JP2015013809A - Heteroaryl sulfonamide compound or salt thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel herbicide.SOLUTION: The present invention provides a heteroaryl sulfonamide compound of the general formula (I) or a salt thereof, and a herbicide containing the compound as an active ingredient. [In the formula, A is O, S, SO, SOor CRR; W is O or S; Z is O, S or CRR; m and n are 0, 1 or 2 and satisfy 0≤n+m≤3; q is 0, 1, or 2; Ris halo C-Calkyl; Ris H or C-Calkoxycarbonyl; Ris a halogen atom, optionally halo-substituted C-Calkyl, C-Calkenyl, alkynyl, C-Ccycloalkyl, C-Calkylsulfonyl, or the like.]

Description

  The present invention relates to a novel heteroarylsulfonamide compound or salt thereof useful as an active ingredient of a herbicide, and a herbicide containing them.

  Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4 below disclose haloalkylsulfonanilide derivatives having a certain structure. However, they do not specifically disclose the heteroarylsulfonamide compounds represented by the general formula (I) described later.

Published Patent Publication No. 2006-265240 Published Patent Publication No. 2008-143895 International Publication No. WO2010 / 026989 International Publication No. WO2010 / 119906

  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. In the development of new herbicides in the future, there is a demand for the creation of compounds that can exhibit the desired herbicidal effect while keeping the amount of applied herbage low. In addition, compounds that have practical residual effects but are less likely to remain in the soil than necessary or have a negative impact on the environment due to the outflow of active ingredients to soils other than the application site due to rainwater, etc. Creation of is demanded. Furthermore, creation of a compound with high animal safety is desired. However, the search for new compounds suitable for such purposes relies on trial and error.

  The inventors of the present invention have made various studies to find a better herbicide that can solve the above-described problems. As a result, the present inventors have found that the novel heteroarylsulfonamide compound exhibits a high herbicidal effect on various weeds at a low dosage and yet exhibits high safety in various useful crops, thereby completing the present invention.

  That is, the present invention relates to the general formula (I):

[Wherein A is an oxygen atom, sulfur atom, SO, SO ₂ or CR ⁸ R ⁹ ; W is an oxygen atom or sulfur atom; Z is an oxygen atom, sulfur atom or CR ¹⁰ R ¹¹ ; m Is 0, 1 or 2; n is 0, 1 or 2; provided that 0 ≦ n + m ≦ 3; q is 0, 1 or 2; R ¹ is haloC ₁ -C ₆ R ² is a hydrogen atom or C ₁ -C ₁₂ alkoxycarbonyl; R ³ is a halogen atom, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C _1- C ₃ -C ₆ cycloalkyl optionally substituted with C ₆ alkyl, halo C ₁ -C ₆ alkyl, halo C ₂ -C ₆ alkenyl, halo C ₂ -C ₆ alkynyl, halo C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkylsulfonyl, halo C ₁ -C ₆ alkylsulfonyl, phenyl or cyano optionally substituted with Y; R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ And R ¹¹ are the same or C ₃ -C ₆ cyclo which may be different and may be substituted with hydrogen atom, halogen atom, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkyl Alkyl, halo C ₁ -C ₆ alkyl, halo C ₂ -C ₆ alkenyl, halo C ₂ -C ₆ alkynyl, halo C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C ₁ -C ₆ alkyl, Y Phenyl optionally substituted with Y, phenyl C ₁ -C ₆ alkyl optionally substituted with Y, C ₁ -C ₆ alkylcarbonyloxy, hydroxyl or cyano; R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ and R ¹⁰ and R ¹¹ can be bonded to each other to form an optionally substituted 3- to 7-membered ring, and the 3- to 7-membered ring is an oxygen atom, a sulfur atom or nitrogen atom (nitrogen atom, is substituted C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, by C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl Also contain one or two heteroatoms selected from may also) well, or can be formed olefin, carbonyl or ^{thiocarbonyl; R 4, R 5, R} 6, R 7, R 8 , R ⁹ , R ¹⁰ and R ¹¹ are any R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ or R on a carbon atom different from the carbon atom to which each is bonded. ¹¹ to form an optionally substituted 3- to 8-membered ring, and the 3- to 8-membered ring is an oxygen atom, a sulfur atom, or a nitrogen atom (the nitrogen atom is C ₁ -C May contain 1 or 2 heteroatoms selected from ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl); R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ can be any R ⁴ , R ⁵ , R ⁶ , R ⁷ on the carbon atom adjacent to the carbon atom to which they are attached. , R ⁸ , R ⁹ , R ¹⁰ Can bind to R ¹¹ ; Y can be substituted with a halogen atom, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkyl _3- C ₆ cycloalkyl, halo C ₁ -C ₆ alkyl, halo C ₂ -C ₆ alkenyl, halo C ₂ -C ₆ alkynyl, halo C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, halo C ₁ --C ₆ alkoxy, C ₁ --C ₆ alkylthio, halo C ₁ --C ₆ alkylthio, C ₁ --C ₆ alkylsulfinyl, halo C ₁ --C ₆ alkylsulfinyl, C ₁ --C ₆ alkylsulfonyl, halo C ₁ --C ₆ alkylsulfonyl, carboxyl, C ₁ -C ₆ alkylcarbonyl, halo C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, halo C ₁ -C ₆ alkoxycarbonyl, amino, mono (C ₁ -C ₆ alkyl ) amino, mono (halo C ₁ -C ₆ alkyl) amino, di (C ₁ C ₆ alkyl) amino, di (halo C ₁ -C ₆ alkyl) amino, cyano, nitro or hydroxyl group]
And a salt thereof.

  The present invention also provides a herbicide containing the heteroarylsulfonamide compound of general formula (I) or a salt thereof as an active ingredient, an herbicidally effective amount of the compound or a salt thereof, an undesirable plant or a place where it grows. The present invention relates to a method for controlling undesired plants or suppressing their growth.

  The heteroarylsulfonamide compound of the general formula (I) or a salt thereof realizes a significant improvement in herbicidal activity against undesirable plants (weeds) as compared with similar conventional compounds. In addition, it has high safety for crops.

  Examples of the halogen atom in the general formula (I) or the halogen as a substituent include each atom of fluorine, chlorine, bromine or iodine. The number of halogen atoms as a substituent may be 1 or 2 or more, and in the case of 2 or more, each halogen atom may be the same or different. Further, the halogen atom may be substituted at any position.

Examples of the alkyl or alkyl moiety in the general formula (I) include a straight chain such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, neopentyl, and normal hexyl. Examples thereof include a branched C ₁ -C ₆ group.

Examples of the alkenyl or alkenyl moiety in the general formula (I) include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-methyl-1-propenyl, and 2-methyl-2. -Propenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-2-butenyl, 1-hexenyl, 2,3-dimethyl-2 - it includes straight chain or branched chain groups of C _{2-C 6} such as butenyl.

Examples of the alkynyl or alkynyl moiety in the general formula (I) include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl- Examples thereof include linear or branched C ₂ -C ₆ groups such as 3-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl and 5-hexynyl.

Examples of the cycloalkyl or cycloalkyl moiety in the general formula (I) include C ₃ -C ₆ groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

In general formula (I), examples of the C ₁ -C ₁₂ alkoxy moiety contained in R ² include methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, secondary butoxy, tertiary butoxy, normal pentyloxy, iso Examples thereof include linear or branched groups such as pentyloxy, neopentyloxy, normal hexyloxy, heptyloxy, decyloxy and dodecyloxy.

  In the general formula (I), “may be substituted with Y” means that when Y is substituted, Y may be 1 or more.

In the general formula (I), R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ and R ¹⁰ and R ¹¹ are bonded to each other to form an optionally substituted 3- to 7-membered ring. The 3- to 7-membered ring can be an oxygen atom, a sulfur atom or a nitrogen atom (the nitrogen atom is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or C ₃ -C ₆ may contain 1 or 2 heteroatoms selected from may also be) substituted by cycloalkyl. Specifically, for example, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ or R ¹¹ together with the carbon to which each is bonded, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, epoxy, tetrahydrofuran , Piperidine and the like can be formed.

In the general formula (I), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are any R on a carbon atom different from the carbon atom to which each is bonded. ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ or R ¹¹ can be combined to form an optionally substituted 3- to 8-membered ring. The member ring is an oxygen atom, sulfur atom or nitrogen atom (the nitrogen atom may be substituted by C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl). 1 or 2 heteroatoms selected from the above may be included. Specifically, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, epoxy, tetrahydrofuran, piperidine and the like can be formed.

The above-mentioned “optionally substituted” means that the carbon may be substituted with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, a halogen atom, a hydroxyl group, an oxo group, etc. Examples include the following structures.

In the general formula (I), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are any R ⁴ on the carbon atom adjacent to the carbon atom to which they are bonded. , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ or R ¹¹ , for example, can form a double bond.

  The salt of the heteroarylsulfonamide compound of the general formula (I) includes any salt that is agriculturally acceptable. For example, an alkali metal salt such as a sodium salt or a potassium salt; a magnesium salt, Alkaline earth metal salts such as calcium salts; amine salts such as dimethylamine salts and triethylamine salts; inorganic acid salts such as hydrochlorides, perchlorates, sulfates and nitrates; acetates and methanesulfonates Such organic acid salts.

