JPH0543706B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has the following features: (1) General formula (): [In the formula, R represents a lower alkyl group, X and Y
each represents a lower alkyl group or a lower alkoxy group, and Z represents an N atom or -CH=. However, the case where R is an ethyl group, X and Y are methoxy groups, and Z is -CH= is excluded. ] The present invention relates to a novel pyrazolesulfonylurea derivative represented by the following, a method for producing the same, and a herbicide containing the derivative as an active ingredient. The compound of the present invention is a new compound that has not been described in any literature and has excellent physiological activity as a herbicide. In JP-A-55-102577 and JP-A-56-139466, pyridine sulfonylurea derivatives are
JP-A-56-169688 describes that pyrrolesulfonylurea derivatives are useful as herbicides. Conventionally, when using herbicides, it has been generally pointed out that the economic cost of using herbicides is influenced by the amount of active ingredient treated per unit area. Research into compounds that exhibit high herbicidal effects has continued for many years. Many compounds are conventionally known as pyrazole derivatives, such as Japanese Patent Publication No. 54-36648, Japanese Patent Application Publication No. 41872-1972, Japanese Patent Application Publication No. 2276-1976, and Japanese Patent Application Publication No. 57-1989.
No. 58670 and Japanese Unexamined Patent Publication No. 133265/1984 are known. As a result of many years of research, the present inventors have discovered that the compound of the present invention has significantly higher herbicidal efficacy than the previously known pyrazole derivatives mentioned above, has selectivity for certain types of crops, and is practically useful. I discovered that. On the other hand, as sulfonylurea derivatives containing a nitrogen-containing heterocycle, the above-mentioned pyrrolesulfonylurea and pyridine sulfonylurea are known, but the present inventors have found that the compound of the present invention exhibits a significantly higher herbicidal effect compared to these known compounds. , we have completed the present invention. In other words, the compound of the present invention can significantly reduce the amount of active ingredient applied per unit area compared to these conventionally known compounds, and has extremely large economic effects compared to conventional herbicides. It can be said to be a revolutionary herbicide that can significantly reduce the risk of environmental pollution when applied. The compound of the present invention represented by the above general formula () can be easily produced by the following reaction formula. Reaction formula 1 [In the formula, R, X, Y and Z have the same meanings as above. ] That is, the pyrazole sulfonyl isocyanate derivative () was mixed with sufficiently dried dioxane,
By dissolving the compound in an inert solvent such as acetonitrile, adding pyrimidine or triazine derivative (2) thereto and stirring, the compound (2) of the present invention can generally be quickly reacted. If the reaction is difficult to proceed, the reaction can be facilitated by adding a small amount of a suitable base such as triethylamine, triethylenediamine, pyridine, sodium ethoxide, sodium hydride, etc. The raw material pyrazole sulfonyl isocyanate can be converted into pyrazole sulfonyl isocyanate by synthesizing pyrazole sulfonamide using the synthesis method described below, and then by referring to the method described in JP-A-55-13266. can. Using the obtained intermediate (), the sulfonamide () can be obtained by several methods described below. Reaction formula 2 That is, the pyrazole sulfonamide derivative () is reacted with an alkyl chlorocarbonate in a solvent such as acetone or methyl ethyl ketone in the presence of a base such as potassium carbonate, and after the reaction, the compound () is precipitated with hydrochloric acid or the like to obtain the compound (). The compound () of the present invention can also be obtained by heating the compound () in a solvent such as toluene. Furthermore, the compound () of the present invention can be more easily obtained by synthesizing R ₁ = C ₆ H ₅ in compound () with reference to JP-A-57-56452 and carrying out the reaction in the same manner as above. . Reaction formula 3 [In the formula, A and B each represent a halogen atom, R ₂
represents a lower alkyl group. ] With reference to JP-A-56-154471, the compound () is synthesized by reacting the pyrazole sulfonamide derivative () with pyrimidine or triazine isocyanate (), and then the compound () is reacted with sodium alcoholate to synthesize the present invention. Compound () can also be synthesized. On the other hand, aminopyrimidines are available from The Chemistry of Heterocyclic Compounds (Interscience Publishers, Inc. New York) [The
Chemistry of Heterocyclic Compounds
(Interscience Publishers Inc. New York)], Volume 16 of The Pyrimidines. Aminotriazines are also listed in the Journal of Organic Chemistry.
