WO2007046440A1 - Herbicide composition - Google Patents

Abstract

[PROBLEMS] To provide a novel herbicide composition and a weeding method. [MEANS FOR SOLVING PROBLEMS] A herbicide composition containing both a compound (A) represented by the general formula (1) and at least one compound selected from among dymron, dimepiperate, and esprocarb; and a weeding method which comprises applying a compound (A) and at least one compound selected from among dymron, dimepiperate, and esprocarb either simultaneously or at an interval: [Chemical formula 1]

Description

 Herbicidal composition

 Technical field

 [0001] The present invention relates to a herbicide composition and a herbicidal method with reduced phytotoxicity to crops, particularly paddy rice.

 Background art

 [0002] Compound (A) is patent-pending as a herbicide for paddy rice, has an extremely low dosage and exhibits an effect on many weeds, and has high safety against paddy rice under normal planting conditions. Under shallow planting and leakage conditions, it may cause phytotoxicity to paddy rice.

 Daimlon, dimethylpiperate, and esprocalp are compounds that have been put to practical use as herbicides for paddy rice, but have been reported so far to reduce the phytotoxicity of compound (A) on paddy rice. ,.

 Patent Document 1 discloses that pyrazole sulfonylureas having a dioxazine ring bonded to a pyrazole ring have herbicidal activity. However, Patent Document 1 does not specifically disclose pyrazole sulfonylureas such as compound (A) in which a substituent is bonded to the dioxazine ring on the virazole ring.

 Patent Document 1: JP-A-7-118269

 Disclosure of the invention

 Problems to be solved by the invention

[0003] Currently, many compounds have been put to practical use as herbicides for paddy rice, but existing drugs always satisfy the requirement to selectively control only target weeds that do not cause phytotoxicity to paddy rice. It ’s not something.

 Means for solving the problem

[0004] As a result of diligent research to solve the above problems, the present inventors have found that a mixture of the compound (A) and Daimlone, dimethylpiperate or esprocarp has an effect of reducing phytotoxicity exceeding expectations. They found that when compound (A) was mixed with certain herbicides, they complemented each other's herbicidal spectrum without antagonizing each other, thereby completing the present invention. Snow That is, the present invention relates to a herbicide composition described in the following [1] and [2] (hereinafter referred to as the present composition), and a herbicidal method described in [3] and [4] (hereinafter referred to as the present invention). It is called a method.)

 (1) Equation (1):

[Chemical 1]

[Wherein R ¹ is a C alkyl group, a C haloalkyl group, a C alkoxy C alkyl group, a

 1-3 1-3 1-3 1-3 represents a phenyl group or a pyridyl group,

R ² is a hydrogen atom, C alkyl group, C haloalkyl group, C alkoxy group or halo.

 1-3 1-3 1-3

Represents a gen atom,

B

Represents an alkyl group, provided that at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is C alkyl

A force representing a 1-3 group or a C haloalkyl group, or R ³ and R ⁴ together represent = CH;

 1-3 2

X and Y are each independently a C alkyl group, C haloalkyl group, C alkoxy group,

 1-3 1-3 1-3 represents a Si group, a C haloalkoxy group, a halogen atom or a di (C alkyl) amino group,

1-3 1-3

 z represents a nitrogen atom or a methine group. And a pyrazole sulfo-lurea compound (A) represented by

A herbicidal composition containing at least one compound selected from the medium strengths of Daimlon, Dimepiperate and Esprocalp.

 [2] A herbicidal composition for paddy rice containing the compound (A) and at least one compound selected from among the mainstays of Daimlon, Dimepiperate, and Esprocalp.

[3] Middle selection of the compound (A) and Daimlon, Dimepiperate, and Esprocalp Herbicidal method for applying at least one kind of compound simultaneously or with a time difference

[4] A paddy field weeding method, wherein the compound (A) and at least one compound selected from Daimlon, dimethylpiperate and esprocarp are applied simultaneously or with a time difference.

 [5] Compound (A) and Group B (where B is a general name of pyrazosulfuron-ethylZ), bensulfuron-methylZ (generic name of bensulfuron-methylZ), synosulfuronZ (generic name of cinosulfuronZ) , ImazosulfuronZ (generic name), azimsulfuronZ (generic name), halosulfuron methyl (halosulfurmethyl)

011—11161; 1 ^ 17-common name), cyclosulfamuron (.7.105111 £ & 11111]: 0117-common name), etoxysulfuron (common name of ethoxysu uronZ), pyrazolate (generic name of pyrazolate), pyrazoxifene ( pyrazoxyf en / —common name), benzofenap / —common name, bromobutide (common name), naproanilideZ (generic name), pretilachlorZ (common name), butachlor (generic name), Thulchlor (generic name), CNP (generic name), chloromethoxynyl (chlome thoxynilZ generic name), bifenoxZ (common name), oxadiazon / (generic name), oxadiargylZ (generic name), pentoxaz (pentoxaz) oneZ generic name), caffeenstrol (cafenstroleZ generic name), ox aziclomefoneZ (common name), indanofan (inda nofanZ (generic name), pyriminobac-methylZ (common name), cyhalofop-butyl (common name), fentrazamide (general name), mefenacet (generic name), butenachlorZ (generic name) ), DithiopylZ (generic name), benfresate (generic name), piributicalp (generic name), beniocarbZ (generic name), molinate (generic name), butamifos / (generic name), kink Mouth rack (quinclorac / generic name), cinmesin (generic name of cinmethylinZ), cimetrin (simetrynZ generic name), bensulide (generic name), dimethametryn (common name), MCPA (generic name), MCP

B (generic name), etobenzanid (generic name), cuminoluron (cumyluron. Common name), benzobicyclon / -common name, pyriftalide (pyriftalid / -common name), bispyribac / -common name, pyrachlor (pyraclonilZ--common name), anilofos /- (Generic name), OK—701 (study name), penoxsulam Z (generic name), AVH—301 (study name), KUH-021 (study name;), TH-547 (study name), Bentazone (BentazoneZ) (Generic name), 2, 4— PA (—generic name), metamihop (generic name), flucetosulfuron (generic name), HOK—201 (—generic name), mesotrione (mesotrioneZ—generic name), properties ( PropanilZ (common name), quinoclaminne (common name) and clomeprop force. ) Strength A herbicidal composition comprising at least one selected compound.

 [6] A paddy rice herbicide composition comprising the compound (A) and at least one compound selected from the group B.

 [7] A herbicidal method in which the compound (A) and the at least one compound selected from group B power are applied simultaneously or with a time difference.

 [8] A method for weeding paddy fields, wherein the compound (A) and the at least one compound selected from the group B force are applied simultaneously or at a time difference.

 The invention's effect

 [0005] According to the present invention, the phytotoxicity to crops, particularly paddy rice, caused by the compound (A) which is an active ingredient of the herbicide is reduced by Daimlon, dimethylpiperate and esprocalp, and the herbicidal effect on various weeds Does not drop. Mixtures of compound (A) with certain herbicides complement each other in the herbicidal spectrum without antagonism. For these reasons, the utility in an actual application scene according to the present invention is extremely high.

 BEST MODE FOR CARRYING OUT THE INVENTION

 In the present specification, the symbol Ph in the formula represents a phenol group, Me represents a methyl group, and Bu represents a butyl group.

 Compound (A) can be produced by the method shown in the following reaction formulas 1 to 3.

 (Reaction formula 1)

[Chemical 2]

 (twenty three)

X、 Yおよび zは前記と同様の意味を表す。〕 反応式 1は 4— (5H, 6H- 1, 4, 2 ジォキサジン— 3—ィル）ピラゾールー 5—ス ルホンアミド（2)を塩基存在下または非存在下、 2—フエノキシカルボ-ルァミノピリミ ジン (またはトリァジン） (3)と反応させて化合物（1)を製造する方法を示す。 [Where,

X, Y, and z represent the same meaning as described above. Reaction Formula 1 is 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfonamide (2) in the presence or absence of a base, 2-phenoxycarbo-laminopyrimidine (or triazine). ) A method for producing compound (1) by reacting with (3) is shown.

 In this reaction, (3) is usually used in an amount of 0.5 to 10-fold mol, preferably 0.9 or 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 dimethylamine, 1,8 diazabicyclo [5. 4. 0] 7undecene and 1,4-diazabicyclo [2.2.2] octane and other organic bases, n-butyllithium and sec-butyllithium and other organic lithiums, lithium diisopropylamide and Organic lithium amides such as lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide can be mentioned. The base is usually used in an amount of 0 to 10-fold mol, preferably 0 to 2-fold mol based on (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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl And mixed solvents thereof. The reaction temperature is usually 90 ° C and 200 ° C, preferably 0 ° C and 120 ° C.

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

 (Reaction formula 2)

[Chemical 3]

X、 Yおよび zは前記と同様の意味を表す。〕 反応式 2は 4— (5H, 6H- 1, 4, 2 ジォキサジン— 3—ィル）ピラゾールー 5—ス ルホニルカーノメート (4)を塩基存在下または非存在下、 2 アミノビリミジン (または トリァジン） (5)と反応させて化合物（1)を製造する方法を示す。 [Where,

X, Y, and z represent the same meaning as described above. Reaction formula 2 is 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfonyl carnomate (4) in the presence or absence of a base and 2-aminopyrimidine (or Triazine) A method for producing compound (1) by reacting with (5) is shown.

 In this reaction, (5) is usually used in an amount of 0.5 to 10-fold mol, preferably 0.9 or 1.1-fold mol with respect to (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 dimethylamine, 1,8 diazabicyclo [5. 4. 0] 7undecene and 1,4-diazabicyclo [2.2.2] octane and other organic bases, n-butyllithium and sec-butyllithium and other organic lithiums, lithium diisopropylamide and Organic lithium amides such as lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide can be mentioned. The base is usually used in an amount of 0 to 10-fold mol, preferably 0 to 2-fold mol based on (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, carbon tetrachloride, chloroform, and 1,2-dichloro Halogenated hydrocarbons such as loetane, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoleketone and methylisobutylketone, and tolyl such as acetonitrile and propio-tolyl And mixed solvents thereof.

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

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

 (Reaction formula 3)

 [Chemical 4]

X、 Yおよび zは前記と同様の意味を表す。〕 反応式 3は 4— (5H, 6H- 1, 4, 2 ジォキサジン— 3—ィル）ピラゾールー 5—ス ルホ-ルイソシアナート（6)を塩基存在下または非存在下、 2 アミノビリミジン (また はトリァジン） (5)と反応させて化合物（1)を製造する方法を示す。 [Where,

X, Y, and z represent the same meaning as described above. Reaction scheme 3 is 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfol isocyanate (6) in the presence or absence of a base in the presence of 2 aminopyrimidine ( Alternatively, a method for producing compound (1) 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 or 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 dimethylamine, 1,8 diazabicyclo [5. 4. 0] 7undecene and 1,4-diazabicyclo [2.2.2] octane and other organic bases, n-butyllithium and sec-butyllithium and other organic lithiums, lithium diisopropylamide and Organic lithium amides such as lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide can be mentioned. The base is usually 0 to 10 times mol, preferably 0, relative to (3). 2 times mole used.

 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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl And mixed solvents thereof.

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

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

[0009] 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5 sulfonamide (2) used in the method shown in Reaction Formula 1 is the method shown in Reaction Formulas 4 and 6. Can be manufactured. Also, 4- (5H, 6H-1, 4, 2, dioxazin-3-yl) pyrazole-5-sulfolcarbamate (4) and 4 (5H, 6H-1) , 4, 2 dioxazine-3-yl) pyrazole-5-sulfol isocyanate (6) is made from 4- (5H, 6H- 1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfonamide (2) It can be synthesized with reference to the methods described in JP-A-59-219281 and JP-A-55-13266.

[0010] [Reaction Formula 4]

[Chemical 5]

I

 (7) (8)

 (9) (2)

R⁴、 R⁵および R⁶は前記と同様の意味を表す。〕 [Where,

R ⁴ , R ⁵ and R ⁶ represent the same meaning as described above. ]

 Reaction Scheme 4 is a method of reacting 5-chlorocap 4- (5H, 6H-1, 4, 2 dioxazine 3-yl) pyrazole (7) with sodium hydrosulfide. , 6H- 1, 4, 2—dioxazine 3-yl) pyrazole (8) (step A), (8) is reacted with chlorine or sodium hypochlorite and other chlorinated agents to give 4- (5H , 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfourel chloride (9) (step B), (9) is reacted with aqueous ammonia or ammonium carbonate (step C). ), 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5 sulfonamide (2).

 In the reaction of Step A, sodium sulfate is usually 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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl , N, N dimethylformamide, N, N dimethylacetamide and N-methyl Examples include amides such as rho-2-pyrrolidone, sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane, water, and mixed solvents thereof.

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

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

[0012] In the reaction of Step B, chlorine or sodium hypochlorite is usually used in an amount of 1 V, 100 times mol, preferably 2! And 10 times mol of (8).

 This reaction can use a solvent as needed. The solvent is not particularly limited as long as it is inert to the reaction. For example, halogenated hydrocarbons such as carbon tetrachloride, black mouth form and 1,2-dichloro mouth ethane, water, and a mixed solvent thereof may be used. Can be mentioned.

 The reaction temperature is usually -90! And 100 ° C, preferably -10! And 50 ° C. The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

[0013] In the reaction of Step C, ammonia or ammonium carbonate is usually 1.

 It is 0 !, then 100 times mole, preferably 2 !, and 5 times mole.

 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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-amides such as 2-pyrrolidone, sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane, water, and mixed solvents thereof It is done.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

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

[Scheme 5]

[Chemical 6] Cl ₂ or

 NaOCI I HCI

および R⁶は前記と同様の意味を表す。〕 [Where,

And R ⁶ represents the same meaning as described above. ]

 Reaction formula 5 is a reaction of 5 benzyl mercapto-4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole (10) with a chlorinating agent such as chlorine or sodium hypochlorite.

, 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfoyl chloride (9) is shown.

 In this reaction, chlorine or sodium hypochlorite is usually 1 to 1 relative to (10).

00 times mole, preferably 2 to 10 times mole is used.

 This reaction can use a solvent as needed. The solvent is not particularly limited as long as it is inert to the reaction. For example, halogenated hydrocarbons such as carbon tetrachloride, black mouth form and 1,2-dichloro mouth ethane, water, and a mixed solvent thereof may be used. Can be mentioned.

 The reaction temperature is usually -90! And 100 ° C, preferably -10! And 50 ° C. The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

 [0015] (9) can be derived into 4- (5H, 6H-1, 4, 2 dioxazine 3 yl) pyrazole-5-sulfonamide (2) by the step C in Reaction Scheme 4. Further, (1) can be produced by reacting (9) and (5) with reference to the method described in JP-A-7-118267.

 [Reaction formula 6]

[Chemical 7]

 (1 1) (12)

R⁵および R⁶は前記と同様の意味を表す。〕 [Where,

R ⁵ and R ⁶ represent the same meaning as described above. ]

 In Reaction Scheme 6, 4-position of 5- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole (11) on the pyrazole ring is n-butyllithium (n BuLi) or lithium diisopropylamide (LDA), etc. And then react with sulfur dioxide to give 4- (5H, 6H-1, 4, 2-dioxazine 3-yl) pyrazole-5-sulfinic acid lithium (12) (Step D) and (12) as N chlorosuccinate. A method for producing 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfourel chloride (9) by reacting with acid imide (Step E) is shown.

[0017] In the reaction of step D 1), n-butyllithium or lithium diisopropylamide is usually used in an amount of 1 to 100-fold mol, preferably 1 to 5-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, and ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran are used. And mixed solvents thereof.

 The reaction temperature is usually 120 ° C and 100 ° C, preferably 78 ° C and 10 ° C. The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

[0018] In the reaction of step D 2), disulfur diacid is usually used in an amount of 1.0 to 100 times mol, preferably 1 to 10 times mol, relative to (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, and ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran are used. As well as these mixed solvents I can get lost.

 The reaction temperature is usually 120 ° C and 100 ° C, preferably 78 ° C and 10 ° C. The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

[0019] In the reaction of Step E, N-chlorosuccinimide is usually used in an amount of 1.0 to 100 times mol, preferably 1 to 10 times mol to (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 These mixed solvents are mentioned.

 The reaction temperature is usually -90! And 100 ° C, preferably -10! And 50 ° C. The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

[0020] (9) can be derived from 4 step 5 of Reaction Scheme 4 to 4 (5H, 6H—1, 4, 2 dioxazine 3 yl) pyrazole-5 sulfonamide (2). 01 [0021] 5-Chromium used in the methods shown in Reaction Formulas 4 to 6 — 4— (5H, 6H— 1, 4, 2 Dioxazine-3-yl) pyrazole (7), 5 Benzyl mercapto-4— (5H, 6H-1, 4, 2 dioxazine-3 yl) pyrazole (10) and 4- (5H, 6H—1, 4, 2 dioxazine-3 yl) pyrazole (11) are It can be manufactured by the method shown in 15.

 (Reaction formula 7)

 [Chemical 8]

 (13) (14) _ = CI

_ = SCH ₂ Ph

 _ = H

R⁵および R⁶は前記と同様の意味を表し、 X¹はハロゲン原子 を表し、 Lは塩素原子、ベンジルチオ基または水素原子を表す。〕 反応式 7は、ピラゾール 4 ヒドロキサム酸（ 13)を隣接ジハロゲンィ匕アルキル（14 )と反応させて 4—(5H, 6H- 1, 4, 2 ジォキサジン 3 ィル）ピラゾール（7)、 ( 10)または（11)を製造する方法を示す。 [Where,

R ⁵ and R ⁶ represent the same meaning as described above, X ¹ represents a halogen atom, and L represents a chlorine atom, a benzylthio group or a hydrogen atom. ] Scheme 7 shows that 4- (5H, 6H-1, 4, 2 dioxazine 3 yl) pyrazole (7), (10) or pyrazole 4 hydroxamic acid (13) is reacted with the adjacent dihalogen alkyl (14). A method for producing (11) will be described.

 In this reaction, (14) is usually used in an amount of 1.0 to 100 times mol, preferably 1 to 5 times mol, relative to (13).

 Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride and other inorganic bases, pyridine, 4-dimethylaminopyridine, Triethylamine, N, N dimethyldiamine, 1,8 diazabicyclo [5. 4. 0] —7 undecene and 1,4 diazabicyclic [2.2.2] Octane and other organic bases, n-butyllithium and sec-butyllithium And 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 times mol, preferably 0 to 2 times mol of (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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N-dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone, sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane, water, and mixed solvents thereof .

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

 The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours. (Reaction formula 8)

[Chemical 9]

R⁴、 R⁵、 R⁶および Lは前記と同様の意味を表し、 X²はハロゲン原 子、 C アルキルスルホ -ルォキシ基または C ハロアルキルスルホ -ルォキシ基を[Where,

R ⁴ , R ⁵ , R ⁶ and L have the same meaning as described above, and X ² represents a halogen atom, a C alkylsulfo-oxy group or a C haloalkyl sulfo-oxy group.

1-3 1-3

To express. ]

 In Reaction Scheme 8, pyrazole 4 carboxylic acid chloride (15) is reacted with alkoxyamine (16) to give pyrazole 4 hydroxamic acid ester (17) (step F), and (17) is reacted with a base (step G), 4- (5H, 6H-1, 4, 2 dioxazine 3 yl) pyrazole (7), (10) or (11) is produced.

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

 Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride and other inorganic bases, pyridine, 4-dimethylamino. Pyridine, triethylamine, N, N dimethyladiline, 1,8 diazabicyclo [5. 4. 0] —7 undecene and 1,4 diazabisic mouth [2.2.2] octane and other organic bases, n-butyllithium and sec Examples include organolithiums such as 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 10 times mol, preferably 0 to 2 times mol for (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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as, jetyl ether, diisopropyl ether, Ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, -tolyls such as acetonitrile and propio-tolyl, N, N-dimethylformamide, N, N-dimethylacetate Amides and amides such as N-methyl 2-pyrrolidone, water, and mixed solvents thereof can be mentioned.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

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

[0024] Bases used in the reaction in Step G 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— Examples 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 10 times mol, preferably 0 to 2 times mol of (17).

 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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

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

[Reaction Formula 9]

[Chemical 10]

 (16a) 17a

 (7a): Shi = CI (7b): Shi = CI

(10a): L = SCH ₂ Ph (10b): L = SCH ₂ Ph

 (1 1 a): L = H (1 1 b): L = H

X¹および Lは前記と同様の意味を表し、 R⁷および R⁸はそ れぞれ独立して水素原子または C アルキル基を表す。〕 [Where,

X ¹ and L represent the same meaning as described above, and R ⁷ and R ^{8 each} independently represent a hydrogen atom or a C alkyl group. ]

 1-3

 In Reaction Scheme 9, pyrazole 4 carboxylic acid chloride (15) is reacted with aryloxyamine (16a) to give pyrazole 4 hydroxamic acid ester (17a) (steps H) and (17a) as halogen or N— 4 (5-Haloalkyl-5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole (7a), (10a) or (11a) by reacting with halogenated succinimide (Step 1), (7a) , (10a) or (11a) is reduced (衙) and 4- (5 alkyl-5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole (7b), (10b) or ( l Shows how to produce ib).

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

Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride and other inorganic bases, pyridine, 4-dimethylaminopyridine, Triethylamine, N, N Dimethyla Diphosphorus, 1,8 diazabicyclo [5. 4. 0] —7 undecene and 1,4 diazabicyclic mouth [2.2.2] octane and other organic bases, n butyl lithium and sec butyl lithium, etc. 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 times mol, preferably 0 to 2 times mol for (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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N-dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

 The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours. In the reaction of Step I, halogen or N-halogenosuccinimide is usually used in an amount of 1 to 100-fold mol, preferably 1 to 5-fold mol based on (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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl , Carboxylic acid esters such as methyl acetate or ethyl acetate, alcohols such as methanol, ethanol or ethylene glycol, amides such as N, N-dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone , Water, and mixed solvents thereof The The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

 The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours. The reducing agent and reduction system used in the reaction of @J include alkali metal such as metallic sodium Z liquid ammonia, metallic lithium Z liquid ammonia and metallic sodium Zt-butyl alcohol-tetrahydrofuran mixed solvent, zinc Z acetic acid Zinc Z Hydroxide Potassium Z System using zinc metal such as Z water, triphenyltin hydride, diphenyltin hydride, tri-n-butyltin hydride, di-n-butyltin hydride, hydrogen Systems using organotin hydrides such as triethyltin and trimethyltin hydride, systems combining the above organotin compounds with free radical initiators such as azobisisobutyl thiol, silanes such as chlorosilane, triethylsilane and trimethylsilane , Lithium aluminum hydride, aluminum hydride sodium , Systems using metal hydride complexes such as sodium bis (2-methoxyethoxy) aluminum hydride, sodium borohydride and sodium cyanoborohydride, and borane derivatives such as diborane, trimethylamine borane and pyridin-borane And catalytic reduction systems such as hydrogen Z palladium carbon and hydrogen Z Raney nickel.

 The reducing agent is usually used in an amount of 1 to 100 times mol, preferably 1 to 5 times mol for (7a), (10a) or (11a).

 This reduction reaction proceeds even without solvent, but a solvent can be used as necessary. The solvent is not particularly limited as long as it is inert to each of the above reduction systems. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1 , Halogenated hydrocarbons such as 2-dichloroethane, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and-such as acetonitrile and propiotolyl Tolyls, carboxylic esters such as methyl acetate or ethyl acetate, alcohols such as methanol, 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! And 200 ° C, preferably -78! And 100 ° C. The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

[0029] [Reaction Scheme 10]

 [Chemical 11]

 (7d) L = CI (7e) L = CI

 (7c): L = C1

(10d) then = SCH ₂ Ph (10e) L = SCH ₂ P (10c): L = SCH ₂ Ph

 (11d) L = H (11e) L = H

 (11 c): L = H

X²および Lは前記と同様の意味を表す。〕 反応式 10は、 4— (5—ハロアルキル— 5H, 6H- 1, 4, 2 ジォキサジン— 3—ィ ル)ピラゾール（7c)、（10c)または（11c)を塩基存在下または非存在下、脱ハロゲン 化水素化して、各々対応する 4 （5 アルキリデン—5H, 6H- 1, 4, 2 ジォキサ ジン 3 ィル)ピラゾール（7d)、（10d)または（l id)とし（工程 K)、（7d)、（10d)ま たは（l id)を還元して（工程 L)、各々対応する 4 （5 アルキル 5H, 6H—1, 4 , 2 ジォキサジンー3 ィル)ピラゾール（7e)、（10e)または（l ie)を製造する方法 を示す。 [Where,

X ² and L have the same meaning as described above. Reaction scheme 10 is 4- (5-haloalkyl-5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole (7c), (10c) or (11c) in the presence or absence of a base, Dehydrohalogenated to the corresponding 4 (5 alkylidene-5H, 6H-1, 4, 2 dioxazine 3 yl) pyrazole (7d), (10d) or (l id) (step K), ( 7d), (10d) or (l id) is reduced (Step L), and the corresponding 4 (5 alkyl 5H, 6H—1, 4, 2 dioxazine-3-yl) pyrazole (7e), (10e ) Or (l ie) is shown.

