WO2017026298A1

WO2017026298A1 - Oxalyl amide compound and use thereof for controlling harmful arthropods

Info

Publication number: WO2017026298A1
Application number: PCT/JP2016/072295
Authority: WO
Inventors: 政樹 ▲高▼橋
Original assignee: 住友化学株式会社
Priority date: 2015-08-10
Filing date: 2016-07-29
Publication date: 2017-02-16

Abstract

The present invention addresses the problem of providing a compound which can exhibit an excellent controlling effect against harmful arthropods. The problem can be solved by an oxalyl amide compound represented by formula (I) [wherein G¹, G² and G³ independently represent -CR⁷R⁸- or a single bond; R¹ and R³ independently represent a hydrogen atom, a halogen atom, -R⁹ or the like; R² represents -R⁹ or the like; R⁴, R⁵ and R⁶ independently represent a hydrogen atom, -R⁹ or the like; R⁷ and R⁸ independently represent a hydrogen atom, -R⁹ or the like; R⁹ represents a C1-C6 linear hydrocarbon group which may have at least one halogen atom; R¹⁰ represents a C1-C3 linear hydrocarbon group; X^a represents -R¹⁰ or the like; X^b represents -R⁹ or the like; n independently represents 0, 1 or 2; and m represents 0, 1, 2, 3 or 4].

Description

Oxalylamide compounds and their use for controlling harmful arthropods

The present invention relates to certain oxalamide compounds and their use for harmful arthropods.

So far, various compounds have been studied and put to practical use for the purpose of controlling harmful arthropods.

Also, certain compounds (for example, see Patent Document 1) are known.

International Publication No. 2012-164698

An object of the present invention is to provide a compound having an excellent controlling effect on harmful arthropods and a method for controlling harmful arthropods using the compound.

[1] Formula (I)

[Where:
G ¹ , G ² and G ³ each independently represent —CR ⁷ R ⁸ — or a single bond (provided that at least one of G ¹ , G ² and G ³ represents —CR ⁷ R ⁸ —) ),
R ¹ and R ³ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, —R ⁹ , —OR ⁹ or —S (O) _p R ⁹ ;
R ² represents —R ⁹ , —OR ⁹ or —S (O) _p R ⁹ ,
R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, —R ⁹ , one or more halogen atoms (C1-C4 alkoxy) C1-C4 alkyl group, —C (O) R ⁹ Or represents —CO ₂ R ⁹ ,
R ⁷ and R ⁸ each independently represent a hydrogen atom or —R ⁹ , or R ⁷ and R ⁸ together with the carbon atom to which they are attached, a C3-C7 cycloalkane {the C3-C7 cyclo The alkane may have one or more substituents selected from the group consisting of a halogen atom and R ^9, and when having two or more substituents, they may be the same or different. },
R ⁹ represents a C1-C6 chain hydrocarbon group which may have one or more halogen atoms,
X ^a represents a halogen atom, a cyano group, —R ¹⁰ or —OR ¹⁰ ;
R ¹⁰ represents a C1-C3 chain hydrocarbon group,
X ^b represents -R ⁹ , -OR ⁹ , a halogen atom or a cyano group,
n and p each independently represent 0, 1 or 2;
m represents 0, 1, 2, 3 or 4. ]
An oxalylamide compound represented by formula (hereinafter also referred to as the present compound).
[2] Any one of G ¹ , G ² and G ³ is —CR ⁷ R ⁸ — (wherein R ⁷ and R ⁸ each independently represents a hydrogen atom or —R ⁹ , or R ⁷ and R ⁸ together with the carbon atom to which they are attached, a C3-C7 cycloalkane {wherein the C3-C7 cycloalkane has one or more substituents selected from the group consisting of a halogen atom and R ⁹ And when two or more substituents are present, they may be the same or different.}, And the other two are each independently —CR ⁷ R ⁸ — ( Wherein R ⁷ and R ⁸ each independently represents a hydrogen atom or —R ⁹ ) or a compound according to [1], which is a single bond.
[3] The compound according to [1] or [2], wherein G ¹ is —CR ⁷ R ⁸ —, and G ² and G ³ are a single bond.
[4] The compound according to [1] or [2], wherein G ¹ and G ² are —CR ⁷ R ⁸ —, and G ³ is a single bond.
[5] The compound according to [1] or [2], wherein G ¹ , G ² and G ³ are —CR ⁷ R ⁸ —. [6] Either ^one of R ¹ and R ³ is a bromine atom, an iodine atom or a C1-C6 alkyl group, and the other is a C1-C6 alkyl group which may have one or more halogen atoms, C1- The oxalylamide compound according to any one of [1] to [5], which is a C6 haloalkoxy group or —S (O) _p R ¹¹ (R ¹¹ represents C1-C6 haloalkyl).
[7] The oxalylamide compound according to [6], wherein R ² is a C1-C6 haloalkyl group.
[8] The oxalylamide compound according to [6], wherein R ² is a C1-C6 haloalkoxy group.
[9] The oxalylamide compound according to [6], wherein R ² is —S (O) _p R ¹¹ .
[10] A harmful arthropod control composition comprising the oxalylamide compound according to any one of [1] to [9] and an inert carrier.
[10-1] The oxalylamide compound according to any one of [1] to [9] for controlling harmful arthropods.
[10-2] Use of the oxalylamide compound according to any one of [1] to [9] in the production of a harmful arthropod control composition.
[11] A method for controlling harmful arthropods, which comprises applying an effective amount of the oxalylamide compound according to any one of [1] to [9] to harmful arthropods or habitats of harmful arthropods.
[12] Formula (II)

[Where:
R ⁶ represents a hydrogen atom, —R ⁹ , a (C1-C4 alkoxy) C1-C4 alkyl group optionally having one or more halogen atoms, —C (O) R ⁹ or —CO ₂ R ⁹ ;
R ⁹ represents a C1-C6 chain hydrocarbon group which may have one or more halogen atoms,
R ¹² represents a hydrogen atom or a C1-C4 alkyl group,
j represents 1, 2 or 3. ]
A compound represented by

Since the compound of the present invention has an excellent control activity against harmful arthropods, it is useful as an active ingredient of a harmful arthropod control agent.

The substituent in the compound of the present invention will be described.

In this specification, “substituent” means an atom and an atomic group.

In this specification, the notation “CX-CY” (X and Y in the notation are natural numbers, respectively) means that the number of carbon atoms is X to Y. For example, the notation “C1-C6” means 1 to 6 carbon atoms.

In the present specification, “halogen atom” means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the present specification, in the “may have one or more halogen atoms”, when having two or more halogen atoms, the halogen atoms may be the same or different from each other.

Examples of the “chain hydrocarbon group” in the present specification include an alkyl group, an alkenyl group, and an alkynyl group.
In the present specification, examples of the “C1-C3 chain hydrocarbon group” include a C1-C3 alkyl group, a C2-C3 alkenyl group, and a C2-C3 alkynyl group.
In the present specification, examples of “C1-C6 chain hydrocarbon group” include C1-C6 alkyl group, C2-C6 alkenyl group and C2-C6 alkynyl group.
Examples of the “alkyl group” include methyl group, ethyl group, propyl group, isopropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, Butyl, sec-butyl, isobutyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3 -Dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, pentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and hexyl group.
Examples of the “alkenyl group” include a vinyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1,2-dimethyl-1-propenyl group, Examples include 1,1-dimethyl-2-propenyl group, 1-ethyl-1-propenyl group, 1-ethyl-2-propenyl group, 3-butenyl group, 4-pentenyl group and 5-hexenyl group.
Examples of the “alkynyl group” include ethynyl group, 1-propynyl group, 2-propynyl group, 1-methyl-2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-ethyl-2-propynyl group, Examples thereof include 2-butynyl group, 4-pentynyl group and 5-hexynyl group.

In the present specification, “(C1-C4 alkoxy) C1-C4 alkyl group optionally having one or more halogen atoms” means that one hydrogen atom of “C1-C4 alkyl group” is “1 or more A C1-C4 alkoxy group optionally having a halogen atom ”such as a methoxymethyl group, an ethoxymethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, 2- (2, 2,2-trifluoroethoxy) ethyl group.

In the present specification, the “C1-C6 haloalkyl group” is a C1-C6 alkyl group substituted with one or more halogen atoms, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 1,1,2,2,3,3-hexafluoropropyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl Groups, trichloromethyl groups, and perfluoropropan-2-yl groups.
In the present specification, the “C1-C6 haloalkoxy group” is a C1-C6 alkoxy group substituted with one or more halogen atoms, and examples thereof include a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group. 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, 1,1,2,2,3,3-hexafluoropropoxy group, 2,2,2-trifluoro-1- (trifluoromethyl) Including ethoxy group and trichloromethoxy group.

In the present specification, examples of “C3-C7 cycloalkane” include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane.

In the present specification, when R ⁷ is more present in the structural formula, selected plurality of R ⁷ is a substituent as defined independently. If R ⁸ is more present in the structural formula, selected plurality of R ⁸ is a substituent as defined independently. If R ⁹ is more present in the structural formula, selected plurality of R ⁹ is a substituent as defined independently.

The oxalylamide compound represented by the formula (I) includes one or more asymmetric centers in the structural formula and may have a plurality of optical isomers. The compound of the present invention includes each of such optical isomers and a mixture containing them in an arbitrary ratio. In addition, the oxalylamide compound represented by the formula (I) may have a plurality of geometric isomers derived from a carbon-carbon double bond in the structure. The compound of the present invention includes each of such geometric isomers and a mixture in which they are contained in an arbitrary ratio.

As described above, in a preferred embodiment of the compound of the present invention, in the formula (I), any one of G ¹ , G ² and G ³ is —CR ⁷ R ⁸ — (where R ⁷ and R or ⁸ represents a hydrogen atom or -R ⁹ each independently, or ^{R 7} and ^{R 8} together with the carbon atoms to which they are attached, C3-C7 cycloalkane {said C3-C7 cycloalkane, halogen And may have one or more substituents selected from the group consisting of an atom and R ^9, and when having two or more substituents, they may be the same or different.}. , And the other two each independently represent —CR ⁷ R ⁸ — (wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or —R ⁹ ) or a single bond.
This means that “C3-C7 cycloalkane existing in the partial structure: —G ¹ -G ² -G ³ — in formula (I) {the C3-C7 cycloalkane consists of a halogen atom and R ⁹ It may have one or more substituents selected from the group, and when it has two or more substituents, they may be the same or different. It means that the number of "}" is only one.

As this invention compound, the compound of the following aspects is mentioned, for example.
[Aspect 1] In the compound of the present invention, R ¹ and R ³ are each independently a hydrogen atom, a halogen atom, —R ⁹ , —OR ⁹ or —S (O) _p R ⁹ , and R ⁴ , R ⁵ And R ⁶ is each independently a C1-C3 chain hydrocarbon group or hydrogen atom which may have one or more halogen atoms, and n is 0.
[Aspect 2] A compound according to Aspect 1, wherein G ¹ is —CR ⁷ R ⁸ —, and G ² and G ³ are single bonds.
[Aspect 3] A compound according to Aspect 2, wherein R ⁷ and R ⁸ are each independently a hydrogen atom or —R ⁹ .
[Aspect 4] A compound according to Aspect 2, wherein R ⁷ and R ⁸ together with the carbon atom to which they are attached form a C3-C7 cycloalkane.
[Aspect 5] A compound according to Aspect 2, wherein R ⁷ and R ⁸ together with the carbon atom to which they are bonded form cyclopropane.
[Aspect 6] A compound according to Aspect 1, wherein G ¹ and G ² are —CR ⁷ R ⁸ — and G ³ is a single bond.
[Aspect 7] A compound according to Aspect 6, wherein R ⁷ and R ⁸ are each independently a hydrogen atom or —R ⁹ .
[Aspect 8] A compound according to Aspect 6, wherein G ¹ is a C3-C7 cycloalkane-1,1-diyl group, and R ⁷ and R ⁸ in G ² are each independently a hydrogen atom or —R ⁹ .
[Aspect 9] A compound according to Aspect 8, wherein G ¹ is a cyclopropane-1,1-diyl group.
[Aspect 10] A compound according to Aspect 8, wherein G ² is a C3-C7 cycloalkane-1,1-diyl group, and R ⁷ and R ⁸ in G ¹ are each independently a hydrogen atom or —R ⁹ .
[Aspect 11] A compound according to Aspect 10, wherein G ² is a cyclopropane-1,1-diyl group.
[Aspect 12] A compound according to Aspect 1, wherein G ¹ , G ² and G ³ are —CR ⁷ R ⁸ —.
[Aspect 13] A compound according to Aspect 12, wherein R ⁷ and R ⁸ are each independently a hydrogen atom or —R ⁹ .
[Aspect 14] A compound according to Aspect 12, wherein G ¹ is a C3-C7 cycloalkane-1,1-diyl group, and R ⁷ and R ⁸ in G ² are each independently a hydrogen atom or —R ⁹ .
[Aspect 15] A compound according to Aspect 14, wherein G ¹ is a cyclopropane-1,1-diyl group.
[Aspect 16] In Aspect 1, G ² is a C3-C7 cycloalkane-1,1-diyl group, and R ⁷ and R ⁸ in G ¹ and G ³ are each independently a hydrogen atom or —R ⁹ . Compound.
[Aspect 17] A compound according to Aspect 16, wherein G ² is a cyclopropane-1,1-diyl group.
[Aspect 18] In Aspect 1, G ³ is a C3-C7 cycloalkane-1,1-diyl group, and R ⁷ and R ⁸ in G ¹ and G ² are each independently a hydrogen atom or —R ⁹ . Compound.
[Aspect 19] A compound according to Aspect 18, wherein G ³ is a cyclopropane-1,1-diyl group.
[Aspect 20] The compound according to Aspect 2, wherein R ⁷ and R ⁸ together with the carbon atom to which they are bonded form cyclopropane or cyclobutane.
[Aspect 21] A compound according to Aspect 8, wherein G ¹ is a cyclopropane-1,1-diyl group or a cyclobutane-1,1-diyl group.
[Aspect 22] A compound according to Aspect 10, wherein G ² is a cyclopropane-1,1-diyl group or a cyclobutane-1,1-diyl group.
[Aspect 23] A compound according to Aspect 14, wherein G ¹ is a cyclopropane-1,1-diyl group or a cyclobutane-1,1-diyl group.
[Aspect 24] A compound according to Aspect 16, wherein G ² is a cyclopropane-1,1-diyl group or a cyclobutane-1,1-diyl group.
[Aspect 25] A compound according to Aspect 18, wherein G ³ is a cyclopropane-1,1-diyl group or a cyclobutane-1,1-diyl group.
[Aspect 26] A compound according to Aspect 1 to Aspect 25, wherein R ² is —R ⁹ .
[Aspect 27] A compound according to Aspect 1 to Aspect 25, wherein R ² is a C1-C3 chain hydrocarbon group.
[Aspect 28] A compound according to Aspect 1 to Aspect 25, wherein R ² is a C1-C6 haloalkyl group.
[Aspect 29] A compound according to Aspect 1 to Aspect 25, wherein R ² is a C1-C6 haloalkoxy group.
[Aspect 30] A compound according to Aspect 1 to Aspect 25, wherein R ² is —S (O) _p R ¹¹ .
[Aspect 31] In the compound of the present invention, any ^one of R ¹ and R ³ may be a hydrogen atom, a bromine atom, an iodine atom or a C1-C6 alkyl group, and the other may have one or more halogen atoms. Good C1-C6 alkyl group, C1-C6 haloalkoxy group or —S (O) _p R ¹¹ , wherein R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, methyl group, ethyl group, propyl group or A compound which is an isopropyl group and n is 0.
[Aspect 32] A compound according to Aspect 31, wherein G ¹ is —CR ⁷ R ⁸ —, and G ² and G ³ are single bonds.
[Aspect 33] A compound according to Aspect 32, wherein R ⁷ and R ⁸ are each independently a hydrogen atom or —R ⁹ .
[Aspect 34] The compound according to aspect 32, wherein R ⁷ and R ⁸ together with the carbon atom to which they are attached form a C3-C7 cycloalkane.
[Aspect 35] The compound according to aspect 32, wherein R ⁷ and R ⁸ together with the carbon atom to which they are attached form cyclopropane.
[Aspect 36] The compound according to Aspect 31, wherein G ¹ and G ² are —CR ⁷ R ⁸ — and G ³ is a single bond.
[Aspect 37] A compound according to Aspect 36, wherein R ⁷ and R ⁸ are each independently a hydrogen atom or —R ⁹ .
[Aspect 38] A compound according to Aspect 36, wherein G ¹ is a C3-C7 cycloalkane-1,1-diyl group, and R ⁷ and R ⁸ in G ² are each independently a hydrogen atom or —R ⁹ .
[Aspect 39] A compound according to Aspect 38, wherein G ¹ forms a cyclopropane-1,1-diyl group.
[Aspect 40] A compound according to Aspect 36, wherein G ² is a C3-C7 cycloalkane-1,1-diyl group, and R ⁷ and R ⁸ in G ¹ are each independently a hydrogen atom or —R ⁹ .
[Aspect 41] A compound according to Aspect 40, wherein G ² is a cyclopropane-1,1-diyl group.
[Aspect 42] A compound according to Aspect 31, wherein G ¹ , G ² and G ³ are —CR ⁷ R ⁸ —.
[Aspect 43] A compound according to aspect 42, wherein R ⁷ and R ⁸ are each independently a hydrogen atom or —R ⁹ .
[Aspect 44] In Aspect 31, G ¹ is a C3-C7 cycloalkane-1,1-diyl group, and R ⁷ and R ⁸ in G ² and G ³ are each independently a hydrogen atom or —R ⁹ . Compound.
[Aspect 45] A compound according to Aspect 44, wherein G ¹ is a cyclopropane-1,1-diyl group.
In [Mode 46] embodiment 31, ^{G 2} is a C3-C7 cycloalkane-1,1-diyl group, is a hydrogen atom or -R ⁹ ^{R 7} and ^{R 8} in ^{G 1} and ^{G 3} are each independently Compound.
[Aspect 47] A compound according to Aspect 46, wherein G ² is a cyclopropane-1,1-diyl group.
[Aspect 48] In Aspect 31, G ³ is a C3-C7 cycloalkane-1,1-diyl group, and R ⁷ and R ⁸ in G ¹ and G ² are each independently a hydrogen atom or —R ⁹ . Compound.
[Aspect 49] A compound according to Aspect 48, wherein G ³ is a cyclopropane-1,1-diyl group.
[Aspect 50] A compound according to Aspect 38, wherein G ¹ forms a cyclopropane-1,1-diyl group or a cyclobutane-1,1-diyl group.
[Aspect 51] A compound according to Aspect 40, wherein G ² is a cyclopropane-1,1-diyl group or a cyclobutane-1,1-diyl group.
[Aspect 52] A compound according to Aspect 44, wherein G ¹ is a cyclopropane-1,1-diyl group or a cyclobutane-1,1-diyl group.
[Aspect 53] A compound according to Aspect 46, wherein G ² is a cyclopropane-1,1-diyl group or a cyclobutane-1,1-diyl group.
[Aspect 54] A compound according to Aspect 48, wherein G ³ is a cyclopropane-1,1-diyl group or a cyclobutane-1,1-diyl group.
[Aspect 55] A compound according to Aspect 31 to Aspect 54, wherein R ² is —R ⁹ .
[Aspect 56] A compound according to Aspect 31 to Aspect 54, wherein R ² is a C1-C3 chain hydrocarbon group.
[Aspect 57] A compound according to Aspect 31 to Aspect 54, wherein R ² is a C1-C6 haloalkyl group.
[Aspect 58] A compound according to Aspect 31 to Aspect 54, wherein R ² is a C1-C6 haloalkoxy group.
[Aspect 59] A compound according to Aspect 31 to Aspect 54, wherein R ² is —S (O) _p R ¹¹ .
[Aspect 60] In the compound of the present invention, G ¹ is a C3-C6 cycloalkane-1,1-diyl group, G ² and G ³ are a single bond, and ^one of R ¹ and R ³ is a halogen atom Or a C1-C6 alkyl group, the other is a halogen atom, a C1-C6 alkyl group or a C1-C6 haloalkoxy group optionally having one or more halogen atoms, and R ² is a C1-C6 haloalkyl group , N is 0, m is 0 or 1, X ^a is a halogen atom or a C1-C6 alkoxy group, R ⁴ is a hydrogen atom, and R ⁵ and R ⁶ are each independently a hydrogen atom or A compound which is a C1-C6 alkyl group.
[Aspect 61] In the compound of the present invention, G ¹ is —CR ⁷ R ⁸ —, G ² and G ³ are single bonds, and R ⁷ and R ⁸ are each independently a hydrogen atom or a C1-C6 alkyl group. Any ^one of R ¹ and R ³ is a halogen atom or a C1-C6 alkyl group, and the other is a halogen atom, a C1-C6 alkyl group which may have one or more halogen atoms, or a C1-C6 halo. An alkoxy group, R ² is a C1-C6 haloalkyl group, n is 0, m is 0 or 1, X ^a is a halogen atom or a C1-C6 alkoxy group, and R ⁴ is a hydrogen atom. A compound in which R ⁵ and R ⁶ are each independently a hydrogen atom or a C1-C6 alkyl group.
[Aspect 62] In Aspect 61, ^one of R ¹ and R ³ is a halogen atom, the other is a C1-C6 haloalkoxy group, R ² is a C1-C6 haloalkyl group, and n and m are 0 And R ⁴ , R ⁵ and R ⁶ are hydrogen atoms.
[Aspect 63] In the compound of the present invention, G ¹ and G ² are —CR ⁷ R ⁸ —, G ³ is a single bond, and R ⁷ and R ⁸ are each independently a hydrogen atom or a C1-C6 alkyl group. Any ^one of R ¹ and R ³ is a halogen atom or a C1-C6 alkyl group, and the other is a halogen atom, a C1-C6 alkyl group which may have one or more halogen atoms, or a C1-C6 halo. An alkoxy group, R ² is a C1-C6 haloalkyl group, n is 0, m is 0 or 1, X ^a is a halogen atom or a C1-C6 alkoxy group, and R ⁴ is a hydrogen atom. A compound in which R ⁵ and R ⁶ are each independently a hydrogen atom or a C1-C6 alkyl group.
[Aspect 64] In Aspect 63, R ⁷ and R ⁸ are hydrogen atoms, one of R ¹ and R ³ is a halogen atom, the other is a C1-C6 haloalkoxy group, and R ² is C1- A compound which is a C6 haloalkyl group, n and m are 0 or 1, R ⁴ and R ⁵ are hydrogen atoms, and R ⁶ is a C1-C6 alkyl group.

