JP2008081406A - Benzoyl pyrazole type compound and herbicide containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel herbicide which exhibits an excellent herbicidal effect over a wide application range such as a farming area and a nonfarming area and a wide application method range such as soil treatment and stem and leaf treatment. <P>SOLUTION: A benzoyl pyrazole type compound is represented by formula (I) (wherein R<SP>1</SP>is an alkyl or a cycloalkyl; R<SP>2</SP>is hydrogen or an alkyl; R<SP>3-a</SP>and R<SP>3-b</SP>are each an alkyl, a haloalkyl, an alkoxyalkyl or the like; R<SP>4</SP>is an alkyl, a haloalkyl, an alkoxy or the like; R<SP>5</SP>is an alkyl, a haloalkyl, an alkoxyalkyl or the like; and R<SP>6</SP>is a haloalkyl, a halogen, nitro or the like) or its salt. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel benzoylpyrazole compound useful as an active ingredient of a herbicide.

  Patent Documents 1 and 2 disclose benzoylpyrazole compounds, respectively. However, they have a different chemical structure from the benzoylpyrazole compounds represented by the following formula (I).

European Patent Publication No. 0352543 European Publication No. 0282944

  Conventionally, there has been a demand for a herbicide that has excellent herbicidal performance against weeds and safety for cultivated crops in order to save labor in controlling weeds and improve productivity of agricultural and horticultural crops. Yes. However, the search for new compounds suitable for such purposes relies on trial and error.

  The inventors of the present invention have completed the present invention as a result of various studies on benzoylpyrazole compounds in order to find better herbicides. That is, the present invention provides a compound of formula (I);

[Wherein, R ¹ is alkyl or cycloalkyl, R ² is a hydrogen atom or alkyl, and R ^3-a and R ^3-b are each independently alkyl; haloalkyl; alkoxyalkyl; cycloalkyl; alkenyl; alkenyl; alkynyl; or a aryl alkyl optionally substituted with R ^8, R ^3-a and R ^3-b is -R 9 bonded to each other ^- may form a next ring structure, R ⁴ is Alkyl, haloalkyl, alkoxy, halogen, nitro, cyano, alkylthio, alkylsulfinyl or alkylsulfonyl, where R ⁵ is alkyl; haloalkyl; alkoxyalkyl; haloalkoxyalkyl; alkoxy; haloalkoxy; alkoxyalkoxy; haloalkoxyalkoxy; Oxy; heterocyclyl Oxy; it may be substituted with, or R ^10; heterocyclylalkoxy; heterocyclylalkyl ^{alkoxyalkyl; -OC (O) SR 7;} -OC (O) OR 7; -C (O) OR 7; -C (O) SR 7 4,5-dihydroisoxazol-3-yl, R ⁶ is haloalkyl, halogen, nitro, cyano, alkylthio, alkylsulfinyl or alkylsulfonyl, and R ⁵ and R ⁶ are bonded to each other to form —R ¹¹ − And may form a ring structure, R ⁷ is halogen, alkyl, or alkoxy, R ⁸ is halogen, alkyl, or alkoxy, and —R ⁹ -is arbitrarily selected from a nitrogen atom, an oxygen atom, or a sulfur atom is also an alkylene chain containing one or more atoms, R ¹⁰ is halogen, alkyl or alkoxy, -R ^{11 -} is coupled to the site where R ⁶ is bonded an oxygen atom, sulfate Atom, -SO- or -SO ₂ - is an alkylene chain which is crosslinked by an atom or functional group selected arbitrarily from, -R ^{11 -} is represented by halogen, may be substituted by alkyl or alkoxy] A benzoylpyrazole compound or a salt thereof, a production method thereof, a herbicide containing them as an active ingredient, and an herbicidally effective amount thereof are applied to an undesired plant or a place where it grows to control or prevent the undesired plant The present invention relates to a method for suppressing growth.

  The compound represented by the formula (I) exhibits an excellent herbicidal effect.

In the compound represented by the formula (I), the alkyl or alkyl moiety may be linear or branched, and specific examples thereof include methyl, ethyl, n-propyl, iso-propyl, n-butyl, Examples thereof include those of C _1-6 such as iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl.
Cycloalkyl or cycloalkyl moieties include, for example, those of C _3-6 such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
The alkenyl or alkenyl moiety may be linear or branched, and specific examples thereof include vinyl, 1-propenyl, 2-propenyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3 -C _2-6 such as butadienyl.

Alkynyl may be linear or branched, and specific examples thereof include C _2-6 such as propargyl and 1-propynyl.
Examples of halogen include each atom of fluorine, chlorine, bromine or iodine.
Aryl moieties include phenyl, naphthyl and the like. The number of substitutions of the aryl moiety may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. Further, the substitution position of the aryl moiety may be any position.

  The heterocyclyl moiety is, for example, a 5-membered or 6-membered ring containing 1 to 4 heteroatoms arbitrarily selected from a nitrogen atom, an oxygen atom or a sulfur atom, Or unsaturated. Specific examples thereof include oxolane and 1,3-dioxolane. In addition, the number of substitutions of the heterocyclyl moiety may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. The substitution position of the heterocyclyl moiety may be any position.

