Pyrazole sulfonylurea compound and herbicide

There is provided a novel herbicide. A pyrazole sulfonylurea compound of formula (1):wherein R1 is C1-3alkyl, etc., R2 is hydrogen atom, C1-3alkyl, C1-3haloalkyl, etc., R3, R4, R5 and R6 independently of one another are hydrogen atom, C1-3alkyl, etc., with a proviso that at least one of R3, R4, R5 and R6 is C1-3alkyl or C1-3haloalkyl, X and Y independently of each other are C1-3alkyl, etc., Z is nitrogen atom or methyne, and a salt thereof that is acceptable as an agrochemical; an agrochemical containing at least one of the compound and the salt thereof that is acceptable as an agrochemical as an active component, and a herbicide containing at least one of the compound and the salt thereof that is acceptable as an agrochemical as an active component.

TECHNICAL FIELD

The present invention relates to pyrazole sulfonylurea compounds and agrochemicals containing them as active components, particularly as herbicides.

BACKGROUND ART

It is disclosed in Patent Document 1 that pyrazole sulfonylureas that a dioxadine ring is bonded on the pyrazole ring have herbicidal activity. However, Patent document 1 does not concretely disclose pyrazole sulfonylureas that any substituents are bonded on the dioxadine ring on the pyrazole ring.

DISCLOSURE OF INVENTION

Problem to be Solved by Invention

An object of the present invention is to provide agrochemicals, particularly herbicides, containing pyrazole sulfonylurea compounds as active components and having excellent efficacy.

Means for Solving Problem

The present inventors eagerly investigated for solving the above-mentioned problems, as a result of it, they found that novel pyrazole sulfonylurea compounds have a herbicidal activity and a selective action for crops, and completed the present invention.

That is, the present invention relates to a pyrazole sulfonylurea compound (hereinafter referred to as “compound of the present invention”) of formula (1):

Effect of Invention

The pyrazole sulfonylurea compound of the present invention has an excellent herbicidal effect against weeds and at the same time shows no crop injury on rice and wheat or barley, and thus it is an excellent selective herbicidal compound for paddy rice and wheat or barley.

BEST MODE FOR CARRYING OUT THE INVENTION

The substituents R1, R2, R3, R4, R5, R6, X, Y and Z in the compound of the present invention and the production intermediate of the compound of the present invention are exemplified. In the meantime, symbols have the following meanings: Me is methyl, Et is ethyl, Pr-n is n-propyl, Pr-iso is isopropyl, Ph is phenyl, and Py is pyridyl.

Concrete Examples of Substituent R1

Concrete Examples of Substituent R2

Concrete Examples of Substituents X and Y

Concrete Examples of Substituent Z

Some of the compounds (1) according to the present invention have optical isomers, and all of the optical isomers are included in the present invention.

In the meantime, among the compounds of the present invention, for example, in which R2is Cl have a low crop injury on rice transplanted at a depth of 0 cm, and they tend to have a low crop injury particularly under water leakage condition near to practical scene also on transplanted rice.

The compound (1) of the present invention can be produced according to methods shown in reaction formulae 1 to 3 described below.

Reaction equation 1 shows the production of the compound (1) of the present invention by reacting 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (2) with 2-phenoxycarbonyl aminopyrimidine (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 0.9 to 1.1-fold over (2).

The base used in this reaction includes inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 10-fold, preferably 0 to 2-fold over (2).

This reaction proceeds even without solvent, but a Solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and Includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 120° C.

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

Reaction equation 2 shows the production of the compound (1) of the present invention by reacting 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonylcarbamate (4) with 2-aminopyrimidine (or triazine) (5) in the presence or absence of a base. In this reaction, (5) is generally used in a molar amount of 0.5 to 10-fold, preferably 0.9 to 1.1-fold over (4).

The base used in this reaction includes inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 10-fold, preferably 0 to 2-fold over (4).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 120° C.

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

Reaction equation 3 shows the production of the compound (1) of the present invention by reacting 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonylisocyanate (6) with 2-aminopyrimidine (or triazine) (5) in the presence or absence of a base. In this reaction, (5) is generally used in a molar amount of 0.5 to 10-fold, preferably 0.9 to 1.1-fold over (6).

The base used in this reaction includes Inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 10-fold, preferably 0 to 2-fold over (6).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 120° C.

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

4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (2) used in Reaction formula 1 can be produced according to the methods shown in Reaction formulae 4 to 6.

In addition, 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl carbamate (4) and 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl isocyanate (6) used in Reaction formulae 2 and 3 can be synthesized by using 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (2) as a starting material by reference to the methods disclosed in JP-A-59-219281 (1984) and JP-A-55-13266 (1980).

Reaction equation 4 shows the production of 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (2) by reacting 5-chloro-4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7) with sodium hydrosulfide to obtain 5-mercapto-4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole (8) (step A), then reacting (8) with a chlorinating agent such as chlorine or sodium hypochlorite to obtain 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl chloride (9) (step B), and reacting (9) with ammonia water or ammonium carbonate (step C).

In step A, sodium hydrosulfide is generally used in a molar amount of 1.0 to 10-fold, preferably 2 to 5-fold over (7).

This reaction proceeds even without solvent, but a solvent can be used if necessary.

The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., sulfur-containing polar solvents such as dimethylsulfoxide and sulfolane, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 120° C.

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

In step B, chlorine or sodium hypochlorite is generally used in a molar amount of 1 to 100-fold, preferably 2 to 10-fold over (8).

In this reaction, a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 100° C., preferably −10 to 50° C.

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

In step C, ammonia or ammonium carbonate is generally used in a molar amount of 1.0 to 10-fold, preferably 2 to 5-fold over (9).

This reaction proceeds even without solvent but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., sulfur-containing polar solvents such as dimethylsulfoxide and sulfolane, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

Reaction equation 5 shows the production of 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl chloride (9) by reacting 5-benzylmercapto-4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole (10) with a chlorinating agent such as chlorine or sodium hypochlorite. In this reaction, chlorine or sodium hypochlorite is generally used in a molar amount of 1 to 100-fold, preferably 2 to 1-fold over (10).

In this reaction, a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 100° C., preferably −50 to 50° C.

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

(9) can be derived into 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (2) according to step C of Reaction formula 4.

