JPS61134373A - Tetrahydrophthalimide derivative, production thereof, and herbicide comprising same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A tetrahydrophthalimide derivative shown by the formula (R is 1-5C alkyl, 3-5C alkenyl, or 3-5C alkynyl). EXAMPLE:N-(2-Fluoro-5-butoxy-4-nitrophenyl)-3,4,5,6-tetrahydrophthalim ide. USE:Useful as a herbicide. Showing effect on broad-leaved weeds such as wild buckwheat, etc., gramineous weeds such as barnyard grass, etc. by foliar treatment and soil treatment in plowed fields, and having no phytotoxicity to main crops such as soybeans, maize, etc. Exhibiting effects on gramineous weeds such as Echinochloa oryzicola Vasing, broad-leaved weeds such as false pimpernel, etc., in paddy fields, and having no phytotoxicity to rice plants. PREPARATION:N-(2-Fluoro-5-hydroxy-4-nitroiphenyl)-3,4,5,6-tetrahyd-rop hthalimi de is reacted with a halide shown by the formula R-X (X is Cl, Br, or I), to give a compound shown by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein R represents a C1-C5 alkyl group, a 03-CII alkenyl group, or a C3-C5 alkynyl group]. ] The present invention relates to a method for producing a tetrahydrophthalimide derivative (hereinafter referred to as the compound of the present invention) represented by the following formula, and a herbicide containing the same as an active ingredient.

Certain tetrahydrophthalimide derivatives, such as N
The use of -(4-nitrophenyl)-3,4°5,6-tetrahydrophthalimide as an active ingredient in herbicides is described in Japanese Patent Publication No. 11940/1983. 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 areas, such as freckle weeds, Japanese knotweed, purslane, chickweed, whiteweed, Japanese radish, Japanese radish, Japanese radish, American hornwort, American hornwort, Japanese commonweed, American commonweed, and other problematic weeds. Broad-leafed weeds such as golden deer, field pansies, yellowtail, morning glory, morning glory, hotokenoza, white-breasted morning glory, dog-eared groundweed, great dog-eared dogfish, Japanese fir tree, sunflower, dog-eared holly, corn marigold, barnyard grass, golden millet, foxtail grass, black-and-white grasshopper, silver grass, and white-breasted grass. , oats, oats, Seiban sorghum, and other grass family weeds; dayflowers and other weeds;
It does not cause any harmful effects on major crops such as corn, wheat, rice, and cotton.

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, japonica, and chickweed, cyperaceae weeds such as bulrushes, and cypress grasses. It has a herbicidal effect on rice plants, etc., and does not cause any harmful effects on rice plants.

The compound of the present invention comprises N-(2-fluoro-5-hydroxy-4-nitrophenyl)-3,4,5゜6-tetrahydrophthalimide and the general formula % formula % (1) [wherein, X is a chlorine atom, It represents a bromine atom or an iodine atom, and R has the same meaning as above. ] It can be produced by reacting a halide represented by the following in a solvent in the presence of a dehydrohalogenating agent at o'c to 40°C for 1.0 to 48 hours.

The base of the reagent used in this reaction is N-(2-fluoro-
5-hydroxy-4-nitrophenyl) -3,4,5
, 6-tetrahydrophthalimide, 1 to 3 equivalents of halide CI) and 1 to 3 equivalents of dehydrohalogenating agent.
It is equivalent.

Examples of solvents include ethers such as dioxane, tetrahydrofuran and ethylene glycol dimethyl ether, nitriles such as acetonitrile and isobutyronitrile, formamide, N,N-dimethylformamide, N,N-
Examples include acid amides such as dimethylacetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, and mixtures thereof.

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

After the reaction is completed, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, chromatography,
The desired compound of the present invention can be obtained by purification by operations such as distillation and recrystallization.

Next, production examples of the compounds of the present invention will be shown.