Examples of the compound represented by the formula (II) (hereinafter also referred to as the compound (II)) include the compounds of the following embodiments.
[Aspect 65] In the formula (II), R ⁶ is a hydrogen atom or a C1-C6 chain hydrocarbon group which may have one or more halogen atoms, and R ¹² is a hydrogen atom or a C1-C4 alkyl group. A compound in which j is 1, 2 or 3.
[Aspect 66] A compound according to Aspect 65, wherein j is 1 or 2.

Next, production methods of the compound of the present invention and compound (II) will be described.

The compound of the present invention, its intermediate compound and compound (II) can be produced, for example, according to the following production methods 1 to 15.

Manufacturing method 1
The compound of the present invention can be produced according to the following method.

[Wherein, Z represents a C1-C4 alkyl group, L represents a chlorine atom, a bromine atom, or an iodine atom, and the other symbols have the same meaning as described above. ]
First, the process (henceforth a manufacturing method) which manufactures the compound (henceforth a compound (M3)) shown by a formula (M3) from the compound (henceforth a compound (M1)) shown by a formula (M1). 1) is also described.

Compound (M3) can be produced by reacting compound (M1) with a compound represented by formula (M2) (hereinafter referred to as compound (M2)) in the presence of a base.

The reaction is usually performed in a solvent.

Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform (hereinafter referred to as aliphatic halogenated hydrocarbons); nitriles such as acetonitrile (hereinafter referred to as nitriles). Tetrahydrofuran, ethylene glycol dimethyl ether, methyl tert-butyl ether (hereinafter referred to as MTBE), ethers such as 1,4-dioxane (hereinafter referred to as ethers), acetone, ethyl methyl ketone, isobutyl methyl ketone, etc. Ketones (hereinafter referred to as ketones); Esters such as methyl acetate and ethyl acetate (hereinafter referred to as esters); Aromatic hydrocarbons such as toluene and xylene (hereinafter referred to as aromatic hydrocarbons) N, N-dimethylformamide (hereinafter referred to as DMF), N Methylpyrrolidone, aprotic polar solvents such as dimethyl sulfoxide (hereinafter, referred to as aprotic polar solvents.); And mixtures thereof.

Examples of the base used in the reaction include organic bases such as triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene (hereinafter referred to as organic bases); Alkali metal carbonates such as sodium and potassium carbonate (hereinafter referred to as alkali metal carbonates); alkaline earth metal carbonates such as calcium carbonate (hereinafter referred to as alkaline earth metal carbonates); sodium hydrogen carbonate and the like Alkali metal hydrogen carbonates (hereinafter referred to as alkali metal hydrogen carbonates); alkali metal hydroxides such as sodium hydroxide and potassium hydroxide (hereinafter referred to as alkali metal hydroxides); Alkaline earth metal hydroxides such as calcium (hereinafter referred to as alkaline earth metal hydroxides); sodium metho Metal alkoxides such as side and sodium ethoxide (hereinafter referred to as metal alkoxides); alkali metal hydrides such as sodium hydride (hereinafter referred to as alkali metal hydrides); and n-butyllithium, And organometallic reagents such as lithium diisopropylamide (hereinafter referred to as organometallic reagents).

In this reaction, the compound (M2) is usually used in a proportion of 1 to 2 mol and the base is usually used in a proportion of 1 to 2 mol with respect to 1 mol of the compound (M1).

The reaction temperature of the reaction is usually in the range of −80 to 150 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

Next, a process for producing a compound represented by the formula (M4) from the compound (M3) (hereinafter referred to as the compound (M4)) (hereinafter also referred to as the second process of the production method 1) will be described.

Compound (M4) can be produced by reducing compound (M3).

The reaction is usually performed in a solvent.

Examples of the solvent used in the reaction include ethers; esters; alcohols such as methanol, ethanol and isopropanol (hereinafter referred to as alcohols); acetic acid; water and a mixture thereof.

Examples of the reducing agent used in the reaction include iron and tin chloride.

In the reaction, an acid may be used as necessary. Examples of the acid used for the reaction include acetic acid, hydrogen chloride, ammonium chloride and the like.

In the reaction, the reducing agent is usually used in a ratio of 3 to 10 moles with respect to 1 mole of the compound (M3).

The reaction temperature of the reaction is usually in the range of 20 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.

Next, a process for producing a compound represented by the formula (M5) from the compound (M4) (hereinafter referred to as the compound (M5)) (hereinafter also referred to as the third process of the production method 1) will be described.

Compound (M5) can be produced by reacting compound (M4) with a compound represented by formula (R1) (hereinafter referred to as compound (R1)) in the presence of a base.

The reaction is usually performed in a solvent.

Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons, nitriles, ethers, ketones, esters, aromatic hydrocarbons, aprotic polar solvents, and mixtures thereof.

Examples of the base used in the reaction include organic bases, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides, and alkaline earth metal hydroxides.

In the reaction, the compound (R1) is usually used in a proportion of 1 to 2 mol and the base is usually used in a proportion of 1 to 2 mol with respect to 1 mol of the compound (M4).

The reaction temperature of the reaction is usually in the range of −30 to 100 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

Next, a process for producing a compound represented by the formula (M6) from the compound (M5) (hereinafter referred to as the compound (M6)) (hereinafter also referred to as the fourth process of the production method 1) will be described.

Compound (M6) can be produced by reacting compound (M5) with a compound represented by formula (R2) (hereinafter referred to as compound (R2)) in the presence of a base.

The reaction is usually performed in a solvent.

In the reaction, the compound (R2) is usually used in a proportion of 1 to 2 mol and the base is usually used in a proportion of 1 to 2 mol with respect to 1 mol of the compound (M5).

The reaction temperature of the reaction is usually in the range of −30 to 150 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

Next, the step of producing the compound of the present invention from the compound (M6) (hereinafter also referred to as the fifth step of production method 1) will be described.

The compound of the present invention can be produced by reacting the compound (M6) with a compound represented by the formula (R3) (hereinafter referred to as compound (R3)).

The reaction is usually performed in a solvent.

Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons, nitriles, ethers, ketones, esters, aromatic hydrocarbons, aprotic polar solvents, alcohols, water, and mixtures thereof. Can be mentioned.

In the reaction, a base may be added as necessary. Examples of the base used in the reaction include organic bases, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides, alkaline earth metal hydroxides, metal alkoxides. And alkali metal hydrides.

In the reaction, the compound (R3) is usually used in a proportion of 1 to 10 mol and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (M6).

Manufacturing method 2
The compound of the present invention can also be produced according to the following method.

[Wherein the symbols have the same meaning as described above. ]
First, a step of producing a compound represented by the formula (M7) (hereinafter referred to as compound (M7)) from compound (M6) (hereinafter also referred to as first step of production method 2) will be described.

Compound (M7) can be produced by hydrolyzing compound (M6) in the presence of a base.

The reaction is usually performed in a solvent.

Examples of the solvent used for the reaction include water and a mixture of alcohol and water.

Examples of the base used in the reaction include alkali metal hydroxides and alkaline earth metal hydroxides.

The base is usually used in a ratio of 1 to 10 mol per 1 mol of the compound (M6).

The reaction temperature of the reaction is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

Next, the step of producing the compound of the present invention from the compound (M7) (hereinafter also referred to as the second step of production method 2) will be described.

The compound of the present invention can be produced by reacting the compound (M7) and the compound (R3) in the presence of a condensing agent.

Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons; nitriles; ethers; ketones; esters; aromatic hydrocarbons; aprotic polar solvents; nitrogen-containing aromatics such as pyridine and quinoline. Compounds (hereinafter referred to as nitrogen-containing aromatic compounds); water and mixtures thereof.

Examples of the condensing agent include carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter referred to as carbodiimides), imidazoles such as N, N′-carbonyldiimidazole (hereinafter referred to as “carbodiimide”). ), O- (7-azabenzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate (hereinafter referred to as HATU), etc. Uroniums (hereinafter referred to as uroniums).

The reaction can be carried out by adding a catalyst as necessary. Examples of the catalyst include 1-hydroxybenzotriazole (hereinafter referred to as HOBt) and 1-hydroxyazabenzotriazole (hereinafter referred to as HOAt).

In the reaction, with respect to 1 mole of the compound (M7), the compound (R3) is usually in a proportion of 0.5 to 2 mole, the condensing agent is usually in a proportion of 1 to 5 mole, and the catalyst is usually 0.01 to 1 mole. It is used in the ratio.

The reaction temperature is usually in the range of 0 to 120 ° C. The reaction time is usually in the range of 0.1 to 24 hours.

Production method 3
The compound of the present invention can also be produced according to the following method.

[Wherein the symbols have the same meaning as described above. ]
The method for producing a compound represented by the formula (M9) from the compound (R3) (hereinafter referred to as compound (M9)) can be carried out according to the method described in the first step of production method 1.

The method for producing a compound represented by the formula (M10) from the compound (M9) (hereinafter referred to as compound (M10)) can be carried out according to the method described in the first step of production method 2.

The method for producing the compound of the present invention from the compound (M10) can be carried out according to the method described in the second step of production method 2.

Manufacturing method 4
The compound of the present invention can be produced by reacting compound (M5) with a compound represented by formula (M11) (hereinafter referred to as compound (M11)) in the presence of a base.

[Wherein the symbols have the same meaning as described above. ]
This reaction can be carried out according to the method described in the first step of production method 1.

Manufacturing method 5
Compound (M1) is a compound represented by formula (M12) (hereinafter referred to as compound (M12)) and a compound represented by formula (R4) (hereinafter referred to as compound (R4)). It can be produced according to the method described in the third step of production method 1.

[Wherein the symbols have the same meaning as described above. ]

Manufacturing method 6
Compound (M3) can also be produced according to the following method.

[Wherein the symbols have the same meaning as described above. ]
A compound represented by formula (M13) (hereinafter referred to as compound (M13)) is produced according to the method described in the first step of production method 1, using compound (M12) and compound (M2). can do.

Compound (M3) can be produced according to the method described in the third step of production method 1, using compound (M13) and compound (R4).

Manufacturing method 7
A compound represented by formula (M15) (hereinafter referred to as compound (M15)) is a compound represented by formula (M14) (hereinafter referred to as compound (M14)) and a compound represented by formula (R5) ( Hereinafter, the compound (R5)) can be used according to the method described in Journal of Fluorine Chemistry, 102 (2000) 293-300.

[Wherein R ^2a represents a chlorine atom, a bromine atom or an iodine atom, R ^2b represents a C1-C6 perfluoroalkyl group, and other symbols have the same meanings as described above. ]

Manufacturing method 8
Compound (M15) is produced according to the method described in JP-A-2001-1222836 using a compound represented by formula (M16) (hereinafter referred to as compound (M16)) and compound (R5). You can also

[Wherein the symbols have the same meaning as described above. ]

Manufacturing method 9
The compound represented by the formula (M19) (hereinafter referred to as the compound (M19)) can be produced according to the following method.

[Wherein, R ^1a represents a chlorine atom, a bromine atom or an iodine atom, and the other symbols have the same meaning as described above. ]
A compound represented by formula (M18) (hereinafter referred to as compound (M18)) is obtained by using a compound represented by formula (M17) (hereinafter referred to as compound (M17)) and compound (R5). It can be produced according to the method described in production method 8.

Next, a process for producing a compound represented by the formula (M19) from the compound (M18) (hereinafter referred to as the compound (M19)) (hereinafter also referred to as the second process of Production Example 9) will be described.

Compound (M19) can be produced by using compound (M18) according to the method described in EP2319830.

Manufacturing method 10
Compound (R3) is a compound represented by formula (R6) (hereinafter referred to as compound (R6)) and a compound represented by formula (R7) (hereinafter referred to as compound (R7)). It can be produced according to the method described in the third step of production method 1.

[Wherein the symbols have the same meaning as described above. ]

Manufacturing method 11
Compound (M9) can also be produced according to the following method.

[Wherein the symbols have the same meaning as described above. ]
A compound represented by formula (M20) (hereinafter referred to as compound (M20)) is produced according to the method described in the fourth step of production method 1, using compound (R6) and compound (R2). can do.

Compound (M9) can be produced according to the method described in the third step of production method 1, using compound (M20) and compound (R7).

Production method 12
Compound (M11) can be produced using compound (M10) according to the method described in International Publication No. 2012/003405.

[Wherein the symbols have the same meaning as described above. ]

Production method 13
The compound (Ia) of the present invention can be produced according to the following method.

[Wherein the symbols have the same meaning as described above. ]
The compound represented by the formula (M21) (hereinafter referred to as the compound (M21)) is described in Journal of the American Chemical Society, 1931, vol. 53, p. It can be produced according to the method described in 3143-3146.

A compound represented by formula (M22) (hereinafter referred to as compound (M22)) is produced according to the method described in the third step of production method 1, using compound (M21) and compound (R4). can do.

The compound represented by the formula (M23) (hereinafter referred to as compound (M23)) can be produced according to the method described in International Publication No. 2005/073165 using compound (M22).

A compound represented by formula (M24) (hereinafter referred to as compound (M24)) is produced using compound (M23) and compound (R5) according to the method described in the third step of production method 1. can do.

A compound represented by formula (M25) (hereinafter referred to as compound (M25)) is produced according to the method described in the fourth step of production method 1, using compound (M24) and compound (R2). can do.

The compound represented by formula (M26) (hereinafter referred to as compound (M26)) can be produced according to the method described in the first step of production method 2 using compound (M25).

A compound represented by formula (M27) (hereinafter referred to as compound (M27)) is produced according to the method described in the second step of production method 2, using compound (M26) and compound (R3). can do.

This invention compound (Ia) can be manufactured according to the method of the manufacturing method 7 using a compound (M26) and a compound (R5).

Manufacturing method 14
The compound (Ib) of the present invention can be produced according to the following method.

[Wherein the symbols have the same meaning as described above. ]

A compound represented by formula (M29) (hereinafter referred to as compound (M29)) is obtained by using a compound represented by formula (M28) (hereinafter referred to as compound (M28)) and compound (R1). It can be produced according to the method described in the third step of production method 1.

A compound represented by formula (M30) (hereinafter referred to as compound (M30)) is produced according to the method described in the second step of production method 2, using compound (M29) and compound (M10). can do.

The compound represented by the formula (M31) (hereinafter referred to as compound (M31)) can be produced using the compound (M30) according to the method described in the first step of production method 2.

A compound represented by the formula (M33) (hereinafter referred to as the compound (M33)) was obtained using a compound (M31) and a compound represented by the formula (M32) (hereinafter referred to as the compound (R32)). It can be produced according to the method described in the second step of production method 2.

A compound represented by the formula (M34) (hereinafter referred to as compound (M34)) can be produced according to the method described in production method 8, using compound (M33) and compound (R5). .

This invention compound (Ib) can be manufactured according to the method as described in the 2nd process of the manufacturing method 9 using a compound (M34).

Production method 15
Of the compound (M10) in Production Method 3, Compound (IIa) and Compound (IIb) can be produced according to the following method.

[Wherein the symbols have the same meaning as described above. ]
A compound represented by the formula (M36) (hereinafter referred to as the compound (M36)) is obtained by using a compound represented by the formula (M35) (hereinafter referred to as the compound (M35)) and the compound (R2). It can be produced according to the method described in the fourth step of production method 1.

A compound represented by the formula (IIa) which is one embodiment of the compound (II) (hereinafter referred to as the compound (IIa)) is obtained by using the compound (M36) and the compound (R7) in the third production method 1. It can be produced according to the method described in the process.

