WO2007116949A1

WO2007116949A1 - Plant protection method

Info

Publication number: WO2007116949A1
Application number: PCT/JP2007/057699
Authority: WO
Inventors: Norihisa Sakamoto; Masato Konobe
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2006-04-03
Filing date: 2007-03-30
Publication date: 2007-10-18

Abstract

A plant can be protected from the pest damage by applying an effective amount of an (N'-methyl)benzoylurea compound represented by the formula (I) or a salt thereof to a root, a seed or a rhizosphere of the plant. (I) wherein X, R1, R2, R3 and m are as defined in the description.

Description

Plant Protection Method Technical Field

The present invention relates to a plant protection method, and more particularly to a plant protection method from harm by pests. Background art

GB 1324293, US 4170657 and US 4243680 describe N′-methylbenzoylurea compounds methylated at the N ′ position.

Disclosure of Invention

As a result of intensive studies to find a new plant protection method, the present inventors have determined that an effective amount of N, monomethyl benzoylurea compound represented by the following formula (I) or a salt thereof is the root or seed of a plant, or a plant It was found that by applying to the root zone of the plant, the plant can be protected from harm by pests, and the present invention has been reached.

That is, the present invention is as follows.

Formula (I)

[Where,

X represents a fluorine atom or a chlorine atom;

R ¹ is a hydrogen atom, a C 1 -C 6 alkyl group which may be substituted with a halogen atom, a C 2 -C 6 alkenyl group which may be substituted with a halogen atom, a C 2 -C 6 alkynyl group, C 6— C 14 aryl group, C 7— C 11 aralkyl group, C 2—C 6 alkoxy alkyl group, C 7— C 14 aryl alkyl group, C 3—C 6N, N-di (alkyl) amino alkyl group, C 2 — C 6 alkylthioalkyl group, C2 1 C 6 alkylsulfinylalkyl group, C 2 -C 6 alkylsulfonyl alkyl group, C 3— C 9 alkoxy alkoxy alkylyl group, C 2—C 6 alkoxy carbon group Ponyl group, C 8— C 12 aralkyloxycarbonyl group, N, N—di (CI—C 6 alkyl) force rubamoyl group, C 2—C 6 alkylcarbonyl group optionally substituted with halogen atom, formyl group, a optionally substituted C 1 -C be the 5 alkylsulfonyl group or a C 6- C 10 § Li one Rusuruhoniru group with a halogen atom, R ² is substituted with C port Gen atom or C port Gen atoms Represents an optionally substituted C 1—C 4 alkyl group,

R ³ may be a halogen atom, a CI-C4 alkyl group that may be substituted with a halogen atom, a C 1 C4 alkoxy group that may be substituted with a halogen atom, or a halogen atom. A C2-C6 alkoxyalkoxy group, a C2-C4 alkenyloxy group optionally substituted with a halogen atom or a C2-C4 alkynyloxy group optionally substituted with an octalogen atom,

m represents one of integers from 0 to 4. ]

(Ν'-methyl) benzoylurea compound (hereinafter sometimes referred to as the present compound) represented by the formula: or a salt thereof, which is applied to the root or seed of a plant or the rhizosphere of a plant A method for protecting plants from harm by pests having 2. In formula (I), R ¹ is a hydrogen atom, R ³ is a halogen atom, C 1 may be substituted with a halogen atom, or C 1 may be substituted with a C 4 alkoxy group or a halogen atom A step of applying an effective amount of a benzoylurea compound or a salt thereof to the root or seed of a plant or the rhizosphere of a plant, which is a 1-C4 alkyl group and m is 0 or 1 (Ν'-methyl) Yes 1. The plant protection method from the harm by the pest described.

3. The plant protection method according to 1. or 2., wherein the plant root or seed or the plant rhizosphere is the plant rhizosphere.

4. The plant protection method according to 3., wherein the rhizosphere of the plant is soil on which the plant grows.

5. A plant protectant from pests containing this compound or a salt thereof and an inert carrier.

6. In formula (I), R ¹ is a hydrogen atom and R ³ is a halogen atom, which may be substituted with a halogen atom C 1 C 1 alkoxy group which may be substituted with a C 4 alkoxy group or a halogen atom —C 4 alkyl group, and m is 0 or 1 (Ν′—methyl) Contains a benzoylurea compound or a salt thereof and an inert carrier. 5. A plant protective agent from harm by pests.

7. The plant protection agent according to 5. or 6, which is used for treatment of the plant rhizosphere. 8. The plant protective agent according to 5 or 6, which is used for treating soil where plants grow.

9. (Ν '-methyl) benzoylurea compound or its salt represented by formula (I) for application to plant roots or seeds or plant rhizosphere to protect plants from harm by pests Use of. In the present invention, represented by R ¹ of the present compound,

Examples of the C 1 -C 6 alkyl group optionally substituted by a halogen atom include a methyl group, a chloromethyl group, a difluoromethyl group, a trichloromethyl group, an ethyl group, a 2-bromoethyl group, 2, 2, 2-trifluor. Oloethyl group, propyl group, 3,3,3-trifluoropropyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 4,4,4 trifluorobutyl group Pentyl group, isopentyl group, neopentyl group, 5, 5, 5-trifluoropentyl group, hexyl group and 6, 6, 6-trifluorohexyl group,

Examples of the C 2 -C 6 alkenyl group which may be substituted with a halogen atom include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 2-butenyl group, and an isobutenyl group. Group, and 3,3-dichloro-2-propenyl group, and C 2 -C 6 alkynyl group includes, for example, echelle group, 2-propynyl group and 1-propynyl group,

Examples of the C 6 -C 14 aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a biphenylyl group,

Examples of the C 7 -C 11 aralkyl group include a benzyl group and a phenethyl group,

Examples of the C 2 -C 6 alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a 1-propoxymethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 3-methoxypropyl group, and a 3-ethoxypropyl group. And

Examples of the C 7 -C 14 aryloxyalkyl group include a phenoxymethyl group and a 2-phenoxychetyl group,

Examples of the C 3 -C 6 N, N-di (alkyl) aminoalkyl group include a dimethylaminomethyl group, a 2- (dimethylamino) ethyl group, a jetylaminomethyl group, and a 2- (jetylamino) ethyl group. And

Examples of the C 2 _C 6 alkylthioalkyl group include a methylthiomethyl group, an ethylthiomethyl group, a 2- (methylthio) ethyl group, and a 2- (ethylthio) ethyl group. W 200

Four

Are mentioned,

Examples of the C 2 -C 6 alkylsulfinylalkyl group include a methylsulfinylmethyl group, an ethylsulfiermethyl group, a 2- (methylsulfier) ethyl group, and a 2- (ethylsulfiel) ethyl group,

Examples of the C 2 -C 6 alkylsulfonylalkyl group include a methylsulfonylmethyl group, an ethylsulfonylmethyl group, a 2- (methylsulfonyl) ethyl group, and a 2- (ethylsulfonyl) ethyl group,

Examples of the C 3 -C 9 alkoxyalkoxyalkyl group include (2-methoxyethoxy) methyl group,

Examples of the C 2 -C 6 alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a normal propoxycarbonyl group, an isopropoxycarbonyl group, a normal butoxycarbonyl group, and a tert-butoxycarbonyl group.

Examples of the C 8 -C 12 aralkyloxycarbonyl group include a benzyloxycarbonyl group,

Examples of N, N-di (C 1 -C 6 alkyl) strong rubamoyl groups include dimethylcarbamoyl and jetylcarbamoyl,

Examples of the C 2 -C 6 alkylcarbonyl group optionally substituted with a halogen atom include an acetyl group, a propionyl group, a trifluoroacetyl group, and a chloroacetyl group,

Examples of the C 1 -C 5 alkylsulfonyl group optionally substituted with a halogen atom include a methanesulfonyl group, an ethanesulfonyl group, and a trifluoromethanesulfonyl group,

Examples of the C 6 -C 10 arylaryl group include a benzenesulfonyl group and a toluenesulfonyl group.

Represented by R ^2,

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

Examples of the C1-C4 alkyl group which may be substituted with a halogen atom include a methyl group, a chloromethyl group, a difluoromethyl group, a trichloromethyl group, a trifluoromethyl group, an ethyl group, a 2-bromoethyl group, 2, 2 , 2-Trifluoroethyl group, Pentafluoroethyl group, Propyl group, 3, 3, 3-Trifluoropropiyl Group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group and 4,4,4-trifluorobutyl group,

Indicated by R ³ ,

Examples of the C 1 -C 4 alkyl group optionally substituted with a halogen atom include a methyl group, a chloromethyl group, a difluoromethyl group, a trichloromethyl group, a trifluoromethyl group, an ethyl group, a 2-bromoethyl group, and 2, , 2-Trifluoroethyl group, Penufluoroethyl group, Propyl group, 3, 3, 3-Trifluoropropyl group, Isopropyl group, Butyl group, Isobutyl group, sec-butyl group, tert-butyl group and 4, 4 , 4 trifluorobutyl group,

Examples of the C 1 -C 4 alkoxy group optionally substituted with a halogen atom include a methoxy group, an ethoxy group, a 1-propyloxy group, an isopropoxy group, a tert-butoxy group, a difluoromethoxy group, and a trifluoro group. Methoxy group, 2, 2, 2-trifluorofluoro group, 1, 1, 2, 2, 2-pentafluoroethoxy group, 1, 1, 2, 2-tetrafluoroethoxy group, 1, 1, 2, 2 , 3, 3, 3 heptane fluor, 1 propoxy group and 1, 1, 2, 3, 3, 3-hexafluoro 1-group poxy group,

Examples of the C 2 -C 6 alkoxyalkoxy group optionally substituted with a halogen atom include 2-trifluoromethoxy-1,1,2-trifluoroethoxy group,

Examples of the C 2 -C 4 alkenyloxy group optionally substituted with a halogen atom include a 2-propenyloxy group and a 3,3-dichloro-2-propenyloxy group,

Examples of the C 2 -C 4 alkynyloxy group which may be substituted with a halogen atom include a 2-propynyloxy group. This compound is capable of forming an acid addition salt in which a basic group such as a dialkylamino group in a substituent in the molecule can be agrochemically acceptable with an inorganic acid or an organic acid. Examples of the inorganic acid addition salt of the compound include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, and perchloric acid, and examples of the organic acid addition salt of the compound include Formic acid, acetic acid, propionic acid, succinic acid, succinic acid, benzoic acid, p-toluenesulfonic acid, meta And salts with sulfonic acid and trifluoroacetic acid. Next, the synthesis method of this compound is shown.

This compound can be produced, for example, by the following (Synthesis Method 1) to (Synthesis Method 4).

(Synthesis Method 1)

Among the compounds, the formula (I 1 1)

[Wherein, X, R ² , R ³ and m represent the same meaning as described above. ]

The compound represented by the formula (II)

[Wherein X represents the same meaning as described above. ]

And a compound represented by the formula (ΙΠ)

[Wherein R ² , R ³ and m represent the same meaning as described above. ]

It can manufacture by making the compound shown by react.

The reaction is usually performed in a solvent.

