JPH072738B2 - Benzothiazolone derivative and herbicide containing the same as active ingredient - Google Patents

Description

TECHNICAL 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.

<Prior Art> Until now, the Herbicide Handbook of the Weed Science Soc
The Society of America, 5th edition, page 40 (1988), etc., describes that benzothiazolone derivative, benazoline, can be used as an active ingredient of herbicides.

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

<Means for Solving Problems> In view of such circumstances, the present inventors have conducted various studies to develop a compound having excellent herbicidal activity, and as a result, 6-
It was found that a 2 (3H) -benzothiazolone derivative in which a fluorine atom is substituted at the position and tetrahydrophthalimide is substituted at the 5-position is a compound having excellent herbicidal activity with few defects as described above, and the present invention has been completed. It was

That is, the present invention has the general formula [In the formula, R represents 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, a lower alkoxy lower alkyl group, a lower alkoxy lower alkoxy lower alkyl group, It represents a cinnamyl group or a cyano lower alkyl group. ] A benzothiazolone derivative represented by the following (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 described in detail.

The compound of the present invention has the general formula [In the formula, R represents the same meaning as described above. ] The aminobenzothiazolone derivative represented by
It can be prepared by reacting with tetrahydrophthalic anhydride.

This reaction is usually carried out in a solvent, and the reaction temperature range is 80
~ 200 ° C, the reaction time range is 1 to 24 hours, and the amount of the reagent used in the reaction is 3,4,5,6-tetrahydrophthalic acid with respect to 1 equivalent of the aminobenzothiazolone derivative [II]. The anhydride is 1 to 3 equivalents.

Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as dioxane and ethylene glycol dimethyl ether, water and the like, or a mixture thereof.

After completion of the reaction, the reaction solution is subjected to usual 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 an operation such as recrystallization.

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

When the compound of the present invention is used as an active ingredient of a herbicide,
Usually, it is mixed with a solid carrier, a liquid carrier, a surfactant and other auxiliaries for formulation to prepare an emulsion, a wettable powder, a suspension, a granule and the like.

These formulations contain the compound of the present invention as an active ingredient in an amount of 0.05 to 90% by weight, preferably 0.1 to 80%.

Examples of the solid carrier include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, fine powder or particles of synthetic hydrous silicon oxide, and the like. As the liquid carrier, xylene, aromatic hydrocarbons such as methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosolve, acetone, cyclohexanone, ketones such as isophorone, soybean oil, vegetable oil such as cottonseed oil, dimethyl sulfoxide, N , N
-Dimethylformamide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, wet extension, etc. include alkyl sulfate ester salts, alkyl sulfonates, alkylaryl sulfonates, dialkylsulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, etc. Anionic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, nonionic surfactants such as sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters. .

Pharmaceutical aids include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(Carboxymethylcellulose) PAP (acidic isopropyl phosphate) and the like.

The compound of the present invention is usually formulated and subjected to soil treatment, foliage treatment or flooding treatment before or after emergence of weeds. The soil treatment includes a soil surface treatment, a soil admixture treatment, and the like, and the foliage treatment includes a treatment from above the plant body and a local treatment such that only the weeds are treated so as not to adhere to the crop.

When the compound of the present invention is used as an active ingredient of a herbicide, its treatment amount is different depending on weather conditions, formulation form, treatment time, method, place, target weed, target crop, etc., but usually 1
The amount is 0.02 g to 100 g, preferably 0.05 g to 50 g per are.
1 to 10 liters per areal (if needed,
It is diluted with water (to which an auxiliary agent such as a spreading agent is added) and treated, and granules and the like are generally treated without being diluted.

As the spreading agent, in addition to the above-mentioned surfactant, polyoxyethylene resin acid (ester), lignin sulfonate,
Examples thereof include abietic acid salt, dinaphthylmethane disulfonic acid salt, and paraffin.

<Examples> Hereinafter, the present invention will be described in more detail with reference to production examples, formulation examples, and test examples, but the present invention is not limited to these examples.

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

Production Example 5-Amino-6-fluoro-3- (2-propynyl)-
0.43 g of 2 (3H) -benzothiazolone and 0.32 g of 3,4,5,6-tetrahydrophthalic anhydride were suspended in 5 ml of acetic acid and heated under reflux for 5 hours. After the reaction mixture has cooled, water is added,
It was extracted with ethyl acetate. The extract was washed with water, washed with sodium bicarbonate water, dried and concentrated, and the obtained residue was purified by silica gel thin layer chromatography (developing solvent ethyl acetate: hexane = 1: 4) to give 2- [6-fluoro-3- ( 2-propynyl)
-2- (3H), benzothiazolone-5-yl] -4,5,6,
7-Tetrahydro-2H-isoindole-1,3-dione 0.
13g was obtained.

mp193−195 ° C IR (KBr, CHCl ₃ ) _cm −1; 3300,3020,1720,1685,1490,138
5,1215,760,665 ¹ HNMR (CDCl ₈ , δ); 1.5 to 2.0 (4H, br.), 2.1 to 2.6,
(5H, br.), 4.61 (2H, d, J = 2.6Hz), 7.06 (1H, d, J =
6.0 Hz), 7.27 (1H, d, J = 9.0 Hz), and further purified by recrystallization from isopropyl alcohol.

