JPS60252465A - 2-phenyl-4,5,6,7-tetrahydro-2h-indazole derivative, its preparation, and herbicide comprising it as active ingredient - Google Patents

Abstract

NEW MATERIAL:A 2-phenyl-4,5,6,7-tetrahydro-2H-indazole derivative shown by the formula I (R is 4-6C alkynyl). EXAMPLE:3-Chloro-2-[4-chloro-2-fluoro-5-( 1-butyn-3-yloxy )phenyl]-4,5,6,7-tetrahydro-2H-indazole. USE:A herbicide having herbicidal effect on various weeds that cause trouble in foliar treatment and soil treatment of paddy field and in flooding treatment of paddy field, showing no phytotoxicity, causing trouble, on main crops. PREPARATION:A compound shown by the formula II is reacted with a compound shown by the formula R-X (X is Cl, Br, I, OSO2CH3, or p-toluenesulfonyloxy), to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein R represents a 04-C6 alkynyl group]. ] 2-phenyl-4,5,6,7-tetrahydro-
The present invention relates to a 2H-indazole 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.

Certain 2-phenyl-4,5,6,7-tetrahydro-2H-indazole derivatives, such as 8-chloro-2
-(2,4-dichloro-5-methoxyphenyl)-4,
5,6,7-tetrahydro-2H-indazole is used as an active ingredient of herbicides in Japanese Patent Application Laid-Open No. 52-5
It is described in Publication No. 1865. However, these compounds cannot always be said to be sufficient as active ingredients in herbicides.

The compounds of the present invention can be used to treat various weeds that are problematic in foliage treatment and soil destruction treatment in upland areas, such as whiteweed and green grass.
Broad-leafed weeds such as Japanese radish, American hornwort, Ebisu grass, Japanese radish, Japanese goldenrod, Japanese morning glory, Japanese morning glory, Japanese Physalis, Japanese fir tree, sunflower, rice plants such as Japanese barnyard grass, Japanese barnyard grass, Japanese foxtail grass, Japanese rice grass, oat, etc. Some of the compounds of the present invention have a herbicidal effect on weeds of the family, and, moreover, do not cause any problematic phytotoxicity to major crops such as corn, wheat, and soybean.

In addition, the compound of the present invention can be applied to volatile weeds that are a problem in paddy field flooding treatment, such as grass weeds such as Japanese millet, broad-leaved weeds such as azalea, cypress grass, and cypress grass, cyperaceae weeds such as bulrushes, and cypress grass. 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 is a compound represented by the general formula and the general formula R-X [m] [wherein R represents the same meaning as above, X is a chlorine atom,
Represents a bromine atom, an iodine atom, a methanesulfonyloxy group or a P-)luenesulfonyloxy group. ] in a solvent, in the presence of a dehydrohalogenating agent and, if necessary, a phase transfer catalyst, at 20°C to 15°C.
It can be produced by reacting at 0°C for 1 to 24 hours.

The amounts of reagents used in the reaction are 1 to 10 equivalents of compound [1+1], 1 to 10 equivalents of dehydrohalogenating agent, and 1 to 10 equivalents of aliphatic hydrocarbons such as phase reactants relative to the equivalent of compound [i]. Examples include aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as diisopropyl ether, dioxane, and ethylene glycol dimethyl ether, sulfur compounds such as dimethyl sulfoxide and sulfolane, water, and mixtures thereof.

Examples of dehydrohalogenation agents include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride.

Examples of the phase transfer catalyst include benzyltri-n-butylammonium chloride and tetra-n-butylammonium bromide.

After completion of the reaction, the reaction solution is subjected to conventional post-treatments such as solvent extraction and concentration, and if necessary, purified by operations such as chromatography and recrystallization to obtain the desired compound of the present invention.

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

Production Example 1 (Rapid production of the compound of the present invention) 8-chloro-2-(4-chloro-2-fluoro-5-hydroxyphenyl)-4,5°6,7-tetrahydro-
2H-indazole lf was suspended in 8.5 ml of 7% aqueous sodium hydroxide solution, and tetra-n-butylammonium bromide ip was added. To this suspension was added 1.851 p-toluenesulfone Ml--ftin-3-yl, and the mixture was heated at 70°C.
The mixture was stirred for 4 hours. After the reaction mixture has cooled, add water and
Extract with ethyl acetate and wash with water. After drying and concentrating this organic layer, the resulting residue was purified by silica gel thin layer chromatography (developing solvent: ether: hexane = 8) to obtain 3-chloro-2-[4-chloro-2-fluoro-5 −
(1-butyn-3-yloxy)tuunyl)-4,5,
0.8y of 6,7-tetrahydro-2H-indazole was obtained. nDl, 5535 Like this! ! I! Table 1 shows some of the compounds of the present invention that can be produced by this method.

Table 1 General Formula Sol Derivatives When the compound of the present invention is used as an active ingredient of a herbicide,
It is usually mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to formulate emulsions, wettable powders, suspensions, granules, etc.

These preparations contain the compound of the present invention as an active ingredient in an X amount ratio of 0.08 to 90%, preferably 0.05 to 80%.

Examples of solid carriers include fine powders or granules such as kaolin clay, attapulgite 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, 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 ether phosphate salts. agent, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether,
Examples include nonionic surfactants such as polyoxyethylene polyoxybrobylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. As formulation aids, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PA
Examples include P (isopropyl acid phosphate).

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. Parts indicate parts by weight.

