TW201841566A - Pest control composition containing pyridone compound and quinoline-based compound, method for controlling pests, and novel quinoline compound - Google Patents

Abstract

An object of the invention is to provide a pest control composition that contains a novel active ingredient and is effective in the control of pests, a method for using such a composition, and a novel quinoline-based compound. The invention provides a pest control composition containing, as an active ingredient, at least one component exhibiting pest control activity selected from the group consisting of compounds represented by formula (1) shown below or salts thereof and quinoline-based compounds, and also provides a novel quinoline-based compound which exhibits pest control activity. In the formula, R1 represents an alkyl group of 1 to 6 carbon atoms which may be substituted, or a haloalkyl group of 1 to 6 carbon atoms or the like, R2 represents a halogen atom, an alkyl group of 1 to 6 carbon atoms which may be substituted, or an alkoxy group of 1 to 6 carbon atoms which may be substituted or the like, R3 represents a hydrogen atom, a halogen atom, or an alkyl group of 1 to 6 carbon atoms which may be substituted or the like, n represents an integer from 0 to 5, X represents an oxygen atom or a sulfur atom, Y represents a phenyl group with a substituent at the ortho position, or a pyridyl group or the like, and the bond that includes the dashed line portion represents a double bond or a single bond.

Description

Pesticide-controlling composition containing pyridone compound and quinoline-based compound, method for controlling pests, and novel quinoline-based compound

The present invention relates to a pest control composition containing a pyridone compound and one or more quinoline compounds as active ingredients, and a novel quinoline compound.

In the agriculture and horticulture industry, in order to prevent pests, pathogenic bacteria, weeds and other harmful organisms, pesticides suitable for the control of various pests have generally been used. Furthermore, in order to prevent various pests and the like at the same time, a mixed composition containing a large number of active ingredients is used.

On the other hand, due to the use of pharmaceuticals for many years, drug-resistant pests and resistant bacteria that have acquired drug resistance have increased, and it has been difficult to control them with conventional pharmaceuticals. Therefore, new pest control agents are continuously required. In addition, in order to reduce the risk of drug-resistant pests and tolerant bacteria, a mixture of active ingredients having different mechanisms of action is used.

Regarding 1,3,5,6-substituted-2-pyridone compounds, it has been disclosed, for example, that GABA alpha-2 / 3 ligands have aryl or heteroaryl 1,3,5,6 at the 3-position -A substituted-2-pyridone compound (see, for example, International Publication No. 98/55480). In addition, as a therapeutic agent for bacterial infections, a 1,3,5,6-substituted-2-pyridone compound having a carboxyl group at the 3-position has been disclosed (for example, refer to the specification of European Patent No. 0308020). However, the applications of the compounds described in International Publication No. 98/55480 and European Patent No. 0308020 are all related to medicine, and are different from the technical field to which the pest control composition of the present invention belongs.

Regarding the quinoline-based compound represented by formula (2a) or formula (2b), Patent Documents 3 and 4 disclose quinoline-based compounds as fungicides, which are effective against Pyricularia oryzae and tomato, cucumber and kidney bean gray mold (Botrytis cinerea), Fusarium oxysporum, and other diseases, such as stem and leaf spread, soil treatment, seed treatment and other treatment methods have shown control effects. In addition, Patent Documents 5 and 6 disclose the mixing of a quinoline-based compound represented by the formula (2a) or the formula (2b) with a certain fungicide, and do not disclose the mixing with the pyridone compound of the present invention. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 98/55480 [Patent Literature 2] European Patent No. 0308020 Specification [Patent Literature 3] International Publication No. 05/070917 [Patent Literature 4] International Publication No. 08/066148 [Patent Literature 5 ] International Publication No. 11/077514 [Patent Document 6] International Publication No. 15/141867

(Problems to be Solved by the Invention)

However, the above-mentioned mixed composition containing many active ingredients may have a lower effect on pests than when used in a single agent, so it is anxious for a mixed composition containing new active ingredients and exhibiting a sufficient control effect on pests. . An object of the present invention is to provide a pest control composition containing a novel pyridone compound or a salt thereof in combination with a quinoline compound, which exhibits a useful control effect, a method for using the same, and a novel quinoline compound which exhibits a useful control effect. (The way to solve the problem)

In order to solve the above-mentioned problems, the inventors of the present case have studied the 1,3,5,6-substituted-2-pyridone compound group and the 1,5,6-substituted-2-pyridone compound group, and found that A group of compounds in which a substituted aryl or heteroaryl group and 6 or more quinoline compounds are introduced as active ingredients in the 2-pyridone skeleton is introduced at the ortho position, and a novel quinoline This compound has excellent pest control activity and has completed the present invention. That is, the present invention is as follows.

[1] A pest control composition comprising a pyridone compound or a salt thereof represented by formula (1), and one or more selected from quinoline-based compounds or salts thereof represented by formula (2a) and formula (2b) Ingredients as effective ingredients; [化 1] [In the formula, R1 represents a hydroxyl group, a cyano group, a C1-C6 alkyl group which may be appropriately substituted by a substituent A, a C1-C6 haloalkyl group, and a C3-C8 ring which may also be appropriately substituted by a substituent A. Alkyl, C2 to C6 alkenyl, which may be appropriately substituted with substituent A, C2 to C6 haloalkenyl, C2 to C6 alkynyl, which may be appropriately substituted with substituent A, C2 to C6 haloalkynyl , C1 ~ C6 alkoxy groups that can be appropriately substituted with substituent A, C1 ~ C6 haloalkoxy groups, C3 ~ C8 cycloalkoxy groups that can also be appropriately substituted with substituent A, or substituents C2 ~ C6 alkenyloxy, C2 ~ C6 haloalkenyloxy suitably substituted by A, C3 ~ C6 alkynyloxy optionally substituted by substituent A, C3 ~ C6 haloalkynyloxy, or R10R11N- Here, R10 and R11 each independently represent a hydrogen atom or an alkyl group of C1 to C6; R2 represents a halogen atom, a hydroxyl group, a cyano group, a nitro group, or a C1 to C6 alkane which may be appropriately substituted by a substituent B Group, C1 to C6 haloalkyl group, C3 to C8 cycloalkyl group which may be appropriately substituted with substituent B, C2 to C6 alkenyl group which may be appropriately substituted with substituent B, and C2 to C6 haloalkenyl group C2 ~ C6 alkynes which can also be appropriately substituted by substituent B , C2 ~ C6 haloalkynyl, C1 ~ C6 alkoxy which can be appropriately substituted by substituent B, C1 ~ C6 haloalkoxy, and C3 ~ C8 cycloalkane which can also be appropriately substituted by substituent B Oxygen, C2 ~ C6 alkenyloxy, which may be appropriately substituted by substituent B, haloalkenoxy of C2 ~ C6, alkynyloxy of C3 ~ C6, which may also be appropriately substituted by substituent B, C3 ~ C6 Haloalkynyloxy, R20C (= O)-, where R20 is C1 ~ C6 alkyl, C1 ~ C6 haloalkyl, C3 ~ C8 cycloalkyl, C1 ~ C6 alkoxy, C1 ~ C6 haloalkoxy, C3 to C8 cycloalkoxy, or R21R22N-. Here, R21 and R22 each independently represent a hydrogen atom, and C1 to C6 alkyl, C1 which may be appropriately substituted by substituent B1. A haloalkyl group of ~ C6, or a cycloalkyl group of C3 ~ C8, or R21 and R22 and a bonded nitrogen atom are integrated to form aziridinyl, tetrahydroazetino, pyrrolidinyl, piperidinyl, Homopiperidinyl, or azaoctyl, R20C (= O) O-, where R20 has the same meaning as above, a 3- to 6-membered ring group containing 1 to 2 oxygen atoms, R23-L2- where, R23 represents alkyl group of C1 ~ C6, or haloalkyl of C1 ~ C6, L2 represents S, SO, or SO _2, R21R22N-, here, R 21 and R22 have the same meanings as above, or R24C (= O) N (R25)-, where R24 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, C1 to C6 alkoxy, C1 to C6 haloalkoxy, C3 to C8 cycloalkoxy, or R21R22N-. Here, R21 and R22 have the same meanings as above, R25 represents a hydrogen atom, and may also be substituted. B1 appropriately substituted C1-C6 alkyl, C1-C6 haloalkyl, or C3-C8 cycloalkyl; R3 represents a hydrogen atom, a halogen atom, a nitro group, or C1 that may be appropriately substituted by a substituent C ~ C6 alkyl, C1 ~ C6 haloalkyl, C3 ~ C8 cycloalkyl which can be appropriately substituted by substituent C, C1 ~ C6 alkoxy which can also be appropriately substituted by substituent C, C1 ~ C6 haloalkoxy, C2 to C6 alkenyl, which may be appropriately substituted with substituent C, C2 to C6 haloalkenyl, C2 to C6 alkynyl, which may be appropriately substituted with substituent C, C2 to C6 Haloalkynyl, R30-L3-, where R30 has the meaning of the aforementioned R23, L3 has the meaning of the aforementioned L2, R31R32N-, and here, R31 and R32 have the meaning of the aforementioned R21 and R22, or R33C (= O)-, Here, R33 represents an alkyl group of C1 to C6, a haloalkyl group of C1 to C6, or a cycloalkyl group of C3 to C8; n is 0 to 5 Integer, but when n is 2 or more, two or more of R2 each independently represents a substituent group; X represents an oxygen atom or a sulfur atom; Y represents phenyl, pyridyl, despair Base, pyrimidinyl, pyridine Base, three Base, four Group, thienyl group, thiazolyl group, isothiazolyl group, or thiadiazolyl group, in the phenyl group, the substituent D is substituted in the ortho position, and further, each of the substituents D1 independently has appropriate 0 to 4 substitutions, and the pyridyl group The pyridine Group, the pyrimidinyl group, the da Base, the three Base, or the four In the group, the substituent D is substituted in the ortho position, and further, each of the substituents D1 is independently substituted with appropriate 0 to 3 substitutions. The group D is substituted in the ortho position, and each of the substituents D1 independently has appropriate 0 to 2 substitutions; the bond containing a dashed line portion represents a double bond or a single bond, and the substituent A is selected from the group consisting of a hydroxyl group and a cyanide Group, C3 to C8 cycloalkyl, C1 to C6 alkoxy, C1 to C6 haloalkoxy, C3 to C8 cycloalkoxy, R12R13N-, and R14-L1- (here, R12 and R13 each independently represents a hydrogen atom, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group, or R12 and R13 and a bonded nitrogen atom to form an aziridine. Group, tetrahydroacryl group, pyrrolidinyl, piperidinyl, homopiperidinyl, or azaoctyl group, where R14 represents a C1-C6 alkyl group or a C1-C6 haloalkyl group L1 represents at least one of the group consisting of S, SO, or SO ₂ ); Substituent B represents a group selected from the group consisting of hydroxy, cyano, cycloalkyl from C3 to C8, alkoxy from C1 to C6, C1 ~ C6 haloalkoxy, C3 ~ C8 cycloalkoxy, C2 ~ C 6 alkoxyalkoxy, R21R22N- (here, R21 and R22 have the same meaning as above), R23-L2- (here, R23 and L2 have the same meaning as above), R26R27R28Si- (here, R26, R27, and R28 , Each independently represents an alkyl group of C1 to C6), R26R27R28Si- (CH ₂ ) sO- (here, s represents an integer of 1 to 3, R26, R27 and R28 have the same meanings as above), R20C (= O)-( Here, R20 has the same meaning as above) and at least one member of the group consisting of a 3 to 6-membered ring containing 1 to 2 oxygen atoms; the substituent B1 represents a alkane selected from the group consisting of cyano and C1 to C6 At least one of the group consisting of oxy, C1 to C6 haloalkoxy, and C3 to C8 cycloalkoxy; the substituent C represents a cycloalkyl group selected from hydroxy, cyano, and C3 to C8 , C1 ~ C6 alkoxy, C1 ~ C6 haloalkoxy, C3 ~ C8 cycloalkoxy, R31R32N- (here, R31 and R32 have the same meaning as R21 and R22 mentioned above), and R30-L3- (Herein, R30 has the meaning of R14 and L3 has the meaning of L1 above); at least one of the group consisting of: D is selected from a halogen atom, an alkyl group of C1 to C6, and a haloalkane of C1 to C6 Group, at least one of the group consisting of C1 ~ C6 alkoxy group and C1 ~ C6 haloalkoxy group; substituent D1, Selected from the group consisting of hydroxyl, halogen atom, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3- At least one member of the group consisting of cycloalkoxy groups of C8; [In the formula, R2a and R2b each independently represent an alkyl group of C1 to C6 which may be appropriately substituted by the substituent E1, an aryl group which may be appropriately substituted by the substituent E2, and a heteroaryl group which may be appropriately substituted by the substituent E3. Group, or an aralkyl group which may be appropriately substituted by the substituent E2, or R2a and R2b may be integrated with the carbon atom to which they are bonded to form a cycloalkyl group of C3 to C10 which may also be appropriately substituted by the substituent E4 Ring; R2c and R2d each independently represent a hydrogen atom, an alkyl group of C1 to C6 which may also be appropriately substituted by a substituent E1, a halogen atom, an alkoxy group of C1 to C6, or a hydroxyl group, or R2c and R2d may be used with them The bonded carbon atoms become one to form a carbonyl group or a cycloalkyl ring of C3 ~ C10 which can also be appropriately substituted by the substituent E4; R2e represents a hydrogen atom, a fluorenyl group of C2 ~ C7, or it may also be substituted by E1 Appropriately substituted C1 to C6 alkyl groups; X1 represents a halogen atom, C1 to C6 alkyl groups that may be appropriately substituted with substituent E5, C2 to C6 alkenyl groups that may also be appropriately substituted with substituent E6, or C2 ~ C6 alkynyl suitably substituted with substituent E7, aryl optionally substituted with substituent E2, and optionally substituted E3 Appropriately substituted heteroaryl, C1-C6 alkoxy groups, amine groups that may also be appropriately substituted with substituents E8, fluorenyl groups from C2-C7, cyano groups, or hydrogen atoms that may also be substituted with a substituent E9 N-hydroxyalkanoimide group; X2 represents a halogen atom, an alkyl group of C1 to C6, an alkoxy group or a hydroxyl group of C1 to C6, n1 represents an integer of 0 to 4, n2 represents an integer of 0 to 6, substituent E1 , Represents at least one selected from the group consisting of a halogen atom, an alkoxy group of C1 to C6, an alkylthio group of C1 to C6, and a phenoxy group; and the substituent E2 represents a group selected from a halogen atom, C1 to C6 Alkyl, C1 ~ C6 haloalkyl, C1 ~ C6 alkoxy, amine, nitro, cyano, hydroxy, mercapto, and C1 ~ C6 alkylthio At least one of the group consisting of; the substituent E3 represents at least one selected from the group consisting of a halogen atom, an alkyl group of C1 to C6, a haloalkyl group of C1 to C6, and an alkoxy group of C1 to C6 The substituent E4 represents at least one selected from the group consisting of a halogen atom, an alkyl group of C1 to C6, an alkoxy group of C1 to C6, and a phenoxy group; the substituent E5 represents a group selected from a halogen atom, C1 ~ C6 alkoxy At least one of the group consisting of a hydroxy group, a hydroxyl group, an alkoxycarbonyl group of C2 to C7, and a phenoxy group; the substituent E6 represents a group selected from a halogen atom, an alkoxy group of C1 to C6, and an alkoxy group of C2 to C7 At least one member of the group consisting of carbonyl and phenoxy groups; the substituent E7 represents at least one member selected from the group consisting of halogen atoms, alkoxy groups of C1 to C6, and phenoxy groups; the substituent group E8 , Represents at least one selected from the group consisting of C1 to C6 alkyl groups and C2 to C7 fluorenyl groups; the substituent E9 represents a group selected from C1 to C6 alkyl groups, C2 to C6 alkenyl groups, C2 to C6 is at least one member of the group consisting of alkynyl, aralkyl, aryl, and heteroaryl].

[2] The pest control composition according to [1], wherein in the pyridone compound represented by the formula (1), R1 represents a cyano group, a C1-C6 alkyl group, and C1- C6 haloalkyl, C3 to C8 cycloalkyl which may be appropriately substituted with substituent A, C2 to C6 alkenyl which may be appropriately substituted with substituent A, C2 to C6 haloalkenyl, or C2 ~ C6 alkynyl, or R10R11N-, which is appropriately substituted by substituent A, where R10 and R11 each independently represent a hydrogen atom or an alkyl group of C1-C6; R2 represents a halogen atom, a hydroxyl group, a cyano group, or C1-C6 alkyl, C1-C6 haloalkyl, which may be appropriately substituted by substituent B, C1-C6 alkoxy, C1-C6 haloalkoxy, which may also be appropriately substituted by substituent B C3 ~ C8 cycloalkoxy groups which may be appropriately substituted with substituent B, C2 ~ C6 alkoxy groups which may be appropriately substituted with substituent B, and C3 ~ C6 alkynyloxy groups which may be appropriately substituted with substituent B , R20C (= O) O- (Here, R20 represents C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 halogen Alkoxy, C3 ~ C8 cycloalkoxy, or R21R22N- (here, R21 and R22 C1-C6 alkyl group, C1-C6 haloalkyl group, C3-C8 cycloalkyl group, or R21 and R22 and bonded nitrogen Atoms are integrated to form aziridinyl, tetrahydroacryl, pyrrolidinyl, piperidinyl, homopiperidinyl, or azaoctyl) Represents C1 ~ C6 alkyl, or C1 ~ C6 haloalkyl, L2 represents S, SO, or SO ₂ ); R3 represents hydrogen atom, halogen atom, or C1 ~ C6 which can be appropriately substituted by substituent C Alkyl, C3 ~ C8 cycloalkyl, which may be appropriately substituted with substituent C, C1 ~ C6 alkoxy, which may be appropriately substituted with substituent C, C2 ~ C6, which may be appropriately substituted with substituent C Alkynyl, or R30-L3-, where R30 has the same meaning as R23 and L3 has the same meaning as L2; Y is phenyl or pyridyl, in which the substituent D is substituted in the ortho position and further substituted Each of the groups D1 independently has appropriate 0 to 4 substitutions. In the pyridyl group, the substituent D is substituted in the ortho position, and further, each of the substituents D1 is independently substituted with appropriate 0 to 3 substitutions.

[3] The pest control composition according to [2], wherein in the pyridone compound represented by the formula (1), R1 represents a C1-C6 alkyl group or a C1-C6 alkyl group which can also be appropriately substituted by a substituent A Haloalkyl; R2 represents a halogen atom, an alkyl group of C1 to C6 which may be appropriately substituted by substituent B, or an alkoxy group of C1 to C6 which may also be appropriately substituted by substituent B; R3 represents a hydrogen atom, a halogen atom Or a C1-C6 alkyl group which may be appropriately substituted by a substituent C.

[4] The pest control composition according to [1], wherein, in the quinoline-based compound represented by formula (2a) or formula (2b), R2a and R2b are each independently C1 which may be appropriately substituted by substituent E1 ~ C6 alkyl, R2c and R2d are each independently a hydrogen atom, an alkyl or halogen atom of C1 ~ C6 which may be appropriately substituted by substituent E1, R2e is a hydrogen atom or C1 which may also be appropriately substituted by substituent E1 An alkyl group of ~ C6, X1 is a halogen atom, X2 is a halogen atom, n1 is an integer of 0 to 4, and n2 is an integer of 0 to 6.

[5] The pest control composition according to [1], wherein the quinoline compound represented by formula (2a) or (2b) is a quinoline compound represented by formula (2c) or (2d); 3] [In the formula, R2f represents a hydrogen atom or a methyl group, X3, X4, and X5 each independently represent a hydrogen atom or a fluorine atom, and X6 and X7 each independently represent a hydrogen atom, a methyl group, or a fluorine atom].

[6] The pest control composition according to [4], wherein the quinoline compound represented by formula (2a) or formula (2b) is selected from the group consisting of 3- (4,4-difluoro-3,3-dimethyl -3,4-dihydroisoquinolin-1-yl) quinoline, 3- (4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl ) -8-fluoroquinoline, 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-1,2,3,4-tetrahydroisoquinolin-1-yl) quine And at least one member of the group consisting of 8-fluoro-3- (5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) quinoline.

[7] A method for controlling pests by applying a pest control composition such as [1].

[8] A method for controlling pests, comprising simultaneously applying a composition containing a pyridone compound or a salt thereof represented by formula (1) as shown in [1] as an active ingredient, and containing a formula (2a) as shown in [1] or A composition in which a quinoline compound or a salt thereof represented by formula (2b) is an active ingredient.

[9] A method for controlling pests by applying a composition containing a pyridone compound or a salt thereof represented by formula (1) as in [1] as an active ingredient, or containing formula (2a) or formula as in [1] Any one of the quinoline-based compounds represented by (2b) or a salt thereof as an active ingredient is applied to the other composition.

[10] A quinoline-based compound or a salt thereof, which is a quinoline-based compound represented by formula (2c) or formula (2d) in [5], R2f is a hydrogen atom or a methyl group, X3 is a fluorine atom, X4, X5 , X6 and X7 are each independently a hydrogen atom or a fluorine atom, but in formula (2c), at least one of X4, X5, X6 or X7 is a fluorine atom, and in formula (2d), any of X4 or X5 is Is a fluorine atom.

[11] The quinoline compound or a salt thereof according to [10], wherein the quinoline compound represented by the formula (2c) or the formula (2d) is 3- (4,4-difluoro-3,3-dimethyl -3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline, 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-1,2, 3,4-tetrahydroisoquinolin-1-yl) quinoline, or 8-fluoro-3- (5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl )quinoline.

[12] The quinoline compound or a salt thereof according to [11], wherein the quinoline compound represented by the formula (2c) or the formula (2d) is 3- (4,4-difluoro-3,3-dimethyl -3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline or 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-1,2, 3,4-tetrahydroisoquinolin-1-yl) quinoline.

[13] A method for controlling pests, comprising the steps of: applying an effective amount of a compound of formula (I) as described in [1] or a plant, seed, soil, seed box, or tray to the pests A salt and a quinoline-based compound represented by formula (2a) or formula (2b) or a salt thereof.

[14] The use of a compound of formula (I) or a salt thereof as in [1] and a quinoline compound or a salt thereof represented by formula (2a) or formula (2b), as a pest control agent. (Effect of the invention)

According to the present invention, it is possible to provide a pest control composition useful for controlling pests containing a novel active ingredient, a method for using the same, and a novel quinoline compound.

This embodiment will be described below. It should be noted that the terms used in the scope of patent application and the description in the specification, unless otherwise specified, are in accordance with the definitions commonly used in the technical field, and the abbreviations used in the specification are described below. DMF: N, N-dimethylformamide, THF: tetrahydrofuran, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, Pentyl: pentyl, Hexyl: hexyl, Ac: acetamidine Group, Ph: phenyl, Py: pyridyl, i: iso, sec: second, t: third, c: ring, =: double bond, ≡: reference bond. In the column of the table, a single “-” stands for no substitution. When Pr, Bu, Pentyl, and Hexyl have no linker, it means normal. -di-:-di-, -tri-:-tri-, -penta-:-penta-, 1,3-dioxolan-2-yl: 1,3-dioxolan-2-yl, 1 , 3-dioxan-2-yl: 1,3-dioxan-2-yl.

The definitions of the terms used in this manual are explained below. The records of Cx ~ Cy represent x to y carbon atoms. The term "may also be appropriately substituted" means substituted or unsubstituted. When this term is used, if the number of substituents is not specified, the number of substituents is 1. The C1-C6 alkyl group may be linear or branched, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, and pentyl , Isopentyl, 2-methylbutyl, neopentyl, 1-ethylpropyl, hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methyl Amyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethyl Butyl, 2,3-dimethylbutyl, or 2-ethylbutyl.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

C1 ~ C6 haloalkyl refers to those obtained by arbitrarily substituting one or more halogen atoms of hydrogen atoms in the aforementioned C1 ~ C6 alkyl groups. When two or more halogen atoms are substituted, these halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as they can exist as substituents. Specific examples of the C1-C6 haloalkyl group include monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, monobromomethyl, monoiodomethyl, chlorodifluoromethyl, and bromodi Fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2 2,2-tetrafluoroethyl, pentafluoroethyl, 2,2,2-trichloroethyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoropropyl, hepta Fluoroisopropyl, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl, nonafluorobutyl, nonafluoro-second butyl, 3,3,4,4,5,5, 5-heptafluoropentyl, undecafluoropentyl, tridecylfluorohexyl and the like.

The fluoroalkyl group of C1 to C6 represents a hydrogen atom in the aforementioned C1 to C6 alkyl group obtained by arbitrarily replacing one or more fluorine atoms. Specific examples of the fluoroalkyl group of C1 to C6 include monofluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, and 2, 2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, 3,3-difluoropropyl, 3,3,3 -Trifluoropropyl, heptafluoropropyl, heptafluoroisopropyl, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl, nonafluorobutyl, nonafluoro-second butyl, 3,3,4,4,5,5,5-heptafluoropentyl, undecafluoropentyl, tridecylfluorohexyl, etc.

C3 ~ C8 cycloalkyl refers to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl.

The C2 to C6 alkenyl group means one having one or two or more double bonds and being a linear or branched unsaturated hydrocarbon group. When there are geometric isomers, it is only one of E-form or Z-form, or a mixture of E-form and Z-form in any ratio, and there is no particular limitation as long as it is within the specified carbon number range. Specific examples of the alkenyl group of C2 to C6 include vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, and 2-pentyl. Alkenyl, 3-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 4-methyl-3-pentenyl, 3-methyl-2-pentenyl, and the like.

C2 ~ C6 haloalkenyl refers to those obtained by arbitrarily replacing one or more halogen atoms of hydrogen atoms in the alkenyl groups of C2 ~ C6. When two or more halogen atoms are substituted, these halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as they can exist as substituents. Specific examples of the haloalkenyl group of C2 to C6 include 2-fluorovinyl, 2,2-difluorovinyl, 2,2-dichlorovinyl, 3-fluoroallyl, and 3,3-difluoroene. Propyl, 3,3-dichloroallyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4-pentenyl, 6,6-difluoro-5-hexene Base etc.

C2 ~ C6 alkynyl refers to those which have one or more than two reference bonds and are linear or branched unsaturated hydrocarbon groups. Specific examples of the alkynyl group of C2 to C6 include ethynyl, 1-propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2- Pentynyl, 3-pentynyl, 4-pentynyl, 1,1-dimethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4- Hexynyl, 5-hexynyl and the like.

C2 ~ C6 haloalkynyl refers to those obtained by arbitrarily replacing one or more halogen atoms of hydrogen atoms in the alkynyl groups of C2 ~ C6. When two or more halogen atoms are substituted, these halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as they can exist as substituents. Specific examples of the haloalkynyl group of C2 to C6 include 2-fluoroethynyl, 2-chloroethynyl, 2-bromoethynyl, 2-iodoethynyl, 3,3-difluoro-1-propynyl, 3 -Chloro-3,3-difluoro-1-propynyl, 3-bromo-3,3-difluoro-1-propynyl, 3,3,3-trifluoro-1-propynyl, 4, 4-difluoro-1-butynyl, 4,4-difluoro-2-butynyl, 4-chloro-4,4-difluoro-1-butynyl, 4-chloro-4,4-di Fluoro-2-butynyl, 4-bromo-4,4-difluoro-1-butynyl, 4-bromo-4,4-difluoro-2-butynyl, 4,4,4-trifluoro -1-butynyl, 4,4,4-trifluoro-2-butynyl, 5,5-difluoro-3-pentynyl, 5-chloro-5,5-difluoro-3-pentyne , 5-bromo-5,5-difluoro-3-pentynyl, 5,5,5-trifluoro-3-pentynyl, 6,6-difluoro-4-hexynyl, 6-chloro -6,6-difluoro-4-hexynyl, 6-bromo-6,6-difluoro-4-hexynyl, 6,6,6-trifluoro-4-hexynyl and the like.

The C1-C6 alkoxy group refers to those in which the C1-C6 alkyl group is bonded via an oxygen atom. Specific examples of the alkoxy group of C1 to C6 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, third butoxy, Pentyloxy, isopentyloxy, 2-methylbutoxy, neopentyloxy, 1-ethylpropoxy, hexyloxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1-methylpentoxy, 3,3-dimethylbutoxy, 2,2-dimethylbutoxy, 1,1-dimethylbutoxy, 1 , 2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy, and 2-ethylbutoxy.

C1 ~ C6 haloalkoxy refers to those obtained by arbitrarily replacing one or more halogen atoms of hydrogen atoms in the alkoxy groups of C1 ~ C6. When two or more halogen atoms are substituted, these halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as they can exist as substituents. Specific examples of the haloalkoxy group of C1 to C6 include difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, and 2,2- Difluoroethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, pentafluoroethoxy, 2,2,2-trichloroethoxy, 3,3-difluoropropoxy, 3,3,3-trifluoropropoxy, heptafluoropropoxy, heptafluoroisopropoxy, 2,2,2-trifluoro-1- (trifluoromethyl ) -Ethoxy, nonafluorobutoxy, nonafluoro-second butoxy, 3,3,4,4,5,5,5-heptafluoropentyloxy, undecylpentyloxy, ten Trifluorohexyloxy and the like.

The cycloalkoxy group of C3 ~ C8 refers to the above-mentioned cycloalkyl group of C3 ~ C8 which is bonded via an oxygen atom. Specific examples of the cycloalkoxy group of C3 to C8 include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

The alkenyloxy group of C2 ~ C6 refers to the aforementioned alkenyl group of C2 ~ C6 which is bonded by an oxygen atom. When there are geometric isomers, it is only one of E-form or Z-form, or a mixture of E-form and Z-form in any ratio, and there is no particular limitation as long as it is within the specified carbon number range. Specific examples of the alkenyloxy group in C2 to C6 include ethyleneoxy, 1-propenyloxy, allyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1- Pentenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 3-methyl-2-butenyloxy, 1-hexenyloxy, 2-hexenyloxy Group, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, 4-methyl-3-pentenyloxy, 3-methyl-2-pentenyloxy and the like.