Examples of the solvent used in the reaction include ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane and heptane, jetyl ether, tetrahydrofuran, 1 , 4-dioxane, 1,2-dimethoxyethane, ethers such as 1,2-diethoxyethane, halogenated hydrocarbons such as chloroform, benzene, dichlorobenzene, nitriles such as acetonitril, N, N —Dimethylformamide, N, N-dimethylase And aprotic polar solvents such as toamide, 1-methyl-2-pyrrolidone, 1,3-dimethylimidazolinone, dimethyl sulfoxide, water, and mixtures thereof.

The amount of the compound represented by the formula (III) used in the reaction is usually 0.5 to 2 mol relative to 1 mol of the compound represented by the formula (II).

The reaction temperature is usually in the range of -78 to 150, and the reaction time is usually in the range of 0.1 to 100 hours.

After completion of the reaction, for example, the reaction mixture is poured into water, extracted with an organic solvent, and then subjected to post-treatment operations such as drying and concentration of the organic layer, whereby the compound represented by the formula (1-1) is obtained. Can be isolated. The isolated compound represented by the formula (1-1) can be further purified by recrystallization, column chromatography or the like.

(Synthesis Method 2)

Among these compounds, the formula (1-2)

[Wherein, X, R ² , R ³ and m represent the same meaning as described above, and R ¹ — ¹ is a C 1 C 6 alkyl group which may be substituted with a halogen atom, and is substituted with a halogen atom. C 2—C 6 alkenyl group, C 2—C 6 alkynyl group, C 6—C 14 aralkyl group, C 7—C 11 aralkyl group, C 2—C 6 alkoxyalkyl group, C7—C 14 4 ally 1-Luoxyalkyl group, C3-C6N, N-di (alkyl) aminoalkyl group, C2-C6 alkylthioalkyl group, C2-C6 alkylsulfinylalkyl group, C2-C6 alkylsulfonylalkyl group or C3-C 9Alkoxy represents an alkoxyalkyl group. ]

The compound represented by formula (IV)

[Wherein, X and R ¹ represent the same meaning as described above. ]

Produced by reacting the compound represented by formula (III) with the compound represented by formula (III) W

8

Can.

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

Examples of the solvent used in the reaction include ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, jetyl ether, and tetrahydrofuran. 1,4-dioxane, 1,2-dimethoxyethane, ethers such as 1,2-diethoxyethane, halogenated hydrocarbons such as chloroform, benzene and dichlorobenzene, nitriles such as acetonitrile and nitrile, N , N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethylimidazolinone, dimethylsulfoxide, and other aprotic polar solvents, water, and mixtures thereof.

Examples of the base used in the reaction include hydroxides of alkali metal or alkaline metal such as sodium hydroxide, lithium hydroxide, calcium hydroxide, sodium hydride, potassium hydride, hydrogenation. Alkali metals such as calcium or alkali earth metal hydrides, alkali metals such as sodium carbonate or potassium carbonate, or alkaline earth metal carbonates, sodium ethylate, sodium methylate, etc. And organic bases such as tributylamine, pyridine, 1,8-diazapicyclo [5,4,0] undecene (hereinafter abbreviated as DBU), and the like.

The amount of the reagent used in the reaction can be used in an excess amount when using a reagent that is liquid under the reaction conditions, but usually the formula (IV) is added to 1 mol of the compound represented by formula (IV). The compound represented by III) is 1 to 4 moles, and the base is 1 to 4 moles.

The reaction temperature is usually in the range of 1 78 to 15 50, and the reaction time is usually in the range of 0.1 to 20 hours.

After completion of the reaction, for example, the reaction mixture is poured into water, extracted with an organic solvent, and then subjected to post-treatment operations such as drying and concentration of the organic layer, whereby the compound represented by the formula (1-2) is obtained. Can be isolated. The isolated compound represented by the formula (1-2) can be further purified by recrystallization, column chromatography or the like.

(Synthesis Method 3) Of these compounds, the formula (I 1 3)

Wherein, X, R ^2, R ³ and m are as defined above, R ¹ - ² is optionally substituted with a halogen atom C 1-C 6 alkyl group, substituted with a halogen atom C 2—C 6 alkenyl group, C 2—C 6 alkynyl group, C 7—C 11 aralkyl group, C 2—C 6 alkoxyalkyl group, C 7—C 14 allyloxyalkyl group, C 3—C 6 N, N—di (alkyl) aminoalkyl group, C 2—C 6 alkyl thioalkyl group, C 2—C 6 alkylsulfinylalkyl group, C 2 -C 6 alkylsulfonylalkyl group, C 3 -C 9Alkoxyalkoxyalkyl group, C 2 —C 6 alkoxycarbonyl group, C 8 -C 12 aralkyloxycarbonyl group, N, N—di (di-6-alkyl), rubamoyl group, substituted with halogen atom C 2-C 6 alkylcarbonyl group, formyl group, halogen Be substituted with a child represents an C 1 one C 5 alkylsulfonyl group or a C 6- C 1 0 Arirusu Ruhoniru group. ]

The compound represented by the formula is a compound represented by the formula (1-1) and the formula (V)

Li— _R i-2 (V)

Wherein, R ¹ - ² are as defined above, L ¹ is a halogen atom (e.g., chlorine atom and bromine atom), methanesulfonyl O alkoxy group, benzenesulfonyl O alkoxy group, toluene sulfonyl O alkoxy group, Represents a methoxysulfonyloxy group or an oxysulfonyloxy group; ]

Can be produced by reacting with a compound represented by the above in the presence of a base.

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

Examples of the solvent used in the reaction include ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, jetyl ether, tetrahydrofuran, 1 , 4-dioxane, ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, halogenated hydrocarbons such as chloroform, chlorobenzene, and dichlorobenzene, nitriles such as acetonitrile, N, N —Dimethylformamide, N, N-dimethyla Examples include aprotic polar solvents such as cetamide, 1-methyl-2-pyrrolidone, 1,3-dimethylimidazolinone and dimethyl sulfoxide, water, and mixtures thereof.

Examples of the base used in the reaction include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, hydroxy hydroxide, calcium hydroxide, and alkali such as sodium hydride, potassium hydride, and calcium hydride. Metal or alkaline earth metal hydrides, sodium carbonate, alkaline earth metal carbonates such as sodium carbonate, alkaline earth metal carbonates, alkali metal alcoholates such as sodium ethylate, sodium methylate, etc. Organic lithium such as normal butyl lithium and lithium diisopropylamide and organic bases such as triethylamine, pyridine and DBU.

The amount of the reagent used in the reaction can be used in an excess amount when a reagent that is liquid under the reaction conditions is used, but usually the amount is 1 mol of the compound represented by the formula (1-1). The compound represented by formula (V) is in a ratio of 1 to 4 mol, and the base is in a ratio of 丄 to 4 mol.

The reaction temperature is usually in the range of −78 to 1550, and the reaction time is usually in the range of 0.1 to 1 hour.

After completion of the reaction, for example, the reaction mixture is poured into water, extracted with an organic solvent, and then subjected to post-treatment operations such as drying and concentration of the organic layer, whereby the compound represented by the formula (1-3) is obtained. Can be isolated. The isolated compound represented by the formula (I 13) can be further purified by recrystallization, column chromatography or the like.

(Synthesis Method 4)

Among the compounds (I), the formula (I 1 2)

[Wherein, X, R ² , R ³ , R ¹ _ ¹ and m represent the same meaning as described above. ]

The compound represented by the formula (VI)

[Wherein, X represents the same meaning as described above, and L ² represents a halogen atom (for example, a chlorine atom, an iodine atom, and an iodine atom). ]

And a compound of formula (VI I)

[Wherein, R ¹ — R ² , R ³ and m represent the same meaning as described above. ]

It can manufacture by making the compound shown by react.

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

Examples of the solvent used in the reaction include ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane and heptane, jetyl ether, tetrahydrofuran, 1 , 4-Dioxane, 1,2-Dimethoxyshetane, Ethers such as 1,2-Diethoxyethane, Halogenated hydrocarbons such as Chromium Form, Chromatic Benzene, and Dichlorobenzene, Nitriles such as Acetitonitrile, N, Aprotic polar solvents such as N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethylimidazolinone, dimethyl sulfoxide, water, and mixtures thereof.

Examples of the base used in the reaction include sodium hydroxide, potassium hydroxide, hydrogenated hydroxide of alkaline metal or alkaline metal such as sodium hydroxide, lithium hydroxide, calcium hydroxide, and the like. Alkali metal such as calcium or alkali earth metal hydride, alkali metal such as sodium carbonate or potassium carbonate or carbonate of alkaline earth metal, sodium ethylate, sodium methylate, etc. Organic lithium such as alcoholate, normal butyl lithium, lithium diisopropylamide, and organic bases such as triethylamine, diisopropylethylamine, pyridine, DBU, and the like.

The amount of the reagent used in the reaction may be an excess amount when using a reagent that is liquid under the reaction conditions. Usually, the compound 1 represented by the formula (VI I) is used. The proportion of the compound represented by the formula (VI) is 1 to 4 mol and the base is 1 to 4 mol with respect to mol.

The reaction temperature is usually in the range of −78 to 180 ° C., and the reaction time is usually in the range of 0.1 to 200 hours.

After completion of the reaction, for example, the reaction mixture is poured into water, extracted with an organic solvent, and then subjected to post-treatment operations such as drying and concentration of the organic layer, whereby the compound represented by the formula (1-2) is obtained. Can be isolated. The isolated compound represented by the formula (I 12) can be further purified by recrystallization, column chromatography or the like. Next, a reference synthesis method of a synthetic intermediate of this compound will be shown.

(Reference Synthesis Method 1)

The compound represented by the formula (IV) is represented by the formula (VI II)

[Wherein X and R ¹ 1 ¹ represent the same meaning as described above. ]

It can be produced by reacting a compound represented by the above formula with a polyalkylalkoxysilane compound and a chlorocarbonylating agent.

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

Examples of the solvent used in the reaction include ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, jetyl ether, tetrahydrofuran, 1 , 4-dioxosan, ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, halogenated hydrocarbons such as chloroform, chlorobenzene, dichlorobenzene, nitriles such as acetonitrile, N, N —Aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide, 1-methyl-1-2-pyrrolidone, 1,3-dimethylimidazolinone, dimethyl sulfoxide, water, and mixtures thereof.

Examples of the base used in the reaction include sodium hydroxide, potassium hydroxide, hydrogenated hydroxide of alkaline metal or alkaline metal such as sodium hydroxide, lithium hydroxide, calcium hydroxide, and the like. Alkali metals such as calcium or alkali earth metal hydrides, alkali metals such as sodium carbonate and potassium carbonate W or alkaline earth metal carbonates, alkali metal alcoholates such as sodium edylate and sodium methylate, organic lithiums such as normal butyl lithium and lithium diisopropylamide, and organic bases such as triethylamine, pyridine and DBU .

Examples of the trialkylchlorosilane compound used in the reaction include trimethylchlorosilane and triethylchlorosilane.

Examples of the chlorocarbonylating agent used in the reaction include phosgene, trichloromethyl chloroformate, and bis (trichloromethyl) carbonate. The amount of the reagent used in the reaction is usually 1 to 4 moles of the trialkylchlorosilane compound, 1 to 4 moles of the chlorocarbonylating agent to 1 mole of the compound represented by the formula (Ή Π), The base is usually in a proportion of 1 to 4 mol.