Organic Chemistry) Vol. 28, pp. 1812-1821 (1963). The intermediate used in the present invention is a new compound, and a synthesis example thereof is shown below as a reference example. Reference Example 1 Synthesis of 4-ethoxycarbonyl-1-methyl-5-pyrazolesulfonamide 1-1 5-hydroxy-1-methyl-4-
Synthesis of ethyl pyrazole carboxylate Diethyl ethoxymethylenemalonate 216g
(1 mol) was dissolved in 216 g of ethanol, and 46 g (1 mol) of methylhydrazine was added at 10°C. Thereafter, the mixture was stirred at room temperature for 1 hour, and then heated and refluxed for another 1 hour. The precipitated crystals were filtered and dried to obtain 148 g of the target compound having a melting point of 134-135°C. 1-2 Synthesis of ethyl 5-chloro-1-methyl-4-pyrazolecarboxylate 10 g of ethyl 5-hydroxy-1-methyl-4-pyrazolecarboxylate and 50 phosphorus oxychloride
ml of the mixture was stirred at 90-100°C for 65 hours.
Excess phosphorus oxychloride was distilled off under reduced pressure, and the residue was poured into ice water. The precipitated crystals were filtered and dried to obtain 4.5 g of 5-chloro-1-methyl-4-pyrazolecarboxylic acid having a melting point of 194-195°C. Also, the liquid was made alkaline with aqueous ammonia, extracted with ether, dried, and the solvent was distilled off to obtain oily 5-chloro-1-
Ethyl methyl-4-pyrazolecarboxylate 4.0g
I got it. 30 ml of thionyl chloride and 0.2 ml of dimethylformamide were added to 5-chloro-1-methyl-4-pyrazolecarboxylic acid, and after heating under reflux for 5 hours, excess thionyl chloride was distilled off and added to dry ethanol.
After stirring at room temperature for 3 hours, the solvent was distilled off, ether was added, washed with water, dried, and the solvent was distilled off to give 5-chloro-1.
-ethyl-methyl-4-pyrazolecarboxylate 4.5
I got g. Total amount of objects: 8.5g. 1-3 Synthesis of ethyl 5-mercapto-1-methyl-4-pyrazolecarboxylate After dissolving 2.2 g (0.094 mol) of sodium metal in 35 ml of ethanol, 50 ml of dimethylformamide was added and most of the ethanol was distilled off. Next, under cooling, hydrogen sulfide gas was blown in to saturate the mixture, and then 7.4 g (0.039 ml) of ethyl 5-chloro-1-methyl-4-pyrazolecarboxylate was added. 3.5 at 70-80℃
After stirring for an hour, the mixture was concentrated under reduced pressure, and ice water was added to the residue to filter out insoluble matter. After making the liquid acidic, it was extracted with chloroform, dried, and the solvent was distilled off to obtain 6.8 g of the target product in the form of an oil. 1-4 4-ethoxycarbonyl-1-methyl-
Synthesis of 5-pyrazole sulfonamide 7.1 g of ethyl 5-mercapto-1-methyl-4-pyrazolecarboxylate and 1.6 g of sodium hydroxide
20 ml of an aqueous solution of g was added to 100 ml of 28% ammonia water. Add 61g of 6% NaOCl aqueous solution to this aqueous solution.
Added at ~10°C. The precipitated crystals were filtered and washed with water, and 5.6 g of sulfenamide obtained was suspended in water, and a saturated aqueous solution of 5.5 g of potassium permanganate was added at room temperature. After stirring vigorously at room temperature, the filtrate was acidified and extracted with ethyl acetate. After drying, the solvent is distilled off,
1.8g of the target product was obtained. Melting point 102-104℃ 1-5 4-ethoxycarbonyl-1-methyl-
Synthesis of 5-pyrazole sulfonamide (alternative method) Add 15 to 20 ml of ethyl 5-mercapto-1-methyl-4-pyrazolecarboxylate to a solution of 50 ml of acetic acid.
