JPH03284678A - Benzothiazolone derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is alkyl, alkenyl or alkynyl). EXAMPLE:2-[3-(2-Propynyl)-2(3H)-benzothiazolon-5-yl]-4,5,6,7- tetrahydroisoindole-1,3-dione. USE:Herbicide. PREPARATION:The compound of formula I can be produced according to the reaction formula by reacting a compound of formula II with a compound of formula III in a solvent (e.g. hexane, benzene or toluene) at a temperature between 60 deg.C and the boiling point of the solvent. The compound of formula I has excellent herbicidal activity and selectivity.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel benzothiazolone derivative and a herbicide containing the same as an active ingredient.

(Prior Art) Until now, it has been reported in Japanese Unexamined Patent Publication No. 158276/1983 that benzothiazolone derivatives can be used as active ingredients of Q removers (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.

In addition, in recent years, there has been a strong demand for herbicides that have a high level of selectivity between crops and weeds, high activity and low dosage to suppress environmental pollution, and residual efficacy necessary for labor saving in agricultural work. ,
This is benzothiazolone 3! ! This is not unrelated to the field of conductors, and the development of better chemicals is desired.

(Means for Solving the Problems) In order to achieve the above object, the present inventors synthesized a number of benzothiazolone derivatives and conducted various studies on their usefulness. As a result, 2H-isoindole-1,
The present invention has been completed based on the finding that a benzothiazolone derivative having a 3-dione-2-yl group as a substituent at the 5-position has excellent herbicidal activity and selectivity that meet two objectives.

That is, the compound of the present invention represented by the general formula (1) can be produced by the following method.

The present invention provides a benzothiazolone derivative represented by the formula (wherein R represents an alkyl group, an alkenyl group, or an alkynyl group) and a herbicide containing the derivative as an active ingredient.

Next, specific examples of the two compounds of the present invention are shown in Table 1, and the compound numbers are referred to in the following description.

Table 1 (CD) This is done by reacting.

As the solvent, for example, hydrocarbons such as hexane, benzene and toluene, ethers such as dioxane, ethylene glycol dimethyl ether and tetrahydrofuran, fatty acids such as formic acid and acetic acid, water, or mixtures thereof can be used.

The -F reaction is carried out at a temperature range from 60°C to the boiling point of the solvent, and is completed in 1 to 24 hours. After the completion of the reaction, water is added, extracted with an organic solvent, washed with water, dried, concentrated, etc. The desired compound of the present invention can be obtained by treatment and, if necessary, purification by operations such as recrystallization and chromatography.

In addition, the compound represented by general formula (11) which is a raw material can be manufactured by the following method.

[■] [In the formula, "C" has the same meaning as above] This method is carried out by reducing the compound represented by the general formula [IV] using a reducing agent.

As the reducing agent, metals such as iron and tin oxide can be used.

Examples of solvents include acids such as acetic acid and hydrochloric acid, aliphatic esters such as ethyl acetate and butyl acetate, toluene, xylene,
Aromatic hydrocarbons such as benzene.

Examples include alcohols such as methyl alcohol and ethyl alcohol, or mixtures thereof.

The above reaction is carried out at a temperature ranging from 0° C. to the boiling point of the solvent, and is completed in 1 to 24 hours.

In addition, the compound represented by the general formula [IV], which is a raw material, can be prepared by the following method: 7(V)(VI)
[I'%)] [In the formula, R has the same meaning as above. ] This method is carried out by reacting a compound represented by the general formula EV) with a compound represented by the linear formula [■] in the presence of a base.

This reaction is usually carried out without a solvent or in a solvent in the presence of a halogenated hydrogenating agent. The reaction temperature range is -50
~100°C, the reaction time ranges from 10 minutes to 24 hours, and the amount of reagent used for the reaction is 1 ml of thiazolone derivative [v]
The amount of compound (Vl) is 1 to 1.5 equivalents.

Benzene, toluene, and xylene are used as solvents.

Aromatic hydrocarbons such as dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, nitriles such as acetonitrile, imbutyronitrile, acid amides such as formamide, N,N-dimethylformamide, acetamide, dimethyl sulfoxide,
Examples include sulfur compounds such as sulfolane, water, and mixtures thereof.

Examples of the base include inorganic bases such as sodium, potassium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride. After the reaction is complete, water is added to the reaction solution, and the reaction solution is extracted with an organic solvent, concentrated, etc. It can be produced by carrying out the usual operations and, if necessary, purifying it by operations such as chromatography and recrystallization.

In addition, the compound represented by the general formula (V) which is a raw material is God, 5ofij, []niv.

