JPH0680046B2 - Pyrazole sulfonylurea derivative, method for producing the same and herbicide containing the derivative - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel pyrazolesulfonylurea derivative, a method for producing the compound and a herbicide containing the compound as an active ingredient.

[0002]

2. Description of the Related Art JP-A-55-102577 and JP-A-56-139
Japanese Patent Laid-Open No. 466688 describes that a pyridinesulfonylurea derivative is useful, and Japanese Patent Laid-Open No. 56-169688 describes that a pyrrolesulfonylurea derivative is useful as a herbicide. On the other hand, conventional pyrazole derivatives include, for example, Japanese Patent Publication
54-36648, JP-A-54-41872, JP-A-57-2276, JP-A-57-58670 and JP-A-51-133265 may be useful as herbicides. Are known.

[0003]

SUMMARY OF THE INVENTION It is essential to use herbicides to protect important crops such as rice, wheat, corn and cotton from weed damage and to increase the yield. In particular, from the viewpoints of preventing environmental pollution, reducing economic costs in transportation, and spraying, research and exploration of compounds that have a high herbicidal effect with the lowest possible dose has been continued for many years. While some compounds with such properties are currently used as herbicides, there is still a need for new compounds with these properties.

Although the above-mentioned pyridinesulfonylurea derivatives and pyrrolesulfonylurea derivatives have excellent herbicidal effects at low doses, they are not always satisfactory, and some of the pyrazole derivatives conventionally known. Although it shows selectivity for rice, it requires a relatively high dose, which is not always satisfactory.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have studied the herbicidal properties of many compounds in order to produce compounds having higher herbicidal activity after many years of research to develop useful herbicides. . As a result, the compound of the present invention represented by the general formula (I) is used for many weeds in both soil treatment and foliage treatment, as compared with known pyridinesulfonylurea derivatives, pyrrolesulfonylurea derivatives and pyrazole derivatives. The present invention has been completed by finding that they also have extremely strong herbicidal activity and high safety against cotton, which is an important crop. Since the compound of the present invention exhibits a high herbicidal activity with a very low dose as compared with conventional herbicides, it is useful as a herbicide for cultivated land, low orchards and non-cultivated lands.

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]

[Wherein R, R ₁ , Me, X, Y and Z have the same meanings as described above. That is, the 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 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

[0009]

[Chemical 3]

[Wherein R, R ₁ , X, Y and Z have the same meanings as described above. R ₄ represents an alkyl group or a phenyl group. That is, the pyrazole sulfonamide derivative (IV) is reacted with a chloroformate or carbonate in the presence of a base such as potassium carbonate in a solvent such as acetone or methyl ethyl ketone, and after the reaction, the compound (VI) is treated with an acidic substance such as hydrochloric acid. ) Get. 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

[0011]

[Chemical 4]

[In the formula, R, R ₁ and Me have the same meanings as described above, E and F represent a halogen atom, R ₅ represents a lower alkyl group, and G represents a nitrogen atom or a ═CH— group. With reference to JP-A-56-154471, a compound (VIII) which is a part of the compound of the present invention was synthesized by reacting a pyrazole sulfonamide derivative (IV) with a pyrimidine or triazine isocyanate (VII). 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 can be synthesized by synthesizing pyrazole sulfonamide by the method described below, and further by referring to the method described in JP-A-55-13266. Although the intermediate pyrazole sulfonamide is also a novel compound,
The synthesis can be performed by the synthetic route described below.

[0013]

[Chemical 5]

[Wherein R, R ₁ and Me have the same meanings as described above. ]

[0015]

[Chemical 6]

[Wherein R ₁ and Me have the same meanings as described above. ]

[0017]

EXAMPLES A synthetic example of an intermediate pyrazole sulfonamide used in the present invention will be described below as a reference example.