[0030] Bases used in the reaction of Step K include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride, pyridine, 4- Organic bases such as dimethylaminopyridine, triethylamine, N, N-dimethylamine, 1,8 diazabicyclo [5.4.0] -7 undecene and 1,4 diazabicyclo [2.2.2] octane, n —Organic lithiums such as butyllithium and 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. Can be mentioned. The base is usually 0 to 100 times mol, preferably 0 to 5 times mol for (7c), (10c) or (11c). used.

 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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl 2-pyrrolidone, water, and mixed solvents thereof.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

 The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours. Examples of the reducing agent and reducing system used in the reaction in Step L include metallic sodium Z liquid ammonia, metallic lithium Z liquid ammonia, metallic lithium Z ethylamine and other alkali metal systems, aluminum mercury Z jetyl ether monohydrate and aluminum. -Moun nickel z Sodium hydroxide Z System using metal aluminum such as water, System using aluminum hydride compounds such as diisobutylaluminum hydride, Hydrosilanes such as triethylsilane trifluoroacetic acid and polymethylhydrosiloxane Z palladium carbon Metal hydride complexes such as lithium aluminum hydride, sodium aluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, sodium borohydride and sodium cyanoborohydride Systems using compounds, systems using borane derivatives such as diborane, trimethylamine borane and pyridine borane, hydrazine hydrate Z air, hydrazine hydrate Z potassium hexocyano (in) and hydroxylamine o-sulfonic acid Z Systems using diimides generated in reaction systems such as sodium hydroxide and sodium, heterogeneous catalytic reduction systems such as hydrogen Z palladium carbon and hydrogen Z Raney nickel, and hydrogen Z chlorotris (triphenylphosphine) rhodium (1 ), Hydrogen Z hydridocarbonyl tris (triphenylphosphine) rhodium (I), hydrogen Z rhodium acetate (Π) and hydrogen Z ruthenium acetate (π).

This reduction reaction proceeds even without solvent, but a solvent can be used as necessary. Solvent is above There is no particular limitation as long as it is inert to each reduction system. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1, 2- Halogenated hydrocarbons such as dichloroethane, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, -tolyls such as acetonitrile and propio-tolyl, Carboxylic acid esters such as methyl acetate or ethyl acetate, alcohols such as methanol, ethanol or ethylene glycol, amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone, water And mixed solvents thereof.

 The reaction temperature is usually -90! And 200 ° C, preferably -78! And 100 ° C. The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

[Scheme 11]

 [Chemical 12]

R⁸および Lは前記と同様の意味を表す。〕 反応式 11は、ピラゾール 4 ヒドロキサム酸エステル（ 17a)または（ 17b)を酸 (H + )と反応させて 4ー（5—ァルキルー511, 6H—1, 4, 2 ジォキサジン 3 ィル） ピラゾール（7b)、 (10b)または（1 lb)を製造する方法を示す。 [Where,

R ⁸ and L have the same meaning as described above. Reaction scheme 11 is a reaction of pyrazole 4 hydroxamic acid ester (17a) or (17b) with acid (H +) to give 4- (5-alkyl-511, 6H—1, 4, 2 dioxazine 3yl) pyrazole ( A method for producing 7b), (10b) or (1 lb) is indicated.

[0033] Examples of acids used in this reaction include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Can be mentioned. The acid is usually used in an amount of 0.01- to 100-fold mol, preferably 0.05 to 10-fold mol based on (17a) or (17b). 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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl 2-pyrrolidone, water, and mixed solvents thereof.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

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

[Reaction Formula 12]

 [Chemical 13]

 (18)

R⁸および X²は前記と同様の意味を表す。〕 [Where,

R ⁸ and X ² represent the same meaning as described above. ]

 Scheme 12 shows the reaction of pyrazole 4 hydroxamic acid (13) with halogenaryl (18) in the presence or absence of a base to form pyrazol 4 hydroxamic acid ester (17a ) Is shown.

[0035] In this reaction, (18) 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 and sodium hydride and other inorganic bases, pyridine, 4-dimethylamino. Pyridine, triethylamine, N, N dimethyladiline, 1,8 diazabicyclo [5. 4. 0] —7 undecene and 1,4 diazabisic mouth [2.2.2] octane and other organic bases, n-butyllithium and sec Butylliciu And 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 !, 100 times mol, preferably 0 !, and 5 times mol with respect to (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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl 2-pyrrolidone, water, and mixed solvents thereof.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

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

[Scheme 13]

 [Chemical 14]

 (19) (20)

R⁸および X²は前記と同様の意味を表す。〕 [Where,

R ⁸ and X ² represent the same meaning as described above. ]

 Scheme 13 shows the reaction of pyrazol 4 hydroxamic acid (13) in the presence or absence of a base with rholine, rhohydrin (19) or oxilan (20) to form a pyrazo 1-luo 4 hydroxamic acid ester used in Scheme 11 The method of manufacturing (17b) is shown.

[0037] In this reaction, (19) or (20) is usually used in an amount of 1 to 100-fold mol, preferably 2 to 5-fold mol with respect to (13).

Bases used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, Inorganic bases such as sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N dimethylaniline, 1,8 diazabicyclo [5. 4.0] —7 Wundecene and 1,4 diazabisic mouth [2.2.2] Organic bases such as octane, organic lithiums such as n-butyllithium and sec-butyllithium, lithium diisopropylamide and lithium bis (trimethylsilyl) amide Examples include organic lithium amides, and metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide. The base is usually used in an amount of 0 !, 100 times mol, preferably 0 !, and 5 times mol with respect to (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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl 2-pyrrolidone, water, and mixed solvents thereof.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

 The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours. (Reaction formula 14)

[Chemical 15]

 (7f): L = CI

(10f): L = SCH ₂ Ph

 (11f): L = H

R⁸および Lは前記と同様の意味を表す。〕 反応式 14は、ピラゾール 4 ヒドロキサム酸（ 13)を塩基存在下または非存在下、 ェピハロヒドリン（21)と反応させて、ピラゾールー 4ーヒドロキサム酸エステル（17c)と し（工程 L)、（17c)を酸または塩基で処理して、 4— (5 ヒドロキシアルキル— 5H, 6 H- 1, 4, 2 ジォキサジン 3 ィル）ピラゾール（7f)、（10f)または（l lf)とし（ェ 程 M)、次に、（7f)、（10f)または（l lf)をハロゲン化またはアルキルスルホニル化す る（工程 N)ことにより、各々対応する、 4一（5—ハロアルキル（またはアルキルスルホ -ルォキシアルキル） 5H, 6H- 1, 4, 2 ジォキサジン 3 ィル）ピラゾール（7 c)、（10c)または（11c)を製造する方法を示す。（7c)、（10c)または（11c)は反応 式 10で使用される。 [Where,

R ⁸ and L have the same meaning as described above. In the reaction scheme 14, pyrazole 4-hydroxamic acid (13) is reacted with epihalohydrin (21) in the presence or absence of a base to form pyrazole 4-hydroxamic acid ester (17c) (steps L) and (17c). Treatment with acid or base to give 4- (5 hydroxyalkyl-5H, 6 H-1, 4, 2 dioxazine 3 yl) pyrazole (7f), (10f) or (l lf) (step M); Next, (7f), (10f) or (l lf) is halogenated or alkylsulfonylated (step N) to give the corresponding 4- (5-haloalkyl (or alkylsulfo-alkyloxyalkyl) 5H, 6H -1, 4, 2 Dioxazine 3 yl) Pyrazole (7c), (10c) or (11c) is produced. (7c), (10c) or (11c) is used in Reaction Scheme 10.

 In the reaction of Step L, (21) is usually used in an amount of 1 to 100 times mol, preferably 1 to 5 times mol, of (13).

Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride. Organic bases, pyridine, 4-dimethylaminopyridine, triethylamine, N, N dimethylaniline, 1,8 diazabicyclo [5. 4. 0] —7 undecene and 1,4 diazabicycline [2.2.2] octane N, organic lithiums such as butyl lithium and sec butyl lithium, organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and sodium methoxide, sodium ethoxide and potassium t -Metal alkoxides such as butoxide. The base is usually used in an amount of 0 !, 100 times mol, preferably 0 !, and 5 times mol with respect to (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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl 2-pyrrolidone, water, and mixed solvents thereof.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours. Acids or bases used in the reaction of Step M 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, water Inorganic bases such as sodium oxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N dimethylamine, 1 , 8 Diazabicyclo [5. 4. 0] —Organic bases such as 7-undecene and 1,4-Diazabicyclo [2.2.2] octane, Organolithiums such as n-butyllithium and sec-butyllithium, Lithium diisopropylamide and Organic lithium amides such as lithium bis (trimethylsilyl) amide And sodium methoxide, and metal alkoxides such as sodium Umuetokishido and potassium t- butoxide. The acid or base is usually used in an amount of 0 to 100-fold mol, preferably 0 to 5-fold mol based on (17c). Used.

 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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

 The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours. In the reaction of Step N, the halogenating agent or alkyl sulfonating agent is usually 1 to 100 times mol, preferably 1 to 5 times mol of (7f), (10 f) or (l lf). Used in moles.

 Examples of the halogenating agent used in this reaction include hydrohalic acids such as hydrogen chloride, hydrogen bromide and hydrogen iodide, phosphorus halides such as phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and phosphorus tribromide. , Phosphonic acid triphenyl z benzil chloride and triphenylphosphine Z tetrasalt-carbon, etc., methanesulfonyl chloride and halogenated sulfone such as P-toluenesulphonyl, and thiol chloride And thionyl halides such as thiol bromide.

 Examples of the alkyl sulfonating agent used in this reaction include halogenated sulfones such as methane chloride chloride and p-toluene 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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as: ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methinoretinoleketone and methylisobutylketone;-such as acetonitrile and propio-tolyl Examples include tolyls, amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone, water, and mixed solvents thereof.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C. The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

[Scheme 15]

 [Chemical 16]

NH ₂ OH

 (15) ^ (13)

 (C base) In Reaction Scheme 15, Pyrazole-4 is a reaction of hydroxyamine with or without a base in the presence or absence of a base. A method for producing 4-hydroxamic acid (13) is shown.

[0043] In this reaction, hydroxylamine is usually used in an amount of 1 to 100-fold mol, preferably 1 to 5-fold mol based on (15).

 Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride and other inorganic bases, pyridine, 4-dimethylamino. Pyridine, triethylamine, N, N dimethyladiline, 1,8 diazabicyclo [5. 4. 0] —7 undecene and 1,4 diazabisic mouth [2.2.2] octane and other organic bases, n-butyllithium and sec Examples include organolithiums such as 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! And 100 times mol, preferably 0! And 5 times mol of (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, carbon tetrachloride, chloroform, and 1,2-dichloroethane. Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, acetone, methinoretinoleketone And ketones such as methyl isobutyl ketone, -tolyls such as acetonitrile and propio-tolyl, amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone, water, and these The mixed solvent is mentioned.

 The reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.

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

[0044] After completion of the reaction, the target product obtained by the above reaction can be isolated and purified by operations such as filtration, extraction, washing, column chromatography, recrystallization and distillation.

 [0045] The ability to specifically describe synthesis examples of compounds below The present invention is not limited by these.

[Synthesis Example 1]

N— ((4, 6-Dimethoxypyrimidine 1-2-yl) aminocarbole) 3—Black mouth 1-Methyl- ₄ ( _5- methyl-5H, 6H-1, 4, 2 Dioxazine 3-yl) pyrazole 5— Synthesis of sulfonamide (Compound No. 1)

 [Chemical 17]

ァセトニトリル（8ml)に 3 クロ口一 1—メチル 4— (5—メチル 5H, 6H— 1, 4, 2 ジォキサジン— 3—ィル）ピラゾールー 5—スルホンアミド（0. 64g、 2. 2mmol)と N— (4, 6 ジメトキシピリミジン— 2—ィル）力ルバミン酸フエ-ル（0. 59g、 2. lmm ol)を溶解し、 1, 8 ジァザビシクロ [5. 4. 0]— 7 ゥンデセン（0. 33g、 2. 2mmol )を加え、室温で 1時間撹拌した。水（8ml)をカ卩えた後、ジェチルエーテルで抽出し た。得られた水層に 12%塩酸をカ卩えて pHlに調整し、ジェチルエーテルで再度抽 出した。得られたジェチルエーテル溶液を水および塩ィ匕ナトリウム飽和水溶液で順 次洗浄後、無水硫酸ナトリウムで乾燥、溶媒留去した。得られた残渣を n—へキサン で洗浄、乾燥して目的物（0.40g)を得た。融点 177— 179°C。プロトン核磁気共鳴 ケミカルシフト値 δ (ppm) (CDCl中） 1.38(d, J = 6.6Hz, 3H), 3.69— 3.72 (

1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfonamide (0.664 g, 2.2 mmol) and N in acetonitrile (8 ml) — Dissolve (4, 6 dimethoxypyrimidine-2-yl) strength rubamate (0.59 g, 2. lmm ol), and add 1,8 diazabicyclo [5. 4. 0] — 7 undecene (0. 33 g, 2.2 mmol) was added and stirred at room temperature for 1 hour. Water (8 ml) was added and extracted with jetyl ether. Add 12% hydrochloric acid to the aqueous layer, adjust to pHl, and extract again with jetyl ether. I put it out. The obtained jetyl ether solution was washed successively with water and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was washed with n-hexane and dried to obtain the desired product (0.40 g). Melting point 177-179 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 1.38 (d, J = 6.6Hz, 3H), 3.69— 3.72 (

 Three

m, IH), 3.96 (s, 6H), 4.13—4.18 (m, IH), 4.30 (s, 3H), 4.49—4.63 (m, IH), 5.77 (s, IH), 7.67 (brs, IH) , 12.91 (brs, 1H).

(Synthesis Example 2)

 N-((4, 6 Dimethoxypyrimidine 1-2-yl) aminocarbole) 3 Black mouth 4— (5 Yodomethyl— 5H, 6H-1, 4, 2 Dioxazine-3-yl) — 1-Methylpyrazo 1 Synthesis of Luo 5-sulfonamide (Compound No. 2)

 [Chemical 18]

原料に 3 クロロー 4 （5 ョードメチルー 5H, 6H-1, 4, 2 ジォキサジンー3 —ィル）—1—メチルビラゾール— 5—スルホンアミド（0.090g、0.21mmol)を用い 、合成例 1と同様にして目的物（0. 10g)を得た。融点 91— 94°C

3 Chloro-4 (5 odomethyl-5H, 6H-1, 4, 2 dioxazin-3-yl) -1-methylbiazole-5-sulfonamide (0.090 g, 0.21 mmol) was used as the raw material in the same manner as in Synthesis Example 1. To obtain the desired product (0.10 g). Melting point 91—94 ° C

. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 3.28—3.42 (m, 2H)

 Three

 , 3.89-4.05 (m, 7Η), 4.04—4.12 (m, IH), 4.31 (s, 3H), 4.56—4.6 0 (m, IH), 5.79 (s, IH), 7.43 (brs, IH), 12.93 (s, 1H).

(Synthesis Example 3)

N-((4, 6 Dimethoxypyrimidine 1-2-yl) aminocarbol) 3 Black mouth 4— (5, 5 Dimethyl-5H, 6H-1, 4, 2 Dioxazine-3-yl) -1-methylpyrazo Synthesis of 5-Lusulfonamide (Compound No. 3) [Chemical 19]

原料に 3 クロ口— 4— (5, 5 ジメチル— 5H, 6H-1, 4, 2 ジォキサジン— 3 —ィル）—1—メチルビラゾールー 5—スルホンアミド（0.47g、 1.5mmol)を用い、 合成例 1と同様にして目的物（0.42g)を得た。融点 189— 191°C。プロトン核磁気 共鳴ケミカルシフト値 δ (ppm) (CDCl中） 1.41 (s, 6H), 3.78 (s, 2H), 3.97 (s

The raw material is 3 black mouth 4— (5,5 dimethyl-5H, 6H-1, 4, 2 dioxazine-3-yl) -1-methylbiazole-5-sulfonamide (0.47 g, 1.5 mmol) The target product (0.42 g) was obtained in the same manner as in Synthesis Example 1. Melting point 189-191 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 1.41 (s, 6H), 3.78 (s, 2H), 3.97 (s

 Three

 , 6H), 4.30 (s, 3H), 5.78 (s, IH), 7.58 (brs, IH), 12.92 (brs, 1H). (Synthesis Example 4)

 N-((4, 6 Dimethoxypyrimidine 1-yl) aminocarbole) 3 Black mouth 4— (5-methyl-5-methyl-5H, 6H-1, 4, 2 dioxazine-3-yl) — Synthesis of 1-methyl bilazole-5-sulfonamide (Compound No. 4)

[Chemical 20]

原料に 3 クロロー 4 （5 ョードメチルー 5—メチルー 5H, 6H-1, 4, 2 ジォ キサジン— 3—ィル）—1—メチルビラゾールー 5—スルホンアミド（0.21g、0.48m mol)を用い、合成例 1と同様にして目的物（0.14g)を得た。融点 90— 93°C。プロト ン核磁気共鳴ケミカルシフト値 δ (ppm) (CDCl中） 1.55(s, 3H), 3.30— 3.49 (

3 Chloro-4 (5 odomethyl-5-methyl-5H, 6H-1, 4,2 dioxazine-3-yl) -1-methylvirazole-5-sulfonamide (0.21 g, 0.48 mmol) was used as a raw material. The target product (0.14 g) was obtained in the same manner as in Synthesis Example 1. Melting point 90-93 ° C. Proto Nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 1.55 (s, 3H), 3.30— 3.49 (

 Three

m, 2H), 3.81-3.84 (m, IH), 3.97 (s, 6H), 4.23-4.30 (m, 4H), 5.8 0 (s, IH), 7.29 (brs, IH), 12.93 (s, 1H ).

(Synthesis Example 5)

 N-((4, 6 Dimethoxypyrimidine-2-yl) aminocarbole) — 1, 3 Dimethyl 4-— (5-Methyl 5H, 6H-1, 4, 2 Dioxazine-3-yl) pyrazole 5- Synthesis of Luhonamide (I Compound No.5)

[Chemical 21]

原料に 1, 3 ジメチルー 4— (5—メチル—5H, 6H-1, 4, 2 ジォキサジン— 3 —ィル）ピラゾールー 5—スルホンアミド（0.070g、0.26mmol)を用い、合成例 1と 同様にして目的物（0.090g)を得た。融点 180— 182°C。プロトン核磁気共鳴ケミカ ルシフト値 δ (ppm) (CDCl中） 1.36(d, J = 6.6Hz, 3H), 2.29 (s, 3H), 3.62

1,3 Dimethyl-4- (5-methyl-5H, 6H-1,4,2 dioxazine-3-yl) pyrazole-5-sulfonamide (0.070 g, 0.26 mmol) was used as a raw material in the same manner as in Synthesis Example 1. To obtain the desired product (0.090 g). Melting point 180—182 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 1.36 (d, J = 6.6Hz, 3H), 2.29 (s, 3H), 3.62

 Three

 -3.69 (m, IH), 3.97 (s, 6H), 4.11—4.16 (m, IH), 4.27 (s, 3H), 4.4 9-4.54 (m, IH), 5.78 (s, IH), 7.23 ( brs, IH), 12.74 (brs, 1H).

(Synthesis Example 6)

 N-((4, 6 Dimethoxypyrimidine 1-2-yl) aminocarbol) 3 Black mouth 4— (5 odomethyl— 5H, 6H-1, 4, 2 Dioxazine-3-yl) — 1-methylpyrazo 1 Lu 5—Synthesis of sulfonamide (Compound No. 6)

[Chemical 22]

原料に 4 （5 ョードメチルー 5H, 6H-1, 4, 2 ジォキサジンー3—ィル） 1, 3 ジメチルビラゾールー 5—スルホンアミド（0.53g、 1.3mmol)を用い、合成例 1 と同様にして目的物（0.34g)を得た。融点 66— 69°C。プロトン核磁気共鳴ケミカル シフト値 δ (ppm) (CDCl中） 2.34 (s, 3H), 3.36 (m, 2H), 3.92—4. 19 (m,

Using 4 (5 odomethyl-5H, 6H-1, 4, 2 dioxazin-3-yl) 1,3 dimethylvirazole-5-sulfonamide (0.53 g, 1.3 mmol) as the starting material Product (0.34 g) was obtained. Melting point 66—69 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 2.34 (s, 3H), 3.36 (m, 2H), 3.92—4. 19 (m,

 Three

 8H), 4.23 (s, 3H), 4.54-4.59 (m, 1H), 5.78 (s, 1H), 7.41 (brs, 1H), 12.64 (brs, 1H).

(Synthesis Example 7)

 N-((4, 6 Dimethoxypyrimidine 1-2-yl) aminocarbol) 1 4— (5, 5 Dimethyl-5H, 6H-1, 4, 2 Dioxazine-3-yl) 1, 3 Dimethylvirazole Synthesis of 5-sulfonamide (Compound No. 7)

[Chemical 23]

原料に 4ー（5, 5 ジメチルー 5H, 6H-1, 4, 2 ジォキサジンー3—ィル） 1, 3 ジメチルビラゾールー 5—スルホンアミド（0.13g、0.45mmol)を用い、合成例 1 と同様にして目的物（0.12g)を得た。融点 199— 201°C。プロトン核磁気共鳴ケミカ ルシフト値 δ (ppm) (CDCl中） 1.39 (s, 6H), 2.27 (s, 3H), 3.75 (s, 2H), 3.

Same as Synthesis Example 1 using 4- (5,5 dimethyl-5H, 6H-1, 4,2 dioxazine-3-yl) 1,3 dimethylbiazole-5-sulfonamide (0.13 g, 0.45 mmol) as raw material In this way, the desired product (0.12 g) was obtained. Melting point 199-201 ° C. Proton Nuclear Magnetic Resonance Chemica Shift value δ (ppm) (in CDCl) 1.39 (s, 6H), 2.27 (s, 3H), 3.75 (s, 2H), 3.

 Three

 97 (s, 6H), 4.27 (s, 3H), 5.78 (s, IH), 7.22 (brs, IH), 12.75 (s, 1H). (Synthesis Example 8)

 N-((4, 6 Dimethoxypyrimidine 1-2-yl) aminocarbol) 4— (5 pseudomethyl 5-methyl-5H, 6H—1, 4, 2 dioxazine-3-yl) 1, 3 dimethyl pyrazole 5- Synthesis of Sulfonamide (Compound No.8)

[Chemical 24]

原料に 4— (5 ョードメチル— 5—メチル—5H, 6H-1, 4, 2 ジォキサジン— 3 —ィル）— 1, 3 ジメチルビラゾール— 5—スルホンアミド（0.080g、0. 19mmol)を 用い、合成例 1と同様にして目的物（0.050g)を得た。融点 133— 135°C。プロトン 核磁気共鳴ケミカルシフト値 δ (ppm) (CDCl中） 1.63 (s, 3H), 2.29 (s, 3H), 3

4— (5-methyl-5-methyl-5H, 6H-1, 4, 2 dioxazine-3-yl) — 1,3 dimethylbiazole-5-sulfonamide (0.080 g, 0.19 mmol) was used as a raw material. The target product (0.050 g) was obtained in the same manner as in Synthesis Example 1. Melting point 133-135 ° C. Proton Nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 1.63 (s, 3H), 2.29 (s, 3H), 3

 Three

 .31-3.46 (m, 2H), 3.78—3.82 (m, IH), 3.97 (s, 6H), 4.17—4.27 (m, 4H), 5.79 (s, IH), 7.40 (brs, IH), 12.76 (brs, 1H).

(Synthesis Example 9)

 N-((4, 6 Dimethoxypyrimidine-2-yl) aminocarbole) — 1, 3 Dimethyl 4-— (6-Methyl 5H, 6H-1, 4, 2 Dioxazine-3-yl) pyrazole 5- Synthesis of Luhonamide (I Compound No.9)

[Chemical 25]

原料に 1, 3 ジメチルー 4— (6—メチル—5H, 6H-1, 4, 2 ジォキサジン— 3 —ィル）ピラゾールー 5—スルホンアミド（0. 14g、0.51mmol)を用い、合成例 1と同 様にして目的物（0.17g)を得た。融点 187— 189°C。プロトン核磁気共鳴ケミカル シフト値 δ (ppm) (CDC1中） 1.28(d, J = 8. OHz, 3H), 2.29 (s, 3H), 3.96 (s

1, 3 Dimethyl-4- (6-methyl-5H, 6H-1,4,2 dioxazine-3-yl) pyrazole-5-sulfonamide (0.14 g, 0.51 mmol) was used as the raw material, the same as in Synthesis Example 1. In this way, the desired product (0.17 g) was obtained. Melting point 187-189 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1.28 (d, J = 8. OHz, 3H), 2.29 (s, 3H), 3.96 (s

 Three

 , 6H), 3.99-4.04 (m, 2H), 4.27 (s, 3H), 4.29—4.33 (m, 1H), 5.78 (s, 1H), 7.26 (brs, 1H), 12.70 (brs, 1H).

