JPH064594B2 - Pyrazolcarboxamide derivative and fungicide containing the same as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group. ] The present invention relates to a pyrazole carboxamide derivative (hereinafter referred to as the compound of the present invention) and a fungicide containing the same as an active ingredient.

As a result of extensive studies on the pyrazole carboxamide compound, the present inventors have found that the compound of the present invention represented by the general formula [I] is prophylactic against many plant pathogens,
The present invention has been completed by finding that it has a therapeutic or osmotic transition control ability.

As a plant disease for which the compound of the present invention has excellent efficacy,
For example, rice blight (Rhizoctonia solani), pseudo-blight blight (Rhizoctonia oryzae, R.solani IIIB), rust of wheat (Puccinia striiformis, P. graminis, P. reco)
ndita, P.hordei), snow rot (Typhula incarrata, T.ishi
kariensis), naked smut (Ustilago tritici, V.nuda),
Rhizoctonia solani of various crops, White silkworm (Co
rticiumrolfsii), potato, beet Rhizoctnia solani, pear red scab (Gymnosporan)
gium haraeanum), apple scab (Venturia inaequa)
leaf rot (Rhizoctoniasolani), etc.
White silkworm (Corticium rolfsii), leaf rust (Uromycestri)
folii), snow rot (Typhula incarnata, T.ishikariensi
s) and the like.

Therefore, the compound of the present invention can be used as an active ingredient of a fungicide such as paddy fields, upland fields, orchards, meadows and lawns.

The compound of the present invention can be produced, for example, by the method shown below.

[Method A] [In the formula, R ¹ and R ² have the same meanings as described above. That is, a method for obtaining the compound of the present invention by reacting pyrazole-4-carboxylic acid chloride represented by the general formula [II] with 1,1,3-trimethyl-4-aminoindane.

[Method B]

[In the formula, X represents a chlorine atom, a bromine atom or an iodine atom, and R ¹ has the same meaning as described above. That is, a method of obtaining the compound of the present invention by a halogen atom (excluding fluorine) / fluorine exchange reaction with potassium fluoride, cesium fluoride or the like.

Examples of the compound of the present invention are shown below, but of course the compound of the present invention is not limited to these examples.

1,3-Dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide-N- (1,1,3-trimethylindan-4-yl)
Pyrazole-4-carboxamide 1,3,5-trimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 1,5-dimethyl-3-fluoro-N- (1,1 , 3-
Trimethylindan-4-yl) pyrazole-4-carboxamide 1,3-dimethyl-5-fluoro-N- (1,1,3-
Trimethylindan-4-yl) pyrazole-4-carboxamide 3-chloro-1,5-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 5-chloro-1,3 -Dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 5-bromo-1,3-dimethyl-N- (1,1,3-trimethylindan-4-yl) Pyrazole-4-carboxamide 1,3-dimethyl-5-iodo-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 1-methyl-3-trifluoromethyl-N- (1 , 1,
3-Trimethylindan-4-yl) pyrazole-4-
Carboxamide 1-methyl-5-trifluoromethyl-N- (1,1,
3-Trimethylindan-4-yl) pyrazole-4-
Carboxamide 3-fluoro-1-methyl-5-trifluoromethyl-
N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 5-fluoro-1-methyl-3-trifluoromethyl-
N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide 3-chloro-1-methyl-5-trifluoromethyl-N
-(1,1,3-Trimethylindan-4-yl) pyrazole-4-carboxamide 5-chloro-1-methyl-3-trifluoromethyl-N
-(1,1,3-Trimethylindan-4-yl) pyrazole-4-carboxamide 5-bromo-1-methyl-3-trifluoromethyl-N
-(1,1,3-Trimethylindan-4-yl) pyrazole-4-carboxamide 5-iodo-1-methyl-3-trifluoromethyl-N
-(1,1,3-Trimethylindan-4-yl) pyrazole-4-carboxamide 1,3-dimethyl-5-trifluoromethyl-N-
(1,1,3-Trimethylindan-4-yl) pyrazole-4-carboxamide 1,5-dimethyl-3-trifluoromethyl-N-
(1,1,3-Trimethylindan-4-yl) pyrazole-4-carboxamide 3,5-bis (trifluoromethyl) -1-methyl-N
-(1,1,3-Trimethylindan-4-yl) pyrazole-4-carboxamide Next, production examples of the compound of the present invention will be shown as reference examples.