Reference Example 1 Synthesis of 1-methylpyrazole-3-sulfonamide 32 g of 1-methyl-3-aminopyrazole, 12 concentrated hydrochloric acid
An aqueous solution of 34.1 g of sodium nitrite was added to a mixed solution of 0 ml and 40 ml of acetic acid at -10 ° C to 0 ° C. This solution was stirred at -5 ° C for 30 minutes, and then in small portions, a sulfurous acid gas-saturated acetic acid solution containing 6.7 g of cuprous chloride 44.
0 ml was added dropwise at -10 to -5 ° C. 4 at 0-5 ° C after dropping
After stirring for an hour, it was poured into ice-cooled water and extracted with ether. The extract was thoroughly washed with water and a saturated aqueous solution of sodium hydrogen carbonate, dried and the solvent was distilled off to obtain 20.8 g of crude sulfonyl chloride. The sulfonyl chloride obtained here is dissolved in 50 ml of tetrahydrofuran, and this is dissolved in 28% ammonia water at a temperature of 10 ° C or lower.
50 ml was added under ice cooling. After 3 hours of stirring at room temperature, the solid obtained by concentrating under reduced pressure was filtered, washed with water and hexane, and dried to obtain 14.2 g of the desired product. Melting point 15
6 ~ 158 ℃

Reference Example 2 4-methoxycarbonyl-1-methylpyrazole-3-
Synthesis of sulfonamide Synthesized from methyl 3-amino-1-methylpyrazole-4-carboxylate according to Reference Example 1. Melting point 191-194 ° C

Reference Example 3 4-Ethoxycarbonyl-1-methylpyrazole-3-
Synthesis of sulfonamide It was synthesized from ethyl 3-amino-1-methylpyrazole-4-carboxylate according to Reference Example 1. Melting point 149-151 ° C

Reference Example 4 Synthesis of 4 -chloro-1-methylpyrazole-3-sulfonamide 32 g of 1-methyl-3-aminopyrazole, concentrated hydrochloric acid 12
An aqueous solution of 34.1 g of sodium nitrite was added to a mixed solution of 0 ml and 40 ml of acetic acid at -10 ° C to 0 ° C. This solution was stirred at -5 ° C for 30 minutes, and then in small portions, a sulfurous acid gas-saturated acetic acid solution containing 6.7 g of cuprous chloride 44.
0 ml was added dropwise at -10 to -5 ° C. 4 at 0-5 ° C after dropping
After stirring for a period of time, it was poured into ice water and extracted with ether. The extract was thoroughly washed with water and a saturated aqueous solution of sodium hydrogen carbonate, dried and the solvent was distilled off to obtain 20.8 g of 1-methylpyrazole-3-sulfonyl chloride. (Boiling point 120 ° C./0.1 mmHg) 8 g of sulfuryl chloride was added to 4 g of the sulfonyl chloride obtained here, and the mixture was heated and stirred at 70 to 80 ° C. for 4 hours. The crude 4-chloro-1-methylpyrazole-3-sulfonyl chloride obtained was dissolved in 4 ml of tetrahydrofuran and added with 28% ammonium water 4% at a temperature below 10 ° C.
ml was added dropwise. After stirring for 3 hours at room temperature, the solid obtained by concentrating under reduced pressure was filtered, washed with water and benzene, and then dried to obtain 3 g of the desired product. Melting point 173-180 ° C

Reference Example 5 Synthesis of 4-bromo-1-methylpyrazole-3-sulfonamide 1-methyl-3-aminopyrazole 9.7 g,
16 g of bromine was dropped into a solution of 40 ml of acetic acid 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.
Recrystallized with a mixed solvent of benzene and hexane to give 3-amino-
10 g of 4-bromo-1-methylpyrazole was obtained. Melting point 100 ° C. to 102 ° C. Then, an aqueous solution of 3.6 g of sodium nitrite is added to a mixed solution of 8.8 g of the above-mentioned aminopyrazole, 17.5 ml of concentrated hydrochloric acid, 5 ml of phosphoric acid, and -10 ° C. to 0 ° C. added. The solution was stirred at -5 ° C for 30 minutes and then added portionwise in portions to 70 ml of a sulfurous acid gas saturated acetic acid solution containing 1.0 g of cuprous chloride at 0-10 ° C. After the dropping, the mixture was stirred at room temperature for 1 hour, then poured into ice water and extracted with ether. The extract was washed with water, dried and the solvent was distilled off to obtain 10.0 g of a crude solid sulfonyl chloride. The sulfonyl chloride obtained here is dissolved in 10 ml of tetrahydrofuran and 28% at a temperature of 10 ° C or lower.
20 ml of ammonia water was added dropwise. After stirring for 1 hour at room temperature,
The solid obtained by concentration under reduced pressure was filtered, washed with water and hexane, and dried to obtain 7.7 g of the desired product. Melting point 195-197 ° C

