JPH0456830B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [In the formula, R represents a C ₁ -C ₄ alkyl group, a C ₃ -C ₄ alkenyl group, or a C ₃ -C ₄ alkynyl group,
X represents a chlorine atom or a bromine atom, and Y represents an oxygen atom or an imino group. ] The present invention relates to a tetrahydroindazole derivative (hereinafter referred to as the compound of the present invention) represented by the following and a herbicide containing the same as an active ingredient. Certain tetrahydroindazole derivatives, such as 2-(2,4-dichloro-5-methoxyphenyl)-3-methyl-4,5,6,7-tetrahydro-2H-indazole, are used as active ingredients in herbicides. This method is described in Japanese Patent Application Laid-Open No. 52-89670. However, these compounds cannot always be said to be sufficient as active ingredients for herbicides. 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 areas, such as buckwheat gullet, purslane, whiteweed, Japanese radish, Japanese radish, American hornwort, Ebisu grass, Japanese radish, American golden deer, American morning glory, Maruba morning glory, Japanese morning glory, Japanese Physalis, Japanese Physalis,
The compound of the present invention has a herbicidal effect on broad-leaved weeds such as Japanese fir tree, sunflower, and corn marigold, as well as grass weeds such as barnyard grass, barnyard grass, foxtail grass, grasshopper, grasshopper, and oat. It does not cause any harmful effects on major crops such as soybean. 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, japonica, and chickweed, cyperaceae weeds such as bulrushes, and cypress grasses. It has a herbicidal effect on rice plants, etc., and does not cause any harmful effects on rice plants. The compound of the present invention has the general formula [In the formula, X and Y represent the same meanings as above. ] A tetrahydroindazole derivative represented by
General formula RZ [] [In the formula, R represents the same meaning as above, and Z represents a chlorine atom, a bromine atom, or an iodine atom. ] It can be produced by reacting a halide represented by the following in a solvent at -80°C to 200°C for 1 hour to 48 hours in the presence of a dehydrohalogenating agent if necessary. The amount of reagents used in this reaction is 1.0 to 2.0 equivalents of the halide [] and the dehydrohalogenating agent per 1 equivalent of the tetrahydroindazole derivative []. Examples of solvents include aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, and dichloroethane, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile and isobutyronitrile,
Examples include acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, water, and mixtures thereof. Examples of dehydrohalogenation agents include organic bases such as pyridine, triethylamine, and N,N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride, sodium methoxide, and sodium hydroxide. Examples include alkali metal alkoxides such as ethoxides. 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, distillation, recrystallization, etc. to obtain the desired compound of the present invention. can be obtained. Furthermore, the compound of the present invention has the general formula [In the formula, R, X and Y represent the same meanings as above. ] A phenylhydrazine derivative represented by the formula and 1.0 to 1.2 equivalents of 2-acetylcyclohexanone are mixed in a catalytic amount of hydrochloric acid, sulfuric acid, acetic acid, P in a solvent such as aromatic hydrocarbons such as xylene and toluene. −
It can be produced by reacting in the presence of toluenesulfonic acid at 80°C to 120°C while dehydrating. After the reaction is complete, the reaction solution is subjected to standard post-treatments such as solvent distillation, and if necessary, chromatography,
The desired compound of the present invention can be obtained by purification by operations such as distillation and recrystallization. Next, production examples of the compounds of the present invention will be shown. Production example 1 2-(4-chloro-2-fluoro-5-hydroxyphenyl)-3-methyl-4,5,6,7-
Tetrahydro-2H-indazole 0.84g, potassium carbonate 0.28g, N,N-dimethylformamide
After stirring 10ml at 30℃ for 10 minutes, add ethyl iodide.
0.6g was added and reacted at 60-70°C for 4 hours. Water was added, extracted with ethyl acetate, and the extract was washed with water, dried, and concentrated. The residue was crystallized from hexane and
0.38 g of -(4-chloro-2-fluoro-5-ethoxyphenyl)-3-methyl-4,5,6,7-tetrahydro-2H-indazole was obtained. mp 98-99℃ Production Example 2 2.1 g of 2-fluoro-4-chloro-5-propargyloxyphenylhydrazine, 1.4 g of 2-acetylcyclohexanone, 30 ml of xylene, and a catalytic amount of acetic acid were added, and the mixture was refluxed while dehydrating for 3 hours. . After cooling, xylene was concentrated under reduced pressure. The residue solidified. After adding methanol and grinding, separate the 2-(4
0.4 g of -chloro-2-fluoro-5-propargyloxyphenyl)-3-methyl-4,5,6,7-tetrahydro-2H-indazole was obtained. mp 143-144°C 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 tetrahydroindazole derivative [] which is a raw material compound can be produced by the following method. (1) In the general formula [], when Y represents an oxygen atom: General formula [In the formula, X represents the same meaning as above. A method for producing the compound of the present invention represented by the general formula [] by reacting the hydroxyphenylhydrazine derivative represented by [] with 2-acetylcyclohexanone, and the aforementioned phenylhydrazine derivative [] and 2-acetylcyclohexanone. A tetrahydroindazole derivative [] (Y=oxygen atom) can be obtained by a similar method. (2) In general formula [], when Y represents an imino group: General formula [In the formula, X represents the same meaning as above. ] and the nitrophenylhydrazine derivative represented by 2
- acetylcyclohexanone, by the same method as the method for producing the compound of the present invention represented by the general formula [] by reacting the phenylhydrazine derivative [] with 2-acetylcyclohexanone. [In the formula, X represents the same meaning as above. ] is obtained, and then this nitrophenyl-tetrahydroindazole derivative [ ] is obtained.
and 2.5 to 10 equivalents of iron powder to this in the presence of a large excess of an acid such as acetic acid or hydrochloric acid at 50°C.
By reacting at 120°C, a tetrahydroindazole derivative [] (Y=imino group) can be obtained. In the production methods (1) and (2) above, after the reaction is completed, the desired tetrahydroindazole Derivative [ ] can be obtained. Next, tetrahydroindazole derivative []
A production example of nitrophenyl-tetrahydroindazole derivative [] is shown as a reference example. Reference Example 1 0.5 g of 4-chloro-2-fluoro-5-hydroxyphenylhydrazine, 0.4 g of 2-acetylcyclohexanone, and a catalytic amount of acetic acid were mixed in 15 ml of xylene, and heated under reflux for 5 hours while dehydrating. After cooling, it was concentrated, and the residue was purified using a silica gel column (eluent: ethyl acetate-hexane).
0.7 g of (4-chloro-2-fluoro-5-hydroxyphenyl)-3-methyl-4,5,6,7-tetrahydro-2H-indazole was obtained. m-p. 188.5-190°C Reference Example 2 A mixed solution of 3 g of iron powder and 10 ml of acetic acid water was heated to 90-100°C and stirred for 10 minutes. Lower the temperature to 80-70℃,
2-(4-chloro-2-fluoro-5-nitrophenyl)-3-methyl-4,5,6,7-tetrahydro-2H-indazole (2 g) was dissolved in 10 ml of acetic acid and 10 ml of ethyl acetate and added dropwise. Furthermore, at the same temperature, 1
After stirring for an hour, the mixture was allowed to cool, the iron powder was separated, and the liquid was extracted with ethyl acetate. Wash the organic layer with saturated sodium bicarbonate solution,
Dry. The solvent was concentrated under reduced pressure and the residue crystallized. Take this crystal, wash it with ether, and
1.8 g of (3-amino-4-chloro-6-fluoro-phenyl)-3-methyl-4,5,6,7-tetrahydro-2H-indazole was obtained. m.
p.107-108°C A tetrahydroindazole derivative [] which can be produced by the same method as in Reference Example 2 is shown below.