Reference Example 1 1.75 g of 1,1,3-trimethyl-4-aminoindan and 2 ml of pyridine in 50 ml of toluene were stirred at room temperature to obtain 1.93 g of 5-chloro-1,3-dimethylpyrazole-4-carboxylic acid chloride. Add 10 ml of toluene solution dropwise,
Then, the mixture was stirred at room temperature for 12 hours. Next, the reaction solution was poured into cold water, and after liquid separation, the aqueous layer was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium oxide, and the solvent was evaporated.

The residue was recrystallized from toluene to give 5-chloro-1,3-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazolecarboxamide 2.72.
g was obtained.

mp. 134.4 ° C. Reference Example 2 100 g of potassium fluoride powder, 800 ml of sulfolane, 100 ml of toluene and 5 g of 18-crown-6 were placed in a reaction vessel, and while being heated to reflux, water in the system was removed by molecular sieves, and then toluene was distilled off. Then cooled. Then add to this 5-chloro-1,3-dimethyl-N-
42 g of (1,1,3-trimethylindan-4-yl) pyrazolecarboxamide was added, and the mixture was added to a nitrogen atmosphere to give 18
The mixture was heated and stirred at 0 to 200 ° C for 10 hours.

After cooling, water and ether were added to the reaction solution for partitioning, the aqueous layer was extracted with ether, the ether layer was washed with saturated brine and dried over anhydrous magnesium sulfate, the solvent was evaporated, and the residue was cyclohexane. By recrystallization using a mixed solvent of -toluene, 31.5 g of 1,3-dimethyl-5-fluoro-N- (1,1,3-trimethylindan-4-yl) pyrazolecarboxamide was obtained.

mp. 136.9 ° C. Table 1 shows some typical compounds of the present invention which can be produced by such a production method.

When the compound of the present invention is used as an active ingredient of a bactericide,
Although it may be used as it is without adding any other ingredients, normally,
It is mixed with a solid carrier, a liquid carrier, a surfactant and other auxiliaries for formulation to prepare an emulsion, a wettable powder, a suspension, a granule, a powder, a liquid and the like.

These preparations contain the compound of the present invention as an active ingredient in an amount of 0.1 to 9.99% by weight, preferably 0.2 to 80%.

As the solid carrier, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, fine powder of synthetic hydrogenated silicon, etc. Alternatively, a granular material may be used, and examples of the liquid carrier include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosolve, ketones such as acetone, cyclohexanone and isophorone, soybean oil and cottonseed oil. Vegetable oil, dimethyl sulfoxide, acetonitrile, water and the like.

As the surfactant used for emulsification, dispersion, wet extension, etc., alkyl sulfate ester salt, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkylsulfosuccinates, polyoxyethylene alkylaryl ether phosphates, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers,
Examples thereof include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. As a formulation auxiliary agent, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PA
P (acidic isopropyl phosphate) and the like can be mentioned.

Formulation examples are shown below. The compounds of the present invention are shown by the compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 50 parts of the compound (2) of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain a wettable powder.

Formulation Example 2 An emulsion is obtained by thoroughly mixing 10 parts of the compound (1) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 parts of xylene.

Formulation Example 3 2 parts of the compound (1) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay were well pulverized and mixed, and after adding water and kneading well, Granulate and dry to obtain granules.

Formulation Example 4 25 parts of the compound (4) of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed and wet-ground until the particle size becomes 5 microns or less to obtain a suspension agent.

Formulation Example 5 2 parts of the compound (5) of the present invention, 88 parts of kaolin clay and 10 parts of talc are well pulverized and mixed to obtain a powder.

Formulation Example 6 10 parts of the compound (5) of the present invention, 1 part of polyoxyethylene styryl phenyl ether and 89 parts of water are mixed to obtain a liquid preparation.

These formulations can be used as is or diluted with water to
The foliage is sprayed, and the powder is sprinkled and dispersed in the soil to be mixed or applied to the soil. In addition, it is expected to enhance the bactericidal effect by mixing with other bactericides. In addition, insecticides,
Acaricide, nematicide, herbicide, plant growth regulator, fertilizer,
It can also be used as a mixture with a soil conditioner.