Reference Example 6 Synthesis of 4-bromo-1,5-dimethylpyrazole-3-sulfonamide According to the method of Reference Example 5, 3-amino-1,5-dimethylpyrazole was converted into 3-amino-4-bromo -1,5-dimethylpyrazole (mp 111-113 ° C) was synthesized and then
I got the object. Melting point 213 to 217 ° 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 6, but the present invention is not limited thereto.

Example 1 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl) -4-ethoxycarbonyl-1-methylpyrazole-3-sulfonamide 4-ethoxycarbonyl-1-methylpyrazole -3-
Sulfonamide 7.8g, dry potassium carbonate 6.90g
To a mixture of 70 ml of acetone in Example 4, 4.00 g of n-butyl isocyanate was added 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 obtain 10.7 g of N- (n-butylcarbamoyl) -4-ethoxycarbonyl-1-methylpyrazole-3-sulfonamide. Melting point 124-
125 ° C.

Then, this was added to 120 ml of dry toluene, and 9.6 g of phosgene was blown in while heating under reflux, followed by heating under reflux for another 1.5 hours. After completion of the reaction, the mixture was concentrated under reduced pressure to obtain a crude sulfonyl isocyanate. 1.0 g of this crude sulfonyl isocyanate was added to a solution of 400 mg of 2-amino-4,6-dimethoxypyrimidine in 20 ml of dry acetonitrile, and the mixture was stirred at room temperature. The crystals formed are filtered off, washed,
By drying, 1.0 g of the target product was obtained. Melting point 150
˜152 ° C. Example 2 N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-bromo-1-methylpyrazole-3
Synthesis of Sulfonamide 4-Bromo-1-methylpyrazole-3-sulfonamide 7.7 g, dry potassium carbonate 6.60 g Acetone 7
3.16 g of n-butyl isocyanate was added to 0 ml of the mixture 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, and the insoluble material was filtered. The filtrate is acid-precipitated with hydrochloric acid, and the precipitated crystals are separated by filtration, washed with water,
Dried N- (n-butylcarbamoyl) -4-bromo-
9.3 g of 1-methylpyrazole-3-sulfonamide was obtained.

Then, this was added to 100 ml of dry toluene, 8.1 g of phosgene was blown thereinto under heating under reflux, and the mixture was further heated under reflux for 1.5 hours. After completion of the reaction, the mixture was concentrated under reduced pressure to obtain a crude sulfonyl isocyanate. 1.3 g of this crude sulfonyl isocyanate was added to a solution of 0.59 g of 2-amino-4,6-dimethoxypyrimidine in 5 ml of dry acetonitrile, and the mixture was stirred at room temperature for 3 hours and then heated under reflux for 5 minutes.
The crystals formed were filtered off, washed and dried to obtain 0.8 g of the desired product. Melting point 148 to 152 ° C. Next, the physical properties of the compounds synthesized according to the above Examples are shown below in Tables 1 and 2 together with the compounds synthesized in the Examples, but the compounds of the present invention are not limited to these. Absent. However, the symbols have the following meanings. Me: methyl group Et: represents an ethyl group.

