DESCRIPTION HERBICIDE COMPOSITION
TECHNICAL FIELD
[0001]
The present invention relates to a herbicide composition which has reduced crop injury particularly to paddy rice, and a weeding method.
BACKGROUND ART
[0002]
As an herbicide for paddy rice, a compound (A) has been applied for a patent. The compound (A) shows herbicidal activity for various weeds in extremely small amount and has high safety for paddy rice under normal planting conditions. However, the compound (A) may cause crop injury to paddy rice in the case of extremely shallow planting or water leakage condition.
Although dymron, dimepiperate and esprocarb are widely used herbicides for paddy rice, an advantage for reducing crop injury caused by the compound (A) to paddy rice has not been reported until now.
Patent Document 1 discloses that pyrazole sulfonylureas, which is formed by bonding a dioxadine ring on a pyrazole ring, has herbicidal activity. However, Patent Document 1 does not specifically disclose pyrazole sulfonylureas, like the compound (A), whose dioxadine ring on the pyrazole ring is bonded to a substitutional group. Patent Document 1: Japanese Patent Application Publication No. JP-A-7-118269
DISCLOSURE OF THE INVENTION
[Problems to be Solved by the Invention] [0003]
Currently, various chemical compounds are practically used for herbicides for paddy rice. However, existing herbicides do not fully satisfy the requirement of

providing no harmful effects to paddy rice and selectively eliminating target weeds
for crop protection.
[Means to Solve the Problems]
[0004]
As a result of an intensive investigation aimed at resolving the problems described above, the inventors of the present invention have discovered that a mixture of the compound (A) and dymron, dimepiperate or esprocarb shows an advantage of better-than-expected reduction of crop injury, and when the compound (A) is combined with certain types of herbicides, the combined mixture complements herbicidal spectrums each other without antagonizing each other. Thus the inventors have completed the present invention. In other words, the present invention relates to an herbicide composition of the below-described aspects [1] and [2] (hereinafter called a "compound according to the present invention"), and a weeding method of the below-described aspects [3] and [4] (hereinafter called a "method according to the present invention").
[1] A herbicide composition containing a pyrazole sulfonylurea compound (A) represented by the general formula (1): [Chemical formula 1 ]

(Formula Removed)
(in which, R1 represents C].3 alkyl group, Ci_3 haloalkyl group, C1-3 alkoxy-Ci.3 alkyl
group, phenyl group or pyridyl group;
R represents hydrogen atom, C1-3 alkyl group, C1.3 haloalkyl group, C1.3 alkoxy group
or halogen atom;
R3, R4, R5, and R6 independently represent hydrogen atom, C1.3 alkyl group or C1-3
haloalkyl group, where at least one of R3, R4, R5, and R6 represents C1.3 alkyl group or
C1.3 haloalkyl group or R3 and R4 are combined together to represent =CH2;

X and Y independently represent C1-3 alkyl group, C1-3 haloalkyl group, C1-3 alkoxy group, C1-3 haloalkoxy group, halogen atom or di( C1-3 alkyl)amino group; and Z represents nitrogen atom and methine group)
and at least one compound selected from dymron, dimepiperate and esprocarb. [2] A herbicide composition for paddy rice containing the compound (A) and at least one compound selected from dymron, dimepiperate and esprocarb. [3] A weeding method including applying the compound (A) and at least one compound selected from dymron, dimepiperate and esprocarb either simultaneously or at an interval.
[4] A weeding method for a paddy field including applying the compound (A) and at least one compound selected from dymron, dimepiperate and esprocarb either simultaneously or at an interval.
[5] A herbicide composition containing the compound (A) and at least one compound selected from a group B consisting of pyrazosulfuron-ethyl (common name), bensulfuron-methyl (common name), cinosulfuron (common name), imazosulfuron (common name), azimsulfuron (common name), halosulfuron-methyl (common name), cyclosulfamuron (common name), ethoxysulfuron (common name), pyrazolate (common name), pyrazoxyfen (common name), benzofenap (common name), bromobutide (common name), naproanilide (common name), pretilachlor (common name), butachlor (common name), thenylchlor (common name), CNP (common name), chlomethoxynil (common name), bifenox (common name), oxadiazon (common name), oxadiargyl (common name), pentoxazone (common name), cafenstrole (common name), oxaziclomefone (common name), indanofan (common name), pyriminobac-methyl (common name), cyhalofop-butyl (common name), fentrazamide (common name), mefenacet (common name), butenachlor (common name), dithiopyl (common name), benfuresate (common name), pyributicarb (common name), benthiocarb (common name), molinate (common name), butamifos (common name), quinclorac (common name), cinmethylin (common name), simetryn (common name), bensulide (common name), dimethametryn (common name), MCPA (common name), MCPB (common name), etobenzanid (common name), cumyluron (common name), benzobicyclon (common name), pyriftalid (common name), bispyribac (common name), pyraclonil (common name), anilofos (common name), OK-701 (test name), penoxsulam (common name), AVH-301 (test name), KUH-021 (test name), TH-547 (test name), Bentazone
(common name), 2,4-PA (common name), metamifop (common name),
flucetosulfuron (common name), HOK-201 (common name), mesotrione (common
name), propanil (common name), quinoclamine (common name) and clomeprop.
[6] A herbicide composition for paddy rice containing the compound (A) and at
least one compound selected from the group B.
[7] A weeding method including applying the compound (A) and at least one
compound selected from the group B either simultaneously or at an interval.
[8] A weeding method for a paddy field including applying the compound (A) and
at least one compound selected from the group B either simultaneously or at an
interval.
[Advantageous Effects of the Invention]
[0005]
According to some aspects of the present invention, crop injury to crops, particularly to paddy rice, caused by the compound (A) acting as an active ingredient of a herbicide is reduced by addition of dymron, dimepiperate and esprocarb and this addition does not decrease weeding effects for various weeds. Moreover, in a mixture of the compound (A) and certain types of herbicides, each component does not antagonize each other and complement herbicidal spectrums. Therefore, practical applications according to the present invention are extremely useful.
BEST MODES FOR CARRYING OUT THE INVENTION
[0006]
In the present invention, Ph, Me and Bu represent phenyl group, methyl group and butyl group in formulae, respectively.
The compound (A) can be produced by methods shown in reaction formulae 1 to 3 described below. [Reaction formula 1 ] [Chemical formula 2]

(Formula Removed)

(in which R1, R2, R3, R4, R5, R6, X, Y and Z have the same meaning as defined above.)
The reaction formula 1 illustrates a method of producing the compound (1) by reacting 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (2) and 2-phenoxycarbonylaminopyrimidine (or triazine) (3) in the presence or absence of a base.
In this reaction, (3) is generally used in a molar amount of 0.5 to 10-fold, preferably a molar amount of 0.9 to 1.1-fold, over (2).
Bases used for this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 10-fold, a molar amount of preferably 0 to 2-fold, over (2).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in this reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 120°C.

A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0007]
[Reaction formula 2] [Chemical formula 3]

(Formula Removed)
(in which R1, R2, R3, R4, R5, R6, X, Y and Z have the same meaning as defined above.)
The reaction formula 2 illustrates a method of producing the compound (1) by reacting 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonylcarbamate (4) and 2-aminopyrimidine (or triazine) (5) in the presense or absence of a base.
In this reaction, (5) is generally used in a molar amount of 0.5 to 10-fold, preferably a molar amount of 0.9 to 1.1-fold, over (4).
Bases used for this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 10-fold, a molar amount of preferably 0 to 2-fold, over (4).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in this reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl

7
ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 120°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0008]
[Reaction formula 3] [Chemical formula 4]
(Formula Removed)
(in which R1, R2, R3, R4, R5, R6, X, Y and Z have the same meaning as defined above.)
The reaction formula 3 illustrates a method of producing the compound (1) by reacting 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonylisocyanate (6) and 2-aminopyrimidine (or triazine) (5) in the presense or absence of a base.
In this reaction, (5) is generally used in a molar amount of 0.5 to 10-fold, preferably a molar amount of 0.9 to 1.1-fold, over (6).
Bases used for this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 10-fold, preferably a molar amount of 0 to 2-fold, over (3).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in this reaction. Examples of such solvents include hydrocarbons such as hexane,

cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 120°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0009]
4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (2) used in the method shown in the reaction formula 1 can be produced by methods shown in the reaction formulae 4 to 6 described below.
In addition, 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonylcarbamate (4) and 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonylisocyanate (6) used in methods shown in the reaction formulae 2 and 3 can be synthesized with 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5 -sulfonamide (2) as a starting material by referring to methods described in Japanese Patent Application Publication No. JP-A-59-219281 and Japanese Patent Application Publication No. JP-A-55-13266 as references. [0010]
[Reaction formula 4] [Chemical formula 5]
(Formula Removed)

2) (in which R1, R2, R3, R4, R5 and R6 have the same meaning as defined above.)
The reaction formula 4 illustrates a method of producing 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5- sulfonamide (2) by reacting 5-chloro-4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole (7) with sodium hydrosulfide to obtain 5»mercapto-4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole (8) (process A); then by reacting (8) with chlorine or a chlorinating agent such as sodium hypochlorite to obtain 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonylchloride (9) (process B); and by reacting (9) with aqueous ammonia or ammonium carbonate (process C). [0011]
In the reaction of the process A, sodium hydrosulfide is generally used in a molar amount of 1.0 to 10-fold, preferably a molar amount of 2 to 5-fold, over (7).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N.N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-

pyrrolidone; sulfur-containing polar solvents such as dimethylsulfoxide and sulfolane; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 120°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0012]
In the reaction of the process B, chlorine or sodium hypochlorite is generally used in a molar ratio of 1 to 100-fold, preferably a molar ratio of 2 to 10-fold, over (8).
In the reaction, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 100°C, and preferably -10°C to 50°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0013]
In the reaction of the process C, ammonia or ammonium carbonate is generally used in a molar amount of 1.0 to 100-fold, preferably a molar amount of 2 to 5-fold, over (9).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfur-containing polar solvents such as dimethylsulfoxide and sulfolane; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0014]

[Reaction formula 5] [Chemical formula 6]

(Formula Removed)
(10) (in which R1, R2, R3, R4, R5 and R6 have the same meaning as defined above.)
The reaction formula 5 illustrates a method of producing 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonylchloride (9) by reacting 5-benzylmercapto-4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole (10) with chlorine or a chlorinating agent such as sodium hypochlorite.
In the reaction, chlorine or sodium hypochlorite is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 2 to 10-fold, over (10).
In the reaction, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 100°C, and preferably -10°C to 50°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0015]
(9) can be derived into 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (2) according to the process C of the reaction formula 4. Moreover, (1) can be produced by reacting (9) and (5) by referring to the method described in Japanese Patent Application Publication No. JP-A-7-118267. [0016]
[Reaction formula 6] [Chemical formula 7]

(Formula Removed)
(in which R1, R2, R3, R4, R5 and R6 have the same meaning as defined above.)
The reaction formula 6 illustrates a method of producing 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonylchloride (9) by lithiating 5-position of the pyrazole ring of 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole (11) with n-butyl lithium (n-BuLi) or lithium diisopropylamide (LDA) and then reacting the resultant compound with sulfur dioxide to obtain 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfinic acid lithium (12) (process D); and by reacting (12) with N-chlorosuccinimide (process E). [0017]
In the reaction 1) of the process D, n-butyl lithium or lithium diisopropylamide is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 1 to 5-fold, over (11).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; and mixed solvents thereof.
A reaction temperature is generally -120°C to 100°C, and preferably -78°C to 10°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0018]
In the reaction 2) of the process D, sulfur dioxide is generally used in a molar amount of 1.0 to 100-fold, preferably a molar amount of 1 to 10-fold, over (11).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; and mixed solvents thereof.

A reaction temperature is generally -120°C to 100°C, and preferably -78°C to 10°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0019]
In the reaction of the process E, N-chlorosuccinimide is generally used in a molar amount of 1.0 to 100-fold, preferably a molar amount of 1 to 10-fold, over (12).
Solvents used in the reaction are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 100°C, and preferably -10°C to 50°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0020]
(9) can be derived into 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (2) according to the process C of the reaction formula 4. [0021]
5-chloro-4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole(7), 5-benzylmercapto-4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole (10) and 4-(5H,6H-l,4,2-dioxadin-3-yl)pyrazole (11) used in methods shown in the reaction formulae 4 to 6 can be produced by methods illustrated in reaction formulae 7 to 15. [Reaction formula 7]
[Chemical formula 8]

(Formula Removed)
(in which R1, R2, R3, R4, R5 and R6 have the same meaning as defined above; X represents halogen atom; and L represents chlorine atom, benzylthio group or hydrogen atom.)

The reaction formula 7 illustrates a method of producing 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7), (10) or (11) by reacting pyrazole-4-hydroxamic acid (13) with adjacently dihalogenated alkyl (14).
In this reaction, (14) is generally used in a molar amount of 1.0 to 100-fold, preferably a molar amount of 1 to 5-fold, over (13).
Bases used for this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 10-fold, preferably a molar amount of 0 to 2-fold, over (13).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfur-containing polar solvents such as dimethylsulfoxide and sulfolane; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0022]
[Reaction formula 8] [Chemical formula 9]

(Formula Removed)
(in which R1, R2, R3, R4, R5, R6 and L have the same meaning as defined above; and X2 represent halogen atom, C1-3 alkylsulfonyloxy group or C 1.3 haloalkylsulfonyloxy group.)
The reaction formula 8 illustrates a method of producing 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7), (10) or (11) by reacting pyrazole-4-carboxylic acid chloride (15) with an alkoxyamine (16) to obtain pyrazole-4-hydroxamic acid ester (17) (process F); and by reacting (17) with a base (process G). [0023]
In the reaction of the process F, (16) is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 2 to 5-fold, over (15).
Bases used for this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 10-fold, preferably a molar amount of 0 to 2-fold, over (15).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile;

amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0024]
Bases used for the reaction of the process G include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 10-fold, preferably a molar amount of 0 to 2-fold, over (17).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0025]
[Reaction formula 9] [Chemical formula 10]

(Formula Removed)
(in which R1, R2, R3, R3, R6, X1 and L have the same meaning as defined above; and R7 and R8 independently represent hydrogen atom or C 1.3 alkyl group.)
The reaction formula 9 illustrates a method of producing 4-(5-alkyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (7b), (10b) or (1 lb) by reacting pyrazole-4-carboxylic acid chloride (15) with allyloxyamine (16a) to obtain pyrazole-4-hydroxamic acid ester (17a) (process H); then reacting (17a) with halogen or N-halogenated succinimide to obtain 4-(5-haloalkyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (7a), (10a) or (11a) (process I); and reducing (7a), (10a) or (1 la) (process J). [0026]
In the reaction of the process H, (16a) is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 2 to 5-fold, over (15).
Bases used for this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium

diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 10-fold, preferably a molar amount of 0 to 2-fold, over (15).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0027]
In the reaction of the process I, halogen or N-halogenated succinimide is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 1 to 5-fold, over (17a).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; carboxylic acid esters such as methyl acetate or ethyl acetate; 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.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0028]

Reducing agents and reducing systems used in the reaction of the process J include systems in which alkali metals are used, such as metal sodium/liquid ammonia, metal lithium/liquid ammonia and metal sodium/t-butyl alcohol-tetrahydrofuran mixed solvent; systems in which metal zinc is used, such as zinc/acetic acid and zinc/potassium hydroxide/water; systems in which organic tin hydrides are used, such as triphenyl tin hydride, diphenyl tin hydride, tri-n-butyl tin hydride, di-n-butyl tin hydride, triethyl tin hydride and trimethyl tin hydride; mixed systems in which the above-mentioned organic tin compounds are combined with free radical initiators such as azobisisobutyronitrile; systems in which silanes such as trichlorosilane, triethylsilane and trimethylsilane are used; systems in which metal hydrogen complex compounds such as lithium aluminum hydride, sodium aluminum hydride, sodium bis(2-methoxyethoxy) aluminum hydride, sodium borohydride and sodium cyanoborohydride are used; systems in which borane derivatives, such as diborane, trimethylamine-borane and pyridine-borane, are used; and catalytic reduction systems such as hydrogen/palladium-carbon and hydrogen/Raney nickel.
A reducing agent is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 1 to 5-fold over (7a), (10a) or (11a).
Although this reductive reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the above-mentioned reducing systems. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; carboxylic acid esters such as methyl acetate or ethyl acetate; 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.
A reaction temperature is generally -90°C to 200°C, and preferably -78°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0029]
[Reaction formula 10] [Chemical formula 11]

(Formula Removed)
(in which R1, R2, R5, R6, R7, R8, X2 and L have the same meaning as defined above.) The reaction formula 10 illustrates a method of producing 4-(5-alkyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (7e), (lOe) or (1 le) by dehydrogen halide reaction of 4-(5-haloalkyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (7c), (10c) or (lie) in the presense or absence of a base to obtain 4-(5-alkyliden-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (7d), (lOd) or (1 Id), respectively (process K); and by reduction (7d), (lOd) or (1 Id), respectively (process L). [0030]
Bases used for the reaction of the process K include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and potassium bicarbonate, sodium bicarbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 100-fold, preferably a molar amount of 0 to 5-fold, over (7c), (10c) or (lie).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the above-mentioned reducing systems. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile;

amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0031]
The reducing agents and reducing systems used in the reaction of the process L include systems in which alkali metals are used, such as metal sodium/liquid ammonia, metal lithium/liquid ammonia and metal lithium/ethyl amine; systems in which metal aluminums are used, such as aluminum-mercury/diethylether-water and aluminum-nickel/sodium hydroxide/water; systems in which aluminum hydride compounds such as diisobutyl aluminum hydride are used; systems in which hydrosilanes such as triethylsilane-trifluoroacetic acid and polymethylhydrosiloxane/palladium-carbon are used; systems in which metal hydrogen complex compounds such as lithium aluminum hydride, sodium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, sodium borohydride and sodium cyanoborohydride are used, systems in which borane derivatives such as diborane, trimethylamine-borane and pyridine-borane are used; systems in which di-imides generated in the reaction systems are used, such as hydrazine hydrate/air, hydrazine hydrate/ potassium hexacyanoferrate (III) and hydroxylamine-O-sulfonic acid/sodium hydroxide; heterogeneous catalytic reduction systems such as hydrogen/palladium-carbon and hydrogen/Raney nickel; and homogeneous catalytic reduction systems such as hydrogen/chlorotris(triphenylphosphine)rhodium (I), hydrogen/hydride carbonyltris(triphenylphosphine)rhodium (I), hydrogen/rhodium (II) acetate and hydrogen/ruthenium (II) acetate.
Although this reductive reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the above-mentioned reducing systems. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; carboxylic acid esters such as methyl acetate or ethyl acetate; 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.
A reaction temperature is generally -90°C to 200°C, and preferably -78°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0032]
[Reaction formula 11 ] [Chemical formula 12]

(Formula Removed)
(in which R1, R2, R3, R5, R6, R7, R8, and L have the same meaning as defined above.) The reaction formula 11 illustrates a method of producing 4-(5-alkyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (7b), (10b) or (1 lb) by reacting pyrazole-4-hydroxamic acid ester (17a) or (17b) with an acid (H+). [0033]
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, methane sulfonic acid, trifluoromethane sulfonic acid or p-toluenesulfonic acid. The acid is generally used in a molar amount of 0.01 to 100-fold, preferably a molar amount of 0.05 to 10-fold, over (17a) or (17b).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; water and mixed solvents thereof.

