JPS60105653A - Indanylbenzamide derivative, production thereof and plant blight controlling agent containing the same as active constituent - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (X is methyl, nitro, halogen or trifluoromethyl). EXAMPLE:N-(1,1-Dimethyl-7-fluoro-4-indanyl)-o-trifluoromethylbenzamide. USE:A plant blight controlling agent capable of exhibiting improved activity against Pellicularia sasaki of rice plants, Puccinia striiformis of wheat and barley and Venturia inaequalis, etc. PREPARATION:A substituted benzoic acid of formula II or a reactive derivative thereof is reacted with an aminofluoroindane derivative of formula III in a solvent, e.g. tetrahydrofuran, or in the absence of the solvent at 0 deg.C- the boiling point of the solvent to give the aimed compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a compound of the general formula (1) [wherein X represents a methyl group, a nitro group, a halogen atom or a trifluoromethyl group]. ] (hereinafter referred to as the compound of the present invention)
, its production method, and a plant disease control agent containing it as an active ingredient.

Scales in which certain benzamide derivatives are used as active ingredients in plant disease control agents are described in JP-A-58-9789, JP-A-50-148821, and German Published Patent Application No. 1907486. . 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 Rbizoctonia 5olani, a fungus that causes rust in wheat, and Puccinia qtriifor.
mis,]:, graminis.

P, recondita, P, hordei),
Snow rot fungus (Typhula sp.

Microneatriella n1valis),
Section smut fungus (Ustilago tritici,
nuda), Lin Go's Black Star Disease 1i (Ventu
ria 1naequalis), pear scab fungus (
Venturia nashicola), Gymnos-porangium haraean
um), a fungus that causes seedling blight of cucurbits (Rhizoctoni
a 5olani), green onion rust fungus (Puccini
a allii), chrysanthemum white rust fungus (Pucc-in
ia horiana), white blight fungus (Co
r-ticium rolfsii).

Therefore, the compound of the present invention can be used in rice fields, fields, orchards, pastures,
It can be used as an active ingredient in plant disease control agents for lawns, etc.

The compound of the present invention has the general formula (l) [wherein X has the same meaning as above, a substituted benzoic acid or a reactive derivative thereof represented by It can be produced by reaction.

In this case, the aminofluoroindane derivative represented by the general formula (1) is generally mixed with a suitable solvent, such as a hydrocarbon such as benzene, toluene, or xylene, or a halogenated hydrocarbon such as chlorobenzene, methylene chloride, chloroform, or 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 further dissolved or suspended in dimethyl sulfoxide, dimethyl formamide, water, etc., or without solvent, Preferably, 0.4 to 1.5 equivalents, preferably 0.5 to 1.1 equivalents of substituted benzoic acid represented by general formula (1) or a reactive derivative thereof is added to the solution dissolved in tetrahydrofuran.

Alternatively, the substituted benzoic acid represented by the general formula (1) or its reactive derivative is dissolved or suspended in the above-mentioned solvents, or the aminofluoroindane derivative represented by the general formula (1) is added and reacted without a solvent. It is also 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 acid represented by the general formula (II) or its reactive derivative to be used may include the corresponding carboxylic acid, acid anhydride, acid chloride, acid bromide, carboxylic acid ester, etc. The reaction can be carried out in the presence of a suitable reaction aid depending on the substituted benzoic acid represented by the general 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, hydroxide l-'
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.

Further, the compound of the present invention can be expressed, for example, by the general formula (IY) [wherein X
has the same meaning as above. ] In the presence of an acid catalyst, the benzoyltetrahydroquinoline derivative represented by -20
It can also be produced by isomerizing at ~150°C for 10,5 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 habenzoyltetrahydroxyphosphorus derivative.

After the reaction is complete, add ice water to the reaction solution and remove the precipitated crystals.
By separating, washing with water, and drying, the compound of the present invention can be produced. If necessary, recrystallize with benzene, toluene-methyl alcohol-ethyl alcohol, diisopropyl ether, hexane, chloroform, etc.
Alternatively, the following is a production example of the compound of the present invention which can be purified by silica gel column chromatography.

Production Example 1 [Production of compound (1) of the present invention] N-(o-trifluoromethylbenzoyl)-2,2-dimethyl-6
-fluoro-1,2゜8.4-tetrahydroquinoline 1
．． i o y (8.18 mmol) in 85% phosphoric acid 8
．． After dissolving in 5 tsl and stirring at 150°C for 1 hour, ice water was added to the resulting reaction solution. The precipitated crystals were separated by furnace, washed with water, dried, and purified by silica gel column chromatography to give 0.76 f/N-(1,1-dimethyl-7-fluoro-4-indanyl)-0-)lifluoromethyl. Benzamide was obtained (yield 69.1%).