A compound represented by formula (IIb) which is another embodiment of compound (II) (hereinafter referred to as compound (IIb)) is obtained by using compound (IIa) which is one embodiment of compound (II). It can be produced according to the method described in the first step of production method 2.

Next, compounds represented by formulas (I-1) to (I-228) [wherein E represents any one of the following substituents (E-1) to (E-108), and “Me” Represents a methyl group and “Et” represents an ethyl group] (hereinafter referred to as the present compound A) as examples of the present compound, but the present invention is not limited thereto.

Compounds of the present invention represented by formulas (I-1) to (I-228) [wherein E represents any of the substituents shown below].

[Substituent E]

Examples of harmful arthropods for which the compounds of the present invention are effective include harmful insects and harmful mites. Specific examples of such harmful arthropods include the following.

Hemiptera pests: Japanese brown planthoppers (Laodelphax striatellus), brown planthoppers (Nilaparvata lugens), white planthoppers (Sogatella furcifera), corn planters (Peregrinus maidis), etc. (Nephotettix nigropictus), Recipe dorsalis, Emporasca onukii, Potato reef hopper (Empoasca fabae), Corn leaf hopper (Dalbulus maidis), Sugarcane ugicine (Suhana) ), Leafhoppers (Cofana spectra), leafhoppers (Nephotettix nigropictus), leafhoppers (Recilia dorsalis), cotton aphids (Aphis gossypii), peach moa Aphids (Myzus persicae), radish aphids (Brevicoryne brassicae), snowy aphids (Aphis spiraecola), tulip beetle aphids (Macrosiphum euphorbiae), potato beetle aphids (Aulacorthum solani), hum ), Peach beetle (Hyalopterus pruni), soybean aphid (Aphis glycines Matsumura), corn aphid (Rhopalosiphum maidis), scallop aphid (Tetraneura nigriabdominalis), grape aphid (Viteusoxvitifiraeae, Pera (Phylloxera devastatrix Pergande), Pecan leaf phylloxera (Phylloxera notabilis pergande), Southern pecan leaf phylloxera (Phylloxera russellae Stoetzel) Stink bug (Scotinophara lurida), Malayan rice black bug (Scotinophara coarctata), blue beetle (Nezara antennata), bark beetle (Eysarcoris parvus), black beetle (Halyomorphastula メ vira) Euskistus heros), Southern green stink bug (Nezara viridula), Red banded stink bug (Piezodorus guildinii), Burrower brown bug (Scaptocoris castanea), Oebalus pugnax, Dichelops melacanthus, etc. Stinkbugs (Leptocorisa chinensis), Helicoptera helicopters (Leptocorisa acuta), Leptocorisa genus, etc. , Chinchi Bugs (Blissus leucopterus leucopterus) and other turtles, whitefly (Trialeurodes vaporariorum), tobacco whitefly (Bemisia tabaci), citrus whitefly (Dialeurodes citri), citrus whitefly (Aleurocanthus spiniferus San Jose scale insect (Comstockaspis perniciosa), citrus snow scale (Unaspis citri), ruby rot beetle (Ceroplastes rubens), Icerya scale insect (Icerya purchasi), Fujicona scale insect (Planococcus kraunhiae), staghorn beetle (Pseuocis) Pseudaulacaspis pentagona), scale insects such as Brevennia リー rehi, Diaphorina citri, psylla pyrisuga, potato topslide (Bacterice) larvae such as rca キ cockerelli), beetles such as Stephanitis 、 nasi, bed bugs such as Cimex lectularius, and Giant Cicada (Quesada。gigas).

Lepidoptera: Chilo suppressalis, Darkheaded stm borer (Chilo polychrysus), Sunpikeza (Tryporyza incertulas), Netloi (Chilo polychrysus), White-meicho (Scirpophaga innotata), Yellow stem borer (Scirpophaga incertulas) Sesamia inferens, Rupela albinella, Cnaphalocrocis medinalis, Marasmia patnalis, Marasmia exigna, Notarcha derogata, Plodia interpunctella, Odalian Hula isla teterrellus), rice case worm (Nymphula depunctalis), Marasmia spp., Hop vine borer (Hydraecia immanis), European corn borer (Ostrinia nubilalis), Lesser cornstalk borer (Elasmopalpus lignosellus), Bean Shoot Borane (Epinotiaapore, Epinotiaatraia) saccharalis), Giant Suga Common moths such as rcane borer (Telchin licus), Spodoptera litura, Spodoptera exigua, Pseudaletia separata, Mamestra brassicae, Sesamia inoptera, Suria inoptera Spodoptera frugiperda, Spodoptera exempta, Tamanayaga (Agrotis ipsilon), Tamanaginuwaba (Plusia nigrisigna), Soybean looper (Pseudoplusia includens), Trichopulsia, Heliothis virescens, etc. Goats such as Velvetbean caterpillar (Anticarsia gammatalis) and Cotton leafworm (Alabama argillacea), white butterflies such as Pieris rapae, genus Adoxofies, Grapholita molesta, Leguminivora glycinivorella , Azukisayamushiga (Matsumuraeses azukivora), apple Coca summer fruit tortrix (Adoxophyes orana fasciata), smaller tea tortrix (Adoxophyes honmai. ), Chamonaki (Homona magnanima), Midelekamonmon (Archips fuscocupreanus), Codialinga (Cydia pomonella), etc., Chanohosoga (Caloptilia theivora), Kinmonhosoga (Phyllonorycter ringoneella), moss borer
(Ecdytolopha aurantiana) and other common moths, Coffee Leaf miner (Leucoptera coffeela), Rionetia sp. ) Potatoes such as potato moth (Phthorimaea operculella), and hitorigers such as Hyphantria cunea.

Common pests: Citrus thrips (Frankliniella occidentalis), Thrips parmi, Scirtothrips dorsalis, Thrips tabaci Thrips such as Kapida thrips (Haplothrips aculeatus), Rice thrips (Stenchaetothrips biformis).

Diptera: Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus and other mosquitoes, Aedes ophegos Genus Anopheles, Chironomid, Musca domestica, Muscina stabulans, etc. Agromyza oryzae), rice leaflet (Hydrellia griseola), tomato leaffly (Liriomyza sativae), beetle leaflet (Liriomyza trifolii), leafhopper (Chromatomyia horticola) and other leafhoppers (Chromatomyia horticola), ryzae and other fruit fly, Dacus cucurbitae, fruit fly such as Ceratitis capitata, Hydrellia philippina, and Fleas such as fleas (Megaselia spiracularis), butterflies such as Clogmia albipunctata, and black fly flies. Crane fly such as Hessian fly (Mayetiola destructor), Oreseolia oryzae, Crane fly such as Diopsis macrophthalma, Common cranefly (Tipula oleracea), European gantry such as Europeanopecranefly (Tipula paludosa).

Coleoptera: Western corn root worm (Diabrotica virgifera virgifera), Southern corn root worm (Diabrotica undecimpunctata howardi), Northern corn root worm (Diabrotica virgifera zeae), Banded cucumber beetle (Diabrotica virgifera zeae) , San Antonio beetle (Diabrotica speciosa), Cucurbit Beetle (Diabrotica speciosa), bean leaf beetle (Cerotoma trifurcata), cereal leaf beetle (Oulema melanopus), cucumber horn beetle (Aulacophora） femoralis), pheasant potato beetle (Phylolsa ラ decor) , Rice beetle (Oulema oryzae), grape colaspis (Colaspis brunnea), corn flare beetle (Chaetocnema pulicaria), potato flare beetle (Epitrix) cucumeris), rice beetle (Dicladispa armigera), Seedcorn beetle (Stenolophus lecontei), Slender seedcorn beetle (Clivinia impressifrons), etc. majalis) carrot beetle (Bothynus gibbosus), Grape Colaspis (Colaspis brunnea), southern Corn leaf beetle (Myochrous denticollis), Holotrichia genus, June beetle (Phyllophaga crinita) (Echinocnemus squameus), rice weevil (Lissorhoptrus oryzophilus), weevil (Sphenophorus venatus), weevil (Anthonomus grandis), Southern Corn Billbug (Sphenophorus scallus) subsignatus) and Sphenophorus levis and other weevil species such as the genus Sphenophorus; Beetles (Anoplophora malasiaca), beetles of Migdolus fryanus, Okinawa beetle (Melanotus okinawensis), spider moth (Agriotes ogurae fuscicollis), legis gris , Anchastus sp., Melanotus sp., Limonius sp., Conoderus sp., Ctenicera sp.), Aedes (Paederus fuscipes), etc.

Insect pests: Tosama locust (Locusta migratoria), Kera (Gryllotalpa africana), Moroccan flying grasshopper (Dociostaurus maroccanus), Australian flying grasshopper (Chortoicetes terminifera), Red-spotted grasshopper (Nomadacris septemfa ciaustal Locna, Loc) melanorhodon), Italian Locust (Calliptamus italicus), Differential grasshopper (Melanoplus differentialis), Twostriped grasshopper (Melanoplus bivittatus), Migratory grasshopper (Melanoplus sanguinipes), Red-Legged grasshopper (Melanoplus sanguinipes), Red-Legged grasshopper (Melanoplus sanguinipes) (Schistocerca gregaria), Yellow-winged locust (Gastrimargus musicus), Spur-throated locust (Austracris guttulosa), Coxenago (Oxya yezoensis), Oxya japonica, Taiwan Chico (Patanga ucci) , House cricket (Acheta domesticus), and Enmakoorogi (Teleogryllus emma), Mormon cricket (Anabrus simplex) or the like crickets acids.

Hymenopteran pests: bees such as Athalia rosae and Japanese bee (Athalia japonica). Fire Ants. Hachiriari such as Brown leaf-cutting ant (Atta capiguara).

Cockroach eye insects: German cockroach (Blattella germanica), Black cockroach (Periplaneta fliginosa), American cockroach (Periplaneta americana), Great cockroach (Periplaneta brunnea), Great cockroach (Blatta orientalis).

Termite insect pests: Yamato termite (Reticulitermes speratus), termite (Coptotermes formosanus), American ant termite (Incisitermes minor), daiko termite (Cryptotermes domesticus), ant-white termite (Odontotermes formosaterm), ants Glyptotermes satsumensis), long term termite (Glyptotermes amamianus), termite termites (Reticulitermes miyatakei), termite termites (Reticulitermes kanmonensis.), termites termites (Nasutitermes takasagoensis), Nitobe Roari (Pericapritermes nitobei), warrior termite (Sinocapritermes mushae), Cornitermes cumulans like.

Acarid pests: Nite spider mite (Tetranychus urticae), Kanzawa spider mite (Tetranychus kanzawai), Scarlet spider mite (Panonychus citri), Apple spider mite (Panonychus ulmi), Oligonicus spp. , Phyllocoptruta citri, tomato rustic mite (Aculops lycopersici), green rustic mite (Calacarus carinatus), green rusted mite (Acaphylla theavagrans), green rust mite (Eriophyes schibalech), ali Dust mites (Polyphagotarsonemus latus), Mite spider mites (Brevipalpus phoenicis), Mite, Mites, Haemaphysalis longicornis, Haemaphysalis flav a), Dermacentor taiwanicus, Dermacentor variabilis, Yamato tick (Ixodes ovatus), Ixodes persulcatus, Black-legged tick (Ixodes scapularis), American thorny tick (Amblyomma america) Tick such as Boophilus microplus, Rhipicephalus sanguineus Kind.

The harmful arthropod control agent of the present invention can contain the compound of the present invention and an inert carrier. The harmful arthropod control agent of the present invention is usually a mixture of the compound of the present invention and an inert carrier such as a solid carrier, a liquid carrier, a gaseous carrier, etc., and if necessary, a surfactant and other adjuvants for formulation. Emulsions, oils, powders, granules, wettable powders, flowables, microcapsules, aerosols, smokers, poisonous baits, resin preparations, shampoos, pastes, foams, carbon dioxide It is formulated into preparations, tablets and the like. These preparations may be used after being processed into mosquito coils, electric mosquito mats, liquid mosquito traps, fumigants, fumigants, sheet preparations, spot-on agents, or oral treatments. Moreover, the harmful arthropod control agent of the present invention can be mixed with other insecticides, acaricides, nematicides, fungicides, plant growth regulators, herbicides and synergists.

The harmful arthropod control agent of the present invention usually contains 0.01 to 95% by weight of the compound of the present invention.

Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur). , Activated carbon, calcium carbonate, hydrated silica, etc.), fine powders and granules of chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, urea, ammonium chloride, etc.), and synthetic resins (polypropylene, polyacrylonitrile, polymethyl methacrylate) Polyester resins such as polyethylene terephthalate, nylon resins such as nylon-6, nylon-11, and nylon-66, polyamide resins, polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-propylene copolymers).

Examples of the liquid carrier include water, alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (Toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, isopropyl myristate, Ethyl oleate, diisopropyl adipate, diisobutyl adipate, propylene glycol monomethyl ether acetate, etc.), nitriles (acetonitrile, isobutyrate) Nitriles), ethers (diisopropyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, etc. ), Acid amides (DMF, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), sulfoxides (dimethylsulfoxide, etc.), propylene carbonate and vegetable oils (soybean oil, cottonseed oil) Etc.).

Examples of the gaseous carrier include fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyethylene glycol fatty acid ester, and anions such as alkyl sulfonate, alkyl benzene sulfonate, and alkyl sulfate. Surfactant is mentioned.

Examples of other adjuvants for preparation include fixing agents, dispersants, colorants and stabilizers, such as casein, gelatin, saccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert- And a mixture of butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

Examples of the base material of the resin preparation include vinyl chloride polymers, polyurethanes, etc., and these base materials include phthalic acid esters (dimethyl phthalate, dioctyl phthalate, etc.) and adipic acid esters as necessary. Further, a plasticizer such as stearic acid may be added. The resin formulation is obtained by kneading the compound in the base material using a normal kneading apparatus, and then molding by injection molding, extrusion molding, press molding, etc., and if necessary, through steps such as molding, cutting, It can be processed into resin preparations such as plate, film, tape, net, and string. These resin preparations are processed, for example, as animal collars, animal ear tags, sheet preparations, attracting strings, or gardening supports.

Examples of the bait base include cereal flour, vegetable oil, sugar, crystalline cellulose and the like, and if necessary, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, and preservatives such as dehydroacetic acid. Additives for preventing accidental eating by children and pets such as pepper powder, pests such as cheese flavor, onion flavor and peanut oil are added.

In the method for controlling harmful arthropods of the present invention, an effective amount of the compound of the present invention is applied directly to harmful arthropods and / or to the place where the harmful arthropods live (plants, soil, households, animal bodies, etc.). Is done. The harmful arthropod control method of the present invention is usually used in the form of the harmful arthropod control agent of the present invention.

When the harmful arthropod control agent of the present invention is used for controlling harmful arthropods in the agricultural field, the application amount is usually 1 to 10,000 g in the amount of the compound of the present invention per 10,000 m ² . When the harmful arthropod control agent of the present invention is formulated into an emulsion, a wettable powder, a flowable agent, etc., it is usually applied by diluting with water so that the active ingredient concentration becomes 0.01 to 10,000 ppm. Granules, powders and the like are usually applied as they are.

These preparations and water dilutions of these preparations may be sprayed directly on harmful arthropods or plants such as crops to be protected from harmful arthropods, and harmful arthropods that inhabit the soil of cultivated land. You may treat to this soil in order to control.

Also, it can be treated by methods such as wrapping a resin preparation processed into a sheet or string around the crop, stretching it around the crop, or laying it on the stock soil.

When the harmful arthropod control agent of the present invention is used for controlling harmful arthropods that live in the house, the amount applied is usually the amount of the compound of the present invention per 1 m ² when treated on the surface. 0.01 to 1000 mg, and when processing in a space, the amount of the compound of the present invention per 1 m ³ of the processing space is usually 0.01 to 500 mg. When the harmful arthropod control agent of the present invention is formulated into an emulsion, a wettable powder, a flowable agent, etc., it is usually diluted with water so that the active ingredient concentration is 0.1 to 10,000 ppm. Apply oils, aerosols, smoke, poison baits, etc. as they are.

When the harmful arthropod control agent of the present invention is used to control ectoparasites of cattle, horses, pigs, sheep, goats, chickens, small animals such as dogs, cats, rats, mice, etc., it is well known in veterinary medicine. Can be used on animals. As a specific method of use, for the purpose of systemic suppression, for example, administration by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) is intended for non-systemic suppression. In this case, for example, an oil agent or an aqueous liquid is sprayed, a pour-on treatment or a spot-on treatment is performed, the animal is washed with a shampoo preparation, or a resin preparation is attached to the animal with a collar or ear tag. The amount of the compound of the present invention when administered to an animal body is usually in the range of 0.1 to 1000 mg per 1 kg body weight of the animal.

Hereinafter, the present invention will be described in more detail with reference to production examples, reference production examples, formulation examples, and test examples, but the present invention is not limited to these examples.

First, reference production examples and production examples are shown for production of the compound of the present invention and compound (II).

Reference production example 1-1
To a mixture of 3.0 g of 1-aminopropionitrile, 0.78 g of 4-dimethylaminopyridine, 12 mL of triethylamine and 49 mL of THF, a mixture of 4.93 mL of methyl chloroglyoxylate and 28 mL of THF was added dropwise at room temperature. Stir for hours. 1N Hydrochloric acid was added to the reaction mixture, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 4.05 g of a compound represented by the following formula (hereinafter referred to as intermediate (M-1)).

¹ H-NMR (DMSO-d6) δ: 9.23 (1H, br s), 3.79 (3H, s), 3.41-3.35 (2H, m), 2.75-2.71 (2H, m).

Reference production example 1-2
To a mixture of 4.00 g of intermediate (M-1) and 47 mL of DMF was added 1.23 g of sodium hydride (purity 60%) under ice-cooling, and the mixture was stirred for 20 minutes. Then, 4.36 g of iodomethane was added, and the mixture was stirred at room temperature for 3 hours. Stir. After adding water to the reaction mixture and extracting with chloroform, the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.06 g of a compound represented by the following formula (hereinafter referred to as intermediate (M-2)).

¹ H-NMR (CDCl ₃ ) δ: (3.91 + 3.90) (3H, s), 3.70-3.63 (2H, m), (3.20 + 3.10) (3H, s), 2.77-2.68 (2H, m).

Reference Production Example 1-3
A mixture of Intermediate (M-2) 1.06 g, 20% aqueous sodium hydroxide solution 1.2 mL, water 0.65 mL and methanol 2 mL was stirred under ice cooling for 1 hour. The reaction mixture was acidified with 12N hydrochloric acid and extracted with chloroform. The organic layer was concentrated under reduced pressure to obtain 0.99 g of a compound represented by the following formula (hereinafter referred to as intermediate (M-3)).

¹ H-NMR (DMSO-d6) δ: 3.60-3.55 (2H, m), (3.00 + 2.89) (3H, s), ((2.88-2.83) + (2.81-2.77)) (2H, m).