The mixture was stirred at ℃ while drawing in chlorine gas. Next, after blowing in nitrogen gas, the reaction mixture was poured into ice water to separate the formed oil. The sulfonyl chloride obtained 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, it was concentrated under reduced pressure, the precipitated crystals were washed separately with water, and further
- Washed with hexane. After drying, 1.3 g of the target product was obtained. Melting point: 102-104°C Reference Example 2 Synthesis of 4-methoxycarbonyl-1-methyl-5-pyrazole sulfonamide Synthesis was performed according to the above Reference Example. Melting point: 127-128°C The physical properties of each intermediate are as follows. Methyl 5-hydroxy-1-methyl-4-pyrazolecarboxylate Melting point 111-113°C Methyl 5-chloro-1-methyl-4-pyrazolecarboxylate Melting point 70-71°C 5-mercapto-1-methyl-4-pyrazole Methyl carboxylate Melting point 64-66°C A specific synthesis example of the compound of the present invention will be explained using the substituted pyrazole sulfonamide () obtained in Reference Example. However, it is not limited to these only. Example 1 N-[(4.6-dimethoxypyrimidine-
Synthesis of 2-yl)aminocarbonyl]-4-ethoxycarbonyl-1-methyl-5-pyrazolesulfonamide 5.0 g of 4-ethoxycarbonyl-1-methyl-5-pyrazolesulfonamide, 4.45 g of dry potassium carbonate, 50 ml of acetone 2.13 g of n-butyl yocyanate was added to the mixture at room temperature, and the mixture was heated under reflux.
Stirred for 3 hours. After the reaction, acetone was distilled off under reduced pressure.
Ice water was added to the residue, and insoluble matter was filtered out. The solution was precipitated with hydrochloric acid, and the precipitated crystals were separated, washed with water, and dried to give N-(n-butylcarbamoyl-4-ethoxycarbonyl-1-methyl-5) with a melting point of 117-119°C.
- 5.1 g of pyrazole sulfonamide were obtained. Next, the mixture was added to 120 ml of dry toluene, heated under reflux, 9.1 g of phosgene was blown into the mixture, and the mixture was further heated under reflux for 1.5 hours. After the reaction was completed, the mixture was concentrated under reduced pressure to obtain crude sulfonyl isocyanate. 0.98g of the above crude sulfonylisocyanate was added to 2-
The mixture was added to a solution of 400 mg of amino-4-6-dimethoxypyrimidine in 20 ml of dry acetonitrile, and the mixture was stirred at room temperature. The generated crystals were separated, washed and dried to obtain 0.8 g of the desired product having a melting point of 170-172°C. Example 2 N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-4
-Synthesis of methoxycarbonyl-1-methyl-5-pyrazolesulfonamide (Compound No. 2) Using the sulfonamide obtained in Reference Example 2 and following the method of Example 1, N-(n-butylcarbamoyl-4 -methoxycarbonyl-1-methyl-5
- Obtain pyrazole sulfonamide. Melting point 88-90
℃. Furthermore, sulfonyl isocyanate was synthesized according to Example 1, and by reacting with 2-amino-4-methoxy-6-methylpyrimidine, the melting point was 183~
The target product was obtained at 184°C. Next, a compound synthesized according to the above example,
They are shown in Table 1 below along with the compound synthesized in Example 2 (Compound No. 2).

[Table] When applying the compound of the present invention as a herbicide, a suitable carrier is generally used, such as a solid carrier such as clay, talc, bentonite, diatomaceous earth, water, alcohols (methanol, ethanol, etc.),
When mixed with liquid carriers such as aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.) Can be applied, optionally emulsifiers,
By adding a dispersant, suspending agent, penetrating agent, spreading agent, stabilizer, etc., it can be put to practical use in any desired dosage form such as a liquid, emulsion, wettable powder, powder, or granule. Next, examples of formulations of herbicides containing the compound of the present invention as an active ingredient will be shown, but the invention is not limited thereto. In addition, in the following formulation examples, "parts" mean parts by weight. Formulation example 1 Wettable powder Compound of the present invention No. 1...50 parts Siegrite A...46 parts (Kaolin clay: Sieglite Industries Co., Ltd. trade name) Solpol 5039...2 parts (Nonionic surfactant and an anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)... 2 parts (White carbon: Shionogi & Co., Ltd. trade name) The above are mixed and pulverized uniformly. Use as a hydrating agent. When using, dilute the above hydrating agent 50 to 50,000 times.
