JP2905981B2 - 3-Substituted phenylpyrazole derivatives or salts thereof, process for producing the same, and herbicides - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel 3-substituted phenylpyrazole derivative, a method for producing the same, and a herbicide containing the compound as an active ingredient.

The present inventors have conducted intensive studies in order to create a novel compound which has little phytotoxicity to crops and has a herbicidal effect at a low dose, and as a result, the compound represented by the following general formula (I): It has been found that substituted phenylpyrazole derivatives or salts thereof are novel compounds that have not been described in the literature, show excellent herbicidal effects on many weeds at low doses, and have low phytotoxicity on crops. The present invention has been completed.

JP-A-50-117936, JP-A-52-91861, JP-A-54-70270 and JP-A-55-9062 disclose pyrazole derivatives as herbicides, which are represented by the general formula (I) of the present invention. No 3-substituted phenylpyrazole derivatives or salts thereof are disclosed at all, and exhibit excellent herbicidal effects at a lower dose than compounds disclosed in these publications, and have less phytotoxicity to crops. Things.

The 3-substituted phenylpyrazole derivative of the present invention or a salt thereof has a general formula (I) [Wherein, R ¹ represents a lower alkyl group, a lower haloalkyl group, a phenyl group or a phenyl group having 1 to 5 substituents which may be the same or different, and R ² represents a halogen atom, a lower alkyl group, a lower haloalkyl A lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower haloalkylthio group, a lower alkylsulfinyl group, a lower haloalkylsulfinyl group, a lower alkylsulfoyl group or a lower haloalkylsulfonyl group, and R ³ represents a hydrogen atom or halogen R ⁴ represents a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkenyl group, a lower haloalkenyl group, a lower alkynyl group, a lower haloalkynyl group, a lower alkoxyalkyl group which may be substituted with a halogen atom, a halogen atom; Lower alkylthio which may be substituted by an atom Alkyl group, cyanoalkyl group, a lower alkoxyalkoxy ^{group, -CO (R 5) CO-} Y
-R ⁶ (wherein, R ⁵ represents a hydrogen atom or a lower alkyl group,
R ⁶ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
A lower alkenyl group, a lower haloalkenyl group, a lower alkynyl group, a lower haloalkynyl group, a lower alkoxyalkyl group or a lower alkylthioalkyl group, and Y is O,
S or —N (R ⁷ ) — (wherein R ⁷ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group), and when Y is O or S, R ⁶ is an alkali metal Atomic or quaternary ammonium salts can also be indicated. ), X represents a hydrogen atom or a halogen atom, A represents O,
S or -N (R ⁷⁾ - (wherein, R ⁷ is the same). Is shown. ] Is represented by

The 3-substituted phenylpyrazole derivative represented by the general formula (I) of the present invention can be produced, for example, by the following production method.

(Wherein R ¹ , R ² , R ³ and X are as defined above, A ¹ represents O or —NH—, and R ^4-1 represents a lower alkyl group, a lower haloalkyl group, a lower alkenyl group, a lower halo group. Alkenyl group, lower alkynyl group, lower haloalkynyl group, lower alkoxyalkyl group optionally substituted by halogen atom, lower alkylthioalkyl group optionally substituted by halogen atom, cyanoalkyl group, lower alkoxyalkoxyalkyl group, -CH (R ⁵ ) CO—Y—R ⁶ (wherein, R ⁵ represents a hydrogen atom or a lower alkyl group, and R ⁶ represents a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkenyl group,
Lower haloalkenyl group, a lower alkynyl group, a lower haloalkynyl group, a lower alkoxyalkyl group or a lower alkylthioalkyl group, Y is O, S or -N (R ⁷⁾ -
(Wherein, R ⁷ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group), and when Y is O or S, R ⁶ represents an alkali metal atom or a quaternary ammonium salt. Can also. S represents a halogen atom. That is, the pyrazole represented by the general formula (II-1) is
A carbonyl insertion reaction is performed with a carbonylation reagent in the presence or absence of an inert solvent and in the presence or absence of a base, and a 3-substituted phenylpyrazole derivative represented by the general formula (I-1) is obtained. Wherein the 3-substituted phenylpyrazole derivative is isolated or not isolated, and is represented by the general formula (II
The 3-substituted phenylpyrazole derivative represented by the general formula (I-2) can be produced by reacting the halide represented by I) with a base and an inert solvent.

A-1. General formula (II-1) → General formula (I-1) As an inert solvent that can be used in this reaction, any solvent that does not significantly inhibit the progress of this reaction may be used. Halogenated hydrocarbons such as carbon chloride, aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; and chain ethers such as methyl cellosolve and diethyl ethere , Dioxane,
Although cyclic ethers such as tetrahydrofuran, sulfolane, dimethyl sulfone, dimethyl sulfoside and the like can be exemplified, the reaction is not limited to these inert solvents, and these inert solvents may be used alone. Alternatively, they can be used as a mixture.