A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0034]
[Reaction formula 12] [Chemical formula 13]
(Formula Removed)
(in which R3, R5, R6, R7, R8, and X2 have the same meaning as defined above.)
The reaction formula 12 illustrates a method of producing pyrazole-4-hydroxamic acid ester (17a) used in the reaction formula 9 and the reaction formula 11 by reacting pyrazole-4-hydroxamic acid (13) and an halogenated allyl (18) in the presense or absence of a base. [0035]
In this reaction, (18) is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 1 to 5-fold, over (13).
Bases used for this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 100-fold, preferably a molar amount of 0 to 5-fold, over (13).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl

ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0036]

(Table Removed)
(in which R3, R5, R6, R7, R8, and X2 have the same meaning as defined above.)
The reaction formula 13 illustrates a method of producing pyrazole-4-hydroxamic acid ester (17b) used in the reaction formula 11 by reacting pyrazole-4-hydroxamic acid (13) and a halohydrin (19) or an oxirane (20) in the presense or absence of abase. [0037]
In this reaction, (19) or (20) is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 2 to 5-fold, over (13).
Bases used for this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 100-fold, preferably a molar amount of 0 to 5-fold, over (13).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the

reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0038]
[Reaction formula 14] [Chemical formula 15]
(Formula Removed)
(in which R1, Rz, R\ R°, R°, R', R5, and L have the same meaning as defined above.) The reaction formula 14 illustrates a method of producing 4-(5-haloalkyl (or alkylsulfonyloxyalkyl)-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (7c), (10c) or (1 lc) by reacting pyrazole-4-hydroxamic acid (13) and an epihalohydrin (21) in the presence or absence of a base to obtain pyrazole-4-hydroxamic acid ester (17c) (process L);
then by treating (17c) with an acid or a base to obtain 4-(5-hydroxyalkyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (7f), (lOf) or (1 If) (process M); and by halogenating or alkylsulfonylating (7f), (lOf) or (1 If) (process N). (7c), (10c) or (lie) is used in the reaction formula 10. [0039]
In the reaction of the process L, (21) is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 1 to 5-fold, over (13).
Bases used for this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 100-fold, preferably a molar amount of 0 to 5-fold, over (13).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0040]
Acids and bases used for the reaction of the process M include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as acetic acid, trifluoroacetic acid, methane sulfonic acid, trifluoromethane sulfonic acid or p-toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium
hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. An acid or a base is generally used in a molar amount of 0 to 100-fold, preferably a molar amount of 0 to 5-fold, over (17c).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0041]
In the reaction of the process N, a halogenation agent or an alkylsulfonylation agent is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 1 to 5-fold, over (7f), (lOf) or (1 If).
Halogenation agents used in this reaction include hydrogen halide acids such as hydrogen chloride, hydrogen bromide and hydrogen iodide; phosphorus halides such as phosphorus trichloride, phosphorus pentachloride, oxyphosphorus chloride and phosphorus tribromide; systems such as triphenyl phosphonate/benzyl chloride and triphenylphosphine/carbon tetrachloride; sulfonium halides such as methane sulfonyl chloride and p-toluene sulfonyl chloride; and thionyl halides such as thionyl chloride and thionyl bromide.
Alkylsulfonylation agents used in this reaction include sulfonium halides such as methane sulfonyl chloride and p-toluene sulfonyl chloride.
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours.
[0042]
[Reaction formula 15]
[Chemical formula 16]
(Formula Removed)
The reaction formula 15 illustrates a method of producing pyrazole-4-hydroxamic acid (13) used in the reaction formula 7 and reaction formulae 12 to 14 by reacting pyrazole-4-carboxylic acid chloride (15) and hydroxyamine in the presence or absence of a base. [0043]
In this reaction, hydroxylamine is generally used in a molar amount of 1 to 100-fold, preferably a molar amount of 1 to 5-fold, over (15).
Bases used for this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride; organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, N,N-dimethylaniline, l,8-diazabicyclo[5.4.0]-7-undecene and l,4-diazabicyclo[2.2.2]-octane; organic lithiums such as n-butyllithium and sec-butyllithium; organic lithium amides such as lithium diisopropylamide and lithium bis(trimethylsilyl)amide; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. A base is generally used in a molar amount of 0 to 100-fold, preferably a molar amount of 0 to 5-fold, over (15).
Although this reaction proceeds without solvents, solvents may optionally be used. Solvents are not particularly restricted as long as they are inactive in the reaction. Examples of such solvents include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone; water and mixed solvents thereof.
A reaction temperature is generally -90°C to 200°C, and preferably 0°C to 100°C.
A reaction time is generally 0.05 to 100 hours, and preferably 0.5 to 10 hours. [0044]
The target products obtained according to the above-mentioned reactions can be isolated and purified by operations such as filtering, extraction, washing, column chromatography, recrystallization and distillation. [0045]
Examples of synthesis of the compounds according to the present invention will be specifically described below, although the present invention is not limited thereto. [0046] Synthesis Example 1
Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (compound No. 1 according to the present invention) [Chemical formula 17] Me
(Formula Removed)
3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3--yl)pyrazole-5-sulfonamide (0.64g, 2.2 mmol) and phenyl N-(4,6-dimethoxypyrimidin-2-yl)carbamate (0.59 g, 2.1 mmol) were dissolved into acetonitrile (8 ml), and 1,8-diazabicyclo[5.4.0]-7-undecene (0.33 g, 2.2 mmol) was added to the resultant solution, and then the obtained mixture was stirred for 1 hour at room temperature. After water (8 ml) was added to the mixture, the resultant mixture was extracted with diethyl ether. The obtained aqueous layer was adjusted to pH 1 by adding 12% hydrochloric acid, and the resultant aqueous layer was re-extracted with diethyl ether. The obtained diethyl ether solution was sequentially washed with water and saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation, and the obtained residue was washed with n-hexane and dried to obtain the target product (0.40 g). Melting point: 177-179°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 1.38 (d, J=6.6 Hz, 3H), 3.69-3.72 (m, 1H), 3.96 (s, 6H), 4.13-4.18 (m, 1H), 4.30 (s, 3H), 4.49-4.63 (m, 1H), 5.77 (s, 1H), 7.67 (brs, 1H), 12.91 (brs, 1H). [0047] Synthesis Example 2
Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazole-5-sulfonamide (compound No. 2 according to the present invention) [Chemical formula 18]
(Formula Removed)
OMe The target product (0.10 g) was obtained in a similar manner as described in Synthesis Example 1 by using 3-chloro-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazole-5-sulfonamide (0.090 g, 0.21 mmol) as a starting material. Melting point: 91-94°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in
CDC13): 3.28-3.42 (m, 2H), 3.89-4.05 (m, 7H), 4.04-4.12 (m, IH), 4.31 (s, 3H), 4.56-
4.60 (m, IH), 5.79 (s, IH), 7.43 (brs, IH) and 12.93 (s, IH).
[0048]
Synthesis Example 3
Synthesis ofN-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-4-(5,5-dimethyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazole-5-sulfonamide (compound No. 3 according to the present invention) [Chemical formula 19]

(Formula Removed)
The target product (0.42 g) was obtained in a similar manner as described in Synthesis Example 1 by using 3-chloro-4-(5,5-dimethyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazole-5-sulfonamide (0.47 g, 1.5 mmol) as a starting material. Melting point: 189-191°C. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDC13): 1.41 (s, 6H), 3.78 (s, 2H), 3.97 (s, 6H), 4.30 (s, 3H), 5.78 (s, IH), 7.58 (brs, IH) and 12.92 (brs, IH). [0049] Synthesis Example 4
Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-4-(5-iodomethyl-5-methyl-5H,6H-1,4,2-dioxadin-3-yl)-1 -methylpyrazole-5-sulfonamide (compound No. 4 according to the present invention) [Chemical formula 20]
(Formula Removed)
The target product (0.14 g) was obtained in a similar manner as described in Synthesis Example 1 by using 3-chloro-4-(5-iodomethyl-5-methyl-5H,6H-1,4,2-dioxadin-3-yl)-l-methylpyrazole-5-sulfonamide (0.21 g, 0.48 mmol) as a starting material. Melting point: 90-93°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 1.55 (s, 3H), 3.30-3.49 (m, 2H), 3.81-3.84 (m, IH), 3.97 (s, 6H), 4.23-4.30 (m, 4H), 5.80 (s, IH), 7.29 (brs, IH) and 12.93 (s, IH). [0050] Synthesis Example 5
Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-l,3-dimethyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (compound No. 5 according to the present invention) [Chemical formula 21] Me
(Formula Removed)
The target product (0.090 g) was obtained in a similar manner as described in Synthesis Example 1 by using l,3-dimethyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (0.070 g, 0.26 mmol) as a starting material. Melting point: 180-182°C. Proton nuclear magnetic resonance chemical shift values § (ppm) (in CDCI3): 1.36 (d, J=6.6 Hz, 3H), 2.29 (s, 3H), 3.62-3.69 (m, IH), 3.97 (s, 6H), 4.11-
4.16 (m, IH), 4.27 (s, 3H), 4.49-4.54 (m, IH), 5.78 (s, IH), 7.23 (brs, IH) and 12.74
(brs, IH).
[0051]
Synthesis Example 6
Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-4-(5-iodomethyl-5H,6H-l ,4,2-dioxadin-3-yl)-l -methylpyrazole-5-sulfonamide (compound No. 6 according to the present invention) [Chemical formula 22]

(Formula Removed)
The target product (0.34 g) was obtained in a similar manner as described in Synthesis Example 1 by using 4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3-dimethylpyrazole-5-sulfonamide (0.53 g, 1.3 mmol) as a starting material. Melting point: 66-69°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 2.34 (s, 3H), 3.36 (m, 2H), 3.92-4.19 (m, 8H), 4.23 (s, 3H), 4.54-4.59 (m, IH), 5.78 (s, IH), 7.41 (brs, IH) and 12.64 (brs, IH). [0052] Synthesis Example 7

Synthesis ofN-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-4-(5,5-dimethyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3-dimethylpyrazole-5-sulfonamide (compound No. 7 according to the present invention) [Chemical formula 23]

(Formula Removed)
The target product (0.12 g) was obtained in a similar manner as described in Synthesis Example 1 by using 4-(5,5-dimethyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3-dimethylpyrazole-5-sulfonamide (0.13 g, 0.45 mmol) as a starting material. Melting point: 199-201°C. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDC13): 1.39 (s, 6H), 2.27 (s, 3H), 3.75 (s, 2H), 3.97 (s, 6H), 4.27 (s, 3H), 5.78 (s, 1H), 7.22 (brs, 1H) and 12.75 (s, 1H). [0053] Synthesis Example 8
Synthesis ofN-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-4-(5-iodomethyl-5-methyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3-dimethylpyrazole-5-sulfonamide (compound No. 8 according to the present invention) [Chemical formula 24]
Me
(Formula Removed)
The target product (0.050 g) was obtained in a similar manner as described in Synthesis Example 1 by using 4-(5-iodomethyl-5-methyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3-dimethylpyrazole-5-sulfonamide (0.080 g, 0.19 mmol) as a starting material. Melting point: 133-135°C. Proton nuclear magnetic resonance chemical shift values 8
(ppm) (in CDCI3): 1.63 (s, 3H), 2.29 (s, 3H), 3.31-3.46 (m, 2H), 3.78-3.82 (m, 1H),
3.97 (s, 6H), 4.17-4.27 (m, 4H), 5.79 (s, 1H), 7.40 (brs, 1H) and 12.76 (brs, 1H).
[0054]
Synthesis Example 9
Synthesis ofN-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-l,3-dimethyl-4-(6-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (compound No. 9 according to the present invention)
[Chemical formula 25]

(Formula Removed)
The target product (0.17 g) was obtained in a similar manner as described in Synthesis Example 1 by using l,3-dimethyl-4-(6-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (0.14 g, 0.51 mmol) as a starting material. Melting point: 187-189°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDCI3): 1.28 (d, J=8.0 Hz, 3H), 2.29 (s, 3H), 3.96 (s, 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) and 12.70 (brs, 1H). [0055] Synthesis Example 10
Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-1 -methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (compound No. 1 according to the present invention) (2nd method)
N-methoxycarbonyl-3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-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 into toluene (100 ml), and the resultant mixture was refluxed with heating for 4 hours under reduced pressure (700 mmHg) with removing byproduced methanol by distillation. After 15 ml of toluene was removed by distillation at the same temperature, the obtained mixture was cooled
to room temperature with stirring. Precipitated solid was filtered, washed with
toluene and dried to obtain the target product (24.1 g). Melting point: 177-179°C.
[0056]
Synthesis Example 11
N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (compound No. 1 according to the present invention) (3rd method)
A toluene (5 ml) solution of 3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonylisocyanate (1.0 g, 3.1 mmol) was added into an acetonitrile (3 ml) solution of 2-amino-4,6-dimethoxypyrimidine (0.46 g, 3.0 mmol), and the resultant mixture was stirred for 3 hours at room temperature. Precipitated solid was filtered, washed with toluene and dried to obtain the target product (1.2 g). Melting point: 177-179°C. [0057] Synthesis Example 12
Synthesis ofN-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (compound No. 1 according to the present invention) (4th method)
Pyridine (0.16 g, 2.0 mol) and sodium cyanate (0.72 g, 11 mmol) were added to an acetonitrile (15 ml) solution of 2-amino-4,6-dimethoxypyrimidine (1.55 g, 10.0 mmol), and then 3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl chloride (3.45 g, 11.0 mmol) was added to the mixture in small portions for 1 hour at 40°C with agitation. The mixture was further stirred for 1.5 hour at 40°C. After cooling the mixture to room temperature, water (60 ml) was added and then the resultant mixture was adjusted to pH 1 with 35% hydrochloric acid, and precipitated solid was filtered to obtain the solid. The obtained solid was washed with methanol and dried to obtain the target product (4.70 g). Melting point: 177-179°C. [0058] Synthesis Example 13
Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (compound No. 10 according to the present invention) [Chemical formula 26]
(Formula Removed)
The target product (0.25 g) was obtained in a similar manner as described in Synthesis Example 1 by using l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (0.20 g, 0.77 mmol) as a starting material. Melting point: 154-157°C. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDC13): 1.35 (d, J=6.3 Hz, 3H), 3.56-3.64 (m, 1H), 4.03-4.13 (m, 7H), 4.34 (s, 3H), 4.44-4.50 (m, 1H), 5.78 (s, 1H), 7.45 (brs, 1H), 7.22 (s, 1H) and 12.66 Hz (brs, 1H). [0059] Synthesis Example 14
Synthesis of the compound No. 1 according to the present invention (2nd method)
3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl chloride (0.32 g, 1.0 mmol) was dissolved into acetonitrile (4 ml), and then 2-amino-4,6-dimethoxypyrimidine (0.16 g, 1.0 mmol) and sodium cyanate (0.07 g, 1.1 mmol) were added and stirred for 10 min at 40°C. Pyridine (0.04 g, 0.5 mmol) was added dropwise to the obtained mixture for 3 min, and the resultant mixture was stirred for 1 hour at 40°C. Methylene chloride (5 ml) was added to the mixture under ice cooling, and then the resultant mixture was adjusted to pH 1 with 12% hydrochloric acid. The obtained mixture was separated, and the water layer was extracted with methylene chloride. The separated methylene chloride solution and extracted methylene chloride were combined, washed with saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate. Solvent of the resultant mixture was removed by distillation, and resultant residue was purified with silica gel column chromatography (developing solvent: n-hexane/ethyl acetate = 1/2) to obtain 0.37 g of the target product. Melting point: 177-179°C. [0060] Synthesis Example 15

Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-1-methyl-4-(5-methylene-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (compound No. 21 according to the present invention) [Chemical formula 27]

3 -chloro-1 -methyl-4-(5 -methyl ene-5H,6H-1,4,2-dioxadin-3 -yl)pyrazole-5 -sulfonamide (0.13 g, 0.44 mmol) and phenyl N-(4,6-dimethoxypyrimidin-2-yl)carbamate (0.13 g, 0.47 mmol) were dissolved into acetonitrile (6 ml), and 1,8-diazabicyclo[5.4.0]-7-undecene (0.07 g, 0.46 mmol) was added to the solution and the obtained mixture was stirred for 1 hour at room temperature. Solvent of the resultant mixture was removed under reduced pressure by distillation. After 2N hydrochloric acid was added to the mixture, the resultant mixture was extracted with ethyl acetate. After the obtained ethyl acetate solution was dried over anhydrous sodium sulfate, the resultant solution was condensed under reduced pressure to obtain oily substance. Mixed solvent of toluene and hexane was added to the oily substance, and precipitated solid was filtered to obtain the solid. After the solid was washed with a small amount of toluene, and dried under reduced pressure to obtain the target product (0.10 g). White solid. Melting point: 164-167°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 3.95 (s, 6H), 4.32 (s, 3H), 4.35 (s, 2H), 4.42 (d, J=2.7 Hz, 1H), 4.78 (d, J=2.7 Hz, 1H), 5.80 (s, 1H), 7.32 (brs, 1H) and 11.98 (brs, 1H). [0061] Reference Example 1
(1) Synthesis of (5-benzylthio-3-chloro-1-methylpyrazol-4-yl)-N-allyloxycarboxylic acid amide [Chemical formula 28]

(Formula Removed)
Triethylamine (2.9 g, 29 mmol) was added to a tetrahydrofuran (20 ml) suspension of ailyloxyamine hydrochloride (2.3 g, 21 mmol) at 0°C, and the resultant mixture was stirred for 5 minutes at room temperature, and then a tetrahydrofuran (10 ml) solution of 5-benzylthio-3-chloro-l-methylpyrazole-4-carboxylic acid chloride (2.1 g, 7.0 mmol) was added dropwise to the resultant mixture. After stirring the mixture for 1 hour at room temperature, water (100 ml) was added and the obtained mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed with saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain the target product (2.4 g). Oily substance. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 3.45 (s, 3H), 4.11 (s, 2H), 4.53 (d, J=6.3 Hz, 2H), 5.34-5.45 (m, 2H), 6.00-6.13 (m, IH), 7.03-7.06 (m, 2H), 7.24-7.28 (m, 3H) and 9.14 (brs, IH). [0062]
(2) Synthesis of 5-benzylthio-3-chloro-4-(5-iodomethyl-5H,6H-l ,4,2-dioxadin-3-yl)-1 -methylpyrazole [Chemical formula 29]

