WO2016163379A1

WO2016163379A1 - Oxalyl amide compound and use thereof for noxious arthropod control

Info

Publication number: WO2016163379A1
Application number: PCT/JP2016/061210
Authority: WO
Inventors: 政樹 ▲高▼橋
Original assignee: 住友化学株式会社
Priority date: 2015-04-09
Filing date: 2016-04-06
Publication date: 2016-10-13

Abstract

The present invention provides a compound that exhibits an excellent control effect against noxious arthropods. The oxalyl amide compound represented by formula (I) has excellent control efficacy against noxious arthropods (in the formula, J¹, J², J³, and J⁴ each independently represent a nitrogen atom or the like, R¹ and R³ each independently represent a hydrogen atom, a halogen atom, -R⁷, or the like, R² represents -R⁷ or the like, each X independently represents -R⁷, a halogen atom, or the like, R⁴ and R⁵ each independently represent a hydrogen atom, -R⁷, or the like, R⁷ represents a C1-C6 chain hydrocarbon group that may have one or more halogen atoms, G¹ and G⁶ each independently represent -CR⁹R¹⁰- or the like, G², G³, G⁴, and G⁵ each independently represent -S(O)_k(Q)_m-, -O-, or the like, R⁹ and R¹⁰ each independently represent a hydrogen atom, -R⁷, or the like, and n represents 0, 1, or 2).

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:
J ¹ , J ² , J ³ and J ⁴ each independently represent a nitrogen atom or CR ⁶ (provided that at least one of J ¹ , J ² , J ³ and J ⁴ represents a nitrogen atom),
R ¹ and R ³ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, —R ⁷ , —OR ⁷ or —S (O) _p R ⁷ ;
R ² represents —R ⁷ , —OR ⁷ or —S (O) _p R ⁷ ,
Each X independently represents —R ⁷ , —OR ⁷ , a halogen atom or a cyano group;
R ⁴ and R ⁵ are each independently a hydrogen atom, —R ⁷ , (C1-C4 alkoxy) C1-C4 alkyl group, —C (O) R ⁷ or —CO ₂ represents R ⁷ ,
R ⁶ represents a hydrogen atom, a halogen atom, —R ⁸ or —OR ⁸ ,
R ⁷ represents a C1-C6 chain hydrocarbon group which may have one or more halogen atoms,
R ⁸ represents a C1-C3 chain hydrocarbon group,
G ¹ and G ⁶ each independently represent —CR ⁹ R ¹⁰ — or —C (O) —,
G ² , G ³ , G ⁴ and G ⁵ are each independently -CR ⁹ R ^10- , -C (O)-, -S (O) _k (Q) _m- , -O-, -NR ¹¹ - or a single bond and represents ^(wherein, G ^2, G 3, at least one of ^{G 4} and ^{G 5} is _{_{-S (O) k (Q)}} m -, - O- or ^{-NR 11} - represents a.) ,
Q represents NR ¹² or NC (O) R ⁷ ;
R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, —R ⁷ , —OR ⁷ , —S (O) _p R ⁷ , —C (O) R ⁷ or —CO ₂ R ⁷ . Represent,
R ¹¹ represents a hydrogen atom, —R ⁷ , —C (O) R ⁷ , —CO ₂ R ⁷ or SO ₂ R ⁷ ,
R ¹² represents a hydrogen atom, a cyano group, or a C1-C6 alkyl group which may have one or more halogen atoms,
k represents 0, 1 or 2,
m represents 0 or 1;
the sum of k and m represents 0, 1 or 2;
n and p each independently represent 0, 1 or 2. ]
An oxalylamide compound represented by formula (hereinafter also referred to as the present compound).
[2] The oxalylamide compound according to [1], wherein any one of J ¹ , J ² , J ³ and J ⁴ is a nitrogen atom and the other is CR ⁶ .
[3] The oxalylamide compound according to [1], wherein any one of J ¹ , J ² , J ³ and J ⁴ is a nitrogen atom and the other is CH.
[4] 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, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, The oxalylamide compound according to any one of [1] to [3], which is a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, or a C1-C6 haloalkylsulfonyl group.
[5] The oxalylamide compound according to [4], wherein R ² is a C1-C6 haloalkyl group.
[6] The oxalylamide compound according to [4], wherein R ² is a C1-C6 haloalkoxy group.
[7] The oxalylamide compound according to [4], wherein R ² is a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, or a C1-C6 haloalkylsulfonyl group.
[8] A harmful arthropod control composition comprising the compound according to any one of [1] to [7] and an inert carrier.
[9] A method for controlling harmful arthropods, which comprises applying an effective amount of the compound according to any one of [1] to [7] to harmful arthropods or habitats of harmful arthropods.

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, the expression “CX-CY” means that the number of carbon atoms is X to Y. For example, the notation “C1-C6” means that the number of carbon atoms is 1 to 6, and the notation “C1-C3” means that the number of carbon atoms is 1 to 3.

In the present specification, examples of the “C1-C6 alkyl group” include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The “C1-C6 alkyl group” includes a “C1-C4 alkyl group” and further a “C1-C3 alkyl group”.

In the present specification, examples of the “C1-C6 alkoxy group” include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. The “C1-C6 alkoxy group” includes a “C1-C4 alkoxy group” and further a “C1-C3 alkoxy group”.

In the present specification, the “C1-C6 haloalkyl group” is a group in which one or more hydrogen atoms of the “C1-C6 alkyl group” are substituted with a halogen atom, for example, a fluoromethyl group, a difluoromethyl group, a trifluoro Methyl group, chlorodifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, or heptafluoroisopropyl group, 1,1,2,2,3,3-hexafluoropropyl Groups, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group and trichloromethyl group.

In the present specification, the “C1-C6 haloalkoxy group” is a group in which one or more hydrogen atoms of the “C1-C6 alkoxy group” are substituted with a halogen atom, such as a fluoromethoxy group, a difluoromethoxy group, Fluoromethoxy group, chlorodifluoromethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, heptafluoropropoxy group, or heptafluoroisopropoxy group, 1,1,2,2,3,3-hexa Examples thereof include a fluoropropoxy group, 2,2,2-trifluoro-1- (trifluoromethyl) ethoxy group, and trichloromethoxy group.

In this specification, the “C1-C6 haloalkylthio group” is a monovalent group in which the “C1-C6 haloalkyl group” is bonded to a sulfur atom, and the “C1-C6 haloalkylsulfinyl group” is the above “C1 The —C6 haloalkyl group ”is a monovalent group bonded to the sulfur atom of S (O), and the“ C1-C6 haloalkylsulfonyl group ”means that the“ C1-C6 haloalkyl group ”is sulfur of S (O) ₂ A monovalent group bonded to an atom.

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 “may have one or more halogen atoms”, “haloalkyl” and “haloalkoxy”, when having two or more halogen atoms, these halogen atoms may be the same or different from each other.

In the present specification, the “chain hydrocarbon group” means an alkyl group, an alkenyl group, or an alkynyl group.

As used herein, “C1-C6 chain hydrocarbon group” means a C1-C6 alkyl group, a C2-C6 alkenyl group, and a C2-C6 alkynyl group. The “C1-C6 chain hydrocarbon group” includes a C1-C3 chain hydrocarbon group.

Here, the “C1-C6 alkyl group” is as described above, and examples of the “C2-C6 alkenyl group” include vinyl group, allyl group, isopropenyl group, crotyl group, and “C2-C6 alkynyl group”. Examples of the “group” include an ethynyl group and a propargyl group.

