JP2001240592A - 5-alkylthiopyrazole-3-carboxamide derivative, its intermediate and agrochemical containing the same as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an new compound that has control effect against disease germ of various kinds of plants. SOLUTION: The compound is a 5-alkylthiopyrazole-3-carbxamide derivative shown by formula (1). [In the formula, R1 shows an alkyl or haloalkyl, R2 shows hydrogen, a halogen or alkyl. R3 and R4 show each hydrogen, alkyl or the like, independently and respectively. X shows hydrogen, a halogen, alkyl, or the like].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 5-alkylthiopyrazole-3-carboxamide derivative and a pesticide, particularly a fungicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art In the field of agriculture and horticulture, various fungicides for controlling various diseases have been developed and put to practical use. However, conventional agricultural and horticultural fungicides are not always satisfactory in terms of bactericidal effect, bactericidal spectrum or residual effect. Further, the demands such as reduction of the number of times of application and the amount of applied medicine have not been satisfied.

[0003] In addition, the emergence of pathogenic bacteria that have acquired resistance to conventional agricultural chemicals has also become a problem. For example, in the cultivation of vegetables, fruit trees, flowers, tea, wheat, rice and the like, various pesticides such as triazole, imidazole, pyrimidine, benzimidazole, dicarboximide, and phenylamide pesticides. Various pathogens which have acquired resistance have emerged in various places, and it has become difficult year by year to control various diseases caused by these pathogens.

[0004] Further, there are pesticides such as dithiocarbamate-based or phthalimide-based pesticides, for which pathogenic bacteria have not yet acquired resistance, but these are generally large in the amount of applied drug and the number of times of application, and are preferable from the viewpoint of environmental pollution and the like. Not something.
Therefore, even with various pathogens that have acquired resistance to conventional general-purpose agricultural and horticultural fungicides, they show a sufficient control effect at low doses,
In addition, there is a strong need for the development of a novel bactericide that has little adverse effect on the environment.

[0005] It is known that pyrazolecarboxamide derivatives have physiological activities such as insecticidal, acaricidal, fungicidal, herbicidal and pharmaceutical activities, respectively, depending on the three substituents on the pyrazole ring and the type of amino group in the carboxamide moiety. Have been. For example, 1-phenylpyrazole-3-carboxamide derivative is disclosed in JP-A-64-25763.
No. includes N-aralkyl having insecticidal and acaricidal activity.
1-phenylpyrazole-3-carboxamide derivatives have been reported. Japanese Unexamined Patent Publication (Kokai) No. 63-91373 discloses N-hydroxy-4-halo-5-unsubstituted-1-phenylpyrazole-3 as a substance having a harm-reducing action of herbicides.
Japanese Patent Application Laid-Open No. 1-283274 discloses a N-alkyl-4-unsubstituted-5-alkyl-carboxamide derivative.
1-phenylpyrazole-3-carboxamide derivatives; and JP-A-63-115867 discloses N-alkyl-4-unsubstituted-1,5-diphenylpyrazole-3-
Although carboxamide derivatives are described, they do not describe bactericidal activity at all. Further, N-alkyl-4-halo-1,5-diphenylpyrazole-3-carboxamide having herbicidal activity is disclosed in JP-A-8-1265.
No. 4 discloses no bactericidal activity.

Furthermore, N-alkyl- having a pharmaceutically active property
4-Unsubstituted-5-alkoxy-1-phenylpyrazole-3-carboxamide derivatives are described in Pharmaceutical Journal, 97, 71
9 (1977) and Journal of Med
Ial Chemistry, vol. 20, p. 80 (19
77), but nothing about the pesticidal activity. Also, N-methyl-4-bromo-5-methoxy-1-phenylpyrazole-3-carboxamide was reported in Nagoya City University Pharmaceutical School Annual Report, Vol. 29, p. 25 (1).
981), but it has no medicinal activity and no description of pesticide activity. The present inventors have previously proposed N- compounds having an alkyl group or an alkoxy group at the 5-position as a compound having a bactericidal activity against plant pathogenic bacteria.
Alkyl-1-phenylpyrazole-3-carboxamide derivatives have been proposed (JP-A-11-171867 and JP-A-11-199566).

