignin sulfonate (4 parts), polyvinyl alcohol (0.5 parts) and white carbon (0.5 parts) that had been previously ground and mixed were added, coated, and then dried and sized to obtain granules.

Formulation Example 15 Granules-3
Pumice (89 parts) was placed in a tumbling granulator and moistened, after which the compound of the present invention (5 parts), sodium ligninsulfonate (3 parts), sodium dioctyl sulfosuccinate (0.5 parts), POE styryl phenyl ether (2 parts) and polyvinyl alcohol (0.5 parts) that had been previously ground and mixed were added, coated, and then dried and sized to obtain granules.

Formulation Example 16 Microgranules-1
The compound of the present invention (2 parts) was dissolved in acetone and mixed with pumice (98 parts) while spraying it. The obtained granular composition was dried and then sieved to obtain fine granules.

Formulation Example 17 Microgranules-2
An air mill-pulverized product of the compound of the present invention (5 parts) and quartz sand (85 parts) were mixed, and then a binder Toxanon GR-31A (10 parts) diluted with a solvent was sprayed while mixing. The resulting mixture was dried and sieved to obtain fine granules.

Formulation Example 18: Dust A compound of the present invention (5 parts), white carbon (5 parts) and clay (90 parts) were uniformly mixed and ground to obtain a dust.

Formulation Example 19: DL Powder A compound of the present invention (5 parts), propylene glycol (0.5 parts) and DL clay (94.5 parts) were uniformly mixed and ground to obtain a dust.

Formulation Example 20 Seed Coating Powder The compound of the present invention (10 parts), sodium ligninsulfonate (6 parts), polyvinyl alcohol (1 part) and clay (83 parts) were uniformly mixed and ground to obtain a seed coating powder.

The effects and usefulness of the compounds of the present invention obtained as described above will now be explained using specific examples.

Test Example 1: Insecticidal effect test against brown planthopper (Nilaparvata lugens) A sufficient amount of diluted emulsion (500 ppm) prepared according to Formulation Example 1 was sprayed with a spray gun onto the leaves of rice seedlings that had been grown in a 60 ml plastic cup for 5 days after sowing. After air drying, the liquid was placed in a polycarbonate plastic container with a nylon gothic lid, and 10 4th instar brown planthopper larvae were released into each container, which was then left to stand in a 25°C thermostatic chamber (illuminated for 16 hours). Five days after release, the number of surviving insects was counted, and the mortality rate (%) was calculated using the following formula (a). The test was conducted in duplicate, with one cup for each group.

Formula (a)
Mortality rate (%) = [1 - (number of surviving insects in the treatment area / number of test insects)] x 100

