JP2007246477A - Sulfonylurea compound and herbicide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an agrochemical, especially a herbicide that comprises a sulfonylurea compound as an active ingredient an has excellent effect. <P>SOLUTION: The agrochemical, especially the herbicide comprises one or more as an active ingredient selected from a sulfonylurea compound that contains a pyrimidine or triazine heterocyclic ring which may contain a specific substituent group on a nitrogen atom, further a 1,4,2-dioxazine ring and a salt acceptable as an agrochemical. A compound represented by formula is exemplified as a concrete compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to sulfonylurea compounds and agricultural chemicals containing them as active ingredients, in particular herbicides.

Patent Document 1 and Patent Document 2 disclose that sulfonylureas having a dioxazine ring in the molecule have herbicidal activity. However, Patent Document 1 and Patent Document 2 do not include sulfonylureas in which a substituted methylene group is bonded to a dioxazine ring.
Japanese Unexamined Patent Publication No. 7-118269 International Patent Application Publication WO2005 / 103044 Pamphlet

  To provide an agrochemical, particularly a herbicide, having a sulfonylurea compound as an active ingredient and having excellent efficacy.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that the novel sulfonylurea compound has herbicidal activity and crop selectivity, and has completed the present invention.

  That is, the present invention provides the formula (1):

[Wherein, X and Y are each independently a C _1-3 alkyl group, a C _1-3 haloalkyl group, a C _1-3 alkoxy group, a C _1-3 haloalkoxy group, a halogen atom, di (C _1-3 Alkyl) amino group or C _1-3 alkylamino group,
Z represents a nitrogen atom or a methine group,
G is

Represents
GJ- represents GJ-1 to GJ-7, where GJ-1 to GJ-7 have the following meanings:

Represents
E represents —CH ₂ —, —O— or —NH—,
R ¹ represents a C _1-3 alkyl group, a C _1-3 haloalkyl group, a C _1-3 alkoxy C _1-3 alkyl group, a phenyl group or a pyridyl group,
R ² represents a hydrogen atom, a C _1-3 alkyl group, a C _1-3 haloalkyl group, a C _1-3 alkoxy group, a halogen atom, —NHCHO or —CH ₂ NHSO ₂ CH ₃ ;
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom, a C _1-3 alkyl group or a C _1-3 haloalkyl group, provided that R ³ , R ⁴ , R ⁵ and R ⁶ , At least one represents a C _1-3 alkyl group or a C _1-3 haloalkyl group. ] A pesticide containing as an active ingredient at least one selected from a sulfonylurea compound represented by the following (hereinafter referred to as “the compound of the present invention”) and a salt acceptable as a pesticide, a compound of the present invention and a salt acceptable as a pesticide. In addition, the present invention relates to a herbicide containing as an active ingredient at least one selected from the compound of the present invention and a salt acceptable as an agricultural chemical.

  In addition, the compound of the present invention and a salt acceptable as an agrochemical exhibit a synergistic herbicidal effect with the herbicide when used in the form of a mixture with a certain herbicide.

  The sulfonylurea compound of the present invention has an excellent herbicidal effect on weeds, and at the same time, is an excellent selective herbicidal active compound for paddy rice and wheat that does not cause phytotoxicity to rice and wheat.

Specific examples of substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, Y, and Z of the compound of the present invention and the intermediate for producing the compound of the present invention are illustrated. However, each symbol has the following meaning.

Me: methyl group, Et: ethyl group, Pr-n: normal propyl group, Pr-iso: isopropyl group, Ph: phenyl group, Py: pyridyl group [specific examples of substituent R ¹ ]
Me, Et, Pr-n, Pr-iso, CH 2 F, CHF 2, CF 3, CH 2 CH 2 F, CH 2 CHF 2, CH 2 CF 3, CH 2 CH 2 CH 2 F, CH 2 CH 2 _{CHF 2, CH 2 CH 2 CF} 3, CH 2 CH 2 Cl, CH 2 CH 2 Br, CH 2 OMe, CH 2 OEt, CH 2 OPr-n, CH 2 OPr-iso, CH 2 CH 2 OMe, CH 2 _{CH 2 OEt, CH 2 CH 2} OPr-n, CH 2 CH 2 OPr-iso, CH 2 CH 2 CH 2 OMe, CH 2 CH 2 CH 2 OEt, CHMeCH 2 OMe, CH 2 CHMeOMe, Ph, 2-Py
[Specific examples of substituent R ² ]
H, Me, Et, Pr- n, Pr-iso, CH 2 F, CHF 2, CF 3, CH 2 CH 2 F, CH 2 CHF 2, CH 2 CF 3, CH 2 CH 2 CH 2 F, CH 2 CH ₂ CHF ₂ , CH ₂ CH ₂ CF ₃ , CH ₂ CH ₂ Cl, OMe, OEt, OPr-n, OPr-iso, F, Cl, Br, I
[Specific examples of substituents R ³ , R ⁴ , R ⁵ and R ⁶ ]
H, Me, Et, Pr- n, Pr-iso, CH 2 F, CHF 2, CF 3, CH 2 Cl, CHCl 2, CCl 3, CH 2 Br, CH 2 I, CH 2 CH 2 F, CH 2 _{CHF 2, CH 2 CF 3,} CH 2 CH 2 CH 2 F
[Specific Examples of Substituents X and Y]
Me, Et, Pr-n, Pr-iso, OCH 3, OCH 2 CH 3, OPr-n, OPr-iso, CH 2 F, CHF 2, CF 3, CH 2 Cl, CHCl 2, CCl 3, CH 2 _{CH 2 F, CH 2 CHF 2} , CH 2 CF 3, CF 2 CF 3, CH 2 CH 2 CH 2 F, CH 2 CH 2 CHF 2, CH 2 CH 2 CF 3, CH 2 CH 2 Cl, CH 2 CH ₂ Br, OCH ₂ F, OCHF ₂ , OCF ₃ , OCH ₂ CH ₂ F, OCH ₂ CHF ₂ , OCH ₂ CF ₃ , OCF ₂ CF ₃ , OCH ₂ CH ₂ CH ₂ F, OCH ₂ CH ₂ CHF ₂ , OCH ₂ CH ₂ CF ₃ , OCH ₂ CH ₂ Cl, OCH ₂ CH ₂ Br, F, Cl, Br, I, Me ₂ N, Et ₂ N, (Pr-n) ₂ N, MeNH, EtNH, (Pr-n ) NH
[Specific examples of substituent Z]
N, CH
The compound (1) of the present invention may have optical isomers, and all of the optical isomers are included in the compound of the present invention.

  The compound (1) of the present invention can be produced by the methods shown in the following reaction formulas 1 to 3.

  [Reaction Formula 1]

  Scheme 1 shows the reaction of (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonamide (2) in the presence or absence of a base with 2-phenoxycarbonylaminopyrimidine. A method for producing the compound (1) of the present invention by reacting with (or triazine) (3) is shown.

  In this reaction, (3) is generally used in an amount of 0.5 to 10-fold mol, preferably 0.9 to 1.1-fold mol based on (2).

  Bases used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N-dimethylaniline, 1 , 8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane and other organic bases, n-butyllithium and sec-butyllithium and other organic lithiums, Examples thereof include organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. The base is generally used in an amount of 0 to 10 moles, preferably 0 to 2 moles compared to (2).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 120 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  [Reaction formula 2]

  Scheme 2 shows the reaction of (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonylcarbamate (4) in the presence or absence of a base with 2-aminopyrimidine (or A method for producing the compound (1) of the present invention by reacting with (triazine) (5) is shown.

  In this reaction, (5) is usually used in an amount of 0.5 to 10-fold mol, preferably 0.9 to 1.1-fold mol based on (4).

  Bases used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N-dimethylaniline, 1 , 8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane and other organic bases, n-butyllithium and sec-butyllithium and other organic lithiums, Examples thereof include organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. The base is generally used in an amount of 0 to 10 moles, preferably 0 to 2 moles compared to (4).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 120 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  [Reaction Formula 3]

  Scheme 3 shows the reaction of (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonyl isocyanate (6) in the presence or absence of a base with 2-aminopyrimidine ( Or the method of manufacturing this invention compound (1) by making it react with (triazine) (5) is shown.