C2 ~ C6 haloalkenyloxy refers to those obtained by arbitrarily replacing the hydrogen atom in the alkenyloxy group of C2 ~ C6 with one or more halogen atoms. When two or more halogen atoms are substituted, these halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as they can exist as substituents. Specific examples of the haloalkenyloxy group of C2 to C6 include 2-fluoroethyleneoxy, 2,2-difluoroethyleneoxy, 2,2-dichloroethyleneoxy, 3-fluoroallyloxy, 3, 3-difluoroallyloxy, 3,3-dichloroallyloxy, 4,4-difluoro-3-butenyloxy, 5,5-difluoro-4-pentenyloxy, 6, 6-difluoro-5-hexenyloxy and the like.

The alkynyloxy group of C3 to C6 refers to the alkynyl group of C2 to C6, and the alkynyl group of C3 to C6 is bonded by an oxygen atom. Specific examples of the alkynyloxy group in C3 to C6 include propargyloxy, 2-butynyloxy, 3-butynyloxy, 2-pentynyloxy, 3-pentynyloxy, and 4-pentynyloxy. Group, 1,1-dimethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-hexynyloxy, 5-hexynyloxy and the like.

C3 ~ C6 haloalkynyloxy refers to those obtained by arbitrarily replacing one or more halogen atoms of hydrogen atoms in the alkynyloxy groups of C3 ~ C6. When two or more halogen atoms are substituted, these halogen atoms may be the same or different, and the number of substitutions is not particularly limited as long as they can exist as substituents. Specific examples of the alkynyloxy group of C3 to C6 include 1,1-difluoro-2-propynyloxy, 4,4-difluoro-2-butynyloxy, 4-chloro-4,4-di Fluoro-2-butynyloxy, 4-bromo-4,4-difluoro-2-butynyloxy, 4,4,4-trifluoro-2-butynyloxy, 5,5-difluoro- 3-pentynyloxy, 5-chloro-5,5-difluoro-3-pentynyloxy, 5-bromo-5,5-difluoro-3-pentynyloxy, 5,5,5-tris Fluoro-3-pentynyloxy, 6,6-difluoro-4-hexynyloxy, 6-chloro-6,6-difluoro-4-hexynyloxy, 6-bromo-6,6-di Fluoro-4-hexynyloxy, 6,6,6-trifluoro-4-hexynyloxy and the like.

The alkoxyalkoxy group of C2 ~ C6 means the hydrogen atom in the alkoxy group of C1 ~ C5 in the alkoxy group of C1 ~ C6 mentioned above is optionally substituted by one or more C1 ~ C5 alkoxy groups Become. There is no special restriction if the total number of carbon numbers is within the specified carbon number range. Specific examples of the alkoxyalkoxy group of C2 to C6 include methoxymethoxy, ethoxymethoxy, propoxymethoxy, isopropoxymethoxy, and methoxyethoxy. , Ethoxyethoxy, propoxyethoxy, isopropoxyethoxy, methoxypropoxy, ethoxypropoxy, propoxypropoxy, isopropoxypropoxy Base etc.

C2 to C12 alkoxyalkyl refers to those in which the aforementioned C1 to C6 alkyl groups are bonded to the aforementioned C1 to C6 alkoxy groups. There is no special restriction if the total number of carbon numbers is within the specified carbon number range. Specific examples of the alkoxyalkyl group of C2 to C12 include a methoxymethyl group, an ethoxymethyl group, a 2-methoxyethyl group, and a 2-ethoxyethyl group.

The alkoxycarbonyl group of C2 to C7 refers to a group in which a carbonyl group is bonded to the alkoxy group of C1 to C6. Specific examples of the alkoxycarbonyl group of C2 to C7 include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, 1-butoxycarbonyl, 2-butoxycarbonyl, and 1- Pentyloxycarbonyl, 1-ethylpropoxycarbonyl, 1-hexylcarbonyl and the like.

The C1-C6 alkylthio group refers to a group in which the C1-C6 alkyl group is bonded with a sulfur atom. Specific examples of the alkylthio group of C1 to C6 include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, and second butylthio group. , Third butylthio, pentylthio, isopentylthio, 2-methylbutylthio, neopentylthio, 1-ethylpropylthio, hexylthio, 4-methyl Pentylthio, 3-methylpentylthio, 2-methylpentylthio, 1-methylpentylthio, 3,3-dimethylbutylthio, 2,2-bis Methylbutylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,3-dimethyl Butylthio, 2-ethylbutylthio, and the like.

The fluorenyl group of C2 to C7 refers to a group in which a carbonyl group is bonded to the aforementioned C1 to C6 alkyl group. Specific examples of the fluorenyl group of C2 to C7 include ethyl fluorenyl, propyl fluorenyl, 1-butyl fluorenyl, 2-methyl propyl fluorenyl, 1-pentyl fluorenyl, 2-methyl butyl fluorenyl, 1-hexane fluorenyl, 2 -Methylpentyl, 2-ethylbutylfluorenyl and the like.

The alkylsulfonylethyl group of C3 ~ C8 is obtained by bonding the aforementioned C1 ~ C6 alkyl group to a sulfur atom of a sulfoethyl group. If the sum of carbon numbers is within the specified carbon number range, there are no special restrictions. Examples of C3 to C8 alkylsulfonylethyl include 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2- (1-propylsulfonyl) ethyl, 2- ( 2-propylsulfonyl) ethyl, 1-methyl-2-methylsulfonylethyl, 1-ethyl-2-methylsulfonylethyl, 2-methyl-2-methyl Sulfonylethyl, 2-ethyl-2-ethylsulfonylethyl, 1-methyl-2-methyl-2methylsulfonylethyl, and the like.

Aryl represents a C1-C14 1-3 aromatic ring. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group.

Heteroaryl refers to a 1 to 3 cyclic aromatic ring containing 5 to 14 members of a heteroatom containing one or two identical or different rings. The type of the hetero atom is not particularly limited, and examples thereof include a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples of the heteroaryl group include furyl, thienyl, pyrrolyl, Oxazolyl, iso Oxazolyl, dihydroiso Oxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, Diazyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, azepine, oxaazepine, etc. 5- to 7-membered monocyclic heteroaryl, benzofuryl, isobenzo Furyl, benzothienyl, indolyl, isoindolyl, indazolyl, benzo Oxazolyl Oxazolyl, benzothiazolyl, benzoisothiazolyl, benzo Diazolyl, benzothiadiazolyl, benzotriazolyl, quinolinyl, isoquinolinyl, Quinolyl, quinazolinyl, quinol Phenyl base, Pyridyl, purinyl, pteridinyl, carbazolyl, carbolinyl, acridinyl, 2-acridyl, 3-acridyl, 4-acridyl, 9-acridyl Base, brown Base Base, brown 8 to 14-membered polycyclic heteroaryl.

An aralkyl group refers to a group in which one or more hydrogen atoms of the C1-C6 alkyl group are substituted by the aryl group. Specific examples of the aralkyl group include benzyl, 1-naphthylmethyl, 2-naphthylmethyl, anthracenemethyl, phenanthrylmethyl, fluorenylmethyl, diphenylmethyl, 1-phenethyl, 2 -Phenethyl, 1- (1-naphthyl) ethyl, 1- (2-naphthyl) ethyl, 2- (1-naphthyl) ethyl, 2- (2-naphthyl) ethyl, 3 -Phenylpropyl, 3- (1-naphthyl) propyl, 3- (2-naphthyl) propyl, 4-phenylbutyl, 4- (1-naphthyl) butyl, 4- (2 -Naphthyl) butyl, 5-phenylpentyl, 5- (1-naphthyl) pentyl, 5- (2-naphthyl) pentyl, 6-phenylhexyl, 6- (1-naphthyl) Hexyl, 6- (2-naphthyl) hexyl.

The C3-C10 cycloalkyl ring refers to a cyclopropyl ring, a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, or a cyclooctyl ring.

The N-hydroxyalkylimino group refers to a hydroxyiminomethyl group, an N-hydroxyethaneimino group, an N-hydroxypropane group imine group, an N-hydroxybutane group imine group, and the like.

Specific examples of the 3- to 6-membered ring group containing 1 to 2 oxygen atoms include 1,2-oxiranyl, propylene oxide, oxolanyl, and oxane (Oxanyl), 1,3-dioxanyl, 1,3-dioxanyl (1,3-dioxanyl), 1,4-dioxanyl (1, 4-dioxanyl) and the like.

The pest control composition of the present invention (hereinafter sometimes referred to as the composition of the present invention) is characterized in that a pyridone compound represented by the following formula (1) or a salt thereof (in this specification, sometimes referred to as the formula (1) Compound represented by the present invention, compound of the present invention), and a quinoline-based compound represented by the formula (2a) or the formula (2b) or a salt thereof (in this specification, the compound represented by the formula (2a) or the formula (2b) may be abbreviated Or collectively referred to as a quinoline-based compound) as an active ingredient.

[Chemical 4] [Chemical 5]

Formula (1) will be described below. R1 in the formula (1) represents a hydroxy group, a cyano group, a C1 to C6 alkyl group which can be appropriately substituted with a substituent A, a C1 to C6 haloalkyl group, and a C3 to C8 ring which can also be appropriately substituted with a substituent A. Alkyl, C2 to C6 alkenyl, which may be appropriately substituted with substituent A, C2 to C6 haloalkenyl, C2 to C6 alkynyl, C2 to C6 haloalkynyl, which may also be appropriately substituted with substituent A , C1 ~ C6 alkoxy groups which can be appropriately substituted with substituent A, C1 ~ C6 haloalkoxy groups, C3 ~ C8 cycloalkoxy groups which can also be appropriately substituted with substituent A, or substituents A is appropriately substituted C2 ~ C6 alkoxy, C2 ~ C6 haloalkoxy, C3 ~ C6 alkynoxy, C3 ~ C6 haloalkoxy, or R10R11N- (Here, R10 and R11 each independently represent a hydrogen atom or an alkyl group of C1 to C6.)

Among them, R1 is preferably a cyano group, an alkyl group of C1 to C6 which can be appropriately substituted by substituent A, a haloalkyl group of C1 to C6, a cycloalkyl group of C3 to C8 which can also be appropriately substituted by substituent A, or C2 to C6 alkenyl, C2 to C6 haloalkenyl appropriately substituted with substituent A, C2 to C6 alkynyl optionally substituted with substituent A, or R10R11N- (here, R10 and R11 are the same as previously described Meaning.) Ideally, especially C1-C6 alkyl groups or C1-C6 haloalkyl groups which can also be appropriately substituted by the substituent A are preferred.

"Substituent A" in formula (1) represents a ring selected from the group consisting of hydroxyl, cyano, cycloalkyl of C3 to C8, alkoxy of C1 to C6, haloalkoxy of C1 to C6, and ring of C3 to C8 Alkoxy, R12R13N- (here, R12 and R13 each independently represent a hydrogen atom, an alkyl group of C1 to C6, a haloalkyl group of C1 to C6, or a cycloalkyl group of C3 to C8, or R12 and R13 and The bonded nitrogen atoms become one to form aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, homopiperidinyl, or azocanyl.) And R14-L1- (here, R14 represents an alkyl group of C1 to C6, or a haloalkyl group of C1 to C6, and L1 represents S, SO, or SO _2. ) At least one of the group consisting of R1 and L1.

Among them, the substituent A is preferably a cyano group, an alkoxy group of C1 to C6, or R14-L1- (here, R14 and L1 have the same meanings as described above.) It is preferable that the cyano group or the alkoxy group of C1 to C6 is particularly Better.

Preferred specific examples of the substituent A include a hydroxyl group; a cyano group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group as the cycloalkyl group of C3 to C8; and a methoxy group as the alkoxy group of C1 to C6. Group, ethoxy group, propoxy group, and isopropoxy group; difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, haloalkoxy group as C1 to C6, 2, 2,2-trifluoroethoxy, 3,3-difluoropropoxy, and 3,3,3-trifluoropropoxy; Examples of cycloalkoxy groups C3 to C8 include cyclopropoxy and cyclobutane An amine group, a cyclopentyloxy group, and a cyclohexyloxy group; an amine group, a dimethylamino group, an ethylmethylamino group, and a diethylamino group as R12R13N- (here, R12 and R13 have the same meanings as described above); And R14-L1- (herein, R14 and L1 have the same meanings as above.) Methylthio, methanesulfinyl, methanesulfonyl, trifluoromethylthio, trifluoromethanesulfinyl, and three Fluoromethanesulfonyl.

More preferable specific examples of the substituent A include a hydroxy group; a cyano group; a cyclopropyl group as a cycloalkyl group of C3 to C8, and a cyclobutyl group; a methoxy group of an alkoxy group of C1 to C6, and an ethoxy group ; C1 ~ C6 haloalkoxy, difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, and 2,2,2-trifluoroethoxy; C3 ~ C8 ring Cyclopropoxy and cyclobutoxy of alkoxy; dimethylamino, ethylmethylamino, and diethylamino as R12R13N- (here, R12 and R13 have the same meanings as above.); And as R14-L1- (herein, R14 and L1 have the same meanings as above.) Methylthio, methanesulfinyl, and methanesulfonyl.

R1 in formula (1) includes a hydroxyl group and a cyano group. The C1-C6 alkyl group of "C1-C6 alkyl group which may also be appropriately substituted by substituent A" in R1 of formula (1) is synonymous with the foregoing definition, preferably methyl, ethyl, propyl , Isopropyl, butyl, or isobutyl, more preferably methyl or ethyl. When having a substituent A, a hydrogen atom in the alkyl group of C1 to C6 may be optionally substituted by the substituent A.

The "C1 to C6 haloalkyl group" in R1 of formula (1) has the same meaning as the foregoing definition, preferably 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoro Ethyl, 3,3-difluoropropyl, or 3,3,3-trifluoropropyl, more preferably 2-fluoroethyl, 2,2-difluoroethyl, or 2,2,2-tri Fluoroethyl.

The cycloalkyl group of C3 ~ C8 of "C3 ~ C8 cycloalkyl group which may also be appropriately substituted by substituent A" in R1 of formula (1) has the same meaning as the foregoing definition, and preferably cyclopropyl group or cyclobutyl group Group, cyclopentyl, or cyclohexyl, more preferably cyclopropyl or cyclobutyl. When the substituent A is present, the hydrogen atom in the cycloalkyl group of C3 to C8 may be optionally substituted by the substituent A.

The alkenyl groups of C2 to C6 of "alkenyl groups of C2 to C6 which may also be appropriately substituted by substituent A" in R1 of formula (1) have the same meanings as the foregoing definitions, preferably vinyl, 1-propenyl, Or allyl, more preferably vinyl, or allyl. When there is a substituent A, the hydrogen atom in the alkenyl group of C2 to C6 may be optionally substituted by the substituent A.

The "haloalkenyl group of C2 to C6" in R1 of formula (1) has the same meaning as the foregoing definition, and is preferably 2-fluorovinyl, 2,2-difluorovinyl, 3-fluoroallyl, or 3,3-difluoroallyl, more preferably 2-fluorovinyl, or 2,2-difluorovinyl.

The alkynyl groups of C2 to C6 of "C2 to C6 alkynyl groups which may also be appropriately substituted by substituent A" in R1 of formula (1) have the same meanings as above, preferably propargyl and 2-butyne Or 3-butynyl, more preferably propargyl. When there is a substituent A, a hydrogen atom in the alkynyl group of C2 to C6 may be optionally substituted by the substituent A.

The "haloalkynyl group of C2 to C6" in R1 of formula (1) has the same meaning as the foregoing definition, and is preferably 4,4-difluoro-2-butynyl, 4-chloro-4,4-difluoro 2-butynyl, 4-bromo-4,4-difluoro-2-butynyl, or 4,4,4-trifluoro-2-butynyl, more preferably 4,4-difluoro- 2-butynyl, or 4,4,4-trifluoro-2-butynyl.

The alkoxy groups of C1 to C6 of "C1 to C6 alkoxy groups that may also be appropriately substituted by substituent A" in R1 of formula (1) have the same meanings as the foregoing definitions, preferably methoxy and ethoxy Group, propoxy, isopropoxy, butoxy, or isobutoxy, more preferably methoxy or ethoxy. When the substituent A is present, the hydrogen atom in the alkoxy group of C1 to C6 may be optionally substituted by the substituent A.

The "haloalkoxy group of C1 to C6" in R1 of formula (1) has the same meaning as the foregoing definition, and is preferably difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropoxy, or 3,3,3-trifluoropropoxy, more preferably difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, or 2,2,2-trifluoroethoxy.

The C3 to C8 cycloalkoxy group of "C3 to C8 cycloalkoxy group that may also be appropriately substituted with substituent A" in R1 of formula (1) has the same meaning as the foregoing definition, and cyclopropyloxy group is preferred. , Cyclobutoxy, cyclopentyloxy, or cyclohexyloxy, more preferably cyclopropoxy or cyclobutoxy. When the substituent A is present, the hydrogen atom in the cycloalkoxy group of C3 to C8 may be optionally substituted by the substituent A.

The alkenyl group of C2 to C6 of the "alkenyl group of C2 to C6 which may also be appropriately substituted by substituent A" in R1 of formula (1) has the same meaning as the foregoing definition, preferably vinyloxy group, 1- Allyloxy or allyloxy is more preferably ethyleneoxy. When there is a substituent A, the hydrogen atom in the alkenyloxy group of C2 to C6 may be optionally substituted by the substituent A.

The "haloalkenyloxy group of C2 to C6" in R1 of formula (1) has the same meaning as the foregoing definition, and is preferably 2-fluoroethyleneoxy, 2,2-difluoroethyleneoxy, 3-fluoroallyl Oxy, or 3,3-difluoroallyloxy, more preferably 2-fluoroethyleneoxy, or 2,2-difluoroethyleneoxy.

The alkynyloxy group of C3 to C6 of "C3 to C6 alkynyloxy group that may also be appropriately substituted by substituent A" in R1 of formula (1) has the same meaning as the foregoing definition, and is preferably propargyloxy, 2 -Butynyloxy or 3-butynyloxy, more preferably propargyloxy. When there is a substituent A, the hydrogen atom in the alkynyloxy group of C3 to C6 may be optionally substituted by the substituent A.

The "C3 to C6 haloalkynyloxy group" in R1 of formula (1) has the same meaning as the foregoing definition, and is preferably 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4- Difluoro-2-butynyloxy, 4-bromo-4,4-difluoro-2-butynyloxy, or 4,4,4-trifluoro-2-butynyloxy, more preferably 4, 4-difluoro-2-butynyloxy, or 4,4,4-trifluoro-2-butynyloxy.

"R10R11N-" in R1 in formula (1) (here, R10 and R11 each independently represent a hydrogen atom or an alkyl group of C1 to C6.) The alkyl group of C1 to C6 has the same meaning as the foregoing definition. "R10R11N-" preferably includes an amino group, a dimethylamino group, an ethylmethylamino group, and a diethylamino group, and more preferably an amino group and a dimethylamino group.

R2 represents a halogen atom, a hydroxyl group, a cyano group, a nitro group, a C1 to C6 alkyl group which may be appropriately substituted by a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 which may also be appropriately substituted Cycloalkyl, C2 to C6 alkenyl, C2 to C6 haloalkenyl, C2 to C6 alkynyl, C2 to C6 halide that may be appropriately substituted with substituent B Alkynyl, C1 ~ C6 alkoxy, which may be appropriately substituted with substituent B, C1 ~ C6 haloalkoxy, C3 ~ C8, cycloalkoxy which may also be appropriately substituted with substituent B, or C2 to C6 alkenyloxy, C2 to C6 haloalkenyloxy appropriately substituted with substituent B, C3 to C6 alkynyloxy, C3 to C6 haloalkynyloxy, R20C (= O)-(Here, R20 represents C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy Group, C3 to C8 cycloalkoxy group, or R21R22N- (here, R21 and R22 each independently represent a hydrogen atom, a C1 to C6 alkyl group that can be appropriately substituted by a substituent B1, or a C1 to C6 haloalkane Or C3 ~ C8 cycloalkyl, or R21 and R22 and the bonded nitrogen atom to form an aziridinyl group, Acridine, pyrrolidinyl, piperidinyl, homopiperidinyl, or azaoctyl.)), R20C (= O) O- (here, R20 has the same meaning as above.), Contains 1 ~ A radical of 3 to 6 members of two oxygen atoms, R23-L2- (Here, R23 represents a C1 to C6 alkyl group, or C1 to C6 haloalkyl group, and L2 represents S, SO, or SO _2. ) , R21R22N- (here, R21 and R22 have the same meaning as above.), Or R24C (= O) N (R25)-(here, R24 represents a hydrogen atom, a C1-C6 alkyl group, and a C1-C6 haloalkyl group , C3 to C8 cycloalkyl, C1 to C6 alkoxy, C1 to C6 haloalkoxy, C3 to C8 cycloalkoxy, or R21R22N- (here, R21 and R22 have the same meanings as above.) R25 represents a hydrogen atom, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group that can also be appropriately substituted by the substituent B1.)

Among them, R2 is preferably a halogen atom, a hydroxyl group, a cyano group, a C1 to C6 alkyl group which may be appropriately substituted by a substituent B, a C1 to C6 haloalkyl group, or a C1 to C6 alkyl group which may also be appropriately substituted by a substituent B. Oxygen, C1 ~ C6 haloalkoxy, C3 ~ C8 cycloalkoxy which can be appropriately substituted with substituent B, C2 ~ C6 alkenoxy which can also be appropriately substituted with substituent B, or The alkynyloxy group of C3 ~ C6 substituted with substituent B, R20C (= O) O- (here, R20 has the same meaning as above), or R23-L2- (here, R23 and L2 have the same meaning as above.) Desirably, a halogen atom, a C1-C6 alkyl group which may be appropriately substituted by a substituent B, or an C1-C6 alkoxy group which may also be appropriately substituted by a substituent B is preferred.

"Substituent B" in formula (1) represents a ring selected from the group consisting of hydroxy, cyano, cycloalkyl of C3 to C8, alkoxy of C1 to C6, haloalkoxy of C1 to C6, and ring of C3 to C8 Alkoxy, C2-C6 alkoxyalkoxy, R21R22N- (here, R21 and R22 have the same meaning as above.), R23-L2- (here, R23 and L2 have the same meaning as above.), R26R27R28Si- ( Here, R26, R27, and R28 each independently represent an alkyl group of C1 to C6.), R26R27R28Si- (CH ₂ ) sO- (here, s represents an integer of 1 to 3, and R26, R27, and R28 are the same as described above. Meaning.), R20C (= O)-(Here, R20 has the same meaning as R20.), And at least one of the group consisting of a 3 to 6 member ring base containing 1 to 2 oxygen atoms.

Among them, the substituent B is preferably a cyano group, a cycloalkyl group of C3 to C8, an alkoxy group of C1 to C6, an alkoxyalkoxy group of C2 to C6, and R23-L2- (here, R23 and L2 are the same as described above) Meaning.), R26R27R28Si- (here, R26, R27, and R28 have the same meaning as above.), R26R27R28Si- (CH ₂ ) sO- (here, s, R26, R27, and R28 have the same meaning as above.), R20C ( = O)-(Here, R20 has the same meaning as above.), Or a 3 to 6 membered ring containing 1 to 2 oxygen atoms is preferred, and a cyano group or an alkoxy group of C1 to C6 is preferred.

Preferred specific examples of the substituent B include a hydroxy group; a cyano group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group as the cycloalkyl group of C3 to C8; and a methoxy group as the alkoxy group of C1 to C6. Group, ethoxy group, propoxy group, isopropoxy group, butoxy group, and isobutoxy group; difluoromethoxy group, trifluoromethoxy group, haloalkoxy group as C1 to C6, 2, 2 -Difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropoxy, and 3,3,3-trifluoropropoxy; as the cycloalkoxy group of C3 ~ C8 Cyclopropyloxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy; methoxymethoxy, ethoxymethoxy, and methoxy as alkoxyalkoxy groups of C2 to C6 Oxyethoxy, ethoxyethoxy, and methoxypropoxy; R21R22N- (here, R21 and R22 have the same meanings as above.) Amino, dimethylamino, ethylmethylamino , Diethylamino, pyrrolidinyl, and piperidinyl; methylthio, methanesulfinyl, methanesulfonyl, and trifluoro as R23-L2- (here, R23 and L2 have the same meanings as above.) Methylthio, trifluoromethanesulfinyl, and trifluoromethanesulfonyl; as R26R27R28Si- (here, R26, R27, And R28 have the same meaning as above.) Trimethylsilyl and triethylsilyl; and R26R27R28Si- (CH ₂ ) sO- (here, s, R26, R27, and R28 have the same meaning as above.) Of 2- (Trimethylsilyl) ethoxy and 2- (triethylsilyl) ethoxy; R20C (= O)-(here, R20 has the same meaning as above.) , Difluoroacetamido, trifluoroacetamido, cyclopropanecarbonyl, methoxycarbonyl, ethoxycarbonyl, 2,2-difluoroethoxycarbonyl, 3,3,3-trifluoropropoxycarbonyl , Cyclopropoxycarbonyl, aminocarbonyl, dimethylaminocarbonyl, ethylmethylaminocarbonyl, diethylaminocarbonyl, pyrrolidinylcarbonyl, and piperidinylcarbonyl; and as containing 1 to 2 oxygen atoms 3- to 6-membered ring radicals, oxetanyl, Alkyl, 1,3-dioxanyl, and 1,3-dioxanyl.

More preferable specific examples of the substituent B include a hydroxyl group; a cyano group; a cyclopropyl group as a cycloalkyl group of C3 to C8, and a cyclobutyl group; a methoxy group as an alkoxy group of C1 to C6, and ethoxy group Difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, and 2,2,2-trifluoroethoxy as haloalkoxy groups of C1 ~ C6; as C3 ~ C8 cyclopropoxy cyclopropoxy and cyclobutoxy; C2 ~ C6 alkoxyalkoxy methoxymethoxy, ethoxymethoxy, methoxyethoxy , And ethoxyethoxy; as dimethylamino, ethylmethylamino, and diethylamino groups of R21R22N- (here, R21 and R22 have the same meanings as above.) As R23-L2- (here , R23 and L2 have the same meaning as above.) Of methylthio, methanesulfinyl, and methanesulfonyl; and trimethylsilyl as R26R27R28Si- (here, R26, R27, and R28 have the same meaning as above.) ; As R (R26R27R28Si- (CH ₂ ) sO- (here, s, R26, R27, and R28 have the same meaning as above)) 2- (trimethylsilyl) ethoxy; as R20C (= O)-(in Therefore, R20 has the same meaning as above.) Ethyl, difluoroethyl, trifluoroethyl, and methoxycarbonyl , Ethoxycarbonyl, aminocarbonyl, dimethylaminocarbonyl, ethylmethylaminocarbonyl, and diethylaminocarbonyl; and as a group of 3 to 6 membered rings containing 1 to 2 oxygen atoms, 3-dioxolyl, and 1,3-dioxanyl.

The "substituent B1" of the formula (1) represents at least one selected from the group consisting of a cyano group, an alkoxy group of C1 to C6, a haloalkoxy group of C1 to C6, and a cycloalkoxy group of C3 to C8. 1 species. Among them, the substituent B1 is preferably a cyano group or an alkoxy group of C1 to C6.

Preferred specific examples of the substituent B1 include a cyano group; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group as the alkoxy group of C1 to C6; and a C1 group ~ C6 haloalkoxy, difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropoxy And 3,3,3-trifluoropropoxy; and cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy, which are cycloalkoxy groups of C3 to C8.

More preferable specific examples of the substituent B1 include cyano; methoxy and ethoxy as alkoxy groups of C1 to C6; difluoromethoxy and trifluoro as alkoxy groups of C1 to C6; Methoxy, 2,2-difluoroethoxy, and 2,2,2-trifluoroethoxy; and cyclopropoxy and cyclobutoxy, which are cycloalkoxy groups of C3 to C8.

The halogen atom in R2 in formula (1) has the same meaning as the foregoing definition, and is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. R2 of formula (1) includes a hydroxyl group, a cyano group, and a nitro group.

The C1-C6 alkyl group of the "C1-C6 alkyl group which may also be appropriately substituted by the substituent B" in R2 of formula (1) has the same meaning as the foregoing definition, preferably methyl, ethyl, propyl , Isopropyl, butyl, or isobutyl, more preferably methyl, ethyl, propyl, or isopropyl. When there is a substituent B, the hydrogen atom in the alkyl group of C1 to C6 may be optionally substituted by the substituent B.

The "C1 to C6 haloalkyl group" in R2 in formula (1) has the same meaning as the foregoing definition, and is preferably difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2, 2-trifluoroethyl, 3,3-difluoropropyl, or 3,3,3-trifluoropropyl, more preferably difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, Or 2,2,2-trifluoroethyl.

The cycloalkyl group of C3 ~ C8 of "C3 ~ C8 cycloalkyl group which may also be appropriately substituted by substituent B" in R2 of formula (1) has the same meaning as the foregoing definition, preferably cyclopropyl group and cyclobutyl group. Group, cyclopentyl, or cyclohexyl, more preferably cyclopropyl or cyclobutyl. When having a substituent B, a hydrogen atom in a cycloalkyl group of C3 to C8 may be optionally substituted by a substituent B.

The alkenyl groups of C2 to C6 in the "alkenyl groups of C2 to C6 which may also be appropriately substituted by the substituent B" in R2 of formula (1) have the same meanings as the foregoing definitions, preferably vinyl, 1-propenyl, Allyl, 1-butenyl, 2-butenyl, or 3-butenyl, more preferably vinyl, 1-propenyl, or allyl. When there is a substituent B, the hydrogen atom in the alkenyl group of C2 to C6 may be optionally substituted by the substituent B.

The "haloalkenyl group of C2 to C6" in R2 of formula (1) has the same meaning as the foregoing definition, preferably 2-fluorovinyl, 2,2-difluorovinyl, and 2,2-dichlorovinyl , 3-fluoroallyl, 3,3-difluoroallyl, or 3,3-dichloroallyl, more preferably 2-fluorovinyl, or 2,2-difluorovinyl.

The alkynyl group of C2 to C6 of "C2 to C6 alkynyl group which may also be appropriately substituted by substituent B" in R2 of formula (1) has the same meaning as the foregoing definition, preferably ethynyl and 1-propynyl , Propargyl, 1-butynyl, 2-butynyl, or 3-butynyl, more preferably ethynyl, 1-propynyl, or propargyl. When there is a substituent B, the hydrogen atom in the alkynyl group of C2 to C6 may be optionally substituted by the substituent B.