As a result, compound numbers 1-72, 1-78, 1-81, 1-82, 1-84, 1-104, 1-128, 1-132, 1-143, 1-149, 1-154, 1-155, 1-160, 1-172, 1-187, 1-191, 1-199, 1-216, 1-238, 1-255, 1-277, 1-312, 1-316, 1-320, 1-325, 1-327, 1-328, 1-329, 1-337, 1-343, 1-344, 1-349, 1-350, 1-351, 1-352, 1-353, 1-354, 1-358, 1-359, 1-360, 1-362, 1-370, 1-371, 1-375, 1-382, 1-395, 1-409, 1-410, 1-413, 1-455, 1-499, 1-521, 1-525, 1-531, 1-536, 1-544, 1-548, 1-555, 1-559, 1-566, 1-709, 1-753, 1-775, 1-785, 1-792, 1-793, 1-794, 1-804, 1-812, 1-836, 1-842, 1-849, 1-851, 1-868, 1-871, 1- 897, 1-908, 1-909, 1-910, 1-911, 1-912, 1-913, 1-914, 1-920, 1-933, 1-946, 1-953, 1-954, 1-973, 1-976, 1-1001, 1-1017, 1-1020, 1-1045, 1-1056, 1-1062, 1-1065, 1-1091, 1-1095, 1-1105, 1-1107, 1-1109, 1-1119, 1-1122, 1-1133, 1-1149, 1-1150, 1-1168, 1-1171, 1-1182, 1- 1198, 1-1199, 1-1210, 1-1212, 1-1213, 1-1214, 1-1215, 1-1216, 1-1217, 1-1218, 1-1219, 1-1220, 1-1223, 1-1224, 1-1225, 1-1226, 1-1227, 1-1228, 1-1229, 1-1230, 1-1231, 1-1232, 1-1233, 1-1234, 1-1235, 1-1237, 1-1238, 1-1239, 1-1240, 1-1244, 1-1246, 1-1247, 1-1248, 1 -1249, 1-1250, 1-1251, 1-1253, 1-1254, 1-1257, 1-1258, 1-1259, 1-1260, 1-1261, 1-1262, 1-1263, 1-1264, 1-1265, 1-1266, 1-1267, 1-1268, 1-1270, 1-1271, 1-1272, 1-1273, 1-1274, 1-1275, 1-1278, 1-1279, 1-1280, 1-1281, 1-1282, 1-1283, 1-1284, 1-1287, 1-1288, 1-1289, 1-1290, 1-1291, 1-1292, 1-1293, 1-1294, 1-1295, 1-1296, 1-1297, 1-1298, 1-1299, 1-1300, 1-1301, 1-1302, 1-1303, 1-1304, 1-1305, 1-1306, 1-1309, 1-1310, 1-1312, 1-1313, 1-1314, 1-1315, 1-1317, 1-1319, 1-1320, 1-1321, 1-1322, 1-1323, 1-1325, 1-1326, 1-1327, 1-1328 , 1-1329, 1-1330, 1-1331, 1-1332, 1-1333, 1-1334, 1-1335, 1-1337, 1-1339, 1-1344, 1-1345, 1-1347, 1-1350, 1-1352, 1-1353, 1-1355, 1-1357, 1-1358, 1-1359, 1-1366, 1-1372, 1-1380, 1-1389, 1-1403, 1-1405, 1-1406, 1-1407, 1-1414, 1-1415, 1-1416, 1-1417, 1-1418, 1-141 The compounds of the present invention, 9, 1-1426, 1-1465, 1-1466, 1-1479, 1-1492, 1-1504, 1-1505, 1-1507, 1-1508, 1-1523, 1-1525, 1-1527, 1-1533, 1-1540, 1-1551, 1-1552, 1-1553, 2-398, 2-626, 2-637, 2-648, 2-736, 2-805, 2-807, 3-78, 4-1, 4-2, 4-3, 4-4, 4-5, 4-6, 4-7, 4-8, 4-9, and 4-10, showed a mortality rate of 80% or more.

Test Example 2: Insecticidal effect test against green rice leafhopper (Nephotettix cincticeps) A sufficient amount of diluted emulsion (500 ppm) prepared according to Formulation Example 1 was sprayed with a spray gun onto the leaves of rice seedlings that had been grown in a 60 ml plastic cup for 5 days after sowing. After air drying, the liquid was placed in a polycarbonate plastic container with a nylon gothic lid, and 10 fourth-instar green rice leafhopper larvae were released into each container, which was then left to stand in a 25°C thermostatic chamber (illuminated for 16 hours). Five days after release, the number of surviving insects was counted, and the mortality rate (%) was calculated using the above formula (a). The test was conducted in duplicate, with one cup for each group.

As a result, the compounds of the present invention, compound numbers 1-116, 1-154, 1-155, 1-488, 1-1017, 1-1020, 1-1219, 1-1229, 1-1239, 1-1382, 2-805, 4-4, and 4-9, showed a mortality rate of 80% or more.

Test Example 3: Test of control effect against bean aphids (Aphis craccivora) Three wingless bean aphids were released on the leaves of potted broad bean seedlings that had been raised for one week after sowing. A sufficient amount of diluted emulsion (500 ppm) prepared according to Formulation Example 1 was sprayed on the stems and leaves of the broad bean seedlings infested with aphids using a spray gun the day after release. After treatment, the plants were placed in a constant temperature room at 25°C (illumination for 16 hours), and the number of parasitic adults and larvae was counted four days after treatment, and the control rate (%) was calculated using the following formula (b). The test was conducted in duplicate, with one pot per plot.

