JPH0759563B2 - Pyrazole derivative, method for producing the same, and herbicide containing the derivative as an active ingredient - Google Patents

Description

TECHNICAL FIELD The present invention relates to a pyrazole derivative, a method for producing the same, and a herbicide containing the derivative as an active ingredient.

DISCLOSURE OF THE INVENTION The pyrazole derivative of the present invention is a novel compound not described in the literature and is represented by the following general formula (I).

[In the formula, R ¹ represents a hydrogen atom or a lower alkyl group. R ² represents a hydroxy group, —OR ³ group, —SR ³ group or —NR ⁴ R ⁵ group. Here, R ³ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a benzyl group. R ⁴ and R ⁵ are the same or different and each is a hydrogen atom, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, a phenyl group which may have a substituent, a benzyl group, or a halogen atom, a cyano group, a hydroxy group and a lower alkoxy group. A lower alkyl group which may have a substituent selected from the group consisting of groups is shown. Further, R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered ring group. X ¹ represents a halogen atom, a trifluoromethyl group, a trifluoromethoxy group or a trifluoromethylthio group. X ² represents a halogen atom. n shows the integer of 1-5. , M is an integer of 1 to 4. The pyrazole derivative of the present invention represented by the above general formula (I) has excellent herbicidal activity and is useful as a herbicide. The pyrazole derivative of the present invention has a high herbicidal activity in fields and paddy fields as described below, but has an excellent feature that it has almost no effect on crops.

Examples of the compound similar to the compound of the present invention include 5-amino-4-bromo-1- as disclosed in JP-A-60-174756.
(2,3,4-trichlorophenyl) pyrazole and the like are described. However, all the compounds described in the publication have weak herbicidal activity and poor crop selectivity.

In the present specification, examples of the lower alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and isohexyl groups. An alkyl group having 1 to 6 carbon atoms can be mentioned.

Examples of the lower alkenyl group include alkenyl groups having 2 to 6 carbon atoms such as vinyl, propenyl and butenyl groups.

Examples of the lower alkynyl group include alkynyl groups having 2 to 6 carbon atoms such as ethynyl, propenyl and butynyl groups.

Examples of the cycloalkyl group include cyclopropyl, cyclopentyl, cyclohexyl, and other cycloalkyl groups having 3 to 8 carbon atoms.

Examples of the substituent of the phenyl group and the benzyl group which may have a substituent include a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a nitro group,
A cyano group etc. can be mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

As the lower alkyl group which may have a substituent selected from the group consisting of a halogen atom, a cyano atom, a hydroxy group and a lower alkoxy group, in addition to the above lower alkyl group, chloromethyl, bromomethyl, 1-chloroethyl,
2-chloroethyl, 1-bromoethyl, 2-bromoethyl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 1-bromopropyl, 2-bromopropyl, 3-bromopropyl, 1,1-dichloroethyl, 1 , 2-
Dichloroethyl, 2,2-dichloroethyl, 1,1-dibromoethyl, 1,2-dibromoethyl, 2,2-dibromoethyl,
Hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, cyanomethyl, 1
-Cyanoethyl, 2-cyanoethyl, 1-cyanopropyl, 2-cyanopropyl, 3-cyanopropyl, methoxymethyl, 1-methoxyethyl, 2-methoxyethyl,
Substitution of 1 to 6 carbon atoms such as 1-methoxypropyl, 2-methoxypropyl, 3-methoxypropyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, butoxymethyl, 1-butoxyethyl, 2-butoxyethyl groups. An alkyl group etc. can be mentioned.

Examples of the 5- or 6-membered ring group formed by combining R ⁴ and R ⁵ with each other include heterocyclic groups such as pyrrole, pyrazole, triazole, imidazole, morpholino and piperazino groups.

The compound of the present invention can be produced by various methods, but generally, it is easily produced by the methods shown in the following reaction schemes-1 and-2.

