JPS62155276A - Benzothiazolone derivative, production thereof and herbicide containing said derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A benzothiazoline derivative expressed by formula I (R is H, lower alkyl, lower alkenyl, lower alkynyl, halo lower alkyl, halo lower alkenyl, halo lower alkynyl, lower alkoxy lower alkyl, lower alkoxy lower alkoxy lower alkyl; cinnamyl or cyano lower alkyl). EXAMPLE:2-[6-Fluoro-3-( 2-propynyl )-2(3H)-benzothiazolon-5-yl]-4,-5,6,7-tetrahydro- 2H-indole-1,3-dione. USE:A herbicide in paddy field, upland field, orchard, pasture, lawn, forest or noncultivated land, etc., without exhibiting phytotoxicity to be a problem for main crops. PREPARATION:A compound expressed by formula II is reacted with 3,4,5,6- tetrahydrophthalic anhydride to afford the aimed compound expressed by formula I.

Description

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

<Conventional technology> Until now, Herbicide Handbook of
the Weed Science 5ociety
of America 5th edition, page 40 (1988)
It has been described that benazoline, a benzothiazolone derivative, is used as an active ingredient in herbicides.

<Problems to be Solved by the Invention> However, these compounds are not necessarily satisfactory because their herbicidal activity is insufficient or their selectivity between crops and weeds is poor.

Measures to Solve the Problems> In view of the above circumstances, the present inventors conducted various studies in order to develop a compound with excellent herbicidal activity, and as a result, they discovered the following 6-
We have discovered that a 2(8H)-benzothiazolone derivative in which a fluorine atom is substituted at the 5-position and a tetrahydrophthalide atom at the 5-position is a compound that has excellent herbicidal activity with few of the above-mentioned drawbacks, and the present invention This led to the invention.

That is, the present invention provides a method using the general formula [wherein R is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo-lower alkenyl group, a halo-lower alkynyl group, a lower alkoxy lower alkyl group, a lower alkoxy lower alkoxy lower Represents an alkyl group, a cinnamyl group, or a cyano lower alkyl group. The present invention provides a benzothiazolone derivative (hereinafter referred to as the compound of the present invention) represented by the formula (hereinafter referred to as the compound of the present invention), a herbicide containing the same as an active ingredient, and a method for producing the same.

Next, the manufacturing method will be explained in detail.

The compound of the present invention has the general formula [wherein R represents the same meaning as above]. It can be produced by reacting the aminobenzothiazolone derivative shown in ] with 8.4.5.6-titrahydrophthalic anhydride.

This reaction is usually carried out in a solvent, and the reaction temperature range is 8.
0 to 200°C, reaction time range is 1 to 24 hours,
The amount of reagents used in the reaction is 1 to 8 equivalents of 8,4,5.6-titrahydrophthalic anhydride per equivalent of aminobenzothiazolone derivative [II].

Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as dioxane and ethylene glycol dimethyl ether, and mixtures thereof.

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 recrystallization.

Next, the compound of the present invention produced by this production method is
Shown in the table.

Table 1 When using the compound of the present invention with the general formula 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, etc.

These preparations contain the compound of the present invention as an active ingredient, ii
It is contained in a t ratio of 0.05 to 90%, preferably 0.1 to 80%.

Examples of solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, siliceous 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 Impropatol, ethylene glycol, and cellosolve, N, N-
Examples include 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 ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. It will be done.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), 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 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.

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.
0.021 to 1001 per are. Preferably 0.
059 to 501, and emulsions, wettable powders, suspension agents, etc. are usually mixed with 1 liter to 10 liters of water per 1 are (adding auxiliary agents such as spreading agents if necessary). 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.

<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 5-Amino-6-fluoro-8-(2-propynyl)-
2(8H)-benzothiazolone 0.481 and 8.4,5
．． 0.82 f/6-titrahydrophthalic anhydride was suspended in 5-acetic acid and heated under reflux for 5 hours. After the reaction mixture was cooled, water was added and extracted with ethyl acetate.

The extract was washed with water and sodium bicarbonate, then dried and concentrated, and the resulting residue was subjected to silica gel thin layer chromatography (developing solvent).
Purified with ethyl acetate:hexane=1:4) to give 2-[6-
Fluoro-8-(2-propynyl)-2(8H)-benzothiazolon-5-yl]-4,5,6,7-tetrahydro-2H-isoindole-1°8-dione 0.1
I got 8 f.

m, p, 198-195°C IR (KBr, CHCl5), -t; 8800.8
020.1720°1G85.1490.1885.1
215.760.6651 ) INMR (CDC1a
, δ): 1.5-2.0 (4H, br, ), 2
．． 1-2.6, (5H, br,), 4.61 (2H,
d, J=2.6Hz), 7.06 (IH, d
, )=6. Qaz N, 7.27 (l)i, de
J=9.0H2) Purified by recrystallization from isopropyl alcohol.

m4), 198-199°C Next, some of the compounds of the present invention produced by this production method are shown in Table 2.

