JPH0660174B2 - Pyrazolsulfonylurea derivative, method for producing the same, and herbicide containing the derivative - Google Patents

Description

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.

JP-A-55-102577 and JP-A-56-139.
No. 466 discloses a pyridinesulfonylurea derivative,
JP-A-56-169688 describes that pyrrolesulfonylurea derivatives are useful as herbicides.

On the other hand, conventional pyrazole derivatives are described in, for example, JP-B-54-36648, JP-A-54-41872, JP-A-57-2276, JP-A-57-58670 and JP-A-51-133265. It is known that these compounds are useful as herbicides.

It is indispensable to use herbicides to protect important crops such as rice, wheat, corn and cotton from weed damage and increase their 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. Although some of the compounds with such properties are currently used as 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, but they are not always satisfactory, and some of the conventionally known pyrazole derivatives are used in rice. Although it shows selectivity, it requires a relatively high dose, which is not always satisfactory.

The present inventors have continued to study for many years to develop a useful herbicide, and in order to produce a compound having higher herbicidal activity, the herbicidal properties of many compounds have been examined. 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 not only in cultivated lands but also in other 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 [Wherein R, R ₁ , Me, X, Y and Z have the same meanings as described above. That is, a pyrazole sulfonyl isocyanate derivative is dissolved in a sufficiently dried inert solvent such as dioxane or 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 [In the formula, 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 [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. 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 be synthesized by reacting with sodium alcoholate. The raw material pyrazole sulfonyl isocyanate used in Reaction Scheme 1 was prepared by synthesizing pyrazole sulfonamide by the method described below.
It can be synthesized with reference to the method described in JP-A-13266. The pyrazole sulfonamide, which is an intermediate, is also a novel compound, but its synthesis can be performed by the synthetic route described below.

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

Reference Example 1 Synthesis of 1-methylpyrazole-3-sulfonamide 32 g of 1-methyl-3-aminopyrazole, 120 m of concentrated hydrochloric acid
l, and 40 ml of acetic acid in a mixed solution of sodium nitrite 34.1
An aqueous solution of g was added at -10 ° C to 0 ° C. -5 this solution
Stir at ℃ for 30 minutes, then in small portions, cuprous chloride 6.7g
-10 to -5 to 440 ml of a solution of sulphite-saturated acetic acid containing
Dropwise at ° C. After the dropwise addition, the mixture was stirred at 0 to 5 ° C for 4 hours, then poured into ice water and extracted with ether. Wash the extract thoroughly with water and saturated aqueous sodium hydrogen carbonate solution,
After drying, the solvent was distilled off to give crude sulfonyl chloride 20.8
g was obtained. The sulfonyl chloride obtained here was dissolved in 50 ml of tetrahydrofuran, and this was added to 150 ml of 28% aqueous ammonia at a temperature of 10 ° C. or lower under ice cooling. After stirring for 3 hours at room temperature, the solid obtained by concentration under reduced pressure was filtered, washed with water and hexane, and dried to obtain 14.2 g of the desired product. Melting point 156-158 ° C Reference Example 2 4-methoxycarbonyl-1-methylpyrazole-3-
Synthesis of Sulfonamide It was 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, 120 m of concentrated hydrochloric acid
l, and 40 ml of acetic acid in a mixed solution of sodium nitrite 34.1
An aqueous solution of g was added at -10 ° C to 0 ° C. -5 this solution
Stir at ℃ for 30 minutes, then in small portions, cuprous chloride 6.7g
-10 to -5 to 440 ml of sulfuric acid gas saturated acetic acid solution containing
Dropwise at ° C. After the dropwise addition, the mixture was stirred at 0 to 5 ° C for 4 hours, then poured into ice water and extracted with ether. Wash the extract thoroughly with water and saturated aqueous sodium hydrogen carbonate solution,
When the solvent was distilled off after drying, 1-methylpyrazole-3-
20.8 g of sulfonyl chloride was obtained. (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 with stirring 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,
4% of 28% ammonia water was added dropwise thereto at a temperature of ℃ or less. 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 16 g of bromine was added dropwise to a solution of 9.7 g of 1-methyl-3-aminopyrazole and 40 ml of acetic acid at 20 ° C. and 1 I left it at night. 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: hexane to give 3-amino-4-brom-1-
10 g of methylpyrazole were obtained. Melting point 100 ° C-102 ° C 8.8 g of the above-obtained aminopyrazole, concentrated hydrochloric acid 17.
An aqueous solution of 3.6 g of sodium nitrite was added to a mixed solution of 5 ml, 5 ml of acetic acid and 5 ml of phosphoric acid at -10 ° C to 0 ° C. This solution was stirred at -5 ° C for 30 minutes, and then added little by little 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 solid crude sulfonyl chloride. The sulfonyl chloride obtained here was dissolved in 10 ml of tetrahydrofuran,
20 ml of 28% aqueous ammonia was added dropwise at a temperature of 10 ° C or lower. After stirring for 1 hour at room temperature, the solid obtained by concentrating under reduced pressure was filtered, washed with water and hexane, and dried to give the desired compound (7.7 g).
was gotten.

