JP2001233861A - Pyrazole oxime compounds, their production and use - Google Patents

Abstract

(57) [Problem] To provide a herbicide and a fungicide characterized by containing a pyrazole oxime compound as an active ingredient. SOLUTION: The herbicide of the present invention has the following formula (1): [Wherein R ¹ represents a C1-4 alkyl group or the like;
² represents a C1~4 alkyl group; R ^3, a phenoxy group, and a halogen atom; R ⁴ is a hydrogen atom, and 1 to 5 alkyl groups of carbon atoms; R ⁵ is a carbon A represents an alkyl group having 1 to 5 atoms, an alkenyl group having 3 to 5 carbon atoms, and the like; A represents a sulfur atom, NR ⁶ (R
⁶ represents a hydrogen atom, a C1-5 alkyl group or the like. )
Represents ] As an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel pyrazole oxime compound, a method for producing the same, and a herbicide or fungicide containing the compound as an active ingredient.

[0002]

2. Description of the Related Art The following compounds (1) and (2) are known as compounds similar to the compound of the present invention. However, the compound of the present invention is a novel compound. The use as a herbicide and a bactericide as shown in the above was not known. (1) JP-A-3-68559 and JP-A-7-173
No. 155 It is described that a carbohydroxymoylazole compound in which a heterocycle is bonded to an oxime carbon has insecticidal activity. (2) JP-A-10-95771 It is described that a compound having a heterocycle and an amino group on an oxime carbon has a bactericidal activity. But,
The amino group is only a substituted carbonylamino group.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a pyrazole oxime compound, a method for producing the same, and a herbicide and a fungicide containing the compound as an active ingredient.

[0004]

Means for Solving the Problems The present inventors have conducted studies to solve the above problems, and as a result, have found that the novel oxime derivative has remarkable agricultural and horticultural herbicidal activity and fungicidal activity. The present invention has been completed. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0005]

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[Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; R ² represents 1 to 4 carbon atoms.
R ³ represents a phenoxy group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a phenylthio group; R ⁴ represents hydrogen; atoms, containing 1-5 alkyl group having a carbon atom, the carbon atoms 1-5 haloalkyl group, a benzyl group, 2-5 acyl group carbon atoms, represents a benzoyl group, R ⁵ has a number of carbon atoms An alkyl group having 1 to 5 alkyl groups, an alkenyl group having 3 to 5 carbon atoms, an alkynyl group having 3 to 5 carbon atoms, a phenyl group, a benzyl group, a morpholinyl group, and an alkylene chain having 2 to 4 carbon atoms. A represents a sulfur atom, NR ⁶ (where R ⁶ is a hydrogen atom, a phenyl group, an alkoxyalkyl group having 2 to 6 carbon atoms)
Represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, an alkynyl group having 3 to 5 carbon atoms, or "6 or 6 together with R ⁵ together with a nitrogen atom.
A 6-membered ring which forms a membered ring and one of the carbon atoms at any position in the ring may be an oxygen atom ". ). And a pyrazole oxime compound represented by the formula: The second invention provides the following formula (2):

[0007]

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(Wherein, R ^{1 to} R ³ are as defined above;
Q represents a halogen atom. )). A third invention relates to a compound represented by the above formula (2) and a compound represented by the following formula (3):

[0009]

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(Wherein R ⁵ is as defined above) or the following formula (4):

[0011]

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(Wherein R ⁵ and R ⁶ are as defined above), and further reacted with a compound represented by the following formula (5):

[0013]

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(Wherein X represents a halogen atom; R ⁴
Is as defined above. The present invention relates to a method for producing a pyrazole oxime compound represented by the above formula (1), characterized by reacting a compound represented by the formula (1).
A fourth invention relates to a herbicide comprising the compound represented by the formula (1) as an active ingredient. A fifth invention relates to a bactericide comprising the compound represented by the formula (1) as an active ingredient.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Equations (1), (2), (3),
The compounds represented by (4) and (5) are hereinafter also referred to as compounds (1), (2), (3), (4) and (5) in order from the left. The compounds (1) and (2) of the present invention can be converted into salts such as, for example, sulfates, hydrochlorides, nitrates and phosphates. And their salts can also be included in the present invention. Compounds (1) and (2) have E-form and Z-form geometric isomers, and the present invention can also include these isomers and mixtures. R ^{1 to} R ⁶ and A of the compounds (1) to (5) shown in the present invention
Is as follows.