As the carbonylation reagent that can be used in this reaction, phosgene, carbonyldiimidazole, disuccinimide carbonate, and the like can be used.Other methods include, for example, a method of adding carbon monoxide using selenium dioxide as a catalyst. However, it is preferable to use disuccinimide carbonate.

Since this reaction is an equimolar reaction, the reaction reagent may be used in an equimolar amount, but it is preferable to use an excess of the carbonylation reagent.

In the present reaction, when phosgene is used as a carbonylation reagent, the reaction is carried out in the presence of a base.As the usable base, an inorganic base or an organic base can be used.As the inorganic base, for example, sodium, potassium, magnesium Or hydroxides, carbonates or alcoholates of alkali metals or alkaline earth metals such as calcium or the like,
Examples of the organic base include triethylamine, pyridine and the like.

The reaction temperature may be selected from the range of room temperature to the boiling point range of the inert solvent used.

The reaction time is not constant depending on the reaction scale and reaction temperature,
It ranges from a few minutes to 48 hours.

After completion of the reaction, the target substance is removed from the reaction mixture by a conventional method, for example, by distilling off an inert solvent under reduced pressure, and, if necessary, by purifying the compound by a recrystallization method, a column chromatography method, or the like to obtain a compound of the general formula (I-1) A 3-substituted phenylpyrazole derivative represented by the following formula can be produced.

A-2. General formula (I-1) → General formula (I-2) The inert solvent that can be used in the present reaction may be any solvent that does not significantly inhibit the progress of the present reaction.
Water or the like can be used in addition to the inert solvent exemplified in,
These inert solvents can be used alone or as a mixture. When a mixed solvent of water and an organic solvent is used, a phase transfer catalyst can be used.

Since this reaction is an equimolar reaction, the reaction reagent may be used in an equimolar amount, but the halide represented by the general formula (III) may be used in excess.

As the base that can be used in this reaction, an inorganic base or an organic base that can be used for A-1 can be used.

The base may be used in an amount ranging from equimolar to excess mol based on the 3-substituted phenylpyrazole derivative represented by the general formula (I-1).

The reaction temperature may be selected from the range of 0 ° C. to the boiling point range of the inert solvent used.

The reaction time is not constant depending on the reaction scale and reaction temperature,
It ranges from a few minutes to 48 hours.

After completion of the reaction, the target compound is represented by the general formula (I-2) by subjecting the reaction product from the reaction solution by a conventional method, for example, by performing an operation such as solvent extraction, and, if necessary, by performing a recrystallization method or a column chromatography method. A 3-substituted phenylpyrazole derivative can be produced.

A-3. A pyrazole derivative represented by the general formula (I), wherein A is-
N (R ⁷⁾ - pyrazole derivative represented by, A is -NH-
And a lower alkyl halide, a lower alkenyl halide, or a lower alkynyl halide in the same manner as above.

(Wherein R ¹ , R ² , R ³ , R ^4-1 and X are the same as above, and Z represents a halogen atom.) That is, the pyrazoles represented by the general formula (II-2) are inactivated. The compound is reacted with a thiocyanate in the presence of a solvent, and then cyclized with a halogen such as bromine to obtain a compound represented by the general formula (II-3):
Wherein the general formula (II-3) is isolated or not subjected to a diazotization / decomposition reaction in the presence of an inert solvent to obtain a pyrazole represented by the general formula (I-3) A 3-substituted phenylpyrazole derivative, which is isolated or not isolated from the general formula (I-3), and further reacted with a halide represented by the general formula (III) in the presence of a base and an inert solvent. To produce a 3-substituted phenylpyrazole derivative represented by the general formula (I-4).

B-1. General formula (II-2) → General formula (II-3) As the inert solvent that can be used in this reaction, for example, organic acids can also be used in addition to mineral acids such as acetic acid and hydrochloric acid. These can be used alone or as a mixture with water.

As the thiocyanate that can be used in this reaction, for example, thiocyanic acid such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate can be used.

Since the amount of the thiocyanate used is an equimolar reaction, the thiocyanate may be used in an equimolar amount with respect to the pyrazole represented by the general formula (II-2), but is preferably used in excess.

Next, as the halogen used for the cyclization reaction, halogen such as chlorine and bromine can be used, and the amount of the halogen used is equimolar to excess molar with respect to the pyrazole represented by the general formula (II-2). It is sufficient to use it within the range, but it is preferable to use it in excess.

The reaction temperature may be selected from the range of 0 to 50 ° C for both the addition reaction and the cyclization reaction of thiocyanic acid.

The reaction time is not fixed depending on the amount of the reactants and the reaction temperature, but may be appropriately selected from several minutes to 48 hours through the addition reaction and the cyclization reaction of the thiocyanate.

After completion of the reaction, it can be isolated from the reaction solution containing the target substance by a conventional method, for example, by a solvent extraction method, solvent evaporation, and the like, and if necessary, purified by a column chromatography method, a recrystallization method, or the like. A pyrazole represented by the general formula (II-3) can be produced.