[0007]

DISCLOSURE OF THE INVENTION The present invention provides an agricultural and horticultural fungicide which has a high control effect against various pathogens which are resistant to conventional agricultural and horticultural fungicides and which has excellent residual effect. It is to provide a new chemical substance useful as an active ingredient.

[0008]

The present inventors have made intensive efforts to solve the above-mentioned problems, and as a result, have found that a novel N-alkyl-1-phenylpyrazole-3-in which an alkylthio group is introduced at the 5-position of the pyrazole ring. The present inventors have found that a carboxamide derivative has the above-mentioned characteristics and is particularly excellent in residual activity, and has completed the present invention. That is, the gist of the present invention is represented by the following general formula (I)

[0009]

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(Wherein R¹Is a hydrogen atom, C₁ ~ C_Four No
Alkyl group or C₁ ~ C_FourRepresents a haloalkyl group. R
^TwoIs a hydrogen atom, a halogen atom, C₁ ~ C_Four The alkyl of
Group, trifluoromethyl group, nitro group, cyano group, C₁
~ C_FourAn alkoxy group of C₁ ~ C _Four Haloalkoxy
Group, C₁ ~ C_Four An alkylthio group of C₁ ~ C_Four Archi
Rusulfinyl group, C₁ ~ C_Four Alkylsulfonyl group of
Is shown. X represents a hydrogen atom, a halogen atom or C₁~ C_Four
Represents an alkyl group. R^ThreeAnd R^FourAre independent
And a hydrogen atom, C₁ ~ C_Four Alkyl or allyl group of
Is shown. 5-alkylthiopyrazole-3 represented by the formula:
-Carboxamide derivative and this derivative as active ingredient
To be contained in pesticides.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The substituent R of the compound of the present invention represented by the general formula (I)
Specific examples of ¹ include C ₁ such as methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group. ~ C ₄ Linear, branched or cyclic alkyl group; fluoromethyl group, a difluoromethyl group, a haloalkyl group of C ₁ -C _4, such as a trifluoromethyl group. Particularly, R ¹ is preferably a methyl group. Specific examples of R ² include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group; Isobutyl group, sec-butyl group,
C ₁ -C ₄ such as t-butyl group Linear, branched or cyclic alkyl group; trifluoromethyl group; nitro group; cyano group; methoxy group, ethoxy group, n-propoxy group,
Isopropoxy group, n-butoxy group, isobutoxy group,
C ₁ such as sec-butoxy group and t-butoxy group ~ C ₄ Alkoxy group; difluoromethoxy group, trifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 2,2
2-trichloroethoxy group, 3-chloropropoxy group,
3-bromopropoxy group, 3,3,3-trifluoropropoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 2,2-dichloro -3,3,3-trifluoropropoxy group, 1,3-difluoro-2-propoxy group,
1,1,1,3,3,3-hexafluoro-2-propoxy group, 3,3,3-trichloropropoxy group, 4-chlorobutoxy group, 4,4,4-trifluorobutoxy group, 3,3 , 4,4,4 C ₁ such as pentafluoro-butoxy group ~ C ₄ Haloalkoxy group; C ₁ corresponding to the above alkyl group ~ C ₄ Alkylthio group; C ₁ corresponding to the above alkyl group ~ C ₄ Alkylsulfinyl group or alkylsulfonyl group. R ² is preferably a halogen atom, C ₁ -C ₄ Alkyl group, trifluoromethyl group, cyano group, C ₁ ~ C ₄ An alkoxy group of C
₁ ~ C ₄ Is preferred, and the substitution position on the benzene ring is preferably para-position to the pyrazole ring. Specific examples of X include, for example, a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group; C ₁ -C ₄ such as isobutyl group, sec-butyl group, t-butyl group, etc. A linear, branched or cyclic alkyl group.
X is particularly preferably a methyl group or a halogen atom.