The reaction temperature is usually in the range of −78 to 150 ° C., and the reaction time is usually in the range of 0.1 to 200 hours.

After completion of the reaction, the compound represented by the formula (IV) can be isolated by performing post-treatment operations such as concentrating the reaction mixture as it is. The isolated compound represented by the formula (IV) can be used in the next step without purification.

(Reference Synthesis Method 2)

The compound represented by the formula (VI I) is represented by the formula (IX)

[Wherein R ² , R ³ and m represent the same meaning as described above. ]

And a compound of formula (X)

H ₂ N—R ^1-1 (X)

[Wherein R ^{1 1} represents the same meaning as described above. ]

It can manufacture by making the compound shown by react.

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

Examples of the solvent used in the reaction include ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane and heptane, jetyl ether, tetrahydrofuran, 1, 4—Zoki Sun, ethers such as 1,2-dimethoxyethane and 1,2-diethoxyethane, halogenated hydrocarbons such as chloroform, chlorobenzene and dichlorobenzene, nitriles such as acetonitrile, N, N-dimethyl Examples include aprotic polar solvents such as formamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethylimidazolinone and dimethyl sulfoxide, water, and mixtures thereof.

Examples of the base used in the reaction include hydroxides of alkali metal or alkaline metal such as sodium hydroxide, lithium hydroxide, calcium hydroxide, sodium hydride, potassium hydride, hydrogenation. Alkali metals such as calcium or alkali earth metal hydrides, alkali metals such as sodium carbonate or potassium carbonate, or alkaline earth metal carbonates, sodium ethylate, sodium methylate, etc. Organic lithium such as normal butyl lithium and lithium diisopropylamide, and organic bases such as triethylamine and DBU. Alternatively, an excess amount of (X) can be used as the base.

The amount of the reagent used in the reaction is 1 to 6 moles of the compound represented by formula (X) and 1 to 6 moles of the base, based on 1 mole of the compound represented by formula (IX). The

The reaction temperature is usually in the range of −78 to 1550, and the reaction time is usually in the range of 0.1 to 2200 hours.

After completion of the reaction, for example, the compound represented by the formula (VI I) is isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then drying and concentrating the organic layer. can do. The isolated compound represented by the formula (VI I) can be further purified by recrystallization, column chromatography or the like. (Reference Synthesis Method 3)

The compound represented by the formula (IX) can be produced by reacting the compound represented by the formula (I I I) with a chlorocarbonylating agent.

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

Examples of the solvent used in the reaction include ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, jetyl ether, tetrahydrofuran, 1 , 4 dioxosan, ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, Halogenated hydrocarbons such as roloform, black benzene, dichlorobenzene, nitriles such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethylimidazolinone And aprotic polar solvents such as dimethyl sulfoxide, water, and mixtures thereof.

Examples of the base used in the reaction include sodium hydroxide, alkaline hydroxide, calcium hydroxide, and other hydroxides of alkaline metals or alkaline metals, hydrogen sodium, potassium hydride, hydrogen Alkali metals such as calcium hydroxide or alkali earth metal hydrides, alkali metals such as sodium carbonate and potassium carbonate, or alkaline earth metal carbonates, sodium ethylate, and alkali metals such as sodium methylate And organic bases such as triethylamine, pyridine, DBU and the like and organic lithiums such as alcoholate, normal butyl lithium and lithium diisopropylamide.

Examples of the chlorocarbonylating agent used in the reaction include phosgene, trichloromethyl chloroformate, bis (trichloromethyl) carbonate, and the like. The amount of the reagent used in the reaction is usually 1 to 4 moles of the chlorocarbonylating agent and 1 to 4 moles of the base, based on 1 mole of the compound represented by the formula (I II).

The reaction temperature is usually in the range of 78 to 150 ° C, and the reaction time is usually in the range of 0.1 to 200 hours.

After completion of the reaction, for example, the compound represented by the formula (IX) is isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then drying and concentrating the organic layer. be able to. The isolated compound represented by the formula (IX) can be further purified by column chromatography or the like. After completion of the reaction, the compound represented by the formula (IX) can also be isolated by performing post-treatment operations such as concentrating the reaction mixture as it is. The compound produced by the above synthesis method is further known per se, for example, alkylation, alkenylation, alkynylation, acylation, amination, sulfidation, sulfinylation, sulfonation, oxidation, reduction, halogenation. The substituent can be converted into other desired substituents by nitration or the like. As an aspect of this compound, the following are mentioned in this compound, for example. m is 0 or 1 (N, —methyl) benzoylurea compound;

X is a fluorine atom (Ν '-methyl) benzoylurea compound;

X is a chlorine atom (Ν '-methyl) benzoylurea compound;

R ¹ is a hydrogen atom (Ν '—methyl) benzoylurea compound;

R ³ is a halogen atom, a C 1-C 4 alkoxy group which may be substituted with a halogen atom or a C 1-C 4 alkyl group which may be substituted with a halogen atom (Ν '-methyl) benzoylurea compound ;

R ³ is a halogen atom, a C 1 -C 4 alkoxy group which may be substituted with a halogen atom, or a C 1 C 4 alkyl group which may be substituted with a halogen atom, and m is 0 or 1 ( Ν '—methyl) benzoylurea compound;

R ¹ is a hydrogen atom, R ³ is a halogen atom, which may be substituted with a halogen atom, or a single C 4 alkoxy group or a C 1 -C 4 alkyl group which may be substituted with a halogen atom, (Ν '-methyl) benzoylurea compound in which m is 0 or 1. The plant protective agent of this invention contains this compound or its salt, and an inert carrier. Examples of the inert carrier include a solid carrier, a liquid carrier, and an ointment base. The plant protective agent of the present invention is usually further formulated with an emulsifier, a suspending agent, a spreading agent, a penetrating agent, a wetting agent, a mucilage agent, a stabilizer, and the like into a suitable form. Examples of such preparations include emulsions, liquids, microemulsions, emulsions, floorables, oils, wettable powders, aqueous solvents, sols, powders, granules, fine granules, microcapsules, tablets Ointments, capsules, pellets, poisonous baits, sprays, aerosols, coatings and the like. In such preparations, the present compound or a salt thereof is usually 0.1 to 80% by weight, preferably Is contained in an amount of about 1 to 80% by weight. Specifically, when the plant protective agent of the present invention is an emulsion, solution, wettable powder or the like, the present compound or a salt thereof is usually from 0.;! To 80% by weight, preferably from 10 to When it is contained in an amount of about 80% by weight and is an oil agent, powder, etc., this compound or a salt thereof is usually contained in an amount of about 0.1 to 50% by weight, preferably about 1 to 20% by weight. In this case, the present compound or a salt thereof is usually contained in an amount of about 0.1 to 50% by weight, preferably about 0.1 to 20% by weight. Examples of solid carriers include vegetable powders (soybean powder, tobacco powder, wheat flour, wood powder, etc.), mineral powders (clays such as kaolin, bentonite, and acid clay), talc powder, mouth Talc such as limestone powder and silica such as diatomaceous earth and mica powder), alumina, sulfur powder, activated carbon, calcium carbonate, ammonium sulfate, sodium hydrogen carbonate, lactose, urea and the like. When a solid carrier is used in the plant protection agent of the present invention, one or more of these solid carriers can be blended at an appropriate ratio. Examples of the liquid carrier include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane). Xanones, etc.), ethers (tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), aliphatic hydrocarbons (kerosene, fuel oil, machine oil, etc.), aromatic hydrocarbons (toluene) , Xylene, solvent naphtha, methyl naphthalene, etc.), halogenated hydrocarbons (dichloromethane, black mouth form, carbon tetrachloride, etc.), acid amides (N, N-dimethylformamide, N, N— Mechirua acetamide, etc. N- methylpyrrolidone), esters (acetate Echiru acetate heptyl, fatty acid glycerol esters, such as § one butyrolactone), and, nitriles such (§ Se Tonitoriru, such as propionic nitrile) and the like. When a liquid carrier is used for the plant protection agent of the present invention, one or more of these liquid carriers can be used in combination at an appropriate ratio. Examples of ointment base materials include polyethylene glycol, pectin, polyhydric alcohol esters of higher fatty acids (such as glyceryl monostearate), cell mouth derivatives (such as methylcellulose), sodium alginate, bentonite, higher alcohols, many Examples include monohydric alcohols (such as glycerin), petrolatum, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hardened oil, and resins. When an ointment base is used for the plant protection agent of the present invention, one or more of these ointment bases can be blended at an appropriate ratio. A surfactant can be further added to the plant protection agent of the present invention as necessary. Surfactants used in such cases include, for example, sarcophagus, polyoxyethylene alkyl aryl ethers [for example, Neugen (trade name) 1 * 1 1 4 2 (EA 1 4 2 (trade name) ); Manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Manufactured by Kao Corporation], alkyl sulfates [e.g., Emar 10 (trade name), emal 40 (trade name); Kao Corporation], alkylbenzene sulfonates [e.g., neogen (trade name), neogen T (Trade name); Daiichi Kogyo Seiyaku Co., Ltd., Neoperex (trade name); Kao Co., Ltd.], polyethylene glycol ethers [For example, Nonipole 8 5 (Product name), Nonipole 1 0 0 (Product name) , Nonipol 1 6 0

(Trade name); manufactured by Sanyo Chemical Co., Ltd.], polyhydric alcohol esters [for example, Tween 20 (trade name), Tween 80 (product name); manufactured by Kao Corporation], alkylsulfosuccinates [ For example, Sanmorin 〇 T 2 0 (trade name); Sanyo Chemical Co., Ltd., Nieucargen 0 Χ 7 0 (trade name); Takemoto Yushi Co., Ltd.), alkylnaphthalene sulfonates, and alkenyl sulfonates [For example, Solpol 5 1 1 5

(Trade name); manufactured by Toho Chemical Co., Ltd.] nonionic and anionic surfactants. In addition to the present compound, the plant protective agent of the present invention includes other insecticides (for example, pyrethroid insecticides, organophosphorus insecticides, carbamate insecticides, neonicotinoid insecticides, natural insecticides). Acaricides, machine oils, nematicides, herbicides, plant hormone agents, plant synthesis Λ regulators, fungicides (eg copper fungicides, organochlorine fungicides, organosulfur fungicides, phenols (Bactericides), synergists, attractants, repellents, safeners, pigments, fertilizers, etc. may be appropriately blended. As an active ingredient of such other types of insecticides, for example,

(1) Organophosphorus compounds

Aluminum phosphide, butathiofos, cadusafos, chlorethoxyfos, chlorfenvinphos, chlorpyr i fos, chlorpyrifos-methyl , Cyanophos (CYAP), diazinone aiaz inon, DCIP (dichlorodi isopropyl ether) ^ dichlorfenthion (EDP), dichlorvos (DDW), dimethoate, dimethoate, dimethylvinphos, disultone foton), EPN, ethion, ethoprophos, etrimfos, fenthion (MPP), fenitrothion (MEP), phos thiazate, formothion, phosphorus Hydrogen fluoride phosphide) isofenphos, isoxathion, malathion, mesulfenfos, methithion dethidathion: DMTP, monocrotophos, monored (BRP), oxydeprofos E, SP (Parathion), phosalone, phosmet (PMP), pirimiphos-methyl, pyridafenthion, quinalphos, phenthoate: PAP, profenofos, Propaphos, prothiofos, pyraclorfos, salithion, sulprofos; tebupirimfos, temephos, tetrachlorvinphos, te (Thio meton), trichlorphon (DEP), vami doth ion, etc .;