  The heteroaryl sulfonamide compound of the general formula (I) may have an isomer such as an optical isomer, but the present invention includes both the isomers and isomer mixtures. In the present specification, unless otherwise specified, isomers are described as a mixture. The present invention includes various isomers other than the isomers within the scope of common technical knowledge in the technical field. In addition, depending on the type of isomer, there may be a chemical structure different from that of the general formula (I). However, since those skilled in the art can sufficiently recognize that they are related to isomers, Obviously, it is within range.

  The heteroarylsulfonamide-based compound of the general formula (I) or a salt thereof (hereinafter abbreviated as the compound according to the present invention) can be produced according to the following production methods and ordinary salt production methods. It is not limited to the method.

  ・ Production method [1]

(In the formula, A, W, Z, m, n, q, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as described above, and R ^2-a is C ₁ -C _12. (Alkoxycarbonyl, L represents a leaving group such as a halogen atom.)
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, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, carbon tetrachloride; benzene, toluene, xylene, nitrobenzene, Aromatic hydrocarbons such as chlorobenzene; esters such as methyl acetate, ethyl acetate, propyl acetate; acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMA), hexamethyl Aprotic polar solvents such as phosphoric acid triamide (HMPA) and sulfolane; ethers such as diethyl ether, tertiary butyl methyl ether, 1,4-dioxane, tetrahydrofuran (THF) and 1,2-dimethoxyethane; etc. Is mentioned. 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 organic base or an inorganic base. Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; 1,8-diazabicyclo [5.4.0] -7-undecene (DBU); pyridine; 4- (dimethylamino) pyridine; Examples include 6-lutidine. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth metals such as calcium carbonate and barium carbonate Examples thereof include metal carbonates; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide. As the base, one or more of these may be appropriately selected and mixed for use.

  The above reaction can be carried out in the presence of a phase transfer catalyst, if necessary. Examples of the phase transfer catalyst include quaternary ammonium salts such as tetranormal butyl ammonium bromide and benzyl triethyl ammonium bromide; 18-crown 6-ether;

  The reaction temperature for the above reaction is usually within a range of 0 ° C to 150 ° C, and the reaction time is usually within a range of 1 minute to 48 hours.

  ・ Production method [2]

(In the formula, A, W, Z, m, n, q, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as described above.)
The compound represented by the general formula (Ia) is obtained by reacting an intermediate (II) that can be synthesized by the method described below with an intermediate (III) that is commercially available or that can be synthesized according to a known method. Can be synthesized.

  The above reaction proceeds even without solvent, but 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, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, carbon tetrachloride; benzene, toluene, xylene, nitrobenzene, Aromatic hydrocarbons such as chlorobenzene; hydrocarbons such as normal hexane and normal heptane; esters such as methyl acetate, ethyl acetate and propyl acetate; acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide Aprotic polar solvents such as (DMSO), dimethylacetamide (DMA), hexamethylphosphoric triamide (HMPA), sulfolane; diethyl ether, tertiary butyl methyl ether, 1,4-dioxane, tetrahydrofuran (THF), 1 A, such as 2-dimethoxyethane Such as Le acids and the like. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be carried out in the presence of a phase transfer catalyst, if necessary. Examples of the phase transfer catalyst include the same catalysts as those exemplified in the production method [1].

  The above reaction can be carried out in the presence of a base as necessary. The base may be either an organic base or an inorganic base, and examples thereof include the same bases as exemplified in the production method [1]. As the base, one or more of these may be appropriately selected and mixed for use.

  The above reaction can be performed in the presence of an acid catalyst, if necessary. Examples of the acid catalyst include organic acids such as formic acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid and trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid and hydrogen bromide; zinc chloride Lewis acids such as titanium tetrachloride, tin chloride, aluminum chloride, iron chloride, and boron trifluoride-ether complex.

  The reaction temperature for the above reaction is usually within the range of 0 ° C to 150 ° C, and the reaction time is usually within the range of 1 minute to 72 hours.

  ・ Production method [3]

(In the formula, A, W, Z, m, n, q, R ¹ , R ^2-a , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as described above.)
The above reaction may be performed according to a method considered in general organic synthetic chemistry. A base can be used. Examples of the base include alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; calcium carbonate and barium carbonate. Alkaline earth metal carbonates such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide. It is done. As the base, one or more of these may be appropriately selected and mixed for use.

    The above reaction can be carried out in the presence of a solvent. Any solvent can be used as long as it is inert to the reaction. For example, alcohols such as methanol, ethanol and isopropanol; acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) ), Aprotic polar solvents such as dimethylacetamide (DMA), hexamethylphosphoric triamide (HMPA), sulfolane; diethyl ether, tertiary butyl methyl ether, 1,4-dioxane, tetrahydrofuran (THF), 1,2 -Ethers such as dimethoxyethane; water and the like. As the solvent, one or more of these can be appropriately selected.

  The reaction temperature for the above reaction is usually within the range of 0 ° C to 100 ° C, and the reaction time is usually within the range of 1 minute to 72 hours.

  ・ Production method [4]

(In the formula, A, Z, m, n, q, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as described above.)
Examples of the sulfurizing agent used in the above reaction include P ₄ S ₁₀ and Lawesson's reagent. The above reaction can be carried out in the presence of a solvent. The solvent used may be any solvent that is inert to the reaction, such as halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, carbon tetrachloride; benzene, toluene, xylene, Aromatic hydrocarbons such as nitrobenzene and chlorobenzene; hydrocarbons such as normal hexane and normal heptane; diethyl ether, tertiary butyl methyl ether, 1,4-dioxane, tetrahydrofuran (THF), 1,2-dimethoxyethane And ethers such as As the solvent, one or more of these can be appropriately selected.

  The reaction temperature for the above reaction is usually within the range of 0 ° C to 150 ° C, and the reaction time is usually within the range of 1 minute to 72 hours.

  Intermediate production method [1]

(In the formula, q, R ¹ , R ³ and L are as described above. R ¹² represents C ₁ -C ₆ alkyl.)
Each step of the intermediate production method [1] will be described in detail below.

Intermediate production method [1-1]
General formula (V) → General formula (IV-a) or General formula (IV-b)
The above reaction proceeds even without solvent, but 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, and examples thereof include the same solvents as those exemplified in the production method [1]. 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 organic base or an inorganic base, and examples thereof include the same bases as exemplified in the production method [1]. 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 within a range of -70 ° C to 150 ° C, and the reaction time is usually within a range of 1 minute to 72 hours.

The above reaction can be performed under an inert gas as necessary. Examples of the inert gas include argon gas and nitrogen gas.
Intermediate production method [1-2]
General formula (IV-b) → General formula (IV-a)
The above reaction proceeds even without solvent, but 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, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, carbon tetrachloride; benzene, toluene, xylene, nitrobenzene, Aromatic hydrocarbons such as chlorobenzene; esters such as methyl acetate, ethyl acetate, propyl acetate; acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMA), hexamethyl Aprotic polar solvents such as phosphoric acid triamide (HMPA) and sulfolane; alcohols such as methanol, ethanol and isopropanol; diethyl ether, tertiary butyl methyl ether, 1,4-dioxane, tetrahydrofuran (THF), 1, 2-Dimethoxyethane Such ethers; and water. 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 organic base or an inorganic base. Examples of the organic base include ammonia and hydroxylamine. As an inorganic base, the base similar to the base illustrated to manufacturing method [1] is mentioned. As the base, one or more of these may be appropriately selected and mixed for use.

  The above reaction can be carried out in the presence of a phase transfer catalyst, if necessary. Examples of the phase transfer catalyst include the same catalysts as those exemplified in the production method [1].

  The reaction temperature for the above reaction is usually within the range of 0 ° C to 150 ° C, and the reaction time is usually within the range of 1 minute to 72 hours.

Intermediate production method [1-3]
General formula (IV-a) or general formula (IV-b) → General formula (IV-c)
The above reaction may be performed according to a method considered in general organic synthetic chemistry. For example, a base can be used, and examples of the inorganic base include the same bases as those exemplified in the production method [1]. As the base, one or more of these may be appropriately selected and mixed for use.

  The solvent used in the above reaction may be any solvent as long as it is inert to the reaction, and examples thereof include the same solvents as those exemplified in the production method [3]. As the solvent, one or more of these can be appropriately selected.

  The reaction temperature for the above reaction is usually in the range of -70 ° C to 150 ° C, desirably in the range of 0 ° C to 100 ° C, and the reaction time is usually in the range of 1 minute to 72 hours.

Intermediate production method [1-4]
General formula (IV-a), general formula (IV-b) or general formula (IV-c) → general formula (II)
Examples of the reducing agent used in the above reaction include lithium aluminum hydride, diisobutylaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, sodium borohydride, lithium borohydride, and borane THF complex. It is done.