  In this reaction, (5) is generally used in an amount of 0.5 to 10-fold mol, preferably 0.9 to 1.1-fold mol based on (6).

  Bases used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N-dimethylaniline, 1 , 8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane and other organic bases, n-butyllithium and sec-butyllithium and other organic lithiums, Examples thereof include organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. The base is usually used in an amount of 0 to 10 moles, preferably 0 to 2 moles compared to (3).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 120 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  The (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonamide (2) used in the method shown in Reaction Scheme 1 is the method shown in Reaction Schemes 4-6. Can be manufactured.

  Further, (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonylcarbamate (4) and (5-alkylidene-) used in the methods shown in Reaction Schemes 2 to 3 are used. 5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonyl isocyanate (6) is (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)- It can be synthesized using (hetero) arylsulfonamide (2) as a raw material with reference to the methods described in JP-A-59-219281 and JP-A-55-13266.

  [Reaction Formula 4]

  Scheme 4 shows the reaction of (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) aryl chloride (7) with sodium hydrosulfide to give (5-methylene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) aryl sulfide (8) (step A) and (8) is reacted with a chlorinating agent such as chlorine or sodium hypochlorite ( 5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonyl chloride (9) (step B), (9) is reacted with aqueous ammonia or ammonium carbonate ( Step C) shows a method for producing (5-methylene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonamide (2).

  In the reaction of Step A, sodium hydrosulfide is generally used in an amount of 1.0 to 10-fold mol, preferably 2 to 5-fold mol based on (7).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as N-methyl-2-pyrrolidone, sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane, water, and a mixed solvent thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 120 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  In the reaction of Step B, chlorine or sodium hypochlorite is usually used in an amount of 1 to 100 times mol, preferably 2 to 10 times mol for (8).

  This reaction can use a solvent as needed. The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, water, and a mixed solvent thereof.

  The reaction temperature is usually -90 to 100 ° C, preferably -10 to 50 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  In the reaction of Step C, ammonia or ammonium carbonate is usually used in an amount of 1.0 to 100-fold mol, preferably 2 to 5-fold mol based on (9).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as N-methyl-2-pyrrolidone, sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane, water, and a mixed solvent thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 100 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  [Reaction Formula 5]

  Scheme 5 shows the reaction of (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylbenzyl sulfide (10) with a chlorinating agent such as chlorine or sodium hypochlorite. A method for producing (5-methylene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonyl chloride (9) by reaction is shown.

  In this reaction, chlorine or sodium hypochlorite is usually used in an amount of 1 to 100 times mol, preferably 2 to 10 times mol for (10).

  This reaction can use a solvent as needed. The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, water, and a mixed solvent thereof.

  The reaction temperature is usually -90 to 100 ° C, preferably -10 to 50 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  (9) can be derived into (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonamide (2) by Step C of Reaction Scheme 4.

  [Reaction Formula 6]

  In Reaction Scheme 6, the 5-position on the pyrazole ring of (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) aryl (11) is n-butyllithium or lithium diisopropylamide, etc. And then reacted with sulfur dioxide to give (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfinate (12) (step D), ( 12) is reacted with N-chlorosuccinimide (step E) to produce (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonyl chloride (9) How to do.

  In the reaction of step D) 1), n-butyllithium or lithium diisopropylamide is usually used in an amount of 1 to 100 times mol, preferably 1 to 5 times mol for (11).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, and mixtures thereof Solvent.

  The reaction temperature is usually -120 to 100 ° C, preferably -78 to 10 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  In the reaction of step D 2), sulfur dioxide is usually used in an amount of 1.0 to 100-fold mol, preferably 1 to 10-fold mol based on (11).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, and mixtures thereof Solvent.

  The reaction temperature is usually -120 to 100 ° C, preferably -78 to 10 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  In the reaction of Step E, N-chlorosuccinimide is usually used in an amount of 1.0 to 100-fold mol, preferably 1 to 10-fold mol based on (12).

  The solvent used in this reaction is not particularly limited as long as it is inert to the reaction. For example, halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, water, and mixtures thereof Solvent.

  The reaction temperature is usually -90 to 100 ° C, preferably -10 to 50 ° C.

The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
(9) can be derived into (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonamide (2) by Step C of Reaction Scheme 4.

  (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonamide (2), (5-alkylidene-5H, used in the method shown in Reaction Schemes 1 to 6 6H-1,4,2-dioxazin-3-yl)-(hetero) arylsulfonylcarbamate (2) (2 ′), (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl) -(Hetero) aryl chloride (7), (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl)-(hetero) arylbenzyl sulfide (10) and (5-alkylidene-5H, 6H) -1,4,2-Dioxazin-3-yl)-(hetero) aryl (11) can be prepared by the method shown in Reaction Schemes 7-11.

  [Reaction Scheme 7]

  Reaction Scheme 9 is a reaction of (hetero) arylcarboxylic acid chloride (15) with allyloxyamine (16a) to give (hetero) arylhydroxamic acid ester (17a) (step F), wherein (17a) is halogenated or N- 4- (5-haloalkyl-5H, 6H-1,4,2-dioxazin-3-yl) (hetero) aryl (2a), (2′a), (2 ″) by reacting with a halogenated succinimide a), (7a), (10a) or (11a) (step G), (2a), (2′a), (2 ″ a), (7a), (10a) or (11a) Hydrogenated (Step H), (5-alkylidene-5H, 6H-1,4,2-dioxazin-3-yl) (hetero) aryl (2b), (2′b) (2 ″ b) , (7b), (10b) or (11 The method of manufacturing b) is shown.

  In the reaction of Step F, (16a) is generally used in an amount of 1 to 100 times mol, preferably 2 to 5 times mol, of (15).

  Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydride and other inorganic bases, pyridine, 4-dimethylaminopyridine, triethylamine, Organic bases such as N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane, n-butyllithium and sec- Examples thereof include organic lithiums such as butyl lithium, organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. The base is generally used in an amount of 0 to 10 moles, preferably 0 to 2 moles compared to (15).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 100 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  In the reaction of Step G, halogen or N-halogenosuccinimide is generally used in an amount of 1 to 100 times mol, preferably 1 to 5 times mol, of (17a).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, carboxylic acid esters such as methyl acetate or ethyl acetate, methanol , Alcohols such as ethanol or ethylene glycol, amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, water, and mixed solvents thereof It is.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 100 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  Examples of the base used in the reaction of Step H include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, Organic bases such as triethylamine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane, n-butyllithium and Examples include organolithiums such as sec-butyllithium, organolithiums such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. The base is usually used in an amount of 0 to 100-fold mol, preferably 0 to 5-fold mol based on (2c), (2′c), (2 ″ c), (7c), (10c) or (11c). .

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 100 ° C.

The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

[Reaction Formula 8]

  Scheme 8 shows (5-haloalkyl (or alkylsulfonyloxyalkyl) -5H, 6H-1,4,2-dioxazin-3-yl) (hetero) aryl (2c), (2'c), (2 ' 'c), (7c), (10c) or (11c) is dehydrohalogenated (or dealkylsulfonated) in the presence or absence of a base to give the corresponding (5-alkylidene-5H, 6H A method for producing -1,4,2-dioxazin-3-yl) (hetero) aryl (2d), (2'd), (2''d), (7d), (10d) or (11d) Show.

  Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydride and other inorganic bases, pyridine, 4-dimethylaminopyridine, triethylamine, Organic bases such as N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane, n-butyllithium and sec- Examples thereof include organic lithiums such as butyl lithium, organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. The base is usually used in an amount of 0 to 100-fold mol, preferably 0 to 5-fold mol based on (2c), (2′c), (2 ″ c), (7c), (10c) or (11c). .

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 100 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  [Reaction Formula 9]

  Scheme 9 is a reaction of (hetero) aryl hydroxamic acid (13) with an allyl compound (18) in the presence or absence of a base to give the (hetero) aryl hydroxamic acid ester (17a) used in Scheme 7 The manufacturing method is shown.

  In this reaction, (18) is generally used in an amount of 1 to 100-fold mol, preferably 1 to 5-fold mol based on (13).

  Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydride and other inorganic bases, pyridine, 4-dimethylaminopyridine, triethylamine, Organic bases such as N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane, n-butyllithium and sec- Examples thereof include organic lithiums such as butyl lithium, organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. The base is generally used in an amount of 0 to 100-fold mol, preferably 0 to 5-fold mol based on (13).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 100 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  [Reaction Formula 10]

  Reaction Scheme 10 is a reaction of (hetero) aryl hydroxamic acid (13) with epihalohydrin (21) in the presence or absence of a base to give (hetero) aryl hydroxamic acid ester (17c) (step I), (17c ) With acid or base to give (5-hydroxyalkyl-5H, 6H-1,4,2-dioxazin-3-yl) (hetero) aryl (2f), (2'f), (2 '' f), (7f), (10f) or (11f) (step J), then (2f), (2′f), (2 ″ f), (7f), (10f) or (11f) ) Is halogenated or alkylsulfonylated (step K) to give the corresponding (5-haloalkyl (or alkylsulfonyloxyalkyl) -5H, 6H-1,4,2-dioxazin-3-yl (Hetero) aryl (2c), illustrates a method of preparing (2'c), (2''c), (7c), (10c) or (11c). (2c), (2′c), (2 ″ c), (7c), (10c) or (11c) is used in Reaction Scheme 8.

  In the reaction of Step I, (21) is usually used in an amount of 1 to 100-fold mol, preferably 1 to 5-fold mol based on (13).

  Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydride and other inorganic bases, pyridine, 4-dimethylaminopyridine, triethylamine, Organic bases such as N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane, n-butyllithium and sec- Examples thereof include organic lithiums such as butyl lithium, organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. The base is generally used in an amount of 0 to 100-fold mol, preferably 0 to 5-fold mol based on (13).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 100 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  Examples of the acid or base used in the reaction of Step J include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid, Inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N-dimethylaniline, 1, Organic bases such as 8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane, organic lithiums such as n-butyllithium and sec-butyllithium, lithium Diisopropylamide and lithium bis (trimethylsilyl ) Organic lithium amide such as amide, and sodium methoxide, metal alkoxides such as sodium ethoxide and potassium t- butoxide. The acid or base is generally used in an amount of 0 to 100-fold mol, preferably 0 to 5-fold mol based on (17c).

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 100 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  In the reaction of Step K, the halogenating agent or alkylsulfonylating agent is usually 1 to 100 with respect to (2f), (2′f), (2 ″ f), (7f), (10f) or (11f). Double moles, preferably 1 to 5 moles are used.

  Examples of the halogenating agent used in this reaction include hydrogen halide acids such as hydrogen chloride, hydrogen bromide and hydrogen iodide, phosphorus halides such as phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and phosphorus tribromide. Phosphonates such as triphenyl / benzyl chloride and triphenylphosphine / carbon tetrachloride, sulfonium halides such as methanesulfonyl chloride and p-toluenesulfonyl chloride, and thionyl halides such as thionyl chloride and thionyl bromide. .

  Examples of the alkylsulfonylating agent used in this reaction include sulfonium halides such as methanesulfonyl chloride and p-toluenesulfonyl chloride.

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 100 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  [Reaction Formula 11]

  Scheme 15 is a scheme in which (hetero) aryl-carboxylic acid chloride (15) or (hetero) aryl-carboxylic acid methyl ester (15 ′) is reacted with hydroxyamine in the presence or absence of a base to form scheme 9 to 1 shows a method for producing (hetero) aryl hydroxamic acid (13) used in No. 10.

  In this reaction, hydroxylamine is generally used in an amount of 1 to 100 times mol, preferably 1 to 5 times mol, of (15) or (15 ').

  Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, sodium hydride and other inorganic bases, pyridine, 4-dimethylamino. Organic bases such as pyridine, triethylamine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane, n-butyl Organic lithiums such as lithium and sec-butyllithium, organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide . The base is generally used in an amount of 0 to 100-fold mol, preferably 0 to 5-fold mol based on (15) or (15 ').

  This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane. , Ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide And amides such as N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

  The reaction temperature is usually -90 to 200 ° C, preferably 0 to 100 ° C.

  The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

  The desired product obtained by the above reaction can be isolated and purified by operations such as filtration, extraction, washing, column chromatography, recrystallization and distillation after completion of the reaction.

  In the above description, J-L is the following.

Represents a structure selected from
[Wherein, G, J, X, Y, Z, R ³ , R ⁴ , R ⁵ , and R ⁶ have the same meanings as described above, X ¹ represents a halogen atom, X ² represents a halogen atom, C _{It represents a 1-3} alkylsulfonyloxy group or a C _1-3 haloalkylsulfonyloxy group, and L represents a sulfonyl carbamate, a sulfonamide, a chlorine atom, a benzylthio group or a hydrogen atom. ]

Although the synthesis example of this invention compound is specifically described as an Example and a reference example below, this invention is not limited to these.

[Example 1]
N-((4,6-dimethoxypyrimidin-2-yl) aminocarbonyl) -3-chloro-1-methyl-4- (5-methylene-5H, 6H-1,4,2-dioxazin-3-yl) Synthesis of pyrazole-5-sulfonamide (the present compound No. 1)

3-Chloro-1-methyl-4- (5-methylene-5H, 6H-1,4,2-dioxazin-3-yl) pyrazole-5-sulfonamide (0.13 g, 0.44 mmol) in acetonitrile (6 ml) ) And phenyl N- (4,6-dimethoxypyrimidin-2-yl) carbamate (0.13 g, 0.47 mmol) are dissolved in 1,8-diazabicyclo [5.4.0] -7-undecene (0 0.07 g, 0.46 mmol) was added, and the mixture was stirred at room temperature for 1 hour. The solvent was evaporated under reduced pressure, 2N hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain an oil. A mixed solvent of toluene and hexane was added to this oily substance, and the precipitated solid was collected by filtration, washed with a small amount of toluene, and dried under reduced pressure to obtain the desired product (0.10 g). White solid. Melting point 164-167 [deg.] C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl ₃ ) 3.95 (s, 6H), 4.32 (s, 3H), 4.35 (s, 2H), 4.42 (d, J = 2.7 Hz, 1H), 4.78 (d, J = 2.7 Hz, 1H), 5.80 (s, 1H), 7.32 (brs, 1H), 11.98 (brs, 1H).
[Reference Example 1]
(1) Synthesis of 3-chloro-1-methyl-5-sulfamoylpyrazole-4-carbohydroxamic acid

A reaction flask was charged with 100 g (394 mmol) of methyl 3-chloro-1-methyl-5-sulfamoylpyrazole-4-carboxylate and 1000 g of water and cooled to 0 ° C. To this solution, 52 g (787 mmol) of 50% aqueous hydroxylamine solution was added dropwise, and then 58 g (783 mmol) of calcium hydroxide was added in three portions. After reacting at the same temperature for 2.5 hours, 210 g of concentrated hydrochloric acid was added dropwise to stop the reaction. The reaction solution was filtered and the residue was washed with 10 g of 1N hydrochloric acid. The resulting solid on the funnel was dried under reduced pressure to obtain 82.8 g (yield 83%) of the target compound. White solid. Melting point 182 ° C. (decomposition). Proton nuclear magnetic resonance chemical shift value δ (ppm) (in d6-DMSO) 3.98 (s, 3H), 8.13 (bs, 1H), 9.27 (bs, 2H), 10.70 (bs, 1H).
(2) Synthesis of 3-chloro-1-methyl-5-aminosulfonylpyrazole-4-carbohydroxamic acid-allyl ester

3-Chloro-1-methyl-5-sulfamoylpyrazole-4-carbohydroxamic acid (0.76 g, 3.0 mmol) was added to a mixed solvent of water (7 ml) and toluene (7 ml). Next, potassium hydrogen carbonate (0.36 g, 3.6 mmol) and allyl bromide (0.43 g, 3.6 mmol) were added and reacted at 60 ° C. for 8 hours. Allyl bromide (0.04 g, 0.36 mmol) was added and reacted at room temperature for an additional 13 hours. The reaction solution was separated, and the resulting aqueous layer was acidified with 2N hydrochloric acid, and then extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate and the solvent was distilled off. The resulting solid (0.74 g) was washed with a mixed solvent of chloroform and hexane and dried under reduced pressure to obtain the desired product (0.61 g). . White solid. Melting point 166-168 [deg.] C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl ₃ ) 4.16 (s, 3H), 4.53 (d, J = 6.6 Hz, 3H), 5.35-5.50 (m, 2H), 5.95-6.12 (m, 1H), 6.40 (brs, 2H), 8.98 (brs, 1H).
(3) Synthesis of 3-chloro-1-methyl-4- (5-iodomethyl-5H, 6H-1,4,2-dioxazin-3-yl) pyrazole-5-sulfonamide

