JPH045014B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] [Wherein, X represents a methyl group, a nitro group, a halogen atom, or a trifluoromethyl group. ] The present invention relates to an indanylbenzamide derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, and a plant disease control agent containing the same as an active ingredient. The fact that certain benzamide derivatives can be used as active ingredients in plant disease control agents was disclosed in Japanese Patent Application Laid-open No.
It is described in JP-A-9739, JP-A-50-148321, and German Published Patent Application No. 1907436. However, as is clear from the test examples described below, these compounds cannot always be said to have sufficient efficacy as active ingredients of plant disease control agents. Under these circumstances, the present inventors have conducted extensive studies on indanylbenzamide derivatives, and have found that the compounds of the present invention have preventive, therapeutic, or systemic bactericidal effects against many plant pathogens. They discovered this and completed the present invention. Plant pathogenic bacteria against which the compounds of the present invention are effective include:
Rhizoctonia solani of rice, rust of wheat (Puccinia striiformis, P.graminis,
P. recondita, P. hordei), snow rot fungus (Typhula
sp., Micronectriella nivalis), Ustilago tritici, U. nuda, Venturia inaequalis on apples, Venturia nashicola on pears, Gymnosporangium haraeanum, and seedling dieback on cucurbits. These include Rhizoctonia solani, onion rust (Puccinia allii), chrysanthemum white rust (Puccinia horiana), and various crops' white silk rust (Corticium rolfsii). Therefore, the compound of the present invention can be used in rice fields, fields, orchards,
It can be used as an active ingredient in plant disease control agents for pastures, lawns, etc. The compound of the present invention has the general formula [] [In the formula, X has the same meaning as above. ] Substituted benzoic acid or its reactive derivative represented by the formula [] It can be produced by reacting with an aminofluoroindane derivative shown in the following. In this case, the aminofluoroindane derivative represented by the general formula [] is generally dissolved in a suitable solvent such as a hydrocarbon such as benzene, toluene,
Chlorbenzene, methylene chloride, chloroform,
Dissolved in halogenated hydrocarbons such as carbon tetrachloride, ethers such as diisopropyl ether, tetrahydrofuran, and dioxane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile, and even dimethyl sulfoxide, dimethyl formamide, water, etc. or suspended or dissolved in tetrahydrofuran without solvent, preferably 0.4 to 1.5 equivalents, preferably
Add 0.5 to 1.1 equivalents of substituted benzoic acid represented by the general formula [] or a reactive derivative thereof. Alternatively, the substituted benzoic acid represented by the general formula [] or its reactive derivative may be dissolved or suspended in the above-mentioned solvents, or the aminofluoroindane derivative represented by the general formula [] may be added and reacted without a solvent. It is possible. The reaction can be carried out at any temperature from the freezing point to the boiling point of the solvent, preferably from 0° C. to the boiling point of the solvent. The substituted benzoic acids represented by the general formula [] or their reactive derivatives to be used include the corresponding carboxylic acids, acid anhydrides, acid chlorides, acid bromides, carboxylic acid esters, etc. The reaction can be carried out in the presence of a suitable reaction aid depending on the substituted benzoic acid represented by the formula [] or its reactive derivative. For example, when using a carboxylic acid, dicyclohexylcarbodiimide, phosphorus pentachloride, etc. can be used, and when using a carboxylic acid ester, sodium methylate, sodium ethylate, etc. can be used. Furthermore, when using acid halides or acid anhydrides, sodium hydroxide, potassium hydroxide, triethylamine, N-methylmorpholine, triethylamine, etc. can be used. These reaction aids are usually used in an amount ranging from a catalytic amount to 2 equivalents, but preferably 0.95 to 1.1 equivalents. After the reaction is completed, the compound of the present invention can be produced by removing the reaction aid or its reaction product by filtration or washing with water, and distilling off the solvent.
