KR900003390B1 - Pyrazol derivatives and agricultural and horticultural fungicides containing said compounds - Google Patents

Abstract

Pyrazol derivs. of fromula (I) are prepd. by reacting pyrazolcarboxylate with aminoacetonitrile. In (I), R1=alkyl, haloalkyl, alkenyl, haloalkenyl or phenyl; R2 and R3 are each H, halo, alkyl, alkoxy or phenyl; R4=alkyl, alkenyl, substd. 2-furyl or zpyrrolyl. (I) are useful as an agricultural and horticultural fungicide.

Description

Pyrazole derivatives, preparation method thereof and agrohorticultural fungicide

The present invention relates to pyrazole derivatives of the general formula (I).

Wherein R ¹ represents an alkyl group, haloalkyl, alkenyl, haloalkenyl or phenyl group: R ² and R ³ each represent a hydrogen or halogen atom or an alkyl, haloalkyl, alkoxy, alkoxyalkyl, or phenyl group: R ⁴ represents an alkyl, alkenyl, haloalkenyl or phenyl group, or a substituted or unsubstituted heterocyclic aromatic group containing at least one oxygen, nitrogen or sulfur atom.

The present invention also relates to a method for producing these pyrazole derivatives and agrohorticultural fungicides containing these derivatives as active ingredients.

Conventionally, many researches on organic synthetic compounds useful for agrohorticulture have been conducted, and many biologically active compounds have been found and put to practical use. Numerous amide active compounds present in the backbone of the compounds according to the invention have been found, some of which have been used as herbicides or fungicides.

For example, as substituted benzamide derivatives, ethyl N-benzoyl-N- (3,4-dichlorophenyl-2-aminopropionate (benzoylpropetyl), useful as herbicide, and 2-methyl-N- (3-iso, useful as fungicide Propoxyphenyl) benzimide (mepronyl) is known.

Moreover, pyrazole type compounds effective as a herbicide are also known, for example, 4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yl P-toluene sulfonate (pyrazolate) And 4- (2,4-dichlorobenzoyl) -5-benzoylmethoxy-1,3-dimethylpyrazole (pyrazoxin) have been widely used as rice herbicides in Japan.

Substituted acylaminoacetonitrile derivatives having a furan ring as a herbicide and fungicide are described in Japanese Patent Application Laid-Open No. 167,978 / 1982, but these compounds are harmful to crops, and this document describes acyl groups as heterocyclic carbonyl groups. 4-pyridylcarbonyl, 2-furylcarbonyl, 2-thienylcarbonyl and 2-benzofurylcarbonyl groups are described.

The chemical abstract describes several methods for the synthesis of acylamino saturated aliphatic derivatives similar to the pyrazole derivatives according to the invention.

In more detail, the synthesis example of 2-benzoylaminobutyronitrile is described in J. Chen. Soc., 1963, pages 2143-2150 and in Synthesis, 1972, No. 11, pages 622-624, for examples of the synthesis of 2-benzoylaminopropionitrile. Soc. Chim. Fr., 1969, No. 11, pages 4108-4111 and Justus Liebigs Ann. Chem., 1972, 764, pages 69-93, although these documents do not mention the biological activity of the subject matter.

As a horticultural fungicide, synthetic compounds having various chemical structures have been used to play an enormous role in controlling plant diseases. As a result, they have greatly contributed to the development of agriculture. However, some of these compounds have never been satisfactory in controlling activity and stability. For example, captapol, TPN, and dithiocarbamate drugs have been widely used for controlling late blight and powdery mildew of various cultivated plants, contributing to the increase of crops, but these compounds mainly have a preventive effect against late blight and powdery mildew. Because of this, the eradication effect cannot be expected at all. Therefore, these compounds cannot be expected to have satisfactory effects when used after disease development. In order to actually control plant diseases, some of these agents must be used after the outbreak. Therefore, these compounds are not only difficult to completely control plant diseases, but in order to exhibit control effects, these compounds must be used in very high concentrations and are prohibited from their use for safety reasons.

In addition, some of the aforementioned compounds cannot ignore the toxicity to fish.

Therefore, as a result of extensive research on novel control agents to solve the above-mentioned problems, metal lacxyl [methyl N- (2,6), which shows excellent prevention and eradication effect as a control agent of plant diseases caused by fungi. -Dimethylphenyl) -N- (2'-methoxyacetyl) alanine] and other derivatives of N-phenylalanine have been developed and are recognized worldwide. However, these N-phenylalanine ester derivatives have a problem in that their bactericidal effect is reduced because fungi obtained resistance to these compounds have already appeared.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art, to provide compounds having excellent properties as agricultural horticultural fungicides, methods for preparing these compounds, and to control harmful microorganisms containing these compounds as active ingredients. More specifically, the present invention has both a prophylactic and eradicating effect on crop diseases such as late blight and downy mildew, and can be widely used, and compounds that do not cause harm to cultivated plants, warm-blooded animals and fish, which are produced in high yield. It is a convenient method to do so and to provide useful pesticide compositions containing these compounds.

The present inventors have conducted extensive research on acylaminoacetonitrile derivatives. As a result, certain kinds of pyrazole derivatives have biological activities that cannot be expected from the above-mentioned compounds. It has been found that it has an excellent control effect, in particular an excellent prevention and eradication effect against crop diseases such as late blight and downy mildew.

That is, according to the present invention, novel pyrazole derivatives of the general formula (I) are provided.

Wherein R ¹ represents an alkyl group, haloalkyl, alkenyl, haloalkenyl or phenyl group: R ² and R ³ each represent a hydrogen or halogen atom or an alkyl, haloalkyl, alkoxy, alkoxyalkyl, or phenyl group: R ⁴ represents an alkyl, alkenyl, haloalkenyl or phenyl group, or a substituted or unsubstituted heterocyclic aromatic group containing at least one oxygen, nitrogen or sulfur atom.

