JPS62103067A - Pyrazole derivative, production thereof, and herbicide and agricultural and horticultural fungicide containing same - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I(R is alkyl, alkenyl, alkoxyalkyl, cycloalkyl, haloalkyl, haloalkenyl or halocycloalkyl). EXAMPLE:Cyclohexanecarbonylamino-(1-pyrazoyl)acetonitrile. USE:A herbicide for paddy fields and an agricultural and horticultural fungicide. Having a wide application range as the herbicide for paddy fields, low phytotoxicity to paddy rice plants, low toxicity to fishes and showing preventing and remedying effects on blights and downy mildew or various crops with a small amount as the fungicide. PREPARATION:An acid chloride shown by the formula II(R<1> is R or cycloalkenyl) is reacted with aminoacetonitrile shown by the formula V to give a compound shown by the formula III, which is reacted with a halogenating agent such as Br2, etc., to give a halogenated intermediate shown by formula IV(X is halogen). Then, this compound is reacted with a pyrazole shown by the formula IV(X is halogen) to give a compound shown by the formula I.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to the general formula (1) (wherein R is an alkyl group, an alkenyl group, an alkoxyalkyl group, a cycloalkyl group, a haloalkyl group, a haloalkenyl group, or a halo The present invention relates to pyrazole derivatives represented by (representing a cycloalkyl group), their production methods, and herbicides for paddy fields and fungicides for agriculture and horticulture containing them as active ingredients.

[Prior art]

Many studies have been conducted on organic synthetic compounds useful in agriculture and horticulture, and many compounds exhibiting physiological activity have been discovered and put into practical use. A large number of active compounds have also been found with respect to compounds containing amide as a backbone, and some of these compounds are used as herbicides or fungicides.

For example, as a substituted benzamide derivative, ethyl-N-
Pensoyl-N-(3,4-dichlorophenyl)-2-
Aminopropionate (benzoylprop-ethyl) is known as a herbicide, and 2-methyl-N-(3-isopropoxyphenyl)benzamide (mepronil) is known as a fungicide. Further, as amide-substituted acetonitrile derivatives, JP-A-57-167978, 57-1
Herbicides and fungicides are disclosed in JP 76938 and JP 58-69866. Among them, JP-A-58-6
Although pyrazolylacetonitrile derivatives are disclosed in Publication No. 9866, there is no description of pyrazolylacetonitrile derivatives as shown in the compounds of the present invention. Further, JP-A-58-69866 describes its use as a herbicide and fungicide.

Herbicides have been tested for pre-emergence and post-emergence herbicidal activity as well as phytotoxicity against sugar beets, rapeseed, cotton, soybeans, corn, wheat, and rice.

However, these derivatives have not been found to have any selectivity for the above crops.

Conventionally, herbicides containing amide compounds and thiol carbamate compounds (of equal length) have been developed and put into practical use as herbicides for paddy fields, but their performance is still not sufficient.The amide compound butachlor Although it is used before and after rice planting, there is always the problem of chemical damage to rice caused by temperature conditions, etc. The use of molinate, a thiol carbamate compound, is regulated due to fish toxicity.

In addition, penthiocarb poses a problem of phytotoxicity to paddy rice under reducing soil conditions. Diphenyl ether compounds, like butachlor, are used immediately after rice planting, but their activity decreases dramatically if treatment is delayed.

All of these herbicides have excellent performance in some respects, so they are widely used and widely used, but their shortcomings and problems have gradually become apparent.
There is a strong need for a new herbicide for rice fields that is easier to use and has superior performance.

On the other hand, the compound described in Japanese Patent Application Laid-open No. 58-69866 is said to be effective as a fungicide against podobe rot and tomato late blight. Captafor, TPN, cabtan, or dithiocarbamate-based drugs have been widely used to treat late blight and downy mildew of various crops, and have contributed to increased crop production. However, all of these compounds mainly have a preventive effect against late blight and downy mildew, and have no therapeutic effect at all (
I can't wait. Therefore, by the time disease outbreaks are recognized, there is a major drawback that sufficient effects cannot be expected.
It has one point. In reality, when considering the spraying of chemicals to control crop diseases, they are more or less sprayed after the disease has appeared, and it is difficult to completely control the disease with these compounds.