[R ¹ ] Examples of R ¹ include an alkyl group having 1 to 4 carbon atoms and a phenyl group. (1) The alkyl group is linear or branched; preferably, it has 1 to 4 carbon atoms;
More preferably, it is a methyl group. (2) The phenyl group may be unsubstituted or substituted; the substituent may be an alkyl group, a halogen atom or the like; preferably unsubstituted.

[R ² ] Examples of R ² include an alkyl group having 1 to 4 carbon atoms. Alkyl groups are straight-chain or branched; preferably have 1 to 4 carbon atoms; more preferably a methyl group.

[R ³ ] R ³ is a phenoxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms. , Phenylthio group. (1) The phenoxy group may be unsubstituted or substituted; examples of the substituent include an alkyl group and a halogen atom; preferably a halogen atom; more preferably, It is a chlorine atom. (2) Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom; preferably a chlorine atom. (3) The alkyl group is linear or branched; preferably, it has 1 to 3 carbon atoms; more preferably, it is a methyl group. (4) The alkoxy group is linear or branched; preferably, it has 1 to 3 carbon atoms; more preferably, it is a methoxy group. (5) The alkylthio group is linear or branched; preferably, it has 1 to 3 carbon atoms; more preferably, it is a methylthio group. (6) The phenylthio group may be unsubstituted or substituted; and the substituent may have 1 to 4 carbon atoms.
Alkyl groups, halogen atoms, etc .; preferably halogen atoms; and more preferably chlorine atoms.

[R ⁴ ] R ⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a benzyl group, an acyl group having 2 to 5 carbon atoms. , Benzoyl group. (1) The alkyl group is linear or branched; preferably, it has 1 to 4 carbon atoms;
More preferably, it is a methyl group. (2) The haloalkyl group is linear or branched; preferably, it has 1 to 4 carbon atoms; more preferably, it is a fluoroethyl group. (3) The benzyl group may be unsubstituted or substituted; the substituent may be an alkyl group, a halogen atom, or the like; preferably unsubstituted. (4) the acyl group is linear or branched;
Preferably, it has 2 to 4 carbon atoms; more preferably, it is an acetyl group. (5) The benzoyl group may be unsubstituted or substituted; examples of the substituent include an alkyl group and a halogen atom; and preferably, unsubstituted.

[R ⁵ ] R ⁵ is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, an alkynyl group having 3 to 5 carbon atoms, a phenyl group or a benzyl group. , A morpholinyl group, a phenyl group having an alkylene chain having 2 to 4 carbon atoms, and an alkoxyalkyl group having 1 to 6 carbon atoms. (1) The alkyl group is linear or branched; preferably, it has 1 to 4 carbon atoms;
More preferred are a methyl group and an i-propyl group. (2) The alkenyl group is linear or branched; preferably, it has 3 to 4 carbon atoms;
More preferably, it is an allyl group. (3) The alkynyl group is linear or branched; preferably, it has 3 to 4 carbon atoms;
More preferably, it is a propargyl group.

(4) The phenyl group may be unsubstituted or substituted; examples of the substituent include an alkyl group having 1 to 4 carbon atoms and a halogen atom; Is an alkyl group; more preferably a methyl group. (5) The morpholinyl group is preferably, for example, one represented by R ⁴ of compound No. 11 in Table 2 described below. (6) The phenyl group having an alkylene chain is an unsubstituted or substituted phenyl group in which the alkylene chain is linear or branched; preferably, the alkylene chain has 1 or 2 carbon atoms, The phenyl group is an unsubstituted or substituted alkenyl group having 1 to 4 carbon atoms. (7) The alkoxyalkyl group is linear or branched; preferably, it has 3 to 5 carbon atoms; more preferably, it is an ethoxyethylene group.