Iodine (5.0 g, 20 mmol) was added to an acetonitrile (70 ml) solution of (5-benzylthio-3-chloro-l-methylpyrazol-4-yl)-N-allyloxycarboxylic acid amide (2.2 g,
6.5 mmol) at 0°C. After stirring the mixture for 6 hours at room temperature, water (150 ml) was added, and the resultant mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was sequentially washed with saturated sodium thiosulfate aqueous solution, saturated sodium hydrogen carbonate aqueous solution, saturated sodium chloride aqueous solution and water and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain the target product (3.0 g). Oily substance. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 3.25 (s, 3H), 3.34-3.42 (m, 2H), 4.04-4.11 (m, 3H), 4.32-4.40 (m, 1H), 4.58-4.65 (m, 1H), 7.00-7.08 (m, 2H) and 7.21-7.27 (m, 3H). [0063]
(3) Synthesis of 5-benzylthio-3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3 -yl)pyrazole [Chemical formula 30] Me
(Formula Removed)
Sodium borohydride (0.47 g, 12 mmol) was added to a dimethylsulfoxide (40 ml) solution of 5-benzylthio-3-chloro-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3 -yl)-1-methylpyrazole (2.9 g, 6.3 mmol). After the resultant mixture was stirred for 0.5 hour at 60°C, 6% hydrochloric acid (200 ml) was added and the obtained mixture was extracted with ethyl acetate. The resultant ethyl acetate solution was sequentially washed with saturated sodium chloride aqueous solution and water and dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain the target product (2.0 g). Oily substance. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDC13): 1.44 (d, J=6.6 Hz, 3H), 3.24 (s, 3H), 3.74-3.85 (m, 1H), 4.04 (s, 2H), 4.22-4.29 (m, 1H), 4.56-4.65 (m, 1H), 6.97-7.06 (m, 2H) and 7.19-7.21 (m,3H). [0064]
(4) Synthesis of 3-chloro-1-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5 -sulfonamide (1st method) [Chemical formula 31 ]
(Formula Removed)
Water (30 ml) and 35% hydrochloric acid (2.3 g, 22 mmol) were added to a methylene chloride (30 ml) solution of 5-benzylthio-3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (1.9 g, 5.6 mmol), and 8% sodium hypochlorite aqueous solution (20.5 g, 22.0 mmol) was added with vigorous stimng at 5°C, and the resultant mixture was stirred for 0.5 hour. After removing excess chlorine from the mixture by introducing nitrogen, water (50 ml) was added to the mixture, and the obtained mixture was extracted with methylene chloride. The obtained methylene chloride solution was concentrated under reduced pressure. After the resultant residue was dissolved in tetrahydrofuran (8 ml), 28% ammonia water (5 ml) was added at 0°C, and stirred for 0.25 hour at room temperature. Water (20 ml) was added to the mixture, and the resultant mixture was extracted with diethyl ether, and the diethyl ether layer was discarded. After the obtained aqueous layer was adjusted to pH 1 by adding 35% hydrochloric acid, the resultant aqueous layer was extracted with diethyl ether again. The obtained diethyl ether solution was washed with saturated sodium chloride aqueous solution, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain the target product (0.64 g). Melting point: 120-122°C. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDC13): 1.43 (d, J=6.3 Hz, 3H), 3.74-3.80 (m, 1H), 4.13 (s, 3H), 4.21-4.26 (m, 1H), 4.57-4.67 (m, 1H) and 6.12 (brs, 2H). [0065] Reference Example 2
Synthesis of 3-chloro-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazol-5-sulfonamide
[Chemical formula 32]
(Formula Removed)
The target product (0.090 g) was obtained in a similar manner as described in the procedure (4) in Reference Example 1 by using 5-benzylthio-3-chloro-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3 -yl)-l-methylpyrazole (0.24 g, 0.52 mmol) as a starting material. Solid. [0066] Reference Example 3
(1) Synthesis of (5-benzylthio-3-chloro-l-methylpyrazol-4-yl)-N-(2-methyl-2-propenyloxy)carboxylic acid amide [Chemical formula 33]
(Formula Removed)
The target product (1.8 g) was obtained in a similar manner as described in the procedure (1) in Reference Example 1 by using 2-methyl-2-propenyloxyamine hydrochloride (1.2 g, 9.7 mmol) as a starting material. Oily substance. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDCI3): 1.88 (s, 3H), 3.36 (s, 3H), 4.11 (s, 2H), 4.45 (s, 2H), 5.08 (d, J=9.9Hz, 2H), 7.01-7.06 (m, 2H), 7.22-7.28 (m, 3H) and 9.15 (brs, 1H). [0067]
(2) Synthesis of 5-benzylthio-3-chloro-4-(5-iodomethyl-5-methyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazole
[Chemical formula 34]

(Formula Removed)

The target product (2.3 g) was obtained in a similar manner as described in the procedure (2) in Reference Example 1 by using (5-benzylthio-3-chloro-l-methylpyrazol-4-yl)-N-(2-methyl-2-propenyloxy)carboxylic acid amide (1.7 g, 4.8 mmol) as a starting material. Oily substance. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 1.61 (s, 3H), 3.23 (s, 3H), 3.39-3.55 (m, 2H), 3.91-3.95 (m, IH), 4.11 (s, 2H), 4.25-4.29 (m, IH), 6.98-7.06 (m, 2H) and 7.21-7.28 (m, 3H). [0068]
(3) Synthesis of 5-benzylthio-3-chloro-l-methyl-4-(5,5-dimethyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole [Chemical formula 35]

(Formula Removed)
The target product (1.3 g) was obtained in a similar manner as described in the procedure (3) in Reference Example 1 by using (5-benzylthio-3-chloro-4-(5-iodomethyl-5-methyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazole (1.7 g, 3.6 mmol) as a starting material. Oily substance. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 1.48 (s, 6H), 3.23 (s, 3H), 3.88 (s, 2H), 4.05 (s, 2H), 6.99-7.06 (m, 2H) and 7.21-7.28 (m, 3H). [0069]

(4) Synthesis of 3-chloro-l-methyl-4-(5,5-dimethyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide [Chemical formula 36]
(Formula Removed)
The target product (0.47 g) was obtained in a similar manner as described in the procedure (4) in Reference Example 1 by using 5-benzylthio-3-chloro-l-methyl-4-(5,5-dimethyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (1.2 g, 3.4 mmol) as a starting material. Solid. [0070] Reference Example 4
Synthesis of 3-chloro-4-(5-iodomethyl-5-methyl-5H,6H-l,4,2-dioxadin-3-yl)-1 -methylpyrazole-5-sulfonamide [Chemical formula 37]
(Formula Removed)
The target product (0.21 g) was obtained in a similar manner as described in the procedure (4) in Reference Example 1 by using 5-benzylthio--3-chloro-4-(5-iodomethyl-5-methyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazole (0.50 g, 1.0 mmol) as a starting material. Solid. [0071] Reference Example 5
(1) Synthesis of (5-benzylthio-1,3-dimethylpyrazol-4-yl)-N-allyloxy carboxylic acid amide [Chemical formula 38]
(Formula Removed)
The target product (1.5 g) was obtained in a similar manner as described in the procedure (1) in Reference Example 1 by using 5 -benzylthio-1,3 -dimethylpyrazole-4-carboxylic acid chloride (1.6 g, 5.7 mmol) as a starting material. Oily substance. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3): 2.50 (s, 3H), 3.34 (s, 3H), 3.92 (s, 2H), 4.48-4.51 (m, 2H), 5.32-5.43 (m, 2H), 6.02-6.11 (m, 1H), 6.96-7.00 (m, 2H), 7.23-7.30 (m, 3H) and 9.77 (s, 1H). [0072]
(2) Synthesis of 5-benzylthio-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-1,3-dimethylpyrazole
[Chemical formula 39]
(Formula Removed)
Me The target product (0.74 g) was obtained in a similar manner as described in the procedure (2) in Reference Example 1 by using (5-benzylthio-l,3-dimethylpyrazol-4-yl)-N-allyloxycarboxylic acid amide (0.92 g, 2.9 mmol) as a starting material. Melting point: 79-81°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 2.37 (s, 3H), 3.29 (s, 3H), 3.36-3.40 (m,
2H), 3.97-4.04 (m, 3H), 4.29-4.34 (m, IH), 4.53-4.60 (m, IH), 7.00-7.06 (m, 2H) and
7.20-7.28 (m, 3H).
[0073]
(3) Synthesis of 5-benzylthio-l,3-dimethyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole [Chemical formula 40] Me
(Formula Removed)
The target product (0.19 g) was obtained in a similar manner as described in the procedure (3) in Reference Example 1 by using 5-benzylthio-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3- dimethylpyrazole (0.71 g, 1.6 mmol) as a starting material. Oily substance. [0074]
Me
(4) Synthesis of 1.3-dimethyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide [Chemical formula 41] Me
(Formula Removed)
Me The target product (0.070 g) was obtained in a similar manner as described in the procedure (4) in Reference Example 1 by using 5-benzylthio-l,3-dimethyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (0.19 g, 0.6 mmol) as a starting material. Solid. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3):
1.42 (s, 3H), 2.33 (s, 3H), 3.71-3.78 (m, IH), 4.10 (s, 3H), 4.21-4.25 (m, IH), 4.60
(m, IH) and 6.15 (s,2H).
[0075]
Reference Example 6
Synthesis of 4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3-dimethylpyrazole-5-sulfonamide [Chemical formula 42]
The target product (0.53 g) was obtained in a similar manner as described in the procedure (4) in Reference Example 1 by using 5-benzylthio-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3- dimethylpyrazole (0.70 g, 1.6 mmol) as a starting material. Solid. [0076] Reference Example 7
(1) Synthesis of (5-benzylthio-l,3-dimethylpyrazol-4-yl)-N-(2-methyl-2-propenyloxy)carboxylic acid amide [Chemical formula 43]
(Formula Removed)
Me The target product (1.15 g) was obtained in a similar manner as described in the procedure (1) in Reference Example 1 by using 5-benzylthio-l,3-dimethylpyrazole-4-carboxylic acid chloride (1.10 g, 3.9 mmol) and 2-methyl-2-
propenyloxy amine hydrochloride (1.30 g, 10.5 mmol) as starting materials. Oily substance. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDC13): 1.89 (s, 3H), 2.51 (s, 3H), 3.33 (s, 3H), 3.91 (s, 2H), 4.42 (s, 2H), 5.06 (d, J=l 1.3Hz, 2H), 6.95-7.01 (m, 2H), 7.24-7.29 (m, 3H) and 9.77 (brs, IH). [0077]
(2) Synthesis of 5-benzylthio-4-(5-iodomethyl-5-methyl-5H,6H-l ,4,2-dioxadin-3-yl)-1,3-dimethylpyrazole [Chemical formula 44]
(Formula Removed)
The target product (0.78 g) was obtained in a similar manner as described in the procedure (2) in Reference Example 1 by using (5-benzylthio-l,3-dimethylpyrazol-4-yl)-N-(2-methyl-2-propenyloxy)carboxylic acid amide (0.60 g, 1.8 mmol) as a starting material. Oily substance. Proton nuclear magnetic resonance chemical shift values 6 (ppm): 1.60 (s, 3H), 2.37 (s, 3H), 3.27 (s, 3H), 3.39-3.52 (m, 2H), 3.88-3.93 (m, IH), 4.00 (s, 2H), 4.19-4.24 (m, IH), 7.00-7.05 (m, 2H) and 7.20-7.24 (m, 3H). [0078]
(3) Synthesis of 5-benzylthio-l,3-dimethyl-4-(5,5-dimethyl-5H,6H-1,4,2-dioxadin-3 -yl)pyrazole [Chemical formula 45] The target product (0.38 g) was obtained in a similar manner as described in the procedure (3) in Reference Example 1 by using 5-benzylthio-4-(5-iodomethyl-5-methyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3-dimethylpyrazole (0.54 g, 1.2 mmol) as a starting material. Oily substance. Proton nuclear magnetic resonance chemical shift values 5 (ppm): 1.47 (s, 6H), 2.34 (s, 3H), 3.26 (s, 3H), 3.86 (s, 2H), 4.00 (s, 2H), 6.98-7.05 (m, 2H) and 7.21-7.25 (m, 3H). [0079]
(4) Synthesis of 1.3-dimethyl-4-(5,5-dimethyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide [Chemical formula 46]
(Formula Removed)
The target product (0.13 g) was obtained in a similar manner as described in the procedure (4) in Reference Example 1 by using 5-benzylthio-l,3-dimethyl-4-(5,5-dimethyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (0.34 g, 1.0 mmol) as a starting material. Solid. [0080] Reference Example 8
Synthesis of 4-(5-iodomethyl-5-methyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3-dimethylpyrazole-5 -sulfonamide [Chemical formula 47]
The target product (0.080 g) was obtained in a similar manner as described in the procedure (4) in Reference Example 1 by using 5-benzylthio-4-(5-iodomethyl-5-methyl-5H,6H-l,4,2-dioxadin-3-yl)-l,3-dimethylpyrazole (0.20 g, 0.44 mmol) as a starting material. Solid. [0081] Reference Example 9
(1) Synthesis of ethyl 2-(l,3-dimethyl-5-benzylthiopyrazol-4-yl)carbonylaminoxy)propanoate [Chemical formula 48]

(Formula Removed)
Ethyl 2-aminooxypropanoate (0.58 g, 4.4 mmol) and N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide hydrochloride (0.83 g, 4.3 mmol) were added to a methylene chloride (20 ml) solution of 5-benzylthio-3-chloro-l-methylpyrazole-4-carboxylic acid (1.0 g, 3.8 mmol), and the resultant mixture was stirred for 12 hours at room temperature. After removing the solvent of the mixture by distillation under reduced pressure, water (50 ml) was added to the mixture and the obtained mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed with saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was purified with silica gel column chromatography (developing solvent: n-hexane/ethyl acetate = 1/1) to obtain 0.88 g of the target product. Oily substance. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3): 1.30 (t, J=8 Hz, 3H), 1.57 (d, J=10 Hz, 3H), 2.47 (s, 3H), 3.28 (s, 3H), 3.40 (q, J=8 Hz, 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). [0082]
(2) Synthesis of (l,3-dimethyl-5-benzylthiopyrazol-4-yl)-N-(2-hydroxyisopropoxy)carboxylic acid amide [Chemical formula 49](Formula Removed)
A diethyl ether (5 ml) solution of ethyl 2-(l,3-dimethyl-5-benzylthiopyrazol-4-yl)carbonylaminooxy)propanoate (0.88 g, 2.3 mmol) was added dropwise to a diethyl ether (20 ml) suspension of lithium aluminum hydride (0.090 g, 2.4 mmol) with stirring at 5°C. After stirring for 2.5 hours at the same temperature, the reaction mixture was poured into ice water (20 ml). The resultant mixture was adjusted to pH 1 by adding 10% hydrochloric acid, and extracted with ethyl acetate. The obtained ethyl acetate solution was washed with water and dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain the target product (0.70 g). Oily substance. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDC13): 1.29 (d, J=8 Hz, 3H), 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, 2H), 7.20-7.32 (m, 3H), 9.60 (brs, 1H). [0083]
(3) Synthesis of 5-benzylthio-l,3-dimethyl-4-(6-methyl-5H,6H-l,4,2-dioxadin-3 -yl)pyrazole [Chemical formula 50]
(Formula Removed)
Thionyl chloride (0.34 ml, 4.6 mmol) was added to a methylene chloride (5 ml) solution of (l,3-dimethyl-5-benzylthiopyrazol-4-yl)-N-(2-hydroxyisopropoxy)carboxylic acid amide (0.70 g, 2.1 mmol), and the resultant mixture was refluxed for 1.5 hour and then the solvent of the mixture was removed by
distillation. The obtained residue was dissolved in N,N-dimethylformamide (10 ml), and 55% sodium hydride (0.10 g, 2.3 mmol) was added to the solution at 5°C. The solution was further stirred for 1 hour at the same temperature. Water (20 ml) was added to the solution, and the resultant mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed with saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was purified with silica gel thin layer chromatography (developing solvent: n-hexane/ethyl acetate = 1/1) to obtain the target product (0.32 g). Solid. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 1.37 (d, J=8 Hz, 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) Synthesis of l,3-dimethyl-4-(6-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide [Chemical formula 51 ]
(Formula Removed)
The target product (0.14 g) was obtained in a similar manner as the procedure (4) in Reference Example 1 by using 5-benzylthio-l,3-dimethyl-4-(6-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (0.32 g, 1.0 mmol) as a starting material. Solid. [0085] Reference Example 10
(1) Synthesis of 3,5-dichloro-l-methylpyrazole-4-carbohydroxamic acid [Chemical formula 52]

A water (200 ml) solution of 85% potassium hydroxide (101.5 g, 1.538 mol) was added to a water (200 ml) solution of hydroxyamine hydrochloride (106.9 g, 1.538 mol) at 5 to 15°C, and the resultant mixture was stirred for 5 minutes at room temperature. Then, a tetrahydrofuran (170 ml) solution of 3,5-dichloro-l-methylpyrazole-4-carboxylic acid chloride (100.0 g, 0.5128 mol) was added dropwise to the mixture for 2 hours at 3 to 8°C. After stirring for 0.5 hour at 5°C, the resultant mixture was adjusted to pH 3-4 by adding 35% hydrochloric acid. Precipitated solid was separated by filtration, washed with water, and dried to obtain the target product (94.9 g). Melting point: 200-202°C (decomposition). Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in dimethylsulfoxide-de): 3.79 (s, 3H), 9.24 (brs, 1H), 10.83 (brs, 1H). [0086]
(2) Synthesis of N-allyloxy-3,5-dichloro-l-methylpyrazole-4-carboxylic acid amide [Chemical formula 53]

