JPH0434993B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [In the formula, R ₁ and R ₂ are lower alkyl groups or R ₁ and
together with R ₂ represents a hexamethylene group,
R ₃ is a cycloalkylalkyl group or 1,3-
represents an alkyl group substituted with a dioxacyclopentan-2-yl group or a 1,3-dioxacyclohexane-2-yl group, and n is 0, 1 or 2
represents. ] The present invention relates to a carbamoyltriazole derivative (hereinafter referred to as the compound of the present invention) represented by the following and a herbicide containing the same as an active ingredient. Certain carbamoyltriazole derivatives, such as 1-diethylcarbamoyl-3-propylsulfonyl-1,2,4-triazole, 1-diethylcarbamoyl-8-propylsulfinyl-1,2,4-triazole, 1-diethyl It is described in JP-A-47-2149 that carbamoyl-3-propylthio-1,2,4-triazole and the like can be used as active ingredients of herbicides.
However, these compounds cannot always be said to be sufficient as active ingredients for herbicides. The compounds of the present invention can be used to treat various weeds that are problematic in the treatment of foliage and soil in upland fields, such as buckwheat, purslane, chickweed, whiteweed, whiteweed, Japanese radish, Japanese radish, shepherd's purse, Japanese radish, morning glory, morning glory, etc. Broad-leaved weeds, barnyard grass, barnyard grass, foxtail grass,
Scrub grass, sycamore, sorghum, oat, oat, seiban sorghum,
It has a herbicidal effect on weeds of the grass family, such as grasshopper, grasshopper, and cypressweed, as well as cyperaceous weeds, such as cyperus spp. It does not show any drug damage that would cause problems. In addition, the compound of the present invention can be applied to various weeds that are problematic in the waterlogging treatment of rice fields, such as grass weeds such as Japanese millet, broad-leaved weeds such as azalea, staghorn grass, and Japanese chickweed, and cyperaceous weeds such as cyperus cyperus, bulrush, cypress, and cyperus cyperus. It has a herbicidal effect on grasses such as Prunus elegans, and does not cause any harmful effects on rice. The compound of the present invention has the general formula [In the formula, R ₃ and n represent the same meanings as above. ] Triazole derivative and general formula shown by [In the formula, X represents a halogen atom, and R ₁ and R ₂ have the same meanings as above. ] It can be produced by reacting a carbamoyl halide represented by the following in a solvent in the presence of a dehydrohalogenating agent. The amount of reagents used in this reaction is 1 to 1.5 equivalents of carbamoyl halide [] and 1 to 10 equivalents of the dehydrohalogenating agent per 1 equivalent of triazole derivative []. As a solvent, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as chloroform, methylene chloride, and chlorobenzene,
Ethers such as diethyl ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, organic bases such as pyridine, triethylamine, and N,N-diethylaniline, acetonitrile,
Examples include N,N-dimethylformamide, dimethyl sulfoxide, and water. Examples of the dehydrohalogenation agent include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate, and organic bases such as pyridine, triethylamine, and N,N-diethylaniline. The reaction temperature is from the freezing point to the boiling point of the solvent, preferably from 0°C to 150°C, and the reaction time is 10°C.