[In the formula, R ¹ , X ¹ , X ² , n and m are the same as defined above. R ² ′ represents a —OR ³ group or a —SR ³ group. R ³ is the same as above. ] [In the formula, R ¹ , X ¹ , X ² , n and m are the same as defined above. R ² ″ is -OR
³ groups, -SR ³ groups or -NR ⁴ R ⁵ groups are shown. R ³ , R ⁴ and R ⁵ are the same as above. According to the above Reaction scheme-1, the compound of the present invention represented by the general formula (Ia) is produced by halogenating the pyrazole derivative represented by the general formula (II). The reaction is carried out in a suitable solvent. Examples of the solvent used here include ethers such as diethyl ether and dibutyl ether, halogenated carbon hydrogens such as methylene chloride, chloroform, dichloroethane and carbon tetrachloride, acetic acid and the like. As the halogenating reagent used in the reaction, conventionally known ones can be widely used, for example, chlorine gas,
Bromine, thionyl chloride, thionyl bromide, sulfuryl chloride,
Examples thereof include phosphorus oxychloride. The ratio of the compound of the general formula (II) and the halogenating reagent to be used is not particularly limited, but the latter is usually used in an amount of about 0.5 to 3 times, preferably about 0.7 to 2 times the mol of the former. Is good. The above reaction may be carried out under cooling, at room temperature or under heating, but normally it suitably proceeds at around 0 to 50 ° C., and the reaction time is generally about 0.5 to 5 hours.

According to Reaction Scheme-2, the compound of the present invention represented by the general formula (Ib) hydrolyzes the pyrazole derivative represented by the general formula (Ic), and then the obtained pyrazole derivative represented by the general formula (III). Is reacted with thionyl chloride, and the resulting pyrazole derivative represented by the general formula (IV) is reacted with a compound represented by the general formula (V).

The hydrolysis reaction of the compound of the general formula (Ic) is carried out in an alkaline solution of alcohols such as methyl alcohol and ethyl alcohol, water and the like or a mixed solvent thereof. Examples of the alkaline substance used here include sodium hydroxide and potassium hydroxide. The concentration of alkali in the alkaline solution is not particularly limited, but it is usually about 0.01 to 10% by weight.
The hydrolysis reaction can be carried out either at room temperature or under heating, but normally it suitably proceeds at room temperature to around 100 ° C., and the reaction time is generally about 0.5 to 5 hours.

The reaction of the compound of the general formula (III) thus obtained with thionyl chloride is usually carried out in a suitable solvent. Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane and carbon tetrachloride. The ratio of the compound of the general formula (III) and thionyl chloride to be used is not particularly limited, but usually the latter is used in an amount of about 0.5 to 5 times mol, preferably about 1 to 3 times mol for the former. Is good. The above reaction generally proceeds suitably at about 50 to 150 ° C., and the reaction time is generally about 1 to 10 hours. The compound of the general formula (IV) thus obtained can be directly used in the next reaction with or without isolation.

The reaction between the compound of general formula (IV) and the compound of general formula (V) is carried out without solvent or in a suitable solvent. Examples of the solvent used here include ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, methylene chloride, chloroform, dichloroethane,
Examples thereof include halogenated hydrocarbons such as carbon tetrachloride and aromatic hydrocarbons such as benzene, toluene and xylene. The ratio of the compound of the general formula (IV) and the compound of the general formula (V) to be used is not particularly limited, but usually the latter is about 0.5 to 5 times mol, preferably 0.7 to 4 times the latter. It is advisable to use about twice the molar amount. In the present invention, it is preferable to allow a basic compound to exist in the reaction system of the above reaction. As the basic compound, conventionally known compounds can be widely used as long as they can capture hydrogen chloride produced by the reaction, and for example, tertiary amines such as triethylamine, tributylamine, dimethylaniline, diethylaniline, pyridine. And pyridines such as picoline. When the compound of the general formula (V) used is an amine derivative, it can also be used as a basic compound. The amount of such a basic compound to be used is usually 0.5 to 5 with respect to the compound of the general formula (IV).
It is about 5 times mol, preferably about 0.7 to 4 times mol. The above reaction can be carried out under cooling, at room temperature or under heating, but normally it suitably proceeds at room temperature to around 100 ° C., and the reaction time is generally about 1 to 10 hours.

In the above Reaction Scheme-1, the compound of the general formula (II) used as a starting material is a novel compound, and the compound is produced, for example, by the method shown in the following Reaction Scheme-3.

[Wherein R ¹ , R ² ′, X ¹ , n and m are the same as above. X ³ and X ⁴
Are differently a halogen atom or a hydroxy group. ].

