JPH069317A - Pyrazolesulfonylurea derivative, its production and selective herbicide containing the same derivative - Google Patents

Abstract

PURPOSE:To provide a 5-substituted pyrazole derivative useful as an intermediate of a new pyrazolesulfonylurea derivative valuable as a selective herbicide. CONSTITUTION:The 5-substituted pyrazole derivative of formula I [A is H, an alkyl or phenyl; B is H or an alkyl; D is H, an alkyl or COOR1 (R1 is H, an alkyl, an allyl, propargyl, an alkoxyalkyl, a haloalkyl, an alkoxyalkylcarbonyl or benzyl), COAr (Ar is phenyl which may be substituted with a halogen), a halogen, NO2 or SO2NR2R3 (R2 and R3 are an alkyl); Q is SO2NH2, SO2NCO or SO2NHCOOR4 (R4 is an alkyl or phenyl)], e.g. 4- chloro-1,3-dimethylpyrazole-5-sulfonamide. This exemplified compound is obtained in the form of a crystal by reacting 1,3-dimethyl-5-hydroxypyrazole with phosphorus pentasulfide, blowing chlorine gas into the resultant 1,3-dimethyl-5- mercaptopyrazole until the solution is saturated to react between them, then adding the resultant reaction solution dropwise into an ammonia water and partly concentrating the solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel pyrazolesulfonylurea derivative, a process for producing the compound and a selective herbicide containing the compound as an active ingredient.

[0002]

2. Description of the Related Art Pyridinesulfonylurea derivatives are useful as herbicides in JP-A-55-102577 and JP-A-56-139466, and pyrrolesulfonylurea derivatives in JP-A-56-169688. The effect is described. On the other hand, as a conventional pyrazole derivative, for example, JP-B-54-36648 is used.
JP-A-54-41872 and JP-A-57-2276.
No. 57-58670 and 51-13.
It is known that the compounds described in Japanese Patent No. 3265 are useful as herbicides.

It is essential to use herbicides to protect important crops such as rice, wheat and corn from weed damage and to increase the yield. Particularly in recent years, in arable land where these useful crops and weeds are mixed, a selective herbicide capable of selectively killing only the weeds without showing phytotoxicity to the crops even when the foliage of the crops and the weeds are simultaneously treated is desired. It is rare. In addition, from the viewpoint of prevention of environmental pollution, reduction of economic costs in transportation and spraying, research and exploration of compounds that show high herbicidal effect with the lowest possible dose has been continued for many years. Although some of the compounds with such properties are currently used as selective herbicides, there is still a need for new compounds with these properties.

The above-mentioned pyridinesulfonylurea derivatives and pyrrolesulfonylurea derivatives have excellent herbicidal effects at low doses as compared with conventional herbicides, but do not show selectivity for useful crops. Although some of the conventionally known pyrazole derivatives show selectivity to rice, they require a relatively high dose and cannot be said to have satisfactory properties.

[0005]

[Means for Solving the Problems] The present inventors have continued to study for many years to develop a herbicide having selectivity for important crops, and produce compounds having higher herbicidal activity and selectivity. Therefore, the herbicidal properties of many compounds have been investigated. As a result, the compound of the present invention represented by the general formula (I) is remarkably superior to many known weeds in both soil treatment and foliage treatment, even when compared with known pyridinesulfonylurea derivatives and pyrrolesulfonylurea derivatives. The present invention has been completed by discovering that it has strong herbicidal activity and high safety against important crops such as rice, wheat and corn. On the other hand, since the compound of the present invention exhibits a high herbicidal activity with a very low dose as compared with conventional herbicides, it is also useful as a herbicide for other orchards and non-arable land.

The compound of the present invention represented by the general formula (I) is a novel compound and can be easily produced by selecting one of the following reaction formulas 1 to 3. Reaction formula 1

[0007]

[Chemical 2]

[In the formula, A, B, D, X, Y and Z have the same meanings as described above. That is, a pyrazole sulfonyl isocyanate derivative is dissolved in a sufficiently dried dioxane, an inert solvent such as acetonitrile, and the pyrimidine or triazine derivative represented by the formula (III) is added thereto and stirred, The compound (I) of the present invention is obtained by promptly reacting. When the reaction is difficult to proceed, the reaction easily proceeds by adding an appropriate base, for example, triethylamine, triethylenediamine, pyridine, sodium alkoxide, sodium hydride and the like in minute amounts.

Reaction formula 2

[0010]

[Chemical 3]

[In the formula, A, B, D, X, Y and Z have the same meanings as described above. R ₆ represents an alkyl group or a phenyl group. ] That is, the pyrazole sulfonamide derivative (IV)
Compound (VI) is obtained by reacting with chloroformic acid ester or carbonic acid ester in the presence of a base such as potassium carbonate in a solvent such as acetone or methyl ethyl ketone, and after the reaction, treating with an acidic substance such as hydrochloric acid. Then, the compound (I) of the present invention can be obtained by heating the compound (III) in a solvent such as toluene.

Reaction formula 3

[0013]

[Chemical 4]

[In the formula, A, B and D have the same meanings as described above. E and F are halogen atoms, R ₅ is a lower alkyl group, and G is a nitrogen atom or a ═CH— group. Compound (VIII) which is a part of the compound of the present invention was synthesized by reacting pyrazole sulfonamide derivative (IV) with pyrimidine or triazine isocyanate (VII) with reference to JP-A-56-154471. Then, the compound (IX), which is also a part of the compound of the present invention, can also be synthesized by reacting with sodium alcoholate. The raw material pyrazole sulfonyl isocyanate used in Reaction Scheme 1 was synthesized into pyrazole sulfonamide by the method described below.
It can be synthesized with reference to the method described in Japanese Patent No. 13266. The pyrazole sulfonamide, which is an intermediate, is also a novel compound, and its synthesis can be performed by appropriately selecting some of the synthetic routes described below.

[0015]

[Chemical 5]

I) POCl ₃ ii) NaSCH ₂ Ph iii) Cl ₂ / MeCOOH / H ₂ O iv) NH ₄ OH v) P ₂ S ₅ vi) NaSH vii) NaOH / NH ₄ OH / NaOCl viii) KMnO ₄ ix ) 1.NaNO ₂ , HCl / 2.SO ₂ copper salt x) n-BuNCO [In the formula, A, B, D, X, Y and Z have the same meanings as described above. ] An example of the synthesis of the intermediate pyrazole sulfonamide used in the present invention is described below as a reference example.

[0017]Reference example 1 4-ethoxycarbonyl-1-methylpyrazole-5-
Synthesis of sulfonamide 1-1 5-hydroxy-1-methylpyrazole-4
-Synthesis of ethyl carboxylate Ethanol with 216 g of diethyl ethoxymethylene malonate
216 g of methyl hydrazine and 10 g of methylhydrazine 46 g.
It was added at ° C. Then, stir at room temperature for 1 hour, then
It was heated under reflux for an hour and left to stand. The precipitated crystals are filtered and dried
This gives 148 g of the desired compound with a melting point of 134-135 ° C.
Was given.1-2 5-chloro-1-methylpyrazole-4-cal
Synthesis of ethyl borate 5-hydroxy-1-methylpyrazole-4-carbo
A mixture of 10 g of ethyl acidate and 50 ml of phosphorus oxychloride was added.
It stirred at 90-100 degreeC for 65 hours. Excess oxysalt
Phosphorus chloride was distilled off under reduced pressure, and the residue was poured into ice water. Deposited
When the crystals are filtered and dried, they have a melting point of 194-195 ° C.
Chlor-1-methylpyrazole-4-carboxylic acid 4.5
g was obtained. Also, the filtrate is alkaline with aqueous ammonia.
, Extract with ether, dry and evaporate the solvent to give an oil.
5-chloro-1-methylpyrazole-4-carboxylic acid
4.0 g of ethyl was obtained. 5-chloro-1-methylpi
Razol-4-carboxylic acid (4.5 g) and thionyl chloride (30)
ml, dimethylformamide 0.2 ml, and added for 5 hours.
After heating under reflux, excess thionyl chloride was distilled off under reduced pressure, and dried ethanol was added.
Added to the knoll. After stirring at room temperature for 3 hours, the solvent was distilled off.
After adding ether, washing with water, drying, and distilling off the solvent, 5-chloro
Ethyl-1-methylpyrazole-4-carboxylate 4.5
g was obtained. A total of 8.5 g of target products. Boiling point 104-11
0 ° C / 3mmHg1-3 5-mercapto-1-methylpyrazole-4-
Synthesis of ethyl carboxylate 2.2 g (0.094 mol) of metallic sodium in ethanol
Add to 35 ml, dissolve and add 50 ml of dimethylformamide.
In addition, most of the ethanol was distilled off. Then, under cooling,
Hydrogen chloride gas was blown in to saturate, and then 5-chloro-1
-Ethyl methylpyrazole-4-carboxylate 7.4 g
(0.039 mol) was added. 3.5 hours at 70-80 ° C
After stirring for a while, concentrate under reduced pressure and add ice water to the residue to form.
The insoluble material was filtered. After acidifying the filtrate, chloroform
Extraction of the solvent, drying, and removal of the solvent by evaporation, an oily target product 6.
8 g was obtained. It solidified on standing. Melting point 80-82
℃1-4 4-ethoxycarbonyl-1-methylpyrazo
Synthesis of ru-5-sulfonamide 5-mercapto-1-methylpyrazole-4-carvone
An aqueous solution of 7.1 g of ethyl acidate and 1.6 g of sodium hydroxide
20 ml was added to 100 ml of 28% ammonia water.
61 g of 6% NaOCl aqueous solution is added to this aqueous solution at 5 to 10 ° C.
added. The precipitated crystals were filtered and washed with water to obtain the
Fenamide (5.6 g) was suspended in water and potassium permanganate was added.
A saturated aqueous solution of 5.5 g of Um was added at room temperature. At room temperature
After vigorous stirring, the mixture is filtered and the filtrate is acidified to ethyl acetate.
It was extracted with. When the solvent is distilled off after drying, crystals of the desired product are obtained.
1.8 g was obtained. Melting point 102-104 ° C1-5 4-ethoxycarbonyl-1-methylpyrazo
Synthesis of 5-L-sulfonamide (alternate method) 5-mercapto-1-methylpyrazole-4-
15 to 30 ml of acetic acid 50 ml solution of ethyl carboxylate
The mixture was stirred at 20 ° C. while blowing chlorine gas. Next
The mixture was stirred while blowing a raw gas. Then blow nitrogen gas
After the reaction, the reaction mixture was poured into ice water, extracted with benzene and dried.
After drying and evaporation of the solvent, oily 4-ethoxycarbonyl-1-me
Tyrpyrazole-5-sulfonyl chloride (melting point 13
0 / 1.2 mmHg) was obtained.