(Formula Removed)
A toluene (60 ml) solution of 3,5-dichloro-l-methylpyrazole-4-carbohydroxamic acid (20.0 g, 95.2 mmol) and allyl bromide (13.8 g, 114 mmol) was added to a water (60 ml) solution of potassium carbonate (15.8 g, 114 mmol), and the resultant mixture was stirred for 3 hours at 50°C. After cooling to room temperature, the mixture was adjusted to pH 1 by adding 35% hydrochloric acid. Precipitated solid was separated by filtration, washed sequentially with water and toluene, and dried to
obtain the target product (17.2 g). Melting point: 96-97°C. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3): 3.84 (s, 3H), 4.51 (d, J=6.3 Hz, 2H), 5.30-5.46 (m, 2H), 5.94-6.13 (m, 1H), 8.80 (brs, 1H). [0087]
(3) Synthesis of 3,5-dichloro-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1 -methylpyrazole [Chemical formula 54]
(Formula Removed)
Iodine (122 g, 481 mmol) was added to an acetonitrile (200 ml) solution of N-allyloxy-3,5-dichloro-l-methylpyrazole-4-carboxylic acid amide (40.0 g, 160 mmol), and the resultant mixture was stirred for 4.5 hours at room temperature. Saturated sodium thiosulfate aqueous solution (150 ml) was added to the mixture, and the obtained mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed sequentially with saturated sodium hydrogen carbonate aqueous solution, saturated sodium chloride aqueous solution and water, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was purified with silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate = 5/2) to obtain the target product (54.0 g). Oily substance. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3): 3.37 (d, J=6.9 Hz, 2H), 3.83 (s, 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-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (1st procedure) [Chemical formula 55]
(Formula Removed)
3,5-dichloro-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazole (2.0 g, 5.3 mmol) was added to an N,N-dimethylformamide (15 ml) solution of sodium borohydride (0.30 g, 7.9 mmol), and the resultant mixture was stirred for 0.5 hour at 60°C. After cooling the mixture to room temperature, water (10 ml) was added to the mixture, and further 35% hydrochloric acid was added to adjust to pH 1, and the resultant mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed sequentially with saturated sodium hydrogen carbonate aqueous solution, saturated sodium chloride aqueous solution and water, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was purified with silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate = 5/2) to obtain the target product (1.1 g). Melting point: 50-51 °C. Boiling point: 142°C/0.3 mmHg. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 1.41 (d, J=6.3 Hz, 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-chloro-5-mercapto-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3 -yl)pyrazole [Chemical formula 56] Me
(Formula Removed)
3,5-dichloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole(3.8 g, 15 mmol) was added to an N,N-dimethylformamide (38 ml) suspension of 70% sodium hydrosulfide (4.3 g, 54 mmol), and the resultant mixture was stirred for 5.5 hours at 80°C. After cooling the mixture to room temperature, water (50 ml) was added to the mixture, and insoluble products were removed by filtration. The filtrate was adjusted to pH 1 by adding 35% hydrochloric acid. Precipitated solid was separated by filtration, washed with water, and dried to obtain the target product (2.55 g). Melting point: 60-64°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 1.48 (d, J=6.3 Hz, 3H), 3.75 (s, 3H), 3.79-3.85 (m, 1H), 4.28-4.32 (m, 1H), 4.64-4.74 (m, 1H). [0090]
(6) Synthesis of 3-chloro-1-methyl-4-(5-methyl-5H,6H-l ,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl chloride [Chemical formula 57] Me
(Formula Removed)
Water (20 ml) was added to a 1,2-dichloroethane (50 ml) solution of 3-chloro-5-mercapto-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (2.5 g, 10 mmol), and under ice cooling, chlorine (2.1 g, 30 mmol) was introduced into the resultant mixture with vigorous stirring. In this process, the temperature rose up to 20°C. After removing excess chlorine by introducing nitrogen, the 1,2-dichloroethane layer was separated. The obtained 1,2-dichloroethane solution was washed sequentially with saturated sodium hydrogen sulfite aqueous solution and water, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain the target product (3.1 g). Melting point: 63-68°C. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3): 1.41 (d, J=6.3 Hz, 3H), 3.75-3.81 (m, 1H), 4.20 (s, 3H), 4.23-4.28 (m, 1H), 4.54-4.64 (m, 1H). [0091]
(7) Synthesis of 3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-
yl)pyrazole-5-sulfonamide (2nd method)
28% ammonia water (1.5 g, 24.7 mmol) was added dropwise to a 1,2-dichloroethane (30 ml) solution of 3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl) pyrazole-5-sulfonyl chloride (3.1 g, 9.9 mmol) with vigorous stirring under ice cooling. After stirring the mixture for 0.5 hours at room temperature, water (20 ml) and 35% hydrochloric acid (5.2 g, 50 mmol) were added to the mixture, and the resultant mixture was extracted with 1,2-dichloroethane. The obtained 1,2-dichloroethane solution was washed with water and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain the target product (2.8 g). Melting point: 120-122°C. [0092]
(8) Synthesis of N-methoxycarbonyl-3-chloro-l-methyl-4-(5-methyl-5H,6H-
l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide
[Chemical formula 58] (Formula Removed)

Anhydrous potassium carbonate (1.8 g, 13 mmol) and methyl chloroformate (0.96 g, 10 mmol) were added to an acetonitrile (15 ml) solution of 3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (3.0 g, 10 mmol), and the resultant mixture was refluxed for 1 hour under heating. Under reduced pressure, the residue obtained by removing the solvent by distillation was dissolved into water (20 ml), and insoluble materials were removed by filtration. Then the obtained mixture was extracted with 1,2-dichloroethane. The obtained aqueous layer was adjusted to pH 1 by adding 35% hydrochloric acid, and precipitated solid was separated by filtration, washed with water and dried to obtain the target product (2.4 g). Melting point: 133-134°C. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3): 1.43 (d, J=6.6 Hz, 3H), 3.72 (s,

3H), 3.74-3.81 (m, IH), 4.21-4.30 (m, IH), 4.25 (s, 3H), 4.56-4.66 (m, IH), 8.83 (brs,
IH).
[0093]
Reference Example 11
(1) Synthesis of 3,5-dichloro-1 -methyl-4-(5-methylene-5H,6H-1,4,2-dioxadin-3 -
yl)pyrazole
[Chemical formula 59]

(Formula Removed)
Potassium t-butoxide (0.52 g, 4.6 mmol) was added to a tetrahydrofuran (10 ml) solution of 3,5-dichloro-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1 -methylpyrazole (1.5 g, 4.0 mmol), and the resultant mixture was stirred for 0.25 hour at room temperature. Saturated ammonium chloride aqueous solution (20 ml) was added to the mixture, and the obtained mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed sequentially with water and saturated sodium chloride aqueous solution, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was purified with silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate = 1/1) to obtain the target product (0.88 g). Melting point: 68-70°C. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3): 3.84 (s, 3H), 4.42 (s, 2H), 4.45 (d, J=1.8 Hz, IH), 4.85 (d, J-1.8 Hz, IH). [0094]
(2) Synthesis of 3,5-dichloro-1 -methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (2nd method) [0095]
5% palladium-carbon (0.56 g) was added to an ethyl acetate (56 ml) solution of 3,5-dichloro-l-methyl-4-(5-methylene-5H,6H-l,4,2-dioxadin-3- yl)pyrazole (2.8 g, 11 mmol), and under hydrogen atmosphere (1 atm), the resultant mixture was stirred

for 17 hours at room temperature. 5% palladium-carbon (0.05 g) was further added to the mixture, and the resultant mixture was further stirred under the above-mentioned condition for 1 hour, and then the catalyst was removed by filtration. The solvent of the filtrate was removed by distillation and the obtained residue was purified with alumina column chromatography (eluting solvent: chloroform) to obtain the target product (2.6 g). Melting point: 50-51 °C. [0096] Reference Example 12
Synthesis of 3,5-dichloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (3rd method) [0097]
Trifluoromethane sulfonic acid (0.10 g, 1.0 mmol) was added to a toluene (5 ml) solution of N-allyloxy-3,5-dichloro-l-methylpyrazole-4-carboxylic acid amide (0.50 g, 2.0 mmol), and the resultant mixture was refluxed for 20 hours. The obtained toluene solution was sequentially washed with saturated potassium carbonate aqueous solution and water and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was purified with silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate - 1/1) to obtain the target product (0.08 g). Melting point: 50-51 °C. [0098] Reference Example 13
(1) Synthesis of N-(n-butylaminocarbonyl)-3-chloro-1 -methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide [Chemical formula 60] Me
(Formula Removed)
Anhydrous potassium carbonate (3.76 g, 27.0 mmol) and n-
butylisocyanate(2.14 g, 21.6 mmol) were added to a 1,2-dichloroethane (30 ml)

solution of 3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (5.31 g, 18.0 mmol), and the resultant mixture was refluxed under heating for 1 hour. After cooling the mixture to room temperature, water (25 ml) was added to the mixture, and the obtained mixture was stirred vigorously. After separating the organic layer, the obtained aqueous layer was adjusted to pH 1 by adding 35% hydrochloric acid, and the resultant mixture was extracted with 1,2-dichloroethane. The obtained 1,2-dichloroethane solution was washed with water and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation. A small amount of diisopropyl ether was added to the obtained residue, and precipitated solid was separated by filtration, washed with water, and dried to obtain the target product (3.53 g). Melting point: 130-133°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDCI3): 0.89 (t, J=7.2 Hz, 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). [0099]
(2) Synthesis of 3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl isocyanate [Chemical formula 61] Me
(Formula Removed)
N-(n-butylaminocarbonyl)-3-chloro-l-methyl-4-(5-methyl-5H,6H-1,4,2-
dioxadin-3-yl)pyrazole-5-sulfonamide (5.0 g, 13 mmol), bistrichloromethyl carbonate
(9.4 g, 32 mmol) and triethylamine (0.1 ml) was added to toluene (15 ml), and the
resultant mixture was refluxed under heating for 8 hours. The solvent of the mixture
was removed by distillation to obtain the target product (4.0 g). Oily substance.
[0100]
Reference Example 14

(1) Synthesis of bis(3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazol-5-yl)disulfide [Chemical formula 62]

(Formula Removed)
Air was introduced into an N,N-dimethylformamide (10 ml) solution of 3-chloro-5-mercapto-l-methyl-4-(5-methyl-5H,6H-l ,4,2-dioxadin-3-yl)pyrazole (1.0 g, 4.0 mmol) with stirring for 3.5 hours at room temperature. Precipitated solid was separated by filtration, washed with water and dried to obtain the target product (0.49 g). Melting point: 165-167°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 1.36 (d, J=6.3 Hz, 3H), 3.49-3.64 (m, 1H), 3.89 (s, 3H), 4.04-4.18 (m, 1H), 4.32-4.48 (m, 1H). [0101]
(2) Synthesis of 3-chloro-1 -methyl-4-(5 -methyl-5 H,6H-1,4,2-dioxadin-3 -yl)pyrazol-5-sulfonyl chloride (2nd method)
Water (20 ml) was added to a 1,2-dichloroethane (50 ml) solution of bis(3-chloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazol-5-yl)disulfide (2.5 g, 5.1 mmol), and under ice cooling, chlorine (2.1 g, 30 mmol) was introduced in the resultant mixture with vigorous stirring. In this process, the temperature rose up to 20°C. After removing excess chlorine by introducing nitrogen, the 1,2-dichloroethane layer was separated. The obtained 1,2-dichloroethane solution was washed sequentially with saturated sodium hydrogen sulfite aqueous solution and water, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain the target product (3.0 g). Melting point: 63-68°C. [0102] Reference Example 15

Synthesis of 3,5-dichloro-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazole (2nd method)
N-iodosuccinimide (0.67 g, 3.0 mmol) was added to an acetonitrile (5 ml) solution of N-allyloxy-3,5-dichloro-l-methylpyrazole-4-carboxylic acid amide (0.50 g, 2.0 mmol), and the resultant mixture was stirred for 15 hours at room temperature. Saturated sodium hydrogen sulfite aqueous solution (10 ml) was added to the mixture, and the obtained mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was sequentially washed with saturated sodium hydrogen carbonate aqueous solution, saturated sodium chloride aqueous solution and water, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was purified with silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate = 3/1) to obtain the target product (0.60 g). Oily substance. [0103] Reference Example 16
(1) Synthesis of 4-(5-bromomethyl-5H,6H-l,4,2-dioxadin-3-yl)~3,5-dichloro-1 -methylpyrazole [Chemical formula 63]

(Formula Removed)
N-bromosuccinimide (17.1 g, 96.0 mmol) was added to an acetonitrile (200 ml) solution of N-allyloxy-3,5-dichloro-l-methylpyrazole-4-carboxylic acid amide (20.0 g, 80.0 mmol), and the resultant mixture was stirred for 1 hour at room temperature. Saturated sodium hydrogen sulfite aqueous solution (100 ml) was added to the mixture, and the acetonitrile of the mixture was removed by distillation. Then, the obtained mixture was extracted with ethyl acetate, and the obtained ethyl acetate solution was washed sequentially with water and saturated sodium chloride aqueous solution, and then dried over anhydrous sodium sulfate. The solvent of the solution

was removed by distillation and the obtained residue was purified with silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate = 3/1) to obtain the target product (18.4 g). Melting point: 53-54°C. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDC13): 3.57-3.61 (d, J=6.9 Hz, 2H), 3.83 (s, 3H), 4.06-4.11 (m, 1H), 4.29-4.33 (m, 1H), 4.65-4.72 (m, 1H). [0104]
(2) Synthesis of 3,5-dichloro-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole (3rd method)
Sodium borohydride (0.11 g, 3.0 mmol) was added to an N-methyl-2-
pyrrolidone (5 ml) solution of 4-(5-bromomethyl-5H,6H-l,4,2-dioxadin-3-yl)-3,5-
dichloro-1-methylpyrazole (0.50 g, 1.5 mmol), and the resultant mixture was stirred for 1 hour at 60°C. After cooling the mixture to room temperature, water (5 ml) was added to the mixture. The resultant mixture was adjusted to pH 1 by adding 35% hydrochloric acid, and extracted with ethyl acetate. The obtained ethyl acetate
solution was washed sequentially with saturated sodium hydrogen carbonate aqueous
solution, saturated sodium chloride aqueous solution and water, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was purified with silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate = 5/2) to obtain the target product (0.31 g). Melting
point: 50-51 °C. [0105] Reference Example 17
(1) Synthesis of 5-benzylthio-l-methylpyrazole-4-carbohydroxamic acid [Chemical formula 64]
(Formula Removed)
Thionyl chloride (11.4 g, 95.8 mmol) and N,N-dimethylformamide (0.1 g) were added to a toluene (100 ml) suspension of 5-benzylthio-l-methylpyrazole-4-carboxylic acid (15.9 g, 64.0 mmol), and the resultant mixture was refluxed with
heating for 4 hours. The residue obtained by removing the solvent by distillation was dissolved into tetrahydrofuran (40 ml).
Separately, a water (40 ml) solution of 85% potassium hydroxide (12.6 g, 191 mmol) was added to a water (40 ml) solution of hydroxylamine hydrochloride (13.3 g, 191 mmol) at 5-15°C, and the resultant mixture was stirred for 15 minutes at room temperature. Then, the above-mentioned tetrahydrofuran solution was added dropwise to the mixture at 3-15°C. After further stirring for 1.5 hour at 3°C, the resultant mixture was adjusted to pH 3-4 by adding 35% hydrochloric acid (20 ml) and the obtained mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed with water and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was purified with silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate = 1/1) to obtain the target product (10.3 g). Resinous substance. Proton nuclear magnetic resonance chemical shift values 5 (ppm) (in CDCI3): 3.42 (s, 3H), 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-allyloxy-5-benzylthio-l-methylpyrazole-4-carboxylic acid amide [Chemical formula 65]
(Formula Removed)
MeA toluene (10 ml) solution of 5-benzylthio-l-methylpyrazole-4-carbohydroxamic acid (2.0 g, 7.6 mmol) and allyl bromide (1.1 g, 9.1 mmol) were added to a water (10 ml) solution of potassium carbonate (1.3 g, 9.4 mmol), and the resultant mixture was stirred for 4 hours at 50°C. After cooling to room temperature, the mixture was adjusted to pH 1 by adding 35% hydrochloric acid and the obtained mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed with water and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain the target product (1.9 g). Oily
substance. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3): 3.42 (s, 3H), 3.95 (s, 2H), 4.49 (d, J=6.3 Hz, 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). [0107]
(3) Synthesis of 5-benzylthio-4-(5-iodomethyl-5H,6H-l ,4,2-dioxadin-3-yl)-l-methylpyrazole [Chemical formula 66]

(Formula Removed)
Iodine (4.5 g, 18 mmol) was added to an acetonitrile (10 ml) solution of N-allyloxy-5-benzylthio-l-methylpyrazole-4-carboxy3ic acid amide (1.8 g, 5.9 mmol), and the resultant mixture was stirred for 8 hours at room temperature. Saturated sodium thiosulfate aqueous solution (30 ml) was added to the mixture, and obtained mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was sequentially washed with saturated sodium hydrogen carbonate aqueous solution, saturated sodium chloride aqueous solution and water, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was purified with silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate = 3/1) to obtain the target product (1.7 g). Resinous substance. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDC13): 3.36-3.42 (m, 5H), 3.98-4.05 (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) Synthesis of 5-benzylthio-l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl) pyrazole [Chemical formula 67]

(Formula Removed)
An N,N-dimethylformamide (5 ml) solution of sodium borohydride (0.21 g, 5.6 mmol) was added dropwise to an N,N-dimethylformamide (8 ml) solution of 5-benzylthio-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)-l-methylpyrazole (1.6 g, 3.7 mmol) for 0.3 hours at 50°C, and the resultant mixture was further stirred for 1 hour at 50°C. After cooling the mixture to room temperature, water (20 ml) was added to the mixture. The obtained mixture was adjusted to pH 1 by adding 35% hydrochloric acid, and extracted with ethyl acetate. The obtained ethyl acetate solution was sequentially washed with 6% hydrochloric acid and water, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain the target product (1.1 g). Resinous substance. Proton nuclear magnetic resonance chemical shift values 8(ppm) (in CDCI3): 1.43 (d, J=6.3 Hz, 3H), 3.36 (s, 3H), 3.69-3.77 (m, 1H), 4.04 (q, J=12.6 Hz, 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 l-methyl-4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide [Chemical formula 68] Me

(Formula Removed)
Water (10 ml) and 35% hydrochloric acid (0.1 g) were added to a 1,2-dichloroethane (10 ml) solution of 5-benzylthio-l -methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl) pyrazole (1.1 g, 3.5 mmol), and chlorine (2.5 g, 35 mmol) was introduced into the resultant mixture at 5°C with vigorous stirring. In this process, the temperature of the reaction mixture rose up to 19°C. After removing excess chlorine by introducing nitrogen, water (20 ml) was added to the mixture, and the obtained mixture was extracted with 1,2-dichloroethane. The obtained 1,2-dichloroethane solution was concentrated to 8 ml under reduced pressure. This solution was added dropwise to a separately prepared 1,2-dichloroethane (8 ml) solution of 28% aqueous ammonia (1 ml) at 5°C with vigorous stirring, and the resultant mixture was further stirred for 0.5 hour at room temperature. The mixture was adjusted to pH 1 by adding 35% hydrochloric acid, and then the obtained mixture was extracted with 1,2-dichloroethane. The obtained 1,2-dichloroethane solution was dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation and the obtained residue was recrystallized from toluene to obtain the target product (0.43 g). Melting point: 97-99°C. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDC13): 1.43 (d, J=6.3 Hz, 3H), 3.70-3.77 (m, 1H), 4.19-4.26 (m, 4H), 4.55-4.62 (m, 1H), 6.49 (brs, 2H), 7.75 (s, 1H). [0110] Reference Example 18
ynthesis of 4-(5-methyl-5H,6H-l,4,2-dioxadin-3-yl)-l-(pyridyl-2-yl)pyrazole-5-sulfonamide [Chemical formula 69] Me