, Whit Fak, ) 67.287-293 (
1976) and others.

Example 2-(3-(2-propynyl)-2(3H)-
Benzothiazolone-5-yl] 4.5.6.7-thitrahydroinindole 1,3
-Production of Dione (Compound 5) 5-Amino-3(2-propynyl)-2(3H) was added to a reaction flask equipped with a Dimroth.
)-benzothiazolone 0.30g (1.5mmo 1
), 4.5°6.7-tetrahydrophthalic anhydride 0.
Add 22 g (1.5 mmol) and 1.0 mΩ of acetic acid,
One reaction was completed by heating under reflux for 2 hours. after that.

Add water to the reaction solution, extract with ethyl acetate, wash with water, dry,
Concentration was performed to obtain a composition. This composition was purified by silica gel chromatography to obtain the target compound 2-[3
0.25 g (yield = 49%) of -(2-propynyl)-2(3H)-benzothiazolon-5-yl)-4,56,7-titrahydroisoindole was obtained.

Melting point: 206-209°C.

The herbicide of the present invention contains a benzothiazolone derivative represented by the general formula ([) as an active ingredient.

Use the compound of the present invention as a herbicide in paddy fields, upland fields, 4! ! garden,
When used on non-agricultural land, the active ingredient can be used in an appropriate dosage form depending on the purpose.

In normal cases, the active ingredient is diluted with an inert liquid or solid carrier, and if necessary, surfactants, dispersants, adjuvants, etc. are added to form powders, wettable powders, emulsions, granules, etc. It can be formulated and used in various forms. Examples of carriers used in formulation include solid carriers such as gicrite, talc, ben-1-night, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate pentaurea, isopropyl alcohol, and xylene. , cyclohexanone, methylnaphthalene, and the like. Examples of surfactants and dispersants include alcohol sulfate salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, and polyoxyethylene sorbitan monoalkylates. . Examples of adjuvants include carboxymethylcellulose, polyethylene glycol, gum arabic, and the like. When used, it can be diluted to an appropriate concentration and sprayed, or applied directly. The amount of application varies depending on the occasion and timing of application, application method, and cultivated crop shade, but in general, the active ingredient of the compound of the present invention is 0 per 10 ares.
．． 1 g-IKg, apply.

Next, the formulation method will be specifically explained using typical formulation examples. In the following description, "1 part" means part by weight.

Formulation Example 1 10 parts of wettable powder compound (3) and 0.5 parts of Emulgen 810 (registered trademark of Kao Corporation)! g, 05 parts of De-Hanru N (registered trademark of Kao Corporation), 20 parts of Kunilite 201 (registered trademark of Kunimine Industries Co., Ltd.), 69 parts of Zeekrite CA (registered trademark of Zeekrite Co., Ltd.) Mix and grind the parts to obtain a wettable powder.

Formulation Example 2 0 parts of wettable powder compound (2), 5 parts of Emulgen 810,
0.5 parts of Demol N, 20 parts of Danilite 20 U, 5 parts of Carplex 80, and 64 parts of Zeekrite CA are mixed and ground to obtain a wettable powder.

Formulation Example 3 To 30 parts of emulsion compound (1), add 60 parts of a compound of xylene and isophorone and 10 parts of the surfactant Tsurupol 800A (registered part of Toho Chemical Industry Co., Ltd.), and stir these thoroughly. An emulsion is obtained by

Formulation Example 4 10 parts of granule compound (4), talc and bentonite]=3
80 parts of bulking agent, 5 parts of white carbon, 2 parts of surfactant Tsurupol 800A, 10 parts of water
Add 100% of
, 05 after extruding through the sieve hole at 7 am and drying.
Cut into ~1 inch length to obtain granules.

(Effects of the Invention) The compound of the present invention represented by the general formula (1) can be used during the germination of annual weeds such as Japanese barnyard grass, Japanese cypress, Japanese cypress, Japanese cypress, Japanese azalea, etc., and perennial weeds such as bulrush, Japanese cypress, and Japanese cypress, which occur in rice fields. It exhibits excellent herbicidal effects at extremely low dosages over a wide range of the growing season, and at the same time is highly safe for paddy rice. In addition, various weeds that can be a problem in fields, such as broad-leaved weeds such as polygonum, Japanese apricot, whiteweed, and Japanese crocodile, as well as weeds of the Cyperaceae family such as cyperus cyperus and cyperus japonica, Japanese barnyard grass, red foxtail grass, foxglove grass, and staghorn grass, etc. It exhibits a high herbicidal effect against grass weeds when treated with soil or foliage, and at the same time is highly safe against soybeans, cotton, corn, upland rice, wheat, etc. It can also be used in orchards, pastures, lawns, non-agricultural lands, etc.

