JPH047344B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [In the formula, R represents a lower alkenyl group or a lower alkynyl group, and X represents a hydrogen atom or a fluorine atom. ] 4,5,6,7-tetrahydro-1,
This invention relates to a 2,3-benztriazole-1-oxide derivative (hereinafter referred to as the compound of the present invention), a method for producing the same, and a herbicide containing the same as an active ingredient. The compounds of the present invention can be used to treat various weeds that are problematic in the treatment of foliage and soil in upland fields, such as purslane, whiteweed, Japanese radish, Japanese radish, shepherd's purse, shepherd's purse, American hornwort, Ebisu grass, Japanese commonweed, American goldenrod, Broad-leafed weeds such as morning glory, morning glory, Convolvulus, Convolvulus, Japanese odorifera, Hotokenoza, Japanese morning glory, Japanese Physalis, Japanese Physalis, Japanese fir tree, sunflower, Japanese chamomile, corn marigold, etc., barnyard grass,
It has a herbicidal effect against weeds of the grass family, such as grasshopper, foxtail grass, crabgrass, sycamore, grasshopper, oat, oat, and seiban sorghum, as well as weeds of the family Cyperaceae, such as dayflower, and weeds of the family Cyperaceae, such as Cyperus japonica.
Moreover, some of the compounds of the present invention are
It does not cause any harmful effects on major crops such as wheat, rice, soybean, 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, staghorn grass, and Japanese chickweed, and cyperaceous weeds such as cyperus cyperus, bulrush, cypress, and cyperus cyperus. It has a herbicidal effect on grasses such as Prunus japonicus and Prunus elegans, and does not cause any harmful effects on rice. The compound of the present invention has the general formula [In the formula, X represents the same meaning as above. ] 2-hydroxyphenyl-4,5,
6,7-tetrahydro-1,2,3-benztriazole-1-oxide derivative and the general formula RZ [] [wherein Z represents a halogen atom, an alkyl-substituted phenylsulfonate group or an alkylsulfonate group, and R is Same meaning as above. ] In a solvent, in the presence of a dehydrohalogenating agent, and if necessary, in the presence of a phase transfer catalyst, produced by reacting with an electrophilic reagent shown at 0°C to 150°C for 0.5 to 24 hours. can do. The amount of reagents used in the reaction is 2-hydroxyphenyl-4,5,6,7-tetrahydro-1,
For 1 equivalent of 2,3-benztriazole-1-oxide derivative [], the electrophile [] is
1.0 to 1.5 equivalents, the dehydrohalogenating agent is 1.0 to 1.5 equivalents, and the phase transfer catalyst is 0.01 to 0.1 equivalents. Examples of solvents include aromatic hydrocarbons such as benzene, toluene, and hexane, ketones such as acetone and methyl ethyl ketone, amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethyl sulfoxide, tetrahydrofuran,
Examples include ethers such as diethyl ether and ethylene glycol dimethyl ether, nitriles such as acetonitrile, water, and mixtures thereof. Examples of dehydrohalogenation agents include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide, and organic bases such as pyridine, triethylamine, N,N-dimethylaniline, and N,N-diethylaniline. . Examples of the phase transfer catalyst include tetrabutylammonium bromide, tributylbenzylammonium chloride, triethylbenzylammonium bromide, and the like. Also, potassium iodide, 1
The addition of valent copper salts may be preferred. After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, purified by chromatography, recrystallization, etc. Next, production examples of the compounds of the present invention will be shown. Production Example (Production of Compound 2 of the Invention) 2-(4-chloro-2-fluoro-5-hydroxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazole-1-oxide 0.6 g of propargyl bromide was added to a mixture of 1 g of potassium carbonate, 0.3 g of potassium carbonate, and 5 ml of dimethylformamide, and the mixture was stirred at 70 to 80°C for 4 hours. After cooling, water was added and the mixture was extracted with ethyl acetate. Wash and dry the organic layer.
The residue was purified by silica gel thin layer chromatography (developing solvent: n-hexane/ethyl acetate) to obtain 2-(4-chloro-2-fluoro-5
-propargyloxyphenyl)-4,5,6,
0.15 g of 7-tetrahydro-1,2,3-benztriazole-1-oxide was obtained. mp 155−156℃. Table 1 shows some of the compounds of the present invention that can be produced by such a production method.