(Formula Removed)
The target product (0.45 g) was obtained in a similar manner as described in Reference Example 1 by using 5-benzylthio-l-(pyridyl-2-yl)pyrazol-4-carboxylic acid chloride (3.63 g, 11.0 mmol) as a starting material. Resinous substance. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3): 1.43 (d, J=6.3 Hz, 3H), 3.77-3.83 (m, 1H), 4.22-4.26 (m, 1H), 4.58-4.63 (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). [0111] Reference Example 19
Synthesis of 3-chloro-l-methyl-4-(5-methylene-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide [Chemical formula 70]

(Formula Removed)
3-chloro-l-methyl-4-(5-iodomethyl-5H,6H-l,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (0.55 g, 1.3 mmol) was dissolved into 1,2-dimethoxyethane (10 ml), and the resultant mixture was stirred under ice cooling. Then, after a methanol solution of 28% sodium methoxide (0.6 g, 3.1 mmol) was slowly added to the mixture at 0°C, the obtained mixture was stirred for 1 hour. The reaction was terminated with 2N hydrochloric acid, and the resultant mixture was extracted with ethyl acetate. The ethyl acetate layer was sequentially washed with water and saturated sodium chloride aqueous solution, and then dried over anhydrous sodium sulfate. The solvent of the solution was removed by distillation to obtain oily substance. The obtained oily substance was purified with silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate = 1/1) to obtain the target product (0.36 g). Colorless solid. Melting point: 116-119°C. Proton nuclear magnetic resonance chemical shift values 8 (ppm) (in CDCI3): 4.15 (s, 3H), 4.52 (s, 2H), 4.53 (cl, J=2.8 Hz, 1H), 4.93 (d, J=2.8 Hz, 1H), 6.03 (brs, 2H). [0112]
Structural formulae and physical properties of the compound (A) synthesized in a similar manner as described in the above-mentioned Synthesis Examples and Reference Examples are shown in the first table below with the compounds described in the above-mentioned Synthesis Examples and Reference Examples. [0113] [Chemical formula 71]

(Table Removed)
[0114]
Combinations of the compound (A) and at least one compound selected from dymron, dimepiperate and esprocarb applied at a time include compound 1/dymron, compound 1/dimepiperate, compound 1/esprocarb, compound 2/dymron, compound 2/dimepiperate, compound 2/esprocarb, compound 3/dymron, compound 3/dimepiperate, compound 3/esprocarb, compound 4/dymron, compound 4/dimepiperate, compound 4/esprocarb, compound 5/dymron, compound 5/dimepiperate, compound 5/esprocarb, compound 6/dymron, compound 6/dimepiperate, compound 6/esprocarb, compound 7/dymron, compound 7/dimepiperate, compound 7/esprocarb, compound 8/dymron, compound 8/dimepiperate, compound 8/esprocarb, compound 9/dymron, compound 9/dimepiperate, compound 9/esprocarb, compound 10/dymron, compound 10/dimepiperate, compound 10/esprocarb, compound 11/dymron, compound 11/dimepiperate, compound 11/esprocarb, compound 12/dymron, compound 12/dimepiperate, compound 12/esprocarb, compound 13/dymron, compound 13/dimepiperate, compound 13/esprocarb, compound 14/dymron, compound 14/dimepiperate, compound 14/esprocarb, compound 15/dymron, compound 15/dimepiperate, compound 15/esprocarb, compound 16/dymron, compound 16/dimepiperate, compound 16/esprocarb, compound 17/dymron, compound 17/dimepiperate, compound 17/esprocarb, compound 18/dymron, compound 18/dimepiperate, compound 18/esprocarb, compound 19/dymron, compound 19/dimepiperate, compound 19/esprocarb, compound 20/dymron, compound 20/dimepiperate, compound 20/esprocarb, compound 21/dymron, compound 21/dimepiperate and compound 21/esprocarb. In addition, herbicides applied at a time with the compound (A) include compounds listed in the second table 2 as compounds of group B other than at least one compound selected from dymron,
dimepiperate and esprocarb. Moreover, when the compound (A) and at least one compound selected from dymron, dimepiperate and esprocarb are applied at a time, compounds listed in the second table below may also be applied at a time. [0115]
In the present invention, for appication, compounds may be applied separately or in combination. When compounds are applied separately, either a simultaneous application or an interval application, as long as such interval is close in time, can be applicable. Either application method described here is included in the present invention. [Table 2] [Second Table]
Example compounds
Pyrazosulfuron-ethyl (common name), bensulfuron-methyl (common name), cinosulfuron (common name), imazosulfuron (common name), azimsulfuron (common name), halosulfuron-methyl (common name), cyclosulfamuron (common name), ethoxysulfuron (common name), pyrazolate (common name), pyrazoxyfen (common name), benzofenap (common name), bromobutide (common name), naproanilide (common name), pretilachlor (common name), butachlor (common name), thenylchlor (common name), CNP (common name), chlomethoxynil (common name), bifenox (common name), oxadiazon (common name), oxadiargyl (common name), pentoxazone (common name), cafenstrole (common name), oxaziclomefone (common name), indanofan (common name), pyriminobac-methyl (common name), cyhalofop-butyl (common name), fentrazamide (common name), mefenacet (common name), butenachlor (common name), dithiopyl (common name), benfuresate (common name), pyributicarb (common name), benthiocarb (common name), molinate (common name), butamifos (common name), quinclorac (common name), cinmethylin (common name), simetryn (common name), bensulide (common name), dimethametryn (common name), MCPA (common name), MCPB (common name), etobenzanid (common name), cumyluron (common name), benzobicyclon (common name), pyriftalid (common name), bispyribac (common name), pyraclonil (common name), anilofos (common name), OK-701 (test name), penoxsulam (common name), AVH-301 (test name), KUH-021 (test name), TH-547 (test name), Bentazone
(common name), 2, 4-PA (common name), metamifop (common name), flucetosulfuron (common name), HOK-201 (common name), mesotrione (common name), propanil (common name), quinoclamine (common name), and clomeprop
[0116]
The third table below shows specific applicable combinations between the compound (A) and compounds listed in the second table. [Third Table]
Example combination of compounds capable of applying simultaneously
Compound 1 / pyrazosulfuron-ethyl, compound 1 / bensulfuron-methyl, compound 1 / cinosulfuron, compound 1 / imazosulfuron, compound 1 / azimsulfuron, compound 1 / halosulfuron-methyl, compound 1 / cyclosulfamuron, compound 1 / ethoxysulfuron, compound 1 / pyrazolate, compound 1 / pyrazoxyfen, compound 1 / benzofenap, compound 1 / bromobutide, compound 1 / naproanilide, compound 1 / pretilachlor, compound 1 / butachlor, compound 1 / thenylchlor, compound 1 / CNP, compound 1 / chlomethoxynil, compound 1 / bifenox, compound 1 / oxadiazon, compound 1 / oxadiargyl, compound 1 / pentoxazone, compound 1 / cafenstrole, compound 1 / oxaziclomefone, compound 1 / indanofan, compound 1 / pyriminobac-methyl, compound 1 / cyhalofop-butyl, compound 1 / fentrazamide, compound 1 / mefenacet, compound 1 / butenachlor, compound 1 / dithiopyl, compound 1 / benfuresate, compound 1 / pyributicarb, compound 1 / benthiocarb, compound 1 / molinate, compound 1 / butamifos, compound 1 / quinclorac, compound 1 / cinmethylin, compound 1 / simetryn, compound 1 / bensulide, compound 1 / dimethametryn, compound 1 / MCPA, compound 1 / MCPB, compound 1 / etobenzanid, compound 1 / cumyluron, compound 1 / benzobicyclon, compound 1 / pyriftalid, compound 1 / bispyribac, compound 1 / pyraclonil, compound 1 / anilofos, compound 1 / OK-701, compound 1 / penoxsulam, compound 1 / AVH-301, compound 1 / KUH-021, compound 1 / TH-547, compound 1 / bentazone, compound 1 / 2, 4-PA, compound 1 / metamifop, compound 1 / flucetosulfuron, compound 1 / HOK-201, compound 1 / mesotrione, compound 1 / propanil, compound 1 / quinoclamine, and compound 1 / clomeprop;
compound 2 / pyrazosulfuron-ethyl, compound 2 / bensulfuron-methyl, compound 2 / cinosulfuron, compound 2 / imazosulfuron, compound 2 / azimsulfuron, compound 2 / halosulfuron-methyl, compound 2 / cyclosulfamuron, compound 2 / ethoxysulfuron, compound 2 / pyrazolate, compound 2 / pyrazoxyfen, compound 2 / benzofenap, compound 2 / bromobutide, compound 2 / naproanilide, compound 2 / pretilachlor, compound 2 / butachlor, compound 2 / thenylchlor, compound 2 / CNP, compound 2 / chlomethoxynil, compound 2 / bifenox, compound 2 / oxadiazon, compound 2 / oxadiargyl, compound 2 / pentoxazone, compound 2 / cafenstrole, compound 2 / oxaziclomefone, compound 2 / indanofan, compound 2 / pyriminobac-methyl, compound 2 / cyhalofop-butyl, compound 2 / fentrazamide, compound 2 / mefenacet, compound 2 / butenachlor, compound 2 / dithiopyl, compound 2 / benfuresate, compound 2 / pyributicarb, compound 2 / benthiocarb, compound 2 / molinate, compound 2 / butamifos, compound 2 / quinclorac, compound 2 / cinmethylin, compound 2 / simetryn, compound 2 / bensulide, compound 2 / dimethametryn, compound 2 / MCPA, compound 2 / MCPB, compound 2 / etobenzanid, compound 2 / cumyluron, compound 2 / benzobicyclon, compound 2 / pyriftalid, compound 2 / bispyribac, compound 2 / pyraclonil, compound 2 /anilofos, compound 2 / OK-701, compound 2 / penoxsulam, compound 2 / AVH-301, compound 2 / KUH-021, compound 2 / TH-547, compound 2 / bentazone, compound 2/2, 4-PA, compound 2 / metamifop, compound 2 / flucetosulfuron, compound 2 / HOK-201, compound 2 / mesotrione, compound 2 / propanil, compound 2 / quinoclamine, and compound 2 / clomeprop;
compound 3 / pyrazosulfuron-ethyl, compound 3 / bensulfuron-methyl, compound 3 / cinosulfuron, compound 3 / imazosulfuron, compound 3 / azimsulfuron, compound 3 / halosulfuron-methyl, compound 3 / cyclosulfamuron, compound 3 / ethoxysulfuron, compound 3 / pyrazolate, compound 3 / pyrazoxyfen, compound 3 / benzofenap, compound 3 / bromobutide, compound 3 / naproanilide, compound 3 / pretilachlor, compound 3 / butachlor, compound 3 / thenylchlor, compound 3 / CNP, compound 3 / chlomethoxynil, compound 3 / bifenox, compound 3 / oxadiazon, compound 3 / oxadiargyl, compound 3 / pentoxazone, compound 3 / cafenstrole, compound 3 / oxaziclomefone, compound 3 / indanofan, compound 3 / pyriminobac-methyl, compound 3 / cyhalofop-butyl, compound 3 / fentrazamide, compound 3 / mefenacet, compound 3 / butenachlor, compound 3 / dithiopyl, compound 3 / benfuresate, compound 3 / pyributicarb, compound 3 / benthiocarb, compound 3 / molinate,
compound 3 / butamifos, compound 3 / quinclorac, compound 3 / cinmethylin, compound 3 / simetryn, compound 3 / bensulide, compound 3 / dimethametryn, compound 3 / MCPA, compound 3 / MCPB, compound 3 / etobenzanid, compound 3 / cumyluron, compound 3 / benzobicyclon, compound 3 / pyriftalid, compound 3 / bispyribac, compound 3 / pyraclonil, compound 3 /anilofos, compound 3 / OK-701, compound 3 / penoxsulam, compound 3 / AVH-301, compound 3 / KUH-021, compound 3 / TH-547, compound 3 / bentazone, compound 3/2, 4-PA, compound 3 / metamifop, compound 3 / flucetosulfuron, compound 3 / HOK-201, compound 3 / mesotrione, compound 3 / propanil, compound 3 / quinoclamine, and compound 3 / clomeprop;
compound 4 / pyrazosulfuron-ethyl, compound 4 / bensulfuron-methyl, compound 4 / cinosulfuron, compound 4 / imazosulfuron, compound 4 / azimsulfuron, compound 4 / halosulfuron-methyl, compound 4 / cyclosulfamuron, compound 4 / ethoxysulfuron, compound 4 / pyrazolate, compound 4 / pyrazoxyfen, compound 4 / benzofenap, compound 4 / bromobutide, compound 4 / naproanilide, compound 4 / pretilachlor, compound 4 / butachlor, compound 4 / thenylchlor, compound 4 / CNP, compound 4 / chlomethoxynil, compound 4 / bifenox, compound 4 / oxadiazon, compound 4 / oxadiargyl, compound 4 / pentoxazone, compound 4 / cafenstrole, compound 4 / oxaziclomefone, compound 4 / indanofan, compound 4 / pyriminobac-methyl, compound 4 / cyhalofop-butyl, compound 4 / fentrazamide, compound 4 / mefenacet, compound 4 / butenachlor, compound 4 / dithiopyl, compound 4 / benfuresate, compound 4 / pyributicarb, compound 4 / benthiocarb, compound 4 / molinate, compound 4 / butamifos, compound 4 / quinclorac, compound 4 / cinmethylin, compound 4 / simetryn, compound 4 / bensulide, compound 4 / dimethametryn, compound 4 / MCPA, compound 4 / MCPB, compound 4 / etobenzanid, compound 4 / cumyluron, compound 4 / benzobicyclon, compound 4 / pyriftalid, compound 4 / bispyribac, compound 4 / pyraclonil, compound 4 /anilofos, compound 4 / OK-701, compound 4 / penoxsulam, compound 4 / AVH-301, compound 4 / KUH-021, compound 4 / TH-547, compound 4 / bentazone, compound 4/2, 4-PA, compound 4 / metamifop, compound 4 / flucetosulfuron, compound 4 / HOK-201, compound 4 / mesotrione, compound 4 / propanil, compound 4 / quinoclamine, and compound 4 / clomeprop;
compound 5 / pyrazosulfuron-ethyl, compound 5 / bensulfuron-methyl, compound 5 / cinosulfuron, compound 5 / imazosulfuron, compound 5 / azimsulfuron, compound 5 /
halosulfuron-methyl, compound 5 / cyclosulfamuron, compound 5 / ethoxysulfuron, compound 5 / pyrazolate, compound 5 / pyrazoxyfen, compound 5 / benzofenap, compound 5 / bromobutide, compound 5 / naproanilide, compound 5 / pretilachlor, compound 5 / butachlor, compound 5 / thenylchlor, compound 5 / CNP, compound 5 / chlomethoxynil, compound 5 / bifenox, compound 5 / oxadiazon, compound 5 / oxadiargyl, compound 5 / pentoxazone, compound 5 / cafenstrole, compound 5 / oxaziclomefone, compound 5 / indanofan, compound 5 / pyriminobac-methyl, compound 5 / cyhalofop-butyl, compound 5 / fentrazamide, compound 5 / mefenacet, compound 5 / butenachlor, compound 5 / dithiopyl, compound 5 / benfuresate, compound 5 / pyributicarb, compound 5 / benthiocarb, compound 5 / molinate, compound 5 / butamifos, compound 5 / quinclorac, compound 5 / cinmethylin, compound 5 / simetryn, compound 5 / bensulide, compound 5 / dimethametryn, compound 5 / MCPA, compound 5 / MCPB, compound 5 / etobenzanid, compound 5 / cumyluron, compound 5 / benzobicyclon, compound 5 / pyriftalid, compound 5 / bispyribac, compound 5 / pyraclonil, compound 5 /anilofos, compound 5 / OK-701, compound 5 / penoxsulam, compound 5 / AVH-301, compound 5 / KUH-021, compound 5 / TH-547, compound 5 / bentazone, compound 5/2, 4-PA, compound 5 / metamifop, compound 5 / flucetosulfuron, compound 5 / HOK-201, compound 5 / mesotrione, compound 5 / propanil, compound 5 / quinoclamine, and compound 5 / clomeprop;
compound 6 / pyrazosulfuron-efhyl, compound 6 / bensulfuron-methyl, compound 6 / cinosulfuron, compound 6 / imazosulfuron, compound 6 / azimsulfuron, compound 6 / halosulfuron-methyl, compound 6 / cyclosulfamuron, compound 6 / ethoxysulfuron, compound 6 / pyrazolate, compound 6 / pyrazoxyfen, compound 6 / benzofenap, compound 6 / bromobutide, compound 6 / naproanilide, compound 6 / pretilachlor, compound 6 / butachlor, compound 6 / thenylchlor, compound 6 / CNP, compound 6 / chlomethoxynil, compound 6 / bifenox, compound 6 / oxadiazon, compound 6 / oxadiargyl, compound 6 / pentoxazone, compound 6 / cafenstrole, compound 6 / oxaziclomefone, compound 6 / indanofan, compound 6 / pyriminobac-methyl, compound 6 / cyhalofop-butyl, compound 6 / fentrazamide, compound 6 / mefenacet, compound 6 / butenachlor, compound 6 / dithiopyl, compound 6 / benfuresate, compound 6 / pyributicarb, compound 6 / benthiocarb, compound 6 / molinate, compound 6 / butamifos, compound 6 / quinclorac, compound 6 / cinmethylin, compound 6 / simetryn, compound 6 / bensulide, compound 6 / dimethametryn,

