JPH0768220B2 - Novel pyrazole derivative, production method thereof, and agricultural / horticultural fungicide containing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is represented by the general formula (I). (In the formula, R ¹ represents an alkyl group, an alkenyl group, a haloalkenyl group, a phenyl group or an alkylcarbamoyl group, R ² represents a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group, and R ³ represents a hydrogen atom or a halogen. Atom, a lower alkyl group or a phenyl group, and R ⁴ and R ⁵ each represent a hydrogen atom, a chlorine atom or a lower alkyl group), a method for producing the same, and agricultural and horticultural products containing them as an active ingredient. It relates to a fungicide.

[Prior art]

Many studies have been conducted on organic synthetic compounds useful in agriculture and horticulture, and many compounds showing physiological activity have been found and put to practical use. A great number of active compounds have been found as amide compounds, and some compounds have been used as herbicides or fungicides. For example, as a substituted benzamide derivative, as a herbicide, ethyl N-benzoyl-N- (3,4-dichlorophenyl)-
2-Aminopropionate (benzoylpropethyl) and 2-methyl-N- (3-isopropoxyphenyl) -benzamide (mepronil) are known as fungicides. Examples of the pyrazole-based compound exhibiting herbicidal activity include p-toluenesulfonic acid 4- (2,
4-dichlorobenzoyl) -1,3-dimethylpyrazole-
5-yl (pyrazolate) or 4- (2,4-dichlorobenzoyl) -5-benzoylmethoxy-1,3-dimethylpyrazole (pyrazoxine) is widely used as a herbicide for paddy fields in Japan. Compounds having bactericidal activity include Australian Journal of Chemistry (Aust.J.Chem.), 36 , pp. 135-47 (1983) and Agricultural Biological Chemistry (Agr. Biol. Chem.), 48 , 45-. On page 50 (1984)
It is described that a 1,3-dimethylpyrazole carboxyanilide derivative has a weak bactericidal action against Rhizoctonia solani and also has a controlling effect against cotton seedling blight caused by it. However, the action of these 1,3-dimethylpyrazole carboxyanilide derivatives seems to be active only in basidiomycetes like the already generally known carboxyanilide compounds such as mepronil.

In Chemical Abstracts, there are a few examples of the synthesis of acylamino saturated aliphatic derivatives closely related to the pyrazole derivatives of the present invention. For example,
Journal of the Chemical Society (J.Ch
em.Soc.), 1963 , pp. 2143-2150 and Synthesis, 1972 , (11), pp. 622-624, 2
-Benzoylaminobutyronitrile was also added to the buretane de la Societe de France (Bull.So
c.Chim.Fr.), 1969 , (11), 4108-4111 and Justus Liebgs Ann.Chem., 1972 , 764, 69-93, 2-benzoylaminopropiononitrile. An example of the synthesis of is illustrated. However, there is no mention of the physiological activity of the compounds described in these documents.

Heretofore, compounds having various chemical structures have been put to practical use as agricultural and horticultural fungicides, and the role of these synthetic compounds in controlling plant diseases and, in turn, in the development of agriculture is immeasurable. However, it is a fact that some of these conventional synthetic compounds cannot be said to have sufficient control action or safety. For example, for the epidemics and downy mildews of various crops, captafol, TPN, captan or dithiocarbamate drugs have been widely and commonly used and have contributed to the increase of crop production. However, all of these compounds have a prophylactic effect against plague and downy mildew, and no therapeutic effect can be expected at all. Therefore, it has a drawback that a sufficient effect cannot be expected already when the occurrence of disease is recognized. In actuality, when considering chemical spraying for crop disease control, it will be sprayed more or less after the disease has occurred, and complete disease control is difficult with these compounds. In addition, these compounds have extremely high concentrations exhibiting a controlling effect, and are regarded as a problem from the viewpoint of safe use of controlling agents, and there are some agents whose toxicity to fish cannot be ignored. In order to improve these points, research on new control agents has been earnestly continued, and for example, N-phenylalanine ester derivatives, which are now effective as disease control agents against algae fungi, also show excellent therapeutic effects,
For example, metalaxyl [N- (2,6-dimethylphenyl)
-N- (2-methoxyacetyl) alanine methyl ester] and the like have been developed and are being put to practical use worldwide. However, these N-phenylalanine ester derivatives have already been problematic in that the control effect is lowered due to the occurrence of drug-resistant bacteria.

[Problems to be Solved by the Invention]

The present invention overcomes the drawbacks of the prior art described above, and provides a compound having excellent properties as an agricultural and horticultural fungicide, a method for producing the same, and a harmful microbial control agent containing them as an active ingredient. And That is, plague of various actions, prophylactic against mildew, etc., a wide range of compounds having an excellent control effect having both a therapeutic effect, or no phytotoxicity to cultivated plants, An object of the present invention is to provide a compound that is not toxic to warm-blooded animals or fish, and to provide a simpler and higher-yield production method thereof, and a useful agrochemical composition containing them.

[Means and Actions for Solving the Problems]

As a result of diligent research on an acylaminoacetonitrile derivative to solve the above-mentioned problems, the pyrazolecarbonylaminoacetonitrile derivative has a physiological activity that cannot be predicted at all from the above exemplified compounds, and is excellent as an agricultural and horticultural fungicide. The present invention has been found to have a wide variety of plant disease control effects, and particularly to prevent epidemics and downy mildews of various crops, and also show excellent control effects for treatment after infection with a disease. did.

That is, the invention has the general formula (I) (In the formula, R ¹ represents an alkyl group, an alkenyl group, a haloalkenyl group, a phenyl group or an alkylcarbamoyl group, R ² represents a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group, and R ³ represents a hydrogen atom or a halogen. Atom, a lower alkyl group or a phenyl group, and R ⁴ and R ⁵ each represent a hydrogen atom, a chlorine atom or a lower alkyl group), which is a novel compound.

R ¹ in the general formula (I) is an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, more preferably a lower alkyl group having 1 to 6 carbon atoms, an alkenyl group, preferably 2 to 2 carbon atoms.
A lower alkenyl group having 6 carbon atoms, a haloalkenyl group, preferably a lower haloalkenyl group having 2 to 6 carbon atoms, a phenyl group or an alkylcarbamoyl group, preferably a lower alkylcarbamoyl group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom. An alkyl group, preferably a lower alkyl group having 1 to 6 carbon atoms,
A haloalkyl group, preferably a lower haloalkyl group having 1 to 6 carbon atoms or a phenyl group, R ³ is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁴ and R ⁵ are Each is a hydrogen atom, a chlorine atom or a lower alkyl group having 1 to 6 carbon atoms.

The present invention further conducted intensive studies on the method for producing the pyrazole derivative represented by the general formula (I), and as a result, found a method for obtaining the target product in high yield and completed the present invention.

That is, the method for producing a pyrazole derivative according to the present invention is represented by the general formula (II) (In the formula, R ¹ , R ² and R ³ each have the above-mentioned meaning,
X represents a halogen atom) and a compound represented by the general formula (III) (In the formula, R ⁴ and R ⁵ each have the above-mentioned meaning) A method for producing a pyrazole derivative represented by the general formula (I) is characterized by reacting with a compound represented by the formula.

The production method of the compound of the present invention represented by the general formula (I) will be described below with reference to reaction scheme A.

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the above-mentioned meanings.) The aldehyde represented by the general formula (IV) is subjected to the Strecker reaction in the presence of HCN and ammonia to obtain α -Aminobutenenitrile derivative (III) is obtained. Then, this was pyrazolecarboxylic acid chloride (II) previously prepared with pyrazolecarboxylic acid (V) and thionyl chloride in the presence of a base.
React with. Examples of the base include triethylamine,
Organic bases such as dimethylaniline, pyridine, picoline,
There are inorganic bases such as, but not limited to, ammonia, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide and ammonium carbonate. This reaction is preferably carried out in a solvent or diluent. Any solvent that is inert to this reaction can be used as the solvent. For example, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, ethers such as dioxane, ethyl acetate,
Esters such as butyl acetate and ethyl propionate, N, N
-Dimethylformamide, 1,3-dimethyl-2-imidazolidinone, aprotic polar solvent such as dimethylsulfoxide, dichloromethane, chloroform, carbon tetrachloride,
Examples thereof include halogenated hydrocarbons such as tetrachloroethylene, organic bases such as pyridine and picoline, and water.
In particular, when an organic base such as pyridine or picoline is used, it also functions as a base as a deoxidizing agent. In this reaction, the intermediate α-aminobutenenitrile derivative (III) does not have good thermal stability.
Further, since there is an exothermic reaction, it is desirable to carry out under cooling (0 to 5 ° C). The charging order can be added in any order,
Usually, it is preferable to charge the solvent of α-aminobutenenitrile derivative (III), add a base, and then add pyrazolecarboxylic acid chloride (II) as it is or after diluting it with a solvent. The reaction time varies depending on the reaction temperature, but is usually in the range of 0.5 to 5 hours. The desired pyrazole derivative thus obtained can be easily isolated and purified by a conventional method such as recrystallization or column chromatography.

Further, the present invention provides a fungicide for agricultural and horticultural use, which comprises the pyrazole derivative represented by the general formula (I) according to the present invention as an active ingredient. When the compound of the present invention is used as a fungicide for agricultural and horticultural use, it exhibits a controlling effect against a wide range of plant diseases, but is particularly effective against plague and downy mildew of various crops caused by algae. Major diseases to be controlled are potato disease, tomato disease, tobacco disease, strawberry disease, adzuki bean disease, downy mildew, cucumber downy mildew, hop downy mildew, jungy mildew downy mildew, or Aphanomyces spp., Pythium spp. Examples include various crop seedling blight caused by fungi.

As a method of applying the compound of the present invention, seed disinfection, foliage spray,
Soil treatment and the like can be mentioned, but any application method usually used by those skilled in the art is sufficiently effective. The applied amount and applied concentration are target crop, target disease, degree of disease occurrence,
Although it varies depending on the dosage form of the compound, the method of application, various environmental conditions, etc., when sprayed, 5 to 200 g per are are suitable, and preferably 10 to 100 g per are. A suitable spray concentration is 10 to 500 ppm, preferably 50 to 500 ppm.
It is 300 ppm.

The agricultural and horticultural fungicides of the present invention are, of course, mixed with other fungicides and insecticides, herbicides, plant growth regulators and other agricultural chemicals, soil improvers or fertilizers, and mixed preparations with these. Is also possible.

The compounds according to the invention may be applied as such, but are preferably applied in the form of a composition in admixture with a carrier which includes a solid or liquid diluent. As used herein, the term carrier means a synthetic or natural inorganic or organic substance that is formulated to help the active ingredient reach the site to be treated and to facilitate the storage, transportation, and handling of the active ingredient compound.

Suitable solid carriers include clays such as montmorillonite and kaolinite, diatomaceous earth, clay, talc, vermiculite, gypsum, calcium carbonate, silica gel, inorganic substances such as ammonium sulfate, soybean flour, sawdust, plant organic substances such as flour, and the like. Examples include urea.

Suitable liquid carriers include aromatic hydrocarbons such as toluene, xylene and cumene, paraffinic hydrocarbons such as kerosene and mineral oil, halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane, acetone and methyl ethyl ketone. Examples thereof include ketones, dioxane, ethers such as tetrahydrofuran, alcohols such as methanol, propanol and ethylene glycol, dimethylformamide, dimethylsulfoxide, water and the like.

Further, in order to enhance the efficacy of the compound of the present invention, the following auxiliary agents may be used alone or in combination according to the purpose in consideration of the dosage form of the preparation, the application scene and the like.

For the purpose of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., a water-soluble base such as lignin sulfonate, an alkylbenzene sulfonate, an anionic surfactant such as an alkyl sulfate ester salt, a polyoxyalkylene alkyl ether,
Polyoxyalkylene alkylaryl ether, polyoxyalkylene alkyl amine, polyoxyalkylene alkyl amide, polyoxyalkylene alkyl thioether, polyoxyalkylene fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxypropylene poly Examples include nonionic surfactants such as oxyethylene block polymers, bone agents such as calcium stearate and wax, stabilizers such as isopropylhydrodiene phosphate, and others such as methylcellulose, carboxymethylcellulose, casein, and gum arabic. However, these components are not limited to the above.

The amount of the active ingredient in the composition of the compound of the present invention is usually 0 in powder.
5-20% by weight, 5-20% by weight for emulsions, 10-9 for wettable powders
0% by weight, 0.1-20% by weight for granules, 10 for flowables
~ 90% by weight.

〔Example〕

Representative examples of the pyrazole derivative represented by the general formula (I) according to the present invention are shown in Table-1.

Next, the method for producing the compound of the present invention will be specifically described with reference to synthetic examples.

Synthesis Example 1 Synthesis of 2- (1,3-dimethylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentenenitrile (Compound No.-1) Ammonium chloride 8.3 g, sodium cyanide 5.0 g and water 50
It was dissolved in ml, and 15 ml of ethyl ether and 8 ml of 28% aqueous ammonia were added thereto. Cool to 5 ° C in an ice bath and stir 3
7.0 g of -methyl-2-butenal was added dropwise, and the mixture was further stirred at the same temperature for 24 hours. After the reaction was completed, the ether layer was separated,
The aqueous layer was extracted with ether three times, then the ether layers were combined and dried over sodium sulfate. The ether layer was concentrated under reduced pressure, 100 ml of ethyl ether was added to the residue, and the mixture was cooled to 0-5 ° C. Then, after adding 4.2 g of triethylamine, 1,3-dimethylpyrazole-4-carboxylic acid chloride was added with stirring.
3.9g was added slowly. After the dropping, stirring was continued for another hour at the same temperature. The precipitated triethylamine hydrochloride was filtered off,
The filtrate was distilled under reduced pressure to remove the solvent. The residue was purified by silica gel column chromatography. Elution from a benzene-ethyl acetate system gave 3.7 g of the desired 2- (1,3-dimethylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentenenitrile.

Yield 64.6% mp110.5-111.5 ℃ Synthesis Example 2 Synthesis of 2- (1,3-dimethylpyrazol-4-ylcarbonylamino) -4-chloro-3-pentenenitrile (Compound No.-4) Ammonium chloride 6.7 g, sodium cyanide 4.0 g and water 50.
It was dissolved in 15 ml of ethyl ether, and 15 ml of ethyl ether and 7 ml of 28% aqueous ammonia were added thereto. Cool to 5 ° C in an ice bath and stir 3
7.0 g of -chloro-2-butenal was added dropwise, and the mixture was further stirred at the same temperature for 12 hours. After completion of the reaction, the ether layer was separated, the aqueous layer was extracted with ether three times, the ether layers were combined, and dried over sodium sulfate. The ether layer was concentrated under reduced pressure, 50 ml of tetrahydrofuran was added to the residue, and the temperature was 0 to 5 ° C.
Cooled to. Then after adding 3.4 g of triethylamine,
With stirring, 3.1 g of 1,3-dimethylpyrazole-4-carboxylic acid chloride was gradually added. After the dropping, stirring was continued for another hour at the same temperature. The precipitated triethylamine hydrochloride was filtered off and the filtrate was distilled under reduced pressure to remove the solvent. The residue was eluted with hexane-ethyl acetate system by silica gel column chromatography to give the desired 2- (1,3-dimethylpyrazol-4-ylcarbonylamino) -4-chloro-3-
2.6 g of pentenenitrile was obtained.

Yield 52.5% mp 113-114 ° C Synthesis Example 3 Synthesis of 2- (1,3-dimethylpyrazol-4-ylcarbonylamino) -3-pentenenitrile (Compound No.-
5) Ammonium chloride 10.0g, sodium cyanide 6.0g water 5
It was dissolved in 0 ml, and 15 ml of ethyl ether and 10 ml of 28% aqueous ammonia were added thereto. The mixture was cooled to 5 ° C in an ice bath, 7.0 g of crotonaldehyde was added dropwise with stirring, and the mixture was further stirred at the same temperature for 24 hours. After completion of the reaction, the ether layer was separated, the aqueous layer was extracted with ether three times, the ether layers were combined, and dried over sodium sulfate. The ether layer was concentrated under reduced pressure, 100 ml of ethyl ether was added to the residue, and the mixture was cooled to 0-5 ° C. Then, after adding 5.1 g of triethylamine, 1,3-
4.6 g of dimethylpyrazole-4-carboxylic acid chloride was gradually added. After the dropping, stirring was continued for another hour at the same temperature. 50 ml of water was added to dissolve the precipitated triethylamine hydrochloride. The ether layer was separated, washed with water and dried over sodium sulfate. The ether layer was distilled under reduced pressure to remove the solvent. The residue was purified by silica gel column chromatography. Elution from a hexane-ethyl acetate system gave 3.8 g of the desired 2- (1,3-dimethylpyrazol-4-ylcarbonylamino) -3-pentenenitrile. Yield 60.0
% Mp 109-110 ° C Synthesis Example 4 Synthesis of 2- (1-allyl-3-methylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentenenitrile (Compound No.-16) Ammonium chloride 8.3 g, sodium cyanide 5.0 g 50
It was dissolved in ml, and 15 ml of ethyl ether and 8 ml of 28% aqueous ammonia were added thereto. Cool to 5 ° C in an ice bath and stir 3
7.0 g of -methyl-2-butenal was added dropwise, and the mixture was further stirred at the same temperature for 24 hours. After the reaction was completed, the ether layer was separated,
The aqueous layer was extracted with ether three times, then the ether layers were combined and dried over sodium sulfate. The ether layer was concentrated under reduced pressure, 100 ml of ethyl ether was added to the residue, and the mixture was cooled to 0-5 ° C. Then 4.2 g of triethylamine was added. Further, according to the method of Reference Example (B) for synthesizing intermediates described below, 1
-Allyl-3-methylpyrazole-4-carboxylic acid chloride was obtained, and 4.5 g of the crude product was gradually added with stirring. After the dropping, stirring was continued for another hour at the same temperature. The precipitated triethylamine hydrochloride was filtered off, and the filtrate was distilled under reduced pressure to remove the solvent. The residue was purified by silica gel column chromatography. Eluted from hexane-ethyl acetate system,
The desired 2- (1-allyl-3-methylpyrazole-4-
4.3 g of ylcarbonylamino) -4-methyl-3-pentenenitrile was obtained.

Yield 67.9% Synthesis Example 5 Synthesis of 2- (1-methyl-3-ethylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentenenitrile (Compound No.-26) Ammonium chloride 2.8 g, sodium cyanide 1.7 g 17
6 ml of ethyl ether and 3 ml of 28% aqueous ammonia were added thereto. Cool to 5 ° C in an ice bath and stir 3
2.5 g of -methyl-2-butenal was added dropwise, and the mixture was further stirred at the same temperature for 24 hours. After the reaction was completed, the ether layer was separated,
The aqueous layer was extracted with ether three times, then the ether layers were combined and dried over sodium sulfate. The ether layer was concentrated under reduced pressure, 20 ml of ethyl ether was added to the residue, and the mixture was cooled to 0-5 ° C. Then 1.1 g of triethylamine was added. 1 in this
20 ml of ethyl ether containing 1.7 g of methyl-3-ethylpyrazole-4-carboxylic acid chloride was slowly added at room temperature with stirring. After the dropwise addition, stirring was continued for 30 minutes at the same temperature, and then the reaction solution was washed with water. The ether layer is separated, washed with water,
After drying over sodium sulfate, ether was distilled off under reduced pressure. The residue was purified by silica gel column chromatography. Elution with a hexane-ethyl acetate system gave the desired 2- (1-methyl-3-ethylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentenenitrile (1.6 g).

Yield 65.0% Synthesis Example 6 Synthesis of 2- (1-n-butyl-3-methylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentenenitrile (Compound No.-21) Ammonium chloride 2.8 g, sodium cyanide 1.7 g The water 17
6 ml of ethyl ether and 3 ml of 28% aqueous ammonia were added thereto. Cool to 5 ° C in an ice bath and stir 3
2.5 g of -methyl-2-butenal was added dropwise, and the mixture was further stirred at the same temperature for 24 hours. After the reaction was completed, the ether layer was separated,
The aqueous layer was extracted with ether three times, then the ether layers were combined and dried over sodium sulfate. The ether layer was concentrated under reduced pressure, 20 ml of ethyl ether was added to the residue, and the mixture was cooled to 0-5 ° C. Then 1.1 g of triethylamine was added. 1 in this
20 ml of ethyl ether containing 2.0 g of -n-butyl-3-methylpyrazole-4-carboxylic acid chloride was gradually added at room temperature with stirring. After the dropwise addition, stirring was continued for 30 minutes at the same temperature, and then the reaction solution was washed with water. The ether layer was separated, washed with water, dried over sodium sulfate, and then the ether was distilled off under reduced pressure. The residue was purified by silica gel column chromatography. Elution with a chloroform-ethyl acetate system gave 1.7 g of the desired 2- (1-n-butyl-3-methylpyrazol-4-ylcarbonylamino) -4-methyl-3-pentenenitrile.

Yield 62.0% Other compounds according to the present invention can also be synthesized according to the methods of Synthesis Examples 1 to 6.

The 3-chloro-2-butenal used as the raw material was "Journal of the Organic Chemistry".
(J. Org. Chem.), 30 , 1126 (1965). Further, other starting material pyrazole-4-carboxylic acid esters and pyrazole-4-carboxylic acids were synthesized according to the methods (A) to (C) shown below. In addition, when it was difficult to separate the isomers at the stage of this intermediate, the crude product was advanced to the next step and separated and purified in the final step.

Method (A) Method described in “Australian Journal of Chemistry” (Aust.J.Chem.), 36 , 135-147 (1983). Method (B) Method of later introducing a substituent into the nitrogen atom of the pyrazole ring (C) Method Pyrazole-4-aldehydes are oxidized to form pyrazole-
Method for obtaining 4-carboxylic acid The production method of pyrazole-4-carboxylic acids will be specifically described below with reference to Reference Examples.

Reference Example (1)-(A) Method Synthesis of 1,3-dimethylpyrazole-4-carboxylic acid A mixture of 18.6 g (0.1 mol) of ethyl 2-ethoxymethyleneacetoacetate and 47 ml of ethanol was cooled to 5 ° C in an ice bath. Then, 6.9 g (0.15 mol) of methylhydrazine was added dropwise with stirring. After the dropping, the reaction solution was heated and stirred under reflux for 4 to 5 hours. After completion of the reaction, the mixture was cooled to room temperature, added with 230 ml of water, salted out, and extracted three times with ethyl acetate. The ethyl acetate layers were combined, washed with saturated brine, and dried over sodium sulfate. The ethyl acetate layer was concentrated under reduced pressure to give crude ester 16.7
got g. To a mixture of sodium hydroxide (16.7 g) and water (33 ml) was added the crude ester (16.7 g) at room temperature with stirring, and the mixture was mixed at 100-110 ° C for 3
Stir for ~ 4 hours. After completion of the reaction, the mixture was cooled to room temperature and 42 ml of water was added. While cooling the reaction mixture, add concentrated hydrochloric acid to add pH 4 to
5, the precipitated crystal was collected by filtration, dried and recrystallized from water to obtain 9.8 g of the desired 1,3-dimethylpyrazole-4-carboxylic acid. Yield 70.0% mp 190-190.5 ° C Elemental analysis value (%) C H N Calc 51.42 5.75 19.99 Found 51.42 5.76 20.01 Reference example (2)-(B) method 1- (γ-chloroallyl) -3-methylpyrazole-4
-Synthesis of carboxylic acid 3-methylpyrazole-4 was added to sodium alcoholate prepared from 0.75 g of metallic sodium and 30 ml of ethanol.
-Add 5.0 g of ethyl carboxylate to a uniform area
3.6 g of 1,3-dichloropropene was added and the mixture was heated under reflux for 2 hours. After completion of the reaction, the reaction product was discharged into water, extracted with ethyl acetate, and purified by silica gel column chromatography. Elute with hexane-ethyl acetate system to give 1- (γ
Ethyl -chloroallyl) -3-methylpyrazole-4-carboxylate Z form 2.5 g (34%) and E form 1.5 g (20%) were obtained. 2.5 g of Z-form, 25 ml of ethanol, 2.5 g of sodium hydroxide
The mixture was heated and stirred with a mixture of water and 25 ml of water for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, and while the reaction solution was being cooled, concentrated hydrochloric acid was added to adjust the pH to 4 to 5. The precipitated crystals were collected by filtration, dried, and recrystallized from water to give the desired 1- (γ-chloroallyl allyl). )
0.3 g of -3-methylpyrazole-4-carboxylic acid Z form was obtained. Yield 14%, mp96-100 ° C Perform the same procedure as above for E-form to obtain 0.34 g of the desired product.
Got Yield 30%, mp152-156 ° C Reference Example (3)-(C) Method Synthesis of 1-methylpyrazole-4-carboxylic acid 1-Methylpyrazole-4-aldehyde ("Journal of Chemical Society" (J. Chem. Soc.), 195
7, 331 described) 3.9 g was dissolved in acetone 20 ml, was added while heating Jones reagent. After completion of the reaction, excess Jones reagent was treated with a dilute aqueous alkali solution, and the precipitate was collected by filtration,
The filtrate was made weakly acidic and extracted with ethyl acetate. After drying over sodium sulfate, it was concentrated under reduced pressure to give 1-methylpyrazole-4.
-2.3 g of carboxylic acid was obtained. Yield 52% mp 205 to 206 ° C. Similarly, other pyrazole-4-used in the present invention
Carboxylic acid was also synthesized.

Representative examples of pyrazole-4-carboxylic acids obtained by the above method are shown in Table 2 together with their physical properties.

The obtained pyrazole-4-carboxylic acid was used as an acid chloride represented by the general formula (II) according to a conventional method. The pyrazole-4-carboxylic acid is not recrystallized, and is directly converted into an acid chloride according to a conventional method, and then the crude product obtained by reacting with the amine represented by the general formula (III) is purified by column chromatography. By doing so, the desired compound of the general formula (I) can be obtained.

Next, a method for producing the agricultural / horticultural germicide of the present invention will be described with reference to formulation examples.

The active ingredient compounds are shown by the compound numbers in Table 1 above.

"Part" represents "part by weight".

Formulation Example 1 Dust Compound (1): 3 parts, diatomaceous earth: 20 parts, clay: 30 parts and talc: 47 parts were uniformly pulverized and mixed to obtain 100 parts of a powder formulation.

Formulation Example 2 Wettable powder Compound (2): 30 parts, diatomaceous earth: 47 parts, white clay: 20 parts, sodium lignin sulfonate: 1 part and sodium alkylbenzene sulfonate: 2 parts are uniformly pulverized and mixed to obtain a wettable powder. I got 100 copies.

Formulation Example 3 Emulsion Compound (3): 20 parts, cyclohexanone: 10 parts, xylene: 50 parts and Sorpol (surfactant manufactured by Toho Chemical) 20
Parts were uniformly dissolved and mixed to obtain 100 parts of emulsion.

Formulation Example 4 Granules Compound (4): 1 part, bentonite: 78 parts, talc: 20 parts and sodium lignin sulfonate: 1 part are mixed, an appropriate amount of water is added and mixed, and then an extrusion granulator is used. The granules were granulated by a usual method and dried to obtain 100 parts of granules.

Formulation Example 5 Granules Compound (3): 5 parts, polyethylene glycol nonylphenyl ether: 1 part, polyvinyl alcohol: 3 parts and clay: 91 parts are uniformly mixed, hydrolyzed and dried to obtain 100 parts of granules. It was

Formulation Example 6 Dust Compound (6): 2 parts, calcium carbonate: 40 parts and clay:
58 parts were uniformly mixed to obtain 100 parts of powder.

Formulation Example 7 Wettable powder Compound (5): 50 parts, talc: 40 parts, sodium lauryl phosphate: 5 parts and sodium alkylnaphthalene sulfonate: 5 parts were mixed to obtain 100 parts of a wettable powder.

Formulation Example 8 Wettable powder Compound (1): 50 parts, sodium lignin sulfonate: 10
Parts, sodium alkylnaphthalene sulfonate: 5 parts, white carbon: 10 parts and diatomaceous earth: 25 parts were mixed and ground to obtain 100 parts of a wettable powder.

Formulation Example 9 Flowable agent Compound (6): 40 parts, carboxymethylcellulose: 3
Parts, sodium ligninsulfonate: 2 parts, dioctylsulfosuccinate sodium salt: 1 part and water 54 parts were wet-milled with a sand grinder to obtain 100 parts of a flowable agent.

Next, the efficacy of the compound of the present invention as an agricultural and horticultural fungicide will be described with reference to test examples. The following compounds were used as targets in the test examples.

Target compound A: 2-benzoylaminopropiononitrile B: 4- (2,4-dichlorobenzoyl) -5-benzoylmethoxy-1,3-dimethylpyrazole [pyrazoxin] C: zinc ethylene bis (dithiocarbamate) [dineb] D: Tetrachloroisophthalonitrile [TPN] The target compound A is the above-mentioned document Justus Liebigs Ann. Chem., 1972 , 764,6
9 to 93, B is a commercially available compound as a herbicide for paddy fields. C and D are commercially available agents for controlling potato epidemics and cucumber downy mildew.

Test Example 1 Potato epidemic control test (preventive effect) A potato (cultivar: baron, plant height of about 25 cm) grown in a pot in a greenhouse has a predetermined concentration of a drug (test compound according to the method of Formulation Example 8 above). Was prepared and diluted with water to a predetermined concentration), and 50 ml per 3 pots was sprayed using a spray gun (1.0 Kg / cm ² ) and air dried. A zoospore suspension was prepared from the Phytophthora infestans cultivated on potato slices for 7 days in advance. This suspension was spray-inoculated onto the potato plants sprayed with chemicals, and the test plants were heated at 17 to 19 ° C and a humidity of 95.
%, The degree of lesion formation was investigated.

The lesion area ratio was observed and evaluated for each leaf to determine the disease degree index, and the disease degree was calculated for each plot by the following formula.

The evaluation criteria are as follows.

Disease severity index 0: Lesion area ratio 0% 〃 1: 〃 1 to 15% 〃 2: 〃 6 to 25% 〃 3: 〃 26 to 50% 〃 4: 〃 51% or more n ₀ : Disease severity index 0 Number of leaves n ₁ : 〃 1 〃 n ₂ : 〃 2 〃 n ₃ : 〃 3 〃 n ₄ : 〃 4 〃 N = n ₀ ＋ n ₁ ＋ n ₂ ＋ n ₃ ＋ n _{4 The} results are shown in Table-3.

Test Example 2 Potato epidemic control test (therapeutic effect) A zoospore suspension was prepared from potato epidemic bacteria cultivated on potato slices for 7 days in advance on potato (cultivar: baron, plant height of about 25 cm) grown in a pot in a greenhouse, Spray inoculated. After holding at 17 to 19 ° C for 20 hours, spray gun with a predetermined concentration of the drug (a test compound was prepared as a wettable powder according to the method of Preparation Example 8 and diluted with water to a predetermined concentration) (1.0 kg / cm ² ) was used to spray 50 ml per 3 pots and air dried. After keeping it at 17-19 ℃ and humidity 95% or more for 6 days,
The degree of lesion formation was investigated. The evaluation criteria and morbidity display method are the same as those described in Test Example 1.

The results are shown in Table-4.

Test Example 3 Cucumber downy mildew control test (prevention result) Cucumbers grown in pots in the greenhouse (variety: Sagamihanshiro,
Spray two leaves (two to three true leaves) with a prescribed concentration of a drug (a test compound was prepared as a wettable powder according to the method of Preparation Example 8 and diluted with water to a prescribed concentration). Gun (1.
30 kg per 3 pots was sprayed using 0 kg / cm ² ) and air dried.
The downy mildew fungus was collected from the spotted cucumber leaf spot affected by downy mildew, a spore suspension was prepared with demineralized water, and spray-inoculated. Immediately after keeping the inoculated pot at 18 to 20 ° C and humidity of 95% or more for 24 hours, move it to a greenhouse (room temperature 18 to 27 ° C),
After 7 days, the degree of lesion formation was investigated.

The evaluation criteria and morbidity display method are the same as those described in Test Example 1.

The results are shown in Table-5.

Test Example 4 Cucumber downy mildew control test (therapeutic effect) A cucumber similar to that used in Test Example 3 was spray-inoculated with the cucumber downy mildew spore suspension prepared in the same manner. Immediately place the inoculated pot at a temperature of 18 to 20 ° C and humidity of 95% or more.
After maintaining for a certain period of time, a spray gun (1.0 Kg / cm ² ) was prepared with a drug having a predetermined concentration (a test compound was prepared as a wettable powder according to the method of Preparation Example 8 and diluted with water to a predetermined concentration). ) Was used to spray 30 ml per 3 pots and air dried. Further, the pot was transferred to a greenhouse (room temperature 18 to 27 ° C.), and after 7 days, the degree of lesion formation was investigated.

The evaluation criteria and morbidity display method are the same as those described in Test Example 1.

The results are shown in Table-6.

Test Example 5 Tomato epidemic control test (soil irrigation treatment) Tomatoes grown in pots in a greenhouse (variety: world's best, plant height)
Approximately 20 cm) pot (diameter 7.5 cm) with a prescribed amount of drug (test compound was prepared as a wettable powder according to the method of Preparation Example 8 and diluted with water to a prescribed concentration) Was irrigated with 2 ml per pot using a pipette and kept in the greenhouse for 5 days. A zoospore suspension was prepared from Phytophthora infestans cultivated on potato slices for 7 days in advance. This suspension was spray-inoculated onto the tomato plants that had been treated with chemicals, and
After being kept at 19 ° C and humidity of 95% or more for 6 days, the degree of formation of lesions was investigated. The evaluation criteria and morbidity display method are Test Example 1
It is as shown in.

The results are shown in Table-7.

From the results shown in Table-3 to Table-7, the compound group of the present invention is not only sprayed against plant diseases caused by algae such as potato epidemic disease, tomato epidemic disease, cucumber downy mildew disease, etc., but also high control effect in soil irrigation treatment. In contrast, the control compound A or B, which is considered to be relatively similar to the compound group of the present invention, shows no controlling effect against these diseases. Further, it has a very low dose and a preventive effect as compared with zinc ethylene bis (dithiocarbamate) or tetrachloroisophthalonitrile, which are currently commercially available and widely used against these plant diseases, and do not have the above two drugs. It is clear that the therapeutic effect and the control effect by soil irrigation treatment are also combined.

[Effects of the Invention] As is clear from the above description, the pyrazole derivative according to the present invention is a fungicide for agriculture and horticulture against various diseases caused by algae of various crops, and it seems that the effects cannot be expected with conventional commercial drugs. It has an excellent control effect at low dose and low concentration. In addition, since it has a therapeutic effect, it can be expected to have a controlling effect even if it is sprayed with a drug after the crop has been sick. Therefore, the compound of the present invention can greatly change the disease controlling system of agricultural and horticultural crops, which is a great labor saving for growers. Is clear. Thus, the pesticide containing the pyrazole derivative according to the present invention has excellent properties as a fungicide for agricultural and horticultural use and is useful.

Claims (6)

[Claims] 1. A general formula (I) (In the formula, R ¹ represents an alkyl group, an alkenyl group, a haloalkenyl group, a phenyl group or an alkylcarbamoyl group, R ² represents a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group, and R ³ represents a hydrogen atom or a halogen. Atom, a lower alkyl group or a phenyl group, and R ⁴ and R ⁵ each represent a hydrogen atom, a chlorine atom or a lower alkyl group). 2. In the general formula (I), R ¹ is a lower alkyl group or a phenyl group, R ² is a lower alkyl group, R ³ is a hydrogen atom, R ⁴ and R ⁵ are methyl groups. The pyrazole derivative according to claim 1, which is characterized in that 3. In the general formula (I), R ¹ and R ² are lower alkyl groups, R ³ is a hydrogen atom, and R ⁴ and R ⁵ are methyl groups. A pyrazole derivative according to claim 1. 4. In the general formula (I), R ¹ , R ² , R ³ and
The pyrazole derivative according to claim 1, wherein R ⁴ is a methyl group and R ⁵ is a hydrogen atom. 5. The general formula (II) (In the formula, R ¹ represents an alkyl group, an alkenyl group, a haloalkenyl group, a phenyl group or an alkylcarbamoyl group, R ² represents a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group, and R ³ represents a hydrogen atom or a halogen. Atom, a lower alkyl group or a phenyl group, and X is a halogen atom) and a compound represented by the general formula (III) (Wherein R ⁴ and R ⁵ each represent a hydrogen atom, a chlorine atom or a lower alkyl group), and a compound represented by the general formula (I) (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each have the above-mentioned meaning). 6. General formula (I) (In the formula, R ¹ represents an alkyl group, an alkenyl group, a haloalkenyl group, a phenyl group or an alkylcarbamoyl group, R ² represents a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group, and R ³ represents a hydrogen atom or a halogen. Atom, a lower alkyl group or a phenyl group, and R ⁴ and R ⁵ each represent a hydrogen atom, a chlorine atom or a lower alkyl group), which is a fungicide for agricultural and horticultural use.