JPH06781B2 - Triazolopyridazinedione derivative and herbicide containing it as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a C _{1 to} C ₅ alkyl group, a C _{3 to} C ₄ alkenyl group, and a C _{3 to} C ₄
It represents an alkynyl group or a C ₁ -C ₄ alkoxymethyl group, and X represents a hydrogen atom or a fluorine atom. ] A triazolopyridazinedione derivative represented by (hereinafter,
It is described as the compound of the present invention. ) And a herbicide containing it as an active ingredient.

The compound of the present invention, in the treatment of stalks and soil in upland fields, various weeds that are problematic, for example, buckwheat vine, Sanaetade, purslane, chickweed, white lobster, agate,
Japanese radish, red-bellied pepper, red horned squirrel, Ebisugusu, hibiscus, American stag deer, field pansy, yaemgra, American morning glory, Malva morning glory, white-billed morning glory, dog physalis, red-billed leafhopper, cornflower, sunflower, dogwood gold leaf, corn, etc. The present invention has a herbicidal activity against grass weeds such as sorghum, Echinochloa chinensis, echinococcus, crabgrass, bluegrass, oak amberjack, oats, oats, sorghum and communis weeds such as communis, and cyperaceae weeds such as hazelnut, and the present invention. The compounds do not show any harmful effects on major crops such as corn, wheat, rice, soybean and cotton.

Further, the compound of the present invention is a variety of weeds that are problematic in the flooding treatment of paddy fields, for example, grass weeds such as Taenia japonicus, azena, yellow grass, broad-leaved weeds such as Mizochabe, firefly,
It has herbicidal activity against cyperaceae weeds such as pine nuts, eels, urchins, and the like, and does not show any harmful phytotoxicity to rice.

The compound of the present invention has the general formula [Wherein R ¹ , R ² and X have the same meanings as described above,
R ³ represents a lower alkyl group. ] The benzoxazine derivative shown by this and 0.01-1 equivalent with respect to this in a solvent are 10 degreeC-100 degree.
It can be produced by reacting at 0 ° C. for 10 minutes to 24 hours and ring closure.

As a solvent, aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and dichlorobenzene. Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone and cyclohexanone,
Alcohols such as methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methyl cellosolve, diethylene glycol, glycerin, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N, N-diethylaniline, tributylamine. , Tertiary amines such as N-methylmorpholine, acid amides such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, and mixtures thereof. To be

As the base, pyridine, triethylamine, N, N-
Examples thereof include organic bases such as diethylaniline, 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 completion of the reaction, the reaction solution after addition of water is subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purification by operations such as chromatography and recrystallization to obtain the desired compound of the present invention. The compound can be obtained.

Next, Table 1 shows the compounds of the present invention produced by this production method.

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

Production Example 1 1.8 g of 1- (4-propargyl-7-fluoro-2H-benzoxazin-3 (4H) -one-6-ylaminocarbonyl) -2-ethoxycarbonylhexahydropyridazine was added to 30 m of methanol, and sodium was added. A catalytic amount of methoxide was added. After heating under reflux for 2 hours, water was added and the mixture was extracted with ethyl acetate. The extract was washed with water, dried and concentrated, and the obtained crystals were washed with ether to give 2- (4-propargyl-7-fluoro-2H-benzoxazine-3.
(4H) -on-6-yl) hexahydro-1H-
[1,2,4] triazolo [1,2-a] pyridazine-
1.1 g of 1,3-dione was obtained. m. p. 229-23
Table 2 shows some of the compounds of the present invention which can be produced by such a production method.

In the case of producing the compound of the present invention, the benzoxazine derivative [II] which is a starting compound has the general formula [In the formula, R ¹ , R ² and X have the same meanings as described above. ] And an isocyanate represented by the general formula [In the formula, R ³ represents a lower alkyl group. ] The hexahydropyridazine carboxylic acid ester shown by these in a solvent in presence of a base, 0 degreeC-100 degreeC, 1 hour-
It can be produced by reacting for 10 hours.

The amount of reagent used in this reaction is isocyanate [II
Hexahydropyridazinecarboxylic acid ester [IV] is 1.0 to 1.1 equivalents, and the base is 1.0 to 1 equivalent to 1 equivalent.
1.1 equivalents.

Examples of the solvent include esters such as ethyl acetate and ethers such as dioxane and dimethoxyethane.

As the base, triethylamine, pyridine, N, N-
Examples thereof include dimethylaniline and N, N-diethylaniline.

After completion of the reaction, the reaction solution is added with water and then subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purification by operations such as chromatography and recrystallization to obtain the desired benzoxazine. The derivative [II] can be obtained.

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 a weight ratio of 0.03 to 90%, preferably 0.05 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, 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, dimethyl sulfoxide, N ，
Examples include N-dimethylformamide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, moistening, etc. include anionic surface active agents such as alkyl sulfate ester salts, alkyl aryl sulfonates, dialkyl sulfosuccinates, and polyoxyethylene alkyl aryl ether phosphate ester salts. Agent, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether,
Examples thereof include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. As a formulation auxiliary agent, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PA
P (acidic isopropyl phosphate) and the like can be mentioned.

Formulation examples are shown below. The compounds of the present invention have the compound numbers shown in Table 1. Parts indicate parts by weight.