  The above reaction can be carried out in the presence of a solvent. The solvent used may be any solvent inert to the reaction, such as halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, carbon tetrachloride; benzene, toluene, xylene, Aromatic hydrocarbons such as chlorobenzene; ethers such as diethyl ether, tertiary butyl methyl ether, 1,4-dioxane, tetrahydrofuran (THF), 1,2-dimethoxyethane, and the like. As the solvent, one or more of these can be appropriately selected.

  The reaction temperature for the above reaction is usually within a range of -70 ° C to 150 ° C, and the reaction time is usually within a range of 1 minute to 72 hours.

  The above reaction can be performed under an inert gas as necessary. Examples of the inert gas include argon gas and nitrogen gas.

  Intermediate production method [2]

(Wherein q, R ¹ , R ³ and R ¹² are as described above.)
The above reaction can be carried out according to the method described in the above intermediate production method [1].

  The compound according to the present invention exhibits an excellent herbicidal effect when used as an active ingredient of a herbicide. The range of application ranges widely from agricultural fields such as paddy fields, upland fields, orchards, mulberry fields, and non-agricultural land such as forests, farm roads, grounds, and factory sites. Applicable methods include soil treatment, foliage treatment, and flooding treatment as appropriate. You can choose.

The compounds according to the present invention can control a wide range of undesirable plants such as annual and perennial weeds. Specifically, for example, barnyardgrass or barnyardgrass (barnyardgrass (Echinochloa crus-galli L. , Echinochloa oryzicola vasing.)), Crabgrass (crabgrass (Digitaria sanguinalis L., Digitaria ischaemum Muhl., Digitaria adscendens Henr., Digitaria microbachne Henr., Digitaria horizontalis Willd.)), Green foxtail ( Setaria viridis L.)), Akino foxtail ( Setaria faberi Herrm.)), Yellow foxtail ( Setaria lutescens Hubb.), Goosegrass ( Eleusine indica ) .)), Oats (wild oat ( Avena fatua L.)), sorghum sorghum (johnsongrass ( Sorghum halepense L.)), shibamugi (quackgrass ( Agropyron repens L.)), velvet millet (alexandergrass ( Brachiaria plantaginea )), guinea millet guineagrass ( Panicummaximum Jacq.)), paragrass ( Panicum purpurascens ), azegaya (sprangletop ( Leptochloa chinensis )), red sprangletop ( Leptochloa panicea )), sparrows (annual bluegrass ( Poa annua L.)), sparrows (black grass ( Alopecurus myosuroides Huds.)), camphorado bluestem ( Agropyron tsukushiense (Honda) Ohwi)), meriden platyphylla Nash)), grass sand ( Cenchrus echinatus L.)), barley (italian ryegrass ( Lolium multiflorum Lam.)), barley (bermudagrass ( Cynodon dactylon Pers.)) (rice flatsedge (Cyperus iria L.) ), purple nutsedge (purple nutsedge (Cyperus rotundus L.) ), yellow nutsedge (yellow nutsedge (Cyperus esculentus L.) ), bulrush (Japanese bulrush (Scirpus juncoides)) , Cyperus (flatsedge (Cyperus serotinus ), small-flower umbrellaplant ( Cyperus difformis )), pine birch (slender spikerush ( Eleocharis acicularis )), crocodile (water chestnut ( Eleocharis kuroguwai) Cyperaceae) such as)); Urikawa (Japanese ribbon waparo ( Sagittaria pygmaea )), Omodaka (arrow-head ( Sagittaria trifolia )), Heramodaka (narrowleaf waterplantain ( Alisma canaliculatum )) alismataceae); vaginalis (monochoria (monochoria vaginalis)), monochoria korsakowii (monochoria species (monochoria korsakowii) pontederiaceae weeds such as); Azetougarashi weeds such as (pontederiaceae) false pimpernel (false pimpernel (Lindernia pyxidaria)) , Abunome (abunome ( Dopatrium junceum )), plantaginaceae; toothcup ( Rotala india ), red stem ( Ammanniamultiflora ), lythraceae; long stem waterwort ( Elatine triandra) SCHK.)) And other weeds (elatinaceae); velvetleaf ( Abutilon theophrasti MEDIC.)), American deer (prickly sida ( S malvaceae such as ida spinosa L.); common flea (common cocklebur ( Xanthium strumarium L.)), common ragweed ( Ambrosia elatior L.), thistle ( Breea setosa (BIEB) .) KITAM.)), Compositae such as hairy galinsoga ( Galinsoga ciliata Blake)), chamomile (wild chamomile ( Matricaria chamomilla L.)), and henbit ( Lamium amplexicaule L.); Inuhouzuki (black nightshade (Solanumnigrum L.)) , Solanaceae weeds such as white-nosed Datura (jimsonweed (Daturastramonium)) (solanaceae ); slender amaranth (slender amaranth (Amaranthus viridis L.) ), pigweed (redroot pigweed (Amaranthus retroflexus L Amaranthaceae such as (pale smartweed ( Polygonumlapathifolium L.)), hartade (ladysthumb ( Polygonumpersicaria L.)), buckwheat (wild buckwheat ( Polygonumconvolvulus L.)), knotwee d ( Polygonumaviculare L.)); Polygonaceeae; flexuous bittercress ( Cardamine flexuosa WITH.), shepherd's-purse ( Capsella bursa-pastoris Medik.), Indian mustard (indian mustard) . Brassica juncea Czern)) cruciferous weeds (cruciferae) such as; Ipomoea purpurea (tall morningglory (Ipomoeapurpurea L.)) , field bindweed (field bindweed (Convolvulusarvensis L.)) , the United States morning glory (ivyleaf morningglory (Ipomoeahederacea Jacq). ) Convolvulaceae; Shiroza (common lambsquarters ( Chenopodium album L.)), Amaran thaceae (such as mexican burningbush ( Kochia scoparia Schrad.)); Common purslane (common purslane ( Portulacoleae (Portulacaoleracea L.)); Leguminosae weed (sicklepod ( Cassia obtusifolia L.)); fabaceae; common chickweed ( St Caryophyllaceae such as ellariamedia L.); Rubiaceae weed such as catchweed ( Galium spurium L.); Euphorbiaceae such as threeseeded copperleaf ( Acalyphaaustralis L.)) Weeds (euphorbiaceae); various harmful weeds such as Commelinaceae such as common dayflower ( Commelina communis L.) can be controlled. Therefore, useful crops such as corn (corn ( Zea mays L.)), soybean (soybean ( Glycine max Merr.)), Cotton (cotton ( Gossypium spp.)), Wheat (wheat ( Triticum spp.)), Rice ( rice ( Oryza sativa L.)), barley (barley ( Hordeum Vulgare L.)), rye (rye ( Secalecereale L.)), oat (oat ( Avena sativa L.)), sorghum (sorgo ( Sorghum bicolor Moench)) Rape , Brassica napus L.), sunflower (sunflower ( Helianthus annuus L.)), sugar beet (suger beet ( Beta Vulgaris L.)), sugar cane (suger cane ( Saccharum officinarum L.)), turf lawngrass ( Zoysia japonica stend )), peanuts (peanut ( Arachis hypogae a L.)), flax (flax ( Linum usitatissimum L.)), tobacco (tobacco ( Nicotiana tabacum L.)), coffee (coffee ( Coffea spp.) ) Etc., it is used effectively when controlling harmful weeds selectively or when controlling non-selective harmful weeds.

  The compound according to the present invention is usually mixed with various agricultural adjuvants, powders, granules, granule wettable powders, wettable powders, tablets, pills, capsules (including forms packaged with water-soluble films). , Aqueous suspension, oil suspension, microemulsion formulation, suspoemulsion formulation, aqueous solvent, emulsion, solution, paste, etc. can be prepared and applied, but fits the purpose of the present invention As long as it is, it can be in any formulation form commonly used in the art.

  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; Water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, alcohol and other solvents; fatty acid salts, benzoic acid Salt, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, alcohol Sulfate ester salt, alkyl sulfonate salt, alkyl aryl sulfonate salt, aryl sulfonate salt, lignin sulfonate salt, alkyl diphenyl ether disulfonate salt, polystyrene sulfonate salt, alkyl phosphate ester salt, alkyl aryl phosphate salt, styryl aryl Phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate Such as polyoxyethylene aryl ether phosphate ester salt, naphthalene sulfonate formalin condensate, alkyl naphthalene sulfonate formalin condensate Surfactants and spreading agents: sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride, fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl Ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid Nonionic surfactants and spreading agents such as esters; olive oil, kapok oil, sunflower Examples thereof include vegetable oil, palm oil, coconut oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, flaxseed oil, linseed oil, liquid paraffin and other vegetable oils and mineral oils. These adjuvants can be used by appropriately selecting one or two or more kinds without departing from the object of the present invention. For example, extenders, thickeners, anti-settling agents, antifreeze agents, dispersion agents Various commonly used adjuvants such as stabilizers, safeners, antifungal agents, foaming agents, disintegrating agents, binders and the like can also be used. The compounding ratio of the compound according to the present invention and various adjuvants is 0.1: 99.9 to 95: 5, desirably 0.2: 99.8 to 85:15.