To acetonitrile (8 ml) was added 3-chloro-1-methyl-5-aminosulfonylpyrazole-4-carbohydroxamic acid-allyl ester (0.61 g, 2.1 mmol) and iodine (1.60 g, 6.3 mmol). Stir at room temperature for 1 hour. A sodium thiosulfate aqueous solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate layer was washed successively with water and saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and evaporated. The obtained residue was purified by silica gel column chromatography (eluent; n-hexane / ethyl acetate = 1/1) to obtain the desired product (0.55 g). Pale yellow oil. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl ₃ ) 3.31-3.48 (m, 2H), 4.04-4.22 (m, 1H), 4.37 (dd, J = 2.7, 11.7 Hz, 1H), 4.59-4.74 (m, 1H), 6.04 (brs, 2H).
(4) Synthesis of 3-chloro-1-methyl-4- (5-methylene-5H, 6H-1,4,2-dioxazin-3-yl) pyrazole-5-sulfonamide

3-Chloro-1-methyl-4- (5-iodomethyl-5H, 6H-1,4,2-dioxazin-3-yl) pyrazole-5-sulfonamide (0.55 g, 1.3 mmol) -Dissolved in dimethoxyethane (10 ml) and stirred under ice cooling. Subsequently, 28% sodium methoxide in methanol (0.6 g, 3.1 mmol) was slowly added at 0 ° C., followed by stirring for 1 hour. 2N hydrochloric acid was added to stop the reaction, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed successively with water and saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and evaporated to give an oil. The obtained oil was purified by silica gel column chromatography (eluent; n-hexane / ethyl acetate = 1/1) to obtain the desired product (0.36 g). Colorless solid. Mp 116-119 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl ₃ ) 4.15 (s, 3H), 4.52 (s, 2H), 4.53 (d, J = 2.8 Hz, 1H), 4 .93 (d, J = 2.8 Hz, 1H) 6.03 (brs, 2H).

  Next, examples of the compounds included in the present invention are shown in Tables 1 to 5 including the compounds synthesized in the above Examples, but the present compounds are not limited thereto. However, the symbols in the table have the same meaning as described above.

  [Table 1]

―――――――――――――――――――――――――――――――
R ² R ³ R ⁴ R ⁵ R ⁶
―――――――――――――――――――――――――――――――
H H H H H
H Me H H H
H H H Me H
H Me Me H H
H Me H Me H
H H H Me Me
H Me Me Me H
H Me H Me Me
H Me Me Me Me
H CH ₂ I H H H
H CH ₂ I Me H H
H Et H H H
6-Me H H H H
6-Me Me H H H
6-Me H H Me H
6-Me Me Me H H
6-Me Me H Me H
6-Me H H Me Me
6-Me Me Me Me H
6-Me Me H Me Me
6-Me Me Me Me Me
6-Me CH ₂ I H H H
6-Me CH ₂ I Me H H
6-Me Et H H H
6-Cl H H H H
6-Cl Me H H H
6-Cl H H Me H
6-Cl Me Me H H
6-Cl Me H Me H
6-Cl H H Me Me
6-Cl Me Me Me H
6-Cl Me H Me Me
6-Cl Me Me Me Me
6-Cl CH ₂ I H H H
6-Cl CH ₂ I Me H H
6-Cl Et H H H
6-F H H H H
6-F Me H H H
6-F H H Me H
6-F Me Me H H
6-F Me H Me H
6-F H H Me Me
6-F Me Me Me H
6-F Me H Me Me
6-F Me Me Me Me
6-F CH ₂ I H H H
6-F CH ₂ I Me H H
6-F Et H H H
6-CF ₃ H H H H
6-CF ₃ Me H H H
6-CF ₃ H H Me H
6-CF ₃ Me Me H H
6-CF ₃ Me H Me H
6-CF ₃ H H Me Me
6-CF ₃ Me Me Me H
6-CF ₃ Me H Me Me
6-CF ₃ Me Me Me Me
6-CF ₃ CH ₂ I H H H
6-CF ₃ CH ₂ I Me H H
6-CF ₃ Et H H H
5-Me-6-Cl H H H H
5-Me-6-Cl Me H H H
5-Me-6-Cl H H Me H
5-Me-6-Cl Me Me H H
5-Me-6-Cl Me H Me H
5-Me-6-Cl H H Me Me
5-Me-6-Cl Me Me Me H
5-Me-6-Cl Me H Me Me
5-Me-6-Cl Me Me Me Me
5-Me-6-Cl CH ₂ I H H H
5-Me-6-Cl CH ₂ I Me H H
5-Me-6-Cl Et H H H
5-I H H H H
5-I Me H H H
5-I H H Me H
5-I Me Me H H
5-I Me H Me H
5-I H H Me Me
5-I Me Me Me H
5-I Me H Me Me
5-I Me Me Me Me
5-I CH ₂ I H H H
5-I CH ₂ I Me H H
5-I Et H H H
5-NHCHO H H H H
5-NHCHO Me H H H
5-NHCHO H H Me H
5-NHCHO Me Me H H
5-NHCHO Me H Me H
5-NHCHO H H Me Me
5-NHCHO Me Me Me H
5-NHCHO Me H Me Me
5-NHCHO Me Me Me Me
5-NHCHO CH ₂ I H H H
5-NHCHO CH ₂ I Me H H
5-NHCHO Et H H H
5-CH ₂ NHSO ₂ Me H H H H
5-CH ₂ NHSO ₂ Me Me H H H
_{5-CH 2 NHSO 2 Me H} H Me H
5-CH ₂ NHSO ₂ Me Me Me H H
5-CH ₂ NHSO ₂ Me Me H Me H
_{5-CH 2 NHSO 2 Me H} H Me Me
5-CH ₂ NHSO ₂ Me Me Me Me H
5-CH ₂ NHSO ₂ Me Me H Me Me
5-CH ₂ NHSO ₂ Me Me Me Me Me
5-CH ₂ NHSO ₂ Me CH ₂ I H H H
5-CH ₂ NHSO ₂ Me CH ₂ I Me H H
5-CH ₂ NHSO ₂ Me Et H H H
―――――――――――――――――――――――――――――――――――――――
[Table 2]

―――――――――――――――――――――――――――――――
R ² R ³ R ⁴ R ⁵ R ⁶
―――――――――――――――――――――――――――――――
H H H H H
H Me H H H
H H H Me H
H Me Me H H
H Me H Me H
H H H Me Me
H Me Me Me H
H Me H Me Me
H Me Me Me Me
H CH ₂ I H H H
H CH ₂ I Me H H
H Et H H H
5-CF ₃ H H H H
5-CF ₃ Me H H H
5-CF ₃ H H Me H
5-CF ₃ Me Me H H
5-CF ₃ Me H Me H
5-CF ₃ H H Me Me
5-CF ₃ Me Me Me H
5-CF ₃ Me H Me Me
5-CF ₃ Me Me Me Me
5-CF ₃ CH ₂ I H H H
5-CF ₃ CH ₂ I Me H H
5-CF ₃ Et H H H
―――――――――――――――――――――――――――――――
[Table 3]

―――――――――――――――――――――――――――――――
R ² R ³ R ⁴ R ⁵ R ⁶
―――――――――――――――――――――――――――――――
H H H H H
H Me H H H
H H H Me H
H Me Me H H
H Me H Me H
H H H Me Me
H Me Me Me H
H Me H Me Me
H Me Me Me Me
H CH ₂ I H H H
H CH ₂ I Me H H
H Et H H H
―――――――――――――――――――――――――――――――
[Table 4]

