JPH04211065A - 3-substituted phenylpyrazole derivative or its salts and their use - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a herbicide. CONSTITUTION:A compound, e.g. ethyl 2-[2-chloro-5-(4-chloro-5- difluoromethoxy-1-methyl-1H-pyrazol-3-yl)-4-fluorobenzoyloxy]acetate expressed by formula I {R<1> is lower alkyl; R<2> is haloalkoxy; R<3> is halogen; R<4> is -(OCH2)n- CO-Z<1>-R<5> [Z<1> is O, S or -N(R<6>)-(R<5> and R<6> are H, alkyl, cycloalkyl, -CH(R<7>)-CO- Z<2>-R<8>, etc., (R<7> is H or lower alkyl; R<8> is same as R<5> and R<6>; Z<2> is -O-, -S-, etc.); n is 0 or 1; when Z<1> or Z<2> is -O-, R<5> and R<6> may be alkali metal or ammonium salt]; X and Y are halogen}. The above-mentioned compound is obtained by reacting a compound expressed by formula II (X<1> is halogen or OH) with a compound expressed by the formula X<2>-Z<1>-R<5> (X<2> is H or halogen).

Description

[Detailed description of the invention]

[0001] The present invention relates to general formula (I)

[Formula, R1 represents a lower argyl group, R2 represents a haloalkoxy group, R3 represents a halogen atom, and R4 represents (
OCH2) n-Co-Z'-R5 (wherein, Zl is -
〇, -8- or -N (R6)-, R5 and R6
may be the same or different, and are a hydrogen atom, an alkyl group, a lower haloalkyl group, a lower alkenyl group, a lower haloalkenyl group, a lower alkynyl group, a cycloalkyl group, a trialkylsilylalkyl group, a lower alkylthioalkyl group, a lower alkoxyalkyl group. group, lower alkoxyalkoxyalkyl group, lower dialkylaminoalkyl group which may be the same or different, aralkyl group which may have a substituent, aryl group which may have a substituent, Good pyridyl group, lower alkylsulfonyl group, cycloalkylidenimino group or -CH(R7)-Co-22-
R8 (wherein Z2 is -0-1-8- or -N (R"
)-, R7 represents a hydrogen atom or a lower alkyl group, R7 and R8 may be the same or different, and a hydrogen atom,
Alkyl group, lower haloalkyl group, lower alkenyl group,
Lower haloalkenyl group, lower alkynyl group, cycloalkyl group, trialkylsilylalkyl group, lower alkylthioalkyl group, lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, lower dialkylaminoalkyl group which may be the same or different, substituent represents an aralkyl group which may have a substituent, an aryl group which may have a substituent, a pyridyl group which may have a substituent, and a lower alkylsulfonyl group. ), and n represents an integer of 0 or 1. In addition, when Z1 or Z2 represents 10-, R5 or R8
can also represent an alkali metal atom or a quaternary ammonium salt. ), and X and Y may be the same or different and represent a halogen atom. The present invention relates to a 3-substituted phenylpyrazole derivative represented by the following formula or a salt thereof, and a herbicide containing the compound as an active ingredient. [0002] The present inventors, in order to create a new herbicide,
As a result of extensive research, we have found that the 3-substituted phenylpyrazole derivative represented by general formula (I) or its salts is a new compound that has not been described in any literature, and that it has a strong herbicidal effect on weeds at low doses. They discovered this and completed the present invention. [0003] As the prior art of the present invention, for example, Japanese Patent Application Laid-open Nos. 50-117936, 52-91861, and 54
Pyrazole compounds are disclosed in JP 70270 and JP 55-9062, etc., but the general formula (I) of the present invention
There is no disclosure of the 3-substituted phenylpyrazole derivative or its salt represented by It has an excellent weeding effect. [0004] The 3-substituted phenylpyrazole derivative represented by the general formula (I) of the present invention or its salt has the structural isomers illustrated below, and these structural isomers are
When a substituted phenyl pyrazole derivative or its salt is produced, it is simultaneously produced and can be produced by separating it by an appropriate separation method, such as recrystallization method, column chromatography method, etc., and the present invention also includes these structural isomers.