  The application rate (herbicidally effective amount) of the herbicide containing the compound according to the present invention cannot be defined unconditionally due to differences in weather conditions, soil conditions, formulation forms, types of undesirable plants targeted, application time, etc. Generally, it is applied so that the amount of the compound according to the present invention is 0.1 to 5,000 g, preferably 0.5 to 3,000 g, more preferably 1 to 1,000 g per hectare. The present invention also includes a method for controlling undesirable plants by applying such herbicides.

  In addition, the herbicide containing the compound according to the present invention can be used in combination with or used in combination with other agricultural chemicals, fertilizers, safeners, etc. In this case, there may be more excellent effects and actions. Other pesticides include herbicides, fungicides, antibiotics, plant hormones, insecticides and the like. In particular, the mixed herbicidal composition in which the compound according to the present invention and one or more compounds as active ingredients of other herbicides are used in combination or in combination, the range of the applicable herbaceous species, the timing of drug treatment, It is possible to improve the herbicidal activity and the like in a preferable direction. In addition, the compound which is the active ingredient of the compound which concerns on this invention and another herbicide may mix and use it at the time of dispersion | distribution, respectively, or may use both together. The above-described mixed herbicidal composition is also included in the present invention.

  The mixing ratio between the compound according to the present invention and the compound that is an active ingredient of other herbicides cannot be defined unconditionally due to differences in weather conditions, soil conditions, drug formulation, application time, application method, etc. Other herbicides are compounded in an amount of 0.001 to 10,000 parts by weight, preferably 0.01 to 1,000 parts by weight, of the active ingredient compound per 1 part by weight of the compound. Further, 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 ingredients per hectare. The present invention also includes a method for controlling undesirable plants by application of such a mixed herbicidal composition.

  Examples of the compound that is an active ingredient of other herbicides include the following compounds (generic names; some of which are included in the application for ISO). If an alkyl ester or the like is present, it is naturally included.

  (1) 2,4-D, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D dimethylammonium (2 , 4-D-dimethylammonimum), 2,4-D-diolamine (2,4-D-diolamine), 2,4-D-ethyl, 2,4-D-2-ethylhexyl (2,4-D-2-ethylhexyl), 2,4-D-isobutyl, 2,4-D-isooctyl, 2,4-D-isopropyl (2,4-D-isopropyl), 2,4-D-isopropylammonium, 2,4-D sodium (2,4-D-sodium), 2,4-D isopropanolammonium (2,4-D-isopropanolammonium), 2,4-D-trolamine (2,4-D-trolamine), 2,4-DB, 2,4-DB-butyl, 2, , 4-DB-dimethylammonium, 2,4-DB iso-o Chill (2,4-DB-isoctyl), 2,4-DB potassium (2,4-DB-potassium), 2,4-DB sodium (2,4-DB-sodium), dichloroprop (dichlorprop), dichloro Propbutyl (dichlorprop-butotyl), dichloroprop-dimethylammonium, dichloroprop-isoctyl, dichlorprop-potassium, dichloroprop-P, dichloroprop -P dimethylammonium, dichloroprop-P-potassium, dichloroprop-P-sodium, MCPA, MCPA-butotyl, MCPA dimethyl Ammonium (MCPA-dimethylammonium), MCPA-2-ethylhexyl, MCPA potassium MCPA-potassium), MCPA sodium (MCPA-sodium), MCPA thioethyl (MCPA-thioethyl), MCPB, MCPB ethyl (MCPB-ethyl), MCPB sodium (MCPB-sodium), mecoprop (mecoprop), mecoprop butyl (mecoprop -butotyl), mecoprop-sodium, mecoprop-P, mecoprop-P-butotyl, mecoprop-P-dimethylammonium, mecoprop-P Phenoxy compounds such as 2-ethylhexyl, mecoprop-P-potassium, naproanilide, clomeprop; 2,3,6-TBA; Dicamba, dicamba-butotyl, dicamba-diglycola mine), dicamba-dimethylammonium, dicamba-diolamine, dicamba-isopropylammonium, dicamba-potassium, dicamba-sodium , Picloram, picloram-dimethylammonium, picloram-isoctyl, picloram-potassium, picloram-triisopropanolammonium, Picloram-triisopropylammonium, picloram-trolamine, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, clopira Aromatic carboxylic acid compounds such as clopyralid, clopyralid-olamine, clopyralid-potassium, clopyralid-triisopropanolammonium, aminopyralid; naptalam, sodium naptalam (naptalam-sodium), benazolin (benazolin), benazolin-ethyl, quinclorac, quinmerac, diflufenzopyr, diflufenzopyr Sodium (diflufenzopyr-sodium), fluoxypyr (fluroxypyr), fluoxypyr-2-butoxy-1-methylethyl (fluroxypyr-2-butoxy-1-methylethyl), fluoxypyrmeptyl (fluroxypyr-meptyl), chloroflurenol (chlorflurenol) ), Chlorofur Compounds such as renolmethyl (chlorflurenol-methyl) that are said to show herbicidal activity by disrupting the hormonal action of plants.

  (2) chlorotoluron, diuron, fluometuron, linuron, isoproturon, metobenzuron, tebuthiuron, dimefuron, isouron, isouron Urea compounds such as karbutilate, methabenzthiazuron, metoxuron, monolinuron, neburon, siduron, terbumeton, trietazine; Simazine, atrazine, atratone, simetryn, promethrin, dimethametryn, hexazinone, metribuzin, terbuthylazine, cyanazine Triazine compounds such as cyanazine, ametryn, cybutryne, terbutryn, propazine, metamitron, and prometon; bromacil, bromacyl- uracil compounds such as lithium), lenacil, terbacil; anilide compounds such as propanil, cypromid; swep, desmedipham, fenmedifam Carbamate compounds such as (phenmedipham); bromoxynil, bromoxynil-octanoate, bromoxynil-heptanoate, ioxynil, ioxynyl octanoate (Ioxynil-octanoate), ioxynilca Hydroxybenzonitrile compounds such as ioxynil-potassium, ioxynil-sodium; other, pyridate, bentazone, bentazone-sodium, amicarbazone, Compounds such as methazole and pentanochlor that have been shown to have herbicidal activity by inhibiting plant photosynthesis.

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

  (4) Nitrofen, Chlomethoxyfen, bifenox, acifluorfen, acifluorfen-sodium, fomesafen, fomesafen-sodium ), Oxyfluorfen, lactofen, aclonifen, ethoxyfen-ethyl, HC-252, fluoroglycofen-ethyl, fluoroglycofen Diphenyl ether compounds; chlorphthalim, flumioxazin, flumiclorac, flumiclorac-pentyl, cinidon-ethyl, fluthiacet-methyl Cyclic imide compounds such as: oxadiargyl, oxadiazon, sulfentrazone, carfentrazone-ethyl, thidiazimin, pentoxazone, azaphenidine (Azafenidin), isopropazole, pyraflufen-ethyl, benzfendizone, butafenacil, saflufenacil, fluazolate, profluazol Inhibiting plant chlorophyll biosynthesis, such as flufenpyr-ethyl and bencarbazone, and causing abnormal accumulation of photosensitized peroxides in plants, suggesting herbicidal efficacy Compound.

  (5) pyridazinone compounds such as norflurazon, chloridazon, metflurazon; pyrazolynate, pyrazoloxyfen, benzofenap, topramezone, BAS-670H, Pyrazole compounds such as pyrasulfotole; others, amitrole, fluridone, flurtamone, diflufenican, methoxyphenone, clomazone, sulcotrione ( sulcotrione, mesotrione, tembotrione, tefuryltrione, AVH-301, isoxaflutole, difenzoquat, difenzoquat methyl difenzoqua Inhibits pigment biosynthesis of plants such as carotenoids such as t-metilsulfate, isoxachlortole, benzobicyclon, bicyclopyron, picolinafen, and biflubutamid. A compound that is said to exhibit herbicidal efficacy characterized by a whitening effect.

  (6) Dicloofop-methyl, diclofop, pyriphenop-sodium, fluazifop-butyl, fluazifop, fluazifop-P (fluazifop-P) Fluazifop-P-butyl, haloxyfop-methyl, haloxyfop, haloxyfop-etotyl, haloxyfop-P, haloxyhop -P-methyl, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-ethyl (quizalofop-P-ethyl) quizalofop-P-tefuryl), cyhalofop-butyl, fenoxaprop-ethyl, phenoxaprop-P fenoxaprop-P), fenoxaprop-P-ethyl, metamifop-propyl, metamifop, clodinafop-propargyl, clodinafop, Aryloxyphenoxypropionic acid compounds such as propaquizafop; alloxydim-sodium, alloxydim, clethodim, sethoxydim, tralkoxydim, butroxydim Inhibiting fatty acid biosynthesis, such as, cyclohexanedione compounds such as tepraloxydim, profoxydim, cycloxydim; phenylpyrazolin compounds such as pinoxaden; Herbicidal effect on plants The compounds are to show.

