JP2000086636A - Pyrazolecarboxylic acid haloalkenyl ester derivative, its production and pest control agent for agriculture and horticulture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having remarkable insecticidal and fungicidal activities for agriculture and horticulture and useful as a pest control agent. SOLUTION: A compound of formula I [R1 is a lower alkyl; R2 is a lower alkyl or phenyl; R3 is a halogen, H or the like; X1 is a halogen or H; X2 is a halogen; (n) is 1-6], for example, 4-chloro-1,3-dimethylpyrazole-5-carboxylic acid 6,6-difluoro-5-hexenyl ester. The compound of formula I is obtained by reacting a pyrazolecarboxylic acid compound of formula II with a compound of formula III (Y is a halogen or a lower alkyl sulfonyloxy) in the presence of a base such as triethylamine in an organic solvent such as benzene in a temperature range of -20 deg.C to the boiling point of the solvent usually for about 0.5 to 5 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel haloalkenyl pyrazole carboxylate derivative which is useful as a pesticide for agricultural and horticultural use.

[0002]

BACKGROUND OF THE INVENTION The pyrazolecarboxylic acid haloalkenyl ester derivative of the present invention is a novel compound,
It is not known to have pest control activity for agricultural and horticultural purposes.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel pyrazole carboxylic acid haloalkenyl ester derivative, a process for producing the same, and a pesticide for agricultural and horticultural use containing the same as an active ingredient.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have studied to solve the above-mentioned problems, and as a result, have found that a novel pyrazole carboxylic acid haloalkenyl ester derivative has remarkable insecticidal and fungicidal activities for agricultural and horticultural use. And 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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The present invention relates to a pyrazole carboxylic acid haloalkenyl ester derivative represented by the formula: In the formula, R ¹ , R ² , R ³ , X ¹ , X ² and n are as follows. R ¹ represents a lower alkyl group. R ² represents a lower alkyl group or a phenyl group. R ³ represents a halogen atom or a hydrogen atom. R ² and R ³ may form a saturated 5- to 7-membered ring together with the carbon atom at the position of their substitution. X ¹ represents a halogen atom or a hydrogen atom. X ² represents a halogen atom. n represents an integer of 1 to 6. The second invention provides the following formula (2):

[0007]

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(Wherein R ¹ , R ² and R ³ are as defined above) and a pyridinecarboxylic acid represented by the following formula (3):

[0009]

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(Wherein, Y represents a halogen atom or a lower alkylsulfonyloxy group; X ¹ , X ² and n have the same meanings as described above). And a method for producing a pyrazole carboxylic acid haloalkenyl ester derivative represented by the above formula (1).

The third invention relates to a pesticidal composition for agricultural and horticultural use, comprising a haloalkenyl pyrazolecarboxylate derivative represented by the above formula (1) as an active ingredient.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Compounds represented by the above formulas (1) to (3) [hereinafter, compounds corresponding to formulas (1) to (3) are referred to as compounds (1) to (3). ] And the like are as follows.

[R ¹ ] R ¹ is a lower alkyl group. Examples of the alkyl group include a linear or branched one having 1 to 4 carbon atoms;
₃ [R ² ] R ² is a lower alkyl group or a phenyl group. Examples of the alkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms; preferably, CH ₃ , C ₂ H ₅ and t-C ₄ H ₉ . Examples of the phenyl group include unsubstituted or substituted ones.
The substitution position is not particularly limited: 4-position substitution is preferred. As the substituent, a halogen atom is preferable. Examples of the substituted halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably, a chlorine atom.

[R ³ ] R ³ is a halogen atom or a hydrogen atom. As the halogen atom, a chlorine atom, an iodine atom,
Examples thereof include a bromine atom and a fluorine atom; preferably a chlorine atom and a bromine atom. The [R ² and R ^3] R ² and R ^3, together with the carbon atoms of the substituent positions may form a 5- to 7-membered saturated ring. 5-7 membered saturated ring may have a substituent R ^4; the ring is 5-membered rings are preferred. [R ⁴ ] R ⁴ is a hydrogen atom or a lower alkyl group. As the alkyl group, there may be mentioned a 1 to 4 carbon atoms of straight or branched; preferably CH _3.