embedded image (In the formula, R1, R2, R3, *i', x and Y are the same as above.) As the salts of the 3-substituted phenylpyrazole derivative represented by the general formula (I) of the present invention, Examples include salts of mineral acids such as hydrochloric acid and sulfuric acid, as well as salts of organic acids such as para-toluenesulfonic acid. [00051 As a typical manufacturing method of the 3-substituted phenylpyrazole derivative represented by general formula (I) or its salts of the present invention, the manufacturing method illustrated below can be exemplified, but the present invention It is not limited to these.

embedded image (wherein R1, R2, R3, R4, R5, X, Y and Z
is the same as above, Xl represents a halogen atom or a hydroxyl group, and X2 represents a hydrogen atom or a halogen atom. ) That is, by reacting a pyrazole represented by general formula (II) with a compound represented by general formula (III) in the presence of an inert solvent and a base, 3- Substituted phenylpyrazole derivatives can be prepared. [0006] Inert solvents that can be used in this reaction include:
Any substance may be used as long as it does not significantly inhibit the progress of this reaction, such as halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene, and xylene, and esters such as ethyl acetate. Nitriles such as acetonitrile and benzonitrile, chain ethers such as methylcellosolve and diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran, and inert solvents such as sulfolane, dimethylsulfone and dimethylsulfoxide can be used. These inert solvents can be used alone or in combination. [0007] As the base that can be used in this reaction, an inorganic base or an organic base can be used, and examples of the inorganic base include water of alkali metal atoms or alkaline earth metal atoms such as sodium, potassium, magnesium, and calcium. oxides, carbonates or alcoholades, and organic bases such as triethylamine, pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5゜4
, O]-7-undecene (DBU) can be used. [0008] The base may be used in a range of equimolar to molar excess relative to the pyrazole represented by the general formula (II). [0009] Since the reaction is an equimolar reaction, each reactant may be used in equimolar amounts, but the compound represented by the general formula (III) can also be used in excess. The reaction temperature may be selected from the range of 0°C to 150°C, preferably from 10°C to 100°C. The reaction time varies depending on the reaction scale, reaction temperature, etc., but may be selected from a range of several minutes to 48 hours. [00101 After the reaction is completed, the reaction solution containing the target product is isolated by a conventional method, such as a solvent extraction method or a solvent distillation method,
If necessary, the 3-substituted phenylpyrazole derivatives represented by the general formula (I) can be produced by purification by recrystallization, column chromatography, or the like.

The salts of the trisubstituted phenylpyrazole derivative represented by the general formula (I) of the present invention include salts of mineral acids such as hydrochloric acid and sulfuric acid, as well as salts of organic acids such as para-toluenesulfonic acid. For example, salts such as [0012] 3 represented by the general formula (I) of the present invention below
Representative compounds of substituted phenyl pyrazole derivatives or salts thereof are illustrated in Table 1, but the present invention is not limited to these compounds. General formula (Ia)

[C5] No. 1 table

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[0013] The pyrazoles represented by the general formula (II) which are the raw material compounds for producing the 3-substituted phenylpyrazole derivative represented by the general formula (I) or its salts of the present invention are: As shown below, ■, when n=0.

[C6] by can do.

[C7] ■, when n=1.