Production Example 2 [Production of compound (2) of the present invention] 1.1-dimethyl-5-fluoro-4-aminoindan 0.40 f
(2,28 mmol), and triethylamine 0
．． In a solution of 271 (2,68 mmol) dissolved in 6 vrl of tetrahydrofuran, 0.49 f (2,85 mmol) of 0-trifluoromethylbenzoyl chloride was dissolved in 8 yxl of tetrahydrofuran while cooling with water and stirring at an internal temperature of 5°C or less. The solution was added dropwise. 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 are washed with rhohexane and dried to obtain 0.
．． 661 N-(1,1-dimethyl-5-fluoro-4
-indanyl)-0-1 trifluoromethylbenzamide was obtained (yield 84.6%).

Production Example 8 [Production of compound (8) of the present invention] Ethyl 0-methylbenzoate 2. Of (12,2 mmol), 1.1
-dimethyl-5-fluoro-4-aminoindan 2.1
8112.2 mmol), sodium ethylate 0.9
14 (18,4 mmol) and benzene 80 g +/
The mixture was refluxed under stirring for 10 hours. The reaction solution was added to dilute hydrochloric acid under water cooling, and then extracted with ethyl acetate. The organic layer was concentrated, and the resulting residue was purified by silica gel column chromatography to obtain 2.40 FI of N-(1,1-dimethyl-5-fluoro-4-indanyl)-〇-methylbenzamide 1166. a%).

Production Example 4 [Production of Compound (4) of the Present Invention] To a solution of 1.57 f (10.0 mmol) of 0-chlorobenzoic acid dissolved in 20 +/- toluene, 2.069 g (2.069 g) of dicyclohexylcarbodiimide ( 10.0mr
A solution of 5 tnl of toluene was added.

After continuing stirring for 1 hour after completion of the dropwise addition, 1.1-dimethyl-5-fluoro-4-aminoindan 1. '19
A solution of f (10.0 mmol) 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 with F, the P solution was concentrated and purified by silica gel column chromatography to obtain 2.17 II.
N-(l,1-dimethyl-5-fluoro-4-indanyl)-〇-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 1 Note that when producing the compound of the present invention, the benzoyltetrahydroquinoline derivative represented by the general formula (IV), which is a raw material compound, and the tetrahydroquinoline derivative represented by the general formula α] have a 1.0 to 2.0 An equivalent amount of the acid halide of the substituted carboxylic acid represented by the general formula [setting] in a solvent, 1
．． In the presence of 0 to 2.0 equivalents of deoxidizer and catalyst, 20 to
It can be produced by reacting at 160°C for 0.5 to 24 hours.

The above-mentioned solvents include benzene, toluene, xylene,
Examples include inert solvents such as tetrahydrofuran and dioxane; examples of deoxidizers include organic bases such as triethylamine, N,N-dimethylaniline, and N-methylmorpholine; and examples of catalysts include N,N-dimethyl- 4-aminopyridine is mentioned.

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, purification is performed by chromatography, distillation, recrystallization, etc.

Next, a reference production example of a benzoyltetrahydroquinoline derivative represented by the general formula (1m') will be shown.

Reference production example 2.2-dimethyl-6-fluoro-1,2°8.4-tetrahydroquinoline 1.50 g (8.88 mmol),
N,N-cymethy1Lt4-7i nobilidine catalyst amount, N,
N-dimethylaniline ta2y (10,9mmo
1) was dissolved in 8 yxl of xylene and added to this under reflux.
-Trifluoromethylbenzoyl chloride 1.81M
(8.80 mmol) dissolved in 8 ml of xylene was added dropwise. After the reaction was completed under reflux for 8 hours, the reaction mixture was poured into ice water, washed with 596 hydrochloric acid, 5% aqueous sodium hydroxide solution and water in this order, and the organic layer was concentrated. 2. By purifying the residue by silica gel column chromatography.
85f N-(0-trifluoromethylbenzoyl)-
2,2-dimethyl-6-fluoro-1,2,8°4-tetrahydroquinoline was obtained (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, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob flour, walnut shell flour, urea, ammonium sulfate, synthetic hydrous silicon oxide cylinder Wl. The liquid phase includes aromatic hydrocarbons such as xylene and methylnafculene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, etc. Examples include vegetable oils such as bean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile, and water.