Reaction equation 6 shows the production of 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonylchloride (9) by subjecting 5-position on the pyrazole ring of 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole (11) to lithiation with lithium n-butyl or lithium diidopropylamide, etc., then reacting with sulfur dioxide to obtain 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonic acid lithium (12) (step D), and reacting (12) with N-chlorosuccinimide (step E).

In reaction 1) of step D, lithium n-butyl or lithium diidopropylamide is generally used in a molar amount of 1 to 100-fold, preferably 1 to 5-fold over (11).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., and mixed solvents thereof.

The reaction temperature is generally −120 to 100° C., preferably −78 to 10° C.

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

In reaction 2) of step D, sulfur dioxide is generally used in a molar amount of 1.0 to 100-fold, preferably 1 to 10-fold over (11).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., and mixed solvents thereof.

The reaction temperature is generally −120 to 100° C., preferably −78 to 10° C.

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

In step E, N-chlorosuccinimide is generally used in a molar amount of 1.0 to 100-fold, preferably 1 to 10-fold over (11).

The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 100° C., preferably −10 to 50° C.

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

(9) can be derived into 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole-sulfonamide (2) according to step C of Reaction formula 4.

5-Chloro-4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7), 5-benzylmercapto-4-(4H,6H-1,4,2-dioxadin-3-yl)pyrazole (10) and 4-(4H,6H-1,4,2-dioxadin-3-yl)pyrazole (11) used in the methods shown in Reaction formulae 4 to 6 can be produced by methods shown in Reaction formulae 7 to 15.

Reaction equation 7 shows the production of 4-(5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7), (10) or (11) by reacting pyrazole-4-hydroxamic acid (13) with an adjacently dihalogenated alkyl (14).

In this reaction, (14) is generally used in a molar amount of 1.0 to 100-fold, preferably 1 to 5-fold over (13).

The base used in this reaction includes Inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 10-fold, preferably 0 to 2-fold over (13).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitrites such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., sulfur-containing polar solvents such as dimethylsulfoxide and sulfolane, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

Reaction equation 8 shows the production of 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) (step F), and reacting (17) with a base (step G).

In the reaction of step F, (16) is generally used in a molar amount of 1 to 100-fold, preferably 2 to 5-fold over (15).

The base used in this reaction includes inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 10-fold, preferably 0 to 2-fold over (15).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

The base used in the reaction of step G includes inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 10-fold, preferably 0 to 2-fold over (17).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

wherein R1, R2, R3, R5, R6, X1and L are as defined above, and R7and R8independently of each other are halogen atom or C1-3alkyl].

In the reaction of step H, (16a) is generally used in a molar amount of 1 to 100-fold, preferably 2 to 5-fold over (15).

The base used in this reaction includes inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The bass is generally used in a molar amount of 0 to 10-fold, preferably 0 to 2-fold over (15).

This reaction proceeds even without solvent, but a solvent can b used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

In the reaction of step I, the halogen or N-halogeno succinimide is generally used in a molar amount of 1 to 100-fold, preferably 1 to 5-fold over (17a).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketone such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., carbonic acid esters such as met acetate or ethyl acetate, etc., alcohols such as methanol, ethanol or ethylene glycol, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

The reducing agents and reducing systems used in the reaction of stop J include a system in which an alkali metal is used, such as metal sodium/liquid ammonia, metal lithium/liquid ammonia and metal sodium/t-butyl alcohol-tetrahydrofuran mixed solvent, etc., a system in which metal zinc is used, such as zinc/acetic acid and zinc/potassium hydroxide/water, etc., a system in which an organic tin hydride is 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, etc., a mixed system in which the above-mentioned organic tin compound is combined with a free radical initiator such as azobisisobutyronitrile, etc., a system in which silanes such as trichlorosilane, triethylsilane and trimethylsilane, etc. are used, a system in which a metal hydrogen complex compound such as aluminum lithium hydride, aluminum sodium hydride, bis(2-methoxyethoxy) aluminum sodium hydride, sodium boron hydride and cyano boron sodium hydride, etc. is used, a system in which a borane derivative such as diborane, trimethylamine-borane and pyridine-borane, etc. is used, and a catalytic reduction system such as hydrogen/palladium-carbon and hydrogen/Raney nickel, etc.

The reducing agent is generally used in a molar amount of 1 to 100-fold, preferably 1 to 5-fold over (7a), (10a) or (11a).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitrites such as acetonitrile and propionitrile, etc., carbonic acid esters such as methyl acetate or ethyl acetate, etc., alcohols such as methanol, ethanol or ethylene glycol, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably −78 to 100° C.

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

Reaction equation 10 shows the production of each 4-(5-alkyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7e), (10e) or (11e) by subjecting 4-(5-haloalkyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7c), (10c) or (11c) to dehydrohalogenation in the presence or absence of a base to obtain each 4-(5-alkylidene-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7d), (10d) or (11d) (step K), reducing (7d), (10d) or (11d) (step L).

The base used in the reaction of step K includes inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 100-fold, preferably 0 to 5-fold over (7c), (10c) or (11c).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

The reducing agents and reducing systems used in the reaction of step L include a system in which an alkali metal is used, such as metal sodium/liquid ammonia, metal lithium/liquid ammonia and metal lithium/ethyl amine, etc., a system in which metal aluminum is used, such as aluminum-mercury/diethylether-water and aluminum-nickel/sodium hydroxide/water, etc., a system in which an aluminum hydride compound such as diisobutyl aluminum hydride, etc. is used, a system in which hydrosilanes such as triethylsilane-trifluoroacetic acid and polymethylhydrosiloxane/palladium-carbon, etc. are used, a system in which a metal hydrogen complex compound such as aluminum lithium hydride, aluminum sodium hydride, bis(2-methoxyethoxy) aluminum sodium hydride, sodium boron hydride and cyano boron sodium hydride, etc. is used, a system in which a borane derivative such as diborane, trimethylamine-borane and pyridine-borane, etc. is used, a system in which a di-imide generated in the reaction system is used, such as hydrazine hydrate/air, hydrazine hydrate/hexacyano iron (III) acid potassium and hydroxyamine-O-sulfonic acid/sodium hydroxide, etc., a heterogeneous catalytic reduction system such as hydrogen/palladium-carbon and hydrogen/Raney nickel, etc., and homogeneous catalytic reduction system such as hydrogen/chlorotris(triphenylphosphine)rhodium (I), hydrogen/hydride carbonyltris(triphenylphosphino)rhodium (I), hydrogen/rhodium (II) acetate and hydrogen/ruthenium (II) acetate, etc.