embedded image (wherein R1, R2, R3, X, Xl and Y are the same as above, R2-1 represents a lower haloalkyl group, and R10
represents a lower alkyl group, and W represents a halogen atom. )
[0014] That is, when n is an integer of 0 in the pyrazole represented by the general formula (III), the compound represented by the general formula (II) and diethyl carbonate are reacted in the presence of an inert solvent. A compound represented by the general formula (VI) is prepared, and the compound (VI) is reacted with a hydrazine represented by the general formula (V) to produce a pyrazole represented by the general formula (III-7). . The general formula (III-7) and the general formula (II
The pyrazole represented by I-6) is a tautomer. Next, the pyrazoles represented by the general formula (III-7) or (III-6) are reacted with the halides represented by the general formula (I■) to obtain the pyrazoles represented by the general formula (III-5). and perform a halogenation reaction on the pyrazole represented by (III-5) using a suitable halogenating agent,
By preparing pyrazoles represented by general formula (III-4) and further subjecting the pyrazoles represented by general formula (III-4) to Sommelet reaction and acid hydrolysis reaction, the general formula (III By producing pyrazoles represented by -3) and oxidizing the pyrazoles formed with (III-3), pyrazoles represented by general formula (III-1) in which Xl is a hydroxyl group can be obtained. The general formula (I) in which Xl is a halogen atom
The pyrazoles represented by II-2) have the general formula (III-
It can be produced by halogenating the pyrazole represented by 1). [0015] Furthermore, in the case of pyrazoles represented by the general formula (III), where n=1, an integer, the general formula (III-4)
The pyrazole represented by the general formula (III-4') produced in the same manner as above is nitrated with a nitrating agent to produce the pyrazole represented by the general formula (III-11), and then the pyrazole represented by the general formula (III-11) is produced. The pyrazoles represented by (IIllo) are subjected to a reduction reaction to produce the pyrazoles represented by the general formula (III-10), and the pyrazoles represented by (IIllo) are further subjected to diazotization and decomposition reactions. pyrazoles represented by the general formula (III-9), and the pyrazoles represented by the general formula (III-9) to the general formula (nI
) is reacted with a compound represented by -general formula (III-8)
A pyrazole represented by is produced. and said (III
-8) to produce a pyrazole represented by the general formula (III-1"), in which Xl is a hydroxyl group, by hydrolyzing the pyrazole represented by the formula (III). The pyrazoles represented by the general formula (III-2'') in which Xl is a halogen atom are represented by the general formula (
It can be produced by halogenating pyrazoles represented by III-1"). [0016] 3 represented by the general formula (I) of the present invention below
Typical examples of -substituted phenylpyrazole derivatives are shown below, but the present invention is not limited thereto. [0017]

[Example 1] Ethyl 2-(2-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-IH-pyrazol-3-yl)-4-fluorobenzoyloxy)acetate (Compound No. 33 ) 2-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-IH-pyrazol-3-yl)-4fluorobenzoic acid 0.28 g (0.8 mmol), acetone 30 ml .Ethyl bromoacetate 0.28g (1
, 7 mmol), powdered potassium hydroxide 0. 12g (
A mixture of 2.1 mmol) was reacted for 3 hours under reflux. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, washed with water, dried, the solvent was distilled off under reduced pressure, and the concentrated residue was purified by column chromatography to obtain the desired product as an oil. .26g was obtained. Physical properties: nDl, 5362 (23.4°C), yield near 5.0% [0018]

[Example 2] Cyclopentyl 2-(5-(4-chloro-5-difluoromethoxy-1-methyl-IH-pyrazol-3-yl)-2,4-dichlorobenzoate (Compound No. 52) [Chemical 10 ] [5-(4-chloro-difluoromethoxy-1-methyl IH-pyrazol-3-yl)-2,4-dichlorobenzoic acid 0.28 g (0, furomillimoles), acetone 30
m1. Cyclohexyl bromoacetate 0.42g (1,9
The reaction was carried out under reflux for 3 hours. After the reaction was completed, the reaction solution was poured into water and extracted with ethyl acetate.
After washing with water and drying, the solvent was distilled off under reduced pressure to obtain 0.29 g of the desired product as an oil.・Physical properties: nDl, 5477 (28.1°C), yield near 7.0% [0019] [Example 3] (5-(4-chloro-5-difluoromethoxy-1-methyl-IH-pyrazole-3) -il)-2
,4-dichloro]S-isopropylbenzoate (compound N
o, 7)

embedded image Isopropyl mercaptan 0. 13 g (1.8 mmol), 30 ml of anhydrous tetrahydrofuran. ) ethylamine 0. After cooling a mixture of 18 (1.8 mmol) with water, [:5-(4-chloro-5-difluoromethoxy1-methyl-IH-pyrazol-3-yl)-
2,4 dichloro]benzoic acid chloride 0. 35g (0
, 9 mmol) was dissolved in 3 ml of anhydrous tetrahydrofuran and added dropwise. After completion of the dropwise addition, the mixture was allowed to react at room temperature for 3 hours. After the reaction was completed, the reaction solution was poured into water, extracted with ethyl acetate, washed with water, dried, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 0.27 g of the desired product as a crystal. Obtained. Physical properties: m, p, 69. 6℃, yield near 0.0% [00
201