[X ¹ ] X ¹ is a halogen atom or a hydrogen atom. As the halogen atom, a chlorine atom, an iodine atom,
Examples thereof include a bromine atom and a fluorine atom; preferably a fluorine atom and a chlorine atom. [X ² ] X ² represents a halogen atom. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like;
It is a chlorine atom. [Y] Y is a halogen atom or a lower alkylsulfonyloxy group. Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably, a chlorine atom and a bromine atom. The alkylsulfonyloxy group, there may be mentioned a straight or branched; preferably -OSO ₂ CH ₃
It is. [N] n is an integer of 1 to 6;
2 or 4.

As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned. From the viewpoint of efficacy, the following compounds are preferred. (1) A compound wherein R ¹ and R ² are a lower alkyl group, R ³ is a halogen atom, n is 4, X ¹ is a hydrogen atom, and X ² is a halogen atom. For example, the compound of Compound No. 1 described in Table 1 below can be mentioned. (2) The compound (1) in which R ¹ and R ² are lower alkyl groups, R ³ is a halogen atom, n is 2, and X ¹ and X ² are halogen atoms. For example, the compound of Compound No. 2 described in Table 1 below can be mentioned. (3) The compound (1) in which R ¹ and R ² are a lower alkyl group, R ³ is a halogen atom, n is 1, X ¹ is a hydrogen atom, and X ² is a halogen atom. For example,
Compound No. 3 described in Table 1 below can be mentioned. (4) A compound (1) in which R ¹ and R ² are lower alkyl groups, R ³ is a halogen atom, n is 2, X ¹ is a hydrogen atom, and X ² is a halogen atom. For example,
Compound No. 4 described in Table 1 below can be mentioned.

(5) A compound ( ¹ ) wherein R ¹ and R ² are lower alkyl groups, R ³ is a hydrogen atom, n is 4, X ¹ is a hydrogen atom, and X ² is a halogen atom. ). For example, the compound of compound No. 6 described in Table 1 below can be mentioned. (6) The compound (1) in which R ¹ and R ² are lower alkyl groups, R ³ is a hydrogen atom, n is 2, and X ¹ and X ² are halogen atoms. For example, the compound of Compound No. 7 described in Table 1 below can be mentioned. (7) R ¹ is a lower alkyl group, R ² and R ³ form a saturated 5- to 7-membered ring, n is 4, X ¹ is a hydrogen atom, and X ² is halogen Compound (1) which is an atom. For example, the compound of Compound No. 8 described in Table 1 below can be mentioned. (8) Compounds in which R ¹ is a lower alkyl group, R ² and R ³ form a saturated 5- to 7-membered ring, n is 2, and X ¹ and X ² are halogen atoms ( 1). For example, the compound of Compound No. 9 described in Table 1 below can be mentioned.

(9) R ¹ is a lower alkyl group; R ² and R ³ form a saturated 5- to 7-membered ring; n is 4; X ¹ is a hydrogen atom; Compound (1) in which ² is a halogen atom. For example, the compound of Compound No. 10 described in Table 1 below can be mentioned. (10) R ¹ is a lower alkyl group, R ² is a phenyl group, R ³ is a hydrogen atom, n is 2, X ¹ and X
Compound (1) in which ² is a halogen atom. For example, the compound of Compound No. 12 described in Table 1 below can be mentioned. (11) a compound wherein R ¹ is a lower alkyl group, R ² is a phenyl group, R ³ is a hydrogen atom, n is 1, X ¹ is a hydrogen atom, and X ² is a halogen atom (1).
For example, the compound of Compound No. 13 described in Table 1 below can be mentioned.

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 (2) and compound (3) in a solvent in the presence of a base as shown below.

[0020]

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(Wherein R ¹ , R ² , R ³ , X ¹ , X ² , Y and n have the same meanings as described above.) The molar ratio of the raw materials can be arbitrarily set. ) The compound (3) is in a ratio of 0.5 to 2 mol per 1 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, etc., nitriles such as acetonitrile, propionitrile, etc., ketones such as acetone, methyl ethyl ketone, etc., N, N-dimethylformamide, dimethyl sulfoxide, sulfolane And aprotic polar solvents such as N, N, N-dimethylimidazolidinone, N-methylpyrrolidone; and mixtures of the above solvents.