B-2. General formula (II-3) → General formula (I-3) This reaction comprises a diazotization and decomposition reaction, and the diazotization reaction uses sodium nitrite, and the sodium nitrite is in powder form or It may be diluted with an appropriate amount of water and used.

The amount of sodium nitrite used may be an equimolar amount to the pyrazoles represented by the general formula (II-3), and may be used in excess.

 The reaction temperature is preferably in the range of -5 ° C to 5 ° C.

Mineral acids such as sulfuric acid and acetic acid used in the reaction and mixtures of these with water can be used.

Then, the obtained diazonium salt of pyrazoles may be isolated or subjected to the next decomposition reaction without isolation.

When the diazonium salt is not isolated as the inert solvent used in the decomposition reaction, the inert solvent used in the diazotization may be used as it is, and when isolated, a 30 to 70% aqueous sulfuric acid solution or the like is used. be able to.

The decomposition reaction is performed in the presence of a catalyst, and the reaction temperature is 10-18.
It is performed in the range of 0 ° C., but it is better to perform in the range of 50 to 180 ° C. when the diazonium salt solution is dropped into the inert solvent, and in the case of using cuprous oxide as a catalyst, the temperature is 10 to 50 ° C. It is better to do in the range.

As a catalyst that can be used in the decomposition reaction, copper sulfate, cuprous oxide, or the like can be used. Copper nitrate is added to the reaction system, and then cuprous oxide may be added.

The amounts of copper nitrate and cuprous oxide used can be appropriately selected from the range of equimolar to 60-fold molar for copper nitrate, preferably 30 to
The reaction is preferably carried out in a molar amount of 60 times, and the amount of cuprous oxide used may be in the range of a catalyst amount to an equimolar amount, preferably about an equimolar amount.

The reaction time is not fixed depending on the amount of the reactant and the reaction temperature, but may be appropriately selected in the range of several minutes to 48 hours for the diazotization and decomposition reaction.

After completion of the reaction, the reaction solution containing the target substance is poured into ice water, and the target substance can be isolated by a method such as solvent extraction, and if necessary, purified by a recrystallization method, a column chromatography method, or the like. 3 represented by the general formula (I-3)
-Substituted phenylpyrazole derivatives can be prepared.

C. General formula (I-3) → General formula (I-4) This reaction is carried out in the same manner as in A-2 to obtain a compound of the general formula (I-
The 3-substituted phenylpyrazole derivative represented by 4) can be produced.

B-4. In the pyrazole derivative represented by the general formula (I), when R ² is a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower haloalkylsulfinyl group or a lower haloalkylsulfonyl group, R ² is a lower alkylthio group or a lower alkylthio group. It can be produced by oxidizing a pyrazole derivative represented by the general formula (I) having a haloalkylthio group with a peroxide such as metachloroperbenzoic acid.

Table 1 shows typical compounds of the 3-substituted phenylpyrazole derivative represented by the general formula (I).

In Table 1, the data of nuclear magnetic resonance spectrum (NMR) of the compound whose physical properties are oil are shown in Table 2.

Examples of the salts of the 3-substituted phenylpyrazole derivative represented by the general formula (I) include salts of mineral acids such as hydrochloric acid and sulfuric acid, and salts of organic acids such as paratoluenesulfonic acid. These salts can be produced by treating the 3-substituted pyrazole derivative represented by the general formula (I) with an appropriate mineral acid, organic acid or the like.

The pyrazoles represented by the general formula (II-1) or (II-2) can be produced by the method shown below.

(Wherein, R ¹ , R ² , R ³ , X and Z are as defined above, R ^3-1 represents a halogen atom, W represents a hydrogen atom or a halogen atom, and R ⁸ represents a lower alkyl group or a lower alkyl group. A haloalkyl group, and R ⁹ represents a lower alkyl group. That is, when R ² is a halogen atom, the compound represented by the general formula (X) is reacted with the compound represented by the general formula (VI). Wherein R ² is a lower alkyl group, a compound represented by the general formula (XI) and a hydrazine represented by the general formula (V) To give a pyrazole represented by the general formula (IV-4-1), and when R ² is a lower alkoxy group or a lower haloalkoxy group, the compound represented by the general formula (XII) is reacted with a dialkyl carbonate The compound (VII) is reacted with a compound represented by the general formula (V) to form a compound represented by the general formula (VII). Oxazines and allowed the general formula to react with a halide compound represented by (IX), the pyrazole of the general formula (IV-4-1), or R ² is a lower alkylthio group or a lower haloalkylthio group By reacting compound (VII) with a Lawesson reagent and a halide represented by the general formula (IX) to give a pyrazole represented by the general formula (IV-4-1), or a compound represented by the general formula (XII) Is reacted with carbon disulfide, and then with a halide represented by the general formula (IX) to give a compound represented by the general formula (VIII). By reacting with a hydrazine represented by (V), a pyrazole represented by the general formula (IV-4-1) can be produced.