Furthermore, the concentration of compounds that exhibit pesticidal effects is extremely high, which is also viewed as a problem in terms of the safe use of pesticides. These points should be improved (research into new pest control agents continues, and N-phenylalanine ester derivatives, such as metalaxyl (:N-(2,6-
dimethylphenyl)-N-(2'-methoxyacetyl)alanine methyl ester] and the like have been developed and are being put into practical use worldwide. However, these N-7 engineered nylalanine ester derivatives have already been viewed as a problem in that they reduce the control effect of fungicides due to the development of drug-resistant bacteria.

In addition, in the conventional methods proposed as methods for producing amide-substituted acetonitrile derivatives (JP-A-57-176938 and JP-A-58-69866), hydrolysis of the nitrile group occurs in the 10-genation step, resulting in formation of carbamoyl derivatives. Therefore, if an acetonitrile derivative was obtained by, for example, pyrazolylating the no-rogen and then dehydrating the carbamoyl group, a long process was required and the yield was low.

[Problem to be solved by the invention]

The present invention overcomes the drawbacks of the prior art described above, and provides a compound having extremely excellent properties as a herbicide for paddy fields and a fungicide for agriculture and horticulture, a method for producing the compound, and a noxious weed control agent containing the compound as an active ingredient. The objective is to provide a microbial control agent.

In other words, as a herbicide, it has a wide range of suitability for paddy fields, has little phytotoxicity to paddy rice, and has low toxicity to fish, and as a fungicide, it has preventive and therapeutic effects against late blight and downy mildew of various crops. Compounds with a wide range of applications that have both of these properties and also have an excellent control effect on soil diseases such as seedling damping-off of various crops, simpler and higher-yielding methods for producing them, and useful materials containing them. The purpose of the present invention is to provide a pesticide composition with the following properties.

[Means and effects for solving the problem] As a result of intensive research on pyrazole derivatives to solve the above problem, it was found that pyrazolylacetonitrile derivatives have physiological activities that could not be predicted from the patent exemplified compounds, As a herbicide for paddy fields, it has a wide range of suitable periods, and is less harmful to paddy rice and less toxic to fish.As a fungicide, it is effective against late blight, downy mildew, etc. of various crops.
We have completed the present invention by discovering that it has both therapeutic effects and also exhibits excellent control effects against soil diseases such as seedling damping-off of various crops.

The pyrazole derivative according to the present invention has the general formula (11 (wherein,
R represents an alkyl group, an alkenyl group, an alkoxyalkyl group, a cycloalkyl group, a haloalkyl group, a haloalkenyl group, or a halocycloalkyl group).

The present invention also provides a method for producing an acylamino-pyrazolylacetonitrile derivative, which is a pyrazole derivative represented by the general formula (1), as a result of intensive studies to overcome the drawbacks of the prior art. The present invention was completed by discovering a method for obtaining the target product in high yield.

That is, the method for producing the acylamino-pyrazolylacetonitrile derivative, which is a pyrazole derivative according to the present invention, is based on the general formula (■) R'-COCl (■) (wherein R' is an alkyl group, an alkenyl group, an alkoxyalkyl group, or a cycloalkyl group). group, cycloalkenyl group,
An acid chloride represented by a haloalkyl group, a haloalkenyl group, or a halocycloalkyl group is reacted with aminoacetonitrile to form a compound represented by the general formula ([1) % formula %() (R' represents the above meaning). acylaminoacetonitrile is obtained, and this is treated with a no-rogenation agent to obtain no-rogen represented by the general formula (IV) (wherein R has the above meaning and X represents a)-rogen atom). The general formula (
This is a method for producing an acylamino-pyrazolylacetonitrile derivative represented by No. 11.

The method for producing the compound of the present invention represented by general formula (1) will be explained below using reaction scheme A.

Reaction scheme A (II) (III) Acylaminoacetoni obtained by reacting the acid chloride represented by the general formula (n) with aminoacetonitrile) IJ
The halogenated intermediate (good) is obtained by treating the compound with a halogenating agent in a suitable solvent. Solvents used in this halogenation reaction include aliphatic halides such as dichloromethane, chloroform, carbon tetrachloride, and 1,4-dichloroethane; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate, and ethyl propionate; Examples include carbon disulfide, but good results can be obtained by using aliphatic carboxylic acid esters, especially ester solvents such as ethyl acetate. ... Bromine, chlorine, phosphorus oxychloride, sulfuryl chloride, phosphorus tribromide, etc. can be used as the rogensing agent. Reaction temperature is 0-120℃
, preferably at room temperature. Note that this reaction may be performed in an inert gas atmosphere. Since the halogenated intermediate is unstable, it is used immediately after its preparation. This halogenated compound is reacted with pyrazole. This reaction can be carried out in the presence of an acid acceptor. Examples of acid acceptors include, but are not limited to, organic bases such as triethylamine, dimethylaniline, pyridine, and inorganic bases such as ammonia, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, and ammonium carbonate. It's not a thing. This reaction is preferably carried out in a solvent or diluent. Pyridine can be used both as a solvent and as an acid acceptor.