The "haloalkynyl group of C2 to C6" in R2 of formula (1) has the same meaning as the foregoing definition, and is preferably 3,3-difluoro-1-propynyl, 3,3,3-trifluoro-1 -Propynyl, 4,4-difluoro-1-butynyl, 4,4-difluoro-2-butynyl, 4,4,4-trifluoro-1-butynyl, or 4,4 , 4-Trifluoro-2-butynyl, more preferably 3,3-difluoro-1-propynyl, or 3,3,3-trifluoro-1-propynyl.

The C1-C6 alkoxy group of "C1-C6 alkoxy group that may also be appropriately substituted by substituent B" in R2 of formula (1) has the same meaning as the foregoing definition, and preferably methoxy group and ethoxy group Group, propoxy, isopropoxy, butoxy, isobutoxy, or pentoxy, more preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, or Pentyloxy. When there is a substituent B, the hydrogen atom in the alkoxy group of C1 to C6 may be optionally substituted by the substituent B.

The "C1 to C6 haloalkoxy group" in R2 of formula (1) has the same meaning as the foregoing definition, and is preferably difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropoxy, or 3,3,3-trifluoropropoxy, more preferably difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, or 2,2,2-trifluoroethoxy.

The C3 to C8 cycloalkoxy group of "C3 to C8 cycloalkoxy group which may also be appropriately substituted with substituent B" in R2 of formula (1) has the same meaning as the foregoing definition, and cyclopropyloxy group is preferred. , Cyclobutoxy, cyclopentyloxy, or cyclohexyloxy, more preferably cyclopropoxy or cyclobutoxy. When there is a substituent B, the hydrogen atom in the cycloalkoxy group of C3 to C8 may be optionally substituted by the substituent B.

The alkenyl group of C2 to C6 of the "alkenyl group of C2 to C6 which may also be appropriately substituted by substituent B" in R2 of formula (1) has the same meaning as the foregoing definition, preferably vinyloxy group, 1- Allyloxy, allyloxy, 1-butenyloxy, 2-butenyloxy, or 3-butenyloxy, more preferably ethyleneoxy, 1-propenyloxy, or allyloxy. When there is a substituent B, the hydrogen atom in the alkenyloxy group of C2 to C6 may be optionally substituted by the substituent B.

The "haloalkenyloxy group of C2 to C6" in R2 of formula (1) has the same meaning as the foregoing definition, and is preferably 2-fluoroethyleneoxy, 2,2-difluoroethyleneoxy, 2,2-di Vinyl chloride, 3-fluoroallyloxy, 3,3-difluoroallyloxy, or 3,3-dichloroallyloxy, more preferably 2-fluoroethyleneoxy, or 2,2 -Difluoroethyleneoxy.

The alkynyloxy group of C3 ~ C6 of "C3 ~ C6 alkynyloxy group which may also be appropriately substituted by substituent B" in R2 of formula (1) has the same meaning as the foregoing definition, preferably propargyloxy, 2 -Butynyloxy or 3-butynyloxy, more preferably propargyloxy. When there is a substituent B, the hydrogen atom in the alkynyloxy group of C3 to C6 may be optionally substituted by the substituent B.

The "C3 to C6 haloalkynyloxy group" in R2 of formula (1) has the same meaning as the foregoing definition, and is preferably 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4- Difluoro-2-butynyloxy, 4-bromo-4,4-difluoro-2-butynyloxy, or 4,4,4-trifluoro-2-butynyloxy, more preferably 4, 4-difluoro-2-butynyloxy, or 4,4,4-trifluoro-2-butynyloxy.

"R20C (= O)-" in R2 of formula (1) (here, R20 represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, and a C1-C6 alkyl group Oxygen, haloalkoxy of C1 to C6, cycloalkoxy of C3 to C8, or R21R22N- (here, R21 and R22 each independently represent a hydrogen atom, and C1 to C6 which may be appropriately substituted by a substituent B1 Alkyl group, C1 ~ C6 haloalkyl group, or C3 ~ C8 cycloalkyl group, or it means that R21 and R22 and the bonded nitrogen atom are integrated to form aziridinyl group, tetrahydroazetino group, pyrrolidinyl group , Piperidinyl, homopiperidinyl, or azaoctyl.)) Each term and the foregoing definition have the same meaning. Examples of "R20C (= O)-" include ethyl, propyl, difluoroethyl, trifluoroethyl, cyclopropanecarbonyl, methoxycarbonyl, ethoxycarbonyl, and 2,2- Difluoroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, cyclopropoxycarbonyl, aminocarbonyl, dimethylaminocarbonyl, ethylmethylaminocarbonyl, diethylaminocarbonyl, pyrrole Pyridylcarbonyl and piperidinylcarbonyl, more preferably, ethynyl, difluoroacetamido, trifluoroacetamido, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, dimethylaminocarbonyl, Ethylmethylaminocarbonyl and diethylaminocarbonyl.

R20 of "R20C (= O) O-" in R2 of formula (1) has the same meaning as described above. "R20C (= O) O-" is preferably exemplified by ethoxyl, propionyloxy, difluoroethoxyl, trifluoroethoxyl, cyclopropanecarbonyloxy, methoxycarbonyloxy, Ethoxycarbonyloxy, 2,2-difluoroethoxycarbonyloxy, 2,2,2-trifluoroethoxycarbonyloxy, cyclopropoxycarbonyloxy, aminocarbonyloxy, di Methylaminocarbonyloxy, ethylmethylaminocarbonyloxy, diethylaminocarbonyloxy, pyrrolidinylcarbonyloxy, and piperidinylcarbonyloxy, more preferably ethoxyl, difluoro Ethoxy, trifluoroethoxy, methoxycarbonyloxy, ethoxycarbonyloxy, aminocarbonyloxy, dimethylaminocarbonyloxy, ethylmethylaminocarbonyloxy, and Diethylaminocarbonyloxy.

The "3 to 6-membered ring group containing 1 to 2 oxygen atoms" in R2 in formula (1) has the same meaning as the foregoing definition, and is preferably an oxetanyl group, Alkyl, 1,3-dioxanyl, or 1,3-dioxanyl, more preferably 1,3-dioxanyl, Or 1,3-dioxanyl.

R2 of formula (1) are of the "R23-L2 -" (Here, R23 represents an alkyl group of C1 ~ C6, or haloalkyl of C1 ~ C6, L2 is S, SO, or SO ₂₎ of each term It has the same meaning as the foregoing definition. "R23-L2-" Preferably, methylthio, methanesulfinyl, methanesulfonyl, trifluoromethylthio, trifluoromethanesulfinyl, trifluoromethanesulfinyl, (chloromethyl) ) Thio, (chloromethane) sulfinyl, and (chloromethane) sulfonyl, more preferably methylthio, methanesulfinyl, methanesulfonyl, (chloromethyl) sulfanyl, ( (Chloromethane) sulfinyl, and (chloromethane) sulfonyl.

R21 and R22 of "R21R22N-" in R2 of formula (1) have the same meanings as described above. "R21R22N-" preferably includes amino, dimethylamino, ethylmethylamino, diethylamino, pyrrolidinyl, and piperidinyl, and more preferably, dimethylamino, ethylmethylamino , And diethylamino.

"R24C (= O) N (R25)-" in R2 of formula (1) (here, R24 represents a hydrogen atom, an alkyl group of C1 to C6, a haloalkyl group of C1 to C6, or a cycloalkane of C3 to C8 Group, C1 to C6 alkoxy group, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group, or R21R22N- (here, R21 and R22 have the same meaning as above.), R25 represents a hydrogen atom, and The C1-C6 alkyl group, C1-C6 haloalkyl group, or C3-C8 cycloalkyl group, which may be appropriately substituted by the substituent B1, have the same meanings as the foregoing definitions. Preferred examples of R24 include a hydrogen atom, methyl, ethyl, difluoromethyl, trifluoromethyl, cyclopropyl, methoxy, ethoxy, 2,2-difluoroethoxy, 2,2, 2-trifluoroethoxy, cyclopropoxy, amino, dimethylamino, ethylmethylamino, diethylamino, pyrrolidinyl, and piperidinyl, more preferably a hydrogen atom, methyl , Difluoromethyl, trifluoromethyl, methoxy, ethoxy, amine, dimethylamino, ethylmethylamino, and diethylamino. Further, R25 preferably includes a hydrogen atom, methyl, ethyl, propyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, cyanomethyl, 2- Cyanoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, and cyclopropyl. More preferred examples include hydrogen atom, methyl, ethyl, methoxymethyl, and ethyl. Oxymethyl, methoxyethyl, ethoxyethyl, cyanomethyl, 2,2-difluoroethyl, and 2,2,2-trifluoroethyl.

N in the formula (1) is an integer of 0 to 5. However, when n is 2 or more, two or more R 2 represent independent substituents, which may be the same or different, and may be arbitrarily selected.

R3 in the formula (1) represents a hydrogen atom, a halogen atom, a nitro group, a C1-C6 alkyl group which may be appropriately substituted by a substituent C, a C1-C6 haloalkyl group, or a C3 which may also be appropriately substituted by a substituent C ~ C8 cycloalkyl, C1 ~ C6 alkoxy which can be appropriately substituted by substituent C, C1 ~ C6 haloalkoxy, C2 ~ C6 alkenyl which can also be appropriately substituted by substituent C, C2 ~ C6 haloalkenyl, C2 ~ C6 alkynyl, C2 ~ C6 haloalkynyl, R30-L3- (where R30 has the same meaning as R23 and L3 has the same meaning as L2 .), R31R32N- (here, R31 and R32 are synonymous with the aforementioned R21 and R22.), Or R33C (= O)-(here, R33 represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, or C3 ~ C8 cycloalkyl.).

Among them, R3 is preferably a hydrogen atom, a halogen atom, an alkyl group of C1 to C6 which may be appropriately substituted by a substituent C, a cycloalkyl group of C3 to C8 which may also be appropriately substituted by a substituent C, or an appropriate substituent C Substituted alkoxy groups of C1 to C6, alkynyl groups of C2 to C6 which may also be appropriately substituted by the substituent C, or R30-L3- (here, R30 and L3 have the same meanings as above.) Ideally, especially hydrogen atoms, A halogen atom or a C1-C6 alkyl group which may be appropriately substituted by a substituent C is preferred.

"Substituent C" in formula (1) represents a group selected from the group consisting of hydroxyl, cyano, cycloalkyl of C3 to C8, alkoxy of C1 to C6, haloalkoxy of C1 to C6, and cycloalkane of C3 to C8 A group consisting of oxygen, R31R32N- (here, R31 and R32 は, the aforementioned R21 and R22 are synonymous.), And R30-L3- (here, R30 has the meaning of the aforementioned R14, and L3 has the meaning of the aforementioned L1.) At least one of the group. Among them, the substituent C is preferably a cyano group, an alkoxy group of C1 to C6, or R30-L3- (here, R30 and L3 have the same meanings as above.) It is preferable, especially a cyano group or an alkoxy group of C1 to C6. good.

Preferred specific examples of the substituent C include a hydroxy group; a cyano group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group as the cycloalkyl group of C3 to C8; and a methoxy group as the alkoxy group of C1 to C6 Group, ethoxy group, propoxy group, isopropoxy group, butoxy group, and isobutoxy group; difluoromethoxy group, trifluoromethoxy group, haloalkoxy group as C1 to C6, 2, 2 -Difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropoxy, and 3,3,3-trifluoropropoxy; as the cycloalkoxy group of C3 ~ C8 Cyclopropyloxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy; as amine groups, dimethylamino groups, R31R32N- (here, R31 and R32 have the same meanings as R21 and R22 described above), Ethylmethylamino, diethylamino, pyrrolidinyl, and piperidinyl; and methylthio, which is R30-L3- (herein, R30 has the meaning of the aforementioned R14, and L3 has the meaning of the aforementioned L1.) Methanesulfinyl, methanesulfonyl, trifluoromethylthio, trifluoromethanesulfinyl, and trifluoromethanesulfinyl.

More preferable specific examples of the substituent C include a hydroxyl group; a cyano group; a cyclopropyl group as a cycloalkyl group of C3 to C8, and a cyclobutyl group; a methoxy group as an alkoxy group of C1 to C6, and ethoxy group Difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, and 2,2,2-trifluoroethoxy as haloalkoxy groups of C1 ~ C6; as C3 ~ C8 cycloalkoxy cyclopropoxy, and cyclobutoxy; R31R32N- (here, R31 and R32 have the same meanings as above.) Dimethylamino, ethylmethylamino, and diethylamino And R30-L3- (herein, R30 and L3 have the same meanings as above.) Methylthio, methanesulfinyl, and methanesulfonyl.

R3 in formula (1) includes a hydrogen atom and a nitro group. The "halogen atom" in R3 in formula (1) has the same meaning as the foregoing definition, and is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

The C1-C6 alkyl group of "C1-C6 alkyl group which may also be appropriately substituted by the substituent C" in R3 of formula (1) has the same meaning as the foregoing definition, preferably methyl, ethyl, propyl , Isopropyl, butyl, or isobutyl, more preferably methyl, ethyl, or propyl. When there is a substituent C, a hydrogen atom in the alkyl group of C1 to C6 may be optionally substituted by the substituent C.

The "C1 to C6 haloalkyl group" in R3 in formula (1) has the same meaning as the foregoing definition, and is preferably difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2, 2-trifluoroethyl, 3,3-difluoropropyl, or 3,3,3-trifluoropropyl, more preferably difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, Or 2,2,2-trifluoroethyl.

The cycloalkyl group of C3 ~ C8 of "C3 ~ C8 cycloalkyl group which may also be appropriately substituted by substituent C" in R3 of formula (1) has the same meaning as the foregoing definition, preferably cyclopropyl group and cyclobutyl group Group, cyclopentyl, or cyclohexyl, more preferably cyclopropyl or cyclobutyl. When the substituent C is present, the hydrogen atom in the cycloalkyl group of C3 to C8 may be optionally substituted by the substituent C.

The alkoxy group of C1 to C6 in the alkoxy group of C1 to C6 which may also be appropriately substituted by the substituent C in R3 of formula (1) has the same meaning as the foregoing definition, preferably methoxy and ethoxy Group, propoxy, isopropoxy, butoxy, or isobutoxy, more preferably methoxy, ethoxy, propoxy, or isopropoxy. When the substituent C is present, the hydrogen atom in the alkoxy group of C1 to C6 may be optionally substituted by the substituent C.

The "haloalkoxy group of C1 to C6" in R3 in formula (1) has the same meaning as the foregoing definition, and is preferably difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropoxy, or 3,3,3-trifluoropropoxy, more preferably difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, or 2,2,2-trifluoroethoxy.

The alkenyl groups of C2 to C6 in "R2 of formula (1)" Alkenyl groups of C2 to C6 which may also be appropriately substituted by substituent C "have the same meanings as above, preferably vinyl, 1-propenyl, Allyl, 1-butenyl, 2-butenyl, or 3-butenyl, more preferably vinyl, 1-propenyl, or allyl. When there is a substituent C, the hydrogen atom in the alkenyl group of C2 to C6 may be optionally substituted by the substituent C.

The "haloalkenyl group of C2 to C6" in R3 of formula (1) has the same meaning as the foregoing definition, and is preferably 2-fluorovinyl, 2,2-difluorovinyl, 2,2-dichlorovinyl , 3-fluoroallyl, 3,3-difluoroallyl, or 3,3-dichloroallyl, more preferably 2-fluorovinyl, or 2,2-difluorovinyl.

The alkynyl groups of C2 to C6 of "alkynyl groups of C2 to C6 which may also be appropriately substituted by substituent C" in R3 of formula (1) have the same meanings as the foregoing definitions, preferably ethynyl and 1-propynyl , Propargyl, 1-butynyl, 2-butynyl, or 3-butynyl, more preferably ethynyl, 1-propynyl, or propargyl. When there is a substituent C, the hydrogen atom in the alkynyl group of C2 to C6 may be optionally substituted by the substituent C.

The "C2 to C6 haloalkynyl group" in R3 of formula (1) has the same meaning as the foregoing definition, and is preferably 3,3-difluoro-1-propynyl, 3,3,3-trifluoro-1 -Propynyl, 4,4-difluoro-1-butynyl, 4,4-difluoro-2-butynyl, 4,4,4-trifluoro-1-butynyl, or 4,4 , 4-Trifluoro-2-butynyl, more preferably 3,3-difluoro-1-propynyl, or 3,3,3-trifluoro-1-propynyl.

In "R30-L3-" in R3 in formula (1), R30 has the same meaning as that of R23, and L3 has the same meaning as that of L2. "R30-L3-" preferably includes methylthio, methanesulfinyl, methanesulfonyl, trifluoromethylsulfanyl, trifluoromethanesulfinyl, and trifluoromethanesulfinyl, and more preferably Examples are methylthio, methanesulfinyl, and methanesulfonyl.

In "R31R32N-" in R3 in formula (1), R31 and R32 have the same meanings as the aforementioned R21 and R22, and are preferably an amino group, dimethylamino group, ethylmethylamino group, diethylamino group, pyrrolidinyl group, Or piperidinyl, more preferably dimethylamino, ethylmethylamino, or diethylamino.

The terms of "R33C (= O)-" in R3 of formula (1) (here, R33 represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a C3-C8 cycloalkyl group) and The foregoing definitions have the same meaning. "R33C (= O)-" preferably includes ethenyl, propionyl, difluoroethylsulfonyl, trifluoroethylsulfonyl, and cyclopropanecarbonyl, and more preferably, ethylsulfonyl and difluoroethylsulfonyl , And trifluoroacetamido.

X in formula (1) represents an oxygen atom or a sulfur atom. Ideally X is an oxygen atom.

Y in formula (1) represents phenyl, pyridyl, Base, pyrimidinyl, pyridine Base, three Base, four Group, thienyl, thiazolyl, isothiazolyl, or thiadiazolyl. In the phenyl group, the substituent D is substituted at the ortho position, and the substituents D1 are each independently suitably substituted with 0 to 4 substituents. The pyridyl, the da Group, the pyrimidinyl group, the pyridine Base, the three Base, or the four Group, the substituent D is substituted at the ortho position, and each of the substituents D1 is independently substituted with 0 to 3 as appropriate. In the thienyl group, the thiazolyl group, the isothiazolyl group, or the thiadiazolyl group, the substituent D is substituted in the ortho position, and the substituents D1 each independently have 0 to 2 substitutions as appropriate.

The "substituent D" of the formula (1) means that it is selected from the group consisting of a halogen atom, an alkyl group of C1 to C6, a haloalkyl group of C1 to C6, an alkoxy group of C1 to C6, and a haloalkoxy group of C1 to C6. At least 1 of the group. Among them, the substituent D is a halogen atom or an alkyl group of C1 to C6, and a halogen atom is particularly preferable.

Preferred specific examples of the substituent D include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom; a methyl group, an ethyl group, and a propyl group as the alkyl group of C1 to C6; and a halogen group as C1 to C6 Difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, and 2,2,2-trifluoroethyl of alkyl; methoxy and ethoxy as alkoxy groups of C1 to C6 , Propoxy, isopropoxy, butoxy, isobutoxy, and tertiary butoxy; and difluoromethoxy, trifluoromethoxy, haloalkoxy as C1 to C6, 2 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3-difluoropropoxy, and 3,3,3-trifluoropropoxy.

More preferable specific examples of the substituent D include a fluorine atom, a chlorine atom, and a bromine atom as a halogen atom; a methyl group and an ethyl group as the alkyl group of C1 to C6; and a methyl group as the alkoxy group of C1 to C6. Oxy, ethoxy, propoxy, and isopropoxy; and difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, haloalkoxy, C1 to C6, And 2,2,2-trifluoroethoxy.

The "substituent D1" of formula (1) represents a group selected from the group consisting of a hydroxyl group, a halogen atom, an alkyl group of C1 to C6, a haloalkyl group of C1 to C6, a cycloalkyl group of C3 to C8, an alkoxy group of C1 to C6, At least one of the group consisting of C1 to C6 haloalkoxy and C3 to C8 cycloalkoxy. Among them, the substituent D1 is preferably a hydroxyl group, a halogen atom, an alkyl group of C1 to C6, an alkoxy group of C1 to C6, or a haloalkyl group of C1 to C6, more preferably a halogen atom, an alkyl group of C1 to C6, C1-C6 alkoxy or C1-C6 haloalkoxy is preferred.

Preferred specific examples of the substituent D1 include a hydroxyl group; a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom; a methyl group, an ethyl group, and a propyl group as the alkyl group of C1 to C6; and a C1 to C6 group Haloalkyl difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, and 2,2,2-trifluoroethyl; cyclopropyl, cyclopropyl Butyl, cyclopentyl, and cyclohexyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tert-butyl as alkoxy groups of C1 to C6 Oxygen; difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 3,3 as haloalkoxy groups of C1 to C6 -Difluoropropoxy, and 3,3,3-trifluoropropoxy; and cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy as the cycloalkoxy groups of C3 to C8 base.

More preferable specific examples of the substituent D1 include a hydroxyl group; a fluorine atom, a chlorine atom, and a bromine atom as a halogen atom; a methyl group and an ethyl group as the C1 to C6 alkyl group; and a haloalkyl group as the C1 to C6 Difluoromethyl and trifluoromethyl; cyclopropyl and cyclobutyl as cycloalkyl groups of C3 to C8; methoxy, ethoxy, and propoxy groups as alkoxy groups of C1 to C6 , And isopropoxy; difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, and 2,2,2-trifluoroethoxy as haloalkoxy groups of C1 to C6 And cyclopropoxy, and cyclobutoxy as cycloalkoxy of C3 to C8.

Specific examples of Y in the formula (1) will be described in detail below. A) When Y is a phenyl group, Y represents a substructure represented by the formula (a) (here, D and D1 have the same meanings as above, and ma represents an integer of 0 to 4). [Chemical 6]

Ma in the formula (a) represents an integer of 0 to 4. When ma in formula (a) is 2 or more, two or more D1 represent independent substituents, which may be the same or different, and may be arbitrarily selected. In the present specification, when Y is a phenyl group, the ortho position is as shown in formula (a), which means a position of a phenyl group having a substituent D. A phenyl group in which the substituent D is in the ortho position becomes a feature of the present invention.

The ideal combination of formula (a) is 2-D-6-D1-phenyl, 2-D-4-D1-phenyl, or 2-D-4-D1-6-D1-phenyl. Here, for example, "2-D-6-D1-phenyl" refers to a disubstituted phenyl group having a substituent D at the 2-position and a substituent D1 at the 6-position. The same applies to the following description.

B) Y is pyridyl, Base, pyrimidinyl, pyridine Base, three Base, or quad At base time, Y is a substructure represented by formula (b) (here, D and D1 are synonymous with the foregoing, and mb represents an integer from 0 to 3.) .

G1, G2, G3, and G4 in formula (b) each independently represent a carbon atom or a nitrogen atom. However, at least one of G1, G2, G3, and G4 is a nitrogen atom. Desirably, any of G1, G2, G3, and G4 is a nitrogen atom in G1, G2, G3, and G4. That is, it is pyridyl. Mb in the formula (b) represents an integer of 0 to 3. When mb of the formula (b) is 2 or more, two or more D1 represent independent substituents, which may be the same or different, and may be arbitrarily selected.

In this specification, Y is pyridyl, Base, pyrimidinyl, pyridine Base, three Base, or quad At base time, the ortho position is as shown in formula (b), and represents the position of the 6-membered ring with substituent D. A specific example of the substructure of the formula (b) is shown below.

[Chemical 8]

Substituent D is ortho-pyridyl, Base, pyrimidinyl, pyridine Base, three Base, or quad The base becomes a feature of the present invention.

The ideal combination of formula (b) is 3-D-2-pyridyl, 3-D-5-D1-2-pyridyl, 2-D-3-pyridyl, 2-D-4-D1-3-pyridine Base, 2-D-6-D1-3-pyridyl, 2-D-4-D1-6-D1-3-pyridyl, 4-D-3-pyridyl, 4-D-2-D1-3 -Pyridyl, 4-D-6-D1-3-pyridyl, 4-D-2-D1-6-D1-3-pyridyl, 3-D-4-pyridyl, or 3-D-5- D1-4-pyridyl.

C) When Y is thienyl, thiazolyl, isothiazolyl, or thiadiazolyl, Y represents a secondary structure represented by formula (c-1), formula (c-2), or formula (c-3); 9】 [Chemical 10] [Chemical 11] Here, D and D1 are synonymous with the foregoing, and mc represents an integer of 0 to 2.

In Formula (c-1), Formula (c-2), and Formula (c-3), G5 and G6 each independently represent a carbon atom or a nitrogen atom. In the formula (c-1), the formula (c-2), and the formula (c-3), mc represents an integer of 0 to 2. When mc of Formula (c-1), Formula (c-2), and Formula (c-3) is 2, two D1 represent independent substituents, which may be the same or different, and may be arbitrarily selected.

In the present specification, when Y is thienyl, thiazolyl, isothiazolyl, or thiadiazolyl, the ortho position is as shown in formula (c-1), formula (c-2), and formula (c-3), Means the position of the 5-membered ring with substituent D. A specific example of the substructure of the formula (c-1) is shown below.

[Chemical 12]

A specific example of the substructure of the formula (c-2) is shown below. [Chemical 13]

Specific examples of the substituent of the substructure of formula (c-3) are shown below. [Chemical 14]

A thienyl, thiazolyl, isothiazolyl, or thiadiazolyl group in which the substituent D is ortho is a feature of the present invention.

In formula (1), the bond including the broken line part represents [化 15] Where to say it. In the formula (1), the bond including the broken line portion represents a double bond or a single bond.

When the bond including the broken line portion in formula (1) is a double bond, it represents the compound represented by formula (1a), or a salt thereof; [Chem. 16]

In the formula, R1, R2, R3, X, Y, and n have the same meaning as in formula (1).

When the bond including the broken line portion in the formula (1) is a single bond, it represents the compound represented by the formula (1b), or a salt thereof; [Chem. 17]

In the formula, R1, R2, R3, X, Y, and n have the same meanings as in formula (1).

In the formula (1b), when R3 is a substituent other than hydrogen, it is only one of the R form and the S form, or a mixture of the R form and the S form in any ratio.

The compound represented by formula (1) may have one or two axis asymmetry. The isomer ratio at this time is a mixing ratio of an individual ratio or an arbitrary ratio, and is not particularly limited. The compound represented by formula (1) may include asymmetric atoms in some cases. The isomer ratio at this time is a mixing ratio of an individual or an arbitrary ratio, and is not particularly limited. The compound represented by formula (1) sometimes includes geometric isomers. The isomer ratio at this time is a mixing ratio of an individual or an arbitrary ratio, and is not particularly limited.

The compound represented by formula (1) may form a salt. Examples thereof include hydrochloric acid, sulfuric acid, acetic acid, fumaric acid, and maleic acid salts, and metal salts such as sodium, potassium, and calcium, but they are not particularly limited as long as they can be used as pesticides.

Then, the specific compound of the pyridone compound represented by the formula (I) of the present invention is expressed by a combination of the structural formula shown in Table 1, (R2) n shown in Table 2, and an oxygen atom or a sulfur atom X. These compounds are used for illustration, and the present invention is not limited to these compounds.

【Table 1】

[Table 2] Continue to Table 1

[Table 3] Continue to Table 1

[Table 4] Continue to Table 1

[Table 5] Continued from Table 1

[Table 6] Continue to Table 1

[Table 7] continued from Table 1

[Table 8] Continue to Table 1

[Table 9] Continue to Table 1

[Table 10] Continued from Table 1

[Table 11] continued to Table 1

[Table 12] continued to Table 1

[Table 13] Continued from Table 1

[Table 14] Continued from Table 1

[Table 15] Continued with Table 1

[Table 16] Continued from Table 1

[Table 17] continued from Table 1

[Table 18] Continued with Table 1

[Table 19] Continued with Table 1

[Table 20] Continued from Table 1

Hereinafter, for example, the description of "2-F-" in Table 2 means that the fluorine atom is bonded at the 2-position of the phenyl group (R2) n-bonded, and the description of "2-F-3-HO-" is It means that there is a fluorine atom bond at the 2-position and a hydroxyl bond at the 3-position. The description of "2,3-di-F" means that there is a fluorine atom bond at the 2-position and the 3-position, and other records are the same.

[Table 21]

[Table 22] Continued with Table 2

[Table 23] Continued with Table 2

[Table 24] Continued with Table 2

[Table 25] continued to Table 2

[Table 26] continued to Table 2

[Table 27] Continued with Table 2

[Table 28] Continued with Table 2

[Table 29] Continued with Table 2

[Table 30] Continued with Table 2

[Table 31] Continued with Table 2

[Table 32] Continued with Table 2

[Table 33] Continued with Table 2

[Table 34] Continued with Table 2

[Table 35] Continued with Table 2

[Table 36] Continued with Table 2

[Table 37] Continued with Table 2

[Table 38] Continued with Table 2

[Table 39] Continued with Table 2

[Table 40] Continued with Table 2

[Table 41] Continued with Table 2

[Table 42] Continued with Table 2

[Table 43] Continued with Table 2

[Table 44] Continued with Table 2

[Table 45] Continued with Table 2

[Table 46] Continued with Table 2

[Table 47] Continued with Table 2

[Table 48] Continued with Table 2

Next, the manufacturing method of the pyridone compound represented by Formula (1) is demonstrated. [Manufacturing method A]

[Chemical 18]

In the formula, R4 represents a hydrogen atom, a hydroxyl group, a cyano group, an alkyl group of C1 to C6 which can be appropriately substituted by substituent A, a haloalkyl group of C1 to C6, or an alkyl group of C3 to C8 which can also be appropriately substituted by substituent A. Cycloalkyl, C2 to C6 alkenyl, C2 to C6 haloalkenyl, C2 to C6 alkynyl, C2 to C6 haloalkynyl, which may be appropriately substituted with substituent A Group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkoxy group, C3-C8 alkoxy group, which may be appropriately substituted by substituent A C2 ~ C6 alkenyloxy, C2 ~ C6 haloalkenyloxy suitably substituted by group A, C3 ~ C6 alkynyloxy optionally substituted by substituent A, C3 ~ C6 haloalkynyloxy, or R10R11N -(Here, R10 and R11 each independently represent a hydrogen atom or an alkyl group of C1 to C6.), R5 represents a hydrogen atom or an alkyl group of C1 to C6, and n, R2, R3, X, and Y have the same meanings as described above. .

Production method A is a method for obtaining a compound represented by the formula (1b-a) containing a compound of the present invention and a production intermediate containing the compound of the present invention, including a step of reacting a compound represented by the formula (3) with R4NH ₂ in the presence of an acid. .