The sulfonyl chloride obtained as described above was dissolved in 20 ml of tetrahydrofuran and added to 50 ml of 28% ammonia water under ice cooling. After stirring at room temperature for 2 hours, the crystals were concentrated under reduced pressure, and the precipitated crystals were filtered, washed with water, and further washed with n-hexane. After drying, 1.3
g of the desired product was obtained. The melting point was in agreement with that previously synthesized.

Reference Example 2 4-methoxycarbonyl-1-methylpyrazole-5-
Synthesis of sulfonamide Synthesized according to Reference Example 1 above. Melting point 127-128
℃ Physical properties of each intermediate are as follows.

Methyl 5-hydroxy-1-methylpyrazole-4-carboxylate Melting point 111-113 ° C. Methyl 5-chloro-1-methylpyrazole-4-carboxylate Melting point 70-71 ° C. 5-Mercapto-1-methylpyrazole- Methyl 4-carboxylate Melting point 64-65 ° C Reference Example 3 Synthesis of 4-chloro-1,3-dimethylpyrazole-5-sulfonamide and 1,3-dimethylpyrazole-5-sulfonamide 3-1 1,3-Dimethyl Synthesis of 5-mercaptopyrazole To 630 ml of xylene, 84 g (0.75 mol) of 1,3-dimethyl-5-hydroxypyrazole was added, and 110
Heat to ~ 120 ° C. Phosphorus pentasulfide 65.3 g (0.2
(94 mol) was added little by little, and the mixture was heated under reflux for an additional 1.5 hours. After filtration while hot, the solvent was distilled off to deposit 21.4 g of the target crystal. Melting point 130-132 ° C. 3-2 4-chloro-1,3-dimethylpyrazole-5
-Synthesis of sulfonamide 1,3-Dimethyl-5 obtained above in 100 ml of acetic acid
12 g (0.094 mol) of mercaptopyrazole and 15 ml of water were added. Chlorine gas was blown into this at 10 ° C. until it became saturated. After stirring for 2 hours, this was added to ice water, extracted with ether, and washed with water. After drying, the ether was distilled off to give oily 4-chloro-1,3-dimethylpyrazole-5-sulfonyl chloride 19.5.
g was obtained. This was dissolved in 50 ml of tetrahydrofuran and added dropwise to 130 ml of 28% ammonia water at a temperature of 10 ° C or lower. After stirring at room temperature for 3 hours and part of the solvent was concentrated, crystals were precipitated. This is filtered and the target crystal 1
0.8 g was obtained. Melting point 135-138 [deg.] C. 3-3 Synthesis of 1,3-dimethylpyrazole-5-sulfonamide The filtrate obtained by filtering the sulfonamide which was the target in Reference Example 3-2 above was washed several times with benzene. After washing, a part of water was distilled off under reduced pressure, and the mixture was concentrated and then extracted with ethyl acetate. The extract was dried and concentrated to obtain 4.0 g of the desired product. Melting point 63-66 [deg.] C.

Reference Example 4 Synthesis of 1,3-dimethyl-4-nitropyrazole-5-sulfonamide 4-1 Synthesis of 5-chloro-1,3-dimethyl-4-nitropyrazole 90% concentrated nitric acid 10 ml concentrated sulfuric acid Add 35g, 75-8
5-chloro-1,3-dimethylpyrazole 13 at 5 ° C
g (0.1 mol) was added dropwise. After dropping, the reaction mixture was stirred at 75 to 85 ° C. for 1.5 hours, poured into ice, and the precipitated solid was filtered, washed with water and dried to obtain 14.5 g of the desired product. Melting point 70 ° C. 4-2 Synthesis of 5-benzylthio-1,3-dimethyl-4-nitropyrazole 21 g of sodium methoxide in dimethylformamide 4
50.8 g of benzyl mercaptan in a 00 ml solution under ice cooling
(0.41 mol) was added, followed by 5-chloro-1,3-
Dimethyl-4-nitropyrazole 65.2 g (0.37
Mol) was added. The reaction mixture was stirred at room temperature for 3 hours, dimethylformamide was evaporated under reduced pressure, and the residue was poured into ice water. The precipitated solid was filtered, washed with water and n-hexane, and dried to obtain 82.4 g of the desired product. Melting point 8
2 to 83 ° C. 4-3 1,3-dimethyl-4-nitropyrazole-5
-Synthesis of sulfonamide 40 g (0.152 mol) of 5-benzylthio-1,3-dimethyl-4-nitropyrazole was dissolved in 300 ml of acetic acid containing 30 ml of water, and chlorine gas was blown into this solution at 3-8 ° C. Stir for 1.5 hours. Then, the reaction mixture was poured into ice water and extracted with ether to obtain crude 1,3-dimethyl-4-nitropyrazole-5-sulfonyl chloride as an oil.

The sulfonyl chloride obtained here was dissolved in a small amount of tetrahydrofuran, and this was added to 150 ml of 28% ammonia water under ice cooling. After stirring for 5 hours at room temperature, the solid obtained by concentrating under reduced pressure was filtered and washed with water and n-
After washing with hexane and drying, 19.6 g of the desired product was obtained. Melting point 138 to 140 ° C. Reference example 5 Synthesis of 1,3-dimethyl-4-dimethylsulfamoylpyrazole-5-sulfonamide 5-1 N, N-dimethyl- (5-chloro-1,3-dimethylpyrazole)- Synthesis of 4-sulfonamide In 150 ml of chlorosulfonic acid under cooling at 5 ° C or lower
Chlor-1,3-dimethylpyrazole 30 g (0.23
Mol) was added dropwise. After the dropping, the mixture was heated and stirred at 100 ° C. for 8 hours. Then, the temperature was lowered to 80 ° C. and thionyl chloride 36
g was added dropwise over 30 minutes. After dropping, the mixture was stirred at 100 ° C. for 2 hours. After that, the reaction mixture was cooled with ice water and carefully poured into ice water to give crude 5-chloro-1,3-
Dimethylpyrazole-4-sulfonyl chloride 50 g
Was obtained as crystals.

Next, 40 g of dimethylamine was dissolved in 250 ml of tetrahydrofuran, and the above sulfonyl chloride was added to the solution while cooling with ice, and the mixture was stirred at room temperature for 3 hours. After the reaction, tetrahydrofuran was distilled off under reduced pressure, ether was added to the residue, washed with water, dried, and the solvent was distilled off to obtain 47 g of the desired product.
was gotten. Melting point 53-55 ° C 5-2 N, N-dimethyl- (5-benzylthio-1,
Synthesis of 3-dimethylpyrazole) -4-sulfonamide According to Reference Example 4-2, N, N-dimethyl- (5-chloro-1,3-dimethylpyrazole) -4-sulfonamide was obtained as a raw material. Melting point 108-109 ° C. 5-3 Synthesis of 1,3-dimethyl-4-dimethylsulfamoylpyrazole-5-sulfonamide N, N-dimethyl- (5-benzylthio-1,3-dimethyl) according to Reference Example 4-3. Pyrazole) -4-sulfonamide was obtained as a raw material. Melting point 209 to 210 ° C. Reference Example 6 Synthesis of 4- (2,4-dichlorobenzoyl) -1-methylpyrazole-5-sulfonamide 6-1 5-chloro-4- (2,4-dichlorobenzoyl)- Synthesis of 1-methylpyrazole 40 g (0.148 mol) of 4- (2,4-dichlorobenzoyl) -5-hydroxy-1-methylpyrazole was added to 150 ml of phosphorus oxychloride and heated at 100 ° C for 6 hours. After the reaction, phosphorus oxychloride was distilled off under reduced pressure, added to ice water, and extracted with benzene. The solvent is distilled off, and the desired product 52.
3 g was obtained as an oil. 6-2 Synthesis of 4- (2,4-dichlorobenzoyl) -1-methyl-5-mercaptopyrazole 5-chloro-4- (2,4-dichlorobenzoyl) -1
A mixture of 50 g of methylpyrazole, 225 g of sodium hydrosulfide dihydrate (70%) and 1000 ml of ethanol was heated under reflux for 5 hours. After completion of the reaction, ethanol was distilled off under reduced pressure, and then 500 ml of water was added to this and extracted with benzene. The aqueous layer was acidified with concentrated hydrochloric acid and washed with chloroform. The organic layer was washed with water and dried, and the solvent was distilled off to obtain 41.4 g of the desired product. Melting point 81-83 ° C. 6-3 Synthesis of 4- (2,4-dichlorobenzoyl) -1-methylpyrazole-5-sulfonamide 4- (2,4-dichlorobenzoyl) -1-methyl-5
A mixture of 12.5 g mercaptopyrazole, 120 ml acetic acid and 20 ml water with chlorine gas at 3-8 ° C.
I breathed time. After the reaction was completed, the reaction solution was poured into ice water, and the precipitated solid was filtered, washed with water and dried. The sulfonyl chloride obtained here was dissolved in a small amount of tetrahydrofuran, and this was added to 100 ml of 28% ammonia water under ice cooling. After stirring at room temperature for 2 hours, the solid obtained by concentrating under reduced pressure was filtered, washed with water and n-hexane, and then dried to obtain 8.6 g of the desired product. Melting point 165-167 ° C Reference Example 7 Synthesis of 4-ethoxycarbonyl-1,3-dimethylpyrazole-5-sulfonamide 5-amino-1,3-dimethyl in a mixed solution of concentrated hydrochloric acid 18 ml, acetic acid 18 ml and phosphoric acid 10 ml. Pyrazole-4-
9.15 g (0.05 mol) of ethyl carboxylate was added. After cooling to -10 ° C, 3.8 g of sodium nitrite dissolved in 7.6 ml of water was added dropwise. Next, add 1.0 g of cuprous chloride to 60 ml of a saturated solution of sulfur dioxide in acetic acid, and add at 0 ° C.
The solution prepared above was added little by little into the cooled solution. After the dropping was completed, the reaction solution was stirred at 10 ° C. for 1 hour, poured into ice water,
Ether extraction yielded 7.2 g of crude 4-ethoxycarbonyl-1,3-dimethylpyrazole-5-sulfonyl chloride. The sulfonyl chloride obtained here was dissolved in 16 ml of tetrahydrofuran and
This was added to 40 ml of 28% aqueous ammonia at a temperature of 0 ° C. or lower under ice cooling. After stirring for 3 hours at room temperature, the solid obtained by concentrating under reduced pressure was filtered, washed with water, and dried to give the desired product 5.
8 g was obtained. Melting point 116-118 ° C. Reference Example 8 Synthesis of 1,3-dimethyl-4-methoxycarbonylpyrazole-5-sulfonamide Synthesized from methyl 5-amino-1,3-dimethylpyrazole-4-carboxylate according to Reference Example 7. did. Melting point 162
~ 164 ° C Reference Example 9 4-Ethoxycarbonyl-1-phenylpyrazole-5
-Synthesis of sulfonamide It was synthesized from ethyl 5-amino-1-phenylpyrazole-4-carboxylate according to Reference Example 7. Melting point 197-2
00 ° C. Reference Example 10 Synthesis of 4-ethoxycarbonylpyrazole-5 (3) -sulfonamide Synthesized from ethyl 5 (3) -aminopyrazole-4-carboxylate according to Reference Example 7. Melting point 179-180 ° C Reference Example 11 4-Butoxycarbonyl-1-methylpyrazole-5-
Synthesis of sulfonamide To 100 ml of 50% methanol water containing 4.74 g of sodium hydroxide, 13.8 g of 4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide was added, and 45
Heated to reflux for minutes. After the reaction, the solvent was distilled off and the residue was 30 m.
1 of water was added, and further 10% hydrochloric acid water was added. The crystals precipitated here were separated by filtration to obtain 11.8 g of crystals of 4-carboxy-1-methylpyrazole-5-sulfonamide. Melting point 192-195 ° C. Then, 6.13 g of the sulfonamide obtained here was n-
It heated at 80 degreeC for 3 hours, blowing hydrogen chloride gas in 60 ml of butanol. After n-butanol was distilled off, the mixture was heated again with n-butanol and hydrogen chloride at 80 ° C. for 3 hours. The crude crystals obtained after distilling off n-butanol were recrystallized from benzene to obtain 5.8 g of the desired product. Melting point 96 to 99 ° C. Reference Example 12 Synthesis of 1-methyl-4-n-propoxycarbonylpyrazole-5-sulfonamide Synthesis was performed according to Reference Example 11. Melting point 71 to 73 ° C. Reference Example 13 Synthesis of 1-methyl-4-i-propoxycarbonylpyrazole-5-sulfonamide Synthesis was performed according to Reference Example 11. Melting point 112 to 115 ° C. Reference Example 14 Synthesis of 4- (2-chloroethoxycarbonyl) -1-methylpyrazole-5-sulfonamide Synthesis was performed according to Reference Example 11. Melting point 107-110 ° C. Reference Example 15 Synthesis of 4- (2-ethoxyethoxycarbonyl) -1-methylpyrazole-5-sulfonamide Synthesis was performed according to Reference Example 11. Melting point 62-67 ° C Reference Example 16 4-allyloxycarbonyl-1-methylpyrazole-
Synthesis of 5-sulfonamide To 8.2 g of 4-carboxy-1-methylpyrazole-5-sulfonamide synthesized in Reference Example 11, 80 ml of allyl alcohol and 5 ml of methanesulfonic acid were added, and the mixture was heated under reflux for 18 hours. After the solvent was distilled off, the solution was poured into ice water and extracted with benzene. After evaporating the dry solvent, 10.7 g of the desired product was obtained. Oily substance.