In the present specification, the “C1-C6 chain hydrocarbon group optionally having one or more halogen atoms” refers to a C1-C6 chain hydrocarbon group or a C1-C6 chain formula having one or more halogen atoms. A hydrocarbon group is meant. The “C1-C6 chain hydrocarbon group having one or more halogen atoms” means a C1-C6 haloalkyl group, a C2-C6 haloalkenyl group, and a C2-C6 haloalkynyl group.

Here, the “C1-C6 haloalkyl group” is as described above, and the “C2-C6 haloalkenyl group” is a group in which one or more hydrogen atoms of the “C2-C6 alkenyl group” are substituted with a halogen atom. The “C2-C6 haloalkynyl group” is a group in which one or more hydrogen atoms of the “C2-C6 alkynyl group” are substituted with a halogen atom.

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

The oxalylamide compound represented by formula (I) according to the present invention may contain one or more asymmetric carbon atoms or asymmetric centers in the structural formula, and two or more optical isomers may be present. Although present in some cases, the present invention includes all the optical isomers and a mixture in which they are contained in an arbitrary ratio. The oxalylamide compound represented by the formula (I) according to the present invention has two or more geometric isomers derived from a carbon-carbon double bond, a sulfur-nitrogen double bond, a cyclic structure, etc. in the structure. However, the present invention includes all the geometric isomers and the mixtures in which they are contained in an arbitrary ratio.

As this invention compound, the following compounds are 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 ⁷ , —OR ⁷ or —S (O) _p R ⁷ ,
R ⁴ and R ⁵ are each independently a hydrogen atom or —R ⁷ ,
R ⁷ is a C1-C3 chain hydrocarbon group which may have one or more halogen atoms,
R ⁸ is a methyl group,
A compound wherein n is 0.
[Aspect 2]
In Embodiment 1, a compound wherein any one of J ¹ , J ² , J ³ and J ⁴ is a nitrogen atom and the other is CR ⁶ .
[Aspect 3]
In embodiment 1, the compound wherein J ¹ is a nitrogen atom and J ² , J ³ and J ⁴ are CR ⁶ .
[Aspect 4]
In embodiment 1, the compound wherein J ² is a nitrogen atom and J ¹ , J ³ and J ⁴ are CR ⁶ .
[Aspect 5]
In embodiment 1, the compound wherein J ³ is a nitrogen atom and J ¹ , J ² and J ⁴ are CR ⁶ .
[Aspect 6]
In embodiment 1, the compound wherein J ⁴ is a nitrogen atom and J ¹ , J ² and J ³ are CR ⁶ .
[Aspect 7]
In embodiment 1, the compound in which any ^{two of} J ¹ , J ² , J ³ and J ⁴ are nitrogen atoms and the other is CR ⁶ .
[Aspect 8]
In embodiment 1, the compound wherein J ¹ and J ² are nitrogen atoms and J ³ and J ⁴ are CR ⁶ .
[Aspect 9]
In embodiment 1, the compound wherein J ¹ and J ³ are nitrogen atoms, and J ² and J ⁴ are CR ⁶ .
[Aspect 10]
In embodiment 1, the compound wherein J ¹ and J ⁴ are nitrogen atoms, and J ² and J ³ are CR ⁶ .
[Aspect 11]
In embodiment 1, the compound wherein J ² and J ³ are nitrogen atoms and J ¹ and J ⁴ are CR ⁶ .
[Aspect 12]
In embodiment 1, the compound wherein J ² and J ⁴ are nitrogen atoms and J ¹ and J ³ are CR ⁶ .
[Aspect 13]
In embodiment 1, the compound wherein J ³ and J ⁴ are nitrogen atoms and J ¹ and J ² are CR ⁶ .
[Aspect 14]
A compound in which R ⁶ is a hydrogen atom in Aspects 1 to 13.
[Aspect 15]
In Embodiments 1 to 14, any one of G ² , G ³ , G ⁴ and G ⁵ is —S (O) _k (Q) —, and the others are —CR ⁹ R ¹⁰ —, —C ( O)-or a compound that is a single bond.
[Aspect 16]
In Embodiments 1 to 14, any one of G ² , G ³ , G ⁴ and G ⁵ is —O—, and the other is —CR ⁹ R ¹⁰ —, —C (O) — or a single bond A compound.
[Aspect 17]
In Embodiments 1 to 14, any one of G ² , G ³ , G ⁴ and G ⁵ is —NR ¹¹ —, and the others are —CR ⁹ R ¹⁰ —, —C (O) — or a single bond A compound that is
[Aspect 18]
A compound in which G ³ , G ⁴ and G ⁵ are a single bond in Aspects 1 to 14.
[Aspect 19]
Aspect 1 to aspect 14, wherein G ⁴ and G ⁵ are a single bond.
[Aspect 20]
In embodiment 1, the compound wherein G ⁵ is a single bond.
[Aspect 21]
Aspect 1 to aspect 20, wherein G ¹ and G ⁶ are each independently —CHR ⁹ — or —C (O) —, and R ⁹ is a hydrogen atom or —R ⁷ .
[Aspect 22]
Aspect 1 to aspect 21 wherein R ² is —R ⁷ or —OR ⁷ .
[Aspect 23]
A compound wherein R ² is —R ⁷ in Aspect 1 to Aspect 22.
[Aspect 24]
A compound in which any ^one of R ¹ and R ³ is a halogen atom or —R ⁷ and the other is —R ⁷ or —OR ⁷ in Aspects 1 to 23.
[Aspect 25]
A compound according to aspect 1 to aspect 24, wherein R ⁴ and R ⁵ are each independently a hydrogen atom, a methyl group or an ethyl group.
[Aspect 26]
In the compounds of the present invention, G ¹ and G ⁶ are each independently —CR ⁹ R ¹⁰ —.
[Aspect 27]
In embodiment 26, G ² , G ³ , G ⁴ and G ⁵ are each independently -CR ⁹ R ^10- , -S (O) _k (Q) _m- , -O- or a single bond (provided that G ² , at least one of G ³ , G ⁴ and G ⁵ represents —S (O) _k (Q) _m — or —O—.
A plurality of R ⁹ are each independently a hydrogen atom or a C1-C3 alkyl group optionally having one or more halogen atoms;
A plurality of R ¹⁰ are each independently a hydrogen atom or a C1-C3 alkyl group optionally having one or more halogen atoms;
R ¹¹ is a C1-C3 alkyl group,
A compound wherein R ¹² is a cyano group.
[Aspect 28]
In embodiment 26, G ² , G ³ , G ⁴ and G ⁵ are each independently -CR ⁹ R ^10- , -S (O) _k (Q) _m- , -O- or a single bond (provided that G ² , at least one of G ³ , G ⁴ and G ⁵ represents —S (O) _k (Q) _m — or —O—.
A plurality of R ⁹ are each independently a hydrogen atom, a methyl group or a trifluoromethyl group;
A plurality of R ¹⁰ are each independently a hydrogen atom, a methyl group or a trifluoromethyl group;
R ¹¹ is a C1-C3 alkyl group,
A compound wherein R ¹² is a cyano group.
[Aspect 29]
In Embodiment 26, R ¹ and R ³ are each independently a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and a C1-C6 alkoxy group optionally substituted with one or more halogen atoms. Or a halogen atom,
A compound in which R ² is a C1-C6 haloalkyl group and n is 0.
[Aspect 30]
In embodiment 27, R ¹ and R ³ are each independently a C1-C6 alkyl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy optionally substituted with one or more halogen atoms. A group or a halogen atom,
A compound in which R ² is a C1-C6 haloalkyl group and n is 0.
[Aspect 31]
In Embodiment 28, R ¹ and R ³ are each independently a C1-C6 alkyl group optionally substituted with one or more halogen atoms, or a C1-C6 alkoxy optionally substituted with one or more halogen atoms. A group or a halogen atom,
A compound in which R ² is a C1-C6 haloalkyl group and n is 0.
[Aspect 32]
In embodiment 26, R ¹ is a bromine atom, an iodine atom or a C1-C6 alkyl group, R ³ is a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a C1-C6 haloalkoxy group,
A compound wherein R ² is a C1-C6 perfluoroalkyl group and n is 0.
[Aspect 33]
In embodiment 27, R ¹ is a bromine atom, an iodine atom or a C1-C6 alkyl group, R ³ is a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a C1-C6 haloalkoxy group,
A compound wherein R ² is a C1-C6 perfluoroalkyl group and n is 0.
[Aspect 34]
In Embodiment 28, R ¹ is a bromine atom, an iodine atom or a C1-C6 alkyl group, R ³ is a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a C1-C6 haloalkoxy group,
A compound wherein R ² is a C1-C6 perfluoroalkyl group and n is 0.
[Aspect 35]
In the compound of the present invention, R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group.
[Aspect 36]
In embodiment 26, the compound wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group.
[Aspect 37]
In embodiment 27, the compound wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group.
[Aspect 38]
In embodiment 28, the compound wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group.
[Aspect 39]
In embodiment 29, the compound wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group.
[Aspect 40]
In embodiment 30, the compound wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group.
[Aspect 41]
In embodiment 31, the compound wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group.
[Aspect 42]
In Embodiment 32, a compound wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group.
[Aspect 43]
In embodiment 33, the compound wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group.
[Aspect 44]
In embodiment 34, the compound wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group.
[Aspect 45]
A compound according to the embodiment 26 to the embodiment 44, wherein any one of J ¹ , J ² , J ³ and J ⁴ is a nitrogen atom and the other is CR ⁶ .
[Aspect 46]
Aspect 26 to 44, wherein any one of J ¹ , J ² , J ³ and J ⁴ is a nitrogen atom and the other is CH.
[Aspect 47]
Aspect 26 to aspect 44, wherein J ¹ is a nitrogen atom, and J ² , J ³ and J ⁴ are CH.
[Aspect 48]
Aspect 26 to aspect 44, wherein J ³ is a nitrogen atom, and J ¹ , J ² and J ⁴ are CH.