R4NH ₂ used in this reaction can be obtained from a commercially available product or can be produced by a known method. R4NH ₂ may also be a salt formed with an acidic compound such as hydrochloric acid and acetic acid, as long as the intended reaction proceeds, and there is no particular limitation.

The R4NH ₂ used in this reaction may be 1 equivalent or more relative to the compound represented by the formula (3), and it is not particularly limited if the intended reaction proceeds, and it is preferably 1 equivalent to 200 equivalents.

Examples of the acid used in the reaction include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid, methanesulfonic acid, and p-toluenesulfonic acid. The reaction can be performed without particular limitation, and acetic acid is preferred. When a salt of R4NH ₂ and an acidic compound is used, it is not necessary to use an acid.

The amount of the acid used in this reaction is only required to be 1 equivalent or more with respect to R4NH ₂ , and it is not particularly limited if the intended reaction will proceed, and it is preferably 1 equivalent to 200 equivalents. When the acid used is a liquid, it can also be used as a solvent.

A solvent can also be used in this reaction, but it is not necessary. The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds. Examples include acidic solvents such as acetic acid and methanesulfonic acid, diethyl ether, diisopropyl ether, methyl-tertiary butyl ether, and dimethoxy group. Ethane, tetrahydrofuran, di Ether solvents such as alkane, alcohol solvents such as methanol, ethanol, isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, acetic acid Ester solvents such as butyl ester, nitrile solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and other amine solvents, 1,3- Urea solvents such as dimethyl-2-imidazolidone, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride. These solvents can be used singly or in a mixture of two or more kinds at any ratio. The solvent is preferably an acidic solvent, and more preferably acetic acid.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by formula (3).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 50 ° C or higher and 180 ° C or lower or the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. are dissolved, and a saline solution can be optionally used. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisocyanate may be added. Ether solvents such as propyl ether and methyl tertiary butyl ether; halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hexane, heptane, cyclohexane, methylcyclohexane Solvents that are not compatible with water, such as hydrocarbon solvents. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, and it can be performed according to the purity and yield of the purpose.

The aforementioned reaction mixture containing the compound represented by the formula (1b-a) can be removed by using a desiccant such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1b-a) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1b-a) obtained after the solvent is distilled off can be purified by using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

According to the production method A, the compound represented by the formula (2) which can be produced when R4 in the compound represented by the formula (1b-a) represents a hydrogen atom can be useful for obtaining the compound represented by the formula (1b) among the compounds of the present invention. Manufacture of intermediates.

Specific examples of the manufacturing intermediate represented by formula (2) can be expressed by a combination of the structural formula shown in Table 3, (R2) n shown in Table 2, and an oxygen atom or a sulfur atom X. These compounds are used for illustration, and the present invention is not limited thereto.

[Table 49]

[Table 50] Continued with Table 3

[Table 51] Continued with Table 3

[Table 52] Continued with Table 3

[Table 53] Continued with Table 3

[Table 54] Continued with Table 3

[Table 55] Continued with Table 3

The method of using the compound represented by the formula (2) as a production intermediate and obtaining the formula (1b) of the present invention will be described.

[Manufacturing Method B] [Chem. 19]

In the formula, Lv represents a leaving group such as methanesulfonyl, trifluoromethanesulfonyl, p-toluenesulfonyl, and halogen atom, and R1, R2, R3, X, Y, and n have the same meanings as described above.

Production method B is a method for obtaining a compound represented by formula (1b), and includes a step of reacting a production intermediate represented by formula (2) with R1Lv in the presence of a base in a solvent.

The R1Lv used in this reaction can be obtained from a commercially available product or manufactured by a known method.

The amount of R1Lv used in this reaction is only 1 equivalent or more with respect to the compound represented by formula (2), and it is sufficient if the intended reaction proceeds, and there is no particular limitation, preferably 1 equivalent or more and 10 equivalents or less.

Examples of the base used in the reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, and sodium hydride, and the reaction can be carried out without particular limitation.

The amount of the base used in this reaction is 1 equivalent or more with respect to the compound represented by the formula (2), and it is sufficient if the intended reaction proceeds. There is no particular limitation, and it is preferably 1 equivalent to 10 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and examples thereof include diethyl ether, diisopropyl ether, methyl-third butyl ether, dimethoxyethane, tetrahydrofuran, and diamine. Ether solvents such as alkane, alcohol solvents such as methanol, ethanol, isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, acetic acid Ester solvents such as butyl ester, nitrile solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and other amine solvents, 1,3- Urea solvents such as dimethyl-2-imidazolidinone, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, sulfur solvents such as dimethylmethylene, cyclobutane, acetone, Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 to 200 times the weight of the compound represented by formula (2).

The temperature at which the reaction is carried out is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C or higher and 150 ° C or lower or the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When using an aqueous solution, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, etc. is dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. are dissolved, and a thio group is dissolved can be optionally used. Aqueous solutions of sulfur salts, such as sodium sulfate and sodium sulfite, and saline solution. During the liquid separation operation, benzene solvents such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, etc .; ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; Ether solvents such as ether, methyl-tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hexane, heptane, cyclohexane, methylcyclohexane, etc. Solvents that are miscible with water, such as hydrocarbon solvents. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be performed according to the purity and yield of the purpose.

The reaction mixture containing the compound represented by the formula (1b) obtained above can be removed by using a desiccant such as sodium sulfate and magnesium sulfate, but it is not necessary.

The reaction mixture containing the compound represented by the formula (1b) obtained above can be distilled off under reduced pressure as long as the compound does not decompose. The reaction mixture containing the compound represented by the formula (1b) obtained after the solvent is distilled off can be purified by using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purpose purity.

[Manufacturing Method C] [Chem. 20]

In the formula, SR represents a vulcanizing agent, and R1, R2, R3, Y, and n have the same meanings as described above.

Production method C is a production method for obtaining a compound represented by formula (1b-c) among the compounds represented by formula (1b), including a step of reacting a compound represented by formula (1b-b) with a vulcanizing agent (SR) in a solvent. .

Examples of the sulfurizing agent used in this reaction include Lawesson's reagent (2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphatidine Alkane-2,4-disulfide (2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide)).

The amount of the vulcanizing agent used in this reaction is only required to be 0.5 equivalent or more with respect to the compound represented by the formula (1b-b), and it is not particularly limited if the intended reaction proceeds, and it is preferably 1 equivalent to 10 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and examples include diethyl ether, diisopropyl ether, methyl-third butyl ether, dimethoxyethane, tetrahydrofuran, and diamine. Ether solvents such as alkane, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1b-b).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 50 ° C or higher and 180 ° C or lower or the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water to the reaction mixture or a suitable aqueous solution for liquid separation. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like are dissolved, and a saline solution can be optionally used. During the liquid separation operation, benzene solvents such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, etc .; ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; Ether solvents such as ether, methyl-tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hexane, heptane, cyclohexane, methylcyclohexane, etc. Hydrocarbon solvents and other solvents that are immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose. In this reaction, a liquid separation operation is not necessary.

The reaction mixture containing the compound represented by the formula (1b-c) obtained above can be removed by using a desiccant such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1b-c) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1b-c) obtained after the solvent is distilled off can be purified by using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing Method D] [Chem. 21]

In the formula, R3a represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, which may be appropriately substituted by a substituent C, or a C3-C8 cycloalkyl group, which may also be appropriately substituted by a substituent C, or may be substituted. C2 to C6 alkenyl, C2 to C6 haloalkenyl, C2 to C6 alkynyl, or C2 to C6 haloalkynyl, which can be appropriately substituted with substituent C, Lv, R1, R2 , X, Y, and n are synonymous with the foregoing.

Production method D is a compound in which R3a in the compound represented by the formula (1b) is a C1-C6 alkyl group, a C1-C6 haloalkyl group that may also be appropriately substituted by a substituent C, or may be appropriately substituted by a substituent C C3 to C8 cycloalkyl, C2 to C6 alkenyl, C2 to C6 haloalkenyl, C2 to C6 alkynyl, or C2 A method for synthesizing a compound represented by the formula (1b-e) of a haloalkynyl group of ~ C6 includes a step of reacting the compound represented by the formula (1b-d) with R3aLv in a solvent in the presence of a base.

The R3aLv used in this reaction can be obtained from a commercially available product or manufactured by a known method. The amount of R3aLv used in this reaction is 1 equivalent or more with respect to the compound represented by the formula (1b-d), and there is no particular limitation as long as the intended reaction proceeds, and it is preferably 1 equivalent to 1.8 equivalents.

Examples of the base used in this reaction include metal hydrides such as sodium hydride, methyllithium, butyllithium, organic lithium such as second butyllithium, third butyllithium, and hexyllithium, lithium diisopropylamino, Metal amines such as lithium hexamethyldisilazane, sodium hexamethyldisilazane, and potassium hexamethyldisilazane.

The amount of the base used in this reaction is 1 equivalent or more with respect to the compound represented by the formula (1b-d), and it is sufficient if the intended reaction proceeds, and there is no particular limitation, and it is preferably 1 equivalent to 10 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and examples include diethyl ether, diisopropyl ether, methyl-third butyl ether, dimethoxyethane, tetrahydrofuran, and diamine. Ether solvents such as alkane, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1b-d).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually -80 ° C to 100 ° C or lower than the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When using an aqueous solution, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, etc. is dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. are dissolved, and a thio group is dissolved can be optionally used Aqueous solutions of sulfur salts, such as sodium sulfate and sodium sulfite, and saline solution. During the liquid separation operation, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisocyanate can be added as needed. Ether solvents such as propyl ether and methyl tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, and chloroform, hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane, etc. Miscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose.

The reaction mixture containing the compound represented by the formula (1b-e) obtained above can be removed by using a desiccant such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1b-e) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1b-e) obtained after the solvent is distilled off can be purified by using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing method E] [Chem. 22]

In the formula, Ox represents an oxidant, and R1, R2, R3, X, Y, and n have the same meanings as described above.

Production method E is a method for obtaining a compound represented by the formula (1a), and includes a step of reacting the compound represented by the formula (1b) with an oxidizing agent (Ox) in a solvent.

As the oxidant used in this reaction, metal oxides such as manganese dioxide, benzoquinones such as 2,3-dichloro-5,6-dicyano-p-benzoquinone, azobisisobutyronitrile, Free radical initiators such as benzamyl peroxide and N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5-dimethyl Combinations of halogenating agents such as methylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin and the like.

The method of the oxidant-based metal oxides will be described below. The amount of the oxidizing agent used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1b), and it is not particularly limited if the intended reaction proceeds, and is usually 1 equivalent to 200 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds. Examples include benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene, methylene chloride, and dichloroethane. , Chloroform, carbon tetrachloride and other halogen solvents. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by formula (1b).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 0 ° C to 150 ° C or lower than the boiling point of the solvent.

After the reaction, undissolved metals can be removed by filtering. Furthermore, a liquid separation operation can be performed by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. are dissolved, and saline are optionally used. During the liquid separation operation, benzene solvents such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, etc .; ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; Ether solvents such as ether, methyl-tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hexane, heptane, cyclohexane, methylcyclohexane, etc. Hydrocarbon solvents and other solvents that are immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose. In this reaction, a liquid separation operation is not necessary.

The reaction mixture containing the compound represented by the formula (1a) obtained above can be removed by using a desiccant such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1a) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1a) obtained after the solvent is distilled off can be purified using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

The following is a description of a method in which the oxidant is a benzoquinone. The amount of the oxidizing agent used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1b), and it is sufficient if the intended reaction proceeds. There is no particular limitation, and it is usually 1 to 20 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds. Examples include benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene, methylene chloride, and dichloroethane. , Chloroform, carbon tetrachloride and other halogen solvents. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1b).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 0 ° C or higher and 150 ° C or lower or the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like are dissolved, and a saline solution can be optionally used. During the liquid separation operation, benzene solvents such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, etc .; ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; Ether solvents such as ether, methyl-tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hexane, heptane, cyclohexane, methylcyclohexane, etc. Hydrocarbon solvents and other solvents that are immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose. In this reaction, a liquid separation operation is not necessary.

The reaction mixture containing the compound represented by the formula (1a) obtained above can be removed by using a desiccant such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1a) obtained above is decomposable, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1a) obtained after the solvent is distilled off can be purified using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

The following describes a method in which the oxidant is a combination of a radical initiator and a halogenating agent. The amounts of the radical initiator and the halogenating agent used in this reaction are only 0.01 equivalents or more and 1.0 equivalents or more relative to the compound represented by formula (1b), and there is no particular limitation as long as the intended reaction proceeds. The free radical initiator is preferably 0.01 to 1 equivalent, and the halogenating agent is preferably 1 to 3 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds. Examples include halogenated benzene solvents such as chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate. Halogen solvents such as methylene chloride, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane; and the like. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1b).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 20 ° C to 150 ° C or lower than the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When using an aqueous solution, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, etc. is dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. are dissolved, and a thio group is dissolved can be optionally used. Aqueous solutions of sulfur salts, such as sodium sulfate and sodium sulfite, and saline solution. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl may be added. Ether solvents such as ether, methyl-tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, and chloroform; hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane; and Water immiscible solvent. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose.

The reaction mixture containing the compound represented by the formula (1a) obtained above can be removed by using a desiccant such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1a) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1a) obtained after the solvent is distilled off can be purified with an appropriate solvent by washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing Method F]

In the formula, R3b represents a halogen atom, HalR represents a halogenating agent, and R1, R2, X, Y, and n have the same meanings as described above.

Production method F is a method for obtaining a compound represented by formula (1a-b) in which R3b represents a halogen atom in the compound represented by formula (1a), which comprises combining the compound represented by formula (1a-a) with a halogenating agent (HalR) in Step of reaction in a solvent.

Examples of the halogenating agent used in this reaction include Selectfluor (N-fluoro-N'-triethylenediamine bis (tetrafluoroborate)), N-chlorosuccinimide, N-bromosuccinimide, and N-iodoamber Arsenimine, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5 , 5-dimethylhydantoin, bromine, iodine, etc.

The amount of the halogenating agent used in this reaction is only required to be 1 equivalent or more for the compound represented by formula (1a-a), and it is not particularly limited if the objective reaction will proceed, and it is preferably 1 equivalent to 10 equivalents. . However, if the amount of the halogenating agent containing hydantoin is 0.5 equivalent or more, as long as the intended reaction can proceed, there is no particular limitation, and it is preferably 1 equivalent to 5 equivalents.

When the halogenating agent used in this reaction is an iodinating agent, acids such as inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, and trifluoromethanesulfonic acid can be added. The amount of acid used when the halogenating agent used in this reaction is an iodinating agent is only 0.01 equivalent or more with respect to the compound represented by the formula (1a-a), and it can be carried out if the intended reaction proceeds, and there is no particular limitation. It is preferably from 0.1 to 3 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds. Examples include acidic solvents such as sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, diethyl ether, and diisopropyl ether. , Methyl-tertiary butyl ether, dimethoxyethane, tetrahydrofuran, di Ether solvents such as alkane, alcohol solvents such as methanol, ethanol, isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, acetic acid Ester solvents such as butyl ester, nitrile solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and other amine solvents, 1,3- Urea solvents such as dimethyl-2-imidazolidone, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1a-a).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 0 ° C to 150 ° C or lower than the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When using an aqueous solution, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, etc. is dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. are dissolved, and a thio group is dissolved can be optionally used. Aqueous solutions of sulfur salts, such as sodium sulfate and sodium sulfite, and saline solution. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose.

The reaction mixture containing the compound represented by the formula (1a-b) obtained above can be removed by using a desiccant such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1a-b) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1a-b) obtained after the solvent is distilled off can be purified by washing with a suitable solvent, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing Method G] [Chem. 24]

In the formula, R3c represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, which may be appropriately substituted by a substituent C, or a C3-C8 cycloalkyl group, which may also be appropriately substituted by a substituent C, or may be substituted. C2 to C6 alkenyl, C2 to C6 haloalkenyl, C2 to C6 alkynyl, or C2 to C6 haloalkynyl, which may be appropriately substituted with substituent C, J represents an oxygen atom or A sulfur atom, Q represents a hydrogen atom or a metal, and R1, R2, R3b, X, Y, and n are synonymous with the foregoing.

Production method G: In the compound represented by formula (1a), R3c represents a C1-C6 alkyl group which may be appropriately substituted by a substituent C, a haloalkyl group of C1-C6, or C3 which may be appropriately substituted by a substituent C. ~ C8 cycloalkyl, C2 ~ C6 alkenyl, C2 ~ C6 haloalkenyl, C2 ~ C6 alkynyl, or C2 ~ A method for a compound represented by the formula (1a-c) having a haloalkynyl group of C6 and J representing an oxygen atom or a sulfur atom, comprising the step of reacting a compound represented by the formula (1a-b) with R3c-JQ in the presence of a transition metal Steps to obtain the combined reaction.

In the compound represented by the formula (1a-b), R3b is preferably a chlorine atom, a bromine atom, or an iodine atom.

R3c-J-Q used in this reaction can be obtained from a commercially available product or manufactured by a known method. Ideally, Q is a hydrogen atom or an alkali metal such as sodium or potassium. The amount of R3c-J-Q used in this reaction may be 1 equivalent or more with respect to the compound represented by formula (1a-b), and it is not particularly limited as long as the intended reaction proceeds. When Q is a hydrogen atom, it can also be used as a solvent.

The transition metals used in this reaction may also have ligands, such as palladium acetate, [1,1'-bis (diphenylphosphino) ferrocene] palladium dichloride, and ginseng (dibenzylideneacetone). Palladium, such as palladium, tris (triphenylphosphine) palladium, and bis (triphenylphosphine) palladium dichloride.

The amount of the transition metal used in this reaction is 0.001 equivalent to 1 equivalent with respect to the compound represented by formula (1a-b), and it is not particularly limited as long as the intended reaction proceeds.

In order for this reaction to proceed efficiently, triphenylphosphine, 1,1'-bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphino-2'4'6'-triiso Phosphine ligands such as propylbiphenyl and 2-di-tert-butylphosphino-2'4'6'-triisopropylbiphenyl.

The amount of the phosphine ligand used in this reaction is 0.001 equivalent or more and 1 equivalent or less based on the compound represented by formula (1a-b), and it is not particularly limited if the intended reaction proceeds.

The bases used in this reaction are inorganic bases such as sodium carbonate, potassium carbonate, and cesium carbonate, and organic bases such as triethylamine, tributylamine, and diisopropylethylamine.

The amount of the base used in this reaction is 1 equivalent or more with respect to the compound represented by the formula (1a-b), and it is sufficient if the intended reaction proceeds, and there is no particular limitation, and it is preferably 1 equivalent to 50 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and examples include R3c-JH (wherein R3c is synonymous with the above, J represents an oxygen atom), an alcohol solvent represented by diethyl ether, and diisopropyl ether , Methyl-tertiary butyl ether, dimethoxyethane, tetrahydrofuran, di Ether solvents such as alkane, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1a-b).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 30 ° C or higher and 200 ° C or lower or the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. are dissolved, and a saline solution can be optionally used. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose. In addition, filtration may be performed to remove insoluble matter, but this is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1a-c) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1a-c) obtained after the solvent is distilled off can be purified using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing method H] [Chem. 25]

In the formula, R3d represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, which may be appropriately substituted with a substituent C, or a C3-C8 cycloalkyl group, which may also be appropriately substituted with a substituent C, or may be substituted. C2 to C6 alkenyl, or C2 to C6 haloalkenyl appropriately substituted with the group C, R3d-B represents organic boric acids, and R1, R2, R3b, X, Y, and n are synonymous with the foregoing.

Production method H: In the compound represented by formula (1a), R3d represents a C1-C6 alkyl group which may be appropriately substituted by a substituent C, a haloalkyl group of C1-C6, or C3 which may be appropriately substituted by a substituent C. A method of a compound represented by the formula (1a-d) of a cycloalkyl group of ~ C8, an alkenyl group of C2 ~ C6, or a haloalkenyl group of C2 ~ C6, which may also be appropriately substituted by a substituent C, comprising making formula (1a- b) A step obtained by reacting a compound represented by an Suzuki-Miyaura coupling with an organic boric acid (R3d-B) in the presence of a transition metal and a base.

In formula (1a-b), R3b is preferably a chlorine atom, a bromine atom, or an iodine atom.

R3d-B used in this reaction represents an organic boric acid such as an organic boric acid or an organic borate, and can be obtained from a commercially available product or produced by a known method. The amount of R3d-B used in this reaction may be 1 equivalent or more relative to the compound represented by formula (1a-b), and it is not particularly limited if the intended reaction will proceed, and it is preferably 1 equivalent to 10 equivalents. .

The transition metals used in this reaction are palladium, nickel, ruthenium, etc., and may have ligands. Preferred are palladium acetate, [1,1'-bis (diphenylphosphino) ferrocene] palladium dichloride, ginsyl (dibenzylideneacetone) dipalladium, tris (triphenylphosphine) palladium, bis (Triphenylphosphine) Palladium such as palladium dichloride.

The amount of the transition metal used in this reaction is 0.001 equivalent to 1 equivalent with respect to the compound represented by formula (1a-b), and it is not particularly limited as long as the intended reaction proceeds.

In order to make this reaction proceed efficiently, phosphine ligands such as triphenylphosphine and tricyclohexylphosphine may be added. The amount of the phosphine ligand used in this reaction is 0.001 equivalent or more and 1 equivalent or less based on the compound represented by formula (1a-b), and it is not particularly limited if the intended reaction proceeds.

The bases used in this reaction are inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, and tripotassium phosphate, and metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide.

The amount of the base used in this reaction is 1 equivalent or more with respect to the compound represented by the formula (1a-b), and it is sufficient if the intended reaction proceeds, and there is no particular limitation, and it is preferably 1 equivalent to 50 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and examples include water solvents, diethyl ether, diisopropyl ether, methyl-third butyl ether, dimethoxyethane, tetrahydrofuran, diamine Ether solvents such as alkane, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1a-b).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 30 ° C or higher and 200 ° C or lower or the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like are dissolved, and a saline solution can be optionally used. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose. In addition, insoluble matter can be removed by performing a filtration operation, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1a-d) obtained above is not decomposed, the solvent can be distilled off under reduced pressure.

The reaction mixture containing the compound represented by the formula (1a-d) obtained after the solvent is distilled off can be purified by using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing Method I] [Chem. 26]

In the formula, R3e represents an alkynyl group of C2 to C6 or a haloalkynyl group of C2 to C6 which may be appropriately substituted by a substituent C, and R1, R2, R3b, X, Y, and n have the same meanings as described above.

Production method I is a compound represented by formula (1a-e) in which R3e in the compound represented by formula (1a) is an alkynyl group of C2 to C6 which may be appropriately substituted by substituent C, or a haloalkynyl group of C2 to C6 The method includes the step of obtaining the compound represented by (1a-b) by a round-head coupling by reacting the compound represented by (1a-b) with a terminal alkyne compound in the presence of a transition metal and a base.

In formula (1a-b), R3b is preferably a chlorine atom, a bromine atom, or an iodine atom.

The terminal alkyne compound used in this reaction can be obtained from a commercially available product or produced by a known method. As the terminal alkyne compound, trimethylsilylacetylene can also be used. At this time, after introducing the trimethylsilylethynyl compound into the compound represented by the formula (1a-b), it is necessary to perform desilylation. For desilication, you can refer to Journal of the American Chemical Society, Vol. 131, No. 2, pp. 634-643 (2009) and Journal of Organometallic Chemistry, Vol. 696, No. 25, pp. 4039-4045 (2011), etc. Patent literature implementation.

The amount of the terminal alkyne compound used in this reaction may be 1 equivalent or more with respect to the compound represented by formula (1a-b), and it is sufficient if the intended reaction proceeds, and is not particularly limited, preferably 1 equivalent to 10 equivalents.

The transition metals used in this reaction may also have ligands, such as palladium acetate, [1,1'-bis (diphenylphosphino) ferrocene] palladium dichloride, and ginseng (dibenzylideneacetone). Palladium, such as palladium, tris (triphenylphosphine) palladium, and bis (triphenylphosphine) palladium dichloride. Moreover, copper, such as copper chloride, copper bromide, and copper iodide, can also be used simultaneously.

The amount of the transition metal used in this reaction is palladium or the like and copper, and each of them should be 0.001 equivalent or more with respect to the compound represented by the formula (1a-b), as long as the intended reaction proceeds, there is no particular limitation. The ideal amount is 0.001 equivalent to 1 equivalent.

Examples of the base used in this reaction include organic amines such as triethylamine, tributylamine, isopropylamine, diethylamine, diisopropylamine, and diisopropylethylamine, and inorganic bases such as sodium carbonate, potassium carbonate, and cesium carbonate. Wait.

The amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1a-b), and it may be carried out if the intended reaction proceeds, and is not particularly limited, and preferably 1 to 50 equivalents. Moreover, those which are organic bases and liquid can be used as a solvent.

In order to make this reaction proceed efficiently, phosphine ligands such as tri-tertiary butylphosphine and 2-dicyclohexylphosphino-2'4'6'-triisopropylbiphenyl can be added, but it is not necessary.

The amount of the phosphine ligand used in this reaction is only required to be 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by formula (1a-b), and there is no particular limitation as long as the intended reaction proceeds.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and examples thereof include diethyl ether, diisopropyl ether, methyl-third butyl ether, dimethoxyethane, tetrahydrofuran, and diamine. Ether solvents such as alkane, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, and nitrile solvents such as acetonitrile , N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and other amine-based solvents, 1,3-dimethyl-2-imidazolidone, and other urea-based solvents Solvents, halogen solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, organic amines such as triethylamine, tributylamine, isopropylamine, diethylamine, diisopropylamine, and diisopropylethylamine Solvents, etc. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1a-b).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 0 ° C to 150 ° C or lower than the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like are dissolved, and a saline solution can be optionally used. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose. In addition, insoluble matter may be removed by a filtration operation, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1a-e) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1a-e) obtained after the solvent is distilled off can be purified by washing with a suitable solvent, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing Method J] [Chem. 27]

In the formula, R2a represents an alkoxy group of C1 to C6, and nb represents an integer of 0 to 4 (but when nb is 2 or more, two or more R2 represent independent substituents.), R1, R2, R3, X, Y and the dashed line portion are synonymous with the foregoing.

Production method J is a method for synthesizing a compound represented by formula (1-b) having a hydroxyl group among compounds represented by formula (1), including a compound represented by formula (1-a) in which R2a is an alkoxy group of C1 to C6. A step obtained by reacting with an acid.

The acids used in this reaction are boron halides such as boron trichloride and boron tribromide.

The amount of the acid used in this reaction is 1 equivalent or more with respect to the compound represented by the formula (1-a), and there is no particular limitation if the intended reaction will proceed, and it is preferably 1 equivalent to 10 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and examples thereof include benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene, nitrile solvents such as acetonitrile, and dichloride. Halogen solvents such as methane, dichloroethane, chloroform, and carbon tetrachloride; and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1-a).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually -80 ° C to 100 ° C or lower than the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like are dissolved, and a saline solution can be optionally used. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose.

The reaction mixture containing the compound represented by the formula (1-b) obtained above may be used to remove moisture using desiccants such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1-b) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1-b) obtained after the solvent is distilled off can be purified by using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing method K] [Chem. 28]

In the formula, R2b-O- represents an alkoxy group of C1 to C6 which may be appropriately substituted by substituent B, a haloalkoxy group of C1 to C6, and a cycloalkoxy group of C3 to C8 which may be appropriately substituted by substituent B. Group, C2 ~ C6 alkenyloxy group, C2 ~ C6 haloalkenyloxy group, which may also be appropriately substituted with substituent B, C3 ~ C6 alkynyloxy group, and C3 ~ C6 halide which may be appropriately substituted with substituent B An alkynyloxy group or an R20C (= O) O- group, Lv, R1, R2, R3, R20, X, Y, nb, and a dashed line are synonymous with the foregoing.

Production method K is a compound represented by formula (1) where R2b-O- represents a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group that may be appropriately substituted by a substituent B, or a substituent B is appropriately substituted C3 ~ C8 cycloalkoxy, C2 ~ C6 alkenyloxy, C2 ~ C6 haloalkoxy, or C3 ~ A method of a compound represented by the formula (1-c) of an alkynyloxy group of C6, a alkynyloxy group of C3 to C6, or an R20C (= O) O- group (R20 has the same meaning as described above.) Includes the following formula (1) a step of reacting the compound represented by -b) with R2b-Lv in a solvent in the presence of a base.

The R2b-Lv used in this reaction can be obtained from a commercially available product or manufactured by a known method. The R2b-Lv used in this reaction may be 1 equivalent or more with respect to the compound represented by formula (1-b), and it may be carried out if the intended reaction proceeds, and is not particularly limited, and is preferably 1 equivalent to 10 equivalents.

Examples of the base used in the reaction include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, and sodium hydride, triethylamine, tributylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, and trimethylamine. Organic bases such as pyridine and dimethylpyridine, but there is no particular limitation as long as the intended reaction proceeds.

The base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1-b), and may be carried out if the intended reaction proceeds, and is not particularly limited, and is preferably 1 equivalent to 10 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and examples thereof include diethyl ether, diisopropyl ether, methyl-third butyl ether, dimethoxyethane, tetrahydrofuran, and diamine. Ether solvents such as alkane, alcohol solvents such as methanol, ethanol, isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, acetic acid Ester solvents such as butyl ester, nitrile solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and other amine solvents, 1,3- Urea solvents such as dimethyl-2-imidazolidinone, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, sulfur solvents such as dimethylmethylene, cyclobutane, acetone, Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1-b).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually -20 ° C to 150 ° C or lower than the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When using an aqueous solution, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium hydrogen carbonate and the like are dissolved, and thiosulfuric acid is dissolved Aqueous solutions of sulfur salts, such as sodium and sodium sulfite, and saline solution. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose.

The reaction mixture containing the compound represented by the formula (1-c) obtained above can be used to remove moisture using desiccants such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1-c) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1-c) obtained after the solvent is distilled off can be purified by using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing Method L] [Chem. 29]

In the formula, R2c represents a halogen atom, and R2d represents a C1-C6 alkyl group which may be appropriately substituted with a substituent B, a C1-C6 haloalkyl group, and a C3-C8 cycloalkyl group which may also be appropriately substituted with a substituent B. , C2 ~ C6 alkenyl, or C2 ~ C6 haloalkenyl, which may also be appropriately substituted by substituent B, R2d-B represents organic boric acids, R1, R2, R3, nb, X, Y, and the broken line portion and The foregoing is synonymous.