compound 6 / MCPA, compound 6 / MCPB, compound 6 / etobenzanid, compound 6 / cumyluron, compound 6 / benzobicyclon, compound 6 / pyriftalid, compound 6 / bispyribac, compound 6 / pyraclonil, compound 6 /anilofos, compound 6 / OK-701, compound 6 / penoxsulam, compound 6 / AVH-301, compound 6 / KUH-021, compound 6 / TH-547, compound 6 / bentazone, compound 6/2, 4-PA, compound 6 / metamifop, compound 6 / flucetosulfuron, compound 6 / HOK-201, compound 6 / mesotrione, compound 6 / propanil, compound 6 / quinoclamine, and compound 6 / clomeprop;
compound 7 / pyrazosulfuron-ethyl, compound 7 / bensulfuron-methyl, compound 7 / cinosulfuron, compound 7 / imazosulfuron, compound 7 / azimsulfuron, compound 7 / halosulfuron-methyl, compound 7 / cyclosulfamuron, compound 7 / ethoxysulfuron, compound 7 / pyrazolate, compound 7 / pyrazoxyfen, compound 7 / benzofenap, compound 7 / bromobutide, compound 7 / naproanilide, compound 7 / pretilachlor, compound 7 / butachlor, compound 7 / thenylchlor, compound 7 / CNP, compound 7 / chlomethoxynil, compound 7 / bifenox, compound 7 / oxadiazon, compound 7 / oxadiargyl, compound 7 / pentoxazone, compound 7 / cafenstrole, compound 7 / oxaziclomefone, compound 7 / indanofan, compound 7 / pyriminobac-methyl, compound 7 / cyhalofop-butyl, compound 7 / fentrazamide, compound 7 / mefenacet, compound 7 / butenachlor, compound 7 / dithiopyl, compound 7 / benfuresate, compound 7 / pyributicarb, compound 7 / benthiocarb, compound 7 / molinate, compound 7 / butamifos, compound 7 / quinclorac, compound 7 / cinmethylin, compound 7 / simetryn, compound 7 / bensulide, compound 7 / dimethametryn, compound 7 / MCPA, compound 7 / MCPB, compound 7 / etobenzanid, compound 7 / cumyluron, compound 7 / benzobicyclon, compound 7 / pyriftalid, compound 7 / bispyribac, compound 7 / pyraclonil, compound 7 /anilofos, compound 7 / OK-701, compound 7 / penoxsulam, compound 7 / AVH-301, compound 7 / KUH-021, compound 7 / TH-547, compound 7 / bentazone, compound 7/2, 4-PA, compound 7 / metamifop, compound 7 / flucetosulfuron, compound 7 / HOK-201, compound 7 / mesotrione, compound 7 / propanil, compound 7 / quinoclamine, and compound 7 / clomeprop;
compound 8 / pyrazosulfuron-ethyl, compound 8 / bensulfuron-methyl, compound 8 / cinosulfuron, compound 8 / imazosulfuron, compound 8 / azimsulfuron, compound 8 / halosulfuron-methyl, compound 8 / cyclosulfamuron, compound 8 / ethoxysulfuron, compound 8 / pyrazolate, compound 8 / pyrazoxyfen, compound 8 / benzofenap,
compound 8 / bromobutide, compound 8 / naproanilide, compound 8 / pretilachlor, compound 8 / butachlor, compound 8 / thenylchlor, compound 8 / CNP, compound 8 / chlomethoxynil, compound 8 / bifenox, compound 8 / oxadiazon, compound 8 / oxadiargyl, compound 8 / pentoxazone, compound 8 / cafenstrole, compound 8 / oxaziclomefone, compound 8 / indanofan, compound 8 / pyriminobac-methyl, compound 8 / cyhalofop-butyl, compound 8 / fentrazamide, compound 8 / mefenacet, compound 8 / butenachlor, compound 8 / dithiopyl, compound 8 / benfuresate, compound 8 / pyributicarb, compound 8 / benthiocarb, compound 8 / molinate, compound 8 / butamifos, compound 8 / quinclorac, compound 8 / cinmethylin, compound 8 / simetryn, compound 8 / bensulide, compound 8 / dimethametryn, compound 8 / MCPA, compound 8 / MCPB, compound 8 / etobenzanid, compound 8 / cumyluron, compound 8 / benzobicyclon, compound 8 / pyriftalid, compound 8 / bispyribac, compound 8 / pyraclonil, compound 8 /anilofos, compound 8 / OK-701, compound 8 / penoxsulam, compound 8 / AVH-301, compound 8 / KUH-021, compound 8 / TH-547, compound 8 / bentazone, compound 8/2, 4-PA, compound 8 / metamifop, compound 8 / flucetosulfuron, compound 8 / HOK-201, compound 8 / mesotrione, compound 8 / propanil, compound 8 / quinoclamine, and compound 8 / clomeprop;
compound 9 / pyrazosulfuron-ethyl, compound 9 / bensulfuron-methyl, compound 9 / cinosulfuron, compound 9 / imazosulfuron, compound 9 / azimsulfuron, compound 9 / halosulfuron-methyl, compound 9 / cyclosulfamuron, compound 9 / ethoxysulfuron, compound 9 / pyrazolate, compound 9 / pyrazoxyfen, compound 9 / benzofenap, compound 9 / bromobutide, compound 9 / naproanilide, compound 9 / pretilachlor, compound 9 / butachlor, compound 9 / thenylchlor, compound 9 / CNP, compound 9 / chlomethoxynil, compound 9 / bifenox, compound 9 / oxadiazon, compound 9 / oxadiargyl, compound 9 / pentoxazone, compound 9 / cafenstrole, compound 9 / oxaziclomefone, compound 9 / indanofan, compound 9 / pyriminobac-methyl, compound 9 / cyhalofop-butyl, compound 9 / fentrazamide, compound 9 / mefenacet, compound 9 / butenachlor, compound 9 / dithiopyl, compound 9 / benfuresate, compound 9 / pyributicarb, compound 9 / benthiocarb, compound 9 / molinate, compound 9 / butamifos, compound 9 / quinclorac, compound 9 / cinmethylin, compound 9 / simetryn, compound 9 / bensulide, compound 9 / dimethametryn, compound 9 / MCPA, compound 9 / MCPB, compound 9 / etobenzanid, compound 9 / cumyluron, compound 9 / benzobicyclon, compound 9 / pyriftalid, compound 9 /

bispyribac, compound 9 / pyraclonil, compound 9 /anilofos, compound 9 / OK-701, compound 9 / penoxsulam, compound 9 / AVH-301, compound 9 / KUH-021, compound 9 / TH-547, compound 9 / bentazone, compound 9/2, 4-PA, compound 9 / metamifop, compound 9 / flucetosulfuron, compound 9 / HOK-201, compound 9 / mesotrione, compound 9 / propanil, compound 9 / quinoclamine, and compound 9 / clomeprop;
compound 10 / pyrazosulfuron-ethyl, compound 10 / bensulfuron-methyl, compound 10 / cinosulfuron, compound 10 / imazosulfuron, compound 10 / azimsulfuron, compound 10 / halosulfuron-methyl, compound 10 / cyclosulfamuron, compound 10 / ethoxysulfuron, compound 10 / pyrazolate, compound 10 / pyrazoxyfen, compound
10 / benzofenap, compound 10 / bromobutide, compound 10 / naproanilide,
compound 10 / pretilachlor, compound 10 / butachlor, compound 10 / thenylchlor,
compound 10 / CNP, compound 10 / chlomethoxynil, compound 10 / bifenox,
compound 10/ oxadiazon, compound 10 / oxadiargyl, compound 10 / pentoxazone,
compound 10 / cafenstrole, compound 10 / oxaziclomefone, compound 10 /
indanofan, compound 10 / pyriminobac-methyl, compound 10 / cyhalofop-butyl,
compound 10 / fentrazamide, compound 10 / mefenacet, compound 10 / butenachlor,
compound 10 / dithiopyl, compound 10 / benfuresate, compound 10 / pyributicarb,
compound 10 / benthiocarb, compound 10 / molinate, compound 10 / butamifos,
compound 10 / quinclorac, compound 10 / cinmethylin, compound 10 / simetryn,
compound 10 / bensulide, compound 10 / dimethametryn, compound 10 / MCPA,
compound 10 / MCPB, compound 10 / etobenzanid, compound 10 / cumyluron,
compound 10 / benzobicyclon, compound 10 / pyriftalid, compound 10 / bispyribac,
compound 10 / pyraclonil, compound 10 /anilofos, compound 10 / OK-701,
compound 10 / penoxsulam, compound 10 / AVH-301, compound 10 / KUH-021,
compound 10 / TH-547, compound 10 / bentazone, compound 10/2, 4-PA,
compound 10 / metamifop, compound 10 / flucetosulfuron, compound 10 / HOK-201,
compound 10 / mesotrione, compound 10 / propanil, compound 10 / quinoclamine,
and compound 10 / clomeprop;
compound 11 / pyrazosulfuron-ethyl, compound 11 / bensulfuron-methyl, compound
11 / cinosulfuron, compound 11/ imazosulfuron, compound 11 / azimsulfuron,
compound 11/ halosulfuron-methyl, compound 11 / cyclosulfamuron, compound 11 /
ethoxysulfuron, compound 11 / pyrazolate, compound 11 / pyrazoxyfen, compound
11 / benzofenap, compound 11 / bromobutide, compound 11 / naproanilide,

compound 11 / pretilachlor, compound 11/ butachlor, compound 11/ thenylchlor, compound 11 / CNP, compound 11 / chlomethoxynil, compound 11 / bifenox, compound 11/ oxadiazon, compound 11/ oxadiargyl, compound 11 / pentoxazone, compound 11 / cafenstrole, compound 11 / oxaziclomefone, compound 11 / indanofan, compound 11 / pyriminobac-methyl, compound 11 / cyhalofop-butyl, compound 11/ fentrazamide, compound 11 / mefenacet, compound 11 / butenachlor, compound 11 / dithiopyl, compound 11 / benfuresate, compound 11 / pyributicarb, compound 11 / benthiocarb, compound 11 / molinate, compound 11 / butamifos, compound 11 / quinclorac, compound 11 / cinmethylin, compound 11 / simetryn, compound 11/ bensulide, compound 11 / dimethametryn, compound 11 / MCPA, compound 11 / MCPB, compound 11 / etobenzanid, compound 11/ cumyluron, compound 11 / benzobicyclon, compound 11 / pyriftalid, compound 11 / bispyribac, compound 11/ pyraclonil, compound 11 /anilofos, compound 11 / OK-701, compound 11 / penoxsulam, compound 11 / AVH-301, compound 11 / KUH-021, compound 11/ TH-547, compound 11 / bentazone, compound 11/2, 4-PA, compound 11 / metamifop, compound 11 / flucetosulfuron, compound 11 / HOK-201, compound 11 / mesotrione, compound 11 / propanil, compound 11 / quinoclamine, and compound 11 / clomeprop;
compound 12 / pyrazosulfuron-ethyl, compound 12 / bensulfuron-methyl, compound 12 / cinosulfuron, compound 12 / imazosulfuron, compound 12 / azimsulfuron, compound 12 / halosulfuron-methyl, compound 12 / cyclosulfamuron, compound 12 / ethoxysulfuron, compound 12 / pyrazolate, compound 12 / pyrazoxyfen, compound 12 / benzofenap, compound 12 / bromobutide, compound 12 / naproanilide, compound 12 / pretilachlor, compound 12 / butachlor, compound 12 / thenylchlor, compound 12 / CNP, compound 12 / chlomethoxynil, compound 12 / bifenox, compound 12 / oxadiazon, compound 12 / oxadiargyl, compound 12 / pentoxazone, compound 12 / cafenstrole, compound 12 / oxaziclomefone, compound 12 / indanofan, compound 12 / pyriminobac-methyl, compound 12 / cyhalofop-butyl, compound 12 / fentrazamide, compound 12 / mefenacet, compound 12 / butenachlor, compound 12 / dithiopyl, compound 12 / benfuresate, compound 12 / pyributicarb, compound 12 / benthiocarb, compound 12 / molinate, compound 12 / butamifos, compound 12 / quinclorac, compound 12 / cinmethylin, compound 12 / simetryn, compound 12 / bensulide, compound 12 / dimethametryn, compound 12 / MCPA, compound 12 / MCPB, compound 12 / etobenzanid, compound 12 / cumyluron,

compound 12 / benzobicyclon, compound 12 / pyriftalid, compound 12 / bispyribac, compound 12 / pyraclonil, compound 12 /anilofos, compound 12 / OK-701, compound 12 / penoxsulam, compound 12 / AVH-301, compound 12 / KUH-021, compound 12 / TH-547, compound 12 / bentazone, compound 12/2, 4-PA, compound 12 / metamifop, compound 12 / flucetosulfuron, compound 12 / HOK-201, compound 12 / mesotrione, compound 12 / propanil, compound 12 / quinoclamine, and compound 12 / clomeprop;
compound 13 / pyrazosulfuron-ethyl, compound 13 / bensulfuron-methyl, compound 13 / cinosulfuron, compound 13 / imazosulfuron, compound 13 / azimsulfuron, compound 13 / halosulfuron-methyl, compound 13 / cyclosulfamuron, compound 13 / ethoxysulfuron, compound 13 / pyrazolate, compound 13 / pyrazoxyfen, compound
13 / benzofenap, compound 13 / bromobutide, compound 13 / naproanilide,
compound 13 / pretilachlor, compound 13 / butachlor, compound 13 / thenylchlor,
compound 13 / CNP, compound 13 / chlomethoxynil, compound 13 / bifenox,
compound 13 / oxadiazon, compound 13 / oxadiargyl, compound 13 / pentoxazone,
compound 13 / cafenstrole, compound 13 / oxaziclomefone, compound 13 /
indanofan, compound 13 / pyriminobac-methyl, compound 13 / cyhalofop-butyl,
compound 13 / fentrazamide, compound 13 / mefenacet, compound 13 / butenachlor,
compound 13 / dithiopyl, compound 13 / benfuresate, compound 13 / pyributicarb,
compound 13 / benthiocarb, compound 13 / molinate, compound 13 / butamifos,
compound 13 / quinclorac, compound 13 / cinmethylin, compound 13 / simetryn,
compound 13/ bensulide, compound 13 / dimethametryn, compound 13 / MCPA,
compound 13 / MCPB, compound 13 / etobenzanid, compound 13 / cumyluron,
compound 13 / benzobicyclon, compound 13 / pyriftalid, compound 13 / bispyribac,
compound 13 / pyraclonil, compound 13 /anilofos, compound 13 / OK-701,
compound 13 / penoxsulam, compound 13 / AVH-301, compound 13 / KUH-021,
compound 13 / TH-547, compound 13 / bentazone, compound 13/2, 4-PA,
compound 13 / metamifop, compound 13 / flucetosulfuron, compound 13 / HOK-201,
compound 13 / mesotrione, compound 13 / propanil, compound 13 / quinoclamine,
and compound 13 / clomeprop;
compound 14 / pyrazosulfuron-ethyl, compound 14 / bensulfuron-methyl, compound
14 / cinosulfuron, compound 14 / imazosulfuron, compound 14 / azimsulfuron,
compound 14 / halosulfuron-methyl, compound 14 / cyclosulfamuron, compound 14 /
ethoxysulfuron, compound 14 / pyrazolate, compound 14 / pyrazoxyfen, compound

14 / benzofenap, compound 14 / bromobutide, compound 14 / naproanilide,
compound 14 / pretilachlor, compound 14 / butachlor, compound 14 / thenylchlor,
compound 14 / CNP, compound 14 / chlomethoxynil, compound 14 / bifenox,
compound 14 / oxadiazon, compound 14 / oxadiargyl, compound 14 / pentoxazone,
compound 14 / cafenstrole, compound 14 / oxaziclomefone, compound 14 /
indanofan, compound 14 / pyriminobac-methyl, compound 14 / cyhalofop-butyl,
compound 14 / fentrazamide, compound 14 / mefenacet, compound 14 / butenachlor,
compound 14 / dithiopyl, compound 14 / benfuresate, compound 14 / pyributicarb,
compound 14 / benthiocarb, compound 14 / molinate, compound 14 / butamifos,
compound 14 / quinclorac, compound 14 / cinmethylin, compound 14 / simetryn,
compound 14 / bensulide, compound 14 / dimethametryn, compound 14 / MCPA,
compound 14 / MCPB, compound 14 / etobenzanid, compound 14 / cumyluron,
compound 14 / benzobicyclon, compound 14 / pyriftalid, compound 14 / bispyribac,
compound 14 / pyraclonil, compound 14 /anilofos, compound 14 / OK-701,
compound 14 / penoxsulam, compound 14 / AVH-301, compound 14 / KUH-021,
compound 14 / TH-547, compound 14 / bentazone, compound 14/2,4-PA,
compound 14 / metamifop, compound 14 / flucetosulfuron, compound 14 / HOK-201,
compound 14 / mesotrione, compound 14 / propanil, compound 14 / quinoclamine,
and compound 14 / clomeprop;
compound 15/ pyrazosulfuron-ethyl, compound 15 / bensulfuron-methyl, compound
15 / cinosulfuron, compound 15/ imazosulfuron, compound 15 / azimsulfuron,
compound 15 / halosulfuron-methyl, compound 15 / cyclosulfamuron, compound 15 /
ethoxysulfuron, compound 15 / pyrazolate, compound 15 / pyrazoxyfen, compound
15 / benzofenap, compound 15 / bromobutide, compound 15/ naproanilide, compound 15 / pretilachlor, compound 15 / butachlor, compound 15 / thenylchlor, compound 15 / CNP, compound 15 / chlomethoxynil, compound 15 / bifenox, compound 15 / oxadiazon, compound 15 / oxadiargyl, compound 15 / pentoxazone, compound 15 / cafenstrole, compound 15 / oxaziclomefone, compound 15 / indanofan, compound 15 / pyriminobac-methyl, compound 15/ cyhalofop-butyl, compound 15 / fentrazamide, compound 15 / mefenacet, compound 15 / butenachlor, compound 15 / dithiopyl, compound 15 / benfuresate, compound 15 / pyributicarb, compound 15 / benthiocarb, compound 15 / molinate, compound 15 / butamifos, compound 15/ quinclorac, compound 15 / cinmethylin, compound 15 / simetryn, compound 15 / bensulide, compound 15 / dimethametryn, compound 15 / MCPA,