―――――――――――――――――――――――――――――――
R ¹ R ² R ³ R ⁴ R ⁵ R ⁶
―――――――――――――――――――――――――――――――
Me H H H H H
Me H Me H H H
Me H H H Me H
Me H Me Me H H
Me H Me H Me H
Me H H H Me Me
Me H Me Me Me H
Me H Me H Me Me
Me H Me Me Me Me
Me H CH ₂ I H H H
Me H CH ₂ I Me H H
Et H H H H H
Et H Me H H H
Et H H H Me H
Et H Me Me H H
Et H Me H Me H
Et H H H Me Me
Et H Me Me Me H
Et H Me H Me Me
Et H Me Me Me Me
Et H CH ₂ I H H H
Et H CH ₂ I Me H H
CH ₂ OMe H H H H H
CH ₂ OMe H Me H H H
CH ₂ OMe H H H Me H
CH ₂ OMe H Me Me H H
CH ₂ OMe H Me H Me H
CH ₂ OMe H H H Me Me
CH ₂ OMe H Me Me Me H
CH ₂ OMe H Me H Me Me
CH ₂ OMe H Me Me Me Me
CH ₂ OMe H CH ₂ I H H H
CH ₂ OMe H CH ₂ I Me H H
Ph H H H H H
Ph H Me H H H
Ph H H H Me H
Ph H Me Me H H
Ph H Me H Me H
Ph H H H Me Me
Ph H Me Me Me H
Ph H Me H Me Me
Ph H Me Me Me Me
Ph H CH ₂ I H H H
Ph H CH ₂ I Me H H
2-Py H H H H H
2-Py H Me H H H
2-Py H H H Me H
2-Py H Me Me H H
2-Py H Me H Me H
2-Py H H H Me Me
2-Py H Me Me Me H
2-Py H Me H Me Me
2-Py H Me Me Me Me
2-Py H CH ₂ I H H H
2-Py H CH ₂ I Me H H
Me Me H H H H
Me Me Me H H H
Me Me H H Me H
Me Me Me Me H H
Me Me Me H Me H
Me Me H H Me Me
Me Me Me Me Me H
Me Me Me H Me Me
Me Me Me Me Me Me Me
Me Me CH ₂ I H H H
Me Me CH ₂ I Me H H
Et Me H H H H
Et Me Me H H H
Et Me H H Me H
Et Me Me Me H H
Et Me Me H Me H
Et Me H H Me Me
Et Me Me Me Me H
Et Me Me H Me Me
Et Me Me Me Me Me Me
Et Me CH ₂ I H H H
Et Me CH ₂ I Me H H
CH ₂ OMe Me H H H H
CH ₂ OMe Me Me H H H
CH ₂ OMe Me H H Me H
CH ₂ OMe Me Me Me H H
CH ₂ OMe Me Me H Me H
CH ₂ OMe Me H H Me Me
CH ₂ OMe Me Me Me Me H
CH ₂ OMe Me Me H Me Me
CH ₂ OMe Me Me Me Me Me
CH ₂ OMe Me CH ₂ I H H H
CH ₂ OMe Me CH ₂ I Me H H
Ph Me H H H H
Ph Me Me H H H
Ph Me H H Me H
Ph Me Me Me H H
Ph Me Me H Me H
Ph Me H H Me Me
Ph Me Me Me Me H
Ph Me Me H Me Me
Ph Me Me Me Me Me
Ph Me CH ₂ I H H H
Ph Me CH ₂ I Me H H
2-Py Me H H H H
2-Py Me Me H H H
2-Py Me H H Me H
2-Py Me Me Me H H
2-Py Me Me H Me H
2-Py Me H H Me Me
2-Py Me Me Me Me H
2-Py Me Me H Me Me
2-Py Me Me Me Me Me
2-Py Me CH ₂ I H H H
2-Py Me CH ₂ I Me H H
Me Cl H H H H
Me Cl Me H H H
Me Cl H H Me H
Me Cl Me Me H H
Me Cl Me H Me H
Me Cl H H Me Me
Me Cl Me Me Me H
Me Cl Me H Me Me
Me Cl Me Me Me Me Me
Me Cl CH ₂ I H H H
Me Cl CH ₂ I Me H H
Et Cl H H H H
Et Cl Me H H H
Et Cl H H Me H
Et Cl Me Me H H
Et Cl Me H Me H
Et Cl H H Me Me
Et Cl Me Me Me H
Et Cl Me H Me Me
Et Cl Me Me Me Me
Et Cl CH ₂ I H H H
Et Cl CH ₂ I Me H H
CH ₂ OMe Cl H H H H
CH ₂ OMe Cl Me H H H
CH ₂ OMe Cl H H Me H
CH ₂ OMe Cl Me Me H H
CH ₂ OMe Cl Me H Me H
CH ₂ OMe Cl H H Me Me
CH ₂ OMe Cl Me Me Me H
CH ₂ OMe Cl Me H Me Me
CH ₂ OMe Cl Me Me Me Me
CH ₂ OMe Cl CH ₂ I H H H
CH ₂ OMe Cl CH ₂ I Me H H
Ph Cl H H H H
Ph Cl Me H H H
Ph Cl H H Me H
Ph Cl Me Me H H
Ph Cl Me H Me H
Ph Cl H H Me Me
Ph Cl Me Me Me H
Ph Cl Me H Me Me
Ph Cl Me Me Me Me
Ph Cl CH ₂ I H H H
Ph Cl CH ₂ I Me H H
2-Py Cl H H H H
2-PyClMeHHH
2-PyClHHMeH
2-PyClMeMeHH
2-PyClMeHMeH
2-PyClHHMeMe
2-PyClMeMeMeH
2-PyClMeHMeMe
2-Py Cl Me Me Me Me
_{2-Py Cl CH 2 I H} H H
_{2-Py Cl CH 2 I Me} H H
Me Br H H H H
Me Br Me H H H
Me Br H H Me H
Me Br Me Me H H
Me Br Me H Me H
Me Br H H Me Me
Me Br Me Me Me H
Me Br Me H Me Me
Me Br Me Me Me Me Me
Me Br CH ₂ I H H H
Me Br CH ₂ I Me H H
Et Br H H H H
Et Br Me H H H
Et Br H H Me H
Et Br Me Me H H
Et Br Me H Me H
Et Br H H Me Me
Et Br Me Me Me H
Et Br Me H Me Me
Et Br Me Me Me Me
Et Br CH ₂ I H H H
Et Br CH ₂ I Me H H
CH ₂ OMe Br H H H H
CH ₂ OMe Br Me H H H
CH ₂ OMe Br H H Me H
CH ₂ OMe Br Me Me H H
CH ₂ OMe Br Me H Me H
CH ₂ OMe Br H H Me Me
CH ₂ OMe Br Me Me Me H
CH ₂ OMe Br Me H Me Me
CH ₂ OMe Br Me Me Me Me
CH ₂ OMe Br CH ₂ I H H H
CH ₂ OMe Br CH ₂ I Me H H
Ph Br H H H H
Ph Br Me H H H
Ph Br H H Me H
Ph Br Me Me H H
Ph Br Me H Me H
Ph Br H H Me Me
Ph Br Me Me Me H
Ph Br Me H Me Me
Ph Br Me Me Me Me
Ph Br CH ₂ I H H H
Ph Br CH ₂ I Me H H
2-Py Br H H H H
2-Py Br Me H H H
2-Py Br H H Me H
2-Py Br Me Me H H
2-Py Br Me H Me H
2-Py Br H H Me Me
2-Py Br Me Me Me H
2-Py Br Me H Me Me
2-Py Br Me Me Me Me
_{2-Py Br CH 2 I H} H H
_{2-Py Br CH 2 I Me} H H
Me OMe H H H H
Me OMe Me H H H
Me OMe H H Me H
Me OMe Me Me H H
Me OMe Me H Me H
Me OMe H H Me Me
Me OMe Me Me Me H
Me OMe Me H Me Me
Me OMe Me Me Me Me
Me OMe CH ₂ I H H H
Me OMe CH ₂ I Me H H
Et OMe H H H H
Et OMe Me H H H
Et OMe H H Me H
Et OMe Me Me H H
Et OMe Me H Me H
Et OMe H H Me Me
Et OMe Me Me Me H
Et OMe Me H Me Me
Et OMe Me Me Me Me
Et OMe CH ₂ I H H H
Et OMe CH ₂ I Me H H
CH ₂ OMe OMe H H H H
CH ₂ OMe OMe Me H H H
CH ₂ OMe OMe H H Me H
CH ₂ OMe OMe Me Me H H
CH ₂ OMe OMe Me H Me H
CH ₂ OMe OMe H H Me Me
CH ₂ OMe OMe Me Me Me H
CH ₂ OMe OMe Me H Me Me
CH ₂ OMe OMe Me Me Me Me
CH ₂ OMe OMe CH ₂ I H H H
CH ₂ OMe OMe CH ₂ I Me H H
Ph OMe H H H H
Ph OMe Me H H H
Ph OMe H H Me H
Ph OMe Me Me H H
Ph OMe Me H Me H
Ph OMe H H Me Me
Ph OMe Me Me Me H
Ph OMe Me H Me Me
Ph OMe Me Me Me Me
Ph OMe CH ₂ I H H H
Ph OMe CH ₂ I Me H H
2-Py OMe H H H H
2-Py OMe Me H H H
2-Py OMe H H Me H
2-Py OMe Me Me H H
2-Py OMe Me H Me H
2-Py OMe H H Me Me
2-Py OMe Me Me Me H
2-Py OMe Me H Me Me
2-Py OMe Me Me Me Me
2-Py OMe CH ₂ I H H H
2-Py OMe CH ₂ I Me H H
Me H Et H H H
Me Me Et H H H
Me Cl Et H H H
Me Br Et H H H
Me OMe Et H H H
Et H Et H H H
Et Me Et H H H
Et Cl Et H H H
Et Br Et H H H
Et OMe Et H H H
CH ₂ OMe H Et H H H
CH ₂ OMe Me Et H H H
CH ₂ OMe Cl Et H H H
CH ₂ OMe Br Et H H H
CH ₂ OMe OMe Et H H H
Ph H Et H H H
Ph Me Et H H H
Ph Cl Et H H H
Ph Br Et H H H
Ph OMe Et H H H
2-Py H Et H H H
2-Py Me Et H H H
2-PyCl Et H H H
2-Py Br Et H H H
2-Py OMe Et H H H
―――――――――――――――――――――――――――――――――――――――
[Table 5]