R ³ and R ⁴ each independently represent a hydrogen atom; methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, t- C ₁ such as butyl group ~ C ₄ A linear, branched or cyclic alkyl group; or an allyl group. Preferably, one of R ³ and R ⁴ is a hydrogen atom and the other is C _{2 to} C ₄ And particularly preferably an n-propyl group. The compound of the present invention represented by the above general formula (I) is a novel compound and can be produced, for example, according to the following reaction.

[0013]

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(Wherein R ¹ , R ² , R ³ , R ⁴ and X are as defined in the above formula (I), and R ⁵ is C ₁ ~ C ₄ Represents an alkoxy group, a hydroxyl group or a halogen atom. In the above formula (II), when R ⁵ represents a halogen atom, the reaction can be carried out in the presence of a solvent in the presence of a base. The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; halogens such as chloroform and methylene chloride. Hydrocarbons; water; alcohols such as methanol, ethanol and propanol;
Esters such as methyl acetate and ethyl acetate; polar solvents such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane and diisopropyl ether; or mixed solvents of the above solvents. .
Examples of the base include sodium hydroxide, potassium hydroxide, pyridine and triethylamine. The reaction temperature is 0 ° C to 30 ° C, preferably 0 ° C to 5 ° C.

In the general formula (II), R ⁵ is C ₁
~ C ₄ When it is an alkoxy group or a hydroxyl group, the reaction can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include alcohols such as methanol, ethanol, and propanol. The reaction temperature is 5-100 ° C, preferably 20-80 ° C.

After the reaction, in order to isolate the target compound represented by the general formula (I), when a solvent soluble in water is used, the solvent is distilled off under reduced pressure and water is added. Afterwards, aromatic hydrocarbons such as benzene, toluene and xylene which are insoluble in water;
Extraction may be performed with a halogenated hydrocarbon such as chloroform, dichloromethane or the like; an ester such as ethyl acetate, washed with a saturated saline solution, dried with a desiccant such as anhydrous sodium sulfate, and the solvent may be distilled off under reduced pressure. When a water-insoluble solvent is used, water is added to the reaction mixture, and the mixture is separated.The organic layer is washed with saturated saline, dried with a drying agent such as anhydrous sodium sulfate, and the solvent is distilled off under reduced pressure. Just leave. The residue obtained after distillation may be sufficiently pure as it is, but if it is impure, wash it with a hydrocarbon such as hexane or heptane that does not substantially dissolve the target substance, or use recrystallization or column chromatography. Purification gives a pure product.

The compound of the general formula (II) as a starting material is a novel compound which has not been described in the literature and can be synthesized, for example, according to the following reaction formula. 1) X is a hydrogen atom, C ₁ ~ C ₄ A compound of an alkyl group;

[0018]

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2) compounds wherein X is a halogen atom;

[0020]

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(In the above formula, R ¹ , R ² and X are as defined in the general formulas (I) and (II).) When the compound of the general formula (IV) is reacted with an alkylating agent,
In the general formula (II), R ¹ is C ₁ ~ C ₄ The compound (II-a) which is an alkylthio group of the formula (I) is obtained. General formula (II-
In a), when a compound in which X is a hydrogen atom is reacted with a halogen or a sulfuryl halide, X in the general formula (II)
Is a compound (II-b) wherein is a halogen atom

The reaction with the above-mentioned alkylating agent can be carried out in the presence or absence of a solvent, in the presence or absence of a base. The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; water;
Esters such as methyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; polar solvents such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane and diisopropyl ether Alcohols such as methanol, ethanol, 2-propanol and ethylene glycol, or mixed solvents of the above solvents. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonate Alkali metal bicarbonates such as sodium and potassium bicarbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; metal alkoxides such as sodium methoxide and sodium ethoxide; and organic bases such as pyridine and triethylamine. . Examples of the alkylating agent include sulfates such as dimethyl sulfate and diethyl sulfate; alkyl halides such as chloromethane, chloroethane, bromomethane, bromoethane, iodomethane, iodoethane, and chlorodifluoromethane; and carbonates such as methyl carbonate and ethyl carbonate. No. The reaction temperature is 5 to 150C, preferably 10 to 100C.