Spray at an amount of active ingredient of 0.005Kg to 10Kg per hectare. Formulation example 2 Wettable powder Compound of the present invention No. 2 ... 75 parts Siegrite A ... 19 parts (Kaolin clay: Sieglite Industries Co., Ltd. trade name) Solpol 5039 ... 2 parts (Nonionic surfactant and an anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)... 4 parts (White carbon: Shionogi & Co., Ltd. trade name) The above was mixed and ground uniformly. Use as a hydrating agent. Formulation example 3 Wettable powder Compound of the present invention No. 3 ... 50 parts Siegrite A ... 46 parts (Kaolin clay: Sieglite Industries Co., Ltd. trade name) Solpol 5039 ... 2 parts (Nonionic surfactant and an anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)... 2 parts (White carbon: Shionogi & Co., Ltd. trade name) The above are mixed and pulverized uniformly. Use as a hydrating agent. Formulation example 4 Wettable powder Compound of the present invention No. 6...25 parts Siegrite A...71 parts (Kaolin clay: brand name of Sieglite Industries Co., Ltd.) Solpol 5039...2 parts (Nonionic surfactant and an anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)... 2 parts (White carbon: Shionogi & Co., Ltd. trade name) The above are mixed and pulverized uniformly. Use as a hydrating agent. Formulation example 5 Wettable powder Compound of the present invention No. 7...50 parts Siegrite A...44 parts (Kaolin clay: brand name of Sieglite Industries Co., Ltd.) Solpol 5039...4 parts (Nonionic surfactant and an anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)... 2 parts (White carbon: Shionogi & Co., Ltd. trade name) The above are mixed and pulverized uniformly. Use as a hydrating agent. Formulation example 6 Wettable powder Compound of the present invention No. 8...45 parts Siegrite A...51 parts (Kaolin clay: Sieglite Industries Co., Ltd. trade name) Solpol 5039...2 parts (Nonionic surfactant and an anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent)... 2 parts (White carbon: Shionogi & Co., Ltd. trade name) The above are mixed and pulverized uniformly. Use as a hydrating agent. Formulation Example 7 Emulsion Compound of the Invention No. 1 ...2 parts Xylene ...78 parts Dimethylformamide ...15 parts Solpol 2680 ...5 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical) Co., Ltd. (product name)) Mix the above ingredients uniformly to make an emulsion. When used, 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 8 Flowable Compound of the Invention No. 9...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: Lorne-Poulenc trade name) Water...44.5 parts Mix the above uniformly to make a flowable agent. Formulation example 9 Granules Compound of the present invention No. 2 ...0.1 part bentonite ...55.0 parts talc ...44.9 parts After uniformly mixing and pulverizing the above, a small amount of water was added, stirring and kneading were carried out, and extrusion molding was carried out. Granulate it with a granulator and dry it to make granules. Formulation example 10 Granules Compound of the present invention No. 3 ...0.25 parts bentonite ...55.0 parts talc ...44.75 parts After uniformly mixing and pulverizing the above, a small amount of water was added and the mixture was stirred and kneaded. Granulate it with a granulator and dry it to make granules. Formulation example 11 Granules Compound of the present invention No. 7 ... 0.5 parts Bentonite ... 55.0 parts Talc ... 44.5 parts After uniformly mixing and pulverizing the above, a small amount of water was added, stirring and kneading were carried out, followed by extrusion manufacturing. Granulate it with a granulator and dry it to make granules. Formulation example 12 Granules Compound of the present invention No. 8 ... 1.0 parts Bentonite ... 55.0 parts Talc ... 44.0 parts After uniformly mixing and pulverizing the above, a small amount of water was added, stirring and kneading were carried out, followed by extrusion manufacturing. Granulate it with a granulator and dry it to make granules. Furthermore, the compound of the present invention may be applied in combination with other herbicides, various insecticides, fungicides, synergists, etc. when preparing or spraying, if necessary. Other types of herbicides mentioned above include, for example, Farm Chemicals Handbook (Farm Chemicals Handbook).