Formula (b)
Control rate (%) = [1 - (number of parasites in treated area/number of parasites in untreated area)] x 100

As a result, compound numbers 1-78, 1-154, 1-155, 1-199, 1-238, 1-312, 1-354, 1-371, 1-410, 1-521, 1-536, 1-544, 1-555, 1-804, 1-920, 1-1107, 1-1133, 1-1149, 1-1182, 1-1217, 1-12 The compounds of the present invention, 23, 1-1224, 1-1229, 1-1230, 1-1240, 1-1248, 1-1254, 1-1259, 1-1262, 1-1264, 1-1282, 1-1290, 1-1326, 1-1327, 1-1328, 1-1329, 1-1330, and 4-5, showed a control rate of 80% or more.

Test Example 4: Test of control effect against cotton aphid (Aphis gosiipii Glover) Three wingless adults of cotton aphid were released on the leaves of potted eggplants that had been raised for one month after sowing. A sufficient amount of diluted emulsion (500 ppm) prepared according to Formulation Example 1 was sprayed on the stems and leaves of the eggplant seedlings infested with aphids using a spray gun the day after release. After treatment, the plants were placed in a constant temperature room at 25°C (illuminated for 16 hours), and the number of parasitic adults and larvae was counted 4 days after treatment, and the control rate (%) was calculated using the above formula (b). The test was conducted in duplicate, with one pot per area.

Test Example 5: Test of control effect against green peach aphid (Myzus persicae) Three wingless adults of green peach aphid were released on the leaves of potted eggplants that had been raised for one month after sowing. A sufficient amount of diluted emulsion (500 ppm) prepared according to Formulation Example 1 was sprayed on the stems and leaves of the eggplant seedlings infested with aphids using a spray gun the day after release. After treatment, the eggplants were placed in a constant temperature room at 25°C (illuminated for 16 hours), and the number of parasitic adults and larvae was counted four days after treatment, and the control rate (%) was calculated using the above formula (b). The test was conducted in duplicate, with one pot per group.

Test Example 6: Egg killing and larval killing test against Trialeurodes vaporariorum Water was poured into a 120 ml polyethylene cup, and a lid with a hole (diameter about 5 mm) was placed in the center. A cotton wool measuring 8 cm long x 1 cm wide was inserted through the hole in the lid so that it was immersed in the water in the cup, and another cotton wool measuring 5 cm x 5 cm was placed on the cotton wool. In this way, four leaf disks (diameter 2 cm) cut from primary leaves of beans on which adults of Trialeurodes vaporariorum had been allowed to lay eggs were placed on the cotton wool in a state where the water in the cup was constantly replenished. The egg laying was performed by keeping potted beans in a greenhouse where whiteflies were occurring for 24 hours. The cups were placed in an acrylic cylinder 50 cm high and 10 cm in diameter, and 3.0 ml of a water-diluted emulsion (500 ppm) prepared according to Formulation Example 1 was sprayed per cup using an airbrush. 14 days after treatment, the control rate was evaluated on a four-point scale of 100 (control rate: 100%), 80 (same: 99-80%), 50 (same: 79-50%), and 0 (same: less than 50%), and the control rate (%) was calculated based on the results using the following formula (c). The test was carried out using one cup for each section.

Formula (c)
Control rate (%) = (A x 100 + B x 80 + C x 50) / (A + B + C + D)
A: 100 disks, B: 80 disks, C: 50 disks, D: 0 disks

As a result, the compounds of the present invention, compound numbers 1-410 and 2-398, showed a control rate of 80% or more.

Test Example 7: Test of control effect against rice blast (Pyricularia oryzae) by foliar spraying Three-leaf-stage seedlings (5 seedlings/pot) of rice (variety: Asahi) cultivated in plastic pots with a diameter of 6 cm in a greenhouse were sprayed (foliar spray) with 10 ml of a diluted emulsion (200 ppm) prepared according to Preparation Example 1 per pot. The day after the drug treatment, 5 ml of a spore suspension (spore concentration 2 x ¹⁰⁶ /mL) of rice blast fungus conidia formed on another rice leaf in advance was sprayed and inoculated on the pots sprayed with the drug, and the pots were left to stand for 24 hours in an inoculation box at 24°C (relative humidity = 100%), and then the disease was allowed to develop in an artificial climate chamber at 24°C. Seven days after the inoculation, the number of rice blast lesions on the third leaf was counted, and the control rate (%) was calculated using the following calculation formula (d). The test was carried out in triplicate with one pot per plot.