Incidentally, the compound of the present invention, paddy field, upland, orchard, meadow,
It can be used as an active ingredient of a bactericide such as lawn.

When the compound of the present invention is used as an active ingredient of a fungicide, its application amount is usually 1 although it varies depending on weather conditions, formulation form, application time, method, place, target disease, target crop and the like.
1 g to 100 g per are, preferably 5 g to 50
When the emulsion, wettable powder, suspension, liquid, etc. is diluted with water before application, the application concentration is 0.001% to 1%, preferably 0.005% to 0.5%. , Powder, etc. are applied as they are without any dilution.

Next, it is shown in Test Examples that the compound of the present invention is useful as an active ingredient of a bactericide. The compounds of the present invention are shown by the compound numbers in Table 1, and the compounds used for comparison and control are shown by the compound symbols in Table 2.

The control efficacy is "5", about 10% if the disease state of the test plant at the time of the survey, that is, the microflora of leaves, stems, etc. If it is admitted, "4", if it is admitted about 30%, it is "3", if it is admitted about 50%, it is "2", if it is admitted about 70%, it is "1". If not, it is evaluated as “0” in 6 levels of 0 to 5, 0, 1,
Shown by 2, 3, 4, and 5.

Test Example 1 Prevention of rice blight prevention effect A plastic pot is filled with sandy loam soil, and rice (Kinki 33
No.) was sowed and grown at room temperature for 60 days. To a rice seedling having 6 to 7 leaves developed, a test compound which was made into an emulsion according to Formulation Example 2 was diluted with water to a predetermined concentration, and the foliage was sprayed so that it was sufficiently attached to the leaf surface. 4 hours after spraying, agar-containing agar pieces of rice wilt disease bacteria were applied and inoculated. 28 ℃ after inoculation,
It was grown under high humidity for 4 days, and the control efficacy was investigated. The results are shown in Table 3.

Test Example 2 Effect of Controlling Rice Blight Disease by Water Surface Application 1/10000 Wagner pot was filled with sandy loam soil, rice (Kinki No. 33) was sown, and grown in a greenhouse for 80 days.
A rice seedling with 9 to 10 leaves developed was diluted with water to give a test compound, which was made into a wettable powder according to Formulation Example 1, and a predetermined amount thereof was irrigated into the soil. After irrigation, the plants were grown in a greenhouse for 7 days, and agar pieces containing rice wilt disease bacteria were applied and inoculated. After inoculation, the plant was grown at 28 ° C. under high humidity for 4 days, and the control efficacy was investigated. The results are shown in Table 4.

Test Example 3 Wheat leaf rust treatment effect test A plastic pot was filled with sandy loam soil, and wheat (Agriculture 73
No.) was sowed and grown in a greenhouse for 10 days. Wheat seedlings developed on the second to third leaves were inoculated with spores of wheat leaf rust fungus. After inoculation, the mixture was grown at 23 ° C. under high humidity for 1 day, and the test compound which was made into an emulsion according to Formulation Example 2 was diluted with water to a predetermined concentration and sprayed on foliage so that it adhered sufficiently to the leaf surface.
After spraying, the seedlings were grown for 7 days under illumination at 23 ° C., and the control efficacy was investigated. The results are shown in Table 5.

Test Example 4 Apple Scab Disease Prevention Effect Test A plastic pot was filled with sandy loam soil, seeded with apples, and grown in a greenhouse for 30 days. The test compound, which was made into a wettable powder according to Preparation Example 1, was diluted with water to a predetermined concentration of apple seedlings having the fifth true leaf developed, and the foliage was sprayed so that the test compound was sufficiently adhered to the leaf surface. Four hours after spraying, a spore suspension of apple scab was spray-inoculated. After inoculation, the plant was grown at 15 ° C. and high humidity for 14 days, and the control effect was investigated. The results are shown in Table 6.

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Tadashi Ozumi 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (72) Inventor Kiyoto Maeda 4-2-1 Takashi, Takarazuka-shi, Hyogo No. 1 Sumitomo Chemical Co., Ltd. (72) Inventor Satoru Inoue 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd.

Claims (2)

[Claims] 1. A general formula [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group. ] The pyrazole carboxamide derivative shown by these. 2. General formula [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group. ] A fungicide characterized by containing a pyrazole carboxamide derivative represented by the following as an active ingredient.