The alkylene chain containing one or two or more atoms arbitrarily selected from a nitrogen atom, oxygen atom or sulfur atom contained in R ⁹ is one or two or more carbon moieties in the alkylene chain having a nitrogen atom, oxygen atom or It is substituted with one or more atoms arbitrarily selected from sulfur atoms.
The number of halogen substitutions such as haloalkyl and haloalkenyl may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. The halogen substitution position may be any position.

  The number of substitutions of alkoxy moieties such as alkoxyalkyl and haloalkoxyalkyl may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. Further, the substitution position of the alkoxy moiety may be any position.

The number of substitutions for R ⁸ or R ¹⁰ may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. In addition, the substitution position of each substituent may be any position.
The number of substitutions of halogen, alkyl or alkoxy as a substituent of R ¹¹ may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. In addition, the substitution position of each substituent may be any position.

  Alkoxyalkoxy means that the same or different alkoxy moieties are bonded to an alkoxy group. Any position may be sufficient as the substitution position of the alkoxy part which substitutes an alkoxy group. The same applies to haloalkoxyalkoxy and the like.

  The salt of the benzoylpyrazole compound represented by the above formula (I) includes any agriculturally acceptable salt, for example, alkali metal salts such as sodium salt and potassium salt; magnesium salt Alkaline earth metal salts such as calcium salts; ammonium salts such as dimethylamine salts and triethylamine salts; inorganic acid salts such as hydrochlorides, perchlorates, sulfates and nitrates; acetates and methanesulfonates Organic acid salts such as

The benzoylpyrazole compound represented by the above formula (I) or a salt thereof (hereinafter abbreviated as the compound of the present invention) can be produced according to the following reactions [A] to [P] and ordinary salt production methods. .
The compound of the present invention represented by the above formula (I) can be produced according to the following reaction [A].

(In the formula, R ¹ , R ² , R ^3-a , R ^3-b , R ⁴ , R ⁵ and R ⁶ are as described above, and Z is a leaving group such as halogen.)
That is, the compound of the present invention represented by the above formula (I) can be produced by reacting the compound represented by the formula (II) with the compound represented by the formula (III).
The above reaction can be carried out in a solvent. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N'-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be carried out in the presence of a base as necessary. The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. An alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate; an alkaline earth metal hydroxide such as calcium hydroxide; an alkaline earth metal carbonate such as calcium carbonate; Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. As the base, one or more of these may be appropriately selected and mixed for use.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The above reaction can also be carried out in a two-phase system of water and a solvent insoluble in water in the above solvent in the presence of a phase transfer catalyst such as a quaternary ammonium salt.
In addition, the compound of the present invention represented by the above formula (I) can be produced according to the following reaction [B].

(Wherein R ¹ , R ² , R ^3-a , R ^3-b , R ⁴ , R ⁵ and R ⁶ are as described above).
That is, the compound of the present invention represented by formula (I) is obtained by reacting a compound represented by formula (IV) or formula (V) or a mixture thereof with a compound represented by formula (VI). Can be manufactured.
The above reaction can be carried out in the presence of a solvent, if necessary. Examples of the solvent include halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, and propyl acetate; Examples include aprotic polar solvents such as acetonitrile, N, N′-dimethylformamide, dimethyl sulfoxide, sulfolane, and dimethoxyethane; ethers such as diethyl ether, dioxane, and tetrahydrofuran. As the solvent, one or more of these can be appropriately selected.

The above reaction can be carried out in the presence of a base. The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. An alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate; an alkaline earth metal hydroxide such as calcium hydroxide; an alkaline earth metal carbonate such as calcium carbonate; Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. As the base, one or more of these may be appropriately selected and mixed for use.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (IV) or formula (V) or a mixture thereof can be produced according to the following reaction [C].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by the formula (IV) or the formula (V), or a mixture thereof can be produced by reacting the compound represented by the formula (II) with thiocarbonyl chloride (CSCl ₂ ). it can.

  The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

The above reaction can be performed in the presence of a base, if necessary. The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. An alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate; an alkaline earth metal hydroxide such as calcium hydroxide; an alkaline earth metal carbonate such as calcium carbonate; Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. As the base, one or more of these may be appropriately selected and mixed for use.
The reaction temperature for the above reaction is usually from -10 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (II) can be produced according to the following reaction [D].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by the formula (II) can be produced by a rearrangement reaction of the compound represented by the formula (VII).
The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate and propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and dimethoxyethane; ethers such as diethyl ether, dioxane and tetrahydrofuran And the like. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be performed in the presence of a base, if necessary. The base may be either an organic base or an inorganic base. Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal cyanides such as sodium cyanide and potassium cyanide. It is done. These bases can be used by appropriately selecting and mixing one or two or more of these at a molar equivalent of 0.01 to 100 moles relative to the number of moles of the compound of formula (VII).

In the above reaction, a catalyst can be added as necessary. As the catalyst, acetone cyanohydrin can be used in an amount of 0.01 to 10 molar equivalents relative to the number of moles of the compound of formula (VII).
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (VII) can be produced according to the following reaction [E].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by the formula (VII) is reacted with the compound represented by the formula (VIII) or a salt thereof, for example, hydrochloride, sulfate, nitrate, etc., and the compound represented by the formula (IX). Can be manufactured.