The amount of the solvent used is 5 to 80 for compound (2).
Weight percent can be used; however, 10
~ 70% by weight is preferred. The type of base is not particularly limited, and organic and inorganic bases, for example, tertiary amines such as triethylamine, aromatic or non-aromatic heterocycles such as pyridine, piperidine, etc., alkali metals and alkaline earths Mention may be made of metal hydrides, hydroxides, carbonates, bicarbonates, alkali metal alcoholates such as sodium methylate, potassium tert-butoxide and the like. The amount of the base to be used is 1 to 5 moles per 1 mole of Compound (2); 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 5 hours. The starting compound (2) can be produced by the method represented by the following formula described in JP-A-7-118238 and the like.

[0024]

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(Wherein R ¹ , R ² , and R ³ have the same meanings as described above, and R ⁵ represents a lower alkyl group.) The starting compound (3) is obtained as a commercial product or Y is an alkyl. A sulfonyl group, X ¹ is a hydrogen atom, X ²
Can be produced by the method shown in the following formula.

[0026]

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(In the formula, n is as defined above.) In addition to the synthesis method 1, the compound (1) can be synthesized by the following scheme.

[0028]

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Where R ¹ , R ² , R ³ , X ¹ , X ² and n
Is as defined above. Examples of compound (1) include compounds 1 to 16 shown in Table 1 below.

[Pest control effect] The pests for agricultural and horticultural use which are controlled by the compound (1) of the present invention include agricultural and horticultural insect pests such as Hemiptera (Cyberidae, leafhoppers, aphids, whiteflies) Etc.), Lepidoptera (Coleoptera,
Occidental beetles, Coleoptera, Pestiformes, Scarab beetles, White butterfly, etc., Coleoptera (Tenebrionidae, Curculionidae, Chrysomelidae, Scarabaeidae, etc.), Acari (Acari: Tetranychidae, Tetranychidae, etc.) Nematodes (e.g., root-knot nematodes, cyst nematodes, nexare nematodes, singare nematodes, pine wood nematodes, etc.);
Flies, mosquitoes, cockroaches, etc.); indoor mites (eg, Dermatophagoides farinae, Dermatophagoides pteronyssinus; Dermatophagoides farinae, Dermatophagoides farinae, etc.); animal parasitic mites (eg, mites, crab mites, dust mites, etc.); Insect pests (such as terrestrial beetles, beetles, etc.);
Wheat rust, barley powdery mildew, cucumber downy mildew, rice blast, tomato late blight, etc.).
In addition, the compound (1) of the present invention has systemic transferability, and can be used for seed treatment, seedling box treatment, stock plant treatment, soil irrigation treatment, and soil mixing treatment as well as leaf stem application.

The agricultural and horticultural pesticidal composition of the present invention has a remarkable insecticidal, acaricidal, nematicidal and fungicidal effect, and contains at least one compound (1) as an active ingredient. is there. 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 according to a conventional method. It is preferable to adjust and use the composition as a wettable powder, wettable powder, aqueous suspension, oily suspension, emulsion, solubilized preparation, oil, microcapsule, aerosol 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. As a fixing agent and a dispersing agent, for example, casein, polyvinyl alcohol,
Carboxymethyl cellulose, bentonite, xanthan gum, gum arabic and the like can be mentioned. 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.

[0035]

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 6,6-difluoro-5-hexenylmethanesulfonate] (1) Synthesis of 5-hydroxypentyl-p-chlorobenzoate 1,5-pentanediol (100 g) was dissolved in 400 ml of tetrahydrofuran, and triethylamine was dissolved. (110
g) was added. Next, the solution was ice-cooled, and p-chlorobenzoyl chloride (84 g) was added dropwise at the same temperature. After the dropwise addition, the mixture was returned to room temperature and stirred for 2 hours. After completion of the reaction, 300 ml of water was added, extracted with toluene, washed with water, and the organic layer was 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-200, toluene: ethyl acetate = (9: 1)].
To (1: 1)] to obtain 80 g of the target substance as a colorless transparent liquid.

(2) Synthesis of 5-oxopentyl-p-chlorobenzoate Oxalyl chloride (37.8 g) was dissolved in 400 ml of dichloromethane, and the solution was cooled to -60 ° C.
First, a solution of dimethylsulfoxide (25.7 g) dissolved in 80 ml of dichloromethane is added dropwise at -50 to -60 ° C, and then 5-hydroxypentyl-p-chlorobenzoate (40.0 g) is added to dichloromethane 160.
The solution dissolved in ml was added dropwise at -50 to -60C. After stirring at −50 to −60 ° C. for 15 minutes, triethylamine (83 g) was added dropwise at −40 to −60 ° C.,
The mixture was further stirred at the same temperature for 5 minutes. After the reaction, return to room temperature,
500 ml of water was added for liquid separation, and the organic layer was 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).
-200, toluene: ethyl acetate = 9: 1) to obtain 40 g of the target substance as a yellow transparent liquid.