Melting point 195 to 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 to 3-amino-4. -Brom-1,5-dimethylpyrazole (melting point: 111-113 ° C) was synthesized, and then the desired product was obtained.

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-
To a mixture of 7.8 g of sulfonamide and 6.90 g of dry potassium carbonate in 70 ml of acetone was added 4.00 g of n-butyl isocyanate 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-ethoxycarbonyl-1-methylpyrazole-3-sulfonamide
10.7 g was obtained. Melting point 124-125 ° C.

Next, this was added to 120 ml of dry toluene and heated under reflux,
After blowing 9.6 g of phosgene, the mixture was heated 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 and dried to obtain the desired product.
1.0 g was obtained. Melting point 150-152 ° C. Example 2 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-bromo-1-methylpyrazole-3-sulfonamide 4-bromo-1-methylpyrazole To a mixture of 7.7 g of -3-sulfonamide and 6.60 g of dry potassium carbonate in 70 ml of acetone was added 3.16 g of n-butyl isocyanate 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 was acid-precipitated with hydrochloric acid, and the precipitated crystals were separated by filtration, washed with water and dried to obtain 9.3 g of N- (n-butylcarbamoyl) -4-bromo-1-methylpyrazole-3-sulfonamide.

Next, this was added to 100 ml of dry toluene and heated under reflux,
8.1 g of phosgene was blown in, and the mixture was heated 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. 1.3 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 acenitonitrile, and the mixture was stirred at room temperature for 3 hours and then heated under reflux for 5 minutes. The crystals formed are filtered off,
0.8 g of the target product was obtained by washing and drying.

Melting point 148 to 152 ° C. Next, the physical properties of the compounds synthesized according to the above Examples are shown in Tables 1 and 2 below together with the compounds synthesized in the Examples, but the compounds of the present invention are not limited to these. Absent.

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, Toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamides), etc. can be mixed and applied, if desired. By adding an emulsifier, a dispersant, a suspending agent, a penetrating agent, a spreading agent, a stabilizer and the like, it can be put into practical use in any dosage form such as liquid, emulsion, wettable powder, powder and granules.

Next, examples of blending a herbicide as an active ingredient of the compound of the present invention are shown, but the invention is not limited thereto. In the following formulation examples, "part" means part by weight.

Formulation Example 1 Wettable powder Compound of the present invention NO.2: 50 parts Dikrite A: 46 parts (Kaolin-based clay: product name of Sikhlite Industry Co., Ltd.) Solpol 5039: 2 parts (Nonionic surfactant And anionic surfactant: Toho Chemical Co., Ltd. trade name Carplex (anti-caking agent) 2 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) To make 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.

Blending Example 2 Wettable powder Compound of the present invention NO.13 ... 75 parts Dikrite A..19 parts (Kaolin clay: product name of Sikelite Co., Ltd.) Solpol 5039..2 parts (Nonionic surfactant And anionic surfactant: Toho Chemical Co., Ltd. trade name Carplex (anti-caking agent) …… 4 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) To make wettable powder.

Formulation Example 3 Wettable powder Compound of the present invention NO.18 …… 50 parts Diklite A …… 46 parts (Kaolin-based clay: product name of Sikhlite Industry Co., Ltd.) Solpol 5039 …… 2 parts (Nonionic surfactant And anionic surfactant: Toho Chemical Co., Ltd. trade name Carplex (anti-caking agent) 2 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) To make wettable powder.

Formulation Example 4 Wettable powder Compound No. 29 of the present invention ...... 25 parts Dikrite A ...... 71 parts (Kaolin clay: product name of Sikhlite Industry Co., Ltd.) Solpol 5039 ...... 2 parts (Nonionic surfactant And anionic surfactant: Toho Chemical Co., Ltd. trade name Carplex (anti-caking agent) 2 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) To make wettable powder.

Formulation Example 5 Emulsion Compound of the present invention NO.30 2 parts Xylene 78 parts Dimethylformamide 15 parts Sorpol 2680 5 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Kagaku) Brand name) The above is uniformly mixed to form an emulsion. At the time of 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 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 parts (Anionic interface Activator: Toho Kagaku Co., Ltd. product name) 1% Rhodopol water ...... 20 parts (Thickener: Lone Poulean company product name) Water ...... 44.5 parts The above ingredients are mixed uniformly 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, a small amount of water is added and the mixture is kneaded with stirring to form an extrusion type product. Granulate with a granulator and dry to give granules.

Formulation 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 the above, a small amount of water is added and the mixture is kneaded with stirring, and extrusion molding is performed. Granulate with a granulator and dry to give granules.