After the reaction, in order to isolate the target compound represented by the general formula (II-a), when a solvent soluble in water is used, the solvent is distilled off under reduced pressure to remove water. After the addition, the mixture is extracted with water-insoluble aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; esters such as ethyl acetate, and the like. What is necessary is just to dry with a drying agent such as described above and distill off the solvent under reduced pressure. When a water-insoluble solvent is used, water is added to the reaction mixture, and the mixture is separated. The organic layer is washed with saturated saline, dried with a drying agent such as anhydrous sodium sulfate, and then the solvent is distilled off under reduced pressure. do it. The residue obtained after distillation may be sufficiently pure as it is, but if it is impure, wash it with a hydrocarbon such as hexane or heptane that does not substantially dissolve the target substance, or use recrystallization or column chromatography. Purification gives a pure product.

The reaction with the above halogen or sulfuryl halide can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as chloroform and dichloromethane. Examples of the halogen or sulfuryl halide include fluorine, chlorine, bromine, iodine, sulfuryl chloride, and sulfuryl bromide. The reaction temperature is 5 to 100 ° C, preferably 10 to 9 ° C.
0 ° C. After the reaction, in order to isolate the compound represented by the general formula (II-b), which is the target substance, an alkali metal carbonate such as sodium carbonate and potassium carbonate; an alkali metal carbonate such as sodium hydrogen carbonate and potassium hydrogen carbonate An aqueous solution of a hydrogen salt or the like is added to neutralize the reaction solution. After liquid separation, the organic phase is washed with saturated saline, dried with a desiccant such as anhydrous sodium sulfate, and the solvent may be distilled off under reduced pressure. The residue obtained after evaporation of the solvent may be sufficiently pure as it is,
If necessary, a pure product can be obtained by washing with a hydrocarbon solvent such as hexane or heptane that hardly dissolves the target substance, or by purifying by means such as recrystallization or column chromatography. 3) when R ⁵ is a hydroxyl group;

[0025]

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(In the above formula, R ¹ , R ² and X are as defined in the above general formulas (I) and (II).) The above reaction is carried out in the presence or absence of a solvent and in the presence of a base. Can be done below. Examples of the solvent include water; alcohols such as methanol, ethanol, propanol, and ethylene glycol; and mixed solvents of the above solvents. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; magnesium hydroxide,
Alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth metals such as calcium carbonate and magnesium carbonate Metal carbonates. The reaction temperature is between 5 and
The temperature is 150 ° C, preferably 10 to 110 ° C. After the reaction,
In order to isolate the target compound represented by the general formula (II-c), the compound is made acidic with a mineral acid such as hydrochloric acid or sulfuric acid; or an organic acid such as acetic acid or propionic acid, and the precipitate is collected by filtration. It may be washed and then dried.

4) when R ⁵ is a halogen atom;

[0028]

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(In the above formula, R ¹ , R ² and X are as defined in the above formulas (I) and (II), and Z represents a halogen atom.) Compound of formula (II-c) Is reacted with a halogenating agent to obtain a compound (II-d) in which R ⁵ is a halogen atom in the general formula (II). The above reaction can be performed in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as chloroform and dichloromethane. Examples of the halogenating agent include thionyl chloride, thionyl bromide, oxalyl chloride, oxalyl bromide, phosphorus pentachloride, phosphorus pentabromide, phosphorus trichloride and the like. The reaction temperature is 5-100 ° C, preferably 20-90.
° C. After the reaction, in order to isolate the target compound represented by the general formula (II-d), the reaction solution is concentrated under reduced pressure,
The obtained residue may be washed with a hydrocarbon, such as hexane or heptane, which hardly dissolves the target substance, and then dried.