[Formula] mp 69-71℃ Reference example 3 4-chloro-2-fluoro-5-nitrophenylhydrazine 4g, xylene 10ml acetic acid in catalytic amount,
From 2.8 g of 2-acetylcyclohexanone, 2-(4-chloro-2-fluoro-5-nitrophenyl)-3-methyl-4,
5,6,7-tetrahydro-2H-indazole
2.3g was obtained. mp 143-144°C When the compound of the present invention is used as an active ingredient in a herbicide, it is usually mixed with a solid carrier, liquid carrier, surfactant, or other formulation auxiliary to form an emulsion, 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 0.05 to 80%, preferably 0.1 to 70%.
contains. Examples of the solid carrier include fine powders or granules such as kaolin clay, attapalgite clay, pentonite, acid clay, pyrofluorite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Examples of 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, and dimethyl sulfoxide. , acetonitrile, water, etc. Surfactants used for emulsification, dispersion, wetting, etc. include anionic surfactants such as alkyl sulfate salts, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, and polyoxyethylene alkylaryl phosphate salts. , polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene alkyl polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and other nonionic surfactants. Examples of formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), and the like. Next, formulation examples are shown. Note that the compound of the present invention is
Indicated by compound number in the table. Parts indicate parts by weight. Formulation Example 1 50 parts of Compound 4 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 2 of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 30 parts of xylene and 40 parts of cyclohexanone are thoroughly mixed to obtain an emulsion. Formulation Example 3 Compound 4 of the present invention, 0.1 part, synthetic hydrated silicon oxide 0.9
1 part, 2 parts of calcium lignosulfonate, 30 parts of bentonite, and 67 parts of kaolin clay are thoroughly ground and mixed, water is added, the mixture is well kneaded, and the mixture is granulated and dried to obtain granules. Formulation Example 4 25 parts of Compound 6 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. In addition, 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 application amount varies depending on weather conditions, emulsion form, application time, method, location, target weeds, target crops, etc., but is usually 0.2 g per are. ~100
g, preferably 0.08 g to 40 g, and emulsions, wetting agents, suspending agents, etc. are usually used in a specified 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. Examples of the spreading agent include, in addition to the above-mentioned surfactants, 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] In addition, the herbicide 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 the compound is not tested. If the test plant dies or its growth is completely inhibited, it is rated 5, and 0.
Rated on a scale of 6 to 5, 0, 1, 2, 3, 4, 5
Indicated by 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 Japanese barnyard grass, Japanese amberjack, Japanese morning glory, and Japanese commonweed were sown and covered with soil. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was added to 1
It was diluted with water equivalent to 10 liters per area, applied to the soil surface with a small sprayer, and thoroughly mixed into the soil 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 results are shown in Table 3.