If necessary, it can be purified by recrystallization from benzene, toluene, methyl alcohol, ethyl alcohol, diisopropyl ether, hexane, chloroform, etc., or by silica gel column chromatography. In addition, the compound of the present invention can be expressed, for example, by the general formula [] [In the formula, X has the same meaning as above. ] It can also be produced by isomerizing the benzoyltetrahydroquinoline derivative shown in the following in the presence of an acid catalyst at -20 to 150°C for 0.5 to 24 hours. In this case, the isomerization reaction proceeds even if an organic solvent is used, but in order to obtain the target compound in high yield, the reaction is performed without a solvent. Examples of the acid catalyst include sulfuric acid and phosphoric acid, the amount of which is in large excess relative to the benzoyltetrahydroquinoline derivative. After the reaction is completed, the compound of the present invention can be produced by adding ice water to the reaction solution, separating the precipitated crystals, washing with water, and drying. If necessary, it can be purified by recrystallization from benzene, toluene, methyl alcohol, ethyl alcohol, diisopropyl ether, hexane, chloroform, etc., or by silica gel column chromatography. Next, production examples of the compounds of the present invention will be shown. Production Example 1 [Production of compound (1) of the present invention] N-(o-trifluoromethylbenzoyl)-
2,2-dimethyl-6-fluoro-1,2,3,
4-tetrahydroquinoline 1.10g (3.13mmol)
was dissolved in 8.5 ml of 85% phosphoric acid, stirred at 150°C for 1 hour, and then ice water was added to the resulting reaction solution. The precipitated crystals were separated, washed with water, dried, purified by silica gel column chromatography, and 0.76 g of N
-(1,1-dimethyl-7-fluoro-4-indanyl)-o-trifluoromethylbenzamide was obtained (yield 69.1%). Production Example 2 [Production of Compound (2) of the Present Invention] In a solution of 0.40 g (2.23 mmol) of 1,1-dimethyl-5-fluoro-4-aminoindan and 0.27 g (2.68 mmol) of triethylamine dissolved in 6 ml of tetrahydrofuran. A solution prepared by dissolving 0.49 g (2.35 mmol) of o-trifluoromethylbenzoyl chloride in 3 ml of tetrahydrofuran was added dropwise under ice cooling and stirring at an internal temperature of 5° C. or below. After completion of the dropwise addition, the mixture was stirred at room temperature overnight, and then water and ethyl acetate were added to separate the layers. The organic layer was washed with 5% hydrochloric acid and water in that order, and then dried over anhydrous sodium sulfate. The crystals obtained by distilling off the solvent were washed with n-hexane and dried to give 0.66 g of N-(1,1
-dimethyl-5-fluoro-4-indanyl)-
O-trifluoromethylbenzamide was obtained (yield 84.6%). Production Example 3 [Production of compound (3) of the present invention] 2.0 g (12.2 mmol) of ethyl o-methylbenzoate,
A mixture of 2.18 g (12.2 mmol) of 1,1-dimethyl-5-fluoro-4-aminoindan, 0.91 g (13.4 mmol) of sodium ethylate, and 30 ml of benzene was refluxed with stirring for 10 hours. The reaction solution was added to dilute hydrochloric acid under ice cooling, and then extracted with ethyl acetate. The organic layer was concentrated, the resulting residue was purified by silica gel column chromatography, and 2.40 g of N-
(1,1-dimethyl-5-fluoro-4-indanyl)-o-methylbenzamide was obtained (yield
66.3%). Production Example 4 [Production of Compound (4) of the Present Invention] 2.06 g of dicyclohexylcarbodiimide was added to a solution of 1.57 g (10.0 mmol) of o-chlorobenzoic acid dissolved in 20 ml of toluene while stirring under ice cooling.
(10.0 mmol) dissolved in 5 ml of toluene was added. After the addition was completed, stirring was continued for 1 hour, and then a solution of 1.79 g (10.0 mmol) of 1,1-dimethyl-5-fluoro-4-aminoindan dissolved in 5 ml of toluene was added dropwise. After completion of the reaction, the reaction solution was gradually raised to room temperature and then reacted under reflux for 10 hours. After separating the dicyclohexylurea produced from the reaction solution, the solution was concentrated and purified by silica gel column chromatography to obtain 2.17 g of N-(1,1-dimethyl-
5-Fluoro-4-indanyl)-o-chlorobenzamide was obtained (yield 68.5%). Table 1 shows some of the compounds of the present invention that can be produced by such a production method.