Reference Example 17 Synthesis of 1-methyl-4-propargyloxycarbonylpyrazole-5-sulfonamide Synthesis was carried out according to Reference Example 16. Melting point 121 to 124 ° C. Reference Example 18 Synthesis of 1-benzyloxycarbonyl-1-methylpyrazole-5-sulfonamide 1.03 g of 4-carboxy-1-methylpyrazole-5-sulfonamide synthesized in Reference Example 11 was added to 10 ml of tetrahydrofuran. In addition, 0.51 g of triethylamine was added. After stirring at room temperature for 10 minutes, 0.86 g of benzyl bromide was added, and the mixture was stirred for 20 hours. After filtering the precipitated solid, the filtrate was poured into water and extracted with benzene. 1.2 g of the target product was obtained by drying and distilling off the solvent. Oily substance.

Reference Example 19 4-Ethoxycarbonylmethyloxycarbonyl-1-
Synthesis of methylpyrazole-5-sulfonamide Synthesized according to Reference Example 18. Melting point 70 to 75 ° C. Reference Example 20 Synthesis of 1,4-dimethylpyrazole-5-sulfonamide Reference Example 7 from 5-amino-1,4-dimethylpyrazole
Was synthesized according to Melting point 119 to 121 ° C. Reference example 21 Synthesis of 4-bromo-1-methylpyrazole-5-sulfonamide 1-Methyl-5-aminopyrazole 9.7 g, acetic acid 40
16 g of bromine was added dropwise to the solution of ml at 20 ° C. and left overnight. The formed solid was collected by filtration, dissolved in water, and made alkaline with an aqueous potassium carbonate solution to precipitate a solid. The crystals were recrystallized from a mixed solvent of benzene and hexane to obtain 13.1 g of 5-amino-4-bromo-1-methylpyrazole. Melting point 1
08-110 ° C. Next, the target product was synthesized according to Reference Example 7. Melting point 120-
125 ° C. Reference Example 22 Synthesis of 4-ethoxycarbonyl-3-ethyl-1-methylpyrazole-5-sulfonamide Ethyl 1-ethoxypropylidene cyanate 19.7
g was added to 50 ml of ethanol, and 4.6 g of methylhydrazine was added dropwise at 10 ° C or lower. After the dropwise addition, the mixture was heated under reflux for 1 hour and then the solvent was distilled off to give 5-amino-4-ethoxycarbonyl-3-ethyl-1-methylpyrazole 1
6.5 g was obtained. Melting point 71 to 73 ° C. Next, the target product was synthesized according to Reference Example 7. Melting point 109-
113 ° C. Reference Example 23 1-n-butyl-4-ethoxycarbonylpyrazole-
Synthesis of 5-sulfonamide According to Reference Example 22, 5-amino-1-n-butyl-4-ethoxycarbonylpyrazole was synthesized from ethyl ethoxymethylene cyanate and n-butylhydrazine. Melting point 56-57 ° C. Next, the target product was synthesized according to Reference Example 7. Oily substance Reference Example 24 4-ethoxycarbonyl-1-ethylpyrazole-5-
Synthesis of Sulfonamide To 3.5 g of the sulfonamide obtained in Reference Example 1, 1.36 g of diethylsulfate was added, and the mixture was heated and stirred at 150 ° C. for 1.5 hours. After cooling the reaction mixture, 30 ml of ethyl acetate,
30 ml of ice water and 20 m of saturated aqueous sodium hydrogen carbonate solution
l, and after stirring at room temperature for 30 minutes, 6N hydrochloric acid 10m
1 was added. The ethyl acetate layer was dried and the solvent was distilled off to obtain 2.8 g of a mixture of 4-ethoxycarbonyl-1-ethylpyrazole-5-sulfonamide and 4-ethoxycarbonyl-1-ethylpyrazole-3-sulfonamide. 0.4 g of the target product was separated from the mixture by silica gel chromatography (eluent: ethyl acetate / methanol = 5/1). Melting point 147 to 152 ° C. Reference Example 25 4-Ethoxycarbonyl-1-t-butylpyrazole-
Concentrated sulfuric acid 15.5g of synthesis 25 - 1 1-t-butyl-4-carboxylate 5-sulfonamide, phosphoric acid (85%) 60 ml, water 20
In a mixed solution of 0 ml, 31.7 g of ethyl 3-amino-1-t-butylpyrazole-4-carboxylate was dissolved, and while cooling to 0 to 5 ° C., sodium nitrite dissolved in 40 ml of water was dissolved. 4 g was added dropwise. This diazotization reaction solution was added dropwise to a 50% aqueous solution of hypophosphorous acid at room temperature. After stirring at room temperature for 1.5 hours, 28% ammonia water was added until the pH reached 6, and extraction with ether, washing with water, drying and evaporation of the solvent were carried out to obtain 29.1 g of the oily target compound. 25-2 Synthesis of 4-ethoxycarbonyl-1-t-butylpyrazole-5-sulfonamide Ethyl 1-t-butylpyrazole-4-carboxylate 9.
8 g was suspended in 100 ml of dry ether and cooled to -60 ° C or lower. Then, a lithium diisopropylamide (1.2 times mole) ether solution was added dropwise. As it is 1
Stir for a period of time and then bubble with sulfurous acid gas for about 30 minutes. After reacting at -60 ° C for 1 hour, the mixture was further stirred at room temperature for 2 hours. The precipitated crystals were filtered and dried to obtain 12 g of solid lithium 4-ethoxycarbonyl-1-t-butylpyrazole-5-sulfonic acid salt. Next, add 200 ml of ice water,
Into a solution of 150 ml of dichloromethane, 6.4 g of N-chlorosuccinimide was added at a temperature of 0 to 5 ° C. After stirring at room temperature for 45 minutes, the dichloromethane layer was separated, and the aqueous layer was extracted with 100 ml of dichloromethane and combined. Ammonia water (28%) 150 m in which the obtained solution of 4-ethoxycarbonyl-1-t-butylpyrazole-5-sulfonyl chloride in dichloromethane was cooled to 10 ° C. or lower.
It was dripped into 1 l. After stirring at room temperature for 1 hour, the solvent was distilled off to obtain 5.1 g of the target sulfonamide. Melting point 1
09 to 111 ° C. Reference Example 26 Synthesis of 4-ethoxycarbonyl-1-i-propylpyrazole-5-sulfonamide Synthesis was performed according to the method of Reference Example 13.