(2) Carbamate compounds

Alanicarb, bendiocarb, benfracarb

(benfuracarb), BPMC, force carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenobucarb, phenothicarp

(fenothiocarb). Fenoxycarb, fenoxycarb, furathiocarb, isoprocarb (isoprocarb: MIPC), metolcarb, methomyl (me thorny 1), methiocarb, comfort, oxamyl, pirimi curve (pirimicurve) , Propoxur (PHC), XMC, thiodicarb, xylylcarb, etc .; (3) Synthetic pyrethroid compounds ''

Acrinathrin, allethrin, benfluthrin, benfluthrin, beta-cyf luthrin, bifenthrin. Cycloprothrin, cyfluthrin, cyhalothrin, cyhalothrin, cyhalothrin cypermethrin), deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucitrinate, flufenprox (flufenoprox), flumethrin (f lumethrin), fluparinate (f luvalinate), halfenprox (halfenprox), imiprothrin, permethrin, perretrin (prallethrin), pyrethrin (pyrethrins), resmelin esmethrin Sigma-cypermethrin, silafluofen, tenuthrin, tralomethrin

(tralomethrin), transnuthrin, 2, 3, 5, 6-tetrafluoro-4 mono (methoxymethyl) benzyl (EZ) _ (1RS, 3 RS; 1 RS, 3 SR) — 2, 2-dimethyl 3-Propyl-1-enylcyclopropanecarboxylate, 2, 3, 5, 6-tetrafluoro-4-methylbenzyl (EZ)-(1 RS, 3 RS; 1 RS, 3 SR)-2, 2-dimethyl-3 —Propyl 1-enylcyclopropanecarboxylate, 2, 3, 5, 6—tetrafluoro-4 (methoxymethyl) benzyl (1RS, 3 RS; 1 RS, 3 SR)-2, 2—dimethyl 3 — (2-Methyl-1-probenyl) cyclopropane carboxylate, etc .; (4) Nereistoxin compounds

Cartap (0 & & 0), Benstrup 0) 6115111 &), Choshikram 1 ^ (^ (; 1 & 111), Monosultap, Bisultap, etc .;

(5) Neonicotinoid compounds

Imidacloprid, nitenpyram, acetamiprid, thiamethoxam, thiacloprid, etc .;

(6) Benzylurea compounds

Chlorfluazuron, bistrifluron, difenthiuron, dif lubenzuron, fluazuron, flucycloxuron, flucycloxuron, flufenoxuron (Flufenoxuron), hexaflumuron, lufenuron, novaluron, novifluimiron, teflubenzuron, trif lumuron, etc .;

(7) Phenylpyrazole compounds Acetoprole, fipronil, vaniliprole, pyriprole, pyrafluprole, etc .; (8) B-toxin insecticide

Live spores and produced crystal toxins from Bacillus thuringiensis, and mixtures thereof;

(9) Hydrazine compounds

Chromafenozide, halofenozide, methoxyfenozide, tebufenozide, etc .;

(10) Organochlorine compounds

Aldrin, dieldrin, dienochlor, endosulfan, methoxychlor etc .;

(11) Natural insecticide

Machine oil, nicotine-sulfate; (12) other insecticides

Avermectin— B, cyenopyrafen, bromopropylate, buprofezin, chlorphenapyr, cyenopyrafen>cyromazine> D— D (1, 3- Dichloropropene, emamectin-benzoate;, fenazaquin, flepirazo, phos (f lupyrazofos, hydroprene), indoxacarb> lepimectin, metoxadiazon ), Milbemycin-A, pymetrozine, pyridalyl, pyriproxyfen u) yriproxyfen), spinosad, sulfluramid, tolfenpyrad, triazemate , Flubendiamide, cyflumet E emissions (cyf lumetofen), arsenic trioxide (Arsenic acid), Benku opening Chiazu (benclothiaz), lime room search (Calcium cyanamide), Calcium polysulfide, chlordane, DDT, DSP, flufenerim, flonicamid, flimonica, nurimfen, formetanate, ammonium

(metam- ammonium), metam- sodium, methyl bromide, nidinotefuran, potassium oleate, protrifenbute, spiromesifen

(spiromesifen), sulfur (Sulfur), metaflumizone (metanumizone), spirote 卜 ramat 卜 (spirotetramat), pyrifl luquinazon _¾ chlorane traniliprol (Chlorantraniliprole), following formula (A)

Formula (A)

[Where,

R ¹ is Me, C 1, Br or F,

R ² is F, Cl, Br, CI-C4 haloalkyl, or C1-C4 haloalkoxy,

R ³ is F, C 1 or Br,

R ⁴ is H, one or more halogen atoms; CN; SMe; S (〇) Me; S (0) ₂ Me and optionally substituted with OMe C 1 mono C4 alkyl, C3—C 4 Alkenyl, C3-C4 alkynyl, C3-C5 cycloalkylalkyl, or C4-C6 cycloalkylalkyl,

R ⁵ is H or Me,

R ⁶ is H, F or C 1,

R ⁷ represents H, F or C 1. ]

And the like. As an active ingredient of an acaricide, for example,

Acequinosyl (aceQuinocyl), amitraz, benzoximate, bromopropylate, quinomethionate (chinomethionat), chlorobenzi late, CPCBS (chlorfenson), clofentezine, kelofol, etoxazole, fenbutatin oxide, fenothiocarbmate, fenpyroxycarbate (Fenpyroximate), flucrypyrim (fluacrypyrim), fullproxyfen (uproxyfen), hexythiazox, propargite (BPPS), polynactins (polynactins), pyridaben, pyrimidifen, pyrimidifen (Tebufenpyrad), tetradifon (spirodiclofen), amidofurmet (amidof lumet), etc. As an active ingredient of nematicide, for example,

DC IP, fosthiazate, levamisol hydrochloride, methyisothiocyanate, morantel tartarate, imicyafos, and the like. S-Methyl (acibenzolar—S-methyl), Annoum mobam ^ Amisulbroni, Ampropylfos, Anilazine, Azoxystrobin, Benalaxyl, Benodanil , Benomyl, benthiaval icarb, benthiazole, bethoxazin, bitertanol, blasticidin-S, pordoid ( Bordeaux mixture), boscalid, bromuconazole, butiobate ( buthiobate), Calcium hypochlorite, Calcium polysulfide, captan, captan, carbendazol, carboxin, carboxin, calip * pamid, clobenathiazone ), Chloroneb, chloropicrin, chlorothalonil (TPN), chlorthiophos, Cinnamaldehyde, clozylacon, CNA (2, 6-Dichloro- 4-nitroaniline) Copper hydroxide ^ Cypersulfate ^ cyazofamide (cyazof amid), Schiff JI / Cyfluphenamid, cyioxanil, cyproconazole, cyprozinyl (cyprodinil), cyproiuram, dazomet, debacarb, dichlof luanid, D-D (1, 3-Dichloropropene), diclocymet, diclomezine, Diethofencarb, difenoconazole, diflumetorim, dimef luazole, dimethirimol> dimethomoi: ph, diniconazole-M, dicupazole-M (Dinocap), edifenphos, enestroburin, epoxiconazole, dimethyl dithiocarbamate nickel, etaconazole, etapoxam, ethirimol, etridiazole, Famoxadone, fenamide Fenamidone, fenarimol, fenbuconazole, fendazosulam. Fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropidin, fenpropidin (Fenpropimoi "ph), fentiazon, fentin hydroxide, fentin hydroxide, ferimzone, f luazinam, fludioxonil, flumetover, flumorph ), Fluoroimide, fluotrimazole, fluoxastrobin, fluQuinconazole, flusilazole, flusulfamide, flutolanil (f lutolanil), flutriafol, Fosetyl (iosetyl- A1), fusaride (fthalide), fuberidazole (iuberidazole;), flalaxil (iuralaxyl), furametpyr (furametpyr), furcarbanil (furcarbanil), fluconazole-cis, hexaconazol (hexaconazole), hymexazol, I BP (IBP), imazalil, imibenconazole, iminoctadine-albesilate, iminooctadine-albesilate Acetate uminoctadine—triacetate j, iodocarb, ipconazole, iprodione, iproval icarb, isoprothiolane, kasugamycin, crepe Methyle (kresoxim-methyl), mancozeb (mancozeb), mandipropamide unandipropamid, manneb (maneb), mepanipiri Mepanipyrim, mepronile (卿 ronil), meptyldinocap, metalaxyl, metalaxyl-, metalaxyl-, metam-sodium, methasulfocarb, methyl broniide, metconazole

(metconazole), metfuroxam, metminominostrobin, metrafenone, methos rehoha, ox

(metsulfovax), mi ldiomycin, milneb ゝ myclobutanil, myclozolin, nabam, orisastrobin, ofurace, oxadixil

(oxadixyl) ^ oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline

(.oxytetracycline), pefurazoate, penconazole

(enconazole), penciclon (encycuron), picoxis trobin

(picoxystrobin), polycarbamate, polyoxin, potassium hydrogen carbonate, probenazol, prochloraz, procymidone, propamocarb hydrochloride (propamidol) propamocarb-hydrochloride), propiconazole

(j) ropiconaole), propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrazophos <j) yrazophos, Piributicarb, pyrifenox, pyrimethanil, pyroqui Ion, quinoxyphene

(qui thigh yf en), quintozene (PCNB), silthiopham, simeconazole, sipconazole, sodium bicarbonate (sodium bibarbonate), sodium hypochlorite (sodium) hypochlorite), spiroxamine, SSF .— 1 2 9 ((E) -2 [2- (2, 5-d ime thy Iphenoxyme thy 1) henyl) -2-methoxyimino-N-methylacetamide) _¾ strike Lev. St reptomycin, sulfur, tebuconazo le, tech mouth phthalam, tecloftalam, tetraconazole, thiabendazole, thiadinil, thiuram thiram: TMTD), thifluzamide, thiophanate-methyl, tolclofos-methyl, TPN (TPN), triadimephone

(triadimefon), triadimenol, triazoxide, W

26

Triclamide, tricyclazole, triridemorph ^ triflumizole (tr.iflumizole), trifloxystrobin, triforine, triticonazole, validamycin, vinclozoline (Vinclozolin), piniconazole, zineb, ziram, syosensamide (zoxamide), and herbicide active ingredients and Z or plant growth regulators include, for example, abscisic acid ( Abscisic acid), Asetokuroru (acetochlor), reed full Orff-ene (acif luor fen-sod ium) ¾ Arakurore (alachlor Arokishijimu (alloxydim), Ametorin (ametryn), amicarbazone (amicarbazone), amidosulfuron

