JPH0545593B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [In the formula, R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group, or an alkoxyalkoxyalkyl group, and R ₂ represents a hydrogen atom or a methyl group. ] The present invention relates to a tetrahydrophthalimide derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, and a herbicide containing the same as an active ingredient. Certain tetrahydrophthalimide derivatives, such as 2-(4-methoxyphenyl)-4,5,
6,7-tetrahydro-2H-isoindole-
It is described in Japanese Patent Publication No. 11940/1983 that 1,8-dione can be used as an active ingredient in 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 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 common grass, golden deer, field pansies, Japanese grass, American morning glory, Malva morning glory, hotokenoza, Japanese morning glory, Japanese dogweed, Japanese whiteflies, Japanese fir, sunflower, Japanese chamomile, corn marigold, barnyard grass, Japanese barnyard grass, foxtail grass, and black grass. It has herbicidal activity against weeds of the grass family, such as cypress, grasshopper, oat, oat, and sorghum, weeds of the family Cyperaceae, such as dayflower, and weeds of the family Cyperaceae, such as cypress does not cause any harmful effects on major crops such as corn, wheat, rice, soybean, and cotton. In addition, the compound of the present invention can be applied to various weeds that are a problem in the waterlogging treatment of rice fields, such as grass weeds such as Japanese millet, broad-leaved weeds such as azalea, commonweed, and chickweed, cyperaceae weeds such as bulrushes, and cyperus spp. It has a herbicidal effect on grasshoppers, etc., and does not cause any harmful effects on rice. The compound of the present invention has the general formula [In the formula, R ₁ and R ₂ have the same meanings as above. ] An aminobenzoxazinone derivative represented by
In contrast, 1.0 to 1.1 equivalents of 3,4,5,6-
Tetrahydrophthalic anhydride in a solvent at 80℃~
It can be produced by reacting at 200°C for 1 to 24 hours. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as dioxane and ethylene glycol dimethyl ether, fatty acids such as formic acid and acetic acid, water, and mixtures thereof. After the reaction is complete, the reaction solution is subjected to normal post-treatments such as adding water and separating the formed crystals, and if necessary, purified by chromatography, recrystallization, etc. to obtain the desired product. The compound of the present invention can be obtained. Next, production examples of the compounds of the present invention will be shown. Production Example 1 (Production of Compound 8 of the Present Invention) 6-amino-4-propargyl-1,4-benzoxazin-2H-3-one 0.8 g, 3,4,
A mixture of 0.61 g of 5,6-tetrahydrophthalic anhydride and 20 ml of acetic acid was heated under reflux for 2 hours. After cooling, water was added and the resulting crystals were separated and washed with water. Recrystallized from ethanol to give 2-(3-oxo-4-propargyl-2H-1,4-benzoxazin-6-yl)
4,5,6,7-tetrahydroisoindole-
0.4 g of 1,3-dione was obtained. mp205-206°C Some of the compounds of the present invention that can be produced by such a production method are shown in Table 1.

[In the formula, R ₁ represents the same meaning as above, and X represents a halogen atom. ]