Formulation Example 1 4, 50 parts of the compound of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain a wettable powder.

Formulation Example 2 The compound of the present invention 3, 5 parts, polyoxyethylene styryl phenyl ether 14 parts, calcium dodecylbenzenesulfonate 6 parts, xylene 30 parts and N, N-dimethylformamide 45 parts are thoroughly mixed to obtain an emulsion.

Formulation Example 3 The compound 6 of the present invention 6, 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 were well pulverized and mixed, and water was added and kneaded well, and then, Granules are dried to obtain granules.

Formulation Example 4 The compound of the present invention (7, 25 parts), polyoxyethylene sorbitan monooleate (3 parts), CMC (3 parts) and water (69 parts) are mixed and wet-ground until the particle size becomes 5 μm or less to obtain a suspension agent.

The compound of the present invention thus prepared is subjected to soil treatment, foliar 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 for treating only the weeds so as not to adhere to the crop.

In addition, the herbicidal effect can be expected to be enhanced by treating it with a mixture with other herbicides. In addition, insecticides, acaricides,
It can also be treated by mixing with nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like.

Incidentally, the compound of the present invention, paddy field, upland, orchard, meadow,
It can be used as an active ingredient of a herbicide for lawn, forest or non-cultivated land.

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
0.01 g to 100 g per are, preferably 0.0
The amount of the emulsion, wettable powder, suspension, etc. is usually 1 liter to 10 liters per 1 are of water (if necessary, an auxiliary agent such as a spreading agent is added) in water. It is diluted and treated, and granules and the like are usually treated as it is without any dilution.

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.

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 as comparative controls 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 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, Malaba morning glory and velvetleaf were sown to cover the soil. The test compound was made into an emulsion according to Formulation Example 2, 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 packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of millet, Japanese radish and hibiscus were sown and grown in a greenhouse for 10 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, and the predetermined amount thereof was 1 per 1 are.
It was diluted with water containing 0 liter of a spreading agent, and foliage treatment was performed 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 field flooding test: Paddy soil was packed in a cylindrical plastic pot with a diameter of 8 cm and a depth of 12 cm, and seeds of rice ball millet, broad-leaved weeds (Azena, Kishigusa, Mizojabe) and firefly were mixed to a depth of 1-2 cm. It is. After watering to make paddy fields, tubers of Urikawa were embedded at a depth of 1 to 2 cm and grown in a greenhouse.
Six days later (the initial stage of the development of each weed), the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof 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 up soil was packed in a vat having an area of 33 × 23 cm ² and a depth of 11 cm, and dies, corn, gall, Maraba's morning glory, velvetleaf, blue-toothed foxtail, Physcomitrella patens, sophora serrata, Enocologsa, and crabgrass seed were sowed. 1-2
The soil was covered to a thickness of cm. The test compound was made into an emulsion according to Formulation Example 2, 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 soil was packed in a vat having an area of 33 × 23 cm ² and a depth of 11 cm, and seeds of wheat, yaemgra, Scutellaria baicalensis, chickweed, white azalea, buckweed, and bluegrass were sowed to a thickness of 1 to 2 cm. Covered with soil. The compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the compound was diluted with water equivalent to 10 liters per arm, 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 efficacy was investigated. The results are shown in Table 8.

Test Example 6 Field foliage treatment test Field soil was packed in a vat having an area of 33 × 23 cm ² and a depth of 11 cm, and corn, wheat, sugar beet, gall, velvetleaf, physalis alba, Malaba morning glory, white lobster, and green locust were sown and grown for 18 days. . Then, Formulation Example 2
The test compound was made into an emulsion in accordance with the procedure described in 1., and a predetermined amount thereof was diluted with 5 liters of water per 1 are containing a spreading agent, and uniformly treated on the entire surface of the foliage from above the plant with a small sprayer. 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 9. This test was conducted in a greenhouse throughout the entire period.

Test Example 7 Paddy field flooding test 1 / 5000a Wagner pots were filled with paddy field soil, and rice ball millet, broad-leaved weeds (Azena, Prickly Pear grass, Mizochabe) and pine bud winter buds were mixed to 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 3-leaf stage was further transplanted and grown in a greenhouse. 6 days later (Early germination period of Tainubie),
The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 10 ml of water and treated on the water surface to make the water depth 4 cm. 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 10. In addition,
From the day after the treatment, the amount of water leakage was 3 days per day, which was equivalent to a depth of 3 cm.

Claims (2)

[Claims] 1. A general formula [In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ²
Is a C ₁ -C ₅ alkyl group, a C ₃ -C ₄ alkenyl group, C
₃ -C ₄ represents an alkynyl group or a _C 1 -C ₄ alkoxymethyl group, X represents a hydrogen atom or a fluorine atom. ] The triazolopyridazine dione derivative shown by these. 2. General formula [In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ²
Is a C ₁ -C ₅ alkyl group, a C ₃ -C ₄ alkenyl group, C
₃ -C ₄ represents an alkynyl group or a _C 1 -C ₄ alkoxymethyl group, X represents a hydrogen atom or a fluorine atom. ] The triazolopyridazinedione derivative shown by these as an active ingredient, The herbicide characterized by the above-mentioned.