Melting point 130-135 ° C. Reference Example 27 4-Dimethylsulfamoyl-1-methylpyrazole-
Synthesis of 5-sulfonamide It was synthesized according to Reference Example 5. Melting point 139 to 141 ° C. Reference Example 28 Synthesis of 1-phenylpyrazole-5-sulfonamide Synthesized from 5-amino-1-phenylpyrazole according to Reference Example 7. Melting point 170-172 ° C. Reference Example 29 Synthesis of 4-bromopyrazole-5 (3) -sulfonamide Reference Example 7 from 5 (3) -amino-4-bromopyrazole
Was synthesized according to (1-2) N- (ethoxycarbonyl) -4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide (alternate method) 1.0 g of ethyl carbamate and 0.59 g of sodium hydride were added to 30 ml of dried tetrahydrofuran. The mixture was stirred at room temperature overnight. Under ice cooling, 4-ethoxycarbonyl-
1-methylpyrazole-5-sulfonyl chloride 2.
8 g was added dropwise, and then the mixture was stirred at 30 ° C. for 4 hours. After the solvent was distilled off, ice water was added, and the mixture was acidified with concentrated hydrochloric acid. After extraction with ether, the residue was purified by silica gel chromatography to obtain 1.0 g of the desired product. Melting point 110 to 112 ° C. Specific synthetic examples of the compound of the present invention are described below using the substituted pyrazole sulfonamides obtained in Reference Examples 1 to 29, but the present invention is not limited thereto.

[0027]

EXAMPLES Example 1 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide (Compound No.
8) 4-Ethoxycarbonyl-1-methylpyrazole-5-
5.0 g of sulfonamide, 4.45 g of dried potassium carbonate
2.13 g of n-butyl isocyanate was added to a mixture of 50 ml of acetone in Example 1 at room temperature, and the mixture was stirred with heating under reflux for 3 hours. After the reaction, acetone was distilled off under reduced pressure, ice water was added to the residue,
The insoluble material was filtered. The filtrate was acid-precipitated with hydrochloric acid, and the precipitated crystals were separated by filtration, washed with water and dried to give N- (n-butylcarbamoyl).
-4-ethoxycarbonyl-1-methylpyrazole-5
-5.1 g of sulfonamide were obtained. Melting point 117-119
° C. Then, this was added to 120 ml of dry toluene, and 9.1 g of phosgene was blown thereinto under heating under reflux, and then 1.
The mixture was heated under reflux for 5 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to give crude 4-ethoxycarbonyl-1-methylpyrazole-5-sulfonyl isocyanate (boiling point 110 ° C / 0.07 mmH
g) was obtained. This crude sulfonyl isocyanate 0.98
g to 2-amino-4,6-dimethoxypyrimidine 400
A solution of 20 mg of dry acetonitrile was added, and the mixture was stirred at room temperature. The crystals formed were filtered off, washed and dried to obtain 0.8 g of the desired product. Melting point 170-172 ° C Example 2 N-[(4-Methoxy-6-methylpyrimidin-2-yl) aminocarbonyl] -4-methoxycarbonyl-1
Synthesis of -Methylpyrazole-5-sulfonamide (Compound No. 2) N- (n-butylcarbamoyl) -4-methoxycarbonyl- was prepared according to the method of Example 1 using the sulfonamide obtained in Reference Example 2. 1-Methylpyrazole-5-sulfonamide is obtained. Melting point 88-90 [deg.] C. Further, according to Example 1, sulfonyl isocyanate was obtained, and 2-amino-4 was obtained.
The desired product was obtained by reacting with -methoxy-6-methylpyrimidine. Melting point 183 to 184 ° C. Example 3 Synthesis of N-[(4,6-dimethylpyrimidin-2-yl) aminocarbonyl] -4-chloro-1,3-dimethylpyrazole-5-sulfonamide (Compound No. 15) (1) N- (ethoxycarbonyl) -4-chloro-1,
Synthesis of 3-dimethylpyrazole-5-sulfonamide 2.1 g of the sulfonamide obtained in Reference Example 3-2, 1.73 g of potassium carbonate and 1.41 g of ethyl chloroformate were added to 30 ml of dry acetone, and the mixture was added at room temperature to Stir for hours. After distilling off the solvent, water was added, acidified with concentrated hydrochloric acid and then extracted with ether. The organic layer was dried and concentrated, and then the precipitated crude crystals were recrystallized with a mixed solvent of benzene-hexane to obtain 2.0 g of the desired product. Melting point 106-109 ° C. (2) Synthesis of N-[(4,6-dimethylpyrimidin-2-yl) aminocarbonyl] -4-chloro-1,3-dimethylpyrazole-5-sulfonamide The above compound 1 was added to 10 ml of xylene. 0.41 g and 2-amino-4,6-dimethylpyrimidine 0.74 g were added, and the mixture was heated under reflux for 2 hours. When left at room temperature, 1.2 g of the desired product was precipitated. Melting point 191-194 ° C Example 4 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonylpyrazole-5 (3) -sulfonamide (Compound No. 64) (1 ) Synthesis of N-phenoxycarbonyl-4-ethoxycarbonylpyrazole-5 (3) -sulfonamide 4-ethoxycarbonylpyrazole-5 (3) -sulfonamide A solution of 8.76 g of dimethylformamide in 40 ml of 55% sodium hydride 1. To a suspension of 75 g of dimethylformamide in 15 ml was added dropwise under ice cooling. Then 8.56 g of diphenyl carbonate dimethylformamide 3
The 0 ml solution was added dropwise under ice cooling and then stirred overnight at room temperature.
The precipitated solid was collected by filtration, added to a mixture of 5% hydrochloric acid 50 ml, ice 50 g and ethyl acetate 300 ml and stirred.
The organic layer was washed with water, dried, concentrated, and then the precipitated crude crystals were washed with ether and dried to obtain 9.0 g of the desired product. Mp 153-155 [deg.] C. (2) Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonylpyrazole-5 (3) -sulfonamide Obtained above in 10 ml of anhydrous dioxane. N-phenoxycarbonyl-4-ethoxycarbonylpyrazole-
1.02 g of 5 (3) -sulfonamide and 465 mg of 2-amino-4,6-dimethoxypyrimidine are added,
The mixture was heated under reflux for 1 hour. After completion of the reaction, dioxane was distilled off under reduced pressure, 5 ml of benzene was added to the residue, and the mixture was stirred. The precipitated crystals were filtered, washed with a small amount of ethyl acetate, and then dried to obtain 0.92 g of the desired product. Melting point 189 to 191 ° C Example 5 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-carboxy-1-methylpyrazole-5-sulfonamide (Compound No. 76) Example To 4.6 g of the compound (Compound No. 8) obtained in 1 above, 200 ml of a 10% aqueous sodium hydroxide solution was added, and the mixture was heated at 60 ° C. for 1 hour. After cooling, acidification with concentrated hydrochloric acid caused crystals to precipitate. The desired product (2.9 g) was obtained by filtration and drying. Melting point 232-238 ° C Example 6 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide (Compound No.
8) (1) N- (Ethoxycarbonyl) -4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide 4-ethoxycarbonyl-1 in 30 ml of dry acetone.
-Methylpyrazole-5-sulfonamide 4.66 g,
Ethyl chloroformate 2.5 g, anhydrous potassium carbonate 4.14
g was added and the mixture was refluxed for 3 hours. After cooling, acetone was distilled off, ice water was added, insoluble matter was removed, and acid precipitation was carried out with hydrochloric acid. After extraction with ether, drying and evaporation of the solvent, crystals were precipitated from a mixed solvent of benzene and hexane. Obtained amount 5.4 g, melting point 110-112
(2) N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonyl-1
-Methylpyrazole-5-sulfonamide To 20 ml of toluene, 2.5 g of the sulfonyl carbamate obtained in the above (1) and 1.4 g of 2-amino-4,6-dimethoxypyrimidine were added, and toluene was distilled off little by little. Refluxed. Reduced toluene was added occasionally. After 8 hours under reflux, a part of toluene was distilled off, and when left standing, crystals of the target substance were precipitated. Yield 3.1g Melting point 170-1
72 ° C. Example 7 N-[(4-methoxy-6-methyltriazin-2-yl) aminocarbonyl] -4-ethoxycarbonyl-1
-Synthesis of methylpyrazole-5-sulfonamide (Compound No. 9) (1) N- (phenoxycarbonyl) -4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide 55% sodium hydride in 10 ml of dimethylformamide. 0.436 g, 4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide 2.33 g were added. Next, 2.57 g of diphenyl carbonate was added under ice cooling, and the mixture was stirred overnight at room temperature. Then, the dimethylformamide was distilled off, washed with ether and dissolved in ice water. After removing the insoluble matter, acidification with hydrochloric acid caused precipitation of a solid. After extraction with benzene and drying, the solvent was distilled off, and crystals were precipitated from a mixed solvent of benzene and hexane. Yield 3.0 g, melting point 10
3 to 106 ° C. (2) N-[(4-methoxy-6-methyltriazine-
2-yl) aminocarbonyl] -4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide 1.8 g of the sulfonyl carbamate obtained in (1) above and 2-amino-4-methoxy-6 in 10 ml of anhydrous dioxane. -Methyltriazine 0.71g was added and it heated and refluxed for 1 hour. After completion of the reaction, the solvent was distilled off, a small amount of benzene was added to the residue, and the mixture was left to stand to precipitate crystals. Yield 0.8g
Melting point 138-139 [deg.] C. Example 8 N-[(4-methoxy-6-methylpyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonyl-1
-Synthesis of Methylpyrazole-5-sulfonamide (Compound No. 7) N- (methoxycarbonyl) -4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide was prepared according to Example 6 using methyl chloroformate. Was synthesized. Melting point 93-95 ° C. Then, similarly according to Example 6, by reacting with 2-amino-4-methoxy-6-methylpyrimidine,
I got the object. Melting point 152-154 ° C Example 9 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -1,3-dimethyl-4-ethoxycarbonylpyrazole-5-sulfonamide (Compound No. 53 ) (1) Synthesis of ethyl (4,6-dimethoxypyrimidin-2-yl) carbamate 2-amino-in 50 ml of dry tetrahydrofuran.
4.8 g of 4,6-dimethoxypyrimidine was added, followed by 3.3 g of sodium hydride (55%) in small portions. After stirring at room temperature for 1 hour, diethyl carbonate 6.6
g was added dropwise under ice cooling. After stirring overnight at room temperature, 6.8 ml of concentrated hydrochloric acid and then 10 ml of saturated saline were added dropwise under ice cooling. After removing the inorganic salt, it was dried over anhydrous sodium sulfate. After filtration and removal of the solvent by distillation, n-hexane and benzene were added and the mixture was allowed to stand, whereby crystals of the target substance were precipitated. Yield 4.7g
Melting point 62-64 ° C (2) Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -1,3-dimethyl-4-ethoxycarbonylpyrazole-5-sulfonamide 1 in 20 ml of dioxane. , 3-Dimethyl-4-ethoxycarbonylpyrazole-5-sulfonamide 2 g, ethyl (4,6-dimethoxypyrimidin-2-yl) carbamate 2 g and 1,5-diazabicyclo [4.3.
0] -5-nonene (2 g) was added, and the mixture was heated at 90 ° C. for 6 hours.
After the reaction, the solvent was distilled off, ice water was added, and the mixture was acidified with concentrated hydrochloric acid. After extraction with chloroform, drying over anhydrous sodium sulfate, distilling off the solvent, a small amount of benzene and n-hexane were added, and the mixture was allowed to stand to precipitate crystals of the desired product. Yield 0.5g melting point 1
44-146 ° C Example 10 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-n-propyloxycarbonyl-1-methylpyrazole-5-sulfonamide (Compound No. 81 ) According to Example 9, it was synthesized from 1-methyl-4-n-propyloxycarbonylpyrazole-5-sulfonamide and methyl (4,6-dimethoxypyrimidin-2-yl) carbamate. Melting point 167-168 ° C Example 11 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -1,3-dimethyl-4-methoxycarbonylpyrazole-5-sulfonamide (Compound No. 48 ) According to Example 9, it was synthesized from 1,3-dimethyl-4-methoxycarbonylpyrazole-5-sulfonamide and phenyl (4,6-dimethoxypyrimidin-2-yl) carbamate. Melting point 159 to 161 ° C. Next, the physical property values of the compounds synthesized according to the above Examples are shown in Table 1 below together with the compounds synthesized in Examples 1 to 11, but the compounds of the present invention are not limited to these. .