[Example 4] 2-(2-chloro-5(4-chloro-5
-difluoromethoxy-1-methyl-IH-virazol-3-yl)-4-fluorobenzoylthio]acetic acid (Compound No. 85) [Formula 12] Ethyl thioglycolate 0. Log (0.8 mmol) was dissolved in 20 ml of anhydrous tetrahydrofuran and, after cooling with water, 2-chloro-5-(4-chloro-
5-difluoromethoxy-1-methyl-IH-pyrazol-3yl)-4-fluorobenzoic acid chloride 0.30
g (0.8 mmol) in 3 ml of anhydrous tetrahydrofuran
was dissolved in the liquid and added dropwise. After completion of the dropwise addition, the mixture was allowed to react at room temperature for 3 hours. After the reaction was completed, the reaction solution was poured into water, extracted with ethyl acetate, washed with water, dried, and the solvent was distilled off under reduced pressure.
Objective] 0.30 g of the target product was obtained as an oily substance. Physical properties: nDl, 5647 (16.9°C), Yield: 8
2.9% [00211

[Example 5] [2-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-IH-pyrazole-3
-yl)-4-fluorobenzoic acid N-allylamide (Compound No. 92) [Formula 13] Allylamine 0. 09 g (1.6 mmol) was dissolved in 25 ml of anhydrous tetrahydrofuran, and after cooling with water, 2-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-IH-pyrazol-3-yl) was dissolved in 25 ml of anhydrous tetrahydrofuran. ) 4-Fluorobenzoic acid chloride 0. 30g (0,
8 mmol) was dissolved in 3 ml of anhydrous tetrahydrofuran and added dropwise. After completion of the dropwise addition, the mixture was allowed to react at room temperature for 3 hours. After the reaction was completed, the reaction solution was poured into water, extracted with ethyl acetate, washed with water, dried, and the solvent was distilled off under reduced pressure to obtain 0.30 g of the desired product as a crystal. Physical properties: m, p, 99.4°C, yield: 94.0% [00
22] The 3-substituted phenylpyrazole derivative represented by the general formula (I) of the present invention or its salts can be used, for example, in the grass field (common name of Japanese field grass, grass family - annual grass, typical harmful grass of paddy fields), Japanese field grass ( Cyperaceae (annual grass, harmful to paddy fields), Cyperaceae (cyperaceae, perennial grass, occurs in wetlands, waterways, and rice fields, a typical perennial pest in paddy fields), Urikawa (cyperaceae)
Omodaceae, perennial harmful grasses that occur in wetlands, ditches, and rice fields),
Firefly (a perennial herb of the Cyperaceae family, occurring in wetlands, waterways, and rice fields), oat (Poaceae – an annual herb, occurring in fields and uplands), and grasshopper (a typical strength of a grass family – an annual herb, a field, and an orchard) (Harmful grass), squeak (perennial Polygonaceae, occurs in fields and roadsides)
, Cyperaceae (Cyperaceae - annual grasses, occurring in fields, roadsides), Aobiyu (Faceae - annual grasses, occurring in fields, roadsides, vacant lots), Yaemegura (Rubiaceae - annual grasses, severely damaging grasses in fields), Pigweed (Asteraceae, a harmful grass in fields and orchards), Chamomile (Asteraceae, a harmful grass in fields and gardens),
Paddy fields, fields, orchards, and wetlands, such as Ichibi (Malvaceae, a severely harmful grass in fields), Onna fir (Asteraceae - annual grass, a grass that is harmful in fields), and Asagao (Convolvulaceae, a severely harmful grass in fields) It has the effect of controlling annual weeds and perennial weeds that occur in other areas. [00231 Since the 3-substituted phenylpyrazole derivative represented by the general formula (I) or its salts of the present invention exhibits an excellent control effect against weeds before and after emergence, the planting of useful plants is The herbicide of the present invention can be applied to the planned area in advance, or after the planting of useful plants (including cases where useful plants have already been planted, such as in a garden), from the beginning of weed emergence to the growing season. It is possible to effectively express the characteristic physiological activity that the compound has. However, the herbicide of the present invention does not have to be used only in this manner; for example, the herbicide of the present invention can not only be used as a herbicide for paddy fields or fields, but also as a herbicide for general weeds. It can also be used, for example, mowing marks, fallow fields, ridges, farm roads, waterways,
It can also be used to exterminate general weeds in grassland, cemeteries, parks, roads, playgrounds, vacant lots around buildings, cultivated land, railroad tracks, forests, etc. In this case, it is economically most effective to treat weeds before they begin to emerge, but this is not necessarily the case, and it is possible to control weeds during the growing season. [0024] When using the 3-substituted phenylpyrazole derivative represented by general formula (I) of the present invention or its salts as a herbicide, it is formulated into a form convenient for use according to the conventional method for pesticide formulation. It is common to use That is,
The 3-substituted phenylpyrazole derivative represented by the general formula (I) or its salts of the present invention can be prepared by blending them in an appropriate inert form or with an adjuvant as necessary in an appropriate ratio. They may be used by dissolving, separating, suspending, mixing, impregnating, adsorbing or adhering them, and formulating them into appropriate dosage forms such as suspensions, emulsions, solutions, wettable powders, granules, powders, tablets, etc. The inert carrier that can be used in the present invention may be either solid or liquid, and examples of materials that can be used as solid carriers include soybean flour, cereal grains, charcoal, bark powder, mineral powder, tobacco stem powder, Walnut shell powder, bran, cellulose powder, residue after extracting plant extracts, synthetic polymers such as crushed synthetic resins, clays (