Chemicals Handbook) 68th edition (1982). The compound of the present invention can be applied to control various weeds in agricultural and horticultural areas such as fields, paddy fields, and orchards, as well as in non-agricultural areas such as playgrounds, vacant lots, and railway edges, and the amount of the applied drug depends on the application situation. There are differences depending on the application time, application method, target grass species, cultivated crops, etc., but in general, the amount of active ingredients per hectare is
Approximately 0.005 to 10 kg is appropriate. Next, the usefulness of the compounds of the present invention as herbicides will be specifically explained in the following test examples. Test Example-1 Weeding effect test by soil treatment Sterilized diluvial soil was placed in a plastic box measuring 15 cm long, 22 cm wide, and 6 cm deep, and rice, Japanese wildflower, Japanese cypress, Japanese cypress, Koakaza, purslane, Japanese leafminer, and dogwood were mixedly sown. After covering the soil with approximately 1.5 cm of soil, the amount of active ingredient was uniformly spread over the soil surface in a predetermined ratio. At the time of spraying, the chemical solution was sprayed over the entire surface using a small sprayer made by diluting the hydrating agent of the formulation example with water. 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 2. Some of the compounds of the invention have selectivity for certain crop species. Judgment criteria 5... Weed killing rate 90% or more (almost complete death) 4... Weed killing rate 70-90% 3... Weed killing rate 40-70% 2... Weed killing rate 20-40% 1... Weed killing rate 5-20 % 0...Weed killing rate 5% or less (almost ineffective) However, the above weed killing rate is calculated by the following formula by measuring the above-ground grass weight in the chemical-treated area and the above-ground grass weight in the untreated area. It is something that Weed killing rate (%) = (1 - above-ground grass weight in treated area / above-ground grass weight in untreated area) x 100

【table】

[Table] Test Example-2 Herbicidal effect test by foliar treatment Sterilized diluvial soil was placed in a plastic box measuring 15 cm long, 22 cm wide, and 6 cm deep, and the soil was placed in a plastic box measuring 15 cm in length, 22 cm in width, and 6 cm in depth, and the soil was placed in a plastic box measuring 15 cm in length, 22 cm in width, and 6 cm in depth. , wheat, and tomato seeds were sown in spots and covered with soil to a depth of about 1.5 cm. When each plant reached the 2-3 leaf stage, the active ingredient was uniformly sprayed onto the stems and leaves so that the amount of the active ingredient was at a predetermined ratio. The chemical solution used for spraying was the wettable powder of the formulation example described above diluted with water and sprayed over the entire surface of the stems and leaves of various weeds using a small sprayer. 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 3. Some of the compounds of the invention have selectivity for certain crop species.

【table】

[Table] Test Example 3 Weeding effect test under flooded conditions After putting alluvial soil in a 1/5000 are Wagner pot, add water and mix to create a flooded condition with a water depth of 2 cm. Seeds of Japanese millet, Japanese cabbage, Japanese azalea, Kikashigusa, and Firefly were mixedly sown in the above-mentioned pots, and tubers of Prunus japonicus and Cyperus japonica were also placed in the beds. Furthermore, rice seedlings at the 2.5 leaf stage were transplanted. The next day, a diluted drug solution was dropped onto the water surface using a measuring pipette to a predetermined dose. Three weeks after dropping the chemical solution, the herbicidal effect on various weeds was investigated according to the criteria of Test Example 1. The results are shown in Table 4.

【table】

Claims (1)

[Claims] 1 General formula (): [In the formula, R represents a lower alkyl group, X and Y
each represents a lower alkyl group or a lower alkoxy group, and Z represents an N atom or -C=. However, R is an ethyl group, X and Y are methoxy groups,
Except when Z is -C=. ] A pyrazole sulfonylurea derivative represented by Quadratic formula (): [In the formula, R represents a lower alkyl group. ] and the following formula (): [In the formula, X and Y each represent a lower alkyl group or a lower alkoxy group, and Z represents an N atom or -C=. General formula () characterized by reacting an aminopyrimidine or aminotriazine derivative represented by ] in an inert solvent: [In the formula, R, X, Y and Z have the same meanings as above. However, the case where R is an ethyl group, X and Y are methoxy groups, and Z is -C= is excluded. ] A method for producing a pyrazole sulfonylurea derivative. 3 General formula (): [In the formula, R represents a lower alkyl group, X and Y
each represents a lower alkyl group or a lower alkoxy group, and Z represents an N atom or -C=. However, R is an ethyl group, X and Y are methoxy groups,
Except when Z is -C=. ] A herbicide characterized by containing one or more pyrazolesulfonylurea derivatives represented by the following as an active ingredient.