Reference production example 1-4
A balloon was attached to the top, and 20.0 g of cyclobutanone, 30.5 g of ammonium chloride, 28.0 g of sodium cyanide, 400 mL of 7M ammonia methanol solution, and 103 g of magnesium sulfate were added to a sealed reaction vessel and stirred at 30 ° C. for 78 hours. did. During the reaction, ammonia gas was bubbled in until bubbling. The insoluble material was collected by filtration, the filtrated product was washed with methanol, and the filtrate was concentrated under reduced pressure. MTBE was added thereto, the precipitate was removed, and the resulting solution was concentrated again under reduced pressure. MTBE was added again, and the precipitate was filtered, and then 284 mL of 1M hydrogen chloride diethyl ether solution was added to the solution under ice cooling, followed by stirring for 30 minutes. The precipitate was collected by filtration and dried to obtain 18.3 g of a compound represented by the following formula (hereinafter referred to as intermediate (M-7)).

¹ H-NMR (DMSO-d6) δ: 9.44-9.32 (2H, m), ((2.63-2.56) + (2.52-2.48) + (2.13-2.02)) (6H, m).

Reference production example 2-1
After stirring a mixture of 5.0 g of 2-fluoro-3-nitro-N- (2,4-dibromo-4-heptafluoroisopropylphenyl) benzamide, 2.03 g of potassium carbonate and 184 mL of methanol at 40 ° C. for 6 hours, Stir at room temperature for 42 hours. After the reaction mixture was concentrated under reduced pressure, the residue was subjected to silica gel column chromatography to obtain 4.93 g of a compound represented by the following formula (hereinafter referred to as intermediate (N-1)).

¹ H-NMR (CDCl ₃ ) δ: 9.35-9.32 (1H, m), 8.48-8.44 (1H, m), 8.17-8.14 (1H, m), 8.10-8.07 (1H, m), 7.95-7.92 ( 1H, m), 7.47-7.41 (1H, m), 4.13 (3H, s).

Reference production example 2-2
A mixture of 4.93 g of intermediate (N-1), 8.00 g of tin (II) chloride, 5.3 mL of 12N hydrochloric acid and 53 mL of ethanol was heated and stirred at 60 ° C. for 1 hour. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, 10% aqueous sodium hydroxide solution was added, the mixture was filtered through Celite (registered trademark), and the residue was washed with MTBE. The filtrate was extracted with MTBE, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 4.50 g of a compound represented by the following formula (hereinafter referred to as intermediate (N-2)). .

¹ H-NMR (CDCl ₃ ) δ: 9.69-9.67 (1H, m), 8.14-8.12 (1H, m), 7.92-7.90 (1H, m), 7.60-7.57 (1H, m), 7.12-7.08 ( 1H, m), 7.01-6.97 (1H, m), (3.97 + 3.21) (3H, s), 3.95-3.91 (2H, m).

Reference production example 2-3
A compound represented by the following formula (hereinafter referred to as intermediate (N-3) is used in accordance with the method described in Reference Production Example 1-1, using intermediate (N-2) instead of 1-aminopropionitrile. .)

1H-NMR (CDCl ₃ ) δ: 9.45-9.42 (1H, m), 9.27-9.25 (1H, m), 8.64-8.60 (1H, m), 8.16-8.14 (1H, m), 8.00-7.97 (1H , m), 7.94-7.92 (1H, m), 7.40-7.36 (1H, m), 4.05-4.02 (6H, m).

Reference production example 2-4
In place of intermediate (M-2), intermediate (N-3) was used, and a compound represented by the following formula (hereinafter referred to as intermediate (N-4) and an intermediate (N-4)) was prepared according to the method described in Reference Production Example 1-3. I wrote.)

1H-NMR (DMSO-d6) δ: 10.61-10.58 (1H, m), 10.01-9.98 (1H, m), 8.44-8.41 (1H, m), 8.16-8.12 (1H, m), 7.98-7.96 ( 1H, m), 7.57-7.53 (1H, m), 7.36-7.31 (1H, m), 3.88 (3H, s).

Reference Production Example 2-5
2- (1,1,2,2-tetrafluoroethoxy) -aniline 10.0 g, sodium dithionite 12.5 g, sodium hydrogen carbonate 6.0 g, tetrabutylammonium hydrogen sulfate 1.8 g, water 50 mL and MTBE 50 mL To the mixture, 28.3 g of heptafluoroisopropyl iodide was added dropwise and stirred at room temperature for 12.5 hours. To the reaction mixture, 8.3 g of sodium dithionite was added and further stirred for 6.5 hours. After extraction with ethyl acetate, the organic layer was washed successively with 5% hydrochloric acid, 5% sodium carbonate solution and saturated brine. After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure to obtain 13.5 g of a compound represented by the following formula (hereinafter referred to as intermediate (Q1-1)).

1H-NMR (CDCl ₃ ) δ: 7.38-7.35 (1H, m), 7.32-7.27 (1H, m), 6.88-6.84 (1H, m), 6.12-5.83 (1H, m).

Reference Production Example 2-6
4.2 g of NBS was added to a mixture of 8.0 g of intermediate (Q-1) and 50 mL of DMF, and the mixture was stirred at room temperature for 2.5 hours. After adding 20% aqueous sodium thiosulfate solution to the reaction mixture, the mixture was extracted with MTBE and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the obtained residue was subjected to silica gel column chromatography to obtain 2.2 g of a compound represented by the following formula (hereinafter referred to as intermediate (Q2-1)).

1H-NMR (CDCl ₃ ) δ: 7.51-7.50 (1H, m), 7.30-7.28 (1H, m), 6.12-5.83 (1H, m), 4.32-4.25 (2H, m).

Reference Production Example 2-7
In place of intermediate (Q-1), 2-methoxy-4-heptafluoroisopropylaniline was used, and a compound represented by the following formula (hereinafter referred to as intermediate (Q2- 2).

1H-NMR (CDCl ₃ ) δ: 7.29-7.27 (1H, m), 6.89-6.87 (1H, m), 4.54-4.46 (2H, m), 3.90 (3H, s).

Reference Production Example 2-8
After dropwise addition of 1.37 g of 3-nitrobenzoyl chloride and 5 mL of DMI to a mixture of 2.81 g of intermediate (Q2-1) and 20 mL of 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as DMI) , And stirred at 100 ° C. for 5 hours. Water was added to the reaction mixture allowed to cool to room temperature, extracted with MTBE, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the obtained residue was subjected to silica gel column chromatography to obtain 2.78 g of a compound represented by the following formula (hereinafter, intermediate Q3-1).

1H-NMR (CDCl ₃ ) δ: 8.75-8.73 (1H, m), 8.49-8.45 (1H, m), 8.27-8.24 (1H, m), 7.83-7.81 (1H, m), 7.78-7.72 (1H , m), 7.58-7.56 (1H, m), 7.50-7.47 (1H, m), 6.03-5.74 (1H, m).

Reference Production Example 2-9
A mixture of 2.78 g of intermediate (Q3-1), 0.77 g of electrolytic iron powder, 0.74 g of ammonium chloride, 72 mL of ethanol and 18 mL of water was stirred at 90 ° C. for 4 hours. Water was added to the reaction mixture which was allowed to cool to room temperature, filtered through celite, and the residue was washed with MTBE. The filtrate was separated, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give a compound represented by the following formula (hereinafter referred to as Intermediate Q4-1). 1.91 g was obtained.

1H-NMR (CDCl ₃ ) δ: 7.78-7.75 (1H, m), 7.54-7.52 (1H, m), 7.46-7.38 (1H, m), 7.30-7.19 (3H, m), 6.90-6.86 (1H , m), 6.01-5.72 (1H, m), 3.91-3.81 (2H, m).

Reference Production Example 2-10
To a mixture of 7.0 g of N- [2-bromo-6- (difluoromethoxy) -4- (heptafluoroisopropyl) phenyl] -3-nitrobenzamide and 70 mL of DMF was added 604 mg of 60% sodium hydride (oily) under ice-cooling. Added and stirred for 25 minutes. To this mixture, 2.15 g of methyl iodide was added, and the mixture was further stirred for 1 hour. The reaction mixture was added to ice water and extracted with MTBE, and then the organic layer was washed successively with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and the obtained residue was subjected to silica gel column chromatography to obtain a compound represented by the following formula (hereinafter referred to as intermediate Q3-8). 0 g was obtained.

1H-NMR (CDCl ₃ ) δ: 8.20-8.13 (2H, m), 7.73-7.70 (1H, m), 7.68-7.66 (1H, m), 7.43-7.37 (1H, m), 7.30-7.28 (1H , m), 6.76-6.39 (1H, m), (3.38 + 3.26) (1H, s).

The intermediates produced by the production methods according to the methods described in Reference Production Examples 2-1 to 2-10 and the physical properties thereof are shown below.

Intermediate (N-5)

¹ H-NMR (CDCl ₃ ) δ: 9.07-9.04 (1H, m), 8.32-8.29 (1H, m), 7.91-7.87 (1H, m), 7.81-7.78 (1H, m), 7.60-7.52 ( 2H, m), 7.40-7.38 (2H, m), 4.03 (3H, s), 2.38 (6H, s).

Intermediate (N-6)

¹ H-NMR (DMSO-d6) δ: 10.94-10.92 (1H, m), 10.00-9.98 (1H, m), 8.39-8.36 (1H, m), 7.98-7.94 (1H, m), 7.78-7.74 (1H, m), 7.56-7.49 (1H, m), 7.46-7.43 (2H, m), 2.28 (6H, s).

Intermediate (N-7)

¹ H-NMR (CDCl ₃ ) δ: 9.54-9.51 (1H, m), 8.29-8.25 (1H, m), 7.88-7.86 (1H, m), 7.76-7.74 (1H, m), 7.35-7.31 ( 2H, m), ((4.44-4.33) + (3.57-3.47)) (2H, m), 4.18-3.99 (3H, m), 3.70 (3H, s), 1.31-1.20 (3H, m).

Intermediate (N-8)

¹ H-NMR (CDCl ₃ ) δ: 9.37-9.34 (1H, m), 8.24-8.20 (1H, m), 7.87-7.85 (1H, m), 7.75-7.74 (1H, m), 7.38-7.31 ( 2H, m), ((4.36-4.26) + (3.62-3.51)) (2H, m), 4.07 (3H, s), 1.30-1.25 (3H, m).

Intermediate (N-9)

¹ H-NMR (CDCl ₃ ) δ: 9.50-9.47 (1H, m), 8.79-8.76 (1H, m), 8.64-8.60 (1H, m), 7.98-7.94 (1H, m), 7.43-7.37 ( 3H, m), 4.06-4.03 (6H, m), 2.41 (6H, s).

Intermediate (N-10)

¹ H-NMR (CDCl ₃ ) δ: 9.60-9.57 (1H, m), 8.77-8.74 (1H, m), 8.57-8.53 (1H, m), 8.01-7.97 (1H, m), 7.44-7.38 ( 3H, m), 4.06-4.04 (3H, m), 2.40 (6H, s).

Intermediate (N-11)

¹ H-NMR (CDCl ₃ ) δ: 9.25-9.21 (1H, m), 8.62-8.57 (1H, m), 7.97-7.92 (1H, m), 7.85-7.79 (1H, m), 7.44-7.38 ( 3H, m), 4.05 (3H, s), 2.40 (6H, s).

Intermediate (N-12)

¹ H-NMR (CDCl ₃ ) δ: 9.37-9.32 (1H, m), 8.56-8.49 (1H, m), 8.02-7.95 (1H, m), 7.87-7.81 (1H, m), 7.46-7.38 ( 3H, m), 2.41-2.38 (6H, m).

Intermediate (N-13)

¹ H-NMR (CDCl ₃ ) δ: 9.23-9.19 (1H, m), 8.64-8.59 (1H, m), 8.20-8.14 (2H, m), 7.97-7.92 (2H, m), 7.42-7.37 ( 1H, m), 4.02 (3H, s).

Intermediate (N-14)

¹ H-NMR (DMSO-d6) δ: 10.78-10.76 (1H, m), 10.56-10.54 (1H, m), 8.44-8.42 (1H, m), 7.99-7.96 (1H, m), 7.89-7.83 (1H, m), 7.59-7.53 (1H, m), 7.42-7.36 (1H, m).

A compound represented by formula (Q3).

In the formula, R ¹ , R ³ , R ⁴ , X ^a1 , X ^a2 , X ^a3 and X ^a4 represent the substituents described in [Table 1] below.

Intermediate (Q3-2)
¹ H-NMR (CDCl ₃ ) δ: 8.82-8.80 (1H, m), 8.51-8.47 (1H, m), 8.36-8.32 (1H, m), 7.80-7.75 (1H, m), 7.60-7.55 ( 2H, m), 7.17-7.15 (1H, m), 3.94 (3H, s).

Intermediate (Q3-3)
¹ H-NMR (CDCl ₃ ) δ: 7.98-7.95 (1H, m), 7.83-7.79 (2H, m), 7.53-7.46 (2H, m), 7.30-7.27 (1H, m), 6.64 (1H, t), 2.67 (3H, s).

Intermediate (Q3-4)
¹ H-NMR (CDCl ₃ ) δ: 8.78-8.76 (1H, m), 8.50-8.47 (1H, m), 8.30-8.27 (1H, m), 7.79-7.74 (1H, m), 7.67-7.65 ( 1H, m), 7.59-7.57 (1H, m), 7.20-7.18 (1H, m), 4.49 (2H, q).

Intermediate (Q3-5)
¹ H-NMR (CDCl ₃ ) δ: 8.81-8.79 (1H, m), 8.55-8.52 (1H, m), 8.35-8.31 (1H, m), 7.93-7.91 (1H, m), 7.84-7.79 ( 1H, m), 7.66-7.62 (2H, m).

Intermediate (Q3-6)
¹ H-NMR (CDCl ₃ ) δ: 9.41-9.39 (1H, m), 8.50-8.46 (1H, m), 8.38-8.35 (1H, m), 8.10-8.07 (1H, m), 7.97-7.95 ( 1H, m), 7.47-7.42 (1H, m), 4.14 (3H, s).

Intermediate (Q3-7)
¹ H-NMR (CDCl ₃ ) δ: 8.79-8.76 (2H, m), 8.52-8.48 (2H, m), 8.26-8.22 (1H, m), 7.82-7.77 (1H, m), 7.62-7.59 ( 1H, m), 7.49-7.47 (1H, m), 6.71 (1H, t).

Intermediate (Q3-9)
¹ H-NMR (CDCl ₃ ) δ: 9.08-9.04 (1H, m), 8.51-8.46 (1H, m), 8.24-8.14 (1H, m), 7.83-7.81 (1H, m), 7.55-7.51 ( 1H, m), 7.48-7.42 (1H, m), 6.61 (1H, t).

Intermediate (Q3-10)
¹ H-NMR (CDCl ₃ ) δ: 8.59-8.57 (1H, m), 8.22-8.18 (1H, m), 8.05-8.00 (1H, m), 7.83-7.81 (1H, m), 7.71-7.68 ( 1H, m), 7.54-7.51 (1H, m), 6.59 (1H, t).

Intermediate (Q3-11)
¹ H-NMR (CDCl ₃ ) δ: 8.65-8.63 (1H, m), 8.48-8.46 (1H, m), 8.27-8.26 (1H, m), 7.83-7.81 (1H, m), 7.67-7.65 ( 1H, m), 7.54-7.52 (1H, m), 6.59 (1H, t).

Intermediate (Q3-12)
¹ H-NMR (CDCl ₃ ) δ: 8.70-8.68 (1H, m), 8.63-8.62 (1H, m), 8.43-8.41 (1H, m), 7.83-7.81 (1H, m), 7.67-7.64 ( 1H, m), 7.54-7.52 (1H, m), 6.59 (1H, t).

Intermediate (Q3-13)
¹ H-NMR (CDCl ₃ ) δ: 8.67-8.63 (1H, m), 8.28-8.23 (1H, m), 7.83-7.80 (1H, m), 7.65-7.62 (1H, m), 7.53-7.47 ( 2H, m), 6.59 (1H, t).

Intermediate (Q3-14)
¹ H-NMR (CDCl ₃ ) δ: 8.45-8.42 (1H, m), 8.20-8.15 (1H, m), 7.81-7.78 (1H, m), 7.63-7.60 (1H, m), 7.52-7.49 ( 1H, m), 7.27-7.22 (1H, m), 6.58 (1H, t), 4.07 (3H, s).

Intermediate (Q3-15)
¹ H-NMR (CDCl ₃ ) δ: 7.84-7.82 (1H, m), 7.75-7.72 (1H, m), 7.57-7.51 (2H, m), 7.28-7.24 (1H, m), 6.64 (1H, t), 2.64 (3H, s).

A compound represented by formula (Q4).

In the formula, R ¹ , R ³ , R ⁴ , X ^a1 , X ^a2 , X ^a3 and X ^a4 represent the substituents described in [Table 2] below.

Intermediate (Q4-2)
¹ H-NMR (CDCl ₃ ) δ: 7.53-7.49 (2H, m), 7.32-7.28 (3H, m), 7.13-7.11 (1H, m), 6.94-6.89 (1H, m), 3.92-3.87 ( 5H, m).

Intermediate (Q4-3)
¹ H-NMR (CDCl ₃ ) δ: 7.80-7.78 (1H, m), 7.52-7.50 (1H, m), 7.32-7.29 (1H, m), 7.16-7.11 (1H, m), 7.07-7.03 ( 1H, m), 6.84-6.45 (2H, m), 3.83-3.79 (2H, m).

Intermediate (Q4-4)
¹ H-NMR (CDCl ₃ ) δ: 7.66-7.64 (1H, m), 7.51-7.49 (1H, m), 7.35-7.25 (3H, m), 7.21-7.19 (1H, m), 6.95-6.91 ( 1H, m), 4.50 (2H, q), 3.92-3.89 (2H, m).

Intermediate (Q4-5)
¹ H-NMR (CDCl ₃ ) δ: 7.89-7.87 (1H, m), 7.61-7.55 (2H, m), 7.36-7.25 (3H, m), 6.96-6.92 (1H, m), 3.94-3.90 ( 2H, m).

Intermediate (Q4-6)
¹ H-NMR (CDCl ₃ ) δ: 9.76-9.74 (1H, m), 8.36-8.33 (1H, m), 7.95-7.93 (1H, m), 7.61-7.58 (1H, m), 7.13-7.08 ( 1H, m), 7.01-6.97 (1H, m), 4.04-3.88 (5H, m).

Intermediate (Q4-7)
¹ H-NMR (CDCl ₃ ) δ: 8.82-8.79 (1H, m), 8.44-8.41 (1H, m), 7.58-7.53 (1H, m), 7.45-7.43 (1H, m), 7.35-7.29 ( 1H, m), 7.25-7.24 (1H, m), 7.21-7.18 (1H, m), 6.94-6.90 (1H, m), 6.65 (1H, t), 3.95-3.88 (2H, m).

Intermediate (Q4-8)
¹ H-NMR (CDCl ₃ ) δ: 7.80-7.76 (1H, m), 7.57-7.54 (1H, m), 7.51-7.47 (1H, m), 7.32-7.20 (3H, m), 6.91-6.87 ( 1H, m), 3.87 (2H, br s).