Next, a method for producing the compound of the present invention will be described.

The compound of the present invention and the intermediate compound can be produced, for example, according to the following production methods 1 to 4.

Manufacturing method 1
The compound of the present invention represented by the formula (I) (hereinafter also referred to as compound (I)) can be produced according to the following method.

[Wherein L represents a chlorine atom, a bromine atom or an iodine atom, Z represents a C1-C4 alkyl group, and other symbols have the same meaning as described above. ]
First, about the 1st process of manufacturing the compound (henceforth a compound (M3)) represented by a formula (M3) from the compound (henceforth a compound (M1)) represented by a formula (M1). Describe.

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. Compound (M1) can be produced according to the method described in JP-A-2001-122836. Compound (M2) can be a commercially available compound or can be produced according to a known method.

The reaction is usually performed in the presence of 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). Ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, methyl tert-butyl ether (hereinafter referred to as MTBE), 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) Dimethylformamide (hereinafter referred to as DMF), N-methylpi Pyrrolidone, 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); butyl lithium, lithium diisopropylamide And the like (hereinafter referred to as organometallic reagents).

In the 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, the second step for producing a compound represented by the formula (M11) from the compound (M3) (hereinafter referred to as compound (M11)) will be described.

Compound (M11) can be produced by reducing compound (M3).

The reaction is usually performed in the presence of 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 mixtures thereof.

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

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

In the reaction, the reducing agent is usually used at a ratio of 3 to 10 mol per 1 mol 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, the third step of producing a compound represented by the formula (M4) from the compound (M11) (hereinafter referred to as compound (M4)) will be described. *

Compound (M4) can be produced according to the method described in International Publication No. 2003/024961.

Next, it describes about the 4th process which manufactures the compound (henceforth a compound (M5)) represented by a formula (M5) from a compound (M4).

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. Compound (R1) is a commercially available compound.

The reaction is usually performed in the presence of 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 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 fifth step for producing compound (I) from compound (M5) will be described.

Compound (I) can be produced by reacting compound (M5) with a compound represented by formula (R2) (hereinafter referred to as compound (R2)).

The reaction is usually performed in the presence of 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.

The reaction can be performed by adding a base 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, with respect to 1 mole of the compound (M5), the compound (R2) is usually used at a ratio of 1 to 10 moles, and the base is usually used at a ratio of 1 to 10 moles.

Manufacturing method 2
Compound (I) can also be produced according to the following method.

[Wherein the symbols have the same meaning as described above. ]
First, it describes about the 1st process which manufactures the compound (henceforth a compound (M6)) represented by a formula (M6) from a compound (M5).

Compound (M6) can be produced by hydrolyzing compound (M5) in the presence of a base.

The reaction is usually performed in the presence of a solvent.

Examples of the solvent used in the reaction include water, a mixture of alcohols and water.

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

When the reaction is carried out by adding a base, the base is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (M5).

The reaction temperature 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 second step for producing compound (I) from compound (M6) will be described.

Compound (I) can be produced by reacting compound (M6) and compound (R2) 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. Examples thereof include 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 performed by adding a catalyst as necessary. Examples of the catalyst include 1-hydroxybenzotriazole (hereinafter referred to as HOBt) and 1-hydroxyazabenzotriol (hereinafter referred to as HOAt).

In the reaction, with respect to 1 mol of the compound (M6), the compound (R2) is usually 0.5 to 2 mol, the condensing agent is usually 1 to 5 mol, and the catalyst is usually 0.01 to 1 mol. Used in proportions.

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
Compound (I) 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 (M8) from the compound (R2) (hereinafter referred to as compound (M8)) can be carried out according to the method described in the first step of production method 1. .

A method for producing a compound represented by the formula (M9) from the compound (M8) (hereinafter referred to as compound (M9)) can be carried out according to the method described in the first step of production method 2. .

The method for producing compound (I) from compound (M9) can be carried out according to the method described in the second step of production method 2.

Manufacturing method 4
Compound (I) can be produced by reacting compound (M4) with a compound represented by formula (M10) (hereinafter referred to as compound (M10)) 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 (M10) can be produced by reacting compound (M9) with a chlorinating agent.

[Wherein the symbols have the same meaning as in formula (I 1). ]
The reaction is performed in the presence or absence of 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 chlorinating agent used in the reaction include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, and phosphorus pentachloride.

In the reaction, the chlorinating agent is usually used at a ratio of 1 to 100 mol per 1 mol of the compound (M9).

After completion of the reaction, the compound (M10) can be obtained by post-treatment such as concentration of the reaction mixture.

Manufacturing method 6
A compound represented by formula (1b) (hereinafter referred to as compound (1b)) and a compound represented by formula (1c) (hereinafter referred to as compound (1c)) can be produced by the following scheme. .