Formulation Example 1 3.50 parts of the compound of the present invention, 8sl 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 1.10 parts of the compound of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 30 parts of xylene, and 40 parts of isophorone.
Mix well to obtain an emulsion.

Formulation Example 8 1.0.1 parts of the compound of the present invention, 0.9 parts of synthetic hydrated silicon oxide, 2 parts of calcium lignosulfonate, 80 parts of bentonite, and 67 parts of Kao IJ Tsukrei were thoroughly ground and mixed, and water was added. After kneading, the mixture is granulated and dried to obtain granules.

Formulation Example 4 4.25 parts of the compound of the present invention, 8 parts of polyoxyethylene sorbitan monooleate, 8 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, pastures,
It can be used as an active ingredient in herbicides for 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, formulation form, application timing, method, location, target weeds, target crops, etc., but usually 1.
0.021 to 100 g per are, preferably 0.021 to 100 g per are.
Emulsions, wetting agents, suspending agents, etc. are usually mixed with 1 liter to 10 liters of water (adding auxiliary agents such as spreading agents, if necessary) per are. Granules and the like are usually treated as they are without any dilution.

Spreading agents include, in addition to the above-mentioned surfactants, polyoxyethylene resin acids (esters), lignin sulfonate, abietate, dinaphthylmethane disulfonate, 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 compound numbers in Table 1, and the compounds used for comparison are indicated by compound symbols in Table 2.

Table 2 In addition, the herbicidal efficacy was determined by visual observation of the degree of budding and main growth inhibition of the test plants during the survey, and the herbicidal efficacy was determined as (4) if there was no or almost no difference from when no compound was tested. ,
A rating of 0.1.2 is given on a scale of 0 to 5, with a score of 5 indicating that the test plant has died or its growth has been completely inhibited.
．． 8.4.5.

Test Example L Upland Soil Treatment Test A cylindrical plastic pot with a diameter of 10 crn and a depth of 10 LyR was filled with upland soil, sown with Japanese barnyard grass, Japanese morning glory, and Japanese staghorn, and covered with soil. 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 3.

Table 8 Test Example 2 Upland Stem and Leaves Treatment Test A cylindrical plastic pot with a diameter of 10 m and a depth of lOα was filled with upland soil, and barnyard grass and Ennokuri 2. Japanese radish and Japanese radish were sown (7. Grown in a greenhouse for 10 days. Then, the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of it was
It was diluted with water containing a spreading agent equivalent to 10 liters per are, and treated with a small blower from above the plant. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 4.

Table 4 Test Example 8 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 8 cm and a depth of 12 strokes was filled with paddy soil, and seeds of Japanese millet and broad-leaved weeds (Azaena, Kikashigusa, Chickweed) were placed at a depth of 1 to 2 cm. Mixed it in. After flooding the rice field to create a paddy field, two-leaf stage rice 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 5 Test Example 4 Paddy field overflow treatment test 115000a Fill a Wagner Posoto with paddy soil, and add 1 to 2 cr of Japanese millet, broad-leaved weeds (Azeena, Kikashigusa, Chickweed), bulrush seeds, and wintering petals
It was mixed to a depth of n. After one year of flooding and turning it into a paddy field,
Furthermore, rice at the 8-leaf stage was transplanted and grown in a greenhouse. After 6 days (the beginning of germination of each weed), 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, and the water depth was set to 4 L:rn. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 6.

Table 6 Test Example 5 Paddy field flooding treatment test A 115000B Wagner Pot 7 container was filled with paddy soil and mixed with Japanese millet, broad-leaved weeds (Azeena, Kikashigusa, Chickweed), bulrush seeds, and overwintering buds of Pinus spp. to a depth of 1 to 2α. It was crowded. After flooding the rice field to create a paddy field, rice at the 8-leaf stage was transplanted and grown in a greenhouse. After 18 days (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, and the water depth was set to 4α. 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 7 Test Example 6 Upland Soil Treatment Test A vat with an area of 88 x 28 cJ and a depth of 11 crn was filled with upland soil, and soybean, Japanese fir tree, Japanese morning glory, Japanese grasshopper, Japanese Physalis, Japanese foxtail grass, and Japanese commonweed were sown.
It was covered with soil to a thickness of ~2α. 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 8.

Table 8 Test Example 7 Upland Soil Treatment Test A vat with an area of 88 x 2 Bcd and a depth of 11 c1n was filled with upland soil, and corn, wheat, Japanese millet, American hornwort, Japanese fir tree, Japanese staghorn, Japanese morning glory, and Physalis were sown and grown for 18 days. . Thereafter, 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 upper part of the plant and the surface of the leaves. processed. At this time, the growth conditions of weeds and crops varied depending on the vehicle type, but they were in the 1-4 leaf stage and the plant height was 2-12α. The herbicidal efficacy was investigated 20 days after the treatment.

The results are shown in Table 9. Note that this test was conducted in a greenhouse throughout the entire period.

Table 9

Claims (2)

[Claims] (1) General formula [wherein R represents a C4-C6 alkynyl group]. ] 2-phenyl-4,5,6,7-tetrahydro-2H-indazole derivative represented by these. (2) Compounds represented by the general formula and the general formula -X [wherein R represents a C4 to C6 alkynyl group, and Represents a sulfonyloxy group. ] In the general formula E, R has the same meaning as above. 2 indicated by ]
-Production method of phenyl-4,5,6,7-tetrahydro-2H-indazole rust conductor. (3) The active ingredient is a 2-phenyl-4,5,6,7-tetrahydro-2H-indazole derivative represented by the general formula [wherein R represents a C4-C-alkynyl group] herbicide.