JPS6212761A - Tetrahydroindazole derivative, production thereof and herbicide containing said derivative as active constituent - Google Patents

Abstract

NEW MATERIAL:A tetrahydroindazole derivative expressed by formula I (R is 1-8C alkyl, 3-7C cycloalkyl, 3-8C alkenyl or 3-8C alkynyl). EXAMPLE:3-Chloro-2-(2-fluoro-4-nitro-5-isopropylaminophenyl)-4,5,6,7-2 H-tetrahydro indazole. USE:Useful as a herbicide having herbicidal effect on various weeds causing problems in foliar treatment and soil treatment in upland field, e.g. broad-leaved weeds such as black bindweed, gramineous weeds such as Deccan grass, without phytotoxicity to main crops, e.g. peanut, corn, wheat, etc., and capable of exhibiting effect on various weeds in treatment under flooded conditions in paddy field without phytotoxicity to rice plants. PREPARATION:A hexahydroindazolone derivative expressed by formula II is chlorinated to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein R is a C8-C, alkyl group, a C8-C, cycloalkyl group, a C1-C, alkenyl group, or a C1-C8
Represents an alkynyl group. ] Tetofhydroindazole pm conductor (hereinafter referred to as the compound of the present invention) shown by 0, its production method, and a herbicide containing it as an active ingredient 0 Certain tetrahydroindazole derivatives, for example 8
-chloro-2-(2-fluoro-4-nitropheny/l
/ ') -4,5,6,7-tetrahydro-2H-indacy-p is used as an active ingredient in herbicides as described in JP-A-52-51865. However, these These compounds are not necessarily sufficient as active ingredients in herbicides.

The compounds of the present invention can be used to treat various weeds that are problematic in foliar and soil treatments in upland fields, such as buckwheat, nuperhyu, whiteweed, white radish, radish, Japanese radish, golden deer, field pansies, morning glory, morning glory, and staghorn. Weeding is effective against broad-leaved weeds such as white-spotted morning glory, dog-eared groundweed, white-spotted weed, Japanese-eared fir tree, dog-eared beetle, and corn maricold; and grass-family weeds such as barnyard grass, Japanese millet, foxtail grass, black-and-white grass, black-and-white grass, oat, sagebrush, staghorn grass, etc. In addition, the compound of the present invention does not cause any problematic phytotoxicity to major crops such as peanut, corn, wheat, rice, and soybean.

In addition, the compound of the present invention can be applied to various weeds that are problematic in the waterlogging treatment of paddy fields, such as grass weeds such as Japanese millet, broad-leaved weeds such as azalea and cypress, and cyperaceae weeds such as cypress, bulrush, cyperus, and cyperus.
The compound of the present invention has a herbicidal effect on grasshoppers, Japanese apricots, and grasshoppers, and does not cause any harmful effects on rice. O solvents that can be produced by reacting with a chlorinating agent in a solvent at 50°C to 200°C for 1 hour to 96 hours include aliphatic hydrocarbons such as hexane, heptane, and ligroin, benzene, and toluene. , aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, ethers such as diisopropyl ether, dioxane, ethylene glycol dimethyl ether, ethyl acetate, acetic acid Examples of chlorinating agents include NTE μ such as butyl, diethyl hypoacid, etc., or mixtures thereof. Examples of chlorinating agents include phosgene, trichloromethyl chloroformate, and oxalic acid chloride. After completion of the reaction, the reaction solution is The desired compound of the present invention can be obtained by carrying out a usual [F] post-treatment such as concentration under reduced pressure, and if necessary, purifying by operations such as chromatography and recrystallization. Production Example 1 (Production of Compound 1 of the Present Invention) 2-(2-)μow-4-nitro-5-isopropylaminofz2/I') -8,8m,4,5 ,6゜7
-hexahydro-2H-indacy-/I/-3-one 8
．． 12 was added to 200 fflJ of 1M phosgene-toluene solution and refluxed for 8 hours. After cooling, it was concentrated under reduced pressure, and the residue was purified by silicage μ column chromatography (eluent: n-hexane-ethyl acetate/L/). Chloro-2-(2
O NMR (CDCJj) δppm 1.85 (6H, d), 1.85 (4H, m),
2.2-2.9 (4H, m) 8.5-4 (IH, m),
6.9 (IH, d), 8.0 (In, d) - 7.8 (I
Some of the compounds of the present invention that can be produced by such a production method are shown in Table 1. The silone derivative is produced by the following route @ -NH closed [In the formula, R represents the same meaning as above] In other words, the nitroaniline derivative (2) is converted into a diazonium salt by a conventional method, and then converted into a diazonium salt. Using 8.0 to 10 equivalents of tin to the nitroaniline derivative (2), -80 to 10°C
Hydrazine derivatives can be prepared by reduction in hydrochloric acid.