[Table 1]

[0029]

[Chemical 6]

[0030]

[Table 1] ─────────────────────────────────── Compound melting point No. A B D X Y Z (℃) ─────────────────────────────────── 1 Me H COOMe Me Me -CH = 196〜198 2 Me H COOMe Me OMe -CH = 183 to 184 3 Me H COOMe OMe OMe -N = 110 to 113 4 Me H COOMe Me OMe -N = 171 to 172 5 Me H COOMe OMe OMe -CH = 163-165 6 Me H COOEt Me Me -CH = 163-165 7 Me H COOEt Me OMe -CH = 152-154 8 Me H COOEt OMe OMe -CH = 170-172 9 Me H COOEt Me OMe -N = 138-139 10 Me H COOEt OMe OMe -N = 142 ~ 144 11 Me Me H Me Me -CH = 184 ~ 187 12 Me Me H Me OMe -CH = 160 ~ 162 13 Me Me H OMe OMe -N = 162 ~ 165 14 Me Me Cl H Me -CH = 178 to 180 15 Me Me Cl Me Me -CH = 181 to 183 16 Me Me Cl Me OMe -CH = 165 to 168 17 Me Me Cl OMe OMe -CH = 176 to 178 18 Me Me Cl Me Cl -CH = 173 to 176 19 Me Me Cl Me O-CH ₂ CH ₂ C = 200 to 201 20 Me Me Cl Me Me -N = 156 to 158 21 Me Me Cl Me OMe -N = 158 to 160 22 Me Me Cl OMe OMe -N = 180 to 183 ────────────────────────────────────

[0031]

[Table 2] [Continued from Table 1] ──────────────────────────────────── Compound melting point No. . A B D X Y Z (° C) ─────────────────────────────────── 23 Me Me NO ₂ Me Me -CH = 194 to 195 24 Me Me NO ₂ Me OMe -CH = 212 to 213 25 Me Me NO ₂ OMe OMe -CH = 166 to 168 26 Me Me NO ₂ Me Cl -CH = 218 to 220 27 Me Me NO ₂ Me O-CH ₂ CH ₂ C = 220 to 222 28 Me Me NO ₂ Me Me -N = 189 to 191 29 Me Me NO ₂ Me OMe -N = 170 to 171 30 Me Me NO ₂ OMe OMe -N = 198 ~ 200 31 Me Me SO ₂ -NMe ₂ Me Me -CH = 212 ~ 215 32 Me Me SO ₂ -NMe ₂ Me OMe -CH = 206 ~ 209 33 Me Me SO ₂ -NMe ₂ OMe OMe -CH = 169 ~ 172 34 Me Me SO ₂ -NMe ₂ Me Cl -CH = 205 to 207 35 Me Me SO ₂ -NMe ₂ Me O-CH ₂ CH ₂ C = 218 to 220 36 Me Me SO ₂ -NMe ₂ Me Me -N = 193 ~ 195 37 Me Me SO ₂ -NMe ₂ Me OMe -N = 175 ~ 177 38 Me Me SO ₂ -NMe ₂ OMe OMe -N = 190 ~ 193 39 Me Me SO ₂ -NMe ₂ Cl NMe ₂ -N = 213 ~ 216 40 Me H 2,4-C l ₂ Bnz Me Me -CH = 199 to 201 41 Me H 2,4-Cl ₂ Bnz Me OMe -CH = 185 to 188 42 Me H 2,4-Cl ₂ Bnz OMe OMe -CH = 168 to 170 43 Me H 2,4-Cl ₂ Bnz Me OMe -N = 178 to 180 ────────────────────────────────────

[0032]

[Table 3] [Continued Table 1] ─────────────────────────────────── Compound melting point No. . A B D X Y Z (° C) ─────────────────────────────────── 44 Me H 2, 4-Cl ₂ Bnz OMe OMe -N = 174 to 177 45 Me H 2,4-Cl ₂ Bnz Me Me -N = 183 to 186 46 Me Me COOMe Me Me CH = 202 to 204 47 Me Me COOMe Me OMe CH = 198 ~ 200 48 Me Me COOMe OMe OMe CH = 159 ~ 161 49 Me Me COOMe Me OMe -N = 169 ~ 171 50 Me Me COOMe OMe OMe -N = 173 ~ 175 51 Me Me COOEt Me Me CH = 189 ~ 191 52 Me Me COOEt Me OMe CH = 183 to 185 53 Me Me COOEt OMe OMe CH = 144 to 146 54 Me Me COOEt Me Me -N = 169 to 171 55 Me Me COOEt Me OMe -N = 162 to 164 56 Me Me COOEt OMe OMe -N = 166 to 167 57 Me Me COOEt Me Cl CH = 185 to 188 58 Ph H COOEt Me Cl CH = 160 to 162 59 Ph H COOEt OMe OMe CH = 183 to 185 60 Ph H COOEt Me OMe -N = 147 ~ 150 61 Ph H COOEt OMe OMe -N = 152 ~ 155 62 HH COOEt Me Me CH = 200 ~ 203 63 H H COOEt Me OMe CH = 188 to 190 64 HH COOEt OMe OMe CH = 189 to 191 ──────────────────────────────── ────

[0033]

[Table 4] [continued from Table 1] ──────────────────────────────────── Compound melting point No. . A B D X Y Z (℃) ─────────────────────────────────── 65 HH COOEt Me OMe -N = 163 to 165 66 HH COOEt OMe OMe -N = 158 to 161 67 Me H COO-Bu-n Me OMe -CH = 109 to 124 68 Me H COO-Bu-n OMe OMe -CH = 122 to 129 69 Me H COO-Bu-n Me OMe -N = 110 ~ 117 70 Me H COO-Bu-n OMe OMe -N = 127 ~ 134 71 Me H Me OMe OMe -CH = 199 ~ 201 72 Me H Me Me OMe- N = 125 ~ 130 73 Me H Br Me OMe -CH = 123 ~ 132 74 Me H Br OMe OMe -CH = 198 ~ 202 75 Me H Br Me OMe -N = 133 ~ 137 112 Et H COOEt OMe OMe -CH = 154 ~ 158 113 Pr-i H COOEt OMe OMe -CH = 151 ~ 154 114 Bu-t H COOEt OMe OMe -CH = 172 ~ 173 115 Me H SO ₂ -NMe ₂ Me OMe -CH = 194 ~ 196 116 Me H SO ₂ -NMe ₂ OMe OMe -CH = 183 to 185 117 Ph HH OMe OMe -CH = 165 to 167 118 Ph HH Me Me -CH = 169 to 171 119 HH Br Me Me -CH = 198 to 200 120 H H Br Me OMe -CH = 180 to 183 121 HH Br OMe OMe -CH = 191 to 193 ────────────────────────────── ────── Me: Methyl group Et: Ethyl group Pr-i: Isopropyl group
2,4-Cl ₂ Bnz: 2,4-dichlorobenzoyl group Ph: Phenyl group Bu-n: n-butyl group Bu-t: t-butyl group.

[Table 2]

[0035]

[Chemical 7]

[0036]

[Table 5] ─────────────────────────────────── Compound melting point No. A B R X Y Z (℃) ─────────────────────────────────── 76 Me HH OMe OMe -CH = 232〜238 77 Me H Et Me OEt -CH = 149 ~ 150 78 Me H Et Me Cl -N = 167 ~ 168 79 Me H Pr-n Me Me -CH = 139 ~ 140 80 Me H Pr-n Me OMe -CH = 162 ~ 167 81 Me H Pr-n OMe OMe -CH = 167 to 168 82 Me H Pr-n OMe OMe -N = 126 to 129 83 Me H Pr-i Me Me -CH = 172 to 175 84 Me H Pr-i Me OMe -CH = 156 to 159 85 Me H Pr-i OMe OMe -CH = 158 to 160 86 Me H Pr-i Me Me -N = 142 to 146 87 Me H Pr-i Me OMe -N = 160 to 163 88 Me H Pr-i OMe OMe -N = 160 to 162 89 Me H CH ₂ CH ₂ Cl Me OMe -CH = 177 to 179 90 Me H CH ₂ CH ₂ Cl OMe OMe -CH = 188 to 190 91 Me H CH ₂ CH = CH ₂ Me Me -CH = 139 to 144 92 Me H CH ₂ CH = CH ₂ Me OMe -CH = 145 to 147 ────────────────────── ─────────────

[0037]

[Table 6] [Continued Table 2] ─────────────────────────────────── Compound melting point No. . A BR X Y Z (° C) ─────────────────────────────────── 93 Me H CH ₂ CH = CH ₂ OMe OMe -CH = 159 to 163 94 Me H CH ₂ CH = CH ₂ Me OMe -N = 102 to 105 95 Me H CH ₂ CH = CH ₂ OMe OMe -N = 138 to 140 96 Me H CH ₂ C ≡ CH OMe OMe -CH = 159 to 160 97 Me H CH ₂ Ph OMe OMe -CH = 171 to 172 98 Me HC ₂ H ₄ OEt OMe OMe -CH = 99 to 102 99 Me H CH ₂ COOEt OMe OMe- CH = 143 ~ 147 100 Me Et Et Me Me -CH = 163 ~ 165 101 Me Et Et Me OMe -CH = 161 ~ 162 102 Me Et Et OMe OMe -CH = 148 ~ 150 103 Me Et Et Me Me -N = 156 ~ 159 104 Me Et Et Me OMe -N = 130 ~ 133 105 Me Et Et OMe OMe -N = 145 ~ 147 106 Bu-n H Et Me Me -CH = 156 ~ 159 107 Bu-n H Et Me OMe- CH = 148 ~ 151 108 Bu-n H Et OMe OMe -CH = 171 ~ 175 109 Bu-n H Et Me Me -N = 150 ~ 153 110 Bu-n H Et Me OMe -N = 148 ~ 152 111 Bu- n H Et O Me OMe -N = 135 to 140 ─────────────────────────────────── The compound of the present invention is used as a herbicide. In applying, generally, a suitable carrier, for example, solid carrier such as clay, talc, bentonite, diatomaceous earth or the like, water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorine It can be used by mixing it with a liquid carrier such as modified hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.), and if desired, emulsifier, dispersant, suspension. The agent, penetrant, spreading agent, stabilizer and the like can be added to the composition for practical use in any dosage form such as liquid, emulsion, wettable powder, powder and granule.