[A] Examples of A include a sulfur atom and NR ⁶ . R ⁶ is a hydrogen atom or a carbon atom having 1 to 1
Represents 5 alkyl groups, alkenyl groups having 3 to 5 carbon atoms, alkynyl groups having 3 to 5 carbon atoms, or "forms a 6-membered ring together with a nitrogen atom together with R5, A 6-membered ring in which one of the carbon atoms at any position in the ring may be an oxygen atom.

(1) The alkyl group is linear or branched; preferably, it has 1 to 4 carbon atoms; more preferably, methyl or i-propyl. It is. (2) The alkenyl group is linear or branched; preferably, it has 3 to 4 carbon atoms;
More preferably, it is an allyl group. (3) The alkynyl group is linear or branched; preferably, it has 3 to 4 carbon atoms;
More preferably, it is a propargyl group. (4) “A 6-membered ring which together with R ⁵ forms a 6-membered ring together with a nitrogen atom, and one of the carbon atoms at any position in the ring may be an oxygen atom” is represented by “R ⁵ and R ⁶ together form a saturated 6-membered ring together with the nitrogen atom, wherein one of the carbon atoms at any position in the ring may be an oxygen atom. A ring "; preferably, for example, as shown by R ⁴ of compound numbers 8, 9 in Table 2 below.

As the compound (1), a compound obtained by combining the above-mentioned various substituents can be mentioned. From the viewpoint of efficacy, the following compounds are preferred. (1) A compound (1) in which R ¹ , R ² , R ⁴ , and R ⁵ are an alkyl group having 1 to 4 carbon atoms, R ³ is a phenoxy group, and A is NR ⁶ . For example, compound number 23 described in Table 3 can be mentioned. (2) A compound (1) in which R ¹ , R ² , and R ⁴ are an alkyl group having 1 to 4 carbon atoms, R ³ is a phenoxy group, and A is a sulfur atom. For example, Compound No. 31 described in Table 4
Can be mentioned.

(3) R ¹ , R ² , R ⁴ and R ⁵ are an alkyl group having 1 to 4 carbon atoms, R ³ is a halogen,
Compound (1) wherein A is NR ⁶ . For example, compound numbers 33 and 39 described in Table 4 can be exemplified. (4) R ¹ , R ² , R ⁴ are an alkyl group having 1 to 4 carbon atoms, R ³ is a halogen atom, R ⁵ is an alkenyl group having 3 to 4 carbon atoms, Is NR ⁶ . For example, Compound No. 34 described in Table 4 can be mentioned. (5) R ¹ , R ² and R ⁴ are an alkyl group having 1 to 4 carbon atoms, R ³ is a phenoxy group, R ⁵ is an alkynyl group having 3 to 4 carbon atoms, Is NR ⁶ . For example, compound number 25 described in Table 3 can be mentioned.

The compounds of the present invention (1), the compound (2) with the corresponding compound (3) or compound (4) is reacted in the presence of a solvent or without solvent, the compound of R ⁴ is a hydrogen atom (1 ) Can be obtained. Further, the compound (5) is reacted with a base in the presence of a solvent or without a solvent to obtain a compound (1) having R ⁴ other than H. Compound (2) used to obtain compound (1) of the present invention is described in J. Am. Org. Ch
em. USSR. 1985, Vol. 21 No. 1
Pyrazole oximes produced by the method described in, for example,
-Bromosuccinimide can be obtained by halogenation with a halogenating agent such as imide. Compounds (3), (4) and (5) can be purchased commercially. Examples of the compound (2) include the compound numbers (2-1) to (2-4) shown in Table 1 below (for example, the compound number (2-1) refers to the compound (2) in the compound (2)). R ¹ and R ² are methyl groups, R ³ is a chlorine atom,
It means that Q is a chlorine atom. ]. Compound (1)
Are the compound numbers 1 to 4 shown in Tables 2 to 4 below.
[For example, compound number 1 is
R ^{1 to} R ³ and R ⁵ in the compound (1) are methyl groups, R ⁴ is a hydrogen atom, and A is NR ⁶ ].