[Synthesis Example 10]

N-((4, 6 Dimethoxypyrimidine 1-yl) aminocarbol) 3 Black mouth 1-Methyl- ₄ ( _5- methyl-5H, 6H-1, 4, 2 Dioxazine 3yl) pyrazole 5-sulfonamide (Compound No.1) (Part 2)

 Toluene (100 ml) with N-methoxycarbo-lu 3 1-methyl 4- (5-methyl-5H, 6H—1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfonamide (20.3 g, 57.5 mmol ) And 2-amino-4,6 dimethoxypyrimidine (9.40 g, 60.6 mmol) were added, and the mixture was heated to reflux for 4 hours while distilling off the by-produced methanol under reduced pressure (700 mmHg). After 15 ml of toluene was distilled off at the same temperature, it was cooled to room temperature with stirring. The precipitated solid was collected by filtration, washed with toluene, and dried to obtain the desired product (24. lg). Melting point 177—79. C.

[Synthesis Example 11]

N— ((4, 6 Dimethoxypyrimidine 1-yl) aminocarbole) 3 Black mouth 1-Methyl- ₄ ( _5- methyl-5H, 6H-1, 4, 2 Dioxazine 3-yl) pyrazole 5-sulfonamide (Compound No.1) (Part 3)

2 Amino 1,4,6 Dimethoxypyrimidine (0.46g, 3. Ommol) Acetonitrile (3ml) 1-methyl-4- (5-methyl-5H, 6H- 1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfol isocyanate (1. Og, 3. lmmol) Toluene (5 ml) solution was added and stirred at room temperature for 3 hours. The precipitated solid was collected by filtration, washed with toluene, and dried to obtain the desired product (1.2 g). Melting point 177-179 ° C.

[Synthesis Example 12]

N— ((4, 6 Dimethoxypyrimidine 1- 2-yl) aminocarbole) 3 Black mouth 1-Methyl- ₄ ( _5- methyl-5H, 6H- 1, 4, 2 Dioxazine 3-yl) pyrazole 5-sulfonamide (Compound No. 1) (Part 4)

 2 To a solution of amino-4,6 dimethoxypyrimidine (1.55 g, 10. Ommol) in acetonitrile (15 ml) was charged with pyridine (0.16 g, 2. Omol) and sodium cyanate (0.72 g, l mmol). 3 Chloro 1-methylolene 4 (5-methinoleyl 5H, 6H-1, 4, 2-dioxazine-3 yl) pyrazole-5 sulfosulfuryl chloride (3.45 g, 11. Ommo 1) for 1 hour at 40 ° C with stirring Over time, it was divided and introduced. The mixture was further stirred at 40 ° C for 1.5 hours. After cooling to room temperature, water (60 ml) was added, pH was adjusted to 35 with 35% hydrochloric acid, and the precipitated solid was collected by filtration. The obtained solid was washed with methanol and dried to obtain the desired product (4.70 g). Melting point 177-179 ° C.

[Synthesis Example 13]

 N— ((4, 6 Dimethoxypyrimidine-2-yl) aminocarbol) — 1-Methyl-4— (5-Methyl-5H, 6H- 1, 4, 2 Dioxazine-3-yl) pyrazole-5-sulfo Synthesis of Namide (Compound No. 10)

 [Chemical 26]

原料に 1ーメチルー 4ー（5—メチルー511, 6H- 1, 4, 2 ジォキサジンー3—ィル )ピラゾールー 5—スルホンアミド（0. 20g、 0. 77mmol)を用い、合成例 1と同様にし て目的物（0. 25g)を得た。融点 154— 157°C。プロトン核磁気共鳴ケミカルシフト値 δ (ppm) (CDC1中） 1. 35 (d, J = 6. 3Hz, 3H) , 3. 56— 3. 64 (m, 1H) , 4. 03

1-methyl-4- (5-methyl-511, 6H- 1, 4, 2 dioxazine-3-yl ) Pyrazole-5-sulfonamide (0.20 g, 0.777 mmol) was used in the same manner as in Synthesis Example 1 to obtain the desired product (0.25 g). Melting point 154—157 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1. 35 (d, J = 6. 3Hz, 3H), 3. 56— 3. 64 (m, 1H), 4.03

 Three

 —4. 13 (m, 7H), 4. 34 (s, 3H), 4. 44—4. 4. 50 (m, 1H), 5. 78 (s, 1H), 7. 4 5 (brs, 1H) , 7. 72 (s, 1H), 12. 66Hz (brs, 1H).

[Synthesis Example 14]

 Synthesis of (Compound No. 1) (Part 2)

 1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2 dioxazine-3 yl) pyrazole-5 sulfosulfuryl chloride (0.32 g, 1. Ommo 1) is dissolved in acetonitrile (4 ml). Add sodium cyanate (0.07 g, 1. 1 mmol), 2 amino-4,6 dimethoxypyrimidine (0.16 g, 1. Ommol) 40. Stir at C for 10 min. Pyridine (0.04 g, 0.5 mmol) was added dropwise over 3 minutes and stirred at 40 ° C for 1 hour. Under ice-cooling, methylene chloride (5 ml) was added, 12% hydrochloric acid was added to adjust to pH 1, and the phases were separated. The aqueous layer was extracted with methylene chloride. The obtained methylene chloride solutions were combined, washed with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (developing solution: n-hexane Z ethyl acetate = 1Z2) to obtain 0.37 g of the desired product. Melting point 177-179. C.

[Synthesis Example 15]

 N— ((4, 6-Dimethoxypyrimidine 1-2-yl) aminocarbole) 3—Black 1-Methyl 4 -— (5-Methylene 1 5H, 6H-1, 4, 2 Dioxazine 1— Yl) pyrazole —5-sulfonamide (Compound No. 21)

 [Chemical 27]

ァセトニトリル（6ml)に 3 クロ口一 1—メチル 4— (5—メチレン一 5H, 6H— 1, 4 , 2 ジォキサジン— 3—ィル）ピラゾールー 5—スルホンアミド（0. 13g、 0. 44mmol )と N— (4, 6 ジメトキシピリミジン一 2—ィル）力ルバミン酸フエ-ル（0. 13g、 0. 47 mmol)を溶解し、 1, 8 ジァザビシクロ [5. 4. 0]—7 ゥンデセン（0. 07g、 0. 46 mmol)を加え、室温で 1時間撹拌した。減圧下溶媒を留去し、 2規定塩酸を加えた 後、酢酸ェチルで抽出した。得られた酢酸ェチル溶液を無水硫酸ナトリウムで乾燥 後、減圧下濃縮すると油状物が得られた。この油状物にトルエンとへキサンの混合溶 媒を加え、析出した固体を濾取し、少量のトルエンで洗浄後、減圧乾燥することにより 、 目的物（0. 10g)を得た。白色固体。融点 164— 167°C。プロトン核磁気共鳴ケミカ ルシフト値 δ (ppm) (CDCl中） 3. 95 (s, 6H) , 4. 32 (s, 3H) , 4. 35 (s, 2H) , 4.

1-methyl 4- (5-methylene-l 5H, 6H— 1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfonamide (0.13 g, 0.44 mmol) with acetonitrile (6 ml) Dissolve N- (4, 6 dimethoxypyrimidine 1- 2-yl) force rubamate (0.13 g, 0.47 mmol) and add 1,8 diazabicyclo [5. 4. 0] —7 undecene (0 07 g, 0.46 mmol) was added and 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 then concentrated under reduced pressure to obtain an oil. To this oily substance, a mixed solvent of toluene and hexane was added, 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 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 3. 95 (s, 6H), 4. 32 (s, 3H), 4. 35 (s, 2H), 4.

 Three

 42 (d, J = 2.7Hz, 1H), 4.78 (d, J = 2.7Hz, 1H), 5.80 (s, 1H), 7.32 (brs, 1H), 11.98 ( brs, 1H).

(Reference Example 1)

 (1) (5 Benzylthio-1, 3, 1-Methylvirazole-4-yl) Synthesis of N-aryloxycarboxylic amide

 [Chemical 28]

ァリルォキシァミン塩酸塩（2. 3g、 21mmol)のテトラヒドロフラン（20ml)懸濁液に 、 0°Cでトリエチルァミン（2. 9g、 29mmol)を加え、室温で 5分間撹拌後、 5 ベンジ ルチオー3 クロロー 1ーメチルピラゾールー 4一力ルボン酸クロリド（2. lg、 7. Omm ol)のテトラヒドロフラン（10ml)溶液を滴下した。室温で 1時間撹拌後、水（100ml)を 加え、酢酸ェチルで抽出した。得られた酢酸ェチル溶液を塩化ナトリウム飽和水溶 液で洗浄、無水硫酸ナトリウムで乾燥、溶媒留去して目的物（2. 4g)を得た。油状物 質。プロトン核磁気共鳴ケミカルシフト値 δ (ppm) (CDCl中） 3. 45 (s, 3H) , 4. 11 (s, 2H), 4.53(d, J = 6.3Hz, 2H), 5.34— 5.45 (m, 2H), 6.00— 6.13 (m , 1H), 7.03-7.06 (m, 2H), 7.24— 7.28 (m, 3H), 9.14(brs, 1H)。

Triethylamine (2.9 g, 29 mmol) was added at 0 ° C to a suspension of allyloximine hydrochloride (2.3 g, 21 mmol) in tetrahydrofuran (20 ml) and stirred at room temperature for 5 minutes. Benzylthio-3 chloro-1-methylpyrazole-4 A solution of rubonic acid chloride (2. lg, 7. Ommol) in tetrahydrofuran (10 ml) was added dropwise. After stirring at room temperature for 1 hour, water (100 ml) was added and extracted with ethyl acetate. The obtained ethyl acetate solution was washed with a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain the desired product (2.4 g). Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 3. 45 (s, 3H), 4.11 (s, 2H), 4.53 (d, J = 6.3Hz, 2H), 5.34— 5.45 (m, 2H), 6.00— 6.13 (m, 1H), 7.03-7.06 (m, 2H), 7.24— 7.28 (m , 3H), 9.14 (brs, 1H).

[0062] (2) Synthesis of 5 benzylthio 1 3 black mouth 4— (5 odomethyl 1 5H, 6H— 1, 4, 2 dioxazine 3 yl) 1-methyl virazole

 [Chemical 29]

(5 -Benzylthio 3 1-methylpyrazole 4-yl)-N-aryloxycarboxylic acid amide (2.2 g, 6.5 mmol) in acetonitrile (70 ml) at 0 ° C with iodine (5.0 g, 20 mmol) I got After stirring at room temperature for 6 hours, water (150 ml) was added and extracted with ethyl acetate. The obtained ethyl acetate solution was washed successively with a saturated aqueous solution of sodium thiosulfate, a saturated aqueous solution of sodium hydrogen carbonate, a saturated aqueous solution of sodium chloride and water, dried over anhydrous sodium sulfate, and evaporated to remove the target product (3. Og) was obtained. Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 3.25 (s, 3H), 3.34— 3.42 (m, 2H)

 Three

 Ll, 4.04-4. Ll (m, 3H) 4.32—4.40 (m, 1H), 4.58—4.65 (m, 1H), 7.00—7.08 (m, 2H), 7.21—7.27 (m, 3H).

[0063] (3) Synthesis of 5-benzylthio 1-chloro 1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2 dioxazine 3 yl) pyrazole

 [Chemical 30]

5 ベンジルチオ一 3 クロ口一 4— (5 ョードメチル一 5H, 6H- 1, 4, 2 ジォ キサジン— 3—ィル）—1—メチルピラゾール（2. 9g、 6. 3mmol)のジメチルスルホキ シド（40ml)溶液に、水素化ホウ素ナトリウム（0. 47g、 12mmol)を加えた。 60°Cで 0 . 5時間撹拌後、 6%塩酸（200ml)を加え、酢酸ェチルで抽出した。得られた酢酸ェ チル溶液を塩ィ匕ナトリウム飽和水溶液および水で順次洗浄後、無水硫酸ナトリウムで 乾燥、溶媒留去して目的物（2. Og)を得た。油状物質。プロトン核磁気共鳴ケミカル シフト値 δ (ppm) (CDC1中） 1. 44 (d, J = 6. 6Hz, 3H) , 3. 24 (s, 3H) , 3. 74—

5 Benzylthio 1 3 Black Mouth 4— (5 Yodomethyl 1 5H, 6H-1, 4, 2 Dioxazine-3-yl) —1-Methylpyrazole (2.9 g, 6.3 mmol) in dimethyl sulfoxide To the (40 ml) solution was added sodium borohydride (0.47 g, 12 mmol). After stirring at 60 ° C for 0.5 hr, 6% hydrochloric acid (200 ml) was added, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed successively with saturated aqueous sodium chloride and water, dried over anhydrous sodium sulfate, and evaporated to give the desired product (2. Og). Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1. 44 (d, J = 6. 6Hz, 3H), 3. 24 (s, 3H), 3. 74—

 Three

 3. 85 (m, 1H), 4.04 (s, 2H), 4.22—4.29 (m, 1H), 4.56—4.65 (m, 1H), 6. 97-7 06 (m, 2H), 7. 19—7.21 (m, 3H).

(4) Synthesis of 1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2 dioxazine 1-3yl) pyrazole-5 sulfonamide (Part 1)

[Chemical 31]

5 Benzylthio 1 3 Black 1-Methyl 4- (5-Methyl 5H, 6H- 1, 4, 2-dioxazine 3 yl) pyrazole (1.9 g, 5.6 mmol) in methylene chloride (30 ml) and water (30 ml) and 35% hydrochloric acid (2.3 g, 22 mmol) were added, and 8% aqueous sodium hypochlorite solution (20.5 g, 22. Ommol) was added at 5 ° C with vigorous stirring. Stir for 5 hours. After introducing nitrogen to drive off excess chlorine, water (50 ml) was added and extracted with methylene chloride. The obtained methylene chloride solution was concentrated under reduced pressure, the residue was dissolved in tetrahydrofuran (8 ml), 28% aqueous ammonia (5 ml) was added at 0 ° C., and the mixture was stirred at room temperature for 0.25 hr. Water (20 ml) was added and extracted with jetyl ether, and the jetyl ether layer was discarded. 35% hydrochloric acid was added to the resulting aqueous layer, adjusted to pH 1 and extracted again with jetyl ether. The resulting jetyl ether solution was washed with a saturated aqueous solution of sodium chloride and anhydrous sulfur Drying with sodium acid and evaporation of the solvent gave the desired product (0.64 g). Melting point 120-122 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1.43 (d, J = 6.3Hz, 3H), 3

 Three

 .74-3.80 (m, 1H), 4.13 (s, 3H), 4.21—4.26 (m, 1H), 4.57—4.67 (m, 1H), 6.12 (brs, 2H).

(Reference Example 2)

 3 Black Mouth— 4— (5 Yodomethyl— 5H, 6H-1, 4, 2 Dioxazine— 3-yl) Synthesis of 1-methylpyrazole-5-sulfonamide

[Chemical 32]

 5 Benzylthio-3-chloro- 4— (5 odomethyl-5H, 6H-1, 4, 2-dioxazine-3-yl) 1-methylvirazole (0.24 g, 0.52 mmol) as the raw material, Reference Example 1 In the same manner as in (4), the desired product (0.090 g) was obtained. solid.

(Reference Example 3)

 (1) (5 Benzylthio-3 Chloro-1-methylpyrazole-4-yl) Synthesis of N— (2-methyl-2-propyloxy) carboxylic acid amide

[Chemical 33]

原料に 2—メチルー 2—プロべ-ルォキシァミン塩酸塩（1.2g、 9.7mmol)を用い 、参考例 1の（1)と同様にして目的物（1.8g)を得た。油状物質。プロトン核磁気共鳴 ケミカルシフト値 δ (ppm) (CDCl中） 1.88 (s, 3H), 3.36 (s, 3H), 4.11 (s, 2H

Using 2-methyl-2-probeoxyamine hydrochloride (1.2 g, 9.7 mmol) as a raw material, the target product (1.8 g) was obtained in the same manner as in Reference Example 1 (1). Oily substance. Proton nuclear magnetic resonance Chemical shift value δ (ppm) (in CDCl) 1.88 (s, 3H), 3.36 (s, 3H), 4.11 (s, 2H

 Three

 ), 4.45 (s, 2H), 5.08 (d, J = 9.9Hz, 2H), 7.01—7.06 (m, 2H), 7.22—7.28 (m, 3H), 9.15 (brs, 1H).

 (2) 5 Benzylthio 1 3 Black Mouth 4— (5 Yodomethyl 1 5-Methyl 5H, 6H— 1, 4, 2 Dioxazine 3-yl) Synthesis of 1-Methylvirazole

[Chemical 34]

原料に（5 べンジルチオー3 クロロー 1ーメチルビラゾールー 4 ィル） N— (2 ーメチルー 2—プロべ-ルォキシ）カルボン酸アミド（1.7g、4.8mmol)を用い、参 考例 1の（2)と同様にして目的物（2.3g)を得た。油状物質。プロトン核磁気共鳴ケミ カルシフト値 δ (ppm) (CDCl中） 1.61 (s, 3H), 3.23 (s, 3H), 3.39— 3.55 (

The raw material was (5 benzylthio-3 chloro-1-methylvirazole-4-yl) N— (2-methyl-2-pro-loxy) carboxylic acid amide (1.7 g, 4.8 mmol), and (2) of Reference Example 1 ) To give the desired product (2.3 g). Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 1.61 (s, 3H), 3.23 (s, 3H), 3.39—3.55 (

 Three

m, 2H), 3.91— 3.95 (m, 1H), 4. ll (s, 2H), 4.25—4.29 (m, 1H), 6.9 8— 7.06 (m, 2H), 7.21— 7.28 (m, 3H) .

 (3) Synthesis of 5 Benzylthio 1 3 Black Mouth 1-Methyl 4— (5,5 Dimethyl-5H, 6H— 1, 4, 2, Dioxazine 3 yl) pyrazole

[Chemical 35]

原料に（5—ベンジルチオ— 3—クロ口— 4— (5—ョードメチル— 5—メチル—5H, 6H-1, 4, 2 ジォキサジン一 3—ィル） 1—メチルビラゾール（1.7g、 3.6mmol )を用い、参考例 1の（3)と同様にして目的物（1. 3g)を得た。油状物質。プロトン核 磁気共鳴ケミカルシフト値 δ (ppm) (CDCl中） 1. 48 (s, 6H) , 3. 23 (s, 3H) , 3.

Raw material (5-Benzylthio-3—Black mouth— 4— (5-Modomethyl-5-methyl-5H, 6H-1, 4, 2 Dioxazine 1-yl) 1-Methylvirazole (1.7 g, 3.6 mmol ) Was used in the same manner as (3) in Reference Example 1 to obtain the desired product (1.3 g). Oily substance. Proton nucleus Magnetic resonance chemical shift value δ (ppm) (in CDCl) 1. 48 (s, 6H), 3. 23 (s, 3H), 3.

 Three

 88 (s, 2H), 4.05 (s, 2H), 6.99—7.06 (m, 2H), 7.21—7.28 (m, 3H). (4) Synthesis of 1-methyl 4- (5-, 5-dimethyl-5H, 6H—1,4,2 dioxazin 3-yl) pyrazole-5-sulfonamide

 [Chemical 36]

原料に 5—ベンジルチオ— 3—クロ口— 1—メチル—4— (5, 5—ジメチルー 5H, 6 H- 1, 4, 2 ジォキサジン 3 ィル）ピラゾール（1. 2g、 3. 4mmol)を用い、参考 例 1の (4)と同様にして目的物 (0. 47g)を得た。固体。

5-Benzylthio-3-chloro- 1-methyl-4- (5,5-dimethyl-5H, 6 H-1, 4, 2 dioxazine 3 yl) pyrazole (1.2 g, 3.4 mmol) was used as a raw material The target product (0.47 g) was obtained in the same manner as in Reference Example 1 (4). solid.

(Reference Example 4)

 3 Black Mouth 4— (5 Yodomethyl 1 5-Methyl 5H, 6H-1, 4, 2 Dioxazine-3 yl)-1-Methylvirazole-5 Sulfonamide

[Chemical 37]

原料に 5—ベンジルチオ一 3—クロ口一 4— (5—ョードメチル一 5—メチル 5H, 6 H- 1, 4, 2 ジォキサジン 3—ィル） 1ーメチルビラゾール（0. 50g、 1. Ommol )を用い、参考例 1の (4)と同様にして目的物 (0. 21g)を得た。固体。

5—Benzylthio-1, 3-chloromethyl 4- (5-methyl-5-methyl-5H, 6 H- 1, 4, 2 dioxazine 3-yl) 1-methylvirazole (0.50 g, 1. Ommol) ) Was used in the same manner as (4) in Reference Example 1 to obtain the desired product (0.21 g). solid.

(Reference Example 5) Dimethyl vilazo

原料に 5 ベンジルチオ—1, 3 ジメチルビラゾール 4 力ルポン酸クロリド（ 1. 6g、 5.7mmol)を用い、参考例 1の（1)と同様にして目的物（1.5g)を得た。油状物 質。プロトン核磁気共鳴ケミカルシフト値 δ (ppm) (CDCl中） 2.50 (s, 3H), 3.34

The target product (1.5 g) was obtained in the same manner as (1) of Reference Example 1 using 5 benzylthio-1,3 dimethylbirazole 4 force ruponic acid chloride (1.6 g, 5.7 mmol) as a raw material. Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 2.50 (s, 3H), 3.34

 Three

 (s, 3H), 3.92 (s, 2H), 4.48—4.51 (m, 2H), 5.32— 5.43 (m, 2H), 6.0 2-6.11 (m, 1H), 6.96— 7.00 (m, 2H), 7.23—7.30 (m, 3H), 9.77 (s, 1H).

 (2) Synthesis of 5 benzylthio-4- (5-iodomethyl-5H, 6H-1,4,2 dioxazine-3 yl) 1,3 dimethylvirazole

[Chemical 39]

原料に（5 べンジルチオ 1, 3 ジメチルビラゾールー 4 ィル）—N ァリルォ キシカルボン酸アミド (0.92g、 2.9mmol)を用い、参考例 1の（2)と同様にして目的 物（0.74g)を得た。融点 79— 81°C。プロトン核磁気共鳴ケミカルシフト値 δ (ppm) (CDCl中） 2.37(s, 3H), 3.29 (s, 3H), 3.36— 3.40 (m, 2H), 3.97—4.0

The starting material (0.74 g) was used in the same manner as (2) in Reference Example 1, using (5-benzylthio-1,3 dimethylbiazole-4-yl) -N allyloxycarboxylate (0.92 g, 2.9 mmol) as the raw material. Got. Melting point 79-81 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 2.37 (s, 3H), 3.29 (s, 3H), 3.36— 3.40 (m, 2H), 3.97—4.0

 Three

4 (m, 3H), 4.29-4.34 (m, 1H), 4.53—4.60 (m, 1H), 7.00—7.06 (m, 2H), 7.20-7.28 (m, 3H).

 (3) Synthesis of 5 benzylthio-1,3 dimethyl-4- (5-methyl-5H, 6H—1,4,2-dioxazine 3-yl) pyrazole

[Chemical 40]

原料に 5 べンジルチオー4 （5 ョードメチルー 5H, 6H- 1, 4, 2 ジォキサ ジンー3—ィル）ー1, 3 ジメチルビラゾール（0. 71g、 1. 6mmol)を用い、参考例 1 の（3)と同様にして目的物 (0. 19g)を得た。油状物質。

5 Benzylthio-4 (5 odomethyl-5H, 6H-1, 4, 2 dioxazin-3-yl) -1,3 dimethylvirazole (0.71 g, 1.6 mmol) was used as a raw material. ) To give the desired product (0.19 g). Oily substance.

 (4) 1,3 Dimethyl— 4— (5-Methyl-5H, 6H-1, 4, 2 Dioxazine-3-yl) pyrazole-5-sulfonamide synthesis

[Chemical 41]

原料に 5 べンジルチオ 1, 3 ジメチルー 4 （5—メチルー 5H, 6H- 1, 4, 2 ージォキサジンー3 ィル）ピラゾール（0. 19g、 0. 6mmol)を用い、参考例 1の（4) と同様にして目的物（0. 070g)を得た。固体。プロトン核磁気共鳴ケミカルシフト値 δ (ppm) (CDCl中） 1. 42 (s, 3H) , 2. 33 (s, 3H) , 3. 71— 3. 78 (m, IH) , 4.

Using 5 benzylthio 1,3 dimethyl-4 (5-methyl-5H, 6H- 1,4,2-dioxazine-3-yl) pyrazole (0.19 g, 0.6 mmol) as the raw material, the same as (4) in Reference Example 1 To obtain the desired product (0.070 g). solid. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 1. 42 (s, 3H), 2. 33 (s, 3H), 3. 71— 3. 78 (m, IH), 4.

 Three

 10 (s, 3H), 4.21-4.25 (m, IH), 4.60 (m, IH), 6.15 (s, 2H).