(3) Synthesis of 6,6-difluoro-5-hexenyl-p-chlorobenzoate 5-oxopentyl-p-chlorobenzoate (40
g) and dibromodifluoromethane (70 g) were dissolved in 100 ml of dimethylacetamide and cooled to 0 ° C. A solution of triphenylphosphine (87 g) dissolved in 100 ml of dimethylacetamide was added dropwise. After the dropwise addition, the mixture was returned to room temperature and stirred for 30 minutes. Further, zinc powder (21 g) was added, and the mixture was stirred at 90 to 100 ° C for 2 hours.
After cooling, 200 ml of water was added, and the mixture was extracted with toluene, and the organic layer was 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-200, hexane: ethyl acetate =
By purifying in 9: 1), 25 g of the target substance was obtained as a yellow transparent liquid.

(4) Synthesis of 6,6-difluoro-5-hexenol 6,6-difluoro-5-hexenyl-p-chlorobenzoate (15 g) was dissolved in 100 ml of ethanol.
An aqueous solution of sodium hydroxide (2.5 g) dissolved in 10 ml of water was added dropwise, and the mixture was heated and stirred at 50 ° C. for 3 hours. After cooling, ethanol was distilled off under reduced pressure, extracted with dichloromethane, and the organic layer was 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-200, hexane:
Purification with ethyl acetate (1: 1) yielded 6.0 g of the target substance as a yellow transparent liquid.

(5) Synthesis of 6,6-difluoro-5-hexenylmethanesulfonate 6,6-Difluoro-5-hexenol (5.0 g) was dissolved in 50 ml of dichloromethane, and triethylamine (3.8 g) was added at a time. . The solution was ice-cooled, and methanesulfonyl chloride (4.5 g) was gradually added dropwise. After the dropwise addition, the temperature was returned to room temperature and stirring was continued for 3 hours. After the completion of the reaction, 50 ml of water was added to carry out liquid separation, and the organic layer was 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).
By purifying with hexane: ethyl acetate = 2: 1), 6.0 g of a colorless and transparent target product was obtained.

Example 1 Synthesis of Compound (1) (1) 4-Chloro-1,3-dimethylpyrazole-5
Synthesis of carboxylic acid-6,6-difluoro-5-hexenyl ester [Compound No. 1] 4-Chloro-1,3-dimethylpyrazole-5-carboxylic acid (0.9 g) was converted to N, N-dimethylformamide (2
0ml), potassium carbonate (0.7g) and 6,6
-Difluoro-5-hexenylmethanesulfonate (1.07 g) was added in that order, and the mixture was stirred at 40 ° C for 3 hours. After completion of the reaction, water was added, and the mixture was extracted with ethyl acetate. The extract is washed with water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the obtained residue is purified by silica gel column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 5: 1). As a result, 1.7 g of a target substance as a colorless liquid was obtained.

(2) 4-chloro-1,3-dimethylpyrazole-5-carboxylic acid-3,4,4-trifluoro-
Synthesis of 3-butenyl ester [Compound No. 2] 4-Chloro-1,3-dimethylpyrazole-5-carboxylic acid (0.9 g) was converted to N, N-dimethylformamide (2
0 ml), potassium carbonate (0.7 g) and 4-bromo-1,1,2-trifluorobutene (0.95 g).
Was added in order and stirred at 50 ° C. for 4 hours. After completion of the reaction, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
The obtained residue is subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 9:
(Eluted with 1) to give 1.0 g of the desired product as a pale yellow liquid.

(3) Synthesis of 4-bromo-1,3-dimethylpyrazole-5-carboxylic acid-3,3-dichloropropenyl ester [Compound No. 3] 4-bromo-1,3-dimethylpyrazole-5-carboxylic acid The acid (1.1 g) was converted to N, N-dimethylformamide (2
0 ml), add potassium carbonate (0.7 g) and 1,
1,3-Trichloropropene (0.75 g) was sequentially added, and the mixture was stirred at 50 ° C for 4 hours. After the reaction is completed, water is added,
Extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography (Wakogel C-2).
Then, 1.3 g of the target substance as a pale yellow liquid was obtained.