[Wherein the symbols have the same meaning as described above. ]
First, a method for producing the compound (Ib) from the compound represented by the formula (Ia) (hereinafter referred to as the compound (Ia)) will be described.

Compound (I b) can be produced by reacting compound (I a) with an oxidizing agent.

The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons, nitriles, alcohols, acetic acid, water, and mixtures thereof.

Examples of the oxidizing agent used in the reaction include sodium periodate, m-chloroperbenzoic acid (hereinafter referred to as mCPBA), and hydrogen peroxide.

When hydrogen peroxide is used as the oxidizing agent, a base or a catalyst may be added as necessary.

As the base used in the reaction, sodium carbonate can be mentioned.

Examples of the catalyst used in the reaction include tungstic acid and sodium tungstate.

In the reaction, with respect to 1 mol of the compound (I a), the oxidizing agent is usually in a proportion of 1 to 1.2 mol, the base is usually in a proportion of 0.01 to 1 mol, and the catalyst is usually in a proportion of 0.01 to 0.5 mol. Used in molar proportions.

The reaction temperature is usually in the range of −20 to 80 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, water is added to the reaction mixture and extracted with an organic solvent, and the organic layer is extracted with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. Wash. Compound (I b) can be obtained by drying and concentrating the organic layer.

Next, a method for producing compound (I c) from compound (I b) will be described.

Compound (Ic) can be produced by reacting compound (Ib) with an oxidizing agent.

Examples of the oxidizing agent used in the reaction include mCPBA and hydrogen peroxide. When hydrogen peroxide is used as the oxidizing agent, a base or a catalyst may be added as necessary.

As the base used in the reaction, sodium carbonate can be mentioned.

Examples of the catalyst used in the reaction include sodium tungstate.

In the reaction, with respect to 1 mol of the compound (I b), the oxidizing agent is usually in a proportion of 1 to 4 mol, the base is usually in a proportion of 0.01 to 1 mol, and the catalyst is usually in a proportion of 0.01 to 0.5 mol. Used in proportions.

The reaction temperature is usually in the range of −20 to 120 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, water is added to the reaction mixture and extracted with an organic solvent, and the organic layer is extracted with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. Wash. Compound (Ic) can be obtained by drying and concentrating the organic layer.

Also, the compound (Ic) can be produced in a one-step reaction (one pot) by reacting the compound (Ic) with an oxidizing agent. The reaction can be carried out according to the method for producing compound (I c) from compound (I b) in Production Method 6 except that the oxidizing agent is 2 to 5 mol.

The method described in production method 6 is not limited to the case where G ³ is a sulfur atom, and oxidation can be performed by the same method when G ² , G ^4, or G ⁵ is a sulfur atom. it can.

Manufacturing method 7
The compound represented by the formula (I e) can be produced by reacting a compound represented by the formula (Id) (hereinafter referred to as the compound (Id)) with an oxidizing agent.

[Wherein the symbols have the same meaning as described above. ]
This reaction can be carried out according to the method for producing compound (Ib) from compound (Ia) in Production Method 6.

Note that the method of Preparation 7 described, ^{G 3} is -S (Q) - it is not limited to the case ^where, G 2, ^{G 4} or ^{G 5} is -S (Q) - be a similar It can be oxidized by this method.

Manufacturing method 8
Compound (Id) can be produced by the following scheme.

[Wherein the symbols have the same meaning as described above. ]
The reaction was carried out in Organic Letters, Vol. 9, no. 19, 2007, 3809-3811.

Note that the method described in Production Example 8 is not limited to the case where G ³ is —S—, and the same method is used when G ² , G ⁴ or G ⁵ is —S—. Can do.

Manufacturing method 9
A compound represented by the formula (If) (hereinafter referred to as compound (If)) can be produced by the following scheme.

[Wherein, R ^1a represents a chlorine atom, a bromine atom or an iodine atom, R ^2a represents a C1-C6 perfluoroalkyl group, and R ^4a and R ^5a each independently represent a C1-C6 alkyl group or C1 —C6 represents a haloalkyl group, and other symbols have the same meanings as described above. ]

The compound represented by formula (M12) (hereinafter referred to as compound (M12)) is Journal of the American Chemical Society, 1931, vol. 53, p. It can be produced according to the method described in 3143-3146.

The compound represented by the formula (M13) (hereinafter referred to as the compound (M13)) can be produced by reacting the compound (M12) and the compound represented by the formula (R4) in the presence of a base. it can. The reaction can be carried out according to the method described in, for example, International Publication No. 2003/024961.

The compound represented by the formula (M14) (hereinafter referred to as the compound (M14)) can be produced using the compound (M13) according to the method described in International Publication No. 2005/073165.

A compound represented by the formula (M15) (hereinafter referred to as compound (M15)) can be produced according to the method described in International Publication No. 2003/024961.

The compound represented by formula (M16) (hereinafter referred to as compound (M16)) can be produced according to the method described in the fourth step of production method 1, using compound (M15).

A compound represented by formula (M17) (hereinafter referred to as compound (M17)) can be produced according to the method described in the first step of production method 2 using compound (M16).

A compound represented by formula (M18) (hereinafter referred to as compound (M18)) can be produced according to the method described in the second step of production method 2, using compound (M17).

Next, a method for producing the compound (If) from the compound (M18) will be described.

Compound (If) can be produced by reacting compound (M18) with a compound represented by formula (R6) (hereinafter referred to as compound (R6)) in the presence of an additive.

The reaction is usually performed in the presence of a solvent. Examples of the solvent used for the reaction include aprotic polar solvents.

Examples of the additive used in the reaction include copper powder activated by the method described in Journal of Fluorine Chemistry, 102 (2000) 293-300.

In the reaction, with respect to 1 mol of the compound (M18), the compound (R6) is usually used in a proportion of 1 to 10 mol, and the additive is usually used in a proportion of 1 to 10 mol.

The reaction temperature is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 48 hours.

After completion of the reaction, the additive is removed by filtration, water is added to the reaction mixture, extraction is performed with an organic solvent, and post-treatment operations such as drying and concentration of the organic layer are performed, whereby compound (If) is obtained. Obtainable.

Manufacturing method 10
A compound represented by the formula (Ig) (hereinafter referred to as compound (Ig)) can be produced by the following scheme.

[Wherein the symbols have the same meaning as described above. ]
A compound represented by formula (M19) (hereinafter referred to as compound (M19)) is produced using compound (M9) and a compound represented by formula (R7) (hereinafter referred to as compound (R7)). It can be produced according to the method described in the second step of Method 2.

The compound represented by the formula (M20) (hereinafter referred to as the compound (M20)) can be produced using the compound (M19) according to the method described in the first step of production method 2.

A compound represented by formula (M21) (hereinafter referred to as compound (M21)) is produced using compound (M20) and a compound represented by formula (R8) (hereinafter referred to as compound (R8)). It can be produced according to the method described in the second step of Method 2. Compound (R7) and compound (R8) are commercially available compounds or can be produced according to known methods.

Next, a method for producing a compound represented by the formula (M22) from the compound (M21) (hereinafter referred to as compound (M22)) will be described.

Compound (M22) can be produced by reacting compound (M21) and compound (R6) in the presence of an additive.

The reaction is usually performed in the presence of 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 additive used in the reaction include dithionite such as sodium dithionite or zinc-sulfite water.