  (7) Chlorimuron-ethyl, chlorimuron, sulfometuron-methyl, sulfometuron, primisulfuron-methyl, primisulfuron, Bensulfuron-methyl, bensulfuron, chlorsulfuron, methsulfuron-methyl, metsulfuron, cinosulfuron, pyrazosulfuron-ethyl , Pyrazosulfuron, flazasulfuron, rimsulfuron, nicosulfuron, imazosulfuron, flucetosulfuron, cyclosulfamuron, prosulfururon (Prosulfuron), flupirsulfuron-methyl-sodium, flupirsulfuron, triflusulfuron-methyl, triflusulfuron, halosulfuron-methyl, Halosulfuron, thifensulfuron-methyl, thifensulfuron, ethoxysulfuron, oxasulfuron, ethametsulfuron, ethametsulfuron, ethametsulfuron -methyl), iodosulfuron, sodium iodosulfuron-methyl-sodium, sulfosulfuron, triasulfuron, tribenuron-methyl, tribenuron ( tribenuron, tritosulfuron, foramsulfuron, trifloxysulfuron, trifloxysulfuron-sodium, mesosulfuron-methyl, mesosulfuron, Sulfonylurea compounds such as orthosulfamuron, amidosulfuron, propyrisulfuron (TH-547), NC-620, compounds described in International Publication WO2005092104; Triazolopyrimidine sulfones such as flumetsulam, metosulam, diclosulam, cloransulam-methyl, florasulam, penoxsulam, pyroxsulam Imazapyr, imazapyr-isopropylammonium, imazethapyr, imazethapyr-ammonium, imazaquin, imazaquin-ammonium, imazaquin-ammonium, Imidazolinone compounds such as imazamox, imazamox-ammonium, imazamethabenz, imazamethabenz-methyl, imazapic; pyrithiobac- sodium, bispyribac-sodium, pyriminobac-methyl, pyribenzoxim, pyriftalid, pyrimisulfan, KUH-021, triafamone, B Pyrimidinyl salicylic acid compounds such as H-100); sulfonylaminocarbonyltria such as flucarbazone, flucarbazone-sodium, propoxycarbazone-sodium, propoxycarbazone Zolinone compounds; other, glyphosate, sodium glyphosate, sodium glyphosate-potassium, glyphosate-ammonium, glyphosate-diammonium, glyphosate isopropylammonium -isopropylammonium), glyphosate-trimesium, glyphosate-sesquisodium, glufosinate, glufosinate an Glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, vilanafos, vilanafos sodium -sodium), compounds such as cinmethylin and the like, which are said to show herbicidal activity by inhibiting plant amino acid biosynthesis.

  (8) Trifluralin, oryzalin, oryzalin, nitalin, pendimethalin, ethalluralin, benfluralin, prodiamine, butralin, dinitramine ( dinitroaniline compounds such as dinitramine; amide compounds such as bensulide, napropamide, propyzamide, pronamide; amiprofos-methyl, butamifos , Organophosphorus compounds such as anilofos, piperophos; phenyl carbamate compounds such as propham, chlorpropham, barban, carbetamide; daimuron ), Cumyl Cumyluron compounds such as cumyluron, bromobutide, methyldymron; others, asuram, asuram-sodium, dithiopyr, thiazopyr, chlorotal dimethyl (Chlorthal-dimethyl), chlorthal, diphenamid, flamprop-M-methyl, flamprop-M, flamprop-M-flamprop-M -isopropyl) and other compounds that are said to show herbicidal efficacy by inhibiting plant cell mitosis.

  (9) alachlor, metazachlor, butachlor, pretilachlor, metolachlor, S-metolachlor, tenylchlor, petoxamide , Chloroacetamide compounds such as acetochlor, acetochlor, propachlor, dimethenamid, dimethenamid-P, propisochlor, dimethachlor; molinate , Dimepiperate, pyributicarb, EPTC, butyrate, vernolate, pebulate, cycloate, prosulfocarb, esprocarb, thiobe Thiocarbamate compounds such as thiobencarb, diallate, tri-allate, orbencarb; others, etobenzanid, mefenacet, flufenacet, trifalate Didiphane, caffenstrole, fentrazamide, oxaziclomefone, indanofan, benfuresate, pyroxasulfone, fenoxasulfone, methiozoline It is removed by inhibiting protein biosynthesis or lipid biosynthesis of plants such as methiozolin, dalapon, dalapon-sodium, TCA sodium (TCA-sodium), and trichloroacetic acid. A compound that has been shown to show herbicidal efficacy.

  (10) A compound that has been shown to have herbicidal activity by inhibiting cellulose biosynthesis of plants such as dichlobenil, triaziflam, indaziflam, flupoxam and the like.

  (11) MSMA, DSMA, CMA, endothal (endothall), endothal dipotassium, endothal sodium (endothall-sodium), endtal mono (N, N-dimethylalkylammonium) (endothall-mono ( N, N-dimethylalkylammonium)), etofumesate, sodium chlorate, pelargonic acid, nonanoic acid), phosamine, fosamine-ammonium, ipfen Carbazone (ipfencarbazone, HOK-201), aclolein, ammonium sulfamate, borax, chloroacetic acid, sodium chloroacete, cyanamide, methylarson Acid (methylarsonic acid) Dimethylarsinic acid, sodium dimethylarsinate, dinoterb, dinoterb-ammonium, dinoterb-diolamine, dinoterb-acetate, DNOC , Ferrous sulfate, flupropanate, sodium flupropanate (flupropanate-sodium), isoxaben, mefluidide, mefluidide-diolamine, metham ( metam, metam-ammonium, metam-potassium, metam-sodium, methyl isothiocyanate, pentachlorophenol, sodium pentachlorophenoxid e) Other herbicides such as pentachlorophenol laurate, quinoclamine, sulfuric acid, urea sulfate.

(12) Xanthomonas campestris (Xanthomonas campestris), epi heart Sils Nematosorusu (Epicoccosirus nematosorus), epi heart Sils Nematosuperasu (Epicoccosirus nematosperus), Ekiserohiramu monoceras (Exserohilum monoseras), parasitic plants such as Drechslera monoceras (Drechsrela monoceras) A compound that is said to show herbicidal efficacy.

  Next, examples of the present invention will be described, but the present invention is not limited thereto. First, synthesis examples of the compounds according to the present invention will be described.

Synthesis example 1
Synthesis of 1,1,1-trifluoro-N- (2-((2-oxopiperidin-1-yl) methyl) thiophen-3-yl) methanesulfonamide (Compound No. 1-1) (1) Nitrogen Under atmosphere, a solution of methyl 3-amino-2-thiophenecarboxylate (7.86 g), triethylamine (6.93 ml) and chloroform (200 ml) was cooled to 0 ° C., trifluoromethanesulfonic anhydride (8.20 ml) and chloroform (20 ml) was added dropwise over 15 minutes. The mixture was further stirred for 20 hours while raising the temperature to room temperature. The reaction solution was washed with water, and the aqueous layer was extracted with chloroform. The organic layers were combined, washed with saturated brine, and then washed twice with 2N aqueous sodium hydroxide solution (100 ml). The separated alkaline aqueous solution was acidified with concentrated hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give a yellow solid (8.70 g). The obtained yellow solid was analyzed by ¹ H-NMR from a mixture of methyl 3- (trifluoromethylsulfonamido) thiophene-2-carboxylate and 3- (trifluoromethylsulfonamido) thiophene-2-carboxylic acid (approximately 1: 3).

The ¹ H-NMR spectrum data of methyl 3- (trifluoromethylsulfonamido) thiophene-2-carboxylate is shown below.
¹ H-NMR (500 MHz, acetone-d6, δppm): 3.92 (s, 3H), 7.35 (d, J = 5.5 Hz, 1H), 7.94 (d, J = 5.5 Hz, 1H).
The ¹ H-NMR spectrum data of 3- (trifluoromethylsulfonamido) thiophene-2-carboxylic acid is shown below.
¹ H-NMR (500 MHz, CDCl ₃ , δppm): 7.39 (d, J = 5.5 Hz, 1H), 7.60 (d, J = 5.5 Hz, 1H), 9.94 (br s, 1H).
(2) The mixture (8.70 g) synthesized in (1) above was dissolved in THF (100 ml), and a suspension of lithium aluminum hydride (3.86 g) and THF (150 ml) that had been ice-cooled in advance under a nitrogen atmosphere. The solution was added dropwise over 35 minutes. The mixture was stirred for 2 hours under reflux, and after cooling, water was added under ice cooling to stop the reaction. Ethyl acetate and 2N aqueous hydrochloric acid solution were added, and the mixture was stirred for a while. The aqueous layer was extracted with ethyl acetate, and the organic layers were combined, washed with saturated brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and crude 1,1,1-trifluoro-N- ( 2- (Hydroxymethyl) thiophen-3-yl) methanesulfonamide (8.13 g) was obtained.
(3) Crude 1,1,1-trifluoro-N- (2- (hydroxymethyl) thiophen-3-yl) methanesulfonamide (1.36 g) synthesized in (2) above was added to toluene (58 ml). After dissolution, p-toluenesulfonic acid monohydrate (665 mg) and 2-piperidone (723 mg) were added. The reaction solution was heated and stirred for 3 hours while performing azeotropic dehydration using a Dean-Stark apparatus. After cooling to room temperature, the mixture was diluted with ethyl acetate and washed with saturated brine. After drying over sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by column chromatography (heptane: ethyl acetate = 9: 1 to 1: 1) to obtain the desired product (1.05 g, compound No. .1-1) was obtained as a light brown solid.