Production method L: In the compound represented by formula (1), R2d is a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a C3 alkyl group that may be appropriately substituted by a substituent B. A method of a compound represented by the formula (1-e) of a cycloalkyl group of ~ C8, an alkenyl group of C2 ~ C6, or a haloalkenyl group of C2 ~ C6, which may also be appropriately substituted by a substituent B, comprising making formula (1-e) (d) A step obtained by reacting a compound represented by an organic boric acid (R2d-B) by a Suzuki-Miyaura coupling.

In the formula (1-d), R 2c is preferably a chlorine atom, a bromine atom, or an iodine atom.

The production method L can be implemented according to the production method H by replacing the compound represented by the formula (1a-b) and R3d-B in the production method H with the compound represented by the formula (1-d) and R2d-B, respectively.

[Manufacturing Method M] [Chem. 30]

In the formula, R2e represents an alkynyl group of C2 to C6 or a haloalkynyl group of C2 to C6 which may be appropriately substituted by a substituent B. R1, R2, R2c, R3, nb, X, Y, and a dashed line portion are as described above. Synonymous.

Production method M is a compound represented by formula (1-f) in which R2e in the compound represented by formula (1) is an alkynyl group of C2 to C6 which can be appropriately substituted by substituent B or a haloalkynyl group of C2 to C6 The method includes the step of obtaining by coupling a compound represented by the formula (1-d) with a terminal alkyne compound.

In the compound represented by formula (1-d), it is preferable that R2c is a chlorine atom, a bromine atom, or an iodine atom.

The manufacturing method M can be carried out according to the manufacturing method I by replacing the compound represented by the formula (1a-b) in the manufacturing method I with a compound represented by the formula (1-d).

[Manufacturing method N] [Chem. 31]

In the formula, Da represents a halogen atom, D1a represents a halogen atom, D1b represents C1 to C6 alkoxy, C1 to C6 haloalkoxy, or C3 to C8 cycloalkoxy, and E represents a halogen-substituted carbon atom. Or a nitrogen atom, R1, R2, R3, n, X, Q, and a broken line portion are synonymous with the foregoing.

Production method N represents that in the compound represented by the formula (1), D1b is an alkoxy group of C1 to C6, a haloalkoxy group of C1 to C6, or a cycloalkoxy group of C3 to C8, and E is a halogen substituted group. A method of a compound represented by the formula (1-h) with a carbon atom or a nitrogen atom includes a step of reacting the compound represented by the formula (1-g) with D1b-Q in a solvent.

D1b-Q used in this reaction can be obtained from a commercially available product or manufactured by a known method. Ideally, Q is a hydrogen atom or an alkali metal such as sodium or potassium.

The amount of D1b-Q used in this reaction may be 1 equivalent or more with respect to the compound represented by formula (1-g), and it may be performed if the objective reaction proceeds, and there is no particular limitation, preferably 1 equivalent to 30 equivalents. . When Q represents a hydrogen atom, it can be used as a solvent.

The base used in this reaction is preferably an inorganic base such as sodium carbonate, potassium carbonate, cesium carbonate, or sodium hydride. When Q is an alkali metal, the use of an alkali is not necessary.

The amount of the base used in this reaction is only required to be 1 equivalent or more with respect to the compound represented by the formula (1-g), and it is not particularly limited if the intended reaction proceeds, and it is preferably 1 equivalent to 30 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and examples thereof include alcohol solvents represented by D1b-H, diethyl ether, diisopropyl ether, methyl-third butyl ether, and dimethoxy group. Ethane, tetrahydrofuran, di Ether solvents such as alkane, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, and nitrile solvents such as acetonitrile , N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and other amine-based solvents, 1,3-dimethyl-2-imidazolidone, and other urea-based solvents Solvents, halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; sulfur-based solvents such as dimethyl sulfene and cyclobutane; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. . These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1-g).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 0 ° C or higher and 150 ° C or lower or the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like are dissolved, and a saline solution can be optionally used. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose.

The aforementioned reaction mixture containing the compound represented by the formula (1-h) can be used to remove moisture using desiccants such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1-h) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1-h) obtained after the solvent is distilled off can be purified by washing with appropriate solvents, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing method O] [Chem. 32]

In the formula, R2e represents an alkoxy group of C1 to C6 which may also be appropriately substituted with a substituent B, R2f represents an alkoxy group of C1 to C6 which may also be appropriately substituted with a substituent B, R2g represents a halogen atom, HalR, R1, R3, X, Y, and dashed lines are synonymous with the foregoing.

Production method O is to obtain R2e in the compound represented by formula (1) as an alkoxy group of C1 to C6 which can also be appropriately substituted by substituent B, and R2f being an alkoxy group of C1 to C6 which can also be appropriately substituted by substituent B R2g is a method for producing a compound represented by the halogen atom formula (1-j), which includes a step of reacting the compound represented by the formula (1-i) with a halogenating agent (HalR) in a solvent.

Examples of the halogenating agent used in this reaction include Selectfluor (N-fluoro-N'-triethylenediamine bis (tetrafluoroborate)), N-chlorosuccinimide, N-bromosuccinimide, and N-iodoamber Arsenimine, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5 , 5-dimethylhydantoin, bromine, iodine, etc.

The amount of the halogenating agent used in this reaction may be 1 equivalent or more relative to the compound represented by formula (1-i), and it may be carried out if the objective reaction proceeds, and there is no particular limitation, preferably 1 equivalent or more and 10 equivalents or less. . However, if the amount of the halogenating agent containing hydantoin is 0.5 equivalent or more, as long as the intended reaction proceeds, there is no particular limitation, and it is preferably 1 equivalent to 5 equivalents.

When the halogenating agent used in this reaction is an iodinating agent, it is possible to add acids such as inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. When the halogenating agent used in this reaction is an iodinating agent, the amount of acid used may be 0.01 equivalent or more with respect to the compound represented by formula (1-i), and if the objective reaction will proceed, there is no particular limitation. It is preferably from 0.1 to 3 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds. Examples include acidic solvents such as sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, diethyl ether, and diisopropyl ether. , Methyl-tertiary butyl ether, dimethoxyethane, tetrahydrofuran, di Ether solvents such as alkane, alcohol solvents such as methanol, ethanol, isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, acetic acid Ester solvents such as butyl ester, nitrile solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and other amine solvents, 1,3- Urea solvents such as dimethyl-2-imidazolidone, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1-i).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 0 ° C or higher and 150 ° C or lower or the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium hydrogen carbonate and the like are dissolved, and thiosulfuric acid is dissolved Sulfur-containing saline solutions such as sodium, sodium sulfite, and saline. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose.

The reaction mixture containing the compound represented by the formula (1-j) obtained above can be used to remove water using desiccants such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (1-j) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (1-j) obtained after the solvent is distilled off can be purified by using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

[Manufacturing Method P] [Chem. 33]

In the formula, La represents S, Lb represents SO or SO ₂ , and Ox 'represents an oxidant.

Production method P is a method for producing a compound represented by formula (Lb) in which Lb contained in R1, R2, and R3 is SO or SO ₂ among the compounds represented by formula (1), and comprises R1, R2 in formula (1) Or the step of reacting a compound represented by the formula (La) in which La is S contained in R3 with an oxidizing agent (Ox ').

Examples of the oxidant used in the reaction include peroxides such as hydrogen peroxide water and m-chloroperbenzoic acid. In addition, transition metals such as sodium tungstate can be added.

The amount of oxidant used in this reaction is usually 1.0 to 1.2 equivalents relative to the compound represented by formula (La) when producing SO, and is usually 2 to 10 equivalents when producing SO ₂ . When a transition metal is added, it is usually 0.001 equivalent to 1 equivalent.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds. Examples include aqueous solvents, acidic solvents such as acetic acid, benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. Solvents, nitrile solvents such as acetonitrile, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (1) having the formula (La).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually -10 ° C or higher and 120 ° C or lower or the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium hydrogen carbonate and the like are dissolved, and thiosulfuric acid is dissolved Aqueous solutions of sulfur salts, such as sodium and sodium sulfite, and saline solution. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose.

The reaction mixture containing the compound represented by the formula (Lb) obtained as described above may be used to remove moisture using desiccants such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (Lb) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (Lb) obtained after the solvent is distilled off can be purified by using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

A method for synthesizing the compound represented by formula (3) described in Production Method A is described below. [Manufacturing method Q] [Chem. 34]

In the formula, R2, R3, R5, n, X and Y have the same meanings as described above.

Production method Q is a production method of a production intermediate represented by formula (3), which includes a step of reacting a compound represented by formula (4) and a compound represented by formula (5) in a solvent in the presence of a base.

The compound represented by formula (4) used in this reaction can be synthesized by referring to, for example, Green Chemistry, Vol. 41, pp. 580-585, The Journal of Organic Chemistry), Vol. 65, No. 20, p. 6458-6461 (2000), etc. .

The compound represented by the formula (5) used in this reaction can be obtained from a commercially available product or produced by a known method. The amount of the compound represented by the formula (5) used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (4), and if the objective reaction will proceed, there is no particular limitation, preferably 1 equivalent or more 3 Below equivalent.

The bases used in this reaction are inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, and tripotassium phosphate, and metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide.

The base used in this reaction can be carried out with a catalyst amount, and the objective reaction can be carried out without any particular limitation. It is preferably 0.01 equivalent to 3 equivalents with respect to the compound represented by formula (4).

Examples of the solvent used in this reaction include diethyl ether, diisopropyl ether, methyl-tertiary butyl ether, dimethoxyethane, tetrahydrofuran, and diethyl ether. Ether solvents such as alkane, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, and nitrile solvents such as acetonitrile , N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and other amine-based solvents, 1,3-dimethyl-2-imidazolidone, and other urea-based solvents Solvents, halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; sulfur-based solvents such as dimethyl sulfene and cyclobutane; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. . These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by the formula (4).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually -50 ° C to 150 ° C or below the boiling point of the solvent.

The post-reaction treatment can be carried out by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like are dissolved, and a saline solution can be optionally used. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose.

The reaction mixture containing the compound represented by the formula (3) obtained above can be used to remove moisture using desiccants such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (3) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (3) obtained after the solvent is distilled off can be purified by washing, reprecipitation, recrystallization, column chromatography, and the like using an appropriate solvent. It can be appropriately set according to the purity of the purpose.

[Manufacturing method R] [Chem. 35]

In the formula, R5a represents an alkyl group of C1 to C6, and R2, R3, n, X, and Y have the same meanings as described above.

Production method R is a production method for producing an intermediate represented by formula (3b) among compounds represented by formula (3), and includes a step of reacting a compound represented by formula (3a) in a solvent under acidic or basic conditions.

First, the reaction to acidic conditions will be explained. Examples of the acid used in the reaction include inorganic acids such as hydrochloric acid, hydrobromic acid, and phosphoric acid, and organic acids such as acetic acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. There is no particular limitation as long as the objective reaction can proceed.

The amount of the acid used in this reaction may also be the amount of the catalyst, as long as the intended reaction will proceed, and there is no particular limitation, it is preferably 0.01 equivalent or more relative to the compound represented by formula (3a). The liquid acid can be used as a solvent.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds. Examples include water solvents, acidic solvents such as acetic acid and methanesulfonic acid, diethyl ether, diisopropyl ether, methyl-tertiary butyl ether, Dimethoxyethane, tetrahydrofuran, di Ether solvents such as alkane, alcohol solvents such as methanol, ethanol, isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, acetic acid Ester solvents such as butyl ester, nitrile solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and other amine solvents, 1,3- Urea solvents such as dimethyl-2-imidazolidone, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by formula (3a).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually 0 ° C to 180 ° C or lower than the boiling point of the solvent.

Then the reaction for alkaline conditions will be explained. Examples of the base used in this reaction include inorganic bases such as lithium hydroxide, sodium hydroxide, and potassium hydroxide. However, if the intended reaction proceeds, there is no particular limitation.

The base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (3a), and may be carried out if the intended reaction proceeds, and is not particularly limited. It is preferably 1 equivalent to 30 equivalents,

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds. Examples include water solvents, diethyl ether, diisopropyl ether, methyl-third butyl ether, dimethoxyethane, tetrahydrofuran, Ether solvents such as alkane, alcohol solvents such as methanol, ethanol, isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, acetic acid Ester solvents such as butyl ester, nitrile solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and other amine solvents, 1,3- Urea solvents such as dimethyl-2-imidazolidone, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride. These solvents may be used singly or as a mixture of two or more kinds in any ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, and is usually 3 to 200 times the weight of the compound represented by formula (3a).

The temperature at which the reaction proceeds is not particularly limited as long as the intended reaction proceeds, and is usually -20 ° C to 180 ° C or the boiling point of the solvent.

Regarding the post-reaction treatment, the reaction under acidic conditions and the reaction under basic conditions can be carried out by a common method. Liquid separation can be performed by adding water or a suitable aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid and the like are dissolved, an alkali aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like are dissolved, and a saline solution can be optionally used. During the liquid separation operation, if necessary, benzene solvents such as toluene, xylene, benzene, chlorobenzene, and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, and diisopropyl ether can be added. , Ether solvents such as methyl, tertiary butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane It is a solvent that is immiscible with water. These solvents may be used alone or as a mixture of two or more of them in an arbitrary ratio. There are no special restrictions on the number of liquid separations, which can be implemented according to the purity and yield of the purpose.

The aforementioned reaction mixture containing the compound represented by the formula (3b) can be used to remove moisture using desiccants such as sodium sulfate and magnesium sulfate, but it is not necessary.

As long as the reaction mixture containing the compound represented by the formula (3b) obtained above is not decomposed, the solvent can be distilled off under reduced pressure. The reaction mixture containing the compound represented by the formula (3b) obtained after the solvent is distilled off can be purified by using an appropriate solvent for washing, reprecipitation, recrystallization, column chromatography, and the like. It can be appropriately set according to the purity of the purpose.

Compounds represented by formula (3b) also include isomers represented by formula (3b '); In the formula, R2, R3, n, X and Y have the same meanings as described above.

The compound represented by the formula (3b ') can be handled in the same manner as the compound represented by the formula (3b), and the production method A can be applied. The compound represented by the formula (3b ') includes an asymmetric carbon, and the mixture ratio of the isomers may be a single or a mixture in any ratio. Furthermore, it may be a mixture of the compound represented by the formula (3b) and the compound represented by the formula (3b '), and the mixing ratio of the isomers may be a single or a mixture in any ratio.

The compound represented by the formula (1) can be produced by arbitrarily combining the production methods A to R described above. Alternatively, a compound represented by the formula (1) may be produced by arbitrarily combining a known method and the production method A to the production method R.

Next, the quinoline-based compound represented by the formula (2a) or the formula (2b) will be described. R2a and R2b of formula (2a) and formula (2b) each independently represent an alkyl group of C1 to C6 which may be appropriately substituted by substituent E1, an aryl group which may be appropriately substituted by substituent E2, or a substituent E3 appropriately substituted heteroaryl, or arylalkyl which may also be appropriately substituted with substituent E2, or R2a and R2b may be integrated with the carbon atom to which they are bonded to form C3, which may also be appropriately substituted with substituent E4 ~ C10 cycloalkyl ring.

Among them, R2a and R2b each independently represent an alkyl group of C1 to C6 which can also be appropriately substituted by the substituent E1, especially an alkyl group of C1 to C6 is preferable, and a methyl group is more preferable.

R2c and R2d of formula (2a) and formula (2b) each independently represent a hydrogen atom, a C1 to C6 alkyl group, a halogen atom, a C1 to C6 alkoxy group, or a hydroxyl group which may also be appropriately substituted by a substituent E1, Alternatively, R2c and R2d may be integrated with the carbon atom to which they are bonded to form a cycloalkyl ring of C3 to C10 which may be appropriately substituted by a carbonyl group or a substituent E4.

Among them, R2c and R2d each independently represent a hydrogen atom, an alkyl group of C1 to C6 which can also be appropriately substituted by the substituent E1, especially an alkyl group of C1 to C6, or a halogen atom is preferred, and a hydrogen atom, a methyl group or a fluorine atom is more preferred ideal.

R2e in formula (2a) and formula (2b) represents a hydrogen atom, a fluorenyl group of C2 to C7, or an alkyl group of C1 to C6 which may be appropriately substituted by a substituent E1.

Among them, R2e is preferably a hydrogen atom or an alkyl group of C1 to C6 which may be appropriately substituted by a substituent E1, especially an alkyl group of C1 to C6 is preferable, and a hydrogen atom or a methyl group is more preferable. Most preferably, it is a hydrogen atom.

X1 in formula (2a) and formula (2b) represents a halogen atom, an alkyl group of C1 to C6 which may be appropriately substituted by substituent E5, an alkenyl group of C2 to C6 which may also be appropriately substituted by substituent E6, or C2 ~ C6 alkynyl suitably substituted with substituent E7, aryl optionally substituted with substituent E2, heteroaryl optionally substituted with substituent E3, alkoxy groups C1-C6, or Substituent E8 is an appropriately substituted amine group, C2 to C7 fluorenyl group, cyano group, or N-hydroxyalkylimino group which may also substitute a hydrogen atom of a hydroxyl group through substituent E9.

Among them, X1 is preferably a halogen atom, and a fluorine atom is more preferable.

X2 in formula (2a) and formula (2b) represents a halogen atom, an alkyl group of C1 to C6, an alkoxy group of C1 to C6, or a hydroxyl group.

Among them, X2 is preferably a halogen atom, and a fluorine atom is more desirable.

In formulas (2a) and (2b), n1 represents an integer of 0 to 4, and n2 represents an integer of 0 to 6.

Among them, n1 is preferably an integer of 0 to 1, and n2 is preferably an integer of 0 to 2, especially an integer of 0 to 1 is preferred.

The substituent E1 of the formula (2a) and the formula (2b) is at least one selected from the group consisting of a halogen atom, an alkoxy group of C1 to C6, an alkylthio group of C1 to C6, and a phenoxy group.

The substituent E2 of the formula (2a) and the formula (2b) is selected from a halogen atom, an alkyl group of C1 to C6, a haloalkyl group of C1 to C6, an alkoxy group of C1 to C6, and may be appropriately substituted by the substituent E8 At least one selected from the group consisting of a substituted amine group, a nitro group, a cyano group, a hydroxyl group, a mercapto group, and a C1 to C6 alkylthio group.

The substituent E3 of the formula (2a) and the formula (2b) is at least 1 selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, and a C1-C6 alkoxy group. Species.

The substituent E4 of the formula (2a) and the formula (2b) is at least one selected from the group consisting of a halogen atom, an alkyl group of C1 to C6, an alkoxy group of C1 to C6, and a phenoxy group.

The substituent E5 of the formula (2a) and the formula (2b) is at least 1 selected from the group consisting of a halogen atom, an alkoxy group of C1 to C6, a hydroxyl group, an alkoxycarbonyl group of C2 to C7, and a phenoxy group. Species.

The substituent E6 of the formula (2a) and the formula (2b) is at least one selected from the group consisting of a halogen atom, an alkoxy group of C1 to C6, an alkoxycarbonyl group of C2 to C7, and a phenoxy group.

The substituent E7 of the formula (2a) and the formula (2b) is at least one selected from the group consisting of a halogen atom, an alkoxy group of C1 to C6, and a phenoxy group.

The substituent E8 of the formula (2a) and the formula (2b) is at least one selected from the group consisting of a C1 to C6 alkyl group and a C2 to C7 fluorenyl group.

The substituent E9 of formula (2a) and formula (2b) is selected from the group consisting of C1 to C6 alkyl, C2 to C6 alkenyl, C2 to C6 alkynyl, aralkyl, aryl, and heteroaryl. At least one of the groups.

Among them, the quinoline compound represented by formula (2a) or (2b) is preferably a quinoline compound represented by formula (2c) or (2d); [Chem 37] [In the formula, R2f represents a hydrogen atom or a methyl group, X3, X4, and X5 each independently represent a hydrogen atom or a fluorine atom, and X6 and X7 each independently represent a hydrogen atom, a methyl group, or a fluorine atom].

In particular, the quinoline-based compound represented by formula (2a) or (2b) is preferably 3- (4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) quine (Compound No .: (2) -1), 3- (4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline (Compound No .: (2) -2), 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-1,2,3,4-tetrahydroisoquinoline-1- ) Quinoline (compound number: (2) -3), or 8-fluoro-3- (5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) quine Porphyrin (compound number: (2) -4) is most preferred. [Chemical 38] [Chemical 39] [Chemical 40] [Chemical 41] .

When a quinoline compound represented by the aforementioned formula (2c) or formula (2d) and X3 or X4, especially X3 is a fluorine atom, were found to be gray mold, rice fever, apple scab, cucumber anthracnose, etc. The effect of the disease is significantly improved, which is ideal.

Especially, it is a quinoline compound represented by formula (2c) or formula (2d), and R2f is a hydrogen atom or a methyl group, X3 is a fluorine atom, X4, X5, X6, and X7 are each independently a hydrogen atom or a fluorine atom, but A quinoline-based compound or a salt thereof in which at least one of X4, X5, X6 or X7 in formula (2c) is a fluorine atom, and either of X4 or X5 in formula (2d) is a fluorine atom. Diseases such as mildew, rice fever, apple scab, cucumber anthracnose, etc. show significant effects and are therefore ideal. In particular, the quinoline-based compounds (2) -2, (2) -3, and (2) -4 are preferable, and the quinoline-based compounds (2) -2 and (2) -3 are preferable.

In addition, it was found that the above-mentioned quinoline compounds (2) -3 and (2) -4 have a half-life period of 7 to 55 days for the soil residue test in the container, and have remarkable environmental dynamic characteristics of low soil residue, which is ideal.

For a quinoline-based compound represented by formula (2a) or formula (2b), biological activity, or a method for controlling a pest using this component, refer to a well-known document (for example, International Publication No. 05/070917 or International Publication No. 08 / 066148). For the production method of the quinoline-based compound represented by the formula (2a) or the formula (2b) and a method for producing the intermediate, refer to a known document (for example, International Publication No. 05/070917, International Publication No. 08/066148, International Publication No. 13/047749, International Publication No. 13/047750, or International Publication No. 13/047751).

Then, the pest control composition of this invention is demonstrated. The pest control composition of the present invention can be manufactured in accordance with a common method for manufacturing general pesticides. That is, the pest control composition can be prepared by mixing two or more types of active ingredients of the compound of the present invention and a quinoline compound, and optionally mixing a carrier and an adjuvant, etc., to produce an active ingredient containing the two. Composition. Alternatively, a composition containing one of the compound of the present invention and a quinoline-based compound may be produced first, and then the other may be added to produce a composition containing the active ingredients of both. Generally, it is preferable to prepare a mixture in which the active ingredients of the two are mixed, and to manufacture the pest control composition. Or the pest control composition of the present invention can be produced by mixing a carrier and an adjuvant, etc., as necessary, with only the active ingredients of a quinoline compound according to a common method related to the production of general pesticides.

In the pest control composition of the present invention, only a combination of the compound of the present invention and a quinoline-based compound or only a quinoline-based compound may be directly used, but it is usually mixed with a support, and a surfactant, etc. may be added if necessary. Adhesives, disintegrating agents, stabilizers, pH adjusters, antibacterial and antifungal agents (preservatives), tackifiers, defoamers, humectants, fixatives, colorants and other auxiliary agents are formulated in a timely manner in accordance with ordinary methods. Hydration, water suspension, granule hydration, OD, powder, liquid, emulsion, granule, patch and other dosage forms. The form is not particularly limited as long as it exhibits effects. In addition, the pest control composition of the present invention may be in the form of a one-dose formulation of the compound of the present invention and a quinoline-based compound, or may be in the form of a group of the two obtained by being formulated into separate dosage forms.

The carrier used in the composition of the present invention refers to a synthetic or natural inorganic or organic substance that helps the active ingredient reach the place to be treated and is blended for easy storage, transportation, and operation of the active ingredient compound, as long as it is generally Pesticide users only need to use solid, liquid or gas. This support is not limited as long as the effect can be exhibited.

The solid support that can be used for the composition of the present invention includes, for example, inorganic substances such as bentonite, montmorillonite, diatomaceous earth, white clay, talc, clay, plant organic substances such as wood flour, sawdust, or urea.

The liquid carriers that can be used for the composition of the present invention include, for example, aromatic hydrocarbons such as xylene and toluene, naphthene, aliphatic hydrocarbons such as n-paraffin and flowing paraffin, ketones such as acetone and methyl ethyl ketone, two Ethers such as alkane and diethylene glycol dimethyl ether, alcohols such as ethanol and ethylene glycol, carbonates such as ethylene carbonate, aprotic solvents such as dimethylformamide, water, and the like. Gas carriers that can be used for the composition of the present invention, for example, nitrogen, carbon dioxide gas, and the like.

Furthermore, in order to enhance the effectiveness of the compounds in the composition of the present invention, an adjuvant may be used. The form of use can be considered alone or in combination depending on the purpose of the preparation, including the dosage form and processing method. Adjuvants, such as surfactants, binding agents, disintegrating agents, stabilizers, pH adjusting agents, antibacterial and antifungal agents, thickeners, antifoaming agents, antifreeze agents, and the like.

As the surfactant that can be used in the composition of the present invention, a surfactant that is generally used for emulsifying, dispersing, expanding, and / or moisturizing a pesticide formulation can be used. The surfactant, such as sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block polymer, alkyl polyoxyethylene Polyoxypropylene block polymer ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid ammonium amine, polyoxyethylene diphenyl ether, polyoxyalkylene adduct of higher alcohol, polyoxyethylene ether, ester polysilicon Non-ionic surfactants such as oxygen and fluorine surfactants; alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene benzyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, paraffin waxes Sulfonate, alkane sulfonate, AOS, dialkyl sulfosuccinate, alkylbenzene sulfonate, lignin sulfonate, polyoxyethylene alkyl phenyl ether sulfonate, fatty acid salt, N-formaldehyde Base-fatty acid sarcosinate, polyoxyethylene alkyl ether phosphate, polyoxyethylene phenyl ether phosphate, polyoxyethylene polyoxypropylene block polymer phosphate, phospholipids choline, phospholipids ethanolimine, alkyl Anionic surfactants such as phosphate and sodium tripolyphosphate; alkyltrimethylammonium chloride, alkane Cationic surfactants such as methyl dimethyl hydroxychloroaniline, benzethonium chloride; amphoteric surfactants such as dialkyldiaminoethyl betaine, alkyl dimethyl benzyl betaine, etc. .

Binders, such as: sodium alginate, polyvinyl alcohol, gum arabic, sodium carboxymethyl cellulose, bentonite, etc.

Disintegrating agents include, for example, sodium carboxymethyl cellulose CMC, croscarmellose sodium and the like.

Stabilizers include, for example, hindered phenol-based antioxidants, benzotriazole-based, and hindered amine-based ultraviolet absorbers.

pH adjusting agent, for example: phosphoric acid, acetic acid, sodium hydroxide and the like.

Antibacterial and antifungal agents, such as: industrial bactericides such as sodium benzoate, potassium sorbate, parabens, 1,2-benzoisothiazolin-3-one, antibacterial and antifungal agents, and the like.

Tackifiers, such as: Sanxian gum, guar gum, sodium carboxymethyl cellulose, acacia gum, polyvinyl alcohol, montmorillonite, etc.

Antifoaming agents, for example: polysiloxane compounds.

Antifreeze, for example: propylene glycol, ethylene glycol, etc.

The adjuvants described above are examples, and the adjuvants used in the composition of the present invention are not particularly limited as long as they exhibit effects.

The content of the compound of the present invention in the composition of the present invention is not particularly limited as long as the effect can be exhibited. Generally, the weight ratio is in the range of 0.01 to 99%, preferably in the range of 0.1 to 90%, and more preferably The range is 1 ~ 80%. In addition, the content of the quinoline-based compound in the composition of the present invention is not particularly limited as long as the effect can be exhibited, and is usually in a range of 0.01 to 99% by weight ratio, preferably in a range of 0.1 to 90%, more It is preferably in the range of 1 to 80%. The total content of the compound of the present invention and the quinoline compound in the composition of the present invention is not particularly limited as long as the effect can be exhibited, and it is usually in the range of 0.01 to 99% by weight ratio, preferably 0.1 to 90. The range of% is more preferably in the range of 1 to 80%.

The mixing ratio of the compound of the present invention and the quinoline compound in the composition of the present invention is not particularly limited as long as the effect can be exhibited. Generally, the quinoline compound is 0.001 to 1000 by weight ratio relative to the compound of the present invention. The ratio is preferably a ratio of 0.01 to 100.

Then, the pest control method using the pest control composition of this invention is demonstrated.

The composition of the present invention can be used for controlling pests in dry fields, paddy fields, tea gardens, orchards, grasslands, lawns, forests, gardens, street trees, and the like.

The agricultural application method of the composition of the present invention is, for example, the treatment of plant stem and leaf spreading, seedling box processing, plug tray processing, soil spreading treatment, soil mixing after soil surface spreading treatment, and soil Injection treatment in the soil, soil mixing after the injection treatment in the soil, soil infusion treatment, soil mixing after the soil infusion treatment, spray treatment on the plant seeds, smear treatment on the plant seeds, immersion treatment on the plant seeds, or For coating of plant seeds, etc. Application methods used by those skilled in the art can generally be used.

Examples of the method for controlling the pest in the present invention include a method for applying the pest control composition of the present invention, a composition containing the compound of the present invention as an active ingredient, and a composition containing a quinoline compound as an active ingredient. A method of applying a composition containing any one of the compounds of the present invention as an active ingredient or a composition containing a quinoline compound as an active ingredient, and then applying the other composition.

Examples of the method for applying the pest control composition of the present invention include a method of applying the pest control composition manufactured by including the compound of the present invention and two or more types of active ingredients of a quinoline compound, or the user A method of preparing a composition containing the compound of the present invention and a quinoline compound and using the composition containing the compound of the present invention as an active ingredient and a composition containing the quinoline compound as an active ingredient before use.

The time (period) after the application of either the composition containing the compound of the present invention as an active ingredient or the composition containing the quinoline compound as an active ingredient until the application of the other composition, as long as the effect is possible There is no particular limitation on the application, for example: 1 minute to 2 weeks after the application of any one of the compositions, preferably 5 minutes to 1 week after the application of any of the compositions, and more preferably the application of any 10 minutes to 3 days after the composition.