It takes from a minute to about 48 hours. After the completion of the reaction, the reaction solution is subjected to conventional post-treatments such as solvent distillation, or further purified by recrystallization, column chromatography, etc., if necessary, to obtain the desired compound of the present invention. Further, in general formula [I], n is 1 or 2
The compound of the present invention is represented by the general formula [In the formula, R ₁ , R ₂ and R ₃ have the same meanings as above. ] It can be manufactured by oxidizing the carbamoyltriazole derivative shown by using an oxidizing agent. Examples of the oxidizing agent include hydrogen peroxide, aromatic peracids such as m-chloroperbenzoic acid, and aliphatic peracids such as peracetic acid and pertrifluoroacetic acid. A solvent does not necessarily need to be used, but if it is used, it depends on the type of oxidizing agent. For example, for hydrogen peroxide, water, glacial acetic acid, acetone, etc. are used; for aromatic peracids, halogenated hydrocarbons such as chloroform, methylene chloride, etc. Ethers such as, diethyl ether, and dioxane are preferred. In the case of aliphatic peracids, it is preferable to use the oxidizing agent itself in excess. The reaction temperature is from the freezing point to the boiling point of the solvent, preferably from 0°C to 100°C, and the reaction time is:
It takes about 10 minutes to 24 hours. After the reaction is completed, the reaction solution is washed with alkaline water,
The desired compound of the present invention can be obtained by performing usual post-treatments such as solvent distillation, or further purifying by recrystallization, column chromatography, etc., if necessary. Next, production examples of the compounds of the present invention will be shown. Production Example 1 (Production of Compound 1 of the Invention) 3-cyclopropylmethylthio-1,2,4-
Dissolve 3.8g of triazole in 30ml of pyridine, add 3.4g of diethylcarbamoyl chloride, and heat to room temperature for 10 minutes.
After leaving it for a while, add 250ml of water and chloroform.
Extracted twice with 150 ml. The chloroform layer was washed twice with 150 ml of 1N hydrochloric acid and once with 200 ml of water, dried over magnesium sulfate, and the solvent was distilled off to give 1-diethylcarbamoyl-3-cyclopropylmethylthio-1,2,4. - 5.2 g of triazole were obtained. Yield 84% Melting point 51-52°C Production Example 2 (Production of Compound 3 of the Invention) Dissolve 2.0 g of 1-diethylcarbamoyl-3-cyclopropylmethylthio-1,2,4-triazole in 100 ml of chloroform, and dissolve metachloroperbenzoic acid. After adding 4.1 g (70% content) over 5 minutes at 5 to 10°C, it was left to stand at room temperature for 15 hours. Washed twice with potassium carbonate aqueous solution, dried with magnesium sulfate,
The solvent was distilled off to give 1-diethylcarbamoyl-3-
cyclopropylmethylsulfonyl-1,2,4-
2.0 g of triazole was obtained. Yield 89% n25.5D 1.5162 Table 1 shows some of the compounds of the present invention that can be produced by such a production method.