The compound of the present invention has a remarkable herbicidal effect or a bactericidal effect, and contains at least one compound (1) as an active ingredient. The active compounds of the invention are effective, for example, on the following weeds and can be used as herbicides for paddy and field crops. As monocotyledon weeds, there are nobies, fireflies, mizuya-yatsuri, tamayatsuri,
Paddy field weeds such as Heramodaka, Konagi, and Urikawa; and field weeds such as Meechishiba, Ohishiba, Enokorogosa, Suzumenotepo, and Suzumeokatabira. Examples of dicotyledonous weeds include paddy field weeds such as Azena, Kikasigusa and Seri; and field weeds such as Shiroza, Inubeyu, Ichibai, Asagao, Onamimomi, Ebisugusa and Nachobe. The active compounds of the present invention can be applied both before and after germination of plants,
The soil can be mixed before sowing.

The dosage of the active compounds according to the invention can be varied over a wide range depending on the type of compound, the type of plant to be applied, the time of application, the place of application, the nature of the desired effect, etc .; Can be used as active compound from about 0.001 to 10 kg per hectare; preferably from 0.01 to 5 kg. The compound (1) can be used alone, but it is usually compounded with a diluent, a surfactant, a dispersant, an auxiliary agent and the like by a usual method, and for example, powders, emulsions, fine granules, granules, It is preferable to prepare and use such compositions as wettable powders, wettable powders, aqueous suspensions, oil suspensions, emulsions, solubilized preparations, oils, microcapsules, aerosols and the like.

Examples of the solid diluent include talc, bentonite, montmorillonite, clay, kaolin, calcium carbonate, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea. Examples of the liquid diluent include hydrocarbons such as kerosene and mineral oil; aromatic hydrocarbons such as benzene, toluene, xylene, dimethylnaphthalene and phenylxylylethane; chlorinated hydrocarbons such as chloroform and tetrachloromethane. Ethers such as dioxane and tetrahydrofuran; ketones such as acetone, cyclohexanone and isophorone; esters such as ethyl acetate, ethylene glycol acetate and dibutyl maleate; alcohols such as methanol and n-hexanol; Ethylene glycol and the like; polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and the like; water and the like.

Examples of the fixing agent and the dispersing agent include casein, polyvinyl alcohol, carboxymethyl cellulose, bentonite, xanthan gum and gum arabic. Aerosol propellants include, for example, air, nitrogen, carbon dioxide, propane, halogenated hydrocarbons and the like. As the stabilizer, for example, 2,6-di-tert-butyl-4-methylphenol (PA
P), isopropyl acid phosphate (BHT) and the like. Examples of the surfactant include an alkyl sulfate salt, an alkyl sulfonate, an alkylbenzene sulfonate, a lignin sulfonate, a dialkyl sulfosuccinate, a naphthalene sulfonate condensate, a polyoxyethylene alkyl ether, and a polyoxyethylene alkyl allyl. Examples thereof include ether, polyoxyethylene alkyl ester, alkyl sorbitan ester, polyoxyethylene sorbitan ester, and polyoxyethylene alkylamine.