(Reference Example 6) 4— (5 Yodomethyl— 5H, 6H-1, 4, 2 Dioxazine-3-yl) 1, 3 Dimethylpyrazole-5-sulfonamide synthesis

[Chemical 42]

原料に 5 べンジルチオー4 （5 ョードメチルー 5H, 6H-1, 4, 2 ジォキサ ジンー3—ィル）ー1, 3 ジメチルビラゾール（0.70g、 1.6mmol)を用い、参考例 1 の (4)と同様にして目的物 (0.53g)を得た。固体。

5 Benzylthio-4 (5 odomethyl-5H, 6H-1, 4, 2 dioxazin-3-yl) -1,3 dimethylvirazole (0.70 g, 1.6 mmol) was used as a raw material, and (4) of Reference Example 1 In the same manner, the desired product (0.53 g) was obtained. solid.

(Reference Example 7)

 (1) Synthesis of (5-benzylthio-1,3 dimethylbiazole 4 yl) N— (2 methyl 2-propyloxy) carboxylic acid amide

[Chemical 43]

原料に 5 ベンジルチオ—1, 3 ジメチルビラゾール 4 カルボン酸クロリド（ 1. 10g、 3.9mmol)と 2—メチル—2—プロべ-ルォキシァミン塩酸塩（1.30g、 10.5 mmol)を用い、参考例 1の（1)と同様にして目的物（1.15g)を得た。油状物質。プ 口トン核磁気共鳴ケミカルシフト値 δ (ppm) (CDCl中） 1.89 (s, 3H), 2.51 (s, 3

Using 5 benzylthio-1,3 dimethylbiazole 4 carboxylic acid chloride (1.10 g, 3.9 mmol) and 2-methyl-2-propyloxyamine hydrochloride (1.30 g, 10.5 mmol) as raw materials, The target product (1.15 g) was obtained in the same manner as (1). Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 1.89 (s, 3H), 2.51 (s, 3

 Three

 H), 3.33 (s, 3H), 3.91 (s, 2H), 4.42 (s, 2H), 5.06 (d, J = ll.3Hz, 2H), 6.95— 7.01 (m, 2H), 7.24— 7.29 ( m, 3H), 9.77 (brs, 1H).

(2) 5 Benzylthio 4- (5-methyl 5-5-methyl 5H, 6H— 1, 4, 2— Sajin-3yl) -1,3 Synthesis of dimethylvirazole

 [Chemical 44]

 Using (5 benzylthio-1,3 dimethylbiazole 4-yl) N- (2-methyl-2-propyloxy) carboxylic acid amide (0.60 g, 1.8 mmol) as the starting material, (2) of Reference Example 1 In the same manner as described above, the desired product (0.78 g) was obtained. Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) l.60 (s, 3H), 2.37 (s, 3H), 3.27 (s, 3H), 3.39—3.52 (m, 2H), 3.88— 3.93 (m, 1H ), 4.00 (s, 2H), 4.19—4.24 (m, 1H), 7.0 0—7.05 (m, 2H), 7.20—7.24 (m, 3H).

 (3) Synthesis of 5 benzylthio-1,3 dimethyl-4- (5,5 dimethyl-5H, 6H—1,4,2 dioxazine 3 yl) pyrazole

[Chemical 45]

原料に 5 べンジルチオー4 （5 ョードメチルー 5—メチルー 5H, 6H—1, 4, 2 ージォキサジンー3—ィル）ー1, 3 ジメチルビラゾール（0.54g、 1.2mmol)を用 い、参考例 1の（3)と同様にして目的物 (0.38g)を得た。油状物質。プロトン核磁気 共鳴ケミカルシフト値 δ (ppm)l.47(s, 6H), 2.34 (s, 3H), 3.26 (s, 3H), 3. 86 (s, 2H), 4.00 (s, 2H), 6.98— 7.05 (m, 2H), 7.21— 7.25 (m, 3H)。

5 Benzylthio-4 (5 odomethyl-5-methyl-5H, 6H-1,4,2-dioxazine-3-yl) -1,3 dimethylvirazole (0.54 g, 1.2 mmol) was used as a raw material. The target product (0.38 g) was obtained in the same manner as 3). Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) l.47 (s, 6H), 2.34 (s, 3H), 3.26 (s, 3H), 3.86 (s, 2H), 4.00 (s, 2H), 6.98— 7.05 (m, 2H), 7.21— 7.25 (m, 3H).

(4) 1, 3 Dimethyl— 4— (5, 5 Dimethyl— 5H, 6H— 1, 4, 2 Dioxazine— Synthesis of 3-yl) pyrazole-5-sulfonamide

[Chem 46]

 Using 5 benzylthio 1,3 dimethyl-4 (5,5 dimethyl-5H, 6H—1,4,2 dioxazine 3 yl) pyrazole (0.34 g, 1. Ommol) as the raw material, In the same manner, the desired product (0.13 g) was obtained. solid.

(Reference Example 8)

 4 (5 odomethyl-5-methyl-5H, 6H- 1, 4, 2 dioxazine 3 yl) 1,3 Dimethylvirazole-5-sulfonamide synthesis

[Chemical 47]

原料に 5 べンジルチオー4 （5 ョードメチルー 5—メチルー 5H, 6H- 1, 4, 2 ージォキサジンー3—ィル）ー1, 3 ジメチルビラゾール（0. 20g、0. 44mmol)を用 い、参考例 1の（4)と同様にして目的物（0. 080g)を得た。固体。

5 Benzylthio-4 (5 odomethyl-5-methyl-5H, 6H-1, 4, 2-dioxazin-3-yl) -1,3 dimethylvirazole (0.20 g, 0.44 mmol) was used as a raw material, and Reference Example 1 In the same manner as in (4), the target product (0.080 g) was obtained. solid.

(Reference Example 9)

 (1) 2— Synthesis of (1, 3 dimethyl 5 benzylthiopyrazole 4 yl) carbo-laminooxy) ethyl propanoate

[Chemical 48]

5 Benzylthio 1 3 Black mouth 1-Methylpyrazole-4-Carboxylic acid (1.0 g, 3.8 mmol) in methylene chloride (20 ml) was added 2 ethyl amoxypropanoate (0.58 g, 4.4 mmol). ) And Nethyl N,-(3 dimethylaminopropyl) carbodiimide hydrochloride (0.83 g, 4.3 mmol) were added, and the mixture was stirred at room temperature for 12 hours. After evaporating the solvent under reduced pressure, water (50 ml) was added, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (developing solution: n-hexane Z ethyl acetate = 1Z1) to obtain 0.88 g of the desired product. Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1. 30 (t, J = 8Hz, 3H), 1. 57 (d, J = 10Hz, 3H), 2. 47 (s, 3H)) ,

Three

 3.28 (s, 3H), 3.40 (q, J = 8Hz, 2H), 4.18—4.32 (m, 2H), 4.62—4.71 (m, 1H), 6. 91-7. 07 (m, 2H), 7. 15—7.31 (m, 3H), 10. 40 (s, 1H). (2) Synthesis of (1, 3 dimethyl-5 benzylthiopyrazole-4 yl) N— (2 hydroxyisopropoxy) carboxylic acid amide

 [Chemical 49]

Lithium aluminum hydride (0.090 g, 2.4 mmol) in a suspension of jetyl ether (20 ml) with stirring at 5 ° C, 2— (1,3 dimethyl-5-benzylthiopyrazole-4-yl) Carbo-laminooxy) ethyl ester of propanoate (0.88 g, 2.3 mmol) A solution of 1 tel (5 ml) was added dropwise. After stirring at the same temperature for 2.5 hours, the reaction mixture was poured into ice water (20 ml), adjusted to pH 1 with 10% hydrochloric acid, and extracted with ethyl acetate. The ethyl acetate solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain the desired product (0.70 g). Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1.29 (d, J = 8Hz, 3H),

 Three

 2.74 (s, 3H), 3.26-3.50 (m, 1H), 3.42 (s, 3H), 3.59— 3.72 (m, 1H), 3.94 (s, 2H), 3.96-4.03 (m, 1H), 4.72 ( brs, 1H), 6.91— 7.02 (m, 2 H), 7.20-7.32 (m, 3H), 9.60 (brs, 1H).

[0083] (3) Synthesis of 5 benzylthio 1,3 dimethyl-4 (6-methyl-5H, 6H-1,4,2 dioxazine 3-yl) pyrazole

 [Chemical 50]

(1, 3 Dimethyl 5 benzylthiopyrazole 4 yl) N— (2 Hydroxysopropoxy) carboxylic acid amide (0.70 g, 2. lmmol) in methylene chloride (5 ml) was added to the salt of thionyl chloride (0.34 ml, 4.6 mmol) was added and refluxed for 1.5 hours, after which the solvent was distilled off. The obtained residue was dissolved in N, N dimethylformamide (10 ml), 55% sodium hydride (0.10 g, 2.3 mmol) was added at 5 ° C., and the mixture was further stirred at the same temperature for 1 hour. Water (20 ml) was added and the mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed with a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel thin layer chromatography (developing solution: n-hexane Z ethyl acetate = 1/1) to obtain the desired product (0.32 g). solid. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1

 Three

.37 (d, J = 8Hz, 3H), 2.33 (s, 3H), 3.28 (s, 3H), 3.95—4.05 (m, 2H), 4.08-4.13 (m, 1H), 4.44—4.51 (m, 1H), 6.99—7.06 (m, 2H), 7.09 -7.15 (m, 3H).

[0084] (4) 1, 3 Dimethyl— 4— (6-Methyl-5H, 6H— 1, 4, 2 Dioxazine-3— L) Synthesis of pyrazole 5-sulfonamide

 [Chemical 51]

原料に 5 べンジルチオ 1, 3 ジメチルー 4 （6—メチルー 5H, 6H- 1, 4, 2 ージォキサジンー3 ィル）ピラゾール（0. 32g、 1. Ommol)を用い、参考例 1の（4) と同様にして目的物 (0. 14g)を得た。固体。

Using 5 benzylthio 1,3 dimethyl-4 (6-methyl-5H, 6H-1,4,2-dioxazine-3 yl) pyrazole (0.32 g, 1. Ommol) as raw material, same as (4) of Reference Example 1 In this way, the desired product (0.14 g) was obtained. solid.

(Reference Example 10)

 (1) Synthesis of 3, 5 dichloro-1-methylbilazole-4 carbohydroxamic acid

[Chemical 52]

 Hydroxyloleamine hydrochloride (106.9 g, 1.538 mol) in water (200 ml) solution [5,5! /, 15 at 85 ° C. with 85% potassium hydroxide (101.5 g, 1.538 mol) A water (200 ml) solution was added and stirred at room temperature for 5 minutes. Next, a tetrahydrofuran solution (170 ml) of 3,5 dichloro-1-methylbiazole-4-carboxylic acid chloride (100.0 g, 0.5128 mol) at 3 to 8 ° C. was added dropwise over 2 hours. Further, after stirring at 5 ° C for 0.5 hour, 35% hydrochloric acid was adjusted to a pH of 3 to 4. The precipitated solid was collected by filtration, washed with water, and dried to obtain the desired product (94.9 g). Melting point 200 202 ° C (decomposition). Proton nuclear magnetic resonance chemical shift value δ (ppm) (in dimethylsulfoxide d) 3.79 (s, 3H), 9.24 (brs, 1H), 10.83 (brs, 1H).

 6

(2) Synthesis of N-aryloxy 3,5 dichloro 1-methylbiazole-4-carboxylic acid amide [Chemical 53]

炭酸カリウム（15. 8g、 114mmol)の水（60ml)溶液に、 3, 5 ジクロロー 1ーメチ ルビラゾールー 4 カルボヒドロキサム酸（20. Og、 95. 2mmol)と臭化ァリル（13. 8 g、 114mmol)のトルエン（60ml)溶液をカロえ、 50°Cにて 3時間撹拌した。室温まで 冷却後、 35%塩酸をカ卩えて pHlに調整し、析出した固体を濾取、水およびトルエン で順次洗浄後、乾燥して目的物（17. 2g)を得た。融点 96— 97°C。プロトン核磁気 共鳴ケミカルシフト値 δ (ppm) (CDC1中） 3. 84 (s, 3H) , 4. 51 (d, J = 6. 3Hz, 2

To a solution of potassium carbonate (15.8 g, 114 mmol) in water (60 ml) was added 3,5 dichloro-1-methylbilazole-4 carbohydroxamic acid (20. Og, 95.2 mmol) and allyl bromide (13.8 g, 114 mmol). Toluene (60 ml) solution was prepared and stirred at 50 ° C. for 3 hours. After cooling to room temperature, 35% hydrochloric acid was added to adjust the pH to 1. The precipitated solid was collected by filtration, washed successively with water and toluene, and dried to obtain the desired product (17.2 g). Melting point 96—97 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 3. 84 (s, 3H), 4. 51 (d, J = 6.3 Hz, 2

 Three

 H), 5.30- 5.46 (m, 2H), 5.94—6.13 (m, 1H), 8.80 (brs, 1H).

 (3) 3,5 dichloro 1- (5 odomethyl 1 5H, 6H— 1, 4, 2 dioxazine 1 3 yl) Synthesis of 1-methylpyrazole

[Chemical 54]

To a solution of N-aryloxy 3,5 dichloro 1-methylbiazole 4 carboxylic acid amide (40. Og, 160 mmol) in aceto-tolyl (200 ml), iodine (122 g, 481 mmol) was added and at room temperature 4. Stir for 5 hours. Saturated aqueous sodium thiosulfate solution (150 ml) was added, extracted with ethyl acetate, and the resulting ethyl acetate solution was washed successively with saturated aqueous sodium bicarbonate solution, saturated aqueous sodium chloride solution and water, then dried over anhydrous sodium sulfate, solvent Distilled off. The obtained residue was subjected to silica gel column chromatography (eluent: n-hexane). Purification with Z ethyl acetate = 5Z2) gave the desired product (54. Og). Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 3.37 (d, J = 6.9Hz, 2H), 3.83 (s

 Three

 , 3H), 3.99-4.06 (m, 1H), 4.32—4.38 (m, 1H), 4.54—4.62 (m, 1H)

[0088] (4) Synthesis of 3,5 dichloro 1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2 dioxazine 3-yl) pyrazole (Part 1)

 [Chemical 55]

 To a solution of sodium borohydride (0.30 g, 7.9 mmol) in N, N dimethylformamide (15 ml), 3, 5 dichloro-4 (5 odomethyl-5H, 6H-1, 4, 2 dioxazin-3-yl) — Add 1-methylvirazole (2.0 g, 5.3 mmol), 60. Stir at C for 0.5 h. After cooling to room temperature, water (10 ml) was added, and 35% hydrochloric acid was added to adjust to pHl, followed by extraction with ethyl acetate. The obtained ethyl acetate solution was washed successively with a saturated aqueous solution of sodium hydrogen carbonate, a saturated aqueous solution of sodium chloride and water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 5Z2) to obtain the desired product (1. lg). Melting point 50-51 ° C, boiling point 142 ° C / 0.3mmHg. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl

 Three

) 1.41 (d, J = 6.3Hz, 3H), 3.69—3.76 (m, 1H), 3.82 (s, 3H), 4.20—4.26 (m, 1H), 4.52—4.61 (m, 1H).

[0089] (5) Synthesis of 3-chromato 5-mercapto 1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2-dioxazine 3-yl) pyrazole

 To a suspension of 70% sodium hydrosulfide (4.3 g, 54 mmol) in N, N dimethylformamide (38 ml), 3, 5 dichloro 1-methyl-4- (5-methyl-5H, 6H- 1, 4, 2 Dioxazine-3-yl) pyrazole (3.8 g, 15 mmol) was added and stirred at 80 ° C. for 5.5 hours. After cooling to room temperature, water (50 ml) was added and insolubles were filtered off. 35% hydrochloric acid was added to the filtrate to adjust to pHI, and the precipitated solid was collected by filtration, washed with water and dried to obtain the desired product (2.55 g). Melting point 6 0—64. C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1. 48 (d, J = 6

 Three

 3Hz, 3H), 3.75 (s, 3H), 3.79— 3.85 (m, 1H), 4.28—4.32 (m, 1H), 4. 64-4.74 (m , 1H).

 (6) Synthesis of 1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2 dioxazine 3-yl) pyrazole-5-sulfo chloride

[Chemical 57]

3 Black mouth 5-Mercapto 1-Methyl 4- (5-Methyl 5H, 6H- 1, 4, 2 Dioxazine 1-yl) Pyrazole (2.5 g, lOmmol) 1,2 Dichloroethane (50 ml) Water (20 ml) was added to the solution, and chlorine (2. lg, 30 mmol) was introduced with vigorous stirring under ice cooling. During this time, the reaction temperature rose to 20 ° C. After introducing nitrogen and removing excess chlorine, the 1,2-dichloroethane layer was separated. The obtained 1,2-dichloroethane solution was washed successively with a saturated aqueous solution of sodium hydrogen sulfite and water, dried over anhydrous sodium sulfate, To obtain the target product (3. lg). Melting point 63-68 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1. 41 (d, J = 6. 3Hz, 3H), 3. 75— 3. 81 (m, 1H), 4. 20 (

 Three

 s, 3H), 4.23-4.28 (m, 1H), 4.54—4.64 (m, 1H).

[0091] (7) 3 1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2 dioxazine

 -3 yl) Synthesis of pyrazole-5 sulfonamide (Part 2)

 3 1-methyl 4- (5-methyl 5H, 6H- 1, 4, 2 dioxazine 1-yl) pyrazole-5-sulfoyl chloride (3. lg, 9.9 mmol) 1, 2 dichloroethane To the (30 ml) solution, 28% aqueous ammonia (1.5 g, 24.7 mmol) was added dropwise with ice-cooling and vigorous stirring. After stirring at room temperature for 0.5 hour, water (20 ml) and 35% hydrochloric acid (5.2 g, 50 mmol) were added, and the mixture was extracted with 1,2-dichloroethane. The obtained 1,2-dichloroethane solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain the desired product (2.8 g). Melting point 120—1-22. C.

 [0092] (8) Synthesis of 1-methyl 4- (5-methyl 5H, 6H —1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfonamide

 [Chemical 58]

3 1-methyl 4- (5-methyl 5H, 6H- 1, 4, 2 dioxazine 1-yl) pyrazole-5-sulfonamide (3. Og, lOmmol) in acetonitrile (15 ml) Anhydrous potassium carbonate (1.8 g, 13 mmol) and methyl chloroformate (0.96 g, 10 mmol) were added, and the mixture was heated to reflux for 1 hour. The residue obtained by distilling off the solvent under reduced pressure was dissolved in water (20 ml), and unnecessary substances were filtered off and extracted with 1,2 dichloroethane. 35% hydrochloric acid was added to the obtained aqueous layer to adjust to pH 1 and the precipitated solid was collected by filtration, washed with water and dried to obtain the desired product (2.4 g). Melting point 133-134 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1. 43 (d, J = 6.6Hz, 3H), 3.72 (s, 3H), 3.74— 3.81 (m, 1H), 4.21—4.30 (m, 1H), 4.25 (s, 3H), 4.56—4.66 (m, 1H ), 8.83 (brs, 1H).

[0093] [Reference Example 11]

 (1) Synthesis of 3,5 dichloro 1-methyl 4- (5-methylene 1 5H, 6H— 1, 4, 2 dioxazine 3-yl) pyrazole

 [Chemical 59]

3,5-Dichloro-4- (5-Hodomethyl-1-5H, 6H-1,4,2-Dioxazine-1-3-yl) 1-Methylbiazole (1.5 g, 4. Ommol) in tetrahydrofuran (10 ml) in potassium t -Butoxide (0.52 g, 4.6 mmol) was added, and the mixture was stirred at room temperature for 0.25 hour. A saturated aqueous solution of ammonium salt (20 ml) was added and extracted with ethyl acetate. The obtained ethyl acetate solution was washed successively with water and saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluent: n-hexane Z acetyl acetate = 1Z1) to obtain the desired product (0.88 g). Melting point 68—70 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 3.84 (s, 3H), 4.42

 Three

 (s, 2H), 4.45 (d, J = l.8Hz, 1H), 4.85 (d, J = l.8Hz, 1H).

[0094] (2) Synthesis of 3,5 dichloro 1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2 dioxazin 3yl) pyrazole (Part 2)

[0095] 3,5 Dichloro 1-methyl 4- (5-Methylene 1 5H, 6H— 1, 4, 2 Dioxazin-3-yl) pyrazole (2.8 g, llmmol) in a solution of ethyl acetate (56 ml) % Palladium-carbon (0.56 g) was added, and the mixture was stirred at room temperature for 17 hours under a hydrogen (1 atm) atmosphere. 5% Palladium-carbon (0.05 g) was added, and the mixture was further stirred for 1 hour under the above conditions, and the catalyst was filtered off. The solvent is also distilled off, and the resulting residue is subjected to alumina column chromatography (solution The resulting product (2.6 g) was obtained by purification with liquid separation (Korokuholm). Melting point 50—51 ° C.

 [0096] [Reference Example 12]

 Synthesis of 3, 5 dichloro 1-methyl 4- (5-methyl 5H, 6H- 1, 4, 2 dioxazine 3-yl) pyrazole (Part 3)

 [0097] N-aryloxy 3,5 dichloro- 1-methylbirazole-4 To a solution of rubonic acid amide (0.50 g, 2. Ommol) in toluene (5 ml), trifluoromethanesulfonic acid (0.10 g, 1 Ommol) was added and refluxed for 20 hours. The obtained toluene solution was washed successively with saturated aqueous potassium carbonate solution and water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 1/1) to obtain the desired product (0.08 g). Melting point 50—51 ° C.

 [0098] [Reference Example 13]

 (1) Synthesis of N- (n-Butylaminocarbol) 3 1-methyl 4— (5-Methyl-5H, 6H—1, 4, 2 Dioxazine-3-yl) pyrazole-5-sulfonamide [ Chemicalization 60]

3 1-methyl 4- (5-methyl 5H, 6H- 1, 4, 2 dioxazine 1-yl) pyrazole-5-sulfonamide (5.31 g, 18. Ommol) 1,2-dichloroethane ( 30 ml) solution was added anhydrous potassium carbonate (3.76 g, 27. Ommol) and n-butyl isocyanate (2.14 g, 21.6 mmol), and the mixture was heated to reflux for 1 hour. After cooling to room temperature, water (25 ml) was added and stirred vigorously. The organic layer was separated, and 35% hydrochloric acid was added to the resulting aqueous layer to adjust to pH 1 and extracted with 1,2-dichloroethane. The obtained 1,2-dichloroethane solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off. A small amount of diisopropyl ether was added to the resulting residue, and the precipitated solid was collected, washed with water, and dried to obtain the desired product (3.53 g). Melting point 130-133 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 0.89

 Three

 (t, J = 7.2Hz, 3H), 1.20-1.50 (m, 7H), 3.10— 3.19 (m, 2H), 3.36— 3.83 (m, 1H), 4.16 (s, 3H), 4.15—4.29 (m, 1H), 4.56-4.67 (m, 1H), 6.56 (t, 1H), 9.50-9.92 (brs, 1H).

 (2) 3 Black mouth 1-methyl 4- (5-methyl 5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfol isocyanate

[Chemical 61]

トルエン（15ml)に N— (n—ブチルァミノカルボ-ル） 3 クロ口一 1—メチル 4 — (5—メチル 5H, 6H-1, 4, 2 ジォキサジン— 3—ィル）ピラゾールー 5—スル ホンアミド（5.0g、 13mmol)、ビストリクロロメチルカーボネート（9.4g, 32mmol)お よびトリェチルァミン (0.1ml)をカ卩え、 8時間加熱還流した。溶媒留去して目的物 (4 . Og)を得た。油状物質。

Toluene (15 ml) with N— (n-Butylaminocarbol) 3 Black mouth 1-Methyl 4 — (5-Methyl 5H, 6H-1, 4, 2 Dioxazine-3-yl) pyrazole-5-Sulfur Honamide (5.0 g, 13 mmol), bistrichloromethyl carbonate (9.4 g, 32 mmol) and triethylamine (0.1 ml) were added and heated to reflux for 8 hours. The solvent was distilled off to obtain the desired product (4. Og). Oily substance.

(Reference Example 14)

 (1) Synthesis of bis (3-chloro 1-methyl 4- (5-methyl 5H, 6H-1, 4, 2 dioxazine 3-yl) pyrazole-5-yl) disulfide

[Chemical 62]

3 クロ口一 5—メルカプト一 1—メチル 4— (5—メチル 5H, 6H- 1, 4, 2 ジ ォキサジン— 3—ィル）ピラゾール（1. 0g、 4. Ommol)の N, N ジメチルホルムアミ ド（10ml)溶液に、室温で撹拌しながら、 3. 5時間にわたり空気を吹き込んだ。析出 した固体を濾取、水洗、乾燥して目的物（0. 49g)を得た。融点 165— 167°C。プロト ン核磁気共鳴ケミカルシフト値 δ (ppm) (CDC1中） 1. 36 (d, J = 6. 3Hz, 3H) , 3

3 Black mouth 5-Mercapto 1-Methyl 4- (5-Methyl 5H, 6H- 1, 4, 2 Dioxazine-3-yl) pyrazole (1.0 g, 4. Ommol) in N, N dimethylform Air was bubbled into the amide (10 ml) solution for 3.5 hours with stirring at room temperature. The precipitated solid was collected by filtration, washed with water and dried to obtain the desired product (0.49 g). Melting point 165-167 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1. 36 (d, J = 6. 3Hz, 3H), 3

 Three

 49- 3.64 (m, 1H), 3.89 (s, 3H), 4. 04—4. 18 (m, 1H), 4. 32—4. 48 (m, 1H).

