JPS63313770A - Isatin derivative and herbicide containing the same as an active ingredient - Google Patents

Abstract

NEW MATERIAL:An isatin derivative of formula I (R is lower alkyl, lower alkenyl, lower alkinyl). EXAMPLE:N-(1-Ethyl-5-fluoroindolin-2,3-dion-6-yl)-3,4,5,6-tetrahydroph thalimide. USE:It is used as a herbicide. It shows excellent herbicidal effect with high selectivity between crop plants and weeds. It can control broad leaf weeds such as pink smartweed, smooth pigweed, rough pigweed; true grasses such as barnyard grass or green foxtail. Further, it shows effects against waterwort, false pimpernel or slender spikerush, which cause troubles in water paddy submerge treatment. It does not damage rice plant, corns and other cereal plants. PREPARATION:The reaction of a compound of formula II with another compound of formula III is carried out in a solvent in the presence of a dehydrohalogenating agent at -10-50 deg.C to give the compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel isatin derivative, a method for producing the same, and a herbicide containing the same as an active ingredient.

<Prior Art> Until now, it has not been known that isatin derivatives can be used as active ingredients of herbicides.

<111 problems to be solved by the invention> Many herbicides are currently in use, but their herbicidal efficacy is insufficient.
It is difficult to say that this method is necessarily satisfactory because of its stiffness and poor selectivity between crops and weeds.

Means for Solving the Eight Problems> As a result of various studies in order to develop an excellent herbicide, the present inventors found that a compound having a tetrahydrophthalimide group at the 6-position of isatin has excellent herbicidal efficacy. , and showed excellent selectivity between crops and weeds, leading to the present invention.

That is, the present invention is based on the general formula [! In formula 1, k represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group. The present invention provides an isatin 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.

Next, the method for producing the compound of the present invention will be explained in detail.

The compound of the present invention is a compound represented by the formula [I] and a compound represented by the general formula [ml RA] [wherein R represents the same meaning as above and A represents a halogen atom. ] It can be obtained by reacting with a compound shown in the following.

The reaction is usually carried out in a solvent in the presence of a dehalogenated water accumulating agent, and the reaction temperature is typically in the range of -10 to 50°C and the reaction time is in the range of 0.5 to 6 hours. The amount of the reagent used in the reaction is 1.0 to 1.5 equivalents of the compound represented by the general formula [1111] and 1.5 equivalents of the dehydrohalogenating agent per 1 equivalent of the compound represented by the formula [I[]. It is 0 to 1.5 equivalents.

Examples of solvents include ethers such as dioxane, tetrahydrofuran, and diethylene glycol dimethyl ether, alcohols such as methanol, ethanol, isopropanol, t-butanol, octatool, cyclohexanol, methyl cellosolve, diethylene glycol, and glycerin, acetonitrile, and isobutyronitrile. nitriles such as formamide, N,N-dimethylformamide, acid amide such as acetamide, dimethyl sulfoxide,
Examples include sulfur compounds such as sulfolane, and mixtures thereof.

Examples of the dehydrohalogenation agent include inorganic bases such as sodium carbonate, potassium carbonate, and sodium hydride, and alkali metal alkoxides such as sodium methoxide and sodium ethoxide.

After the reaction is complete, the reaction solution is subjected to the usual post-treatment of organic solvent extraction and concentration, and if necessary, chromatography,
It can be purified by operations such as recrystallization.

Further, among the compounds of the present invention, those in which R is a lower alkyl group are represented by the general formula [3/] [wherein R' represents a lower alkyl group]. ] It can also be produced by oxidizing the indole derivative shown. The oxidation reaction is described, for example, by Frank D., Pop.
Advances in Heterocycle by p.
cChemistry Volume 18, Page 2 (1975,
It can be carried out according to the description in ``Academi cPress Publishing''.