Further, the compound of the present invention may be mixed and applied with other kinds of herbicides, various insecticides, fungicides, synergists and the like at the time of preparation or spraying, if necessary.

Examples of the above-mentioned other types of herbicides include, for example, Farm Chemicals. Handbook (Farm Chemicals Handbook) 68
And the compounds described in Edition (1982).

The compound of the present invention can be applied to the control of various weeds in non-agricultural fields such as fields, paddy fields, orchards in fields other than agricultural and horticultural fields such as orchards, and its application dosage is Although there are differences depending on the time of application, method of application, target grass species, cultivated crops, etc., it is generally appropriate that the amount of active ingredient is 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.

Some of the compounds of this invention are selective for certain crops.

Test Example-1 Herbicidal Effect Test by Soil Treatment Put sterilized diluvial soil in a plastic box having a length of 15 cm, a width of 22 cm, and a depth of 6 cm, and then add rice, novier, crabgrass, cyperaceae, koa azalea, purslane, cottonseed, dogtail and cotton. After mixed sowing and covering with about 1.5 cm of soil, the mixture was sprayed uniformly on the soil surface so that the amount of 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.

Criteria 5 ... Weed kill rate 90% or more (almost complete death) 4 ... Weed kill rate 70-90% 3 ... Weed kill rate 40-70% 2 ... Weed kill rate 20-40% 1 ... Weed kill rate 5 20% 0 ...... 5% or less herbicidal rate (almost no effect) However, the above-mentioned herbicidal rate is the above formula by measuring the above-ground weed weight of the chemical treatment area and the above-ground weed weight of the untreated area. It is what I asked for.

Test Example-2 Herbicidal effect test by foliar treatment 15 cm in length, 22 cm in width, 6 cm in depth and put in a sterilized diluvial soil in a plastic box, rice, crabgrass, cyperus,
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 solution 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) Control compound B (described in JP-A-56-169688) Control compound C (described in JP-A-56-169688) Control compound D (described in JP-A-55-102577)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihiko Oguchi 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Inside Biochemical Research Laboratories, Nissan Chemical Industries, Ltd. Misao Takanashi, Examiner, Biochemistry Research Institute, Chemical Industry Co., Ltd. (56) Reference JP-A-58-219179 (JP, A) JP-A-59-1480 (JP, A)

Claims (3)

[Claims] 1. General formula (I): Or general formula (I '): [Wherein R is a hydrogen atom, a halogen atom or COOR ₂ (R ₂
Represents a lower alkyl group. ) Is shown. R ₁ represents a hydrogen atom or a lower alkyl group. Me represents a methyl group. X and Y are each independently a hydrogen atom, a lower alkyl group,
Lower alkoxy group, a dimethylamino group or a halogen atom, Z is a nitrogen atom or = CR ₃ - shows the (R ₃ is a hydrogen atom or a halogenated alkyl group.). ] The pyrazole sulfonyl urea derivative represented by these. 2. General formula (II): [Wherein R is a hydrogen atom, a halogen atom or COOR ₂ (R ₂
Represents a lower alkyl group. ) Is shown. R ₁ represents a hydrogen atom or a lower alkyl group. Me represents a methyl group. ] The pyrazole sulfonyl isocyanate derivative represented by the following formula (III): Or the following formula (III ′): [X and Y each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a dimethylamino group or a halogen atom, Z is a nitrogen atom or = CR _3- (R ₃ is a hydrogen atom or a halogenated alkyl group. It shows). ] An aminopyrimidine or aminotriazine derivative represented by the following formula is reacted in an inert solvent, represented by the general formula (I): Or general formula (I '): [Wherein R is a hydrogen atom, a halogen atom or COOR ₂ (R ₂
Represents a lower alkyl group. ) Is shown. R ₁ represents a hydrogen atom or a lower alkyl group. Me represents a methyl group. X and Y are each independently a hydrogen atom, a lower alkyl group,
Lower alkoxy group, a dimethylamino group or a halogen atom, Z is a nitrogen atom or = CR ₃ - shows the (R ₃ is a hydrogen atom or a halogenated alkyl group.). ] The manufacturing method of the pyrazole sulfonyl urea derivative represented by these. 3. General formula (I): Or general formula (I '): [Wherein R is a hydrogen atom, a halogen atom or COOR ₂ (R ₂
Represents a lower alkyl group. ) Is shown. R ₁ represents a hydrogen atom or a lower alkyl group. Me represents a methyl group. X and Y are each independently a hydrogen atom, a lower alkyl group,
Lower alkoxy group, a dimethylamino group or a halogen atom, Z is a nitrogen atom or = CR ₃ - shows the (R ₃ is a hydrogen atom or a halogenated alkyl group.). ] A herbicide containing one or more pyrazole sulfonylurea derivatives represented by the following as an active ingredient.