The reaction represented by Reaction Formula-3 is performed without solvent or in a suitable solvent. Examples of the solvent used here include ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane and carbon tetrachloride, alcohols such as methyl alcohol and ethyl alcohol. , Dimethylformamide, dimethylsulfoxide, water and the like. The ratio of the compound of the general formula (VI) and the compound of the general formula (VII) to be used is not particularly limited, but usually the latter is used for the former.
It is recommended to use about 0.5 to 2 times mol, preferably about 0.7 to 1.5 times mol. In the present invention, it is preferable to allow a basic compound to exist in the reaction system of the above reaction. As the basic compound, conventionally known compounds can be widely used as long as they can capture the hydrogen halide produced by the reaction,
For example, sodium carbonate such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, metallic sodium, sodium methylate and sodium ethylate, sodium hydride, triethylamine, tributylamine, tertiary amine such as dimethylaniline and diethylaniline. And the like. The amount of such a basic compound used is usually 0.5 with respect to the compound of the general formula (VI).
It is about 2 to 2 times mol, preferably about 0.7 to 1.5 times mol. The above reaction can be carried out either at room temperature or under heating, but normally proceeds suitably at room temperature to around 150 ° C,
The reaction time is generally about 0.5 to 5 hours.

Further, the compound of the present invention represented by the general formula (Ic) used as a starting material in Reaction scheme-2 can be easily produced according to the method shown in the above Reaction scheme-1.

The compound of the present invention obtained by the above method can be easily isolated and purified from the reaction mixture by a usual separation means, for example, solvent extraction method, solvent dilution method, recrystallization method, column chromatography, etc. The compounds of the invention may be prepared in high purity.

The compound of the present invention has high herbicidal activity in upland fields and paddy fields, and has an excellent feature that it exerts almost no effect on crops. The compound of the present invention is, for example, in the field, against white clover, swordfish, indigo, speruhiyu, barkwood, burlap, harsh grass, Enocologsa, Prunus chinensis, cyperaceae, agasa, velvetleaf, morning glory, Jihonson grass, etc., and in the paddy field, for example. It is possible to exert a controlling effect on pre-emergence treatment and weeding season treatment of weeds against such as Azena, Scutellariae, Rhizoma edulis, Pleurotus cornucopiae, Pleurotus cornucopiae, Konagi, Firefly, Spodoptera litura, Urikawa. On the other hand, the compound of the present invention is resistant to crops such as rice, soybean, sunflower, cotton, wheat and corn, and can be used as a selective herbicide.

As described above, the compound of the present invention has safety against crops while having a very broad herbicidal spectrum, and therefore controls weeds in paddy fields, various vegetables, various cereals, fruit trees, mulberry fields, and non-crop lands. Can be used effectively.

When the compound of the present invention is applied as a herbicide, the compound of the present invention may be used as it is, but it is generally used by mixing it with an auxiliary agent usually used in the formulation of agricultural chemicals. The dosage form is not particularly limited, but powders, emulsions, wettable powders, flowables and granules are preferable.
As the auxiliary agent, those usually used in this field can be widely used, for example, diatomaceous earth, kaolin, clay, bentonite, white carbon, extenders such as talc, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether. , Polyoxyethylene sorbitan fatty acid ether, polyoxyethylene fatty acid ether, sodium alkylbenzene sulfonate, sodium lignin sulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, surfactants such as sodium polyoxyethylene alkyl sulfate, benzene, toluene, xylene, acetone, cyclohexanone, Examples thereof include organic solvents such as methanol, ethanol, isopropyl alcohol, dioxane, dimethylformamide, dimethyl sulfoxide, carbon tetrachloride and the like.

The amount of the compound of the present invention to be blended in the herbicide of the present invention is not particularly limited, but it is preferable to appropriately add the above-mentioned auxiliary agents so that the active ingredient is usually about 0.1 to 90% by weight.

In using the herbicide of the present invention, the herbicide of the present invention may be sprayed as it is without being diluted, 500 to 500
You may dilute about 0 times and spray. Appropriate amount of application depends on the formulation form of the drug, application method, application time, target weeds, etc. and cannot be said unequivocally, but when normally used in paddy fields, the active ingredient is 0.01 to 5 kg / ha, preferably 0.05 to 2 kg / When used in the field, the active ingredient should be 0.05 to 5k
It is recommended to spray so as to be g / ha, preferably 0.1 to 3 kg / ha.