In the preparation of the present agent, the above-mentioned diluents, surfactants, dispersants and adjuvants can be used alone or in appropriate combination according to the respective purposes.
When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in an emulsion, and usually 0.3% in a powder.
25 to 25% by weight, usually 1 to 90 for wettable powder and wettable powder.
%, Usually 0.5 to 10% by weight for granules, usually 0.5 to 40% by weight for suspensions, usually 1 to 30% by weight for emulsions, usually 0.5 to 20% for solubilized preparations. % For aerosol, usually 0.1 to 5% by weight. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0032]

The present invention will be specifically described below with reference to examples. Note that these examples do not limit the scope of the present invention. Example 1 Synthesis of Compound (2) (1) Synthesis of 1,3-dimethyl-5-chloro-4-pyrazolecarboxyhydroxymoyl chloride [Compound No. (2-1)] 1,3-dimethyl-5- Chloro-4-pyrazole aldehyde oxime (6.01 g, 34.6 mmol) was dissolved in dimethylformamide (40 ml), N-chlorosuccinimide (5.08 g, 38.1 mmol) was added, and the mixture was stirred at room temperature for 5 hours. The mixture was extracted with diethyl ether, washed sequentially with water and brine, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was dried to obtain 6.62 g of a slightly yellow solid.

(2) Synthesis of other compound (2) in Table 1 According to the method of (1), other compound (2) in Table 1 was synthesized. Table 1 shows the compounds (2) synthesized as described above and their physical property values.

[0034]

[Table 1]

Example 2 [Synthesis of Compound (1)] (1) [O-methyl-1,3-dimethyl-5- (4'-
Synthesis of [chlorophenoxy) -4-pyrazolecarbohydroxymoyl] -N, N-dimethylamine [Compound No. 22] 1,3-dimethyl-5- (4′-chlorophenoxy)-
4-Pyrazolecarbohydroxymoyl] -N, N-dimethylamine (206 mg, 0.67 mmol) was dissolved in dimethyl sulfoxide (5 ml), and potassium hydroxide powder (0.1 g, 1.78 mmol) and iodomethane (0.48) were dissolved.
g (3.4 mmol) was added and stirred at room temperature for one day. The mixture was extracted with ethyl acetate, washed successively with water and brine, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography (toluene: ethyl acetate = 4:
Purification in 1) gave 0.16 g of a colorless oil.

(2) Synthesis of [O-isopropyl-1,3-dimethyl-5-chloro-4-pyrazolecarbohydroxymoyl] -N, N-dimethylamine [Compound No. 3]
9] 1,3-dimethyl-5-chloro-4-pyrazolecarbohydroxymoyl] -N, N-dimethylamine 0.59
g (2.72 mmol) in 10 m of dimethyl sulfoxide
of potassium hydroxide powder 0.23 g (4.10
mmol) and 2.0 g of 2-iodopropane (3.4 mm
ol) and stirred at room temperature for 5 hours. After extraction with ethyl acetate, washing with water and brine in that order, drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (toluene: ethyl acetate = 1: 1).
0.18 g of a colorless oil was obtained.

(3) Synthesis of [O-benzyl-1,3-dimethyl-5-chloro-4-pyrazolecarbohydroxymoyl] -N, N-dimethylamine [Compound No. 4]
0] 1,3-dimethyl-5-chloro-4-pyrazolecarbohydroxymoyl] -N, N-dimethylamine 0.53
g (2.45 mmol) was dissolved in 20 ml of acetonitrile, and 0.68 g (4.89 mmol) of potassium carbonate, 0.78 g (6.16 mmol) of benzyl chloride and 0.05 g of tetrabutylammonium bromide were added thereto.
Heated to reflux for an hour. The reaction solution was concentrated under reduced pressure, and the residue was subjected to column chromatography (toluene: ethyl acetate = 1: 1).
Purification in 1) gave 0.65 g of a pale yellow oil.

(4) Synthesis of [O-acetyl-1,3-dimethyl-5-chloro-4-pyrazolecarbohydroxymoyl] -N, N-dimethylamine [Compound No. 4]
1] 1,3-dimethyl-5-chloro-4-pyrazolecarbohydroxymoyl] -N, N-dimethylamine 0.42
g (1.94 mmol), 10 ml of dichloromethane and 0.39 g (3.88 mmol) of triethylamine were added, and 0.23 g (2.91 mmol) of acetyl chloride was added.
Was added and stirred at room temperature for 5 hours. Extract with ethyl acetate,
After washing with saturated aqueous sodium hydrogen carbonate and brine in that order, drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography (toluene: ethyl acetate =
1: 1) to give 0.31 g of a pale yellow oil.