That is, it is produced by using chromic anhydride in a ratio of 2/8 to 8 mol per 1 mol of the indole derivative represented by the general formula [1/] and reacting it in a solvent at 20 to 150°C. As the solvent, organic acids such as acetic acid and propionic acid or water-containing mixtures thereof are used. After the reaction is completed, usual post-treatments such as organic solvent extraction and concentration are performed, and if necessary, purification such as column chromatography is performed.

The compound represented by formula [I[], which is a raw material for producing the compound of the present invention, is produced as follows.

5-fluoro-2,4-dinitrotoluene in a solvent (for example, N,N-dimethylformamide, 1,4-dioxane, 1,2-jethoxyethane, etc. are used), 5
-5-Fluoro-2 obtained by reacting 1.0 to 1.1 equivalents of N,N-dimethylformamide dimethyl acecool to 1 equivalent of fluoro-2,4-dinitrotoluene at 40 to 160°C. , 4-dinitro-β-dimethylaminostyrene is hydrogenated in an alcohol such as ethanol or propatool in the presence of a catalytic amount of acid using a reduction catalyst such as palladium on carbon or platinum oxide at 10 to 80°C under normal pressure. 6-amino-5 by reduction and ring closure
- A fluoroindole is produced. Next, 6-amino-5-
1.0 to 1.05 equivalents of 8.4,5.6-titrahydrophthalic anhydride to 1 equivalent of fluoroindole.
A compound represented by the formula tl[] is produced by reacting at 0 to 150°C.

In addition, the raw material compound represented by the general formula [1/] is
It is manufactured according to the method described in No. 2-5628.

Specific examples of R in the compounds of the present invention include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 8-butyl group, allyl group, 1-methyl-2-
propenyl group, 2-methyl-2-propenyl group, 8-methyl-2-butenyl group, 2-methyl-2-butenyl group,
Examples include propargyl group, 1-methylpropargyl group, 1-methyl-2-butynyl group, and 1-ethylpropargyl group.

The compounds of the present invention have excellent herbicidal efficacy and exhibit excellent selectivity between crops and weeds. That is, the compound of the present invention is
Various weeds that pose problems in the treatment of foliage and soil damage in upland fields, such as snail knotweed, purslane, whiteweed,
Broad-leafed weeds such as Japanese radish, Japanese radish, Japanese radish, Japanese sorghum, American gold deer, field pansies, Marpa morning glory, Hotokenoza, white banana 1, Japanese morning glory, Japanese Physalis, Japanese sorghum, Japanese sorghum, etc. The compound of the present invention has a herbicidal effect against grass weeds, etc., and does not cause any problematic phytotoxicity to major crops such as corn, wheat, barley, soybean, peanut, cotton, and sugar beet.

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 weed, and chickweed, cyperaceae weeds such as pine snail, and cyperus weeds. It has a herbicidal effect on rice, and does not cause any harmful effects on rice.

When using the compound of the present invention as an active ingredient of a herbicide,
It is usually mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to formulate emulsions, wettable powders, suspensions, granules, and the like.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.5 to 80%, preferably 1 to 70%.

Examples of solid carriers include fine powders or granules such as kaolin clay, aphthapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide purple. 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, and dimethyl Sulfoxide, N, N
- Dimethylformamide, acetonitrile, water, etc.

Surfactants used for emulsification, dispersion, wetting layers, etc. include alkyl sulfate salts, alkyl sulfonate salts, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, polyoxyethylene alkylaryl ether phosphate salts, etc. Nonionic surfactants such as anionic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. .

Other formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), and the like.

The compound of the present invention is usually formulated and treated with soil, foliage, or flooding before or after the emergence of weeds. Soil treatment includes soil surface treatment, soil breaking mixing treatment, etc. Stalk 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 using it in combination 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, pastures,
It can be used as an active ingredient in lawns, forests or non-agricultural lands.