[Table] When producing the compound of the present invention, the starting compound 2-hydroxyphenyl-4,5,6,7-tetrahydro-1,2,3-benztriazole-
1-oxide derivative [] has the general formula [In the formula, X represents a hydrogen atom or a fluorine atom. ] Hydrazone shown by and 1.0 to 1.5 for this
It can be produced by reacting an equivalent amount of an oxidizing agent in a solvent at 0°C to 150°C for 1.0 to 24 hours. Examples of the solvent include water, tetrahydrofuran, pyridine, ether, and mixtures thereof. Examples of the oxidizing agent include lead tetraacetate, mercury oxide, divalent copper salts, etc., and it is particularly preferable to use divalent copper salts in the presence of a base such as pyridine. After the reaction is completed, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, purified by chromatography, recrystallization, etc. Moreover, hydrazone [ ] can be produced by the following method. That is, the general formula [In the formula, X represents the same meaning as above. ] After diazotizing the aniline derivative shown at -10°C to 10°C, using a reducing agent such as stannous chloride, -30
After reduction at ℃~-10℃, the general formula [In the formula, X represents the same meaning as above. ] Obtain a phenylhydrazine derivative represented by [ ] and the general formula of 1.0 to 1.1 equivalents to this phenylhydrazine derivative [] [In the formula, R ₁ and R ₂ are the same or different,
It represents a lower alkyl group, or a cycloalkyl group in which R ₁ and R ₂ together form a ring containing or not containing an oxygen atom. ] Hydrazone [ ] can be produced by reacting the enamines represented by the formula at 0°C to 100°C in the presence of an acid catalyst if necessary. Next, the raw material compound 2-hydroxyphenyl-4,5,6,7-tetrahydro-1,2,3-
Benztriazole-1-oxide derivative []
A manufacturing example of is shown as a reference example. Reference Example 1 32.5 g of 4-chloro-2-fluoro-5-hydroxyaniline was added to 300 ml of concentrated hydrochloric acid to form a salt, and then an aqueous solution of 15.2 g of sodium nitrite dissolved in 20 ml of water was added at 0° to -5°C. . 0-5℃ for another 30 minutes
After stirring, urea was added to remove excess nitrite ions, and the mixture was cooled to -30°C. Add to this 92g of stannous chloride,
A solution of 160 ml of hydrochloric acid was added, and the mixture was stirred at 0 to -10°C for 3 hours. The reaction solution was separated, and the obtained crystals were dissolved in water, neutralized with sodium hydroxide, and extracted with ethyl acetate. The organic layer was washed with water, dried, and concentrated. The residue was treated with ether to obtain 8.4 g of 4-chloro-2-fluoro-5-hydroxyphenylhydrazine as crystals. This was added to a solution of 9.35 g of 2-hydroxyiminocyclohexanonemorpholinoenamine, 90 ml of ethanol, and acetic acid (catalytic amount), and heated under reflux for 3 hours. After cooling, ethanol was removed, water was added, and the mixture was extracted with ethyl acetate. It was dried and concentrated, and the residue was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane) to obtain 2-
(4-chloro-2-fluoro-5-hydroxyphenyl)hydrazonocyclohexanone oxime 8
Crystals of g were obtained. Add this to 50% tetrahydrofuran
ml, suspended in 112 ml of 15% pyridine water, 11.2 g of copper sulfate (CuSO ₄ .5H ₂ O) dissolved in 40 ml of water was added, and the mixture was further heated under reflux for 2 hours. After cooling, water was added and extracted with ethyl acetate. The organic layer was washed with an aqueous copper sulfate solution, dried, and concentrated. This was subjected to silica gel column chromatography (eluent: ethyl acetate/n
2-(4-chloro-2-
Fluoro-5-hydroxyphenyl)-4,5,
4 g of crystals of 6,7-tetrahydro-1,2,3-benztriazole-1-oxide were obtained. mp
220-221 (Decomposition) Reference Example 2 In the same manner as Reference Example 1, 2-(4-chloro-3-hydroxyphenyl)-4,5,6,7-tetrahydro- was produced from 4-chloro-3-hydroxyaniline. 1,2,3-benztriazole-1-oxide, mp 189-191°C (decomposition) was obtained. When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant, and other formulation auxiliaries to form an emulsion, wettable powder, etc.
Formulate into suspensions, granules, etc. These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.01 to 80%, preferably 0.01 to 50%.
contains. Solid carriers include fine powders or granules such as kaolin clay, attapalgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include 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,
Examples include acetonitrile and water. Surfactants used for emulsification, dispersion, wetting, etc. include anionic interfaces such as alkyl sulfate salts, alkyl (aryl) sulfone hydrochloric acids, dialkyl sulfosuccinates, and polyoxyethylene alkylaryl ether phosphate salts. Examples include activators, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Formulation auxiliaries include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethylcellulose), and PAP (isopropyl acid phosphate).
etc. 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 2 of the present invention, 3 parts of calcium lignosulfonate, 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 3 of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 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 lignin sulfonate, 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 25 parts of the compound of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water are mixed and wet-pulverized until the particle size becomes 5 microns or less to obtain a suspension. The compound of the present invention thus formulated is 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. 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, fungicides, plant growth regulators, fertilizers, soil conditioners, and the like. The compound of the present invention can be used in rice fields, fields, orchards,
It can be used as an active ingredient in herbicides for pastures, lawns, forests, non-agricultural lands, etc. When the compound of the present invention is used as an active ingredient of a herbicide, the amount of application varies depending on weather conditions, formulation form, application time, method, location, target weeds, target crops, etc., but is usually 0.005 g per are. ~40
g, preferably 0.01 g to 10 g, and emulsions, hydrating agents, suspending agents, etc. are usually used in a predetermined amount of 1 liter to 10 liters per are (if necessary, auxiliary agents such as spreading agents etc.) Granules, etc. are usually treated as they are without any dilution. In addition to the above-mentioned surfactants, the spreading agent includes polyoxyethylene resin acid (ester), lignin sulfonate, abietate, dinaphthylmethane disulfonate, paraffin, and the like. Next, test examples will show 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] In addition, the herbicidal efficacy is determined by visually observing the degree of inhibition of budding and growth of the test plants during the survey, and ``0'' indicates that there is no or almost no difference from when no compound is tested. A rating of 0 to 5 indicates that the plant is withering or its growth is completely inhibited.
It is evaluated in 6 stages of 5, and is shown as 0, 1, 2, 3, 4, and 5. Test example 1 Paddy field flooding treatment test A 1/5000a Wagner pot was filled with paddy soil.
Japanese millet, broad-leaved weeds (Azeena, Aspergillus japonica, Chickweed), bulrush seeds, and overwintering buds of Pinus spp. were mixed in at a depth of 1 to 2 cm. After flooding the rice field to create a paddy field, three-leaf stage rice was transplanted and grown in a greenhouse. After 3 days (in the early stages of the outbreak of blueberry),
The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was diluted with 10 milliliters of water and applied to the water surface to a depth of 4 cm. After treatment, they were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The result is the third
Shown in the table. In addition, for two days from the day after the treatment, water leaked in an amount equivalent to a water depth of 3 cm per day.