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., carbonic acid esters such as methyl acetate or ethyl acetate, etc., alcohols such as methanol, ethanol or ethylene glycol, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc. water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably −78 to 100° C.

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

Reaction equation 11 shows the production of 4-(5-alkyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7b), (10b) or (11b) by reacting pyrazole-4-hydroxamic acid ester (17a) or (17b) with an acid.

The acid used in this reaction includes inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, etc., organic acids such as acetic acid, trifluoroacetic acid, methane sulfonic acid, trifluoromethane sulfonic acid or p-toluenesulfonic acid, etc.

The acid is generally used in a molar amount of 0.01 to 100-fold, preferably 0.05 to 10-fold over (17a) or (17a).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and Includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

Reaction equation 12 shows the production of pyrazole-4-hydroxamic acid ester (17a) by reacting pyrazole-4-hydroxamic acid (13) with halogenated allyl (18) in the presence or absence of a base.

In this reaction, (8) is generally used in a molar amount of 1- to 100-fold, preferably 1- to 5-fold over (13).

The base used in this reaction includes inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 100-fold, preferably 0 to 5-fold over (13).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

Reaction equation 13 shows the production of pyrazole-4-hydroxamic acid ester (17b) used in Reaction formula 11 by reacting pyrazole-4-hydroxamic acid (13) with halohydrin (19) or oxyrane (20) in the presence or absence of a base.

In this reaction, (19) or (20) is generally used in a molar amount of 1 to 100 fold, preferably 2 to 5-fold over (13).

The base used in this reaction includes inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 100-fold, preferably 0 to 5-fold over (13).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

Reaction equation 14 shows the production of each 4-(5-haloalkyl (or alkylsulfonyloxyalkyl)-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7c), (10c) or (11c) by reacting pyrazole-4hydroxamic acid (13) with epihalohydrin (21) in the presence or absence of a base to obtain pyrazole-4-hydroxamic acid ester (17c) (step L), treating (17c) with an acid or a base to obtain 4-(5-hydroxyalkyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (7f), (10f) or (11f) (step M), and then subjecting (7f), (10f) or (11f) to halogenation or alkylsulfonylation (step N).

In the reaction of step L, (21) is generally used in a molar amount of 1 to 100-fold, preferably 1 to 5-fold over (13).

The base used in this reaction includes inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 10-fold, preferably 0 to 5-fold over (13).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., others such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

The acid or base used in the reaction of step M includes inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, etc., organic acids such as acetic acid, trifluoroacetic acid, methane sulfonic acid, trifluoromethane sulfonic acid or p-toluenesulfonic acid, etc., inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The acid or bass is generally used in a molar amount of 0 to 100-fold, preferably 0 to 5-fold over (17c).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., carbonic acid esters such as methyl acetate or ethyl acetate, etc., alcohols such as methanol, ethanol or ethylene glycol, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably −78 to 100° C.

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

In the reaction of step N, the halogenation agent or the alkylsulfonylation agent is generally used in a molar amount of 1 to 100-fold, preferably 1 to 5-fold over (7f), (10f) or (11f).

The halogenation agent used in this reaction includes hydrogen halogenic acids such as hydrogen chloride, hydrogen bromide and hydrogen iodide, etc., halogenated phosphorus such as phosphorus trichloride, phosphorus pentachloride, oxyphosphorus chloride and phosphorus tribromide, etc., a system such as triphenyl phosphonate/benzyl chloride and triphenylphosphine/carbon tetrachloride, etc., halogenated sulfonium such as methane sulfonyl chloride and p-toluene sulfonyl chloride, etc., and halogenated thionyl such as thionyl chloride and thionyl bromide, etc.

The alkylsulfonylation agent used in this reaction includes halogenated sulfonium such as methane sulfonyl chloride and p-toluene sulfonyl chloride, etc.

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetone, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., carbonic acid esters such as methyl acetate or ethyl acetate, etc., alcohols such as methanol, ethanol or ethylene glycol, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably −78 to 100° C.

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

Reaction equation 15 shows the production of pyrazole-4-hydroxamic acid (13) used in Reaction formulae 7 and 12 to 14 by reacting pyrazole-4-carboxylic acid chloride (15) with hydroxyamine in the presence or absence of a base.

In this reaction, hydroxyamine is generally used in a molar amount of 1 to 100-fold, preferably 1 to 5-fold over (15).

The base used in this reaction includes inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, etc., organic bases such as pyridine, 4-dimethylamino pyridine, triethyl amine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,4-diazabicyclo[2.2.2]octane, etc., organic lithiums such as n-butyl lithium and sec-butyl lithium, etc., organic lithium amides such as lithium diisopropyl amide and lithium bis(trimethylsilyl)amide, etc., and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, etc. The base is generally used in a molar amount of 0 to 100-fold, preferably 0 to 5-fold over (15).

This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent is not specifically limited so long as it is inactive in this reaction, and includes for example hydrocarbons such as hexane, cyclohexane, benzene and toluene, etc., halogen-containing hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, etc., ethers such as diethyl other, disopropyl ether, dioxane and tetrahydrofuran, etc., ketones such as acetonitrile, methyl ethyl ketone and methylisobutyl ketone, etc., nitriles such as acetonitrile and propionitrile, etc., amides such as N,N-dimethylformamide, N,N-dimethylacetamide and H-methyl-2-pyrrolidone, etc., water, and mixed solvents thereof.

The reaction temperature is generally −90 to 200° C., preferably 0 to 100° C.

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

The aimed products obtained according to the above-mentioned reactions can be isolated and purified by an operation such as filtering, extraction, washing, column chromatography, recrystallization and distillation, etc.

Hereinafter, synthetic examples of the compounds according to the present invention will be concretely described as examples and referential examples but the present invention is not limited thereto.