The compound of the present invention represented by the general formula (I)
It has a high bactericidal effect against various plant pathogenic fungi such as blast fungus, rust fungus, downy mildew fungus and plague fungus, and is useful as an active ingredient of pesticides, especially fungicides for agricultural and horticultural use. However, the phytopathogenic bacteria to be controlled by the compound of the present invention are not limited to those exemplified above. When the compound of the present invention represented by the general formula (I) is used as a fungicide for agricultural and horticultural use, it may be used alone, but preferably as a composition containing an agricultural chemical adjuvant commonly used in the art. It is preferably used. The dosage form of the fungicide for agricultural and horticultural use is not particularly limited, but is preferably in the form of, for example, emulsion, wettable powder, powder, flowable, fine granule, granule, tablet, oil, spray, aerosol, etc. It is. One or two of the above compounds
More than one species can be included as active ingredients.

Agrochemical auxiliaries used for producing agricultural and horticultural fungicides include, for example, the improvement of the effect of agricultural and horticultural fungicides,
A substance having an effect of stabilizing and improving dispersibility, for example, a carrier (diluent), a spreading agent, an emulsifier, a wetting agent, a dispersant, a disintegrant, and the like can be used. Examples of the liquid carrier include water; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, butanol, and glycol; ketones such as acetone; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; methylnaphthalene Cyclohexane; animal and vegetable oils; and fatty acids. As the solid carrier, for example, clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose,
Starch, gum arabic and the like. Usable emulsifiers and dispersants include ordinary surfactants, for example, anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine; A nonionic surfactant; a zwitterionic surfactant; or the like can be used. A spreading agent such as polyoxyethylene nonyl phenyl ether and polyoxyethylene lauryl phenyl ether; a wetting agent such as dialkyl sulfosuccinate; a fixing agent such as carboxymethyl cellulose and polyvinyl alcohol; sodium lignin sulfonate and sodium lauryl sulfate; Can be used.

The content of the active ingredient in the fungicide for agricultural and horticultural use of the present invention is selected from the range of 0.1 to 99.5%, and may be appropriately determined according to various conditions such as the form of preparation and the method of application. For example, in the case of powder, about 0.5 to 20% by weight,
Preferably 1 to 10% by weight, about 1 to 90% by weight, preferably 10 to 80% by weight for wettable powders,
About 90% by weight, preferably 10 to 40% by weight, and about 1 to 90% by weight, preferably 10 to 5% for a flowable agent.
It is preferred to prepare them so as to contain 0% by weight of the active ingredient.

For example, in the case of an emulsion, an emulsion of a stock solution can be prepared by mixing a solvent, a surfactant and the like with the above-mentioned compound which is an active ingredient. Dilute with and apply. In the case of a flowable agent, a stock solution can be produced by mixing water, a surfactant and the like with the compound of the general formula (I) as an active ingredient. Dilute and apply. In the case of a wettable powder, the compound is produced by mixing the above-mentioned compound of the active ingredient, a solid carrier, a surfactant and the like, and further diluted with water to a predetermined concentration before use. In the case of a powder, the compound of the active ingredient and the solid carrier can be mixed and applied as it is, and in the case of a granule, the compound of the active ingredient, the solid carrier and a surfactant can be mixed and granulated. It can be manufactured and applied as it is. However, the production method of each of the above-mentioned preparation forms is not limited to the above-mentioned one, and can be appropriately selected by those skilled in the art according to the kind of the active ingredient, the purpose of application, and the like.

The agricultural and horticultural fungicide of the present invention comprises an active ingredient
Unless the activity of a compound of the general formula (I) is impaired,
Fungicides, insecticides, acaricides, herbicides, insect growth regulation
Agent, fertilizer, soil improver, etc.
Good. The method for applying the agricultural and horticultural fungicide of the present invention is not particularly limited.
Foliage application, water application, soil treatment, seeds
It can be applied by any method such as child treatment. An example
For example, in the case of foliage application, 5 to 1,000 ppm is preferable.
Or 10-500ppm solution in a concentration range of 10-500ppm
It can be used at an application rate of about 100 to 200 L per
Wear. In the case of surface application, the application amount is usually 5 to 5
For 15% granules, 1-10kg per 10 ares
You. For soil treatment, concentration range of 5 to 1,000 ppm
1m of solution ^Two Use at an application rate of about 1 to 10 L per
be able to. In case of seed treatment, per 1kg of seed weight
A solution in a concentration range of 10 to 1,000 ppm
About 0 ml can be applied.