(amidosulfuron;, aminoethoxyvinylglycine, aminopyralid, AC94, 377, amiprof os-methyl ^ ansimidol, aslamid, atrazine) , Aviglycine, azimsulfuron, beflubutamid, benfluralin, benfuresate, bensulfuron-methyl, bensulide (SAP), benyulide Benzone, benthiocarb, benzamizole, benzfendizone, benzobicyclon, benzofenap, benzyladenine ^ benzylaminopurine (benzyl) aminopurine), hialaphos, bifuenox (bi fenox), brassinolide, bromacil, bromobutide, butachlor, butafenacil, butamifos: butyrate, cafenstrole , Calcium carbonate, Calcium peroxide, carbaryl, chlomethoxynil, chloridazon, chlorimuron-ethyl, chlorphthaliin , Chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid (DCBN), choline chloride, cinidon-ethyl, cinmethyrin (cinmethylin), cinosulfuron, clethodim, clomeprop, cloxyfonac—sodium, chlormequat chloride, 4 CPA (4-chlorophenoxyacetic acid), cliprop), clofencet, cumyluron, cyanazine, cyclanilide, cyclosulfamuron

(cyclosulfamron), cyhalofop-butyl, 2, 4 1 D salt (2, 4-Dichlorophenoxyacet ic acid salts), dichlorpate 7 aichlorprop: 2, 4- DP), Daimui; on ), Dalapon (DPA), Dimethenamide-P

(dimethenamid—P), daminozide, dazomet, n-Decyl alcohol, dicamba-sodium (MDBA), dichlobenil (DBN), diflufenican ), Jikeglac

(dikegulac), dimepiperate (dimethametryn), diquat, diquat, dithiopyr, diuron, endothal, epocholeone, , Ethephon, ethidimuron, ethoxysulfuron, etychlozate, etobenzanid, fenarimol, fenoxaprop-ethyl, fenoxaprop-ethyl, ent , Flazasulfuron, florasulfam, fluazifop-butyl, fluzolato ;, flurocarbazone

(flucarbazone), f lucetosulfuron, fruena set

(flufenacet), flufenpyr, flumetralin, flumioxazin, full-propanate sodium

(Flupropanate-sodium), flupyrsulfuron-methyl 'isocyanatomethyl Li Umm (f lupyrsul furon-methyl-sodium ) ¾ flurprimidol (nurprimidol), full Chiasetto * methyl (fluthiacet-methyl), Huo Lummus iodosulfuron (foramsulfuron), Hol Chlorenuron (forchlorfenuron), homeesafen (formesafen), gibberellin, glufosinate, glyphosate, halosulfuron-methyl, hexazinone, imazamox ( imazamox), imazapic, imazapyr, imazaquin, imazosulfuron, inabenfide

(inabenfide), Indole acetic acid (IAA), Indole butyric acid (Indole butyric acid), iodosulfuron, ioxynil-octanoate, isouron, isoxachlortole, isoxadifen, isoxadifen, karbutilate, lactofen Lenacil, linuron, LGC-42153 (LGC-42153), maleic hydrazide, mecoprop (MCPP), MCP salt (2-Methyl-4-chlorophenoxyacetic acid) salts), MC PA · thioethyl, MCPB (2-methy 1 -4-ch 1 or ophenoxybutanoic acid ethyl ester), mefenacet, mefluidide (mefluidide unepiquat), Mesosulfuron, mesotrione, methyl daimuron, metolachlor, metribuzin, metsulfur 'Metsulfuron-methyl, molinate, naphthylacetic acid, NAD (1-naphthaleneacetamide), naproanilide, napropamide, decyl alcohol , Nicosulfuron, n-phenylph thalamic acid _¾ orbencarb, orthosulfanuron, oxadiazon, oxaziclomefone, Oxine-sulfate, paclobutrazol, paraquat, pelargonic acid, pendimethalin, pentoxazone, petoxamide ( pethoxaraide), fenmeifam (.p enmedipham), picloram, picolinafen, pinoxaden > Piperonyl butoxide, piperophos, pretilachlor, primisulfuron-methyl, procarbazone, procarbazone, profluazol, profluazol, profluazol Profoxydim, prohexadione-calcium, prohydrojasmon, promethrin, propanil, propoxycarbazone, propyzamide, pyraflufen 'Pyraflufen-ethyl', pyrasulfotole, pyrazolate (pyrazolate), virazosulfuron 'ethyl, pyrazosulfuron-ethyl, pyrazoxifene (pyrazoxyfen), pyribenzoxoxime (pyribenzoxim), pyributicarb, pyridafol, pyridate, pyriphthalide (pyrifbali), pyriminobac-methyl ^ pyrithiobac, kink mouth rack (quiclorac) Quinoclamine, quizalofop-ethyl rimsulfuron, sethoxydim, siduron, simazine, simetryn, sodium chlorate, Sulfosulfuron, Swep

(swep: MCC)> tebuthiuron, tefuryltrione, tempotrione, tembotrione, tepraIoxydim, terbacil, terbucil: terbucarb: MBPMC, tenenylchlor, Thiazafluron (thidiazaron), thiencarbazone methyl, thifensulfuron-methyl, triaziflam, triaziflam, tribufos, triclopytridiphan trifloxysulfuron), trifluralin (tri flural in), trinexapac-ethyl, tritosulfuron (tritosulfuron), unicotisol. P (uniconazole-P), pernaredo (vemolate: PPTC), frucetosulfuron (f lucetosulfuron) , Orthosulfanuron (ort hosulfanuron, pinoxaden, pyrasul fotole, tefuryltrione, tempotrione (tembotrione), and thiencarbazone methyl, for example. Piperonyl butoxide, sesamex, sulfoxide, N— (2-ethylhexyl) —8, 9, 10-trinorborn-5-en-2-, 3-dicarboximide (MGK 264) ), WARF—WARF-antiresistant, diety lmaleate, and the active ingredients of safeners include, for example, benoxanol (benoxacor), cloquintocet-mexyl ), Cyometrinil, daimuron, dichlormid, funk Fenchlorazole-ethyl, fenclorim, flurazole, flufofenim, furilazole, mefenpyr-jetyl (mefenpyr-diethyl), MG19K naphthalic anhydride, oxabetrinil. In addition to the present compound or a salt thereof, the above-mentioned insecticide, acaricide, machine oil, nematicide, herbicide, plant hormone agent, plant growth regulator, fungicide, synergist , Attractants, repellents, safeners, pigments, fertilizers, etc., the content of these active ingredients in the plant protection agent of the present invention is usually 1 to 80% by weight, preferably 1 About 20% by weight.

Further, the content of the above-mentioned insecticide, herbicide, acaricide and additives other than Z or fungicide in the plant protective agent of the present invention depends on the type and content, or the dosage form of the preparation. Although it is different, it is usually from about 0.000 to 99.9% by weight, preferably about 1 to 99% by weight. More specifically, the surfactant is usually 1 to 20% by weight, preferably about 1 to 15% by weight, the flow aid is about 1 to 20% by weight, a carrier (liquid carrier, solid carrier, The ointment base is usually about 1 to 90% by weight. More specifically, in the case of a liquid agent, the surfactant is usually contained in an amount of about 1 to 20% by weight, preferably about 1 to 10% by weight, and about 20 to 90% by weight of water. Is preferred. When the plant protective agent of the present invention is an emulsion or a wettable powder (eg, a granular wettable powder), it is usually diluted appropriately with water to a volume ratio of about 10 to 500 times. Used. The plant protection method of the present invention is usually carried out by applying the plant protection agent of the present invention directly to the root or seed of a plant to be protected from pest damage or by applying it to the root zone of the plant.

In the present invention, the plant rhizosphere means the soil and other surrounding parts where the roots are affected. For example, soil in dry fields, paddy fields, upland fields, tea gardens, orchards, seedling cultivation soils and seedlings in seedling boxes, etc. Matte, hydroponic solution on hydroponic farm. Specific methods for directly applying to roots or seeds include, for example, spraying, spraying, dipping, impregnating, coating, and filming the plant protective agent of the present invention onto the roots or seeds of plants. Examples thereof include a coating method and a pellet coating method. As a method of applying to the rhizosphere of a plant, in the case of a hydroponic liquid, the plant protective agent of the present invention may be mixed, for example, mixed with a hydroponic liquid or mixed with a hydroponic liquid depending on the state of the rhizosphere of the plant. The method to do is mentioned. For example, planting hole treatments (planting hole spraying, Planting hole treatment soil admixture, plant root treatment (stock source spraying, stock source soil mixing, stock source irrigation, late seedling season, plant source treatment), grooving treatment (planting groove spraying, grooving soil mixing), cropping treatment ( Crop spreading, Crop soil mixing, Growing season cropping), Crop treatment during sowing (Crop application during sowing, Crop soil mixing during sowing), Full treatment (spreading over the whole surface, mixing over the whole soil), etc. Spraying treatment (growth surface foliar spraying, under crown or around main trunk, soil surface spraying, soil surface mixing, sowing hole spraying, buttocks surface spraying, inter-plant spraying), other irrigation treatment (soil irrigation, seedling irrigation, Chemical infusion treatment, local irrigation, chemical drip irrigation, Chemigation), seedling box processing (nursing box spraying, seedling box irrigation), seedling tray processing (nursing tray spraying, seedling tray irrigation), nursery treatment (seed bed spraying, Nursery irrigation, water seedling spraying, seedling soaking), mixed soil Treatment (seedbed soil mixing, before sowing bed soil mixing), other treatment (soil mixing, plow, topsoil mixed, rain drop unit earth 壌混 sum, planting position treatment, flower cluster spraying, paste fertilizer mixing) a method for. The application amount of the present compound or a salt thereof in the plant protection method of the present invention can be appropriately changed according to the application time, application place, application method, formulation form, etc., but when applied to the root zone of a plant, The amount of the present compound or a salt thereof per hectare is usually about 3 to 300,000 g, preferably about 50 to 300 g, and when applied directly to the root of a plant or seed The present compound or a salt thereof per one plant body or one seed of the plant is usually in a ratio of about 0.005 to 0.lg, preferably about 0.000 to 0.02 g. is there. In the plant protection method of the present invention, the application time of the present compound or a salt thereof is expected to be harmful to the target plant by a pest, and when the protection is performed in advance, and depending on the pest to the target plant. It can be selected as appropriate depending on the case where it is carried out for protection after the harm has been confirmed, and is not limited at all. Specifically, for example, fruit vegetables such as eggplant and tomato, cabbage, lettuce, etc. In the case of crops that have undergone the seedling stage such as leafy vegetables, etc. The growing stage in the field is bald. In addition, in the case of crops that are directly sown in normal fields, such as ivy, corn, and soybean, there are, for example, the seed stage, the seeding stage in the field, and the growth stage.

As a method of applying the present compound or a salt thereof to the rhizosphere of a plant, a method of applying the present compound or a salt thereof to soil or the like after the root of the plant has developed, and the present compound or a salt thereof in advance. A method of developing plant roots in the soil after applying salt to the soil and the like is mentioned. The plant protection method of the present invention is generally applied to "crop". Examples of such “crop” include the following “crop”.