Further, the pyrazole represented by the general formula (IV-4-2) can be produced by halogenating the pyrazole represented by the general formula (IV-4-1).

The pyrazoles represented by the general formula (IV-4) obtained by the above-mentioned production method are nitrated to give pyrazoles represented by the general formula (IV-3), and represented by the general formula (IV-3) When W is a halogen atom in a pyrazole, the general formula (IV-
3) The pyrazoles represented by the general formula (II-1-2) are obtained by reacting the pyrazoles represented by the general formula (VI-5) with ammonia to obtain a pyrazole represented by the general formula (II-1-2). The pyrazoles represented by the general formula (IV-3) are produced or reacted with an alcoholate to form a pyrazole represented by the general formula (IV-2), and further dealkylated with an acid. A compound represented by the formula (IV-1) is converted to a pyrazole represented by the general formula (II-1-1) by reducing the compound represented by the general formula (IV-1). it can.

The pyrazoles represented by the general formula (II-1) can be produced by the above production method.

Further, the pyrazoles represented by the general formula (II-2) are obtained by the above method when the pyrazoles represented by the general formula (IV-3) and W is a hydrogen atom are represented by the general formula (IV-3) Can be produced by reducing a pyrazole represented by

Hereinafter, typical examples of the present invention will be described, but the present invention is not limited thereto.

Example 1. 5- (4-chloro-5-difluoromethoxy-1-methylpyrazol-3-yl) -6-fluoro-
Production of 2 (3H) -benzoxazolone (Compound No. 4) 3- (5-amino-2-fluoro-4-hydroxyphenyl) -4-chloro-5-difluoromethoxy-1-
To a solution of 0.61 g (1.98 mmol) of methylpyrazole in 60 ml of acetonitrile was added dropwise a solution of 0.51 g (1.98 mmol) of dissuccinimide carbonate in 60 ml of acetonitrile. After the completion of the dropwise addition, the reaction was carried out at room temperature for 3 hours.

After completion of the reaction, the solvent was distilled off from the reaction solution containing the target compound under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0.35 g of the target product.

Physical properties Oily substance Yield 53.0% NMR (CDCl ₃ / TMS, δ value, ppm) 3.82 (3H, s), 6.12 (1H, t, J = 72 Hz), 7.08 (1H, d, J =
9Hz), 7.14 (1H, d, J = 5Hz), 11.22 (1H, brs). Example 2. 5- (4-Chloro-5-difluoromethoxy-1-methylpyrazol-3-yl) -6-fluoro-
Production of 3- (2-propynyl) -2 (3H) -benzoxazolone (Compound No. 9) 5- (4-chloro-5-difluoromethoxy-1-methylpyrazol-3-yl) -6-fluoro-2 (3H)
-0.35 g (1.05 mmol) of benzoxazolone in 17 ml of dimethyl sulfoxide and 0.09 g (1.5
0.19 g (1.6 mmol) of propargyl bromide was added to the mixture (8 mmol), and the mixture was reacted at room temperature for 1 hour.

After completion of the reaction, the reaction solution containing the desired product was poured into cold diluted hydrochloric acid, extracted with ethyl acetate, the extract was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was dissolved in ether and n-hexane. Recrystallization afforded 0.25 g of the desired product.

Physical properties mp118.0 ° C Yield 64.1% Example 3. 6-Chloro-5- (4-chloro-1-methyl-5-methylthiopyrazol-3-yl) -2 (3H)-
Production of Benzithiazolone (Compound No. 1) 3-1. 2-Amino-6-chloro-5- (4-chloro-
Production of 1-methyl-5-methylthiopyrazol-3-yl) benzothiazole 11.3 g of 3- (5-amino-2-chlorophenyl) -4-chloro-1-methyl-5-methylthiopyrazole (39.
2 mmol) was dissolved in 38 ml of 95% glacial acetic acid, and 7.45 g (98 mmol) of ammonium thiocyanate was added, followed by stirring at room temperature until a homogeneous solution was obtained. Next, bromine was added to the reaction solution.
A solution of 7.21 g (45.08 mmol) in 11 ml of glacial acetic acid was added dropwise. After completion of the dropwise addition, the mixture was allowed to stand at room temperature overnight, and then the reaction solution was heated to 100 ° C., 76 ml of hot water was added to the reaction solution, the mixture was filtered while hot, and the filtrate was cooled. The desired product was extracted with ethyl acetate. Extract solution with water, 5
% Sodium hydrogencarbonate solution and brine, dried over anhydrous sodium sulfate, the extract was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate to give 2.47 g of the desired product.