(e.g. kaolin, bentonite, acid clay, etc.), talc (e.g. talc, pyrophyllite, etc.), silica (e.g. diatomaceous earth, silica sand, mica, white carbon Some contain calcium as a main component.]
), activated carbon, sulfur powder, pumice, calcined diatomaceous earth, crushed bricks, fly ash, sand, inorganic mineral powders such as calcium carbonate and calcium phosphate, ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea,
Examples include chemical fertilizers such as ammonium chloride, compost, etc. These may be used alone or in the form of a mixture of two or more. [0025] Materials that can serve as liquid carriers are selected from those that themselves have solvent ability, as well as those that have solvent ability but can disperse the active ingredient compound with the help of adjuvants. Examples include the following carriers, which may be used alone or in a mixture of two or more, such as water, alcohols (e.g. methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.), ketones, etc. (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone,
diisobutylketone, cyclohexanone, etc.), ethers (e.g. ethyl ether, dioxane, cellosolve,
dipropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g. gasoline, mineral oil, etc.), aromatic hydrocarbons (e.g. benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, etc.), halogenated hydrocarbons (e.g. dichloroethane) , chloroform, carbon tetrachloride, etc.), esters (e.g., ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.), amides (e.g., dimethylformamide, diethylformamide, dimethylacetamide, etc.), nitriles (e.g., acetonitrile, etc.), Dimethyl sulfoxides and the like can be mentioned. Other adjuvants include the following typical adjuvants, and these adjuvants are used depending on the purpose and may be used alone, in some cases two or more adjuvants may be used in combination, or In some cases it is also possible to use no adjuvants at all. [0026] Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and/or wetting the active ingredient compounds, such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene higher fatty acid ester. , polyoxyethylene resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylaryl sulfonate, naphthalene sulfonic acid condensate,
Examples include surfactants such as lignin sulfonate and higher alcohol sulfate. Also, for the purpose of dispersion stabilization, adhesion and/or binding of active ingredient compounds,
It is also possible to use the following auxiliary agents, such as casein, gelatin, starch, methyl cellulose, carboxymethyl cellulose, gum arabic, polyvinyl alcohol, pine oil, bran oil, bentonite, lignin sulfonate, etc. You can also do it. [0027] The following adjuvants may also be used to improve the flowability of the solid product, for example adjuvants such as waxes, stearates, phosphoric acid alkyl esters, etc. Auxiliary agents such as naphthalene sulfonic acid condensates, condensed phosphates, etc. can also be used as peptizers for suspension products. As the antifoaming agent, auxiliary agents such as silicone oil can also be used. The blending ratio of the active ingredient compound can be adjusted as necessary, for example, 0.01 to 50% by weight in the case of powders or granules, and 0.01 to 50% in the case of emulsions or wettable powders. Weight % is appropriate. [0028] The herbicide containing the 3-substituted pyrazole derivative represented by general formula (I) or its salts as an active ingredient of the present invention can be used to kill various weeds or suppress their growth.
Apply to the weeds in an effective amount to kill or suppress their growth, either as is, diluted with water, etc., or suspended, in an amount effective for killing or suppressing the growth of the weeds.
Or, in places where the emergence or growth of the weed is unfavorable, it can be applied to foliage or soil. [00291 The amount of the herbicide containing the 3-substituted pyrazole derivative represented by the general formula (I) or its salt of the present invention as an active ingredient depends on various factors, such as the purpose, the target weed, and the occurrence/growth of the weed or crop. Although it varies depending on the situation, weed growth tendency, weather, environmental conditions, dosage form, application method, application place, application time, etc., the active ingredient compound should be selected as appropriate from the range of 0.1 g to 5 kg per hectare depending on the purpose. Good. When using the herbicide containing the 3-substituted pyrazole derivative represented by general formula (I) or its salts as an active ingredient of the present invention as a herbicide for paddy fields or upland fields, for example, the amount of the active ingredient is 100 g or less per hectare. It is sufficient to select a dosage that does not cause phytotoxicity to crops and can selectively control the target weeds, and when used as a herbicide for non-agricultural land, the amount of active ingredient should be selected. It is sufficient to select a dosage of 100g or more per hectare that can kill the target weeds. [00301 The herbicide containing the 3-substituted pyrazole derivative represented by the general formula (I) of the present invention or its salts as an active ingredient is further used to expand the target herb species to be controlled, the appropriate period for control, or to reduce the dosage. It can also be used in combination with other herbicides for this purpose. [0031] Typical test examples and formulation examples of the composition of the present invention are illustrated below. In addition, in the prescription examples, parts indicate parts by weight. [0032]