EXAMPLES The present invention will be further clarified with reference to Reference Examples, Examples, Formulation Examples and Test Examples below.

Reference Example 1 Production of ethyl 2- [1- (2,3,4-trichlorophenyl) pyrazol-5-yloxy] propionate 2.6 g of 60% oily sodium hydride was washed with dry hexane to remove mineral oil. After that, 100 ml of dimethylformamide
Suspended in. Under cooling and stirring, 1- (2,3,
4-Trichlorophenyl) pyrazol-5-one 15.2 g of dimethylformamide solution 100 ml was gradually added dropwise. Then, 50 ml of a dimethylformamide solution containing 10.5 g of ethyl α-bromopropionate was gradually added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 1 hour. The reaction mixture was poured into diluted hydrochloric acid containing crushed ice, acidified with hydrochloric acid, and extracted with chloroform (× 3 times). The chloroform extract was washed with water, dried, and concentrated under reduced pressure to obtain 20.3 g of the desired product as a reddish orange oil.

Example 1 Preparation of ethyl 2- [4-bromo-1- (2,3,4-trichlorophenyl) pyrazol-5-yloxy] propionate 2- [1- (2,3,4-trichlorophenyl) To 150 ml of a carbon tetrachloride solution containing 20.3 g of ethyl pyrazol-5-yloxy] propionate, 30 ml of a carbon tetrachloride solution containing 8.93 g of bromine was added dropwise over 30 minutes with stirring under cooling. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After 100 ml of chloroform was added to the reaction mixture to make it uniform, the reaction mixture was transferred to a liquid separation route, and washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated saline. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain 19.8 g of the desired product as a red-orange oily substance.

The NMR spectrum of the above oily substance in deuterated chloroform was
It was as follows.

δ (ppm): 1.20 (t, 3H), 1.47 (d, 3H), 4.05 (q, 2H), 5.10 (q, 1H), 7.23 (d, 1H), 7.38 (s, 1H), 7.40 (d , 1H) Elemental analysis value (C ₁₄ H ₁₂ N ₂ O ₃ BrCl ₃ = 442.527) C H N actual value (%) 37.88 2.81 6.02 Calculated value (%) 38.00 2.73 From the above 6.33 results It was confirmed.

Example 2 Preparation of 2- [4-bromo-1- (2,3,4-trichlorophenyl) pyrazol-5-yloxy] propionic acid 2- [4-Bromo-1- (2,3,4-trichloro) Phenyl) pyrazol-5-yloxy] ethyl propionate
Dissolve 21 g in 130 ml ethanol and add 20% (w / v) to it.
20 ml of an aqueous sodium hydroxide solution was added, and the mixture was heated under reflux for 30 minutes. The reaction mixture was allowed to cool to room temperature, ethanol was distilled off under reduced pressure, water was added to the obtained residue, and the mixture was extracted with chloroform. The aqueous layer was acidified with concentrated hydrochloric acid, and the precipitated gum-like substance was extracted with chloroform. The chloroform layer was dried and concentrated under reduced pressure to obtain 19.8 g of the desired product as a reddish orange oil.

The NMR spectrum of the above oily substance in deuterated chloroform was
It was as follows.

δ (ppm): 1.49 (d, 3H), 5.14 (q, 1H), 7.13 (d, 1H), 7.31 (d, 1H), 7.40 (s, 1H), 9.57 (s, 1H) Elemental analysis value ( C ₁₂ H ₈ N ₂ O ₃ BrCl ₃ = 414.473) C H N actual value (%) 34.81 2.03 6.59 Calculated value (%) 34.77 1.95 6.76 From the above results It was confirmed.

Example 3 Preparation of ethyl 2- [4-chloro-1- (2,3,4-trichlorophenyl) pyrazol-5-yloxy] propionate 2- [1- (2,3,4-trichlorophenyl) A solution of ethyl pyrazol-5-yloxy] propionate (15.0 g) in carbon tetrachloride (120 ml) was added dropwise over 30 minutes. After the dropping is completed,
Stirred for another 30 minutes at room temperature. About 50 ml of chloroform was added to the reaction mixture to make it uniform, and then transferred to a separating funnel,
The extract was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give the desired product (15.5 g) as an orange-yellow oil.