  The above reaction can be carried out in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate and propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and dimethoxyethane; ethers such as diethyl ether, dioxane and tetrahydrofuran And the like. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be performed in the presence of a base, if necessary. As the base, the base may be either an inorganic base or an organic base. Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; Examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. These bases can be used by appropriately selecting and mixing one or two or more of these at 1 to 100 molar equivalents relative to the number of moles of the compound of the formula (IX).

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (IX) can be produced according to the following reaction [F].

(Wherein R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by the formula (IX) can be produced by reacting the compound represented by the formula (X) with a halogenating agent.
In the above reaction, a halogenating agent such as thionyl chloride or oxalyl chloride can be reacted in an amount of 1 to 100 molar equivalents relative to the number of moles of the compound represented by the formula (X).

  The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

In the above reaction, a catalyst can be used as necessary. Examples of the catalyst include DMF.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
In addition to the above method, the compound represented by the formula (VII) can be produced according to the following reaction [G].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by the formula (VII) is obtained by dehydrating a compound represented by the formula (VIII) or a salt thereof such as hydrochloride, sulfate, nitrate, and the compound represented by the formula (X). It can manufacture by making it react using an agent.
Examples of the dehydrating agent used in the above reaction include DCC (dicyclohexylcarbodiimide) and 1-ethyl 3- (3-dimethylaminopropyl) -carbodiimide hydrochloride.

  The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

The above reaction can be performed in the presence of a base, if necessary. Examples of the base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. These bases can be used by appropriately selecting and mixing one or two or more of these at 1 to 100 molar equivalents relative to the number of moles of the compound represented by the formula (X).
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (X) can be produced according to the following reaction [H].

(In the formula, R ⁴ , R ⁵ and R ⁶ are as described above, and L is a protecting group such as alkyl.)
The compound represented by the formula (X) can be produced by hydrolyzing the compound represented by the formula (XI).
The above reaction can be carried out in the presence of a solvent, if necessary. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and dimethoxyethane; such as diethyl ether, dioxane and tetrahydrofuran Ethers; alcohols such as methanol and ethanol; water and the like. As a solvent, these 1 type (s) or 2 or more types can be selected suitably.

  The above reaction can be performed in the presence of a base or an acid, if necessary. The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide; alkali metal carbonates such as potassium carbonate and sodium carbonate; alkaline earth metal carbonates such as calcium carbonate and barium carbonate. Can be mentioned. Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine. Examples of the acid include hydrochloric acid, sulfuric acid, perchloric acid and the like. These bases or acids can be used by appropriately selecting and mixing one or more of these at 1 to 100 molar equivalents relative to the number of moles of the compound represented by formula (XI). .

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
Among the compounds represented by the formula (XI), the compound represented by the formula (XI-a-1) in which R ⁵ is R ^5-a-1 can be produced according to the following reaction [I]. .

Wherein R ⁴ , R ⁶ and L are as described above, and R ^5-a-1 is alkoxy, haloalkoxy, alkoxyalkoxy, haloalkoxyalkoxy, heterocyclyloxy, heterocyclylalkoxy, —OC (O) SR ⁷ Or —OC (O) OR ⁷ and R ^α is alkyl, haloalkyl, alkoxyalkyl, haloalkoxyalkyl, heterocyclyl, heterocyclylalkyl, —C (O) SR ⁷ or —C (O) OR ⁷ .
That is, the compound represented by the formula (XI-a-1) can be produced by reacting the compound represented by the formula (XII) with the compound represented by the formula (XIII) using a dehydrating agent. it can.

Examples of the dehydrating agent used in the above reaction include DCC (dicyclohexylcarbodiimide), 1-ethyl 3- (3-dimethylaminopropyl) -carbodiimide hydrochloride, diethyl azodicarboxylate, and the like.
The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

The above reaction can be performed in the presence of a base, if necessary. Examples of the base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. These bases can be used by appropriately selecting and mixing one or two or more of these at 1 to 100 molar equivalents relative to the number of moles of the compound represented by the formula (XII).
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
In addition to the above method, the compound represented by the formula (XI-a-1) can also be produced according to the following reaction [J].

(In the formula, R ⁴ , R ^5-a-1 , R ⁶ , R ^α and L are as described above. X represents a leaving group such as halogen or a methanesulfonyloxy group.)
That is, the compound represented by the formula (XI-a-1) can be produced by reacting the compound represented by the formula (XII) and the compound represented by the formula (XIV) in the presence of a base. it can.

  The above reaction can be carried out in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate and propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and dimethoxyethane; ethers such as diethyl ether, dioxane and tetrahydrofuran And the like. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be performed in the presence of a base, if necessary. The base may be either an inorganic base or an organic base. Examples of the organic base include triethylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal hydrides such as sodium hydride and potassium hydride. Is mentioned. These bases can be used by appropriately selecting and mixing one or more of these at a molar equivalent of 0.5 to 100 moles relative to the number of moles of the compound of the formula (XII).

The above reaction can be carried out in the presence of a catalyst, if necessary. Examples of the catalyst include potassium iodide and tetranormal butyl ammonium iodide.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XII) can be produced according to the following reaction [K].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XII) can be produced by reacting the compound represented by the formula (XV) with a Lewis acid such as BBr ₃ .