(4) Synthesis of Other Compound (1) in Table 1 Other compounds (1) in Table 1 were synthesized according to the methods (1) to (3) described above. Compound (1) synthesized as described above
And their physical properties are shown in Table 1.

[0045]

[Table 1]

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, sodium dodecylbenzenesulfonate 1
Parts by weight and 2 parts by weight of sodium ligninsulfonate were mixed uniformly, then a small amount of water was added and kneaded, and the mixture was extruded, granulated and dried 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 salt of isobutylene maleic anhydride copolymer 0.5 part by weight was uniformly mixed and then pulverized with an air mill to obtain a wettable powder.

(3) Preparation of emulsion 10 parts by weight of compound (1) and N-methylpyrrolidone 3
To 0 parts by weight, 10 parts by weight of xylene, and 40 parts by weight of phenylxylylethane, 10 parts by weight of Solpol 3885 (trade name, manufactured by Toho Chemical Co., Ltd.) were added, mixed uniformly, and dissolved to obtain an emulsion.

(4) Preparation of Dust 5 parts by weight of the compound (1), 50 parts by weight of talc and 45 parts by weight of kaolin clay were uniformly mixed and then pulverized by a hammer mill to obtain a powder.

Example 3 [Efficacy Test] (1) Effect on Spodoptera litura The water containing each surfactant of compound (1) shown in Table 1 adjusted according to Example 2 and containing a surfactant (0.01%) 500p
pm, the soybean leaves were immersed in each of these solutions for 30 seconds, air-dried, and then placed in a plastic cup. Ten second instar larvae of Spodoptera litura were released, covered, and left in a constant temperature room at 25 ° C. Two days later, the number of live and dead insects was counted, and the result of calculating the mortality was shown in Table 2. Table 2 shows that the mortality was 10
A for 0%, B for 99-80%, 79-60
% And C if not more than 59%.

[0051]

[Table 2]

(2) Efficacy test on brown planthopper Each wettable powder of compound (1) shown in Table 1 prepared according to Example 2 was added to water containing a surfactant (0.01%) for 30 times each.
After dilution to 0 ppm, 30 rice seedlings were added to each of these solutions.
After immersion for 2 seconds and air drying, it was inserted into a glass cylinder. Release 10 fourth instar larvae of the brown planthopper, stopper with a porous plug,
It was left in a constant temperature room. After 4 days, the number of live and dead insects was counted, and the mortality was determined. The results of the evaluation of the insecticidal effect are shown in Table 3 using the four-step evaluation method described in the above (1).

[0053]

[Table 3]

(3) Efficacy test on adult female spider mite (Acari: Tetranychidae)
m) and tested. On the other hand, the leaf pieces were placed for 15 seconds in a solution prepared by diluting each wettable powder of the compound (1) shown in Table 1 adjusted according to Example 2 to 300 ppm with water containing a surfactant (0.01%). Dipped. After being left in a constant temperature room at 25 ° C., three days later, the number of live and dead insects was counted, and the mortality was determined. The results of the evaluation of the insecticidal effect are shown in Table 4 using the four-step evaluation method described in the above (1).

[0055]

[Table 4]

(4) Efficacy test on spider mite eggs Five adult female spider mites were treated with kidney bean leaves (diameter 20 mm).
Were inoculated and spawned for 24 hours to remove female adults. On the other hand, compound (1) shown in Table 1 adjusted according to Example 2
The leaf pieces were immersed for 15 seconds in a chemical solution in which each of the wettable powders was diluted to 300 ppm with water containing a surfactant (0.01%). After standing in a constant temperature room at 25 ° C., the number of hatching larvae was counted after 7 days, and the ovulation rate was determined. The results of the evaluation of the insecticidal effect are shown in Table 5 by the four-step evaluation method described in the above (1).

[0057]

[Table 5]

(5) Efficacy test for Acarina acarina A filter paper having a length of 2.5 cm and a width of 0.5 cm is impregnated with an acetone solution of the compound shown in Table 1 in an amount of 0.01 to 0.1 g / m 2, and air-dried, and the resulting product is air-dried. I got 6m for each filter paper
1 volume of each screw-capped vial, 20 each
Two days later, the number of live and dead mites was counted, and the mortality was determined. Judgment of the acaricidal effect is performed in four stages (A: 95% or more, B: less than 95 to 9) depending on the range of the mortality.
0%, C: less than 90 to 50%, D: less than 50%). In addition, the comparative compound was used in the same test method as the compound of the present invention. The comparative compound is permethrin (trade name; Adion) and has the following formula:

[0059]

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## EQU5 ## Table 6 shows the results.