The NMR spectrum of the above oily substance in deuterated chloroform was
It was as follows.

δ (ppm): 1.18 (t, 3H), 1.47 (d, 3H), 4.05 (q, 2H), 5.09 (q, 1H), 7.18 (d, 1H), 7.32 (s, 1H), 7.38 (d , 1H) Elemental analysis value (C ₁₄ H ₁₂ N ₂ O ₃ Cl ₄ = 398.076) CHN measured value (%) 42.21 3.12 7.11 Calculated value (%) 42.24 3.04 7.04 From the above results It was confirmed.

Example 4 Preparation of 2- [4-chloro-1- (2,3,4-trichlorophenyl) pyrazol-5-yloxy] propionic acid 2- [4-chloro-1- (2,3,4-trichloro Phenyl) pyrazol-5-yloxy] ethyl propionate
11.0 g was dissolved in 80 ml of ethanol, 11 ml of 20% (w / v) sodium hydroxide aqueous solution was added thereto, and the mixture was heated under reflux for 30 minutes. The reaction mixture was allowed to cool to room temperature, ethanol was distilled off under reduced pressure, water was added to the obtained residue, and the mixture was extracted with chloroform. The aqueous layer was acidified with concentrated hydrochloric acid, and the precipitated gum-like substance was extracted with chloroform. The chloroform layer was dried and concentrated under reduced pressure to give the desired product (9.5 g) as a brown oil.

The NMR spectrum of the above oily substance in deuterated chloroform was
It was as follows.

δ (ppm): 1.49 (d, 3H), 5.10 (q, 1H), 7.09 (d, 1H), 7.28 (d, 1H), 7.32 (s, 1H), 8.70 (s, 1H) Elemental analysis value ( C ₁₂ H ₈ N ₂ O ₃ Cl ₄ = 370.022) C H N measured value (%) 38.76 2.23 7.46 Calculated value (%) 38.95 2.18 7.57 From the above results It was confirmed.

Example 5 Preparation of 2- [4-bromo-1- (2,3,4-trichlorophenyl) pyrazol-5-yloxy] propionic acid chloride 2- [4-Brom-1- (2,3,4- Trichlorophenyl) pyrazol-5-yloxy] propionic acid 20.1
A mixture of g, 100 ml of chloroform and 11.6 g of thionyl chloride was gently heated to reflux for 2 hours. After completion of the reaction, chloroform and excess thionyl chloride were distilled off under reduced pressure to obtain 20.0 g of acid chloride as a dark brown oily substance.

This product was used in the next reaction without purification.

Example 6 Preparation of 2- [4-bromo-1- (2,3,4-trichlorophenyl) pyrazol-5-yloxy] propionic acid benzylamide 10.0 g of the acid chloride obtained in Example 5 is added to 120 ml of methylene chloride. Dissolved. While cooling and stirring, 50 ml of a methylene chloride solution containing 7.5 g of benzylamine was gradually added dropwise. After the dropping is completed,
The reaction mixture was returned to room temperature and further stirred for 30 minutes. The reaction mixture was poured into diluted hydrochloric acid containing crushed ice, acidified with hydrochloric acid, and extracted with chloroform. The chloroform extract was washed with saturated brine, dried and concentrated under reduced pressure to give 10.5 g of crude product.
Was obtained as a brown oil.

The NMR spectrum of the above oily substance in deuterated chloroform was
It was as follows.

δ (ppm): 1.35 (d, 3H), 4.24 (d, 2H), 4.80 (q, 1H), 6.62 (t, 1H), 7.0 to 7.3 (m, 7H), 7.35 (s, 1H) Elemental analysis Value (C ₁₉ H ₁₅ N ₃ O ₂ BrCl ₃ = 503.613) C H N actual value (%) 45.36 2.96 8.21 Calculated value (%) 45.31 3.00 8.34 From the above results It was confirmed.

Example 7 Preparation of 2- [4-chloro-1- (2,3,4-trichlorophenyl) pyrazol-5-yloxy] propionic acid chloride 2- [4-chloro-1- (2,3,4- 3.2 g of trichlorophenyl) pyrazol-5-yloxy] propionic acid,
A mixture of 30 ml of chloroform and 2.4 g of thionyl chloride was gently heated to reflux for 2 hours. After completion of the reaction, chloroform and excess thionyl chloride were distilled off under reduced pressure to obtain 3.4 g of acid chloride as a brown oily substance.