Table 1

[0028]

[Chemical 7]

[0029]

[Table 1] ─────────────────────────────────── Compound No. RXYZ Melting point (℃) ── ───────────────────────────────── 1 H Me Me CH 212〜215 2 H Me OMe CH 185〜186 3 H OMe Oh CH 182-183 4 H Me Me N 182-184 5 H Me OMe N 176-180 6 H OMe OMe N 181-184 7 H Me Cl CH 195-197 8 H Me Cl CCH ₂ CH ₂ Cl 204- 206 9 H Me OCH ₂ CH ₂ C 211 ~ 213 10 H NMe ₂ Cl N 197 ~ 200 11 COOMe Me Me CH 184 ~ 187 12 COOMe Me OMe CH 182 ~ 185 13 COOMe OMe OMe CH 187 ~ 190 14 COOMe Me OMe N 182-185 15 COOMe OMe OMe N 186-189 16 COOEt Me Me CH 159-161 17 COOEt Me OMe CH 154-156 18 COOEt OMe OMe CH 150-152 19 COOEt Me Cl CH 180-182 20 COOEt Me Me N 144- 146 21 COOEt Me OMe N 130 to 135 22 COOEt OMe OMe N 157 to 159 23 Cl Me Me CH ───────────────────────────── ───────

[0030]

[Table 2] Table 1 (continued) ─────────────────────────────────── Compound No. RXYZ Fusion Point (℃) ─────────────────────────────────── 24 Cl Me OMe CH 182〜186 25 Cl OMe OMe CH 180 ~ 186 26 Cl Me OMe N 132 ~ 137 27 Cl OMe OMe N 147 ~ 152 28 Br Me Me CH 196 ~ 204 29 Br Me OMe CH 172 ~ 178 30 Br OMe OMe CH 148 ~ 152 31 Br Me OMe N 151 to 158 32 Br OMe OMe N 165 to 172 ─────────────────────────────────── Table 2

[0031]

[Chemical 8]

[0032]

[Table 3] ─────────────────────────────────── Compound No. RXYZ Melting point (℃) ── ───────────────────────────────── 33 Br Me OMe CH 184-187 34 Br OMe OMe CH 174-177 35 Br Me OMe N 168 to 173 36 Br OMe OMe N 165 to 170 ───────────────────────────────────── In applying the compound of the present invention as a herbicide, generally, a suitable carrier, such as clay, talc, bentonite, a solid carrier such as diatomaceous earth or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, Mixed with liquid carriers such as toluene and xylene), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.) If desired, an emulsifying agent, a dispersing agent, a suspending agent, a penetrating agent, a spreading agent, a stabilizer, etc. may be added to give an arbitrary dosage form such as a liquid preparation, an emulsion, a wettable powder, a powder, and a granule. It can be put to practical use.

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.

Blending Example 1 Wettable powder Compound of the present invention No. 2 ────────── 50 parts Dikhlite A ───────── 46 parts (Kaolin clay: Sikhlite Industry Co., Ltd. ) Brand name) Solpol 5039 ───────── 2 parts (mixture of nonionic and anionic surfactants: Toho Chemical Co., Ltd. brand name) Carplex (anti-caking agent) ──── 2 parts (White carbon: trade name of Shionogi Pharmaceutical Co., Ltd.) The above is uniformly mixed and ground to obtain a wettable powder. At the time of 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. 13 ───────────────────────────────────────────────────────────── 19 ) Brand name) Solpol 5039 ────────── 2 parts (mixture of nonionic and anionic surfactants: Toho Chemical Co., Ltd. brand name) Carplex (anti-caking agent) ) ──── 4 parts (White carbon: trade name of Shionogi Pharmaceutical Co., Ltd.) The above is uniformly mixed and pulverized to obtain a wettable powder.

Formulation Example 3 Wettable powder Compound of the present invention No. 18 ───────── 50 parts Dichlorite A ────────── 46 parts (Kaolin clay: Sikhlite Industry Co., Ltd. ) Brand name) Solpol 5039 ────────── 2 parts (mixture of nonionic and anionic surfactants: Toho Chemical Co., Ltd. brand name) Carplex (anti-caking agent) ) ──── 2 parts (White carbon: trade name of Shionogi Seiyaku Co., Ltd.) The above is uniformly mixed and ground to obtain a wettable powder.

Formulation Example 4 Wettable powder Compound No. 29 of the present invention ───────── 25 parts Dichlorite A ────────── 71 parts (Kaolin clay: Siglite Industrial Co., Ltd. ) Brand name) Solpol 5039 ────────── 2 parts (mixture of nonionic and anionic surfactants: Toho Chemical Co., Ltd. brand name) Carplex (anti-caking agent) ) ──── 2 parts (White carbon: trade name of Shionogi Seiyaku Co., Ltd.) The above is uniformly mixed and ground to obtain a wettable powder.