[0061]

[Table 6]

(6) Rice Hydroponic Efficacy Test on Brown Planthopper (Osmotic Migration) A wettable powder of compound (1) shown in Table 1 prepared according to Example 2 was weighed into an Erlenmeyer flask and diluted with water to 100 ppm. did. Next, the roots of rice seedlings were thoroughly washed with water, and only the roots were immersed in a chemical solution. Thereafter, a glass cylinder was set, and ten fourth-instar larvae of the brown planthopper were released, plugged with gauze, and left in a constant temperature room at 25 ° C. After 4 days, the number of live and dead insects was counted, and the mortality was determined. In Table 7, those with 100% mortality are A, 9
9-80% B, 79-60% C, 59
% Is shown as D.

[0063]

[Table 7]

(7) Cabbage pot soil treatment efficacy test against Japanese moth (osmotic transferability) A wettable powder of the compound (1) shown in Table 1 prepared according to the working conditions and containing a surfactant (0.01%) 500pp with water
20 ml of the drug solution diluted to 1 m was irrigated into the cabbage root of a 7-8 leaf stage potted cabbage plant and left in a glass greenhouse. 7
After a day, the leaves were cut off and placed in plastic cups. Thereafter, ten third instar larvae of the Japanese moth were released, covered, and left in a constant temperature room at 25 ° C. Two days later, the number of live and dead insects was counted, and the result of determining the mortality was shown in Table 8. Table 8 shows that the mortality rate is 100
% For A, 99-80% for B, 79-60%
Is indicated as C, and those with 59% or less are indicated as D.

[0065]

[Table 8]

(8) Antibacterial test A PDA (potato dextrose agar) medium was mixed with an acetone solution of a reagent so as to have a final concentration of 20 ppm to prepare a plate medium. The flora of Plum yellow rot fungus and rice blast fungus grown on a PDA plate medium in advance was cut into a 1 mm square with a scalpel and inoculated into the prepared plate medium containing the drug. The cells were cultured in the dark at 25 ° C. for 3 days, and the control value was determined by comparing the microflora diameter with the group without addition of the drug. Based on this control value, a 6-point evaluation of 0 to 5 was performed (0: 0 to 10).
%, 1:10 to less than 45%, 2:45 to less than 70%, 3:70 to less than 85%, 4:85 to less than 95%,
5: 95-100%). The results are shown in Table 9.

[0067]

[Table 9]

[0068]

Industrial Applicability The novel pyrazole carboxylic acid haloalkenyl ester derivative of the present invention has an excellent agricultural and horticultural pest control effect.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasushi Yasushi Nakabu, Ube City, Yamaguchi Prefecture, 1978 Kogushi, 5 Ube Research & Development Co., Ltd. Ube Research Laboratory ￥ plain F term (reference) 4H011 AA01 AC01 AC04 AC08

Claims (3)

[Claims] (1) The following formula (1): A pyrazole carboxylic acid haloalkenyl ester derivative represented by the formula: In the formula, R ¹ , R ² , R ³ , X ¹ , X ² and n are as follows. R ¹ represents a lower alkyl group. R ² represents a lower alkyl group or a phenyl group. R ³
Represents a halogen atom or a hydrogen atom. R ² and R ³ are
Together with the carbon atom at their substitution position, the saturated 5
It can also form a 7-membered ring. X ¹ represents a halogen atom or a hydrogen atom. X ² represents a halogen atom.
n represents an integer of 1 to 6. 2. The following formula (2): (Wherein R ¹ , R ² and R ³ are as defined in claim 1) and a pyrazole carboxylic acid represented by the following formula (3): (Wherein, Y represents a halogen atom or a lower alkylsulfonyloxy group; X ¹ , X ² and n have the same meanings as in claim 1). A method for producing a pyrazolecarboxylic acid haloalkenyl ester derivative represented by the formula (1) according to claim 1. 3. A pest control agent comprising, as an active ingredient, a pyrazole carboxylic acid haloalkenyl ester derivative represented by the formula (1) according to claim 1.