  The above reaction can be carried out in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; benzene, toluene, xylene; methyl acetate, ethyl acetate, acetic acid And aromatic hydrocarbons such as esters such as propyl. As the solvent, one or more of these can be appropriately selected.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XV) can be produced according to the following reaction [L].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XV) can be produced by a reaction in which the protective group L is introduced into the compound represented by the formula (XVI).
The above reaction can be carried out in the presence of a solvent, if necessary. Examples of solvents include alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as methyl acetate, ethyl acetate and propyl acetate; methylene chloride, chloroform, dichloroethane and trichloroethane. Halogenated hydrocarbons such as: aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, and dimethoxyethane. As the solvent, one or more of these can be appropriately selected.

The above reaction can be performed in the presence of an acid, if necessary. Examples of the acid that can be used in the above reaction include hydrochloric acid and sulfuric acid.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
Among the compounds represented by the above formula (XI), a compound in which R ⁵ is R ^5-a-2 can be produced according to the following reaction [M].

(Wherein R ⁴ , R ⁶ and L are as described above, and R ^5-a-2 is alkylthiocarbonyl.)
That is, the compound represented by the formula (XI-a-2) can be produced by reacting the compound represented by the formula (XVIII) with an alkylthiol.
The above reaction can be carried out in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. For example, ethers such as diethyl ether, dioxane and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; methyl acetate; Examples include esters such as ethyl acetate and propyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane. As the solvent, one or more of these can be appropriately selected.

  In the said reaction, it can be made to react in presence of a base as needed. The base may be either an inorganic base or an organic base. Examples of the organic base include triethylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. Examples of the inorganic base include alkali metal carbonates such as potassium carbonate and sodium carbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal hydrides such as sodium hydride and potassium hydride. It is done. As the base, one or more of these may be appropriately selected and mixed for use.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XVIII) can be produced according to the following reaction [N].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XVIII) can be produced by reacting the compound represented by the formula (XIX) with a halogenating agent. This reaction can be carried out in the same manner as the above-mentioned reaction [F].
The compound represented by the above formula (XIX) can be produced according to the following reaction [O].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XIX) can be produced by oxidizing the compound represented by the formula (XX).
Examples of the oxidizing agent in the above reaction include potassium permanganate and chromium trioxide.

The above reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. For example, ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate, ethyl acetate and propyl acetate; diethyl ether, dioxane and tetrahydrofuran Such ethers. As the solvent, one or more of these can be appropriately selected.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XX) can be produced according to the following reaction [P].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XX) can be produced by reacting the compound represented by the formula (XXI) with an oxidizing agent in the presence of a solvent.
Examples of the oxidizing agent used in the above reaction include N-methylmorpholine oxide.

The solvent used in the above reaction may be any solvent as long as it is inert to the reaction. For example, an aprotic polar solvent such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; Examples include ethers such as diethyl ether, dioxane and tetrahydrofuran. As the solvent, one or more of these can be appropriately selected.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.

  The compound of the present invention exhibits an excellent herbicidal effect when used as an active ingredient of a herbicide. The range of application ranges from paddy fields, upland fields, orchards, mulberry fields and other non-agricultural lands such as forests, farm roads, grounds, and factory premises. You can choose.

  The compounds of the present invention include, for example, Inobie, Agaricus, Enokorogusa, Akinoenokorogusa, Oshiba, Otsunomugi, Seiban sorghum, Shibamugi, Velvet millet, Paragrass, Azegaya, Izaegaya, Suzumenokatabira, Suzumenotepuga Cyperaceae weeds such as Tamagayatsuri, Matsubai, Kurogwai, etc. , Ichibi, Maruba morning glory, Shiroza, American stag beetle, Siberian leopard, Aubiyu, Aogateto, Ebisugusa, Inabaduki, Sanaetade, Ha Because it can control harmful weeds such as broadleaf weeds such as maize, soybeans, cotton, cotton buds, red fir tree, seedlings, photokenoza, ragweed, jaegras, convolvulaceae, white-winged duckweeds, broadleaf weeds Selectively control harmful weeds or non-selectively control harmful weeds in the cultivation of wheat, rice, barley, oat, sorghum, rape, sunflower, sugar beet, sugarcane, turf, peanut, flax, tobacco, coffee It is used effectively when In particular, the compound of the present invention is used for the cultivation of corn, soybean, cotton, wheat, rice, rape, sunflower, sugar beet, sugar cane, turf, peanut, flax, tobacco, coffee, etc., among them, the cultivation of corn, soybean, wheat, rice, etc. Effectively used when selectively controlling harmful weeds.