[Table] Test example 2 Upland soil treatment test Upland soil was filled into a vat with an area of 33 x 23 cm ² and a depth of 11 cm, and soybean, cotton, sugar beet, corn,
Wheat, Japanese morning glory, Japanese fir tree, Japanese yam, Japanese barnyard grass, barnyard grass, Seiban sorghum, and foxtail grass were sown and covered with soil to a thickness of 1 to 2 cm. The test compound was made into an emulsion according to Formulation Example 2, 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. 20 after processing
The plants were grown in a greenhouse for one day and their herbicidal efficacy was investigated. The results are shown in Table 4.

[Table] Test example 3 Field soil 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 soybean, cotton, sugar beet, corn,
Wheat, mulva morning glory, Japanese sorghum, Japanese sorghum, Japanese sorghum, Japanese millet, Japanese barnyard grass, and Seiban sorghum were sown and grown for 18 days. Then, make an emulsion of the test compound according to Formulation Example 2, dilute the specified amount with water equivalent to 5 liters per are containing a spreading agent, and use a small sprayer to spread it evenly over the entire stem and leaf area from above the plant body. 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 cm. Herbicidal efficacy was investigated 20 days after treatment. The results are shown in Table 5. This test was conducted in a greenhouse throughout the entire period.

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Claims (1)

[Claims] 1. General formula [In the formula, R represents a lower alkenyl group or a lower alkynyl group, and X represents a hydrogen atom or a fluorine atom. ] 4,5,6,7-tetrahydro-1,
2,3-benztriazole-1-oxide derivative. 2 General formula [In the formula, X represents a hydrogen atom or a fluorine atom. ] 2-hydroxyphenyl-4,5,
6,7-tetrahydro-1,2,3-benztriazole-1-oxide derivative and the general formula RZ [wherein R represents a lower alkynyl group or a lower alkenyl group, Z represents a halogen atom, an alkyl-substituted phenyl sulfonate group Or represents an alkylsulfonate group. ] A general formula characterized by reacting with an electrophilic reagent represented by [In the formula, R and X have the same meanings as above. ] 4,5,6,7-tetrahydro-1,
A method for producing a 2,3-benztriazole-1-oxide derivative. 3 General formula [In the formula, R represents a lower alkenyl group or a lower alkynyl group, and X represents a hydrogen atom or a fluorine atom. ] 4,5,6,7-tetrahydro-1,
A herbicide comprising a 2,3-benztriazole-1-oxide derivative as an active ingredient.