This reaction does not have good thermal stability of the intermediate, so it is not desirable to react at too high a temperature, and since it is an exothermic reaction, it is desirable to carry out the reaction under cooling. At low temperatures, reaction intermediates tend to precipitate and the reaction rate becomes slow (and impractical), so it is desirable to carry out the reaction at -30 to 50°C, preferably -20 to 20°C.

The desired acylamino-pyrazolylacetonitrile derivative obtained in this manner can be easily isolated and purified by conventional methods such as recrystallization and column chromatography.

Furthermore, the present invention provides a herbicide for rice fields and a fungicide for agricultural and horticultural purposes, which contain as an active ingredient an acylamino-pyrazolylacetonitrile derivative, which is a pyrazole derivative represented by the general formula (1) according to the present invention. It is something to do. When the compound of the present invention is used as a herbicide for paddy fields, the application amount varies depending on the growth stage of the weed, the type of weed, the dosage form of the preparation, the application method, various environmental conditions, etc., but is usually 90.1 per R. -100 g/a is suitable, preferably 0.5-25 g/a.

Its herbicidal activity is characteristically strong against grass weeds, but it also has a strong herbicidal activity against other weeds, although the degree varies depending on the type.
Shows strong inhibitory effect. In particular, weeds of the Cyperaceae family, such as Cyperaceae and Firefly, are particularly strongly suppressed. Such characteristics work advantageously when applying a mixture with conventional agents that are weak against grass weeds, or when performing a mixed application using a tank mix or the like.

In addition, the timing of application of the compound of the present invention is wide, from before the emergence of weeds to the growing season. It has a wide range of excellent characteristics that have not been seen before, and can be an easy-to-use herbicide with fewer restrictions on treatment timing.The practical amount of herbicidal activity against Japanese millet naturally depends on the treatment timing, but 3. While bentiocarb and butachlor are insufficiently effective at practical dosages for Japanese millet at the five-leaf stage, the compounds of the present invention exhibit sufficient activity for practical use at dosages lower than those practical dosages.

The compound of the present invention has extremely low phytotoxicity to transplanted paddy rice no matter when it is used at any time of treatment.

When the compound of the present invention is used as an agricultural and horticultural fungicide, it is not only effective against late blight and downy mildew of various crops caused by algal fungi, but also effective against diseases caused by various other plant pathogenic fungi. It is also effective.

The main diseases to be controlled are potato late blight, tomato late blight, tobacco late blight, strawberry late blight, adzuki bean stem blight, pudobe blight, cucumber blight, hop blight, shungikube blight, Aquanomyces spp., Pythium spp. Various crop seedling damping-off diseases can be mentioned.

Methods for applying the compound of the present invention include seed disinfection, foliage spraying,
Examples include soil treatment, but any application method commonly used by those skilled in the art will exhibit sufficient efficacy. The application amount and concentration will depend on the target crop, target disease, degree of disease occurrence,
It varies depending on the dosage form of the compound, application method, various environmental conditions, etc., but when spraying, the amount is 5 to 200 g per area.
is suitable, and desirably 910 to 100 g per radius.

The appropriate spray concentration is 20 to 1,000 ppm, preferably 50 to 500 ppm.

The herbicides and agricultural and horticultural fungicides of the present invention can of course be used in combination with other fungicides, insecticides, herbicides, pesticides such as plant growth regulators, soil conditioners, or fertilizing substances. Mixed preparations are also possible.

The compounds of the invention may be applied neat or preferably in the form of a composition mixed with a carrier, including solid or liquid diluents. As used herein, carrier means an inorganic or organic substance, synthetic or natural, which is incorporated to aid in the delivery of the active ingredient to the site to be treated and to facilitate storage, transport and handling of the active ingredient compound.