This product was used in the next reaction without purification.

Example 8 Preparation of 2- [4-chloro-1- (2,3,4-trichlorophenyl) pyrazol-5-yloxy] propionic acid benzyl ester 3.4 g of the acid chloride obtained in Example 7 in 35 ml of methylene chloride Was dissolved in, and 1.2 g of benzyl alcohol was added thereto. While cooling and stirring, 10 ml of a methylene chloride solution containing 0.9 g of pyridine was gradually added dropwise to this mixture. After the dropping, the reaction mixture was returned to room temperature and further stirred for 30 minutes. The reaction mixture was poured into diluted hydrochloric acid containing crushed ice, acidified with hydrochloric acid, and extracted with chloroform. The chloroform extract was washed with saturated brine, dried and concentrated to give 4.0 g of a crude product as a reddish orange oil.

The NMR spectrum of the above oily substance in deuterated chloroform was
It was as follows.

δ (ppm): 1.45 (d, 3H), 4.96 (s, 2H), 5.15 (q, 1H), 7.09 (t, 1H), 7.0 to 7.2 (m, 2H), 7.39 (s, 1H) Elemental analysis Value (C ₁₉ H ₁₄ N ₂ O ₃ Cl ₄ = 460.147) C H N Actual value (%) 49.46 3.05 5.98 Calculated value (%) 49.59 3.07 6.09 From the above results It was confirmed.

Examples 9 to 78 The compounds of Examples 9 to 78 were produced in the same manner as in Reference Example 1 and Examples 1 to 8. The physical properties of the compound are shown in Table 1.

Formulation Example 1 Emulsion parts by weight Compound of the present invention 30 Polyoxyethylene alkylphenyl ether 12 Sodium alkylbenzenesulfonate 3 Xylene 55 100 The above various components were well mixed and stirred to obtain a 30% emulsion.

Formulation Example 2 Wettable powder parts by weight Compound of the present invention 30 White carbon 40 Diatomaceous earth 15 Sodium lauryl sulfate 3 2,2'-Dinaphthylmethanesulfonic acid sodium salt 2 Alkylphenylphenol sulfate 10 100 The above various components are mixed using a mixer. After mixing well, it was pulverized with a pulverizer to obtain 30% wettable powder.

Formulation Example 3 Granules Part by weight Compound of the present invention 5 Synthetic hydrous silicon oxide 1 Calcium lignin sulfonate 2 Bendite 25 Kaolin clay 67 100 The above components are well pulverized and mixed, and water is well kneaded, and then granulated and dried. Then, 5% granules were obtained.

Test Example 1 Paddy field weeding before emergence Flood treatment 1/5000 ares of Wagner pots were filled with a certain amount of paddy soil for planting, and seeds of Tainubie, broad-leaved leaves (Koenagi, Kishigusa, Azena and Mizohakobe) and cypress (Cyperus japonicus) were fixed. The amount was seeded. Furthermore, tubers of Urikawa were embedded at a depth of 1 cm from the surface layer of the soil, and water was poured at a depth of 3 cm, and then the wettable powder prepared in Formulation Example 2 was treated with 1.5 g, 3.0 g, 6.0 g of the active ingredient per are. dilute to g,
It was dropped into the submerged water. After another 3 days, rice seedlings at the 2.5 leaf stage were transplanted. The herbicidal effect and the presence or absence of phytotoxicity on rice were investigated 30 days after the chemical treatment. The results are shown in Table 2.
The survey criteria were as follows. The compound No. in Table 2 corresponds to the above Example No. The same applies to Tables 3 and 4 below.

Weeding effect index 5: Complete weeding 4: 80% weeding 3: 60% 〃 2: 40% weeding 1: 20% 〃 0: No efficacy Drug damage index −: Harmless ＋: Minor harm ： Small harm ： Medium Harm: Very bad x: Withered Test Example 2 Weed pre-emergence soil treatment A pot with a diameter of 8 cm was filled with a fixed amount of field soil, and
Sow seeds of Enocorogosa, Inubiyu and Polygonum soybeans,
I covered about 1 cm of soil. The wettable powder prepared in Formulation Example 2 was diluted so that the active ingredient was 15 g and 30 g per are, and the whole soil was treated. The herbicidal effect was investigated on the 20th day of drug treatment. The results are shown in Table 3. The investigation criteria are the same as in Test Example 1.