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

In the reaction, a phase transfer catalyst can be used as necessary. Examples of the phase transfer catalyst used in the reaction include quaternary ammonium salts such as tetrabutylammonium hydrogen sulfate, organic phosphorus salts such as tetrabutylphosphonium bromide, and alkylpolyetheralkylamine compounds such as tris (methoxyethoxyethyl) amine. Is mentioned.

In the reaction, with respect to 1 mol of compound (M21), compound (R6) is usually in a proportion of 1 to 10 mol, additive is usually in a proportion of 0.1 to 2 mol, base is usually in a proportion of 1 to 10 mol, A phase transfer catalyst is usually used in a proportion of 0.01 to 2 mol.

After completion of the reaction, the compound (M22) can be obtained by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer.

Next, a method for producing a compound (Ig) from the compound (M22) will be described.

Compound (Ig) can be produced by reacting compound (M22) with a halogenating agent.

Examples of the halogenating agent used in the reaction include N-chlorosuccinimide (hereinafter referred to as NCS), chlorine, N-bromosuccinimide (hereinafter referred to as NBS), bromine, and N-iodosuccinic acid. Examples include imide (hereinafter referred to as NIS), iodine and the like.

In the reaction, the halogenating agent is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (M22).

The reaction temperature is usually in the range of 0 to 100 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, compound (I g) can be obtained by adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer.

Compound represented by formula (R10) (hereinafter referred to as compound (R10)), compound represented by formula (R11) (hereinafter referred to as compound (R11)), compound represented by formula (R12) (hereinafter referred to as compound) (Denoted as R12) and a compound represented by the formula (R13) (hereinafter referred to as compound (R13)) can be produced by the following scheme.

[Wherein the symbols have the same meaning as described above. ]
Compound (R10) can be produced according to the method described in production method 8 using the compound represented by formula (R9) (hereinafter referred to as compound (R9)).

Compound (R11) can be produced according to the method described in Production Method 7 using Compound (R10).

Compound (R12) and Compound (R13) can be produced according to the method described in Production Method 6 using Compound (R9).

Compound (R9) can be a commercially available compound or can be produced according to a known method.

The method described in Production Example 10 is not limited to the case where G ³ is a sulfur atom, and the same method can be used when G ² , G ^4, or G ⁵ is a sulfur atom. .

Next, although the specific example of this invention compound is shown below, this invention is not limited to this.
In the present specification, “Me” represents a methyl group, and “Et” represents an ethyl group.
Compounds of the present invention represented by the formulas (I-1) to (I-176) [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, and Coffee Barry Borer (Hypothenemus hampei).

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 Chicos (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 miyatakei), white termite (Reticulitermes flaviceps amamianus), common termite (Reticulitermes sp.), white termite (Nasutitermes takasagoensis), nitobeshi Lori (Pericapritermes nitobei), Mushy termite (Sinocapritermes mushae), Cornitermes cumulans, etc.

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 contains 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.

Reference production example 1
A mixture of 2.49 g of 5-nitronicotinic acid, 10 mg of benzyltriethylammonium chloride and 30 mL of thionyl chloride was stirred with heating under reflux for 3 hours. The reaction mixture allowed to cool to room temperature was concentrated under reduced pressure to obtain 5-nitronicotinic acid chloride. The resulting 5-nitronicotinic acid chloride is added dropwise to a mixture of 3.0 g of 2-bromo-6- (difluoromethoxy) -4- (heptafluoroisopropyl) aniline and 30 mL of 1,3-dimethyl-2-imidazolidinone. And stirred at 90 ° C. for 5 hours. The reaction mixture was allowed to reach room temperature, water was added, and the mixture was extracted with MTBE. 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 3.38 g of a compound represented by the following formula (hereinafter referred to as intermediate (M-1)).

¹ H-NMR (CDCl ₃ ) δ: 9.68-9.66 (1H, m), 9.48-9.46 (1H, m), 9.03-9.01 (1H, m), 7.85-7.81 (2H, m), 7.56-7.53 ( 1H, m), 6.61 (1H, t).

Reference production example 2
While stirring a mixture of Intermediate (M-1) 2.10 g, ethanol 32 mL and water 6 mL at 70 ° C., 0.60 g of ammonium chloride and 0.63 g of electrolytic iron powder were added. The mixture was stirred at 90 ° C. for 5 hours. Water was added to the reaction mixture, and the mixture was filtered through celite. After the filtrate was extracted with MTBE, 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 2.08 g of a compound represented by the following formula (hereinafter referred to as intermediate (M-2)).

¹ H-NMR (CDCl ₃ ) δ: 8.53-8.52 (1H, m), 8.30-8.29 (1H, m), 7.81-7.79 (1H, m), 7.65-7.63 (1H, m), 7.53-7.50 ( 2H, m), 6.60 (1H, t), 3.99-3.94 (2H, m).

Reference production example 3
To a mixture of 2.08 g of intermediate (M-2), 72 mg of DMAP, 0.83 mL of triethylamine and 20 mL of THF, 0.36 mL of methyl chloroglyoxylate was added dropwise under ice cooling, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was ice-cooled again, 0.06 mL of methyl chloroglyoxylate was added dropwise, and the mixture was stirred at room temperature for 30 minutes. After adding water to the reaction mixture and extracting with MTBE, 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 2.01 g of a compound represented by the following formula (hereinafter referred to as intermediate (M-3)).

¹ H-NMR (CDCl ₃ ) δ: 9.14-9.09 (1H, m), 9.03-8.98 (2H, m), 8.77-8.74 (1H, m), 7.89-7.80 (2H, m), 7.54-7.51 ( 1H, m), 6.61 (1H, t), 4.04-4.02 (3H, m).

Reference production example 4
A mixture of 1.00 g of intermediate (M-3), 1.6 mL of 2N aqueous sodium hydroxide solution and 16 mL of ethanol was stirred at 50 ° C. for 2 hours. The reaction mixture was brought to room temperature, water was added, and the mixture was washed with MTBE. The aqueous layer was adjusted to pH 2-3 with 2N hydrochloric acid and extracted with MTBE. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 0.66 g of a compound represented by the following formula (hereinafter referred to as intermediate (M-4)).

¹ H-NMR (DMSO-D6) δ: 11.20-11.15 (1H, m), 10.72-10.69 (1H, m), 9.10-9.07 (1H, m), 8.90-8.88 (1H, m), 8.71-8.69 (1H, m), 7.92-7.89 (1H, m), 7.56-7.53 (1H, m), 7.32 (1H, t).

The compounds produced by the production method according to the method described in the above Reference Production Examples and their physical property values are shown in the table.
Formula (N)

In which T is represented by [Table 1] and [Table 2].

Formula (N5)

In which R ¹ and R ³ are represented by [Table 3].

Formula (N6)

In which R ¹ and R ³ are represented by [Table 4].

Formula (N7)

In which R ¹ and R ³ are represented by [Table 5].

Formula (N8)

In which R ¹ and R ³ are represented by [Table 6] and [Table 7].