Table 2 General formulas Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 2. Parts are parts by weight.

Formulation Example 1 Compound 2 or 4.50 parts of the present invention, 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 6.5 parts of the compound of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 80 parts of xylene and 45 parts of cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 8 8.12 or 16.2 parts of the compound of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 80 parts of bentonite, and 65 parts of kaolin clay are thoroughly ground and mixed, and water is added and kneaded well. After that, the mixture is granulated and dried to obtain granules.

Formulation Example 4 4.16 or 29.25 parts of the compound of the present invention, 8 parts of HoIJ oxyethylene sorbitan monooleate, UMCa part, and 69 parts of water were mixed and suspended by wet grinding until the particle size became 5 ton chlorine or less. get the agent.

Formulation Example 6 Compound of the present invention 2.8.4.5.12.16.28.29
Or, 81.5 parts of polyoxyethylene steryl phenyl ether, 14 m of polyoxyethylene steryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 80 parts of xylene and 45 parts of N,N-dimethylformamide are thoroughly mixed to obtain an emulsion.

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 2, and the compounds used for comparison are indicated by the compound symbols in Table 8.

Table 8 In addition, the herbicidal efficacy was determined by visually observing the degree of inhibition of budding and growth of the test plants during the survey, and 10 was determined when there was no or almost no difference from when the compound was not tested. A score of "5" indicates that the plant has withered or its growth is completely inhibited, and is evaluated on a 6-level scale from θ to 5, ranging from 0.1 to 2.
8.4.5.

Test Example 1 Upland Soil Surface Treatment Test A cylindrical plastic pot with a diameter of 10 cWI and a depth of 1051 mm was filled with upland soil, and covered with soil and sown with barnyard grass, oat, Marupa morning glory, and Japanese radish. The test compound was made into an emulsion according to Formulation Example 2 or 5, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the soil surface was treated with 1ζ 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 2 Upland field soil treatment test A cylindrical plastic pot with a diameter of 10 ann and a depth of 10 cyn was filled with upland soil.1. Japanese barnyard grass, 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 or 5, and the predetermined amount was
The mixture was diluted with water containing a spreading agent equivalent to 10 liters per area, and treated with a small sprayer from above the plant. 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 8 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 8cI11 and a depth of 12eM was filled with paddy soil, and Japanese millet and mild grasses of broad-leaved weeds (Azaena, Azalea, Lamina and Chickweed) were placed at a depth of 1 to 2 depths. Mixed it in. After flooding the rice field and making it into a paddy field, tubers of Urikawa were buried at a depth of 1 to 2 depths, and then rice at the 2-leaf stage was transplanted and grown in a greenhouse. 6 days later (early stage of emergence of each weed)
The test compound was made into an emulsion according to Formulation Example 2 or 5, 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 6.

Table 6 Test Example 4 Upland Soil Treatment Test A vat with an area of 88 x 28 cnl and a depth of 11 m was filled with upland soil and tested for soybean, groundnut, cotton, corn, morning glory, Japanese radish, Japanese cabbage, Japanese physalis, white cabbage, epispermum, and goldenberry. Seiban sorghum and hackberry were sown and covered with soil to a thickness of 1 to 2 G.

The test compound was made into an emulsion according to Formulation Example 2 or 5, 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 the 7th section.
Shown in the table.

Table 7 Test Example 5 Upland Soil Treatment Test A vat with an area of 88 x 28 i and a depth of 11 cm was filled with upland soil, and soybean, groundnut, cotton, corn, trumpet gum, morning glory, Japanese fir tree, Japanese velvet, Ebisu grass, Japanese Physalis, American golden deer, American Cucumber sorghum, Japanese spurge, spurge, white-spotted morning glory, white sage, wild mustard, European bindweed, purslane, Japanese sagebrush, sorghum, foxtail grass, goldenrod, and Seiban sorghum were sown and covered with soil to a thickness of 1 to 2 α. A predetermined amount of the test compound made into an emulsion according to Formulation Example 2 or 6 was diluted with water equivalent to 10 liters per are, and applied to the soil surface using a small sprayer. B was grown outdoors 20 days after treatment, and its herbicidal efficacy was investigated. The results are shown in Table 8.

Test Example 6 Upland Soil Treatment Test A vat with an area of 88 x 2 am and a depth of 11 m was filled with upland soil, and wheat, Japanese knotweed, Japanese grasshopper, chickweed, stagweed, and sagebrush were sown to a depth of 1 to 2 cm.
It was covered with soil to a thickness of . The test compound was made into an emulsion according to Formulation Example 2 or 5, 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 9.