Production Example 1 (Production of Compound 3 of the Invention) 0.6f of N-(2-fluoro-5-hydroxy-4-nitrophenyl)-3,4,5,6-tetrahydrophthalimide was added to 5 ml of N,N-dimethylformamide. and added to a suspension of 0.1f1N of sodium hydride and 511Il of N-dimethylformamide at -10 to 0°C. After the generation of hydrogen was completed, n-butyl iodide o,6y was added at 0°C, and the mixture was stirred at 20 to 25°C for 6 hours. Water was added to the reaction solution and extracted with ether. The extract was washed with water, dried, and concentrated, and the resulting residue was separated using silica gel thin layer chromatography to obtain N-(2-fluoro-5-butoxy-4-nitrophenyl)-3,4,5,6-tetrahydrophthalimide. I got .141. nOt, 5498NMRδp
pm (CDC1a) 1.0 (8H, t), 4.1 (
2H,t), 7.0 (IHe d), 7.75 (L
H.

d) Some of the compounds of the present invention that can be produced by such a production method are shown in Table 1.

Table 1 General formula When producing the compound of the present invention, the raw material compound N-(2
-Fluoro-5-hydroxy-4-nitrophenyl)-
3,4,5,6-tetrahydrophthalimide is N-(
Mochiden 2-fluoro-5-hydroxyphenyl) -3,
4゜5.6-Tetrahydrophthalimide and a nitrate such as sodium nitrate or potassium nitrate in chloroform, 1.2
- in a solvent such as dichloroethane, in the presence of concentrated sulfuric acid, at 0°C
It can be produced by reacting at ~40°C for 1 to 5 hours and nitration.

The amount of reagents used in this reaction is N(2-fluoro-5
-Hydroxyphenyl) -a.

The amount of nitrate is 1.0 to 1.5 equivalents, and the amount of concentrated sulfuric acid is 1.0 to a large excess amount relative to 1 equivalent of 4,5.6-tetrahydrophthalimide.

After the completion of the reaction, the reaction solution is subjected to the usual post-treatment of the nitration reaction, and if necessary, purified by operations such as chromatography, distillation, and recrystallization to obtain the desired N-(
2-fluoro-5-hydroxy-4-nitrophenyl)
-3,4,5,6-tetrahydrophthalimide can be obtained.

Next, a manufacturing example thereof will be shown as a reference example.

Reference example N-(2-fluoro-5-hydroxyphenyl)-3
, 4,5,6-tetrahydrophthalimide 7.2 to 1
．． It was added to a mixed solution of 280 g of 2-dichloroera/10 g of concentrated sulfuric acid at a temperature below 109C.

To this, 3.6y of potassium nitrate was added little by little at 10°C, and the mixture was stirred at 20-30°C for 2 hours. The reaction solution was poured into water and extracted with chloroform. The extract was washed with water, aqueous sodium bicarbonate, dried, and concentrated.

The residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate) to obtain N-(2-fluoro-
5-hydroxy-4-nitrophenyl) -(,4,5
, 6-titrahydro 07 talimide 2.91 was obtained. m,
9.108.8°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 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 0.1 to 90%, preferably 0.2 to 80%.

Examples of solid carriers include fine powders or granules such as kaolin clay, attapulgite 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, and dimethyl sulfoxide. , acetonitrile, water, etc.

Surfactants used for emulsification, dispersion, wetting layers, etc. include anionic surfactants such as alkyl sulfate salts, alkylaryl sulfonates, dialkyl sulfosuccinates, and phoroxyethylene alkylaryl ether phosphate salts. agent, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether,
Examples include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. As formulation aids, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PA
Examples include P (isopropyl acid phosphate).

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. The area indicates the tumor area.

Formulation Example 1 5.50 parts of the compound of the present invention, 8 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 4.5 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 cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 3 4.2 parts of the compound of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite, and 65 parts of kaolin clay were thoroughly ground and mixed, water was added, and the mixture was thoroughly kneaded. The granules are dried 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 0M0, 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, which has been formulated as a cloth, 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 foliar treatment includes treatment from above the plant 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 amendments, 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 herbicides for lawns, forests, non-agricultural lands, etc.