 [0101] (2) 3 1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2 Dioxazine

 -3yl) pyrazole-5 sulphoyluclide (part 2)

 1,2-methyl 4- (5-methyl 5H, 6H- 1, 4, 2 dioxazine-3-yl) pyrazole-5-yl) disulfide (2.5 g, 5. lmmol) 1, Water (20 ml) was added to a solution of 2 dichloroethane (50 ml), and chlorine (2.lg, 3 Ommol) was introduced with vigorous stirring under ice cooling. During this time, the reaction temperature rose to 20 ° C. After introducing nitrogen to remove excess chlorine, the 1,2-dichloroethane layer was separated. The obtained 1,2-dichloroethane solution was washed successively with a saturated aqueous solution of sodium hydrogen sulfite and water, dried over anhydrous sodium sulfate, and evaporated to give the desired product (3. Og). Melting point 63-68 ° C.

 [0102] [Reference Example 15]

 3, 5 Dichloro 1- (5-Hodomethyl 1 5H, 6H- 1, 4, 2 Dioxazine 3- 3-yl) Synthesis of 1-methylpyrazole (Part 2)

 To a solution of N-aryloxy 3,5 dichloro 1-methylbiazole 4 carboxylic acid amide (0.50 g ァ 2. Ommol) in acetonitrile (5 ml), add N-odosuccinimide (0.67 g, 3. Ommol). The mixture was stirred and stirred at room temperature for 15 hours. Obtain a saturated aqueous solution of sodium hydrogen sulfite (10 ml), extract with ethyl acetate, wash the resulting ethyl acetate solution with saturated aqueous solution of sodium bicarbonate, saturated aqueous solution of sodium chloride and water, and then dry over anhydrous sodium sulfate. The solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 3 Zl) to obtain the desired product (0.60 g). Oily substance.

 [0103] [Reference Example 16]

(1) 4— (5 Bromomethyl-5H, 6H-1, 4, 2 Dioxazine-3-yl) —3, 5— Synthesis of methylpyrazole

N-aryloxy 3,5 dichloro 1-methylbiazole 4 carboxylic acid amide (20 Og, 80. Ommol) solution in acetonitrile (200 ml) [this, N bromoconoxyimide (1 7. lg, 96. Ommol) was added and stirred at room temperature for 1 hour. Sodium hydrogen sulfite saturated aqueous solution (100 ml) was added, and acetonitrile was distilled off. Next, extraction with ethyl acetate was performed, and the resulting ethyl acetate solution was washed successively with water and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 3 Zl) to obtain the desired product (18.4 g). Melting point 53-54. C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 3. 57— 3.6

 Three

l (d, J = 6.9Hz, 2H), 3.83 (s, 3H), 4.06—4.11 (m, 1H), 4.29—4.33 (m, 1H), 4. 65-4. 72 (m, 1H).

 (2) Synthesis of 3, 5 dichloro 1-methyl 4- (5-methyl 5H, 6H— 1, 4, 2 dioxazine 3-yl) pyrazole (part 3)

4— (5 Bromomethyl-5H, 6H-1, 4, 2 Dioxazine-3-yl) —3,5 Dichloro 1-methylpyrazole (0.50 g, 1.5 mmol) of N-methyl 2 pyrrolidone ( 5 ml) solution was charged with sodium borohydride (0.1 lg, 3. Ommol) and stirred at 60 ° C for 1 hour. After cooling to room temperature, water (5 ml) was added, and 35% hydrochloric acid was added to adjust to pHl, followed by extraction with ethyl acetate. The obtained ethyl acetate solution was washed successively with a saturated aqueous solution of sodium hydrogen carbonate, a saturated aqueous solution of sodium chloride and water, then dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 5Z2) to obtain the desired product (0.31 g). Melting point 50—51 ° C. [0105] [Reference Example 17]

 (1) Synthesis of 5-Benzylthio 1-methylvirazole-4 Carbohydroxamic acid

[Chemical 64]

5 To a suspension of benzylthio-1-methylpyrazole-4-carboxylic acid (15.9 g, 64. Ommol) in toluene (100 ml) was added thiol chloride (11.4 g, 95.8 mmol) and N, N-dimethyl. Tylformamide (0. lg) was added and heated to reflux for 4 hours. The residue obtained by distilling off the solvent was dissolved in tetrahydrofuran (40 ml).

 Further IJ, hydroxynoreamine hydrochloride (13.3 g, 191 mmol) in water (40 ml) at 5 or 15 ° C in 85% potassium hydroxide (12.6 g, 191 mmol) in water (40 ml) Was stirred and stirred at room temperature for 15 minutes. Next, the tetrahydrofuran solution was added dropwise at 3 to 15 ° C. over 0.25 hours. After further stirring at 3 ° C for 1.5 hours, 35% hydrochloric acid (20 ml) was added to adjust the pH to 3 or 4, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting residue was purified by silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 1/1). The target product (10.3 g) was obtained. Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 3. 42 (s, 3

 Three

 H), 3. 95 (s, 2H), 6. 93— 7. 01 (m, 2H), 7. 20— 7.28 (m, 3H), 8. 04 (s, 1H), 9. 76 (brs, 1H).

[0106] (2) Synthesis of N-aryloxy-5 benzylthio 1 methylbiazole 4 carboxylic acid amide

[Chemical 65]

炭酸カリウム（1. 3g、 9. 4mmol)の水（10ml)溶液に、 5 べンジルチオー1ーメ チルピラゾールー 4 カルボヒドロキサム酸（2. 0g、 7. 6mmol)と臭化ァリル（1. lg 、 9. lmmol)のトルエン（10ml)溶液を加え、 50°Cにて 4時間撹拌した。室温まで冷 却後、 35%塩酸を加えて pHlに調整し、酢酸ェチルで抽出した。得られた酢酸ェチ ル溶液を水洗後、無水硫酸ナトリウムで乾燥し、溶媒留去して目的物（1. 9g)を得た 。油状物質。プロトン核磁気共鳴ケミカルシフト値 δ (ppm) (CDCl中） 3. 42 (s, 3H

A solution of potassium carbonate (1.3 g, 9.4 mmol) in water (10 ml) was added to 5 benzylthio-1-methylpyrazole-4 carbohydroxamic acid (2.0 g, 7.6 mmol) and allyl bromide (1.lg, 9. lmmol) in toluene (10ml) was added and stirred at 50 ° C for 4 hours. After cooling to room temperature, 35% hydrochloric acid was added to adjust to pHl, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain the desired product (1.9 g). Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDCl) 3. 42 (s, 3H

 Three

 ), 3.95 (s, 2H), 4.49 (d, J = 6.3Hz, 2H), 5.33—5.43 (m, 2H), 6.00—6.16 (m, 1H ), 6.93—7.00 (m, 2H), 7.21— 7.30 (m, 3H), 8.06 (s, 1H), 9.68 (brs, 1H).

 (3) Synthesis of 5-benzylthio 4- (5-iodomethyl 5-H, 6H— 1, 4, 2 dioxazine 3-yl) 1-methylpyrazole

[Chemical 66]

Iodine (4.5 g, 18 mmol) was added to a solution of N-aryloxy-5 benzylthio 1 methylbiazole 4 carboxylic acid amide (1.8 g, 5.9 mmol) in acetonitrile (10 ml), and the mixture was stirred at room temperature for 8 hours. A saturated aqueous sodium thiosulfate solution (30 ml) was added, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was mixed with a saturated aqueous solution of sodium bicarbonate, salt The organic layer was washed successively with a saturated aqueous sodium chloride solution and water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 3 Zl) to obtain the desired product (1.7 g). Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 3.36—3.42 (m, 5H), 3.98—4.0

 Three

 5 (m, 3H), 4.31-4.38 (m, 1H), 4.54—4.59 (m, 1H), 6.97—7.02 (m, 2H), 7.20-7.24 (m, 3H), 7.79 (s, 1H).

[0108] (4) 5 Synthesis of benzylthio-1-methyl-4- (5-methyl-5H, 6H— 1, 4, 2 dioxazine 3-yl) pyrazole

 [Chemical 67]

5 Benzylthio-4- (5-methyl-5H, 6H-1,4,2 dioxazine-3-yl) -1-methylpyrazole (1.6 g, 3.7 mmol) in N, N dimethylformamide (8 ml) A solution of sodium borohydride (0.21 g, 5.6 mmol) in N, N-dimethylformamide (5 ml) was added dropwise at 0.3 ° C. over 0.3 hours, and the mixture was further stirred at 50 ° C. for 1 hour. After cooling to room temperature, water (20 ml) was added, 35% hydrochloric acid was added to adjust to pHl, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed successively with 6% hydrochloric acid and water, dried over anhydrous sodium sulfate, and evaporated to obtain the desired product (1. lg). Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1.43 (d, J = 6.3Hz, 3H)

 Three

 , 3.36 (s, 3H), 3.69-3.77 (m, 1H), 4.04 (q, J = 12.6Hz, 2H), 4.21— 4.27 (m, 1H), 4.55—4.61 (m, 1H), 6.98— 7.03 (m, 2H), 7.19— 7.24 (m, 3H), 7.76 (s, 1H).

[0109] (5) Synthesis of 1-methyl-4- (5-methyl-5H, 6H—1, 4, 2 dioxazine 3-yl) pyrazole 5-sulfonamide [Chemical 68]

5-Benzylthio-1-methyl-4- (5-methyl-5H, 6H-1,4,2-dioxazin-1-yl) pyrazole (1. lg, 3.5 mmol) in 1,2-dichloroethane (10 ml) Water (10 ml) and 35% hydrochloric acid (0. lg) were added thereto, and chlorine (2.5 g, 35 mmol) was introduced at 5 ° C. with vigorous stirring. During this time, the reaction solution exothermed to 19 ° C. After introducing nitrogen to drive out excess chlorine, water (20 ml) was removed and extracted with 1,2-dichloroethane. The obtained 1,2-dichloroethane solution was concentrated at about 8 m under reduced pressure. This solution was added dropwise to a separately prepared 1,2-dichloroethane (8 ml) solution containing 28% aqueous ammonia (l ml) at 5 ° C with vigorous stirring, and further at room temperature for 0.5 hours. Stir. 35% hydrochloric acid was added, adjusted to pH 1 and extracted with 1,2-dichloroethane. The obtained 1,2-dichloroethane solution was dried over anhydrous sodium sulfate, the solvent was distilled off, and the resulting residue was recrystallized from toluene to obtain the desired product (0.43 g). Melting point 97—99 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CD CI) 1. 43 (d, J = 6.3 Hz, 3H), 3. 70— 3. 77 (m, 1H), 4. 19—4. 26 (m, 4

Three

 H), 4. 55-4. 62 (m, 1H), 6.49 (brs, 2H), 7.75 (s, 1H).

(Reference Example 18)

 4— (5-Methyl— 5H, 6H- 1, 4, 2-Dioxazine-3-yl) —1— (Pyridyl-2-yl) pyrazole-5-sulfonamide synthesis

[Chem 69]

原料に 5 -ベンジルチオ 1 (ピリジル -2-ィル）ピラゾール 4 カルボン酸ク ロリド（3.63g、 11. Ommol)を用い、参考例 1と同様にして目的物（0.45g)を得た。 榭脂状物質。プロトン核磁気共鳴ケミカルシフト値 δ (ppm) (CDC1中） 1.43 (d, J

The target product (0.45 g) was obtained in the same manner as in Reference Example 1 using 5-benzylthio 1 (pyridyl-2-yl) pyrazole 4 carboxylic acid chloride (3.63 g, 11. Ommol) as a raw material. Oily substance. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC1) 1.43 (d, J

 Three

 = 6.3Hz, 3H), 3.77-3.83 (m, 1H), 4.22—4.26 (m, 1H), 4.58—4.6 3 (m, 1H), 6.41 (brs, 2H), 7.42—7.44 (m, 1H) 7.78—7.80 (m, 1H), 7.87 (s, 1H) 7.93-7.98 (m, 1H), 8.48—8.50 (m, 1H).

(Reference Example 19)

 3 Chloro 1-methynole 4 (5-Methylene 5H, 6H-1, 4, 2 Dioxazine-3-yl) pyrazole 5-Synthesis of sulfonamides

 [Chemical 70]

3 Black mouth 1-Methyl 4- (5 HODOMETHYL 5H, 6H-1, 4, 2 Dioxazine-3-yl) Pyrazole-5-sulfonamide (0.55g, 1.3mmol) in 1,2 dimethoxyethane (10ml ) And stirred under ice cooling. Next, 28% sodium methoxide in methanol (0.6 g, 3. 1 mmol) was slowly added at 0 ° C., followed by stirring for 1 hour. The reaction was stopped by adding 2N hydrochloric acid and 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 an oil. was gotten. The obtained oily substance was purified by silica gel column chromatography (eluent; nxan Z ethyl acetate = 1Z1) to obtain the desired product (0.36 g). Colorless solid. Melting point 116 — 119 ° C. Proton nuclear magnetic resonance chemical shift value δ (ppm) (in CDC13) 4.15 (s, 3H), 4.52 (s, 2H), 4.53 (d, J = 2.8Hz, 1H), 4.93 (d, J = 2.8Hz, 1H) 6.03 (b rs, 2H) ₀

 [0112] The structural formulas and physical properties of the compound (A) synthesized by using the same method as in the synthesis examples and reference examples are shown in Table 1 together with the compounds described in the synthesis examples and reference examples. Shown in

 [0113] [Chemical 71]

[table 1]

(Table 1)

N o. R ¹ R ² R ³ R ⁴ R ⁵ R ^fi XY Physical properties (melting point.

 1 Me C 1 Me H H H Me! O Me O CH 1 7 7- 1 79

2 Me C 1 I CH ₂ HHH Mt O Me: O CH 9 1-94

3 Me C 1 Me Me H H Me: o Me o CH 1 8 9-1 9 1

4 Me C 1 Me I CH H H M (o Me: o CH 90-93

5 Me Me Me H H H Me: o Me o CH 1 80- 1 82

6 Me Me I CH ₂ HHHM (O Me o CH 66-69

7 Me Me Me Me H H Me: o Me o CH 1 9 9-20 1

8 Me Me Me I CH H H Me o Me o CH 1 3 3-1 3 5

9 Me Me H H Me H Me; o Me o CH 1 8 7— 1 89

1 0 Me H Me H H H Me: o Me o CH 1 54-1 57

1 1 Me C 1 Me H H H Mi o Me CH 1 8 1-1 82

1 2 Me C 1 Me H H H Me Me CH 1 76-1 7 7

1 3 Me C 1 Me H H H Me; o Me o N 1 50- 1 5 1

1 4 Me C 1 Me H H H Me 〇 Me N 1 9 1-1 9 3

1 5 Me C 1 Me H H H Me Me N

 1 6 Me C 1 E t H H H M «o Me ○ CH

 1 7 Me Me Et H H H Mc ； o Me o CH

 1 8 Me H E t H H H M «o Me o CH

 1 9 2— P y H Me H H H Mi o Me: o CH 100—101

2 0 Me C 1 Me H H H Mf o C 1 CH 157-158

2 1 Me C 1 = CH ₂ HH Me o Me o CH 1 64- 1 67 Compound (A) and at least one compound selected from the power of Daimlon, Dimepiperate and Esprocarb Combinations include Compound 1Z Daimlone, Compound 1Z Dimepiperate, Compound 1Z Esprocarp, Compound 2Z Daimlon

, Compound 2Z dimepiperate, compound 2Z esprocarp, compound 3Z dimelolone, compound 3Z dimepiperate, compound 3Z esprocalp, compound 4Z dimemron, compound 4Z dimepiperate, compound 4Z esprocarp, compound 5Z dimprolone, compound 5Z dimepiperate, Compound 5Z Esprocalp, Compound 6Z Daimlone, Compound 6Z Dimepiperate, Compound 6Z Esprocalp, Compound 7Z Daimlon, Compound 7Z Dimepiperate, Compound 7Z Esprocalp, Compound 8Z Dimelon, Compound 8Z Dimepiperate, Compound 8Z Esprocarp, Compound 9Z Diimron , Compound 9Z Dimepiperate, Compound 9Z Esprocarp, Compound 10Z Dimelon, Compound 10Z Dimepiperate, Compound 10Z Esprocarp, Compound liz Daimlon, Compound liZ Dimepiperate, Compound liZ Esproca Flop, Compound 12Z dymron, compound 12Z Jimepi Bae rate, compound 12Z Esprocarb, Compound 13Z Daimlone, Compound 13; z Dimepiperate, Compound 13Z Esprocarb, Compound 14Z Daimlone, Compound 14 z Dimepiperate, Compound 14Z Esprocarb, Compound 15Z Daimlon, Compound 15 Dimepiperate, Compound 15Z Esprocarb, Compound 16Z Daimlone , Compound 16 'Z Dimepiperate, Compound 16Z Esprocarb, Compound 17Z Daimlone, Compound 17 ζ Dimepiperate, Compound 17Z Esprocarb, Compound 18Z Daimlone, Compound 18; ζ Dimepiperate, Compound 18Z Esprocarb, Compound 19Z Didimlon, Compound 19 'Z dimethylpiperate, compound 19Z esprocarb, compound 20Z dimprolone, compound 2G ι メ dimepiperate, compound 20Ζ esprocarb, compound 21Z dimepilone, compound 21 ζ dimepiperate, compound 21Z esprocarb And the like. In addition to the compound (ii) and at least one compound selected from among Daimlon, dimethylpiperate and esprocarp as herbicides that can be applied at the same time, the compounds listed in Table 2 as compounds of the group IV Can be mentioned. Further, when applying at least one kind of compound (ii) and at least one kind of compound selected from Daimron, Dimepiperate and Esprocarp at the same time, the compounds listed in Table 2 can be applied simultaneously.

 In the present invention, each compound may be applied individually or as a mixed composition in application. When each is applied individually, it can be applied at the same time, or can be processed separately as long as they are close in time.

[Table 2]

[Table 2] Compound examples: virazosulefon-ethyl Z (generic name), benzreflonmethy bensulfuron-methyl (generic name), sinoleflon (cynosulfuron / generic name), imazosnoreflon (i ma zosulfuron / (Common name), azimsulfuron (azimsulfuron / —common name), ros, rosnolev mouth methylenole (ha 1 osulfuron—methyl / —common name, cyclosnorefumron (eye 1 osu 1 fa mu ron / 1 Jl name) , Ethoxysulfuron (generic name), pyrazolate (pyrazo 1 ate / generic name), birazoxyfen (pyrazoxyfen / generic name), benzofenap / (generic name), promobutide (br omo butid eZ —Common name, naproanilid eZ—common name , Pretilachlor (common name), butachlor (butachlor Z—common name), turchlor (thenylchlor / —common name), C NP (—common name), chrometoxynil (chl om cthoxynil / —common name), bifueno (Bifenox / -common name), oxadiazon / (common name), oxadiaarginole (oxadiargyl / -common name), pentoxazone (pentoxazon eZ--common name), caffeentrole (cafenstro 1 e _ /-common name), oxadiclo Mehon (oazic 1 omefone / generic name), Inta, 'Nophan (indanofan / generic name), Pyriminobac-me thyl (generic name), Cyhalofop-butyl (generic name), Fentrazamide (fentrazamide / generic name) Mefenacet (generic name), butenachlor (butenachlor Z—common name), dithiopyr (dithiopy 1 Z—common name), benfuresate Z (common name), pilibuticarb / (generic name), bento curve ( benthiocar bZ—common name), morinet (common name), butamifos (common name), quinclorac (common name), cinmethrin (ci nm ethylin / common name), symtrime (Simctryn / -common name), Bensulide (bensulide)

[Table 3] / Generic name), dimethametryn /-common name, MC PA (—common name), MC PB (—common name), etbenzanid (—common name), cuminoles (cumy) 1 ur ο η / —common name), benzobicyclon (—-common name), pyriftalide (pyriftalid / —common name), bispyribac (common name), pirac mouth-nore (pyrac 1 oni 1 / Generic name), anilofos (ani 1 ofos / generic name), OK—700 (test name), penoxsuram (penoxsu)

1 am / —common name), AVH_ 3 0 1 (study name), KUH— 0 2 1 (study name), TH— 5 4 7 (study name), bentazone (Bentazone / —common name), 2, 4 — PA (--generic name), metamihop (common name), flucetosulfuron / (common name), HO K— 2 0 1 (—common name), mesotrione (common name), propanil (Propani 1 / common name), quinoclamin (quinoclamine Z—common name) and chrome prop (c 1 o me prop)

Specific combinations with the compounds listed in Table 2 that can be applied simultaneously with Compound (A) are shown in Table 3.

[Table 3] Examples of combinations of compounds that can be applied simultaneously Compound 1Z virazosulfuronethyl, compound 1Z bensulfuron methyl, compound 1Z cinnosulfuron, compound 1Z imazosulfuron, compound 1Z azimusulfuron, compound 1Z halosulfuron methyl, compound 1Z cyclosulfur Famron, Compound 1Z Ethoxysulfuron, Compound 1Z Pyrazolate, Compound 1Z Birazoxifene, Compound 1Z Benzophenap, Compound 1Z Bromobutide, Compound 1Z Naproanilide, Compound 1Z Pretilachlor, Compound 1Z Butachlor, Compound 1Z Tenenylchlor, Compound IZCNP, Compound iZ Compound iZ Bifnox, Compound iZ Oxadiazone, Compound iZ Oxadialgyl, Compound iZ Pentoxazone, Compound iZ Caffentrol, Compound iZ Oxadichromone, Compound iZ Indanofuan compound iZ pyriminobac-methyl, compound iZ cyhalofop-butyl, compound iZ fentrazamide, compound iZ Mefuenase , Compound iZ Butenachlor, Compound 1Z Dithiopyr, Compound 1Z Benfresate, Compound 1Z Piritypical, Compound iZ Benchocurve, Compound iZ Molinate, Compound iZ Butamifos, Compound iZ Kink Mouth Rack, Compound iZ Simmesrin, Compound iZ Cimethrin, Compound iZ Benthuride , Compound iZ Dimetamethrin, Compound IZMCPA, Compound

1 / MCPB, Compound 1Z Etobenzad, Compound 1Z Cumyluron, Compound 1Z Benzobicyclone, Compound iZ Pyriphthalide, Compound iZ Bispyribac, Compound iZ Pyracol, Compound 1Z Anilophos, Compound 1ZOK—701, Compound 1Z Penoxsulam, Compound 1 ZAVH — 301, Compound 1ZKUH— 021, Compound ΐΖΤΗ— 547, Compound lZ Ventazone, Compound 1Z2, 4-— PA, Compound lZ Metamihop, Compound 1Z Flucetosulfuron, Compound 1ZHOK—201, Compound 1Z Mesotrione, Compound 1Z Propanil, Compound 1Z Kinoclamine, y compound 1 / chromeprop,

Compound 2Z Virazosulfuronethyl, Compound 2Z Bensulfuron methyl, Compound 2Z Cynosulfuron, Compound 2Z Imazosulfuron, Compound 2Z Azimusulfuron, Compound 2Z Halosulfuron methyl, Compound 2Z Cyclosulfamlone, Compound 2Z Ethoxysulfuron, Compound 2Z Pyrazolate, Compound 2Z Birazoxifen, Compound 2Z Benzophenap, Compound 2Z Bromobutide, Compound 2Z Naproanilide, Compound 2Z Pretilachlor, Compound 2Z Butachlor, Compound 2Z Tenenylchlor, Compound 2ZCNP, Compound 2Z Clomethoxynil, Compound 2Z Bif ヱ nox, Compound 2Z Oxadizone Oxadialgyl, Compound 2Z Pentoxazone, Compound 2Z Caffentrol, Compound 2Z Oxadiclomephone, Compound 2Z Indanophane, Compound 2Z Pyriminobacmethy , Compound 2Z Cihalohop Butyl, Compound 2Z Fentolazamide, Compound 2Z Mefenacet, Compound 2Z Butenachlor, Compound 2Z Dithiopyr, Compound 2Z Benfrate, Compound 2Z Pipripipalp, Compound 2Z Bencho curve, Compound 2Z Molinate, Compound 2Z Butamiphos, Compound 2Z Kink Mouth rack, Compound 2Z Simmesrin, Compound 2Z Cymethrin, Compound 2Z Benthuride, Compound 2Z Dimetamethrin, Compound 2ZMCPA, Compound 2 / MCPB, Compound 2Z Etobenzazade, Compound 2Z Cumylron, Compound 2Z Benzobicyclone, Compound 2Z Pyriphthalide, Compound 2Z Bispyribac , Compound 2Z pyrachlor, Compound 2Z Anilophos, Compound 2ZOK—701, Compound 2Z Penoxsulam, Compound 2 ZAVH—301, Compound 2ZKUH—021, Compound 2ZTH—547, Compound 2ΖBentazone, Compound 2Ζ2, 4—ΡΑ, Compound 2ΖMetamihop, Compound 2ΖFurcetosulfuron, Compound 2ΖΗΟΚ—201, Compound 2ΖMesotrione, Compound 2Ζpropanyl, Compound 2Ζ Kinoclamine, 匕 Compound 2 / Chromprop,