compound 15 / MCPB, compound 15 / etobenzanid, compound 15 / cumyluron, compound 15/ benzobicyclon, compound 15 / pyriftalid, compound 15 / bispyribac, compound 15 / pyraclonil, compound 15 /anilofos, compound 15 / OK-701, compound 15 / penoxsulam, compound 15 / AVH-301, compound 15 / KUH-021, compound 15 / TH-547, compound 15 / bentazone, compound 15/2, 4-PA, compound 15 / metamifop, compound 15 / flucetosulfuron, compound 15 / HOK-201, compound 15 / mesotrione, compound 15 / propanil, compound 15/ quinoclamine, and compound 15 / clomeprop;
compound 16 / pyrazosulfuron-ethyl, compound 16 / bensulfuron-methyl, compound 16 / cinosulfuron, compound 16 / imazosulfuron, compound 16 / azimsulfuron, compound 16 / halosulfuron-methyl, compound 16 / cyclosulfamuron, compound 16 / ethoxysulfuron, compound 16 / pyrazolate, compound 16 / pyrazoxyfen, compound
16 / benzofenap, compound 16 / bromobutide, compound 16 / naproanilide,
compound 16 / pretilachlor, compound 16 / butachlor, compound 16 / thenylchlor,
compound 16 / CNP, compound 16 / chlomethoxynil, compound 16 / bifenox,
compound 16 / oxadiazon, compound 16 / oxadiargyl, compound 16 / pentoxazone,
compound 16 / cafenstrole, compound 16 / oxaziclomefone, compound 16 /
indanofan, compound 16 / pyriminobac-methyl, compound 16 / cyhalofop-butyl,
compound 16 / fentrazamide, compound 16 / mefenacet, compound 16 / butenachlor,
compound 16 / dithiopyl, compound 16 / benfuresate, compound 16 / pyributicarb,
compound 16 / benthiocarb, compound 16 / molinate, compound 16 / butamifos,
compound 16 / quinclorac, compound 16 / cinmethylin, compound 16 / simetryn,
compound 16 / bensulide, compound 16 / dimethametryn, compound 16 / MCPA,
compound 16 / MCPB, compound 16 / etobenzanid, compound 16 / cumyluron,
compound 16 / benzobicyclon, compound 16 / pyriftalid, compound 16 / bispyribac,
compound 16 / pyraclonil, compound 16 /anilofos, compound 16 / OK-701,
compound 16 / penoxsulam, compound 16 / AVH-301, compound 16 / KUH-021,
compound 16 / TH-547, compound 16 / bentazone, compound 16/2, 4-PA,
compound 16 / metamifop, compound 16 / flucetosulfuron, compound 16 / HOK-201,
compound 16 / mesotrione, compound 16 / propanil, compound 16 / quinoclamine,
and compound 16 / clomeprop;
compound 17 / pyrazosulfuron-ethyl, compound 17 / bensulfuron-methyl, compound
17 / cinosulfuron, compound 17/ imazosulfuron, compound 17 / azimsulfuron,
compound 17 / halosulfuron-methyl, compound 17 / cyclosulfamuron, compound 17 /

ethoxysulfuron, compound 17/ pyrazolate, compound 17 / pyrazoxyfen, compound 17/ benzofenap, compound 17 / bromobutide, compound 17/ naproanilide, compound 17/ pretilachlor, compound 17 / butachlor, compound 17 / thenylchlor, compound 17 / CNP, compound 17 / chlomethoxynil, compound 17 / bifenox, compound 17 / oxadiazon, compound 17 / oxadiargyl, compound 17 / pentoxazone, compound 17 / cafenstrole, compound 17 / oxaziclomefone, compound 17 / indanofan, compound 17 / pyriminobac-methyl, compound 17 / cyhalofop-butyl, compound 17 / fentrazamide, compound 17 / mefenacet, compound 17 / butenachlor, compound 17/ dithiopyl, compound 17 / benfuresate, compound 17 / pyributicarb, compound 17 / benthiocarb, compound 17 / molinate, compound 17 / butamifos, compound 17 / quinclorac, compound 17 / cinmethylin, compound 17 / simetryn, compound 17 / bensulide, compound 17 / dimethametryn, compound 17 / MCPA, compound 17 / MCPB, compound 17 / etobenzanid, compound 17 / cumyluron, compound 17 / benzobicyclon, compound 17/ pyriftalid, compound 17 / bispyribac, compound 17 / pyraclonil, compound 17 /anilofos, compound 17 / OK-701, compound 17 / penoxsulam, compound 17 / AVH-301, compound 17 / KUH-021, compound 17 / TH-547, compound 17 / bentazone, compound 17/2, 4-PA, compound 17 / metamifop, compound 17 / flucetosulfuron, compound 17 / HOK-201, compound 17/ mesotrione, compound 17 / propanil, compound 17/ quinoclamine, and compound 17 / clomeprop;
compound 18 / pyrazosulfuron-ethyl, compound 18 / bensulfuron-methyl, compound 18 / cinosulfuron, compound 18 / imazosulfuron, compound 18 / azimsulfuron, compound 18 / halosulfuron-methyl, compound 18/ cyclosulfamuron, compound 18 / ethoxysulfuron, compound 18/ pyrazolate, compound 18/ pyrazoxyfen, compound 18 / benzofenap, compound 18 / bromobutide, compound 18 / naproanilide, compound 18 / pretilachlor, compound 18 / butachlor, compound 18 / thenylchlor, compound 18 / CNP, compound 18 / chlomethoxynil, compound 18 / bifenox, compound 18 / oxadiazon, compound 18/ oxadiargyl, compound 18 / pentoxazone, compound 18 / cafenstrole, compound 18 / oxaziclomefone, compound 18/ indanofan, compound 18 / pyriminobac-methyl, compound 18 / cyhalofop-butyl, compound 18 / fentrazamide, compound 18 / mefenacet, compound 18 / butenachlor, compound 18 / dithiopyl, compound 18 / benfuresate, compound 18 / pyributicarb, compound 18 / benthiocarb, compound 18 / molinate, compound 18 / butamifos, compound 18 / quinclorac, compound 18 / cinmethylin, compound 18 / simetryn,

compound 18/ bensulide, compound 18 / dimethametryn, compound 18 / MCPA, compound 18 / MCPB, compound 18 / etobenzanid, compound 18 / cumyluron, compound 18 / benzobicyclon, compound 18 / pyriftalid, compound 18/ bispyribac, compound 18 / pyraclonil, compound 18 /anilofos, compound 18 / OK-701, compound 18 /penoxsulam, compound 18 / AVH-301, compound 18 /KUH-021, compound 18 / TH-547, compound 18 / bentazone, compound 18/2, 4-PA, compound 18 / metamifop, compound 18 / flucetosulfuron, compound 18 / HOK-201, compound 18/ mesotrione, compound 18/ propanil, compound 18 / quinoclamine, and compound 18/ clomeprop;
compound 19/ pyrazosulfuron-ethyl, compound 19/ bensulfuron-mefhyl, compound 19 / cinosulfuron, compound 19 / imazosulfuron, compound 19 / azimsulfuron, compound 19 / halosulfuron-methyl, compound 19 / cyclosulfamuron, compound 19 / ethoxysulfuron, compound 19 /pyrazolate, compound 19 / pyrazoxyfen, compound
19 / benzofenap, compound 19 / bromobutide, compound 19 / naproanilide,
compound 19 / pretilachlor, compound 19 / butachlor, compound 19/ thenylchlor,
compound 19 / CNP, compound 19 / chlomethoxyrtil, compound 19 / bifenox,
compound 19 / oxadiazon, compound 19 / oxadiargyl, compound 19 / pentoxazone,
compound 19 / cafenstrole, compound 19 / oxaziclomefone, compound 19 /
indanofan, compound 19 / pyriminobac-methyl, compound 19 / cyhalofop-butyl,
compound 19 / fentrazamide, compound 19 / mefenacet, compound 19 / butenachlor,
compound 19/ dithiopyl, compound 19 / benfuresate, compound 19 / pyributicarb,
compound 19 / benthiocarb, compound 19 / molinate, compound 19 / butamifos,
compound 19 / quinclorac, compound 19 / cinmethylin, compound 19 / simetryn,
compound 19 / bensulide, compound 19 / dimethametryn, compound 19 / MCPA,
compound 19 / MCPB, compound 19 / etobenzanid, compound 19 / cumyluron,
compound 19 / benzobicyclon, compound 19 / pyriftalid, compound 19 / bispyribac,
compound 19 / pyraclonil, compound 19 /anilofos, compound 19 / OK-701,
compound 19 / penoxsulam, compound 19 / AVH-301, compound 19 / KUH-021,
compound 19 / TH-547, compound 19 / bentazone, compound 19/2, 4-PA,
compound 19 / metamifop, compound 19 / flucetosulfuron, compound 19 / HOK-201,
compound 19 / mesotrione, compound 19 / propanil, compound 19 / quinoclamine,
and compound 19 / clomeprop;
compound 20 / pyrazosulfuron-ethyl, compound 20 / bensulfuron-mefhyl, compound
20 / cinosulfuron, compound 20 / imazosulfuron, compound 20 / azimsulfuron,

compound 20 / halosulfuron-methyl, compound 20 / cyclosulfamuron, compound 20 / ethoxysulfuron, compound 20 / pyrazolate, compound 20 / pyrazoxyfen, compound
20 / benzofenap, compound 20 / bromobutide, compound 20 / naproanilide,
compound 20 / pretilachlor, compound 20 / butachlor, compound 20 / thenylchlor,
compound 20 / CNP, compound 20 / chlomethoxynil, compound 20 / bifenox,
compound 20 / oxadiazon, compound 20 / oxadiargyl, compound 20 / pentoxazone,
compound 20 / cafenstrole, compound 20 / oxaziclomefone, compound 20 /
indanofan, compound 20 / pyriminobac-methyl, compound 20 / cyhalofop-butyl,
compound 20 / fentrazamide, compound 20 / mefenacet, compound 20 / butenachlor,
compound 20 / dithiopyl, compound 20 / benfuresate, compound 20 / pyributicarb,
compound 20 / benthiocarb, compound 20 / molinate, compound 20 / butamifos,
compound 20 / quinclorac, compound 20 / cinmethylin, compound 20 / simetryn,
compound 20 / bensulide, compound 20 / dimethametryn, compound 20 / MCPA,
compound 20 / MCPB, compound 20 / etobenzanid, compound 20 / cumyluron,
compound 20 / benzobicyclon, compound 20 / pyriftalid, compound 20 / bispyribac,
compound 20 / pyraclonil, compound 20 /anilofos, compound 20 / OK-701,
compound 20 / penoxsulam, compound 20 / AVH-301, compound 20 / KUH-021,
compound 20 / TH-547, compound 20 / bentazone, compound 20 / 2, 4-PA,
compound 20 / metamifop, compound 20 / flucetosulfuron, compound 20 / HOK-201,
compound 20 / mesotrione, compound 20 / propanil, compound 20 / quinoclamine,
and compound 20 / clomeprop;
compound 21 / pyrazosulfuron-ethyl, compound 21 / bensulfuron-methyl, compound
21 / cinosulfuron, compound 21 / imazosulfuron, compound 21 / azimsulfuron,
compound 21 / halosulfuron-methyl, compound 21 / cyclosulfamuron, compound 21 /
ethoxysulfuron, compound 21 / pyrazolate, compound 21 / pyrazoxyfen, compound
21 / benzofenap, compound 21 / bromobutide, compound 21 / naproanilide,
compound 21 / pretilachlor, compound 21 / butachlor, compound 21 / thenylchlor,
compound 21 / CNP, compound 21 / chlomethoxynil, compound 21 / bifenox,
compound 21 / oxadiazon, compound 21 / oxadiargyl, compound 21 / pentoxazone,
compound 21 / cafenstrole, compound 21 / oxaziclomefone, compound 21 /
indanofan, compound 21 / pyriminobac-methyl, compound 21 / cyhalofop-butyl,
compound 21 / fentrazamide, compound 21 / mefenacet, compound 21 / butenachlor,
compound 21 / dithiopyl, compound 21 / benfuresate, compound 21 / pyributicarb,
compound 21 / benthiocarb, compound 21 / molinate, compound 21 / butamifos,

compound 21 / quinclorac, compound 21 / cinmethylin, compound 21 / simetryn, compound 21 / bensulide, compound 21 / dimethametryn, compound 21 / MCPA, compound 21 / MCPB, compound 21 / etobenzanid, compound 21 / cumyluron, compound 21 / benzobicyclon, compound 21 / pyriftalid, compound 21 / bispyribac, compound 21 / pyraclonil, compound 21 /anilofos, compound 21 / OK-701, compound 21 /penoxsulam, compound 21 / AVH-301, compound 21 / KUH-021, compound 21 / TH-547, compound 21 / bentazone, compound 21/2, 4-PA, compound 21 / metamifop, compound 21 / flucetosulfuron, compound 21 / HOK-201, compound 21 / mesotrione, compound 21 / propanil, compound 21 / quinoclamine, and compound 21 / clomeprop.
[0117]
In the present invention, generally 0.001-100 parts by mass, preferably 0.01-30 parts by mass of at least one compound selected from dymron, dimepiperate and esprocarb are applied per part by mass of the compound (A).
An application amount of the compound (A) is generally 1 g to 10 kg/ha, preferably 10 g to 1 kg/ha. An application amount of at least one compound selected from dymron, dimepiperate and esprocarb is generally 1 g to 10 kg/ha, preferably 10 g to 3 kg/ha.
Generally, by mixing with an adequate liquid carrier or solid carrier and optionally by adding additives such as surfactants, penetrants, spreading agents, thickeners, antifreezing agents, binders, anticaking agents, disintegrating agents, antifoaming agents, antiseptic agents and stabilizing agents, the compounds according to the present invention can be applied in practical use to form optional formulation such as soluble concentrate, emulsifiable concentrate, wettable powder, water soluble powder, water dispersible granule, water soluble granule, suspension concentrate, concentrated emulsion, suspoemulsion, microemulsion, dustable powder, granule and gel. In addition, from the viewpoint of laborsaving and safety enhancement, the above-mentioned formulations in any optional forms may be encapsulated into a water-soluble bag. Herbicides of the present invention may also be used by mixing with other herbicides, insecticides, bactericides, plant growth regulators and fertilizers when forming formulation or applying, if necessary.

Examples of solid carriers include natural minerals such as quartz, kaolinite, pyrophilite, celicite, talc, bentonite, acid clay, attapulgite, zeolite and diatomaceous earth; inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate and potassium chloride; synthetic silica, and synthetic silicate.
Examples of liquid carriers include alcohols such as ethylene glycol, propylene glycol and isopropanol; aromatic hydrocarbons such as xylene, an alkylbenzene and an alkylnaphthalene; ethers such as butyl cellosolve; ketones such as cyclohexanone; esters such as y-butyrolactone; acid amides such as N-methylpyrrolidone and N-octylpyrrolidone; vegetable oils such as soybean oil, canola oil, cottonseed oil and castor oil; and water.
These solid and liquid carriers may be used singly or in combination.
Examples of surfactants include nonionic surfactants such as a polyoxyethylene alkylether, a polyoxyethylene alkylarylether, polyoxyethylene styrylphenylether, a polyoxyethylene polyoxypropylene block copolymer, a polyoxyethylene fatty acid ester, a sorbitan fatty acid ester and a polyoxyethylene sorbitan fatty acid ester; anionic surfactants such as an alkylsulfate, an alkylbenzenesulfonate, ligninsulfonate, an alkylsulfosuccinate, naphthalenesulfonate, an alkylnaphthalenesulfonate, a formalin condensate salt of naphthalene sulfonic acid, a formalin condensate salt of alkylnaphthalene sulfonic acid, a polyoxyethylene alkylarylether sulfate and phosphate, polyoxyethylene styrylphenylether sulfate and phosphate, a polycarboxylic acid salt and a polystyrenesulfonate; cationic surfactants such as an alkylamine salt, a quaternary alkylammonium salt; and amphoteric surfactants such as an amino acid type surfactant and a betaine type surfactant.
A content of these surfactants is not particularly restricted. However, a desirable range is generally 0.05-20 parts by mass per 100 parts of the formulations according to the present invention. These surfactants may be used singly or in combination.
At this time, herbicides according to the present invention may be used by mixing with other herbicides, insecticides, bactericides, plant growth regulators and fertilizers. Particularly, by adding one or more herbicides, herbicidal spectrum can be extended and effects according to the present invention can be more stable. [0118]
Composition examples of formulations using compounds according to the present invention are described below, although the composition examples according

to the present invention are not limited thereto. "Parts" means parts by mass in the following composition examples described below.
Wettable powder
Composition according to the present invention 0.1 -80 parts
Solid carrier 5-98.9 parts
Surfactant 1-10 parts
Other components 0-5 parts
Examples of other components include an anticaking agent and a stabilizing agent.
Emulsifiable concentrate
Composition according to the present invention 0.1-30 parts
Liquid carrier 45-95 parts
Surfactant 4.9-15 parts
Other components 0-10 parts
Examples of other components include spreading agents and stabilizing agents.
Suspension concentrate
Composition according to the present invention 0.1-70 parts
Liquid carrier 15-98.89 parts
Surfactant 1-12 parts
Other components 0.01-30 parts
Examples of other components include antifreezing agents and thickeners.
Water dispersible granule
Composition according to the present invention 0.1 -90 parts
Solid carrier 0-98.9 parts
Surfactant 1 -20 parts
Other components 0-10 parts
Examples of other components include binders and stabilizing agents.
Soluble concentrate
Composition according to the present invention 0.01 -70 parts
Liquid carrier 20-99.99 parts
Other components 0-10 parts
Examples of other components include antifreezing agents and spreading agents.

