JPH0321032B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [In the formula, R represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group, and X represents a chlorine atom or a bromine atom. ] The present invention relates to a 4-phenylurazole derivative (hereinafter referred to as the compound of the present invention) shown in the following, a method for producing the same, and a herbicide containing the same as an active ingredient. The compound of the present invention can be used to treat various weeds that are problematic in foliar and soil treatments in upland fields, such as freckle weeds, Japanese knotweed, purslane, chickweed, whiteweed, Japanese radish, Japanese radish, Japanese radish, shepherd's shepherd's purse, American hornwort, Ebisu grass, and Japanese radish. , broadleaf weeds such as golden deer, field pansies, Japanese violets, morning glories, common morning glories, European bindweed, staghorn lilies, hotokenoza, staghorn morning glories, Physalis spp., Physalis spp. It has a herbicidal effect against grass weeds such as grasshopper, foxtail grass, black grass, black grass, blackgrass, oat, oat, Seiban sorghum, grass wheat, and cyperus weeds, as well as cyperus weeds such as cyperus japonica and cyperus japonica.
Moreover, the compounds of the present invention do not cause any problematic phytotoxicity to major crops such as corn, wheat, soybeans, and cotton. In addition, the compound of the present invention can be applied to various weeds that are a problem in rice fields, such as grass weeds such as Japanese grasshopper and Japanese grasshopper, broad-leaved weeds such as azalea, japonica, and chickweed; It has a herbicidal effect on paddy field weeds such as . 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 or non-agricultural lands. The compound of the present invention has the general formula [In the formula, R and X have the same meanings as above, and R' represents a lower alkyl group. ] Tetrahydropyridazine carboxylic acid ester represented by and a catalytic amount of base in a solvent at 0°C to 200°C,
It can be produced by reacting for 1 to 24 hours. As a solvent, aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc.
Chloroform, carbon tetrachloride, dichloroethane,
Halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran,
Examples include ethers such as diethylene glycol dimethyl ether, alcohols such as methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methyl cellosolve, diethylene glycol, and glycerin, water, and mixtures thereof. Bases include pyridine, triethylamine,
Organic bases such as N,N-diethylaniline, sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic bases such as potassium carbonate and sodium hydride,
Examples include alkali metal alkoxides such as sodium methoxide and sodium ethoxide. After completion of the reaction, usual post-treatments are carried out, and if necessary, purification is carried out by chromatography, distillation, recrystallization, etc. Next, a production example of the compound of the present invention will be shown. Production Example 1 (Production of Compound 2 of the Invention) Ethyl 2-[4-chloro-2-fluoro-5
-(1-methylethoxy)phenyl]aminothioxomethyl-3,4,5,6-tetrahydro-1
0.66 g of -(2H)-pyridazine carboxylate was dissolved in 200 ml of toluene, several drops of sodium methoxide were added, and the mixture was refluxed for 3 hours. After cooling, water was added and extracted with toluene. The toluene layer was washed with saturated brine, dried, and concentrated to give 2-[4-chloro-2-
Fluoro-(1-methylethoxy)phenyl]-
0.3 g of 5,6,7,8-tetrahydro-1H-[1.2.4]triazolo-[1.2-a]-pyridazin-3-thioxo-1-(2H)-one was obtained. ^n25D _{_}
1.5720 Some of the compounds of the present invention that can be produced by such a production method are shown in Table 1.