[Table] When producing the compound of the present invention, the benzoyltetrahydroquinoline derivative represented by the general formula [], which is a raw material compound, is prepared by the general formula [] and a tetrahydroquinoline derivative represented by 1.0
~2.0 equivalents of the acid halide of the substituted carboxylic acid represented by the general formula [] in a solvent, in the presence of 1.0 to 2.0 equivalents of a deoxidizing agent and a catalyst, at 20 to 160°C.
It can be produced by reacting for 24 hours. Examples of the above-mentioned solvent include inert solvents such as benzene, toluene, xylene, tetrahydrofuran, and dioxane, and examples of the deoxidizing agent include organic bases such as triethylamine, N,N-dimethylaniline, and N-methylmorpholine. , and examples of the catalyst include N,N-dimethyl-4-aminopyridine. After the reaction is completed, the reaction solution is washed with dilute hydrochloric acid, aqueous alkaline solution, water, etc., and then concentrated to obtain the desired compound. If necessary, chromatography, distillation,
Purification is performed by recrystallization, etc. Next, a reference production example of a benzoyltetrahydroquinoline derivative represented by the general formula [] will be shown. Reference production example 2,2-dimethyl-6-fluoro-1,2,
3,4-tetrahydroquinoline 1.50g
(8.38 mmol), N,N-dimethyl-4-aminopyridine catalytic amount, N,N-dimethylaniline 1.32g
(10.9 mmol) was dissolved in 8 ml of xylene, and a solution prepared by dissolving 1.83 g (8.80 mmol) of o-trifluoromethylbenzoyl chloride in 3 ml of xylene was added dropwise to the solution under reflux. After the reaction was completed under reflux for 3 hours, the reaction mixture was poured into ice water, washed with 5% hydrochloric acid, 5% aqueous sodium hydroxide solution and water in this order, and the organic layer was concentrated. The residue was purified by silica gel column chromatography to obtain 2.35 g of N-(o-trifluoromethylbenzoyl)-2,2-dimethyl-6-fluoro-1,2,3,4-tetrahydroquinoline ( yield 79.9%). When the compound of the present invention is used as an active ingredient in a disinfectant, it may be used as is without adding any other ingredients, but it is usually mixed with a solid carrier, liquid carrier, surfactant, or other formulation auxiliary to form an emulsion. Formulated into wettable powders, suspensions, granules, powders, liquids, oils, etc. These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99.9%, preferably 0.2 to 80%. The solid carriers mentioned above include kaolin clay, attapalgite clay, bentonite, acid clay,
There are fine powders or granules such as pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide, and liquid carriers include aromatic compounds such as xylene and methylnaphthalene. Examples include hydrocarbons, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile, and water.
In addition, surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfate salts, alkyl (aryl) sulfonate salts, dialkyl sulfosuccinate salts, polyoxyethylene alkylaryl ether phosphate salts, naphthalene sulfonate salts, etc. Examples include anionic surfactants such as acid formalin condensates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), and PAP (isopropyl acid phosphate). Examples of formulations are shown below. In addition, the compound of the present invention is the first
Indicated by compound number in the table. Parts are parts by weight. Formulation Example 1 50 parts of the compound of the present invention (3), 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder. Formulation Example 2 10 parts of the compound (6) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 parts of xylene are thoroughly mixed to obtain an emulsion. Formulation Example 3 2 parts of the compound of the present invention (1), 1 part of synthetic hydrous silicon oxide,
2 parts of calcium ligninsulfonate, 30 parts of bentonite and 65 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, followed by granulation and drying to obtain granules. Formulation Example 4 25 parts of the compound of the present invention (4), 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water
A suspension is obtained by mixing the two parts and wet-milling until the particle size of the active ingredient is less than 5 microns. Formulation Example 5 Two parts of the compound (2) of the present invention, 88 parts of kaolin clay and 10 parts of talc are thoroughly ground and mixed to obtain granules. Formulation Example 6 10 parts of the compound of the present invention (5), 1 part of polyoxyethylene styrylphenyl ether, and 89 parts of water are mixed to obtain a liquid preparation. These preparations can be used as they are or diluted with water, etc., and treated with foliage or soil. For soil treatment, spray the preparation on the soil surface (if necessary,
Mix with soil after spraying. ) or irrigate the soil. Furthermore, by mixing and using it with other plant disease control agents, it can be expected that the control effect will be enhanced. Furthermore, it can also be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, and soil conditioners. When the compound of the present invention is used as an active ingredient of a fungicide, the application rate is usually 1 to 100% per are.
g, preferably 5 to 50 g, emulsion, hydrating agent,
When applying suspensions, solutions, etc. diluted with water, the application concentration is 0.001 to 1%, preferably 0.005 to 0.5.
%, and granules, powders, etc. are applied as is without any dilution. Next, test examples demonstrate that the compound of the present invention is useful as an active ingredient of a plant disease control agent. In addition,
Compounds of the present invention are indicated by compound numbers in Table 1, and compounds used for comparison are indicated by compound symbols in Table 2.