Suitable solid carriers include clays such as montmorillonite and kaolinite, inorganic substances such as diatomaceous earth, clay, talc, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate, vegetable organic substances such as soybean flour, sawdust, and wheat flour; 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; ketones such as acetone and methyl ethyl ketone; Examples include alcohols such as methanol such as dioxane and tetrahydrofuran, propatool and ethylene glycol, dimethylformamide, dimethyl sulfoxide, and water.

Furthermore, in order to enhance the efficacy of the compound of the present invention, the following adjuvants may be used individually or in combination depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc.

For the purpose of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as genin sulfonate, nonionic surfactants such as alkylbenzene sulfonate, alkyl sulfate, calcium stearate, wax, etc. lubricants, stabilizers such as isopropylhydrodiene phosphate, and others such as methylcellulose, carboxymethylcellulose, casein, and gum arabic. but,
These components are not limited to those mentioned above.

The amount of active ingredient in the composition of the compound of the present invention is usually 0 when used as a powder.
．． The content is 5 to 20% by weight, 5 to 30% by weight for emulsions, 10 to 90% by weight for wettable powders, 0.1 to 20% by weight for granules, and 10 to 90% by weight for flowables.

〔Example〕

Representative examples of pyrazole derivatives represented by general formula (11) according to the present invention are shown in Table 1.

Next, the method for producing the compound of the present invention will be specifically explained by giving a synthesis example.

Synthesis Example 1 Cyclohexanecarbonylamino-(1-pyrazolyl)
Synthesis of IJ (Compound No.-1) Cyclohexanecarbonylaminoacetonitrile 4.0
9- in ethyl acetate group 200 at room temperature, bromine 3.81
added at once. When the color of bromine in the reaction solution disappeared, the reaction solution was cooled to 0 to 5°C. Pyrazole 2.0? and triethylamine 5.4p to tetrahydrofuran 3Qyn
1 and added dropwise to the previously cooled ethyl acetate solution.

After the completion of the dropwise addition, the reaction was continued at the same temperature for an additional 30 minutes. The triethylamide/hydrobromide salt was filtered off, and the filtrate was distilled under reduced pressure to remove the solvent. The residue was recrystallized from dichloromethane to give the desired cyclohexanecarbonylamino-(1-pyrazolyl)acetonitrile as a white solid with 4.3? Obtained. Yield 76.9%, m, p, 166"-168°C Synthesis Example 2 Synthesis of (2-methylvalerylamino)-(1-pyrazolyl)acetonyl) Bromine (4.2z) was added all at once to a solution of 4.0y- of acetonitrile (4.0y-) in ethyl acetate at room temperature. After stirring until the color of bromine in the reaction solution disappeared, the reaction solution was cooled to 0-5°C. Pyrazole 2.11 and triethylamine 5.81 were dissolved in 30 mA! of ethyl acetate and added dropwise to the previously cooled ethyl acetate solution.After the dropwise addition was completed, the reaction was continued at the same temperature for another 30 minutes, and then water 1
00ml was added to dissolve the precipitated triethylamine hydrobromide salt. The oil layer was separated, washed with water, dried, and then the solvent was distilled off under reduced pressure. The residue was recrystallized from dichloromethane to give the desired (2-methylvalerylamine)-(1-pyrazolyl)acetonitrile as a white solid with a concentration of 3.6? Obtained.