  The compounds of the present invention are usually mixed with various agricultural adjuvants such as powders, granules, granule wettable powders, wettable powders, aqueous suspensions, oily suspensions, aqueous solvents, emulsions, tablets, capsules, etc. Although it is formulated into a form and used as a herbicide, it can be in any conventional form used in the art as long as it meets the purpose of the present invention. Adjuvants used in the formulation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch, etc. Solvents such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, alcohol; fatty acid salts, benzoates, Alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkyl sulfate, alkyl sulfate, alkyl aryl sulfate, alkyl diglycol ether sulfate, alcohol sulfate, al Sulfonate, alkylaryl sulfonate, aryl sulfonate, lignin sulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate ester salt, alkyl aryl phosphate, styryl aryl phosphate, poly Oxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate, naphthalene sulfonic acid formalin Anionic surfactants and spreading agents such as salts of condensates; sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid polyglycerides, fatty acid alcohol polyols Glycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene Nonionic surfactants and spreading agents such as sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid ester; olive oil, kapok oil, castor oil, palm oil, straw oil, Vegetable oil such as coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, cutting oil, liquid paraffin And mineral oil. These adjuvants can be selected from those known in the art without departing from the object of the present invention. In addition, various commonly used adjuvants such as a bulking agent, thickener, anti-settling agent, antifreezing agent, dispersion stabilizer, safener, and antifungal agent can also be used. The compounding ratio of the compound of the present invention and various adjuvants is 0.1: 99.9 to 95: 5, preferably 0.2: 99.8 to 85:15.

  The application rate of the herbicide containing the compound of the present invention cannot be defined unconditionally due to differences in weather conditions, soil conditions, formulation forms, types of target weeds, application time, etc., but generally the compound of the present invention is 0.5 to 5,000 per hectare. g, preferably 1 to 1,000 g, more preferably 10 to 500 g. The present invention includes a method for controlling harmful weeds by application of such a herbicide.

  In addition, the herbicide containing the compound of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, safeners and the like, and in this case, more excellent effects and functions may be exhibited. Other pesticides include herbicides, fungicides, antibiotics, plant hormones, insecticides and the like. In particular, a mixed herbicidal composition in which the compound of the present invention and one or more active ingredient compounds of other herbicides are mixed or used in combination has a range of applicable herb species, timing of chemical treatment, herbicidal activity, etc. It is possible to improve in the preferred direction. In addition, the compound of the present invention and other herbicidal active ingredient compounds may be prepared separately and mixed at the time of spraying, or both may be used together. The above-described mixed herbicidal composition is also included in the present invention.

  The mixing ratio of the compound of the present invention and the active ingredients of other herbicides cannot be defined unconditionally due to differences in weather conditions, soil conditions, drug formulation, application time, application method, etc. On the other hand, other herbicides contain 0.001 to 10,000 parts by weight, preferably 0.01 to 1,000 parts by weight of the active ingredient per one kind. In addition, the appropriate amount to be applied is 0.1 to 10,000 g, preferably 0.2 to 5,000 g, more preferably 10 to 3,000 g as the total amount of active ingredient compounds per hectare. The present invention also includes a method for controlling harmful weeds by application of such a mixed herbicidal composition.

Examples of the active ingredients of other herbicides include those listed below (generic names; including those for which some ISO applications have been filed), but salts, alkyl esters, etc. exist in these compounds even if not specifically described. Of course, they are also included.
(1) 2,4-D, 2,4-DB, 2,4-DP, MCPA, MCPB, MCPP, naproanilide, phenoxy type such as clomeprop, 2,3,6-TBA, Aromatic carboxylic acids such as dicamba, dichlobenil, picloram, triclopyr, clopyralid, aminopyralid, other naptalam, benazolin, quinro It is said to show herbicidal efficacy by disrupting the hormonal action of plants such as quinclorac, quinmerac, diflufenzopyr, thiazopyr.

  (2) urea systems such as chlorotoluron, diuron, fluometuron, linuron, isoproturon, metobenzuron, tebuthiuron, simazine, Atrazine, atratone, simetrin, promethrin, dimethametryn, hexazinone, metribuzin, terbuthylazine, cyanazine, ametrine, ametrine Triazines such as cybutryne, triaziflam, propazine, uracils such as bromacil, lenacil, terbacil, propanil, cypromid A Carbamates such as Lido, swep, desmedipham, phenmedipham, hydroxybenzo such as bromoxynil, bromoxynil-octanoate, ioxynil Nitriles, other pyridates, bentazone, amicarbazone, methazole, etc. are said to show herbicidal efficacy by inhibiting plant photosynthesis.

  (3) Quaternary ammonium salt systems such as paraquat and diquat, which are said to themselves become free radicals in the plant body and generate active oxygen to show rapid herbicidal efficacy.

  (4) Nitrofen, Chlomethoxyfen, bifenox, acifluorfen-sodium, fomesafen, oxyfluorfen, lactofen, ethoxyphenethyl Diphenyl ethers such as (ethoxyfen-ethyl), chlorphthalim, flumioxazin, flumiclorac-pentyl, cyclic imides such as fluthiacet-methyl, and other oxadiargyl ( oxadiargyl), oxadiazon, sulfentrazone, carfentrazone-ethyl, thidiazimin, pentoxazone, azafenidin, isopropazol Isopropazole, pyraflufen-ethyl, benzfendizone, butafenacil, metobenzuron, cinidon-ethyl, flupoxam, fluazolate, Inhibits plant chlorophyll biosynthesis, such as profluazol, pyrachlonil, and flufenpyr-ethyl, and causes abnormal accumulation of photosensitized peroxides in plants. It is said to show herbicidal efficacy.