【table】

[Table] When producing the compound of the present invention, the compound in which n is 0 among the triazole derivatives [ ] that are the raw material compounds has the general formula R ₃ Y [ ] [where Y represents a halogen atom and R ₃ Same meaning as above. ] A halogen compound represented by and 3-mercapto-
1,2,4-triazole in a solvent in the presence of a dehydrohalogenating agent at 0°C to 150°C for 10 minutes to 24
It can be produced by reacting for a period of time. The amount of reagent used in this reaction is 3-mercapto-1, 3-mercapto-1,
The amount of 2,4-triazole is 0.9 to 1.2 equivalents, and the amount of dehydrohalogenating agent is 1 to 10 equivalents. As a solvent, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as chloroform, methylene chloride, and chlorobenzene,
Ethers such as diethyl ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, organic bases such as pyridine, triethylamine, and N,N-diethylaniline, acetonitrile,
Examples include N,N-dimethylformamide, dimethyl sulfoxide, and water. Examples of dehydrohalogenation agents include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, pyridine, triethylamine, N,N- Examples include organic bases such as diethylaniline. After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as solvent distillation, or further purified by recrystallization, column chromatography, etc., if necessary, to obtain the desired product. In addition, n is 1 in the triazole derivative []
or 2 can be produced by oxidizing a triazole derivative [] where n is 0 using an oxidizing agent. Examples of the oxidizing agent include hydrogen peroxide, aromatic peracids such as m-chloroperbenzoic acid, and aliphatic peracids such as peracetic acid and pertrifluoroacetic acid. A solvent does not necessarily need to be used, but if it is used, it depends on the type of oxidizing agent. For example, for hydrogen peroxide, use water, glacial acetic acid, acetone, etc.; for aromatic peracids, use halogenated hydrocarbons such as chloroform, methylene chloride, etc. , diethyl ether, dioxane and the like are preferred. In the case of aliphatic peracids, it is preferable to use the oxidizing agent itself in excess. The reaction temperature is from the freezing point to the boiling point of the solvent, preferably from 0°C to 100°C, and the reaction time is:
It takes about 10 minutes to 24 hours. After the reaction is completed, the reaction solution is washed with alkaline water,
The desired product can be obtained by performing usual post-treatments such as solvent distillation, or further purifying by recrystallization, column chromatography, etc., if necessary. Next, a production example of the triazole derivative of the general formula [] will be shown. Reference example 3-mercapto-1,2,4-triazole
7.1g and 3.8g of sodium methoxide in methanol
Dissolve cyclopropylmethylbromide in 100ml
9.5g was added and left at room temperature for 10 hours. After distilling off the solvent, the residue was extracted with chloroform, and the chloroform was distilled off to give 3-cyclopropylmethylthio-
10.8 g of 1,2,4-triazole was obtained. Yield 99
% melting point 69-70°C When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant, and other formulation auxiliaries to prepare emulsions, wettable powders,
Formulate into suspensions, granules, etc. These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 90%, preferably 1 to 80%. Solid carriers include fine powders or granules such as kaolin clay, attapalgite clay, pentonite, acid clay, pyrofluorite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexane, and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide,
Examples include acetonitrile and water. Surfactants used for emulsification, dispersion, wetting, etc. include anionic surfactants such as alkyl sulfate salts, alkyl (aryl) sulfonate salts, dialkyl sulfosuccinate salts, and polyoxyethylene alkylaryl ether phosphate salts. surfactant,
Examples include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), and PAP (isopropyl acid phosphate). Examples of formulations are shown below. In addition, the compound of the present invention is the first
Indicated by compound number in the table. Parts indicate parts by weight. Formulation Example 1 1.50 parts of the compound of the present invention, 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder. Formulation Example 2 3.2 parts of the compound of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 78 parts of isophorone are thoroughly mixed to obtain an emulsion. Formulation Example 3 6.2 parts of the compound of the present invention, 1 part of synthetic hydrated silicon oxide
1 part, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 65 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, followed by granulation and drying to obtain granules. Formulation Example 4 14.25 parts of the compound of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water are mixed and pulverized until the particle size becomes 5 microns or less to obtain a suspension. The compound of the present invention thus formulated is treated with soil, foliage, or flooding before or after the emergence of weeds. Soil treatment includes soil surface treatment, soil mixing treatment, etc., and foliage treatment includes treatment from the soil side of plants, as well as local treatment that treats only weeds so that they do not attach to crops. Furthermore, by mixing it with other herbicides, it can be expected to increase the herbicidal efficacy. Furthermore, it can be used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners, and the like. In addition, the compound of the present invention can be used in rice fields, fields, orchards,
It can be used as an active ingredient in herbicides for pastures, lawns, forests, non-agricultural lands, etc. When using the compound of the present invention as an active ingredient of a herbicide, the application amount varies depending on weather conditions, formulation form, application time, method, location, target weeds, target crops, etc., but is usually 0.5g per are. ~200g,
Preferably, the amount is 1 g to 100 g, and includes emulsions, hydrating agents,
Suspending agents, etc. are usually used in a specified amount at a rate of 1 per are.
It is treated by diluting it with 1 to 10 liters of water (adding an auxiliary agent such as a spreading agent if necessary), and granules are usually treated as they are without any dilution. In addition to the above-mentioned surfactants, the spreading agent includes polyoxyethylene resin acid (ester), lignin sulfonate, abietate, dinaphthylmethane disulfonate, paraffin, and the like. Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients of herbicides. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