Yield 63.0%, m, p, 103-105°C Synthesis Example 3 Synthesis of (1,2-Schiff"como-1-methylpropanecarbonylamino)-(1-pyrazolyl)acetonitrile (Compound No. 28) Amino sulfate Acetonitrile 1.6851- to water 10rn
5 ml of an aqueous solution containing 1.21 g of potassium hydroxide was added dropwise. After stirring at 6° C. for 20 minutes, 10 ml of toluene was added, and at the same temperature, a toluene solution of 3.141 ml of 2,3-dibromo-2-methylbutanoic acid chloride was added dropwise. After stirring at 10-15°C for 2 hours, drain into water,
After extraction with ethyl acetate, the organic layer was washed with water, dried, and concentrated under reduced pressure to obtain 3.4 J of (1,2-dibromo-1-methylpropanecarbonylamino)acetonitrile. Then (1
, 2-dibromo-1-methylpropanecarbonylamino)acetonitrile in 5 Qml of ethyl acetate at room temperature, 1.81 ml of bromine was added with stirring. After stirring until the color of bromine in the reaction solution disappeared, the reaction solution was heated to 10°C.
It was cooled to 0.77 p of pyrazole and 2.31 p of triethylamine were dissolved in 10 g of ethyl acetate and added dropwise to the previously cooled ethyl acetate solution. After the dropwise addition was completed, the reaction was continued at the same temperature for another 2 hours, and then 100 ml of water was added to dissolve the precipitated triethylamine hydrobromide salt. The oil layer was separated, washed with water, dried, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (solvent system, n-hexane-ethyl acetate) to obtain the desired (1,2-dibromo-1-methylpropanecarbonylamino)-(1
-pyrazolyl)acetonitrile 2.3y- was obtained. Yield 57.0%, m, p, 124-125°C Synthesis Example 4 (2,3-dibromo-2-methylvalerylamino)-(
Synthesis of 1-pyrazolyl)acetonitrile (Compound No. 13) 6.3y- of aminoacetonitrile sulfate was dissolved in 3Qrnl of water, and under water cooling, 6.73% of potassium hydroxide was dissolved. 15ml of an aqueous solution dissolved in 2-methyl-2-henthenic acid (IJ)' was added dropwise, and after stirring for 20 minutes at 5-6°C, 30ml of toluene was added and a 7.95% toluene solution of 2-methyl-2-henthenic acid (IJ)' was added dropwise at the same temperature. . After stirring at 10-15°C for 2 hours, it was drained into water, extracted with ethyl acetate, and the organic layer was washed with water, dried, and concentrated under reduced pressure. Got the OP.

Then (1-methyl-1-butenecarbonylamine)acetonitrile 9.0? At room temperature, 7.8% of bromine was added to 59ml of ethyl acetate solution. was added while stirring.

After stirring until the color of bromine in the reaction solution disappeared, the reaction solution was cooled to 10°C. Pyrazole 1.11 and triethylamine 10.17? - was dissolved in 10 ml of ethyl acetate and added dropwise to the previously cooled ethyl acetate solution. After the dropwise addition was completed, the reaction was continued at the same temperature for another 2 hours, and then 200% of water was added.
rnA! was added to dissolve the precipitated triethylamine hydrogen bromide salt. The oil layer was separated, washed with water, dried, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (solvent system: n-hexane-ethyl acetate) to obtain the desired (2,3-dibromo-2-methylvalerylamino)-(1-pyrazolyl)acetonitrile 0.535'
I got it.

Yield 11.7%, m, p, 107-109°C Next, the method for producing the herbicide for paddy fields or the fungicide for agriculture and horticulture of the present invention will be explained using formulation examples.

The active ingredient compound is indicated by the compound number of Cloth-1. "Part" means "part by weight".

Formulation Example 1 Powder compound (1): 3 parts, diatomaceous earth: 20 parts, white clay = 30
and talc: 47 parts were uniformly ground and mixed to make a powder of 10 parts.
I got 0 copies.

Formulation Example 2 Wettable powder compound (21: 30 parts, diatomaceous earth: 47 parts, white clay:
20 parts of sodium ligninsulfonate, 1 part of sodium ligninsulfonate, and 2 parts of sodium alkylbenzenesulfonate were uniformly ground and mixed to obtain 100 parts of a wettable powder.

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

Formulation Example 4 Granule compound (4): 1 part, bentonite: 78 parts, talc:
After mixing 20 parts and 1 part of sodium ligninsulfonate, adding an appropriate amount of water and kneading, the mixture was granulated in a conventional manner using an extrusion granulator, and after drying, 100 parts of granules were obtained.

Formulation Example 5 Granule Compound (10) Near part, Polyethylene glycol nonylphenyl ether: 1 part, Polyvinyl alcohol: 3
and 89 parts of clay were uniformly mixed, granulated with water, and dried to obtain 100 parts of granules.

Formulation Example 6 Powder Compound (6): 2 parts, calcium carbonate = 40 parts, and clay: 58 parts were uniformly mixed to obtain 100 parts of a 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 (6): 50 parts, sodium lignin sulfonate = 10 parts, sodium alkylnaphthalene sulfonate = 5 parts, white carbon: 10 parts, diatomaceous earth: 2
5 parts were mixed and ground to obtain 100 parts of a wettable powder.

Formulation Example 9 Flowable agent compound (40 parts of crab, carboxymethyl cellulose: 3
1 part, sodium ligninsulfonate = 2 parts, dioctyl sulfosuccinate sodium salt: 1 part, and 54 parts of water were wet-pulverized with a sand grinder to obtain a flowable agent of 10 parts.
I got 0 copies.