Production Example 1
A mixture of 0.69 g of intermediate (M-2), 0.23 g of oxo (thiomorpholin-4-yl) acetic acid, 0.50 g of HATU, 0.23 mL of diisopropylethylamine and 26 mL of DMF was stirred at 50 ° C. for 4 hours. The reaction mixture was allowed to reach room temperature, water was added, and the mixture was extracted with MTBE. 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 0.75 g of the present compound 1a-1 shown below.
Compound 1a-1 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.58-9.55 (1H, m), 8.99-8.97 (2H, m), 8.72-8.70 (1H, m), 7.85-7.80 (2H, m), 7.54-7.51 ( 1H, m), 6.61 (1H, t), 4.45-4.41 (2H, m), 4.01-3.98 (2H, m), 2.83-2.74 (4H, m).

Production Example 2
To a mixture of the compound 1a-1 (0.60 g) of the present invention and 30 mL of chloroform, 0.33 g of m-chloroperbenzoic acid (purity 65% or more) was added under ice cooling, and the mixture was stirred at room temperature for 4 hours. A saturated aqueous sodium thiosulfate solution and a saturated aqueous sodium hydrogen carbonate solution were 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 0.24 g of the present compound 1a-2 and 0.32 g of the present compound 1a-3 shown below.
Compound 1a-2 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.46-9.44 (1H, m), 8.99-8.97 (2H, m), 8.71-8.69 (1H, m), 7.83-7.81 (1H, m), 7.69-7.67 ( 1H, m), 7.54-7.52 (1H, m), 6.61 (1H, t), 5.25-5.18 (1H, m), 4.64-4.57 (1H, m), 4.36-4.28 (1H, m), 4.00- 3.92 (1H, m), 3.04-2.75 (4H, m).
Compound 1a-3 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.45-9.43 (1H, m), 9.00-8.98 (2H, m), 8.69-8.67 (1H, m), 7.83-7.81 (1H, m), 7.74-7.72 ( 1H, m), 7.54-7.52 (1H, m), 6.61 (1H, t), 4.73-4.68 (2H, m), 4.27-4.22 (2H, m), 3.30-3.16 (4H, m).

Production Example 3
Following the method described in Production Example 1, using thiomorpholine instead of intermediate (M-2) and intermediate (N8-1) instead of oxo (thiomorpholin-4-yl) acetic acid The present compound 2a-1 was obtained.
Compound 2a-1 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.65-9.62 (1H, m), 9.40-9.37 (1H, m), 8.46-8.43 (1H, m), 8.11-8.07 (1H, m), 8.03-7.98 ( 1H, m), 7.81-7.78 (1H, m), 7.54-7.51 (1H, m), 6.61 (1H, t), 4.43-4.39 (2H, m), 4.03-3.99 (2H, m), 2.84- 2.80 (2H, m), 2.79-2.75 (2H, m).

Production Example 4
NBS 0.11 g was added to a mixture of the present compound 2a-1 (0.28 g), cyanamide 22 mg, tert-butoxypotassium 55 mg and methanol 14 mL, and the mixture was stirred at room temperature for 3 hours. A saturated aqueous sodium thiosulfate solution was added to the reaction mixture, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The obtained residue was subjected to silica gel column chromatography to obtain 0.27 g of the present compound 2a-4 shown below.
Compound 2a-4 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.68-9.65 (1H, m), 9.39-9.36 (1H, m), 8.42-8.38 (1H, m), 8.14-8.10 (1H, m), 8.05-7.99 ( 2H, m), 7.82-7.79 (1H, m), 7.53-7.51 (1H, m), 6.62 (1H, t), 5.03-4.95 (1H, m), 4.63-4.46 (2H, m), 4.23- 4.08 (1H, m), 3.35-3.03 (4H, m).

Production Example 5
To a mixture of Compound 2a-4 (0.20 g) of the present invention, 0.12 g of potassium carbonate and 9 mL of ethanol, 0.11 g of mCPBA (purity 65% or more) was added under ice cooling, and the mixture was stirred at room temperature for 4 hours. A saturated aqueous sodium thiosulfate solution and a saturated aqueous sodium hydrogen carbonate solution were sequentially added to the reaction mixture, extracted with MTBE, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the resulting residue was subjected to silica gel column chromatography to obtain 90 mg of the present compound 2a-5 shown below.
Compound 2a-5 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.62-9.60 (1H, m), 9.35-9.33 (1H, m), 8.41-8.38 (1H, m), 8.15-8.12 (1H, m), 8.07-8.01 ( 1H, m), 7.82-7.79 (1H, m), 7.54-7.51 (1H, m), 6.61 (1H, t), 5.29-5.22 (1H, m), 4.80-4.72 (1H, m), 4.22- 4.14 (1H, m), 3.84-3.58 (4H, m), 3.46-3.37 (1H, m).

Production Example 6
A mixture of the present compound 2a-1 (0.28 g), trifluoroacetamide 93 mg, iodobenzene diacetate 0.20 g, magnesium oxide 66 mg, zirconium (II) tetraacetate 9 mg and chloroform 14 mL was stirred at room temperature for 3 hours. did. To the reaction mixture were added 0.19 g of trifluoroacetamide, 0.40 g of iodobenzene diacetate, 0.13 g of magnesium oxide, and 18 mg of dirhodium (II) tetraacetate, and the mixture was further stirred at room temperature for 2 hours. The reaction mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to obtain 0.23 g of the present compound 2a-6 shown below.
Compound 2a-6 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.64-9.61 (1H, m), 9.37-9.35 (1H, m), 8.43-8.40 (1H, m), 8.14-8.11 (1H, m), 8.05-8.01 ( 1H, m), 7.82-7.79 (1H, m), 7.54-7.51 (1H, m), 6.61 (1H, t), 5.29-5.22 (1H, m), 4.76-4.69 (1H, m), 4.28- 4.19 (1H, m), 3.91-3.82 (1H, m), 3.52-3.45 (2H, m), 3.35-3.26 (1H, m), 3.15-3.05 (1H, m).

Production Example 7
21 mg of 55% sodium hydride (oil) was added to a mixture of the compound 2a-1 of the present invention (0.13 g) and 19 mL of DMF under ice cooling, and the mixture was stirred for 20 minutes. To this mixture, 81 mg of methyl iodide was added, and the mixture was further stirred at 40 ° C. for 2 hours. The mixture was allowed to cool to room temperature, water was added, and the mixture was extracted with MTBE. 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 obtain 0.12 g of the present compound 2d-1 shown below.
Compound 2d-1 of the present invention

¹ H-NMR (CDCl ₃ ) δ: ((8.04-7.66) + (7.53-7.50) + (7.42-7.33) + (7.30-7.15)) (5H, m), 6.79-6.41 (1H, m), ((4.02-3.23) + (2.85-2.38)) (14H, 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 in the table.

A compound represented by formula (1a).

E in the formula represents a substituent described in [Table 8] below.

A compound represented by formula (1b).

E in the formula represents a substituent described in [Table 9] below.

A compound represented by formula (2a).

E in the formula represents a substituent described in [Table 10] below.

A compound represented by formula (2b-1).

Compound 2b-1 of the present invention
¹ H-NMR (CDCl ₃ ) δ: 9.62-9.59 (1H, m), 9.51-9.49 (1H, m), 8.47-8.44 (1H, m), 8.16-8.14 (1H, m), 8.12-8.09 ( 1H, m), 8.03-7.99 (1H, m), 7.93-7.91 (1H, m), 4.42-4.39 (2H, m), 4.02-3.98 (2H, m), 2.84-2.80 (2H, m), 2.79-2.75 (2H, m).

A compound represented by formula (2c).

E in the formula represents a substituent described in [Table 11] below.