[0035]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and test examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Reference Example 1 <Synthesis of ethyl 1- (4-chlorophenyl) -5-thiopyrazole-3-carboxylate> 20.0 g of ethyl 1- (4-chlorophenyl) -5-hydroxypyrazole-3-carboxylate was added to toluene 400
Dissolve in 1 ml, Lawsonson's Reagent 1
8.2 g was added and the mixture was heated under reflux for 1 hour. The reaction solution was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 11.5 g of the desired product. Melting point was 92-94 ° C.

Example 1 <1- (4-chlorophenyl)
Synthesis of ethyl-5-methylthiopyrazole-3-carboxylate> 7.61 g of the compound obtained in Reference Example 1 and 5.2 of potassium carbonate
2 g of ethanol was suspended in 200 ml of ethanol, 4.12 g of dimethyl sulfate was added, and the mixture was heated at 70 ° C. for 0.5 hour. The mixture was concentrated under reduced pressure, water was added to the obtained residue, and the mixture was extracted with ethyl acetate. The organic phase was washed with water and saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was washed with hexane, and the compound No. shown in Table 1 was used. 1 to 6.
51 g were obtained. Melting point was 90-91 ° C.

Example 2 <Synthesis of ethyl 4-chloro-1- (4-chlorophenyl) -5-methylthiopyrazole-3-carboxylate> 1- (4-Chlorophenyl) -5-methylthiopyrazole obtained in Example 1 2.97 g of ethyl-3-carboxylate
And 1.0 ml of sulfuryl chloride was heated under reflux for 10 minutes in 7 ml of methylene chloride. After the reaction solution was cooled to room temperature, it was added to ice water and neutralized by adding sodium carbonate. The mixture was extracted with methylene chloride, washed with water and saturated saline, and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel chromatography. 2.01 g of Compound 5 was obtained. Melting point was 56-58 ° C.

Example 3 <Synthesis of 4-chloro-1- (4-chlorophenyl) -5-methylthiopyrazole-3-carboxylic acid> 4-Chloro-1- (4-chlorophenyl) -5 obtained in Example 2 -Methylthiopyrazole-3-carboxylate (2.45 g) and sodium hydroxide (0.59 g) were added to water 6
Heated to reflux in 1 ml for 1 hour. After cooling the reaction solution to room temperature,
Hydrochloric acid was added to make it acidic, and the precipitate was collected by filtration, washed with water and dried. 1.95 g of Compound 7 was obtained. The melting point was 185-186 ° C.

Example 4 <Synthesis of 4-chloro-1- (4-chlorophenyl) -5-methylthiopyrazole-3-carboxylic acid chloride> 4-Chloro-1- (4-chlorophenyl)-obtained in Example 3 5-methylthiopyrazole-3-carboxylic acid
85 g of the mixture was heated under reflux in 5 ml of thionyl chloride for 1 hour and then concentrated. The obtained residue was washed with hexane to obtain the desired product.

Example 5 According to the method of Examples 1 to 3, the compounds shown in Table 1 were obtained.

[0041]

[Table 1]

Example 6 <Synthesis of 4-chloro-1- (4-chlorophenyl) -5-methylthio-NN-propylpyrazole-3-carboxamide> 4-Chloro-1- (4) obtained in Example 5 -Chlorophenyl) -5-methylthiopyrazole-3-carboxylic acid chloride (0.48 g) was added to a solution of 0.44 g of n-propylamine in 5 ml of ethyl acetate, followed by stirring at room temperature for 1 hour. Water was added and extracted with ethyl acetate. The organic phase was washed with saturated saline and dried over anhydrous sodium sulfate. Concentrate under reduced pressure,
The obtained residue was washed with hexane to obtain 0.38 g of the compound (No. 8) shown in Table 2. Melting point 76-77 ° C
Met.