Test Example 3 Weeding period treatment Pots with a diameter of 8 cm were filled with a fixed amount of field soil, and
When the seeds of Enocorogusa, Inubiyu, and Japanese Polygonum are sown and grown, and grown in the 3 to 4 leaf stage, the wettable powder prepared in Formulation Example 2 is diluted so that the active ingredient per Earl is 7.5 g and 15 g, Sprayed on plants. The herbicidal effect was investigated 20 days after the chemical treatment. The results are shown in Table 4. The investigation criteria are the same as in Test Example 1.

Claims (4)

[Claims] 1. A general formula [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group. R ² represents a hydroxy group, —OR ³ group, —SR ³ group or —NR ⁴ R ⁵ group. Here, R ³ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a benzyl group. R ⁴ and R ⁵ are the same or different and each is a hydrogen atom, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, a phenyl group which may have a substituent, a benzyl group, or a halogen atom, a cyano group, a hydroxy group and a lower alkoxy group. A lower alkyl group which may have a substituent selected from the group consisting of groups is shown. Further, R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered ring group. X ¹ represents a halogen atom, a trifluoromethyl group, a trifluoromethoxy group or a trifluoromethylthio group. X ² represents a halogen atom. n is an integer of 1 to 5 and m is an integer of 1 to 4. ] The pyrazole derivative represented by these. 2. General formula [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group. R ² ′ is
Indicates an -OR ³ group or a -SR ³ group. Where R ³ is a lower alkyl group,
A lower alkenyl group, a lower alkynyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a benzyl group is shown. X ¹ is a halogen atom, a trifluoromethyl group,
A trifluoromethoxy group or a trifluoromethylthio group is shown. n is an integer of 1 to 5 and m is an integer of 1 to 4. ] A general formula characterized by halogenating a pyrazole derivative represented by [Wherein R ¹ , R ² ′, X ¹ , n and m are the same as above. X ² represents a halogen atom. ] The manufacturing method of the pyrazole derivative represented by these. 3. General formula [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group. X ¹ represents a halogen atom, a trifluoromethyl group, a trifluoromethoxy group or a trifluoromethylthio group. X ² represents a halogen atom. n is an integer of 1 to 5 and m is an integer of 1 to 4. ] The pyrazole derivative represented by [In the formula, R ¹ , X ¹ , X ² , n and m are the same as defined above. ] The general formula obtained by reacting a pyrazole derivative represented by [In the formula, R ¹ , X ¹ , X ² , n and m are the same as defined above. ] The pyrazole derivative represented by the general formula H—R ² ″ [wherein R ² ″ represents a —OR ³ group, a —SR ³ group or a —NR ⁴ R ⁵ group. Here, R ³ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a benzyl group. R ⁴ and R ⁵ are the same or different and each is a hydrogen atom, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, a phenyl group which may have a substituent, a benzyl group, or a halogen atom, a cyano group, a hydroxy group and a lower alkoxy group. A lower alkyl group which may have a substituent selected from the group consisting of groups is shown. Further, R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered ring group. ] A general formula characterized by reacting a compound represented by [Wherein R ¹ , R ² ″, X ¹ , X ² , n and m are the same as defined above]. 4. A general formula [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group. R ² represents a hydroxy group, —OR ³ group, —SR ³ group or —NR ⁴ R ⁵ group. Here, R ³ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a benzyl group. R ⁴ and R ⁵ are the same or different and each is a hydrogen atom, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, a phenyl group which may have a substituent, a benzyl group, or a halogen atom, a cyano group, a hydroxy group and a lower alkoxy group. A lower alkyl group which may have a substituent selected from the group consisting of groups is shown. Further, R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered ring group. X ¹ represents a halogen atom, a trifluoromethyl group, a trifluoromethoxy group or a trifluoromethylthio group. X ² represents a halogen atom. n is an integer of 1 to 5 and m is an integer of 1 to 4. ] A herbicide containing a pyrazole derivative represented by the following as an active ingredient.