JPS605588B2 - Pyrazole derivative - Google Patents

Description

[Detailed description of the invention] The present invention relates to pyrazole derivatives.

More specifically, the present invention is based on the general formula [where Y is a chlorine atom or a nitro group, and Z is an allyl group, a propargyl group, a 4-nitrobenzyl group, a phenethyl group, a phenacyl group, a 4-chlorophenacyl group] , 2,4-dichlorophenacyl group, 4-methylsulfonylphenacyl group or 2,4-dinitrophenyl group].

The pyrazole derivatives according to the present invention are generally produced by the following method.

In the above reaction formula, Y and Z are as described above, and Hal is a halogen atom.

Examples of the solvent used in the above reaction include aprotic polar solvents such as acetone, methyl ethyl ketone, and dimethyl formamide, and examples of the alkali include potassium carbonate, sodium carbonate, and sodium hydroxide. Note that the reactivity can be improved when a cuprous halide catalyst such as copper iodide or steel fluoride is present.Next, specific synthesis examples according to the present invention will be described.

Production example 11,3-dimethyl-4-(2,4-dichloroo
benzoyl)-5-(204-dinitrophenoxy)pyrazole 1 and 3-dimethyl-4-(2
- 1.43 g of 4-dichlorobenzoyl)-5-hydroxypyrazole was added and dissolved in 15 g of methyl ethyl ketone.

To this, 1.38 g of anhydrous potassium carbonate was added, and 0.93 g of 2,4-jetrophenyl fluoride was added dropwise while stirring, and the mixture was reacted under reflux conditions for 3 hours after the dropwise addition was completed. The contents of the flask were heated and methyl ethyl ketone was distilled off to obtain a reaction precipitate, which was dissolved in methylene chloride. This solution and a saturated aqueous sodium bicarbonate solution were mixed and separated, the organic layer was taken out, and methylene chloride was distilled off to obtain a solid. This solid was washed with benzene and had a melting point of 190-1.
9〆C target object 1.58 minutes was obtained. Production example 2103-dimethyl-4-(2.

4-dichlorobenzoyl)-5-propargyloxypyrazo-'re214-dinitrophenyl fluoride 0.9
The reaction was carried out in the same manner as in Preparation Example 1 above, except that 0.71 mm of propargyl bromide was used instead of 3 mm, and the target product with a refractive index of 1.585 was obtained with 0.93 mm. I got it.

Production Example 3 103-dimethyl-4-(2,4-dichlorobenzoyl)-5-(4-chlorobenzoylmethoxy)pyrazole 2,4-dinitrophenyl fluoride 0.93 p-chlorophenacylbromide The reaction was carried out in the same manner as in Preparation Example 1 except that 1.0 mm was used, and the product was purified to obtain 1.72 mm of a brown semi-solid target product.

Production Example 4 1.43 hours of 1,3-dimethyl-4-(204-dichlorobenzoyl)-5-hydroxypyrazole was added to a 4-ton flask. and dissolved in 15 ml of methyl ethyl ketone.

Add 1.38 g of anhydrous potassium carbonate to this and drop 1.0 g of phenacylbromide while praying, and after the completion of the dripping, 3 g
The reaction was carried out under reflux conditions for a period of time. The melt in the flask was heated in a furnace to remove methyl ethyl ketone to obtain a reaction precipitate, which was dissolved in methylene chloride. This solution and a saturated aqueous sodium bicarbonate solution were mixed, the layers were separated, the organic layer was taken out, and the methylene chloride was removed to obtain 1.92 kg of the desired product with a melting point of 102 to 104 qo. Compounds produced according to the above production method or production example are listed in the following table.

Table 1 The pyrazole derivatives of the present invention are as shown in the test examples below.
Shows suitable effects when used as an active ingredient in herbicides.

In particular, the present invention effectively controls harmful weeds such as grasshopper, cyperus japonica, cyperus japonica, fireweed, and weed without substantially harming crops such as rice. The herbicide of the present invention has an excellent herbicidal effect on various weeds, so it can be applied to paddy fields, fields, orchards, mulberry orchards, forests, etc.
It can be applied to a wide range of fields, including farm roads, grounds, and factory grounds, and the application method can be selected as appropriate, including soil treatment and foliage treatment.

The herbicide of the present invention can be prepared by directly dissolving or dispersing the above-mentioned active ingredient, i.e., a pyrazole derivative, in water to form an aqueous solution or aqueous dispersion. ,
Supports such as ziecrite; Solvents such as benzene, toluene, xylene, solvent naphtha, ethanol, dioxane, acetone, isophoront methyl isobutyl ketone, dimethylformamide, dimethyl sulfoxide, water, etc.
Furthermore, as necessary, sodium alkyl sulfate, sodium alkylbenzene sulfonate, sodium lignin sulfonate, polyoxyethylene lauryl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, polyoxyethylene solpitan fatty acid ester It can be used by appropriately blending anionic or nonionic surfactants such as, for example, emulsions, wettable powders, solutions, powders, and granules.