Example 7 According to the method of Example 6, the compounds shown in Table 2 were obtained.

[0044]

[Table 2]

The following are examples of preparations of agricultural and horticultural fungicides containing the compound of the present invention as an active ingredient, but the form of the agricultural chemical of the present invention is not limited to the following. In addition, Compound No. Is the compound No. in Tables 1 and 2. Corresponding to

<Production Example 1> Wetting agent Compound No. 8 in 20 parts by weight, Carplex # 80
(White carbon, Shionogi & Co., Ltd., trade name) 2
0 parts by weight, 52 parts by weight of ST kaolin clay (Kaolinite, Tsuchiya Kaolin Co., Ltd.), Solpol 9047K
(Anionic surfactant, Toho Chemical Co., Ltd., trade name)
5 parts by weight and 3 parts by weight of Lunox P65L (anionic surfactant, Toho Chemical Co., Ltd., trade name) were blended and uniformly mixed and pulverized to obtain a wettable powder containing 20% by weight of the active ingredient.

<Production Example 2> Powder Compound No. 8 in 2 parts by weight, clay (manufactured by Nippon Talc)
93 parts by weight and 5 parts by weight of Carplex # 80 (white carbon, Shionogi & Co., Ltd., trade name) were uniformly mixed and pulverized to produce a powder of 2% by weight of the active ingredient.

<Production Example 3> Emulsion Compound No. 8 was dissolved in a mixed solvent consisting of 20 parts by weight, 35 parts by weight of xylene and 30 parts by weight of dimethylformamide, and dissolved in Solpol 3005X (a mixture of a nonionic surfactant and an anionic surfactant, Toho Chemical Co., (Name) 15 parts by weight to obtain an emulsion containing 20% by weight of the active ingredient.

<Production Example 4> Flowable agent Compound No. 8 in 30 parts by weight, Solpol 9047K
5 parts by weight, sorbone T-20 (nonionic surfactant,
3 parts by weight of Toho Chemical Co., Ltd., 8 parts by weight of ethylene glycol and 44 parts by weight of water were wet-pulverized with a Dynomill (manufactured by Shinmaru Enterprises), and 1% by weight of xanthan gum (natural polymer) was added to this slurry-like mixture. ) Add 10 parts by weight of an aqueous solution, mix well and pulverize to obtain the active ingredient 2.
0% by weight of a flowable agent was obtained.

<Test Example 1> Sterilizing effect on rice blast 10 rice plants (variety: Akinishiki) were grown per pot in a resin pot having a diameter of 6 cm. The fungicide (emulsion) for agriculture and horticulture of the present invention prepared according to the formulation of Formulation Example 3 was diluted with water to a predetermined concentration and sprayed on the rice (3 to 4 leaf stage) at a ratio of 10 ml per pot with foliage. After the sprayed drug solution was air-dried, the rice blast fungus (Magnaporthe grisea) cultured in oatmeal medium was added to the rice.
Was spray inoculated with a spore suspension (5.0 × 10 ⁵ spores / ml) and kept in a moist chamber at 25 ° C. for 24 hours. Then, it was left to stand in a greenhouse (22 to 25 ° C.) for 7 days, the area ratio of the appeared lesions was measured, and the control value was calculated by the following formula. Table 3 shows the results.
Shown in In addition, Compound No. Is the compound No. in Table 2. Corresponding to

[0051]

(Equation 1)

[0052]

[Table 3]