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 of the present compounds 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 In a mixture of 35 parts of xylene and 35 parts of DMF, 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added and mixed to obtain each preparation.

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 mixed, and the compounds 1a-1 to 1a-5, 1b-1, 1b-2, 2a of the present invention are further mixed. -1 to 2a-12, 2b-1, 2c-1, 2c-2, and 2d-1 20 parts are added and mixed to obtain each wettable powder.

Formulation Example 3
Compound 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 Then, 1 part of 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 by a granulator, and dried by ventilation to obtain each granule.

Formulation Example 4
Compound 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 Dissolve in an appropriate amount of acetone, add 5 parts of synthetic hydrous hydroxide fine powder, 0.3 part of isopropyl acid phosphate and 93.7 parts of fusami clay, stir and mix thoroughly, and evaporate and remove acetone to remove each powder. Get.

Formulation Example 5
35 parts of a mixture (weight ratio 1: 1) of polyoxyethylene alkyl ether sulfate ammonium salt and white carbon, and compounds 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12 of the present invention Each flowable agent is obtained by mixing 10 parts of any one of 2b-1, 2c-1, 2c-2 and 2d-1 and 55 parts of water and finely pulverizing them by a wet pulverization method.

Formulation Example 6
Compounds 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 of the present invention 0.1 1 part is dissolved in a mixture of 5 parts xylene and 5 parts trichloroethane, and this is mixed with 89.9 parts kerosene to obtain each oil.

Formulation Example 7
Compounds of the present invention 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 Dissolve in 0.5 mL and drop this solution into 5 g of animal solid feed powder (solid feed powder CE-2 for breeding, product of Nippon Claire Co., Ltd.) and mix uniformly. Then acetone is evaporated to dryness to obtain each poisonous bait.

Formulation Example 8
Compounds 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 of the present invention 0.1 Part, neothiozole (manufactured by Chuo Kasei Co., Ltd.) 49.9 parts in an aerosol can, and after mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are added, shaken, and an actuator aerosol is attached by attaching an actuator. obtain.

Formulation Example 9
Compounds of the present invention 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 0.6 Parts, BHT (2,6-di-tert-butyl-4-methylphenol) 0.01 part, xylene 5 parts, kerosene 3.39 parts and emulsifier {Rheodor MO-60 (manufactured by Kao Corporation)} 1 part After the mixture and 50 parts of distilled water are filled in an aerosol container and a valve is mounted, 40 parts of propellant (LPG) is pressurized and filled through the valve to obtain an aqueous aerosol.

Formulation Example 10
Compounds 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 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
Compound 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 Melt 95 parts of ethylene-methyl methacrylate copolymer (ratio of methyl methacrylate in the copolymer: 10% by weight, ACLIFT (registered trademark) WD301, manufactured by Sumitomo Chemical Co., Ltd.) with a closed pressure kneader (Moriyama Seisakusho) 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
Compound 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 95 parts of a soft vinyl chloride resin is 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 to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm. obtain.

Formulation Example 13
Compounds of the present invention 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 100 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 are mixed and the resulting mixture is Compress to size to obtain tablets.

Formulation Example 14
Compound 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 60 mg, corn starch 25 mg, carmellose calcium 6 mg, and 5% hydroxypropylmethylcellulose proper amount are mixed, and the obtained mixture is filled into a hard shell gelatin capsule or hydroxypropylmethylcellulose capsule to obtain a capsule.

Formulation Example 15
Compound 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 Distilled to 500 mL of acid, 2000 mg of sodium chloride, 150 mg of methylparaben, 50 mg of propylparaben, 25000 mg of granular sugar, 13000 mg of sorbitol (70% solution), 100 mg of VeegumK (VanderbiltCo.), 35 mg of fragrance, and 500 mg of colorant to a final volume of 100 mL Add water and mix to obtain a suspension for oral administration.

Formulation Example 16
Compound 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2, and 2d-1 5% by weight Is dissolved in 5% by weight of polysorbate 85, 3% by weight of benzyl alcohol and 30% by weight of propylene glycol, and a phosphate buffer solution is added so that the pH of this solution is 6.0 to 6.5. 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, any one of the compounds 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 10 Distribute the weight percentage to obtain a paste preparation for oral administration.

Formulation Example 18
Compound 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2, and 2d-1 5% by weight Is mixed with 95% by weight of limestone powder to obtain granules for oral administration using the wet granulation method.

Formulation Example 19
5 parts of any one of the present compounds 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 Dissolve in 80 parts of diethylene glycol monoethyl ether and mix with 15 parts of propylene carbonate to obtain a spot-on solution.

Formulation Example 20
10 parts of any one of the present compounds 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 Dissolve in 70 parts of diethylene glycol monoethyl ether and mix with 20 parts of 2-octyldodecanol to obtain a pour-on solution.

Formulation Example 21
Compounds of the present invention 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 Any one of 0.5 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 to the resulting mixture, and the mixture was stirred and mixed until a homogeneous solution was obtained. Add 5 parts and further stir and mix to obtain a shampoo of a uniform solution.

Formulation Example 22
Compounds of the present invention 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 Any one of 0.15 The animal feed premix is obtained by sufficiently stirring and mixing 4.85% by weight of a mixture consisting of dilute calcium phosphate, diatomaceous earth, Aerosil, and carbonate (or chalk).

Formulation Example 23
Compounds of the present invention 1a-1 to 1a-5, 1b-1, 1b-2, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 Any one kind 7.2g , 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 form, cooled and solidified 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
Formulations of the compounds 1a-1 to 1a-4, 2a-1 to 2a-12, 1b-1, 1b-2, 2c-1, 2c-2 and 2d-1 obtained according to Formulation Example 5 Each was diluted with water so that the concentration of the compound of the present invention was 500 ppm to obtain a diluted solution.

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. The seedling 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 treatment in the untreated section Cai: number of parasitic live insects at the time of investigation in the untreated section Tb: number of insects before the treatment in the treated section Tai: number of parasitic live insects at the time of survey in the treated section The group refers to a 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, in all treatment sections where the present compounds 1a-1 to 1a-4, 2a-1 to 2a-12, 1b-1, 1b-2, 2c-1, 2c-2 or 2d-1 were tested. The control value was 90% or more.

Test example 2
Formulations of the compounds 1a-1 to 1a-5, 2a-1 to 2a-12, 1b-1, 1b-2, 2c-1, 2c-2 and 2d-1 obtained according to Formulation Example 5 Each was diluted with water so that the concentration of the compound of the present invention was 500 ppm to obtain a diluted solution.

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, in all treatment sections where the present compounds 1a-1 to 1a-5, 2a-1 to 2a-12, 1b-1, 1b-2, 2c-1, 2c-2 or 2d-1 were tested. The death rate was 80% or more.

Test example 3
Compounds of the present invention 1a-1, 1a-4, 1a-5, 2a-1 to 2a-4, 2a-6 to 2a-12, 1b-1, 2b-1, 2c- obtained according to Formulation Example 5 The preparations 1, 2c-2 and 2d-1 were each diluted with water so that the concentration of the compound of the present invention was 500 ppm to obtain a diluted solution.

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 was placed, and 2 mL of the diluted solution was irrigated. After air drying, 5 third instar larvae of Spodoptera litura were released and covered. 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 present compounds 1a-1, 1a-4, 1a-5, 2a-1 to 2a-4, 2a-6 to 2a-12, 1b-1, 2b-1, 2c-1, 2c-2 or In all of the treatment areas where 2d-1 was tested, the death rate was 80% or more.