In formula (I), R ¹ is an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a haloalkyl group, preferably a lower haloalkyl group having 1 to 6 carbon atoms , Alkenyl group, preferably a lower alkenyl group having 2 to 6 carbon atoms, a haloalkenyl group, preferably a lower haloalkenyl group having 2 to 6 carbon atoms or a phenyl group. R ² and R ³ are each a hydrogen atom, a halogen atom, preferably a lower alkyl group having 1 to 6 carbon atoms, a haloalkyl group, preferably a lower alkyl group having 1 to 6 carbon atoms, a haloalkyl group, preferably having 1 to 6 carbon atoms 6 lower haloalkyl groups, alkoxy groups, preferably lower alkoxy groups having 1 to 6 carbon atoms, alkoxyalkyl groups, preferably lower alkoxyalkyl groups having 2 to 6 carbon atoms or phenyl groups. R ⁴ is an alkyl group, preferably a lower alkyl group having 1 to 6 carbon atoms, an alkenyl group, preferably an alkenyl group having 2 to 12 carbon atoms, more preferably a lower alkenyl group having 2 to 6 carbon atoms, a haloalkenyl group, Heterocyclic phase containing 2 to 6 carbon atoms of lower haloalkenyl group, phenyl group, or at least one oxygen, nitrogen or sulfur atom, preferably substituted or unsubstituted by furyl, thienyl or pyrrolyl group. An aromatic group is shown.

In addition, the inventors of the present invention have conducted extensive research on the preparation method of the pyrazole derivatives of the general formula (I), and have found a method of obtaining the target product in high yield.

Accordingly, according to the present invention, there is provided a method for preparing a pyrazole derivative of formula (I) characterized by reacting a compound of formula (III) with aminoacetonitrile of formula (IV) or a salt thereof: do.

(R ¹ , R ² , R ³ and R ⁴ are as defined in formula (I) above.)

Most of the pyrazole carboxylic acid chlorides (III) used as starting materials in the process of the invention are, for example, Aust. J. Chem. 36, 135 (1983) and Berichte der Deutschen Chemischen Gesellschaft, Vol. 59, 601 (1926), according to the methods described in the following reaction processes (A) to (E). There is a number.

[Reaction Process Formula (A)]

When R ² or R ³ is a methoxy group, the compounds of the general formula (III) can be synthesized by the following reaction formula (B) according to the method described in Japanese Patent Application Laid-Open No. 122,488 / 1984.

[Reaction Process Formula (B)]

In addition, as described in the following reaction process formula (C), a substituent may be introduced later into the nitrogen atom of the pyrazole ring using R ¹ x (R ¹ and x are as defined above).

[Reaction Process Formula (C)]

Pyrazole carboxylic acids can be obtained by oxidation of pyrazole aldehydes by reaction process formula (D).

[Reaction Process Formula (D)]

Pyrazole-5-carboxylic acids can be obtained by the method described in reaction process formula (E).

[Reaction Process Formula (E)]

Amino acetonitrile (IV) can be easily obtained by what is called the sheet trekger reaction described in the following reaction process formula (F).

Reaction Process Formula (F)

Specifically, aldehydes of general formula (V) and hydrogen cyanide (VI, M = H) or alkali metal cyanide (VI, M = alkali metal) and ammonia or ammonium chloride are water or two-layer water and organic It can be obtained easily by reacting in a solvent. The order of addition of aldehyde (V), cyanide (VI) and ammonia or ammonium chloride is arbitrary, and in most cases, the reaction proceeds more efficiently by adding a phase transfer catalyst.

Since the resulting aminoacetonitriles are unstable, it is preferable to immediately carry out the next step of reaction. However, inorganic acid salts of aminoacetonitriles are stable solids and can be stored for a long time.

The manufacturing method of the compound of general formula (I) which concerns on this invention is represented by the following reaction process formula (G).

[Reaction Process Formula (G)]

The aminoacetonitrile (lV) is dissolved in a solvent inert to the reaction and an equivalent or slightly excess base is added. Next, pyrazolecarboxylic acid chloride (III) is slowly added dropwise. When aminoacetonitrile salts are used, additional bases necessary for neutralization of aminoacetonitrile salts are supplemented. Examples of inert solvents include ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane: hydrocarbons such as benzene, toluene, xylene and ligroin: halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride: ethyl acetate And esters such as ethyl propionate: aprotic polar solvents such as N, N-diethylformamide, dimethyl sulfoxide and 1,3-dimethylimidazolidinone. Pyridine can be used for two purposes: base and solvent. Examples of the base include organic bases such as triethyl amine, dimethylaniline and pyridine and inorganic bases such as ammonia, carium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide and ammonium carbonate. This reaction has low thermal stability of the alpha-aminoacetonitrile derivative (IV), so care must be taken not to carry out the reaction at too high a temperature.

In addition, since this reaction is exothermic, it is preferable to carry out the reaction under cooling (0 to 5 ° C). After completion of the addition, the reaction is terminated when the mixture is stirred at room temperature. The reaction time depends on the reaction temperature, but is usually 0.5 to 4 hours. After the reaction is completed, a crude product is obtained by a conventional method. The resulting pyrazole derivatives can be easily separated and purified by tonal methods such as recrystallization and column chromatography.

According to the present invention, there is also provided a horticultural fungicide containing a pyrazole derivative of formula (I) as an active ingredient. As agrohorticultural fungicides, the compounds according to the present invention exhibit a control effect against a wide range of plant diseases, in particular, late blight and downy mildew of various crops caused by crude fungi. The main plant diseases that can be controlled by the compounds according to the present invention include potato late blight (Phytophthora in festans), tomato blight (Phytophthora infestants), tobacco blight (phytophthora Parasitica Var. Nicotiana), berry blight (Phyto-Phthora Cactorum) , Various diseases caused by the fungus of Peronospora Chrysanthemi, P. aureus, Psemopara Viticola, Pseudo Peronospora cubensis, Pseudo peronospora humuli, and Pythium and Aphanomyces spp. There is a number.

Compounds according to the present invention can be used by seed fertilization, foliar application, and soil treatment. The present compounds exhibit satisfactory effects by any method commonly employed by those skilled in the art. The rate of use and concentration of the drug depends on the protective crop, the name of the control disease, the frequency of disease, the preparation of the drug, the method of use, and various environmental conditions, but the use rate by spraying is suitably 5 to 200 g / are, and 10 to 100 g. / are is preferred and the spray concentration is preferably 10 to 500ppm, preferably 50 to 300ppm.

Agrohorticultural fungicides according to the present invention can be used with other fungicides, insecticides, herbicides or plant growth regulators, soil conditioners, fertilizers, etc., these can be prepared as a mixed preparation before use.

The compounds according to the present invention may be used directly, but are preferably used in the form of a composition containing a solid or liquid carrier including a solid or liquid diluent. As used herein, the term carrier refers to synthetic or natural inorganic or organic materials that are incorporated to make the active ingredients easily reach the site to be treated or to facilitate storage, transport and handling of the active ingredients.

Suitable solid carriers include, for example, clays such as montmorillonite and kaolin: inorganic materials such as diatomaceous earth, clay, talc, vermiculite, gypsum, calcium carbonate, silica gel, ammonium sulfate, etc. Organic materials can be listed.

Suitable liquid carriers include, for example, aromatic hydrocarbons such as toluene, xylene, cumene, etc .: paraffinic hydrocarbons such as light oil and mineral oil: halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane: ketones such as acetone and methyl ethyl ketone. Ethers such as dioxane and tetrahydrofuran; alcohols such as methanol, propanol and ethylene glycol; dimethylformamide; diethyl sulfoxide; and water.

In order to further enhance the effect of the compounds according to the present invention, various auxiliaries may be used alone or in combination depending on the type of preparation, the place of use, and the like. For example, anionic surfactants such as lignosulfonates, alkylbenzenesulfonates, alkyl sulfate esters for the purposes of emulsification, dispersion, electrodeposition, hydration, bonding, stabilization, etc .: polyoxyalkylene alkyl ethers, poly Oxyalkylene alkylaryl ethers, polyoxyalkylene alkylamines, polyoxyalkylene alkylamides, polyoxyalkylene alkylthioethers, polyoxyalkylene fatty acid esters, glycerol fatty acid esters, sorbitan fatty acid esters Nonionic surfactants, such as polyoxyalkylene sorbitan fatty acid esters and polyoxypropylene polyoxyethylene block copolymers: Lubricants, such as calcium stearate wax: Stabilizers, such as isopropyl hydrogen phosphate: Methylcellulose: Carboxymethylcellulose: Casein and gum arabic can be used.

The content of the active ingredient in the composition of the compound according to the present invention is usually 0.5 to 20% by weight for powder, 5 to 20% by weight for an emulsifier stock solution, 10 to 90% by weight for hydrating agent, and 0.1 to 20% by weight for granulation. And from 10 to 90% by weight of the flow agent. In addition, the content of the carrier in the formulation is usually 60 to 99% by weight for powder, 60 to 95% by weight for emulsifier stock solution, 10 to 90% by weight for wetting agent, 80 to 99% by weight for granulation, and In the case of 10 to 90% by weight. The content of the auxiliary agent is usually 0.1 to 20% by weight for powder, 1 to 20% by weight for emulsion stock solution, 0.1 to 20% by weight for hydrating agent, 0.1 to 20% for granule, and 0.1 to 20% by weight for fluid %to be.

Exemplary pyrazole derivatives of the present invention represented by general formula (I) are shown in Table 1 below.

TABLE 1a

TABLE 1b

TABLE 1c

TABLE 1d

TABLE 1e

TABLE 1f

Table 1g

Table 1h

TABLE 1i

TABLE 1j

Table 1k

TABLE 1L

[Table 1m]

TABLE 1n

The preparation method of the compounds of the present invention will be described in detail by listing synthetic examples below.

Synthesis Example 1

Synthesis of alpha- (1,3-dimethylpyrazol-4-yl-carbonylamino)-(2-furyl) acetonitrile (Compound No. 33):

8.3 g of ammonium chloride and 5.0 g of sodium cyanide are dissolved in 50 ml of water, and 15 ml of diethyl ether, 8.0 ml of 28% ammonia water and 1.0 g of triethylbenzyl ammonium bromide are added to the solution. The mixture is cooled to 5 ° C. on an ice bath. 8.0 g of 2-furylaldehyde is added dropwise under stirring and the mixture is stirred at this temperature for 25 hours. After completion of the reaction, the ether layer was separated and the aqueous layer was extracted three times with diethyl ether. The ether layers are combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is mixed with 100 mL of ethyl acetate and cooled to 0-5 ° C. Next, 4.2 g of triethylamine are added, and 3.9 g of 1,3-dimethylparazol-4-carboxylic acid chloride is slowly added with stirring.

After the addition is complete, the mixture is stirred at room temperature for another 2 hours. 50 ml of water is added, and the precipitated triethylamine hydrochloride is dissolved. The ethyl acetate layer is separated, washed with water and dried over anhydrous sodium sulfate, and then the solvent is distilled off under reduced pressure. The residue was chromatographed on a silica gel column and the column was eluted with hexane / ethyl acetate to give the desired alpha- (1,3-dimethylpyrazol-4-ylcarbonylamino)-(2-furyl) acetonitrile 3.9 g is obtained (yield 65.0%).

Melting Point: 121.5-122.5 ℃

Synthesis Example 2

Synthesis of alpha- (1-isopropyl-3-methylpyrazol-4-ylcarbonylamino)-(2-thienyl) acetonitrile (Compound No. 32):

6.7 g of ammonium chloride and 4.0 g of sodium cyanide are dissolved in 50 ml of water, and to this solution is added 15 ml of diethyl ether, 7.0 ml of 28% ammonia water and 1.0 g of triethylbenzylammonium chloride. The mixture is cooled to 5 ° C. on an ice bath and 7.5 g of 2-thiophenaldehyde is added dropwise with stirring. The mixture is further stirred at this temperature for 20 hours. After completion of the reaction, the ether layer was separated and the aqueous layer was extracted three times with diethyl ether. The ether layers are combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is mixed with 50 ml of tetrahydrofuran and cooled to 0-5 ° C. Next, 3.4 g of triethylamine are added, and 4.1 g of 1-isopropyl-3-methylpyrazole-4-carboxylic acid chloride is slowly added. After the addition is complete, the mixture is stirred at room temperature for another 3 hours. Precipitated triethylamine hydrochloride is filtered off, and the filtrate is distilled under reduced pressure to distill the solvent. The residue is chromatographed on a silica gel column. The column was eluted with hexane / ethyl acetate to afford 3.2 g of the desired alpha- (1-isopropyl-3-methylpyrazol-4-ylcarbonylamino)-(2-thienyl) -acetonitrile (yield, 50.4%).

Melting Point: 140.5 ~ 141.5 ℃

Synthesis Example 3

Synthesis of alpha- (1,3-dimethylpyrazol-4-yl-carbonylamino)-(3-thienyl) acetonitrile (Compound No. 38):

10.0 g of ammonium chloride and 6.0 g of sodium cyanide are dissolved in 50 ml of water, to which 15 ml of diethyl ether, 9.5 ml of 28% ammonia water and 1.0 g of triethylbenzyl-ammonium chloride are added. The mixture is cooled to 5 ° C. on an ice bath, and 11.2 g of 3-thiophenylaldehyde is added dropwise while stirring. The mixture is stirred at this temperature for another 24 hours. After completion of the reaction, the ether layer was separated and the aqueous layer was extracted three times with diethyl ether. The ether layers are combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is mixed with 100 mL of diethyl ether and cooled to 0-5 ° C. Next, 4.2 g of triethylamine are added, and 3.9 g of 1,3-dimethylpyrazole-4-carboxylic acid chloride is slowly added dropwise while stirring. After the addition is completed, the mixture is further stirred for 1 hour at this temperature. Precipitated triethylamine hydrochloride is filtered off, and the filtrate is distilled under reduced pressure to distill the solvent. The residue is chromatographed on a silica gel column. The column is eluted with benzene / ethyl acetate to give 4.8 g of alpha- (1,3-dimethylpyrazol-4-yl-carbonylamino)-(3-thienyl) -acetonitrile (yield, 75.0%).

Melting Point: 113.0 ~ 114.5 ℃

Synthesis Example 4

Synthesis of alpha- (1-methyl-3-methoxymethylpyrazol-4-ylcarbonylamino)-(2-furyl) acetonitrile (Compound No. 46):

Suspend 3.2 g of alpha- (2-furyl) -aminoacetonitrile hydrochloride in 100 ml of ethyl acetate and add 4.5 g of triethylamine under ice-cooling. Next, 3.8 g of 1-methyl-3-methoxymethylpyrazole-4-carboxylic acid chloride is slowly added under stirring at 0? 5 占 폚. After the addition is complete, the mixture is stirred for another 2 hours at room temperature. 50 ml of water is added to dissolve the precipitated triethylamine hydrochloride. The ethyl acetate layer is separated, washed with water, dried over anhydrous sodium sulfate, and then distilled under reduced pressure to distill the solvent. The residue is chromatographed on a silica gel column and the column is eluted with hexanes / ethyl acetate to give the desired alpha- (1-methyl-3-methoxymethylpyrazole)-(4-ylcarbonylamino)-(2- 4.3 g of furyl) acetonitrile are obtained (yield, 78.6%).

Synthesis Example 5

Synthesis of alpha- (1,3-dimethylpyrazol-4-ylcarbonylamino)-(2-pyrrolyl) acetonitrile (Compound No. 42):

8.3 g of ammonium chloride and 5.0 g of sodium cyanide are dissolved in 50 ml of water, and 15 ml of diethyl ether, 8.0 ml of 28% ammonia water and 1.0 g of triethylbenzyl ammonium bromide are added to the solution. The mixture is cooled to 5 ° C. on an ice bath, 8.0 g of pyrrole-2-carboxyaldehyde is added dropwise with stirring, and then the mixture is stirred at this temperature for 24 hours. After completion of the reaction, the ether layer was separated and the aqueous layer was extracted three times with diethyl ether. The ether layers are combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is mixed with 100 ml of ethyl acetate and cooled to 0-5 ° C. Next, 4.2 g of triethylamine are added, and 3.9 g of 1,3-dimethylpyrazole-4-carboxylic acid chloride is slowly added while stirring. After the addition is complete, the mixture is stirred for another 2 hours at room temperature. 50 ml of water is added to dissolve the precipitated triethylamine hydrochloride. The ethyl acetate layer was separated, washed with water, dried over anhydrous sodium acetate, and distilled under reduced pressure to distill the solvent. The residue was chromatographed on a silica gel column and the column was eluted with hexane / ethyl acetate to give the desired alpha- (1,3-dimethylpyrazol-4-ylcarbonylamino)-(2-pyrrolyl) acetonitrile Obtain 4.4 g (yield, 73.1%).

Melting Point: 174 ~ 176 ℃

Synthesis Example 6

Synthesis of 2- (1,3-dimethylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentennitrile (Compound No. 1):

8.3 g of ammonium chloride and 5.0 g of sodium cyanide are dissolved in 50 ml of water, and 15 ml of diethyl ether and 8 ml of 28% ammonia water are added to the solution. The mixture is cooled to 5 ° C. on an ice bath and 7.0 g of 3-methyl-2-butenal is added with stirring. The mixture is stirred for another 24 hours at this temperature. After completion of the reaction, the ether layer was separated and the aqueous layer was extracted three times with diethyl ether. The ether layers are combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is mixed with 100 mL of diethyl ether and cooled to 0-5 ° C. Next, 4.2 g of triethylamine are added, and 3.9 g of 1,3-dimethylpyrazole-4-carboxylic acid chloride is slowly added while stirring. After the addition is complete, the mixture is stirred for another hour at this temperature. Precipitated triethylamine hydrochloride is filtered off, and the filtrate is distilled under reduced pressure to distill the solvent. The residue was chromatographed on a silica gel column and the column was eluted with benzene / ethyl acetate to give 3.7 g of the desired 2- (1,3-dimethylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentennitrile. (Yield 64.6%).

Melting Point: 110.5 ~ 111.5 ℃

Synthesis Example 7

Synthesis of 2- (1,3-dimethylpyrazol-4-ylcarbonylamino) -4-chloro-3-pentennitrile (Compound No. 4):

6.7 g of ammonium chloride and 4.0 g of sodium cyanide are dissolved in 50 ml of water, to which 15 ml of diethyl ether and 7 ml of 28% ammonia water are added. The mixture is cooled to 5 ° C. on an ice bath and 7.0 g of 3-chloro-2-butenal is added with stirring. The mixture is stirred for another 12 hours at this temperature. After completion of the reaction, the ether layer was separated and the aqueous layer was extracted three times with diethyl ether. The ether layers are combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is mixed with 50 ml of tetrahydrofuran and cooled to 0-5 ° C. Next, 3.4 g of triethylamine are added, and 3.1 g of 1,3-dimethylpyrazole-4-carboxylic acid chloride is slowly added while stirring. After the addition is complete, the mixture is stirred for another hour at this temperature. Precipitated triethylamine hydrochloride is filtered off, and the filtrate is distilled under reduced pressure to distill the solvent. The residue was chromatographed on a silica gel column and the column was eluted with hexanes / ethyl acetate to give 2.6 g of the desired 2- (1,3-dimethylpyrazol-4-ylcarbonylamino) -4-chloro-3-pentenenitrile. (Yield 52.5%).

Melting Point: 113-114 ° C

Synthesis Example 8

Synthesis of 2- (1-allyl-3-methylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentennitrile (Compound No. 14):

8.3 g of ammonium chloride and 5.0 g of sodium cyanide are dissolved in 50 ml of water, to which 15 ml of diethyl ether and 8.0 ml of 28% ammonia water are added. The mixture is cooled to 5 ° C. under ice cooling, and 7.0 g of 3-methyl-2-butenal is added dropwise while stirring. The mixture is stirred for another 24 hours at this temperature. After completion of the reaction, the ether layer was separated and the aqueous layer was extracted three times with diethyl ether. The ether layers are combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is mixed with 100 mL of diethyl ether and cooled to 0-5 ° C. Next, 4.2 g of triethylamine are added. Furthermore, crude 1-allyl-3-methylpyrazole-4-carboxylic acid synthesized by Method B in the Reference Synthesis Examples described below is 1-allyl-3-methylpyrazole by conventional method. Convert to -4-carboxylic acid chloride.

4.5 g of crude product are slowly added by stirring. After the addition is complete, the mixture is stirred for another hour at this temperature. Precipitated triethylamine hydrochloride is filtered off, and the filtrate is distilled under reduced pressure to distill the solvent. The residue is chromatographed on a silica gel column and the column is eluted with hexanes / ethyl acetate to give the desired 2- (1-allyl-3-methylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentene 4.3 g of nitrile are obtained (yield, 67.9%).

Synthesis Example 9

Synthesis of 2- (1,3-dimethylpyrazol-5-ylcarbonylamino) -4-methyl-3-pentennitrile (Compound No. 52):

8.3 g of ammonium chloride and 5.0 g of sodium cyanide are dissolved in 50 ml of water, to which 15 ml of diethyl ether and 8.0 ml of 28% ammonia water are added. The mixture is cooled to 5 ° C. on an ice bath and 7.0 g of 3-methyl-2-butenal is added dropwise with stirring. The mixture is stirred for another 24 hours at this temperature. After completion of the reaction, the ether layer was separated and the aqueous layer was extracted three times with diethyl ether. The ether layers are combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is mixed with 100 mL of diethyl ether and cooled to 0-5 ° C. Next, 4.2 g of triethylamine are added, and 3.9 g of 1,3-dimethylpyrazole-5-carboxylic acid chloride is slowly added while stirring. After the addition is complete, the mixture is stirred for another hour at this temperature. Precipitated triethylamine hydrochloride is filtered off, and the filtrate is distilled under reduced pressure to distill the solvent. The residue is chromatographed on a silica gel column and the column is eluted with benzene / ethyl acetate to give the desired 2- (1,3-dimethylpyrazol-5-ylcarbonylamino) -4-methyl-3-pentennitrile 3.7 g is obtained (yield 64.6%).

Melting point: 92.5 ~ 94.0 ℃

Synthesis Example 10

Synthesis of 2- (1,3-dimethylpyrazole-5-ylcarbonylamino) pentanenitrile (Compound No. 56):

A mixture of 3.6 g of n-butylaldehyde and 10 ml of methanol was added dropwise to a mixture of 7.9 g of ammonium chloride, 6.6 g of sodium cyanide, 47 ml of 28% ammonia water and 23 ml of ethanol at 25 to 30 ° C., and the mixture was stirred at 5 ° C. above. Stir again for an hour. After the reaction was completed, the reaction mixture was released in 100 ml of water and extracted three times with diethyl ether. The ether layers are combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is mixed with 100 mL of diethyl ether and cooled to 0-5 ° C.

Next, 4.2 g of triethylamine are added, and 3.9 g of 1,3-dimethylpyrazole-5-carboxylic acid chloride is slowly added while stirring. After the addition is complete, the mixture is stirred for another hour at this temperature. Precipitated triethylamine hydrochloride is filtered off, and the filtrate is distilled under reduced pressure to distill the solvent. The residue is chromatographed on a silica gel column and the column is eluted with hexanes / ethyl acetate to give 4.1 g of the desired 2- (1,3-dimethylpyrazol-5-ylcarbonylamino-pentanenitrile as an oil ( Yield, 75.6%).

Synthesis Example 11

Synthesis of alpha- (1,3-dimethylpyrazol-5-ylcarbonylamino) -phenylacetonitrile (Compound No. 57):

1.6 g of mandelonitrile is dissolved in 30 ml of methanol, and ammonia gas is stirred and blown into the solution until the starting material mandelonitrile disappears. The reaction product is concentrated under reduced pressure, and 50 ml of diethyl ether and then 2.5 g of triethylamine are added to the residue. The mixture is cooled to 5 ° C. on an ice bath and 1.6 g of 1,3-dimethylpyrazole-5-carboxylic acid chloride is slowly added while stirring. After the addition is complete, the mixture is stirred for another hour at this temperature. Precipitated triethylamine hydrochloride is filtered off, and the filtrate is distilled under reduced pressure to distill the solvent. The residue is chromatographed on a silica gel column and the column is eluted with hexane / ethyl acetate to afford 1.7 g of the desired alpha- (1,3-dimethylpyrazol-5-ylcarbonylamino) -phenylacetonitrile (yield). , 67.0%).

Melting Point: 135-136 ° C

Reference examples are listed below to specifically describe the production method of starting materials pyrazole carboxylic acid esters and pyrazole carboxylic acids. If separation of the isomers from the intermediate is difficult, the crude product is provided directly to the next reaction step and purified in the final step.

Reference Example 1

Synthesis of 1,3-dimethylpyrazole-4-carboxylic acid [Compound No.I-1: According to Method (A)]:

A mixture of 18.6 g (0.1 mol) of ethyl 2-ethoxymethyleneacetoacetate and 47 ml of ethanol is cooled to 5 DEG C on an ice bath, and 6.9 g (0.15 water) of methylhydrazine is added dropwise with stirring. After the addition is complete, the mixture is stirred at reflux for 4-5 hours. After the reaction is completed, the reaction mixture is cooled to room temperature and 230 ml of water is added. After dyeing, the reaction mixture is extracted three times with ethyl acetate. The ethyl acetate layers are combined, washed with saturated aqueous sodium chloride solution, dried over sodium sulfate and concentrated under reduced pressure to give 16.7 g of crude ester. To a mixture of 16.7 g of sodium hydroxide and 33 ml of water, 16.7 g of crude ester was stirred and added at room temperature. The mixture is stirred at 100 to 110 ° C. for 3 to 4 hours. After the reaction is completed, the reaction mixture is cooled to room temperature and 42 ml of water is added. The pH is adjusted to 4-5 by cooling the reaction solution and adding concentrated hydrochloric acid. The precipitated crystals are filtered off, dried and recrystallized in water to obtain 9.8 g of the desired 1,3-dimethylpyrazole-4-carboxylic acid (yield, 70%).

Melting Point: 190 to 190.5 ° C

Reference Example 2

Synthesis of 1-methyl-5-methoxypyrazole-4-carboxylic acid [by method (B)]:

3.4 g of ethyl 5-hydroxy-1-methylpyrazole-4-carboxylate (Japanese Patent Publication No. 122,488 / 1984) obtained from ethyl ethoxymethylenemalonate and methyl hydrazine was added to 80 ml of tetrahydrofuran. Dissolve and convert to salt with 0.8 g sodium hydride. 2.8 g of methyl iodide is added and the mixture is stirred at 40 ° C. for 3 hours. After the reaction was completed, the mixture was filtered and the filtrate was concentrated to give 1.7 g of 1-methyl-5-methoxypyrazole-4-carboxylate (yield, 46%).

1.4 g of ethyl 1-methyl-5-methoxypyrazole-4-carboxylate is stirred with 10 ml of 30 ml of ethanol and 2 g of potassium hydroxide for 2 hours at room temperature. Ethanol is removed under reduced pressure from the reaction solution. Acid precipitation from the aqueous layer yields 1.2 g of the desired 1-methyl-5-methoxypyrazole-4-carboxylic acid (yield, 99%).

Melting Point: 225 ℃ (Decomposition)

Reference Example 3

Synthesis of 1- (gamma-chloroallyl) -3-methylpyrazole-4-carboxylic acid [compounds No. 1-10 and 1-11: by method (C)]:

5.0 g of ethyl 3-methylpyrazole-4-carboxylate is added to sodium alcoholate prepared from 0.75 g of sodium metal and 30 ml of ethanol. 3.6 g of 1,3-dichloropropene are added to the homogeneous mixture and the mixture is refluxed for 2 hours. After the reaction is completed, the reaction mixture is released into water and extracted with ethyl acetate. The extract was chromatographed on a silica gel column and the column was extracted with hexane / ethyl acetate to give 2.5 g (34%) of Z isomer of ethyl 1- (gamma-chloroallyl) -3-methylpyrazole-4-carboxylate. Obtain 1.5 g (20%) of the E isomer. 2.5 g of Z isomer is heated and stirred for 4 hours with a mixture of 25 ml of ethanol, 2.5 g of sodium hydroxide and 25 ml of water. After the reaction is completed, the reaction mixture is cooled to room temperature, and concentrated to pH 4 to 5 by adding concentrated hydrochloric acid under ice cooling. The precipitated crystals are filtered and dried. Recrystallization from water affords 0.3 g of the Z isomer of 1- (gamma-chloroallyl) -3-methylpyrazole-4-carboxylic acid (yield, 14%).

Melting Point: 96-100 ℃

By the same operation, 0.34 g of the E isomer thereof is obtained (yield, 30%).

Melting Point: 152 ~ 156 ℃

Reference Example 4

Synthesis of 1-methylpyrazole-4-carboxylic acid [Compound No.I-5: According to Method (D)]:

3.9 g of 1-methylpyrazole-4-aldehyde (described in J. Chem. Soc., Page 3314, 1957) is dissolved in 20 ml of acetone and the solution is heated and simultaneously Jones reagent is added. After completion of the reaction, the excess Jones reagent is treated with a dilute alkaline aqueous solution to precipitate the precipitate. The filtrate is weakly acidified and extracted with ethyl acetate. The extract is dried over dilute sodium sulfate and concentrated under reduced pressure to yield 2.3 g of 1-methylpyrazole-4-carboxylic acid (yield, 52%).

Melting Point: 205-206 ° C

Reference Example 5

Synthesis of ethyl 1,3-dimethylpyrazole-5-carboxylate [by Method (E)]:

To a mixture of 30 g of acetpyruvic acid and 120 ml of ethanol, 10 g of methylhydrazine is added dropwise under ice-cooled stirring. The mixture is changed from a colorless solution to a yellow solution while generating heat. This solution is then stirred under reflux for 3 hours. The low boiling water was evaporated under reduced pressure to give 33.6 g of a yellow oil. Chromatography of the yellow oil on a silica gel column (eluent: benzene / ethyl acetate = 1/1) yielded 8.6 g (yield, 27%) of ethyl 1,3-dimethylpyrazole-5-carboxylate as an oil. Obtained.

NMR (CDCl ₃ ) δ: 1.46 (3H, t, J = 7.0 Hz), 2.38 (3H, s), 4.18 (3H, s), 4.47 (2H, q, J = 7.0 Hz), 6.65 (1H, s )

As isomer, 22.0 g (yield, 69%) of ethyl 1,5-dimethylpyrazole-3-carboxylic acid is obtained as a colorless oil.

NMR (CDCl ₃ ) δ: 1.38 (3H, t, J = 7.0 Hz), 2.31 (3H, s), 3.82 (3H, s), 4.32 (2H, q, J = 7.0 Hz), 6.26 (1H, s )

By the same method as above, the pyrazole carboxylic acid according to the present invention is synthesized. The compounds and their properties are listed in Table 2 below. The resulting pyrazolecarboxylic acids are used after conversion to the acid salts of the general formula (III) by the conventional method.

The target compounds of formula (I) are converted to acid chlorides without recrystallization by pyrosolcarboxylic acids by the conventional method, reacted with aminoacetonitriles of formula (IV), and then the crude product is subjected to column chromatography. It can obtain by refine | purifying.

Other compounds according to the present invention can be substantially synthesized by the procedures of Synthesis Examples 1 to 11.

TABLE 2a

TABLE 2b

TABLE 2c

TABLE 2d

TABLE 2e

Production of agrohorticultural fungicides according to the present invention will be described in detail by enumerating the following formulation examples.

[Example 1]

Powder: 3 parts of compound No. 1, 20 parts of diatomaceous earth, 30 parts of clay, and 47 parts of talc are uniformly ground and mixed to obtain 100 parts of powder.

[Example 2]

Hydrating agent: 30 parts of compound No. 2, 47 parts of diatomaceous earth, 20 parts of white clay, 1 part of sodium lignosulfonate and 2 parts of sodium alkylbenzenesulfonate are pulverized and mixed to obtain 100 parts of hydrating agent.

[Example 3]

Emulsion stock solution: 20 parts of compound No. 3, 10 parts of cyclohexane, 50 parts of xylene, and 20 parts of Sorpol (Japanese Eastern Chemical Co., Surfactant) are uniformly dissolved and mixed to obtain 100 parts of emulsion solution.

[Example 4]

Granules: Compound No.4.1 parts, bentonite 78 parts, talc 20 parts and sodium lignosulfonate 1 part are mixed and mixed with an appropriate amount of water. The mixture is granulated in a conventional manner by an extrusion granulator, and then dried to obtain 100 parts of granules.

[Example 5]

Granulation: 5 parts of compound No. 3, 1 part of polyethylene glycol nonylphenyl ether, 3 parts of polyvinyl alcohol, and 91 parts of clay are mixed uniformly, and then added with water, and granulated and dried to obtain 100 parts of granules.

[Example 6]

Powder: 2 parts of compound No. 33, 40 parts of calcium carbonate, and 58 parts of clay are mixed uniformly, and 100 parts of powder are obtained.

[Example 7]

Hydrating agent: 50 parts of compound No. 5, talc 40 parts, 5 parts of lauryl sodium phosphate and 5 parts of sodium alkylnaphthalene sulfonate are mixed to obtain 100 parts of hydrating agents.

[Example 8]

Hydrating agent: 50 parts of compound No. 1, 10 parts of sodium lignin sulfonate, 5 parts of sodium alkylnaphthalene, 10 parts of white carbon and 25 parts of diatomaceous earth are mixed and ground to obtain 100 parts of hydrating agents.

[Example 9]

Fluidizing agent: 40 parts of Compound No. 30, 3 parts of carboxymethylcellulose, 2 parts of sodium lignosulfonate, 1 part and 54 parts of sodium dioctylsulfosuccinate are wet milled with a sand grinder to obtain 100 parts of a fluidizing agent.

The effectiveness of the compounds according to the invention as agrohorticultural fungicides will be explained by the following test examples. In these test examples, the following compounds were used as controls.

A: alpha- (2,6-dichloropyridin-4-ylcarbonylamino)-(2-furyl) acetonitrile

B: alpha- (2-furylcarbonylamino)-(2-furyl) acetonitrile

C: 4- (2,4-dichlorobenzoyl) -5-benzoylmethoxy-1,3-dimethylpyrazole

D: alpha-benzoylaminopropioacetonitrile

E: zinc ethylenebis (dithiocarbamate) [Zineb]

F: Tetrachloro isophthalonitrile [TPN]

Control compounds A and B are described in the above-mentioned Japanese Patent Publication No. 167978/1982, compound C is a commercial herbicide, and compound D is the aforementioned Justus Liebigs Ann. Chem., 1972, 764, pages 69-93. Compounds E and F are commercially available agents for controlling late blight of potato and downy mildew of cucumber.

[Test Example 1]

Potato Plague Control Test (Prevention Effect): Potatoes (breed: Baron, male: about 25cm) are raised in pot in greenhouse. From each of the test compounds, a hydrating agent was prepared according to the method of Formulation Example 8, and diluted with water to a predetermined concentration to prepare a test agent. The spray gun is used to spray the agent at a rate of 50 ml per three pots and then air dried. Yuju suspension is prepared from the late blight strain cultured on potato slices in advance for 7 days. This dweller suspension is spray inoculated onto pharmaceutical sprayed potato plants. After the test plants are maintained at 17 to 19 ° C. and humidity of 95% or more for 6 days, the extent of lesion formation is examined.

Observe and evaluate the area ratio of lesions for each leaf and determine the lesion index. For each zone, the degree of disease is calculated by the following equation.

Evaluation criteria are as follows.

Incidence index Lesion area ratio

0 0%

1 1-5%

2 6-25%

3 26-50%

4 over 51%

n ₀ : leaf number of the disease index 0, n ₁ : leaf number of the disease index 1, n ₂ : leaf number of the disease index 2, n ₃ : leaf number of the disease index 3, n ₄ : index of the disease index 4, leaf number.

N = n ₀ + n ₁ + n ₂ + n ₃ + n ₄

The results are shown in Table 3.

[Test Example 2]

Potato blight control test (Eradication effect): Sprayed inoculated with a potato suspension of potato blight bacteria strain prepared as in Test Example 1 to potatoes grown in pots in a greenhouse (variety: baron, height: about 25 cm). Let's do it. The to-be-tested plant is maintained at 17 to 19 ° C. and at least 95% humidity for 20 hours. Formulations of a hydrating agent were prepared from each of the disclosed compounds according to the method of Formulation Example 8, and diluted to a predetermined concentration with water, and then a predetermined concentration of the drug was obtained at a rate of 1.0 ml (1.0 kg / cm 2) for three ports. Spray with a spray gun. After air drying, the subjects were again maintained for 6 days at a temperature of 17-19 ° C. and a humidity of 95% or more and the extent of lesion formation was examined.

Evaluation criteria and a degree of disease were carried out as in Test Example 1, and these results are shown in Table 3.

[Test Example 3]

Cucumber germ disease control test (prophylactic effect): Formulated with the method of Formulation Example 8 to prepare a hydrate of each compound and dilute to a predetermined concentration with water to obtain a predetermined concentration of the cucumber (variety: white hairy rice cake, rice cake leaf) Sprayed at a rate of 30 ml for the three pots and then air dried. Pseudoperonospora Cubensis is harvested from the lesions of cucumber leaves infected with Downy mildew, and deionized water suspension is prepared using deionized water. The suspension is sprayed onto the cucumber plants in the pot. The pots are then maintained at a temperature of 18-20 ° C. and at least 95% humidity for 24 hours and then transferred into the greenhouse (room temperature, 18-27 ° C.). After 7 days, Lee Byeong-Do is examined.

Evaluation criteria and a degree of disease were carried out as in Test Example 1, and these results are shown in Table 3.

[Test Example 4]

Cucumber Buccal Disease Control Test (Eradication Effect): A juvenile suspension of Cucumber Buccal Disease strain (Pseudoperonospora Cubensis) was prepared and sprayed onto the same cucumber specimen as used in Test Example 3 to inoculate fungus. The plants to be maintained for 24 hours at a temperature of 18 to 20 ℃ and humidity of 95% or more. Using a spray gun (1.0 kg / cm 2) at a rate of 30 ml with respect to three pots of the test plants, a predetermined concentration of a drug obtained by removing the hydrating agent of each of the disclosed compounds and diluting the predetermined concentration with water in the same manner as in Preparation Example 8 Spray. These pots are then transferred to a greenhouse at 18-27 ° C. and checked for disease after 7 days.

Evaluation criteria and Lee Byeong-do are carried out as in Test Example 1, and the results are shown in Table 3.

[Test Example 5]

Tomato Plague Control (Soil Application): A tomato obtained by irradiating a hydration agent of each of the disclosed compounds and diluting with a predetermined concentration by water according to the method of Formulation Example 8 in a pot (diameter, 7.5 cm) in a greenhouse. Varieties: World day (世界 一), height: about 20 ㎝) Using a pipette, soak at a rate of 2 ml per pot. The tested plants are kept in the greenhouse for 5 days. Sake suspension of tomato blight strains is incubated for 7 days in advance on potato slices. This suspension is sprayed onto a pharmaceutical-treated tomato plant and maintained for 6 days at a temperature of 17-19 ° C. and a humidity of at least 95%, and the extent of lesion formation is investigated.

Evaluation criteria and Lee Byeong degree are carried out as in Test Example 1, and these results are shown in Table 3.

In the above test examples, the concentration of the active ingredient is 100 ppm for spraying and 15 g / are for soil application.

TABLE 3a

TABLE 3b

TABLE 3c

Table 3d

From the results of Table 3, it is clear that the compounds according to the present invention show a high control effect against plant diseases caused by coliforms such as potato blight, tomato blight and cucumber fungal disease not only by spraying but also by soil application. I can see. It is also in stark contrast to the fact that control compounds A, B, C, and D, which are very similar in chemical structure to the compounds according to the present invention, show little or no control effect on these diseases. In addition, compared to zinc ethylene bis (dithiocarbamate) and tetrachloroisophthalonitrile, which are currently commercially available and widely used against these plant diseases, the compounds according to the present invention exhibit a prophylactic effect even at a much lower dosage and at the same time, It has the effect of eradication and prevention by applying soil that does not have one of two commercial pesticides.

From the above description, it can be clearly seen that the pyrazole derivatives according to the present invention have an excellent control effect as a horticultural fungicide against various crop diseases caused by crude fungi. Since the pyrazine derivatives according to the present invention have an effect of eradication, a control effect can be expected even after the crop is infected.

Compounds produced by the present invention can greatly change the control method of agricultural horticultural crop disease, can greatly reduce the worker's labor duties from this fact. Therefore, the pesticides containing the pyrazole derivatives according to the present invention are very useful because they have excellent properties as agricultural horticultural fungicides.

Claims (8)

Pyrazole derivatives characterized by the following general formula (I)

Wherein R ¹ represents an alkyl group, haloalkyl, alkenyl, haloalkenyl or phenyl group: R ² and R ³ each represent a hydrogen or halogen atom or an alkyl, haloalkyl, alkoxy, alkoxyalkyl, or phenyl group: R ⁴ represents an alkyl, alkenyl, haloalkenyl or phenyl group, or a substituted or unsubstituted heterocyclic aromatic group containing at least one oxygen, nitrogen or sulfur atom. A ² -furyl, 3-furyl, 2 according to claim 1, wherein in formula (I), R ¹ and R ² are lower alkyl groups, R ³ is a hydrogen atom, and R ⁴ is unsubstituted or substituted with a methyl group or a halogen atom. -A pyrazole derivative characterized by a thienyl, 3-thienyl or 2-pyrrolyl group. The pyrazole derivative according to claim 2, wherein R ⁴ in general formula (I) is a 2-furyl, 3-furyl, 2-thienyl or 3-thienyl group. The pyrazole derivative according to claim 1, wherein in formula (I), R ¹ and R ² are lower alkyl groups, R ³ is a hydrogen atom, and R ⁴ is a 2-methylpropen-1-yl group. The pyrazole derivative according to claim 1, which is represented by the following general formula (II).

Wherein R ¹ and R ² are lower alkyl groups and R ³ is a hydrogen atom and R ⁴ is a 2-furyl, 3-furyl, 2-thienyl or 3-thienyl group. The pyrazole derivative according to claim 5, wherein R ⁴ in formula (II) is a 2-methylpropen-1-yl group. A method for producing a pyrazole derivative of formula (I), characterized by reacting a compound of formula (III) with aminoacetonitrile of formula (IV) or a salt thereof.

In the formulas, R ¹ represents an alkyl group, haloalkyl, alkenyl, haloalkenyl or phenyl group: R ² and R ³ each represent a hydrogen or halogen atom or an alkyl, haloalkyl, alkoxy, alkoxyalkyl, or phenyl group R ⁴ represents an alkyl, alkenyl, haloalkenyl or phenyl group, or a substituted or unsubstituted heterocyclic aromatic group containing at least one or more oxygen nitrogen or sulfur atoms, and X represents a halogen atom. Agrohorticultural fungicides containing the pyrazole derivatives of the general formula (I) as active ingredients

Wherein R ¹ represents an alkyl group, haloalkyl, alkenyl, haloalkenyl or phenyl group: R ² and R ³ each represent a hydrogen or halogen atom or an alkyl, haloalkyl, alkoxy, alkoxyalkyl, or phenyl group: R ⁴ represents an alkyl, alkenyl, haloalkenyl or phenyl group, or a substituted or unsubstituted heterocyclic aromatic group containing at least one oxygen, nitrogen or sulfur atom.