In addition, this hydrofuzine derivative diagram shows the cypholonitrobenzene derivative concave, and the hydration of 2.0 to 10 equivalents,
It can also be produced by reacting hydrazino or anhydrous hydrazine in a solvent such as ethanol, methanol-μ, tetrahydrofuran, etc. at 0 to 40°C. Hydofuzine derivative (2) obtained in this way, on the other hand, has a Hexahydroindasilone derivatives can be produced by reacting .0 to 1.1 equivalent of 2-acoxycarboniμcyclohexanone in a solvent such as acetic acid at 50 to 200°C.

Next, these production examples will be shown as reference examples.

Reference Example 1 (Manufacture of hexahydroindasilone conductor) 2-fluoro-4-nitro-5-isopropylaminophene hydrazine 5.6F, 2-ethoxycarboxylic acid p
4 with cyclohexanone 4.2fFr acetic acid 100mj
The 90 reaction solution was refluxed for an hour, poured into water, extracted with ethyl acetate μ, the 90 extract was washed with water and aqueous sodium bicarbonate, dried, and concentrated. The 0 residue was purified using a V Rikagu μ column. 2-Fluoro-4-nitro-5-isopropylaminophenyv
) -8,8a,4,5.6.7-hexahydro-2H
- Om, p, 1 obtained indazol-8-one 4.4f
90-191°C Similarly, the following were obtained @ Reference Example 2 (Production of Hydofuzine Derivative 4) N-isopropyl/L/-8,4-difluoro-6-nitroaniline 6.
8t was dissolved in tetrahydrofuran toomi, 2.22 g of saturated aqueous hydrazino was added thereto at 5°C to 10°C, and the mixture was stirred overnight at 10 to 20°C ◇The resulting crystals were separated by F,
Washing with water and drying yielded 2-fluoro-4-nitro-5-isopropylaminophenylhydrazine 6,1 f t-.

O general formula' 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, active agents, and other formulation auxiliaries to formulate emulsions, aqueous preparations, suspensions, granules, etc. These preparations contain the compound of the present invention as an active ingredient. , weight ratio is 0.0 to OO, preferably 0.14 to 80 g6
O Containing solid carriers include fine powders or granules such as kaolin clay, attapagite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, urea, ammonium sulfate, and synthetic hydrous silicon oxide; Examples include aromatic hydrocarbons such as xylene and methylnaphthalene, isopropano-p, and ethylene crico! , alcohols such as cellosolve, ketones such as acetone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethysulfoxide, acetonitrile, water, etc. Emulsification, dispersion, wet carbon, etc. Examples of surfactants used for
Anionic surfactants such as sulfonic acid salts, siaμkyls〃phosuccinates, polyoxyethylene 7~kiμaryl ether phosphate ester salts, polyoxyethylene alkyl ethers, polyoxyethylene 7~kiμaryμ Examples include nonionic surfactants such as TE, polyoxine ethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. ◎ Formulation adjuvants include lignin sulfonate, Alginate, polyvinyl alcohol-μ, gum arabic, CMC (μboxymethylcellulose),
Examples include PAP (isopropyl acid phosphate), etc.0 Next, the compounds of the present invention are shown in the compound numbers in Table 1, and 0 parts indicate parts by weight.O Formulation Example 1 Compounds of the present invention 1. 50 parts of lignin μphonic acid, 8 parts of sodium lauryl sulfate, and 46 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain an irrigation agent. Formulation Example 2 1.10 parts of the compound of the present invention, poly Oxyethylene styrene μ
Pheny-ether/L/141H5,) 6 parts of dec[mu]benzene[mu]phonic acid, 80 parts of xylene and 40 parts of cyclohexanone are thoroughly mixed to obtain an emulsion. Formulation Example 8 4.2 parts of the compound of the present invention, synthetic water content 1 part of silicon oxide, 2 parts of lignin sulfonic acid strength/L/V um, 80 parts of bentonite and 65 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, then granulated and dried to form granules. obtain.

Formulation Example 4 6.25 parts of the compound of the present invention, 8 parts of polyoxyethylene sobitansenooleate, 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 broken soil surface treatment, soil mixing treatment, etc.), and foliage treatment includes treatment from above the plant body, as well as local treatment for weeds to prevent them from adhering to crops. In addition, by mixing with other herbicides, it is expected that the herbicidal efficacy will be enhanced. ◇In addition, it can be used as an insecticide, acaricide, nematicide, fungicide, plant growth regulator, fertilizer, soil improvement agent, etc. The compound of the present invention can also be used in combination with other agents such as rice paddies, fields, orchards, pastures, etc.
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 in herbicides, the amount to be treated depends on weather conditions, formulation form, treatment time, Although it varies depending on the method, location, target weed, and target crop, it is usually 0.1f to 20%
0 f, preferably 0.32 to 100 t, and emulsions, irrigation agents, suspension agents, etc. are usually used in predetermined amounts at 1 ar/V and 0.5 liters/L/ to 10 liters μ. Dilute with water (adding auxiliary agents such as spreading agents if necessary) and treat.
Granules, etc. are usually treated as is without any dilution. In addition to the above-mentioned surfactants, the spreading agents include polyoxyethylene resin acid (Este/!/), Lignia 7-μ
Fontate, abietate, dinaphthylmethane disulfonate, paraffin, etc. are used.