Synthesis example 2
Synthesis of isobutyl (2-((2-oxopiperidin-1-yl) methyl) thiophen-3-yl) ((trifluoromethyl) sulfonyl) carbamate (Compound No. 1-7)
1,1,1-trifluoro-N- (2-((2-oxopiperidin-1-yl) methyl) thiophen-3-yl) methanesulfonamide (210 mg) was dissolved in toluene (6 ml), Pyridine (0.10 ml) and isobutyl chloroformate (0.16 ml) were added, and the mixture was stirred at room temperature for 17 hours. After 2 N hydrochloric acid aqueous solution was added to stop the reaction, the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate = 9: 1 to 1: 1) to obtain the desired product (218 mg, compound No. 1-7) as a pale brown oily substance.

Synthesis example 3
Synthesis of 1,1,1-trifluoro-N- (4-methyl-2-((2-oxopiperidin-1-yl) methyl) thiophen-3-yl) methanesulfonamide (Compound No. 13-1) (1) Under a nitrogen atmosphere, a solution of methyl 3-amino-4-methylthiophene-2-carboxylate (5.41 g), triethylamine (5.26 ml) and chloroform (200 ml) was cooled to −4 ° C. to obtain trifluoromethanesulfone. A mixed solution of acid anhydride (10.7 g) and chloroform (20 ml) was added dropwise over 25 minutes. The mixture was further stirred for 1 hour while cooling with ice, and water was added to stop the reaction. The aqueous layer was extracted with chloroform. The organic layers were combined and washed twice with 2N aqueous sodium hydroxide solution (100 ml). The aqueous alkaline solution was separated and stirred at reflux for 20 minutes. After cooling to room temperature, it was acidified with concentrated hydrochloric acid. The suspension was stirred while cooling with ice, and the resulting solid was filtered, washed with water, and then dried under reduced pressure to give 4-methyl-3- (trifluoromethylsulfonamido) thiophene-2-carboxylic acid. The acid was obtained as a pale pink solid (3.09 g). (Melting point 164-166 ° C)
¹ H-NMR (500 MHz, CDCl ₃ , δppm): 2.34 (s, 3H), 7.29 (s, 1H), 8.45 (br s, 1H).
(2) 4-Methyl-3- (trifluoromethylsulfonamido) thiophene-2-carboxylic acid (2.82 g) obtained in (1) above was dissolved in THF (50 ml), and iced in advance under a nitrogen atmosphere. The solution was added dropwise to a cooled suspension of lithium aluminum hydride (1.15 g) and THF (50 ml) over 20 minutes. The mixture was stirred for 1 hour under reflux, and after cooling, water was added under ice cooling to stop the reaction. Ethyl acetate and 2N aqueous hydrochloric acid solution were added, and the mixture was stirred for a while. The aqueous layer was extracted with ethyl acetate, and the organic layers were combined, washed with 2N aqueous hydrochloric acid and saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give crude 1,1,1 -Trifluoro-N- (2- (hydroxymethyl) -4-methylthiophen-3-yl) methanesulfonamide (2.89 g) was obtained.
(3) Crude 1,1,1-trifluoro-N- (2- (hydroxymethyl) -4-methylthiophen-3-yl) methanesulfonamide (1.45 g) synthesized in (2) above was added to toluene (1.45 g). 40 ml), p-toluenesulfonic acid monohydrate (760 mg) and 2-piperidone (793 mg) were added. The reaction solution was heated and stirred for 2 hours with azeotropic dehydration using a Dean-Stark distillation apparatus. After cooling to room temperature, the mixture was diluted with ethyl acetate and washed with saturated brine. After drying with sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by column chromatography (heptane: ethyl acetate = 9: 1 to 1: 1) to obtain a crude target product (785 mg, Compound No. 13-1) was obtained as a pale yellow solid.

Synthesis example 4
Synthesis of ethyl (4-methyl-2-((2-oxopiperidin-1-yl) methyl) thiophen-3-yl) ((trifluoromethyl) sulfonyl) carbamate (Compound No. 13-3)
1,1,1-trifluoro-N- (4-methyl-2-((2-oxopiperidin-1-yl) methyl) thiophen-3-yl) methanesulfonamide (785 mg) in toluene (10 ml) , Pyridine (0.36 ml) and ethyl chloroformate (0.42 ml) were added, and the mixture was stirred at room temperature for 2 hours. After 2 N hydrochloric acid aqueous solution was added to stop the reaction, the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate = 9: 1 to 1: 1) to obtain the desired product (760 mg, compound No. 13-3) as a pale brown oily substance.

Synthesis example 5
Synthesis of 1,1,1-trifluoro-N- (2-((2-thioxopiperidin-1-yl) methyl) thiophen-3-yl) methanesulfonamide (Compound No. 1-46)
1,1,1-trifluoro-N- (2-((2-oxopiperidin-1-yl) methyl) thiophen-3-yl) methanesulfonamide (321 mg) was dissolved in toluene (10 ml), Lawesson's reagent (469 mg) was added thereto, and the mixture was stirred under reflux for 5 hours. The mixture was cooled to room temperature and purified by column chromatography (heptane: ethyl acetate = 9: 1 to 0:10) to obtain the desired product (243 mg, compound No. 1-46) as a pale yellow solid.

Synthesis example 6
Synthesis of ethyl (2-((2-thioxopiperidin-1-yl) methyl) thiophen-3-yl) ((trifluoromethyl) sulfonyl) carbamate (Compound No. 1-48)
1,1,1-trifluoro-N- (2-((2-thioxopiperidin-1-yl) methyl) thiophen-3-yl) methanesulfonamide (163 mg) was dissolved in toluene (3 ml). Pyridine (0.10 ml) and ethyl chloroformate (0.10 ml) were added, and the mixture was stirred at room temperature for 2 hours. After 2 N hydrochloric acid aqueous solution was added to stop the reaction, the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate = 9: 1 to 6: 4) to obtain the desired product (191 mg, compound No. 1-48) as a pale yellow solid.

Synthesis example 7
Synthesis of 1,1,1-trifluoro-N- (2-((3-oxomorpholino) methyl) thiophen-3-yl) methanesulfonamide (Compound No. 6-1) (1) Hydrogen in a nitrogen atmosphere A solution of sodium halide (60 wt%, 1.2 g) and dioxane (25 ml) was cooled to 0 ° C., ethanolamine (1.5 ml) was added, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was cooled to 0 ° C., ethyl chloroacetate (2.7 ml) was added, and the mixture was stirred at room temperature for 30 min, and further stirred for 40 min under heating under reflux. After cooling the reaction solution, the solid was removed by filtration. The filtrate was concentrated under reduced pressure, and the obtained residue was purified by column chromatography (ethyl acetate: methanol = 19: 1) to obtain morpholin-3-one (500 mg) as a colorless solid.
¹ H-NMR (500 MHz, CDCl ₃ , δppm): 3.43-3.45 (m, 2H), 3.84 (t, J = 5.0 Hz, 2H), 4.18 (s, 2H).
(2) Under a nitrogen atmosphere, a solution of methyl 3-amino-2-thiophenecarboxylate (3.0 g), N, N-diisopropylethylamine (10.0 ml) and acetonitrile (95 ml) was cooled to −30 ° C., and trifluoromethane was added. Sulfonic anhydride (9.6 ml) was added dropwise over 15 minutes. The mixture was further stirred for 75 minutes while maintaining the temperature between -30 ° C and 20 ° C. Water was added to stop the reaction, and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (heptane: ethyl acetate = 3: 1) and methyl 3- (1,1,1-trifluoro-N-((trifluoromethyl) sulfonyl) methylsulfonamido) thiophen-2- Carboxylate (7.0 g) was obtained as a yellow solid.
¹ H-NMR (500 MHz, CDCl ₃ , δppm): 3.95 (s, 3H), 7.13 (d, J = 6.0 Hz, 1H), 7.60 (d, J = 6.0 Hz, 1H).
(3) Methyl 3- (1,1,1-trifluoro-N-((trifluoromethyl) sulfonyl) methylsulfonamido) thiophene-2-carboxylate (4.0 g) synthesized in (2) above was converted to THF ( 47 ml), and diisobutylaluminum hydride (1 M toluene solution, 23.7 ml) was added dropwise over 15 minutes at 0 ° C. in a nitrogen atmosphere. After warming to room temperature and stirring for 14.5 hours, 2 N hydrochloric acid was added to the reaction solution at 0 ° C., and the mixture was stirred at room temperature for 30 minutes. Water was added to the reaction mixture, and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate = 7: 1 to 2: 1) and 1,1,1-trifluoro-N- (2- (hydroxymethyl) thiophen-3-yl) -N-((trifluoromethyl) sulfonyl) methanesulfonamide (2.2 g) was obtained as a brown oil.
¹ H-NMR (500 MHz, CDCl ₃ , δppm): 4.82 (d, J = 5.0 Hz, 2H), 6.96 (d, J = 5.5 Hz, 1H), 7.38 (d, J = 5.5 Hz, 1H).
(4) 1,1,1-trifluoro-N- (2- (hydroxymethyl) thiophen-3-yl) -N-((trifluoromethyl) sulfonyl) methanesulfonamide (800) synthesized in (3) above mg) was dissolved in ethanol (16 ml), an aqueous solution (4 ml) of sodium hydroxide (244 mg) was added at 0 ° C., and the mixture was stirred at 0 ° C. for 1 hour. Water and 2N hydrochloric acid were added to the reaction solution to acidify the reaction solution, and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain crude 1,1,1-trifluoro-N- (2- (hydroxymethyl) thiophene. -3-yl) methanesulfonamide (530 mg) was obtained as a light brown oil.
(5) Crude 1,1,1-trifluoro-N- (2- (hydroxymethyl) thiophen-3-yl) methanesulfonamide (530 mg) synthesized in (4) above was added to toluene (10 ml). After dissolving, p-toluenesulfonic acid monohydrate (40 mg) and morpholin-3-one (410 mg) synthesized in (1) above were added, and the mixture was stirred for 1 hour under heating to reflux. Water was added to stop the reaction, and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate = 1: 2) to obtain the desired product (260 mg, compound No. 6-1) as a colorless solid.