(5) Synthesis of [O-benzoyl-1,3-dimethyl-5-chloro-4-pyrazolecarbohydroxymoyl] -N, N-dimethylamine [Compound No. 4]
2] 1,3-dimethyl-5-chloro-4-pyrazolecarbohydroxymoyl] -N, N-dimethylamine 0.30
g (1.38 mmol), 10 ml of dichloromethane and 0.28 g (2.77 mmol) of triethylamine were added, and 0.32 g (2.28 mmol) of benzoyl chloride was added.
l) was added and the mixture was stirred at room temperature for 1 hour. Extracted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate and brine sequentially,
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (toluene: ethyl acetate = 1: 1) to obtain 0.42 g of a colorless oil.

(6) [1,3-dimethyl-5- (4'-
Synthesis of [chlorophenoxy) -4-pyrazolecarbohydroxymoyl] -N, N-dimethylamine [Compound No. 1] 1,3-dimethyl-5- (4′-chlorophenoxy)-
4-pyrazolecarbohydroxymoyl chloride 1.0
1 g (3.37 mmol) in tetrahydrofuran 30 m
Dissolved in 50% dimethylamine aqueous solution 0.38g
(4.2 mmol) and stirred at room temperature for one day. The solvent was distilled off under reduced pressure, the residue was dissolved in chloroform, dried over magnesium sulfate, the solvent was distilled off again under reduced pressure, and the residue was subjected to column chromatography (toluene: ethyl acetate =
Purification by 1: 1) yielded 0.30 g of slightly yellow crystals.

(7) [O-methyl-1,3-dimethyl-
Synthesis of 5- (4'-chlorophenoxy) -4-pyrazolecarbohydroxymoyl] methyl sulfide [Compound No. 31] 1,3-dimethyl-5- (4'-chlorophenoxy)-
4-pyrazolecarbohydroxymoyl] methyl sulfide (0.48 g, 1.54 mmol) in acetone 20 m
and 0.44 g (3.18 mmol) of potassium carbonate.
l) and 1.1 g (7.7 mmol) of iodomethane were added, and the mixture was heated under reflux for 10 hours. The reaction solution was filtered, the solvent of the filtrate was distilled off under reduced pressure, and the residue was purified by column chromatography (toluene: ethyl acetate = 2: 1) to obtain 0.33 g of an oil.

(8) [1,3-dimethyl-5- (4'-
Synthesis of [chlorophenoxy) -4-pyrazolecarbohydroxymoyl] methyl sulfide [Compound No. 12] 1,3-dimethyl-5- (4′-chlorophenoxy)-
4-pyrazolecarbohydroxymoyl chloride 0.8
8 g (2.93 mmol) of tetrahydrofuran in 15 m
The solution was added to 2.1 g (4.5 mmol) of a 15% sodium methyl mercaptan solution, and stirred at room temperature for one day. After extraction with ethyl acetate, washing with water and brine in that order, drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography (toluene: ethyl acetate =
1: 1) to give 0.72 g of colorless crystals.

(9) Other compounds in Tables 2 to 4 (1)
Other compounds (1) in Tables 2 to 4 were synthesized according to the methods (1) to (4). The compounds (1) synthesized as described above and their physical property values are shown in Tables 2 to 5.

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

[Table 5]

Example 3 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound (1), 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of sodium decylbenzenesulfonate and sodium ligninsulfonate 2 parts by weight were uniformly mixed, and then a small amount of water was added and kneaded, followed by extrusion granulation and drying to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound (1), 70 parts by weight of kaolin clay, 18 parts by weight of white carbon, 1.5 parts by weight of sodium dodecylbenzenesulfonate and sodium formalin β-naphthalenesulfonate 0.5 part by weight of the condensate was uniformly mixed and then pulverized by air mill to obtain a wettable powder.

(3) Preparation of emulsion Compound (1) was added to 20 parts by weight and xylene to 70 parts by weight.
10 parts by weight of Solpol 3005A (trade name; manufactured by Toho Chemical Co., Ltd.) were added, mixed uniformly, and dissolved to obtain an emulsion.

(4) Preparation of Dust A powder was obtained by uniformly mixing 5 parts by weight of compound (1), 50 parts by weight of talc and 45 parts by weight of kaolin clay.

Example 4 [Biological test] (1) Paddy field weeding test A 1/5000 arel Wagner pot was filled with Ube soil (alluvial clay loam), seedlings or tubers of rice seedlings and congers were planted, and water was added. To a depth of 3 cm. Example 3
The wettable powder of the target compound (1) shown in Tables 2 to 4 adjusted according to the following was diluted with water containing a surfactant (0.05%),
The effective concentration of compound (1) in each of these drug solutions is 2
000 g / ha was dropped using a pipette. After controlling for 3 weeks in a glass room at an average temperature of 25 ° C., their herbicidal effect was investigated. The evaluation of the herbicidal effect was shown in the following six stages as compared with the state of the non-treated section. [Herbicidal effect] 0: Normal growth, 1: Slight harm, 2: Small harm, 3: Medium harm, 4:
Major harm 5: Complete mortality The results are shown in Table 6.

[0053]

[Table 6]

(2) Upland soil treatment test A 1/5000 arel Wagner pot was filled with Ube soil (alluvial clay loam) and covered with seeds of Meishiba, Shiroza and Inubiyu. Tables 2 to 4 prepared according to Example 3
And a surfactant (0. 1).
(0.5%), and sprayed uniformly on the surface of each soil so that the effective concentration of Compound (1) in each of these chemical solutions would be 2000 g / ha. And average temperature 25
After 3 weeks of management in a glass room at ℃, their herbicidal effect was investigated. Evaluation of the herbicidal effect was performed in the same manner as in the above (1). Table 7 shows the results.

[0055]

[Table 7]

(3) Field-growing foliage treatment test Volcanic ash soil was filled in a 1/5000 arel Wagner pot, seeds of Meishishiba, Shiroza and Inubiyu were planted and covered with soil, and cultivated in a glass room at an average temperature of 25 ° C for about 2 weeks. . At the time when each plant grew appropriately, the wettable powder of the target compound (1) shown in Tables 2 to 4 prepared according to Example 3 was reduced to 2000 ppm with water containing a surfactant (0.05%). Each of the above plants was diluted and sprayed uniformly. After controlling for 3 weeks in a glass room at an average temperature of 25 ° C., their herbicidal effect was investigated. Evaluation of the herbicidal effect was performed in the same manner as in the above (1). Table 8 shows the results.

[0057]

[Table 8] In addition, "-" shows an untested.

(4) Test for controlling efficacy against barley powdery mildew (preventive effect) Ten barleys (cultivar: black wheat) were grown per pot in a plastic flowerpot having a diameter of 6 cm, and a 1.5-leaf seedling. In addition, a wettable powder of the target compound (1) shown in Tables 2 to 4 prepared according to Example 3 was added to a surfactant (0.05%).
%) Drug diluted to 500 ppm with water
0 ml was sprayed. After spraying, grow in a glass greenhouse for 2 days,
Next, conidiospores of barley powdery mildew fungus were collected from the diseased leaves and sprinkled evenly over the plants to inoculate them. After inoculation, they were raised in a glass greenhouse for one week, and the degree of barley powdery mildew spots that appeared on the first leaf was investigated. The drug effect was determined by comparing the degree of the lesion in the untreated plot. Evaluation of the herbicidal effect was performed in the same manner as in (1). The control value was shown in 6 stages from 0 to 5 as follows based on the percentage of the lesion area relative to the untreated plot. [Control value] 0% = 5, 1 to 10% = 4, 11 to 30% = 3,
31-50% = 2, 51-80% = 1, 81-100
= 0 The results are shown in Table 9.

[0059]

[Table 9]

(5) Test for Control Effect on Wheat Leaf Rust (Preventive Effect) Ten wheat (cultivar: Kobushi wheat) were grown per pot in a plastic flowerpot having a diameter of 6 cm, and the seedlings were grown at 1.5-leaf stage. The wettable powder of the target compound (1) shown in Tables 2 to 4 adjusted according to Example 3 contains a surfactant (0.
(05%) 20 ml of a drug diluted to 500 ppm with water was sprayed per pot. After spraying, cultivate in a glass greenhouse for 2 days, then spore suspension of wheat leaf rust (3 × 10 ⁵ )
Was spray inoculated uniformly. After the inoculation, they were raised in a glass greenhouse for one week, and the degree of wheat leaf rust spots on the first leaf was examined. The drug effect was determined by comparing the degree of the lesion in the untreated plot. Evaluation of the control effect was performed in the same manner as in the above (4). Table 10 shows the results.

[0061]

[Table 10]

[0062]

The drug containing the novel pyrazole oxime compound of the present invention as an active ingredient is:
Has excellent herbicidal and bactericidal effects.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 231/22 C07D 231/22 Z 401/06 401/06 (72) Inventor Satoshi Ohita Ube City, Yamaguchi Prefecture 1978 Obe Kogushi, Ube Research Laboratories Ube Research Institute (72) Inventor Takehiko Asahara 1978 Obe City, Yamaguchi Prefecture 578 Ube Kosan Ube Research Laboratories (72) Inventor Tomoya Noritake Oji Kobe, Ube City, Yamaguchi Prefecture 1978, 5 Ube Industries, Ltd., Ube Research Laboratories (72) Inventor Yasuhisa Fukuda, Obe, Yamaguchi Prefecture BA01 BB09 BB10 BC01 BC07 BC18 BC20 DA02 DA15 DA16 DD01 DD03 DD04 DE15

Claims (5)

[Claims] (1) The following formula (1): Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms and a phenyl group; R ² represents an alkyl group having 1 to 4 carbon atoms; R ³ represents a phenoxy group and a halogen atom Represents an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a phenylthio group; R ⁴ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, Up to 5 haloalkyl groups, benzyl groups, 2 carbon atoms
R ⁵ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, an alkynyl group having 3 to 5 carbon atoms, phenyl Group, benzyl group, morpholinyl group, 2 to 2 carbon atoms
Phenyl group having 4 alkylene chains, 2 carbon atoms
A represents a sulfur atom, NR ⁶ (where R ⁶ represents a hydrogen atom, a carbon atom number of 1 to 5).
Alkyl groups, alkenyl groups having 3 to 5 carbon atoms,
Represents an alkynyl group having 3 to 5 carbon atoms, or “forms a 6-membered ring together with a nitrogen atom together with R ⁵ ,
A 6-membered ring in which one of the carbon atoms at any position in the ring may be an oxygen atom. ). A pyrazole oxime compound represented by the formula: 2. The following formula (2): (Wherein, R ^{1 to} R ³ are as defined in claim 1;
Represents a halogen atom. A) a pyrazole hydroxymoyl halide compound represented by the formula: 3. A compound represented by the formula (2) according to claim 2, and a compound represented by the following formula (3): (Wherein, R ⁵ has the same meaning as in claim 1) or the following formula (4): (Wherein R ⁵ has the same meaning as described above; R ⁶ has the same meaning as described in claim 1).
Further, the following formula (5): (Wherein, X represents a halogen atom; R ⁴ is, claim 1
Is synonymous with the description. The method for producing a pyrazole oxime compound represented by the formula (1) according to claim 1, wherein the compound represented by the formula (1) is reacted. 4. A herbicide comprising the compound represented by the formula (1) according to claim 1 as an active ingredient. 5. A fungicide comprising the compound represented by the formula (1) according to claim 1 as an active ingredient.