EXAMPLES

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 of the present invention)

Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1-methylpyrazole-5-sulfonamide (Compound No. 2 of the present invention)

Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-4-(5,5-dimethyl-5H,6H-1,4,2-dioxadin-3-yl)-1-ethylpyrazole-5-sulfonamide (Compound No. 3 of the present invention)

Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-1,3-dimethyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (Compound No. 5 of the present invention)

Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-chloro-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1-methylpyrazole-5-sulfonamide (Compound No. 6 of the present invention)

Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-4-(5,5-dimethyl-5H,6H-1,4,2-dioxadin-3-yl)-1,3-dimethylpyrazole-5-sulfonamide (Compound No. 7 of the present invention)

Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-4-(5-iodomethyl-5-methyl-5H,6H-1,4,2-dioxadin-3-yl)-1,3-dimethylpyrazole-5-sulfonamide (Compound No. 8 of the present invention)

Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-1,3-dimethyl-4-(6-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (Compound No. 9 of the present invention)

In toluene (100 ml), N-methoxycarbonyl-3-chloro-1-methyl-4-(5-methyl-5H,6H-1,4,2-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, and under reduced pressure (700 mmHg), refluxed under heating for 4 hours while methanol as by-product was distilled off. After 15 ml of toluene was distilled off at the same temperature, the mixture was cooled to room temperature with stirring. Precipitated solid was filtered off, washed with toluene and dried to obtain the aimed product (24.1 g). Melting point 177-179° C.

In a solution of 2-amino-4,6-dimethoxypyrimidine (0.46 g, 3.0 mmol) in acetonitrile (3 ml), a solution of 3 chloro-1-methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonylisocyanate (1.0 g, 3.1 mmol) in toluene (5 ml) was added, and stirred at room temperature for 3 hours. Precipitated solid was filtered off, washed with toluene and dried to obtain the aimed product (1.2 g). Melting point 177-179° C.

In a solution of 2-amino-4,6-dimethoxypyrimidine (1.55 g, 10.0 mmol) in acetonitrile (15 ml), pyridine (0.16 g, 2.0 mol) and sodium cyanate (0.72 g, 11 mmol) were added, and with stirring, 3-chloro-1-methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl chloride (3.45 g, 11.0 mmol) was added by portions over 1 hour at 40° C. At 40° C., the mixture was further stirred for 1.5 hour. After cooling to room temperature, water (60 ml) was added, the mixture was adjusted to pH 1 with 35% hydrochloric acid, and precipitated solid was filtered off. The resulting solid was washed with methanol and dried to obtain the aimed product (4.70 g). Melting point 177-179° C.

Synthesis of N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-1-methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonamide (Compound No. 10 of the present invention)

(1) Synthesis of (5-benzylthio-3-chloro-1-methylpyrazol-4-yl)-N-allyloxycarboxylic acid amide

In a solution of (5-benzylthio-3-chloro-1-methylpyrazol-4-yl)-N-allyloxycarboxylic acid amide (2.2 g, 6.5 mmol) in acetonitrile (70 ml), iodine (5.0 g, 20 mmol) was added at 0° C. After stirring at room temperature for 6 hours, water (150 ml) was added, and extracted with ethyl acetate. The resulting ethyl acetate solution was washed with saturated sodium thiosulfate aqueous solution, saturated sodium hydrogen carbonate aqueous solution, saturated sodium chloride aqueous solution and water in that order, dried over anhydrous sodium sulfate and the solvent was distilled off to obtain the desired product (3.0 g). Oily substance. Proton nuclear magnetic resonance chemical shift values δ (ppm) (in CDCl3) 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), 7.21-7.27 (m, 3H).

In a solution of 5-benzylthio-3-chloro-1-methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (1.9 g, 5.6 mmol) in methylene chloride (30 ml), water (30 ml) and 35% hydrochloric acid (2.3 g, 22 mmol) were added, and 8% sodium hypochlorite aqueous solution (20.5 g, 22.0 mmol) was added with vigorously stirring at 5° C., and stirred for 0.5 hour. After excluding excess chlorine by introducing nitrogen, water (50 ml) was added, and extracted with methylene chloride. The resulting methylene chloride solution was concentrated under reduced pressure, and then the residue was dissolved in tetrahydrofuran (8 ml), 28% ammonia water (5 ml) was added at 0° C., and stirred at room temperature for 0.25 hour. Water (20 ml) was added, extracted with diethyl ether, and the diethyl ether phase was discarded. After adjusting to pH 1 by adding 35% hydrochloric acid in the resulting aqueous phase, the phase was extracted with diethyl ether again. The resulting diethyl ether solution was washed with saturated sodium chloride aqueous solution, and then dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain the aimed product (0.64 g). Melting point 120-122° C. Proton nuclear magnetic resonance chemical shift values δ (ppm) (in CDCl3) 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), 6.12 (brs, 2H).

Synthesis of 3-chloro-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1-methylpyrazol-5-sulfonamide

The procedure similar to that of (4) in Referential Example 1 was carried by using 5-benzylthio-3-chloro-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1-methylpyrazole (0.24 g, 0.52 mmol) as a starting material to obtain the aimed product (0.090 g). Solid.

(1) Synthesis of (5-benzylthio-3-chloro-1-methylpyrazol-4-yl)-N-(2-methyl-2-propenyloxy)carboxylic acid amide

The procedure similar to that of (4) in Referential Example 1 was carried by using 5-benzylthio-3-chloro-1-methyl-4-(5,5-dimethyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (1.2 g, 3.4 mmol) as a starting material to obtain the aimed product (0.47 g). Solid.

Synthesis of 3-chloro-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1-methylpyrazole-5-sulfonamide

The procedure similar to that of (4) in Referential Example 1 was carried by using 5-benzylthio-3-chloro-4-(5-iodomethyl-5-methyl-5H,6H-1,4,2-dioxadin-3-yl)-1-methylpyrazole (0.50 g, 1.0 mmol) as a starting material to obtain the aimed product (0.21 g). Solid.

(1) Synthesis of (5-benzylthio-1,3-dimethylpyrazol-4-yl)-N-allyloxy carboxylic acid amide

The procedure similar to that of (3) in Referential Example 1 was carried by using 5-benzylthio-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1,3-dimethylpyrazole (0.71 g, 1.6 mmol) as a starting material to obtain the aimed product (0.19 g). Oily substance.

Synthesis of 4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1,3-dimethylpyrazol-5-sulfonamide

The procedure similar to that of (4) in Referential Example 1 was carried by using 5-benzylthio-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1,3-dimethylpyrazole (0.70 g, 1.6 mmol) as a starting material to obtain the aimed product (0.53 g). Solid.