―――――――――――――――――――――――――――――――
R ² R ³ R ⁴ R ⁵ R ⁶
―――――――――――――――――――――――――――――――
H H H H H
H Me H H H
H H H Me H
H Me Me H H
H Me H Me H
H H H Me Me
H Me Me Me H
H Me H Me Me
H Me Me Me Me
H CH ₂ I H H H
H CH ₂ I Me H H
H Et H H H
Cl H H H H
Cl Me H H H
Cl H H Me H
Cl Me Me H H
Cl Me H Me H
Cl H H Me Me
Cl Me Me Me H
Cl Me H Me Me
Cl Me Me Me Me
Cl CH ₂ I H H H
Cl CH ₂ I Me H H
Cl Et H H H
Me H H H H
Me Me H H H
Me H H Me H
Me Me Me H H
Me Me H Me H
Me H H Me Me
Me Me Me Me H
Me Me H Me Me
Me Me Me Me Me
Me CH ₂ I H H H
Me CH ₂ I Me H H
Me Et H H H
CF ₃ H H H H
CF ₃ Me H H H
CF ₃ H H Me H
CF ₃ Me Me H H
CF ₃ Me H Me H
CF ₃ H H Me Me
CF ₃ Me Me Me H
CF ₃ Me H Me Me
CF ₃ Me Me Me Me
CF ₃ CH ₂ I H H H
CF ₃ CH ₂ I Me H H
CF ₃ Et H H H
―――――――――――――――――――――――――――――――
The application amount of the compound of the present invention as a herbicide varies depending on the application scene, application time, application method, target weeds, cultivated crops, etc., but generally the amount of active ingredient is about 0.001 to 50 kg per hectare (ha). About 0.01 to 10 kg is preferable.

  The compound of the present invention can be used as a herbicide for paddy fields in any treatment method of soil treatment and foliage treatment under flooded water. As paddy field weeds, for example, weeping family (Potamogetonaceacetae) represented by Potamogeton distinctus, etc. ) Weeds, Gramineae weeds such as Leptochloa chinensis, Echinochloa crus-galli, Echinochloa oryzicola, etc. Juncoids, Shizui (Cirpus nipponicus), Cyperus seratinus (Cyperus difficile) and other species of Cyperaceae (Cyperaceae) (Lemnaceae) weeds, Cyprinaceae weeds represented by Murdania keisak, etc., Mizoroi korsakowii and Monochori vaginalids , Elytineaceae weeds typified by Elatine tridra, etc., Elytinaidae lysidae, represented by Amanania multiflora, Rotalae diaceae, etc. Oenotheraceae weeds, Abomame (Dopatrium junceum), Azena (Lindernia pyxidaria) and American Azena (Lindernia dubias), and the American genus Drosophila weed (Scrophularidae) (Bidens tripartita) Asteraceae represented by such (Compositae) weeds, and the like.

  Further, the compound of the present invention can be used as a field herbicide in any treatment method of soil treatment, soil admixture treatment, and foliage treatment. Examples of upland field weeds include Solanumae weeds represented by Solanum nigrum, Datura stramonium, etc., Siberacea weeds, and Sida spinosa represented by Sida spinosa. Convolvulaceae weeds, Convolvulaceae weeds such as Ipomoea purps. Amarant family represented by retroflexus aceae) weeds, cocklebur (xanthium pensylvanicum), ragweed (Ambrosia artemisiaefolia), sunflower (Helianthus annuus), galinsoga quadriradiata (Galinsoga ciliata), representative to the western thorns thistle (Cirsium arvense), Senecio vulgaris (Senecio vulgaris), Himejon (Erigeron annus), etc. Compositae weed, Rupippa indica, Shirapi (Sinapis arvensis), Raspberry (Caspella Bursapastoris) weed, Cypiferae weed, i) Weeds (Polygonaceae) typified by Polygonum convolvulus, etc., Species of genus Porphyraceuae (Portulacaeae) typified by Portulaca oleacea, etc. (Chechopadiacea) weeds represented by (Kochia scoparia) etc., Caryophyllaceae weeds represented by Stellaria mediaa (Caryophyllaceae) weeds, Veronica persicaceae weeds, etc. Tsuyukusa ( Cyprinaceae weeds, such as Commelina communis, Lamia ampleicaule, Ebium bursae (Liamium purpureum), Eurasians (Liamium purpureum) Euphorbiaceae weeds represented by E., etc., Rubiaceae weeds represented by Galium spurium, Rubia akane, etc., and Viraceae represented by Viola mansura (cereal), etc. Weed, American horned sanem Broad-leaved weeds such as leguminosae weeds represented by ia exaltata), Cassia obtusifolia, and the like.

  Wild sorghum (Sorgham dichotomiflorum), Johnson grass (Sorghum halo chilli), Echinochloa cru-galli var. Crus-galli , Barnyard grass (Digitaria ciliaris), oats (Avena fatua), blackgrass (Alopecurus myosuroides), barnyard grass (Eleusine indica), Enocologosa (Sateria viridis), Akinoe faberi), blackgrass (Alopecurus aegualis) gramineous weeds (Graminaceous weeds typified etc.), Cyperus (Cyperus rotundus, Cyperus esculentus) Cyperaceae weeds (Cyperaceous weeds typified like).

  The compound of the present invention can be applied not only to agricultural and horticultural fields such as paddy fields, upland fields and orchards, but also to the control of various weeds in non-agricultural fields such as playgrounds, open spaces and track ends.

  The compound of the present invention may be mixed and applied with other types of herbicides, various insecticides, fungicides, plant growth regulators, synergists, and the like, as necessary, during formulation or spraying.

  In particular, when mixed with other herbicides, cost reduction due to a decrease in the amount of applied medicine, expansion of the herbicidal spectrum due to the synergistic action of the mixed drugs, and higher herbicidal effects can be expected. At this time, a combination with a plurality of known herbicides is also possible.