Physical properties Crystals Yield 18.3% NMR (CDCl ₃ / TMS, δ value, ppm) 2.40 (3H, s), 3.96 (3H, s), 7.26 (1H, s), 7.33 (2H,
brs), 7.66 (1H, s) 3-2. 6-Chloro-5- (4-chloro-1-methyl-
Production of 5-methylthiopyrazol-3-yl) -2 (3H) -benzothiazolone (Compound No. 1) 2-amino-6-chloro-5- (4
-Chloro-1-methyl-5-methylthiopyrazole-3
-Yl) benzothiazole 1.87 g (5.4 mmol), 4 ml of concentrated sulfuric acid, 4 ml of acetic acid and 4 ml of water were cooled in an ice bath, and then 0.41 g (5.9 mmol) of sodium nitrite was added to the mixture.
Was added dropwise at a temperature of 0 to 5 ° C.
A stirring reaction was performed for one hour. Then, a solution prepared by dissolving 78.27 g (324 mmol) of copper nitrate in 117.4 ml of water was added dropwise, and after the temperature of the reaction solution was raised to 15 ° C., 0.77 g (5.4 mmol) of cuprous oxide was added until foaming was completed. The reaction was performed.

After completion of the reaction, the target substance was extracted from the reaction solution containing the target substance with ethyl acetate. The extract was washed successively with water, 5% aqueous sodium hydrogen carbonate solution and brine, dried over anhydrous sodium sulfate, the extract was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0.41 g of the desired product. .

Physical properties Oily substance Yield 21.9% NMR (CDCl ₃ / TMS, δ value, ppm) 2.41 (3H, s), 3.98 (3H, s), 7.07 (1H, s), 7.43 (1H,
s), 10.18 (1H, brs).

Examples of the 3-substituted phenylpyrazole derivative represented by the general formula (I) of the present invention or a salt thereof include, for example, nobies (common name of rice brassicae, annual grasses of the family Poaceae, typical strong harmful plants of paddy fields)
Oyster fossil (Cyperaceae annual annual grass, paddy field pest), pine bye (Cyperaceae perennial grass, wetland, waterway, paddy field, typical perennial grass of rice field) Perennial weeds, fireflies (periwinkle, perennial grasses, swamps, waterways, paddy fields), oats (grass annuals, grasses,
Occurrence in the field), crabgrass (grass annual grass, field, a strong grass in the orchard), Rigid grass (Poaceae perennial grass, field,
Occurs on the roadside), Kogomeka-tsuri (Cyperaceae annuals, upland, on the roadside)
It has the effect of controlling annual and perennial weeds that occur in paddy fields, upland fields, orchards, wetlands, and the like, such as in fields, roadsides, and open spaces.

The 3-substituted phenylpyrazole derivative represented by the general formula (I) or a salt thereof according to the present invention has an excellent control effect on weeds before and after budding, and therefore, is useful in place where useful plants are to be planted. Treated or after planting of useful plants (including cases where useful plants are already planted as in an orchard). By treating from the early stage of weed development to the growing stage, the characteristic physiological activity of the herbicide of the present invention is obtained. Can be effectively expressed. However, the herbicide of the present invention does not have to be used only in such an embodiment. For example, the herbicide of the present invention can be used not only as a herbicide for paddy fields but also as a herbicide for general weeds. Such as mowing traces, fallow fields and ridges, farm roads, waterways, pasture lands, cemeteries, parks,
It can also be used to control general weeds such as roads, playgrounds, vacant lots around buildings, reclaimed land, railway tracks, and forests. In this case, it is most economically effective to treat the weeds until the beginning of the emergence of the weeds, but it is not necessarily limited to this, and it is possible to control the weeds in the growing season.

When the 3-substituted phenylpyrazole derivative represented by the general formula (I) of the present invention or a salt thereof is used as a herbicide, it should be formulated into a convenient form in accordance with a conventional method for pesticide formulation. General. That is, the 3-substituted phenylpyrazole derivative represented by the general formula (I) of the present invention or a salt thereof is blended with a suitable inert carrier or, if necessary, with an auxiliary in an appropriate ratio. Dissolved, decomposed, suspended, mixed, impregnated, adsorbed or attached,
What is necessary is just to formulate and use an appropriate dosage form, for example, a suspension, an emulsion, a liquid, a wettable powder, a granule, a powder, a tablet and the like. The inert carrier that can be used in the present invention may be either solid or liquid, and as a material that can be a solid carrier, for example, soybean flour, cereal flour, wood flour, bark flour, saw flour, tobacco stem flour,
Walnut shell powder, bran, fibrous powder, residue after extraction of plant extract, synthetic polymer such as pulverized synthetic resin, clays (eg, kaolin, bentonite, acid clay), talcs (eg, talc, pyrophyllite, etc.), Silica (for example, diatomaceous earth, silica sand, mica, white carbon [a synthetic high-dispersion silicic acid which is also called hydrous finely divided silicon or hydrous silicic acid, and which contains calcium silicate as a main component depending on the product]), activated carbon, sulfur powder, pumice stone, Examples include inorganic mineral powders such as calcined diatomaceous earth, crushed bricks, fly ash, sand, calcium carbonate, and calcium phosphate; chemical fertilizers such as ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, and salt ammonium; and compost. These are used alone or in the form of a mixture of two or more.