The application amount and dilution ratio of the composition of the present invention can be appropriately selected and determined according to the target crop, the target pest, the occurrence degree of the pest, the dosage form of the composition of the present invention, the application method and various environmental conditions.

When dispersing the composition of the present invention, its application amount is not particularly limited as long as the effect can be exerted. Generally, it is 1 to 10,000 g per 1 hectare, preferably 10 to 5000 g per 1 hectare, in terms of effective ingredient amount conversion. In addition, when the composition of the present invention is used as a seed disinfectant, its application amount is not particularly limited as long as the effect can be exhibited. Generally, in terms of effective ingredient conversion, the seed is 0.001 to 100 g per 1 kg, preferably 0.01 to 50 g. . In addition, when the hydrating agent, granular hydrating agent, liquid agent, OD agent, aqueous suspension, or emulsion of the composition of the present invention is diluted with water and dispersed, the dilution ratio is not particularly limited as long as the effect can be exhibited, usually 5 ~ 50,000 times, preferably 10 ~ 10000 times.

The "plant" referred to in the present invention refers to a person who photosynthesizes without moving. Specific examples include cereals such as rice, wheat, barley, and corn, grapes, apples, pears, peaches, cherries, persimmons, citrus, and other fruit trees, beans, beans, beans and other peas, strawberries, watermelons, and other fruits, potatoes, Sweet potatoes, taro, coriander and other taro, cabbage, lettuce, tomato, cucumber, eggplant, beet, spinach, pumpkin, green pepper and other vegetables, linseed, cotton, sunflower, tulip, chrysanthemum and other flowers or sugar cane, tobacco, grassland Etc., but not limited to them.

The "seed" as referred to in the present invention is a user who accumulates nutritional components of young plants for germination and is used in agricultural reproduction. Specific examples include seeds of corn, soybean, cotton, coriander, leaf beet, wheat, barley, sunflower, tomato, cucumber, eggplant, spinach, pea, pumpkin, sugarcane, tobacco, green pepper, rapeseed, etc .; taro, potato, sweet potato Taro and other taro species, bulbs such as edible cucumbers and tulips, seed bulbs such as chives, or plants derived from human manipulation such as genes, such as soybeans, corn, cotton, etc. that impart herbicide tolerance that did not exist in nature; adaptation Rice, tobacco, etc. in cold regions; corn, cotton, potato, etc., which have been given insecticidal substance production capacity, have undergone transformed seeds, but are not limited to these.

In this specification, pests refer to organisms that cause adverse effects on the growth of plants, such as bacteria, fungi, viruses, and other pathogenic bacteria, pests, and weeds. Pathogens can infect plants and cause plant diseases. Pests can parasite and damage plants. As weeds flourish on or near plant growth sites, they compete with plants for light synthesis and nutrient absorption. For these reasons, harmful organisms can cause poor plant growth, withering, and reduced yield, and are harmful to plants. The composition and control method of the present invention are effective for such pests. Specific pathogenic bacteria and pests to be controlled in the present invention are exemplified below.

Pathogens, such as: Magnaporthe grisea, Thanatephorus cucumeris, Ceratobasidium setariae, Waitea circinata, Thanatephorus cucumeris ), Sclerotium hydrophilum, Wairea circinata, Entyloma dactylidis, Magnaporthe salvinii, Ceratobasidium cornigerum, Sesame leaf withered Cochliobolus miyabeanus, Sphaerulina oryzina, Gibberella fujikuroi, Pythium spp., Fusarium spp., Trichoderma spp., Rhizopus spp., Solizorconia ), Pythium spp., Achlya spp., Dictyuchus spp.), Claviceps virens, Tilletia barclayana, Curvularia spp., Alternaria spp., Yellowing Sclerophthora macrospora, Xanthomonas oryzae pv. Oryzae, Acidovorax avenae subsp. avenae), Erwinia ananas, Burkholderia plantarii, Burkholderia glumae, Pseudomonas fuscovaginae, Pseudomonas syringae pv.oryzae), Erwinia chrysanthemi, Phytoplasma oryzae, Rice stripe tenuivirus, Rice dwarf reovirus; Blumeria graminis f. sp. Hordei; f.sp.tritici), Puccinia striiformis, Puccinia graminis, Puccinia recondita, Puccinia hordei, Pyrenophora graminea, Pyrenophora teres, Gibberella zeae, Fusarium culmorum, Fusarium avenaceum, Monographella nivalis), snow rot fungus (Typhula incarnata, Typhula ishikariensis, Monographella nivalis), naked smut (Ustilago nuda), smut black fungus (Tilletia caries, Tilletia controversa), sclerotinia cereus herpes (orse) ), Ceratobasidium gramineum, Rhynchosporium secalis, Septoria tritici, Phaeosphaeria nodorum, Fusarium spp., Pythium spp., Rhizoctonia spp., Septoria spp., Pyrenophora spp. Gaeumannomyces graminis, Colletotrichum graminicola, Claviceps purpurea, Cochliobolus sativus, Pseudomonas syringae pv. Syringae, Gibberella zeae, etc. ), Fusarium avenaceum, Penicillium spp, Pythium spp., Rhizoctonia spp.), Puccinia sorghi, Cochliobolus heterostrophus, Ustilago maydis, and anthracnose Colletotrichum graminicola), Cochliobolus carbonum, Acidovorax avenae subsp.avenae, Burkholderia andropogonis, Erwinia chrysanthemi pv. Zeae, Erwinia stewara ; Grape Plasmopara viticola, rust fungus (Physo pella ampelopsidis), Uncinula necator, Elsinoe ampelina, Glomerella cingulata, Colletotrichum acutatum, Guignardia bidwellii, Phomopsis viticola, Brown spot disease Zygophiala jamaicensis), Botrytis cinerea, Diaporthe medusaea, Helicobasidium mompa, Rosellinia necatrix, Agrobacterium vitis; Root cancer Pathogens (Podosphaera leucotricha), Venturia inaequalis, Alternaria mali, Gymnosporangium yamadae, Monilinia mali, Rot fungus (Valsa ceratosperma), Botryiana ), Colletotrichum acutatum, Glomerella cingulata, Zygophiala jamaicensis, Gloeodes pomigena, Mycosphaerella pomi, Helicobasidium mompa (Rosellinia necatrix), Phomopsis mal i, Diaporthe tanakae), Diplocarpon mali, Erwinia amylovora, Agrobacterium tumefaciens, Agrobacterium rhizogenes; Alternaria kikuchiana, Black Venturia nashicola, Gymnosporangium asiaticum, Botryosphaeria berengeriana f.sp. piricola, Phomopsis fukushii, Erwinia sp., Root nodule Agrobacterium tumefaciens), Erwinia chrysanthemi pv. Chrysanthemi, Pseudomonas syringae pv. Syringae; Phytophthora cactorum, Phytophthora syringae, Phytophthora sp. ); Cladosporium carpophilum, Phomopsis sp., Phytophthora sp., Colletotrichum gloeosporioides, Taphrina deformans, perforation Xhanthomonas campestris pv. Pruni, Agrobacterium tu mefaciens); Cherry anthracnose (Glomerella cingulata), young fruit sclerotinia (Monilinia kusanoi), gray star disease (Monilinia fructicola), root head cancer (Agrobacterium tumefaciens), resinous bacteria (Pseudomonas syringae pv. syringae) ; Glomerella cingulata, Cercospora kaki, Mycosphaerella nawae, Phyllactinia kakikora, Agrobacterium tumefaciens, Diaporthe citri (Penicillium digitatum), Penicillium italicum, Elsinoe fawcettii, Phytophthora citrophthora, Xhanthomonas campestris pv. Citri, Pseudomonas syringae pv. Pathogens (Liberibactor asiaticus), Agrobacterium tumefaciens; Tomato, cucumber, legume, strawberry, potato, cabbage, eggplant, lettuce and other gray mold (Botrytis cinerea); tomato, cucumber, legume, strawberry, potato , Rapeseed, Sclerotinia sclerotiorum, cabbage, eggplant, lettuce, etc .; tomato, cucumber, beans, turnip, watermelon, eggplant, rapeseed, sweet pepper, spinach, beet and other vegetables, Rhizoctonia spp. , Pythium spp., Fusarium spp., Phythophthora spp., Sclerotinia sclerotiorum, etc.); Rapeseed, fungus (Ralstonia solanacearum); Pseudoperonospora cubensis (SphaeroCollele tricigi) orbiculare), Didymella bryoniae, Fusarium oxysporum, Phytophthora parasitica, Phytophthora melonis, Phytophthora nicotianae, Phytophthora drechsleri, Phytophthora capsici bacteria, etc. , Erwinia carotovora subsp. Carotovora, Pseudomonas syringae pv. Lachrymans, Pseudomonas marginalis pv. Marginalis, Streptomyces sp., Agrobacterium rhizogenes Leaf virus (Cucumber mosaic virus); Alternaria solani, Fulvia fulva, Phytophthora infestans, Fusarium oxysporum, Pythium myriotylum, Pythium dissotocum Colletotrichum gloeosporioides, Clavibacter michiganensis, Pseudomonas corrugata, Pseudomonas viridiflava, Erwinia carotovora subsp. Carotovora, Cryne .), Phytoplasma asteris, Tabaco leaf curl subgroup III geminivirus; Sphaerotheca fuliginea, etc .; Mycovellosiella nattrassii, Phytophthora infestans, brown Phytophthora capsici, Pseudomonas cichorii, Pseudomonas corrugata, Erwinia chrysanthemi, Erwinia carotovora subsp. Carotovora, Pseudomonas spse . ); Alternaria brassicae, Xhanthomonas campestris pv. Campestris, Pseudomonas syringae pv. Maculicola, Erwinia carotovora, cruciferous vegetables Pathogens (Alternaria brassicae, etc.), Cercosporella brassicae, Phoma lingam, Plasmodiophora brassicae, Peronospora parasitica, Black rot (Xhanthomonas campestris pv. Campestris), Black spot Bacterial bacteria (Pseudomonas syringae pv. Maculicola), soft rot (Erwinia carotovora subsp. Carotovora); cabbage rot (Thanatephorus cucumeris), Fusarium oxysporum (Farsarium oxysporum), Alternaria brassisicola; Rhizoctonia solani, Verticillium dahliae; Puccinia allii, Alternaria porri, Sclerotium rolfsii, Phytophthora porri, Black rot Sclerotium cepivorum; onion ulcer (C urtobacterium flaccumfaciens), Erwinia carotovora subsp. carotovora, Pseudomonas syringae pv. syringae, Erwinia rhapontici, Burkholderia gladioli, Phytoplasma Erwinia carotovora subsp. Carotovora, Pseudomonas marginalis pv.marginalis; Cercospora kikuchii, Elsinoe glycines, Diaporthe phaseolorum, and Rhizoctonia solani Rhizoctonia solani, Phytophthora sojae, Peronospora manshurica, Phakopsora pachyrhizi, Colletotrichum truncatum, etc., Xhanthomonas campestris pv. ), Pseudomonas syringae pv. Glycinea; Colletotrichum lindemuthianum, Ralstonia solanacearum, Pseudomonas syringae pv. Phaseolicola, Pseifimonmonas viridis ,leaf Xhanthomonas campestris pv. Phaseoli; Mycosphaerella berkeleyi, Mycosphaerella arachidis, Ralstonia solanacearum; Erysiphe pisi, Peronospora ), Pseudomonas syringae pv.pisi, Xhanthomonas campestris pv. Pisi; Peronospora viciae, Phytophthora nicotianae; Phytophthora nicotianae; Alternaria solani ), Thanatephorus cucumeris, Phytophthora infestans, Helminthosporium solani, Fusarium oxysporum, Fusarium solani, Spongospora subterranea Ralstonia solanacearum), Erwinia carotovora subsp. atroseptica, Streptomyces scabies, Streptomyces acidiscabies, Erwinia carotovora subsp. carotovora, Crostridium spp. subsp .sepedonicus); Streptomyces ipomoeae; Cercospora beticola, Peronospora schachtii, Aphanomyces cochioides, Phoma betae, roots Agrobacterium tumefaciens, Streptomyces scabies, Pseudomonas syringae pv. Aptata; Alternaria dauci, Rhizobacter dauci, Agrobacterium tumefaciens), Streptomyces spp., Erwinia carotovora subsp. carotovora; Sphaerotheca aphanis var. aphanis, Phytophthora nicotianae, etc. ), Pythium ultimum, Ralstonia solanacearum, Xhanthomonas campestris, Pseudomonas marginalis pv. Marginalis; Exobasidium reticulatum, White Star Germs (Elsinoe leucospila), Anthrax (Colletotrichum theae-sinensis), Pestalotiopsis longiseta, Pseudomonas syringae pv. Theae, Xhanthomonas campestris pv. Theicola, Pseudomonas sp .; Alternaria nicotianae alternata), Erysiphe cichoracearum, Colletotrichum gloeosporioides, Phytophthora nicotianae, Pseudomonas syringae pv. tabaci, Pseudomonas syringae pv. Erwinia carotovora subsp. Carotovora), Ralstonia solanacearum, Tobacco mosaic virus, Hemileia vastatrix, Mycosphaerella fijiensis, Fusarium oxysporum f. sp cubense); Fusarium oxysporum, Ramularia areola; Sclerotinia sclerotiorum, Xhanthomonas campestris pv.malvacearum, Erwinia carotovora subsp. carotovora subsp. carotovora subsp. ),spot Bacterial bacteria (Pseudomonas syringae pv.helianthi); Diplocarpon rosae, Sphaerotheca pannosa, etc., Phytophthora megasperma, Peronospora sparsa, Agrobacterium tumefaciens ); Septoria obesa, Puccinia horiana, Phytophthora cactorum, Pseudomonas cichorii, Erwinia carotovora subsp. Carotovora, root cancer Agrobacterium tumefaciens), Agrobacterium rhizogenes, Phytoplasma aurantifolia; Rhizoctonia solani, Sclerotinia homoeocarpa, Curvularia sp., Puccinia spp. zoysiae), Helminthosporium, Cochliobolus sp., Rhynchosporium secalis, Gaeumannomyces graminis, Colletotrichum sp. (Typhula incarnata), snow rot black small sclerotia Bacteria (Typhula ishikariensis), Snow rot Sclerotinia sclerotinia (Myriosclerotinia borealis), Fairy ring (Marasmius oreades, etc.), Pythium aphanidermatum (Pythium aphanidermatum, etc.), Pyricularia grisea, etc.

In addition, pests such as: Adoxophyes honmai, Adoxophyes orana faciata, Apple chips breviplicanus, Grapholita inopinata, Apple chips fuscocupreanus, Pear small Grapholita molesta, Choristoneura magnanima, Leguminivora glycinivorella, Olethreutes mori, Caloptilia zachrysa, Argyresthia conjugella, Argyresthia conjugella Spulerrina astaurota), Matsumuraeses phaseoli, Pandemis heparana, Bucculatrix pyrivorella (Bucculatrix pyrivorella), Lyoniaia clerkella, Carposina niponensis Leaf Moth (Lyonetia prunifoliella malinella), Caloptilia theivora, Phyllonorycter ringoniella, Phyllocnistis citrella, Acrolepiopsis sapporensis, Acrolepiopsis suzukiella Plutella xylostella ), Stathmopoda masinissa, Helcystogramma triannulella (Helcystogramma triannulella), Pectinophora gossypiella, Carposina sasakii, Chilo suppressalis, Cnaphalocrocis medinalis , Ephestiaelutella, Conogethes punctiferalis, Diaphania indica, Etiella zinckenella, Glyphodes pyloalis Scirpophaga incertulas), Hellula undalis, Asian corn borer (Ostrinia furnacalis), European corn borer (Ostrinia scapulalis), Parapediasia teterrella, Parnara guttata, Great white butterfly Pieris brassicae, Pieris rapae crucivora, Papilio xuthus, Ascotis selenaria, Pseudoplusia includens, Euproctis pseudoconspersa, Lymantria dispar, Orgyia thyellina, Hyphantria cunea, Lemyra imparilis, Leafworm (Adris tyrannus), Aedia leucomelas, Agrotis ipsilon, Agrotis segetum, Cabbage silverworm (Autographa nigrisigna), Silverweed (Ctenoplusia) agnata), Apple moth (Cydla pomonella), Helicoverpa armigera, Helicoverpa assulta, Helicoverpa zea, Heliothis virescens, European corn borer (Heliothis virescens) Ostrinia nubilalis, Mamestra brassicae, Mythimna separata, Sesamia inferens, Naranga aenescens, Spodoptera eridania, Beet Spodoptera exigua, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Spodoptera depravata, Trichoplusia ni , Lepidoptera insects such as Grape fruit tapeworm (Endopiza viteana), Tomato hawk moth (Manduca quinquemaculata), Tobacco hawk moth (Manduca sexta), Arboridia apicalis, yellow-green two-chamber Cicada (Balclutha saltuella), Two-pointed Leaf Clover (Epiacanthus stramineus), Empoasca fabae (Empoasca fabae), Empoasca nipponica, Empoasca onukii, Empoasca macros, sakaii (Macrosteles striifrons), Black-tailed Dust (Nephotettix cinctinceps), Psuedatomoscelis seriatus (Psuedatomoscelis seriatus), Laodelphax striatella, Nilaparvata lugens, Rice white-backed lice (Sogatella citrus) Diaphorina citri), Psylla pyrisuga, Aleurocanthus spiniferus, Bemisia argentifolii, Bemisia tabaci, Dialeurodes citri, Greenhouse whitefly Trialeurodes vaporariorum), Aleurolobus taonabae, Viteus vitifolii, Lipaphis erysimi, Cotton aphid (Aphis gossypii), Aphis spiraecola, Myzus persicae), Toxoptera aurantii, Drosicha corpulenta, Icerya purchasi , Lycoris aureus, Phenacoccus solani, Pulvinaria aurantii, Planococcus citri, Pseudaonidia duplex, Planococcus kuraunhiae, Pseudococcus comstocki, Comstockaspis perniciosa, Ceroplastes ceriferus, Ceroplastes rubens, Aonidiella aurantii, tea Fiorinia theae, Pseudaonidia paeoniae, Pseudaulacaspis pentagona, Pseudaulacaspis prunicola, Unaspis euonymi ), Arrow scale insect (Unaspis yanonensis), temperate bug (Cimex lectularius), Dolycoris baccarum (Dolycoris baccarum), vegetable pile elephant (Eurydema rugosum), Guang Erxing Chun (Eysarcoris aeneus), large spiny white star pile elephant (Eysarcoris lewisi) Eysarcoris ventralis, Glaucias subpunctatus, Halyomorpha halys, Nezara antennata, Southern Green Pole Elephant (Nezara viridula), Pinezodorus hybneri, Platynia crossota, Scotinophora lurida, Cletus punctiger, Chinese spider margin pile Elephant (Leptocorisa chinensis), Riptortus clavatus, Rhopalus msculatus, Cavererius saccharivorus, Togo hemipterus, Dysdercus cingulatus Stephanitis pyrioides, Halticus insularis, Lygus lineolaris, Stenodema sibiricum (Stenodema sibiricum), Stenotus rubrovittatus, Trigonotylus caelestialium (Trigonotyl) ) And other elephant insects, Anomala cuprea, Anomala rufocuprea, Gametis jucunda, Heptophylla picea, Popilia japonica, Lepinotarsa decemlineata), Epilachna varivestis, Melanotus fortnumi, sugarcane beetle (Melanotus tamsuyensis), Tobacco beetle (Lasioderma serricorne), Brown mealworm (Lyctusbrunneus), Pine beetle (Tomicus piniperda), Rhizopertha dominica, Epuraea domina (Epuraea domina), Ladybug (Epilachna varives) Epilachna vigintioctopunctata, Tenebrio molitor, Tribolium castaneum, Anoplophora malasiaca, Monochamus alternatus, Yellow star beetle (Psacothea hilaris), grape tiger spotted beetle (Xylotrechus pyrrhoderus), mung bean elephant (Callosobruchus chinensis), yellow guard melon (Aulacophora femoralis), negative mudworm (Oulema oryzae), beet jumping beetle (Chaetocnema concinna), eleven star melon leaves Diabrotica undecimpunctata, Diabrotica virgifera, Diabrotica barberi, Phyllotreta striolata, Tomato leaf fleas (Psylliodes angusticollis) Rhynchites heros), sweet potato ant elephant (Cylas formicarius), cotton boll weevil (Anthonomus grandis), rice weevil (Echinocnemus sq uameus), sweet potato weevil (Euscepes postfasciatus), alfalfa weevil (Hypera postica), rice water weevil (Lissorhoptrus oryzophilus), Otiorhynchus sulcatu (Otiorhynchus sulcatus), corn elephant (Sitophilus granarius), corn elephant (Sitophilus granarius) ), Sphenophorus venatus vestitus (Sphenophorus venatus vestitus), Coleoptera, such as Paederus fuscipes, Taiwan flower thrips (Frankliniella intonsa), light-color thrips (Thrips flavus), western flower thrips (Frankliniella) occidentalis, Heliothrips haemorrhoidalis, Scirtothrips dorsalis, Thrips palmi, Thrips tabaci, Ponticulothrips diospyrosi and other thrips Insects, Asphondylia yushimai, Sitodiplosis mosellana (Sitodiplosis mosellana), Bactrocera cucurbitae, Bactrocera dorsalis, Ceratitis capitata, Hydrellia griseola), Drosophila suzukii, Agromyza oryzae Chromatomyia horticola, Liriomyza bryoniae, Liriomyza chinensis, Liriomyza sativae, Liriomyza trifolii, Delia platura , Onion fly (Delia antique), Beet leaf fly (Pegomya cunicularia), Apple fruit fly (Rhagoletis pomonella), Mayetiola destructor, Musca domestica, Musca domestica, Musca hervei, Northern Musca bezzii, Stomoxys calcitrans, Haematobia irritans, wool lice fly (Melophagus ovinus), cattle fly (Hypoderma bovis), American cattle fly (Hypoderma lineatum), sheep fly (Oestrus ovis), Tsetse flies (Glossina palpalis, Glossina morsitans), Prosimulium yezoensis (Prosimulium yezoensis), Simulium iwatens (Simulium iwatens), Tabanus trigonus (Tabanus trigonus), White-spotted butterfly fly (Telmatoscopus albopopopuncopusopipopuncopus) nipponensis), Culicoides oxystoma, Anopheles hyracanus sinesis (Anopheles hyracanus sinesis), Gambi Anopheles gambiae, Anopheles arabiensis, Anopheles funestus, Anopheles melas, Anopheles minimus, Anopheles dirus, Anopheles dirus, Anopheles stephensi, Anopheles albimanus, Culex pipiens pallens, Culex pipiens molestus, Culex quinquefasciatus, Culex restuans , Culex tarsalis, Culex modestus, Culex tritaeniorhynchus, Aedes aegypti, Aedes albopicutus, Aedes japonica japonicus), Aedes vexans and other diptera insects, Apethymus kuri (Apethymus kuri), Athalia rosae (Athalia rosae), Rose trilobite (Arge pagana), European new pine bee (Neodiprion sertifer), chestnut Stingray bee (Dryocosmus kuriphilus), Eciton burchelli (Eciton schmitti), Japanese bowback ant (Camponotus japonicus), Vespa mandarina, Australian ant (Myrmecia spp. ), Solenopsis spp., Monomorium pharaonis and other Hymenoptera insects, Teleogryllus emma, Gryllotalpa orientalis, Locusta migratoria, Little wings Orthoptera insects such as rice locust (Oxya yezoensis), desert locust (Schistocerca gregaria), Onychiurus folsomi, Onychiurus sibiricus, Bouletiella hortensis, etc. Insects, Periplaneta fuliginosa, Periplaneta japonica, Blattella germanica, Periplaneta Americana, etc., Coptotermes formosanus, Reticulitermes speratus), Taiwan termites (Odontotermes formosanus), termites, cat flea (Ctenocephalidae felis), dog flea (Ctenocephalides canis), chicken flea (Echidnophaga gallinacea), human flea (Pulex irritans), rat flea (Xenopsylla cheopis) and other fleas Order insects, large chicken lice (Menacanthus stramineus), cattle hair lice (Bovicola bovis) and other feather insects, cattle blood (Haematopinus eurysternus), Haematopinus suis, Linognathus vituli, Solenopotes capillatus, Damiania ovis, Phytonemus dust mites, such as pallidus, Polyphagotarsonemus latus, Tarsonemus bilobatus, true foot mites, such as Chinese cabbage mite (Penthaleus erythrocephalus), wheat mite (Penthaleus major), Oligonychus shinkajii), citrus spider mite (Panonychus citri), Panonychus mori (Panonychus mori), apple spider mite (Panonychus ulmi), Tetranychus kanzawai, Tetranychus urticae, etc. Acaphylla theavagrans, Aceria tulipae, Aculops lycopersici, Aculops pelekassi, Aculus schlechtendali, Eriophyes chibaensis ), Arthropod ticks such as Phyllocoptruta oleivora, Rhizoglyphus robini, Tyrophagus putrescentiae, Tyropha Acaroid mites such as gus similis (Tyrophagus similis), dust mites (Dermatophagoides pteronyssinus), chigger mites such as Dermatophagoides farinae, bee mites such as Varroa jacobsoni (Varroa jacobsoni), Australian cattle tick (Boophilus microplus), Rhipicephalus sanguineus, Haemaphysalis longicornis, Haemaphysalis flava, Haemaphysalis campanulata, Haemaphysalis japonica, Haemaphysalis megaspinosa (Haemaphysalis megaspinosa) Ixodes ovatus, Ixodes persulcatus, Ixodes nipponensis, Ixodes pacifcus (Ixodes pacifcus), Ixodes ricinus, Ixodes scapularis , Amblyomma americanum, Amblyomma maculatum, Amblyomma spp., Dermacentor recticulatus, Dermacentor taiwanesis, Dermacentor andersoni ), West Coast Dermacentor occidentalis, Dermacentor variabilis, Leather True ticks such as Dermacentor spp., Claw mites such as Cheyletiella yasguri, cheyletiella blakei, Demodex canis, and Demodex cati), such as Demodex follicles, itch mites, such as sheep mites (Psoroptes ovis), chigger mites (Sarcoptes scabiei), notoedres cati, knemidocoptes spp., etc. Crustaceans such as Armadillidium vulgare, Pomacea canaliculata, Achatina fulica, Meghimatium bilineatum, Limax Valentiana, Acusta despecta sieboldiana, Japan Land snails (Euhadra peliomphala) and other gastropods, Prathylenchus coffeae, Prathylenchus penetrans, Prathylenchus vulnus, Globodera rostochiensis, Heterodeides glycerides ), Meloidogyne hapla, Meloidogyne incognita, Aphelenchoides besseyi, Pine Nematodes such as Bursaphelenchus xylophilus, Rhizopoda, such as Amoeba, Mishigo, Leishmania, Trichomonas, Malaria, Toxoplasma Sporozoea and other protozoa such as Ciliophora, Nematoda such as Ascaris and hookworm, Acannthocephala and other needleworms Linear animals (Nematomorpha), trematodes such as liver flukes (Trematoda), maggots such as hookworms (Cestoda), worms, Ascaris, Toxocara, Toxascaris, Parascaris, Ascaridia, Heterakis, Oxyuris, Capillaria, Trichinella, Strongylus, Triodontophorus, Trichodonma , Stephanurus, Desophagostomum, Chabertia, Syngamus, Ancylostoma, Uncinaria, Necator, Bunostomum, Trichostrongylus, Cooper hair Coeperia, fine Nematodirus, Haemonchus, Ostertagia, Dictyocaulus, Metastrongylus, Dirofilaria, Parafilaria, and Silkworm Setaria), Onchocerca, Habronema, Arduenna, Acuaria, and other nematodes, Diphyllobothrium, Anoplocephara, Moniezia, and Dogworm Ascaris such as Dipylidium, Taenia, Taenia, Dithyridium, Raillietina, Echinococcus, Schistosoma, Paramphistomum ), Liver fluke (Fasciola) and other flukes.

Specific formulation examples are disclosed below, but are not limited thereto.

[Preparation Example 1 Water Suspension] The compound of the present invention (10 parts by mass), a quinoline compound (10 parts by mass), a sodium salt (5 parts by mass) of a formaldehyde condensate of naphthalenesulfonic acid, and polyoxyethylene arylphenyl ether (1 part by mass), propylene glycol (5 parts by mass), silicon-based defoamer (0.1 part by mass), Sanxian gum (0.2 part by mass), and ion-exchanged water (68.7 parts by mass) are mixed into a slurry. KDL, wet crushing with glass beads having a diameter of 1.0 mm to obtain an aqueous suspension.

[Preparation Example 2 Emulsion] The compound (5 parts by mass) of the present invention and a quinoline compound (5 parts by mass) were dissolved in a mixed solution of xylene (35 parts by mass) and cyclohexane (35 parts by mass). Tween 20 (20 parts by mass) was added and mixed to obtain an emulsion.

[Hydrant of Formulation Example 3] A compound of the present invention (10 parts by mass), a quinoline compound (10 parts by mass), white carbon (10 parts by mass), polyvinyl alcohol (2 parts by mass), and dioctylsulfoamber The sodium salt (0.5 parts by mass), the sodium salt of alkylbenzenesulfonic acid (5 parts by mass), the calcined diatomaceous earth (10 parts by mass), and the kaolin clay (52.5 parts by mass) were thoroughly mixed, and pulverized with a jet mill. Obtain a hydrating agent. [Example]

Hereinafter, the pyridone compound and the quinoline-based compound used in the present invention will be further specifically described with reference to synthesis examples and test examples. However, the content of the present invention is not limited to these synthesis examples and test examples.

[Synthesis Example 1] Step 1: 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -3,4-dihydropyridine-2 (1H)- Ketone Synthesis

[Chemical 42]

10 ml of an acetic acid solution containing 1.47 g of 4- (2-chloro-5-methoxyphenyl) -5- (2,6-difluorophenyl) -5-pentoxypentanoic acid and 6.75 g of ammonium acetate was added to The reaction was carried out at 130 ° C for 14 hours. After cooling to room temperature, ethyl acetate and water were added to the reaction mixture and the layers were separated. Water was added to the obtained organic layer, and potassium carbonate was added until bubbling ceased, followed by liquid separation. Next, the organic layer was washed with saturated brine and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the precipitate was washed with diisopropyl ether. The obtained purple solid was the title compound, 0.98 g. ¹ H-NMR (CDCl ₃ ) δ: 7.25-7.21 (1H, m), 7.19 (1H, d, J = 8.8Hz), 6.83-6.76 (3H, m), 6.65 (1H, dd, J = 8.8, 3.4Hz), 6.53 (1H, d, J = 3.4Hz), 3.61 (3H, s), 2.91-2.76 (4H, m).

Step 2: 5- (2-Chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethyl-3,4-dihydropyridine-2 (1H)- Ketone Synthesis (Compound No. 52)

[Chemical 43]

DMF solution containing 0.50 g of 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -3,4-dihydropyridine-2 (1H) -one In 5 ml, 346 μl of iodoethane and 1.41 g of cesium carbonate were added, and the mixture was stirred at 60 ° C. for 2 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with an aqueous sodium thiosulfate solution and saturated brine in this order, and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 0.54 g of a white solid.

[Synthesis Example 2] Synthesis of 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethylpyridine-2 (1H) -one (compound (No. 53)

[Chemical 44]

Contains 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethyl-3,4-dihydropyridine-2 (1H) -one To 20 ml of 520 mg of a carbon tetrachloride solution, 258 mg of N-bromosuccinimide and 23 mg of azobisisobutyronitrile were added, and stirred at 80 ° C for 90 minutes. After cooling to room temperature, water was added to the reaction mixture, and carbon tetrachloride was distilled off under reduced pressure. After ethyl acetate was added thereto and the mixture was separated, the obtained organic layer was sequentially washed with an aqueous sodium thiosulfate solution and saturated brine, and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 467 mg of a white solid.

[Synthesis Example 3] 3-chloro-5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethylpyridine-2 (1H) -one Synthesis (Compound No. 54)

[Chemical 45]

To 2 ml of a DMF solution containing 110 mg of 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one 43 mg of N-chlorosuccinimide was stirred at 70 ° C for 1 hour. After cooling to room temperature, ethyl acetate and water were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with saturated brine, and then dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound obtained was 114 mg of a white solid.

[Synthesis Example 4] Synthesis of 5- (2-chloro-5-hydroxyphenyl) -6- (2,6-difluorophenyl) -1-ethylpyridine-2 (1H) -one (Compound No. 234 )

[Chemical 46]

Dichloromethane solution containing 4.0 g of 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethylpyridine-2 (1H) -one 40ml was ice-cold, and 23.4ml of a 1.0 mol / l boron tribromide dichloromethane solution was added dropwise. After stirring for 30 minutes under ice-cooling, a water solution was added to the reaction mixture. The obtained organic layer was washed with a sodium thiosulfate aqueous solution and a saturated sodium bicarbonate aqueous solution in this order and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was washed with hexane. The title compound obtained was 3.9 g of a white solid.

[Synthesis Example 5] 5- (2-chloro-5- (methoxymethoxy) phenyl) -6- (2,6-difluorophenyl) -1-ethylpyridine-2 (1H)- Ketone Synthesis (Compound No. 97)

[Chemical 47]

Contains 0.08 g of sodium hydride (approximately 60% by weight, dispersed in a flowing paraffin) and 5- (2-chloro-5-hydroxyphenyl) -6- (2,6-difluorophenyl) -1-ethyl A solution of 0.62 g of pyridin-2 (1H) -one in THF was added with 0.08 g of chloromethyl methyl ether, and the mixture was stirred at room temperature for 3 hours. After adding water and ethyl acetate to the reaction mixture and separating the liquids, the obtained organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 0.46 g of a white solid.

[Synthesis Example 6] 3-chloro-5- (2-chloro-5- (methoxymethoxy) phenyl) -6- (2,6-difluorophenyl) -1-ethylpyridine-2 Synthesis of (1H) -one (Compound No. 127)

[Chemical 48]

219 mg of 5- (2-chloro-5- (methoxymethoxy) phenyl) -6- (2,6-difluorophenyl) -1-ethylpyridine-2 (1H) -one was mixed with 3 ml of a DMF solution of 79 mg of N-chlorosuccinimide was stirred at 70 ° C for 1 hour. After cooling to room temperature, a saturated sodium bicarbonate aqueous solution and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with an aqueous sodium thiosulfate solution and saturated brine in this order, and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 203 mg of a yellow chewing gum.

[Synthesis Example 7] 5- (2-chloro-5-methoxyphenyl) -1- (2,2-difluoroethyl) -6- (2,6-difluorophenyl) -3,4 -Dihydropyridine-2 (1H) -one (Compound No. 192)

[Chemical 49]

0.50 g containing 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -3,4-dihydropyridine-2 (1H) -one, p-toluene 0.68 g of 2,2-difluoroethyl sulfonate and 10 ml of a DMF solution of 1.40 g of cesium carbonate were stirred at 80 ° C for 4 hours. Water and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with 1N hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution and a saturated saline solution in this order, and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 0.48 g of a white solid.

[Synthesis Example 8] 5- (2-chloro-5-methoxyphenyl) -1- (2,2-difluoroethyl) -6- (2,6-difluorophenyl) pyridine-2 ( Synthesis of 1H) -one (Compound No. 194)

[Chemical 50]

Contains 5- (2-chloro-5-methoxyphenyl) -1- (2,2-difluoroethyl) -6- (2,6-difluorophenyl) -3,4-dihydro To 15 ml of a carbon tetrachloride solution of 0.42 g of pyridine-2 (1H) -one were added 190 mg of N-bromosuccinimide and 16 mg of azobisisobutyronitrile, and the mixture was stirred at 80 ° C for 15 minutes. After cooling to room temperature, water was added to the reaction mixture, and carbon tetrachloride was distilled off under reduced pressure. After ethyl acetate was added thereto and the mixture was separated, the obtained organic layer was sequentially washed with an aqueous sodium thiosulfate solution and saturated brine, and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 0.38 g of a white solid.

[Synthesis Example 9] 3-bromo-5- (2-chloro-5-methoxyphenyl) -1- (2,2-difluoroethyl) -6- (2,6-difluorophenyl) Synthesis of pyridine-2 (1H) -one (Compound No. 198)

[Chemical 51]

Will contain 5- (2-chloro-5-methoxyphenyl) -1- (2,2-difluoroethyl) -6- (2,6-difluorophenyl) pyridine-2 (1H)- 5 ml of a DMF solution of 125 mg of ketone and 65 mg of N-bromosuccinimide was stirred at 70 ° C for 2 hours. 27 mg of N-bromosuccinimide was added thereto, and the mixture was stirred at 70 ° C for 2 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was sequentially washed with an aqueous sodium thiosulfate solution and a saturated saline solution, and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 109 mg of an off-white solid.

[Synthesis Example 10] 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethyl-3-methyl-3,4-dihydro Synthesis of pyridine-2 (1H) -one

[Chemical 52]

Will contain 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethyl-3,4-dihydropyridine-2 (1H) -one 10 ml of a 500 mg THF solution was cooled to -78 ° C, and 1.33 mol / l of a solution of lithium diisopropylamino lithium in THF was added dropwise, and stirred at the same temperature for 30 minutes. Next, 2 ml of a THF solution containing 82 µl of methyl iodide was added dropwise thereto, and the mixture was stirred at -78 ° C for 2 hours, and then the temperature was raised to room temperature. After stirring at room temperature for 2 hours, a saturated ammonium chloride aqueous solution and ethyl acetate were added to the reaction mixture, and the mixture was separated. The obtained organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 101 mg of a white solid. The title compound obtained was a stereoisomeric mixture. ¹ H-NMR (CDCl ₃ ) δ: 7.24-7.17 (1H, m: mixture), 7.15-7.13 (1H, m: mixture), 6.87-6.71 (2H, m: mixture), 6.57-6.49 (2H, m : Mixture), 3.70-3.14 (2H, m: mixture), 3.65 (3H, s: major), 3.58 (3H, s: minor), 2.98-2.70 (2H, m: mixture), 2.46-2.37 (1H, m: mixture), 1.35 (3H, d, J = 6.7Hz: minor), 1.33 (3H, d, J = 7.0Hz: major), 1.00-0.96 (3H, m). Stereoisomer mixture ratio: about 57 : 43

[Synthesis Example 11] 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethyl-3-methylpyridine-2 (1H)- Ketone Synthesis (Compound No. 329)

[Chem 53]

Will contain 5- (2-chloro-5-methoxyphenyl) -6- (2,6-difluorophenyl) -1-ethyl-3-methyl-3,4-dihydropyridine-2 10 ml of a methylene chloride solution of 413 mg of (1H) -one and 5.48 g of manganese dioxide was stirred under reflux for 11 hours. Furthermore, 1.83 g of manganese dioxide was added, and it stirred under heating and refluxing for 3 hours. After cooling to room temperature, the reaction mixture was filtered through celite. The solvent was distilled off under reduced pressure from the filtrate, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 291 mg of a white solid.

[Synthesis Example 12] Step 1: 5- (2-chloro-5-fluorophenyl) -6- (2,4,6-trifluorophenyl) -3,4-dihydropyridine-2 (1H)- Ketone Synthesis

[Chem. 54]

25 ml of an acetic acid solution containing 4.46 g of 4- (2-chloro-5-fluorophenyl) -5- pendantoxy-5- (2,4,6-trifluorophenyl) valeric acid and 45.9 g of ammonium acetate was added to Stir at 130 ° C for 2 hours. After cooling to room temperature, ethyl acetate and water were added to the reaction mixture and the layers were separated. Water was added to the obtained organic layer, and potassium carbonate was added until foaming ceased, followed by liquid separation. The organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the precipitate was washed with diisopropyl ether. The title compound was obtained as a white solid, 2.24 g. Further, the filtrate generated when the precipitate was washed was distilled off the solvent under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The white solid obtained from the filtrate was also the title compound, 0.46 g. ¹ H-NMR (CDCl ₃ ) δ: 7.28-7.26 (1H, m), 7.18 (1H, brs), 6.86-6.83 (1H, m), 6.74-6.72 (1H, m), 6.61-6.59 (2H, br m), 2.85-2.74 (4H, br m).

Step 2: 5- (2-Chloro-5-fluorophenyl) -1-ethyl-6- (2,4,6-trifluorophenyl) -3,4-dihydropyridine-2 (1H)- Ketone Synthesis (Compound No. 320)

[Chem 55]

Will contain 5- (2-chloro-5-fluorophenyl) -6- (2,4,6-trifluorophenyl) -3,4-dihydropyridine-2 (1H) -one 2.70 g, cesium carbonate 32ml of 7.42g and 3.55g of iodoethane in DMF was stirred at 55 ° C for 2 hours. After cooling to room temperature, ethyl acetate and water were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 2.47 g of a red-purple chewing gum-like substance.

[Synthesis Example 13] Synthesis of 5- (2-chloro-5-fluorophenyl) -1-ethyl-6- (2,4,6-trifluorophenyl) pyridine-2 (1H) -one (compound (No. 321)

[Chemical] 56

Will contain 5- (2-chloro-5-fluorophenyl) -1-ethyl-6- (2,4,6-trifluorophenyl) -3,4-dihydropyridine-2 (1H) -one 5 ml of a toluene solution of 0.21 g and 1.42 g of manganese dioxide was stirred at 90 ° C for 5 hours. After cooling to room temperature, the reaction mixture was filtered through celite. The filtrate was subjected to solvent distillation under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 0.14 g of a white solid.

[Synthesis Example 14] 3-bromo-5- (2-chloro-5-fluorophenyl) -1-ethyl-6- (2,4,6-trifluorophenyl) pyridine-2 (1H) -one Synthesis (Compound No. 381)

[Chemical] 57

0.60 g containing 5- (2-chloro-5-fluorophenyl) -1-ethyl-6- (2,4,6-trifluorophenyl) pyridine-2 (1H) -one and N-bromoamber 30 ml of a solution of rhenium imine 0.33 g in DMF was stirred at 75 ° C for 2.5 hours. Furthermore, 0.10 g of N-bromosuccinimide was added, and it stirred at 75 degreeC for 1.5 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with saturated brine, and then dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 0.64 g of a white solid.

[Synthesis Example 15] 5- (2-chloro-5-fluorophenyl) -1-ethyl-3-methyl-6- (2,4,6-trifluorophenyl) pyridine-2 (1H)- Ketone Synthesis (Compound No. 461)

[Chemical] 58

250 mg of 3-bromo-5- (2-chloro-5-fluorophenyl) -1-ethyl-6- (2,4,6-trifluorophenyl) pyridine-2 (1H) -one, A mixed solution of 49 mg of methylboronic acid, 6 mg of palladium (II) acetate, 403 mg of tripotassium phosphate, and 15 mg of tricyclohexylphosphine in 8 ml of toluene and 0.8 ml of water was stirred at 100 ° C for 7 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with saturated brine, and then dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 116 mg of a white solid.

[Synthesis Example 16] 3-bromo-5- (2-chloro-5-fluorophenyl) -6- (2,6-difluoro-4-methoxyphenyl) -1-ethylpyridine-2 ( Synthesis of 1H) -one (Compound No. 476)

[Chemical 59]

300 mg of 3-bromo-5- (2-chloro-5-fluorophenyl) -1-ethyl-6- (2,4,6-trifluorophenyl) pyridine-2 (1H) -one in methanol To 8 ml was added 0.63 ml of a 28% by weight sodium methoxide in methanol solution, and the mixture was stirred under reflux for 13 hours. After cooling to room temperature, a saturated ammonium chloride aqueous solution and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 271 mg of a white solid.

[Synthesis Example 17] Step 1: 5- (3,5-dimethoxyphenyl) -6- (2,4,6-trifluorophenyl) -3,4-dihydropyridine-2 (1H) -Ketone Synthesis

[Chemical 60]

Unrefined 4- (3,5-dimethoxyphenyl) -5- pendantoxy-5- (2,4,6-trifluorophenyl) pentanoic acid obtained in Reference Example 3, and ammonium acetate was added 14.18 g and 15 ml of acetic acid were stirred at 120 ° C for 10 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and a saturated saline solution in this order, and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, isopropyl ether was added to the obtained solid and washed. The title compound obtained was 0.99 g of a brown solid. ¹ H-NMR (CDCl ₃ ) δ: 6.68 (1H, s), 6.62 (2H, td, J = 8.7, 1.4Hz), 6.26 (1H, t, J = 2.1Hz), 6.16 (2H, d, J = 2.1Hz), 3.65 (6H, s), 2.87-2.86 (2H, m), 2.73-2.71 (2H, m).

Step 2: 5- (3,5-Dimethoxyphenyl) -1-methyl-6- (2,4,6-trifluorophenyl) -3,4-dihydropyridine-2 (1H) -Ketone Synthesis

[Chem. 61]

Contains 343 mg of 5- (3,5-dimethoxyphenyl) -6- (2,4,6-trifluorophenyl) -3,4-dihydropyridine-2 (1H) -one, methyl iodide 176 μl of 6 ml of a DMF solution with 1.85 g of cesium carbonate was stirred at room temperature for 3 hours. Water and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with water, an aqueous sodium thiosulfate solution and a saturated saline solution in this order, and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 346 mg of a white solid. ¹ H-NMR (CDCl ₃ ) δ: 6.62-6.60 (2H, m), 6.23 (1H, t, J = 2.1Hz), 6.13 (2H, d, J = 2.1Hz), 3.65 (6H, s), 2.87 (3H, s), 2.76-2.74 (4H, m).

[Synthesis Example 18] Synthesis of 5- (3,5-dimethoxyphenyl) -1-methyl-6- (2,4,6-trifluorophenyl) pyridine-2 (1H) -one ( (Compound No. 134)

[Chem 62]

Will contain 5- (3,5-dimethoxyphenyl) -1-methyl-6- (2,4,6-trifluorophenyl) -3,4-dihydropyridine-2 (1H)- 320 ml of ketone and 12 ml of dichloromethane solution of 4.42 g of manganese dioxide were stirred under reflux for 5 hours. After cooling to room temperature, the reaction mixture was filtered through celite. The solvent was distilled off under reduced pressure from the filtrate, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 263 mg of a white solid.

[Synthesis Example 19] 5- (2-chloro-3,5-dimethoxyphenyl) -1-methyl-6- (2,4,6-trifluorophenyl) pyridine-2 (1H)- Ketone Synthesis (Compound No. 136)

[Chem 63]

Contains 163 mg of 5- (3,5-dimethoxyphenyl) -1-methyl-6- (2,4,6-trifluorophenyl) pyridine-2 (1H) -one and N-chloroamber 6 ml of a solution of arsenimide in 64 mg of DMF was stirred at 80 ° C for 5 hours. An additional 45 mg of N-chlorosuccinimide was added, and the mixture was stirred at 100 ° C for 4 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with an aqueous sodium thiosulfate solution and saturated brine in this order, and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound obtained was 150 mg of a white solid.

<Reference Example 1> Step 1: Synthesis of 2- (2-chloro-5-methoxyphenyl) -1- (2,6-difluorophenyl) ethanone

[Chemical 64]

After cooling 30 ml of a THF solution containing 2.05 g of 2- (2-chloro-5-methoxyphenyl) acetic acid to -78 ° C, 1.9 mol / L of hexamethyldisilazane was added dropwise below -50 ° C. 17.21 ml of a sodium THF solution was stirred at -78 ° C for 40 minutes. Then, 10 ml of a THF solution containing 1.76 g of methyl 2,6-difluorobenzoate was added dropwise at -78 ° C, and the temperature was raised to room temperature, followed by stirring for 1.5 hours. A saturated ammonium chloride aqueous solution was added to the reaction mixture, and after stirring, ethyl acetate was added and the mixture was separated. The obtained organic layer was washed with saturated brine and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography to obtain the title compound (2.58 g) as a yellow oily substance. ¹ H-NMR (CDCl ₃ ) δ: 7.40-7.38 (1H, m), 7.28-7.27 (1H, m), 6.96-6.94 (2H, m), 6.83 (1H, d, J = 3.1Hz), 6.78 (1H, dd, J = 8.9, 3.1Hz), 4.27 (2H, s), 3.79 (3H, s).

Step 2: Synthesis of 4- (2-chloro-5-methoxyphenyl) -5- (2,6-difluorophenyl) -5-pentoxypentanoate

[Chem. 65]

To 15 ml of a THF solution containing 1.30 g of 2- (2-chloro-5-methoxyphenyl) -1- (2,6-difluorophenyl) ethanone, 98 mg of potassium tert-butoxide and ethyl acrylate were added. The ester was 525 μl and stirred overnight under ice-cooling. 1N hydrochloric acid and ethyl acetate were added to the reaction mixture, and the resulting organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.69 g of the title compound as a yellow oily substance. It was used in the next reaction without further purification. ¹ H-NMR (CDCl ₃ ) δ: 7.36-7.25 (1H, m), 7.19 (1H, d, J = 8.9Hz), 6.83 (2H, t, J = 8.1Hz), 6.74-6.71 (2H, m ), 4.91 (1H, t, J = 7.2Hz), 4.13 (2H, q, J = 7.1Hz), 3.76 (3H, s), 2.57-2.53 (1H, m), 2.42-2.29 (2H, m) , 2.16-2.07 (1H, m), 1.25 (3H, t, J = 7.1Hz).

Step 3: Synthesis of 4- (2-chloro-5-methoxyphenyl) -5- (2,6-difluorophenyl) -5- pendant valeric acid

[Chemical 66]

In a mixed solution of 40 ml of THF and 10 ml of water containing 1.69 g of 4- (2-chloro-5-methoxyphenyl) -5- (2,6-difluorophenyl) -5-pentoxyvalerate To the solution, 0.74 g of lithium hydroxide monohydrate was added, and the mixture was stirred at 60 ° C for 3 hours. After cooling to room temperature, the solvent of the reaction mixture was distilled off until the liquid volume became about half. Water and diethyl ether were added thereto, and the layers were separated. Concentrated hydrochloric acid and ethyl acetate were added to the obtained aqueous layer, and the layers were separated. The obtained organic layer was washed with saturated brine and dried over sodium sulfate. Then, the solvent was distilled off under reduced pressure to obtain 1.47 g of a yellow chewing gum-like substance of the title compound. It was used in the next reaction without further purification. ¹ H-NMR (CDCl ₃ ) δ: 7.28-7.27 (1H, m), 7.19 (1H, d, J = 8.6Hz), 6.83 (2H, t, J = 8.3Hz), 6.75-6.74 (1H, m ), 6.71 (1H, dd, J = 8.6, 3.1Hz), 4.92 (1H, t, J = 7.3Hz), 3.75 (3H, s), 2.60-2.34 (3H, m), 2.15-2.12 (1H, m).

<Reference Example 2> Step 1: Synthesis of N '-(2-chloro-5-fluorobenzylidene) -4-methylbenzenesulfonylhydrazine

[Chemical 67]

250 ml of an ethanol solution containing 25.43 g of 2-chloro-5-fluorobenzaldehyde and 29.87 g of 4-methylbenzenesulfonylhydrazine was stirred at room temperature for 4 hours. The reaction mixture was then stirred under ice-cooling for 1 hour, and the precipitate was filtered to obtain 40.74 g of the title compound as a white solid. ¹ H-NMR (CDCl ₃ ) δ: 8.27 (1H, s), 8.10 (1H, d, J = 1.8Hz), 7.88 (2H, d, J = 8.2Hz), 7.58 (1H, dd, J = 9.2 , 3.1Hz), 7.34 (2H, d, J = 8.2Hz), 7.30-7.28 (1H, m), 7.02-6.99 (1H, m), 2.43 (3H, s).

Step 2: Synthesis of 2- (2-chloro-5-fluorophenyl) -1- (2,4,6-trifluorophenyl) ethanone

[Chemical 68]

To 600 ml of an aqueous solution containing 4.0 g of sodium hydroxide was added 32.7 g of N '-(2-chloro-5-fluorobenzylidene) -4-methylbenzenesulfonylhydrazine and 2,4,6-trifluorobenzene. 8.0 g of formaldehyde was stirred at 80 ° C. for 1 hour. After cooling to room temperature, 15.0 g of ethyl acetate and ammonium chloride were added to the reaction mixture, and the mixture was stirred for liquid separation. The obtained organic layer was washed with saturated brine, and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. This gave 6.13 g of the title compound as a pale yellow solid. ¹ H-NMR (CDCl ₃ ) δ: 7.36-7.34 (1H, m), 7.04-7.02 (1H, m), 6.98-6.96 (1H, m), 6.76-6.72 (2H, m) 4.26 (2H, s ).

Step 3: Synthesis of 4- (2-chloro-5-fluorophenyl) -5-lanthoxy-5- (2,4,6-trifluorophenyl) valerate

[Chemical 69]

75 ml of a THF solution containing 6.13 g of 2- (2-chloro-5-fluorophenyl) -1- (2,4,6-trifluorophenyl) ethanone was ice-cooled, 0.45 g of potassium tert-butoxide and acrylic acid were added 2.23 g of ethyl ester was stirred at room temperature for 8 hours. After adding 10% hydrochloric acid to the reaction mixture, water and ethyl acetate were added and the layers were separated. The obtained organic layer was washed with saturated brine, and then dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. This gave 4.97 g of the title compound as a pale yellow oily substance. ¹ H-NMR (CDCl ₃ ) δ: 7.30 (1H, dd, J = 8.9, 5.2Hz), 7.01-6.98 (1H, m), 6.92-6.90 (1H, m), 6.66-6.60 (2H, m) , 4.89 (1H, t, J = 7.2Hz), 4.13 (2H, q, J = 7.2Hz), 2.54-2.52 (1H, m), 2.35-2.31 (2H, m), 2.12-2.09 (1H, m ), 1.25 (3H, t, J = 7.2Hz).

Step 4: Synthesis of 4- (2-chloro-5-fluorophenyl) -5- pendantoxy-5- (2,4,6-trifluorophenyl) pentanoic acid

[Chemical 70]

To 100 ml of a THF solution containing 4.97 g of ethyl 4- (2-chloro-5-fluorophenyl) -5- pendantoxy-5- (2,4,6-trifluorophenyl) valerate was added water 25ml and 2.59g of lithium hydroxide monohydrate were stirred at 60 ° C for 2 hours. After cooling to room temperature, the reaction mixture was distilled off the solvent under reduced pressure. Water and diethyl ether were added thereto and the layers were separated. Then, concentrated hydrochloric acid was added to the obtained aqueous layer to make it acidic, and then extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain 4.46 g of the title compound as a colorless transparent gel-like substance. It was used in the next reaction without further purification. ¹ H-NMR (CDCl ₃ ) δ: 7.32-7.29 (1H, m), 7.00-6.97 (1H, m), 6.94-6.89 (1H, m), 6.64-6.60 (2H, m), 4.89 (1H, t, J = 7.2Hz), 2.58-2.06 (4H, m).

<Reference Example 3> Step 1: Synthesis of N '-(3,5-dimethoxybenzylidene) -4-methylbenzenesulfonylhydrazine

[Chemical 71]

100 ml of an ethanol solution containing 10.0 g of 3,5-dimethoxybenzaldehyde and 11.2 g of 4-methylbenzenesulfonylhydrazine was stirred at room temperature for 5 hours. The obtained reaction mixture was distilled off the solvent under reduced pressure to obtain 20.0 g of the title compound as a yellow solid. ¹ H-NMR (CDCl ₃ ) δ: 8.13 (1H, s), 7.87 (2H, d, J = 7.8Hz), 7.68 (1H, s), 7.30 (2H, d, J = 7.8Hz), 6.72 ( 2H, d, J = 2.4Hz), 6.46 (1H, t, J = 2.4Hz), 3.79 (6H, s), 2.40 (3H, s).

Step 2: Synthesis of 2- (3,5-dimethoxyphenyl) -1- (2,4,6-trifluorophenyl) ethanone

[Chemical 72]

To 100 ml of an aqueous solution containing 6.68 g of N '-(3,5-dimethoxybenzylidene) -4-methylbenzenesulfonylhydrazine, 20 ml of an aqueous solution of 0.80 g of sodium hydroxide and 2, 1.60 g of 4,6-trifluorobenzaldehyde was stirred at 80 ° C for 90 minutes. After cooling to room temperature, ethyl acetate was added to the reaction mixture and the layers were separated. The obtained organic layer was sequentially washed with a saturated aqueous ammonium chloride solution and a saturated saline solution, and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. This gave 1.85 g of the title compound as a yellow oily substance. ¹ H-NMR (CDCl ₃ ) δ: 6.68-6.66 (2H, m), 6.35 (3H, s), 4.06 (2H, s), 3.75 (6H, s).

Step 3: Synthesis of 4- (3,5-dimethoxyphenyl) -5-sideoxy-5- (2,4,6-trifluorophenyl) valerate

[Chemical 73]

To 18 ml of a THF solution containing 1.85 g of 2- (3,5-dimethoxyphenyl) -1- (2,4,6-trifluorophenyl) ethanone, 67 mg of potassium tert-butoxide and acrylic acid were added. 714 μl of ethyl acetate was stirred overnight under ice-cooling. A saturated aqueous ammonium chloride solution and ethyl acetate were added to the reaction mixture, and the layers were separated. The obtained organic layer was washed with saturated brine, and then dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. Obtained 1.51 g of the title compound as a brown oily substance. ¹ H-NMR (CDCl ₃ ) δ: 6.61-6.57 (2H, m), 6.31-6.29 (3H, m), 4.19 (1H, t, J = 7.3Hz), 4.13 (2H, q, J = 7.1Hz ), 3.73 (6H, s), 2.49-2.47 (1H, m), 2.30 (2H, t, J = 7.5Hz), 2.09-2.07 (1H, m), 1.25 (3H, t, J = 7.1Hz)

Step 4: Synthesis of 4- (3,5-dimethoxyphenyl) -5- pendantoxy-5- (2,4,6-trifluorophenyl) pentanoic acid

[Chemical 74]

An acetic acid solution containing 1.51 g of 4- (3,5-dimethoxyphenyl) -5- pendantoxy-5- (2,4,6-trifluorophenyl) valerate and 3 ml of concentrated hydrochloric acid 15 ml was stirred at 60 ° C for 3 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture and the layers were separated. The obtained organic layer was washed with water and saturated brine in this order, and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain the title compound. The reaction in the next step was used without further purification.

Table 4 shows compounds synthesized according to the foregoing examples, but the compounds of the present invention are not limited thereto. Structure A is shown below.

[Chemical 75]

Structure B is shown below.

[Chemical 76]

Structure C is shown below.

[Chemical 77]

Structure D is shown below.

[Chem. 78]

[Table 56]

[Table 57] Continued with Table 4

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[Table 74] Continued with Table 4

[Table 75] Continued with Table 4

The compounds shown in Table 4 are shown below, and Table 1 shows their ¹ H-NMR data.

[Table 76]

[Table 77] Continued with Table 5

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[Table 132] Continued with Table 5

[Synthesis Example 20] 3- (4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline (Compound No .: (2) -2)

Step 1: Production of 3- (3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline In a 2L three-necked flask, place (Z) -2- (3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) -3-hydroxyacryl (23 g, 0.1 mol) and 2-fluoroaniline (16.7 g, 0.16 mol) in xylene After the solution (300 ml) was heated and refluxed for 3 hours, the EATON reagent (phosphorus pentoxide-methanesulfonic acid solution, weight ratio 1:10) (300 ml) was added dropwise, followed by heating and refluxing for 3 hours. Water (500 ml) was added to the reaction solution under ice-cooling, and the aqueous layer washed with xylene was basified with potassium carbonate, extracted with ethyl acetate, dried over magnesium sulfate, filtered and concentrated. The obtained residue was purified by silica gel column chromatography (hexane / ethyl acetate = 7/3) to obtain 3- (3,3-dimethyl-3,4-dihydroisoquinolin-1-yl). -8-fluoroquinoline (17.7 g) as a white solid, yield 58%. ¹ H-NMR (CDCl ₃ ) δ: 9.14 (1H, d, J = 2.1Hz), 8.42 (1H, t, J = 1.7Hz), 7.68 (1H, d, J = 8.0Hz), 7.53 (1H, td, J = 8.0, 4.9Hz), 7.47-7.41 (2H, m), 7.28 (1H, dd, J = 7.6, 0.6Hz), 7.26-7.23 (1H, m), 7.17 (1H, dd, J = 7.8, 0.8Hz), 2.88 (2H, s), 1.34 (6H, s)

Step 2: Manufacture of 3- (4,4-dibromo-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline in a 1L three-necked flask, To a solution of 3- (3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline (17.7 g, 58 mmol) in chlorobenzene (400 ml) was added 1,3 -Dibromo-5,5-dimethylhydantoin (19.1g, 66.8mmol) and PEROYL TCP (bis (4-third butylcyclohexyl) peroxydicarbonate), at 70 ° C for 3 hours Heat and stir. The reaction solution was filtered, and the filtrate was concentrated to obtain brown 3- (4,4-dibromo-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline. A solid, which was used directly in the next step.

