JPH0576477B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula

[In the formula, R ₁ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, or a trifluoromethyl group, R ₂ represents a hydrogen atom, a lower alkyl group, or a halogen atom, R ₃ and R ₄ are the same or different and represent a hydrogen atom or a lower alkyl group, or are bonded at the terminal to represent -(CH ₂ ) ₄ - or -(CH ₂ ) ₅ -, and R ₅ represents a hydrogen atom or a methyl group; represented, X is -CH=CH-,

[Formula] −CH ₂ −CH ₂ −,

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[Formula] or -OCH ₂ -, Y represents N or CH. ] Carbamoylazole derivative (hereinafter referred to as
The present invention relates to a compound of the present invention) and a herbicide containing the compound as an active ingredient. The compounds of the present invention can be used to treat various weeds that are problematic in foliar and soil treatments in upland fields, such as freckle weeds, Japanese knotweed, purslane, chickweed, whiteweed, Japanese radish, Japanese daikon radish, Japanese hornwort, American hornwort, Ebisu grass, and other weeds.
Broad-leafed weeds such as Japanese commonweed, American golden deer, field pansies, American morning glory, Malva morning glory, Japanese staghorn grass, Japanese Physalis, Japanese Physalis, Japanese Physalis, Japanese fir, sunflower, dog mite, Japanese barnyard grass, Japanese millet, Japanese foxtail grass, etc.
Scrub grass, sycamore, sorghum, oat, oat, seiban sorghum,
The compound of the present invention has a herbicidal effect on weeds of the grass family, such as grasshopper, grasshopper, and soybean grass, as well as weeds of the cyperaceae family, such as dayflower, as well as weeds of the cyperaceae family, such as cyperus spp. It does not cause any harmful chemical damage to major crops such as. 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 japonicus and 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 ₁ , R ₂ , R ₃ , R ₄ and X have the same meanings as above. ] Carbamoyl chloride derivative and general formula shown by

[In the formula, R ₅ and Y represent the same meanings as above. ] It can be produced by reacting the azoles represented by the following in a solvent in the presence of a dehydrochlorination agent at -30°C to 150°C for 0.1 to 24 hours. The amounts of the reagents used in the reaction are 0.5 to 10 equivalents and 1.0 to 10 equivalents of the azole [] and the dehydrochlorination agent, respectively, per 1 equivalent of the carbamoyl chloride derivative []. As a solvent, aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, etc.
Halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, etc. Ketones, esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate, nitrites such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N,N-diethylaniline, Examples include tertiary amines such as tributylamine and N-methylmorpholine, acid amides such as formamide, N,N-dimethylformamide, and N,N-dimethylacetamide, and mixtures thereof. Examples of the dehydrochlorination agent include organic bases such as pyridine, triethylamine, and N,N-diethylaniline, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride. After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, purified by chromatography, distillation, recrystallization, etc. to obtain the desired compound of the present invention. can be obtained. Next, production examples of the compounds of the present invention will be shown. Production example 1 N-chlorocarbonyl-2,2-dimethyl-6
0.70 g of -chloro-1,2,3,4-tetrahydroquinoline, 0.55 g of imidazole, 0.33 g of triethylamine, and 0.45 g of potassium carbonate were added to 10 ml of tetrahydrofuran, and the mixture was reacted under reflux for 4 hours. After cooling, water and chloroform were added to separate the layers, and the organic layer was concentrated. The residue was purified by column chromatography packed with silica gel (eluent: n-hexane/ethyl acetate) to obtain N-(1-imidazolylcarbonyl)-2,2-dimethyl-6-
Chloro-1,2,3,4-tetrahydroquinoline
0.66 g was obtained as crystals. (yield 84.6%) mp
124.7℃ Production example 2 4-(chlorocarbonyl)-3,3,6,7-tetramethyl-1,2,3,4-tetrahydro-2
-quinoxalinone 1.30g, imidazole 1.00g,
Triethylamine and 0.81 g of potassium carbonate were added to 20 ml of tetrahydrofuran, and the mixture was reacted under reflux for 4 hours. After cooling, add water and chloroform to separate the liquids.
The organic layer was concentrated. By adding n-hexane and ether to the residue and cooling it, 4-(1-imidazolylcarbonyl)-3,3,6,7-tetramethyl-1,2,3,4-tetrahydro-2-quinoxaline) 1.32g was obtained as crystals. (yield
90.4%) mp185.4°C Some of the compounds of the present invention that can be produced by such production examples are shown in Table 1.

