JPH042590B2 - - 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 the same or different and represent a hydrogen atom or a methyl group, and R ₃ represents a lower alkyl group. ] 4,5,6,7-tetrahydro-2H represented by
-Isoindole-1,3-dione derivative (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 tetrahydro-2H-isoindole-1,3-dione derivatives, such as 2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione, 2-
(2-Fluoro-4-chloro-5-carboxyphenyl)-4,5,6,7-tetrahydro-2H-
The fact that isoindole-1,3-dione can be used as an active ingredient in herbicides was reported in the Japanese Patent Publication No. 1973-
It is described in JP-A No. 11940 and JP-A-57-112371. 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 currant, snail knotweed, purslane, whiteweed, blueberry, American hornwort,
Ebisugusa, Ichibi, Golden Deer, Field Pansy, Yaemugura, American Morning Glory, Mulva Morning Glory, Western Convolvulus, Helicoptera vulgaris, Hotokenoza, Prunus spp.
The present invention has a herbicidal effect on broad-leaved weeds such as corn marigold, grass weeds such as barnyard grass, barnyard grass, foxtail grass, and grass weeds, as well as weeds of the Cyperaceae family such as dayflower, and Cyperaceae weeds such as Cyperus japonica. The compound does not cause any problematic phytotoxicity to major crops such as corn, wheat, rice, and soybean. 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 grasshopper, broad-leaved weeds such as azalea, azalea, and chickweed; It has a herbicidal effect on paddy field weeds such as weeds, Japanese grasshopper, and rice field weeds, 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 and R ₃ have the same meanings as above. ] It can be produced by reacting the aniline derivative represented by the following with 3,4,5,6-tetrahydrophthalic anhydride in a solvent at 80° C. to the boiling point of the solvent for 1 hour to 24 hours. The amount of reagents used in the reaction is 1.0 to 1.05 equivalents of 3,4,5,6-tetrahydrophthalic anhydride per equivalent of aniline derivative []. Solvents include aliphatic hydrocarbons such as hexane, heptane, and ligroin, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene. Ethers such as diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone, isophorone, and cyclohexanone, fatty acids such as formic acid, acetic acid, and oleic acid, ethanol, isopropanol,
Alcohols such as t-butanol, octanol, cyclohexanol, methyl cellosolve, diethylene glycol, glycerin, ethyl formate,
Esters such as ethyl acetate, butyl acetate, and diethyl carbonate, nitrides such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine,
N,N-diethylaniline, tributylamine,
Tertiary amines such as N-methylmorpholine, acid amides such as formamide, N,N-dimethylformamide and acetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, water, etc.
There are mixtures of them. After the reaction is completed, usual post-treatments are carried out, and if necessary, purification is carried out by chromatography, distillation, recrystallization, etc. Or general formula [In the formula, R ₁ and R ₂ have the same meanings as above. ] A carboxylic acid represented by the general formula R ₃ OH [ ] [wherein R ₃ represents the same meaning as above. ] It can be produced by reacting the alcohol represented by the following in the presence or absence of a solvent, using a catalytic amount of a dehydrating agent, at the boiling point of the solvent or alcohol (). The amount of alcohol [ ] used in this reaction is
The amount is 1.0 to large excess equivalent to 1 equivalent of carboxylic acid.Solvents include aromatic hydrocarbons such as toluene and benzene, and dehydrating agents include concentrated sulfuric acid, alkylsulfonic acids, and aryl. Examples include sulfonic acid. Next, production examples of the compounds of the present invention will be shown. Production Example 1 (Production of Compound 1 of the Invention) 0.24 g of ethyl 3-amino-6-chloro-4-fluoro-cinnamate and 0.16 g of 3,4,5,6-tetrahydrophthalic anhydride were mixed with 5 ml of acetic acid. The mixture was heated under reflux for 1.5 hours. After cooling, water and toluene were added and extracted with toluene. The toluene layer was washed with saturated sodium bicarbonate solution, dried, and concentrated. The residue was crystallized from methanol, recrystallized from ethanol,
2-[4-chloro-2-fluoro-5-(2-ethoxycarbonylvinylene)phenyl]-4,5,
6,7-tetrahydro-2H-isoindole-
0.15 g of 1,3-dione was obtained. mp129-130°C Production Example 2 (Production of Compound 3 of the Invention) 2-[4-chloro-2-fluoro-5-(2-carboxy-1-methylvinylene)phenyl]-4,
The mixture was heated under reflux for 3 hours with 1 g of 5,6,7-tetrahydro-2H-isoindole-1,3-dione, 20 ml of methanol, and several drops of concentrated sulfuric acid. Methanol was distilled off under reduced pressure, and water and toluene were added to the residue for extraction. The toluene layer was washed with water and saturated sodium bicarbonate solution, dried and concentrated, and the residue was purified using a silica gel column to obtain 2-[4-chloro-2-fluoro-5-(2-methoxycarbonyl-1-methylvinylene)phenyl]. 0.6 g of -4,5,6,7-tetrahydro-2H-isoindole-1,3-dione was obtained. _n ^21.5D