Formula (d)
Control rate (%) = [1 - (number of lesions in treated area/number of lesions in untreated area)] x 100

As a result, compound numbers 1-72, 1-96, 1-97, 1-117, 1-118, 1-119, 1-128, 1-146, 1-172, 1-238, 1-255, 1-277, 1-312, 1-316, 1-325, 1-326, 1-341, 1-362, 1-371, 1-409, 1-510, 1-521, 1-785, 1-789, 1-790, 1-792, 1-796, 1-812, 1-868, 1-910, 1-920, 1-933, 1-936, 1-976, 1-1065 , 1-1091, 1-1107, 1-1133, 1-1168, 1-1226, 1-1229, 1-1233, 1-1237, 1-1248, 1-1253, 1-1262, 1-1264, 1-1281, 1-1289, 1-1291, 1-1293, 1-1295, 1-1325, 1-1326, 1-1327, 1-1329, 1-1355, 1-1364, 1-1426, 2-182, 2-323, 2-336, 2-398, and 2-806 were found to have a control value of 80% or more.

Test Example 8: Test of the control effect of cucumber downy mildew (Pseudoperonospora cubensis) by foliar spraying 10 mL of the diluted emulsion (200 ppm) prepared according to Preparation Example 1 was sprayed per pot on 1.5-leaf-stage cucumber seedlings (variety: Sagami Hanshiro) cultivated in plastic pots with a diameter of 6 cm in a greenhouse (foliar spraying). The day after the drug treatment, 5 mL of a spore suspension (spore concentration 5 x ¹⁰⁵ /mL) of cucumber downy mildew fungus formed on another cucumber leaf in advance was sprayed and inoculated on the pots sprayed with the drug, and the pots were left to stand for 24 hours in an inoculation box at 20°C (relative humidity = 100%), and then the disease was controlled in an artificial climate chamber at 24°C. Five days after the inoculation, the percentage of lesion area (%) on the first leaf was investigated, and the control value was calculated by the following calculation formula (e). The test was carried out in triplicate with one pot per plot.

Formula (e)
Control value (%) = [1 - (percentage of lesion area in treated area/percentage of lesion area in untreated area)] x 100

As a result, compound numbers 1-69, 1-75, 1-86, 1-88, 1-90, 1-93, 1-95, 1-96, 1-97, 1-111, 1-119, 1-132, 1-151, 1-174, 1-185, 1-325, 1-326, 1-334, 1-361, 1-362, 1-370 , 1-395, 1-413, 1-437, 1-525, 1-548, 1-790, 1-795, 1-797, 1-812, 1-840, 1-842, 1-853, 1-868, 1-897, 1-911, 1-912, 1-917, 1-920, 1-936, 1-946, 1-961, 1- The compounds of the present invention, 976, 1-1017, 1-1045, 1-1062, 1-1065, 1-1091, 1-1095, 1-1104, 1-1105, 1-1119, 1-1198, 1-1220, 1-1222, 1-1241, 1-1253, 1-1264, 1-1276, 1-1292, 1-1293, 1-1294, 1-1295, 1-1301, 1-1311, 1-1348, 1-1380, 1-1415, 1-1465, 1-1525, 1-1533, 1-1543, 2-92, 2-182, 2-323, 2-406, and 2-802, showed a control value of 80% or more.