[Table] When producing the compound of the present invention, the tetrahydropyridazine carboxylic acid ester of general formula [], which is a raw material compound, is [In the formula, R and X have the same meanings as above. ] phenyl isothiocyanate shown by 1.0~
General formula for 1.1 equivalent [In the formula, R′ represents the same meaning as above. ] It can be produced by reacting an alkyl 3,4,5,6-tetrahydropyridazine-1-(2H)-carboxylate represented by in a solvent at 0°C to 100°C for 1 hour to 48 hours. can. Examples of the solvent include toluene, benzene, chloroform, and tetrahydrofuran. After completion of the reaction, usual post-treatments are carried out, and if necessary, purification is carried out by chromatography, distillation, recrystallization, etc. Next, an example of the production of tetrahydropyridazine carboxylic acid ether of the general formula [] will be shown. Production Example 2 2.8 g of 4-chloro-2-fluoro-5-(1-methylethoxy)phenylisothiocyanate,
Add several drops of triethylamine to a mixture of 1.8 g of 2-ethoxycarbonyl-3,4,5,6-tetrahydro-(1H,2H)-pyridazine and 5 ml of toluene.
Stirred at 25°C overnight. Water was added to separate the toluene layer, washed with water, dried, and concentrated. The residue was purified using a silica gel column, and ethyl 2-[4-chloro-
2-Fluoro-5-(1-methylethoxy)phenylaminothioxomethyl]-3,4,5,6-
2 g of tetrahydro-1-(2H)-pyridazinecarboxylate were obtained. n ^27.5 _D 1.5534 When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, liquid carrier, surfactant or other formulation auxiliary agent, and prepared as an emulsion, a wettable powder, or
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 1 to 80%. Solid carriers include kaolin clay, attapulgiaite clay, bentonite, acid clay, pyrofluorite, talc, diatomaceous earth, calcite, walnut powder,
There are fine powders or granules such as urea, ammonium sulfate, and synthetic hydrous silicon oxide, and liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, acetone, cyclohexanone, Examples include ketones such as isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile, and water. Surfactants used for emulsification, dispersion, wetting, etc. include negative salts such as alkyl sulfate salts, alkyl (aryl) sulfonate salts, dialkyl sulfosuccinate salts, and polyoxyethylene alkylaryl ether phosphate salts. Examples include ionic surfactants, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, and polyoxysorbitan fatty acid ester. Formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol,
Examples include gum arabic, CMC (carboxymethylcellulose), and PAP (isopropyl acid phosphate). Examples of formulations are shown below. In addition, the compound of the present invention is the first
Indicated by compound number in the table. Parts indicate parts by weight. Formulation Example 1 50 parts of Compound 1 of the present invention, 3 parts of calcium ligninsulfonate, 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 10 parts of Compound 2 of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecybenzenesulfonate, 30 parts of xylene and 40 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 hydrated silicon oxide
1 part, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 65 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, followed by granulation and drying to obtain granules. Formulation Example 4 Compound 3 of the present invention, 25 parts, polyoxyethylene sorbitan monooleate 3 parts, CMC 3 parts, and water 69 parts were mixed and wet-pulverized until the particle size of the active ingredient became 5 microns or less to form a suspension. obtain. Formulation Example 5 10 parts of Compound 4 of the present invention, 7 parts of polyoxyethylene alkylaryl ether, 3 parts of alkylaryl sulfonate and 80 parts of cyclohexanone are thoroughly mixed to obtain an emulsion. These preparations can be used as they are or diluted with water, etc., and treated with foliage or soil. For soil treatment, spray the preparation on the soil surface (if necessary,
Mix with soil after spraying. ) or irrigate the soil. 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, plant growth regulators, fertilizers, soil conditioners, and the like. When the compound of the present invention is used as an active ingredient of a herbicide, the application amount is usually 0.1 g to 1 are.
50g, preferably 0.2g to 30g, emulsion,
Wettable powders, suspending agents, etc. are 1 liter per are.
Dilute with 10 liters of water (if necessary, add a spreading agent such as a spreading agent) and apply. Granules etc. should be applied as is without any dilution. In addition to the above-mentioned surfactants, spreading agents include polyoxyethylene resin acids (esters), lignin sulfonates, abietates, dinaphthylmethane disulfonates, paraffin, and the like. 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】

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【formula】

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【formula】

[Formula] In addition, the herbicidal efficacy against weeds and crops in Test Examples 1, 2, 3, and 4 was determined by visually observing the degree of germination and growth inhibition of the test plants at the time of the investigation. A score of 0 indicates that there is almost no difference, and a score of 5 indicates that the test plant has died or its growth has been completely inhibited.
Shown as 4 and 5. The herbicidal efficacy against weeds in Test Examples 5 and 6 was determined by measuring the fresh weight of the above-ground parts of the plants that remained withered during the investigation, and calculating the ratio (%) when compared with the fresh weight of the plants in the untreated area. It is indicated by a number from 0 to 5 based on the criteria in Table 3.

[Table] Test Example 1 Upland Soil Mixing Treatment Test Upland soil was filled into a cylindrical plastic pot with a diameter of 10 cm and a depth of 10 cm, and barnyard grass, oats, morning glory, and Japanese strawberry were sown and covered with soil. Dilute the test compound in an emulsion with water equivalent to 10 liters per area according to Formulation Example 2, spray the specified amount on the soil surface with a small sprayer, and thoroughly mix the soil surface to a depth of 4 cm. , and then transplanted the clumps of Japanese commonweed. After spraying, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 4.