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.
0.059 to 100 g per are, preferably 0.059 to 100 g per are.
Emulsions, wettable powders, suspension agents, etc. are usually mixed with 1 liter to 10 liters of water (adding auxiliary agents such as spreading agents, if necessary) per are. Granules and the like are usually treated 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.

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 2 In addition, herbicidal efficacy is determined by visually observing the degree of budding and growth inhibition of the test plants during the survey, and ``0'' indicates that there is no or almost no difference from the case where no compound is used. If the plant is withered or its growth is completely inhibited, it is evaluated as "5", and evaluated on a scale of 0 to 5, 0.1, 2.
8.4.5.

Test Example 1 Upland Soil Treatment Test A cylindrical plastic pot with a diameter of 103 mm and a depth of 101'11 was filled with upland soil, sown with Japanese barnyard grass, Japanese morning glory, and Japanese staghorn, 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, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 3.

Table 8 Test Example 2 Upland Stem and Leaves Treatment Test Upland soil was packed into a cylindrical plastic hotpot with a diameter of 10 cII, 11 and a depth of 103 cm, and barnyard grass, Japanese radish, and Japanese radish were sown and grown in a greenhouse for 10 days. Thereafter, test compound 1 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 4.

Table 4 Test Example 8 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 8α and a depth of 121 is filled with paddy soil, and seeds of Japanese millet and broadleaf colossus (Azaena, Kikashigusa, Chickweed) are placed at a depth of 1 to 21. Mixed it in. After flooding and turning it into a paddy field, add 2 tubers of Urikawa to 1
The rice was buried at a depth of ~2c11, and then two-leaf stage rice was transplanted and grown in a greenhouse. Six days later (at the beginning of the emergence of each weed), the test compound was made into an emulsion according to Formulation Example 2, the required amount 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.

Table 5 Test Example 4 Upland Soil Treatment Test A vat with an area of 8 B x 28 d and a depth of 111 was filled with upland soil, and soybeans, corn, barley, rice, Marupa morning glory, Japanese cabbage, Japanese staghorn, Japanese Physalis, Japanese commonweed, and Japanese foxtail were sown. Covered with soil to a thickness of ~21 mm. 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, and treated on the soil surface with 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 6.

Test Example 5 Upland soil treatment test area 3 (23 d x 113 d) vats were filled with upland soil, and corn, wheat, Japanese fir, Japanese morning glory, Japanese sorghum, whiteberry, Japanese foxtail, and Seiban sorghum were sown and grown for 18 days. , the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was added to 1 containing a spreading agent.
The solution was diluted with water equivalent to 5 liters per area and uniformly applied to the entire stem and leaves from the top of the plant using a small sprayer. 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 2-12 ff.

The herbicidal efficacy was investigated 20 days after the treatment. The results are shown in Table 7. Note that this test was conducted in a greenhouse throughout the entire period.

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a C_1 to C_5 alkyl group, C_3 to C_
5 alkenyl group or C_3-C_5 alkynyl group. ] A tetrahydrophthalimide derivative represented by (2) N-(2-fluoro-5-hydroxy-4-nitrophenyl)-3,4,5,6-tetrahydrophthalimide and the general formula R-X [wherein, R is a C_1 to C_5 alkyl group, C_3 to C_
5 alkenyl group or C_3-C_5 alkynyl group, and X represents a chlorine atom, a bromine atom or an iodine atom. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting with halides shown by ▼ [In the formula, R represents the same meaning as above. ] A method for producing a tetrahydrophthalimide derivative represented by (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a C_1 to C_5 alkyl group, C_3 to C_
5 alkenyl group or C_3-C_5 alkynyl group. ] A herbicide characterized by containing a tetrahydrophthalimide derivative represented by the following as an active ingredient.