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 as comparative controls are indicated by compound symbols in Table 2. The degree of OJ is determined by self-observation, and when there is no or almost no difference from when no compound is used, it is defined as rOJ, and when the test plant dies or its growth is completely inhibited, it is defined as ``5'', and 0. Rated on a scale of 6 to 6, o, i, 2
．． As shown in 8.4.6 ◎ Test Example 1 Field field stem and leaf treatment test A cylindrical plastic pot with a diameter of IQm and a depth of 10 aw was filled with field soil, and barnyard grass, oat, Malva morning glory,
Ichibi was sown and grown in a greenhouse for 10 days.
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 5 liters of 17-atm, and the foliage was treated from above the plant using a small sprayer. After that, they were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 8.

Test example 2 Paddy field flooding treatment test Diameter 8cI11, depth 12110 yen Wi type Goufstitch?
dl) Fill the excavated dust with K water, and mix the seeds of Japanese millet and broad-leaved weeds (Azeena, Kikashigusa, Chickweed) to the depth of 1 to 2 wounds.After flooding and making it into a paddy field, the tubers of Urikawa were mixed. 06 days after planting in a depth of 1 to 2 cI11 and transplanting rice at the second leaf stage and growing it in a greenhouse (at the beginning of each weed's emergence), emulsify the test compound according to If-Formulation Example 2, and A predetermined amount was applied to the water surface, and the herbicidal efficacy was investigated by growing in a greenhouse for 20 days after treatment.
Shown in the table.

Table 4 Test Example 8 Field soil stem and leaf treatment test A vat with an area of 88 x 2 Bcd and a depth of 11 cI was filled with field soil, and seeds of Tsukkasekudais, Ichibi, Mapa morning glory, Onagiri, Shiroza, and Aogate were sown and grown for 25 days @afterwards The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was mixed with a spreading agent at 1 ar/I/m.

It was diluted with 910 liters of water and uniformly applied from the top of the plant to the surface of the stems and leaves using a small sprayer.At this time, the growth conditions of weeds and crops differed depending on the vehicle type, but the weeds and crops were at the 2-5 leaf stage and the plant height was 4. The herbicidal efficacy was investigated 30 days after the 0 treatment in ~18 countries ◎ The results are shown in Table 5 0 This test was conducted in a greenhouse throughout the period O Test Example 4 Paddy field flooding treatment test 200 - No. 1) Filled with K paddy soil, and mixed with seeds of Japanese millet, broad-leaved weeds (Azeena, Kikashigusa, and Chickweed) and overwintering stems of Pinus japonicum to a depth of 1 to 2 as. After flooding and making it into a paddy field, 1 to 2 eI1 of Urikawa tubers are grown.
1, and then transplanted rice at the 8-leaf stage, grown it in a greenhouse, and after 9.11 days (2nd and 0th stages of Japanese millet),
The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was applied to the water surface, and the water depth was adjusted to 4 tm.
The herbicidal efficacy of the plants was investigated by growing them in a greenhouse for 1 day.The results are shown in Table 6.For 2 days from the day after the treatment, water leakage equivalent to a water depth of 8 m per day was not allowed. Na90 Chapter 6 Table Test Example 5 Field Land Destruction Treatment Test

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a C_1 to C_8 alkyl group, C_3 to C_
7 represents a cycloalkyl group, a C_3-C_8 alkenyl group, or a C_3-C_8 alkynyl group. ] A tetrahydroindazole derivative represented by: (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a C_1 to C_8 alkyl group, C_3 to C_
7 represents a cycloalkyl group, a C_3-C_8 alkenyl group, or a C_3-C_8 alkynyl group. ] A general formula characterized by chlorinating a hexahydroindazolone derivative represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R represents the same meaning as above. ] A method for producing a tetrahydroindazole derivative. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a C_1 to C_8 alkyl group, C_3 to C_
7 represents a cycloalkyl group, a C_3-C_8 alkenyl group, or a C_3-C_8 alkynyl group. ] A herbicide characterized by containing a tetrahydroindazole derivative represented by the following as an active ingredient.