Test Example 9: Test of control effect against barley powdery mildew (Erysiphe graminis) by foliar spraying Barley (variety: Mikamo Golden) seedlings at the 1.5-leaf stage grown in a plastic pot with a diameter of 6 cm in a greenhouse were sprayed (foliar sprayed) with 10 mL of a diluted emulsion (200 ppm) prepared according to Formulation Example 1 per pot. The day after the drug treatment, a spore suspension (spore concentration 5 x ¹⁰⁵ spores/mL) of barley powdery mildew fungus formed on another barley leaf in advance was sprayed and inoculated on the pots sprayed with the drug at 5 mL per pot, and disease development was controlled in an artificial climate chamber at 20°C. Seven days after the inoculation, the percentage of lesion area (%) of barley powdery mildew on the first leaf was investigated, and the control value was calculated by the above-mentioned calculation formula (e). The test was carried out in triplicate with one pot per plot.

As a result, the compounds of the present invention, compound numbers 1-362, 1-790, 1-795, 1-936, 1-1221, 1-1289, and 1-1303, showed a control value of 80% or more.

Test Example 10: Test of control effect by foliar spray against cucumber gray mold 1.5-leaf stage seedlings of cucumber (variety: Tokiwa C series) cultivated in a plastic pot with a diameter of 6 cm in a greenhouse were sprayed with 10 mL of a diluted emulsion (200 ppm) prepared according to Formulation Example-1 per pot (foliar spray). The day after the drug treatment, a piece of agar containing cucumber gray mold (Botrytis cinerea) (diameter 5 mm) previously cultured on a potato decoction medium was inoculated onto the first leaf of the drug-treated cucumber and placed in a greenhouse at 20 ° C. Four days after inoculation, the lesion diameter (cm) was measured, and the control value (%) was calculated according to the following formula (f). The test was carried out in triplicate, with one pot per group.

Formula (f)
Control value (%) = [1 - (lesion diameter in sprayed area/lesion diameter in unsprayed area)] x 100

As a result, the compounds of the present invention with compound numbers 1-121, 1-841, and 1-1108 showed a control value of 80 or more.

Test Example 11: Test of the control effect of wheat brown rust by foliar spraying. 10 mL of the diluted solution (200 ppm) of the wettable powder prepared according to Preparation Example 1 was sprayed per pot on 1.5-leaf stage seedlings of wheat (variety: Norin 61) grown in a plastic pot with a diameter of 6 cm in a greenhouse (foliar spraying). The day after the drug treatment, ⁵ mL of a suspension of uredospores (spore concentration 5 x 105/mL) of wheat brown rust fungus (Puccinia recondita) formed on another wheat leaf in advance was sprayed and inoculated on the pot sprayed with the drug, and the pot was left to stand for 24 hours in an inoculation box at 20 ° C. (relative humidity = 100%), and then the disease was controlled in an artificial climate room at 20 ° C. 10 days after the inoculation, the lesion area percentage (%) on the first leaf was investigated, and the control value was calculated by the above calculation formula (e). The test was carried out in triplicate with one pot per plot.

As a result, the compounds of the present invention, compound numbers 1-102, 1-172, 1-238, 1-255, 1-316, 1-326, 1-521, 1-787, 1-790, 1-791, 1-841, 1-849, 1-929, 1-936, 1-1104, 1-1108, 1-1198, 1-1221, 1-1253, 1-1293, 1-1294, 1-1309, 1-1316, 1-1329, 1-1333, 2-84, 2-323, 2-336, 2-805, and 2-809, showed a control value of 80% or more.

Test Example 12: Test of the control effect of sheath blight by foliar spraying on rice 7-leaf-stage seedlings (pots) of rice (variety: Asahi) cultivated in a plastic pot with a diameter of 6 cm in a greenhouse were sprayed (foliar sprayed) with 10 mL of a diluted emulsion (200 ppm) prepared according to Formulation Example-1 per pot. The day after the drug treatment, a culture of rice sheath blight fungus (Thanatephorus cucumeris) previously cultured in a rice straw medium was inoculated at the base of the pot sprayed with the drug, and the disease was allowed to develop in an artificial climate room at 26°C (relative humidity = 100%). Seven days after the inoculation, the height of the lesions (height from the base of the plant) of rice sheath blight was investigated, and the control value (%) was calculated by the following formula (g). The test was conducted in triplicate with one pot per area.