For example, the compounding ratio at the time of formulation is 1 to 9 weight% of the active ingredient.
"Preferably 1 to 7% by weight, 5 to 9% by weight of carrier or solvent."
Suitably 9% by weight, preferably 25-9% by weight of surfactant, 0-3% by weight, preferably 1-2% by weight of surfactant. Furthermore, the herbicide of the present invention can be mixed or used in combination with other herbicides, pesticides such as insecticides, fungicides, fertilizers, soil, etc., and in this case may exhibit even better effects.

The appropriate amount of the herbicide of the present invention to be applied cannot be determined unconditionally due to differences in weather conditions, soil conditions, drug formulation, application timing, application method, type of target weed, etc., but in general, the amount of active ingredient applied per are is 1. ~500 evenings, preferably 10
~100 evenings. Next, examples of plant tests and formulations of herbicides according to the present invention will be described, but of course the present invention is not limited to these descriptions. Test Example 1 Paddy soil was put into a 1/2000 are pot and saturated with water, and then the food seeds were sown, lightly covered with soil, and germinated in the field.

When cotyledon failure appeared, it was flooded with water to a depth of 3.5 cm, and an aqueous dispersion of each test compound was added dropwise to a concentration of 100 μm per active ingredient. Three weeks after the chemical solution treatment, the growth state was observed with the naked eye, and the degree of growth inhibition was expressed based on the following criteria (5-point scale from 1 to 5), and the results are listed in Table 2. Growth suppression degree 5
: Complete dead state 1: Growth test example 2 similar to untreated plot. The test was conducted in the same manner as in Test Example 1, except that the amount of the active ingredient was reduced.

Table 3 Test Example 3 After paddy soil was placed in a 1/2000 are pot and saturated with water, soil containing a large amount of firefly seeds was sprinkled on the soil surface of each pot.

When the fireflies reached the first hollyhock stage, water was applied to the water to a depth of 3, and a predetermined amount of an aqueous dispersion of each test compound was added dropwise to the water. Three weeks after the chemical solution treatment, the growth state was observed with the naked eye, and the degree of growth inhibition was expressed using the same criteria as in Test Example 1, and the results shown in Table 4 were obtained. Table 4 Test Example 4 Tubers of Urikawa were planted in a 1'2,000-are pot, filled with water to a depth of 3, and grown in a greenhouse.

When the cucumber reached the two-leaf stage, a predetermined amount of an aqueous dispersion of each test compound was added dropwise to the plant. Three weeks after the chemical solution treatment, the growth state was observed with the naked eye, and the degree of growth inhibition was expressed using the same criteria as in Test Example 1, and the results shown in Table 5 were obtained. Table 5 Test Example 5 After filling a 1/2000 are pot with paddy soil and saturating it with water, 2. Paddy rice seedlings in the Maniwa season were transplanted and grown under water.

On the third day after transplantation, an aqueous dispersion of the test compound was dropped to a predetermined amount at a water depth of 3 arcs. Four weeks after the treatment, all the individuals were taken out, their air-dry weights were weighed, and an index was determined, with the untreated group being 100. Table 6 Formulation example 1 ○｝Pennite 5 parts by weight [
21 Sieglite 30 〃
'3} Sodium ligninsulfonate 5 Mix the above ingredients, granulate them, dilute this with an appropriate amount of acetone, and add 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(2,4- A herbicide (granules) of the present invention was obtained by spraying 7 parts by weight of dinitrophenoxy)pyrazole.

Formulation example 2 [1} Parts by weight of 103-dimethyl-4-(2,4-dichlorobenzoyl)-5-allyloxypyrazole 2 xylene 16 parts by weight [3
'Solpol 280 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 2 parts by weight or more of each component are uniformly mixed, and the herbicide of the present invention (
Emulsion) was obtained.

Formulation example 3 ○'1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-benzoylmethoxypyrazole
Weight part of 2■ Siekrite
75 parts by weight Glue Labelin S (trade name: Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts by weight Sodium lignin sulfonate 3 parts by weight or more of each component were uniformly mixed to obtain the herbicide (wettable powder) of the present invention .

Claims (1)

[Claims] 1 General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, Y is a chlorine atom or a nitro group, and Z is an allyl group, propargyl group, 4-nitrobenzyl group, phenethyl group. phenacyl group, 4-chlorophenacyl group, 2,4-dichlorophenacyl group, 4-methylsulfonylphenacyl group or 2,4-dinitrophenyl group].