Intermediate (Q4-9)
¹ H-NMR (CDCl ₃ ) δ: 8.34-8.27 (1H, m), 7.80-7.78 (1H, m), 7.52-7.49 (1H, m), 7.43-7.39 (1H, m), 7.06-7.00 ( 1H, m), 6.87-6.82 (1H, m), 6.60 (1H, t), 3.80-3.74 (2H, m).

Intermediate (Q4-10)
¹ H-NMR (CDCl ₃ ) δ: 7.80-7.78 (1H, m), 7.51-7.48 (2H, m), 7.01-6.99 (1H, m), 6.95-6.91 (1H, m), 6.78-6.40 ( 2H, m), 4.03-4.00 (2H, m).

Intermediate (Q4-11)
¹ H-NMR (CDCl ₃ ) δ: 7.80-7.77 (1H, m), 7.53-7.39 (2H, m), 7.21-7.19 (1H, m), 7.10-7.08 (1H, m), 6.89-6.87 ( 1H, m), 6.58 (1H, t), 3.99-3.96 (2H, m).

Intermediate (Q4-12)
¹ H-NMR (CDCl ₃ ) δ: 7.80-7.78 (1H, m), 7.52-7.46 (2H, m), 7.36-7.34 (1H, m), 7.15-7.13 (1H, m), 7.06-7.04 ( 1H, m), 6.59 (1H, t), 3.98-3.95 (2H, m).

Intermediate (Q4-13)
¹ H-NMR (CDCl ₃ ) δ: 7.79-7.77 (1H, m), 7.52-7.48 (2H, m), 7.40-7.37 (1H, m), 7.26-7.21 (1H, m), 7.14-7.08 ( 1H, m), 6.59 (1H, t), 3.97-3.94 (2H, m).

Intermediate (Q4-14)
¹ H-NMR (CDCl ₃ ) δ: 7.81-7.78 (1H, m), 7.55-7.51 (2H, m), 7.36-7.31 (2H, m), 6.91-6.88 (1H, m), 6.62 (1H, t), 4.10-3.95 (5H, m).

Intermediate (Q4-15)
¹ H-NMR (CDCl ₃ ) δ: 7.81-7.79 (1H, m), 7.52-7.50 (1H, m), 7.23-7.22 (1H, m), 6.83-6.45 (3H, m), 3.95-3.92 ( 2H, m), 2.26 (3H, s).

A compound represented by formula (Q5).

R ¹ , R ³ , R ⁴ , X ^a1 , X ^a2 , X ^a3 and X ^a4 in the formula represent the substituents described in [Table 3] below.

Intermediate (Q5-1)
¹ H-NMR (DMSO-d6) δ: 11.03-10.98 (1H, m), 10.27-10.22 (1H, m), 8.32-8.28 (1H, m), 8.10-8.07 (1H, m), 7.95-7.91 (1H, m), 7.78-7.69 (2H, m), 7.56-7.50 (1H, m), 6.85-6.55 (1H, m), 3.86 (3H, s).

Intermediate (Q5-2)
¹ H-NMR (CDCl ₃ ) δ: 9.04-9.01 (1H, m), 8.25-8.23 (1H, m), 7.97-7.94 (1H, m), 7.82-7.79 (1H, m), 7.60-7.53 ( 3H, m), 7.15-7.13 (1H, m), 4.04 (3H, s), 3.93 (3H, s).

Intermediate (Q5-3)
¹ H-NMR (CDCl ₃ ) δ: 8.94-8.92 (1H, m), 8.18-8.14 (1H, m), 7.82-7.80 (1H, m), 7.53-7.49 (2H, m), 7.43-7.38 ( 1H, m), 7.36-7.34 (1H, m), 6.64 (1H, t), 4.01 (3H, s), 2.49 (3H, s).

Intermediate (Q5-4)
¹ H-NMR (CDCl ₃ ) δ: 9.05-9.03 (1H, m), 8.25-8.22 (1H, m), 7.99-7.95 (1H, m), 7.80-7.76 (1H, m), 7.67-7.65 ( 1H, m), 7.63-7.56 (2H, m), 7.22-7.20 (1H, m), 4.50 (2H, q), 4.03 (3H, s).

Intermediate (Q5-5)
¹ H-NMR (CDCl ₃ ) δ: 9.07-9.04 (1H, m), 8.30-8.28 (1H, m), 7.96-7.92 (1H, m), 7.91-7.89 (1H, m), 7.82-7.78 ( 1H, m), 7.74-7.72 (1H, m), 7.63-7.58 (2H, m), 4.04 (3H, s).

Intermediate (Q5-6)
¹ H-NMR (CDCl ₃ ) δ: 9.45-9.41 (1H, m), 9.35-9.33 (1H, m), 8.64-8.61 (1H, m), 8.37-8.35 (1H, m), 8.02-7.99 ( 1H, m), 7.97-7.95 (1H, m), 7.41-7.36 (1H, m), 4.05 (3H, s), 4.03 (3H, s).

Intermediate (Q5-7)
¹ H-NMR (CDCl ₃ ) δ: 9.03-9.00 (1H, m), 8.78-8.74 (1H, m), 8.48-8.45 (1H, m), 8.24-8.21 (1H, m), 7.92-7.88 ( 1H, m), 7.72-7.67 (1H, m), 7.59-7.52 (2H, m), 7.46-7.43 (1H, m), 6.68 (1H, t), 4.01 (3H, s).

Intermediate (Q5-8)
¹ H-NMR (CDCl ₃ ) δ: ((8.99-8.97) + (8.75-8.72)) (1H, m), ((7.99-7.97) + (7.85-7.83) + (7.79-7.75) + (7.63 -7.60) + (7.56-7.41) + (7.36-7.19)) (6H, m), 7.01-6.39 (1H, m), (4.02 + 3.97 + 3.37 + 3.27) (6H, s).

Intermediate (Q5-9)
¹ H-NMR (CDCl ₃ ) δ: 9.03-9.00 (1H, m), 8.31-8.25 (2H, m), 8.10-8.07 (1H, m), 7.81-7.80 (1H, m), 7.53-7.50 ( 1H, m), 7.33-7.26 (1H, m), 6.60 (1H, t), 4.00 (3H, s).

Intermediate (Q5-10)
¹ H-NMR (CDCl ₃ ) δ: 9.11-9.09 (1H, m), 7.97-7.95 (1H, m), 7.83-7.78 (2H, m), 7.75-7.73 (1H, m), 7.52-7.50 ( 1H, m), 7.49-7.45 (1H, m), 6.59 (1H, t), 4.01 (3H, s).

Intermediate (Q5-11)
¹ H-NMR (CDCl ₃ ) δ: 9.04-9.00 (1H, m), 8.11-8.08 (1H, m), 7.94-7.90 (1H, m), 7.80-7.69 (3H, m), 7.50-7.45 ( 1H, m), 6.55 (1H, t), 3.97 (3H, s).

Intermediate (Q5-12)
¹ H-NMR (CDCl ₃ ) δ: 9.07-9.05 (1H, m), 8.23-8.21 (1H, m), 8.13-8.11 (1H, m), 7.93-7.91 (1H, m), 7.84-7.82 ( 1H, m), 7.75-7.73 (1H, m), 7.55-7.53 (1H, m), 6.62 (1H, t), 4.03 (3H, s).

Intermediate (Q5-13)
¹ H-NMR (CDCl ₃ ) δ: 9.25-9.21 (1H, m), 9.02-8.98 (1H, m), 7.88-7.82 (2H, m), 7.81-7.78 (1H, m), 7.52-7.49 ( 1H, m), 7.36-7.29 (1H, m), 6.60 (1H, t), 4.02 (3H, s).

Intermediate (Q5-14)
¹ H-NMR (CDCl ₃ ) δ: 9.60-9.57 (1H, m), 9.04-9.02 (1H, m), 7.93-7.89 (2H, m), 7.82-7.80 (1H, m), 7.54-7.51 ( 1H, m), 7.11-7.08 (1H, m), 6.63 (1H, t), 4.06 (3H, s), 4.03 (3H, s).

Intermediate (Q5-15)
¹ H-NMR (CDCl ₃ ) δ: 9.03-9.00 (1H, m), 8.15-8.11 (1H, m), 7.83-7.80 (1H, m), 7.53-7.50 (1H, m), 7.30-7.28 ( 1H, m), 7.21-7.18 (1H, m), 6.63 (1H, t), 4.02 (3H, s), 2.46 (3H, s).

Intermediate (Q5-16)
¹ H-NMR (CDCl ₃ ) δ: 9.03-9.00 (1H, m), 8.27-8.25 (1H, m), 7.93-7.90 (1H, m), 7.81-7.75 (2H, m), 7.69-7.67 ( 1H, m), 7.59-7.55 (1H, m), 7.53-7.51 (1H, m), 6.61 (1H, t), 4.01 (3H, s).

Intermediate (Q5-17)
¹ H-NMR (DMSO-d6) δ: 11.08-11.05 (1H, m), 10.99-10.93 (1H, m), 8.39-8.36 (1H, m), 8.30-8.28 (1H, m), 8.05-8.02 (1H, m), 8.00-7.97 (1H, m), 7.85-7.82 (1H, m), 7.62-7.56 (1H, m), 3.87 (3H, s).

Intermediate (Q5-18)
¹ H-NMR (CDCl ₃ ) δ: 9.23-9.18 (1H, m), 8.65-8.60 (1H, m), 8.38-8.35 (1H, m), 8.23-8.16 (1H, m), 7.98-7.93 ( 2H, m), 7.44-7.38 (1H, m), 4.03 (3H, s).

A compound represented by formula (Q6).

R ¹ , R ³ , R ⁴ , X ^a1 , X ^a2 , X ^a3 and X ^a4 in the formula represent the substituents described in [Table 4] below.

Intermediate (Q6-1)
¹ H-NMR (DMSO-d6) δ: 10.91-10.88 (1H, m), 10.25-10.22 (1H, m), 8.35-8.32 (1H, m), 8.10-8.07 (1H, m), 7.96-7.91 (1H, m), 7.76-7.70 (2H, m), 7.55-7.49 (1H, m), 6.86-6.55 (1H, m).

Intermediate (Q6-2)
¹ H-NMR (CDCl ₃ ) δ: 9.17-9.13 (1H, m), 8.27-8.25 (1H, m), 7.94-7.90 (1H, m), 7.86-7.83 (1H, m), 7.64-7.53 ( 3H, m), 7.16-7.13 (1H, m), 3.93 (3H, s).

Intermediate (Q6-3)
¹ H-NMR (DMSO-d6) δ: 10.52-10.50 (1H, m), 10.43-10.41 (1H, m), 7.92-7.90 (1H, m), 7.59-7.22 (5H, m), 2.28 (3H , s).

Intermediate (Q6-4)
¹ H-NMR (CDCl ₃ ) δ: 9.24-9.20 (1H, m), 8.27-8.23 (1H, m), 7.94-7.90 (1H, m), 7.81-7.77 (1H, m), 7.68-7.64 ( 2H, m), 7.61-7.56 (1H, m), 7.21-7.19 (1H, m), 4.50 (2H, q).

Intermediate (Q6-5)
¹ H-NMR (CDCl ₃ ) δ: 9.22-9.20 (1H, m), 8.30-8.29 (1H, m), 7.95-7.89 (2H, m), 7.85-7.81 (1H, m), 7.72-7.70 ( 1H, m), 7.65-7.60 (2H, m).

Intermediate (Q6-6)
¹ H-NMR (DMSO-d6) δ: 10.54-10.51 (1H, m), 10.31-10.29 (1H, m), 8.51-8.49 (1H, m), 8.47-8.43 (1H, m), 7.97-7.94 (1H, m), 7.47-7.44 (1H, m), 7.31-7.27 (1H, m), 3.87 (3H, s).

Intermediate (Q6-7)
¹ H-NMR (DMSO-d6) δ: 9.95-9.91 (1H, m), 9.20-9.17 (1H, m), 7.38-7.35 (1H, m), 7.11-7.07 (1H, m), 7.00-6.95 (1H, m), 6.75-6.71 (1H, m), 6.68-6.63 (1H, m), 6.58-6.50 (2H, m), 6.29 (1H, t).

Intermediate (Q6-8)
¹ H-NMR (CDCl ₃ ) δ: ((9.18-9.14) + (8.94-8.88)) (1H, m), ((7.98-7.96) + (7.87-7.85) + (7.83-7.76) + (7.67 -7.64) + (7.61-7.50) + (7.40-7.25)) (6H, m), 6.80-6.41 (1H, m), (3.40 + 3.28) (3H, s).

Intermediate (Q6-9)
¹ H-NMR (DMSO-d6) δ: 10.00-9.97 (1H, m), 9.43-9.40 (1H, m), 7.21-7.16 (1H, m), 6.98-6.93 (1H, m), 6.92-6.89 (1H, m), 6.55-6.16 (3H, m).

Intermediate (Q6-10)
¹ H-NMR (DMSO-d6) δ: 10.13-10.10 (1H, m), 9.51-9.49 (1H, m), 7.24-7.21 (1H, m), 6.91-6.86 (2H, m), 6.57-6.52 (2H, m), 6.32 (1H, t).

Intermediate (Q6-11)
¹ H-NMR (CDCl ₃ ) δ: 9.34-9.29 (1H, m), 8.10-8.04 (1H, m), 7.98-7.94 (1H, m), 7.86-7.69 (3H, m), 7.52-7.48 ( 1H, m), 6.58 (1H, t).

Intermediate (Q6-12)
¹ H-NMR (CDCl ₃ ) δ: 9.23-9.20 (1H, m), 8.19-8.15 (2H, m), 7.95-7.93 (1H, m), 7.84-7.82 (1H, m), 7.69-7.66 ( 1H, m), 7.55-7.53 (1H, m), 6.62 (1H, t).

Intermediate (Q6-13)
¹ H-NMR (CDCl ₃ ) δ: 9.35-9.30 (1H, m), 8.94-8.89 (1H, m), 7.88-7.73 (3H, m), 7.53-7.48 (1H, m), 7.38-7.31 ( 1H, m), 6.59 (1H, t).

Intermediate (Q6-14)
¹ H-NMR (CDCl ₃ ) δ: 9.70-9.67 (1H, m), 8.97-8.95 (1H, m), 7.93-7.89 (1H, m), 7.83-7.81 (1H, m), 7.68-7.66 ( 1H, m), 7.55-7.53 (1H, m), 7.14-7.10 (1H, m), 6.64 (1H, t), 4.08 (3H, s).

Intermediate (Q6-15)
¹ H-NMR (DMSO-d6) δ: 10.62-10.59 (1H, m), 10.46-10.43 (1H, m), 7.90-7.87 (1H, m), 7.60-7.22 (3H, m), 7.19-7.14 (1H, m), 2.24 (3H, s).

Intermediate (Q6-16)
¹ H-NMR (CDCl ₃ ) δ: 9.20-9.14 (1H, m), 8.28-8.24 (1H, m), 7.92-7.87 (1H, m), 7.82-7.77 (2H, m), 7.71-7.66 ( 1H, m), 7.62-7.55 (1H, m), 7.53-7.49 (1H, m), 6.60 (1H, t).

Intermediate (Q6-17)
¹ H-NMR (DMSO-d6) δ: 10.95-10.93 (2H, m), 8.41-8.39 (1H, m), 8.31-8.28 (1H, m), 8.05-8.03 (1H, m), 8.01-7.97 (1H, m), 7.83-7.79 (1H, m), 7.61-7.55 (1H, m).

Intermediate (Q6-18)
¹ H-NMR (DMSO-d6) δ: 10.76-10.74 (1H, m), 10.41-10.38 (1H, m), 8.53-8.50 (1H, m), 8.17-8.09 (1H, m), 7.97-7.94 (1H, m), 7.51-7.46 (1H, m), 7.40-7.35 (1H, m).

A compound represented by formula (Q7-1).

Intermediate (Q7-1)
¹ H-NMR (CDCl ₃ ) δ: 7.54-7.52 (1H, m), 7.33-7.31 (1H, m), 4.75 (2H, br s).

A compound represented by the formula (Q7-2).

Intermediate (Q7-2)
¹ H-NMR (CDCl ₃ ) δ: 8.78-8.75 (1H, m), 8.51-8.46 (1H, m), 8.31-8.26 (1H, m), 7.84-7.80 (1H, m), 7.80-7.74 ( 1H, m), 7.67-7.62 (1H, m), 7.61-7.59 (1H, m).

A compound represented by the formula (Q7-3).

Intermediate (Q7-3)
¹ H-NMR (CDCl ₃ ) δ: 7.80-7.76 (1H, m), 7.57-7.54 (1H, m), 7.51-7.47 (1H, m), 7.32-7.20 (3H, m), 6.91-6.87 ( 1H, m), 3.87 (2H, br s).

A compound represented by the formula (Q7-4).

Intermediate (Q7-4)
¹ H-NMR (DMSO-d6) δ: 11.03-10.98 (1H, m), 10.49-10.45 (1H, m), 8.32-8.26 (2H, m), 7.95-7.90 (2H, m), 7.75-7.71 (1H, m), 7.56-7.49 (1H, m), 3.84 (3H, s).

A compound represented by formula (Q7-5).

Intermediate (Q7-5)
¹ H-NMR (DMSO-d6) δ: 10.95-10.92 (1H, m), 10.49-10.47 (1H, m), 8.37-8.35 (1H, m), 8.32-8.30 (1H, m), 7.98-7.93 (2H, m), 7.76-7.72 (1H, m), 7.57-7.52 (1H, m).

Production Example 1
3- (oxaloamino) -N- [2-bromo-6- (difluoromethoxy) -4- (heptafluoroisopropyl) phenyl] benzamide 0.20 g, 1-aminocyclopropanecarbonitrile hydrochloride 40 mg, HATU 0.13 g, A mixture of 0.12 mL diisopropylethylamine and 4 mL DMF was stirred at room temperature for 9 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the obtained residue was subjected to silica gel column chromatography to obtain 0.17 g of a compound shown below (hereinafter referred to as the present compound 1a-1).

¹ H-NMR (CDCl ₃ ) δ: 9.27-9.25 (1H, m), 8.26-8.24 (1H, m), 7.96-7.94 (1H, m), 7.86-7.83 (1H, m), 7.81-7.79 ( 1H, m), 7.79-7.75 (1H, m), 7.65-7.64 (1H, m), 7.59-7.54 (1H, m), 7.52-7.51 (1H, m), 6.60 (1H, t), 1.71- 1.67 (2H, m), 1.43-1.38 (2H, m).

Production Example 2
3-amino-N- [2-bromo-6- (difluoromethoxy) -4-heptafluoroisopropylphenyl] benzamide 0.30 g, 96 mg postscript intermediate P-3, HATU 0.22 g, diisopropylethylamine 99 μL and DMF 19 mL Was stirred at 50 ° C. for 4 hours. Water was added to the reaction mixture allowed to cool to room temperature, extracted with methyl-tert-butyl ether, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the obtained residue was subjected to silica gel column chromatography to obtain 0.35 g of a compound shown below (hereinafter referred to as the present compound 1a-2).