Compound 3ΖVilazosulfuronethyl, Compound 3ΖBensulfuron methyl, Compound 3ΖSinosulfuron, Compound 3ΖImazosulfuron, Compound 3ΖAzimusulfuron, Compound 3ΖHalosulfuron methyl, Compound 3ΖCyclosulfamlone, Compound 3ΖEthoxysulfuron, Compound 3Ζ Pyrazolate, Compound 3ΖBrazoxifene, Compound 3ΖBenzophenap, Compound 3ΖBromobutide, Compound 3ΖNaproanilide, Compound 3ΖPretilachlor, Compound 3ΖButachlor, Compound 3ΖTenylchlor, Compound 3ZCNP, Compound 3Z Clomethoxynil, Compound 3Z Bif ヱ noxone, Compound 3Z Oxadizone Oxadialgyl, Compound 3Z Pentoxazone, Compound 3Z Caffentrol, Compound 3Z Oxadichlormephone, Compound 3Z Indanophane, Compound 3Z Pyrimino Cicmethyl, Compound 3Z Cihalohop Butyl, Compound 3Z Fentrazamide, Compound 3Z Mefenacet, Compound 3Z Butenachlor, Compound 3Z Dithiopyr, Compound 3Z Benfrate, Compound 3Z Pipipipalp, Compound 3Z Benchocarb, Compound 3Z Molinate, Compound 3Z Butamiphos, Compound 3Z Kink Mouth Rack, Compound 3Z Simmesrin, Compound 3Z Cymethrin, Compound 3Z Benthuride, Compound 3Z Dimetamethrin, Compound 3ZMCPA, Compound 3 / MCPB, Compound 3Z Etobenzazade, Compound 3Z Cumylron, Compound 3Z Benzobicyclone, Compound 3Z Pyriphthalide, Compound 3Z Bispyribac, compound 3Z pyrachlor, compound 3Z anilophos, compound 3ZOK—701, compound 3Z penoxsulam, compound 3 ZAVH—301, compound 3ZKUH—021, compound 3ZTH—547, compound 3Z bentazone, compound 3Z2, 4— PA, compound 3Z metamihop, compound 3Z flucetosulfuron, compound 3ZHOK—201, compound 3Z mesotrione, compound 3Z propanil, compound 3Z quinocuramin, compound 3 / chromeprop,

Compound 4Z Virazosulfuronethyl, Compound 4Z Bensulfuron methyl, Compound 4Z Synosulfuron, Compound 4Z Imazosulfuron, Compound 4Z Azimusulfuron, Compound 4Z Halosulfuron methyl, Compound 4Z cyclosulfamuron, Compound 4Z ethoxysulfuron , Compound 4Z pyrazolate, compound 4Z birazoxifen, compound 4Z benzophenap, compound 4Z bromobutide, compound 4Z naproanilide, compound 4Z pretilachlor, compound 4Z butachlor, compound 4Z tenenyl chlor, compound 4ZCNP, compound 4Z cromethoxyl, compound 4Z bifunox, Compound 4Z Oxadiazone, Compound 4Z Oxadialgyl, Compound 4Z Pentoxazone, Compound 4Z Caffentrol, Compound 4Z Oxadiclomephone, Compound 4Z Indanophane, Compound 4Z Pyriminobacmethyl, Compound 4Z Cihalohop Butyl, Compound 4Z Fentrazamide, Compound 4Z mefenacet, compound 4Z butenachlor, compound 4Z dithiopyr, compound 4Z benfrecetate, compound 4Z piritypcarp, compound 4Z bencho curve, compound 4Z molinate, compound 4Z Butamiphos, Compound 4Z Kink Mouth Rack, Compound 4Z Simmesrin, Compound 4Z Cymethrin, Compound 4Z Benthuride, Compound 4Z Dimetamethrin, Compound 4ZMCPA, Compound 4 / MCPB, Compound 4Z Etobenzad, Compound 4Z Cumylron, Compound 4Z Benzobicyclone, Compound 4Z Pyriphthalide, Compound 4Z Bispyribac, Compound 4Z Pyracol, Compound 4Z Anilophos, Compound 4ZOK—701, Compound 4Z Penoxsulam, Compound 4 ZAVH—301, Compound 4ZKUH—021, Compound 4ZTH—547, Compound 4Z Ventazone, Compound 4Z2 , 4—PA, compound 4Z metamihop, compound 4Z flucetosulfuron, compound 4ZHOK—201, compound 4Z mesotrione, compound 4Z propanyl, compound 4Z quinoclamin, compound 4 / chromeprop,

Compound 5Z Virazosulfuronethyl, Compound 5Z Bensulfuron methyl, Compound 5Z Cynosulfuron, Compound 5Z Imazosulfuron, Compound 5Z Azimusulfuron, Compound 5Z Halosulfuron methyl, Compound 5Z Cyclosulfamlone, Compound 5Z Ethoxysulfuron, Compound 5Z Pyrazolate, Compound 5Z Birazoxifene, Compound 5Z Benzophenap, Compound 5Z Bromobutide, Compound 5Z Naproanilide, Compound 5Z Pretilachlor, Compound 5Z Butachlor, Compound 5Z Tenenylchlor, Compound 5ZCNP, Compound 5Z Chromethoxyl, Compound 5Z Bif ヱ noxone, Compound 5Z Oxadizone Compound 5Z Oxadialgyl, Compound 5Z Pentoxazone, Compound 5Z Caffentrol, Compound 5Z Oxadichrome Mephon, Compound 5Z Indanophane, Compound 5Z Pyriminobackmethy Compound 5Z cyhalofop-butyl, compound 5Z fentrazamide, compound 5Z Mefuenase , Compound 5Z butenachlor, compound 5Z dithiopyr, compound 5Z benfrecetate, compound 5Z piritypcarp, compound 5Z beni curve, compound 5Z molinate, compound 5Z butamifos, compound 5Z kink mouth rack, compound 5Z symmethrin, compound 5Z simethrin, compound 5Z benzulide , Compound 5Z Dimetamethrin, Compound 5ZMCPA, Compound 5 / MCPB, Compound 5Z Etobenzad, Compound 5Z Cumylron, Compound 5Z Benzobicyclone, Compound 5Z Pyriphthalide, Compound 5Z Bispyribac, Compound 5Z Pyracol, Compound 5Z Anilophos, Compound 5ZOK—701 , Compound 5Z Penoxsulam, Compound 5 ZAVH—301, Compound 5ZKUH—021, Compound 5ZTH—547, Compound 5Z Ventazone, Compound 5Z2, 4-—PA, Compound 5Z Metamihop, Compound 5Z Fulcetosulfuron, Compound 5ZHOK—201, Compound 5Z Mesoto One, Compound 5Z propanil, compound 5Z quinoclamine, I 匕合 was 5 / clomeprop,

Compound 6Z Virazosulfuronethyl, Compound 6Z Bensulfuron methyl, Compound 6Z Cynosulfuron, Compound 6Z Imazosulfuron, Compound 6Z Azimusulfuron, Compound 6Z Halosulfuron methyl, Compound 6Z Cyclosulfamlone, Compound 6Z Ethoxysulfuron, Compound 6Z Pyrazolate, Compound 6Z Birazoxifen, Compound 6Z Benzophenap, Compound 6Z Bromobutide, Compound 6Z Naproanilide, Compound 6Z Pretilachlor, Compound 6Z Butachlor, Compound 6Z Tenenylchlor, Compound 6ZCNP, Compound 6Z Chromethoxyl, Compound 6Z Bifoxane, Compound 6Z Oxadizone Compound 6Z Oxadialgyl, Compound 6Z Pentoxazone, Compound 6Z Caffenstrol, Compound 6Z Oxadiclomephone, Compound 6Z Indanophane, Compound 6Z Pyriminobackmethy , Compound 6Z Cihalohop Butyl, Compound 6Z Fentolazamide, Compound 6Z Mefenacet, Compound 6Z Butenachlor, Compound 6Z Dithiopyr, Compound 6Z Benfrate, Compound 6Z Pipripipalp, Compound 6Z Benchocarb, Compound 6Z Molinate, Compound 6Z Butamiphos, Compound 6Z Kink Mouth rack, compound 6Z simmesrin, compound 6Z cymetrine, compound 6Z benzulide, compound 6Z dimetamethrin, compound 6ZMCPA, compound 6 / MCPB, compound 6Z etozanzad, compound 6Z cumylron, compound 6Z benzobicyclone, compound 6Z pyriftalide, compound 6Z bispyribak , Compound 6Z pyrachlor, Compound 6Z Anilophos, Compound 6ZOK—701, Compound 6Z Penoxsulam, Compound 6 ZAVH—301, Compound 6ZKUH—021, Compound 6ZTH—547, Compound 6ΖVentazone, Compound 6Ζ2, 4—ΡΑ, Compound 6ΖMetamihop, Compound 6ΖFrucetosulfuron, Compound 6ΖΗΟΚ201, Compound 6ΖMesotrione, Compound 6Ζpropanyl, Compound 6Ζ Kinoclamine, y compound 6 / chromeprop,

Compound 7ΖVilazosulfuronethyl, Compound 7ΖBensulfuron methyl, Compound 7ΖSinosulfuron, Compound 7ΖImazosulfuron, Compound 7ΖAzimusulfuron, Compound 7ΖHalosulfuron methyl, Compound 7ΖCyclosulfamlone, Compound 7ΖEthoxysulfuron, Compound 7Ζ Pyrazolate, Compound 7ΖBrazoxifene, Compound 7ΖBenzophenap, Compound 7ΖBromobutide, Compound 7ΖNaproanilide, Compound 7ΖPretilachlor, Compound 7ΖButachlor, Compound 7ΖTenylchlor, Compound 7ZCNP, Compound 7Z Clomethoxynil, Compound 7Z Bif ヱ nox, Compound 7Z Oxadizone Oxadialgyl, Compound 7Z Pentoxazone, Compound 7Z Caffentrol, Compound 7Z Oxadichromemephone, Compound 7Z Indanophane, Compound 7Z Pyrimino Cicmethyl, Compound 7Z Cihalohop Butyl, Compound 7Z Fentrazamide, Compound 7Z Mefenacet, Compound 7Z Butenachlor, Compound 7Z Dithiopyr, Compound 7Z Benfrate, Compound 7Z Pipipipalp, Compound 7Z Benchocarb, Compound 7Z Molinate, Compound 7Z Butamiphos, Compound 7Z Kink Mouth Rack, Compound 7Z Simmesrin, Compound 7Z Cymethrin, Compound 7Z Benthuride, Compound 7Z Dimetamethrin, Compound 7ZMCPA, Compound 7 / MCPB, Compound 7Z Etobenzazade, Compound 7Z Cumylron, Compound 7Z Benzobicyclone, Compound 7Z Pyriphthalide, Compound 7Z Bispyribac, Compound 7Z pyrachlor, Compound 7Z Anilophos, Compound 7ZOK—701, Compound 7Z Penoxsulam, Compound 7 ZAVH—301, Compound 7ZKUH—021, Compound 7ZTH—547, Compound 7Z Ventazone, Compound 7Z2, 4— PA, compound 7Z metamihop, compound 7Z flucetosulfuron, compound 7ZHOK—201, compound 7Z mesotrione, compound 7Z propanyl, compound 7Z quinocuramin, compound 7 / chromeprop,

Compound 8Z Virazosulfuronethyl, Compound 8Z Bensulfuron methyl, Compound 8Z Sinosulfuron, Compound 8Z Imazosulfuron, Compound 8Z Azimusulfuron, Compound 8Z Halosulfuron methyl, Compound 8Z Cyclosulfamlone, Compound 8Z Ethoxysulfuron , Compound 8Z Pyrazolate, Compound 8Z Birazoxifene, Compound 8Z Benzophenap, Compound 8Z Bromobutide, Compound 8Z Naproanilide, Compound 8Z Pretilachlor, Compound 8Z Butachlor, Compound 8Z Tenenylchlor, Compound 8ZCNP, Compound 8Z Chromethoxyl, Compound 8Z Biphenolox, Compound 8Z Oxadiazone, Compound 8Z Oxadialgyl, Compound 8Z Pentoxazone, Compound 8Z Cafenstrol, Compound 8Z Oxadiclomephone, Compound 8Z Indanophane, Compound 8Z Pyriminobacmethyl, Compound 8Z Cihalohop Butyl, Compound 8Z Fentrazamide, Compound 8Z Mefenacet, Compound 8Z Butenachlor, Compound 8Z Dithiopyr, Compound 8Z Benfresate, Compound 8Z Pirtipalp, Compound 8Z Bengiocurve, Compound 8Z Molinate, Compound 8Z Butamiphos, Compound 8Z Kink Mouth Rack, Compound 8Z Simmesrin, Compound 8Z Cymethrin, Compound 8Z Benthlide, Compound 8Z Dimetamethrin, Compound 8ZMCPA, Compound 8 / MCPB, Compound 8Z Etobenzad, Compound 8Z Cumylron, Compound 8Z Benzobicyclone, Compound 8Z Pyriphthalide, Compound 8Z Bispyribac, Compound 8Z Pyracol, Compound 8Z Anilophos, Compound 8ZOK—701, Compound 8Z Penoxsulam, Compound 8 ZAVH—301, Compound 8ZKUH—021, Compound 8ZTH—547, Compound 8Z Ventazone, Compound 8Z2 , 4—PA, compound 8Z metamihop, compound 8Z flucetosulfuron, compound 8ZHOK—201, compound 8Z mesotrione, compound 8Z propanyl, compound 8Z quinoclamine, compound 8 / chromeprop,

Compound 9Z Virazosulfuronethyl, Compound 9Z Bensulfuron methyl, Compound 9Z Cynosulfuron, Compound 9Z Imazosulfuron, Compound 9Z Azimusulfuron, Compound 9Z Halosulfuron methyl, Compound 9Z cyclosulfamuron, Compound 9Z ethoxysulfuron, Compound 9Z Pyrazolate, Compound 9Z Birazoxifene, Compound 9Z Benzophenap, Compound 9Z Bromobutide, Compound 9Z Naproanilide, Compound 9Z Pretilachlor, Compound 9Z Butachlor, Compound 9Z Tenenylchlor, Compound 9ZCNP, Compound 9Z Chromethoxyur, Compound 9Z Bifoxane, Compound 9Z Oxadizone Compound 9Z Oxadialgyl, Compound 9Z Pentoxazone, Compound 9Z Caffentrol, Compound 9Z Oxadichromeme, Compound 9Z Indanophane, Compound 9Z Pyriminobackmethy Compound 9Z cyhalofop-butyl, compound 9Z fentrazamide, compound 9Z Mefuenase , Compound 9Z butenachlor, compound 9Z dithiopyr, compound 9Z benfresate, compound 9Z piripycarp, compound 9Z beni curve, compound 9Z molinate, compound 9Z butamifos, compound 9Z kink mouth rack, compound 9Z cinmethrin, compound 9Z simethrin, compound 9Z benzulide , Compound 9Z Dimetamethrin, Compound 9ZMCPA, Compound 9 / MCPB, Compound 9Z Etobenzad, Compound 9Z Cumyluron, Compound 9Z Benzobicyclone, Compound 9Z Pyriphthalide, Compound 9Z Bispyribac, Compound 9Z Pyrochlor, Compound 9Z Anilophos, Compound 9ZOK—701 , Compound 9Z Penoxsulam, Compound 9 ZAVH—301, Compound 9ZKUH—021, Compound 9ZTH—547, Compound 9Z Ventazone, Compound 9Z2, 4-—PA, Compound 9Z Metamihop, Compound 9Z flucetosulfuron, Compound 9ZHOK—201, Compound 9Z Mesoto On compound 9Z propanil, compound 9Z quinoclamine, it 匕合 compound 9 / clomeprop,

Compound 10Z Virazosulfuronethyl, Compound 10Z Bensulfuron methyl, Compound 10

Z Sinosulfuron, Compound 10Z Imazosulfuron, Compound 10Z Azimusulfuron, Compound 10Z Halosulfuron methyl, Compound 10Z Cyclosulfamlone, Compound 10Z Ethoxysulfuron, Compound 10Z Pyrazolate, Compound 10Z Birazoxifen, Compound 10 Z Benzophenap, Compound 10Z Bromobutide, Compound 10Z Napro-Alide, Compound 10Z Pretilachlor, Compound 10Z Butachlor, Compound 10Z Turculol, Compound 10ZCNP, Compound ΙΟΖChromethoxyl, Compound 10Z Bif Knox, Compound 1 οΖoxadiazone, Compound ιοΖoxadialgyl, Compound ιοΖ , Compound 10Z Caffentrol, Compound 10Z Oxadiclomephone, Compound 10Z Indanophan, Compound ιοΖPyriminobacmethyl, Compound ιοΖCihalohopbutyl, Compound 1 οΖ Fentrazamide, Compound ιοΖ Mefnaset, Compound ιοΖ Butenachlor, Compound ιοΖ Dithiopyr, Compound ιοΖ Benfrecetate, Compound ιοΖ Pyributicalp, Compound ιοΖ Benchabure, Compound ιοΖ Molinate, Compound ιοΖ Butamiphos, Compound ιοΖ Butamiphos, Compound 1 , Compound ιοΖ Bensuride, Compound ιοΖ Dimetamethrin, Compound IOZMCPA, Compound IOZMCPB, Compound loz Etobenzad, Compound 10Z Cumyllon, Compound 10Z Benzobicyclone, Compound OZ-Lofos, Compound 10ΖΟΚ-701, Compound 10Z Penoxsulam, Compound 10ZA VH—301, Compound 10ZKUH—021, Compound ΙθΖΤΗ-547, Compound ΙθΖBentazone, Compound 10Z2, 4-PA, Compound 10Z Metamihop, Compound 10Z Flucetosulf Ron, Compound 10ZHOK—201, Compound 10Z Mesotrione, Compound 10Z Propaer, Compound 10Z Quinocamine, Compound 10Z Chromepprop,

Compound 11 Z virazosulfuronethyl, compound liZ bensulfuron methyl, compound 11 Z cinnosulfuron, compound liZ imazosulfuron, compound liZ azimylsulfuron, compound 11 Z halosulfuron methyl, compound liZ cyclosulfamuron, compound liZ etoxysulfuron , Compound liZ Pyrazolate, Compound 11 Z Birazoxifen, Compound 11 Z Benzofenap, Compound liZ Bromobutide, Compound liZ Naproa-Lide, Compound liZ Pretilachlor, Compound liZ Butachlor, Compound liZ Turculol, Compound IIZCNP, Compound liZ Chrometoxy Shell, Compound liZ Bif Knox, Compound 1 1Z Oxadiazone, Compound 11 Z Oxadialgyl, Compound liZ Pentoxazone, Compound liZ Caffentrol, Compound liZ Oxadichromemephone, Compound liZ Indanophan, Compound liZ pyriminobacmethyl, compound liZ cyhalohop butyl, compound 1 1Z fentolazamide, compound liZ mefnaset, compound liZ butenachlor, compound liZ dithiopyr, compound liZ benferate, compound liZ pyributicalp, compound liZ bench curve, compound liZ molinate, compound liZ Butamifos, Compound 1 1Z Kink Mouth Rack, Compound liZ Simmesrin, Compound liZ Cymethrin, Compound liZ Benslide, Compound liZ Dimetamethrin, Compound IIZMCPA, Compound IIZMCPB, Compound liZ Etobenzazade, Compound liZ Cumylron, Compound liZ benzobicyclon, Compound Compound liZ pyriftalide, compound liZ bispyribac, compound liZ pyrachlor, compound 1

1Z-lophos, Compound 11ΖΟΚ-701, Compound llZ Penoxsulam, Compound 11ZA VH—301, Compound 11ZKUH—021, Compound llZTH—547, Compound llZ Ventazone, Compound 11Z2, 4—PA, Compound llZ Metamihop, Compound 11Z Furcetosulf Ron, Compound 11ZHOK—201, Compound 11Z Mesotrione, Compound 11Z Propael, Compound 11 Z Quinocamine, Compound 11Z Chromepprop,

Compound 12Z Vilasulfuronethyl, Compound 12Z Bensulfuron methyl, Compound 12 Z Sinosulfuron, Compound 12Z Imazosulfuron, Compound 12Z Azimusulfuron, Compound 12Z Halosulfuron methyl, Compound 12Z Cyclosulfamlone, Compound 12Z Ethoxysulfuron, Compound 12Z Pyrazolate, Compound 12Z Birazoxifen, Compound 12 Z Benzophenap, Compound 12Z Bromobutide, Compound 12Z Naproalide, Compound 12Z Pretilachlor, Compound 12Z Butachlor, Compound 12Z Turchlor, Compound 12ZCNP, Compound 12Z Clomethoxyl, Compound 12Z Bifunox, Compound 1 2Z Oxadiazone, Compound 12Z Oxadialgyl, Compound 12Z Pentoxazone , Compound 12Z Caffentrol, Compound 12Z Oxadichromemephone, Compound 12Z Indanophan, Compound 12Z Pyriminobacmethyl, Compound 12Z Cihalohopbutyl, Compound 1 2Z Fentraza Compound, 12Z Mefnaset, Compound 12Z Butenachlor, Compound 12Z Dithiopyr, Compound 12Z Benfresate, Compound 12Z Pyributicalp, Compound 12Z Benchacurve, Compound 12Z Molinate, Compound 12Z Butamifos, Compound 1 2Z Kink Luck, Compound 12Z Synmethrin, Compound 12Z Cymethrin , Compound 12Z Bensulide, Compound 12Z Dimetamethrin, Compound 12ZMCPA, Compound 12ZMCPB, Compound 12Z Etobenzad, Compound 12Z Cumyllon, Compound 12Z Benzobicyclone, Compound 12Z Pyriphthalide, Compound 12Z Bispyribac, Compound 12Z Pyracol, Compound 1 2Zarophos, Compound 12ZOK—701, Compound 12Z Penoxsulam, Compound 12ZA VH—301, Compound 12ZKUH—021, Compound 12ZTH—547, Compound 12Z Ventazone, Compound 12Z2, 4——, Compound 12Z Metamihop, Compound 12Z full Cetosulfuron, Compound 12ZHOK—201, Compound 12Z Mesotrione, Compound 12Z Propael, Compound 12ΖQuinoclamine, Compound 12ΖChromepprop,

Compound 13Z Vilasulfuronethyl, Compound 13Z Bensulfuron methyl, Compound 13 ΖSinosulfuron, Compound 13Z Imazosulfuron, Compound 13Z Azimusulfuron, Compound 13Z Halosulfuron methyl, Compound 13Z Cyclosulfamlone, Compound 13Z Etoxysulfuron, Compound 13Z pyrazolate, compound 13Z birazoxifene, compound 13 Ζ benzophenap, compound 13Z bromobutide, compound 13Z naproalide, compound 13Z pretilachlor, compound 13Z butachlor, compound 13Z turcurol, compound 13ZCNP, compound 13Z cromethoxyl, compound 13Z Bif Knox, Compound 1 3Z Oxadiazone, Compound 13Z Oxadialgyl, Compound 13Z Pentoxazone, Compound 13Z Caffentrol, Compound 13Z Oxadiclomephone, Compound 13Z Indanophan, Compound 13Z Pyriminobacmethyl, Compound 13Z Cihalohop Butyl, Compound 1 3Z Fentrazamide , Compound 13Z mefnaset, Compound 13Z butenachlor, Compound 13Z Dithiopyr, Compound 13Z Benfresate, Compound 13Z Pyributicalp, Compound 13Z Benchacarb, Compound 13Z Molinate, Compound 13Z Butamifos, Compound 1 3Z Kinkucklak, Compound 13Z Cymmethrin, Compound 13Z Cymethrin Compound 13Z Benslide, Compound 13Z Dimetamethrin, Compound 13ZMCPA, Compound 13ZMCPB, Compound 13Z Etobenzad, Compound 13Z Cumyllon, Compound 13Z Benzobicyclone, Compound 13Z Pyriphthalide, Compound Compound 13Z Bispyribac, Compound 13Z Pyrochlor, Compound 1 3Z-arophos, Compound 13ZOK—701, Compound 13Z Penoxsulam, Compound 13ZA VH—301, Compound 13ZKUH—021, Compound 13ZTH—547, Compound 13Z Ventazone , Compound 13Z2, 4—ΡΑ, Compound 13Z Metamihop, Compound 13Z Flucetosulfuron, Compound 13ZHOK—201, Compound 13Z Mesotrione, Compound 13Z Propael, Compound 13Z Quinocamine, Compound 13Z Chlomeprop, Compound 14Z Virazosulfuronethyl, Compound 14Z Bensulfuron Methyl, Compound 14Z Sinosulfuron, Compound 14Z Imazosulfuron, Compound 14Z Azimusulfuron, Compound 14Z Halosulfuron Methyl, Compound 14Z Cyclosulfamlone, Compound 14Z Ethoxysulfuron, Compound 14Z Villa zolate, Compound 14Z Birazoxifen, Compound 14Z Benzophenap , Compound 14Z Bromobutide, Compound 14Z Naproa-Lide, Compound 14Z Pretilachlor, Compound 14 Ζ Butachlor, Compound 14Z Turculol, Compound 14ZCNP, Compound 14Z Chrometoxichel, Compound 14Z Bif ヱ nox, Compound 14Z Oxadiazone, Compound 14Z Oxadialgyl, Compound 14Z Pentoxazone Compound 14Z Caffentrol, Compound 14Z Oxadichromemephone, Compound 14Z Indanophane, Compound 14Z Pyriminobacmethyl, Compound 14Z Cyhalohop Butyl, Compound 14Z Fentrazamide, Compound 14Z Mefenacet, Compound 14Z Butenachlor, Compound 14Z Dithiopyr, Compound 14Z Benfrate, Compound 14Z Pyributicalp, Compound 14Z Benchocurve, Compound 14Z Molinate, Compound 14Z Butamiphos, Compound 14Z Kink Mouth Rack, Compound 14Z Thin Mesulin, Compound 14Z Cimetrine, Compound 14Z Benthuride, Compound 14Z Dimetamethrin, Compound 14ZMCPA, Compound 14ZMCPB, Compound 14Z Etobenzanide, Compound 14 Z Cumyluron, Compound 14Z Benzobicyclone, Compound 14Z Pyriphthalide, Compound 14Z Bispiriback, Compound 14Z Pyracrole , Compound 14Zarofos, Compound 14ZOK—701, Compound 14Z Penoxsulam, Compound 14ZAVH—301, Compound 14ZKUH—021, Compound 14ZTH—547, Compound 14Z Ventazone, Compound 14Z2, 4—PA, Compound 14Z Metamihop, Compound 14Z flucetosulfuron, compound 14ZHOK—201, compound 14Z mesotrione, compound 14Z propanyl, compound 14Z quinoclamine, compound 14 / chromepprop,