Formula (g)
Control value (%) = [1 - (lesion spot height in treated area/lesion spot height in untreated area)] x 100

As a result, the compounds of the present invention, compound numbers 1-936, 1-1065, 1-1091, 1-1521, and 1-1533, showed a control value of 80% or more.

The present invention provides novel bicyclic pyridine derivatives and salts thereof, pest control agents containing the derivatives or salts thereof as active ingredients, and methods for using the same.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Patent Application No. 2022-192492) filed on November 30, 2022, the contents of which are incorporated herein by reference.

Claims

General formula (1)

In the formula,
R 1 is a hydrogen atom, a hydroxyl group, a formyl group, a hydroxycarbonyl group, a cyano group, a nitro group, a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted by U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkenyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 haloalkoxycarbonyl group, a C3-C6 cyclo Alkylcarbonyl group, C3-C6 cycloalkyloxycarbonyl group, C1-C6 alkylcarbonyloxy group, C1-C6 haloalkylcarbonyloxy group, C1-C6 alkoxycarbonyloxy group, C1-C6 haloalkoxycarbonyloxy group, C3-C6 cycloalkylcarbonyloxy group, C3-C6 cycloalkyloxycarbonyloxy group, C1-C6 alkylthio group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylthio group, C1-C6 haloalkylsulfinyl group, C1-C6 haloalkylsulfonyl group, C3-C6 cyclo an alkylthio group, a C3-C6 cycloalkylsulfinyl group, a C3-C6 cycloalkylsulfonyl group, a carbamoyl group which may be mono- or poly-substituted by K, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5- or 6-membered ring), an aryl group which may be mono- or poly-substituted by W, a heterocyclic group which may be mono- or poly-substituted by W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a C7-C11 aralkyloxy group which may be mono- or poly-substituted with W, a C7-C11 aralkylthio group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group;
R 2 is a hydrogen atom, a hydroxyl group, a formyl group, a hydroxycarbonyl group, a cyano group, a nitro group, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 haloalkoxycarbonyl group, a C3-C6 cycloalkyloxy group, a C3-C6 cycloalkyloxycarbonyl group, a C1-C6 alkylcarbonyloxy group, a C1-C6 haloalkylcarbonyloxy group, a C1-C6 alkoxycarbonyloxy group, a C1-C6 haloalkoxycarbonyloxy group, a C3-C6 cycloalkylcarbonyloxy group, a C3-C6 cycloalkyloxycarbonyloxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfonyl ... a rufinyl group, a C1-C6 haloalkylsulfonyl group, a C3-C6 cycloalkylthio group, a C3-C6 cycloalkylsulfinyl group, a C3-C6 cycloalkylsulfonyl group, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl group moieties in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-membered ring, a 4-membered ring, a 5-membered ring or a 6-membered ring), an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, an aryloxy group which may be mono- or poly-substituted with W, a heterocyclic oxy group which may be mono- or poly-substituted with W, a benzoyl group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group;
U represents a hydroxyl group, a cyano group, a C1-C6 alkoxy group, or an aryloxy group which may be mono- or poly-substituted by W;
K represents a C1-C6 alkyl group or a C1-C6 alkoxy group;
W is a hydroxyl group, a formyl group, a cyano group, a nitro group, a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted with T, a C1-C6 haloalkyl group, a C1-C6 alkoxy group which may be mono- or poly-substituted with C1-C6 alkoxy groups, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C3-C6 cycloalkylC1-C6 alkoxy group, a C1-C6 a an alkylsulfonyloxy group, a C3-C6 cycloalkylsulfonyloxy group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5- or 6-membered ring); an aryl group which may be mono- or poly-substituted by V, a heterocyclic group which may be mono- or poly-substituted by V, an aryloxy group which may be mono- or poly-substituted by V, a C7-C11 aralkyl group which may be mono- or poly-substituted by V, or a C7-C11 aralkyloxy group which may be mono- or poly-substituted by V,
T represents a hydroxyl group, a cyano group, a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxycarbonyl group, a hydroxyimino group, a C1-C6 alkoxyimino group, or an aryl group which may be mono- or poly-substituted by V;
V represents a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, or a C3-C6 cycloalkyl group;