[Test Example 1] Herbicidal effect on paddy rice weeds after emergence 1/10,000 soil was packed in a pot to create a paddy field, and paddy field weeds such as field weeds, seeds of Japanese field weeds, seeds of Japanese firefly, and tubers of Japanese cypress and Japanese apricot were adjusted to the single-leaf stage. . This was treated with a spray solution containing a compound of the present invention (compounds listed in Table 1) at a predetermined concentration as an active ingredient. The herbicidal effect was investigated 21 days after the treatment, and the herbicidal rate was calculated in comparison with no treatment, and the evaluation was made according to the following criteria. At the same time, phytotoxicity to paddy rice was investigated and phytotoxicity was determined according to the following criteria. Criterion 5 for herbicidal activity: 95% or more weed killing. 4...70% or more and less than 90% weed killing. 3...50% or more and less than 70% weed killing. 2: Killing weeds by 30% or more and less than 50%. 1...10% or more and less than 30% weed killing. 0...Less than 10% weed killing. Judgment criteria for phytotoxicity 0: No phytotoxicity 1: Browning occurs, but it recovers early and there is almost no growth inhibition. 2...Clear growth suppression is observed along with browning, but recovery occurs at an early stage. 3... Browning and growth suppression are significant, and recovery is slow. 4... Significant browning and growth suppression, and some solids are seen to wither and die. 5... All solids are almost dead. The results are shown in Table 2. Table 2 Comparative Compound Compound A is 3-phenyl-5-methylthiopyrazole described on page 5 of JP-A-52-91861, B is the compound described in Example 1 on page 4 of the same publication, and C Compound No. 8 described in JP-A-54-70270 was used as a comparative compound, and compound No. 159 described in JP-A-55-9062, page 9 was used as a comparative compound for D.

[Chemical formula 14] [0033]

[Test Example 2] Herbicidal effect on field weeds before emergence Vertical 10
Fill a polyethylene vat measuring 20 cm x 20 cm x 5 cm high with soil, and fill it with field weeds such as field weeds, grasshoppers, etc.
Seeds of Soybean fir, Soybean occidentalis, Soybean occidentalis, and field crops such as soybean and wheat were sown and covered with soil. This was treated with a drug containing the compound of the present invention (compounds listed in Table 1) as an active ingredient in the form of a predetermined concentrated skin spray solution. Processing 1
After 4 days, the herbicidal effect was investigated, and the herbicidal rate was calculated and judged in the same manner as Test Example 1. At the same time, phytotoxicity to soybeans and wheat was investigated, and phytotoxicity was determined according to the standards of Test Example 1. The results are shown in Table 3. Table 3 [0034]