Next, the effects of the compounds of the present invention will be explained by giving test examples.

Test example], (herbicidal effect test by paddy soil treatment) 100
rm' plastic pots were filled with paddy soil, and after puddling, seeds of Japanese millet, Japanese cypress, Japanese cypress, and bulrush were sown, and the pots were submerged in water to a depth of 3 cm. The next day, a wettable powder prepared in a til format according to Formulation Example 1 was diluted with water and dropped onto the water surface. The application amount is 10 per active ingredient
It was set to 0g. Thereafter, the plants were grown in a greenhouse, and the herbicidal effect was investigated on the 21st day of treatment according to the standards in Table 2. The results are shown in Table 3, Table 2 Table 3 Test Example 2 (Herbicidal effect test by field soil foliage treatment) 120
Fill a cm2 plastic pot with field soil and plant knotweed,
Seeds of Aobiyu, Shiroza, and Kogomegayari were sown.
The barnyard grass was grown in a greenhouse until it reached the three-leaf stage. At the 3-leaf stage of Japanese barnyard grass, add hot pepper to Formulation Example 1! Dilute the wettable powder with water so that the active ingredient is 400g per cup.
A small sprayer was used to spray 100 fl/10 are over the entire plant from above. Thereafter, the plants were grown in a greenhouse, and the herbicidal effect was investigated on the 21st day of treatment according to the standards in Table 2. The results are shown in Table 4.

Table 4 Table 5 Test Example 3 (Herbicidal effect test by field soil treatment) 120c
Two plastic pots were filled with upland soil, and seeds of Japanese millet, Japanese knotweed, Japanese knotweed, Japanese violet, Japanese whiteberry, and Japanese cypress were sown and covered with soil. A wettable powder prepared according to Formulation Example 1 was diluted with water.

1oOQ per 10 ares was uniformly sprayed on the soil surface using a small sprayer so that the active ingredient was 100 g per 10 ares. After that, it was grown in a greenhouse, and the herbicidal effect was investigated according to the standards in Table 2 after 21 days of treatment.
Shown in the table.

Test example 4 (medicinal efficacy and phytotoxicity test by paddy soil treatment) 1 /
Paddy soil was filled in a 5,000 a.
2 m, 2 plants were transplanted and submerged in water at a depth of 311 m. ! ! rRsi! according to Formulation Example 1. A predetermined amount of the active ingredient of the wettable powder was diluted with water and dropped onto the water surface. Thereafter, they were grown in a greenhouse, and on day 30 of treatment, their herbicidal effects and phytotoxicity were investigated according to the standards in Table 2. The results are shown in Table 6.

We investigated Table 6 harm. The results are shown in Table 7-A and Table 7-B.

Table 7-A Test Example 5 (Crop selectivity test in field stem and foliage treatment) 60
Fill each 0 cm" plastic pot with upland soil.

B: Rice, wheat, knotweed, blueberry, and whiteweed were sown. Absorb water from the bottom of the pot,
The barnyard grass was grown in a greenhouse until it reached the three-leaf stage. A predetermined amount of the active ingredient of an irrigation agent prepared in g according to Formulation Example 1 at the third leaf stage of Japanese barnyard grass was diluted with 100 Q of water per 10 are, and sprayed onto the soil surface using a small sprayer. After that, it was grown again in the greenhouse, and the herbicidal effect was determined according to the standards in Table 2 after 21 days of treatment.
0 cH' Fill each plastic pot with upland soil, A: corn, soybean, cotton, barnyard grass, crabgrass,
After absorbing water from the bottom of a pot in which B: wheat, turgsum, cotton, polygonum, Japanese apricot, whiteweed, and Japanese grass were sown, the predetermined amount of the active ingredient of the hydrating powder prepared according to Formulation Example C was added. ] 1OO per 0 are
It was diluted with water from Q and uniformly sprayed on the soil surface using a small sprayer. After that, it was grown again in the greenhouse, and on the second day of treatment, the herbicidal effect and phytotoxicity were investigated according to the standards in Table 2. The results are shown in Table 8-A and Table 8-B.

Table 8-A Table 8-B

Claims (2)

[Claims] (1) A benzothiazolone derivative represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents an alkyl group, an alkenyl group, or an alkynyl group.) (2) A herbicide containing as an active ingredient a benzothiazolone derivative represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents an alkyl group, an alkenyl group, or an alkynyl group.)