Table 9 Test Example 7 Field soil stem and leaf treatment test A vat with an area of 88 x 28 j and a depth of 113 was filled with field soil, and corn, Japanese fir tree, Japanese yam, Japanese morning glory, Japanese Physalis, and Japanese cabbage were sown and grown for 18 days. Thereafter, make the test compound into an emulsion according to Formulation Example 2 or 6, dilute the specified amount with water equivalent to 5 liters per are containing a spreading agent, and use a small sprayer to spray the entire stem and leaf area from above the plant body. was uniformly 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 am. The herbicidal efficacy was investigated 20 days after the treatment. The results are shown in Table 10. Note that this test was conducted in a greenhouse throughout the entire period.

Table 10 Test Example 8 Field soil, stem, and leaf treatment test A vat with an area of 88 x 28 js and a depth of 110 mm was filled with field soil, and wheat, huskweed, japonica, chickweed, and chinensis were sown and grown for 18 days. Thereafter, make the test compound into an emulsion according to Formulation Example 2 or 5, dilute the specified amount with water equivalent to 5 liters per are containing a spreading agent, and use a small sprayer to spray the entire stem and leaf area from above the plant body. was uniformly processed. At this time, the growth conditions of weeds and crops vary depending on the grass cover, but they are at the 1-4 leaf stage and the plant height is 2-12 am.
Met. The herbicidal efficacy was investigated 20 days after the treatment. The results are shown in Table 11. Note that this test was conducted in a greenhouse throughout the entire period.

Table 11 Test Example 9 Field Soil Treatment Test In a field with ridges extending 1m across the top surface, corn, Japanese velvet, Japanese cabbage, and Japanese Physalis were sown,
Each plot was divided into 8 test plots. A predetermined amount of the test compound was made into an emulsion according to Formulation Example 2 or 5, diluted with water equivalent to 10 liters per are, and the entire surface of the test plot was treated with a small sprayer.

The repetition was 8 times, and the herbicidal efficacy was investigated after 82 days. The results are shown in Table 12.

Table 12 <Effects of the Invention> As explained above, the compound of the present invention can be used to treat various weeds that are problematic in the treatment of foliage and soil in fields, such as sop vine, huskweed, staghorn knotweed, purslane, chickweed, white locust, staghorn weed, Japanese radish, Japanese radish, shepherd's purse, American hornwort, Ebisu grass, Japanese radish, American king deer, field pansy, Japanese radish, American morning glory, Marupa morning glory, European bindweed, white radish, Japanese morning glory, Japanese Physalis, Japanese Physalis, Japanese fir, Japanese fir, Sunflower, Japanese chamomile,
Broad-leaved weeds such as corn marigolds and spurge, barnyard grass, goldenrod, foxtail grass, crabgrass, and sycamore
Tabila, gnome, oat, oat,
The compound of the present invention has a herbicidal effect on weeds of the grass family such as Seiban sorghum, barley, japonica, japonica, and japonica, as well as weeds of the cyperaceae family such as dayflower, and weeds of the cyperus family such as cypress. It does not cause any harmful effects on major crops such as barley, rice, soybeans, peanuts, 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; It has a herbicidal effect on plants such as Prunus japonicus, and does not cause any harmful effects on rice.

Furthermore, the compound of the present invention can be used as a herbicide in rice fields, fields, orchards, pastures, lawns, forests, non-agricultural lands, etc., and can also be used in combination with other herbicides to kill weeds. It can be expected to increase efficacy. Furthermore, it can be used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners, and the like.

Claims (3)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo-lower alkyl group, a halo-lower alkenyl group, a halo-lower alkynyl group , lower alkoxy lower alkyl group, lower alkoxy lower alkoxy lower alkyl group, cinnamyl group or cyano lower alkyl group. ] A benzothiazolone derivative represented by. (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo-lower alkyl group, a halo-lower alkenyl group, a halo-lower alkynyl group , lower alkoxy lower alkyl group, lower alkoxy lower alkoxy lower alkyl group, cinnamyl group or cyano lower alkyl group. ] and the aminobenzthiazolone derivative represented by 3,4,5
, 6-tetrahydrophthalic anhydride ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R represents the same meaning as above. ] A method for producing a benzothiazolone derivative. (3) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo-lower alkyl group, a halo-lower alkenyl group, a halo-lower alkynyl group , lower alkoxy lower alkyl group, lower alkoxy lower alkoxy lower alkyl group, cinnamyl group or cyano lower alkyl group. ] A herbicide characterized by containing a benzothiazolone derivative represented by the following as an active ingredient.