Next, examples of blending a herbicide containing the compound of the present invention as an active ingredient are shown, but the present invention is not limited thereto. In the following formulation examples, "part" means part by weight. Formulation Example 1 Wettable powder Compound No. 3 of the present invention: 50 parts Dikrite A: 46 parts (Kaolin clay: product name of Zikrite Industry Co., Ltd.) Solpol 5039: 2 Part (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)… 2 parts (white carbon: Shionogi Pharmaceutical Co., Ltd. trade name) The above is uniformly mixed and pulverized to obtain a wettable powder. Upon use, the wettable powder is diluted 50 to 50,000 times and sprayed so that the amount of the active ingredient is 0.005 kg to 10 kg per hectare.

Formulation Example 2 Wettable powder Compound of the present invention No. 8 ............ 75 parts Di-Crite A ............ 19 parts (Kaolin clay: product name of Siglite Industrial Co., Ltd.) Solpol 5039 ...... 2 parts (mixture of nonionic surfactant and anionic surfactant: trade name of Toho Chemical Co., Ltd.) Carplex (anti-caking agent)… 4 parts (white carbon: Shionogi & Co., Ltd.) Brand name) Mix the above uniformly and pulverize to make wettable powder.

Formulation Example 3 Wettable powder Compound of the present invention No. 12: 50 parts Dikrite A: 46 parts (Kaolin clay: trade name of Sikhlite Industry Co., Ltd.) Solpol 5039 …… 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)… 2 parts (white carbon: Shionogi Pharmaceutical Co., Ltd.) Brand name) Mix the above uniformly and pulverize to make wettable powder.

Formulation Example 4 Wettable powder Compound of the present invention No. 50 ............ 25 parts Dikrite A ............ 71 parts (Kaolin-based clay: trade name of Sikhlite Industry Co., Ltd.) Solpol 5039 ...... 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)… 2 parts (white carbon: Shionogi Pharmaceutical Co., Ltd.) Brand name) Mix the above uniformly and pulverize to make wettable powder.

Formulation Example 5 Wettable powder Compound of the present invention No. 54 ............ 50 parts Dikrite A ............ 44 parts (Kaolin clay: trade name of Sikhlite Industry Co., Ltd.) Solpol 5039 ...... ...... 4 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)… 2 parts (white carbon: Shionogi Pharmaceutical Co., Ltd.) Brand name) Mix the above uniformly and pulverize to make wettable powder.

Blending Example 6 Wettable powder Compound of the present invention No. 55 ............ 45 parts Dikrite A ............ 51 parts (Kaolin-based clay: trade name of Sikhlite Industry Co., Ltd.) Solpol 5039 ...... ...... 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)… 2 parts (white carbon: Shionogi Pharmaceutical Co., Ltd.) Brand name) Mix the above uniformly and pulverize to make wettable powder.

Formulation Example 7 Wettable powder Compound of the present invention No. 49 ………… 2 parts Xylene ………… 78 parts Dimethylformamide ………… 15 parts Solpol 2680 ………… 5 parts (nonionic interface Mixture of activator and anionic surfactant: Toho Chemical Co., Ltd. trade name) The above is uniformly mixed to form an emulsion. In use, the above emulsion is diluted 10 to 10,000 times and sprayed so that the amount of the active ingredient is 0.005 kg to 10 kg per hectare.

Formulation Example 8 Flowable compound of the present invention No. 56 ............ 25 parts Agrisol S-710 ............ 10 parts (Nonionic surfactant: Kao Atlas Co., Ltd. trade name) Lunox 1000C 0.5 part (Anionic surfactant: Toho Chemical Co., Ltd. product name) 1% Rhodopol water ............ 20 parts (Thickener: Lone Poulean company product name) Water ............ 44.5 The above parts are uniformly mixed to obtain a flowable agent.

Compounding Example 9 Granules Compound of the present invention No. 52 ............ 0.1 part Bentonite ………… 55.0 parts Talc ………… 44.9 parts After uniformly mixing and grinding the above, Add a small amount of water, knead with stirring and kneading, granulate with an extrusion granulator, and dry to give granules.

Formulation Example 10 Granules Compound of the present invention No. 53: 0.5 part Bentonite: 55.0 parts Talc: 44.5 parts After uniformly mixing and grinding the above, Add a small amount of water, knead with stirring and kneading, granulate with an extrusion granulator, and dry to give granules.

Formulation Example 11 Granules Compound of the present invention No. 55: 1.0 part Bentonite: 55.0 parts Talc: 44.0 parts After uniformly mixing and grinding the above, Add a small amount of water, knead with stirring and kneading, granulate with an extrusion granulator, and dry to give granules.

If desired, the compound of the present invention may be mixed with other herbicides, various insecticides, fungicides, synergists and the like at the time of preparation or spraying. Examples of the above-mentioned other types of herbicides include compounds described in Farm Chemicals Handbook 68th edition (1982).

The compound of the present invention can be applied to the control of various weeds in non-agricultural fields such as sports fields, open spaces, and track ends, as well as agricultural and horticultural fields such as upland fields, paddy fields and orchards.
The applied dose varies depending on the application scene, application time, application method, target grass species, cultivated crops, etc., but in general, the amount of the active ingredient is preferably about 0.005 to 10 kg per hectare.

Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples. Test Example-1 Herbicidal Effect Test by Soil Treatment A sterilized diluvial soil was put in a plastic box having a length of 15 cm, a width of 22 cm, and a depth of 6 cm.
Cyperaceae, koa kaza, purslane, syringa,
The red peppers were mixed-sown and covered with soil for about 1.5 cm, and then uniformly sprayed on the soil surface so that the amount of the active ingredient was a predetermined ratio.

The chemical solution for spraying was prepared by diluting the wettable powder of the above formulation example with water and spraying it over the entire surface with a small spray. Four weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the following criteria. The results are shown in Table 3. Some of the compounds of this invention are selective for certain crops.

Criteria 5 ... Herbicide rate 90% or more (almost complete death) 4 ... Herbicide rate 70-90% 3 ... Herbicide rate 40-70% 2 ... Herbicide rate 20-40% 1 ... Herbicide rate 5-20% 0 ... Herbicidal rate 5% or less (almost no effect) However, the above-mentioned herbicidal rate is obtained by measuring the above-ground weed weight of the chemical treatment area and the above-ground weed weight of the untreated area by the following formula. is there. Herbicidal rate = [1- (above-ground fresh grass weight of treated area / above-ground fresh grass weight of untreated area)] x 100 Test Example-2 Herbicidal effect test by foliar treatment 15 cm long, 22 cm wide, 6 cm deep plastic The sterilized diluvial soil was put in a box, and seeds of rice, crabgrass, cyperaceae, koa kaza, syringa, dentaria, corn, soybean, wheat, and tomato were sowed in spots to cover about 1.5 cm of soil. 2-3 kinds of plants
When the leaf stage was reached, the active ingredients were sprayed evenly on the foliage so as to have a predetermined ratio.

The chemical solution for spraying was prepared by diluting the wettable powder of the above-mentioned formulation example with water and spraying it over the entire surface of the foliage of various weeds with a small spray. Four weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the criteria of Test Example-1. The results are shown in Table 4. Test Example 3 Herbicidal effect test in submerged condition After alluvial soil was put in a 1/5000 are Wagner pot, water was added to mix it to obtain a fresh water condition of a water depth of 2 cm. The seeds of the sea urchin, the Japanese eel, the azalea, the yellow cypress, and the firefly were mixed-sown in the above-mentioned pot, and further tubers of Urikawa, Mizugaya-tsuri, and Kurogui were placed. Further, rice seedlings at the 2.5 leaf stage were transplanted. The next day, the drug diluted solution was dropped on the water surface with a measuring pipette so that a predetermined amount of the drug was obtained.

The herbicidal effect on various weeds was examined 3 weeks after the dropping of the drug according to the criteria of Test Example 1. The results are shown in Table 5.