A halide represented by is mixed in a solvent at room temperature to 150°C in the presence of 1.0 to 1.1 equivalents of a dehydrohalogenating agent.
It can be produced by reacting for 0.5 to 6 hours. Examples of solvents include nitriles such as acetonitrile and isobutyronitrile, acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, hexamethylphosphoramide, etc. , their mixture is opened. Examples of the dehydrohalogenation agent include alkali metal alkoxides such as sodium methoxide and sodium ethoxide, and bases such as sodium hydride. After the reaction is complete, the reaction solution is poured into water and subjected to usual post-treatments such as organic solvent extraction and concentration using ethyl acetate, etc., and if necessary, chromatography,
By purifying by operations such as recrystallization, the desired nitrobenzoxazinone derivative of the general formula [] can be obtained. Next, a production example of the aminobenzoxazinone derivative of the general formula [] will be shown. Production Example 8 4.1 g of 2-methyl-6-nitro-1,4-benzoxazin-2H-3-one was added to a mixture of 1 g of 60% sodium hydride and 5 ml of N,N-dimethylformamide at a temperature below 20°C. After stirring for another 30 minutes, 3.7 g of propargyl bromide was added, and 3.7 g of propargyl bromide was added.
Allowed time to react. After cooling, add water, extract with ethyl acetate, wash with water, dry, and concentrate to obtain crude 2-methyl-4-
5 g of propargyl-6-nitro-1,4-benzoxazin-2H-3-one were obtained as a red oil. Dissolve this in a mixture of 50 ml of acetic acid and 50 ml of ethyl acetate, and add 6 g of iron powder and 50 ml of 5% acetic acid water for 80~
It was added dropwise at 90°C. After the addition, the mixture was stirred under reflux for 1 hour. After cooling, the iron was separated and water was added to the liquid to decompose it. The aqueous layer was extracted with ethyl acetate, the organic layers were combined, washed with saturated aqueous sodium bicarbonate, dried, and concentrated. The residue was crystallized from methanol and 6-amino-2-methyl-4-
Propargyl-1,4-benzoxazine-2H
2.2 g of -3-one was obtained. mp158-159℃ 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 solubilizing agents to form an emulsion, a wettable powder,
Formulate into suspensions, granules, etc. These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.05 to 90%, preferably 0.1 to 80%.
contains. Examples of solid carriers include fine powders or granules such as kaolin clay, attapalgite clay, bentonite, acid clay, pyrofluorite, talc, diatomaceous earth, calcite, walnut, 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, acetone,
Examples include ketones such as cyclohexanone and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, 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. and 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 8, 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 9.5 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 45 parts of isophorone are thoroughly mixed to obtain an emulsion. Formulation Example 3 Compound 3 of the present invention, 2 parts, synthetic hydrated silicon oxide 1
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 8, 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 that the herbicidal efficacy will be enhanced. Furthermore, it can be used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners, and the like. 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 0.02 g per are. ~100
g, preferably 0.05 g to 50 g, and for emulsions, wetting agents, suspension agents, etc., the prescribed amount is usually 1 liter to 10 liters per arm, and if necessary, auxiliary agents such as spreading agents are used. (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, abietates, dinaphthylmethane disulfonates, paraffin, and the like. Next, test examples will show 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 was determined by visually observing the degree of budding and growth inhibition of the test plants at the time of the survey, and if there was no difference at all from the case where no compound was tested, the herbicidal efficacy was evaluated as "0". 0 to 5, with ``5'' indicating that the plant has died or its growth has been completely inhibited.
It is evaluated in 6 stages and is indicated as 1, 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, sown with Japanese barnyard grass, Japanese morning glory, and Japanese sardine, 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. 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 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 for 10 days at room temperature. 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】

[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 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 5.

[Table] Test example 4 Upland soil treatment test Pack field soil into a vat with an area of 33 x 23 cm ² and a depth of 11 cm, and sow soybean, corn, Japanese fir tree, Japanese morning glory, Japanese radish, blueberry, Japanese Physalis, Japanese commonweed, and foxtail grass. 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 6.

[Table] Test example 5 Upland 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 wheat, Japanese violet, Japanese grasshopper,
Chickweed, whitewort, Japanese knotweed, buckwheat, and sycamore were sown and 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, the plants were grown in a greenhouse for 27 days and their herbicidal efficacy was investigated. The results are shown in Table 7.

【table】

[Table] Test Example 6 Field soil, stem, and leaf 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, sugar beet, Japanese fir, Japanese radish, Japanese Physalis, Maruba morning glory, Shiroza, and Japanese foxtail were sown. It was grown for 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 varied depending on the grass species, but they were in the 1-4 leaf stage and the plant height was 2-12 cm.
Herbicidal efficacy was investigated 20 days after treatment. The results are shown in Table 8. This test was conducted in a greenhouse throughout the entire period.

[Table] Test example 7 Paddy field flooding treatment test Fill a 1/5000a Wagner pot with paddy soil.
Japanese millet, broad-leaved weeds (Azeena, Azalea, Chickweed), bulrush seeds, and overwintering buds of Atsubai were mixed in at a depth of 1 to 2 cm. After flooding the rice field to create a paddy field, three-leaf stage rice was transplanted and grown in a greenhouse. After 6 days (the beginning of germination 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 result is the 9th
Shown in the table. In addition, for two days from the day after the treatment, water leaked in an amount equivalent to a water depth of 3 cm per day.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group, or an alkoxyalkoxyalkyl group, and R ₂ represents a hydrogen atom or a methyl group. ] A tetrahydrophthalimide derivative represented by 2 General formula [In the formula, R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxyalkyl group, or an alkoxyalkoxyalkyl group, and R ₂ represents a hydrogen atom or a methyl group. ] A herbicide characterized by containing a tetrahydrophthalimide derivative represented by the following as an active ingredient.