Test example 4
The compounds of the present invention 1a-1 to 1a-5, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 and 2d-1 obtained according to Formulation Example 5 are each compound of the present invention. The resulting solution was diluted with water so that the concentration thereof became 200 ppm to obtain a diluted solution.

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 mortality rate was measured in all treatments where the compounds 1a-1 to 1a-5, 2a-1 to 2a-12, 2b-1, 2c-1, 2c-2 or 2d-1 were tested. It showed 80% or more.

Test Example 5
Compounds of the present invention 1a-1, 1a-4, 1a-5, 2a-1 to 2a-12, 1b-1, 1b-2, 2b-1, 2c-1, 2c- obtained according to Formulation Example 5 The preparations 2 and 2d-1 were each diluted with water so that the concentration of the compound of the present invention was 500 ppm to obtain a diluted solution.

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 compound 1a-1, 1a-4, 1a-5, 2a-1 to 2a-12, 1b-1, 1b-2, 2b-1, 2c-1, 2c-2 or 2d-1 In all treatment sections tested, a mortality rate of 100% was shown.

Test Example 6
Compounds of the present invention 1a-1 to 1a-5, 2a-1 to 2a-4, 2a-6 to 2a-12, 1b-1, 1b-2, 2b-1, 2c- obtained according to Formulation Example 5 The preparations 1, 2c-2 and 2d-1 were each diluted with water so that the concentration of the compound of the present invention was 500 ppm to obtain a diluted solution.

The diluted solution (0.7 mL) was added to ion-exchanged water (100 mL) (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-5, 2a-1 to 2a-4, 2a-6 to 2a-12, 1b-1, 1b-2, 2b-1, 2c-1, 2c-2 or In all of the treatment areas where 2d-1 was tested, the death rate was 91% or more.

Test Example 7
Formulations of the present compounds 2a-1 to 2a-3, 2a-6 to 2a-12, 1b-1, 2b-1, 2c-1, 2c-2 and 2d-1 obtained according to Formulation Example 5 Each was diluted with water so that the concentration of the compound of the present invention was 200 ppm to obtain a diluted solution.

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. 20 mL each of the diluted solution was sprayed on the seedlings.

Cb: number of insects before treatment in the untreated group Cai: number of parasitic live insects at the time of survey in the untreated group Tb: number of insects before the treatment in the treated group Tai: number of parasitic insects at the time of survey in the treated group

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, in all treatment sections where the present compounds 2a-1 to 2a-3, 2a-6 to 2a-12, 1b-1, 2b-1, 2c-1, 2c-2 or 2d-1 were tested. The control value was 90% or more.

Test Example 8
Formulations of the compounds 1a-4, 1a-5, 2a-1 to 2a-12, 1b-2, 2b-1, 2c-1, 2c-2 and 2d-1 obtained according to Formulation Example 5 Each was diluted with water so that the concentration of the compound of the present invention was 200 ppm to obtain a diluted solution.

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, in all the treatment sections where the present compounds 1a-4, 1a-5, 2a-1 to 2a-12, 1b-2, 2b-1, 2c-1, 2c-2 or 2d-1 were tested. The death rate was 80% or more.

Test Example 9
Formulations of the present compounds 1a-4, 2a-1 to 2a-8, 2a-11, 1b-2, 2b-1, 2c-1, 2c-2 and 2d-1 obtained according to Formulation Example 5 Each was diluted with water so that the concentration of the compound of the present invention was 500 ppm to obtain a 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, in all the treatment sections where the present compounds 1a-4, 2a-1 to 2a-8, 2a-11, 1b-2, 2b-1, 2c-1, 2c-2 or 2d-1 were tested. The control rate was 90% or more.

Test Example 10
The preparations of the compounds of the present invention 2a-1 to 2a-4, 2a-7 to 2a-9, 2a-11, 2b-1, 2c-1 and 2d-1 obtained according to Formulation Example 5 are respectively represented in the present invention. It diluted with water so that the density | concentration of a compound might be 500 ppm, and the dilution liquid 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 mortality rate was measured in all treatments where the compounds 2a-1 to 2a-4, 2a-7 to 2a-9, 2a-11, 2b-1, 2c-1 or 2d-1 were tested. 100%.

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

Claims

Formula (I)

[Where:
J 1 , J 2 , J 3 and J 4 each independently represent a nitrogen atom or CR 6 (provided that at least one of J 1 , J 2 , J 3 and J 4 represents a nitrogen atom),
R 1 and R 3 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, —R 7 , —OR 7 or —S (O) p R 7 ;
R 2 represents —R 7 , —OR 7 or —S (O) p R 7 ,
Each X independently represents —R 7 , —OR 7 , a halogen atom or a cyano group;
R 4 and R 5 are each independently a hydrogen atom, —R 7 , (C1-C4 alkoxy) C1-C4 alkyl group, —C (O) R 7 or —CO 2 represents R 7 ,
R 6 represents a hydrogen atom, a halogen atom, —R 8 or —OR 8 ,
R 7 represents a C1-C6 chain hydrocarbon group which may have one or more halogen atoms,
R 8 represents a C1-C3 chain hydrocarbon group,
G 1 and G 6 each independently represent —CR 9 R 10 — or —C (O) —,
G 2 , G 3 , G 4 and G 5 are each independently -CR 9 R 10- , -C (O)-, -S (O) k (Q) m- , -O-, -NR 11 - or a single bond and represents (wherein, G 2, G 3, at least one of G 4 and G 5 is -S (O) k (Q) m -, - O- or -NR 11 - represents a.) ,
Q represents NR 12 or NC (O) R 7 ;
R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, a cyano group, —R 7 , —OR 7 , —S (O) p R 7 , —C (O) R 7 or —CO 2 R 7 . Represent,
R 11 represents a hydrogen atom, —R 7 , —C (O) R 7 , —CO 2 R 7 or SO 2 R 7 ,
R 12 represents a hydrogen atom, a cyano group, or a C1-C6 alkyl group which may have one or more halogen atoms,
k represents 0, 1 or 2,
m represents 0 or 1;
the sum of k and m represents 0, 1 or 2;
n and p each independently represent 0, 1 or 2. ]
An oxalylamide compound represented by:
The oxalylamide compound according to claim 1, wherein any one of J 1 , J 2 , J 3 and J 4 is a nitrogen atom, and the other is CR 6 .
The oxalylamide compound according to claim 1, wherein any one of J 1 , J 2 , J 3 and J 4 is a nitrogen atom and the other is CH.
Any one of R 1 and R 3 is a bromine atom, an iodine atom or —R 13 , and the other is a —R 7A , —R 7B , —OR 7B or —S (O) p R 7B group; The oxalylamide compound according to any one of claims 1 to 3, wherein R 7A is a C1-C6 alkyl group, and R 7B is a C1-C6 alkyl group having one or more halogen atoms.
The oxalylamide compound according to claim 4, wherein R 2 is -R 7B .
The oxalylamide compound according to claim 4, wherein R 2 is -OR 7B .
The oxalylamide compound according to claim 4, wherein R 2 is -S (O) p R 7B .
A harmful arthropod control composition comprising the compound according to any one of claims 1 to 7 and an inert carrier.
A method for controlling harmful arthropods, which comprises applying an effective amount of the compound according to any one of claims 1 to 7 to harmful arthropods or habitats of harmful arthropods.