[0056]

[Chemical 8]

[0057]

[Table 7] [Table 3] ──────────────────────────────────────────────────────────────────────────────────────────────── Amount of processed chemical compound No. kg / ha No. kg / ha Amount of chemical compound ──────────────────────────────────────────────────────────────────────────────────────────────────────────────── ─────────────────────────── No.1 0.16 5 5 5 5 5 5 5 5 5 No.1 0.08 4 4 4 5 4 4 4 4 No. 2 0.16 5 5 5 5 5 5 5 5 5 No. 2 0.08 5 5 5 5 5 5 5 5 5 No. 3 0.16 5 5 5 5 5 5 5 5 5 No. 3 0.08 5 5 5 5 5 5 5 5 5 5 No.4 0.16 5 5 5 5 5 5 5 5 5 5 No.4 0.08 5 5 4 5 5 5 5 5 5 No. 5 0.16 5 5 5 5 5 5 4 5 4 No. 5 0.08 5 4 5 5 4 4 5 4 No. 6 0.16 5 5 5 5 5 5 5 5 5 No. 6 0.08 4 4 4 5 4 4 4 No. 7 0.16 5 5 5 5 5 5 5 5 5 5 No. 7 0.08 5 5 5 5 5 5 5 5 5 5 No. 8 0.16 5 5 5 5 5 5 5 5 5 5 No. 8 0. 08 5 5 5 5 5 5 5 5 5 ────────────────────────────────────

[0058]

[Table 8] [Continued in Table 3] ─────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────── Amount of chemical compound Amount of processed compound Escarica Gabariza Himaera No. kg / ha Guisagi Saku ─────── ───────────────────────────── No. 9 0.16 5 5 5 5 5 5 5 5 5 No. 9 0.08 5 4 4 5 4 5 5 5 No.10 0.16 5 5 5 5 5 5 4 5 5 No.10 0.08 5 4 5 5 4 3 4 4 4 No.12 0.16 5 5 4 5 5 5 5 5 5 No .12 0.08 5 5 4 5 5 5 5 5 4 No.17 0.16 5 5 5 5 5 5 5 5 5 5 No.17 0.08 5 5 5 5 4 5 5 5 4 No.32 0.16 5 5 5 5 5 5 5 5 5 No.32 0.08 5 5 5 5 5 5 5 5 5 5 No.33 0.16 5 5 5 5 5 5 5 5 5 No.33 0.08 5 5 5 5 5 5 5 5 5 No.38 0.16 5 5 5 5 5 5 5 5 5 5 No.38 0.08 5 5 5 5 5 5 5 5 5 5 No.46 0.16 5 5 5 5 5 5 5 5 5 No.46 0. 08 5 5 5 5 5 5 4 5 5 ────────────────────────────────────

[0059]

[Table 9] [Continued Table 3] ───────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────── Amount of chemical compound Amount of processed compound Escarica Gabariza Himaera No. kg / ha Guisagi Saku ─────── ───────────────────────────── No.47 0.16 5 5 5 5 5 5 5 5 5 No.47 0.08 5 5 5 5 5 5 5 5 5 No.48 0.16 5 5 5 5 5 5 5 5 5 No.48 0.08 5 5 5 5 5 5 5 5 5 No.49 0.16 5 5 5 5 5 5 5 5 5 5 No .49 0.08 5 5 5 5 5 5 5 5 5 5 No.50 0.16 5 5 5 5 5 5 5 5 5 No.50 0.08 5 5 5 5 5 5 5 5 5 No.51 0.16 4 5 5 5 5 5 5 5 No.51 0.08 3 5 5 5 5 5 5 5 5 No.52 0.16 4 5 5 5 5 5 5 5 5 No.52 0.08 3 5 5 5 5 5 5 5 No.53 0.16 4 5 5 5 5 5 5 5 5 No.53 0.08 3 5 5 5 5 5 5 4 4 No.58 0.16 5 5 5 4 5 5 5 5 5 5 No.58 0.08 5 5 3 5 5 5 5 5 5 5 ────────────────────────────────────

[0060]

[Table 10] [Continued in Table 3] ────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────── Amount of chemical compound Amount of processed compound Escarica Gabariza Himaera No. kg / ha Guisagi Saku ─────── ───────────────────────────── No.59 0.16 5 5 4 5 5 5 5 5 5 No.59 0.08 5 5 4 5 5 5 5 5 5 No.60 0.16 5 4 0 5 5 5 5 5 5 No.60 0.08 5 4 0 5 5 5 4 5 5 No.63 0.16 5 5 5 5 5 5 5 5 5 No .63 0.08 5 5 5 5 5 5 5 5 5 5 No.64 0.16 5 5 5 5 5 5 5 5 5 5 No. 64 0.08 5 5 5 5 5 5 5 5 5 No.71 0.16 5 5 5 5 5 5 5 5 No.71 0.08 4 5 5 5 5 5 5 5 5 No.80 0.16 5 5 5 5 5 5 5 5 5 No.80 0.08 5 5 4 4 5 5 5 5 No.81 0.16 5 5 4 5 5 5 5 5 5 No.81 0.08 5 5 4 5 5 5 5 5 5 No.88 0.16 5 5 4 5 5 5 5 5 5 No.88 0.8. 08 5 5 4 5 5 5 5 5 5 ────────────────────────────────────

[0061]

[Table 11] [continued from Table 3] ──────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────── Amount of chemical compound Amount of processed compound Escarica Gabariza Himaera No. kg / ha Guisagi Saku ─────── ───────────────────────────── No.89 0.16 5 5 5 5 5 5 5 5 5 No.89 0.08 4 5 4 5 5 5 5 5 5 No.90 0.16 5 5 5 5 5 5 5 5 5 No.90 0.08 5 5 5 5 5 5 5 5 5 No.92 0.16 5 5 5 5 5 5 5 5 5 5 No .92 0.08 5 5 5 5 5 5 5 5 5 5 No.93 0.16 5 5 5 5 5 5 5 5 5 5 No.93 0.08 5 5 5 5 5 5 5 5 5 No. 96 0.16 5 5 5 5 5 5 5 5 No.96 0.08 4 5 5 5 5 5 5 5 5 No.98 0.16 5 5 5 5 5 5 5 5 5 No.98 0.08 5 5 5 5 5 5 5 5 No.101 0.16 1 5 5 5 5 5 3 5 5 No.101 0.08 1 5 4 5 5 5 3 5 5 No.102 0.16 3 5 5 5 5 5 5 5 5 No.102 0. 08 2 5 5 5 5 5 5 5 5 ────────────────────────────────────

[0062]

[Table 12] [Continued in Table 3] ────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────── Amount of chemical compound Amount of processed compound Escarica Gabariza Himaera No. kg / ha Guisagi Saku ─────── ───────────────────────────── Control Compound A 0.16 3 2 2 4 3 2 2 3 3 Control Compound A 0.082 0 1 4 1 1 1 1 3 Control compound B 0.16 4 4 3 3 4 3 4 4 Control compound B 0.08 3 3 3 1 3 2 3 3 Control compound C 0.16 3 2 2 4 3 2 2 3 Control Compound C 0.08 2 1 1 2 1 1 1 1 2 Control compound D 0.16 5 4 4 4 3 3 3 4 Control compound D 0.08 4 3 4 3 3 3 3 3 3 3 ────────── ────────────── ───────────

[0063]

[Table 13] [Table 4] ───────────────────────────────────────────────────────────────────────────────────── Kakoite Da Kotone Nehiya Aki Nu ｜ Imma Compound Treatment Amount Shigada Gamozu Gito Bari Zameraro No. kg / ha ────────────────────────────────── No. 1 0.15 5 5 5 5 5 5 5 5 5 2 5 No. 1 0.08 5 4 5 5 5 5 5 5 5 5 1 4 No. 2 0.16 5 5 5 5 5 5 5 5 5 5 4 5 No. 2 0.08 5 4 5 5 5 5 5 5 5 5 3 5 No. 3 0.16 5 5 5 5 5 5 5 5 5 2 5 No. 3 0.08 4 4 5 5 5 5 5 5 5 1 4 No. 4 0.16 5 4 5 5 5 5 5 5 5 5 2 3 No. 4 0 .08 4 3 5 5 5 5 5 5 5 0 1 No. 5 0.16 5 5 5 5 5 5 5 5 5 5 3 5 No. 5 0.04 4 4 5 5 4 4 5 2 4 No.6 0.16 5 4 5 5 5 5 5 5 5 2 5 No.6 0.08 5 3 5 5 5 5 5 5 5 1 4 No.7 0.16 5 5 5 5 5 5 5 5 5 3 5 No. 7 0.08 5 4 5 5 5 5 5 5 5 2 3 No. 8 0.16 5 4 5 5 5 5 5 5 5 2 4 No. 8 0.08 4 3 5 5 5 5 5 5 5 1 2 ────────────────────────────────────

[0064]

[Table 14] [Continued Table 4] ──────────────────────────────────── The active ingredient of the present invention Ikamakohaito Dacotone Hiya Akinu ｜ Imma compound processing amount Shitada gamozu Gitobariza zararo No. kg / ha Guigico saks ─────────────────────────────────── No. 9 0.16 4 3 5 5 5 5 5 5 5 2 3 No. 9 0.08 3 2 5 5 4 5 4 4 4 0 1 No. 10 0.16 5 3 5 5 5 5 5 5 5 2 5 No. 10 0.08 4 3 5 5 4 5 4 4 4 4 1 4 No.46 0.15 5 5 5 5 5 5 5 5 5 5 5 5 No.46 0.08 4 5 5 5 5 5 5 5 5 5 5 5 No.47 0.16 5 5 5 5 5 5 5 5 5 5 5 5 No. 47 0.08 4 5 5 4 4 4 2 5 5 5 3 No. 48 0.16 4 5 5 5 5 5 5 5 5 5 5 5 No. 48 0.08 3 5 4 5 5 5 5 5 5 5 No.49 0.16 5 5 5 5 5 5 5 5 5 5 5 No.49 0.08 4 5 5 4 5 5 5 5 5 5 5 No.50 0.16 5 5 5 5 5 5 5 5 5 5 5 5 No. 50 0.08 4 5 5 5 4 5 5 5 5 5 5 4 No. 51 0.16 4 4 5 5 5 5 5 5 5 4 4 No. 51 0.08 3 4 5 5 5 4 3 4 3 3 ───────────────────────────────────

[0065]

[Table 15] [Continued Table 4] ─────────────────────────────────── The active ingredient of the present invention Ikamakohaito Dacotone Hiya Akinu ｜ Imma compound processing amount Shitada gamozu Gitobariza zararo No. kg / ha Guigico saks ─────────────────────────────────── No.52 0.16 4 4 5 4 5 5 5 5 5 5 3 No. 52 0.08 3 4 5 3 5 5 4 4 5 4 2 No. 53 0.16 4 4 5 3 3 5 4 5 5 2 3 No. 53 0.08 3 4 5 3 5 5 3 5 5 2 3 No.63 0.16 4 5 5 5 4 5 5 5 5 5 5 5 No.63 0.08 3 5 5 5 2 5 5 5 5 5 5 5 No.64 0.16 5 5 5 5 5 5 5 5 5 5 5 5 No. 64 0.08 4 5 5 5 5 4 5 5 5 5 5 5 No.90 0.16 4 4 5 5 5 5 5 5 5 5 1 No.90 0.08 3 3 5 5 4 5 5 5 0 0 Reference compound A 0.16 4 4 4 4 4 4 4 4 4 2 Reference compound A 0.08 3 4 4 4 4 4 4 4 3 2 Reference compound B 0.16 3 3 3 3 3 3 3 3 4 2 2 Control Compound B 0.08 3 2 2 3 2 3 3 2 3 3 1 2 Control Compound D 0.16 3 4 3 3 4 3 3 3 3 2 2 Control Compound D 0.08 3 3 3 3 3 3 3 3 3 2 2 2 ───────────────────────────────────