Synthesis example 8
Synthesis of ethyl (2-((3-oxomorpholino) methyl) thiophen-3-yl) ((trifluoromethyl) sulfonyl) carbamate (Compound No. 6-3)
1,1,1-trifluoro-N- (2-((3-oxomorpholino) methyl) thiophen-3-yl) methanesulfonamide (150 mg) was dissolved in toluene (4.4 ml) and pyridine (0.06 ml ) And ethyl chloroformate (0.07 ml) were added, and the mixture was stirred at room temperature for 15 hours. Water was added to stop the reaction, and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate = 1: 1) to obtain the desired product (120 mg, compound No. 6-3) as a pale brown oily substance.

Synthesis example 9
N- (2-((6,6-dimethyl-2-oxo-1,3-oxazinan-3-yl) methyl) thiophen-3-yl) -1,1,1-trifluoromethanesulfonamide (Compound No. Synthesis of 2-33) (1) 3-Hydroxy-3-methylbutyronitrile (10 ml) was dissolved in THF (50 ml) and pre-ice-cooled lithium aluminum hydride (8.0 g) in a nitrogen atmosphere. It was added dropwise to a suspension of THF (150 ml) over 20 minutes. The mixture was stirred for 4 hours under reflux, and after cooling, sodium sulfate decahydrate and potassium fluoride were added under ice cooling. After stirring for 30 minutes at room temperature, filtration was performed using Celite. The filtrate was dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain crude 3-amino-1,1-dimethyl-1-propanol (12.7 g) as a light brown oily substance.
(2) 3-Amino-1,1-dimethyl-1-propanol (6.0 g) obtained in (1) above was dissolved in methanol (60 ml), and 4-methoxybenzaldehyde (12.2 ml) was added under a nitrogen atmosphere. And a catalytic amount of acetic acid were added. The mixture was stirred for 1 hour under reflux, and after cooling, sodium borohydride (4.38 g) was added under ice cooling, followed by stirring at room temperature for 2 hours. A 3N aqueous hydrochloric acid solution was added and the mixture was stirred for 10 minutes, followed by extraction with ethyl acetate, and the aqueous layer was further washed with ethyl acetate. The aqueous layer was made basic by adding 6N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 3- (4-methoxybenzylamino) -1,1-dimethyl-1-propanol (6.67 g) as a brown oily substance. .
¹ H-NMR (500 MHz, CDCl ₃ , δppm): 1.19 (s, 6H), 1.60 (t, J = 5.5 Hz, 2H), 2.90 (t, J = 5.5 Hz, 2H), 3.70 (s, 2H ), 3.78 (s, 3H), 6.84 (d, J = 8.5 Hz, 2H), 7.20 (d, J = 8.5 Hz, 2H).
(3) 3- (4-Methoxybenzylamino) -1,1-dimethyl-1-propanol (6.67 g) obtained in (2) above is dissolved in toluene (100 ml), and iced in advance under a nitrogen atmosphere. The mixture was added dropwise to a cooled suspension of sodium hydride (60 wt%, 1.55 g) and toluene (200 ml) over 10 minutes. After stirring at room temperature for 30 minutes, diethyl carbonate (5.44 ml) was added dropwise, and the mixture was stirred under reflux for 12 hours. Saturated aqueous ammonia chloride was added at room temperature to stop the reaction, and the aqueous layer was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by column chromatography (heptane: ethyl acetate = 3: 7-0: 10), 3- (4-Methoxybenzyl) -6,6-dimethyl-1,3-oxazinan-2-one (4.21 g) was obtained as a light brown solid.
¹ H-NMR (500 MHz, CDCl ₃ , δppm): 1.36 (s, 6H), 1.82 (t, J = 6.5 Hz, 2H), 3.17 (t, J = 6.5 Hz, 2H), 3.80 (s, 3H ), 4.51 (s, 2H), 6.86 (d, J = 9.0 Hz, 2H), 7.23 (d, J = 9.0 Hz, 2H).
(4) 3- (4-Methoxybenzyl) -6,6-dimethyl-1,3-oxazinan-2-one (4.21 g) obtained in (3) above was dissolved in acetonitrile (168 ml) Then, ammonium cerium (IV) nitrate (27.77 g) and water (84 ml) were added and stirred for 12 hours. The solvent was distilled off under reduced pressure, followed by filtration to remove solids. The obtained filtrate was dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by column chromatography (ethanol: ethyl acetate = 0: 10-1: 9) to give 6,6-dimethyl. -1,3-oxazinan-2-one (2.10 g) was obtained as a light brown oil.
¹ H-NMR (500 MHz, CDCl ₃ , δppm): 1.44 (s, 6H), 1.94 (br s, 2H), 3.56 (br s, 2H).
(5) 1,1,1-trifluoro-N- (2- (hydroxymethyl) thiophen-3-yl) methanesulfonamide (0.79 g) was dissolved in toluene (55 ml), and p-toluenesulfonic acid Hydrate (0.63 g) and 6,6-dimethyl-1,3-oxazinan-2-one (0.43 g) obtained in (4) above were added. The reaction solution was heated and stirred for 2 hours with azeotropic dehydration using a Dean-Stark distillation apparatus. After cooling to room temperature, the mixture was diluted with ethyl acetate and washed with saturated brine. After drying over sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by column chromatography (heptane: ethyl acetate = 3: 7-0: 10) to obtain a crude target product (0.14 g, Compound No. 2-33) was obtained as a light brown oil.

Synthesis example 10
Ethyl (2-((6,6-dimethyl-2-oxo-1,3-oxazinan-3-yl) methyl) thiophen-3-yl) ((trifluoromethyl) sulfonyl) carbamate (Compound No. 2-35 ) Synthesis
N- (2-((6,6-Dimethyl-2-oxo-1,3-oxazinan-3-yl) methyl) thiophen-3-yl) -1,1,1-trifluoromethanesulfonamide (0.14 g) Was dissolved in toluene (5.0 ml), pyridine (59.3 mg) and ethyl chloroformate (81.4 mg) were added, and the mixture was stirred at room temperature for 2 hours. After 2 N hydrochloric acid aqueous solution was added to stop the reaction, the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by column chromatography (heptane: ethyl acetate = 7: 3 to 3: 7) to obtain the desired product (79 mg, compound No. 2-35) as a light brown solid.

Next, typical examples of the compounds according to the present invention are listed in Tables 1 to 13. These compounds can be synthesized based on the above synthesis examples or the various production methods described above. In Tables 1 to 13, the numerical values described in the physical properties column represent melting points (° C.), and for the compounds described as NMR, their ¹ H-NMR spectral data are listed in Table 14. In Tables 1 to 14, No. indicates the compound number. In the table, Me is a methyl group, Et is an ethyl group, n-Pr is a normal propyl group, i-Pr is an isopropyl group, c-Pr is a cyclopropyl group, and n-Bu is a normal butyl group. S-Bu represents a secondary butyl group, i-Bu represents an isobutyl group, t-Bu represents a tertiary butyl group, Ph represents a phenyl group, and C = O represents a carbonyl group. In addition, 3-CF ₃ Ph represents a phenyl group substituted with CF _{3 at the} 3-position, and other similar descriptions are based on this.

・ 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) barnyardgrass ( Echinochloa crus-galli L.); 1.0-3.0 leaf stage, (2) crabgrass ( Digitaria sanguinalis L.); 1.0-3.0 leaf stage (3) Green foxtail ( Setariaviridis L.); 1.5-3.0 leaf stage, (4) Red root pigweed ( Amaranthus retroflexus L.); 0.2-2.0 leaf stage, (5) American golden beetle (prickly) sida ( Sida spinosa L.)); cotyledons to 2.0 leaves, (6) velvetleaf ( Abutilon theophrasti MEDIC.); 0.2 to 2.0 leaves, (7) rice (rice ( Oryza sativa L.)); 1.2 -2.5 leaf stage, (8) corn (corn ( Zea mays L.)); 2.5-3.5 leaf stage, (9) wheat (wheat ( Triticum spp.)); 2.5-4.0 leaf stage, (10) cotton (cotton) ( Gossypium spp.)); Primary leaves to 0.5 leaves, (11) soybean ( Glycine max Merr.); Primary leaves to 0.5 leaves) Wet powder prepared according to The emulsion was weighed to make a predetermined amount of active ingredient per hectare 500 liters water corresponding: diluted (agricultural spreader (Kusarino manufactured by Nihon Nohyaku) 0.1 volume% containing). The prepared spray was treated with a small spray.