  Preferred herbicides to be used in combination with the compound of the present invention include, for example, pyrazosulfuron-ethyl (general name), bensulfuron methyl (bensulfuron-methyl / generic name), and sinosulfuron (cinosulfuron / generic name). , Imazosulfuron (generic name), azisulfuron (generic name), halosulfuron methyl (general name), pretilachlor (pretilachlor / generic name), esprocarbz (generic name) Generic name), pyrazoxifene (general name), benzophenap (ben) offenap / generic name), diimron (common name), bromobutide (general name), naproanilide (generic name / generic name), clomeprop (generic name), CNP (generic name), clomethoxynyl name ), Bifenox (bifenox / generic name), oxadiazone (generic name), oxadialgyl (generic name), fenfentrol (general name), oxadiclomephone (generic name), indanophan / indofan Pentoxazone (Pentoxazole / generic name), pyriminobacmethyl (pyri) inobac-methyl / generic name), cihalohop-butyl (cyalofop-butyl / generic name), fentrazamide (fentrazamide / generic name), mefenacet (mefenacet / generic name), butachlor (butachlor / generic name), butenachlor (butenachlor) Name), dithiopyr (dithiopyl / generic name), benfrecetate (benfuresate / generic name), piributicalbu (pyributicarb / generic name), beniocarb (bentiocarb / generic name), dimethyl piperate (dimipeperate / generic name), molinate , Butamifos (general name), quinclorac (general) Name), simmethrin (common name), simethrin (common name), bensulide (common name), dimethamethrin (common name), MCPA, MCPB, etobenzanid (common name) ), Tenylchlor (tenylchlor / generic name), ethoxysulfuron (ethoxysulfuron / generic name), quinoclamamine (quinoclamine / generic name), benzobicyclone (benzoficlon / generic name), pyriftalid / bis (py) HSA-961 (test name), anilofos (generic name), O -701 (study name), cyclosulfamuron (general name), DASH-001 (study name), AVH-301 (study name), KUH-021 (study name), TH-547 (study name), etc. Can be given.

  When the compound of the present invention is applied as a herbicide, it is generally mixed with a suitable solid carrier or liquid carrier, and if desired, a surfactant, penetrant, spreading agent, thickener, antifreeze agent, binder. In addition, an anti-caking agent or an anti-decomposition agent can be added and put into practical use in any dosage form such as a solution, emulsion, wettable powder, dry flowable agent, flowable agent, powder or granule.

  In addition, from the viewpoint of labor saving and safety improvement, a preparation of any of the above dosage forms can be enclosed in a water-soluble package.

  Examples of the solid support include natural minerals such as kaolinite, pyrophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite and diatomaceous earth, inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate and potassium chloride, Synthetic silicic acid, synthetic silicate, etc. are mentioned.

  Examples of the liquid carrier include water, alcohols (ethylene glycol, propylene glycol, isopropanol, etc.), aromatic hydrocarbons (xylene, alkylbenzene, alkylnaphthalene, etc.), ethers (butyl cellosolve, etc.), ketones (cyclohexanone, etc.), Examples include esters (γ-butyrolactone, etc.), acid amides (N-methylpyrrolidone, N-octylpyrrolidone, etc.), vegetable oils (soybean oil, rapeseed oil, cottonseed oil, castor oil, etc.) and the like.

  These solid and liquid carriers may be used alone or in combination of two or more.

  As the surfactant, for example, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene fatty acid ester, sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester Surfactant, alkylbenzene sulfonate, lignin sulfonate, alkyl sulfosuccinate, naphthalene sulfonate, alkyl naphthalene sulfonate, salt of formalin condensate of naphthalene sulfonic acid, formalin condensate of alkyl naphthalene sulfonic acid Salts, polyoxyethylene alkylaryl ether sulfates or phosphates, polyoxyethylene styryl phenyl ether sulfates or phosphates and Ionic surfactants such as Kiruamin salts.

  The content of these surfactants is not particularly limited, but is usually in the range of 0.05 to 20 parts by weight with respect to 100 parts by weight of the preparation of the present invention. These surfactants may be used alone or in combination of two or more.

Next, formulation examples of the preparation when the compound of the present invention is used are shown. However, the formulation examples of the present invention are not limited to these. In the following formulation examples, “parts” means parts by weight.
Wettable compound of the present invention 0.1 to 80 parts Solid carrier 5 to 98.9 parts Surfactant 1 to 10 parts Others 0 to 5 parts Others include, for example, anti-caking agent, decomposition inhibitor and the like.
Emulsified compound of the present invention 0.1 to 30 parts Liquid carrier 55 to 95 parts Surfactant 4.9 to 15 parts Flowable agent Compound of the present invention 0.1 to 70 parts Liquid carrier 15 to 98.89 parts Surfactant 1 to 12 parts and others 0.01 to 30 parts Others include, for example, antifreezing agents and thickeners.
Dry flowable agent compound of the present invention 0.1 to 90 parts Solid carrier 0 to 98.9 parts Surfactant 1 to 20 parts Others 0 to 10 parts Others include, for example, binders, decomposition inhibitors and the like.
Liquid compounds of the present invention 0.01 to 30 parts Liquid carrier 0.1 to 50 parts Water 50 to 99.89 parts Others 0 to 10 parts Others include, for example, antifreezing agents and spreading agents.
Granules Compound of the present invention 0.01 to 10 parts Solid carrier 90 to 99.99 parts Others 0 to 10 parts Others include, for example, binders, decomposition inhibitors and the like.

  In use, the preparation is applied as it is or diluted 1 to 10,000 times with water.

Formulation Examples Next, specific examples of agrochemical formulations containing the compound of the present invention as an active ingredient are shown, but the invention is not limited thereto. In the following formulation examples, “parts” means parts by weight.

[Formulation Example 1] wettable powder compound of the present invention 1 20 parts Pyrophyllite 76 parts Solpol 5039 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industries, Ltd. trade name)
Carplex # 80 2 parts (Synthetic hydrous silicic acid: Shionogi & Co., Ltd. trade name)
The above is uniformly mixed and ground to obtain a wettable powder.

[Formulation Example 2] Milk Compound of the present invention No. 1 5 parts xylene 75 parts N-methylpyrrolidone 15 parts Solpol 2680 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name)
The above is uniformly mixed to obtain an emulsion.

[Composition Example 3] Flowable Agent Compound No. 1 25 parts Agrisol S-710 10 parts (nonionic surfactant: trade name of Kao Corporation)
Lnox 1000C 0.5 part (anionic surfactant: Toho Chemical Co., Ltd. trade name)
Xanthan gum 0.02 parts Water 64.48 parts After uniformly mixing the above, wet milling to obtain a flowable agent.

[Formulation Example 4] Dry flowable agent compound of the present invention No. 1 75 parts Hytenol NE-15 5 parts (anionic surfactant: Daiichi Kogyo Seiyaku Co., Ltd. trade name)
Vanillex N 10 parts (anionic surfactant: Nippon Paper Industries Co., Ltd. trade name)
Carplex # 80 10 parts (Synthetic hydrous silicic acid: Shionogi & Co., Ltd. trade name)
After uniformly mixing and pulverizing the above, a small amount of water is added and stirred and kneaded, granulated with an extrusion granulator, and dried to obtain a dry flowable agent.

[Formulation Example 5] Granules Invention compound No. 1 part bentonite 55 parts talc 44 parts After uniformly mixing and pulverizing the above, a small amount of water is added and stirred and mixed, granulated with an extrusion granulator, and dried to form granules.

  In addition, said DBSN means sodium dodecylbenzenesulfonate.

  Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples.

[Test Example 1] Herbicidal effect test by pretreatment of weed generation under flooding conditions After alluvial soil was put into a 1 / 30,000 are styrene cup, water was added and mixed to create a flooding condition with a depth of 4 cm. After seeding Nobies, firefly and koi seeds in the cup, rice seedlings at the 2.5 leaf stage were transplanted. On the day of sowing, the emulsion of the compound of the present invention prepared according to Formulation Example 2 was diluted with water to a predetermined dose and treated on the water surface. The cup was placed in a greenhouse at 25 to 30 ° C. to grow the plant, and 3 weeks after the chemical treatment, the herbicidal effect on various plants was examined according to the following criteria. The results are shown in Table 6.