[Table] In addition, the control efficacy is evaluated by visually observing the disease state of the test plants at the time of investigation, that is, the degree of bacterial flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, it is rated "5";
If about 10% of the compound is observed, it will be ``4'', if about 30% of the compound is observed, it will be ``3'', if about 50% of the compound is observed, it will be ``2'', if about 70% of the compound is observed, it will be ``1'', and if the compound is not supplied beyond that level. If there is no difference from the disease onset state, it is evaluated as "0" and evaluated on a scale of 0 to 5.
Shown as 1, 2, 3, 4, 5. Test Example 1 Rice sheath blight control test (preventive effect) A plastic pot was filled with sandy loam, and rice (Kikaku No. 33) was sown and grown in a greenhouse for 60 days. A test compound prepared as an emulsion in accordance with Formulation Example 2 was diluted with water to a predetermined concentration and sprayed on the foliage of rice seedlings in which the sixth true leaf had developed so as to sufficiently adhere to the leaf surface. After 4 hours, an agar piece containing the rice sheath blight fungus was pasted and inoculated. After inoculation, the seeds were grown for 4 days at 27℃ under high humidity.
The pesticidal efficacy was investigated. The results are shown in Table 3.

[Table] Test Example 2 Rice sheath blight control test (residual effect) A plastic pot was filled with sandy loam, and rice (Kikaku No. 33) was sown and grown in a greenhouse for 60 days. A test compound prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the mixture was sprayed on the foliage of rice seedlings in which the sixth true leaf had developed so as to sufficiently adhere to the leaf surface. After spraying, the plants were grown in a greenhouse for 7 days and inoculated with agar pieces containing the rice sheath blight fungus. 27℃ after inoculation,
The plants were grown for 4 days in a humid environment and their pesticidal efficacy was investigated. The results are shown in Table 4.

[Table] Test Example 3 Test for controlling cucumber seedling blight (preventive effect) A plastic pot was filled with sandy loam, and pathogenic soil in which seedling blight bacteria had been cultured was evenly inoculated onto the soil surface. The test compound made into an emulsion according to Formulation Example 2 was diluted with water, and a predetermined amount of the diluted product was sprinkled onto the soil. Two hours later, 10 seeds of cucumber (variety: Kaga Kyoiku Setsei) were sown. The seeds were grown in a greenhouse for 10 days after sowing, and the pest control effect was investigated. The results are shown in Table 5.

[Table] Test Example 4 Common bean white silk disease control test (preventive effect) A plastic bag was filled with sandy loam, and 10 ml of pathogenic soil in which white silk disease fungi had been cultured was evenly inoculated onto the soil surface. A test compound made into a wettable powder according to Formulation Example 1 was diluted with water, and a predetermined amount of the solution was sprinkled onto the soil. Two hours later, 10 seeds of green beans (variety: Honkintoki) were sown. After sowing, the seeds were grown in a greenhouse for 14 days and their pesticidal efficacy was investigated. The results are shown in Table 6.

[Table] Test Example 5 Wheat rust control test (therapeutic effect) A plastic pot was filled with sandy loam, and wheat (Norin No. 61) was sown and grown in a greenhouse for 7 days.
Wheat seedlings developed by the first main business were inoculated with spores of the wheat rust fungus. After inoculation, at 23℃ and under high humidity.
The test compound was grown for 16 hours, made into a suspension according to Formulation Example 4, diluted with water to a predetermined concentration, and sprayed on the leaves so as to sufficiently adhere to the leaf surface. 23 after spraying
The plants were grown for 10 days under fluorescent lighting at ℃, and their pesticidal efficacy was investigated. The results are shown in Table 7.

【table】

Claims (1)

[Claims] 1. General formula [Wherein, X represents a methyl group, a nitro group, a halogen atom, or a trifluoromethyl group. ] An indanylbenzamide derivative represented by 2 General formula [Wherein, X represents a methyl group, a nitro group, a halogen atom, or a trifluoromethyl group. ] Substituted benzoic acid or its reactive derivative represented by the formula A general formula characterized by reacting with an aminofluoroindane derivative represented by [In the formula, X has the same meaning as above. ] A method for producing an indanylbenzamide derivative represented by 3 General formula [Wherein, X represents a methyl group, a nitro group, a halogen atom, or a trifluoromethyl group. ] A general formula characterized by isomerizing the benzoyltetrahydroquinoline derivative represented by in the presence of an acid catalyst. [In the formula, X has the same meaning as above. ] A method for producing an indanylbenzamide derivative represented by 4 General formula [Wherein, X represents a methyl group, a nitro group, a halogen atom, or a trifluoromethyl group. ] A plant disease control agent characterized by containing an indanylbenzamide derivative represented by the following as an active ingredient.