1.5609 Table 1 shows some of the compounds of the present invention that can be produced by such a production method.

[Table] When producing the compound of the present invention, the raw materials aniline derivative [] and carboxylic acid [] can be produced by the following route. [In the formula, R ₁ and R ₂ represent the same meanings as above,
R ₄ represents a hydrogen atom or a lower alkyl group. ] In other words, in the case of producing aniline derivatives [ ], R ₄ = lower alkyl in the above route, and after producing carboxylic acids ( ) from ketones ( ) with a suitable Whittig reagent or a reagent such as alkyl malonate. , Nitrobenzene ( ) was obtained by nitration with a mixed acid of nitric acid and sulfuric acid, and then the nitro group was selectively reduced using iron in acetic acid to obtain an aniline derivative ( ) (where R ₄ = lower alkyl group) can be obtained. In addition, in the case of producing carboxylic acid [], in the above route, R ₄ = hydrogen atom, and in the same manner as above, aniline derivative () (However, R ₄ =
A carboxylic acid () can be obtained by further reacting with 3,4,5,6-tetrahydrophthalic anhydride in the presence of a solvent such as acetic acid, water, or toluene. Next, a production example of the aniline derivative [] will be shown as a reference example. Reference example 1 Dissolve 5 g of 2-chloro-4-fluoro-benzaldehyde in 5 ml of benzene, and add 7.1 g of triethylphosphonoacetate and sodium hydride (50%).
It was added dropwise to a benzene solution of Whittig reagent prepared from 1.6 g and 15 ml of benzene at 10 to 20°C. Another 20~
After stirring at 30°C for 3 hours, water was added and the benzene layer was separated, dried and concentrated to obtain 7 g of crude ethyl 2-chloro-4-fluorocinnamate. This was dissolved in 5 ml of concentrated sulfuric acid, a mixed acid of 2.5 g of fuming nitric acid and 2 ml of concentrated sulfuric acid was added dropwise at room temperature, and the mixture was stirred at 20 to 30°C for 1 hour.
After pouring into water, the mixture was extracted with ether, washed with water, dried, and concentrated. The residue was purified using a silica gel column,
0.6 g of ethyl 2-chloro-4-fluoro-5-nitro-cinnamate was obtained. (mp105-105.5℃) Furthermore, dissolve this in 5ml of acetic acid, 0.6g of iron powder,
The mixture was added dropwise to a system containing 10 ml of 5% aqueous acetic acid under reflux. After the dropwise addition, the mixture was refluxed for 30 minutes, allowed to cool, and extracted with chloroform. The chloroform layer was washed with water and saturated sodium hydrogen chloride solution, dried, and concentrated to obtain 0.28 g of ethyl 3-amino-4-fluoro-6-chloro-cinnamate. (mp127-127.5°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, liquid carrier, surfactant, or other formulation auxiliary agent, and then prepared as an emulsion, a wettable powder, or
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 95%, preferably 0.1 to 80%.
contains. Solid carriers include fine powders or granules such as kaolin clay, attapalgite clay, bentonite, acid clay, pyrophyllite, 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, 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, alkyl (aryl) sulfonate salts, dialkyl sulfosuccinate salts, and polyoxyethylene alkylaryl ether phosphate salts. Examples include nonionic surfactants such as surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Formulation auxiliaries include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethylcellulose), and PAP (isopropyl acid phosphate).