  (5) Pyridazinones such as norflurazon, chloridazon, metflurazon, pyrazolate, pyrazoxifene, benzofenap, topramezone, BAS-670H, pyra Pyrazoles such as pyrasulfotole, other amitrol, fluridone, flurtamone, diflufenican, methoxyphenone, clomazone, sulcotrione, Mesotrione, Tefuryltrione, AVH-301, Isoxaflutole, Difenzoquat, Isoxachlortole, Benzobicyclon Picolinafen (picolinafen), Bifurubutamido (beflubutamid) inhibiting dye biosynthesis of plants, such as carotenoids, such as, what is showing a herbicidal activity characterized by whitening effect.

  (6) Diclohopop-methyl, flamprop-M-methyl, pyriphenop-sodium, fluazifop-butyl, haloxyhop-methyl ( Aryloxyphenoxy such as haloxyfop-methyl, quizalofop-ethyl, cyhalofop-butyl, fenoxaprop-ethyl, metamifop-propyl Propionic acid, alloxydim-sodium, clethodim, sethoxydim, tralkoxydim, butroxydim, tepraloxydim, caloxydim, clefoxydim , Cyclohexanedione such as profoxydim What is specifically herbicidal activity to grasses are found strongly, such as.

  (7) Chlorimuron-ethyl, sulfometuron-methyl, primisulfuron-methyl, bensulfuron-methyl, chlorsulfuron, methos Methylsulfuron-methyl, Cinosulfuron, pyrazosulfuron-ethyl, azimsulfuron, flazasulfuron, rimsulfuron, nicosulfuron, imazosulfuron imazosulfuron, cyclosulfamuron, prosulfuron, flupirsulfuron, trisulfuron-methyl, halosulfuron-methyl, thifensulfuron-methyl ), Et Cissulfuron, oxasulfuron, ethametsulfuron, flupirsulfuron, iodosulfuron, sulfosulfuron, triasulfuron, tribenuron Methyl (tribenuron-methyl), tritosulfuron (tritosulfuron), forum sulfururon (foramsulfuron), trifloxysulfuron (trifloxysulfuron), isosulfuron-methyl (isosulfuron-methyl), flucetosulfuron (flucetosulfuron), mesosulfuron methyl Sulfonylureas such as mesosulfuron-methyl, flumetsulam, metosulam, diclosulam, cloransulam-methyl, florasulam, metosulfam, penoxus Triazolopyrimidinesulfonamides such as penoxsulam, imazapyr, imazethapyr, imazaquin, imazamox, imazameth, imazamethabenz, imazamethabenz, imazamethabenz, imazapica (im) Imidazolinones, pyrithiobac-sodium, bispyribac-sodium, pyriminobac-methyl, pyribenzoxim, pyriftalid, KUH-021 Pyrimidinyl salicylic acid such as flucarbazone, sulfonylaminocarbonyltriazolinone such as procarbazone-sodium, other glyphosate, glyphosate ammonium salt (glyphosate -ammonium), glyphosate-isopropylamine, sulfosate, glufosinate, glufosinate-ammonium, bilanafos, etc. to inhibit plant amino acid biosynthesis It is said to show herbicidal efficacy.

  (8) Dinitroaniline series such as trifluralin, oryzalin, oryzalin, nitraline, pendimethalin, ethalfluralin, benfluralin, prodiamine, benzulide (Bensulide), amides such as napronamide, pronamide, amiprofos-methyl, butamifos, anilofos, organic phosphorus such as piperophos, Propham, chlorpropham, phenyl carbamates such as barban, daimuron, cumyluron, cumylamines such as bromobutide, other aslam, dithiopyr (Dithiopyr), thiazopyr (Thiazopyr), etc. that are said to show herbicidal efficacy by inhibiting cell mitosis of plants.

  (9) alachlor, butachlor, pretilachlor, metolachlor, S-metolachlor, tenylchlor, petoxamide, acetochlor , Chloroacetamides such as propachlor, propisochlor, etobenzanid, mefenacet, flufenacet, tridiphane, caffenstrole, Fentrazamide, oxaziclomefone, indanofan, dimethenamid, etc. that are said to show herbicidal activity by inhibiting plant protein biosynthesis or lipid biosynthesis

  (10) EPTC, butyrate, vernolate, molinate, pebulate, cycloate, dimepiperate, prosulfocarb, esprocarb, thiobencarb ( Thiocarbamates such as thiobencarb, pyributicarb, diallate, triallate, other MSMA, DSMA, endothall, etofumesate, sodium chlorate, pelargonic acid (Pelargonic acid), phosamine, pinoxaden, HOK-201 and the like.

(11) What is said to show herbicidal efficacy by infesting plants such as Xanthomonas campestris , Epicoccosurus nematosurus , Exserohilum monoseras , Drechsrela monoceras .

  Next, examples of the present invention will be described, but the present invention is not limited thereto. Hereafter, the synthesis example of this invention compound is described.

Synthesis example 1
Synthesis of 5- (morpholino-4-ylthiocarbonyloxy) -1-ethylpyrazol-4-yl 3- (methoxycarbonyl) -2-methyl-4- (methylsulfonyl) phenyl ketone (compound No. 15 below)
5-hydroxy-1-ethylpyrazol-4-yl 3- (methoxycarbonyl) -2-methyl-4- (methylsulfonyl) phenyl ketone (300 mg, 0.82 mmol), morpholin-4-ylthiocarbonyl chloride (271 mg) , 1.64 mmol) and dry dioxane (30 mL) were mixed and heated to reflux for 4 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The extract was washed with an aqueous sodium hydrogen carbonate solution and then dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 2: 8) to obtain the desired product (177 mg, 0.36 mmol) as a crystal (yield 43.6%).