(1) Synthesis of (5-benzylthio-1,3-dimethylpyrazol-4-yl)-N-(2-methyl-2-propenyloxy) carboxylic acid amide

The procedure similar to that of (4) in Referential Example 1 was carried by using 5-benzylthio-1,3-dimethyl-4-(5,5-dimethyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (0.34 g, 1.0 mmol) as a starting material to obtain the aimed product (0.13 g). Solid.

Synthesis of 4-(5-iodomethyl-5-methyl-5H,6H-1,4,2-dioxadin-3-yl)-1,3-dimethylpyrazole-5-sulfonamide

The procedure similar to that of (4) in Referential Example 1 was carried by using 5-benzylthio-4-(5-iodomethyl-5-methyl-5H,6H-1,4,2-dioxadin-3-yl)-1,3-dimethylpyrazole (0.20 g, 0.44 mmol) as a starting material to obtain the aimed product (0.080 g). Solid.

(2) Synthesis of (1,3-dimethyl-5-benzylthiopyrazol-4-yl)-N-(2-hydroxyisopropoxy)carboxylic acid amide

The procedure similar to that of (4) in Referential Example 1 was carried by using 5-benzylthio-1,3-dimethyl-4-(6-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (0.32 g, 1.0 mmol) as a starting material to obtain the aimed product (0.14 g). Solid.

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

In a solution of hydroxyamine hydrochloride (106.9 g, 1.538 mol) in water (200 ml), a solution of 85% potassium hydroxide (101.5 g, 1.538 mol) in water (200 ml) was added at 5 to 15° C., and stirred at room temperature for 5 minutes. Then, a solution of 3,5-dichloro-1-methylpyrazole-4-carboxylic acid chloride (100.0 g, 0.5128 mol) in tetrahydrofuran (170 ml) was added dropwise at 3 to 8° C. over 2 hours. After stirring at 5° C. for 0.5 hour, the mixture was adjusted to pH 3-4 by adding 35% hydrochloric acid. Precipitated solid was filtered off, washed with water, and dried to obtain the aimed product (94.9 g). Melting point 200-202° C. (decomposition). Proton nuclear magnetic resonance chemical shift values δ (ppm) (in dimethylsulfoxide-d6) 3.79 (s, 3H), 9.24 (brs, 1H), 10.83 (brs, 1H).

(2) Synthesis of N-allyloxy-3,5-dichloro-1-methylpyrazole-4-carboxylic acid amide

In a solution of N-allyloxy-3,5-dichloro-1-methylpyrazole-4-carboxylic acid amide (40.0 g, 160 mmol) in acetonitrile (200 ml), iodine (122 g, 481 mmol) was added, and stirred at room temperature for 4.5 hours. Saturated sodium thiosulfate aqueous solution (150 ml) was added, extracted with ethyl acetate, the resulting ethyl acetate solution was washed with saturated sodium hydrogen carbonate, saturated sodium chloride aqueous solution and water in that order, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=5/2) to obtain the aimed product (54.0 g). Oily substance. Proton nuclear magnetic resonance chemical shift values δ (ppm) (In CDCl3) 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).

In a solution of sodium boron hydride (0.30 g, 7.9 mmol) in N,N-dimethylformamide (15 ml), 3,5-dichloro-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1-methylpyrazole (2.0 g, 5.3 mmol) was added, and stirred at 60° C. for 0.5 hour. After cooling to room temperature, water (10 ml) was added, and further 35% hydrochloric acid was added to adjust to pH 1, and extracted with ethyl acetate. The resulting ethyl acetate solution was washed with saturated sodium hydrogen carbonate, saturated sodium chloride aqueous solution and water in that order, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=5/2) to obtain the aimed product (1.1 g). Melting point 50-51° C. Boiling point 142° C./0.3 mmHg. Proton nuclear magnetic resonance chemical shift values δ (ppm) (in CDCl3) 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).

(6) Synthesis of 3-chloro-1-methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl chloride

In a solution of 3-chloro-5-mercapto-1-methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (2.5 g, 10 mmol) In 1,2-dichloroethane (50 ml), water (20 ml) was added, and under ice cooling, chlorine (2.1 g, 30 mmol) was introduced with vigorously stirring. In this process the temperature rised to 20° C. After excluding excess chlorine by introducing nitrogen, 1,2-dichloroethane phase was separated. The resulting 1,2-dichloroethane solution was wished with saturated sodium hydrogen sulfite aqueous solution and water in that order, and then dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain the aimed product (3.1 g). Melting point 63-68° C. Proton nuclear magnetic resonance chemical shift values δ (ppm) (in CDCl3) 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).

In a solution of 3-chloro-1-methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole-5-sulfonyl chloride (3.1 g, 9.9 mmol) In 1,2-dichloroethane (30 ml), 28% ammonia water (1.5 g, 24.7 mmol) was added dropwise with vigorously stirring under ice cooling. After stirring at room temperature for 0.5 hour, water (20 ml) and 35% hydrochloric acid (5.2 g, 50 mmol) were added, and extracted with 1,2-dichloroethane. The resulting 1,2-dichloroethane solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain the aimed product (2.8 g). Melting point 120-122° C.

In a solution of 3,5-dichloro-4-(5-iodomethyl-5H,6H-1,4,2-dioxadin-3-yl)-1-methylpyrazole (1.5 g, 4.0 mmol) in tetrahydrofuran (10 ml), potassium t-butoxide (0.52 g, 4.6 mmol) was added, and stirred at room temperature for 0.25 hour. Saturated ammonium chloride aqueous solution (20 ml) was added, extracted with ethyl acetate, the resulting ethyl acetate solution was washed with water and saturated sodium chloride aqueous solution in that order, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=1/1) to obtain the aimed product (0.88 g). Melting point 68-70° C. Proton nuclear magnetic resonance chemical shift values δ (ppm) (in CDCl3) 3.84 (s, 3H), 4.42 (s, 2H), 4.45 (d, J=1.8 Hz, 1H), 4.85 (d, J=1.8 Hz, 1H).

In a solution of 3,5-dichloro-1-methyl-4-(5-methylene-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (2.8 g, 11 mmol) in ethyl acetate (58 ml), 5% palladium-carbon (0.56 g) was added, and under hydrogen atmosphere (1 atm), the mixture was stirred at room temperature for 17 hours. 5% palladium-carbon (0.05 g) was further added, and further stirred under the abovementioned condition for 1 hour, and the catalyst was filtered off. The solvent was distilled off from the filtrate, and the resulting residue was purified with alumina column chromatography (developing solution: chloroform) to obtain the aimed product (2.6 g). Melting point 50-51° C.