【table】

[Table] In addition, the herbicidal efficacy is determined by visually observing the degree of inhibition of budding and growth of the test plants during the survey, and ``0'' indicates that there is no or almost no difference from when no compound is tested. A rating of 0 to 5 indicates that the plant is withering or its growth is completely inhibited.
It is evaluated in 6 stages of 5, and is shown as 0, 1, 2, 3, 4, and 5. Test Example 1 Upland Soil Mixing Treatment Test A cylindrical plastic pot with a diameter of 10 cm and a depth of 10 cm was filled with upland soil, and millet, oat, morning glory, and Japanese radish were sown and covered with soil. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was added to 1
It was diluted with water equivalent to 10 liters per area, applied to the soil surface with a small sprayer, and thoroughly mixed into the soil surface to a depth of 4 cm. After treatment, they were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 3.

【table】

[Table] Test Example 2 Upland Soil Treatment Test Upland soil was filled into a vat with an area of 33 x 23 cm ² and a depth of 11 cm, and soybeans, cotton, corn, Japanese jackfruit, chickweed, foxtail grass, snail grass, Seiban sorghum, and Japanese millet were sown. It was covered with soil to a thickness of ~2 cm. The test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the emulsion was applied to the soil surface using a small sprayer. After treatment, they were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 4.

[Table] Test Example 3 Field soil treatment test A cylindrical plastic pot with a diameter of 10 cm and a depth of 10 cm was filled with field soil, and barnyard grass, oats, radish, and Japanese radish were sown and grown in a greenhouse for 10 days.
Thereafter, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water containing a spreading agent equivalent to 10 liters per are, and the foliage was treated from above the plant using a small sprayer. After treatment, they were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The result is the fifth
Shown in the table.

【table】

[Table] Test Example 4 Field soil treatment test A vat with an area of 33 x 23 cm ² and a depth of 11 cm was filled with field soil, and corn, wheat, crabgrass, foxtail grass, and Japanese millet were sown and grown for 18 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2,
A predetermined amount of the solution was diluted with water equivalent to 5 liters per are containing a spreading agent, and the mixture was uniformly applied from the top of the plant to the entire stem and leaf area using a small sprayer. At this time, the growth conditions of weeds and crops varied depending on the grass species, but they were in the 2-4 leaf stage and the plant height was 2-12 cm. Herbicidal efficacy was investigated 20 days after treatment. The result is the 6th
Shown in the table. This test was conducted in a greenhouse throughout the entire period.

[Table] Test Example 5 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 8 cm and a depth of 12 cm was filled with paddy soil, and seeds of Japanese millet, broad-leaved weeds (Azaena, Kikashigusa, Chickweed), and firefly were added to a depth of 1 to 2 cm. mixed into. After flooding the rice field to create a paddy field, two-leaf stage rice was transplanted and grown in a greenhouse. Six days later (at the beginning of each weed's emergence), the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with 5 milliliters of water, and the emulsion was applied to the water surface.
After treatment, they were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 7.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R ₁ and R ₂ are lower alkyl groups or R ₁ and
together with R ₂ represents a hexamethylene group,
R ₃ is a cycloalkylalkyl group or 1,3-
represents an alkyl group substituted with a dioxacyclopentan-2-yl group or a 1,3-dioxacyclohexane-2-yl group, and n is 0, 1 or 2
represents. ] A carbamoyltriazole derivative represented by 2 General formula [In the formula, R ₁ and R ₂ are lower alkyl groups or R ₁ and
together with R ₂ represents a hexamethylene group,
R ₃ is a cycloalkylalkyl group or 1,3-
represents an alkyl group substituted with a dioxacyclopentan-2-yl group or a 1,3-dioxacyclohexane-2-yl group, and n is 0, 1 or 2
represents. ] A herbicide characterized by containing a carbamoyltriazole derivative represented by the following as an active ingredient.