etc. 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 Compound 1 of the present invention, 50 parts, calcium lignin sulfonate, 3 parts, sodium lauryl sulfate, 2 parts, and 45 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder. Formulation Example 2 10 parts of Compound 4 of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 parts of cyclohexanone 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 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 25 parts of Compound 1 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., and foliage treatment includes treatment from above the plant body, 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 the compound of the present invention is used as an active ingredient of a herbicide, the application amount varies depending on weather conditions, lumber form, application time, method, location, target weeds, target crops, etc., but is usually 0.05 g to 1 are. 20g,
Preferably, it is 0.1g to 10g, and emulsions, hydrating agents,
Suspension agents, etc. should be diluted with water (adding a spreading agent or other dispersion aid if necessary) and applied at a rate of 1 liter to 10 liters per are; granules, etc.
Apply as is without any dilution. In addition to the above-mentioned surfactants, the spreading agent includes polyoxyethylene resin acid (ester), lignin sulfonate, abietate, inaphthylmethane 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] 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 shown as 0, 1, 2, 3, 4, and 5. Test Example 1 Upland Soil Mixing Treatment Test Upland soil was filled into a cylindrical plastic pot with a diameter of 10 cm and a depth of 10 cm, and Japanese barnyard grass, Japanese amberjack, Japanese morning glory, and Japanese commonweed were sown and covered with soil. Prepare the test compound as a wettable powder according to Formulation Example 1, dilute the specified amount with water, spray it on the soil surface with a small sprayer at a rate of 10 liters per are, and then spray it on the soil surface to a depth of 4 cm. The soil surface layer was thoroughly mixed. After spraying
The plants 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 Japanese barnyard grass, Japanese grasshopper, Japanese morning glory, and Japanese commonweed were sown and grown in a greenhouse for 10 days. The test compound was made into an emulsion according to Example 2, and a predetermined amount of the emulsion was diluted with water containing a spreading agent.
The foliage was sprayed from above the plant using a miniaturized sprayer at a rate of 10 liters per area. 20 after spraying
The plants were grown in a greenhouse for one day 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 (Azana, Kikashigusa, and Chickweed) were placed in a cylindrical plastic pot with a diameter of 8 cm and a depth of 12 cm.
Mixed to a depth of cm. After flooding to create a paddy field, tubers of Urikawa were buried at a depth of 1 to 2 cm, and then rice at the two-leaf stage was transplanted and grown in a greenhouse. Six days later (at the beginning of each weed's emergence), the test compound was made into granules according to Formulation Example 3, diluted with water in a predetermined amount, and dropped onto the water surface at a rate of 5 milliliters per pot. After application, the plants 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 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 the soil was filled with field soil, and the soil was filled with field soil, and the soil was filled with field soil. Sowing wheat, soybeans and corn, 18
It was grown for days. Thereafter, make an emulsion of the sample compound according to Formulation Example 2, dilute it with water containing a spreading agent, and spray it uniformly over the entire dry part of the stem from the top of the plant using a small sprayer at a rate of 5 liters per are. Spread. At this time, the growth of each plant varied depending on the grass species, but it was in the 1-4 leaf stage and the plant height was 2-12 cm. Weed efficacy was investigated 20 days after spraying. The result is the 6th
Shown in the table. Note that this test was conducted at room temperature throughout the entire period.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a methyl group, and R ₃ represents a lower alkyl group. ] 4,5,6,7-tetrahydro-2H represented by
-isoindole-1,3-dione derivative. 2 General formula [In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a methyl group, and R ₃ represents a lower alkyl group. ] General formula characterized by reacting the aniline derivative represented by and 3,4,5,6-tetrahydrophthalic anhydride [In the formula, R ₁ , R ₂ and R ₃ have the same meanings as above. ] 4,5,6,7-tetrahydro-2H represented by
-Production method of isoindole-1,3-dione derivative. 3 General formula [In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a methyl group. ] A carboxylic acid represented by the general formula R ₃ OH [wherein R ₃ represents a lower alkyl group]. ] A general formula characterized by reacting with an alcohol represented by [In the formula, R ₁ , R ₂ and R ₃ have the same meanings as above. ] 4,5,6,7-tetrahydro-2H represented by
-Production method of isoindole-1,3-dione derivative. 4 General formula [In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a methyl group, and R ₃ represents a lower alkyl group. ] 4,5,6,7-tetrahydro-2H represented by
- A herbicide comprising an isoindole-1,3-dione derivative as an active ingredient.