【table】

[Table] Test Example 2 Upland soil mixing treatment test Upland soil was filled in a vat with an area of 33 x 23 cm ² and a depth of 11 cm, and Seiban sorghum, black grass, crabgrass, Japanese radish, Japanese morning glory, dogberry,
Buckwheat was sown and covered with soil to a thickness of 1 to 2 cm. 1 of the test compound made into an emulsion according to Formulation Example 2
It was diluted with water equivalent to 10 liters per area, and a predetermined amount of it was sprayed on the soil surface using a small sprayer, and the soil surface layer up to a depth of 4 cm was thoroughly mixed. Furthermore, seeds of corn, cotton, and soybean were embedded to a depth of 2 cm. Grow indoors for 20 days after spraying,
The herbicidal efficacy was investigated. The results are shown in Table 5.

[Table] Test example 3 Field soil, stem, and leaf treatment test Field soil was filled in a vat with an area of 33 x 23 cm ² and a depth of 11 cm, and corn, wheat, Japanese yam, Japanese fir, Japanese mulberry, Japanese white radish, Japanese brilliance, and Japanese violet were sown and grown for 18 days. did. Thereafter, the test compound made into an emulsion according to Formulation Example 2 was diluted with water equivalent to 5 liters per are containing a spreading agent, and a predetermined amount of it was uniformly applied from the top of the plant to the entire stem and leaf area using a small sprayer. was dispersed. At this time, the growth of each plant varied depending on the grass species, but it was in the 1-4 leaf stage and the plant height was 2-12 cm. Herbicidal efficacy was investigated 20 days after spraying. The results are shown in Table 6. This test was conducted in a greenhouse throughout the entire period.

[Table] Test example 4 Paddy soil and foliage treatment test Fill a 1/5000a Wagner pot with paddy soil.
Japanese millet, broad-leaved weeds (Azeena, Azalea, Chickweed), bulrush seeds, and overwintered buds of Pinus vulgare were mixed in at a depth of 1 to 2 cm. After flooding the fields to create a paddy field, tubers of Urikawa were buried at a depth of 1 to 2 cm, followed by transplanting rice at the 3-leaf stage and growing them in a greenhouse. After 11 days (at the two-leaf stage of Japanese millet), the test compound made into an emulsion according to Formulation Example 2 was diluted with 10 milliliters of water per pot, and a predetermined amount of it was dropped onto the water surface. After dropping, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 7.

[Table] Test Example 5 Soil surface treatment test A plastic beaker with a diameter of 10 cm and a height of 10 cm was filled with field soil, and barnyard grass, oats, morning glory, and Japanese strawberry were sown and covered with soil. The supplied compound, which was made into an emulsion according to Formulation Example 5, was diluted with water equivalent to 5 parts per are, and a predetermined amount was spread on the soil surface using a small sprayer. The plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 8.

[Table] Test Example 6 Field Soil Treatment Test A plastic pot with a diameter of 10 cm and a depth of 10 cm was filled with field soil, and Magelotus tubers were transplanted and grown in a greenhouse for 2 to 4 weeks. Separately, seeds of millet, oat, radish, and Japanese radish were sown in similar pots and grown for two weeks in a greenhouse. The test compound made into an emulsion according to Formulation Example 5 was diluted with water containing 5 equivalents of a spreading agent per are, and a predetermined amount was sprayed over the leaves of the plant using a small sprayer. The plants were grown in a greenhouse for 3 weeks and their herbicidal efficacy was investigated. The lotus beetles were grown in a greenhouse for another two weeks,
The degree of recovery was investigated compared to the case without treatment. A: No recovery, B: 1-10% recovery, C: 11-50% recovery, D: 51% or more recovery. The results are shown in Table 9.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group, and X represents a chlorine atom or a bromine atom. ] A 4-phenylurazole derivative represented by the following. 2 General formula [In the formula, R represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group, R' represents a lower alkyl group, and X represents a chlorine atom or a bromine atom. ] A general formula characterized by reacting a tetrahydropyridazine carboxylic acid ester and a base with [In the formula, R and X have the same meanings as above. ] A method for producing a 4-phenylurazole derivative. 3 General formula [In the formula, R represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group, and X represents a chlorine atom or a bromine atom. ] A herbicide characterized by containing a 4-phenylurazole derivative represented by the following as an active ingredient.