"produce"

Corn, rice, wheat, barley, rye, empak, sorghum, rice cake, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, evening paco, etc .;

Eggplant vegetables (eggplants, tomatoes, peppers, peppers, potatoes, etc.), cucurbitaceae vegetables (brown cucumbers, capochia, zucchini, watermelon, melon etc.), cruciferous vegetables (daikon, turnips, cirrus radish, koru rubi, Chinese cabbage) , Cabbage, mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, shiyungiku, artichoke york, lettuce, etc.), lily family vegetables (leek, onion, garlic, asparagus, etc.), celery family vegetables (carrot, parsley, Celery, American Bow Fu, etc.), Akaza vegetables (Hourenso, Fudansou, etc.), Lamiaceae vegetables (Perilla, Mint, Basil, etc.), Strawberries, Satsumaimo, Yamanoimo, Satoimo, etc .;

'Hana'

Foliage plant;

Berries (apples, pears, two pears, quince, quince mouth, etc.), drupes (peaches, plums, nectarines, ume, sweetweed, apricots, plums, etc.) , Grapefruit, etc.), nuts (chestnut, walnut, hazel, almond, bisyucho, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, Bean paste, banana, coffee, date palm, coconut, etc .;

Chia, kuon, flowering trees, street trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, ripe, oak, poplar, hanazo, fu, sycamore, oyster, kurobe, mominoki, tsuga, nezu, pine, Spruce, yew, etc.);

Lawn grasses such as Noshiba, Kouraishipa, Bermudagrass, bentgrass, ryegrass, bullgrass, fescue;

Pastures such as ryegrass, orchardgrass, fescue, bluegrass, clover, and alfa alpha. The above “crop” includes crops that have been given tolerance to herbicides by classical breeding methods, genetic recombination techniques, and the like. In crops tolerant to herbicides, HPPD inhibitors such as isoxaflutol; ALS inhibitors such as imazeupir pills and tifensulfurum methyl; EPSP synthase inhibitors; daryumin synthase inhibitors; Application of herbicides such as CoA carboxyxylase inhibitors; or promoxinil does not cause phytotoxicity problems.

Examples of crops that have been given tolerance to herbicides by classical breeding methods include Clear fi el d® canola that has been given resistance to imidazolinone herbicides; STS soybeans that have been given resistance to sulfonylurea herbicides And SR corn that has been given resistance to acetyl acetylene inhibitors. A crop imparted with tolerance to a acetyl acetylene inhibitor is described in, for example, Proc. Natl. Acad. Sci. USA 1990, 87, 7175.

A mutant acetyl-CoA lpoxylase that develops resistance to a acetyl-CoA lpoxylase inhibitor is known, for example, from Weed Science 53: 728-746, 2005. If the gene encoding this mutant type of acetyl CoA carboxylase is introduced by genetic recombination technology, or if the gene encoding acetyl CoA carboxyxylase is introduced with a mutation related to conferring resistance to acetyl CoA carboxyxylase, Can be conferred with resistance to acetyl-CoA carboxyxylase-inhibiting herbicides.

For example, maize varieties that have been given tolerance to Darifosarta glufosinate are known as “crops” that have been given tolerance to herbicides by genetic engineering techniques. Some of these corn varieties are sold under the trade names RoundupReady® and LibertyLink®. The above “crop” also includes crops that have been given the ability to produce insecticidal toxins by genetic engineering techniques.

Such insecticidal toxins include, for example, insecticidal proteins derived from Bacillus cereus and Bacillus popilie; CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C derived from Bacillus thuringiensis, VIPK VIP2, Insecticidal protein such as VIP3 or VIP3A; Nematode-derived insecticidal protein; produced by animals such as scorpion toxin, spider toxin, bee toxin or insect-specific neurotoxin Toxins; filamentous fungi toxins; plant lectins; agglutinins; trypsin inhibitors, serine protease inhibitors, protease inhibitors such as pachintin, cisyuchin, papain inhibitors; ricin, maize RIP, abrin Ribosome-inactivating protein (RIP) such as bryodin; 3-hydroxysteroidoxidase, ecdysterolide UDP-darcosyltransferase, steroid metabolic enzymes such as cholesterol oxidase; ecdysone inhibitor; HMG-C0A reductase; sodium Ion channel inhibitors such as channels and calcium channel inhibitors; juvenile hormone esterase; diuretic hormone receptor; stilbene synthase; bibenzyl synthase; chitinase;

The insecticidal toxin includes a hybrid protein of the above-mentioned insecticidal protein and a protein in which a part of amino acids constituting the above-mentioned insecticidal protein is deleted or substituted. The hybrid protein is created by combining different domains of the above insecticidal protein by gene recombination technology. As a toxin lacking a part of amino acids constituting the insecticidal protein, for example, CrylAb lacking a part of amino acids is known.

For example, EP-A- 0 374 753, W0 93/07278, W0 95/34656, EP-A- 0 427 529, EP-A-451 878, and W0 03/052073.

“Crops” that have been granted the ability to produce insecticidal toxins by genetic engineering techniques are resistant to attack from, for example, Coleoptera, Diptera, Z or Lepidoptera. “Crops” that have been given the ability to produce insecticidal toxins through genetic engineering techniques are commercially available such as YieldGard® (a corn variety that expresses CrylAb toxin), YieldGard Rootworm® (Cry3Bbl toxin) Corn varieties), YieldGard Plus® (a corn variety that expresses CrylAb and Cry3Bbl toxins), Herculex I® (phosphinothricin N-acetyltransferase (PAT) to confer resistance to CrylFa2 toxin and glufosinate) Corn varieties that express), NuC0TN33B® (an evening varieties that express CrylAc toxin), Bol lgard I® (an evening varieties that express CrylAc toxin), Bol lgard II® (which expresses CrylAc and Cry2Ab toxins) Varieties), VIPC0T® (a potato variety expressing VIP toxin), NewLeaf® (a potato variety expressing Cry3A toxin), NatureGard®Agri sure®GT Advantage (GA21 Third-resistant traits), Agrisure® CB Advantage (Btll corn polar (CB) trait), and Protecta®. The above “crop” also includes crops that have been given the ability to produce anti-pathogen substances by genetic engineering techniques.

Anti-pathogenic substances produced by microorganisms include, for example, PR proteins (PRPs, described in EP-A-0392 225); sodium channel inhibitors, calcium channel inhibitors (virus produced KP1, ΚΡ4, ΚΡ6 toxins, etc.) Ion channel inhibitors such as; stilbene synthase; bibenzyl synthase; chitinase; dulcanase; PR protein; peptide antibiotics, heterocyclic antibiotics; and proteins involved in plant disease resistance (Described in W0 03/000906) and the like.

Examples of crops that have been given the ability to produce anti-pathogenic substances by genetic recombination techniques include those described in EP-A-0 392 225, W095 / 33818, and EP-A-0 353 191. Can be mentioned. By the plant protection method of the present invention, it is possible to protect plants from harm by pests that cause harm such as feeding and sucking (for example, harmful arthropods such as harmful insects and harmful mites). Specific examples of such pests include the following.

Hemiptera pests: Laodelphax striatellus: Nunaparvata lugens, Suna Loonfish (Sogatella furcifera), etc., Nephotettix cincticeps, Nephotettix c Aphis gossypii), Myzus persicae, Brevicoryne brassicae, Macros iphum euphorbiae ^ Aulacorthmn solani: Aphids such as the citrus aphid (Toxoptera ci tricidus), Nezaraantennata, Riptortus clavetus, Leptocorisa chinensis, Eysarcorisly mi st a), stink bugs such as Lygus lineolaris, whitefly (Trialeurodes vaporariorum), whiteflies such as Bemisia argentifolii, Aonidiella aurantii, San scale scale insects (Comstockaspis perniciosa), Unaspis citri> Ceroplastes rubens, Icerya purchasi, and other scale insects, dipterans, pheasants, etc .; Lepidoptera Chilo suppressalis, Tryporyza incertulas, Cnaphalocrocis medinalis, Phydia, Plodia interpunctella, Plodia interpunctella, Ostrinia furrel, iP ), Spodoptera litura, Spodoptera exigua, Pseudaletia separata ^ Mamestra brassicae, Agroiis ipsilon> Evening mana sign Genus, Heliotis, Gills of the genus Rikoberpa, Pieris rapae, etc. fasciata), Tycho nocturnal spider (Adoxophyes sp.), Chiyano, Maki (Homona magnanima), Midare Kakumonzo, Maki

(Archips fuscocupreanus), codling moth (Cydia pomonella), etc. Limantria, Euplectites genus, etc., Paga (Tinea translucens), Koiga (Tineola bisselliella), etc .; Azamuma pests: Frankliniellaoccidentalis, Thrips parmi, Thrips parrs, S ), Negia Zamima (Thrips tabaci), Razz Hana § The Miu Ma (Frankliniella intonsa), Tapakoazamiuma (Frankliniella fusca) § The Miuma such as the like; Diptera: Musca domestical (Culex popiens pallens), Usiab (Tabanus tri gonus), Evening fly (Hy 1 emya an ti qua), Fly fly (Hy 1 emya platura), Syringa power (Anopheles sinensis), Agromyza oryzae, Hydrellia griseola, Drosophila (Chlorops oryzae), Dacus cucurbitae, Ceratitis capitata, Lirio trifoli Epilachna vigintioctopunctata, Aulacophora femoral is, Phyllotreta striolata ^ Oulema oryzae, Echinocnemus squameus or Liss trus , Azuki beetle (Cal losobruchus chinensis), Shibao weevil (Sp henophorus venatus) ^ Rice beetle (Popi 11 ia japonica), Douga buoy (Anomala cuprea), Cornroot worm mate (Diabrotica spp.), Colorado beetle (Leptinotarsa decemlineata), Rotifer beetle (Agriotes spp.) Bamboo beetle (Lasioderma serricorne), Amaranthus verascu (Tribolium castaneunu), Lyctus brunneus, Anoplophora malasiaca, Periwinkle (Locustamigratoria), Kera (Gryllotalpa africana), Oxya yezoensis, Oxya japonic a, etc .; Hymenoptera: Athalia rosae, Acromyrmex spp. ) Etc. Nematodes: Aphelenchoides besseyi, strawberry Senchu © (Nothotylenchus acris, and the like; Blattodea pests: Chiya panel cockroach (Blattella germanica), black cockroach (Periplaneta fuliginosa), Wamonkokiburi (Periplaneta americana) _¾ Tohyi port cockroach (Periplaneta brunnea), oriental cockroach (Blatta orientalis) and the like; Mite order pests: Namihadani (Tetranychus urticae), Nigirihadani (Panonychus citri), Nigellanus spp., Aculops pelekassi, etc., Fushida nigiri (Polyphagotarsonemus latus), Spider mites, Crested spider mites, Tyrophagus putrescent iae, and other mites, Dermatophagoides farinae, Frog mite

(Dermatophagoides ptrenyssnus) and other ticks, Cheetletus eruditus, Cheletus malaccensis, Southern ticks

Ticks such as (Cheyletus moorei). Next, although a synthesis example, a formulation example, a test example, etc. are given and this invention is demonstrated further in detail, this invention is not limited to these.

Note that in the ¹ H- NMR unless otherwise stated, in the case of using a heavy black port Holm (CDC 1 ₃₎ as a measuring solvent was used tetramethylsilane (TMS) as internal standard. First, a synthesis example of this compound is shown.

Synthesis example 1

2-Fluoro-N-methyl-4- (1, 1, 2, 2-tetrafluoroethoxy) aniline 0.30 g in a solution of 7 ml 1 in ethyl acetate, A solution prepared by dissolving 0.25 g of benzoyl isocyanate in 1 ml of ethyl acetate was added and stirred at room temperature for 2 hours. The reaction mixture was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (n—hexane: ethyl acetate = 3: 1) to give 1— (2-chloro 6-fluorobenzoyl)-3-[2-fluoro-4 1, 1, 2, 2, —tetrafluoroethoxy) phenyl] —3-methylurea (hereinafter referred to as the present compound (1)) 0.50 g was obtained.