Synthesis example 2
5- (N, N-diethylthiocarbamoyloxy) -1-methylpyrazol-4-yl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone (compound No. 18 below) Composition
5-hydroxy-1-methylpyrazol-4-yl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone (516 mg, 1.40 mmol), N, N-diethylthiocarbamoyl chloride ( Purity 95%, 246 mg, 1.54 mmol) and dry tetrahydrofuran (15 mL) were mixed, and triethylamine (283 mg, 2.80 mmol) was added thereto while cooling with ice water. The mixture was stirred for 16 hours while gradually raising the reaction temperature to room temperature. The reaction mixture was poured into ice water and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 4: 6) to obtain an oily target product (560 mg, 1.16 mmol) (yield 82.6%).

Next, typical examples of the compounds of the present invention represented by the formula (I) are listed in Table ¹ , and their ¹ H-NMR spectral data are listed in Table 2. These compounds can be synthesized based on the above synthesis examples or various production methods of the above-described compounds of the present invention. In Tables 1 and 2, No. indicates a compound number. Me represents a methyl group, Et represents an ethyl group, n-Pr represents a normal propyl group, i-Pr represents an isopropyl group, c-Pr represents a cyclopropyl group, and t-Bu represents a tertiary butyl group. . When R ⁵ and R ⁶ were bonded to form a ring structure, the left end of the chain group in the table was bonded to the position where R ⁵ was originally bonded, and the right end was originally bonded to R ⁶ Represents binding to a site. For example, “—CH ₂ CH ₂ CH ₂ SO ₂ —” means that the —CH ₂ side is bonded to the R ⁵ position and the SO ₂ — side is bonded to the R ⁶ position.

Next, test examples are described.
Test example 1
A field crop soil was filled in a 1 / 170,000 hectare pot and seeds of various plants were sown. After that, the plant had a certain leaf age ((1) Nobier; 1.0-2.5 leaf stage, (2) Bark beetle; 1.0-3.0 leaf stage, (3) Enokorogusa; 1.5-2.7 leaf stage, (4) Aogateto; 0.3-2.0 Leaf stage, (5) American stag beetle; 0.1-0.5 leaf stage, (6) green leaf; 0.3-1.5 leaf stage, (7) rice; 1.4-2.5 leaf stage, (8) wheat; 2.0-3.0 leaf stage, ( 9) Corn; 2.5 to 3.5 leaf stage, (10) Soybean; cotyledon stage to 0.3 leaf stage), and a wettable powder or emulsion prepared according to a conventional formulation method is used as a predetermined active ingredient amount. And was diluted with water equivalent to 500 liters per hectare. Further, 0.1% by volume of an agricultural spreading agent was added to the diluted solution, and the leaves were treated with a small spray.
On the 17th to 22nd day after the chemical treatment, the growth state of various plants was observed with the naked eye, and the herbicidal effect was evaluated at a herbicidal rate (%) of 0 (equivalent to the untreated group) to 100 (completely killed). The result was obtained.

Test example 2
A field crop soil was filled in a 1 / 170,000 hectare pot, and seeds of various plants (Nobie, mosquito, Enocologosa, Aogaeto, American King Deer, Ichibi, Rice, Wheat, Corn, and Soybean) were sown. On the day after sowing, the wettable powder or emulsion prepared according to the usual formulation method of the compound of the present invention is weighed so as to have a predetermined active ingredient amount, diluted in water equivalent to 500 liters per hectare, and treated with a small spray. did.
On the 19th to 20th day after the chemical treatment, the growth state of various plants was observed with the naked eye, and the herbicidal effect was evaluated at a herbicidal rate (%) from 0 (equivalent to the untreated area) to 100 (complete withering) The result was obtained.

Test example 3
Paddy soil was stuffed in 1 / 1,000,000 hectare pots, seeds of nobier and firefly were sown, and lightly covered with soil. Thereafter, the tube was allowed to stand in a greenhouse at a water depth of 0.5 to 1 cm, and Urikawa tubers were planted the next day or two days later. Thereafter, the water depth was maintained at 3 to 4 cm, and when the nobier and firefly reached the 0.5 leaf stage and the urikawa reached the primary leaf stage, the compound of the present invention was diluted with water in a wettable powder or emulsion prepared according to the usual formulation method. The liquid was dropped evenly with a pipette so as to obtain a predetermined active ingredient amount. In addition, paddy soil was stuffed into 1 / 1,000,000 hectare pots, paddling was carried out, the inundation depth was 3-4 cm, and the next leaf rice (variety: Nipponbare) was transplanted to a transplant depth of 3 cm on the next day. On the 4th day after transplantation, the compound of the present invention was treated as described above.
Visual observation of growth of nobies, firefly and urikawa 13 to 15 days after drug treatment, and rice growth state 21 to 23 days after drug treatment, 0 (equivalent to untreated area) to 100 (completely) The results of Table 5 and Table 6 were obtained by evaluating with the herbicidal rate (%) of “killing”.