¹ H-NMR (CDCl ₃ ) δ: ((9.38-9.33) + (9.16-9.11)) (1H, m), 8.31-8.27 (1H, m), 7.92-7.87 (1H, m), 7.85-7.74 (3H, m), 7.61-7.52 (2H, m), 6.83-6.44 (1H, m), (3.56 + 3.21) (3H, s), 1.75-1.69 (2H, m), 1.45-1.39 (2H, m).

Production Example 3
To a mixture of 0.46 g of the compound 1a-12 of the present invention and 14 mL of DMF was added 95 mg of 60% sodium hydride (oil) under ice cooling, and the mixture was stirred for 10 minutes. To this mixture was added 0.39 g of methyl iodide, and the mixture was stirred at 40 ° C. for 2 hours. Water was added to the reaction mixture cooled to room temperature, and extracted with MTBE. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and the obtained residue was subjected to silica gel column chromatography to give 0.38 g of the following compound (hereinafter referred to as the present compound 1a-15). Obtained.

¹ H-NMR (CDCl ₃ ) δ: ((7.83-7.81) + (7.69-7.54) + (7.52-7.47) + (7.40-7.36) + (7.31-7.18) + (7.06-7.01) + (6.75- 6.25)) (7H, m), ((3.44-2.87) + (2.82-2.41) + (2.29-1.73)) (15H, m).

Production Example 4
To a mixture of 3.0 g of 1-aminocyclopropanecarbonitrile hydrochloride, 0.47 g of 4-dimethylaminopyridine, 10.7 mL of triethylamine and 29 mL of THF, a mixture of 2.91 mL of methyl chloroglyoxylate and 6 mL of THF was added dropwise under ice cooling. The mixture was stirred at room temperature for 3 hours. 1N Hydrochloric acid was added to the reaction mixture, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 3.12 g of a compound represented by the following formula (hereinafter referred to as intermediate P-1).

¹ H-NMR (DMSO-d6) δ: 9.86 (1H, br s), 3.76 (3H, s), 1.56-1.51 (2H, m), 1.29-1.24 (2H, m).

Production Example 5
2. Add 0.63 g of sodium hydride (purity 60%) under ice-cooling to a mixture of 20 g of intermediate P-1 and DMF 24 mL, stir for 20 minutes, then add 2.23 g of iodomethane, and stir at room temperature for 1 hour did. After adding water to the reaction mixture and extracting with chloroform, the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.60 g of a compound represented by the following formula (hereinafter referred to as intermediate P-2).

¹ H-NMR (CDCl ₃ ) δ: (3.96 + 3.89) (3H, s), (3.11 + 3.09) (3H, s), 1.69-1.56 (2H, m), 1.43-1.37 (2H, m).

Production Example 6
A mixture of 1.60 g of intermediate P-2, 1.7% of 20% aqueous sodium hydroxide, 1 mL of water and 3 mL of methanol was stirred for 1 hour under ice cooling. The reaction mixture was acidified with 12N hydrochloric acid and extracted with chloroform. The organic layer was concentrated under reduced pressure to obtain 1.27 g of a compound represented by the following formula (hereinafter referred to as intermediate P-3).

¹ H-NMR (DMSO-d6) δ: (3.01 + 2.93) (3H, s), ((1.65-1.50) + (1.43-1.38)) (4H, m).

The compounds described in the above production examples, the compounds produced by the production methods according to the methods described in the above production examples, and physical properties thereof are shown below. In the present specification, “Me” represents a methyl group, “Et” represents an ethyl group, and “ ⁱ Pr” represents an isopropyl group.

A compound represented by formula (1a).

R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , X ^a1 and k in the formula represent the substituents described in the following [Table 5] and [Table 6].

Compound 1a-3 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.52-9.49 (1H, m), 8.58-8.52 (1H, m), 8.24-8.17 (2H, m), 8.03-7.97 (1H, m), 7.97-7.94 ( 2H, m), 7.45-7.40 (1H, m), 1.76-1.71 (2H, m), 1.47-1.42 (2H, m).

Compound 1a-4 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.56-9.51 (1H, m), 8.60-8.54 (1H, m), 8.26-8.17 (2H, m), 8.03-7.94 (2H, m), 7.90-7.86 ( 1H, m), 7.45-7.39 (1H, m), 2.97-2.88 (2H, m), 2.60-2.50 (2H, m), 2.42-2.13 (2H, m).

Compound 1a-5 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.61-9.57 (1H, m), 8.59-8.53 (1H, m), 8.26-8.17 (2H, m), 8.02-7.94 (2H, m), 7.67-7.64 ( 1H, m), 7.45-7.40 (1H, m), 2.58-2.49 (2H, m), 2.30-2.21 (2H, m), 2.05-1.86 (4H, m).

Compound 1a-6 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.63-9.57 (1H, m), 8.60-8.54 (1H, m), 8.26-8.16 (2H, m), 8.03-7.94 (2H, m), 7.57-7.53 ( 1H, m), 7.46-7.40 (1H, m), 2.55-2.45 (2H, m), 1.88-1.72 (7H, m), 1.46-1.33 (1H, m).

Compound 1a-7 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.34-9.31 (1H, m), 8.29-8.27 (1H, m), 8.05-8.03 (1H, m), 7.87-7.84 (1H, m), 7.80-7.76 ( 1H, m), 7.60-7.54 (1H, m), 7.53-7.51 (1H, m), 7.40-7.38 (2H, m), 2.38 (6H, s), 1.74-1.69 (2H, m), 1.45- 1.41 (2H, m).

Compound 1a-8 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.33-9.30 (1H, m), 8.18-8.15 (1H, m), 7.85-7.83 (1H, m), 7.74-7.71 (1H, m), 7.69-7.67 ( 1H, m), 7.36-7.28 (2H, m), ((4.25-4.15) + (3.66-3.56)) (2H, m), 4.06 (3H, s), 1.58-1.51 (2H, m), ( (1.36-1.21) + (0.93-0.88)) (5H, m).

Compound 1a-9 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.76-9.73 (1H, m), 8.82-8.80 (1H, m), 8.56-8.53 (1H, m), 8.02-7.97 (2H, m), 7.42-7.37 ( 3H, m), 4.06 (3H, s), 2.41 (6H, s), 1.76-1.71 (2H, m), 1.47-1.43 (2H, m).

Compound 1a-10 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.51-9.48 (1H, m), 8.53-8.48 (1H, m), 8.00-7.95 (2H, m), 7.86-7.80 (1H, m), 7.43-7.38 ( 3H, m), 2.40 (6H, s), 1.75-1.71 (2H, m), 1.47-1.42 (2H, m).

Compound 1a-11 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.74-9.72 (1H, m), 9.33-9.32 (1H, m), 8.59-8.56 (1H, m), 8.19-8.17 (1H, m), 8.05-7.99 ( 2H, m), 7.97-7.95 (1H, m), 7.43-7.38 (1H, m), 4.08 (3H, s), 1.76-1.71 (2H, m), 1.47-1.43 (2H, m).

Compound 1a-12 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.33-9.30 (1H, m), 8.31-8.29 (1H, m), 7.93-7.90 (1H, m), 7.88-7.78 (3H, m), 7.74-7.71 ( 1H, m), 7.63-7.57 (1H, m), 7.56-7.53 (1H, m), 6.64 (1H, t), 2.97-2.88 (2H, m), 2.59-2.50 (2H, m), 2.38- 2.14 (2H, m).

Compound 1a-13 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.38-9.35 (1H, m), 8.31-8.29 (1H, m), 7.87-7.78 (3H, m), 7.73-7.67 (2H, m), 7.62-7.57 ( 1H, m), 7.56-7.54 (1H, m), 6.63 (1H, t), 2.57-2.48 (2H, m), 2.28-2.20 (2H, m), 2.05-1.86 (4H, m).

Compound 1a-14 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.41-9.38 (1H, m), 8.32-8.30 (1H, m), 7.86-7.78 (3H, m), 7.76-7.73 (1H, m), 7.62-7.57 ( 2H, m), 7.56-7.53 (1H, m), 6.63 (1H, t), 2.54-2.43 (2H, m), 1.86-1.71 (7H, m), 1.47-1.32 (1H, m).

Compound 1a-16 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.53-9.48 (1H, m), 8.56-8.50 (1H, m), 8.11-8.05 (1H, m), 7.98-7.92 (1H, m), 7.88-7.85 ( 1H, m), 7.83-7.80 (1H, m), 7.54-7.50 (1H, m), 7.43-7.37 (1H, m), 6.61 (1H, t), 2.95-2.86 (2H, m), 2.58- 2.49 (2H, m), 2.40-1.96 (2H, m).

Compound 1a-17 of the present invention
¹ H-NMR (DMSO-d6) δ: ((10.55-10.46) + (7.92-7.86) + (7.61-7.18)) (9H, m), 2.29 (3H, s), 1.59-1.54 (2H, m ), 1.37-1.32 (2H, m).

Compound 1a-18 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.26-9.23 (1H, m), 8.16-8.13 (1H, m), 7.88-7.86 (1H, m), 7.82-7.80 (1H, m), 7.53-7.49 ( 2H, m), 7.43-7.37 (1H, m), 6.64 (1H, t), 2.94-2.86 (2H, m), 2.58-2.48 (5H, m), 2.37-2.12 (2H, m).

Compound 1a-19 of the present invention
¹ H-NMR (CDCl ₃ ) δ: ((9.26-9.22) + (9.03-8.99)) (1H, m), ((8.01-7.95) + (7.90-7.84) + (7.78-7.72) + (7.66 -7.63) + (7.59-7.42) + (7.39-7.21)) (7H, m), 6.78-6.40 (1H, m), ((3.40-3.37) + (3.28-3.26)) (3H, m), ((1.75-1.68) + (1.44-1.37) + (1.31-1.26)) (4H, m).

Compound 1a-20 of the present invention
¹ H-NMR (CDCl ₃ ) δ: ((9.27-9.24) + (9.04-9.00)) (1H, m), ((7.97-7.95) + (7.92-7.90) + (7.86-7.84) + (7.80 -7.76) + (7.75-7.71) + (7.66-7.63) + (7.57-7.50) + (7.48-7.45) + (7.38-7.33) + (7.30-7.20)) (7H, m), 6.77-6.38 ( 1H, m), ((3.39-3.36) + (3.27-3.22)) (3H, m), 2.94-2.85 (2H, m), 2.56-2.45 (2H, m), 2.35-2.11 (2H, m) .

Compound 1a-21 of the present invention
¹ H-NMR (CDCl ₃ ) δ: ((9.33-9.30) + (9.10-9.07)) (1H, m), 8.28-8.25 (1H, m), 7.92-7.63 (4H, m), 7.58-7.50 (2H, m), 6.80-6.41 (1H, m), 4.11-4.03 (2H, m), ((1.79-1.69) + (1.49-1.37)) (7H, m).

Compound 1a-22 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.37-9.34 (1H, m), 8.29-8.26 (1H, m), 7.82-7.73 (3H, m), 7.66-7.63 (1H, m), 7.57-7.51 ( 2H, m), 6.61 (1H, t), 4.03 (2H, q), 2.87-2.78 (2H, m), 2.54-2.44 (2H, m), 2.32-2.19 (1H, m), 2.03-1.93 ( 1H, m), 1.40 (3H, t).

Compound 1a-23 of the present invention
¹ H-NMR (CDCl ₃ ) δ: ((9.38-9.36) + (9.14-9.11)) (1H, m), 8.32-8.28 (1H, m), 7.93-7.87 (1H, m), 7.84-7.76 (3H, m), 7.61-7.52 (2H, m), 6.63 (1H, t), 4.02-3.95 (1H, m), 1.96-1.58 (7H, m), 1.46-1.38 (2H, m), 1.07 -0.99 (3H, m).

Compound 1a-24 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.37-9.34 (1H, m), 8.28-8.25 (1H, m), 7.81-7.73 (3H, m), 7.67-7.64 (1H, m), 7.57-7.50 ( 2H, m), 6.60 (1H, t), 3.99-3.93 (2H, m), 2.85-2.76 (2H, m), 2.52-2.41 (2H, m), 2.32-2.17 (1H, m), 2.02- 1.91 (1H, m), 1.81-1.69 (2H, m), 0.98-0.92 (3H, m).

Compound 1a-25 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.28-9.26 (1H, m), 8.22-8.20 (1H, m), 7.99-7.98 (1H, m), 7.89-7.85 (1H, m), 7.77-7.73 ( 1H, m), 7.64-7.63 (1H, m), 7.59-7.53 (2H, m), 7.19-7.17 (1H, m), 4.48 (2H, q), 1.72-1.67 (2H, m), 1.43- 1.39 (2H, m).

Compound 1a-26 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.29-9.26 (1H, m), 8.23-8.21 (1H, m), 7.90-7.83 (2H, m), 7.77-7.73 (1H, m), 7.65-7.63 ( 1H, m), 7.59-7.54 (2H, m), 7.19-7.17 (1H, m), 4.48 (2H, q), 2.94-2.85 (2H, m), 2.56-2.47 (2H, m), 2.35- 2.12 (2H, m).

Compound 1a-27 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.27-9.24 (1H, m), 8.21-8.18 (1H, m), 7.98-7.96 (1H, m), 7.85-7.82 (1H, m), 7.79-7.78 ( 1H, m), 7.74-7.71 (1H, m), 7.57-7.52 (2H, m), 7.48-7.46 (1H, m), 6.03-5.74 (1H, m), 1.72-1.67 (2H, m), 1.43-1.38 (2H, m).

Compound 1a-28 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.28-9.25 (1H, m), 8.22-8.20 (1H, m), 7.89-7.87 (1H, m), 7.84-7.78 (2H, m), 7.75-7.71 ( 1H, m), 7.57-7.52 (2H, m), 7.50-7.47 (1H, m), 6.03-5.74 (1H, m), 2.93-2.86 (2H, m), 2.56-2.47 (2H, m), 2.35-2.11 (2H, m).

Compound 1a-29 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.28-9.26 (1H, m), 8.26-8.24 (1H, m), 7.97-7.95 (1H, m), 7.88-7.84 (2H, m), 7.79-7.75 ( 1H, m), 7.65-7.64 (1H, m), 7.60-7.52 (2H, m), 1.72-1.68 (2H, m), 1.43-1.39 (2H, m).

Compound 1a-30 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.29-9.27 (1H, m), 8.27-8.26 (1H, m), 7.88-7.83 (3H, m), 7.79-7.76 (1H, m), 7.65-7.63 ( 1H, m), 7.60-7.52 (2H, m), 2.94-2.86 (2H, m), 2.56-2.47 (2H, m), 2.35-2.12 (2H, m).

Compound 1a-31 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.26-9.24 (1H, m), 8.22-8.20 (1H, m), 7.97-7.95 (1H, m), 7.88-7.84 (1H, m), 7.80-7.77 ( 1H, m), 7.58-7.50 (3H, m), 7.13-7.11 (1H, m), 3.90 (3H, s), 1.72-1.67 (2H, m), 1.43-1.38 (2H, m).

Compound 1a-32 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.29-9.26 (1H, m), 8.24-8.21 (1H, m), 7.90-7.83 (2H, m), 7.80-7.76 (1H, m), 7.58-7.50 ( 3H, m), 7.12-7.10 (1H, m), 3.90 (3H, s), 2.94-2.85 (2H, m), 2.56-2.47 (2H, m), 2.35-2.11 (2H, m).

Compound 1a-33 of the present invention
¹ H-NMR (DMSO-d6) δ: 11.05-11.02 (1H, m), 10.94-10.91 (1H, m), 10.00-9.98 (1H, m), 8.49-8.47 (1H, m), 8.32-8.29 (1H, m), 8.05-8.00 (2H, m), 7.85-7.81 (1H, m), 7.62-7.57 (1H, m), 1.60-1.56 (2H, m), 1.36-1.32 (2H, m) .

Compound 1a-34 of the present invention
¹ H-NMR (DMSO-d6) δ: 11.05-11.03 (1H, m), 10.94-10.92 (1H, m), 10.09-10.07 (1H, m), 8.51-8.49 (1H, m), 8.32-8.29 (1H, m), 8.06-8.00 (2H, m), 7.85-7.81 (1H, m), 7.63-7.57 (1H, m), 2.70-2.49 (4H, m), 2.13-1.95 (2H, m) .

Compound 1a-35 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.34-9.32 (1H, m), 8.41-8.39 (1H, m), 8.31-8.29 (1H, m), 8.03-8.01 (1H, m), 8.00-7.98 ( 1H, m), 7.90-7.87 (2H, m), 7.83-7.79 (1H, m), 7.64-7.59 (1H, m), 1.75-1.71 (2H, m), 1.46-1.42 (2H, m).

Compound 1a-36 of the present invention
¹ H-NMR (CDCl ₃ ) δ: ((9.34-9.32) + (9.13-9.10)) (1H, m), ((8.41-8.38) + (8.30-8.26) + (8.04-7.78) + (7.63 -7.57)) (7H, m), (3.58 + 3.22) (3H, s), 1.78-1.40 (4H, m).

Compound 1a-37 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.54-9.51 (1H, m), 8.59-8.53 (1H, m), 8.41-8.39 (1H, m), 8.29-8.24 (1H, m), 8.04-7.96 ( 3H, m), 7.46-7.41 (1H, m), 1.77-1.72 (2H, m), 1.48-1.43 (2H, m).

Compound 1a-38 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.75-9.72 (1H, m), 9.43-9.41 (1H, m), 8.60-8.57 (1H, m), 8.41-8.38 (1H, m), 8.07-8.04 ( 1H, m), 8.03-7.98 (2H, m), 7.44-7.39 (1H, m), 4.10 (3H, s), 1.77-1.72 (2H, m), 1.48-1.44 (2H, m).

Compound 1a-39 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.31-9.28 (1H, m), 8.79-8.76 (1H, m), 8.46-8.44 (1H, m), 8.27-8.24 (1H, m), 7.91-7.89 ( 1H, m), 7.84-7.80 (1H, m), 7.72-7.68 (1H, m), 7.59-7.53 (2H, m), 7.45-7.43 (1H, m), 6.67 (1H, t), 2.95- 2.86 (2H, m), 2.58-2.48 (2H, m), 2.37-2.12 (2H, m).

A compound represented by formula (1b).

R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , X ^a2 and k in the formula represent the substituents described in [Table 7] below.

Compound 1b-1 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.30-9.27 (1H, m), 8.31-8.24 (2H, m), 8.13-8.08 (1H, m), 8.01-7.99 (1H, m), 7.85-7.83 ( 1H, m), 7.56-7.54 (1H, m), 7.36-7.32 (1H, m), 6.64 (1H, t), 1.74-1.70 (2H, m), 1.45-1.41 (2H, m).

Compound 1b-2 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.30-9.28 (1H, m), 8.32-8.25 (2H, m), 8.12-8.06 (1H, m), 7.91-7.88 (1H, m), 7.85-7.83 ( 1H, m), 7.56-7.54 (1H, m), 7.36-7.32 (1H, m), 6.64 (1H, t), 2.96-2.88 (2H, m), 2.59-2.49 (2H, m), 2.38- 2.11 (2H, m).