As a material that can be a liquid carrier, in addition to those having a solvent function per se, selected from those capable of dispersing the active ingredient compound with the aid of an auxiliary agent without having a solvent function, for example, as a representative example The following carriers can be exemplified, and these may be used alone or in the form of a mixture of two or more types. Examples thereof include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.) and ketones (eg, acetone). , Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.), ethers (eg, ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, gasoline, mineral oil, etc.), aromatic hydrocarbons (Eg benzene, tolue , Xylene, solvent naphtha,
Alkylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloroethane, chloroform, carbon tetrachloride, etc.), esters (eg, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.),
Examples include amides (eg, dimethylformamide, diethylformamide, dimethylacetamide, etc.), nitriles (eg, acetonitrile, etc.), dimethylsulfoxides, and the like.

Examples of the other adjuvants include the following representative adjuvants. These adjuvants are used according to the purpose, and may be used alone or in combination of two or more kinds. In some cases, it is possible to use no auxiliaries at all.

Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compound, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene higher fatty acid ester, polyoxyethylene Examples of surfactants such as resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonate, naphthalene sulfonic acid condensate, lignin sulfonate, higher alcohol sulfate, and the like. Can be.

For the purpose of stabilizing the dispersion of the active ingredient compound, adhering and / or binding, the following auxiliaries can be used. For example, casein, gelatin, starch, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol Auxiliaries such as pine oil, bran oil, bentonite, and lignin sulfonate can also be used.

The following auxiliaries can also be used for improving the flowability of solid products, such as waxes, stearates,
Auxiliaries such as alkyl phosphates can be used.

As a peptizer for the suspension product, a double auxiliary such as naphthalenesulfonic acid condensate, condensed phosphate and the like can also be used.

As an antifoaming agent, for example, an auxiliary agent such as silicone oil can be used.

The compounding ratio of the active ingredient compound can be adjusted according to need, for example, 0.01 to 50% by weight when it is made into a powder or granules, and 0.01 to 50% by weight when it is made into an emulsion or a wettable powder. is there.

The herbicide containing the 3-substituted pyrazole derivative represented by the general formula (I) of the present invention or a salt thereof as an active ingredient can kill various weeds or suppress the growth thereof.
Or by appropriately diluting with water or the like, or applying an amount effective for suppressing weeding or growth in a suspended form to the foliage or soil in a place where the occurrence or growth of the weed is undesirable. use.

The amount of the herbicide containing the 3-substituted pyrazole derivative represented by the general formula (I) of the present invention or a salt thereof as an active ingredient can be varied depending on various types of stamps, for example, the purpose, target weed, weed or crop occurrence / growth status, The active ingredient compound may be appropriately selected from the range of 1 g to 10 kg per hectare depending on the purpose, although it varies depending on the tendency of weed occurrence, weather, environmental conditions, dosage form, application method, application place, application time, and the like.

The herbicide containing the 3-substituted pyrazole derivative represented by the general formula (I) of the present invention or a salt thereof as an active ingredient is further used for the purpose of controlling the plant species to be controlled, suitable control period, or reducing the amount of drug. It is also possible to use a mixture with other herbicides.

The following shows typical test examples and prescription examples of the present invention,
The present invention is not limited to these.

Test Example 1. Herbicidal effect on paddy rice weeds before germination A 1 / 10,000 aret pot was filled with bed soil, seeds were sown with prepared seeds, and the soil mixed with seeds of fireflies and onions was prepared. Covered soil (1 cm) and flooded. Then, a drug containing the compound of the present invention (the compound described in Table 1) as an active ingredient was treated as a spray solution having a predetermined concentration. Twenty-one days after the treatment, the herbicidal effect was investigated, and the herbicidal rate was calculated by comparing with a non-magazine.

Judgment statement of herbicidal activity 5 .... 95% or more of weed killing.

 4 ... 70% or more and less than 95% weed killing.

 3 ... Weed killing 50% or more and less than 70%.

 2 ... 30% or more and less than 50% weed killing.

 1 ... Weed killing 10% or more and less than 30%.

 0 ... less than 10% weed killing.

 The results are shown in Table 3.

In addition, the comparative compound A was disclosed in JP-A-52-91861, No. 5
3-phenyl-5-methylthiopyrazole as described on page
B is the compound described in Example 1 on page 4 of the publication;
No. 8 described in JP-A-54-70270 and D is disclosed in
Compound No. 159 described on page 9 of JP-A 9062 was used as a comparative control compound.

Test Example 2. Herbicidal effect on paddy rice weeds after emergence A 1 / 10,000 aret pot was filled with soil, put into paddy fields, and the rice field weeds Nobie, firefly seeds, tubers of Misayayatsuri and urikawa were adjusted to the single leaf stage. .