Next, formulation examples of the present invention will be described.
Formulation Example 1
(1) Compound of the present invention 75 parts by weight (2) Geropone T-77 (trade name; manufactured by Rhone-Poulenc) 14.5 parts by weight (3) NaCl 10 parts by weight (4) dextrin 0.5 parts by weight or more The ingredients are put into a high-speed mixing fine granulator, 20% water is further added thereto, and granulated and dried to obtain a granulated wettable powder.

Formulation Example 2
(1) Kaolin 78 parts by weight (2) Labelin FAN (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts by weight (3) Solpol 5039 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 5 parts by weight (4 ) Carplex (trade name; manufactured by Shionogi Pharmaceutical Co., Ltd.) 15 parts by weight or more, a mixture of the components (1) to (4) and the compound of the present invention are mixed at a weight ratio of 9: 1 to obtain a wettable powder. Is obtained.

Formulation Example 3
(1) High filler No. 10 (trade name; manufactured by Matsumura Sangyo Co., Ltd.) 33 parts by weight (2) Solpol 5050 (trade name; manufactured by Toho Chemical Co., Ltd.) 3 parts by weight (3) Solpol 5073 (trade name; Toho Chemical Industries, Ltd.) Product) 4 parts by weight (4) Compound of the present invention 60 parts by weight or more of (1) to (4) are mixed to obtain a wettable powder.

Formulation Example 4
(1) Compound of the present invention 4 parts by weight (2) bentonite 30 parts by weight (3) calcium carbonate 61.5 parts by weight (4) Toxanone GR-31A (trade name; manufactured by Sanyo Chemical Industries, Ltd.) 3 parts by weight (5 ) Calcium lignin sulfonate 1.5 parts by weight Premixed (1), (2) and (3), mixed with (4), (5) and water, and extruded Grain. Thereafter, the granules are obtained by drying and sizing.

Formulation Example 5
(1) Compound of the present invention 30 parts by weight (2) Siegrite (trade name; manufactured by Siegrite Co., Ltd.) 60 parts by weight (3) New Calgen WG-1 (trade name; manufactured by Takemoto Yushi Co., Ltd.) 5 parts by weight (4) New Calgen FS-7 (trade name; manufactured by Takemoto Yushi Co., Ltd.) 5 parts by weight (1), (2) and (3) are mixed, passed through a pulverizer, and (4) is added. After kneading, extrusion granulation is performed. Thereafter, it is dried and sized to obtain a granulated wettable powder.

Formulation Example 6
(1) Compound of the present invention 28 parts by weight (2) Sopropol FL (trade name; manufactured by Rhone-Poulein) 2 parts by weight (3) Solpol 355 (trade name; manufactured by Toho Chemical Co., Ltd.) 1 part by weight (4) IP solvent 1620 (trade name; manufactured by Idemitsu Petrochemical Co., Ltd.) 32 parts by weight (5) ethylene glycol 6 parts by weight (6) water 31 parts by weight or more of components (1) to (6) are mixed and wet pulverized An aqueous suspension is obtained by pulverization using a machine (Dyno-Mill).

Claims (3)

Formula (I);

[Wherein, R ¹ is alkyl or cycloalkyl, R ² is a hydrogen atom or alkyl, and R ^3-a and R ^3-b are each independently alkyl; haloalkyl; alkoxyalkyl; cycloalkyl; alkenyl; alkenyl; alkynyl; or a aryl alkyl optionally substituted with R ^8, R ^3-a and R ^3-b is -R 9 bonded to each other ^- may form a next ring structure, R ⁴ is Alkyl, haloalkyl, alkoxy, halogen, nitro, cyano, alkylthio, alkylsulfinyl or alkylsulfonyl, where R ⁵ is alkyl; haloalkyl; alkoxyalkyl; haloalkoxyalkyl; alkoxy; haloalkoxy; alkoxyalkoxy; haloalkoxyalkoxy; Oxy; heterocyclyl Oxy; it may be substituted with, or R ^10; heterocyclylalkoxy; heterocyclylalkyl ^{alkoxyalkyl; -OC (O) SR 7;} -OC (O) OR 7; -C (O) OR 7; -C (O) SR 7 4,5-dihydroisoxazol-3-yl, R ⁶ is haloalkyl, halogen, nitro, cyano, alkylthio, alkylsulfinyl or alkylsulfonyl, and R ⁵ and R ⁶ are bonded to each other to form —R ¹¹ − And may form a ring structure, R ⁷ is halogen, alkyl, or alkoxy, R ⁸ is halogen, alkyl, or alkoxy, and —R ⁹ -is arbitrarily selected from a nitrogen atom, an oxygen atom, or a sulfur atom is also an alkylene chain containing one or more atoms, R ¹⁰ is halogen, alkyl or alkoxy, -R ^{11 -} is coupled to the site where R ⁶ is bonded an oxygen atom, sulfate Atom, -SO- or -SO ₂ - is an alkylene chain which is crosslinked by an atom or functional group selected arbitrarily from, -R ^{11 -} is represented by halogen, may be substituted by alkyl or alkoxy] A benzoylpyrazole compound or a salt thereof. A herbicide containing the benzoylpyrazole compound or salt thereof according to claim 1 as an active ingredient. A method of applying an herbicidally effective amount of the benzoylpyrazole compound or a salt thereof according to claim 1 to an undesired plant or a place where the undesired plant grows to control or suppress the undesired plant.