Formulation Example 5 Emulsion Compound No. 30 of the present invention ──────── 2 parts Xylene ────────────── 78 parts Dimethylformamide ───────── 15 parts Solpol 2680 ────────── 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name) To do. At the time of use, the above emulsion is diluted 10 to 10,000 times and sprayed so that the amount of active ingredient is 0.005 kg to 10 kg per hectare.

Formulation Example 6 Flowable compound of the present invention No. 28 ───────── 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. trade name) 1% Rhodopol water ─────────── 20 parts ( Thickener: Trade name of Loan Poulin Co., Ltd.) Water ───────────────── 44.5 parts Mix evenly to make a flowable agent.

Formulation Example 7 Granules Compound of the present invention No. 3 ───────── 0.1 part Bentonite ──────────── 55.0 parts Talc ────────── ────── 44.9 parts After uniformly mixing and pulverizing the above, add a small amount of water, knead with stirring and kneading, granulate with an extrusion granulator, and dry to give granules.

Compounding Example 8 Granules Compound of the present invention No. 12 ───────── 0.5 part Bentonite ──────────── 55.0 parts Talc ────────── ───── 44.5 parts After uniformly mixing and pulverizing, 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 kinds of 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 athletic fields, open spaces, and track ends, as well as agricultural and horticultural fields such as upland fields, paddy fields and orchards.
The amount of application varies depending on the application scene, application time, application method, target grass species, cultivated crops, etc., but in general, about 0.005 to 10 kg per hectare of the active ingredient is appropriate.

Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples. Some of the compounds of this invention are selective for certain crops.

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, and rice, novier, crabgrass, cyperaceae, koa kaza, purslane, pearl oyster, corngrass. Then, cotton was mixed and sown, and the soil was covered by 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 liquid 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. 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 ... Herbicide rate 5% or less (almost no effect) However, the above-mentioned herbicidal rate is obtained by measuring the above-ground vegetation weight of the chemical treatment area and the above-ground vegetation weight of the non-treatment area by the following formula. Herbicide 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: sterilized diluvial soil was placed in a plastic box having a length of 15 cm, a width of 22 cm, and a depth of 6 cm, and rice, crabgrass, cyperaceae,
Koa kaza, leaf-shaped sage, dog pepper, corn,
Seeds of soybean, wheat and cotton were sown in spots and covered with about 1.5 cm of soil. When various plants reached the 2-3 leaf stage, the active ingredients were sprayed evenly on the foliage so that the amount of the active ingredient became a predetermined ratio.

The chemical liquid for spraying was prepared by diluting the wettable powder of the above 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. Control compound A (described in JP-A-56-169688)

[0049]

[Chemical 9]

Control compound B (described in JP-A-56-169688)

[0051]

[Chemical 10]

Control compound C (described in JP-A-56-169688)

[0053]

[Chemical 11]

Control compound D (described in JP-A-55-102577)

[0055]

[Chemical 12]

[0056]

[Table 4] Table 3 ─────────────────────────────────── Inventive active ingredient Kakosu Hiwa compound No. Processing amount Behiya Abekinu kg / ha Nesitz Kalida Gatabariza Himerag Yugi Saku ──────── ──────────────────────────── 2 0.16 5 5 5 5 5 5 5 5 5 5 1 2 0.08 5 4 5 5 5 4 4 5 5 5 0 3 0.16 5 5 5 5 5 5 5 5 5 5 1 3 0.08 5 4 5 5 5 5 5 5 5 5 0 12 0.16 5 5 5 5 5 5 5 5 5 5 0 12 0.08 5 4 4 4 4 4 4 4 4 0 13 0.16 5 5 5 5 5 5 5 0 13 0.08 5 5 5 5 5 5 5 5 5 5 0 17 0.16 5 5 5 5 5 5 5 5 5 5 1 17 0.08 5 4 4 4 4 4 4 4 4 0 18 0.16 5 5 5 5 5 5 5 5 5 5 2 18 0.08 5 5 5 5 5 5 5 5 5 5 1 28 0.16 5 5 5 5 5 5 5 5 0 28 0.08 5 5 5 5 5 5 5 5 5 5 0 29 0.16 5 5 5 5 5 5 5 5 5 5 1 29 0.08 5 5 5 5 5 5 5 5 5 5 0 ─────────────── ─────────────────────