Next, Table 2 shows some of the compounds of the present invention produced by this production method.

Formulation examples are shown below. The compounds of the present invention are shown by the compound numbers in Table 2. Parts are parts by weight.

Formulation Example 1 The wettable powder is obtained by thoroughly pulverizing and mixing 50 parts of the present compound 2 or 4, 50 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide.

Formulation Example 2 Emulsion is obtained by thoroughly mixing 5 parts of the compound of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate, 30 parts of xylene and 45 parts of cyclohexanone.

Formulation Example 3 The present compound 3, 12 parts or 16, 2 parts, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed,
After adding water and kneading well, it is granulated and dried to obtain granules.

Formulation Example 4 The compound of the present invention 4, 16 or 29, 25 parts, polyoxyethylene sorbitan monooleate 3 parts, CMC 3 parts, and water 69 parts are mixed, and wet-milled until the particle size becomes 5 microns or less, and a suspension agent. To get

Formulation Example 5 Compound of the present invention 2, 3, 4, 5, 12, 16, 28, 29 or 3
1, 5 parts, polyoxyethylene styryl phenyl ether 14 parts, calcium dodecylbenzene sulfonate 6 parts,
An emulsion is obtained by thoroughly mixing 30 parts of xylene and 45 parts of N, N-dimethylformamide.

Next, Test Examples will show that the compound of the present invention is useful as an active ingredient of a herbicide. The compounds of the present invention are shown by the compound numbers in Table 2, and the compounds used for comparison and control are shown by the compound symbols in Table 3.

Regarding the herbicidal efficacy, the degree of budding and growth inhibition of the test plant at the time of the survey was visually observed, and when there was no or almost no difference from when the compound was not tested, the test plant died. Or, the one whose growth is completely inhibited is defined as "5" and evaluated in 6 levels of 0 to 5, 0, 1, 2,
Shown as 3, 4, and 5.

Test Example 1 Field soil surface treatment test Field soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of millet, oats, malaba morning glory and velvetleaf were sown and covered with soil. The test compound was made into an emulsion according to Formulation Example 2 or 5, and a predetermined amount thereof was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 20 days and the herbicidal efficacy was investigated. The results are shown in Table 4.

Test Example 2 Field foliage treatment test Field soil was filled in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of millet, Japanese radish and velvetleaf were sown and grown in a greenhouse for 10 days. Thereafter, the test compound was made into an emulsion in accordance with Formulation Example 2 or 5, and the predetermined amount was changed to 10 per 1 are.
It was diluted with water containing a spreading agent equivalent to 1 liter and foliage-treated from above the plant with a small sprayer. After the treatment, the plants were grown in a greenhouse for 20 days and the herbicidal efficacy was investigated. The results are shown in Table 5.

Test Example 3 Paddy Water Submersion Treatment Test Paddy soil was packed in a cylindrical plastic pot having a diameter of 8 cm and a depth of 12 cm, and seeds of Taenia japonicus and broad-leaved weeds (Azena, Kishigusa, Mizojabe) were mixed at a depth of 1 to 2 cm. After inundation and making it into a paddy field, 1 to 1 tuber of Urikawa
It was embedded at a depth of 2 cm, and rice at the second leaf stage was further transplanted and grown in a greenhouse. Six days later (the initial stage of each weed development), the test compound was made into an emulsion according to Formulation Example 2 or 5, and a predetermined amount of the compound was diluted with 5 ml of water and treated on the water surface. After the treatment, the plants were grown in a greenhouse for 20 days and the herbicidal efficacy was investigated. The results are shown in Table 6.

Test Example 4 Upland soil treatment test Field soil was packed in a vat having an area of 33 × 23 cm ² and a depth of 11 cm,
Soybean, peanut, cotton, corn, malaga morning glory, velvetleaf, blue-toothed pea, dog physalis, white,
Ebisugusa, barnyard grass, sorghum, and green sorghum were sowed and covered with a soil having a thickness of 1 to 2 cm. The test compound was made into an emulsion according to Formulation Example 2 or 5, and a predetermined amount thereof was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 20 days and the herbicidal efficacy was investigated. The results are shown in Table 7.

Test Example 5 Upland soil treatment test Field up soil was packed in a vat with an area of 33 × 23 cm ² and a depth of 11 cm,
Soybean, peanut, cotton, corn, sorghum,
Malaba morning glory, Black-faced fir, Black-necked squirrel, Ebisugusha, Dog-nosed hawk, American stag deer, horned hemlock, blue-spotted pearl millet, Euphorbiaceae, white-billed morning glory, white-billed harbor, white-necked peach, bindweed,
Purslane, cane millet, crabgrass, green foxtail,
Barnyard grass and sorghum sorghum were sown and covered with a soil having a thickness of 1 to 2 cm. A predetermined amount of the test compound, which was made into an emulsion according to Formulation Example 2 or 5, was diluted with water corresponding to 10 liters per are, and the soil surface was treated with a small sprayer. After processing 20
The plants were cultivated outdoors for one day and the herbicidal efficacy was investigated. The results are shown in Table 8.