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[Table] When producing the compound of the present invention, the carbamoyl chloride derivative [], which is a raw material compound, has the general formula

[In the formula, R ₁ , R ₂ , R ₃ , R ₄ and X have the same meanings as above. ] An aniline derivative represented by
It can be produced by reacting 50 equivalents of phosgene in a solvent such as an aromatic hydrocarbon such as toluene or xylene or an ester such as ethyl acetate at 0°C to 150°C for 1 to 24 hours. . After completion of the reaction, the reaction solution is subjected to post-treatment such as concentration under reduced pressure, and if necessary, purified by operations such as distillation and recrystallization to obtain the desired carbamoyl chloride derivative [ ]. In addition, the aniline derivative [] is an organic
Syntheses Col.Vol.3 P.329, Synthesis, 71
(1982), J.Org.Chem., 40 1906 (1975), J.Med.
Chem., 16 251 (1973) and others. Next, a production example of carbamoyl chloride derivative [] will be shown as a reference example. (Reference example) 2,2-dimethyl-6-chloro-1,2,3,
1.96g of 4-tetrahydroquinoline and 4g of phosgene
was added to a solution of 100 ml of toluene, and the mixture was reacted under reflux for 6 hours, and then the reaction solution was concentrated under reduced pressure. By adding n-hexane to the resulting residue and cooling it, N-chlorocarbonyl-2,2-dimethyl-
2.00 g of 6-chloro-1,2,3,4-tetrahydroquinoline was obtained as crystals. (Yield: 77.5%) 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 form emulsions, wettable powders, etc.
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 0.2 to 80%. Examples of the solid carrier include fine powders or granules such as kaolin clay, attapalgite clay, bentonite, acid clay, pyrofluorite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, 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, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, and polyoxyethylene alkylaryl ether phosphate salts. 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. Examples of formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), and the like. 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 27.50 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 11.10 parts of the compound of the present invention. 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 30 parts of xylene and 40 parts of cyclohexanone are thoroughly mixed to obtain an emulsion. Formulation Example 3 9.2 parts of the compound of the present invention, 1 part of synthetic hydrated silicon oxide
1 part, 2 parts of calcium lignin sulfonate, 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 1.25 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 wet-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.
For foliage treatment, in addition to treatment from above the plant body,
There are local treatments that treat 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 the compound of the present invention is used 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 0.2 g per are. ~200
g, preferably 0.5 g to 100 g, and emulsions, hydrating agents, suspending agents, etc. are usually used in a predetermined amount of 1 liter to 10 liters per are (if necessary, an auxiliary agent such as a spreading agent may be added). (added) and treated by diluting with water,
Granules and the like are usually processed as is without any dilution. Examples of the spreading agent include, in addition to the above-mentioned surfactants, polyoxyethylene resin acids (esters), lignin sulfonates, abietenates, dinaphthylmethane disulfonates, 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] 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 Treatment Test A cylindrical plastic pot with a diameter of 10 cm and a depth of 10 cm was filled with upland soil, and Japanese barnyard grass, Japanese foxglove, Japanese morning glory, and Japanese commonweed were sown and covered with soil. 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. 20 after processing
The plants were grown in a greenhouse for one day and their herbicidal efficacy was investigated. The results are shown in Table 3.

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[Table] Test Example 2 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, Japanese 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 results are shown in Table 4.

[Table] Test Example 3 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 1 to 2 seeds of Japanese millet and broad-leaved weeds (Azaena, Kikashigusa, Chickweed) were added to the pot.
Mixed to a depth of cm. After flooding to create a paddy field, two-leaf stage rice was transplanted and grown in a greenhouse. After 6 days (the beginning of the emergence of each weed), 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
The plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 5.