Then, a drug containing the compound of the present invention (the compound described in Table 1) as an active ingredient was treated as a spray solution having a predetermined concentration. processing
Twenty-one days later, the herbicidal effect was investigated, and the herbicidal rate was calculated and determined in the same manner as in Test Example 1. At the same time, the phytotoxicity of paddy rice was investigated and phytotoxicity was determined according to the following criteria.

Criteria for phytotoxicity H: Large phytotoxicity.

 M …….

 L: Small phytotoxicity.

 N: No harm.

 The results are shown in Table 4.

Test Example 3. Herbicidal effect on field weeds before emergence A polyethylene vat of 10 cm in length × 20 cm in width × 5 cm in height was filled with soil, and field crops (soybean and wheat) and upland field weeds (Nobie, ichibi, Onamimomi, Seed cover of seeds of A. americana (Yeugura).

Then, a drug containing the compound of the present invention (the compound described in Table 1) as an active ingredient was treated as a spray solution having a predetermined concentration. processing
After 14 days, the herbicidal effect was examined, and the herbicidal rate was calculated and determined in the same manner as in Test Example 1. At the same time, phytotoxicity to soybean and wheat was investigated and phytotoxicity was determined according to the criteria of Test Example 2.

 The results are shown in Table 5.

Test Example 4. Herbicidal effect on field weeds after emergence A polyethylene vat measuring 10 cm in length × 20 cm in width × 5 cm in height was filled with soil, and the following field crops (soybean and wheat) and field harmful weeds (Nobie, ichibi) , Onami fir,
Sowing seeds and covering soil
Each was grown until the following leaf stage, and treated with a drug containing the compound of the present invention (the compound described in Table 1) as an active ingredient as a spray solution of a predetermined concentration. Fourteen days after the treatment, the herbicidal effect was investigated, and the herbicidal rate was calculated and determined in the same manner as in Test Example 1. At the same time, phytotoxicity to soybean and wheat was investigated and phytotoxicity was determined according to the criteria of Test Example 2.

Test weed species and their leaf stage and soybean and wheat leaf stage.

 Wheat 2 leaf stage Soybean 1 leaf stage Nobie 2 leaf stage Ichibi 2 leaf stage Onami fir 1 leaf stage Oinonufuguri 1 leaf stage Yaemugura 2 leaf stage The results are shown in Table 6.

Formulation Example 1. Compound No. 1 50 parts Clay mainly composed of clay and white carbon 45 parts Polyoxyethylene nonyl phenyl ether 5 parts The above components are uniformly mixed and pulverized to obtain a wettable powder.

Formulation Example 2. 5 parts of compound No.4 90 parts of a mixture of clay and bentonite 5 parts of calcium ligninsulfonate 5 parts or more are uniformly mixed and ground, and kneaded by adding an appropriate amount of water.
Granulate to make a powder.

Formulation Example 3 Compound No. 9 50 parts Xylene 40 parts A mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzene sulfonate 10 parts or more is uniformly mixed and dissolved to form an emulsion.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI C07D 417/04 231 C07D 417/04 231 (58) Investigated field (Int. Cl. ⁶ , DB name) C07D 403/04 C07D 413/04 C07D 417/04 CA. REGISTRY (STN)

Claims (5)