A compound represented by formula (1c).

R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , X ^a3 and k in the formula represent the substituents described in [Table 8] below.

Compound 1c-1 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.38-9.36 (1H, m), 7.99-7.94 (2H, m), 7.85-7.80 (2H, m), 7.64-7.62 (1H, m), 7.57-7.54 ( 1H, m), 7.52-7.48 (1H, m), 6.63 (1H, t), 1.76-1.71 (2H, m), 1.47-1.42 (2H, m).

Compound 1c-2 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.38-9.35 (1H, m), 7.96-7.93 (1H, m), 7.91-7.80 (3H, m), 7.63-7.61 (1H, m), 7.57-7.54 ( 1H, m), 7.53-7.48 (1H, m), 6.63 (1H, t), 2.97-2.89 (2H, m), 2.60-2.50 (2H, m), 2.43-1.99 (2H, m).

Compound 1c-3 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.35-9.32 (1H, m), 8.10-8.09 (1H, m), 8.00-7.98 (2H, m), 7.84-7.82 (1H, m), 7.77-7.75 ( 1H, m), 7.65-7.63 (1H, m), 7.55-7.53 (1H, m), 6.62 (1H, t), 1.75-1.70 (2H, m), 1.46-1.41 (2H, m).

Compound 1c-4 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.38-9.36 (1H, m), 8.10-8.08 (1H, m), 7.99-7.96 (1H, m), 7.93-7.91 (1H, m), 7.84-7.81 ( 1H, m), 7.77-7.72 (2H, m), 7.55-7.53 (1H, m), 6.62 (1H, t), 2.96-2.87 (2H, m), 2.59-2.49 (2H, m), 2.38- 2.14 (2H, m).

Compound 1c-5 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.35-9.33 (1H, m), 8.16-8.14 (1H, m), 8.13-8.10 (1H, m), 8.02-8.00 (1H, m), 7.91-7.89 ( 1H, m), 7.83-7.81 (1H, m), 7.67-7.66 (1H, m), 7.55-7.53 (1H, m), 6.62 (1H, t), 1.75-1.70 (2H, m), 1.46- 1.41 (2H, m).

Compound 1c-6 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.32-9.31 (1H, m), 8.16-8.14 (1H, m), 8.13-8.11 (1H, m), 7.92-7.91 (1H, m), 7.88-7.85 ( 1H, m), 7.84-7.82 (1H, m), 7.63-7.61 (1H, m), 7.56-7.54 (1H, m), 6.62 (1H, t), 2.96-2.88 (2H, m), 2.59- 2.50 (2H, m), 2.38-2.15 (2H, m).

Compound 1c-7 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.58-9.56 (1H, m), 8.44-8.41 (2H, m), 8.28-8.26 (1H, m), 8.05-8.02 (2H, m), 7.87-7.85 ( 1H, m), 7.77-7.74 (1H, m), 6.65 (1H, t), 1.72-1.67 (2H, m), 1.44-1.40 (2H, m).

Compound 1c-8 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.69-9.66 (1H, m), 8.67-8.65 (1H, m), 8.46-8.43 (1H, m), 8.28-8.26 (1H, m), 8.07-8.05 ( 2H, m), 7.89-7.87 (1H, m), 7.80-7.77 (1H, m), 6.68 (1H, t), 2.94-2.85 (2H, m), 2.60-2.50 (2H, m), 2.36- 2.14 (2H, m).

A compound represented by formula (1d).

R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , X ^a4 and k in the formula represent the substituents described in [Table 9] below.

Compound 1d-1 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.52-9.49 (1H, m), 8.97-8.93 (1H, m), 7.95-7.92 (1H, m), 7.88-7.82 (2H, m), 7.63-7.61 ( 1H, m), 7.57-7.54 (1H, m), 7.40-7.34 (1H, m), 6.63 (1H, t), 1.76-1.72 (2H, m), 1.47-1.43 (2H, m).

Compound 1d-2 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.55-9.51 (1H, m), 9.00-8.96 (1H, m), 7.88-7.81 (3H, m), 7.65-7.62 (1H, m), 7.57-7.54 ( 1H, m), 7.40-7.34 (1H, m), 6.64 (1H, t), 2.98-2.89 (2H, m), 2.60-2.51 (2H, m), 2.40-2.15 (2H, m).

Compound 1d-3 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.83-9.81 (1H, m), 8.96-8.94 (1H, m), 8.00-7.97 (1H, m), 7.89-7.85 (1H, m), 7.83-7.81 ( 1H, m), 7.66-7.64 (1H, m), 7.56-7.52 (1H, m), 7.12-7.08 (1H, m), 6.64 (1H, t), 4.06 (3H, s), 1.74-1.70 ( 2H, m), 1.46-1.41 (2H, m).

Compound 1d-4 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.87-9.84 (1H, m), 8.98-8.96 (1H, m), 7.90-7.85 (2H, m), 7.84-7.81 (1H, m), 7.68-7.66 ( 1H, m), 7.56-7.53 (1H, m), 7.12-7.08 (1H, m), 6.64 (1H, t), 4.05 (3H, s), 2.97-2.88 (2H, m), 2.60-2.50 ( 2H, m), 2.39-2.15 (2H, m).

A compound represented by formula (1e).

R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , X ^a1 , X ^a3 and k in the formula represent the substituents described in [Table 10] below.

Compound 1e-1 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.36-9.34 (1H, m), 8.13-8.08 (1H, m), 7.98-7.96 (1H, m), 7.86-7.83 (1H, m), 7.56-7.54 ( 1H, m), 7.29-7.27 (1H, m), 7.26-7.22 (1H, m), 6.66 (1H, t), 2.50 (3H, s), 1.76-1.71 (2H, m), 1.48-1.43 ( 2H, m).

Compound 1e-2 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.39-9.37 (1H, m), 8.15-8.10 (1H, m), 7.90-7.88 (1H, m), 7.86-7.83 (1H, m), 7.56-7.53 ( 1H, m), 7.32-7.29 (1H, m), 7.26-7.21 (1H, m), 6.66 (1H, t), 2.98-2.89 (2H, m), 2.61-2.52 (2H, m), 2.49 ( 3H, s), 2.40-2.16 (2H, m).

A compound represented by formula (2a).

R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and X ^a2 in the formula represent the substituents described in the following [Table 11] and [Table 12].

Compound 2a-1 of the present invention
¹ H-NMR (DMSO-d6) δ: 11.05-11.02 (1H, m), 10.43-10.39 (1H, m), 9.73-9.68 (1H, m), 8.46-8.44 (1H, m), 8.02-7.98 (1H, m), 7.93-7.90 (1H, m), 7.81-7.76 (1H, m), 7.59-7.16 (3H, m), 4.29-4.25 (2H, m).

Compound 2a-2 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.41-9.38 (1H, m), 8.31-8.29 (1H, m), 7.87-7.75 (4H, m), 7.67-7.64 (1H, m), 7.62-7.56 ( 1H, m), 7.55-7.53 (1H, m), 6.63 (1H, t), 2.46-2.35 (1H, m), 1.75 (3H, s), 1.25-1.21 (3H, m), 1.17-1.12 ( 3H, m).

Compound 2a-3 of the present invention
¹ H-NMR (CDCl ₃ ) δ: ((9.61-9.58) + (9.45-9.43)) (1H, m), 8.31-8.26 (1H, m), 7.84-7.74 (4H, m), 7.59-7.51 (2H, m), 6.82-6.39 (1H, m), ((4.78-4.76) + (4.24-4.23) + (3.84-3.81) + (3.62-3.60) + (3.20-3.19)) (5H, m ).

Compound 2a-4 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.34-9.31 (1H, m), 8.30-8.28 (1H, m), 7.92-7.78 (4H, m), 7.75-7.72 (1H, m), 7.62-7.57 ( 1H, m), 7.56-7.54 (1H, m), 6.63 (1H, t), 4.99-4.90 (1H, m), 1.73 (3H, d).

Compound 2a-5 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.35-9.33 (1H, m), 8.27-8.25 (1H, m), 7.85-7.75 (3H, m), 7.70-7.68 (1H, m), 7.64-7.62 ( 1H, m), 7.59-7.54 (1H, m), 7.53-7.51 (1H, m), 6.60 (1H, t), 1.82 (6H, s).

Compound 2a-6 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.35-9.33 (1H, m), 8.29-8.27 (1H, m), 7.84-7.75 (3H, m), 7.68-7.66 (1H, m), 7.60-7.50 ( 3H, m), 6.60 (1H, t), 2.10 (4H, q), 1.12 (6H, t).

A compound represented by formula (3a).

R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ^7a , R ^8a , R ^7b , R ^8b and X ^a3 in the formula represent the substituents described in [Table 13] below.

Compound 3a-1 of the present invention
¹ H-NMR (CDCl ₃ ) δ: ((9.54-9.50) + (9.44-9.41) (1H, m), ((8.30-8.27) + (8.25-8.23) (1H, m), 7.87-7.73 ( 4H, m), 7.63-7.45 (2H, m), 6.63 (1H, t), ((4.24-4.19) + (3.81-3.76) (2H, m), ((3.68-3.67) + (3.25-3.23 )) (3H, m), ((2.95-2.90) + (2.80-2.75)) (2H, m).

A compound represented by formula (4a-1).

Compound 4a-1 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.33-9.31 (1H, m), 8.28-8.25 (1H, m), 7.88-7.69 (5H, m), 7.59-7.53 (1H, m), 7.52-7.50 ( 1H, m), 6.60 (1H, t), ((1.62-1.60) + (1.55-1.52) + (1.49-1.47) + (1.28-1.21)) (8H, m).

A compound represented by formula (5a-1).

Compound 5a-1 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.35-9.33 (1H, m), 8.28-8.26 (1H, m), 7.98-7.92 (1H, m), 7.90-7.86 (1H, m), 7.80-7.78 ( 1H, m), 7.78-7.74 (1H, m), 7.69-7.66 (1H, m), 7.59-7.54 (1H, m), 7.53-7.51 (1H, m), 6.61 (1H, t), 3.51 ( 2H, d), 1.38-1.33 (2H, m), 1.14-1.10 (2H, m).

A compound represented by formula (6a-1).

Compound 6a-1 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.26-9.24 (1H, m), 8.24-8.21 (1H, m), 7.96-7.93 (1H, m), 7.87-7.83 (1H, m), 7.81-7.79 ( 1H, m), 7.77-7.73 (1H, m), 7.61-7.51 (3H, m), 1.71-1.67 (2H, m), 1.42-1.38 (2H, m).

A compound represented by formula (P).

R ⁶ , Z and k in the formula represent the substituents described in [Table 14] below.

Intermediate P-4
¹ H-NMR (CDCl ₃ ) δ: 7.50-7.42 (1H, m), 3.98-3.91 (3H, m), 2.89-2.80 (2H, m), 2.53-2.42 (2H, m), 2.31-2.04 ( 2H, m).

Intermediate P-5
¹ H-NMR (DMSO-d6) δ: 9.82-9.80 (1H, m), 2.64-2.41 (4H, m), 2.06-1.92 (2H, m).

Intermediate P-6
¹ H-NMR (CDCl ₃ ) δ: 3.93-3.89 (3H, m), 2.99-2.95 (3H, m), ((2.79-2.71) + (2.61-2.42)) (4H, m), 2.30-2.16 (1H, m), 2.01-1.91 (1H, m).

Intermediate P-7
¹ H-NMR (CDCl ₃ ) δ: 2.98-2.75 (3H, m), 2.74-2.61 (2H, m), ((2.51-2.10) + (2.03-1.79)) (4H, m).

Intermediate P-8
¹ H-NMR (CDCl ₃ ) δ: 3.98-3.88 (3H, m), 3.60-3.37 (2H, m), 1.72-1.34 (7H, m).

Intermediate P-9
¹ H-NMR (DMSO-d6) δ: 3.48-3.25 (2H, m), 1.67-1.60 (2H, m), 1.56-1.50 (1H, m), 1.41-1.36 (1H, m), 1.29-1.17 (3H, m).

Intermediate P-10
¹ H-NMR (CDCl ₃ ) δ: 3.89 (3H, s), 3.47-3.39 (2H, m), 2.83-2.75 (2H, m), 2.52-2.41 (2H, m), 2.32-2.20 (1H, m), 2.02-1.92 (1H, m), 1.34-1.28 (3H, m).

Intermediate P-11
¹ H-NMR (CDCl ₃ ) δ: 3.97-3.89 (2H, m), 2.84-2.76 (2H, m), 2.52-2.42 (2H, m), 2.31-2.18 (1H, m), 2.02-1.92 ( 1H, m), 1.39-1.34 (3H, m).

Intermediate P-12
¹ H-NMR (CDCl ₃ ) δ: (3.96 + 3.89) (3H, s), 3.48-3.24 (2H, m), 1.90-1.76 (2H, m), 1.71-1.57 (2H, m), 1.45- 1.32 (2H, m), 1.02-0.94 (3H, m).

Intermediate P-13
¹ H-NMR (CDCl ₃ ) δ: 3.62-3.31 (2H, m), 1.91-1.68 (4H, m), 1.48-1.35 (2H, m), 1.03-0.95 (3H, m).

Intermediate P-14
¹ H-NMR (CDCl ₃ ) δ: 3.89 (3H, s), 3.34-3.29 (2H, m), 2.82-2.75 (2H, m), 2.51-2.40 (2H, m), 2.31-2.19 (1H, m), 2.02-1.91 (1H, m), 1.74-1.63 (2H, m), 0.96-0.90 (3H, m).

Intermediate P-15
¹ H-NMR (DMSO-d6) δ: 3.38-3.26 (2H, m), 2.69-2.58 (2H, m), 2.55-2.44 (2H, m), 2.11-1.83 (2H, m), 1.59-1.48 (2H, m), 0.87-0.81 (3H, m).

Next, the formulation example of this invention compound is shown. In addition, a part represents a weight part.

Formulation Example 1
10 parts of any one compound of the compound A of the present invention is added to a mixture of 35 parts of xylene and 35 parts of DMF, and then 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added and mixed to each. To obtain a formulation.

Formulation Example 2
4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic silicon hydroxide fine powder and 54 parts of diatomaceous earth are added, and 20 parts of any one of the compounds A of the present invention are added and mixed to each water. Get a glaze.

Formulation Example 3
To 1 part of any one compound of the compound A of the present invention, 1 part of a synthetic silicon hydrous fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are added and mixed. Next, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated with a granulator, and dried by ventilation to obtain each granule.

Formulation Example 4
1 part of any one of the compounds A of the present invention is added to an appropriate amount of acetone, and 5 parts of a synthetic silicon hydroxide fine powder, 0.3 parts of isopropyl acid phosphate and 93.7 parts of fusami clay are added and mixed with sufficient stirring. Then, acetone is removed by evaporation to obtain each powder.

Formulation Example 5
35 parts of a mixture of polyoxyethylene alkyl ether sulfate ammonium salt and white carbon (weight ratio 1: 1), 10 parts of any one of the compounds A of the present invention and 55 parts of water are mixed, and finely divided by a wet grinding method. Each flowable agent is obtained by grinding.

Formulation Example 6
0.1 part of any one compound of the compound A of the present invention is added to a mixture of 5 parts of xylene and 5 parts of trichloroethane, and this is mixed with 89.9 parts of kerosene to obtain each oil.

Formulation Example 7
10 mg of any one of the compounds A of the present invention is added to 0.5 mL of acetone, and this solution is added dropwise to 5 g of animal solid feed powder (solid feed powder CE-2 for breeding and breeding, a product of Nippon Claire Co., Ltd.). To mix. Then acetone is evaporated to dryness to obtain each poisonous bait.

Formulation Example 8
0.1 part of any one of the compounds A of the present invention, 49.9 parts of neothiozole (manufactured by Chuo Kasei Co., Ltd.) are placed in an aerosol can, and after mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are filled and shaken. And an oil aerosol is obtained by mounting the actuator.

Formulation Example 9
0.6 part of any one of the compounds A of the present invention, 0.01 part of BHT (2,6-di-tert-butyl-4-methylphenol), 5 parts of xylene, 3.39 parts of kerosene and an emulsifier {Leodol MO -60 (manufactured by Kao Corporation)} 1 part mixed and 50 parts distilled water are filled into an aerosol container, and after the valve is mounted, 40 parts of propellant (LPG) is pressure filled through the valve. To obtain an aqueous aerosol.

Formulation Example 10
0.1 g of any one compound of the present compound A is mixed with 2 mL of propylene glycol and impregnated into a porous ceramic plate of 4.0 × 4.0 cm and a thickness of 1.2 cm to obtain a heating smoke. .

Formulation Example 11
5 parts of any one of the compounds A of the present invention and 95 parts of an ethylene-methyl methacrylate copolymer (ratio of methyl methacrylate in the copolymer: 10% by weight, ACRIFT (registered trademark) WD301, manufactured by Sumitomo Chemical) The mixture is melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is extruded from an extruder through a molding die to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

Formulation Example 12
5 parts of any one of the compounds A of the present invention and 95 parts of a soft vinyl chloride resin are melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is extruded from an extrusion molding machine through a molding die. A rod-shaped molded body having a length of 15 cm and a diameter of 3 mm is obtained.

Formulation Example 13
Any one compound of the present compound A 100 mg, lactose 68.75 mg, corn starch 237.5 mg, microcrystalline cellulose 43.75 mg, polyvinylpyrrolidone 18.75 mg, sodium carboxymethyl starch 28.75 mg, and magnesium stearate 2. 5 mg is mixed and the resulting mixture is compressed to an appropriate size to obtain tablets.

Formulation Example 14
Compound 1 of the present invention A 25 mg, lactose 60 mg, corn starch 25 mg, carmellose calcium 6 mg, and 5% hydroxypropylmethylcellulose are mixed in an appropriate amount, and the resulting mixture is filled into a hard shell gelatin capsule or hydroxypropylmethylcellulose capsule And a capsule is obtained.

Formulation Example 15
Any one compound of the present compound A 100 mg, fumaric acid 500 mg, sodium chloride 2000 mg, methylparaben 150 mg, propylparaben 50 mg, granule sugar 25000 mg, sorbitol (70% solution) 13000 mg, Veegum K (Vanderbilt Co.) 100 mg, flavor 35 mg, and coloring Distilled water is added to 500 mg of the preparation so that the final volume becomes 100 mL, and mixed to obtain a suspension for oral administration.

Formulation Example 16
5% by weight of any one of the compounds A of the present invention is added to 5% by weight of polysorbate 85, 3% by weight of benzyl alcohol, and 30% by weight of propylene glycol so that the pH of this solution is 6.0 to 6.5. After adding a phosphate buffer solution, water is added as the balance to obtain a solution for oral administration.

Formulation Example 17
5% by weight of aluminum distearate in 57% by weight of fractionated coconut oil and 3% by weight of polysorbate 85 is added and dispersed by heating. This is cooled to room temperature and 25% by weight of saccharin is dispersed in the oily vehicle. To this, 10% by weight of any one of the compounds A of the present invention is allocated to obtain a paste preparation for oral administration.