Step 3: Manufacture of 3- (4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline in 500mL of PFA In a trifluoroethylene) flask, 3- (4,4-dibromo-3,3-dimethyl-3,4-dihydroisoquinoline-1- was added to triethylamine hydrogen trifluoride (18.7 g, 116 mmol). A solution of chloro) -8-fluoroquinoline (24.4 g, 58 mmol) in chlorobenzene (45 ml) was heated and stirred at 85 ° C for 5 hours. 20% potassium hydroxide (100 ml) was added to the reaction solution, the layers were separated, and the organic layer was dried over magnesium sulfate, filtered, and concentrated. The obtained residue was purified by silica gel column chromatography (hexane / ethyl acetate = 7/3) to obtain 3- (4,4-difluoro-3,3-dimethyl-3,4-dihydroiso Quinolin-1-yl) -8-fluoroquinoline (18.4 g) as a white solid, yield 93%. ¹ H-NMR (CDCl ₃ ) δ: 9.18 (1H, d, J = 2.1Hz), 8.44 (1H, t, J = 1.7Hz), 7.89 (1H, d, J = 7.6Hz), 7.70-7.66 ( 2H, m), 7.59-7.53 (2H, m), 7.49 (1H, ddd, J = 10.4, 7.8, 1.4Hz), 7.31 (1H, dd, J = 7.6, 0.9Hz), 1.46 (6H, s)

[Synthesis Example 21] 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-1,2,3,4-tetrahydroisoquinolin-1-yl) quinoline (compound No .: (2) -3)

Step 1: Production of 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl) quinoline in a 500 mL three-necked flask In a concentrated sulfuric acid (115 mL), 3-cyano-8-fluoroquinoline (20.6 g, 0.12 mol) and 3- (2-fluorophenyl) -2,3-dimethylbutane were added dropwise under ice cooling. A solution of 2-alcohol (28.3 g, 0.144 mmol) in dichloroethane (40 ml) was stirred at room temperature for 18 hours. Ice and ethyl acetate were added to the reaction solution, and the aqueous layer was basified with aqueous ammonia, extracted with ethyl acetate, dried over magnesium sulfate, filtered, and concentrated. The obtained residue was dissolved in chloroform, the insoluble matter was separated and filtered, and the filtrate was concentrated. The obtained residue was crystallized from a mixed solution of isopropyl ether and ethyl acetate to obtain 8-fluoro-3- (5-fluoro-3, 3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl) quinoline (16.7 g) as a white solid with a yield of 40%. ¹ H-NMR (CDCl ₃ ) δ: 9.06 (1H, d, J = 2.1Hz), 8.36 (1H, t, J = 1.7Hz), 7.67 (1H, d, J = 8.3Hz), 7.53 (1H, td, J = 8.0, 4.9Hz), 7.46 (1H, ddd, J = 10.5, 7.7, 1.3Hz), 7.23-7.15 (2H, m), 6.94 (1H, dd, J = 7.0, 1.8Hz), 1.46 (6H, s), 1.34 (6H, d, J = 13.1Hz)

Step 2: Production of 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-1,2,3,4-tetrahydroisoquinolin-1-yl) quinoline in nitrogen 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl) quinoline in a 2L three-necked flask under ambient conditions (16.7 g, 47.7 mmol) in ethanol (477 mL) was added with sodium borohydride (5.4 g, 0.14 mol), and the mixture was stirred at room temperature for 0.5 hours, and then heated under reflux for 3 hours. Water was added to the reaction solution, and ethanol was distilled off. Water and ethyl acetate were added to the obtained residue. The organic layer was dried over magnesium sulfate, filtered, and concentrated. The obtained residue was crystallized from a mixed liquid crystal of isopropyl ether and ethyl acetate to obtain 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-1,2,3,4-tetramethyl Hydroisoquinolin-1-yl) quinoline (8.7 g) as a pale yellow solid with a yield of 52%. ¹ H-NMR (CDCl ₃ ) δ: 8.84 (1H, d, J = 2.1Hz), 8.09 (1H, t, J = 1.8Hz), 7.58 (1H, d, J = 8.3Hz), 7.48 (1H, td, J = 8.0, 5.0Hz), 7.38 (1H, ddd, J = 10.6, 7.7, 1.3Hz), 6.95 (1H, td, J = 8.0, 5.2Hz), 6.90-6.85 (1H, m), 6.43 (1H, d, J = 7.6Hz), 5.41 (1H, s), 1.54 (3H, s), 1.46 (3H, d, J = 4.6Hz), 1.31 (3H, s), 1.20 (3H, s)

[Synthesis Example 22] 8-fluoro-3- (5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) quinoline (Compound No .: (2) -4) In a 200 mL three-necked flask under nitrogen, 3-cyano-8-fluoroquinoline (9.3 g, 54 mmol) and 1- (trifluoromethanesulfonic acid (100 g, 0.67 mol)) were added dropwise under ice cooling. 2-fluorophenyl) -2-methylpropan-2-ol (10.9 g, 65 mmol), and stirred at room temperature for 18 hours. The reaction solution was poured into ice water, the aqueous layer washed with ethyl acetate was basified with ammonia water, extracted with ethyl acetate, the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated. To the obtained residue was added 10% sodium hydroxide water (50 ml), and the mixture was heated under reflux for 1 hour. The reaction solution was extracted with ethyl acetate, dried over magnesium sulfate, filtered, and concentrated to obtain 8-fluoro-3- (5-fluoro-3,3-dimethyl-3,4-dihydroisoquinoline-1- ) Quinoline (10.2 g) as a white solid, yield 59%. ¹ H-NMR (CDCl ₃ ) δ: 9.12 (1H, d, J = 2.0Hz), 8.41 (1H, t, J = 1.8Hz), 7.68 (1H, d, J = 8.3Hz), 7.53 (1H, td, J = 7.9, 4.9Hz), 7.46 (1H, ddd, J = 10.4, 7.8, 1.3Hz), 7.25-7.16 (2H, m), 7.00 (1H, dd, J = 6.6, 2.0Hz), 2.89 (2H, s), 1.35 (6H, d, J = 9.5Hz)

[Test Example 1] Antibacterial test of Septoria tritici and Botrytis cinerera using dimethylsulfene to produce the compounds of the present invention and quinoline compounds (2) -1, (2) 1000 ppm solution of -2, (2) -3, (2) -4. Then, an appropriate amount of each of the 1000 ppm dimethylarsine solution of each compound and the spore suspension of each pathogenic bacteria (cell density 1 × 10 ⁵ cells / mL) was dispensed one by one into a 96-well microtiter plate and mixed to make the active ingredients The final concentration is 10 ppm of the compound of the present invention, or 10 ppm of a quinoline compound, or a combination thereof. The microtiter plate was cultured in a closed container at a dark temperature of 18 ° C, and the proliferation degree of the bacteria in the drug-treated area and the drug-free treatment area was measured after 0 to 7 days. Calculate the growth inhibition rate of the bacteria caused by the chemical treatment according to the following calculation formula. Growth inhibition rate = (1-proliferation degree in the drug treatment area / proliferation degree in the drug-free treatment area) × 100 The results of the antibacterial test on the combination of the compound of the present invention and a quinoline compound are shown in Table 6, Table 7, Table 8, and Table 9 (wheat blight of wheat), and Tables 10, 11, 12, and 13 (gray mildew). In the table, "H" represents a growth inhibition rate greater than 75%, "M" represents a growth inhibition rate of 40% to 75%, "L" represents a growth inhibition rate of less than 40%, and "ND" represents a failure to calculate growth inhibition. rate. In addition, "No treatment" in the numbered column in the table means that the compound of the present invention or the quinoline-based compound is not included.

[Table 133]

[Table 134]

[Table 135]

[Table 136]

[Table 137]

[Table 138]

[Table 139]

[Table 140]

[Test Example 2] Disease control test In this test example, quinoline compounds (2) -2, (2) -3, and (2) -4 were applied to tomato gray mold disease (denoted as GM) and rice fever (Denoted as B), cucumber anthracnose (denoted as A), apple scab (denoted as AS), and control of cabbage brown disease (denoted as CA). Details of the test method are disclosed below.

(Tomato gray mold: GM) After planting the test plants (tomato varieties: large-scale Fushou), the plants were cultivated until the leaf was expanded to 3 pieces. In the test, a diluted solution in which each compound was diluted with distilled water to a concentration of 50 ppm was spread. After the seedlings were sprayed for 1 day, the conidia of Botrytis cinerea were spray-inoculated, and then placed in an inoculation room at a room temperature of 20 to 23 ° C for about 48 hours to promote disease. The degree of disease onset 2 days after the inoculation was checked and the effect was evaluated. (Rice fever: B) Test plants (rice varieties: Xingfeng) are sown and cultivated until the second leaf is opened. In the test, a diluent diluted with distilled water to a concentration of 50 ppm for each compound was dispersed. After spraying the seedlings 1 day after inoculation with conidia of Magnaporthe grisea, the seedlings were placed in an inoculation room at a room temperature of 20 to 23 ° C for about 24 hours to promote disease. The degree of disease onset 10 days after the inoculation was checked and the effect was evaluated. (Cucumber anthracnose: A) After the test plants (cucumber varieties: Sagami half white) were sown, they were cultivated until the leaf was expanded to one piece. In the test, a diluent diluted with distilled water to a concentration of 50 ppm for each compound was dispersed. . After spraying the seedlings 1 day after inoculation, the conidia of Colletotrichum orbiculare were spray-inoculated, and then placed in an inoculation room at a room temperature of 20 to 23 ° C for about 24 hours to promote disease. The degree of disease onset 10 days after the inoculation was checked and the effect was evaluated. (Apple scab: AS) After the test plant (Apple variety: Wang Lin) was sown, it was cultivated until the leaf was expanded to 4 pieces. In the test, a diluent diluted with distilled water to a concentration of 50 ppm for each compound was dispersed. After spraying the seedlings 1 day after inoculation with the conidia of Venturia inaequalis, the seedlings were placed in an inoculation room at room temperature 18-20 ° C for about 24 hours to promote disease. The degree of disease onset 10 days after the inoculation was checked and the effect was evaluated. (Cabbage dark brown disease: CA) After the test plants (cabbage varieties: obtained in four seasons) were sown, they were cultivated until the cotyledons developed. The test was carried out by diluting a dilute solution with distilled water to a concentration of 250 ppm for each compound. After spraying the seedlings 1 day after inoculation with conidia of Brassica oleracea (Alternaria brassicicola), the seedlings were placed in an inoculation room at a room temperature of 20 to 23 ° C for about 48 hours to promote disease. The degree of morbidity after 2 days of inoculation was checked and the effect was evaluated.

For the disease control tests evaluated by the methods listed above, the following indicators were used to evaluate the incidence of disease. In addition, the control price is calculated from the degree of onset. [Degree of incidence] 0: no incidence 0.1: incidence area is about 3% 0.3: incidence area is approximately 10% 0.8: incidence area is approximately 25% 1.5: incidence area is approximately 50% 2: incidence area is approximately 70% 3: The area of disease is more than 95% [control price] Control price = 100 {1- (n / N)} N = the degree of disease in the untreated area, n = the degree of disease in each area The results of the control test of quinoline compounds. Tomato gray mold, rice fever, cucumber anthracnose, apple scab, black cabbage brown disease, compounds (2) -2, (2) -3, (2) -4 show control prices above 95% Control effect.

[Test Example 3] The antibacterial test against various pathogenic bacteria was performed in the same manner and at the same concentration as in Test Example 1. The quinoline-based compounds were tested against Fusarium oxysporum f.sp. cucumerinum and Glomerella cingulata. ), The antibacterial activity of rice sesame leaf blight (Cochlobolus miyabeanus), grape black head (Elinoe ampelina). As a result of the antibacterial test of quinoline-based compounds, compounds (2) -2, (2) -3, (2) -4 were completely inhibited against C. spp. The growth of various pathogenic bacteria. [Industrial availability]

The pest control composition and the novel quinoline-based compound of the present invention exhibit excellent pest control effects, and therefore have a utilization value in terms of pesticides.

Claims (14)

A pest control composition comprising, as a pyridone compound or a salt thereof represented by the formula (1), one or more components selected from the group consisting of a quinoline compound or a salt thereof represented by the formula (2a) and the formula (2b) Active ingredient [In the formula, R1 represents a hydroxyl group, a cyano group, a C1-C6 alkyl group which may be appropriately substituted by a substituent A, a C1-C6 haloalkyl group, and a C3-C8 ring which may also be appropriately substituted by a substituent A. Alkyl, C2 to C6 alkenyl, which may be appropriately substituted with substituent A, C2 to C6 haloalkenyl, C2 to C6 alkynyl, which may be appropriately substituted with substituent A, C2 to C6 haloalkynyl , C1 ~ C6 alkoxy groups that can be appropriately substituted with substituent A, C1 ~ C6 haloalkoxy groups, C3 ~ C8 cycloalkoxy groups that can also be appropriately substituted with substituent A, or substituents C2 ~ C6 alkenyloxy, C2 ~ C6 haloalkenyloxy suitably substituted by A, C3 ~ C6 alkynyloxy optionally substituted by substituent A, C3 ~ C6 haloalkynyloxy, or R10R11N- Here, R10 and R11 each independently represent a hydrogen atom or an alkyl group of C1 to C6; R2 represents a halogen atom, a hydroxyl group, a cyano group, a nitro group, or a C1 to C6 alkane which may be appropriately substituted by a substituent B Group, C1 to C6 haloalkyl group, C3 to C8 cycloalkyl group which may be appropriately substituted with substituent B, C2 to C6 alkenyl group which may be appropriately substituted with substituent B, and C2 to C6 haloalkenyl group C2 ~ C6 alkynes which can also be appropriately substituted by substituent B , C2 ~ C6 haloalkynyl, C1 ~ C6 alkoxy which can be appropriately substituted by substituent B, C1 ~ C6 haloalkoxy, and C3 ~ C8 cycloalkane which can also be appropriately substituted by substituent B Oxygen, C2 ~ C6 alkenyloxy, which may be appropriately substituted by substituent B, haloalkenoxy of C2 ~ C6, alkynyloxy of C3 ~ C6, which may also be appropriately substituted by substituent B, C3 ~ C6 Haloalkynyloxy, R20C (= O)-, where R20 is C1 ~ C6 alkyl, C1 ~ C6 haloalkyl, C3 ~ C8 cycloalkyl, C1 ~ C6 alkoxy, C1 ~ C6 haloalkoxy, C3 to C8 cycloalkoxy, or R21R22N-. Here, R21 and R22 each independently represent a hydrogen atom, and C1 to C6 alkyl, C1 which may be appropriately substituted by substituent B1. A haloalkyl group of ~ C6, or a cycloalkyl group of C3 ~ C8, or R21 and R22 and a bonded nitrogen atom are integrated to form aziridinyl, tetrahydroazetino, pyrrolidinyl, piperidinyl, Homopiperidinyl, or azaoctyl, R20C (= O) O-, where R20 has the same meaning as above, a 3- to 6-membered ring group containing 1 to 2 oxygen atoms, R23-L2- where, R23 represents alkyl group of C1 ~ C6, or haloalkyl of C1 ~ C6, L2 represents S, SO, or SO _2, R21R22N-, here, R 21 and R22 have the same meanings as above, or R24C (= O) N (R25)-, where R24 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, C1 to C6 alkoxy, C1 to C6 haloalkoxy, C3 to C8 cycloalkoxy, or R21R22N-. Here, R21 and R22 have the same meanings as above, R25 represents a hydrogen atom, and may also be substituted. B1 appropriately substituted C1-C6 alkyl, C1-C6 haloalkyl, or C3-C8 cycloalkyl; R3 represents a hydrogen atom, a halogen atom, a nitro group, or C1 that may be appropriately substituted by a substituent C ~ C6 alkyl, C1 ~ C6 haloalkyl, C3 ~ C8 cycloalkyl which can be appropriately substituted by substituent C, C1 ~ C6 alkoxy which can also be appropriately substituted by substituent C, C1 ~ C6 haloalkoxy, C2 to C6 alkenyl, which may be appropriately substituted with substituent C, C2 to C6 haloalkenyl, C2 to C6 alkynyl, which may be appropriately substituted with substituent C, C2 to C6 Haloalkynyl, R30-L3-, where R30 has the meaning of the aforementioned R23, L3 has the meaning of the aforementioned L2, R31R32N-, and here, R31 and R32 have the meaning of the aforementioned R21 and R22, or R33C (= O)-, Here, R33 represents an alkyl group of C1 to C6, a haloalkyl group of C1 to C6, or a cycloalkyl group of C3 to C8; n is 0 to 5 Integer, but when n is 2 or more, two or more of R2 each independently represents a substituent group; X represents an oxygen atom or a sulfur atom; Y represents phenyl, pyridyl, despair Base, pyrimidinyl, pyridine Base, three Base, four Group, thienyl group, thiazolyl group, isothiazolyl group, or thiadiazolyl group, in the phenyl group, the substituent D is substituted in the ortho position, and further, each of the substituents D1 independently has appropriate 0 to 4 substitutions, and the pyridyl group The pyridine Group, the pyrimidinyl group, the da Base, the three Base, or the four In the group, the substituent D is substituted in the ortho position, and further, each of the substituents D1 is independently substituted with appropriate 0 to 3 substitutions. The group D is substituted in the ortho position, and each of the substituents D1 independently has appropriate 0 to 2 substitutions; the bond containing a dashed line portion represents a double bond or a single bond, and the substituent A is selected from the group consisting of a hydroxyl group and a cyanide Group, C3 to C8 cycloalkyl, C1 to C6 alkoxy, C1 to C6 haloalkoxy, C3 to C8 cycloalkoxy, R12R13N-, and R14-L1- (here, R12 and R13 each independently represents a hydrogen atom, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group, or R12 and R13 and a bonded nitrogen atom to form an aziridine. Group, tetrahydroacryl group, pyrrolidinyl, piperidinyl, homopiperidinyl, or azaoctyl group, where R14 represents a C1-C6 alkyl group or a C1-C6 haloalkyl group L1 represents at least one of the group consisting of S, SO, or SO ₂ ); Substituent B represents a group selected from the group consisting of hydroxy, cyano, cycloalkyl from C3 to C8, alkoxy from C1 to C6, C1 ~ C6 haloalkoxy, C3 ~ C8 cycloalkoxy, C2 ~ C 6 alkoxyalkoxy, R21R22N- (here, R21 and R22 have the same meaning as above), R23-L2- (here, R23 and L2 have the same meaning as above), R26R27R28Si- (here, R26, R27, and R28 , Each independently represents an alkyl group of C1 to C6), R26R27R28Si- (CH ₂ ) sO- (here, s represents an integer of 1 to 3, R26, R27 and R28 have the same meanings as above), R20C (= O)-( Here, R20 has the same meaning as above) and at least one member of the group consisting of a 3 to 6-membered ring containing 1 to 2 oxygen atoms; the substituent B1 represents a alkane selected from the group consisting of cyano and C1 to C6 At least one of the group consisting of oxy, C1 to C6 haloalkoxy, and C3 to C8 cycloalkoxy; the substituent C represents a cycloalkyl group selected from hydroxy, cyano, and C3 to C8 , C1 ~ C6 alkoxy, C1 ~ C6 haloalkoxy, C3 ~ C8 cycloalkoxy, R31R32N- (here, R31 and R32 have the same meaning as R21 and R22 mentioned above), and R30-L3- (Herein, R30 has the meaning of R14 and L3 has the meaning of L1 above); at least one of the group consisting of: D is selected from a halogen atom, an alkyl group of C1 to C6, and a haloalkane of C1 to C6 Group, at least one of the group consisting of C1 ~ C6 alkoxy group and C1 ~ C6 haloalkoxy group; substituent D1, Selected from the group consisting of hydroxyl, halogen atom, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, and C3- At least one member of the group consisting of cycloalkoxy groups of C8; [In the formula, R2a and R2b each independently represent an alkyl group of C1 to C6 which may be appropriately substituted by the substituent E1, an aryl group which may be appropriately substituted by the substituent E2, and a heteroaryl group which may be appropriately substituted by the substituent E3. Group, or an aralkyl group which may be appropriately substituted by the substituent E2, or R2a and R2b may be integrated with the carbon atom to which they are bonded to form a cycloalkyl group of C3 to C10 which may also be appropriately substituted by the substituent E4 Ring; R2c and R2d each independently represent a hydrogen atom, an alkyl group of C1 to C6 which may also be appropriately substituted by a substituent E1, a halogen atom, an alkoxy group of C1 to C6, or a hydroxyl group, or R2c and R2d may be used with them The bonded carbon atoms become one to form a carbonyl group or a cycloalkyl ring of C3 ~ C10 which can also be appropriately substituted by the substituent E4; R2e represents a hydrogen atom, a fluorenyl group of C2 ~ C7, or it may also be substituted by E1 Appropriately substituted C1 to C6 alkyl groups; X1 represents a halogen atom, C1 to C6 alkyl groups that may be appropriately substituted with substituent E5, C2 to C6 alkenyl groups that may also be appropriately substituted with substituent E6, or C2 ~ C6 alkynyl suitably substituted with substituent E7, aryl optionally substituted with substituent E2, and optionally substituted E3 Appropriately substituted heteroaryl, C1-C6 alkoxy groups, amine groups that may also be appropriately substituted with substituents E8, fluorenyl groups from C2-C7, cyano groups, or hydrogen atoms that may also be substituted with a substituent E9 N-hydroxyalkanoimide group; X2 represents a halogen atom, an alkyl group of C1 to C6, an alkoxy group or a hydroxyl group of C1 to C6, n1 represents an integer of 0 to 4, n2 represents an integer of 0 to 6, substituent E1 , Represents at least one selected from the group consisting of a halogen atom, an alkoxy group of C1 to C6, an alkylthio group of C1 to C6, and a phenoxy group; and the substituent E2 represents a group selected from a halogen atom, C1 to C6 Alkyl, C1 ~ C6 haloalkyl, C1 ~ C6 alkoxy, amine, nitro, cyano, hydroxy, mercapto, and C1 ~ C6 alkylthio At least one of the group consisting of; the substituent E3 represents at least one selected from the group consisting of a halogen atom, an alkyl group of C1 to C6, a haloalkyl group of C1 to C6, and an alkoxy group of C1 to C6 The substituent E4 represents at least one selected from the group consisting of a halogen atom, an alkyl group of C1 to C6, an alkoxy group of C1 to C6, and a phenoxy group; the substituent E5 represents a group selected from a halogen atom, C1 ~ C6 alkoxy At least one of the group consisting of a hydroxy group, a hydroxyl group, an alkoxycarbonyl group of C2 to C7, and a phenoxy group; the substituent E6 represents a group selected from a halogen atom, an alkoxy group of C1 to C6, and an alkoxy group of C2 to C7 At least one member of the group consisting of carbonyl and phenoxy groups; the substituent E7 represents at least one member selected from the group consisting of halogen atoms, alkoxy groups of C1 to C6, and phenoxy groups; the substituent group E8 , Represents at least one selected from the group consisting of C1 to C6 alkyl groups and C2 to C7 fluorenyl groups; the substituent E9 represents a group selected from C1 to C6 alkyl groups, C2 to C6 alkenyl groups, C2 to C6 is at least one member of the group consisting of alkynyl, aralkyl, aryl, and heteroaryl]. For example, in the pest control composition of the scope of application for patent, in the pyridone compound represented by the formula (1), R1 represents a cyano group, a C1-C6 alkyl group, and C1- C6 haloalkyl, C3 to C8 cycloalkyl which may be appropriately substituted with substituent A, C2 to C6 alkenyl which may be appropriately substituted with substituent A, C2 to C6 haloalkenyl, or C2 ~ C6 alkynyl, or R10R11N-, which is appropriately substituted by substituent A, where R10 and R11 each independently represent a hydrogen atom or an alkyl group of C1-C6; R2 represents a halogen atom, a hydroxyl group, a cyano group, or C1-C6 alkyl, C1-C6 haloalkyl, which may be appropriately substituted by substituent B, C1-C6 alkoxy, C1-C6 haloalkoxy, which may also be appropriately substituted by substituent B C3 ~ C8 cycloalkoxy groups which may be appropriately substituted with substituent B, C2 ~ C6 alkoxy groups which may be appropriately substituted with substituent B, and C3 ~ C6 alkynyloxy groups which may be appropriately substituted with substituent B , R20C (= O) O- (Here, R20 means C1 ~ C6 alkyl, C1 ~ C6 haloalkyl, C3 ~ C8 cycloalkyl, C1 ~ C6 alkoxy, C1 ~ C6 halogen Alkoxy, C3 ~ C8 cycloalkoxy, or R21R22N- ( Here, R21 and R22 each independently represent a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a C3-C8 cycloalkyl group, or R21 and R22, which can also be appropriately substituted by a substituent B1. Integrates with the bonded nitrogen atom to form aziridinyl, tetrahydroacryl, pyrrolidinyl, piperidinyl, homopiperidinyl, or azacyclooctyl)), or R23-L2- (Here, R23 represents an alkyl group of C1 to C6, or a haloalkyl group of C1 to C6, and L2 represents S, SO, or SO ₂ ); R3 represents a hydrogen atom, a halogen atom, or may be appropriately substituted by a substituent C C1-C6 alkyl group, C3-C8 cycloalkyl group which may be appropriately substituted by the substituent C, C1-C6 alkoxy group which may also be appropriately substituted by the substituent C, and may also be appropriately substituted by the substituent C C2 ~ C6 alkynyl, or R30-L3-, where R30 has the same meaning as R23, and L3 has the same meaning as L2; Y is phenyl or pyridyl. In the pyridine group, the substituent D1 is substituted in the ortho position, and further in the pyridine group, the substituent D1 is independently substituted with appropriate 0 to 3 substitutions. For example, in the pest control composition of the second scope of the patent application, among the pyridone compounds represented by formula (1), R1 represents a C1-C6 alkyl group or a C1-C6 alkyl group which can also be appropriately substituted by a substituent A. Haloalkyl; R2 represents a halogen atom, an alkyl group of C1 to C6 which may be appropriately substituted by substituent B, or an alkoxy group of C1 to C6 which may also be appropriately substituted by substituent B; R3 represents a hydrogen atom, a halogen atom Or a C1-C6 alkyl group which may be appropriately substituted by a substituent C. For example, in the pest control composition of the scope of patent application, in the quinoline-based compound represented by formula (2a) or formula (2b), R2a and R2b are each independently C1 which may be appropriately substituted by substituent E1. ~ C6 alkyl, R2c and R2d are each independently a hydrogen atom, an alkyl or halogen atom of C1 ~ C6 which may be appropriately substituted by substituent E1, R2e is a hydrogen atom or C1 which may also be appropriately substituted by substituent E1 An alkyl group of ~ C6, X1 is a halogen atom, X2 is a halogen atom, n1 is an integer of 0 to 4, and n2 is an integer of 0 to 6. For example, the pest control composition of the scope of application for patent, wherein the quinoline compound represented by formula (2a) or (2b) is a quinoline compound represented by formula (2c) or (2d); 3] [In the formula, R2f represents a hydrogen atom or a methyl group, X3, X4, and X5 each independently represent a hydrogen atom or a fluorine atom, and X6 and X7 each independently represent a hydrogen atom, a methyl group, or a fluorine atom]. For example, the pest control composition of claim 4 in which the quinoline compound represented by formula (2a) or (2b) is selected from 3- (4,4-difluoro-3,3-dimethyl -3,4-dihydroisoquinolin-1-yl) quinoline, 3- (4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl ) -8-fluoroquinoline, 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-1,2,3,4-tetrahydroisoquinolin-1-yl) quine And at least one member of the group consisting of 8-fluoro-3- (5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) quinoline. A method for controlling pests is to apply a pest control composition such as the one in the scope of patent application. A method for controlling pests is to simultaneously apply a composition containing a pyridone compound or a salt thereof represented by formula (1) as set forth in item 1 of the scope of patent application as an active ingredient, and a composition containing the formula as set forth in item 1 of the scope of patent application A composition in which a quinoline compound or a salt thereof represented by Formula 2a) or Formula (2b) is an active ingredient. A method for controlling pests by applying a composition containing, as an active ingredient, a pyridone compound or a salt thereof represented by formula (1) in item 1 of the scope of patent application, or containing formula (2a) in item 1 of scope of patent application ) Or a quinoline-based compound represented by formula (2b) or a salt thereof as an active ingredient, and then the other composition is applied. A quinoline-based compound or a salt thereof is a quinoline-based compound represented by formula (2c) or formula (2d) in item 5 of the scope of the patent application, R2f is a hydrogen atom or a methyl group, X3 is a fluorine atom, X4, X5 , X6 and X7 are each independently a hydrogen atom or a fluorine atom, but in formula (2c), at least one of X4, X5, X6 or X7 is a fluorine atom, and in formula (2d), any of X4 or X5 is Is a fluorine atom. For example, a quinoline compound or a salt thereof according to item 10 of the application, wherein the quinoline compound represented by formula (2c) or formula (2d) is 3- (4,4-difluoro-3,3-dimethyl -3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline, 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-1,2, 3,4-tetrahydroisoquinolin-1-yl) quinoline, or 8-fluoro-3- (5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl )quinoline. For example, a quinoline-based compound or a salt thereof according to item 11 of the application, wherein the quinoline-based compound represented by formula (2c) or formula (2d) is 3- (4,4-difluoro-3,3-dimethyl -3,4-dihydroisoquinolin-1-yl) -8-fluoroquinoline or 8-fluoro-3- (5-fluoro-3,3,4,4-tetramethyl-1,2, 3,4-tetrahydroisoquinolin-1-yl) quinoline. A method for controlling pests, comprising the steps of: applying an effective amount of a compound of formula (I) as described in item 1 of the patent application scope, or a plant, seed, soil, seed box, or tray to which pest control is required; A salt and a quinoline-based compound represented by formula (2a) or formula (2b) or a salt thereof. The use of a compound of formula (I) or a salt thereof and a quinoline-based compound represented by formula (2a) or formula (2b) or a salt thereof as in item 1 of the scope of application for a patent is a pest control agent.