Next, the efficacy of the compound of the present invention as a herbicide and a fungicide for agricultural and horticultural purposes will be explained using test examples. In addition, the following compounds were used as controls in the test examples.

Control compound A: 2-benzoylamino-2-pyrazolylacetonitrile B: (3,5-dichlorobenzoylamine)-pyrazolylacetonitrile C: 2-chloro-2',6'-diethyl-N-(p.

Toxymethyl)acetanilide [Butachlor] 5-p-chlorobenzyl D-nidiethylthiocarbamate [Benthiocarb] E: Zinc ethylene bis(dithiocarbamate) [Zineb] F: Tetrachloroisophthalonitrile [TPN] Control compounds A and B are A compound described in JP-A-58-69866. C and D are commercially available herbicides for paddy fields. E and F are commercially available agents for controlling potato late blight, chyme blight, etc.

Test Example 1 Paddy field pre-emergence weed control test R/Fill soil in a 5000 Wagner pot, and test for weeds such as Japanese millet, broad-leaved weeds (Kikashigusa, Azena, Prunus japonicus, etc.).
Seeds of firefly, Heraomodaka and Tamagayatsuri were sown, and the area was flooded. Two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. One day after transplanting paddy rice and before weeds appeared, a predetermined amount of the test compound was submerged in water using granules prepared according to the method described in Formulation Example 5 above. Processing 30
A day later, weed growth and chemical damage to paddy rice were investigated. The results are shown in Table-2.

In the table, the degree of chemical damage to crops and the herbicidal effect on weeds are expressed by comparing the state of emergence or growth of crops or weeds with the amount of air drying without treatment, and according to the evaluation criteria below. The test compounds were indicated by the compound number of Cloth-1 (the same applies hereinafter).

Evaluation standard 0: Survival rate shown by air dry weight ratio vs. untreated area 91-100
%1: “71~90
%2: // 41
~70%3: //
11-40% 4: 〃
6-10% 5: 〃
O ~ 5% Test Example 2 Rice paddy growing season weeding test R/ Fill a 5000 Wagner Posoto with soil, remove grass weeds, broad-leaved weeds (Kikashigusa, Azena, Prunus japonicus, etc.).
Seeds of firefly, Heraomodaka and Tamagayatsuri were sown, and the area was flooded. Two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. During the weed growth period 12 days after transplanting paddy rice, a predetermined amount of the test compound was submerged in water using granules prepared according to the method described in Formulation Example 4 above. Processing 3
After 0 days, weed growth status and chemical damage to paddy rice were investigated. The results are shown in Table-3.

In the table, the degree of chemical damage to crops and the growth state of weeds are expressed according to the method shown in Test Example 1.

From the results shown in Tables 2 and 3, it is clear that the compounds of the present invention can be applied to a wide variety of harmful weeds that are a problem in rice fields, both in pre-emergence treatments and in the growing season, where it has been difficult to achieve herbicidal effects. It is clear that it is an excellent compound that exhibits herbicidal activity and has almost no phytotoxicity to paddy rice.

In addition, the group of compounds disclosed in JP-A No. 58-69866, such as benzoylamino-pyrazolylacetonitrile or (3,5-dichlorobenzoylamino)-pyrazolylacetonitrile, was used in a weeding test before rice field emergence or during the rice field growing season. In a herbicidal test, the compounds of the present invention showed no phytotoxicity to paddy rice and had no selectivity as herbicides for paddy fields, whereas the compounds of the present invention did not cause phytotoxicity to paddy rice and showed excellent selectivity. It is clear that the compound disclosed in No. 58-69866 has excellent properties that could not be expected.

Test Example 3 Potato Phytophthora control test Potatoes grown in pots in a greenhouse (variety Nibaron, plant height approximately 25 cm) were treated with a prescribed concentration of a chemical (the test compound was used as an irrigation agent by the method of Example 8 above). diluted with water to a specified concentration) with a spray gun (1.0 kg/
50 g per 6 pots was applied using the following method (CRL) and air-dried. A zoospore suspension was prepared from Potato Phytophthora blight which had been previously cultured on potato sections for 7 days. This suspension was sprayed and inoculated onto the potato plants sprayed with the drug, and the test plants were kept at 17-19'C1 humidity of 95 degrees or higher for 6 days, and then the degree of lesion formation was investigated.

The lesion area ratio was observed and evaluated for every 6 leaves to determine the lesion index, and the lesions were determined for each plot using the following formula.