In a solution of N-allyloxy-3,5-dichloro-1-methylpyrazole-4-carboxylic acid amide (0.50 g, 2.0 mmol) in toluene (5 ml), trifluoromethane sulfonic acid (0.10 g, 1.04 mmol) was added, and refluxed for 20 hours. The resulting toluene solution was washed with saturated potassium carbonate aqueous solution and water in that order, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=1/1) to obtain the aimed product (0.08 g). Melting point 50-51° C.

In a solution of bis(3-chloro-1-methyl (5-methyl-5H,8H-1,4,2-dioxadin-3-yl)pyrazol-5-yl)disulfide (2.5 g, 5.1 mmol) in 1,2-dichloroethane (50 ml), water (20 ml) was added, and under ice cooling, chlorine (2.1 g, 30 mmol) was introduced with vigorously stirring. In this process the temperature rised to 20° C. After excluding excess chlorine by introducing nitrogen, 1,2-dichloroethane phase was separated The resulting 1,2-dichloroethane solution was washed with saturated sodium hydrogen sulfite aqueous solution and water in that order, and then dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain the aimed product (3.0 g). Melting point 63-68° C.

In a solution of N-allyloxy-3,5-dichloro-1-methylpyrazole-4-carboxylic acid amide (0.50 g, 2.0 mmol) in acetonitrile (5 ml), N-iodosuccinimide (0.67 g, 3.0 mmol) was added, and stirred at room temperature for 15 hours. Saturated sodium thiosulfite aqueous solution (10 ml) was added, extracted with ethyl acetate, the resulting ethyl acetate solution was washed with saturated sodium hydrogen carbonate, saturated sodium chloride aqueous solution and water in that order, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=3/1) to obtain the aimed product (0.60 g). Oily substance.

In a solution of N-allyloxy-3,5-dichloro-1-methylpyrazole-4-carboxylic acid amide (20.0 g, 80.0 mmol) in acetonitrile (200 ml), N-bromosuccinimide (17.1 g, 96.0 mmol) was added, and stirred at mom temperature for 1 hour. Saturated sodium thiosulfate aqueous solution (100 ml) was added, and acetonitrile was distilled off. Then, the mixture was extracted with ethyl acetate, the resulting ethyl acetate solution was washed with water and saturated sodium chloride aqueous solution in that order, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=3/1) to obtain the aimed product (18.4 g). Melting point 53-54° C. Proton nuclear magnetic resonance chemical shift values δ (ppm) (in CDCl3) 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).

In a solution of 4-(5-bromomethyl-5H,6H-1,4,2-dioxadin-3-yl)-3,5-dichloro-1-methylpyrazole (0.50 g, 1.5 mmol) in N-methyl-2-pyrrolidone (5 ml), sodium boron hydride (0.11 g, 3.0 mmol) was added, and stirred at 60° C. for 1 hour. After cooling to room temperature, water (5 ml) was added, and adjusted to pH 1 by adding 35% hydrochloric acid, and extracted with ethyl acetate. The resulting ethyl acetate solution was washed with saturated sodium hydrogen carbonate, saturated sodium chloride aqueous solution and water in that order, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=5/2) to obtain the aimed product (0.31 g). Melting point 50-51° C.

(1) Synthesis of 5-benzylthio-1-methylpyrazole-4-carbohydroxamic acid

In a suspension of 5-benzylthio-1-methylpyrazole-4-carboxylic acid (15.9 g, 64.0 mmol) in toluene (100 ml), thionyl chloride (11.4 g, 95.8 mmol) and N,N-dimethylformamide (0.1 g) were added, and refluxed for 4 hours. The residue obtained by distilling off the solvent was dissolved in tetrahydrofuran (40 ml), On the other hand, in a solution of hydroxyamine hydrochloride (13.3 g, 191 mmol) in water (40 ml), a solution of 85% potassium hydroxide (12.6 g, 191 mmol) in water (40 ml) was added at 5-15° C., and stirred at room temperature for 15 minutes. Then, the above-mentioned tetrahydrofuran solution was added dropwise at 3-15° C. After further stirring at 3° C. for 1.5 hour, the mixture was adjusted to pH 3-4 by adding 35% hydrochloric acid (20 ml) and extracted with ethyl acetate. The resulting ethyl acetate solution was washed with water, dried over anhydrous sodium suite, and the solvent was distilled off. The resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=1/1) to obtain the aimed product (10.3 g). Resinous substance. Proton nuclear magnetic resonance chemical shift values δ (ppm) (in CDCl3) 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).

(2) Synthesis of N-allyloxy-5-benzylthio-1-methylpyrazole-4-carboxylic acid amide

In a solution of 5-benzylthio-1-methyl-4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)pyrazole (1.1 g, 3.5 mmol) in 1,2-dichloroethane (10 ml), water (10 ml) and 35% hydrochloric acid (0.1 g) were added, and chlorine (2.5 g, 35 mmol was introduced at 5° C. with vigorously stirring in this process, the reaction solution generated heat to 19° C. After excluding excess chlorine by introducing nitrogen, water (20 ml) was added, and extracted with 1,2-dichloroethane. The resulting 1,2-dichloroethane was concentrated to 8 ml under reduced pressure. This solution was added dropwise in a separately prepared solution of 1,2-dichloroethane (8 ml) in which 28% ammonia water was added at 5° C. with vigorously stirring, and further stirred for 0.5 hour The resulting solution was adjusted to pH 1 by adding 35% hydrochloric acid, and extracted with 1,2-dichloroethane. The resulting 1,2-dichloroethane solution was dried over anhydrous sodium sulfate and the residue obtained by distilling off the solvent was recrystallized from toluene to obtain the desired product (0.43 g). Melting point 97-99° C. Proton nuclear magnetic resonance chemical shift values δ (ppm) (in CDCl3) 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, 2M), 7.75 (s, 1H).

Synthesis of 4-(5-methyl-5H,6H-1,4,2-dioxadin-3-yl)-1-(pyridin-2-yl)pyrazole-5-sulfonamide

Table 1 shows the structural formulae and physical properties of the compounds synthesized by using the procedure similar to that of Examples and Referential Examples mentioned above together with the compounds described in Examples and Referential Examples mentioned above.