When the compound of the present invention is used as an active ingredient of a herbicide, the amount to be treated will vary depending on weather conditions, formulation form, treatment time, method, location, target weeds, target crops, etc., but usually 1.
1f~200g per are, preferably 10j'~
Emulsions, wettable powders, suspension agents, etc. are usually diluted in a specified amount with 1 liter to 10 liters of water per are (if necessary, auxiliary agents such as spreading agents are added). Granules and the like are usually processed as they are without any dilution.

In addition to the above-mentioned surfactants, the spreading agents include polyoxyethylene resin acid (ester), lignin sulfonate,
Examples include abietate, dinaphthylmethane disulfonate, and paraffin.

<Effects of the Invention> The compound of the present invention has excellent herbicidal efficacy against various weeds that are problematic in soil destruction treatment and foliage treatment of fields, as well as hot water treatment of rice fields, and has an excellent weed control effect between major crops and weeds. Since it exhibits selectivity, it can be used for various purposes as an active ingredient in herbicides.

<Examples> The present invention will be explained in more detail below using production examples, formulation examples, and test examples, but the present invention is not limited to these examples.

First, a production example of the compound of the present invention will be shown.

Production Example 1 (Production of Compound (6) of the Present Invention) N-(5-fluoro-indolin-2,8-dion-6-yl)-8
, 0.88f of 4,5,6-titrahydrophthalimide was added little by little to a mixture of 0.046f of sodium hydride (60% oil) and 10++d of dimethylformamide at -10 to θ°C. Next, after stirring at the same temperature for 80 minutes, 0.14 F of propargyl bromide was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1.5 hours, and then the reaction solution was poured into ice water and extracted with ether.

After washing the ether layer with water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was treated with silica gel column chromatography to obtain N-(5-fluoro-1-propargylindoline-2,8-dione- 6-il)-8
0.18f of 4.5.6-titrahydrophthalimide was obtained. n”,:” 1.5686 Production Example 2 (Production of Compound (1) of the Present Invention) N-(1-ethyl-5-fluoroindol-6-yl)-8,4,5
, 2.291 gd of 6-titrahydrophthalimide was added to a mixture of 1.6 F chromic anhydride, 65 gd of acetic acid, and 5.4 gd of water at 20-80°C. Next, test water stirred at 100° C. for 0.5 hours was added and extracted with ether. The ether layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residual liquid was treated with silica gel column chromatography to obtain N-(1-ethyl-5-fluoroindoline-2
, 8-dione-6-yl)-8,4°5.6-titrahydrophthalide 0.16 f was obtained. mpl 98
．． 5 to 199.5°C Next, Table 1 shows some of the compounds of the present invention produced according to these production methods.

Table 1 Next, production examples of the compound represented by formula [1], which is a wave velocity raw material for the compound of the present invention, are shown as reference examples.

Reference example Production of N-(5-fluoroindolin-2°8-dion-6-yl)-8,4,5°6-titrahydrophthalimide (i) 5-fluoro-2,4-dinitro-β-dimethyl Production of aminostyrene 5-fluoro-2,4-dinitrotoluene 15y, N,
N-dimethylformamide dimethyl acecool8.98
A mixture of 1 and dioxane 75 was stirred at 96-100°C for 1.5 hours. Next, after cooling to room temperature, ether was added and the resulting crystals were collected.

The crystals were further washed with ether to give 5-fluoro-2,4
-dinitro-β-dimethylaminostyrene 6.7f was obtained. ml) 184-186°C (i) Production of 6-amino-6-fluoroindole 5-fluoro-2,4-sinitro β- obtained above
Dimethylaminostyrene 5.7f ethanol 200d
0.81% of 10% palladium on carbon was added, and about 6.24% of hydrogen was blown into the solution under normal pressure. Remove the catalyst from the furnace, P
The liquid was concentrated under reduced pressure to obtain 8.8 g of 6-amino-5-fluoroindole.