[0057]

[Table 5] Table 3 (continued) ──────────────────────────────────── Inventive active ingredient High-performance compound No. Processing amount Large amount kg / ha Nes- ical kalida Gatabariza Hime-rag Yugi-saku ──── ─────────────────────────────── 30 0.16 5 5 5 5 5 5 5 5 5 5 3 30 0.08 5 5 5 5 5 5 5 5 5 5 2 A 0.16 3 2 2 4 3 2 2 3 4 A 0.08 2 0 1 4 1 1 1 3 2 2 B 0.16 4 4 3 3 4 3 4 4 4 4 B 0.08 3 3 3 1 3 2 3 3 3 3 C 0.16 3 2 2 4 3 2 2 3 3 C 0.08 2 1 1 2 1 1 1 1 2 2 2 D 0.16 5 4 4 4 3 3 3 3 4 4 D 0.08 4 3 4 3 3 3 3 3 3 3 2 2 ───────── ──────────────────────── ─

[0058]

[Table 6] Table 4 ─────────────────────────────────── Inventive active ingredient Processing amount of Codaite Coba Compound No. Hiyaaki Nui kg kg / ha Nestec Gadamozu Giza Barariza Meralog Gishi Kosaku ── ───────────────────────────────── 3 0.16 5 3 5 5 5 5 4 5 5 5 5 1 3 0.08 4 3 5 5 4 4 4 4 4 1 12 0.16 5 5 5 5 5 5 5 5 5 5 5 1 12 0.08 5 4 5 4 4 4 4 4 4 4 4 0 13 0.16 5 5 5 5 5 5 5 3 5 5 5 1 13 0.08 5 5 5 5 5 5 3 5 5 5 0 17 0.16 5 5 5 5 5 4 3 5 5 5 5 2 17 0.08 5 4 4 5 5 4 3 4 5 4 4 1 18 0.16 5 5 5 5 5 5 4 5 5 5 5 2 18 0.08 5 5 5 5 5 5 5 4 5 5 5 1 28 0.16 5 5 5 5 5 5 5 5 5 5 1 28 0.08 4 5 5 5 4 4 5 5 5 5 0 29 0.16 5 5 5 5 5 5 5 5 5 5 5 0 29 0.08 4 5 5 5 5 5 5 5 5 5 5 0 30 0.16 5 5 5 5 5 5 5 5 5 5 5 3 30 0.08 5 5 5 5 5 5 5 5 2 ────────────────────────────────────

[0059]

[Table 7] Table 4 (continued) ──────────────────────────────────────────── Processing amount of compound No. Imekacoit compound No. Hiyaakinum kg / ha Nestec Gadamozu Gizabararizameralogugishikosaku ─────────────────────────────────── A 0.16 4 4 4 4 4 4 4 4 4 4 4 A 0.08 3 4 4 4 4 4 4 4 4 3 3 B 0.16 3 3 3 3 3 3 3 3 3 4 2 2 B 0.08 3 2 2 3 3 2 3 3 3 1 2 D 0.16 3 4 3 3 4 3 3 3 3 2 3 D 0.08 3 3 3 3 3 3 3 3 2 2 2 ────────────────────────────────────

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihiko Oguchi 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Inside the Institute for Biological Science, Nissan Kagaku Kogyo Co., Ltd. Nissan Kagaku Kogyo Co., Ltd. Biological Science Research Institute Examiner Misao Takanashi

Claims (1)

[Claims] 1. The general formula (IX): [In the formula, R ′ represents a halogen atom or COOR ₂ (R ₂ represents a lower alkyl group). R ₁ represents a hydrogen atom or a lower alkyl group. J is SO ₂ Cl or SO ₂
Indicates NH ₂ . Me represents a methyl group. ] Represented by 1
-Methylpyrazole derivatives.