This compound (1)

FO o ^F ^ ^OCF 2CHF ₂ ^ -NMR (DMSO—d ₆ , measuring temperature 80. C) δ (ppm): 3.21 (3H, s), 6.70 (1H, tt), 7. 15-7.22 (2H, m) , 7. 24—7. 32 (2H, m), 7. 38— 7. 45 (1H, m), 7. 49 (1H, t), 10. 52 (1H, s) Synthesis Example 2

2-Fluoro-N-methyl-4-one (1, 1, 2, 2-tetrafluoroethoxy) aniline in a solution of 0.30 g dissolved in 7 ml 1 of ethyl acetate, 2,6-dichlorobenzoyl A solution of 0.27 g of sulfonate in 1 ml of ethyl acetate was added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was attached to a silica gel column chromatography (n—hexane: ethyl acetate = 4: 1) and 1- (2,6-dichlorobenzoyl) —3— [2-fluoro-4- (1, 1, 2,2-tetrafluorooxy) phenyl] 1-3-methylurea (hereinafter referred to as the present compound (2)) 0.50 g was obtained.

This compound (2)

— NMR (DMSO—d ₆ , measuring temperature 80 ° C) δ (ppm): 3. 20 (3H, s), 6. 71 (1H, tt), 7. 13-7. 19 (1 H, m) , 7. 23-7. 29 (1H, m), 7. 34- 7. 44 (3H, m), 7. 48 (1 H, t), 10. 48 (1H, brs) Synthesis Example 3

(4) A solution of 0.30 g of chloro-N-methylaniline dissolved in 7 ml of ethyl acetate, and a solution of 0.42 g of 2-chloro-6-fluorobenzoyl isocyanate in 1 ml of ethyl acetate. And stirred at room temperature for 2 hours. The reaction mixture was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained solid was washed with tert-butyl methyl ether and dried under reduced pressure to give 1- (2-chloro-6-fluorobenzoyl) 1 3- (4-chloro-phenyl) 1-3-methi. Lurea (hereinafter referred to as the present compound (3)) 0.64 g was obtained.

This compound (3)

^ -NMR (DMS 0 1 d ₆ , measuring temperature 80 ° C) δ (p pm): 3. 23 (3H, s), 7. 18-7. 24 (1 H, m), 7. 27— 7 32 (3H, m), 7. 3 9-7. 46 (3H, m), 10. 28 (1H, brs) Synthesis Example 4

4 In a solution of 0.30 g of chloro-N-methylaniline in 7 ml of ethyl acetate, a solution of 2,6-dichlorobenzoic isocyanate 0.46 ^ in ethyl acetate 1111 1 In addition, the mixture was stirred at room temperature for 2 hours. The reaction mixture was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained solid was washed with tert-butyl methyl ether and dried under reduced pressure to give 3- (4 monocyclophenyl)-1-(2, 6-dichlorobenzoyl) trimethyl urea (hereinafter, This compound (4) is described.) 0.66 g was obtained.

This compound (4)

^X H-NMR (DMSO—d ₆ , measuring temperature 80 ° C) δ (p pm): 3. 23 (3H, s), 7. 27-7. 33 (2H, m), 7. 3.4-7. 46 (5H, m), 10. 25 (1 H, brs) Synthesis Example 5

2-Fluoro-N-methyl-4 monotrifluoromethyl dilin 0.57 g in a solution of 10 ml of ethyl acetate was added to 2-chloro-salt-6-fluorobenzoyl isocyanate 0.63 g Was added to a solution dissolved in 3 ml of ethyl acetate and stirred at room temperature for 2 hours. The reaction mixture was washed successively with water and saturated brine, and then anhydrous magnesium sulfate W

41

And concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 3: 1) to give 1— (2-chloro-6-fluorobenzoyl) —3— (2-fluoro-4-trifluoromethylphenyl) 3-57-methylurea (hereinafter referred to as the present compound (5)) 0.57 g was obtained.

This compound (5)

^X H-NMR (CDC 1 ₃ ) δ (ρ pm): 3. 24 (3H, s), 7.04 (1 H, t), 7.21 (1Η, d), 7. 29-7. 37 (1H, m), 7. 44-7. 5 4 (3Η, m), 8. 21 (1Η, brs) Synthesis Example 6

2-Fluoro-N-methyl-4-trifluoromethylaniline 0.50 g in a solution of 10 ml of ethyl acetate, 2,6-dichlorobenzoic isocyanate 0. A solution of 5′6 g dissolved in 2 ml of ethyl acetate was added and stirred at room temperature for 2 hours. The reaction mixture was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 3: 1), and 1 1 (2, 6-dichlorobenzoyl) 1 3 (2 monofluoro-4 monotrifluoromethylphenyl) ) 1-trimethylurea (hereinafter referred to as the present compound (6)) 0.57 g was obtained.

This compound (6)

^ -NMR (CDC 1 ₃ ) δ (ppm): 3. 25 (3H, s), 7. 24-7. 37 (3H, m), 7. 45 -7. 58 (3H, m), 7. 86 (1H, brs) Synthesis Example 7

1 1 (2-chloro-6-fluorobenzoyl) 1 3— [2-Fluoro 4 1 Rifluoromethyl) phenyl] To a solution of 1-methylurea 1.01 dissolved in 10.0 ml of 1-methyl-2-pyrrolidone, 122 mg of sodium hydride was added and stirred at 2 ° C for 30 minutes. To the mixture was added 0.338 ml of methyl iodide at 1.5 and stirred at 2-3 for 3 hours. Under ice-cooling, a mixture of 10 ml of saturated aqueous ammonium chloride and 10 ml of water was added to the reaction mixture, and the mixture was extracted 3 times with 20 ml of ethyl acetate. The organic layers were combined, washed with saturated brine three times, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography (ethyl acetate: black mouth form: hexane = 1: 1: 4) to give 1 1 (2-chloro-6-fluobenzoyl) —3— [2— Fluoro-4 mono (trifluoromethyl) phenyl] 1,1,3-dimethylurea (hereinafter referred to as the present compound (7)) 0.88 g was obtained.

Compound of the present invention (7)

^ -NMR (DMSO—d ₆ , 80 ° C) δ (p pm): 3. 00 (3H, brs), 3. 32 (3H, brs), 7. 21-7. 26 (1H, m), 7. 31-7. 3 3 (1H, m), 7. 45-7. 50 (1 H, m), 7. 60 (2H, brs), 7. 71 -7. 73 (1H, m) Synthesis Example 8

1— (2,6-Dichlorobenzoyl) —3— [2-Fluoro-4- (trifluoromethyl) phenyl] 1 3-Methylurea 0.82 g in 1-methyl-2-pyrrolidone in a solution of 8.2 ml 96 mg of sodium hydride was added and stirred at 2 for 30 minutes. To the mixture, 0.3 ml of methyl iodide was added at 2 ° C and stirred at 2-3 for 3 hours. A mixture of 8 ml of saturated aqueous ammonium chloride and 8 ml of water was added to the reaction mixture under ice cooling, and the mixture was extracted 3 times with 20 ml of ethyl acetate. The organic layers were combined, washed 3 times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography (ethyl acetate: chloroform: hexane = 1: 1: 4) to give 1 (2, 6-dichlorobenzoyl) —3— [2-fluoro-4— (Trifluoromethyl) phenyl] 1,3-dimethylurea (hereinafter referred to as the present compound (8)) 0.63 g was obtained. Compound of the present invention (8)

^X H-NMR (DMSO— d ₆ , 80) 6 (ppm): 2. 87 (3H, brs), 3. 35 (3H, brs), 7. 40— 7. 47 (3H, m), 7. 60—7.63 (1H, m), 7.73-7.75 (2H, m) Synthesis Example 9

1-(2-Chloro-6-fluorobenzoyl)-3-(4 monophenyl)-3-methylurea in a solution of 1.01 g in 1-methyl-2-pyrrolidone 10.0 ml Sodium chloride 14 lmg was added and stirred at 2 ° C for 30 minutes. To the mixture, 0.44 ml of methyl iodide was added at 2 ° C, and the mixture was stirred at 2-3 ° C for 3 hours. To the reaction mixture, a mixture of 10 ml of saturated aqueous ammonium chloride and 10 ml of water was added under ice-cooling, and the mixture was extracted 3 times with 2 ml of ethyl acetate. The organic layers were combined, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography (ethyl acetate: black mouth form: hexane = 1: 1: 4) to give 1 (2—black mouth—6-fluorobenzoyl) —3— (4-Chroophenyl) 1,3-dimethylurea (hereinafter referred to as the present compound (9)) 0.94 g was obtained.

Compound of the present invention (9)

^ -NMR (DMSO-d ₆ , 80 ° C) δ (p pm): 2. 93 (3H, brs),

3. 26 (3H, b rs), 7. 22— 7. 33 (4H, m), 7. 41-7. 5

0 (3H, m) Synthesis Example 10

1-(4 Monoclonal Phenyl) -3- (2, 6-Diclonal Benzoyl) 1-Methylurea 1.01 g in 1-methyl-2-pyrrolidone in 10.0 ml Sodium hydride 13 Omg was added and stirred at 2 ° C for 30 minutes. To the mixture 0.42 ml of methyl fluoride was added at 2 and stirred at 2-3 for 3 hours. A mixture of saturated ammonium chloride aqueous solution 10 ml and water 10 ml was added to the reaction mixture under ice-cooling, and the mixture was extracted 3 times with 2 Oml of ethyl acetate. The organic layers were combined, washed with saturated brine three times, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography (ethyl acetate: chloroform: hexane = 1: 1: 4), and 1- (4-chlorodiphenyl) 1-3- (2,6-dichlorobenzo ) — 1,3-Dimethylurea (hereinafter referred to as the present compound (10)) 0.87 g was obtained.

Compound of the present invention (10)

^ -NMR (with DMS 0 1 d ₆ , 80) δ (ppm): 2. 83 (3H, brs), 3. 32 (3H, brs), 7. 40-7. 50 (7H, br) Synthesis Example 11

1 1 (2-Chloro 6-Fluorobenzoyl)-3-[2-Fluoro 4— (1, 1, 2, 2-tetrafluoromethoxy) phenyl] 1 3-Methylurea 0.75 g 1 To a solution dissolved in 7.5 ml of monomethyl-2-pyrrolidone, 82 mg of sodium hydride was added and stirred at 2 ° C for 30 minutes. To the mixture, 0.25 ml of methyl iodide was added at 1.5 ° C and stirred at 2-3 ° C for 3 hours. Under ice-cooling, a mixture of saturated aqueous ammonium chloride 7.5 ml and water 7.5 ml was added to the reaction mixture, and the mixture was extracted 3 times with 15 ml of ethyl acetate. The organic layers were combined, washed 3 times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography (ethyl acetate: black mouth form: hexane = 1: 1: 4) and 1- (2-chloro-6-fluobenzoyl)-3-[2 —Fluoro-4 (1,1,2,2-tetrafluoromethoxy) phenyl] —1,3-dimethylurea (hereinafter referred to as the present compound (11)) 0.68 g was obtained.