In addition, surfactants used for emulsification, dispersion, wet layers, etc. include alkyl sulfate salts, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan Examples include nonionic surfactants such as fatty acid esters and polyoxyethylene sorbitan fatty acid esters. Formulation auxiliaries include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CM
Examples include C (carboxydimethylcellulose) and pAr (isopropyl acid phosphate).

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 50 parts of the compound of the present invention (3), 8 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 of the present invention (6), 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium do-f'sylbenzenesulfonate and 70 parts of xylene are thoroughly mixed to obtain an emulsion.

Formulation Example 8 2 parts of the compound of the present invention (1), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite and 65 parts of kaolin clay were thoroughly ground and mixed, and water was added and kneaded thoroughly. Granulate and dry to obtain granules.

Formulation Example 4 25 parts of the compound of the present invention (4), 8 parts of polyoxyethylene sorbitan monooleate, C! M (38 parts and 6 parts water)
A suspension is obtained by mixing 9 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 A liquid preparation is obtained by mixing 10 parts of the compound of the present invention (0.01 parts), 1 part of polyoxyethylene styrylphenyl ether, and 89 parts of water.

These preparations can be used as they are or diluted with water, etc., and treated with foliage or soil. For soil treatment, the formulation can be applied to the soil surface (if necessary, mixed with the soil after application) or irrigated into 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 amount is usually 1 to 100 g per are, preferably 5 to 5 oy, and the emulsion, wettable powder, suspension, solution, etc. is diluted with water. When applied, the application concentration is 0.001
~1%, preferably 0.005~0.5%, and granules, powders, etc. are applied as they are 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.

The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 In addition, the control efficacy is determined 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, l'-5J. , "4" if the 10th grade is recognized, "8" if the 80% is recognized, 50%
If it is recognized to a certain extent, it will be ``2'', and if it is recognized to be 70%, it will be ``1''.
'', and if there is no difference from the disease onset state when no compound is tested, it is evaluated as [-〇] on a 6-point scale from 0 to 5, and 0.1.2.8.4.5. show.

Test Example 1 Rice sheath blight control test (preventive effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) 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, a edible agar piece of the rice sheath blight fungus was pasted and inoculated. After inoculation, the plants were grown for 4 days at 27°C under humid conditions, and their pesticidal efficacy was investigated. The results are shown in Table 8.
8 Table Test Example 2 Rice sheath blight control test (residual effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) 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 edible agar pieces of the rice sheath blight fungus. 27° after inoculation
C1 was grown for 4 days under humid conditions, and its pesticidal efficacy was investigated. The results are shown in Table 4.

Table 4 Test Example 3 Cucumber seedling damping-off control test (preventive effect) A plastic pot was filled with sandy loam, and pathogenic soil in which seedling damping-off 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,
The specified amount was irrigated into the soil. Two hours later, 10 seeds of cucumber (product: Kaga Seisetsu) were sown. The seeds were grown in a greenhouse for 10 days after sowing, and their pesticidal efficacy was investigated. The results are shown in Table 5.

Table 5 Test Example 4 French bean white silk disease control test (preventive effect) A plastic bag was filled with sandy loam, and 1 (1+/) of pathogenic soil in which the white leaf blight fungus had been cultured was uniformly inoculated onto the soil surface. Preparation The test compound made into a hydrating powder according to Example 1 was diluted with water, and a predetermined amount of the compound was sprinkled onto the soil. After 2 hours, the green beans (
Ten seeds of the cultivar Nibonkintoki) were sown each. After sowing 1
The plants were grown in a greenhouse for 4 days and their pesticidal efficacy was investigated. The results are shown in Table 6.

Table 6 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 that had developed their first true leaves were inoculated with spores of the wheat rust fungus.

After inoculation, the plants were grown for 16 hours at 28°C under high humidity, and the test compound was made into a suspension according to Formulation Example 4, diluted with water to a predetermined concentration, and sprayed on the foliage to ensure sufficient adhesion to the leaf surface. . After spraying, the plants were grown for 10 days under fluorescent lighting at 28°C, and their pesticidal efficacy was investigated. The results are shown in Table 7.

Table 7

Claims (1)

[Scope of 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] [In the formula, X has the same meaning as above. ] A method for producing an indanylbenzamide derivative. (8) General formula [wherein X represents a methyl group, a nitro group, a halogen atom or a trifluoromethyl group. ] A general formula characterized by isomerizing a benzoyltetrahydroquinoline derivative represented by the following in the presence of an acid catalyst [wherein X has the same meaning as above]. ] A method for producing an indanylbenzamide m conductor (7). (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,