Test Example 2 Soil Degradability Test 20 g of paddy field soil (water content: 30% by weight) was collected in a glass beaker (100 ml), and 20 ml of distilled water was added thereto. 27 with lid
Pre-incubation was performed in a thermostat at room temperature for 1 week. The compound no. 10 dimethylsulfoxide solution (10 mg / 50 ml) was added with a microsyringe to 200
μl was added and mixed uniformly. The beaker was capped with aluminum foil having fine holes, and allowed to stand in a thermostat at 27 ° C. The mixture was allowed to stand for 7 days while appropriately replenishing water so that the total weight in the beaker was 40 g. After adding 40 ml of acetonitrile to the beaker and extracting with an ultrasonic cleaner for 5 minutes, the soil and acetonitrile were centrifuged. The layers were separated. The soil was extracted three more times with acetonitrile. The separated acetonitriles were put together in an eggplant flask, and concentrated to about 20 ml with a rotary evaporator. 50 ml of 2% saline was added to the remaining liquid, and the mixture was placed in a separating funnel and extracted four times with 40 ml of n-hexane. The extracts were combined and concentrated to dryness using a rotary evaporator. The residue was dissolved in acetonitrile, and the compound No. 1 was purified by high performance liquid chromatography. Quantify 10 and
The residual rate was determined. Similarly, the residual ratio of Comparative Compounds 1 to 3 (compounds described in JP-A-11-199566) was determined. The results are shown in Table-4.

[0054]

[Table 4]

The comparative compound has the following structure.

[0056]

Embedded image

[0057]

According to the present invention, the 5-alkylthiopyrazole-
3-Carboxamide has an excellent control effect on plant pathogenic bacteria, has an excellent residual rate in soil, and is useful as an agricultural chemical.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H011 AA01 BA01 BA05 BB09 BC01 BC06 BC18 BC20 DA02 DA15 DA16 DC01 DC05 DD03 DE15 DG05

Claims (9)

[Claims] 1. A compound represented by the following general formula (I):(Where R¹Is a hydrogen atom, C₁ ~ C_Four The alkyl group of
Is C₁ ~ C_Four Represents a haloalkyl group. R^TwoIs hydrogen field
Child, halogen atom, C₁ ~ C_Four Alkyl group, triflu
Oromethyl group, nitro group, cyano group, C₁ ~ C_Four Al
Coxy group, C₁ ~ C _Four Haloalkoxy group, C₁ ~ C_Four
An alkylthio group of C₁ ~ C_Four Alkylsulfinyl
Group, C₁ ~ C_Four Represents an alkylsulfonyl group. X is water
Elementary atom, halogen atom or C₁ ~ C_Four The alkyl group of
Show. R^ThreeAnd R^FourIs independently a hydrogen atom, C
₁ ~ C_Four Represents an alkyl group or an allyl group. )
5-alkylthiopyrazole-3-carboxamide
Derivatives. 2. The 5-alkylthiopyrazole-3-carboxamide derivative according to claim 1, wherein R ¹ in the general formula (I) is a methyl group. 3. R in the general formula (I)^TwoIs a halogen field
Child, C₁ ~ C_Four An alkyl group, a trifluoromethyl group,
Cyano group, C₁ ~ C_Four An alkoxy group of C₁ ~ C_Four No ha
Selected from the alkoxy group and bonding of a pyrazole ring
Characterized in that it is a substituent at the para-position of the moiety
The 5-alkylthiopyra according to claim 1 or 2,
A sol-3-carboxamide derivative. 4. The method according to claim 1, wherein one of R ^{3 and} R ⁴ in the general formula (I) is a hydrogen atom, and the other is a C ₂ -C ₄ alkyl group. A 5-alkylthiopyrazole-3-carboxamide derivative as described above. 5. The compound according to claim 1, wherein one of R ^{3 and} R ⁴ in the general formula (I) is a hydrogen atom, and the other is an n-propyl group. Alkylthiopyrazole-3-carboxamide derivatives. 6. The 5-alkylthiopyrazole-3-carboxamide derivative according to claim 1, wherein X in the general formula (I) is a methyl group or a chlorine atom. 7. The following general formula (II):(Where R¹, R^TwoAnd X are the same as in the case of the general formula (I)
Has the significance of R^FiveIs C ₁ ~ C_Four An alkoxy group of
A loxyl group or a halogen atom).
Alkylthiopyrazole-3-carboxylic acid derivatives. 8. A pesticide comprising the 5-alkylthiopyrazole-3-carboxamide derivative according to claim 1 as an active ingredient. 9. The bactericide according to claim 8, wherein the bactericide is a bactericide.
Pesticides as described.