(57) [Claims] 1. The compound of the general formula (I) [Wherein, R ¹ represents a lower alkyl group, a lower haloalkyl group, a phenyl group or a phenyl group having 1 to 5 substituents which may be the same or different, and R ² represents a halogen atom, a lower alkyl group, a lower haloalkyl Group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower haloalkylthio group, a lower alkylsulfinyl group, a lower haloalkylsulfinyl group, a lower alkylsulfonyl group or a lower haloalkylsulfonyl group, and R ³ represents a hydrogen atom or a halogen atom the indicated, R ⁴ is a hydrogen atom, a lower alkyl group, lower haloalkyl group, a lower alkenyl group, a lower haloalkenyl group, a lower alkynyl group, a lower haloalkynyl group, a lower alkoxyalkyl group may be substituted by a halogen atom, a halogen atom Lower alkylthio which may be substituted by Alkyl group, cyanoalkyl group, a lower alkoxyalkoxy ^{group, -CH (R 5) CO-} Y
-R ⁶ (wherein, R ⁵ represents a hydrogen atom or a lower alkyl group,
R ⁶ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
A lower alkenyl group, a lower haloalkenyl group, a lower alkynyl group, a lower haloalkynyl group, a lower alkoxyalkyl group or a lower alkylthioalkyl group, and Y is O,
S or -N (R ⁷⁾ - (. Wherein, R ⁷ is hydrogen atom, a lower alkyl group, a lower alkenyl group or lower alkynyl group) indicates, Y in the case of O or S, R ⁶ is an alkali metal Atomic or quaternary ammonium salts can also be indicated. ), X represents a hydrogen atom or a halogen atom, A represents O,
S or —N (R ⁷ ) — (wherein R ⁷ is as defined above). The 3-substituted phenylpyrazole derivative represented by these, or its salts. 2. In the general formula (I), R ¹ represents a lower alkyl group, R ² represents a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group or a lower haloalkylthio group, and R ³ represents a halogen atom. R ⁴ is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower haloalkenyl group,
X represents a lower alkynyl group or a lower haloalkynyl group;
Represents a hydrogen atom or a halogen atom, and A represents O, S or-
N (R ⁷⁾ - (. Wherein, R ⁷ is hydrogen atom, a lower alkyl group, lower alkenyl group or a lower alkynyl group) 3-substituted phenylpyrazole derivative or a salt thereof as in claim 1 wherein indicating the. 3. A compound of the formula (I-5) (Wherein, R ¹ represents a lower alkyl group, a lower haloalkyl group, a phenyl group or a phenyl group having 1 to 5 substituents which may be the same or different, and R ² represents a halogen atom, a lower alkyl group, a lower haloalkyl A lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower haloalkylthio group, a lower alkylsulfinyl group, a lower haloalkylsulfinyl group, a lower alkylsulfonyl group or a lower haloalkylsulfonyl group, and R ³ represents a hydrogen atom or a halogen atom. X represents a hydrogen atom or a halogen atom, and A ² represents O or S.) A 3-phenyl-substituted pyrazole derivative represented by the general formula (III) R ^4-1 · Z (III) In the formula, R ^4-1 is a lower alkyl group, a lower haloalkyl group,
Lower alkenyl group, lower haloalkenyl group, lower alkynyl group, lower haloalkynyl group, lower alkoxyalkyl group optionally substituted by halogen atom, lower alkylthioalkyl group optionally substituted by halogen atom, cyanoalkyl group, lower alkoxy An alkoxyalkyl group, —CH (R ⁵ ) CO—Y—R ⁶ (wherein, R ⁵ represents a hydrogen atom or a lower alkyl group, and R ⁶ represents a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkenyl group, lower haloalkenyl group, a lower alkynyl group, a lower haloalkenyl group, a lower alkoxyalkyl group or a lower alkylthioalkyl group, Y is O, S or -N (R ⁷⁾ - (wherein, R ⁷ is a hydrogen atom, a lower Alkyl, lower alkenyl or lower alkynyl), wherein Y is O or S
In the case of R ⁶ can also represent an alkali metal atom or a quaternary ammonium salt. Z represents a halogen atom. And a halide represented by the general formula (I '): (In the formula, R ¹ , R ² , R ³ , R ^4-1 , A ² and X are the same as described above.) Or a method for producing a 3-substituted phenylpyrazole derivative or a salt thereof. 4. A compound of the formula (I) [Wherein, R ¹ represents a lower alkyl group, a lower haloalkyl group, a phenyl group or a phenyl group having 1 to 5 substituents which may be the same or different, and R ² represents a halogen atom, a lower alkyl group, a lower haloalkyl A lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a lower haloalkylthio group, a lower alkylsulfinyl group, a lower haloalkylsulfinyl group, a lower alkylsulfonyl group or a lower haloalkylsulfonyl group, and R ³ represents a hydrogen atom or a halogen atom. the indicated, R ⁴ is a hydrogen atom, a lower alkyl group, lower haloalkyl group, a lower alkenyl group, a lower haloalkenyl group, a lower alkynyl group, a lower haloalkynyl group, a lower alkoxyalkyl group may be substituted by a halogen atom, a halogen atom Lower alkylthio which may be substituted by Alkyl group, cyanoalkyl group, a lower alkoxyalkoxy ^{group, -CH (R 5) CO-} Y
-R ⁶ (wherein, R ⁵ represents a hydrogen atom or a lower alkyl group,
R ⁶ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
A lower alkenyl group, a lower haloalkenyl group, a lower alkynyl group, a lower haloalkynyl group, a lower alkoxyalkyl group or a lower alkylthioalkyl group, and Y is O,
S or —N (R ⁷ ) — (wherein R ⁷ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group), and when Y is O or S, R ⁶ is an alkali metal Atomic or quaternary ammonium salts can also be indicated. ), X represents a hydrogen atom or a halogen atom, A represents O,
S or —N (R ⁷ ) — (wherein R ⁷ is as defined above). ] The herbicide characterized by containing the 3-substituted phenyl pyrazole derivative represented by these, or its salt as an active ingredient. 5. In the general formula (I), R ¹ represents a lower alkyl group, R ² represents a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group or a lower haloalkylthio group, and R ³ represents a halogen atom. R ⁴ is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower haloalkenyl group,
X represents a lower alkynyl group or a lower haloalkynyl group;
Represents a hydrogen atom or a halogen atom, and A represents O, S or-
N (R ⁷⁾ - (wherein, R ⁷ is a hydrogen atom, a lower alkyl group, lower alkenyl group or a lower alkynyl group.) That contains the indicating 3-substituted phenylpyrazole derivative or a salt thereof as an active ingredient The herbicide according to claim 4, characterized in that: