JP2001348378A - 5-(1-fluoroethyl)-3-methylisoxazole-4-carboxylic acid derivative and pest controlling agent for agriculturf, and horticulture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a 5-(1-fluoroethyl)-3-methylisoxazole-4-carboxylic acid derivative as a pest controlling agent for agricultufe and horticulture. SOLUTION: The 5-(1-fluoroethyl)-3-methylisoxazole-4-carboxylic acid derivative is expressed by the formula (1) (wherein, R is a (substituted) phenyl, a (substituted) phenoxy, a (substituted) pyridyl or methyl; A is a direct bond, or a 1-12C normal or branched alkylene; and X is an amino group or an oxygen atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel 5- (1-fluoroethyl) -3-methylisoxazole-4-carboxylic acid derivative useful as a pesticide for agricultural and horticultural use.

[0002]

BACKGROUND OF THE INVENTION 5- (1-Fluoroethyl)-of the present invention
Since 3-methylisoxazole-4-carboxylic acid derivative is a novel compound, it is not known to have pest control activity for agricultural and horticultural use.

[0003]

An object of the present invention is to provide a novel 5- (1-fluoroethyl) -3-methylisoxazole-4-carboxylic acid derivative and an agricultural and horticultural pest comprising the same as an active ingredient. It is to provide a controlling agent.

[0004]

The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, a novel 5- (1-fluoroethyl) -3-methylisoxazole-4-carboxylic acid derivative has been obtained. The present inventors have found that they are useful as pest control agents for agricultural and horticultural use, and have completed the present invention. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0005]

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5- (1-fluoroethyl)-represented by
It relates to a 3-methylisoxazole-4-carboxylic acid derivative. Here, R, A and X in the formula are as follows. R represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenoxy, a substituted or unsubstituted pyridyl group, or a methyl group. A represents a direct bond, a linear or branched alkylene having 1 to 12 carbon atoms. X is
Represents an amino group or an oxygen atom. The second invention provides the following formula (2):

[0007]

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The present invention relates to a 4-fluoro-3-pyrrolidino-2-pentenoate compound represented by the formula:
In the formula, R ¹ represents a lower alkyl group having 1 to 4 carbon atoms. The compound (2) represented by the formula (2) is an intermediate for producing the compound (3). The third invention is
The following equation (3):

[0009]

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5- (1-fluoroethyl)-
It relates to a 3-methylisoxazole-4-carboxylic acid ester compound. In the formula, R ¹ represents a lower alkyl group having 1 to 4 carbon atoms. The compound (3) represented by the formula (3) is an intermediate for producing the compound (4). A fourth invention provides the following equation (4):

[0011]

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5- (1-fluoroethyl)-
It relates to 1-methylpyrazole-4-carboxylic acid. The compound (4) represented by the formula (4) is an intermediate for producing the compound (1).

A fifth aspect of the present invention is a pest control for agricultural and horticultural use, which comprises a 5- (1-fluoroethyl) -3-methylisoxazole-4-carboxylic acid derivative represented by the above formula (1) as an active ingredient. It relates to the agent.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The various substituents represented by the above compounds are as follows. In the description of the present invention, parenthesized numbers, symbols, and the like attached to chemical formulas are also referred to as "compounds (numerals, symbols, and the like)." For example, a compound represented by the formula (1) is also referred to as a compound (1). ]. [R] R represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenoxy, a substituted or unsubstituted pyridyl group, or a methyl group.

(1) The substituted or unsubstituted phenyl group includes a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched alkoxy group having 1 to 4 carbon atoms. Group, methylenedioxy group, linear or branched haloalkoxy group having 1 to 4 carbon atoms, and phenyl group which may be substituted with a halogen atom; Chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 3,4-dichlorophenyl group, 4-trifluoromethylphenyl group,
Methoxyphenyl group, 3,4-dimethoxyphenyl group,
3,4,6-trimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 4-trifluoromethoxyphenyl group, 3-isopropoxyphenyl group, 4-isopropylphenyl group, 3-chloro-6-nitrophenyl Group. (2) As the substituted or unsubstituted phenoxy, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, a halogen atom And a phenoxy group which may be substituted with a trifluoromethoxy group;
It is a trifluoromethoxyphenoxy group. (3) Examples of the substituted or unsubstituted pyridyl group include a pyridyl group substituted with a linear or branched alkoxy group having 1 to 4 carbon atoms; preferably a pyridyl group or 2-methoxy It is a pyridyl group.

[R ¹ ] R ¹ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and an n-butyl group; preferably, an ethyl group. [A] A represents a direct bond, a linear or branched alkylene having 1 to 12 carbon atoms. Examples of the linear or branched alkylene having 1 to 12 carbon atoms include methylene, methylmethylene, ethylmethylene, i-propylmethylene, ethylene, propylene, butylene, and 1-methyloctylene. A methylene group, a methylmethylene group, an ethylene group, and a 1-ethyloctylene group. [X] X represents an amino group or an oxygen atom.

As the compound (1), a compound obtained by combining the above-mentioned various substituents can be mentioned, and from the viewpoint of efficacy, the following compounds are preferred. (1) A is a methylene group, X is an amino group, R
Is a substituted or unsubstituted phenyl group. (2) A is a methylene group, X is an amino group, R
Is a substituted or unsubstituted pyridyl group. (3) A is a methylene group, X is an oxygen atom, R
Is a substituted or unsubstituted phenyl group.

(4) A is an ethylene group, X is an amino group, and R is substituted with an alkoxy group having 1 to 4 carbon atoms or a haloalkoxy group having 1 to 4 carbon atoms. A compound that is a phenyl group. (5) The compound wherein A is an ethylene group, X is an amino group, and R is a phenoxy group substituted with a haloalkoxy group having 1 to 4 carbon atoms. (6) The compound wherein A is a 1-methyloctylene group, X is an amino group, and R is a methyl group. (7) Compound wherein A is a direct bond, X is an amino group, and R is a phenyl group substituted by an alkoxy group having 1 to 4 carbon atoms. (8) A is a direct bond, and X is A compound wherein R is a pyridyl group substituted with an alkoxy group having 1 to 4 carbon atoms, which is an amino group;

The method for synthesizing the compound (1) of the present invention is as follows:
This will be described in more detail. Compound (1) can be synthesized by the following synthesis method 1 or 2. (Synthesis Method 1) Compound (1) can be synthesized by reacting compound (4) with compound (5) in a solvent in the presence of a condensing agent as shown below.

[0020]

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(In the formula, R, A and X have the same meanings as described above.) The molar ratio of the raw materials can be arbitrarily set, but usually, the molar ratio of the compound (5) is 0.1 to 1 mol of the compound (4). It is a ratio of 5 to 2 mol. The type of the solvent is not particularly limited as long as it does not directly participate in the reaction, for example, benzene,
Chlorinated or unchlorinated aromatic, aliphatic, cycloaliphatic such as toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, dichloroethane, trichloroethylene Hydrocarbons; ethers such as tetrahydrofuran, dioxane, diethyl ether and the like; and mixtures of the above-mentioned solvents.

The amount of the solvent used is 5 to 80 for compound (4).
Weight percent can be used; however, 10
~ 70% by weight is preferred. As the condensing agent, N, N'-
Dicyclohexylcarbodiimide (abbreviation: DCC) or 1
Dehydration condensing agents such as -ethyl-3- (3-dimethylaminopropyl) -carbodiimide (abbreviation: WSC) can be mentioned; preferably, it is 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide. . The amount of the condensing agent to be used is 1 to 5 moles relative to compound (4); preferably 1.0 to 1.5 moles.

The reaction temperature is not particularly limited, but may be -20.
C. to a temperature below the boiling point of the solvent; preferably between room temperature and 50.degree. The reaction time varies depending on the above concentration and temperature; it is usually 0.5 to 8 hours. The starting compound (5) can be obtained as a commercial product or can be produced by the method shown in the following formula. (1) When A is a linear alkylene group and X is an amino group

[0024]

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Wherein R is as defined above;
¹ is a linear alkylene group; Y represents a halogen atom. In addition, as the halogen atom for Y, a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like can be mentioned; preferably, a chlorine atom and a bromine atom are used. The starting compounds (6) and (7) can be obtained as commercial products. (2) When A is a branched alkylene group and X is an amino group

[0026]

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Wherein R is as defined above;
² is a branched alkylene group; R ² has 1 to 1 carbon atoms
Represents three lower alkyl groups. ) The starting compound (9) can be obtained as a commercial product.

Compound (2) can be produced by the method shown in the following formula.

[0029]

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(In the formula, R ¹ has the same meaning as described above.) The starting compound (10) can be produced by the method described in JP-A-11-171834, and (11) is obtained as a commercial product be able to. As the compound (2), for example, the compound shown in Example 1 described later can be mentioned. Compound (3) can be produced by the method shown by the following formula.

[0031]

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(In the formula, R ¹ has the same meaning as described above.) The starting compound (12) can be obtained as a commercial product. As the compound (3), for example, the following Example 1
Can be mentioned. Compound (4)
Can be manufactured by the method shown in the following formula.

[0033]

Embedded image (In the formula, R ¹ has the same meaning as described above.)

(Synthesis Method 2) Compound (1) can also be synthesized according to the following scheme.

[0035]

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(In the formula, R, A, X and Y have the same meanings as described above.) Examples of the compound (1) include the compound numbers 1 to 30 shown in Tables 1 and 2 below. Can be.

[Pest control effect] The pests for agricultural and horticultural use which are effective in controlling the compound (1) of the present invention include agricultural and horticultural pests (eg, brown planthoppers, spider mites, sweet potato nematodes, etc.), and agricultural and horticultural pathogens (eg, Wheat red rust, barley powdery mildew, cucumber downy mildew, rice blast, tomato late blight, etc.), and agricultural and horticultural weeds (eg, mehisiba, nobie, shiroza, inubeyu, morning glory). Further, the compound (1) of the present invention can be used for spraying leaves, irrigating the soil, and mixing the soil.

The pesticidal composition for agricultural and horticultural use of the present invention contains at least one compound (1) as an active ingredient. 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 an ordinary method, for example, a dressing agent, an emulsion, a fine granule, a granule. It is preferable to adjust and use such compositions as wettable powders, wettable powders, wettable powders, aqueous suspensions, oily 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 dimethylxylylethane; chlorinated hydrocarbons such as chloroform. Ethers such as dioxane and tetrahydrofuran; ketones;
For example, acetone, cyclohexanone, isophorone, etc .; esters, for example, ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc .; alcohols, for example, methanol, n-hexanol, ethylene glycol, etc .; polar solvents, for example, N, N -Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and the like; water and the like. Examples of the individual adhesive and dispersant include casein, polyvinyl alcohol, carboxymethylcellulose, bentonite, xanthan gum, and gum arabic. Aerosol propellants include, for example, air, nitrogen, carbon dioxide, propane, halogenated hydrocarbons and the like. Examples of the stabilizer include PAP, BHT and the like.

Examples of the surfactant include alcohol sulfates, alkyl sulfate salts, alkyl sulfonates, alkyl benzene sulfonates, lignin sulfonates, dialkyl sulfosuccinates, naphthalene sulfonate condensates, and polyoxyethylene. Examples thereof include alkyl ether, polyoxyethylene allyl 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, and 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.

[0042]

EXAMPLES The present invention will be specifically described below with reference examples and examples. Note that these examples do not limit the scope of the present invention.

Reference Example Synthesis of [Compound (10)] Synthesis of ethyl 4-fluoro-3-oxopentanoate 60% NaH in tetrahydrofuran (5 ml)
Oil (5.2 g) was added, and the mixture was heated and stirred at 35 ° C. Then, 1-fluoropropionic acid ethyl ester (12
g) and ethyl acetate (11.4 g) in toluene (10 m
The solution dissolved in 1) is slowly added dropwise so as not to exceed 40 ° C. After completion of the dropwise addition, the reaction was continued at 35 ° C. for 2 hours to complete the reaction. 12N hydrochloric acid (26.4 g) in water (40
ml) was added thereto, and the mixture was stirred under ice-cooling, and the reaction mixture was gradually added dropwise thereto. Ethyl acetate was added for liquid separation, and the separated organic layer was washed with saturated saline. After drying with sodium sulfate, the residue obtained by evaporating the solvent under reduced pressure was purified by vacuum distillation to obtain ethyl 4-fluoro-3-oxopentanoate (14.6 g).

B. p. 70-75 ° C./15 mmHg ¹ H-NMR (CDCl ₃ , δ ppm) 1.23 to 1.33 (3H, t), 1.47 to 1.57
(3H, m), 3.63 (2H, s), 4.18-4.
26 (2H, q), 4.87-5.30 (1H, q-
q),

Example 1 Synthesis of [Compounds (1) to (4)] (1) Synthesis of [Compound (2)] of 4-fluoro-3-pyrrolidino-2-pentenoic acid ethyl ester Oxopentanoic acid ethyl ester (25 g) and pyrrolidine (12 g) were dissolved in toluene (80 m
l) In addition, the mixture was refluxed and stirred for 3 hours while removing generated water. After completion of the reaction, toluene was distilled off under reduced pressure to obtain 4
-Fluoro-3-pyrrolidino-2-pentenoic acid ethyl ester (32 g) was obtained. Mass spectrometry (CI-MS) m / e = 216 (M + 1)

(2) 3- (1-fluoroethyl) -5
Synthesis of ethyl methylisoxazole-4-carboxylate [Compound (3)] Chloride 4-fluoro-3-pyrrolidino-2-pentenoic acid ethyl ester (12.3 g), nitroethane (13 g) and triethylamine anhydride (60 ml) Methylene (1
50 ml). Under ice-cooling and stirring, phosphorus oxychloride (17 ml) was added dropwise over about 2 hours.
Stir for 5 hours. After completion of the reaction, the reaction mixture was slowly poured into ice water, and the organic layer was separated. 2N-HCl, water, 2
The extract was washed with N-NaOH, water and saturated saline in this order, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (Wakogel C-gel).
200, eluted with toluene: ethyl acetate = 20: 1) to obtain 13 g of the target substance as a pale yellow liquid.
Obtained.

[0047]

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¹ H-NMR (CDCl ₃ , δ ppm) 1.34 to 1.40 (3H, t), 1.71 to 1.81
(3H, m), 2.47 (3H, s), 4.31-4.
38 (2H, q), 6.14 to 6.31 (1H, q-
q),

(3) 5- (1-fluoroethyl) -1-
Synthesis of methylpyrazole-4-carboxylic acid [compound (4)] 3- (1-Fluoroethyl) -5-methylisoxazole-4-carboxylic acid ethyl ester (12 g) was dissolved in ethanol (50 ml), and NaOH ( 4 g) in water (10 ml) was added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, ethanol was distilled off under reduced pressure, 12N hydrochloric acid was gradually added under ice-cooling to adjust the pH to 2, and the precipitated crystals were collected by filtration and washed with water to give colorless powdery crystals. 10 g were obtained. m. p. 139-142 ° C

(4) N- (2,4-dichlorobenzyl)
Synthesis of 3- (1-fluoroethyl) -5-methylisoxazole-4-carboxylic acid amide [Synthesis of compound (1) represented by compound No. 1] 3- (1-fluoroethyl) -5-methyliso Oxazole-4-carboxylic acid (0.8 g) and 2,4-chlorobenzylamine (1.2 g) were added to dichloromethane (30 m
1), 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride (1.5 g) was added, and the mixture was stirred at room temperature for 6 hours. After completion of the reaction, water was added to separate a methylene chloride layer, which was washed with 0.2N hydrochloric acid, a saturated aqueous solution of sodium hydrogen carbonate and water in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography [Wakogel C-2.
[00, n-hexane: ethyl acetate = 2: 1] to obtain 0.9 g of the target compound as colorless powdery crystals.

M. p. 81 to 84 ° C ¹ H-NMR (CDCl ₃ , δ ppm) 1.72 to 1.83 (3H, m), 2.46 (3H,
s) 4.60 to 4.63 (2H, d), 5.83 to
6.05 (1H, qq), 6.77 (1H, s),
7.22 to 7.42 (3H, m),

(5) N- [2- (3,4-dimethoxyphenyl) ethyl] -3- (1-fluoroethyl) -5
Synthesis of methylisoxazole-4-carboxylic acid amide [Synthesis of compound (1) represented by compound No. 13] 3- (1-Fluoroethyl) -5-methylisoxazole-4-carboxylic acid (0.8 g) Thionyl chloride (0.6 g) was added, and the mixture was heated under reflux for 30 minutes. Then, the residue was dissolved in toluene (20 ml) and stirred under ice-cooling with 2- (3,4).
-Dimethoxyphenyl) ethylamine (1.0 g) and triethylamine (0.6 g) were added, and the mixture was stirred at room temperature for 2 hours. After the completion of the reaction, water was added and toluene was separated off.
The extract was washed with 2N hydrochloric acid, a saturated aqueous solution of sodium hydrogen carbonate and water in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography [Wakogel C-200, n-hexane: ethyl acetate = 2: 1] to give the desired product as a colorless viscous liquid. 0.0 g was obtained.

[0053]

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(6) O- (4-chlorobenzyl) -3-
Synthesis of (1-fluoroethyl) -5-methylisoxazole-4-carboxylic acid ester [Synthesis of compound (1) represented by compound No. 23] 3- (1-fluoroethyl) -5-methylisoxazole-4 Carboxylic acid (0.7 g) and 4-chlorobenzyl alcohol (1.5 g) in dichloromethane (30 m
1), 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride (1.5 g) was added, and the mixture was stirred under reflux for 6 hours. After completion of the reaction, water was added to separate a methylene chloride layer, and a saturated aqueous sodium hydrogen carbonate solution was added.
The extract was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography [Wakogel C-200, n-hexane: ethyl acetate = 2: 1] to give the target compound as a colorless viscous liquid. 0.5 g was obtained.

[0055]

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¹ H-NMR (CDCl ₃ , δ ppm) 1.61 to 1.78 (3H, m), 2.45 (3H,
s), 5.38 (2H, s), 6.06 to 6.28 (1
H, q-q), 7.32-7.39 (4H, m),

(6) Synthesis of Other Compounds (1) in Tables 1 and 2 Other compounds (1) in Tables 1 and 2 were synthesized according to the above methods (4) and (5). . The compounds (1) synthesized as described above and their physical properties are shown in Tables 1 and 2.

[0058]

[Table 1]

[0059]

[Table 2]

Example 2 [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 dodecylbenzenesulfonate and 2 parts of sodium ligninsulfonate The 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 0.5 part by weight of β-naphthalenesulfonate sodium formalin condensate are uniformly mixed,
Subsequently, it was pulverized with an air mill to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of compound (1) and 70 parts by weight of xylene, 10 parts by weight of Solpol 3005X (trade name, manufactured by Toho Chemical Co., Ltd.) were added, mixed uniformly, and dissolved to obtain an emulsion. Was.

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

Example 3 [Efficacy Test] (1) Test for controlling efficacy against grape downy mildew (prevention test) One grape (cultivar: Neo Muscat) was grown per pot in a plastic flower pot having a diameter of 9 cm. An acetone solution of the compound (1) described in Tables 1 and 2 was added to the grape seedlings at the 6-leaf stage with water containing a surfactant (0.01%) for 50 days.
It diluted to 0 ppm and sprayed 15 ml per pot.
After spraying, cultivate in a glass greenhouse for one day, and then prepare a suspension of grape downy mildew spores (5 × 10 ⁴ cells / ml),
This was spray-inoculated on the back of the leaf. 20 days for 2 days after inoculation
C. and kept in a wet room, cultivated in a glass greenhouse for 11 days, and examined the degree of downy mildew appearing on the first to sixth leaves.
The effect was judged by comparing the degree of onset in the untreated plot to 5 with no lesions, 4 to 20% for lesion areas of 10% or less, 3.40% to 3,40%, and 2.60% to 1 The test was performed in 6 stages from 5 to 0, with the total disease being regarded as 0. As a result,
The compounds of Compound Nos. 4, 6, 13, and 19 exhibited an effect of 3 or more.

(2) Control effect test for wheat leaf rust (preventive effect) Ten wheats (variety: Kobushi wheat) were grown per pot in a plastic flower pot having a diameter of 6 cm. This 1.5
An acetone solution of the compound (1) shown in Tables 1 and 2 was diluted to 500 ppm with water containing a surfactant (0.01%), and 10 ml per pot was sprayed on the young plants at the leaf stage. . After spraying, the plants are cultivated for one day in a glass greenhouse, and then a suspension of wheat rust spores (3 × 10 ⁵ / m)
l) was adjusted, and this was spray-inoculated evenly to the plant body. After inoculation, the plants were kept in a humidity chamber at 20 ° C. for 1 day, cultivated in a glass greenhouse for 9 days, and the occurrence of leaf rust on the first leaves was examined. The effect was determined by comparing the degree of onset in the untreated section with 5 without lesions, 5 or less with a lesion area of 10% or less, about 4 or 20%, about 3 or 40% and about 2 or 60% with 1 or less. The test was performed in 6 stages from 5 to 0, with the total disease being regarded as 0. Table 3 shows the results.

[0066]

[Table 3]

(3) Test for controlling efficacy against rice blast (preventive test) Ten rice plants (variety: Nipponbare) were grown per pot in a plastic flowerpot having a diameter of 6 cm. An acetone solution of the compound (1) shown in Tables 1 and 2 was added to the 2.5-leaf seedling at 300 pp with water containing a surfactant (0.01%).
m and sprayed 10 ml per pot. After spraying, the plants were cultivated in a glass greenhouse for one day, and then a blast conidia spore suspension (3 × 10 ⁵ cells / ml) was prepared, and the suspension was sprayed and inoculated uniformly on the plants. 20 days for 2 days after inoculation
After cultivation in a glass greenhouse for 5 days, the degree of blast disease appearing on the third leaf was investigated.
The effect was judged by comparing the degree of onset in the untreated plot to 5 with no lesions, 4 to 20% for lesion areas of 10% or less, 3.40% to 3,40%, and 2.60% to 1 The test was performed in 6 stages from 5 to 0, with the total disease being regarded as 0. As a result,
The compounds of Compound Nos. 20, 23 and 28 exhibited an effect of 3 or more.

(4) Herbicidal activity test (field foliage treatment test) A 1 / 5000-are Wagner pot was filled with volcanic ash soil, and seeds of Meishishiba, Shiroza, Inubeyu and Asagao were planted and covered with soil. Cultivated in the room for about 2 weeks. At the time when each plant grew moderately, the wettable powder of the compound (1) described in Tables 1 and 2 prepared according to Example 2 was 2,000 pp in water containing a surfactant (0.05%).
m and sprayed uniformly on each of the above plants. 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 untreated section. [0: Normal growth, 1: Slight harm, 2: Small harm, 3: Medium harm, 4: Major harm,
5: Complete withering]

As a result, Compound Nos. 1, 2, 8, 17,
28, 30 show 4 or more effects on crabgrass; Compound Nos. 1, 2, 4, 5, 6, 15, 17, 19, 2
3,24,28,30 show more than 4 effects on Siroza; Compound Nos.1,2,4,5,6,15,17,
19,23,24,27,28,30 show more than 4 effects on dogwood; Compound Nos. 1,4,23,2
4,28 showed 4 or more effects on morning glory.

(5) Efficacy test against sweet potato nematode Each wettable powder of compound (1) shown in Tables 1 and 2 prepared according to Example 2 was diluted to 300 ppm with water, and 0.1 ml of the diluted water was placed in a test tube. 0.9 ml of a solution containing 500 sweet potato root-knot nematodes was added. Next, these test tubes were allowed to stand in a low-temperature room at 25 ° C. and observed under a microscope two days later to determine the nematicidal rate. As a result, Compound 2,
15 showed 80% nematicidal activity.

(6) Test for adult female spider mite (Acari: Tetranychidae) Each wettable powder of compound (1) shown in Tables 1 and 2 prepared according to Example 2 was prepared by adding 300 ppm of a surfactant to water containing (0.01%). , And each bean leaf piece (diameter: 20 mm) in which ten adult female spider mites were parasitized was immersed in each of these solutions for 15 seconds. Next, each leaf piece was left in a constant temperature room at 25 ° C., and three days later, the number of live and dead insects in each leaf piece was counted to determine the acaricidal rate. As a result, compounds 1, 4, 5, 6, 13, 19, 23, 28 and 30 are
It showed acaricidal activity of 80% or more.

[0072]

According to the present invention, 5- (1-fluoroethyl)-
The 1-methylpyrazole-4-carboxylic acid amide derivative has an excellent agricultural and horticultural pest control effect.

Continued on the front page F term (reference) 4C056 AA01 AB01 AC01 AD01 AE03 FB16 FB17 4H011 AA01 AA03 AB01 AC01 BA01 BB09 BB10 BB11 BC01 BC07 BC18 BC19 BC20 DA02 DA15 DA16 DC01 DC05 DD03 DE15 DH03

Claims (5)

[Claims] (1) The following formula (1): 5- (1-fluoroethyl) -3-methylisoxazole-4-carboxylic acid derivative represented by the formula: Here, R, A and X in the formula are as follows. R represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenoxy, a substituted or unsubstituted pyridyl group, or a methyl group. A represents a direct bond, a linear or branched alkylene having 1 to 12 carbon atoms. X represents an amino group or an oxygen atom. 2. The following formula (2): 4-fluoro-3-pyrrolidino-2-pentenoic acid ester compound represented by the formula: In the formula, R ¹ has 1 to 1 carbon atoms.
4 represents a lower alkyl group. 3. The following formula (3): 5- (1-fluoroethyl) -3-methylisoxazole-4-carboxylic acid ester compound represented by the formula: In the formula, R ¹ represents a lower alkyl group having 1 to 4 carbon atoms. 4. The following formula (4): 5- (1-fluoroethyl) -3-methylisoxazole-4-carboxylic acid represented by 5. The compound represented by the formula (1) according to claim 1,
A pest control agent comprising a (1-fluoroethyl) -3-methylisoxazole-4-carboxylic acid derivative as an active ingredient.