Next, examples of the compounds included in the present invention are in Table 2 together with the compounds synthesized in Examples mentioned above. However, the present invention is not limited thereto. In the meantime, the symbols in the table are as defined above.

Although the application dosage of the compound of the present invention as herbicide is varied depending on the applied scene, the applied season, applied method, weed to be prevented and cultivated crop, etc., generally it is about 0.001 to 50 kg, preferably about 0.01 to 10 kg of the active component per hectare (ha). The compound of the present invention can be use for either submerged soil treatment or foliage treatment as herbicide for paddy. The woods of paddy include for example weeds of Potamogetonaceae represented byPotamogeton disinctus, etc., weeds of Alismataceae represented byAlisma canaliculatum, Sagittaria pygmaeaand,Sagttaria trifolla, etc., weds of Gramineae represented byLeptochloa chinensis, Echinochloa crus-galliandEchinochloa oryzicola, etc., weeds of Cyperaceae represented byEiocharis kuroguwai, Scirpus juncoides, Scripus nipponicus, Cyperus serotinusandCyperus difformis, etc., weeds of Lemnaceae represented bySpirodela polyrhizaandLemna paucicostata, etc., weeds of Commelinaceae represented byMurdannia keisak, etc., weeds of Pontederiaceae presented byMonochoria korsakowiiandMonochoriavaginalis, etc., weeds of Elatinaceae represented byElatine triandra, etc., weeds of Lythraceae represented byAmmannia multifloraandRotala indica, etc., weeds of Oenotheraceae represented byLidwigla epiloblodes, etc., weeds of Scrophulariaceae represented byDopatrium junceum, Lindemia pyxidariaandLindemia dubia, etc., and weeds of Composite represented byBidens frondosaandBidens tripartita, etc., or the like.

In addition, the compound of the present invention can be used for any treatment processes of soil treatment, soil Incorporation treatment and foliage treatment as herbicide for dry field. It can be applied for preventing several weeds on not only agricultural and horticultural area such as paddy, dry field and orchard, etc., but also non-crop lands such as playing field, vacant space and sides of rail track, etc. The compound of the present invention may be applied together with other kinds of herbicides, various kinds of insecticides, fungicides, vegetable growth regulators or synergists, and the like when it formulated or sprayed if necessary.

Particularly, the combined application with other herbicides can lead to low cost due to decrease in applied herbicide amount, enlargement of herbicidal spectrum due to synergistic effect, and higher herbicidal effect. Further, the compound of the present invention can be combined with plural known herbicide simultaneously.

When the compound of the present invention is applied as a herbicide, it can be practically provided in an arbitrary formulation form such as liquid formulations, emulsifiable concentrate, wettable powders, dry flowables, flowables, dust formulations or granules, etc. generally by mixing with a suitable solid carrier or liquid carrier, optionally along with surfactant, penetrating agent, spreading agent, thickner, anti-freezing agent, binder, anti-caking agent or disintegrating agent, etc.

In addition, from the viewpoint of an elimination or reduction of labor and an improvement of safety, the formulations in any desired forms described above may be included into a water-soluble bag.

The solid carrier includes, for example, natural minerals such as kaolinite, pyrofilite, celicite, talc, bentonite, acid china clay, attapulgite, zeolite and diatomaceous earth, etc., inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate and potassium chloride, etc., synthetic silica, and synthetic silicate, and the like.

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

A content of these surfactants is not specifically limited, and it is desirably in the range of 0.05 to 20 parts by weight in general based on 100 parts by weight of the preparation according to the present invention. Also, these surfactants may be used alone or in combination of two or more kinds in combination.

Next, formulation examples of the preparation in case where the compound of the present invention is used are shown below. Provided that formulation examples of the present invention am not limited only thereto. In the interim, in the following Formulation Examples, “part(s)” mean part(s) by weight.

Wettable Powder

Compound of the present invention0.1 to 80partsSolid carrier5 to 98.9partsSurfactant1 to 10partsOthers0 to 5parts

As other components, there may be mentioned, for example, a non-caking agent, a decomposition preventing agent, and the like.

Compound of the present invention0.1 to 30partsLiquid carrier55 to 95partsSurfactant4.9 to 15parts

Compound of the present invention0.1 to 70partsLiquid carrier15 to 98.89partsSurfactant1 to 12partsOther components0.01 to 30parts

As other components, there may be mentioned, for example, an antifreezing agent, a thickening agent, and the like.

Dry Flowable

Compound of the present invention0.1 to 90partsSolid carrier0 to 98.9partsSurfactant1 to 20partsOther components0 to 10parts

As other components, there may be mentioned, for example, a binder, a decomposition preventing agent, and the like.

Liquid Formulation

Compound of the present invention0.01 to 30partsLiquid carrier0.1 to 50partsWater50 to 99.89partsOther components0 to 10parts

As other components, there may be mentioned, for example, an antifreezing agent, a spreading agent, and the like.

Compound of the present invention0.01 to 10partsSolid carrier90 to 99.99partsOther components0 to 10parts

As other components, there may be mentioned, for example, a binder, a decomposition preventing agent, and the like.

The above-mentioned formulation is sprayed as such or in a form diluted with water by 1- to 10000-fold.

Formulation Examples

Next, agrochemical-formulation examples using the compound of the present invention as an active component are concretely described, but the present invention is not limited thereto. In the interim, in the following Formulation Examples, “part(s)” mean part(s) by weight.

Formulation Example 1

Wettable Powder

The above materials are uniformly mixed and pulverized to make wettable powder.

Formulation Example 2

Compound of the present invention No. 15partsXylene75partsN-methylpyrrolidone15partsSolpol 26805parts(A mixture of a nonionic surfactant and an anionicsurfactant available from TOHO Chemical IndustryCo., LTD, Trade-name)

The above materials are uniformly mixed to make emulsifiable concentrate.

Formulation Example 3

The above materials are uniformly mixed, and then, wet pulverized to make a flowable.

Formulation Example 4

Dry Flowable

(Synthetic hydrated silicic acid: available from Shionogi & Co., Ltd., Trade-name) The above materials are uniformly mixed and pulverized, and then, a small amount of water is added to the mixture and the resulting mixture is mixed under stirring, granulated by an extrusion granulator, and dried to make a dry flowable.