Compound 15Z Vilasulfuronethyl, Compound 15Z Bensulfuron methyl, Compound 15 Z Cinosulfuron, Compound 15Z Imazosulfuron, Compound 15Z Azimusulfuron, Compound 15Z Halosulfuron methyl, Compound 15Z Cyclosulfamlone, Compound 15Z Ethoxysulfuron, Compound 15Z pyrazolate, compound 15Z birazoxifene, compound 15Z benzofenap, compound 15Z bromobutide, compound 15Z naproa-lide, compound 15Z pretilachlor, compound 15Z butachlor, compound 15Z turcrol, compound 15ZCNP, compound 15Z cromethoxyl, compound 15Z bifunox, Compound 1 5Z Oxadiazone, Compound 15Z Oxadialgyl, Compound 15Z Pentoxazone, Compound 15Z Caffentrol, Compound 15Z Oxadiclomephone, Compound 15Z Indanophan, Compound 15Z Liminobacmethyl, Compound 15Z Cihalohop Butyl, Compound 1 5Z Fentrazamide, Compound 15Z Mefenaset, Compound 15Z Butenachlor, Compound 15Z Dithiopyr, Compound 15Z Benfresate, Compound 15Z Pyributicalp, Compound 15Z Benchocurve, Compound 15Z Molinate, Compound 15Z Butamifos, Compound 1 5Z Kink Mouth Rack, Compound 15Z Simmesrin, Compound 15Z Cymetrine, Compound 15Z Bensulide, Compound 15Z Dimetamethrin, Compound 15ZMCPA, Compound 15ZMCPB, Compound 15Z Etobenzad, Compound 15Z Cumyllon, Compound 15Z Benzobicyclone, Compound 15Z Pyriphthalide, Compound 15Z Bispyribac, Compound 15Z Pyrochlor, Compound 15 5Zarophos, Compound 15ZOK—701, Compound 15Z Penoxsulam, Compound 15ZA VH—301, Compound 15ZKUH—021, Compound 15ZTH—547 Things 15Z Venta Zon, Compound 15Z2, 4-PA, Compound 15Z Metamihop, Compound 15Z Flucetosulfuron, Compound 15ZHOK-201, Compound 15Z Mesotrione, Compound 15Z Propael, Compound 15Z Quinocuramin, Compound 15Z Chromepprop,

Compound 16Z Virazosulfuronethyl, Compound 16Z Bensulfuronmethyl, Compound 16Z Cinosulfuron, Compound 16Z Imazosulfuron, Compound 16Z Azimusulfuron, Compound 16Z Halosulfuronmethyl, Compound 16Z Cyclosulfamlone, Compound 16Z Ethoxysulfuron, Compound 16Z pyrazolate, compound 16Z birazoxifene, compound 16Z benzofenap, compound 16Z bromobutide, compound 16Z naproalide, compound 16Z pretilachlor, compound 16Z butachlor, compound 16Z turcurol, compound 16ZCNP, compound 16Z cromethoxyl, compound 16Z bifnox, Compound 1 6Z Oxadiazone, Compound 16Z Oxadialgyl, Compound 16Z Pentoxazone, Compound 16Z Caffentrol, Compound 16Z Oxadiclomephone, Compound 16Z Indanophan, Compound 16Z Liminobacmethyl, Compound 16Z Cihalohop Butyl, Compound 1 6Z Fentrazamide, Compound 16Z Mefnaset, Compound 16Z Butenachlor, Compound 16Z Dithiopyr, Compound 16Z Benflate, Compound 16Z Pyributicalp, Compound 16Z Benchocurve, Compound 16Z Molinate, Compound 16Z Butamifos, Compound 1 6Z Kink Mouth Rack, Compound 16Z Simmesrin, Compound 16Z Cymetrine, Compound 16Z Bensulide, Compound 16Z Dimetamethrin, Compound 16ZMCPA, Compound 16ZMCPB, Compound 16Z Etobenzad, Compound 16Z Cumyllon, Compound 16Z Benzobicyclone, Compound 16Z Pyriphthalide, Compound 16Z Bispyribac, Compound 16Z Pyralchlor, Compound 1 6Zarophos, Compound 16ZOK—701, Compound 16Z Penoxsulam, Compound 16ZA VH—301, Compound 16ZKUH—021, Compound 16ZTH—547, Compound 16Z preventor Zon, compounds 16Z2, 4- PA, compound 16Z metamifop, compound 16Z Furusetosurufu Ron, compounds 16ZHOK- 201, Compound 16Z mesotrione, compound 16Z Puropaeru compound 16Z quinoclamine, compound 16Z clomeprop,

Compound 17Z Virazosulfuronethyl, Compound 17Z Bensulfuronmethyl, Compound 17Z Cinosulfuron, Compound 17Z Imazosulfuron, Compound 17Z Azimusulfuron, Compound 17Z Halosulfuronmethyl, Compound 17Z Cyclosulfamuron, Compound 17Z Et Xylsulfuron, compound 17Z pyrazolate, compound 17Z birazoxifene, compound 17Z benzofenap, compound 17Z bromobutide, compound 17Z naproa-lide, compound 17Z pretilachlor, compound 17Z butachlor, compound 17Z turcurol, compound 17ZCNP, compound 17Z chrometox Shell, Compound 17Z Bifnox, Compound 1 7Z Oxadiazone, Compound 17Z Oxadialgyl, Compound 17Z Pentoxazone, Compound 17Z Caffentrol, Compound 17Z Oxadichromemephone, Compound 17Z Indanophan, Compound 17Z Pyriminobacmethyl, Compound 17Z Cihalohop Butyl, Compound 1 7Z Fentrazamide, Compound 17Z Mefnaset, Compound 17Z Butenachlor, Compound 17Z Dithiopyr, Compound 17Z Benfresate, Compound 17Z Pyributicalp, Compound 17Z Benchocar , Compound 17Z Molinate, Compound 17Z Butamiphos, Compound 1 7Z Kink Mouth Rack, Compound 17Z Simmesrin, Compound 17Z Cymetrine, Compound 17Z Benslide, Compound 17Z Dimetamethrin, Compound 17ZMCPA, Compound 17ZMCPB, Compound 17Z Etobenzad, Compound 17Z Cumylron, Compound 17Z Benzobicyclone, Compound 17Z Pyriphthalide, Compound 17Z Bispyribac, Compound 17Z Pyracol, Compound 1 7Z-Lofos, Compound 17ZOK—701, Compound 17Z Penoxsulam, Compound 17ZA VH-301, Compound 17ZKUH— 021, Compound 17ZTH—547, Compound 17Z Ventazone, Compound 17Z2, 4-—ΡΑ, Compound 17Z Metamihop, Compound 17Z Flucetosulfuron, Compound 17ZHOK—201, Compound 17Z Mesotrione, Compound 17Z Propaer, Compound 17ΖQuinoclamine, Compound 17ΖCromepprop,

Compound 18Z Virazosulfuronethyl, Compound 18Z Bensulfuron methyl, Compound 18 ΖSinosulfuron, Compound 18Z Imazosulfuron, Compound 18Z Azimusulfuron, Compound 18Z Halosulfuron methyl, Compound 18Z Cyclosulfamlone, Compound 18Z Ethoxysulfuron, Compound 18Z pyrazolate, compound 18Z birazoxifene, compound 18 Ζ benzofenap, compound 18Z bromobutide, compound 18Z naproalide, compound 18Z pretilachlor, compound 18Z butachlor, compound 18Z turcrol, compound 18ZCNP, compound 18Z cromethoxyl, compound 18Z bifnox, Compound 1 8Z Oxadiazone, Compound 18Z Oxadialgyl, Compound 18Z Pentoxazone, Compound 18Z Caffentrol, Compound 18Z Oxadiclomephone, Compound 18Z Indano Fan, Compound 18Z Pyriminobacmethyl, Compound 18Z Cihalohop Butyl, Compound 1 8Z Fentrazamide, Compound 18Z Mefenaset, Compound 18Z Butenachlor, Compound 18Z Dithiopyr, Compound 18Z Benfresate, Compound 18Z Pyributicalp, Compound 18Z Benchocurve, Compound 18Z Molinate , Compound 18Z Butamiphos, Compound 1 8Z Kink Mouth Rack, Compound 18Z Simmesrin, Compound 18Z Cymetrine, Compound 18Z Benslide, Compound 18Z Dimetamethrin, Compound 18ZMCPA, Compound 18ZMCPB, Compound 18Z Etobenzazade, Compound 18Z Cumylron, Compound 18Z Benzobicyclo Compound 18Z Pyriphthalide, Compound 18Z Bispyribac, Compound 18Z Pyracol, Compound 1 8Z-Lolophos, Compound 18ZOK—701, Compound 18Z Penoxsulam, Compound 18ZA VH—301, Compound 18ZKUH—021, Compound 18ZTH- 547, Compound 18Z preventor Zon, compounds 18Z2, 4- PA, compound 18Z metamifop, compound 18Z Furusetosurufu Ron, compounds 18ZHOK- 201, Compound 18Z mesotrione, compound 18Z Puropaeru compound 18Z quinoclamine, compound 18Z clomeprop,

Compound 19Z Virazosulfuronethyl, Compound 19Z Bensulfuron methyl, Compound 19 Z Cinosulfuron, Compound 19Z Imazosulfuron, Compound 19Z Azimusulfuron, Compound 19Z Halosulfuron methyl, Compound 19Z Cyclosulfamuron, Compound 19Z Ethoxysulfuron, Compound 19Z pyrazolate, compound 19Z birazoxifene, compound 19Z benzofenap, compound 19Z bromobutide, compound 19Z naproalide, compound 19Z pretilachlor, compound 19Z butachlor, compound 19Z turcurol, compound 19ZCNP, compound 19Z cromethoxyl, compound 19Z bifunox, Compound 1 9Z Oxadiazone, Compound 19Z Oxadialgyl, Compound 19Z Pentoxazone, Compound 19Z Caffentrol, Compound 19Z Oxadiclomephone, Compound 19Z Indanophan, Compound 19Z Liminobacmethyl, Compound 19Z Cihalohop Butyl, Compound 1 9Z Fentrazamide, Compound 19Z Mefnaset, Compound 19Z Butenachlor, Compound 19Z Dithiopyr, Compound 19Z Benfresate, Compound 19Z Pyributicalp, Compound 19Z Benchocarb, Compound 19Z Molinate, Compound 19Z Butamifos, Compound 1 9Z Kink Mouth Rack, Compound 19Z Simmesrin, Compound 19Z Cymetrine, Compound 19Z Benslide, Compound 19Z Dimetamethrin, Compound 19ZMCPA, Compound 19ZMCPB, Compound Compound 19Z etozanzade, compound 19Z cumyluron, compound 19Z benzobicyclone, compound 19Z pyriftalide, compound 19Z bispyrivac, compound 19Z pyrachlor, compound 1 9Z-arophos, compound 19ZOK-701, compound 19Z penoxsulam, compound 19ZA VH—301, Compound 19ZKUH—021, Compound 19ZTH—547, Compound 19Z Ventazone, Compound 19Z2, 4—ΡΑ, Compound 19Z Metamihop, Compound 19Z Flucetosulfuron, Compound 19ZHOK—201, Compound 19Z Mesotrione, Compound 19Z Propaer , Compound 19Ζ quinoclamine, Compound 19Ζ Chromepprop,

Compound 20ΖVirazosulfuronethyl, Compound 20ΖBensulfuron methyl, Compound 20ΖSinosulfuron, Compound 20ΖImazosulfuron, Compound 20ΖAzimusulfuron, Compound 20ΖHalosulfuron methyl, Compound 20ΖCyclosulfamlone, Compound 20ΖEthoxysulfuron, Compound 20 Pyrazolate, Compound 20 Birazoxifene, Compound 20 Benzofenap, Compound 20 Bromobutide, Compound 20 Naproalide, Compound 20 Pretilachlor, Compound 20 Butachlor, Compound 20 Turculol, Compound 20ZCNP, Compound 20Z Chlomethoxyl, Compound 20Z bifnox, Compound 20 0Z Oxadiazone, Compound 20 Oxadialgyl, Compound 20 Pentoxazone, Compound 20 Kafuentrol, Compound 20 Oxadiclomephone, Compound 20 O Indanov Compound 20 化合物 Pyriminobacmethyl, Compound 20ΖCyhalohopbutyl, Compound 20ΖFentrazamide, Compound 20ΖMefenacet, Compound 20ΖButenachlor, Compound 20ΖDithiopyr, Compound 20ΖBenfrecate, Compound 20ΖPyributicalp, Compound 20ΖBenchocurve, Compound 20ΖMolinate , Compound 20-Buta mifos, Compound 20 Kink mouth rack, Compound 20 Cymmesrin, Compound 20-Cymethrin, Compound 20-Benslide, Compound 20 Dimetamethrin, Compound 20ZMCPA, Compound 20ZMCPB, Compound Z20Z Etobenzad, Compound 20Z Cumylron, Compound 20Z benzobicyclone, compound 20Z pyriftalide, compound 20Z bispyribak, compound 20Z pyrachlor, compound 20Zarophos, compound 20ZOK—701, compound 20Z penoxsulam, compound 20Z AVH—301, compound 20Z KUH—021, Compound 2θΖΤΗ-547, Compound 20ΖVentazone, Compound 20Ζ2, 4—ΡΑ, Compound 20ΖMetamihop, Compound 20ΖFurcetosulfuron, Compound 20ΖΗΟΚ201, Compound 20ΖMesotrione, Compound 20Ζproperol , Compound 20Z Kinoclamine, Compound 20Ζ Chromepprop

Compound 21Z Virazosulfuronethyl, Compound 21Z Bensulfuronmethyl, Compound 21 ΖSinosulfuron, Compound 21Z Imazosulfuron, Compound 21Z Azimusulfuron, Compound 21Z Halosulfuronmethyl, Compound 21Z Cyclosulfamlone, Compound 21Z Ethoxysulfuron, Compound 21Z pyrazolate, compound 21Z birazoxifene, compound 21 Ζ benzophenap, compound 21Z bromobutide, compound 21Z naproalide, compound 21Z pretilachlor, compound 21Z butachlor, compound 21Z turcrol, compound 2lZCNP, compound 21Z cromethoxyl, compound 21Z Bifnox, Compound 2 1Z Oxadiazone, Compound 21 Z Oxadialgyl, Compound 21 Z Pentoxazone, Compound 21Z Caffentrol, Compound 21Z Oxadiclomephone, Compound 21Z Indanophan, Compound 21Z Pyriminobacmethyl, Compound 21Z Cihalohop Butyl, Compound 2 1Z Fentrazamide, Compound 21Z Mefenaset, Compound 21Z Butenachlor, Compound 21Z Dithiopyr, Compound 21Z Benfresate, Compound 21Z Pyributicalp, Compound 21Z Benchocurve, Compound 21Z Molinate Butamifos, Compound 2 1Z Kink Mouth Rack, Compound 21Z Simmesrin, Compound 21Z Cymetrine, Compound 21Z Bensulide, Compound 21Z Dimetamethrin, Compound 2lZMCPA, Compound 2lZMCPB, Compound 21Z Etobenzazade, Compound 21Z Cumylron, Compound 21Z Benzobicyclone, Compound Compound 21Z pyriftalide, compound 21Z bispyribak, compound 21Z pyrachlor, compound 2 1Z-arophos, compound 21ZOK—701, compound 21Z penoxsulam, compound 21ZA VH—301, compound 21ZKUH—021, compound 21ZTH—547, Compound 21Z Bentazone, Compound 21Z2, 4-— ΡΑ, Compound 21Z Metamihop, Compound 21Z Flucetosulfuron, Compound 21ZHOK— 201, Compound 21Z Mesotrione, Compound 21Z Propael, Compound 21Z Quinoclamine, Compound 21Z Chromepprop In the present invention, Compound (A) 1 At least one compound selected from Daimron, Dimepiperate, and Espelo force Lube is usually applied in an amount of 0.001 to 100 parts by weight, preferably 0.01 to 30 parts by weight per part by weight.

The application rate of compound (Α) is usually lg-10 kgZha, preferably 10 g-lkgZha. Daimlon, dimethylpiperate and esprocarp medium strength The application rate of at least one compound selected is usually lg—10 kgZha, preferably 10 g—3 kgZha.

 The composition of the present invention is usually mixed with an appropriate solid carrier or liquid carrier, and if desired, a surface active agent, a penetrating agent, a spreading agent, a thickening agent, an antifreezing agent, a binder, an anti-caking agent, a disintegration. Agent, antifoaming agent, antiseptic and anti-degradation agent, etc., added, soluble concentrate, emulsion (.emulsifiable concentrate), wettable powder, water soluble powder, granule hydration Water dispersible granule, water soluole granule, suspension concentrate, concentrate rated emulsion, suspoemulsion, microemulsion (m icroemulsion), It can be put to practical use in preparations of any dosage form such as dustable powder, granule and gel. In addition, from the viewpoint of labor saving and safety improvement, the preparations of any of the above dosage forms can be enclosed in a water-soluble package. If necessary, it can be mixed with other herbicides, insecticides, fungicides, plant growth regulators, fertilizers, etc. during formulation or spraying.

 Examples of the solid carrier include quartz, kaolinite, neurophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite, and diatomaceous earth, calcium carbonate, ammonium sulfate, sodium sulfate and salt. Inorganic salts such as potassium, synthetic silicic acid and synthetic silicate.

 Examples of the liquid carrier include alcohols such as ethylene glycol, propylene glycol, and isopropanol, aromatic hydrocarbons such as xylene, alkylbenzene, and alkylnaphthalene, ethers such as butylcetosolve, ketones such as cyclohexanone, —Esters such as butaguchi ratataton, acid amides such as N-methylpyrrolidone and N-octylpyrrolidone, vegetable oils such as soybean oil, rapeseed oil, cottonseed oil and castor oil, and water.

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

Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene fatty acid ether. Nonionic surfactants such as stealth, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters, alkyl sulfates, alkylbenzene sulfonates, lignin sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, alkyl naphthalene sulfonates , Formalin condensate salt of naphthalene sulfonic acid, salt of formalin condensate of alkyl naphthalene sulfonic acid, polyoxyethylene alkyl aryl ether sulfate and phosphate, polyoxyethylene styryl ether ether sulfate and phosphate, poly Carboxylic acid surfactants such as carboxylates and polystyrene sulfonates, cationic surfactants such as alkylamine salts and alkyl quaternary ammonium salts, and amphoteric surfactants such as amino acids and betaines Agents.

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

 At this time, a plurality of other herbicides, insecticides, fungicides, plant growth regulators, fertilizers and the like can be used in combination. In particular, when one or more other herbicides are added, the herbicidal spectrum can be expanded, and the effects of the present invention can be made more stable.

 Next, formulation examples of preparations when using the composition of the present invention are shown. However, the blending examples of the present invention are not limited to these. In the following formulation examples, “parts” means parts by mass.

 (Wettable powder)

The present composition 0.1 to 80 parts

Solid carrier 5-98.9 parts

1-10 parts of surfactant

Other 0-5

 Other examples include anti-caking agents and decomposition inhibitors.

 (孚 L agent, emmsifiable concentrate) J

Composition of the present invention 0.1-30 parts

45-95 parts of liquid carrier Surfactant 4. 9-15 parts Others 0-10 parts

 Other examples include spreading agents and decomposition inhibitors.

(Suspension concentrate)

The composition of the present invention 0.1-70 parts

Liquid carrier 15-98.89 parts

1 to 12 parts surfactant

Others 0.01-30

 Other examples include antifreezing agents and thickeners.

[Water dispersible granule]

The composition of the present invention 0.1-90 parts

Solid carrier 0 ~ 98.9 9 parts

1-20 parts of surfactant

Other 0-10 copies

 Other examples include a binder and a decomposition inhibitor.

[Soluble concentrate]

The composition of the present invention 0.01-70 parts

Liquid carrier 20-99.99 parts

Other 0-10 copies

 Other examples include antifreezing agents and spreading agents.

[Granule]

The present composition 0.01 to 80 parts

Solid carrier 10-99.99 parts

Other 0-10 copies

 Other examples include a binder and a decomposition inhibitor.

[Dustable powder]

Composition of the present invention 0.01-30 parts

Solid carrier 65-99.99 parts Other 0-5 parts

 Other examples include a drift inhibitor and a decomposition inhibitor.

 In use, the above preparation is diluted with water 1 to: LOOOO times or not diluted, and the active ingredient strength is 0.001 to 50 kg per hectare (ha), preferably ί or 0.001 to LOkg. Scatter.

 Example

[0119] Formulation examples

 Next, specific examples of agrochemical formulations containing the compound as an active ingredient are shown, but the invention is not limited to these examples. In the following formulation examples, “part” means part by mass.

 Hogi Case 1] wettable powder

 Compound (A) 10 parts

 Daimlon 10 parts

 Neurophylite 74 words

 Solpol 5039 4 parts

 (Mixture of nonionic surfactant and ionic surfactant: Toho Chemical Co., Ltd. product name)

 Carplex # 80D 2 parts

 (Synthetic hydrous silicate: Shionogi Pharmaceutical Co., Ltd., trade name)

 The above is uniformly mixed and ground to obtain a wettable powder.

[0120] Honomi Case 2] Emulsifiable concentrate

 Compound (A) 2 parts

 Daimron 3 parts

 75 parts of xylene

 N-Methylolpyrrolidone 15 parts

 Sonoreponore 2680 5

 (Mixture of nonionic surfactant and ionic surfactant: Toho Chemical Co., Ltd. product name)

The above is uniformly mixed to obtain an emulsion. [0121] Hogi Case 3] Suspension concentrate

 Compound (A) 15 parts

 Daimlon 10 parts

 Agrisol S-710 10 parts

 (Nonionic surfactant: Kao Co., Ltd. trade name)

 LUNOX 1000C 0.5 part

 (Anionic surfactant: Toho Chemical Co., Ltd. trade name)

 Xanthan gum 0.2 parts

 Water 64.3

 After the above is uniformly mixed, wet pulverization is performed to obtain a suspension.

[0122] Ho S case 4) water dispersible granule

 Compound (A) 25 parts

 Daimlon 50 parts

 Haitenol NE-15 5 parts

 (Anionic surfactant: Daiichi Kogyo Seiyaku Co., Ltd., trade name)

 Vanillex N 10 parts

 (Aon surfactant: Nippon Paper Industries Co., Ltd. trade name)

 Carplex # 80D 10 parts

 (Synthetic hydrous silicate: Shionogi Pharmaceutical Co., Ltd., trade name)

 After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to obtain a granulated wettable powder.

[0123] Ho S Case 5) Granule

 Compound (A) 3 parts

 Daimlon 2nd part

 50 parts of bentonite

 Tanorek 45

After uniformly mixing and pulverizing the above, a small amount of water is added, mixed with stirring, granulated with an extrusion granulator, and dried to form granules. [0124] Example 6] dustable powder

 Compound (A) 1 part

 Daimlon 2nd part

 Carplex # 80D 0.5

 (Synthetic hydrous silicate: Shionogi Pharmaceutical Co., Ltd., trade name)

 95 copies of Kaolinite

 Diisopropinole diacid 1.5

 The above is uniformly mixed and pulverized to obtain a powder.