Formulation Example 18
5% by weight of any one of the compounds A of the present invention is mixed with 95% by weight of limestone powder, and granules for oral administration are obtained using a wet granulation method.

Formulation Example 19
5 parts of any one compound of the present compound A is added to 80 parts of diethylene glycol monoethyl ether, and 15 parts of propylene carbonate is mixed therewith to obtain a spot-on solution.

Formulation Example 20
10 parts of any one of the compounds A of the present invention are added to 70 parts of diethylene glycol monoethyl ether, and 20 parts of 2-octyldodecanol is mixed with this to obtain a pour-on solution.

Formulation Example 21
To 0.5 parts of any one of the compounds A of the present invention, 60 parts of Nikkor (registered trademark) TEALS-42 (42% aqueous solution of Nikko Chemicals lauryl sulfate triethanolamine) and 20 parts of propylene glycol were added, and uniform. After sufficiently stirring and mixing until a solution is obtained, 19.5 parts of water is added and further stirring and mixing is performed to obtain a shampoo agent of a uniform solution.

Formulation Example 22
Any one of the compounds A of the present invention 0.15% by weight, animal feed 95% by weight, and 4.85% by weight of a mixture comprising dicalcium phosphate, diatomaceous earth, Aerosil, and carbonate (or chalk) are sufficiently stirred and mixed. Obtain a premix for animal feed.

Formulation Example 23
7.2 g of any one of the compounds A of the present invention and 92.8 g of Fosco (registered trademark) S-55 (manufactured by Maruishi Pharmaceutical Co., Ltd.) are dissolved and mixed at 100 ° C., poured into a suppository, and solidified by cooling. To obtain a suppository.

Next, the efficacy of the compound of the present invention against harmful arthropods is shown by test examples.

Test example 1
Compounds of the present invention 1a-1 to 1a-4, 1a-7, 1a-8, 1a-10, 1a-12, 1a-15, 1a-16, 1a-19 to 1a- obtained according to Formulation Example 5 23, 1a-31, 1a-33, 1a-35 to 1a-37, 1c-1 to 1c-7, 1d-2, 2a-1, 2a-3, 2a-5, 3a-1, 4a-1 and Each preparation of 5a-1 was diluted with water so that the concentration of the compound of the present invention was 500 ppm, and each diluted solution was obtained.

On the other hand, about 30 Aphis gossypi (all stages) were inoculated into cucumber seedlings (first true leaf development stage) planted in plastic cups and left for 1 day. Each of these seedlings was sprayed with 20 mL of the diluted solution.

6 days after spraying, the number of live cotton aphids that parasitized on the cucumber leaves was investigated, and the control value was determined by the following formula.

Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: number of insects before spraying in the untreated area Cai: number of parasitic live insects when investigating the untreated area Tb: number of insects before spraying in the treated area Tai: number of parasitic live insects when investigating the treated area

Here, the untreated group means a group in which a preparation obtained by diluting the preparation not containing the compound of the present invention in Preparation Example 5 with the same amount of water as the treated group was sprayed.

As a result, the compounds 1a-1 to 1a-4, 1a-7, 1a-8, 1a-10, 1a-12, 1a-15, 1a-16, 1a-19 to 1a-23, 1a-31, 1a-33, 1a-35 to 1a-37, 1c-1 to 1c-7, 1d-2, 2a-1, 2a-3, 2a-5, 3a-1, 4a-1 and 5a-1 were used. All of the treatment sections showed a control value of 90% or more.

Test example 2
Compounds of the present invention 1a-1 to 1a-8, 1a-10 to 1a-13, 1a-15, 1a-16, 1a-19 to 1a-26, 1a-29 to 1a- obtained according to Formulation Example 5 38, 1b-1, 1c-1 to 1c-8, 1d-1, 1d-2, 1e-1, 2a-1 to 2a-6, 3a-1, 4a-1 and 5a-1 It diluted with water so that the density | concentration of this invention compound might be set to 500 ppm, and each diluted solution was obtained.

On the other hand, the diluted solution was sprayed at a rate of 20 mL / cup on a three-leaf cabbage planted in a polyethylene cup. After spraying, the plants were air-dried, the stems and leaves were cut out and accommodated in a 50 mL cup, and 5 second-instar larvae (Plutella xylostella) were released and capped. After storing at 25 ° C., the number of dead insects was counted after 5 days, and the death rate was calculated from the following formula.

Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the compounds 1a-1 to 1a-8, 1a-10 to 1a-13, 1a-15, 1a-16, 1a-19 to 1a-26, 1a-29 to 1a-38, 1b-1, All treatments using 1c-1 to 1c-8, 1d-1, 1d-2, 1e-1, 2a-1 to 2a-6, 3a-1, 4a-1 and 5a-1 are dead insects. The rate was 80% or more.

Test example 3
Compounds of the present invention 1a-1 to 1a-5, 1a-7 to 1a-13, 1a-15, 1a-16, 1a-19 to 1a-26, 1a-29 to 1a- obtained according to Formulation Example 5 39, 1b-1, 1c-1 to 1c-7, 1d-1, 1d-2, 2a-1, 2a-2, 2a-4 to 2a-6, 3a-1, 4a-1 and 5a-1 Each preparation was diluted with water so that the concentration of the compound of the present invention was 200 ppm, and each diluted solution was obtained.

The diluted solution was sprayed at a rate of 20 mL / cup on a three-leaf cabbage planted in a polyethylene cup. After spraying, the plants were air-dried, the stems and leaves were cut out and accommodated in a 50 mL cup, and 5 second-instar larvae (Plutella xylostella) were released and capped. After storing at 25 ° C., the number of dead insects was counted after 5 days, and the death rate was calculated from the following formula.

Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the compounds 1a-1 to 1a-5, 1a-7 to 1a-13, 1a-15, 1a-16, 1a-19 to 1a-26, 1a-29 to 1a-39, 1b-1, 1c-1 to 1c-7, 1d-1, 1d-2, 2a-1, 2a-2, 2a-4 to 2a-6, 3a-1, 4a-1 and 5a-1 Also showed a death rate of 80% or more.

Test example 4
Compounds of the present invention 1a-1 to 1a-8, 1a-10 to 1a-13, 1a-15, 1a-16, 1a-19 to 1a-25, 1a-29, 1a- obtained according to Formulation Example 5 30, 1a-33 to 1a-38, 1b-1, 1c-1 to 1c-7, 1d-1, 1d-2, 2a-1 to 2a-5, 3a-1, 4a-1 and 5a-1 Each preparation was diluted with water so that the concentration of the compound of the present invention was 500 ppm, and each diluted solution was obtained.

A filter paper of the same size was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, in-sector LF (Nihon Nosan Co., Ltd.) sliced into 6 mm thickness and cut in half, and 2 mL of the diluted solution was irrigated. After air-drying, 5 third-instar larvae of Spodoptera litra were released and capped. Six days later, the number of dead insects was counted, and the death rate was obtained from the following formula.

Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the compounds of the present invention 1a-1 to 1a-8, 1a-10 to 1a-13, 1a-15, 1a-16, 1a-19 to 1a-25, 1a-29, 1a-30, 1a-33 to 1a-38, 1b-1, 1c-1 to 1c-7, 1d-1, 1d-2, 2a-1 to 2a-5, 3a-1, 4a-1 and 5a-1 Also showed a death rate of 80% or more.

Test Example 5
Compounds of the present invention 1a-1 to 1a-13, 1a-15, 1a-16, 1a-19 to 1a-23, 1a-25, 1a-29 to 1a-31, 1a- obtained according to Formulation Example 5 33 to 1a-38, 1b-1, 1c-1 to 1c-7, 1d-1, 1d-2, 2a-1 to 2a-6, 3a-1, 4a-1 and 5a-1 It diluted with water so that the density | concentration of an invention compound might be 200 ppm, and each diluted solution was obtained.

The diluted solution was sprayed at a rate of 20 mL / cup on 5-6 leaf cabbage (Brassicae oleracea) planted in a polyethylene cup. After spraying, the plants were air-dried, covered with a polyethylene cup (capacity 400 mL), 10 4th instars of Spodoptera litura were released, and capped with Tetorongose. After storing at 25 ° C., the number of surviving insects was counted after 6 days, and the death rate was determined from the following formula.

Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the compounds 1a-1 to 1a-13, 1a-15, 1a-16, 1a-19 to 1a-23, 1a-25, 1a-29 to 1a-31, 1a-33 to 1a-38, 1b-1, 1c-1 to 1c-7, 1d-1, 1d-2, 2a-1 to 2a-6, 3a-1, 4a-1 and 5a-1 are all treated with dead insects. The rate was 80% or more.

Test Example 6
Compounds of the present invention 1a-1 to 1a-5, 1a-8, 1a-15, 1a-16, 1a-19 to 1a-21, 1a-23, 1a-24, 1a- obtained according to Formulation Example 5 28-1a-30, 1a-33-1a-39, 1b-1, 1c-1 to 1c-7, 1c-9, 1d-1, 2a-1, 2a-4, 2a-5 and 3a-1 Each preparation was diluted with water so that the concentration of the compound of the present invention was 200 ppm, and each diluted solution was obtained.
On the other hand, the diluted solution was sprayed at a rate of 10 ml / cup on cucumber seedlings planted in plastic cups (second leaf development stage). Thereafter, the first true leaves were cut out and accommodated in a polyethylene cup, and about 20 larvae of Franklinella occidentalis were released on the cucumber leaves and covered with a polyethylene lid. Seven days after spraying, the number of surviving insects on the cucumber leaves was examined, and the control value was determined by the following formula.
Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: number of insects in the untreated section when released Cai: number of insects in the untreated section observed Tb: number of insects in the treated section released Taii: number of insects in the treated section observed Here Means the group in which a preparation diluted with the same amount of water as the treatment group was sprayed on the preparation not containing the compound of the present invention in Preparation Example 5.
As a result, the compounds 1a-1 to 1a-5, 1a-8, 1a-15, 1a-16, 1a-19 to 1a-21, 1a-23, 1a-24, 1a-28 to 1a-30, 1a-33 to 1a-39, 1b-1, 1c-1 to 1c-7, 1c-9, 1d-1, 2a-1, 2a-4, 2a-5 and 3a-1 The control value was 90% or more.

Test Example 7
The compounds of the present invention 1a-1, 1a-2, 1a-12, 1a-15, 1a-21, 1a-22, 1a-29, 1a-33, 1a-36, 1c- obtained according to Formulation Example 5 1, 1c-2, 1c-5, 1d-1, 1d-2, 2a-1, 2a-3, 2a-5 and 3a-1 were each prepared with water so that the concentration of the compound of the present invention was 500 ppm. Dilution was performed to obtain each diluted solution.

About 40 adult spider mite (Tetranychus urticae) females were inoculated on the seedling seedlings in the primary leaf development stage planted in a polyethylene cup, and 30 mL of the diluted solution was sprayed one day after the inoculation.

After 13 days of spraying, the number of surviving ticks on the leaves of the periwinkle was investigated, and the control rate was calculated by the following formula.

Control rate (%) = 100 × {1− (number of surviving ticks in treated area) / (number of surviving ticks in untreated area)}
As a result, the compounds 1a-1, 1a-2, 1a-12, 1a-15, 1a-21, 1a-22, 1a-29, 1a-33, 1a-36, 1c-1, 1c-2, All of the treatment groups using 1c-5, 1d-1, 1d-2, 2a-1, 2a-3, 2a-5 and 3a-1 showed a control rate of 90% or more.

Test Example 8
Compounds of the present invention 1a-2 to 1a-5, 1a-7 to 1a-12, 1a-15, 1a-16, 1a-19, 1a-21 to 1a-23, 1a- obtained according to Formulation Example 5 25, 1a-29 to 1a-31, 1a-33 to 1a-38, 1b-1, 1c-2 to 1c-8, 1d-2, 2a-1, 2a-2, 2a-4, 2a-5, The preparations 3a-1, 4a-1 and 5a-1 were each diluted with water so that the concentration of the compound of the present invention was 500 ppm, and each diluted solution was obtained.

A filter paper of the same size was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, 0.7 mL of the diluted solution was dropped on the filter paper, and 30 mg of sucrose was uniformly added as food. Ten female fly (Musca domestica) females were released into the polyethylene cup and covered. One day later, the life and death of the house fly was investigated, the number of dead insects was counted, and the death rate was calculated by the following formula.

Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the compounds of the present invention 1a-2 to 1a-5, 1a-7 to 1a-12, 1a-15, 1a-16, 1a-19, 1a-21 to 1a-23, 1a-25, 1a-29 to 1a-31, 1a-33 to 1a-38, 1b-1, 1c-2 to 1c-8, 1d-2, 2a-1, 2a-2, 2a-4, 2a-5, 3a-1, 4a- Both treatment groups using 1 and 5a-1 showed 100% mortality.

Test Example 9
Compounds of the present invention 1a-1 to 1a-13, 1a-15 to 1a-17, 1a-19 to 1a-23, 1a-25, 1a-29 to 1a-31, 1a- obtained according to Formulation Example 5 33-1a-39, 1b-1, 1c-1 to 1c-8, 1c-10, 1d-1 to 1d-3, 1e-1, 2a-1 to 2a-6, 3a-1, 4a-1, The preparations 5a-1 and 6a-1 were each diluted with water so that the concentration of the compound of the present invention was 500 ppm to obtain respective diluted solutions.

The 0.7 mL of the diluted solution was added to 100 mL of ion-exchanged water (active ingredient concentration 3.5 ppm). Twenty instar larvae of Culex pipiens pallens were released into the solution, and the number of dead insects was counted one day later, and the death rate was determined.

Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the present compounds 1a-1 to 1a-13, 1a-15 to 1a-17, 1a-19 to 1a-23, 1a-25, 1a-29 to 1a-31, 1a-33 to 1a-39, 1b-1, 1c-1 to 1c-8, 1c-10, 1d-1 to 1d-3, 1e-1, 2a-1 to 2a-6, 3a-1, 4a-1, 5a-1 and 6a- All of the treatment groups using 1 showed a death rate of 91% or more.

Test Example 10
Compounds of the present invention 1a-2 to 1a-4, 1a-7, 1a-8, 1a-10, 1a-16, 1a-19, 1a-21, 1a-23, 1a- obtained according to Formulation Example 5 29, 1a-31, 1a-33, 1a-35, 1a-37, 1c-3, 2a-1 and 5a-1 were diluted with water so that the concentration of the compound of the present invention was 500 ppm, Each dilution was obtained.

A filter paper of the same size was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, 0.7 mL of the diluted solution was dropped on the filter paper, and 30 mg of sucrose was uniformly added as food. Two adult male cockroaches (Blattalla germanica) were released into the polyethylene cup and covered. One day later, the number of dead insects was counted to determine the death rate.

Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the compounds 1a-2 to 1a-4, 1a-7, 1a-8, 1a-10, 1a-16, 1a-19, 1a-21, 1a-23, 1a-29, 1a-31, All of the treatment sections using 1a-33, 1a-35, 1a-37, 1c-3, 2a-1 and 5a-1 showed a mortality rate of 100%.

Reference example 1
The compound 1a-2 of the present invention and the compound 1-18 described in International Publication No. 2012-164698 were subjected to a test according to the above Test Example 6. As a result, the compound 1a-2 of the present invention was controlled at a concentration of 0.8 ppm. While the value was 100%, Compound 1-18 had a concentration of 0.8 ppm and a control value of 10%.

The compound of the present invention exhibits an excellent control effect against harmful arthropods.

Claims

Formula (I)

[Where:
G 1 , G 2 and G 3 each independently represent —CR 7 R 8 — or a single bond (provided that at least one of G 1 , G 2 and G 3 represents —CR 7 R 8 —) ),
R 1 and R 3 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, —R 9 , —OR 9 or —S (O) p R 9 ;
R 2 represents —R 9 , —OR 9 or —S (O) p R 9 ,
R 4 , R 5 and R 6 are each independently a hydrogen atom, —R 9 , one or more halogen atoms (C1-C4 alkoxy) C1-C4 alkyl group, —C (O) R 9 Or represents —CO 2 R 9 ,
R 7 and R 8 each independently represent a hydrogen atom or —R 9 , or R 7 and R 8 together with the carbon atom to which they are attached, a C3-C7 cycloalkane {the C3-C7 cyclo The alkane may have one or more substituents selected from the group consisting of a halogen atom and R 9, and when having two or more substituents, they may be the same or different. },
R 9 represents a C1-C6 chain hydrocarbon group which may have one or more halogen atoms,
X a represents a halogen atom, a cyano group, —R 10 or —OR 10 ;
R 10 represents a C1-C3 chain hydrocarbon group,
X b represents -R 9 , -OR 9 , a halogen atom or a cyano group,
n and p each independently represent 0, 1 or 2;
m represents 0, 1, 2, 3 or 4. ]
An oxalylamide compound represented by:
Any one of G 1 , G 2 and G 3 is —CR 7 R 8 — (wherein R 7 and R 8 each independently represents a hydrogen atom or —R 9 , or R 7 and R 8 together with the carbon atom to which they are attached, a C3-C7 cycloalkane (the C3-C7 cycloalkane may have one or more substituents selected from the group consisting of halogen atoms and R 9 In the case of having two or more substituents, they may be the same or different.}, And the other two are each independently —CR 7 R 8 — (where 2. The compound according to claim 1, wherein R 7 and R 8 each independently represents a hydrogen atom or —R 9 ) or a single bond.
G 1 is -CR 7 R 8 - and is,
The compound according to claim 1 or 2, wherein G 2 and G 3 are a single bond.
G 1 and G 2 are —CR 7 R 8 —,
The compound according to claim 1 or 2, wherein G 3 is a single bond.
A compound according to claim 1 or claim 2 in which - G 1, G 2 and G 3 is -CR 7 R 8.
One of R 1 and R 3 is a bromine atom, an iodine atom or a C1-C6 alkyl group, and the other is a C1-C6 alkyl group which may have one or more halogen atoms, a C1-C6 haloalkoxy group The oxalylamide compound according to any one of claims 1 to 5, which is a group or -S (O) p R 11 (R 11 represents C1-C6 haloalkyl).
The oxalylamide compound according to claim 6, wherein R 2 is a C1-C6 haloalkyl group.
The oxalylamide compound according to claim 6, wherein R 2 is a C1-C6 haloalkoxy group.
The oxalylamide compound according to claim 6, wherein R 2 is a —S (O) p R 11 group.
A harmful arthropod control composition comprising the oxalylamide compound according to any one of claims 1 to 9 and an inert carrier.
A method for controlling harmful arthropods, which comprises applying an effective amount of the oxalylamide compound according to any one of claims 1 to 9 to harmful arthropods or habitats of harmful arthropods.
Formula (II)

[Where:
R 6 represents a hydrogen atom, —R 9 , a (C1-C4 alkoxy) C1-C4 alkyl group optionally having one or more halogen atoms, —C (O) R 9 or —CO 2 R 9 ;
R 9 represents a C1-C6 chain hydrocarbon group which may have one or more halogen atoms,
R 12 represents a hydrogen atom or a C1-C4 alkyl group,
j represents 1, 2 or 3. ]
A compound represented by