Formulation Example 5

Compound of the present invention No. 15partsBentonite55partsTalc44parts

The above materials are uniformly mixed and pulverized, and then, a small amount of water is added to the mixture and the resulting mixture is mixed under stirring, granulated by an extrusion granulator, and dried to make a granule.

In the meantime, the above-mentioned DBSN means sodium dodecyl benzene sulfonate.

Hereinafter, the availability of the compound of the present invention as herbicide will be concretely described based on the following test examples.

Test Example 1

Herbicidal Effect Test in Submerged Condition by Treatment Before Weed-Generation (1)

After alluvial soil was placed in a styrol cup of 1/30000 are, water was poured therein and mixed, and adjusted to a submerged condition of water depth 4 cm. After seeds ofEchinochloa crus-galli, Scirpus juncoidesandMonochoria vaginaliswere sown in the cup, rice seedlings at 2.5th leaf stage were transplanted. On the day when the seeds were sown, the wettable powder of the present invention prepared according to Formulation Example 1 was diluted wt water so as to give a predetermined formulation amount, and the surface of the water was treated with the diluted wettable powder. The plants were grown by putting the cup in a green house at 25 to 30° C., and investigated on herbicidal effect against each weed 3 weeks after treatment with the herbicide according to the following criteria. The results are shown in Table 3.

Criteria

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%

Test Example 2

Herbicidal Effect Test in Submerged Condition by Treatment During Weed-Growth Stage (1)

After alluvial soil was placed in a styrol cup of 1/30000 are, water was poured therein and mixed, and adjusted to a submerged condition of water depth 4 cm. After seeds ofEchinochloa crus-galli, Scirpus juncoidesandMonochoria vaginaliswere sown in the cup, the plants were grown by putting the cup in a green house at 25 to 30° C. WhenEchinochloa crus-galli, Scirpus JuncoidesandMonochoria vaginalisreached 1st to 2nd leaf stage, the wettable powder of the present invention prepared according to Formulation Example 1 was diluted with water so as to give a predetermined formulation amount, and the surface of the water was treated with the diluted wettable powder. The herbicidal effect for each plant was investigated 3 weeks after treatment with the herbicide according to the criteria indicated in Test Example 1. The result are shown in Table 4.

Test Example 3

Herbicidal Effect Test by Soil Treatment

Sterilized diluvial soil was placed in a plastic box having a size of length 21 cm, width 13 cm and depth 7 cm, seedsEchinochloa crus-galli, Digitaria adscendes, Setaria viridis, Avena fatua, Black-grass,Abutilon avicennae, Ambrosia elatior, Amaranthus retroflexus, Chenopodium album, Polygonum blumei, Stellaria media, Zea mays(corn),Glycine max(soybean),Oryza sativa(rice),Triticum aestivum(wheat) andBeta vulgaris(beat) were sown interspatially, covered with about 1.5 cm of soil, and then the wettable powder of the present invention prepared according to Formulation Example 1 was diluted with water so as to give a predetermined formulation amount, and the surface of the soil was uniformly treated with the diluted wettable powder by use of a small-sized spray. The herbicidal effect for each plant was investigated 3 weeks after treatment with the herbicide according to the criteria indicated in Test Example 1. The results are shown in Table 5.

Test Example 4

Herbicidal Elect Test by Foliage Treatment

Sterilized diluvial soil was placed in a plastic box having a size of length 21 cm, width 13 an and depth 7 cm, seeds ofEchinochloa crus-galli, Digitaria adscendes, Setaria viridis, Avena fatua, Black-grass,Abutilon avicennae, Ambrosia elatior, Amaranthus retroflexus, Chenopodium album, Polygonum blumei, Stellaria media, Zea mays, Glycine max, Oryza sativa, Triticum aestivumandBeta vulgariswere sown interspatially, covered with a 1.5 cm of soil, and then the plants were grown by putting the box in a green house t 25 to 30° C. After growth of 14 days, the wettable powder of the present invention prepared according to Formulation Example 1 was diluted with water so as to give a predetermined formulation amount, and the foliage part was uniformly treated with the diluted wettable powder by use of a small-sized spray. The herbicidal effect for each plant was investigated 3 weeks after treatment with the herbicide according to the criteria indicated in Test Example 1. The results are shown in Table 6.

Test Example 5

Herbicidal Effect Test in Submerged Condition by Treatment Before Weed-Generation (2)

Paddy surface soil was placed in a plastic pot of 1/10000 are, water was poured therein and mixed. After seeds ofScirpus juncoideswee sown, paddy surface soil was added by 2 cm, and submerged with water, and then seeds ofEchinochloa crus-galli, Scirpus juncoides, Monochoria vaginalis, Rotala indicaandLindernia pyxidariawere sown together. In addition, rice seedlings at 2.5th leaf stage were transplanted, and fixed to the paddy surface in a state where the roots were exposed on the other side. On the day when the seeds were sown, the wettable powder of the present invention prepared according to Formulation Example 1 was diluted with water so as to give a predetermined formulation amount, and the surface of the water was treated with the diluted wettable powder. The plants were grown by putting the pot in a green house at 25 to 30° C. The herbicidal effort for each plant was investigated 3 weeks after treatment with the herbicide according to the criteria indicated in Test Example 1. The results are shown in Table 7.

Test Example 6

Crop Injury Test on Rice in Water Leakage Condition

A mixed soil of alluvial soil and individual soil was placed in a plastic pot perforated at the bottom of 1/10000 are, water was poured therein and mixed, and then rice seedlings et 2.5th leaf stage were transplanted. War leakage treatment was carried out by placing the pot in a plastic vat, and controlling the amount of water in the vat kept at a condition of 2 cm/day×3 days. The pot was put in a green house at 25 to 30° C., on third day after transplantation, the wettable powder of the present invention prepared according to Formulation Example 1 was diluted water so as to give a predetermined formulation amount, and the surface of the water was treated with the diluted wettable powder. The crop injury on rice was investigated 3 weeks after treatment with the herbicide according to the criteria indicated in Test Example 1 The results are shown in Table 8.

Comparative Compounds 1 and 2 are the following compounds disclosed in JP-A-7-118269 (1995).

INDUSTRIAL APPLICABILITY

The pyrazole sulfonyl urea compound of the present invention is useful as a selective herbicide for paddy rice and wheat or barley.