Criterion 5 ... More than 90% of herbicide rate (almost completely dead)
4 ... Herbicidal Rate 70% or more and less than 90% 3 ... Herbicidal Rate 40% or more and less than 70% 2 ... Herbicidal Rate 20% or more and less than 40% 1 ... Herbicidal Rate 5% or more but less than 20% 0 ... Herbicidal Rate 5% or less (almost effective) None)
[Test Example 2] Herbicidal effect test by treatment with weed growing season under submerged conditions After alluvial soil was put into a 1 / 30,000 are styrene cup, water was added and mixed to prepare submerged conditions with a depth of 4 cm. Nobies, firefly, and oak seeds were mixed in the above cups and placed in a greenhouse at 25-30 ° C. to grow the plants. When Nobies, Firefly and Konagi reached the 1st to 2nd leaf stage, the emulsion of the compound of the present invention prepared according to Formulation Example 2 was diluted with water to a prescribed dose and treated on the water surface. Three weeks after the drug treatment, the herbicidal effect on various plants was examined according to the criteria of Test Example 1. The results are shown in Table 7.

[Test Example 3] Herbicidal effect test by soil treatment Put sterilized large soil in a plastic box 21cm long, 13cm wide and 7cm deep, and then use Nobie, Barbarella, Enocologosa, Oats, Blackgrass, Ichibibi, Ragweed, Aogateto, Shiroza, Inuta, Jacobe, Corn, Soybean, Rice, Wheat and Beet Seeds were sown in a spot shape, covered with about 1.5 cm of soil, and then the emulsion of the compound of the present invention prepared according to Formulation Example 2 was used as a prescribed medicine. It diluted with water so that it might become quantity, and it processed uniformly with the small spray to the soil surface. Three weeks after the drug treatment, the herbicidal effect on various plants was examined according to the criteria of Test Example 1. The results are shown in Table 8.

[Test Example 4] Herbicidal effect test by foliar treatment Put sterilized piled soil in a plastic box 21cm long, 13cm wide, 7cm deep, nobies, barbarella, green locust, oats, blackgrass, ibis, ragweed, bluehead, Shiroza, Inuta, Jacobe, Corn, Soybean, Rice, Wheat and Beet seeds were sown in a spot shape, covered with about 1.5 cm, and then grown in a greenhouse at 25 to 30 ° C. After growing for 14 days, the emulsion of the compound of the present invention prepared according to Formulation Example 2 was diluted with water to a predetermined dose, and uniformly treated with a small spray on the foliage. Three weeks after the drug treatment, the herbicidal effect on various plants was examined according to the criteria of Test Example 1. The results are shown in Table 9.

The symbols in Tables 6 to 9 represent the following meanings.
A: Nobies, B: Firefly, C: Konagi, D: Beetle, E: Enochorosa, F: Oats, G: Blackgrass, H: Ichibibi, I: Ragweed, J: Blue-headed, K: Shiroza, L: Inutade, M : Jacobe, a: transplanted rice, b: corn, c: soybean, d: direct sowing rice, e: wheat, f: beet [Table 6]
―――――――――――――――――――――――――
Compound Treatment dose A B C a
No. (G / a)
―――――――――――――――――――――――――
1 0.64 4 5 5 0
―――――――――――――――――――――――――
[Table 7]
―――――――――――――――――――――――――
Compound Treatment dose A B C
No. (G / a)
―――――――――――――――――――――――――
1 0.64 5 5 5
―――――――――――――――――――――――――
[Table 8]
―――――――――――――――――――――――――――――――――――
Compound Treatment dose A DF FGHI J KL M bc de ef
No. (G / a)
―――――――――――――――――――――――――――――――――――
1 1.6 4 3 1 0 0 1 5 5 4 5 5 3 1 0 2 5
―――――――――――――――――――――――――――――――――――
[Table 9]
―――――――――――――――――――――――――――――――――――
Compound Treatment dose A DF FGHI J KL M bc de ef
No. (G / a)
―――――――――――――――――――――――――――――――――――
1 1.6 4 2 4 0 0 5 5 5 5 5 5 5 4 3 0 0 5
―――――――――――――――――――――――――――――――――――
[Test Example 5] Herbicidal effect test on sulfonylurea herbicide-resistant weeds by pre-treatment of weed generation under flooded conditions After putting paddy field soil into a 1/10000 are plastic pot, add water and mix to a depth of 4 cm. The conditions were flooded. The above-mentioned pots were mixed with Inu firefly, Konagi and Azena, which are resistant to sulfonylurea herbicides, and the other pots were mixed with Inuta firefly, Konagi and Azena sensitive to sulfonylurea herbicides. On the day after sowing, the wettable powder of the compound of the present invention prepared according to the formulation example was diluted with water so that the active ingredient became a predetermined dosage on the water surface and treated on the water surface. Six weeks after drug treatment, the herbicidal effect on various weeds was investigated according to the criteria of the test examples. The results are shown in Table 10.

The symbols in Table 10 have the following meanings.
AR: Inu firefly resistant to conventional sulfonylurea herbicides, AS: Inu firefly sensitive to sulfonylurea herbicides, BR: Konagi resistant to conventional sulfonylurea herbicides, BS: sulfonylurea Konagi sensitive to herbicides, CR: Azena resistant to conventional sulfonylurea herbicides, CS: Azena sensitive to sulfonylurea herbicides [Table 10]
―――――――――――――――――――――――――――――――――――
Compound Treatment dose A R A S B B R B C C R C
No. (G / a)
―――――――――――――――――――――――――――――――――――
0.063 3 3 3 4 5 5
0.25 4 5 5 5 5 5
1 5 5 5 5 5 5
―――――――――――――――――――――――――――――――――――

  The pyrazole sulfonylurea compound of the present invention is useful as a selective herbicide for paddy rice and wheat.

Claims (12)

Formula (1):

[Wherein, X and Y are each independently a C _1-3 alkyl group, a C _1-3 haloalkyl group, a C _1-3 alkoxy group, a C _1-3 haloalkoxy group, a halogen atom, di (C _1-3 Alkyl) amino group or C _1-3 alkylamino group,
Z represents a nitrogen atom or a methine group,
G is

Represents
GJ- represents GJ-1 to GJ-7, where GJ-1 to GJ-7 have the following meanings:

Represents
E represents —CH ₂ —, —O— or —NH—,
R ¹ represents a C _1-3 alkyl group, a C _1-3 haloalkyl group, a C _1-3 alkoxy C _1-3 alkyl group, a phenyl group or a pyridyl group,
R ² represents a hydrogen atom, a C _1-3 alkyl group, a C _1-3 haloalkyl group, a C _1-3 alkoxy group, a halogen atom, —NHCHO or —CH ₂ NHSO ₂ CH ₃ ;
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom, a C _1-3 alkyl group or a C _1-3 haloalkyl group] and pesticidally acceptable salts thereof. R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, X and Y represent a methoxy group or a methyl group, and Z represents a nitrogen atom or a methine group. Its salt. G-J-represents GJ-1, represents R ² is a hydrogen atom, a methyl group, an iodine atom, a trifluoromethyl group, a fluorine atom, a chlorine atom, a -NHCHO or -CH ₂ NHSO ₂ CH _3, claim 2 The described compounds and their pharmaceutically acceptable salts G-J-represents GJ-2, E is -CH ₂ -, - represents O- or -NH- and, R ² represents a hydrogen atom, acceptable salts thereof The compounds and pesticides according to claim 2, wherein . The compound according to claim 2, wherein GJ- represents GJ-3, and R ² represents a hydrogen atom or a trifluoromethyl group, and an agrochemically acceptable salt thereof. The compound according to claim 2, wherein G-J- represents GJ-4 and R ² represents a hydrogen atom, and an pesticidally acceptable salt thereof. The compound according to claim 2, wherein G-J- represents GJ-5, R ¹ represents a methyl group, and R ² represents a hydrogen atom, a methyl group or a chlorine atom, and an agrochemically acceptable salt thereof. The compound according to claim 2, wherein G-J- represents GJ-6 and R ² represents a hydrogen atom, a methyl group or a chlorine atom, and a pesticide acceptable salt thereof. G-J- represents GJ-7, R ¹ represents a methyl group, an ethyl group, a methoxymethyl group, a phenyl group and a 2-pyridyl group, and R ² represents a hydrogen atom, a methyl group or a chlorine atom. 2. The compound according to 2, and an pesticidally acceptable salt thereof. 10. The compound according to claim 3 to 9, wherein R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, and an pesticidally acceptable salt thereof. A pesticide containing as an active ingredient at least one selected from the sulfonylurea compounds according to claim 1 and salts acceptable as pesticides. A herbicide containing as an active ingredient at least one selected from the sulfonylurea compounds according to claim 1 and salts acceptable as agricultural chemicals.