The evaluation criteria are as follows.

Disease severity index 0: Lesion area ratio 0%1:
1 to 5% 2: 6 to 25% 6: 26 to 50 inches 4: 51 inches or more No. 2 Number of leaves with disease severity index 0 n□: 1N n2: 2# n3: 3yn, @ 4.

N=no-)-n□+n2-)-n3-1-n.

The results are shown in Table-4.

Table 4 Results of Potato Phytophthora control test Test Example 4 Kikucurbita and disease control test Kikucurbita grown in pots in a greenhouse (variety: Sumo Hanshiro,
A spray gun (1,0 Ky/cnl) was used to spray a prescribed concentration of the drug (the test compound was made into an irrigation agent using the method of Formulation Example 8 above, and diluted with water to a prescribed concentration) onto two leaves (spread out).
) was used to spray 50 rnl per 3 pots and air dry. Downy mildew fungi were collected from the lesions of downy mildew-infested leaves of cucurbits, a spore suspension was prepared with demineralized water, and the suspension was inoculated by spraying.

The inoculated pots were immediately kept at 18-20°C and a humidity of 95°C or higher for 24 hours, and then placed in a greenhouse (room temperature 18-27°C).
After 7 days, the degree of lesion formation was examined.

The evaluation criteria and lesion display method were as shown in Test Example 3.

The results are shown in Table-5.

Table 5 Results of control test for algae and diseases The results shown in Tables 4 and 5 show that the compound group of the present invention has a high control effect on plant diseases caused by algae, such as late blight of potato and blight of potato fungi. That is clear. Moreover, the compound group of the present invention is disclosed in JP-A-58-69
The group of compounds disclosed in Publication No. 866, that is, benzoylamino-pyrazolylacetonitrile, or (5
, 5-dichlorobenzoylamine)-pyrazolylacetonitrile, etc., which show only a low pesticidal effect or show severe chemical damage, and as expected from the above-mentioned prior art, it has an excellent pesticidal effect. It is clear that

〔Effect of the invention〕

As is clear from the above explanation, the pyrazole derivative according to the present invention exhibits an excellent herbicidal effect with a wide range of suitable periods as a herbicide for paddy fields, which was not expected with the herbicide 1. Furthermore, as a fungicide for agriculture and horticulture, it has excellent control effects against various diseases caused by algae and fungi on various crops, including soil diseases, at a low dose and concentration, which is not expected to be effective with conventional commercially available drugs. The agricultural chemical containing the pyrazole derivative according to the present invention has excellent properties and is useful as a herbicide and a fungicide for agriculture and horticulture.

In the method for producing pyrazole derivatives according to the present invention, since the nitrile group does not undergo hydrolysis in the halogenation step, the ``1''! By adding reaction raw materials, the desired product can be easily produced in a substantially short process and in high yield, which is excellent.

Claims (3)

[Claims] (1) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R is an alkyl group, an alkenyl group, an alkoxyalkyl group, a cycloalkyl group, a haloalkyl group, a haloalkenyl group, or a halocyclo A pyrazole derivative represented by (representing an alkyl group). (2) General formula (II) R'-COCl (II) (wherein R' is an alkyl group, an alkenyl group, an alkoxyalkyl group, a cycloalkyl group, a cycloalkenyl group,
Acid chloride represented by a haloalkyl group, haloalkenyl group or halocycloalkyl group) is reacted with aminoacetonitrile to form the general formula (III) R'-CONHCH_2CN(III) (wherein R' has the above meaning). ) is obtained, and this is treated with a halogenating agent to obtain the general formula (IV) ▲ Numerical formula, chemical formula, table, etc. ▼ (IV) (wherein R is an alkyl group, an alkenyl group, A halogenated intermediate represented by an alkoxyalkyl group, a cycloalkyl group, a haloalkyl group, a haloalkenyl group, or a halocycloalkyl group, and X represents a halogen atom) is obtained, and then this is reacted with pyrazole. General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (
I) A method for producing a pyrazole derivative represented by the formula (wherein R has the meaning described above). (3) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R is an alkyl group, an alkenyl group, an alkoxyalkyl group, a cycloalkyl group, a haloalkyl group, a haloalkenyl group, or a halocyclo A herbicide for paddy fields and a fungicide for agriculture and horticulture, characterized by containing a pyrazole derivative represented by (representing an alkyl group) as an active ingredient.