Test Example 6 Upland soil treatment test Field up soil was packed in a vat with an area of 33 × 28 cm ² and a depth of 11 cm,
Wheat, sanaetade, yaemgra, chickweed, Spodoptera litura, and Spodoptera litura were sown and covered with a thickness of 1-2 cm. The test compound was made into an emulsion according to Formulation Example 2 or 5, and a predetermined amount thereof was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. After the treatment, the plants were grown in a greenhouse for 27 days and the herbicidal effect was investigated. The results are shown in Table 9.

Test Example 7 Field foliage treatment test A bat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with field soil,
Maize, black fir, velvetleaf, Malaga morning glory, physalis sycamore, and blue-spotted gall were sowed and cultivated for 18 days.
After that, the test compound was made into an emulsion according to Formulation Example 2 or 5, and a predetermined amount thereof was diluted with 5 liters of water equivalent to 1 are containing a spreading agent, and the whole foliage was planted from above the plant with a small sprayer. Uniformly processed. At this time, the growth conditions of weeds and crops differed depending on the grass species, but at the 1 to 4 leaf stage, the plant height was 2 to 12 cm. The herbicidal efficacy was investigated 20 days after the treatment. The results are shown in Table 10. This test was conducted in a greenhouse throughout the entire period.

Test Example 8 Field and foliage treatment test A bat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with field soil,
Wheat, Harutade, Yaemgra, Chickweed, and Scutellaria barbata were sown and cultivated for 18 days. After that, the test compound was made into an emulsion according to Formulation Example 2 or 5, and a predetermined amount thereof was diluted with 5 liters of water equivalent to 1 are containing a spreading agent, and the whole foliage was planted from above the plant with a small sprayer. Uniformly processed. At this time, the growth conditions of weeds and crops differed depending on the grass species, but at the 1 to 4 leaf stage, the plant height was 2 to 12 cm. The herbicidal efficacy was investigated 20 days after the treatment. The result is No. 11
Shown in the table. This test was conducted in a greenhouse throughout the entire period.

Test Example 9 Upland soil treatment test In a field ridged to have a top width of 1 m, corn, velvetleaf, blue-toothed pearl millet, and periwinkle were sowed.
The test area was divided into 8 m ² per area. An emulsion was prepared in accordance with Formulation Example 2 or 5, and a predetermined amount of the test compound was diluted with water equivalent to 10 liters per are, and the whole surface of the test area was surface-treated with a small sprayer. The repetition was repeated three times, and the herbicidal efficacy was investigated after 32 days. The results are shown in Table 12.

<Effects of the Invention> As described above, the compound of the present invention is used for various weeds that are problematic in the foliar treatment and soil treatment of upland fields, such as buckwheat vine, Harutade, Sanaetade, purslane,
Chickweed, white lizard, blue-toothed radish, Japanese radish, velvetleaf, nazuna, horned hemlock, Ebisugusa, hornbill, American stag deer, field pansy, yaemgra, American morning glory, Malva morning glory, common bindweed, white-billed hemlock, dog physalis,
Broad-leaved weeds such as Scutellaria baicalensis, Onami fir, Sunflower, dog chamomile, corn marigold, Euphorbiaceae, millet, lobster, green foxtail, scabbard, Ophiaceae, etc. Weeds and Commelinae weeds such as Commelina, having herbicidal activity against weeds such as Cyperaceae weeds such as Kogomenogaya, and the compound of the present invention, corn, sorghum, wheat, barley,
It does not show any harmful effects on major crops such as rice, soybean, peanut, and cotton.

Further, the compound of the present invention, in the flooding treatment of paddy fields, various weeds that are problematic, for example, grass weeds such as Taenia japonicus, asena, broad-leaved weeds such as Aedna, Kishigusa, Mizohakobe, Cyperaceae weeds such as Pinegrass, matsuba, etc. ,
It has a weeding effect against Urikawa and the like, and does not show any harmful phytotoxicity against rice.

Furthermore, the compound of the present invention can be used as a herbicide for paddy fields, upland fields, orchards, meadows, lawns, forests or non-agricultural lands, and by mixing with other herbicides, weeding It can be expected to enhance the efficacy. Furthermore, it can be used by mixing with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like.

Claims (2)

[Claims] 1. A general formula [In the formula, R represents 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, a lower alkoxy lower alkyl group, a lower alkoxy lower alkoxy lower alkyl group, It represents a cinnamyl group or a cyano lower alkyl group. ] The benzothiazolone derivative shown by these. 2. General formula [In the formula, R represents 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, a lower alkoxy lower alkyl group, a lower alkoxy lower alkoxy lower alkyl group, It represents a cinnamyl group or a cyano lower alkyl group. ] A herbicide containing a benzothiazolone derivative represented by the following as an active ingredient.