Z represents an oxygen atom, a sulfur atom, -SO-, -SO 2 -, -CH 2 -, or -CF 2 -;
n represents 0 or 1;
A 1 represents a nitrogen atom or CH;
A2 represents a nitrogen atom or CH;
A3 represents a nitrogen atom or CH.
However, this does not include the case where A 1 is a nitrogen atom, A 2 is CH, and A 3 is a nitrogen atom.
or a salt thereof.
In the general formula (1),
The bicyclic pyridine derivative or salt thereof according to claim 1, wherein R 1 is a halogen atom, a C1-C6 alkyl group optionally mono- or poly-substituted with U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5- or 6-membered ring), an aryl group optionally mono- or poly-substituted with W, a heterocyclic group optionally mono- or poly-substituted with W, a C7-C11 aralkyl group optionally mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group.
In the general formula (1),
R 1 is a halogen atom, a C1-C6 alkyl group which may be mono- or poly-substituted by U, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C3-C6 cycloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, a C1-C6 alkylamino group, a di-C1-C6 alkylamino group (the C1-C6 alkyl alkyl portions in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5-, or 6-membered ring), an aryl group which may be mono- or poly-substituted by W, a heterocyclic group which may be mono- or poly-substituted by W, a C7-C11 aralkyl group which may be mono- or poly-substituted by W, or a C3-C6 cycloalkyl C1-C6 alkyl group;
A1 is CH;
The bicyclic pyridine derivative or a salt thereof according to claim 1, wherein A3 is a nitrogen atom.
In the general formula (1),
R 2 is a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylthio group, a C1-C6 haloalkylthio group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups may be bonded to each other via alkylene groups to form a 3-, 4-, 5- or 6-membered ring), W is 2. The bicyclic pyridine derivative or a salt thereof according to claim 1, which is an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, an aryloxy group which may be mono- or poly-substituted with W, a heterocyclic oxy group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group.
In the general formula (1),
R 2 is a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyloxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkylthio group, a C1-C6 haloalkylthio group, a di-C1-C6 alkylamino group (the C1-C6 alkyl groups in the di-C1-C6 alkylamino group may be the same or different, and the groups are bonded to each other via alkylene groups to form a 3-membered ring, a 4-membered ring, a 5-membered ring, or a 6-membered ring). ), an aryl group which may be mono- or poly-substituted with W, a heterocyclic group which may be mono- or poly-substituted with W, an aryloxy group which may be mono- or poly-substituted with W, a heterocyclic oxy group which may be mono- or poly-substituted with W, a C7-C11 aralkyl group which may be mono- or poly-substituted with W, a heterocyclic C1-C6 alkyl group which may be mono- or poly-substituted with W, or a C3-C6 cycloalkyl C1-C6 alkyl group;
A1 is CH;
The bicyclic pyridine derivative or a salt thereof according to claim 1, wherein A3 is a nitrogen atom.
An agricultural and horticultural agent containing the bicyclic pyridine derivative or its salt according to any one of claims 1 to 5 as an active ingredient.
An insecticide containing the bicyclic pyridine derivative or its salt according to any one of claims 1 to 5 as an active ingredient.
A miticide containing the bicyclic pyridine derivative or its salt according to any one of claims 1 to 5 as an active ingredient.
A nematicide containing the bicyclic pyridine derivative or its salt according to any one of claims 1 to 5 as an active ingredient.
A fungicide containing the bicyclic pyridine derivative or its salt according to any one of claims 1 to 5 as an active ingredient.
A method for controlling plant pests, comprising the step of treating pests and/or their habitat and/or seeds and/or plants and/or plant propagation materials with the agricultural and horticultural agent according to claim 6.
A method for controlling plant pests, comprising a step of treating a place where a useful crop is to be grown or where the useful crop is being grown, or the growing crop, with the agricultural and horticultural agent according to claim 6.
A method for preparing an agricultural or horticultural agent, comprising the step of mixing the bicyclic pyridine derivative or its salt according to any one of claims 1 to 5 with a bulking agent and/or a surfactant.