Compound of the present invention (11)

^X H-NMR (DMSO-d ₆ , 80) δ (ppm): 2. 97 (3H, brs), 3. 28 (3H, brs), 6. 57-6. 85 (1 H, m), 7. 16-7. 3 3 (4H, m), 7. 44-7.50 (2H, m) Synthesis Example 12

1 1 (2, 6-Dichlorobenzo) 1 3-[2-Fluoro-4 _ (1, 1, 2, 2-tetrafluoromethoxy) phenyl] —3-Methylurea 1. 0 18 to 1— To a solution dissolved in 10.0 ml of methyl-2-pyrrolidone, 10 5 mg of sodium hydride was added and stirred at 2 ° C for 30 minutes. To the mixture, 0.33 ml of methyl iodide was added at 2 ° C, and the mixture was stirred at 2-3 for 3 hours. A mixture of 10 ml of saturated aqueous ammonium chloride and 10 ml of water was added to the reaction mixture under ice-cooling, and the mixture was extracted 3 times with 20 ml of ethyl acetate. The organic layers were combined, washed 3 times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography (ethyl acetate: black mouth form: hexane = 1: 1: 4) to give 1 1 (2, 6-diclonal benzoyl) — 3— [2— Fluoro-4- (1, 1, 2, 2-tetrafluoromethoxy) phenyl] 1,3-dimethylurea (hereinafter referred to as the present compound (12) ′) 0.88 g was obtained.

Compound of the present invention (12)

_{XH-NMR (DMSO- d 6,} 80.C) d (p pm): 2. 85 (3H, brs), 3. 32 (3H, brs), 6. 59 - 6. 85 (1 H, m) , 7. 17— 7. 1 9 (1H, m), 7. 28-7. 31 (1 H, m), 7. 40- 7. 49 (3H, m), 7. 58-7. 63 ( 1 H, m) Next, formulation examples are shown. In addition, a part represents a weight part.

Formulation Example 1.

10 parts of this compound (1) to (12) are dissolved in a mixture of 35 parts of xylene and 35 parts of N, N-dimethylformamide, 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate Add 10% of each emulsion. Formulation Example 2

Add 20 parts of this compound (1) to (12) to a mixture of 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 and mix well. Get each 20% wettable powder. Formulation Example 3

Add 1 part of synthetic silicon hydroxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay to 2 parts of this compound (1)-(12) and mix well. Next, an appropriate amount of water is added to these mixtures, and the mixture is further stirred, granulated with a granulator, and dried by ventilation to obtain 2% granules. Formulation Example 4

1 part of this compound (1)-(12) is dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder, 0.3 part of PAP and 93.7 parts of Fubasami clay are added to this, and mixed thoroughly. Acetone is removed by evaporation to obtain each 1% powder formulation example 5

By mixing 10 parts of this compound (1) to (12); 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt; and 55 parts of water, Get each 10% flowable. Formulation Example 6

This compound (1)-(12) 0.1 part is melt | dissolved in 5 parts of xylene and 5 parts of trichloroethane, this is mixed with 89.9 parts of deodorizing kerosene, and each 0.1% oil agent is obtained. Formulation Example 7

Dissolve 10 mg of this compound (1) to (12) in 0.5 ml of acetone, and treat this solution to 5 g of animal solid feed powder (solid feed powder for breeding CE-2, product of Nippon Claire Co., Ltd.). Mix evenly. The acetone is then evaporated to dryness to obtain each bait. Next, test examples show that the plant protection method of the present invention is useful.

Test example 1

This compound (1), (2), (3), (5), (6), (7), (8), (9), (11) and (1 2) 5 mg each of Sorgen TW-20 ( Daiichi Kogyo Seiyaku Co., Ltd.) and acetone mixed solution (mixing volume ratio; Sorgen TW-20: acetone = 1: 19) 0.1. Dissolved in 1 ml, diluted to 3 ml with ion-exchanged water, for testing of test compounds A drug solution was prepared. Cabbage seedlings were grown in a seedling container (capacity: 27 ml, height: 5.0 cm) to 2.5 leaf stage. The whole amount of the test chemical solution was irrigated on the surface of the cabbage seedling. 5 days after treatment, the roots of the cabbage seedlings were removed, the stems and leaves were placed in a polyethylene cup (capacity 180 ml), the first instar larvae 10 S of Spodoptera litura were released, and stored at 25 ° C for an additional 7 days. did. The cabbage seedlings were then inspected to determine the degree of damage caused by the larvae of the monkeys, comparing the case where the test compound was treated (treated area) and the case where it was not treated (untreated area). Asked. Damage control effect (%) = X 100

As a result, in the treatment area of this compound (1), (2), (3), (5), (6), (7), (8), (9), (1 1) and (12), In both cases, the damage control effect was 90% or more, and the cabbage seedlings were able to protect against the damage caused by the lotus root. Test example 2

In this compound (1), (2), (5), (6), (7), (8), (11) and (12), 5 mg each of Sorgen TW-20 (Daiichi Kogyo Seiyaku) and acetone (Mixed volume ratio; Sorgen TW-20: Acetone = 1:19) 0.1 Dissolved in 1 ml, diluted to 3 ml with ion-exchanged water to prepare a test chemical solution for the test compound. A seedling container (capacity: 27 ml, height: 5. O cm) was filled with soil and sown with cabbage. The whole amount of the test chemical was irrigated on the soil surface of the seedling container. The cabbage was raised until 28 days after the treatment. The roots of the cabbage seedlings were removed, the foliage was placed in a polyethylene cup (capacity 180 m 1), 10 second-instar larvae of Plutellaxylostella were released, and stored at 2 for an additional 7 days. The cabbage seedlings were then inspected for the degree of damage caused by the diamondback larvae, comparing the case where the test compound was treated (treated area) and the case where it was not treated (untreated area). Asked. (Degree of food damage in treatment area

Damage suppression effect (%) = 1 X 100

\ Untreated area © Food damage level No. As a result, in the treated area of this compound (1), (2), (5), (6), (7), (8), (11) and (1 2) All of them showed a damage suppression effect of 90% or more, and were able to protect cabbage seedlings from damage caused by Japanese pear. Industrial applicability

According to the present invention, plants can be protected from harmful organisms.

Claims

Claim Formula (I)

[Where,

X represents a fluorine atom or a chlorine atom,

R ¹ is a hydrogen atom, a C 1 _C 6 alkyl group which may be substituted with a halogen atom, a C 2 -C 6 alkenyl group which may be substituted with a halogen atom, a C 2 _C 6 alkynyl group, C 6—C 14 aryl group, C 7 -C 11 alkyl group, C 2 -C 6 alkoxyalkyl group, C 7—C 14 aryloxyalkyl group, C 3—C 6 N, N-di (alkyl) aminoalkyl group, C2-C6 alkylthioalkyl group, C2-1C6 alkylsulfinylalkyl group, C2-C6 alkylsulfonylalkyl group, C3-C9 alkoxyalkoxyalkyl group, C 2-C 6 alkoxycarbonyl group, C 8-C 1 2 aralkyloxycarbonyl group, N, N-di (C 1 1 C 6 alkyl) force rubamoyl group, optionally substituted with halogen atom C 2 -C 6 Alkylcarbonyl, formyl, optionally substituted with halogen atom C 1 represents a C 5 alkylsulfonyl group or a C 6 -C 10 aryl sulfonyl group, R ² represents a halogen atom or a C 1 C 4 alkyl group optionally substituted with a halogen atom,

R ³ is a halogen atom, an optionally substituted C 1—C 4 alkyl group, an optionally substituted C 1—C 4 alkoxy group, or an optionally substituted C atom. A 2-C6 alkoxyalkoxy group, a C2-C4 alkenyloxy group optionally substituted with a halogen atom or a C2-C4 alkynyloxy group optionally substituted with a halogen atom;

m represents an integer of 0 to 4. ]

A method for protecting a plant from harm by a pest having a step of applying an effective amount of a (N, -methyl) benzoylurea compound or a salt thereof represented by the formula to a root or a seed of a plant or a rhizosphere of a plant .

2. In formula (I), R ¹ is a hydrogen atom, and R ³ is a halogen atom, C 1 optionally substituted with a halogen atom C 1 alkoxy group optionally substituted with a halogen atom or C 1 (1) a C4 alkyl group and m is 0 or 1 (N, -methyl) having a step of applying an effective amount of a benzoylurea compound or a salt thereof to the root or seed of a plant or the rhizosphere of a plant A method for protecting plants from harm by pests according to claim 1.

3. The plant protection method according to claim 1, wherein the root or seed of the plant or the root zone of the plant is the root zone of the plant.

4. The plant protection method according to claim 3, wherein the rhizosphere of the plant is soil on which the plant grows.

5. Formula (I)

[Where,

X represents a fluorine atom or a chlorine atom,

R ¹ is a hydrogen atom, a C1-C6 alkyl group that may be substituted with a halogen atom, a C2-C6 alkenyl group, a C2-C6 alkynyl group that may be substituted with a halogen atom, C6 — C 14 allyl group, C 7 _C 11 aralkyl group, 2—06 alkoxyalkyl group, C7—C 14 aralkyloxy group, C 3 -C 6 N, N —di (alkyl) aminoalkyl group C2-C6 alkylthioalkyl group, C2-C6 alkylsulfinylalkyl group, C2-C6 alkylsulfonylalkyl group, C3-C9 alkoxyalkoxyalkyl group, C2-C6 alkoxycarbonyl group C8-C 12 aralkyloxycarbonyl group, N, N—di (C 1 1 C 6 alkyl) force rubamoyl group, C 2—C 6 alkylcarbonyl group optionally substituted with halogen atom, Formyl group, C 1 -C 5 optionally substituted with halogen atom It represents alkylsulfonyl group or a C 6- C 10 § Li one Rusuruhoniru group, R ² represents a halogen atom or a C 1 may be substituted with a halogen atom one C 4 alkyl group, R ³ is a halogen atom, a C 1—C 4 alkyl group that may be substituted with a halogen atom, a C 1—C 4 alkoxy group that may be substituted with a halogen atom, or a C 2 that may be substituted with a halogen atom -C6 alkoxyalkoxy group, a C2-C4 alkenyloxy group optionally substituted with a halogen atom or a C2-C4 alkynyloxy group optionally substituted with a halogen atom,

m represents an integer of 0 to 4. ]

(Ν'-methyl) A plant protective agent against harm by pests containing a benzoylurea compound or a salt thereof and an inert carrier.

6. In formula (I), R ¹ is a hydrogen atom and R ³ is a halogen atom, which may be substituted with a halogen atom C 1 C 1 alkoxy group which may be substituted with a C 4 alkoxy group or a halogen atom The plant protective agent from harmful organisms according to claim 5, which is a —C4 alkyl group, and m is 0 or 1 (Ν′—methyl). A benzoylurea compound or a salt thereof and an inert carrier.

7. The plant protective agent according to claim 5, which is used for treatment of a plant into the rhizosphere.

8. The plant protection agent according to claim 5, which is used for treating soil in which plants grow. 9. It is applied to the root or seed of a plant or the rhizosphere of a plant to protect the plant from damage by pests. Use of (Ν'-methyl) benzoyl 'urea compound or a salt thereof represented by the formula (I).