  After the chemical treatment, the growth state of various plants was visually observed on the 13th to 15th days, and the herbicidal effect was evaluated at a growth inhibition rate (%) of 0 (equivalent to the untreated group) to 100 (completely killed). The results shown in Table 15 were obtained.

・ Test Example 2
1 / 170,000 hectare pot filled with upland field soil, various plants (barnyardgrass ( Echinochloa crus-galli L.)), barkyard (crabgrass ( Digitaria sanguinalis L.)), green foxtail (green foxtail ( Setaria viridis L.)), Red root pigweed ( Amaranthus retroflexus L.), American deer (prickly sida ( Sida spinosa L.)), green velvetleaf ( Abutilon theophrasti MEDIC.), Rice (rice ( oryza sativa L.)), maize ( Corn ( Zea mays L.)), wheat (wheat ( Triticum spp.)), cotton (cotton ( Gossypium spp.)), soybean (soybean ( Glycine max Merr.))) were sown. On the day after sowing, a wettable powder or emulsion prepared according to the usual formulation method of the compound according to the present invention is weighed so as to have a predetermined active ingredient amount, diluted in water equivalent to 500 liters per hectare, and a small spray Soil treatment.

  On the 14th to 21st days after the chemical treatment, the growth state of various plants was observed with the naked eye, and the herbicidal effect was evaluated at a growth inhibition rate (%) of 0 (equivalent to the untreated group) to 100 (completely killed). The results of Table 16 were obtained.

・ Test Example 3
Paddy soil was packed in a 1 / 1,000,000 hectare pot, and seeds of barnyardgrass ( Echinochloa oryzicola vasing.) And firefly (Japanese bulrush ( Scirpus juncoides )) were sown and lightly covered with soil. Thereafter, the tube was left in a greenhouse at a depth of 0.5 to 1 cm, and the tuber of Urikawa (Japanese ribbon waparo ( Sagittaria pygmaea )) was planted the next day. Thereafter, the water depth was maintained at 3 to 4 cm, and when the Tainubier and firefly reached the 0.5 leaf stage and Urikawa reached the primary leaf stage, the compound according to the present invention was prepared according to a usual formulation method or a wettable powder or emulsion. The aqueous diluted solution was uniformly dropped with a pipette so as to obtain a predetermined active ingredient amount. In addition, paddy soil is packed in a 1 / 1,000,000 hectare pot, padded, and the water depth is 3-4 cm. The next day rice ( Oryza sativa L.) (variety: Nipponbare) is transplanted 3 cm deep Transplanted. On the day after transplantation, the compound according to the present invention was treated in the same manner as described above.

  After the drug treatment, the growth state of Tainubie, firefly and urikawa was observed on the 11th to 14th days, and the growth state of rice was observed on the 14th to 16th days after the drug treatment. Evaluation was made with a growth inhibition rate (%) of 100 (complete killing), and the results in Table 17 were obtained.

  Next, formulation examples of the present invention will be described.

Formulation example 1
(1) Compound according to 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 (1) to (4) 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 DSL Japan Co., Ltd.) 15 parts by weight or more of a mixture of the components (1) to (4) and the compound according to the present invention are mixed at a weight ratio of 9: 1. A Japanese medicine 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.) 4 parts by weight (4) Compound according to the present invention 60 parts by weight or more of each component of (1) to (4) is mixed to obtain a wettable powder.

Formulation example 4
(1) Compound according to 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 Pre-ground (1), (2) and (3) are mixed, and (4), (5) and water are added and mixed there. Extrude granulate. Then, a granule is obtained by drying and sizing.

Formulation example 5
(1) Compound according to 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 Part by weight (4) New Calgen FS-7 (trade name; manufactured by Takemoto Yushi Co., Ltd.) 5 parts by weight After mixing (1), (2) and (3) above and passing through a pulverizer, (4) After kneading and extruding granulation. Then, a granule wettable powder is obtained by drying and sizing.

Formulation Example 6
(1) Compound according to the present invention 28 parts by weight (2) Sopropol FL (trade name; manufactured by Rhône-Poulenc) 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 the components (1) to (6) An aqueous suspension is obtained by pulverization using a wet pulverizer (Dyno mill).

  The heteroarylsulfonamide-based compound or a salt thereof according to the present invention realizes a significant improvement in herbicidal activity against undesirable plants as compared with similar conventional compounds. In addition, it has high safety for crops. Therefore, the heteroaryl sulfonamide compound or a salt thereof according to the present invention exhibits an excellent herbicidal effect when used as an active ingredient of a herbicide. The range of application ranges widely from agricultural fields such as paddy fields, upland fields, orchards, mulberry fields, and non-agricultural land such as forests, farm roads, grounds, and factory sites. Applicable methods include soil treatment, foliage treatment, and flooding treatment as appropriate. You can choose.

Claims (3)

Formula (I):

[Wherein A is an oxygen atom, sulfur atom, SO, SO ₂ or CR ⁸ R ⁹ ; W is an oxygen atom or sulfur atom; Z is an oxygen atom, sulfur atom or CR ¹⁰ R ¹¹ ; m Is 0, 1 or 2; n is 0, 1 or 2; provided that 0 ≦ n + m ≦ 3; q is 0, 1 or 2; R ¹ is haloC ₁ -C ₆ R ² is a hydrogen atom or C ₁ -C ₁₂ alkoxycarbonyl; R ³ is a halogen atom, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C _1- C ₃ -C ₆ cycloalkyl optionally substituted with C ₆ alkyl, halo C ₁ -C ₆ alkyl, halo C ₂ -C ₆ alkenyl, halo C ₂ -C ₆ alkynyl, halo C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkylsulfonyl, halo C ₁ -C ₆ alkylsulfonyl, phenyl or cyano optionally substituted with Y; R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ And R ¹¹ are the same or C ₃ -C ₆ cyclo which may be different and may be substituted with hydrogen atom, halogen atom, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkyl Alkyl, halo C ₁ -C ₆ alkyl, halo C ₂ -C ₆ alkenyl, halo C ₂ -C ₆ alkynyl, halo C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl C ₁ -C ₆ alkyl, Y Phenyl optionally substituted with Y, phenyl C ₁ -C ₆ alkyl optionally substituted with Y, C ₁ -C ₆ alkylcarbonyloxy, hydroxyl or cyano; R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ and R ¹⁰ and R ¹¹ can be bonded to each other to form an optionally substituted 3- to 7-membered ring, and the 3- to 7-membered ring is an oxygen atom, a sulfur atom or nitrogen atom (nitrogen atom, is substituted C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, by C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl Also contain one or two heteroatoms selected from may also) well, or can be formed olefin, carbonyl or ^{thiocarbonyl; R 4, R 5, R} 6, R 7, R 8 , R ⁹ , R ¹⁰ and R ¹¹ are any R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ or R on a carbon atom different from the carbon atom to which each is bonded. ¹¹ to form an optionally substituted 3- to 8-membered ring, and the 3- to 8-membered ring is an oxygen atom, a sulfur atom, or a nitrogen atom (the nitrogen atom is C ₁ -C May contain 1 or 2 heteroatoms selected from ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl); R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ can be any R ⁴ , R ⁵ , R ⁶ , R ⁷ on the carbon atom adjacent to the carbon atom to which they are attached. , R ⁸ , R ⁹ , R ¹⁰ Can bind to R ¹¹ ; Y can be substituted with a halogen atom, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkyl _3- C ₆ cycloalkyl, halo C ₁ -C ₆ alkyl, halo C ₂ -C ₆ alkenyl, halo C ₂ -C ₆ alkynyl, halo C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, halo C ₁ --C ₆ alkoxy, C ₁ --C ₆ alkylthio, halo C ₁ --C ₆ alkylthio, C ₁ --C ₆ alkylsulfinyl, halo C ₁ --C ₆ alkylsulfinyl, C ₁ --C ₆ alkylsulfonyl, halo C ₁ --C ₆ alkylsulfonyl, carboxyl, C ₁ -C ₆ alkylcarbonyl, halo C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, halo C ₁ -C ₆ alkoxycarbonyl, amino, mono (C ₁ -C ₆ alkyl ) amino, mono (halo C ₁ -C ₆ alkyl) amino, di (C ₁ C ₆ alkyl) amino, di (halo C ₁ -C ₆ alkyl) amino, cyano, nitro or hydroxyl group]
Or a salt thereof.   A herbicide containing the heteroarylsulfonamide compound according to claim 1 or a salt thereof as an active ingredient.   A method of applying a herbicidally effective amount of the heteroarylsulfonamide compound or a salt thereof according to claim 1 to an undesirable plant or a place where it grows, and controlling or suppressing the growth of the undesirable plant.