[0125] Hogi Case 7] wettable powder

 Compound (A) 10 parts

 Zimepiperate 10 copies

 Neurophylite 74 words

 Solpol 5039 4 parts

 (Mixture of nonionic surfactant and ionic surfactant: Toho Chemical Co., Ltd. product name)

 Carplex # 80D 2 parts

 (Synthetic hydrous silicate: Shionogi Pharmaceutical Co., Ltd., trade name)

 The above is uniformly mixed and ground to obtain a wettable powder.

[0126] Honomi Case 8] Emulsifiable concentrate

 Compound (A) 2 parts

 Zimepiperate 3 parts

 75 parts of xylene

 N-Methylolpyrrolidone 15 parts

 Sonoreponore 2680 5

 (Mixture of nonionic surfactant and ionic surfactant: Toho Chemical Co., Ltd. product name)

 The above is uniformly mixed to obtain an emulsion.

[0127] Hojigo 9) Suspension concentrate Compound (A) 15 parts

 Zimepiperate 10 copies

 Agrisol S-710 10 parts

 (Nonionic surfactant: Kao Co., Ltd. trade name)

 LUNOX 1000C 0.5 part

 (Anionic surfactant: Toho Chemical Co., Ltd. trade name)

 Xanthan gum 0.2 parts

 Water 64.3

 After the above is uniformly mixed, wet pulverization is performed to obtain a suspension.

[0128] Honoki case 10] water dispersible granule

 Compound (A) 25 parts

 Zimepiperate 50 copies

 Haitenol NE-15 5 parts

 (Anionic surfactant: Daiichi Kogyo Seiyaku Co., Ltd., trade name)

 Vanillex N 10 parts

 (Aon surfactant: Nippon Paper Industries Co., Ltd. trade name)

 Carplex # 80D 40 parts

 (Synthetic hydrous silicate: Shionogi Pharmaceutical Co., Ltd., trade name)

 After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to obtain a granulated wettable powder.

[0129] Self Example 11] Granule

 Compound (A) 3 parts

 Zimepiperate 2 parts

 50 parts of bentonite

 Tanorek 45

 After uniformly mixing and pulverizing the above, a small amount of water is added, mixed with stirring, granulated with an extrusion granulator, and dried to form granules.

[0130] Self Example 12] dustable powder Compound (A) 1 part

 Zimepiperate 2 parts

 Carplex # 80D 0.5

 (Synthetic hydrous silicate: Shionogi Pharmaceutical Co., Ltd., trade name)

 95 copies of Kaolinite

 Diisopropinole diacid 1.5

 The above is uniformly mixed and pulverized to obtain a powder.

[0131] Hogi Case 13] wettable powder

 Compound (A) 10 parts

 Esprocanolev 10 copies

 Neurophylite 74 words

 Solpol 5039 4 parts

 (Mixture of nonionic surfactant and ionic surfactant: Toho Chemical Co., Ltd. product name)

 Carplex # 80D 2 parts

 (Synthetic hydrous silicate: Shionogi Pharmaceutical Co., Ltd., trade name)

 The above is uniformly mixed and ground to obtain a wettable powder.

[0132] Honomi Case 14] Emulsifiable concentrate

 Compound (A) 2 parts

 Esprocanolev 3 parts

 75 parts of xylene

 N-Methylolpyrrolidone 15 parts

 Sonoreponore 2680 5

 (Mixture of nonionic surfactant and ionic surfactant: Toho Chemical Co., Ltd. product name)

 The above is uniformly mixed to obtain an emulsion.

[0133] Hogi Case 15] Suspension concentrate

Compound (A) 15 parts Esprocanolev 10 copies

 Agrisol S-710 10 parts

 (Nonionic surfactant: Kao Co., Ltd. trade name)

 LUNOX 1000C 0.5 part

 (Anionic surfactant: Toho Chemical Co., Ltd. trade name)

 Xanthan gum 0.2 parts

 Water 64.3

 After the above is uniformly mixed, wet pulverization is performed to obtain a suspension.

[0134] Ho S Case 16] Granule wettable powder (water dispersible granule)

 Compound (A) 25 parts

 Esprocanolev 50 copies

 Haitenol NE-15 5 parts

 (Anionic surfactant: Daiichi Kogyo Seiyaku Co., Ltd., trade name)

 Vanillex N 10 parts

 (Aon surfactant: Nippon Paper Industries Co., Ltd. trade name)

 Carplex # 80D 40 parts

 (Synthetic hydrous silicate: Shionogi Pharmaceutical Co., Ltd., trade name)

 After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to obtain a granulated wettable powder.

[0135] Ho S Case 17) Granule

 Compound (A) 3 parts

 Esprocanolev 2nd part

 50 parts of bentonite

 Tanorek 45

 After uniformly mixing and pulverizing the above, a small amount of water is added, mixed with stirring, granulated with an extrusion granulator, and dried to form granules.

[0136] Self-regular case 18] dustable powder

Compound (A) 1 part Esprocanolev 2nd part

 Carplex # 80D 0.5

 (Synthetic hydrous silicate: Shionogi Pharmaceutical Co., Ltd., trade name)

 95 copies of Kaolinite

 Diisopropinole diacid 1.5

 The above is uniformly mixed and pulverized to obtain a powder.

[0137] The usefulness of the composition of the present invention as a herbicide will be specifically described in the following test examples.

 The phytotoxicity reduction effect or herbicidal effect of each test example was investigated according to the following criteria!

 Judgment criteria

 5 · · · Over 90% killing rate (almost completely dead)

 4 .... Hericide rate 70% or more, less than 90%

 3 ...

 2 ... Hericide rate 20% or more, less than 40%

 1 ...

 0 · · · 5% or less killing rate (almost no effect)

 [Test Example 1] Chemical damage test under water leakage conditions

 After alluvial soil was put into a 1/10000 are plastic pot with a hole in the bottom, water was added and mixed to create a 4 cm flood condition. A 2.5-leaf rice seedling was transplanted into the above pot, and the suspension of the prescribed concentration of the reagent was dropped using a wettable powder prepared according to the formulation example on the 9th day after transplanting. . Water leakage was performed by placing a pot in a plastic vat and draining the water in the vat, and leaking water 2 cm / day for 3 consecutive days after chemical treatment. On the 28th day after drug treatment, phytotoxicity to rice was investigated according to the above criteria. As a result, Compound (A) + Daimlone, Compound (A) + Dimepiperate, and Compound (A) + Esprocarb all showed a phytotoxicity-reducing effect on rice compared to Compound (A) alone.

[0138] [Test Example 2] phytotoxicity test under standing seedlings and leakage conditions The seedling condition was 4 cm submersion conditions after alluvial soil was put into a 1Z10000 are plastic pot and water was mixed. A 2.5-leaf rice seedling was fixed on the rice pad with the roots exposed. On the other hand, water leakage conditions were the same as in Test Example 1, and 2.5-leaf rice seedlings were transplanted. Under both conditions, a suspension of a predetermined concentration of the reagent was dropped with a wettable powder prepared according to the formulation example on the 6th day after transplantation. On the 24th day after drug treatment, the phytotoxicity of rice was investigated according to the above criteria. As a result, all of Compound (A) + Dimron, Compound (A) + Dimepiperate, and Compound (A) + Esprocalp showed a phytotoxicity-reducing effect on rice compared to Compound (A) alone. It was.

 [Test Example 3] Herbicidal effect test by pretreatment of weeds in flooded condition

 After alluvial soil was put into a 1/10000 are plastic pot, water was added and mixed to create a 4 cm flood condition. The seeds of Novier, Inuhotarui, Konagi, Kakashigusa and Azena were sown, and a suspension of a predetermined concentration of the reagent was dropped using a wettable powder prepared according to the formulation example on the second day after sowing. On the 38th day after the chemical treatment, the herbicidal effect on various weeds was investigated according to the above criteria. As a result, all of Compound (A) + Daimlone, Compound (A) + Dimepiperate, and Compound (A) + Esprocalp have the ability to show no decrease in herbicidal effect compared to the case of Compound (A) alone. I got it.

 [0140] [Test Example 4] Herbicidal effect test by post-weed weed treatment under flooded conditions

 After putting alluvial soil into a 1/10000 are plastic pot, seeding Inuhotarui seeds, covering with paddy field topsoil, seeding Nobies, Konagi, Kakashidasa, Azena seeds, adding water, 4 cm Water conditions were used. On the 14th day after seeding, a suspension of a predetermined concentration of the reagent was dropped using a hydrating agent prepared according to the formulation example. On the 38th day after drug treatment, the herbicidal effect on various weeds was investigated according to the above criteria. As a result, the compound (A) + dimron, compound (A) + dimepiperate, and compound (A) + esprocarp showed no decrease in herbicidal effect compared to the case of compound (A) alone. I helped.

 [0141] [Test Example 5] Chemical damage test under rice seedling conditions

After alluvial soil was put into a 1/10000 are plastic pot, water was added and mixed to create a 4 cm flood condition. A 2.5-leaf rice seedling was fixed on the rice pad with the roots exposed. Using the wettable powder prepared according to the formulation example on the 6th day of transplantation, A suspension having a predetermined concentration was dropped. On the 24th day after drug treatment, phytotoxicity to rice was investigated according to the above criteria. The results are shown in Table 4.

[Table 4]

[Table 4] Compound treatment dose amount Seedling

 (g / a) Compound 1 1 .5 1

 3 3

 Compound 9 1 .5 2

 3 3

 Compound 2 1 1. 5 1

 3 2

 Compound 1 + Daimlone 1.5 + 1 0 0

 3 + 1 0 0

 Compound 9 + Daimlone 1.5 + 1 0 0

 3 + 1 0 0

 Compound 2 1 + Daimlone 1.5 + 1 0 0

 3 + 1 0 0

 Compound 1 + Espurolube 1.5 + 5 0

 3 + 5 1

 Compound 9 + Esprocalp 1.5 + 5 1

 3 + 5 2

 Compound 2 1 + Esprocalp 1.5 + 5 0

 3 + 5 1

 Compound 1 + Dimepiperate 1.5 + 5 0

 3 + 5 1

 Compound 9 + Dimepiperate 1.5 + 5 1

 3 + 5 2

 Compound 2 1 + Dimepiperate 1.5 + 5 0

 3 + 5 0 [Test Example 6] Herbicidal effect test by post-treatment after generation of Azegaya in flooded condition

After alluvial soil was put into a 1/10000 are plastic pot, seeds were seeded and grown in a greenhouse. After growing for 20 days, water was added so that the water depth was 2 cm, and a suspension of a predetermined concentration of the reagent was dropped using a wettable powder prepared according to the combination example. On the 20th day after the chemical treatment, the herbicidal effect against Azegaya was investigated according to the above criteria. The results are shown in Table 5. [0143] [Test Example 7] Herbicidal effect test by post-treatment of nobies in flooded condition

After alluvial soil was put into a 1/10000 are plastic pot, seeds of Nobies were sown and grown in a greenhouse. After growing for 14 days, water was added so that the water depth was 4 cm, and the suspension solution with the prescribed concentration of the reagent was dropped using the wettable powder prepared according to the formulation example the next day. . On the 21st day after drug treatment, the herbicidal effect on nobies was investigated according to the above criteria. The results are shown in Table 5.

 [0144] [Test Example 8] Herbicidal effect test by pre-treatment of Inuhotarui under flooding conditions

 After alluvial soil was put into a 1/10000 are plastic pot, water was added and mixed to create a 4 cm flood condition. Innuhotarui seeds (from Honjo, Akita Prefecture) were sown in the pot, and a suspension with a predetermined concentration of the reagent was dropped using a wettable powder prepared according to the formulation example on the first day of sowing. On the 21st day after drug treatment, the herbicidal effect on nobies was investigated according to the above criteria. The results are shown in Table 5.

[Table 5]

[Table 5] Compound treatment dose Azegaya Nobie Firefly

 (g / a) Compound 1 0. 5 0 5 0 Compound 9 0. 5 0 5 0 Compound 21 0. 5 0 5 0 Pyrazos noreph nuchinol Snoreflon 0. 9 0 1 0 Azimusulfuron 0. 2 2 4 0

/ ヽ D Snolev C3 Methinole 0. 6 0 0 0 Cyclos Nolef Amron 0. 6 0 0 0 Etoxys / Leflon 0. 2 1 2 0 Bromobutide 9 0 0 5 Pretiracronore 4.5 5 3 2 5 Butacronore 7.5 3 2 5 Oxadiazone 4. 5 1 2 5 Pentoxazone 3 1 2 5 Cuffenströnole 2.5 5 5 5 5 Oxazik mouth mephone 0. 8 5 5 5 Lindanophan 1. 5 5 5 5 Cihalohop butyl 1. 5 5 5 0 Fentrazamide 3 5 5 5 Mef Nassette 10 5 5 5 Molinate 20 5 5 5 Kink mouth rack 3 0 5 0 Dimetameline 0. 6 0 0 0

P CMB 2. 4 0 0 5 Benzobicyclone 2 4 4 5 Piroclani nore 1. 8 2 3 5

AVH- 30 1 4 3 3 5 Mesotrione 0.5 3 3 5 Chromprop 3.5 5 0 0 5 Compound 1 + Pyrazosulfuronetinore 0.5 + 0. 2 2 5 0 Compound 1 + Bensulfurn methyl + 0. 5 0 5 0 Compound 1 + Imazosulfone 0.5 0.5 + 0. 9 1 5 0 Compound 1 + Azimusulfone 0.5 0.5 + 0. 2 3 5 0 Compound 1 + Rosnoreflon methyl 0. 5 + 0. 6 0 5 0 Compound 1 + Cyclosnorefamlon 0.5 + 0. 6 0 5 0 Compound 1 + Ethoxysulfuron 0.5 + 0. 2 0 5 0 Compound 1 + Bromobutide 0.5 + 9 0 5 5 Compound 1 + Pretilachlor 0.5 + 4. 5 3 5 5 Compound 1 + Butachlor 0.5 .5 + 7. 5 3 5 5 Compound 1 + Oxadiazone 0.5 + 4.5 5 Compound 5 0. 5 + 3 2 5 5

[Table 6] Compound 1 + Cafence Tronore 0 5 + 2. 5 5 5 5 Compound 1 + Oxadichrome Fone 0 5 + 0. 8 5 5 5 Compound 1 + Linda Juan 0 5 + 1. 5 5 5 5 Compound 1 + Cihalohop butyl 0 5 + 1. 5 5 5 0

'Compound 1 + Fentrazamide 0 5 + 3 5 5 5

'Composite 1 + Mefner Set 0 5 + 10 5 5 5 Composite 1 + Molinaito 0 5 + 20 5 5 5

'Compound 1 + Kink mouth rack 0 5 + 3 0 5 0

'Compound 1 + Dimetamethrin 0 5 + 0. 6 0 5 0

'Compound 1 + PCMB 0 5 + 2. 4 0 5 5

'Compound 1 + Benzovicone 0 5 + 2 4 5 5 Compound 1 + Pyrocraninore 0 5+ 1. 8 2 5 5 Compound 1 + A VH- 301 0 5 + 4 3 5 5 Compound 1 + Mesotrione 0 5 + 0. 5 3 5 5

'Compound 1 + Chromprop 0 5 + 3. 5 0 5 5

'Composite 9 + Pyrazos Norev Neckinore 0 5 + 0. 2 2 5 0

'Composite 9 + Bensnoleph Michinore 0 5 + 0. 5 0 5 0

'Composite 9 + Imazo Snorev mouth 0 5 + 0. 9 1 5 0

'Composite 9 + Azimus Noreflon 0 5 + 0. 2 2 5 0

'Hy compound 9 + Nos Roth Nore Fron Mechinole 0 5 + 0. 6 0 5 0

'Compound 9 + Cyclos norefum mouth 0 5 + 0. 6 0 5 0

'Compound 9 + Etoxys noreflon 0 5 + 0. 2 0 5 ϋ

'Compound 9 + Bromobutide 0 5 + 9 0 5 5

'Compound 9 + Pretilachlor 0 5 + 4. 5 3 5 5

'Composite 9 + Butacronore 0 5 + 7. 5 3 5 5

'Compound 9 + Oxadiazon 0 5 + 4. 5 2 5 5

'Compound 9 + pentoxazone 0 5 + 3 1 5 5

'Composite 9 + Caffence Troll 0 5 + 2.5 5 5 5

'Compound 9 + Oxadichrome Mephone 0 5 + 0. 8 5 5 5

'Compound 9 + Lindano Juan 0 5+ 1. 5 5 5 5

'Compound 9 + Cihalohop Butyl 0 5 +1. 5 5 5 0

'Compound 9 + Fentrazamide 0 5 + 3 5 5 5

'Composite 9 + Mehuena set 0 5 +1 0 5 5 5

'Composite 9 + Moline 1 0 5 + 2 υ 5 5 5

'Composite 9 + Kink mouth rack 0 5 + 3 0 5 0

'Hy compound 9 + dimetamethrin 0 5 + 0. 6 0 5 0

'Compound 9 + P CMB 0 5 + 2. 4 0 5 5

'Composite 9 + benzobisic mouth 0 5 + 2 4 5 5

: Compound 9 + Pirocraninore 0 5+ 1. 8 2 5 5

'Composite 9 + AVH- 301 0 5 + 4 3 5 5

'Compound 9 + Mesotrione 0 5 + 0. 5 3 5 5

[Compound 9 + Chromepprop 0 5 + 3. 5 0 5 5 Compound 21 + Virazosulfuronethyl 0.5 + 0. 2 2 5 0 Compound 21 + Bensulfuron methyl 0.5 + 0. 5 0 5 0 Compound 21 + Imazosulfuron 0.5 + 0. 9 0 5 0 Compound 2 1 + Azimusulfuron 0.5 + 0. 2 2 5 0 [Compound 2 1 + Halos / Leflon methinole 0.5 + 0. 6 0 5 0 [Compound 21 + Cyclosulfamuron 0.5 + 0. 6 0 5 0 Compound 2 1 + Ethoxysulfuron 0.5 + 0. 2 2 5 0 [Table 7] Compound 2 1 + Bromotide 0.5.5 + 9 0 5 5 Compound 2 1 + Pretilaclonorole 0.5.5 + 4. 5 3 5 5 Compound 2 1 + Butachlor 0.5.5 + 7. 5 3 5 5 Compound 2 1 + Oxadiazone 0.5 + 4. 5 1 5 5 Compound 2 1 + Pentoxazone 0.5.5 + 3 2 5 5 Compound 2 1 + Cafence Tronoreno 0.5.5 + 2. 5 5 5 5 Compound 2 1 + Oxadichromemephone 0.5 + 0. 8 5 5 5 Compound 2 1 + Indanophane 0.5 0.5 +1. 5 5 5 5 Compound 2 1 + Cyhalohop butyl 0.5 5 +1. 5 5 5 0 Compound 2 1 + Fentrazamide 0.5 + 3 5 5 5 Compound 2 1 + Mefenacet 0.5.5 +1 0 5 5 5 Compound 2 1 + Molinate 10.5 + 20 5 5 5 Compound 2 1 + Kink mouth rack 0. 5 + 3 0 5 0 Compound 2 1 + Dimetamethrin 0.5 + 0. 6 0 5 0 Compound 2 1 + P CMB 0.5 + 2. 4 0 5 5 Compound 2 1 + Benzobicyclone 0.5 + 2 4 5 5 Compound 2 1 + Pilocura Ninore 0.5 1 + 1 8 2 5 5 Compound 2 1 + AVH- 301 0.5 + 4 3 5 5 Compound 2 1 + Method ON 0.5 + 0. 5 3 5 5 Compound 2 1 + Chlomeprop 0.5 + 3.5 5 5 5 [Test Example 9] Herbicidal effect test by foliar treatment

 After alluvial soil was put into a 1Z 10000 are plastic pot, water was added and mixed to make a 4 cm flood condition. Nobies seeds were sown in the pot, and Mizugayari tubers were placed on the pot and grown in a greenhouse. After growing for 14 days, the surface water was extracted, the wettable powder prepared according to the formulation example was diluted with water to a prescribed dosage, and uniformly treated with a small spray on the foliage. On the 21st day after the chemical treatment, the herbicidal effect on both plants was investigated according to the above criteria. The results are shown in Table 6.

[¾8] [Table 6: Compound treatment dose Nobie Mizugayari

 (g / a) Compound 1 1 5 5 Compound 9 1 5 5 Compound 2 1 1 5 5 Propaninole 20 5 1

 2, 4 -PA 10 0 0 Bentazone 10 0 5 Compound 1 + Propanyl 1 + 20 5 5 Compound 1 + 2, 4 -PA 1 + 10 5 5 Compound 1 + Bentazone 1 + 10 5 5 Compound 9 + Propanyl 1 + 20 5 5 Compound 9 + 2, 4-PA 1 + 10 5 5 Compound 9 + Bentazone 1 + 10 5 5 Compound 21 + Propanyl 1 + 20 5 5 Compound 21 + 2, 4-PA 1 + 10 5 5 Compound 21 + Bentazone 1 + 1 0 5 5 Industrial Applicability

 As is clear from the above results, the composition of the present invention is useful, for example, as a herbicide for paddy fields.

Claims

Claim [1] Formula (1)  [Chemical 1]

[Wherein R ¹ is a C alkyl group, a C haloalkyl group, a C alkoxy C alkyl group, a  1-3 1-3 1-3 1-3  Represents a phenyl group or a pyridyl group, R ² is a hydrogen atom, C alkyl group, C haloalkyl group, C alkoxy group or halo.  1-3 1-3 1-3  Represents a gen atom, B

Represents an alkyl group, provided that at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is C alkyl A force representing a 1-3 group or a C haloalkyl group, or R ³ and R ⁴ together represent = CH;  1-3 2 X and Y are each independently a C alkyl group, C haloalkyl group, C alkoxy group,  1-3 1-3 1-3 represents a Si group, a C haloalkoxy group, a halogen atom or a di (C alkyl) amino group, 1-3 1-3  z represents a nitrogen atom or a methine group. And a pyrazole sulfo-lurea compound (A) represented by  A herbicidal composition containing at least one compound selected from the medium strengths of Daimlon, Dimepiperate and Esprocalp.  [2] A herbicidal composition for paddy rice containing the compound (A) and at least one compound selected from among the powers of Daimlon, Dimepiperate and Esprocalp.  [3] A herbicidal method wherein the compound (A) and at least one compound selected from among the medium strengths of Daimlon, Dimepiperate and Esprocarp are applied simultaneously or with a time difference. [4] Selected among the above compounds (A), Daimron, Dimepiperate and Esprocarp A method of paddy field weeding, which is applied with at least one compound at the same time or with a time difference. Compound (A), Group B (however, Group B is a general name of pyrazosulfuron-ethylZ), Benz Ruflon methyl (bensulfuron-methylZ generic name), sinosulfuron (cinosulfuron generic name), imazosulfuron (generic name), azimsulfuron (azimsulfuron generic name), halosulfuron methyl (halosulfuron-methylZ generic name), cyclosulfamuronZ (Generic name), ethoxysulfuron / (common name), pyrazolate (pyrazolate / -common name), pyrazoxifene (-common name), benzofenapZ (generic name), bromobutideZ (generic name), Naproanilide (common name), pretilachlor (common name), pork claw (Butachlor / —common name), terechlor (thenylchlor common name), CNP (—common name), clomethoxynyl (chlometho xynilZ common name), bifenox (bifenoxZ common name), oxadiazon (generic name), oxadiargylZ (general name) Name), pentoxazone (generic name for pentoxazone Z), caffeenstrol (generic name for cafenstroleZ), oxazic lomefone (generic name), indanofan (indanofan / generic name), pyriminopac methyl (p yriminobac —Methyl / —common name), cyhalofop-butyl / —common name, fentrazamide (generic name for fentrazamideZ), mefenacet (generic name for mefenacetZ), butenachlor (generic name for butenachlorZ), dithiopylZ (generic name) , Benfuresate (generic name), piributicarb (generic name), bencho curve (benthiocarbZ Common name), Molinate (generic name), ButamifosZ (generic name), Kinkrac (generic name), Simmesrin (c inmethylinZ—generic name), Cymetrin (simetrynZ—generic name), Bensulide (bensulideZ—generic name) Name), dimethamethrin (generic name), MCPA (generic name), MCPB (—generic name), etobenzanidZ (generic name), cumyluronZ (generic name), benzobicyclonZ (generic name), pyriftalide (pyriftalid / —common name), bispiribac (—common name), pyrachlor (pyraclonil / —common name), arofos (anilofos / —common name), OK—701 (test name), page Nox slam (common name) ), AVH 301 (study name), KUH-021 (study name), TH-547 (study name), bentazone (general name BentazoneZ), 2, 4—PA (—common name), metamihop (common name), flucetol Also includes chlorofluorocarbon (flucetosulfuronZ generic name), HOK-201 (generic name), mesotrione (mesotrion eZ generic name), prop (propanilZ generic name), quinoclamin (quinoclamineZ generic name) and clomeprop. ) Strength A herbicidal composition comprising at least one selected compound. [6] A herbicide composition for paddy rice containing the compound (A) and at least one compound selected from the group B.  [7] A herbicidal method in which the compound (A) and at least one compound for which the group B power is also selected are applied simultaneously or with a time difference. [8] A method for weeding paddy fields, wherein the compound (A) and at least one compound for which the group B force is also selected are applied simultaneously or with a time difference.