(b) N-(5-fluoroindol-6-yl)-
Preparation of 8,4,5,6-titrahydrophthalimide 6-amino-5-fluoroindole 8 obtained above
．． 8g and 4.2y of 8.4.5.6-titrahydrophthalic anhydride were heated under reflux in 25cm of acetic acid for 8 hours. Next, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was treated with silica gel column chromatography to obtain N-(5-fluoroindol-6-yl)-8,4, 5,6-tetrahydrophthalimide5.
I got 41.

m9202~204℃ (b) N-(5-fluoroindolin-2,8-dione-6-yl) = 8-4 #5 #6 ”-Production of tetrahydrophthalimide Chromic anhydride 8F, acetic acid 80- and water 6- N-(5-fluoroindol-6-yl)-8,4°5.6-tetrahydrophthalimide 4f obtained above was added to the mixture of
was added at 20-80°C, then 0 at 80-50°C.
．． Stirred for 5 hours. After cooling, water was added to the reaction solution and extracted with ether. The ether layer was washed with water, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was treated with silica gel column chromatography to obtain the desired hemolyte (5
-Fluoroindoline-2゜8-dione-6-yl)-
8,4,5,6-tetrahydrophthalimide 1f was obtained.

mp 268.5-264.5°C Next, formulation examples are shown. The compounds of the present invention are indicated by compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 50 parts of the compound of the present invention (1), (2) or (8), 8 parts of calcium lignin sulfonate, 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 10 parts of the compound (5) or (6) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 80 parts of xylene and 40 parts of cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 8 2 parts of the compound (2) or (4) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 80 parts of bentonite and 66 parts of kaolin clay were thoroughly ground and mixed, and water was added and kneaded well. After combining, granulation and drying are performed to obtain granules.

Formulation Example 4 25 parts of the present compound (4) or (5), 8 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC,
A suspension is obtained by mixing 69 parts of water and wet milling until the particle size is 5 microns or less.

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 compound numbers in Table 91. In addition, isatin represented by the formula (compound symbol (6)) was used as a comparative compound.

In addition, for evaluation of herbicidal efficacy and chemical damage, the germination and growth conditions of the test plants (weeds and crops) at the time of the survey were determined to be that there was no or almost no difference in the state of emergence and growth compared to untreated plants.
θ ~
Divided into 11 stages of 10: 0.1.2.3.4.5.6.
7.8.9.10.

Test Example 1 Upland Soil Surface Treatment Test A cylindrical plastic pot with a diameter of 103 cm and a depth of 10 eIH was filled with upland soil, and corn, soybean, physalis, and Japanese radish were sown and covered with soil. The test compound was made into an emulsion according to Formulation Example 2, and the prescribed form was 10
It was diluted with a liter of water and applied to the soil surface using a small sprayer. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 2.

ゝ＼ Table 2 Test Example 2 Field soil stem and leaf treatment test Diameter 10er! 1. Field soil was filled in a cylindrical plastic pot with a depth of 10 m, and Japanese barnyard grass, Japanese morning glory, 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, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 8.

Table 8 Test Example 8 Paddy field full water treatment test A cylindrical plastic pot with a diameter of 800 mm and a depth of 12 pots was filled with paddy soil, and the seeds of Japanese millet, broad-leaved weeds (Azaena, Kikashigusa, Chickweed), and firefly were placed at a depth of 1 to 2 cm. I mixed it in. After filling the field with water and making it into a paddy field, tubers of Urikawa were buried at a depth of 1 to 23, and then rice at the 8-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 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 and phytotoxicity were investigated. The results are shown in Table 4.

Table 4 (25 completed)

Claims (4)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group. ] isatin derivative represented by. (2) Compounds represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and the general formula R-A [wherein R represents a lower alkyl group, lower alkenyl group, or lower alkynyl group, and A represents a halogen atom] . ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R represents the same meaning as above. ] A method for producing an isatin derivative represented by. (3) General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R' represents a lower alkyl group. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by oxidizing indole derivatives represented by ▼ [In the formula, R' represents the same meaning as above. ] A method for producing an isatin derivative. (4) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group. A herbicide characterized by containing an isatin derivative represented by the following as an active ingredient.