Granule
Composition according to the present invention 0.01-80 parts
Solid carrier 10-99.99 parts
Other components 0-10 parts
Examples of other components include binders and stabilizing agents.
Dustable powder
Composition according to the present invention 0.01-30 parts
Solid carrier 65-99.99 parts
Other components 0-5 parts
Examples of other components include anti-scattering agents and stabilizing agents.
An application amount of active ingredient of the above-mentioned formulations is 0.001-50 kg per hectare, preferably 0.01-10 kg per hectare with diluting the above-mentioned formulations to 1 to 10,000-fold with water or without dilution.
EXAMPLES
[0119]
Formulation Example
Examples of agrichemical formulations in which compounds according to the present invention act as active ingredients are specifically described below, although the formulation examples according to the present invention are not limited thereto. "Parts" means parts by mass in the following composition examples described below.
Composition Example 1 Wettable powder
Compound (A) 10 parts
Dymron 10 parts
Pyrophylite 74 parts
Solpol 5039 4 parts
(a mixture of a nonionic surfactant and an anionic surfactant: manufactured by TOHO
Chemical Industry Co., LTD, Trade name)
Carplex #80D 2 parts
(synthetic hydrated silicic acid: manufactured by Shionogi & Co., Ltd., Trade name)

The above-mentioned components are uniformly mixed and pulverized to produce a wettable powder. [0120]
Composition Example 2 Emulsifiable concentrate
Compound (A) 2 parts
Dymron 3 parts
Xylene 75 parts
N-methylpyrrolidone 15 parts
Solpol 2680 5 parts
(a mixture of a nonionic surfactant and an anionic surfactant: manufactured by TOHO Chemical Industry Co., LTD, Trade name)
The above-mentioned components are uniformly mixed to produce an emulsifiable concentrate. [0121]
Composition Example 3 Suspension concentrate
Compound (A) 15 parts
Dymron 10 parts
Agrizole S-710 10 parts
(a nonionic surfactant: manufactured by Kao Corporation, Trade name)
LunoxlOOOC 0.5 parts
(an anionic surfactant: manufactured by TOHO Chemical Industry Co., LTD, Trade name)
Xanthan gum 0.2 parts
Water 64.3 parts
The above-mentioned components are uniformly mixed and then wet-pulverized to produce a suspension concentrate. [0122]
Composition Example 4 Water dispersible granule
Compound (A) 25 parts
Dymron 50 parts
HITENOLNE-15 5 parts
(an anionic surfactant: manufactured by Dai-ichi Kogyo Seiyaku Cc, Ltd., Trade
name)
VANILLEXN 10 parts

(an anionic surfactant: manufactured by Nippon Paper Chemicals Co., Ltd., Tradename)
Carplex#80D 10 parts
(synthetic hydrated silicic acid: manufactured by Shionogi & Co., Ltd., Trade name)
The above-mentioned components are uniformly mixed and pulverized, and then a small amount of water is added to the mixture. The resultant mixture is mixed with stirring, granulated by an extrusion granulator, and dried to produce a water dispersible granule. [0123]
Composition Example 5 Granule
Compound (A) 3 parts
Dymron 2 parts
Bentonite 50 parts
Talc 45 parts
The above-mentioned components are uniformly mixed and pulverized, and then a small amount of water is added to the mixture. The resultant mixture is mixed with stirring, granulated by an extrusion granulator, and dried to produce a granule. [0124]
Composition Example 6 Dustable powder
Compound (A) 1 part
Dymron 2 parts
Carplex #80D 0.5 parts
(synthetic hydrated silicic acid: manufactured by Shionogi & Co., Ltd., Trade name)
Kaolinite 95 parts
diisopropyl phosphate 1.5 parts
The above-mentioned components are uniformly mixed and pulverized to produce a dustable powder. [0125]
Composition Example 7 Wettable powder
Compound (A) 10 parts
Dimepiperate 10 parts
Pyrophylite 74 parts
Solpol 5039 4 parts

(a mixture of a nonionic surfactant and an anionic surfactant: manufactured by TOHO
Chemical Industry Co., LTD, Trade name)
Carplex #80D 2 parts
(synthetic hydrated silicic acid: manufactured by Shionogi & Co., Ltd., Trade name)
The above-mentioned components are uniformly mixed and pulverized to produce a wettable powder. [0126]
Composition Example 8 Emulsifiable concentrate
Compound (A) 2 parts
Dimepiperate 3 parts
Xylene 75 parts
N-methylpyrrolidone 15 parts
Solpol 2680 5 parts
(a mixture of a nonionic surfactant and an anionic surfactant: manufactured by TOHO Chemical Industry Co., LTD, Trade name)
The above-mentioned components are uniformly mixed to produce an emulsifiable concentrate. [0127]
Composition Example 9 Suspension concentrate
Compound (A) 15 parts
Dimepiperate 10 parts
Agrizole S-710 10 parts
(a nonionic surfactant: manufactured by Kao Corporation, Trade name)
LunoxlOOOC 0.5 parts
(an anionic surfactant: manufactured by TOHO Chemical Industry Co., LTD, Trade name)
Xanthan gum 0.2 parts
Water 64.3 parts
The above-mentioned components are uniformly mixed and then wet-pulverized to produce a suspension concentrate. [0128]
Composition Example 10 Water dispersible granule
Compound (A) 25 parts
Dimepiperate 50 parts

HITENOLNE-15 5 parts
(an anionic surfactant: manufactured by Dai-ichi Kogyo Seiyaku Cc, Ltd., Trade name)
VANILLEXN 10 parts
(an anionic surfactant: manufactured by Nippon Paper Chemicals Co., Ltd., Tradename)
Carplex #80D 40 parts
(synthetic hydrated silicic acid: manufactured by Shionogi & Co., Ltd., Trade name)
The above-mentioned components are uniformly mixed and pulverized, and then a small amount of water is added to the mixture. The resultant mixture is mixed with stirring, granulated by an extrusion granulator, and dried to produce a water dispersible granule. [0129]
Composition Example 11 Granule
Compound (A) 3 parts
Dimepiperate 2 parts
Bentonite 50 parts
Talc 45 parts
The above-mentioned components are uniformly mixed and pulverized, and then a small amount of water is added to the mixture. The resultant mixture is mixed with stirring, granulated by an extrusion granulator, and dried to produce a granule. [0130]
Composition Example 12 Dustable powder
Compound (A) 1 part
Dimepiperate 2 parts
Carplex #80D 0.5 parts
(synthetic hydrated silicic acid: manufactured by Shionogi & Co., Ltd., Trade name)
Kaolinite 95 parts
diisopropyl phosphate 1.5 parts
The above-mentioned components are uniformly mixed and pulverized to produce a dustable powder. [0131]
Composition Example 13 Wettable powder
Compound (A) 10 parts

Esprocarb 10 parts
Pyrophylite 74 parts
Solpol 5039 4 parts
(a mixture of a nonionic surfactant and an anionic surfactant: manufactured by TOHO
Chemical Industry Co., LTD, Trade name)
Carplex #80D 2 parts
(synthetic hydrated silicic acid: manufactured by Shionogi & Co., Ltd., Trade name)
The above-mentioned components are uniformly mixed and pulverized to produce a wettable powder. [0132]
Composition Example 14 Emulsifiable concentrate
Compound (A) 2 parts
Esprocarb 3 parts
Xylene 75 parts
N-methylpyrrolidone 15 parts
Solpol 2680 5 parts
(a mixture of a nonionic surfactant and an anionic surfactant: manufactured by TOHO Chemical Industry Co., LTD, Trade name)
The above-mentioned components are uniformly mixed to produce an emulsifiable concentrate. [0133]
Composition Example 15 Suspension concentrate
Compound (A) 15 parts
Esprocarb 10 parts
AgrizoleS-710 10 parts
(a nonionic surfactant: manufactured by Kao Corporation, Trade name)
LunoxlOOOC 0.5 parts
(an anionic surfactant: manufactured by TOHO Chemical Industry Co., LTD, Trade name)
Xanthan gum 0.2 parts
Water 64.3 parts
The above-mentioned components are uniformly mixed and then wet-pulverized to produce a suspension concentrate. [0134]

Composition Example 16 Water dispersible granule
Compound (A) 25 parts
Esprocarb 50 parts
HITENOLNE-15 5 parts
(an anionic surfactant: manufactured by Dai-ichi Kogyo Seiyaku Cc, Ltd., Trade name)
VANILLEXN 10 parts
(an anionic surfactant: manufactured by Nippon Paper Chemicals Co., Ltd., Tradename)
Carplex #80D 40 parts
(synthetic hydrated silicic acid: manufactured by Shionogi & Co., Ltd., Trade name)
The above-mentioned components are uniformly mixed and pulverized, and then a small amount of water is added to the mixture. The resultant mixture is mixed with stirring, granulated by an extrusion granulator, and dried to produce a water dispersible granule. [0135]
Composition Example 17 Granule
Compound (A) 3 parts
Esprocarb 2 parts
Bentonite 50 parts
Talc 45 parts
The above-mentioned components are uniformly mixed and pulverized, and then a small amount of water is added to the mixture. The resultant mixture is mixed with stirring, granulated by an extrusion granulator, and dried to produce a granule. [0136]
Composition Example 18 Dustable powder
Compound (A) 1 part
Esprocarb 2 parts
Carplex #80D 0.5 parts
(synthetic hydrated silicic acid: manufactured by Shionogi & Co., Ltd., Trade name)
Kaolinite 95 parts
diisopropyl phosphate 1.5 parts
The above-mentioned components are uniformly mixed and pulverized to produce a dustable powder.

[0137]
Usefulness of the compositions according to the present invention as a herbicide will be specifically described based on results from the following test examples.
Effects of reducing crop injury and weeding in each test example were investigated according to the following criteria. Criteria
5 Herbicidal rate 90% or more (almost complete weeding) 4 Herbicidal rate 70% or more and less than 90% 3 Herbicidal rate 40% or more and less than 70% 2 Herbicidal rate 20% or more and less than 40% 1 Herbicidal rate 5% or more and less than 20% 0 Herbicidal rate 5% or less (almost no effect)
Test Example 1 Crop injury test in a water leakage condition
After alluvial soil was placed in a 1/10,000-are plastic pot having a hole in the bottom, water was poured into the soil and mixed to prepare a submerged condition of 4-centimeter water depth. Rice seedlings at the 2.5th leaf stage were transplanted to the pot, and 9 days after the transplantation, a suspension of a testing agent, prepared by using a wettable powder formulated according to the composition examples, having a predetermined concentration was applied dropwise. Water leakage operation was performed by placing the pot on a plastic vat and discharging water in the plastic vat to decrease the water level by 2 centimeters/day for 3 successive days after the formulation treatment. Twenty-eight days after the formulation treatment, crop injury to paddy was investigated according to the above-mentioned criteria. As a result, the application of every combination of the compound (A) and dymron, the compound (A) and dimepiperate, and the compound (A) and esprocarb showed a greater reduction effect of crop injury to paddy than the application of only the compound (A). [0138]
Test Example 2 Crop injury test in a stocked seedling condition and a water leakage condition
A stocked seedling condition was defined that after alluvial soil was placed in a 1/10,000-are plastic pot, water was poured into the soil and mixed to prepare a

submerged condition of 4-centimeter water depth. Then, in this pot, rice seedlings at the 2.5th leaf stage were fixed on the paddy surface with their roots exposed. Meanwhile, for a water leakage condition, seedlings at the 2.5th leaf stage were transplanted in a similar manner to described in Test Example 1. In both conditions, 6 days after the transplantation, a suspension of a testing agent, prepared by using a wettable powder formulated according to the composition examples, having a predetermined concentration was applied dropwise. Twenty-four days after the formulation treatment, crop injury to paddy was investigated according to the above-mentioned criteria. As a result, the application of every combination of the compound (A) and dymron, the compound (A) and dimepiperate, and the compound (A) and esprocarb showed a greater reduction effect of crop injury to paddy than the application of only the compound (A). [0139]
Test Example 3 Herbicidal effect test in a submerged condition by treatment before weed-generation
After alluvial soil was placed in a 1/10,000-are plastic pot, water was poured into the soil and the resultant mixture was mixed to prepare a submerged condition of 4-centimeter water depth. Seeds of Echinochloa crus-galli, Scirpus juncoides Roxb. var. ohwianus T. Koyama, Monochoria vaginalis, Rotala indica and Lindernia procumbens were sown, and 2 days after the sowing, a suspension of a testing agent, prepared by using a wettable powder formulated according to the composition examples, having a predetermined concentration was applied dropwise. Thirty-eight days after the formulation treatment, herbicidal effect to each weed type was investigated according to the above-mentioned criteria. As a result, the application of every combination of the compound (A) and dymron, the compound (A) and dimepiperate, and the compound (A) and esprocarb showed no decrease in herbicidal effect compared with the application of only the compound (A). [0140]
Test Example 4 Herbicidal effect test in a submerged condition by treatment after weed-generation
After alluvial soil was placed in a 1/10,000-are plastic pot, seeds of Scirpus juncoides Roxb. var. ohwianus T. Koyama were sown and covered with paddy surface soil, and then the seeds of Echinochloa crus-galli, Monochoria vaginalis, Rotala indica and Lindernia procumbens were sown, and water was poured into the soil and

mixed to prepare a submerged depth condition of 4-centimeter water depth. Fourteen days after the sowing, a suspension of a testing agent, prepared by using a wettable powder formulated according to the composition examples, having a predetermined concentration was applied dropwise. Thirty-eight days after the formulation treatment, herbicidal effect to each weed type was investigated according to the above-mentioned criteria. As a result, the application of every combination of the compound (A) and dymron, the compound (A) and dimepiperate, and the compound (A) and esprocarb showed no decrease in herbicidal effect compared with the application of only the compound (A). [0141]
Test Example 5 Crop injury test in a condition of rice stocked seedlings After alluvial soil was placed in a 1/10,000-are plastic pot, water was poured into the soil and the resultant mixture was mixed to prepare a submerged condition of 4-centimeter water depth. In this pot, rice seedlings at the 2.5th leaf stage were fixed on a paddy surface with their roots exposed. Sixth days after the transplantation, a suspension of a testing agent, prepared by using a wettable powder formulated according to the composition examples, having a predetermined concentration was applied dropwise. Twenty-four days after the formulation treatment, herbicidal effect to paddy was investigated according to the above-mentioned criteria. Results are listed in the fourth table below. [Table 4] [Fourth Table]
(Table Removed)
[0142]
Test Example 6 Herbicidal effect test in a submerged condition by treatment after Leptochloa chinensis (L.) Nees generation
After alluvial soil was placed in a 1/10,000-are plastic pot, seeds of Leptochloa chinensis (L.) Nees were sown and raised in a greenhouse. After raising the Leptochloa chinensis (L.) Nees for 20 days, water was poured to a submerged depth of 2 centimeters, and a suspension of a testing agent, prepared by using a wettabie powder formulated according to the composition examples, having a predetermined concentration was applied dropwise. Twenty days after the formulation treatment, herbicidal effect to Leptochloa chinensis (L.) Nees was investigated according to the above-mentioned criteria. Results are listed in the fifth table below. [0143]
Test Example 7 Herbicidal effect test in a submerged condition by treatment after Echinochloa crus-galli generation
After alluvial soil was placed in a 1/10,000-are plastic pot, seeds of Echinochloa crus-galli were sown and raised in a greenhouse. After raising the Echinochloa crus-galli for 14 days, water was poured to a submerged depth of 4 centimeters, and a suspension of a testing agent, prepared by using a wettabie powder formulated according to the composition examples, having a predetermined

concentration was applied dropwise on the next day. Twenty-one days after the formulation treatment, herbicidal effect to Echinochloa crus-galli was investigated according to the above-mentioned criteria. Results are listed in the fifth table below. [0144]
Test Example 8 Herbicidal effect test in a submerged condition by treatment before Scirpus juncoides Roxb. var. ohwianus T. Koyama generation
After alluvial soil was placed in a 1/10,000-are plastic pot, water was poured into the soil and the resultant mixture was mixed to prepare a 4-centimeter submerged depth condition. Seeds of Scirpus juncoides Roxb. var. ohwianus T. Koyama (produced in Honjo City, Akita Prefecture) were sown in the pot, and 1 day after the sowing, a suspension of a testing agent, prepared by using a wettable powder formulated according to the composition examples, having a predetermined concentration was applied dropwise. Twenty-one days after the formulation treatment, herbicidal effect to Echinochloa crus-galli was investigated according to the above-mentioned criteria. Results are listed in the fifth table below. [Table 5] [Fifth Table]
(Table Removed)
[0145]
Test Example 9 Herbicidal effect test by foliage treatment
After alluvial soil was placed in a 1/10,000-are plastic pot, water was poured
into the soil and the resultant mixture was mixed to prepare a submerged condition of
4-centimeter water depth. Seeds of Echinochloa crus-galli were sown in the pot, and
a tuber of Cyperus serotinus Rottb was planted and raised in a greenhouse. Fourteen
days after raising the Cyperus serotinus Rottb, water on the paddy surface was
drained. A wettable powder formulated according to the composition examples was
diluted with water to a predetermined amount of active component and the diluted
mixture was uniformly applied to the tuber part of the Cyperus serotinus Rottb with a
small spraying apparatus. Twenty-one days after the formulation treatment,
herbicidal effect to the two plants was investigated according to the above-mentioned
criteria. Results are listed in the sixth table below.
[Table 8]
[Sixth Table]
(Table Removed)
INDUSTRIAL APPLICABILITY
[0146]
The above-mentioned results obviously show that the composions according to the present invention are useful as a herbicide for, for example, paddy fields.

CLAIMS
1. A herbicide composition comprising:
a pyrazole sulfonylurea compound (A) represented by the general formula (1): [Chemical formula 1]

(Formula Removed)

(wherein, R1 represents C1.3 alkyl group, C1.3 haloalkyl group, C1.3 alkoxy-Ci.3 alkyl
group, phenyl group or pyridyl group;
R2 represents hydrogen atom, C1.3 alkyl group, C1.3 haloalkyl group, C1.3 alkoxy group
or halogen atom;
R3, R4, R5, and R6 independently represent hydrogen atom, C1-3 alkyl group or C 1.3
haloalkyl group, where at least one of R3, R4, R3, and R6 represents C1-3 alkyl group or
C1-3 haloalkyl group or R3 and R4 are combined together to represent =CH2;
X and Y independently represent C1-3 alkyl group, C1.3 haloalkyl group, C1.3 alkoxy
group, C1.3 haloalkoxy group, halogen atom or di(Ci-3 alkyl)amino group; and
Z represents nitrogen atom or methine group); and
at least one compound selected from dymron, dimepiperate and esprocarb.
2. A herbicide composition for paddy rice comprising:
the compound (A); and
at least one compound selected from dymron, dimepiperate and esprocarb.
3. A weeding method comprising applying the compound (A) and at least one
compound selected from dymron, dimepiperate and esprocarb either simultaneously
or at an interval.
4. A weeding method for a paddy field comprising applying the compound (A)
and at least one compound selected from dymron, dimepiperate and esprocarb either
simultaneously or at an interval.
5. A herbicide composition comprising:
the compound (A); and
at least one compound selected from a group B consisting of pyrazosulfuron-ethyl (common name), bensulfuron-methyl (common name), cinosulfuron (common name), imazosulfuron (common name), azimsulfuron (common name), halosulfuron-methyl (common name), cyclosulfamuron (common name), ethoxysulfuron (common name), pyrazolate (common name), pyrazoxyfen (common name), benzofenap (common name), bromobutide (common name), naproanilide (common name), pretilachlor (common name), butachlor (common name), thenylchlor (common name), CNP (common name), chlomethoxynil (common name), bifenox (common name), oxadiazon (common name), oxadiargyl (common name), pentoxazone (common name), cafenstrole (common name), oxaziclomefone (common name), indanofan (common name), pyriminobac-methyl (common name), cyhalofop-butyl (common name), fentrazamide (common name), mefenacet (common name), butenachlor (common name), dithiopyl (common name), benfuresate (common name), pyributicarb (common name), benthiocarb (common name), molinate (common name), butamifos (common name), quinclorac (common name), cinmethylin (common name), simetryn (common name), bensulide (common name), dimethametryn (common name), MCPA (common name), MCPB (common name), etobenzanid (common name), cumyluron (common name), benzobicyclon (common name), pyriftalid (common name), bispyribac (common name), pyraclonil (common name), anilofos (common name), OK-701 (test name), penoxsulam (common name), AVH-301 (test name), KUH-021 (test name), TH-547 (test name), Bentazone (common name), 2,4-PA (common name), metamifop (common name), flucetosulfuron (common name), HOK-201 (common name), mesotrione (common name), propanil (common name), quinoclamine (common name) and clomeprop.
6. A herbicide composition for paddy rice comprising:
the compound (A); and
at least one compound selected from the group B.
7. A weeding method comprising applying the compound (A) and at least one compound selected from the group B either simultaneously or at an interval.
8. A weeding method for a paddy field comprising applying the compound (A) and at least one compound selected from the group B either simultaneously or at an interval.