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[Table] Test Example 4 Upland Soil Treatment Test Upland soil was filled into a pot with an area of 33 x 23 cm ² and a depth of 11 cm, and soybean, cotton, corn, wheat, rice, barnyard grass, foxtail grass, Seiban sorghum, Malva morning glory, and Japanese strawberry were sown. The soil was then covered with soil to a thickness of 1 to 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 6.

[Table] Test Example 5 Field soil treatment test Field soil was filled into a vat with an area of 33 x 23 cm ² and a depth of 11 cm, and corn, wheat, barnyard grass, foxtail grass, Seiban sorghum, Malva morning glory, and Japanese strawberry were sown and grown for 18 days. . Then, make an emulsion of the test compound according to Formulation Example 2, dilute the specified amount with water equivalent to 5 liters per are containing a spreading agent, and use a small sprayer to spread it evenly over the entire stem and leaf area from above the plant body. processed. At this time, the growth conditions of weeds and crops vary depending on the grass species, but at the 1-4 leaf stage,
The plant height was 2 to 12 cm. Herbicidal efficacy was investigated 20 days after treatment. The results are shown in Table 7. This test was conducted in a greenhouse throughout the entire period.

[Table] Test Example 6 Paddy field flooding treatment test A 1/5000a Wagner pot was filled with paddy soil.
Japanese millet, broad-leaved weeds (Azeena, Aspergillus japonica, Chickweed), bulrush seeds, and overwintering buds of Pinus spp. were mixed in at a depth of 1 to 2 cm. After flooding to create a paddy field, two-leaf stage rice was transplanted and grown in a greenhouse. 5 days later (beginning of the outbreak of brown millet)
The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was diluted with 10 milliliters of water and applied to the water 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 8. In addition, for two days from the day after the treatment,
The amount of water leaking was equivalent to 3 cm of water depth per day.

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[Table] Test Example 8 Paddy field flooded stem, leaf and soil treatment test Fill a 1/5000a Wagner pot with paddy soil.
Japanese millet, broad-leaved weeds (Azeena, Aspergillus japonica, Chickweed), bulrush seeds, and overwintering buds of Pinus spp. were mixed in at a depth of 1 to 2 cm. After flooding to create a paddy field, two-leaf stage rice was transplanted and grown in a greenhouse. 12 days later (3-leaf stage of Japanese millet)
The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was diluted with 10 milliliters of water and applied to the water 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 9. In addition, for two days from the day after the treatment,
The amount of water leaking was equivalent to 3 cm of water depth per day.

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Claims (1)

[Scope of Claims] 1 General Formula: [In the formula, R ₁ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, or a trifluoromethyl group, and R ₂ represents a hydrogen atom, a lower alkyl group, or a trifluoromethyl group. represents a halogen atom, R ₃ and R ₄ are the same or different and represent a hydrogen atom or a lower alkyl group, or are bonded at the terminal to represent -(CH ₂ ) ₄ - or -(CH ₂ ) ₅ -, R ₅ represents a hydrogen atom or a methyl group, X represents -CH=CH-, [formula] -CH ₂ -CH ₂ -, [formula] [formula] [formula] or -OCH ₂ -, and Y represents N Or represents CH. However, when R ₃ , R ₄ and R ₅ are all hydrogen atoms and Y is CH, X is not -CH ₂ -CH ₂ -. ] A carbamoylazole derivative represented by: 2 General formula: [In the formula, R ₁ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, or a trifluoromethyl group, R ₂ represents a hydrogen atom, a lower alkyl group, or a halogen atom, and R ₃ and R ₄ are the same or different and represent a hydrogen atom or a lower alkyl group, or are bonded at the terminal to represent -(CH ₂ ) ₄ - or -(CH ₂ ) ₅ -, and R ₅ is a hydrogen atom or represents a methyl group; X represents -CH=CH-, [Formula] -CH ₂ -CH ₂ -, [Formula] [Formula] [Formula] or -OCH ₂ -; However, when R ₃ , R ₄ and R ₅ are all hydrogen atoms and Y is CH, X is not -CH ₂ -CH ₂ -. ] A herbicide characterized by containing a carbamoylazole derivative represented by the following as an active ingredient.