[0066]

[Table 16] [Table 5] ──────────────────────────────────────────────────────────────────────────────────────────────────────────────── Amount of chemical compound Treatment amount of compound Nugina sewage No. kg / ha No. kg / ha Food ───────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────── ───────────────────────────── 2 0.04 0 5 5 5 5 5 5 5 5 5 5 2 0.02 0 5 5 5 5 5 5 5 5 5 5 2 0.001 0 4 5 5 5 5 5 5 5 5 5 3 0.04 0 5 5 5 5 5 5 5 5 5 3 3 0.02 0 5 5 5 5 5 5 5 5 5 5 3 3 0 01 0 4 5 5 5 5 5 5 5 5 7 0.04 0 5 5 5 5 5 5 5 5 5 7 7 0.02 0 5 5 5 5 5 5 5 5 5 7 7 01 0 4 5 5 5 5 5 5 5 5 5 8 0.04 0 5 5 5 5 5 5 5 5 5 8 0.02 0 5 5 5 5 5 5 5 5 5 5 8 0.0 0 4 5 5 5 5 5 5 5 5 5 46 0.02 1 5 5 5 5 5 5 5 5 5 5 46 0. 01 0 4 5 5 5 5 5 5 5 5 46 0.005 0 4 5 5 5 5 5 5 5 5 5 ── ──────────────────────────────────

[0067]

[Table 17] [Continued Table 5] ─────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────―― Itako Aki Hou Miku Nine Cateryzed Amount of compound processed Nugina Siru Kagag Biwa Iwa Yawa No. kg / ha Eza Tiri ──── ─────────────────────────────── 47 0.02 0 5 5 5 5 5 5 5 5 5 5 47 47 0.014 5 5 5 5 5 5 5 5 47 0.005 0 3 5 5 5 5 5 5 5 4 48 0.02 0 5 5 5 5 5 5 5 5 5 5 48 0. 01 0 4 5 5 5 5 5 5 5 5 5 48 0.005 0 3 5 5 5 5 5 5 5 5 4 49 0.04 0 5 5 5 5 5 5 5 5 5 5 49 0.02 0 5 5 5 5 5 5 5 5 5 49 0. 01 0 4 5 5 5 5 5 5 5 5 5 50 0 .04 0 5 5 5 5 5 5 5 5 5 5 50 0.02 0 5 5 5 5 5 5 5 5 5 5 50 0. 1 0 4 5 5 5 5 5 5 5 5 5 51 0.04 0 5 5 5 5 5 5 5 5 5 5 51 0.02 0 5 5 5 5 5 5 5 5 5 51 0 0.01 0 4 5 5 5 5 5 5 5 5 ─ ───────────────────────────────────

[0068]

[Table 18] [Continued in Table 5] ─────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────―― Itako Aki Hou Miku Nine Cateryzed Amount of compound processed Nugina Siru Kagag Biwa Iwa Yawa No. kg / ha Eza Tiri ──── ─────────────────────────────── 52 0.04 0 5 5 5 5 5 5 5 5 5 5 52 0.02 0 5 5 5 5 5 5 5 5 5 52 0.01 01 0 4 5 5 5 5 5 5 5 5 53 0.04 0 5 5 5 5 5 5 5 5 5 5 53 0.02 0 5 5 5 5 5 5 5 5 5 5 53 0.01 0 4 5 5 5 5 5 5 5 5 5 55 0.04 0 5 5 5 5 5 5 5 5 5 5 55 0.02 0 5 5 5 5 5 5 5 5 5 55 0. 01 0 4 5 5 5 5 5 5 5 5 5 56 0 .04 0 5 5 5 5 5 5 5 5 5 5 56 0.02 0 5 5 5 5 5 5 5 5 5 5 56 0.01 4 5 5 5 5 5 5 5 5 58 0.04 0 4 5 5 5 5 5 5 5 5 58 0.02 0 3 3 5 5 5 5 5 5 5 5 8 0.001 0 3 5 5 5 5 5 5 5 5 4 ─── ────────────────────────────────

[0069]

[Table 19] [Continued in Table 5] ──────────────────────────────────── The active ingredient of the present invention Itako Aki Hou Miku Nine Cateryzed Amount of compound processed Nugina Siru Kagag Biwa Iwa Yawa No. kg / ha Eza Tiri ──── ─────────────────────────────── 59 0.04 0 4 5 5 5 5 5 5 5 5 5 59 0.02 0 3 5 5 5 5 5 5 5 5 59 0.01 0 2 5 5 5 5 5 5 5 4 63 0.04 0 4 5 5 5 5 5 5 5 5 63 63 0.02 0 4 5 5 5 5 5 5 5 5 5 63 0.01 0 3 5 5 5 5 5 5 5 5 4 64 0.04 1 5 5 5 5 5 5 5 5 5 5 64 0.02 0 5 5 5 5 5 5 5 5 5 64 0. 01 0 4 5 5 5 5 5 5 5 5 4 71 0 .04 0 4 5 5 5 5 5 5 5 5 5 71 0.02 0 3 5 5 5 5 5 5 5 5 5 71 0.01 3 5 5 5 5 5 5 5 4 81 0.04 0 4 5 5 5 5 5 5 5 5 81 81 0.02 0 4 5 5 5 5 5 5 5 5 81 0.01 0 3 5 5 5 5 5 5 5 5 4 ─── ────────────────────────────────

[0070]

[Table 20] [Continued in Table 5] ──────────────────────────────────── The active ingredient of the present invention Itako Aki Hou Miku Nine Cateryzed Amount of compound processed Nugina Siru Kagag Biwa Iwa Yawa No. kg / ha Eza Tiri ──── ─────────────────────────────── 89 0.04 0 5 5 5 5 5 5 5 5 5 5 89 0.02 0 4 5 5 5 5 5 5 5 5 89 0.001 0 4 5 5 5 5 5 5 5 4 90 0.04 0 5 5 5 5 5 5 5 5 5 5 90 0.02 0 4 5 5 5 5 5 5 5 5 5 90 0.01 0 3 5 5 5 5 5 5 5 5 4 92 0.04 0 4 5 5 5 5 5 5 5 5 5 92 0.02 0 3 5 5 5 5 5 5 5 5 92 0. 01 0 3 5 5 5 5 5 5 5 5 4 93 0 .04 0 4 5 5 5 5 5 5 5 5 5 93 0.02 0 3 5 5 5 5 5 5 5 5 5 93 0.01 3 5 5 5 5 5 5 5 4 96 0.04 0 4 5 5 5 5 5 5 5 5 96 0.02 0 3 3 5 5 5 5 5 5 5 96 96.01 0 3 5 5 5 5 5 5 5 5 4 ─── ────────────────────────────────

[0071]

[Table 21] [Continued in Table 5] ──────────────────────────────────── The active ingredient of the present invention Itako Aki Hou Miku Nine Cateryzed Amount of compound processed Nugina Siru Kagag Biwa Iwa Yawa No. kg / ha Eza Tiri ──── ─────────────────────────────── 98 0.04 0 4 5 5 5 5 5 5 5 5 5 98 0.02 0 3 5 5 5 5 5 5 5 5 98 0.001 0 3 5 5 5 5 5 5 5 4 102 0.04 0 4 5 5 5 5 5 5 5 5 102 0.02 0 4 5 5 5 5 5 5 5 5 5 102 0.01 0 3 5 5 5 5 5 5 5 4 Control compound A 0.04 3 2 3 3 3 3 3 3 2 Control compound A 0.02 3 1 2 2 2 2 2 2 1 1 Control compound A 0.01 2 1 1 1 1 1 1 1 1 0 Control compound B 0.04 4 2 3 3 3 2 2 2 2 2 Reference compound B 0.02 3 1 2 2 2 2 2 1 2 1 Reference compound B 0.011 2 0 1 1 1 1 1 0 1 0 Control compound C 0.04 3 2 2 2 2 2 2 2 2 1 Reference compound C 0 .02 2 1 1 1 1 1 1 1 1 0 Control compound C 0.01 1 1 0 1 1 1 1 1 1 1 1 0 0 ────────────────────────── ───────────

[0072]

[Table 22] [Continued in Table 5] ──────────────────────────────────── The active ingredient of the present invention Itako Aki Hou Miku Nine Cateryzed Amount of compound processed Nugina Siru Kagag Biwa Iwa Yawa No. kg / ha Eza Tiri ──── ─────────────────────────────── Reference Compound D 0.04 4 2 3 3 3 2 3 3 2 2 Reference Compound D 0 .02 3 2 2 2 2 2 2 2 2 Control compound D 0.01 2 1 2 2 2 1 1 1 1 0 0 ──────────────────────── ───────────

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location C07D 307: 00) (72) Inventor Takashi Inoi 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Prefecture Nissan Kagaku Kogyo Biological Science Research Institute, Inc. (72) Inventor Toshihiko Oguchi 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Nissan Chemical Industry Co., Ltd. Biological Science Research Institute

Claims (1)

[Claims] 1. General formula (X-1): [Wherein A represents a hydrogen atom, a lower alkyl group or a phenyl group, B represents a hydrogen atom or a lower alkyl group, and D
Is a hydrogen atom, a lower alkyl group, COOR ₁ (R ₁ represents a hydrogen atom, a lower alkyl group, an allyl group, a propargyl group, a lower alkoxyalkyl group, a haloalkyl group, a lower alkoxycarbonylalkyl group or a benzyl group), CO
Ar (Ar represents a phenyl group which may be substituted with a halogen atom), a halogen atom, a nitro group or SO ₂ NR ₂ R
₃ (R ₂ and R ₃ each represent a lower alkyl group) and Q represents SO ₂ NH ₂ , SO ₂ NCO or SO ₂ NHCOOR ₄ (R ₄ represents a lower alkyl group or a phenyl group). . However, the case where A is a phenyl group, B is a methyl group, D is a chlorine atom and Q is SO ₂ NH ₂ is excluded. ] The 5-substituted pyrazole derivative represented by these.