【table】

[Table] Test Example 2 Field soil treatment test A cylindrical plastic pot with a diameter of 10 cm and a depth of 10 cm was filled with field soil, and barnyard grass, Japanese radish, and Japanese radish were sown and grown in a greenhouse for 10 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water containing a spreading agent equivalent to 10 liters per are, and the foliage was treated from above the plant using a small sprayer. After treatment, they were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 4.

[Table] Test Example 3 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 8 cm and a depth of 12 cm was filled with paddy soil, and 1 to 2 seeds of Japanese millet and broad-leaved weeds (Azaena, Kikashigusa, Chickweed) were added to the pot.
Mixed to a depth of cm. After flooding the fields to create a paddy field, tubers of Urikawa were buried at a depth of 1 to 2 cm, and then rice at the two-leaf stage was transplanted and grown in a greenhouse. Six days later (at the beginning of each weed's emergence), the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with 5 milliliters of water, and the emulsion was applied to the water surface. After treatment
The plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 5.

[Table] Test Example 4 Field soil stem and leaf treatment test Field soil was filled into a vat with an area of 33 x 23 cm ² and a depth of 11 cm, and corn, wheat, soybean, goldenrod, American hornwort, Japanese fir tree, Japanese crocodile,
Seeds of morning glory, blueberry, and brilliance 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 6. This test was conducted in a greenhouse throughout the entire period.

[Table] Test example 5 Upland soil treatment test Field soil was filled in a pot with an area of 33 x 23 cm ² and a depth of 11 cm, and soybeans, Japanese fir, Japanese morning glory, Ebisu grass, Japanese Physalis, Japanese thorn, Japanese foxglove,
Golden millet was 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. After treatment
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 6 Paddy field flooding treatment test Fill a 1/5000a Wagner pot 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 4 days (at the beginning of germination of each weed), make an emulsion of the test compound according to Formulation Example 2, dilute the specified amount with 10 milliliters of water, and apply it to the water surface.
The depth of the water was 4 cm. After treatment, they were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 8.

[Table] Test example 7 Paddy foliage and soil treatment test Fill a 1/5000a Wagner pot with paddy soil.
1 to 2 seeds of Japanese millet, broad-leaved weeds (Azeena, Kikashigusa, Chickweed) and overwintering buds of Japanese grasshopper
Mixed to a depth of cm. After flooding the rice field to create a paddy field, three-leaf stage rice was transplanted and grown in a greenhouse.
After 11 days (at the two-leaf stage of Japanese millet), 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 results are shown in Table 9.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R represents a C ₁ -C ₄ alkyl group, a C ₃ -C ₄ alkenyl group, or a C ₃ -C ₄ alkynyl group,
X represents a chlorine atom or a bromine atom, and Y represents an oxygen atom or an imino group. ] A tetrahydroindazole derivative represented by: 2 General formula [In the formula, R represents a C ₁ -C ₄ alkyl group, a C ₃ -C ₄ alkenyl group, or a C ₃ -C ₄ alkynyl group,
X represents a chlorine atom or a bromine atom, and Y represents an oxygen atom or an imino group. ] A herbicide characterized by containing a tetrahydroindazole derivative represented by the following as an active ingredient.