[Test Example 3] Herbicidal effect on field weeds after emergence Vertical 10
A polyethylene bat measuring 20 cm x 20 cm x 5 cm high is filled with soil, and seeds of the following field noxious weeds and soybean and wheat seeds as field crops are sown and covered with soil.
Each plant was grown until the following leaf stage was reached, and treated with a spray solution containing a compound of the present invention (compounds listed in Table 1) as an active ingredient at a predetermined concentration. The herbicidal effect was investigated 14 days after the treatment, and the herbicidal rate was calculated and judged in the same manner as Test Example 1. At the same time, phytotoxicity to soybeans and wheat was investigated, and phytotoxicity was determined according to the standards of Test Example 1. Test weed species, their leaf stages, and leaf stages of soybean and wheat
Two-leaf stage Ichibi
Two-leaf stage giant dogfish
One-leaf stage Onamia
One leaf stage Yaemugura
Two-leaf stage wheat
Two-leaf soybean
The results at the first leaf stage are shown in Table 4. Table 4 [0035]

[Formulation Example 1] Compound of the present invention
50 parts clay/white carbon mixture mainly consisting of clay
45 parts polyoxyethylene nonylphenyl ether 5 parts or more are uniformly mixed and ground to prepare a wettable powder. [0036]

[Formulation Example 2] Compound of the present invention
5 parts bentonite clay mixture
90 parts Calcium ligninsulfonate 5 parts or more are uniformly mixed and pulverized, an appropriate amount of water is added, kneaded, and granulated to obtain granules. [0037]

[Formulation Example 3] Compound of the present invention
50 parts xylene
40 parts mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate
Mix and dissolve 10 parts or more uniformly,
Make it into an emulsion.

Claims (1)

[Scope of Claims] [Claim 1] General formula (I) [Formula 1] (wherein, R1 represents a lower alkyl group, R2 represents a haloalkoxy group, R3 represents a halogen atom, and R4 represents (
OCH2) n-Co-Z'-R" (wherein, Zl
represents -0, -8- or -N (R6)-, R and R6 may be the same or different, and represent a hydrogen atom, an alkyl group, a lower haloalkyl group, a lower alkenyl group, a lower haloalkenyl group, a lower alkynyl group. group, cycloalkyl group, trialkylsilylalkyl group, lower alkylthioalkyl group, lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, lower dialkylaminoalkyl group which may be the same or different, aralkyl which may have a substituent. group, an aryl group that may have a substituent, a pyridyl group that may have a substituent, a lower alkylsulfonyl group, a cycloalkylidenimino group, or -CH(R7)-Co-2
2-R8 (wherein Z2 is -0-1-8- or -N (R
”)-, R7 represents a hydrogen atom or a lower alkyl group, R7 and R8 may be the same or different, and represent a hydrogen atom, an alkyl group, a lower haloalkyl group, a lower alkenyl group, a lower haloalkenyl group, a lower alkynyl group. group, cycloalkyl group, trialkylsilylalkyl group, lower alkylthioalkyl group, lower alkoxyalkyl group, lower alkoxyalkoxyalkyl group, lower dialkylaminoalkyl group which may be the same or different, aralkyl which may have a substituent. group, an aryl group which may have a substituent, a pyridyl group which may have a substituent, a lower alkylsulfonyl group), where n is an integer of 0 or 1. Also, Zl or Z2 10-, R5 or R6 can also represent an alkali metal atom or a quaternary ammonium salt), and X and Y may be the same or different and represent a halogen atom. [Claim 2] The 3-substituted phenylpyrazole derivative or salt thereof according to claim 1, wherein Y represents a chlorine atom. [Claim 3] X represents a chlorine atom or 3-substituted phenylpyrazole derivative or salt thereof according to claim 2, which represents a fluorine atom.Claim 4: The 3-substituted phenylpyrazole derivative or salt thereof according to claim 2, wherein R1 represents a methyl group, R2 represents a difluoromethoxy group, and R3 represents a chlorine atom. 3
3-substituted phenylpyrazole derivative or salt thereof as described in 1. 5. A herbicide comprising the 3-substituted phenylpyrazole derivative or its salts according to claim 1 as an active ingredient. 6. A herbicide comprising the 3-substituted phenylpyrazole derivative or its salts according to claim 2 as an active ingredient. 7. A herbicide comprising the 3-substituted phenylpyrazole derivative or its salts according to claim 3 as an active ingredient. 8. A herbicide comprising the 3-substituted phenylpyrazole derivative or its salts according to claim 4 as an active ingredient.